JP6361907B2 - Unsaturated polyester resin composition - Google Patents
Unsaturated polyester resin composition Download PDFInfo
- Publication number
- JP6361907B2 JP6361907B2 JP2014016300A JP2014016300A JP6361907B2 JP 6361907 B2 JP6361907 B2 JP 6361907B2 JP 2014016300 A JP2014016300 A JP 2014016300A JP 2014016300 A JP2014016300 A JP 2014016300A JP 6361907 B2 JP6361907 B2 JP 6361907B2
- Authority
- JP
- Japan
- Prior art keywords
- unsaturated polyester
- hexahydro
- resin composition
- polyester resin
- diallyl phthalate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims description 34
- 229920006337 unsaturated polyester resin Polymers 0.000 title claims description 28
- 229920000642 polymer Polymers 0.000 claims description 27
- 239000004641 Diallyl-phthalate Substances 0.000 claims description 26
- 229920006305 unsaturated polyester Polymers 0.000 claims description 17
- -1 allyl compound Chemical class 0.000 claims description 16
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 13
- 230000000379 polymerizing effect Effects 0.000 claims description 12
- 125000006841 cyclic skeleton Chemical group 0.000 claims description 10
- 239000003505 polymerization initiator Substances 0.000 claims description 10
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- 125000000746 allylic group Chemical group 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 239000011256 inorganic filler Substances 0.000 claims description 7
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 239000012778 molding material Substances 0.000 description 9
- 238000001723 curing Methods 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 7
- 150000007519 polyprotic acids Polymers 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 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
- 238000006116 polymerization reaction 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
- 230000015572 biosynthetic process Effects 0.000 description 4
- 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 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- 238000001721 transfer moulding Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-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
- 238000004458 analytical method Methods 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003365 glass fiber 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012783 reinforcing fiber Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 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
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-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
- 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
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- IDCBOTIENDVCBQ-UHFFFAOYSA-N TEPP Chemical compound CCOP(=O)(OCC)OP(=O)(OCC)OCC IDCBOTIENDVCBQ-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
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 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
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate 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
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 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
- 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
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development 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
- 239000012933 diacyl peroxide Substances 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
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 238000012812 general test Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000005484 gravity Effects 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
- 150000004677 hydrates Chemical class 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection 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
- 238000004898 kneading Methods 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 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
- 239000000843 powder Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は、流動性にすぐれた不飽和ポリエステル樹脂組成物に関するものである。 The present invention relates to an unsaturated polyester resin composition having excellent fluidity.
最近、コンデンサー、コイル、抵抗体等の電子部品において、信頼性や生産性向上を目的として、封止用樹脂が用いられるようになってきている。封止用樹脂として求められる性能は、電子部品の形状や大きさによって異なるが、物理的性能として、耐湿性・低応力性・高熱伝導性・耐衝撃性等が挙げられる。この性能を満足する樹脂としてジアリルフタレート樹脂や不飽和ポリエステル樹脂等の熱硬化性樹脂が用いられている。 Recently, in electronic parts such as capacitors, coils and resistors, sealing resins have been used for the purpose of improving reliability and productivity. The performance required for the sealing resin varies depending on the shape and size of the electronic component, but examples of physical performance include moisture resistance, low stress, high thermal conductivity, and impact resistance. Thermosetting resins such as diallyl phthalate resins and unsaturated polyester resins are used as resins that satisfy this performance.
しかしながら、近年の電子情報機器の進展に伴い、封止用樹脂に対する要求性能がますます厳しくなっている。特に、小型部品向けの封止用樹脂において、生産効率の点から高い流動性が求められている。 However, with the recent development of electronic information devices, the required performance for sealing resins has become increasingly severe. In particular, in a sealing resin for small parts, high fluidity is required from the viewpoint of production efficiency.
流動性を上げる方法として、特許文献１には硬化触媒として、２，５−ジメチル−２，５−ビス（ベンゾイルパーオキシ）ヘキサンを配合してなることを特徴とするジアリルフタレート樹脂成形材料が記載されている。しかしながら、記載されているジアリルフタレート樹脂成形材料は、硬化速度を維持しながら優れた流動性を有し、低圧成形性に優れた樹脂成形材料としては、不十分であった。 As a method for increasing fluidity, Patent Document 1 describes a diallyl phthalate resin molding material comprising 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane as a curing catalyst. Has been. However, the described diallyl phthalate resin molding material has an excellent fluidity while maintaining the curing speed, and is insufficient as a resin molding material excellent in low-pressure moldability.
また、特許文献２には、樹脂組成物中にモノマー成分を添加することで、硬化速度を速め、流動性を確保しつつ、耐熱性、強度の発現に効果的であることが記載されている。しかしながら、樹脂組成物中にモノマー成分を添加することにより、成形品への着色、硬化不足によるＶＯＣ（揮発性有機物）の問題等が懸念されている。 Patent Document 2 describes that by adding a monomer component to the resin composition, the curing rate is increased and the fluidity is ensured while the heat resistance and the strength are effectively expressed. . However, there is a concern about the problem of VOC (volatile organic matter) due to coloring of the molded product and insufficient curing due to the addition of the monomer component in the resin composition.
本発明の目的は、流動性に優れる不飽和ポリエステル樹脂組成物を提供することにある。 An object of the present invention is to provide an unsaturated polyester resin composition having excellent fluidity.
本発明者は、鋭意研究の結果、不飽和ポリエステル（Ａ）と、
一般式（Ｉ）で表されるアリル系化合物を重合して得られるアリル系重合体（Ｂ）と
（ＣＨＲ１＝ＣＲ２−ＣＨ２−Ｏ−ＣＯ)ｎ−Ｘ （Ｉ）
[Ｒ１およびＲ２は、それぞれ、ＨまたはＣＨ３を表し、
Ｘはアルキル置換基を有していてもよい飽和の４〜８員環の環状骨格を表し、ｎは２または３を表す。]
重合開始剤（Ｃ）を、含有してなる不飽和ポリエステル樹脂組成物を用いることにより、流動性に優れ、成形性が向上した樹脂組成物が得られることを見出し、本発明を完成した。
As a result of intensive studies, the present inventor has found that the unsaturated polyester (A)
An allyl polymer (B) obtained by polymerizing an allyl compound represented by the general formula (I) and (CHR 1 = CR 2 —CH 2 —O—CO) n —X (I)
[R 1 and R 2 each represent H or CH 3 ;
X represents a saturated 4- to 8-membered cyclic skeleton optionally having an alkyl substituent, and n represents 2 or 3. ]
By using an unsaturated polyester resin composition containing the polymerization initiator (C), it was found that a resin composition having excellent fluidity and improved moldability was obtained, and the present invention was completed.
項１． 不飽和ポリエステル（Ａ）と、
一般式（Ｉ）で表されるアリル系化合物を重合して得られるアリル系重合体（Ｂ）と
（ＣＨＲ１＝ＣＲ２−ＣＨ２−Ｏ−ＣＯ)ｎ−Ｘ （Ｉ）
[Ｒ１およびＲ２は、それぞれ、ＨまたはＣＨ３を表し、
Ｘはアルキル置換基を有していてもよい飽和の４〜８員環の環状骨格を表し、ｎは２または３を表す。]
重合開始剤（Ｃ）を、含有してなる不飽和ポリエステル樹脂組成物。
項２． アリル系重合体（Ｂ）が、項１記載の式（Ｉ）中のＸが以下の環状骨格の少なくとも１つを有するアリル系化合物を重合したものである項１に記載の組成物。
項３． 一般式（Ｉ）で表されるアリル系化合物を重合して得られるアリル系重合体がヘキサヒドロ−１，２−ジアリルフタレート、ヘキサヒドロ−１，３−ジアリルイソフタレート、ヘキサヒドロ−１，４−ジアリルテレフタレート、３−メチル−ヘキサヒドロ−１，２−ジアリルフタレート、４−メチル−ヘキサヒドロ−１，２−ジアリルフタレート、３，６−エンドメチレン−３−メチル−ヘキサヒドロ−１，２−ジアリルフタレート、３，６−エンドメチレン−４−メチル−ヘキサヒドロ−１，２−ジアリルフタレートからなる群より選択される少なくとも1種以上を、重合することで得られるアリル系重合体である項１又は２に記載の組成物。
項４． さらに、無機充填剤（Ｄ）を含有する項１〜３のいずれかに記載の組成物。
項５． 項１〜４のいずれかに記載の不飽和ポリエステル樹脂組成物を熱硬化することによって得られる硬化物。
項６． 項１〜４のいずれかに記載の不飽和ポリエステル樹脂組成物を成形してなることを特徴とする成形品。
Item 1. Unsaturated polyester (A);
An allyl polymer (B) obtained by polymerizing an allyl compound represented by the general formula (I) and (CHR 1 = CR 2 —CH 2 —O—CO) n —X (I)
[R 1 and R 2 each represent H or CH 3 ;
X represents a saturated 4- to 8-membered cyclic skeleton optionally having an alkyl substituent, and n represents 2 or 3. ]
An unsaturated polyester resin composition comprising a polymerization initiator (C).
Item 2. Item 2. The composition according to Item 1, wherein the allylic polymer (B) is obtained by polymerizing an allylic compound in which X in Formula (I) according to Item 1 has at least one of the following cyclic skeletons.
Item 3. The allyl polymer obtained by polymerizing the allyl compound represented by the general formula (I) is hexahydro-1,2-diallyl phthalate, hexahydro-1,3-diallyl isophthalate, hexahydro-1,4-diallyl terephthalate. 3-methyl-hexahydro-1,2-diallyl phthalate, 4-methyl-hexahydro-1,2-diallyl phthalate, 3,6-endomethylene-3-methyl-hexahydro-1,2-diallyl phthalate, 3,6 Item 3. The composition according to Item 1 or 2, which is an allylic polymer obtained by polymerizing at least one selected from the group consisting of endomethylene-4-methyl-hexahydro-1,2-diallylphthalate. .
Item 4. Furthermore, the composition in any one of claim | item 1 -3 containing an inorganic filler (D).
Item 5. Item 5. A cured product obtained by thermally curing the unsaturated polyester resin composition according to any one of Items 1 to 4.
Item 6. Item 5. A molded article obtained by molding the unsaturated polyester resin composition according to any one of Items 1 to 4.
本発明は、上記知見に基づき完成されたものであり、成形の際、流動性に優れた不飽和ポリエステル樹脂組成物を提供する。 This invention is completed based on the said knowledge, and provides the unsaturated polyester resin composition excellent in the fluidity | liquidity in the case of shaping | molding.
本発明によれば、硬化速度を維持しながら優れた流動性を有し、低圧成形性に優れた耐熱性、強度の発現に効果的である不飽和ポリエステル樹脂組成物が得られる。 According to the present invention, it is possible to obtain an unsaturated polyester resin composition having excellent fluidity while maintaining a curing rate, and effective in developing heat resistance and strength excellent in low-pressure moldability.
以下、本発明を詳細に説明する。
不飽和ポリエステル樹脂組成物
本発明は、不飽和ポリエステル（Ａ）と、
一般式（Ｉ）で表されるアリル系化合物を重合して得られるアリル系重合体（Ｂ）と
（ＣＨＲ１＝ＣＲ２−ＣＨ２−Ｏ−ＣＯ)ｎ−Ｘ （Ｉ）
[Ｒ１およびＲ２は、それぞれ、ＨまたはＣＨ３を表し、
Ｘはアルキル置換基を有していてもよい飽和の４〜８員環の環状骨格を表し、ｎは２または３を表す。]
重合開始剤（Ｃ）を、含有してなる不飽和ポリエステル樹脂組成物である。
Hereinafter, the present invention will be described in detail.
Unsaturated polyester resin composition The present invention, unsaturated polyester (A),
An allyl polymer (B) obtained by polymerizing an allyl compound represented by the general formula (I) and (CHR 1 = CR 2 —CH 2 —O—CO) n —X (I)
[R 1 and R 2 each represent H or CH 3 ;
X represents a saturated 4- to 8-membered cyclic skeleton optionally having an alkyl substituent, and n represents 2 or 3. ]
It is an unsaturated polyester resin composition containing a polymerization initiator (C).
不飽和ポリエステル（Ａ）
本発明で用いる不飽和ポリエステル（Ａ）は、特に限定されず、当該技術分野において公知のものを用いることができる。不飽和ポリエステルは、一般的に、多価アルコールを不飽和多塩基酸や飽和多塩基酸と重縮合（エステル化）させて得られた化合物であり、所望の特性に応じて適宜選択して用いることができる。
Unsaturated polyester (A)
The unsaturated polyester (A) used in the present invention is not particularly limited, and those known in the technical field can be used. An unsaturated polyester is generally a compound obtained by polycondensation (esterification) of a polyhydric alcohol with an unsaturated polybasic acid or a saturated polybasic acid, and is appropriately selected and used according to desired properties. be able to.
本発明における不飽和ポリエステル（Ａ）の重量平均分子量（Ｍｗ）は、特に限定されないが、好ましくは５，０００〜２０，０００である。なお、本明細書において「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（昭和電工株式会社製Ｓｈｏｄｅｘ ＧＰＣ−１０１）を用いて常温で測定し、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。 Although the weight average molecular weight (Mw) of the unsaturated polyester (A) in this invention is not specifically limited, Preferably it is 5,000-20,000. In the present specification, the “weight average molecular weight” is a value obtained by measuring at normal temperature using gel permeation chromatography (Shodex GPC-101 manufactured by Showa Denko KK) and using a standard polystyrene calibration curve. Means.
本発明の不飽和ポリエステル（Ａ）の合成に用いられる多価アルコールとしては、特に限定されず、公知のものを用いることができる。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、ネオペンチルグリコール、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、水素化ビスフェノールＡ、ビスフェノールＡ、グリセリン等を例示することができる。これらの中でも、耐熱性、機械的強度及び成形性の観点から、プロピレングリコール、ネオペンチルグリコール、及びビスフェノールＡ又は水素化ビスフェノールＡが好ましい。これらの多価アルコールは、単独又は複数を組み合わせて用いることができる。 It does not specifically limit as a polyhydric alcohol used for the synthesis | combination of the unsaturated polyester (A) of this invention, A well-known thing can be used. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, neopentyl glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, pentanediol, hexanediol, hydrogenated bisphenol A, bisphenol A, glycerin and the like. be able to. Among these, propylene glycol, neopentyl glycol, and bisphenol A or hydrogenated bisphenol A are preferable from the viewpoints of heat resistance, mechanical strength, and moldability. These polyhydric alcohols can be used alone or in combination.
本発明の不飽和ポリエステル（Ａ）の合成に用いられる不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。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、イタコン酸等を例示することができる。これらは、単独又は複数を組み合わせて用いることができる。 It does not specifically limit as an unsaturated polybasic acid used for the synthesis | combination of the unsaturated polyester (A) of this invention, A well-known thing can be used. Examples of the unsaturated polybasic acid include maleic anhydride, fumaric acid, citraconic acid, itaconic acid and the like. These can be used alone or in combination.
不飽和ポリエステルの合成に用いられ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、ヘット酸、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、エンドメチレンテトラヒドロ無水フタル酸等を例示することができる。これらは、単独又は複数を組み合わせて用いることができる。上記の中でも、耐熱性、機械的強度及び成形性等の観点から、不飽和多塩基酸が好ましく、無水マレイン酸及びフマル酸がより好ましい。 It does not specifically limit as a saturated polybasic acid used for the synthesis | combination of unsaturated polyester, A well-known thing can be used. Examples of saturated polybasic acids include phthalic anhydride, isophthalic acid, terephthalic acid, het acid, succinic acid, adipic acid, sebacic acid, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, endomethylenetetrahydrophthalic anhydride, etc. It can be illustrated. These can be used alone or in combination. Among these, from the viewpoints of heat resistance, mechanical strength, moldability, and the like, unsaturated polybasic acids are preferable, and maleic anhydride and fumaric acid are more preferable.
本発明の不飽和ポリエステル（Ａ）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。こ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必要があるが、一般的に、窒素等の不活性ガス気流中、１４０〜２３０℃の温度にて加圧又は減圧下でエステル化させればよい。この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。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、及び酢酸コバルト等の公知の触媒を例示することができる。これらは、単独又は複数を組み合わせて用いることができる。 The unsaturated polyester (A) of the present invention can be synthesized by a known method using the raw materials as described above. Various conditions in this synthesis need to be set as appropriate according to the raw material used and the amount thereof, but in general, in an inert gas stream such as nitrogen, at a temperature of 140 to 230 ° C. under pressure or reduced pressure. Can be esterified. In this esterification reaction, an esterification catalyst can be used as needed. Examples of the catalyst include known catalysts such as manganese acetate, dibutyltin oxide, stannous oxalate, zinc acetate, and cobalt acetate. These can be used alone or in combination.
本発明の不飽和ポリエステル（Ａ）の含有量は、不飽和ポリエステル樹脂組成物全量に対して、５〜９５重量％の範囲であればよく、１０〜９０重量％の範囲が好ましく、１０〜７０重量％の範囲がより好ましい。上記範囲内であれば、本発明の効果を十分に得ることができる。 Content of unsaturated polyester (A) of this invention should just be the range of 5-95 weight% with respect to the unsaturated polyester resin composition whole quantity, the range of 10-90 weight% is preferable, and 10-70 is preferable. A range of% by weight is more preferred. If it is in the said range, the effect of this invention can fully be acquired.
アリル系重合体（Ｂ）
本発明で用いるアリル系重合体（Ｂ）は、一般式（Ｉ）で表されるアリル系化合物を重合して得られるアリル系重合体を例示することができる。
（ＣＨＲ１＝ＣＲ２−ＣＨ２−Ｏ−ＣＯ)ｎ−Ｘ （Ｉ）
[Ｒ１およびＲ２は、それぞれ、ＨまたはＣＨ３を表し、
Ｘはアルキル置換基を有していてもよい飽和の４〜８員環の環状骨格を表し、ｎは２または３を表す。]
Allyl polymer (B)
The allyl polymer (B) used in the present invention can be exemplified by an allyl polymer obtained by polymerizing an allyl compound represented by the general formula (I).
(CHR 1 = CR 2 -CH 2 -O-CO) n -X (I)
[R 1 and R 2 each represent H or CH 3 ;
X represents a saturated 4- to 8-membered cyclic skeleton optionally having an alkyl substituent, and n represents 2 or 3. ]
また、アリル系重合体（Ｂ）の重量平均分子量は、特に制限されないが、例えば、１，０００〜３００，０００であればよく、５，０００〜２００，０００が好ましく、２０，０００〜１００，０００がより好ましい。上記範囲内であれば、本発明の効果を十分に得ることができる。 The weight average molecular weight of the allylic polymer (B) is not particularly limited, and may be, for example, 1,000 to 300,000, preferably 5,000 to 200,000, and 20,000 to 100,000. 000 is more preferable. If it is in the said range, the effect of this invention can fully be acquired.
式（Ｉ）におけるＸの具体例として、以下の環状骨格を例示できる。
式（Ｉ）におけるＸの好ましいものとして、以下の環状骨格を例示できる。
式（Ｉ）におけるＸのより好ましいものとして、以下の環状骨格を例示できる。
Ｘの環上におけるＣＨＲ１＝ＣＲ２−ＣＨ２−Ｏ−ＣＯ−基の置換位置は何れの組み合わせであっても良く、それらの混合物でも良い。特に、２つのＣＨＲ１＝ＣＲ２−ＣＨ２−Ｏ−ＣＯ−基が６員環のＸに結合するときに、２つのＣＨＲ１＝ＣＲ２−ＣＨ２−Ｏ−ＣＯ−基は、オルト配向またはメタ配向またはパラ配向のいずれでもよいが、オルト配向またはメタ配向であることが好ましい。 The substitution positions of the CHR 1 ═CR 2 —CH 2 —O—CO— group on the ring of X may be any combination, or a mixture thereof. In particular, when two CHR 1 ═CR 2 —CH 2 —O—CO— groups are bonded to a 6-membered X, the two CHR 1 ═CR 2 —CH 2 —O—CO— groups are ortho-oriented. Alternatively, either meta orientation or para orientation may be used, but ortho orientation or meta orientation is preferred.
Ｘは、分子内で架橋されていても良い（例えば、アダマンタン、ノルボルネン、ノルボルナン）。また、Ｘは、芳香族の６員環ではない。 X may be crosslinked in the molecule (for example, adamantane, norbornene, norbornane). X is not an aromatic 6-membered ring.
上記式中、置換基Ｒ１１は、それぞれ同一または異なって、アルキル基（炭素数１〜５、特にメチル基およびエチル基）である。
Ｘの環上におけるＲ１１基の置換位置は何れであっても良く、それらの混合物でも良い。
ｐの下限値は０である。ｐの上限値は、［（環の炭素数）−（１、２または３）］である。ｐは一般に０〜４、例えば０〜３、特に０〜２、さらには０である。
ｎは、２または３、好ましくは２である。
In the above formula, the substituents R 11 are the same or different and each is an alkyl group (having 1 to 5 carbon atoms, particularly a methyl group and an ethyl group).
The substitution position of the R 11 group on the ring of X may be any, or a mixture thereof.
The lower limit of p is 0. The upper limit of p is [(ring carbon number) − (1, 2 or 3)]. p is generally 0-4, such as 0-3, in particular 0-2, and even 0.
n is 2 or 3, preferably 2.
上記式（Ｉ）で表されるアリル系化合物としては、特に限定されず、市販されているものを購入して用いてもよく、合成したものを用いてもよい。具体例としては、ヘキサヒドロ−１，２−ジアリルフタレート、ヘキサヒドロ−１，３−ジアリルイソフタレート、ヘキサヒドロ−１，４−ジアリルテレフタレート、３−メチル−ヘキサヒドロ−１，２−ジアリルフタレート、４−メチル−ヘキサヒドロ−１，２−ジアリルフタレート、３，６−エンドメチレン−３−メチル−ヘキサヒドロ−１，２−ジアリルフタレート、３，６−エンドメチレン−４−メチル−ヘキサヒドロ−１，２−ジアリルフタレート等を例示することができ、好ましくはヘキサヒドロ−１，２−ジアリルフタレート、３−メチル−ヘキサヒドロ−１，２−ジアリルフタレート、４−メチル−ヘキサヒドロ−１，２−ジアリルフタレートである。中でも、ヘキサヒドロ−１，２−ジアリルフタレートが好ましい。上記アリル系化合物からなる群より選択される少なくとも１種以上を、重合することで得られるアリル系重合体を不飽和ポリエステル樹脂組成物に用いることができる。 The allyl compound represented by the above formula (I) is not particularly limited, and a commercially available one may be purchased or synthesized. Specific examples include hexahydro-1,2-diallyl phthalate, hexahydro-1,3-diallyl isophthalate, hexahydro-1,4-diallyl terephthalate, 3-methyl-hexahydro-1,2-diallyl phthalate, 4-methyl- Hexahydro-1,2-diallyl phthalate, 3,6-endomethylene-3-methyl-hexahydro-1,2-diallyl phthalate, 3,6-endomethylene-4-methyl-hexahydro-1,2-diallyl phthalate, etc. Preferred examples include hexahydro-1,2-diallyl phthalate, 3-methyl-hexahydro-1,2-diallyl phthalate, and 4-methyl-hexahydro-1,2-diallyl phthalate. Among these, hexahydro-1,2-diallyl phthalate is preferable. An allyl polymer obtained by polymerizing at least one selected from the group consisting of the above allyl compounds can be used for the unsaturated polyester resin composition.
上記式（Ｉ）で表されるアリル系化合物の重合方法は、特に限定されず、通常の重合反応を用いることができる。また、重合反応において、未反応のアリル系化合物の単量体を回収し、再び重合反応に用いてもよい。 The polymerization method of the allylic compound represented by the above formula (I) is not particularly limited, and a normal polymerization reaction can be used. In the polymerization reaction, unreacted allylic monomer may be recovered and used again for the polymerization reaction.
本発明に用いる式（Ｉ）で表されるアリル系化合物の単量体は、空気中の酸素により重合し得るので、重合開始剤を用いることなく、重合することができる。また、必要に応じて、適宜重合開始剤を添加してもよい。重合開始剤を用いることで、より高分子量の重合体を短時間に得ることができる。 Since the monomer of the allylic compound represented by the formula (I) used in the present invention can be polymerized by oxygen in the air, it can be polymerized without using a polymerization initiator. Moreover, you may add a polymerization initiator suitably as needed. By using a polymerization initiator, a higher molecular weight polymer can be obtained in a short time.
本発明のアリル系重合体（Ｂ）の含有量は、不飽和ポリエステル（Ａ）１００重量部に対して、５〜９００重量部であればよく、１０〜８００重量部であることが好ましく、１０〜３００重量部であることがより好ましく、１０〜２００重量部であることがさらに好ましい。上記範囲内であれば、本発明の効果を十分に得ることができる。 The content of the allylic polymer (B) of the present invention may be 5 to 900 parts by weight, preferably 10 to 800 parts by weight, with respect to 100 parts by weight of the unsaturated polyester (A). More preferably, it is -300 weight part, and it is further more preferable that it is 10-200 weight part. If it is in the said range, the effect of this invention can fully be acquired.
重合開始剤（Ｃ）
本発明に用いる重合開始剤（Ｃ）は、ジ−ｔｅｒｔ−ブチルパーオキサイド、ジクミルパーオキサイドの如きジアルキルパーオキサイド類やジアリルパーオキサイド類、ｔｅｒｔ−ブチル−ペルオキシベンゾエートのようなペルオキシエステル類、ｔｅｒｔ−ブチル−ペルオキシ−イソプロピルカーボネートペルオキシド類、１，１−ジ−ｔｅｒｔ−ブチル−ペルオキシ−シクロヘキサンのようなペルオキシケタール類、ベンゾイルパーオキサイド、２，４−ジクロルベンゾインパーオキサイドのようなジアロイルパーオキサイド類やジアシルパーオキサイド類、ヒドロペルオキシドのようなヒドロペルオキシド類、アゾビスイソブチロニトリルのようなアゾ化合物等を例示することができる。
Polymerization initiator (C)
The polymerization initiator (C) used in the present invention is composed of dialkyl peroxides such as di-tert-butyl peroxide and dicumyl peroxide, diallyl peroxides, peroxy esters such as tert-butyl-peroxybenzoate, tert -Peroxyketals such as butyl-peroxy-isopropyl carbonate peroxides, 1,1-di-tert-butyl-peroxy-cyclohexane, benzoyl peroxide, diaroyl peroxides such as 2,4-dichlorobenzoin peroxide And diacyl peroxides, hydroperoxides such as hydroperoxide, azo compounds such as azobisisobutyronitrile, and the like.
本発明の重合開始剤（Ｃ）の使用量は、不飽和ポリエステル（Ａ）１００重量部に対して、０．１〜２０重量部が好ましく、３〜１０重量部がより好ましい。硬化速度を維持し成形性を良くするには３重量部以上が望ましい。また、機械的強度の低下を防止するためには１０重量部以下であることが望ましい。 0.1-20 weight part is preferable with respect to 100 weight part of unsaturated polyester (A), and, as for the usage-amount of the polymerization initiator (C) of this invention, 3-10 weight part is more preferable. In order to maintain the curing rate and improve the moldability, 3 parts by weight or more is desirable. Moreover, in order to prevent a mechanical strength fall, it is desirable that it is 10 weight part or less.
無機充填剤（Ｄ）
本発明の不飽和ポリエステル樹脂組成物には、必要に応じて無機充填剤（Ｄ）を添加してもよい。無機充填剤（Ｄ）として、溶融シリカ、結晶シリカ、アルミナ、石英ガラス、炭酸カルシウム、水酸化アルミニウム、硫酸カルシウム等の金属類の水和物、ガラス粉末、タルク、マイカ等を例示することができる。無機充填剤の粒径は、０．１〜１００μｍである。好ましくは、０．５〜６０μｍである。粒径が小さすぎると、組成物粘度が大きくなり、強化繊維に十分含浸せず、材料内部にエアーを混入しやすくなり、成形品に巣が入りやすい。一方、粒径が大きすぎると、粒子の比表面積が小さくなることにより、流動性が低下する。
Inorganic filler (D)
You may add an inorganic filler (D) to the unsaturated polyester resin composition of this invention as needed. Examples of the inorganic filler (D) include fused silica, crystalline silica, alumina, quartz glass, hydrates of metals such as calcium carbonate, aluminum hydroxide, and calcium sulfate, glass powder, talc, and mica. . The particle size of the inorganic filler is 0.1 to 100 μm. Preferably, it is 0.5-60 micrometers. If the particle size is too small, the composition viscosity increases, the reinforcing fibers are not sufficiently impregnated, air is likely to be mixed into the material, and the molded product tends to nest. On the other hand, if the particle size is too large, the specific surface area of the particles becomes small, and the fluidity is lowered.
本発明の無機充填剤（Ｄ）の添加量は、不飽和ポリエステル（Ａ）１００重量部に対して、１０〜１０００重量部であればよく、２００〜８００重量部がより好ましい。添加量が少ないと、成形前の材料の取扱い性が低下する。また、添加量が多いと、粘度が大幅に上昇し、成形加工時の流動性が低下するとともに、強化繊維に対する含浸性が低下し、材料内部にエアーを混入しやすくなり、成形品に巣が入りやすい。 The addition amount of the inorganic filler (D) of the present invention may be 10 to 1000 parts by weight, and more preferably 200 to 800 parts by weight with respect to 100 parts by weight of the unsaturated polyester (A). When the addition amount is small, the handleability of the material before molding decreases. In addition, if the amount added is large, the viscosity is greatly increased, the fluidity during the molding process is lowered, the impregnation property for the reinforcing fibers is lowered, air is easily mixed into the material, and the molded product has a nest. Easy to enter.
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、繊維強化剤、低収縮剤、離型剤、増粘剤、顔料、減粘剤等の当該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。 In addition to the above components, the unsaturated polyester resin composition of the present invention contains components known in the art such as fiber reinforcing agents, low shrinkage agents, mold release agents, thickeners, pigments, thickeners, etc. In the range which does not inhibit the effect of this invention, it can contain.
本発明に用いられる繊維強化剤としては、特に限定されず、当該技術分野において公知のものを用いることができる。繊維強化材の例としては、ガラス繊維、パルプ繊維、テトロン（登録商標）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例示することができる。中でも、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を用いることが好ましい。 It does not specifically limit as a fiber reinforcement used for this invention, A well-known thing can be used in the said technical field. Examples of fiber reinforcing materials include various organic fibers and inorganic fibers such as glass fibers, pulp fibers, Tetron (registered trademark) fibers, vinylon fibers, carbon fibers, aramid fibers, and wollastonite. Among them, it is preferable to use chopped strand glass cut to a fiber length of about 1.5 to 25 mm.
本発明に用いられる低収縮剤としては、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。これらは、単独又は２種以上を組み合わせて用いることができる。 Examples of the low shrinkage agent used in the present invention include thermoplastic polymers generally used as low shrinkage agents such as polystyrene, polymethyl methacrylate, polyvinyl acetate, saturated polyester, and styrene-butadiene rubber. These can be used alone or in combination of two or more.
本発明に用いられる離型剤としては、ステアリン酸、ステアリン酸亜鉛、ステアリン酸カルシウム、ステアリン酸アルミニウム、ステアリン酸マグネシウム、カルナバワックス等を例示することができる。これらは、単独又は２種以上を組み合わせて用いることができる。
本発明に用いられる増粘剤としては、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金属酸化物、及びイソシアネート化合物等を例示することができる。これらは、単独又は２種以上を組み合わせて用いることができる。
Examples of the mold release agent used in the present invention include stearic acid, zinc stearate, calcium stearate, aluminum stearate, magnesium stearate, carnauba wax and the like. These can be used alone or in combination of two or more.
Examples of the thickener used in the present invention include metal oxides such as magnesium oxide, magnesium hydroxide, calcium hydroxide, and calcium oxide, and isocyanate compounds. These can be used alone or in combination of two or more.
本発明の不飽和ポリエステル樹脂組成物は、当該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混練することによって製造することができる The unsaturated polyester resin composition of the present invention can be produced by kneading using a method usually performed in the technical field, for example, a kneader.
本発明の不飽和ポリエステル樹脂組成物は、所望の形状に成形して硬化することによって成形物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、当該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、射出成形等を用いることができる。 The unsaturated polyester resin composition of the present invention can be molded into a desired shape and cured to produce a molded product. The molding and curing method is not particularly limited, and a method usually performed in the technical field, for example, compression molding, transfer molding, injection molding, or the like can be used.
実施例
以下、実施例を挙げて、本発明をより具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
Examples Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
（分析方法）
後述する製造例において、アリル系重合体の分析は下記に記載の方法を用いて行った。
(Analysis method)
In the production examples described later, the analysis of the allyl polymer was performed using the method described below.
１）アリル系重合体の重量平均分子量（Ｍｗ）、分子量分布（Ｍｗ／Ｍｎ）
重量平均分子量（Ｍｗ）、分子量分布（Ｍｗ／Ｍｎ）はＧＰＣを用いて測定した。標準ポリスチレン換算の重量平均分子量の値である。
カラム：ＳｈｏｄｅｘＫＦ−８０６Ｌ、ＫＦ−８０４、ＫＦ−８０３、ＫＦ−８０２、ＫＦ−８０１を直列に接続
流速：１．０ｍＬ／ｍｉｎ
温度：４０℃
検出：ＲＩＤ−６Ａ
試料：試料２０ｍｇをテトラヒドロフラン８ｍＬに溶解させ測定用のサンプルとした。
1) Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of allyl polymer
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured using GPC. It is a value of weight average molecular weight in terms of standard polystyrene.
Column: Shodex KF-806L, KF-804, KF-803, KF-802, KF-801 connected in series Flow rate: 1.0 mL / min
Temperature: 40 ° C
Detection: RID-6A
Sample: A sample for measurement was prepared by dissolving 20 mg of a sample in 8 mL of tetrahydrofuran.
製造例１
ヘキサヒドロ−１，２−ジアリルフタレート重合体の重合
３Ｌのセパラブルフラスコにヘキサヒドロ−１，２−ジアリルフタレート（和光純薬工業株式会社）６００ｇを加え、１６０℃で加熱攪拌し、５時間反応させた。その後、氷浴にて６０℃まで冷却した後、フラスコにメタノール１．８ｋｇを加え得られた重合体を沈殿させた。その後、バス温度６０℃で１時間還流させ、得られた重合体からモノマーの抽出を行った。モノマー抽出後に得られた重合体を４０℃で８時間減圧乾燥した。(収量：１２０ｇ，収率：２０％)。得られた重合体（Ｍｗ＝６．１万，Ｍｗ／Ｍｎ＝３．９）を実施例に用いた。
Production Example 1
Polymerization of hexahydro-1,2-diallyl phthalate polymer To a 3 L separable flask, 600 g of hexahydro-1,2-diallyl phthalate (Wako Pure Chemical Industries, Ltd.) was added and stirred at 160 ° C. for 5 hours. . Then, after cooling to 60 degreeC with an ice bath, 1.8 kg of methanol was added to the flask, and the obtained polymer was precipitated. Thereafter, the mixture was refluxed for 1 hour at a bath temperature of 60 ° C., and monomers were extracted from the obtained polymer. The polymer obtained after the monomer extraction was dried under reduced pressure at 40 ° C. for 8 hours. (Yield: 120 g, yield: 20%). The obtained polymer (Mw = 61,000, Mw / Mn = 3.9) was used in the examples.
実施例１、及び比較例１
表１に示す各材料を配合し、組成物を得た。得られた組成物を予備混合後、１２０〜１３０℃の加熱ロールで溶融混練し、冷却後粉砕して各成形材料を得た。
Example 1 and Comparative Example 1
Each material shown in Table 1 was blended to obtain a composition. The obtained composition was premixed, melted and kneaded with a heating roll at 120 to 130 ° C., cooled and pulverized to obtain each molding material.
（表１の注）
※１ 不飽和ポリエステル樹脂：日本ユピカ株式会社製「不飽和ポリエステル８５４２」
※２ ヘキサヒドロ−１，２−ジアリルフタレート重合体：製造例１で重合した重合体
※３ ジアリルフタレート樹脂：ダイソー株式会社製「ダイソーダップＡ」
※４ 昭和電工株式会社製「ハイジライトＨ−３２」
※５ ガラス繊維：オーエンスコーニングジャパン株式会社製「０３ＩＥ８３０Ａ」
※６ 日油株式会社製「パークミルＤ」
※７ 堺化学工業株式会社製「ステアリン酸亜鉛」
(Note to Table 1)
* 1 Unsaturated polyester resin: "Unsaturated polyester 8542" manufactured by Iupika Japan
* 2 Hexahydro-1,2-diallyl phthalate polymer: polymer polymerized in Production Example 1 * 3 Diallyl phthalate resin: Daiso Dup A manufactured by Daiso Corporation
* 4 "Hijilite H-32" manufactured by Showa Denko KK
* 5 Glass fiber: “03IE830A” manufactured by Owens Corning Japan
* 6 “Park Mill D” manufactured by NOF Corporation
* 7 “Zinc stearate” manufactured by Sakai Chemical Industry Co., Ltd.
実施例および比較例で得られた各成形材料の流動性を下記の条件で測定した。測定結果を表２に示す。 The fluidity of each molding material obtained in the examples and comparative examples was measured under the following conditions. The measurement results are shown in Table 2.
流動性の測定
各成形材料が、細い渦巻き状の蚊取り線香の如きスパイラル状に硬化成形された部分の最長長さを測定し、その長さを流動性とし、その長さの変化を時系列的に測定した。測定は以下の条件で行った。
成形機械：３７トン移送成形機（北十字社製「トランスファーＡＴＡ３７型」）
測定金型：ＥＭＭＩスパイラルフロー（ダイソー自社製作）
測定温度：１５０℃（金型温度）
注入圧力：４９０ＭＰａ（５０ｋｇ／ｃｍ２）
試料量：１５ｃｃ×比重（約３０ｇ前後）
加圧時間：１８０ｓｅｃ
Measurement of fluidity Measure the longest length of each molding material that has been hardened and molded into a spiral shape like a thin spiral mosquito coil, make that length fluid, and change the length over time. It was measured. The measurement was performed under the following conditions.
Molding machine: 37-ton transfer molding machine ("Transfer ATA37 type" manufactured by North Cross)
Measurement mold: EMMI spiral flow (manufactured by Daiso)
Measurement temperature: 150 ° C. (mold temperature)
Injection pressure: 490 MPa (50 kg / cm 2 )
Sample amount: 15cc x specific gravity (about 30g)
Pressurization time: 180 sec
曲げ強さ
各成形材料を金型温度１６０度、成形時間４分間で圧縮成形および移送成形により作製し、成形品を得、ＪＩＳ−Ｋ６９１１「熱硬化性プラスチック一般試験方法」に準じて、株式会社東洋精機製作所製ＳＴＲＯＧＲＡＰＨ Ｗを用いて測定を行った。
Bending strength Each molding material was produced by compression molding and transfer molding at a mold temperature of 160 ° C. and a molding time of 4 minutes to obtain a molded product. According to JIS-K6911 “General Thermosetting Plastic Testing Method” Measurement was performed using STROGRAPH W manufactured by Toyo Seiki Seisakusho.
体積抵抗率
圧縮成形により成形品を得、ＪＩＳ−Ｋ６９１１「熱硬化性プラスチック一般試験方法」に準じてＨＥＷＬＥＴＴ ＰＡＣＫＡＲＤ社製４３２９Ａ ＨＩＧＨ ＲＥＳＩＳＴＡＮＣＥ ＭＥＴＥＲを用いて測定を行った。
Volume resistivity A molded product was obtained by compression molding, and measurement was performed using a 4329A HIGH RESISTANCE METER manufactured by HEWLETT PACKARD in accordance with JIS-K6911 “General Test Method for Thermosetting Plastics”.
表２に示すように、新規アリル系重合体を用いた不飽和ポリエステル樹脂組成物は、モノマー成分を添加することなく従来のものと比較して高い流動性を持つことがわかった。 As shown in Table 2, it was found that the unsaturated polyester resin composition using the novel allylic polymer has higher fluidity than the conventional one without adding a monomer component.
本発明の不飽和ポリエステル樹脂組成物は、電気的特性及び機械的特性を実質的に損なうことなく非常に優れた流動性を有した不飽和ポリエステル樹脂成形材料に関するものである。本発明の不飽和ポリエステル樹脂成形材料は、優れた流動性を生かし、例えば小型・肉薄のコイルボビン、スイッチケース、端子板、コネクター、マグネットスイッチ等の電気・電子部等に使用できる。 The unsaturated polyester resin composition of the present invention relates to an unsaturated polyester resin molding material having excellent flowability without substantially impairing electrical and mechanical properties. The unsaturated polyester resin molding material of the present invention makes use of excellent fluidity and can be used, for example, in electric / electronic parts such as small and thin coil bobbins, switch cases, terminal plates, connectors, and magnet switches.
Claims (5)
一般式（Ｉ）で表されるアリル系化合物を重合して得られるアリル系重合体（Ｂ）と
（ＣＨＲ１＝ＣＲ２−ＣＨ２−Ｏ−ＣＯ)ｎ−Ｘ （Ｉ）
[Ｒ１およびＲ２は、それぞれ、ＨまたはＣＨ３を表し、
Ｘはアルキル置換基を有していてもよい飽和の４〜８員環の環状骨格を表し、ｎは２または３を表す。]
重合開始剤（Ｃ）を、含有してなる電気・電子部品用不飽和ポリエステル樹脂組成物であって、
アリル系重合体（Ｂ）が、式（Ｉ）中のＸが以下の環状骨格の少なくとも１つを有するアリル系化合物を重合したものである組成物。
An allyl polymer (B) obtained by polymerizing an allyl compound represented by the general formula (I) and (CHR 1 = CR 2 —CH 2 —O—CO) n —X (I)
[R 1 and R 2 each represent H or CH 3 ;
X represents a saturated 4- to 8-membered cyclic skeleton optionally having an alkyl substituent, and n represents 2 or 3. ]
An unsaturated polyester resin composition for electric and electronic parts, comprising a polymerization initiator (C),
The composition in which the allylic polymer (B) is obtained by polymerizing an allylic compound in which X in the formula (I) has at least one of the following cyclic skeletons.
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