JP4159157B2 - Resin composition molded body - Google Patents

Description

（式中、Ａｒは、二価の芳香族残基であり、例えば、フェニレン、ナフチレン、ビフェニレン、ピリジレンや、下記化２で表されるものが挙げられる。）
【００１５】
【化２】

（式中、Ａｒ¹ 及びＡｒ² は、それぞれアリーレン基である。例えばフェニレン、ナフチレン、ビフェニレン、ピリジレン等の基を表し、Ｙは化３で表されるアルキレン基または置換アルキレン基である。）
【００１６】
【化３】

（式中、Ｒ¹ 、Ｒ² 、Ｒ³ 及びＲ⁴ はそれぞれ独立に水素原子、低級アルキル基、シクロアルキル基、アリール基、アラルキル基であって、場合によりハロゲン原子、アルコキシ基で置換されていてもよく、ｋは３〜１１の整数であり、Ｒ５及びＲ６ は、各Ｘについて個々に選択され、お互いに独立に水素原子、または低級アルキル基、アリール基であって、場合によりハロゲン原子、アルコキシ基で置換されていてもよく、Ｘは炭素原子を表す。）
また、下記化４で示される二価の芳香族残基を共重合体成分として含有していても良い。
【００１７】
【化４】

（式中、Ａｒ¹ 、Ａｒ² は化２と同じ。Ｚは単なる結合、または、−Ｏ−、−ＣＯ−、−Ｓ−、−ＳＯ₂ −、−ＣＯ₂ −、−ＣＯＮ（Ｒ¹ ）−（Ｒ¹ は化３と同じ）等の二価の基である。）
これら二価の芳香族残基の例としては、下記の化５及び化６で表されるもの等が挙げられる。
【００１８】
【化５】

【００１９】
【化６】

（式中、Ｒ⁷ 及びＲ⁸ は、それぞれ独立に、水素、ハロゲン、Ｃ₁ 〜Ｃ₁₀アルキル基、Ｃ₁ 〜Ｃ₁₀アルコキシ基、Ｃ₁ 〜Ｃ₁₀シクロアルキル基またはフェニル基である。ｍ及びｎは１〜４の整数で、ｍが２〜４の場合には各Ｒ⁷ はそれぞれ同一でも異なるものであってもよいし、ｎが２〜４の場合は各Ｒ⁸ はそれぞれ同一でも異なるものであっても良い。）
なかでも、下記化７で表されるものが好ましい一例である。特に、下記の化７で表されるものをＡｒとする繰り返しユニットを８５モル％以上含むものが好ましい。
【００２０】
【化７】

また、本発明に用いられるポリカーボネートは、三価以上の芳香族残基を共重合成分として含有していても良い。
【００２１】
ポリマー末端の分子構造は特に限定されないが、フェノール性水酸基、アリールカーボネート基、アルキルカーボネート基から選ばれた１種以上の末端基を結合することができる。アリールカーボネート末端基は、下記化８で表され、具体例としては、例えば、化９が挙げられる。
【００２２】
【化８】

（式中、Ａｒ³ は一価の芳香族残基であり、芳香環は置換されていても良い。）
【００２３】
【化９】

アルキルカーボネート末端基は下記化１０で表され、具体例としては、例えば下記化１１等が挙げられる。
【００２４】
【化１０】

（式中、Ｒ⁷ は炭素数１〜２０の直鎖もしくは分岐アルキル基を表す。）
【化１１】

これらの中で、フェノール性水酸基、フェニルカーボネート基、ｐ−ｔ−ブチルフェニルカーボネート基、ｐ−クミルフェニルカーボネート等が好ましく用いられる。
【００２５】
本願において、フェノール性水酸基末端と他の末端との比率は、特に限定されないが、全末端にしめるフェノール性水酸基末端比率が２０〜８０モル％の範囲あることが好ましい。
フェノール性水酸基末端量の測定方法は、一般にＮＭＲを用いて測定する方法や、チタン法や、ＵＶもしくはＩＲ法で求める方法が知られているが、本発明においては、ＮＭＲ法で求めた。
【００２６】
本発明に用いられるポリカーボネートの重量平均分子量（Ｍｗ）は、一般に重量平均分子量で５，０００〜１００，０００の範囲にあり、特に限定されない。
本発明における重量平均分子量（Ｍｗ）の測定は、ＧＰＣを用いて行い、測定条件は下記の方法によった。テトラヒドロフラン溶媒、ポリスチレンゲルを使用し、標準単分散ポリスチレンの構成曲線から下式による換算分子量較正曲線を用いて求めた。
【００２７】
Ｍ_PC＝０．３５９１Ｍ_PS ^1.0388
（Ｍ_PCはポリカーボネートの分子量、Ｍ_PSはポリスチレンの分子量）
これらポリカーボネートは、公知の方法で製造できる。具体的には、芳香族ジヒドロキシ化合物とカーボネート前駆体と反応せしめる公知の方法、例えば、芳香族ジヒドロキシ化合物とホスゲンを水酸化ナトリウム水溶液及び塩化メチレン溶媒の存在下に反応させる界面重合法（ホスゲン法）、芳香族ジヒドロキシ化合物とジフェニルカーボネートと反応させるエステル交換法（溶融法）、結晶化カーボネートプレポリマーを固相重合する方法（特開平１−１５８０３３、１−２７１４２６、３ー６８６２７号等）等の方法により製造できる。
【００２８】
本発明の（ｂ−１）ビニル化合物共重合体の構成成分である、アルキル（メタ）アクリレート単量体としては、メチルメタクリレート、メチルアクリレート、ブチルアクリレート、エチルアクリレート等が挙げられ、好ましくは、ブチルアクリレートである。芳香族ビニル単量体としては、スチレン、α−メチルスチレン、パラメチルスチレン等が挙げられ、好ましくはスチレンである。シアン化ビニル単量体としては、アクリロニトリル、メタアクリロニトリル等が挙げられる、好ましくは、アクリロニトリルである。
本発明の（ｂ−１）ビニル化合物共重合体中に占める、アルキル（メタ）アクリレート単量体成分の割合が、０．５〜８０重量％である必要があり、好ましくは、０．５〜６０重量％、さらに好ましくは、１〜４０重量％である。０．５重量％未満の場合は、高流動性が得られず、さらに耐衝撃強度の改善効果も小さい。また、８０重量％を越える場合は、耐熱性が著しく低下する。
【００２９】
本発明のゴム状重合体（Ｃ）としては、ポリブタジエン、ポリイソプレン、ポリクロロプレン、ブタジエン−スチレン共重合体、ブタジエン−アクリロニトリル共重合体などの共役ジエン系ゴム、エチレン−プロピレンゴム、アクリル酸エチル、アクリル酸ブチルなどのアクリル系ゴム、シリコーン系ゴム、シリコン−アクリルゴム等のゴム状重合体、及び、上記ゴム状重合体の粒子に更にスチレンや上記ビニル単量体が単独もしくは２種以上のでグラフト重合された複合ゴム状重合体が挙げられる。また、複合ゴム状重合体には一般に、複合ゴム状重合体を製造する過程で、該ゴム状重合体にグラフトせずに重合したスチレンやビニル単量体の重合体を含んでいるが、該成分は熱可塑性樹脂として把握される。
【００３０】
本発明のゴム状重合体（ｃ−１）は、ポリオルガノシロキサンゴム成分とポリアルキル（メタ）アクリレートゴム成分とが交互に絡み合って複合一体化されている構造を有する複合ゴムに、１種以上のビニル系単量体がグラフト重合されてなる複合ゴム系グラフト共重合体、例えば、特開昭６４−７９２５７号公報に記載された方法で製造できるゴム状重合体が好ましく用いられる。
【００３１】
複合ゴム状重合体の製造方法としては、特に限定はされないが、乳化重合で製造されたラテックス状のゴム状重合体にビニル化合物をグラフト重合させる乳化グラフト重合方式、および、乳化グラフト重合と溶液重合や懸濁重合を組み合わせた、二段重合法などが例示される。これらは、連続式、バッチ式、セミバッチ式いずれも可能である。また、上記の方法であらかじめ高ゴム含量の複合ゴム状重合体をつくり、後に塊状重合、乳化重合や懸濁重合で製造したグラフト重合時に用いたビニル化合物を主成分とする熱可塑性樹脂を配合しておくことも可能である。 その場合、複合ゴム状重合体はゴム状重合体成分（Ｃ）として、熱可塑性樹脂は（Ａ）もしくは（Ｂ）成分として把握される。
【００３２】
ゴム状重合体の好ましい粒子径については、マトリックスになる熱可塑性樹脂の種類により異なるため特に限定されないが、数平均円相当直径で０．０５〜３μで、好ましくは０．０５〜１．５μ、さらに好ましくは０．０５〜１．０μである。粒子径が０．０５μｍより小さいと耐衝撃性が得られず、また３μを越えると耐衝撃性が低下し、光沢値が低下する。
【００３３】
本発明における難燃剤（Ｄ）とは、いわゆる一般の難燃剤であり、リン系化合物やハロゲン系有機化合物、シリコン系化合部の他、メラミン等の窒素含有有機化合物、水酸化マグネシウム、水酸化アルミニウム等の無機化合物、酸化アンチモン、酸化ビスマス、また、酸化亜鉛、酸化スズなどの金属酸化物、赤リン、ホスフィン、次亜リン酸、亜リン酸、メタリン酸、ピロリン酸、無水リン酸などの無機系リン化合物、カーボンファイバー、グラスファイバー、などの繊維、膨張黒鉛、シリカ、シリカ系ガラス溶融物などが用いられるが、好ましくはハロゲン系有機化合物、リン系化合物、シリコン系化合部及びこれらの併用である。
【００３４】
ハロゲン系有機化合物としては、一般のハロゲン系難燃剤および含ハロゲンリン酸エステル全般を指す。例えば、ハロゲン系有機化合物としては、ヘキサクロロペンタジエン、ヘキサブロモジフェニル、オクタブロモジフェニルオキシド、トリブロモフェノキシメタン、デカブロモジフェニル、デカブロモジフェニルオキシド、オクタブロモジフェニルオキシド、テトラブロモビスフェノールＡ、テトラブロモフタルイミド、ヘキサブロモブテン、ヘキサブロモシクロドデカン等があるが好ましくは、下記化１２の（１）の構造を有するハロゲン系有機化合物であり、特に好ましいのは下記化１３の（２）のハロゲン系有機化合物である。
【００３５】
【化１２】

【００３６】
【化１３】

一方、含ハロゲンリン酸エステルとしては、トリス・クロロエチルホスフェート、トリス・ジクロロプロピルホスフェート、トリス・β−クロロプロピルホスフェート、トリス（トリブロモフェニル）ホスフェート、トリス（ジブロモフェニル）ホスフェート、トリス（トリブロモネオペンチルホスフェート）およびこれらの縮合リン酸エステル等があるが、好ましくは、トリス（トリブロモネオペンチルホスフェート）、トリス（トリブロモフェニル）ホスフェート、トリス（ジブロモフェニル）ホスフェートである。これらのハロゲン系有機化合物は１種類でも、２種類以上組み合わせて用いることもできる。
リン系化合物としては、下記化１４で表される。
【００３７】
【化１４】

（式中、Ａｒ１、Ａｒ２、Ａｒ３、Ａｒ４は、それぞれ独立に、アルキル基、シクロアルキル基、アリール基である。これら、芳香族残基、シクロアルキル基、アリール基は、アルキル基やアルコキシ基等で置換されていてもよい。ｎは０〜５の自然数であり、単独の化合物であっても良いし、ｎの異なる化合物の混合物であってもよい。）
式中、Ｒは下記化１５、化１６より選ばれる基。
【００３８】
【化１５】

【００３９】
【化１６】

具体的には、例えば、トリメチルホスフェート、トリエチルホスフェート、トリブチルホスフェート、トリオクチルホスフェート、トリブトキシエチルホスフェート、トリフェニルホスフェート、トリクレジルホスフェート、クレジルフェニルホスフェート、オクチルジフェニルホスフェート、ジイソプロピルフェニルホスフェート、トリス（クロロエチル）ホスフェート等のリン酸エステル類や、化１６に示される縮合リン酸エステル類が挙げられる。これらの中でも、トリフェニルホスフェートおよび下記化１７に示される縮合リン酸エステル類が好ましく用いられる。
【００４０】
【化１７】

また、シリコン系難燃剤としては、例えば、ＲＳｉＯを含む化合物が挙げられ、Ｒは例えば、フェニル基、キシリル基等のアリール基、メチル基、プロピル基等のアルキル基、また、アルケニル基等がある。一般的に、ポリオルガノシロキサン類として知られている。
これらリン系難燃剤は単独または２種類以上を併用して用いることができる。
【００４１】
難燃剤の配合量は必要な難燃性のレベルに応じて決められるが、熱可塑性樹脂とゴム状重合体の合計量１００重量部に対して、０．１〜３０重量部であることが必要である。０．１重量部未満では必要な難燃効果が発揮されない。３０重量部を超えると樹脂の機械的強度を低下させる。好ましくは１〜２５重量部の範囲であり、特に好ましい範囲としては３〜２２重量部である。難燃剤としてハロゲン系化合物を用いる場合、難燃効果を高める為に難燃助剤を用いることが出来る。難燃助剤として好ましくは、元素周期律表におけるＶＡに属する元素を含む化合物で、具体的には、窒素含有化合物、リン含有化合物、酸化アンチモン、酸化ビスマス等がある。また、酸化鉄、酸化亜鉛、酸化スズなどの金属酸化物も効果的である。この中でも特に好ましくは、酸化アンチモンであり、具体的には三酸化アンチモン、五酸化アンチモンがあげられる。これらの難燃助剤は樹脂中への分散を改善する目的および／または樹脂の熱的安定性を改善する目的で表面処理を施されているものを用いてもよい。
【００４２】
難燃助剤の添加量は、０．５〜２０重量部が好ましい、０．５部未満の場合、難燃助剤の効果が十分でなく、２０重量部を越える場合、樹脂の機械的強度および加工流動性が低下する。より好ましくは１〜１５重量部で、特に好ましくは１〜１０重量部である。
本発明の成形体を形成するための樹脂組成物を製造する方法は、従来から公知の方法で行うことが出来、特に限定されない。例えば、各成分をヘンシェルミキサー、スーパーミキサー、ターンブルミキサー、リボンブレンダー等で均一に混合した後、単軸押出機や二軸押出機、バンバリーミキサー等で溶融混練する方法等がある。また、その際、本発明の趣旨を妨げない範囲で、公知の酸化防止剤、紫外線吸収剤、滑剤、離型剤、帯電防止剤、着色剤、フィラー等の添加剤を加えることは任意である。
【００４３】
さらに、これらの樹脂組成物から本発明の成形体を製造する方法は、押し出し成形、圧縮成型、射出成形、ガスアシスト成形等があり、特に限定されない。しかしながら、本発明の特定比率で分配したモルフォロジーを有する成形体を得るためには、樹脂組成物の成形体を成形するにあたって、該樹脂組成物の溶融状態での保持条件が、１００００Ｐａ・ｓ以下の溶融粘度で静的に保持されている時間が２分以内にあること、及び冷却固化の条件が冷却開始直後の溶融状態から３００００Ｐａ・ｓの溶融粘度になるまでの時間が２０秒以内となる条件下で成形されることが必要である。上記冷却開始直後の溶融状態からとは、例えば、射出成形においては金型キャビティーへの樹脂の充填が９５％以上終了した時点を言う。また、３００００Ｐａ・ｓになる時間の認定は、例えば、レオメーター等で、樹脂温度と溶融粘度の関係を測定し、３００００Ｐａ・ｓになる温度を決定する。そして、実際の成形において、金型内での樹脂温度の変化を、熱電対等で測定し、該温度になるまでの時間を測定することで決定される。求める固化時間が２０秒を越えると、ゴム状重合体同士が凝集し、耐衝撃強度が低下する。好ましくは、１０秒以内が好ましい。
【００４４】
該樹脂組成物の溶融状態での保持条件が、１００００Ｐａ・ｓ以下の溶融粘度で静的に保持されている時間が２分を越えると、マトリックス相を形成している熱可塑性樹脂中に分散しているゴム状重合体が、凝集し、本発明のモルフォロジーを形成できず、耐衝撃強度が低下し、また、光沢度も低下する。
また、樹脂組成物の冷却固化の条件が冷却開始直後の溶融状態から３００００Ｐａ・ｓの溶融粘度になるまでの時間が２０秒を越えると、本発明のモルフォロジーを維持したまま固化できず、ゴム状重合体の急速な凝集が発生し、耐衝撃強度が低下し、また、光沢度も低下する。
【００４５】
【発明の実施の形態】
本発明の実施例における測定方法は以下の通りである。
（１）溶融粘度の測定
Ｄｙｎａｍｉｃ Ａｎａｌｙｚｅｒ ＲＤＡＩＩ（レオメトリックス社製）を使用して、昇温速度 ３℃／分、周波数１Ｈｚで測定した。
（２）成型機金型内での樹脂固化時間の測定
金型内に熱電対をセットし、成型中の温度を連続的にモニターした。金型キャビティーへの樹脂の充填が９５％以上終了した時点から（１）で測定した粘度が３００００Ｐａ・ｓになる温度迄の時間を固化時間とした。
（３）Ｉｚｏｄ衝撃強度
ＡＳＴＭ Ｄ２５６に従って、射出成形された１／８インチ厚さの試験片を用いてノッチ付きで測定した。
（４）ＭＦＲ
ＡＳＴＭ Ｄ１２３８に従って、温度２２０℃、荷重１０ｋｇで測定した。
（５）難燃性
ＵＬ９４規格５ＶＢ燃焼試験（厚み１／１０インチ）に基づく試験により測定した。
【００４６】
適合を○で示し、不適合を×で示す。
（６）光沢度
１０ｃｍ×１０ｃｍ×２ｍｍの平板を射出成形し、ＡＳＴＭ Ｄ５２３−６２Ｔに基づき、光沢計（Ｇｌｏｓｓｍｅｔｅｒ）により、入射角、反射角とも６０度として表面光沢を求めた。
（７）ＨＤＴ
ＡＳＴＭ Ｄ６４８に基づく試験により測定した。
（８）モルフォロジー形態観察
Ｉｚｏｄ衝撃強度テストピースを切り出し、オスニウム酸とルテニウム酸で染色した超薄膜切片を、ＴＥＭで観察した。
（９）ゴム状重合体の存在率の観察
上記（７）で得られた写真を、画像解析装置ＩＰ−１０００（旭化成工業社製）で解析し、円相当面積を求め、各熱可塑性樹脂中に分配する各ゴム状重合体の存在率を求めた。
【００４７】
なお、表中に表している数値は、
分配率（Ｃ）／（Ａ）：ゴム状重合体（Ｃ）が熱可塑性樹脂（Ａ）に分配した比率（％）
分配率（Ｃ）／（Ｂ）：ゴム状重合体（Ｃ）が熱可塑性樹脂（Ｂ）に分配した比率（％）
【００４８】
以下に実施例に用いる配合剤を説明する。なお、部数は重量部とする。
・熱可塑性樹脂（Ａ）
（ＰＣ−１）
溶融エステル交換法で製造されたビスフェノールＡ系ポリカーボネート
Ｍｗ＝２０５００、ヒドロキシ基末端比率＝２３％
（ＰＣ−２）
ホスゲン法で製造されたビスフェノールＡ系ポリカーボネート
Ｍｗ＝２００００
ヒドロキシ基末端比率＝２％
・熱可塑性樹脂（Ｂ）
（ＢＡＡＳ）
ブチルアクリレート−アクリロニトリル−スチレン共重合体
スタイラック−ＡＳ Ｔ８７０４ （旭化成工業社製）
ブチルアクリレート含有量１０重量％
（ＡＳ）
アクリロニトリル−スチレン共重合体
スタイラック−ＡＳ Ｔ８８０１ （旭化成工業社製）
【００４９】
・ゴム状重合体
（ゴム状重合体−１）
メチルメタクリレート−ブチルアクリレート−ジメチルシロキサン共重合体メタブレン Ｓ−２００１ （三菱レーヨン社製）
（ゴム状重合体２）
ＡＢＳレジン ＲＣ （三菱レーヨン社製）
（ゴム状重合体−３）
エチレン−プロピレンゴム
ＥＰ０２Ｐ （日本合成ゴム社製）
・難燃剤
（難燃剤−１）
ＣＲ−７４１ （大八化学工業社製）
（難燃剤−２）
【００５０】
以下の方法で合成した、化式１７の（１０）の混合物を主成分とする縮合リン酸エステル系難燃剤。
ビスフェノールＡ１１４ｇ（０．５モル）、オキシ塩化リン１９２ｇ（１．２５モル）、及び無水塩化マグネシウム１．４ｇ（０．０１５モル）を攪拌機・還流管付きの５００ｍｌ四つ口フラスコに仕込み、窒素気流下７０〜１４０℃にて４時間反応させた。反応終了後、反応温度を維持しつつ、フラスコを真空ポンプにて２００mmHg以下に減圧し、未反応のオキシ塩化リンをトラップにて回収した。ついでフラスコを室温まで冷却し、２，６キシレノール１２２ｇ（１．０モル）、及び無水塩化アルミニウム２．０ｇ（０．０１５モル）を加え、１００〜１５０℃に加熱して４時間反応させた。ついでフラスコを室温まで冷却し、フェノール９４ｇ（１．０モル）を加え、１００〜１５０℃に加熱して４時間保持し、反応を完結させた。そのままの温度で１mmHgまで減圧し、未反応のフェノール類を溜去した。反応時に発生する塩化水素ガスは水酸化ナトリウム水溶液にて捕集し、中和滴定によりその発生量を測定して反応の進行をモニターした。生成した粗リン酸エステルを蒸留水で洗浄した後、濾紙（アドバンテック社製＃１３１）により固形分を除去した。真空乾燥して淡黄色透明な精製物を得た。
【００５１】
ＨＰＬＣ測定（島津製ＬＣ−１０Ａ、カラム：東ソーＴＳＫｇｅｌ ＯＤＳ−８０Ｔ、溶媒：メタノール／水 ９０／１０）の結果、式（１０）成分の純度は７５重量％であった。
（難燃剤−３）
２，６キシレノール１２２ｇ（１．０モル）をシクロヘキサノール９９ｇ（１．０モル）に代えた以外は難燃剤−２と同様の方法で製造、精製した。
（フッ素系樹脂）
テフロン３０Ｊ （三井デュポンフロロケミカル社製）
【００５２】
【実施例】
（実施例１〜４、比較例１、２，５，６）
表−１記載の配合でブレンドし、シリンダー温度を２５０℃に設定した２軸押出機（ＺＳＫ−２５、Ｗ＆Ｐ社製）で、回転数３００ｒｐｍで溶融混練し、押出機の途中から難燃剤をポンプで圧入し、造粒し、ペレットを得た。
【００５３】
得られたペレットを乾燥し、シリンダー温度２６０℃、金型温度６５℃、スクリュー回転数１００ｒｐｍ、射出速度２００ｍｍ／分、射出保圧時間１０秒、冷却時間１５秒に設定された射出成型機（オートショット５０Ｄ、ファナック社製）で成形し、Ｉｚｏｄ衝撃強度評価用試験片形状成形体と、燃焼試験用試験片形状成形体、光沢度測定用平板を得た。なお、冷却開始直後の溶融状態から３００００Ｐａ・ｓの溶融粘度になるまでの時間は、いずれも３秒以内であった。また、１００００Ｐａ・ｓ以下の溶融粘度での溶融状態で、静的に保持されている時間は５秒であった。
評価結果を表−１及び図４、５に示す。
【００５４】
（比較例３）
表−１記載の配合でブレンドし、シリンダー温度を２５０℃に設定した２軸押出機（ＺＳＫ−２５、Ｗ＆Ｐ社製）で、回転数３００ｒｐｍで溶融混練し、押出機の途中から難燃剤をポンプで圧入し、造粒し、ペレットを得た。
得られたペレットを乾燥し、シリンダー温度２６０℃、金型温度６５℃、スクリュー回転数１００ｒｐｍ、射出速度２００ｍｍ／分、射出保圧時間１０秒、冷却時間１５秒に設定された射出成型機（オートショット５０Ｄ、ファナック社製）で成形し、Ｉｚｏｄ衝撃強度評価用試験片形状成形体と、燃焼試験用試験片形状成形体、光沢度測定用平板を得た。なお、冷却開始直後の溶融状態から３００００Ｐａ・ｓの溶融粘度になるまでの時間は、３秒以内であった。また、１００００Ｐａ・ｓ以下の溶融粘度での溶融状態で、静的に保持されている時間は１８０秒であった。
評価結果を表−１に示す。
【００５５】
（比較例４）
表−１記載の配合（単位は重量部）でブレンドし、シリンダー温度を２５０℃に設定した２軸押出機（ＺＳＫ−２５、Ｗ＆Ｐ社製）で、回転数３００ｒｐｍで溶融混練し、押出機の途中から難燃剤をポンプで圧入し、造粒し、ペレットを得た。
得られたペレットを乾燥し、金型温度２６０℃で圧縮成形し、平板状成形体を得た。該成形において、冷却開始直後の溶融状態から３００００Ｐａ・ｓの溶融粘度になるまでの時間は、３０秒であり、１００００Ｐａ・ｓ以下の溶融粘度での溶融状態で、静的に保持されている時間は２４０秒であった。また、該平板状成形体からＩｚｏｄ衝撃強度評価用試験片形状成形体と、燃焼試験用試験片形状成形体を切り出して得た。
評価結果を表−１及び図６に示す。
【００５６】
（実施例５、６、比較例７）表−２記載の配合で２軸押出機のシリンダー温度を２６０℃にする以外は、実施例１と同様に実施した。評価結果を表−２に示す。
（比較例８）表−２記載の配合（単位は重量部）でブレンドし、シリンダー温度を２６０℃に設定した２軸押出機（ＺＳＫ−２５、Ｗ＆Ｐ社製）で、回転数３００ｒｐｍで溶融混練し、造粒し、ペレットを得た。得られたペレットを乾燥し、比較例４と同様に圧縮成形して、成形体を得た。評価結果を表−２に示す。
【００５７】
【表１】

【００５８】
【表２】

【００５９】
【発明の効果】
薄肉成形性に優れた、特に高流動性の樹脂組成物から成形された光沢等の外観及び耐衝撃強度に優れた成形品、更に難燃性に優れた成形品を得ることが出来る。
【図面の簡単な説明】
【図１】本願成形品の分散形態を説明するための模式図
【図２】本願成形品の分散形態を説明するための比較模式図
【図３】本願成形品の分散形態を説明するための比較模式図
【図４】実施例１の成形品のモルフォロジー形態を観察した透過型電子顕微鏡写真。
【図５】比較例１の成形品のモルフォロジー形態を観察した透過型電子顕微鏡写真。
【図６】比較例４の成形品のモルフォロジー形態を観察した透過型電子顕微鏡写真。
【符号の説明】
Ａ：熱可塑性樹脂（Ａ）相
Ｂ：熱可塑性樹脂（Ｂ）相
Ｃ：ゴム状重合体（Ｃ）[0001]
BACKGROUND OF THE INVENTION
The present invention has a morphology in which a rubber-like polymer is distributed at a specific ratio in one of two or more thermoplastic resins, has an excellent appearance such as gloss, and has a high impact strength. The present invention also relates to a molded body having a specific morphology that maintains high impact strength even when a flame retardant is blended.
[0002]
[Prior art]
In recent years, socialization of information has rapidly spread, and the demand for OA devices such as computers, printers, and copiers has increased, and portable information devices such as mobile computers have increased. For this reason, there is an increasing demand for thinner and lighter molded articles made of thermoplastic resins such as housings and parts used in information devices and the like, and to improve the appearance.
[0003]
Therefore, attempts have been made to improve the fluidity of the thermoplastic resin composition to be used and produce a thin lightweight molded product in order to produce molded products in the above-mentioned fields. For example, it is known that a molded article made of polycarbonate widely used for the above applications improves the fluidity of the resin composition by blending ABS and obtains a thin lightweight molded article. It is known that the resin component and the rubber-like polymer constituting the molded body form a morphology as shown in FIG. 2 (cited literature, “molding”, Vol. 8, No. 1 (1996). Year) separate volume). However, in this morphology, in order to meet the recent demand for further thinning, when polycarbonate is made to have a low molecular weight, impact resistance is lowered, and it is very difficult to obtain a molded article excellent in both high fluidity and impact resistance strength. So far, it has not been possible to obtain a molded article excellent in both high fluidity and impact strength.
[0004]
For this reason, attempts have been made to improve the impact resistance of the molded article by further blending a specific rubber such as silicon acrylic rubber or core-shell type rubber or increasing the rubber content. For example, JP-A-6-1897 and JP-A-7-207085 disclose improvements in impact strength by blending silicon acrylic rubber. However, in these methods, the fluidity is lowered by adding a specific rubber, and the gloss of the obtained molded article is lowered. In particular, the improvement of the fluidity has not been sufficient.
In addition, with the intensification of flame retardant regulations, resin flame retardant technology has become an important technology in various fields, especially in the OA field such as computers, word processors and copiers, and in general such as TVs and game machines. It is becoming one of the indispensable characteristics in the home appliance field.
[0005]
Therefore, it has become necessary to provide a method of making the resin flame-retardant and further obtaining the above-mentioned molded product having high fluidity and impact resistance. Generally, a flame retardant is blended as a method of flame-retarding the resin. Things have been done. However, although the flame retardancy and fluidity are improved by blending a flame retardant, the impact strength of the obtained molded product is inevitably lowered. Therefore, JP-A-6-240127 attempts to improve impact resistance by blending a specific rubber such as silicon acrylic rubber. Furthermore, in order to obtain high fluidity, Japanese Patent Application Laid-Open No. 8-127686 discloses lowering the molecular weight of a material resin in addition to the above specific rubber compounding. However, in these methods, by adding rubber, the fluidity is lowered, and the gloss and flame retardancy of the obtained molded article are lowered. Particularly, the improvement of high fluidity and impact resistance is not yet sufficient. It was.
As described above, with a highly fluid resin composition excellent in thin moldability, a molded product excellent in molding appearance such as gloss and impact resistance has not been obtained, and is further made flame retardant and gloss. The molded article was excellent in molding appearance and particularly in impact resistance, and no molded product was obtained.
[0006]
[Problems to be solved by the present invention]
The present invention has the above-mentioned problems, that is, a molded product excellent in appearance such as gloss formed from a resin composition excellent in high fluidity and impact strength superior in thin-wall formability, and further molded in excellent flame retardancy. The purpose is to provide goods.
[0007]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the inventors of the present application have studied many high-fluidity resin compositions and have carefully studied the morphology of the molded products obtained from the compositions, and have continued intensive research. . As a result, a rubber component is blended in the sea phase with two or more thermoplastic resins that form a sea-island structure, and in one sea phase with two or more thermoplastic resins that form a sea-sea structure, Furthermore, the rubber component is dispersed with a specific morphology. Particularly in a resin composition having a polycarbonate resin as a sea phase, an alkyl (meth) acrylate, an aromatic vinyl monomer, and a vinyl cyanide monomer are co-polymerized. It is surprising that the above problem can be solved by a combination with a rubber-like polymer component obtained by grafting a vinyl monomer onto a composite rubber containing a copolymer, polyorganosiloxane and polyalkyl (meth) acrylate as a constituent component of the coalescence. The present invention has been found by finding the facts.
[0008]
  That is, the present invention
1. The composition is composed of a thermoplastic resin (A), (B) and a rubbery polymer (C) that have a sea-island or sea-sea structure, and the distribution of the rubbery polymer (C) If the thermoplastic resin forms a sea-island structure,Of thermoplastic resin (A)During the sea phase and when the thermoplastic resin forms a sea-sea structure,Of thermoplastic resin (A)It has a morphology distributed selectively to the sea phase at a ratio of 70 to 100% by weight.And the thermoplastic resin (A) is a polycarbonate resin (a-1), the thermoplastic resin (B) is a butyl acrylate-acrylonitrile-styrene copolymer (b-1), and the rubbery polymer (C) is poly. A composite rubber-based graft copolymer (c-1) obtained by grafting a vinyl monomer onto a composite rubber containing an organosiloxane and a polyalkyl (meth) acrylate, and the content ratio of each component is (a-1) 90 Parts by weight to 50 parts by weight, (b-1) 1 to 40 parts by weight, and (c-1) 1 to 30 parts by weight. The resin composition is shaped and cooled and solidified from a molten state to produce a molded body. In this case, the holding condition in the molten state of the resin composition is within a period of 2 minutes in which the resin composition is statically held at a melt viscosity of 10,000 Pa · s or less, and the condition for cooling and solidification is immediately after the start of cooling. 30 from the molten state Time until the melt viscosity of 00Pa · s is equal to or obtained by the process is within 20 secondsMolded body.
2. The rubber-like polymer (C) has a number average equivalent circle diameter and a particle size of 0.05 to 3 μm.1The molded body described.
3. The composition contains 0.1 to 30 parts by weight of flame retardant (D) and 0.01 to 5 parts by weight of anti-dripping agent (E) with respect to 100 parts by weight in total of (A) to (C). 2. The molded product according to 1 or 2 characterized by the above.
4). The polycarbonate resin (a-1) is a polycarbonate produced by an ester exchange method from an aromatic dihydroxy compound and a carbonic acid diester in which the proportion of terminal hydroxy groups in all terminals is in the range of 20 to 80 mol%. Characterized by1 to 3The molded body described.
[0009]
5. The flame retardant (D) is one or more flame retardants selected from halogen flame retardants, silicon flame retardants, phosphate ester flame retardants, and condensed phosphate ester flame retardants.3 or 4The molded body described.
6). The composition contains an anti-dripping agent (E) tetrafluoroethylene resin (PTFE).In any one of 3-5The molded body described.
[0010]
Hereinafter, the present invention will be described in detail.
The observation method of the morphology of the resin composition of the present invention is performed with a transmission electron microscope (TEM). At that time, the distribution ratio of each component and the measurement of the number average circle equivalent diameter can be obtained by image analysis of the obtained TEM photograph.
The morphology of the molded product of the present invention will be described using schematic diagrams.
FIG. 1 schematically shows an example of a specific morphology that satisfies the requirements of the present invention. There are thermoplastic resins (A) and (B) forming a phase separation structure, and 70% by weight or more of the rubber-like polymer (C) is selectively dispersed in the thermoplastic resin (A).
The molded product of the present application has such a morphology, and as a result, excellent impact resistance can be maintained even when the resin component is made high in fluidity by low molecular weight.
[0011]
On the other hand, the morphologies different from the molded product of the present application are shown in FIGS. FIG. 2 is a schematic view of the morphology of a molded body composed of PC and ABS. The rubber-like polymer (C) is not dispersed in the thermoplastic resin (A: polycarbonate), but is mostly dispersed in the thermoplastic resin (B: AS resin). In such a form, if the polycarbonate is made to have a low molecular weight and the composition is fluidized, the polycarbonate is not sufficiently reinforced and the impact resistance is lowered. FIG. 3 shows a rubbery polymer (C) having a large particle diameter, which is equally dispersed in both the thermoplastic resins (A) and (B). In this case, since the rubber-like polymer (C) is uniformly dispersed in the thermoplastic resin (A) (B), the rubber-like polymer (C) into the thermoplastic resin (A) (B) The abundance is almost equal to the composition ratio of (A) to (B). Thus, the rubber-like polymer that is not compatible with the thermoplastic resin has a large particle size and is ineffective in improving the impact resistance.
[0012]
Examples of the thermoplastic resins (A) and (B) used in the present invention include polystyrene resins, polyolefin resins, polyamide resins, polyoxymethylene resins, polyphenylene ether resins, polycarbonate resins, polyester resins, and the like. Engineering plastics, polymethylmethacrylate resins, and the like. Examples of styrene resins include styrene homopolymers, copolymers of styrene and vinyl monomers, and rubber-modified styrene resins. Examples of vinyl monomers include aromatic vinyl compounds such as styrene, α-methylstyrene, and paramethylstyrene, alkyl (meth) acrylates such as methyl methacrylate, methyl acrylate, butyl acrylate, and ethyl acrylate, acrylic acid, methacrylic acid, and the like. (Meth) acrylic acids, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, α, β-unsaturated carboxylic acids such as maleic anhydride, N-phenylmaleimide, N-methylmaleimide, N-cyclohexylmaleimide And glycidyl group-containing compounds such as glycidyl methacrylate, preferably aromatic vinyl compounds, alkyl (meth) acrylates, vinyl cyanide compounds, maleimide compounds, and more preferably , Su Ren, acrylonitrile, N- phenylmaleimide, butyl acrylate. These vinyl compounds can be used alone or in combination of two or more. In the present application, a resin that forms at least two or more phase separation structures is selected from the thermoplastic resins as the thermoplastic resins (A) and (B).
[0013]
Among the above thermoplastic resins, in particular, the thermoplastic resin (A) is a polycarbonate resin, (B) is an alkyl (meth) acrylate monomer, an aromatic vinyl monomer, and a vinyl cyanide monomer. A vinyl compound copolymer contained as a constituent component is preferred.
The polycarbonate-based resin (a-1) preferably used in the present invention has a main chain composed of repeating units represented by the following chemical formula 1.
[0014]
[Chemical 1]

(In the formula, Ar is a divalent aromatic residue, and examples thereof include phenylene, naphthylene, biphenylene, pyridylene, and those represented by the following chemical formula 2.)
[0015]
[Chemical 2]

(Wherein Ar¹And Ar²Are each an arylene group. For example, it represents a group such as phenylene, naphthylene, biphenylene, pyridylene, and Y is an alkylene group or a substituted alkylene group represented by Chemical formula 3. )
[0016]
[Chemical 3]

(Wherein R¹, R², R^ThreeAnd R^FourEach independently represents a hydrogen atom, a lower alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, optionally substituted with a halogen atom or an alkoxy group, k is an integer of 3 to 11, and R5 And R6 are individually selected for each X and independently of each other are a hydrogen atom, a lower alkyl group or an aryl group, optionally substituted with a halogen atom or an alkoxy group, and X represents a carbon atom. To express. )
Moreover, you may contain the bivalent aromatic residue shown by following Chemical formula 4 as a copolymer component.
[0017]
[Formula 4]

(Wherein Ar¹, Ar²Is the same as Chemical 2 Z is a simple bond, or -O-, -CO-, -S-, -SO₂-, -CO₂-, -CON (R¹)-(R¹Is the same as in Chemical Formula 3). )
Examples of these divalent aromatic residues include those represented by the following chemical formulas 5 and 6.
[0018]
[Chemical formula 5]

[0019]
[Chemical 6]

(Wherein R⁷And R⁸Are each independently hydrogen, halogen, C₁~ C_TenAlkyl group, C₁~ C_TenAlkoxy group, C₁~ C_TenA cycloalkyl group or a phenyl group; m and n are integers of 1 to 4, and when m is 2 to 4, each R⁷May be the same or different, and when n is 2 to 4, each R⁸May be the same or different. )
Especially, what is represented by following Chemical formula 7 is a preferable example. In particular, those containing 85 mol% or more of a repeating unit in which Ar is represented by the following chemical formula 7 are preferred.
[0020]
[Chemical 7]

The polycarbonate used in the present invention may contain a trivalent or higher aromatic residue as a copolymerization component.
[0021]
Although the molecular structure of the polymer terminal is not particularly limited, one or more terminal groups selected from a phenolic hydroxyl group, an aryl carbonate group, and an alkyl carbonate group can be bonded. The aryl carbonate terminal group is represented by the following chemical formula 8, and specific examples thereof include chemical formula 9.
[0022]
[Chemical 8]

(Wherein Ar^ThreeIs a monovalent aromatic residue, and the aromatic ring may be substituted. )
[0023]
[Chemical 9]

The alkyl carbonate terminal group is represented by the following chemical formula 10, and specific examples thereof include the chemical formula 11 below.
[0024]
[Chemical Formula 10]

(Wherein R⁷Represents a linear or branched alkyl group having 1 to 20 carbon atoms. )
Embedded image

Of these, phenolic hydroxyl groups, phenyl carbonate groups, pt-butylphenyl carbonate groups, p-cumylphenyl carbonate, and the like are preferably used.
[0025]
In the present application, the ratio of the phenolic hydroxyl group terminal to the other terminal is not particularly limited, but the phenolic hydroxyl group terminal ratio of all terminals is preferably in the range of 20 to 80 mol%.
As a method for measuring the phenolic hydroxyl terminal amount, a method of measuring using NMR, a method of obtaining by a titanium method, a UV method or an IR method are generally known, but in the present invention, it was obtained by an NMR method.
[0026]
The weight average molecular weight (Mw) of the polycarbonate used in the present invention is generally in the range of 5,000 to 100,000 in terms of weight average molecular weight, and is not particularly limited.
The weight average molecular weight (Mw) in the present invention was measured using GPC, and the measurement conditions were as follows. A tetrahydrofuran solvent and polystyrene gel were used, and the molecular weight was determined from the standard monodisperse polystyrene composition curve using a reduced molecular weight calibration curve according to the following formula.
[0027]
M_PC= 0.3591M_PS ^1.0388
(M_PCIs the molecular weight of polycarbonate, M_PSIs the molecular weight of polystyrene)
These polycarbonates can be produced by known methods. Specifically, a known method of reacting an aromatic dihydroxy compound and a carbonate precursor, for example, an interfacial polymerization method in which an aromatic dihydroxy compound and phosgene are reacted in the presence of an aqueous sodium hydroxide solution and a methylene chloride solvent (phosgene method). A transesterification method (melting method) in which an aromatic dihydroxy compound and diphenyl carbonate are reacted, a method of solid-phase polymerization of a crystallized carbonate prepolymer (Japanese Patent Laid-Open Nos. 1-158033, 1-271426, 3-68627, etc.) Can be manufactured.
[0028]
Examples of the alkyl (meth) acrylate monomer that is a constituent of the vinyl compound copolymer (b-1) of the present invention include methyl methacrylate, methyl acrylate, butyl acrylate, and ethyl acrylate, and preferably butyl. Acrylate. Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, paramethylstyrene, and the like, and styrene is preferable. Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile, and acrylonitrile is preferable.
The proportion of the alkyl (meth) acrylate monomer component in the vinyl compound copolymer (b-1) of the present invention needs to be 0.5 to 80% by weight, preferably 0.5 to 60% by weight, more preferably 1 to 40% by weight. When the amount is less than 0.5% by weight, high fluidity cannot be obtained, and the impact strength improvement effect is small. On the other hand, when it exceeds 80% by weight, the heat resistance is remarkably lowered.
[0029]
As the rubber-like polymer (C) of the present invention, conjugated diene rubbers such as polybutadiene, polyisoprene, polychloroprene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, ethylene-propylene rubber, ethyl acrylate, Grafted with rubber-like polymers such as acrylic rubber such as butyl acrylate, silicone-based rubber, silicon-acrylic rubber, etc., and with the rubber-like polymer particles, either styrene or the above vinyl monomer, alone or in combination. A polymerized composite rubber-like polymer may be mentioned. The composite rubber-like polymer generally includes a polymer of styrene or vinyl monomer that is polymerized without grafting to the rubber-like polymer in the process of producing the composite rubber-like polymer. The component is understood as a thermoplastic resin.
[0030]
The rubber-like polymer (c-1) of the present invention includes one or more composite rubbers having a structure in which a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component are alternately intertwined and combined and integrated. A composite rubber-based graft copolymer obtained by graft polymerization of a vinyl-based monomer such as a rubber-like polymer that can be produced by the method described in JP-A No. 64-79257 is preferably used.
[0031]
The production method of the composite rubbery polymer is not particularly limited, but an emulsion graft polymerization method in which a vinyl compound is graft polymerized to a latex rubbery polymer produced by emulsion polymerization, and emulsion graft polymerization and solution polymerization. And a two-stage polymerization method combined with suspension polymerization. These can be continuous, batch, or semi-batch. In addition, a composite rubber-like polymer having a high rubber content is prepared in advance by the above-mentioned method, and a thermoplastic resin mainly composed of a vinyl compound used at the time of graft polymerization manufactured by bulk polymerization, emulsion polymerization or suspension polymerization is blended. It is also possible to keep it. In that case, the composite rubber-like polymer is grasped as the rubber-like polymer component (C), and the thermoplastic resin is grasped as the component (A) or (B).
[0032]
The preferred particle size of the rubbery polymer is not particularly limited because it varies depending on the type of thermoplastic resin used as the matrix, but the number average equivalent circle diameter is 0.05 to 3 μ, preferably 0.05 to 1.5 μ. More preferably, it is 0.05-1.0 micrometer. If the particle diameter is smaller than 0.05 μm, impact resistance cannot be obtained, and if it exceeds 3 μm, impact resistance is lowered and gloss value is lowered.
[0033]
The flame retardant (D) in the present invention is a so-called general flame retardant, and includes a phosphorus compound, a halogen organic compound, a silicon compound, a nitrogen-containing organic compound such as melamine, magnesium hydroxide, and aluminum hydroxide. Inorganic compounds such as antimony oxide, bismuth oxide, metal oxides such as zinc oxide and tin oxide, inorganics such as red phosphorus, phosphine, hypophosphorous acid, phosphorous acid, metaphosphoric acid, pyrophosphoric acid, and phosphoric anhydride Fibers such as phosphorus compounds, carbon fibers, glass fibers, etc., expanded graphite, silica, silica glass melts, etc. are used, preferably halogen organic compounds, phosphorus compounds, silicon compounds and combinations thereof. is there.
[0034]
As the halogen-based organic compound, it refers to general halogen-based flame retardants and halogen-containing phosphate esters in general. For example, the halogen-based organic compounds include hexachloropentadiene, hexabromodiphenyl, octabromodiphenyl oxide, tribromophenoxymethane, decabromodiphenyl, decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromobisphenol A, tetrabromophthalimide, hexa Although there are bromobutene, hexabromocyclododecane, etc., a halogen-based organic compound having the structure of (1) shown below is preferable, and a halogen-based organic compound of (2) shown below is particularly preferable. .
[0035]
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[0036]
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On the other hand, halogen-containing phosphate esters include tris-chloroethyl phosphate, tris-dichloropropyl phosphate, tris-β-chloropropyl phosphate, tris (tribromophenyl) phosphate, tris (dibromophenyl) phosphate, tris (tribromoneo Pentyl phosphate) and condensed phosphoric acid esters thereof. Tris (tribromoneopentyl phosphate), tris (tribromophenyl) phosphate, and tris (dibromophenyl) phosphate are preferable. These halogen organic compounds can be used alone or in combination of two or more.
As a phosphorus compound, it represents with following Chemical formula 14.
[0037]
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(In the formula, Ar1, Ar2, Ar3, and Ar4 are each independently an alkyl group, a cycloalkyl group, and an aryl group. These aromatic residues, cycloalkyl groups, and aryl groups are alkyl groups, alkoxy groups, and the like. And n is a natural number of 0 to 5, may be a single compound, or may be a mixture of different compounds of n.)
In the formula, R is a group selected from the following chemical formulas 15 and 16.
[0038]
Embedded image

[0039]
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Specifically, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, diisopropylphenyl phosphate, tris (chloroethyl) ) Phosphate esters such as phosphate, and condensed phosphate esters represented by Chemical formula 16 are included. Among these, triphenyl phosphate and condensed phosphates represented by the following chemical formula 17 are preferably used.
[0040]
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Examples of the silicon flame retardant include a compound containing RSiO, and R includes, for example, an aryl group such as a phenyl group and a xylyl group, an alkyl group such as a methyl group and a propyl group, and an alkenyl group. . Generally known as polyorganosiloxanes.
These phosphorus flame retardants can be used alone or in combination of two or more.
[0041]
The blending amount of the flame retardant is determined according to the required level of flame retardancy, but should be 0.1 to 30 parts by weight with respect to 100 parts by weight of the total amount of the thermoplastic resin and the rubbery polymer. It is. If it is less than 0.1 part by weight, the necessary flame retardant effect is not exhibited. If it exceeds 30 parts by weight, the mechanical strength of the resin is lowered. The range is preferably 1 to 25 parts by weight, and particularly preferably 3 to 22 parts by weight. When a halogen compound is used as the flame retardant, a flame retardant aid can be used to enhance the flame retardant effect. The flame retardant aid is preferably a compound containing an element belonging to VA in the periodic table of elements, and specifically includes a nitrogen-containing compound, a phosphorus-containing compound, antimony oxide, bismuth oxide, and the like. Metal oxides such as iron oxide, zinc oxide, and tin oxide are also effective. Of these, antimony oxide is particularly preferable, and specific examples include antimony trioxide and antimony pentoxide. These flame retardant aids may be used that have been surface-treated for the purpose of improving dispersion in the resin and / or improving the thermal stability of the resin.
[0042]
The addition amount of the flame retardant aid is preferably 0.5 to 20 parts by weight. When the amount is less than 0.5 part, the effect of the flame retardant aid is not sufficient. When the amount exceeds 20 parts by weight, the mechanical strength of the resin And processing fluidity is reduced. More preferably, it is 1-15 weight part, Most preferably, it is 1-10 weight part.
The method for producing the resin composition for forming the molded article of the present invention can be performed by a conventionally known method and is not particularly limited. For example, after mixing each component uniformly with a Henschel mixer, a super mixer, a turnbull mixer, a ribbon blender or the like, there is a method of melt kneading with a single screw extruder, a twin screw extruder, a Banbury mixer, or the like. Further, at that time, it is optional to add additives such as known antioxidants, ultraviolet absorbers, lubricants, mold release agents, antistatic agents, colorants, fillers and the like within the range not impairing the gist of the present invention. .
[0043]
Furthermore, the method for producing the molded article of the present invention from these resin compositions includes extrusion molding, compression molding, injection molding, gas assist molding and the like, and is not particularly limited. However, in order to obtain a molded article having a morphology distributed at a specific ratio according to the present invention, when molding a molded article of the resin composition, the holding condition in the molten state of the resin composition is 10000 Pa · s or less. The time for which the melt viscosity is statically maintained is within 2 minutes, and the time for the solidification condition to be within 30 seconds from the melted state immediately after the start of cooling to the melt viscosity of 30000 Pa · s is within 20 seconds. It is necessary to be molded below. From the melted state immediately after the start of cooling, for example, in injection molding, refers to the time when filling of the resin into the mold cavity has been completed by 95% or more. In addition, the time at which 30000 Pa · s is reached is determined by, for example, measuring the relationship between the resin temperature and the melt viscosity with a rheometer or the like and determining the temperature at which 30000 Pa · s is reached. In actual molding, the change in the resin temperature in the mold is measured with a thermocouple or the like, and the time until the temperature is reached is determined. When the required solidification time exceeds 20 seconds, the rubber-like polymers are aggregated and the impact resistance strength is lowered. Preferably, it is within 10 seconds.
[0044]
If the holding condition in the molten state of the resin composition is statically held at a melt viscosity of 10,000 Pa · s or less exceeds 2 minutes, the resin composition is dispersed in the thermoplastic resin forming the matrix phase. The rubber-like polymer is agglomerated and cannot form the morphology of the present invention, the impact strength is lowered, and the glossiness is also lowered.
If the time required for the cooling and solidification conditions of the resin composition to reach a melt viscosity of 30000 Pa · s from the melted state immediately after the start of cooling exceeds 20 seconds, the resin composition cannot be solidified while maintaining the morphology of the present invention. Rapid aggregation of the polymer occurs, impact strength is reduced, and glossiness is also reduced.
[0045]
DETAILED DESCRIPTION OF THE INVENTION
The measuring method in the Example of this invention is as follows.
(1) Measurement of melt viscosity
Using a Dynamic Analyzer RDAII (manufactured by Rheometrics), measurement was performed at a temperature rising rate of 3 ° C./min and a frequency of 1 Hz.
(2) Measurement of resin solidification time in molding machine mold
A thermocouple was set in the mold, and the temperature during molding was continuously monitored. The time from when the filling of the resin into the mold cavity to 95% or more to the temperature at which the viscosity measured in (1) reaches 30000 Pa · s was defined as the solidification time.
(3) Izod impact strength
Measurements were made with a notch using an injection molded 1/8 inch thick specimen according to ASTM D256.
(4) MFR
Measurement was performed at a temperature of 220 ° C. and a load of 10 kg according to ASTM D1238.
(5) Flame resistance
It measured by the test based on UL94 standard 5VB combustion test (thickness 1/10 inch).
[0046]
Conformity is indicated by ○ and nonconformity is indicated by ×.
(6) Glossiness
A 10 cm × 10 cm × 2 mm flat plate was injection-molded, and the surface gloss was determined by a gloss meter based on ASTM D523-62T with an incident angle and a reflection angle of 60 degrees.
(7) HDT
Measured by a test based on ASTM D648.
(8) Morphological morphology observation
An Izod impact strength test piece was cut out and an ultrathin film section stained with osmic acid and ruthenic acid was observed with TEM.
(9) Observation of abundance of rubbery polymer
The photograph obtained in the above (7) is analyzed with an image analyzer IP-1000 (Asahi Kasei Kogyo Co., Ltd.), the equivalent area of the circle is obtained, and the abundance of each rubber-like polymer distributed in each thermoplastic resin is determined. Asked.
[0047]
The numbers shown in the table are
Distribution ratio (C) / (A): Ratio (%) of rubber-like polymer (C) distributed to thermoplastic resin (A)
Distribution ratio (C) / (B): Ratio (%) of rubber-like polymer (C) distributed to thermoplastic resin (B)
[0048]
The compounding agent used for an Example below is demonstrated. The number of parts is parts by weight.
・ Thermoplastic resin (A)
(PC-1)
Bisphenol A polycarbonate produced by melt transesterification
Mw = 20500, hydroxy group terminal ratio = 23%
(PC-2)
Bisphenol A polycarbonate produced by the phosgene method
Mw = 20000
Hydroxy group terminal ratio = 2%
・ Thermoplastic resin (B)
(BAAS)
Butyl acrylate-acrylonitrile-styrene copolymer
Stylac-AS T8704 (Asahi Kasei Kogyo Co., Ltd.)
Butyl acrylate content 10% by weight
(AS)
Acrylonitrile-styrene copolymer
Stylac-AS T8801 (Asahi Kasei Kogyo Co., Ltd.)
[0049]
・ Rubber polymer
(Rubber polymer-1)
Methyl methacrylate-butyl acrylate-dimethyl siloxane copolymer methabrene S-2001 (Mitsubishi Rayon Co., Ltd.)
(Rubber polymer 2)
ABS resin RC (Mitsubishi Rayon Co., Ltd.)
(Rubber polymer-3)
Ethylene-propylene rubber
EP02P (Nippon Synthetic Rubber)
·Flame retardants
(Flame retardant-1)
CR-741 (manufactured by Daihachi Chemical Industry Co., Ltd.)
(Flame retardant-2)
[0050]
A condensed phosphate ester flame retardant synthesized by the following method and containing as a main component a mixture of the formula (10) (10).
Bisphenol A (114 g, 0.5 mol), phosphorus oxychloride (192 g), (1.25 mol), and anhydrous magnesium chloride (1.4 g, 0.015 mol) were charged into a 500 ml four-necked flask equipped with a stirrer / reflux tube and a nitrogen stream. It was made to react at 70-140 degreeC below for 4 hours. After completion of the reaction, while maintaining the reaction temperature, the flask was decompressed to 200 mmHg or less with a vacuum pump, and unreacted phosphorus oxychloride was recovered with a trap. Next, the flask was cooled to room temperature, 122 g (1.0 mol) of 2,6 xylenol and 2.0 g (0.015 mol) of anhydrous aluminum chloride were added, and the mixture was heated to 100 to 150 ° C. and reacted for 4 hours. The flask was then cooled to room temperature, 94 g (1.0 mol) of phenol was added, heated to 100-150 ° C. and held for 4 hours to complete the reaction. The pressure was reduced to 1 mmHg at the same temperature, and unreacted phenols were distilled off. Hydrogen chloride gas generated during the reaction was collected with an aqueous sodium hydroxide solution, and the amount of the generated hydrogen chloride was measured by neutralization titration to monitor the progress of the reaction. The produced crude phosphate ester was washed with distilled water, and then the solid content was removed with a filter paper (# 131 manufactured by Advantech). It was vacuum dried to obtain a pale yellow transparent purified product.
[0051]
As a result of HPLC measurement (LC-10A manufactured by Shimadzu, column: Tosoh TSKgel ODS-80T, solvent: methanol / water 90/10), the purity of the formula (10) component was 75% by weight.
(Flame retardant-3)
It was produced and purified in the same manner as flame retardant-2 except that 122 g (1.0 mol) of 2,6 xylenol was replaced with 99 g (1.0 mol) of cyclohexanol.
(Fluorine resin)
Teflon 30J (Mitsui DuPont Fluorochemicals)
[0052]
【Example】
(Examples 1-4, Comparative Examples 1, 2, 5, 6)
Blended with the formulation shown in Table 1 and melt kneaded at a rotational speed of 300 rpm with a twin screw extruder (ZSK-25, manufactured by W & P) with a cylinder temperature set at 250 ° C., and pumped the flame retardant from the middle of the extruder Was pressed and granulated to obtain pellets.
[0053]
The obtained pellets were dried and an injection molding machine (automatic) set to a cylinder temperature of 260 ° C., a mold temperature of 65 ° C., a screw rotation speed of 100 rpm, an injection speed of 200 mm / min, an injection pressure holding time of 10 seconds, and a cooling time of 15 seconds. Shot 50D (manufactured by FANUC) was used to obtain an Izod impact strength evaluation specimen-shaped molded body, a combustion test specimen-shaped molded body, and a gloss measurement flat plate. The time from the melted state immediately after the start of cooling to the melt viscosity of 30000 Pa · s was within 3 seconds. In addition, the static holding time was 5 seconds in a molten state at a melt viscosity of 10,000 Pa · s or less.
The evaluation results are shown in Table 1 and FIGS.
[0054]
(Comparative Example 3)
Blended with the formulation shown in Table 1 and melt kneaded at a rotational speed of 300 rpm with a twin screw extruder (ZSK-25, manufactured by W & P) with a cylinder temperature set at 250 ° C., and pumped the flame retardant from the middle of the extruder Was pressed and granulated to obtain pellets.
The obtained pellets were dried and an injection molding machine (automatic) set to a cylinder temperature of 260 ° C., a mold temperature of 65 ° C., a screw rotation speed of 100 rpm, an injection speed of 200 mm / min, an injection pressure holding time of 10 seconds, and a cooling time of 15 seconds. Shot 50D (manufactured by FANUC) was used to obtain an Izod impact strength evaluation specimen-shaped molded body, a combustion test specimen-shaped molded body, and a gloss measurement flat plate. The time from the melted state immediately after the start of cooling to the melt viscosity of 30000 Pa · s was within 3 seconds. Further, the static holding time in a molten state at a melt viscosity of 10,000 Pa · s or less was 180 seconds.
The evaluation results are shown in Table-1.
[0055]
(Comparative Example 4)
Blended in the formulation shown in Table 1 (unit: parts by weight), melt-kneaded at a rotational speed of 300 rpm with a twin screw extruder (ZSK-25, manufactured by W & P) with a cylinder temperature set at 250 ° C. From the middle, a flame retardant was injected with a pump and granulated to obtain pellets.
The obtained pellets were dried and compression-molded at a mold temperature of 260 ° C. to obtain a flat molded body. In this molding, the time from the melted state immediately after the start of cooling to the melt viscosity of 30000 Pa · s is 30 seconds, and the time in which the melt is kept static in the melt state at a melt viscosity of 10000 Pa · s or less. Was 240 seconds. Moreover, the test piece shape molded object for Izod impact strength evaluation and the test piece shape molded object for combustion tests were cut out from this flat molded body, and obtained.
The evaluation results are shown in Table 1 and FIG.
[0056]
(Example 5,6, Comparative Example 7) The same procedure as in Example 1 was performed except that the cylinder temperature of the twin screw extruder was changed to 260 ° C. with the formulation shown in Table-2. The evaluation results are shown in Table-2.
(Comparative Example 8) Melting and kneading at a rotation speed of 300 rpm with a twin screw extruder (ZSK-25, manufactured by W & P), blended with the formulation shown in Table 2 (unit: parts by weight) and setting the cylinder temperature to 260 ° C And granulated to obtain pellets. The obtained pellets were dried and compression molded in the same manner as in Comparative Example 4 to obtain a molded body. The evaluation results are shown in Table-2.
[0057]
[Table 1]

[0058]
[Table 2]

[0059]
【The invention's effect】
It is possible to obtain a molded product having excellent thin-wall moldability, in particular, a molded product having excellent appearance such as gloss and impact strength and molded from a highly fluid resin composition, and further excellent in flame retardancy.
[Brief description of the drawings]
FIG. 1 is a schematic diagram for explaining a dispersion form of a molded product of the present application.
FIG. 2 is a comparative schematic diagram for explaining the dispersion form of the molded product of the present application.
FIG. 3 is a comparative schematic diagram for explaining the dispersion form of the molded product of the present application.
4 is a transmission electron micrograph showing the morphology of the molded article of Example 1. FIG.
5 is a transmission electron micrograph showing the morphology of the molded article of Comparative Example 1. FIG.
6 is a transmission electron micrograph showing the morphology of the molded article of Comparative Example 4. FIG.
[Explanation of symbols]
A: Thermoplastic resin (A) phase
B: Thermoplastic resin (B) phase
C: Rubber-like polymer (C)

Claims (6)

The composition is composed of a thermoplastic resin (A), (B) and a rubbery polymer (C) that have a sea-island or sea-sea structure, and the distribution of the rubbery polymer (C) When the thermoplastic resin forms a sea-island structure, in the sea phase of the thermoplastic resin (A), and when the thermoplastic resin forms a sea-sea structure, one thermoplastic resin ( have a morphology which is selectively distributed in a ratio of 70 to 100% by weight in the sea phase of a), and the thermoplastic resin (a) is polycarbonate resin (a-1), the thermoplastic resin (B) is butyl acrylate -A composite rubber graft copolymer in which an acrylonitrile-styrene copolymer (b-1) and a rubber-like polymer (C) are grafted with a vinyl monomer on a composite rubber containing polyorganosiloxane and polyalkyl (meth) acrylate. Polymer (c-1), and The content ratio of the components is (a-1) 90 parts by weight to 50 parts by weight, (b-1) 1 to 40 parts by weight, and (c-1) 1 to 30 parts by weight. When manufacturing a molded body by shaping and cooling and solidifying, the holding condition in the molten state of the resin composition should be kept statically at a melt viscosity of 10000 Pa · s or less within 2 minutes. And a molded product obtained by a production method in which the time from the molten state immediately after the start of cooling to the melt viscosity of 30000 Pa · s is within 20 seconds .   The molded article according to claim 1, wherein the rubber-like polymer (C) has a number average equivalent circle diameter and a particle diameter of 0.05 to 3 µm.   The composition contains 0.1 to 30 parts by weight of the flame retardant (D) and 0.01 to 5 parts by weight of the anti-dripping agent (E) with respect to 100 parts by weight in total of (A) to (C). The molded article according to claim 1 or 2, wherein The polycarbonate resin (a-1) is a polycarbonate produced by an ester exchange method from an aromatic dihydroxy compound and a carbonic acid diester in which the proportion of terminal hydroxy groups in all terminals is in the range of 20 to 80 mol%. The molded product according to any one of claims 1 to 3 . Flame retardant (D) is a halogen-based flame retardant, silicone-based flame retardant, phosphoric ester-based flame retardant, according to claim 3 or 4 is at least one flame retardant selected from condensed phosphoric acid ester-based flame retardant Molded body. The composition according to any one of claims 3 to 5, wherein the composition contains an anti-dripping agent (E) tetrafluoroethylene resin (PTFE).

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