JPS63291942A - Thermoplastic resin composition - Google Patents
Thermoplastic resin compositionInfo
- Publication number
- JPS63291942A JPS63291942A JP12907687A JP12907687A JPS63291942A JP S63291942 A JPS63291942 A JP S63291942A JP 12907687 A JP12907687 A JP 12907687A JP 12907687 A JP12907687 A JP 12907687A JP S63291942 A JPS63291942 A JP S63291942A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- copolymer
- latex
- reaction
- 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
- 239000011342 resin composition Substances 0.000 title abstract description 40
- 229920005992 thermoplastic resin Polymers 0.000 title abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 43
- 229920001577 copolymer Polymers 0.000 claims abstract description 41
- 229920000126 latex Polymers 0.000 claims abstract description 38
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 25
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 22
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims abstract description 20
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 aromatic vinyl compound Chemical class 0.000 claims abstract description 16
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 12
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims abstract description 11
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 10
- 239000008121 dextrose Substances 0.000 claims abstract description 10
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 10
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 10
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 10
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims abstract description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 5
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims abstract description 4
- 229940048086 sodium pyrophosphate Drugs 0.000 claims abstract description 4
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims abstract description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 52
- 239000000178 monomer Substances 0.000 claims description 51
- 239000004816 latex Substances 0.000 claims description 35
- 238000006116 polymerization reaction Methods 0.000 claims description 28
- 239000012190 activator Substances 0.000 claims description 18
- 239000003995 emulsifying agent Substances 0.000 claims description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 13
- 239000012986 chain transfer agent Substances 0.000 claims description 6
- 239000012966 redox initiator Substances 0.000 claims description 6
- 229920002959 polymer blend Polymers 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 57
- 239000011347 resin Substances 0.000 abstract description 57
- 230000000704 physical effect Effects 0.000 abstract description 16
- 238000002156 mixing Methods 0.000 abstract description 6
- 150000001993 dienes Chemical class 0.000 abstract description 3
- 229920001971 elastomer Polymers 0.000 description 23
- 238000000034 method Methods 0.000 description 20
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 3
- 239000008116 calcium stearate Substances 0.000 description 3
- 235000013539 calcium stearate Nutrition 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000002932 luster Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 2
- 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 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920006258 high performance thermoplastic Polymers 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
皇呈上少剋■立！
本発明は熱可塑性樹脂組成物に間し、詳しくは、高いゲ
ル含量を有するエチレン・プロピレン・非共役ジエン共
重合体ゴムを高含量にて含有して、特に、耐衝撃性、耐
熱性及び表面光沢にすぐれる成形物を与える熱可塑性樹
脂組成物に関する。[Detailed Description of the Invention] The Emperor's Presentation of the Emperor! The present invention relates to a thermoplastic resin composition, in particular, a thermoplastic resin composition containing a high content of ethylene/propylene/non-conjugated diene copolymer rubber having a high gel content, which particularly improves impact resistance, heat resistance and surface properties. The present invention relates to a thermoplastic resin composition that provides molded products with excellent gloss.
獲米Ω且歪
エチレン・プロピレン・非共役ジエン共重合体ゴムにス
チレンとアクリロニトリルとを共重合させて得られるグ
ラフト共重合体や、このグラフト共重合体に更にリジッ
ド成分と称されているスチレンとアクリロニトリル等と
の共重合体を混合してなるゴム強化樹脂組成物は、従来
、ＡＢＳ樹脂として知られている。このような樹脂は、
ポリスチレンやスチレン・アクリロニトリル共重合体に
比べて耐衝撃性が改善され、また、ＡＢＳ樹脂に比べて
耐候性が改善されているものの、耐熱性及び表面光沢に
ついては、未だ十分ではない。Graft copolymers obtained by copolymerizing strained ethylene propylene non-conjugated diene copolymer rubber with styrene and acrylonitrile, and styrene, which is called a rigid component, are added to this graft copolymer. A rubber-reinforced resin composition formed by mixing a copolymer with acrylonitrile or the like is conventionally known as an ABS resin. Such resin is
Although it has improved impact resistance compared to polystyrene and styrene/acrylonitrile copolymer, and improved weather resistance compared to ABS resin, its heat resistance and surface gloss are still insufficient.
従来、このようなＡＢＳ樹脂を得るためには、エチレン
・プロピレン・非共役ジエン共重合体ゴムに懸濁重合、
溶液重合又は塊状重合によってスチレンやアクリロニト
リル等をグラフト共重合させる方法が知られているが、
重合時の反応系の安定性、得られるＡＢＳ樹脂の物性や
、更には、経済性の点から、現在では、溶液重合法によ
るグラフト共重合が主流を占めている。しかしながら、
溶液重合法によるときは、その重合形態からエチレン・
プロピレン・非共役ジエン共重合体ゴムを高含量にて含
有する物性バランスのすぐれた共重合体を得ることは困
難である。Conventionally, in order to obtain such ABS resin, suspension polymerization of ethylene/propylene/non-conjugated diene copolymer rubber,
A method of graft copolymerizing styrene, acrylonitrile, etc. by solution polymerization or bulk polymerization is known, but
Graft copolymerization by solution polymerization is currently the mainstream method in view of the stability of the reaction system during polymerization, the physical properties of the resulting ABS resin, and economic efficiency. however,
When using the solution polymerization method, ethylene and
It is difficult to obtain a copolymer containing a high content of propylene/nonconjugated diene copolymer rubber and having an excellent balance of physical properties.
そこで、乳化重合によるＡＢＳ樹脂の製造も、例えば、
特公昭４９−１４５４９号公報に記載されているように
、種々提案されているが、従来、知られている乳化重合
法によっても、高いゲル含量を有するエチレン・プロピ
レン・非共役ジエン共重合体ゴムを高含量にて含有する
ＡＢＳ樹脂を安定して、且つ、再現性よく製造すること
は困難である。Therefore, the production of ABS resin by emulsion polymerization, for example,
As described in Japanese Patent Publication No. 49-14549, although various proposals have been made, ethylene/propylene/non-conjugated diene copolymer rubber having a high gel content has been produced by the conventionally known emulsion polymerization method. It is difficult to stably and reproducibly produce an ABS resin containing a high content of .
他方、特開昭６１−２３８８４４号公報には、ゲル含量
が４０〜９５重量％であるエチレン・プロピレン・非共
役ジエン共重合体ゴムに芳香族ビニル化合物及びシアン
化ビニル単量体を乳化グラフト共重合させることによっ
て、耐衝撃性、耐候性及び表面光沢等にすぐれる熱可塑
性グラフト共重合体を得ることができることが記載され
ている。On the other hand, JP-A No. 61-238844 discloses a method in which an aromatic vinyl compound and a vinyl cyanide monomer are co-emulsified and grafted onto an ethylene/propylene/non-conjugated diene copolymer rubber having a gel content of 40 to 95% by weight. It is described that a thermoplastic graft copolymer having excellent impact resistance, weather resistance, surface gloss, etc. can be obtained by polymerization.
しかし、この方法によるときも、樹脂の耐熱性を向上さ
せることを目的としてα−メチルスチレンを用いるとき
、単量体の転化率が高くないうえに、重合安定性が必ず
しも十分ではなく、更に、得られるＡＢＳ樹脂は耐衝撃
性においても、十分でない。However, even when using this method, when α-methylstyrene is used for the purpose of improving the heat resistance of the resin, the monomer conversion rate is not high and the polymerization stability is not necessarily sufficient. The resulting ABS resin also has insufficient impact resistance.
更に、ＡＢＳ樹脂の物性を改善するために、例えば、特
開昭５７−７０１４８号公報や特開昭５９−１８４２４
３号公報等に記載されているように、ゴム状重合体への
グラフト共重合体と、芳香族ビニル化合物、アクリロニ
トリル、Ｎ−フェニルマレイミド等からなる共重合体と
してのリジッド成分とを混合してなる熱可塑性樹脂組成
物も種々提案されている。しかし、いずれも、耐衝撃性
において、尚満足できるものではなく、従って、諸物性
がバランスのとれた高性能の樹脂組成物を得ることがで
きない。Furthermore, in order to improve the physical properties of ABS resin, for example, JP-A-57-70148 and JP-A-59-18424 have been proposed.
As described in Publication No. 3, etc., a graft copolymer to a rubber-like polymer and a rigid component as a copolymer consisting of an aromatic vinyl compound, acrylonitrile, N-phenylmaleimide, etc. are mixed. Various thermoplastic resin compositions have also been proposed. However, none of these methods is still satisfactory in terms of impact resistance, and therefore it is not possible to obtain a high-performance resin composition with well-balanced physical properties.
日が ゛ しようとする４ 声
本発明者らは、上記したような従来のＡＢＳ樹脂とリジ
ッド成分とからなる熱可塑性樹脂組成物における問題を
解決するために鋭意研究した結果、高０ゲル含量を有す
るエチレン・プロピレン・非共役ジエン共重合体ゴムに
所定のレドックス開始剤を用いて、所定量の芳香族ビニ
ル化合物及びシアン化ビニル単量体を連鎖移動剤の不存
在下に高温下に乳化グラフト共重合させることによって
、高転化率にて、且つ、安定してＡＢＳ樹脂を得ること
ができ、更に、このＡＢＳ樹脂を所定の芳香族ビニル化
合物とシアン化ビニル単量体とＮ−フェニルマレイミド
との共重合体からなるリジッド成分と混合して、熱可塑
性樹脂組成物とするとき、この樹脂組成物が特に耐衝撃
性、耐熱性及び表面光沢にすぐれる成形物を与えること
を見出して、本発明に至ったものである。As a result of intensive research in order to solve the above-mentioned problems with conventional thermoplastic resin compositions made of ABS resin and rigid components, the present inventors have found that they have a high zero gel content. A predetermined amount of an aromatic vinyl compound and a vinyl cyanide monomer are emulsified and grafted onto the ethylene/propylene/nonconjugated diene copolymer rubber at high temperature in the absence of a chain transfer agent using a predetermined redox initiator. By copolymerizing, ABS resin can be obtained stably at a high conversion rate, and furthermore, this ABS resin can be copolymerized with a predetermined aromatic vinyl compound, vinyl cyanide monomer, and N-phenylmaleimide. The present inventors have discovered that when mixed with a rigid component consisting of a copolymer of This led to the invention.
を ゛ るための
本発明による熱可塑性樹脂組成物は、
” （ａ） ゲル含量が４０〜９５重量％であるエチ
レン・プロピレン・非共役ジエン共重合体ゴムラテツク
ス４０〜８０重量部に、芳香族ビニル化合物６０〜７６
重量％とシアン化ビニル化合物４０〜２４重量％とから
なるビニル単量体混合物６０〜２０重量部を合計量１０
０重量部となるようにして、クメンハイドロパーオキサ
イド、硫酸第一鉄、ビロリン酸ナトリウム及びデキスト
ローズからなるレドックス開始剤の存在下に連鎖移動剤
の不存在下に７０〜９５℃の温度にて反応させ、且つ、
その際、硫酸第一鉄、ビロリン酸ナトリウム及びデキス
トローズからなる重合活性剤をその全量に対する量比に
て０．３〜０．８を反応開始時に上記ラテックスに一括
して加えると共に、反応開始時から少なくとも１時間の
添加時間にわたって上記ビニル単量体混合物及びクメン
ハイドロパーオキサイドの全量を連続的に上記ラテック
スに加え、且つ、上記重合活性剤の残部及び乳化剤を上
記ビニル単量体混合物及びクメンハイド６バーオキサイ
ドの添加時間よりも３０分以上長い時間にわたって連続
的に上記ラテックスに加えることによって得られるグラ
フト共重合体１０〜６０重量部、及山） 上記グラフト
共重合体との合計量が１００重量部となるように、α−
メチルスチレン３０〜５５重量％、スチレン０〜２０重
量％、アクリロニトリル１０〜３５重量％及びＮ−フェ
ニルマレイミド１〜２５重量％からなる単量体組成を有
する共重合体４０〜９０重量部
とからなることを特徴とする。The thermoplastic resin composition according to the present invention for the purpose of Compounds 60-76
A total amount of 10 to 20 parts by weight of a vinyl monomer mixture consisting of 40 to 24 weight % of a vinyl cyanide compound
0 parts by weight in the presence of a redox initiator consisting of cumene hydroperoxide, ferrous sulfate, sodium birophosphate and dextrose at a temperature of 70-95°C in the absence of a chain transfer agent. react, and
At that time, a polymerization activator consisting of ferrous sulfate, sodium birophosphate, and dextrose is added at once to the latex at a ratio of 0.3 to 0.8 to the total amount, and at the same time, at the start of the reaction, The entire amount of the vinyl monomer mixture and cumene hydroperoxide is continuously added to the latex over an addition time of at least 1 hour, and the remainder of the polymerization activator and emulsifier are added to the vinyl monomer mixture and cumene hydroperoxide 6 10 to 60 parts by weight of the graft copolymer obtained by continuously adding it to the latex over a period of at least 30 minutes longer than the addition time of peroxide; So that α−
40-90 parts by weight of a copolymer having a monomer composition of 30-55% by weight of methylstyrene, 0-20% by weight of styrene, 10-35% by weight of acrylonitrile and 1-25% by weight of N-phenylmaleimide. It is characterized by
本発明において用いるゲルを含むエチレン・プロピレン
・非共役ジエン共重合体ゴムは、例えば、前記した特開
昭６１−２３８８４４号公報に記載されているように、
既に知られている。しかしながら、本発明においては、
かかるエチレン・プロピレン・非共役ジエン共重合体ゴ
ムは、トルエンに対して不溶性のゴム分として規定され
るゲル含量が４０〜９５重量％であることを必要とし、
特に、５０〜８０重量％の範囲のゲル含量を有すること
が好ましい、ゲル含量が４０重量％よりも少ないときは
、得られるＡＥＳ樹脂をリジッド成分と混合して熱可塑
性樹脂組成物としたとき、目的とする高い耐衝撃性とす
ぐれた成形外観を得ることができず、他方、ゲル含量が
９５重量％よりも多いときは、得られる樹脂組成物が耐
衝撃性において著しく劣ることとなるからである。The ethylene/propylene/non-conjugated diene copolymer rubber containing the gel used in the present invention is, for example, as described in JP-A-61-238844,
Already known. However, in the present invention,
Such ethylene propylene non-conjugated diene copolymer rubber needs to have a gel content of 40 to 95% by weight, defined as the rubber content insoluble in toluene,
In particular, it is preferable to have a gel content in the range of 50 to 80% by weight, and when the gel content is less than 40% by weight, when the resulting AES resin is mixed with a rigid component to form a thermoplastic resin composition, The desired high impact resistance and excellent molded appearance cannot be obtained, and on the other hand, if the gel content is more than 95% by weight, the resulting resin composition will be significantly inferior in impact resistance. be.
更に、上記エチレン・プロピレン・非共役ジエン共重合
体ゴムは、エチレンとプロピレンの重量比が８５：１５
〜３０ニア０の範囲にあることが好ましく、また、非共
役ジエン成分は、好ましくは１，４−へキサジエン、５
−エチリデン−２−ノルボルネン、５−ビニルノルボル
ネン、ジシクロペンタジェン等である。Furthermore, the ethylene/propylene/non-conjugated diene copolymer rubber has a weight ratio of ethylene and propylene of 85:15.
The non-conjugated diene component is preferably in the range of 1,4-hexadiene, 5
-ethylidene-2-norbornene, 5-vinylnorbornene, dicyclopentadiene, etc.
本発明においてエチレン・プロピレン・非共役ジエン共
重合体ゴムにグラフト共重合させるビニル単量体は、芳
香族ビニル化合物とシアン化ビニル化合物との混合物か
らなり、上記芳香族ビニル化合物としては、例えば、ス
チレンやα−メチルスチレンが好ましく用いられる、ま
た、シアン化ビニル単量体としてはアクリロニトリルや
メタクリロニトリルが好ましく用いられる。上記単量体
混合物において、芳香族ビニル化合物は６０〜７６重量
％の範囲にあり、シアン化ビニル化合物は４０〜２４重
量％の範囲にあることが必要である。In the present invention, the vinyl monomer to be graft copolymerized to the ethylene/propylene/nonconjugated diene copolymer rubber is a mixture of an aromatic vinyl compound and a vinyl cyanide compound, and examples of the aromatic vinyl compound include: Styrene and α-methylstyrene are preferably used, and as the vinyl cyanide monomer, acrylonitrile and methacrylonitrile are preferably used. In the above monomer mixture, it is necessary that the aromatic vinyl compound is in the range of 60 to 76% by weight, and the cyanide vinyl compound is in the range of 40 to 24% by weight.
単量体混合物において、芳香族ビニル化合物が６０重量
％よりも少ないときは、得られる樹脂組成物が熱安定性
において著しく劣り、他方、７６重量％を越えるときは
、得られる樹脂組成物が耐熱性及び耐衝撃性において劣
るからである。In the monomer mixture, if the aromatic vinyl compound is less than 60% by weight, the resulting resin composition will be significantly inferior in heat stability, while if it exceeds 76% by weight, the resulting resin composition will have poor heat resistance. This is because they are inferior in strength and impact resistance.
本発明によれば、前記ゲルを含むエチレン・プロピレン
・非共役ジエン共重合体ゴム４０〜８０重量部に合計量
が１００重量部となるように上記単量体混合物６０〜２
０重量部をグラフト共重合させる。このグラフト共重合
反応において、上記共重合体ゴムが４０重量部よりも少
ないときは、得られる樹脂組成物が耐衝撃性及び耐熱性
において劣り、一方、８０重量部よりも多いときは、樹
脂組成物が耐衝撃性に劣ることとなるからである。According to the present invention, 60 to 2 parts by weight of the monomer mixture is added to 40 to 80 parts by weight of the ethylene/propylene/non-conjugated diene copolymer rubber containing the gel so that the total amount is 100 parts by weight.
Graft copolymerize 0 parts by weight. In this graft copolymerization reaction, when the copolymer rubber is less than 40 parts by weight, the resulting resin composition is inferior in impact resistance and heat resistance, while when it is more than 80 parts by weight, the resin composition This is because the object will have poor impact resistance.
本発明においては、重合開始剤として、特に、クメンハ
イドロパーオキサイド、硫酸第一鉄、ビロリン酸ナトリ
ウム及びデキストローズからなるレドックス開始剤が用
いられる。In the present invention, as the polymerization initiator, in particular, a redox initiator consisting of cumene hydroperoxide, ferrous sulfate, sodium birophosphate and dextrose is used.
本発明の方法によれば、このように特定されたレドック
ス開始剤を用いると共に、後述するように、重合反応に
おいて、硫酸第一鉄、ビロリン酸ナトリウム及びデキス
トローズからなる重合活性剤；クメンハイドロパーオキ
サイド、ビニル単量体混合物及び乳化剤の添加量や、ラ
テックスへの添加時期、添加時間等を本発明に従って調
整し、更に、所定の反応温度にて、連鎖移動剤の不存在
下に反応させることによって、乳化剤の使用量を従来の
約１／３程度に低減して、単量体の転化率を高く、且つ
、重合安定性を格段に高めて、目的とするすぐれた性質
を有するＡＥＳ樹脂を得ることができるのである。According to the method of the present invention, in addition to using the redox initiator specified in this way, as described below, in the polymerization reaction, a polymerization activator consisting of ferrous sulfate, sodium birophosphate, and dextrose; The amount of the oxide, vinyl monomer mixture, and emulsifier, the timing of addition to the latex, the addition time, etc. are adjusted according to the present invention, and the reaction is further carried out at a predetermined reaction temperature in the absence of a chain transfer agent. By reducing the amount of emulsifier used to about 1/3 of the conventional amount, increasing the conversion rate of monomers and significantly increasing polymerization stability, we have been able to produce AES resins with the desired excellent properties. You can get it.
例えば、本発明にて規定する以外のレドックス開始剤を
用いるときは、通常、単量体の転化率が低いか、若しく
はラテックスの安定性が悪く、反応系が反応途中で固結
し、又は得られる樹脂組成物が耐衝撃性や成形外観に劣
る。For example, when using a redox initiator other than those specified in the present invention, the monomer conversion rate is usually low or the latex stability is poor, resulting in the reaction system solidifying during the reaction, or The resulting resin composition has poor impact resistance and molded appearance.
本発明においては、硫酸第一鉄、ビロリン酸ナトリウム
及びデキストローズからなる重合活性剤は、その全量に
対する量比にて０．３〜０．８が反応開始時に一括して
ラテックスに加えられると共に、反応開始時から少なく
とも１時間の添加時間にわたって、ビニル単量体混合物
とクメンハイドロパーオキサイドの全量が連続的にラテ
ックスに加えられる。更に、前記重合活性剤の残部と乳
化剤の全量は、上記ビニル単量体混合物とクメンハイド
ロパーオキサイドの添加時間よりも３０分以上長い時間
にわたって、反応開始時からラテックスに連続的に加え
られる。In the present invention, a polymerization activator consisting of ferrous sulfate, sodium birophosphate, and dextrose is added to the latex in a quantity ratio of 0.3 to 0.8 to the total amount at the start of the reaction, and The entire amount of vinyl monomer mixture and cumene hydroperoxide is continuously added to the latex over an addition period of at least 1 hour from the start of the reaction. Further, the remainder of the polymerization activator and the entire amount of the emulsifier are continuously added to the latex from the start of the reaction over a period of 30 minutes or more longer than the addition time of the vinyl monomer mixture and cumene hydroperoxide.
例えば、重合活性剤の全量と乳化剤とをラテックスへの
ビニル単量体混合物の添加の前に一括して加えるときは
、重合反応時におけるラテックスの安定性が悪く、凝固
物の析出量が多くなるうえに、単量体の転化率が低い、
その他の条件を同じとして、乳化剤の使用量を増やせば
、ラテックスの安定性は改善され、また、単量体の転化
率も高まるが、得られる樹脂が衝撃強度において劣る。For example, when adding the entire amount of polymerization activator and emulsifier to the latex at once before adding the vinyl monomer mixture, the stability of the latex during the polymerization reaction is poor and the amount of precipitated coagulum increases. Moreover, the monomer conversion rate is low.
If the amount of emulsifier used is increased, other conditions being the same, the stability of the latex is improved and the monomer conversion rate is also increased, but the resulting resin is inferior in impact strength.
他方、重合活性剤と乳化剤の全量を連続的にラテックス
に加えるときは、反応に誘導期が現われ、また、得られ
る樹脂が物性に劣ることとなる。On the other hand, when the entire amount of the polymerization activator and emulsifier is added continuously to the latex, an induction period appears in the reaction and the resulting resin has poor physical properties.
更に、重合活性剤の全量を反応開始時に一括してラテッ
クスに加え、乳化剤を連続的に加える方法によるときは
、ラテックスの安定性は改善されるものの、単量体の転
化率が低い、また、重合活性剤、乳化剤及び水の添加時
間が単量体の添加時間よりも短いときは、単量体転化率
が低い。Furthermore, when the entire amount of the polymerization activator is added to the latex at once at the start of the reaction and the emulsifier is added continuously, although the stability of the latex is improved, the monomer conversion rate is low. When the addition time of the polymerization activator, emulsifier, and water is shorter than the monomer addition time, the monomer conversion rate is low.
更に、本発明の方法によれば、ｔ−ドデシルメルカプタ
ンのような連鎖移動剤の不存在下にエチレン・プロピレ
ン・非共役ジエン共重合体ゴムに前記単量体混合物をグ
ラフト共重合させることが必要である。Furthermore, according to the method of the present invention, it is necessary to graft-copolymerize the monomer mixture onto the ethylene-propylene-nonconjugated diene copolymer rubber in the absence of a chain transfer agent such as t-dodecylmercaptan. It is.
また、本発明の方法において、反応温度は７０〜９５℃
であり、特に、重合反応中、ラテックスが高い安定性を
有し、更には、得られる樹脂組成物にすぐれた耐衝撃性
を付与することができる観点から、反応温度は８０〜９
０℃の範囲が好ましい。Furthermore, in the method of the present invention, the reaction temperature is 70 to 95°C.
In particular, from the viewpoint that the latex has high stability during the polymerization reaction and can further impart excellent impact resistance to the resulting resin composition, the reaction temperature is 80 to 9.
A range of 0°C is preferred.
特に、本発明の方法においては、前記単量体混合物は、
反応開始時から、好ましくは１〜３時間にわたって連続
的に加え、７０〜９０℃、好ましくは８０〜９０℃の温
度で反応させることが望ましい。In particular, in the method of the invention, the monomer mixture is
It is desirable to add continuously from the start of the reaction, preferably for 1 to 3 hours, and to react at a temperature of 70 to 90°C, preferably 80 to 90°C.
本発明による熱可塑性樹脂組成物は、以上のようにして
得られるＡＥＳ樹脂に所定の組成を有する単量体の共重
合体としてのリジッド成分を混合することによって得る
ことができる。The thermoplastic resin composition according to the present invention can be obtained by mixing a rigid component as a copolymer of monomers having a predetermined composition with the AES resin obtained as described above.
即ち、本発明による熱可塑性樹脂組成物は、上記ＡＥＳ
樹脂１０〜６０重量部と、α−メチルスチレン３０〜５
５重量％、ステレフ０〜２０重量％、アクリロニトリル
１０〜３５重量％及びＮ−フェニルマレイミド１〜２５
重量％からなる単量体組成を有する共重合体４０〜９０
重量部とからなり、合計量にて１００重量部を構成する
。That is, the thermoplastic resin composition according to the present invention has the above-mentioned AES
10 to 60 parts by weight of resin and 30 to 5 parts by weight of α-methylstyrene
5% by weight, 0-20% by weight of Stereph, 10-35% by weight of acrylonitrile and 1-25% by weight of N-phenylmaleimide.
Copolymer having a monomer composition consisting of 40 to 90% by weight
The total amount constitutes 100 parts by weight.
樹脂組成物１００重量部において、ＡＥＳ樹脂が１０！
１１部よりも少ないときは、樹脂組成物は耐衝撃性に劣
り、他方、６０重量部を越えるときは、耐熱性に劣る。In 100 parts by weight of the resin composition, the AES resin is 10!
When the amount is less than 11 parts, the resin composition has poor impact resistance, while when it exceeds 60 parts by weight, the resin composition has poor heat resistance.
更に、リジッド共重合体の単量体成分において、α−メ
チルスチレンが３０重量％よりも少ないか、或いはスチ
レンが２０重量％よりも多いときは、耐熱性が低下し、
他方、アクリロニトリルが３５％を越えるときは、樹脂
の着色が著しくなる。また、Ｎ−フェニルマレイミドが
１重量％よりも少ないときは、樹脂組成物が耐熱性にお
いて十分でなく、他方、２５重量％よりも多いときは、
得られる樹脂組成物が耐衝撃性において劣ると共に、樹
脂着色も顕著となるので好ましくない。Furthermore, when the monomer component of the rigid copolymer contains less than 30% by weight of α-methylstyrene or more than 20% by weight of styrene, the heat resistance decreases,
On the other hand, when the acrylonitrile content exceeds 35%, the resin becomes significantly colored. Furthermore, when N-phenylmaleimide is less than 1% by weight, the resin composition does not have sufficient heat resistance, while when it is more than 25% by weight,
This is not preferable because the resulting resin composition has poor impact resistance and is also noticeably colored.
上記リジッド成分は、従来より知られているように、乳
化重合、懸濁重合、溶液重合、塊状重合等、通常の方法
によって得ることができる。また、このリジッド成分の
製造においては、分子量調整剤としての連鎖移動剤、例
えば、ｔ−ドデシルメルカプタンやα−メチルスチレン
ダイマー等を適宜量用いることによって、所要の分子量
を有するものを得ることができる。前記ＡＥＳ樹脂とこ
のようなリジッド成分とを必要に応じて酸化防止剤、滑
剤、加工助剤、顔料、充填剤等と共に混合し、例えば、
押出機、バンバリー・ミキサー、混練ロール等にて混練
し、ペレット化することによって、熱可塑性樹脂組成物
を得ることができる。The above-mentioned rigid component can be obtained by conventional methods such as emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization, as is conventionally known. In addition, in the production of this rigid component, a product having the required molecular weight can be obtained by using an appropriate amount of a chain transfer agent as a molecular weight regulator, such as t-dodecyl mercaptan or α-methylstyrene dimer. . The AES resin and such a rigid component are mixed together with an antioxidant, a lubricant, a processing aid, a pigment, a filler, etc. as necessary, and, for example,
A thermoplastic resin composition can be obtained by kneading with an extruder, Banbury mixer, kneading roll, etc. and pelletizing.
光ユ旦塾来
以上のように、本発明による熱可塑性樹脂組成物は、Ａ
ＥＳ樹脂として、高ゲル含量を有するエチレン・プロピ
レン・非共役ジエン共重合体ゴムへの所定量の芳香族ビ
ニル化合物及びシアン化ビニル単量体からなる単量体混
合物のグラフト共重合体を用いると共に、かかるＡＥＳ
樹脂に所定の組成を有するリジッド成分を混合してなる
ので、特に、耐衝撃性、耐熱性及び表面光沢にすぐれ、
諸物性のバランスのよい高性能の熱可塑性樹脂成形物を
与える。As described above, the thermoplastic resin composition according to the present invention has A
As the ES resin, a graft copolymer of a monomer mixture consisting of a predetermined amount of an aromatic vinyl compound and a vinyl cyanide monomer to an ethylene/propylene/non-conjugated diene copolymer rubber having a high gel content is used. , such AES
Since it is made by mixing resin with a rigid component having a predetermined composition, it has particularly excellent impact resistance, heat resistance, and surface gloss.
Provides a high-performance thermoplastic resin molded product with well-balanced physical properties.
従って、本発明によるグラフト共重合体を含む樹脂組成
物は、例えば、自動車部品、建材等の分野における成形
材料として好適に用いることができる。Therefore, the resin composition containing the graft copolymer according to the present invention can be suitably used as a molding material in the fields of automobile parts, building materials, etc., for example.
叉１■
以下に実施例を挙げて本発明を説明するが、本発明はこ
れら実施例により何ら限定されるものでハナい、尚、以
下において、エチレン・プロピレン・非共役ジエン共重
合体ゴムのゲル含量は、共重合体ゴムラテックスを希硫
酸にて凝固させ、水洗乾燥した後、これを１ｇ採取し、
２００ｍ１のトルエン中に４０時間浸漬し、次いで、２
００メツシユのステンレス金網にて濾過し、残渣を乾燥
することによって求めたものである。1. The present invention will be explained below with reference to Examples, but the present invention is not limited by these Examples in any way. To determine the gel content, copolymer rubber latex was coagulated with dilute sulfuric acid, washed with water and dried, and then 1 g of this was collected.
Soaked in 200 ml of toluene for 40 hours, then 2
It was obtained by filtering through a 00 mesh stainless wire mesh and drying the residue.
実施例１
攪拌機を備えた反応容器に第１表に示すように、蒸留水
、非共役ジエン成分が５−エチリデン−２−ノルボルネ
ンであり、ゲル含量が７２重量％であるエチレン・プロ
ピレン・非共役ジエン共重合体ゴム（平均粒子径０．５
μｍ）、水酸化ナトリウム、ピロリン酸ナトリウム、硫
酸第一鉄、及びデキストローズを仕込み（この仕込みを
組成Ａという、）、８０℃に昇温した。Example 1 In a reaction vessel equipped with a stirrer, as shown in Table 1, distilled water, ethylene propylene non-conjugated with a non-conjugated diene component of 5-ethylidene-2-norbornene and a gel content of 72% by weight were prepared. Diene copolymer rubber (average particle size 0.5
μm), sodium hydroxide, sodium pyrophosphate, ferrous sulfate, and dextrose (this charge is referred to as composition A), and the temperature was raised to 80°C.
別に、それぞれ第１表に示す所定量のアクリロニトリル
、スチレン及びクメンハイドロパーオキサイドからなる
混合物を調製しくこの混合物を組成りという。）、また
、これと共に、それぞれ第１表に示す所定量の硫酸第一
鉄、ビロリン酸ナトリウム、デキストローズ、オレイン
酸ナトリウム及び水からなる混合物を調製しくこの混合
物を組成Ｃという、）、これらを上記反応容器にそれぞ
れ１５０分及び１８０分間にわたって連続的に加え、こ
の後、８０℃で更に６０分間反応させた。Separately, a mixture consisting of acrylonitrile, styrene and cumene hydroperoxide in predetermined amounts shown in Table 1 was prepared, and this mixture was referred to as the composition. ), together with this, prepare a mixture consisting of ferrous sulfate, sodium birophosphate, dextrose, sodium oleate, and water in the prescribed amounts shown in Table 1. This mixture is referred to as composition C). They were added continuously to the above reaction vessels for 150 minutes and 180 minutes, respectively, and then reacted at 80° C. for an additional 60 minutes.
得られたラテックスを凝固させ、洗浄、乾燥して、第１
表に示すように、本発明によるグラフト共重合体及び比
較例としてのグラフト共重合体、即ち、ＡＥＳ樹脂１−
１から１−８を得た。このグラフト共重合反応における
ビニル単量体混合物の転化率と、反応終了時の凝固物の
析出量にてラテックスの安定性とを併せて第１表に示す
。The obtained latex is coagulated, washed and dried, and the first
As shown in the table, the graft copolymer according to the present invention and the graft copolymer as a comparative example, namely AES resin 1-
1 to 1-8 were obtained. Table 1 shows the conversion rate of the vinyl monomer mixture in this graft copolymerization reaction and the stability of the latex in terms of the amount of coagulated material precipitated at the end of the reaction.
別に、攪拌機を備えたオートクレーブ内を十分に窒素置
換した後、第２表に示すように、それぞれ所定量の単量
体、蒸留水、界面活性剤、有機過酸化物等を仕込み、３
５０ｒｐｍの割合で攪拌しつつ、内温を８０℃まで昇温
し、この温度で９時間重合させた。次いで、２．５時間
を要して内湯を１２０℃まで昇温し、この温度で２時間
反応させた。Separately, after thoroughly purging the inside of an autoclave equipped with a stirrer with nitrogen, predetermined amounts of monomers, distilled water, surfactants, organic peroxides, etc. were charged, as shown in Table 2.
While stirring at a rate of 50 rpm, the internal temperature was raised to 80° C., and polymerization was carried out at this temperature for 9 hours. Next, the temperature of the indoor bath was raised to 120° C. over 2.5 hours, and the reaction was carried out at this temperature for 2 hours.
得られたスラリーを洗浄し、乾燥して、リジッド成分と
しての共重合体２−１から２−４を得た。The obtained slurry was washed and dried to obtain copolymers 2-1 to 2-4 as rigid components.
反応温度を７５℃、反応時間を６時間とした以外は、上
記と同じ方法にて重合させ、得られたラテックスを凝固
させ、洗浄、乾燥して、リジッド成分としての共重合体
２−２を得た。Polymerization was carried out in the same manner as above, except that the reaction temperature was 75°C and the reaction time was 6 hours, and the obtained latex was coagulated, washed, and dried to obtain copolymer 2-2 as a rigid component. Obtained.
次に、第３表に示すように、得られる樹脂組成物におけ
るエチレン・プロピレン・非共役ジエン共重合体ゴム量
が一定（２４，５重量％）となるように、上記リジッド
成分のうちの２−１を前記ＡＥＳ樹脂、ステアリン酸カ
ルシウム０．５重量部、及びＮ、 Ｎ’−エチレンビス
ステアリルアミド１．５重量部と共に粉末混合し、バン
バリー・ミキサーにて混練した後、ベレット化した。こ
のベレットをシリンダ一温度２６０℃の２オンス射出成
形機にて成形し、樹脂成形物３−１から３−８を得た。Next, as shown in Table 3, two of the rigid components were adjusted so that the amount of ethylene/propylene/nonconjugated diene copolymer rubber in the resulting resin composition was constant (24.5% by weight). -1 was powder-mixed with the AES resin, 0.5 parts by weight of calcium stearate, and 1.5 parts by weight of N,N'-ethylenebisstearylamide, kneaded in a Banbury mixer, and pelletized. This pellet was molded using a 2-ounce injection molding machine with a cylinder temperature of 260° C. to obtain resin molded products 3-1 to 3-8.
これらについての物性の測定結果を第３表に示す。本発
明の方法によるＡＥＳ樹脂を含む樹脂組成物からの成形
物がアイゾツト衝撃値、熱変形温度及び成形外観に特に
すぐれることが明らかである。Table 3 shows the measurement results of the physical properties of these. It is clear that molded articles made from resin compositions containing AES resins according to the method of the present invention are particularly excellent in Izot impact value, heat distortion temperature and molded appearance.
実施例２
実施例１において得た前記ＡＥＳ樹脂１１−６と前記リ
ジッド成分２−１から２−４とを第４表に示す割合にて
混合して、樹脂組成物を得、これをベレット化し、射出
成形して、前記樹脂成形＠！Ｊ３−６．３−９から３−
１１を得た。Example 2 The AES resin 11-6 obtained in Example 1 and the rigid components 2-1 to 2-4 were mixed in the proportions shown in Table 4 to obtain a resin composition, which was made into pellets. , injection molding and said resin molding@! J3-6.3-9 to 3-
I got 11.
これらについての物性の測定結果を第４表に示す０本発
明の方法によるＡＥＳ樹脂を含む樹脂組成物が熱変形温
度にすぐれ、耐衝撃性と耐熱性のバランスにすぐれるこ
とが理解される。The measurement results of the physical properties of these are shown in Table 4. It is understood that the resin composition containing the AES resin prepared by the method of the present invention has an excellent heat distortion temperature and an excellent balance between impact resistance and heat resistance.
実施例３
先ず、比較のために、第５表に示す組成Ａ、 Ｂ及びＣ
を用いて、重合活性剤と乳化剤を反応開始時に一括して
ラテックスに加える方法、重合活性剤と乳化剤を反応開
始時から連続的にラテックスに加える方法、又は重合活
性剤と乳化剤をビニル単量体混合物の連続添加時間より
も短い時間内に加える方法によって、比較例としてのＡ
ＥＳ樹脂１〜９から１〜１４を得た。Example 3 First, for comparison, compositions A, B, and C shown in Table 5 were used.
Adding the polymerization activator and emulsifier to the latex all at once at the start of the reaction, adding the polymerization activator and emulsifier to the latex continuously from the start of the reaction using By adding the mixture within a shorter time than the continuous addition time, A as a comparative example
ES resins 1-14 were obtained from ES resins 1-9.
次に、実施例１と同様にして、第６表に示すように、こ
れらＡＥＳ樹脂を前記リジッド成分２−１、ステアリン
酸カルシウム０．５重量部、及びＮ、Ｎ”−エチレンビ
スステアリルアミド１．５重量部と共に粉末混合して、
樹脂組成物を得、これをバンバリー・ミキサーにて混練
した後、ベレット化した。このペレットをシリンダ一温
度２６０℃の２オンス射出成形機にて成形して、樹脂成
形物３−１２から３−１７についての物性を測定した。Next, in the same manner as in Example 1, as shown in Table 6, these AES resins were mixed with the rigid component 2-1, 0.5 parts by weight of calcium stearate, and 1.5 parts by weight of N,N''-ethylenebisstearylamide. Mix the powder with 5 parts by weight,
A resin composition was obtained, which was kneaded in a Banbury mixer and then formed into pellets. This pellet was molded using a 2-ounce injection molding machine with a cylinder temperature of 260° C., and the physical properties of resin molded products 3-12 to 3-17 were measured.
結果を第６表に示す。The results are shown in Table 6.
第５表と第６表に示すように、ＡＥＳ樹脂１−９及び１
−１０によれば、重合活性剤と乳化剤の全量をビニル単
量体混合物のラテックスへの添加の前に一括して加えた
ので、ラテックスの安定性が悪く、凝固物の析出量が多
く、また、最終的な単量体の転化率も低い。乳化剤の添
加量を増した以外は、上記と同じ条件にて重合を行なう
ときは、ＡＥＳ樹脂１−１１にみられるように、ラテッ
クスの安定性は改善され、また、単量体の転化率も上昇
するものの、得られる樹脂の衝撃強度が低い。As shown in Tables 5 and 6, AES resins 1-9 and 1
According to No. 10, since the entire amount of polymerization activator and emulsifier was added all at once before adding the vinyl monomer mixture to the latex, the stability of the latex was poor and the amount of coagulum precipitated was large. , the final monomer conversion is also low. When polymerization is carried out under the same conditions as above except that the amount of emulsifier added is increased, the stability of the latex is improved and the monomer conversion rate is also improved, as seen in AES resin 1-11. Although it increases, the impact strength of the resulting resin is low.
更に、ＡＥＳ樹脂１−１２にみられるように、重合活性
剤と乳化剤の全量を連続的にラテックスに加えると、ラ
テックスの安定性と単量体転化率は改善されるが、反応
に誘導期が現われることとなり、また、得られる樹脂の
物性も低下する。重合活性剤の全量を一括して仕込み、
乳化剤のみを連続的に添加するときは、ＡＥＳ樹脂１−
１３にみられるように、ラテックスの安定性は改善され
るが、単量体転化率が低い。重合活性剤及び乳化剤を単
量体の連続添加時間よりも短い時間内に添加するときは
、ＡＥＳ樹脂１−１４にみられるように、単量体転化率
が低下する。Furthermore, as seen in AES Resin 1-12, when the entire amount of polymerization activator and emulsifier is added continuously to the latex, the stability of the latex and monomer conversion are improved, but there is an induction period in the reaction. In addition, the physical properties of the resin obtained also deteriorate. Charge the entire amount of polymerization activator at once,
When adding only the emulsifier continuously, AES resin 1-
As seen in No. 13, the stability of the latex is improved, but the monomer conversion is low. When the polymerization activator and emulsifier are added within a time shorter than the continuous addition time of monomers, the monomer conversion rate decreases as seen in AES resin 1-14.
次に、実施例１と同様にして、第７表に示す組成Ａ、Ｂ
及びＣを用いて、エチレン・プロピレン・非共役ジエン
共重合体ゴムにおけるゲル含量が種々異なる本発明によ
るＡＥＳ樹脂及び比較例としてのＡＥＳ樹脂１−６及び
１−１５から１−２０を調製した。Next, in the same manner as in Example 1, compositions A and B shown in Table 7 were prepared.
and C were used to prepare AES resins according to the present invention and AES resins 1-6 and 1-15 to 1-20 as comparative examples having various gel contents in ethylene-propylene-nonconjugated diene copolymer rubber.
次に、第８表に示すように、実施例工と同様にして、こ
れらＡＥＳ樹脂を前記リジッド成分２−１１ステアリン
酸カルシウム０．５重量部、及びＮ、 Ｎ’−エチレン
ビスステアリルアミド１．５重量部と共に粉末混合して
、樹脂組成物を得、これをバンバリー・ミキサーにて混
練した後、ベレット化した。このペレットをシリンダ一
温度２６０℃の２オンス射出成形機にて成形して、樹脂
成形物３−６と共に、３−１８から３−２３についての
物性を測定した。結果を第８表に示す。Next, as shown in Table 8, these AES resins were mixed with 0.5 parts by weight of the rigid component 2-11 calcium stearate and 1.5 parts by weight of N,N'-ethylenebisstearylamide in the same manner as in the examples. A resin composition was obtained by powder mixing together with parts by weight, which was kneaded in a Banbury mixer and then formed into pellets. This pellet was molded using a 2-ounce injection molding machine with a cylinder temperature of 260° C., and the physical properties of resin molded products 3-6 and 3-18 to 3-23 were measured. The results are shown in Table 8.
本発明の方法によるＡＥＳ樹脂を含む樹脂組成物からの
樹脂成形物がアイゾツト衝撃値、光沢及び成形外観に特
にすぐれることが明らかである。It is clear that resin moldings made from resin compositions containing AES resins according to the method of the invention have particularly good Izot impact values, gloss and molded appearance.
実施例４
第９表に示すように、組成Ａ、Ｂ及びＣにおいて、重合
開始剤を種々に変え、第９表に示す反応温度にてエチレ
ン・プロピレン・非共役ジエン共重合体ゴムにアクリロ
ニトリルとスチレンとを乳化グラフト共重合させて、比
較例によるＡＥＳ樹脂１−２１から１−２５を得た。こ
の反応におけるラテックスの安定性及び単量体の転化率
を本発明による前記ＡＥＳ樹脂１−６における結果と共
に第９表に示す。Example 4 As shown in Table 9, in compositions A, B, and C, various polymerization initiators were used, and acrylonitrile and acrylonitrile were added to ethylene-propylene-nonconjugated diene copolymer rubber at the reaction temperatures shown in Table 9. AES resins 1-21 to 1-25 according to comparative examples were obtained by emulsion graft copolymerization with styrene. The stability of the latex and the monomer conversion rate in this reaction are shown in Table 9 together with the results for the AES resin 1-6 according to the present invention.
本発明の方法によれば、ラテックスの安定性を保持して
、単量体を高転化率にてエチレン・プロピレン・非共役
ジエン共重合体ゴムにグラフト共重合させることができ
る。According to the method of the present invention, it is possible to graft copolymerize a monomer into an ethylene/propylene/nonconjugated diene copolymer rubber at a high conversion rate while maintaining the stability of the latex.
次に、第１０表に示すように、上記ＡＥＳ樹脂と前記リ
ジッド成分２−１とを所定の割合にて混合して、樹脂組
成物とし、これをペレット化し、射出成形して、樹脂成
形物３−６と共に、３−２４からから３−２６を得た。Next, as shown in Table 10, the above AES resin and the above rigid component 2-1 are mixed at a predetermined ratio to obtain a resin composition, which is pelletized and injection molded to form a resin molded product. Along with 3-6, 3-26 was obtained from 3-24.
これらの樹脂成形物についての物性の測定結果を第１０
表に示す。The measurement results of the physical properties of these resin molded products are shown in the 10th section.
Shown in the table.
本発明の方法によるＡＥＳ樹脂を含む樹脂組成物が耐衝
撃性、耐熱性及び外観にすぐれ、バランスのよい成形物
を与えることが理解される。It is understood that the resin composition containing the AES resin produced by the method of the present invention provides a well-balanced molded product with excellent impact resistance, heat resistance, and appearance.
実施例５
第１１表に示す組成ＡＳＢ及びＣを用い、反応温度を種
々に変えて、第１１表に示すように、本発明及び比較例
によるＡＥＳ樹脂１−６．１−２６から１−２９を得た
。この反゛応におけるラテックスの安定性及び単量体の
転化率を第１１表に示す。Example 5 Using the compositions ASB and C shown in Table 11 and varying the reaction temperature, AES resins 1-6.1-26 to 1-29 according to the present invention and comparative examples were prepared as shown in Table 11. I got it. Table 11 shows the stability of the latex and the monomer conversion rate in this reaction.
本発明の方法によれば、ラテックスの安定性を保持して
、単量体を高転化率にてエチレン・プロピレン・非共役
ジエン共重合体ゴムにグラフト共重合させることができ
る。According to the method of the present invention, it is possible to graft copolymerize a monomer into an ethylene/propylene/nonconjugated diene copolymer rubber at a high conversion rate while maintaining the stability of the latex.
次に、このようにして得られたＡＥＳ樹脂を第１２表に
示すように前記リジッド成分２−１と所定割合にて混合
し、ペレット化し、射出成形して、樹脂成形物３−６．
３−２７からから３−３０を得た。これらについての物
性の測定結果を第１２表に示す。Next, the AES resin thus obtained is mixed with the rigid component 2-1 at a predetermined ratio as shown in Table 12, pelletized, and injection molded to form a resin molded product 3-6.
3-30 was obtained from 3-27. Table 12 shows the measurement results of the physical properties of these.
本発明の方法によるＡＥＳ樹脂を含む樹脂組成物が耐衝
撃性に特にすぐれるのみならず、耐熱性や成形外観にお
いてもすぐれ、かくして、バランスのよい成形物を与え
ることが理解される。It is understood that the resin composition containing the AES resin produced by the method of the present invention not only has particularly excellent impact resistance, but also has excellent heat resistance and molded appearance, thus providing a well-balanced molded product.
実施例６
第１３表に示す組成Ａ、Ｂ及びＣを用い、反応温度を８
０℃として、単量体混合物を反応開始に際して一括して
加えるか、又は連続して加える時間を種々に変えて、第
１３表に示すように、本発明及び比較例によるＡＥＳ樹
脂１−６．１−３０から１−３６を得た。この反応にお
けるラテックスの安定性及び単量体の転化率を第１３表
に示す。Example 6 Using compositions A, B and C shown in Table 13, the reaction temperature was 8.
AES resins 1-6 according to the present invention and comparative examples were prepared by adding the monomer mixture all at once at the start of the reaction at 0°C, or by varying the time of continuous addition as shown in Table 13. 1-36 was obtained from 1-30. Table 13 shows the latex stability and monomer conversion in this reaction.
本発明の方法によれば、ラテックスの安定性を保持して
、単量体を高転化率にてエチレン・プロピレン・非共役
ジエン共重合体ゴムにグラフト共重合させることができ
る。According to the method of the present invention, it is possible to graft copolymerize a monomer into an ethylene/propylene/nonconjugated diene copolymer rubber at a high conversion rate while maintaining the stability of the latex.
次に、このようにして得られたＡＥＳ樹脂を第１４表に
示すように前記リジッド成分２−１と所定割合にて混合
し、ペレット化し、射出成形して、樹脂成形物３−６．
３−３１からから３−３７を得た。これら樹脂成形物に
ついての物性の測定結果を第１４表に示す。Next, the AES resin thus obtained is mixed with the rigid component 2-1 at a predetermined ratio as shown in Table 14, pelletized, and injection molded to form a resin molded product 3-6.
3-37 was obtained from 3-31. Table 14 shows the measurement results of the physical properties of these resin molded products.
本発明の方法によるＡＥＳ樹脂を含む樹脂組成物が耐衝
撃性に特にすぐれるのみならず、耐熱性、外観、光沢等
においてもすぐれ、か゛くして、バランスのよい成形物
を与えることが理解される。It is understood that the resin composition containing the AES resin produced by the method of the present invention not only has particularly excellent impact resistance, but also has excellent heat resistance, appearance, gloss, etc., and thus provides well-balanced molded products. .
実施例７
前記樹脂成形物３−４から３−６についての耐候性の試
験結果を第１５表に示す。Example 7 Table 15 shows the weather resistance test results for the resin molded products 3-4 to 3-6.
比較のための成形物３−３８として、ブタジエン成分を
２０重量％含有する汎用ＡＢＳ樹脂についての結果も、
第１５表に示す。As molded article 3-38 for comparison, the results for general-purpose ABS resin containing 20% by weight of butadiene component were also shown.
It is shown in Table 15.
これらの結果から明らかなように、本発明によるＡＢＳ
樹脂を含む樹脂組成物は、比較例による樹脂成形物に比
べて、耐候性が格段にすぐれることが明らかである。As is clear from these results, the ABS according to the present invention
It is clear that the resin composition containing the resin has much better weather resistance than the resin molded product according to the comparative example.
尚、以上の実施例において、樹脂成形物の物性の測定方
法は以下による。In addition, in the above examples, the method of measuring the physical properties of the resin molded product is as follows.
ノツチ付きアイゾツト衝撃値 ＡＳＴＭ Ｄ ２５６に準じた。Notched Izot impact value According to ASTM D 256.
熱変形温度 ＡＳＴＩＩ Ｄ ６４８−５６に準じた。heat distortion temperature According to ASTII D 648-56.
引張強さ ＡＳＴＭ ０６３８に準じた。Tensile strength According to ASTM 0638.
曲げ強さ ＡＳＴＭ Ｄ ７９０に準じた。bending strength According to ASTM D790.
光沢
ＪＩＳ Ｚ ８７４１ （入射角６０°の反射率）に準
じた。Gloss According to JIS Z 8741 (reflectance at an incident angle of 60°).
成形外観の評価 次の基準にて肉眼評価した。Evaluation of molded appearance Visual evaluation was performed based on the following criteria.
○ 真珠様光沢感のむらがない。○ No uneven pearl-like luster.
Δ 真珠様光沢感のむらが幾分認められる。Δ Some unevenness of pearl-like luster is observed.
× 真珠様光沢感のむらが明瞭に認められる。× Uneven pearl-like luster is clearly observed.
流動性
２６０℃における射出成形時の最小充填圧力（ｋｇ／Ｃ
ＩＡ）にて評価した。Minimum filling pressure during injection molding at 260°C (kg/C
IA).
耐候性
試験片をウェザ−メーター（スガ試験機製サンシャイン
・スーパーロングライフ・キセノン・ウェザ−メーター
ＷＥ！Ｌ−６ＸＳ−ＨＣ）ｌ−８）を用いて、ブラック
パネル温度８３℃（降雨なし）で２００時間及び４００
時間後のアイゾツト衝撃値（ＡＳＴＭ Ｄ ２５６に準
じた。−３０℃、ノツチなし）を測定し、この衝撃値に
て評価した。The weather resistance test piece was tested using a weather meter (Suga Test Instruments Sunshine Super Long Life time and 400
After a period of time, the Izot impact value (according to ASTM D 256, -30°C, no notch) was measured, and evaluation was made based on this impact value.
Claims (1)
ン・プロピレン・非共役ジエン共重合体ゴムラテックス
４０〜８０重量部に、芳香族ビニル化合物６０〜７６重
量％とシアン化ビニル化合物４０〜２４重量％とからな
るビニル単量体混合物６０〜２０重量部を合計量１００
重量部となるようにして、クメンハイドロパーオキサイ
ド、硫酸第一鉄、ピロリン酸ナトリウム及びデキストロ
ーズからなるレドックス開始剤の存在下に連鎖移動剤の
不存在下に７０〜９５℃の温度にて反応させ、且つ、そ
の際、硫酸第一鉄、ピロリン酸ナトリウム及びデキスト
ローズからなる重合活性剤をその全量に対する量比にて
０．３〜０．８を反応開始時に上記ラテックスに一括し
て加えると共に、反応開始時から少なくとも１時間の添
加時間にわたつて上記ビニル単量体混合物及びクメンハ
イドロパーオキサイドの全量を連続的に上記ラテックス
に加え、且つ、上記重合活性剤の残部及び乳化剤を上記
ビニル単量体混合物及びクメンハイドロパーオキサイド
の添加時間よりも３０分以上長い時間にわたつて連続的
に上記ラテックスに加えることによつて得られるグラフ
ト共重合体１０〜６０重量部、及び （ｂ）上記グラフト共重合体との合計量が１００重量部
となるように、α−メチルスチレン３０〜５５重量％、
スチレン０〜２０重量％、アクリロニトリル１０〜３５
重量％及びＮ−フェニルマレイミド１〜２５重量％から
なる単量体組成を有する共重合体４０〜９０重量部 とからなることを特徴とする熱可塑性樹脂組成物。(1) (a) 40 to 80 parts by weight of ethylene/propylene/nonconjugated diene copolymer rubber latex with a gel content of 40 to 95% by weight, 60 to 76% by weight of an aromatic vinyl compound, and 40 parts by weight of a vinyl cyanide compound. 60 to 20 parts by weight of a vinyl monomer mixture consisting of ~24% by weight in a total amount of 100%
The reaction is carried out in the presence of a redox initiator consisting of cumene hydroperoxide, ferrous sulfate, sodium pyrophosphate and dextrose in the absence of a chain transfer agent at a temperature of 70 to 95° C. in the following proportions by weight: At this time, a polymerization activator consisting of ferrous sulfate, sodium pyrophosphate, and dextrose is added at once to the latex at a ratio of 0.3 to 0.8 to the total amount of the polymerization activator at the start of the reaction. , the entire amount of the vinyl monomer mixture and cumene hydroperoxide is continuously added to the latex over an addition time of at least 1 hour from the start of the reaction, and the remainder of the polymerization activator and emulsifier are added to the vinyl monomer mixture and the emulsifier. (b) 10 to 60 parts by weight of a graft copolymer obtained by continuously adding the polymer mixture to the latex over a period of 30 minutes or more longer than the addition time of the cumene hydroperoxide; and (b) the graft copolymer. 30 to 55% by weight of α-methylstyrene so that the total amount with the copolymer is 100 parts by weight,
Styrene 0-20% by weight, acrylonitrile 10-35%
% by weight and 40 to 90 parts by weight of a copolymer having a monomer composition of 1 to 25 weight % of N-phenylmaleimide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12907687A JPS63291942A (en) | 1987-05-25 | 1987-05-25 | Thermoplastic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12907687A JPS63291942A (en) | 1987-05-25 | 1987-05-25 | Thermoplastic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63291942A true JPS63291942A (en) | 1988-11-29 |
| JPH0548779B2 JPH0548779B2 (en) | 1993-07-22 |
Family
ID=15000483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12907687A Granted JPS63291942A (en) | 1987-05-25 | 1987-05-25 | Thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63291942A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5352738A (en) * | 1991-03-04 | 1994-10-04 | Ube Cycon, Ltd. | Method for production of thermoplastic resin composition and graft copolymer |
-
1987
- 1987-05-25 JP JP12907687A patent/JPS63291942A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5352738A (en) * | 1991-03-04 | 1994-10-04 | Ube Cycon, Ltd. | Method for production of thermoplastic resin composition and graft copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0548779B2 (en) | 1993-07-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5091470A (en) | Molding resin | |
| KR20140118986A (en) | A styrene-based resin blend comprising particles having a tri-layer structure and the preparation method thereof | |
| US4433102A (en) | Thermoplastic molding materials | |
| WO2003037977A2 (en) | Acrylonitrile-butadiene-styrene copolymer transparent resin having superior chemical resistance and transparency and prepartion thereof | |
| US4021509A (en) | Production of impact-resistant, thermoplastic resin compositions | |
| EP0096527B1 (en) | A process for producing a rubber-modified thermoplastic resin | |
| CA1218484A (en) | Polymer alloys having a mat surface | |
| KR101072037B1 (en) | Low-gloss thermoplastic resin composition having excellent impact resistance and heat resistance | |
| US6288167B1 (en) | Polymer blends with improved colorability | |
| KR100274658B1 (en) | A preparing method of core-shell composite particles for toughening agent of polymethyl methacrylate resin and composition containing the same | |
| EP0620236B1 (en) | Process for producing high impact polystyrene | |
| JPH02212534A (en) | Polymer mixture | |
| KR20040057408A (en) | Perparation of thermoplastic resin composition having excellent thermal stability and power properties | |
| JPS63291942A (en) | Thermoplastic resin composition | |
| KR100423873B1 (en) | A process for preparing transparent thermoplastic resin composition | |
| JPS63291943A (en) | Thermoplastic resin composition | |
| JP3541512B2 (en) | Low gloss and heat resistant resin composition with excellent flow / impact balance | |
| JPH0478645B2 (en) | ||
| JPS63132956A (en) | Impact-resistant resin composition | |
| JP2001323129A (en) | Copolymer composition and vinyl chloride resin composition containing the same | |
| KR20040094211A (en) | Thermoplastic Resin Composition with Reduced Cold Stress Whitening | |
| KR20180050064A (en) | A method for preparing thermoplastic resin | |
| JPH03124757A (en) | Thermoplastic resin composition | |
| JPH0379366B2 (en) | ||
| JPH03163163A (en) | Impact-resistant thermoplastic resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |