JP5010205B2 - ポリカーボネート系樹脂組成物及び薄肉成形品の耐屈曲性の改善方法 - Google Patents
ポリカーボネート系樹脂組成物及び薄肉成形品の耐屈曲性の改善方法 Download PDFInfo
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- JP5010205B2 JP5010205B2 JP2006213355A JP2006213355A JP5010205B2 JP 5010205 B2 JP5010205 B2 JP 5010205B2 JP 2006213355 A JP2006213355 A JP 2006213355A JP 2006213355 A JP2006213355 A JP 2006213355A JP 5010205 B2 JP5010205 B2 JP 5010205B2
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Images
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- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明のポリカーボネート系樹脂組成物は、ポリカーボネート系樹脂(A)と、ジエン系ゴム成分に少なくともスチレン系単量体がグラフトしたゴム含有スチレン系樹脂(B)と、酸変性オレフィン化合物(C)と、炭素繊維(D)とで構成されており、薄肉成形品を形成するための樹脂組成物である。このような樹脂組成物は、薄肉成形しても、得られる薄肉成形品の耐屈曲性を改善可能である。
前記樹脂組成物を構成するポリカーボネート系樹脂(A)としては、芳香族ポリカーボネート系樹脂、例えば、二価フェノール類とカーボネート前駆体[例えば、カルボニルハライド(ホスゲンなど)、カルボニルエステル(ジフェニルカーボネートなど)またはハロホルメート(2価フェノールのジハロホルメートなど)など]とを慣用の方法(界面重縮合法、エステル交換法など)で反応させることにより得ることができるポリカーボネートなどが挙げられる。
本発明におけるゴム含有スチレン系樹脂(B)としては、ジエン系ゴム成分に少なくともスチレン系単量体がグラフト重合したスチレン系グラフト樹脂(ジエン系ゴム−グラフトスチレン系樹脂又はジエン系ゴム強化スチレン系樹脂)を用いる。
酸変性オレフィン化合物(C)としては、酸変性オレフィン系ワックス[例えば、ポリエチレン、ポリプロピレンワックスなどのポリオレフィン系ワックスを、不飽和ポリカルボン酸又はその酸無水物(マレイン酸、無水マレイン酸など)などで処理した変性オレフィンワックス;前記ポリオレフィン系ワックスの構成モノマー(エチレン、プロピレンなどのα−オレフィンなど)と、共重合成分としての不飽和カルボン酸又は酸無水物((メタ)アクリル酸、マレイン酸、無水マレイン酸など)などとの共重合により形成される変性オレフィンワックスなど]の他、酸変性オレフィン系樹脂などが使用できる。これらの変性オレフィン化合物は、単独で又は二種以上組み合わせて使用できる。また、前記変性オレフィン系ワックスと、変性オレフィン系樹脂とを併用してもよい。これらの変性オレフィン化合物のうち、熱可塑性樹脂組成物を効率よく改質して、強度(耐衝撃性、ウェルド強度など)、耐屈曲性を向上できる点から、少なくとも酸変性オレフィン系樹脂を用いるのが好ましい。
炭素繊維(D)としては、慣用の炭素繊維、例えば、ピッチ系炭素繊維、フェノール樹脂系炭素繊維、再生セルロース系炭素繊維(例えば、レーヨン系炭素繊維、ポリノジック系炭素繊維など)、セルロース系炭素繊維、ポリアクリロニトリル系炭素繊維、ポリビニルアルコール系炭素繊維などが挙げられる。炭素繊維は単独で又は二種以上組み合わせて使用できる。これらの炭素繊維のうち、ピッチ系炭素繊維などが好ましい。
前記樹脂組成物において、ポリカーボネート系樹脂(A)とゴム含有スチレン系樹脂(B)との割合(重量比)は、例えば、(A)/(B)=80/20〜97/3、好ましくは83/17〜96/4、さらに好ましくは85/15〜95/5程度である。
前記樹脂組成物は、さらに難燃剤(E)を含有してもよい。このような難燃剤としては、ハロゲン系難燃剤を使用してもよいが、通常、非ハロゲン系難燃剤、例えば、有機酸金属塩系難燃剤(パーフルオロアルカンスルホン酸金属塩、トリハロベンゼンスルホン酸金属塩、ジフェニルスルホン−ジスルホン酸金属塩、ジフェニルスルホンスルホン酸金属塩などの有機カルボン酸又は有機スルホン酸のアルカリ金属(Na、Kなど)塩、アルカリ土類金属塩など)、リン系難燃剤、シリコーン系難燃剤、ホスファゼン系難燃剤、金属酸化物(酸化アンチモンなど)など]などが使用できる。これらの難燃剤は単独で又は二種以上組み合わせて使用できる。これらの難燃剤のうち、リン系難燃剤が好ましい。リン系難燃剤は、他の難燃剤と組み合わせて用いてもよい。
本発明の成形体は、前記ポリカーボネート系樹脂組成物で形成されており、厚みの薄い薄肉部を有する薄肉成形体である。成形体は、慣用の方法、例えば、射出成形、押出成形、ブロー成形、プレス成形、真空成形などにより前記ポリカーボネート系樹脂組成物を成形することにより得られる。
実施例及び比較例で得られた試験片から、ゲート方向に対して平行に幅4cmの板を切り出して、試験片を作製した。
表1及び表2に示す割合で各成分をV型ブレンダーで混合した後、スクリュー径30mmのベント式二軸押出機[日鋼(株) 二軸押出機TEX30α]によりシリンダー温度260℃で混練、ペレット化した。得られたペレットを射出成形機[住友重機工業(株) SH100]によりシリンダー温度250℃、金型温度60℃で射出成形し、縦12cm、横12cm、厚み1mmの試験片を作製した。試験片は、各試験に応じて、適宜、切り出して用いた。
(ii)ABS:ABS樹脂(三菱A&L(株)製、AT05)
MBS:MBS樹脂(呉羽化学工業(株)製、パラロイドEXL2602)。
C−2:無水マレイン酸共重合ポリエチレンワックス(三菱化学(株)製、ダイヤカルナ30B、Mw20,000、Mn6,600)
C−3:無水マレイン酸変性ポリプロピレン(イーストマンケミカルズ社製、エポレンE43、Mw9,100、Mn3,900)
C−4:無水マレイン酸グラフト化ポリプロピレン(アトフィナ社製、CA100、Mw78,000、Mn25,000)
C−5:無水マレイン酸共重合ポリエチレンワックス(三菱化学(株)製、ダイヤカルナ30、Mw9,000、Mn3,800)。
(v)難燃剤:有機リン系難燃剤(アデカ(株)製、アデカスタブFP−500)
(vi)難燃助剤:ポリテトラフルオロエチレン(三井デュポンフルオロケミカル(株)製、CD141)
(vii)熱安定剤:チバスペシャルティーケミカルズ(株)製、SU168
(viii)タルク:林化成(株)製、5000S。
2…試験片の長さ方向における中央部
3…円柱状治具
Claims (11)
- ポリカーボネート系樹脂(A)と、ジエン系ゴム成分に少なくともスチレン系単量体がグラフトしたゴム含有スチレン系樹脂(B)と、酸変性オレフィン化合物(C)と、炭素繊維(D)とで構成され、かつ耐屈曲性が改善された薄肉成形品を形成するためのポリカーボネート系樹脂組成物であって、
(a)ポリカーボネート系樹脂(A)とゴム含有スチレン系樹脂(B)とを、前者/後者=85/15〜95/5(重量比)の割合で含み、
(b)酸変性オレフィン化合物(C)が、重量平均分子量1.5×104〜20×104を有し、酸成分として無水マレイン酸が1〜10重量%の割合で導入された無水マレイン酸変性オレフィン系ワックス及び無水マレイン酸変性オレフィン系樹脂から選択された成分であり、
(c)酸変性オレフィン化合物(C)1重量部に対するゴム含有スチレン系樹脂(B)の割合が1〜20重量部であるポリカーボネート系樹脂組成物。 - 縦12cm、横4cm及び厚み1mmの薄肉成形品を、半径の異なる円柱に巻き付けて屈曲させたとき、前記成形品の破壊に至る円柱の半径が、1〜11.5mmである請求項1記載の樹脂組成物。
- 薄肉成形品が破壊に至るときの円柱の半径が、1.5〜10mmである請求項2記載の樹脂組成物。
- ゴム含有スチレン系樹脂(B)の割合が、前記酸変性オレフィン化合物(C)1重量部に対して2〜15重量部であり、前記炭素繊維(D)の割合が、前記酸変性オレフィン化合物(C)における酸成分量1重量部に対して20〜200重量部である請求項1記載の樹脂組成物。
- (b)前記酸変性オレフィン化合物(C)が重量平均分子量1.5×104〜17×104を有し、(c)酸変性オレフィン化合物(C)1重量部に対するゴム含有スチレン系樹脂(B)の割合が3〜10重量部であり、(d)ポリカーボネート系樹脂(A)及びゴム含有スチレン系樹脂(B)の総量100重量部に対して、酸変性オレフィン化合物(C)の割合が0.5〜5重量部であり、(e)酸変性オレフィン化合物(C)の酸成分1重量部に対するゴム含有スチレン系樹脂(B)の割合が17〜200重量部である請求項1又は4記載の樹脂組成物。
- ポリカーボネート系樹脂(A)が、粘度平均分子量1.5×104〜3×104を有する芳香族ポリカーボネート系樹脂であり、ゴム含有スチレン系樹脂(B)が、アクリロニトリル−ブタジエンゴム−スチレン樹脂及びメタクリル酸メチル−ブタジエンゴム−スチレン樹脂から選択された少なくとも一種であり、酸変性オレフィン化合物(C)が、重量平均分子量1.5×104〜17×104を有し、炭素繊維(D)が、平均繊維径0.5〜50μm及び平均繊維長5〜400mmを有する請求項1記載の樹脂組成物。
- (e)酸変性オレフィン化合物(C)の酸成分1重量部に対するゴム含有スチレン系樹脂(B)の割合が17〜100重量部であり、(d)ポリカーボネート系樹脂(A)及びゴム含有スチレン系樹脂(B)の総量100重量部に対して、酸変性オレフィン化合物(C)の割合が0.5〜5重量部であり、炭素繊維(D)の割合が5〜20重量部である請求項1記載の樹脂組成物。
- さらに、有機リン系難燃剤を含有する請求項1記載の樹脂組成物。
- 請求項1記載のポリカーボネート系樹脂組成物で形成された薄肉成形体。
- トナーカートリッジ、オフィスオートメーション機器筐体、又はコンピュータ筐体である請求項9記載の成形体。
- ポリカーボネート系樹脂(A)、ジエン系ゴム成分に少なくともスチレン系単量体がグラフトしたゴム含有スチレン系樹脂(B)、請求項1に記載の酸変性オレフィン化合物(C)及び炭素繊維(D)を混合して、請求項1に記載の樹脂組成物を製造し、この樹脂組成物で形成される薄肉成形品の耐屈曲性を改善する方法。
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