CN115698108A - Resin composition, pipe duct repairing material and pipe duct repairing method - Google Patents
Resin composition, pipe duct repairing material and pipe duct repairing method Download PDFInfo
- Publication number
- CN115698108A CN115698108A CN202180042670.8A CN202180042670A CN115698108A CN 115698108 A CN115698108 A CN 115698108A CN 202180042670 A CN202180042670 A CN 202180042670A CN 115698108 A CN115698108 A CN 115698108A
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- CN
- China
- Prior art keywords
- resin composition
- unsaturated polyester
- structure derived
- polyester oligomer
- canal
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 125
- 239000000463 material Substances 0.000 title claims description 89
- 238000000034 method Methods 0.000 title claims description 34
- 229920006305 unsaturated polyester Polymers 0.000 claims abstract description 65
- 239000000178 monomer Substances 0.000 claims abstract description 39
- 150000003077 polyols Chemical class 0.000 claims abstract description 34
- 229920005862 polyol Polymers 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 32
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 26
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 26
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims abstract description 24
- 239000003999 initiator Substances 0.000 claims abstract description 22
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001530 fumaric acid Substances 0.000 claims abstract description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 12
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000008439 repair process Effects 0.000 claims description 40
- 239000000126 substance Substances 0.000 claims description 32
- 229920005989 resin Polymers 0.000 claims description 30
- 239000011347 resin Substances 0.000 claims description 30
- 229920001567 vinyl ester resin Polymers 0.000 claims description 24
- 150000007519 polyprotic acids Polymers 0.000 claims description 20
- 230000001678 irradiating effect Effects 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000000016 photochemical curing Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 239000003365 glass fiber Substances 0.000 claims description 5
- 239000002990 reinforced plastic Substances 0.000 claims description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 description 65
- 238000001723 curing Methods 0.000 description 29
- 150000003254 radicals Chemical class 0.000 description 24
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 229920006337 unsaturated polyester resin Polymers 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920001187 thermosetting polymer Polymers 0.000 description 6
- 238000010276 construction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- -1 benzildimethylketal compound Chemical class 0.000 description 4
- 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 4
- 239000002244 precipitate Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000009418 renovation Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- DJKGDNKYTKCJKD-BPOCMEKLSA-N (1s,4r,5s,6r)-1,2,3,4,7,7-hexachlorobicyclo[2.2.1]hept-2-ene-5,6-dicarboxylic acid Chemical compound ClC1=C(Cl)[C@]2(Cl)[C@H](C(=O)O)[C@H](C(O)=O)[C@@]1(Cl)C2(Cl)Cl DJKGDNKYTKCJKD-BPOCMEKLSA-N 0.000 description 2
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical class C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- JYSDROPYFMOQPO-UHFFFAOYSA-N CC1=C(C(=O)C=2C(=C(C=CC=2)P(C2=CC=CC=C2)=O)C(C2=C(C=C(C=C2C)C)C)=O)C(=CC(=C1)C)C Chemical compound CC1=C(C(=O)C=2C(=C(C=CC=2)P(C2=CC=CC=C2)=O)C(C2=C(C=C(C=C2C)C)C)=O)C(=CC(=C1)C)C JYSDROPYFMOQPO-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 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
- 238000007664 blowing Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- NIDNOXCRFUCAKQ-UMRXKNAASA-N (1s,2r,3s,4r)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1[C@H]2C=C[C@@H]1[C@H](C(=O)O)[C@@H]2C(O)=O NIDNOXCRFUCAKQ-UMRXKNAASA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- ZQHJVIHCDHJVII-OWOJBTEDSA-N (e)-2-chlorobut-2-enedioic acid Chemical compound OC(=O)\C=C(\Cl)C(O)=O ZQHJVIHCDHJVII-OWOJBTEDSA-N 0.000 description 1
- 229940083957 1,2-butanediol Drugs 0.000 description 1
- 229940031723 1,2-octanediol Drugs 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- QTCNKIZNNWURDV-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol Chemical compound OCC(C)(C)CO.OCC(C)(C)CO QTCNKIZNNWURDV-UHFFFAOYSA-N 0.000 description 1
- OJRJDENLRJHEJO-UHFFFAOYSA-N 2,4-diethylpentane-1,5-diol Chemical compound CCC(CO)CC(CC)CO OJRJDENLRJHEJO-UHFFFAOYSA-N 0.000 description 1
- ZWNMRZQYWRLGMM-UHFFFAOYSA-N 2,5-dimethylhexane-2,5-diol Chemical compound CC(C)(O)CCC(C)(C)O ZWNMRZQYWRLGMM-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- PUBNJSZGANKUGX-UHFFFAOYSA-N 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=C(C)C=C1 PUBNJSZGANKUGX-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- PCKZAVNWRLEHIP-UHFFFAOYSA-N 2-hydroxy-1-[4-[[4-(2-hydroxy-2-methylpropanoyl)phenyl]methyl]phenyl]-2-methylpropan-1-one Chemical compound C1=CC(C(=O)C(C)(O)C)=CC=C1CC1=CC=C(C(=O)C(C)(C)O)C=C1 PCKZAVNWRLEHIP-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
- 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
- MWCBGWLCXSUTHK-UHFFFAOYSA-N 2-methylbutane-1,4-diol Chemical compound OCC(C)CCO MWCBGWLCXSUTHK-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- XIRDTMSOGDWMOX-UHFFFAOYSA-N 3,4,5,6-tetrabromophthalic acid Chemical compound OC(=O)C1=C(Br)C(Br)=C(Br)C(Br)=C1C(O)=O XIRDTMSOGDWMOX-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- YVPZFPKENDZQEJ-UHFFFAOYSA-N 4-propylcyclohexan-1-ol Chemical compound CCCC1CCC(O)CC1 YVPZFPKENDZQEJ-UHFFFAOYSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
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- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
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- PRRGXULZOZTZDK-UHFFFAOYSA-N [(2,6-dichlorobenzoyl)-(2,5-dimethylphenyl)phosphoryl]-(2,6-dichlorophenyl)methanone Chemical compound CC1=CC=C(C)C(P(=O)(C(=O)C=2C(=CC=CC=2Cl)Cl)C(=O)C=2C(=CC=CC=2Cl)Cl)=C1 PRRGXULZOZTZDK-UHFFFAOYSA-N 0.000 description 1
- RZITUYVIQBQJGJ-UHFFFAOYSA-N [(2,6-dichlorobenzoyl)-(4-ethoxyphenyl)phosphoryl]-(2,6-dichlorophenyl)methanone Chemical compound C1=CC(OCC)=CC=C1P(=O)(C(=O)C=1C(=CC=CC=1Cl)Cl)C(=O)C1=C(Cl)C=CC=C1Cl RZITUYVIQBQJGJ-UHFFFAOYSA-N 0.000 description 1
- ZEDSKTISNTXEQI-UHFFFAOYSA-N [(2,6-dichlorobenzoyl)-(4-propylphenyl)phosphoryl]-(2,6-dichlorophenyl)methanone Chemical compound C1=CC(CCC)=CC=C1P(=O)(C(=O)C=1C(=CC=CC=1Cl)Cl)C(=O)C1=C(Cl)C=CC=C1Cl ZEDSKTISNTXEQI-UHFFFAOYSA-N 0.000 description 1
- DNRISHWSPBDRTH-UHFFFAOYSA-N [(2,6-dichlorobenzoyl)-phenylphosphoryl]-(2,6-dichlorophenyl)methanone Chemical compound ClC1=CC=CC(Cl)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(Cl)C=CC=C1Cl DNRISHWSPBDRTH-UHFFFAOYSA-N 0.000 description 1
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- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
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- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 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
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
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- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
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- 239000003086 colorant Substances 0.000 description 1
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- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
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- 239000003822 epoxy resin Substances 0.000 description 1
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- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- FLBJFXNAEMSXGL-UHFFFAOYSA-N het anhydride Chemical compound O=C1OC(=O)C2C1C1(Cl)C(Cl)=C(Cl)C2(Cl)C1(Cl)Cl FLBJFXNAEMSXGL-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- LJZULWUXNKDPCG-UHFFFAOYSA-N nonane-1,2-diol Chemical compound CCCCCCCC(O)CO LJZULWUXNKDPCG-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- AEIJTFQOBWATKX-UHFFFAOYSA-N octane-1,2-diol Chemical compound CCCCCCC(O)CO AEIJTFQOBWATKX-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
-
- E—FIXED CONSTRUCTIONS
- E03—WATER SUPPLY; SEWERAGE
- E03F—SEWERS; CESSPOOLS
- E03F7/00—Other installations or implements for operating sewer systems, e.g. for preventing or indicating stoppage; Emptying cesspools
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L55/00—Devices or appurtenances for use in, or in connection with, pipes or pipe systems
- F16L55/18—Appliances for use in repairing pipes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Public Health (AREA)
- Hydrology & Water Resources (AREA)
- Inorganic Chemistry (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
A resin composition comprising (A) an unsaturated polyester oligomer, (B) a radically polymerizable monomer, and (C) a photopolymerization initiator, wherein the unsaturated polyester oligomer (A) comprises a structure derived from a polyol component (a 1) containing 55 to 85 mol% of neopentyl glycol relative to 100 mol% of the total polyol components, a structure derived from a polyacid component (a 2) containing isophthalic acid and/or terephthalic acid, and a structure derived from an unsaturated dibasic acid component (a 3) containing maleic anhydride and/or fumaric acid, and comprises 30 to 60 mol of the structure derived from the polyacid component (a 2) and 40 to 70 mol of the structure derived from the unsaturated dibasic acid component (a 3) relative to 100 mol of the structure derived from the polyol component (a 1).
Description
Technical Field
The present invention relates to a resin composition, a cured product, a method for producing a cured product, a material for repairing a pipe duct, and a method for repairing a pipe duct.
This application claims priority based on Japanese application No. 2020-130660, 7/31/2020, the contents of which are incorporated herein by reference.
Background
Conventionally, as a method for repairing an existing pipe duct such as a gas pipe, a water supply pipe, a sewer pipe, an agricultural water pipe, or the like, there is a method using a pipe duct repairing material in which a base material made of fibers is impregnated with a resin composition. Specifically, a canal repair material is placed at a predetermined position in an existing canal, and then a resin composition contained in the canal repair material is cured to repair the canal. Among these methods, there are a thermosetting application method using a thermosetting resin as a resin composition and a photocuring application method using a photocuring resin. In the thermosetting application method, the resin composition is cured using a heat medium such as warm water or steam. In the photo-curing method, the resin composition is cured by irradiating the pipe duct repair material with light such as ultraviolet light or visible light.
Patent document 1 describes a thermosetting resin composition for pipe lining materials, which contains an unsaturated polyester resin (a), a styrene monomer (b), and silica powder (c) as essential components.
Patent document 2 describes a resin composition for pipe duct repair containing (a) a vinyl ester resin composition, (B) a urethane (meth) acrylate composition, (C) an unsaturated polyester resin composition, and (D) a curing agent containing cumene hydroperoxide and t-butyl peroxybenzoate.
Patent document 3 describes a tubular photocurable lining material containing a photocurable resin composition containing an unsaturated polyester resin or vinyl ester resin, styrene, and a photopolymerization initiator.
In recent years, the distance of light-curing in a repair work for a pipe duct has been increased. This is because the curing speed of the resin composition is high and the working time is short as compared with the thermosetting working method. Further, the photo-curing method has advantages that the resin composition is less likely to be cured and shrunk, curing defects are less likely to occur, heat generation during curing is less, and emission of combustible gas during curing is less, as compared with the thermosetting method.
In the photocuring construction method, a gallium lamp, a metal halide lamp, a mercury lamp, or the like is used as a light source. Patent document 4 describes a lining method for a pipe in which a resin layer is irradiated with light using a light-emitting diode (LED) that mainly irradiates ultraviolet light. LEDs generate less heat, save energy, have a long life, and are excellent as light sources.
Documents of the prior art
Patent literature
Patent document 1: japanese patent No. 4055300
Patent document 2: japanese patent No. 6460999
Patent document 3: japanese patent No. 6095278
Patent document 4: japanese patent laid-open No. 2008-142996
Disclosure of Invention
Problems to be solved by the invention
However, in the conventional technique, even when light is irradiated to the pipe duct repair material used in the photocuring construction method, a repair surface having excellent heat resistance and chemical resistance may not be obtained.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a resin composition which is less likely to cause curing failure, can give a cured product having excellent heat resistance and chemical resistance, and can be preferably used as a material for a pipe duct repairing material.
It is another object of the present invention to provide a cured product obtained by curing the resin composition of the present invention, which has excellent heat resistance and chemical resistance, and a method for producing the same.
It is another object of the present invention to provide a pipe duct repair material which comprises a base material and the resin composition of the present invention impregnated in the base material and can provide a repaired surface having excellent heat resistance and chemical resistance.
In addition, an object of the present invention is to provide a method for repairing a canal using the canal repair material of the present invention.
Means for solving the problems
The present inventors have focused attention on the curing reaction of the resin composition in order to solve the above problems, and have made extensive studies.
As a result, they have found that a resin composition containing a specific unsaturated polyester oligomer which is considered to have a wide intermolecular distance and to be easily transmitted by light having a wavelength of 315 to 460 can be obtained by a structure containing a polyol component sufficiently containing neopentyl glycol. It is presumed that since the resin composition has good light transmittance, the irradiation light easily reaches not only the light irradiation surface but also the inside, and curing failure is less likely to occur.
The present inventors have confirmed that a cured product having excellent heat resistance and chemical resistance can be obtained by irradiating only light having a full-width at half maximum of 4 to 35nm and a central wavelength of 315 to 460nm, which does not include high-energy ultraviolet light having a wavelength of 200 to 314nm, to the resin composition.
That is, the present invention relates to the following matters.
[1] A resin composition, comprising:
(A) An unsaturated polyester oligomer;
(B) A radical polymerizable monomer; and
(C) A photopolymerization initiator,
the above-mentioned (A) unsaturated polyester oligomer comprises:
a structure derived from a polyol component (a 1), the polyol component (a 1) containing neopentyl glycol 55 to 85 mol% with respect to 100 mol% of the entire polyol component;
a structure derived from a polybasic acid component (a 2), said polybasic acid component (a 2) comprising isophthalic acid and/or terephthalic acid; and
a structure derived from an unsaturated dibasic acid component (a 3), the unsaturated dibasic acid component (a 3) containing maleic anhydride and/or fumaric acid,
wherein the structure derived from the polybasic acid component (a 2) is contained in an amount of 30 to 60 moles and the structure derived from the unsaturated dibasic acid component (a 3) is contained in an amount of 40 to 70 moles, based on 100 moles of the structure derived from the polyhydric alcohol component (a 1).
[2] The resin composition according to [1], wherein the content of isophthalic acid and/or terephthalic acid in the polybasic acid component (a 2) is 75 mol% or more,
the content of maleic anhydride and/or fumaric acid in the unsaturated dibasic acid component (a 3) is 90 mol% or more.
[3] The resin composition according to [1] or [2], wherein the unsaturated polyester oligomer (A) has a weight average molecular weight of 1000 to 20000.
[4] The resin composition according to any one of [1] to [3], wherein the content of the radically polymerizable monomer (B) is 20 to 60 parts by mass in 100 parts by mass of the total of the unsaturated polyester oligomer (A) and the radically polymerizable monomer (B),
the content of the photopolymerization initiator (C) is 0.01 to 10 parts by mass relative to 100 parts by mass of the total of the unsaturated polyester oligomer (A) and the radical polymerizable monomer (B).
[5] The resin composition according to any one of [1] to [4], further comprising (D) 10 to 30 parts by mass of a vinyl ester resin per 100 parts by mass of the total of the unsaturated polyester oligomer (A) and the radically polymerizable monomer (B).
[6] The resin composition according to any one of [1] to [5], wherein the photopolymerization initiator (C) is an acylphosphine compound and/or a benzil ketal compound.
[7] A cured product of the resin composition according to any one of [1] to [6], having a deflection temperature under load of 85 ℃ or higher as measured in accordance with JIS A7511, and having a mass change rate of ± 0.3% or less in a nitric acid resistance test of a chemical resistance test of a reinforced plastic composite pipe for sewer in accordance with the standards of the Japan sewer Association.
[8] A method for producing a cured product, which comprises curing a resin composition according to any one of [1] to [6] by irradiating the resin composition with light having a half-value width of 4 to 35nm and a central wavelength of 315 to 460 nm.
[9] A pipe repairing material comprising a base material and the resin composition according to any one of [1] to [6] impregnated in the base material.
[10] The canal patching material according to [9], wherein the base material is made of glass fiber and/or organic fiber.
[11] The canal repairing material according to [9] or [10], wherein the base material is tubular.
[12] A pipe repairing method comprises the following steps:
an installation step of installing the canal repairing material according to any one of [9] to [11] in an existing canal; and
and a photocuring step of irradiating the canal repairing material with light having a half-peak width of 4 to 35nm and a center wavelength of 315 to 460 nm.
ADVANTAGEOUS EFFECTS OF INVENTION
The resin composition of the present invention is less likely to cause curing failure, and can provide a cured product having excellent heat resistance and chemical resistance. Therefore, the resin composition of the present invention can be preferably used as a material for a canal repair material.
The canal repair material of the present invention comprises a base material and the resin composition of the present invention impregnated in the base material. Therefore, by providing the canal repair material in the existing canal and irradiating light having a half-peak width of 4 to 35nm and a central wavelength of 315 to 460nm, for example, a repaired surface having excellent heat resistance and chemical resistance can be obtained.
Drawings
Fig. 1 is a schematic perspective view for explaining an example of the canal repairing material according to the present embodiment.
Fig. 2 is a schematic perspective view showing an example of an existing canal repaired using the canal repairing material shown in fig. 1.
Detailed Description
The resin composition, cured product, method for producing cured product, material for repairing conduit and method for repairing conduit of the present invention will be described in detail below. The present invention is not limited to the embodiments described below.
[ resin composition ]
The resin composition of the present embodiment includes (a) an unsaturated polyester oligomer, (B) a radical polymerizable monomer, and (C) a photopolymerization initiator. The resin composition of the present embodiment may further contain (D) a vinyl ester resin, if necessary.
In the resin composition of the present embodiment, a part of the (a) unsaturated polyester oligomer and the (B) radically polymerizable monomer may be contained as a polymer of the (a) unsaturated polyester oligomer and the (B) radically polymerizable monomer.
< (A) unsaturated polyester oligomer
(A) The unsaturated polyester oligomer is copolymerized with (B) a radical polymerizable monomer to form an unsaturated polyester resin.
(A) The unsaturated polyester oligomer comprises: a structure derived from a polyol component (a 1), wherein the polyol component (a 1) contains neopentyl glycol 55 to 85 mol% with respect to 100 mol% of the total polyol components; a structure derived from a polybasic acid component (a 2), wherein the polybasic acid component (a 2) comprises isophthalic acid and/or terephthalic acid; and a structure derived from an unsaturated dibasic acid component (a 3), wherein the unsaturated dibasic acid component (a 3) contains maleic anhydride and/or fumaric acid.
(A) The unsaturated polyester oligomer can be synthesized by a known method.
The polyol component (a 1) used as a raw material of the unsaturated polyester oligomer (a) contains neopentyl glycol (2, 2-dimethyl-1, 3-propanediol) in an amount of 55 to 85 mol%, preferably 60 to 80 mol%, and more preferably 65 to 75 mol%.
The 2 methyl groups present in the side chain of neopentyl glycol extend the intermolecular distance of the unsaturated polyester oligomer (a) and allow light having a wavelength of 315 to 460 to easily pass therethrough. When neopentyl glycol is contained in an amount of 55 mol% or more in the polyol component (a 1), the unsaturated polyester oligomer (a) having good light transmittance can be obtained. The resin composition containing the unsaturated polyester oligomer (A) is easy to reach not only the light irradiation surface but also the inside by the irradiated light, is not easy to cause curing failure, and has high photocuring speed. Therefore, a cured product can be obtained without irradiating light in a high-energy ultraviolet region. Specifically, a cured product having a high density and good heat resistance can be obtained by irradiating only light having a half-value width of 4 to 35nm and a central wavelength of 315 to 460 nm. Further, 2 methyl groups present in the side chain of neopentyl glycol protect ester bond sites in the (a) unsaturated polyester oligomer synthesized using neopentyl glycol. Therefore, if a resin composition containing (a) an unsaturated polyester oligomer synthesized using (a 1) a polyol component containing neopentyl glycol in an amount of 55 mol% or more is cured, a cured product having good chemical resistance can be obtained.
Further, since neopentyl glycol contained in the polyol component (a 1) is 85 mol% or less, a precipitate is less likely to precipitate during the reaction for synthesizing the unsaturated polyester oligomer (a), and the synthesis can be easily performed. Further, since the neopentyl glycol contained in the polyol component (a 1) is 85 mol% or less, precipitates derived from high crystallinity are less likely to be generated in the resin composition, and the stability with time is improved.
As the polyol component (a 1) other than neopentyl glycol, conventionally known ones can be used. Specifically, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 2-methyl-1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, 2, 3-butanediol, 2-methyl-1, 4-butanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 2, 4-diethyl-1, 5-pentanediol, 1, 6-hexanediol, 2-ethyl-1, 3-hexanediol, 2, 5-dimethyl-2, 5-hexanediol, 1, 2-octanediol, 1, 2-nonanediol, 1, 4-cyclohexanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, bisphenol A and bisphenol F, bisphenol S, 2-bis (4-hydroxycyclohexyl) propane, polyethylene glycol, polypropylene glycol, and other 2-membered alcohols, glycerol, methyl ethane, pentaerythritol, ditrimethylolpropane, and the like can be used.
Among them, the polyol component (a 1) other than neopentyl glycol preferably contains ethylene glycol and/or propylene glycol, and particularly preferably contains propylene glycol, from the viewpoints of physical properties such as strength, heat resistance, and chemical resistance of a cured product obtained by curing the resin composition, impregnation of a substrate such as glass fibers and/or organic fibers with the resin composition, and cost. As the polyol component (a 1) other than neopentyl glycol, only one kind selected from the above may be used, or two or more kinds may be used.
The polybasic acid component (a 2) used as a raw material for the unsaturated polyester oligomer (a) contains isophthalic acid and/or terephthalic acid. The content of isophthalic acid and/or terephthalic acid in the polybasic acid component (a 2) is preferably 75 mol% or more, and more preferably 80 mol% or more, from the viewpoint of physical properties such as strength, heat resistance, chemical resistance, and the like of a cured product obtained by curing the resin composition, and from the viewpoint of cost. The polybasic acid component (a 2) may be solely isophthalic acid and/or terephthalic acid.
As the polybasic acid component (a 2) other than isophthalic acid and terephthalic acid, conventionally known ones can be used. Specifically, phthalic anhydride, succinic acid, adipic acid, sebacic acid, tetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, hexahydrophthalic acid (1, 2-cyclohexanedicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid), naphthalenedicarboxylic acid, trimellitic acid, pyromellitic acid, chlorendic acid (chlorendic acid), tetrabromophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, succinic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, and the like can be used.
Among them, the polybasic acid component (a 2) other than isophthalic acid and terephthalic acid preferably contains phthalic anhydride from the viewpoint of strength properties and cost of a cured product obtained by curing the resin composition. As the polybasic acid component (a 2) other than isophthalic acid and terephthalic acid, only one selected from the above may be used, or two or more selected from them may be used.
The unsaturated polyester oligomer (a) in the resin composition of the present embodiment contains 30 to 60 moles, preferably 40 to 50 moles, of the structure derived from the polybasic acid component (a 2) per 100 moles of the structure derived from the polyhydric alcohol component (a 1). Since the structure derived from the polybasic acid component (a 2) is contained by 30 moles or more per 100 moles of the structure derived from the polyhydric alcohol component (a 1), a cured resin having more excellent strength, heat resistance, and chemical resistance can be obtained. Since the structure derived from the polybasic acid component (a 2) is contained in an amount of 60 mol or less, turbidity of the resin composition due to precipitation of an acid component having high crystallinity with time hardly occurs. Therefore, the photocurability of the resin composition is not easily impaired.
The unsaturated dibasic acid component (a 3) used as a raw material of the unsaturated polyester oligomer (a) contains maleic anhydride and/or fumaric acid. The content of maleic anhydride and/or fumaric acid in the unsaturated dibasic acid component (a 3) is preferably 90 mol% or more from the viewpoints of physical properties such as strength, heat resistance, and chemical resistance of a cured product obtained by curing the resin composition, copolymerizability with (B) a radical polymerizable monomer such as styrene, and cost. The unsaturated dibasic acid component (a 3) may be only maleic anhydride and/or fumaric acid.
As the unsaturated dibasic acid component (a 3) other than maleic anhydride and fumaric acid, conventionally known ones can be used. Specifically, itaconic acid, citraconic acid, chloromaleic acid, and the like can be used. As the unsaturated dibasic acid component (a 3) other than maleic anhydride and fumaric acid, only one kind selected from the above may be used, or two or more kinds may be used.
The unsaturated polyester oligomer (a) in the resin composition of the present embodiment contains 40 to 70 moles, preferably 45 to 65 moles, of the structure derived from the unsaturated dibasic acid component (a 3) with respect to 100 moles of the structure derived from the polyol component (a 1). Since the structure derived from the unsaturated dibasic acid component (a 3) is contained in an amount of 40 moles or more based on 100 moles of the structure derived from the polyol component (a 1), the photocuring speed is high. Further, since the structure derived from the unsaturated dibasic acid component (a 3) is contained by 40 moles or more, the amount of the unsaturated acid which becomes a crosslinking point (starting point of curing) at the time of curing is not insufficient, and a cured product having excellent strength, heat resistance, and chemical resistance can be obtained. Further, since the structure derived from the unsaturated dibasic acid component (a 3) is 70 mol or less, the heat generation temperature at the time of curing can be prevented from becoming excessively high, and a cured product free from cracks can be obtained. Further, since the structure derived from the unsaturated dibasic acid component (a 3) is 70 mol or less, the amount of the unsaturated acid is excessive, and thus a cured product is not brittle, and a cured product having high toughness can be obtained.
(A) The unsaturated polyester oligomer preferably has a weight average molecular weight in terms of polystyrene of 1000 to 20000, more preferably 4000 to 17000, and still more preferably 7000 to 15000. When the unsaturated polyester oligomer (A) has a weight average molecular weight of 1000 or more, a cured product having more excellent heat resistance and chemical resistance can be obtained. If the weight average molecular weight of the unsaturated polyester oligomer (A) is 20000 or less, the viscosity of the resin composition is less likely to increase due to the high molecular weight unsaturated polyester resin. The unsaturated polyester oligomer (a) having a weight average molecular weight of 20000 or less has good uniformity of molecular weight. Therefore, it is preferable that the unsaturated polyester oligomer (a) has a weight average molecular weight of 20000 or less, since a cured product having uniform characteristics can be easily obtained.
The content of the unsaturated polyester oligomer (a) contained in the resin composition of the present embodiment can be calculated by a method of analyzing the composition of the resin composition using a Nuclear Magnetic Resonance (NMR) apparatus.
The structure derived from the polyol component (a 1), the structure derived from the polyacid component (a 2), and the structure derived from the unsaturated dibasic acid component (a 3) contained in the unsaturated polyester oligomer (a) of the resin composition of the present embodiment can be obtained by subjecting the unsaturated polyester oligomer (a) to reaction with a Nuclear Magnetic Resonance (NMR) apparatus 1 H-NMR measurement was carried out by calculating the composition and composition ratio (molar ratio) of the components from the number of protons and the integrated value obtained.
< free radical polymerizable monomer (B) >
(B) The radical polymerizable monomer is copolymerized with an unsaturated bond in the molecular skeleton of the unsaturated polyester oligomer (A) to form an unsaturated polyester resin. (B) The radical polymerizable monomer is a compound having an olefinic carbon-carbon double bond (C = C).
As the radical polymerizable monomer (B), styrene monomers such as styrene, compounds obtained by bonding a substituent selected from the group consisting of an alkyl group, a nitro group, a cyano group, an amide group, a halogen group and a vinyl group to any of the α -position, the ortho-position, the meta-position and the para-position of styrene, and ester derivatives thereof can be used. The radical polymerizable monomer (B) may be used alone or two or more kinds selected from the above. Among the above, styrene is particularly preferably used as the radical polymerizable monomer (B) in order to achieve good copolymerizability with the unsaturated polyester oligomer (a).
(A) The content of the radical polymerizable monomer (B) in 100 parts by mass of the total of the unsaturated polyester oligomer and the radical polymerizable monomer (B) is preferably 20 to 60 parts by mass, and more preferably 35 to 55 parts by mass. When the content of the radical polymerizable monomer (B) is 20 parts by mass or more, a resin composition capable of obtaining a cured product having excellent strength is obtained. If the content of the radical polymerizable monomer (B) is 60 parts by mass or less, the resin composition does not excessively become high in viscosity. Therefore, for example, when the resin composition is used as a resin composition for a base material impregnated with a pipe duct repair material, the resin composition is preferable because it has good wettability and permeability to the base material and can achieve excellent workability.
[ C ] photopolymerization initiator
As the photopolymerization initiator (C), a known intramolecular cleavage type photopolymerization initiator can be used, and 1 or 2 or more types can be appropriately selected and used according to the wavelength of irradiation light from a light source used for curing the resin composition.
Examples of the intramolecular cleavage type photopolymerization initiator include benzildimethylketal compounds, α -hydroxyalkylphenone compounds, α -aminoalkylphenone compounds, acylphosphine compounds, benzildione compounds, and the like.
Examples of the benzildimethylketal compound include 2, 2-dimethoxy-1, 2-diphenylethan-1-one.
Examples of the α -hydroxyalkylphenone compounds include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl ] -phenyl } -2-methyl-propan-1-one, and oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone).
Examples of the α -aminoalkylphenone-based compound include 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinophenyl) -1-butanone, and the like.
Examples of the acylphosphine-based compound include bis (2, 4, 6-trimethylbenzoyl) -diphenylphosphine oxide, bis (2, 6-dichlorobenzoyl) -phenylphosphine oxide, bis (2, 6-dichlorobenzoyl) -2, 5-dimethylphenylphosphine oxide, bis (2, 6-dichlorobenzoyl) -4-ethoxyphenylphosphine oxide, bis (2, 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2, 4-trimethylpentylphosphine oxide, and the like.
Among these photopolymerization initiators (C), in particular, in order to efficiently generate active species by absorbing light having a wavelength of 315 to 460nm, when light having a wavelength of 315 to 460nm is irradiated to the resin composition, 2-dimethoxy-1, 2-diphenylethan-1-one or bis (2, 4, 6-trimethylbenzoyl) -diphenylphosphine oxide is preferably used.
(C) The content of the photopolymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, and still more preferably 0.20 to 5 parts by mass, based on 100 parts by mass of the total of the unsaturated polyester oligomer (a) and the radical polymerizable monomer (B). If the content of the photopolymerization initiator (C) is 0.01 parts by mass or more, the effect of accelerating the initiation of the radical polymerization of the unsaturated polyester oligomer (a) and the radical polymerizable monomer (B) and the polymerization rate of the radical polymerization becomes remarkable. Therefore, a resin composition which can give a cured product having high density and excellent heat resistance is obtained. When the content of the photopolymerization initiator (C) is 10 parts by mass or less, rapid curing reaction and heat generation are less likely to occur during curing of the resin composition, and a cured product free from cracks and fissures can be obtained.
< D vinyl ester resin >
Examples of the vinyl ester resin (D) include epoxy (meth) acrylates obtained by reacting an epoxy resin with (meth) acrylic acid. As the vinyl ester resin (D), a bisphenol type vinyl ester resin is preferably used in order to obtain a resin composition which can give a cured product having further excellent heat resistance and chemical resistance.
(D) The vinyl ester resin preferably has a weight average molecular weight of 500 to 6000, more preferably 1000 to 5000. When the weight average molecular weight is 500 or more, a resin composition which can give a cured product having more excellent heat resistance and chemical resistance is obtained. If the weight average molecular weight is 6000 or less, the viscosity of the resin composition due to the high molecular weight vinyl ester resin is not easily increased, and therefore, it is preferable.
(D) The vinyl ester resin is contained in an amount of preferably 10 to 30 parts by mass, more preferably 12 to 28 parts by mass, and still more preferably 14 to 26 parts by mass, based on 100 parts by mass of the total of the unsaturated polyester oligomer (a) and the radically polymerizable monomer (B). When the vinyl ester resin (D) is contained in an amount of 10 parts by mass or more, a resin composition which can give a cured product having further excellent heat resistance and chemical resistance is obtained. When the content of the (D) vinyl ester resin is 30 parts by mass or less, the decrease in photocurability due to the decrease in the concentration of unsaturated groups and the decrease in photocurability due to the generation of turbidity accompanying the decrease in compatibility of the (D) vinyl ester resin with the (a) unsaturated polyester oligomer do not occur. Therefore, a cured product having better heat resistance and chemical resistance can be obtained. Further, if the content of the vinyl ester resin (D) is 30 parts by mass or less, the viscosity increase due to hydrogen bonds formed by hydroxyl groups in the side chain of the vinyl ester resin (D) is less likely to occur, and a resin composition having good impregnation properties into a substrate such as glass fibers and/or organic fibers is preferable.
The resin composition of the present embodiment may contain other additives as necessary within a range not impairing the effects of the present invention. Examples of the additives include ultraviolet absorbers, coupling agents, thickeners, colorants, flame retardants, and fillers.
< method for producing resin composition >
The resin composition of the present embodiment can be produced by a method of mixing (a) an unsaturated polyester oligomer, (B) a radical polymerizable monomer, (C) a photopolymerization initiator, (D) a vinyl ester resin and other additives, which are added as needed.
The resin composition of the present embodiment can be produced by the following method.
For example, an unsaturated polyester resin in which (a) an unsaturated polyester oligomer is dissolved in (B) a radically polymerizable monomer is produced by mixing (a) an unsaturated polyester oligomer and (B) a radically polymerizable monomer.
Then, the unsaturated polyester resin obtained can be produced by a method of mixing the unsaturated polyester resin, (C) a photopolymerization initiator, (D) a vinyl ester resin and other additives, if necessary.
The method for mixing the components contained in the resin composition of the present embodiment is not particularly limited, and for example, the mixing may be performed using a stirring blade powered by a motor, a homogenizer, or the like.
[ cured product ]
The cured product of the present embodiment is obtained by curing the resin composition of the present embodiment.
The deflection temperature under load of the cured product of the present embodiment measured in accordance with JIS a 7511 is preferably 85 ℃ or more, and more preferably 90 ℃ or more. The resin composition with the load deflection temperature of a cured product being more than 85 ℃ is used as the resin composition for impregnating the base material of the canal repairing material, so that the characteristic of the load deflection temperature in a ' canal renovation construction method ' 1236512395123124276. Construction management 12460124521248912512512521125125125521251251251255 ' is satisfied under the condition that the canal repairing material is used for renovating a sewer pipe.
The tensile elongation at break of the cured product of the present embodiment measured in accordance with JIS a 7511 is preferably 3.5% or more, and more preferably 5.0% or more. A resin composition with a tensile elongation at break of a cured product of 3.5% or more is used as a resin composition impregnated into a base material of a canal repair material, so that the characteristic of the tensile elongation at break in a ' canal renovation construction method ' 123652312412362696 is satisfied in a ' canal renovation construction method ' \12427336aconstruction management 12412452124891252112552125125521251251984 '.
The cured product of the present embodiment preferably has a mass change rate of ± 0.3% or less, preferably ± 0.25% or less in the nitric acid resistance test in the chemical resistance test of the reinforced plastic composite pipe for sewer (K-2) in accordance with the standard of japan sewer association (JSWAS). By using a resin composition in which the rate of change in mass in a nitric acid resistance test of a cured product is within ± 0.3% as a resin composition impregnated into a base material of a canal repair material, the canal repair material can satisfy the nitric acid resistance characteristics in a reinforced plastic composite pipe for a sewer of the japan sewer association standard and can obtain a repaired surface having good chemical resistance.
[ method for producing cured product ]
The method for producing the cured product of the present embodiment is not particularly limited, and a method of irradiating the resin composition of the present embodiment with light to cure the resin composition may be used.
As a light source for irradiating light to the resin composition of the present embodiment, a general Light Emitting Diode (LED) can be used. The LED generates less heat, saves energy, has a long life, and is preferable as a light source.
As the light source, any light source may be used as long as the resin composition of the present embodiment can be cured, and for example, a light source that irradiates light in a wide wavelength range, such as a gallium lamp, a metal halide lamp, or a mercury lamp, may be used. In this case, the resin composition of the present embodiment is also easily cured to be a cured product.
The resin composition of the present embodiment is less likely to cause curing failure. Therefore, in the method for producing a cured product of the present embodiment, for example, a method of irradiating only light not containing light in a high-energy ultraviolet region to the resin composition of the present embodiment with LED or the like and curing the same can be used.
As the light not containing the light of the high-energy ultraviolet region, for example, light having a half-value width of 4 to 35nm and a center wavelength of 315 to 460nm can be used. The center wavelength of the light ranges from the region on the high energy side of UV-Sup>A to the blue region in the visible region. The central wavelength of light irradiated to the resin composition can be appropriately determined depending on the thickness of a desired cured product (molded article).
The resin composition of the present embodiment may be cured by irradiation with only a single wavelength light having a high wavelength purity. Therefore, the half-width of light not including light in the high-energy ultraviolet region may be 6 to 25nm, or 8 to 15nm.
The light irradiated to the resin composition of the present embodiment may be light having a half-width of 4 to 35nm and a center wavelength of 340 to 430nm, or light having a half-width of 4 to 35nm and a center wavelength of 350 to 405 nm.
In the method for producing a cured product according to the present embodiment, the illuminance and the irradiation time of light irradiated to the resin composition may be appropriately determined depending on the thickness of a desired cured product (molded product), the wavelength of the irradiation light, and the like, and are not particularly limited.
The resin composition of the present embodiment includes (a) an unsaturated polyester oligomer, (B) a radical polymerizable monomer, and (C) a photopolymerization initiator. The unsaturated polyester oligomer (a) in the resin composition of the present embodiment has a structure derived from a polyol component (a 1) containing 55 to 85 mol% of neopentyl glycol with respect to 100 mol% of the total polyol components, a structure derived from a polyacid component (a 2) containing isophthalic acid and/or terephthalic acid, and a structure derived from an unsaturated dibasic acid component (a 3) containing maleic anhydride and/or fumaric acid. The resin composition of the present embodiment contains 30 to 60 moles of the structure derived from the polybasic acid component (a 2) and 40 to 70 moles of the structure derived from the unsaturated dibasic acid component (a 3) per 100 moles of the structure derived from the polyhydric alcohol component (a 1).
Therefore, the resin composition of the present embodiment is less likely to cause curing failure, and a cured product having excellent heat resistance and chemical resistance can be obtained. More specifically, the polyol component (a 1) of the unsaturated polyester oligomer (a) in the resin composition of the present embodiment contains 55 to 85 mol% of neopentyl glycol, and the structure derived from the polyol component (a 1), the structure derived from the polyacid component (a 2), and the structure derived from the unsaturated dibasic acid component (a 3) are contained at specific ratios. Therefore, the unsaturated polyester oligomer (A) has good light transmittance and ester bond sites are protected. As a result, the resin composition of the present embodiment can easily reach not only the light irradiation surface but also the inside with the irradiated light, and the photocuring speed is high. Further, the cured product of the resin composition of the present embodiment has high density and good heat resistance and chemical resistance.
Therefore, the resin composition of the present embodiment can be preferably used as a material for a canal repair material.
[ Material for repairing canals ]
Fig. 1 is a schematic perspective view for explaining an example of the canal repair material according to the present embodiment.
The canal repair material 11 of the present embodiment includes a base 10 and a resin composition impregnated into the base 10. The canal repairing material 11 of the present embodiment is obtained by impregnating the base 10 with the resin composition of the above-described embodiment.
The base material 10 is made of a material having appropriate flexibility and strength to follow the shape of the inner wall of the pipe duct and having gaps into which the resin composition can be impregnated. Specifically, the substrate 10 is preferably made of glass fibers and/or organic fibers. Examples of the organic fibers include fibers made of polyester, polypropylene, polyethylene, vinylon, nylon, acrylic, and the like.
The shape of the substrate 10 is preferably tubular (cylindrical) as shown in fig. 1. If the base material 10 is tubular, the pipe channel repair material 11 can be easily provided annularly along the inner peripheral surface of the pipe channel.
A known resin film may be provided on the inner surface and/or the outer portion of the canal repair material 11. The resin film protects the surface of the canal repair material 11 and improves workability in repairing a canal using the canal repair material 11. The resin film provided on the inner surface of the canal repair material 11 may be peeled and removed from the canal repair material 11 after curing the resin composition impregnated into the base material 10.
The shape of the substrate 10 is not limited to the tubular shape shown in fig. 1, and may be, for example, a sheet shape.
[ method of repairing pipe canal ]
Next, as an example of the pipe duct repairing method of the present embodiment, a case where a pipe duct is repaired using the pipe duct repairing material 11 shown in fig. 1 will be described as an example.
Fig. 2 is a schematic perspective view showing an example of an existing canal repaired using the canal repairing material shown in fig. 1. In fig. 2, reference numeral 20 denotes a pipe duct. The pipe conduit 20 to be repaired by the pipe conduit repairing method according to the present embodiment includes, for example, existing pipe conduits such as gas pipes, tap water pipes, sewer pipes, agricultural water pipes, industrial water pipes, power pipes, and communication pipes.
As a method for repairing the canal 20 using the canal repair material 11 shown in fig. 1, for example, the following method can be used. The canal repair material 11 is installed at a predetermined position in the longitudinal direction in the canal 20 by a known method (installation step). Next, pressure is applied to the inner surface of the canal repair material 11, for example, using air, so that the outer surface of the canal repair material 11 is brought into close contact with the inner surface of the canal 20. Further, the canal repair material 11 is irradiated with light from the inside of the canal repair material 11 using a known light irradiation device (photocuring step). Thereby, the resin composition of the base 10 impregnated with the canal repair material 11 is cured. In the present embodiment, light having a half-peak width of 4 to 35nm and a center wavelength of 315 to 460nm can be used as light to be irradiated to the canal repairing material 11. As the light source, a Light Emitting Diode (LED) is preferably used.
The canal repairing material 11 of the present embodiment includes a base 10 and the resin composition of the present embodiment impregnated into the base 10. Therefore, by setting the canal repairing material 11 in the existing canal 20 and irradiating the canal repairing material 11 with only light having a half-value width of 4 to 35nm and a central wavelength of 315 to 460nm and not containing light in a high-energy ultraviolet region, curing failure does not easily occur even if the resin composition is cured, and a repaired surface having good heat resistance and chemical resistance can be obtained. Therefore, when the canal 20 is repaired using the canal repair material 11 of the present embodiment, a general Light Emitting Diode (LED) can be used as a light source for irradiating light to the canal repair material 11.
Examples
The present invention will be described in more detail below with reference to examples and comparative examples. The present invention is not limited to the following examples.
< Synthesis of unsaturated polyester oligomer (UPE-1 to UPE-10) >
In a four-necked flask equipped with a thermometer, a stirrer, an inert gas blowing tube and a reflux condenser, polyol (1) and polyacid (2) shown in tables 1 and 2 were added in the proportions shown in tables 1 and 2. Further, the polymerization reaction was carried out at 215 ℃ for 10 hours while blowing nitrogen into the four-necked flask. Then, the reaction solution was cooled until it became 150 ℃.
To the cooled reaction solution, (3) unsaturated dibasic acids shown in tables 1 and 2 were added in the proportions shown in tables 1 and 2, and the temperature was raised to 215 ℃ to conduct condensation reaction for 10 hours.
By the above-mentioned steps, (A) unsaturated polyester oligomers (UPE-1 to UPE-9) were obtained.
In the polyol component (a 1) containing UPE-10 having neopentyl glycol content of 90 mol%, the unsaturated polyester oligomer (a) is not obtained because precipitates precipitate and turbidity occurs by the reaction for synthesizing the unsaturated polyester oligomer (a).
TABLE 1
TABLE 2
The unsaturated polyester oligomers (UPE-1 to UPE-9) (A) were examined for their weight average molecular weights by the following methods. The results are shown in tables 1 and 2.
The weight average molecular weights shown in tables 1 and 2 were determined by Gel Permeation Chromatography (GPC) under the following conditions based on standard polystyrene.
Column: \124711251912454
Column temperature: 40 deg.C
Sample preparation: (A) 0.2% tetrahydrofuran solution of unsaturated polyester oligomer
Developing solvent: tetrahydrofuran (THF)
A detector: differential refractometer (\124711251912454\124871248312463s (manufactured by showa electrician corporation)
Flow rate: 1 mL/min
"examples 1 to 10, comparative examples 1 to 4"
Unsaturated polyester resins were produced by mixing (a) unsaturated polyester oligomers (UPE-1 to UPE-9) and styrene as a radical polymerizable monomer (B) at the ratios shown in tables 3 and 4, and polymerizing them by using a stirring blade powered by a motor.
The obtained unsaturated polyester resin, the photopolymerization initiator (C) shown in tables 3 and 4, and the vinyl ester resin (D) added as needed were added in the proportions shown in tables 3 and 4, and mixed by using a stirring blade powered by a motor, to obtain resin compositions of examples 1 to 10 and comparative examples 1 to 4.
The content of the radical polymerizable monomer (B) shown in tables 3 and 4 is the content (parts by mass) of 100 parts by mass of the total of the unsaturated polyester oligomer (a) and the radical polymerizable monomer (B).
The content of the photopolymerization initiator (C) shown in tables 3 and 4 is a content (part by mass) based on 100 parts by mass of the total of the unsaturated polyester oligomer (a) and the radical polymerizable monomer (B).
The content of the vinyl ester resin (D) shown in tables 3 and 4 is a content (part by mass) based on 100 parts by mass of the total of the unsaturated polyester oligomer (a) and the radical polymerizable monomer (B). Further, as the (D) vinyl ester resin, a bisphenol type vinyl ester resin (R-806; weight average molecular weight 2400; manufactured by Showa Denko K.K..
TABLE 4
Next, the resin compositions of examples 1 to 8 and 10 and comparative examples 1 to 4 were cured by the following methods to obtain cured products.
The resin composition was charged into a mold, and as a light source, a light emitting diode (trade name; UV-LED irradiator H-4MLH84-V2-1S12-SM1 (usable wavelength: 385 nm) manufactured by HOYA Co., ltd.) having a half-peak width of 10nm and a center wavelength of 385nm was used at an irradiation illuminance of 40mW/cm 2 A (illuminance meter: 1245412471124580. An ultraviolet illuminance meter UIT-201) was irradiated for 30 minutes to obtain a cured product in the form of a sheet having a length of 200mm, a width of 200mm and a thickness of 4 mm.
The cured products of examples 1 to 8 and 10 and comparative examples 1 to 4 were measured for "deflection temperature under load (heat resistance)" and "tensile elongation at break (toughness)" in accordance with JIS a 7511, and evaluated according to the criteria shown in tables 3 and 4.
The cured products of examples 1 to 8 and 10 and comparative examples 1 to 4 were evaluated by the criteria shown in tables 3 and 4, respectively, by measuring the "nitric acid resistance (chemical resistance)" according to the chemical resistance test of reinforced plastic composite pipe for sewer (K-2) of the japanese sewer association standard (JSWAS). The results are shown in tables 3 and 4. The numerical values (mass change rates) of the nitric acid resistance of JWAS K-2 shown in tables 3 and 4 are absolute values.
Next, a #450 chopped strand mat (trade name: ECM450-501/T, 12475125238812521\\125641242,12473125011246,12412549124150,12496125150 mm, manufactured by 12540409, was prepared, and 6 square pieces of 150mm in length and 150mm in width were cut out, and a laminate was obtained by impregnating about 38g of the resin composition of example 9 with a defoaming roller. The laminate thus obtained was irradiated with 40mW/cm of light from a light-emitting diode (trade name; UV-LED irradiator H-4MLH84-V2-1S12-SM1 (usable wavelength: 385 nm) manufactured by HOYA Co., ltd.) having a half-peak width of 10nm and a center wavelength of 385nm 2 A cured product of example 9, which had a plate shape of 150mm in length, 150mm in width and 5mm in thickness, was obtained by irradiating light for 3 minutes from a photometer 1245412471124580.
The cured product of example 9 and the cured product of example 3 obtained in this way were measured for "flexural strength" according to JIS a 7511, and evaluated according to the following criteria.
The results are shown in table 3.
(Standard)
○；100～149MPa
◎；≥150MPa
As shown in Table 3, the cured products of examples 1 to 8 and 10 were evaluated as "good" or "excellent" in terms of "heat resistance", "chemical resistance" and "toughness". In particular, the cured products of examples 1 and 2 produced using the resin composition containing (D) a vinyl ester resin all had very good evaluations for "heat resistance", "chemical resistance", and "toughness".
Further, as shown in Table 3, the cured product of example 3 was evaluated as "flexural strength". Further, the cured product of example 9 produced using the same resin composition as the cured product of example 3 and the base material was evaluated as "flexural strength" having an excellent value.
In contrast, as shown in Table 4, the cured product of comparative example 1 using UPE-3 containing 50 mol% of neopentyl glycol as the polyol component (a 1) was evaluated for "chemical resistance".
The cured product of comparative example 2 using UPE-4 containing 20 mol% of neopentyl glycol was evaluated for "chemical resistance".
Further, the cured product of comparative example 3 using UPE-6 in which the polyol component (a 1) contained 65 moles of the structure derived from the polyacid component (a 2) and 35 moles of the structure derived from the unsaturated dibasic acid component (a 3) was evaluated as "heat resistance" and "chemical resistance" to be x.
In addition, the cured product of comparative example 4 using UPE-9 in which the polyol component (a 1) contained 25 moles of structures derived from the polyacid component (a 2) and 75 moles of structures derived from the unsaturated dibasic acid component (a 3) cracked when the resin composition was cured, and a cured product could not be obtained.
Description of the symbols
10. Base material, 11. Canal repair material, 20. Canal.
Claims (12)
1. A resin composition, comprising:
(A) An unsaturated polyester oligomer;
(B) A radical polymerizable monomer; and
(C) A photopolymerization initiator,
the (A) unsaturated polyester oligomer comprises:
a structure derived from a polyol component (a 1), the polyol component (a 1) containing neopentyl glycol 55 to 85 mol% with respect to 100 mol% of the entire polyol component;
a structure derived from a polybasic acid component (a 2), said polybasic acid component (a 2) comprising isophthalic acid and/or terephthalic acid; and
a structure derived from an unsaturated dibasic acid component (a 3), the unsaturated dibasic acid component (a 3) containing maleic anhydride and/or fumaric acid,
wherein the structure derived from the polybasic acid component (a 2) is contained in an amount of 30 to 60 moles and the structure derived from the unsaturated dibasic acid component (a 3) is contained in an amount of 40 to 70 moles, based on 100 moles of the structure derived from the polyhydric alcohol component (a 1).
2. The resin composition according to claim 1, wherein the content of isophthalic acid and/or terephthalic acid in the polybasic acid component (a 2) is 75 mol% or more,
the content of maleic anhydride and/or fumaric acid in the unsaturated dibasic acid component (a 3) is 90 mol% or more.
3. The resin composition according to claim 1 or 2, wherein the unsaturated polyester oligomer (A) has a weight average molecular weight of 1000 to 20000.
4. The resin composition according to any one of claims 1 to 3, wherein the content of the (B) radically polymerizable monomer is 20 to 60 parts by mass in 100 parts by mass in total of the (A) unsaturated polyester oligomer and the (B) radically polymerizable monomer,
the content of the photopolymerization initiator (C) is 0.01 to 10 parts by mass relative to 100 parts by mass of the total of the unsaturated polyester oligomer (A) and the radical polymerizable monomer (B).
5. The resin composition according to any one of claims 1 to 4, further comprising (D) 10 to 30 parts by mass of a vinyl ester resin per 100 parts by mass of the total of the unsaturated polyester oligomer (A) and the radically polymerizable monomer (B).
6. The resin composition according to any one of claims 1 to 5, wherein the photopolymerization initiator (C) is an acylphosphine-based compound and/or a benzil ketal-based compound.
7. A cured product of the resin composition according to any one of claims 1 to 6, having a deflection temperature under load of 85 ℃ or higher as measured in accordance with JIS A7511, and having a mass change rate of ± 0.3% or less in a nitric acid resistance test of a chemical resistance test of a reinforced plastic composite pipe for sewer in accordance with the standards of the Japan sewer Association.
8. A method for producing a cured product, comprising irradiating the resin composition according to any one of claims 1 to 6 with light having a half-value width of 4 to 35nm and a central wavelength of 315 to 460nm to cure the resin composition.
9. A pipe duct repair material comprising a base material and the resin composition according to any one of claims 1 to 6 impregnated in the base material.
10. The canal repair material of claim 9, wherein the base material is composed of glass fibers and/or organic fibers.
11. The canal repair material according to claim 9 or 10, wherein the base material is tubular.
12. A pipe repairing method comprises the following steps:
a setting step of setting the canal repairing material according to any one of claims 9 to 11 in an existing canal; and
and a photocuring step of irradiating the canal repair material with light having a half-peak width of 4 to 35nm and a center wavelength of 315 to 460 nm.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020-130660 | 2020-07-31 | ||
| JP2020130660 | 2020-07-31 | ||
| PCT/JP2021/027840 WO2022025097A1 (en) | 2020-07-31 | 2021-07-28 | Resin composition, conduit repair material, and conduit repair method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115698108A true CN115698108A (en) | 2023-02-03 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202180042670.8A Pending CN115698108A (en) | 2020-07-31 | 2021-07-28 | Resin composition, pipe duct repairing material and pipe duct repairing method |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP7435788B2 (en) |
| KR (1) | KR20230009915A (en) |
| CN (1) | CN115698108A (en) |
| WO (1) | WO2022025097A1 (en) |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50154390A (en) * | 1974-06-03 | 1975-12-12 | ||
| JP3893605B2 (en) * | 1997-07-25 | 2007-03-14 | 日本ゼオン株式会社 | Irradiation curable unsaturated polyester resin composition and method for molding the composition |
| JP4055300B2 (en) | 1999-08-30 | 2008-03-05 | 日立化成工業株式会社 | Thermosetting resin composition for pipe lining material, pipe lining material and pipe lining method |
| JP2002062644A (en) | 2000-05-30 | 2002-02-28 | Nippon Shokubai Co Ltd | Photosensitive resin composition, covering material and matrix material for frp |
| JP2003049974A (en) | 2001-08-07 | 2003-02-21 | Hitachi Chem Co Ltd | Polymerizable composition, photopolymerizable resin composition, and pipe-lining material and pipe-lining method using the same |
| JP5512069B2 (en) * | 2006-04-21 | 2014-06-04 | 東亜グラウト工業株式会社 | Curable resin composition, lining material and tubular lining material |
| JP2008142996A (en) | 2006-12-08 | 2008-06-26 | S G C Gesuido Center Kk | Method for lining piping and photocuring apparatus |
| JP2013041241A (en) | 2011-07-19 | 2013-02-28 | Ricoh Co Ltd | Electrophotographic photoconductor and method for manufacturing the same |
| JP6095278B2 (en) | 2012-04-20 | 2017-03-15 | 吉佳エンジニアリング株式会社 | Existing pipe repair method |
| SG11201602627VA (en) | 2013-10-18 | 2016-05-30 | Showa Denko Kk | Resin composition for repairing pipe culvert, material for repairing pipe culvert, and method for repairing existing pipe culvert |
-
2021
- 2021-07-28 JP JP2022539516A patent/JP7435788B2/en active Active
- 2021-07-28 WO PCT/JP2021/027840 patent/WO2022025097A1/en active Application Filing
- 2021-07-28 KR KR1020227042465A patent/KR20230009915A/en unknown
- 2021-07-28 CN CN202180042670.8A patent/CN115698108A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JP7435788B2 (en) | 2024-02-21 |
| WO2022025097A1 (en) | 2022-02-03 |
| KR20230009915A (en) | 2023-01-17 |
| JPWO2022025097A1 (en) | 2022-02-03 |
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Address after: Tokyo, Japan Applicant after: Lishennoco Co.,Ltd. Address before: Tokyo, Japan Applicant before: Showa electrical materials Co.,Ltd. |
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