JPH0320144B2 - - Google Patents
Info
- Publication number
- JPH0320144B2 JPH0320144B2 JP1473886A JP1473886A JPH0320144B2 JP H0320144 B2 JPH0320144 B2 JP H0320144B2 JP 1473886 A JP1473886 A JP 1473886A JP 1473886 A JP1473886 A JP 1473886A JP H0320144 B2 JPH0320144 B2 JP H0320144B2
- Authority
- JP
- Japan
- Prior art keywords
- block copolymer
- weight
- vinyl aromatic
- molecular weight
- copolymer resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920001400 block copolymer Polymers 0.000 claims description 70
- -1 vinyl aromatic compound Chemical class 0.000 claims description 44
- 229920002554 vinyl polymer Polymers 0.000 claims description 27
- 229920005989 resin Polymers 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 23
- 239000011342 resin composition Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 description 23
- 239000000178 monomer Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- 238000001746 injection moulding Methods 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-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
- 239000011230 binding agent Substances 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 125000001979 organolithium group Chemical group 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229920000359 diblock copolymer Polymers 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920000428 triblock copolymer Polymers 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- FEXBEKLLSUWSIM-UHFFFAOYSA-N 2-Butyl-4-methylphenol Chemical compound CCCCC1=CC(C)=CC=C1O FEXBEKLLSUWSIM-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical class C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- DBOSBRHMHBENLP-UHFFFAOYSA-N 4-tert-Butylphenyl Salicylate Chemical compound C1=CC(C(C)(C)C)=CC=C1OC(=O)C1=CC=CC=C1O DBOSBRHMHBENLP-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- VIZORQUEIQEFRT-UHFFFAOYSA-N Diethyl adipate Chemical compound CCOC(=O)CCCCC(=O)OCC VIZORQUEIQEFRT-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 229920001890 Novodur Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229920001744 Polyaldehyde Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- IORUEKDKNHHQAL-UHFFFAOYSA-N [2-tert-butyl-6-[(3-tert-butyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenyl] prop-2-enoate Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)OC(=O)C=C)=C1O IORUEKDKNHHQAL-UHFFFAOYSA-N 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 150000001934 cyclohexanes Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 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
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000010102 injection blow moulding Methods 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 1
- 239000012778 molding material Substances 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 229910000489 osmium tetroxide Inorganic materials 0.000 description 1
- 239000012285 osmium tetroxide Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000314 poly p-methyl styrene Polymers 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920006216 polyvinyl aromatic Chemical class 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
［産業上の利用分野］
本発明は透明で物理的特性に優れたブロツク共
重合体樹脂組成物に関する。
更に詳しくは、透明で、流動性、表面硬度、剛
性、耐衝撃性のバランスに優れた、MIの異なる
２種以上のブロツク共重合体より構成されるブロ
ツク共重合体樹脂組成物に関する。
［従来の技術］
従来ポリスチレンは優れた透明性、光沢、剛性
等の諸特性のほか、安価で加工性に優れるという
特長を有するため、広く一般に利用されている。
しかし、耐衝撃性に劣るところから、シートやフ
イルム、一部成形品の分野での用途に制限があ
る。
一方、耐衝撃性ポリスチレンは、未加硫ゴムの
スチレン溶液を塊状重合、溶液重合、或いは塊状
−懸濁重合して得られたもので、耐衝撃性には優
れるものの、一般に不透明であり、透明性を要求
される用途には使用できない。
ポリスチレンの透明性と耐衝撃性ポリスチレン
の耐衝撃性を併せ持つスチレン系樹脂として、ア
ニオン重合法によるビニル芳香族化合物と共役ジ
エン化合物とのブロツク共重合体に関する提案が
近年数多く見られるようになつてきた。
そのようなものとして例えば特公昭47−3252号
公報、特公昭47−28915号公報には、ビニル芳香
族化合物単量体と共役ジエン化合物単量体を交互
に、かつ各々２回以上添加反応させて得られる所
謂マルチブロツク共重合体について開示されてい
る。
また、特公昭48−2423号公報、特公昭58−
10410号公報には、両末端にビニル芳香族化合物
重合体ブロツクを有し、中間に共役ジエン化合物
を主体とする重合体ブロツクを配した所謂３型漸
減ブロツク共重合体について開示されている。
更に、特開昭59−187048号公報には、ビニル芳
香族化合物と共役ジエン化合物とからなる放射状
のブロツク共重合体樹脂に、それよりも共役ジエ
ン含有量が高い直鎖状のブロツク共重合体をブレ
ンドした組成物が開示されている。
しかしながら、これらブロツク共重合体樹脂は
いずれも共通して、耐衝撃性の改良と同時に、流
動性、表面硬度、剛性が低下するという問題を有
している。
［発明が解決しようとする問題点］
以上に述べた如く、従来の技術で得られるブロ
ツク共重合体樹脂の耐衝撃性と、流動性、表面硬
度、剛性とは二律背反の関係にあり、これらを同
時に満足する技術は未だ見出せていない。
本発明者らは、かかる状況下において、透明
で、耐衝撃性と流動性、表面硬度、剛性とのバラ
ンスに優れたブロツク共重合体樹脂の開発を目的
として鋭意検討を行なつた。
その結果、特定のMIの範囲を有するブロツク
共重合体を特定の組成で混合することによつて、
透明で、流動性、表面硬度、剛性を損うことなく
耐衝撃性を改良し得るという、従来の知見では予
想し得なかつた事実を見出し、本発明を完成する
に至つた。
［問題点を解決するための手段］
即ち、本発明は、ビニル芳香族化合物含量が70
重量％を越え95重量％以下である、少なくとも２
個のビニル芳香族化合物を主体とするハードセグ
メントと少なくとも１個の共役ジエン化合物を主
体とするソフトセグメントからなるブロツク共重
合体樹脂の混合物よりなる樹脂組成物であつて、
該ブロツク共重合体樹脂の混合物が、
(a) メルトフローインデツクス（以下MIと略す。
単位ｇ／10分）が7.0未満である上記ブロツク
共重合体の少なくとも１種以上からなり、その
平均MIが1.0≦MI＜7.0の範囲にあるブロツク
共重合体の群、20〜80重量％、
(b) MIが7.0≦MI＜15である上記ブロツク共重
合体の少なくとも１種以上からなり、その平均
MIが7.0≦MI＜15の範囲にあるブロツク共重
合体の群、０〜60重量％、
(c) MIが15以上である上記ブロツク共重合体の
少なくとも１種以上からなり、その平均MIが
15≦MI＜100の範囲にあるブロツク共重合体の
群、０〜70重量％
から構成され、かつ(b)成分を含む場合は(b)成分と
(a)成分の平均MI比（(b)／(a)）が2.5以上15未満で
あることを特徴とする2.5以上30未満のMIを有す
るブロツク共重合体樹脂組成物に関し、透明で、
耐衝撃性と流動性、表面硬度、剛性とのバランス
に優れたブロツク共重合体樹脂を提供するもので
ある。
本発明におけるブロツク共重合体樹脂組成物
は、優れた透明性を有し、かつ、従来の単一MI、
或いは単一に近いMIを有するブロツク共重合体
樹脂に比し、流動性、表面硬度、剛性が同等の場
合にはより優れた耐衝撃性を有し、耐衝撃性が同
等の場合は、より優れた流動性、表面硬度、剛性
を有するという特徴を示す。
即ち、本発明のブロツク共重合体樹脂組成物の
物性バランスは、単一MIのブロツク共重合体樹
脂では達成し得ないものである。
以下に本発明の詳細を説明する。
本発明のブロツク共重合体樹脂組成物は上記の
如く、(a)、(b)、(c)の３成分からなるが、(a)成分が
必須成分である。
しかし、(a)成分単独では本発明の効果は得られ
ず、(b)成分又は(c)成分、或いはその両方と混合す
る必要がある。その際(a)成分は少なくとも20重量
％以上混合物中に含まれていなければならず、20
重量％未満では優れた耐衝撃性を得ることができ
ない。また、(a)成分が80重量％を越えると耐衝撃
性のほか、流動性もやや劣るものとなる。
中間のMI値を有する(b)成分は組成物中に含ま
れていずともよい。含まれる場合は(b)成分と(a)成
分の平均MIの比が少なくとも2.5以上になるよう
双方の平均MI値に差がなくとはならない。平均
MI比が2.5未満では優れた耐衝撃性を発現するこ
とができない。(b)成分は最高60重量％まで混合す
ることができるが、60重量％を越えるとやはり耐
衝撃性の劣つたものとなつてしまう。
(c)成分は(b)成分の含まれていない場合に必須成
分となるが、70重量％を越えることは出来ない。
(a)、(b)、(c)３成分のより好ましい組成は、(a)成
分30〜70重量％、(b)成分０〜50重量％、(c)成分０
〜60重量％であるが、特に好ましい組成は(a)成分
30〜70重量％、(b)成分が含まれておらず、(c)成分
70〜30重量％である。
尚、(a)成分の平均MIが1.0未満、或いは(c)成分
の平均MIが100以上となる場合は、優れた物性バ
ランスを得ることができない。
本発明を構成する、ビニル芳香族化合物含量が
70重量％を越え95重量％以下で、少なくとも２個
のビニル芳香族化合物を主体とするハードセグメ
ントと少なくとも１個の共役ジエン化合物を主体
とするソフトセグメントとからなるブロツク共重
合体は一例として以下の如き一般式で表わされ
る。
一般式
Ａ（−Ｂ−Ａ）o、（Ａ−Ｂ）o+1、Ｂ（−Ａ−Ｂ）o+
1、
［（Ａ−Ｂ）−o］−nＸ、［（Ａ−Ｂ）−oＡ］−nＸ、
［（Ｂ−
Ａ）−o］−nＸ、［（Ｂ−Ａ）−oＢ］−nＸ
ここに、Ａはビニル芳香族化合物を主体とする
ホードセグメント、Ｂは共役ジエン化合物を主体
とするソフトセグメントを表わし、ｎは１〜５の
整数、ｍは２〜20の整数を示す。またＸは多官能
性結合剤の残基を表わす。
Ａブロツクを形成するビニル芳香族化合物とし
ては、スチレン、パラメチルスチレン、第３級ブ
チルスチレン、α−メチルスチレン等があり、こ
の中から１種またはそれ以上が選ばれる。好適に
はスチレンが用いられる。
Ｂブロツクを形成する共役ジエン化合物として
は、１，３−ブタジエン、イソプレン等があり、
この中から１種又はそれ以上が選ばれる。好適に
は１，３−ブタジエンが用いられる。
多官能性結合剤としては、酢酸エチル、アジピ
ン酸ジエチル、テレフタル酸ジメチルの如きモノ
エステル、及びポリエステル、エポキシ化大豆
油、エポキシ化亜麻仁油、エポキシ化１、２−ポ
リブタジエンの如きポリエポキサイド、ジブロム
エタン、四塩化ケイ素の如きポリハライド、ビジ
ニルベンゼンの如きポリビニル芳香族化合物、ト
ルエンジイソシアネート、その他ポリイミン、ポ
リアルデヒド、ポリケトン、ポリアンハイドラン
ド等に該当する種々の化合物が使用できる。
前記一般式において、ＡブロツクとＢブロツク
の境界は双方の単量体ユニツトの濃度が連続的に
変化する所謂テーパー構造であつても良いし、明
瞭に各ブロツクが区別される所謂完全ブロツク構
造であつても良い。
また、Ａブロツク中のビニル芳香族化合物含
量、及びＢブロツク中と共役ジエン化合物含量は
各々少なくとも80重量％以上、好ましくは90重量
％以上必要とする。
更に、各ブロツク共重合体中のビニル芳香族化
合物含量は70重量％を越え95重量％以下、好まし
くは72〜85重量％である。
ブロツク共重合体の製造方法としては従来公知
の手法をそのまま用いることができる。
即ち、不活性炭化水素溶媒中、アニオン重合開
始剤として有機リチウム化合物を用いて、ビニル
芳香族化合物と共役ジエン化合物とを共重合する
ものである。
不活性炭化水素溶媒としては、シクロヘキサ
ン、ベンゼンが好ましく用いられるが、他にｎ−
ペニタン、ｎ−ヘキサン、イソオクタン、トルエ
ン、キシレン等が使用できる。これらの２種以上
を併用してもよい。また、有機リチウム化合物と
しては、ｎ−ブチルリチウム、ｓ−ブチルリチウ
ムが好ましく用いられるが、他にエチルリチウ
ム、ｎ−プロピルリチウム、ｎ−デシルリチウ
ム、フエニルリチウム、２−ナフチルリチウム、
４−ブチルフエニルリチウム、シクロヘキシルリ
チウム等が使用できる。単量体の反応速度を増加
させるために、重合に先立つて不活性溶媒中に少
量のエーテル類、第三段アミン類等の極性化合物
を共存させておいても良い。
エーテル類として、ジエチルエーテル、ジフエ
ニルエーテル、テトラヒドロフラン、ジエチレン
グリコールメチルエーテル等が、第三級アミン類
としてはトリメチルアミン、トリエチルアミン、
テトラメチルエチレンジアミン等がある。
ブロツク共重合体製造の一例として以下の方法
がある。
不活性炭化水素溶媒中、有機リチウム開始剤を
用い、第一段としてのビニル芳香族化合物単量体
を反応せしめ、反応終了後系内に第二段としての
共役ジエン化合物単量体を添加反応してジブロツ
ク型ポリマーを形成し、更に第三段としてビニル
芳香族化合物単量体を添加反応して直鎖状のＡ−
Ｂ−Ａ型ブロツク共重合体を得る方法。或いは二
段目以降の反応を繰り返してＡ−（Ｂ−Ａ）o型マ
ルチブロツク共重合体を得る方法。
上記方法において、第二段としてビニル芳香族
化合物単量体と共役ジエン化合物単量体を同時に
系内に添加反応して所謂テーパー構造を含むＡ−
Ｂ−Ａ型ブロツク共重合体を得る方法。或いは第
二段の反応を繰り返すことによつてテーパー構造
を含むＡ−（Ｂ−Ａ）o型マルチブロツク共重合体
を得る方法。
第二段として共役ジエンを添加反応した後、前
記多官能性結合剤で処理し、放射状ブロツク共重
合体を得る方法。
第一段としてビニル芳香族化合物単量体と共役
ジエン化合物単量体の混合物を反応し、少なくと
もこの操作を２回以上繰り返して直鎖状の（Ｂ−
Ａ）o+1型ブロツク共重合体を得る方法。
本発明においてはいかなる重合法で得られたも
のであつてもよいが、好ましくは完全ブロツクＡ
−Ｂ−Ａ型が用いられる。
尚、本発明で言うメルトフローインデツクス
（MI）とは、ASTMD1238、Ｇ条件（温度200℃、
荷重５Kg）で測定された値を言い、単量体の量に
対する有機リチウム化合物の量によつてコントロ
ールされる。
該ブロツク共重合体製造時、時として反応活性
を失つたＡ−Ｂジブロツク共重合体を生成するこ
とがあるが、最終生成物中に含まれるＡ−Ｂジブ
ロツク共重合体の量は多くとも40％以内、好まし
くは30％以内にとどめることが好ましい。
該ブロツク共重合体中のハードセグメントの分
子量は通常5000〜200000の範囲にあるが、ブロツ
ク共重合体分子鎖中に含まれる最も高分子量のハ
ードセグメントと最も低分子量のハードセグメン
トの分子量比（高分子量／低分子量）が1.0〜3.0
であることが好ましい。
該分子量比が3.0を越えると成形品、特に射出
成形品等において、射出方向に対して平行と直角
方向で収縮挙動が異なり、そのため成形品が反つ
たり、物理特性に方向性が出たりする問題を生じ
ることがある。
ハードセグメントの分子量比は以下の如き方法
で算出する。
ブロツク共重合体が完全ブロツク型である場合
は、単量体使用量と分子量は比例するため、各ヒ
ードセグメント形成に用いた単量体重量の最大値
と最小値の比をそのままハードセグメントの分子
量比とする。
ブロツク共重合体がテーパー構造を有するも
の、例えばB1−S1−B2−S2において、B1−S1間、
B2−S2間にテーパー構造を有する場合、B1−S1
部、及びB1−S1−B2−S2部夫々についてエル・
エム・コルトフ（L.M.KOLTHNOFF）の方法
〈ビニル芳香族化合物と共役ジエンとの共重合体
を四酸化オスミウム触媒の存在下、ジ・ターシヤ
リーブチルハイドロパーオキサイドで酸化分解
し、共重合体中のブロツク状に結合したビニル芳
香族炭化水素化合物の量を測定する方法。ジヤー
ナル・オブ・ポリマーサイエント、第１巻、第
429頁（1946年）〔J.Polym.sci，１、429（1946）〕
に記載〉でブロツク状に結合したビニル状に結合
したビニル芳香族化合物の量を求める。ブロツク
状に結合したビニル芳香族化合物の量がハードセ
グメントの量と等しいものとして、B1−S1部と
B2−S2部それぞれに含まれるハードセグメント
量を求める。それらの比をハードセグメントの分
子量比として用いる。
本発明を構成するブロツク共重合体のポリマー
構造は、通常前記一般式から選択された１種から
なるが、(a)、(b)、(c)３成分が互いに異なるポリマ
ー構造を有していてもさしつかえないし、各１成
分が異なるポリマー構造のブロツク共重合体より
成り立つものであつても良い。
本発明のブロツク共重合体樹脂組成物全体のビ
ニル芳香族化合物含量は、70重量％を越え95重量
％以下であることが必要である。70重量％以下で
は表面硬度、剛性の著しく低いものとなり、95重
量％を越えるともはや優れた耐衝撃性を維持し得
なくなる。好ましくは72〜85重量％である。
本発明のブロツク共重合体樹脂組成物全体の
MIは2.5〜30の範囲にあることが好ましい。2.5未
満では流動性が劣るため、成形性が損なわれ、30
を越えると耐衝撃性の改良効果が見られなくな
る。流動性と耐衝撃性の面からより好ましいMI
範囲は5.0〜25である。
本発明のブロツク共重合体樹脂組成物を調製す
る方法としては、例えば以下の如きものがある。
バツチ式反応において、有機リチウム開始剤添
加量を種々に変えることによつて得たMIの異な
るブロツク共重合体のポリマー溶液を特定の組成
で均一混合した後、スチームストリツピング法、
或いは熱ロール法によつて溶媒を除去、固形のブ
ロツク共重合体樹脂組成物を得る方法。
連続的反応において、反応時間と経過と共に有
機リチウム開始剤の添加量を断続的に変え、所望
のMI値と組成になるよう調製し、反応終了後得
られたポリマー溶液を更に均一混合し、前記方法
で固形のブロツク共重合体樹脂組成物を得る方
法。
MIの異なる固形のブロツク共重合体を特定の
組成で予めドライブレンドし、押出機等で均一混
合する方法。
いずれの方法を用いても良く、上級に応じて適
宜選択すれば良い。
本発明のブロツク共重合体樹脂組成物には更に
他の目的で各種改質材、添加剤を配合することが
できる。
改質材の例としては、ビニル芳香族化合物含有
量が70％以下のビニル芳香族化合物と共役ジエン
化合物とのブロツク共重合体エラストマー、汎用
ポリスチレン、ポリパラメチルスチレン、ポリα
−メチルスチレン、アクリロニトリル−スチレン
系樹脂、スチレン−ブタジエン−アクリロニトリ
ル系樹脂、メチルメタクリレート−スチレン系樹
脂、スチレン−無水マレイン酸系樹脂、ゴム変性
耐衝撃性ポリスチレン、ポリフエニレンエーテル
樹脂、ポリカーボネート樹脂等があり、これらか
ら１種、或いは目的に応じて数種を適宜組み合わ
せて用いることができる。
また、添加剤の例としては、酸化防止剤、紫外
線吸収剤、光安定剤、ブロツキング防止剤、滑
剤、帯電防止剤、顔料、可塑剤、粘着付与剤等が
ある。
このうち酸化防止剤としては、一例として２，
６−ジ−ｔ−ブチル−４−メチルフエノール、ト
リス（ノニルフエニル）ホスフアイト、２−ｔ−
ブチル−６−（３−ｔ−ブチル−２−ヒドロキシ
−５−メチルベンジル）−４−メチルフエニルア
クリレート、ｎ−オクタデジル−３−（4′−ヒド
ロキシ−3′−5′−ジ−ｔ−ブチルフエニル）プロ
ピオネート、２−2′−メチレン−ビス（４−メチ
ル−６−ｔ−ブチルフエノール）等が、紫外線吸
収剤、光安定剤としては、一例として２−（2′−
ヒドロキシ−5′−メチルフエニル）ベンゾトリア
ゾール、２−（2′−ヒドロキシ−3′−ｔ−ブチル
−5′−メチルフエニル）−５−クロロベンゾトリ
アゾール、ｐ−ｔ−ブチルフエニルサリシレー
ト、ビス（２，２，６，６−テトラメチル−４−
ピペリジン）セバケート、ビス（１，２，２，
６，６−ペンタメチル−４−ピペリジル）セバケ
ート等がある。
またブロツキング防止剤、滑剤、帯電防止剤と
しては、一例として脂肪酸アマイド、エチレンビ
スステアロアマイド、ソルビタンモノステアレー
ト、脂肪族アルコールの飽和脂肪酸エステル、ベ
ンタエリスリトール脂肪酸エステル等の中から選
択することができる。
もちろん、ここに挙げた以外のものも使用可能
である。これら改質材、添加剤等は従来公知の方
法で背後することができる。
［実施例］
以下に本発明の実施例を示す。
実施例１〜７及び比較例１〜11
ジヤケツトと撹拌機のついたステンレス製反応
機を用いて、MIの異なる10種類のA1−Ｂ−A2型
のブロツク共重合体樹脂を調製した。
十分に窒素置換した反応器に脱水処理したシク
ロヘキサン550重量部とテトラヒドロフラン0.15
重量部を仕込んだ。次いで、第一段目としてのス
チレンモノマー42重量部を仕込み、ジヤケツトに
温水を通じて内容物温度を70℃に設定した。各種
量のｎ−ブチルリチウムを10重量％シクロヘキサ
ン溶液の形で系内に添加、反応を開始した。
スチレンの反応ピーク温度検出後10分で第二段
目として１、３−ブタジエンモノマー23重量部を
添加し、反応を続けた。１，３−ブタジエンの反
応ピーク温度検出後10分で第三段目として更にス
チレンモノマー35重量部添加し、反応を完結させ
た。反応終了後ポリマー溶液に２、６−ジ−ｔ−
ブチル−４−メチルフエノールとトリス（ノニル
フエニル）ホスフアイトを各0.5重量部添加した。
かくして得られた10種のポリマー溶液を、まず
個別に熱ロールにて溶媒を除去し押出機でペレツ
ト化し、各ペレツトを東芝機械(株)社製IS−80A
（５オンス射出成形機）を用い200℃にて厚さ３mm
の射出成形板を得た。
第１表に各ペレツトの基本特性と射出成形物性
を示す。
次いで、上記ポリマー溶液を種々の組み合わせ
で所定量混合し、同様の操作で射出成形板を得
た。
第２表にそれらの射出成形物性を示す。
[Industrial Application Field] The present invention relates to a block copolymer resin composition that is transparent and has excellent physical properties. More specifically, the present invention relates to a block copolymer resin composition that is transparent, has an excellent balance of fluidity, surface hardness, rigidity, and impact resistance, and is composed of two or more block copolymers with different MI. [Prior Art] Conventionally, polystyrene has been widely used because it has various properties such as excellent transparency, gloss, and rigidity, as well as being inexpensive and easy to process.
However, due to poor impact resistance, its use in the fields of sheets, films, and some molded products is limited. On the other hand, impact-resistant polystyrene is obtained by bulk polymerization, solution polymerization, or bulk-suspension polymerization of a styrene solution of unvulcanized rubber, and although it has excellent impact resistance, it is generally opaque and transparent. It cannot be used for applications that require high performance. In recent years, many proposals have been made for block copolymers of vinyl aromatic compounds and conjugated diene compounds produced by anionic polymerization as styrenic resins that have both the transparency and impact resistance of polystyrene. . As such, for example, Japanese Patent Publication No. 47-3252 and Japanese Patent Publication No. 47-28915 disclose a method in which a vinyl aromatic compound monomer and a conjugated diene compound monomer are added alternately and reacted two or more times each. A so-called multi-block copolymer obtained by the method is disclosed. Also, Special Publication No. 48-2423, Special Publication No. 58-
Publication No. 10410 discloses a so-called type 3 gradually decreasing block copolymer having vinyl aromatic compound polymer blocks at both ends and a polymer block mainly composed of a conjugated diene compound in the middle. Furthermore, JP-A-59-187048 discloses that in addition to a radial block copolymer resin consisting of a vinyl aromatic compound and a conjugated diene compound, a linear block copolymer resin having a higher conjugated diene content is used. A composition comprising a blend of the following is disclosed. However, all of these block copolymer resins have a common problem in that, while improving impact resistance, fluidity, surface hardness, and rigidity decrease. [Problems to be Solved by the Invention] As stated above, the impact resistance, fluidity, surface hardness, and rigidity of block copolymer resins obtained by conventional techniques are in an antinomic relationship. A technique that satisfies both requirements has not yet been found. Under these circumstances, the present inventors conducted extensive studies with the aim of developing a block copolymer resin that is transparent and has an excellent balance between impact resistance, fluidity, surface hardness, and rigidity. As a result, by mixing block copolymers with a specific MI range in a specific composition,
The present invention was completed based on the discovery that the material is transparent and that impact resistance can be improved without impairing fluidity, surface hardness, or rigidity, which could not be expected based on conventional knowledge. [Means for Solving the Problems] That is, the present invention has a vinyl aromatic compound content of 70
more than 95% by weight, at least 2
A resin composition comprising a mixture of a block copolymer resin comprising a hard segment mainly composed of a vinyl aromatic compound and a soft segment mainly composed of at least one conjugated diene compound, the resin composition comprising:
The mixture of block copolymer resins has the following properties: (a) melt flow index (hereinafter abbreviated as MI);
A group of block copolymers consisting of at least one of the above block copolymers having an average MI in the range of 1.0≦MI<7.0, 20 to 80% by weight, (b) Consisting of at least one of the above block copolymers whose MI is 7.0≦MI<15, the average of which is
A group of block copolymers having an MI of 7.0≦MI<15, 0 to 60% by weight;
A group of block copolymers in the range of 15≦MI<100, consisting of 0 to 70% by weight and containing component (b), if it contains component (b).
A transparent block copolymer resin composition having an MI of 2.5 or more and less than 30, characterized in that the average MI ratio ((b)/(a)) of component (a) is 2.5 or more and less than 15.
The present invention provides a block copolymer resin with an excellent balance of impact resistance, fluidity, surface hardness, and rigidity. The block copolymer resin composition of the present invention has excellent transparency, and the conventional single MI,
Or, compared to block copolymer resins with near-uniform MI, if the fluidity, surface hardness, and rigidity are the same, they have better impact resistance; Characterized by excellent fluidity, surface hardness, and rigidity. That is, the physical property balance of the block copolymer resin composition of the present invention cannot be achieved with a block copolymer resin of a single MI. The details of the present invention will be explained below. As mentioned above, the block copolymer resin composition of the present invention consists of three components (a), (b), and (c), of which component (a) is an essential component. However, the effects of the present invention cannot be obtained with component (a) alone, and it is necessary to mix it with component (b) or component (c), or both. In this case, component (a) must be contained in the mixture at least 20% by weight, and 20% by weight must be contained in the mixture.
If the amount is less than % by weight, excellent impact resistance cannot be obtained. Furthermore, if the content of component (a) exceeds 80% by weight, not only the impact resistance but also the fluidity will be slightly inferior. Component (b) having an intermediate MI value may not be included in the composition. If it is included, there must be a difference in the average MI value of both components so that the ratio of the average MI of component (b) and component (a) is at least 2.5. average
If the MI ratio is less than 2.5, excellent impact resistance cannot be exhibited. Component (b) can be mixed up to a maximum of 60% by weight, but if it exceeds 60% by weight, the impact resistance will still be poor. Component (c) becomes an essential component when component (b) is not included, but it cannot exceed 70% by weight. A more preferable composition of the three components (a), (b), and (c) is: (a) component 30 to 70% by weight, (b) component 0 to 50% by weight, and (c) component 0.
~60% by weight, but a particularly preferred composition is component (a)
30-70% by weight, does not contain component (b), component (c)
It is 70-30% by weight. Note that if the average MI of component (a) is less than 1.0, or if the average MI of component (c) is 100 or more, an excellent balance of physical properties cannot be obtained. The vinyl aromatic compound content constituting the present invention is
An example of a block copolymer consisting of a hard segment mainly composed of at least two vinyl aromatic compounds and a soft segment mainly composed of at least one conjugated diene compound, which is more than 70% by weight and less than 95% by weight, is as follows. It is expressed by a general formula such as. General formula A(-B-A) o , (A-B) o+1 , B(-A-B) o+
1 ,
[(A-B)-o] -nX , [(A-B) -oA ] -nX ,
[(B-
A)-o ] -n X, [(B-A) -o B ] -n where n is an integer of 1 to 5 and m is an integer of 2 to 20. Further, X represents a residue of a polyfunctional binding agent. Examples of the vinyl aromatic compound forming the A block include styrene, paramethylstyrene, tertiary butylstyrene, α-methylstyrene, etc., and one or more of these may be selected. Styrene is preferably used. Conjugated diene compounds forming the B block include 1,3-butadiene, isoprene, etc.
One or more types are selected from these. 1,3-butadiene is preferably used. Polyfunctional binders include monoesters such as ethyl acetate, diethyl adipate, dimethyl terephthalate, and polyesters, polyepoxides such as epoxidized soybean oil, epoxidized linseed oil, epoxidized 1,2-polybutadiene, dibromoethane, Polyhalides such as silicon tetrachloride, polyvinyl aromatic compounds such as vinylbenzene, toluene diisocyanate, and various other compounds corresponding to polyimines, polyaldehydes, polyketones, polyanhydrands, etc. can be used. In the above general formula, the boundary between the A block and the B block may have a so-called tapered structure in which the concentrations of both monomer units change continuously, or it may have a so-called complete block structure in which each block is clearly distinguished. It's okay if it's hot. Further, the content of the vinyl aromatic compound in the A block and the content of the conjugated diene compound in the B block must each be at least 80% by weight, preferably 90% by weight or more. Further, the vinyl aromatic compound content in each block copolymer is greater than 70% by weight and less than 95% by weight, preferably from 72 to 85% by weight. As a method for producing the block copolymer, conventionally known methods can be used as they are. That is, a vinyl aromatic compound and a conjugated diene compound are copolymerized in an inert hydrocarbon solvent using an organolithium compound as an anionic polymerization initiator. As the inert hydrocarbon solvent, cyclohexane and benzene are preferably used, but other n-
Penitane, n-hexane, isooctane, toluene, xylene, etc. can be used. Two or more of these may be used in combination. In addition, as the organic lithium compound, n-butyllithium and s-butyllithium are preferably used, but ethyllithium, n-propyllithium, n-decyllithium, phenyllithium, 2-naphthyllithium,
4-Butylphenyllithium, cyclohexyllithium, etc. can be used. In order to increase the reaction rate of the monomers, a small amount of polar compounds such as ethers and tertiary amines may be present in the inert solvent prior to polymerization. Ethers include diethyl ether, diphenyl ether, tetrahydrofuran, diethylene glycol methyl ether, etc. Tertiary amines include trimethylamine, triethylamine,
Examples include tetramethylethylenediamine. The following method is an example of producing a block copolymer. Using an organolithium initiator in an inert hydrocarbon solvent, a vinyl aromatic compound monomer as the first stage is reacted, and after the reaction is completed, a conjugated diene compound monomer as the second stage is added to the system for reaction. A diblock type polymer is formed, and in the third step, a vinyl aromatic compound monomer is added and reacted to form a linear A-
A method for obtaining a B-A type block copolymer. Alternatively, a method of repeating the second and subsequent reactions to obtain an A-(B-A) o type multi-block copolymer. In the above method, in the second step, a vinyl aromatic compound monomer and a conjugated diene compound monomer are simultaneously added and reacted in the system to form an A-
A method for obtaining a B-A type block copolymer. Alternatively, a method of obtaining an A-(B-A) o type multi-block copolymer containing a tapered structure by repeating the second stage reaction. In the second step, a conjugated diene is added and reacted, and then treated with the polyfunctional binder to obtain a radial block copolymer. In the first step, a mixture of a vinyl aromatic compound monomer and a conjugated diene compound monomer is reacted, and this operation is repeated at least twice to form a linear (B-
A) Method for obtaining o+1 type block copolymer. In the present invention, it may be obtained by any polymerization method, but preferably complete block A
-B-A type is used. In addition, the melt flow index (MI) referred to in the present invention refers to ASTMD1238, G conditions (temperature 200℃,
The value is measured under a load of 5 kg) and is controlled by the amount of organic lithium compound relative to the amount of monomer. During the production of the block copolymer, an A-B diblock copolymer that has lost its reaction activity is sometimes produced, but the amount of A-B diblock copolymer contained in the final product is at most 40%. % or less, preferably 30% or less. The molecular weight of the hard segment in the block copolymer is usually in the range of 5,000 to 200,000, but the molecular weight ratio (high molecular weight) between the highest molecular weight hard segment and the lowest molecular weight hard segment contained in the block copolymer molecular chain is molecular weight/low molecular weight) is 1.0 to 3.0
It is preferable that If the molecular weight ratio exceeds 3.0, the shrinkage behavior of molded products, especially injection molded products, will be different in parallel and perpendicular directions to the injection direction, resulting in warping of the molded product and directional changes in physical properties. This may cause problems. The molecular weight ratio of the hard segment is calculated by the following method. If the block copolymer is a completely block type, the amount of monomer used is proportional to the molecular weight, so the ratio of the maximum and minimum monomer weights used to form each hard segment can be directly adjusted to form the hard segment. Molecular weight ratio. When the block copolymer has a tapered structure, for example, B 1 -S 1 -B 2 -S 2 , between B 1 and S 1 ,
If there is a tapered structure between B 2 −S 2 , B 1 −S 1
and B 1 −S 1 −B 2 −S for each of the 2 parts.
LMKOLTHNOFF's method: A copolymer of a vinyl aromatic compound and a conjugated diene is oxidatively decomposed with di-tert-butyl hydroperoxide in the presence of an osmium tetroxide catalyst to form a block-like structure in the copolymer. A method for measuring the amount of vinyl aromatic hydrocarbon compounds bound to. Journal of Polymer Scientists, Volume 1, No.
429 pages (1946) [J.Polym.sci, 1, 429 (1946)]
Determine the amount of vinyl aromatic compounds bonded in a block-like manner as described in . Assuming that the amount of vinyl aromatic compounds bonded in block form is equal to the amount of hard segments, 1 part of B 1 −S and
B 2 −S Find the amount of hard segments included in each of the two parts. The ratio is used as the molecular weight ratio of the hard segment. The polymer structure of the block copolymer constituting the present invention usually consists of one type selected from the above general formula, but the three components (a), (b), and (c) have different polymer structures from each other. Alternatively, each component may be composed of a block copolymer having a different polymer structure. The vinyl aromatic compound content of the entire block copolymer resin composition of the present invention must be more than 70% by weight and less than 95% by weight. If it is less than 70% by weight, the surface hardness and rigidity will be extremely low, and if it exceeds 95% by weight, it will no longer be possible to maintain excellent impact resistance. Preferably it is 72 to 85% by weight. The entire block copolymer resin composition of the present invention
Preferably, the MI is in the range 2.5-30. If it is less than 2.5, the fluidity will be poor and the moldability will be impaired.
If it exceeds this value, the effect of improving impact resistance will not be seen. MI is more preferable in terms of fluidity and impact resistance.
Range is 5.0-25. Examples of methods for preparing the block copolymer resin composition of the present invention include the following. In a batch reaction, polymer solutions of block copolymers with different MI obtained by varying the amount of organolithium initiator added were homogeneously mixed with a specific composition, and then steam stripping was performed.
Alternatively, the solvent is removed by a hot roll method to obtain a solid block copolymer resin composition. In a continuous reaction, the amount of the organolithium initiator added is intermittently changed as the reaction time progresses to obtain the desired MI value and composition, and after the reaction is completed, the resulting polymer solution is further homogeneously mixed, and then A method for obtaining a solid block copolymer resin composition by a method. A method in which solid block copolymers with different MIs are dry-blended in a specific composition in advance and mixed uniformly using an extruder, etc. Either method may be used and may be selected as appropriate depending on the level of skill. The block copolymer resin composition of the present invention may further contain various modifiers and additives for other purposes. Examples of modifiers include block copolymer elastomers of vinyl aromatic compounds and conjugated diene compounds with a vinyl aromatic compound content of 70% or less, general-purpose polystyrene, polyparamethylstyrene, polyα
- Methyl styrene, acrylonitrile-styrene resin, styrene-butadiene-acrylonitrile resin, methyl methacrylate-styrene resin, styrene-maleic anhydride resin, rubber-modified high-impact polystyrene, polyphenylene ether resin, polycarbonate resin, etc. One type or a combination of several types can be used depending on the purpose. Examples of additives include antioxidants, ultraviolet absorbers, light stabilizers, antiblocking agents, lubricants, antistatic agents, pigments, plasticizers, and tackifiers. Among these, examples of antioxidants include 2,
6-di-t-butyl-4-methylphenol, tris(nonylphenyl)phosphite, 2-t-
Butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, n-octadecyl-3-(4'-hydroxy-3'-5'-di-t- Butylphenyl) propionate, 2-2'-methylene-bis(4-methyl-6-t-butylphenol), etc. are examples of UV absorbers and light stabilizers.
Hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, p-t-butylphenyl salicylate, bis(2, 2,6,6-tetramethyl-4-
piperidine) sebacate, bis(1,2,2,
6,6-pentamethyl-4-piperidyl) sebacate and the like. Further, the antiblocking agent, lubricant, and antistatic agent may be selected from fatty acid amide, ethylene bisstearamide, sorbitan monostearate, saturated fatty acid ester of aliphatic alcohol, bentaerythritol fatty acid ester, etc. . Of course, other materials than those listed here can also be used. These modifiers, additives, etc. can be added by conventionally known methods. [Example] Examples of the present invention are shown below. Examples 1 to 7 and Comparative Examples 1 to 11 Using a stainless steel reactor equipped with a jacket and a stirrer, ten types of A1 -B- A2 type block copolymer resins having different MI were prepared. 550 parts by weight of dehydrated cyclohexane and 0.15 parts of tetrahydrofuran are placed in a reactor that has been sufficiently purged with nitrogen.
I prepared the weight section. Next, 42 parts by weight of styrene monomer as the first stage was charged, and hot water was poured into the jacket to set the content temperature at 70°C. Various amounts of n-butyllithium were added to the system in the form of a 10% by weight cyclohexane solution to initiate the reaction. Ten minutes after the detection of the reaction peak temperature of styrene, 23 parts by weight of 1,3-butadiene monomer was added as a second step, and the reaction was continued. Ten minutes after the detection of the reaction peak temperature of 1,3-butadiene, 35 parts by weight of styrene monomer was further added as a third step to complete the reaction. After the reaction is complete, add 2,6-di-t- to the polymer solution.
0.5 parts by weight each of butyl-4-methylphenol and tris(nonylphenyl)phosphite were added. The 10 kinds of polymer solutions obtained in this way were first individually heated to remove the solvent and then pelletized using an extruder.
(5oz injection molding machine) at 200℃ to a thickness of 3mm.
An injection molded plate was obtained. Table 1 shows the basic characteristics and injection molding properties of each pellet. Next, predetermined amounts of the above polymer solutions were mixed in various combinations, and injection molded plates were obtained in the same manner. Table 2 shows their injection molding properties.
【表】【table】
【表】
第１表に示される単一MIのブロツク共重合体
樹脂は透明性と表面硬さには優れるものの、流動
性の向上（MI値の増加）と同時にダート衝撃値
が著しく低下する。
一方、第２表に示される本発明のブロツク共重
合体樹脂組成物は、もとは第１表のポリマーと同
一のものでありながら、流動性とダート衝撃値の
バランスが大きく改良され、しかも、透明性、表
面硬度は全く損なわれていないことがわかる。
実施例８、９及び比較例12、13
前述と同じ要領でA1−Ｂ／A2型テーパードブ
ロツク共重合体樹脂を調製した。
−Ｂ／A2部は１、３−ブタジエンモノマーと
スチレンモノマーを同時に系内に添加して反応し
たことを意味する。得られたポリマーの基本特性
を第３表に、それらの射出成形物性を第４表に示
す。
本発明のブロツク共重合体樹脂組成物のダート
衝撃値と剛性、表面硬度のバランスが、単一MI
値わ有するものに比べ大きく改良されていること
がわかる。[Table] Although the single MI block copolymer resin shown in Table 1 has excellent transparency and surface hardness, the dart impact value decreases significantly at the same time as the fluidity improves (MI value increases). On the other hand, the block copolymer resin composition of the present invention shown in Table 2 is originally the same as the polymer shown in Table 1, but the balance between fluidity and dart impact value is greatly improved, and It can be seen that the transparency and surface hardness were not impaired at all. Examples 8 and 9 and Comparative Examples 12 and 13 A 1 -B/A 2 type tapered block copolymer resin was prepared in the same manner as described above. -B/A 2 parts means that 1,3-butadiene monomer and styrene monomer were simultaneously added to the system and reacted. The basic properties of the obtained polymers are shown in Table 3, and their injection molding properties are shown in Table 4. The balance between dart impact value, rigidity, and surface hardness of the block copolymer resin composition of the present invention is achieved by a single MI
It can be seen that this is a great improvement compared to the value-added version.
【表】【table】
【表】【table】
【表】
実施例 10〜12
前述と同じ要領で、S2／S1組成とMIの異なる
S1−Ｂ−S2型ブロツク共重合体樹脂の調製を行な
つた。評価に供したブロツク共重合体樹脂は、い
ずれも(a)成分に相当する1.0≦MI＜7.0の範囲の
MIを有するものと、(c)成分に相当する15≦MI＜
100の範囲のMIを有するものとの等量ブレンド物
とした。
それらの基本特性と射出成形物性を第５表に示
す。成形品のそりがハードセグメントの分子量比
が大きくなるに連れ、悪化することがわかる。[Table] Examples 10 to 12 Same procedure as above, different S 2 /S 1 composition and MI
A S1 - B-S type 2 block copolymer resin was prepared. All of the block copolymer resins subjected to evaluation had 1.0≦MI<7.0, which corresponds to component (a).
Those with MI and 15≦MI< corresponding to component (c)
Equivalent blends were made with MI in the range of 100. Table 5 shows their basic characteristics and injection molding properties. It can be seen that the warpage of the molded product worsens as the molecular weight ratio of the hard segment increases.
【表】【table】
【表】
［発明の効果］
本発明のブロツク共重合体樹脂組成物は、透明
で、優れた耐衝撃性、表面硬さ、剛性を有するた
め、各種成形品の成形素材として好適である。
即ち、通常の熱可塑性樹脂と同様に射出成形、
射出中空成形、押出成形、インフレーシヨン成形
等の加工ができ、種々の成形品、シート、フイル
ム、チユーブとすることができる。
本発明のブロツク共重合体樹脂組成物は更に、
流動性に優れ、成形時の反りがなく、物理特性が
均一であるところから、特に大型の射出成形品用
途に適している。そのようなものとしては、例え
ば、コンテナー、収納ケース、OA機器部品、弱
電部品、玩具、食品容器、日用品、雑貨等が挙げ
られる。
かくして得られた成形品は、透明、表面肌が滑
らか、割れにくい、傷が付きにくい、応力に対し
て変形しにくい、物性が均一、と言つた数々の特
徴を有するものである。[Table] [Effects of the Invention] The block copolymer resin composition of the present invention is transparent and has excellent impact resistance, surface hardness, and rigidity, and is therefore suitable as a molding material for various molded products. In other words, injection molding as well as ordinary thermoplastic resins,
It can be processed by injection blow molding, extrusion molding, inflation molding, etc., and can be made into various molded products, sheets, films, and tubes. The block copolymer resin composition of the present invention further comprises:
Because it has excellent fluidity, no warping during molding, and uniform physical properties, it is especially suitable for use in large injection molded products. Examples of such items include containers, storage cases, OA equipment parts, light electrical parts, toys, food containers, daily necessities, and miscellaneous goods. The molded product thus obtained has a number of characteristics such as being transparent, having a smooth surface, not easily cracking, not easily being scratched, not easily deformed by stress, and having uniform physical properties.
Claims (1)
重量％以下である、少なくとも２個のビニル芳香
族化合物を主体とするハードセグメントと少なく
とも１個の共役ジエン化合物を主体とするソフト
セグメントからなるブロツク共重合体樹脂の混合
物よりなる樹脂組成物であつて、該ブロツク共重
合体樹脂の混合物が、 (a) メルトフローインデツクス（以下MIと略す。
単位ｇ／10分）が7.0未満である上記ブロツク
共重合体の少なくとも１種以上からなり、その
平均MIが1.0≦MI＜7.0の範囲にあるブロツク
共重合体の群、20〜80重量％、 (b) MIが7.0≦MI＜15である上記ブロツク共重
合体の少なくとも１種以上からなり、その平均
MIが7.0≦MI＜15の範囲にあるブロツク共重
合体の群、０〜60重量％、 (c) MIが15以上である上記ブロツク共重合体の
少なくとも１種以上からなり、その平均MIが
15≦MI＜100の範囲にあるブロツク共重合体の
群、０〜70重量％ から構成され、かつ(b)成分を含む場合は(b)成分と
(a)成分の平均MI比（(b)／(a)）が2.5以上15未満で
あることを特徴とする2.5以上30未満のMIを有す
るブロツク共重合体樹脂組成物。 ２ ビニル芳香族化合物含量が70重量％を越え95
重量％以下である、少なくとも２個のビニル芳香
族化合物を主体とするハードセグメントと少なく
とも１個の共役ジエン化合物を主体とするソフト
セグメントからなるブロツク共重合体樹脂分子鎖
中に含まれる最も高分子量のハードセグメントと
最も低分子量のハードセグメントの分子量比（高
分子量／低分子量）が1.0〜3.0であることを特徴
とする特許請求の範囲第１項記載のブロツク共重
合体樹脂組成物。[Scope of Claims] 1 The vinyl aromatic compound content exceeds 70% by weight95
A resin composition comprising a mixture of a block copolymer resin comprising hard segments mainly composed of at least two vinyl aromatic compounds and soft segments mainly composed of at least one conjugated diene compound in an amount of % by weight or less. Therefore, the mixture of block copolymer resins has the following properties: (a) melt flow index (hereinafter abbreviated as MI);
A group of block copolymers consisting of at least one of the above block copolymers whose average MI is in the range of 1.0≦MI<7.0, 20 to 80% by weight, (b) Consisting of at least one of the above block copolymers whose MI is 7.0≦MI<15, the average of which is
A group of block copolymers having an MI in the range of 7.0≦MI<15, 0 to 60% by weight;
A group of block copolymers in the range of 15≦MI<100, consisting of 0 to 70% by weight and containing component (b), if it contains component (b).
A block copolymer resin composition having an MI of 2.5 or more and less than 30, characterized in that the average MI ratio ((b)/(a)) of component (a) is 2.5 or more and less than 15. 2 The vinyl aromatic compound content exceeds 70% by weight95
The highest molecular weight contained in the molecular chain of a block copolymer resin consisting of a hard segment mainly composed of at least two vinyl aromatic compounds and a soft segment mainly composed of at least one conjugated diene compound, which is less than or equal to % by weight. 2. The block copolymer resin composition according to claim 1, wherein the molecular weight ratio (high molecular weight/low molecular weight) of the hard segment of the block copolymer and the lowest molecular weight hard segment is 1.0 to 3.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1473886A JPS62174250A (en) | 1986-01-28 | 1986-01-28 | Block copolymer resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1473886A JPS62174250A (en) | 1986-01-28 | 1986-01-28 | Block copolymer resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62174250A JPS62174250A (en) | 1987-07-31 |
| JPH0320144B2 true JPH0320144B2 (en) | 1991-03-18 |
Family
ID=11869461
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1473886A Granted JPS62174250A (en) | 1986-01-28 | 1986-01-28 | Block copolymer resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62174250A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4714020B2 (en) | 2003-03-19 | 2011-06-29 | 電気化学工業株式会社 | Linear block copolymer composition |
-
1986
- 1986-01-28 JP JP1473886A patent/JPS62174250A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62174250A (en) | 1987-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0761704B1 (en) | Conjugated diene/monovinylarene block copolymers | |
| US6835778B2 (en) | Conjugated diene/monovinylarene block copolymers blends | |
| KR100364160B1 (en) | Monovinylaromatic / Conjugated Diene Copolymer and Manufacturing Method | |
| KR100235553B1 (en) | Monovinyl aromatic conjugated diene copolymers and method of preparation of the same | |
| US4418180A (en) | Preparation of branched block copolymers | |
| KR19980070384A (en) | Block copolymers, block copolymer compositions and heat-shrinkable films made therefrom | |
| JPS6392629A (en) | Bimodal star block copolymer showing excellent optical characteristic and resistance and its production | |
| JP5062936B2 (en) | Block copolymer and composition thereof | |
| JP5046469B2 (en) | Block copolymer composition | |
| KR101023000B1 (en) | Block copolymer composition | |
| KR101006039B1 (en) | Block copolymer mixture containing star-branched block copolymer | |
| JP3489597B2 (en) | Method for producing monovinylarene / conjugated diene copolymer | |
| US3939112A (en) | Thermoplastic resin composition having high impact strength | |
| JPH07216038A (en) | Star block copolymer of aromatic vinyl monomer with conjugated diene, its production, and composition containing this copolymer and crystalline polystyrene | |
| JPH07216187A (en) | Transparent high-strength resin composition | |
| JPH0320144B2 (en) | ||
| EP2138541B2 (en) | Molding material for md shrink and md shrink film | |
| JPH0797418A (en) | Transparent high-strength block copolymer | |
| JPH02117909A (en) | Shape memorizing block copolymer, use thereof and shape memorizing molded article | |
| EP3153547B1 (en) | Resin composition containing block copolymer | |
| JP3992473B2 (en) | Composition for injection molding | |
| JP3934379B2 (en) | Injection molding composition | |
| JPH02113007A (en) | Impact-resistant block copolymer | |
| JPS63258933A (en) | Novel block copolymer composition | |
| KR20050016403A (en) | Conjugated diene/monovinylarene block copolymers blends |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |