JP3725440B2 - Transparent polystyrene resin composition - Google Patents
Transparent polystyrene resin composition Download PDFInfo
- Publication number
- JP3725440B2 JP3725440B2 JP2001116934A JP2001116934A JP3725440B2 JP 3725440 B2 JP3725440 B2 JP 3725440B2 JP 2001116934 A JP2001116934 A JP 2001116934A JP 2001116934 A JP2001116934 A JP 2001116934A JP 3725440 B2 JP3725440 B2 JP 3725440B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- polystyrene resin
- transparent polystyrene
- parts
- styrene
- 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 - Lifetime
Links
- 229920005990 polystyrene resin Polymers 0.000 title claims description 95
- 239000011342 resin composition Substances 0.000 title claims description 63
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 80
- 229920001577 copolymer Polymers 0.000 claims description 57
- 239000000178 monomer Substances 0.000 claims description 53
- 238000006243 chemical reaction Methods 0.000 claims description 49
- 229920000642 polymer Polymers 0.000 claims description 42
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 36
- -1 pentaerythritol ester compound Chemical class 0.000 claims description 22
- 229920001971 elastomer Polymers 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 18
- 229920001400 block copolymer Polymers 0.000 claims description 17
- 239000005060 rubber Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 238000001746 injection moulding Methods 0.000 claims description 10
- 150000001993 dienes Chemical class 0.000 claims description 8
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 claims description 4
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 claims description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 claims description 4
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 claims description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- 235000021357 Behenic acid Nutrition 0.000 claims description 2
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 claims description 2
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005639 Lauric acid Substances 0.000 claims description 2
- 235000021353 Lignoceric acid Nutrition 0.000 claims description 2
- CQXMAMUUWHYSIY-UHFFFAOYSA-N Lignoceric acid Natural products CCCCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 CQXMAMUUWHYSIY-UHFFFAOYSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- 235000021314 Palmitic acid Nutrition 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 2
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 2
- 235000021342 arachidonic acid Nutrition 0.000 claims description 2
- 229940114079 arachidonic acid Drugs 0.000 claims description 2
- 229940116226 behenic acid Drugs 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 229920003244 diene elastomer Polymers 0.000 claims description 2
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 claims description 2
- FARYTWBWLZAXNK-WAYWQWQTSA-N ethyl (z)-3-(methylamino)but-2-enoate Chemical compound CCOC(=O)\C=C(\C)NC FARYTWBWLZAXNK-WAYWQWQTSA-N 0.000 claims description 2
- 229940033355 lauric acid Drugs 0.000 claims description 2
- 229960004488 linolenic acid Drugs 0.000 claims description 2
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 229940098695 palmitic acid Drugs 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 229960004274 stearic acid Drugs 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 description 70
- 229920005989 resin Polymers 0.000 description 41
- 239000011347 resin Substances 0.000 description 41
- 239000000243 solution Substances 0.000 description 36
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 30
- 238000004519 manufacturing process Methods 0.000 description 22
- OCKWAZCWKSMKNC-UHFFFAOYSA-N [3-octadecanoyloxy-2,2-bis(octadecanoyloxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(COC(=O)CCCCCCCCCCCCCCCCC)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC OCKWAZCWKSMKNC-UHFFFAOYSA-N 0.000 description 21
- 238000000034 method Methods 0.000 description 20
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 18
- 239000002994 raw material Substances 0.000 description 17
- 239000004342 Benzoyl peroxide Substances 0.000 description 16
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 16
- 235000019400 benzoyl peroxide Nutrition 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 15
- 239000003960 organic solvent Substances 0.000 description 15
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 15
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 14
- 125000005641 methacryl group Chemical group 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- 239000004793 Polystyrene Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000000465 moulding Methods 0.000 description 12
- 229920002223 polystyrene Polymers 0.000 description 12
- 229920001890 Novodur Polymers 0.000 description 9
- 239000008188 pellet Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 239000003999 initiator Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 3
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 238000010559 graft polymerization reaction Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 description 2
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 2
- KIKBJYQCJJXCBZ-UHFFFAOYSA-N 1-octylpyrrole-2,5-dione Chemical compound CCCCCCCCN1C(=O)C=CC1=O KIKBJYQCJJXCBZ-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- PFBWBEXCUGKYKO-UHFFFAOYSA-N ethene;n-octadecyloctadecan-1-amine Chemical compound C=C.CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC PFBWBEXCUGKYKO-UHFFFAOYSA-N 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 2
- 150000002900 organolithium compounds Chemical group 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- ZUDLIFVTNPYZJH-UHFFFAOYSA-N 1,1,2,2-tetraphenylethylbenzene Chemical compound C1=CC=CC=C1C(C(C=1C=CC=CC=1)(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 ZUDLIFVTNPYZJH-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- FWWSGNRCZFIRQI-UHFFFAOYSA-N 1,3-dibromo-4-phenylpyrrole-2,5-dione Chemical compound O=C1N(Br)C(=O)C(Br)=C1C1=CC=CC=C1 FWWSGNRCZFIRQI-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- KPQOXMCRYWDRSB-UHFFFAOYSA-N 1-(2-chlorophenyl)pyrrole-2,5-dione Chemical compound ClC1=CC=CC=C1N1C(=O)C=CC1=O KPQOXMCRYWDRSB-UHFFFAOYSA-N 0.000 description 1
- FECSFBYOMHWJQG-UHFFFAOYSA-N 1-(4-bromophenyl)pyrrole-2,5-dione Chemical compound C1=CC(Br)=CC=C1N1C(=O)C=CC1=O FECSFBYOMHWJQG-UHFFFAOYSA-N 0.000 description 1
- SJLLJZNSZJHXQN-UHFFFAOYSA-N 1-dodecylpyrrole-2,5-dione Chemical compound CCCCCCCCCCCCN1C(=O)C=CC1=O SJLLJZNSZJHXQN-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-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
- FBPVUBVZRPURIU-UHFFFAOYSA-N 1-hexylpyrrole-2,5-dione Chemical compound CCCCCCN1C(=O)C=CC1=O FBPVUBVZRPURIU-UHFFFAOYSA-N 0.000 description 1
- NQDOCLXQTQYUDH-UHFFFAOYSA-N 1-propan-2-ylpyrrole-2,5-dione Chemical compound CC(C)N1C(=O)C=CC1=O NQDOCLXQTQYUDH-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- QRIMLDXJAPZHJE-UHFFFAOYSA-N 2,3-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CO QRIMLDXJAPZHJE-UHFFFAOYSA-N 0.000 description 1
- QZLAEIZEPJAELS-UHFFFAOYSA-N 2,4,4-trimethylpentane-2-thiol Chemical compound CC(C)(C)CC(C)(C)S QZLAEIZEPJAELS-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- NPSJHQMIVNJLNN-UHFFFAOYSA-N 2-ethylhexyl 4-nitrobenzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=C([N+]([O-])=O)C=C1 NPSJHQMIVNJLNN-UHFFFAOYSA-N 0.000 description 1
- 239000004808 2-ethylhexylester Substances 0.000 description 1
- XPQNCCVGADKLSD-UHFFFAOYSA-N 2-ethylpentyl prop-2-enoate Chemical compound CCCC(CC)COC(=O)C=C XPQNCCVGADKLSD-UHFFFAOYSA-N 0.000 description 1
- MPBLPZLNKKGCGP-UHFFFAOYSA-N 2-methyloctane-2-thiol Chemical compound CCCCCCC(C)(C)S MPBLPZLNKKGCGP-UHFFFAOYSA-N 0.000 description 1
- SEDMFAYCVMLBFB-UHFFFAOYSA-N 2-methylpentyl prop-2-enoate Chemical compound CCCC(C)COC(=O)C=C SEDMFAYCVMLBFB-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- UFQHFMGRRVQFNA-UHFFFAOYSA-N 3-(dimethylamino)propyl prop-2-enoate Chemical compound CN(C)CCCOC(=O)C=C UFQHFMGRRVQFNA-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- SSMDYRHBKZVGNR-UHFFFAOYSA-N 3-propan-2-ylpyrrole-2,5-dione Chemical compound CC(C)C1=CC(=O)NC1=O SSMDYRHBKZVGNR-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
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 description 1
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- FWCDLNRNBHJDQB-UHFFFAOYSA-N [2-(hydroxymethyl)-3-octadecanoyloxy-2-(octadecanoyloxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(COC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC FWCDLNRNBHJDQB-UHFFFAOYSA-N 0.000 description 1
- YUGHSWSVZKPPEG-UHFFFAOYSA-N [3-dodecanoyloxy-2,2-bis(dodecanoyloxymethyl)propyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCC(COC(=O)CCCCCCCCCCC)(COC(=O)CCCCCCCCCCC)COC(=O)CCCCCCCCCCC YUGHSWSVZKPPEG-UHFFFAOYSA-N 0.000 description 1
- WXZIKFXSSPSWSR-UHFFFAOYSA-N [Li]CCCCC Chemical compound [Li]CCCCC WXZIKFXSSPSWSR-UHFFFAOYSA-N 0.000 description 1
- BZEZSORUWZUMNU-UHFFFAOYSA-N [Li]CCCC[Li] Chemical compound [Li]CCCC[Li] BZEZSORUWZUMNU-UHFFFAOYSA-N 0.000 description 1
- TVKQVMQEOOKKMN-UHFFFAOYSA-N [Li]CCC[Li] Chemical compound [Li]CCC[Li] TVKQVMQEOOKKMN-UHFFFAOYSA-N 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000004703 alkoxides 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
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- LEKSIJZGSFETSJ-UHFFFAOYSA-N cyclohexane;lithium Chemical compound [Li]C1CCCCC1 LEKSIJZGSFETSJ-UHFFFAOYSA-N 0.000 description 1
- CMKBCTPCXZNQKX-UHFFFAOYSA-N cyclohexanethiol Chemical compound SC1CCCCC1 CMKBCTPCXZNQKX-UHFFFAOYSA-N 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- CIKJANOSDPPCAU-UHFFFAOYSA-N ditert-butyl cyclohexane-1,4-dicarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1CCC(C(=O)OOC(C)(C)C)CC1 CIKJANOSDPPCAU-UHFFFAOYSA-N 0.000 description 1
- VMRTVQZUEDMYNS-UHFFFAOYSA-N ditert-butyl nonanediperoxoate Chemical compound CC(C)(C)OOC(=O)CCCCCCCC(=O)OOC(C)(C)C VMRTVQZUEDMYNS-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 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
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- CETVQRFGPOGIQJ-UHFFFAOYSA-N lithium;hexane Chemical compound [Li+].CCCCC[CH2-] CETVQRFGPOGIQJ-UHFFFAOYSA-N 0.000 description 1
- YNXURHRFIMQACJ-UHFFFAOYSA-N lithium;methanidylbenzene Chemical compound [Li+].[CH2-]C1=CC=CC=C1 YNXURHRFIMQACJ-UHFFFAOYSA-N 0.000 description 1
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- QJAOYSPHSNGHNC-UHFFFAOYSA-N octadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCCCS QJAOYSPHSNGHNC-UHFFFAOYSA-N 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- AMLFJZRZIOZGPW-UHFFFAOYSA-N prop-1-en-1-amine Chemical compound CC=CN AMLFJZRZIOZGPW-UHFFFAOYSA-N 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 1
- DEDZSLCZHWTGOR-UHFFFAOYSA-N propylcyclohexane Chemical compound CCCC1CCCCC1 DEDZSLCZHWTGOR-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- HVQSLQDEWCORBX-UHFFFAOYSA-N tert-butyl 5-(8-tert-butylperoxy-8-oxooctyl)-2-hexylcyclohexane-1-carboperoxoate Chemical compound CCCCCCC1CCC(CCCCCCCC(=O)OOC(C)(C)C)CC1C(=O)OOC(C)(C)C HVQSLQDEWCORBX-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
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は透明ポリスチレン系樹脂組成物に関するものである。詳しくは、本発明は、優れた透明性と加工性を有すると同時に成形加工時における金型の汚れを大幅に改善した透明ポリスチレン系樹脂組成物に関する。
【０００２】
【従来の技術及び発明が解決しようとする課題】
スチレン系樹脂は、良好な強度と成形加工性を有している材料である。特に透明のスチレン系樹脂は広く透明食品容器、包装用材料などの家庭用品、家電製品、およびOA機器周辺部品等に応用されているが、製品の薄肉化および大型化のニーズが日々増しており、より高度な成形加工性が要求されている。物性を低下させないで樹脂成型品の加工性を増すために、既存の方法では例えばスチレン系樹脂中に少量の滑剤を成形補助剤として添加して成形加工時の流動性を改善している。スチレン系樹脂に使われる成形補助剤は一般的に脂肪酸金属塩類が挙げられ、その中で、ステアリン酸カルシウム、ステアリン酸亜鉛、脂肪酸アミド類（例えばエチレンビスステアリルアミド）が加工性改善に効果を示す。例えば特公平2-52923号には、スチレン系樹脂の製造において反応槽に1〜8重量部のエチレンビスステアリルアミド溶液を加入することによって樹脂の加工性を改善することが開示されている。特開昭63-33455号には、スチレン系樹脂中にステアリン酸カルシウムあるいはステアリン酸亜鉛を加えて混合すれば樹脂成形加工時の離型性が改善されることが開示されている。
【０００３】
また、特開平7-82439号には、スチレン系樹脂にステアリン酸ブチルおよび少量のトリグリセライドを添加すれば樹脂の流動性と耐衝撃性が改善されることが開示されている。
【０００４】
以上のように、それぞれの先行技術では（透明の）スチレン系樹脂に滑剤あるいは離型剤などの添加物を添加して樹脂の加工性および離型性が改善できるが、それらの添加物は樹脂の透明性を悪くして良好な透明度を持つスチレン系樹脂を得ることはできなくなる。また添加剤によって射出成形時に金型汚れをもたらすことがあり、特に高温、薄肉化の射出成形時においてその問題がより顕著となる。
【０００５】
【課題を解決するための手段】
上記の欠点を解決するために、本発明は透明性、加工性が良く且つ成形加工時に金型汚れが無い透明ポリスチレン系樹脂組成物を提供するものである。
【０００６】
すなわち、本発明は、（Ｉ）100重量部の透明ポリスチレン系樹脂に対して、（II）0.01〜4重量部のペンタエリスリトール系エステル類化合物を含有する透明ポリスチレン系樹脂組成物であって、前記（Ｉ）透明ポリスチレン系樹脂のジクロロメタン可溶分中の分子量350未満の低分子量重合体の比率が2.0重量％以下であり、且つ下記式(1)を満たす透明ポリスチレン系樹脂組成物に関する。
0.52＜X＋2Y＜4.50 式(1)
X；前記（Ｉ）透明ポリスチレン系樹脂100重量部に対する（II）ペンタエリスリトール系エステル類化合物の重量部
Y；前記（Ｉ）透明ポリスチレン系樹脂のジクロロメタン可溶分中の分子量350未満の低分子量重合体の重量％。
【０００７】
本発明において、「透明」のポリスチレン系樹脂とは、光線透過率が60％以上の透明性を有するものを指す。
【０００８】
【発明の実施の形態】
本発明の（Ｉ）透明ポリスチレン系樹脂は二種類に分けられ、即ちゴム変性の透明ポリスチレン系樹脂とゴムを含まない透明ポリスチレン系樹脂である。ゴムを含まない透明ポリスチレン系樹脂はスチレン系モノマーが30重量％以上であるスチレン系樹脂が好ましく、スチレン系モノマー100〜30重量％とその他の共重合モノマー0〜70重量％から成るものが挙げられる。その他の共重合モノマーに関しては特別な制限が無くスチレンモノマーと共重合できて且つ一定の透明性に達するものであれば良い。スチレン系モノマーは、後述のゴム変性した透明スチレン系樹脂のゴム状重合体で例示するものが使用できる。
【０００９】
ゴムを含まない本発明の（Ｉ）透明ポリスチレン系樹脂に用いられる共重合モノマーとしては、例えば（メタ）アクリル酸エステル系モノマー、アクリロニトリル系モノマー、マレイミド系モノマー、（メタ）アクリル酸、および無水マレイン酸が挙げられる。
【００１０】
その中で、（メタ）アクリル酸エステル系モノマーとしてはアクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、メタクリル酸メチル、メタクリル酸ベンジル、メタクリル酸ヘキシル、メタクリル酸サイクロヘキシル、メタクリル酸ドデシル、メタクリル酸2-ヒドロキシエチル、メタクリル酸グリセリン、およびメタクリル酸ジメチルアミノエチルなどが挙げられる。その中で、メタクリル酸メチルがより好ましい。
【００１１】
アクリロニトリル系モノマーはアクリロニトリルとα-メタクリロニトリルがあるが、アクリロニトリルがより好ましい。
【００１２】
マレイミド系モノマーはN-メチルマレイミド、N-イソプロピルマレイミド、N-ブチルマレイミド、N-ヘキシルマレイミド、N-オクチルマレイミド、N-ドデシルマレイミド、N-サイクロヘキシルマレイミド、N-フェニルマレイミド、N-2,3-ジメチルフェニルマレイミド、N-2,4-ジメチルフェニルマレイミド、N-2,3-ジエチルフェニルマレイミド、N-2,4-ジエチルフェニルマレイミド、N-2,3-ジブチルフェニルマレイミド、N-2,4-ジブチルフェニルマレイミド、N-2,6-ジメチルフェニルマレイミド、N-2,3-ジクロロフェニルマレイミド、N-2,4-ジクロロフェニルマレイミド、N-2,3-ジブロムフェニルマレイミド、N-2,4-ジブロムフェニルマレイミドなどが挙げられるが、N-フェニルマレイミドがより好ましい。
【００１３】
ゴムを含まない（Ｉ）透明ポリスチレン系樹脂の具体例としては、ポリスチレン等のスチレン系重合体、スチレン系−アクリロニトリル系共重合体、スチレン系−（メタ）アクリル酸エステル系共重合体、スチレン系−N-置換マレイミド系−アクリロニトリル系共重合体、スチレン系−N-置換マレイミド系共重合体、スチレン系−（メタ）アクリル酸エステル系−N-置換マレイミド系共重合体、スチレン系−N-置換マレイミド系−アクリロニトリル系−（メタ）アクリル酸エステル系共重合体などがある。これらは二種以上を併用してもよい。
【００１４】
本発明のもう一種類の透明ポリスチレン系樹脂はゴム変性した透明ポリスチレン系樹脂であり、より好ましくはジエン系ゴムで変性した透明ポリスチレン系樹脂である。該樹脂は、ゴムとゴムを含まない透明ポリスチレン系樹脂の混合物、あるいはゴムとスチレン系モノマー及びその他の共重合可能なモノマーでグラフト重合して得られるものが挙げられる。上述のゴムは例えばブタジエンゴム、ブタジエン−スチレン共重合体が挙げられる。グラフト重合で得られるゴム変性の透明ポリスチレン系樹脂についての好ましい構造は、ゴム状重合体からなるゴム粒子分散相(A)およびスチレン系モノマー12〜70重量％、（メタ）アクリル酸エステル系モノマー20〜80重量％、アクリロニトリル系モノマー0〜20重量％、その他の共重合可能なモノマー0〜40重量％からなる共重合体連続相(B)から構成されるものである。
【００１５】
上述の分散相(A)におけるゴム状重合体は、好ましくはスチレン系モノマー5〜50重量％およびジエン系モノマー95〜50重量％から構成されるゴム状共重合体である。このようなゴム状共重合体は、例えば有機溶剤存在下において有機リチウム化合物を開始剤としてスチレン系モノマー、ジエン系モノマー、および適量の溶剤でアニオン重合反応を行いブロック共重合体として得られる。このようなゴム状共重合体は、ムーニー(Mooney)粘度(ＭＬ1+4)が20〜80、25℃における5重量％のスチレンモノマー溶液の粘度が3〜60cps、ジエン系ユニット中の1,2-ビニル構造が8重量％以上、ポリスチレンブロックの含有量がゴム状共重合体の5〜35重量％を占めることが好ましい。上記のゴム状共重合体の構造は、各ブロックは均一重合体のブロック(Block)構造、部分ランダムブロック構造、テーパーブロック(taper-block)構造、線状型構造および分枝構造などがある。代表的な構造は下記の通りである。
【００１６】
（１）線状型ブロック共重合体
（１−１） (Ａ−Ｂ)n
（１−２） Ａ−(Ｂ−Ａ)n
（１−３） Ｂ−(Ａ−Ｂ)n
ここで、Ａはスチレン系を主成分とする重合体ブロック、Ｂはジエン系を主成分とする重合体ブロックを指すが、ＡブロックとＢブロック間の境界は特に明確な区別が無く、またnは１以上の整数である。
【００１７】
（２）分岐型ブロック重合体
（２−１） [(Ｂ−Ａ)n]m-2Ｘ
（２−２） [(Ａ−Ｂ)n]m-2Ｘ
（２−３） [(Ｂ−Ａ)nＢ]m-2Ｘ
（２−４） [(Ａ−Ｂ)nＡ]m-2Ｘ
ここで、Ａ、Ｂは（１）と同じだが、Ｘはカップリング剤の残基（例えばテトラクロロシラン、テトラクロロ錫など）または多官能の有機リチウム化合物残基である。nおよびmは1〜10の整数である。
【００１８】
（３）上述の（１）項および（２）項の任意形式の混合物。
【００１９】
また、テーパーブロック構造はスチレンテーパーブロック構造あるいはブタジエンテーパーブロック構造であり、具体例は下記である。
Ｄ-Ｄ/Ｓ-Ｓ、(Ｓ-Ｄ/Ｓ)n-Ｓ、Ｄ-Ｓ-Ｄ/Ｓ-Ｓ、Ｄ/Ｓ-(Ｓ-Ｄ/Ｓ)n、Ｄ-Ｓ-Ｄ/Ｓ-Ｓ-Ｄ、Ｘ-[(Ｓ-Ｄ/Ｓ)n]m+1、Ｓ-Ｄ-Ｄ/Ｓ-Ｓ、Ｘ-[(Ｄ/Ｓ-Ｓ)n]m+1、Ｄ/Ｓ-Ｓ-Ｄ-Ｓ、Ｘ-[(Ｓ-Ｄ/Ｓ)n-Ｓ]m+1、Ｓ-Ｄ/Ｓ-Ｓ、Ｘ-[(Ｄ/Ｓ-Ｓ)n-Ｄ/Ｓ]m+1、(Ｓ-Ｄ/Ｓ)n、Ｄ-Ｄ/Ｓ-Ｓ-Ｓ-Ｄ/Ｓ-Ｄ
ここで、Ｓはポリスチレン系ブロック、Ｄはポリジエン系ブロック、Ｄ/Ｓはスチレン系あるいはジエン系のテーパーブロック、Ｘは多官能性開始剤の残基または多官能性カップリング剤の残基、m、nは1〜10の整数を指す。上記の例の中で好ましいのはＤ-Ｄ/Ｓ-ＳあるいはＤ-Ｓ-Ｄ/Ｓ-Ｓ、Ｄ-Ｄ/Ｓ-Ｓ-Ｓ-Ｄ/Ｓ-Ｄである。本発明においてテーパーブロック構造はより適切である。
【００２０】
スチレン系モノマーとしては、スチレン、α−メチルスチレン、パラメチルスチレン、メタメチルスチレン、エチルスチレン、2,4-ジメチルスチレン、パラ-t-ブチルスチレン、ブロムスチレンなどが挙げられる。これらのモノマーは１種あるいは２種以上を併用しても良い。
【００２１】
ジエン系モノマーとしては、1,3-ブタジエン、2-メチル-1,3-ブタジエン、2,3-ジメチル-1,3-ブタジエン、1,3-ペンタジエン、1,3-ヘキサジエンなどが挙げられる。これらのモノマーは１種あるいは２種以上を併用しても良い。その中で1,3-ブタジエンまたは2-メチル-1,3-ブタジエンがより好ましい。
【００２２】
上記ゴム状共重合体の製造に使われる有機リチウム化合物触媒はその分子中に一個以上のリチウム原子を含む化合物で、例えばエチルリチウム、ｎ-ペンチルリチウム、イソプロピルリチウム、ｎ-ブチルリチウム、sec-ブチルリチウム、ヘキシルリチウム、サイクロヘキシルリチウム、フェニルリチウム、ベンジルリチウム、ナフタリルリチウム、t-ブチルリチウム、トリメチレンジリチウム、テトラメチレンジリチウム、ブタジエニルジリチウム、およびイソプレニルジリチウムなどが挙げられ、これらは一種または二種以上の混用ができる。
【００２３】
上記ゴム状共重合体の、重合する時の重合速度、1,2-ビニル基の含有量、およびジエン系モノマーとスチレン系モノマーとの反応速度およびランダム化度は、極性化合物またはランダム化剤で調整できる。その極性化合物またはランダム化剤としては、例えばエーテル類、アミン類、チオエーテル、アルキルベンゼンスルホン酸類のアルカリ塩、カリウムまたはナトリウムのアルコキシドが挙げられる。
【００２４】
また、本発明において、共重合体連続相（B）は12〜70重量％のスチレン系モノマー、20〜80重量％の（メタ）アクリル酸エステル系モノマー、0〜20重量％のアクリロニトリル系モノマー、0〜40重量％のその他の共重合モノマーから成るものが好ましい。その中でスチレン系モノマーは上述のゴム状共重合体で例示する如きものが使用できる。
【００２５】
また、共重合体連続相（B）の製造に用いられる（メタ）アクリル酸エステル系モノマーとしては、メタクリル酸エステル類ではメタクリル酸メチル、メタクリル酸エチル、メタクリル酸ブチル、メタクリル酸グリシジルなどがあり、アクリル酸エステル類ではアクリル酸メチル、アクリル酸エチル、アクリル酸n-ブチル、アクリル酸2-メチルペンチル、アクリル酸2-エチルペンチル、アクリル酸オクチル、アクリル酸ジエチルアミノエチル、アクリル酸ジメチルアミノプロピルなどが挙げられるが、メタクリル酸メチルとアクリル酸n-ブチルがより好ましい。
【００２６】
また、共重合体連続相（B）の製造に用いられるアクリロニトリル系モノマーはアクリロニトリル、α-メチルアクリロニトリルなどがある。
【００２７】
また、共重合体連続相（B）の製造に用いられる共重合可能なモノマーは共重合体のモノマー比率の0〜40重量％を占めるが、その種類に関しては特別な制限が無く、必要によって各共重合モノマーの含有量比を調製して最終的な樹脂組成物が一定の透明度に達するようにする。具体的に例を挙げると、イタコン酸、マレイン酸、フマル酸、ブテン酸、シンナミン酸などの不飽和脂肪酸、N-メチルマレイミド、N-エチルマレイミド、N-ブチルマレイミド、N-オクチルマレイミド、N-イソプロピルマレイミド、N-フェニルマレイミド、N-パラブロモ-フェニルマレイミド、N-オルトクロロ-フェニルマレイミド、N-サイクロヘキシルマレイミドなどのマレイミド類、無水マレイン酸、無水イタコン酸、無水シトラコン酸などの不飽和無水物、及びプロペニルアミンや、アクリルアミド、N-メチルアクリルアミドなどのアクリルアミド系モノマーなどが挙げられる。
【００２８】
本発明の樹脂組成物の共重合体連続相(B)の重量平均分子量に関しては特別な制限が無いが、一般的には50,000〜300,000、好ましくは60,000〜200,000、より好ましくは70,000〜150,000である。重量平均分子量が50,000以上であれば樹脂組成物の耐衝撃強度が良好となる。一方重量平均分子量が300,000以下であれば樹脂組成物の流動性が良好となり加工性と透明性が良くなる。また、本発明において、分散相(A)のゴム粒子の重量平均粒径に関しては特に制限が無いが、一般的には0.1〜2.0μm、好ましくは0.1〜1.5μm、より好ましくは0.2〜1.0μmである。ゴム粒子の重量平均粒径が0.1μm以上であれば樹脂組成物の衝撃強度が良好となる。重量平均粒径が2.0μm以下であれば樹脂組成物の透明性が良好となる。上記のゴム粒子の重量平均粒径は透過型電子顕微鏡（超薄切片法）の写真から求められる。写真中から粒子を最低300個以上取出してサイズを測定する。その重量平均粒径は下式により算出される。
【００２９】
【数１】
本発明の樹脂組成物のゲル含有量はトルエン／アセトン（重量比１／１）にての不溶分として求められるが特別な制限が無く、一般的に２〜40重量％、好ましくは8〜35重量％、より好ましくは12〜30重量％である。また、本発明の樹脂組成物の膨潤指数に関しては特別な制限が無いが一般的に2〜25、好ましくは3〜20、より好ましくは5〜15である。
【００３１】
本発明の（Ｉ）透明ポリスチレン系樹脂は、そのジクロロメタン可溶分中、分子量が350より小さい低分子量重合体の比率が可溶分全体の2.0重量％以下であり、好ましくは1.0重量％以下、より好ましくは0.6重量％以下である。この比率が2.0重量％以下であればポリスチレン系樹脂の成形加工時に金型汚れ現象が抑制でき製品の斑も発生しにくくなる。ここで分子量が350未満の低分子重合体は、透明ポリスチレン系樹脂をジクロロメタン溶剤に溶かして溶けた部分（可溶分）についてGC-MS分析法（ガスクロマトグラフ−質量分析法）を用いて分子量350未満の低分子量重合体の含有量を測定することによって得られる（スチレン標準面積で換算）。分子量が350未満の低分子量重合体（例えば三量体、二量体）としては、例えばＡＭＳ、ＭＭＳ、ＡＳ、ＭＳＳ、ＳＳＳ、ＭＳなどがある。ここでＡはアクリロニトリルモノマー、Ｍは（メタ）アクリル酸メチルモノマー、Ｓはスチレンモノマーを表わす。
【００３２】
本発明の透明ポリスチレン系樹脂組成物に使用されるペンタエリスリトール系エステル類化合物は、ペンタエリスリトールとカルボン酸とが反応してできたエステル化合物である。カルボン酸としては、ラウリン酸、パルミチン酸、ステアリン酸、アラキドン酸、ベヘン酸、リグノセリン酸、セロチン酸、モンタン酸、オレイン酸、エライジン酸、エルカ酸、リノール酸、リノレン酸などが挙げられる。これらのカルボン酸は二種以上を併用してもよい。
【００３３】
本発明の透明ポリスチレン系樹脂組成物に用いられるペンタエリスリトールのエステル類の具体例としては、ペンタエリスリトールトリステアレート、ペンタエリスリトールテトラステアレート、ペンタエリスリトールテトララウレート等が挙げられるが、好ましくはペンタエリスリトールテトラステアレートである。上記のエステル化合物はエステル反応によって得られるが、場合によって触媒（例えば有機錫）を使う。反応中のアルコールとカルボン酸の使用量はその種類および量で決定される。
【００３４】
本発明における（II）ペンタエリスリトール系エステル類の添加量は100重量部の（Ｉ）透明ポリスチレン系樹脂に対して0.01〜4重量部であり、好ましくは0.02〜3重量部、より好ましくは0.05〜1.5重量部である。（II）ペンタエリスリトール系エステル類の添加量がこの範囲内の場合、本発明の透明ポリスチレン系樹脂組成物の成形加工性、離型性、金型汚れ防止性、透明性及び耐熱性が優れるほか、衝撃強度も良くなる。具体的には、該添加量が0.01重量部より小さい場合はスチレン系樹脂の成形加工性、離型性が悪くなる。一方その添加量が5重量部より大きくなると金型汚れが酷くなり、樹脂組成物の耐熱性および透明性が悪くなる。
【００３５】
本発明の透明ポリスチレン系樹脂組成物は、前記式(1)を満たすが、好ましくは0.60＜X＋2Y＜3.50、より好ましくは0.70＜X＋2Y＜3.00を満たす。式(1)を満たさないと、成形加工性、離型性、金型汚れ防止性が改善され、優れた透明性を有するポリスチレン系樹脂組成物は得られない。
【００３６】
ペンタエリスリトール系エステル類化合物の添加方式には特別な制限が無いが、（Ｉ）透明ポリスチレン系樹脂の重合の時に添加する方法、または重合後に添加する方法、または押出機あるいは混合機方式で添加する方法などがある。
【００３７】
本発明の（Ｉ）透明ポリスチレン系樹脂の製法は乳化、懸濁、塊状（または溶液）重合法、または上記重合法の組合せが考えられるが、好ましくは乳化または塊状（または溶液）重合法、より好ましくは塊状（または溶液）重合法である。
【００３８】
また、本発明の（Ｉ）樹脂のうち、ゴム変性透明ポリスチレン系樹脂の製法の一つとしては、ゴム状共重合体の存在下においてスチレン系モノマー、（メタ）アクリル酸エステル系モノマー、アクリロニトリル系モノマーおよび必要に応じてその他の共重合可能なモノマーをバッチ式または連続式塊状または溶液重合法にてグラフト重合反応をさせる方法が挙げられる。連続式溶液重合を例に取ると、先ず上記のゴム状共重合体およびモノマーを適量の溶剤に加えて原料混合溶液を形成する。その原料混合溶液は高剪断、高攪拌能力を有する溶解槽で溶解させる。その溶解槽には、帯状螺旋式攪拌葉、螺旋櫂式攪拌葉、またはその他高剪断力を発生する攪拌葉などが設置され、十分に時間を掛けて上記のゴム状共重合体を完全に溶解させてゴム溶液状にし、それをポンプで反応器へ送る。上記の原料溶液またはモノマー溶液をそれぞれ連続的に第一反応器および／または第二反応器、および／またはその後続の反応器供給する。必要に応じて第一及び／または第二および／またはその後続の反応器に連鎖移動剤、開始剤を添加してグラフト重合反応を行う。
【００３９】
上記の反応槽は連続攪拌式（CSTR）、プラグフロー式（plug flow reactor）、静力混合式（static）の一種または二種以上の組合せで良い。反応温度は70〜230℃に保ち、最終モノマー転化率は30〜95％、好ましくは50〜90％である。
【００４０】
本発明の（Ｉ）透明ポリスチレン系樹脂の重合に用いられる溶剤としては、芳香族炭化水素化合物、ケトン類、エステル類が挙げられるが、好ましくは芳香族炭化水素化合物である。具体例としては、トルエン、エチルベンゼンおよびキシレンが挙げられる。ケトン類では好ましくはブタノンである。エステル類では好ましくは酢酸エチルである。その他、サイクロヘキサン、n-ヘプタンなどの脂肪族炭化水素化合物は溶剤の一部分として使用できる。
【００４１】
本発明の（Ｉ）透明ポリスチレン系樹脂は、製造中に開始剤を使用する。使われる開始剤としては、ベンゾイルパーオキシド（過酸化ベンゾイル）、ジクミルパーオキシド、t-ブチルパーオキシド、t-ブチルハイドロパーオキシド、クーメンハイドロパーオキシド、t-ブチルパーオキシベンゾエート、ジ−2−エチルヘキシルパーオキシジカルボネート、t-ブチルパーオキシイソプロピルカルボネート（略称BPIC）、サイクロヘキサノンパーオキシド、2,2'−アゾ-ビス-イソブチロニトリル、1,1'−アゾ-ビス-1−サイクロヘキサンカルボニトリル、2,2'−アゾ-ビス-2−メチルブチロニトリル、アゾ-ビス-イソブチロニトリル、1,1−ジ-(t-ブチルパーオキシ)サイクロヘキサン（略称TX-22）、1,1−ジ−(t-ブチルパーオキシ)3,3,5−トリメチルサイクロヘキサン（略称TX-29A）、2,5−ジメチル−2,5‐ビス‐（2-エチルヘキサノキシパーオキシ）ヘキサン、4−(t-ブチルパーオキシカルボニル)‐3‐ヘキシル-6‐[7−(t-ブチルパーオキシカルボニル)ヘプチル]サイクロヘキサン、ジーt-ブチル-ジパーオキシアゼレート、2,5−ジメチル−2,5−ビス−（ベンゾイルパーオキシ）ヘキサン、ジ-t-ブチルパーオキシヘキサハイドロ-テレフタレート（略称BPHTP）、2,2−ビス−（4,4−ジ‐t-ブチルパーオキシ）サイクロヘキサニルプロパンなどが挙げられる。
【００４２】
本発明の透明ポリスチレン系樹脂組成物の製造に当たって必要に応じて連鎖移動剤を使う。連鎖移動剤としては以下のものが挙げられる。
・メルカプタン類：メチルメルカプタン、n-ブチルメルカプタン、サイクロヘキシルメルカプタン、n-ドデシルメルカプタン、ステアリルメルカプタン、t-ドデシルメルカプタン(略称TDM)、n-プロピルメルカプタン、n-オクチルメルカプタン、t-オクチルメルカプタン、t-ノニルメルカプタン、メルカプトプロピオン酸の2-エチルヘキシルエステル等。
・アルキルアミン類：モノエチルアミン、ジエチルアミン、トリエチルアミン、モノイソプロピルアミン、ジイソプロピルアミン、モノブチルアミン、ジ−n-ブチルアミン、トリ‐n-ブチルアミン等。
・その他：ペンタフェニルエタン、α−メチルスチレンダイマー、テルピノレン等。
【００４３】
上述の重合反応終了後に反応器からものを取出し脱揮発装置を経て未反応のモノマー、溶剤などの低揮発成分を除き、重合体を回収することにより透明ポリスチレン系樹脂が得られる。
【００４４】
上記の通り、（II）ペンタエリスリトール系エステル類化合物の添加方式には特別な制限は無いが、具体的な添加方式として、得られた（Ｉ）透明ポリスチレン系樹脂に溶融混練する方法が挙げられる。例えば、バンバリーミキサー、ロール混練機および一軸または二軸押出機などの溶融混練機を用いて、一般的に160〜280℃、好ましくは180〜250℃の温度で混練する。混練後押出して得られた押出し物は冷却後製粒されペレット状となして成形に供される。また、混練を行う時の各成分の添加順序については特別に制限がない。
【００４５】
本発明の樹脂組成物の効果を著しく阻害させない範囲内においてその他の成分を加えることができる。例えば着色剤、充填剤、難燃剤、難燃助剤（酸化アンチモンなど）、光安定剤、熱安定剤、可塑剤、滑剤、離型剤、増粘剤、帯電防止剤、酸化防止剤、導電剤などの添加剤が挙げられる。具体例としては、鉱物油、ステアリン酸ブチルなどのエステル系可塑剤、ポリエステル系可塑剤、ポリジメチルシロキサンのような有機ポリシロキサン類、高級脂肪酸および金属塩、立体障害アミン系酸化防止剤、ガラス繊維などがある。それぞれは単独使用または混合併用ができる。上記のエステル系可塑剤または鉱物油の使用量は100重量部の樹脂組成物に対して一般的に0〜5重量部であり、好ましくは0.05〜2重量部である。一方、有機ポリシロキサンの使用量は一般的に0〜0.5重量部であり、好ましくは0.002〜0.2重量部であり、その構造としては、特にジメチルポリシロキサン分子量が800〜10万のものが好ましい。
【００４６】
【発明の効果】
本発明によれば、優れた透明性と加工性を有すると同時に成形加工時における金型の汚れを大幅に改善した透明ポリスチレン系樹脂組成物が得られる。
【００４７】
【実施例】
［物性測定］
（１）透明性（霧度、Haze）
厚さ3mmの射出成形シートを用いて、ASTM D-1003標準に従って透明性を測定する。Haze値が高ければ高いほど透明性が悪いことを表わす。
【００４８】
（２）透過率（Transmittance）
ASTM-1003基準に従い厚さ3mmの試験片を測定する。単位は％で表わす。
【００４９】
（３）加工性（Spiral flow）
透明ポリスチレン系樹脂組成物を東芝IS100EN射出成形機にて、シリンダー温度は220℃、金型温度は60℃、射出圧力は600kg／cm2の成形条件で、肉厚2mmのスパイラル形状金型に射出成形し、そのスパイラル流動長から流動性を評価する。
【００５０】
（４）溶融指数（Melt index、MI）
ASTM D-1238法で測定する。
【００５１】
（５）金型汚れ
280℃で50ショットを連続射出した後、金型の表面と成型品の外観を観察し以下の基準で評価する。
◎：汚染されない。
○：わずかに汚染される。
×：酷く汚染される。
【００５２】
（６）（Ｉ）樹脂のジクロロメタン可溶分中の分子量350未満の低分子量重合体の比率
ポリスチレン系樹脂組成物をジクロロメタン溶剤に溶解して遠心分離器で分離し、上層の可溶分をGC-MS測定器で分析を行う。分子量350未満の低分子量重合体を、スチレン標準面積を基準にして測定し、（Ｉ）透明ポリスチレン系樹脂中の重量％として算出する。GC-MS測定器はヒューレット・パッカード（Hewlett Packard）社「シリーズ番号5890A」を使用した。
【００５３】
実施例１
四個の容量40リットルの完全混合型反応槽を順に繋いで連続重合装置を構成し、透明ポリスチレン系樹脂組成物の製造に用いる。ゴム状共重合体8.4重量部（スチレン／ブタジエン＝25／75重量％、1,2-ビニル基含有量＝15.4％、Mooney粘度が45であるテーパーブロック共重合体）、スチレン23.4重量部、メタクリル酸メチル38.2重量部、エチルベンゼン30重量部、ドデシルメルカプタン0.08重量部、ペンタエリスリトールテトラステアレート0.045重量部、およびベンゾイルパーオキシド0.08重量部を原料溶液とし、ポンプで35kg／hrの流量で連続的に反応槽へ送り重合を行う。第一反応槽の温度は109℃、第二反応槽の温度は114℃、第三反応槽の温度は130℃、第四反応槽の温度は140℃で、総重合転化率は60％となる。重合後重合溶液を反応槽から連続的に脱揮発装置へ送り、脱揮発の真空度を200Torrに保ち未反応のモノマー及び有機溶剤などの揮発性物質を分離させ、出来た樹脂を押出機でペレット状にする。
【００５４】
得られた透明ポリスチレン系樹脂の共重合体連続相の組成はスチレン単位が36重量部、メタクリル酸メチル単位が64重量部であり、分散相ゴム粒子の重量平均粒径は0.42μmである。また、（Ｉ）透明ポリスチレン系樹脂のジクロロメタン可溶分中の分子量350未満の低分子量重合体の比率（以下、単に低分子量重合体の比率という）0.62重量％である。なお、樹脂組成物のペンタエリスリトールテトラステアレートの含有量は0.1重量部（100重量部の透明ポリスチレン系樹脂基準）である。
【００５５】
実施例２
四個の容量40リットルの完全混合型反応槽を順に繋いで連続重合装置を構成し、透明ポリスチレン系樹脂組成物の製造に用いる。ゴム状共重合体8.4重量部（スチレン／ブタジエン＝25／75重量％、1,2-ビニル基含有量＝15.4％、Mooney粘度が45であるテーパーブロック共重合体）、スチレン23.4重量部、メタクリル酸メチル38.2重量部、エチルベンゼン30重量部、ドデシルメルカプタン0.09重量部、ペンタエリスリトールテトラステアレート0.14重量部、およびベンゾイルパーオキシド0.09重量部を原料溶液とし、ポンプで35kg／hrの流量で連続的に反応槽へ送り重合を行う。第一反応槽の温度は103℃、第二反応槽の温度は107℃、第三反応槽の温度は122℃、第四反応槽の温度は132℃で、総重合転化率は60％となる。重合後重合溶液を反応槽から連続的に脱揮発装置へ送り、脱揮発の真空度を130Torrに保ち未反応のモノマー及び有機溶剤などの揮発性物質を分離させ、出来た樹脂を押出機でペレット状にする。
【００５６】
得られた透明ポリスチレン系樹脂の共重合体連続相の組成はスチレン単位が36重量部、メタクリル酸メチル単位が64重量部であり、分散相ゴム粒子の重量平均粒径は0.41μmである。また、低分子量重合体の比率は0.43重量％である。なお、樹脂組成物のペンタエリスリトールテトラステアレートの含有量は0.3重量部（100重量部の透明ポリスチレン系樹脂基準）である。
【００５７】
実施例３
四個の容量40リットルの完全混合型反応槽を順に繋いで連続重合装置を構成し、透明ポリスチレン系樹脂組成物の製造に用いる。ゴム状共重合体8.4重量部（スチレン／ブタジエン＝25／75重量％、1,2-ビニル基含有量＝15.4％、Mooney粘度が45であるテーパーブロック共重合体）、スチレン22.8重量部、メタクリル酸メチル37.0重量部、アクリロニトリル1.8重量部、エチルベンゼン30重量部、ドデシルメルカプタン0.1重量部、ペンタエリスリトールテトラステアレート0.32重量部、およびベンゾイルパーオキシド0.1重量部を原料溶液とし、ポンプで35kg／hrの流量で連続的に反応槽へ送り重合を行う。第一反応槽の温度は102℃、第二反応槽の温度は106℃、第三反応槽の温度は117℃、第四反応槽の温度は127℃で、総重合転化率は60％となる。重合後重合溶液を反応槽から連続的に脱揮発装置へ送り、脱揮発の真空度を80Torrに保ち未反応のモノマー及び有機溶剤などの揮発性物質を分離させ、出来た樹脂を押出機でペレット状にする。
【００５８】
得られた透明ポリスチレン系樹脂の共重合体連続相の組成はスチレン単位が34重量部、メタクリル酸メチル単位が63重量部、アクリロニトリル単位が３重量部であり、分散相ゴム粒子の重量平均粒径は0.35μmである。また、低分子量重合体の比率は0.22重量％である。なお、樹脂組成物のペンタエリスリトールテトラステアレートの含有量は0.7重量部（100重量部の透明ポリスチレン系樹脂基準）である。
【００５９】
実施例４
四個の容量40リットルの完全混合型反応槽を順に繋いで連続重合装置を構成し、透明ポリスチレン系樹脂組成物の製造に用いる。ゴム状共重合体8.4重量部（スチレン／ブタジエン＝25／75重量％、1,2-ビニル基含有量＝15.4％、Mooney粘度が45であるテーパーブロック共重合体）、スチレン22.8重量部、メタクリル酸メチル37.0重量部、アクリロニトリル1.8重量部、エチルベンゼン30重量部、ドデシルメルカプタン0.1重量部、ペンタエリスリトールテトラステアレート0.91重量部、およびベンゾイルパーオキシド0.1重量部を原料溶液とし、ポンプで35kg／hrの流量で連続的に反応槽へ送り重合を行う。第一反応槽の温度は102℃、第二反応槽の温度は106℃、第三反応槽の温度は117℃、第四反応槽の温度は127℃で、総重合転化率は60％となる。重合後重合溶液を反応槽から連続的に脱揮発装置へ送り、脱揮発の真空度を80Torrに保ち未反応のモノマー及び有機溶剤などの揮発性物質を分離させ、出来た樹脂を押出機でペレット状にする。
【００６０】
得られた透明ポリスチレン系樹脂の共重合体連続相の組成はスチレン単位が34重量部、メタクリル酸メチル単位が63重量部、アクリロニトリル単位が３重量部であり、分散相ゴム粒子の重量平均粒径は0.35μmである。また、低分子量重合体の比率は0.21重量％である。なお、樹脂組成物のペンタエリスリトールテトラステアレートの含有量は2.0重量部（100重量部の透明ポリスチレン系樹脂基準）である。
【００６１】
実施例５
四個の容量40リットルの完全混合型反応槽を順に繋いで連続重合装置を構成し、透明ポリスチレン系樹脂組成物の製造に用いる。ゴム状共重合体8.4重量部（スチレン／ブタジエン＝25／75重量％、1,2-ビニル基含有量＝15.4％、Mooney粘度が45であるテーパーブロック共重合体）、スチレン22.8重量部、メタクリル酸メチル37.0重量部、アクリロニトリル1.8重量部、エチルベンゼン30重量部、ドデシルメルカプタン0.1重量部、およびベンゾイルパーオキシド0.1重量部を原料溶液とし、ポンプで35kg／hrの流量で連続的に反応槽へ送り重合を行う。第一反応槽の温度は102℃、第二反応槽の温度は106℃、第三反応槽の温度は117℃、第四反応槽の温度は127℃で、総重合転化率は60％となる。重合後重合溶液を反応槽から連続的に脱揮発装置へ送り、脱揮発の真空度を80Torrに保ち未反応のモノマー及び有機溶剤などの揮発性物質を分離させ、出来た樹脂を押出機でペレット状にする。そして上記のスチレン系樹脂100重量部に対して0.3重量部のペンタエリスリトールテトラステアレートを混合均一させて押出機で混練してペレット状にする
得られた透明ポリスチレン系樹脂の共重合体連続相の組成はスチレン単位が34重量部、メタクリル酸メチル単位が63重量部、アクリロニトリル単位が３重量部であり、分散相ゴム粒子の重量平均粒径は0.33μmである。また、低分子量重合体の比率は0.24重量％である。なお、樹脂組成物のペンタエリスリトールテトラステアレートの含有量は0.3重量部（100重量部の透明ポリスチレン系樹脂基準）である。
【００６２】
比較例１
四個の容量40リットルの完全混合型反応槽を順に繋いで連続重合装置を構成し、透明ポリスチレン系樹脂組成物の製造に用いる。ゴム状共重合体8.4重量部（スチレン／ブタジエン＝25／75重量％、1,2-ビニル基含有量＝15.4％、Mooney粘度が45であるテーパーブロック共重合体）、スチレン22.8重量部、メタクリル酸メチル37.0重量部、アクリルニトリル1.8重量部、エチルベンゼン30重量部、ドデシルメルカプタン0.06重量部、ペンタエリスリトールテトラステアレート0.48重量部、およびベンゾイルパーオキシド0.05重量部を原料溶液とし、ポンプで35kg／hrの流量で連続的に反応槽へ送り重合を行う。第一反応槽の温度は114℃、第二反応槽の温度は120℃、第三反応槽の温度は135℃、第四反応槽の温度は155℃で、総重合転化率は64％となる。重合後重合溶液を反応槽から連続的に脱揮発装置へ送り、脱揮発の真空度を250Torrに保ち未反応のモノマー及び有機溶剤などの揮発性物質を分離させ、出来た樹脂を押出機でペレット状にする。
【００６３】
得られた透明ポリスチレン系樹脂の共重合体連続相の組成はスチレン単位が34重量部、メタクリル酸メチル単位が63重量部、アクリロニトリル単位が３重量部であり、分散相ゴム粒子の重量平均粒径は0.45μmである。また、低分子量重合体の比率は2.2重量％である。
【００６４】
なお、樹脂組成物のペンタエリスリトールテトラステアレートの含有量は1.0重量部（100重量部の透明ポリスチレン系樹脂基準）である。
【００６５】
比較例２
四個の容量40リットルの完全混合型反応槽を順に繋いで連続重合装置を構成し、透明ポリスチレン系樹脂組成物の製造に用いる。ゴム状共重合体8.4重量部（スチレン／ブタジエン＝25／75重量％、1,2-ビニル基含有量＝15.4％、Mooney粘度が45であるテーパーブロック共重合体）、スチレン22.8重量部、メタクリル酸メチル37.0重量部、アクリロニトリル1.8重量部、エチルベンゼン30重量部、ドデシルメルカプタン0.1重量部、およびベンゾイルパーオキシド0.1重量部を原料溶液とし、ポンプで35kg／hrの流量で連続的に反応槽へ送り重合を行う。第一反応槽の温度は102℃、第二反応槽の温度は106℃、第三反応槽の温度は117℃、第四反応槽の温度は127℃で、総重合転化率は60％となる。重合後重合溶液を反応槽から連続的に脱揮発装置へ送り、脱揮発の真空度を80Torrに保ち未反応のモノマー及び有機溶剤などの揮発性物質を分離させ、出来た樹脂を押出機でペレット状にする。
【００６６】
得られた透明ポリスチレン系樹脂の共重合体連続相の組成はスチレン単位が34重量部、メタクリル酸メチル単位が63重量部、アクリロニトリル単位が３重量部であり、分散相ゴム粒子の重量平均粒径は0.37μmである。また、低分子量重合体の比率は0.25重量％であり、出来た樹脂組成物はその射出成形時での離型性が悪い。
【００６７】
比較例３
四個の容量40リットルの完全混合型反応槽を順に繋いで連続重合装置を構成し、透明ポリスチレン系樹脂組成物の製造に用いる。ゴム状共重合体8.4重量部（スチレン／ブタジエン＝25／75重量％、1,2-ビニル基含有量＝15.4％、Mooney粘度が45であるテーパーブロック共重合体）、スチレン22.8重量部、メタクリル酸メチル37.0重量部、アクリロニトリル1.8重量部、エチルベンゼン30重量部、ドデシルメルカプタン0.09重量部、およびベンゾイルパーオキシド0.1重量部を原料溶液とし、ポンプで35kg／hrの流量で連続的に反応槽へ送り重合を行う。第一反応槽の温度は102℃、第二反応槽の温度は106℃、第三反応槽の温度は117℃、第四反応槽の温度は127℃で、総重合転化率は60％となる。重合後重合溶液を反応槽から連続的に脱揮発装置へ送り、脱揮発の真空度を80Torrに保ち未反応のモノマー及び有機溶剤などの揮発性物質を分離させ、出来た樹脂を押出機でペレット状にする。そして上記のスチレン系樹脂100重量部に対して6重量部のペンタエリスリトールテトラステアレートを混合均一させて押出機で混練してペレット状にする
得られた透明ポリスチレン系樹脂の共重合体連続相の組成はスチレン単位が34重量部、メタクリル酸メチル単位が63重量部、アクリロニトリル単位が３重量部であり、分散相ゴム粒子の重量平均粒径は0.40μmである。また、低分子量重合体の比率は0.24重量％である。なお、樹脂組成物のペンタエリスリトールテトラステアレートの含有量は6重量部（100重量部の透明ポリスチレン系樹脂基準）である。
【００６８】
比較例４
四個の容量40リットルの完全混合型反応槽を順に繋いで連続重合装置を構成し、透明ポリスチレン系樹脂組成物の製造に用いる。ゴム状共重合体8.4重量部（スチレン／ブタジエン＝25／75重量％、1,2-ビニル基含有量＝15.4％、Mooney粘度が45であるテーパーブロック共重合体）、スチレン22.8重量部、メタクリル酸メチル37.0重量部、アクリロニトリル1.8重量部、エチルベンゼン30重量部、ドデシルメルカプタン0.09重量部、およびベンゾイルパーオキシド0.09重量部を原料溶液とし、ポンプで35kg／hrの流量で連続的に反応槽へ送り重合を行う。第一反応槽の温度は103℃、第二反応槽の温度は107℃、第三反応槽の温度は123℃、第四反応槽の温度は131℃で、総重合転化率は60％となる。重合後重合溶液を反応槽から連続的に脱揮発装置へ送り、脱揮発の真空度を130Torrに保ち未反応のモノマー及び有機溶剤などの揮発性物質を分離させ、出来た樹脂を押出機でペレット状にする。そして上記のスチレン系樹脂100重量部に対して2重量部のステアリン酸メチルを混合均一させて押出機で混練してペレット状にする
得られた透明ポリスチレン系樹脂の共重合体連続相の組成はスチレン単位が34重量部、メタクリル酸メチル単位が63重量部、アクリロニトリル単位が３重量部であり、分散相ゴム粒子の重量平均粒径は0.40μmである。また、低分子量重合体の比率は0.43重量％である。
【００６９】
比較例５
四個の容量40リットルの完全混合型反応槽を順に繋いで連続重合装置を構成し、透明ポリスチレン系樹脂組成物の製造に用いる。ゴム状共重合体8.4重量部（スチレン／ブタジエン＝25／75重量％、1,2-ビニル基含有量＝15.4％、Mooney粘度が45であるテーパーブロック共重合体）、スチレン22.8重量部、メタクリル酸メチル37.0重量部、アクリロニトリル1.8重量部、エチルベンゼン30重量部、ドデシルメルカプタン0.08重量部、およびベンゾイルパーオキシド0.08重量部を原料溶液とし、ポンプで35kg／hrの流量で連続的に反応槽へ送り重合を行う。第一反応槽の温度は104℃、第二反応槽の温度は109℃、第三反応槽の温度は125℃、第四反応槽の温度は135℃で、総重合転化率は60％となる。重合後重合溶液を反応槽から連続的に脱揮発装置へ送り、脱揮発の真空度を200Torrに保ち未反応のモノマー及び有機溶剤などの揮発性物質を分離させ、出来た樹脂を押出機でペレット状にする。そして上記のスチレン系樹脂100重量部に対して2重量部のステアリン酸ブチルを混合均一させて押出機で混練してペレット状にする。
【００７０】
得られた透明ポリスチレン系樹脂の共重合体連続相の組成はスチレン単位が34重量部、メタクリル酸メチル単位が63重量部、アクリロニトリル単位が３重量部であり、分散相ゴム粒子の重量平均粒径は0.41μmである。また、低分子量重合体の比率は0.62重量％である。
【００７１】
比較例６
四個の容量40リットルの完全混合型反応槽を順に繋いで連続重合装置を構成し、透明ポリスチレン系樹脂組成物の製造に用いる。ゴム状共重合体8.4重量部（スチレン／ブタジエン＝25／75重量％、1,2-ビニル基含有量＝15.4％、Mooney粘度が45であるテーパーブロック共重合体）、スチレン22.8重量部、メタクリル酸メチル37.0重量部、アクリロニトリル1.8重量部、エチルベンゼン30重量部、ドデシルメルカプタン0.1重量部、およびベンゾイルパーオキシド0.1重量部を原料溶液とし、ポンプで35kg／hrの流量で連続的に反応槽へ送り重合を行う。第一反応槽の温度は102℃、第二反応槽の温度は106℃、第三反応槽の温度は117℃、第四反応槽の温度は127℃で、総重合転化率は60％となる。重合後重合溶液を反応槽から連続的に脱揮発装置へ送り、脱揮発の真空度を80Torrに保ち未反応のモノマー及び有機溶剤などの揮発性物質を分離させ、出来た樹脂を押出機でペレット状にする。そして上記のスチレン系樹脂100重量部に対して2重量部のエチレンビスステアリンアミドを混合均一させて押出機で混練してペレット状にする
得られた透明ポリスチレン系樹脂の共重合体連続相の組成はスチレン単位が34重量部、メタクリル酸メチル単位が63重量部、アクリロニトリル単位が３重量部であり、分散相ゴム粒子の重量平均粒径は0.35μmである。低分子量重合体の比率は0.21重量％である。
【００７２】
比較例７
四個の容量40リットルの完全混合型反応槽を順に繋いで連続重合装置を構成し、透明ポリスチレン系樹脂組成物の製造に用いる。ゴム状共重合体8.4重量部（スチレン／ブタジエン＝25／75重量％、1,2-ビニル基含有量＝15.4％、Mooney粘度が45であるテーパーブロック共重合体）、スチレン22.8重量部、メタクリル酸メチル37.0重量部、アクリロニトリル1.8重量部、エチルベンゼン30重量部、ドデシルメルカプタン0.1重量部、ミネラルオイル〔エッソ(ESSO)社、Primol 382〕0.91重量部、およびベンゾイルパーオキシド0.1重量部を原料溶液とし、ポンプで35kg／hrの流量で連続的に反応槽へ送り重合を行う。第一反応槽の温度は102℃、第二反応槽の温度は106℃、第三反応槽の温度は117℃、第四反応槽の温度は127℃で、総重合転化率は60％となる。重合後重合溶液を反応槽から連続的に脱揮発装置へ送り、脱揮発の真空度を80Torrに保ち未反応のモノマー及び有機溶剤などの揮発性物質を分離させ、出来た樹脂を押出機でペレット状にする。
【００７３】
得られた透明ポリスチレン系樹脂の共重合体連続相の組成はスチレン単位が34重量部、メタクリル酸メチル単位が63重量部、アクリロニトリル単位が３重量部であり、分散相ゴム粒子の重量平均粒径は0.37μmである。低分子量重合体の比率は0.21重量％である。なお、樹脂組成物中のミネラルオイルの含有量は2重量部（100重量部の透明ポリスチレン系樹脂基準）である。
【００７４】
比較例８
四個の容量40リットルの完全混合型反応槽を順に繋いで連続重合装置を構成し、透明ポリスチレン系樹脂組成物の製造に用いる。ゴム状共重合体8.4重量部（スチレン／ブタジエン＝25／75重量％、1,2-ビニル基含有量＝15.4％、Mooney粘度が45であるテーパーブロック共重合体）、スチレン22.8重量部、メタクリル酸メチル37.0重量部、アクリルニトリル1.8重量部、エチルベンゼン30重量部、ドデシルメルカプタン0.1重量部、およびベンゾイルパーオキシド0.1重量部を原料溶液とし、ポンプで35kg／hrの流量で連続的に反応槽へ送り重合を行う。第一反応槽の温度は102℃、第二反応槽の温度は106℃、第三反応槽の温度は117℃、第四反応槽の温度は127℃で、総重合転化率は60％となる。重合後重合溶液を反応槽から連続的に脱揮発装置へ送り、脱揮発の真空度を80Torrに保ち未反応のモノマー及び有機溶剤などの揮発性物質を分離させ、出来た樹脂を押出機でペレット状にする。そして上記のスチレン系樹脂100重量部に対して2重量部のポリエチレンワックス（三井化学社、200P）を混合均一させて押出機で混練してペレット状にする。
【００７５】
得られた透明ポリスチレン系樹脂の共重合体連続相の組成はスチレン単位が34重量部、メタクリル酸メチル単位が63重量部、アクリロニトリル単位が３重量部であり、分散相ゴム粒子の重量平均粒径は0.37μmである。低分子量重合体の比率は0.22重量％である。なお、樹脂組成物中のポリエチレンワックスの含有量は2重量部（100重量部の透明ポリスチレン系樹脂基準）である。
【００７６】
比較例９
四個の容量40リットルの完全混合型反応槽を順に繋いで連続重合装置を構成し、透明ポリスチレン系樹脂組成物の製造に用いる。ゴム状共重合体8.4重量部（スチレン／ブタジエン＝25／75重量％、1,2-ビニル基含有量＝15.4％、Mooney粘度が45であるテーパーブロック共重合体）、スチレン22.8重量部、メタクリル酸メチル37.0重量部、アクリルニトリル1.8重量部、エチルベンゼン30重量部、ドデシルメルカプタン0.08重量部、ペンタエリスリトールテトラステアレート1.21重量部、およびベンゾイルパーオキシド0.06重量部を原料溶液とし、ポンプで35kg／hrの流量で連続的に反応槽へ送り重合を行う。第一反応槽の温度は110℃、第二反応槽の温度は115℃、第三反応槽の温度は140℃、第四反応槽の温度は150℃で、総重合転化率は63％となる。重合後重合溶液を反応槽から連続的に脱揮発装置へ送り、脱揮発の真空度を250Torrに保ち未反応のモノマー及び有機溶剤などの揮発性物質を分離させ、出来た樹脂を押出機でペレット状にする。
【００７７】
得られた透明ポリスチレン系樹脂の共重合体連続相の組成はスチレン単位が34重量部、メタクリル酸メチル単位が63重量部、アクリロニトリル単位が３重量部であり、分散相ゴム粒子の重量平均粒径は0.46μmである。また、低分子量重合体の比率は1.52重量％である。
【００７８】
なお、樹脂組成物のペンタエリスリトールテトラステアレートの含有量は2.5重量部（100重量部の透明ポリスチレン系樹脂基準）である。
【００７９】
上記の実施例１〜５および比較例１〜９の物性測定結果を表１に示す。
【００８０】
【表１】
実施例６
ポリスチレン100重量部に対して0.6重量部のペンタエリスリトールテトラステアレートを均一混合させて押出機で混練してペレット状にする。これを用いて測定した結果、低分子量重合体の比率は0.55重量％、Ｘ＋２Ｙは1.7、加工性（MI）は3.4、透明性（Haze）は1.2％、透過率は90.0％、射出成形の離型性が良好である。
【００８２】
比較例10
実施例６と同じポリスチレン（ペンタエリスリトールテトラステアレートを添加しないもの）を用いて測定した結果、低分子量重合体の比率は0.55重量％、Ｘ＋２Ｙは1.1、加工性（MI）は2.9、透明性（Haze）は0.9％、透過率は91.1％であるが、樹脂の射出成形の離型性が不良である。
【００８３】
実施例７
スチレン−アクリロニトリル共重合物（アクリロニトリル単位24重量％）100重量部に対して0.5重量部のペンタエリスリトールテトラステアレートを混合均一させて押出機で混練してペレット状にする。これを用いて測定した結果、低分子量重合体の比率は1.20重量％、Ｘ＋２Ｙは2.9、加工性（MI）は2.8、透明性（Haze）は1.8％、透過率は90.2％、射出成形の離型性が良好である。
【００８４】
比較例11
実施例７と同じスチレン−アクリロニトリル共重合物（ペンタエリスリトールテトラステアレートを添加しないもの）を用いて測定した結果、低分子量重合体の比率は1.20重量％、Ｘ＋２Ｙは2.4、加工性（MI）は2.4、透明性（Haze）は1.5％、透過率は91.1％であるが、樹脂の射出成形の離型性が良くない。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a transparent polystyrene resin composition. Specifically, the present invention relates to a transparent polystyrene-based resin composition that has excellent transparency and processability, and at the same time has greatly improved mold stains during molding.
[0002]
[Prior art and problems to be solved by the invention]
Styrenic resin is a material having good strength and moldability. In particular, transparent styrenic resins are widely applied to household items such as transparent food containers and packaging materials, home appliances, and peripheral parts for office automation equipment, but the need for thinner and larger products is increasing day by day. Therefore, higher moldability is required. In order to increase the processability of a resin molded product without deteriorating the physical properties, in the existing method, for example, a small amount of a lubricant is added as a molding aid in a styrene resin to improve the fluidity during the molding process. In general, fatty acid metal salts are used as molding aids used in styrene resins, among which calcium stearate, zinc stearate, and fatty acid amides (for example, ethylene bisstearyl amide) are effective in improving processability. For example, Japanese Patent Publication No. 2-52923 discloses that in the production of a styrene resin, the processability of the resin is improved by adding 1 to 8 parts by weight of an ethylene bisstearylamide solution to a reaction vessel. Japanese Patent Application Laid-Open No. 63-33455 discloses that when calcium stearate or zinc stearate is added to a styrene resin and mixed, the releasability during resin molding is improved.
[0003]
JP-A-7-82439 discloses that the flowability and impact resistance of a resin can be improved by adding butyl stearate and a small amount of triglyceride to a styrene resin.
[0004]
As described above, in each of the prior arts, additives such as lubricants or mold release agents can be added to (transparent) styrene resins to improve the processability and mold release of the resin. It becomes impossible to obtain a styrenic resin having good transparency by deteriorating the transparency. In addition, the additive may cause mold contamination during injection molding, and the problem becomes more prominent particularly during injection molding at high temperatures and thinning.
[0005]
[Means for Solving the Problems]
In order to solve the above-mentioned drawbacks, the present invention provides a transparent polystyrene resin composition having good transparency and processability and free from mold contamination during molding.
[0006]
That is, the present invention provides (I) a transparent polystyrene resin composition containing (II) 0.01 to 4 parts by weight of a pentaerythritol ester compound relative to 100 parts by weight of a transparent polystyrene resin, (I) The present invention relates to a transparent polystyrene resin composition in which the ratio of a low molecular weight polymer having a molecular weight of less than 350 in the dichloromethane soluble content of a transparent polystyrene resin is 2.0% by weight or less and satisfies the following formula (1).
0.52 <X + 2Y <4.50 Formula (1)
X: parts by weight of (II) pentaerythritol ester compound with respect to 100 parts by weight of the transparent polystyrene resin (I)
Y:% by weight of the low molecular weight polymer having a molecular weight of less than 350 in the dichloromethane-soluble component of the transparent polystyrene resin (I).
[0007]
In the present invention, the “transparent” polystyrene-based resin refers to one having a light transmittance of 60% or more.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The (I) transparent polystyrene resin of the present invention is classified into two types, that is, a rubber-modified transparent polystyrene resin and a transparent polystyrene resin not containing rubber. The transparent polystyrene resin not containing rubber is preferably a styrene resin having a styrene monomer content of 30% by weight or more, and includes a styrene monomer of 100 to 30% by weight and other copolymerization monomers of 0 to 70% by weight. . Other copolymerization monomers are not particularly limited as long as they can be copolymerized with styrene monomers and reach a certain transparency. As the styrene monomer, those exemplified by a rubber-like polymer of a rubber-modified transparent styrene resin described later can be used.
[0009]
Examples of the copolymerization monomer used in the transparent polystyrene resin (I) of the present invention that does not contain rubber include, for example, (meth) acrylic acid ester monomers, acrylonitrile monomers, maleimide monomers, (meth) acrylic acid, and maleic anhydride. Examples include acids.
[0010]
Among them, (meth) acrylic acid ester monomers include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, benzyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, methacrylic acid 2 -Hydroxyethyl, glyceryl methacrylate, dimethylaminoethyl methacrylate and the like. Among them, methyl methacrylate is more preferable.
[0011]
Acrylonitrile monomers include acrylonitrile and α-methacrylonitrile, with acrylonitrile being more preferred.
[0012]
Maleimide monomers are N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-2,3 -Dimethylphenylmaleimide, N-2,4-dimethylphenylmaleimide, N-2,3-diethylphenylmaleimide, N-2,4-diethylphenylmaleimide, N-2,3-dibutylphenylmaleimide, N-2,4 -Dibutylphenylmaleimide, N-2,6-dimethylphenylmaleimide, N-2,3-dichlorophenylmaleimide, N-2,4-dichlorophenylmaleimide, N-2,3-dibromophenylmaleimide, N-2,4- Examples thereof include dibromophenylmaleimide, and N-phenylmaleimide is more preferable.
[0013]
Specific examples of (I) transparent polystyrene resins not containing rubber include styrene polymers such as polystyrene, styrene-acrylonitrile copolymers, styrene- (meth) acrylate copolymers, styrene -N-substituted maleimide-acrylonitrile copolymer, styrene-N-substituted maleimide copolymer, styrene- (meth) acrylate ester-N-substituted maleimide copolymer, styrene-N- Examples include substituted maleimide-acrylonitrile- (meth) acrylic acid ester copolymers. Two or more of these may be used in combination.
[0014]
Another type of transparent polystyrene resin of the present invention is a rubber-modified transparent polystyrene resin, more preferably a transparent polystyrene resin modified with a diene rubber. Examples of the resin include a mixture of rubber and a transparent polystyrene resin not containing rubber, or a resin obtained by graft polymerization with rubber, a styrene monomer, and other copolymerizable monomers. Examples of the rubber include butadiene rubber and butadiene-styrene copolymer. A preferable structure for the rubber-modified transparent polystyrene resin obtained by graft polymerization is a rubber particle dispersed phase (A) composed of a rubber-like polymer, 12 to 70% by weight of a styrene monomer, a (meth) acrylic acid ester monomer 20 It consists of a copolymer continuous phase (B) composed of ˜80 wt%, acrylonitrile monomer 0-20 wt%, and other copolymerizable monomers 0-40 wt%.
[0015]
The rubbery polymer in the dispersed phase (A) is preferably a rubbery copolymer composed of 5 to 50% by weight of a styrene monomer and 95 to 50% by weight of a diene monomer. Such a rubbery copolymer can be obtained as a block copolymer by performing an anionic polymerization reaction with a styrene monomer, a diene monomer, and an appropriate amount of solvent using an organic lithium compound as an initiator in the presence of an organic solvent. Such a rubbery copolymer has a Mooney viscosity (ML).1 + 4) Is 20-80, the viscosity of a 5% by weight styrene monomer solution at 25 ° C. is 3-60 cps, the 1,2-vinyl structure in the diene unit is 8% by weight or more, and the polystyrene block content is rubbery co-polymer. It preferably accounts for 5 to 35% by weight of the coalescence. As for the structure of the above rubber-like copolymer, each block includes a uniform polymer block structure, a partially random block structure, a taper-block structure, a linear structure, and a branched structure. A typical structure is as follows.
[0016]
(1) Linear block copolymer
(1-1) (AB)n
(1-2) A- (BA)n
(1-3) B- (AB)n
Here, A indicates a polymer block mainly composed of styrene, and B indicates a polymer block mainly composed of a diene. However, the boundary between the A block and the B block has no particular distinction, and n Is an integer of 1 or more.
[0017]
(2) Branched block polymer
(2-1) [(BA)n]m-2X
(2-2) [(AB)n]m-2X
(2-3) [(BA)nB]m-2X
(2-4) [(AB)nA]m-2X
Here, A and B are the same as (1), but X is a residue of a coupling agent (for example, tetrachlorosilane, tetrachlorotin, etc.) or a polyfunctional organolithium compound residue. n and m are integers of 1-10.
[0018]
(3) A mixture of any of the above-mentioned items (1) and (2).
[0019]
The taper block structure is a styrene taper block structure or a butadiene taper block structure, and specific examples are as follows.
DD / SS, (SD / S)n-S, D-S-D / S-S, D / S- (S-D / S)n, D-S-D / S-S-D, X-[(S-D / S)n]m + 1, S-D-D / S-S, X-[(D / S-S)n]m + 1, D / S-S-D-S, X-[(S-D / S)n-S]m + 1, SD / SS, X-[(D / SS)n-D / S]m + 1, (S-D / S)n, D-D / S-S-S-D / S-D
Here, S is a polystyrene block, D is a polydiene block, D / S is a styrene or diene taper block, X is a residue of a polyfunctional initiator or a residue of a polyfunctional coupling agent, m , N refers to an integer of 1-10. Among the above examples, DD / SS, DSD / SS, DD / SSSS / SD is preferred. In the present invention, the tapered block structure is more appropriate.
[0020]
Examples of the styrene monomer include styrene, α-methyl styrene, paramethyl styrene, metamethyl styrene, ethyl styrene, 2,4-dimethyl styrene, para-t-butyl styrene, bromostyrene, and the like. These monomers may be used alone or in combination of two or more.
[0021]
Examples of the diene monomer include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. These monomers may be used alone or in combination of two or more. Among them, 1,3-butadiene or 2-methyl-1,3-butadiene is more preferable.
[0022]
The organolithium compound catalyst used in the production of the rubbery copolymer is a compound containing one or more lithium atoms in its molecule, such as ethyl lithium, n-pentyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl. Lithium, hexyl lithium, cyclohexyl lithium, phenyl lithium, benzyl lithium, naphthalyl lithium, t-butyl lithium, trimethylene dilithium, tetramethylene dilithium, butadienyl dilithium, and isoprenyl dilithium, etc. These can be used alone or in combination of two or more.
[0023]
The polymerization rate of the rubbery copolymer, the content of 1,2-vinyl group, the reaction rate of the diene monomer and the styrene monomer, and the degree of randomization are determined with a polar compound or a randomizing agent. Can be adjusted. Examples of the polar compound or randomizing agent include ethers, amines, thioethers, alkali salts of alkylbenzene sulfonic acids, and alkoxides of potassium or sodium.
[0024]
In the present invention, the copolymer continuous phase (B) is 12 to 70% by weight of a styrene monomer, 20 to 80% by weight of a (meth) acrylic acid ester monomer, 0 to 20% by weight of an acrylonitrile monomer, Those consisting of 0 to 40% by weight of other copolymerization monomers are preferred. Among them, as the styrenic monomer, those exemplified in the above rubbery copolymer can be used.
[0025]
The (meth) acrylic acid ester monomer used for the production of the copolymer continuous phase (B) includes methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, etc. Examples of acrylic esters include methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-methylpentyl acrylate, 2-ethylpentyl acrylate, octyl acrylate, diethylaminoethyl acrylate, and dimethylaminopropyl acrylate. However, methyl methacrylate and n-butyl acrylate are more preferred.
[0026]
Examples of the acrylonitrile monomer used for the production of the copolymer continuous phase (B) include acrylonitrile and α-methylacrylonitrile.
[0027]
The copolymerizable monomer used in the production of the copolymer continuous phase (B) occupies 0 to 40% by weight of the copolymer monomer ratio, but there is no special limitation on the type, and each of the monomers can be used as necessary. The content ratio of the comonomer is adjusted so that the final resin composition reaches a certain transparency. Specific examples include unsaturated fatty acids such as itaconic acid, maleic acid, fumaric acid, butenoic acid, cinnamic acid, N-methylmaleimide, N-ethylmaleimide, N-butylmaleimide, N-octylmaleimide, N- Maleimides such as isopropylmaleimide, N-phenylmaleimide, N-parabromo-phenylmaleimide, N-orthochloro-phenylmaleimide, N-cyclohexylmaleimide, unsaturated anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, And propenylamine, and acrylamide monomers such as acrylamide and N-methylacrylamide.
[0028]
The weight average molecular weight of the copolymer continuous phase (B) of the resin composition of the present invention is not particularly limited, but is generally 50,000 to 300,000, preferably 60,000 to 200,000, more preferably 70,000 to 150,000. . If the weight average molecular weight is 50,000 or more, the impact strength of the resin composition will be good. On the other hand, when the weight average molecular weight is 300,000 or less, the fluidity of the resin composition is good, and the processability and transparency are improved. In the present invention, the weight average particle diameter of the dispersed phase (A) rubber particles is not particularly limited, but is generally 0.1 to 2.0 μm, preferably 0.1 to 1.5 μm, more preferably 0.2 to 1.0 μm. It is. If the weight average particle diameter of the rubber particles is 0.1 μm or more, the impact strength of the resin composition will be good. When the weight average particle diameter is 2.0 μm or less, the transparency of the resin composition is good. The weight average particle diameter of the rubber particles is determined from a photograph taken with a transmission electron microscope (ultra thin section method). Remove at least 300 particles from the photograph and measure the size. The weight average particle diameter is calculated by the following formula.
[0029]
[Expression 1]
The gel content of the resin composition of the present invention is determined as an insoluble matter in toluene / acetone (weight ratio 1/1), but is not particularly limited and is generally 2 to 40% by weight, preferably 8 to 35%. % By weight, more preferably 12-30% by weight. The swelling index of the resin composition of the present invention is not particularly limited, but is generally 2 to 25, preferably 3 to 20, and more preferably 5 to 15.
[0031]
The (I) transparent polystyrene-based resin of the present invention is such that the proportion of the low molecular weight polymer having a molecular weight of less than 350 in the dichloromethane-soluble component is 2.0% by weight or less, preferably 1.0% by weight or less, More preferably, it is 0.6% by weight or less. If this ratio is 2.0% by weight or less, the mold stain phenomenon can be suppressed during the molding process of the polystyrene-based resin, and product spots are less likely to occur. Here, a low molecular weight polymer having a molecular weight of less than 350 has a molecular weight of 350 using a GC-MS analysis method (gas chromatograph-mass spectrometry method) for a portion (soluble matter) obtained by dissolving a transparent polystyrene resin in a dichloromethane solvent. It is obtained by measuring the content of a low molecular weight polymer of less than (converted to styrene standard area). Examples of the low molecular weight polymer (for example, trimer, dimer) having a molecular weight of less than 350 include AMS, MMS, AS, MSS, SSS, MS, and the like. Here, A represents acrylonitrile monomer, M represents methyl (meth) acrylate monomer, and S represents styrene monomer.
[0032]
The pentaerythritol ester compound used in the transparent polystyrene resin composition of the present invention is an ester compound formed by reacting pentaerythritol with a carboxylic acid. Examples of the carboxylic acid include lauric acid, palmitic acid, stearic acid, arachidonic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, oleic acid, elaidic acid, erucic acid, linoleic acid, and linolenic acid. Two or more of these carboxylic acids may be used in combination.
[0033]
Specific examples of the esters of pentaerythritol used in the transparent polystyrene resin composition of the present invention include pentaerythritol tristearate, pentaerythritol tetrastearate, pentaerythritol tetralaurate, etc., preferably pentaerythritol. Tetrastearate. The ester compound is obtained by an ester reaction, but a catalyst (for example, organic tin) is used in some cases. The amount of alcohol and carboxylic acid used in the reaction is determined by the type and amount.
[0034]
The addition amount of (II) pentaerythritol ester in the present invention is 0.01 to 4 parts by weight, preferably 0.02 to 3 parts by weight, more preferably 0.05 to 4 parts by weight based on 100 parts by weight of (I) transparent polystyrene resin. 1.5 parts by weight. (II) When the amount of pentaerythritol ester is within this range, the transparent polystyrene resin composition of the present invention is excellent in moldability, mold release, mold stain prevention, transparency and heat resistance. Also, the impact strength is improved. Specifically, when the addition amount is less than 0.01 parts by weight, the molding processability and mold release property of the styrene resin are deteriorated. On the other hand, when the addition amount is more than 5 parts by weight, the mold stains become severe, and the heat resistance and transparency of the resin composition are deteriorated.
[0035]
The transparent polystyrene resin composition of the present invention satisfies the above formula (1), but preferably satisfies 0.60 <X + 2Y <3.50, more preferably 0.70 <X + 2Y <3.00. If the formula (1) is not satisfied, the molding processability, mold release property and mold dirt prevention property are improved, and a polystyrene resin composition having excellent transparency cannot be obtained.
[0036]
There are no particular restrictions on the method of adding the pentaerythritol-based ester compound, but (I) a method of adding at the time of polymerization of the transparent polystyrene resin, a method of adding after polymerization, or an extruder or a mixer method. There are methods.
[0037]
The method for producing the transparent polystyrene resin (I) of the present invention may be emulsification, suspension, bulk (or solution) polymerization, or a combination of the above polymerization methods, but preferably emulsion or bulk (or solution) polymerization. A bulk (or solution) polymerization method is preferred.
[0038]
In addition, among the (I) resins of the present invention, one of the methods for producing a rubber-modified transparent polystyrene resin is a styrene monomer, (meth) acrylate monomer, acrylonitrile resin in the presence of a rubbery copolymer. Examples thereof include a method in which a monomer and, if necessary, other copolymerizable monomers are subjected to a graft polymerization reaction by a batch or continuous bulk or solution polymerization method. Taking continuous solution polymerization as an example, first, the above rubbery copolymer and monomer are added to an appropriate amount of solvent to form a raw material mixed solution. The raw material mixed solution is dissolved in a dissolution tank having high shear and high stirring ability. The dissolution tank is equipped with a belt-like spiral stirring leaf, a spiral rod stirring leaf, or other stirring leaf that generates a high shear force, and the above rubber-like copolymer is completely dissolved over a sufficient amount of time. To a rubber solution which is pumped to the reactor. The raw material solution or the monomer solution is continuously fed to the first reactor and / or the second reactor and / or the subsequent reactor, respectively. If necessary, a graft transfer reaction is carried out by adding a chain transfer agent and an initiator to the first and / or second and / or subsequent reactors.
[0039]
The reaction vessel may be one of a continuous stirring type (CSTR), a plug flow type, a static mixing type (static), or a combination of two or more types. The reaction temperature is kept at 70-230 ° C. and the final monomer conversion is 30-95%, preferably 50-90%.
[0040]
Examples of the solvent used for the polymerization of the transparent polystyrene resin (I) of the present invention include aromatic hydrocarbon compounds, ketones, and esters, and aromatic hydrocarbon compounds are preferred. Specific examples include toluene, ethylbenzene and xylene. Of the ketones, butanone is preferred. For esters, ethyl acetate is preferred. In addition, aliphatic hydrocarbon compounds such as cyclohexane and n-heptane can be used as a part of the solvent.
[0041]
The (I) transparent polystyrene resin of the present invention uses an initiator during production. Initiators used include benzoyl peroxide (benzoyl peroxide), dicumyl peroxide, t-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxybenzoate, di-2 -Ethylhexylperoxydicarbonate, t-butylperoxyisopropylcarbonate (abbreviation BPIC), cyclohexanone peroxide, 2,2'-azo-bis-isobutyronitrile, 1,1'-azo-bis-1- Cyclohexanecarbonitrile, 2,2'-azo-bis-2-methylbutyronitrile, azo-bis-isobutyronitrile, 1,1-di- (t-butylperoxy) cyclohexane (abbreviation TX-22) ), 1,1-di- (t-butylperoxy) 3,3,5-trimethylcyclohexane (abbreviation TX-29A), 2,5-dimethyl-2,5-bis- (2-ethylhexanoxy) Paoki ) Hexane, 4- (t-butylperoxycarbonyl) -3-hexyl-6- [7- (t-butylperoxycarbonyl) heptyl] cyclohexane, di-t-butyl-diperoxyazelate, 2,5 -Dimethyl-2,5-bis- (benzoylperoxy) hexane, di-t-butylperoxyhexahydro-terephthalate (abbreviation BPHTP), 2,2-bis- (4,4-di-t-butylperoxy ) Cyclohexanylpropane and the like.
[0042]
A chain transfer agent is used as necessary in the production of the transparent polystyrene resin composition of the present invention. Examples of the chain transfer agent include the following.
Mercaptans: methyl mercaptan, n-butyl mercaptan, cyclohexyl mercaptan, n-dodecyl mercaptan, stearyl mercaptan, t-dodecyl mercaptan (abbreviation TDM), n-propyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, t- Nonyl mercaptan, 2-ethylhexyl ester of mercaptopropionic acid, etc.
-Alkylamines: monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, monobutylamine, di-n-butylamine, tri-n-butylamine and the like.
Other: pentaphenylethane, α-methylstyrene dimer, terpinolene, etc.
[0043]
After the above polymerization reaction is completed, the product is taken out from the reactor, passed through a devolatilizer to remove low-volatile components such as unreacted monomers and solvents, and the polymer is recovered to obtain a transparent polystyrene resin.
[0044]
As described above, there is no particular limitation on the method of adding the (II) pentaerythritol ester compound, but a specific method of addition includes a method of melt-kneading the obtained (I) transparent polystyrene resin. . For example, kneading is generally performed at a temperature of 160 to 280 ° C., preferably 180 to 250 ° C., using a melt kneader such as a Banbury mixer, a roll kneader, and a single or twin screw extruder. The extrudate obtained by extruding after kneading is granulated after cooling to form a pellet and used for molding. Moreover, there is no restriction | limiting in particular about the addition order of each component when kneading | mixing.
[0045]
Other components can be added as long as the effects of the resin composition of the present invention are not significantly impaired. For example, colorants, fillers, flame retardants, flame retardant aids (antimony oxide, etc.), light stabilizers, heat stabilizers, plasticizers, lubricants, mold release agents, thickeners, antistatic agents, antioxidants, conductive An additive such as an agent can be mentioned. Specific examples include mineral oils, ester plasticizers such as butyl stearate, polyester plasticizers, organic polysiloxanes such as polydimethylsiloxane, higher fatty acids and metal salts, sterically hindered amine antioxidants, glass fibers. and so on. Each can be used alone or in combination. The amount of the ester plasticizer or mineral oil used is generally 0 to 5 parts by weight, preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the resin composition. On the other hand, the amount of the organic polysiloxane used is generally 0 to 0.5 parts by weight, preferably 0.002 to 0.2 parts by weight, and the structure thereof preferably has a dimethylpolysiloxane molecular weight of 800 to 100,000.
[0046]
【The invention's effect】
According to the present invention, it is possible to obtain a transparent polystyrene resin composition having excellent transparency and workability, and at the same time, having greatly improved mold contamination during molding.
[0047]
【Example】
[Physical property measurement]
(1) Transparency (mistiness, Haze)
Transparency is measured according to ASTM D-1003 standard using a 3mm thick injection molded sheet. The higher the Haze value, the worse the transparency.
[0048]
(2) Transmittance
Measure a 3mm thick specimen in accordance with ASTM-1003 standards. The unit is expressed in%.
[0049]
(3) Spiral flow
Transparent polystyrene resin composition is used with Toshiba IS100EN injection molding machine, cylinder temperature is 220 ° C, mold temperature is 60 ° C, injection pressure is 600kg / cm2Under the molding conditions, injection molding is performed on a spiral mold having a thickness of 2 mm, and the fluidity is evaluated from the spiral flow length.
[0050]
(4) Melt index (MI)
Measured by ASTM D-1238 method.
[0051]
(5) Mold dirt
After 50 shots are continuously injected at 280 ° C, the surface of the mold and the appearance of the molded product are observed and evaluated according to the following criteria.
A: Not contaminated.
○: Slightly contaminated.
X: Severely contaminated.
[0052]
(6) (I) Ratio of low molecular weight polymer having a molecular weight of less than 350 in the dichloromethane-soluble component of the resin
The polystyrene resin composition is dissolved in a dichloromethane solvent and separated with a centrifugal separator, and the soluble content of the upper layer is analyzed with a GC-MS measuring instrument. A low molecular weight polymer having a molecular weight of less than 350 is measured on the basis of the standard area of styrene, and is calculated as (%)% by weight in the transparent polystyrene resin. The GC-MS measuring instrument used was “Hewlett Packard” “series number 5890A”.
[0053]
Example 1
Four continuous mixing reactors with a capacity of 40 liters are connected in order to constitute a continuous polymerization apparatus, which is used for the production of a transparent polystyrene resin composition. 8.4 parts by weight of rubber-like copolymer (styrene / butadiene = 25/75% by weight, 1,2-vinyl group content = 15.4%, tapered block copolymer having Mooney viscosity of 45), styrene 23.4 parts by weight, methacryl 38.2 parts by weight of methyl acid, 30 parts by weight of ethylbenzene, 0.08 part by weight of dodecyl mercaptan, 0.045 part by weight of pentaerythritol tetrastearate, and 0.08 part by weight of benzoyl peroxide are used as a raw material solution and continuously reacted at a flow rate of 35 kg / hr. It is sent to the tank and polymerization is performed. The temperature of the first reactor is 109 ° C, the temperature of the second reactor is 114 ° C, the temperature of the third reactor is 130 ° C, the temperature of the fourth reactor is 140 ° C, and the total polymerization conversion is 60%. . After polymerization, the polymerization solution is continuously sent from the reaction vessel to the devolatilizer, the devolatilization vacuum is kept at 200 Torr, volatile substances such as unreacted monomers and organic solvents are separated, and the resulting resin is pelletized with an extruder. Shape.
[0054]
The composition of the copolymer continuous phase of the obtained transparent polystyrene resin is 36 parts by weight of styrene units and 64 parts by weight of methyl methacrylate units, and the weight average particle diameter of the dispersed phase rubber particles is 0.42 μm. Further, (I) the ratio of the low molecular weight polymer having a molecular weight of less than 350 in the dichloromethane-soluble component of the transparent polystyrene resin (hereinafter simply referred to as the ratio of the low molecular weight polymer) is 0.62% by weight. In addition, content of the pentaerythritol tetrastearate of a resin composition is 0.1 weight part (100 weight part transparent polystyrene type resin reference | standard).
[0055]
Example 2
Four continuous mixing reactors with a capacity of 40 liters are connected in order to constitute a continuous polymerization apparatus, which is used for the production of a transparent polystyrene resin composition. 8.4 parts by weight of rubber-like copolymer (styrene / butadiene = 25/75% by weight, 1,2-vinyl group content = 15.4%, tapered block copolymer having Mooney viscosity of 45), styrene 23.4 parts by weight, methacryl 38.2 parts by weight of methyl acid, 30 parts by weight of ethylbenzene, 0.09 part by weight of dodecyl mercaptan, 0.14 part by weight of pentaerythritol tetrastearate, and 0.09 part by weight of benzoyl peroxide are used as raw material solutions and continuously reacted at a flow rate of 35 kg / hr. It is sent to the tank and polymerization is performed. The temperature of the first reactor is 103 ° C, the temperature of the second reactor is 107 ° C, the temperature of the third reactor is 122 ° C, the temperature of the fourth reactor is 132 ° C, and the total polymerization conversion is 60%. . After polymerization, the polymerization solution is continuously sent from the reaction vessel to the devolatilizer, the devolatilization vacuum is kept at 130 Torr, volatile substances such as unreacted monomers and organic solvents are separated, and the resulting resin is pelletized with an extruder. Shape.
[0056]
The composition of the copolymer continuous phase of the obtained transparent polystyrene resin is 36 parts by weight of styrene units and 64 parts by weight of methyl methacrylate units, and the weight average particle diameter of the dispersed phase rubber particles is 0.41 μm. The ratio of the low molecular weight polymer is 0.43% by weight. In addition, content of the pentaerythritol tetrastearate of a resin composition is 0.3 weight part (100 weight part transparent polystyrene type resin reference | standard).
[0057]
Example 3
Four continuous mixing reactors with a capacity of 40 liters are connected in order to constitute a continuous polymerization apparatus, which is used for the production of a transparent polystyrene resin composition. 8.4 parts by weight of rubber-like copolymer (styrene / butadiene = 25/75% by weight, 1,2-vinyl group content = 15.4%, tapered block copolymer having Mooney viscosity of 45), styrene 22.8 parts by weight, methacryl 37.0 parts by weight of methyl acid, 1.8 parts by weight of acrylonitrile, 30 parts by weight of ethylbenzene, 0.1 part by weight of dodecyl mercaptan, 0.32 part by weight of pentaerythritol tetrastearate, and 0.1 part by weight of benzoyl peroxide are used as a raw material solution, and the flow rate is 35 kg / hr with a pump. And continuously polymerize to the reaction vessel. The temperature of the first reactor is 102 ° C, the temperature of the second reactor is 106 ° C, the temperature of the third reactor is 117 ° C, the temperature of the fourth reactor is 127 ° C, and the total polymerization conversion is 60%. . After polymerization, the polymerization solution is continuously sent from the reaction vessel to the devolatilizer, the devolatilization vacuum is kept at 80 Torr, volatile substances such as unreacted monomers and organic solvents are separated, and the resulting resin is pelletized with an extruder. Shape.
[0058]
The composition of the copolymer continuous phase of the obtained transparent polystyrene resin is 34 parts by weight of styrene units, 63 parts by weight of methyl methacrylate units, and 3 parts by weight of acrylonitrile units. Is 0.35 μm. The ratio of the low molecular weight polymer is 0.22% by weight. The content of pentaerythritol tetrastearate in the resin composition is 0.7 parts by weight (based on 100 parts by weight of transparent polystyrene resin).
[0059]
Example 4
Four continuous mixing reactors with a capacity of 40 liters are connected in order to constitute a continuous polymerization apparatus, which is used for the production of a transparent polystyrene resin composition. 8.4 parts by weight of rubber-like copolymer (styrene / butadiene = 25/75% by weight, 1,2-vinyl group content = 15.4%, tapered block copolymer having Mooney viscosity of 45), styrene 22.8 parts by weight, methacryl 37.0 parts by weight of methyl acid, 1.8 parts by weight of acrylonitrile, 30 parts by weight of ethylbenzene, 0.1 part by weight of dodecyl mercaptan, 0.91 part by weight of pentaerythritol tetrastearate, and 0.1 part by weight of benzoyl peroxide are used as a raw material solution, and the flow rate is 35 kg / hr with a pump. And continuously polymerize to the reaction vessel. The temperature of the first reactor is 102 ° C, the temperature of the second reactor is 106 ° C, the temperature of the third reactor is 117 ° C, the temperature of the fourth reactor is 127 ° C, and the total polymerization conversion is 60%. . After polymerization, the polymerization solution is continuously sent from the reaction vessel to the devolatilizer, the devolatilization vacuum is kept at 80 Torr, volatile substances such as unreacted monomers and organic solvents are separated, and the resulting resin is pelletized with an extruder. Shape.
[0060]
The composition of the copolymer continuous phase of the obtained transparent polystyrene resin is 34 parts by weight of styrene units, 63 parts by weight of methyl methacrylate units, and 3 parts by weight of acrylonitrile units. Is 0.35 μm. The ratio of the low molecular weight polymer is 0.21% by weight. The content of pentaerythritol tetrastearate in the resin composition is 2.0 parts by weight (based on 100 parts by weight of transparent polystyrene resin).
[0061]
Example 5
Four continuous mixing reactors with a capacity of 40 liters are connected in order to constitute a continuous polymerization apparatus, which is used for the production of a transparent polystyrene resin composition. 8.4 parts by weight of rubber-like copolymer (styrene / butadiene = 25/75% by weight, 1,2-vinyl group content = 15.4%, tapered block copolymer having Mooney viscosity of 45), styrene 22.8 parts by weight, methacryl 37.0 parts by weight of methyl acid, 1.8 parts by weight of acrylonitrile, 30 parts by weight of ethylbenzene, 0.1 part by weight of dodecyl mercaptan, and 0.1 part by weight of benzoyl peroxide are used as raw material solutions and continuously sent to a reaction vessel at a flow rate of 35 kg / hr by a pump. I do. The temperature of the first reactor is 102 ° C, the temperature of the second reactor is 106 ° C, the temperature of the third reactor is 117 ° C, the temperature of the fourth reactor is 127 ° C, and the total polymerization conversion is 60%. . After polymerization, the polymerization solution is continuously sent from the reaction vessel to the devolatilizer, the devolatilization vacuum is kept at 80 Torr, volatile substances such as unreacted monomers and organic solvents are separated, and the resulting resin is pelletized with an extruder. Shape. Then, 0.3 parts by weight of pentaerythritol tetrastearate is mixed and homogenized with 100 parts by weight of the styrenic resin and kneaded in an extruder to form a pellet.
The composition of the copolymer continuous phase of the obtained transparent polystyrene resin is 34 parts by weight of styrene units, 63 parts by weight of methyl methacrylate units, and 3 parts by weight of acrylonitrile units. Is 0.33 μm. The ratio of the low molecular weight polymer is 0.24% by weight. In addition, content of the pentaerythritol tetrastearate of a resin composition is 0.3 weight part (100 weight part transparent polystyrene type resin reference | standard).
[0062]
Comparative Example 1
Four continuous mixing reactors with a capacity of 40 liters are connected in order to constitute a continuous polymerization apparatus, which is used for the production of a transparent polystyrene resin composition. 8.4 parts by weight of rubber-like copolymer (styrene / butadiene = 25/75% by weight, 1,2-vinyl group content = 15.4%, tapered block copolymer having Mooney viscosity of 45), styrene 22.8 parts by weight, methacryl 37.0 parts by weight of methyl acid, 1.8 parts by weight of acrylonitrile, 30 parts by weight of ethylbenzene, 0.06 parts by weight of dodecyl mercaptan, 0.48 parts by weight of pentaerythritol tetrastearate, and 0.05 parts by weight of benzoyl peroxide are used as a raw material solution, and 35 kg / hr by a pump. Polymerization is carried out by continuously sending to the reaction vessel at a flow rate. The temperature of the first reactor is 114 ° C, the temperature of the second reactor is 120 ° C, the temperature of the third reactor is 135 ° C, the temperature of the fourth reactor is 155 ° C, and the total polymerization conversion is 64%. . After polymerization, the polymerization solution is continuously sent from the reaction vessel to the devolatilizer, the devolatilization vacuum is kept at 250 Torr, volatile substances such as unreacted monomers and organic solvents are separated, and the resulting resin is pelletized with an extruder. Shape.
[0063]
The composition of the copolymer continuous phase of the obtained transparent polystyrene resin is 34 parts by weight of styrene units, 63 parts by weight of methyl methacrylate units, and 3 parts by weight of acrylonitrile units. Is 0.45 μm. The ratio of the low molecular weight polymer is 2.2% by weight.
[0064]
The content of pentaerythritol tetrastearate in the resin composition is 1.0 part by weight (based on 100 parts by weight of transparent polystyrene resin).
[0065]
Comparative Example 2
Four continuous mixing reactors with a capacity of 40 liters are connected in order to constitute a continuous polymerization apparatus, which is used for the production of a transparent polystyrene resin composition. 8.4 parts by weight of rubber-like copolymer (styrene / butadiene = 25/75% by weight, 1,2-vinyl group content = 15.4%, tapered block copolymer having Mooney viscosity of 45), styrene 22.8 parts by weight, methacryl 37.0 parts by weight of methyl acid, 1.8 parts by weight of acrylonitrile, 30 parts by weight of ethylbenzene, 0.1 part by weight of dodecyl mercaptan, and 0.1 part by weight of benzoyl peroxide are used as raw material solutions and continuously sent to a reaction vessel at a flow rate of 35 kg / hr by a pump. I do. The temperature of the first reactor is 102 ° C, the temperature of the second reactor is 106 ° C, the temperature of the third reactor is 117 ° C, the temperature of the fourth reactor is 127 ° C, and the total polymerization conversion is 60%. . After polymerization, the polymerization solution is continuously sent from the reaction vessel to the devolatilizer, the devolatilization vacuum is kept at 80 Torr, volatile substances such as unreacted monomers and organic solvents are separated, and the resulting resin is pelletized with an extruder. Shape.
[0066]
The composition of the copolymer continuous phase of the obtained transparent polystyrene resin is 34 parts by weight of styrene units, 63 parts by weight of methyl methacrylate units, and 3 parts by weight of acrylonitrile units. Is 0.37 μm. Further, the ratio of the low molecular weight polymer is 0.25% by weight, and the resulting resin composition has poor release properties at the time of injection molding.
[0067]
Comparative Example 3
Four continuous mixing reactors with a capacity of 40 liters are connected in order to constitute a continuous polymerization apparatus, which is used for the production of a transparent polystyrene resin composition. 8.4 parts by weight of rubber-like copolymer (styrene / butadiene = 25/75% by weight, 1,2-vinyl group content = 15.4%, tapered block copolymer having Mooney viscosity of 45), styrene 22.8 parts by weight, methacryl 37.0 parts by weight of methyl acid, 1.8 parts by weight of acrylonitrile, 30 parts by weight of ethylbenzene, 0.09 part by weight of dodecyl mercaptan, and 0.1 part by weight of benzoyl peroxide are used as raw material solutions and continuously sent to a reaction tank at a flow rate of 35 kg / hr by a pump. I do. The temperature of the first reactor is 102 ° C, the temperature of the second reactor is 106 ° C, the temperature of the third reactor is 117 ° C, the temperature of the fourth reactor is 127 ° C, and the total polymerization conversion is 60%. . After polymerization, the polymerization solution is continuously sent from the reaction vessel to the devolatilizer, the devolatilization vacuum is kept at 80 Torr, volatile substances such as unreacted monomers and organic solvents are separated, and the resulting resin is pelletized with an extruder. Shape. Then, 6 parts by weight of pentaerythritol tetrastearate is mixed and homogenized with 100 parts by weight of the styrenic resin and kneaded with an extruder to form a pellet.
The composition of the copolymer continuous phase of the obtained transparent polystyrene resin is 34 parts by weight of styrene units, 63 parts by weight of methyl methacrylate units, and 3 parts by weight of acrylonitrile units. Is 0.40 μm. The ratio of the low molecular weight polymer is 0.24% by weight. The content of pentaerythritol tetrastearate in the resin composition is 6 parts by weight (based on 100 parts by weight of transparent polystyrene resin).
[0068]
Comparative Example 4
Four continuous mixing reactors with a capacity of 40 liters are connected in order to constitute a continuous polymerization apparatus, which is used for the production of a transparent polystyrene resin composition. 8.4 parts by weight of rubber-like copolymer (styrene / butadiene = 25/75% by weight, 1,2-vinyl group content = 15.4%, tapered block copolymer having Mooney viscosity of 45), styrene 22.8 parts by weight, methacryl 37.0 parts by weight of methyl acid, 1.8 parts by weight of acrylonitrile, 30 parts by weight of ethylbenzene, 0.09 part by weight of dodecyl mercaptan, and 0.09 part by weight of benzoyl peroxide are used as raw material solutions and continuously sent to a reaction vessel at a flow rate of 35 kg / hr by a pump. I do. The temperature of the first reactor is 103 ° C, the temperature of the second reactor is 107 ° C, the temperature of the third reactor is 123 ° C, the temperature of the fourth reactor is 131 ° C, and the total polymerization conversion is 60%. . After polymerization, the polymerization solution is continuously sent from the reaction vessel to the devolatilizer, the devolatilization vacuum is kept at 130 Torr, volatile substances such as unreacted monomers and organic solvents are separated, and the resulting resin is pelletized with an extruder. Shape. Then, 2 parts by weight of methyl stearate is mixed and homogenized with 100 parts by weight of the styrenic resin and kneaded with an extruder to form pellets.
The composition of the copolymer continuous phase of the obtained transparent polystyrene resin is 34 parts by weight of styrene units, 63 parts by weight of methyl methacrylate units, and 3 parts by weight of acrylonitrile units. Is 0.40 μm. The ratio of the low molecular weight polymer is 0.43% by weight.
[0069]
Comparative Example 5
Four continuous mixing reactors with a capacity of 40 liters are connected in order to constitute a continuous polymerization apparatus, which is used for the production of a transparent polystyrene resin composition. 8.4 parts by weight of rubber-like copolymer (styrene / butadiene = 25/75% by weight, 1,2-vinyl group content = 15.4%, tapered block copolymer having Mooney viscosity of 45), styrene 22.8 parts by weight, methacryl 37.0 parts by weight of methyl acid, 1.8 parts by weight of acrylonitrile, 30 parts by weight of ethylbenzene, 0.08 part by weight of dodecyl mercaptan, and 0.08 part by weight of benzoyl peroxide are used as raw material solutions and continuously sent to a reaction vessel at a flow rate of 35 kg / hr by a pump. I do. The temperature of the first reactor is 104 ° C, the temperature of the second reactor is 109 ° C, the temperature of the third reactor is 125 ° C, the temperature of the fourth reactor is 135 ° C, and the total polymerization conversion is 60%. . After polymerization, the polymerization solution is continuously sent from the reaction vessel to the devolatilizer, the devolatilization vacuum is kept at 200 Torr, volatile substances such as unreacted monomers and organic solvents are separated, and the resulting resin is pelletized with an extruder. Shape. Then, 2 parts by weight of butyl stearate is mixed and homogenized with 100 parts by weight of the styrenic resin and kneaded with an extruder to form pellets.
[0070]
The composition of the copolymer continuous phase of the obtained transparent polystyrene resin is 34 parts by weight of styrene units, 63 parts by weight of methyl methacrylate units, and 3 parts by weight of acrylonitrile units. Is 0.41 μm. The ratio of the low molecular weight polymer is 0.62% by weight.
[0071]
Comparative Example 6
Four continuous mixing reactors with a capacity of 40 liters are connected in order to constitute a continuous polymerization apparatus, which is used for the production of a transparent polystyrene resin composition. 8.4 parts by weight of rubber-like copolymer (styrene / butadiene = 25/75% by weight, 1,2-vinyl group content = 15.4%, tapered block copolymer having Mooney viscosity of 45), styrene 22.8 parts by weight, methacryl 37.0 parts by weight of methyl acid, 1.8 parts by weight of acrylonitrile, 30 parts by weight of ethylbenzene, 0.1 part by weight of dodecyl mercaptan, and 0.1 part by weight of benzoyl peroxide are used as raw material solutions and continuously sent to a reaction vessel at a flow rate of 35 kg / hr by a pump. I do. The temperature of the first reactor is 102 ° C, the temperature of the second reactor is 106 ° C, the temperature of the third reactor is 117 ° C, the temperature of the fourth reactor is 127 ° C, and the total polymerization conversion is 60%. . After polymerization, the polymerization solution is continuously sent from the reaction vessel to the devolatilizer, the devolatilization vacuum is kept at 80 Torr, volatile substances such as unreacted monomers and organic solvents are separated, and the resulting resin is pelletized with an extruder. Shape. Then, 2 parts by weight of ethylene bis stearamide is mixed and homogenized with 100 parts by weight of the styrenic resin and kneaded with an extruder to form pellets.
The composition of the copolymer continuous phase of the obtained transparent polystyrene resin is 34 parts by weight of styrene units, 63 parts by weight of methyl methacrylate units, and 3 parts by weight of acrylonitrile units. Is 0.35 μm. The proportion of low molecular weight polymer is 0.21% by weight.
[0072]
Comparative Example 7
Four continuous mixing reactors with a capacity of 40 liters are connected in order to constitute a continuous polymerization apparatus, which is used for the production of a transparent polystyrene resin composition. 8.4 parts by weight of rubber-like copolymer (styrene / butadiene = 25/75% by weight, 1,2-vinyl group content = 15.4%, tapered block copolymer having Mooney viscosity of 45), styrene 22.8 parts by weight, methacryl 37.0 parts by weight of methyl acid, 1.8 parts by weight of acrylonitrile, 30 parts by weight of ethylbenzene, 0.1 part by weight of dodecyl mercaptan, 0.91 part by weight of mineral oil (ESSO, Primol 382), and 0.1 part by weight of benzoyl peroxide as a raw material solution, The polymerization is carried out continuously by a pump at a flow rate of 35 kg / hr to the reaction vessel. The temperature of the first reactor is 102 ° C, the temperature of the second reactor is 106 ° C, the temperature of the third reactor is 117 ° C, the temperature of the fourth reactor is 127 ° C, and the total polymerization conversion is 60%. . After polymerization, the polymerization solution is continuously sent from the reaction vessel to the devolatilizer, the devolatilization vacuum is kept at 80 Torr, volatile substances such as unreacted monomers and organic solvents are separated, and the resulting resin is pelletized with an extruder. Shape.
[0073]
The composition of the copolymer continuous phase of the obtained transparent polystyrene resin is 34 parts by weight of styrene units, 63 parts by weight of methyl methacrylate units, and 3 parts by weight of acrylonitrile units. Is 0.37 μm. The proportion of low molecular weight polymer is 0.21% by weight. In addition, content of the mineral oil in a resin composition is 2 weight part (100 weight part transparent polystyrene resin reference | standard).
[0074]
Comparative Example 8
Four continuous mixing reactors with a capacity of 40 liters are connected in order to constitute a continuous polymerization apparatus, which is used for the production of a transparent polystyrene resin composition. 8.4 parts by weight of rubber-like copolymer (styrene / butadiene = 25/75% by weight, 1,2-vinyl group content = 15.4%, tapered block copolymer having Mooney viscosity of 45), styrene 22.8 parts by weight, methacryl 37.0 parts by weight of methyl acid, 1.8 parts by weight of acrylonitrile, 30 parts by weight of ethylbenzene, 0.1 part by weight of dodecyl mercaptan, and 0.1 part by weight of benzoyl peroxide are used as raw material solutions and continuously sent to the reaction tank at a flow rate of 35 kg / hr. Polymerize. The temperature of the first reactor is 102 ° C, the temperature of the second reactor is 106 ° C, the temperature of the third reactor is 117 ° C, the temperature of the fourth reactor is 127 ° C, and the total polymerization conversion is 60%. . After polymerization, the polymerization solution is continuously sent from the reaction vessel to the devolatilizer, the devolatilization vacuum is kept at 80 Torr, volatile substances such as unreacted monomers and organic solvents are separated, and the resulting resin is pelletized with an extruder. Shape. Then, 2 parts by weight of polyethylene wax (Mitsui Chemicals Co., Ltd., 200P) is mixed and homogenized with 100 parts by weight of the styrenic resin and kneaded with an extruder to form pellets.
[0075]
The composition of the copolymer continuous phase of the obtained transparent polystyrene resin is 34 parts by weight of styrene units, 63 parts by weight of methyl methacrylate units, and 3 parts by weight of acrylonitrile units. Is 0.37 μm. The proportion of low molecular weight polymer is 0.22% by weight. The content of polyethylene wax in the resin composition is 2 parts by weight (based on 100 parts by weight of transparent polystyrene resin).
[0076]
Comparative Example 9
Four continuous mixing reactors with a capacity of 40 liters are connected in order to constitute a continuous polymerization apparatus, which is used for the production of a transparent polystyrene resin composition. 8.4 parts by weight of rubber-like copolymer (styrene / butadiene = 25/75% by weight, 1,2-vinyl group content = 15.4%, tapered block copolymer having Mooney viscosity of 45), styrene 22.8 parts by weight, methacryl 37.0 parts by weight of methyl acid, 1.8 parts by weight of acrylonitrile, 30 parts by weight of ethylbenzene, 0.08 parts by weight of dodecyl mercaptan, 1.21 parts by weight of pentaerythritol tetrastearate, and 0.06 parts by weight of benzoyl peroxide are used as a raw material solution, and 35 kg / hr by a pump. Polymerization is carried out by continuously sending to the reaction vessel at a flow rate. The temperature of the first reactor is 110 ° C, the temperature of the second reactor is 115 ° C, the temperature of the third reactor is 140 ° C, the temperature of the fourth reactor is 150 ° C, and the total polymerization conversion is 63%. . After polymerization, the polymerization solution is continuously sent from the reaction vessel to the devolatilizer, the devolatilization vacuum is kept at 250 Torr, volatile substances such as unreacted monomers and organic solvents are separated, and the resulting resin is pelletized with an extruder. Shape.
[0077]
The composition of the copolymer continuous phase of the obtained transparent polystyrene resin is 34 parts by weight of styrene units, 63 parts by weight of methyl methacrylate units, and 3 parts by weight of acrylonitrile units. Is 0.46 μm. The ratio of the low molecular weight polymer is 1.52% by weight.
[0078]
The content of pentaerythritol tetrastearate in the resin composition is 2.5 parts by weight (based on 100 parts by weight of transparent polystyrene resin).
[0079]
Table 1 shows the physical property measurement results of Examples 1 to 5 and Comparative Examples 1 to 9.
[0080]
[Table 1]
Example 6
0.6 parts by weight of pentaerythritol tetrastearate is uniformly mixed with 100 parts by weight of polystyrene and kneaded with an extruder to form pellets. As a result of measurement using this, the ratio of the low molecular weight polymer was 0.55% by weight, X + 2Y was 1.7, the processability (MI) was 3.4, the transparency (Haze) was 1.2%, the transmittance was 90.0%, and the injection molding was separated. Good moldability.
[0082]
Comparative Example 10
As a result of measurement using the same polystyrene as in Example 6 (without adding pentaerythritol tetrastearate), the ratio of the low molecular weight polymer was 0.55% by weight, X + 2Y was 1.1, workability (MI) was 2.9, and transparency ( Haze) is 0.9%, and the transmittance is 91.1%, but the releasability of resin injection molding is poor.
[0083]
Example 7
0.5 parts by weight of pentaerythritol tetrastearate is mixed and homogenized with respect to 100 parts by weight of a styrene-acrylonitrile copolymer (acrylonitrile unit: 24% by weight), and kneaded with an extruder to form pellets. As a result of measurement using this, the ratio of the low molecular weight polymer was 1.20% by weight, X + 2Y was 2.9, the processability (MI) was 2.8, the transparency (Haze) was 1.8%, the transmittance was 90.2%, and the injection molding was separated. Good moldability.
[0084]
Comparative Example 11
As a result of measurement using the same styrene-acrylonitrile copolymer (without adding pentaerythritol tetrastearate) as in Example 7, the ratio of the low molecular weight polymer was 1.20% by weight, X + 2Y was 2.4, and the workability (MI) was 2.4. The transparency (Haze) is 1.5% and the transmittance is 91.1%, but the mold release property of resin injection molding is not good.
Claims (10)
当該透明ポリスチレン系樹脂組成物は、厚さ３ｍｍの射出成形シートを用いて、ASTM D-1003標準に従って測定されるHaze値が6.0以下であり、
前記（Ｉ）透明ポリスチレン系樹脂のジクロロメタン可溶分中の分子量350未満の低分子量重合体の比率が2.0重量％以下であり、
且つ下記式(1)を満たす、射出成形用の透明ポリスチレン系樹脂組成物。
0.6＜X＋2Y＜3.50 式(1)
X；前記（Ｉ）透明ポリスチレン系樹脂100重量部に対する（II）ペンタエリスリトール系エステル類化合物の重量部
Y；前記（Ｉ）透明ポリスチレン系樹脂のジクロロメタン可溶分中の分子量350未満の低分子量重合体の重量％(I) A transparent polystyrene resin composition containing (II) 0.01 to 4 parts by weight of a pentaerythritol ester compound relative to 100 parts by weight of a transparent polystyrene resin,
The transparent polystyrene resin composition has a Haze value of 6.0 or less measured using an injection molded sheet having a thickness of 3 mm according to the ASTM D-1003 standard,
The ratio of the low molecular weight polymer having a molecular weight of less than 350 in the dichloromethane soluble content of the transparent polystyrene resin (I) is 2.0% by weight or less,
A transparent polystyrene resin composition for injection molding satisfying the following formula (1).
0.6 <X + 2Y < 3.50 formula (1)
X: parts by weight of (II) pentaerythritol ester compound with respect to 100 parts by weight of the transparent polystyrene resin (I)
Y:% by weight of the low molecular weight polymer having a molecular weight of less than 350 in the dichloromethane-soluble component of the transparent polystyrene resin (I)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW089114834 | 2000-07-25 | ||
| TW89114834A TW506973B (en) | 2000-07-25 | 2000-07-25 | Transparent styrenic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002053721A JP2002053721A (en) | 2002-02-19 |
| JP3725440B2 true JP3725440B2 (en) | 2005-12-14 |
Family
ID=21660531
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001116934A Expired - Lifetime JP3725440B2 (en) | 2000-07-25 | 2001-04-16 | Transparent polystyrene resin composition |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3725440B2 (en) |
| TW (1) | TW506973B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6806313B2 (en) * | 2003-03-05 | 2004-10-19 | W. R. Grace & Co.-Conn. | Erucamide-free closure and liner compositions |
| TWI481651B (en) * | 2013-05-23 | 2015-04-21 | Chi Mei Corp | (meth) acrylate-styrene based copolymer composition and the molding product thereof |
| TWI503362B (en) * | 2013-10-28 | 2015-10-11 | Chi Mei Corp | Rubber-modified polystyrene-based resin composition and molding product |
-
2000
- 2000-07-25 TW TW89114834A patent/TW506973B/en not_active IP Right Cessation
-
2001
- 2001-04-16 JP JP2001116934A patent/JP3725440B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002053721A (en) | 2002-02-19 |
| TW506973B (en) | 2002-10-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6515072B2 (en) | Transparent rubber-modified styrenic resin composition | |
| CN117500876A (en) | High clarity and ductile molding compositions comprising SMMA copolymer and SBC-block copolymer | |
| US4879343A (en) | Heat and impact resistant resin composition | |
| CN107041144A (en) | The method for preparing thermoplastic resin | |
| JP3725440B2 (en) | Transparent polystyrene resin composition | |
| EP3187529B1 (en) | Thermoplastic resin composition and product formed therefrom | |
| JP4101175B2 (en) | Transparent rubber-modified copolymer resin and resin composition thereof | |
| CN103087274B (en) | Transparent rubber modified styrene resin | |
| CN104610694B (en) | Styrene resin composition and molded article obtained therefrom | |
| KR20130068871A (en) | Heat-resistant abs resin composition with excellent processability and resistance for discoloration at high temperature and method for preparing the same | |
| WO1998044034A1 (en) | Conjugated diene polymer composition and rubber-reinforced styrene resin | |
| JP4112528B2 (en) | Transparent rubber-modified styrene resin | |
| JP5632447B2 (en) | Thermoplastic resin composition and molded article thereof | |
| JPH04126745A (en) | Impact-resistant thermoplastic resin composition | |
| JP5016199B2 (en) | Transparent resin composition excellent in surface hardness and transparent resin molded product formed by molding the resin composition | |
| CN108690339A (en) | Thermoplastic resin composition and molded article | |
| KR19980027068A (en) | Styrenic resin composition | |
| JP3206076B2 (en) | Thermoplastic resin composition | |
| TW202216803A (en) | Thermoplastic resin composition and molded article manufactured using the same | |
| JPH0641393A (en) | Resin pellet having high nitrile content | |
| JPS61235450A (en) | Resin composition | |
| KR100356461B1 (en) | Thermoplastic Resin Composition | |
| JP2005179644A (en) | Transparent rubber-modified polystyrene resin | |
| JP3361360B2 (en) | Resin composition and CFC-resistant molded article for refrigerator exterior | |
| JPH0665321A (en) | Heat resistance improver and thermoplastic resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20040224 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20040524 |
|
| A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20040531 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040823 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20050222 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20050427 |
|
| A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20050530 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20050823 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20050921 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 3725440 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090930 Year of fee payment: 4 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090930 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100930 Year of fee payment: 5 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110930 Year of fee payment: 6 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120930 Year of fee payment: 7 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130930 Year of fee payment: 8 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |