JPH04120172A - Thermoplastic resin composition - Google Patents
Thermoplastic resin compositionInfo
- Publication number
- JPH04120172A JPH04120172A JP23876390A JP23876390A JPH04120172A JP H04120172 A JPH04120172 A JP H04120172A JP 23876390 A JP23876390 A JP 23876390A JP 23876390 A JP23876390 A JP 23876390A JP H04120172 A JPH04120172 A JP H04120172A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- polycarbonate
- parts
- compounds
- unsaturated carboxylic
- 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.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 16
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 9
- 239000004417 polycarbonate Substances 0.000 claims abstract description 54
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 52
- 239000004952 Polyamide Substances 0.000 claims abstract description 30
- 229920002647 polyamide Polymers 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 22
- -1 maleimide compound Chemical class 0.000 claims abstract description 20
- 229920001971 elastomer Polymers 0.000 claims abstract description 15
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 12
- 229920001890 Novodur Polymers 0.000 claims description 9
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 125000005439 maleimidyl group Chemical class C1(C=CC(N1*)=O)=O 0.000 claims 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 46
- 229920005989 resin Polymers 0.000 abstract description 17
- 239000011347 resin Substances 0.000 abstract description 17
- 239000000126 substance Substances 0.000 abstract description 10
- 229920000642 polymer Polymers 0.000 abstract description 9
- 239000005060 rubber Substances 0.000 abstract description 6
- 229920002554 vinyl polymer Polymers 0.000 abstract description 5
- 150000002825 nitriles Chemical class 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 11
- 230000000379 polymerizing effect Effects 0.000 description 11
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 10
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 10
- 229920000578 graft copolymer Polymers 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 9
- 229920002292 Nylon 6 Polymers 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 238000010556 emulsion polymerization method Methods 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 230000032798 delamination Effects 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 3
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229920000299 Nylon 12 Polymers 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene 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
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000006085 branching agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 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
- 150000003951 lactams Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- KYPOHTVBFVELTG-OWOJBTEDSA-N (e)-but-2-enedinitrile Chemical compound N#C\C=C\C#N KYPOHTVBFVELTG-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
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-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
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QUBNFZFTFXTLKH-UHFFFAOYSA-N 2-aminododecanoic acid Chemical compound CCCCCCCCCCC(N)C(O)=O QUBNFZFTFXTLKH-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
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 241000257465 Echinoidea Species 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- 229920000577 Nylon 6/66 Polymers 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 241000287530 Psittaciformes Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- TZYHIGCKINZLPD-UHFFFAOYSA-N azepan-2-one;hexane-1,6-diamine;hexanedioic acid Chemical compound NCCCCCCN.O=C1CCCCCN1.OC(=O)CCCCC(O)=O TZYHIGCKINZLPD-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- VUKHQPGJNTXTPY-UHFFFAOYSA-N but-2-enylbenzene Chemical compound CC=CCC1=CC=CC=C1 VUKHQPGJNTXTPY-UHFFFAOYSA-N 0.000 description 1
- GHWVXCQZPNWFRO-UHFFFAOYSA-N butane-2,3-diamine Chemical compound CC(N)C(C)N GHWVXCQZPNWFRO-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- ZMUCVNSKULGPQG-UHFFFAOYSA-N dodecanedioic acid;hexane-1,6-diamine Chemical compound NCCCCCCN.OC(=O)CCCCCCCCCCC(O)=O ZMUCVNSKULGPQG-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002184 metal Substances 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
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- PBLZLIFKVPJDCO-UHFFFAOYSA-N omega-Aminododecanoic acid Natural products NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 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
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 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、ポリカーボネート、ゴム強化ｙ、−ｙ−レン
糸樹脂、変性ポリカーボネートおよびポリアミドからな
る耐薬品性、熱安定性、耐熱性、耐衝撃性に優れ、かつ
層剥離のない熱可塑性樹脂組成物に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention provides chemical resistance, thermal stability, heat resistance, and impact resistance made of polycarbonate, rubber-reinforced y, -y-len thread resin, modified polycarbonate, and polyamide. The present invention relates to a thermoplastic resin composition that has excellent properties and does not peel off.
「従来の技術〕
従来よシ、耐熱性と耐衝撃性に優れた材料としてポリカ
ーボネートとゴム強化スチレン系樹脂とからなる組成物
が知られているが、かかる組成物は他のエンジニアリン
グプラスチックスに比べ耐薬品性に劣るため、その使用
においては種々の制約を受けている。このためポリカポ
ネートとゴム強化スチレン系樹脂とからなる組成物の耐
薬品性改善としてポリアミドや飽和ポリエステルの配合
が提案されている。``Prior art'' Compositions made of polycarbonate and rubber-reinforced styrene resin have been known as materials with excellent heat resistance and impact resistance, but such compositions are inferior to other engineering plastics. Due to its poor chemical resistance, its use is subject to various restrictions.For this reason, blending polyamide or saturated polyester has been proposed to improve the chemical resistance of compositions made of polycarbonate and rubber-reinforced styrene resin. .
しかしながら、ポリカーボネートとゴム強化スチレン系
樹脂とからなる組成物とポリアミドとの相溶性が悪いだ
め、ポリアミドを多量に配合すると層剥離を起し、十分
な耐薬品性を得ることが困難である。又、飽和ポリエヌ
テルを配合するとポリカーボネートと容易にエステル交
換反応を起すため、熱安定性に劣るといった問題点を有
している。However, since the compatibility between polyamide and a composition made of polycarbonate and rubber-reinforced styrene resin is poor, when a large amount of polyamide is blended, layer peeling occurs and it is difficult to obtain sufficient chemical resistance. Furthermore, when saturated polyester is blended, it easily undergoes a transesterification reaction with polycarbonate, resulting in a problem of poor thermal stability.
本発明者は、ポリカーボネートとゴム強化スチレン系樹
脂とからなる樹脂組成物の優れた特性である耐熱性、耐
衝撃性を犠牲にすることなく耐薬品性を改善し、しかも
層剥離のない組成物について鋭意研究した結果、該樹脂
組成物に変性ポリカーボネートとポリアミドを特定量配
合してなり、かつ不飽和カルボン酸又はその無水物がゴ
ム強化スチレン系樹脂および／または目的とする優れた
特性を有していることを見出し、本発明に到達したもの
である。The present inventor has developed a composition that improves chemical resistance without sacrificing the excellent properties of heat resistance and impact resistance of a resin composition made of polycarbonate and rubber-reinforced styrenic resin, and that does not cause delamination. As a result of intensive research, we have found that the resin composition is formulated with specific amounts of modified polycarbonate and polyamide, and that the unsaturated carboxylic acid or its anhydride has rubber-reinforced styrenic resin and/or the desired excellent properties. The present invention was achieved by discovering that
すなわち、本発明は、ポリカーボネート（Ａ）１０〜９
０重量％とゴム質重合体１０〜９０重量り６、芳香族ビ
ニル化合物、不飽和二） ＩＪ ／し化合物、不飽和カ
ルボン酸アルキルエステル化合物およびマレイミド化合
物から選択された一種以上の化合物１０〜８０重量％お
よび不飽和カルボン酸又はその無水物０〜１０重量％か
らなるゴム強化スチレン系樹脂（Ｂ）９０〜１０重量％
からなる樹脂組成物（Ｉ）１００重量部当り、ポリカー
ボネート２０〜７０重量％、芳香族ビニル化合物、不飽
和二） ＩＪル化合物、不飽和カルボン酸アルキルエス
テル化合物およびマレイミド化合物から選択された一種
以上の化合ボネート（Ｉｔ ） ０．１〜３０重量部お
よびポリアミド（Ｉ［１）１０〜１００重量部配合置型
なり、かつゴム強化スチレン系樹脂（Ｂ）と変性ポリカ
ーボネー）（ＩＩ）の合計当り、不飽和カルボン酸又は
その無水物を０．０１〜８重量％含有することを特徴と
する耐薬品性、熱安定性、耐熱性、耐衝撃性に優れ、か
つ層剥離のない熱可塑性樹脂組成物を提供するものであ
る。That is, the present invention provides polycarbonate (A) 10 to 9
0% by weight and rubbery polymer 10-90% by weight 6, aromatic vinyl compound, unsaturated di(IJ) compound, unsaturated carboxylic acid alkyl ester compound and maleimide compound 10-80 Rubber-reinforced styrenic resin (B) consisting of 90-10% by weight and 0-10% by weight of unsaturated carboxylic acid or its anhydride
Per 100 parts by weight of the resin composition (I), 20 to 70% by weight of polycarbonate, an aromatic vinyl compound, one or more selected from unsaturated carboxylic acid alkyl ester compounds, unsaturated carboxylic acid alkyl ester compounds, and maleimide compounds. Compound carbonate (It) 0.1 to 30 parts by weight and polyamide (I [1) 10 to 100 parts by weight, and based on the total of rubber reinforced styrene resin (B) and modified polycarbonate (II), A thermoplastic resin composition containing 0.01 to 8% by weight of a saturated carboxylic acid or its anhydride, which has excellent chemical resistance, thermal stability, heat resistance, and impact resistance, and is free from delamination. This is what we provide.
以下、本発明の熱可塑性樹脂組成物につき詳細に説明す
る。Hereinafter, the thermoplastic resin composition of the present invention will be explained in detail.
０ポリカーボネート（Ａ）
本発明の組成物を構成するポリカーボネートとしては、
芳香族ポリカーボネート、脂肪族ポリカーボネート、脂
肪族−芳香族ポリカーボネート等々を挙げることができ
る。一般には、２．２−ビス（４−オキシフェニ）ｖ
）アルカン系、ビス（４−オギシフェニ）Ｖ ）エーテ
ル系、ビス（４−オキシフェニ）Ｖ ）スルホン、スル
フィドまたはスルホキサイド糸などのビスフェノール類
からなる重合体、もしくは共重合体であり、目的に応じ
てハロゲンで置換されたビスフェノール類を用いた重合
体、もしくは共重合体や分岐剤を用いて重合してなる分
岐重合体を用いることもできる。0 Polycarbonate (A) As the polycarbonate constituting the composition of the present invention,
Examples include aromatic polycarbonate, aliphatic polycarbonate, aliphatic-aromatic polycarbonate, and the like. Generally, 2,2-bis(4-oxypheny)v
) Alkane-based, bis(4-oxyphenylated) V) Ether-based, bis(4-oxyphenylated) V) Polymer or copolymer consisting of bisphenols such as sulfone, sulfide, or sulfoxide threads, and may contain halogen depending on the purpose. It is also possible to use a polymer using bisphenols substituted with or a branched polymer obtained by polymerizing using a copolymer or a branching agent.
ポリカーボネートの分子量にも特に制限はないが粘度平
均分子量１万〜１０万のものが好ましい。又、製造法に
も特に制限はなく、ホスゲン法、エステル交換法などが
用いられる。There is no particular restriction on the molecular weight of the polycarbonate, but a viscosity average molecular weight of 10,000 to 100,000 is preferred. Further, there is no particular restriction on the production method, and phosgene method, transesterification method, etc. are used.
０ゴム強化ヌチレン、１樹脂（Ｂ）
ゴム強化スチレン系樹脂とは、ゴム質重合体（＋）１０
〜９０重量％、芳香族ビニル化合物、不飽和二） ＩＪ
／し化合物、不飽和カルボン酸アルキルエステル化合
物およびマレイミド化合物から選択された一種以上の化
合物（Ｉ１）１０〜８０重量％および不飽和カルボン酸
又はその無水物（ＩＩＩ ） ０〜１０重量％とから構
成される樹脂である。かかる範囲外では、目的とする組
成物を得ることが困難である。好ましくは、ゴム質重合
体（＋）１５〜７０重量％、化合物（Ｉ１）３０〜８２
重量％および酸又は無水物（ＩＩＩ ） ０〜８重量％
である。0 Rubber-reinforced nutyrene, 1 Resin (B) Rubber-reinforced styrene resin is a rubbery polymer (+) 10
~90% by weight, aromatic vinyl compound, unsaturated 2) IJ
Consisting of 10 to 80% by weight of one or more compounds (I1) selected from /silicon compounds, unsaturated carboxylic acid alkyl ester compounds, and maleimide compounds, and 0 to 10% by weight of unsaturated carboxylic acids or their anhydrides (III) This is the resin that is used. Outside this range, it is difficult to obtain the desired composition. Preferably, rubbery polymer (+) 15-70% by weight, compound (I1) 30-82%
% by weight and acid or anhydride (III) 0-8% by weight
It is.
より具体的には、ゴム質重合体の存在下、上述の化合物
（Ｉ１）又は化合物（Ｉ１）と不飽和カルボン酸又はそ
の無水物（ｌｌｉ ）を重合してなるグラフト重合体又
は、該グラフト重合体と上述の化合物（Ｉ１）又は化合
物（Ｉ１）と不飽和カルボン酸又はその無水害ス重合し
てなる（共）重合体との混合物である。More specifically, a graft polymer obtained by polymerizing the above-mentioned compound (I1) or compound (I1) and an unsaturated carboxylic acid or its anhydride (lli) in the presence of a rubbery polymer, or the graft polymer It is a mixture of the above-mentioned compound (I1) or an unsaturated carboxylic acid or a (co)polymer obtained by polymerizing the compound (I1) with anhydrous hydrogen atom.
特に、ゴム質重合体（Ｉ）と化合物（Ｉ１）とからなる
グラフト重合体と、化合物（Ｉ１）と酸又は無水物（■
１）とからなる共重合体との混合物が好ましい。In particular, a graft polymer consisting of a rubbery polymer (I) and a compound (I1), a compound (I1) and an acid or anhydride (■
A mixture with a copolymer consisting of 1) is preferred.
ゴム質重合体（Ｉ）としては、ポリブタジェン、スチレ
ン−ブタジェン共重合体、アクリロニトリル−ブタジェ
ン共重合体、エチレン−プロピレン系共重合体、アクリ
ル酸エステル系共重合体、塩素化ポリエチレン等が例示
され、単独または二種以上用いることができる。これら
のゴム状重合体は乳化重合、溶液重合、懸濁重合、塊状
重合等により製造される。なお、乳化質
重合により製造する場合におけるゴム■重合体の粒子径
およびゲル含有率については特に制限はないが、平均粒
子径０．１〜１μｍおよびゲル含有率０〜９５％である
ことが望ましい。Examples of the rubbery polymer (I) include polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, ethylene-propylene copolymer, acrylic ester copolymer, chlorinated polyethylene, etc. They can be used alone or in combination of two or more. These rubbery polymers are produced by emulsion polymerization, solution polymerization, suspension polymerization, bulk polymerization, and the like. There are no particular restrictions on the particle size and gel content of the rubber polymer when produced by emulsion polymerization, but it is desirable that the average particle size is 0.1 to 1 μm and the gel content is 0 to 95%. .
芳香族ビニル化合物としては、スチレン、αメチルスチ
レン、０−メチルスチレン、ｍ−メチルスチレン、ｐ−
メチルスチレン、ｔ−ブチルスチレン、α−メチルビニ
ルトルエン、ジメチルスチレン、クロルスチレン、ジク
ロルスチレン、ブロムスチレン、ジブロムスチレン、ビ
ニルナフタレン等が例示され、単独または二種以上用い
ることができる。特にスチレンならヒニα−メチルスチ
レンが好ましい。Examples of aromatic vinyl compounds include styrene, α-methylstyrene, 0-methylstyrene, m-methylstyrene, and p-methylstyrene.
Examples include methylstyrene, t-butylstyrene, α-methylvinyltoluene, dimethylstyrene, chlorostyrene, dichlorostyrene, bromustyrene, dibromustyrene, vinylnaphthalene, and the like, which can be used alone or in combination of two or more. In particular, when it comes to styrene, α-methylstyrene is preferred.
Ｔ［ｌ和ニトリル化合物としては、アクリロニド リ
ル、 メ タ り リ ロ ニ ト リ ル、 エ
タ り リ ロ ニ トリル、フマロニトリル等が例
示され、単独又は二種以上用いることができる。特にア
クリロニトリルが好ましい。As a nitrile compound, acrylonide
Examples include metal lylonitrile, ethylylonitrile, fumaronitrile, and the like, which can be used alone or in combination of two or more. Acrylonitrile is particularly preferred.
不飽和カルボン酸アルキルエステル化合物としては、メ
チルアクリレート、エチルアクリレト、グチルアクリレ
ート、２−エチルヘキシルアクリレート、メチルメタク
リレート、エチルメタクリレート、プロピルメタクリレ
ート、ターシャリ−ブチルメタクリレート、２−エチル
へキシルメタクリレート等が例示され、単独又は二種以
上用いることができる。特にメチルメタクリレートが好
ましい。Examples of unsaturated carboxylic acid alkyl ester compounds include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, etc. They can be used alone or in combination of two or more. Particularly preferred is methyl methacrylate.
マレイミド化合物としては、マレイミド、Ｎ−フェニル
マレイミド、Ｎ−メチルマレイミド、Ｎ−シクロヘキシ
ルマレイミド等が例示すし、単独又は二種以上用いるこ
とができる。特にＮ−フェニルマレイミドが好ましい。Examples of the maleimide compound include maleimide, N-phenylmaleimide, N-methylmaleimide, N-cyclohexylmaleimide, and the like, and they can be used alone or in combination of two or more. Particularly preferred is N-phenylmaleimide.
化合物（Ｉ１）としては上述の芳香族ビニル化合物、不
飽和二ｌ−Ｕ ／し化合物、不飽和カルボン酸アルキル
エステル化合物およびマレイミド化合物から選択された
一種以上の化合物であるがアルキルエステル化合物およ
びマレイミド化合物のいずれか一種以上の化合物■との
併用が好ましい。Compound (I1) is one or more compounds selected from the above-mentioned aromatic vinyl compounds, unsaturated 2-U/2 compounds, unsaturated carboxylic acid alkyl ester compounds, and maleimide compounds, but alkyl ester compounds and maleimide compounds are preferred. Preferably, it is used in combination with one or more of the following compounds (1).
不飽和カルボン酸又はその無水物（■１）としては、ア
クリル酸、メタクリル酸、マレイン酸、フマル酸、イタ
コン酸、無水マレイン酸等が例示され、単独又は二種以
上用いることができる。Examples of the unsaturated carboxylic acid or its anhydride (1) include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, and maleic anhydride, which can be used alone or in combination of two or more.
特にメタクリル酸が好ましい。Particularly preferred is methacrylic acid.
グラフト重合体におけるグラフト率についても制限はな
いが２５〜１５０％であることが望ましい。There is no limit to the grafting rate of the graft polymer, but it is preferably 25 to 150%.
グラフト重合体ならびに（共）重合体の重合方法として
は、公知の乳化重合、懸濁重合、塊状重合、溶液重合ま
たはこれらを組み合わせた方法が用いられる。As a polymerization method for the graft polymer and the (co)polymer, known methods such as emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, or a combination thereof are used.
Ｏ樹脂組成物（Ｉ）
ポリカーボネートとゴム強化スチレン系樹脂との配合比
率は、それぞれ両者合計に基き１０〜９０重量％、９０
〜１０重量％である。かかる範囲外では耐熱性と耐衝撃
性のバランスに劣シ好ましくない。両物性のバランスな
らびに加工性の面より、特にポリカーボネート２０〜８
０重量％、ゴム強化ヌチレン系樹脂８０〜２０重量％が
好ましい。O resin composition (I) The blending ratio of polycarbonate and rubber-reinforced styrene resin is 10 to 90% by weight and 90% by weight, respectively, based on the total of both.
~10% by weight. Outside this range, the balance between heat resistance and impact resistance is unfavorable. In terms of the balance of both physical properties and processability, polycarbonate 20 to 8 is particularly preferred.
0% by weight, and preferably 80 to 20% by weight of the rubber-reinforced nutylene resin.
Ｏ変性ポリカーボネー）（Ｉｔ）
本発明で用いられる変性ポリカーボネートとは、ポリカ
ーボネート（Ｉ）２０〜７０重量％、芳香族ビニル化合
物、不飽和二） Ｕ ／Ｌ／化合物、不飽和カルボン酸
アルキルエステル化合物およびマレイミド化合物から選
択された一種以上の化合物（ＩＩ ） ２０〜８０重量
％および不飽和カルボン酸又はその無水物（ｉｔ ）
ｏ〜１０重量％からなる重合体である。O-modified polycarbonate) (It) The modified polycarbonate used in the present invention is polycarbonate (I) 20 to 70% by weight, an aromatic vinyl compound, an unsaturated compound, an unsaturated carboxylic acid alkyl ester compound and one or more compounds selected from maleimide compounds (II) 20 to 80% by weight and an unsaturated carboxylic acid or its anhydride (it)
It is a polymer consisting of o to 10% by weight.
かかる範囲外では、目的とする組成物を得ることが困難
である。好ましくは、ポリカーボネート（Ｉ）８０〜６
５重量％、化合物（Ｉ１）３０〜７０重量％および酸又
は無水物（■）０〜１０重量％である。Outside this range, it is difficult to obtain the desired composition. Preferably polycarbonate (I) 80-6
5% by weight, 30-70% by weight of compound (I1) and 0-10% by weight of acid or anhydride (■).
よシ具体的にはポリカーボネートの存在下、上述の化合
物（Ｉ１）又は化合物（Ｉ１）と不飽和カルボン酸又は
その無水物（Ｉｌｌ ）を重合してなるグラフト又はブ
ロック重合体である。More specifically, it is a graft or block polymer obtained by polymerizing the above-mentioned compound (I1) or compound (I1) and an unsaturated carboxylic acid or its anhydride (Ill) in the presence of polycarbonate.
変性ポリカーボネートを構成するポリカーボネート（＋
）、化合物（Ｉ１）および酸又は無水物（ＩＩ ）と
しては、ポリカーボネートならびにゴム強化スチレン系
樹脂の項にて例示されたものと同様のものである。ポリ
カーボネートの反応性を高めるため、主鎖又は末端に不
飽和基を導入したポリカーボネートも用いることができ
る。Polycarbonate (+
), the compound (I1) and the acid or anhydride (II) are the same as those exemplified in the section of polycarbonate and rubber-reinforced styrenic resin. In order to increase the reactivity of polycarbonate, polycarbonate having an unsaturated group introduced into the main chain or the terminal can also be used.
化合物（Ｉ１）としては上述の芳香族ビニル化合物、不
飽和二） ＩＪ ／し化合物、不飽和カルボン酸アルキ
ルエステル化合物およびマレイミド化合物から選択され
た一種以上の化合物であるが、アルキルエステル化合物
およびマレイミド化合物のいずれか一種以上の化合物■
との併用が好ましい。Compound (I1) is one or more compounds selected from the above-mentioned aromatic vinyl compounds, unsaturated di(IJ) compounds, unsaturated carboxylic acid alkyl ester compounds, and maleimide compounds, and alkyl ester compounds and maleimide compounds. Compound of one or more of ■
It is preferable to use it in combination with
変性ポリカーボネートは、特公昭４７−６７５１の如く
溶液重合法はもとより公知の懸濁重合法等により製造す
ることができる。The modified polycarbonate can be produced not only by a solution polymerization method as disclosed in Japanese Patent Publication No. 47-6751, but also by a known suspension polymerization method.
０ポリアミド（Ｉ［Ｉ）
本発明で用いられるポリアミドとしては、エチレンジア
ミン、ジアミノブタン、ヘキサメチレンジアミン、デカ
メチレンジアミン、ドデカメチレンジアミン、２．２．
４−おｘｏ：２．４．４−トリメチルへキサメチレンジ
アミン、１．３および１，４−ビス（アミノメチ）Ｖ
）シクロヘキサン、ビス（ｐ−アミノシクロへキシ）Ｖ
）メタン、メタキシリレンジアミン、パラキシリレン
ジアミンなどの脂肪族、脂環族、芳香族ジアミンとアジ
ピン酸、スペリン酸、セバシン酸、シクロヘキサンジカ
ルボン酸、テレフタｌし酸、イソフタル酸などの脂肪族
、脂環族、芳香族ジカルボン酸とから導かれるポリアミ
ド、ξ〜カプロラクタム、ω−ドデカラクタムなどのラ
クタム類の開環重合によってえられるポリアミド、６−
アミノカプロン酸、１１−アミノウンデカン酸、１２−
アミノドデカン酸などから導かれるポリアミドおよびこ
れらの共重合ポリアミド、混合ポリアミド、さらにはポ
リアミドをハードセグメントとし、かつボリエーデ〜を
ソフトセグメントとするポリアミドエラストマーなどが
挙げられる。0 Polyamide (I [I) Polyamides used in the present invention include ethylene diamine, diaminobutane, hexamethylene diamine, decamethylene diamine, dodecamethylene diamine, 2.2.
4-oxo: 2.4.4-trimethylhexamethylenediamine, 1.3 and 1,4-bis(aminomethy)V
) cyclohexane, bis(p-aminocyclohexy)V
) Aliphatic, alicyclic, and aromatic diamines such as methane, metaxylylene diamine, and paraxylylene diamine; Polyamides derived from alicyclic and aromatic dicarboxylic acids, polyamides obtained by ring-opening polymerization of lactams such as ξ-caprolactam and ω-dodecalactam, 6-
Aminocaproic acid, 11-aminoundecanoic acid, 12-
Examples include polyamides derived from aminododecanoic acid, copolyamides thereof, mixed polyamides, and polyamide elastomers having polyamide as a hard segment and polyade as a soft segment.
工業的に安価かつ大量に製造されているという意味でポ
リカプロアミド（ナイロン６）、ポリドデカアミド（ナ
イロン１２）、ポリテトラメチレンアジパミド（ナイロ
ン４６）、ポリヘキサメチレンアジパミド（ナイロン６
６）、ポリへキサメチレンジアミン（ナイロン６１０）
、およびこれらの共重合体、たとえばナイロン６／ ６
６ （／／ ／＼＼印は共重合体であることを意味する
）、ナイロン６／６１０、ナイロ６／１２、＋イ１：’
７６６／１２、ナイロン６／６６／６１゜／１２、およ
びこれらの混合体などが有用である。また、ビス（ｐ−
アミノシクロへキシ）Ｖ ）メタン／テレフタル酸／イ
ソフタル酸系のポリアミドも有用である。Polycaproamide (nylon 6), polydodecaamide (nylon 12), polytetramethylene adipamide (nylon 46), and polyhexamethylene adipamide (nylon 6) are industrially produced at low cost and in large quantities.
6) Polyhexamethylene diamine (nylon 610)
, and copolymers thereof, such as nylon 6/6
6 (// /\\ sign means copolymer), nylon 6/610, nylon 6/12, +i1:'
Useful materials include 766/12, nylon 6/66/61°/12, and mixtures thereof. Also, bis(p-
Aminocyclohexy)V) Polyamides based on methane/terephthalic acid/isophthalic acid are also useful.
なお、用いられるポリアミド樹脂の重合度には制限はな
く、濃硫酸相対粘度（ポリマー１２を９８％濃硫酸１０
０ ｙｘｌに溶解し、２５℃で測定、以下同じ）が１．
８〜６．０の範囲内にあるポリアミドを任意に選択でき
る。Note that there is no limit to the degree of polymerization of the polyamide resin used, and the relative viscosity of concentrated sulfuric acid (Polymer 12 is 98%
0 yxl and measured at 25°C, the same applies hereinafter) is 1.
Any polyamide within the range of 8 to 6.0 can be selected.
ポリアミド樹脂の分子構造についても制限はなく、線状
ポリアミド、分岐ポリアミドなどいずれを用いても構わ
ない。線状ポリアミドは通常の方法によって製造される
が、分岐ポリアミドは原料中にポリアミド形成可能な官
能基を３つ以上有する分岐剤、たとえばビス（ω−アミ
ノへキシ／Ｘ／）アミン、ジエチレントリアミン、トリ
メシン酸、ビスラクタムなどを少量添加して重合する。There is no restriction on the molecular structure of the polyamide resin, and either linear polyamide, branched polyamide, etc. may be used. Linear polyamides are produced by conventional methods, but branched polyamides are produced by using branching agents that have three or more functional groups capable of forming polyamides in the raw materials, such as bis(ω-aminohexy/X/)amine, diethylenetriamine, and trimesine. Polymerize by adding a small amount of acid, bislactam, etc.
重合方法は溶融重合、界面重合、溶液重合、塊状重合、
固相重合およびこれらの方法を組み合せた方法が利用さ
れ、−船釣には溶融重合が最も適当である。また特にポ
リアミド原料がラクタム類の場合にはアニオン重合によ
ってポリマーを得てもよい。Polymerization methods include melt polymerization, interfacial polymerization, solution polymerization, bulk polymerization,
Solid state polymerization and combinations of these methods are used; melt polymerization is most suitable for boat fishing. Further, particularly when the polyamide raw material is a lactam, the polymer may be obtained by anionic polymerization.
Ｏ熱可塑性樹脂組成物
本発明の熱可塑性樹脂組成物は、上述のポリカーボネー
ト１０〜９０重量％とゴム強化スチレン系樹脂９０〜１
０重量％からなる樹脂組成物１００ｉ量部当υ、変性ポ
リカーボネート０、１〜３０重量部ならびにポリアミド
１０〜１００重量部配合してなり、かつゴム強化スチレ
ン系樹脂（Ｂ）と変性ポリカーボネート（ＩＩ）の合計
当り、不飽和カルボン酸又はその無水物を０．０１〜８
重量％含有する組成物である。O Thermoplastic Resin Composition The thermoplastic resin composition of the present invention contains 10 to 90% by weight of the above-mentioned polycarbonate and 90 to 1% by weight of a rubber-reinforced styrene resin.
100 parts by weight of a resin composition consisting of 0% by weight, 0, 1 to 30 parts by weight of modified polycarbonate, and 10 to 100 parts by weight of polyamide, and rubber-reinforced styrenic resin (B) and modified polycarbonate (II) 0.01 to 8 of unsaturated carboxylic acid or its anhydride per total of
% by weight.
変性ポリカーボネートが０．１重量部未満では耐衝撃性
に劣ると共に層剥離が改善されない、一方３０重量部を
超すと耐熱性が低下する。好ましくは０．５〜ＩＯ重量
部である。又ポリアミドが１０重量部未満では耐薬品性
に劣り、１００重量部を超すと耐熱性が低下する。好ま
しくは１５〜５０重量部である。If the amount of the modified polycarbonate is less than 0.1 parts by weight, the impact resistance will be poor and delamination will not be improved, while if it exceeds 30 parts by weight, the heat resistance will decrease. Preferably it is 0.5 to IO parts by weight. Furthermore, if the polyamide content is less than 10 parts by weight, the chemical resistance will be poor, and if it exceeds 100 parts by weight, the heat resistance will be reduced. Preferably it is 15 to 50 parts by weight.
ゴム強化スチレン系樹脂（Ｂ）及び変性ポリカーボネー
ト（ｎ）からもたらされる不飽和カルボン酸又はその無
水物の合計が（Ｂ ）＋（Ｉｔ）の合計当ｆｉｏ、０１
重量％未満では充分な耐衝撃性を得ることが困難となる
。一方８重量％を超すと耐熱性が低下する。好ましくは
０．０５〜５重量％である。The sum of the unsaturated carboxylic acids or their anhydrides produced from the rubber-reinforced styrenic resin (B) and the modified polycarbonate (n) is the sum of (B) + (It), 01
If it is less than % by weight, it will be difficult to obtain sufficient impact resistance. On the other hand, if it exceeds 8% by weight, heat resistance will decrease. Preferably it is 0.05 to 5% by weight.
ポリカーボネート、
ゴム強化スチレン系樹脂、
変性ポリカーボネート及びポリアミドの混合方法につい
ては特に制限はなく、粉末、ビーズ、ペレット等いずれ
の形態でも混合することができる。又、それらの混合順
序についても特に制限はなく、四成分の一括混合、特定
成分を予備混合した後桟る成分を混合する方法のいずれ
でも良い。溶融混練方法としては、バンバリーミキサ−
ロール、押出機等の公知の方法を採用する事ができる。There are no particular restrictions on the method of mixing polycarbonate, rubber-reinforced styrene resin, modified polycarbonate, and polyamide, and they can be mixed in any form such as powder, beads, or pellets. Further, there is no particular restriction on the order of mixing them, and either a method of mixing the four components at once or a method of premixing a specific component and then mixing other components may be used. As a melt kneading method, Banbury mixer is used.
Known methods such as rolls and extruders can be used.
なお、混合時に、必要に応じて酸化防止剤、紫外線吸収
剤、帯電防止剤、滑剤、染料、顔料、可塑剤、難燃剤、
離型剤等の添加剤を配合する事ができる。又、ポリアセ
タール、ポリブチレンテレフタレート、ホリフエニレン
オキサイド、ポリメチルメタクリレート、ポリ塩化ビニ
ル等の熱可塑性樹脂を適宜配合する事もできる。In addition, when mixing, antioxidants, ultraviolet absorbers, antistatic agents, lubricants, dyes, pigments, plasticizers, flame retardants,
Additives such as a mold release agent can be added. Further, thermoplastic resins such as polyacetal, polybutylene terephthalate, polyphenylene oxide, polymethyl methacrylate, and polyvinyl chloride can also be appropriately blended.
次に実施例および比較例により本発明を具体的に説明す
る。尚、部数およびパーセントについてはいずれも重量
基準で示した。Next, the present invention will be specifically explained using Examples and Comparative Examples. Note that all parts and percentages are expressed on a weight basis.
実施例および比較例
ポリカーボネート、ゴム強化スチレン系樹脂、変性ポリ
カーボネートおよびポリアミドを第１〜３表に示す配合
組成で混合し、４０１１１の２軸押出機を用いて溶融混
合、造粒した。Examples and Comparative Examples Polycarbonate, rubber-reinforced styrene resin, modified polycarbonate, and polyamide were mixed in the compositions shown in Tables 1 to 3, and melt-mixed and granulated using a 40111 twin-screw extruder.
得られた組成物の各種物性を第１〜３表に示す。Various physical properties of the obtained composition are shown in Tables 1 to 3.
なお、用いられた樹脂は以下のとおり。The resins used are as follows.
０ポリカーボネート
ＰＣ：ビスフェノー／Ｌ／Ａとホスゲンとの脱塩重縮合
反応により得られたポリカーボネート（粘度平均分子量
２８０００）。0 Polycarbonate PC: Polycarbonate (viscosity average molecular weight 28,000) obtained by desalting polycondensation reaction of bisphenol/L/A and phosgene.
０ゴム強化スチレン系樹脂
ＡＢＳ−■＝ポリブタジェンラテックス５０部（固形分
）、スチレン３５部およびアクリロニトリル１５部を公
知の乳化重合法で重合してなるグラフト重合体６０％と
スチレン７０部とアクリロニトリル１５部を公知の乳化
重合法で重合してなる共重合体４０％とからなるＡＢＳ
樹脂。0 Rubber reinforced styrenic resin ABS- ■ = 60% graft polymer obtained by polymerizing 50 parts of polybutadiene latex (solid content), 35 parts of styrene, and 15 parts of acrylonitrile by a known emulsion polymerization method, 70 parts of styrene, and acrylonitrile. ABS consisting of 40% of a copolymer obtained by polymerizing 15 parts by a known emulsion polymerization method.
resin.
ＡＢＳ−■：ＡＢＳ−■で用いられたグラフト重合体６
０％とフチレフ６フ、５部、アクリロニトリル３０部お
よびメタアクリル酸２．５部を公知の乳化重合法で重合
してなる共重合体４０％とからなるＡＢＳ樹脂。ABS-■: Graft polymer 6 used in ABS-■
An ABS resin consisting of 0% and 40% of a copolymer obtained by polymerizing 5 parts of Futilef 6F, 30 parts of acrylonitrile, and 2.5 parts of methacrylic acid using a known emulsion polymerization method.
ＡＢＳ−■：ＡＢＳ−■で用いられたグラフト重合体６
０％とスチレン７０部、アクリロニトリル２５部および
メタアクリル酸５部を公知の乳化重合法で重合してなる
共重合体４０％とからなるＡＢＳ樹脂。ABS-■: Graft polymer 6 used in ABS-■
0% and 40% of a copolymer obtained by polymerizing 70 parts of styrene, 25 parts of acrylonitrile, and 5 parts of methacrylic acid using a known emulsion polymerization method.
ＡＥＳ−■：エチレンープロピレンーエチリデンノルホ
ルネンゴム４０部、スチレン４５部およびアクリロニト
リル１５部を公知の懸濁重合法で重合してなるグラフト
重合体７０％とスチレン７０部とアクリロニトリＩＬ／
３０部を公知の乳化重合法で重合してなる共重合体３０
％とからなるＡＢＳ樹脂。AES-■: 70% graft polymer obtained by polymerizing 40 parts of ethylene-propylene-ethylidene norhorne rubber, 45 parts of styrene, and 15 parts of acrylonitrile by a known suspension polymerization method, 70 parts of styrene, and acrylonitrile IL/
Copolymer 30 obtained by polymerizing 30 parts by a known emulsion polymerization method
ABS resin consisting of %.
ＡＥＳ−■：ＡＥＳ−■で用いられたグラフト重合体７
０％とスチレン７０部、アクリロニトリル２８部および
メタアクリル酸２部を公知の乳化重合法で重合してなる
共重合体３０％とからなるＡＢＳ樹脂。AES-■: Graft polymer 7 used in AES-■
0% and 30% of a copolymer obtained by polymerizing 70 parts of styrene, 28 parts of acrylonitrile, and 2 parts of methacrylic acid using a known emulsion polymerization method.
○変性ポリカーボネート
ＰＣ−Ｇ−１：ビスフェノールＡとホスゲンとの脱塩重
縮合反応により得られた粘度平均分子量２１０００のポ
リカーボネート１００部、スチレン５０部およびアクリ
ロニトリル２０部を一般的な懸濁重合に基づき重合を行
った。○Modified polycarbonate PC-G-1: 100 parts of polycarbonate with a viscosity average molecular weight of 21,000 obtained by desalting polycondensation reaction of bisphenol A and phosgene, 50 parts of styrene, and 20 parts of acrylonitrile are polymerized based on general suspension polymerization. I did it.
ＰＣ−Ｇ−２： ＰＣ−Ｇ −１におけるスチレン５０
部を、スチレン４０部およびメタアクＵ ／し酸１０部
に変更し、ＰＣ−Ｇ−１同様重合を行った。PC-G-2: Styrene 50 in PC-G-1
Polymerization was carried out in the same manner as PC-G-1 except that the parts were changed to 40 parts of styrene and 10 parts of methacrylic acid/phosphoric acid.
ＰＣ−Ｇ−８：粘度平均分子量８２０００のポリカーボ
ネート１００部当りスチレン５０部、アクリロニトリル
４０部およびメチルメタクリレート４０部を用いてＰＣ
−Ｇ−１と同様に重合を行った。PC-G-8: PC using 50 parts of styrene, 40 parts of acrylonitrile and 40 parts of methyl methacrylate per 100 parts of polycarbonate with a viscosity average molecular weight of 82,000.
- Polymerization was carried out in the same manner as in G-1.
ＰＣ−Ｇ−４： ＰＣ−Ｇ−３におけるメチルメタクリ
レート４０部を、メチルメタクリシト２０部およびアク
ＩＪ ／し酸２０部に変更し、ＰＣ−Ｇ−１同様重合を
行った。PC-G-4: 40 parts of methyl methacrylate in PC-G-3 was changed to 20 parts of methyl methacrylate and 20 parts of Ac IJ/cyanic acid, and polymerization was carried out in the same manner as in PC-G-1.
○ポリアミド
ＰＡ−６：ナイロン６、濃硫酸相対粘度２．６ＰＡ−６
６：ナイロン１２、濃硫酸相対粘度３．０耐熱性：ＡＳ
ＴＭ Ｄ−６４８
１８，６１’ｌｒ／ｃｒＩ、アニールなし耐衝撃性：Ａ
ＳＴＭ Ｄ−２５６
１／４インチ厚、ノツチ付アイゾツト
耐薬品性：射出成形されたＡＳＴＭ Ｉ型ダンベ／Ｌ
／（Ｉ／８インチ厚、全長２１７１Ｂ）を両端に止め具
を有する円弧状治具上
に固定する。（治具の曲率より試験片
の表面歪を１％又は１．５％とする。）試験片表面にケ
ロシンを塗布し、
６０℃、２４時間放置する。その後試
験片の折れ、及び試験片表面上のクラ
ックの有無を確認する。○Polyamide PA-6: Nylon 6, concentrated sulfuric acid Relative viscosity 2.6 PA-6
6: Nylon 12, concentrated sulfuric acid Relative viscosity 3.0 Heat resistance: AS
TM D-648 18,61'lr/crI, impact resistance without annealing: A
STM D-256 1/4" Thick, Notched Izot Chemical Resistance: Injection Molded ASTM Type I Dumbbell/L
/ (1/8 inch thick, total length 2171B) is fixed on an arcuate jig with stops at both ends. (Set the surface strain of the test piece as 1% or 1.5% based on the curvature of the jig.) Apply kerosene to the surface of the test piece and leave it at 60°C for 24 hours. After that, check for bends in the test piece and for cracks on the surface of the test piece.
○：クランク無
△：クランク有
×：折れ
ウニｐド強度：２点ゲート金型を用いて中央部にウェル
ド部を有する試験片（５ｃｍ Ｘ５ｍ×３鵡）を作成す
る。○: No crank △: With crank ×: Broken sea urchin Strength: Using a two-point gate mold, a test piece (5 cm x 5 m x 3 parrots) having a weld part in the center is prepared.
一３０℃に調整された試験片の上方 ４゜ ５０ｍの高さから５９の鋼球を試験片 中心部に落下させ、割れの有無を確認 する。Above the test piece adjusted to -30℃ 4゜ Test specimen of 59 steel balls from a height of 50m Drop it to the center and check for cracks. do.
０８割れず
×：割れ
層剥離二下記成形条件にて図に示される試験片を作成し
た後、ゲート部で曲げてスプ
ル一部を除去した際の成形品部での層
剥離の有無を確認する。08 No cracking ×: Cracked layer peeling 2 After creating the test piece shown in the figure under the following molding conditions, check whether there is any layer peeling at the molded part when bending at the gate and removing part of the sprue. .
本発明は、従来公知の組成物に比べ耐衝撃性、耐薬品性
に優れ、かつ層剥離のない組成物を提供するものであり
、車両、電気・電子機器等の分野において新たな用途を
可能にする。The present invention provides a composition that has superior impact resistance and chemical resistance compared to conventionally known compositions and does not peel off, and enables new applications in fields such as vehicles and electrical/electronic equipment. Make it.
第１図は、層剥離の有無を評価するために用いられた試
験片の平面図、又第２図は断面図である。
■二ゲート
■
フ
ィルムゲー
ト
■：
成形品
曲げ方向FIG. 1 is a plan view of a test piece used to evaluate the presence or absence of delamination, and FIG. 2 is a cross-sectional view. ■Two gates■ Film gate■: Molded product bending direction
Claims (1)
体１０〜９０重量％、芳香族ビニル化合物、不飽和ニト
リル化合物、不飽和カルボン酸アルキルエステル化合物
およびマレイミド化合物から選択された一種以上の化合
物１０〜８０重量％および不飽和カルボン酸又はその無
水物０〜１０重量％からなるゴム強化スチレン系樹脂（
Ｂ）９０〜１０重量％からなる樹脂組成物（ I ）１０
０重量部当り、ポリカーボネート２０〜７０重量％、芳
香族ビニル化合物、不飽和ニトリル化合物、不飽和カル
ボン酸アルキルエステル化合物およびマレイミド化合物
から選択された一種以上の化合物２０〜８０重量％およ
び不飽和カルボン酸又はその無水物０〜１０重量％から
なる変性ポリカーボネート（II）０．１〜３０重量部お
よびポリアミド（III）１０〜１００重量部配合してな
り、かつゴム強化スチレン系樹脂（Ｂ）と変性ポリカー
ボネート（II）の合計当り、不飽和カルボン酸又はその
無水物を０．０１〜８重量％含有することを特徴とする
熱可塑性樹脂組成物。10 to 90% by weight of polycarbonate (A), 10 to 90% by weight of a rubbery polymer, and 10 to 10 or more compounds selected from aromatic vinyl compounds, unsaturated nitrile compounds, unsaturated carboxylic acid alkyl ester compounds, and maleimide compounds. Rubber-reinforced styrenic resin consisting of 80% by weight and 0 to 10% by weight of unsaturated carboxylic acid or its anhydride (
B) Resin composition (I) consisting of 90 to 10% by weight 10
0 parts by weight, 20-70% by weight of polycarbonate, 20-80% by weight of one or more compounds selected from aromatic vinyl compounds, unsaturated nitrile compounds, unsaturated carboxylic acid alkyl ester compounds, and maleimide compounds, and unsaturated carboxylic acids. or 0.1 to 30 parts by weight of modified polycarbonate (II) consisting of 0 to 10% by weight of its anhydride and 10 to 100 parts by weight of polyamide (III), and rubber-reinforced styrenic resin (B) and modified polycarbonate A thermoplastic resin composition containing 0.01 to 8% by weight of an unsaturated carboxylic acid or anhydride thereof based on the total amount of (II).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2238763A JP3012910B2 (en) | 1990-09-07 | 1990-09-07 | Thermoplastic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2238763A JP3012910B2 (en) | 1990-09-07 | 1990-09-07 | Thermoplastic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04120172A true JPH04120172A (en) | 1992-04-21 |
| JP3012910B2 JP3012910B2 (en) | 2000-02-28 |
Family
ID=17034904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2238763A Expired - Fee Related JP3012910B2 (en) | 1990-09-07 | 1990-09-07 | Thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3012910B2 (en) |
-
1990
- 1990-09-07 JP JP2238763A patent/JP3012910B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3012910B2 (en) | 2000-02-28 |
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