JPS63238147A - Thermoplastic resin composition - Google Patents
Thermoplastic resin compositionInfo
- Publication number
- JPS63238147A JPS63238147A JP7229487A JP7229487A JPS63238147A JP S63238147 A JPS63238147 A JP S63238147A JP 7229487 A JP7229487 A JP 7229487A JP 7229487 A JP7229487 A JP 7229487A JP S63238147 A JPS63238147 A JP S63238147A
- Authority
- JP
- Japan
- Prior art keywords
- thermoplastic resin
- aromatic vinyl
- vinyl
- resin composition
- block copolymer
- 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.)
- Granted
Links
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 50
- 239000011342 resin composition Substances 0.000 title abstract description 27
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 75
- -1 aromatic vinyl compound Chemical class 0.000 claims abstract description 37
- 239000000178 monomer Substances 0.000 claims abstract description 37
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 37
- 229920001400 block copolymer Polymers 0.000 claims abstract description 36
- 229920001577 copolymer Polymers 0.000 claims abstract description 28
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 18
- 150000001993 dienes Chemical class 0.000 claims abstract description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 12
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims description 11
- 150000002978 peroxides Chemical class 0.000 abstract description 17
- 238000002156 mixing Methods 0.000 abstract description 10
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 abstract description 2
- 239000003999 initiator Substances 0.000 abstract 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 31
- 238000000034 method Methods 0.000 description 15
- 239000004793 Polystyrene Substances 0.000 description 10
- 229920002223 polystyrene Polymers 0.000 description 10
- 238000004898 kneading Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 2
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 239000012933 diacyl peroxide Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 150000002432 hydroperoxides Chemical class 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920000638 styrene acrylonitrile Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- QYOJZFBQEAZNEW-UHFFFAOYSA-N 1-(2-methylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC=CC=C1N1C(=O)C=CC1=O QYOJZFBQEAZNEW-UHFFFAOYSA-N 0.000 description 1
- FPZQYYXSOJSITC-UHFFFAOYSA-N 1-(4-chlorophenyl)pyrrole-2,5-dione Chemical compound C1=CC(Cl)=CC=C1N1C(=O)C=CC1=O FPZQYYXSOJSITC-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- BAWHYOHVWHQWFQ-UHFFFAOYSA-N 1-naphthalen-1-ylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC2=CC=CC=C12 BAWHYOHVWHQWFQ-UHFFFAOYSA-N 0.000 description 1
- RZRNAYUHWVFMIP-KTKRTIGZSA-N 1-oleoylglycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-KTKRTIGZSA-N 0.000 description 1
- YEKDUBMGZZTUDY-UHFFFAOYSA-N 1-tert-butylpyrrole-2,5-dione Chemical compound CC(C)(C)N1C(=O)C=CC1=O YEKDUBMGZZTUDY-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
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-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
- 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
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 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
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 description 1
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- SQHOHKQMTHROSF-UHFFFAOYSA-N but-1-en-2-ylbenzene Chemical compound CCC(=C)C1=CC=CC=C1 SQHOHKQMTHROSF-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 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
- 229920001971 elastomer Polymers 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229920006352 transparent thermoplastic Polymers 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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、透明性に優れ、かつ、耐衝撃性及び耐成形品
割れが改良された熱可塑性樹脂組成物に関し、特に熱可
塑性樹脂と芳香族ビニル・共役ジエン系ブロック共重合
体をビニル単量体及びラジカルの存在下で溶融混練する
ことにより得られる、透明性、耐衝撃性、耐成形品割れ
の優れた熱可塑性樹脂組成物に関するものである。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a thermoplastic resin composition that has excellent transparency and improved impact resistance and molded product cracking resistance. A thermoplastic resin composition with excellent transparency, impact resistance, and molded product cracking resistance obtained by melt-kneading a group vinyl/conjugated diene block copolymer in the presence of a vinyl monomer and radicals. It is.
従来、ポリスチレン、スチレン・アクリロニトリル共重
合体（以下単にｒ ＳＡＮ樹脂」と略記する）、ポリメ
タクリル酸メチル（以下単にｒ ＭＭＡ樹脂」と略記す
る）などの熱可塑性樹脂は、優れた透明性を有すること
から、その特性をいかして食品用容器、家庭用品、自動
車用部品、家電用品、工業用品など各種用途に幅広く用
いられている。Conventionally, thermoplastic resins such as polystyrene, styrene-acrylonitrile copolymer (hereinafter simply referred to as rSAN resin), and polymethyl methacrylate (hereinafter simply referred to as rMMA resin) have excellent transparency. Therefore, by taking advantage of its properties, it is widely used in various applications such as food containers, household goods, automobile parts, home appliances, and industrial goods.
しかし、これらの有用な熱可塑性樹脂も、用途によって
は耐衝撃性が未だ不足しており、必ずしも満足すべき材
料ではなかった０例えば、ポリスチレンは安価で加工性
に優れ、しかもその成形品が透明性及び外観に優れてい
ることから、極めて有用な樹脂ではあるが、該ポリスチ
レンは耐衝撃性に欠けているため、単独で使用される時
にはその用途が著しく限定されてしまっている。However, these useful thermoplastic resins still lack impact resistance depending on the application, and are not necessarily satisfactory materials.For example, polystyrene is inexpensive and has excellent processability, and its molded products are transparent. Although polystyrene is an extremely useful resin due to its excellent properties and appearance, its uses are severely limited when used alone because it lacks impact resistance.
したがって、このようなポリスチレンの耐衝撃性を改良
するために、ゴム変性ポリスチレンが製造された。しか
し、該ゴム変性ポリスチレンは耐′＃撃性についてはか
なり改良されてはいるけれども、ポリスチレン本来の特
性である透明性が著しく低下しているので、透明性が要
求される用途への利用は制限を受けていた。Therefore, in order to improve the impact resistance of such polystyrenes, rubber modified polystyrenes have been produced. However, although the rubber-modified polystyrene has considerably improved impact resistance, its transparency, which is an inherent property of polystyrene, has significantly decreased, so its use in applications that require transparency is limited. was receiving.
また、前記ＳＡＮ樹脂においても、成形加工性、剛性及
び透明性などの性質が優れているため、電気、電子関係
のハウジングや日用品などの分野への材料として多量に
使用されているが、該ＳＡＮ樹脂は耐衝撃性が低く、か
つ脆いため、工業用部品や日用品などに成形加工される
際、しばしば「割れ」が発生するといった問題点があっ
た。In addition, the SAN resin has excellent properties such as moldability, rigidity, and transparency, so it is used in large quantities as a material for electrical and electronic housings and daily necessities. Since resin has low impact resistance and is brittle, it often suffers from cracking when molded into industrial parts or daily necessities.
しかし、最近になって、これら熱可塑性樹脂の問題点、
特に耐衝撃性を改良する方法として、スチレンとブタジ
ェンからなるブロック共重合体をこれら熱可塑性樹脂に
配合する方法、例えば、特公昭５３−４１７号公報や特
開昭５８−１４１２３３号公報には熱可塑性樹脂に共役
ジオレフィン・ビニル芳香族化合物からなるブロック共
重合体を配合して耐衝撃性を改良する方法が提案されて
いる。However, recently, problems with these thermoplastic resins,
In particular, as a method for improving impact resistance, a method of blending a block copolymer consisting of styrene and butadiene with these thermoplastic resins, for example, Japanese Patent Publication No. 53-417 and Japanese Patent Application Laid-Open No. 58-141233, A method has been proposed to improve impact resistance by blending a block copolymer consisting of a conjugated diolefin/vinyl aromatic compound with a plastic resin.
しかしながら、このような方法によって得られる、熱可
塑性樹脂とブロック共重合体からなる組成物においても
、用途によっては未だ＋ｍ衝撃性が不充分であったり、
あるいは、透明性が低下したり、光沢が低下したりする
ことが生じるので、ユーザーからは耐衝撃性と透明性が
共に優れる熱可塑性樹脂組成物の開発が切望されていた
。However, even in compositions made of thermoplastic resin and block copolymer obtained by such a method, the +m impact strength may still be insufficient depending on the application.
Alternatively, the transparency or gloss may decrease, so users have been eager to develop a thermoplastic resin composition that has excellent impact resistance and transparency.
本発明者らはかかる現状に鑑み、耐衝撃性と透明性を同
時に満足するバランスの良い熱可塑性樹脂組成物を開発
すべく、鋭意検討した結果、スチレン系樹脂及びアクリ
ル系樹脂の１種又は２種以上の樹脂に、芳香族ビニル・
共役ジエン系ブロック共重合体を配合し、さらに、これ
をビニル系単量体及びラジカルの存在下で溶融混練する
ことによって、従来の熱可塑性樹脂に比べて耐衝撃性と
透明性のバランスが高水準となった熱可塑性樹脂組成物
が得られることを見出し、本発明を完成させた。In view of the current situation, the present inventors conducted intensive studies to develop a well-balanced thermoplastic resin composition that satisfies impact resistance and transparency at the same time. Aromatic vinyl, resin
By blending a conjugated diene block copolymer and melt-kneading it in the presence of vinyl monomers and radicals, it has a higher balance of impact resistance and transparency than conventional thermoplastic resins. It was discovered that a thermoplastic resin composition that has become standard can be obtained, and the present invention was completed.
すなわち本発明は、（ａ）芳香族ビニル化合物の重合体
、芳香族ビニル化合物と他のビニル系単量体との共重合
体、（メタ）アクリル酸メチル重合体及び（メタ）アク
リル酸メチルと他のビニル系単量体との共重合体の中か
ら選ばれた少なくとも一種の熱可塑性樹脂２５〜８７重
量％と、（ｂ）芳香族ビニル化合物を１０〜９０重量％
含有する芳香族ビニル−共役ジエン系ブロック共重合体
３〜７５重量％とを、ビニル系単量体及びラジカルの存
在下に溶融混練して得られた熱可塑性樹脂組成物である
。That is, the present invention provides (a) polymers of aromatic vinyl compounds, copolymers of aromatic vinyl compounds and other vinyl monomers, methyl (meth)acrylate polymers, and methyl (meth)acrylates. 25 to 87% by weight of at least one thermoplastic resin selected from copolymers with other vinyl monomers and (b) 10 to 90% by weight of an aromatic vinyl compound.
This is a thermoplastic resin composition obtained by melt-kneading 3 to 75% by weight of an aromatic vinyl-conjugated diene block copolymer in the presence of a vinyl monomer and a radical.
佐皮基テ
（ａ）熱可塑性樹脂成分
本発明の熱可塑性樹脂組成物の（ａ）成分として用いら
れる芳香族−ビニル化合物重合体、及び芳香族ビニル化
合物と他のビニル系単量体との共重合体としては、芳香
族ビニル化合物の単独重合体あるいは芳香族ビニル化合
物と他のビニル系単量体との共重合体が用いられる。(a) Thermoplastic resin component The aromatic-vinyl compound polymer used as the component (a) of the thermoplastic resin composition of the present invention, and the combination of the aromatic vinyl compound and other vinyl monomers. As the copolymer, a homopolymer of an aromatic vinyl compound or a copolymer of an aromatic vinyl compound and another vinyl monomer is used.
前記芳香族ビニル化合物としては、スチレン、０−メチ
ルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン
、クロルスチレン、ジクロルスチレン、ブロムスチレン
、ジブロムスチレン、α−メチルスチレン、α−エチル
スチレン、メチル−α−メチルスチレン、ジメチルスチ
レン、ビニルナフタリンなどがあり、この中でスチレン
、ｐ−メチルスチレン、α−メチルスチレン、あるいは
、これらの混合物が好ましく、特にスチレン、α−メチ
ルスチレンあるいはこれらの混合物が好ましい。Examples of the aromatic vinyl compounds include styrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, chlorostyrene, dichlorostyrene, bromustyrene, dibromstyrene, α-methylstyrene, α-ethylstyrene, and methyl. -α-methylstyrene, dimethylstyrene, vinylnaphthalene, etc. Among these, styrene, p-methylstyrene, α-methylstyrene, or a mixture thereof is preferred, and styrene, α-methylstyrene, or a mixture thereof is particularly preferred. preferable.
これら芳香族ビニル化合物と共重合されるビニル系単量
体としては、例えばアクリロニトリル、メタクリロニト
リル等のシアン化ビニル、（メタ）アクリル酸等の不飽
和酸単量体、（メタ）アクリル酸メチル、（メタ）アク
リル酸エチル、（メタ）アクリル酸ブチル、（メタ）ア
クリル酸−２−エチルヘキシルなどの（メタ）アクリル
酸のアルキルエステル、無水マレイン酸、無水イタコン
酸等の不飽和酸無水物、Ｎ−フェニルマレイミド、Ｎ−
メチルマレイミド、Ｎ−エチルマレイミド、Ｎ−ｔ−ブ
チルマレイミド、Ｎ−シクロヘキシルマレイミド、Ｎ−
ｐ−クロロフェニルマレイミド、Ｎ−ナフチルマレイミ
ドなどのＮ−置換マレイミドなどがあるが、これらの中
でもアクリロニトリル、無水マレイン酸、メタクリル酸
メチル、Ｎ−フェニルマレイミド、Ｎ−シクロヘキシル
マレイミド、Ｎ−ｏ−メチルフェニルマレイミドなどが
好ましい。Examples of vinyl monomers copolymerized with these aromatic vinyl compounds include vinyl cyanide such as acrylonitrile and methacrylonitrile, unsaturated acid monomers such as (meth)acrylic acid, and methyl (meth)acrylate. , alkyl esters of (meth)acrylic acid such as ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; N-phenylmaleimide, N-
Methylmaleimide, N-ethylmaleimide, N-t-butylmaleimide, N-cyclohexylmaleimide, N-
There are N-substituted maleimides such as p-chlorophenylmaleimide and N-naphthylmaleimide, among which acrylonitrile, maleic anhydride, methyl methacrylate, N-phenylmaleimide, N-cyclohexylmaleimide, and N-o-methylphenylmaleimide. etc. are preferable.
これら芳香族ビニル化合物重合体または共重合体の製造
方法としては、一般に公知の重合又は共重合方法によっ
て製造することができる。These aromatic vinyl compound polymers or copolymers can be produced by generally known polymerization or copolymerization methods.
好ましい芳香族ビニル化合物の重合体または共重合体と
しては、ポリスチレン、スチレン・アクリロニトリル共
重合体、スチレン・メタクリル酸メチル共重合体、スチ
レン・無水マレイン酸共重合体、スチレン・Ｎ−置換マ
レイミド共重合体などであり、これら共重合体中には芳
香族ビニル化合物単位が５０重量２以上、特に６０重量
２゛以上含有されていることが好ましい。Preferred aromatic vinyl compound polymers or copolymers include polystyrene, styrene/acrylonitrile copolymer, styrene/methyl methacrylate copolymer, styrene/maleic anhydride copolymer, and styrene/N-substituted maleimide copolymer. It is preferable that these copolymers contain aromatic vinyl compound units in an amount of 50% by weight or more, particularly 60% by weight or more.
さらに、本発明の熱可塑性樹脂組成物の（ａ）成分とし
て用いられる、もう一方の（メタ）アクリル酸メチル重
合体、及び（メタ）アクリル酸メチルと他のビニル系単
量体の共重合体としては、（メタ）アクリル酸メチルの
単独重合体あるいは（メタ）アクリル酸メチルと他のビ
ニル系単量体との共重合体が用いられる。Furthermore, another methyl (meth)acrylate polymer and a copolymer of methyl (meth)acrylate and another vinyl monomer are used as component (a) of the thermoplastic resin composition of the present invention. As the material, a homopolymer of methyl (meth)acrylate or a copolymer of methyl (meth)acrylate and another vinyl monomer is used.
前記（メタ）アクリル酸メチルとしては、メタクリル酸
メチル及び／又はアクリル酸メチルであり、中でもメタ
クリル酸メチルが好ましい。これら（メタ）アクリル酸
メチルと共重合されるビニル系単量体としては前述のビ
ニル系単量体から（メタ）アクリル酸メチルを除き、前
記芳香族ビニル化合物を加えたものである。The methyl (meth)acrylate is methyl methacrylate and/or methyl acrylate, and methyl methacrylate is particularly preferred. The vinyl monomer to be copolymerized with these methyl (meth)acrylates is one obtained by removing methyl (meth)acrylate from the above-mentioned vinyl monomers and adding the above-mentioned aromatic vinyl compound.
これらビニル系単量体の中でも、スチレン、α−メチル
スチレンを使用することが好ましい。Among these vinyl monomers, styrene and α-methylstyrene are preferably used.
これら（メタ）アクリル酸メチル重合体及び共重合体の
製造方法としては、一般に公知の重合又は共重合方法に
よって製造することができる。These methyl (meth)acrylate polymers and copolymers can be produced by generally known polymerization or copolymerization methods.
好ましい（メタ）アクリル酸メチル重合体又は共重合体
としては、ポリメタアクリル酸メチル。A preferred methyl (meth)acrylate polymer or copolymer is polymethyl methacrylate.
メタアクリル酸メチル・スチレン共重合体などであり、
前に共重合体中の（メタ）アクリル酸メチル単位の含有
量は５０重量２以上、特に６０重量２以上であることが
好ましい。Methyl methacrylate/styrene copolymer, etc.
The content of methyl (meth)acrylate units in the copolymer is preferably 50% by weight or more, particularly 60% by weight or more.
これら熱可塑性樹脂（ａ）成分の中では、芳香族ビニル
化合物重合体、又は芳香族ビニル化合物と他のビニル系
単量体からなる共重合体を用いることが好ましく、更に
芳香族ビニル化合物と他のビニル系単量体からなる共重
合体を用いることが好ましく、特にスチレン自アクリロ
ニトリル共重合体を用いることが好ましい。Among these thermoplastic resin (a) components, it is preferable to use an aromatic vinyl compound polymer or a copolymer consisting of an aromatic vinyl compound and another vinyl monomer, and furthermore, an aromatic vinyl compound and another vinyl monomer. It is preferable to use a copolymer consisting of vinyl monomers, and it is particularly preferable to use a styrene self-acrylonitrile copolymer.
（ｂ）芳香族ビニル会共役ジエン系ブロック共重合体成
分
本発明の熱可塑性樹脂組成物の（ｂ）成分として用いら
れる芳香族ビニル・共役ジエン系ブロック共重合体は、
該ブロック共重合体を構成する芳香族ビニル化合物とし
て前記熱可塑性樹脂（ａ）成分において示した芳香族ビ
ニル化合物が使用でき、これら芳香族ビニル化合物の中
では特にスチレンが好ましい。(b) Aromatic vinyl-conjugated diene block copolymer component The aromatic vinyl-conjugated diene block copolymer used as the component (b) of the thermoplastic resin composition of the present invention is:
As the aromatic vinyl compound constituting the block copolymer, the aromatic vinyl compounds shown in the thermoplastic resin (a) component can be used, and among these aromatic vinyl compounds, styrene is particularly preferred.
一方、上記ブロック共重合体を構成する共役ジエン化合
物として用いられるものは、例えばブタジェン、イソプ
レン、ピペリレンなどが挙げられ、これらの共役ジエン
化合物の中では、ブタジェン、イソプレンを用いること
が好ましい。On the other hand, examples of the conjugated diene compound used in the block copolymer include butadiene, isoprene, piperylene, etc. Among these conjugated diene compounds, butadiene and isoprene are preferably used.
本発明の熱可塑性樹脂組成物で使用される、好ましい芳
香族ビニルｅ共役ジエン系ブロック共重合体（ｂ）とし
ては、一般式
％式％
で示されるブロック共重合体が用いられる。ただし、上
記一般式中、Ａは芳香族ビニル化合物の重合体ブロック
であり、全ブ西ツク共重合体（ｂ）成分の５０重ＭＷ以
上を含むことが好ましく、さらに好ましくは５０〜９７
重量％含んでいるのが好ましい、また、Ｂは共役ジエン
あるいはＢ中に５０重量２以下の芳香族ビニル化合物が
共重合された共役ジエン重合体ブロックであり、Ａの合
計含有量は全芳香族ビニル化合物の５０〜１００重量２
である。As the preferred aromatic vinyl e-conjugated diene block copolymer (b) used in the thermoplastic resin composition of the present invention, a block copolymer represented by the general formula % is used. However, in the above general formula, A is a polymer block of an aromatic vinyl compound, which preferably contains 50 times MW or more of the whole vinyl copolymer (b) component, more preferably 50 to 97
In addition, B is a conjugated diene or a conjugated diene polymer block in which an aromatic vinyl compound of 50% by weight or less is copolymerized in B, and the total content of A is wholly aromatic. 50-100 weight of vinyl compound2
It is.
Ｘはカップリング剤の残基を示す、＋ｉは１以上、好ま
しくは１〜４の整数、ｎは２〜６、好ましくは３〜６の
整数である。X represents a residue of a coupling agent, +i is an integer of 1 or more, preferably 1 to 4, and n is an integer of 2 to 6, preferably 3 to 6.
これらブロック共重合体（ｂ）中の全芳香族ビニル化合
物の含量は１０〜９０重量％、好ましくは１５〜８５ｍ
Ｍ ％である。ブロック共重合体（ｂ）中の全芳香族
ビニル化合物の含量が１０重量％未満であると、本発明
の熱可塑性樹脂組成物の透明性、耐衝撃性が低下し、Ｓ
Ｏ重量％ｔ−超えると耐衝撃性が低下するので好ましく
ない。The content of wholly aromatic vinyl compounds in these block copolymers (b) is 10 to 90% by weight, preferably 15 to 85% by weight.
M%. If the content of the wholly aromatic vinyl compound in the block copolymer (b) is less than 10% by weight, the transparency and impact resistance of the thermoplastic resin composition of the present invention will decrease, and S
If it exceeds 0% by weight, the impact resistance decreases, which is not preferable.
これらブロック共重合体（ｂ）の中でも特に好ましいブ
ロック共重合体としては、特開昭６０−１７９４４９号
公報に記載されている、次の一般式で表わされる構造を
有するブロック共重合体が用いられ、該ブロック共重合
体を用いた熱可塑性樹脂組成物はウェルド強度の優れた
ものが得られる。Among these block copolymers (b), a block copolymer having a structure represented by the following general formula, which is described in JP-A-60-179449, is used. A thermoplastic resin composition using the block copolymer has excellent weld strength.
一般式
％式％）
（式中、Ａはビニル芳香族化合物重合体ブロックであっ
て、Ａの合計量は、ブロック共重合体中のビニル芳香族
化合物全体の５０〜８７重量％を含んでいる。またＢは
共役ジエンとビニル芳香族化合物との共重合体であって
、Ｂ部分がビニル芳香族化合物が漸増するテーパーブロ
ックを２〜１０個含有している。ｎは３〜６の整数、Ｘ
はカップリング剤の残基を示す、）
であって、かつ、ビニル芳香族化合物がモノマ一単位で
１個もしくは４（Ｉｌ以下で連らなった連鎖結合単位
を構成するビニル芳香族化合物単位の含量がブロック共
重合体中のビニル芳香族化合物全体の５〜２５重量２で
ある構造を有している。これらブロック共重合体（ｂ）
は水素添加されたものであってもよい。(General formula % formula %) (wherein A is a vinyl aromatic compound polymer block, and the total amount of A includes 50 to 87% by weight of the entire vinyl aromatic compound in the block copolymer. In addition, B is a copolymer of a conjugated diene and a vinyl aromatic compound, and the B portion contains 2 to 10 tapered blocks in which the vinyl aromatic compound gradually increases. n is an integer of 3 to 6; X
represents a residue of a coupling agent), and one vinyl aromatic compound is 1 or 4 (Il or less) of vinyl aromatic compound units constituting a chain bond unit in one monomer unit. These block copolymers (b) have a structure in which the content is 5 to 25% by weight of the total vinyl aromatic compound in the block copolymer.
may be hydrogenated.
（ｃ）ビニル単量体成分
本発明において用いられるビニル系単量体としては、前
記熱可塑性樹脂（ａ）成分の所で示したビニル系単量体
が使用できる。好ましいビニル糸車単量体としては、前
記熱可塑性樹脂（ａ）成分の重合成分と同類あるいは同
じビニル系単量体である。これらビニル系単量体として
は１種又は２種以上混合して使用することができる。(c) Vinyl monomer component As the vinyl monomer used in the present invention, the vinyl monomers listed above for the thermoplastic resin (a) component can be used. Preferred vinyl spinning wheel monomers are vinyl monomers similar to or the same as the polymerization component of the thermoplastic resin (a) component. These vinyl monomers may be used alone or in combination of two or more.
（ｄ）ラジカル成分
本発明において溶融混合時に存在させるラジカルとして
は、過酸化物やアゾビス化合物のようなラジカル発生剤
を添加する方法や、光分解や熱分解でラジカルを発生さ
せる方法などいずれの方法でもよい。(d) Radical component In the present invention, the radicals to be present during melt mixing can be prepared by any method such as adding a radical generator such as peroxide or an azobis compound, or generating radicals by photolysis or thermal decomposition. But that's fine.
これらの中ではラジカル発生剤を添加する方法が好まし
く、特に過酸化物を添加する方法が好ましい。Among these, the method of adding a radical generator is preferred, and the method of adding a peroxide is particularly preferred.
前記過酸化物としては、ｔ−ブチルペルオキシベンゾエ
ート、ｔ−ブチルペルオキシレートなどのペルオキシエ
ステル類、キュメンヒドロペルオキシド、ｔ−ブチルヒ
ドロペルオキシドなどのヒドロペルオキシド類、ジクミ
ルペルオキシド、ジ−ｔ−ブチルペルオキシドなどのジ
アルキルペルオキシド類、メチルエチルケトンペルオキ
シド、メチルイソブチルケトンペルオキシドなどのケト
ンペルオキシド類、ラウロイルペルオキシド、ベンゾイ
ルペルオキシドなどのジアシルペルオキシド類、ペルオ
キシジカーボネート類、ポリメリックペルオキシド類及
び過酸水素などが挙げられるが、これらの中ではジアル
キルペルオキシド類、ヒドロペルオキシド類、ジアシル
ペルオキシド類、ポリメリックペルオキシド類が好まし
い。これら過酸化物は１種又は２種以上併用することが
でき、さらに、反応助剤と組合せて使用することもでき
る。Examples of the peroxide include peroxyesters such as t-butyl peroxybenzoate and t-butyl peroxylate, hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide, dicumyl peroxide, and di-t-butyl peroxide. These include dialkyl peroxides, ketone peroxides such as methyl ethyl ketone peroxide and methyl isobutyl ketone peroxide, diacyl peroxides such as lauroyl peroxide and benzoyl peroxide, peroxydicarbonates, polymeric peroxides, and hydrogen peroxide. Preferred are dialkyl peroxides, hydroperoxides, diacyl peroxides, and polymeric peroxides. These peroxides can be used alone or in combination of two or more, and can also be used in combination with a reaction aid.
（ｅ）その他の成分
本発明の熱可塑性樹脂組成物には、通常の熱可塑性樹脂
において用いられる添加剤を必要に応じて添加すること
ができる。これら添加剤としては１例えば、オレイン酸
モノグリセライド、ポリオキシエチレングリセリンモノ
ステアレートとなどの界面活性剤、シリカ、タルク、ガ
ラス１−Ｊｌｌ！ａなどの充填剤または補強剤、あるい
は、酸化防止剤、紫外線吸収剤、帯電防止剤、難燃剤、
滑剤、発泡剤、着色剤、顔料、核剤、架橋剤、可塑剤架
橋助剤などがあり、これらは混合して用いることができ
る。(e) Other components Additives used in ordinary thermoplastic resins can be added to the thermoplastic resin composition of the present invention as necessary. Examples of these additives include surfactants such as oleic acid monoglyceride and polyoxyethylene glycerin monostearate, silica, talc, and glass. Fillers or reinforcing agents such as a, or antioxidants, ultraviolet absorbers, antistatic agents, flame retardants,
There are lubricants, foaming agents, coloring agents, pigments, nucleating agents, crosslinking agents, plasticizers, crosslinking aids, etc., and these can be used in combination.
その他必要に応じてゴム状重合体１例えば、ＳＢＲ、Ｎ
ＢＲ、ＢＲ，ＥＰＴ 、 ＥＰＲ、ＮＲ，ＩＲ，１，２
−ポリブタジェン、ＡＲ，ＣＲｌＩＩＲ、ＨＳＲ等を本
発明の目的を損なわない範囲内で添加することができる
。Other rubber-like polymers 1, for example, SBR, N
BR, BR, EPT, EPR, NR, IR, 1, 2
- Polybutadiene, AR, CRlIIR, HSR, etc. can be added within a range that does not impair the purpose of the present invention.
ｌ几
前記熱可塑性樹脂（ａ）成分とブロック共重合体（ｂ）
成分の使用割合は（ａ） ／（ｂ）が２５〜９７／３〜
７５重量２．好マシくは４０〜９０／ １０〜ｅＯ重量
％ノＲ囲内で用いることが必要である。熱可塑性樹脂（
ａ）成分が２５５重量部満（ブロック共重合体（ｂ）が
７５５重量部超える）であると、熱可塑性樹脂組成物の
剛性の低下や成形時の金型からの成形品の離型時の白化
現象が起る。また、熱可塑性樹脂（ａ）成分が９７７重
量部超える（ブロック共重合体（ｂ）成分が３重量２未
満）場合には、耐衝撃性が十分でなくなる。The thermoplastic resin (a) component and the block copolymer (b)
The ratio of ingredients used is (a)/(b) from 25 to 97/3
75 weight 2. It is preferable to use it within the range of 40 to 90/10 to eO weight %. Thermoplastic resin(
If the amount of component a) is less than 255 parts by weight (the block copolymer (b) exceeds 755 parts by weight), the rigidity of the thermoplastic resin composition may decrease or the molded product may be released from the mold during molding. A bleaching phenomenon occurs. Moreover, when the thermoplastic resin (a) component exceeds 977 parts by weight (the block copolymer (b) component is less than 3 parts by weight), the impact resistance becomes insufficient.
本発明の熱可塑性樹脂組成物に溶融混練するビニル系単
量体の添加量は、熱可塑性樹脂（ａ）成分とブロック共
重合体（ｂ）成分の合計１ｏｏ重量部に対し通常は０．
５〜５０重量部、好ましくは １〜３０重量部、特に好
ましくは３〜２０重量部の範囲で使用される。The amount of the vinyl monomer to be melt-kneaded into the thermoplastic resin composition of the present invention is usually 0.000 parts by weight per 10 parts by weight of the thermoplastic resin (a) component and block copolymer (b) component.
It is used in an amount of 5 to 50 parts by weight, preferably 1 to 30 parts by weight, particularly preferably 3 to 20 parts by weight.
また、ラジカル発生剤を添加して溶融混練する場合、そ
の添加量は、熱可塑性樹脂（ａ）成分とブロック共重合
体（ｂ）成分の合計１ｏｏ重量部に対して通常はｏ、ｏ
ｏｉ〜５重量部、好ましくは０．０１〜３．５重量部、
特に好ましくは０．０５〜２．０重量部の範囲で使用さ
れる。In addition, when a radical generator is added and melt-kneaded, the amount added is usually o, o to 100 parts by weight in total of the thermoplastic resin (a) component and the block copolymer (b) component.
oi to 5 parts by weight, preferably 0.01 to 3.5 parts by weight,
It is particularly preferably used in an amount of 0.05 to 2.0 parts by weight.
産致里１
本発明において行なわれる溶融混練の方法は、従来より
公知の方法が使用できる。Sanchiri 1 As the melt-kneading method carried out in the present invention, conventionally known methods can be used.
本発明において熱可塑性樹脂（ａ）成分と、ブロック共
重合体（ｂ）成分とを、ビニル系単量体及び過酸化物の
存在下に、必要により前記界面活性剤や充填剤などの各
種添加剤を添加して行なわれる溶融混練は、押出機（車
軸、二輪）、ロール、バンバリーミキサ−、ニーダ−な
どの公知の混練、混合装置及び方法を用いて行なうこと
ができる。また、ビニル系単量体及び／又は過酸化物の
添加方法としては、溶融混練前に混合してもよく、また
、溶融混練途中に一括して、あるいは分割して、もしく
は連続的に添加してもよい。In the present invention, the thermoplastic resin (a) component and the block copolymer (b) component are mixed in the presence of a vinyl monomer and a peroxide, with the addition of various surfactants, fillers, etc. as necessary. The melt-kneading performed by adding the agent can be performed using known kneading and mixing equipment and methods such as an extruder (axle, two-wheeled), roll, Banbury mixer, kneader, and the like. Furthermore, the vinyl monomer and/or peroxide may be added by mixing before melt-kneading, or may be added all at once, in parts, or continuously during melt-kneading. It's okay.
口 朔
このようにして得られた熱可塑性樹脂組成物は、前記ビ
ニル単量体成分（ｃ）が過酸化物成分（ｄ）や熱可塑性
樹脂成分（ａ）およびブロック共重合体成分（ｂ）と共
に溶融混練されて、ビニル単量体の重合物が前記熱可塑
性樹脂成分（ａ）あるいはブロック共重合体（ｂ）にグ
ラフト共重合され、熱可塑性樹脂組成物中に含有されて
おり、それによって熱可塑性樹脂組成物全体の透明性及
び耐衝撃性の顕著な改良効果が生じる。In the thus obtained thermoplastic resin composition, the vinyl monomer component (c) is a peroxide component (d), a thermoplastic resin component (a), and a block copolymer component (b). The vinyl monomer polymer is graft copolymerized to the thermoplastic resin component (a) or the block copolymer (b), and is contained in the thermoplastic resin composition. This results in a significant improvement in the transparency and impact resistance of the entire thermoplastic resin composition.
また前記の方法で得た熱可塑性樹脂組成物の成形加工に
は、公知の方法１例えば、押出成形、射出成形、中空成
形、圧縮成形、カレンダー加工などの方法によって実用
上有用な成形品に成形加工することができる。また必要
に応じて、塗装、メッキなどの加工を施すことも出来る
。In addition, the thermoplastic resin composition obtained by the above method can be molded into a practically useful molded product by known methods such as extrusion molding, injection molding, blow molding, compression molding, and calendering. Can be processed. Further, if necessary, processing such as painting or plating can be applied.
本発明の熱可塑性樹脂組成物は、前記成形加工法により
各種用途に適した形状に成形加工されて、優れた透明性
、耐衝撃性、加工性、相溶性、塗装性、印刷性、接着性
を活してテレビ、ステレオ、掃除機などの家電用品、バ
ンパ一部品、テールランプ、ボディーパネル、サイドシ
ールなどの自動車部品その他１日用品、レジャー用品、
玩具、工業用品など幅広い用途に用いることができる。The thermoplastic resin composition of the present invention can be molded into a shape suitable for various uses by the above-mentioned molding method, and has excellent transparency, impact resistance, processability, compatibility, paintability, printability, and adhesion. Utilizing this technology, we produce home appliances such as TVs, stereos, vacuum cleaners, automobile parts such as bumper parts, tail lamps, body panels, side seals, other daily necessities, leisure goods,
It can be used for a wide range of purposes such as toys and industrial supplies.
これら用途の中でも射出成形及びシート成形成形による
用途において、本発明の熱可塑性樹脂組成物の効果が有
効に発揮される０本発明の組成物は透明性、耐衝撃性等
に優れているので、特に射出成形用組成物として用いる
のが好ましい。Among these applications, the effects of the thermoplastic resin composition of the present invention are effectively exhibited in applications involving injection molding and sheet molding.Since the composition of the present invention has excellent transparency, impact resistance, etc., It is particularly preferable to use it as an injection molding composition.
以下に本発明の実施例をあげて詳細に説明するが、本発
明の主旨を越えない限り、この実施例に限定されるもの
ではない。The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples unless the gist of the present invention is exceeded.
実施例１〜１７及び比較例１〜１９
く配合成分〉
１匪１並ＪＩ！
ＧＰＰＳ ：汎用ポリスチレン
ＨＩＰＳ ：耐衝撃性ポリスチレン
ＳＡＮ ：スチレン番アクリロニトリル共重合体（Ｓ
Ｍ／ＡＮ−８８／３２）
ＰＭＭＡ ：ポリメタクリル酸メチル
ＭＳ：スチレン−ＭＭＡ共重合体
（ＳＭ／ＨＭＡ＝７０／３０）
ＳＭＡ ：スチレン・無水マレイン酸共重合体Ｃ’３
Ｍ／ＭＡ−７０／３０）
ブローク 〜体
ブロック共重合体（Ｂｌ） ：
日本合成ゴム株制１．ｌＳＲＳＩＳ ５０００ブロック
共重合体（８２） ：
日本合成ゴム株製、ＪＳＲＴＲ２０００ブロック共重合
体（Ｂ３） ：
日本合成ゴム株製、ＪＳＲＴＲ２４００ブロック共重合
体（Ｂ４）：
電気化学■製、クリアレン５３０
ζ三亙ヱユ上
ＳＭ／ＡＮ ：スチレン／アクリロニトリルＳＭ： ス
チレン
ＨＭＡ ：メチルメタアクリレート
ＨＭＡ／ＳＭ：メチルメタクリレート／スチレンＳ阿／
ＭＡＡ： スチレン／ｍ水マレイン酸４醜豆ｊ
過酸化物（ＰＩ）： ２，５−ジメチル−２，５−ジ（
ｔ−ブチルペルオキシ）ヘキサン
過酸化物（Ｐ２）ニジイソピルベンゼンペルオキシド
過酸化物（Ｐ３）：ラウロイルベルオキシドく溶融混線
〉
上記配合成分を表−１及び２に示す配合量で配合し、５
０履鳳φ二軸押出機で溶融混練してペレット化した。た
だし、実施例１−１７のビニル系単量体及び過酸化物は
予め均一に混合した後、押出機内の溶融混練される途中
の位置へ連続的に添加しながら配合物を溶融混練した。Examples 1 to 17 and Comparative Examples 1 to 19 Ingredients> 1 mo JI! GPPS: General purpose polystyrene HIPS: Impact resistant polystyrene SAN: Styrene number acrylonitrile copolymer (S
M/AN-88/32) PMMA: Polymethyl methacrylate MS: Styrene-MMA copolymer (SM/HMA=70/30) SMA: Styrene/maleic anhydride copolymer C'3
M/MA-70/30) Broke block copolymer (Bl): Japan Synthetic Rubber Co., Ltd. 1. lSRSIS 5000 block copolymer (82): manufactured by Japan Synthetic Rubber Co., Ltd., JSRTR2000 block copolymer (B3): manufactured by Japan Synthetic Rubber Co., Ltd., JSRTR2400 block copolymer (B4): manufactured by Denki Kagaku ■, Clearene 530 ζ Sanno Eyuu SM/AN: Styrene/Acrylonitrile SM: Styrene HMA: Methyl methacrylate HMA/SM: Methyl methacrylate/Styrene SA/
MAA: Styrene/m water maleic acid 4-ugly beanj Peroxide (PI): 2,5-dimethyl-2,5-di(
t-Butylperoxy)hexane peroxide (P2) diisopylbenzene peroxide (P3): lauroyl peroxide Melt mixing> The above ingredients were blended in the amounts shown in Tables 1 and 2, and 5
The mixture was melt-kneaded and pelletized using a 0-diameter twin-screw extruder. However, the vinyl monomer and peroxide of Examples 1-17 were uniformly mixed in advance, and then the blend was melt-kneaded while being continuously added to a position in the extruder where they were being melt-kneaded.
く物性測定〉
上記溶融混練して得た熱可塑性樹脂組成物のベレットを
射出成形機を用いて試験片を成形し、透明性（ヘイズ）
及びデュポン衝撃強度を測定した。Measurement of physical properties> The pellet of the thermoplastic resin composition obtained by melt-kneading the above was molded into a test piece using an injection molding machine, and the transparency (haze) was measured.
and DuPont impact strength were measured.
また、製品離型時の割れを確認するため１００×１５０
Ｘ ３０ｍ／ｍの箱型成形品を東芝機械（ｌＳ−１２
５ＣＮＩＩ、バイザー付）射出成形機により成形して、
成形体の割れを目視により評価した。In addition, in order to check for cracks when releasing the product, a 100 x 150
Toshiba Machine (lS-12
5CNII, with visor) molded with an injection molding machine,
Cracks in the molded bodies were evaluated visually.
・ その結果を表−１及び表−２に示す。・The results are shown in Table-1 and Table-2.
なお、各種測定及び評価基準は下記の方法によった。In addition, various measurements and evaluation criteria were based on the following methods.
ヘイズ ＪＩＳ Ｋ ６７１４に準じて測定した。haze Measured according to JIS K 6714.
デュポン−。Dupont.
デュポン衝撃試験機（東洋精機■製）を用いて測定した
。It was measured using a DuPont impact tester (manufactured by Toyo Seiki ■).
試験片：縦５５ｍ／ｍ Ｘ横８０＋＊／ｍ Ｘ厚２．４
ｍ／ａ、受け４３ｍ１ｌφ、打撃棒１２．７ｍｍφｌ
れ 目 １
０：ヒビ、割れまったくなし。Test piece: length 55m/m x width 80++/m x thickness 2.4
m/a, receiver 43mlφ, striking rod 12.7mmφl
Eyes 1 0: No cracks or splits at all.
Δ：ヒビは若干認められるが、割れまでには至っていな
い。Δ: Some cracks are observed, but they have not reached the level of cracking.
×：製品の一部が欠損するなどの割れがある。×: There is cracking such as part of the product missing.
表−１及び表−２の結果から本発明の熱可塑性樹脂組成
・物は透明性及び耐衝撃性に優れていることがわかる。From the results in Tables 1 and 2, it can be seen that the thermoplastic resin compositions and products of the present invention have excellent transparency and impact resistance.
比較例より明らかな如く、透明性を有する熱可塑性樹脂
にブロック共重合体を配合する従来の方法では、耐衝撃
性の改良効果が十分でなく、かつ、透明性が大幅に低下
してしまうことが理解できる。As is clear from the comparative examples, the conventional method of blending a block copolymer into a transparent thermoplastic resin does not have a sufficient effect of improving impact resistance, and the transparency is significantly reduced. I can understand.
以上実施例などで述べたごとく、本発明の熱可塑性樹脂
組成物は、透明性の低下が少なく、大幅に＃衝撃性が改
良され、しかも成形時の成形品の割れもないので、透明
性が要求される熱可塑性樹脂の用途が広い分野に展開さ
れ、極めて工業的価値の高い材料である。As described in the examples above, the thermoplastic resin composition of the present invention has little decrease in transparency, significantly improved impact resistance, and no cracking of molded products during molding, so transparency is high. The required thermoplastic resin is used in a wide range of fields, and is a material with extremely high industrial value.
Claims (1)
と他のビニル系単量体との共重合体、（メタ）アクリル
酸メチル重合体及び（メタ）アクリル酸メチルと他のビ
ニル系単量体との共重合体の中から選ばれた少なくとも
一種の熱可塑性樹脂２５〜９７重量％と、 （ｂ）芳香族ビニル化合物を１０〜９０重量％含有する
芳香族ビニル−共役ジエン系ブロック共重合体３〜７５
重量％とを、 ビニル系単量体及びラジカルの存在下に溶融混練して得
られた熱可塑性樹脂組成物。[Claims] (a) An aromatic vinyl compound polymer, a copolymer of an aromatic vinyl compound and another vinyl monomer, a methyl (meth)acrylate polymer, and a methyl (meth)acrylate. 25 to 97% by weight of at least one thermoplastic resin selected from copolymers with other vinyl monomers; and (b) an aromatic vinyl compound containing 10 to 90% by weight of an aromatic vinyl compound. Conjugated diene block copolymer 3-75
% by weight in the presence of a vinyl monomer and a radical.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62072294A JP2581062B2 (en) | 1987-03-26 | 1987-03-26 | Method for producing thermoplastic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62072294A JP2581062B2 (en) | 1987-03-26 | 1987-03-26 | Method for producing thermoplastic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63238147A true JPS63238147A (en) | 1988-10-04 |
| JP2581062B2 JP2581062B2 (en) | 1997-02-12 |
Family
ID=13485102
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62072294A Expired - Lifetime JP2581062B2 (en) | 1987-03-26 | 1987-03-26 | Method for producing thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2581062B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005112958A (en) * | 2003-10-06 | 2005-04-28 | Asahi Kasei Chemicals Corp | Method for producing styrene-based resin composition and resin composition |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59129243A (en) * | 1979-11-30 | 1984-07-25 | ザ・ダウ・ケミカル・カンパニ− | Physically improved styrene polymer/thermoplastic elastomer polyblends |
-
1987
- 1987-03-26 JP JP62072294A patent/JP2581062B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59129243A (en) * | 1979-11-30 | 1984-07-25 | ザ・ダウ・ケミカル・カンパニ− | Physically improved styrene polymer/thermoplastic elastomer polyblends |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005112958A (en) * | 2003-10-06 | 2005-04-28 | Asahi Kasei Chemicals Corp | Method for producing styrene-based resin composition and resin composition |
| JP4522681B2 (en) * | 2003-10-06 | 2010-08-11 | 旭化成ケミカルズ株式会社 | Method for producing styrenic resin composition and resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2581062B2 (en) | 1997-02-12 |
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