JPH04279646A - Polystyrene-based resin composition excellent in impact and heat resistance - Google Patents
Polystyrene-based resin composition excellent in impact and heat resistanceInfo
- Publication number
- JPH04279646A JPH04279646A JP6536591A JP6536591A JPH04279646A JP H04279646 A JPH04279646 A JP H04279646A JP 6536591 A JP6536591 A JP 6536591A JP 6536591 A JP6536591 A JP 6536591A JP H04279646 A JPH04279646 A JP H04279646A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- resin composition
- latex
- polystyrene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 20
- 229920002223 polystyrene Polymers 0.000 title abstract description 7
- 239000004793 Polystyrene Substances 0.000 title abstract description 6
- 229920000126 latex Polymers 0.000 claims abstract description 52
- 239000004816 latex Substances 0.000 claims abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 25
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 10
- 229920003244 diene elastomer Polymers 0.000 claims description 16
- 229920002554 vinyl polymer Polymers 0.000 claims description 16
- 229920005990 polystyrene resin Polymers 0.000 claims description 10
- 239000000839 emulsion Substances 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- 238000010559 graft polymerization reaction Methods 0.000 claims description 7
- 229920001971 elastomer Polymers 0.000 abstract description 5
- 239000005060 rubber Substances 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 150000001993 dienes Chemical class 0.000 abstract description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 2
- 125000002348 vinylic group Chemical group 0.000 abstract 1
- -1 poly(alkyl styrene Chemical compound 0.000 description 35
- 230000000052 comparative effect Effects 0.000 description 20
- 238000000034 method Methods 0.000 description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 11
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 8
- 229920005992 thermoplastic resin Polymers 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 239000004609 Impact Modifier Substances 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000000149 argon plasma sintering Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 3
- 150000003440 styrenes Polymers 0.000 description 3
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000003011 styrenyl group Polymers [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 239000012285 osmium tetroxide Substances 0.000 description 1
- 229910000489 osmium tetroxide Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001608 poly(methyl styrenes) Polymers 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- OGRPJZFGZFQRHZ-UHFFFAOYSA-M sodium;4-octoxy-4-oxo-3-sulfobutanoate Chemical compound [Na+].CCCCCCCCOC(=O)C(S(O)(=O)=O)CC([O-])=O OGRPJZFGZFQRHZ-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は耐衝撃性を改質したポリ
スチレン系樹脂組成物に関する。さらに詳しくは耐熱性
が高く、且つ耐衝撃性にすぐれたシンジオタクチック構
造のポリスチレン系樹脂組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polystyrene resin composition with improved impact resistance. More specifically, the present invention relates to a polystyrene resin composition having a syndiotactic structure that has high heat resistance and excellent impact resistance.
【０００２】0002
【従来の技術】シンジオタクチック構造を有するポリス
チレンを用いて耐熱性に優れる熱可塑性樹脂を提供する
方法が特開昭６２−２５７９５０号公報に開示されてい
る。また、特開昭６３−２６８７１１号公報にはシンジ
オタクチックポリスチレンの成形性を改良する方法が開
示されている。しかしながら、このシンジオタクチック
構造のポリスチレンは、耐衝撃性に劣るため、実用的に
は限られた分野にしか利用できない難点がある。2. Description of the Related Art A method for providing a thermoplastic resin having excellent heat resistance using polystyrene having a syndiotactic structure is disclosed in Japanese Patent Application Laid-Open No. 62-257950. Furthermore, Japanese Patent Application Laid-Open No. 63-268711 discloses a method for improving the moldability of syndiotactic polystyrene. However, polystyrene with a syndiotactic structure has poor impact resistance, so it has the disadvantage that it can only be used in a limited number of practical fields.
【０００３】0003
【発明が解決しようとする課題】本発明は、耐熱性に優
れ、かつ耐衝撃性にも優れたシンジオタクチック構造の
ポリスチレン系樹脂組成物を提供することを目的とする
。SUMMARY OF THE INVENTION An object of the present invention is to provide a polystyrene resin composition having a syndiotactic structure that has excellent heat resistance and impact resistance.
【０００４】0004
【課題を解決するための手段】すなわち本発明は、（Ａ
）シンジオタクチック構造のポリスチレン系樹脂９７〜
６０重量部と、（Ｂ）重量平均粒子径が０．３μｍ以上
のジエン系ゴム重合体を５０重量％以上含むジエン系ゴ
ム重合体ラテックス４０〜８０重量％（固形分換算）の
存在下に、アクリル系単量体１〜２０重量％、芳香族ビ
ニル系単量体１〜６０重量％及び共重合可能なビニル系
単量体０〜２０重量％を乳化グラフト重合して得られた
グラフト共重合体３〜４０重量部［（Ａ）と（Ｂ）との
合計量１００重量部］からなる耐衝撃性、耐熱性に優れ
たポリスチレン系樹脂組成物である。[Means for Solving the Problems] That is, the present invention provides (A
) Polystyrene resin with syndiotactic structure 97~
In the presence of 60 parts by weight and (B) 40 to 80% by weight (in terms of solid content) of a diene rubber polymer latex containing 50% by weight or more of a diene rubber polymer having a weight average particle diameter of 0.3 μm or more, A graft copolymer obtained by emulsion graft polymerization of 1 to 20% by weight of an acrylic monomer, 1 to 60% by weight of an aromatic vinyl monomer, and 0 to 20% by weight of a copolymerizable vinyl monomer. It is a polystyrene-based resin composition having excellent impact resistance and heat resistance, comprising 3 to 40 parts by weight of the combined product [total amount of (A) and (B): 100 parts by weight].
【０００５】本発明の組成物（Ａ）成分のポリスチレン
系樹脂は、シンジオタクチック構造、すなわち、炭素−
炭素結合からなる主鎖に対し、側鎖のフェニル基或いは
置換フェニル基が交互に反対方向に位置する立体構造を
有するものである。ポリスチレン系樹脂としては、ポリ
スチレン、ポリ（アルキルスチレン）、ポリ（ハロゲン
化スチレン）ポリ（アルコキシスチレン）、ポリ（安息
香酸エステルスチレン）及びこれらの混合物、或いはこ
れらを主成分とする共重合体などが用いられる。なお、
ポリ（アルキルスチレン）としては、ポリ（メチルスチ
レン）、ポリ（エチルスチレン）、ポリ（イソプロピル
スチレン）、ポリ（タ−シャリ−ブチルスチレン）など
があり、ポリ（ハロゲン化スチレン）としては、ポリ（
クロロスチレン）、ポリ（ブロモスチレン）などがある
。またポリ（アルコキシスチレン）としては、ポリ（メ
トキシスチレン）、ポリ（エトキシスチレン）などがあ
る。The polystyrene resin component (A) of the composition of the present invention has a syndiotactic structure, that is, a carbon-
It has a three-dimensional structure in which side chain phenyl groups or substituted phenyl groups are alternately located in opposite directions with respect to a main chain consisting of carbon bonds. Examples of polystyrene resins include polystyrene, poly(alkyl styrene), poly(halogenated styrene) poly(alkoxystyrene), poly(benzoate styrene), mixtures thereof, or copolymers containing these as main components. used. In addition,
Examples of poly(alkylstyrene) include poly(methylstyrene), poly(ethylstyrene), poly(isopropylstyrene), and poly(tert-butylstyrene), and examples of poly(halogenated styrene) include poly(styrene).
chlorostyrene), poly(bromostyrene), etc. Examples of poly(alkoxystyrene) include poly(methoxystyrene) and poly(ethoxystyrene).
【０００６】次に本発明の組成物の（Ｂ）成分について
説明する。（Ｂ）成分のグラフト共重合体は、耐衝撃性
改良の目的で用いられる。このグラフト共重合体の調製
に使用するジエン系ゴム重合体ラテックスは、重量平均
粒子径が０．３μｍ以上の「大粒径」のジエン系ゴム重
合体ラテックスを５０重量％以上、好ましくは７０重量
％以上（固形分換算）含むジエン系ゴム重合体ラテック
スである。Next, component (B) of the composition of the present invention will be explained. The graft copolymer of component (B) is used for the purpose of improving impact resistance. The diene rubber polymer latex used to prepare this graft copolymer contains 50% by weight or more, preferably 70% by weight of a "large particle size" diene rubber polymer latex with a weight average particle diameter of 0.3 μm or more. % or more (in terms of solid content).
【０００７】上記の「大粒径」のジエン系ゴム重合体ラ
テックスは、その重量平均粒子径が０．３μｍ未満の場
合には、最終的に得られる樹脂組成物の衝撃強度を充分
に高めることができない。また、この「大粒径」のジエ
ン系ゴム重合体ラテックスの、ジエン系ゴム重合体ラテ
ックス中に占める割合が、５０重量％未満では、「大粒
径」ゴムラテックスを使用する効果が薄れ、０．３μｍ
未満のジエン系ゴム重合体ラテックスを単独で使用した
場合と同じく、衝撃強度が低い樹脂組成物しか得られな
い。[0007] When the above-mentioned "large particle diameter" diene rubber polymer latex has a weight average particle diameter of less than 0.3 μm, it is possible to sufficiently increase the impact strength of the final resin composition. I can't. Furthermore, if the proportion of this "large particle size" diene rubber polymer latex in the diene rubber polymer latex is less than 50% by weight, the effect of using the "large particle size" rubber latex will be diminished, and the .3μm
As in the case where a diene-based rubber polymer latex of less than 10% is used alone, only a resin composition with low impact strength can be obtained.
【０００８】上記ジエン系ゴム重合体としては、ポリブ
タジエン重合体、或いはブタジエンを主成分とするブタ
ジエン−スチレン共重合体、ブタジエン−アクリロニト
リル共重合体、ブタジエン−アクリル酸ブチル共重合体
等が用いられる。最も一般的には、ポリブタジエン重合
体或いはブタジエン−スチレン共重合体が用いられる。
これらのジエン系ゴム重合体ラテックスの重量平均粒子
径は、ラテックスの電子顕微鏡写真から測定するか、或
いは光散乱法などにより測定できる。これらの測定方法
については、室井宗一著「高分子ラテックスの化学」（
昭和４５年５月５日株式会社高分子刊行会発行、）に詳
説されている。As the diene rubber polymer, polybutadiene polymers, butadiene-styrene copolymers containing butadiene as a main component, butadiene-acrylonitrile copolymers, butadiene-butyl acrylate copolymers, etc. are used. Most commonly, polybutadiene polymers or butadiene-styrene copolymers are used. The weight average particle size of these diene rubber polymer latexes can be measured from an electron micrograph of the latex, or by a light scattering method. Regarding these measurement methods, please refer to "Chemistry of Polymer Latex" by Soichi Muroi (
(published by Kobunshi Publishing Co., Ltd. on May 5, 1971).
【０００９】本発明の組成物の（Ｂ）成分のグラフト共
重合体は、上記のジエン系ゴム重合体ラテックスの存在
下にアクリル系単量体及び芳香族ビニル系単量体を乳化
グラフト重合することにより得られたものである。この
際に他の共重合可能なビニル系単量体を併用しても良い
。The graft copolymer as component (B) of the composition of the present invention is prepared by emulsion graft polymerization of an acrylic monomer and an aromatic vinyl monomer in the presence of the diene rubber polymer latex. This was obtained by At this time, other copolymerizable vinyl monomers may be used in combination.
【００１０】ここで用いられるアクリル系単量体として
は、アルキル基の炭素数が１〜４個のものが好ましく、
例えばメタクリル酸メチル、メタクリル酸エチル、メタ
クリル酸プロピル、メタクリル酸イソプロピル、メタク
リル酸ｎ−ブチル、メタクリル酸イソブチル及びメタク
リル酸タ−シャリブチル等が挙げられ、特にメタクリル
酸メチルが好ましい。The acrylic monomer used here preferably has an alkyl group of 1 to 4 carbon atoms,
Examples include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate and tert-butyl methacrylate, with methyl methacrylate being particularly preferred.
【００１１】また、芳香族ビニル化合物としては、スチ
レンが代表に挙げられるが、その他に、α−置換スチレ
ン、核置換スチレン及びその誘導体、例えばα−メチル
スチレン、クロルスチレン、ビニルトルエン等を用いて
も良い。[0011] Styrene is a typical aromatic vinyl compound, but in addition, α-substituted styrene, nuclear-substituted styrene, and derivatives thereof, such as α-methylstyrene, chlorstyrene, vinyltoluene, etc. Also good.
【００１２】また、共重合可能なビニル系単量体として
は、アクリル酸メチル、アクリル酸エチル、アクリル酸
プロピル、アクリル酸ｎ−ブチル、アクリル酸ｉ−ブチ
ル、アクリル酸ｔ−ブチル、アクリル酸２−エチルヘキ
シル、アクリル酸ｎ−オクチル等のアクリル酸アルキル
エステルやアクリロニトリル等を用いることができる。[0012] Examples of copolymerizable vinyl monomers include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, and di-acrylate. - Acrylic acid alkyl esters such as ethylhexyl and n-octyl acrylate, acrylonitrile, and the like can be used.
【００１３】グラフト共重合体に占めるジエン系ゴム重
合体の割合は、固形分に換算して４０〜８０重量％であ
ることが好ましい。この割合が８０重量％を上廻る場合
には、最終の樹脂組成物の混合性が著しく低下し、いわ
ゆるブツ、フィッシュアイ等の表面外観を悪化させる問
題が生じ、また、反対に４０重量％未満では、樹脂組成
物の耐衝撃性改良効果が少なく、いずれの場合も好まし
くない。The proportion of the diene rubber polymer in the graft copolymer is preferably 40 to 80% by weight in terms of solid content. If this proportion is more than 80% by weight, the mixability of the final resin composition will be significantly reduced, causing a problem of deterioration of the surface appearance such as so-called bumps and fish eyes; In this case, the effect of improving the impact resistance of the resin composition is small, and either case is not preferable.
【００１４】乳化グラフト重合に供するアクリル系単量
体、芳香族ビニル系単量体及び共重合可能なビニル系単
量体の割合は、得られたグラフト共重合体の、その後の
工程で混合されるシンシオタクチックポリスチレン系樹
脂との親和性の点から、アクリル系単量体１〜２０重量
％、芳香族ビニル系単量体１〜６０重量％、共重合可能
なビニル系単量体０〜２０重量％の割合が好ましく、更
に好ましくは、アクリル系単量体５〜２０重量％、芳香
族ビニル系単量体５〜４０重量％、共重合可能なビニル
系単量体０〜２０重量％である。[0014] The proportions of the acrylic monomer, aromatic vinyl monomer and copolymerizable vinyl monomer to be subjected to emulsion graft polymerization are determined by the proportions of the obtained graft copolymer, which are mixed in a subsequent step. From the viewpoint of affinity with the syncytactic polystyrene resin, 1 to 20% by weight of acrylic monomer, 1 to 60% by weight of aromatic vinyl monomer, and 0 to 0 to 60% of copolymerizable vinyl monomer. The proportion is preferably 20% by weight, more preferably 5 to 20% by weight of acrylic monomer, 5 to 40% by weight of aromatic vinyl monomer, and 0 to 20% by weight of copolymerizable vinyl monomer. It is.
【００１５】本発明組成物において、耐衝撃性改質剤と
して用いられる成分（Ｂ）のグラフト共重合体は、通常
の乳化グラフト重合法で製造するのが好ましい。この乳
化グラフト重合において、乳化剤としては、脂肪酸塩、
アルキル硫酸エステル塩、アルキルベンゼンスルフォン
酸塩、アルキルリン酸エステル塩、ジアルキルスルフォ
コハク酸塩等のアニオン性界面活性剤、またポリオキシ
エチレンアルキルエ−テル、ポリオキシエチレン脂肪酸
エステル、ソルビタン脂肪酸エステル、グリセリン脂肪
酸エステル等のノニオン性界面活性剤、更にアルキルア
ミン塩等のカチオン性界面活性剤を使用することができ
る。これらの界面活性剤は単独で又は併用して使用する
ことができる。また乳化剤の種類により、重合系のｐＨ
がアルカリ側となる時は、アクリル酸アルキルエステル
の加水分解を防止するため、適当なｐＨ調節剤を使用す
ることもできる。In the composition of the present invention, the graft copolymer of component (B) used as an impact modifier is preferably produced by a conventional emulsion graft polymerization method. In this emulsion graft polymerization, the emulsifiers include fatty acid salts,
Anionic surfactants such as alkyl sulfates, alkylbenzene sulfonates, alkyl phosphates, dialkyl sulfosuccinates, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, glycerin Nonionic surfactants such as fatty acid esters and cationic surfactants such as alkylamine salts can be used. These surfactants can be used alone or in combination. Also, depending on the type of emulsifier, the pH of the polymerization system
When the acrylic acid alkyl ester is alkaline, an appropriate pH adjuster may be used to prevent hydrolysis of the acrylic acid alkyl ester.
【００１６】重合開始剤としては、通常重合開始剤とし
て用いられている過硫酸塩などの無機開始剤、又は有機
過酸化物、アゾ化合物等を単独で用いるか、或いは上記
化合物と亜硫酸塩、亜硫酸水素塩、チオ硫酸塩、第一金
属塩、ナトリウムホルムアルデヒドスルホキシレ−ト等
とを組合わせ、レドックス系開始剤として用いることも
できる。重合開始剤として好ましい過硫酸塩は、過硫酸
ナトリウム、過硫酸カリウム、過硫酸アンモニウム等で
ある。好ましい有機過酸化物としては、ｔ−ブチルハイ
ドロパ−オキシド、クメンヒドロパ−オキシド、過酸化
ベンゾイル、過酸化ラウロイル等がある。As the polymerization initiator, inorganic initiators such as persulfates, which are commonly used as polymerization initiators, organic peroxides, azo compounds, etc. may be used alone, or the above compounds may be combined with sulfites, sulfites, etc. It can also be used as a redox initiator in combination with hydrogen salts, thiosulfates, first metal salts, sodium formaldehyde sulfoxylate, etc. Preferred persulfates as polymerization initiators include sodium persulfate, potassium persulfate, ammonium persulfate, and the like. Preferred organic peroxides include t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, and lauroyl peroxide.
【００１７】グラフト共重合体の分子量、及びグラフト
率を調節するために、連鎖移動剤又は架橋剤を使用して
もよく、連鎖移動剤としては炭素数５〜２０のアルキル
メルカプタン等が使用でき、架橋剤としては、ジビニル
ベンゼン、１，３ブチレングリコ−ルジメタクリレ−ト
などの多官能性モノマ−が使用できる。In order to adjust the molecular weight and grafting rate of the graft copolymer, a chain transfer agent or a crosslinking agent may be used. As the chain transfer agent, an alkyl mercaptan having 5 to 20 carbon atoms or the like can be used. As the crosslinking agent, polyfunctional monomers such as divinylbenzene and 1,3 butylene glycol dimethacrylate can be used.
【００１８】乳化グラフト重合は、重合開始剤の分解温
度以上の温度にて、通常の乳化重合条件下で行う。この
重合の際に、各段階いずれの重合についても、各単量体
又は単量体の混合物の全量を一度に、或いは全量又は一
部を連続的に添加しながら行うことができる。ただし、
重合の安定性、重合反応熱の除去等の点からは全量又は
一部を添加しながら重合を行うことが好ましい。得られ
たグラフト共重合体のラテックスは、通常、塩析或いは
酸析凝固し、瀘過、水洗し粉末状で回収するか、或いは
噴霧乾燥、凍結乾燥等を行い、粉末状にして回収するこ
とができる。Emulsion graft polymerization is carried out under normal emulsion polymerization conditions at a temperature higher than the decomposition temperature of the polymerization initiator. During this polymerization, the entire amount of each monomer or a mixture of monomers can be added at once, or the entire amount or a portion thereof can be added continuously at each stage. however,
From the viewpoint of stability of polymerization, removal of heat of polymerization reaction, etc., it is preferable to carry out polymerization while adding all or part of it. The obtained latex of the graft copolymer is usually coagulated by salting out or acid precipitation, filtered and washed with water, and recovered in powder form, or spray-dried, freeze-dried, etc., and recovered in powder form. Can be done.
【００１９】本発明において、耐衝撃性改質剤として用
いられる成分（Ｂ）のグラフト共重合体と成分（Ｂ）の
シンジオタクチックポリスチレン系樹脂との配合は、好
ましくは、粉末状で、例えばリボンブレンダ−、ヘンシ
ェルミキサ−等により均一に行い、引き続いて、公知の
混練機、例えばミキシングロ−ル、バンバリ−ミキサ−
で混練し、押出機及び射出成形機等によって成形加工す
る。In the present invention, the graft copolymer of component (B) used as an impact modifier and the syndiotactic polystyrene resin of component (B) are preferably blended in powder form, for example. The mixture is uniformly mixed using a ribbon blender, Henschel mixer, etc., and then kneaded using a known kneading machine such as a mixing roll, Banbury mixer, etc.
The mixture is kneaded and molded using an extruder, injection molding machine, etc.
【００２０】また、本発明の熱可塑性樹脂組成物は、必
要に応じて、公知の安定剤、可塑剤、滑剤、紫外線吸収
剤、剥離剤、離型剤、着色剤、難燃剤等を添加含有して
もよい。本発明のポリスチレン系樹脂組成物は、家庭用
品、電気製品、自動車用材料或いは各種の機械部品材料
として有利に使用することができる。The thermoplastic resin composition of the present invention may also contain known stabilizers, plasticizers, lubricants, ultraviolet absorbers, release agents, mold release agents, colorants, flame retardants, etc., as necessary. You may. The polystyrene resin composition of the present invention can be advantageously used as household goods, electrical appliances, automobile materials, or materials for various mechanical parts.
【００２１】[0021]
【実施例】次に実施例を挙げて、本発明を詳細に説明す
るが、本発明はこれらの実施例により、限定されるもの
ではない。なお、実施例中、％及び部は、それぞれ重量
％及び重量部を意味する。EXAMPLES Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples. In addition, in the examples, % and parts mean weight % and parts by weight, respectively.
【００２２】実施例１（本発明例Ｃ）
（１）ブタジエン重合体（Ａ−１）ラテックスの合成。
１，３−ブタジエン１００部、ラウリン酸ソ−ダ４部、
ｎ−ラウリルメルカプタン０．５部、過硫酸カリウム０
．４部及び脱イオン水１８０部の混合物を、窒素置換を
行なったオ−トクレ−プ中に仕込み、撹拌しながら６０
℃で５０時間重合させてゴムラテックス（平均粒子径０
．０９μｍ）を得た。Example 1 (Invention Example C) (1) Synthesis of butadiene polymer (A-1) latex. 100 parts of 1,3-butadiene, 4 parts of sodium laurate,
0.5 parts of n-lauryl mercaptan, 0 potassium persulfate
．． A mixture of 4 parts of deionized water and 180 parts of deionized water was charged into an autoclave that had been purged with nitrogen, and heated to 60 parts with stirring.
Polymerized at ℃ for 50 hours to form rubber latex (average particle size 0).
．． 09 μm) was obtained.
【００２３】（２）肥大化用ラテックス（Ｂ）の合成。
エチルアクリレ−ト
８０ 部 メタクリル酸
２０ 部
過硫酸カリウム
０．５部 ノンサ−ルＴＫ−１（日本油脂
ＫＫ製、半硬化牛脂カリ石ケン） ２．０部
ラビゾ−ル８０（日本油脂ＫＫ製、ソディウムオクチル
スルホ サクシネ
−ト）
１．０部 水
２００ 部上記成分を７０℃で４時間重合させ、ｐＨ
６．２のエマルジョンラテックスを得た。(2) Synthesis of latex for enlargement (B). Ethyl acrylate
80 parts methacrylic acid
20 copies
potassium persulfate
0.5 parts Nonsal TK-1 (manufactured by NOF KK, semi-hardened beef tallow potash soap) 2.0 parts
Ravisol 80 (manufactured by NOF KK, sodium octyl sulfosuccinate)
1.0 part water
200 parts The above ingredients were polymerized at 70°C for 4 hours, and the pH
6.2 emulsion latex was obtained.
【００２４】（３）肥大化ラテックス（Ａ−２）の合成
。
前記ブタジエン重合体ラテックス（Ａ−１）１００部（
固形分）を撹拌機を備えた反応釜に入れ、それに前記肥
大化用ラテックス（Ｂ）２．０部（固形分）を撹拌しな
がら１０秒間で添加し、肥大化ラテックス（Ａ−２）を
得た。この肥大化ラテックスは、重量平均粒子径０．５
μｍの「大粒径」ラテックスであった。(3) Synthesis of enlarged latex (A-2). 100 parts of the butadiene polymer latex (A-1) (
Solid content) was placed in a reaction pot equipped with a stirrer, and 2.0 parts (solid content) of the enlarged latex (B) was added thereto for 10 seconds while stirring to form the enlarged latex (A-2). Obtained. This enlarged latex has a weight average particle diameter of 0.5
It was a "large particle size" latex of μm.
【００２５】（４）混合ゴムラテックス（Ａ−３）の製
造。
前記工程（１）及び（３）で得られた小粒径ゴムラテッ
クス（Ａ−１）と大粒径ゴムラテックス（Ａ−２）とを
２０／８０の重量比で室温にて均一に混合し、混合ゴム
ラテックス（Ａ−３）を得た。この混合ゴムラテックス
（Ａ−３）について、重量平均粒子径及び粒子径０．３
μｍ以上のゴムの重量比を測定した。この測定は、光散
乱法〔大塚電子（株）製ダイナミック光散乱光度計ＤＬ
Ｓ−７００〕により、そしてゴムラテックスを四酸化オ
スミウム水溶液にて処理し、透過型電子顕微鏡〔日本電
子（株）製ＪＥＭ−１００Ｓ〕写真により、個々に測定
した。いずれの方法においても重量平均粒子径はよく一
致していることが確認された。光散乱法による測定結果
を第１表の本発明例Ｃの欄に示す。(4) Production of mixed rubber latex (A-3). The small particle size rubber latex (A-1) obtained in the above steps (1) and (3) and the large particle size rubber latex (A-2) were mixed uniformly at room temperature at a weight ratio of 20/80. A mixed rubber latex (A-3) was obtained. Regarding this mixed rubber latex (A-3), the weight average particle size and particle size are 0.3
The weight ratio of rubber with a diameter of μm or more was measured. This measurement was performed using a light scattering method [Dynamic Light Scattering Photometer DL manufactured by Otsuka Electronics Co., Ltd.]
S-700] and the rubber latex was treated with an aqueous osmium tetroxide solution, and individually measured using a transmission electron microscope (JEM-100S, manufactured by JEOL Ltd.). It was confirmed that the weight average particle diameters were in good agreement with each other in both methods. The measurement results by the light scattering method are shown in the column of Invention Example C in Table 1.
【００２６】（５）グラフト共重合体（Ｇ−１）の合成
。
前記工程（４）で得られた混合ゴムラテックス（Ａ−３
）を６０部（固形分換算）、還元剤としてロンガリット
を０．１５部仕込み、内温を７０℃に保って、キュメン
ハイドロパ−オキサイド（以下ＣＨＰと略称する）０．
０４部を加えたメタクリル酸メチル８部とアクリル酸エ
チル２部との混合液を１時間で連続滴下し、更に１時間
保持した。その後、第２段として、スチレン２５部にＣ
ＨＰを０．１部混合したものを１時間で連続滴下し、更
に２時間保持した。次いで、第３段として、メタクリル
酸メチル４部、アクリル酸エチル１部及びＣＨＰ０．０
２部からなる混合液を１５分で滴下し、更に１時間保持
して重合を終了させた。得られたラテックスに熱安定剤
として２，６−ジ−第三ブチル−Ｐ−クレゾ−ル（Ｂ．
Ｈ．Ｔ）１．０部を添加し、０．２％硫酸水溶液で凝固
させ、温水で洗浄し、乾燥してグラフト共重合体（Ｇ−
１）を得た。(5) Synthesis of graft copolymer (G-1). Mixed rubber latex (A-3) obtained in step (4)
) and 0.15 parts of Rongalit as a reducing agent, and while keeping the internal temperature at 70°C, 0.0 parts of cumene hydroperoxide (hereinafter abbreviated as CHP) was added.
A mixed solution of 8 parts of methyl methacrylate and 2 parts of ethyl acrylate to which 4 parts of 0.04 parts was added was continuously added dropwise over 1 hour, and the mixture was maintained for an additional 1 hour. Then, as a second stage, add C to 25 parts of styrene.
A mixture of 0.1 part of HP was continuously added dropwise over a period of 1 hour, and the mixture was maintained for an additional 2 hours. Then, as the third stage, 4 parts of methyl methacrylate, 1 part of ethyl acrylate and 0.0 parts of CHP
A mixed solution consisting of 2 parts was added dropwise over 15 minutes and maintained for an additional hour to complete the polymerization. 2,6-di-tert-butyl-P-cresol (B.
H. 1.0 part of G-
1) was obtained.
【００２７】（６）シンジオタクチックポリスチレンの
合成。
反応器に、
スチレン ４．５ｍｏｌ／
ｌＴｉ（ＯＢｕ）４ １．４×１０−４
ｍｏｌ／ｌメチルアルモキサン １．４×１０−
１ｍｏｌ／ｌ溶媒としてトルエンを用い、全容積を５リ
ットルとして５０℃で７時間重合した。重合後、生成ポ
リマ−をメタノ−ルで沈澱させ、メタノ−ルによる洗浄
、瀘過の後、乾燥した。重合収率は１５％であった。次
に生成ポリマ−をメチルエチルケトンを用い抽出し、９
４．２％の不溶部を得た。この重合体は重量平均分子量
が２７５，０００、数平均分子量が５６，０００であり
、融点は２７０℃、核磁気共鳴による分析から求めたシ
ンジオタクティシティ−は９５％であった。(6) Synthesis of syndiotactic polystyrene. Styrene 4.5 mol/into the reactor
lTi(OBu)4 1.4×10-4
mol/l methylalumoxane 1.4×10-
Polymerization was carried out at 50° C. for 7 hours using toluene as a 1 mol/l solvent in a total volume of 5 liters. After polymerization, the resulting polymer was precipitated with methanol, washed with methanol, filtered, and dried. The polymerization yield was 15%. Next, the produced polymer was extracted using methyl ethyl ketone, and
An insoluble fraction of 4.2% was obtained. This polymer had a weight average molecular weight of 275,000, a number average molecular weight of 56,000, a melting point of 270° C., and a syndiotacticity of 95% as determined by nuclear magnetic resonance analysis.
【００２８】（７）熱可塑性樹脂組成物の製造。
前記工程（５）で得られたグラフト共重合体（Ｇ−１）
と前工程（６）で得られたシンジオタクチックポリスチ
レンとを２５／７５の重量比でミキサ−を用いて充分混
合し、２５ｍｍφベント付押出器を用い２８０℃で溶融
混連しペレット化した。このペレットを真空乾燥後、射
出成形し〔三城精器（株）製ＳＡＶ−６０、射出圧４０
Ｋｇ／ｃｍ２、金型温度６０℃〕、得られた成形品の耐
衝撃性及び耐熱性を測定した。その結果を下記の第１表
の本発明例Ｃの欄に示す。なお、耐衝撃性はノッチ付ア
イゾッドインパクトをＡＳＴＭ−Ｄ−２５６の規格によ
り、また、耐熱性はビッカ−ト軟化温度をＶＤＥ法に基
づき５Ｋｇ荷重にて測定した。(7) Production of thermoplastic resin composition. Graft copolymer (G-1) obtained in step (5) above
and the syndiotactic polystyrene obtained in the previous step (6) were thoroughly mixed using a mixer at a weight ratio of 25/75, and the mixture was melt-mixed and pelletized at 280°C using a 25 mmφ vented extruder. After vacuum drying, the pellets were injection molded [SAV-60 manufactured by Miki Seiki Co., Ltd., injection pressure 40].
kg/cm2, mold temperature 60°C], and the impact resistance and heat resistance of the obtained molded product were measured. The results are shown in the column of Invention Example C in Table 1 below. The impact resistance was measured by notched Izod impact according to the ASTM-D-256 standard, and the heat resistance was measured by Bickert softening temperature based on the VDE method under a load of 5 kg.
【００２９】実施例２（本発明例Ａ、Ｂ、Ｄ）前記実施
例１に記載の手法を繰返した。但し、本例の場合、前記
工程（４）で示される小粒径ゴムラテックス（Ａ−１）
と大粒径ゴムラテックス（Ａ−２）との混合比を、第１
表の本発明例Ａ、Ｂ、Ｄの欄に示す通りに変更した。各
成形品の物性測定結果を、それぞれ第１表の本発明例Ａ
、Ｂ、Ｄの欄に示す。Example 2 (Inventive Examples A, B, D) The procedure described in Example 1 above was repeated. However, in the case of this example, the small particle size rubber latex (A-1) shown in the step (4)
The mixing ratio of the large particle size rubber latex (A-2) was
The changes were made as shown in the columns of Invention Examples A, B, and D in the table. The physical property measurement results of each molded article are shown in Table 1.
, B, and D columns.
【００３０】比較例１（比較例Ａ、Ｂ、Ｃ及びＤ）前記
実施例１に記載の手法を繰返した。但し、本例の場合、
前記工程（４）で示される小粒径ゴムラテックス（Ａ−
１）と大粒径ゴムラテックス（Ａ−２）との混合比を、
第１表の比較例Ａ、Ｂ、Ｃ、Ｄの欄に示す通りに変更し
た。各成形品の物性を測定した結果を第１表の比較例Ａ
〜Ｄの欄に示す。比較例Ｄではシンジオタクチックポリ
スチレンのみで測定した。Comparative Example 1 (Comparative Examples A, B, C and D) The procedure described in Example 1 above was repeated. However, in this example,
The small particle size rubber latex (A-
The mixing ratio of 1) and large particle size rubber latex (A-2) is
The changes were made as shown in the columns of Comparative Examples A, B, C, and D in Table 1. The results of measuring the physical properties of each molded product are shown in Comparative Example A in Table 1.
- Shown in columns D. In Comparative Example D, only syndiotactic polystyrene was used.
【００３１】[0031]
【表１】[Table 1]
【００３２】実施例３（本発明例Ｅ〜Ｉ）前記実施例１
に記載の手法を繰り返した。但し、本例の場合、前記実
施例１の工程（２）の肥大化用ラテックス（Ｂ）の合成
において、エチルアクリレ−トとメタクリル酸の重量比
を、第２表の本発明例Ｅ、Ｆ、Ｇ、Ｈ、Ｉの欄に示す通
りに変更した。各成形品の物性測定結果を表２の本発明
例Ｅ〜Ｉの欄に示す。Example 3 (Examples E to I of the present invention) Example 1 above
The method described in was repeated. However, in the case of this example, in the synthesis of the enlargement latex (B) in step (2) of Example 1, the weight ratio of ethyl acrylate and methacrylic acid was changed to Inventive Examples E, F in Table 2, Changes were made as shown in columns G, H, and I. The physical property measurement results of each molded article are shown in the columns of Invention Examples E to I in Table 2.
【００３３】比較例２（比較例Ｅ〜Ｈ）前記実施例１に
記載の手法を繰り返した。但し、本例の場合、前記工程
（２）の肥大化用高分子ラテックス（Ｂ）の合成におい
て、エチルアクリレ−トとメタクリル酸の重量比を、第
２表の比較例Ｅ、Ｆ、Ｇ、Ｈの欄に示す通りに変更した
。各成形品の物性測定結果を表２の本発明例Ｅ〜Ｈの欄
に示す。比較例Ｈではシンジオタクチックポリスチレン
のみで測定を行なった。Comparative Example 2 (Comparative Examples E-H) The procedure described in Example 1 above was repeated. However, in the case of this example, in the synthesis of the thickening polymer latex (B) in step (2), the weight ratio of ethyl acrylate and methacrylic acid was changed to Comparative Examples E, F, G, and H in Table 2. Changes were made as shown in the column. The physical property measurement results of each molded article are shown in the columns of Invention Examples E to H in Table 2. In Comparative Example H, measurements were conducted using only syndiotactic polystyrene.
【００３４】[0034]
【表２】[Table 2]
【００３５】実施例４（本発明例Ｊ−Ｍ）（１）ブタジ
エン−スチレン共重合体（Ａ−４）ラテックスの製造
１，３−ブタジエン
７５
部 スチレン
２５ 部 ジビニルベン
ゼン
１ 部
ジイソプロピルベンゼンヒドロパ−オキシド
０．２ 部 ピロリン
酸ソ−ダ
０．５ 部
硫酸第１鉄
０．０１部 テキストロ−ズ
１．０ 部 オレイン酸カリウ
ム
２．０ 部 水
２０
０ 部上記成分を耐圧オ−トクレ−プ中にて
５０℃で重合を行なった。８時間で重合は完成し、得ら
れたゴムの平均粒子径は０．０８μｍであった。Example 4 (Invention Examples J-M) (1) Production of butadiene-styrene copolymer (A-4) latex 1,3-butadiene
75
Part styrene
25 parts divinylbenzene
1 part diisopropylbenzene hydroperoxide
0.2 part Sodium pyrophosphate
0.5 part ferrous sulfate
0.01 part text rose
1.0 part potassium oleate
2.0 parts water
20
0 parts The above components were polymerized at 50°C in a pressure-resistant autoclave. Polymerization was completed in 8 hours, and the average particle size of the obtained rubber was 0.08 μm.
【００３６】（２）上記ゴムラテックス（Ａ−４）を、
前記実施例１の工程（２）の肥大化用ラテックス（Ｂ）
を用いて肥大化し、前記実施例１の工程（３）と同様に
して肥大化ラテックス（Ａ−５：平均粒子径０．５３μ
ｍ）を得た。引き続いて、前記実施例１の工程（４）〜
（６）に記載の手法を繰り返した。前記ブタジエン−ス
チレンゴムラテックス（Ａ−４）及び肥大化ラテックス
（Ａ−５）を、第３表の本発明例Ｊ、Ｋ、Ｌ、Ｍの欄に
示す重量比で用いた熱可塑性樹脂組成物の成形品の機械
的性質及び熱的性質を測定した。その結果を第３表の本
発明例Ｊ〜Ｍの欄に示す。(2) The above rubber latex (A-4),
Latex for enlargement (B) in step (2) of Example 1
The enlarged latex (A-5: average particle diameter 0.53μ
m) was obtained. Subsequently, step (4) of Example 1
The method described in (6) was repeated. A thermoplastic resin composition using the butadiene-styrene rubber latex (A-4) and the enlarged latex (A-5) in the weight ratios shown in the columns of Invention Examples J, K, L, and M in Table 3. The mechanical and thermal properties of the molded articles were measured. The results are shown in the columns of Invention Examples J to M in Table 3.
【００３７】比較例３（比較例Ｉ〜Ｋ）前記実施例４に
記載の手法を繰り返した。但し、本例の場合、前記ブタ
ジエン−スチレンゴムラテックス（Ａ−４）及び肥大化
ラテックス（Ａ−５）の重量比を、第３表の比較例Ｉ、
Ｊ、Ｋの欄に示す重量比に変更した。各成形品の機械的
性質及び熱的性質の測定結果を第３表の比較例Ｉ〜Ｋの
欄に示す。Comparative Example 3 (Comparative Examples I-K) The procedure described in Example 4 above was repeated. However, in the case of this example, the weight ratio of the butadiene-styrene rubber latex (A-4) and the enlarged latex (A-5) was changed to Comparative Example I in Table 3.
The weight ratios were changed to those shown in columns J and K. The measurement results of the mechanical properties and thermal properties of each molded article are shown in the Comparative Examples IK column of Table 3.
【００３８】[0038]
【表３】[Table 3]
【００３９】実施例５（本発明例Ｎ〜Ｑ）前記実施例１
に記載の手法を繰り返した。但し、本例の場合、前記実
施例１の工程（４）で得られた混合ゴムラテックス（Ａ
−３）を固形分として６０部、還元剤としてロンガリッ
トを０．１５部仕込み、内温を７０℃に保った。ＣＨＰ
０．１５部加えた、第４表の本発明例欄Ｎ、Ｏ、Ｐ、Ｑ
に示す割合のメタクリル酸メチル、スチレン及びアクリ
ロニトリルの混合液を２時間で連続滴下し、更に２時間
保持して重合を終了さ、得られたラテックスに熱安定剤
としてＢ．Ｈ．Ｔを１．０部添加し、乾燥してグラフト
共重合体を得た。各熱可塑性樹脂組成物の成形品の機械
的性質を第４表の本発明例Ｎ〜Ｑの欄に示す。Example 5 (Examples N to Q of the present invention) Example 1 above
The method described in was repeated. However, in the case of this example, the mixed rubber latex (A
-3) as a solid content and 0.15 parts of Rongalite as a reducing agent were added, and the internal temperature was maintained at 70°C. C.H.P.
Added 0.15 parts to Table 4, invention example columns N, O, P, Q
A mixed solution of methyl methacrylate, styrene, and acrylonitrile in the proportions shown is continuously added dropwise over a period of 2 hours, and maintained for an additional 2 hours to complete the polymerization.B. H. 1.0 part of T was added and dried to obtain a graft copolymer. The mechanical properties of molded articles of each thermoplastic resin composition are shown in the columns of Invention Examples N to Q in Table 4.
【００４０】比較例Ｌ〜Ｏ：前記実施例５に記載の手法
を繰り返した。但し、本例の場合、メタクリル酸メチル
とスチレン及びアクリロニトリルの重量比を第４表の比
較例欄Ｌ、Ｍ、Ｎ、Ｏに示す割合に変更した。得られた
各熱可塑性樹脂組成物の成形品の機械的性質を下記の第
４表の比較例Ｌ〜Ｏの欄に示す。Comparative Examples L-O: The procedure described in Example 5 above was repeated. However, in the case of this example, the weight ratio of methyl methacrylate to styrene and acrylonitrile was changed to the ratios shown in Comparative Example column L, M, N, and O in Table 4. The mechanical properties of the molded articles of each thermoplastic resin composition obtained are shown in the columns of Comparative Examples L to O in Table 4 below.
【００４１】[0041]
【表４】[Table 4]
【００４２】実施例６（本発明例Ｒ〜Ｕ）：前記実施例
１に記載の手法を繰り返した。但し、本例の場合、前記
実施例１の（４）で得られた混合ゴムラテックス（Ａ−
３）の使用量を重量比（固形分）で、第５表の本発明例
欄Ｒ、Ｓ、Ｔ、Ｕに示すように変更し、それに応じて前
記実施例１の工程（５）におけるグラフト処方の重量比
を変更した。得られた熱可塑性樹脂組成物の成形品の機
械的性質及び目視による表面外観を測定した。その結果
を第５表の本発明例Ｒ〜Ｕの欄に示す。Example 6 (Inventive Examples R to U): The procedure described in Example 1 above was repeated. However, in the case of this example, the mixed rubber latex (A-
The amount used in 3) was changed in terms of weight ratio (solid content) as shown in the invention examples column R, S, T, and U in Table 5, and the grafting in step (5) of Example 1 was changed accordingly. The weight ratio of the prescription was changed. The mechanical properties and visual surface appearance of the molded article of the obtained thermoplastic resin composition were measured. The results are shown in the columns of invention examples R to U in Table 5.
【００４３】比較例４（比較例Ｐ及びＱ）前記実施例６
に記載の手法を繰り返した。但し、本例の場合、固形分
としての混合ゴムラテックス量を第５表の比較例欄Ｐ、
Ｑに示す通りに変更した。得られた熱可塑性樹脂組成物
の成形品の機械的性質及び目視による表面外観を測定し
た。その結果を第５表の比較例Ｐ及びＱの欄に示す。Comparative Example 4 (Comparative Examples P and Q) Example 6
The method described in was repeated. However, in the case of this example, the amount of mixed rubber latex as solid content is shown in Comparative example column P of Table 5.
Changes were made as shown in Q. The mechanical properties and visual surface appearance of the molded article of the obtained thermoplastic resin composition were measured. The results are shown in the columns of Comparative Examples P and Q in Table 5.
【００４４】[0044]
【表５】[Table 5]
【００４５】[0045]
【発明の効果】本発明は、シンジオタクチックポリスチ
レン系樹脂の耐衝撃性改質剤として配合する、ジエン系
ゴム重合体ラテックスとアクリル系単量体、芳香族ビニ
ル系単量体及び共重合可能なビニル系単量体とのグラフ
ト共重合体として、重量平均粒子径が０．３μｍ以上の
ジエン系ゴム重合体ラテックスを５０重量％以上含むジ
エン系ゴム重合体ラテックスの存在下で共重合させたグ
ラフト共重合体を用いたので、シンジオタクチックポリ
スチレンの耐衝撃性を著しく向上させることができる。
したがって、本発明の組成物は、優れた耐熱性と共に優
れた耐衝撃性を有し、またその成形品の表面外観も優れ
ている。Effects of the Invention The present invention is formulated with a diene rubber polymer latex, an acrylic monomer, an aromatic vinyl monomer, and a copolymerizable material to be blended as an impact modifier for syndiotactic polystyrene resin. A graft copolymer with a vinyl monomer is copolymerized in the presence of a diene rubber polymer latex containing 50% by weight or more of a diene rubber polymer latex with a weight average particle diameter of 0.3 μm or more. Since the graft copolymer is used, the impact resistance of syndiotactic polystyrene can be significantly improved. Therefore, the composition of the present invention has excellent heat resistance and impact resistance, and the surface appearance of molded articles thereof is also excellent.
Claims (1)
レン系樹脂９７〜６０重量部と、（Ｂ）重量平均粒子径
が０．３μｍ以上のジエン系ゴム重合体を５０重量％以
上含むジエン系ゴム重合体ラテックス４０〜８０重量％
（固形分換算）の存在下に、アクリル系単量体１〜２０
重量％、芳香族ビニル系単量体１〜６０重量％及び共重
合可能なビニル系単量体０〜２０重量％を乳化グラフト
重合して得られたグラフト共重合体３〜４０重量部［（
Ａ）と（Ｂ）との合計量１００重量部］からなる耐衝撃
性、耐熱性に優れたポリスチレン系樹脂組成物。Claim 1: A diene rubber containing (A) 97 to 60 parts by weight of a polystyrene resin having a syndiotactic structure and (B) 50% by weight or more of a diene rubber polymer having a weight average particle diameter of 0.3 μm or more. Polymer latex 40-80% by weight
(in terms of solid content), acrylic monomer 1 to 20
3 to 40 parts by weight of a graft copolymer obtained by emulsion graft polymerization of 1 to 60 weight % of an aromatic vinyl monomer and 0 to 20 weight % of a copolymerizable vinyl monomer [(
A polystyrene resin composition having excellent impact resistance and heat resistance, comprising 100 parts by weight of A) and (B) in total.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6536591A JPH04279646A (en) | 1991-03-07 | 1991-03-07 | Polystyrene-based resin composition excellent in impact and heat resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6536591A JPH04279646A (en) | 1991-03-07 | 1991-03-07 | Polystyrene-based resin composition excellent in impact and heat resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04279646A true JPH04279646A (en) | 1992-10-05 |
Family
ID=13284868
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6536591A Pending JPH04279646A (en) | 1991-03-07 | 1991-03-07 | Polystyrene-based resin composition excellent in impact and heat resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04279646A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996017889A1 (en) * | 1994-12-07 | 1996-06-13 | Idemitsu Petrochemical Co., Ltd. | Polystyrene resin composition and oriented polystyrene film |
| WO2003082973A1 (en) * | 2002-03-29 | 2003-10-09 | Kaneka Corporation | Impact-resistant thermoplastic resin composition |
-
1991
- 1991-03-07 JP JP6536591A patent/JPH04279646A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996017889A1 (en) * | 1994-12-07 | 1996-06-13 | Idemitsu Petrochemical Co., Ltd. | Polystyrene resin composition and oriented polystyrene film |
| WO2003082973A1 (en) * | 2002-03-29 | 2003-10-09 | Kaneka Corporation | Impact-resistant thermoplastic resin composition |
| EP1491584A1 (en) * | 2002-03-29 | 2004-12-29 | Kaneka Corporation | Impact-resistant thermoplastic resin composition |
| EP1491584A4 (en) * | 2002-03-29 | 2005-06-08 | Kaneka Corp | Impact-resistant thermoplastic resin composition |
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