WO1997033942A1 - Unsaturated polyester resin composition and sheetlike molding material - Google Patents
Unsaturated polyester resin composition and sheetlike molding material Download PDFInfo
- Publication number
- WO1997033942A1 WO1997033942A1 PCT/JP1997/000673 JP9700673W WO9733942A1 WO 1997033942 A1 WO1997033942 A1 WO 1997033942A1 JP 9700673 W JP9700673 W JP 9700673W WO 9733942 A1 WO9733942 A1 WO 9733942A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- unsaturated polyester
- polyester resin
- resin composition
- weight
- parts
- Prior art date
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- 229920006337 unsaturated polyester resin Polymers 0.000 title claims abstract description 97
- 239000000203 mixture Substances 0.000 title claims abstract description 81
- 239000012778 molding material Substances 0.000 title claims description 46
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 48
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012779 reinforcing material Substances 0.000 claims description 40
- 239000000945 filler Substances 0.000 claims description 21
- 239000000835 fiber Substances 0.000 claims description 18
- 239000003638 chemical reducing agent Substances 0.000 claims description 14
- 239000002562 thickening agent Substances 0.000 claims description 13
- 239000011342 resin composition Substances 0.000 claims description 8
- 238000000465 moulding Methods 0.000 abstract description 15
- 238000002156 mixing Methods 0.000 abstract description 13
- 238000001816 cooling Methods 0.000 abstract description 10
- 230000000994 depressogenic effect Effects 0.000 abstract 1
- 239000003677 Sheet moulding compound Substances 0.000 description 20
- 230000000704 physical effect Effects 0.000 description 15
- 229920006305 unsaturated polyester Polymers 0.000 description 14
- 239000002253 acid Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- 239000004412 Bulk moulding compound Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- -1 diaryl phthalate Chemical compound 0.000 description 10
- 239000003365 glass fiber Substances 0.000 description 10
- 239000003112 inhibitor Substances 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 239000000654 additive Substances 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical class C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 150000008064 anhydrides Chemical class 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
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000011521 glass 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
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003756 stirring Methods 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
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-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
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004135 Bone phosphate Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000002928 artificial marble Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 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
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- JBRVDBBLWMNHDA-UHFFFAOYSA-N ethane-1,2-diol;dihydrochloride Chemical compound Cl.Cl.OCCO JBRVDBBLWMNHDA-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 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
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920001778 nylon Polymers 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
- 239000012766 organic filler Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- DBSDMAPJGHBWAL-UHFFFAOYSA-N penta-1,4-dien-3-ylbenzene Chemical compound C=CC(C=C)C1=CC=CC=C1 DBSDMAPJGHBWAL-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 239000012749 thinning agent Substances 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/06—Unsaturated polyesters
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Definitions
- the present invention relates to an unsaturated polyester resin suitably used for a sheet-like molding material such as SMC (sheet molding compound), or a bulk-forming material such as BMC (bulk molding compound).
- SMC sheet molding compound
- BMC bulk molding compound
- the present invention relates to a composition and a sheet-like molding material containing the unsaturated polyester resin composition.
- unsaturated polyester resins have been suitably used for, for example, SMC and BMC.
- molding materials such as SMC and BMC using unsaturated polyester resin shrink during curing, and the reinforcing glass fibers emerge, so that the cured product (molded product) loses its surface smoothness. There is a problem that.
- thermoplastic polymer as a low-shrinkage agent at the time of curing in order to prevent the reinforcing glass fiber from floating and to improve the surface smoothness.
- the amount of the thermoplastic polymer is increased to sufficiently prevent the glass arrowhead from rising, the thermoplastic polymer will rise (scumming), and the surface smoothness will decrease. This causes the problem of causing
- Japanese Patent Publication No. 51-12776 Japanese Patent Publication No. 63-613 44 No. 4 discloses an unsaturated polyester using ⁇ -dimensional styrene polymer as a low-shrinking agent to reduce shrinkage during curing, prevent such scumming, and improve surface smoothness.
- a resin composition is disclosed.
- the unsaturated polyester resin composition shrinks not only at the time of curing but also at the time of cooling after molding of the molded article. Therefore, even if only the shrinkage during curing is reduced, good surface smoothness cannot be obtained.
- the above-mentioned conventional unsaturated polyester resin composition can reduce shrinkage during curing by using a three-dimensional styrene polymer as a low-shrinkage agent, but also reduces shrinkage during cooling after molding. It cannot be done, and it is hard to say that the surface smoothness of vermilion is sufficient.
- the use of a large amount of a low-shrinking agent causes an increase in the viscosity of the unsaturated polyester resin composition, which impairs the impregnation property of reinforcing materials such as glass fibers and reduces defects such as blistering of molded articles. It is easy to occur.
- the viscosity of the unsaturated polyester resin composition increases, molding becomes difficult when the unsaturated polyester resin composition is used for a sheet-like molding material such as SMC. This is because sheet-like molding materials such as SMC use unsaturated polyester resin composition as compared to BMC, etc., which can knead a composition containing a reinforcing agent by using a kneader or the like. This is due to the remarkable decrease in the impregnation property of the steel.
- the present invention has been made in view of the above-mentioned conventional problems, and has an object to provide an unsaturated polyester resin composition and a sheet-like composition capable of obtaining a molded article having excellent physical properties such as surface smoothness and gloss. It is to provide a molding material. Disclosure of the invention
- the inventors of the present application have conducted intensive studies to achieve the above object, and as a result, have found that an unsaturated polyester resin having a hydrogenated bisfunol skeleton, a low-shrinking agent containing a three-dimensional styrene polymer, and an unsaturated resin containing a narrowing agent
- the polyester resin composition can suppress not only shrinkage upon curing but also shrinkage upon cooling after molding, whereby a molded article having excellent physical properties such as surface smoothness and gloss can be obtained. And completed the present invention.
- the inventors of the present application have stated that the above-mentioned unsaturated polyester resin composition can be suitably used for a sheet-like molding material, and that the sheet-like molding material containing the unsaturated polyester resin composition is cured. It has been found that, in addition to the shrinkage, the shrinkage upon cooling after molding can be suppressed, whereby a molded article having excellent physical properties such as surface smoothness and gloss can be obtained.
- the unsaturated polyester resin composition of the present invention comprises: an unsaturated polyester resin having a hydrogenated bisphenol skeleton; a low-shrinking agent containing a three-dimensional styrene polymer; It is characterized by containing an agent.
- the unsaturated polyester resin composition of the present invention is a low-shrinking agent containing a three-dimensional styrene polymer with respect to 100 parts by weight of an unsaturated polyester resin having a hydrogenated bisphenol skeleton. 1
- a mixture containing 1 part by weight to 20 parts by weight and a filler of 190 parts by weight to 350 parts by weight is adjusted by using a viscosity reducing agent so that the viscosity at 35 ° C. becomes 1000 boise or less.
- a sheet-like molding material of the present invention is characterized by including the above-mentioned unsaturated polyester resin composition in order to solve the above-mentioned problems.
- the above configuration in addition to shrinkage during curing, shrinkage during cooling after molding can be suppressed, thereby obtaining a molded article having excellent physical properties such as surface smoothness and gloss.
- the unsaturated polyester resin composition can be suitably used, for example, for a sheet-like molding material such as SMC and a bulk-like molding material such as BMC.
- the unsaturated polyester resin composition is excellent in impregnating property with respect to the reinforcing material
- a sheet-like molding material in which the viscosity of a component (compound) other than the reinforcing material greatly affects the impregnating property with respect to the reinforcing material, It can be particularly preferably used.
- the unsaturated polyester resin composition according to the present invention contains an unsaturated polyester resin having a hydrogenated bisphenol skeleton, a low-shrinking agent containing three-dimensional styrene polymer, and a viscosity reducing agent.
- the unsaturated Boriesuteru resin used in the present invention as long as it has a hydrogen mold Sufuwenoru backbone, especially c unsaturated Boriesuteru resin is not limited in the acid component, such as hydrogenated Bisufu Nord A like Can be easily obtained by dissolving the unsaturated polyester obtained by the condensation reaction with an alcohol component containing hydrogenated bisphenols in a polymerizable monomer.
- the acid component is not particularly limited, but specifically, for example, unsaturated dibasic acids such as maleic acid, fumaric acid, itaconic acid, and anhydrides thereof; And saturated dibasic acids such as tetrahydrophthalic acid, isophthalic acid, terephthalic acid, adipic acid, sebacic acid, and acetic acid; and anhydrides thereof. Also, if necessary, A tribasic or higher polybasic acid such as ritic acid and pyromellitic acid may be used. One of these acid components may be used alone, or two or more of them may be appropriately mixed and used.
- Alcohol components other than hydrogenated bisphenols are not particularly limited, but specific examples include ethylene glycol and its multimers, propylene glycol and its multimers, neopentyl glycol, butanediol, and hexane. Examples include dihydric alcohols such as diol, propylene oxide, and ethylene oxide. If necessary, a trihydric or higher polyhydric alcohol such as trimethylol brono, olefin, glycerin, and pen-erythritol may be used. One of these alcohol components may be used alone, or two or more thereof may be appropriately mixed and used.
- the content of the above hydrogenated bisphenols in all alcohol components is not particularly limited, but is preferably 10 mol% or more. If the content of the above hydrogenated bisphenols is less than 10 mol%, after the obtained molding material containing the unsaturated polyester resin composition is molded, the molded article shrinks when cooled (hereinafter referred to as heat shrinkage). ) May not be sufficiently suppressed. As described above, by reacting the acid component with the alcohol component containing hydrogenated bisphenols, an unsaturated polyester resin having a high heat distortion temperature (HDT) and thus capable of suppressing the above-mentioned heat shrinkage can be obtained. .
- HDT heat distortion temperature
- the method for producing the above-mentioned unsaturated polyester is not particularly limited-a conventional method can be used.
- the mixing ratio of each component, that is, the acid component and the alcohol component is not particularly limited, and the presence or absence of other additives and the amount used thereof are not particularly limited.
- the reaction time and reaction temperature in the above reaction may be appropriately set so that the above reaction is completed, and are not particularly limited.
- a polymerization inhibitor in order to prevent gelation due to polymerization and to adjust the storage stability or curability of the resulting unsaturated polyester.
- the polymerization inhibitor is not particularly limited, and a conventionally known polymerization inhibitor can be used.
- Specific examples of the polymerization inhibitor include, for example, hydroquinone, methyl hydroquinone, p-t-butyl catechol, t-butyl hydroquinone, toluhydroquinone, p-benzoquinone, naphthoquinone, and hydroquinone. Monomethyl ether, phenothiazine, copper naphthenate and the like.
- One of these polymerization inhibitors may be used alone, or two or more thereof may be appropriately mixed and used.
- the amount of the polymerization inhibitor added is not particularly limited.
- the polymerizable monomer for dissolving the unsaturated polyester is not particularly limited, but specific examples thereof include styrene, methyl methacrylate, butyl acetate, vinyl toluene, and diaryl phthalate. Is mentioned. These polymerizable monomers may be used alone or in a combination of two or more.
- the amount of the polymerizable monomer is not particularly limited, but is preferably in the range of 10% by weight to 70% by weight, and more preferably in the range of 30% by weight to 50% by weight based on the amount of the unsaturated polyester. Is more preferred.
- the low-shrinkage agent used in the present invention is a three-dimensional styrene in order to sufficiently suppress shrinkage (hereinafter, referred to as cure shrinkage) during curing of a molding material using the unsaturated polyester resin composition.
- cure shrinkage a three-dimensional styrene in order to sufficiently suppress shrinkage (hereinafter, referred to as cure shrinkage) during curing of a molding material using the unsaturated polyester resin composition.
- cure shrinkage a three-dimensional styrene in order to sufficiently suppress shrinkage (hereinafter, referred to as cure shrinkage) during curing of a molding material using the unsaturated polyester resin composition.
- cure shrinkage a three-dimensional styrene in order to sufficiently suppress shrinkage (hereinafter, referred to as cure shrinkage) during curing of a molding material using the unsaturated polyester resin composition.
- the three-dimensional styrene polymer is a three-dimensional polymer obtained by polymerizing a sty
- the monomer copolymerizable with the above-mentioned styrene monomer that is, the other monomer used as needed in the production of the three-dimensional styrene polymer, is not particularly limited, but specifically, Examples thereof include vinyl acetate, (meth) acrylic acid, (meth) acrylic acid esters, acrylonitrile, and acrylamide. One of these monomers may be used alone, or two or more of them may be appropriately mixed and used. The amount of the other monomer is not particularly limited.
- the crosslinking agent is not particularly limited, but specifically, for example, divinylbenzene derivatives such as divinylbenzene and divinyltoluene; and alkylglycol dichloride such as ethylene glycol dichloride. Derivatives; alkyl glycol dimethacrylate derivatives such as ethylene glycol dimethacrylate; and diaryl phthalate.
- divinylbenzene derivatives such as divinylbenzene and divinyltoluene
- alkylglycol dichloride such as ethylene glycol dichloride.
- alkyl glycol dimethacrylate derivatives such as ethylene glycol dimethacrylate
- diaryl phthalate a compound formed from ethylene glycol dimethacrylate
- One of these crosslinking agents may be used alone, or two or more of them may be appropriately used in combination.
- crosslinking agents is not particularly limited, but is preferably adjusted so that the crosslinking density of the obtained three-dimensional styrene polymer is in the range of 0.2% to 30%. It is more preferable that the adjustment is made in the range of 5% to 10%.
- the low-shrinking agent other than the above-mentioned three-dimensional styrene polymer include polystyrene, polymethyl methacrylate, polyethylene, and polyethylene.
- Olefin-based addition polymers and copolymers such as propylene; and saturated polymers such as saturated polyesters, nylons, and polyurethanes, but are not particularly limited thereto.
- these low-shrinkage agents may be used alone or in a combination of two or more.
- the narrowing agent used in the present invention is not particularly limited as long as it can reduce the viscosity of the obtained unsaturated polyester resin composition.
- a thickener include, for example, a saturated polyester compound, BYK (registered trademark; product names W900, W905, W960, W966, W98) 0, W990, W99 5. W99 6. W910) and the like. These thickeners may be used alone or in a combination of two or more.
- the unsaturated polyester resin composition of the present invention comprises the above-mentioned unsaturated polyester resin having a bisphenol X-nord skeleton, a low-shrinking agent containing three-dimensional styrene polymer, and a viscosity reducing agent.
- the unsaturated polyester resin composition further contains additives such as a filler and a reinforcing material, the unsaturated polyester resin composition has more excellent physical properties and can be used as a molding material that can be used for various uses. .
- the above-mentioned filler examples include aluminum hydroxide, magnesium carbonate, barium sulfate, calcium sulfate, calcium carbonate, anoremina, stone powder, silica (silica sand), glass powder, clay,
- examples include inorganic fillers such as kaolin and talc, and organic fillers, but are not particularly limited. One of these fillers may be used alone, or two or more of them may be appropriately used in combination. Among these fillers, calcium carbonate and aluminum hydroxide are particularly preferred. Also, the average of the filler g
- the form such as the particle size is not particularly limited.
- the unsaturated resin composition further includes a filler, the curing shrinkage and the heat shrinkage can be further reduced.
- the reinforcing material include, for example, inorganic arrowheads such as glass fibers, carbon fibers, metal fibers, and fibers made of ceramic; organic fibers such as aramid and polyester; and natural fibers.
- inorganic arrowheads such as glass fibers, carbon fibers, metal fibers, and fibers made of ceramic
- organic fibers such as aramid and polyester
- natural fibers there is no particular limitation.
- One of these reinforcing materials may be used alone, or two or more of them may be appropriately used in combination.
- the form of the fiber include roving, chopped strand, mat, and cloth (woven fabric), and the fiber length and the number of converged fibers are not particularly limited.
- the above-mentioned fiber length is preferably 1/4 inch or less, and a molded article finally obtained by using a fiber having a fiber length of 1/4 inch or less as the reinforcing material. Can be further improved in surface smoothness.
- the unsaturated polyester resin composition further contains a reinforcing material
- the unsaturated polyester resin composition according to the present invention comprises, in addition to the unsaturated polyester resin, a low-shrinking agent, a thickening agent, a filler, and a reinforcing material, if necessary, other additives. May be included.
- a low-shrinking agent e.g., a low-shrinking agent
- a thickening agent e.g., a filler
- a reinforcing material if necessary, other additives.
- other additives e.g., various additives generally used can be adopted, and are not particularly limited.
- the above-mentioned other additives depend on desired physical properties and applications, but include, for example, a release agent, a curing agent, a polymerization inhibitor, a polymerizable monomer, and a coloring agent.
- a thickener may be used at the time of use.
- These other additives use only one kind Or two or more of them may be used as appropriate.
- the release agent include fatty acids such as stearic acid and lauric acid, and metal salts thereof.
- the enlarging agent include, for example, alkaline earth metal oxides such as magnesium oxide, calcium oxide, and beryllium oxide; alkaline earth metals such as magnesium hydroxide and calcium hydroxide. Metal hydroxide and the like.
- the curing agent include, for example, organic peroxides such as t-butyl veroxy benzoate and t-butyl vinyl oxycarbonate; azo compounds such as azobisisobutyl nitrile; Known radical polymerization initiators and the like can be mentioned.
- the polymerization inhibitor and the polymerizable monomer for example, the same compounds as the compounds exemplified in the method for producing the unsaturated polyester resin can be used.
- the coloring agent include known inorganic pigments and organic pigments.
- the unsaturated polyester resin composition according to the present invention comprises an unsaturated polyester resin having the above-mentioned hydrogenated bisphenol skeleton, a low-shrinking agent containing a three-dimensional styrene polymer, a viscosity reducing agent, and a filler if necessary. It can be easily obtained by mixing (kneading) the reinforcing material and other additives.
- the content of each raw material (that is, the mixing ratio of each raw material) in the unsaturated polyester resin composition is not particularly limited, the mixing ratio of the low shrinkage agent to the unsaturated polyester resin (that is, The total blending ratio of the original styrene polymer and the other low-shrinking agent is preferably within the range of 11 to 20 parts by weight of the low-shrinking agent per 100 parts by weight of the unsaturated polyester resin. If the blending ratio of the above-mentioned low shrinkage agent is less than 11 parts by weight, It is not preferable because shrinkage cannot be sufficiently suppressed.
- the upper limit of the amount of the above-mentioned low-shrinkage agent is not particularly limited, because the more the amount of the above-mentioned shrinkage agent, the more the effect of suppressing shrinkage can be exhibited.
- the blending ratio of the above-mentioned low-shrinking agent exceeds 20 parts by weight, the viscosity of the resulting unsaturated polyester resin composition becomes too high, and the workability is reduced, or when a reinforcing material or the like is used.
- the impregnation property of the reinforcing material or the like is reduced. There is a possibility that the molded article may swell. For this reason, in practical use, it is preferable that the amount is 20 or less.
- the ratio of the three-dimensional styrene polymer is 7 to 20 parts by weight based on 100 parts by weight of the unsaturated polyester resin. It is preferable to use within the range of parts.
- the mixing ratio of the thickener to the unsaturated polyester resin is preferably in the range of 1 part by weight to 8 parts by weight for 100 parts by weight of the unsaturated polyester resin.
- the unsaturated polyester resin composition according to the present invention contains a viscosity reducing agent, it is possible to increase the amount of a low-shrinkage agent and a filler added without changing the viscosity, and to enhance a reinforcing material such as glass fiber. Thus, it is possible to maintain the impregnation property of the molded article and improve the surface smoothness of the finally obtained molded article.
- the unsaturated polyester resin composition of the present application is excellent in impregnating property with respect to a reinforcing material by containing the above-mentioned viscosity reducing agent, and can be used not only for bulk molding materials such as BMC but also for sheet molding materials such as SMC. It can be suitably used.
- the amount of the thinning agent, the viscosity of the unsaturated Boriesuteru resin composition, Chi immediately, the ⁇ during mixing of the raw materials may be an amount which can be adjusted to 1000 Boyes following 35 e C, There is no particular limitation. However, if the compounding ratio of the above-mentioned viscosity reducing agent is less than 1 part by weight, the unsaturated polyester having the desired physical properties can be obtained. It is not preferable because the ester resin composition may not be able to be obtained. If the addition ratio of the above-mentioned thickener is too small, especially as a molding material
- the amount of the filler is not particularly limited, but is 350 parts by weight or less based on 100 parts by weight of the unsaturated polyester resin composition. Is preferred. However, in order to obtain a remarkable effect of suppressing curing shrinkage and heat shrinkage due to the addition of the filler, it is particularly preferable to use the filler in the range of 190 parts by weight to 350 parts by weight. As described above, by highly filling the filler, the curing shrinkage and the heat shrinkage can be sufficiently suppressed. If the content of the unsaturated polyester resin composition is more than 350 parts by weight, the viscosity of the resulting unsaturated polyester resin composition becomes too high, resulting in reduced workability or the use of a reinforcing material or the like. In such a case, the impregnating property of the reinforcing material or the like is reduced, and the molded product may be swollen.
- the unsaturated polyester resin composition of the present invention is characterized in that the low-shrinkage agent containing the three-dimensional styrene polymer is used in an amount of from 11 parts by weight to 100 parts by weight of the unsaturated polyester resin having a hydrogenated bisphenol skeleton. If it contains 20 parts by weight and 190 to 350 parts by weight of filler, the resulting mixture is at 35 The degree of change is more than 1 000 voices. Therefore, the mixture is adjusted to have a viscosity of not more than 1000 Boys at 35 using a viscosity reducing agent. In addition to the shrinkage during curing, it is also possible to suppress the shrinkage during cooling after molding. It is possible to obtain an unsaturated polyester resin composition capable of obtaining a molded article having excellent physical properties such as surface smoothness and gloss.
- the amount of other additives used as required is not particularly limited, and the type and combination with other raw materials such as an unsaturated polyester resin, a low-shrinking agent, and a viscosity-reducing agent are also not limited.
- the use of the unsaturated polyester resin composition and the desired physical properties may be appropriately set, and the amount of the reinforcing material added when the reinforcing material is added may be determined based on the amount of the unsaturated polyester resin composition. Although it depends on the composition, application, and desired physical properties, etc., it is preferable to add the unsaturated polyester resin composition so that the content thereof is in the range of 1% by weight to 30% by weight, preferably 7% by weight to 15% by weight. It is more preferable to add so as to be within the range of% by weight.
- the method of addition (mixing) when the above-mentioned reinforcing material is added is not particularly limited, and may be appropriately set according to the form of the reinforcing material.
- the reinforcing material when the reinforcing material is a mat cloth or the like, the reinforcing material may be impregnated with a component other than the reinforcing material (hereinafter, referred to as a compound for convenience of explanation).
- the compound may be kneaded with the reinforcing material.
- the unsaturated polyester resin composition thus obtained can be used as various molding materials per se, but is also suitably used as a resin composition for a sheet-like molding material or a bulk-like molding material.
- sheet-like molding materials are prepared according to the usual method.
- -A method of impregnating a sheet-like (mat-like) reinforcing material 2 A method of stretching a compound into a sheet and sandwiching the reinforcing material with this sheet-like material; 3 A chopped strand-like reinforcement on a release film A method in which a material is dropped, a compound is supplied on the compound in a uniform thickness, and a demolding film is placed over the compound to remove bubbles.
- Unsaturated ballet with mixed (kneaded) reinforcing material It can be obtained by forming the steal resin composition into a sheet by various methods, such as a method of stretching it in a sheet shape.
- the sheet-like molding material obtained in this way can be wrapped with a release film such as polyethylene, polypropylene, or aluminum-deposited film and aged to be a sheet-like molding material having excellent moldability.
- the bulk molding material is formed into a bulk by kneading an unsaturated polyester resin composition containing, for example, a reinforcing material filler, a release agent, and the like using a kneading machine such as a double-arm kneader. In this way, it can be easily obtained.
- the bulk molding material obtained in this way can be made into a bulk molding material having excellent moldability by wrapping with the above release film and aging.
- Molding materials such as sheet-like molding materials and bulk-like molding materials are molded by, for example, compression molding, injection molding, transfer molding, or the like to obtain molded products having excellent physical properties such as gloss and surface smoothness. Can be.
- the method of curing the unsaturated polyester resin composition of the present invention and various molding materials containing the same is not particularly limited. That is, the unsaturated polyester resin composition according to the present invention is applicable to various molding methods. As described above, the molded product obtained by molding the unsaturated polyester resin composition according to the present invention and the molding material containing the same has gloss and surface smoothness. Physical properties such as properties are improved than before.
- the unsaturated polyester resin composition according to the present invention is configured to include an unsaturated polyester resin having a hydrogenated bisphenol skeleton, a low-shrinking agent containing a three-dimensional styrene polymer, and a thickening agent. It is.
- the ratio of the low-shrinking agent and the thickening agent to 100 parts by weight of the unsaturated polyester resin is in the range of 11 to 20 parts by weight of the low-shrinking agent and in the range of 1 to 8 parts by weight of the thickening agent.
- the unsaturated polyester resin composition preferably further contains a reinforcing material.
- a fiber having a fiber length of 1/4 inch or less is suitable.
- the unsaturated polyester resin composition according to the present invention comprises 11 parts by weight to 20 parts by weight of a low-shrinking agent containing a three-dimensional styrene polymer with respect to 100 parts by weight of the unsaturated polyester resin having a hydrogenated bisphenol skeleton.
- Filler 1 A mixture containing 90 parts by weight to 350 parts by weight is adjusted by using a viscosity reducing agent such that the viscosity at 35 wt.
- the sheet-like molding material according to the present invention is configured to include the above-mentioned unsaturated polyester resin composition.
- the present invention can provide an unsaturated polyester resin composition which can be used.
- the unsaturated polyester resin composition can be suitably used, for example, as a sheet-like molding material such as SMC, or a bulk-like molding material such as BMC. Since the unsaturated polyester resin composition is excellent in impregnating property with respect to a reinforcing material, it is particularly suitably used for a sheet-like molding material in which the viscosity of a compound greatly affects the impregnating property with respect to a reinforcing material. thing Can be. For this reason, the sheet-like molding material containing the unsaturated polyester resin composition can also suppress shrinkage upon cooling after molding, in addition to shrinkage upon curing, thereby improving surface smoothness and the like. A molded product with excellent physical properties such as gloss can be obtained.
- Examples of molded articles using the unsaturated polyester resin composition according to the present invention include various articles used outdoors such as so-called daylighting domes, benches, tables, tanks, public notice boards, waterproof boards, etc .; , Components of automobiles, railway vehicles, ships, etc .; exterior materials of structures, such as roofs and walls; artificial marble suitable for bathtubs and kitchen counters; and electrical components. is not.
- the obtained SMC was wrapped in an aluminum vapor-deposited film and aged at 40 ° C. for about 20 hours.
- the SMC is applied to a die adjusted with an upper die 145'C and a lower die 135, and is pressed and maintained at a pressure of 70 kgf Zcm 2 (surface pressure) for 4 minutes to form a 30 cm ⁇ 30 cm flat plate. Molded. The surface smoothness and gloss of the obtained molded product were visually evaluated. Table 1 shows the results.
- Example 1 a fiber length of 1/4 was used instead of the glass fiber having a fiber length of 1 inch.
- An SMC was prepared by performing the same blending and operation as in Example 1 except that the glass fiber of INCH was used. Thereafter, using the SMC, a molded article was obtained in the same manner as in Example 1. The surface smoothness and gloss of the obtained molded product were visually evaluated. Table 1 shows the results.
- the unsaturated polyester resin composition according to the present invention can suppress not only shrinkage during curing but also shrinkage during cooling after molding. Therefore, when the unsaturated polyester resin composition according to the present invention is used, a molded article having excellent physical properties such as surface smoothness and gloss can be obtained.
- the unsaturated ballistic resin composition can be suitably used, for example, as a sheet-like molding material such as SMC, or a bulk-like molding material such as BMC. Since the unsaturated ball polyester resin composition has excellent impregnation property with respect to the strength-imparting material, it is less than a reinforcing material. It can be particularly suitably used for a sheet-like molding material in which the viscosity of an external component (compound) greatly affects the impregnation property of the reinforcing material.
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Abstract
An unsaturated polyester resin composition is prepared by blending an unsaturated polyester resin having a hydrogenated bisphenol skeleton with a shrinkage lowering agent comprising a three-dimensional styrene polymer and a viscosity depressant. This composition is inhibited from shrinkage both in curing and in cooling after molding. Thus, the composition can give molded articles excellent in surface smoothness, gloss and so on.
Description
明 細 害 不飽和ポリエステル樹脂組成物およびシ一 ト状成形材料 技術分野 Field damage Unsaturated polyester resin composition and sheet-like molding material
本発明は、 例えば S MC (シ一トモ一ルディ ングコンパウン ド） 等の シー ト状成形材料や、 BMC (バルクモ一ルディ ングコンパウン ド） 等 のバルク状成形材料に好適に用いられる不飽和ボリエステル樹脂組成物. および、 該不飽和ボリエステル樹脂組成物を含むシ一 ト状成形材料に関 するものである。 背景技術 The present invention relates to an unsaturated polyester resin suitably used for a sheet-like molding material such as SMC (sheet molding compound), or a bulk-forming material such as BMC (bulk molding compound). The present invention relates to a composition and a sheet-like molding material containing the unsaturated polyester resin composition. Background art
従来より、 不飽和ボリエステル樹脂は、 例えば、 SMCや BMC等に 好適に用いられている。 しかしながら、 不飽和ボリエステル樹脂を用い た SMCや BMC等の成形材料は、 硬化時に収縮が起こり、 補強用のガ ラス繊維が浮き出すため、 その硬化物 （成形品） の表面平滑性が失われ るという問題点を有している。 Conventionally, unsaturated polyester resins have been suitably used for, for example, SMC and BMC. However, molding materials such as SMC and BMC using unsaturated polyester resin shrink during curing, and the reinforcing glass fibers emerge, so that the cured product (molded product) loses its surface smoothness. There is a problem that.
そこで、 補強用のガラス織維の浮き出しを防止し、 上記表面平滑性を 向上させるために、 硬化時の低収縮化剤として熱可塑性重合体を使用す ることが知られている。 ところが、 ガラス鏃維の浮きだしを充分に防止 するために上記熱可塑性重合体の添加量を增すと、 熱可塑性重合体の浮 きだし （スカ ミ ンング） が起こり、 かえって表面平滑性を低下させると いう問題が生じる。 Therefore, it is known to use a thermoplastic polymer as a low-shrinkage agent at the time of curing in order to prevent the reinforcing glass fiber from floating and to improve the surface smoothness. However, if the amount of the thermoplastic polymer is increased to sufficiently prevent the glass arrowhead from rising, the thermoplastic polymer will rise (scumming), and the surface smoothness will decrease. This causes the problem of causing
そこで、 例えば、 特公昭 5 1 - 1 2 7 6号公報、 特公昭 6 3 - 6 1 3
4 4号公報等には、 硬化時の収縮を低減させ、 このようなスカ ミ ンング を防止し、 表面平滑性を向上させるために、 低収縮化剤として Ξ次元ス チレンボリマーを用いた不飽和ボリエステル樹脂組成物が開示されてい 。 Therefore, for example, Japanese Patent Publication No. 51-12776, Japanese Patent Publication No. 63-613 44 No. 4 discloses an unsaturated polyester using ボ -dimensional styrene polymer as a low-shrinking agent to reduce shrinkage during curing, prevent such scumming, and improve surface smoothness. A resin composition is disclosed.
しかしながら、 一般に、 不飽和ボリエステル樹脂組成物は、 硬化時以 外にも、 成形品の成形後の冷却時にも収縮が起こる。 このため、 硬化時 の収縮のみを低減しても、 良好な表面平滑性を得ることはできない。 つ まり、 上記従来の不飽和ボリエステル樹脂組成物は、 低収縮化剤として 三次元スチレンポリマーを用いることによって、 硬化時の収縮を低減さ せることはできるものの、 成形後の冷却時における収縮を低減させるこ とはできず、 その表面平滑性は、 朱だ充分であるとは言い難い。 However, generally, the unsaturated polyester resin composition shrinks not only at the time of curing but also at the time of cooling after molding of the molded article. Therefore, even if only the shrinkage during curing is reduced, good surface smoothness cannot be obtained. In other words, the above-mentioned conventional unsaturated polyester resin composition can reduce shrinkage during curing by using a three-dimensional styrene polymer as a low-shrinkage agent, but also reduces shrinkage during cooling after molding. It cannot be done, and it is hard to say that the surface smoothness of vermilion is sufficient.
さらに、 低収縮化剤を多量に使用することは、 不飽和ポリエステル樹 脂組成物の粘度の上昇を招くため、 ガラス繊維等の補強材に対する含浸 性が低下し、 成形品の膨れ等の欠陥を生じ易くなる。 特に、 不飽和ボリ エステル樹脂組成物の粘度が高くなると、 該不飽和ボリエステル樹脂組 成物を S M C等のシ一 ト状成形材料に用いる場合の成形が困難となる。 これは、 S M C等のシー ト状成形材料は、 ニーダ一等を使用することに より補強剤を含んだ組成物の混練が可能な B M C等に比べて、 不飽和ポ リエステル樹脂組成物の補強材に対する含浸性の低下が顕著であること による。 In addition, the use of a large amount of a low-shrinking agent causes an increase in the viscosity of the unsaturated polyester resin composition, which impairs the impregnation property of reinforcing materials such as glass fibers and reduces defects such as blistering of molded articles. It is easy to occur. In particular, when the viscosity of the unsaturated polyester resin composition increases, molding becomes difficult when the unsaturated polyester resin composition is used for a sheet-like molding material such as SMC. This is because sheet-like molding materials such as SMC use unsaturated polyester resin composition as compared to BMC, etc., which can knead a composition containing a reinforcing agent by using a kneader or the like. This is due to the remarkable decrease in the impregnation property of the steel.
本発明は、 上記従来の問題点に鑑みなされたものであり、 その目的は. 表面平滑性や光沢等の物性に優れた成形品を得ることができる不飽和ボ リエステル樹脂組成物およびシー ト状成形材料を提供することにある。
発明の開示 The present invention has been made in view of the above-mentioned conventional problems, and has an object to provide an unsaturated polyester resin composition and a sheet-like composition capable of obtaining a molded article having excellent physical properties such as surface smoothness and gloss. It is to provide a molding material. Disclosure of the invention
本願発明者等は、 上記目的を達成すべく鋭意検討した結果、 水素化ビ スフユノール骨格を有する不飽和ボリエステル樹脂と、 三次元スチレン ボリマーを含む低収縮化剤と、 減拈剤とを含む不飽和ボリエステル樹脂 組成物が、 硬化時の収縮に加えて、 成形後の冷却時の収縮をも抑制する ことができ、 これにより、 表面平滑性や光沢等の物性に優れた成形品を 得ることができることを見いだして本発明を完成させるに至った。 また. 本願発明者等は、 上記不飽和ボリエステル樹脂組成物は、 シー ト状成形 材料に好適に用いることができると共に、 該不飽和ポリエステル樹脂組 成物を含むシー ト状成形材料が、 硬化時の収縮に加えて、 成形後の冷却 時の収縮をも抑制することができ、 これにより、 表面平滑性や光沢等の 物性に優れた成形品を得ることができることを見いだした。 The inventors of the present application have conducted intensive studies to achieve the above object, and as a result, have found that an unsaturated polyester resin having a hydrogenated bisfunol skeleton, a low-shrinking agent containing a three-dimensional styrene polymer, and an unsaturated resin containing a narrowing agent The polyester resin composition can suppress not only shrinkage upon curing but also shrinkage upon cooling after molding, whereby a molded article having excellent physical properties such as surface smoothness and gloss can be obtained. And completed the present invention. Further, the inventors of the present application have stated that the above-mentioned unsaturated polyester resin composition can be suitably used for a sheet-like molding material, and that the sheet-like molding material containing the unsaturated polyester resin composition is cured. It has been found that, in addition to the shrinkage, the shrinkage upon cooling after molding can be suppressed, whereby a molded article having excellent physical properties such as surface smoothness and gloss can be obtained.
即ち、 本発明の不飽和ポリエステル樹脂組成物は、 上記の課題を解決 するために、 水素化ビスフヱノール骨格を有する不飽和ボリエステル樹 脂と、 三次元スチレンポリマ一を含む低収縮化剤と、 減粘剤とを含むこ とを特徴としている。 That is, in order to solve the above problems, the unsaturated polyester resin composition of the present invention comprises: an unsaturated polyester resin having a hydrogenated bisphenol skeleton; a low-shrinking agent containing a three-dimensional styrene polymer; It is characterized by containing an agent.
また、 本発明の不飽和ボリエステル樹脂組成物は、 上記の課題を解決 するために、 水素化ビスフェノール骨格を有する不飽和ボリエステル樹 脂 100重量部に対して、 三次元スチレンボリマ一を含む低収縮化剤 1 1重 量部〜 20重量部および充塡剤 190重量部〜 350重量部を含む混合物を、 減粘剤を用いて 35°Cにおける粘度が 1000ボイズ以下となるように調整し てなることを特徴としている。 Further, in order to solve the above-mentioned problems, the unsaturated polyester resin composition of the present invention is a low-shrinking agent containing a three-dimensional styrene polymer with respect to 100 parts by weight of an unsaturated polyester resin having a hydrogenated bisphenol skeleton. 1 A mixture containing 1 part by weight to 20 parts by weight and a filler of 190 parts by weight to 350 parts by weight is adjusted by using a viscosity reducing agent so that the viscosity at 35 ° C. becomes 1000 boise or less. Features.
さらに、 本発明のシー ト状成形材料は、 上記の課題を解決するために. 上記の不飽和ボリエステル樹脂組成物を含むことを特徴としている。
上記の構成によれば、 硬化時の収縮に加えて、 成形後の冷却時の収縮 をも抑制することができ、 これにより、 表面平滑性や光沢等の物性に優 れた成形品を得ることができる不飽和ボリエステル樹脂組成物を提供す ることができる。 該不飽和ボリエステル樹脂組成物は、 例えば、 S M C 等のシー ト状成形材料や、 B M C等のバルク状成形材料等に好適に用い ることができる。 該不飽和ボリエステル樹脂組成物は、 補強材に対する 含浸性に優れているため、 補強材以外の成分 （コンバウン ド） の粘度が 補強材に対する含浸性に大きく影饗を及ぼすシー ト状成形材料に、 特に 好適に用いることができる。 Furthermore, a sheet-like molding material of the present invention is characterized by including the above-mentioned unsaturated polyester resin composition in order to solve the above-mentioned problems. According to the above configuration, in addition to shrinkage during curing, shrinkage during cooling after molding can be suppressed, thereby obtaining a molded article having excellent physical properties such as surface smoothness and gloss. It is possible to provide an unsaturated polyester resin composition which can be used. The unsaturated polyester resin composition can be suitably used, for example, for a sheet-like molding material such as SMC and a bulk-like molding material such as BMC. Since the unsaturated polyester resin composition is excellent in impregnating property with respect to the reinforcing material, a sheet-like molding material in which the viscosity of a component (compound) other than the reinforcing material greatly affects the impregnating property with respect to the reinforcing material, It can be particularly preferably used.
以下、 本発明を更に詳しく説明する。 Hereinafter, the present invention will be described in more detail.
本発明にかかる不飽和ボリエステル樹脂組成物は、 水素化ビスフェノ —ル骨格を有する不飽和ポリエステル樹脂と、 三次元スチレンボリマ一 を含む低収縮化剤と、 減粘剤とを含んでいる。 The unsaturated polyester resin composition according to the present invention contains an unsaturated polyester resin having a hydrogenated bisphenol skeleton, a low-shrinking agent containing three-dimensional styrene polymer, and a viscosity reducing agent.
本発明において用いられる上記不飽和ボリエステル樹脂は、 水素化ビ スフヱノール骨格を有するものであれば、 特に限定されるものではない c 該不飽和ボリエステル樹脂は、 酸成分と、 例えば水素化ビスフ ノール A等の水素化ビスフヱノ一ル類を含むアルコール成分との縮合反応によ り得られた不飽和ボリエステルを、 重合性単量体に溶解させることによ り容易に得ることができる。 The unsaturated Boriesuteru resin used in the present invention, as long as it has a hydrogen mold Sufuwenoru backbone, especially c unsaturated Boriesuteru resin is not limited in the acid component, such as hydrogenated Bisufu Nord A like Can be easily obtained by dissolving the unsaturated polyester obtained by the condensation reaction with an alcohol component containing hydrogenated bisphenols in a polymerizable monomer.
上記の酸成分としては、 特に限定されるものではないが、 具体的には, 例えば、 マレイン酸、 フマル酸、 ィタコン酸、 およびこれらの無水物等 の不飽和二塩基酸 ； フ夕ル酸、 テトラヒ ドロフ夕ル酸、 イソフタル酸、 テレフタル酸、 アジピン酸、 セバシン酸、 へッ ト酸、 およびこれらの無 水物等の飽和二塩基酸 ；等が挙げられる。 また、 必要に応じて、 ト リ メ
リ ッ ト酸、 ピロメ リ ッ ト酸等の 3価以上の多塩基酸等を用いてもよい。 これら酸成分は、 一種類のみを用いてもよく、 また、 二種類以上を適宜 混合して用いてもよい。 The acid component is not particularly limited, but specifically, for example, unsaturated dibasic acids such as maleic acid, fumaric acid, itaconic acid, and anhydrides thereof; And saturated dibasic acids such as tetrahydrophthalic acid, isophthalic acid, terephthalic acid, adipic acid, sebacic acid, and acetic acid; and anhydrides thereof. Also, if necessary, A tribasic or higher polybasic acid such as ritic acid and pyromellitic acid may be used. One of these acid components may be used alone, or two or more of them may be appropriately mixed and used.
水素化ビスフヱノール類以外のアルコール成分としては、 特に限定さ れるものではないが、 具体的には、 例えば、 エチレングリコールおよび その多量体、 プロピレングリ コールおよびその多量体、 ネオペンチルグ リコール、 ブタンジオール、 へキサンジオール、 酸化プロピレン、 酸化 エチレン等の 2価アルコールが挙げられる。 また、 必要に応じて、 ト リ メチロールブロノ、 'ン、 グリセリ ン、 ペン夕エリスリ トール等の 3価以上 の多価アルコールを用いてもよい。 これらアルコール成分は、 一種類の みを用いてもよく、 また、 二種類以上を適宜混合して用いてもよい。 Alcohol components other than hydrogenated bisphenols are not particularly limited, but specific examples include ethylene glycol and its multimers, propylene glycol and its multimers, neopentyl glycol, butanediol, and hexane. Examples include dihydric alcohols such as diol, propylene oxide, and ethylene oxide. If necessary, a trihydric or higher polyhydric alcohol such as trimethylol brono, olefin, glycerin, and pen-erythritol may be used. One of these alcohol components may be used alone, or two or more thereof may be appropriately mixed and used.
全アルコール成分中における上記水素化ビスフェノール類の含有量は, 特に限定されるものではないが、 10モル％以上であることが好ましい。 上記水素化ビスフ ノール類の含有量が 10モル％未満であれば、 得られ る不飽和ボリエステル樹脂組成物を含む成形材料を成形後、 冷却する際 の成形品の収縮 （以下、 熱収縮と記す） を充分に抑制することができな くなる虞れがある。 このように、 酸成分と、 水素化ビスフヱノール類を 含むアルコール成分とを反応させることによって、 熱変形温度 （H D T ) が高く、 よって上記熱収縮の抑制が可能な不飽和ボリエステル樹脂を 得ることができる。 The content of the above hydrogenated bisphenols in all alcohol components is not particularly limited, but is preferably 10 mol% or more. If the content of the above hydrogenated bisphenols is less than 10 mol%, after the obtained molding material containing the unsaturated polyester resin composition is molded, the molded article shrinks when cooled (hereinafter referred to as heat shrinkage). ) May not be sufficiently suppressed. As described above, by reacting the acid component with the alcohol component containing hydrogenated bisphenols, an unsaturated polyester resin having a high heat distortion temperature (HDT) and thus capable of suppressing the above-mentioned heat shrinkage can be obtained. .
上記不飽和ボリエステルの製造方法は、 特に限定されるものではなく - 常用の方法を用いることができる。 また、 各成分、 即ち、 酸成分とアル コール成分との配合割合は特に限定されるものではなく、 その他の添加 剤の有無並びにその使用量も特に限定されるものではない。 さらに、 上
記反応における反応時間並びに反応温度は、 上記反応が完結するように 適宜設定すればよく、 特に限定されるものではない。 The method for producing the above-mentioned unsaturated polyester is not particularly limited-a conventional method can be used. In addition, the mixing ratio of each component, that is, the acid component and the alcohol component is not particularly limited, and the presence or absence of other additives and the amount used thereof are not particularly limited. In addition, The reaction time and reaction temperature in the above reaction may be appropriately set so that the above reaction is completed, and are not particularly limited.
また、 上記反応に際して、 或いは反応後、 重合によるゲル化の防止や、 得られる不飽和ボリエステルの保存安定性または硬化性を調整するため に、 重合禁止剤を添加することが好ましい。 In addition, at or after the above reaction, it is preferable to add a polymerization inhibitor in order to prevent gelation due to polymerization and to adjust the storage stability or curability of the resulting unsaturated polyester.
上記重合禁止剤としては、 特に限定されるものではなく、 従来公知の 重合禁止剤を用いることができる。 上記重合禁止剤としては、 具体的に は、 例えば、 ハイ ドロキノ ン、 メチルハイ ドロキノ ン、 p- t -プチルカテ コール、 t -ブチルハイ ドロキノ ン、 トルハイ ドロキノ ン、 p-ベンゾキノ ン、 ナフ トキノ ン、 ハイ ドロキノ ンモノ メチルエーテル、 フエノチアジ ン、 ナフテン酸銅等が挙げられる。 これら重合禁止剤は、 一種類のみを 用いてもよく、 また、 二種類以上を適宜混合して用いてもよい。 尚、 上 記重合禁止剤の添加量は、 特に限定されるものではない。 The polymerization inhibitor is not particularly limited, and a conventionally known polymerization inhibitor can be used. Specific examples of the polymerization inhibitor include, for example, hydroquinone, methyl hydroquinone, p-t-butyl catechol, t-butyl hydroquinone, toluhydroquinone, p-benzoquinone, naphthoquinone, and hydroquinone. Monomethyl ether, phenothiazine, copper naphthenate and the like. One of these polymerization inhibitors may be used alone, or two or more thereof may be appropriately mixed and used. The amount of the polymerization inhibitor added is not particularly limited.
上記不飽和ボリエステルを溶解するための重合性単量体としては、 特 に限定されるものではないが、 具体的には、 例えば、 スチレン、 メタク リル酸メチル、 酢酸ビュル、 ビニルトルエン、 ジァリルフタレー ト等が 挙げられる。 これら重合性単量体は、 一種類のみを用いてもよいし、 二 種類以上を適宜混合して用いてもよい。 上記重合性単量体の配合量は、 特に限定されるものではないが、 不飽和ボリエステルに対して、 10重量 %〜70重量％の範囲内が好ましく、 30重量％〜50重量％の範囲内がさら に好ましい。 The polymerizable monomer for dissolving the unsaturated polyester is not particularly limited, but specific examples thereof include styrene, methyl methacrylate, butyl acetate, vinyl toluene, and diaryl phthalate. Is mentioned. These polymerizable monomers may be used alone or in a combination of two or more. The amount of the polymerizable monomer is not particularly limited, but is preferably in the range of 10% by weight to 70% by weight, and more preferably in the range of 30% by weight to 50% by weight based on the amount of the unsaturated polyester. Is more preferred.
また、 本発明において用いられる低収縮化剤は、 該不飽和ボリエステ ル樹脂組成物を用いた成形材料の硬化時における収縮 （以下、 硬化収縮 と記す） を充分に抑制するために、 三次元スチレンポリマーを含んでい
る。 上記三次元スチレンボリマーとは、 スチレ ンモノマーを単独で、 あ るいは、 スチレ ンモノマーと該スチレンモノマーと共重合可能な単量体 とを、 架橋剤の存在下で重合させることにより得られる三次元の網目構 造を有する架橋重合体である。 In addition, the low-shrinkage agent used in the present invention is a three-dimensional styrene in order to sufficiently suppress shrinkage (hereinafter, referred to as cure shrinkage) during curing of a molding material using the unsaturated polyester resin composition. Contains polymer You. The three-dimensional styrene polymer is a three-dimensional polymer obtained by polymerizing a styrene monomer alone or a styrene monomer and a monomer copolymerizable with the styrene monomer in the presence of a crosslinking agent. It is a crosslinked polymer having the following network structure.
上記スチ レ ンモノマーと共重合可能な単量体、 即ち、 三次元スチ レン ボリマーの製造において必要に応じて用いられるその他の単量体として は、 特に限定されるものではないが、 具体的には、 例えば、 酢酸ビニル、 (メタ） ァク リル酸、 （メタ） アタ リル酸エステル類、 ァク リ ロ二 ト リ ル、 アク リ ルア ミ ド等が挙げられる。 これら単量体は、 一種類のみを用 いてもよいし、 二種類以上を適宜混合して用いてもよい。 尚、 上記その 他の単量体の配合量は、 特に限定されるものではない。 The monomer copolymerizable with the above-mentioned styrene monomer, that is, the other monomer used as needed in the production of the three-dimensional styrene polymer, is not particularly limited, but specifically, Examples thereof include vinyl acetate, (meth) acrylic acid, (meth) acrylic acid esters, acrylonitrile, and acrylamide. One of these monomers may be used alone, or two or more of them may be appropriately mixed and used. The amount of the other monomer is not particularly limited.
架橋剤と しては、 特に限定されるものではないが、 具体的には、 例え ば、 ジビニルベンゼン、 ジビニル トルエン等のジビニルベンゼン誘導体 ； エチレングリ コールジ了ク リ レー ト等のアルキルグリ コールジァク リ レー ト誘導体 ； エチレングリ コールジメタク リ レー ト等のアルキルグリ コールジメ タク リ レー ト誘導体 ； ジァリルフタ レー ト等が挙げられる。 これら架橋剤は、 一種類のみを用いてもよく、 適宜、 二種類以上を混合 して用いてもよい。 The crosslinking agent is not particularly limited, but specifically, for example, divinylbenzene derivatives such as divinylbenzene and divinyltoluene; and alkylglycol dichloride such as ethylene glycol dichloride. Derivatives; alkyl glycol dimethacrylate derivatives such as ethylene glycol dimethacrylate; and diaryl phthalate. One of these crosslinking agents may be used alone, or two or more of them may be appropriately used in combination.
これら架橋剤の添加量は、 特に限定されるものではないが、 得られる 三次元スチ レ ンポリマーの架橋密度が 0. 2%〜30 %の範囲内となるよう に調整することが好ましく、 0. 5 %〜10 %の範囲内となるように調整す ることがさ らに好ましい。 The addition amount of these crosslinking agents is not particularly limited, but is preferably adjusted so that the crosslinking density of the obtained three-dimensional styrene polymer is in the range of 0.2% to 30%. It is more preferable that the adjustment is made in the range of 5% to 10%.
上記三次元スチレンボリマー以外の低収縮化剤としては、 具体的には. 例えば、 ボリスチレン、 ポリ メチルメタク リ レー ト、 ポリエチレン、 ボ
リプロピレン等のォレフィ ン系付加重合体および共重合体 ；飽和ボリェ ステル、 ナイロン、 ボリウレタン等の縮合重合体等が挙げられるが、 特 に限定されるものではない。 また、 これら低収縮化剤は、 一種類のみを 用いてもよく、 適宜、 二種類以上を混合して用いてもよい。 Specific examples of the low-shrinking agent other than the above-mentioned three-dimensional styrene polymer include polystyrene, polymethyl methacrylate, polyethylene, and polyethylene. Olefin-based addition polymers and copolymers such as propylene; and saturated polymers such as saturated polyesters, nylons, and polyurethanes, but are not particularly limited thereto. In addition, these low-shrinkage agents may be used alone or in a combination of two or more.
また、 本発明において用いられる上記減拈剤としては、 得られる不飽 和ボリエステル樹脂組成物の粘度を低下させることができるものであれ ば、 特に限定されるものではない。 このような减粘剤としては、 具体的 には、 例えば、 飽和ポリエステル系化合物、 B YK (登録商標 ； 品名 W 9 0 0. W 9 0 5 W 9 6 0、 W 9 6 5、 W 9 8 0、 W 9 9 0、 W 9 9 5. W 9 9 6. W 9 0 1 0 ) 等が挙げられる。 これら減粘剤は、 一種 類のみを用いてもよく、 適宜二種類以上を混合して用いてもよい。 In addition, the narrowing agent used in the present invention is not particularly limited as long as it can reduce the viscosity of the obtained unsaturated polyester resin composition. Specific examples of such a thickener include, for example, a saturated polyester compound, BYK (registered trademark; product names W900, W905, W960, W966, W98) 0, W990, W99 5. W99 6. W910) and the like. These thickeners may be used alone or in a combination of two or more.
本発明の不飽和ボリエステル樹脂組成物は、 上記水素化ビスフ Xノー ル骨格を有する不飽和ボリエステル樹脂と、 三次元スチレンボリマ一を 含む低収縮化剤と、 減粘剤とを含んでなる。 また、 該不飽和ポリエステ ル樹脂組成物が充塡剤や補強材等の添加剤をさらに含むことで、 さらに 優れた物性を有すると共に、 種々の用途に使用可能な成形材料として用 いることができる。 The unsaturated polyester resin composition of the present invention comprises the above-mentioned unsaturated polyester resin having a bisphenol X-nord skeleton, a low-shrinking agent containing three-dimensional styrene polymer, and a viscosity reducing agent. In addition, when the unsaturated polyester resin composition further contains additives such as a filler and a reinforcing material, the unsaturated polyester resin composition has more excellent physical properties and can be used as a molding material that can be used for various uses. .
上記充塡剤としては、 具体的には、 例えば、 水酸化アルミニウム、 炭 酸マグネシウム、 硫酸バリ ウム、 硫酸カルシウム、 炭酸カルシウム、 ァ ノレミ ナ、 石粉、 シリ 力 （珪砂） 、 ガラス粉、 ク レー、 カオリ ン、 タルク 等の無機充塡剤、 および、 有機充塡剤が挙げられるが、 特に限定される ものではない。 これら充填剤は、 一種類のみを用いてもよく、 適宜、 二 種類以上を混合して用いてもよい。 これら充塡剤のなかでも、 炭酸カル シゥムおよび水酸化アルミニウムが特に好ましい。 また、 充塡剤の平均
g Specific examples of the above-mentioned filler include aluminum hydroxide, magnesium carbonate, barium sulfate, calcium sulfate, calcium carbonate, anoremina, stone powder, silica (silica sand), glass powder, clay, Examples include inorganic fillers such as kaolin and talc, and organic fillers, but are not particularly limited. One of these fillers may be used alone, or two or more of them may be appropriately used in combination. Among these fillers, calcium carbonate and aluminum hydroxide are particularly preferred. Also, the average of the filler g
粒径等の形態は、 特に限定されるものではない。 上記不飽和ボ ' jエステ ル樹脂組成物がさらに充填剤を含むことで、 前記硬化収縮および熱収縮 をさらに低減させることができる。 The form such as the particle size is not particularly limited. When the unsaturated resin composition further includes a filler, the curing shrinkage and the heat shrinkage can be further reduced.
補強材としては、 具体的には、 例えば、 ガラス織維、 炭素繊維、 金属 繊維、 セラ ミ ツクからなる織維等の無機鏃維； ァラミ ドゃポリエステル 等からなる有機繊維；天然繊維等が挙げられるが、 特に限定されるもの ではない。 これら補強材は、 一種類のみを用いてもよく、 適宜、 二種類 以上を混合して用いてもよい。 また、 繊維の形態は、 例えば、 ロービン グ、 チョ ップトス トランド、 マッ ト、 クロス （織物） 等が挙げられ、 そ の繊維長や収束本数等も特に限定されるものではない。 そのなかでも上 記織維長は、 1/4 インチ以下であることが好ましく、 上記補強材として 1/4 インチ以下の繊維長を有する織維を用いることで、 最終的に得られ る成形品の表面平滑性を一層向上させることができる。 このように、 該 不飽和ボリエステル樹脂組成物がさらに補強材を含むことで、 例えば S M C等のシー ト状成形材料や B M C等のバルク状成形材料等に好適に用 いることができる。 Specific examples of the reinforcing material include, for example, inorganic arrowheads such as glass fibers, carbon fibers, metal fibers, and fibers made of ceramic; organic fibers such as aramid and polyester; and natural fibers. However, there is no particular limitation. One of these reinforcing materials may be used alone, or two or more of them may be appropriately used in combination. Examples of the form of the fiber include roving, chopped strand, mat, and cloth (woven fabric), and the fiber length and the number of converged fibers are not particularly limited. Among them, the above-mentioned fiber length is preferably 1/4 inch or less, and a molded article finally obtained by using a fiber having a fiber length of 1/4 inch or less as the reinforcing material. Can be further improved in surface smoothness. As described above, since the unsaturated polyester resin composition further contains a reinforcing material, it can be suitably used for a sheet-like molding material such as SMC or a bulk-forming material such as BMC.
また、 本発明にかかる不飽和ボリエステル榭脂組成物は、 上記不飽和 ポリエステル樹脂、 低収縮化剤、 減粘剤、 充塡剤、 および補強材以外に. 必要に応じて、 その他の添加剤を含んでいてもよい。 上記その他の添加 剤は、 一般に用いられている各種の添加剤を採用することができ、 特に 限定されるものではない。 上記その他の添加剤としては、 所望する物性 や用途にもよるが、 例えば、 離型剤、 硬化剤、 重合禁止剤、 重合性単量 体、 着色剤等が挙げられる。 また、 作業性を向上させるために、 使用時 に増粘剤を用いてもよい。 これらその他の添加剤は、 一種類のみを用い
てもよいし、 適宜、 二種類以上を混合して用いてもよい。 In addition, the unsaturated polyester resin composition according to the present invention comprises, in addition to the unsaturated polyester resin, a low-shrinking agent, a thickening agent, a filler, and a reinforcing material, if necessary, other additives. May be included. As the above-mentioned other additives, various additives generally used can be adopted, and are not particularly limited. The above-mentioned other additives depend on desired physical properties and applications, but include, for example, a release agent, a curing agent, a polymerization inhibitor, a polymerizable monomer, and a coloring agent. Moreover, in order to improve workability, a thickener may be used at the time of use. These other additives use only one kind Or two or more of them may be used as appropriate.
上記離型剤としては、 具体的には、 例えば、 ステアリ ン酸、 ラウリル 酸等の脂肪酸およびその金属塩等が挙げられる。 また、 増拈剤としては、 具体的には、 例えば、 酸化マグネシウム、 酸化カルシウム、 酸化ベリ リ ゥム等のアルカ リ土類金属酸化物 ； 水酸化マグネシウム、 水酸化カルシ ゥ厶等のアルカリ土類金属水酸化等が挙げられる。 硬化剤 （重合開始剤 ) としては、 具体的には、 例えば、 t-ブチルバーォキシべゾエー ト、 t - ブチルバ一ォキシカーボネー ト等の有機過酸化物 ； ァゾビスイソプチ口 二ト リル等のァゾ化合物等、 従来公知のラジカル重合開始剤等が挙げら れる。 重合禁止剤や重合性単量体としては、 例えば、 前記不飽和ポリエ ステル樹脂の製造方法においてそれぞれ例示した化合物と同様の化合物 を用いることができる。 また、 着色剤としては、 公知の無機顔料や有機 顔料等が挙げられる。 Specific examples of the release agent include fatty acids such as stearic acid and lauric acid, and metal salts thereof. Examples of the enlarging agent include, for example, alkaline earth metal oxides such as magnesium oxide, calcium oxide, and beryllium oxide; alkaline earth metals such as magnesium hydroxide and calcium hydroxide. Metal hydroxide and the like. Examples of the curing agent (polymerization initiator) include, for example, organic peroxides such as t-butyl veroxy benzoate and t-butyl vinyl oxycarbonate; azo compounds such as azobisisobutyl nitrile; Known radical polymerization initiators and the like can be mentioned. As the polymerization inhibitor and the polymerizable monomer, for example, the same compounds as the compounds exemplified in the method for producing the unsaturated polyester resin can be used. Examples of the coloring agent include known inorganic pigments and organic pigments.
本発明にかかる不飽和ボリエステル樹脂組成物は、 上記水素化ビスフ ェノール骨格を有する不飽和ボリエステル樹脂、 三次元スチレンボリマ 一を含む低収縮化剤、 減粘剤、 および、 必要に応じて充塡剤や補強材、 その他の添加剤等を混合 （混練） することにより、 容易に得ることがで さる。 The unsaturated polyester resin composition according to the present invention comprises an unsaturated polyester resin having the above-mentioned hydrogenated bisphenol skeleton, a low-shrinking agent containing a three-dimensional styrene polymer, a viscosity reducing agent, and a filler if necessary. It can be easily obtained by mixing (kneading) the reinforcing material and other additives.
上記不飽和ボリエステル樹脂組成物における各原料の含有量 （即ち、 各原料の配合割合） は、 特に限定されるものではないが、 不飽和ポリエ ステル樹脂に対する低収縮化剤の配合割合 （即ち、 三次元スチレンポリ マ一とその他の低収縮化剤との合計の配合割合） は、 不飽和ボリエステ ル樹脂 100重量部に対して、 低収縮化剤 11重量部〜 20重量部の ίδ囲内が 好ましい。 上記低収縮化剤の配合割合が 11重量部未満であれば、 硬化収
縮を充分に抑制することができなくなるため好ましくない。 上記低収縮 化剤は、 その配合量が多い程、 収縮抑制効果を顕著に発揮することがで きるため、 その配合量の上限としては、 特に限定されるものではない。 しかしながら、 上記低収縮化剤の配合割合が 20重量部を越えると、 得ら れる不飽和ボリエステル樹脂組成物の粘度が高くなりすぎ、 作業性が低 下したり、 捕強材等を用いた場合に、 補強材等に対する含浸性が低下し. 成形品の膨れ等を招く虞れがある。 このため、 実使用上、 20重尊部以下 であることが好ましい。 さらに、 上記硬化収縮を充分に抑制するために, 低収縮化剤のなかでも、 特に、 三次元スチレンボリマーの割合は、 不飽 和ボリエステル樹脂 100重量部に対して、 7重量部〜 20重量部の範囲内 で使用することが好ましい。 Although the content of each raw material (that is, the mixing ratio of each raw material) in the unsaturated polyester resin composition is not particularly limited, the mixing ratio of the low shrinkage agent to the unsaturated polyester resin (that is, The total blending ratio of the original styrene polymer and the other low-shrinking agent is preferably within the range of 11 to 20 parts by weight of the low-shrinking agent per 100 parts by weight of the unsaturated polyester resin. If the blending ratio of the above-mentioned low shrinkage agent is less than 11 parts by weight, It is not preferable because shrinkage cannot be sufficiently suppressed. The upper limit of the amount of the above-mentioned low-shrinkage agent is not particularly limited, because the more the amount of the above-mentioned shrinkage agent, the more the effect of suppressing shrinkage can be exhibited. However, if the blending ratio of the above-mentioned low-shrinking agent exceeds 20 parts by weight, the viscosity of the resulting unsaturated polyester resin composition becomes too high, and the workability is reduced, or when a reinforcing material or the like is used. In addition, the impregnation property of the reinforcing material or the like is reduced. There is a possibility that the molded article may swell. For this reason, in practical use, it is preferable that the amount is 20 or less. Further, in order to sufficiently suppress the curing shrinkage, among the low-shrinking agents, particularly, the ratio of the three-dimensional styrene polymer is 7 to 20 parts by weight based on 100 parts by weight of the unsaturated polyester resin. It is preferable to use within the range of parts.
また、 上記不飽和ボリエステル樹脂に対する減粘剤の配合割合は、 不 飽和ボリエステル樹脂 100重量部に対して、 減粘剤 1重量部〜 8重量部 の範囲内が好ましい。 本発明にかかる不飽和ポリエステル樹脂組成物が 減粘剤を含むことで、 粘度を変えずに低収縮化剤や充塡剤等の添加量を 増大させることができると共に、 ガラス繊維等の補強材に対する含浸性 を維持し、 最終的に得られる成形品の表面平滑性を向上させることがで きる。 このため、 本願の不飽和ボリエステル樹脂組成物は、 上記減粘剤 を含むことで補強材に対する含浸性に優れ、 B M C等のバルク状成形材 料だけでなく S M C等のシー ト状成形材料にも好適に用いることができ る。 上記減粘剤の配合量は、 不飽和ボリエステル樹脂組成物の粘度、 即 ち、 各原料の混合時の拈度を、 35eCで 1000ボイズ以下に調整することが できる量であればよく、 特に限定されるものではない。 但し、 上記減粘 剤の配合割合が 1重量部未満であれば、 所望する物性を備えた不飽和ポ
リエステル樹脂組成物を得ることができなくなる虞れがあるので好まし くない。 上記減粘剤の添加割合が少なすぎると、 特に、 成形材料としてThe mixing ratio of the thickener to the unsaturated polyester resin is preferably in the range of 1 part by weight to 8 parts by weight for 100 parts by weight of the unsaturated polyester resin. When the unsaturated polyester resin composition according to the present invention contains a viscosity reducing agent, it is possible to increase the amount of a low-shrinkage agent and a filler added without changing the viscosity, and to enhance a reinforcing material such as glass fiber. Thus, it is possible to maintain the impregnation property of the molded article and improve the surface smoothness of the finally obtained molded article. For this reason, the unsaturated polyester resin composition of the present application is excellent in impregnating property with respect to a reinforcing material by containing the above-mentioned viscosity reducing agent, and can be used not only for bulk molding materials such as BMC but also for sheet molding materials such as SMC. It can be suitably used. The amount of the thinning agent, the viscosity of the unsaturated Boriesuteru resin composition, Chi immediately, the拈度during mixing of the raw materials, may be an amount which can be adjusted to 1000 Boyes following 35 e C, There is no particular limitation. However, if the compounding ratio of the above-mentioned viscosity reducing agent is less than 1 part by weight, the unsaturated polyester having the desired physical properties can be obtained. It is not preferable because the ester resin composition may not be able to be obtained. If the addition ratio of the above-mentioned thickener is too small, especially as a molding material
S M C等のシー ト状成形材料を得る場合には、 B M C等のバルク状成形 材料を得る場合に比べてガラス繊維等の補強材に対する含浸性が低下す る。 このため、 成形が困難となる虞れがある。 また、 上記減粘剤の配合 割合が 8重量部を越えると、 該不飽和ボリエステル樹脂組成物の増拈後 の粘度が、 成形作業等に好適な所定の値に達しないか、 若しくは達する までに長時間を有する虞れがある。 このため、 実使用上、 上記範囲内に おいて用いることが好ましい。 When a sheet-like molding material such as SMC is obtained, the impregnation property with respect to a reinforcing material such as glass fiber is lower than when a bulk-forming material such as BMC is obtained. For this reason, molding may be difficult. When the mixing ratio of the above-mentioned viscosity reducing agent exceeds 8 parts by weight, the viscosity of the unsaturated polyester resin composition after enrichment does not reach a predetermined value suitable for molding work or the like, or until the viscosity reaches the predetermined value. There is a risk of having a long time. For this reason, in practical use, it is preferable to use within the above range.
また、 充¾剤を添加する場合には、 該充墳剤の添加量は、 特に限定さ れるものではないが、 不飽和ボリエステル樹脂組成物 1 00重量部に対し て、 350重量部以下であることが好ましい。 但し、 該充塡剤を添加した ことによる顕著な硬化収縮および熱収縮の抑制効果を得るためには、 1 90重量部〜 350重量部の範囲内で用いることが特に好ましい。 このよう に、 上記充塡剤を高充塡することで、 上記硬化収縮および熱収縮を充分 に抑制することが可能となる。 尚、 上記不飽和ボリエステル樹脂組成物 に対する上記配合割合が 350重量部を越えると、 得られる不飽和ボリエ ステル樹脂組成物の粘度が高くなりすぎ、 作業性が低下したり、 補強材 等を用いた場合に、 補強材等に対する含浸性が低下し、 成形品の膨れ等 を招く虞れがあるので好ましくない。 When a filler is added, the amount of the filler is not particularly limited, but is 350 parts by weight or less based on 100 parts by weight of the unsaturated polyester resin composition. Is preferred. However, in order to obtain a remarkable effect of suppressing curing shrinkage and heat shrinkage due to the addition of the filler, it is particularly preferable to use the filler in the range of 190 parts by weight to 350 parts by weight. As described above, by highly filling the filler, the curing shrinkage and the heat shrinkage can be sufficiently suppressed. If the content of the unsaturated polyester resin composition is more than 350 parts by weight, the viscosity of the resulting unsaturated polyester resin composition becomes too high, resulting in reduced workability or the use of a reinforcing material or the like. In such a case, the impregnating property of the reinforcing material or the like is reduced, and the molded product may be swollen.
このように、 本発明の不飽和ボリエステル樹脂組成物が、 水素化ビス フ ノール骨格を有する不飽和ボリエステル樹脂 1 00重量部に対して、 三次元スチレンボリマ—を含む低収縮化剤 1 1重量部〜 20重量部および充 塡剤 190重量部〜 350重量部を含む場合、 得られる混合物の 35でにおけ
る拈度は 1 000ボイズ以上となる。 そこで、 該混合物を、 減粘剤を用いて 35でにおける粘度が 1000ボイズ以下となるように調整することによって. 硬化時の収縮に加えて、 成形後の冷却時の収縮をも抑制することができ. 表面平滑性や光沢等の物性に優れた成形品を得ることができる不飽和ボ リエステル樹脂組成物を得ることができる。 As described above, the unsaturated polyester resin composition of the present invention is characterized in that the low-shrinkage agent containing the three-dimensional styrene polymer is used in an amount of from 11 parts by weight to 100 parts by weight of the unsaturated polyester resin having a hydrogenated bisphenol skeleton. If it contains 20 parts by weight and 190 to 350 parts by weight of filler, the resulting mixture is at 35 The degree of change is more than 1 000 voices. Therefore, the mixture is adjusted to have a viscosity of not more than 1000 Boys at 35 using a viscosity reducing agent. In addition to the shrinkage during curing, it is also possible to suppress the shrinkage during cooling after molding. It is possible to obtain an unsaturated polyester resin composition capable of obtaining a molded article having excellent physical properties such as surface smoothness and gloss.
また、 必要に応じて用いられるその他の添加剤の使用量も特に限定さ れるものではなく、 その種類や、 不飽和ボリエステル樹脂、 低収縮化剤. および減粘剤等のその他の原料との組み合わせ、 不飽和ボリエステル樹 脂組成物の用途、 並びに、 所望する物性等に応じて適宜設定すればよい, また、 補強材を添加する場合における補強材の添加量は、 不飽和ボリ エステル樹脂組成物の組成や用途、 並びに、 所望する物性等にもよるが. 不飽和ボリエステル樹脂組成物における含有量が 1重量％〜30重量％の 範囲内となるように添加することが好ましく、 7重量％〜15重量％の範 囲内となるように添加することがさらに好ましい。 Also, the amount of other additives used as required is not particularly limited, and the type and combination with other raw materials such as an unsaturated polyester resin, a low-shrinking agent, and a viscosity-reducing agent are also not limited. The use of the unsaturated polyester resin composition and the desired physical properties may be appropriately set, and the amount of the reinforcing material added when the reinforcing material is added may be determined based on the amount of the unsaturated polyester resin composition. Although it depends on the composition, application, and desired physical properties, etc., it is preferable to add the unsaturated polyester resin composition so that the content thereof is in the range of 1% by weight to 30% by weight, preferably 7% by weight to 15% by weight. It is more preferable to add so as to be within the range of% by weight.
上記補強材を添加する場合の添加 （混合） 方法は、 特に限定されるも のではなく、 補強材の形態に応じて適宜設定すればよい。 例えば、 補強 材の形態がマツ トゃクロス等である場合には、 該補強材に、 補強材以外 の成分 （以下、 説明の便宜上、 コンパゥン ドと称する） を含浸させれば よい。 また、 例えば、 補強材の形態が口一ビングやチョ ップトス トラン ド等である場合には、 該補強材とコンパウン ドとを混練すればよい。 このようにして得られた不飽和ポリエステル樹脂組成物は、 それ自身. 各種成形材料として用いることができるが、 シー ト状成形材料やバルク 状成形材料用の樹脂組成物としても好適に用いられる。 The method of addition (mixing) when the above-mentioned reinforcing material is added is not particularly limited, and may be appropriately set according to the form of the reinforcing material. For example, when the reinforcing material is a mat cloth or the like, the reinforcing material may be impregnated with a component other than the reinforcing material (hereinafter, referred to as a compound for convenience of explanation). Further, for example, when the form of the reinforcing material is a mouth bing or a chopped strand, the compound may be kneaded with the reinforcing material. The unsaturated polyester resin composition thus obtained can be used as various molding materials per se, but is also suitably used as a resin composition for a sheet-like molding material or a bulk-like molding material.
例えば、 シート状成形材料は、 常法に従い、 ①上記コンパゥン ドをシ
ー ト状 （マッ ト状） の補強材に含浸させる方法、 ②コンパウン ドをシー ト状に延伸し、 このシート状物で補強材を挟む方法、 ③離型性フィルム 上にチョ ップトストランド状の補強材を落下させ、 その上にコンパゥン ドを均一な厚さに供給し、 さらにコンパゥン ドの上方から離型性フィル ムを被せて脱泡させる方法、 ④補強材を混合 （混練） した不飽和ボリエ ステル樹脂組成物をシ一ト状に延伸する方法等、 種々の方法によりシー ト状とすることで得ることができる。 このようにして得られたシート状 成形材料は、 ボリエチレン、 ポリプロピレン、 アルミ蒸着フイルム等の 離型性フィルムで包んで熟成させることにより、 成形性に優れたシー ト 状成形材料とすることができる。 For example, sheet-like molding materials are prepared according to the usual method. -A method of impregnating a sheet-like (mat-like) reinforcing material; ② A method of stretching a compound into a sheet and sandwiching the reinforcing material with this sheet-like material; ③ A chopped strand-like reinforcement on a release film A method in which a material is dropped, a compound is supplied on the compound in a uniform thickness, and a demolding film is placed over the compound to remove bubbles. (4) Unsaturated ballet with mixed (kneaded) reinforcing material It can be obtained by forming the steal resin composition into a sheet by various methods, such as a method of stretching it in a sheet shape. The sheet-like molding material obtained in this way can be wrapped with a release film such as polyethylene, polypropylene, or aluminum-deposited film and aged to be a sheet-like molding material having excellent moldability.
また、 例えば、 バルク状成形材料は、 例えば補強材ゃ充塡剤、 離型剤 等を含む不飽和ボリエステル樹脂組成物を双腕型ニーダ等の混練機を用 いて混練することによりバルク状とすることで、 容易に得ることができ る。 このようにして得られたバルク状成形材料は、 上記離型性フイ ルム で包んで熟成させることにより、 成形性に優れたバルク状成形材料とす ることができる。 Also, for example, the bulk molding material is formed into a bulk by kneading an unsaturated polyester resin composition containing, for example, a reinforcing material filler, a release agent, and the like using a kneading machine such as a double-arm kneader. In this way, it can be easily obtained. The bulk molding material obtained in this way can be made into a bulk molding material having excellent moldability by wrapping with the above release film and aging.
そして、 これらシー ト状成形材料やバルク状成形材料等の成形材料は、 例えば圧縮成形や射出成形、 トランスファー成形等により成形すること で、 光沢や表面平滑性等の物性に優れる成形品を得ることができる。 Molding materials such as sheet-like molding materials and bulk-like molding materials are molded by, for example, compression molding, injection molding, transfer molding, or the like to obtain molded products having excellent physical properties such as gloss and surface smoothness. Can be.
尚、 本発明の不飽和ポリエステル樹脂組成物およびこれを含む各種成 形材料の硬化方法は、 特に限定されるものではない。 即ち、 本発明にか かる不飽和ボリエステル樹脂組成物は、 種々の成形方法に適用可能であ る。 そして、 このように、 本発明にかかる不飽和ボリエステル樹脂組成 物およびこれを含む成形材料を成形してなる成形品は、 光沢や表面平滑
性等の物性が従来よりも改善されている。 The method of curing the unsaturated polyester resin composition of the present invention and various molding materials containing the same is not particularly limited. That is, the unsaturated polyester resin composition according to the present invention is applicable to various molding methods. As described above, the molded product obtained by molding the unsaturated polyester resin composition according to the present invention and the molding material containing the same has gloss and surface smoothness. Physical properties such as properties are improved than before.
以上のように、 本発明にかかる不飽和ポリエステル樹脂組成物は、 水 素化ビスフ ノール骨格を有する不飽和ボリエステル樹脂と、 三次元ス チレンボリマーを含む低収縮化剤と、 減粘剤とを含む構成である。 上記 不飽和ボリエステル樹脂 100重量部に対する低収縮化剤および減粘剤の 割合は、 低収縮化剤 1 1重量部〜 20重量部の範囲内および減粘剤 1重量部 〜 8重量部の範囲内であることが好ましい。 上記不飽和ボリエステル樹 脂組成物は、 さらに、 補強材を含むことが好ましく、 上記補強材として は、 1 /4インチ以下の繊維長を有する繊維が好適である。 また、 本発明 にかかる不飽和ボリエステル樹脂組成物は、 水素化ビスフヱノール骨格 を有する不飽和ボリエステル樹脂 100重量部に対して、 三次元スチレン ボリマーを含む低収縮化剤 1 1重量部〜 20重量部および充塡剤 1 90重量部 〜 350重量部を含む混合物を、 減粘剤を用いて 35てにおける粘度が 1000 ボイズ以下となるように調整してなる構成である。 そして、 本発明にか かるシー ト状成形材料は、 上記の不飽和ボリエステル樹脂組成物を含む 構成である。 As described above, the unsaturated polyester resin composition according to the present invention is configured to include an unsaturated polyester resin having a hydrogenated bisphenol skeleton, a low-shrinking agent containing a three-dimensional styrene polymer, and a thickening agent. It is. The ratio of the low-shrinking agent and the thickening agent to 100 parts by weight of the unsaturated polyester resin is in the range of 11 to 20 parts by weight of the low-shrinking agent and in the range of 1 to 8 parts by weight of the thickening agent. It is preferred that The unsaturated polyester resin composition preferably further contains a reinforcing material. As the reinforcing material, a fiber having a fiber length of 1/4 inch or less is suitable. Further, the unsaturated polyester resin composition according to the present invention comprises 11 parts by weight to 20 parts by weight of a low-shrinking agent containing a three-dimensional styrene polymer with respect to 100 parts by weight of the unsaturated polyester resin having a hydrogenated bisphenol skeleton. Filler 1 A mixture containing 90 parts by weight to 350 parts by weight is adjusted by using a viscosity reducing agent such that the viscosity at 35 wt. The sheet-like molding material according to the present invention is configured to include the above-mentioned unsaturated polyester resin composition.
従って、 本発明によれば、 硬化時の収縮に加えて、 成形後の冷却時の 収縮をも抑制することができ、 これにより、 表面平滑性や光沢等の物性 に優れた成形品を得ることができる不飽和ボリエステル樹脂組成物を提 供することができる。 該不飽和ポリエステル樹脂組成物は、 例えば、 S M C等のシート状成形材料や、 B M C等のバルク状成形材料等に好適に 用いることができる。 該不飽和ボリエステル樹脂組成物は、 補強材に対 する含浸性に優れているため、 コンバウンドの粘度が補強材に対する含 浸性に大きく影響を及ぼすシ一 ト状成形材料に、 特に好適に用いること
ができる。 このため、 該不飽和ボリエステル樹脂組成物を含むシート状 成形材料もまた、 硬化時の収縮に加えて、 成形後の冷却時の収縮をも抑 制することができ、 これにより、 表面平滑性や光沢等の物性に優れた成 形品を得ることができる。 Therefore, according to the present invention, in addition to shrinkage during curing, shrinkage during cooling after molding can be suppressed, thereby obtaining a molded article having excellent physical properties such as surface smoothness and gloss. The present invention can provide an unsaturated polyester resin composition which can be used. The unsaturated polyester resin composition can be suitably used, for example, as a sheet-like molding material such as SMC, or a bulk-like molding material such as BMC. Since the unsaturated polyester resin composition is excellent in impregnating property with respect to a reinforcing material, it is particularly suitably used for a sheet-like molding material in which the viscosity of a compound greatly affects the impregnating property with respect to a reinforcing material. thing Can be. For this reason, the sheet-like molding material containing the unsaturated polyester resin composition can also suppress shrinkage upon cooling after molding, in addition to shrinkage upon curing, thereby improving surface smoothness and the like. A molded product with excellent physical properties such as gloss can be obtained.
本発明にかかる不飽和ボリエステル樹脂組成物を用いてなる成形品と しては、 例えば、 所謂採光ドーム、 ベンチ、 テーブル、 タンク、 公告板、 防水板等の、 屋外で使用される各種物品 ； 浄化槽、 自動車、 鉄道車両、 船舶等を構成する構成材 ； 屋根 ·壁等の、 構造物の外装材； バスタブや キッチンカウン夕として好適な人工大理石 ； 電気部品等が挙げられるが、 特に限定されるものではない。 Examples of molded articles using the unsaturated polyester resin composition according to the present invention include various articles used outdoors such as so-called daylighting domes, benches, tables, tanks, public notice boards, waterproof boards, etc .; , Components of automobiles, railway vehicles, ships, etc .; exterior materials of structures, such as roofs and walls; artificial marble suitable for bathtubs and kitchen counters; and electrical components. is not.
本発明のさらに他の目的、 特徴、 および優れた点は、 以下に示す記載 によって十分わかるであろう。 また、 本発明の利益は、 次の説明で明白 になるであろう。 発明を実施するための最良の形態 Further objects, features, and advantages of the present invention will be made clear by the description below. Also, the benefits of the present invention will become apparent in the following description. BEST MODE FOR CARRYING OUT THE INVENTION
以下、 実施例および比較例により、 本発明をさらに詳細に説明するが、 本発明はこれらにより何ら限定されるものではない。 尚、 実施例および 比較例に記載の 「部 J は、 「重量部」 を示している。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, “part J” described in Examples and Comparative Examples indicates “parts by weight”.
〔実施例 1 〕 (Example 1)
温度計、 冷却器、 窒素ガス導入管、 および攪拌機を備えた反応容器に、 酸成分としての無水マレイン酸 980 g、 および、 アルコール成分として の水素化ビスフエノール A 472 g、 プロピレングリ コール 473 g、 ジブ ロビレングリ コール 157 g、 ネオペンチルグリコール 104 gを仕込んだ, 次いで、 該反応容器内を窒素ガス置換した後、 215 'Cに昇温し、 該反応
温度を保ちながら約 8時間攪拌することにより反応を完了させて不飽和 ボリエステルを得た。 所定の方法により測定した該不飽和ボリエステル の酸価は 24mgK◦ HZgであった。 その後、 該不飽和ボリエステル 100 部に対して、 重合禁止剤としてのハイ ドロキノ ン 0.01部を加え 後、 重 合性単暈体としてのスチレンモノマー 75部に溶解させることにより、 液 状の不飽和ボリエステル樹脂を得た。 In a reaction vessel equipped with a thermometer, a cooler, a nitrogen gas inlet tube, and a stirrer, 980 g of maleic anhydride as an acid component, 472 g of hydrogenated bisphenol A as an alcohol component, and 473 g of propylene glycol, 157 g of divinylene glycol and 104 g of neopentyl glycol were charged. Then, the inside of the reaction vessel was purged with nitrogen gas, and the temperature was raised to 215'C. The reaction was completed by stirring for about 8 hours while maintaining the temperature to obtain an unsaturated polyester. The acid value of the unsaturated polyester measured by a predetermined method was 24 mgK • HZg. Thereafter, 0.01 part of hydroquinone as a polymerization inhibitor was added to 100 parts of the unsaturated polyester, and then dissolved in 75 parts of a styrene monomer as a polymer monomer to obtain a liquid unsaturated polyester. A resin was obtained.
次に、 上記不飽和ボリエステル樹脂 80部、 スチレンモノマー 25部、 減 粘剤 （ビックケミ一 · ジャパン株式会社製 ； 商品名 B YK— W 9 0 1 0 ) 4部、 重合禁止剤としてのパラべンゾキノ ン 0.05部、 硬化剤として の t-ブチルバ一ォキシイソプロピルカーボネー ト 1部、 低収縮化剤とし ての三次元スチレンポリマー （綜研化学株式会社製 ；商品名 S G P - 7 0 C) 15部、 離型剤としてのステァリ ン酸亜鉛 5部、 および充填剤と しての炭酸カルシウム 250部を混合し、 均一に分散するまで充分攪拌し た。 その後、 該混合物に、 さらに増粘剤としての酸化マグネシウム 1部 を添加した後、 得られた不飽和ボリエステル樹脂組成物中の含有量が 15 重量％となるように、 補強材としての繊維長 1 インチのガラス繊維をさ らに添加し、 常法に基づいて SMCを作成した。 Next, 80 parts of the above-mentioned unsaturated polyester resin, 25 parts of styrene monomer, 4 parts of a thickener (manufactured by BYK-Chemical Japan Co., Ltd .; trade name: BYK-W910), parabenzoquino as a polymerization inhibitor 0.05 parts, t-butyl isopropyl isopropyl carbonate as a curing agent 1 part, a three-dimensional styrene polymer as a low shrinkage agent (manufactured by Soken Chemical Co., Ltd .; trade name SGP-70C) 15 parts, Five parts of zinc stearate as a release agent and 250 parts of calcium carbonate as a filler were mixed and sufficiently stirred until uniformly dispersed. Thereafter, 1 part of magnesium oxide as a thickener was further added to the mixture, and the fiber length as a reinforcing material was adjusted so that the content in the obtained unsaturated polyester resin composition was 15% by weight. An inch glass fiber was further added, and an SMC was prepared according to a conventional method.
次いで、 得られた S MCをアルミ蒸着フィルムに包み、 40°Cで約 20時 間熟成した。 その後、 該 S MCを上型 145'C、 下型 135でに調整した金 型に供絵し、 圧力 70kgf Zcm2 (面圧） で 4分間加圧保持することによ り、 30cmx30cmの平板に成形した。 得られた成形品の表面平滑性および 光沢を目視により評価した。 この結果を表 1 に示す。 Next, the obtained SMC was wrapped in an aluminum vapor-deposited film and aged at 40 ° C. for about 20 hours. After that, the SMC is applied to a die adjusted with an upper die 145'C and a lower die 135, and is pressed and maintained at a pressure of 70 kgf Zcm 2 (surface pressure) for 4 minutes to form a 30 cm × 30 cm flat plate. Molded. The surface smoothness and gloss of the obtained molded product were visually evaluated. Table 1 shows the results.
〔実施例 2〕 (Example 2)
実施例 1 において、 繊維長 1 ィンチのガラス織維に代えて繊維長 1/4
ィンチのガラス繊維を用いた以外は実施例 1 と同様の配合および操作を 行って S MCを作成した。 その後、 該 S MCを用いて、 実施例 1 と同様 の方法により成形品を得た。 得られた成形品の表面平滑性および光沢を 目視により評価した。 この結果を表 1 に示す。 In Example 1, a fiber length of 1/4 was used instead of the glass fiber having a fiber length of 1 inch. An SMC was prepared by performing the same blending and operation as in Example 1 except that the glass fiber of INCH was used. Thereafter, using the SMC, a molded article was obtained in the same manner as in Example 1. The surface smoothness and gloss of the obtained molded product were visually evaluated. Table 1 shows the results.
〔比較例 1〕 (Comparative Example 1)
実施例 1 と同様の反応容器に、 酸成分としてのフマル酸 1161 g、 およ び、 アルコール成分としてのプロビレングリ コール 837gを仕込んだ。 次いで、 該反応容器内を窒素ガス置換した後、 200 'Cに昇温し、 該反応 温度を保ちながら約 9時間攪拌することにより反応を完了させて不飽和 ボリエステルを得た。 所定の方法により測定した該不飽和ボリエステル の酸価は 30mgK 0 HZgであった。 その後、 該不飽和ポリエステル 100 部に対して、 ハイ ドロキノ ン 0.01部を加えた後、 スチレ ンモノマ一 75部 に溶解させることにより、 比較用の液状の不飽和ボリエステル樹脂を得 次に、 上記比較用の不飽和ポリエステル樹脂 80部、 スチ レンモノマー 25部、 パラべンゾキノ ン 0.05部、 t-ブチルバ一ォキシイソプロピルカー ボネ一 ト 1部、 三次元スチレ ンボリ マー （綜研化学株式会社製 ； 商品名 S G P— 7 0 C) 10部、 ステアリ ン酸亜鉛 5部、 炭酸カルシウム 150 部を混合し、 均一に分散するまで充分攪拌した。 その後、 該混合物に、 さらに酸化マグネシウム 1.5部を添加した後、 得られた不飽和ボリエス テル樹脂組成物中の含有量が 15重量 となるように、 繊維長 1 イ ンチの ガラス繊維をさらに添加し、 常法に基づいて SMCを作成した。 次いで. 得られた上記 SMC、 即ち、 比較用の SMCを用いて、 実施例 1 と同様 の方法により成形品を得た。 得られた成形品の表面の平滑性および光沢
を目視により評価した。 この結果を表 1 に示す, 表 1 In a reaction vessel similar to that in Example 1, 1161 g of fumaric acid as an acid component and 837 g of propylene glycol as an alcohol component were charged. Next, after the inside of the reaction vessel was replaced with nitrogen gas, the temperature was raised to 200 ° C., and the reaction was completed by stirring for about 9 hours while maintaining the reaction temperature to obtain an unsaturated polyester. The acid value of the unsaturated polyester measured by a predetermined method was 30 mg K 0 HZg. Thereafter, 0.01 part of hydroquinone was added to 100 parts of the unsaturated polyester, and then dissolved in 75 parts of styrene monomer to obtain a liquid unsaturated polyester resin for comparison. 80 parts of unsaturated polyester resin, 25 parts of styrene monomer, 0.05 parts of parabenzoquinone, 1 part of t-butyl isopropyl isopropyl carbonate, three-dimensional styrene polymer (manufactured by Soken Chemical Co., Ltd .; trade name: SGP — 70 C) 10 parts, 5 parts of zinc stearate, and 150 parts of calcium carbonate were mixed and thoroughly stirred until uniformly dispersed. Thereafter, 1.5 parts of magnesium oxide was further added to the mixture, and then glass fibers having a fiber length of 1 inch were further added so that the content in the obtained unsaturated polyester resin composition was 15% by weight. An SMC was created based on standard methods. Then, a molded article was obtained in the same manner as in Example 1 using the obtained SMC, that is, the SMC for comparison. Surface smoothness and gloss of the resulting molded article Was visually evaluated. The results are shown in Table 1.
評価基準 ： 良 © >〇> Δ > χ 不良 表 1 に記載の結果から明らかなように、 本実施例によれば、 従来より も、 光沢および表面平滑性に優れた成形品が得られることが判った。 尚、 発明を実施するための最良の形態の項においてなした具体的な実 施態様または実施例は、 あく までも、 本発明の技術内容を明らかにする ものであって、 そのような具体例にのみ限定して狭義に解釈されるべき ものではなく、 本発明の精神と次に記載する特許請求の範囲内で、 いろ いろと変更して実施することができるものである。 産業上の利用可能性 Evaluation criteria: good ©> 〇> Δ> 不良 poor As is clear from the results described in Table 1, according to the present example, it is possible to obtain a molded article having better gloss and surface smoothness than before. understood. It should be noted that the specific embodiments or examples made in the section of the best mode for carrying out the invention merely clarify the technical contents of the present invention, and such specific examples The present invention should not be construed as being limited to only the above, but can be implemented with various modifications within the spirit of the present invention and the scope of the claims described below. Industrial applicability
本発明に係る不飽和ボリエステル樹脂組成物は、 硬化時の収縮に加え て、 成形後の冷却時の収縮をも抑制することができる。 このため、 本発 明に係る不飽和ポリエステル樹脂組成物を用いれば、 表面平滑性や光沢 等の物性に優れた成形品を得ることができる。 また、 該不飽和ボリエス テル樹脂組成物は、 例えば、 S M C等のシー ト状成形材料や、 B M C等 のバルク状成形材料等に好適に用いることができる。 該不飽和ボリエス テル樹脂組成物は、 捕強材に対する含浸性に優れているため、 補強材以
外の成分 （コンパウンド） の粘度が補強材に対する含浸性に大きく影響 を及ぼすシ一ト状成形材料に、 特に好適に用いることができる。
The unsaturated polyester resin composition according to the present invention can suppress not only shrinkage during curing but also shrinkage during cooling after molding. Therefore, when the unsaturated polyester resin composition according to the present invention is used, a molded article having excellent physical properties such as surface smoothness and gloss can be obtained. In addition, the unsaturated ballistic resin composition can be suitably used, for example, as a sheet-like molding material such as SMC, or a bulk-like molding material such as BMC. Since the unsaturated ball polyester resin composition has excellent impregnation property with respect to the strength-imparting material, it is less than a reinforcing material. It can be particularly suitably used for a sheet-like molding material in which the viscosity of an external component (compound) greatly affects the impregnation property of the reinforcing material.
Claims
1 . 水素化ビスフユノール骨格を有する不飽和ボリエステル樹脂と、 三 次元スチレンボリマ一を含む低収縮化剤と、 減粘剤とを含むことを特徴 とする不飽和ポリエステル樹脂組成物。 1. An unsaturated polyester resin composition comprising: an unsaturated polyester resin having a hydrogenated bisphenol skeleton; a low-shrinking agent containing a three-dimensional styrene polymer; and a viscosity reducing agent.
2 . 上記不飽和ボリエステル樹脂 100重量部に対する低収縮化剤および 減粘剤の割合が、 低収縮化剤 1 1重量部〜 20重量部の範囲内および减粘剤 2. The ratio of the low-shrinking agent and the thickening agent to 100 parts by weight of the unsaturated polyester resin is within the range of 11 to 20 parts by weight of the low-shrinking agent and the thickening agent.
1重量部〜 8重量部の範囲内であることを特徵とするク レーム 1記載の 不飽和ボリエステル樹脂組成物。 The unsaturated polyester resin composition according to claim 1, wherein the amount is in the range of 1 part by weight to 8 parts by weight.
3 . さらに、 補強材を含むことを特徵とするク レーム 1記載の不飽和ポ リエステル樹脂組成物。 3. The unsaturated polyester resin composition according to claim 1, further comprising a reinforcing material.
4 . 上記補強材が 1 /4インチ以下の繊維長を有する繊維であることを特 徵とするクレーム 3記載の不飽和ボリエステル樹脂組成物。 4. The unsaturated polyester resin composition according to claim 3, wherein the reinforcing material is a fiber having a fiber length of 1/4 inch or less.
5 . 水素化ビスフエノール骨格を有する不飽和ボリエステル樹脂 100重 量部に対して、 三次元スチレンポリマーを含む低収縮化剤 1 1重量部〜 20 重量部および充塡剤 190重量部〜 350重量部を含む混合物を、 減粘剤を 用いて 35'Cにおける粘度が 1000ボイズ以下となるように調整してなるこ とを特徴とする不飽和ボリエステル樹脂組成物。 5. With respect to 100 parts by weight of unsaturated polyester resin having a hydrogenated bisphenol skeleton, 11 to 20 parts by weight of a low-shrinking agent containing a three-dimensional styrene polymer and 190 to 350 parts by weight of a filler An unsaturated polyester resin composition characterized in that a mixture containing the following is adjusted with a viscosity reducer so that the viscosity at 35'C is 1000 boise or less.
6 . 水素化ビスフヱノール骨格を有する不飽和ボリエステル樹脂と、 三 次元スチレンボリマーを含む低収縮化剤と、 減粘剤とを含む不飽和ボリ エステル樹脂組成物を含むことを特徵とするシー ト状成形材料。 6. A sheet characterized by containing an unsaturated polyester resin having an unsaturated polyester resin having a hydrogenated bisphenol skeleton, a low-shrinking agent containing a three-dimensional styrene polymer, and a viscosity reducing agent. Molding material.
7 . 水素化ビスフエノール骨格を有する不飽和ボリエステル樹脂 100重 量部に対して、 三次元スチレンボリマ一を含む低収縮化剤 1 1重量部〜 20 重量部および充填剤 190重量部〜 350重量部を含む混合物を、 弒粘剤を
用いて 35eCにおける粘度が 1000ボイズ以下となるように調整してなる不 飽和ボリエステル樹脂組成物を含むことを特徴とするシー ト状成形材料 <
7. To 100 parts by weight of the unsaturated polyester resin having a hydrogenated bisphenol skeleton, 11 to 20 parts by weight of a low-shrinking agent containing three-dimensional styrene polymer and 190 to 350 parts by weight of a filler are added. The mixture containing Sheet-like molding material which results in a viscosity at 35 e C is characterized in that it comprises an unsaturated Boriesuteru resin composition comprising adjusted to 1000 Boise below using <
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8055177A JPH09241496A (en) | 1996-03-12 | 1996-03-12 | Unsaturated polyester resin composition and sheet-like molding material |
| JP8/55177 | 1996-03-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1997033942A1 true WO1997033942A1 (en) | 1997-09-18 |
Family
ID=12991452
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP1997/000673 WO1997033942A1 (en) | 1996-03-12 | 1997-03-05 | Unsaturated polyester resin composition and sheetlike molding material |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPH09241496A (en) |
| KR (1) | KR19990007951A (en) |
| CN (1) | CN1181772A (en) |
| WO (1) | WO1997033942A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508828B (en) * | 2009-02-11 | 2011-07-20 | 常州市华润复合材料有限公司 | Saturated polyester resin for molding compound as shrinking agent and production method thereof |
| CN103410290A (en) * | 2013-08-28 | 2013-11-27 | 四川迪弗电工科技有限公司 | New applications of sheet molding compound (SMC) material |
| CN103613715A (en) * | 2013-07-02 | 2014-03-05 | 大连当代兴达发展有限公司 | Sheet molding compound with high stability and high uniformity and preparation method therefor |
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| KR100343599B1 (en) * | 1999-08-11 | 2002-07-11 | 정광수 | Manufacturing method of ceiling board |
| KR100427555B1 (en) * | 2001-02-21 | 2004-04-27 | 주식회사 엘지화학 | Sheet Molding Compound Water-Proof Flooring Having Core Layer and the Method of Manufacturing thereof |
| JP3454358B2 (en) * | 2001-07-10 | 2003-10-06 | 日東紡績株式会社 | Flame retardant glass fiber reinforced unsaturated polyester resin molded plate and method for producing the same |
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| CN102061053B (en) * | 2009-10-22 | 2013-05-08 | 上海琥达投资发展有限公司 | Resin matrix composite material sanitary appliance and preparation method thereof |
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| CN102060985B (en) * | 2010-12-17 | 2013-04-17 | 常州华科树脂有限公司 | Unsaturated polyester resin for sheet or bulk molding compound and preparation method thereof |
| CN102060987A (en) * | 2010-12-21 | 2011-05-18 | 常州华日新材有限公司 | Preparation method of unsaturated polyester resin for high-rigidity and high-thermal deformation temperature casting |
| CN102358799B (en) * | 2011-09-16 | 2013-01-02 | 无锡创达电子有限公司 | Unsaturated polyester molding compound and preparation method thereof |
| CN105111769A (en) * | 2015-09-22 | 2015-12-02 | 无锡澳明威环保新材料有限公司 | Anti-aging and anti-ultraviolet SMC (sheet molding compound) and preparation method thereof |
| JP6901257B2 (en) * | 2016-12-02 | 2021-07-14 | 昭和電工株式会社 | Arc resistance BMC |
| CN108972929A (en) * | 2018-09-26 | 2018-12-11 | 上海应用技术大学 | DMC process for producing composite materials and system |
| JP7186602B2 (en) * | 2018-12-25 | 2022-12-09 | 昭和電工株式会社 | Thermosetting resin composition, molding and lamp reflector |
| JP7616071B2 (en) * | 2019-12-16 | 2025-01-17 | 株式会社レゾナック | Thermosetting resin composition |
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| JPS4881984A (en) * | 1972-02-07 | 1973-11-01 | ||
| JPS5252989A (en) * | 1975-10-27 | 1977-04-28 | Kuraray Co Ltd | Unsaturated polyester esin compositions |
| JPS52141890A (en) * | 1976-05-21 | 1977-11-26 | Dainippon Ink & Chem Inc | Unsaturated polyester resin composition |
| JPS57143315A (en) * | 1981-02-28 | 1982-09-04 | Nitto Electric Ind Co Ltd | Unsaturated polyester resin composition for molded article |
| JPS58127718A (en) * | 1982-01-27 | 1983-07-29 | Toshiba Corp | Unsaturated polyester resin composition and colored molding |
| JPH07126504A (en) * | 1993-11-02 | 1995-05-16 | Sekisui Chem Co Ltd | Unsaturated polyester resin composition |
-
1996
- 1996-03-12 JP JP8055177A patent/JPH09241496A/en not_active Withdrawn
-
1997
- 1997-03-05 CN CN97190171A patent/CN1181772A/en active Pending
- 1997-03-05 WO PCT/JP1997/000673 patent/WO1997033942A1/en not_active Application Discontinuation
- 1997-03-05 KR KR1019970707474A patent/KR19990007951A/en not_active IP Right Cessation
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4881984A (en) * | 1972-02-07 | 1973-11-01 | ||
| JPS5252989A (en) * | 1975-10-27 | 1977-04-28 | Kuraray Co Ltd | Unsaturated polyester esin compositions |
| JPS52141890A (en) * | 1976-05-21 | 1977-11-26 | Dainippon Ink & Chem Inc | Unsaturated polyester resin composition |
| JPS57143315A (en) * | 1981-02-28 | 1982-09-04 | Nitto Electric Ind Co Ltd | Unsaturated polyester resin composition for molded article |
| JPS58127718A (en) * | 1982-01-27 | 1983-07-29 | Toshiba Corp | Unsaturated polyester resin composition and colored molding |
| JPH07126504A (en) * | 1993-11-02 | 1995-05-16 | Sekisui Chem Co Ltd | Unsaturated polyester resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508828B (en) * | 2009-02-11 | 2011-07-20 | 常州市华润复合材料有限公司 | Saturated polyester resin for molding compound as shrinking agent and production method thereof |
| CN103613715A (en) * | 2013-07-02 | 2014-03-05 | 大连当代兴达发展有限公司 | Sheet molding compound with high stability and high uniformity and preparation method therefor |
| CN103410290A (en) * | 2013-08-28 | 2013-11-27 | 四川迪弗电工科技有限公司 | New applications of sheet molding compound (SMC) material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09241496A (en) | 1997-09-16 |
| CN1181772A (en) | 1998-05-13 |
| KR19990007951A (en) | 1999-01-25 |
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