JPS6261234B2 - - Google Patents
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- Publication number
- JPS6261234B2 JPS6261234B2 JP14338181A JP14338181A JPS6261234B2 JP S6261234 B2 JPS6261234 B2 JP S6261234B2 JP 14338181 A JP14338181 A JP 14338181A JP 14338181 A JP14338181 A JP 14338181A JP S6261234 B2 JPS6261234 B2 JP S6261234B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- resin
- compounds
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- 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.)
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Links
- 229920006324 polyoxymethylene Polymers 0.000 claims description 18
- 239000011354 acetal resin Substances 0.000 claims description 17
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 5
- 150000008360 acrylonitriles Chemical class 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 18
- 229920000578 graft copolymer Polymers 0.000 description 10
- -1 polyethylene Polymers 0.000 description 8
- 150000001993 dienes Chemical class 0.000 description 7
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920001897 terpolymer Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 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 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- VYXHVRARDIDEHS-QGTKBVGQSA-N (1z,5z)-cycloocta-1,5-diene Chemical compound C\1C\C=C/CC\C=C/1 VYXHVRARDIDEHS-QGTKBVGQSA-N 0.000 description 1
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical class CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- XHAFIUUYXQFJEW-UHFFFAOYSA-N 1-chloroethenylbenzene Chemical compound ClC(=C)C1=CC=CC=C1 XHAFIUUYXQFJEW-UHFFFAOYSA-N 0.000 description 1
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-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
- 229920004943 Delrin® Polymers 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000012662 bulk polymerization Methods 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
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- DPUXQWOMYBMHRN-UHFFFAOYSA-N hexa-2,3-diene Chemical compound CCC=C=CC DPUXQWOMYBMHRN-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、耐候性、耐衝撃性および塗装性に優
れる熱可塑性樹脂組成物に関する。
アセタール樹脂は、機械的強度、耐熱性、寸法
安定性、および耐摩耗性に優れており、機械工業
部品、自動車部品、電気部品などに広く用いられ
ている。しかしながらアセタール樹脂は他のエン
ジニアリングプラスチツクに比較して耐候性およ
び耐衝撃性に劣り使用上種々制限を受けている。
従来よりアセタール樹脂に他の高分子材料（例
えばポリエチレン）や添加剤（例えば脂肪族アル
コール）を添加することにより機械的強度や流動
性を改善する試みは種々行われているが耐候性改
善に関しては未だ有効な方法は提案されていな
い。また、耐衝撃性もまだ不充分である。
本発明者らは、アセタール樹脂の特長を損なう
ことなくかかる欠点を解消すべく鋭意研究した結
果、アセタール樹脂とエチレン―プロピレン系ゴ
ム強化重合体からなる組成物が優れた耐衝撃性、
耐候性および塗装性を有することを見出し、本発
明に到達した。
即ち、本発明は、アセタール樹脂90〜10重量％
とエチレン―プロピレン系ゴム質共重合体と芳香
族ビニル化合物、シアン化ビニル化合物および他
の重合性単量体化合物のうち少なくとも二群より
選ばれるおのおの一種以上の化合物からなる
AES樹脂10〜90重量％とからなる耐衝撃性、耐
候性および塗装性に優れる熱可塑性樹脂を提供す
るものである。
アセタール樹脂とは、一般式〔―Ｒ・CHO
―〕oで表わされる直鎖状高分子であり、ホルムア
ルデヒドの均一体であるホモポリマーおよびエチ
レンオキサイドとの共重合体などが挙げられる。
デユポン社より“デルリン”およびポリプラスチ
ツク社より“ジユラコン”などの名称にて市販さ
れている。
アセタール樹脂の製造法等については、日刊工
業新聞社発行（昭和45年６月30日）の“ポリアセ
タール樹脂”に詳しく記載されている。
本発明におけるAES樹脂を構成するエチレン
―プロピレン系ゴム質共重合体とは、エチレンと
プロピレンからなる二元共重合体（EPR）、エチ
レン、プロピレンおよび非共役ジエンからなる三
元共重合体（EPDM）などであり、一種または二
種以上用いられる。
三元共重合体（EPDM）における非共役ジエン
としては、ジシクロペンタジエン、エチリデンノ
ルボルネン、1.4―ヘキサジエン、1.4―シクロヘ
プタジエン、1.5―シクロオクタジエン等が挙げ
られる。
二元共重合体（EPR）および三元共重合体
（EPDM）におけるエチレンとプロピレンのモル
比は５：１から１：３の範囲であることが好まし
い。
また、三元共重合体（EPDM）においては非共
役ジエンの割合がヨウ素価に換算して２〜50の範
囲のものが好ましい。
AES樹脂を構成する芳香族ビニル化合物とし
ては、スチレン、α―メチルスチレン、α―クロ
ルスチレン、ビニルトルエンなど挙げられ、特に
スチレンが好ましい。シアン化ビニル化合物とし
ては、アクリロニトリル、メタアクリロニトリル
などが挙げられ、特にアクリロニトリルが好まし
い。さらに、他の重合性単量体化合物としては、
メチル、エチル、プロピル、ブチル、ベンジル、
ヘキシルなどのアクリル酸エステル化合物および
メタアクリル酸エステル化合物などが挙げられ、
特にメタアクリル酸メチルが好ましい。
エチレン―プロピレン系ゴム質重合体の存在
下、上述の芳香族ビニル化合物、シアン化ビニル
化合物ならびに他の重合性単量体化合物のうち少
なくとも二群より選ばれるおのおの一種以上の化
合物がグラフト重合される。
重合におけるこれら化合物とゴムとの重量比は
その目的に応じて適当な範囲を選ぶことができ
る。通常、化合物95〜30重量％に対しゴム５〜70
重量％、好ましくは、化合物55〜40重量％に対し
ゴム45〜60重量％である。
AES樹脂は、エチレン―プロピレン系ゴム質
重合体に化合物がグラフトしたグラフト重合体
か、またはかかるグラフト重合体と芳香族ビニル
化合物、シアン化ビニル化合物ならびに他の重合
性単量体化合物のうち少なくとも二群より選ばれ
るおのおの一種以上の化合物からなる共重合体と
の混合物である。
グラフト重合体および共重合体は、懸濁重合
法、塊状重合法、乳化重合法、溶液重合法など公
知の方法にて作られる。
本発明の組成物は、アセタール樹脂90〜10重量
％とAES樹脂10〜90重量％からなる。アセター
ル樹脂が10重量％未満ではアセタール樹脂の特長
である耐摩耗性等が低下し、かつ塗装性に劣り好
ましくない。またアセタール樹脂が90重量％を超
えると耐衝撃性及び耐候性が改善されず好ましく
ない。
アセタール樹脂とAES樹脂との混合方法とし
ては、バンバリーミキサー、押出機等を用いた公
知の混合方法が挙げられる。
また混合時、公知の染顔料、安定剤、可塑剤、
帯電防止剤、紫外線吸収剤、滑剤、充填剤等の添
加も十分可能である。
なお、本発明の塗装性を次のように定義する。
一般にABS樹脂、AES樹脂等のゴム強化スチ
レン樹脂は、その大半が射出成形により成形され
ている。射出成形では１点又は多点の小さなゲー
ト口より溶融樹脂を流入させるため、ゲート部の
樹脂は他の箇所に比べて成形時の残留歪（配向）
が大きい。
一方、これらの製品は商品価値を高めるため塗
装される場合が多い。塗料には一般に顔料、ビー
クル、有機溶剤等が含まれており、製品に塗料が
塗装されると残留歪の大きいゲート部では有機溶
剤によるゴムの緩和が起こり表面にミクロクラツ
クが発生（一般にストレスクラツクキング（吸い
込み現象）と呼ばれ樹脂の耐溶剤性の試験に適用
されている）し、表面が艷消し状態となり著しく
外観不良となる。
この艷消し状態（吸い込み現象）の有無によ
り、本発明の組成物における塗装性を判断する。
以下に実施例を用いて本発明を具体的に説明す
るが本発明は、これらによつて何ら制限されるも
のでない。
実施例及び比較例
〈アセタール樹脂〉
ポリプラスチツク社製アセタール樹脂“ジユラ
コンＭ―90”
〈AES樹脂〉
ヨウ素価8.5、ムーニー粘度61、プロピレン含
有量43重量％、ジエン成分としてエチリデンノル
ボルネンを含むEPDM370重量部をｎ―ヘキサン
3000重量部および二塩化エチレン1500重量部に溶
解し、スチレン250重量部、アクリロニトリル130
重量部および過酸化ベンゾイル13重量部を加え、
67℃、10時間窒素雰囲気中で重合した。重合液を
大過剰のメタノールと接触させ、折出した沈殿物
を分離、乾燥後グラフト重合体（AES―１）を
得た。
ヨウ素価21、ムーニー粘度75、プロピレン含有
量50重量％、ジエン成分としてエチリデンノルボ
ルネンを含むEPDM370重量部、スチレン100重量
部、メチルメタクリレート150重量部、アクリロ
ニトリル130重量部を用いてAES―１と同様に溶
液重合し、グラフト重合体（AES―２）を得
た。
水450重量部に懸濁安定剤としてポリビニルア
ルコール0.3重量部を溶解した後、ヨウ素価15、
ムーニー粘度75、プロピレン含有量50重量％、ジ
エン成分としてジシクロペンタジエンを含む
EPDM100重量部、スチレン80重量部、アクリロ
ニトリル35重量部およびｔ―ブチルパーオキシピ
バレート３重量部を加え、26℃で１時間撹拌した
後、110℃に昇温し重合を行つた。その後、反応
物を過、乾燥しグラフト重合体（AES―３）
を得た。
ヨウ素価９、ムーニー粘度87、プロピレン含有
量50重量％、ジエン成分としてエチリデンノルボ
ルネンを含むEPDM100重量部、スチレン50重量
部、メチルメタクリレート50重量部を用いて
AES―３と同様に懸濁重合し、グラフト重合体
（AES―４）を得た。
上述のグラフト重合体（AES―３）40重量％
と別途公知の懸濁重合法で得られたスチレン―ア
クリロニトリル共重合体（スチレン含有量70重量
％）60重量％とを混練し、重合体（AES―５）
を得た。
〈ACN―EPDM重合体〉
スチレン50重量部およびメチルメタクリレート
50重量部の代わりにアクリロニトリル100重量部
を用いて、AES―４と同様に懸濁重合し、グラ
フト重合体（ACN―EPDM）を得た。
アセタール樹脂、AES樹脂およびACN―
EPDM重合体を表に示す比率にて混練（200℃、
３分間）し、熱可塑性樹脂組成物（組成物No.１〜
16）を得た。
日本製鋼製Ｎ―140型射出成形機（７オンス）
を用いて得られた組成物より各種試験片を作成し
た。
試験結果を表に示す。
The present invention relates to a thermoplastic resin composition that has excellent weather resistance, impact resistance, and paintability. Acetal resin has excellent mechanical strength, heat resistance, dimensional stability, and wear resistance, and is widely used in mechanical industrial parts, automobile parts, electrical parts, etc. However, acetal resins are inferior in weather resistance and impact resistance compared to other engineering plastics, and are subject to various limitations in use. Various attempts have been made to improve mechanical strength and fluidity by adding other polymeric materials (e.g. polyethylene) or additives (e.g. aliphatic alcohol) to acetal resin, but improvements in weather resistance have not been achieved. No effective method has been proposed yet. Furthermore, impact resistance is still insufficient. The inventors of the present invention have conducted extensive research to eliminate these drawbacks without sacrificing the features of acetal resin, and have found that a composition consisting of acetal resin and an ethylene-propylene rubber-reinforced polymer has excellent impact resistance,
It was discovered that it has weather resistance and paintability, and the present invention was achieved. That is, in the present invention, the acetal resin is 90 to 10% by weight.
and an ethylene-propylene rubbery copolymer, and one or more compounds each selected from at least two groups of aromatic vinyl compounds, vinyl cyanide compounds, and other polymerizable monomer compounds.
The present invention provides a thermoplastic resin containing 10 to 90% by weight of AES resin and having excellent impact resistance, weather resistance, and paintability. Acetal resin has the general formula [-R・CHO
-] It is a linear polymer represented by o , and includes homopolymers, which are homogeneous formaldehyde, and copolymers with ethylene oxide.
It is commercially available under the names of "Delrin" from DuPont and "Dyuracon" from Polyplastics. The manufacturing method of acetal resin is described in detail in "Polyacetal Resin" published by Nikkan Kogyo Shimbun (June 30, 1971). The ethylene-propylene rubbery copolymer constituting the AES resin in the present invention is a binary copolymer of ethylene and propylene (EPR), a terpolymer of ethylene, propylene, and a non-conjugated diene (EPDM), ), and one or more types may be used. Examples of the non-conjugated diene in the terpolymer (EPDM) include dicyclopentadiene, ethylidenenorbornene, 1.4-hexadiene, 1.4-cycloheptadiene, 1.5-cyclooctadiene, and the like. The molar ratio of ethylene to propylene in the binary copolymer (EPR) and terpolymer (EPDM) is preferably in the range of 5:1 to 1:3. Further, in the terpolymer (EPDM), it is preferable that the proportion of non-conjugated diene is in the range of 2 to 50 in terms of iodine value. Examples of the aromatic vinyl compound constituting the AES resin include styrene, α-methylstyrene, α-chlorostyrene, and vinyltoluene, with styrene being particularly preferred. Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile, with acrylonitrile being particularly preferred. Furthermore, other polymerizable monomer compounds include:
Methyl, ethyl, propyl, butyl, benzyl,
Examples include acrylic ester compounds and methacrylic ester compounds such as hexyl,
Particularly preferred is methyl methacrylate. In the presence of the ethylene-propylene rubbery polymer, one or more compounds selected from at least two groups of the above-mentioned aromatic vinyl compounds, vinyl cyanide compounds, and other polymerizable monomer compounds are graft-polymerized. . The weight ratio of these compounds and rubber in polymerization can be selected within an appropriate range depending on the purpose. Usually 5 to 70% rubber to 95 to 30% by weight of compound.
% by weight, preferably 45-60% by weight of rubber to 55-40% by weight of compound. AES resin is a graft polymer in which a compound is grafted onto an ethylene-propylene rubbery polymer, or such a graft polymer is combined with at least two of an aromatic vinyl compound, a vinyl cyanide compound, and other polymerizable monomer compounds. It is a mixture with a copolymer consisting of one or more compounds each selected from the group. Graft polymers and copolymers are produced by known methods such as suspension polymerization, bulk polymerization, emulsion polymerization, and solution polymerization. The composition of the invention consists of 90-10% by weight of acetal resin and 10-90% by weight of AES resin. If the acetal resin is less than 10% by weight, the abrasion resistance, which is a feature of the acetal resin, will decrease, and the paintability will be poor, which is not preferable. Moreover, if the acetal resin exceeds 90% by weight, impact resistance and weather resistance will not be improved, which is not preferable. Examples of the method for mixing the acetal resin and AES resin include known mixing methods using a Banbury mixer, an extruder, and the like. Also, when mixing, known dyes and pigments, stabilizers, plasticizers,
It is also possible to add antistatic agents, ultraviolet absorbers, lubricants, fillers, etc. Note that the paintability of the present invention is defined as follows. In general, most rubber-reinforced styrene resins such as ABS resin and AES resin are molded by injection molding. In injection molding, molten resin is introduced through small gate openings at one or multiple points, so the resin at the gate part has more residual strain (orientation) during molding than other parts.
is large. On the other hand, these products are often painted to increase their commercial value. Paints generally contain pigments, vehicles, organic solvents, etc. When paint is applied to a product, the organic solvent relaxes the rubber at the gate area where residual strain is large, causing microcracks on the surface (generally known as stress cracks). (This phenomenon is called "king (sucking phenomenon)" and is applied to test the solvent resistance of resins), and the surface becomes faded, resulting in a significantly poor appearance. The paintability of the composition of the present invention is determined by the presence or absence of this faded state (sucking phenomenon). The present invention will be specifically explained below using Examples, but the present invention is not limited thereto. Examples and Comparative Examples <Acetal resin> Acetal resin "Dyuracon M-90" manufactured by Polyplastics <AES resin> Iodine number 8.5, Mooney viscosity 61, propylene content 43% by weight, EPDM 370 parts by weight containing ethylidene norbornene as the diene component n-hexane
Dissolved in 3000 parts by weight and 1500 parts by weight of ethylene dichloride, 250 parts by weight of styrene, 130 parts by weight of acrylonitrile.
parts by weight and 13 parts by weight of benzoyl peroxide,
Polymerization was carried out at 67°C for 10 hours in a nitrogen atmosphere. The polymerization solution was brought into contact with a large excess of methanol, and the precipitate precipitated was separated and dried to obtain a graft polymer (AES-1). Same as AES-1 using iodine number 21, Mooney viscosity 75, propylene content 50% by weight, 370 parts by weight of EPDM containing ethylidene norbornene as the diene component, 100 parts by weight of styrene, 150 parts by weight of methyl methacrylate, and 130 parts by weight of acrylonitrile. Solution polymerization was performed to obtain a graft polymer (AES-2). After dissolving 0.3 parts by weight of polyvinyl alcohol as a suspension stabilizer in 450 parts by weight of water, the iodine value was 15.
Mooney viscosity 75, propylene content 50% by weight, contains dicyclopentadiene as diene component
100 parts by weight of EPDM, 80 parts by weight of styrene, 35 parts by weight of acrylonitrile and 3 parts by weight of t-butyl peroxypivalate were added, and after stirring at 26°C for 1 hour, the temperature was raised to 110°C to carry out polymerization. After that, the reaction product was filtered and dried to form a graft polymer (AES-3).
I got it. Using iodine number 9, Mooney viscosity 87, propylene content 50% by weight, 100 parts by weight of EPDM containing ethylidene norbornene as the diene component, 50 parts by weight of styrene, and 50 parts by weight of methyl methacrylate.
Suspension polymerization was carried out in the same manner as AES-3 to obtain a graft polymer (AES-4). 40% by weight of the above graft polymer (AES-3)
and 60% by weight of a styrene-acrylonitrile copolymer (styrene content: 70% by weight) separately obtained by a known suspension polymerization method to form a polymer (AES-5).
I got it. <ACN-EPDM polymer> 50 parts by weight of styrene and methyl methacrylate
Suspension polymerization was carried out in the same manner as AES-4 using 100 parts by weight of acrylonitrile instead of 50 parts by weight to obtain a graft polymer (ACN-EPDM). Acetal resin, AES resin and ACN—
Knead EPDM polymer at the ratio shown in the table (200℃,
3 minutes), and the thermoplastic resin composition (Composition No. 1 ~
16). Nippon Steel N-140 type injection molding machine (7oz)
Various test pieces were prepared from the compositions obtained using the method. The test results are shown in the table.
【表】
―塗装性―
射出成形試験片（70mm×120mm×３mm）にウレ
タン系塗料“プラネツトPA”※とシンナー
“＃210”※（フオードカツプによる粘度9.5秒）
を用いてスプレー塗布し、ゲート部における吸い
込みの有無を観察する。
※ オリジン電気社製。[Table] - Paintability - Injection molded test piece (70mm x 120mm x 3mm) urethane paint "Planet PA"* and thinner "#210"* (viscosity 9.5 seconds by food cup)
Spray the product using a spray paint and observe the presence or absence of suction at the gate. * Manufactured by Origin Electric.
Claims (1)
プロピレン系ゴム質共重合体と芳香族ビニル化合
物、シアン化ビニル化合物および他の重合性単量
体化合物のうち少なくとも二群より選ばれるおの
おの一種以上の化合物からなるAES樹脂10〜90
重量％とからなることを特徴とする熱可塑性樹脂
組成物。1 90-10% by weight of acetal resin and ethylene
AES resin 10-90 consisting of a propylene-based rubbery copolymer and one or more compounds each selected from at least two groups of aromatic vinyl compounds, vinyl cyanide compounds, and other polymerizable monomer compounds
% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14338181A JPS5845252A (en) | 1981-09-10 | 1981-09-10 | Thermoplastic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14338181A JPS5845252A (en) | 1981-09-10 | 1981-09-10 | Thermoplastic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5845252A JPS5845252A (en) | 1983-03-16 |
| JPS6261234B2 true JPS6261234B2 (en) | 1987-12-21 |
Family
ID=15337448
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14338181A Granted JPS5845252A (en) | 1981-09-10 | 1981-09-10 | Thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5845252A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0124879B1 (en) * | 1983-05-10 | 1992-02-26 | Mitsui Petrochemical Industries, Ltd. | Acetal resin composition |
| AU630241B2 (en) * | 1989-10-12 | 1992-10-22 | E.I. Du Pont De Nemours And Company | Polyoxymethylene/thermoplastic polyurethane/amorphous thermoplastic polymer blends |
| CN113061305A (en) * | 2020-01-02 | 2021-07-02 | 合肥杰事杰新材料股份有限公司 | High-performance resin special for automobile exterior trim and preparation method thereof |
-
1981
- 1981-09-10 JP JP14338181A patent/JPS5845252A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5845252A (en) | 1983-03-16 |
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