WO2022137686A1 - Unsaturated polyester resin composition and molded object - Google Patents
Unsaturated polyester resin composition and molded object Download PDFInfo
- Publication number
- WO2022137686A1 WO2022137686A1 PCT/JP2021/035157 JP2021035157W WO2022137686A1 WO 2022137686 A1 WO2022137686 A1 WO 2022137686A1 JP 2021035157 W JP2021035157 W JP 2021035157W WO 2022137686 A1 WO2022137686 A1 WO 2022137686A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- unsaturated polyester
- polyester resin
- inorganic filler
- resin composition
- mass
- Prior art date
Links
- 229920006337 unsaturated polyester resin Polymers 0.000 title claims abstract description 68
- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 239000011256 inorganic filler Substances 0.000 claims abstract description 62
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 62
- 239000002245 particle Substances 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 239000000835 fiber Substances 0.000 claims description 21
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- 239000012779 reinforcing material Substances 0.000 claims description 14
- 239000000344 soap Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- 238000000465 moulding Methods 0.000 abstract description 25
- 229920005989 resin Polymers 0.000 abstract description 8
- 239000011347 resin Substances 0.000 abstract description 8
- 239000000047 product Substances 0.000 description 39
- 229920006305 unsaturated polyester Polymers 0.000 description 15
- 238000001723 curing Methods 0.000 description 12
- 150000007519 polyprotic acids Polymers 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000000748 compression moulding Methods 0.000 description 7
- 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 6
- 230000005484 gravity Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000001721 transfer moulding Methods 0.000 description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- -1 pulp Substances 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004641 Diallyl-phthalate Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-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
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000011261 inert gas 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
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-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
- 238000012546 transfer Methods 0.000 description 2
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-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
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-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
- QHWKHLYUUZGSCW-UHFFFAOYSA-N Tetrabromophthalic anhydride Chemical compound BrC1=C(Br)C(Br)=C2C(=O)OC(=O)C2=C1Br QHWKHLYUUZGSCW-UHFFFAOYSA-N 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 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
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
Definitions
- the present invention relates to an unsaturated polyester resin composition and a molded product.
- An unsaturated polyester resin composition obtained by blending an unsaturated polyester resin with a fiber reinforcing material or an inorganic filler has good resin fluidity during molding, and is a cured product having excellent dimensional accuracy, heat resistance, and mechanical strength. It is widely used in the manufacture of OA equipment, chassis of office equipment, lamp reflectors of automobile head lamps, and the like.
- Patent Document 1 and Patent Document 2 disclose an unsaturated polyester resin composition containing an inorganic filler, a fiber reinforcing material, a hollow filler, and the like.
- the unsaturated polyester resin composition flows into the gaps in the mold clearance and hardens, causing burrs on the molded product. Since burrs need to be removed in the removal process, there is a problem that the manufacturing cost increases when a large amount of burrs are generated.
- the present invention has been made to solve the above-mentioned problems, and has good resin fluidity during molding, excellent appearance, dimensional accuracy, and strength physical properties of the molded product, and molding with reduced burrs. It is an object of the present invention to provide an unsaturated polyester resin composition capable of giving a body.
- the present inventors have set the content of the inorganic filler in a specific range in the unsaturated polyester resin composition, and the inorganic filler having three kinds of average particle diameters is selected in a specific ratio.
- the unsaturated polyester resin composition which has good resin fluidity at the time of molding, is excellent in appearance, dimensional accuracy, and strength physical properties of a molded product, and can give a molded product with reduced burrs. And came to complete the present invention.
- An unsaturated polyester resin composition containing (a) an unsaturated polyester resin, (b) an inorganic filler, (c) a metal soap, (d) a low shrinkage agent, (e) a fiber reinforcing material, and (f) a curing agent.
- the content of the (b) inorganic filler is 250 to 600 parts by mass with respect to 100 parts by mass of the (a) unsaturated polyester resin.
- the (b) inorganic filler includes (b1) an inorganic filler having an average particle diameter of 0.5 to 5.0 ⁇ m, and (b2) an inorganic filler having an average particle diameter of 6.0 to 50.0 ⁇ m.
- an unsaturated polyester resin composition which has good resin fluidity at the time of molding, is excellent in appearance, dimensional accuracy, and strength physical properties of a molded product, and can give a molded product with reduced burrs. Can be provided. Further, by curing the unsaturated polyester resin composition, it is possible to provide a molded product having excellent appearance, dimensional accuracy and strength physical characteristics of the molded product and having reduced burrs.
- the "ethylenically unsaturated bond” means a double bond formed between carbon atoms other than the carbon atom forming the aromatic ring.
- ⁇ Unsaturated polyester resin composition In one embodiment of the present invention, (a) unsaturated polyester resin, (b) inorganic filler, (c) metal soap, (d) low shrinkage agent, (e) fiber reinforcing material, and (f) curing agent are used. It is an unsaturated polyester resin composition containing.
- unsaturated polyester resin composition containing.
- the unsaturated polyester resin is a cross-linking of a condensation product (unsaturated polyester) obtained by esterifying a polyhydric alcohol with an unsaturated polybasic acid and a saturated polybasic acid as an optional component.
- a composition dissolved in an agent also referred to as a "reactive diluent"
- the unsaturated polybasic acid is a polybasic acid having a polymerizable ethylenically unsaturated bond
- the saturated polybasic acid is a polybasic acid having no polymerizable ethylenically unsaturated bond.
- Such unsaturated polyester resins are generally known in the technical field of the present invention, and are, for example, "Polyester Resin Handbook” (Nikkan Kogyo Shimbun, published in 1988) and "Paint Glossary” (edited by Japan Society of Color Material, 1993). (Issued annually), etc.
- the polyhydric alcohol used as a raw material for unsaturated polyester is not particularly limited, and those known in the technical field of the present invention can be used.
- Examples of polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, pentanediol, hexanediol, neopentanediol, hydrogenated bisphenol A, bisphenol A and glycerin.
- the polyhydric alcohol can be used alone or in combination of two or more.
- At least one selected from the group consisting of propylene glycol, neopentanediol, bisphenol A, and hydrogenated bisphenol A is preferable from the viewpoint of excellent heat resistance, mechanical strength, and resin fluidity during molding. ..
- the unsaturated polybasic acid used as a raw material for the unsaturated polyester is not particularly limited, and those known in the technical field of the present invention can be used.
- unsaturated polybasic acids include maleic anhydride, fumaric acid, citraconic acid, itaconic acid and het acid.
- the unsaturated polybasic acid can be used alone or in combination of two or more.
- maleic anhydride or fumaric acid is preferable from the viewpoint of excellent heat resistance, mechanical strength, resin fluidity during molding, and the like.
- the saturated polybasic acid used as an arbitrary raw material for unsaturated polyester is not particularly limited, and known ones can be used.
- saturated polybasic acids include phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, tetrachlorophthalic anhydride and tetrabromophthalic anhydride.
- the saturated polybasic acid can be used alone or in combination of two or more.
- Unsaturated polyester can be synthesized by a known method using the above raw materials.
- Various conditions in the synthesis of unsaturated polyester can be appropriately set according to the raw materials used and the amount thereof.
- a method of esterifying under pressure or reduced pressure at a temperature of 140 to 230 ° C. in an inert gas stream such as nitrogen gas can be mentioned.
- an esterification catalyst can be used if necessary.
- the esterification catalyst include known catalysts such as manganese acetate, dibutyltin oxide, stannous oxalate, zinc acetate and cobalt acetate.
- the esterification catalyst can be used alone or in combination of two or more.
- the weight average molecular weight (MW) of the unsaturated polyester is not particularly limited. It is preferably 3,000 to 25,000, more preferably 5,000 to 20,000, and even more preferably 7,000 to 18,000.
- the "weight average molecular weight” is measured by gel permeation chromatography (Polystyrene (registered trademark) GPC-101, Showa Denko KK) at room temperature (23 ° C.) under the following conditions. It means a value obtained using a standard polystyrene calibration curve.
- the cross-linking agent (reactive diluent) that dissolves the unsaturated polyester is not particularly limited as long as it has a polymerizable ethylenically unsaturated bond with the unsaturated polyester, and is known in the technical field of the present invention. Can be used.
- the cross-linking agent include styrene monomer, diallyl phthalate monomer, diallyl phthalate prepolymer, methyl methacrylate and triallyl isocyanurate. These can be used alone or in combination of two or more.
- the content of the cross-linking agent (reactive diluent) in the unsaturated polyester resin is not particularly limited.
- the content of the cross-linking agent (reactive diluent) in the unsaturated polyester resin is the unsaturated polyester and the cross-linking agent from the viewpoint of workability, polymerizability, shrinkage of the molded product, and degree of freedom in adjusting the amount. It is preferably 25 to 70% by mass, more preferably 30 to 68% by mass, and further preferably 35 to 65% by mass with respect to the total of.
- the unsaturated polyester resin may contain a polymerization inhibitor such as hydroquinone, if necessary.
- the unsaturated polyester resin composition of one embodiment has a specific range of the content of the inorganic filler, and the inorganic filler having three kinds of average particle diameters is used at a specific ratio.
- the type of the inorganic filler is not particularly limited, and those known in the technical field of the present invention can be used.
- Examples of the inorganic filler include calcium carbonate, silica, alumina, aluminum hydroxide, barium sulfate, wallastnite, clay, talc, mica, gypsum, silicic acid anhydride, and glass powder. These can be used alone or in combination of two or more. Among them, it is preferable to use at least calcium carbonate from the viewpoint of surface smoothness, cost reduction, and availability of the obtained molded product.
- the shape of the inorganic filler is not particularly limited, and examples thereof include a substantially true sphere, an ellipsoid, a scaly shape, and an amorphous shape.
- the true specific gravity of the inorganic filler is not particularly limited, and is preferably 1 to 10 g / cm 3 , more preferably 1.5 to 8 g / cm 3 , and even more preferably 2 to 5 g. / Cm 3 .
- the true specific gravity of the inorganic filler is 1 g / cm 3 or more, the mechanical properties of the obtained molded product are better, and when the true specific gravity of the inorganic filler is 10 g / cm 3 or less, the unsaturated polyester resin composition is obtained. The kneadability of the product becomes better.
- the blending amount of the inorganic filler is 250 to 600 parts by mass, more preferably 300 to 550 parts by mass, and further preferably 350 to 450 parts by mass with respect to 100 parts by mass of (a) unsaturated polyester resin. It is a department.
- the blending amount of the inorganic filler is 250 parts by mass or more, the mechanical properties of the obtained molded product become better. Further, when (b) the blending amount of the inorganic filler is 600 parts by mass or less, (b) the inorganic filler is more uniformly dispersed in the unsaturated polyester resin composition, so that a homogeneous molded body is produced. Can be done.
- the (b) inorganic filler has (b1) an inorganic filler having an average particle diameter of 0.5 to 5.0 ⁇ m (hereinafter, also referred to as “(b1) inorganic filler”) and (b2) an average particle diameter.
- An inorganic filler of 6.0 to 50.0 ⁇ m hereinafter, also referred to as “(b2) inorganic filler”
- an inorganic filler having an average particle size of 70.0 ⁇ m or more hereinafter, “(b3)
- inorganic filler also referred to as "inorganic filler” and at least three types are used in combination.
- the fluidity of the unsaturated polyester resin composition at the time of molding is improved, and the obtained molded product can be obtained.
- the appearance, dimensional accuracy, and physical characteristics of strength can be improved, and burrs of the molded product can be reduced.
- the average particle size of the inorganic filler is preferably 0.7 ⁇ m or more, more preferably 1.0 ⁇ m or more.
- the average particle size of the inorganic filler is preferably 4.0 ⁇ m or less, more preferably 3.0 ⁇ m or less.
- the average particle size of the inorganic filler is preferably 6.5 ⁇ m or more, more preferably 7.0 ⁇ m or more.
- the average particle size of the inorganic filler is preferably 40.0 ⁇ m or less, more preferably 30.0 ⁇ m or less.
- the average particle size of the inorganic filler is preferably 100 ⁇ m or more, more preferably 200 ⁇ m or more.
- the average particle size of the inorganic filler is preferably 500 ⁇ m or less, more preferably 400 ⁇ m or less, still more preferably 360 ⁇ m or less.
- (b1) :( b2) :( b3) is 60 with respect to a total of 100% by mass of the inorganic fillers (b1), (b2), and (b3). It is contained in a ratio of ⁇ 75: 7 ⁇ 15: 15 ⁇ 30. In addition to further reducing burrs in the obtained molded product, it is preferably contained in a ratio of 60 to 70:10 to 15:20 to 25 in terms of excellent surface smoothness and mechanical strength.
- the mass ratio of the inorganic fillers (b1) to (b3) in the above range, it is possible to achieve both the excellent appearance and strength physical properties of the obtained molded product and the reduction of burrs, and the mass ratio is the above. If it is out of the range, any of the properties of the appearance, strength and physical properties of the molded body, and the reduction of burrs are impaired.
- Metal soap is a component generally used as a mold release agent in the technical field of the present invention.
- the metal soap is not particularly limited, and a soap known in the technical field of the present invention can be used.
- Examples of the metal soap include calcium stearate, zinc stearate, aluminum stearate, and magnesium stearate.
- the metal soap can be used alone or in combination of two or more.
- the amount of the (c) metal soap is not particularly limited, and is preferably 1 to 15 parts by mass, preferably 2 to 10 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin (a). Is more preferable.
- the low shrinkage agent is not particularly limited, and those known in the technical field of the present invention can be used.
- the low shrinkage agent include thermoplastic polymers generally used as a low shrinkage agent such as polystyrene, polymethylmethacrylate, polyvinyl acetate, saturated polyester, and styrene-butadiene rubber.
- the low shrinkage agent can be used alone or in combination of two or more.
- the content of (d) the low shrinkage agent is preferably 10 to 40 parts by mass, more preferably 20 to 35 parts by mass with respect to 100 parts by mass of (a) unsaturated polyester resin.
- D When the blending amount of the low shrinkage agent is 10 parts by mass or more, the shrinkage rate of the molded product becomes small, and desired dimensional accuracy can be obtained. On the other hand, when (d) the blending amount of the low shrinkage agent is 40 parts by mass or less, the mechanical properties of the molded product become better.
- the fiber reinforcing material is a material having an aspect ratio of 3 or more.
- the aspect ratio can be measured by the microscopic method described in Japanese Industrial Standards JIS Z 890-1: 2008 "Particles for Verification of Particle Size Measuring Device".
- the fiber reinforcing material is not particularly limited, and a material known in the technical field of the present invention can be used.
- the (e) fiber reinforcing material include various organic fibers such as glass fiber, pulp, polyethylene terephthalate fiber, vinylon fiber, carbon fiber, aramid fiber, and wallastnite, and inorganic fiber. Among them, glass fiber is preferable, and chopped strand glass cut to a fiber length of about 1.5 to 25 mm is more preferable.
- the content of (e) the fiber reinforcing material is preferably 70 to 120 parts by mass, more preferably 75 to 100 parts by mass with respect to 100 parts by mass of (a) unsaturated polyester resin.
- (E) When the blending amount of the fiber reinforcing material is 70 parts by mass or more, the mechanical properties of the molded product become better. On the other hand, when the blending amount of the (e) fiber reinforcing material is 120 parts by mass or less, the (e) fiber reinforcing material is more uniformly dispersed in the unsaturated polyester resin composition, and a uniform molded body can be produced. can.
- the (f) curing agent is not particularly limited as long as it is a radical polymerization initiator capable of polymerizing an ethylenically unsaturated bond, and those known in the technical field of the present invention can be used.
- the curing agent include t-butylperoxyoctate, benzoyl peroxide, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, and t-butylperoxyisopropylcarbonate. , T-butylperoxybenzoate, dicumyl peroxide, di-t-butyl peroxide and other organic peroxides.
- the curing agent can be used alone or in combination of two or more.
- the content of the curing agent may be appropriately set according to the raw material used, and is not particularly limited.
- the content of (f) the curing agent is preferably 1 to 10 parts by mass, more preferably 1 to 8 parts by mass, and further preferably 1 to 1 to 100 parts by mass with respect to 100 parts by mass of (a) unsaturated polyester resin. 5 parts by mass.
- the unsaturated polyester resin composition of the present invention contains, in addition to the above-mentioned components, components known in the technical field of the present invention such as a thickener, a pigment, and a thickener, as long as the effects of the present invention are not impaired. be able to.
- the thickener is not particularly limited, and examples thereof include (b) metal oxides other than the inorganic filler such as magnesium oxide, magnesium hydroxide, calcium hydroxide, and calcium oxide, and isocyanate compounds.
- the thickener can be used alone or in combination of two or more.
- the unsaturated polyester resin composition can be produced by kneading each component using a method usually used in the technical field of the present invention, for example, a kneader or the like.
- a molded product can be produced by molding an unsaturated polyester resin composition into a desired shape and curing it.
- the molding and curing methods are not particularly limited, and examples thereof include methods usually performed in the technical field of the present invention, such as compression molding, transfer molding, and injection molding.
- a styrene monomer was added to the obtained unsaturated polyester so as to be 30% by mass based on the total of the unsaturated polyester and the styrene monomer to obtain (a) an unsaturated polyester resin.
- an unsaturated polyester resin composition which has good resin fluidity at the time of molding, is excellent in appearance, dimensional accuracy, and strength physical properties of a molded product, and can give a molded product with reduced burrs. Can be provided.
Abstract
Provided is an unsaturated polyester resin composition which has satisfactory resin flowability during molding and can give molded objects excellent in terms of molded-article appearance, dimensional accuracy, and strength and having few burrs. The unsaturated polyester resin composition contains inorganic fillers in an amount in a specific range, the inorganic fillers comprising a specific proportion of three inorganic fillers having respective average particle diameters.
Description
本発明は、不飽和ポリエステル樹脂組成物及び成形体に関する。
The present invention relates to an unsaturated polyester resin composition and a molded product.
不飽和ポリエステル樹脂に繊維強化材や無機充填材を配合した不飽和ポリエステル樹脂組成物は、成形時の樹脂流動性が良好であると共に、寸法精度、耐熱性、及び機械的強度に優れた硬化物を与えるため、ＯＡ機器、事務機器のシャーシ、自動車用ヘッドランプのランプリフレクター等の製造において広く使用されている。
An unsaturated polyester resin composition obtained by blending an unsaturated polyester resin with a fiber reinforcing material or an inorganic filler has good resin fluidity during molding, and is a cured product having excellent dimensional accuracy, heat resistance, and mechanical strength. It is widely used in the manufacture of OA equipment, chassis of office equipment, lamp reflectors of automobile head lamps, and the like.
例えば、特許文献１及び特許文献２には、無機充填材、繊維強化材、中空フィラー等を含有する不飽和ポリエステル樹脂組成物が開示されている。
For example, Patent Document 1 and Patent Document 2 disclose an unsaturated polyester resin composition containing an inorganic filler, a fiber reinforcing material, a hollow filler, and the like.
成形体を製造する際、金型クリアランスの隙間に不飽和ポリエステル樹脂組成物が流れ込んで硬化し、成形体にバリが発生する。バリは除去工程で取り除く必要があるため、バリが多量に発生すると、製造コストが増大する問題があった。
When manufacturing a molded product, the unsaturated polyester resin composition flows into the gaps in the mold clearance and hardens, causing burrs on the molded product. Since burrs need to be removed in the removal process, there is a problem that the manufacturing cost increases when a large amount of burrs are generated.
本発明は上記のような問題を解決するためになされたものであり、成形時の樹脂流動性が良好であるとともに、成形品外観、寸法精度、及び強度物性に優れ、バリが低減された成形体を与えることのできる、不飽和ポリエステル樹脂組成物を提供することを目的とする。
The present invention has been made to solve the above-mentioned problems, and has good resin fluidity during molding, excellent appearance, dimensional accuracy, and strength physical properties of the molded product, and molding with reduced burrs. It is an object of the present invention to provide an unsaturated polyester resin composition capable of giving a body.
本発明者らは鋭意検討の結果、不飽和ポリエステル樹脂組成物において、無機充填材の含有量を特定の範囲とし、当該無機充填材として、３種類の平均粒子径を有するものを特定の比率で用いれば、成形時の樹脂流動性が良好であるとともに、成形品外観、寸法精度、及び強度物性に優れ、バリが低減された成形体を与えることのできる、不飽和ポリエステル樹脂組成物を実現できることを見出し、本発明を完成させるに至った。
As a result of diligent studies, the present inventors have set the content of the inorganic filler in a specific range in the unsaturated polyester resin composition, and the inorganic filler having three kinds of average particle diameters is selected in a specific ratio. When used, it is possible to realize an unsaturated polyester resin composition which has good resin fluidity at the time of molding, is excellent in appearance, dimensional accuracy, and strength physical properties of a molded product, and can give a molded product with reduced burrs. And came to complete the present invention.
すなわち、本発明は以下の態様を含む。
［態様１］
（ａ）不飽和ポリエステル樹脂、（ｂ）無機充填材、（ｃ）金属石鹸、（ｄ）低収縮剤、（ｅ）繊維強化材、及び（ｆ）硬化剤を含む不飽和ポリエステル樹脂組成物であって、
前記（ｂ）無機充填材の含有量は、前記（ａ）不飽和ポリエステル樹脂１００質量部に対して２５０～６００質量部であり、
前記（ｂ）無機充填材は、（ｂ１）平均粒子径が０．５～５．０μｍの無機充填材と、（ｂ２）平均粒子径が６．０～５０．０μｍの無機充填材と、（ｂ３）平均粒子径が７０．０μｍ以上の無機充填材とを、無機充填材（ｂ１）、（ｂ２）、及び（ｂ３）の合計１００質量％に対して、（ｂ１）：（ｂ２）：（ｂ３）＝６０～７５：７～１５：１５～３０となる割合で含む、
不飽和ポリエステル樹脂組成物。
［態様２］
前記（ｂ）無機充填材の含有量は、前記（ａ）不飽和ポリエステル樹脂１００質量部に対して３５０～４５０質量部である、態様１に記載の不飽和ポリエステル樹脂組成物。
［態様３］
前記（ｂ）無機充填材は、炭酸カルシウムを含む態様１又は２のいずれかに記載の不飽和ポリエステル樹脂組成物。
［態様４］
前記（ｅ）繊維強化材の含有量は、（ａ）不飽和ポリエステル樹脂１００質量部に対して７０～１２０質量部である、態様１～３のいずれか一態様に記載の不飽和ポリエステル樹脂組成物。
［態様５］
態様１～４のいずれか一態様に記載の不飽和ポリエステル樹脂組成物の硬化物を含む成形体。 That is, the present invention includes the following aspects.
[Aspect 1]
An unsaturated polyester resin composition containing (a) an unsaturated polyester resin, (b) an inorganic filler, (c) a metal soap, (d) a low shrinkage agent, (e) a fiber reinforcing material, and (f) a curing agent. There,
The content of the (b) inorganic filler is 250 to 600 parts by mass with respect to 100 parts by mass of the (a) unsaturated polyester resin.
The (b) inorganic filler includes (b1) an inorganic filler having an average particle diameter of 0.5 to 5.0 μm, and (b2) an inorganic filler having an average particle diameter of 6.0 to 50.0 μm. b3) With respect to the total 100% by mass of the inorganic fillers (b1), (b2), and (b3) with an inorganic filler having an average particle diameter of 70.0 μm or more, (b1) :( b2) :( b3) = 60 to 75: 7 to 15: 15 to 30.
Unsaturated polyester resin composition.
[Aspect 2]
The unsaturated polyester resin composition according to embodiment 1, wherein the content of the (b) inorganic filler is 350 to 450 parts by mass with respect to 100 parts by mass of the (a) unsaturated polyester resin.
[Aspect 3]
The unsaturated polyester resin composition according to any one of aspects 1 or 2, wherein the inorganic filler (b) contains calcium carbonate.
[Aspect 4]
The unsaturated polyester resin composition according to any one of aspects 1 to 3, wherein the content of the (e) fiber reinforcing material is 70 to 120 parts by mass with respect to 100 parts by mass of the (a) unsaturated polyester resin. thing.
[Aspect 5]
A molded product containing a cured product of the unsaturated polyester resin composition according to any one of aspects 1 to 4.
［態様１］
（ａ）不飽和ポリエステル樹脂、（ｂ）無機充填材、（ｃ）金属石鹸、（ｄ）低収縮剤、（ｅ）繊維強化材、及び（ｆ）硬化剤を含む不飽和ポリエステル樹脂組成物であって、
前記（ｂ）無機充填材の含有量は、前記（ａ）不飽和ポリエステル樹脂１００質量部に対して２５０～６００質量部であり、
前記（ｂ）無機充填材は、（ｂ１）平均粒子径が０．５～５．０μｍの無機充填材と、（ｂ２）平均粒子径が６．０～５０．０μｍの無機充填材と、（ｂ３）平均粒子径が７０．０μｍ以上の無機充填材とを、無機充填材（ｂ１）、（ｂ２）、及び（ｂ３）の合計１００質量％に対して、（ｂ１）：（ｂ２）：（ｂ３）＝６０～７５：７～１５：１５～３０となる割合で含む、
不飽和ポリエステル樹脂組成物。
［態様２］
前記（ｂ）無機充填材の含有量は、前記（ａ）不飽和ポリエステル樹脂１００質量部に対して３５０～４５０質量部である、態様１に記載の不飽和ポリエステル樹脂組成物。
［態様３］
前記（ｂ）無機充填材は、炭酸カルシウムを含む態様１又は２のいずれかに記載の不飽和ポリエステル樹脂組成物。
［態様４］
前記（ｅ）繊維強化材の含有量は、（ａ）不飽和ポリエステル樹脂１００質量部に対して７０～１２０質量部である、態様１～３のいずれか一態様に記載の不飽和ポリエステル樹脂組成物。
［態様５］
態様１～４のいずれか一態様に記載の不飽和ポリエステル樹脂組成物の硬化物を含む成形体。 That is, the present invention includes the following aspects.
[Aspect 1]
An unsaturated polyester resin composition containing (a) an unsaturated polyester resin, (b) an inorganic filler, (c) a metal soap, (d) a low shrinkage agent, (e) a fiber reinforcing material, and (f) a curing agent. There,
The content of the (b) inorganic filler is 250 to 600 parts by mass with respect to 100 parts by mass of the (a) unsaturated polyester resin.
The (b) inorganic filler includes (b1) an inorganic filler having an average particle diameter of 0.5 to 5.0 μm, and (b2) an inorganic filler having an average particle diameter of 6.0 to 50.0 μm. b3) With respect to the total 100% by mass of the inorganic fillers (b1), (b2), and (b3) with an inorganic filler having an average particle diameter of 70.0 μm or more, (b1) :( b2) :( b3) = 60 to 75: 7 to 15: 15 to 30.
Unsaturated polyester resin composition.
[Aspect 2]
The unsaturated polyester resin composition according to embodiment 1, wherein the content of the (b) inorganic filler is 350 to 450 parts by mass with respect to 100 parts by mass of the (a) unsaturated polyester resin.
[Aspect 3]
The unsaturated polyester resin composition according to any one of aspects 1 or 2, wherein the inorganic filler (b) contains calcium carbonate.
[Aspect 4]
The unsaturated polyester resin composition according to any one of aspects 1 to 3, wherein the content of the (e) fiber reinforcing material is 70 to 120 parts by mass with respect to 100 parts by mass of the (a) unsaturated polyester resin. thing.
[Aspect 5]
A molded product containing a cured product of the unsaturated polyester resin composition according to any one of aspects 1 to 4.
本発明によれば、成形時の樹脂流動性が良好であるとともに、成形品外観、寸法精度、及び強度物性に優れ、バリが低減された成形体を与えることのできる、不飽和ポリエステル樹脂組成物を提供することができる。また、上記不飽和ポリエステル樹脂組成物を硬化させることにより、成形品外観、寸法精度、及び強度物性に優れ、バリが低減された成形体を提供することができる。
According to the present invention, an unsaturated polyester resin composition which has good resin fluidity at the time of molding, is excellent in appearance, dimensional accuracy, and strength physical properties of a molded product, and can give a molded product with reduced burrs. Can be provided. Further, by curing the unsaturated polyester resin composition, it is possible to provide a molded product having excellent appearance, dimensional accuracy and strength physical characteristics of the molded product and having reduced burrs.
以下、本発明の実施形態について詳細に説明する。ただし、本発明は、以下に示す実施形態に限定されるものではない。
Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments shown below.
本開示において、「エチレン性不飽和結合」とは、芳香環を形成する炭素原子を除く炭素原子間で形成される二重結合を意味する。
In the present disclosure, the "ethylenically unsaturated bond" means a double bond formed between carbon atoms other than the carbon atom forming the aromatic ring.
＜不飽和ポリエステル樹脂組成物＞
本発明の一実施態様は、（ａ）不飽和ポリエステル樹脂、（ｂ）無機充填材、（ｃ）金属石鹸、（ｄ）低収縮剤、（ｅ）繊維強化材、及び（ｆ）硬化剤を含む不飽和ポリエステル樹脂組成物である。以下、各成分について説明する。 <Unsaturated polyester resin composition>
In one embodiment of the present invention, (a) unsaturated polyester resin, (b) inorganic filler, (c) metal soap, (d) low shrinkage agent, (e) fiber reinforcing material, and (f) curing agent are used. It is an unsaturated polyester resin composition containing. Hereinafter, each component will be described.
本発明の一実施態様は、（ａ）不飽和ポリエステル樹脂、（ｂ）無機充填材、（ｃ）金属石鹸、（ｄ）低収縮剤、（ｅ）繊維強化材、及び（ｆ）硬化剤を含む不飽和ポリエステル樹脂組成物である。以下、各成分について説明する。 <Unsaturated polyester resin composition>
In one embodiment of the present invention, (a) unsaturated polyester resin, (b) inorganic filler, (c) metal soap, (d) low shrinkage agent, (e) fiber reinforcing material, and (f) curing agent are used. It is an unsaturated polyester resin composition containing. Hereinafter, each component will be described.
［（ａ）不飽和ポリエステル樹脂］
本開示において、（ａ）不飽和ポリエステル樹脂は、多価アルコールと、不飽和多塩基酸及び任意成分として飽和多塩基酸とを、エステル化反応させた縮合生成物（不飽和ポリエステル）を、架橋剤（「反応性希釈剤」ともいう。）に溶解した組成物を指す。不飽和多塩基酸とは、重合可能なエチレン性不飽和結合を有する多塩基酸であり、飽和多塩基酸とは、重合可能なエチレン性不飽和結合を有さない多塩基酸である。 [(A) Unsaturated polyester resin]
In the present disclosure, (a) the unsaturated polyester resin is a cross-linking of a condensation product (unsaturated polyester) obtained by esterifying a polyhydric alcohol with an unsaturated polybasic acid and a saturated polybasic acid as an optional component. Refers to a composition dissolved in an agent (also referred to as a "reactive diluent"). The unsaturated polybasic acid is a polybasic acid having a polymerizable ethylenically unsaturated bond, and the saturated polybasic acid is a polybasic acid having no polymerizable ethylenically unsaturated bond.
本開示において、（ａ）不飽和ポリエステル樹脂は、多価アルコールと、不飽和多塩基酸及び任意成分として飽和多塩基酸とを、エステル化反応させた縮合生成物（不飽和ポリエステル）を、架橋剤（「反応性希釈剤」ともいう。）に溶解した組成物を指す。不飽和多塩基酸とは、重合可能なエチレン性不飽和結合を有する多塩基酸であり、飽和多塩基酸とは、重合可能なエチレン性不飽和結合を有さない多塩基酸である。 [(A) Unsaturated polyester resin]
In the present disclosure, (a) the unsaturated polyester resin is a cross-linking of a condensation product (unsaturated polyester) obtained by esterifying a polyhydric alcohol with an unsaturated polybasic acid and a saturated polybasic acid as an optional component. Refers to a composition dissolved in an agent (also referred to as a "reactive diluent"). The unsaturated polybasic acid is a polybasic acid having a polymerizable ethylenically unsaturated bond, and the saturated polybasic acid is a polybasic acid having no polymerizable ethylenically unsaturated bond.
このような不飽和ポリエステル樹脂は、本発明の技術分野において一般に公知であり、例えば、「ポリエステル樹脂ハンドブック」（日刊工業新聞社、１９８８年発行）や「塗料用語辞典」（色材協会編、１９９３年発行）等に記載されている。
Such unsaturated polyester resins are generally known in the technical field of the present invention, and are, for example, "Polyester Resin Handbook" (Nikkan Kogyo Shimbun, published in 1988) and "Paint Glossary" (edited by Japan Society of Color Material, 1993). (Issued annually), etc.
不飽和ポリエステルの原料となる多価アルコールとしては、特に限定されず、本発明の技術分野において公知のものを用いることができる。多価アルコールの例としては、エチレングリコール、プロピレングリコール、ブタンジオール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、ペンタンジオール、ヘキサンジオール、ネオペンタンジオール、水素化ビスフェノールＡ、ビスフェノールＡ、グリセリンが挙げられる。多価アルコールは、単独で又は複数種を組み合わせて用いることができる。
The polyhydric alcohol used as a raw material for unsaturated polyester is not particularly limited, and those known in the technical field of the present invention can be used. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, pentanediol, hexanediol, neopentanediol, hydrogenated bisphenol A, bisphenol A and glycerin. The polyhydric alcohol can be used alone or in combination of two or more.
これらの中では、耐熱性、機械的強度、及び成形時の樹脂流動性に優れる観点から、プロピレングリコール、ネオペンタンジオール、ビスフェノールＡ、及び水素化ビスフェノールＡからなる群より選ばれる少なくとも１種が好ましい。
Among these, at least one selected from the group consisting of propylene glycol, neopentanediol, bisphenol A, and hydrogenated bisphenol A is preferable from the viewpoint of excellent heat resistance, mechanical strength, and resin fluidity during molding. ..
不飽和ポリエステルの原料となる不飽和多塩基酸としては、特に限定されず、本発明の技術分野において公知のものを用いることができる。不飽和多塩基酸の例としては、無水マレイン酸、フマル酸、シトラコン酸、イタコン酸、ヘット酸が挙げられる。不飽和多塩基酸は、単独で又は複数種を組み合わせて用いることができる。
The unsaturated polybasic acid used as a raw material for the unsaturated polyester is not particularly limited, and those known in the technical field of the present invention can be used. Examples of unsaturated polybasic acids include maleic anhydride, fumaric acid, citraconic acid, itaconic acid and het acid. The unsaturated polybasic acid can be used alone or in combination of two or more.
これらの中では、耐熱性、機械的強度、及び成形時の樹脂流動性等に優れる観点から、無水マレイン酸又はフマル酸が好ましい。
Among these, maleic anhydride or fumaric acid is preferable from the viewpoint of excellent heat resistance, mechanical strength, resin fluidity during molding, and the like.
不飽和ポリエステルの任意の原料となる飽和多塩基酸としては、特に限定されず、公知のものを用いることができる。飽和多塩基酸の例としては、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、セバシン酸、テトラクロロ無水フタル酸、テトラブロモ無水フタル酸が挙げられる。飽和多塩基酸は、単独で又は複数種を組み合わせて用いることができる。
The saturated polybasic acid used as an arbitrary raw material for unsaturated polyester is not particularly limited, and known ones can be used. Examples of saturated polybasic acids include phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, tetrachlorophthalic anhydride and tetrabromophthalic anhydride. The saturated polybasic acid can be used alone or in combination of two or more.
不飽和ポリエステルは、上記のような原料を用いて公知の方法で合成することができる。不飽和ポリエステルの合成における各種条件は、使用する原料やその量に応じて適宜設定することができる。一般的に、窒素ガス等の不活性ガス気流中にて、１４０～２３０℃の温度で、加圧又は減圧下でエステル化させる方法が挙げられる。エステル化反応では、必要に応じてエステル化触媒を使用することができる。エステル化触媒の例としては、酢酸マンガン、ジブチル錫オキサイド、シュウ酸第一錫、酢酸亜鉛、酢酸コバルト等の公知の触媒が挙げられる。エステル化触媒は、単独で又は複数種を組み合わせて用いることができる。
Unsaturated polyester can be synthesized by a known method using the above raw materials. Various conditions in the synthesis of unsaturated polyester can be appropriately set according to the raw materials used and the amount thereof. Generally, a method of esterifying under pressure or reduced pressure at a temperature of 140 to 230 ° C. in an inert gas stream such as nitrogen gas can be mentioned. In the esterification reaction, an esterification catalyst can be used if necessary. Examples of the esterification catalyst include known catalysts such as manganese acetate, dibutyltin oxide, stannous oxalate, zinc acetate and cobalt acetate. The esterification catalyst can be used alone or in combination of two or more.
不飽和ポリエステルの重量平均分子量（ＭＷ）は、特に限定されない。好ましくは３，０００～２５，０００であり、より好ましくは５，０００～２０，０００であり、さらに好ましくは７，０００～１８，０００である。なお、本開示において「重量平均分子量」とは、ゲルパーミエーションクロマトグラフィー（Ｓｈｏｄｅｘ（登録商標）ＧＰＣ－１０１、昭和電工株式会社）を用いて、常温（２３℃）にて下記条件で測定し、標準ポリスチレン検量線を用いて求めた値のことを意味する。
カラム：ＬＦ－８０４（昭和電工株式会社）
カラム温度：４０℃
試料：不飽和ポリエステルの０．２質量％テトラヒドロフラン溶液
流量：１ｍＬ／分
溶離液：テトラヒドロフラン
検出器：ＲＩ－７１Ｓ The weight average molecular weight (MW) of the unsaturated polyester is not particularly limited. It is preferably 3,000 to 25,000, more preferably 5,000 to 20,000, and even more preferably 7,000 to 18,000. In the present disclosure, the "weight average molecular weight" is measured by gel permeation chromatography (Polystyrene (registered trademark) GPC-101, Showa Denko KK) at room temperature (23 ° C.) under the following conditions. It means a value obtained using a standard polystyrene calibration curve.
Column: LF-804 (Showa Denko KK)
Column temperature: 40 ° C
Sample: 0.2 mass% tetrahydrofuran solution of unsaturated polyester Flow rate: 1 mL / min Eluent: Tetrahydrofuran Detector: RI-71S
カラム：ＬＦ－８０４（昭和電工株式会社）
カラム温度：４０℃
試料：不飽和ポリエステルの０．２質量％テトラヒドロフラン溶液
流量：１ｍＬ／分
溶離液：テトラヒドロフラン
検出器：ＲＩ－７１Ｓ The weight average molecular weight (MW) of the unsaturated polyester is not particularly limited. It is preferably 3,000 to 25,000, more preferably 5,000 to 20,000, and even more preferably 7,000 to 18,000. In the present disclosure, the "weight average molecular weight" is measured by gel permeation chromatography (Polystyrene (registered trademark) GPC-101, Showa Denko KK) at room temperature (23 ° C.) under the following conditions. It means a value obtained using a standard polystyrene calibration curve.
Column: LF-804 (Showa Denko KK)
Column temperature: 40 ° C
Sample: 0.2 mass% tetrahydrofuran solution of unsaturated polyester Flow rate: 1 mL / min Eluent: Tetrahydrofuran Detector: RI-71S
不飽和ポリエステルを溶解する架橋剤（反応性希釈剤）としては、不飽和ポリエステルと重合可能なエチレン性不飽和結合を有しているものであれば特に限定されず、本発明の技術分野において公知のものを用いることができる。架橋剤の例としては、スチレンモノマー、ジアリルフタレートモノマー、ジアリルフタレートプレポリマー、メタクリル酸メチル、トリアリルイソシアヌレートが挙げられる。これらは、単独で又は複数種を組み合わせて用いることができる。
The cross-linking agent (reactive diluent) that dissolves the unsaturated polyester is not particularly limited as long as it has a polymerizable ethylenically unsaturated bond with the unsaturated polyester, and is known in the technical field of the present invention. Can be used. Examples of the cross-linking agent include styrene monomer, diallyl phthalate monomer, diallyl phthalate prepolymer, methyl methacrylate and triallyl isocyanurate. These can be used alone or in combination of two or more.
（ａ）不飽和ポリエステル樹脂における架橋剤（反応性希釈剤）の含有量は、特に限定されるものではない。（ａ）不飽和ポリエステル樹脂における架橋剤（反応性希釈剤）の含有量は、作業性、重合性、成形体の収縮性、及び量調整の自由度の観点からは、不飽和ポリエステル及び架橋剤の合計に対して、好ましくは２５～７０質量％、より好ましくは３０～６８質量％、さらに好ましくは３５～６５質量％である。
(A) The content of the cross-linking agent (reactive diluent) in the unsaturated polyester resin is not particularly limited. (A) The content of the cross-linking agent (reactive diluent) in the unsaturated polyester resin is the unsaturated polyester and the cross-linking agent from the viewpoint of workability, polymerizability, shrinkage of the molded product, and degree of freedom in adjusting the amount. It is preferably 25 to 70% by mass, more preferably 30 to 68% by mass, and further preferably 35 to 65% by mass with respect to the total of.
（ａ）不飽和ポリエステル樹脂は、必要に応じて、ハイドロキノン等の重合禁止剤を含んでいてもよい。
(A) The unsaturated polyester resin may contain a polymerization inhibitor such as hydroquinone, if necessary.
［（ｂ）無機充填材］
一実施態様の不飽和ポリエステル樹脂組成物は、無機充填材の含有量を特定の範囲とし、当該無機充填材として、３種類の平均粒子径を有するものを特定の比率で用いる。 [(B) Inorganic filler]
The unsaturated polyester resin composition of one embodiment has a specific range of the content of the inorganic filler, and the inorganic filler having three kinds of average particle diameters is used at a specific ratio.
一実施態様の不飽和ポリエステル樹脂組成物は、無機充填材の含有量を特定の範囲とし、当該無機充填材として、３種類の平均粒子径を有するものを特定の比率で用いる。 [(B) Inorganic filler]
The unsaturated polyester resin composition of one embodiment has a specific range of the content of the inorganic filler, and the inorganic filler having three kinds of average particle diameters is used at a specific ratio.
（ｂ）無機充填材の種類としては、特に限定されず、本発明の技術分野において公知のものを用いることができる。（ｂ）無機充填材の例としては、炭酸カルシウム、シリカ、アルミナ、水酸化アルミニウム、硫酸バリウム、ワラストナイト、クレー、タルク、マイカ、石膏、無水ケイ酸、ガラス粉末が挙げられる。これらは、単独で又は複数種を組み合わせて用いることができる。中では、得られる成形品の表面平滑性、コスト低減、入手容易性の観点から、少なくとも炭酸カルシウムを用いることが好ましい。
(B) The type of the inorganic filler is not particularly limited, and those known in the technical field of the present invention can be used. (B) Examples of the inorganic filler include calcium carbonate, silica, alumina, aluminum hydroxide, barium sulfate, wallastnite, clay, talc, mica, gypsum, silicic acid anhydride, and glass powder. These can be used alone or in combination of two or more. Among them, it is preferable to use at least calcium carbonate from the viewpoint of surface smoothness, cost reduction, and availability of the obtained molded product.
（ｂ）無機充填材の形状としては、特に制限されるものではなく、例えば、略真球、楕円体、鱗片状、無定形が挙げられる。
(B) The shape of the inorganic filler is not particularly limited, and examples thereof include a substantially true sphere, an ellipsoid, a scaly shape, and an amorphous shape.
（ｂ）無機充填材の真比重は、特に限定されるものではなく、好ましくは１～１０ｇ／ｃｍ３であり、より好ましくは１．５～８ｇ／ｃｍ３であり、さらに好ましくは２～５ｇ／ｃｍ３である。
(B) The true specific gravity of the inorganic filler is not particularly limited, and is preferably 1 to 10 g / cm 3 , more preferably 1.5 to 8 g / cm 3 , and even more preferably 2 to 5 g. / Cm 3 .
無機充填材の真比重が１ｇ／ｃｍ３以上であれば、得られる成形体の機械的特性がより良好となり、無機充填材の真比重が１０ｇ／ｃｍ３以下であれば、不飽和ポリエステル樹脂組成物の混練性がより良好となる。
When the true specific gravity of the inorganic filler is 1 g / cm 3 or more, the mechanical properties of the obtained molded product are better, and when the true specific gravity of the inorganic filler is 10 g / cm 3 or less, the unsaturated polyester resin composition is obtained. The kneadability of the product becomes better.
（ｂ）無機充填材の配合量は、（ａ）不飽和ポリエステル樹脂１００質量部に対して２５０～６００質量部であり、より好ましくは３００～５５０質量部であり、さらに好ましくは３５０～４５０質量部である。
(B) The blending amount of the inorganic filler is 250 to 600 parts by mass, more preferably 300 to 550 parts by mass, and further preferably 350 to 450 parts by mass with respect to 100 parts by mass of (a) unsaturated polyester resin. It is a department.
（ｂ）無機充填材の配合量が２５０質量部以上であれば、得られる成形体の機械的特性がより良好となる。また、（ｂ）無機充填材の配合量が６００質量部以下であれば、不飽和ポリエステル樹脂組成物中で（ｂ）無機充填材がより均一に分散するため、均質な成形体を製造することができる。
(B) When the blending amount of the inorganic filler is 250 parts by mass or more, the mechanical properties of the obtained molded product become better. Further, when (b) the blending amount of the inorganic filler is 600 parts by mass or less, (b) the inorganic filler is more uniformly dispersed in the unsaturated polyester resin composition, so that a homogeneous molded body is produced. Can be done.
（ｂ）無機充填材は、（ｂ１）平均粒子径が０．５～５．０μｍの無機充填材（以下、「（ｂ１）無機充填材」とも言う。）と、（ｂ２）平均粒子径が６．０～５０．０μｍの無機充填材（以下、「（ｂ２）無機充填材」とも言う。）と、（ｂ３）平均粒子径が７０．０μｍ以上の無機充填材（以下、「（ｂ３）無機充填材」とも言う。）と、の少なくとも３種を併用する。
The (b) inorganic filler has (b1) an inorganic filler having an average particle diameter of 0.5 to 5.0 μm (hereinafter, also referred to as “(b1) inorganic filler”) and (b2) an average particle diameter. An inorganic filler of 6.0 to 50.0 μm (hereinafter, also referred to as “(b2) inorganic filler”) and (b3) an inorganic filler having an average particle size of 70.0 μm or more (hereinafter, “(b3)). Also referred to as "inorganic filler") and at least three types are used in combination.
平均粒子径が異なる、（ｂ１）～（ｂ３）の少なくとも３種の無機充填材を併用することにより、成形時の不飽和ポリエステル樹脂組成物の流動性を良好なものとし、得られる成形体の外観、寸法精度、及び強度物性を優れたものとすることができ、且つ成形体のバリを低減することができる。
By using at least three kinds of inorganic fillers (b1) to (b3) having different average particle sizes in combination, the fluidity of the unsaturated polyester resin composition at the time of molding is improved, and the obtained molded product can be obtained. The appearance, dimensional accuracy, and physical characteristics of strength can be improved, and burrs of the molded product can be reduced.
本開示において（ｂ）無機充填材の「平均粒子径」とは、空気透過法によって求めた比表面積から、以下の式に従って求めた粒子径を意味する。
平均粒子径［μｍ］＝（６×１００００）／（真比重［ｇ／ｃｍ３］×比表面積［ｃｍ２／ｇ］） In the present disclosure, (b) the "average particle size" of the inorganic filler means the particle size obtained from the specific surface area obtained by the air permeation method according to the following formula.
Average particle diameter [μm] = (6 × 10000) / (true specific density [g / cm 3 ] × specific surface area [cm 2 / g])
平均粒子径［μｍ］＝（６×１００００）／（真比重［ｇ／ｃｍ３］×比表面積［ｃｍ２／ｇ］） In the present disclosure, (b) the "average particle size" of the inorganic filler means the particle size obtained from the specific surface area obtained by the air permeation method according to the following formula.
Average particle diameter [μm] = (6 × 10000) / (true specific density [g / cm 3 ] × specific surface area [cm 2 / g])
（ｂ１）無機充填材の平均粒子径は、０．７μｍ以上が好ましく、１．０μｍ以上がより好ましい。（ｂ１）無機充填材の平均粒子径は、４．０μｍ以下が好ましく、３．０μｍ以下がより好ましい。（ｂ１）無機充填材を用いることにより、外観や強度物性に優れた成形体を得ることができる。
(B1) The average particle size of the inorganic filler is preferably 0.7 μm or more, more preferably 1.0 μm or more. (B1) The average particle size of the inorganic filler is preferably 4.0 μm or less, more preferably 3.0 μm or less. (B1) By using the inorganic filler, it is possible to obtain a molded body having excellent appearance and strength and physical characteristics.
（ｂ２）無機充填材の平均粒子径は、６．５μｍ以上が好ましく、７．０μｍ以上がより好ましい。（ｂ２）無機充填材の平均粒子径は、４０．０μｍ以下が好ましく、３０．０μｍ以下がより好ましい。（ｂ２）無機充填材を用いることにより、優れた外観や強度物性と、バリの低減とが両立した成形体を得ることができる。
(B2) The average particle size of the inorganic filler is preferably 6.5 μm or more, more preferably 7.0 μm or more. (B2) The average particle size of the inorganic filler is preferably 40.0 μm or less, more preferably 30.0 μm or less. (B2) By using the inorganic filler, it is possible to obtain a molded product having both excellent appearance and strength physical properties and reduction of burrs.
（ｂ３）無機充填材の平均粒子径は、１００μｍ以上が好ましく、２００μｍ以上がより好ましい。（ｂ３）無機充填材の平均粒子径は、５００μｍ以下が好ましく、４００μｍ以下がより好ましく、３６０μｍ以下がさらに好ましい。（ｂ３）無機充填材を用いることにより、バリが低減した成形体を得ることができる。
(B3) The average particle size of the inorganic filler is preferably 100 μm or more, more preferably 200 μm or more. (B3) The average particle size of the inorganic filler is preferably 500 μm or less, more preferably 400 μm or less, still more preferably 360 μm or less. (B3) By using the inorganic filler, a molded product with reduced burrs can be obtained.
（ｂ１）～（ｂ３）無機充填材は、無機充填材（ｂ１）、（ｂ２）、及び（ｂ３）の合計１００質量％に対して、（ｂ１）：（ｂ２）：（ｂ３）が、６０～７５：７～１５：１５～３０の割合で含まれる。得られる成形体のバリをさらに低減するとともに、優れた表面平滑性及び機械的強度の面からは、好ましくは６０～７０：１０～１５：２０～２５の割合で含まれる。
In the inorganic fillers (b1) to (b3), (b1) :( b2) :( b3) is 60 with respect to a total of 100% by mass of the inorganic fillers (b1), (b2), and (b3). It is contained in a ratio of ~ 75: 7 ~ 15: 15 ~ 30. In addition to further reducing burrs in the obtained molded product, it is preferably contained in a ratio of 60 to 70:10 to 15:20 to 25 in terms of excellent surface smoothness and mechanical strength.
（ｂ１）～（ｂ３）無機充填材の質量比を上記の範囲とすることにより、得られる成形体の優れた外観や強度物性と、バリの低減とを両立させることができ、質量比が上記範囲外である場合には、成形体の外観、強度物性、及びバリの低減のいずれかの特性が損なわれる。
By setting the mass ratio of the inorganic fillers (b1) to (b3) in the above range, it is possible to achieve both the excellent appearance and strength physical properties of the obtained molded product and the reduction of burrs, and the mass ratio is the above. If it is out of the range, any of the properties of the appearance, strength and physical properties of the molded body, and the reduction of burrs are impaired.
［（ｃ）金属石鹸］
（ｃ）金属石鹸は、本発明の技術分野において、一般に離型剤として用いられている成分である。（ｃ）金属石鹸としては、特に限定されず、本発明の技術分野において公知のものを用いることができる。（ｃ）金属石鹸の例としては、ステアリン酸カルシウム、ステアリン酸亜鉛、ステアリン酸アルミニウム、ステアリン酸マグネシウムが挙げられる。（ｃ）金属石鹸は、単独で又は複数種を組み合わせて用いることができる。 [(C) Metal soap]
(C) Metal soap is a component generally used as a mold release agent in the technical field of the present invention. (C) The metal soap is not particularly limited, and a soap known in the technical field of the present invention can be used. (C) Examples of the metal soap include calcium stearate, zinc stearate, aluminum stearate, and magnesium stearate. (C) The metal soap can be used alone or in combination of two or more.
（ｃ）金属石鹸は、本発明の技術分野において、一般に離型剤として用いられている成分である。（ｃ）金属石鹸としては、特に限定されず、本発明の技術分野において公知のものを用いることができる。（ｃ）金属石鹸の例としては、ステアリン酸カルシウム、ステアリン酸亜鉛、ステアリン酸アルミニウム、ステアリン酸マグネシウムが挙げられる。（ｃ）金属石鹸は、単独で又は複数種を組み合わせて用いることができる。 [(C) Metal soap]
(C) Metal soap is a component generally used as a mold release agent in the technical field of the present invention. (C) The metal soap is not particularly limited, and a soap known in the technical field of the present invention can be used. (C) Examples of the metal soap include calcium stearate, zinc stearate, aluminum stearate, and magnesium stearate. (C) The metal soap can be used alone or in combination of two or more.
（ｃ）金属石鹸の配合量は、特に限定されるものではなく、（ａ）不飽和ポリエステル樹脂１００質量部に対して、１～１５質量部であることが好ましく、２～１０質量部であることがより好ましい。
The amount of the (c) metal soap is not particularly limited, and is preferably 1 to 15 parts by mass, preferably 2 to 10 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin (a). Is more preferable.
（ｃ）金属石鹸の配合量が１質量部以上であれば、得られる成形体の離型性がより良好となる。一方、（ｃ）金属石鹸の配合量が１５質量部以下であれば、成形体の表面に（ｃ）金属石鹸がブリードすることを防ぐことができるため、所望のフォギング性及びアンダーコート剤の塗装性を満足させる成形体を得ることができる。
(C) When the blending amount of the metal soap is 1 part by mass or more, the releasability of the obtained molded product becomes better. On the other hand, when (c) the blending amount of the metal soap is 15 parts by mass or less, (c) the metal soap can be prevented from bleeding on the surface of the molded product, so that the desired fogging property and coating of the undercoat agent can be applied. It is possible to obtain a molded product that satisfies the properties.
［（ｄ）低収縮剤］
（ｄ）低収縮剤としては、特に限定されず、本発明の技術分野において公知のものを用いることができる。低収縮剤の例としては、ポリスチレン、ポリメチルメタクリレート、ポリ酢酸ビニル、飽和ポリエステル、スチレン－ブタジエン系ゴム等の低収縮剤として一般に使用されている熱可塑性ポリマーが挙げられる。（ｄ）低収縮剤は、単独で又は２種以上を組み合わせて用いることができる。 [(D) Hypo-shrinkant]
(D) The low shrinkage agent is not particularly limited, and those known in the technical field of the present invention can be used. Examples of the low shrinkage agent include thermoplastic polymers generally used as a low shrinkage agent such as polystyrene, polymethylmethacrylate, polyvinyl acetate, saturated polyester, and styrene-butadiene rubber. (D) The low shrinkage agent can be used alone or in combination of two or more.
（ｄ）低収縮剤としては、特に限定されず、本発明の技術分野において公知のものを用いることができる。低収縮剤の例としては、ポリスチレン、ポリメチルメタクリレート、ポリ酢酸ビニル、飽和ポリエステル、スチレン－ブタジエン系ゴム等の低収縮剤として一般に使用されている熱可塑性ポリマーが挙げられる。（ｄ）低収縮剤は、単独で又は２種以上を組み合わせて用いることができる。 [(D) Hypo-shrinkant]
(D) The low shrinkage agent is not particularly limited, and those known in the technical field of the present invention can be used. Examples of the low shrinkage agent include thermoplastic polymers generally used as a low shrinkage agent such as polystyrene, polymethylmethacrylate, polyvinyl acetate, saturated polyester, and styrene-butadiene rubber. (D) The low shrinkage agent can be used alone or in combination of two or more.
（ｄ）低収縮剤の含有量は、（ａ）不飽和ポリエステル樹脂１００質量部に対して、１０～４０質量部であることが好ましく、２０～３５質量部であることがより好ましい。（ｄ）低収縮剤の配合量が１０質量部以上であれば、成形体の収縮率が小さくなり、所望の寸法精度を得ることができる。一方、（ｄ）低収縮剤の配合量が４０質量部以下であれば、成形体の機械的特性がより良好となる。
The content of (d) the low shrinkage agent is preferably 10 to 40 parts by mass, more preferably 20 to 35 parts by mass with respect to 100 parts by mass of (a) unsaturated polyester resin. (D) When the blending amount of the low shrinkage agent is 10 parts by mass or more, the shrinkage rate of the molded product becomes small, and desired dimensional accuracy can be obtained. On the other hand, when (d) the blending amount of the low shrinkage agent is 40 parts by mass or less, the mechanical properties of the molded product become better.
［（ｅ）繊維強化材］
（ｅ）繊維強化材は、アスペクト比が３以上である材料である。アスペクト比は、日本工業規格ＪＩＳ Ｚ ８９００－１：２００８「粒子径測定装置検定用粒子」に記載されている顕微鏡法によって、測定することができる。 [(E) Fiber Reinforcement Material]
(E) The fiber reinforcing material is a material having an aspect ratio of 3 or more. The aspect ratio can be measured by the microscopic method described in Japanese Industrial Standards JIS Z 890-1: 2008 "Particles for Verification of Particle Size Measuring Device".
（ｅ）繊維強化材は、アスペクト比が３以上である材料である。アスペクト比は、日本工業規格ＪＩＳ Ｚ ８９００－１：２００８「粒子径測定装置検定用粒子」に記載されている顕微鏡法によって、測定することができる。 [(E) Fiber Reinforcement Material]
(E) The fiber reinforcing material is a material having an aspect ratio of 3 or more. The aspect ratio can be measured by the microscopic method described in Japanese Industrial Standards JIS Z 890-1: 2008 "Particles for Verification of Particle Size Measuring Device".
（ｅ）繊維強化材としては、特に限定されず、本発明の技術分野において公知のものを用いることができる。（ｅ）繊維強化材の例としては、ガラス繊維、パルプ、ポリエチレンテレフタレート繊維、ビニロン繊維、カーボン繊維、アラミド繊維、ワラストナイト等の様々な有機繊維及び無機繊維を挙げることができる。中では、ガラス繊維が好ましく、より好ましくは、繊維長１．５～２５ｍｍ程度に切断したチョップドストランドガラスである。
(E) The fiber reinforcing material is not particularly limited, and a material known in the technical field of the present invention can be used. Examples of the (e) fiber reinforcing material include various organic fibers such as glass fiber, pulp, polyethylene terephthalate fiber, vinylon fiber, carbon fiber, aramid fiber, and wallastnite, and inorganic fiber. Among them, glass fiber is preferable, and chopped strand glass cut to a fiber length of about 1.5 to 25 mm is more preferable.
（ｅ）繊維強化材の含有量は、（ａ）不飽和ポリエステル樹脂１００質量部に対して、７０～１２０質量部であることが好ましく、７５～１００質量部であることがより好ましい。（ｅ）繊維強化材の配合量が７０質量部以上であれば、成形体の機械的特性がより良好となる。一方、（ｅ）繊維強化材の配合量が１２０質量部以下であれば、不飽和ポリエステル樹脂組成物中で（ｅ）繊維強化材がより均一に分散し、均質な成形体を製造することができる。
The content of (e) the fiber reinforcing material is preferably 70 to 120 parts by mass, more preferably 75 to 100 parts by mass with respect to 100 parts by mass of (a) unsaturated polyester resin. (E) When the blending amount of the fiber reinforcing material is 70 parts by mass or more, the mechanical properties of the molded product become better. On the other hand, when the blending amount of the (e) fiber reinforcing material is 120 parts by mass or less, the (e) fiber reinforcing material is more uniformly dispersed in the unsaturated polyester resin composition, and a uniform molded body can be produced. can.
［（ｆ）硬化剤］
（ｆ）硬化剤としては、エチレン性不飽和結合を重合できるラジカル重合開始剤であれば、特に限定されず、本発明の技術分野において公知のものを用いることができる。（ｆ）硬化剤の例としては、ｔ－ブチルパーオキシオクトエート、ベンゾイルパーオキサイド、１，１－ジ－ｔ－ブチルパーオキシ－３，３，５－トリメチルシクロヘキサン、ｔ－ブチルパーオキシイソプロピルカーボネート、ｔ－ブチルパーオキシベンゾエート、ジクミルパーオキサイド、ジ－ｔ－ブチルパーオキサイド等の有機過酸化物が挙げられる。（ｆ）硬化剤は、単独で又は２種以上を組み合わせて用いることができる。 [(F) Curing agent]
The (f) curing agent is not particularly limited as long as it is a radical polymerization initiator capable of polymerizing an ethylenically unsaturated bond, and those known in the technical field of the present invention can be used. (F) Examples of the curing agent include t-butylperoxyoctate, benzoyl peroxide, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, and t-butylperoxyisopropylcarbonate. , T-butylperoxybenzoate, dicumyl peroxide, di-t-butyl peroxide and other organic peroxides. (F) The curing agent can be used alone or in combination of two or more.
（ｆ）硬化剤としては、エチレン性不飽和結合を重合できるラジカル重合開始剤であれば、特に限定されず、本発明の技術分野において公知のものを用いることができる。（ｆ）硬化剤の例としては、ｔ－ブチルパーオキシオクトエート、ベンゾイルパーオキサイド、１，１－ジ－ｔ－ブチルパーオキシ－３，３，５－トリメチルシクロヘキサン、ｔ－ブチルパーオキシイソプロピルカーボネート、ｔ－ブチルパーオキシベンゾエート、ジクミルパーオキサイド、ジ－ｔ－ブチルパーオキサイド等の有機過酸化物が挙げられる。（ｆ）硬化剤は、単独で又は２種以上を組み合わせて用いることができる。 [(F) Curing agent]
The (f) curing agent is not particularly limited as long as it is a radical polymerization initiator capable of polymerizing an ethylenically unsaturated bond, and those known in the technical field of the present invention can be used. (F) Examples of the curing agent include t-butylperoxyoctate, benzoyl peroxide, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, and t-butylperoxyisopropylcarbonate. , T-butylperoxybenzoate, dicumyl peroxide, di-t-butyl peroxide and other organic peroxides. (F) The curing agent can be used alone or in combination of two or more.
（ｆ）硬化剤の含有量は、使用する原料に応じて適宜設定すればよく、特に限定されない。（ｆ）硬化剤の含有量は、（ａ）不飽和ポリエステル樹脂１００質量部に対して、好ましくは１～１０質量部であり、より好ましくは１～８質量部であり、さらに好ましくは１～５質量部である。
(F) The content of the curing agent may be appropriately set according to the raw material used, and is not particularly limited. The content of (f) the curing agent is preferably 1 to 10 parts by mass, more preferably 1 to 8 parts by mass, and further preferably 1 to 1 to 100 parts by mass with respect to 100 parts by mass of (a) unsaturated polyester resin. 5 parts by mass.
［その他の成分］
本発明の不飽和ポリエステル樹脂組成物は、上記の成分に加えて、増粘剤、顔料、減粘剤等の本発明の技術分野において公知の成分を、本発明の効果を阻害しない範囲において含むことができる。 [Other ingredients]
The unsaturated polyester resin composition of the present invention contains, in addition to the above-mentioned components, components known in the technical field of the present invention such as a thickener, a pigment, and a thickener, as long as the effects of the present invention are not impaired. be able to.
本発明の不飽和ポリエステル樹脂組成物は、上記の成分に加えて、増粘剤、顔料、減粘剤等の本発明の技術分野において公知の成分を、本発明の効果を阻害しない範囲において含むことができる。 [Other ingredients]
The unsaturated polyester resin composition of the present invention contains, in addition to the above-mentioned components, components known in the technical field of the present invention such as a thickener, a pigment, and a thickener, as long as the effects of the present invention are not impaired. be able to.
増粘剤としては、特に限定されないが、例えば、酸化マグネシウム、水酸化マグネシウム、水酸化カルシウム、酸化カルシウム等の（ｂ）無機充填材以外の金属酸化物、及びイソシアネート化合物が挙げられる。増粘剤は、単独で又は２種以上を組み合わせて用いることができる。
The thickener is not particularly limited, and examples thereof include (b) metal oxides other than the inorganic filler such as magnesium oxide, magnesium hydroxide, calcium hydroxide, and calcium oxide, and isocyanate compounds. The thickener can be used alone or in combination of two or more.
［不飽和ポリエステル樹脂組成物の製造方法］
不飽和ポリエステル樹脂組成物は、本発明の技術分野において通常行われる方法、例えば、ニーダー等を用いて各成分を混練することによって製造することができる。 [Manufacturing method of unsaturated polyester resin composition]
The unsaturated polyester resin composition can be produced by kneading each component using a method usually used in the technical field of the present invention, for example, a kneader or the like.
不飽和ポリエステル樹脂組成物は、本発明の技術分野において通常行われる方法、例えば、ニーダー等を用いて各成分を混練することによって製造することができる。 [Manufacturing method of unsaturated polyester resin composition]
The unsaturated polyester resin composition can be produced by kneading each component using a method usually used in the technical field of the present invention, for example, a kneader or the like.
［不飽和ポリエステル樹脂組成物の成形体の製造方法］
不飽和ポリエステル樹脂組成物を、所望の形状に成形して硬化することによって、成形体を製造することができる。成形及び硬化方法としては、特に限定されず、本発明の技術分野において通常行われる方法、例えば、圧縮成形、トランスファー成形、射出成形を挙げることができる。 [Method for manufacturing a molded product of unsaturated polyester resin composition]
A molded product can be produced by molding an unsaturated polyester resin composition into a desired shape and curing it. The molding and curing methods are not particularly limited, and examples thereof include methods usually performed in the technical field of the present invention, such as compression molding, transfer molding, and injection molding.
不飽和ポリエステル樹脂組成物を、所望の形状に成形して硬化することによって、成形体を製造することができる。成形及び硬化方法としては、特に限定されず、本発明の技術分野において通常行われる方法、例えば、圧縮成形、トランスファー成形、射出成形を挙げることができる。 [Method for manufacturing a molded product of unsaturated polyester resin composition]
A molded product can be produced by molding an unsaturated polyester resin composition into a desired shape and curing it. The molding and curing methods are not particularly limited, and examples thereof include methods usually performed in the technical field of the present invention, such as compression molding, transfer molding, and injection molding.
以下、実施例及び比較例によって本発明を詳細に説明するが、これらによって本発明が限定されるものではない。
Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
＜（ａ）不飽和ポリエステル樹脂の調製＞
温度計、撹拌機、不活性ガス導入口、及び還流冷却器を備えた４つ口フラスコに、無水マレイン酸０．９３ｋｇ（９．５モル）と、無水フタル酸０．０７ｋｇ（０．５モル）と、プロピレングリコール０．７６ｋｇ（１０モル）とを仕込んだ。続いて、窒素ガス気流下で加熱撹拌しながら２００℃まで昇温してエステル化反応を行うことで、不飽和ポリエステルを得た。得られた不飽和ポリエステルは、不飽和度９５モル％、重量平均分子量８，０００であった。続いて、得られた不飽和ポリエステルにスチレンモノマーを、不飽和ポリエステルとスチレンモノマーの合計に対して３０質量％となるように添加して、（ａ）不飽和ポリエステル樹脂を得た。 <(A) Preparation of unsaturated polyester resin>
0.93 kg (9.5 mol) of maleic anhydride and 0.07 kg (0.5 mol) of phthalic anhydride in a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. ) And 0.76 kg (10 mol) of propylene glycol were charged. Subsequently, the temperature was raised to 200 ° C. while heating and stirring under a nitrogen gas stream, and an esterification reaction was carried out to obtain an unsaturated polyester. The obtained unsaturated polyester had an unsaturated degree of 95 mol% and a weight average molecular weight of 8,000. Subsequently, a styrene monomer was added to the obtained unsaturated polyester so as to be 30% by mass based on the total of the unsaturated polyester and the styrene monomer to obtain (a) an unsaturated polyester resin.
温度計、撹拌機、不活性ガス導入口、及び還流冷却器を備えた４つ口フラスコに、無水マレイン酸０．９３ｋｇ（９．５モル）と、無水フタル酸０．０７ｋｇ（０．５モル）と、プロピレングリコール０．７６ｋｇ（１０モル）とを仕込んだ。続いて、窒素ガス気流下で加熱撹拌しながら２００℃まで昇温してエステル化反応を行うことで、不飽和ポリエステルを得た。得られた不飽和ポリエステルは、不飽和度９５モル％、重量平均分子量８，０００であった。続いて、得られた不飽和ポリエステルにスチレンモノマーを、不飽和ポリエステルとスチレンモノマーの合計に対して３０質量％となるように添加して、（ａ）不飽和ポリエステル樹脂を得た。 <(A) Preparation of unsaturated polyester resin>
0.93 kg (9.5 mol) of maleic anhydride and 0.07 kg (0.5 mol) of phthalic anhydride in a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser. ) And 0.76 kg (10 mol) of propylene glycol were charged. Subsequently, the temperature was raised to 200 ° C. while heating and stirring under a nitrogen gas stream, and an esterification reaction was carried out to obtain an unsaturated polyester. The obtained unsaturated polyester had an unsaturated degree of 95 mol% and a weight average molecular weight of 8,000. Subsequently, a styrene monomer was added to the obtained unsaturated polyester so as to be 30% by mass based on the total of the unsaturated polyester and the styrene monomer to obtain (a) an unsaturated polyester resin.
＜実施例１～２、比較例１～７＞
表１に示す配合組成で、不飽和ポリエステル樹脂組成物を構成する各材料を仕込み、双腕型ニーダーを用いて２５℃にて３０分間混練することで、不飽和ポリエステル樹脂組成物を得た。なお、表１に示す（ａ）不飽和ポリエステル樹脂は、上記の方法により得られたものであり、スチレンモノマーを３０質量％含有する。 <Examples 1 and 2, Comparative Examples 1 to 7>
Each material constituting the unsaturated polyester resin composition was charged with the compounding composition shown in Table 1 and kneaded at 25 ° C. for 30 minutes using a dual-arm kneader to obtain an unsaturated polyester resin composition. The unsaturated polyester resin (a) shown in Table 1 was obtained by the above method and contains 30% by mass of a styrene monomer.
表１に示す配合組成で、不飽和ポリエステル樹脂組成物を構成する各材料を仕込み、双腕型ニーダーを用いて２５℃にて３０分間混練することで、不飽和ポリエステル樹脂組成物を得た。なお、表１に示す（ａ）不飽和ポリエステル樹脂は、上記の方法により得られたものであり、スチレンモノマーを３０質量％含有する。 <Examples 1 and 2, Comparative Examples 1 to 7>
Each material constituting the unsaturated polyester resin composition was charged with the compounding composition shown in Table 1 and kneaded at 25 ° C. for 30 minutes using a dual-arm kneader to obtain an unsaturated polyester resin composition. The unsaturated polyester resin (a) shown in Table 1 was obtained by the above method and contains 30% by mass of a styrene monomer.
＜材料＞
実施例及び比較例において用いた材料は、以下のとおりである。
（ｂ）無機充填材
（ｂ１）炭酸カルシウム（Ｓ－１２００ＢＭ、備北粉化工業株式会社、平均粒子径：１．８μｍ、真比重：２．７ｇ／ｃｍ３）
（ｂ２）炭酸カルシウム（タンカルＲ重炭、丸尾カルシウム株式会社、平均粒子径：７．４μｍ、真比重：２．７ｇ／ｃｍ３）
（ｂ３）炭酸カルシウム（寒水石ＫＤ－７０、株式会社カルファイン、平均粒子径：３００μｍ、真比重：２．７ｇ／ｃｍ３）
（ｃ）金属石鹸
ステアリン酸カルシウム（淡南化学工業株式会社）
（ｄ）低収縮剤
ポリスチレン（重量平均分子量２００，０００、積水化成品工業株式会社）
（ｅ）繊維強化材
チョップドストランドガラス（繊維長：９ｍｍ、日本電気硝子株式会社）
（ｆ）硬化剤
ｔ－ブチルパーオキシベンゾエート（日油株式会社） <Material>
The materials used in the examples and comparative examples are as follows.
(B) Inorganic filler (b1) Calcium carbonate (S-1200BM, Bikita Powder Industry Co., Ltd., average particle diameter: 1.8 μm, true specific gravity: 2.7 g / cm 3 )
(B2) Calcium carbonate (Tancal R Heavy Charcoal, Maruo Calcium Co., Ltd., average particle size: 7.4 μm, true specific gravity: 2.7 g / cm 3 )
(B3) Calcium carbonate (Kanmizuishi KD-70, Calfine Co., Ltd., average particle size: 300 μm, true specific gravity: 2.7 g / cm 3 )
(C) Metal soap Calcium stearate (Tannan Chemical Industry Co., Ltd.)
(D) Polystyrene, a low shrinkage agent (weight average molecular weight 200,000, Sekisui Plastics Co., Ltd.)
(E) Fiber reinforced material Chopped strand glass (fiber length: 9 mm, Nippon Electric Glass Co., Ltd.)
(F) Curing agent t-butyl peroxybenzoate (NOF CORPORATION)
実施例及び比較例において用いた材料は、以下のとおりである。
（ｂ）無機充填材
（ｂ１）炭酸カルシウム（Ｓ－１２００ＢＭ、備北粉化工業株式会社、平均粒子径：１．８μｍ、真比重：２．７ｇ／ｃｍ３）
（ｂ２）炭酸カルシウム（タンカルＲ重炭、丸尾カルシウム株式会社、平均粒子径：７．４μｍ、真比重：２．７ｇ／ｃｍ３）
（ｂ３）炭酸カルシウム（寒水石ＫＤ－７０、株式会社カルファイン、平均粒子径：３００μｍ、真比重：２．７ｇ／ｃｍ３）
（ｃ）金属石鹸
ステアリン酸カルシウム（淡南化学工業株式会社）
（ｄ）低収縮剤
ポリスチレン（重量平均分子量２００，０００、積水化成品工業株式会社）
（ｅ）繊維強化材
チョップドストランドガラス（繊維長：９ｍｍ、日本電気硝子株式会社）
（ｆ）硬化剤
ｔ－ブチルパーオキシベンゾエート（日油株式会社） <Material>
The materials used in the examples and comparative examples are as follows.
(B) Inorganic filler (b1) Calcium carbonate (S-1200BM, Bikita Powder Industry Co., Ltd., average particle diameter: 1.8 μm, true specific gravity: 2.7 g / cm 3 )
(B2) Calcium carbonate (Tancal R Heavy Charcoal, Maruo Calcium Co., Ltd., average particle size: 7.4 μm, true specific gravity: 2.7 g / cm 3 )
(B3) Calcium carbonate (Kanmizuishi KD-70, Calfine Co., Ltd., average particle size: 300 μm, true specific gravity: 2.7 g / cm 3 )
(C) Metal soap Calcium stearate (Tannan Chemical Industry Co., Ltd.)
(D) Polystyrene, a low shrinkage agent (weight average molecular weight 200,000, Sekisui Plastics Co., Ltd.)
(E) Fiber reinforced material Chopped strand glass (fiber length: 9 mm, Nippon Electric Glass Co., Ltd.)
(F) Curing agent t-butyl peroxybenzoate (NOF CORPORATION)
＜評価＞
得られた実施例及び比較例の不飽和ポリエステル樹脂組成物について、混練性、樹脂組成物の型内流動性、成形品表面平滑性、成形収縮率、強度物性（曲げ強さ及び曲げ弾性率）、及び低バリ性確認として薄肉流動金型を用いての流動性について、測定又は評価を行った。測定方法及び評価方法は、次のとおりである。結果を表１に示す。 <Evaluation>
Regarding the obtained unsaturated polyester resin compositions of Examples and Comparative Examples, kneading property, in-mold fluidity of the resin composition, surface smoothness of the molded product, molding shrinkage rate, strength physical properties (bending strength and bending elastic modulus). , And the fluidity using a thin-walled fluidized mold was measured or evaluated to confirm the low burr property. The measurement method and evaluation method are as follows. The results are shown in Table 1.
得られた実施例及び比較例の不飽和ポリエステル樹脂組成物について、混練性、樹脂組成物の型内流動性、成形品表面平滑性、成形収縮率、強度物性（曲げ強さ及び曲げ弾性率）、及び低バリ性確認として薄肉流動金型を用いての流動性について、測定又は評価を行った。測定方法及び評価方法は、次のとおりである。結果を表１に示す。 <Evaluation>
Regarding the obtained unsaturated polyester resin compositions of Examples and Comparative Examples, kneading property, in-mold fluidity of the resin composition, surface smoothness of the molded product, molding shrinkage rate, strength physical properties (bending strength and bending elastic modulus). , And the fluidity using a thin-walled fluidized mold was measured or evaluated to confirm the low burr property. The measurement method and evaluation method are as follows. The results are shown in Table 1.
（１）混練性
不飽和ポリエステル樹脂組成物を調製する際（双腕型ニーダーを用いて２５℃にて３０分間混練）に、分散不良がない均一な不飽和ポリエステル樹脂組成物が得られるか否かを、目視にて評価した。評価基準を以下に示す。
良：不飽和ポリエステル樹脂組成物が均一である。
不良：不飽和ポリエステル樹脂組成物に分散不良がある。 (1) Kneadability When preparing an unsaturated polyester resin composition (kneading at 25 ° C. for 30 minutes using a dual-arm kneader), whether or not a uniform unsaturated polyester resin composition without poor dispersion can be obtained. Was visually evaluated. The evaluation criteria are shown below.
Good: The unsaturated polyester resin composition is uniform.
Defective: The unsaturated polyester resin composition has poor dispersion.
不飽和ポリエステル樹脂組成物を調製する際（双腕型ニーダーを用いて２５℃にて３０分間混練）に、分散不良がない均一な不飽和ポリエステル樹脂組成物が得られるか否かを、目視にて評価した。評価基準を以下に示す。
良：不飽和ポリエステル樹脂組成物が均一である。
不良：不飽和ポリエステル樹脂組成物に分散不良がある。 (1) Kneadability When preparing an unsaturated polyester resin composition (kneading at 25 ° C. for 30 minutes using a dual-arm kneader), whether or not a uniform unsaturated polyester resin composition without poor dispersion can be obtained. Was visually evaluated. The evaluation criteria are shown below.
Good: The unsaturated polyester resin composition is uniform.
Defective: The unsaturated polyester resin composition has poor dispersion.
（２）樹脂組成物の型内流動性
トランスファー成形機（株式会社テクノマルシチ）にスパイラルフロー金型（断面形状：上辺６ｍｍ、底辺８ｍｍ、高さ２ｍｍの台形状）を取り付けて、金型温度１５０℃、注入圧力１０ＭＰａの条件下で、スパイラルフロー試験を行い、流動長（ｃｍ）を測定した。測定結果及び評価結果を、表１に示す。流動長が３０ｃｍ以上であると、樹脂組成物の型内流動性が良好である。 (2) In-mold flowability of resin composition A spiral flow mold (cross-sectional shape: top side 6 mm, bottom side 8 mm, height 2 mm trapezoidal shape) is attached to a transfer molding machine (Techno Marushichi Co., Ltd.), and the mold temperature is 150. A spiral flow test was performed under the conditions of ° C. and an injection pressure of 10 MPa, and the flow length (cm) was measured. The measurement results and evaluation results are shown in Table 1. When the flow length is 30 cm or more, the in-mold fluidity of the resin composition is good.
トランスファー成形機（株式会社テクノマルシチ）にスパイラルフロー金型（断面形状：上辺６ｍｍ、底辺８ｍｍ、高さ２ｍｍの台形状）を取り付けて、金型温度１５０℃、注入圧力１０ＭＰａの条件下で、スパイラルフロー試験を行い、流動長（ｃｍ）を測定した。測定結果及び評価結果を、表１に示す。流動長が３０ｃｍ以上であると、樹脂組成物の型内流動性が良好である。 (2) In-mold flowability of resin composition A spiral flow mold (cross-sectional shape: top side 6 mm, bottom side 8 mm, height 2 mm trapezoidal shape) is attached to a transfer molding machine (Techno Marushichi Co., Ltd.), and the mold temperature is 150. A spiral flow test was performed under the conditions of ° C. and an injection pressure of 10 MPa, and the flow length (cm) was measured. The measurement results and evaluation results are shown in Table 1. When the flow length is 30 cm or more, the in-mold fluidity of the resin composition is good.
（３）成形品表面平滑性
トランスファー成形機（株式会社テクノマルシチ）を用いて、成形温度１５０℃、射出圧力２０ＭＰａ、成形時間１分の条件下にて、トランスファー成形体（φ１１７ｍｍ、厚さ３ｍｍ）を作製した。得られたトランスファー成形体の外観を目視で確認し、以下の評価基準で評価した。
良：全体にツヤがあり、且つ全体にヒケがない。
不良：全体若しくは部分的にツヤがない、又は全体若しくは部分的にヒケがある。 (3) Surface smoothness of molded product A transferred molded product (φ117 mm, thickness 3 mm) under the conditions of a molding temperature of 150 ° C., an injection pressure of 20 MPa, and a molding time of 1 minute using a transfer molding machine (Technomarushichi Co., Ltd.). Was produced. The appearance of the obtained transfer molded product was visually confirmed and evaluated according to the following evaluation criteria.
Good: There is gloss on the whole and there is no sink mark on the whole.
Defective: Totally or partially dull, or wholly or partially sink marks.
トランスファー成形機（株式会社テクノマルシチ）を用いて、成形温度１５０℃、射出圧力２０ＭＰａ、成形時間１分の条件下にて、トランスファー成形体（φ１１７ｍｍ、厚さ３ｍｍ）を作製した。得られたトランスファー成形体の外観を目視で確認し、以下の評価基準で評価した。
良：全体にツヤがあり、且つ全体にヒケがない。
不良：全体若しくは部分的にツヤがない、又は全体若しくは部分的にヒケがある。 (3) Surface smoothness of molded product A transferred molded product (φ117 mm, thickness 3 mm) under the conditions of a molding temperature of 150 ° C., an injection pressure of 20 MPa, and a molding time of 1 minute using a transfer molding machine (Technomarushichi Co., Ltd.). Was produced. The appearance of the obtained transfer molded product was visually confirmed and evaluated according to the following evaluation criteria.
Good: There is gloss on the whole and there is no sink mark on the whole.
Defective: Totally or partially dull, or wholly or partially sink marks.
（４）成形収縮率
圧縮成形機（コンプレッション成形機、株式会社テクノマルシチ）を用いて、ＪＩＳ Ｋ－６９１１ ５．７に規定される収縮円盤（φ９０ｍｍ×１１ｍｍ）を、成形温度１６０℃、成形圧力１０ＭＰａ、成形時間３分の条件下で、圧縮成形にて作製し、ＪＩＳ Ｋ－６９１１ ５．７に準拠して、成形収縮率（％）を算出した。結果を表１に示す。 (4) Molding shrinkage rate Using a compression molding machine (compression molding machine, Techno Marushichi Co., Ltd.), a shrinkage disk (φ90 mm × 11 mm) specified in JIS K-6911 5.7 is molded at a molding temperature of 160 ° C and molding pressure. It was manufactured by compression molding under the conditions of 10 MPa and a molding time of 3 minutes, and the molding shrinkage rate (%) was calculated according to JIS K-6911 5.7. The results are shown in Table 1.
圧縮成形機（コンプレッション成形機、株式会社テクノマルシチ）を用いて、ＪＩＳ Ｋ－６９１１ ５．７に規定される収縮円盤（φ９０ｍｍ×１１ｍｍ）を、成形温度１６０℃、成形圧力１０ＭＰａ、成形時間３分の条件下で、圧縮成形にて作製し、ＪＩＳ Ｋ－６９１１ ５．７に準拠して、成形収縮率（％）を算出した。結果を表１に示す。 (4) Molding shrinkage rate Using a compression molding machine (compression molding machine, Techno Marushichi Co., Ltd.), a shrinkage disk (φ90 mm × 11 mm) specified in JIS K-6911 5.7 is molded at a molding temperature of 160 ° C and molding pressure. It was manufactured by compression molding under the conditions of 10 MPa and a molding time of 3 minutes, and the molding shrinkage rate (%) was calculated according to JIS K-6911 5.7. The results are shown in Table 1.
（５）強度物性（曲げ強さ及び曲げ弾性率）
圧縮成形機（コンプレッション成形機、株式会社テクノマルシチ）を用いて、ＪＩＳ Ｋ－６９１１ ５．１７に規定される曲げ弾性率試験片（９０ｍｍ×１０ｍｍ×４ｍｍ）を、成形温度１５０℃、成形圧力１０ＭＰａ、成形時間３分の条件下で、圧縮成形にて作製し、ＪＩＳ Ｋ－６９１１ ５．１７に準拠して、曲げ強さ（ＭＰａ）及び曲げ弾性率（ＭＰａ）を測定し、以下の評価基準で評価した。測定結果及び強度物性評価結果を、表１に示す。
良：曲げ強さが１３０ＭＰａ以上、且つ曲げ弾性率が１３ＭＰａ以上
不良：曲げ強さが１３０ＭＰａ未満、又は曲げ弾性率が１３ＭＰａ未満 (5) Strength physical properties (flexural strength and flexural modulus)
Using a compression molding machine (compression molding machine, Techno Marushichi Co., Ltd.), a flexural modulus test piece (90 mm × 10 mm × 4 mm) specified in JIS K-6911 5.17 was subjected to a molding temperature of 150 ° C. and a molding pressure of 10 MPa. , Made by compression molding under the condition of molding time of 3 minutes, and measured the flexural strength (MPa) and flexural modulus (MPa) according to JIS K-6911 5.17, and the following evaluation criteria. Evaluated in. Table 1 shows the measurement results and the strength physical property evaluation results.
Good: Flexural strength of 130 MPa or more and flexural modulus of 13 MPa or more Defective: Flexural strength of less than 130 MPa or flexural modulus of less than 13 MPa
圧縮成形機（コンプレッション成形機、株式会社テクノマルシチ）を用いて、ＪＩＳ Ｋ－６９１１ ５．１７に規定される曲げ弾性率試験片（９０ｍｍ×１０ｍｍ×４ｍｍ）を、成形温度１５０℃、成形圧力１０ＭＰａ、成形時間３分の条件下で、圧縮成形にて作製し、ＪＩＳ Ｋ－６９１１ ５．１７に準拠して、曲げ強さ（ＭＰａ）及び曲げ弾性率（ＭＰａ）を測定し、以下の評価基準で評価した。測定結果及び強度物性評価結果を、表１に示す。
良：曲げ強さが１３０ＭＰａ以上、且つ曲げ弾性率が１３ＭＰａ以上
不良：曲げ強さが１３０ＭＰａ未満、又は曲げ弾性率が１３ＭＰａ未満 (5) Strength physical properties (flexural strength and flexural modulus)
Using a compression molding machine (compression molding machine, Techno Marushichi Co., Ltd.), a flexural modulus test piece (90 mm × 10 mm × 4 mm) specified in JIS K-6911 5.17 was subjected to a molding temperature of 150 ° C. and a molding pressure of 10 MPa. , Made by compression molding under the condition of molding time of 3 minutes, and measured the flexural strength (MPa) and flexural modulus (MPa) according to JIS K-6911 5.17, and the following evaluation criteria. Evaluated in. Table 1 shows the measurement results and the strength physical property evaluation results.
Good: Flexural strength of 130 MPa or more and flexural modulus of 13 MPa or more Defective: Flexural strength of less than 130 MPa or flexural modulus of less than 13 MPa
（６）薄肉流動性（バリ評価）
バリ性の評価として、トランスファー成形機（株式会社テクノマルシチ）を用いて、成形温度１５０℃、射出圧力２０ＭＰａ、成形時間１分の条件下にて、トランスファー成形体を作製し、得られたトランスファー成形体に発生したバリの長さ（ｍｍ）を測定し、以下の評価基準で評価した。測定結果及びバリ評価結果を、表１に示す。
良：金型の１４０μｍの隙間部分に２０ｍｍ以上のバリが発生していない。
不良：金型の１４０μｍの隙間部分に２０ｍｍ以上のバリが発生した。 (6) Thin-walled liquidity (burr evaluation)
As an evaluation of variability, a transfer molding machine (Technomarsichi Co., Ltd.) was used to prepare a transfer molded product under the conditions of a molding temperature of 150 ° C., an injection pressure of 20 MPa, and a molding time of 1 minute, and the obtained transfer molding was performed. The length (mm) of the burr generated on the body was measured and evaluated according to the following evaluation criteria. The measurement results and burr evaluation results are shown in Table 1.
Good: No burrs of 20 mm or more are generated in the 140 μm gap of the mold.
Defectiveness: Burrs of 20 mm or more were generated in the 140 μm gap of the mold.
バリ性の評価として、トランスファー成形機（株式会社テクノマルシチ）を用いて、成形温度１５０℃、射出圧力２０ＭＰａ、成形時間１分の条件下にて、トランスファー成形体を作製し、得られたトランスファー成形体に発生したバリの長さ（ｍｍ）を測定し、以下の評価基準で評価した。測定結果及びバリ評価結果を、表１に示す。
良：金型の１４０μｍの隙間部分に２０ｍｍ以上のバリが発生していない。
不良：金型の１４０μｍの隙間部分に２０ｍｍ以上のバリが発生した。 (6) Thin-walled liquidity (burr evaluation)
As an evaluation of variability, a transfer molding machine (Technomarsichi Co., Ltd.) was used to prepare a transfer molded product under the conditions of a molding temperature of 150 ° C., an injection pressure of 20 MPa, and a molding time of 1 minute, and the obtained transfer molding was performed. The length (mm) of the burr generated on the body was measured and evaluated according to the following evaluation criteria. The measurement results and burr evaluation results are shown in Table 1.
Good: No burrs of 20 mm or more are generated in the 140 μm gap of the mold.
Defectiveness: Burrs of 20 mm or more were generated in the 140 μm gap of the mold.
本発明によれば、成形時の樹脂流動性が良好であるとともに、成形品外観、寸法精度、及び強度物性に優れ、バリが低減された成形体を与えることのできる、不飽和ポリエステル樹脂組成物を提供することができる。
According to the present invention, an unsaturated polyester resin composition which has good resin fluidity at the time of molding, is excellent in appearance, dimensional accuracy, and strength physical properties of a molded product, and can give a molded product with reduced burrs. Can be provided.
Claims (5)
- （ａ）不飽和ポリエステル樹脂、（ｂ）無機充填材、（ｃ）金属石鹸、（ｄ）低収縮剤、（ｅ）繊維強化材、及び（ｆ）硬化剤を含む不飽和ポリエステル樹脂組成物であって、
前記（ｂ）無機充填材の含有量は、前記（ａ）不飽和ポリエステル樹脂１００質量部に対して２５０～６００質量部であり、
前記（ｂ）無機充填材は、（ｂ１）平均粒子径が０．５～５．０μｍの無機充填材と、（ｂ２）平均粒子径が６．０～５０．０μｍの無機充填材と、（ｂ３）平均粒子径が７０．０μｍ以上の無機充填材とを、無機充填材（ｂ１）、（ｂ２）、及び（ｂ３）の合計１００質量％に対して、（ｂ１）：（ｂ２）：（ｂ３）＝６０～７５：７～１５：１５～３０となる割合で含む、
不飽和ポリエステル樹脂組成物。 An unsaturated polyester resin composition containing (a) an unsaturated polyester resin, (b) an inorganic filler, (c) a metal soap, (d) a low shrinkage agent, (e) a fiber reinforcing material, and (f) a curing agent. There,
The content of the (b) inorganic filler is 250 to 600 parts by mass with respect to 100 parts by mass of the (a) unsaturated polyester resin.
The (b) inorganic filler includes (b1) an inorganic filler having an average particle diameter of 0.5 to 5.0 μm, and (b2) an inorganic filler having an average particle diameter of 6.0 to 50.0 μm. b3) With respect to the total 100% by mass of the inorganic fillers (b1), (b2), and (b3) with an inorganic filler having an average particle diameter of 70.0 μm or more, (b1) :( b2) :( b3) = 60 to 75: 7 to 15: 15 to 30.
Unsaturated polyester resin composition. - 前記（ｂ）無機充填材の含有量は、前記（ａ）不飽和ポリエステル樹脂１００質量部に対して３５０～４５０質量部である、請求項１に記載の不飽和ポリエステル樹脂組成物。 The unsaturated polyester resin composition according to claim 1, wherein the content of the (b) inorganic filler is 350 to 450 parts by mass with respect to 100 parts by mass of the (a) unsaturated polyester resin.
- 前記（ｂ）無機充填材は、炭酸カルシウムを含む請求項１又は２のいずれかに記載の不飽和ポリエステル樹脂組成物。 The unsaturated polyester resin composition according to claim 1 or 2, wherein the (b) inorganic filler contains calcium carbonate.
- 前記（ｅ）繊維強化材の含有量は、（ａ）不飽和ポリエステル樹脂１００質量部に対して７０～１２０質量部である、請求項１～３のいずれか一項に記載の不飽和ポリエステル樹脂組成物。 The unsaturated polyester resin according to any one of claims 1 to 3, wherein the content of the (e) fiber reinforcing material is 70 to 120 parts by mass with respect to 100 parts by mass of the (a) unsaturated polyester resin. Composition.
- 請求項１～４のいずれか一項に記載の不飽和ポリエステル樹脂組成物の硬化物を含む成形体。 A molded product containing a cured product of the unsaturated polyester resin composition according to any one of claims 1 to 4.
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| CN202180084264.8A CN116745330A (en) | 2020-12-21 | 2021-09-24 | Unsaturated polyester resin composition and molded article |
| JP2022571057A JPWO2022137686A1 (en) | 2020-12-21 | 2021-09-24 |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10296727A (en) * | 1997-04-24 | 1998-11-10 | Hitachi Chem Co Ltd | Sheet molding compound and molded body made thereof |
| WO2013100174A1 (en) * | 2011-12-27 | 2013-07-04 | パナソニック株式会社 | Thermally conductive resin composition |
| JP2013209609A (en) * | 2012-02-28 | 2013-10-10 | Panasonic Corp | Heat conductive resin composition for led illumination substrate, method for manufacturing the same, and led illumination substrate |
| WO2014155975A1 (en) * | 2013-03-28 | 2014-10-02 | パナソニック株式会社 | Insulating thermally conductive resin composition |
| JP2018090695A (en) * | 2016-12-02 | 2018-06-14 | 昭和電工株式会社 | Arc resistant bmc |
| WO2019116691A1 (en) * | 2017-12-11 | 2019-06-20 | 昭和電工株式会社 | Unsaturated polyester resin composition, molded article containing cured product thereof, and lamp reflector including said molded article |
| JP2019151785A (en) * | 2018-03-06 | 2019-09-12 | 三菱電機株式会社 | Fouling deterioration resistant resin insulation article |
-
2021
- 2021-09-24 CN CN202180084264.8A patent/CN116745330A/en active Pending
- 2021-09-24 JP JP2022571057A patent/JPWO2022137686A1/ja active Pending
- 2021-09-24 WO PCT/JP2021/035157 patent/WO2022137686A1/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10296727A (en) * | 1997-04-24 | 1998-11-10 | Hitachi Chem Co Ltd | Sheet molding compound and molded body made thereof |
| WO2013100174A1 (en) * | 2011-12-27 | 2013-07-04 | パナソニック株式会社 | Thermally conductive resin composition |
| JP2013209609A (en) * | 2012-02-28 | 2013-10-10 | Panasonic Corp | Heat conductive resin composition for led illumination substrate, method for manufacturing the same, and led illumination substrate |
| WO2014155975A1 (en) * | 2013-03-28 | 2014-10-02 | パナソニック株式会社 | Insulating thermally conductive resin composition |
| JP2018090695A (en) * | 2016-12-02 | 2018-06-14 | 昭和電工株式会社 | Arc resistant bmc |
| WO2019116691A1 (en) * | 2017-12-11 | 2019-06-20 | 昭和電工株式会社 | Unsaturated polyester resin composition, molded article containing cured product thereof, and lamp reflector including said molded article |
| JP2019151785A (en) * | 2018-03-06 | 2019-09-12 | 三菱電機株式会社 | Fouling deterioration resistant resin insulation article |
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| CN116745330A (en) | 2023-09-12 |
| JPWO2022137686A1 (en) | 2022-06-30 |
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