JP6183900B2 - Base proliferating agent-encapsulated microcapsule, method for producing base proliferating agent-encapsulated microcapsule, and photosensitive epoxy resin composition - Google Patents
Base proliferating agent-encapsulated microcapsule, method for producing base proliferating agent-encapsulated microcapsule, and photosensitive epoxy resin composition Download PDFInfo
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- JP6183900B2 JP6183900B2 JP2013234416A JP2013234416A JP6183900B2 JP 6183900 B2 JP6183900 B2 JP 6183900B2 JP 2013234416 A JP2013234416 A JP 2013234416A JP 2013234416 A JP2013234416 A JP 2013234416A JP 6183900 B2 JP6183900 B2 JP 6183900B2
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- Prior art keywords
- base
- proliferating agent
- base proliferating
- epoxy resin
- encapsulated
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- 239000003094 microcapsule Substances 0.000 title claims description 92
- 230000002062 proliferating effect Effects 0.000 title claims description 88
- 239000003822 epoxy resin Substances 0.000 title claims description 70
- 229920000647 polyepoxide Polymers 0.000 title claims description 70
- 239000000203 mixture Substances 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 63
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 229920000642 polymer Polymers 0.000 claims description 31
- 239000000178 monomer Substances 0.000 claims description 30
- 239000002585 base Substances 0.000 description 192
- -1 amine compound Chemical class 0.000 description 21
- 239000002245 particle Substances 0.000 description 19
- 239000000126 substance Substances 0.000 description 16
- 230000035755 proliferation Effects 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 150000003254 radicals Chemical class 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- 239000002270 dispersing agent Substances 0.000 description 10
- 238000003860 storage Methods 0.000 description 9
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 8
- 239000003995 emulsifying agent Substances 0.000 description 8
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 238000013329 compounding Methods 0.000 description 6
- 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 6
- 239000002904 solvent Substances 0.000 description 6
- 238000007720 emulsion polymerization reaction Methods 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- BFXRTDMOQOYJTP-UHFFFAOYSA-N (4,5-dimethoxy-2-nitrophenyl)methylcarbamic acid Chemical compound COC1=CC(CNC(O)=O)=C([N+]([O-])=O)C=C1OC BFXRTDMOQOYJTP-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 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 3
- 239000002775 capsule Substances 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 238000012674 dispersion polymerization Methods 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 2
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products 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
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 229920002396 Polyurea Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-O guanidinium Chemical compound NC(N)=[NH2+] ZRALSGWEFCBTJO-UHFFFAOYSA-O 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 230000000644 propagated effect Effects 0.000 description 2
- RGBXDEHYFWDBKD-UHFFFAOYSA-N propan-2-yl propan-2-yloxy carbonate Chemical compound CC(C)OOC(=O)OC(C)C RGBXDEHYFWDBKD-UHFFFAOYSA-N 0.000 description 2
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 2
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- 238000003756 stirring Methods 0.000 description 2
- 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 2
- BOOBDAVNHSOIDB-UHFFFAOYSA-N (2,3-dichlorobenzoyl) 2,3-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC=CC(C(=O)OOC(=O)C=2C(=C(Cl)C=CC=2)Cl)=C1Cl BOOBDAVNHSOIDB-UHFFFAOYSA-N 0.000 description 1
- JMYZLRSSLFFUQN-UHFFFAOYSA-N (2-chlorobenzoyl) 2-chlorobenzenecarboperoxoate Chemical compound ClC1=CC=CC=C1C(=O)OOC(=O)C1=CC=CC=C1Cl JMYZLRSSLFFUQN-UHFFFAOYSA-N 0.000 description 1
- AWOKSNNHYRGYIA-UHFFFAOYSA-N (4,5-dimethoxy-2-nitrophenyl)methyl carbamate Chemical compound COC1=CC(COC(N)=O)=C([N+]([O-])=O)C=C1OC AWOKSNNHYRGYIA-UHFFFAOYSA-N 0.000 description 1
- MIJOCHWITRUYLZ-UHFFFAOYSA-N 1,1-dimethoxyethyl N-benzylcarbamate Chemical class COC(OC(NCC1=CC=CC=C1)=O)(C)OC MIJOCHWITRUYLZ-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
- YWBMNCRJFZGXJY-UHFFFAOYSA-N 1-hydroperoxy-1,2,3,4-tetrahydronaphthalene Chemical compound C1=CC=C2C(OO)CCCC2=C1 YWBMNCRJFZGXJY-UHFFFAOYSA-N 0.000 description 1
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
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- WZHRFIACUJRXNQ-UHFFFAOYSA-N 2-[(1-amino-2-cyclopropyl-1-iminopropan-2-yl)diazenyl]-2-cyclopropylpropanimidamide Chemical compound C1CC1C(C(N)=N)(C)N=NC(C)(C(N)=N)C1CC1 WZHRFIACUJRXNQ-UHFFFAOYSA-N 0.000 description 1
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- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
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- 150000003868 ammonium compounds Chemical class 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- ZWDNVDDEDBXBMD-UHFFFAOYSA-N anthracen-9-ylmethyl n,n-diethylcarbamate Chemical compound C1=CC=C2C(COC(=O)N(CC)CC)=C(C=CC=C3)C3=CC2=C1 ZWDNVDDEDBXBMD-UHFFFAOYSA-N 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 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
- NEPKLUNSRVEBIX-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OCC2OC2)C=CC=1C(=O)OCC1CO1 NEPKLUNSRVEBIX-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
- KTPIWUHKYIJBCR-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohex-4-ene-1,2-dicarboxylate Chemical compound C1C=CCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 KTPIWUHKYIJBCR-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
- KBWLNCUTNDKMPN-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) hexanedioate Chemical compound C1OC1COC(=O)CCCCC(=O)OCC1CO1 KBWLNCUTNDKMPN-UHFFFAOYSA-N 0.000 description 1
- GYCUTPICSQQWKP-UHFFFAOYSA-N bis[2-(5-methyl-4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene Chemical compound N1C(C)CN=C1C(C)(C)N=NC(C)(C)C1=NCC(C)N1 GYCUTPICSQQWKP-UHFFFAOYSA-N 0.000 description 1
- KULVLHITTUZALN-UHFFFAOYSA-N bromomethyl benzenecarboperoxoate Chemical compound BrCOOC(=O)C1=CC=CC=C1 KULVLHITTUZALN-UHFFFAOYSA-N 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- VBWIZSYFQSOUFQ-UHFFFAOYSA-N cyclohexanecarbonitrile Chemical compound N#CC1CCCCC1 VBWIZSYFQSOUFQ-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
- PAFZNILMFXTMIY-UHFFFAOYSA-O cyclohexylammonium Chemical compound [NH3+]C1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-O 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-O dicyclohexylazanium Chemical compound C1CCCCC1[NH2+]C1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-O 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 125000005842 heteroatom Chemical group 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
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229940047889 isobutyramide Drugs 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-M isobutyrate Chemical compound CC(C)C([O-])=O KQNPFQTWMSNSAP-UHFFFAOYSA-M 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- WVFLGSMUPMVNTQ-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-[[1-(2-hydroxyethylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCO WVFLGSMUPMVNTQ-UHFFFAOYSA-N 0.000 description 1
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- AMEVLYGGLRIBIO-UHFFFAOYSA-N octoxycarbonyloxy octyl carbonate Chemical compound CCCCCCCCOC(=O)OOC(=O)OCCCCCCCC AMEVLYGGLRIBIO-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920001290 polyvinyl ester Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- KOPQZJAYZFAPBC-UHFFFAOYSA-N propanoyl propaneperoxoate Chemical compound CCC(=O)OOC(=O)CC KOPQZJAYZFAPBC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Description
本発明は、貯蔵安定性にも硬化特性にも優れた硬化剤としてエポキシ樹脂等の硬化に好適に用いられる塩基増殖剤封入マイクロカプセルに関する。また、本発明は、該塩基増殖剤封入マイクロカプセルの製造方法、及び、該塩基増殖剤封入マイクロカプセルを含有する感光性エポキシ樹脂組成物に関する。 The present invention relates to a base proliferating agent-encapsulated microcapsule suitably used for curing an epoxy resin or the like as a curing agent having excellent storage stability and curing characteristics. The present invention also relates to a method for producing the base proliferating agent-encapsulated microcapsules and a photosensitive epoxy resin composition containing the base proliferating agent-encapsulated microcapsules.
エポキシ樹脂に代表される、塩基により重合又は架橋され硬化する材料は、接着剤、シール剤、コーティング剤、賦型剤等の様々な用途に用いられている。一般的に、エポキシ樹脂には、硬化反応を進行させるための成分（即ち、塩基）としてアミン系等の硬化剤及び／又は硬化促進剤が添加される。特に、硬化剤又は硬化促進剤とエポキシ樹脂とを一液にするために、潜在性をもたせた硬化剤又は硬化促進剤が多用されている。 Materials that are polymerized or cross-linked by a base, such as epoxy resins, and are cured are used in various applications such as adhesives, sealants, coating agents, and shaping agents. Generally, an amine-based curing agent and / or curing accelerator is added to the epoxy resin as a component (that is, a base) for advancing the curing reaction. In particular, in order to make the curing agent or the curing accelerator and the epoxy resin into one liquid, a latent curing agent or curing accelerator is frequently used.
例えば、特許文献１には、所定の粉末状アミン化合物（Ａ）をコアとし、上記アミン化合物（Ａ）とエポキシ樹脂（Ｂ）の反応生成物をシェルとしてなる硬化剤が記載されている。また、特許文献２には、アミンアダクト（Ａ）と低分子アミン化合物（Ｂ）を主成分とする所定のエポキシ樹脂用硬化剤（Ｃ）からなるコアの表面を所定のシェルによって被覆されている構造を持つマイクロカプセル型エポキシ樹脂用硬化剤が記載されている。
しかしながら、特許文献１及び２に記載のマイクロカプセルは、アミン系硬化剤とエポキシ樹脂とを途中段階まで反応させて得られた粉体であり、アミン系硬化剤とエポキシ樹脂との接触界面が硬化しているにすぎない。そのため、このようなマイクロカプセルは時間の経過とともに硬化反応が進行しやすく、充分な貯蔵安定性を得ることは困難である。また、このようなマイクロカプセルは硬化時にシェルの架橋も進行することから、内包された硬化剤又は硬化促進剤が充分に放出されず、その結果、エポキシ樹脂が充分に硬化しないという問題もある。
For example, Patent Document 1 describes a curing agent having a predetermined powdery amine compound (A) as a core and a reaction product of the amine compound (A) and the epoxy resin (B) as a shell. Moreover, in patent document 2, the surface of the core which consists of the predetermined | prescribed hardening | curing agent for epoxy resins (C) which has an amine adduct (A) and a low molecular weight amine compound (B) as a main component is coat | covered with the predetermined | prescribed shell. A microcapsule type epoxy resin curing agent having a structure is described.
However, the microcapsules described in Patent Documents 1 and 2 are powders obtained by reacting an amine curing agent and an epoxy resin to an intermediate stage, and the contact interface between the amine curing agent and the epoxy resin is cured. I'm just doing it. Therefore, such a microcapsule is likely to undergo a curing reaction over time, and it is difficult to obtain sufficient storage stability. Further, since such microcapsules also undergo crosslinking of the shell during curing, there is a problem that the encapsulated curing agent or curing accelerator is not sufficiently released, and as a result, the epoxy resin is not sufficiently cured.
近年、貯蔵安定性と硬化特性とを両立できる材料として、活性エネルギー線を照射したり、熱を与えたりすることによって塩基を発生する「塩基発生剤」が知られており、更に、塩基発生剤等により発生した塩基によって塩基増殖反応を引き起こす「塩基増殖剤」も提案されている。例えば、特許文献３には、塩基の作用によって新たな塩基を発生し、かつ塩基増殖反応が効率的に進行し得る塩基増殖剤が記載されている。特許文献３に記載の塩基増殖剤は、塩基源がなければ貯蔵安定性に優れるものである。
しかしながら、特許文献３に記載の塩基増殖剤が分子レベルでエポキシ樹脂中に配合されている場合、発生した塩基がエポキシ樹脂の硬化に使用されてしまい、塩基増殖反応が充分には進行しないことがある。
In recent years, “base generators” that generate bases by irradiating active energy rays or applying heat have been known as materials that can achieve both storage stability and curing characteristics. A “base proliferating agent” that causes a base proliferative reaction by a base generated by the above has also been proposed. For example, Patent Document 3 describes a base proliferating agent that generates a new base by the action of a base and that allows a base proliferating reaction to proceed efficiently. The base proliferating agent described in Patent Document 3 is excellent in storage stability without a base source.
However, when the base proliferating agent described in Patent Document 3 is blended in the epoxy resin at the molecular level, the generated base is used for curing the epoxy resin, and the base proliferating reaction may not proceed sufficiently. is there.
そこで、本願出願人らは、特許文献４に、表面に活性エネルギー線又は熱によって塩基が生成する基を有する、所定のラジカル重合性モノマーを重合させることによって得られる微粒子を提案している。
特許文献４に記載の微粒子においては、塩基発生剤等により発生した塩基が粒子表面に到達すると、塩基増殖反応が粒子内部で起こって粒子内部で充分な塩基濃度になるため、エポキシ樹脂中へ拡散するまで、塩基増殖反応によって発生した塩基はエポキシ樹脂の硬化には使用されない。そのため、特許文献４に記載の微粒子は、極めて効率的に塩基増殖反応が進行し、その結果、硬化に充分な塩基を供給できるものである。
しかしながら、特許文献４に記載の微粒子は、粒子全体がポリマーからなるものであり、粒子内部での塩基増殖反応速度（塩基発生速度）には限界がある。従って、塩基発生速度を更に向上させ、エポキシ樹脂の硬化特性を高めることが求められている。
Therefore, the applicants of the present application have proposed, in Patent Document 4, fine particles obtained by polymerizing a predetermined radical polymerizable monomer having a group that generates a base by active energy rays or heat on the surface.
In the fine particles described in Patent Document 4, when a base generated by a base generator or the like reaches the particle surface, a base multiplication reaction takes place inside the particle, resulting in a sufficient base concentration inside the particle, so that it diffuses into the epoxy resin. Until then, the base generated by the base propagation reaction is not used to cure the epoxy resin. For this reason, the fine particles described in Patent Document 4 have a very efficient base multiplication reaction, and as a result, can supply a sufficient base for curing.
However, the fine particles described in Patent Document 4 are composed entirely of polymer, and there is a limit to the base growth reaction rate (base generation rate) inside the particle. Accordingly, there is a demand for further improving the base generation rate and enhancing the curing characteristics of the epoxy resin.
本発明は、貯蔵安定性にも硬化特性にも優れた硬化剤としてエポキシ樹脂等の硬化に好適に用いられる塩基増殖剤封入マイクロカプセルを提供することを目的とする。また、本発明は、該塩基増殖剤封入マイクロカプセルの製造方法、及び、該塩基増殖剤封入マイクロカプセルを含有する感光性エポキシ樹脂組成物を提供することを目的とする。 An object of the present invention is to provide a base proliferating agent-encapsulated microcapsule suitably used for curing an epoxy resin or the like as a curing agent having excellent storage stability and curing characteristics. Another object of the present invention is to provide a method for producing the base proliferating agent-encapsulated microcapsules and a photosensitive epoxy resin composition containing the base proliferating agent-encapsulated microcapsules.
本発明は、シェルに、塩基増殖反応を引き起こす基を有する塩基増殖剤がコアとして封入されている塩基増殖剤封入マイクロカプセルである。
以下、本発明を詳述する。
The present invention relates to a base proliferating agent-encapsulated microcapsule in which a base proliferating agent having a group that causes a base proliferating reaction is encapsulated in a shell as a core.
The present invention is described in detail below.
本発明者らは、シェルに、塩基増殖反応を引き起こす基を有する塩基増殖剤がコアとして封入されている塩基増殖剤封入マイクロカプセルにおいては、塩基増殖反応がシェルの内部で起こるため、塩基増殖反応のみが選択的に進行し、マイクロカプセルという限られた空間内で極めて高濃度の塩基が高速に発生すること、また、このような塩基増殖剤封入マクロカプセルをエポキシ樹脂等へ分散させた場合、シェルの内部で発生した高濃度の塩基を一気に放出できるため、エポキシ樹脂等の硬化特性が向上することを見出した。
更に、塩基発生剤等により発生した塩基がシェルの内部に取り込まれ、シェルの内部で塩基増殖反応が進行し、更に、マイクロカプセルから放出された塩基が、隣接するマイクロカプセルのシェルの内部に取り込まれ、塩基増殖反応が進行するという連鎖的な塩基増殖反応が進行する。このため、光の届かないところへも塩基を伝搬することができるため、厚膜のエポキシ樹脂等を硬化することができる。
更に、このような塩基増殖剤封入マイクロカプセルにおいては、塩基増殖反応がシェルの内部で起こるため、塩基増殖反応によって発生した塩基がエポキシ樹脂等の硬化に使用されてしまうことを抑制することもできる。
本発明者らは、このような塩基増殖剤封入マイクロカプセルは、貯蔵安定性にも硬化特性にも優れた硬化剤としてエポキシ樹脂等の硬化に好適に用いられることを見出し、本発明を完成させるに至った。
In the base proliferating agent-encapsulated microcapsules in which a base proliferating agent having a group that causes a base proliferating reaction is encapsulated in the shell, the base proliferating reaction occurs inside the shell. Only when it proceeds selectively, a very high concentration of base is generated at a high speed in a limited space called a microcapsule, and when such a base proliferating agent-encapsulated macrocapsule is dispersed in an epoxy resin, It was found that the high concentration of the base generated inside the shell can be released at once, so that the curing characteristics of epoxy resin and the like are improved.
Furthermore, the base generated by the base generator or the like is taken into the shell, and the base proliferation reaction proceeds inside the shell, and further, the base released from the microcapsule is taken into the shell of the adjacent microcapsule. As a result, a chain base proliferation reaction that a base proliferation reaction proceeds proceeds. For this reason, since a base can be propagated to a place where light does not reach, a thick film epoxy resin or the like can be cured.
Furthermore, in such a microcapsule encapsulating a base proliferating agent, since the base proliferating reaction occurs inside the shell, it is possible to prevent the base generated by the base proliferating reaction from being used for curing an epoxy resin or the like. .
The present inventors have found that such a base proliferating agent-encapsulated microcapsule is suitably used for curing an epoxy resin or the like as a curing agent having excellent storage stability and curing characteristics, and completes the present invention. It came to.
（塩基増殖剤）
本発明の塩基増殖剤封入マイクロカプセルは、シェルに、塩基増殖反応を引き起こす基を有する塩基増殖剤がコアとして封入されているものである。
(Base proliferating agent)
The base proliferating agent-encapsulated microcapsules of the present invention are those in which a base proliferating agent having a group that causes a base proliferating reaction is encapsulated in a shell as a core.
上記塩基増殖剤は、塩基増殖反応を引き起こす基を有するものであり、低分子化合物であってもよいし、高分子化合物であってもよい。なかでも、塩基発生速度が更に増すことから、低分子化合物が好ましい。
本明細書中、塩基増殖反応を引き起こす基とは、塩基発生剤等により発生した塩基の存在下で加熱される等により分解し、新たに塩基を発生する基をいう。発生した塩基は新たな触媒として機能し、自己触媒的に多数の塩基を発生する。
このようにして発生した塩基は硬化剤となってエポキシ樹脂等と反応し、硬化物を形成することから、本発明の塩基増殖剤封入マイクロカプセルは、エポキシ樹脂等の硬化に好適に用いられる。また、上記塩基増殖反応を引き起こす基は、塩基発生剤等により発生した塩基の作用ではじめて分解することから、本発明の塩基増殖剤封入マイクロカプセルは、エポキシ樹脂等に配合されても、得られる硬化性樹脂組成物の貯蔵安定性を低下させることはない。
The base proliferating agent has a group that causes a base proliferating reaction, and may be a low molecular compound or a high molecular compound. Of these, low molecular weight compounds are preferred because the base generation rate is further increased.
In the present specification, a group that causes a base proliferation reaction refers to a group that decomposes when heated in the presence of a base generated by a base generator or the like to newly generate a base. The generated base functions as a new catalyst and generates a large number of bases in an autocatalytic manner.
The base generated in this manner becomes a curing agent and reacts with the epoxy resin or the like to form a cured product. Therefore, the base proliferating agent-encapsulated microcapsules of the present invention are suitably used for curing an epoxy resin or the like. In addition, since the group causing the base proliferation reaction is decomposed only by the action of the base generated by the base generator or the like, the base capsule encapsulating microcapsules of the present invention can be obtained even when blended in an epoxy resin or the like. The storage stability of the curable resin composition is not lowered.
上記塩基増殖反応を引き起こす基は、塩基発生剤等により発生した塩基の存在下で、分解し、新たに塩基を発生することが好ましい。 The group causing the base proliferation reaction is preferably decomposed in the presence of a base generated by a base generator or the like to newly generate a base.
上記塩基増殖反応を引き起こす基は特に限定されないが、下記一般式（１）で表される塩基増殖反応を引き起こす構造を有することが好ましい。 The group causing the base proliferation reaction is not particularly limited, but preferably has a structure causing the base proliferation reaction represented by the following general formula (1).
一般式（１）中、Ｒ１及びＲ２はそれぞれ水素又は炭化水素基であるか、或いは、連結して含窒素環を形成するものである。 In the general formula (1), R 1 and R 2 are each hydrogen or a hydrocarbon group, or are linked to form a nitrogen-containing ring.
上記炭化水素基として、例えば、炭素数１〜１８のアルキル基、炭素数５〜１０のシクロアルキル基、炭素数６〜１４のアリール基、炭素数７〜１５のアリールアルキル基等が挙げられる。具体的には例えば、エチル基、プロピル基、ブチル基、ヘキシル基、シクロヘキシル基、シクロオクチル基、フェニル基、トリル基、ナフチル基、ベンジル基、フェネチル基、ナフチルメチル基が挙げられる。
上記炭化水素基は、アミノ基、アルコキシ基、アルコキシカルボニル基、アシル基、アシルオキシ基、ヒロドロキシル基等の置換基を有していてもよい。
上記Ｒ１及びＲ２は、連結して含窒素環を形成してもよい。この場合、含窒素環は、構成原子として複数のヘテロ原子（窒素、酸素、硫黄等）を含有してもよい。
Examples of the hydrocarbon group include an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an arylalkyl group having 7 to 15 carbon atoms. Specific examples include an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, a cyclooctyl group, a phenyl group, a tolyl group, a naphthyl group, a benzyl group, a phenethyl group, and a naphthylmethyl group.
The hydrocarbon group may have a substituent such as an amino group, an alkoxy group, an alkoxycarbonyl group, an acyl group, an acyloxy group, or a hydroxyl group.
R 1 and R 2 may be linked to form a nitrogen-containing ring. In this case, the nitrogen-containing ring may contain a plurality of heteroatoms (nitrogen, oxygen, sulfur, etc.) as constituent atoms.
上記一般式（１）で表される塩基増殖反応を引き起こす構造を有する塩基増殖剤として、例えば、下記式（１−１）〜（１−１４）で表される塩基増殖剤が挙げられる。 Examples of the base proliferating agent having a structure that causes the base proliferating reaction represented by the general formula (1) include base proliferating agents represented by the following formulas (1-1) to (1-14).
（塩基発生剤）
本発明の塩基増殖剤封入マイクロカプセルにおいては、上記塩基増殖剤に加えて、更に、塩基発生剤がコアとして封入されていることが好ましい。
本明細書中、塩基発生剤とは、活性エネルギー線を照射したり、熱を与えたりすることによって塩基を発生する物質をいう。なお、活性エネルギー線として、例えば、赤外線、可視光線、紫外線等の光や、Ｘ線、γ線等の放射線や、イオンビーム等が挙げられる。
(Base generator)
In the base proliferating agent-encapsulated microcapsule of the present invention, in addition to the base proliferating agent, a base generator is preferably encapsulated as a core.
In the present specification, the base generator refers to a substance that generates a base by irradiating active energy rays or applying heat. Examples of active energy rays include light such as infrared rays, visible rays, and ultraviolet rays, radiation such as X-rays and γ rays, ion beams, and the like.
上記塩基発生剤のうち、光を照射することによって塩基を発生する光塩基発生剤としては、例えば、オキシムエステル系化合物、アンモニウム系化合物、ベンゾイン系化合物、ジメトキシベンジルウレタン系化合物、オルトニトロベンジツウレタン系化合物等が挙げられる。具体的には例えば、９−アンスリルメチル Ｎ，Ｎ−ジエチルカルバメート、（Ｅ）−１−［３−（２−ヒドロキシフェニル）−２−プロペノイル］ピペリジン、グアニジニウム２−（３−ベンゾイルフェニル）プロピオネート、１−（アントラキノン−２−イル）エチルイミダゾールカルボキシレート、２−ニトロフェニルメチル４−メタクリロイルオキシピペリジン−１−カルボキシラート、１−（アントラキノン−２−イル）−エチルＮ，Ｎ−ジシクロヘキシルカルバメート、ジシクロヘキシルアンモニウム２−（３−ベンゾイルフェニル）プロピオネート、シクロヘキシルアンモニウム２−（３−ベンゾイルフェニル）プロピオナート、９−アントリルメチルＮ，Ｎ−ジシクロヘキシルカルバメート、１，２−ジイソプロピル−３−〔ビス（ジメチルアミノ）メチレン〕グアニジウム２−（３−ベンゾイルフェニル）プロピオネート、１，６−ヘキサメチレン−ビス（４，５−ジメトキシ−２−ニトロベンジルカルバメート）等が好ましい。 Among the above base generators, examples of the photobase generator that generates a base upon irradiation with light include oxime ester compounds, ammonium compounds, benzoin compounds, dimethoxybenzyl urethane compounds, and orthonitrobenzurethanes. System compounds and the like. Specifically, for example, 9-anthrylmethyl N, N-diethylcarbamate, (E) -1- [3- (2-hydroxyphenyl) -2-propenoyl] piperidine, guanidinium 2- (3-benzoylphenyl) propionate 1- (anthraquinone-2-yl) ethylimidazole carboxylate, 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate, 1- (anthraquinone-2-yl) -ethyl N, N-dicyclohexyl carbamate, dicyclohexyl Ammonium 2- (3-benzoylphenyl) propionate, cyclohexylammonium 2- (3-benzoylphenyl) propionate, 9-anthrylmethyl N, N-dicyclohexylcarbamate, 1,2-diisopropyl-3- Bis (dimethylamino) methylene] guanidinium 2- (3-benzoylphenyl) propionate, 1,6-hexamethylene - bis (4,5-dimethoxy-2-nitrobenzyl carbamate) and the like are preferable.
コアとして封入される上記塩基発生剤の配合量は特に限定されないが、上記塩基増殖剤１００重量部に対する好ましい下限が０．０１重量部、好ましい上限が１００重量部である。上記塩基発生剤の配合量が０．０１重量部未満であると、塩基増殖反応を開始させる塩基の発生量が少なすぎ、塩基増殖反応が極めて遅くなったり、充分な塩基増殖反応を開始させることができなくなったりすることがある。上記塩基発生剤の配合量が１００重量部を超えると、マイクロカプセル中の塩基増殖剤の含有量が少なくなりすぎ、充分な量の塩基が発生しないことがある。上記塩基発生剤の配合量は、上記塩基増殖剤１００重量部に対するより好ましい下限が０．１重量部、より好ましい上限が５０重量部である。 The blending amount of the base generator encapsulated as a core is not particularly limited, but a preferable lower limit with respect to 100 parts by weight of the base proliferating agent is 0.01 parts by weight, and a preferable upper limit is 100 parts by weight. When the blending amount of the base generator is less than 0.01 parts by weight, the amount of the base that initiates the base growth reaction is too small, the base growth reaction becomes extremely slow, or a sufficient base growth reaction is started. May become impossible. When the blending amount of the base generator exceeds 100 parts by weight, the content of the base proliferating agent in the microcapsules may become too small to generate a sufficient amount of base. As for the compounding quantity of the said base generator, the more preferable minimum with respect to 100 weight part of said base propagation agents is 0.1 weight part, and a more preferable upper limit is 50 weight part.
本発明の塩基増殖剤封入マイクロカプセルにおいては、上述した塩基増殖剤、必要に応じて添加される上述した塩基発生剤等が、コアとしてシェルに封入されている。
このような構造であることにより、塩基増殖反応がシェルの内部で起こるため、塩基増殖反応のみが選択的に進行し、マイクロカプセルという限られた空間内で極めて高濃度の塩基が高速に発生する。また、このような塩基増殖剤封入マクロカプセルをエポキシ樹脂等へ分散させた場合、シェルの内部で発生した高濃度の塩基を一気に放出できるため、エポキシ樹脂等の硬化特性が向上する。
更に、塩基発生剤等により発生した塩基がシェルの内部に取り込まれ、シェルの内部で塩基増殖反応が進行し、更に、マイクロカプセルから放出された塩基が、隣接するマイクロカプセルのシェルの内部に取り込まれ、塩基増殖反応が進行するという連鎖的な塩基増殖反応が進行する。このため、光の届かないところへも塩基を伝搬することができるため、厚膜のエポキシ樹脂等を硬化することができる。
更に、塩基増殖反応がシェルの内部で起こるため、塩基増殖反応によって発生した塩基がエポキシ樹脂等の硬化に使用されてしまうことを抑制することもできる。
In the base proliferating agent-encapsulated microcapsule of the present invention, the base proliferating agent described above, the base generating agent added as necessary, and the like are encapsulated in a shell as a core.
With this structure, the base growth reaction takes place inside the shell, so only the base growth reaction proceeds selectively, and a very high concentration of base is generated at high speed in a limited space called a microcapsule. . In addition, when such a base proliferating agent-encapsulated macrocapsule is dispersed in an epoxy resin or the like, a high concentration of the base generated inside the shell can be released at a stretch, so that the curing characteristics of the epoxy resin or the like are improved.
Furthermore, the base generated by the base generator or the like is taken into the shell, and the base proliferation reaction proceeds inside the shell, and further, the base released from the microcapsule is taken into the shell of the adjacent microcapsule. As a result, a chain base proliferation reaction that a base proliferation reaction proceeds proceeds. For this reason, since a base can be propagated to a place where light does not reach, a thick film epoxy resin or the like can be cured.
Furthermore, since the base multiplication reaction occurs inside the shell, it is possible to prevent the base generated by the base growth reaction from being used for curing an epoxy resin or the like.
上記シェルは、塩基により主鎖及び／又は側鎖が分解するポリマーを含有することが好ましい。このようなポリマーを含有するシェルは、塩基により崩壊しやすく、シェルの内部で発生した高濃度の塩基を一気に放出できるため、エポキシ樹脂等の硬化特性が更に向上する。 The shell preferably contains a polymer whose main chain and / or side chain is decomposed by a base. A shell containing such a polymer is easily broken by a base, and a high-concentration base generated inside the shell can be released all at once, so that the curing characteristics of an epoxy resin and the like are further improved.
（塩基により主鎖が分解するポリマー）
上記塩基により主鎖が分解するポリマーは、塩基により分解する基を主鎖中に有する。塩基により主鎖が分解するため、シェルの内部で発生した塩基によりシェルが崩壊しやすく、そのため、発生した塩基の放出が容易となる。
上記塩基により主鎖が分解するポリマーとしては、例えば、ポリエステル樹脂、ポリカーボネート樹脂、ポリウレタン樹脂、ポリウレア樹脂、ポリアミド樹脂、ポリエーテル樹脂等が挙げられる。なかでも、下記式（２−１）で表されるポリマーが好ましい。
(Polymer whose main chain is decomposed by base)
The polymer whose main chain is decomposed by the base has a group that is decomposed by the base in the main chain. Since the main chain is decomposed by the base, the shell is easily collapsed by the base generated inside the shell, and thus the generated base is easily released.
Examples of the polymer whose main chain is decomposed by the base include polyester resins, polycarbonate resins, polyurethane resins, polyurea resins, polyamide resins, and polyether resins. Among these, a polymer represented by the following formula (2-1) is preferable.
（塩基により側鎖が分解するポリマー）
上記塩基により側鎖が分解するポリマーは、塩基により分解する基を側鎖に有する。シェルの内部で発生した塩基によりポリマー側鎖が分解するため、シェル壁に緩みが生じ、そのため、発生した塩基の放出が容易となる。
上記塩基により側鎖が分解するポリマーとしては、例えば、ポリエステル樹脂、ポリカーボネート樹脂、ポリウレタン樹脂、ポリウレア樹脂、ポリアクリルアミド樹脂、ポリエーテル樹脂、ポリアセタール樹脂、ポリビニルエーテル樹脂、ポリビニルエステル樹脂、（メタ）アクリル樹脂等が挙げられる。なかでも、塩基により分解する基を有するラジカル重合性モノマーを主成分とするラジカル重合性モノマーを重合させることによって得られたポリマーであることが好ましい。
上記塩基により分解する基を有するラジカル重合性モノマーは特に限定されないが、下記一般式（３）で表されるモノマーが好ましい。
(Polymer whose side chain is decomposed by base)
The polymer whose side chain is decomposed by the base has a group that is decomposed by the base in the side chain. Since the polymer side chain is decomposed by the base generated inside the shell, the shell wall is loosened, so that the generated base is easily released.
Examples of the polymer whose side chain is decomposed by the base include, for example, polyester resin, polycarbonate resin, polyurethane resin, polyurea resin, polyacrylamide resin, polyether resin, polyacetal resin, polyvinyl ether resin, polyvinyl ester resin, (meth) acrylic resin. Etc. Especially, it is preferable that it is a polymer obtained by polymerizing the radically polymerizable monomer which has as a main component the radically polymerizable monomer which has the group decomposed | disassembled with a base.
Although the radically polymerizable monomer which has the group decomposed | disassembled by the said base is not specifically limited, The monomer represented by following General formula (3) is preferable.
上記一般式（３）で表されるモノマーとしては、具体的には例えば、下記式（３−１）〜（３−２３）で表されるモノマー等が挙げられる。 Specific examples of the monomer represented by the general formula (3) include monomers represented by the following formulas (3-1) to (3-23).
上記塩基により分解する基を有するラジカル重合性モノマーを主成分とするラジカル重合性モノマーは、必要に応じて、他のラジカル重合性モノマーを含有していてもよい。
上記他のラジカル重合性モノマーは特に限定されず、例えば、（メタ）アクリル酸、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸２−エチルヘキシル等の（メタ）アクリル酸及びそのエステル、（メタ）アクリルアミド、イソプロピルアクリルアミド等の（メタ）アクリルアミド誘導体、塩化ビニル、塩化ビニリデン、酢酸ビニル、メチルビニルエーテル、スチレン、ジビニルベンゼン、（メタ）アクリロニトリル等のビニルモノマー、イソプレン等の不飽和二重結合を有する化合物等が挙げられる。
The radical polymerizable monomer containing as a main component a radical polymerizable monomer having a group that can be decomposed by a base may contain other radical polymerizable monomers as necessary.
The other radical polymerizable monomer is not particularly limited. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate (Meth) acrylic acid and its esters, (meth) acrylamide derivatives such as (meth) acrylamide and isopropylacrylamide, vinyl chloride, vinylidene chloride, vinyl acetate, methyl vinyl ether, styrene, divinylbenzene, vinyl such as (meth) acrylonitrile Examples thereof include compounds having an unsaturated double bond such as a monomer and isoprene.
上記他のラジカル重合性モノマーの配合量は特に限定されないが、主成分である上記塩基により分解する基を有するラジカル重合性モノマー１００重量部に対する好ましい上限が５０重量部である。上記他のラジカル重合性モノマーの配合量が５０重量部を超えると、得られるシェル中の塩基により分解する基の含有量が少なくなり、塩基により分解された後のシェル壁の緩みが少なくなり、充分な塩基の放出が困難となることがある。 The blending amount of the other radical polymerizable monomer is not particularly limited, but a preferable upper limit with respect to 100 parts by weight of the radical polymerizable monomer having a group that is decomposed by the base as a main component is 50 parts by weight. When the blending amount of the other radical polymerizable monomer exceeds 50 parts by weight, the content of the group that is decomposed by the base in the resulting shell is reduced, and the shell wall is less loose after being decomposed by the base, It may be difficult to release sufficient base.
（塩基増殖剤封入マイクロカプセルの製造方法）
本発明の塩基増殖剤封入マイクロカプセルの製造方法は特に限定されず、例えば、少なくとも、コアを構成する塩基増殖反応を引き起こす基を有する塩基増殖剤と、シェルポリマーとの共存下、塩基増殖剤封入マイクロカプセルを製造することができる。この場合、例えば、乳化、転層乳化、析出法等の公知の方法を用いることができる。
また、少なくとも、コアを構成する塩基増殖反応を引き起こす基を有する塩基増殖剤と、シェルポリマーを形成するモノマーとの共存下、塩基増殖剤封入マイクロカプセルを製造することができる。この場合、例えば、懸濁重合、乳化重合、分散重合、転層乳化重合等の公知の方法を用いることができる。上記シェルポリマーを形成するモノマーは、上述した塩基により分解する基を有するラジカル重合性モノマーを含有するラジカル重合性モノマーが好ましい。
これらの塩基増殖剤封入マイクロカプセルの製造方法もまた、本発明の１つである。
(Manufacturing method of base capsule-encapsulating microcapsules)
The production method of the base proliferating agent-encapsulated microcapsule of the present invention is not particularly limited. For example, the base proliferating agent is encapsulated in the presence of at least a base proliferating agent having a group that causes a base proliferating reaction constituting the core and a shell polymer. Microcapsules can be manufactured. In this case, for example, known methods such as emulsification, inversion emulsification, and precipitation can be used.
In addition, a base proliferating agent-encapsulated microcapsule can be produced in the presence of at least a base proliferating agent having a group that causes a base proliferating reaction constituting the core and a monomer that forms a shell polymer. In this case, for example, known methods such as suspension polymerization, emulsion polymerization, dispersion polymerization, and phase inversion emulsion polymerization can be used. The monomer that forms the shell polymer is preferably a radical polymerizable monomer containing a radical polymerizable monomer having a group that can be decomposed by the above-described base.
The production method of these base proliferating agent-encapsulated microcapsules is also one aspect of the present invention.
（分散剤）
上記懸濁、懸濁重合又は分散重合を行う際の分散剤は特に限定されず、例えば、ポリビニルアルコール、ポリビニルピロリドン、アラビアガム、ゼラチン、アルキルセルロース、ヒドロキシアルキルセルロース、カルボキシアルキルセルロース、ポリアクリルアミド、ポリアクリル酸、ポリメタクリル酸、ポリアクリル酸アルキルエステル、ポリメタクリル酸アルキルエステル、コロイダルシリカ、ポリシロキサン等が挙げられる。
上記分散剤の配合量は特に限定されないが、上記シェルポリマー又は上記シェルポリマーを形成するモノマー１００重量部に対する好ましい下限が０．００１重量部、好ましい上限が１０重量部である。上記分散剤の配合量が０．００１重量部未満であると、分散剤を用いることによる分散安定効果が充分に得られないことがある。上記分散剤の配合量が１０重量部を超えると、得られるマイクロカプセルの表面への吸着等によりマイクロカプセルに取り込まれる分散剤が増加し、期待するシェルの特性が得られないことがある。
(Dispersant)
The dispersant used for the suspension, suspension polymerization or dispersion polymerization is not particularly limited. For example, polyvinyl alcohol, polyvinyl pyrrolidone, gum arabic, gelatin, alkyl cellulose, hydroxyalkyl cellulose, carboxyalkyl cellulose, polyacrylamide, polyacrylamide Examples include acrylic acid, polymethacrylic acid, polyacrylic acid alkyl ester, polymethacrylic acid alkyl ester, colloidal silica, and polysiloxane.
The blending amount of the dispersant is not particularly limited, but a preferable lower limit with respect to 100 parts by weight of the shell polymer or the monomer forming the shell polymer is 0.001 part by weight, and a preferable upper limit is 10 parts by weight. When the blending amount of the dispersant is less than 0.001 part by weight, the dispersion stabilizing effect by using the dispersant may not be sufficiently obtained. If the amount of the dispersant exceeds 10 parts by weight, the amount of the dispersant incorporated into the microcapsule increases due to adsorption to the surface of the obtained microcapsule, and the expected shell characteristics may not be obtained.
（乳化剤）
上記乳化又は乳化重合を行う際の乳化剤は特に限定されず、例えば、アルキル硫酸塩、アルキルスルホン酸塩、アルキルベンゼンスルホン酸塩、ポリオキシエチレンアルキルエーテル、アルキルアンモニウム塩等が挙げられる。
上記乳化剤の配合量は特に限定されないが、上記シェルポリマーを形成するモノマー１００重量部に対する好ましい下限が０．０１重量部、好ましい上限が１０重量部である。上記乳化剤の配合量が０．０１重量部未満であると、得られるマイクロカプセルの粒子径を充分に小さくすることができないことがあり、また、形成したマイクロカプセルが凝集してしまうことがある。上記乳化剤の配合量が１０重量部を超えると、得られるマイクロカプセルの粒子純度が低下することがある。
(emulsifier)
The emulsifier for carrying out the above emulsion or emulsion polymerization is not particularly limited, and examples thereof include alkyl sulfates, alkyl sulfonates, alkyl benzene sulfonates, polyoxyethylene alkyl ethers, and alkyl ammonium salts.
Although the compounding quantity of the said emulsifier is not specifically limited, The preferable minimum with respect to 100 weight part of monomers which form the said shell polymer is 0.01 weight part, and a preferable upper limit is 10 weight part. If the amount of the emulsifier is less than 0.01 parts by weight, the particle size of the obtained microcapsules may not be sufficiently reduced, and the formed microcapsules may aggregate. When the compounding amount of the emulsifier exceeds 10 parts by weight, the particle purity of the obtained microcapsules may be lowered.
（溶媒）
本発明の塩基増殖剤封入マイクロカプセルは、水及び／又は有機溶剤中で製造される。このような溶媒は特に限定されず、塩基増殖剤、シェルポリマー又はシェルポリマーを形成するモノマー等の種類、或いは、製造方法によって異なるが、水、メタノール、エタノール、イソプロピルアルコール、シクロヘキサン、トルエン、キシレン及びこれらの混合物が好ましい。
(solvent)
The base growth agent-encapsulated microcapsules of the present invention are produced in water and / or an organic solvent. Such a solvent is not particularly limited, and varies depending on the type of the base proliferating agent, the shell polymer or the monomer forming the shell polymer, or the production method, but water, methanol, ethanol, isopropyl alcohol, cyclohexane, toluene, xylene and These mixtures are preferred.
（重合開始剤）
本発明の塩基増殖剤封入マイクロカプセルが、懸濁重合、乳化重合、分散重合、転層乳化重合等により製造される場合、ラジカル重合開始剤等の重合開始剤が用いられる。このような重合開始剤は、シェルポリマーを形成するモノマーの種類又は溶媒によって適宜選択される。
上記ラジカル重合開始剤は、親油性であっても、親水性であってもよい。上記ラジカル重合開始剤として、例えば、過酸化物、アゾ化合物等が挙げられる。
親油性の過酸化物は特に限定されず、例えば、ベンゾイルパーオキサイド、ジイソプロピルパーオキシカーボネート、ジオクチルパーオキシジカーボネート、ｔ−ブチルパーオキシラウレート、ラウロイルパーオキサイド、ジオクタノイルパーオキサイド等が挙げられる。親油性のアゾ化合物は特に限定されず、例えば、アゾビスイソブチロニトリル、アゾビス（２，４−ジメチルバレロニトリル）、１，１−アゾビス（シクロヘキサン−１−カルボニトリル）、ジメチル２，２−アゾビス（２−メチルプロピオネート）等が挙げられる。また、親油性のラジカル重合開始剤として、ＡＩＢＮ、Ｉｒｇａｃｕｒｅ８１９等の光ラジカル重合開始剤を用いてもよい。これらは単独で用いられてもよく、２種以上が併用されてもよい。
(Polymerization initiator)
When the base capsule encapsulating microcapsules of the present invention are produced by suspension polymerization, emulsion polymerization, dispersion polymerization, phase inversion emulsion polymerization, or the like, a polymerization initiator such as a radical polymerization initiator is used. Such a polymerization initiator is appropriately selected depending on the type of monomer or solvent that forms the shell polymer.
The radical polymerization initiator may be lipophilic or hydrophilic. Examples of the radical polymerization initiator include peroxides and azo compounds.
The lipophilic peroxide is not particularly limited, and examples thereof include benzoyl peroxide, diisopropyl peroxycarbonate, dioctyl peroxydicarbonate, t-butyl peroxylaurate, lauroyl peroxide, dioctanoyl peroxide and the like. . The lipophilic azo compound is not particularly limited. For example, azobisisobutyronitrile, azobis (2,4-dimethylvaleronitrile), 1,1-azobis (cyclohexane-1-carbonitrile), dimethyl 2,2- And azobis (2-methylpropionate). Moreover, you may use photoradical polymerization initiators, such as AIBN and Irgacure819, as a lipophilic radical polymerization initiator. These may be used independently and 2 or more types may be used together.
親水性の過酸化物は特に限定されず、例えば、過酸化水素、過酸化アセチル、過酸化クミル、過酸化ｔ−ブチル、過酸化プロピオニル、過酸化ベンゾイル、過酸化クロロベンゾイル、過酸化ジクロロベンゾイル、過酸化ブロモメチルベンゾイル、過酸化ラウロイル、過硫酸アンモニウム、過硫酸ナトリウム、過硫酸カリウム、ペルオキシ炭酸ジイソプロピル、テトラリンヒドロペルオキシド、１−フェニル−２−メチルプロピル−１−ヒドロペルオキシド、過トリフェニル酢酸ｔ−ブチルヒドロペルオキシド、過蟻酸ｔ−ブチル、過酢酸ｔ−ブチル、過安息香酸ｔ−ブチル、過フェニル酢酸ｔ−ブチル、過メトキシ酢酸ｔ−ブチル、過Ｎ−（３−トルイル）カルバミン酸ｔ−ブチル、重硫酸アンモニウム、重硫酸ナトリウム等が挙げられる。親水性のアゾ化合物は特に限定されず、例えば、２，２’−アゾビス（２−アミジノプロパン）、２，２’−アゾビス（Ｎ，Ｎ’−ジメチレンイソブチルアミジン）、２，２’−アゾビス［２−（５−メチル−２−イミダゾリン−２−イル）プロパン］、１，１’−アゾビス（１−アミジノ−１−シクロプロピルエタン）、２，２’−アゾビス（２−アミジノ−４−メチルペンタン）、２，２’−アゾビス（２−Ｎ−フェニルアミノアミジノプロパン）、２，２’−アゾビス（１−イミノ−１−エチルアミノ−２−メチルプロパン）、２，２’−アゾビス（１−アリルアミノ−１−イミノ−２−メチルブタン）、２，２’−アゾビス（２−Ｎ−シクロへキシルアミジノプロパン）、２，２’−アゾビス（２−Ｎ−ベンジルアミジノプロパン）及びその塩酸、硫酸、酢酸塩等、４，４’−アゾビス（４−シアノ吉草酸）及びそのアルカリ金属塩、アンモニウム塩、アミン塩等、２−（カルバモイルアゾ）イソブチロニトリル、２，２’−アゾビス（イソブチルアミド）、２，２’−アゾビス［２−メチル−Ｎ−（２−ヒドロキシエチル）プロピオンアミド］、２，２’−アゾビス［２−メチル−Ｎ−（１，１’−ビス（ヒドロキシメチル）エチル）プロピオンアミド］、２，２’−アゾビス［２−メチル−Ｎ−１，１’−ビス（ヒドロキシエチル）プロピオンアミド］、２，２’−アゾビス［Ｎ−（２−カルボキシエチル）−２−メチルプロピオンアミド］等が挙げられる。これらは単独で用いられてもよく、２種以上が併用されてもよい。 The hydrophilic peroxide is not particularly limited. For example, hydrogen peroxide, acetyl peroxide, cumyl peroxide, t-butyl peroxide, propionyl peroxide, benzoyl peroxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, Bromomethylbenzoyl peroxide, lauroyl peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, t-butyl perphenylacetate Hydroperoxide, t-butyl performate, t-butyl peracetate, t-butyl perbenzoate, t-butyl perphenylacetate, t-butyl permethoxyacetate, t-butyl per-N- (3-toluyl) carbamate, Examples thereof include ammonium bisulfate and sodium bisulfate. The hydrophilic azo compound is not particularly limited. For example, 2,2′-azobis (2-amidinopropane), 2,2′-azobis (N, N′-dimethyleneisobutylamidine), 2,2′-azobis [2- (5-Methyl-2-imidazolin-2-yl) propane], 1,1′-azobis (1-amidino-1-cyclopropylethane), 2,2′-azobis (2-amidino-4- Methylpentane), 2,2′-azobis (2-N-phenylaminoamidinopropane), 2,2′-azobis (1-imino-1-ethylamino-2-methylpropane), 2,2′-azobis ( 1-allylamino-1-imino-2-methylbutane), 2,2′-azobis (2-N-cyclohexylamidinopropane), 2,2′-azobis (2-N-benzylamidinopropane) And hydrochloric acid, sulfuric acid, acetate, etc., 4,4′-azobis (4-cyanovaleric acid) and alkali metal salts, ammonium salts, amine salts thereof, 2- (carbamoylazo) isobutyronitrile, 2,2 ′ -Azobis (isobutyramide), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis [2-methyl-N- (1,1'-bis) (Hydroxymethyl) ethyl) propionamide], 2,2′-azobis [2-methyl-N-1,1′-bis (hydroxyethyl) propionamide], 2,2′-azobis [N- (2-carboxy Ethyl) -2-methylpropionamide] and the like. These may be used independently and 2 or more types may be used together.
（塩基増殖剤封入マイクロカプセル）
本発明の塩基増殖剤封入マイクロカプセルの体積平均粒子径は特に限定されないが、好ましい下限は０．０３μｍ、好ましい上限は１μｍである。体積平均粒子径が０．０３μｍ未満であると、マイクロカプセル中に充分な塩基増殖剤を封入できず、充分な塩基が供給できないことがある。体積平均粒子径が１μｍを超えると、マイクロカプセルが活性エネルギー線を遮ることで、硬化性樹脂組成物の充分な硬化を行うことができないことがある。体積平均粒子径のより好ましい下限は０．０５μｍ、より好ましい上限は０．５μｍである。
本明細書中、体積平均粒子径は、動的光散乱式粒度分布計（Ｐａｒｔｉｃｌｅ Ｓｉｚｉｎｇ Ｓｙｓｔｅｍｓ社製、「ＮＩＣＯＭＰ ｍｏｄｅｌ ３８０ ＺＬＳ−Ｓ」）により測定した値を意味する。
(Base capsule encapsulating microcapsules)
The volume average particle diameter of the base proliferating agent-encapsulated microcapsules of the present invention is not particularly limited, but a preferable lower limit is 0.03 μm and a preferable upper limit is 1 μm. When the volume average particle diameter is less than 0.03 μm, a sufficient base proliferating agent cannot be encapsulated in the microcapsules, and a sufficient base may not be supplied. When the volume average particle diameter exceeds 1 μm, the microcapsule may block the active energy ray, and the curable resin composition may not be sufficiently cured. The more preferable lower limit of the volume average particle diameter is 0.05 μm, and the more preferable upper limit is 0.5 μm.
In the present specification, the volume average particle diameter means a value measured by a dynamic light scattering particle size distribution analyzer (manufactured by Particle Sizing Systems, “NICOMP model 380 ZLS-S”).
本発明の塩基増殖剤封入マイクロカプセルのコア内包率は特に限定されないが、好ましい下限は６．４重量％、好ましい上限は９４重量％である。コア内包率が６．４重量％未満であると、硬化性樹脂組成物の充分な硬化を行うためには多量のマイクロカプセルを配合しなければならず、粘度が高くなりすぎることがある。コア内包率が９４重量％を超えると、シェルが薄くなりすぎ、エポキシ樹脂等へ分散させる際にマイクロカプセルが崩壊することがある。コア内包率のより好ましい下限は２２重量％、より好ましい上限は８８．５重量％である。
本明細書中、コア内包率は、マイクロカプセル全重量中のコアの重量（含有率）を意味する。
The core encapsulation rate of the base proliferating agent-encapsulated microcapsules of the present invention is not particularly limited, but the preferred lower limit is 6.4% by weight and the preferred upper limit is 94% by weight. If the core encapsulation rate is less than 6.4% by weight, a large amount of microcapsules must be blended in order to sufficiently cure the curable resin composition, and the viscosity may become too high. If the core encapsulation rate exceeds 94% by weight, the shell becomes too thin and the microcapsules may collapse when dispersed in an epoxy resin or the like. A more preferable lower limit of the core inclusion rate is 22% by weight, and a more preferable upper limit is 88.5% by weight.
In the present specification, the core inclusion ratio means the weight (content ratio) of the core in the total weight of the microcapsules.
本発明の塩基増殖剤封入マイクロカプセルのシェル厚みは特に限定されないが、好ましい下限はマイクロカプセルの平均粒子径の１％である。シェル厚みがマイクロカプセルの平均粒子径の１％未満であると、シェルが薄すぎて、マイクロカプセルの強度が不足することがある。シェル厚みのより好ましい下限はマイクロカプセルの平均粒子径の２％である。
また、シェル厚みの好ましい上限は０．３μｍである。シェル厚みが０．３μｍを超えると、シェルの内部内で発生した塩基が充分に放出されないことがある。シェル厚みのより好ましい上限は０．２μｍである。
本明細書中、シェル厚みは、マイクロカプセルの全重量からコアの重量（含有率）を引いた残りの重量を、シェル厚みとして換算したものを意味する。
The shell thickness of the base proliferating agent-encapsulated microcapsules of the present invention is not particularly limited, but the preferred lower limit is 1% of the average particle diameter of the microcapsules. If the shell thickness is less than 1% of the average particle diameter of the microcapsules, the shell may be too thin and the strength of the microcapsules may be insufficient. A more preferable lower limit of the shell thickness is 2% of the average particle diameter of the microcapsules.
Moreover, the upper limit with preferable shell thickness is 0.3 micrometer. When the shell thickness exceeds 0.3 μm, the base generated inside the shell may not be sufficiently released. A more preferable upper limit of the shell thickness is 0.2 μm.
In this specification, shell thickness means what converted the remaining weight which subtracted the weight (content rate) of the core from the total weight of the microcapsule as shell thickness.
本発明の塩基増殖剤封入マイクロカプセルの用途は特に限定されないが、硬化剤としてエポキシ樹脂等に配合され、硬化性樹脂組成物とされることが好ましい。なかでも、本発明の塩基増殖剤封入マイクロカプセルは、エポキシ樹脂及び光塩基発生剤に配合され、活性エネルギー線照射によって硬化する感光性エポキシ樹脂組成物とされることがより好ましい。
エポキシ樹脂と、光塩基発生剤と、本発明の塩基増殖剤封入マイクロカプセルとを含有する感光性エポキシ樹脂組成物もまた、本発明の１つである。
Although the use of the microcapsule encapsulating the base proliferating agent of the present invention is not particularly limited, it is preferably blended with an epoxy resin or the like as a curing agent to form a curable resin composition. Among these, the base proliferating agent-encapsulated microcapsules of the present invention are more preferably a photosensitive epoxy resin composition that is blended with an epoxy resin and a photobase generator and cured by irradiation with active energy rays.
The photosensitive epoxy resin composition containing an epoxy resin, a photobase generator, and the base proliferating agent-encapsulated microcapsules of the present invention is also one aspect of the present invention.
上記エポキシ樹脂は特に限定されないが、水系エポキシ樹脂が好ましい。本発明の塩基増殖剤封入マイクロカプセルは、上記エポキシ樹脂が水系エポキシ樹脂であっても、水系エポキシ樹脂に対して均一に分散することができ、均一で信頼性の高い硬化物を形成することができる。
上記水系エポキシ樹脂は特に限定されず、公知の水系エポキシ樹脂を使用することができ、例えば、ビスフェノールＡのジグリシジルエーテル及びそのオリゴマー、水素化ビスフェノールＡのジグリシジルエーテル及びそのオリゴマー、オルソ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、テレフタル酸ジグリシジルエステル、ｐ−オキシ安息香酸ジグリシジルエステル、テトラハイドロフタル酸ジグリシジルエステル、ヘキサハイドロフタル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、アジピン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、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、１，４−ブタンジオールジグリシジルエーテル、１，６−ヘキサンジオ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類、トリメリット酸トリグリシジルエステル、トリグリシジルイソシアヌレート、１，４−ジグリシジルオキシベンゼン、ジグリシジルプロピレン尿素、グリセロールトリグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ペンタエリスリトールトリグリシジルエーテル、グリセロールアルキレンオキサイド付加物のトリグリシジルエーテル等が挙げられる。これらは単独で用いられてもよく、２種以上が併用されてもよい。なかでも、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテルが好ましい。
Although the said epoxy resin is not specifically limited, A water-based epoxy resin is preferable. Even if the epoxy resin is a water-based epoxy resin, the base proliferating agent-encapsulated microcapsules of the present invention can be uniformly dispersed in the water-based epoxy resin and form a uniform and highly reliable cured product. it can.
The water-based epoxy resin is not particularly limited, and a known water-based epoxy resin can be used, for example, diglycidyl ether of bisphenol A and its oligomer, diglycidyl ether of hydrogenated bisphenol A and its oligomer, diglycidyl orthophthalate Ester, Isophthalic acid diglycidyl ester, Terephthalic acid diglycidyl ester, p-oxybenzoic acid diglycidyl ester, Tetrahydrophthalic acid diglycidyl ester, Hexahydrophthalic acid diglycidyl ester, Succinic acid diglycidyl ester, Adipic acid diglycidyl ester , Sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1 6-hexanediol diglycidyl ether, polyalkylene glycol diglycidyl ethers, trimellitic acid triglycidyl ester, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylolpropane Examples include triglycidyl ether, pentaerythritol triglycidyl ether, triglycidyl ether of glycerol alkylene oxide adduct, and the like. These may be used independently and 2 or more types may be used together. Of these, ethylene glycol diglycidyl ether and propylene glycol diglycidyl ether are preferred.
上記水系エポキシ樹脂の市販品として、例えば、Ｗ２８０１、Ｗ２８１１Ｒ７０、Ｗ２８２１Ｒ７０、Ｗ３４３２Ｒ６７、ＤＸ２５５（以上、ｊＥＲシリーズ、三菱化学社製）、３５２０ＷＹ５５、３５４０ＷＹ５５、５００３Ｗ５５、５５２２ＷＹ５５、６００６Ｗ７０（以上、エピレッツシリーズ、三菱化学社製）、アデカレジンＥＭシリーズ（ＡＤＥＫＡ社製）、ＥＸ−６１１、ＥＸ−６１２、ＥＸ−６１４、ＥＸ−６１４Ｂ、ＥＸ−５１２、ＥＸ−５２１、ＥＸ−４２１、ＥＸ−３１３、ＥＸ−３１４、ＥＸ−３２１、ＥＸ−８１０、ＥＸ−８１１、ＥＸ−８５０、ＥＸ−８５１、ＥＸ−８２１、ＥＸ−８３０、ＥＸ−８３２、ＥＸ−８４１、ＥＸ−８６１、ＥＸ−９１１、ＥＸ−９４１、ＥＸ−９２０、ＥＸ−１４５、ＥＸ−１７１（以上、ナガセケムテックス社製）等が挙げられる。 Commercially available products of the above water-based epoxy resins include, for example, W2801, W2811R70, W2821R70, W3432R67, DX255 (above, jER series, manufactured by Mitsubishi Chemical), 3520WY55, 3540WY55, 5003W55, 5522WY55, 6006W70 (above, Epiletts series, Mitsubishi Chemical) Adeka Resin EM Series (manufactured by ADEKA), EX-611, EX-612, EX-614, EX-614B, EX-512, EX-521, EX-421, EX-313, EX-314, EX -321, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-861, EX-911, EX-941, EX-920 , EX-145, EX-17 (Above, manufactured by Nagase Chemtex Corporation), and the like.
上記光塩基発生剤として、例えば、本発明の塩基増殖剤封入マイクロカプセルにおいてコアとして封入されている、上述した光塩基発生剤等が挙げられる。
上記光塩基発生剤の配合量は特に限定されないが、上記エポキシ樹脂１００重量部に対する好ましい下限が０．５重量部、好ましい上限が１５重量部である。上記光塩基発生剤の配合量が０．５重量部未満であると、エポキシ樹脂の硬化効率が低下することがある。上記光塩基発生剤の配合量が１５重量部を超えると、光塩基発生剤の光吸収が強いため、感光性エポキシ樹脂組成物の深部に光が到達せず、硬化不良を引き起こすことがある。上記光塩基発生剤の配合量は、上記エポキシ樹脂１００重量部に対するより好ましい下限が１．０重量部、より好ましい上限が１０重量部である。
Examples of the photobase generator include the above-described photobase generator encapsulated as a core in the base proliferator-encapsulated microcapsule of the present invention.
Although the compounding quantity of the said photobase generator is not specifically limited, The preferable minimum with respect to 100 weight part of said epoxy resins is 0.5 weight part, and a preferable upper limit is 15 weight part. When the blending amount of the photobase generator is less than 0.5 parts by weight, the curing efficiency of the epoxy resin may be lowered. When the amount of the photobase generator exceeds 15 parts by weight, light absorption of the photobase generator is strong, so that light does not reach the deep part of the photosensitive epoxy resin composition, which may cause poor curing. As for the compounding quantity of the said photobase generator, the more preferable minimum with respect to 100 weight part of said epoxy resins is 1.0 weight part, and a more preferable upper limit is 10 weight part.
本発明の塩基増殖剤封入マイクロカプセルの配合量は特に限定されないが、上記エポキシ樹脂１００重量部に対する好ましい下限が０．５重量部、好ましい上限が５０重量部である。本発明の塩基増殖剤封入マイクロカプセルの配合量が０．５重量部未満であると、エポキシ樹脂の硬化効率が低下することがある。本発明の塩基増殖剤封入マイクロカプセルの配合量が５０重量部を超えると、マイクロカプセルの分解に基づく硬化物の体積収縮が大きくなることがある。本発明の塩基増殖剤封入マイクロカプセルの配合量は、上記エポキシ樹脂１００重量部に対するより好ましい下限が１．０重量部、より好ましい上限が２０重量部である。 Although the compounding quantity of the base growth agent enclosure microcapsule of this invention is not specifically limited, The preferable minimum with respect to 100 weight part of said epoxy resins is 0.5 weight part, and a preferable upper limit is 50 weight part. When the blending amount of the base proliferating agent-encapsulated microcapsules of the present invention is less than 0.5 parts by weight, the curing efficiency of the epoxy resin may be lowered. When the blending amount of the base proliferating agent-encapsulated microcapsules of the present invention exceeds 50 parts by weight, the volume shrinkage of the cured product based on the decomposition of the microcapsules may increase. The blending amount of the base proliferating agent-encapsulated microcapsules of the present invention is more preferably 1.0 part by weight and more preferably 20 parts by weight based on 100 parts by weight of the epoxy resin.
本発明の感光性エポキシ樹脂組成物は、活性エネルギー線照射直後からの硬化時間の好ましい下限が０．５分、好ましい上限が２．０時間である。硬化時間が０．５分未満であると、マイクロカプセルからの塩基の放出が充分に起こらないことがある。硬化時間が２．０時間を超えると、信頼性の高い硬化物を得るには時間がかかってしまい、生産性に劣ることがある。本発明の感光性エポキシ樹脂組成物は、活性エネルギー線照射直後からの硬化時間のより好ましい下限が１．０分、より好ましい上限が３０分である。 In the photosensitive epoxy resin composition of the present invention, the preferable lower limit of the curing time immediately after irradiation with active energy rays is 0.5 minutes, and the preferable upper limit is 2.0 hours. When the curing time is less than 0.5 minutes, the release of the base from the microcapsule may not occur sufficiently. When the curing time exceeds 2.0 hours, it takes time to obtain a highly reliable cured product, which may be inferior in productivity. In the photosensitive epoxy resin composition of the present invention, the more preferable lower limit of the curing time immediately after irradiation with active energy rays is 1.0 minute, and the more preferable upper limit is 30 minutes.
本発明によれば、貯蔵安定性にも硬化特性にも優れた硬化剤としてエポキシ樹脂等の硬化に好適に用いられる塩基増殖剤封入マイクロカプセルを提供することができる。また、本発明によれば、該塩基増殖剤封入マイクロカプセルの製造方法、及び、該塩基増殖剤封入マイクロカプセルを含有する感光性エポキシ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 base growth agent enclosure microcapsule used suitably for hardening of an epoxy resin etc. can be provided as a hardening | curing agent excellent in the storage stability and the hardening characteristic. Moreover, according to this invention, the manufacturing method of this base proliferation agent enclosure microcapsule and the photosensitive epoxy resin composition containing this base proliferation agent enclosure microcapsule can be provided.
以下に実施例を掲げて本発明の態様を更に詳しく説明するが、本発明はこれら実施例のみに限定されない。 Examples of the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
（実施例１）
下記に示す油層［１］と水層［１］とを混合し、ホモジナイザーを用いて１０００ｒｐｍで乳化させることにより、油層の乳化液滴を調製した。
＜油層［１］＞
親油性溶媒：クロロホルム（和光純薬工業社製） ５０重量部
塩基増殖剤：式（１−１２）で表される塩基増殖剤 １０重量部
光塩基発生剤：１，６−ヘキサメチレン−ビス（４，５−ジメトキシ−２−ニトロベンジルカルバメート） ２重量部
シェルポリマー：式（２−１）で表されるポリマー １重量部
＜水層［１］＞
水性溶媒：イオン交換水 ５００重量部
分散剤：ポリビニルピロリドンＫ３０（和光純薬工業社製） ５重量部
乳化剤：ドデシルベンゼンスルホン酸ナトリウム（和光純薬工業社製）１重量部
Example 1
The oil layer [1] and the water layer [1] shown below were mixed and emulsified at 1000 rpm using a homogenizer to prepare emulsified droplets of the oil layer.
<Oil layer [1]>
Lipophilic solvent: Chloroform (manufactured by Wako Pure Chemical Industries, Ltd.) 50 parts by weight Base proliferating agent: Base proliferating agent represented by formula (1-12) 10 parts by weight Photobase generator: 1,6-hexamethylene-bis ( 4,5-dimethoxy-2-nitrobenzylcarbamate) 2 parts by weight Shell polymer: polymer represented by formula (2-1) 1 part by weight <aqueous layer [1]>
Aqueous solvent: 500 parts by weight of ion-exchanged water Dispersant: Polyvinylpyrrolidone K30 (manufactured by Wako Pure Chemical Industries) 5 parts by weight Emulsifier: 1 part by weight of sodium dodecylbenzenesulfonate (manufactured by Wako Pure Chemical Industries)
更に、５０℃にてクロロホルムを減圧留去することにより、マイクロカプセルを得た。得られたマイクロカプセルをメタノールで洗浄後、減圧乾燥して、式（２−１）で表されるポリマーを含有するシェルに、式（１−１２）で表される塩基増殖剤がコアとして封入されているマイクロカプセル（体積平均粒子径２３０ｎｍ）を得た。 Furthermore, the microcapsule was obtained by depressurizingly distilling chloroform at 50 degreeC. The obtained microcapsule was washed with methanol and dried under reduced pressure, and the base proliferating agent represented by the formula (1-12) was enclosed as a core in the shell containing the polymer represented by the formula (2-1). Microcapsules (volume average particle diameter of 230 nm) were obtained.
（実施例２）
下記に示す油層［２］と水層［２］とを混合し、ホモジナイザーを用いて１０００ｒｐｍで乳化させることにより、油層の乳化液滴を調製した。
＜油層［２］＞
親油性溶媒：アセトン（和光純薬工業社製） ５０重量部
塩基増殖剤：式（１−１２）で表される塩基増殖剤 １０重量部
光塩基発生剤：１，６−ヘキサメチレン−ビス（４，５−ジメトキシ−２−ニトロベンジルカルバメート） ２重量部
シェルポリマーを形成するモノマー：式（３−１５）で表されるモノマー １重量部
ラジカル開始剤：Ｖ−５０（和光純薬工業社製） ０．１重量部
＜水層［２］＞
水性溶媒：イオン交換水 ５００重量部
分散剤：ポリビニルピロリドンＫ３０（和光純薬工業社製） ５重量部
乳化剤：ドデシルベンゼンスルホン酸ナトリウム（和光純薬工業社製）１重量部
ラジカル開始剤：Ｖ−５０（和光純薬工業社製） ０．１重量部
(Example 2)
The oil layer [2] and the water layer [2] shown below were mixed and emulsified at 1000 rpm using a homogenizer to prepare emulsified droplets of the oil layer.
<Oil layer [2]>
Lipophilic solvent: Acetone (manufactured by Wako Pure Chemical Industries, Ltd.) 50 parts by weight Base proliferating agent: Base proliferating agent represented by formula (1-12) 10 parts by weight Photobase generator: 1,6-hexamethylene-bis ( 4,5-dimethoxy-2-nitrobenzylcarbamate) 2 parts by weight Monomer forming shell polymer: monomer represented by formula (3-15) 1 part by weight radical initiator: V-50 (manufactured by Wako Pure Chemical Industries, Ltd.) ) 0.1 part by weight <aqueous layer [2]>
Aqueous solvent: 500 parts by weight of ion-exchanged water Dispersant: Polyvinylpyrrolidone K30 (manufactured by Wako Pure Chemical Industries) 5 parts by weight Emulsifier: 1 part by weight of sodium dodecylbenzenesulfonate (manufactured by Wako Pure Chemical Industries) Radical initiator: V-50 (Wako Pure Chemical Industries, Ltd.) 0.1 parts by weight
更に、１０００ｍＬ容の丸底セパラブルフラスコに、上記乳化液を移した後、攪拌しながらフラスコ内を窒素雰囲気下にした。その後、６０℃で５時間加熱重合することで、マイクロカプセルを得た。得られたマイクロカプセルをメタノールで洗浄後、減圧乾燥して、式（３−１５）で表されるモノマーからなるポリマーを含有するシェルに、式（１−１２）で表される塩基増殖剤がコアとして封入されているマイクロカプセル（体積平均粒子径２８０ｎｍ）を得た。 Further, after the emulsion was transferred to a 1000 mL round bottom separable flask, the inside of the flask was put under a nitrogen atmosphere while stirring. Then, microcapsules were obtained by heat polymerization at 60 ° C. for 5 hours. The obtained microcapsules were washed with methanol and then dried under reduced pressure, and the base proliferating agent represented by the formula (1-12) was added to the shell containing the polymer composed of the monomer represented by the formula (3-15). Microcapsules (volume average particle diameter 280 nm) encapsulated as a core were obtained.
（実施例３）
下記に示す油層［３］と水層［３］とを混合し、ホモジナイザーを用いて１０００ｒｐｍで乳化させることにより、油層の乳化液滴を調製した。
＜油層［３］＞
親油性溶媒：アセトン（和光純薬工業社製） ５０重量部
塩基増殖剤：式（１−５）で表される塩基増殖剤 １０重量部
光塩基発生剤：１，６−ヘキサメチレン−ビス（４，５−ジメトキシ−２−ニトロベンジルカルバメート） ２重量部
シェルポリマーを形成するモノマー：式（３−１５）で表されるモノマー １重量部
ラジカル開始剤：Ｖ−５０（和光純薬工業社製） ０．１重量部
(Example 3)
The oil layer [3] and the water layer [3] shown below were mixed and emulsified at 1000 rpm using a homogenizer to prepare emulsified droplets of the oil layer.
<Oil layer [3]>
Lipophilic solvent: acetone (manufactured by Wako Pure Chemical Industries, Ltd.) 50 parts by weight Base proliferating agent: base proliferating agent represented by formula (1-5) 10 parts by weight photobase generator: 1,6-hexamethylene-bis ( 4,5-dimethoxy-2-nitrobenzylcarbamate) 2 parts by weight Monomer forming shell polymer: monomer represented by formula (3-15) 1 part by weight radical initiator: V-50 (manufactured by Wako Pure Chemical Industries, Ltd.) ) 0.1 parts by weight
＜水層［３］＞
水性溶媒：イオン交換水 ５００重量部
分散剤：ポリビニルピロリドンＫ３０（和光純薬工業社製） ５重量部
乳化剤：ドデシルベンゼンスルホン酸ナトリウム（和光純薬工業社製）１重量部
ラジカル開始剤：Ｖ−５０（和光純薬工業社製） ０．１重量部
<Water layer [3]>
Aqueous solvent: 500 parts by weight of ion-exchanged water Dispersant: Polyvinylpyrrolidone K30 (manufactured by Wako Pure Chemical Industries) 5 parts by weight Emulsifier: 1 part by weight of sodium dodecylbenzenesulfonate (manufactured by Wako Pure Chemical Industries) Radical initiator: V-50 (Wako Pure Chemical Industries, Ltd.) 0.1 parts by weight
更に、１０００ｍＬ容の丸底セパラブルフラスコに、上記乳化液を移した後、攪拌しながらフラスコ内を窒素雰囲気下にした。その後、６０℃で５時間加熱重合することで、マイクロカプセルを得た。得られたマイクロカプセルをメタノールで洗浄後、減圧乾燥して、式（３−１５）で表されるモノマーからなるポリマーを含有するシェルに、式（１−５）表される塩基増殖剤がコアとして封入されているマイクロカプセル（体積平均粒子径２８０ｎｍ）を得た。 Further, after the emulsion was transferred to a 1000 mL round bottom separable flask, the inside of the flask was put under a nitrogen atmosphere while stirring. Then, microcapsules were obtained by heat polymerization at 60 ° C. for 5 hours. The obtained microcapsules were washed with methanol and then dried under reduced pressure, and the base proliferating agent represented by the formula (1-5) was cored in the shell containing the polymer composed of the monomer represented by the formula (3-15). As a result, microcapsules (volume average particle diameter of 280 nm) were obtained.
（実施例４）
実施例１で得られたマイクロカプセル０．１重量部と、エポキシ樹脂（ＥＸ−５１２、ナガセケムテックス社製）１０重量部とを、遊星式攪拌機にて均一に分散させ、感光性エポキシ樹脂組成物を得た。得られた感光性エポキシ樹脂組成物を直径５ｍｍのガラス製平底試験管に高さが３ｃｍとなるように充填し、周囲をアルミホイルで遮光した後、波長３６５ｎｍのＵＶを３０００ｍＪ／ｃｍ２照射し、その後、１２０℃のオーブン中で３０分間加熱し、硬化物を得た。
Example 4
0.1 parts by weight of the microcapsules obtained in Example 1 and 10 parts by weight of an epoxy resin (EX-512, manufactured by Nagase ChemteX Corp.) are uniformly dispersed with a planetary stirrer to produce a photosensitive epoxy resin composition I got a thing. The obtained photosensitive epoxy resin composition was filled in a glass flat bottom test tube having a diameter of 5 mm so as to have a height of 3 cm, and the surroundings were shielded from light with aluminum foil, and then UV of wavelength 365 nm was irradiated at 3000 mJ / cm 2. Then, it heated for 30 minutes in 120 degreeC oven, and hardened | cured material was obtained.
（実施例５）
実施例２で得られたマイクロカプセルを用いた以外は実施例４と同様にして、感光性エポキシ樹脂組成物と、その硬化物とを得た。
(Example 5)
A photosensitive epoxy resin composition and a cured product thereof were obtained in the same manner as in Example 4 except that the microcapsules obtained in Example 2 were used.
（実施例６）
実施例３で得られたマイクロカプセルを用いた以外は実施例４と同様にして、感光性エポキシ樹脂組成物と、その硬化物とを得た。
(Example 6)
A photosensitive epoxy resin composition and a cured product thereof were obtained in the same manner as in Example 4 except that the microcapsules obtained in Example 3 were used.
（比較例１）
式（１−６）で表される塩基増殖剤０．１重量部と、光塩基発生剤として１，６−ヘキサメチレン−ビス（４，５−ジメトキシ−２−ニトロベンジルカルバメート）０．０２重量部と、エポキシ樹脂（ＥＸ−５１２、ナガセケムテックス社製）１０重量部とを、遊星式攪拌機にて均一に分散させ、感光性エポキシ樹脂組成物を得た。得られた感光性エポキシ樹脂組成物を用いた以外は実施例４と同様にして、硬化物を得た。
(Comparative Example 1)
0.1 part by weight of a base proliferating agent represented by the formula (1-6) and 0.02 part by weight of 1,6-hexamethylene-bis (4,5-dimethoxy-2-nitrobenzylcarbamate) as a photobase generator Part and 10 parts by weight of an epoxy resin (EX-512, manufactured by Nagase ChemteX Corporation) were uniformly dispersed with a planetary stirrer to obtain a photosensitive epoxy resin composition. A cured product was obtained in the same manner as in Example 4 except that the obtained photosensitive epoxy resin composition was used.
＜評価＞
実施例４〜６及び比較例１で得られた感光性エポキシ樹脂組成物の硬化物について、以下の評価を行った。結果を表１に示す。
<Evaluation>
The following evaluation was performed about the hardened | cured material of the photosensitive epoxy resin composition obtained in Examples 4-6 and Comparative Example 1. FIG. The results are shown in Table 1.
（１）厚膜硬化特性
硬化物を得た後、ガラス製平底試験管を除去し、メチルエチルケトンで洗浄することにより、未硬化部分を除去し、硬化物の厚みを測定した。硬化物の厚みが厚い程、厚膜硬化特性が高いことを意味する。
(1) Thick film curing characteristics After obtaining a cured product, the glass flat bottom test tube was removed and washed with methyl ethyl ketone to remove the uncured portion, and the thickness of the cured product was measured. A thicker cured product means higher thick film curing characteristics.
（２）硬化物の信頼性
得られた硬化物の硬度を鉛筆硬度試験により評価した。鉛筆硬度試験では、硬化膜を鉛筆で引っかいて３ｍｍ以上のキズが入った状態を不具合とし、キズが生じなかった最も硬い鉛筆硬度を評価した。鉛筆硬度が高いほど、硬化物の信頼性が高いことを意味する。
(2) Reliability of cured product The hardness of the obtained cured product was evaluated by a pencil hardness test. In the pencil hardness test, the cured film was scratched with a pencil, and a state in which scratches of 3 mm or more were included was regarded as a defect, and the hardest pencil hardness without scratches was evaluated. Higher pencil hardness means higher reliability of the cured product.
本発明によれば、貯蔵安定性にも硬化特性にも優れた硬化剤としてエポキシ樹脂等の硬化に好適に用いられる塩基増殖剤封入マイクロカプセルを提供することができる。また、本発明によれば、該塩基増殖剤封入マイクロカプセルの製造方法、及び、該塩基増殖剤封入マイクロカプセルを含有する感光性エポキシ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 base growth agent enclosure microcapsule used suitably for hardening of an epoxy resin etc. can be provided as a hardening | curing agent excellent in the storage stability and the hardening characteristic. Moreover, according to this invention, the manufacturing method of this base proliferation agent enclosure microcapsule and the photosensitive epoxy resin composition containing this base proliferation agent enclosure microcapsule can be provided.
Claims (5)
少なくとも、コアを構成する塩基増殖反応を引き起こす基を有する塩基増殖剤と、シェルポリマーとの共存下、塩基増殖剤封入マイクロカプセルを製造する
ことを特徴とする塩基増殖剤封入マイクロカプセルの製造方法。 A method for producing a microcapsule encapsulating a base proliferating agent according to claim 1 or 2 ,
A base proliferating agent-encapsulated microcapsule characterized by producing a base proliferating agent-encapsulated microcapsule in the presence of at least a base proliferating agent having a group that causes a base proliferating reaction constituting a core and a shell polymer.
少なくとも、コアを構成する塩基増殖反応を引き起こす基を有する塩基増殖剤と、シェルポリマーを形成するモノマーとの共存下、塩基増殖剤封入マイクロカプセルを製造する
ことを特徴とする塩基増殖剤封入マイクロカプセルの製造方法。 A method for producing a microcapsule encapsulating a base proliferating agent according to claim 1 or 2 ,
A base proliferating agent-encapsulated microcapsule characterized by producing a base proliferating agent-encapsulated microcapsule in the presence of a base proliferating agent having a group that causes a base proliferating reaction constituting a core and a monomer that forms a shell polymer. Manufacturing method.
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| JP6873417B2 (en) * | 2016-11-10 | 2021-05-19 | 学校法人東京理科大学 | Photoreactive composition |
| CN112552853B (en) * | 2020-12-29 | 2022-08-02 | 烟台信友新材料有限公司 | Ultraviolet light initiated normal temperature fast curing single-component epoxy adhesive and preparation method thereof |
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| JPH07268312A (en) * | 1994-03-30 | 1995-10-17 | Fuji Photo Film Co Ltd | Method for generating base |
| JPH07323668A (en) * | 1994-05-30 | 1995-12-12 | Ricoh Co Ltd | Microcapsule and production thereof |
| JP2000330270A (en) * | 1999-05-24 | 2000-11-30 | Kunihiro Ichimura | Base propagator, base propagator composition, reactive base composition and pattern forming method |
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