JPH04372649A - Unsaturated polyester resin composition, production of cured article, and molding material - Google Patents
Unsaturated polyester resin composition, production of cured article, and molding materialInfo
- Publication number
- JPH04372649A JPH04372649A JP14880591A JP14880591A JPH04372649A JP H04372649 A JPH04372649 A JP H04372649A JP 14880591 A JP14880591 A JP 14880591A JP 14880591 A JP14880591 A JP 14880591A JP H04372649 A JPH04372649 A JP H04372649A
- Authority
- JP
- Japan
- Prior art keywords
- unsaturated polyester
- resin composition
- polyester resin
- compsn
- molding material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000012778 molding material Substances 0.000 title claims abstract description 7
- 239000000203 mixture Substances 0.000 title claims description 33
- 229920006337 unsaturated polyester resin Polymers 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims abstract description 28
- -1 alkyl phosphate Chemical compound 0.000 claims abstract description 20
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 9
- 239000010452 phosphate Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000945 filler Substances 0.000 claims abstract description 3
- 229920006305 unsaturated polyester Polymers 0.000 claims description 11
- 150000003682 vanadium compounds Chemical class 0.000 claims description 10
- 239000003505 polymerization initiator Substances 0.000 claims description 8
- 239000012779 reinforcing material Substances 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 13
- 229910052720 vanadium Inorganic materials 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 2
- 239000003999 initiator Substances 0.000 abstract 2
- 238000013329 compounding Methods 0.000 abstract 1
- 229920000728 polyester Polymers 0.000 abstract 1
- 230000002787 reinforcement Effects 0.000 abstract 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 239000011342 resin composition Substances 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 7
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229940041260 vanadyl sulfate Drugs 0.000 description 6
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 5
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000001879 gelation Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000005287 vanadyl group Chemical group 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-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
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-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
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 238000009776 industrial production Methods 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
- 238000002156 mixing Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000010422 painting Methods 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
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000013008 thixotropic agent Substances 0.000 description 2
- 150000004992 toluidines Chemical class 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
- 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
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- QYXHDJJYVDLECA-UHFFFAOYSA-N 2,5-diphenylcyclohexa-2,5-diene-1,4-dione Chemical compound O=C1C=C(C=2C=CC=CC=2)C(=O)C=C1C1=CC=CC=C1 QYXHDJJYVDLECA-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
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical class OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229920000298 Cellophane Polymers 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- NBICYCZLCAMSBG-UHFFFAOYSA-L [Co+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O Chemical compound [Co+2].CCCCCC=CC([O-])=O.CCCCCC=CC([O-])=O NBICYCZLCAMSBG-UHFFFAOYSA-L 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
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N butyl alcohol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-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
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 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
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002990 reinforced plastic Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は不飽和ポリエステル樹脂
組成物、さらに詳しくは強化プラスチック（ＦＲＰ）用
、注形用、ボタン用、化粧板用、塗装用などに好適な不
飽和ポリエステル樹脂組成物、これを用いた硬化物の製
造法および成形材料に関する。[Industrial Application Field] The present invention relates to an unsaturated polyester resin composition, more specifically, an unsaturated polyester resin composition suitable for reinforced plastics (FRP), casting, buttons, decorative boards, painting, etc. , relates to a method for producing a cured product using the same, and a molding material.
【０００２】0002
【従来の技術】従来、不飽和ポリエステル樹脂組成物の
硬化は、重合開始剤を添加して加温もしくは常温で、ま
たは重合開始剤とともに促進剤を加えて行われている。
常温で硬化する方法は、経済的に望ましいばかりでなく
、加熱を避けなければならない木材製品のような加工製
品の製造に際して特に必要な方法であり、重合開始剤と
促進剤の組合わせによる種々の方法が提案されている。BACKGROUND OF THE INVENTION Conventionally, unsaturated polyester resin compositions have been cured by adding a polymerization initiator and heating or at room temperature, or by adding an accelerator together with the polymerization initiator. The method of curing at room temperature is not only economically desirable but also particularly necessary in the production of processed products such as wood products, where heating must be avoided. A method is proposed.
【０００３】重合開始剤と促進剤の組合わせとしては、
ベンゾイルパーオキサイドとジアルキルアニリンやトル
イジン誘導体の組合わせ、メチルエチルケトンパーオキ
サイドとナフテン酸コバルトまたはそれらにジアルキル
アニリンやトルイジン誘導体を加えた組合わせなどが知
られている。しかし、これらの促進剤を用いた場合には
、硬化物の色相が黄褐色または淡赤紫色を呈するという
欠点があり、例えばボタン、化粧板等のように硬化物の
色相が特に問題となるような製品には用いることができ
なかった。また冬期屋外の低温時におけるＦＲＰ成形な
どの際には硬化速度が低下するという問題があった。[0003] As a combination of a polymerization initiator and an accelerator,
Combinations of benzoyl peroxide and dialkylaniline or toluidine derivatives, methyl ethyl ketone peroxide and cobalt naphthenate, or combinations of these with dialkylaniline or toluidine derivatives are known. However, when these accelerators are used, there is a drawback that the hue of the cured product is yellowish brown or pale reddish-purple. It could not be used for such products. Furthermore, there is a problem in that the curing speed decreases when FRP molding is performed outdoors at low temperatures in winter.
【０００４】このような問題を解決するため、バナジウ
ム化合物とジアルキルリン酸エステルを組合わせた促進
剤（英国特許９０７３６３号）、バナジウム化合物と還
元性イオウ化合物とを組合わせた促進剤（公告昭３９−
２９１９５号公報）などが提案されている。これらの促
進剤を用いると常温または低温時の硬化性は向上するが
、時間の経過とともに重合反応が部分的に進行し、ゲル
状物を生成するため、貯蔵安定性に著しく劣り、工業的
生産が困難であるという問題があった。[0004] In order to solve these problems, an accelerator consisting of a combination of a vanadium compound and a dialkyl phosphate ester (British Patent No. 907363), an accelerator consisting of a combination of a vanadium compound and a reducing sulfur compound (Public Announcement No. 1983), −
No. 29195) and the like have been proposed. Using these accelerators improves curing properties at room or low temperatures, but over time the polymerization reaction partially progresses and forms a gel, resulting in significantly poor storage stability and impeding industrial production. The problem was that it was difficult.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、上記の従来
技術の問題を解決し、常温における硬化速度に優れ、し
かも淡色透明な硬化物色相を有し、かつ、貯蔵安定性に
優れた不飽和ポリエステル樹脂組成物、これを用いた硬
化物の製造法および成形材料を提供するものである。Problem to be Solved by the Invention The present invention solves the above-mentioned problems of the prior art, and provides a cured product that has an excellent curing speed at room temperature, has a pale transparent color, and has excellent storage stability. The present invention provides a saturated polyester resin composition, a method for producing a cured product using the same, and a molding material.
【０００６】[0006]
【課題を解決するための手段】本発明者等は、上記課題
に鑑み、鋭意検討した結果、バナジウム化合物およびア
ルキルリン酸エステルの組合わせによる促進剤に、メチ
ルハイロドキノンを存在させることにより、速硬化性、
硬化物色相の淡色透明性を保持しつつ、貯蔵安定性を著
しく向上させることができることを見出した。すなわち
、本発明は、（Ａ） 酸成分とアルコール成分を反応さ
せて得られる不飽和ポリエステル、（Ｂ） 架橋性モノ
マー、（Ｃ） バナジウム化合物、（Ｄ） アルキルリ
ン酸エステルおよび（Ｅ） メチルハイドロキノンを含
有してなる不飽和ポリエステル樹脂組成物、この不飽和
ポリエステル樹脂組成物を重合開始剤の存在下に硬化す
る硬化物の製造法および上記不飽和ポリエステル樹脂組
成物を用いた成形材料に関する。[Means for Solving the Problems] In view of the above-mentioned problems, the present inventors have made extensive studies and found that by adding methylhydroquinone to an accelerator consisting of a combination of a vanadium compound and an alkyl phosphate ester, fast curing,
It has been found that the storage stability can be significantly improved while maintaining the pale color transparency of the cured product. That is, the present invention comprises (A) an unsaturated polyester obtained by reacting an acid component and an alcohol component, (B) a crosslinkable monomer, (C) a vanadium compound, (D) an alkyl phosphate ester, and (E) methylhydroquinone. The present invention relates to an unsaturated polyester resin composition containing the above unsaturated polyester resin composition, a method for producing a cured product by curing the unsaturated polyester resin composition in the presence of a polymerization initiator, and a molding material using the unsaturated polyester resin composition.
【０００７】本発明に用いられる不飽和ポリエステル（
Ａ） は、酸成分およびアルコール成分を公知の方法に
より反応させて得られる。酸成分としては、例えば無水
マレイン酸、マレイン酸、フマル酸、イタコン酸等の不
飽和二塩基酸が用いられる。また必要に応じてフタル酸
、無水フタル酸、イソフタル酸、テレフタル酸、コハク
酸、アジピン酸、セバチン酸等の飽和二塩基酸、安息香
酸、トリメリット酸等の二塩基酸以外の酸等を用いるこ
とができる。アルコール成分としては、エチレングリコ
ール、プロピレングリコール、ジエチレングリコール、
ジプロピレングリコール、ネオペンチルグリコール、水
素添加ビスフェノール、１，６−ヘキサンジオール等の
グリコールが用いられる。必要に応じてグリセリン、ペ
ンタエリスリトール等のグリコール以外のアルコールも
用いることができる。Unsaturated polyester used in the present invention (
A) is obtained by reacting an acid component and an alcohol component by a known method. As the acid component, unsaturated dibasic acids such as maleic anhydride, maleic acid, fumaric acid, and itaconic acid are used. If necessary, acids other than saturated dibasic acids such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, and sebacic acid, and dibasic acids such as benzoic acid and trimellitic acid are used. be able to. Alcohol components include ethylene glycol, propylene glycol, diethylene glycol,
Glycols such as dipropylene glycol, neopentyl glycol, hydrogenated bisphenol, and 1,6-hexanediol are used. Alcohols other than glycols such as glycerin and pentaerythritol can also be used if necessary.
【０００８】本発明に用いられる架橋性モノマー（Ｂ）
としては、スチレン、ビニルトルエン、クロロスチレ
ン、α−メチルスチレン、ジビニルベンゼン、メタクリ
ル酸メチル、アクリル酸メチル、アクリル酸エチル、酢
酸ビニル、ジアクリルフタレート等が挙げられる。該架
橋性モノマー（Ｂ） の配合量には特に制限はなく、反
応性、作業性、その他種々の目的に応じて調整すること
ができる。総量を１００重量部として不飽和ポリエステ
ル（Ａ） の７０〜４０重量部に対して架橋性モノマー
（Ｂ）を３０〜６０重量部の範囲で用いることが好まし
い。本発明に用いられるバナジウム化合物（Ｃ） とし
ては、３〜５価のバナジウムまたはバナジル化合物、例
えばバナジウムクロリド（ＶＣｌ３ ）、バナジルクロ
リド（ＶＯＣｌ３ ）、五酸化バナジウム（Ｖ２ Ｏ５
）、バナジル硫酸（ＶＯＳＯ４ ｎＨ２ Ｏ、ｎ＝０
〜５）、バナジル−ｐ−トルエンスルフォン酸、バナジ
ル酢酸、バナジルシュウ酸等の無機酸または有機酸の塩
、酒石酸、リンゴ酸、クエン酸またはグロタミン酸等の
アミノ酸のバナジル錯塩を含む有機酸錯化合物、アセチ
ルアセトン、アセト酢酸エステル類等のβ−ジケトン化
合物のバナジウム、バナジル錯塩等の可溶性化合物が挙
げられる。バナジウム化合物（Ｃ）の配合量は、不飽和
ポリエステル（Ａ） および架橋性モノマー（Ｂ）の総
量に対して０．０００１〜０．０５重量％が好ましい。Crosslinkable monomer (B) used in the present invention
Examples include styrene, vinyltoluene, chlorostyrene, α-methylstyrene, divinylbenzene, methyl methacrylate, methyl acrylate, ethyl acrylate, vinyl acetate, diacryl phthalate, and the like. The amount of the crosslinking monomer (B) is not particularly limited and can be adjusted depending on reactivity, workability, and various other objectives. It is preferable to use the crosslinkable monomer (B) in a range of 30 to 60 parts by weight relative to 70 to 40 parts by weight of the unsaturated polyester (A), with the total amount being 100 parts by weight. The vanadium compound (C) used in the present invention includes trivalent to pentavalent vanadium or vanadyl compounds, such as vanadium chloride (VCl3), vanadyl chloride (VOCl3), vanadium pentoxide (V2O5
), vanadyl sulfate (VOSO4 nH2O, n=0
-5) Salts of inorganic or organic acids such as vanadyl-p-toluenesulfonic acid, vanadyl acetic acid, and vanadyl oxalic acid; organic acid complex compounds containing vanadyl complex salts of amino acids such as tartaric acid, malic acid, citric acid, or grotamic acid; Examples include soluble compounds such as vanadium and vanadyl complex salts of β-diketone compounds such as , acetylacetone, and acetoacetic esters. The blending amount of the vanadium compound (C) is preferably 0.0001 to 0.05% by weight based on the total amount of the unsaturated polyester (A) and the crosslinkable monomer (B).
【０００９】本発明に用いられるアルキルリン酸エステ
ル（Ｄ） としては、ジブチルリン酸エステル、トリブ
チルリン酸エステル、トリエチルリン酸エステルなどが
挙げられる。アルキルリン酸エステル（Ｄ） の配合量
は、不飽和ポリエステル（Ａ） および架橋性モノマー
（Ｂ） の総量に対して０．１〜２．０重量％が好まし
い。本発明には重合禁止剤としてメチルハイドロキノン
（Ｅ） が用いられる。メチルハイドロキノン（Ｅ）
は、上記したバナジウム化合物（Ｃ） およびアルキル
リン酸エステルからなる促進剤とともに存在して、淡色
速硬化性を保持しつつ貯蔵安定性を向上させることがで
きる。その使用量は不飽和ポリエステル（Ａ） および
架橋性モノマー（Ｂ） の総量に対して０．００１〜０
．１重量％が好ましい。本発明の目的に影響を与えない
範囲であれば、ハイドロキノン、ｐ−ｔ−ブチルカテコ
ール、２，５−ジ−ｔ−ブチルハイドロキノン、モノ−
ｔ−ブチルハイドロキノン、ｐ−ベンゾキノン、ナフト
キノン、パラ−キシロキノン、２，５−ジフェニル−ｐ
−ベンゾキノン、メチルハイドロキノン、２，６−ジ−
ｔ−ブチル−ｐ−クレゾール、α−ナフトール、ナフテ
ン酸銅などの重合禁止剤を併用してもよい。[0009] Examples of the alkyl phosphate ester (D) used in the present invention include dibutyl phosphate, tributyl phosphate, and triethyl phosphate. The blending amount of the alkyl phosphate ester (D) is preferably 0.1 to 2.0% by weight based on the total amount of the unsaturated polyester (A) and the crosslinkable monomer (B). In the present invention, methylhydroquinone (E) is used as a polymerization inhibitor. Methylhydroquinone (E)
is present together with the above-mentioned vanadium compound (C) and an accelerator consisting of an alkyl phosphate ester, and can improve storage stability while maintaining light color fast curing properties. The amount used is 0.001 to 0 based on the total amount of unsaturated polyester (A) and crosslinkable monomer (B).
．． 1% by weight is preferred. Hydroquinone, pt-butylcatechol, 2,5-di-t-butylhydroquinone, mono-
t-Butylhydroquinone, p-benzoquinone, naphthoquinone, para-xyquinone, 2,5-diphenyl-p
-benzoquinone, methylhydroquinone, 2,6-di-
A polymerization inhibitor such as t-butyl-p-cresol, α-naphthol, or copper naphthenate may be used in combination.
【００１０】バナジウム化合物（Ｃ） 、アルキルリン
酸エステル（Ｄ）およびメチルハイドロキノン（Ｅ）
は、実用上溶剤に溶解して用いることができる。溶剤と
しては、溶解性、不飽和ポリエステル樹脂との相溶性、
硬化性、貯蔵安定性を示し、硬化物色相に影響を与えな
いものが好ましく、例えばメチルアルコール、エチルア
ルコール、プロピレンアルコール、ブチルアルコール、
ベンジルアルコールのような脂肪族ならびに芳香族アル
コール化合物、トリエチレングリコール、ヘキシレング
リコールのようなグリコール化合物、メチルセルソルブ
、エチルセルソルブのようなグリコールモノエーテル化
合物などが挙げられる。これらのうちメチルセルソルブ
が実用上特に好ましい。溶剤の使用量は、不飽和ポリエ
ステル（Ａ） および架橋性モノマー（Ｂ） の総量に
対して０．１〜５．０重量％が好ましい。Vanadium compound (C), alkyl phosphate ester (D) and methylhydroquinone (E)
can be practically used by dissolving it in a solvent. As a solvent, solubility, compatibility with unsaturated polyester resin,
Those that exhibit curability and storage stability and do not affect the hue of the cured product are preferred, such as methyl alcohol, ethyl alcohol, propylene alcohol, butyl alcohol,
Examples thereof include aliphatic and aromatic alcohol compounds such as benzyl alcohol, glycol compounds such as triethylene glycol and hexylene glycol, and glycol monoether compounds such as methyl cellosolve and ethyl cellosolve. Among these, methylcellosolve is particularly preferred from a practical standpoint. The amount of the solvent used is preferably 0.1 to 5.0% by weight based on the total amount of the unsaturated polyester (A) and the crosslinkable monomer (B).
【００１１】不飽和ポリエステル樹脂組成物の硬化の際
には、例えばベンゾイルパーオキサイド、ターシャリー
ブチルパーベンゾエート等のパーエステル化合物、ジア
シルパーオキサイド化合物、キュメンハイドロパーオキ
サイド等のハイドロパーオキサイド化合物、ジキュミル
パーオキサイド等のジアルキルパーオキサイド化合物、
メチルエチルケトンパーオキサイド、シクロヘキサノン
パーオキサイド等のケトンパーオキサイド化合物などの
重合開始剤が用いられる。重合開始剤の使用量は、通常
、不飽和ポリエステル樹脂組成物に対して０．５〜３．
０重量％であり、その種類により異なるが、おおむね５
℃以上から１５０℃程度の範囲で硬化される。本発明の
不飽和ポリエステル樹脂組成物には、ガラス繊維等の補
強剤、炭酸カルシウム等の充填剤、エロジール等の揺変
剤、ワックス等の表面乾燥性付与剤等を含んでもよい。When curing the unsaturated polyester resin composition, for example, perester compounds such as benzoyl peroxide and tert-butyl perbenzoate, hydroperoxide compounds such as diacyl peroxide compounds and cumene hydroperoxide, dialkyl peroxide compounds such as mil peroxide,
A polymerization initiator such as a ketone peroxide compound such as methyl ethyl ketone peroxide or cyclohexanone peroxide is used. The amount of polymerization initiator used is usually 0.5 to 3.0% based on the unsaturated polyester resin composition.
0% by weight, although it varies depending on the type, it is approximately 5% by weight.
It is cured at temperatures ranging from 150°C to 150°C. The unsaturated polyester resin composition of the present invention may contain a reinforcing agent such as glass fiber, a filler such as calcium carbonate, a thixotropic agent such as Erosil, a surface drying agent such as wax, and the like.
【００１２】0012
【実施例】以下、本発明を実施例により詳しく説明する
。実施例中の部は特に断らない限り重量部を意味する。
実施例１
無水マレイン酸０．５０モル、無水フタル酸０．５０モ
ル、プロピレングリコール０．８モルおよびエチレング
リコール０．３モルを、加熱装置、温度計、窒素ガス吹
込み装置、縮合水留出装置を備えた反応釜に入れ、窒素
雰囲気中で攪拌しながら、１５０℃に加熱してハーフエ
ステル化させた後、２１０℃で酸価が約２０になるまで
反応させて不飽和ポリエステルを合成した。この不飽和
ポリエステル６５部を、メチルハイドロキノン０．０１
部を溶解したスチレンモノマー３５部に溶解させて樹脂
組成物 （Ｉ） を得た。[Examples] The present invention will be explained in detail below using examples. Parts in the examples mean parts by weight unless otherwise specified. Example 1 0.50 mol of maleic anhydride, 0.50 mol of phthalic anhydride, 0.8 mol of propylene glycol and 0.3 mol of ethylene glycol were added to a heating device, a thermometer, a nitrogen gas blowing device, and a condensed water distillate. The mixture was placed in a reaction vessel equipped with a device and heated to 150°C while stirring in a nitrogen atmosphere to half-esterify it, and then reacted at 210°C until the acid value reached approximately 20 to synthesize an unsaturated polyester. . 65 parts of this unsaturated polyester was mixed with 0.01 parts of methylhydroquinone.
A resin composition (I) was obtained by dissolving one part in 35 parts of styrene monomer.
【００１３】この樹脂組成物 （Ｉ） １００部に、硫
酸バナジルのメチルセルソルブ溶液（バナジルイオン０
．５重量％、以下同じ）０．５部およびジ−ｎ−ブチル
リン酸エステル０．５部を溶解して不飽和ポリエステル
樹脂組成物Ｉを調製した。この不飽和ポリエステル樹脂
組成物Ｉの５０℃での貯蔵安定性、２５℃でのメチルエ
チルケトンパーオキサイド（活性酸素量１０．０％）１
．０重量％を添加して常温硬化させたときの常温ゲル化
時間および硬化物の目視による色相を調べ、その結果を
表１に示した。なお、貯蔵安定性の測定は、試料樹脂１
０ｇを直径１８ｍｍ試験管に注入後、５０℃の恒温槽中
でゲル化までの時間を測定して行った。また常温ゲル化
時間は、ＪＩＳＫ ６９０１の方法によって測定した
。To 100 parts of this resin composition (I) was added a methylcellosolve solution of vanadyl sulfate (vanadyl ion 0
．． An unsaturated polyester resin composition I was prepared by dissolving 0.5 part of 5% by weight (the same applies hereinafter) and 0.5 part of di-n-butyl phosphate. Storage stability of this unsaturated polyester resin composition I at 50°C, methyl ethyl ketone peroxide (active oxygen content 10.0%) 1 at 25°C
．． When 0% by weight was added and cured at room temperature, the gelation time at room temperature and the visual hue of the cured product were examined, and the results are shown in Table 1. Note that the storage stability was measured using sample resin 1.
After injecting 0 g into a test tube with a diameter of 18 mm, the time until gelation was measured in a constant temperature bath at 50°C. Moreover, the room temperature gelation time was measured by the method of JISK 6901.
【００１４】[0014]
【表１】[Table 1]
【００１５】比較例１〜４
実施例１の樹脂組成物 （Ｉ） の製造において、メチ
ルハイドロキノンの代わりにハイドロキノンを用いて得
られた樹脂組成物（ＩＩ）に、硫酸バナジルのメチルセ
ルソルブ溶液０．５部を溶解して不飽和ポリエステル樹
脂組成物ＩＩとした （比較例１）。該樹脂組成物（Ｉ
Ｉ）１００部に硫酸バナジルのメチルセルソルブ溶液０
．５部およびジ−ｎ−ブチルリン酸エステル０．５部を
溶解して不飽和ポリエステル樹脂組成物ＩＩＩ を調製
した（比較例２）。また実施例１において、樹脂組成物
（Ｉ） の調製の際にメチルハイドロキノンの代わり
に２，５−ジ−ｔ−ブチルハイドロキノンおよびα−ナ
フトキノンをそれぞれ用いた以外は実施例１と同様にし
て不飽和ポリエステル樹脂組成物ＩＶおよびＶを調製し
た（比較例３、４）。得られた不飽和ポリエステル樹脂
組成物ＩＩ〜Ｖを用いて実施例１と同様にして貯蔵安定
性、常温ゲル化時間および硬化物色相を調べ、その結果
を表１に示した。表１から、メチルハイドロキノン、硫
酸バナジルおよびジブチルリン酸エステルを含む不飽和
ポリエステル樹脂組成物Ｉでは、その硬化物が淡色で、
かつ速硬化性であり、しかも他の不飽和ポリエステル樹
脂組成物ＩＩ〜Ｖに較べて貯蔵安定性が著しく向上する
ことが示される。Comparative Examples 1 to 4 In the production of the resin composition (I) of Example 1, a methylcellosolve solution of vanadyl sulfate was added to the resin composition (II) obtained by using hydroquinone instead of methylhydroquinone. .5 parts were dissolved to prepare unsaturated polyester resin composition II (Comparative Example 1). The resin composition (I
I) Methylcellosolve solution of vanadyl sulfate in 100 parts 0
．． 5 parts and 0.5 parts of di-n-butyl phosphate were dissolved to prepare an unsaturated polyester resin composition III (Comparative Example 2). Further, in Example 1, the same procedure as in Example 1 was carried out except that 2,5-di-t-butylhydroquinone and α-naphthoquinone were used instead of methylhydroquinone when preparing the resin composition (I). Saturated polyester resin compositions IV and V were prepared (Comparative Examples 3 and 4). Using the obtained unsaturated polyester resin compositions II to V, the storage stability, gelation time at room temperature, and color of the cured product were examined in the same manner as in Example 1, and the results are shown in Table 1. From Table 1, the cured product of unsaturated polyester resin composition I containing methylhydroquinone, vanadyl sulfate, and dibutyl phosphate is light in color,
It is shown that the composition has fast curing properties and has significantly improved storage stability compared to other unsaturated polyester resin compositions II to V.
【００１６】実施例２および比較例５
無水マレイン酸０．５モル、無水フタル酸０．５モル、
プロピレングリコール０．９モルおよびジプロピレング
リコール０．２モルを実施例１と同様にして反応させて
得られた不飽和ポリエステル４０部を、ハイドロキノン
０．０１部を溶解したスチレンモノマー４０部に溶解さ
せ、これに揺変剤（アエロジル２００、日本アエロジル
社製）０．６部を加えて充分に混合して樹脂組成物（Ｖ
Ｉ）を得た。一方、メタノール３５．９５部に、メチル
ハイドロキノンおよび２，６−ジ−ｔ−ブチル−ｐ−ク
レゾールをそれぞれ４部、硫酸バナジル０．０５部なら
びにジブチルリン酸エステル６０部を加えて溶解して促
進剤ＡおよびＢとした。上記樹脂組成物（ＶＩ）１００
部に促進剤ＡおよびＢをそれぞれ０．５部添加して不飽
和ポリエステル樹脂組成物ＶＩおよびＶＩＩ を得た。
これらの貯蔵安定性および２５℃でキュメンハイドロパ
ーオキサイド（活性酸素量７．７％）１．０重量％を添
加した場合の常温ゲル化時間を調べ、その結果を表２に
示した。Example 2 and Comparative Example 5 0.5 mol of maleic anhydride, 0.5 mol of phthalic anhydride,
40 parts of unsaturated polyester obtained by reacting 0.9 mol of propylene glycol and 0.2 mol of dipropylene glycol in the same manner as in Example 1 was dissolved in 40 parts of styrene monomer in which 0.01 part of hydroquinone was dissolved. , 0.6 parts of a thixotropic agent (Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.) was added and mixed thoroughly to form a resin composition (V
I) was obtained. Separately, 4 parts each of methylhydroquinone and 2,6-di-t-butyl-p-cresol, 0.05 parts of vanadyl sulfate, and 60 parts of dibutyl phosphate were added and dissolved in 35.95 parts of methanol to form an accelerator. A and B. The above resin composition (VI) 100
0.5 parts of each of accelerators A and B were added to obtain unsaturated polyester resin compositions VI and VII. The storage stability of these and the gelation time at room temperature when 1.0% by weight of cumene hydroperoxide (active oxygen content 7.7%) was added at 25°C were investigated, and the results are shown in Table 2.
【００１７】[0017]
【表２】
表２から、重合禁止剤としてハイドロキノンおよび
メチルハイドロキノンを含む不飽和ポリエステル樹脂組
成物ＶＩでは、貯蔵安定性が著しく向上することが示さ
れる。Table 2 shows that the unsaturated polyester resin composition VI containing hydroquinone and methylhydroquinone as polymerization inhibitors has significantly improved storage stability.
【００１８】実施例３および比較例６
実施例２の不飽和ポリエステル樹脂組成物Ｖ１および樹
脂組成物（ＶＩ）に、それぞれオクテン酸コバルト（金
属コバルト６．０％）０．３重量％とジメチルアニリン
０．０３重量％を添加して不飽和ポリエステル樹脂組成
物ＶＩＩＩおよびＩＸを調製した。この不飽和ポリエス
テル樹脂組成物ＶＩＩＩおよびＩＸのそれぞれ５０部に
、２５℃および１５℃においてメチルエチルケトンパー
オキサイド（活性酸素量１０．０％）１．０重量％を添
加し、これをガラスマット（１５０ｍｍ×１５０ｍｍ）
３層に含浸させ、セロハンに包み、脱泡、硬化させてＦ
ＲＰを作製した。得られたＦＲＰの硬化時間、硬度およ
び硬化物色相を調べ、その結果を表３に示す。Example 3 and Comparative Example 6 0.3% by weight of cobalt octenoate (metallic cobalt 6.0%) and dimethylaniline were added to the unsaturated polyester resin composition V1 and resin composition (VI) of Example 2, respectively. Unsaturated polyester resin compositions VIII and IX were prepared by adding 0.03% by weight. To 50 parts each of these unsaturated polyester resin compositions VIII and IX, 1.0% by weight of methyl ethyl ketone peroxide (active oxygen content 10.0%) was added at 25°C and 15°C, and this was mixed into a glass mat (150 mm x 150mm)
Impregnated in 3 layers, wrapped in cellophane, defoamed, hardened and F
RP was produced. The curing time, hardness, and color of the cured product of the obtained FRP were examined, and the results are shown in Table 3.
【００１９】[0019]
【表３】
（注）バーコール硬度計（バーコル９３５）を用い、硬
度６０に達する時間表３から、本発明の不飽和ポリエス
テル樹脂組成物を用いた実施例３では、ＦＲＰの硬化時
間が長いにもかかわらず、硬度６０に達する時間が速く
、また硬化物の色相にも優れることが示される。[Table 3] (Note) Time to reach hardness of 60 using a Barcol hardness meter (Barcol 935) From Table 3, in Example 3 using the unsaturated polyester resin composition of the present invention, the curing time of FRP was longer. Nevertheless, it was shown that the hardness reached 60 quickly, and the color of the cured product was also excellent.
【００２０】[0020]
【発明の効果】本発明になる不飽和ポリエステル樹脂組
成物によれば、バナジウム化合物を含む促進剤により迅
速な硬化性と硬化物の色相の淡色透明性を保持すること
ができ、かつメチルハイドロキノンの存在により貯蔵安
定性を工業的生産上、充分実用に供し得るだけの長さに
向上させることができる。本発明の不飽和ポリエステル
樹脂組成物は、ＦＲＰ用、注形用、ボタン用、化粧板用
、塗装用として特に有用である。Effects of the Invention According to the unsaturated polyester resin composition of the present invention, it is possible to maintain rapid curability and light transparency of the color of the cured product by using an accelerator containing a vanadium compound, and it is possible to maintain the light color and transparency of the cured product, and also to maintain the light color and transparency of the cured product. Its presence can improve storage stability to a length sufficient for practical use in industrial production. The unsaturated polyester resin composition of the present invention is particularly useful for FRP, casting, buttons, decorative boards, and painting.
Claims (3)
応させて得られる不飽和ポリエステル、（Ｂ） 架橋性
モノマー、（Ｃ） バナジウム化合物、（Ｄ） アルキ
ルリン酸エステルおよび（Ｅ） メチルハイドロキノン
を含有してなる不飽和ポリエステル樹脂組成物。Claim 1: (A) an unsaturated polyester obtained by reacting an acid component and an alcohol component, (B) a crosslinkable monomer, (C) a vanadium compound, (D) an alkyl phosphate ester, and (E) methylhydroquinone. An unsaturated polyester resin composition containing.
脂組成物を重合開始剤の存在下に硬化する硬化物の製造
法。2. A method for producing a cured product, comprising curing the unsaturated polyester resin composition according to claim 1 in the presence of a polymerization initiator.
脂組成物、重合開始剤ならびに補強材および／または充
填材を含有してなる成形材料。3. A molding material comprising the unsaturated polyester resin composition according to claim 1, a polymerization initiator, and a reinforcing material and/or a filler.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14880591A JPH04372649A (en) | 1991-06-20 | 1991-06-20 | Unsaturated polyester resin composition, production of cured article, and molding material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14880591A JPH04372649A (en) | 1991-06-20 | 1991-06-20 | Unsaturated polyester resin composition, production of cured article, and molding material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04372649A true JPH04372649A (en) | 1992-12-25 |
Family
ID=15461105
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14880591A Pending JPH04372649A (en) | 1991-06-20 | 1991-06-20 | Unsaturated polyester resin composition, production of cured article, and molding material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04372649A (en) |
-
1991
- 1991-06-20 JP JP14880591A patent/JPH04372649A/en active Pending
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