JP2021155674A - Resin composition for photocurable lining material, photocurable lining material, and cured product thereof - Google Patents
Resin composition for photocurable lining material, photocurable lining material, and cured product thereof Download PDFInfo
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- JP2021155674A JP2021155674A JP2020060181A JP2020060181A JP2021155674A JP 2021155674 A JP2021155674 A JP 2021155674A JP 2020060181 A JP2020060181 A JP 2020060181A JP 2020060181 A JP2020060181 A JP 2020060181A JP 2021155674 A JP2021155674 A JP 2021155674A
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- JP
- Japan
- Prior art keywords
- lining material
- meth
- resin composition
- photocurable lining
- acrylate
- 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.)
- Pending
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- 239000000463 material Substances 0.000 title claims abstract description 52
- 239000011342 resin composition Substances 0.000 title claims abstract description 35
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 51
- 239000004593 Epoxy Substances 0.000 claims abstract description 29
- 229920005989 resin Polymers 0.000 claims abstract description 25
- 239000011347 resin Substances 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 239000003822 epoxy resin Substances 0.000 claims description 19
- 229920000647 polyepoxide Polymers 0.000 claims description 19
- 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 18
- -1 phenoxyethyl Chemical group 0.000 claims description 12
- 239000003365 glass fiber Substances 0.000 claims description 8
- 239000012779 reinforcing material Substances 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 239000000047 product Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 238000001723 curing Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 4
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 229920003986 novolac Polymers 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
- JMIZWXDKTUGEES-UHFFFAOYSA-N 2,2-di(cyclopenten-1-yloxy)ethyl 2-methylprop-2-enoate Chemical compound C=1CCCC=1OC(COC(=O)C(=C)C)OC1=CCCC1 JMIZWXDKTUGEES-UHFFFAOYSA-N 0.000 description 2
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229960002130 benzoin Drugs 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
- 239000011230 binding agent Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 238000006116 polymerization reaction 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-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
- 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
- DKEGCUDAFWNSSO-UHFFFAOYSA-N 1,8-dibromooctane Chemical compound BrCCCCCCCCBr DKEGCUDAFWNSSO-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
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N 2,2-dimethylbutane Chemical compound CCC(C)(C)C HNRMPXKDFBEGFZ-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
- LZHUBCULTHIFNO-UHFFFAOYSA-N 2,4-dihydroxy-1,5-bis[4-(2-hydroxyethoxy)phenyl]-2,4-dimethylpentan-3-one Chemical compound C=1C=C(OCCO)C=CC=1CC(C)(O)C(=O)C(O)(C)CC1=CC=C(OCCO)C=C1 LZHUBCULTHIFNO-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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- RQZUWSJHFBOFPI-UHFFFAOYSA-N 2-[1-[1-(oxiran-2-ylmethoxy)propan-2-yloxy]propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COC(C)COCC1CO1 RQZUWSJHFBOFPI-UHFFFAOYSA-N 0.000 description 1
- FGTYTUFKXYPTML-UHFFFAOYSA-N 2-benzoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 FGTYTUFKXYPTML-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- MYISVPVWAQRUTL-UHFFFAOYSA-N 2-methylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3SC2=C1 MYISVPVWAQRUTL-UHFFFAOYSA-N 0.000 description 1
- GRWFFFOEIHGUBG-UHFFFAOYSA-N 3,4-Epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclo-hexanecarboxylate Chemical compound C1C2OC2CC(C)C1C(=O)OCC1CC2OC2CC1C GRWFFFOEIHGUBG-UHFFFAOYSA-N 0.000 description 1
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 1
- 125000004861 4-isopropyl phenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- BWPYBAJTDILQPY-UHFFFAOYSA-N Methoxyphenone Chemical compound C1=C(C)C(OC)=CC=C1C(=O)C1=CC=CC(C)=C1 BWPYBAJTDILQPY-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 description 1
- DBHQYYNDKZDVTN-UHFFFAOYSA-N [4-(4-methylphenyl)sulfanylphenyl]-phenylmethanone Chemical compound C1=CC(C)=CC=C1SC1=CC=C(C(=O)C=2C=CC=CC=2)C=C1 DBHQYYNDKZDVTN-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 239000012615 aggregate Substances 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 1
- 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
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- QDVNNDYBCWZVTI-UHFFFAOYSA-N bis[4-(ethylamino)phenyl]methanone Chemical compound C1=CC(NCC)=CC=C1C(=O)C1=CC=C(NCC)C=C1 QDVNNDYBCWZVTI-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 230000007797 corrosion Effects 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
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- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
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- 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 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
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- 238000005470 impregnation Methods 0.000 description 1
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- 230000005865 ionizing radiation Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- NWAHZAIDMVNENC-UHFFFAOYSA-N octahydro-1h-4,7-methanoinden-5-yl methacrylate Chemical compound C12CCCC2C2CC(OC(=O)C(=C)C)C1C2 NWAHZAIDMVNENC-UHFFFAOYSA-N 0.000 description 1
- WKGDNXBDNLZSKC-UHFFFAOYSA-N oxido(phenyl)phosphanium Chemical compound O=[PH2]c1ccccc1 WKGDNXBDNLZSKC-UHFFFAOYSA-N 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
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- 229920006267 polyester film Polymers 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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Abstract
Description
本発明は、光硬化型ライニング材用樹脂組成物、光硬化型ライニング材、及びその硬化物に関する。 The present invention relates to a resin composition for a photocurable lining material, a photocurable lining material, and a cured product thereof.
下水道等の老朽化管の補修法として、スチレン系不飽和ポリエステル樹脂組成物及びビニルエステル樹脂組成物を用いたライニング材による熱硬化型の更生工法が多用されているが、これらの材料には、施工時の臭気対策及び施工時間の短縮が求められている。 As a method for repairing aged pipes such as sewers, a thermosetting rehabilitation method using a styrene-based unsaturated polyester resin composition and a vinyl ester resin composition with a lining material is often used. It is required to take measures against odor during construction and shorten the construction time.
このような状況下、不飽和ポリエステル、単官能性(メタ)アクリレート系モノマー、及び熱可塑性樹脂粉末を含有する光硬化型硬化性樹脂組成物が提案されている（例えば、特許文献１参照。）。しかしながら、この光硬化型硬化性樹脂組成物を用いたライニング材では、厚膜形成時の硬化性が不十分であるという問題があった。 Under such circumstances, a photocurable curable resin composition containing an unsaturated polyester, a monofunctional (meth) acrylate-based monomer, and a thermoplastic resin powder has been proposed (see, for example, Patent Document 1). .. However, the lining material using this photocurable curable resin composition has a problem that the curability at the time of forming a thick film is insufficient.
本発明が解決しようとする課題は、速硬化性及び厚膜硬化性に優れる光硬化型ライニング材が得られる光硬化型ライニング材用樹脂組成物を提供することである。 An object to be solved by the present invention is to provide a resin composition for a photocurable lining material, which can obtain a photocurable lining material having excellent fast-curing property and thick film curing property.
本発明者等は、特定の樹脂成分と光重合開始剤とを含有する光硬化型ライニング材用樹脂組成物が、上記課題を解決できることを見出し、本発明を完成した。 The present inventors have found that a resin composition for a photocurable lining material containing a specific resin component and a photopolymerization initiator can solve the above problems, and have completed the present invention.
すなわち、エポキシ（メタ）アクリレート（ａ１）及び不飽和単量体（ａ２）を必須成分とする樹脂成分（Ａ）と光重合開始剤（Ｂ）とを含有する光硬化型ライニング材用樹脂組成物であって、前記樹脂成分（Ａ）の屈折率が１．５３０〜１．５５０の範囲であることを特徴とする光硬化型ライニング材用樹脂組成物に関する。 That is, a resin composition for a photocurable lining material containing a resin component (A) containing an epoxy (meth) acrylate (a1) and an unsaturated monomer (a2) as essential components and a photopolymerization initiator (B). The present invention relates to a resin composition for a photocurable lining material, wherein the refractive index of the resin component (A) is in the range of 1.530 to 1.550.
本発明の光硬化型ライニング材用樹脂組成物から得られる光硬化型ライニング材は、速硬化性及び厚膜硬化性に優れることから、下水道管等の管更生に好適に用いることができる。また、上水道管をはじめとしたガス管、電力管等のインフラ補修用途、及び浴室の防水床等の補修用プリプレグにも用いることができる。 The photocurable lining material obtained from the resin composition for a photocurable lining material of the present invention is excellent in quick-curing property and thick film curable property, and therefore can be suitably used for pipe rehabilitation of sewer pipes and the like. It can also be used for infrastructure repair applications such as water pipes and other gas pipes and power pipes, and for repair prepregs such as waterproof floors in bathrooms.
本発明の光硬化型ライニング材用樹脂組成物は、エポキシ（メタ）アクリレート（ａ１）及び不飽和単量体（ａ２）を必須成分とする樹脂成分（Ａ）と光重合開始剤（Ｂ）とを含有する光硬化型ライニング材用樹脂組成物であって、前記樹脂成分（Ａ）の屈折率が１．５３０〜１．５５０の範囲であるものである。 The resin composition for a photocurable lining material of the present invention comprises a resin component (A) containing an epoxy (meth) acrylate (a1) and an unsaturated monomer (a2) as essential components, and a photopolymerization initiator (B). A resin composition for a photocurable lining material containing the above, wherein the refractive index of the resin component (A) is in the range of 1.530 to 1.550.
なお、本発明において、「（メタ）アクリレート」とは、アクリレートとメタアクリレートの一方又は両方をいい、「（メタ）アクリル酸」とは、アクリル酸とメタクリル酸の一方又は両方をいう。 In the present invention, "(meth) acrylate" means one or both of acrylate and methacrylate, and "(meth) acrylic acid" means one or both of acrylic acid and methacrylic acid.
前記エポキシ（メタ）アクリレート（ａ１）は、例えば、エポキシ樹脂と（メタ）アクリル酸とを反応させることで得られる。 The epoxy (meth) acrylate (a1) can be obtained, for example, by reacting an epoxy resin with (meth) acrylic acid.
前記エポキシ樹脂としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールフルオレン型エポキシ樹脂、ビスクレゾールフルオレン型等のビスフェノール型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂等のノボラック型エポキシ樹脂、オキゾドリドン変性エポキシ樹脂、これらの樹脂の臭素化エポキシ樹脂等のフェノールのグリシジルエーテル、ジプロピレングリコールジ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、ビスフェノールＡのアルキレンオキサイド付加物のジグリシジルエーテル、水素化ビスフェノールＡのジグリシジルエーテル等の多価アルコールのグリシジルエーテル、３，４−エポキシ−６−メチルシクロヘキシルメチル−３，４−エポキシ−６−メチルシクロヘキサンカルボキシレート、１−エポシエチル−３，４−エポキシシクロヘキサン等の脂環式エポキシ樹脂、フタル酸ジグリシジルエステル、テトラヒドロフタル酸ジグリシジルエステル、ジグリシジル−ｐ−オキシ安息香酸、ダイマー酸グリシジルエステルなどのグリシジルエステル、テトラグリシジルジアミノジフェニルメタン、テトラグリシジル−ｍ−キシレンジアミン、トリグリシジル−ｐ一アミノフェノール、Ｎ，Ｎ−ジグリシジルアニリンなどのグリシジルアミン、１，３−ジグリシジル−５，５−ジメチルヒダントイン、トリグリシジルイソシアヌレートなどの複素環式エポキシ樹脂などが挙げられるが、これらの中でも、前記樹脂成分（Ａ）の屈折率を一定の範囲に調整しやすく、厚膜硬化性をより向上できることから、ビスフェノールＡ型エポキシ樹脂が好ましい。なお、これらのエポキシ樹脂は、単独で用いることも２種以上併用することもできる。 Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol fluorene type epoxy resin, bisphenol fluorene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin and the like. Novolak type epoxy resin, oxodoridone modified epoxy resin, glycidyl ether of phenol such as brominated epoxy resin of these resins, dipropylene glycol diglycidyl ether, trimethylpropan triglycidyl ether, diglycidyl ether of alkylene oxide adduct of bisphenol A , Glycidyl ether of polyhydric alcohol such as diglycidyl ether of bisphenol A hydride, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 1-epoxyethyl-3,4 -Alicyclic epoxy resin such as epoxycyclohexane, phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, diglycidyl-p-oxybenzoic acid, glycidyl ester such as dimer acid glycidyl ester, tetraglycidyl diaminodiphenylmethane, tetraglycidyl-m -Xylenediamine, triglycidyl-p monoaminophenol, glycidylamine such as N, N-diglycidylaniline, heterocyclic epoxy resin such as 1,3-diglycidyl-5,5-dimethylhydantin, triglycidyl isocyanurate, etc. Among these, the bisphenol A type epoxy resin is preferable because the refractive index of the resin component (A) can be easily adjusted within a certain range and the thick film curability can be further improved. These epoxy resins may be used alone or in combination of two or more.
前記したエポキシ樹脂と（メタ）アクリル酸との反応は、エステル化触媒を用い、６０〜１４０℃において行われることが好ましい。また、重合禁止剤等を使用することもできる。 The reaction between the epoxy resin and (meth) acrylic acid is preferably carried out at 60 to 140 ° C. using an esterification catalyst. Further, a polymerization inhibitor or the like can also be used.
前記不飽和単量体（ａ２）としては、例えば、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、ポリエチレングリコール（メタ）アクリレートアルキルエーテル、ポリプロピレングリコール（メタ）アクリレートアルキルエーテル、２−エチルヘキシルメタクリレート、イソデシル（メタ）アクリレート、ラウリル（メタ）アクリレート、イソトリデシル（メタ）アクリレート、ｎ−ステアリル（メタ）アクリレート、テトラヒドロフルフリルメタクリレート、イソボルニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、ジシクロペンタニルメタクリレート等の単官能（メタ）アクリレート化合物；エチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、１，４−ブタンジオールジ（メタ）アクリレート、１，３−ブタンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ビスフェノールジ（メタ）アクリレート、１，４−シクロヘキサンジメタノールジ（メタ）アクリレート等のジ（メタ）アクリレート化合物；ジアリルフタレート、ジビニルベンゼンなどが挙げられるが、これらの中でも、前記樹脂成分（Ａ）の屈折率を一定の範囲に調整しやすく、厚膜硬化性をより向上できることから、フェノキシエチル（メタ）アクリレートがより好ましい。なお、これらの不飽和単量体は単独で用いることも、２種以上併用することもできる。 Examples of the unsaturated monomer (a2) include benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate alkyl ether, and polypropylene glycol (meth) acrylate. Alkyl ether, 2-ethylhexyl methacrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, isotridecyl (meth) acrylate, n-stearyl (meth) acrylate, tetrahydrofurfuryl methacrylate, isobornyl (meth) acrylate, dicyclopentenyloxyethyl Monofunctional (meth) acrylate compounds such as (meth) acrylate and dicyclopentanyl methacrylate; ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1, 3-Butandiol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol di (meth) acrylate, 1,4-cyclohexanedimethanol di (meth) acrylate Di (meth) acrylate compounds such as, diallyl phthalate, divinyl benzene, etc. Among these, the refractive index of the resin component (A) can be easily adjusted within a certain range, and the thick film curability can be further improved. Therefore, phenoxyethyl (meth) acrylate is more preferable. These unsaturated monomers may be used alone or in combination of two or more.
前記ラジカル硬化性樹脂（ａ１）と前記不飽和単量体（ａ２）との質量比（ａ１／ａ２）は、繊維への樹脂含浸性、及び硬化性のバランスがより向上することから、３０／７０〜７０／３０の範囲が好ましく、４０／６０〜６０／４０の範囲がより好ましい。 The mass ratio (a1 / a2) of the radical curable resin (a1) and the unsaturated monomer (a2) is 30 / because the balance between the resin impregnation property into the fiber and the curability is further improved. The range of 70 to 70/30 is preferable, and the range of 40/60 to 60/40 is more preferable.
前記樹脂成分（Ａ）の屈折率は、１．５３０〜１．５５０の範囲であるが、厚膜硬化性がより向上することから、１．５３５〜１．５５０の範囲が好ましい。 The refractive index of the resin component (A) is in the range of 1.530 to 1.550, but is preferably in the range of 1.535 to 1.550 because the thick film curability is further improved.
前記樹脂成分（Ａ）は、前記エポキシ（メタ）アクリレート（ａ１）及び前記不飽和単量体（ａ２）を必須成分として含有するものであるが、屈折率が１．５３０〜１．５５０の範囲であれば、その他の樹脂成分を含有してもよい。 The resin component (A) contains the epoxy (meth) acrylate (a1) and the unsaturated monomer (a2) as essential components, and has a refractive index in the range of 1.530 to 1.550. If so, other resin components may be contained.
前記光重合開始剤（Ｂ）としては、例えば、４−フェノキシジ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−ヒドロキシシクロヘキシルフェニルケトン、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、２−メチル−［４−（メチルチオ）フェニル］−２−モルフォリノ−１−プロパノン、２，２−ジメトキシ−２−フェニルアセトフェノン等のアセトフェノン化合物；ベンゾイン、ベンゾインメチルエーテル、ベンゾインイソエチルエーテル、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等のベンゾイン化合物；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、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化合物；チオキサントン、２−クロロチオキサントン、２，４−ジクロロチオキサントン、２−メチルチオキサントン、２，４−ジメチルチオキサントン、２，４−ジエチルチオキサントン、イソプロピルチオキサントン、２，４−ジイソプロピルチオキサントン等のチオキサントン化合物；４，４’−ジメチルアミノチオキサントン（別名＝ミネラーズケトン）、４，４’−ジエチルアミノベンゾフェノン、α−アシロキシムエステル、ベンジル、メチルベンゾイルホルメート（「バイアキュア５５」）、２−エチルアンスラキノン等のアンスラキノン化合物；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、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等のアシルフォスフィンオキサイド化合物；３，３’，４，４’−テトラ（ｔｅｒｔ−ブチルオパーオキシカルボニル）ベンゾフェノン、アクリル化ベンゾフェノン等を用いることができる。なお、これらの光重合開始剤（Ｂ）は、単独で用いることも２種以上併用することもできる。 Examples of the photopolymerization initiator (B) include 4-phenoxydichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2. -Hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-methyl- [4- (methylthio) Phenyl] -2-morpholino-1-propanone, 2,2-dimethoxy-2-phenylacetophenone and other acetophenone compounds; benzoin, benzoin methyl ether, benzoin isoethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin compounds; benzophenone , Benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3'-dimethyl-4-methoxybenzophenone and other benzophenone compounds; thioxanthone, 2-chloro Thioxanthone compounds such as thioxanthone, 2,4-dichlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone; 4,4'-dimethylaminothioxanthone. Anthracinone compounds such as (also known as Minerals ketone), 4,4'-diethylaminobenzophenone, α-acyloxime ester, benzyl, methylbenzoylformate ("Biacure 55"), 2-ethylanthraquinone; 2,4 Acylphosphine oxide compounds such as 6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide; 3,3', 4,4'-tetra (tert-butyloperoxycarbonyl) benzophenone , Acrylicized benzophenone and the like can be used. These photopolymerization initiators (B) may be used alone or in combination of two or more.
前記光重合開始剤（Ｂ）の使用量は、速硬化性及び厚膜硬化性に優れることから、前記樹脂成分（Ａ）１００質量部に対して、０．１〜３質量部の範囲が好ましく、０．１〜２質量部の範囲がより好ましい。 The amount of the photopolymerization initiator (B) used is preferably in the range of 0.1 to 3 parts by mass with respect to 100 parts by mass of the resin component (A) because it is excellent in quick curability and thick film curability. , 0.1 to 2 parts by mass is more preferable.
本発明の光硬化型ライニング材用樹脂組成物は、樹脂成分（Ａ）及び光重合開始剤（Ｂ）を含有するものであるが、必要に応じてその他の添加剤を含有してもよい。 The resin composition for a photocurable lining material of the present invention contains a resin component (A) and a photopolymerization initiator (B), but may contain other additives if necessary.
前記その他の添加剤としては、例えば、重合禁止剤、酸化防止剤、光安定剤、溶媒、消泡剤、チキソ付与剤、増感剤、レベリング剤、粘着付与剤、帯電防止剤、難燃剤、硬化促進剤、顔料、充填剤、補強材、骨材等が挙げられる。 Examples of the other additives include polymerization inhibitors, antioxidants, photostabilizers, solvents, defoamers, thixo-imparting agents, sensitizers, leveling agents, tackifiers, antistatic agents, flame retardants, and the like. Examples include curing accelerators, pigments, fillers, reinforcing materials, aggregates and the like.
本発明の光硬化型ライニング材は、前記光硬化型ライニング材用樹脂組成物及びガラス繊維強化材を含有するものである。 The photocurable lining material of the present invention contains the resin composition for a photocurable lining material and a glass fiber reinforcing material.
前記ガラス繊維強化材の形態としては、例えば、ロービングを平織にしたロービンククロス、２インチにカットしたチョップドストランドをランダムに配向させバインダーで固着し、不織布としたチョップドストランドマット、ロービングを同方向に引き揃え、補助よこ糸やバインダーで一体化させた一方向シート、上記、一方向に引き揃えたシートを多方向に積層し、ステッチ糸で一体化した多軸ステッチ基材、一方向に引き揃えたシート材とランダムに配向させたチョップドストランドをステッチで一体化させたステッチマット等の筒状、マット状にしたものが用いられる。また、これらのガラス繊維強化材は、単独で用いることも２種類以上併用することもできる。 As the form of the glass fiber reinforcing material, for example, a chopped strand mat in which rovings are plain weave, chopped strands cut into 2 inches are randomly oriented and fixed with a binder, and chopped strand mats and rovings made into a non-woven fabric are formed in the same direction. Alignment, unidirectional sheet integrated with auxiliary weft thread and binder, multi-axis stitch base material integrated with stitch thread by laminating the above unidirectionally aligned sheet in multiple directions, aligned in one direction A tubular or mat-shaped material such as a stitch mat in which a sheet material and chopped strands randomly oriented are integrated by stitching is used. Further, these glass fiber reinforcing materials may be used alone or in combination of two or more.
前記ガラス繊維としては、例えば、含アルカリガラス（Ｃガラス）、低アルカリガラス、無アルカリガラス（Ｅガラス）等を原料にして得られたものを使用することもできるが、インフラ補修用途における機械的特性と耐蝕性に優れる耐酸ガラス（ＥＣＲガラス）を使用することが好ましい。 As the glass fiber, for example, those obtained by using alkali-containing glass (C glass), low-alkali glass, non-alkali glass (E glass) or the like as raw materials can be used, but mechanically in infrastructure repair applications. It is preferable to use acid resistant glass (ECR glass) having excellent properties and corrosion resistance.
本発明の光硬化型ライニング材中の前記ガラス繊維強化材の含有率は、機械的物性がより向上することから、３０〜６０質量％の範囲が好ましい。 The content of the glass fiber reinforcing material in the photocurable lining material of the present invention is preferably in the range of 30 to 60% by mass because the mechanical properties are further improved.
本発明のライニング材の施工、適用方法としては、コンクリート等の補修面に直接本発明の光硬化型ライニング樹脂組成物とガラス繊維強化材を積層、含浸しライニング材層を形成する方法や、予め、工場等で本発明の光硬化型ライニング樹脂組成物とガラス繊維強化材を積層、含浸し、両面をフィルムで覆ったプリプレグとして作成、補修現場にて必要により被着面のフィルムを剥離した後、補修箇所の形状に合わせローラー等で加圧圧着、光の照射により硬化させるものである。 As a method of constructing and applying the lining material of the present invention, a method of directly laminating and impregnating the photocurable lining resin composition of the present invention and a glass fiber reinforcing material on a repair surface such as concrete to form a lining material layer, or in advance. After laminating and impregnating the photocurable lining resin composition of the present invention and the glass fiber reinforcing material at a factory, etc., and creating a prepreg with both sides covered with a film, the film on the adherend surface is peeled off as necessary at the repair site. , It is hardened by pressure crimping with a roller or the like according to the shape of the repaired part and irradiation with light.
本発明の光硬化型ライニング材を硬化させる方法としては、例えば、紫外線、電子線、α線、β線、γ線のような電離放射線を照射する方法が挙げられるが、具体的なエネルギー源または硬化装置としては、例えば、殺菌灯、紫外線用蛍光灯、カーボンアーク、キセノンランプ、複写用高圧水銀灯、中圧または高圧水銀灯、超高圧水銀灯、無電極ランプ、メタルハライドランプ、蛍光ケミカルランプ、ＬＥＤランプ、自然光等を光源とする紫外線、または走査型、カーテン型電子線加速器による電子線等が挙げられる。 Examples of the method for curing the photocurable lining material of the present invention include a method of irradiating ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Examples of the curing device include sterilizing lamps, fluorescent lamps for ultraviolet rays, carbon arcs, xenon lamps, high-pressure mercury lamps for copying, medium-pressure or high-pressure mercury lamps, ultra-high-pressure mercury lamps, electrode-free lamps, metal halide lamps, fluorescent chemical lamps, LED lamps, etc. Examples thereof include ultraviolet rays using natural light as a light source, or electron beams using a scanning type or curtain type electron beam accelerator.
本発明の光硬化型ライニング材は、速硬化性及び厚膜硬化性に優れることから、下水道管等の管更生に好適に用いることができる。また、上水道管をはじめとしたガス管、電力管等のインフラ補修用途、及び浴室の防水床等の補修用プリプレグにも用いることができる。 Since the photocurable lining material of the present invention is excellent in quick-curing property and thick film curing property, it can be suitably used for pipe rehabilitation of sewer pipes and the like. It can also be used for infrastructure repair applications such as water pipes and other gas pipes and power pipes, and for repair prepregs such as waterproof floors in bathrooms.
以下に本発明を具体的な実施例を挙げてより詳細に説明する。なお、樹脂成分の屈折率は、ユニバーサルアッベ屈折率計（エルマ販売株式会社製「ＥＲ−７ＭＷ」）を用いて測定し、酸価はＪＩＳ−Ｋ−６９０１、エポキシ当量はＪＩＳ−Ｋ−７２３６に準拠してそれぞれ測定した。 Hereinafter, the present invention will be described in more detail with reference to specific examples. The refractive index of the resin component was measured using a universal Abbe refractive index meter (“ER-7MW” manufactured by Elma Sales Co., Ltd.), and the acid value was JIS-K-6901 and the epoxy equivalent was JIS-K-7236. Each was measured according to the rules.
（合成例１：エポキシ（メタ）アクリレート（ａ１−１）の合成）
温度計、窒素導入管、撹拌機を設けた２Ｌフラスコに、窒素と空気とを１対１で混合したガス流通雰囲気下、ビスフェノールＡ型エポキシ樹脂（ＤＩＣ株式会社製「エピクロン８５０」、エポキシ当量１８８）４８８．８質量部、メタクリル酸２１５．７質量部、及びｔ−ブチルハイドロキノン０．２５質量部を仕込み、９０℃に昇温して１時間反応させた後、２−メチルイミダゾール０．７質量部を添加して、反応温度を１１０℃まで昇温して２時間反応させた。その後さらに２−メチルイミダゾール ０．７質量部を添加して酸価、エポキシ当量を測定した。酸価が７．０以下、エポキシ当量が５０００以上になったことを確認後、反応を終了した。５０℃付近まで冷却した後、ｔ−ブチルハイドロキノン０．０５質量部を加えて、反応容器より取り出し、エポキシ（メタ）アクリレート（ａ１−１）を得た。
(Synthesis Example 1: Synthesis of Epoxy (Meta) Acrylate (a1-1))
Bisphenol A type epoxy resin ("Epiclon 850" manufactured by DIC Corporation, epoxy equivalent 188) in a gas flow atmosphere in which nitrogen and air are mixed 1: 1 in a 2L flask equipped with a thermometer, a nitrogen introduction tube, and a stirrer. ) 488.8 parts by mass, 215.7 parts by mass of methacrylic acid, and 0.25 parts by mass of t-butylhydroquinone were charged, heated to 90 ° C. and reacted for 1 hour, and then 0.7 mass by mass of 2-methylimidazole. The part was added, the reaction temperature was raised to 110 ° C., and the reaction was carried out for 2 hours. After that, 0.7 parts by mass of 2-methylimidazole was further added, and the acid value and epoxy equivalent were measured. After confirming that the acid value was 7.0 or less and the epoxy equivalent was 5000 or more, the reaction was terminated. After cooling to around 50 ° C., 0.05 part by mass of t-butylhydroquinone was added, and the mixture was taken out from the reaction vessel to obtain an epoxy (meth) acrylate (a1-1).
（合成例２：エポキシ（メタ）アクリレート（ａ１−２）の合成）
温度計、窒素導入管、撹拌機を設けた２Ｌフラスコに窒素流通下、ビスフェノールＡ型エポキシ樹脂（ＤＩＣ株式会社製「エピクロン８５０」、エポキシ当量１８８）３６８．３質量部を加えて６０℃に加温した後、ビスフェノールＡ ８３．４質量部を加えて、１１０℃まで昇温させた。その後、２−メチルイミダゾール０.５５質量部を添加して、エポキシ当量が３７５±１０の範囲内になることを確認して、１００℃まで冷却した。真空ポンプを用いて窒素除去後、空気置換した。続いて、窒素と空気とを１対１で混合したガス流通雰囲気下、１００℃でメタクリル酸１０２．２質量部、ｔ−ブチルハイドロキノン０．２０質量部を仕込み、２時間反応させた後、２−メチルイミダゾール０．２７７質量部を添加して酸価、エポキシ当量を測定した。酸価が３．０〜７．０、エポキシ当量が５０００〜１００００の範囲になったことを確認後、反応を終了した。ｔ−ブチルハイドロキノン０．０５質量部を加えて、５０℃付近まで冷却した後、反応容器より取り出し、エポキシ（メタ）アクリレート（ａ１−２）を得た。
(Synthesis Example 2: Synthesis of Epoxy (Meta) Acrylate (a1-2))
Add 368.3 parts by mass of bisphenol A type epoxy resin (“Epiclon 850” manufactured by DIC Corporation, epoxy equivalent 188) to a 2L flask equipped with a thermometer, nitrogen introduction tube, and stirrer under nitrogen flow, and add to 60 ° C. After warming, 83.4 parts by mass of bisphenol A was added and the temperature was raised to 110 ° C. Then, 0.55 parts by mass of 2-methylimidazole was added, and it was confirmed that the epoxy equivalent was within the range of 375 ± 10, and the mixture was cooled to 100 ° C. After removing nitrogen using a vacuum pump, air was replaced. Subsequently, 102.2 parts by mass of methacrylic acid and 0.20 parts by mass of t-butylhydroquinone were charged at 100 ° C. under a gas flow atmosphere in which nitrogen and air were mixed 1: 1 and reacted for 2 hours, and then 2 -Methylimidazole 0.277 parts by mass was added, and the acid value and epoxy equivalent were measured. After confirming that the acid value was in the range of 3.0 to 7.0 and the epoxy equivalent was in the range of 5000 to 10000, the reaction was terminated. After adding 0.05 part by mass of t-butylhydroquinone and cooling to around 50 ° C., the mixture was taken out from the reaction vessel to obtain an epoxy (meth) acrylate (a1-2).
（実施例１：光硬化型ライニング材用樹脂組成物（１）の製造）
合成例１で得たエポキシ（メタ）クリレート（ａ１−１）７０質量部、フェノキシエチルメタクリレート３０質量部、２，２−ジメトキシ−２−フェニルアセトフェノン０．１５質量部、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０．１５質量部を混合し、光硬化型ライニング材用樹脂組成物（１）を得た。
ここで、エポキシ（メタ）クリレート（ａ１−１）及びフェノキシエチルメタクリレートからなる樹脂成分（Ａ−１）の屈折率は１．５４０８であった。
(Example 1: Production of resin composition (1) for photocurable lining material)
70 parts by mass of epoxy (meth) clearate (a1-1) obtained in Synthesis Example 1, 30 parts by mass of phenoxyethyl methacrylate, 0.15 parts by mass of 2,2-dimethoxy-2-phenylacetophenone, bis (2,4,6) -Trimethylbenzoyl) Phenylphosphine oxide 0.15 parts by mass was mixed to obtain a resin composition (1) for a photocurable lining material.
Here, the refractive index of the resin component (A-1) composed of epoxy (meth) clearate (a1-1) and phenoxyethyl methacrylate was 1.5408.
（実施例２：光硬化型ライニング材用樹脂組成物（２）の製造及び評価）
実施例１で用いたエポキシ（メタ）アクリレート（ａ１−１）７０質量部及びフェノキシエチルメタクリレート３０質量部を、エポキシ（メタ）アクリレート（ａ１−２）５５質量部及びフェノキシエチルメタクリレート４５質量部に変更し、２，２−ジメトキシ−２−フェニルアセトフェノン０．１５質量部、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０．１５質量部を、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１．０質量部に変更した以外は、実施例１と同様にして、光硬化型ライニング材用樹脂組成物（２）を得た。
ここで、エポキシ（メタ）クリレート（ａ１−２）及びフェノキシエチルメタクリレートからなる樹脂成分（Ａ−２）の屈折率は１．５４８９であった。
(Example 2: Production and evaluation of resin composition (2) for photocurable lining material)
70 parts by mass of epoxy (meth) acrylate (a1-1) and 30 parts by mass of phenoxyethyl methacrylate used in Example 1 were changed to 55 parts by mass of epoxy (meth) acrylate (a1-2) and 45 parts by mass of phenoxyethyl methacrylate. Then, 0.15 parts by mass of 2,2-dimethoxy-2-phenylacetophenone, 0.15 parts by mass of bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. A resin composition (2) for a photocurable lining material was obtained in the same manner as in Example 1 except that the content was changed to 1.0 part by mass.
Here, the refractive index of the resin component (A-2) composed of epoxy (meth) clearate (a1-2) and phenoxyethyl methacrylate was 1.5489.
（実施例３：光硬化型ライニング材用樹脂組成物（３）の製造及び評価）
実施例１で用いたエポキシ（メタ）アクリレート（ａ１−１）７０質量部及びフェノキシエチルメタクリレート３０質量部を、エポキシ（メタ）アクリレート（ａ１−２）３０質量部及びフェノキシエチルメタクリレート７０質量部に変更し、２，２−ジメトキシ−２−フェニルアセトフェノン０．１５質量部、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０．１５質量部を、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１．０質量部に変更した以外は、実施例１と同様にして、光硬化型ライニング材用樹脂組成物（３）を得た。
ここで、エポキシ（メタ）クリレート（ａ１−２）及びフェノキシエチルメタクリレートからなる樹脂成分（Ａ−３）の屈折率は１．５３５０であった。
(Example 3: Production and evaluation of resin composition (3) for photocurable lining material)
70 parts by mass of epoxy (meth) acrylate (a1-1) and 30 parts by mass of phenoxyethyl methacrylate used in Example 1 were changed to 30 parts by mass of epoxy (meth) acrylate (a1-2) and 70 parts by mass of phenoxyethyl methacrylate. Then, 0.15 parts by mass of 2,2-dimethoxy-2-phenylacetophenone, 0.15 parts by mass of bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. A resin composition (3) for a photocurable lining material was obtained in the same manner as in Example 1 except that the content was changed to 1.0 part by mass.
Here, the refractive index of the resin component (A-3) composed of epoxy (meth) clearate (a1-2) and phenoxyethyl methacrylate was 1.5350.
（比較例１：光硬化型ライニング材用樹脂組成物（Ｒ１）の調製及び評価）
実施例１で用いたフェノキシエチルメタクリレート３０質量部を、ジシクロペンテニルオキシエチルメタクリレート１５質量部及びネオペンチルグリコールジメタクリレート１５質量部に変更した以外は、実施例１と同様にして、光硬化型ライニング材用樹脂組成物（Ｒ１）を得た。
ここで、エポキシ（メタ）クリレート（ａ１−１）、ジシクロペンテニルオキシエチルメタクリレート、及びネオペンチルグリコールジメタクリレートからなる樹脂成分（ＲＡ−１）の屈折率は１．５２９６であった。
(Comparative Example 1: Preparation and Evaluation of Resin Composition (R1) for Photocurable Lining Material)
Photocurable lining in the same manner as in Example 1 except that 30 parts by mass of phenoxyethyl methacrylate used in Example 1 was changed to 15 parts by mass of dicyclopentenyloxyethyl methacrylate and 15 parts by mass of neopentyl glycol dimethacrylate. A resin composition for materials (R1) was obtained.
Here, the refractive index of the resin component (RA-1) composed of epoxy (meth) clearate (a1-1), dicyclopentenyloxyethyl methacrylate, and neopentyl glycol dimethacrylate was 1.5296.
［光硬化型ライニング材の製造］
３５cm×３５cmのガラス上に、ECRロービングクロス（５８０ｇ/ｍ2）を重ね、その上に上記で得た光硬化型ライニング材用樹脂組成物（１）を含浸する操作を5回繰り返して、３ｍｍ厚の積層板を得た後、この上に厚み０．２ｍｍのポリエステルフィルムを被覆して、光硬化型ライニング材（１）を作製した。
[Manufacturing of photo-curing lining material]
The operation of stacking an ECR roving cloth (580 g / m 2 ) on a 35 cm × 35 cm glass and impregnating the resin composition (1) for a photocurable lining material obtained above on the ECR roving cloth (580 g / m 2) was repeated 5 times to make 3 mm. After obtaining a thick laminated plate, a polyester film having a thickness of 0.2 mm was coated on the laminated plate to prepare a photocurable lining material (1).
［速硬化性及び厚膜硬化性の評価］
上記で得た光硬化型ライニング材（１）の表面に、高さ２０ｃｍからコールドミラーを備えたアイグラフィック株式会社製メタルハライドランプＭ０４５−３１Ｌ（発光長：３７５ｍｍ、４．５ｋＷ）を１．０ｍ／分の速度で２回通過させて、硬化物（１）を得た。バーコール硬度計（バーバー・コールマン社製「型式：ＧＹＺＪ９３４−１」）で硬化物の裏面バーコール硬さを測定し、以下の基準により、速硬化性及び厚膜硬化性を評価した。
〇：硬度５０以上
×：硬度５０未満
[Evaluation of fast curability and thick film curability]
On the surface of the photocurable lining material (1) obtained above, a metal halide lamp M045-31L (emission length: 375 mm, 4.5 kW) manufactured by Eye Graphic Co., Ltd. equipped with a cold mirror from a height of 20 cm is 1.0 m / The cured product (1) was obtained by passing the mixture twice at a rate of 1 minute. The backside Barcol hardness of the cured product was measured with a Barcol hardness tester (“Model: GYZJ934-1” manufactured by Barber Coleman), and the fast curability and thick film curability were evaluated according to the following criteria.
〇: Hardness 50 or more ×: Hardness less than 50
上記で得た光硬化型ライニング材用樹脂組成物（１）〜（３）、及び（Ｒ１）の評価結果を表１に示す。 Table 1 shows the evaluation results of the resin compositions (1) to (3) and (R1) for the photocurable lining material obtained above.
実施例１〜３の本発明の光硬化型ライニング材用樹脂組成から得られる光硬化型ライニング材は、速硬化性及び厚膜硬化性に優れることが確認された。 It was confirmed that the photocurable lining material obtained from the resin composition for the photocurable lining material of the present invention of Examples 1 to 3 was excellent in quick curability and thick film curability.
一方、比較例１は、樹脂成分の屈折率が本発明の下限である１．５３０より低い例であるが、厚膜硬化性が不十分であることが確認された。 On the other hand, Comparative Example 1 is an example in which the refractive index of the resin component is lower than the lower limit of 1.530 of the present invention, but it was confirmed that the thick film curability is insufficient.
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| CN113861359B (en) * | 2021-10-11 | 2024-01-30 | 中国电建集团中南勘测设计研究院有限公司 | Modified halloysite nanotube, photo-curing lining material, and preparation methods and applications thereof |
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