JPH03250009A - Production of rubber-modified styrene resin - Google Patents
Production of rubber-modified styrene resinInfo
- Publication number
- JPH03250009A JPH03250009A JP4569590A JP4569590A JPH03250009A JP H03250009 A JPH03250009 A JP H03250009A JP 4569590 A JP4569590 A JP 4569590A JP 4569590 A JP4569590 A JP 4569590A JP H03250009 A JPH03250009 A JP H03250009A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- styrene
- resin
- polymerization
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 32
- 239000011347 resin Substances 0.000 title claims abstract description 32
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 229920001971 elastomer Polymers 0.000 claims abstract description 114
- 239000005060 rubber Substances 0.000 claims abstract description 107
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 150000003440 styrenes Chemical class 0.000 claims abstract 3
- 238000006116 polymerization reaction Methods 0.000 claims description 64
- 239000002245 particle Substances 0.000 claims description 57
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 19
- 229920001890 Novodur Polymers 0.000 claims description 17
- 229920002857 polybutadiene Polymers 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000008961 swelling Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims 2
- 239000002904 solvent Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 6
- 229920001400 block copolymer Polymers 0.000 abstract description 5
- 230000000379 polymerizing effect Effects 0.000 abstract description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000704 physical effect Effects 0.000 description 25
- 238000004132 cross linking Methods 0.000 description 20
- 238000011156 evaluation Methods 0.000 description 17
- 230000007423 decrease Effects 0.000 description 14
- 238000000034 method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 229920005990 polystyrene resin Polymers 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 239000004793 Polystyrene Substances 0.000 description 7
- 229920002223 polystyrene Polymers 0.000 description 7
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 238000012662 bulk polymerization Methods 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- -1 that is Polymers 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 238000000635 electron micrograph Methods 0.000 description 4
- 150000001451 organic peroxides Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-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
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- 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
- RFRKTGYVXQRDJH-UHFFFAOYSA-N 2,3-dibutyl-4-methylphenol Chemical compound CCCCC1=C(C)C=CC(O)=C1CCCC RFRKTGYVXQRDJH-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OAOZZYBUAWEDRA-UHFFFAOYSA-N 3,4-dimethylidenehexane Chemical compound CCC(=C)C(=C)CC OAOZZYBUAWEDRA-UHFFFAOYSA-N 0.000 description 1
- IGLWCQMNTGCUBB-UHFFFAOYSA-N 3-methylidenepent-1-ene Chemical compound CCC(=C)C=C IGLWCQMNTGCUBB-UHFFFAOYSA-N 0.000 description 1
- LGLDSEPDYUTBNZ-UHFFFAOYSA-N 3-phenylbuta-1,3-dien-2-ylbenzene Chemical compound C=1C=CC=CC=1C(=C)C(=C)C1=CC=CC=C1 LGLDSEPDYUTBNZ-UHFFFAOYSA-N 0.000 description 1
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 description 1
- OXGOEZHUKDEEKS-UHFFFAOYSA-N 3-tert-butylperoxy-1,1,5-trimethylcyclohexane Chemical compound CC1CC(OOC(C)(C)C)CC(C)(C)C1 OXGOEZHUKDEEKS-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- FPVVYTCTZKCSOJ-UHFFFAOYSA-N Ethylene glycol distearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCOC(=O)CCCCCCCCCCCCCCCCC FPVVYTCTZKCSOJ-UHFFFAOYSA-N 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- PBGVMIDTGGTBFS-UHFFFAOYSA-N but-3-enylbenzene Chemical compound C=CCCC1=CC=CC=C1 PBGVMIDTGGTBFS-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 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
- 238000004090 dissolution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はゴム変性スチレン系樹脂の製造方法の改良に関
するものである。さらに詳しくいえば、本発明は、ＡＢ
Ｓ樹脂に匹敵する光沢及び耐衝撃性を有するとともに、
特性バランスに優れ、例えば家電製品やＯＡ機器などの
部品材料として好適なゴム変性スチレン系樹脂を効率よ
く製造する方法ｌ２関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an improvement in a method for producing a rubber-modified styrenic resin. More specifically, the present invention provides AB
It has gloss and impact resistance comparable to S resin, and
The present invention relates to a method 12 for efficiently producing a rubber-modified styrenic resin that has excellent property balance and is suitable as a component material for, for example, home appliances and OA equipment.
［従来の技術］
従来、ポリスチレンの耐衝撃性を改良する目的で、ゴム
状重合体の存在下に、スチレンを重合させることにより
、該ゴム状重合体にスチレンが一部グラフト重合され、
かつスチレンの残部がポリスチレンとなって、実質上ゴ
ム状重合体／スチレンのグラフト共重合体とポリスチレ
ンとが混在された状態とし、いわゆるゴム変性ポリスチ
レン樹脂とすることが工業的に行われている。[Prior Art] Conventionally, for the purpose of improving the impact resistance of polystyrene, styrene is partially graft-polymerized onto the rubbery polymer by polymerizing styrene in the presence of the rubbery polymer.
In addition, the remainder of the styrene becomes polystyrene, so that a rubber-like polymer/styrene graft copolymer and polystyrene are substantially mixed, and it is industrially practiced to form a so-called rubber-modified polystyrene resin.
このゴム状重合体としては、ポリブタジェンゴムとスチ
レン−ブタシュン共重合体ゴムが一般的に使用されてい
る。As this rubbery polymer, polybutadiene rubber and styrene-butashene copolymer rubber are generally used.
このようなゴム変性ポリスチレン樹脂、すなわち耐衝撃
性ポリスチレンは、耐衝撃性及び剛性に浸れ、かつ成形
加工性が良い二七から、各種用途に広く用いられている
。しかしながら、該ゴム変性ポリスチレン樹脂は、一般
にＡ Ｂ Ｓ Ｉｆｆ脂に比較して成形品表面の光沢に
劣り、かつ衝撃強度も低いという欠点を有している。最
近、ＡＢＳ樹脂に匹敵する光沢や耐衝撃性を有するゴム
変性ポリスチレンの出現の要望が、コストダウンや薄肉
化志向により市場から強まってきている。Such rubber-modified polystyrene resins, that is, high-impact polystyrenes, are widely used in various applications because of their high impact resistance and rigidity, as well as good moldability. However, the rubber-modified polystyrene resin generally has the disadvantages that the surface of the molded article is inferior in gloss and the impact strength is low compared to ABS If resin. Recently, demand for rubber-modified polystyrene with gloss and impact resistance comparable to ABS resins has been increasing in the market due to the desire for cost reduction and thinner walls.
ところで、ゴム変性ポリスチレンＨＲ脂に？いては、通
常ゴム状重合体はスチレン系重合体中に、粒子状に分散
しており、この粒子の大きさと、耐衝撃性及び光沢とは
密接な関係を有することは、良く知られている。すなわ
ち、光沢は、該ゴム状重合体の粒子が小さいほど優れて
いるが、その反面、耐衝撃性は該ゴム状重合体の粒子が
小さくなるのに比例して低下し、ある限度以上になると
、実質的に耐衝撃性の改良効果がなくなる。By the way, what about rubber modified polystyrene HR fat? It is well known that rubbery polymers are usually dispersed in styrene polymers in the form of particles, and that the size of these particles has a close relationship with impact resistance and gloss. . In other words, the smaller the particles of the rubbery polymer, the better the gloss, but on the other hand, the impact resistance decreases in proportion to the smaller the particles of the rubbery polymer, and beyond a certain limit, the impact resistance decreases. , the effect of improving impact resistance is virtually eliminated.
従来のゴム変性ポリスチレン樹脂組成物においては、所
望の耐衝撃性を得るために、ゴム状重合体を、粒径が１
μｍ以上、通常１−１０μｍの範囲の粒子として、ポリ
スチレン樹脂相中に分散させているが、光沢などに劣る
ために、用途の制限を免れないという問題があった。In conventional rubber-modified polystyrene resin compositions, in order to obtain the desired impact resistance, the rubbery polymer is mixed with a particle size of 1.
Particles with a size of 1 to 10 μm or more are dispersed in a polystyrene resin phase, but the problem is that the gloss is poor and the use of these particles is limited.
一方、前記ゴム変性ポリスチレン樹脂における耐衝撃性
の発現は軟質成分（スチレン系重合体を内蔵したゴム状
物質）に依存することから、耐衝撃性に優れたゴム変性
ポリスチレン樹脂を得るためには、該軟質成分の組成及
び構造を制御する必要があることも知られている。まｊ
；、該軟質成分の組成及び構造を示す指標の１つとして
軟質成分の膨潤指数があり、このｗｍｒｔｔ数に耐衝撃
性を最大にする領域があることも公知である。On the other hand, since the expression of impact resistance in the rubber-modified polystyrene resin depends on the soft component (rubber-like material containing a styrene polymer), in order to obtain a rubber-modified polystyrene resin with excellent impact resistance, It is also known that there is a need to control the composition and structure of the soft component. Maj
It is also known that the swelling index of the soft component is one of the indicators indicating the composition and structure of the soft component, and that there is a range in which the impact resistance is maximized in this wmrtt number.
他方、ゴム成分として、スチレン−ブタジエン系ブロッ
ク共重合体ゴムを使用し、スチレンの塊状重合により、
ゴム粒子を微細化させた光沢及び耐衝撃性に優れるゴム
変性ポリスチレン樹脂が開示されている（特公昭６０−
５７４３３号公報、特開昭６３−１１２６４６号公報）
。しかしながら、通常のスチレン−ブタジエン系ブロッ
ク共重合体ゴムを使用すると、未反応モノマーや、溶剤
を脱揮する後処理工程において、ゴム粒子の破壊が生じ
やすく、光沢低下を招くおそれがあり、特に脱揮器とし
て動機械を使用しｔ；場合には、剪断力による破壊が顕
著となるという問題が生じる。On the other hand, a styrene-butadiene block copolymer rubber is used as the rubber component, and by bulk polymerization of styrene,
A rubber-modified polystyrene resin with fine rubber particles and excellent gloss and impact resistance has been disclosed (Japanese Patent Publication No. 1983-
57433, Japanese Patent Application Laid-Open No. 112646/1983)
. However, when ordinary styrene-butadiene block copolymer rubber is used, the rubber particles tend to be destroyed in the post-treatment step to devolatilize unreacted monomers and solvents, which may lead to a decrease in gloss. If a moving machine is used as a vaporizer, a problem arises in that damage due to shearing force becomes significant.
〔発明が解決しようとする課題１
本発明は、このような塊状重合によるゴム変性ポリスチ
レン樹脂の製造方法が有する欠点を克服し、ＡＢＳ樹脂
に匹敵する光沢及び耐衝撃性を有するとともに、特性バ
ランスに優れたゴム変性スチレン系樹脂を効率よく製造
する方法を提供することを目的としてなされｔ；もので
ある。[Problem to be Solved by the Invention 1] The present invention overcomes the drawbacks of the manufacturing method of rubber-modified polystyrene resin by bulk polymerization, and has a gloss and impact resistance comparable to that of ABS resin, as well as a balanced property. This invention was developed for the purpose of providing a method for efficiently producing an excellent rubber-modified styrenic resin.
［課題を解決するための手段Ｊ
本発明者らは前記目的を達成するために鋭意研究を重ね
ｌ；結果、塊状重合によるゴム変性ポリスチレン樹脂の
製造において、ゴム成分として、１１，２−ビニル結合
含有量及びスチレン単位含有量が特定の範囲にあるスチ
レン−ブタジエン系ブロック共重合体ゴム、又はこのも
のとポリブタジェンゴムとの混合物を用い、かつ脱揮器
供給前の重合後期で、温度、転化率及び滞留時間を制御
して、ゴムの架橋度をコントロールすることにより、そ
の目的を達成しうろことを見い出し、この知見に基づい
て本発明を完成するに至った。[Means for Solving the Problems J The present inventors have conducted extensive research in order to achieve the above object; as a result, in the production of rubber-modified polystyrene resin by bulk polymerization, 11,2-vinyl bonds were used as the rubber component. Using a styrene-butadiene block copolymer rubber whose content and styrene unit content are within a specific range, or a mixture of this and polybutadiene rubber, and in the late stage of polymerization before supplying to the devolatilizer, the temperature, It was discovered that the objective could be achieved by controlling the degree of crosslinking of the rubber by controlling the conversion rate and residence time, and based on this knowledge, the present invention was completed.
すなわち、本発明は、１１，２−ビニル結合含有量が５
〜２０％で、かつスチレン単位含有量が２０〜５０重量
％のスチレン−ブタジエン系ブロック共重合体ゴム、又
はこのスチレン−ブタジエン系ブロック共重合体ゴム５
０重量％以上とポリブタジェンゴム５０重量％以下との
混合物を含有するスチレン系単量体溶液を、最終重合器
出口における転化率が少なくとも６５％になるように重
合させ、次いでこの重合液を１５０〜２８０℃の温度に
おいて３〜６０分間加熱処理したのち、脱揮器に供給す
ることを特徴とするゴム変性スチレン系樹脂の製造方法
を提供するものである。That is, in the present invention, the 11,2-vinyl bond content is 5
~20% and a styrene unit content of 20 to 50% by weight, or this styrene-butadiene block copolymer rubber 5
A styrenic monomer solution containing a mixture of 0% by weight or more and 50% by weight or less of polybutadiene rubber is polymerized such that the conversion rate at the exit of the final polymerization vessel is at least 65%, and then this polymerization solution is The present invention provides a method for producing a rubber-modified styrenic resin, which comprises heating the resin at a temperature of 150 to 280°C for 3 to 60 minutes, and then supplying the resin to a devolatilizer.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明のゴム変性スチレン系樹脂の製造方法においては
、塊状重合が適用され、原料単量体としてスチレン系単
量体が用いられる。該スチレン系単量体は、スチレン単
独であってもよいし、スチレンと共重合可能な単量体と
の混合物であってもよい。該共重合可能な単量体として
は、例えばσ−メチルスチレン、ビニルトルエン、ビニ
ルエチルベンゼン、ビニルキシレン、ｐ−ｔ−ブチルス
チレン、σ−メチルーｐ−メチルスチレン、ビニルナフ
タレンなどの芳香族モノビニル化合物、アクリロニトリ
ル、メタクリル酸メチル、アクリル酸メチル、メタクリ
ル酸、アクリル酸、無水マレイン酸、フェニルマレイミ
ドなどを挙げることができる。これらの単量体は１種用
いてもよいし、２種以上を組み合わせて用いてもよいが
、スチレンを含む全単量体に対して、通常５０重量％以
下、好ましくは４０重量％以下の割合で用いられる。In the method for producing a rubber-modified styrenic resin of the present invention, bulk polymerization is applied, and a styrenic monomer is used as a raw material monomer. The styrenic monomer may be styrene alone or a mixture of styrene and a monomer copolymerizable with styrene. Examples of the copolymerizable monomer include aromatic monovinyl compounds such as σ-methylstyrene, vinyltoluene, vinylethylbenzene, vinylxylene, pt-butylstyrene, σ-methyl-p-methylstyrene, and vinylnaphthalene; Examples include acrylonitrile, methyl methacrylate, methyl acrylate, methacrylic acid, acrylic acid, maleic anhydride, and phenylmaleimide. These monomers may be used alone or in combination of two or more types, but they usually account for 50% by weight or less, preferably 40% by weight or less, based on the total monomers containing styrene. Used in percentages.
本発明においては、ゴム成分としてスチレン−ブタジエ
ン系ブロック共重合体ゴム、又はスチレン−ブタジエン
系ブロック共重合体ゴムとポリブタジェンゴムとの混合
物が用いられる。In the present invention, a styrene-butadiene block copolymer rubber or a mixture of a styrene-butadiene block copolymer rubber and a polybutadiene rubber is used as the rubber component.
本発明においては、前記スチレン−ブタジエン系ブロッ
ク共重合体ゴムとして、ｌ、２−ビニル結合含有量が５
〜２０％で、かつスチレン単位含有量が２０〜５０重量
％、好ましくは２５〜４５重量％の範囲にあるものを用
いることが必要である。該１１，２一ビニル結合含有量
が５％未満では架橋の進行が遅いため、脱揮器において
、ゴム粒子の破壊が生じやすいし、２０％を超えると後
処理系において架橋度が進みすぎて、耐衝撃性が低下す
る傾向がみられる。このゴムの架橋の進行度合いは、得
られる樹脂の軟質成分、すなわちスチレン系重合体を内
蔵しＩ；ゴム状物質の膨潤指数（Ｓｗｅｌｌｉｎｇ
Ｉｎｄｅｘ＝ＳＩ値）により評価が可能である。本発明
においては、該Ｓｌ値は７〜１７の範囲であることが好
ましく、このＳＩ値が７未満ではゴムの架橋が進行しす
ぎて耐衝撃性が十分に発揮されないおそれがあるし、１
７を超えると架橋が不十分で粒子が破壊されやすく、光
沢が低下するおそれが生じる。In the present invention, the styrene-butadiene block copolymer rubber has a l,2-vinyl bond content of 5
~20% and the styrene unit content is in the range of 20 to 50% by weight, preferably 25 to 45% by weight. If the 11,2-vinyl bond content is less than 5%, the progress of crosslinking is slow, so rubber particles are likely to be destroyed in the devolatilizer, and if it exceeds 20%, the degree of crosslinking will progress too much in the post-treatment system. , there is a tendency for impact resistance to decrease. The degree of crosslinking of this rubber is determined by the soft component of the resulting resin, i.e., the styrene polymer incorporated therein;
Evaluation is possible using Index=SI value). In the present invention, the SI value is preferably in the range of 7 to 17; if the SI value is less than 7, crosslinking of the rubber may proceed too much and the impact resistance may not be sufficiently exhibited;
If it exceeds 7, the crosslinking will be insufficient and the particles will be easily destroyed, leading to a risk of lowering the gloss.
さらに、スチレン−ブタジエン系ブロック共重合体ゴム
中のスチレン単位の含有量が２０重量％未満ではポリブ
タジェンゴムの性質に近ずき、相転移が起こる転化率が
低く、初期重合での粒径制御が困難となり分布が広がり
やすく、その結果光沢が低下するおそれがあるし、５０
重量％を超えるとゴム粒子が繊細化しすぎて耐衝撃性が
低下する傾向がみられる。Furthermore, if the content of styrene units in the styrene-butadiene block copolymer rubber is less than 20% by weight, the properties approach those of polybutadiene rubber, the conversion rate at which phase transition occurs is low, and the particle size at the initial polymerization is It is difficult to control, the distribution tends to spread, and as a result, the gloss may decrease.
If it exceeds the weight percentage, the rubber particles tend to become too fine and the impact resistance tends to decrease.
前記スチレン−ブタジエン系ブロック共重合体ゴムは完
全ブロック型であってもよいし、テーノく−ブロック型
であってもよいが、テーパーブロック型の場合には、ス
チレンのブロック率が５０モル％以上のものが有利であ
る。The styrene-butadiene block copolymer rubber may be of a complete block type or a tapered block type, but in the case of a tapered block type, the styrene block rate is 50 mol% or more. is advantageous.
このようなスチレン−ブタジエン系ブロック共重合体ゴ
ムとしては、スチレン単位と１１，３−ブタジェン単位
とか成るものが挙げられるが、所望により、この共重合
体において、スチレン単位の一部を全ビニル系単量体単
位に対して５０１１量％以下、好ましくは、４０重量％
以下の割合でスチレンと共重合可能なビニル系単量体単
位に置き換えたもの又は１１，３−ブタジェン単位の一
部を全ジオレフィン系単量体単位に対して５０重量％以
下、好ましくは、４０重量％以下の割合で１，３−ブタ
ジェン以外の他のジオレフィン単位に置き換えたもの、
あるいはその両方のものであってもよい。Examples of such styrene-butadiene block copolymer rubbers include those consisting of styrene units and 11,3-butadiene units. 5011% by weight or less, preferably 40% by weight based on the monomer unit
One in which a vinyl monomer unit copolymerizable with styrene is substituted or a part of 11,3-butadiene unit is substituted with a vinyl monomer unit copolymerizable with styrene in the following proportion, preferably 50% by weight or less based on the total diolefin monomer unit, Substituted with other diolefin units other than 1,3-butadiene in a proportion of 40% by weight or less,
Or it may be both.
スチレンと共重合可能なビニル系単量体としては、前記
スチレン系単量体の説明において例示したものが挙げら
れ、それらは１種用いてもよいし、２種以上を組み合わ
せて用いてもよい。Examples of vinyl monomers copolymerizable with styrene include those exemplified in the explanation of the styrene monomers above, and they may be used alone or in combination of two or more. .
また、１１，３−ブタジェン以外の他のジオレフィンと
しては、例えばインブレン、ｌ、３−ペンタジェン、２
．３−ジメチル−１，３−ブタジェン、２−エチル−１
，３−ブタジェン、２．３−ジエチル−１，３−ブタジ
ェン、２．３−ジフェニル−１，３−ブタジェンなどを
挙げることができ、これらは、−積用いてもよいし、２
種以上を組合せて用いてもよい。In addition, other diolefins other than 11,3-butadiene include, for example, inbrene, l,3-pentadiene, 2
．． 3-dimethyl-1,3-butadiene, 2-ethyl-1
, 3-butadiene, 2,3-diethyl-1,3-butadiene, 2,3-diphenyl-1,3-butadiene, etc.
You may use combinations of more than one species.
このようなスチレン−ブタジエン系ブロック共重合体ゴ
ムは、公知の方法（特開昭５０−１５７４９３号公報、
特公昭５４−１９０３１号公報）、例えば有機リチウム
系触媒の存在下、ヘキサン、ヘプタン、ベンゼンなどの
不活性の炭化水素溶媒中において、スチレンと１，３−
ブタジェンとを完全ブロック型又はテーパブロック型に
なるように共重合させる方法によって、製造することが
できる。前記完全ブロック拒とは、スチレン単位の含有
量が共重合体のポリマー鎖に沿って断続的に減少する組
成を有するスチレン−ブタジエン系ブロック共重合体を
意味し、一方テーバブロック型とはスチレン単位の含有
量が共重合体のポリマー鎖に沿って、連続的に減少する
漸減組成を有するスチレン−ブタジエン系ブロック共重
合体を意味する。Such styrene-butadiene block copolymer rubber can be produced by a known method (Japanese Patent Application Laid-open No. 157493/1983,
(Japanese Patent Publication No. 54-19031), for example, styrene and 1,3-
It can be produced by copolymerizing with butadiene to form a complete block type or tapered block type. The complete block type refers to a styrene-butadiene block copolymer having a composition in which the content of styrene units decreases intermittently along the polymer chain of the copolymer, while the Taber block type refers to a styrene-butadiene block copolymer in which the content of styrene units decreases intermittently along the polymer chain of the copolymer. It refers to a styrene-butadiene-based block copolymer having a gradually decreasing composition in which the content of is continuously decreased along the polymer chain of the copolymer.
このスチレン−ブタジエン系ブロック共重合体ゴムは１
種用いてもよいし、２種以上を組み合わせて用いてもよ
い。This styrene-butadiene block copolymer rubber has 1
A species may be used, or two or more species may be used in combination.
本発明においては、ゴム成分として、前記スチレン−ブ
タジエン系ブロック共重合体ゴムを単独で用いてもよい
し、このスチレン−ブタジエン系ブロック共重合体ゴム
とポリブタジェンゴムとの混合物を用いてもよいが、後
者の場合、ポリブタジェンゴムの使用量は、混合ゴム成
分の重量に基ずき５０重量％以下の割合で用いることが
必要である。この量が５０重量％を超えると前記と同様
に相転移が起こる転化率が低下し、初期重合での粒径制
御が困難となり、分布が広がりやすく、その結果光沢が
低下する傾向がみられる。In the present invention, the styrene-butadiene block copolymer rubber may be used alone as the rubber component, or a mixture of the styrene-butadiene block copolymer rubber and polybutadiene rubber may be used. However, in the latter case, it is necessary to use polybutadiene rubber in an amount of 50% by weight or less based on the weight of the mixed rubber component. If this amount exceeds 50% by weight, the conversion rate at which phase transition occurs similarly to the above decreases, particle size control during initial polymerization becomes difficult, the distribution tends to widen, and as a result, gloss tends to decrease.
このポリブタジェンゴムの１１，２−ビニル結合含有量
については特に制限はなく、該含有量が２〜３％のハイ
シス系ゴムから、１２％以上のローシス系ゴムまで使用
可能であるが、ゴムの架橋が進みにくい系においては、
ローシス系ゴムの使用がゴム粒子の安定化、すなわち光
沢発現の点から有利であり、一方、ゴムの架橋が進みや
すい系においては、耐衝撃性保持の点から、ハイシス系
ゴムの使用が有利である。There is no particular restriction on the 11,2-vinyl bond content of this polybutadiene rubber, and it can be used from high-cis rubbers with a content of 2 to 3% to low-cis rubbers with a content of 12% or more. In systems where crosslinking is difficult to proceed,
The use of low-cis rubber is advantageous from the viewpoint of stabilizing rubber particles, that is, from the viewpoint of gloss development.On the other hand, in systems where rubber crosslinking tends to proceed, the use of high-cis rubber is advantageous from the viewpoint of maintaining impact resistance. be.
本発明方法においては、まず、前記ゴム成分をスチレン
系単量体中に通常５〜２０重量％の濃度になるように溶
解させる。この濃度が５重量％未満では得られるゴム変
性スチレン系樹脂の耐衝撃性が十分に発揮されないおそ
れがあるし、２０重量％を超えると反応系が極めて高粘
度となるため、反応器の動力や除熱がネックとなって、
運転上のトラブルが生じやすくなり、かつ得られるゴム
変性スチレン系樹脂は剛性が低下し、成形時にクラック
が発生しやすくなる傾向がみられる。In the method of the present invention, the rubber component is first dissolved in a styrene monomer to a concentration of usually 5 to 20% by weight. If this concentration is less than 5% by weight, the impact resistance of the resulting rubber-modified styrenic resin may not be sufficiently exhibited, and if it exceeds 20% by weight, the reaction system will have extremely high viscosity, which will reduce the power of the reactor. Heat removal becomes a bottleneck,
Operational troubles tend to occur, and the resulting rubber-modified styrenic resin tends to have reduced rigidity and cracks tend to occur during molding.
次に、前記のゴム含有スチレン系単量体溶液を、相転移
直前の転化率が１０〜３０％程度になるまで初期重合す
る。この初期重合の反応器としては完全混合型が一般的
であるが、リサイクルにより除゛熱効率を高めた静止型
反応器も使用することができる。Next, the rubber-containing styrenic monomer solution is subjected to initial polymerization until the conversion rate immediately before the phase transition reaches about 10 to 30%. A complete mixing type reactor is generally used for this initial polymerization, but a stationary type reactor with improved heat removal efficiency through recycling can also be used.
次いで、所定のゴム粒子系に制御するために、必要な剪
断力を付与しうる重合器を使用して相転移を行う。ここ
での転化率は３０〜６５％が適当であり、また、重合器
としてはプラグフロー性の高いｇＥ型反応器や静止型の
管型反応器などが好ましく用いられるが、他のタイプの
重合器も使用することができる。Next, in order to control the rubber particle system to a predetermined value, phase transition is carried out using a polymerization vessel capable of applying a necessary shearing force. The appropriate conversion rate here is 30 to 65%, and as the polymerization vessel, a gE type reactor with high plug flow property or a static tubular reactor is preferably used, but other types of polymerization utensils can also be used.
続く最終重合器においては、１５０℃以上の温度におい
て、転化率が６５％以上となるように重合させる。この
温度が１５０℃未満で、転化率が６５％未満では、架橋
が進行せず、ゴム粒子の破壊が生じやすくなる。本発明
においては前記最終重合器から出た重合液を、１５０〜
２８０℃、好ましくは１９０〜２６０℃の範囲の温度に
おいて３〜６０分間、好ましくは５〜３０分間加熱処理
して、ゴム粒子の架橋を進行させてから、脱揮器に供給
することが必要である。この加熱処理は、通常最終重合
器出口から脱揮器までの配管を二重管としてジャケット
加熱したりプレートフィン型熱交換器や多管式熱交換器
等の種々の熱交換器により加熱することにより行われる
。この際の温度が１５０℃未満や滞留時間が３分間より
短い場合、ゴム粒子の架橋が十分に進行せず、脱揮器で
のゴム粒子の破壊が生じやすくなるし、温度が２８００
０を超える場合や滞留時間が６０分を超える場合は、ゴ
ム粒子の架橋が進行しすぎて耐衝撃性が低下するおそれ
がある。In the subsequent final polymerization vessel, polymerization is carried out at a temperature of 150° C. or higher to achieve a conversion rate of 65% or higher. If this temperature is less than 150° C. and the conversion rate is less than 65%, crosslinking will not proceed and the rubber particles will be easily destroyed. In the present invention, the polymerization liquid discharged from the final polymerization vessel is
It is necessary to heat the rubber particles at a temperature in the range of 280°C, preferably 190 to 260°C, for 3 to 60 minutes, preferably 5 to 30 minutes, to advance crosslinking of the rubber particles, and then feed the rubber particles to the devolatilizer. be. This heat treatment is usually performed by jacket heating the piping from the final polymerizer outlet to the devolatilizer as a double pipe, or by heating with various heat exchangers such as a plate-fin heat exchanger or a shell-and-tube heat exchanger. This is done by If the temperature at this time is less than 150°C or the residence time is shorter than 3 minutes, crosslinking of the rubber particles will not proceed sufficiently, and the rubber particles will be easily destroyed in the devolatilizer.
If it exceeds 0 or if the residence time exceeds 60 minutes, there is a risk that crosslinking of the rubber particles will progress too much and the impact resistance will decrease.
次に、このようにして加熱処理された重合液は脱揮器に
供給されて、未反応モノマーや所望に応じて用いられる
溶媒が除去される。該脱揮器の形式については、前記条
件を満たしておれば時に制限はないが、剪断力の小さい
機器、例えばフラッシュドラムシステムを用いれば、よ
り一層ゴム粒子の安定化が図れる。この脱揮器の条件に
ついては、従来塊状重合によるポリスチレンの製造にお
いて慣用されている条件であればよく、特に制限はない
が、通常温度２００〜３００℃、圧力０．１〜７６０Ｔ
ｏｒｒ、滞留時間２〜６０分の条件で脱揮処理が行われ
る。Next, the polymerization liquid heat-treated in this manner is supplied to a devolatilizer to remove unreacted monomers and a solvent used as desired. There are no restrictions on the type of devolatilizer as long as it satisfies the above conditions, but rubber particles can be further stabilized by using equipment with low shearing force, such as a flash drum system. The conditions of this devolatilizer are not particularly limited as long as they are the conditions commonly used in the production of polystyrene by conventional bulk polymerization, but the usual temperature is 200 to 300°C and the pressure is 0.1 to 760T.
The devolatilization process is performed under the conditions of 2 to 60 minutes of residence time.
前記初期重合帯域における重合温度は、重合に有機過酸
化物を使用する場合は、その分解温度に応じて、通常２
０〜２００℃の範囲で選ばれる。When an organic peroxide is used in the polymerization, the polymerization temperature in the initial polymerization zone is usually 2 or more depending on the decomposition temperature of the organic peroxide.
The temperature is selected within the range of 0 to 200°C.
本発明における重合においては、必要に応じ、連鎖移動
剤（分子量調節剤）、酸化防止剤、溶剤、ミネラルオイ
ル、シリコンオイルなどを添加することができる。なお
、連鎖移動剤を初期重合系に添加した場合は、添加量に
応じて、分子量低下とゴム粒径の肥大化を同時にもたら
すことが可能であり、また、有機過酸化物を使用するこ
とにより、逆にゴム粒径を小さくすることができる。In the polymerization in the present invention, chain transfer agents (molecular weight regulators), antioxidants, solvents, mineral oil, silicone oil, etc. can be added as necessary. In addition, when a chain transfer agent is added to the initial polymerization system, it is possible to reduce the molecular weight and increase the rubber particle size at the same time depending on the amount added. On the contrary, the rubber particle size can be reduced.
前記有機過酸化物としては、例えば１１，１−ビス（１
−ブチルペルオキシ）シクロヘキサン、１、Ｌ−ビス（
ｔ−ブチルペルオキシ）３，３．５−トリメチルシクロ
ヘキサンなどのペルオキシケタール類、ジクミルペルオ
キシド、ジ−ｔ−ブチルペルオキシド、２．５−ジメチ
ル−２，５−ジ（ｔ−ブチルペルオキシ）ヘキサンなど
のジアルキルペルオキシド類、ベンゾイルペルオキシド
、ｍ−）ルオイルベルオキシドなどのジアリールペルオ
キシド類、シミリスチルペルオキシジカーボネートなど
のペルオキシジカーボネート類、【−プチルペルオキシ
イソグロビルカーボネートなどのペルオキシエステル類
、シクロヘキサノンペルオキシドなどのケトンペルオキ
シド類、ｐ−メンタンハイドロペルオキシドなどのハイ
ドロペルオキシド類などの有機過酸化物などを挙げるこ
とができる。As the organic peroxide, for example, 11,1-bis(1
-butylperoxy)cyclohexane, 1, L-bis(
peroxyketals such as (t-butylperoxy)3,3.5-trimethylcyclohexane, dicumyl peroxide, di-t-butylperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, etc. Dialkyl peroxides, benzoyl peroxide, diaryl peroxides such as m-)luoyl peroxide, peroxydicarbonates such as simiristyl peroxydicarbonate, peroxy esters such as [-butylperoxyisoglobyl carbonate, etc.], cyclohexanone peroxide, etc. Examples include organic peroxides such as ketone peroxides and hydroperoxides such as p-menthane hydroperoxide.
また、連鎖移動剤としては、例えばσ−メチルスチレン
ダイマー、ｎ−ドデシルメルカプタン、ｔ−ドデシルメ
ルカプタン、１−フェニルブテン−２−フルオレン、ジ
ペンテン、クロロホルムなどのメルカプタン類、テルペ
ン類、ノ１０ゲン化合物などを挙げることができるが、
これらの中で特にｎ−ドデシルメルカプタンが好適であ
る。In addition, examples of chain transfer agents include mercaptans such as σ-methylstyrene dimer, n-dodecylmercaptan, t-dodecylmercaptan, 1-phenylbutene-2-fluorene, dipentene, and chloroform, terpenes, and 10-gen compounds. can be mentioned, but
Among these, n-dodecylmercaptan is particularly preferred.
本発明においては、必要に応じ溶剤を用いてもよい。該
溶剤としては、例えばトルエン、キシレン、エチルベン
ゼン及びこれらの混合物などの芳香族炭化水素を用いる
ことができる。さらに、ゴム成分及びスチレン系単量体
からの重合生成物の溶解を損なわない範囲で他の溶剤、
例えば脂肪族炭化水素、ジアルキルケトン類などを、前
記芳香族炭化水素と併用することができる。該溶剤の使
用量は、ゴム成分とスチレン系単量体との合計重量に基
づき、通常０〜２５重量％の範囲で選ばれる。この量が
２５重量％を超えると重合速度が著しく低下する傾向が
みられ、かつ後処理系での脱揮処理においてゴム粒子の
破壊が生じやすくなり、得られるゴム変性スチレン系樹
脂の耐衝撃性及び光沢が低下する傾向が生じるとともに
、溶剤回収エネルギーが大きく、経済的に不利となる。In the present invention, a solvent may be used if necessary. As the solvent, aromatic hydrocarbons such as toluene, xylene, ethylbenzene, and mixtures thereof can be used. Furthermore, other solvents may be used as long as they do not impair the dissolution of the rubber component and the polymerization product from the styrene monomer.
For example, aliphatic hydrocarbons, dialkyl ketones, etc. can be used in combination with the aromatic hydrocarbons. The amount of the solvent to be used is usually selected within the range of 0 to 25% by weight, based on the total weight of the rubber component and styrene monomer. If this amount exceeds 25% by weight, there is a tendency for the polymerization rate to decrease significantly, and the rubber particles are likely to be destroyed during the devolatilization treatment in the post-treatment system, resulting in a decrease in the impact resistance of the resulting rubber-modified styrenic resin. In addition, the gloss tends to decrease, and the energy required to recover the solvent is large, which is economically disadvantageous.
このようにして得られたゴム変性スチレン系樹脂は、ス
チレン系重合体を内蔵したゴム状物質、すなわち軟質成
分が均質に分散したものであって、通常軟質成分のゴム
粒径が０．２〜１１，５μｍ１面積平均ゴム粒径／数平
均ゴム粒径の比Ｄ ｓ ／ Ｄ ｎが２．５以下及び膨
潤指数が７〜１７の範囲番こある。The rubber-modified styrenic resin thus obtained is a rubber-like material containing a styrene polymer, that is, a soft component is homogeneously dispersed, and the rubber particle size of the soft component is usually 0.2 to The ratio D s /D n of 11.5 μm 1 area average rubber particle size/number average rubber particle size is 2.5 or less and the swelling index is in the range of 7 to 17.
該軟質成分のゴム粒径、Ｄ ｓ ／ Ｄ ｎ及び膨潤指
数が前記範囲を逸脱すると本発明の目的が十分に達せら
れない。If the rubber particle size, D s / D n and swelling index of the soft component deviate from the above ranges, the object of the present invention cannot be fully achieved.
本発明方法で得られたゴム変性スチレン系樹脂には、所
望に応じ、通常用いられている種々の添加剤、例えばス
テアリン酸、ベヘニン酸、ステアリン酸亜鉛、ステアリ
ン酸カルシウム、ステアリン酸マグネシウム、エチレン
ビスステアロアミドなどの滑剤や、有機ポリシロキサン
、ミネラルオイル、あるいは２，６−ジー【−ブチル−
４−メチルフェノール、ステアリル−β−（３，５−ジ
−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネー
ト、トリエチレグリコールービス−３−（３−ｔ−ブチ
ル−４−ヒドロキシ−５−メチルフェニル）プロピオネ
ートなどのヒンダードフェノール系やトリ（２，４−ジ
−ｔ−ブチルフェニル）ホスファイト、４．４″−ブチ
リデンビス（３−メチル−６−ｔ−ブチルフェニル−ジ
−トリデシル）ホスファイトなどのリン系の酸化防止剤
、紫外線吸収剤、難燃剤、帯電防止剤、離型剤、可塑剤
、染料、顔料、各種充填剤などを添加することができる
。また、他のポリマー、例えばポリスチレンやポリフェ
ニレンエーテルなどを配合する。こともできる。The rubber-modified styrenic resin obtained by the method of the present invention may optionally contain various commonly used additives, such as stearic acid, behenic acid, zinc stearate, calcium stearate, magnesium stearate, and ethylene bisstearate. Lubricant such as Roamide, organic polysiloxane, mineral oil, or 2,6-di[-butyl-
4-methylphenol, stearyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, triethylene glycol-bis-3-(3-t-butyl-4-hydroxy-5-methylphenyl) ) propionate and other hindered phenols, tri(2,4-di-t-butylphenyl) phosphite, 4.4″-butylidenebis(3-methyl-6-t-butylphenyl-di-tridecyl) phosphite, etc. Phosphorous antioxidants, ultraviolet absorbers, flame retardants, antistatic agents, mold release agents, plasticizers, dyes, pigments, various fillers, etc. can be added.Also, other polymers such as polystyrene and It is also possible to blend polyphenylene ether, etc.
［実施例］
次に、実施例により本発明をさらに詳細に説明するが、
本発明はこれらの例によってなんら限定されるものでは
ない。[Example] Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited in any way by these examples.
なお、スチレン系樹脂の特性及びゴム成分の１１，２−
ビニル結合含有量は次に示す方法により求めた。In addition, the characteristics of the styrene resin and the 11,2-
The vinyl bond content was determined by the method shown below.
（１）光沢 ＪＩＳＫ−７１０５に準拠して求めた。(1) Gloss It was determined in accordance with JISK-7105.
（２）アイゾツト衝撃強度
ＪＩＳ Ｋ−７１１０（２３℃、ノツチ付）に準拠し
て求めた。(2) Izot impact strength was determined in accordance with JIS K-7110 (23°C, notched).
（３）平均ゴム粒子径、粒径分布
樹脂の超薄切片法により作成したサン
プルの透過型電子Ｍ微鏡写真（拡大倍率１０．０００＠
）を撮影し、写真中の分数粒子約１，０００個の径を測
定する。ただし、電子顕微鏡写真に写った分散粒子は完
全な円形でないので、粒子の長手方向径ａと短幅方向Ｂ
ｉｂを測り、次式により粒子径を算出する。(3) Average rubber particle size, particle size distribution Transmission electron M micrograph of a sample prepared by the ultra-thin section method of resin (magnification: 10.000@
) and measure the diameters of approximately 1,000 fractional particles in the photograph. However, since the dispersed particles shown in the electron micrograph are not completely circular, the diameter a in the longitudinal direction and the diameter B in the short width direction of the particles are
Measure ib and calculate the particle diameter using the following formula.
粒子径−ｆ丁７丁
平均ゴム粒子径Ｄｓ−Σ□Ｄ１１／Σ、、Ｄ 、”粒径
分布Ｄｓ／Ｄｎ＝
（Σ１Ｄ、”／Σ、、Ｄ Ｉ”）／（Σ、、ｒｉ、／Σ
１１，）（ただし、ｎｉは粒子径Ｄｉを有する分散粒子
の個数である）
なお、ゴム粒子の破壊有無の判定は該写真によって行っ
た。Particle diameter - f 7 average rubber particle diameter Ds - Σ□D11/Σ,,D,"Particle size distribution Ds/Dn= (Σ1D,"/Σ,,DI")/(Σ,,ri,/ Σ
11,) (where ni is the number of dispersed particles having a particle diameter Di) Note that the presence or absence of destruction of rubber particles was determined based on the photograph.
（４）軟質成分の膨潤指数（Ｓｗｃｌｌｉｏｔ Ｉ＋ｄ
ｅｘ＝ Ｓ Ｉ ）樹脂のトルエン不溶分のトルエンに
よる膨潤度をいう。具体的には、樹脂２．０ｇをトルエ
ン１００ｍ１に溶解したのち、遠心分離により不溶分を
分離し、その不溶分、すなわちｒＩｉ潤軟質成分を秤量
しＡｇとする０次に、この湿潤軟質成分をメタノール再
沈したのち、ｌ昼夜真空乾燥して、乾燥軟質成分を秤量
しＢｇとすると、軟質成分の膨潤指数はＡ／Ｂで表され
る。(4) Swelling index of soft component (Swcliot I+d
ex= S I ) Refers to the degree of swelling of the toluene-insoluble portion of the resin with toluene. Specifically, after dissolving 2.0 g of resin in 100 ml of toluene, the insoluble matter is separated by centrifugation, and the insoluble matter, that is, the wet soft component is weighed and defined as Ag. After reprecipitation with methanol, vacuum drying is carried out for 1 day and night, and the dried soft component is weighed and designated as Bg, and the swelling index of the soft component is expressed as A/B.
（５）ゴム成分の１，２−ビニル結合含有量モレロ法（
ｒＣｈ ｉｍ、＆Ｉ ｎｄ、Ｊ第４１巻、第７５８ペー
ジ（１９５９年）〕により、赤外分光光度計を使用して
測定しｔ；。(5) 1,2-vinyl bond content of rubber component Morello method (
rCh im, & I nd, J Vol. 41, p. 758 (1959)] using an infrared spectrophotometer.
なお、１１，２−ビニル、１１，４−シス、１１，４−
トランス結合は各々９１０ｃｍ−’７３５ｃｍ−’、９
６５ ｃｙａ−’に特性吸収があるので、各々の吸光度
より計算し、１１，２−ビニル結合含有量の割合（％）
を求めた。In addition, 11,2-vinyl, 11,4-cis, 11,4-
The trans bonds are 910cm-'735cm-', 9, respectively.
Since there is a characteristic absorption at 65 cya-', it is calculated from each absorbance and the percentage of 11,2-vinyl bond content (%)
I asked for
実施例１
スチレン単位含有量４０ｗｔ％、ｌ、２−ビニル結合含
有量８．３％のＳＢブロックゴム（バイエル社製、ＢＬ
−６５３３）とＰＢゴム〔旭化成（株）製、ＮＦ−３５
ＡＳ）とを、重量比８０ ： ２０の割合で用い、濃度
が１３ｗｔ％になるようにスチレンに溶解した。次に、
このゴム溶液ｌｓ、ｏｌ／ｈｒと、ゴム溶液に対し、１
５００ｐｐｍの量で酸化防止剤［イルガノックス１０７
６Ｊ （チバガイギー社製）を溶解したエチルベンゼ
ン溶液１１，８ｆｆｉ／ｈｒを、内容積２１１の完全混
合種型の第１重合器に供給し、重合温度１３７℃で、ス
チレンの転化率２０％まで初期重合を行った。Example 1 SB block rubber (manufactured by Bayer AG, BL
-6533) and PB rubber [manufactured by Asahi Kasei Corporation, NF-35]
AS) were used at a weight ratio of 80:20 and dissolved in styrene to a concentration of 13 wt%. next,
This rubber solution ls, ol/hr and 1
Antioxidant [Irganox 107] in an amount of 500 ppm
An ethylbenzene solution of 11.8 ffi/hr in which 6J (manufactured by Ciba Geigy) was dissolved was supplied to the first polymerization vessel of a complete mixing type with an internal volume of 211, and the initial polymerization was carried out at a polymerization temperature of 137° C. to a styrene conversion rate of 20%. I did it.
次いで、この重合液を内容積３３１の多段パドル翼付塔
型の第２！合器に供給し、回転数４Ｏｒｐｍの撹拌下、
１４８℃で転化率５０％まで重合させるとともに、相転
移を起こさせゴム粒径を制御した。さらに、この重合液
を第２重合器と同様の形状を有する第３重合器に供給し
、１０ｒｐｍ、１８０℃で転化率８０％まで重合させｔ
こ。Next, this polymerization liquid was transferred to a second tube in a multi-stage paddle-winged tower having an internal volume of 331 cm. Supplied to a mixer, under stirring at a rotation speed of 4 Orpm,
Polymerization was carried out at 148° C. to a conversion rate of 50%, and the rubber particle size was controlled by causing a phase transition. Furthermore, this polymerization solution was supplied to a third polymerization vessel having the same shape as the second polymerization vessel, and polymerized at 10 rpm and 180°C to a conversion rate of 80%.
child.
次に、第３重合益田口の重合液は、ジャケット付の二重
管で、２００℃、２０分間加熱したのち、２軸混練機型
脱揮器に供給し、３００Ｔｏｒｒ。Next, the polymerization solution of the third polymerization Masudaguchi was heated at 200°C for 20 minutes in a jacketed double pipe, and then supplied to a twin-screw kneader type devolatilizer at 300 Torr.
２４０°Ｃの条件で揮発分除去を行い、次いで付属の押
出機でペレット化を行った。得られたゴム変性スチレン
系樹脂のゴム粒子形状と物性の評価結果を第１表に示す
。Volatile matter was removed under conditions of 240°C, and then pelletization was performed using an attached extruder. Table 1 shows the evaluation results of the rubber particle shape and physical properties of the obtained rubber-modified styrenic resin.
この樹脂は、軟質成分のＳｌが１２．５であり、ゴ・ム
の架橋が適度に進行し、光沢と衝撃特性に優れたバラン
スを有している。また、電子顕微鏡写真でも綺麗なワン
オクルージＢン構造を主体としたゴム粒子がみられ、破
壊ゴム粒子は確認されなかっｌ二。This resin has a soft component Sl of 12.5, crosslinking of rubber progresses appropriately, and has an excellent balance between gloss and impact properties. In addition, rubber particles mainly having a beautiful one-occlusion structure can be seen in electron micrographs, and no broken rubber particles were observed.
実施例２
実施例１と同一条件で重合させた重合液を、ジャケット
付の二重管で１６０℃、５０分間加熱したのち、実施例
１と同じ２軸脱揮器に供給し、同様の処理を行った。得
られた樹脂は、実施例１と同様優れた物性を有している
。運転条件と物性の評価結果を第１表に示す。Example 2 A polymerization solution polymerized under the same conditions as in Example 1 was heated at 160°C for 50 minutes in a jacketed double tube, then supplied to the same twin-screw devolatilizer as in Example 1, and subjected to the same treatment. I did it. The obtained resin has excellent physical properties similar to Example 1. Table 1 shows the operating conditions and evaluation results of physical properties.
実施例３
実施例１と同一条件で重合させた重合液を、ジャケット
付の二重管で２６０℃、１０分間加熱したのち、実施例
１と同じ２軸脱揮器に供給し、同様の処理を行っＩ；。Example 3 A polymerization solution polymerized under the same conditions as in Example 1 was heated at 260°C for 10 minutes in a jacketed double tube, then supplied to the same twin-screw devolatilizer as in Example 1, and subjected to the same treatment. Perform I;.
得られた樹脂は、実施例１と同様優れた物性を有してい
る。運転条件と物性の評価結果を第１表に示す。The obtained resin has excellent physical properties similar to Example 1. Table 1 shows the operating conditions and evaluation results of physical properties.
実施例４
第２重合器までは実施例１と同一条件で重合させたのち
、実施例１と同一形状の第３重合器にて、１０ ｒ ｐ
ｍ％ １５５℃で転化率７０％まで重合させた。この重
合液をジャケット付の二重管で２００°Ｃｌ２Ｏ分間加
熱したのち、実施例１と同じ２軸脱揮器に供給し、同様
の処理を行っＩ；。Example 4 After polymerizing under the same conditions as in Example 1 up to the second polymerization vessel, in the third polymerization vessel having the same shape as Example 1, 10 r p
m% Polymerization was carried out at 155°C to a conversion rate of 70%. This polymerization solution was heated for 200°CCl2O minutes in a jacketed double tube, then fed to the same twin-screw devolatilizer as in Example 1, and subjected to the same treatment.
得られた樹脂は実施例１と同様、優れた物性を有してい
る。運転条件と物性の評価結果を第１表に示す。The obtained resin has excellent physical properties as in Example 1. Table 1 shows the operating conditions and evaluation results of physical properties.
実施例５
第２１！ｒ合器までは実施例１と同一条件で重合させた
のち、実施例１と同一形状の第３重合器にて、１０ ｒ
ｐｍ％ １７５℃で転化率９０％まで重合させた。こ
の重合液をジャケット付の二重管で２００℃、２０分間
加熱したのち、実施例１と同じ２軸脱揮器に供給し、同
様の処理を行った。Example 5 21st! After polymerization was carried out under the same conditions as in Example 1 up to the r polymerization vessel, 10 r
pm% Polymerization was carried out at 175°C to a conversion rate of 90%. This polymerization solution was heated in a jacketed double tube at 200° C. for 20 minutes, then supplied to the same twin-screw devolatilizer as in Example 1, and subjected to the same treatment.
得られた樹脂は実施例１と同様、優れた物性を有してい
る。運転条件と物性の評価結果を第１表に示す。The obtained resin has excellent physical properties as in Example 1. Table 1 shows the operating conditions and evaluation results of physical properties.
比較例！
・実施例４と同一条件で重合させた重合液を、ジャケッ
ト付の二重管で１４０℃、２０分間加熱したのち、実施
例１と同じ２軸脱揮器に供給し、同様の処理を行っｔ；
。得られＩ；樹脂は、軟質成分のＳｌが１８．１であっ
て、ゴムの架橋が進行しておらず、電子顕微鏡写真でも
ゴム粒子の破壊が確認され、結果として、光沢の低いも
のとなった。Comparative example!・The polymerization solution polymerized under the same conditions as in Example 4 was heated at 140°C for 20 minutes in a jacketed double tube, and then supplied to the same twin-screw devolatilizer as in Example 1 and subjected to the same treatment. t;
. Obtained I: The resin has a soft component Sl of 18.1, rubber crosslinking has not progressed, destruction of rubber particles is confirmed in electron micrographs, and as a result, the resin has low gloss. Ta.
運転条件と物性の評価結果を第１表に示す。Table 1 shows the operating conditions and evaluation results of physical properties.
比較例２
実施例４と同一条件で重合させた重合液を、ジャケット
付の二重管で３００℃、７０分間加熱したのち、実施例
１と同じ２軸脱揮器に供給し、同様の処理を行った。得
られた樹脂は、軟質成分のＳｌが６．７であって、ゴム
の架橋が進行しすぎて固くなり、結果として、衝撃強度
が低いものとなった。運転条件と物性の評価結果を第１
表に示す。Comparative Example 2 A polymerization solution polymerized under the same conditions as in Example 4 was heated at 300°C for 70 minutes in a jacketed double pipe, then supplied to the same twin-screw devolatilizer as in Example 1, and subjected to the same treatment. I did it. The resulting resin had a soft component Sl of 6.7, and the crosslinking of the rubber progressed too much to make it hard, resulting in low impact strength. First, evaluate the operating conditions and physical properties.
Shown in the table.
比較例３
比較例１と同一条件で重合させた重合液を、滞留時間２
分間以下で、内容積１５１の２４０℃、３５０Ｔｏｒｒ
で運転される手堅フラッシュドラム（Ｆ／Ｄ）に直接抜
き出した。次いで、Ｆ／Ｄボトムのギヤポンプより排出
されたストランドを再ペレット化してサンプルを得、評
価した。得られた樹脂は、軟質成分のＳＩが１８．７で
あって、ゴムの架橋が進行しておらず、電子顕微鏡写真
でもゴム粒子の破壊が確認され、結果として、光沢の低
いものとなった。運転条件と物性の評価結果を第１表に
示す。Comparative Example 3 A polymerization solution polymerized under the same conditions as Comparative Example 1 was
240℃, 350Torr with an internal volume of 151 minutes or less
The liquid was extracted directly to a handheld flash drum (F/D) operated by the F/D. Next, the strand discharged from the F/D bottom gear pump was re-pelletized to obtain a sample and evaluated. In the obtained resin, the SI of the soft component was 18.7, rubber crosslinking had not progressed, and destruction of rubber particles was confirmed in electron micrographs, resulting in low gloss. . Table 1 shows the operating conditions and evaluation results of physical properties.
比較例４
第１重合器までは実施例１と同一条件で重合させたのち
、実施例１と同一形状の第２．３重合器にて、それぞれ
４０ｒｐｍ、１３９℃、転化率４５％及び１０ｒｐｍ、
１４０℃、転化率６０％まで重合させた。この重合液を
実施例１と同一条件でジャケット付の二重管で加熱した
のち、２軸脱揮器に供給し、同様の処理を行った。得ら
れた樹脂は、軟質成分のＳｌが１７．２であって、ゴム
の架橋が進行しておらず、電子＊＊鏡写真でも粒子の破
塊が確認され、光沢が低いものであっｔ；。Comparative Example 4 After polymerizing under the same conditions as Example 1 up to the first polymerization vessel, polymerization was performed in the second and third polymerization vessels of the same shape as Example 1 at 40 rpm, 139°C, conversion rate of 45%, and 10 rpm, respectively.
Polymerization was carried out at 140° C. to a conversion rate of 60%. This polymerization liquid was heated in a jacketed double tube under the same conditions as in Example 1, and then supplied to a twin-screw devolatilizer and subjected to the same treatment. The obtained resin had a soft component Sl of 17.2, rubber crosslinking had not progressed, broken particles were confirmed in electronic mirror photography, and the gloss was low. .
運転条件と物性の評価結果を第１表に示す。Table 1 shows the operating conditions and evaluation results of physical properties.
実施例６
実施例４において、ＰＢゴムをｒＢＲ−１５ＨＢＪ
［宇部興産（株）製］に変えた以外は、実施例４と同様
な操作を行った。得られた樹脂は、実施例１と同様、優
れＩ；物性を有していた。運転条件と物性の評価結果を
第１表に示す。Example 6 In Example 4, the PB rubber was rBR-15HBJ.
The same operation as in Example 4 was performed except that the material was changed to [manufactured by Ube Industries, Ltd.]. The obtained resin had excellent physical properties as in Example 1. Table 1 shows the operating conditions and evaluation results of physical properties.
実施例７
実施例４と同一条件で重合させた重合液を、同一条件で
ジャケット付の二重管で加熱したのち、２軸脱揮器に替
え、内部にプレヒーターを有する内径４７０ｍｍの７ラ
ツシユドラム２段システムに供給し、１段目を２３０℃
、４００Ｔｏｒｒ。Example 7 The polymerization solution was polymerized under the same conditions as in Example 4, and then heated in a jacketed double tube under the same conditions, and then replaced with a twin-shaft devolatilizer and a 7-lush drum with an inner diameter of 470 mm and a preheater inside. Supply to a two-stage system, first stage at 230℃
, 400 Torr.
２段目を２６０℃、５Ｔｏｒｒの条件で運転し、出口の
ストランドをカッターで切断してベレットを得た。この
樹脂は、実施例４のものより、さらにゴム粒径分布の狭
い、光沢の優れるものであった。運転条件と物性の評価
結果を第１表に示す。The second stage was operated at 260° C. and 5 Torr, and the exit strand was cut with a cutter to obtain a pellet. This resin had a narrower rubber particle size distribution and better gloss than that of Example 4. Table 1 shows the operating conditions and evaluation results of physical properties.
実！ｔＬ例８
実施例１と同一のゴム種を使用して、ＳＢゴムとＰＢゴ
ムとの併用比率を６０ 二４０とし、かつ禦２重合器の
回転数をｓｏｒｐｍとした以外は、実施例４と同一条件
で重合を実施して、最終転化率を７０％としたのち、ジ
ャケット付の二重管で２４０℃、２０分間加熱し、実施
例７と同一条件で脱揮処理を実施しｌ；。得られた５ｔ
Ｉｆ１は、実施例１と同様、優れた物性を有していた。fruit! tL Example 8 The same procedure as Example 4 was used except that the same rubber type as in Example 1 was used, the combined ratio of SB rubber and PB rubber was 60 240, and the rotation speed of the 2nd polymerization vessel was set to sorpm. Polymerization was carried out under the same conditions to achieve a final conversion of 70%, followed by heating at 240°C for 20 minutes in a jacketed double tube, and devolatilization was carried out under the same conditions as in Example 7. Obtained 5t
Like Example 1, If1 had excellent physical properties.
運転条件と物性の評価結果を第１表に示す。Table 1 shows the operating conditions and evaluation results of physical properties.
実施例９
実施例１で使用したＳＢブロックゴムのみを、ゴム濃度
が１５ｗｔ％になるように溶解し、かつ第２重合器の回
転数を１ Ｏｒ ｐｍとした以外は、実施例１と同一条
件で実施し、実施例８と同一条件で加熱脱揮処理を行っ
Ｉ；。得られＩ；樹脂は、実施例１と同様、優れた物性
を有していた。運転条件と物性の評価結果を第１表に示
す。Example 9 Same conditions as Example 1, except that only the SB block rubber used in Example 1 was dissolved so that the rubber concentration was 15 wt%, and the rotation speed of the second polymerization vessel was set to 1 Or pm. The heat devolatilization treatment was carried out under the same conditions as in Example 8. Obtained I: The resin had excellent physical properties as in Example 1. Table 1 shows the operating conditions and evaluation results of physical properties.
実施例１０
実施例１において、ゴム成分として、スチレン単位含有
量２３Ｗ【％、１１，２−ビニル結合含有量１８．６％
のＳＢブロックゴム［日本ゼオン（株）製、ＺＬＳ−０
１１のみを使用し、かつ第２１１１合器の回転数を７Ｏ
ｒｐｍとした以外は、実施例１と同様な操作を行った。Example 10 In Example 1, the rubber component had a styrene unit content of 23W% and a 11,2-vinyl bond content of 18.6%.
SB block rubber [manufactured by Nippon Zeon Co., Ltd., ZLS-0]
11 only, and the rotation speed of the 2111th combiner is 7O.
The same operation as in Example 1 was performed except that the rpm was changed.
得られた樹脂は、実施例１と同様、優れた物性を有して
いた。運転条件と物性の評価結果を第１表に示す。The obtained resin had excellent physical properties as in Example 1. Table 1 shows the operating conditions and evaluation results of physical properties.
製造例Ｉ ＳＢブロックゴムの製造
１１，３−ブタジエン４５！！量部を含む濃度２０ｗｔ
％のヘキサン溶液に、ｎ−ブチルリチウム０．３Ｉｉ量
部を含む濃度１５ｗｔ％のｎ−ヘキサン溶液と１１，２
−ビニル結合調製剤としてのテトラヒドロフラン（ＴＨ
Ｆ）０．１８［置部とを加えて、８０℃で３９？間！を
合させた。１１，３−ブタジェンの全量が重合しｔ；の
ち、重合活性末端を有するポリブタジェンに、スチレン
５５重量部を加えて、さらに４時間重合を行い、ｌ、３
−ブタジェン重合体ブロックとスチレン重合体ブロック
とから成るブロック共重合体溶液を得た。この共重合体
溶液に、共重合体１００重量部当たり、ジー【−ブチル
−ｐ−クレゾール１重量部を安定剤として加え、溶媒を
加熱留去し、目的とするＳＲブロックゴムを単離した。Production Example I Production of SB block rubber 11,3-butadiene 45! ! Concentration 20wt including parts
% hexane solution, an n-hexane solution with a concentration of 15 wt% containing 0.3 parts of n-butyllithium, and 11,2
- Tetrahydrofuran (TH) as vinyl bond preparation agent
F) 0.18 [39? while! were combined. After the entire amount of 11,3-butadiene was polymerized, 55 parts by weight of styrene was added to the polybutadiene having a polymerizable active end, and polymerization was further carried out for 4 hours.
- A block copolymer solution consisting of a butadiene polymer block and a styrene polymer block was obtained. To this copolymer solution, 1 part by weight of di-butyl-p-cresol was added as a stabilizer per 100 parts by weight of the copolymer, and the solvent was distilled off under heating to isolate the desired SR block rubber.
このもののスチレン単位含有量は５５ｗ（％、１１，２
−ビニル結合含有量は１３．５％であった。The styrene unit content of this product is 55w (%, 11,2
- The vinyl bond content was 13.5%.
製造例２ ５Ｂブロツクゴムの製造
製造例１において、ｌ、３−ブタジェンを８５重量部、
スチレンを１５重量部、ｎ−ブチルリチウムを０．０８
！ｉ量部、スチレンの重合時間を２時間とした以外は、
製造例１と同様にしてＳＢブロックゴムを得た。このも
ののスチレン単位含有量は１５ｗｔ％、１１，２−ビニ
ル結合含有量は２３．６％であった。Production Example 2 Production of 5B block rubber In Production Example 1, 85 parts by weight of 1,3-butadiene,
15 parts by weight of styrene, 0.08 parts of n-butyllithium
! i part, except that the polymerization time of styrene was 2 hours.
An SB block rubber was obtained in the same manner as in Production Example 1. The styrene unit content of this product was 15 wt%, and the 11,2-vinyl bond content was 23.6%.
製造例３ ＳＢブロックゴムの製造
製造例１において、１１，３−ブタジェンを６０重量部
、スチレンを４０重量部、ｎ−ブチルリチウムを０．２
Ｉｌ量部、ＴＨＦを０．１３重量部、スチレンの重合時
間を３時間とした以外は、製造例１と同様にしてＳＢブ
ロックゴムを得た。このもののスチレン単位含有量は４
０ｗｔ％、ｌ、２−ビニル結合含有量は２４．４％であ
った。Production Example 3 Production of SB block rubber In Production Example 1, 60 parts by weight of 11,3-butadiene, 40 parts by weight of styrene, and 0.2 parts by weight of n-butyllithium.
An SB block rubber was obtained in the same manner as in Production Example 1, except that the amount of Il was changed to 0.13 parts by weight, and the polymerization time of styrene was changed to 3 hours. The styrene unit content of this product is 4
0 wt%, l,2-vinyl bond content was 24.4%.
比較例５
ゴム成分として、製造例１で得たスチレン単位含有量５
５ｗ【％、１１，２−ビニル結合含有量１３．５％のＳ
ＢブロックゴムとＰＢゴムｒＢＲ−１５ＨＢＪ （宇
部興産（株）製〕とを重量比８０ ： ２０の割合で用
いた以外は、実施例４と同様な操作を行った。得られた
樹脂は、軟質成分のＳｌ値が適当であったが、ゴム粒径
が０．２５μｍと小さく、衝撃強度が低いものとなった
。Comparative Example 5 As a rubber component, the styrene unit content obtained in Production Example 1 was 5
5w [%, S with 11,2-vinyl bond content 13.5%
The same operation as in Example 4 was performed except that B block rubber and PB rubber rBR-15HBJ (manufactured by Ube Industries, Ltd.) were used at a weight ratio of 80:20. Although the Sl value of the components was appropriate, the rubber particle size was small at 0.25 μm, and the impact strength was low.
運転条件と物性の評価結果を第１表に示す。Table 1 shows the operating conditions and evaluation results of physical properties.
比較例６
ゴム成分として、製造例２で得たスチレン単位含有量１
５ｗｔ％、１１，２−ビニル結合含有量２３．６％のＳ
ＢブロックゴムとＰＢゴムｒＮＦ−３５ＡＳＪ （旭
化成（株）製〕とを重量比８０ ： ２０の割合で用い
た以外は、実施例１と同一条件で重合させたのち、この
重合液をジャケット付の二重管で２６０℃、２０分間加
熱し、実施例１と同一条件で脱気処理を実施した。得ら
れた樹脂は、ゴムの架橋が進行しすぎて衝撃強度が低下
し、かつスチレン単位含有量が少ないことにより、ゴム
粒径が肥大化して、光沢も低下した。Comparative Example 6 As a rubber component, the styrene unit content obtained in Production Example 2 was 1
5 wt%, 11,2-vinyl bond content 23.6% S
After polymerizing under the same conditions as in Example 1 except that B block rubber and PB rubber rNF-35ASJ (manufactured by Asahi Kasei Corporation) were used at a weight ratio of 80:20, the polymerization solution was poured into a jacketed tube. The resin was heated at 260°C for 20 minutes in a double tube and degassed under the same conditions as in Example 1.The resulting resin had excessive rubber crosslinking, reduced impact strength, and contained styrene units. Due to the small amount, the rubber particle size increased and the gloss decreased.
運転条件と物性の評価結果を第１表に示す。Table 1 shows the operating conditions and evaluation results of physical properties.
比較例７
比較例６において、ＳＢブロックゴムとして、製造例３
で得たスチレン単位含有量４０Ｗ【％、１１，２−ビニ
ル結合含有量２４．４％のＳＢブロックゴムを用いｔ；
以外は、比較例６と同様な操作を行った。得られた樹脂
は、ゴム粒径は適当で光沢が良好であったが、ゴムの架
橋が進行しすぎて、衝撃強度が低いものとなった。運転
条件と物性の評価結果を第１表に示す。Comparative Example 7 In Comparative Example 6, Production Example 3 was used as the SB block rubber.
Using the SB block rubber with a styrene unit content of 40W% and a 11,2-vinyl bond content of 24.4% obtained in t;
Except for this, the same operation as in Comparative Example 6 was performed. The obtained resin had a suitable rubber particle size and good gloss, but the crosslinking of the rubber progressed too much and the impact strength was low. Table 1 shows the operating conditions and evaluation results of physical properties.
（以下余白）
【発明の効果］
本発明によると、塊状重合によるゴム変性スチレン系樹
脂の製造において、ゴム成分として、１１，２−ビニル
結合含有量及びスチレン単位含有量が特定の範囲にある
スチレン−ブタジエン系ブロック共重合体ゴム、又はこ
のものとポリブタジェンゴムとの混合物を用い、かつ脱
揮器供給前の重合後期で、温度、転化率及び滞留時間を
制御して、ゴムの架橋度をコントロールすることにより
、ＡＢＳ樹脂に匹敵する光沢及び耐衝撃性を有するとと
もに、特性バランスに優れたゴム変性スチレン系樹脂を
容易に製造することができる。(The following is a blank space) [Effects of the Invention] According to the present invention, in the production of rubber-modified styrenic resin by bulk polymerization, styrene having a 11,2-vinyl bond content and a styrene unit content within a specific range is used as a rubber component. - Using butadiene-based block copolymer rubber or a mixture of this and polybutadiene rubber, and controlling the temperature, conversion rate, and residence time in the late stage of polymerization before supplying the devolatilizer to increase the degree of crosslinking of the rubber. By controlling this, it is possible to easily produce a rubber-modified styrenic resin that has gloss and impact resistance comparable to ABS resin and has an excellent balance of properties.
本発明方法で得られたゴム変性スチレン系樹脂は、前記
のような優れた特徴を有することから、例えばＯＡ機器
や家電製品などの部品材料とじて好適に用いられる。Since the rubber-modified styrenic resin obtained by the method of the present invention has the above-mentioned excellent characteristics, it can be suitably used, for example, as a component material for OA equipment, home appliances, and the like.
Claims (1)
チレン単位含有量が２０〜５０重量％のスチレン−ブタ
ジエン系ブロック共重合体ゴムを含有するスチレン系単
量体溶液を、最終重合器出口における転化率が少なくと
も６５％になるように重合させ、次いでこの重合液を１
５０〜２８０℃の温度において３〜６０分間加熱処理し
たのち、脱揮器に供給することを特徴とするゴム変性ス
チレン系樹脂の製造方法。 ２ １，２−ビニル結合含有量が５〜２０％で、かつス
チレン単位含有量が２０〜５０重量％のスチレン−ブタ
ジエン系ブロック共重合体ゴム５０重量％以上とポリブ
タジエンゴム５０重量％以下との混合物を含有するスチ
レン系単量体溶液を、最終重合器出口における転化率が
少なくとも６５％になるように重合させ、次いでこの重
合液を１５０〜２８０℃の温度において３〜６０分間加
熱処理したのち、脱揮器に供給することを特徴とするゴ
ム変性スチレン系樹脂の製造方法。 ３ ゴム変性スチレン系樹脂が、スチレン系重合体を内
蔵したゴム状物質が分散したものであり、かつ該ゴム状
物質の粒子径が０．２〜１．５μｍ、面積平均粒子径／
数平均粒子径の比Ｄｓ／Ｄｎが２．５以下及び膨潤指数
が７〜１７のものである請求項１又は２記載のゴム変性
スチレン系樹脂の製造方法。[Scope of Claims] 1. A styrenic monomer containing a styrene-butadiene block copolymer rubber having a 1,2-vinyl bond content of 5 to 20% and a styrene unit content of 20 to 50% by weight. The polymerization solution is polymerized such that the conversion at the final polymerization vessel outlet is at least 65%, and then the polymerization solution is
A method for producing a rubber-modified styrenic resin, which comprises heating at a temperature of 50 to 280°C for 3 to 60 minutes, and then supplying the resin to a devolatilizer. 2 50% by weight or more of a styrene-butadiene block copolymer rubber having a 1,2-vinyl bond content of 5 to 20% and a styrene unit content of 20 to 50% by weight and a polybutadiene rubber of 50% by weight or less The styrenic monomer solution containing the mixture is polymerized so that the conversion rate at the exit of the final polymerization vessel is at least 65%, and then the polymerization liquid is heat-treated at a temperature of 150 to 280 ° C. for 3 to 60 minutes. , a method for producing a rubber-modified styrenic resin, characterized by supplying it to a devolatilizer. 3. The rubber-modified styrene-based resin is one in which a rubber-like substance containing a styrene-based polymer is dispersed, and the particle size of the rubber-like substance is 0.2 to 1.5 μm, and the area average particle size/
3. The method for producing a rubber-modified styrenic resin according to claim 1, wherein the number average particle diameter ratio Ds/Dn is 2.5 or less and the swelling index is 7 to 17.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4569590A JPH03250009A (en) | 1990-02-28 | 1990-02-28 | Production of rubber-modified styrene resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4569590A JPH03250009A (en) | 1990-02-28 | 1990-02-28 | Production of rubber-modified styrene resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03250009A true JPH03250009A (en) | 1991-11-07 |
Family
ID=12726521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4569590A Pending JPH03250009A (en) | 1990-02-28 | 1990-02-28 | Production of rubber-modified styrene resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03250009A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011012236A (en) * | 2009-07-06 | 2011-01-20 | Kuraray Co Ltd | Methacrylic resin composition and method for producing the same |
-
1990
- 1990-02-28 JP JP4569590A patent/JPH03250009A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011012236A (en) * | 2009-07-06 | 2011-01-20 | Kuraray Co Ltd | Methacrylic resin composition and method for producing the same |
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