JPH0415249A - Liquid-crystal polyester carbonate resin composition - Google Patents
Liquid-crystal polyester carbonate resin compositionInfo
- Publication number
- JPH0415249A JPH0415249A JP11752690A JP11752690A JPH0415249A JP H0415249 A JPH0415249 A JP H0415249A JP 11752690 A JP11752690 A JP 11752690A JP 11752690 A JP11752690 A JP 11752690A JP H0415249 A JPH0415249 A JP H0415249A
- Authority
- JP
- Japan
- Prior art keywords
- polyester carbonate
- liquid crystalline
- carbonate resin
- crystalline polyester
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 45
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 44
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 7
- 239000011342 resin composition Substances 0.000 title claims description 10
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- MZZYGYNZAOVRTG-UHFFFAOYSA-N 2-hydroxy-n-(1h-1,2,4-triazol-5-yl)benzamide Chemical compound OC1=CC=CC=C1C(=O)NC1=NC=NN1 MZZYGYNZAOVRTG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 36
- 239000002253 acid Substances 0.000 claims description 23
- 239000006078 metal deactivator Substances 0.000 claims description 20
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims description 4
- 125000005586 carbonic acid group Chemical group 0.000 claims description 3
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 7
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000465 moulding Methods 0.000 abstract description 6
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 abstract description 3
- 230000000937 inactivator Effects 0.000 abstract 2
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- -1 Polyethylene terephthalate Polymers 0.000 description 22
- 238000000034 method Methods 0.000 description 9
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 230000006866 deterioration Effects 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 150000001555 benzenes Chemical group 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 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
- 238000004898 kneading Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 description 1
- CRKDNNLDFYKBEE-RMKNXTFCSA-N (e)-benzylidenehydrazine Chemical compound N\N=C\C1=CC=CC=C1 CRKDNNLDFYKBEE-RMKNXTFCSA-N 0.000 description 1
- BLDLRWQLBOJPEB-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfanylphenol Chemical compound OC1=CC=CC=C1SC1=CC=CC=C1O BLDLRWQLBOJPEB-UHFFFAOYSA-N 0.000 description 1
- XSVZEASGNTZBRQ-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfinylphenol Chemical compound OC1=CC=CC=C1S(=O)C1=CC=CC=C1O XSVZEASGNTZBRQ-UHFFFAOYSA-N 0.000 description 1
- QUWAJPZDCZDTJS-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfonylphenol Chemical compound OC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1O QUWAJPZDCZDTJS-UHFFFAOYSA-N 0.000 description 1
- RURPJGZXBHYNEM-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]propyliminomethyl]phenol Chemical compound C=1C=CC=C(O)C=1C=NC(C)CN=CC1=CC=CC=C1O RURPJGZXBHYNEM-UHFFFAOYSA-N 0.000 description 1
- FLZYQMOKBVFXJS-UHFFFAOYSA-N 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoic acid Chemical compound CC1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O FLZYQMOKBVFXJS-UHFFFAOYSA-N 0.000 description 1
- DUENUEBQBZJTEY-UHFFFAOYSA-N 3-(4-hydroxyphenyl)-N'-[3-(4-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound Oc1ccc(CCC(=O)NNC(=O)CCc2ccc(O)cc2)cc1 DUENUEBQBZJTEY-UHFFFAOYSA-N 0.000 description 1
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- GZDFHIJNHHMENY-UHFFFAOYSA-N Dimethyl dicarbonate Chemical compound COC(=O)OC(=O)OC GZDFHIJNHHMENY-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- VDACCTGBJAMTDN-UHFFFAOYSA-N N'-acetyl-2-hydroxybenzohydrazide Chemical compound CC(=O)NNC(=O)C1=CC=CC=C1O VDACCTGBJAMTDN-UHFFFAOYSA-N 0.000 description 1
- DKOAWDCKXYTFOL-UHFFFAOYSA-N OC1=C(C=CC=C1)C(=O)C1=C(C=CC=C1)O.OC1=C(C=CC=C1)OC1=C(C=CC=C1)O Chemical compound OC1=C(C=CC=C1)C(=O)C1=C(C=CC=C1)O.OC1=C(C=CC=C1)OC1=C(C=CC=C1)O DKOAWDCKXYTFOL-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical compound NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- OFLXLNCGODUUOT-UHFFFAOYSA-N acetohydrazide Chemical compound C\C(O)=N\N OFLXLNCGODUUOT-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- FFYPMLJYZAEMQB-UHFFFAOYSA-N diethyl pyrocarbonate Chemical compound CCOC(=O)OC(=O)OCC FFYPMLJYZAEMQB-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 235000010300 dimethyl dicarbonate Nutrition 0.000 description 1
- 239000004316 dimethyl dicarbonate Substances 0.000 description 1
- 150000002009 diols Chemical group 0.000 description 1
- GWZCCUDJHOGOSO-UHFFFAOYSA-N diphenic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1C(O)=O GWZCCUDJHOGOSO-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- SWRGUMCEJHQWEE-UHFFFAOYSA-N ethanedihydrazide Chemical compound NNC(=O)C(=O)NN SWRGUMCEJHQWEE-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- SKLVOJWBZJWSEN-UHFFFAOYSA-N n,n'-bis(2-hydroxyphenyl)oxamide Chemical compound OC1=CC=CC=C1NC(=O)C(=O)NC1=CC=CC=C1O SKLVOJWBZJWSEN-UHFFFAOYSA-N 0.000 description 1
- CPTBDGGVCRZAGB-UHFFFAOYSA-N n,n'-bis(3,5-ditert-butyl-4-hydroxyphenyl)propanehydrazide Chemical compound C=1C(C(C)(C)C)=C(O)C(C(C)(C)C)=CC=1N(C(=O)CC)NC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 CPTBDGGVCRZAGB-UHFFFAOYSA-N 0.000 description 1
- FTWUXYZHDFCGSV-UHFFFAOYSA-N n,n'-diphenyloxamide Chemical compound C=1C=CC=CC=1NC(=O)C(=O)NC1=CC=CC=C1 FTWUXYZHDFCGSV-UHFFFAOYSA-N 0.000 description 1
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000343 polyazomethine Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 238000000646 scanning calorimetry Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、優れた耐熱安定性及び機械的、熱的特性を有
する液晶性ポリエステルカーポネーｈ樹脂組成物に関す
るものであり、本発明の樹脂組成物は自動車１機械、建
築、電子機器及びその他の諸工業の分野で、外装部品、
機械部品として好適に用いられる。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a liquid crystalline polyester carbonate resin composition having excellent heat resistance stability and mechanical and thermal properties. is used in the fields of automobile machinery, architecture, electronic equipment, and other industries, including exterior parts,
Suitable for use as mechanical parts.
従来の技術
ポリエチレンテレフタレートは、優れた耐薬品性及び機
械的性質を有しており、繊維、フィルム、プラスチック
等の成形材料として広く用いられている。しかしながら
、ポリエチレンテレフタレートは、熱変形温度が比較的
低く、また特に工ンジニアリングプラスチックとして使
用する場合には強度的にも十分であるとは言えず、この
ため例えばガラス繊維で強化するなどして使用している
状況にある。BACKGROUND OF THE INVENTION Polyethylene terephthalate has excellent chemical resistance and mechanical properties, and is widely used as a molding material for fibers, films, plastics, and the like. However, polyethylene terephthalate has a relatively low heat distortion temperature and cannot be said to have sufficient strength, especially when used as an engineering plastic. I am in a situation where I am
方、カラスｍ維等の補強材を用いなくても、十分に高い
耐熱性及び機械的強度の得られる溶融成形可能なポリエ
ステルとして、各種の液晶性ポリエステルが提案されて
いる。On the other hand, various liquid crystalline polyesters have been proposed as melt-formable polyesters that can provide sufficiently high heat resistance and mechanical strength without using reinforcing materials such as glass m-fibers.
かかる液晶性ポリエステルの一種として、ｐ−オキシ安
息香酸を主とする芳香族オギシカルポン酸の残基、ハイ
ドロキノンを主とする芳香族ジヒドロキシ化合物の残基
及び炭酸の残基より構成された芳香族ポリエステルカー
ボネートが知られており（特公昭５９−３０７２７号公
報参照）、この芳香族ポリエステルカーボネートは溶融
成形性が良好で成形物の機械的特性に優れているため、
成形材料として種々の利点を有する。One type of such liquid crystalline polyester is an aromatic polyester carbonate composed of residues of aromatic oxycarboxylic acid mainly consisting of p-oxybenzoic acid, residues of aromatic dihydroxy compounds mainly consisting of hydroquinone, and residues of carbonic acid. is known (see Japanese Patent Publication No. 59-30727), and this aromatic polyester carbonate has good melt moldability and excellent mechanical properties of molded products.
It has various advantages as a molding material.
また、金属不活性剤については、「自動酸化の理論と実
際（大勝端−著、化学工業社刊昭和６１年） 、１ ノ
＋４１ベージに記載されているように光安定性を増加し
、屋外におけるプラスチックスの使用範囲を拡大するの
に有用であることが開示されている。Regarding metal deactivators, as described in ``The Theory and Practice of Autooxidation'' (Author: Ohkatsuta, published by Kagaku Kogyosha, 1986), page 1 no + 41, metal deactivators increase photostability and is disclosed to be useful for expanding the scope of use of plastics in
発明が解決しようとする課題
しかしながら、液晶性ポリエステルカーボネートは、成
形中の熱劣化による物性低下を生じたり、また高温下で
の長期的な使用に対する物性の安定性が不十分であり、
過酷な条件で使用する成形品の成形材料としては適当で
ない。Problems to be Solved by the Invention However, liquid crystalline polyester carbonate suffers from deterioration of physical properties due to thermal deterioration during molding, and insufficient stability of physical properties for long-term use at high temperatures.
It is not suitable as a molding material for molded products used under harsh conditions.
本発明の目的は、液晶性ポリエステルカーボネートが持
つ利点を維持しながら、成形中の熱劣化などが生ぜずに
、物性低下のない樹脂組成物を提供するものである。An object of the present invention is to provide a resin composition that does not suffer from thermal deterioration during molding and does not suffer from deterioration in physical properties while maintaining the advantages of liquid crystalline polyester carbonate.
課題を解決するための手段
本発明者らは、上述の目的を達成すべく鋭意研究の結果
、液晶性ポリエステルカーボネートに、金属不活性剤を
配合することにより、液晶性ポリエステルカーボネート
の利点を損なうことなく成形中の熱劣化を防ぐという事
実を見いだし、本発明に到達したものである。Means for Solving the Problems In order to achieve the above object, the present inventors have conducted extensive research and found that by blending a metal deactivator into liquid crystalline polyester carbonate, the advantages of liquid crystalline polyester carbonate can be impaired. The present invention was achieved by discovering the fact that thermal deterioration during molding can be prevented without any problems.
すなわち、本発明は、液晶性ポリエステルカーホ２−ト
系樹脂１００重嫉部に対し、金属不活性剤を００１〜５
重量部配合置部てなる液晶性ポリエステルカーボネート
樹脂組成物である。That is, in the present invention, the metal deactivator is added in an amount of 001 to 5 parts per 100 parts of the liquid crystalline polyester carbonate resin.
It is a liquid crystalline polyester carbonate resin composition consisting of parts by weight.
本発明における液晶性ポリエステルカーボネート樹脂は
、溶融詩に光学異方性を示すサーモトロビ、り液晶性ポ
リエステルカーボネートであり、また液晶性を損なわな
い範囲であればポリマーブレンドであってもよい。The liquid crystalline polyester carbonate resin in the present invention is a thermotrobi liquid crystalline polyester carbonate that exhibits optical anisotropy when melted, and may also be a polymer blend as long as it does not impair liquid crystallinity.
異方性溶融相の性質は、直交偏光子を利用した慣用の偏
光検査法により確認することができる。The nature of the anisotropic melt phase can be confirmed by conventional polarization testing using crossed polarizers.
より具体的には、異方性溶融相の確認は偏光顕微鏡を利
用し、ホットステージにのせた試料を観察することによ
り実施できる。More specifically, the anisotropic melt phase can be confirmed by observing a sample placed on a hot stage using a polarizing microscope.
本発明における液晶性ポリエステルカーボネート樹脂は
、
ａ）芳香族オキシカルボン酸残基
ｂ）芳香族ジオール残基
Ｃ）炭酸残基
ｄ）芳香族ジカルボン酸残基
より成り、そのモル比か
０≦ａ／（ａ＋ｂ）≦０．９！］
０、０１≦ｃ／（ｃ＋ｄ）≦１．Ｏ
ａ＋ｄ＞０
であることが好ましい。The liquid crystalline polyester carbonate resin in the present invention consists of a) aromatic oxycarboxylic acid residue b) aromatic diol residue C) carbonic acid residue d) aromatic dicarboxylic acid residue, and the molar ratio thereof is 0≦a/ (a+b)≦0.9! ] 0, 01≦c/(c+d)≦1. It is preferable that O a+d>0.
本発明においてａ）成分は、芳香族オキシカルボン酸残
基よりなる。In the present invention, component a) consists of aromatic oxycarboxylic acid residues.
原料とする芳香族オキシカルボン酸は５例えばｐ−オキ
シ安り、香酸、またはその核置換誘導体（例えば塩素原
子、臭素原子等の如きハロゲン原子、メチル基、エチル
基等の如き低級アルキル基、メトキシ基、エトキシ基の
如きアルコキシ基等の原子または基でベンゼン核の水素
原子の少なくとも１つが置換されているｐ−オキシ安息
香酸誘導体）、またはｐ−オキシ安息香酸の一部または
全部を他の芳香族オキシカルボン酸（例えばｍ−オキシ
安息香酸、オキシナフトエ酸、オキシジフェニルカルボ
ン酸及びこれらの核置換誘導体等）のＩＭまたは２種以
上でｔき検えたもの等が挙げられ゛る。The aromatic oxycarboxylic acid used as a raw material is 5, for example, p-oxyalkaline acid, aromatic acid, or its nuclear substituted derivatives (e.g., halogen atoms such as chlorine atom, bromine atom, etc., lower alkyl groups such as methyl group, ethyl group, etc.), (p-oxybenzoic acid derivatives in which at least one hydrogen atom of the benzene nucleus is substituted with an atom or group such as an alkoxy group such as a methoxy group or an ethoxy group), or p-oxybenzoic acid derivatives in which part or all of p-oxybenzoic acid is substituted with other Examples include aromatic oxycarboxylic acids (for example, m-oxybenzoic acid, oxynaphthoic acid, oxydiphenylcarboxylic acid, and their nuclear-substituted derivatives) that have been tested with IM or two or more thereof.
ここでＰ−オキシ安息香酸及びその核置換誘導体として
は、例えば、Ｐ−オキシ安息香酸、３−グロルー４−オ
キシ安息＃鑓、３−ブロム−４オキシ安息香酸、３−メ
チル−４−オキシ安息香酸、３−メトキシ−４−オキシ
安Ｐ、香醒、３，５−ジクロル−４−オキシ安思香酸、
３，５−ジブロム−４−オキシ安息香酸等が含まれる。Examples of P-oxybenzoic acid and its nuclear substituted derivatives include P-oxybenzoic acid, 3-gloro-4-oxybenzoic acid, 3-bromo-4oxybenzoic acid, and 3-methyl-4-oxybenzoic acid. acid, 3-methoxy-4-oxybenzoic acid, 3,5-dichloro-4-oxybenzizoic acid,
Includes 3,5-dibromo-4-oxybenzoic acid and the like.
ｂ）成分は、芳香族ジオール残基よりなる。Component b) consists of aromatic diol residues.
このｂ）成分の原料となる芳香族ジオールは１例えば、
ジオキシジフェニル、またはその核置換誘導体（例えば
塩素原子、臭素原子等の如きハロゲン原子、メチル基、
エチル基等の如き低級アルキル基、メトキシ基、エトキ
シ基の如きアルコキシ基及びフェニル基等の原子または
官能基でベンゼン核の水素原子の少なくとも１つが置換
されているジオキシジフェニル誘導体）、またはジオキ
シジフェニルの一部または全部を他の芳香族ジオール（
例えば、ヒドロキノン、レソルシン、ジオキシナフタレ
ン、ビス（ヒドロキシフェニル）スルフィド、ビス（ヒ
ドロキシフェニル）エーテルビス（ヒドロキシフェニル
）ケトン、ビス（ヒドロキシフェニル）スルホキシド、
ビス（ヒドロキシフェニル）スルホン、４．４゛−ビス
（ヒドロキシフェニル）ジインプロピルベンゼン、２．
２−ビス（４−ヒドロキシフェニル）プロパン、１゜ｌ
−ビス（４−ヒドロキシフェニル）シクロヘキサン及び
これらの核置換誘導体等）、あるいは液晶性を損なわな
い範囲で脂肪族ジオール（例えばエチレングリコール、
ネオペンチルグリコール等）や脂環族ジオール（例えば
シクロヘキサンジメチロール、シクロヘキサンジオール
等）の如き他種ジオールの１種または２種以上で置き換
えたものが挙げられる。The aromatic diol used as the raw material for component b) is 1, for example,
Dioxydiphenyl or its nuclear substituted derivatives (e.g. halogen atoms such as chlorine atom, bromine atom, etc., methyl group,
dioxydiphenyl derivatives in which at least one hydrogen atom of the benzene nucleus is substituted with an atom or functional group such as a lower alkyl group such as an ethyl group, an alkoxy group such as a methoxy group or an ethoxy group, or a phenyl group), or dioxy Part or all of the diphenyl can be replaced with other aromatic diols (
For example, hydroquinone, resorcin, dioxynaphthalene, bis(hydroxyphenyl) sulfide, bis(hydroxyphenyl)ether bis(hydroxyphenyl) ketone, bis(hydroxyphenyl) sulfoxide,
Bis(hydroxyphenyl)sulfone, 4.4′-bis(hydroxyphenyl)diinpropylbenzene, 2.
2-bis(4-hydroxyphenyl)propane, 1゜l
-bis(4-hydroxyphenyl)cyclohexane and their nuclear substituted derivatives, etc.), or aliphatic diols (e.g. ethylene glycol,
Neopentyl glycol, etc.) and alicyclic diols (for example, cyclohexane dimethylol, cyclohexane diol, etc.) may be substituted with one or more diols.
ここでジオキシジフェニル及びその核置換誘導体として
は、例えばジオキシジフェニル、塩化ジオキシジフェニ
ル、臭化ジオキシジフェニル、メチルジオギシジフェニ
ル、メトキシジオキシジフェニル及びフエニルジオキシ
ジフェニル等が含まれる。Examples of dioxydiphenyl and its nuclear-substituted derivatives include dioxydiphenyl, dioxydiphenyl chloride, dioxydiphenyl bromide, methyldiogydiphenyl, methoxydioxydiphenyl, and phenyldioxydiphenyl.
Ｃ）成分は、炭酸残基よりなる。Component C) consists of carbonic acid residues.
この炭酸残基を与える化合物としては１例えばジフェニ
ルカーボネート、ジトリルカーボネートフェニルトリル
カーボネート及びジナフチルカーボネートのようなジア
リールカーボネート、及び／または、例えばジエチルカ
ーボネート、ジメチルカーボネート、ジメチルジカーボ
ネート及びジエチルジカーボネートのようなシアリレキ
ルカーボネート、グリコールカーボネート等が含まれる
。Compounds providing this carbonic acid residue include 1 diaryl carbonates such as diphenyl carbonate, ditolyl carbonate, phenyl tolyl carbonate and dinaphthyl carbonate, and/or diaryl carbonates such as diethyl carbonate, dimethyl carbonate, dimethyl dicarbonate and diethyl dicarbonate. These include sialylekyl carbonate, glycol carbonate, etc.
ｄ）成分は、芳香族ジカルボン酸残基よりなる。Component d) consists of aromatic dicarboxylic acid residues.
該芳香族ジカルボン酸残基としては、８〜２４個の炭素
原子を有し、芳香族環１個あたり４個までの０１〜Ｃ４
アルキル基、Ｃ１〜Ｃ４アルコキシ基もしくはハロゲン
原子によって置換されていてもよく、例えばナフタレン
−１，５−ジカルボン酸、ジフェニル−２，２′−ジカ
ルボン酸、ジフェニル−４，４′−ジカルボン酸、ジフ
ェニルメタン−４，４°−ジカルボン酸、ジフェニルエ
ーテル−４，４′−ジカルボン酸、ジフェニルスルホン
−４，４“−ジカルボン酸、テレフタル酸、イソフタル
酸、ナフタレン−２，６−ジカルボン酸及びそれらの核
Ｗ！！！！誘導体等が含まれる。またｄ）成分の一部を
液晶性を損なわない範囲で、コハク酸、アジピン酸等の
如き脂肪族ジカルボン酸、シクロヘキサンジカルボン酸
の如き脂環族ジカルボン酸等の残基で置き換えてもよい
。The aromatic dicarboxylic acid residue has 8 to 24 carbon atoms, and up to 4 01 to C4 per aromatic ring.
It may be substituted with an alkyl group, a C1-C4 alkoxy group or a halogen atom, such as naphthalene-1,5-dicarboxylic acid, diphenyl-2,2'-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenylmethane -4,4°-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, diphenylsulfone-4,4''-dicarboxylic acid, terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid and their nuclei W! !!!Includes derivatives, etc.In addition, a part of component d) may be aliphatic dicarboxylic acids such as succinic acid, adipic acid, etc., alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, etc., within a range that does not impair liquid crystallinity. May be replaced with a residue.
本発明で用いる上記ａ）、ｂ）、Ｃ）及びｄ）成分より
なる液晶性ポリエステルカーボネート系樹脂のそれ゛ぞ
れの成分のモル比は
Ｏ≦ａ／（ａ＋ｂ）≦０．９９
０、０１≦ｃ／（ｃ＋ｄ）≦１．０
ａ＋ｄ＞０
であることが好ましいが、より好適には０、０１≦ａ／
（ａ＋ｂ）≦０．９８
０．０１≦ｃ／（ｃ＋ｄ）≦１．０
であることを満足するのがよい。The molar ratio of each component of the liquid crystalline polyester carbonate resin consisting of the above components a), b), C) and d) used in the present invention is O≦a/(a+b)≦0.99 0,01 It is preferable that ≦c/(c+d)≦1.0 a+d>0, more preferably 0, 01≦a/
It is preferable to satisfy the following conditions: (a+b)≦0.98 0.01≦c/(c+d)≦1.0.
本発明における液晶性ボリエステルカーボネト樹脂は、
通常のポリエステルの重縮合法によって得ることが可能
である。The liquid crystalline polyester carbonate resin in the present invention is
It can be obtained by the usual polyester polycondensation method.
本発明においては、上記液晶性ポリエステルカーボネー
ト系樹脂１００重量部に対し、金属不活性剤を０．１〜
５重量重量部中る。In the present invention, a metal deactivator of 0.1 to 100 parts by weight is added to 100 parts by weight of the liquid crystalline polyester carbonate resin.
Contains 5 parts by weight.
本発明で用いられる金属不活性剤としては、３− （Ｎ
−サリチロイル）アミノ−１，２，４−トリアゾール、
デカメチレンジカルボン酸ジサリチロイルヒドラジドン
、Ｎ、Ｎ’−ビス（３−（３゜５−ジ−ｔ−ブチル−４
−ヒドロキシフェニル）プロピオニル〕ヒドラジン、ア
ジピン酸ビス（アセチルヒドラジド）、Ｎ、Ｎ’ −へ
キサメチレン−ビス（３，５−ジ−ｔ−ブチル−４−ヒ
ドロキシ−ヒドロシナミツド）、Ｎ、Ｎ’−ビス〔３−
（４−ヒドロキシフェニル）プロピオニル〕ヒドラジン
、オキサル酸ビス（ベンジリデン−ヒドラジッド）、Ｎ
、Ｎ’ −ジサリチリデンオキサリルジヒドラジッド、
Ｎ−サリチロイル−Ｎ’ −（２−ヒドロキシ）ベンジ
リデンヒドラジン、Ｎ−サリチロイル−Ｎ゛−アセチル
ヒドラジン、Ｎ、Ｎ’−ジフェニルオキサミド、Ｎ、Ｎ
’ −ジ（２−ヒドロキシフェニル）オキサミド、フタ
ル酸ビス（２−２エノキシ−プロビオニルヒドラジッド
）、インフタル酸ビス（２−フェノキシプロピオこルヒ
ドラジッド）、Ｎ、Ｎ’−ビス（３、５ジーｔ−ブチル
−４−ヒドロキシフェニル）プロピオニルオキシエチル
〕オキサミド等が挙げられ、これらの１種または２種以
上の組合せで使用できる。この中でも特に好ましい金属
不活性剤は、３−（Ｎ−サリチロイル）アミノ−１，２
゜４−トリアゾール、デカメチレンジカルボン酸ジサリ
チロイルヒドラジドンである。The metal deactivator used in the present invention includes 3-(N
-salicyloyl)amino-1,2,4-triazole,
Decamethylenedicarboxylic acid disalicyloylhydrazidone, N,N'-bis(3-(3゜5-di-t-butyl-4
-hydroxyphenyl)propionyl]hydrazine, adipate bis(acetylhydrazide), N,N'-hexamethylene-bis(3,5-di-t-butyl-4-hydroxy-hydrocinamide), N,N'-bis[ 3-
(4-hydroxyphenyl)propionyl]hydrazine, oxalate bis(benzylidene-hydrazide), N
, N'-disalicylidene oxalyl dihydrazide,
N-Salicyloyl-N'-(2-hydroxy)benzylidenehydrazine, N-Salicyloyl-N'-acetylhydrazine, N,N'-diphenyloxamide, N,N
'-di(2-hydroxyphenyl)oxamide, bis(2-2-enoxy-probionyl hydrazide) phthalate, bis-inphthalate (2-phenoxypropiochlorhydrazide), N,N'-bis(3,5-di- Examples include t-butyl-4-hydroxyphenyl)propionyloxyethyl]oxamide, which can be used alone or in combination of two or more. Among these, a particularly preferred metal deactivator is 3-(N-salicyloyl)amino-1,2
゜4-triazole, decamethylene dicarboxylic acid disalicyloylhydrazidone.
本発明においては、液晶性ポリエステルカーボネート系
樹脂１００重量部に対し、上記金属不活性剤は０．０１
〜５重量部配置部る。 ０．０１重量部より少ない量で
は、耐酸化性（耐熱安定性）改良に対する効果は発現せ
ず、５重量部より多い量では樹脂組成物の強度低下や成
形性低下があり好ましくない、一般に好ましい配合量は
０．０３〜２重量部、更に好ましくは０．０５〜０．５
重量部である。In the present invention, the amount of the metal deactivator is 0.01 parts by weight per 100 parts by weight of the liquid crystalline polyester carbonate resin.
~5 parts by weight. If the amount is less than 0.01 parts by weight, no effect on improving oxidation resistance (thermal stability) will be exhibited, and if the amount is more than 5 parts by weight, the strength and moldability of the resin composition will decrease, which is not desirable, but is generally preferred. The blending amount is 0.03 to 2 parts by weight, more preferably 0.05 to 0.5 parts by weight.
Parts by weight.
本発明における組成物には、ａ）液晶性ポリエステルカ
ーボネート樹脂以外のサーモトロピック液晶性ポリマー
、ｂ）溶融時に液晶性を示さない熱可塑性樹脂、Ｃ）熱
硬化性樹脂のうちの一種あるいはそれ以りを含有してい
てもよい。The composition of the present invention includes one or more of a) thermotropic liquid crystalline polymers other than liquid crystalline polyester carbonate resins, b) thermoplastic resins that do not exhibit liquid crystallinity when melted, and C) thermosetting resins. may contain.
上記のサーモトロピック液晶性ポリマーとしては、完全
及び非完全芳香族ポリエステル、芳香族脂肪族ポリエス
テル、芳香族ポリアゾメチン、完全及び非完全芳香族ポ
リエステル−アミド等が挙げられる。Examples of the above-mentioned thermotropic liquid crystalline polymers include fully and partially aromatic polyesters, aromatic aliphatic polyesters, aromatic polyazomethines, fully and partially aromatic polyester-amides, and the like.
上記ｂ）の熱可塑性樹脂としては、例えばポリスチレン
、耐１＋ｌｔ性ポリスチレン、ＡＳ樹脂、ＡＢＳ樹脂、
ポリエチレン、ポリプロピレン、ポリ酢酸ビニル、ポリ
塩化ビニル、ポリウレタン、ポリアセタール、ポリカー
ボネート、ポリエチレンテレフタレート、ポリブチレン
テレフタレート、ポリアミド、ポリエーテルイミド、ポ
リアミドイミド、ポリエーテルエーテルケトン、ポリス
ルフォン、ポリフェニレンスルフィド、ポリフェニレン
オキサイド等を挙げることができる。Examples of the thermoplastic resin b) above include polystyrene, 1+lt resistant polystyrene, AS resin, ABS resin,
Examples include polyethylene, polypropylene, polyvinyl acetate, polyvinyl chloride, polyurethane, polyacetal, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyetherimide, polyamideimide, polyetheretherketone, polysulfone, polyphenylene sulfide, polyphenylene oxide, etc. be able to.
上記Ｃ）の熱硬化性樹脂としては、例えばフェノール樹
脂、エポキシ樹脂、メラミン樹脂、ユリア樹脂、不飽和
ポリエステル樹脂等が含まれる。Examples of the thermosetting resin C) include phenol resins, epoxy resins, melamine resins, urea resins, and unsaturated polyester resins.
また、本発明の液晶性ポリエステルカーボネート樹脂組
成物に対し、ガラス繊維、炭素繊維、タルク等の強化材
、充填剤、抗酸化剤、核剤、難燃剤、顔料、安定剤、可
塑剤、滑剤、離型剤等の添加剤を配合して、成形品の所
望の特性を付与することができる。In addition, the liquid crystalline polyester carbonate resin composition of the present invention may include reinforcing materials such as glass fiber, carbon fiber, and talc, fillers, antioxidants, nucleating agents, flame retardants, pigments, stabilizers, plasticizers, lubricants, Additives such as a mold release agent can be blended to impart desired properties to the molded article.
本発明の組成物の調製は、従来の樹脂組成物調製法とし
て一般に用いられている公知の方法により容易に調製さ
れる。The composition of the present invention can be easily prepared by a known method that is generally used for preparing conventional resin compositions.
例えば、各成分を混合した後、押出機により溶融混練し
てペレットを調製し、しかる後成形する方法、−旦組成
の異なるペレットを調製し、そのペレットを所定量混合
して成形し、成形後に目的組成の成形品を得る方法、成
形機に各成分を直接仕込む方法等何れも使用できる。For example, after mixing each component, melt kneading with an extruder to prepare pellets, and then molding. Any method can be used, such as a method for obtaining a molded article having the desired composition or a method for directly charging each component into a molding machine.
また、本発明の必須成分である金属不活性剤を液晶性ポ
リエステルカーボネートの原料から製造・加工工程中の
任意の時期に全部または一部を加えることも可能である
。Further, it is also possible to add all or part of the metal deactivator, which is an essential component of the present invention, at any time during the production and processing steps from the raw material of the liquid crystalline polyester carbonate.
実施例
以下、実施例及び比較例により、本発明の内容を具体的
に説明する。尚、実施例中に用いた液晶性ポリエステル
カーボネートの耐酸化性の評価方法は次の通りである。EXAMPLES The contents of the present invention will be specifically explained below using examples and comparative examples. The method for evaluating the oxidation resistance of the liquid crystalline polyester carbonate used in the examples is as follows.
評価方法
メトラー社製の熱天秤ＴＧ−５０を用いて、サンプル樹
脂的２０■ｇを窒素気流中において昇温速度２０”Ｃ／
ｓｉｎ、で３００℃まで昇温し、 ３００℃にて保持し
た時の重量の経時変化（１０００，３０００秒経過時）
を測定した。３００℃に昇温した時の重量を基準として
重量減少率を求めた。Evaluation method Using a thermobalance TG-50 manufactured by Mettler, 20g of sample resin was heated at a rate of 20"C/20"C in a nitrogen stream.
Change in weight over time when heated to 300℃ and held at 300℃ (after 1000 and 3000 seconds)
was measured. The weight loss rate was determined based on the weight when the temperature was raised to 300°C.
実施例１〜３、比較例１〜３
原料として、ｐ−ヒドロキシ安息香酸２２重量部、４，
４′−ジヒドロキシジフェニル２０重量部、炭酸ジフェ
ニル６２重量部を用いて、溶融重縮合反応を行ない、淡
茶色のポリエステルカーボネートを得た。Examples 1 to 3, Comparative Examples 1 to 3 As raw materials, 22 parts by weight of p-hydroxybenzoic acid, 4,
A melt polycondensation reaction was carried out using 20 parts by weight of 4'-dihydroxydiphenyl and 62 parts by weight of diphenyl carbonate to obtain a light brown polyester carbonate.
インヘレント粘度［η］は２．９８であった。また、示
を走査熱量測定（ＤＳＣ）により、結晶相から液晶相へ
の転移温度は２６７℃であった。そして、偏光顕微鏡で
光学異方相が２８０℃以上で観察された。熱重量分析に
より、熱分解開始温度（Ｔｄ）は、４６３℃であった。The inherent viscosity [η] was 2.98. Moreover, the transition temperature from the crystal phase to the liquid crystal phase was 267° C. as determined by scanning calorimetry (DSC). Then, an optically anisotropic phase was observed at 280° C. or higher using a polarizing microscope. According to thermogravimetric analysis, the thermal decomposition onset temperature (Td) was 463°C.
上記の方法により調製した液晶性ポリエステルカーボネ
ートを１４０℃にて５時間以上乾燥させた後、その液晶
性ポリエステルカーボネートに対し金属不活性剤を表１
に示す割合で混合し、射出成形機を用いて、射出温度２
８０℃、金型温度８０℃にて射出成形を行なった。得ら
れたサンプル樹脂の重量減少率を表１に示す。After drying the liquid crystalline polyester carbonate prepared by the above method at 140°C for 5 hours or more, a metal deactivator was added to the liquid crystalline polyester carbonate as shown in Table 1.
Mix in the proportions shown in and use an injection molding machine at injection temperature 2.
Injection molding was performed at a temperature of 80°C and a mold temperature of 80°C. Table 1 shows the weight loss rate of the sample resin obtained.
同様に比較例として、上記液晶性ポリエステルカーボネ
ートを射出成形機を用いて、射出温度２８０℃、金型温
度８０℃にて射出成形を行なった。Similarly, as a comparative example, the above liquid crystalline polyester carbonate was injection molded using an injection molding machine at an injection temperature of 280°C and a mold temperature of 80°C.
更に、上記液晶性ポリエステルカーボネートに対し抗酸
化剤を表１に示す割合で混合し、射出成形機を用いて、
射出温度２８０℃、金型温度８０℃にて射出成形を行な
った。得られたサンプル樹脂の重量減少率を表１に示す
。Furthermore, an antioxidant was mixed with the liquid crystalline polyester carbonate in the proportion shown in Table 1, and using an injection molding machine,
Injection molding was performed at an injection temperature of 280°C and a mold temperature of 80°C. Table 1 shows the weight loss rate of the sample resin obtained.
表１の結果から明らかなように、金属不活性剤を配合す
ることにより、重量減少率は低下し、耐酸化性が改善し
たことがわかる。As is clear from the results in Table 1, it can be seen that by blending the metal deactivator, the weight loss rate was reduced and the oxidation resistance was improved.
表 １
ＰＥＣ：液晶性ポリエステルカーボネート金属不活性剤
’）：３−（Ｎ−サリチロイル）アミノ−１，２，４−
トリアゾール
金属不活性剤２）：デカメチレンジカルボン酸ジサリチ
ロイルヒドラジドン
金属不活性剤３）：Ｎ、Ｎ’−ビス（３、５−ジ−ｔ−
ブチル−４−ヒドロキシフェニル）プロピオニル〕ヒド
ラジン
フェノール系抗酸化剤ニトリエチレングリコール−ヒス
（３−（３−ｔ−ブチル−５−メチル−４＝ヒドロキシ
フエニル）プロピオネートコチオエーテル系抗酸化剤：
テトラキス〔メチレン−３−（ドデシルチオ）プロピオ
ナートコメタン実施例４、比較例４
原料として、Ｐ−ヒドロキシ安息香酸２５重量部、４，
４゛ −ジヒドロキシジフェニル１５ｉ１部、炭酸ジフ
ェニル６６重量部を用いて、溶融重縮合反応を行ない、
薄茶色のポリエステルカーボネート樹脂を得た。Table 1 PEC: Liquid crystalline polyester carbonate metal deactivator'): 3-(N-salicyloyl)amino-1,2,4-
Triazole metal deactivator 2): decamethylene dicarboxylic acid disalicyloylhydrazidone metal deactivator 3): N,N'-bis(3,5-di-t-
Butyl-4-hydroxyphenyl)propionyl hydrazine phenolic antioxidant Nitriethylene glycol-his(3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate cothioether antioxidant:
Tetrakis[methylene-3-(dodecylthio)propionate comethane Example 4, Comparative Example 4 As raw materials, 25 parts by weight of P-hydroxybenzoic acid, 4,
Performing a melt polycondensation reaction using 1 part of 15i of 4'-dihydroxydiphenyl and 66 parts by weight of diphenyl carbonate,
A light brown polyester carbonate resin was obtained.
得られた樹脂の結晶相から液晶相への転移温度は、示差
走査熱量測定（Ｄ Ｓ Ｃ）から２６２℃であり、偏光
顕微鏡下でも２６２℃以上で光学異方相が観察された。The transition temperature from the crystal phase to the liquid crystal phase of the obtained resin was determined to be 262° C. by differential scanning calorimetry (D SC), and an optically anisotropic phase was observed at 262° C. or higher even under a polarizing microscope.
液晶性ポリエステルカーボネートを１４０℃で８時間乾
燥した後、樹脂１００重量部、金属不活性剤０．２重量
部を、東洋精機製作所製デルタ型２ブレードミキサー（
ラボプラストミルーペレフトミキサーＤ−２００ＥＸＨ
型）に仕込み、２７５℃で５分間混練後ストランド状に
押出し、切断してペレットとした。用いた金属不活性剤
は実施例１の場合と同一とした。After drying the liquid crystalline polyester carbonate at 140°C for 8 hours, 100 parts by weight of the resin and 0.2 parts by weight of the metal deactivator were mixed in a delta type 2-blade mixer manufactured by Toyo Seiki Seisakusho (
Labo Plastomi Loupe Left Mixer D-200EXH
After kneading at 275° C. for 5 minutes, the mixture was extruded into strands and cut into pellets. The metal deactivator used was the same as in Example 1.
上記方法で得られた組成物のペレットを１４０℃で８時
間乾煙し、型締力１２トンの射出成形ａ！（日本製鋼所
製Ｊ１２−３ＢＩＩ）を用いて、バレル温度３０５℃、
金型温度１００℃で１２７１履Ｘ １２．７ｍｍ、厚さ
３．２ｍ腸の平板を成形し、ＡＳＴ）！ −０７９０に
準拠して曲げ強度と曲げ弾性率をそれぞれ測定した。The pellets of the composition obtained by the above method were dry-smoked at 140°C for 8 hours, and injection molded with a mold clamping force of 12 tons a! (J12-3BII made by Japan Steel Works), the barrel temperature was 305℃,
At a mold temperature of 100°C, a flat plate of 1271 mm x 12.7 mm and 3.2 m thick is molded and AST)! Bending strength and bending elastic modulus were each measured in accordance with -0790.
これらの結果を金属不活性剤を配合しない場合の物性と
比較するために、液晶性ポリエステルカーボネートを上
記の方法で溶融混線、射出成形し物性評価した。In order to compare these results with the physical properties when no metal deactivator is blended, liquid crystalline polyester carbonate was melt mixed and injection molded using the above method and the physical properties were evaluated.
以上の結果を表２に示す。The above results are shown in Table 2.
表２の結果から明らかなように、金属不活性剤を配合す
ることにより機械的物性も向上していることがわかる。As is clear from the results in Table 2, it can be seen that the mechanical properties are also improved by blending the metal deactivator.
表２
発明の効果
本発明のごとく、液晶性ポリエステルカーボネートに金
属不活性剤を配合することにより、液晶性ポリエステル
カーボネートの加熱時の重量減少率は低下し、耐醜化性
が改善され、強度、弾性率の優れた射出成形品、Ｊｉ！
維及びフィルム等が得られる。Table 2 Effects of the invention By blending a metal deactivator into liquid crystalline polyester carbonate as in the present invention, the weight loss rate of the liquid crystalline polyester carbonate upon heating is reduced, the disfiguring resistance is improved, and the strength and elasticity of the liquid crystalline polyester carbonate are improved. Injection molded products with excellent efficiency, Ji!
Fibers and films can be obtained.
Claims (1)
部に対し、金属不活性剤を０．０１〜５重量部配合した
ことを特徴とする液晶性ポリエステルカーボネート樹脂
組成物。 （２）液晶性ポリエステルカーボネート樹脂が、ａ）芳
香族オキシカルボン酸残基 ｂ）芳香族ジオール残基 ｃ）炭酸残基 ｄ）芳香族ジカルボン酸残基 より成り、そのモル比が ０≦ａ／（ａ＋ｂ）≦０．９９ ０．０１≦ｃ／（ｃ＋ｄ）≦１．０ ａ＋ｄ＞０ である請求項１記載の液晶性ポリエステルカーボネート
樹脂組成物。 （３）金属不活性剤が、３−（Ｎ−サリチロイル）アミ
ノ−１、２、４−トリアゾール、デカメチレンジカルボ
ン酸ジサリチロイルヒドラジドン、Ｎ、Ｎ’−ビス〔３
−（３、５−ジ−ｔ−ブチル−４−ヒドロキシフェニル
）プロピオニル〕ヒドラジンである請求項１または２記
載の液晶性ポリエステルカーボネート樹脂組成物。Scope of Claims: (1) A liquid crystal polyester carbonate resin composition characterized in that 0.01 to 5 parts by weight of a metal deactivator is blended with 100 parts by weight of the liquid crystal polyester carbonate resin. (2) The liquid crystalline polyester carbonate resin consists of a) aromatic oxycarboxylic acid residue b) aromatic diol residue c) carbonic acid residue d) aromatic dicarboxylic acid residue, and the molar ratio thereof is 0≦a/ The liquid crystalline polyester carbonate resin composition according to claim 1, wherein (a+b)≦0.99 0.01≦c/(c+d)≦1.0 a+d>0. (3) The metal deactivator is 3-(N-salicyloyl)amino-1,2,4-triazole, decamethylenedicarboxylic acid disalicyloylhydrazidone, N,N'-bis[3
The liquid crystalline polyester carbonate resin composition according to claim 1 or 2, which is -(3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11752690A JPH0415249A (en) | 1990-05-09 | 1990-05-09 | Liquid-crystal polyester carbonate resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11752690A JPH0415249A (en) | 1990-05-09 | 1990-05-09 | Liquid-crystal polyester carbonate resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0415249A true JPH0415249A (en) | 1992-01-20 |
Family
ID=14713971
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11752690A Pending JPH0415249A (en) | 1990-05-09 | 1990-05-09 | Liquid-crystal polyester carbonate resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0415249A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6426622A (en) * | 1987-04-01 | 1989-01-27 | Mitsui Toatsu Chemicals | Polymer for plastic lens having high refractive index and lens composed of said polymer |
| JPH0236216A (en) * | 1987-09-19 | 1990-02-06 | Mitsui Toatsu Chem Inc | Resin for plastic lens having high refractive index and lens made thereof |
| US5834621A (en) * | 1995-08-22 | 1998-11-10 | Sumitomo Seika Chemicals Co., Ltd. | Novel sulfur-containing compound and method for preparing the same |
| WO2008114765A1 (en) | 2007-03-16 | 2008-09-25 | Mitsubishi Gas Chemical Company, Inc. | Resin composition for optical member and optical member obtained from the same |
| JP2020172407A (en) * | 2019-04-10 | 2020-10-22 | 住友金属鉱山株式会社 | Fine particle dispersing liquid excellent in high temperature stability and fine particle dispersion |
-
1990
- 1990-05-09 JP JP11752690A patent/JPH0415249A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6426622A (en) * | 1987-04-01 | 1989-01-27 | Mitsui Toatsu Chemicals | Polymer for plastic lens having high refractive index and lens composed of said polymer |
| JPH0236216A (en) * | 1987-09-19 | 1990-02-06 | Mitsui Toatsu Chem Inc | Resin for plastic lens having high refractive index and lens made thereof |
| US5834621A (en) * | 1995-08-22 | 1998-11-10 | Sumitomo Seika Chemicals Co., Ltd. | Novel sulfur-containing compound and method for preparing the same |
| WO2008114765A1 (en) | 2007-03-16 | 2008-09-25 | Mitsubishi Gas Chemical Company, Inc. | Resin composition for optical member and optical member obtained from the same |
| EP2463318A1 (en) | 2007-03-16 | 2012-06-13 | Mitsubishi Gas Chemical Company, Inc. | Resin composition for optical member and optical member obtained from the same |
| EP2799455A2 (en) | 2007-03-16 | 2014-11-05 | Mitsubishi Gas Chemical Company, Inc. | Resin composition for optical member and optical member obtained from the same |
| JP2020172407A (en) * | 2019-04-10 | 2020-10-22 | 住友金属鉱山株式会社 | Fine particle dispersing liquid excellent in high temperature stability and fine particle dispersion |
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