JPH0157700B2 - - Google Patents
Info
- Publication number
- JPH0157700B2 JPH0157700B2 JP55147552A JP14755280A JPH0157700B2 JP H0157700 B2 JPH0157700 B2 JP H0157700B2 JP 55147552 A JP55147552 A JP 55147552A JP 14755280 A JP14755280 A JP 14755280A JP H0157700 B2 JPH0157700 B2 JP H0157700B2
- Authority
- JP
- Japan
- Prior art keywords
- component
- weight
- polymer
- copolymer
- vinyl aromatic
- 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.)
- Expired
Links
- 239000000203 mixture Substances 0.000 claims description 67
- -1 vinyl aromatic compounds Chemical class 0.000 claims description 65
- 229920001400 block copolymer Polymers 0.000 claims description 58
- 229920000642 polymer Polymers 0.000 claims description 48
- 229920002554 vinyl polymer Polymers 0.000 claims description 43
- 229920001577 copolymer Polymers 0.000 claims description 40
- 239000000805 composite resin Substances 0.000 claims description 31
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 25
- 239000000178 monomer Substances 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 18
- 125000000524 functional group Chemical group 0.000 claims description 16
- 125000001142 dicarboxylic acid group Chemical group 0.000 claims description 12
- 229920002857 polybutadiene Polymers 0.000 claims description 11
- 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 claims description 10
- 239000005062 Polybutadiene Substances 0.000 claims description 10
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims description 5
- 229920002635 polyurethane Polymers 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 239000001530 fumaric acid Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000011976 maleic acid Substances 0.000 claims description 4
- 229920006122 polyamide resin Polymers 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 32
- 238000002156 mixing Methods 0.000 description 19
- 238000000034 method Methods 0.000 description 16
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 12
- 239000003365 glass fiber Substances 0.000 description 10
- 229920006112 polar polymer Polymers 0.000 description 10
- 150000008064 anhydrides Chemical class 0.000 description 8
- 229920003048 styrene butadiene rubber Polymers 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 239000006260 foam Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 229920000768 polyamine Polymers 0.000 description 6
- 238000010526 radical polymerization reaction Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000004604 Blowing Agent Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 125000005442 diisocyanate group Chemical group 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920001228 polyisocyanate Polymers 0.000 description 3
- 239000005056 polyisocyanate Substances 0.000 description 3
- 229920005990 polystyrene resin Polymers 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 2
- PNNFEYPWPCDLOC-UPHRSURJSA-N (z)-2,3-dichlorobut-2-enedioic acid Chemical compound OC(=O)C(\Cl)=C(\Cl)C(O)=O PNNFEYPWPCDLOC-UPHRSURJSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 2
- 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 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
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000001746 injection moulding Methods 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
- 239000000155 melt Substances 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-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
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 229920003225 polyurethane elastomer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- SOWPGKJPEXNMCS-OWOJBTEDSA-N (e)-2-bromobut-2-enedioic acid Chemical compound OC(=O)\C=C(\Br)C(O)=O SOWPGKJPEXNMCS-OWOJBTEDSA-N 0.000 description 1
- ZQHJVIHCDHJVII-OWOJBTEDSA-N (e)-2-chlorobut-2-enedioic acid Chemical compound OC(=O)\C=C(\Cl)C(O)=O ZQHJVIHCDHJVII-OWOJBTEDSA-N 0.000 description 1
- SASYHUDIOGGZCN-ARJAWSKDSA-N (z)-2-ethylbut-2-enedioic acid Chemical compound CC\C(C(O)=O)=C\C(O)=O SASYHUDIOGGZCN-ARJAWSKDSA-N 0.000 description 1
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical compound BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-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
- QQHQTCGEZWTSEJ-UHFFFAOYSA-N 1-ethenyl-4-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(C=C)C=C1 QQHQTCGEZWTSEJ-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-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
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- OMNYXCUDBQKCMU-UHFFFAOYSA-N 2,4-dichloro-1-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C(Cl)=C1 OMNYXCUDBQKCMU-UHFFFAOYSA-N 0.000 description 1
- 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 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
- BEWCNXNIQCLWHP-UHFFFAOYSA-N 2-(tert-butylamino)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCNC(C)(C)C BEWCNXNIQCLWHP-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
- QLIBJPGWWSHWBF-UHFFFAOYSA-N 2-aminoethyl methacrylate Chemical compound CC(=C)C(=O)OCCN QLIBJPGWWSHWBF-UHFFFAOYSA-N 0.000 description 1
- NRSMWHGLCNBZSO-UHFFFAOYSA-N 2-ethylidenebutanedioic acid Chemical compound CC=C(C(O)=O)CC(O)=O NRSMWHGLCNBZSO-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-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
- UWRZIZXBOLBCON-UHFFFAOYSA-N 2-phenylethenamine Chemical compound NC=CC1=CC=CC=C1 UWRZIZXBOLBCON-UHFFFAOYSA-N 0.000 description 1
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-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
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- XDOLZJYETYVRKV-UHFFFAOYSA-N 7-Aminoheptanoic acid Chemical compound NCCCCCCC(O)=O XDOLZJYETYVRKV-UHFFFAOYSA-N 0.000 description 1
- VWPQCOZMXULHDM-UHFFFAOYSA-N 9-aminononanoic acid Chemical compound NCCCCCCCCC(O)=O VWPQCOZMXULHDM-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 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
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical group CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920001890 Novodur Polymers 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-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
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000005263 alkylenediamine group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229940059260 amidate Drugs 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- CJYXCQLOZNIMFP-UHFFFAOYSA-N azocan-2-one Chemical compound O=C1CCCCCCN1 CJYXCQLOZNIMFP-UHFFFAOYSA-N 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 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 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000002666 chemical blowing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- ILUAAIDVFMVTAU-UHFFFAOYSA-N cyclohex-4-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CC=CCC1C(O)=O ILUAAIDVFMVTAU-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000002897 diene group Chemical group 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- NPUKDXXFDDZOKR-LLVKDONJSA-N etomidate Chemical compound CCOC(=O)C1=CN=CN1[C@H](C)C1=CC=CC=C1 NPUKDXXFDDZOKR-LLVKDONJSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- CVMNKHMWNZSNLW-UHFFFAOYSA-N hexane-1,6-diol;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.OCCCCCCO CVMNKHMWNZSNLW-UHFFFAOYSA-N 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000012693 lactam polymerization Methods 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- XMMDVXFQGOEOKH-UHFFFAOYSA-N n'-dodecylpropane-1,3-diamine Chemical compound CCCCCCCCCCCCNCCCN XMMDVXFQGOEOKH-UHFFFAOYSA-N 0.000 description 1
- ONCPEIKLFULSSA-UHFFFAOYSA-N n'-ethylbutane-1,4-diamine Chemical compound CCNCCCCN ONCPEIKLFULSSA-UHFFFAOYSA-N 0.000 description 1
- SCZVXVGZMZRGRU-UHFFFAOYSA-N n'-ethylethane-1,2-diamine Chemical compound CCNCCN SCZVXVGZMZRGRU-UHFFFAOYSA-N 0.000 description 1
- UKNVXIMLHBKVAE-UHFFFAOYSA-N n'-hexadecylpropane-1,3-diamine Chemical compound CCCCCCCCCCCCCCCCNCCCN UKNVXIMLHBKVAE-UHFFFAOYSA-N 0.000 description 1
- QHJABUZHRJTCAR-UHFFFAOYSA-N n'-methylpropane-1,3-diamine Chemical compound CNCCCN QHJABUZHRJTCAR-UHFFFAOYSA-N 0.000 description 1
- OWKYZAGJTTTXOK-UHFFFAOYSA-N n'-propylpropane-1,3-diamine Chemical compound CCCNCCCN OWKYZAGJTTTXOK-UHFFFAOYSA-N 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical compound CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920006327 polystyrene foam Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
本発明は、新規な複合樹脂組成物に関し、さら
に詳しくは、エチレン系不飽和ジカルボン酸無水
物と該モノマーと共重合可能なビニル系モノマー
を共重合して得られる多元共重合体と、ビニル芳
香族化合物−共役ジエン化合物共重合体をエチレ
ン系不飽和ジカルボン酸またはその誘導体で変性
したブロツク共重合体と、ジカルボン酸基または
その誘導体基と反応可能な官能基群を少なくとも
２個以上有する物質とを含有して成る耐衝撃性、
機械的強度、耐熱性に優れた成型用材料として好
適な複合樹脂組成物に関する。
例えばスチレン−無水マレイン酸共重合体で代
表されるビニル芳香族化合物−エチレン系不飽和
ジカルボン酸無水物共重合体は、従来のポリスチ
レン樹脂と比べ、熱変形温度が高く、さらにガラ
ス繊維混入時の機械的強度が極めて優れており、
同時にガラス繊維混入物の耐熱性も優れているこ
とが知られている。また、スチレン−無水マレイ
ン酸共重合体は耐熱性樹脂でありながら、加工性
が超耐熱性ABS樹脂と比べはるかに優れており、
ポリスチレン樹脂に近い押出、射出成形時の流動
特性を有している。その上、ポリスチレン樹脂と
同様に発泡体に加工成形が可能であり、従来のポ
リスチレン発泡体の耐熱性改良品として高温部の
断熱材、家電製品のハウジング部等の各種成型品
用途に多く使用されている。
しかし、スチレン−無水マレイン酸共重合体は
耐熱性、機械的強度に優れるものの、耐衝撃性に
劣り、ポリスチレン樹脂の耐衝撃性の改良品（ハ
イインパクトポリスチレン）、アクリロニトリル
−スチレン共重合体の耐衝撃性の改良品（ABS
樹脂）ほど広く耐衝撃性の改良がなされておら
ず、耐熱性、機械的強度、耐衝撃性の優れたスチ
レン−無水マレイン酸共重合体が望まれているの
が現状である。
本発明者らは、このような背景のもとで、上記
の問題点を改良するべく鋭意研究を重ねた結果、
従来技術によつては開示されていない組成物が、
エチレン系不飽和ジカルボン酸無水物と該モノマ
ーと共重合可能なビニル系モノマーとを共重合し
て得られる多元共重合体の所望の性質を損うこと
なしに優れた耐衝撃性を発揮し、成型材料用途等
に好適な組成物であることを見い出し本発明に到
達した。
すなわち、本発明は、(a)；エチレン系不飽和ジ
カルボン酸無水物と該モノマーと共重合可能なビ
ニル系モノマーを共重合して得られる多元共重合
体の(a)成分と、(b)；少なくとも１個のビニル芳香
族化合物を主体とする重合体ブロツクと、少なく
とも１個の共役ジエン化合物を主体とする重合体
ブロツクとを有し、該ビニル芳香族化合物と共役
ジエン化合物の重量比が５／95〜95／５であるブ
ロツク共重合体に、エチレン系不飽和ジカルボン
酸基またはその誘導体基を含む分子単位を該ブロ
ツク共重合体100重量部あたり0.05〜20重量部結
合せしめて成る変性ブロツク共重合体の(b)成分
と、(c)；ジカルボン酸基またはその誘導体基と反
応可能な官能基として水酸基、アミノ基、エポキ
シ基、イソシアネート基、ウレタン基から選ばれ
た官能基を少なくとも２個以上有する化合物また
は重合体である(c)成分とを含有して成る複合樹脂
組成物であり、(a)成分と(b)成分の合計が50重量％
以上、99重量％以下、(c)成分を１重量％以上50重
量％以下を含有し、さらに、(a)成分が(a)成分と(b)
成分の合計に対し、１重量％以上、99重量％以下
含有することを特徴とする複合樹脂組成物であ
る。
以下、本発明に関して詳しく述べる。
本発明の目的を達成するには、本発明の構成成
分である(a)成分、(b)成分、(c)成分が不可欠であ
り、これらの成分のどの一つが欠けても本発明の
目的は達成できない。すなわち、本発明は、従来
の樹脂ブレンドと異なり、官能基が有している反
応性を利用した官能性化合物または官能性重合体
のブレンドに関する技術的に意義深い思想に基づ
くものであり、(a)成分、(b)成分、(c)成分のそれぞ
れが有する官能基の反応によつてのみ達成される
複合樹脂組成物である。
本発明で用いられる(a)成分の多元共重合体は、
エチレン系不飽和ジカルボン酸無水物と該エチレ
ン不飽和ジカルボン酸無水物と共重合可能なモノ
マーを共重合して得られる多元共重合体であり、
具体的な共重合可能モノマーとしては、例えばビ
ニル芳香族化合物が挙げられる。
ビニル芳香族化合物として有用なモノマーは、
スチレン、ｏ−メチルスチレン、ｍ−メチルスチ
レン、ｐ−メチルスチレン、エチルスチレン、ジ
メチルスチレン、ジビニルベンゼン、α−メチル
スチレン、ｐ−メトキシスチレン、ｐ−クロルス
チレン、２・４−ジクロルスチレン、２・５−ジ
クロルスチレン、ｐ−ブロムスチレン、α−メチ
ル−ｐ−メチルスチレン、ｐ−イソプロピルスチ
レン、ビニルナフタリンおよびその類似物が含ま
れ、さらに所望により、これらのビニル芳香族化
合物の２種類またはそれ以上の混合物も使用する
ことができる。
共重合体の必須成分であるエチレン系不飽和ジ
カルボン酸無水物として成り得る単量体として
は、酸無水物の無水マレイン酸、エチレン系不飽
和ジカルボン酸であるマレイン酸、フマル酸、イ
タコン酸、シトラコン酸、メサコン酸、エチルマ
レイン酸、メチルイタコン酸、クロルマレイン
酸、ジクロルマレイン酸、ブロムマレイン酸、ジ
ブロム−マレイン酸およびこれら無水物があげら
れ、さらにエチレン系不飽和ジカルボン酸から生
ずる半エステルも使用することができる。これら
の酸および半エステル基を有する共重合体は、最
終的にはエチレン系不飽和半エステルまたはジカ
ルボン酸の酸素含有基から環状の無水物基を生ぜ
しめる操作を行ない、無水物成分を有するビニル
芳香族化合物と無水物の共重合体を得る。
さらに本発明で用いられる(a)成分は、上記に挙
げたビニル芳香族化合物−エチレン系不飽和ジカ
ルボン酸無水物共重合体のほかに、エチレン系不
飽和ジカルボン酸無水物と該モノマーと共重合可
能であるモノマー、例えば、スチレン、エチレ
ン、プロピレン、１−ブテン、酢酸ビニル、ビニ
ルエーテル、アクリロニトリル、メタクリル酸、
メチルメタクリレート、アクリル酸、アクリル酸
エステル、塩化ビニルの１種または２種以上を共
重合して得られる多元共重合体がある。
これら共重合体の製造方法は、公知の重合方
法、例えば、溶液重合法、塊状重合法、塊状−懸
濁重合法、懸濁重合法等によるラジカル重合方法
が工業的に有利に用いられる。
このようにして得られるエチレン系不飽和ジカ
ルボン酸無水物を共重合した多元共重合体は、低
分子量の共重合体も使用できるが、好ましくは重
量平均分子量が20000〜1000000、さらに好ましく
は50000〜500000のものが使用され、共重合体中
の無水マレイン酸含有量は３〜50モル％が好まし
く、さらに好ましい無水マレイン酸含有量は５〜
30モル％である。
つぎに本発明で用いられる(b)成分は、ビニル芳
香族化合物を主体とする重合体ブロツク１個以上
と、共役ジエン化合物を主体とする重合体ブロツ
ク１個以上とを含有し、ビニル芳香族化合物と共
役ジエン化合物の重量比が５／95〜95／５である
ブロツク共重合体に、不飽和ジカルボン酸または
その誘導体が付加した変性ブロツク共重合体であ
る。
ここでビニル芳香族化合物を主体とする重合体
ブロツクとは、ビニル芳香族化合物重合体ブロツ
クまたはビニル芳香族化合物の含有量が50重量％
を超え、好ましくは70重量％以上であるビニル芳
香族化合物と共役ジエン化合物との共重合体ブロ
ツクであり、共役ジエン化合物を主体とする重合
体ブロツクとは、共役ジエン化合物重合体ブロツ
クまたは共役ジエン化合物の含有量が50重量％を
超え、好ましくは70重量％以上であるビニル芳香
族化合物と共役ジエン化合物との共重合体ブロツ
クである。
上記変性ブロツク共重合体の基体となるビニル
芳香族化合物−共役ジエン化合物ブロツク共重合
体（以下単に「ブロツク共重合体」という）は、
ビニル芳香族化合物を主体とする重合体ブロツク
１個以上、好ましくは２個以上と、共役ジエン化
合物を主体とする重合体ブロツク１個以上とを含
有するものである。該ブロツク共重合体におい
て、ビニル芳香族化合物と共役ジエン化合物の重
量比は５／95〜95／５、好ましくは10／90〜90／
10、さらに好ましくは20／80〜80／20の組成範囲
である。
該ブロツク共重合体は、ビニル芳香族化合物の
含有量が70重量％以下の場合はエラストマー的な
性質を示し、70重量％を超える場合は樹脂的な性
質を示す。
またブロツク共重合体のビニル芳香族化合物を
主体とする重合体ブロツク、共役ジエン化合物を
主体とする重合体ブロツクは、この重合体ブロツ
クにおける分子鎖中の共役ジエン化合物またはビ
ニル芳香族化合物の分布がランダム、テーパード
（分子鎖に沿つてモノマー成分が増加または減少
するもの）、一部ブロツク状またはこれらの任意
の組合せで成つていてもよい。ビニル芳香族化合
物を主体とする重合体ブロツクが２個以上である
場合は、各ブロツクは同一構造であつてもよく、
異なる構造であつてもよい。また、共役ジエン化
合物を主体とする重合体ブロツクを２個以上含有
する場合は、各ブロツクは同一の構造であつても
よく、異なる構造であつてもよい。
ブロツク共重合体を構成するビニル芳香族化合
物としては、例えば、スチレン、α−メチルスチ
レン、ビニルトルエン、ｐ−tert−ブチルスチレ
ン等のうちから１種または２種以上が選ばれ、中
でもスチレンが特に好ましい。また共役ジエン化
合物としては、例えば、ブタジエン、イソプレ
ン、１・３−ペンタジエン、２・３−ジメチル−
１・３−ブタジエン等のうちから１種または２種
以上が選ばれ、中でもブタジエンまたはブタジエ
ンを主体とする共役ジエン化合物の組合せが好ま
しく、特にブタジエンが好ましい。
該ブロツク共重合体の数平均分子量は5000〜
1000000、好ましくは10000〜800000、さらに好ま
しくは30000〜500000の範囲であり、分子量分布
（重量平均分子量と数平均分子量の比）は10以下
である。
さらに、ブロツク共重合体の分子構造は、直鎖
状、分岐状、放射状あるいはこれらの任意の組合
せのいずれであつてもよい。また上記ブロツク共
重合体は、その特性を失わない限りにおいて有機
化合物あるいは無機化合物によつて若干の変性が
行なわれていてもよい。
本発明で用いるブロツク共重合体は、通常、ヘ
キサン、シクロヘキサン、ベンゼン、トルエン等
の不活性炭化水素溶媒中で、ブチルリチウム等の
有機リチウム化合物を重合触媒として、ビニル芳
香族化合物と共役ジエン化合物をアニオン共重合
することによつて得られ、この際、モノマーの添
加方法や添加順序を変えたり、多官能性のリチウ
ム化合物を使用することにより、各種構造のブロ
ツク共重合体が得られる。また上記方法で得られ
るリチウム活性末端を有するブロツク共重合体を
多官能カツプリング剤、たとえば、四塩化炭素、
四塩化ケイ素等に反応させることにより、分岐
状、放射状のブロツク共重合体とすることが可能
である。その他、いかなる製造方法で得られたビ
ニル芳香族化合物−共役ジエン化合物ブロツク共
重合体であつても、前記限定の範囲内であれば使
用できる。
上記ブロツク共重合体は、１種だけでなく２種
類以上のものを組合わせたものでもよく、これら
の組合わせの例としては、スチレン−ブタジエン
ブロツク共重合体の組合せ、分子量の異なる２種
のスチレン−ブタジエンブロツク共重合体の組合
せ、スチレン含量の異なる２種のスチレン−ブタ
ジエンブロツク共重合体の組合せ、ブロツク構造
がスチレン−ブタジエン−スチレンの３つのセグ
メントからなるものと、ブタジエン−スチレン−
ブタジエン−スチレンの４つのセグメントからな
るもの等の異なるスチレン−ブタジエンブロツク
共重合体の組合せなどがある。
つぎに、ブロツク共重合体にグラフトした不飽
和ジカルボン酸またはその誘導体について説明す
る。これら不飽和ジカルボン酸またはその誘導体
は、活性な不飽和結合の位置でブロツク共重合体
の共役ジエン部分に付加している。これらはブロ
ツク共重合体100重量部あたり0.05〜20重量部、
好ましくは0.05〜10重量部、さらに好ましくは
0.1〜２重量部付加していることが、スチレン系
複合樹脂組成物の目的の特性を引き出すために必
要である。付加量が0.05重量部未満では、未変性
のブロツク共重合体に比してほとんど改良効果が
なく、付加量を20重量部を超えても改善効果はそ
れ以上向上しない。
上記不飽和ジカルボン酸またはその誘導体の例
としては、マレイン酸、フマル酸、イタコン酸、
ジクロロマレイン酸、シス−４−シクロヘキセン
−１・２−ジカルボン酸、エンド−シス−ビシク
ロ〔２，２，１〕−５−ヘプテン−２・３−ジカ
ルボン酸などや、これらジカルボン酸の酸無水
物、エステル、アミド、ジカルボン酸イミドなど
があげられる。ジカルボン酸の各種誘導体は、誘
導体のままブロツク共重合体に付加させてもよ
く、また不飽和ジカルボン酸をブロツク共重合体
に付加させた後、しかるべき反応によつてカルボ
ン酸基を対応する誘導体に変換してもよい。かか
るカルボン酸基からその誘導体への変換反応は、
エチレン系不飽和ジカルボン酸無水物を共重合し
て得られる多元共重合体(a)成分と、ジカルボン酸
変性したブロツク共重合体(b)成分とを混合して成
る組成物の段階で任意に実施してもよい。
上記のブロツク共重合体を変性する不飽和ジカ
ルボン酸またはその誘導体の中では、マレイン
酸、フマル酸、無水マレイン酸が好ましい。
本発明の変性ブロツク共重合体は、前記ブロツ
ク共重合体に、不飽和ジカルボン酸またはその誘
導体を溶融状態または溶液状態において、ラジカ
ル開始剤を使用あるいは使用せずしてグラフト反
応させることにより得られる。これら変性ブロツ
ク共重合体の製造方法に関しては、本発明では特
に限定しないが、得られた変性ブロツク共重合体
中にゲル等の好ましくない成分が含まれていた
り、その流動性が低下して加工性が悪化するよう
な製造方法は好ましくない。好ましい方法として
は、たとえば押出機中で、パーオキサイドを添加
せずにブロツク共重合体を不飽和ジカルボン酸ま
たはその誘導体と反応させる方法がある。
つぎに本発明で用いられる(c)成分は、(a)成分、
(b)成分が有するジカルボン酸基またはその誘導体
基と反応可能な官能基を少なくとも２個持つた化
合物または重合体である。ジカルボン酸基または
その誘導体基と反応可能な官能基を持つた化合物
または重合体としては、水酸基、アミノ基、エポ
キシ基、イソシアネート基、ウレタン基のうちか
ら選ばれた官能基で構成されたものである。な
お、(c)成分はジカルボン酸基またはその誘導体基
と反応し共有結合を形成する化合物であり、可逆
的な結合であるイオン結合を形成するようなイオ
ン架橋剤化合物は含まない。
上記ジカルボン酸基またはその誘導体と反応可
能な官能基を持つ好適な重合体は、水酸基変性ポ
リブタジエン、エポキシ変性ポリブタジエン、ア
ミン変性ポリブタジエン、イソシアネート変性ポ
リブタジエンである。これら官能基変性ポリブタ
ジエンは、その基体であるポリブタジエンを末端
あるいは側鎖の位置で変性したもので、分子量
500〜10000、さらに好ましくは1000〜8000の液状
重合体である。この官能基変性ポリブタジエン以
外に基体となる重合体は、スチレン−ブタジエン
共重合体オリゴマーでもよく、他に１・３−ペン
タジエン、イソプレン等のジエン系オリゴマー、
スチレン系オリゴマーも好適である（以下単に
「官能性オリゴマー」という）。これら官能性オリ
ゴマーまたは官能性オリゴマーの基体となるオリ
ゴマーは、公知のいかなる製造方法で得ることが
でき、アニオン重合方法、カチオン重合方法、ラ
ジカル重合方法が工業的に有用である。
さらに好適な(c)成分の重合体としては、上記に
掲げた官能性オリゴマーの他に、ビニルアルコー
ル系重合体（共重合体も含む）、ポリアルキレン
グリコール重合体（共重合体も含む）、ビニル性
グリシジル重合体（共重合体も含む）、ポリアミ
ド樹脂、エポキシ樹脂、ポリウレタン（以下、単
に極性重合体という）がある。これら極性重合体
は、好ましくは10000を超える分子量を有するも
のであるが、分子鎖中にジカルボン酸またはその
誘導体と反応可能な官能基を２個以上有する低分
子量体単位であつてもかまわない。
ここで掲げた極性重合体は、重合可能な極性化
合物をラジカル重合することによつて得られる極
性重合体のほかに、極性化合物をポリ付加または
ポリ縮合することによつて得られる極性重合体で
あり、重合体主鎖末端または重合体側鎖の位置に
ジカルボン酸またはその誘導体と反応可能な、水
酸基、アミノ基、エポキシ基、イソシアネート
基、ウレタン基のうちから選ばれた官能基を少な
くとも２個以上有する極性重合体である。
有用である重合可能な極性化合物としては、酢
酸ビニル、アリルグリシジルエーテル、グリシジ
ルアクリレート、グリシジルメタクリレート、グ
リシジルエタクリレート、ポリエチレングリコー
ルモノメタクリレート、アリルアルコール、ヒド
ロキシスチレン、２−ヒドロキシエチルメタクリ
レート、２−ヒドロキシエチルアクリレート、２
−ヒドロキシプロピルメタクリレート、アミノエ
チルメタクリレート、ジアリルアミン、ｔ−ブチ
ルアミノエチルメタクリレート、Ｎ−メチロール
メタクリレート、アクリルアミド、アクリルアミ
ド置換体、モノアミノスチレンがある。さらに所
望により、これらビニルモノマーと共重合可能な
ビニルモノマー、たとえば、スチレン、アクリロ
ニトリル、アクリル酸エステル、メタクリル酸エ
ステル、エチレン等と共重合を行なつて、極性重
合体ホモポリマーまたは極性共重合体を得る。こ
れら極性（共）重合体は、公知のいかなる重合方
法、たとえば、乳化重合法、溶液重合法、塊状重
合法、懸濁重合法等によるラジカル重合方法によ
り、工業的に有利に製造される。
さらに有用な極性重合体であるポリアミド樹脂
は、通常２〜20個の炭素原子を有する二塩基酸ま
たはその誘導体と、２〜15個の炭素原子を有する
ジアミンとを等モル量において縮合させるか、３
員環以上のラクタムをラクタム重合させるか、ω
−アミノ酸などを重縮合することによつて工業的
に有利に製造される。
有用なジアミンとしては、ヘキサメチレンジア
ミン、ノナメチレンジアミン、ウンデカメチレン
ジアミン、ドデカメチレンジアミン、メタキシリ
レンジアミン等があげられ、有用な二塩基酸とし
ては、アジピン酸、セバシン酸、テレフタル酸、
イソフタル酸、ドデカン二塩基酸、グルタール酸
等があげられる。さらにε−カプロラクタム、エ
ナントラクタム、α−ピロリドン、α−ピペリド
ン、アミノカプロン酸、７−アミノヘプタン酸、
９−アミノノナン酸、11−アミノウンデカン酸な
どの重合体がある。これらの重合体または共重合
体であるポリアミド樹脂は、ナイロン４、６、
７、８、11、12、６・６、６・９、６・10、６・
11、６・12、6T、６／６・６、６／12、６／6T
などである。
極性重合体として有用なポリウレタンは、分子
量500〜10000のポリエステルまたはポリエーテル
を〔NCO〕／〔OH〕＋〔COOH〕または
〔NCO〕／〔OH〕約１〜２の条件でジイソシア
ネートと反応させた末端に遊離のイソシアネート
基を有するマクロジイソシアネート（プレポリマ
ー）である。さらに所望により、このプレポリマ
ーをヒドラジン、ジアミン、エチレングリコー
ル、水等の活性水素を有する鎖伸長反応剤を加
え、それぞれビスウレイン結合、尿素結合、ウレ
タン結合をつくつて高重合度ポリマーにしたもの
でもよい。ポリウレタンの基体となるポリエステ
ルは、従来の通常の方法で製造され、たとえば、
アジピン酸またはアゼライン酸とポリエチレング
リコールまたはポリプロピレングリコールとを反
応させ、両末端にOH基を存在させたものも好適
に使用できる。さらにポリウレタンの基体となる
ポリエーテルも同様に、従来の通常の方法で製造
され、具体的には、酸化エチレン、酸化プロピレ
ンからのポリエーテルを基礎にした両末端OH基
を有するものも好適に使用できる。これらポリエ
ステルまたはポリエーテルと反応させるジイソシ
アネートとしては、たとえば、１・５−ナフチル
ジイソシアネート、トルイレンジイソシアネー
ト、４・4′−ジフエニルメタンジイソシアネート
があげられる。ポリウレタンエラストマーとして
好適なものは、分子中に遊離のイソシアネート基
を実質的に含有せず、ウレタン結合を重量で10〜
50％含有し、かつ200℃における溶融粘度が1.0〜
102〜５×104ポイズのポリウレタンエラストマー
が好適である。
さらに極性重合体として有用なエポキシ樹脂
は、たとえばビスフエノールとエピクロルヒドリ
ンの縮合反応によつて、両末端にエポキシ基、側
鎖に水酸基を有した好適なエポキシ樹脂である。
また先に掲げたグリシジルアクリレート、グリシ
ジルメタクリレート、グリシジルエタクリレート
も有用なエポキシ基を持つており、これら単量体
をラジカル重合して得られるホモポリマーの他
に、所望により、これら単量体と共重合可能な単
量体、たとえばスチレン、塩化ビニル系、メチル
メタクリレート、アクリロニトリル等をラジカル
重合して得られる共重合体も好適なエポキシ基含
有重合体である。
上記に挙げた極性（共）重合体の他に、(c)成分
として好適な化合物は、ポリアミン、ポリイソシ
アネート、ポリオールが挙げられる。
ポリアミンは１級または２級アミンを少なくと
も２個以上有しており、ジカルボン酸無水物基と
反応してイミド、アミド化する。用いられるポリ
アミンの具体的な例としては、たとえば、エチレ
ンジアミン、プロピレンジアミン、ブチレンジア
ミン、ヘキシレンジアミン、オクチレンジアミ
ン、メチルアミノプロピルアミン、エチルアミノ
エチルアミン、エチルアミノブチルアミン、プロ
ピルアミノプロピルアミン、オクチルアミノプロ
ピルアミン、ドデシルアミノプロピルアミン、ヘ
キサデシルアミノプロピルアミン、アミノエチル
エタノールアミンなどのアルキレンジアミンまた
はその置換体、フエニレンジアミン、キシリレン
ジアミンなどの芳香族アミンまたはその置換体、
ジエチレントリアミン、トリエチレンテトラミ
ン、テトラエチレンペンタミン、ジ（メチルエチ
レン）トリアミン、ヘキサプロピレンヘプタミ
ン、トリ（エチルエチレン）テトラミン、ペンタ
（１−メチルプロピレン）ヘキサミン、テトラブ
チレンペンタミンなどのポリアルキレンアミンま
たはその置換体などが挙げられ、なかでも炭素数
20以下のポリアミンが好適に用いられる。これら
のポリアミンは２種以上を併用してもよく、また
ポリアミンとともに１級または２級のモノアミン
を本発明の効果を本質的に妨げない範囲で併用す
ることもできる。
用いられるポリイソシアネートの具体的な例と
しては、たとえば、トルイレンジイソシアネー
ト、４・4′−ジフエニルメタンジイソシアネー
ト、１・５−ナフタレンジイソシアネート、ポリ
メリツク−４・4′−ジフエニルメタンジイソシア
ネート、トリフエニルメタントリイソシアネー
ト、３・3′−ジメチル−４・4′−ビスフエニルジ
イソシアネート、ヘキサメチレンジイソシアネー
ト、キシレンジイソシアネート、４・4′ジシクロ
ヘキシルメタンジイソシアネートなどが挙げら
れ、さらに芳香族ジイソシアネートのトリマー
体、芳香族ジイソシアネートと脂肪族ジイソシア
ネートのコトリマー体、カルボジイミド型イソシ
アネート（ウレトンイミン）や、プレポリマー型
およびアダクト型ポリイソシアネートが好適に使
用できる。
さらに用いられるポリオール化合物の具体的な
例としては、エチレングリコール、１・２−プロ
ピレングリコール、１・４−ブタンジオール、
１・６−ヘキサンジオールジエチレングリコー
ル、ネオペンチルグリコール、トリメチロールプ
ロパン等が好適に使用できる。
本発明の複合樹脂組成物は、上記に掲げた(a)成
分、(b)成分、(c)成分から構成されるものであり、
本発明の主旨を損わない限り、さらに所望の他の
熱可塑性樹脂を混合してもかまわない。
本発明で用いられる(a)成分、(b)成分に対して、
用いる(c)成分は、(a)成分、(b)成分が有するジカル
ボン酸基またはその誘導体基と反応可能な官能基
を有するものであり、本発明の効果を本質的に妨
げない範囲で、任意に(c)成分として挙げられる化
合物または重合体を併用することができる。
本発明の複合樹脂組成物は、エチレン系不飽和
ジカルボン酸無水物と該モノマーと共重合可能な
ビニル系モノマーを共重合して得られる多元共重
合体(a)と、少なくとも１個のビニル芳香族化合物
を主体とする重合体ブロツクと、少なくとも１個
の共役ジエン化合物を主体とする重合体ブロツク
とからなるブロツク共重合体に、エチレン系不飽
和ジカルボン酸基またはその誘導体基を含む分子
単位を結合せしめて成る変性ブロツク共重合体(b)
を50重量％以上99重量％以下含有し、(a)成分、(b)
成分が有するジカルボン酸基またはその誘導体基
と反応可能な官能基を有する化合物または重合体
(c)を１重量％以上50重量％以下含有する組成物で
ある。このうち、(a)成分が(a)成分と(b)成分の合計
に対して１重量％以上50重量％以下の場合におい
ても、また(a)成分が(a)成分と(b)成分の合計に対し
て50重量％を超え99重量％以下である場合におい
ても、得られる複合樹脂組成物は各種成型材料に
好適に使用できる。
本発明の複合樹脂組成物は、その各成分の組成
比に応じて通常の高分子物質の混合に用いられる
各種混合装置によつて、溶融状態で混合すること
によつて調製できる。それらの混合装置として好
適なものは、たとえば、一軸または多軸のスクリ
ユー型押出機、ミキシングロール、バンバリーミ
キサー、ニーダー、プラベンダー等のプラスチツ
ク混合装置が挙げられる。
本発明の組成物を調製するにあたり、(a)成分、
(b)成分、(c)成分を同時に混合するか、(a)成分と(b)
成分を前もつて混合し、次いで(c)成分を添加し混
合するか、または(b)成分と(c)成分を前もつて混合
し、次いで(a)成分を添加し混合する等、任意に調
製方法を選ぶことができる。また本発明の組成物
を調製するための混合条件は、本発明の構成成分
(a)、(b)、(c)各成分が、本発明の主旨である官能基
による反応を十分達成するような混合温度、混合
時間が選ばれる。通常、混合温度は、各成分の融
点以上で行なわれ、混合時間は各成分が相互に分
散するまで行なわれるが、変性ブロツク共重合体
がゲル化するような高い温度ないし長時間混合を
続けることは好ましくない。この混合の際、必要
に応じて官能基どうしの反応を促進させるため
に、第３級アミン、アンモニウム塩、有機酸塩、
無機塩、有機キレート化合物等の触媒を添加して
もよい。
また、本発明の組成物は、上記に示した混合装
置による混合の他に、本発明の構成成分または必
要に応じて触媒を適当な溶媒中で混合して得るこ
とも可能である。
該複合樹脂組成物は、さらに他の熱可塑性樹
脂、たとえば、スチレン系樹脂のポリスチレン、
ハイインパクトポリスチレン、ABS樹脂、AS樹
脂、ゴム変性スチレン−無水マレイン酸共重合体
等やポリオレフインを、その性質を損わない程度
に混合してもよく、また添加剤として、たとえ
ば、酸化防止剤、熱安定剤、紫外線吸収剤、着色
剤、滑剤、難燃剤、顔料等を添加することも可能
である。
本発明で得られる複合樹脂組成物は、耐熱性、
耐衝撃性、機械的特性、成形加工性に優れるた
め、従来からのスチレン系樹脂やポリオレフイン
樹脂等の成形に用いられている射出成形、押出成
形（インフレーシヨン法やＴダイ法によるシート
およびフイルム、共押出しラミネーシヨンや一軸
延伸方法あるいは二軸延伸方法によるフイルムお
よびシートの製造や、ストレートダイ、オフセツ
トダイ、クロスヘツドダイによるパイプ押出し
等）や、薄物シートの成形方法のカレンダー成
形、圧縮成形、円形金型内に粉末状樹脂を入れ、
加熱、回転して成形する回転成形、発泡体ペレツ
トを金型内に充填し加熱発泡させて成形する注型
成形、シート類の真空成形、二軸延伸シート等の
圧空成形等、各種成形方法を用いることも可能で
ある。これらの成形物は、フイルム、シート、成
形品等の形態で包装材料、雑貨玩具、電気部品、
機械部品、自動車部品、その他各種用途において
広い利用範囲があり、有用な組成物である。
また、本発明の複合樹脂組成物に補強充填剤、
たとえば、ガラス繊維、ガラスフレーク、炭素繊
維、チタン酸カリウム、二酸化チタン、チタン酸
ホイスカー、無水マイカ、ケイ酸カルシウム、無
水ケイ酸、ワラステナイト、炭酸カルシウム、ガ
ラス球、アスベスト、アルミナ、アルミニウム、
鉄、ニツケル等を添加し、補強充填剤強化複合樹
脂組成物を得ることができる。中でも、ガラス繊
維、炭素繊維が補強充填剤として好ましい。ガラ
ス繊維を用いる場合、使用するガラス繊維は、通
常のガラス繊維強化樹脂で用いられるものでよ
く、通常その直径が５〜13μであり、長さは加工
性、実用物性上最も適当とされる長さに切断され
たものを使用するのが好ましく、ガラス繊維の表
面をシラン系処理剤またはクロム系処理剤で表面
処理されたものが使用される。
さらに、本発明の複合樹脂組成物に発泡剤、た
とえば、物理発泡剤（ｎ−プロパン、ｎ−ブタ
ン、ｎ−ペンタン等の炭化水素類）や、化学発泡
剤（アゾ系発泡剤、ニトロソ系発泡剤、スルホニ
ルヒドラジド系発泡剤）や、無機系の発泡剤とし
ての重炭酸塩等を混入または圧入し、発泡させた
スチレン系複合樹脂発泡体組成物を得ることがで
きる。
これら複合樹脂組成物から得られる補強充填剤
強化複合樹脂組成物および複合樹脂発泡体組成物
は、ともに耐熱性、耐衝撃性に優れるため、ベー
スポリマーである複合樹脂組成物と同様に、機械
部品、電気部品、自動車部品等の各種用途におい
て広い利用範囲があり、有用な組成物である。
以下、若干の実施例を示すが、これは本発明を
より具体的に説明するものであつて、本発明の範
囲をこれらの例に限定するものではないことは言
うまでもない。
参考例
〔変性ブロツク共重合体の調製〕
スチレン−ブタジエンブロツク共重合体の熱可
塑性エラストマーである試料ｐを用いて、以下に
示す方法により、無水マレイン酸がグラフトした
変性ブロツク共重合体（試料Ｐ）を得た。なお、
試料ｐはヘキサン溶液中においてｎ−ブチルリチ
ウムを触媒として得られたものであり、以下にそ
の基本特性を示す。
ポリマー構造；Ｂ−Ｓ−Ｂ−Ｓ（直鎖状）
（Ｂ；ブタジエン、Ｓ；スチレン）
スチレン含有量；42重量％
ブロツク・スチレン含有量；36重量％
重量平均分子量（Mw）；79000
数平均分子量（Mn）；61000
メルト・インデツクス；12.0ｇ／10min
（JIS−Ｋ−6870、荷重５Kg、200℃）
試料ｐの100重量部に対し、４重量部の無水マ
レイン酸、ゲル化防止剤として0.3重量部のBHT
（ブチルヒドロキシトルエン）と、0.3重量部のフ
エノチアジンを添加し、これらをミキサーを用い
て均一に混合した。
この混合物を窒素雰囲気下で、40mm押出機（単
軸、フルフライト型スクリユー、Ｌ／Ｄ＝24）に
供給し、シリンダー温度190℃〜260℃で変性反応
を行なつた。得られたポリマーは、未反応の無水
マレイン酸を減圧乾燥により除去した。変性ブロ
ツク共重合体（試料Ｐ）の分析結果は、メルトイ
ンデツクスが8.5ｇ／10min、トルエン不溶分が
0.05重量％、ナトリウムメチラートによる滴定で
測定した無水マレイン酸の付加量がブロツク共重
合体100重量部あたり2.3重量部であつた。
さらに、試料ｐとポリマー構造が異なるスチレ
ン−ブタジエン共重合体（試料ｑ、ｒ、ｓ、ｔ）
を試作し、上記と同様な方法で、表１に示す不飽
和カルボン酸を付加し、試料Ｑ、Ｒ、Ｓ、Ｔ、す
なわち変性ブロツク共重合体である本発明の(b)成
分を得た。
表１に得られた試料の結果を示した。
The present invention relates to a novel composite resin composition, and more specifically, a multicomponent copolymer obtained by copolymerizing an ethylenically unsaturated dicarboxylic acid anhydride and a vinyl monomer copolymerizable with the monomer, and a vinyl aromatic copolymer. A block copolymer obtained by modifying a group compound-conjugated diene compound copolymer with an ethylenically unsaturated dicarboxylic acid or a derivative thereof, and a substance having at least two or more functional groups that can react with a dicarboxylic acid group or a derivative group thereof. Impact resistance comprising
The present invention relates to a composite resin composition suitable as a molding material with excellent mechanical strength and heat resistance. For example, vinyl aromatic compound-ethylenically unsaturated dicarboxylic anhydride copolymer, such as styrene-maleic anhydride copolymer, has a higher heat distortion temperature than conventional polystyrene resin, and furthermore, when mixed with glass fiber, It has extremely good mechanical strength,
At the same time, it is known that the heat resistance of glass fibers is also excellent. In addition, although styrene-maleic anhydride copolymer is a heat-resistant resin, its processability is far superior to that of ultra-heat-resistant ABS resin.
It has flow characteristics during extrusion and injection molding that are similar to polystyrene resin. Furthermore, like polystyrene resin, it can be processed and molded into foam, and as a heat-resistant product with improved heat resistance of conventional polystyrene foam, it is often used for various molded products such as insulation for high-temperature parts and housing parts of home appliances. ing. However, although styrene-maleic anhydride copolymer has excellent heat resistance and mechanical strength, it has poor impact resistance. Improved impact resistance (ABS
At present, the impact resistance has not been improved as extensively as the resins), and a styrene-maleic anhydride copolymer with excellent heat resistance, mechanical strength, and impact resistance is desired. Against this background, the present inventors have conducted extensive research to improve the above problems, and as a result, have found that:
Compositions not disclosed by the prior art include
A multi-component copolymer obtained by copolymerizing an ethylenically unsaturated dicarboxylic acid anhydride and a vinyl monomer copolymerizable with the monomer exhibits excellent impact resistance without impairing the desired properties, The present invention was achieved by discovering that the composition is suitable for use as a molding material, etc. That is, the present invention comprises (a) component (a) of a multicomponent copolymer obtained by copolymerizing an ethylenically unsaturated dicarboxylic acid anhydride and a vinyl monomer copolymerizable with the monomer; and (b) has a polymer block mainly composed of at least one vinyl aromatic compound and a polymer block mainly composed of at least one conjugated diene compound, and the weight ratio of the vinyl aromatic compound and the conjugated diene compound is A modification in which 0.05 to 20 parts by weight of a molecular unit containing an ethylenically unsaturated dicarboxylic acid group or its derivative group is bonded to a block copolymer having a molecular weight of 5/95 to 95/5 per 100 parts by weight of the block copolymer. component (b) of the block copolymer; and (c); at least a functional group selected from a hydroxyl group, an amino group, an epoxy group, an isocyanate group, and a urethane group as a functional group capable of reacting with a dicarboxylic acid group or its derivative group. A composite resin composition comprising component (c), which is a compound or polymer having two or more, and the total of component (a) and component (b) is 50% by weight.
or more, 99% by weight or less, contains component (c) from 1% to 50% by weight, and further contains component (a) and component (b).
The composite resin composition is characterized in that the content is 1% by weight or more and 99% by weight or less based on the total amount of components. The present invention will be described in detail below. In order to achieve the object of the present invention, components (a), (b), and (c), which are the constituent components of the present invention, are essential, and even if any one of these components is missing, the object of the present invention will not be achieved. cannot be achieved. That is, unlike conventional resin blends, the present invention is based on a technically significant idea regarding blends of functional compounds or functional polymers that utilize the reactivity of functional groups. This is a composite resin composition that is achieved only by the reaction of the functional groups of components (), (b), and (c). The multicomponent copolymer of component (a) used in the present invention is:
A multicomponent copolymer obtained by copolymerizing an ethylenically unsaturated dicarboxylic anhydride and a monomer copolymerizable with the ethylenically unsaturated dicarboxylic anhydride,
Specific copolymerizable monomers include, for example, vinyl aromatic compounds. Monomers useful as vinyl aromatic compounds include:
Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, ethylstyrene, dimethylstyrene, divinylbenzene, α-methylstyrene, p-methoxystyrene, p-chlorostyrene, 2,4-dichlorostyrene, 2・Contains 5-dichlorostyrene, p-bromstyrene, α-methyl-p-methylstyrene, p-isopropylstyrene, vinylnaphthalene and their analogues, and optionally two or more of these vinyl aromatic compounds. Further mixtures can also be used. Monomers that can form the ethylenically unsaturated dicarboxylic acid anhydride, which is an essential component of the copolymer, include acid anhydride maleic anhydride, ethylenically unsaturated dicarboxylic acids maleic acid, fumaric acid, itaconic acid, Examples include citraconic acid, mesaconic acid, ethylmaleic acid, methylitaconic acid, chloromaleic acid, dichloromaleic acid, bromomaleic acid, dibromaleic acid, and their anhydrides, as well as half esters produced from ethylenically unsaturated dicarboxylic acids. can also be used. These copolymers having acid and half-ester groups are finally produced by an operation that generates a cyclic anhydride group from the oxygen-containing group of an ethylenically unsaturated half-ester or dicarboxylic acid, and then a vinyl having an anhydride component is produced. A copolymer of aromatic compound and anhydride is obtained. In addition to the above-mentioned vinyl aromatic compound-ethylenically unsaturated dicarboxylic anhydride copolymer, component (a) used in the present invention is a copolymer of ethylenically unsaturated dicarboxylic anhydride and the monomer. Possible monomers such as styrene, ethylene, propylene, 1-butene, vinyl acetate, vinyl ether, acrylonitrile, methacrylic acid,
There is a multicomponent copolymer obtained by copolymerizing one or more of methyl methacrylate, acrylic acid, acrylic ester, and vinyl chloride. For the production of these copolymers, known polymerization methods, such as radical polymerization methods such as solution polymerization, bulk polymerization, bulk-suspension polymerization, and suspension polymerization, are advantageously used industrially. The multicomponent copolymer obtained by copolymerizing the ethylenically unsaturated dicarboxylic acid anhydride thus obtained preferably has a weight average molecular weight of 20,000 to 1,000,000, more preferably 50,000 to 1,000,000, although low molecular weight copolymers can be used. 500,000 is used, and the maleic anhydride content in the copolymer is preferably 3 to 50 mol%, and more preferably 5 to 50 mol%.
It is 30 mol%. Next, the component (b) used in the present invention contains one or more polymer blocks mainly composed of a vinyl aromatic compound and one or more polymer blocks mainly composed of a conjugated diene compound. This is a modified block copolymer in which an unsaturated dicarboxylic acid or a derivative thereof is added to a block copolymer in which the weight ratio of the compound to the conjugated diene compound is 5/95 to 95/5. Here, the polymer block mainly composed of vinyl aromatic compounds refers to a vinyl aromatic compound polymer block or a polymer block containing 50% by weight of vinyl aromatic compounds.
A copolymer block of a vinyl aromatic compound and a conjugated diene compound that exceeds 70% by weight, preferably 70% by weight or more, and a polymer block mainly composed of a conjugated diene compound It is a copolymer block of a vinyl aromatic compound and a conjugated diene compound in which the content of the compound is more than 50% by weight, preferably 70% by weight or more. The vinyl aromatic compound-conjugated diene compound block copolymer (hereinafter simply referred to as "block copolymer") that serves as the base of the above-mentioned modified block copolymer is:
It contains one or more, preferably two or more, polymer blocks mainly composed of a vinyl aromatic compound, and one or more polymer blocks mainly composed of a conjugated diene compound. In the block copolymer, the weight ratio of the vinyl aromatic compound to the conjugated diene compound is 5/95 to 95/5, preferably 10/90 to 90/5.
The composition range is 10, more preferably 20/80 to 80/20. The block copolymer exhibits elastomeric properties when the content of the vinyl aromatic compound is 70% by weight or less, and exhibits resinous properties when it exceeds 70% by weight. In addition, a polymer block mainly composed of a vinyl aromatic compound of a block copolymer or a polymer block mainly composed of a conjugated diene compound is characterized in that the distribution of the conjugated diene compound or vinyl aromatic compound in the molecular chain of the polymer block is It may be random, tapered (monomer component increases or decreases along the molecular chain), partially block-like, or any combination thereof. When there are two or more polymer blocks mainly composed of vinyl aromatic compounds, each block may have the same structure,
They may have different structures. Further, when two or more polymer blocks mainly composed of a conjugated diene compound are contained, each block may have the same structure or may have a different structure. As the vinyl aromatic compound constituting the block copolymer, for example, one or more types are selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, etc. Among them, styrene is particularly preferred. preferable. Examples of conjugated diene compounds include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-
One or more types are selected from 1,3-butadiene and the like, and among them, butadiene or a combination of conjugated diene compounds mainly composed of butadiene is preferred, and butadiene is particularly preferred. The number average molecular weight of the block copolymer is 5000~
The range is 1,000,000, preferably 10,000 to 800,000, more preferably 30,000 to 500,000, and the molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is 10 or less. Furthermore, the molecular structure of the block copolymer may be linear, branched, radial, or any combination thereof. Further, the above-mentioned block copolymer may be slightly modified with an organic compound or an inorganic compound as long as its properties are not lost. The block copolymer used in the present invention is usually prepared by polymerizing a vinyl aromatic compound and a conjugated diene compound in an inert hydrocarbon solvent such as hexane, cyclohexane, benzene, or toluene using an organolithium compound such as butyllithium as a polymerization catalyst. It is obtained by anionic copolymerization, and block copolymers with various structures can be obtained by changing the method and order of addition of monomers or by using a polyfunctional lithium compound. In addition, the block copolymer having lithium active terminals obtained by the above method may be combined with a polyfunctional coupling agent such as carbon tetrachloride.
By reacting with silicon tetrachloride or the like, it is possible to form a branched or radial block copolymer. In addition, any vinyl aromatic compound-conjugated diene compound block copolymer obtained by any production method may be used as long as it falls within the range of the above limitations. The above block copolymers may be not only one type but also a combination of two or more types. Examples of these combinations include a combination of styrene-butadiene block copolymers, and two types of block copolymers with different molecular weights. A combination of styrene-butadiene block copolymers, a combination of two types of styrene-butadiene block copolymers with different styrene contents, a combination of styrene-butadiene block copolymers with a block structure consisting of three segments of styrene-butadiene-styrene, and a combination of styrene-butadiene-styrene blocks.
These include combinations of different styrene-butadiene block copolymers, such as those consisting of four segments of butadiene-styrene. Next, the unsaturated dicarboxylic acid or its derivative grafted onto the block copolymer will be explained. These unsaturated dicarboxylic acids or derivatives thereof are added to the conjugated diene moiety of the block copolymer at an active unsaturated bond position. These are 0.05 to 20 parts by weight per 100 parts by weight of the block copolymer,
Preferably 0.05 to 10 parts by weight, more preferably
It is necessary to add 0.1 to 2 parts by weight in order to bring out the desired properties of the styrenic composite resin composition. If the amount added is less than 0.05 parts by weight, there will be almost no improvement effect compared to the unmodified block copolymer, and if the amount added exceeds 20 parts by weight, the improvement effect will not be further improved. Examples of the unsaturated dicarboxylic acids or derivatives thereof include maleic acid, fumaric acid, itaconic acid,
Dichloromaleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endo-cis-bicyclo[2,2,1]-5-heptene-2,3-dicarboxylic acid, etc., and acid anhydrides of these dicarboxylic acids , ester, amide, dicarboxylic acid imide, etc. Various derivatives of dicarboxylic acids may be added to the block copolymer as they are, or after adding the unsaturated dicarboxylic acid to the block copolymer, a carboxylic acid group may be added to the corresponding derivative by an appropriate reaction. It may be converted to The conversion reaction from such a carboxylic acid group to its derivative is
Optionally, at the stage of a composition formed by mixing a multicomponent copolymer (a) component obtained by copolymerizing an ethylenically unsaturated dicarboxylic acid anhydride and a dicarboxylic acid-modified block copolymer (b) component, May be implemented. Among the unsaturated dicarboxylic acids or derivatives thereof that modify the above-mentioned block copolymers, maleic acid, fumaric acid, and maleic anhydride are preferred. The modified block copolymer of the present invention can be obtained by grafting the block copolymer with an unsaturated dicarboxylic acid or a derivative thereof in a molten state or a solution state, with or without the use of a radical initiator. . The method for producing these modified block copolymers is not particularly limited in the present invention, but the modified block copolymers obtained may contain undesirable components such as gel, or may have poor fluidity and be processed. A manufacturing method that deteriorates properties is not preferred. A preferred method is to react the block copolymer with an unsaturated dicarboxylic acid or a derivative thereof without adding peroxide, for example in an extruder. Next, the component (c) used in the present invention is the component (a),
A compound or polymer having at least two functional groups capable of reacting with the dicarboxylic acid group or its derivative group contained in component (b). The compound or polymer having a functional group that can react with a dicarboxylic acid group or its derivative group is one composed of a functional group selected from a hydroxyl group, an amino group, an epoxy group, an isocyanate group, and a urethane group. be. Note that component (c) is a compound that reacts with a dicarboxylic acid group or its derivative group to form a covalent bond, and does not include an ionic crosslinking agent compound that forms a reversible ionic bond. Suitable polymers having a functional group capable of reacting with the dicarboxylic acid group or its derivative are hydroxyl-modified polybutadiene, epoxy-modified polybutadiene, amine-modified polybutadiene, and isocyanate-modified polybutadiene. These functional group-modified polybutadienes are made by modifying the base polybutadiene at the terminal or side chain position, and have a molecular weight of
It is a liquid polymer with a molecular weight of 500 to 10,000, more preferably 1,000 to 8,000. The base polymer other than this functional group-modified polybutadiene may be a styrene-butadiene copolymer oligomer, and diene oligomers such as 1,3-pentadiene and isoprene,
Styrenic oligomers are also suitable (hereinafter simply referred to as "functional oligomers"). These functional oligomers or oligomers serving as the base of the functional oligomers can be obtained by any known production method, and anionic polymerization methods, cationic polymerization methods, and radical polymerization methods are industrially useful. In addition to the functional oligomers listed above, more preferred polymers for component (c) include vinyl alcohol polymers (including copolymers), polyalkylene glycol polymers (including copolymers), There are vinyl glycidyl polymers (including copolymers), polyamide resins, epoxy resins, and polyurethanes (hereinafter simply referred to as polar polymers). These polar polymers preferably have a molecular weight of over 10,000, but may be low molecular weight units having two or more functional groups capable of reacting with dicarboxylic acids or derivatives thereof in their molecular chains. The polar polymers listed here include polar polymers obtained by radical polymerization of polymerizable polar compounds, as well as polar polymers obtained by polyaddition or polycondensation of polar compounds. At least two or more functional groups selected from hydroxyl groups, amino groups, epoxy groups, isocyanate groups, and urethane groups that can react with dicarboxylic acids or derivatives thereof are located at the end of the main chain of the polymer or in the side chain of the polymer. It is a polar polymer with Useful polar polymerizable compounds include vinyl acetate, allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, polyethylene glycol monomethacrylate, allyl alcohol, hydroxystyrene, 2-hydroxyethyl methacrylate, 2-hydroxyethyl Acrylate, 2
-Hydroxypropyl methacrylate, aminoethyl methacrylate, diallylamine, t-butylaminoethyl methacrylate, N-methylol methacrylate, acrylamide, acrylamide substituted product, and monoaminostyrene. Furthermore, if desired, a polar polymer homopolymer or a polar copolymer is obtained by copolymerizing with a vinyl monomer copolymerizable with these vinyl monomers, such as styrene, acrylonitrile, acrylic ester, methacrylic ester, ethylene, etc. obtain. These polar (co)polymers can be advantageously produced industrially by any known polymerization method, such as radical polymerization methods such as emulsion polymerization, solution polymerization, bulk polymerization, and suspension polymerization. Polyamide resins, which are further useful polar polymers, are prepared by condensing equimolar amounts of a dibasic acid or a derivative thereof, usually having from 2 to 20 carbon atoms, and a diamine having from 2 to 15 carbon atoms; 3
Do lactam polymerization of lactams with more than one membered ring or ω
-Produced industrially advantageously by polycondensing amino acids and the like. Useful diamines include hexamethylene diamine, nonamethylene diamine, undecamethylene diamine, dodecamethylene diamine, metaxylylene diamine, etc., and useful dibasic acids include adipic acid, sebacic acid, terephthalic acid,
Examples include isophthalic acid, dodecane dibasic acid, and glutaric acid. Furthermore, ε-caprolactam, enantholactam, α-pyrrolidone, α-piperidone, aminocaproic acid, 7-aminoheptanoic acid,
There are polymers such as 9-aminononanoic acid and 11-aminoundecanoic acid. Polyamide resins that are these polymers or copolymers include nylon 4, 6,
7, 8, 11, 12, 6.6, 6.9, 6.10, 6.
11, 6・12, 6T, 6/6・6, 6/12, 6/6T
etc. Polyurethanes useful as polar polymers are produced by reacting polyesters or polyethers with a molecular weight of 500 to 10,000 with diisocyanates under conditions of [NCO]/[OH] + [COOH] or [NCO]/[OH] of about 1 to 2. It is a macrodiisocyanate (prepolymer) with a free isocyanate group at the end. Furthermore, if desired, a highly polymerized polymer may be obtained by adding a chain elongating agent having active hydrogen such as hydrazine, diamine, ethylene glycol, or water to this prepolymer to form bisurein bonds, urea bonds, and urethane bonds, respectively. . Polyester, which is the base material for polyurethane, is manufactured using conventional methods, such as
It is also preferable to use a product obtained by reacting adipic acid or azelaic acid with polyethylene glycol or polypropylene glycol so that OH groups are present at both ends. Furthermore, the polyether that serves as the base of polyurethane is similarly produced by conventional methods, and specifically, polyethers based on ethylene oxide and propylene oxide and having OH groups at both ends are also preferably used. can. Examples of the diisocyanate to be reacted with these polyesters or polyethers include 1,5-naphthyl diisocyanate, tolylene diisocyanate, and 4,4'-diphenylmethane diisocyanate. Suitable polyurethane elastomers contain substantially no free isocyanate groups in the molecule and have urethane bonds of 10 to 10% by weight.
Contains 50% and has a melt viscosity of 1.0 to 200℃
A polyurethane elastomer having a poise strength of 10 2 to 5×10 4 poise is preferred. Furthermore, an epoxy resin useful as a polar polymer is a suitable epoxy resin having an epoxy group at both ends and a hydroxyl group on a side chain, for example, by a condensation reaction of bisphenol and epichlorohydrin.
In addition, the glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate listed above also have useful epoxy groups, and in addition to homopolymers obtained by radical polymerization of these monomers, if desired, these monomers can be used as well. Copolymers obtained by radical polymerization of copolymerizable monomers such as styrene, vinyl chloride, methyl methacrylate, acrylonitrile, etc. are also suitable epoxy group-containing polymers. In addition to the polar (co)polymers listed above, compounds suitable as component (c) include polyamines, polyisocyanates, and polyols. A polyamine has at least two primary or secondary amines, and reacts with a dicarboxylic anhydride group to form an imide or amidate. Specific examples of polyamines used include ethylenediamine, propylene diamine, butylene diamine, hexylene diamine, octylene diamine, methylaminopropylamine, ethylaminoethylamine, ethylaminobutylamine, propylaminopropylamine, octylaminopropyl. amines, alkylene diamines such as dodecylaminopropylamine, hexadecylaminopropylamine, and aminoethylethanolamine or substituted products thereof; aromatic amines such as phenylene diamine and xylylene diamine or substituted products thereof;
Polyalkylene amines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, di(methylethylene)triamine, hexapropyleneheptamine, tri(ethylethylene)tetramine, penta(1-methylpropylene)hexamine, and tetrabutylenepentamine, or their Examples include substitution products, among which carbon number
Polyamines of 20 or less are preferably used. Two or more of these polyamines may be used in combination, and a primary or secondary monoamine may also be used in combination with the polyamine within a range that does not essentially impede the effects of the present invention. Specific examples of the polyisocyanate used include toluylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, polymeric-4,4'-diphenylmethane diisocyanate, and triphenylmethane. Examples include triisocyanate, 3,3'-dimethyl-4,4'-bisphenyl diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, 4,4' dicyclohexylmethane diisocyanate, and also trimers of aromatic diisocyanates, aromatic diisocyanates. Cotrimers of aliphatic diisocyanates, carbodiimide isocyanates (uretonimines), and prepolymer and adduct polyisocyanates can be suitably used. Further, specific examples of polyol compounds that can be used include ethylene glycol, 1,2-propylene glycol, 1,4-butanediol,
1,6-hexanediol diethylene glycol, neopentyl glycol, trimethylolpropane, etc. can be suitably used. The composite resin composition of the present invention is composed of the components (a), (b), and (c) listed above,
Other desired thermoplastic resins may be mixed as long as the gist of the present invention is not impaired. For the (a) component and (b) component used in the present invention,
The component (c) to be used has a functional group that can react with the dicarboxylic acid group or its derivative group that the component (a) and component (b) have, and within the range that does not essentially impede the effects of the present invention, Optionally, a compound or polymer listed as component (c) can be used in combination. The composite resin composition of the present invention comprises a multicomponent copolymer (a) obtained by copolymerizing an ethylenically unsaturated dicarboxylic acid anhydride and a vinyl monomer copolymerizable with the monomer, and at least one vinyl aromatic copolymer (a). A block copolymer consisting of a polymer block mainly composed of a group compound and a polymer block mainly composed of at least one conjugated diene compound is added with a molecular unit containing an ethylenically unsaturated dicarboxylic acid group or a derivative group thereof. Modified block copolymer (b) formed by bonding
Contains 50% by weight or more and 99% by weight or less of (a) component, (b)
A compound or polymer that has a functional group that can react with the dicarboxylic acid group or its derivative group that the component has
A composition containing (c) in an amount of 1% by weight or more and 50% by weight or less. Among these, even if component (a) is 1% to 50% by weight of the total of components (a) and (b), Even when the amount is more than 50% by weight and not more than 99% by weight based on the total amount, the resulting composite resin composition can be suitably used in various molding materials. The composite resin composition of the present invention can be prepared by mixing the components in a molten state using various mixing devices commonly used for mixing polymeric substances, depending on the composition ratio of each component. Suitable mixing devices include, for example, plastic mixing devices such as single-screw or multi-screw extruders, mixing rolls, Banbury mixers, kneaders, and prabenders. In preparing the composition of the present invention, component (a),
Mix component (b) and (c) at the same time, or mix component (a) and (b) together.
Optionally, the ingredients may be pre-mixed and then the (c) ingredient added and mixed, or the (b) and (c) ingredients may be pre-mixed and then the (a) ingredient added and mixed. You can choose the preparation method. Further, the mixing conditions for preparing the composition of the present invention include the constituent components of the present invention.
The mixing temperature and mixing time are selected such that each component (a), (b), and (c) sufficiently achieves the reaction by the functional group, which is the gist of the present invention. Normally, the mixing temperature is higher than the melting point of each component, and the mixing time is until each component is mutually dispersed, but mixing must not be continued at such a high temperature or for such a long time that the modified block copolymer gels. is not desirable. During this mixing, tertiary amines, ammonium salts, organic acid salts,
A catalyst such as an inorganic salt or an organic chelate compound may be added. Furthermore, the composition of the present invention can be obtained by mixing the constituent components of the present invention or, if necessary, a catalyst in an appropriate solvent, in addition to mixing using the mixing apparatus shown above. The composite resin composition further includes other thermoplastic resins, such as polystyrene, which is a styrenic resin,
High-impact polystyrene, ABS resin, AS resin, rubber-modified styrene-maleic anhydride copolymer, etc., and polyolefin may be mixed to the extent that their properties are not impaired, and additives such as antioxidants, It is also possible to add heat stabilizers, ultraviolet absorbers, colorants, lubricants, flame retardants, pigments, etc. The composite resin composition obtained by the present invention has heat resistance,
Due to its excellent impact resistance, mechanical properties, and moldability, injection molding and extrusion molding (inflation method and T-die method) are conventionally used to mold styrene resins and polyolefin resins. , production of films and sheets using coextrusion lamination, uniaxial or biaxial stretching methods, pipe extrusion using straight dies, offset dies, crosshead dies, etc.), as well as thin sheet forming methods such as calendar molding, compression molding, and circular molding. Put powdered resin into the mold,
Various molding methods are available, including rotary molding, which involves heating and rotating, casting molding, which involves filling a mold with foam pellets and heating and foaming them, vacuum forming of sheets, and pressure forming, such as biaxially stretched sheets. It is also possible to use These molded products can be used as packaging materials, miscellaneous toys, electrical parts, etc. in the form of films, sheets, molded products, etc.
It is a useful composition with a wide range of uses in mechanical parts, automobile parts, and various other uses. In addition, reinforcing fillers are added to the composite resin composition of the present invention.
For example, glass fiber, glass flakes, carbon fiber, potassium titanate, titanium dioxide, titanate whiskers, anhydrous mica, calcium silicate, silicic anhydride, wollastenite, calcium carbonate, glass bulbs, asbestos, alumina, aluminum,
By adding iron, nickel, etc., a reinforcing filler-reinforced composite resin composition can be obtained. Among them, glass fibers and carbon fibers are preferred as reinforcing fillers. When using glass fibers, the glass fibers used may be those used in ordinary glass fiber reinforced resins, and the diameter is usually 5 to 13μ, and the length is the most appropriate length in terms of processability and practical physical properties. It is preferable to use glass fibers that have been cut into small pieces, and those whose surfaces have been treated with a silane-based treatment agent or a chromium-based treatment agent are used. Furthermore, a blowing agent such as a physical blowing agent (hydrocarbons such as n-propane, n-butane, n-pentane, etc.) or a chemical blowing agent (azo blowing agent, nitroso blowing agent, etc.) may be added to the composite resin composition of the present invention. A styrene-based composite resin foam composition can be obtained by mixing or press-injecting a sulfonyl hydrazide foaming agent) or a bicarbonate as an inorganic foaming agent. Both the reinforcing filler-reinforced composite resin composition and the composite resin foam composition obtained from these composite resin compositions have excellent heat resistance and impact resistance. It is a useful composition that has a wide range of uses in various applications such as electrical parts, automobile parts, etc. Hereinafter, some examples will be shown, but these are intended to explain the present invention more specifically, and it goes without saying that the scope of the present invention is not limited to these examples. Reference Example [Preparation of modified block copolymer] Using Sample P, which is a thermoplastic elastomer of styrene-butadiene block copolymer, a modified block copolymer grafted with maleic anhydride (Sample P) was prepared by the method shown below. ) was obtained. In addition,
Sample p was obtained using n-butyllithium as a catalyst in a hexane solution, and its basic characteristics are shown below. Polymer structure: B-S-B-S (linear) (B: butadiene, S: styrene) Styrene content: 42% by weight Block styrene content: 36% by weight Weight average molecular weight (Mw): 79000 Number average Molecular weight (Mn): 61000 Melt index: 12.0 g/10 min (JIS-K-6870, load 5 kg, 200°C) 4 parts by weight of maleic anhydride and 0.3 parts by weight as an anti-gelling agent for 100 parts by weight of sample p. BHT by weight
(butylated hydroxytoluene) and 0.3 parts by weight of phenothiazine were added, and these were mixed uniformly using a mixer. This mixture was supplied to a 40 mm extruder (single screw, full-flight screw, L/D=24) under a nitrogen atmosphere, and a modification reaction was carried out at a cylinder temperature of 190°C to 260°C. The obtained polymer was dried under reduced pressure to remove unreacted maleic anhydride. The analysis results of the modified block copolymer (sample P) show that the melt index is 8.5g/10min and the toluene insoluble content is 8.5g/10min.
The amount of maleic anhydride added was 2.3 parts by weight per 100 parts by weight of the block copolymer, as determined by titration with sodium methylate. Furthermore, styrene-butadiene copolymers (samples q, r, s, t) with different polymer structures from sample p
Samples Q, R, S, and T, namely component (b) of the present invention, which is a modified block copolymer, were obtained by adding the unsaturated carboxylic acids shown in Table 1 in the same manner as above. . Table 1 shows the results of the obtained samples.
【表】【table】
【表】
実施例１、２および比較例１、２
(a)成分；スチレン−無水マレイン酸共重合体と
して商品名「ダイラーク232」（アーコ社製）、
(b)成分；参考例で得た変性ブロツク共重合体
（試料Ｐ）および未変性のブロツク共重合体（試
料ｐ）、
(c)成分；ビニルアルコール系重合体として、エ
チレン−酢酸ビニル共重合体のケン化物である商
品名「EVAL−EP−Ｅ」（クラレ製）を表２に示
す配合割合で配合したものを、180℃のミキシン
グロールで10分間混練することによりスチレン系
複合樹脂組成物を得た。
これらの組成物の圧縮成形品（200℃で成形）
の物性値およびダイラーク232の圧縮成形品（200
℃で成形）の物性値を表２に示した。
表２に示す如く、実施例１の組成物は、比較例
１の組成物と比較して、耐衝撃性、引張特性に優
れる組成物であることが明らかである。また実施
例２も本発明の範囲内にある組成物であり、耐衝
撃性、引張特性の優れた組成物である。[Table] Examples 1 and 2 and Comparative Examples 1 and 2 (a) Component: Styrene-maleic anhydride copolymer with trade name "Dylark 232" (manufactured by Arco), (b) component: Obtained in Reference Example Modified block copolymer (sample P) and unmodified block copolymer (sample p), component (c); As a vinyl alcohol polymer, the product name "EVAL", which is a saponified product of ethylene-vinyl acetate copolymer, is used as a vinyl alcohol-based polymer. -EP-E" (manufactured by Kuraray) in the proportions shown in Table 2 and kneaded with a mixing roll at 180°C for 10 minutes to obtain a styrenic composite resin composition. Compression molded products of these compositions (molded at 200°C)
Physical property values and compression molded product of Dilarc 232 (200
Table 2 shows the physical property values of the molded product (molded at ℃). As shown in Table 2, it is clear that the composition of Example 1 has superior impact resistance and tensile properties compared to the composition of Comparative Example 1. Example 2 is also a composition within the scope of the present invention, and is a composition with excellent impact resistance and tensile properties.
【表】
実施例３、４、５、６および比較例３、４、５、
６、７、８
(b)成分として試料記号Ｑ、Ｒ、Ｓ、Ｔ、ｑ、
ｒ、ｓ、ｔを用いたほかは、実施例１と同様の(a)
成分と(c)成分を用い、40mm押出機で混練しペレツ
ト化した後、このペレツトを圧縮成形し、圧縮成
形品の物性を測定した。その結果を表３に示し
た。
表３に示す如く、基体となるブロツク共重合体
の構造の異なる変性ブロツク共重合体を(b)成分と
して添加した実施例３〜６は、対応する未変性で
あるブロツク共重合体を添加した比較例３〜６と
比較して、耐衝撃性、引張強度が著しく優れてお
り、変性ブロツク共重合体がスチレン−無水マレ
イン酸共重合体の改質剤として好ましいことが明
らかである。
また、本発明は、(a)成分、(b)成分、(c)成分の３
成分によつて、耐衝撃性、機械的特性に優れたス
チレン系複合樹脂組成物を得ることができ、比較
例７、８に示すように、(b)成分、(c)成分のいずれ
か１つが欠けても本発明の効果を引き出すことが
不可能であることが明らかである。[Table] Examples 3, 4, 5, 6 and Comparative Examples 3, 4, 5,
6, 7, 8 (b) Sample symbols Q, R, S, T, q, as components
(a) Same as Example 1 except that r, s, and t were used.
The components and (c) were kneaded using a 40 mm extruder to form pellets, and then the pellets were compression molded and the physical properties of the compression molded product were measured. The results are shown in Table 3. As shown in Table 3, in Examples 3 to 6, in which modified block copolymers with different structures of the base block copolymers were added as component (b), the corresponding unmodified block copolymers were added. Compared with Comparative Examples 3 to 6, the impact resistance and tensile strength are significantly superior, and it is clear that the modified block copolymer is preferable as a modifier for the styrene-maleic anhydride copolymer. In addition, the present invention provides three components: (a) component, (b) component, and (c) component.
Depending on the components, a styrenic composite resin composition with excellent impact resistance and mechanical properties can be obtained, and as shown in Comparative Examples 7 and 8, either one of component (b) and component (c) It is clear that it is impossible to bring out the effects of the present invention even if these elements are missing.
【表】
実施例 ７、８、９
(a)成分として商品名「ダイラーク232」（アーコ
社製）、(b)成分として参考例で得た変性ブロツク
共重合体（試料Ｐ）、および表４に示す(c)成分を
用いて、プラベンダープラストグラフで220℃、
10分間混練することによりスチレン系複合樹脂組
成物を得た。
これらの組成物の圧縮成形品（220℃で成形）
の物性値を表４に示した。
表４に示す如く、(c)成分がグリシジル基、ウレ
タン基、アミノ基を有する重合体であつても、得
られるスチレン系複合樹脂組成物は、耐衝撃性、
機械的強度に優れた特性を発揮することが明らか
である。[Table] Examples 7, 8, 9 (a) component is the trade name "Dylark 232" (manufactured by Arco), (b) component is the modified block copolymer obtained in the reference example (sample P), and Table 4 Using component (c) shown in 220℃ with a Prabender Plastograph,
A styrenic composite resin composition was obtained by kneading for 10 minutes. Compression molded products of these compositions (molded at 220°C)
The physical property values are shown in Table 4. As shown in Table 4, even if component (c) is a polymer having a glycidyl group, a urethane group, or an amino group, the resulting styrenic composite resin composition has impact resistance,
It is clear that it exhibits excellent properties in mechanical strength.
【表】【table】
【表】
実施例10および比較例９
実施例１と同様なスチレン系複合樹脂組成物
を、40mm押出機を用いてペレツトの形状で得た。
このペレツトと表面処理したガラスチヨツプドス
トランドを、40mmベント型単軸押出機にて混練押
出してガラス繊維強化スチレン系複合樹脂組成物
を得、その組成物を圧縮成形し、物性を測定し
た。
一方、比較のため、スチレン−無水マレイン酸
共重合体である商品名「ダイラーク232」（アーコ
社製）に、前記と同様の表面処理したガラスチヨ
ツプドストランドを配合した本発明の範囲外であ
る組成物についても、物性測定を行なつた。これ
らの結果を表５に示した。
表５より明らかな如く、本発明のガラス繊維強
化スチレン系複合樹脂組成物は、極めて耐衝撃性
に優れることがわかる。[Table] Example 10 and Comparative Example 9 A styrenic composite resin composition similar to that of Example 1 was obtained in the form of pellets using a 40 mm extruder.
The pellets and surface-treated glass chopped strands were kneaded and extruded using a 40 mm bent single screw extruder to obtain a glass fiber reinforced styrene composite resin composition, which was compression molded and its physical properties were measured. . On the other hand, for comparison, a styrene-maleic anhydride copolymer under the trade name "Dylarc 232" (manufactured by Arco) was blended with glass chopped strands that had been surface-treated in the same way as described above, which was outside the scope of the present invention. Physical properties were also measured for the composition. These results are shown in Table 5. As is clear from Table 5, the glass fiber reinforced styrene composite resin composition of the present invention has extremely excellent impact resistance.
【表】【table】
【表】
の集束チツプ、シラン処理
実施例 11
実施例１で得たスチレン系複合樹脂100重量部
と、15重量部のｎ−ブタンを主成分とする発泡剤
を40mmφ押出機の先端に接続された混合機に圧入
し、よく混和して、混合機先端の細孔を有する口
金より押出し、たゞちに20℃に保たれた水中に導
き急冷固化し、ペレタイザーに導き粒径約１mmの
スチレン系複合樹脂発泡体組成物のペレツトを得
た。
その結果、本発明のスチレン系複合樹脂の発泡
性粒子は、型成形性、発泡剤の保持性に優れ、こ
れより得られた発泡体は緩衝性に優れるものであ
つた。[Table] Example 11 of silane treatment of focusing chips 100 parts by weight of the styrene composite resin obtained in Example 1 and 15 parts by weight of a blowing agent whose main component is n-butane were connected to the tip of a 40 mmφ extruder. The mixture was then press-fitted into a mixer, mixed well, extruded through a nozzle with pores at the tip of the mixer, immediately poured into water maintained at 20°C, rapidly cooled and solidified, and then passed through a pelletizer to produce styrene particles with a particle size of approximately 1 mm. Pellets of a composite resin foam composition were obtained. As a result, the expandable particles of the styrenic composite resin of the present invention had excellent moldability and foaming agent retention, and the foam obtained therefrom had excellent cushioning properties.
Claims (1)
物と該モノマーと共重合可能なビニル系モノマー
を共重合して得られる多元共重合体と (b)成分；少なくとも１個のビニル芳香族化合物
を主体とする重合体ブロツクと、少なくとも１個
の共役ジエン化合物を主体とする重合体ブロツク
とを有し、該ビニル芳香族化合物と共役ジエン化
合物の重量比が５／95〜95／５であるブロツク共
重合体に、エチレン系不飽和ジカルボン酸基また
はその誘導体基を含む分子単位を該ブロツク共重
合体100重量部あたり0.05〜20重量部結合せしめ
て成る変性ブロツク共重合体と (c)成分；ジカルボン酸基またはその誘導体基と
反応可能な官能基として水酸基、アミノ基、エポ
キシ基、イソシアネート基、ウレタン基から選ば
れた官能基を少なくとも２個以上有する化合物ま
たは重合体 とを含んで成る複合樹脂組成物であり、(a)成分と
(b)成分の合計が50重量％以上、99重量％以下、(c)
成分を１重量％以上、50重量％以下含有し、さら
に、(a)成分が(a)成分と(b)成分の合計に対し、１重
量％以上、99重量％以下含有することを特徴とす
る複合樹脂組成物。 ２ (a)成分がビニル芳香族化合物−エチレン系不
飽和ジカルボン酸無水物共重合体、またはビニル
芳香族化合物およびエチレン系不飽和ジカルボン
酸無水物と共重合可能なビニル系モノマーを共重
合して得られる多元共重合体である特許請求の範
囲第１項記載の組成物。 ３ (a)成分のビニル芳香族化合物−エチレン系不
飽和ジカルボン酸無水物共重合体がスチレン−無
水マレイン酸共重合体である特許請求の範囲第２
項記載の組成物。 ４ (b)成分がブロツク共重合体にマレイン酸また
は無水マレイン酸またはフマル酸を結合して成る
変性ブロツク共重合体である特許請求の範囲第１
項記載の組成物。 ５ (a)成分が(a)成分と(b)成分の合計に対し１重量
％以上50重量％以下である特許請求の範囲第１項
記載の組成物。 ６ (a)成分が(a)成分と(b)成分の合計に対し50重量
％を超え99重量％以下である特許請求の範囲第１
項記載の組成物。 ７ (a)成分のスチレン−無水マレイン酸共重合体
が無水マレイン酸を３〜50モル％含有する共重合
体である特許請求の範囲第３項記載の組成物。 ８ (a)成分のスチレン−無水マレイン酸共重合体
が重量平均分子量20000以上の分子量を有する重
合体である特許請求の範囲第３項記載の組成物。 ９ (b)成分のビニル芳香族化合物と共役ジエン化
合物とからなるブロツク共重合体中のビニル芳香
族化合物の含有量が５〜70重量％である特許請求
の範囲第１項記載の組成物。 １０ (b)成分のビニル芳香族化合物と共役ジエン
化合物とからなるブロツク共重合体中のビニル芳
香族化合物の含有量が70重量％を超え95重量％以
下である特許請求の範囲第１項記載の組成物。 １１ (c)成分が分子量500〜10000の液状重合体で
ある特許請求の範囲第１項記載の組成物。 １２ (c)成分が水酸基変性ポリブタジエン、エポ
キシ変性ポリブタジエン、アミン変性ポリブタジ
エン、イソシアネート変性ポリブタジエン等の末
端あるいは側鎖変性の重合体である特許請求の範
囲第１１項記載の組成物。 １３ (c)成分が分子量10000を超える重合体であ
る特許請求の範囲第１項記載の組成物。 １４ (c)成分がビニルアルコール系重合体（共重
合体も含む）、ポリアルキレングリコール重合体
（共重合体も含む）、ビニル性グリシジル重合体
（共重合体も含む）、ポリアミド樹脂、エポキシ樹
脂、ポリウレタン等の重合体である特許請求の範
囲第１３項記載の組成物。[Claims] 1. Component (a); a multicomponent copolymer obtained by copolymerizing an ethylenically unsaturated dicarboxylic acid anhydride and a vinyl monomer copolymerizable with the monomer; and Component (b); at least one a polymer block mainly composed of vinyl aromatic compounds, and a polymer block mainly composed of at least one conjugated diene compound, and the weight ratio of the vinyl aromatic compound and the conjugated diene compound is 5/95. A modified block copolymer obtained by bonding a molecular unit containing an ethylenically unsaturated dicarboxylic acid group or its derivative group in an amount of 0.05 to 20 parts by weight per 100 parts by weight of the block copolymer to a block copolymer having a molecular weight of ~95/5. Combination and component (c): A compound or polymer having at least two functional groups selected from hydroxyl groups, amino groups, epoxy groups, isocyanate groups, and urethane groups as functional groups capable of reacting with dicarboxylic acid groups or derivative groups thereof. A composite resin composition comprising component (a) and
(b) The total content of the ingredients is 50% by weight or more and 99% by weight or less; (c)
It is characterized by containing 1% by weight or more and 50% by weight or less of a component, and further containing component (a) by 1% by weight or more and 99% by weight or less based on the total of components (a) and (b). Composite resin composition. 2. Component (a) is a vinyl aromatic compound-ethylenically unsaturated dicarboxylic acid anhydride copolymer, or a vinyl monomer copolymerizable with a vinyl aromatic compound and an ethylenically unsaturated dicarboxylic acid anhydride. The composition according to claim 1, which is a multicomponent copolymer obtained. 3. Claim 2, wherein the vinyl aromatic compound-ethylenically unsaturated dicarboxylic anhydride copolymer of component (a) is a styrene-maleic anhydride copolymer.
Compositions as described in Section. 4. Claim 1, wherein component (b) is a modified block copolymer formed by bonding maleic acid, maleic anhydride, or fumaric acid to a block copolymer.
Compositions as described in Section. 5. The composition according to claim 1, wherein component (a) is present in an amount of 1% by weight or more and 50% by weight or less based on the total of components (a) and (b). 6 Claim 1 in which component (a) is more than 50% by weight and not more than 99% by weight of the total of components (a) and (b)
Compositions as described in Section. 7. The composition according to claim 3, wherein the styrene-maleic anhydride copolymer as component (a) is a copolymer containing 3 to 50 mol% of maleic anhydride. 8. The composition according to claim 3, wherein the styrene-maleic anhydride copolymer as component (a) is a polymer having a weight average molecular weight of 20,000 or more. 9. The composition according to claim 1, wherein the content of the vinyl aromatic compound in the block copolymer consisting of the vinyl aromatic compound and the conjugated diene compound as component (b) is 5 to 70% by weight. 10 The content of the vinyl aromatic compound in the block copolymer consisting of the vinyl aromatic compound and the conjugated diene compound as the component (b) is more than 70% by weight and not more than 95% by weight, as described in claim 1 Composition of. 11. The composition according to claim 1, wherein component (c) is a liquid polymer having a molecular weight of 500 to 10,000. 12. The composition according to claim 11, wherein component (c) is a terminal- or side-chain-modified polymer such as hydroxyl-modified polybutadiene, epoxy-modified polybutadiene, amine-modified polybutadiene, or isocyanate-modified polybutadiene. 13. The composition according to claim 1, wherein component (c) is a polymer having a molecular weight of over 10,000. 14 Component (c) is a vinyl alcohol polymer (including copolymers), polyalkylene glycol polymer (including copolymers), vinyl glycidyl polymer (including copolymers), polyamide resin, epoxy resin 14. The composition according to claim 13, which is a polymer such as polyurethane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55147552A JPS5773042A (en) | 1980-10-23 | 1980-10-23 | Novel composite resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55147552A JPS5773042A (en) | 1980-10-23 | 1980-10-23 | Novel composite resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5773042A JPS5773042A (en) | 1982-05-07 |
| JPH0157700B2 true JPH0157700B2 (en) | 1989-12-07 |
Family
ID=15432902
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP55147552A Granted JPS5773042A (en) | 1980-10-23 | 1980-10-23 | Novel composite resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5773042A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992001019A1 (en) * | 1990-07-13 | 1992-01-23 | Nippon Steel Chemical Co., Ltd. | Resin composition for composite vibration damping material and composite vibration damping material produced therefrom |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60184546A (en) * | 1984-03-05 | 1985-09-20 | Denki Kagaku Kogyo Kk | Thermoplastic resin composition for foam molding |
| US4806597A (en) * | 1987-10-29 | 1989-02-21 | General Electric Company | Composition comprising aromatic polycarbonate, polyolefin, ethylene vinyl alcohol copolymer, and a modified hydrogenated alkylidene vinyl aromatic block copolymer |
| JP5545943B2 (en) * | 2009-10-22 | 2014-07-09 | 旭化成ケミカルズ株式会社 | Modified block copolymer, composition thereof and method for producing the same |
| JP5460240B2 (en) * | 2009-10-30 | 2014-04-02 | 旭化成ケミカルズ株式会社 | Modified block copolymer and composition thereof |
| JP2011094074A (en) * | 2009-10-30 | 2011-05-12 | Asahi Kasei Chemicals Corp | Modified block copolymer for foamed article and composition of the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55149341A (en) * | 1979-04-24 | 1980-11-20 | Idemitsu Kosan Co Ltd | Thermoplastic resin composition and laminate thereof |
-
1980
- 1980-10-23 JP JP55147552A patent/JPS5773042A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55149341A (en) * | 1979-04-24 | 1980-11-20 | Idemitsu Kosan Co Ltd | Thermoplastic resin composition and laminate thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992001019A1 (en) * | 1990-07-13 | 1992-01-23 | Nippon Steel Chemical Co., Ltd. | Resin composition for composite vibration damping material and composite vibration damping material produced therefrom |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5773042A (en) | 1982-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5506299A (en) | High impact resistant blends of thermoplastic polyamides and modified block copolymers | |
| JPH0541662B2 (en) | ||
| US4582876A (en) | High-impact polyester/styrene-maleic anhydride copolymer blends | |
| US4486570A (en) | Heat resistant high impact polymer compositions and method of making same | |
| US4329438A (en) | Thermosetting unsaturated polyester resin composition and method for preparation thereof | |
| WO2012014981A1 (en) | Resin composition and article molded therefrom | |
| US8034875B2 (en) | Elastomer and vulcanizate compositions having desirable high temperature properties | |
| JPS6230225B2 (en) | ||
| JPH0157700B2 (en) | ||
| JPS6345403B2 (en) | ||
| JPH0253468B2 (en) | ||
| JPS631343B2 (en) | ||
| US5773517A (en) | Process for the production of thermoplastic resin composition | |
| JP2542147B2 (en) | Polyamide resin composition with excellent impact resistance | |
| JPH02167342A (en) | Graft copolymer elastomer composition | |
| EP0081015B1 (en) | Improved heat resistant high impact polymer compositions and method of making same | |
| JPS6329707B2 (en) | ||
| US5599879A (en) | Modified radial polymers | |
| JP3049753B2 (en) | Polyamide blow molding | |
| US5115022A (en) | Thermoplastics of polyalkylene terephthalates impact modified with functionalized polymers and use thereof for producing moldings | |
| JPH06184366A (en) | Thermoplastic resin molding | |
| KR102486051B1 (en) | Thermoplastic resin composition and article manufactured using the same | |
| JPS6252780B2 (en) | ||
| JPS6061213A (en) | Improved manufacture of polymer pellet having free flowability | |
| JPH0532423B2 (en) |