JPH0267366A - Thermoplastic resin composition - Google Patents
Thermoplastic resin compositionInfo
- Publication number
- JPH0267366A JPH0267366A JP63218163A JP21816388A JPH0267366A JP H0267366 A JPH0267366 A JP H0267366A JP 63218163 A JP63218163 A JP 63218163A JP 21816388 A JP21816388 A JP 21816388A JP H0267366 A JPH0267366 A JP H0267366A
- Authority
- JP
- Japan
- Prior art keywords
- aromatic
- liquid crystal
- monomer
- acrylate
- resin
- 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
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 18
- 239000011342 resin composition Substances 0.000 title claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 33
- 229920000106 Liquid crystal polymer Polymers 0.000 claims abstract description 26
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 125000000524 functional group Chemical group 0.000 claims abstract description 13
- 125000003277 amino group Chemical group 0.000 claims abstract description 11
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 9
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- 125000004018 acid anhydride group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 27
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 23
- 239000000126 substance Substances 0.000 abstract description 21
- -1 aromatic diol Chemical class 0.000 abstract description 18
- 239000000203 mixture Substances 0.000 abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 10
- 229920001634 Copolyester Polymers 0.000 abstract description 8
- 229920001577 copolymer Polymers 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-M 4-hydroxybenzoate Chemical compound OC1=CC=C(C([O-])=O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-M 0.000 abstract 1
- 239000004593 Epoxy Substances 0.000 abstract 1
- 150000008065 acid anhydrides Chemical class 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 22
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 17
- 229920000728 polyester Polymers 0.000 description 16
- 238000002844 melting Methods 0.000 description 12
- 230000008018 melting Effects 0.000 description 12
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 9
- 229920001890 Novodur Polymers 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 9
- 229920003232 aliphatic polyester Polymers 0.000 description 8
- 229920000578 graft copolymer Polymers 0.000 description 8
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 7
- XCZKKZXWDBOGPA-UHFFFAOYSA-N 2-phenylbenzene-1,4-diol Chemical compound OC1=CC=C(O)C(C=2C=CC=CC=2)=C1 XCZKKZXWDBOGPA-UHFFFAOYSA-N 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 4
- 229920000343 polyazomethine Polymers 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 3
- 229920006038 crystalline resin Polymers 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 2
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 2
- 229920001893 acrylonitrile styrene Polymers 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 229960004050 aminobenzoic acid Drugs 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
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 239000008121 dextrose Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 229920006015 heat resistant resin Polymers 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 2
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- ORTVZLZNOYNASJ-OWOJBTEDSA-N (e)-but-2-ene-1,4-diol Chemical compound OC\C=C\CO ORTVZLZNOYNASJ-OWOJBTEDSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 1
- KIKBJYQCJJXCBZ-UHFFFAOYSA-N 1-octylpyrrole-2,5-dione Chemical compound CCCCCCCCN1C(=O)C=CC1=O KIKBJYQCJJXCBZ-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 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
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- DNUYOWCKBJFOGS-UHFFFAOYSA-N 2-[[10-(2,2-dicarboxyethyl)anthracen-9-yl]methyl]propanedioic acid Chemical compound C1=CC=C2C(CC(C(=O)O)C(O)=O)=C(C=CC=C3)C3=C(CC(C(O)=O)C(O)=O)C2=C1 DNUYOWCKBJFOGS-UHFFFAOYSA-N 0.000 description 1
- UGIJCMNGQCUTPI-UHFFFAOYSA-N 2-aminoethyl prop-2-enoate Chemical compound NCCOC(=O)C=C UGIJCMNGQCUTPI-UHFFFAOYSA-N 0.000 description 1
- UGCSBAYAYZNGRD-UHFFFAOYSA-N 2-anilinoethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCNC1=CC=CC=C1 UGCSBAYAYZNGRD-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- UPZFLZYXYGBAPL-UHFFFAOYSA-N 2-ethyl-2-methyl-1,3-dioxolane Chemical compound CCC1(C)OCCO1 UPZFLZYXYGBAPL-UHFFFAOYSA-N 0.000 description 1
- UWRZIZXBOLBCON-UHFFFAOYSA-N 2-phenylethenamine Chemical class NC=CC1=CC=CC=C1 UWRZIZXBOLBCON-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- NMSZFQAFWHFSPE-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxycarbonyl)but-3-enoic acid Chemical compound OC(=O)CC(=C)C(=O)OCC1CO1 NMSZFQAFWHFSPE-UHFFFAOYSA-N 0.000 description 1
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 description 1
- SNCMCDMEYCLVBO-UHFFFAOYSA-N 3-aminopropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCN SNCMCDMEYCLVBO-UHFFFAOYSA-N 0.000 description 1
- CXJAFLQWMOMYOW-UHFFFAOYSA-N 3-chlorofuran-2,5-dione Chemical compound ClC1=CC(=O)OC1=O CXJAFLQWMOMYOW-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- LBSXSAXOLABXMF-UHFFFAOYSA-N 4-Vinylaniline Chemical compound NC1=CC=C(C=C)C=C1 LBSXSAXOLABXMF-UHFFFAOYSA-N 0.000 description 1
- NGUGWHFIVAQVMN-UHFFFAOYSA-N 4-aminobut-3-en-2-one Chemical compound CC(=O)C=CN NGUGWHFIVAQVMN-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- PXGZQGDTEZPERC-IZLXSQMJSA-N OC(=O)[C@H]1CC[C@H](C(O)=O)CC1 Chemical compound OC(=O)[C@H]1CC[C@H](C(O)=O)CC1 PXGZQGDTEZPERC-IZLXSQMJSA-N 0.000 description 1
- 239000007977 PBT buffer Substances 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000008364 bulk solution Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000003869 coulometry Methods 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 1
- FGDAXMHZSNXUFJ-UHFFFAOYSA-N ethene;prop-1-ene;prop-2-enenitrile Chemical group C=C.CC=C.C=CC#N FGDAXMHZSNXUFJ-UHFFFAOYSA-N 0.000 description 1
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical group C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920006229 ethylene acrylic elastomer Polymers 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 229920005555 halobutyl Polymers 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 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
- 229920002681 hypalon Polymers 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000314 lubricant Substances 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
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- IJFXRHURBJZNAO-UHFFFAOYSA-N meta--hydroxybenzoic acid Natural products OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- IQFXJRXOTKFGPN-UHFFFAOYSA-N n-ethenyl-n-ethylethanamine Chemical compound CCN(CC)C=C IQFXJRXOTKFGPN-UHFFFAOYSA-N 0.000 description 1
- IOXXVNYDGIXMIP-UHFFFAOYSA-N n-methylprop-2-en-1-amine Chemical compound CNCC=C IOXXVNYDGIXMIP-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-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
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) 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
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
a、産業上の利用分野
本発明は、加工性、耐薬品性および耐熱性に優れた熱可
塑性樹脂組成物に関する。さらに詳しくは、スチレン系
樹脂に液晶ポリマーをブレンドすることにより、加工性
、耐薬品性および耐熱性を顕著に改善せしめた熱可塑性
樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Application The present invention relates to a thermoplastic resin composition having excellent processability, chemical resistance and heat resistance. More specifically, the present invention relates to a thermoplastic resin composition that has significantly improved processability, chemical resistance, and heat resistance by blending a styrene resin with a liquid crystal polymer.
b、従来の技術
アクリロニトリル−ポリブタジェン−スチレン(ABS
)樹脂、アクリロニトリル−エチレンプロピレンゴム−
スチレン(AES )樹脂、アクリロニトリル−スチレ
ン(AS)樹脂およびメチルメタクリレート−スチレン
(MS)樹脂をはじめとするスチレン系樹脂は、優れた
機械的性質に加えて成形性に優れているため、産業界で
幅広い用途に利用されている。b. Prior art acrylonitrile-polybutadiene-styrene (ABS
) Resin, acrylonitrile - ethylene propylene rubber -
Styrenic resins, including styrene (AES) resin, acrylonitrile-styrene (AS) resin, and methyl methacrylate-styrene (MS) resin, are widely used in industry due to their excellent mechanical properties and excellent moldability. It is used for a wide range of purposes.
これらの樹脂は、用途によっては耐熱性や機械的強度が
不足するため、ガラス繊維などの無機フィラーを添加し
て、これらの特性を向上させている。また、耐薬品性を
向上させるために、上記無機フィラーと共に結晶性樹脂
をブレンドすることなどが最近行われている。These resins lack heat resistance and mechanical strength depending on their use, so inorganic fillers such as glass fiber are added to improve these properties. Furthermore, in order to improve chemical resistance, blending of a crystalline resin with the above-mentioned inorganic filler has recently been carried out.
しかしながら、スチレン系樹脂の剛性を向上すべく、ガ
ラス繊維などの無機フィラーを添加すると、弾性率や耐
熱性および耐薬品性は向上するが、成形時に成形機が摩
耗するとか、溶融粘度が上昇するため、加工性が低下す
るといった問題が生じる。また、得られる成形品の外観
が劣ることも多い。However, adding inorganic fillers such as glass fibers to improve the rigidity of styrenic resins improves the elastic modulus, heat resistance, and chemical resistance, but may cause wear of the molding machine during molding or increase the melt viscosity. Therefore, a problem arises in that workability is reduced. Furthermore, the appearance of the resulting molded product is often poor.
これらの欠点を解決すべく、ポリアミドのような結晶性
樹脂(特開昭58−93745号公報) PPE樹脂(
特開昭59−193951号公報)あるいはポリスルホ
ン、スチレン−無水マレイン酸樹脂などの耐熱性樹脂の
添加が試みられているが、結晶性樹脂を添加すると耐熱
性が不足し、耐熱性樹脂を添加すると強度的に脆くなる
ことが多い。In order to solve these drawbacks, crystalline resins such as polyamide (Japanese Unexamined Patent Publication No. 58-93745), PPE resins (
Attempts have been made to add heat-resistant resins such as JP-A-59-193951) or polysulfone, styrene-maleic anhydride resin, but adding crystalline resins results in insufficient heat resistance, and adding heat-resistant resins results in insufficient heat resistance. It is often strong and brittle.
C9発明が解決しようとする課題
本発明者らは、加工性、耐薬品性および耐熱性に優れた
スチレン系樹脂組成物を得るべく鋭意検討した結果、液
晶ポリマーを特定の官能基を有する樹脂に特定の比率で
ブレンドすることによって、上記の点に優れた熱可塑性
樹脂が得られることを見いだし、本発明に到達した。C9 Problems to be Solved by the Invention The present inventors have made intensive studies to obtain a styrenic resin composition with excellent processability, chemical resistance, and heat resistance. It has been discovered that a thermoplastic resin excellent in the above points can be obtained by blending in a specific ratio, and the present invention has been achieved.
60課題を解決するための手段
すなわち本発明の熱可塑性樹脂組成物は、(a)カルボ
キシル基、酸無水物基、エポキシ基、ヒドロキシル基お
よびアミノ基から選ばれた少なくとも1種の官能基を有
する共重合可能な単量体の少なくとも1種が、樹脂中に
0.1〜30重量%共重合されている芳香族ビニルおよ
び/または(メタ)アクリル酸アルキルエステルを必須
成分とする樹脂10〜99重量%と、(b)液晶ポリマ
ー90−1重量%とからなることを特徴とする。60 Means for Solving the Problems, that is, the thermoplastic resin composition of the present invention has (a) at least one functional group selected from a carboxyl group, an acid anhydride group, an epoxy group, a hydroxyl group, and an amino group. Resins 10 to 99 whose essential components are aromatic vinyl and/or (meth)acrylic acid alkyl esters, in which at least one copolymerizable monomer is copolymerized in an amount of 0.1 to 30% by weight. (b) 90-1% by weight of liquid crystal polymer.
本発明の(a)成分の樹脂としては、
(1) 芳香族ビニルおよび/または(メタ)アクリ
ル酸アルキルエステルと、官能基を有する共重合可能な
単量体を共重合させて得られる共重合体樹脂;(2)
(1)にさらに共重合可能な単量体を加え、共重合さ
せて得られる共重合体樹脂;
(3)ゴム状重合体の存在下に、上記の(1)または(
2)の単量体を重合して得られるグラフト共重合体樹脂
;(4)官能基を有する単量体で変性されたゴム状重合
体の存在下に、上記の(1)または(2)の単量体を重
合して得られるグラフト共重合体樹脂;あるいは(5)
上記の(1)、(2)、(3)、(4)などと、官能基
を有する単量体を共重合しない(1)、(2)、(3)
、(4)などとの混合物、が挙げられる。The resin of component (a) of the present invention includes (1) a copolymer obtained by copolymerizing an aromatic vinyl and/or (meth)acrylic acid alkyl ester with a copolymerizable monomer having a functional group; Combined resin; (2)
A copolymer resin obtained by further adding a copolymerizable monomer to (1) and copolymerizing it; (3) In the presence of a rubbery polymer, the above (1) or (
A graft copolymer resin obtained by polymerizing the monomer of (2); (4) the above (1) or (2) in the presence of a rubbery polymer modified with a monomer having a functional group; A graft copolymer resin obtained by polymerizing the monomers; or (5)
Do not copolymerize monomers with functional groups with the above (1), (2), (3), (4), etc. (1), (2), (3)
, (4), etc.
(a)成分の樹脂が芳香族ビニルを主成分とするもので
あると、加工性に優れ、一方(メタ)アクリル酸アルキ
ルエステルを主成分とするものであると、耐候性および
耐薬品性に優れる。When the resin of component (a) is mainly composed of aromatic vinyl, it has excellent processability, while when it is composed mainly of (meth)acrylic acid alkyl ester, it has poor weather resistance and chemical resistance. Excellent.
上記芳香族ビニルとしては、スチレン、α−メチルスチ
レン、メチルスチレン、ビニルキシレン、モノクロルス
チレン、ジクロルスチレン、モツプロムスチレン、ジブ
ロムスチレン、p−ターシャリ−ブチルスチレン、エチ
ルスチレン、ビニルナフタレンなどがあり、これらは1
種または2種以上で使用される。好ましい芳香族ビニル
はスチレンである。Examples of the aromatic vinyls mentioned above include styrene, α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, motsupromustyrene, dibromustyrene, p-tert-butylstyrene, ethylstyrene, and vinylnaphthalene. , these are 1
Used in one species or in combination of two or more. A preferred aromatic vinyl is styrene.
上記(メタ)アクリル酸アルキルエステルとしては、(
メタ)アクリル酸メチル、(メタ)アクリル酸エチル、
(メタ)アクリル酸プロピル、(メタ)アクリル酸ブチ
ル、(メタ)アクリル酸ラウリル、(メタ)アクリル酸
シクロヘキシル、(メタ)アクリル酸2−エチルヘキシ
ルなどが挙げられ、これらは一種または二種以上用いる
ことができる。好ましい(メタ)アクリル酸アルキルは
、(メタ)アクリル酸メチルである。As the above (meth)acrylic acid alkyl ester, (
Methyl acrylate, ethyl (meth)acrylate,
Propyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc. may be used, and one or more of these may be used. Can be done. A preferred alkyl (meth)acrylate is methyl (meth)acrylate.
上記官能基をもつ共重合可能を単量体としては、芳香族
ビニル化合物およびまたは(メタ)アクリル酸アルキル
エステルと共重合可能な、カルボキシル基、酸無水物基
、エポキシ基、ヒドロキシル基およびアミノ基から選ば
れた少なくとも1種の官能基を有する化合物の少なくと
も1種が使用される。これによって、(a)成分と液晶
ポリマーとの相溶性を高めることができる。Examples of copolymerizable monomers having the above functional groups include carboxyl groups, acid anhydride groups, epoxy groups, hydroxyl groups, and amino groups that are copolymerizable with aromatic vinyl compounds and/or (meth)acrylic acid alkyl esters. At least one compound having at least one functional group selected from the following is used. This can improve the compatibility between component (a) and the liquid crystal polymer.
上記カルボキシル基含有不飽和化合物としては、アクリ
ル酸、メタクリル酸、イタコン酸、マレイン酸などがあ
り、好ましくはアクリル酸およびメタクリル酸である。Examples of the carboxyl group-containing unsaturated compound include acrylic acid, methacrylic acid, itaconic acid, and maleic acid, with acrylic acid and methacrylic acid being preferred.
これらは、1種または2種以上で使用される。These may be used alone or in combination of two or more.
酸無水物基含有不飽和化合物としては、無水マレイン酸
、無水イタコン酸、クロロ無水マレイン酸などがあり、
とくに好ましい化合物は無水マレイン酸である。Examples of unsaturated compounds containing acid anhydride groups include maleic anhydride, itaconic anhydride, and chloromaleic anhydride.
A particularly preferred compound is maleic anhydride.
エポキシ基含有不飽和化合物としては、分子中にオレフ
ィンおよびエチレン系不飽和化合物と共重合しうる不飽
和基とエポキシ基をそれぞれ有する化合物がある。Examples of the epoxy group-containing unsaturated compound include compounds each having an unsaturated group and an epoxy group in the molecule that can be copolymerized with an olefin and an ethylenically unsaturated compound.
好ましいエポキシ基含有不飽和化合物としては、下記−
船人
で示される化合物および下記−船人
で示される化合物が挙げられる。Preferred epoxy group-containing unsaturated compounds include the following -
Examples include the compound represented by ``Funajin'' and the compound represented by ``Funajin'' below.
好ましい具体例としては、アクリル酸グリシジル、メタ
クリル酸グリシジル、エタクリル酸グリシジル、イタコ
ン酸グリシジル、アリルグリシジルエーテルがあり、と
くに好ましいエポキシ基含有不飽和化合物は、アクリル
酸グリシジル、メタクリル酸グリシジルおよびアリルグ
リシジルエーテルなどが挙げられ。これらのエポキシ基
含有不飽和化合物は、1種または2種以上で使用される
。Preferred specific examples include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, allyl glycidyl ether, and particularly preferred epoxy group-containing unsaturated compounds include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, etc. is mentioned. These epoxy group-containing unsaturated compounds may be used alone or in combination of two or more.
ヒドロキシル基含有不飽和化合物としては、少なくとも
1個の不飽和結合を有し、かつヒドロキシル基を含有す
る化合物がある。この代表的なものとしては、二重結合
ないしは三重結合を有するアルコール、−価または二価
の不飽和カルボン酸と非置換二価アルコールとのエステ
ルなどが挙げられる。ヒドロキシル基含有不飽和化合物
のうち、好適なものとしては、例えば2−ヒドロキシエ
チルアクリレート、2−ヒドロキシエチルメタクリレー
ト、3−ヒドロキシプロピルアクリレート、3−ヒドロ
キシプロピルメタクリレート、2,3,4.5−テトラ
ヒドロキシペンチルアクリレートなどのアクリル酸、エ
ステル、メタクリル酸エステルや、3−ヒドロキシ−1
−プロペン、4−ヒドロキシ−1−ブテン、trans
−1,4−ジヒドロキシ−2−ブテンなどが挙げられ、
これらは1種または2種以上で使用される。Examples of the hydroxyl group-containing unsaturated compound include compounds that have at least one unsaturated bond and also contain a hydroxyl group. Typical examples thereof include alcohols having double or triple bonds, esters of -valent or divalent unsaturated carboxylic acids, and unsubstituted dihydric alcohols. Among the hydroxyl group-containing unsaturated compounds, suitable examples include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, and 2,3,4.5-tetrahydroxy. Acrylic acid, ester, methacrylic acid ester such as pentyl acrylate, 3-hydroxy-1
-propene, 4-hydroxy-1-butene, trans
-1,4-dihydroxy-2-butene, etc.
These may be used alone or in combination of two or more.
とくに好ましいヒドロキシル基含有不飽和化合物は、2
−ヒドロキシルエチルアクリレート、2〜ヒドロキシル
エチルメタクリレートおよび3−ヒドロキシルプロピル
メタクリレートである。Particularly preferred hydroxyl group-containing unsaturated compounds are 2
-hydroxylethyl acrylate, 2-hydroxylethyl methacrylate and 3-hydroxylpropyl methacrylate.
アミノ基含有不飽和化合物としては、下記−船人で表さ
れるアミノ基または置換アミノ基の少なくとも1種を有
するビニル系単量体があり、具体例としてはアクリルア
ミド、メタクリルアミド、N−メチルアクリルアミドな
どのアクリルアミドまたはメタクリルアミド系誘導体、
アクリル酸アミノエチル、メタクリル酸アミノプロピル
、メタクリル酸ジメチルアミノエチル、メタクリル酸フ
ェニルアミノエチルなどのアクリル酸またはメタクリル
酸のアルキルエステル系誘m 体IN、N−ビニルジエ
チルアミン、N−アセチルビニルアミンなどのビニルア
ミン系誘導体類、アリルアミン、メタクリルアミン、N
−メチルアリルアミンなどのアリルアミン系誘導体類お
よびP−アミノスチレンなどのアミノスチレン類が挙げ
られる。これらのアミノ基または置換アミノ基含有不飽
和化合物は1種または2種以上で使用される。Examples of unsaturated compounds containing an amino group include vinyl monomers having at least one of the following amino groups or substituted amino groups, and specific examples include acrylamide, methacrylamide, and N-methylacrylamide. acrylamide or methacrylamide derivatives, such as
Alkyl ester derivatives of acrylic acid or methacrylic acid such as aminoethyl acrylate, aminopropyl methacrylate, dimethylaminoethyl methacrylate, and phenylaminoethyl methacrylate; vinyl amines such as N-vinyldiethylamine and N-acetylvinylamine; derivatives, allylamine, methacrylamine, N
- Allylamine derivatives such as methylallylamine and aminostyrenes such as P-aminostyrene. These amino group- or substituted amino group-containing unsaturated compounds may be used alone or in combination of two or more.
とくに好ましいアミノ基含有不飽和化合物は、アクリル
アミド、メタクリルアミドなどの(メタ)アクリルアミ
ド誘導体である。Particularly preferred amino group-containing unsaturated compounds are (meth)acrylamide derivatives such as acrylamide and methacrylamide.
上記各種官能基含有単量体の使用量は、樹脂(a)中に
0.1〜30重量%の範囲であり、好ましくは0.2〜
20重景%電量り、さらに好ましくは0.3〜lO重量
%である。0.1重量%未満では、(b)成分である液
晶ポリマーと、ブレンドすべき(a)成分であるスチレ
ン系樹脂との相溶性が悪<、30重量%を越える場合は
耐熱性および流動性の低下などが生じ、好ましくない。The amount of the various functional group-containing monomers used in the resin (a) ranges from 0.1 to 30% by weight, preferably from 0.2 to 30% by weight.
The coulometric content is 20% by weight, more preferably 0.3 to 10% by weight. If it is less than 0.1% by weight, the compatibility between the liquid crystal polymer (b) component and the styrene resin which is the component (a) to be blended will be poor; if it exceeds 30% by weight, the heat resistance and fluidity will be poor. This is not desirable as it may cause a decrease in
上記(2)の共重合可能な単量体としては、アクリロニ
トリル、メタクリレートリル、などのビニルシアン化合
物、メチルアクリレート、エチルアクリレート、ブチル
アクリレート、2−エチルへキシルアクリレート、フェ
ニルアクリレートなどのアクリル酸アルキルエステル類
、メチルメタクリレート、オクチルメタクリレート、ヘ
キシルメタクリレート、ドデシルメタクリレートなどの
メタクリル酸アルキルエステルIN、N−フェニルマレ
イミド、N−オクチルマレイミド、N−シクロヘキシル
マレイミドなどのマレイミド化合物などがあり、これら
共重合可能な単量体は1種または2種以上を使用できる
。Examples of the copolymerizable monomers in (2) above include vinyl cyanide compounds such as acrylonitrile and methacrylate, and acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and phenyl acrylate. methacrylic acid alkyl esters IN such as methyl methacrylate, octyl methacrylate, hexyl methacrylate, and dodecyl methacrylate, maleimide compounds such as N-phenylmaleimide, N-octylmaleimide, and N-cyclohexylmaleimide, and monomers that can be copolymerized with these. One type or two or more types can be used.
上記(3)のグラフト共重合体樹脂中のゴム状重合体は
、好ましくは5〜80重川%、用らに好ましくはlO〜
50重壜%であって、ポリブタジェン、ポリイソプレン
およびスチレンの含量が50重量%以下の熱可塑性のス
チレン−ブタジェン共重合体およびスチレン−エチレン
共重合体、スチレン−プロピレン共重合体などのブロッ
ク共重合体、アクリルゴム、ニトリルゴム、塩素化ポリ
エチレン、EPDM、EPMなどのオレフィンゴムがあ
り、これらは1種または2種以上で使用される。The rubbery polymer in the graft copolymer resin of (3) above is preferably 5 to 80%, preferably 10 to 80%.
Thermoplastic styrene-butadiene copolymers, styrene-ethylene copolymers, styrene-propylene copolymers, and other block copolymers containing 50% by weight and a content of polybutadiene, polyisoprene, and styrene of 50% by weight or less There are olefin rubbers such as rubber, acrylic rubber, nitrile rubber, chlorinated polyethylene, EPDM, and EPM, and these may be used alone or in combination of two or more.
本発明の目的に役立つような変性しうるスチレン系樹脂
の具体例としては、ポリスチレン、スチレン−アクリロ
ニトリル共重合体(^S樹脂)、MS樹脂などが挙げら
れる。Specific examples of modifiable styrenic resins useful for the purposes of the present invention include polystyrene, styrene-acrylonitrile copolymers (^S resins), MS resins, and the like.
また、ゴム状重合体を基質とした変性しうるグラフトポ
リマーとしては、ABS樹脂、メチルメタクリレート−
ポリブタジェン−スチレン(MBS)樹脂、ABS樹脂
、アクリロニトリル−塩素化ポリエチレン−スチレン(
AC5)樹脂などが挙げられる。In addition, examples of graft polymers that can be modified using rubber-like polymers as substrates include ABS resin, methyl methacrylate-
Polybutadiene-styrene (MBS) resin, ABS resin, acrylonitrile-chlorinated polyethylene-styrene (
AC5) Resin, etc. can be mentioned.
本発明の(a)成分である樹脂は、公知の重合法、例え
ば乳化重合法、塊状重合法、懸濁重合法、溶液重合法、
塊状−懸濁重合法、塊状−溶液重合法によって重合する
ことができる。The resin which is component (a) of the present invention can be produced by a known polymerization method, such as an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, a solution polymerization method,
Polymerization can be carried out by a bulk-suspension polymerization method or a bulk-solution polymerization method.
本発明のΦ)成分である液晶ポリマーは、溶融時に光学
的異方性を示す、いわゆるサーモトロピック液晶性高分
子と呼ばれるものであり、100〜400°C1好まし
くは150〜370°C1さらに好ましくは200〜3
50°Cで溶融加工でき、得られた成形品が優れた機械
的性質を示すものを指す。具体的には、完全芳香族ポリ
エステル、芳香族−脂肪族ポリエステル、完全芳香族ポ
リエステルアミド、芳香族−脂肪族ポリエステルアミド
、芳香族ポリアゾメチン、芳香族ポリエステルカーボネ
ート、側鎖に液晶性を示す剛直部分(メソゲン基)をも
つ側鎖型液晶ポリマー、およびこれらの混合物が挙げら
れる。The liquid crystal polymer which is the component Φ) of the present invention is a so-called thermotropic liquid crystal polymer that exhibits optical anisotropy when melted, and has a temperature of 100 to 400°C, preferably 150 to 370°C, and more preferably 150 to 370°C. 200-3
Refers to products that can be melt-processed at 50°C and the resulting molded products exhibit excellent mechanical properties. Specifically, fully aromatic polyester, aromatic-aliphatic polyester, fully aromatic polyester amide, aromatic-aliphatic polyester amide, aromatic polyazomethine, aromatic polyester carbonate, and rigid portions exhibiting liquid crystallinity in their side chains. Examples include side chain type liquid crystal polymers having (mesogen groups) and mixtures thereof.
上記完全芳香族ポリエステルは、テレフタル酸、イソフ
タル酸、2.6−ジカルボキシナフタレンなどの芳香族
ジカルボン酸と、ハイドロキノン、メチルハイドロキノ
ン、フェニルハイドロキノン、クロルハイドロキノン、
ターシャリ−ブチルハイドロキノン、2.6−シヒドロ
キシナフタレン、ビフエノールなどのジオールおよびp
−ヒドロキシ安息香酸、m−ヒドロキシ安息香酸、2.
6−シメチルヒドロキシ安息香酸などの芳香族ヒドロキ
シカルボン酸の共重合体からなる。The above-mentioned fully aromatic polyester includes aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and 2,6-dicarboxynaphthalene, hydroquinone, methylhydroquinone, phenylhydroquinone, chlorohydroquinone,
Diols and p
-hydroxybenzoic acid, m-hydroxybenzoic acid, 2.
It consists of a copolymer of aromatic hydroxycarboxylic acids such as 6-dimethylhydroxybenzoic acid.
上記芳香族−脂肪族ポリエステルは、上記芳香族ポリエ
ステルで用いられた単量体以外に、trans −1,
4−ジカルボキシシクロヘキサン、cis −1゜4−
ジカルボキシシクロヘキサン、これらのアルキル、アリ
ール置換体からなる脂環族ジカルボン酸やエチレングリ
コール、1,4−ブタンジオール、trans−1,4
−ジヒドロキシシクロヘキサンなどの脂環族、脂肪族ジ
オールを適当量共重合した化合物からなる。In addition to the monomers used in the aromatic polyester, the aromatic-aliphatic polyester contains trans -1,
4-dicarboxycyclohexane, cis -1°4-
Dicarboxycyclohexane, alicyclic dicarboxylic acids consisting of alkyl and aryl substituted products of these, ethylene glycol, 1,4-butanediol, trans-1,4
- Consists of a compound copolymerized with an appropriate amount of alicyclic or aliphatic diol such as dihydroxycyclohexane.
上記完全芳香族ポリエステル、芳香族−脂肪族ポリエス
テルのなかで、本発明の(b)成分として好ましいもの
は、
(1) p−ヒドロキシ安息香酸4o〜70モル%と
上記芳香族ジカルボン酸30〜15モル%と、芳香族ジ
オール30〜15モル%からなるコポリエステル:(2
)テレフタル酸および/またはイソフタル酸と、クロル
ハイドロキノン、フェニルハイドロキノン、ターシャリ
−ブチルハイドロキノンおよび/またはハイドロキノン
からなるコポリエステル;(3)p−ヒドロキシ安息香
酸20〜80モル%と、2−ヒドロキシナフタレン−6
−カルボン酸80〜20モル%からなるコポリエステル
;
(4)p−ヒドロキシ安息香酸50〜80モル%と、ポ
リエチレンテレフタレート50〜20モル%を共重合し
てなるコポリエステル;
などである。Among the above fully aromatic polyesters and aromatic-aliphatic polyesters, preferred as component (b) of the present invention are (1) 40 to 70 mol% of p-hydroxybenzoic acid and 30 to 15% of the above aromatic dicarboxylic acid. Copolyester consisting of mol% and 30 to 15 mol% of aromatic diol: (2
) A copolyester consisting of terephthalic acid and/or isophthalic acid and chlorohydroquinone, phenylhydroquinone, tert-butylhydroquinone and/or hydroquinone; (3) 20 to 80 mol% of p-hydroxybenzoic acid and 2-hydroxynaphthalene-6
-Copolyester consisting of 80 to 20 mol% of carboxylic acid; (4) Copolyester formed by copolymerizing 50 to 80 mol% of p-hydroxybenzoic acid and 50 to 20 mol% of polyethylene terephthalate;
また、上記完全芳香族ポリエステルアミドおよび芳香族
−脂肪族ポリエステルアミドは、上記ポリエステルに、
p−アミノ安息香酸、p−フェニレンジアミン、m−フ
ェニレンジアミンなどの芳香族アミンやヘキサメチレン
ジアミンなどの脂肪族ジアミンを共重合したものである
。Further, the fully aromatic polyester amide and the aromatic-aliphatic polyester amide include the polyester,
It is a copolymer of aromatic amines such as p-aminobenzoic acid, p-phenylenediamine, m-phenylenediamine, and aliphatic diamines such as hexamethylenediamine.
上記芳香族ポリアゾメチンは、下記−船人で示される゛
?ゾメチン部分を芳香族主鎖中に含む化合物である。The above-mentioned aromatic polyazomethine is represented by the symbol ``?'' below. It is a compound containing a zometine moiety in its aromatic main chain.
主鎖中に含む化合物である。A compound contained in the main chain.
上記側鎖型液晶ポリマーは、エチレン系主鎖、シロキサ
ン系主鎖等にメソゲン基が側鎖として連なった下記構造
式を繰り返し単位とする液晶ポリマーである。The above-mentioned side chain type liquid crystal polymer is a liquid crystal polymer having a repeating unit of the following structural formula in which a mesogenic group is connected as a side chain to an ethylene-based main chain, a siloxane-based main chain, or the like.
上記芳香族ポリエステルカーボネートは、下記−船人で
示されるカーボネートエステル部分を芳香族R,は水素
原子またはメチル基、nは0〜I2の整数である。ただ
し、n=0のときは−0−(CH2±70−は−O−と
する。また、Xは下記−船人の中から選ばれた構造を有
する。The above-mentioned aromatic polyester carbonate has a carbonate ester moiety represented by the following symbol R, where R is a hydrogen atom or a methyl group, and n is an integer from 0 to I2. However, when n=0, -0-(CH2±70- is -O-. Also, X has a structure selected from the following -Sailor).
これら液晶ポリマーは、一般的に(a)成分であるスチ
レン系樹脂より溶融温度が高いため、溶融温度の非常に
高い液晶ポリマーとスチレン系樹脂を溶融加工すると、
加工中にスチレン系樹脂の熱劣化を生じるため、実際的
には、液晶ポリマーとしてスチレン系樹脂の加工温度(
一般的には、300°C以下)に近いものが好ましく使
用される。These liquid crystal polymers generally have a higher melting temperature than the styrene resin, which is component (a), so when a liquid crystal polymer with a very high melting temperature and a styrene resin are melt-processed,
Since thermal deterioration of styrenic resin occurs during processing, in practice, the processing temperature of styrenic resin (
In general, temperatures close to 300°C or lower are preferably used.
好ましい液晶ポリマーとして溶融温度が300°C以下
の完全芳香族ポリエステル、芳香族−脂肪族ポリエステ
ル、完全芳香族ポリエステルアミド、芳香族−脂肪族ポ
リエステルアミド、芳香族ポリアゾメチン、芳香族ポリ
エステルカーボネート、側鎖型液晶ポリマーが使用され
る。Preferred liquid crystal polymers include fully aromatic polyesters, aromatic-aliphatic polyesters, fully aromatic polyesteramides, aromatic-aliphatic polyesteramides, aromatic polyazomethines, aromatic polyester carbonates, and side chains having a melting temperature of 300°C or less. type liquid crystal polymer is used.
具体的には、完全芳香族ポリエステル、芳香族脂肪族ポ
リエステルとして、
(1) p−ヒドロキシ安息香酸、芳香族ジカルボン
酸、芳香族ジオールからなる全芳香族ポリエステルのう
ち、融点が300℃以下のもの。Specifically, fully aromatic polyesters and aromatic aliphatic polyesters include: (1) fully aromatic polyesters consisting of p-hydroxybenzoic acid, aromatic dicarboxylic acids, and aromatic diols with a melting point of 300°C or lower; .
(2)テレフタル酸および/またはイソフタル酸とクロ
ルハイドロキノン、フェニルハイドロキノン、ターシャ
リ−ブチルハイドロキノンおよび/またはハイドロキノ
ンからなるコポリエステルのうち、融点が300″C以
下のもの。(2) Among copolyesters consisting of terephthalic acid and/or isophthalic acid and chlorohydroquinone, phenylhydroquinone, tert-butylhydroquinone and/or hydroquinone, those having a melting point of 300″C or less.
(3)P−ヒドロキシ−安息香酸、2−ヒドロキシナフ
タレン−6−カルボン酸からなるコポリエステルのうち
、融点が300°C以下のもの。(3) Among copolyesters consisting of P-hydroxybenzoic acid and 2-hydroxynaphthalene-6-carboxylic acid, those having a melting point of 300°C or less.
(4)p−ヒドロキシ−安息香酸、ポリエチレンテレフ
タレートを共重合してなるコポリエステルのうち、融点
が300 ’C以下のもの。(4) Among copolyesters formed by copolymerizing p-hydroxybenzoic acid and polyethylene terephthalate, those having a melting point of 300'C or less.
などがあり、
上記(1)〜(4)のポリエステルに、p−アミノ安息
香酸、p−フェニレンジアミン、m−フェニレンジアミ
ンなどの芳香族ジアミンやヘキサメチレンジアミンなど
の脂肪族ジアミンを共重合して、完全芳香族ポリエステ
ルアミドや芳香族−脂肪族ポリエーテルアミトが得られ
るが、これらも融点が300°C以下ならば、好適に使
用可能である。etc., by copolymerizing the polyesters (1) to (4) above with aromatic diamines such as p-aminobenzoic acid, p-phenylenediamine, and m-phenylenediamine, and aliphatic diamines such as hexamethylenediamine. , fully aromatic polyesteramides and aromatic-aliphatic polyetheramides can be obtained, but these can also be suitably used if their melting points are below 300°C.
その他、芳香族ポリアゾメチン、芳香族ポリエステルカ
ーボネート、側鎖型液晶ポリマーも融点が300°C以
下のものが好ましく使用される。In addition, aromatic polyazomethine, aromatic polyester carbonate, and side chain type liquid crystal polymer having a melting point of 300° C. or lower are preferably used.
さらに好ましい液晶ポリマーとして、スチレン系樹脂と
溶融温度が近く、本発明の目的である、耐薬品性、加工
性改良という点から、完全芳香族ポリエステル、芳香族
−脂肪族ポリエステル、完全芳香族ポリエステルアミド
、芳香族−脂肪族ポリエステルアミドが使用される。More preferred liquid crystal polymers include fully aromatic polyesters, aromatic-aliphatic polyesters, and fully aromatic polyester amides, since they have a melting temperature close to that of styrene resins and improve chemical resistance and processability, which are the objectives of the present invention. , aromatic-aliphatic polyesteramides are used.
これら(b)成分は、本発明の熱可塑性樹脂組成物中に
、90〜1重量%の範囲で配合され、好ましくは60〜
2重量%の範囲で配合される。さらに、49〜2重量%
の範囲で配合されると、−段と優れた本発明の効果が得
られる。配合量が1重量%未満だと、加工性および耐薬
品性の改良に顕著な効果がみられない。These (b) components are blended in the thermoplastic resin composition of the present invention in an amount of 90 to 1% by weight, preferably 60 to 1% by weight.
It is blended in a range of 2% by weight. Furthermore, 49-2% by weight
When blended within this range, the effects of the present invention which are much more excellent can be obtained. If the amount is less than 1% by weight, no significant effect on improving processability and chemical resistance will be observed.
一方、90重量%を越えると、液晶ポリマー本来の性質
に近づくため、強度異方性を生じ、得られた成形品の外
観も劣る。On the other hand, if it exceeds 90% by weight, the properties approach the original properties of the liquid crystal polymer, resulting in strength anisotropy and the resulting molded product having poor appearance.
本発明の熱可塑性樹脂を得るための混錬には、各種押出
機、バンバリーミキサ−、ニーダ−、ロールなどが使用
される。好ましい混錬方法は押出機を用いる方法である
。Various extruders, Banbury mixers, kneaders, rolls, etc. are used for kneading to obtain the thermoplastic resin of the present invention. A preferred kneading method is a method using an extruder.
混錬温度は、混合するスチレン系樹脂(a)成分および
液晶ポリマーC#3)成分の融点以上の温度であること
が必要であり、約200〜350°Cが好ましい。The kneading temperature needs to be higher than the melting points of the styrenic resin (a) component and the liquid crystal polymer C#3) component to be mixed, and is preferably about 200 to 350°C.
本発明の熱可塑性樹脂組成物の使用に際して、ガラス繊
維、炭素繊維、金属繊維、ガラスピーズ、アスベスト、
ウォラスナイト、炭酸カルシウム、タルク、硫酸バリウ
ムなどの充填剤を単独でまたは組み合せて用いることが
できる。また、液晶ポリマー((b)成分)の繊維をそ
の融点以下で混合し、熱可塑性樹脂組成物を得ることも
できる。When using the thermoplastic resin composition of the present invention, glass fibers, carbon fibers, metal fibers, glass beads, asbestos,
Fillers such as wallasnite, calcium carbonate, talc, barium sulfate, etc. may be used alone or in combination. Alternatively, a thermoplastic resin composition can be obtained by mixing fibers of the liquid crystal polymer (component (b)) at a temperature below its melting point.
これらの充填剤のうち、ガラス繊維、炭素繊維および液
晶ポリマー繊維の形状としては、6〜60μmの繊維径
と30μm以上の繊維長を有するものが好ましい。Among these fillers, glass fibers, carbon fibers, and liquid crystal polymer fibers preferably have a fiber diameter of 6 to 60 μm and a fiber length of 30 μm or more.
これらの充填剤は目的に応じて、本発明の熱可塑性樹脂
組成物100重量部に対して、1〜50重量部混置部る
ことができる。These fillers can be mixed in an amount of 1 to 50 parts by weight based on 100 parts by weight of the thermoplastic resin composition of the present invention, depending on the purpose.
また、公知の難燃剤、酸化防止剤、可塑剤、着色剤、滑
剤などの添加物を添加して用いることができる。Additionally, known additives such as flame retardants, antioxidants, plasticizers, colorants, and lubricants may be added.
さらに、目的によっては、耐衝撃性をさらに向上させる
ために、他のゴム質重合体および熱可塑性エラストマー
を併用することもできる。Furthermore, depending on the purpose, other rubbery polymers and thermoplastic elastomers may be used in combination to further improve impact resistance.
併用しうるゴム質重合体としては、前述のグラフトポリ
マーの製造において挙げられたちの以外に、フッ素ゴム
、シリコンゴム、クロロプレンゴム、ブチルゴム、ハロ
ゲン化ブチルゴム、エチレンアクリルゴム、クロロスル
ホン化ポリエチレン、エチレン酢酸ビニル共重合体、多
硫化ゴム、エピクロルヒドリンゴム、ウレタンゴム、ブ
タジェンゴム、カルボキシ基やアミノ基末端変性ニトリ
ルゴム等の液状ゴム等が挙げられ、これらは目的に応じ
て1種または2種以上で使用される。Rubbery polymers that can be used in combination include, in addition to those mentioned in the production of the graft polymer, fluororubber, silicone rubber, chloroprene rubber, butyl rubber, halogenated butyl rubber, ethylene acrylic rubber, chlorosulfonated polyethylene, and ethylene acetic acid. Examples include liquid rubbers such as vinyl copolymers, polysulfide rubbers, epichlorohydrin rubbers, urethane rubbers, butadiene rubbers, and nitrile rubbers modified with carboxyl groups or amino groups, and these may be used singly or in combination of two or more depending on the purpose. Ru.
さらに要求される性能に応じて他の重合体、例えば、ポ
リエチレン、ポリプロピレン、MMA樹脂、PET 、
PBT 、 PPE 、ポリアミド、ポリカーボネー
ト、ポリアセタール、ポリアクリレート、ポリスルホン
、ポリエーテルスルホン、PPS、ポリエーテルエーテ
ルケトン、ポリイミド、ポリフッ化ビニリデンなどのふ
っ素樹脂などを適宜ブレンドすることができる。Furthermore, other polymers may be used depending on the required performance, such as polyethylene, polypropylene, MMA resin, PET,
PBT, PPE, polyamide, polycarbonate, polyacetal, polyacrylate, polysulfone, polyethersulfone, PPS, polyetheretherketone, polyimide, fluororesin such as polyvinylidene fluoride, etc. can be blended as appropriate.
本発明の熱可塑性樹脂組成物は、射出成形、シート押出
、真空成形、異形成形、発泡成形などによって各種成形
品として用いることができる。とくに射出成形において
は、液晶ポリマー((b)成分)を配向させるために、
十分な射出速度で成形することが好ましい。The thermoplastic resin composition of the present invention can be used as various molded products by injection molding, sheet extrusion, vacuum molding, irregular molding, foam molding, and the like. Particularly in injection molding, in order to orient the liquid crystal polymer (component (b)),
It is preferable to mold at a sufficient injection speed.
上記成形法によって得られた各種成形品は、その優れた
性質を利用して、自動車外装内装部材、電気電子関連の
各種部品、ハウジングなどに使用することができる。The various molded products obtained by the above molding method can be used for automobile exterior and interior parts, various electrical and electronic related parts, housings, etc. by utilizing their excellent properties.
e、実施例
以下に、実施例により本発明をさらに詳細に説明するが
、これらは例示的なものであって、本発明の内容を限定
するものではない。e. Examples Hereinafter, the present invention will be explained in more detail with reference to Examples, but these are merely illustrative and do not limit the content of the present invention.
なお、以下の実施例において、部および%はそれぞれ重
量部、重量%を示す。In addition, in the following examples, parts and % indicate parts by weight and % by weight, respectively.
(製造例I)スチレン系基質(変性AS樹脂)M−1−
M−5の製造:
撹拌機を備えた7リツトルのガラス製フラスコに、表−
1に示す薬液を加え、窒素で内部の空気を置換したのち
、ジャケットを70″Cにコントロールしながら内部を
50°C昇温しで、水4部に溶解した過硫酸カリウム0
.3部と水1部に溶解した亜硫酸ナトリウム0.1部を
添加し3時間反応させた。(Production Example I) Styrenic substrate (modified AS resin) M-1-
Preparation of M-5: In a 7 liter glass flask equipped with a stirrer,
After adding the chemical solution shown in 1 and displacing the air inside with nitrogen, the inside was heated to 50°C while controlling the jacket to 70"C, and potassium persulfate dissolved in 4 parts of water was added.
.. 3 parts and 0.1 part of sodium sulfite dissolved in 1 part of water were added and reacted for 3 hours.
得られたスチレン系基質重合体ラテックスに、塩化カル
シウムをポリマー100部に対し2部の割合で加え、9
0″Cで凝固した。これを分離、水洗、脱水、乾燥して
、表−1に示すスチレン系基質M−1〜M5を得た。Calcium chloride was added to the obtained styrenic matrix polymer latex at a ratio of 2 parts to 100 parts of polymer, and 9
It solidified at 0''C. This was separated, washed with water, dehydrated, and dried to obtain styrenic substrates M-1 to M5 shown in Table 1.
(製造例2)グラフト共重合体樹脂G−1およびG−2
の製造;
撹拌機を備えた7リツトルのガラス製フラスコに、表−
2に示すバッチ仕込の薬液を加え、窒素で内部を置換し
たのち、ジャケットを70°Cにコントロールしながら
、内部を40°Cに昇温して、水10部に溶解したピロ
リン酸ナトリウム0.3部、デキストローズ0.35部
および硫酸第一鉄0.01部と、クメンハイドロパーオ
キサイド0.1部を添加し、反応させた。(Production Example 2) Graft copolymer resins G-1 and G-2
Preparation: In a 7 liter glass flask equipped with a stirrer,
After adding the batch-prepared chemical solution shown in 2 and purging the inside with nitrogen, the inside was heated to 40°C while controlling the jacket at 70°C, and 0.2 parts of sodium pyrophosphate dissolved in 10 parts of water was added. 3 parts of dextrose, 0.35 parts of dextrose, and 0.01 part of ferrous sulfate, and 0.1 part of cumene hydroperoxide were added and reacted.
反応を開始してから1時間後に表−2に示すインクレメ
ント混合物を、3時間にわたって連続的に添加し、さら
に1時間反応を続けた。One hour after starting the reaction, the incremental mixture shown in Table 2 was added continuously over a period of three hours, and the reaction was continued for an additional hour.
得られたグラフト共重合体ラテックスに、老化防止剤と
して2,6−ジ−ターシャリ−ブチルパラクレゾール1
.0部を添加したのち、硫酸をポリマー100部に対し
2部の割合で加え、90°Cで凝固した。これを分離、
水洗、脱水、乾燥して、表−2に示すグラフト共重合体
G−1およびG−2を得た。2,6-di-tert-butyl para-cresol 1 was added to the obtained graft copolymer latex as an anti-aging agent.
.. After adding 0 parts, sulfuric acid was added at a ratio of 2 parts to 100 parts of polymer and coagulated at 90°C. Separate this,
After washing with water, dehydration, and drying, graft copolymers G-1 and G-2 shown in Table 2 were obtained.
表
グラフトv■に到本G
1、G
実施例1〜7および比較例1〜5:
製造例1で得られたスチレン系基質M−1−M5、製造
例2で得られたG−1、G−2、および日本合成ゴム■
製スチレンーアシクロニトリル共重合樹脂へ5240
(結合アクリロニトリル24.5重量%、メチルエチル
ケトン、30″Cでのη=0.60)を用い、液晶ポリ
マーとして三菱化成■製EPE−240(ポリエチレン
テレフタレー)/p−ヒドロキシ安息香酸共重合体より
なるサーモトロピック液晶性ポリエステル、溶融加工温
度範囲240〜320°C)、またはポリプラスチック
社製ベクトラA−950(p−ヒドロキシ安息香酸/、
6−ヒドロキシ−2−ナフトエ酸を主成分としたサーモ
トロピック液晶性芳香族ポリエステル)を用いて、表−
3に示す割合と条件に従ってヘンシェルミキサーを用い
て混合し、30mm二軸ベント付き押出機を用いて造粒
した。G1, G Examples 1 to 7 and Comparative Examples 1 to 5: Styrenic substrates M-1 to M5 obtained in Production Example 1, G-1 obtained in Production Example 2, G-2 and Japanese synthetic rubber ■
5240 to styrene-acyclonitrile copolymer resin
(24.5% by weight of bound acrylonitrile, methyl ethyl ketone, η=0.60 at 30"C), and EPE-240 (polyethylene terephthalate)/p-hydroxybenzoic acid copolymer manufactured by Mitsubishi Kasei ■ was used as the liquid crystal polymer. thermotropic liquid crystalline polyester, melt processing temperature range 240-320°C), or Vectra A-950 manufactured by Polyplastics (p-hydroxybenzoic acid/,
Using a thermotropic liquid crystalline aromatic polyester containing 6-hydroxy-2-naphthoic acid as the main component,
The mixture was mixed using a Henschel mixer according to the proportions and conditions shown in Section 3, and granulated using a 30 mm twin-screw vented extruder.
得られたペレット状の熱可塑性樹脂組成物を、真空乾燥
機にて十分乾燥したのち、射出成形機にて、表−3に示
す条件に従って成形することにより試験片を作製し、下
記の条件で耐薬品性および耐熱性を評価し、さらに乾燥
後のペレットを用いて加工性を評価した。The obtained pellet-shaped thermoplastic resin composition was sufficiently dried in a vacuum dryer, and then molded in an injection molding machine according to the conditions shown in Table 3 to prepare test pieces. Chemical resistance and heat resistance were evaluated, and processability was further evaluated using pellets after drying.
耐薬品性:定歪ソルベントクラック
試験片(l/8″×115″×5)に歪率0.5%の定
歪を加え、たわみ部分にブレーキオイル(以下、BOと
いう。)を塗布し、23゛Cにて放置したときの破断に
いたるまでの時間を測定した。また、歪率1.0%の条
件でジオクチルフタレート(以下、DOPという。)を
用い同様の測定を行った。時間が長いほど耐薬品性が良
好であることを示す。Chemical resistance: A constant strain with a strain rate of 0.5% was applied to a constant strain solvent crack test piece (l/8″ x 115″ x 5), and brake oil (hereinafter referred to as BO) was applied to the deflected part. The time taken to break when the film was left at 23°C was measured. Further, similar measurements were conducted using dioctyl phthalate (hereinafter referred to as DOP) under the condition of a strain rate of 1.0%. The longer the time, the better the chemical resistance.
耐熱性:857M D648に従って、厚み1/2“、
荷重18.6kg/c1ilで、熱変形温度を測定した
。Heat resistance: 857M according to D648, thickness 1/2",
The heat distortion temperature was measured at a load of 18.6 kg/c1il.
加工性: JIS K7210に従って、260°C1
荷重10kgでメルトフローレー) (MFR)を測定
した。Workability: 260°C1 according to JIS K7210
Melt flow rate (MFR) was measured at a load of 10 kg.
表−3に示す実施例1〜7と比較例1の比較から明らか
なように、本発明の熱可塑性樹脂組成物は、耐薬品性お
よび加工性に優れた樹脂である。As is clear from the comparison of Examples 1 to 7 and Comparative Example 1 shown in Table 3, the thermoplastic resin composition of the present invention is a resin with excellent chemical resistance and processability.
比較例2の組成物は、官能基含有単量体成分が含まれて
いないので、実施例2および3の組成物と比べて、耐薬
品性が大幅に劣り、加工性(流動性)の改良効果も乏し
い。Since the composition of Comparative Example 2 does not contain a functional group-containing monomer component, it has significantly inferior chemical resistance and improved processability (fluidity) compared to the compositions of Examples 2 and 3. It is also not very effective.
比較例3の組成物も、官能基含有単量体成分が含まれて
いないものであり、実施例4の組成物と比べて耐薬品性
が大幅に劣り、加工性(流動性)の改良効果が小さい。The composition of Comparative Example 3 also does not contain a functional group-containing monomer component, has significantly inferior chemical resistance compared to the composition of Example 4, and has no effect on improving processability (fluidity). is small.
比較例4の組成物は、官能基含有単量体成分として、メ
タクリル酸を35重量%含むスチレン系基質を含有して
いる組成物の例であるが、加工性が大幅に低下する。The composition of Comparative Example 4 is an example of a composition containing a styrene substrate containing 35% by weight of methacrylic acid as a functional group-containing monomer component, but the processability is significantly reduced.
比較例5の組成物は、ガラス繊維を添加した例であるが
、加工性が低下し、耐薬品性も改良されない。Although the composition of Comparative Example 5 is an example in which glass fiber is added, the processability is reduced and the chemical resistance is not improved.
「0発明の効果
本発明の熱可塑性樹脂組成物はスチレン系樹脂((a)
成分)に液晶ポリマー((b)成分)を添加することに
より、スチレン系樹脂の耐薬品性、加工性および耐熱性
が大幅に改良される。とくにガラス繊維充填系を添加し
たものと比べて、加工性および耐薬品性に優れた熱可塑
性樹脂が得られる。"0 Effects of the Invention The thermoplastic resin composition of the present invention has styrenic resin ((a)
By adding a liquid crystal polymer (component (b)) to component (component), the chemical resistance, processability, and heat resistance of the styrenic resin are significantly improved. In particular, thermoplastic resins with excellent processability and chemical resistance can be obtained compared to those containing glass fiber filling systems.
また、本発明の熱可塑性樹脂組成物においては、液晶ポ
リマー(0))成分)とスチレン系樹脂((a)成分)
との相溶性を改良することにより、耐薬品性、加工性お
よび耐熱性の優れた樹脂が得られる。In addition, in the thermoplastic resin composition of the present invention, liquid crystal polymer (0) component) and styrene resin ((a) component)
A resin with excellent chemical resistance, processability, and heat resistance can be obtained by improving the compatibility with.
Claims (1)
ロキシル基およびアミノ基から選ばれた少なくとも1種
の官能基を有する共重合可能な単量体の少なくとも1種
が樹脂中に0.1〜30重量%共重合されている、芳香
族ビニルおよび/または(メタ)アクリル酸アルキルエ
ステルを必須成分とする樹脂10〜99重量%と、 (b)液晶ポリマー90〜1重量% とからなることを特徴とする熱可塑性樹脂組成物。[Scope of Claims] (a) At least one copolymerizable monomer having at least one functional group selected from a carboxyl group, an acid anhydride group, an epoxy group, a hydroxyl group, and an amino group is a resin. (b) 10 to 99 weight % of a resin containing aromatic vinyl and/or (meth)acrylic acid alkyl ester as an essential component, copolymerized with 0.1 to 30 weight %; (b) 90 to 1 weight % of a liquid crystal polymer; % of a thermoplastic resin composition.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63218163A JPH0267366A (en) | 1988-08-31 | 1988-08-31 | Thermoplastic resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63218163A JPH0267366A (en) | 1988-08-31 | 1988-08-31 | Thermoplastic resin composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0267366A true JPH0267366A (en) | 1990-03-07 |
Family
ID=16715619
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP63218163A Pending JPH0267366A (en) | 1988-08-31 | 1988-08-31 | Thermoplastic resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0267366A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001247785A (en) * | 2000-03-07 | 2001-09-11 | Polymatech Co Ltd | Composite thermoplastic elastomer composition and molding therefrom |
JP2020007394A (en) * | 2018-07-03 | 2020-01-16 | ポリプラスチックス株式会社 | Liquid crystalline resin composition for sliding wear-resistant members, and sliding wear-resistant member including the same |
-
1988
- 1988-08-31 JP JP63218163A patent/JPH0267366A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001247785A (en) * | 2000-03-07 | 2001-09-11 | Polymatech Co Ltd | Composite thermoplastic elastomer composition and molding therefrom |
JP2020007394A (en) * | 2018-07-03 | 2020-01-16 | ポリプラスチックス株式会社 | Liquid crystalline resin composition for sliding wear-resistant members, and sliding wear-resistant member including the same |
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