JP2006213746A - Radically curable resin composition - Google Patents
Radically curable resin composition Download PDFInfo
- Publication number
- JP2006213746A JP2006213746A JP2005025025A JP2005025025A JP2006213746A JP 2006213746 A JP2006213746 A JP 2006213746A JP 2005025025 A JP2005025025 A JP 2005025025A JP 2005025025 A JP2005025025 A JP 2005025025A JP 2006213746 A JP2006213746 A JP 2006213746A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- resin composition
- acrylate
- curable resin
- oligomer
- 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.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 65
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 80
- -1 thiourea compound Chemical class 0.000 claims abstract description 58
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 9
- 239000004593 Epoxy Substances 0.000 claims abstract description 8
- 150000003254 radicals Chemical class 0.000 claims description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 11
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 9
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- ZYTMANIQRDEHIO-KXUCPTDWSA-N isopulegol Chemical compound C[C@@H]1CC[C@@H](C(C)=C)[C@H](O)C1 ZYTMANIQRDEHIO-KXUCPTDWSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- PCFHYANYPQEMPU-UHFFFAOYSA-N 4-(2,2,3-trimethyl-5-bicyclo[2.2.1]heptanyl)cyclohexan-1-ol Chemical compound CC1(C)C(C)C2CC1CC2C1CCC(O)CC1 PCFHYANYPQEMPU-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- FOWDOWQYRZXQDP-UHFFFAOYSA-N adamantan-2-ol Chemical compound C1C(C2)CC3CC1C(O)C2C3 FOWDOWQYRZXQDP-UHFFFAOYSA-N 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 claims description 3
- 239000001871 (1R,2R,5S)-5-methyl-2-prop-1-en-2-ylcyclohexan-1-ol Substances 0.000 claims description 3
- MXUCIEHYJYRTLT-UHFFFAOYSA-N 1,2-dihydroacenaphthylen-1-ol Chemical compound C1=CC(C(O)C2)=C3C2=CC=CC3=C1 MXUCIEHYJYRTLT-UHFFFAOYSA-N 0.000 claims description 3
- GWQOQQVKVOOHTI-UHFFFAOYSA-N 2,3-dihydro-1,4-benzodioxin-3-ylmethanol Chemical compound C1=CC=C2OC(CO)COC2=C1 GWQOQQVKVOOHTI-UHFFFAOYSA-N 0.000 claims description 3
- JKOZWMQUOWYZAB-UHFFFAOYSA-N 2-methyladamantan-2-ol Chemical compound C1C(C2)CC3CC1C(C)(O)C2C3 JKOZWMQUOWYZAB-UHFFFAOYSA-N 0.000 claims description 3
- KZMYFIUFUAOZHP-UHFFFAOYSA-N 4-(1-adamantyl)phenol Chemical compound C1=CC(O)=CC=C1C1(C2)CC(C3)CC2CC3C1 KZMYFIUFUAOZHP-UHFFFAOYSA-N 0.000 claims description 3
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 claims description 3
- VLLNJDMHDJRNFK-UHFFFAOYSA-N adamantan-1-ol Chemical compound C1C(C2)CC3CC2CC1(O)C3 VLLNJDMHDJRNFK-UHFFFAOYSA-N 0.000 claims description 3
- 238000007259 addition reaction Methods 0.000 claims description 3
- YIAPLDFPUUJILH-UHFFFAOYSA-N indan-1-ol Chemical compound C1=CC=C2C(O)CCC2=C1 YIAPLDFPUUJILH-UHFFFAOYSA-N 0.000 claims description 3
- 229940095045 isopulegol Drugs 0.000 claims description 3
- 229940041616 menthol Drugs 0.000 claims description 3
- ZYTMANIQRDEHIO-UHFFFAOYSA-N neo-Isopulegol Natural products CC1CCC(C(C)=C)C(O)C1 ZYTMANIQRDEHIO-UHFFFAOYSA-N 0.000 claims description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- UKANCZCEGQDKGF-UHFFFAOYSA-N 1-methylpiperidin-3-ol Chemical compound CN1CCCC(O)C1 UKANCZCEGQDKGF-UHFFFAOYSA-N 0.000 claims 1
- 229920006305 unsaturated polyester Polymers 0.000 abstract description 8
- 230000006866 deterioration Effects 0.000 abstract 1
- 229920013730 reactive polymer Polymers 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 32
- 239000011347 resin Substances 0.000 description 32
- 230000015572 biosynthetic process Effects 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- 239000002253 acid Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000003822 epoxy resin Substances 0.000 description 10
- 229920000647 polyepoxide Polymers 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- 239000000835 fiber Substances 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- 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 8
- 238000006243 chemical reaction Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000004925 Acrylic resin Substances 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 7
- 150000002009 diols Chemical class 0.000 description 7
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 150000007519 polyprotic acids Polymers 0.000 description 6
- 229920000178 Acrylic resin Polymers 0.000 description 5
- 229920001577 copolymer Chemical class 0.000 description 5
- 239000011256 inorganic filler Substances 0.000 description 5
- 150000005846 sugar alcohols Polymers 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229940059574 pentaerithrityl Drugs 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000006188 syrup Substances 0.000 description 4
- 235000020357 syrup Nutrition 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 230000008719 thickening Effects 0.000 description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- 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 3
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 239000002928 artificial marble Substances 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229920006337 unsaturated polyester resin Polymers 0.000 description 3
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- VLCDUOXHFNUCKK-UHFFFAOYSA-N N,N'-Dimethylthiourea Chemical compound CNC(=S)NC VLCDUOXHFNUCKK-UHFFFAOYSA-N 0.000 description 2
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-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
- 239000005062 Polybutadiene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- IAXXETNIOYFMLW-GYSYKLTISA-N [(1r,3r,4r)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C(=C)C)C[C@@H]1C2(C)C IAXXETNIOYFMLW-GYSYKLTISA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 235000019437 butane-1,3-diol Nutrition 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
- 239000003054 catalyst Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000012766 organic filler Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- 239000000080 wetting agent Substances 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
- HLEKFSJNCHVOAA-UHFFFAOYSA-N (2,6-ditert-butylphenyl)methanol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1CO HLEKFSJNCHVOAA-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
- ROZDMUUELHCVQC-ARJAWSKDSA-N (z)-4-oxo-4-(2-prop-2-enoyloxyethoxy)but-2-enoic acid Chemical compound OC(=O)\C=C/C(=O)OCCOC(=O)C=C ROZDMUUELHCVQC-ARJAWSKDSA-N 0.000 description 1
- JAEZSIYNWDWMMN-UHFFFAOYSA-N 1,1,3-trimethylthiourea Chemical compound CNC(=S)N(C)C JAEZSIYNWDWMMN-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- NWFVONWTBGQHGT-UHFFFAOYSA-N 1,3-didodecylthiourea Chemical compound CCCCCCCCCCCCNC(=S)NCCCCCCCCCCCC NWFVONWTBGQHGT-UHFFFAOYSA-N 0.000 description 1
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 1
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- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 1
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- 238000011978 dissolution method Methods 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
- 238000001035 drying Methods 0.000 description 1
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- 125000004185 ester group Chemical group 0.000 description 1
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- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- MHCLJIVVJQQNKQ-UHFFFAOYSA-N ethyl carbamate;2-methylprop-2-enoic acid Chemical compound CCOC(N)=O.CC(=C)C(O)=O MHCLJIVVJQQNKQ-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 230000001747 exhibiting effect Effects 0.000 description 1
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- 238000001879 gelation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
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- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
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- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- 238000000691 measurement method Methods 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920003986 novolac Polymers 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
- 239000012860 organic pigment Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
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- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
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- 229920005862 polyol Polymers 0.000 description 1
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- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
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- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([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])[H] 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、ラジカル硬化性樹脂組成物に関し、更に詳しくは収縮性が小さく、成形品の表面悪化がなく、しかも透明性を損なうことがないラジカル硬化性樹脂組成物に関する。 The present invention relates to a radical curable resin composition, and more particularly to a radical curable resin composition that has low shrinkage, does not deteriorate the surface of a molded product, and does not impair transparency.
不飽和ポリエステル樹脂、ビニルエステル樹脂、ウレタンアクリレート樹脂、アクリル樹脂に代表されるラジカル硬化性熱硬化性樹脂は複合材料用樹脂として、塗料、ライニング、人造大理石製品、プラスチックコンクリート、板金用パテなど多岐にわたって利用されている。 Radical curable thermosetting resins such as unsaturated polyester resins, vinyl ester resins, urethane acrylate resins, and acrylic resins are used as composite materials, such as paints, linings, artificial marble products, plastic concrete, and putty for sheet metal. It's being used.
ラジカル硬化性樹脂は硬化する際に一定の成形収縮を伴うため用途によっては問題となる場合があり、例えば、収縮により発生する応力を緩和するために柔軟な成分を混合せざるを得ず耐熱性が低下して不都合となる場合がある。これを解決するために低収縮剤を用いた低収縮化に関する研究も数多くなされている。例えば、特許文献１に、常温または中温成形において低硬化収縮性で耐水性を有する収縮性の不飽和ポリエステル樹脂組成物として、α、β−不飽和二塩基酸の占める割合が４０〜１００モル％である不飽和ポリエステル樹脂に、Ａセグメントとして酢酸ビニル系ポリマーと、Ｂセグメントとしてスチレン系ポリマーからなるＡ−Ｂ型ブロック共重合体を配合した不飽和ポリエステル樹脂組成物が提案されている。
また、人造大理石に（メタ）アクリル系樹脂に無機系充填剤を配合したＳＭＣ，ＢＭＣが使用されているが、成形時に発生するメチルメタクリレートモノマーにより表面の光沢ムラが発生したり、重合時の収縮により表面にヒケが発生し製品の表面性が悪く、また、成形品の寸法公差性が得にくい等の不都合が生じ易い問題がある。これを解消するため、例えば、特許文献２に、（メタ）アクリル系樹脂組成物として特定構造のエステル基を有する（メタ）アクリルモノマーを含有させた成形品の線収縮率が低く、寸法安定性、耐熱水性等が良好で、光沢ムラの発生がない外観を有する成形品が得られる（メタ）アクリル系樹脂組成物が提案されている。
また、低収縮化に熱可塑性ポリマーを低収縮剤に用いた場合には、使用される熱可塑ポリマーが相分離したり、低収縮剤と使用するポリマー成分との界面で発生するミクロクラックにより成形体の透明性が失われ用途を限定される。
Radical curable resin may cause problems depending on the application because it involves certain molding shrinkage when cured.For example, in order to relieve stress generated by shrinkage, flexible components must be mixed and heat resistant. May decrease and become inconvenient. In order to solve this, many studies have been made on the reduction of shrinkage using a low shrinkage agent. For example, in Patent Document 1, as a shrinkable unsaturated polyester resin composition having low curing shrinkage and water resistance in normal temperature or medium temperature molding, the proportion of α, β-unsaturated dibasic acid is 40 to 100 mol%. An unsaturated polyester resin composition in which an A-B type block copolymer composed of a vinyl acetate polymer as an A segment and a styrene polymer as a B segment has been proposed.
In addition, although SMC and BMC are used in which artificial marble is blended with (meth) acrylic resin and inorganic filler, surface gloss unevenness occurs due to methyl methacrylate monomer generated during molding, and shrinkage during polymerization As a result, sink marks are generated on the surface, the surface property of the product is poor, and inconveniences such as difficulty in obtaining the dimensional tolerance of the molded product are likely to occur. In order to solve this problem, for example, Patent Document 2 discloses that a (meth) acrylic resin composition containing a (meth) acrylic monomer having an ester group having a specific structure as a (meth) acrylic resin composition has a low linear shrinkage ratio and dimensional stability. In addition, a (meth) acrylic resin composition has been proposed that provides a molded product having an appearance that has good hot water resistance and the like and does not have uneven gloss.
Also, when a thermoplastic polymer is used as a low shrinkage agent to reduce shrinkage, the thermoplastic polymer used is phase-separated or molded by microcracks that occur at the interface between the low shrinkage agent and the polymer component used. The transparency of the body is lost, and the application is limited.
本発明は、上記の事情に鑑み為されたもので、低収縮剤を使用することなしに収縮性が小さく、成形品の表面悪化がなく、しかも透明性を損なうことがないラジカル硬化性樹脂組成物を提供することを目的とするものである。 The present invention was made in view of the above circumstances, and is a radically curable resin composition that has low shrinkage without using a low shrinkage agent, does not deteriorate the surface of the molded product, and does not impair transparency. The purpose is to provide goods.
本発明者らは上記課題につき鋭意研究した結果、以下に示す特定組成の樹脂組成物により、上記課題を解決し得ることを見出した。 As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by a resin composition having a specific composition shown below.
すなわち、本発明は、
（１）（ａ）分子中に脂環構造を有する単官能ウレタン（メタ）アクリレート反応性オリゴマー、（ｂ）（メタ）アクリル系ポリマー、エポキシ（メタ）アクリレートオリゴマー、多官能性ウレタン（メタ）アクリレートオリゴマー及び不飽和ポリエステルオリゴマーから選ばれるポリマー又はオリゴマーの少なくとも一種、及び、（ｃ）重合性単量体を含有してなることを特徴とするラジカル硬化性樹脂組成物に関する。
（２）更に上記硬化性樹脂組成物に、（ｄ）チオ尿素化合物を含有してなることを特徴とする上記（１）記載のラジカル硬化性樹脂組成物、
（３）成分（ａ）の分子中に脂環構造を有する単官能ウレタン（メタ）アクリレート反応性オリゴマーは、分子内に１個の水酸基及び脂環構造を有する化合物(イ)、脂肪族及び／又は脂環式多価イソシアネート（ロ）及びヒドロキシアルキル（メタ）アクリレート化合物（ハ）を付加反応させて得られるものであることを特徴とする上記（１）又は（２）記載のラジカル硬化性樹脂組成物、
（４）成分（ａ）を形成する分子内に1つの水酸基と脂環構造を有する化合物が、シクロヘキサノール、イソカンフィルシクロヘキサノール、イソプレゴール、メントール、1-アダマンタノール、２−アダマンタノール、２−メチル-２-アダマンタノール、４−（１−アダマンチル）フェノール、１−アセナフテノール、ボロネオール、フルフリルアルコール、１−ヒドロキシインダン、２−ヒドロキシメチル−１，４−ベンゾジオキサン、３−ヒドロキシ−１−メチルピペリジン、トリシクロデカンアルコールの群より選ばれる少なくとも1種である上記（１）〜（３）いずれかに記載のラジカル硬化性樹脂組成物、
（５）成分（ｃ）の重合性単量体が、環状エーテル化合物を側鎖に有する（メタ）アクリレート化合物であることを特徴とする上記（１）〜（４）のいずれかに記載のラジカル硬化性樹脂組成物、
（６）成分（ｂ）のポリマー又はオリゴマーが分子中に環状アセタール骨格を有するものであることを特徴とする上記（１）〜（５）のいずれかに記載のラジカル硬化性樹脂組成物、
（７）成分（ｂ）が、（メタ）アクリル系ポリマーであることを特徴とする上記（１）〜（６）のいずれかに記載に記載のラジカル硬化性樹脂組成物、
（８）環状エーテル化合物を側鎖に有する（メタ）アクリレート化合物が、テトラヒドロフルフリル（メタ）アクリレートであることを特徴とする上記（１）〜（７）のいずれかに記載のラジカル硬化性樹脂組成物、
を要旨とするものである。
That is, the present invention
(1) (a) Monofunctional urethane (meth) acrylate reactive oligomer having an alicyclic structure in the molecule, (b) (meth) acrylic polymer, epoxy (meth) acrylate oligomer, polyfunctional urethane (meth) acrylate The present invention relates to a radical curable resin composition comprising at least one polymer selected from an oligomer and an unsaturated polyester oligomer, or an oligomer and (c) a polymerizable monomer.
(2) The radical curable resin composition according to the above (1), further comprising (d) a thiourea compound in the curable resin composition,
(3) The monofunctional urethane (meth) acrylate reactive oligomer having an alicyclic structure in the molecule of component (a) is a compound (a) having one hydroxyl group and alicyclic structure in the molecule, aliphatic and / or Alternatively, the radical curable resin as described in (1) or (2) above, which is obtained by addition reaction of an alicyclic polyvalent isocyanate (b) and a hydroxyalkyl (meth) acrylate compound (c) Composition,
(4) A compound having one hydroxyl group and an alicyclic structure in the molecule forming component (a) is cyclohexanol, isocamphylcyclohexanol, isopulegol, menthol, 1-adamantanol, 2-adamantanol, 2- Methyl-2-adamantanol, 4- (1-adamantyl) phenol, 1-acenaphthenol, boroneol, furfuryl alcohol, 1-hydroxyindane, 2-hydroxymethyl-1,4-benzodioxane, 3-hydroxy-1 -Radical curable resin composition in any one of said (1)-(3) which is at least 1 sort (s) chosen from the group of methylpiperidine and tricyclodecane alcohol,
(5) The radical according to any one of (1) to (4) above, wherein the polymerizable monomer of component (c) is a (meth) acrylate compound having a cyclic ether compound in the side chain. Curable resin composition,
(6) The radical curable resin composition according to any one of the above (1) to (5), wherein the polymer or oligomer of the component (b) has a cyclic acetal skeleton in the molecule,
(7) The component (b) is a (meth) acrylic polymer, the radical curable resin composition according to any one of the above (1) to (6),
(8) The radical curable resin according to any one of (1) to (7) above, wherein the (meth) acrylate compound having a cyclic ether compound in the side chain is tetrahydrofurfuryl (meth) acrylate. Composition,
Is a summary.
本発明に係るラジカル硬化性樹脂組成物は、その特異的な構造の単官能ウレタン（メタ）アクリレート反応性オリゴマーを含有することにより、従来にみない低収縮性を示す。
更に、熱可塑ポリマーに代表される低収縮剤を使用しなくても優れた低収縮性を示すため、従来の技術に比べ用途の限定がなく幅広く使用することができる。また、本発明の硬化性樹脂組成物は、チオ尿素化合物を併用することにより常温において速硬化を示し、および無着色で低収縮樹脂硬化物を得ることができる。
また、ビニルモノマーとして環状エーテル化合物を側鎖に含む（メタ）アクリレートを使用することで低収縮効果を維持しながら低粘度化できる。環状アセタール骨格を有するポリマーもしくはオリゴマーを併用することで更に低収縮な硬化性樹脂組成物とすることができる等の種々の効果を奏する。
したがって、本発明の単官能ウレタン（メタ）アクリレート反応性オリゴマーおよび、これを用いたラジカル硬化型樹脂組成物は複合材料用樹脂として塗料、ライニング、人造大理石、プラスチックコンクリート、板金用パテなど多岐にわたって利用できる。
The radically curable resin composition according to the present invention contains a monofunctional urethane (meth) acrylate reactive oligomer having a specific structure, thereby exhibiting low shrinkage that is not seen in the past.
Furthermore, since it exhibits excellent low shrinkage without using a low shrinkage agent typified by a thermoplastic polymer, it can be used in a wide range without limitation of use compared to conventional techniques. Moreover, the curable resin composition of the present invention can be rapidly cured at room temperature by using a thiourea compound in combination, and can obtain a low-shrinkage resin cured product without coloring.
Further, by using (meth) acrylate containing a cyclic ether compound in the side chain as a vinyl monomer, the viscosity can be lowered while maintaining a low shrinkage effect. By using a polymer or oligomer having a cyclic acetal skeleton in combination, there are various effects such as a curable resin composition having a further low shrinkage.
Therefore, the monofunctional urethane (meth) acrylate reactive oligomer of the present invention and the radical curable resin composition using the same are widely used as a resin for composite materials such as paint, lining, artificial marble, plastic concrete, and putty for sheet metal. it can.
本発明の特徴の一つは、特異的な構造を有する単官能ウレタン（メタ）アクリレート反応性オリゴマーを含有する低収縮性を示すラジカル硬化性樹脂組成物(以下、単に硬化性樹脂組成物と記すことがある)である。 One of the characteristics of the present invention is a radically curable resin composition having a low shrinkage containing a monofunctional urethane (meth) acrylate reactive oligomer having a specific structure (hereinafter simply referred to as a curable resin composition). There are things).
本発明の単官能ウレタン（メタ）アクリレート反応性オリゴマーは、特徴ある原料、すなわち分子内に1つの水酸基と脂環構造を有する化合物、脂肪族および／または脂環式多価イソシアネート及びヒドロキシ（メタ）アクリレート化合物を反応させることによりその特異的な構造が得られるものである。 The monofunctional urethane (meth) acrylate reactive oligomer of the present invention is a characteristic raw material, that is, a compound having one hydroxyl group and an alicyclic structure in the molecule, aliphatic and / or alicyclic polyvalent isocyanate, and hydroxy (meth). The specific structure can be obtained by reacting the acrylate compound.
本発明における分子内に1つの水酸基と脂環構造を有する化合物において、「脂環構造」とは共立出版（株）発行の「化学大辞典４」の１５６頁記載の脂環式化合物の欄に定義されているものをいう。
分子内に1つの水酸基と脂環構造を有する化合物(以下脂環式モノアルコールと記載する)としては、シクロヘキサノール、イソカンフィルシクロヘキサノール、イソプレゴール、メントール、1-アダマンタノール、２−アダマンタノール、２−メチル−２−アダマンタノール、４−（１−アダマンチル）フェノール、１−アセナフテノール、ボロネオール、フルフリルアルコール、１−ヒドロキシインダン、２−ヒドロキシメチル−１，４−ベンゾジオキサン、３−ヒドロキシ−１−メチルピペリジン、トリシクロデカンアルコールが例示できる。これらは、２種類以上を適宜混合して用いてもよい。
In the compound having one hydroxyl group and an alicyclic structure in the molecule of the present invention, “alicyclic structure” is a column of alicyclic compound described in page 156 of “Chemical Dictionary 4” issued by Kyoritsu Shuppan Co., Ltd. This is what is defined.
As a compound having one hydroxyl group and an alicyclic structure in the molecule (hereinafter referred to as alicyclic monoalcohol), cyclohexanol, isocamphylcyclohexanol, isopulegol, menthol, 1-adamantanol, 2-adamantanol, 2-methyl-2-adamantanol, 4- (1-adamantyl) phenol, 1-acenaphthenol, boronneol, furfuryl alcohol, 1-hydroxyindane, 2-hydroxymethyl-1,4-benzodioxane, 3-hydroxy Examples thereof include -1-methylpiperidine and tricyclodecane alcohol. Two or more of these may be used in appropriate mixture.
脂肪族および／または脂環式多価イソシアネートとしては、脂肪族多価イソシアネートとしてヘキサメチレンジイソシアネート、トリメチルジイソシアネートが例示され、脂環式ジイソシアネートとしては、イソホロンジイソシアネート、メチレン（ビス）４−シクロヘキシルイソシアネートが例示される。これらは、２種類以上を適宜混合して用いてもよい。 Examples of the aliphatic and / or alicyclic polyisocyanate include hexamethylene diisocyanate and trimethyl diisocyanate as the aliphatic polyisocyanate, and examples of the alicyclic diisocyanate include isophorone diisocyanate and methylene (bis) 4-cyclohexyl isocyanate. Is done. Two or more of these may be used in appropriate mixture.
ヒドロキシ（メタ）アクリレート化合物は、特に制限されないが、代表的なものとして２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレートが例示される。これらは、２種類以上を適宜混合して用いてもよい。 The hydroxy (meth) acrylate compound is not particularly limited, but representative examples include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. Two or more of these may be used in appropriate mixture.
本発明における成分（ａ）の単官能ウレタン（メタ）アクリレート反応性オリゴマーを得る方法は、例えば、まず脂環式モノアルコールと多価イソシアネートとを−OH基と−NCO基のモル比が１以下となる割合で混合し、錫化合物の触媒存在下で反応させて前駆体を得る。次にこの前駆体にヒドロキシ（メタ）アクリレートを残存する−NCO基に対してモル比が１となる割合で加えて反応させる。得られたオリゴマーはビニルモノマーに溶解して取り出すのが好ましい。 The method of obtaining the monofunctional urethane (meth) acrylate reactive oligomer of the component (a) in the present invention is, for example, first by combining an alicyclic monoalcohol and a polyvalent isocyanate with a molar ratio of —OH group to —NCO group of 1 or less. And a precursor is obtained by reacting in the presence of a tin compound catalyst. Next, hydroxy (meth) acrylate is added to this precursor at a ratio such that the molar ratio is 1 with respect to the remaining -NCO groups and reacted. The obtained oligomer is preferably taken out by dissolving in a vinyl monomer.
本発明の硬化性樹脂組成物は、上記（ａ）単官能ウレタン（メタ）アクリレート反応性オリゴマーに、（ｂ）（メタ）アクリルポリマー、エポキシ（メタ）アクリレートオリゴマー、多官能性ウレタン（メタ）アクリレートオリゴマー及び不飽和ポリエステルオリゴマーから選ばれるポリマー又はオリゴマーの少なくとも一種、及び、（ｃ）重合性単量体を混合することにより調製される。 The curable resin composition of the present invention includes the (a) monofunctional urethane (meth) acrylate reactive oligomer, the (b) (meth) acrylic polymer, the epoxy (meth) acrylate oligomer, and the multifunctional urethane (meth) acrylate. It is prepared by mixing at least one polymer or oligomer selected from oligomers and unsaturated polyester oligomers, and (c) a polymerizable monomer.
本発明の硬化性硬化性組成物には、さらに（ｄ）チオ尿素化合物を配合することにより、常温〜低温領域における硬化性を促進することができ常温〜低温性樹脂組成物に調製することができる。また硬化物の着色を抑制する効果を奏する。 In the curable curable composition of the present invention, by further blending (d) a thiourea compound, the curability in the normal temperature to low temperature region can be promoted, and the normal temperature to low temperature resin composition can be prepared. it can. Moreover, there exists an effect which suppresses coloring of hardened | cured material.
本発明における（ｂ）成分は硬化物に機械的強度や柔軟性、耐熱性、耐水性、耐薬品性、耐汚染性等を付与する効果を有する。尚、下記に記載する（ｂ）成分のポリマー又はオリゴマーはビニルモノマーに溶解して反応容器から取り出すのが好ましい。 The component (b) in the present invention has the effect of imparting mechanical strength, flexibility, heat resistance, water resistance, chemical resistance, stain resistance, and the like to the cured product. The polymer or oligomer of component (b) described below is preferably dissolved in the vinyl monomer and taken out from the reaction vessel.
本発明の上記（ｂ）成分の(メタ)アクリルポリマーは、メタクリル酸メチルを主体とする（メタ）アクリレートモノマーを懸濁重合、乳化重合、溶液重合、塊状重合等の公知の重合方法により重合させて得られるものである。本発明の(メタ)アクリルポリマーは、適切な作業性を有する成形材料とするために増粘機能を付与することができる。増粘機能としては金属酸化物と反応するカルボキシル基を分子鎖に導入する方法がある。導入方法としては、例えば、（メタ）アクリル酸エステルの一部を酸基含有ビニルモノマーで置き換え重合させる方法や、水酸基含有ビニルモノマーを使用して水酸基を導入した重合体と酸無水物とを反応させる方法等が酸基導入に使用できるがこれらは特に制限されない。ここで用いる酸基含有ビニルモノマーとしては、特に制限を受けないが、入手が容易なこと、経済性、取り扱い性が良好なこと、機械的特性、耐水性等のバランスがとれていること等から、（メタ）アクリル酸が好ましく用いられる。これら酸基含有ビニルモノマーは、二種類以上を適宜混合して用いても良い。これらポリ（メタ）アクリレートの重量平均分子量は、１００００〜６０００００の範囲にあるものが機械的特性、成形性が良好で好ましく、３００００〜２５００００の範囲であることが更に好ましい。重量平均分子量が１００００未満であると、得られる成形品の機械的物性が低下し、６０００００を超えると、メタクリル酸メチル含有樹脂の粘度が高くなりすぎ作業性が低下するため好ましくない。尚、得られたポリマーを（メタ）アクリルモノマーで希釈したいわゆるアクリルシラップとして取り扱うのが常法である。 The (meth) acrylic polymer of the component (b) of the present invention is obtained by polymerizing a (meth) acrylate monomer mainly composed of methyl methacrylate by a known polymerization method such as suspension polymerization, emulsion polymerization, solution polymerization or bulk polymerization. Is obtained. The (meth) acrylic polymer of the present invention can be imparted with a thickening function in order to obtain a molding material having appropriate workability. As a thickening function, there is a method of introducing a carboxyl group that reacts with a metal oxide into a molecular chain. Examples of the introduction method include a method in which a part of (meth) acrylic acid ester is replaced with an acid group-containing vinyl monomer, and a polymer in which a hydroxyl group is introduced using a hydroxyl group-containing vinyl monomer is reacted with an acid anhydride. However, these methods are not particularly limited. The acid group-containing vinyl monomer used here is not particularly limited, but it is easy to obtain, economical, easy to handle, balanced in mechanical properties, water resistance, etc. , (Meth) acrylic acid is preferably used. Two or more kinds of these acid group-containing vinyl monomers may be appropriately mixed and used. The weight average molecular weight of these poly (meth) acrylates is preferably in the range of 10,000 to 600,000 because of good mechanical properties and moldability, and more preferably in the range of 30000 to 250,000. When the weight average molecular weight is less than 10,000, the mechanical properties of the obtained molded product are lowered, and when it exceeds 600,000, the viscosity of the methyl methacrylate-containing resin becomes too high, and the workability is lowered, which is not preferable. In addition, it is usual to handle the obtained polymer as so-called acrylic syrup diluted with a (meth) acrylic monomer.
本発明の上記（ｂ）成分のエポキシ（メタ）アクリレートオリゴマー（以下、単に「エポキシアクリレート」いう）は、それ自体公知の方法で製造することができる。例えば、特公昭４５−４００６９号公報、特開昭５９−３６１１８公報に記載されているように公知の反応触媒、重合禁止剤を共存させエポキシ樹脂と不飽和一塩基酸とを反応させることにより得られるエポキシアクリレートを使用することができる。該エポキシアクリレートの製造に使用されるエポキシ樹脂としては、例えば、ビスフェノールA、ビスフェノールＦ、ビスフェノールＳ等、あるいはこれらの誘導体から得られるビスフェノール型エポキシ樹脂、ビキシレノールおよびその誘導体から得られるビキシレノール型エポキシ樹脂、またナフタレンおよびその誘導体から得られるナフタレン型エポキシ樹脂、またはノボラック型エポキシ樹脂などのエポキシ樹脂が挙げられる。これらのうち衝撃性が高く、得られる樹脂及び硬化物の色が無色透明に近いことからエピクロルヒドリンとビスフェノールＡとの反応により得られるビスフェノールＡ型エポキシ樹脂を使用することが望ましい。エポキシ樹脂の分子量の目安になるエポキシ当量は３００〜１０００ｅｑ／ｇのものが好ましい。エポキシ当量３００ｅｑ／ｇ未満では硬化物が硬く脆くなる傾向があり好ましくない。１０００ｅｑ／ｇを超えるものは樹脂粘度が高く取り扱い性が悪い。エポキシ樹脂と反応させる不飽和一塩基酸としては、アクリル酸またはメタクリル酸が使用されるが、中でも耐熱水性に優れたメタクリル酸を使用することが好ましい。エポキシ樹脂と不飽和一塩基酸との反応は、反応中のゲル化、貯蔵安定性、着色等を考慮してそれぞれの官能基が等量になるように仕込むことが好ましい。本発明のエポキシアクリレートには増粘機能を付与するために酸基を導入することが出来る。酸基の導入方法としては、特に制限されないが、エポキシアクリレートの水酸基に二塩基酸の酸無水物を反応させる方法が好んで用いられる。二塩基酸の酸無水物としては無水マレイン酸、無水フタル酸、テトラヒドロ無水フタル酸等を使用することができ、その配合量としては、カルボキシル基を付加したエポキシアクリレート中のカルボキシル基濃度（カルボキシル基を中和するのに必要な水酸化カリウム量）で５〜４０ｍｇＫＯＨ／ｇの範囲のものが良好な増粘性を与える。５ｍｇＫＯＨ／ｇ未満では、増粘度が低く粘着性のないコンパウンドが得られない。４０ｍｇＫＯＨ／ｇを超える場合は耐水性が極端に悪くなるので好ましくない。 The epoxy (meth) acrylate oligomer (hereinafter simply referred to as “epoxy acrylate”) of the component (b) of the present invention can be produced by a method known per se. For example, as described in JP-B-45-40069 and JP-A-59-36118, it can be obtained by reacting an epoxy resin with an unsaturated monobasic acid in the presence of a known reaction catalyst and polymerization inhibitor. Epoxy acrylates can be used. Examples of the epoxy resin used in the production of the epoxy acrylate include bisphenol type epoxy resin obtained from bisphenol A, bisphenol F, bisphenol S, etc., or derivatives thereof, bixylenol and derivatives thereof. Examples thereof include epoxy resins such as naphthalene type epoxy resins obtained from resins and naphthalene and derivatives thereof, or novolak type epoxy resins. Among these, it is desirable to use a bisphenol A type epoxy resin obtained by the reaction of epichlorohydrin and bisphenol A because the impact property is high and the color of the resulting resin and cured product is almost colorless and transparent. The epoxy equivalent serving as a measure of the molecular weight of the epoxy resin is preferably 300 to 1000 eq / g. If the epoxy equivalent is less than 300 eq / g, the cured product tends to be hard and brittle, which is not preferable. Those exceeding 1000 eq / g have high resin viscosity and poor handleability. As the unsaturated monobasic acid to be reacted with the epoxy resin, acrylic acid or methacrylic acid is used. Among them, methacrylic acid having excellent hot water resistance is preferably used. The reaction between the epoxy resin and the unsaturated monobasic acid is preferably carried out so that each functional group has an equivalent amount in consideration of gelation, storage stability, coloring and the like during the reaction. An acid group can be introduced to the epoxy acrylate of the present invention in order to impart a thickening function. The method for introducing an acid group is not particularly limited, but a method of reacting a dibasic acid anhydride with a hydroxyl group of epoxy acrylate is preferably used. Maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, etc. can be used as the acid anhydride of the dibasic acid, and the blending amount thereof is the carboxyl group concentration (carboxyl group) in the epoxy acrylate to which the carboxyl group is added. The amount of potassium hydroxide required to neutralize the amount of 5 to 40 mg KOH / g gives good thickening. If it is less than 5 mgKOH / g, a compound having low viscosity and no tackiness cannot be obtained. When it exceeds 40 mgKOH / g, the water resistance is extremely deteriorated, which is not preferable.
本発明の上記（ｂ）成分の多官能性ウレタン（メタ）アクリレートオリゴマーは、分子内に少なくとも２つの水酸基を有する化合物と、多価イソシアネートとヒドロキシ（メタ）アクリレート化合物との付加反応により得られる。分子内に少なくとも２つの水酸基を有する化合物としては、例えば、ポリ（エチレンオキサイド）ジオール、ポリ（プロピレンオキサイド）ジオール、コポリ（テトラメチレン）オキサイドジオール、スピログリコール、ポリエステルポリオール、（水添）ポリブタジエンポリオール、カプロラクトン変性ジオール、ポリカーボネートジオール等の多価アルコール類、不飽和ポリエステルもしくは飽和ポリエステルも例示できる。これらは、２種類以上を適宜混合して用いてもよい。多価イソシアネート化合物としては、例えば、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、水添ジフェニルメタンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、キシリレンジイソアイアネート、水添キシリレンジイソアイアネートを例示でき、これらを単独或いは2種類以上を混合して使用できる。また、ヒドロキシ（メタ）アクリレート化合物は上記単官能ウレタン（メタ）アクリレートオリゴマーの項に記載したものと同等ものが用いられる。 The polyfunctional urethane (meth) acrylate oligomer of the component (b) of the present invention is obtained by an addition reaction of a compound having at least two hydroxyl groups in the molecule, a polyvalent isocyanate and a hydroxy (meth) acrylate compound. Examples of the compound having at least two hydroxyl groups in the molecule include poly (ethylene oxide) diol, poly (propylene oxide) diol, copoly (tetramethylene) oxide diol, spiroglycol, polyester polyol, (hydrogenated) polybutadiene polyol, Examples thereof include polyhydric alcohols such as caprolactone-modified diol and polycarbonate diol, unsaturated polyester or saturated polyester. Two or more of these may be used in appropriate mixture. Examples of the polyvalent isocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and hydrogenated xylylene diisocyanate. A mixture of more than one type can be used. The hydroxy (meth) acrylate compound is the same as that described in the section of the monofunctional urethane (meth) acrylate oligomer.
本発明の上記（ｂ）成分の不飽和ポリエステルオリゴマーは、不飽和多塩基酸又は場合により飽和多塩基酸を含む不飽和多塩基酸と多価アルコールとの重縮合反応により得られる不飽和ポリエステルを使用することができる。不飽和多塩基酸としては、例えば、フマル酸、マレイン酸、無水マレイン酸、イタコン酸、シトラコン酸、メサコン酸、クロロマレイン酸、あるいはこれらのジアルキルエステルを挙げることができる。不飽和多塩基酸の一部を置き換える飽和多塩基酸としては、例えば、フタル酸、無水フタル酸、イソフタル酸、テレフタル酸、ヘット酸、ヘキサヒドロ無水フタル酸、アジピン酸、セバチン酸、アゼライン酸を挙げることができる。多価アルコールとしては、例えば、エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリメチレングリコール、１,２−ブタンジオール、１,３−ブタンジオール、１,４−ブタンジオール、１,２−ペンタンジオール、１,６−ヘキサンジオール、シクロヘキサンジオール、ネオペンチルグリコール、２,２,４−トリメチル−１,３−ペンタンジオール、グリセリンモノアリルエーテル、水素化ビスフェノールＡ、２,２−ビス（４−ヒドロキシエトキシフェニル）プロパン、２,２−ビス（４−ヒドロキシプロポキシフェニル）プロパンなどのジオール類、トリメチロールプロパンなどのトリオール類、ペンタエリスリトールなどのテトラオール類を挙げることができる。これらの多価アルコールは、それぞれ単独或いは２種以上を組み合わせて用いることができる。ここで使用される不飽和ポリエステルは、重量平均分子量２０００〜１００００、酸価５〜４０ｍｇＫＯＨ／ｇのものを用いることができる。重量平均分子量が２０００未満では機械的特性、耐熱水性が低下し、１００００を超えるものは樹脂粘度が高くなりすぎ作業性が低下するため好ましくない。 The unsaturated polyester oligomer of the component (b) of the present invention is an unsaturated polyester obtained by a polycondensation reaction of an unsaturated polybasic acid or an unsaturated polybasic acid containing a saturated polybasic acid and a polyhydric alcohol. Can be used. Examples of the unsaturated polybasic acid include fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, chloromaleic acid, and dialkyl esters thereof. Examples of the saturated polybasic acid that replaces part of the unsaturated polybasic acid include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, het acid, hexahydrophthalic anhydride, adipic acid, sebacic acid, and azelaic acid. be able to. Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,2-pentane. Diol, 1,6-hexanediol, cyclohexanediol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, glycerin monoallyl ether, hydrogenated bisphenol A, 2,2-bis (4-hydroxy Examples include diols such as ethoxyphenyl) propane, 2,2-bis (4-hydroxypropoxyphenyl) propane, triols such as trimethylolpropane, and tetraols such as pentaerythritol. These polyhydric alcohols can be used alone or in combination of two or more. As the unsaturated polyester used here, those having a weight average molecular weight of 2000 to 10,000 and an acid value of 5 to 40 mgKOH / g can be used. If the weight average molecular weight is less than 2,000, the mechanical properties and hot water resistance decrease, and those exceeding 10,000 are not preferable because the resin viscosity becomes too high and workability decreases.
本発明における（ｂ）成分のポリマー又はオリゴマーは、環状アセタール骨格を含有しているものが硬化性樹脂組成物を更に低収縮性とすることができる観点から好ましい。これら環状アセタールの導入方法は特に限定されないが、例えば、３，９−ビス（１，１−ジメチル−２−ヒドロキシエチル）−２，４，８，１０−テトラオキサスピロ〔５．５〕ウンデカン、５−メチロール−５−エチル−２−（１，１−ジメチル−２−ヒドロキシエチル）−１，３−ジオキサン等のジオールを、ウレタン（メタ）アクリレートオリゴマーもしくは不飽和ポリエステルオリゴマー製造の際のジオール成分として使用する方法が簡便で好ましい。 The polymer or oligomer of the component (b) in the present invention is preferably one containing a cyclic acetal skeleton from the viewpoint that the curable resin composition can be further reduced in shrinkage. The method for introducing these cyclic acetals is not particularly limited. For example, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, A diol component such as 5-methylol-5-ethyl-2- (1,1-dimethyl-2-hydroxyethyl) -1,3-dioxane is used for producing a urethane (meth) acrylate oligomer or an unsaturated polyester oligomer. The method used as is simple and preferred.
本発明の硬化性樹脂組成物における（ｃ）成分の重合性単量体としては、従来から使用されているスチレン、ビニルトルエン、α−メチルスチレン、酢酸ビニル、メタクリル酸メチル、メタクリル酸、アクリル酸、ベンジル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、トリデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、グリシジル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、２−メトキシエチル（メタ）アクリレート、２−エトキシエチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ノルボルニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンタニル（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、アクリル（メタ）アクリレート、2−ヒドロキシエチル（メタ）アクリレート、コハク酸２−（メタ）アクロイルオキシエチル、マレイン酸２−（メタ）アクロイルオキシエチル、フタル酸２−（メタ）アクロイルオキシエチル、ヘキサヒドロフタル酸２−（メタ）アクリオイルオキシエチル、ペンタメチルピペリジル（メタ）アクリレート、テトラメチルピペリジル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート等が例示できる。これらは、２種類以上を適宜混合して用いてもよい。 As the polymerizable monomer of the component (c) in the curable resin composition of the present invention, conventionally used styrene, vinyl toluene, α-methyl styrene, vinyl acetate, methyl methacrylate, methacrylic acid, acrylic acid , Benzyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate , Stearyl (meth) acrylate, glycidyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate , Norbornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, acrylic (meth) acrylate, 2-hydroxyethyl (meth) acrylate 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl maleate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate And pentamethylpiperidyl (meth) acrylate, tetramethylpiperidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and the like. Two or more of these may be used in appropriate mixture.
また、多官能単量体も使用することができる。該多官能単量体としては、例えば、エチレングリコールジ（メタ）アクリレート、ジ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、１,３−ブチレングリコールジ（メタ）アクリレート、１,４−ブチレングリコールジ（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、ジメチロールエタンジ（メタ）アクリレート、１，１−ジメチロールプロパンジ（メタ）アクリレート、２,２−ジメチロールプロパンジ（メタ）アクリレート、トリメチロールエタントリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、テトラメチロールメタントリ（メタ）アクリレート、テトラメチロールメタンジ（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、及び（メタ）アクリル酸とポリエチレングリコール、ポリプロピレングリコール、ペンタエリスリトール、ジペンタエリスリトール等の多価アルコールとの多価エステル、ジビニルベンゼン、トリアリールイソシアヌレート、アリールメタクリレート、ジアリルフタレート等を例示できる。これらは、必要に応じて単独であるいは２種以上を併用して使用することができる。 Moreover, a polyfunctional monomer can also be used. Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, and 1,4- Butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, dimethylolethane di (meth) acrylate, 1,1-dimethylolpropane di (meth) acrylate, 2,2-dimethylolpropane di (Meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane di (meth) acrylate, neopentyl glycol di (me E.g., polyacrylates of (meth) acrylic acid and (meth) acrylic acid and polyhydric alcohols such as polyethylene glycol, polypropylene glycol, pentaerythritol, dipentaerythritol, divinylbenzene, triaryl isocyanurate, aryl methacrylate, diallyl phthalate, etc. it can. These may be used alone or in combination of two or more as required.
本発明における（ａ）成分の単官能ウレタン（メタ）アクリレート反応性オリゴマーの配合比は樹脂組成物中２〜９５重量％の範囲で使用するのが好ましい。更に好ましくは５〜９０重量％である。２重量％より少ないと低収縮効果が発現せず、９５重量％を超えると樹脂粘度が高く取り扱い性が困難となる。（ｂ）成分のポリマー又はオリゴマーは樹脂組成物中７０重量％以下の範囲で使用され、５〜６０重量％が好ましく、更に好ましくは１０〜５０重量％である。７０重量％を超えると樹脂粘度が高くなり好ましくない。
（ｃ)成分の重合性単量体は５〜７０重量％が好ましく、１０〜５０重量％が更に好ましい。５重量％より少ないと粘度が高く取り扱い性不良となり、７０重量％を超えると低収縮効果が失われる。
The compounding ratio of the monofunctional urethane (meth) acrylate reactive oligomer of the component (a) in the present invention is preferably in the range of 2 to 95% by weight in the resin composition. More preferably, it is 5 to 90% by weight. When the amount is less than 2% by weight, the low shrinkage effect is not exhibited. When the amount exceeds 95% by weight, the resin viscosity is high and the handling property becomes difficult. The polymer or oligomer of component (b) is used in the range of 70% by weight or less in the resin composition, preferably 5 to 60% by weight, more preferably 10 to 50% by weight. If it exceeds 70% by weight, the resin viscosity is undesirably increased.
The polymerizable monomer of component (c) is preferably 5 to 70% by weight, more preferably 10 to 50% by weight. If the amount is less than 5% by weight, the viscosity is high and the handling property is poor, and if it exceeds 70% by weight, the low shrinkage effect is lost.
本発明において収縮率を十分に抑制して低粘度化し得るのに好適な重合性単量体として環状エーテル化合物を側鎖に含む（メタ）アクリレートの使用が好ましい。更に、入手が容易であることの理由からテトラヒドロフルフリル（メタ）アクリレートもしくはアクリロイルモルホリンが好適である。使用する量は特に制限されないが、経済性を考慮して使用する重合性単量体を１００としたとき５〜３０％の範囲で使用するのが好ましい。 In the present invention, it is preferable to use (meth) acrylate containing a cyclic ether compound in the side chain as a polymerizable monomer suitable for sufficiently reducing the shrinkage rate and reducing the viscosity. Furthermore, tetrahydrofurfuryl (meth) acrylate or acryloylmorpholine is preferred because it is easily available. The amount to be used is not particularly limited, but it is preferably used in the range of 5 to 30% when the polymerizable monomer to be used is 100 in consideration of economy.
本発明の硬化性樹脂組成物には通常ラジカル重合開始剤が配合され、このようなラジカル重合開始剤は、加熱もしくは触媒の作用により自らもしくはその分解物が、反応性オリゴマーや（メタ）アクリル系モノマーの活性部位と反応し、硬化反応を開始する作用を有するものである。このような重合開始剤は特に限定されないが、次のようなものが例示される。例えば、ケトンパーオキサイド、パーオキシケタール、ハイドロパーオキサイド、ジアルキルパーオキサイド、ジアシルパーオキサイド、パーオキシジカーボネート、パーオキシエステル等の過酸化物が用いられる。これらのなかで４０〜８０℃の中温硬化ではパーオキシジカーボネートが好ましく、０〜４０℃の低温ないし常温硬化では、ハイドロパーオキサイド、クメンハイドロパーオキサイドが好ましく、特にクメンハイドロパーキサイドが好ましい。 The curable resin composition of the present invention is usually mixed with a radical polymerization initiator, and such a radical polymerization initiator may be a reactive oligomer or a (meth) acrylic compound itself or a decomposition product thereof by heating or the action of a catalyst. It has the effect | action which reacts with the active site | part of a monomer and starts hardening reaction. Although such a polymerization initiator is not specifically limited, The following are illustrated. For example, peroxides such as ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, and peroxyester are used. Among these, peroxydicarbonate is preferable for medium temperature curing at 40 to 80 ° C., and hydroperoxide and cumene hydroperoxide are preferable for low temperature or normal temperature curing of 0 to 40 ° C., particularly cumene hydroperoxide.
上記した重合開始剤の他に２００〜５００nmの波長範囲の紫外線または可視光線で励起され活性化する光重合開始剤を使用することもできる。このような光重合開始剤としては特に限定されるものではないが、例えば、ベンゾイン誘導体、ベンジルケタール類、α−ヒドロキシアセトフェノン類、α−アミノアセトフェノン類、チオキサントン類、アシルフォスフィンオキサイド類が例示できる。 In addition to the polymerization initiator described above, a photopolymerization initiator that is excited and activated by ultraviolet rays or visible rays in the wavelength range of 200 to 500 nm can also be used. Such a photopolymerization initiator is not particularly limited, and examples thereof include benzoin derivatives, benzyl ketals, α-hydroxyacetophenones, α-aminoacetophenones, thioxanthones, and acylphosphine oxides. .
上記の重合開始剤は、単独であるいは２種以上を適宜組み合わせて用いてもよい。また、その使用量は特に限定されないが、樹脂組成物（反応性オリゴマーと稀釈剤）１００重量部に対して０．１〜５．０重量部が好ましい。０．１重量部未満では、硬化時間が長くかかり、５．０重量部を超えると硬化反応が急激過ぎて好ましくない。 The above polymerization initiators may be used alone or in appropriate combination of two or more. Moreover, the usage-amount is although it does not specifically limit, 0.1-5.0 weight part is preferable with respect to 100 weight part of resin compositions (reactive oligomer and diluent). If it is less than 0.1 parts by weight, it takes a long time to cure, and if it exceeds 5.0 parts by weight, the curing reaction is too rapid.
本発明において、上記硬化性樹脂組成物にさらに配合される（ｄ）成分のチオ尿素化合物はラジカル重合開始剤の作用を助ける促進剤の作用を有し、特に低温〜常温領域での硬化反応に有用である。ここに用いられるチオ尿素化合物としては、チオ尿素または置換チオ尿素化合物であり、具体例としては、チオ尿素、Ｎ，Ｎ’−ジフェニルチオ尿素、Ｎ，Ｎ’−ジオルトトリルチオ尿素、エチレンチオ尿素、ジエチルチオ尿素、ジブチルチオ尿素、トリメチルチオ尿素、テトラメチルチオ尿素、ジメチルエチルチオ尿素、ジラウリルチオ尿素、ジメチルチオ尿素等が挙げられる。なかでもジエチルチオ尿素、エチレンチオ尿素、ジメチルチオ尿素が好ましい。これらのチオ尿素化合物の効果を有効に発現するのは、特に制限されないが重合開始剤のクメンハイドロパーオキサイドとの併用が好適である。 In the present invention, the thiourea compound of component (d) further blended in the curable resin composition has an accelerator action that assists the action of the radical polymerization initiator, and is particularly suitable for a curing reaction in a low temperature to normal temperature range. Useful. The thiourea compound used here is a thiourea or a substituted thiourea compound, and specific examples include thiourea, N, N′-diphenylthiourea, N, N′-diortolylthiourea, ethylenethiourea. Diethylthiourea, dibutylthiourea, trimethylthiourea, tetramethylthiourea, dimethylethylthiourea, dilaurylthiourea, dimethylthiourea and the like. Of these, diethylthiourea, ethylenethiourea, and dimethylthiourea are preferable. Although it does not restrict | limit especially that the effect of these thiourea compounds is expressed effectively, combined use with the cumene hydroperoxide of a polymerization initiator is suitable.
本発明において、チオ尿素化合物は樹脂組成物に予め適量溶解して、いわゆるプロモートタイプの樹脂として使用するのが好ましい。この際の溶解させる量は必要とする所望硬化時間等により調整すればよく特に制限されない。また溶解方法も特に制限されないが４０〜８０℃に加熱、溶解して加える方法、もしくはメタノール等のアルコール系溶剤に溶解した後添加する等の方法で溶解すればよい。その使用量は、樹脂組成物１００重量部に対して、０．０１〜３．０重量部が好ましく、０．０３〜１．０重量部が更に好ましい。０．０１重量部より少ない場合は添加効果が発現せず硬化不良となる虞があり、一方、３．０重量部を超える量では硬化速度が速すぎて好ましくない。 In the present invention, the thiourea compound is preferably dissolved in an appropriate amount in the resin composition in advance and used as a so-called promote type resin. The amount to be dissolved at this time is not particularly limited as long as it is adjusted depending on the desired curing time required. The dissolution method is not particularly limited, but may be dissolved by heating, dissolving at 40 to 80 ° C. or adding after dissolving in an alcohol solvent such as methanol. The amount used is preferably 0.01 to 3.0 parts by weight, more preferably 0.03 to 1.0 parts by weight, with respect to 100 parts by weight of the resin composition. If the amount is less than 0.01 parts by weight, the effect of addition may not be exhibited and curing may be poor.
本発明に係る硬化性樹脂組成物にはガラスもしくは金属との接着性を高める目的で、（メタ）アクリル酸、２−ヒドロキシエチル(メタ)アクリレート、２−（（メタ）アクリロイロキシ）エチルアシッドフォスフェート、ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ−（（メタ）アクリロキシプロピル）トリメトキシシラン、γ−（（メタ）アクリロキシプロピル）トリエトキシシラン、γ−（（メタ）アクリロキシプロピル）メチルジメトキシシラン、γ−（（メタ）アクリロキシプロピル）メチルジエトキシシランの群から選ばれる化合物の１種もしくは２種以上を添加することができる。 The curable resin composition according to the present invention has (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 2-((meth) acryloyloxy) ethyl acid phosphate for the purpose of enhancing the adhesion to glass or metal. , Vinyltrimethoxysilane, vinyltriethoxysilane, γ-((meth) acryloxypropyl) trimethoxysilane, γ-((meth) acryloxypropyl) triethoxysilane, γ-((meth) acryloxypropyl) methyl One or more compounds selected from the group of dimethoxysilane and γ-((meth) acryloxypropyl) methyldiethoxysilane can be added.
本発明の硬化性樹脂組成物には、硬化物に半透明の風合いを付与し、また収縮率を更に低下させる目的で無機系または有機系充填材を併用することができる。無機系充填材としては、具体的には、水酸化アルミニウム、シリカ、ガラスパウダー、炭酸カルシウム、アルミナ、クレー、タルク、ミルドファイバー、珪砂、川砂、珪藻土、雲母粉末、石膏、寒水砂、アスベスト粉等の無機系充填材、および、ポリマービーズ等の有機系充填材が挙げられる。上記充填材のうち、水酸化アルミニウム、シリカ、およびガラスパウダーからなる群より選ばれる少なくとも一種の無機系充填材が特に好ましい。上記充填材は、単独で用いてもよく、また、二種類以上を適宜組み合わせて用いてもよい。また、充填材の平均粒径や形状等の形態は、特に限定されるものではない。 In the curable resin composition of the present invention, an inorganic or organic filler can be used in combination for the purpose of imparting a translucent texture to the cured product and further reducing the shrinkage. Specific examples of the inorganic filler include aluminum hydroxide, silica, glass powder, calcium carbonate, alumina, clay, talc, milled fiber, quartz sand, river sand, diatomaceous earth, mica powder, gypsum, cold water sand, asbestos powder, etc. Inorganic fillers, and organic fillers such as polymer beads. Of the fillers, at least one inorganic filler selected from the group consisting of aluminum hydroxide, silica, and glass powder is particularly preferable. The said filler may be used independently and may be used in combination of 2 or more types as appropriate. Further, the form such as the average particle diameter and shape of the filler is not particularly limited.
本発明の硬化性樹脂組成物にはその他の公知の添加剤を使用することができる。具体的には、機械強度を向上させる効果がある繊維強化材、重合調節剤、酸化防止剤、湿潤剤(減粘剤)、着色剤、紫外線吸収剤、チクソトロピー付与剤、難燃剤等それ自体公知のものを例示できる。これら、添加剤の使用量はその種類、目的および所望する効果により適宜定めればよく特に限定されるものではない。また、その使用方法も単独で用いてもよく、２種類以上を適宜組み合わせて用いてもよい。 Other known additives can be used in the curable resin composition of the present invention. Specifically, fiber reinforcing materials having an effect of improving mechanical strength, polymerization regulators, antioxidants, wetting agents (thickening agents), coloring agents, ultraviolet absorbers, thixotropy imparting agents, flame retardants, etc. are known per se. Can be illustrated. The amount of these additives used is not particularly limited as long as it is appropriately determined depending on the type, purpose and desired effect. Moreover, the usage method may be used independently and may be used in combination of 2 or more types as appropriate.
紫外線吸収剤は、サリチル酸エステル系、ベンゾフェノン系 ベンゾトリアゾール系、シアノアクリレート系、シュウ酸アニリド系が例示できる。紫外線吸収剤の量は、０．０５〜５重量部が好ましい。０．０５重量部未満では紫外線の吸収効果が悪く、５重量部を超えると樹脂との相溶性が悪い。 Examples of the ultraviolet absorber include salicylic acid ester type, benzophenone type benzotriazole type, cyanoacrylate type, and oxalic acid anilide type. The amount of the ultraviolet absorber is preferably 0.05 to 5 parts by weight. If it is less than 0.05 part by weight, the effect of absorbing ultraviolet rays is poor, and if it exceeds 5 parts by weight, the compatibility with the resin is poor.
本発明の硬化性樹脂組成物は、低収縮剤を使用しなくとも優れた低収縮性を示すが、必要に応じて、従来から使用されている低収縮剤を添加することもできる。このような低収縮剤としては、具体的には、ポリスチレン、ポリエチレン、ポリメタクリル酸メチル、ポリ塩化ビニル、ポリ酢酸ビニル、ポリカプロラクタム、飽和ポリエステル、スチレン-アクリロニトリル共重合体、酢酸ビニル-スチレン共重合体、スチレン−ジビニルベンゼン共重合体、メタクリル酸メチル−多官能メタクリレート共重合体、ポリブタジエン、ポリイソプレン、スチレン-ブタジエン共重合体、アクリロニトリル-ブタジエン共重合体などのゴム状重合体などが用いられる。また、これらの熱可塑ポリマーは部分的に架橋構造を導入されたものであってもよい。使用量に関しては、特に限定されないが、硬化性樹脂組成物１００重量部に対して、２０重量部以下の範囲とするのが好適である。２０重量部を超える場合は成形体の透明感等を著しく低下させるため好ましくない。 Although the curable resin composition of the present invention exhibits excellent low shrinkage without using a low shrink agent, a conventionally used low shrink agent can be added as required. Specific examples of such a low shrinkage agent include polystyrene, polyethylene, polymethyl methacrylate, polyvinyl chloride, polyvinyl acetate, polycaprolactam, saturated polyester, styrene-acrylonitrile copolymer, vinyl acetate-styrene copolymer. Polymers, rubber-like polymers such as styrene-divinylbenzene copolymer, methyl methacrylate-polyfunctional methacrylate copolymer, polybutadiene, polyisoprene, styrene-butadiene copolymer, and acrylonitrile-butadiene copolymer are used. These thermoplastic polymers may be partially introduced with a crosslinked structure. The amount used is not particularly limited, but it is preferably 20 parts by weight or less with respect to 100 parts by weight of the curable resin composition. When the amount exceeds 20 parts by weight, the transparency of the molded article is remarkably lowered, which is not preferable.
繊維強化材としては、具体的には、例えば、ガラス繊維、炭素繊維、金属繊維、セラミックからなる繊維等の無機繊維；アラミドやポリエステル等からなる有機繊維；天然繊維等が挙げられるが、特に限定されるものではない。また、繊維の形態は、ロービング、クロス、マット、織物、チョップドロービング、チョップドストランド等が挙げられるが、特に限定されるものではない。これら繊維補強材は、単独で用いてもよく、二種類以上を適宜混合して用いてもよい。使用量に関しては、特に限定されないが、硬化性樹脂組成物１００重量部に対して、２０重量部以下の範囲とするのが好ましい。２０重量部を超える場合は樹脂組成物の粘度が高くなり不適である。 Specific examples of the fiber reinforcing material include inorganic fibers such as glass fibers, carbon fibers, metal fibers, and ceramic fibers; organic fibers such as aramid and polyester; natural fibers, and the like. Is not to be done. Moreover, although the form of a fiber includes roving, cloth, mat, woven fabric, chopped roving, chopped strand, etc., it is not particularly limited. These fiber reinforcing materials may be used alone or in combination of two or more. The amount used is not particularly limited, but it is preferably 20 parts by weight or less with respect to 100 parts by weight of the curable resin composition. When the amount exceeds 20 parts by weight, the viscosity of the resin composition increases, which is not suitable.
湿潤剤としては、市販されているものが使用できる。例えば、ビッグケミー株式会社から市販されている「Ｗ−９９５」、「Ｗ−９９６」、「Ｗ−９０１０」、「Ｗ−９６０」、「Ｗ−９６５」、「Ｗ−９９０」等が挙げられる。また、消泡剤として、同じくビッグケミー株式会社から市販されている「Ａ−５１５」等が挙げられる。これらはその使用目的によって適宜選択して使用される。 A commercially available wetting agent can be used. For example, “W-995”, “W-996”, “W-9010”, “W-960”, “W-965”, “W-990”, etc., commercially available from Big Chemie Co., Ltd. may be mentioned. Moreover, as an antifoamer, "A-515" etc. which are marketed similarly from Big Chemie Co., Ltd. are mentioned. These are appropriately selected depending on the purpose of use.
重合調整剤としては、例えば、ハイドロキノン、メチルハイドロキノン、メトキシハイドロキノン、ｔ−ブチルハイドロキノン等の重合禁止剤、チオール化合物等の連鎖移動剤が挙げられる。また酸化防止剤としては、２，６−ジ−ｔ−ブチルヒドロキシトルエン等のヒンダードフェノール系のものが好んで用いられる。上記着色剤は、公知の無機顔料や有機顔料、チクソトロピー付与剤は、シリカ等、難燃剤は、リン酸エステル類等それぞれ市販されているものが使用できる。 Examples of the polymerization regulator include polymerization inhibitors such as hydroquinone, methylhydroquinone, methoxyhydroquinone, and t-butylhydroquinone, and chain transfer agents such as thiol compounds. As the antioxidant, a hindered phenol type such as 2,6-di-t-butylhydroxytoluene is preferably used. Commercially available inorganic pigments and organic pigments, thixotropy-imparting agents such as silica, and flame retardants such as phosphoric esters can be used as the colorant.
以下に、実施例および比較例により、本発明をさらに詳細に説明するが、本発明はこれらにより何ら限定されるものではない。尚、「部」は「重量部」を示し、「％」は「重量％」を示す。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. “Part” indicates “part by weight”, and “%” indicates “% by weight”.
合成例、実施例における各測定方法、試験方法を下記に示す。
（１）粘度
ＪＩＳ Ｋ ６９０１ ５．５に準じてブルックフィールドＢ型粘度計にて測定（温度：２５℃）した。
（２）体積収縮率
ＪＩＳ Ｋ ６９０１ ５．１２に従い硬化前後の密度の差により求めた。
（３）引っ張り試験における破断強度、破断伸び率
ＪＩＳ Ｋ ７１１３に従った。 樹脂組成物を硬化させ1号型ダンベル状に調整した試験片を１．０ｍｍ／ｍｉｎ．で引張り試験を行い、破断強度および破断伸び率を測定した。
（４）ガラス転移温度（Ｔｇ）
動的粘弾性測定により耐熱性の指標となるＴｇを測定した。試験機は、ORIENTEC社製RHEOVIBRON,RHEO-1023を用いた。測定は２５℃〜２００℃まで行なった．昇温速度は、２℃/ｍｉｎ．、加振周波数は単一波形１０Ｈｚ、振幅は２５μｍで測定した。得られたtanδ曲線のピーク温度をＴｇとした。
（５）透明性
日本電色工業社製 ＮＤＨ−１００１ＤＰにて成形物（注型板）の光線透過率を測定した。数値は空気中を透過する光を１００として％で表した。
Each measurement method and test method in Synthesis Examples and Examples are shown below.
(1) Viscosity Measured with a Brookfield B-type viscometer (temperature: 25 ° C.) according to JIS K 6901 5.5.
(2) Volume shrinkage rate Determined by the difference in density before and after curing in accordance with JIS K 6901 5.12.
(3) Breaking strength and elongation at break in tensile test JIS K 7113 was followed. A test piece prepared by curing the resin composition and adjusting it to a No. 1 type dumbbell was 1.0 mm / min. A tensile test was conducted to measure the breaking strength and elongation at break.
(4) Glass transition temperature (Tg)
Tg as an index of heat resistance was measured by dynamic viscoelasticity measurement. The testing machine used was RHEOVIBRON, RHEO-1023 manufactured by ORIENTEC. The measurement was performed from 25 ° C to 200 ° C. The heating rate is 2 ° C./min. The excitation frequency was measured with a single waveform of 10 Hz, and the amplitude was 25 μm. The peak temperature of the obtained tan δ curve was defined as Tg.
(5) Transparency The light transmittance of the molded product (casting plate) was measured with NDH-1001DP manufactured by Nippon Denshoku Industries Co., Ltd. The numerical value is expressed in%, where 100 is the light transmitted through the air.
合成例１
（（ａ）成分；単官能ウレタン（メタ）アクリレート反応性オリゴマー含有樹脂の合成）
温度計、還流冷却機、攪拌装置を取り付けたセパラブル４つ口フラスコに脂環式ジイソシアネートであるイソホロンジイソシアネート３８９．７ｇ（１．７６mol）、ジブチル錫ラウレート ０．３ｇを投入し、窒素雰囲気下シクロヘキサノール１７５．５ｇ（１．７６mol）を滴下し、滴下後は５０℃で４時間反応させた。次いで、２，６−ジ−ｔ−ブチル−４−メチルフェノール(精工化学社製、商品名：スワノックス)０．５ｇを加え、２−ヒドロキシエチルメタクリレート ２３４．０ｇ（１．８０mol）を滴下しながら、窒素雰囲気下８０℃でさらに４時間反応させた。次いでメタクリル酸メチル２００ｇを加え溶解して単官能ウレタン（メタ）アクリレート反応性オリゴマー含有樹脂（ＵＡ−１と記す）を得た。得られた単官能ウレタン（メタ）アクリレート反応性オリゴマー含有樹脂の粘度は１０００mPa・sであった。
Synthesis example 1
(Component (a): Synthesis of monofunctional urethane (meth) acrylate reactive oligomer-containing resin)
Into a separable four-necked flask equipped with a thermometer, reflux condenser, and stirrer was charged 389.7 g (1.76 mol) of cyclophoric diisocyanate and 0.3 g of dibutyltin laurate, and cyclohexanol in a nitrogen atmosphere. 175.5 g (1.76 mol) was added dropwise, and after the addition, the mixture was reacted at 50 ° C. for 4 hours. Next, 0.5 g of 2,6-di-t-butyl-4-methylphenol (trade name: Swanox, manufactured by Seiko Chemical Co., Ltd.) was added, and 234.0 g (1.80 mol) of 2-hydroxyethyl methacrylate was added dropwise. The mixture was further reacted at 80 ° C. for 4 hours under a nitrogen atmosphere. Next, 200 g of methyl methacrylate was added and dissolved to obtain a monofunctional urethane (meth) acrylate reactive oligomer-containing resin (referred to as UA-1). The viscosity of the obtained monofunctional urethane (meth) acrylate reactive oligomer-containing resin was 1000 mPa · s.
合成例２
（（ａ）成分；単官能ウレタン（メタ）アクリレート反応性オリゴマー含有樹脂の合成）
シクロヘキサノールの代わりにイソカンフィルシクロヘキサノール(高砂香料社製 商品名：Santalex T)を４１６．１ｇ（１．７６mol）使用し、ジシクロペンタニルメタクリレート(日立化成社製 商品名：FA-513M)を６９４ｇ使用する以外は合成例１と同様にして、単官能ウレタン（メタ）アクリレート反応性オリゴマー含有樹脂（ＵＡ−２と記す）を得た。得られた樹脂の粘度は３０００mPa・sであった。
Synthesis example 2
(Component (a): Synthesis of monofunctional urethane (meth) acrylate reactive oligomer-containing resin)
Instead of cyclohexanol, 416.1 g (1.76 mol) of isocamphylcyclohexanol (trade name: Santalex T, manufactured by Takasago Inc.) was used and dicyclopentanyl methacrylate (trade name: FA-513M, manufactured by Hitachi Chemical Co., Ltd.). A monofunctional urethane (meth) acrylate reactive oligomer-containing resin (referred to as UA-2) was obtained in the same manner as in Synthesis Example 1 except that 694 g was used. The viscosity of the obtained resin was 3000 mPa · s.
合成例３
（（ａ）成分；単官能ウレタン（メタ）アクリレート反応性オリゴマー含有樹脂の合成）
シクロヘキサノールの代わりに２−アダマンタノール(東京化成工業社製 試薬)を２６８．０ｇ（１．７６mol）使用し、イソボルニルメタクリレート(共栄社化学社製 商品名：ライトエステルIB-X)を７１６．４ｇ使用する以外は合成例１と同様にして、単官能ウレタン（メタ）アクリレート反応性オリゴマー含有樹脂（ＵＡ−3と記す）を得た。得られた樹脂の粘度は２５００mPa・sであった。
Synthesis example 3
(Component (a): Synthesis of monofunctional urethane (meth) acrylate reactive oligomer-containing resin)
Instead of cyclohexanol, 268.0 g (1.76 mol) of 2-adamantanol (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) was used, and isobornyl methacrylate (trade name: Light Ester IB-X manufactured by Kyoeisha Chemical Co., Ltd.) was used at 716. A monofunctional urethane (meth) acrylate reactive oligomer-containing resin (referred to as UA-3) was obtained in the same manner as in Synthesis Example 1 except that 4 g was used. The viscosity of the obtained resin was 2500 mPa · s.
合成例４
（（ｂ）成分；環状アセタール骨格含有ウレタン（メタ）アクリレートオリゴマー含有樹脂の合成）
合成例１と同様の反応装置にイソホロンジイソシアネート ２６３．４ｇ（１．１９mol）、ジブチル錫ラウレート ０．３ｇを投入し、窒素雰囲気下３，９−ビス（１，１−ジメチル−２−ヒドロキシエチル）−２，４，８，１０−テトラオキサスピロ〔５．５〕ウンデカン（三菱ガス化学社製 スピログリコール）１８０．５ｇ（０．５９mol）を加え、５０℃で４時間反応させた。次いで、２，６−ジ−ｔ−ブチル−４−メチルフェノール０．５ｇを加え、２−ヒドロキシエチルメタクリレート １５５．８ｇ（１．２０mol）を滴下しながら、窒素雰囲気下８０℃でさらに４時間反応させた。次いでメタクリル酸メチル３９９．８ｇを加え溶解して、ウレタン（メタ）アクリレートオリゴマー含有樹脂（ＳＰＧ−ＵＡと記す）を得た。得られた樹脂の粘度は３０００mPa・sであった。
Synthesis example 4
(Component (b): Synthesis of resin containing cyclic acetal skeleton-containing urethane (meth) acrylate oligomer)
In the same reactor as in Synthesis Example 1, 263.4 g (1.19 mol) of isophorone diisocyanate and 0.3 g of dibutyltin laurate were added and 3,9-bis (1,1-dimethyl-2-hydroxyethyl) was added in a nitrogen atmosphere. 180.5 g (0.59 mol) of -2,4,8,10-tetraoxaspiro [5.5] undecane (spiro glycol manufactured by Mitsubishi Gas Chemical Company) was added and reacted at 50 ° C. for 4 hours. Next, 0.5 g of 2,6-di-t-butyl-4-methylphenol was added, and the reaction was further performed at 80 ° C. for 4 hours in a nitrogen atmosphere while dropping 155.8 g (1.20 mol) of 2-hydroxyethyl methacrylate. I let you. Next, 399.8 g of methyl methacrylate was added and dissolved to obtain a urethane (meth) acrylate oligomer-containing resin (referred to as SPG-UA). The viscosity of the obtained resin was 3000 mPa · s.
実施例１
（ａ）成分として合成例１で得たＵＡ−１ ２０部、（ｂ）成分として、アクリルシラップ(日本ユピカ社製 ユピカ８９００ ；ポリマー含有率 ２３％)７０部及び（ｃ）成分としてテトラヒドロフルフリルメタクリレート（共栄社化学社製、商品名：ライトエステルTHF）１０部、消泡剤（ビックケミー社製、商品名：BYK−Ａ５１５）０．０５部、重合開始剤（日本油脂社製 商品名：パーセロイルＴＣＰ）１．０部を高速攪拌装置で混合し硬化性樹脂組成物を調整した。得られた硬化性樹脂組成物は注入しやすい粘度であった。３０ｃｍ角のガラス板２枚と厚み３ｍｍのスペーサーにより作製したガラスセルに硬化性樹脂組成物を流し込み、６０℃に調整した乾燥炉にて６０分で硬化、１２０℃で２時間後硬化を行った。上記方法により注型板を評価した。
Example 1
20 parts of UA-1 obtained in Synthesis Example 1 as the component (a), 70 parts of acrylic syrup (Iupica 8900 manufactured by Iupika Japan; polymer content 23%) as the component (b), and tetrahydrofurfuryl as the component (c) 10 parts of methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light Ester THF), 0.05 part of antifoaming agent (trade name: BYK-A515, trade name of BYK-A515), polymerization initiator (trade name: Perceloyl TCP, manufactured by NOF Corporation) ) 1.0 part was mixed with a high-speed stirrer to prepare a curable resin composition. The obtained curable resin composition had a viscosity that was easy to inject. The curable resin composition was poured into a glass cell prepared with two 30 cm square glass plates and a 3 mm thick spacer, cured in a drying furnace adjusted to 60 ° C. in 60 minutes, and post-cured at 120 ° C. for 2 hours. . The cast plate was evaluated by the above method.
実施例２
（ａ）成分として合成例１で得たＵＡ−２ ２０部、（ｂ）成分としてスチレン希釈のエポキシアクリレート樹脂(日本ユピカ社製 商品名：ネオポール8１０１；オリゴマー含有率 ６１%)７０部、（ｃ）成分としてテトラヒドロフルフリルメタクリレート １０部、BYK−Ａ５１５ ０．０５部、パーセロイルＴＣＰ１．０部を使用する以外は実施例１と同様にして硬化性樹脂組成物を得た。得られた硬化性樹脂組成物は注入しやすい粘度であった。実施例１と同様にして注型板を得て同様に評価した。
Example 2
(A) 20 parts of UA-2 obtained in Synthesis Example 1 as a component, 70 parts of (b) component as a styrene-diluted epoxy acrylate resin (trade name: Neopole 8101; oligomer content 61%, manufactured by Nippon Pica) ) A curable resin composition was obtained in the same manner as in Example 1 except that 10 parts of tetrahydrofurfuryl methacrylate, 0.05 parts of BYK-A515 and 1.0 part of perceloyl TCP were used as components. The obtained curable resin composition had a viscosity that was easy to inject. A cast plate was obtained in the same manner as in Example 1 and evaluated in the same manner.
実施例３
（ａ）成分として合成例１で得たＵＡ−３ ２０部、（ｂ）成分としてメタクリル酸メチル希釈のウレタンアクリレート樹脂(日本ユピカ社製 ユピカ８９３６；オリゴマー含有率 ８０％)７０部、（ｃ）成分としてテトラヒドロフルフリルメタクリレート １０部、（ｄ）成分としてエチレンチオ尿素(三新化学社製 商品名：サンセラー２２-C)０．２部、BYK−Ａ５１５ ０．０５部、重合開始剤（日本油脂社製、商品名：パークミルH−８０）１．０部を加えて更に混合して硬化性樹脂組成物を調整した。得られた硬化性樹脂組成物は注入しやすい粘度であった。実施例１と同様のガラスセルに樹脂組成物を注入して２５℃、６０分で硬化、１２０℃で２時間後硬化を行った。得られた注型板は無着色であった。実施例１と同様に注型板を評価した。
Example 3
(A) 20 parts of UA-3 obtained in Synthesis Example 1 as a component, 70 parts of urethane methacrylate resin diluted with methyl methacrylate (Iupica 8936; oligomer content 80%, Nippon Iupika Co., Ltd.) as component (b), (c) 10 parts of tetrahydrofurfuryl methacrylate as component, 0.2 parts of ethylenethiourea (trade name: Sunseller 22-C manufactured by Sanshin Chemical Co., Ltd.) as component (d), 0.05 part of BYK-A515, polymerization initiator (Nippon Yushi Co., Ltd.) Manufactured, trade name: Park Mill H-80) 1.0 part was added and further mixed to prepare a curable resin composition. The obtained curable resin composition had a viscosity that was easy to inject. The resin composition was injected into the same glass cell as in Example 1, cured at 25 ° C. for 60 minutes, and post-cured at 120 ° C. for 2 hours. The resulting cast plate was uncolored. The cast plate was evaluated in the same manner as in Example 1.
実施例４
（ａ）成分として合成例１で得たＵＡ−１ ２０部、（ｂ）成分として合成例４で得たＳＰＧ−ＵＡ ７０部、（ｃ）成分としてテトラヒドロフルフリルメタクリレート １０部、ＢＹＫ−Ａ５１５ ０．０５部、パーセロイルＴＣＰ１．０部を使用する以外は実施例１と同様にして硬化性樹脂組成物を得た。得られた硬化性樹脂物は注入しやすい粘度であった。実施例１と同様にして注型板を得て同様に評価した。
Example 4
20 parts of UA-1 obtained in Synthesis Example 1 as the component (a), 70 parts of SPG-UA obtained in Synthesis Example 4 as the component (b), 10 parts of tetrahydrofurfuryl methacrylate as the component (c), BYK-A515 0 A curable resin composition was obtained in the same manner as in Example 1 except that 0.05 part and 1.0 part of Perceloyl TCP were used. The obtained curable resin product had a viscosity that was easy to inject. A cast plate was obtained in the same manner as in Example 1 and evaluated in the same manner.
比較例１
アクリルシラップ(日本ユピカ社製 ユピカ８９００)９０部、架橋ポリスチレン（総研化学社製 SGP-７０C）１０部、ＢＹＫ−Ａ５１５ ０．０５部及びパーセロイルＴＣＰ１．０部を使用する以外は実施例１と同様にして硬化性樹脂組成物を得た。得られた硬化性樹脂組成物は注入するのにはやや高い粘度であった。実施例１と同様にして注型板を得て同様に評価した。
Comparative Example 1
Example 1 except that 90 parts of acrylic syrup (Yupika 8900, manufactured by Iupika Japan Co., Ltd.), 10 parts of crosslinked polystyrene (SGP-70C, manufactured by Soken Chemical Co., Ltd.), 0.05 part of BYK-A515 and 1.0 part of parceloyl TCP are used. Thus, a curable resin composition was obtained. The resulting curable resin composition had a slightly higher viscosity for injection. A cast plate was obtained in the same manner as in Example 1 and evaluated in the same manner.
比較例２
スチレン希釈のエポキシアクリレート樹脂(日本ユピカ社製 商品名：ネオポール８１０９)９０部、架橋ポリスチレン（総研化学社製 SGP-７０C）１０部、ＢＹＫ−Ａ５１５ ０．０５部及びパーセロイルＴＣＰ１．０部を使用する以外は実施例１と同様にして硬化性樹脂組成物を得た。得られた硬化性樹脂組成物は注入するのにはやや高い粘度であった。実施例１と同様にして注型板を得て同様に評価した。
Comparative Example 2
Use 90 parts of epoxy acrylate resin diluted with styrene (trade name: Neopol 8109, manufactured by Nippon Iupika Co., Ltd.), 10 parts of crosslinked polystyrene (SGP-70C, manufactured by Soken Chemical Co., Ltd.), 0.05 part of BYK-A515, and 1.0 part of parceloyl TCP. Except for the above, a curable resin composition was obtained in the same manner as in Example 1. The resulting curable resin composition had a slightly higher viscosity for injection. A cast plate was obtained in the same manner as in Example 1 and evaluated in the same manner.
上記の表１から、
（１）実施例１〜４より明らかなように、本発明の単官能ウレタン（メタ）アクリレート反応性オリゴマーに市販の樹脂および（メタ）アクリレートモノマーを配合した本発明の硬化型樹脂組成物は、比較例１および２で示されるアクリルシラップに低収縮剤を配合した硬化型樹脂組成物に比べて低収縮であり、且つ透明性に優れている。他の物性に関しても充分に高いものであった。
（２）チオ尿素化合物を配合した硬化性樹脂組成物を使用した実施例３は常温にて容易に着色なく硬化可能であった。
From Table 1 above,
(1) As is clear from Examples 1 to 4, the curable resin composition of the present invention in which a commercially available resin and a (meth) acrylate monomer were blended with the monofunctional urethane (meth) acrylate reactive oligomer of the present invention, Compared with the curable resin composition in which the acrylic syrup shown in Comparative Examples 1 and 2 is blended with a low shrinkage agent, it has low shrinkage and is excellent in transparency. The other physical properties were sufficiently high.
(2) Example 3 using a curable resin composition containing a thiourea compound was easily curable without coloring at room temperature.
Claims (8)
The radical curable resin composition according to claim 1, wherein the (meth) acrylate compound having a cyclic ether compound in the side chain is tetrahydrofurfuryl (meth) acrylate.
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| US11680039B2 (en) | 2016-08-10 | 2023-06-20 | Arkema France | Compounds containing cyclic structural elements, urethane/ureido linkages and a free radical-polymerizable functional group |
| WO2019176568A1 (en) | 2018-03-16 | 2019-09-19 | 三菱ケミカル株式会社 | Sheet molding compound and carbon fiber composite material molded article |
| US11512412B2 (en) | 2018-03-16 | 2022-11-29 | Mitsubishi Chemical Corporation | Sheet molding compound and carbon fiber composite material molded article |
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