JP4363601B2 - Flame retardant resin composition - Google Patents

Description

［式中、Ｘ⁶は（メタ）アリル基、（メタ）アクリロイル基または１−プロペニル基を示す。Ｙ⁶は水素、または−ＳＯ₃Ｍ⁶（Ｍ⁶は水素、アルカリ金属、アルカリ土類金属、アンモニウムまたは炭素数１〜４のヒドロキシアルキルアンモニウムを示す。）で表される硫酸エステル塩形成基、または−ＣＨ₂ＣＯＯＭ⁶（Ｍ⁶は水素、アルカリ金属、アルカリ土類金属、アンモニウムまたは炭素数１〜４のヒドロキシアルキルアンモニウムを示す。）で表されるカルボン酸塩、または下記化２で表されるリン酸モノエステル塩形成基を示す。Ｒ^6'は炭素数１〜１８のアルキル基、アルケニル基もしくはアラルキル基、Ｒ^6''は水素または炭素数１〜１８のアルキル基、アルケニル基もしくはアラルキル基、Ｒ^6'''は水素またはプロペニル基、Ａ⁶は炭素数２〜４のアルキレン基または置換アルキレン基、ｍは１〜２００の整数を示す。］
【００４９】
【化２】

（式中、各Ｍ^6'は水素、アルカリ金属、アルカリ土類金属、アンモニウム又は炭素数１〜４のヒドロキシアルキルアンモニウムであり、各Ｍ^6'は同一のものでも異なるものでもよい。）
【００５０】
他の例として、下記化３で表される（メタ）アリルグリセリルエーテル誘導体および（メタ）アクリルグリセリルエステル誘導体があげられる。
【００５１】
【化３】

［式中、Ｘ⁷は、（メタ）アリル基または（メタ）アクリロイル基を示す。Ｙ⁷は、水素、または−ＳＯ₃Ｍ⁷（Ｍ⁷は、水素、アルカリ金属、アルカリ土類金属、アンモニウムまたは炭素数１〜４のヒドロキシアルキルアンモニウムを示す。）で表される硫酸エステル塩形成基、または−ＣＨ₂ＣＯＯＭ^7'（Ｍ^7'は、水素、アルカリ金属、アルカリ土類金属を示す。）で表されるカルボン酸塩、または上記化２で表されるリン酸モノエステル塩形成基、または、下記化４で表される基を示す。Ｚ⁷は、炭素数８〜３０のアルキル基、置換アルキル基、アルケニル基、置換アルケニル基、アルキルアリール基、置換アルキルアリール基、アラルキルアリール基、置換アラルキルアリール基、アシル基または置換アシル基を示す。Ａ⁷は、炭素数２〜４のアルキレン基または置換アルキレン基、ｍは０〜１００、ｎは０〜５０の整数を示す。］
【００５２】
【化４】

（式中、Ｍ^6''は、水素、アルカリ金属、アルカリ土類金属、アンモニウム、炭素数１〜４のヒドロキシアルキルアンモニウムまたは炭素数２〜４のアルキレンオキサイド単位を有してもよい炭素数８〜３０のアルキル基であり、Ｍ^6'''は、水素、アルカリ金属、アルカリ土類金属、アンモニウム、炭素数１〜４のヒドロキシアルキルアンモニウムである。）
又、他の例として、下記化５で表されるコハク酸誘導体があげられる。
【００５３】
【化５】

［式中、Ｘ⁸は、（メタ）アリル基または（メタ）アクリロイル基を示す。Ｂ⁸、Ｂ^8'は、次に表されるＹ⁸またはＺ⁸を示し、Ｂ⁸、Ｂ^8'は、異なるものである。Ｙ⁸は、Ｍ⁸または−ＳＯ₃Ｍ⁸（Ｍ⁸は水素、アルカリ金属、アルカリ土類金属、アンモニウムまたは炭素数１〜４のヒドロキシアルキルアンモニウムを示す。）で表される硫酸エステル塩形成基を示す。Ｚ⁸は、炭素数８〜３０のアルキル基またはアルケニル基を示す。Ａ⁸は、炭素数２〜４のアルキレン基、置換基を有するアルキレン基であり、ｍ、ｎは０〜５０の整数である。］
更に、他の例として、下記化６で表される化合物があげられる。
【００５４】
【化６】

［式中、Ｘ⁹は、（メタ）アリル基または（メタ）アクリロイル基を示す。Ｙ⁹は、水素、または−ＳＯ₃Ｍ⁹（Ｍ⁹は水素、アルカリ金属、アルカリ土類金属、アンモニウムまたは炭素数１〜４のヒドロキシアルキルアンモニウムを示す。）で表される硫酸エステル塩形成基、または−ＣＨ₂ＣＯＯＭ⁹（Ｍ⁹は水素、アルカリ金属、アルカリ土類金属、アンモニウムまたは炭素数１〜４のヒドロキシアルキルアンモニウム）で表されるカルボン酸塩を示す。各Ｒ⁹は、水素、または炭素数１〜２５のアルキル基で、それぞれ同一であっても異なってもよく、各Ｒ^9'は、炭素数１〜２５のアルキル基、ベンジル基、またはスチリル基を示し、それぞれ同一であっても異なってもよく、ｐは０〜２の整数を示す。Ａ⁹は、炭素数２〜４のアルキレン基、置換基を有するアルキレン基であり、ｍ、ｎは０〜５０の整数を示す。］
更に、他の例として、下記化７で表される（メタ）アリルエーテル誘導体および（メタ）アクリルエステル誘導体があげられる。
【００５５】
【化７】

［式中、Ｘ²⁷は，（メタ）アリル基または（メタ）アクリロイル基を示す。Ｙ²⁷は、水素、またはメチル基、または−ＳＯ₃Ｍ²⁷（Ｍ²⁷は水素、アルカリ金属、アルカリ土類金属、アンモニウムまたは炭素数１〜４のヒドロキシアルキルアンモニウムを示す。）で表される硫酸エステル塩形成基、または−ＣＨ₂ＣＯＯＭ²⁷（Ｍ²⁷は、水素、アルカリ金属、アルカリ土類金属、アンモニウムまたは炭素数１〜４のヒドロキシアルキルアンモニウムを示す。）で表されるカルボン酸塩、または化２で表されるリン酸モノエステル塩形成基を示す。Ｚ²⁷は、炭素数８〜３０のアルキル基を示す。Ａ²⁷は、炭素数２〜４のアルキレン基または置換アルキレン基、ｍは０〜２０、ｎは０〜５０の整数を示す。］
更に、他の例として、下記化８で表されるジオール化合物があげられる。
【００５６】
【化８】

（式中、Ａ³⁰は炭素数２〜４のアルキレン基であり、Ｒ³⁰は炭素数８〜２４の炭化水素基であり、Ｒ^30'は水素またはメチル基であり、ｍおよびｎはｍ＋ｎが０〜１００の間の値となるようなそれぞれ０〜１００の数であり、Ｍ³⁰は水素原子、アルカリ金属、アルカリ土類金属、アンモニウムまたは炭素数１〜４のヒドロキシアルキルアンモニウムである。）
更に、他の例として、下記化９で表せる化合物があげられる。
【００５７】
【化９】

［式中、Ｘ³²は、（メタ）アリル基、（メタ）アリロキシ基または（メタ）アクリロイル基、（メタ）アクリロイルオキシ基または下記化１０を示す。Ｙ³²は水素、または−ＳＯ₃Ｍ³²（Ｍ³²は、水素、アルカリ金属、アルカリ土類金属、アンモニウムまたは炭素数１〜４のヒドロキシアルキルアンモニウムを示す。）で表される硫酸エステル塩形成基、または−ＣＨ₂ＣＯＯＭ³²（Ｍ³²は、水素、アルカリ金属、アルカリ土類金属、アンモニウムまたは炭素数１〜４のヒドロキシアルキルアンモニウムを示す。）で表されるカルボン酸塩、または化２で表されるリン酸モノエステル塩形成基、または、化４で表されるスルホコハク酸モノエステル塩形成基を示す。Ｚ³²は炭素数６〜３０の置換基を有してもよいアルキレン基を示す。Ａ³²は炭素数２〜４のアルキレン基または置換アルキレン基、ｎ、ｍは０〜５０の整数を示す。］
【００５８】
【化１０】

（式中Ｒ^32'、Ｒ^32''は水素またはメチル基を表す。）
【００５９】
本発明に用いられるポリカーボネート樹脂（Ａ−ｅ）は、芳香族ポリカーボネート樹脂であり、芳香族ジヒドロキシ化合物とホスゲンからの、均一系での反応または不均一系での２相界面反応による方法、またはやはり芳香族ジヒドロキシ化合物と炭酸ジエステルの反応により溶融エステル交換法の何れかで製造される芳香族ポリカーボネート樹脂を用いることが出来る。
【００６０】
芳香族ジヒドロキシ化合物としては、ビスフェノール類が好ましく、特に２，２−ビス（４−ヒドロキシフェニル）プロパン（以下ビスフェノールＡと記す）が好ましい。また、ビスフェノールＡの一部または、全部を他の２価フェノール化合物で置換してもよい。ビスフェノールＡ以外の芳香族ジヒドロキシ化合物は、例えば、ハイドロキノン、４，４−ジヒドロキシジフェニル、ビス（４−ヒドロキシフェニル）スルフィド、ビス（４−ヒドロキシフェニル）スルフォン、ビス（４−ヒドロキシフェニル）ケトンなどの化合物である。これらの芳香族ジヒドロキシ化合物のホモポリマー、または、２種以上のコポリマーあるいは、これらのブレンド品であってもよい。
【００６１】
溶融エステル交換法に用いる炭酸ジエステルとしては、ジアリールカーボネート類、特にジフェニルカーボネートが好ましい。
【００６２】
芳香族ポリカーボネート類は本発明の目的を損なわない範囲で少量の、３ないしは３以上の多官能性化合物を加えることにより分岐を導入することが出来る。多官能性化合物の例としては、多価フェノールを挙げることができる。
【００６３】
本発明におけるポリカーボネート樹脂（Ａ−ｅ）は、重量平均分子量が５０００〜３０００００の範囲が好ましい。上記範囲より重量平均分子量が小さい場合は、機械的強度が低く好ましくはなく、上記範囲より大きい場合は流動性が低下し好ましくはない。更に好ましくは、重量平均分子量が７０００〜１０００００の範囲であり、より好ましくは１００００〜８００００の範囲にある。
【００６４】
ポリマーの末端分子構造は特に限定はされないが、ヒドロキシル基、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一種以上の末端基とすることが出来る。ヒドロキシル基は、用いた芳香族ジヒドロキシ化合物から誘導される末端であり、その割合は、実質的に含まないものから全末端の５０％あるものまで用いることが出来る。
【００６５】
熱可塑性樹脂（Ａ）としてポリカーボネート系樹脂（Ａ−ｅ）と、ゴム強化樹脂（Ａ−ｄ）からなる樹脂組成物を用いることが特に好ましい。その好ましい配合組成は、ポリカーボネート系樹脂（Ａ−ｅ）５〜９８重量部に対しゴム強化樹脂（Ａ−ｄ）９５〜２重量部であり、さらに好ましくは、ポリカーボネート系樹脂（Ａ−ｅ）２０〜９０重量部に対しゴム強化樹脂（Ａ−ｄ）８０〜１０重量部であり、更に好ましくはポリカーボネート系樹脂（Ａ−ｅ）４０〜８５重量部に対しゴム強化樹脂（Ａ−ｄ）６０〜１５重量部である。
【００６６】
本発明において用いられるフッ素系樹脂（Ｂ）は、樹脂組成物中において主に０．５ミクロン以下の太さのフィブリル状の形をなし、フィブリルが、ネットワーク構造及び／又は分岐状で存在するフッ素系樹脂は、一般に、ポリテトラフルオロエチレン（ＰＴＦＥ）やフッ化エチレンプロピレン（ＦＥＰ）樹脂等のパーフルオロアルカン樹脂、及びパーフルオロアルコキシ（ＰＦＡ）樹脂から選ばれ、特に、ＰＴＦＥが好ましい。
【００６７】
フッ素系樹脂の配合量は、熱可塑性樹脂（Ａ）１００重量部に対して０．０１〜５重量部が好ましい。０．０１部未満の場合、滴下防止の効果が十分でなく、５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０．０２〜２重量部で、特に好ましくは０．１〜１重量部である。
【００６８】
本発明において、フィブリル状の形のフッ素系樹脂（Ｂ）の樹脂組成物中の分散形態は具体的には以下の方法で観察される。すなわち、樹脂組成物のＵＬ９４垂直燃焼試験用テストピースを射出成形で成形し、それから引張り試験で得られる引張り破断面を走査型電子顕微鏡（ＳＥＭ）で観察することにより、複数のフッ素系樹脂フィブリルが上に記載した分散形態で存在することを確認する。本発明において、ＳＥＭ観察における上記以外の条件は特に限定されないが、例えば、熱可塑性樹脂（Ａ）としてポリカーボネート系樹脂（Ａ−ｅ）と、ゴム強化樹脂（Ａ−ｄ）からなる樹脂組成物を用いた場合には、実際には下記の条件でＳＥＭ観察を行なう。
【００６９】
（射出成形）
成型機 ：Ｍ−ＪＥＣ１０（日本国、モダンマシナリー社製）
成形温度 ：２６０℃
金型温度 ：６０℃
射出速度 ：５００（設定値）
テストピース：１／２×５×１／１６ｉｎｃｈ
（ＳＥＭ観察用サンプルの作成）
引っ張り試験器（オートグラフ５０００Ｄ、日本国、島津製作所製）を用いて、速度５ｍｍ／分で破断するまで引っ張る。
【００７０】
（ＳＥＭ観察）
前処理 ：サンプル破断面に、金の厚さが２００オングストローム以上になるように金蒸着を行う。（蒸着装置：日本国、日本電子社製 ＪＦＣ １５００ QUICK AUTO COATER)
観察装置：ＪＳＭ−５３００（日本国、日本電子社製）
加速電圧：１５ｋＶ
【００７１】
以下に、本発明においてフッ素系樹脂分散フィブリルが示すネットワーク構造及び／又は分岐構造を有する分散形態について、図１、図３〜９に参照して説明する。尚、図１はフッ素系樹脂フィブリルの分散形態の１例を示す模式図であり、図３〜９は分散形態の種々の例を示すＳＥＭ写真である。フッ素系樹脂は、図１では実線で示した部分であり、図３〜９では白く見える部分である。
【００７２】
上記のように、本発明においては、ＵＬ−９４規格に記載の垂直燃焼法による難燃性試験用に射出成形法によって作成される樹脂組成物の試験片にそれを破断させて破断面を形成するのに十分な引張り応力を加えることによって得られた破片の破断面について、全体にフィブリルが分散した７ミクロン×７ミクロンの領域を走査型電子顕微鏡で調べた時に、該分散フィブリルが示す分散形態が、該複数のフィブリルがその総延長の５０％以上に相当する長さにわたって０．５ミクロン以下の直径を有し、且つ、該複数のフィブリルが、少なくとも２本のフィブリルが互いに交差する交差点を１つ以上有するネットワーク構造と、１本のフィブリルが少なくとも２本のフィブリルに分岐する分岐点を１つ以上有する分岐構造からなる群から選ばれる少なくとも１つの構造を有し、該交差点と該分岐点からなる群から選ばれる５個以上の点が該７ミクロン×７ミクロンの領域に存在する、ことが必要である。
【００７３】
フッ素系樹脂のフィブリルは、フィブリルがその総延長の５０％以上に相当する長さにわたって０．５ミクロン以下の直径を有する必要がある。図１の符号ｃで示されるような０．５ミクロンを越える太さのフィブリルの存在は可能であるが、例えば図６のＳＥＭ写真に見られるように、該７ミクロン×７ミクロンの領域に存在するフィブリルの総延長の５０％以上に相当する長さにわたって０．５ミクロン以下の直径を有する必要があり、好ましくは７０％以上、更に好ましくは９０％以上である。０．５ミクロン以下の直径を有するフィブリルの長さがフィブリルの総延長に占める割合が５０％未満であると、優れた滴下防止効果を得られない。
【００７４】
また、本発明にいうネットワーク構造は、図１の模式図に符号ａで示した部分のように、２本以上のフィブリルが互いに交差する交差点を１つ以上有する。また、本発明にいう分岐構造は、図１の模式図に符号ｂで示した部分のように、１本のフィブリルが少なくとも２本のフィブリルに分岐する分岐点を１つ以上有する。ネットワーク構造と分岐構造は、ともに３次元の広がりを持つ。この交差点と分岐点からなる群から選ばれる５個以上の点が該７ミクロン×７ミクロンの領域に存在することが必要である。この交差点と分岐点からなる群から選ばれる点が５個未満であると、優れた滴下防止効果を得られない。
【００７５】
ＳＥＭで観察された該７ミクロン×７ミクロンの領域にフッ素系樹脂分散フィブリルが上記のような特定の分散形態を示すことは、樹脂組成物中におけるフッ素系樹脂分散フィブリルの密な存在を反映している。この様な密なフッ素系樹脂分散フィブリルの存在により、燃焼時のフィブリルの３次元的な収縮が生起し、効果的な滴下防止が達成されると推定される。
【００７６】
フッ素系樹脂は、例えば「ふっ素樹脂ハンドブック」（日本国、日刊工業新聞社 １９９０年刊）に記載のように、懸濁重合または乳化重合で製造される。本発明の目的のためには、乳化重合で合成したフッ素系樹脂が好ましく、水を溶媒として用いる乳化重合でフッ素系樹脂ラテックスを得て、得られたラテックスを凝析・乾燥したファインパウダーや、上記のフッ素系樹脂ラテックスを濃縮・安定化した水性ディスパージョンが用いられる。
【００７７】
フッ素系樹脂水性ディスパージョンは市販されている。市販のフッ素系樹脂水性ディスパージョンのうち、ＰＴＦＥディスパージョンの例としては、日本国の三井・デュポンフロロケミカル社から市販される“テフロン３０−J”（固形分濃度６０重量％、粒子径０．２３ミクロン、界面活性剤濃度がＰＴＦＥ重量に対して６重量％、ｐＨ値９〜１０）、や日本国のダイキン工業社から市販される“ポリフロンＴＦＥディスパージョンＤ−１”（固形分濃度約６０重量％、粒子径０．２０〜０．４０ミクロン、ｐＨ値９〜１０）などを挙げることができる。
【００７８】
本発明においては、フッ素系樹脂水性ディスパージョンの使用が特に好ましい。フッ素系樹脂水性ディスパージョンの好ましい固形分濃度は、１０〜７０重量％である。通常の市販のフッ素系樹脂水性ディスパージョンは、固形分濃度が６０重量％付近で供給されることが多いが、必要に応じて水で希釈するか、または濃縮して所望の濃度に調整して用いることが出来る。
【００７９】
フッ素系樹脂は、樹脂組成物中で、熱可塑性樹脂や難燃剤との溶融混練時にネットワーク構造及び／又は分岐構造を形成するために、繊維形成能を有するものを用いるが、このようなフッ素系樹脂については、ＵＳＰ３，００５，７９５号、３，６７１，４８７号、４，４６３，１３０号を参照できる。
【００８０】
本発明における難燃剤（Ｃ）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、酸化アンチモン、酸化ビスマス等の無機化合物を用いることができる。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無機繊維、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、好ましくはリン系化合物、またはハロゲン系有機化合物および、ハロゲン系有機化合物と酸化アンチモンの併用である。又、リン酸エステル系難燃剤及び縮合リン酸エステル系難燃剤を挙げることができる。
【００８１】
ハロゲン系有機化合物としては、一般に難燃剤として用いられるハロゲン系有機化合物および含ハロゲンリン酸エステルを指す。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１１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１４のハロゲン系有機化合物である。
【００８２】
【化１１】

ｎ＝０または自然数、Ｘは独立に塩素、または臭素を示し、ｉ、ｊ、ｋ、ｐはそれぞれ１〜４の整数であり、Ｒ¹およびＲ²はそれぞれ独立に水素、メチル基、下記化１２、
【００８３】
【化１２】

で表わせる基、フェニル基または、下記化１３（ただし、ｍは０、１、２または３を示す）
【００８４】
【化１３】

で表わせる基。
【００８５】
【化１４】

ｎ＝０または自然数、Ｒ³およびＲ⁴は各々、独立して、下記化１５
【００８６】
【化１５】

で表わせる基、フェニル基または、下記化１６
【００８７】
【化１６】

で表わせる基。
【００８８】
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。
【００８９】
リン酸エステル系難燃剤としては、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、トリプロピルホスフェート、トリブチルホスフェート、トリペンチルホスフェート、トリヘキシルホスフェート、トリシクロヘキシルホスフェート、トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、ジメチルエチルホスフェート、メチルジブチルホスフェート、エチルジプロピルホスフェート、ヒドロキシフェニルジフェニルホスフェートなどのリン酸エステルやこれらを各種置換基で変性した化合物がある。
【００９０】
縮合リン酸エステル系難燃剤としては、下記一般式化１７で表わされるものを用いることができる。
【００９１】
【化１７】

（式中、ｎは１〜１０の整数であり、Ａｒ¹〜Ａｒ⁴は各々独立に、フェニル基、トリル基またはキシリル基である。また、ｎが２以上の場合、複数あるＡｒ⁴は各々同一でも異なってもよい。また、Ｒ⁵は下記化１８のＡ１〜Ａ４から選ばれる基である。）
【００９２】
【化１８】

上記化１７で表わされる縮合リン酸エステル系難燃剤のなかで好ましいものは、下記の化１９〜化２２で表される縮合リン酸エステル化合物であり、これらのリン酸エステル化合物は難燃化効果、および、耐熱性が特に優れる。
【００９３】
【化１９】

【００９４】
【化２０】

【００９５】
【化２１】

【００９６】
【化２２】

（式中、Ａｒ⁵〜Ａｒ⁷は各々、独立して、フェニル基、トリル基、または、２，６−キシリル基以外のキシリル基であり、Ｒは、式（５）のＲ⁵で定義したＡ４と同じである。）
これらは単独または２種類以上を併用して用いることができる。
【００９７】
難燃剤の配合量は望まれる難燃性のレベルに応じて決められるが、熱可塑性樹脂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重量部未満では望まれる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。
【００９８】
難燃助剤として好ましくは、元素周期律表におけるＶ族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、酸化ビスマスである。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。
【００９９】
難燃助剤の添加量は、熱可塑性樹脂（Ａ）１００重量部に対して０．５〜２０重量部が好ましい。０．５重量部未満の場合、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。
【０１００】
本発明において望ましいフッ素系樹脂フィブリルの分散形態を有する樹脂組成物を製造する方法としては、例えば、フッ素系樹脂としてファインパウダーを用いる場合、−２０℃以上にならない状態で粉砕したフッ素系樹脂と、冷却した原料樹脂を１０℃以下の温度でブレンドし、溶融混練することでも達成出来る。しかし、本発明の樹脂組成物を構成する成分の中で、ファインパウダー、ディスパージョン等のフッ素系樹脂を除く、所望量の熱可塑性樹脂の一部又は全部と、もし望まれるならば、所望量の難燃剤の一部又は全部を溶融混練し、その後、フッ素系樹脂を配合して混練する製造方法をとるのが好ましい。
【０１０１】
最も好ましくは、フッ素系樹脂としてディスパージョンを用い、溶融した熱可塑性樹脂に配合するのが好ましい。この方法により、溶融樹脂中にラテックス粒子が均一に分散され、凝集等が抑えられ、樹脂組成物中での剪断により、均一な繊維化が促進され、フッ素系樹脂のネットワーク構造及び／または分岐構造が形成され易くなると考えられる。
【０１０２】
以下に、本発明の樹脂組成物の好ましい製造方法について、さらに詳細に説明する。
好ましい製造方法としては、例えば、目的とする難燃性樹脂組成物が熱可塑性樹脂１００重量部、フッ素系樹脂０．０１〜５重量部、及び難燃剤０．１〜３０重量部を包含する樹脂組成物であるなら、まず、１０〜１００重量部の熱可塑性樹脂（Ａ）と、０〜３０重量部の難燃剤（Ｃ）を溶融混練して溶融混練物を形成し、この溶融混練物に０．０１〜５重量部のフッ素系樹脂（Ｂ）を加えて共に溶融混練してフッ素系樹脂含有熱可塑性樹脂組成物を形成した後、もし、熱可塑性樹脂（Ａ）／難燃剤（Ｃ）の重量比が１００／０．１〜３０を満足していない場合には、この比になるように成分（Ａ）及び／又は成分（Ｃ）を該フッ素系樹脂含有熱可塑性樹脂組成物に加えて更に溶融混練する方法が挙げられる。
【０１０３】
即ち、本発明においては、
熱可塑性樹脂１００重量部、フッ素系樹脂０．０１〜５重量部、及び難燃剤０．１〜３０重量部を包含する難燃性樹脂組成物の製造方法において、
（１）１０〜１００重量部の熱可塑性樹脂（Ａ）と０〜３０重量部の難燃剤（Ｃ）を溶融混練して溶融混練物を形成し、
（２）該溶融混練物に０．０１〜５重量部のフッ素系樹脂（Ｂ）を加えて共に溶融混練してフッ素系樹脂含有熱可塑性樹脂組成物を形成する
ことを包含し、その際該フッ素系樹脂（Ｂ）は水性分散媒に該フッ素系樹脂が分散した水性ディスパージョンの形で用い、該水性ディスパージョンは、フッ素系樹脂粒径が０．０５〜０．５ミクロンで、固形分濃度が１０〜７０重量％であり、
工程（１）で溶融混練する成分（Ａ）と成分（Ｃ）が成分（Ａ）／成分（Ｃ）重量比が１００／０．１〜３０の範囲の所望比を満足していない場合は、成分（Ａ）と成分（Ｃ）から選ばれる少なくとも１種の成分を、工程（２）で形成されるフッ素系樹脂含有熱可塑性樹脂組成物に成分（Ａ）／成分（Ｃ）重量比１００／０．１〜３０の所望比を満足するのに必要な量、その後の少なくとも１段の付加的工程で加えて各工程で更に溶融混練する、
ことを特徴とする難燃性樹脂組成物の製造方法が提供される。
【０１０４】
溶融混練は従来から公知の方法で行うことが出来る。例えば、フッ素系樹脂以外の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、単軸押出し機、二軸押出し機、バンバリーミキサー等で、溶融混練し、その溶融した樹脂組成物中にフッ素系樹脂のディスパージョンを配合し、さらに溶融混練を行うことにより本発明の樹脂組成物を製造できる。
【０１０５】
また、本発明の効果が得られる限り、公知の安定剤（例えば酸化防止剤、紫外線吸収剤など）、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り、なかでもリン系安定剤（リン系酸化防止剤や熱安定剤など）の併用は好ましく、その配合順序も、フッ素系樹脂配合の前後いずれでも良い。
【０１０６】
本発明の樹脂組成物に所望により用いることの出来る充填剤としては、ガラスファイバー、ガラスフレーク、カーボンファイバー、タルク、マイカ等を挙げることができる。これらの種類は、必要とする機械的強度、剛性、成形加工性、耐熱性に応じて決めればよい。配合量は、熱可塑性樹脂（Ａ）１００重量部に対して、０〜５０重量部の範囲である。
【０１０７】
具体的にフッ素系樹脂のディスパージョンの配合方法を例示すると、溶融混練に押出し機を使用する場合、押出し機の途中、樹脂の溶融が完了した後段に液添用のノズルを設け、ポンプにより、上記のノズルからディスパージョンを注入することが出来る。ポンプとしてはチューブポンプ、ギヤポンプ、プランジャーポンプ等を用いることが出来る。送液中のフッ素系樹脂の凝集を防ぐためにディスパージョンは冷却するのが好ましく、またポンプもチューブポンプが好ましい。
【０１０８】
フッ素系樹脂のディスパージョンのこの他の好ましい配合方法としては、図２に示すように、押出し機の途中にベント口等の開口部（３）を設け、そこへ冷却用のジャケットを備えた配管（２）を設置し、この配管よりディスパージョンを滴下する方法がある。この方法を用いると、フッ素系樹脂のディスパージョンに圧力をかける必要がなく、ポンプ部分（Ｐ）でのフッ素系樹脂のディスパージョンの凝集が防止でき、さらに、滴下部分の配管が押出し機に接触していないため、冷却ジャケットで冷却されたディスパージョンの昇温も少なく、フッ素系樹脂の凝集が抑制でき好ましい。さらにベント口（３）から滴下と共にディスパージョンの水性分散媒が蒸発により効率的に除去されるので好ましい。ポンプとしてはチューブポンプ、ギヤポンプ、プランジャーポンプ等を用いることが出来、チューブポンプが好ましい。
【０１０９】
即ち、本発明の更に他の態様によれば、本発明の高難燃性樹脂組成物の上記した製造方法において、途中に開口部を有する押出し機を用い、該開口部より該フッ素系樹脂（Ｂ）水性ディスパージョンを滴下して、上記の工程（１）で形成された溶融混練物と共に溶融混練しながら、該フッ素系樹脂（Ｂ）水性ディスパージョンの水性分散媒を該開口部から蒸発させる方法が提供される。
【０１１０】
図２は、本発明の上記の態様により開口部を途中に有する押出し機を用いて本発明の難燃性樹脂組成物を製造する方法を説明するための概略図であるが、本発明の製造方法はこの図によって制限されるものではない。尚、例えば、図２に示す押出し機のホッパー１と（フッ素系樹脂ディスパージョンを供給するための）開口部３の間に別の少なくとも１つの更なる開口部（図示せず）を設けて、ホッパー１とその更なる開口部から熱可塑性樹脂の少なくとも一部と難燃剤の少なくとも一部をそれぞれ供給することもできる。また、図２の開口部３の（押出し方向に対して）上流で熱可塑性樹脂及び／又は難燃剤の供給を完了しない場合は、開口部３の後段（下流）に別の少なくとも１つの更なる開口部（図示せず）を設けて、その更なる開口部から残りの成分を供給することができる。
【０１１１】
このようにして得られた熱可塑性樹脂組成物からなる成形品の成型方法は特に限定されないが、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げられ、中でも射出成形が好ましい。
成形品の例としては、ノート型パソコン、コピー機、プリンターのハウジング等のＯＡ機器筐体、ＯＡ機器シャーシ、携帯電話のハウジング等が挙げられる。
【０１１２】
【発明の実施の形態】
以下、実施例及び比較例により本発明の実施の形態を具体的に説明するが、本発明はこれらの例によって何ら限定されるものではない。
【０１１３】
本発明の実施例及び比較例における測定および評価方法は以下の通りである。
（１）重量平均分子量
ゲルパーミエーションクロマトグラフィー（ＧＰＣ）にて測定した。
装置：日本国、東ソー ＨＬＣ−８０２０
溶媒：ＴＨＦ
カラム：日本国、東ソー ＴＳＫゲル（Ｔ５０００ＨＸＬ＋Ｔ４０００ＨＸＬ）
【０１１４】
（２）熱可塑性樹脂組成物中のフッ素系樹脂の形態観察明細書に記載の方法に準じて観察した。
（試験片の射出成形）
成型機 ：ＭＪＥＣ−１０（日本国、モダンマシナリー社製）
成形温度 ：２６０℃
金型温度 ：６０℃
射出速度 ：５００（設定値）
テストピース：１／２×５×１／１６ｉｎｃｈ
【０１１５】
但し成形温度と金型温度は、熱可塑性樹脂として、後述の（Ａ−１）を単独で用いる場合は、それぞれ２８０℃、８０℃に変更して実施した。同様に、熱可塑性樹脂として、後述の（Ａ−２）を単独で用いる場合は、それぞれ２９０℃、８０℃に変更して実施した。また熱可塑性樹脂として、後述の（Ａ−６）を単独で用いる場合は、それぞれ２３０℃、５０℃に変更して実施した。
【０１１６】
（ＳＥＭ観察用サンプルの作成）
引っ張り試験機（オートグラフ５０００Ｄ、日本国、島津製作所製）を用いて、上記の射出成形で得た試験片を速度５ｍｍ／分で破断するまで引っ張る。
【０１１７】
（ＳＥＭ観察）
前処理 ：サンプル破断面に、金の厚さが２００オングストローム以上になるように金蒸着を行う。（蒸着装置：日本国、日本電子社製 ＪＦＣ １５００ＱＵＩＣＫＡＵＴＯＣＯＡＴＥＲ）
観察装置：ＪＳＭ−５３００（日本国、日本電子社製）
加速電圧：１５ｋＶ
全体にフィブリルが分散した７ミクロン×７ミクロンの領域をＳＥＭで調べて、分散フィブリルが示す分散形態における、０．５ミクロン以下の直径を有するフィブリルの長さがフィブリルの総延長に占める割合（％）と、フィブリルの交差点と分岐点の数を測定した。
【０１１８】
（３）難燃性
ＵＬ９４規格２０ＭＭ垂直燃焼試験（厚み１／１６インチ）に基づく試験により、評価した。この試験においては、Ｖ−０又はＶ−１と評価されているときは火種の滴下がなく、火種の落下が認められたときはＶ−２と評価される。
【０１１９】
（４）光沢度
それぞれの樹脂組成物に適合した温度で射出成形した１０ｃｍｘ１０ｃｍｘ２ｍｍの平板を射出成形し、ＡＳＴＭ−Ｄ−５２３−６２Ｔに基づき光沢計（Ｇｌｏｓｓｍｅｔｅｒ）により、入射角、反射角６０度として表面光沢を測定した。（光沢計による測定で得られた値が高いほど、表面が滑らかで光沢度が高い。）
【０１２０】
（５）フローマーク
それぞれの樹脂組成物に適合した温度で１０ｃｍｘ１０ｃｍｘ２ｍｍの平板を射出成形し、その表面を目視によりフローマークまたはシルバーの有無を調べ、以下のように判定した。
○：フローマーク、シルバーの発生なし
×：フローマークまたはシルバーの発生あり
【０１２１】
以下に実施例に用いる配合剤を説明する。
（ポリカーボネート樹脂Ａ−１）
重量平均分子量２２，５００であるビスフェノールＡ
に由来する芳香族ポリカーボネート樹脂
【０１２２】
（ポリフェニレンエーテル樹脂Ａ−２）
米国特許４，７８８，２７７号明細書（日本国特願昭６２−７７５７０号に対応）に記載されている方法に従って、ジブチルアミンの存在下に、２，６−キシレノールを酸化カップリング重合した、還元粘度がηｓｐ／ｃ＝０．４２ｄｌ／ｇであって、２８０℃で１４０ｓｅｃ^-1の剪断速度で測定した溶融粘度が４９，０００ｐｏｉｓｅである、ポリ（２，６−ジメチル−１，４−フェニレン）エーテル（以下ＰＰＥと略す）樹脂７５重量部と、重量平均分子量２１０，０００の一般ポリスチレン樹脂２５重量部をあらかじめ溶融混練した、変性ＰＰＥ樹脂。
【０１２３】
（ゴム強化樹脂Ａ−３）
ブタジエンゴムラテックス（透過型電子顕微鏡より求めたラテックスの重量平均粒子径は０．２８ミクロン）４０重量部、イオン交換水１００重量部、ロジン酸カリウム０．３重量部を１０リットル反応器に入れ、気相部を窒素置換した後、この初期溶液を７０℃に昇温した。重合前のｐＨの調整は炭酸ガスを反応器内でバブルして約７に調整した。次に以下に示す組成からなる水溶液１と単量体混合液３、さらに乳化剤としてロジン酸カリウムを含んだ水溶液２を反応器に５時間にわたり連続的に添加した。添加終了後、１時間温度を保ち、反応を完結させた。
【０１２４】
水溶液１の組成は次の通りである。
硫酸第一鉄０．００５重量部、ソジウムフォルムアルデヒドスルホキシレート（ＳＦＳ）０．１重量部、エチレンジアミンテトラ酢酸二ナトリウム（ＥＤＴＡ）０．０４重量部、イオン交換水５０重量部。
水溶液２の組成は次の通りである。
ロジン酸カリウム１．０重量部、イオン交換水２０重量部。
単量体混合液３の組成は次の通りである。
アクリロニトリル１８重量部、スチレン４２重量部、ｔ−ドデシルメルカプタン（ｔ−ＤＭ）０．６重量部、クメンハイドロパーオキサイド（ＣＨＰ）０．１重量部。
【０１２５】
次に作成したグラフト重合体ラテックスに酸化防止剤を添加した後、塩析し、水洗浄、脱水した後加熱乾燥し、粉末を得た。
さらに、アクリロニトリル成分比２７重量％で、重量平均分子量が１２０，０００のＡＳ樹脂（アクリロニトリル−スチレン樹脂）と、上で得られた粉末とを混合し、以下の組成のＡＢＳ（アクリロニトリル−ブタジエン−スチレン）樹脂を得た。
【０１２６】
アクリロニトリル成分 ２４重量％
ブタジエン成分 １０重量％
スチレン成分 ６６重量％
（ゴム強化樹脂Ａ−４）
ゴム強化樹脂Ａ−３と同様にして、以下の組成のＡＢＳ樹脂を得た。
アクリロニトリル成分 １８重量％
ブタジエン成分 ３３重量％
スチレン成分 ４９重量％
（ゴム強化樹脂Ａ−５）
アクリロニトリル成分 １８重量％
ブタジエン成分 ２０重量％
スチレン成分 ５０重量％
Ｎ−フェニルマレイミド成分 １２重量％
からなるゴム強化樹脂
（ゴム強化樹脂Ａ−６）
ブタジエン成分 １０重量％
スチレン成分 ９０重量％
からなるＨＩＰＳ樹脂（ハイインパクトポリスチレン樹脂）
【０１２７】
（フッ素系樹脂ＰＴＦＥのディスパージョン Ｂ−１）
日本国、ダイキン工業社製 ポリフロンＴＦＥディスパージョン Ｄ−１（固形分濃度約６０重量％、粒子径０．２０〜０．４０ミクロン、ｐＨ値９〜１０）
（フッ素系樹脂ＰＴＦＥのディスパージョン Ｂ−２）
日本国、三井デュポンフロロケミカル社製、テフロン３０−Ｊ（固形分濃度６０重量％、粒子径０．２３ミクロン、界面活性剤濃度はＰＴＦＥ重量に対して６重量％、ｐＨ値９〜１０）
【０１２８】
（フッ素系樹脂ＰＴＦＥファインパウダー Ｂ−３）
日本国、ダイキン工業社製、ポリフロンＦ−２０１Ｌ
（フッ素系樹脂ＰＴＦＥファインパウダー Ｂ−４）
日本国、三井デュポンフロロケミカル社製、テフロン６２−Ｊ
【０１２９】
（難燃剤Ｃ−１）
明細書記載の式（２）で表され、
ｎ＝０又は自然数、ＲとＲ’は式（４）に記載の基で表される化合物であって、軟化温度が１０５℃である難燃剤。
（難燃剤Ｃ−２）
トリフェニルホスフェート
【０１３０】
（難燃剤Ｃ−３）
前記化２０と化２１の混合物を主成分とする縮合リン酸エステル系難燃剤であり、以下の方法で合成した。
ビスフェノールＡ １１４ｇ（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。
【０１３１】
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［日本国、アドバンテック東洋（株）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。
ＨＰＬＣ分析（日本国、島津製ＬＣ−１０Ａ、カラム：日本国、東ソーＴＳＫｇｅｌ ＯＤＳ−８０Ｔ、溶媒：メタノール／水 ９０／１０）の結果、化２０と化２１成分の合計の純度は７５重量％であった。
【０１３２】
【実施例】
実施例１〜７、比較例７
以上のように調製したフッ素系樹脂を除く樹脂を冷却（３℃）し、ドライアイスとともに粉砕（サンプルミル、ＳＫ−Ｍ１０型、日本国、協立理工社製）したフッ素系樹脂（Ｂ−３、Ｂ−４）を、表１、２に掲げる組成（単位は重量部）でブレンドし、２軸押出機（ＺＳＫ−２５、ドイツ国、Ｗerner＆Ｐfleiderer社製）で混練造粒し、ペレットを得て、評価を行った。押出し機の設定温度は、実施例１〜３、比較例７は２９０℃、実施例４、６は２５０℃、実施例５、７は２２０℃にして実施した。樹脂組成物中のフッ素樹脂の分散形態の観察結果と、難燃性の評価結果を表１、２に示す。
【０１３３】
比較例１〜６、８
以上のように調製した樹脂を表２に掲げる組成（単位は重量部）で一括ブレンド（室温、２５℃）し、２軸押出機（ＺＳＫ−２５）で混練造粒し、ペレットを得て、評価を行った。押出し機の設定温度は比較例１と比較例６、８は２９０℃、比較例３、５は２５０℃、比較例２、４は２２０℃にして実施した。樹脂組成物中のフッ素樹脂の分散形態の観察結果と、難燃性の評価結果を表２に示す。
比較例６は押出しが困難であった。
【０１３４】
実施例８〜１５、比較例１７
表３、４の組成（単位は重量部）に従い、下記のように実施した。
フッ素系樹脂と難燃剤を除いて各原料をブレンドし、２軸押出機（ＺＳＫ−２５）で混練し、押出機の途中から冷却（３℃）したフッ素系樹脂のディスパージョンを図２の様な装置で溶融した原料に滴下混練し、その後段で難燃剤を溶融した樹脂中にポンプで圧入し造粒し、ペレットを得て、評価を行った。押出し機の設定温度は、実施例８〜１１と比較例１７は２９０℃、実施例１２〜１５は２５０℃にして実施した。樹脂組成物中のフッ素樹脂の分散形態の観察結果と、難燃性、光沢、フローマークの評価結果を表３、４に示す。
比較例１７は、押出しが困難であった。
【０１３５】
実施例１６〜１８
表３の組成（単位は重量部）に従い、下記のように実施した。
フッ素系樹脂を除き各原料をブレンドし、２軸押出機（ＺＳＫ−２５）で混練し、押出機の途中から冷却（３℃）したフッ素系樹脂のディスパージョンを図２の様な装置で溶融した原料に滴下し、さらに混練後ペレットを得て、評価を行った。押しだし機の設定温度は、実施例１６、１８は２２０℃、実施例１７は２５０℃にして実施した。樹脂組成物中のフッ素樹脂の分散形態の観察結果と、難燃性、光沢、フローマークの評価結果を表３に示す。
【０１３６】
比較例９〜１４、１８
表４の組成（単位は重量部）に従い、下記のように実施した。
難燃剤を除き、各原料をブレンドし、２軸押出機（ＺＳＫ−２５）で混練し、押出機の途中から難燃剤を溶融した樹脂中にポンプで圧入し造粒し、ペレットを得て、評価を行った。押出し機の設定温度は、比較例９〜１２と比較例１８は２９０℃、比較例１３、１４は２５０℃にして実施した。樹脂組成物中のフッ素樹脂の分散形態の観察結果と、難燃性、光沢、フローマークの評価結果を表４に示す。
【０１３７】
比較例１５、１６
表４の組成（単位は重量部）に従い、下記のように実施した。
全原料を一括してブレンドし、シリンダー温度が比較例１５に対しては２５０℃、比較例１６に対しては２２０℃に設定された２軸押出機（ＺＳＫ−２５）で混練し、ペレットを得て、評価を行った。樹脂組成物中のフッ素樹脂の分散形態の観察結果と、難燃性、光沢、フローマークの評価結果を表４に示す。
【０１３８】
実施例１９
表３（単位は重量部）に従い、下記のように実施した。
フッ素系樹脂と難燃剤を除いて各原料をブレンドし、シリンダー温度が２５０℃に設定された２軸押出機（ＺＳＫ−２５）で混練し、まず難燃剤を溶融した樹脂中にポンプで圧入し、その後段で冷却（３℃）したフッ素系樹脂のディスパージョンを図２の様な装置で溶融した原料に滴下混練し、造粒し、ペレットを得て、評価を行った。樹脂組成物中のフッ素樹脂の分散形態の観察結果と、難燃性、光沢、フローマークの評価結果を表３に示す。
【０１３９】
比較例１９
ゴム強化樹脂Ａ−３の調製で記述した、グラフト重合体ラテックスに酸化防止剤を添加した後、塩析し、水洗浄、脱水した後加熱乾燥して得られた粉末 １５重量部に、フッ素系樹脂のディスパージョン Ｂ−１を０．５重量部を均一にブレンドし、乾燥させた。このブレンド物に、ポリカーボネート樹脂Ａ−１ ８０重量部、アクリロニトリル成分比２７重量％で、重量平均分子量が１２０，０００のＡＳ樹脂（アクリロニトリル−スチレン樹脂） ５重量部をブレンドし、シリンダー温度が２５０℃に設定された２軸押出機（ＺＳＫ−２５）で混練し、押出機の途中から難燃剤Ｃ−３ ８重量部を溶融した樹脂中にポンプで圧入し造粒し、ペレットを得て、評価を行った。樹脂組成物中のフッ素樹脂の分散形態の観察結果と、難燃性、光沢、フローマークの評価結果を表４に示す。
【０１４０】
実施例２０
ポリカーボネート樹脂Ａ−１ ８０重量部をシリンダー温度が２９０℃に設定された２軸押出機（ＺＳＫ−２５）で溶融し、まず難燃剤Ｃ−３ ８重量部を溶融した樹脂中にポンプで圧入し、その後段では、シリンダー温度を２５０℃に設定し、冷却（３℃）したフッ素系樹脂のディスパージョンＢ−１ ０．５重量部を図２の様な装置で溶融した原料に滴下混練し、さらにその後段でゴム強化樹脂Ａ−４ ２０重量部をサイドフィーダーを用いて配合し、造粒し、ペレットを得て、評価を行った。樹脂組成物中のフッ素樹脂の分散形態の観察結果と、難燃性、光沢、フローマークの評価結果を表３に示す。
【０１４１】
実施例１〜７と比較例１〜８とを比較すると分かるように、本発明の特定のネットワーク構造及び／又は特定の分岐構造を有する分散形態でフッ素系樹脂を包含する熱可塑性樹脂組成物は、そのようなネットワーク構造を有さないフッ素系樹脂組成物を包含する熱可塑性樹脂組成物に比べ、難燃性、特に燃焼時の滴下防止性に優れていることがわかる。
【０１４２】
また実施例８〜２０と比較例９〜１９とを比較すると分かるように、溶融した熱可塑性樹脂組成物にフッ素系樹脂のディスパージョンを特定のやり方で配合、溶融混練する本発明の方法は、それ以外の方法に比べて、本発明の特定のネットワーク構造及び／または特定の分岐構造を有する分散形態でフッ素系樹脂を包含する熱可塑性樹脂組成物の製造に適しており、得られる樹脂組成物は、難燃性、特に燃焼時の滴下防止性に優れているばかりでなく、その樹脂組成物を成形して得られる成型品の外観にも優れていることがわかる。
【０１４３】
【表１】

【０１４４】
【表２】

【０１４５】
【表３】

【０１４６】
【表４】

【０１４７】
【発明の効果】
本発明の難燃性樹脂組成物は、熱可塑性樹脂及び難燃剤とともに、特定の分散形態を有するフッ素系樹脂分散フィブリルを包含しており、難燃性、特に燃焼時の滴下防止性に優れているばかりでなく、その樹脂組成物を成形して得られる成型品の外観にも優れている。また、フッ素系樹脂水性ディスパージョンを用い、それを熱可塑性樹脂及び難燃剤と特定のやり方で溶融混練する本発明の方法は、特定の分散形態を有するフッ素系樹脂分散フィブリルを含有する上記の難燃性樹脂組成物の製造に適している。
よって本発明の樹脂組成物、およびその製造方法は、火災時の安全性向上への要求から材料への難燃化の要求の強い分野、例えばコンピュータやワープロ、プリンター、複写機等のＯＡ機器分野や、テレビ、ゲーム機等の一般家電分野、携帯電話のハウジング材料などの分野で特に有利に用いることが出来る。
【図面の簡単な説明】
【図１】図１は、本発明の難燃性樹脂組成物より得られる成型品の引張破断面のフッ素系樹脂フィブリルの分散形態を現す模式図である。なお、図１において実線で示した部分がフッ素系樹脂である。
【図２】図２は、本発明に用いることのできる押出し機の一例の内部構造を示す概略側面図である。
【図３】図３は、実施例４の樹脂組成物成型品の引張破断面のフッ素系樹脂フィブリルの分散形態を観察した走査電子顕微鏡写真であり、図３の写真においては、白く観察される部分がフッ素系樹脂である。
【図４】図４は、比較例５の樹脂組成物成型品の引張破断面のフッ素系樹脂フィブリルの分散形態を観察した走査電子顕微鏡写真であり、図４の写真においては、白く観察される部分がフッ素系樹脂である。
【図５】図５は、実施例８の樹脂組成物成型品の引張破断面のフッ素系樹脂フィブリルの分散形態を観察した走査電子顕微鏡写真であり、図５の写真においては、白く観察される部分がフッ素系樹脂である。
【図６】図６は、実施例１２の樹脂組成物成型品の引張破断面のフッ素系樹脂フィブリルの分散形態を観察した走査電子顕微鏡写真であり、図６の写真においては、白く観察される部分がフッ素系樹脂である。
【図７】図７は、実施例１３の樹脂組成物成型品の引張破断面のフッ素系樹脂フィブリルの分散形態を観察した走査電子顕微鏡写真であり、図７の写真においては、白く観察される部分がフッ素系樹脂である。
【図８】図８は、実施例１５の樹脂組成物成型品の引張破断面のフッ素系樹脂フィブリルの分散形態を観察した走査電子顕微鏡写真であり、図８の写真においては、白く観察される部分がフッ素系樹脂である。
【図９】図９は、比較例１４の樹脂組成物成型品の引張破断面のフッ素系樹脂フィブリルの分散形態を観察した走査電子顕微鏡写真であり、図９の写真においては、白く観察される部分がフッ素系樹脂である。
【符号の説明】
ａ：ネットワーク構造におけるフィブリルの交差点（少なくとも２本のフィブリルが互いに交差する点）
ｂ：分岐構造におけるフィブリルの分岐点（１本のフィブリルが少なくとも２本のフィブリルに分岐する点）
ｃ：０．５ミクロンを越える太さを有するフィブリル
１：押出機のホッパー
２：フッ素系樹脂のディスパージョンを添加するためのジャケット付き配管（ノズル）
３：押出機の途中の開口部
４：押出機のスクリュー
Ｐ：ポンプ[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to a flame retardant resin composition including a thermoplastic resin, a fluorine resin, and a flame retardant, and a method for producing the same. More specifically, the present invention relates to a flame retardant resin composition comprising specific amounts of a thermoplastic resin, a fluorine resin and a flame retardant, wherein the fluorine resin is present in the form of a plurality of fibrils, and the thermoplastic resin The flame retardant is present in the form of a mixture, and the fibrils are dispersed throughout the fracture surface of the fragments obtained by applying tensile stress to the test piece of the resin composition prepared by the injection molding method. 7 microns x 7 micronsAreaThe present invention relates to a flame retardant resin composition, and a method for producing the resin composition, characterized in that the dispersed fibrils exhibit a specific dispersion form when examined with a scanning electron microscope. The flame-retardant resin composition of the present invention has excellent flame retardancy, in particular, dripping prevention during combustion, and is also excellent in appearance of molded products such as high gloss and reduced flow marks.
[0002]
[Prior art]
Flame retardant regulations have been strengthened due to demands for safety improvement in the event of fire, and resin flame retardant technology has become an important technology, especially in the OA field such as computers, word processors, printers, copiers, etc. It is one of the characteristics that is indispensable in the field of general home appliances such as TVs and game machines.
[0003]
In order for the resin to be ranked at a high flame retardant level in the UL Flammability Test (UL94) according to the Underwriters Laboratories regulations in the United States, it is important that the specimen does not drip in the course of the UL vertical burn test, In order to prevent the spread of fire during an actual fire, prevention of resin dripping is an important issue.
[0004]
In response to these requests, a dripping inhibitor is added to thermoplastic resins for the purpose of preventing dripping of the resin during combustion. For example, in the resin composition described in Japanese Patent Laid-Open No. 3-190958, a silicon resin is added for the purpose of preventing dripping. However, in general, many proposals have been made to add a fluororesin having fiber-forming ability in order to improve the anti-dripping property. A composition of a fluororesin having a fiber-forming property and a thermoplastic resin is disclosed in USP 3,005,795.
[0005]
However, this is the addition of a fiber-forming fluororesin in order to increase the melt viscosity of the resin, and is not intended to prevent dripping that is the object of the present invention. The following is known as an example of using a fluororesin for improving flame retardancy, in particular, dripping prevention. For example, Japanese Unexamined Patent Publication No. 59-64651 (corresponding USP 4,463,130) discloses a system in which polytetrafluoroethylene (PTFE) is added to a resin composition comprising a polycarbonate resin, a styrene resin, and a flame retardant. ing. Japanese Laid-Open Patent Publication No. 63-286463 (corresponding USP 4,786,686) also discloses a composition in which a fluoropolymer having a fibril-forming property is contained in a composition of a polycarbonate and a rubber-like polymer.
[0006]
In these two prior arts, improvement of dripping prevention is given as an effect, but there is no mention of fibril finer fibrils, network structure and branch structure, and how to achieve them. However, no technique has been achieved that achieves a highly reproducible anti-drip property with the addition of a small amount of fluororesin.
[0007]
Japanese National Patent Publication No. 5-504582 (corresponding USP 5,109,044) and Japanese National Patent Publication No. 4-506629 (corresponding USP 5,276,078) are composed of polycarbonate, ABS resin and flame retardant. A resin composition in which a fiber structure is formed in the resin composition and PTFE having a thermal shrinkage of 15% or more is blended is disclosed.
[0008]
This resin composition also has the effect of preventing dripping at the time of combustion, and the fiber structure of PTFE and its heat shrinkability are described as factors for the manifestation of the effect. There is no mention of miniaturization, network structuring and branching structuring, and how to achieve them, and technology that achieves efficient and reproducible dripping prevention with the addition of a small amount of fluororesin is achieved It has not been.
[0009]
Moreover, the following is known as a blending method of the fluororesin into the resin composition. For example, Japanese Patent Application Laid-Open No. 60-13844 (corresponding USP 4,810,739) and Japanese Patent Application Laid-open No. Hei 2-332154 (corresponding USP 5,061,745) disclose a resin comprising a polycarbonate, an ABS resin and a flame retardant. In blending PTFE into the composition, a composition obtained by coagulating a dispersion of PTFE into an aqueous dispersion medium (solid content: about 60% by weight) and an aqueous ABS resin emulsion is obtained as a polycarbonate and a flame retardant. And a method of melt-kneading is disclosed. This method improves flame retardancy and dripping prevention, and states that surface defects are eliminated.
[0010]
Japanese Laid-Open Patent Publication No. 4-272957 (corresponding EP 483510) discloses a method of blending a fiber-forming PTFE after coating the surface of elastomer particles when blending a polycarbonate and an elastomeric impact resistance improving material. ing. It is stated that by this method, dispersion is improved, aggregates are eliminated, and a resin composition excellent in appearance and flame retardancy can be obtained.
[0011]
In Japanese Laid-Open Patent Publication No. 8-188653 (corresponding EP 718346), in dispersing a solid additive such as PTFE in a thermoplastic resin, a solvent is removed from the mixture of the thermoplastic resin solution and the PTFE dispersion by spray drying or the like. A technique for melt-kneading a composition obtained by simultaneous removal is disclosed. As a result of improving dispersibility of PTFE and the like by this method, maintenance of mechanical properties and improvement in appearance are described.
[0012]
However, even with the above method, although the fibrous PTFE dispersibility is improved as compared with the conventional method, the appearance and the like are improved, but only the dispersibility of the conventional fibrous PTFE is improved, and the dripping prevention performance of PTFE is improved. The flame retardancy and dripping prevention performance are still not sufficient, and the appearance cannot be improved sufficiently.
In recent years, in the OA field, coloring by blending a colorant is mainly performed and coating is not performed so much, and there is a demand for reduction of flow marks after molding and improvement of appearance.
[0013]
[Problems to be solved by the invention]
An object of the present invention is to provide a flame retardant property, particularly an anti-drip property, and excellent performance in improving the appearance of a molded product when a fluororesin is used as an anti-drip agent in a thermoplastic resin and flame retardant composition. It is providing the thermoplastic resin composition which has a specific form of a fluorine resin. The other subject of this invention is providing the manufacturing method which manufactures the said resin composition.
[0014]
[Means for Solving the Problems]
  As a result of intensive studies to solve the above problems, the present inventors have found that in the flame retardant resin composition containing a specific amount of thermoplastic resin, fluorine resin and flame retardant, the fluorine resin is It is present in the form of a plurality of fibrils, and the thermoplastic resin and the flame retardant are present in the form of a mixture, which is obtained by applying tensile stress to the test piece of the resin composition prepared by an injection molding method and causing it to break. 7 micron x 7 micron with fibrils dispersed throughout the fracture surfaceAreaAnd the dispersion form exhibited by the dispersed fibrils has a diameter of 0.5 microns or less over a length corresponding to 50% or more of the total extension of the dispersed fibrils, and The plurality of fibrils are composed of a network structure having one or more intersections where at least two fibrils intersect each other and a branch structure having one or more branch points where one fibril branches into at least two fibrils. 5 or more points selected from the group consisting of the intersection and the branch point are 7 microns × 7 micronsAreaIt was found that the flame retardant resin composition characterized in that it is excellent in flame retardancy, in particular, anti-dripping property, and in appearance such as gloss of the resulting molded product.
[0015]
Furthermore, the present inventors, when producing a resin composition including a thermoplastic resin, a fluorine resin, and a specific amount of a flame retardant, remove the fluorine resin from an aqueous dispersion (particle size: 0.05 to 0.5 μm; Used in the form of a solid content of 10 to 70% by weight, and melt-kneaded a composition containing a desired amount of a part or all of a thermoplastic resin and, if desired, a desired amount of a part or all of a flame retardant Then, after blending the above dispersion and melt-kneading together, if the amount of the thermoplastic resin and the flame retardant is less than the desired amount, the above amount is adjusted so that the desired amount is obtained. When the raw materials other than the dispersion, that is, the thermoplastic resin and the flame retardant, are blended in at least one additional step thereafter and further melt-kneaded in each step, the above-mentioned specific of the fluororesin is obtained in the resulting resin composition. Form Be achieved easily, flame retardancy, especially excellent anti-dripping properties, and found that superior thermoplastic resin composition in appearance can be obtained.
[0016]
Based on the above findings, the present invention has been achieved. Accordingly, one object of the present invention is to provide a highly flame-retardant resin composition that exhibits excellent flame retardancy, particularly anti-dripping properties, and appearance, in which the contained fluororesin has a specific dispersion form. It is in.
[0017]
Another object of the present invention is to provide a highly flame retardant resin composition that exhibits excellent flame retardancy, particularly anti-dripping property and appearance, in which the contained fluororesin has a specific dispersion form, and is effective and efficient. It is to provide a method of manufacturing well.
[0018]
  According to the present invention, a flame retardant resin comprising (A) 100 parts by weight of a thermoplastic resin, (B) 0.01-5 parts by weight of a fluororesin, and (C) 0.1-30 parts by weight of a flame retardant. In the composition, the fluororesin (B) is present in the form of a plurality of fibrils, and the thermoplastic resin (A) and the flame retardant (C) are present in the form of a mixture, as described in the UL-94 standard. Of a piece of resin obtained by applying sufficient tensile stress to form a fracture surface by breaking a test piece of a resin composition prepared by an injection molding method for flame retardant test of the vertical combustion method of 7 micron x 7 micron with fibrils dispersed throughout the fracture surfaceAreaAnd the dispersion form exhibited by the dispersed fibrils has a diameter of 0.5 microns or less over a length corresponding to 50% or more of the total extension of the dispersed fibrils, and The plurality of fibrils are composed of a network structure having one or more intersections where at least two fibrils intersect each other and a branch structure having one or more branch points where one fibril branches into at least two fibrils. 5 or more points selected from the group consisting of the intersection and the branch point are 7 microns × 7 micronsAreaThere is provided a flame retardant resin composition characterized by the following.
[0019]
Next, in order to facilitate understanding of the present invention, basic features and preferred embodiments of the present invention will be listed first.
[0020]
1. (A) A polycarbonate resin having a weight average molecular weight of 10,000 to 80,000, or 5 to 98 parts by weight of a polycarbonate resin having a weight average molecular weight of 10,000 to 80,000, and at least a rubber polymer capable of graft copolymerization with the rubber polymer. 100 parts by weight of a thermoplastic resin comprising 95 to 2 parts by weight of a rubber-reinforced resin containing a graft copolymer obtained by graft copolymerizing one kind of vinyl compound and a vinyl polymer, (B) 0.01% fluorine-based resin In the flame retardant resin composition comprising -5 parts by weight and (C) 3-22 parts by weight of the flame retardant, the fluororesin (B) is present in the form of a plurality of fibrils, and the thermoplastic resin (A ) And flame retardant (C) are present in the form of a mixture, for flame retardant testing by the vertical combustion method described in the UL-94 standard.Of the following conditionsOf resin composition made by injection molding method1/2 x 5 x 1/16 inchTest piecesWas pulled at a speed of 5 mm / min using a tensile tester to break the test piece.7 micron x 7 micron with fibrils dispersed throughout the fracture surfaceAreaAnd the dispersion form exhibited by the dispersed fibrils has a diameter of 0.5 microns or less over a length corresponding to 50% or more of the total extension of the dispersed fibrils, and The plurality of fibrils are composed of a network structure having one or more intersections where at least two fibrils intersect each other and a branch structure having one or more branch points where one fibril branches into at least two fibrils. 5 or more points selected from the group consisting of the intersection and the branch point are 7 microns × 7 micronsAreaA flame retardant resin composition, which is present in
(Test piece injection molding conditions)
  Molding machine: MJEC-10 (made by Modern Machinery, Japan)
  Molding temperature: 280 ° C. for polycarbonate resin alone, 260 ° C. for thermoplastic resin consisting of 5 to 98 parts by weight of polycarbonate resin and 95 to 2 parts by weight of rubber reinforced resin
  Mold temperature: 80 ° C. for polycarbonate resin alone, 60 ° C. for thermoplastic resin consisting of 5 to 98 parts by weight of polycarbonate resin and 95 to 2 parts by weight of rubber reinforced resin
Injection speed: 500 (setting value)
[0021]
2. The plurality of fibrils have a diameter of 0.5 microns or less over a length corresponding to 70% or more of the total extension, and 10 or more points selected from the group consisting of the intersection and the branch point are 7 microns. × 7 micronsArea2. The resin composition according to item 1, which is present in item 1.
[0024]
3. 3. The resin composition according to item 1 or 2, wherein the fluororesin (B) is polytetrafluoroethylene (PTFE).
[0025]
4. 3. The resin composition according to item 1 or 2, wherein the flame retardant (C) is a halogen flame retardant.
[0026]
5. 3. The resin composition according to item 1 or 2, wherein the flame retardant (C) is a phosphate ester flame retardant.
[0027]
6. 3. The resin composition according to item 1 or 2, wherein the flame retardant (C) is a condensed phosphate ester flame retardant.
[0030]
7. 1- above6A molded product obtained from the resin composition according to any one of the above.
[0031]
Hereinafter, the present invention will be described in detail.
Examples of the thermoplastic resin (A) used in the present invention include styrene polymer resins, olefin polymer resins, polyamide resins, oxymethylene polymer resins, phenylene ether polymer resins, polycarbonate resins, and polyesters. Engineering plastics such as resin and methyl methacrylate polymer resin. These resins may be either homopolymers or copolymers. These may be used alone or in combination of two or more.
[0032]
Here, styrene polymer resin, polyester resin, and polycarbonate resin are particularly preferable as the thermoplastic resin. The styrene polymer resin is a rubber-modified styrene polymer resin or a rubber non-modified styrene polymer resin. More preferred as the thermoplastic resin is a rubber-modified styrene polymer resin or a resin composition comprising a rubber-modified styrene polymer resin and a polycarbonate resin. [Hereinafter, the rubber-modified styrenic polymer resin is often referred to as “rubber reinforced resin (Ad)”, and the polycarbonate resin is referred to as “polycarbonate resin (Ae)”. ]
[0033]
Examples of the vinyl monomer used in the rubber-modified styrene polymer resin or the rubber non-modified styrene polymer resin include aromatic vinyl compounds such as styrene, α-methylstyrene, and paramethylstyrene, methyl methacrylate, and methyl acrylate. , Alkyl (meth) acrylates such as butyl acrylate and ethyl acrylate, (meth) acrylic acids such as acrylic acid and methacrylic acid, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, and α, β- such as maleic anhydride Examples thereof include maleimide monomers such as unsaturated carboxylic acid, N-phenylmaleimide, N-methylmaleimide, and N-cyclohexylmaleimide, and glycidyl group-containing monomers such as glycidyl methacrylate.
[0034]
Among them, preferred are aromatic vinyl compounds, alkyl (meth) acrylates, vinyl cyanide monomers and maleimide monomers, and more preferred are styrene, acrylonitrile, N-phenylmaleimide and butyl acrylate. is there. These vinyl compounds can be used alone or in combination of two or more.
[0035]
The rubber-modified styrenic polymer resin is a polymer in which a rubber-like polymer is dispersed in a particle form in a matrix made of a vinyl aromatic polymer. It can be obtained by adding a monomer and, if necessary, a vinyl monomer copolymerizable therewith, and subjecting the monomer mixture to known bulk polymerization, bulk suspension polymerization, solution polymerization, or emulsion polymerization.
[0036]
As said rubber-like polymer, if a glass transition temperature is 0 degrees C or less, it can be used. Specifically, diene rubber such as polybutadiene, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, acrylic rubber such as polybutyl acrylate, polyisoprene, polychloroprene, ethylene-propylene rubber, ethylene- Propylene-diene terpolymer rubber, block copolymers such as styrene-butadiene block copolymer rubber and styrene-isoprene block copolymer rubber, and hydrogenated products thereof can be used.
[0037]
Examples of rubber-modified styrene polymer resins include impact-resistant polystyrene, ABS resin (acrylonitrile-butadiene-styrene copolymer), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), AES resin (acrylonitrile-ethylene). Propylene rubber-styrene copolymer) and the like.
[0038]
Next, a preferred composition and production method of the rubber reinforced resin (Ad) used in the present invention will be described.
The rubber-reinforced thermoplastic resin (Ad) used in the present invention can be obtained by graft-polymerizing a vinyl compound that can be graft-polymerized to a rubber-like polymer, and is produced by homopolymerization of the vinyl compound in this graft-polymerization process. Vinyl polymers may be included. In the present invention, a vinyl polymer may be produced separately from the graft polymer and blended with the above graft polymer. Of the vinyl polymers contained in the rubber-reinforced thermoplastic resin (Ad) in the present invention, at least 1% by weight of the vinyl polymer is preferably grafted to the rubber-like polymer.
[0039]
Rubber-like polymers used in the present invention include polybutadiene, polyisoprene and polychloroprene; conjugated diene rubbers such as butadiene-styrene copolymers and butadiene-acrylonitrile copolymers; ethylene-propylene rubbers; and ethyl acrylate, Acrylic rubbers such as butyl acrylate are preferable, and polybutadiene, butadiene-styrene copolymer and butadiene-acrylonitrile copolymer which are conjugated diene rubbers are preferable. Moreover, these can be used in combination of 2 or more types.
[0040]
The content of the rubber-like polymer in the rubber-reinforced thermoplastic resin (Ad) is 5 to 65% by weight, preferably 10 to 60% by weight. If it is less than 5% by weight, impact resistance cannot be obtained, and if it exceeds 65% by weight, the fluidity during molding and the gloss of the molded product are undesirably lowered.
[0041]
Regarding the preferable particle size of the rubbery polymer in the rubber-reinforced thermoplastic resin (Ad), the vinyl weight constituting the sea part in the rubber-reinforced resin (Ad) having an island-in-sea configuration is described. For example, in the case of an ABS resin, the particle diameter is 150 to 600 nm, preferably 200 to 500 nm, more preferably 250 to 450 nm, as measured with particles before graft polymerization. If the particle diameter is smaller than 150 nm, impact resistance cannot be obtained, and if it exceeds 600 nm, the gloss value of a molded product produced from the resin composition obtained is lowered.
[0042]
Examples of vinyl monomers that can be graft-polymerized on the rubber-like polymer particles used in the present invention include aromatic vinyl compounds such as styrene, α-methylstyrene, and paramethylstyrene; methyl methacrylate, methyl acrylate, butyl acrylate, ethyl acrylate, and the like. Alkyl (meth) acrylates; (meth) acrylic acids such as acrylic acid and methacrylic acid; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; α, β-unsaturated carboxylic acids such as maleic anhydride; N- Maleimide monomers such as phenylmaleimide, N-methylmaleimide and N-cyclohexylmaleimide; and glycidyl group-containing monomers such as glycidyl methacrylate are preferable, and aromatic vinyl compounds and alkyl (meth) acrylates are preferable. , Cyanide Le monomer, a maleimide monomer, more preferably, styrene, acrylonitrile, N- phenylmaleimide, butyl acrylate.
These vinyl monomers can be used alone or in combination of two or more.
[0043]
Examples of the monomer constituting the vinyl polymer that can be contained in the rubber-reinforced thermoplastic resin (Ad) include aromatic vinyl compounds such as styrene, α-methylstyrene, and paramethylstyrene; methyl methacrylate, methyl acrylate Alkyl (meth) acrylates such as butyl acrylate and ethyl acrylate; (meth) acrylic acids such as acrylic acid and methacrylic acid; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; α, β- such as maleic anhydride Unsaturated carboxylic acids; maleimide monomers such as N-phenylmaleimide, N-methylmaleimide, N-cyclohexylmaleimide; glycidyl group-containing monomers such as glycidylmethacrylate, preferably aromatic vinyl Compounds, alkyl (meth) acrylates, Ann vinyl monomer, a maleimide monomer, more preferably, styrene, acrylonitrile, N- phenylmaleimide, butyl acrylate.
These vinyl monomers can be used singly or in combination of two or more or copolymerized.
[0044]
The method for producing the rubber-reinforced thermoplastic resin (Ad) in the present invention is not particularly limited, but an emulsion graft polymerization method in which a vinyl compound is graft-polymerized on a rubber-like polymer latex produced by emulsion polymerization, and Examples thereof include a two-stage polymerization method in which a vinyl compound is further added to the reaction mixture containing the graft copolymer obtained by the above emulsion graft polymerization, followed by further graft polymerization by solution polymerization or suspension polymerization. These can be continuous, batch, or semi-batch. In addition, a graft polymer having a high rubber content is prepared in advance by the above 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. The method of making the rubber content of.
[0045]
As a method for producing the rubber-reinforced thermoplastic resin (Ad) in the present invention, a rubbery polymer is produced by emulsion polymerization, and then a vinyl compound is continuously added together with an initiator, a molecular weight regulator and the like. An emulsion graft polymerization method in which grafting is carried out by stretching is preferred.
Moreover, although there is no limitation in particular also at the time of superposition | polymerization, neutral vicinity (pH 7-9) is preferable from the surface of graft reaction.
[0046]
As an emulsifier used for emulsion polymerization, an emulsifier generally used for emulsion polymerization can be used. Examples of such an emulsifier include rosinate, higher fatty acid salt, alkyl sulfate ester salt, alkylbenzene sulfonate, alkyl Anionic emulsifiers such as diphenyl ether disulfonate, polyoxyethylene alkylphenyl ether sulfate and dialkyl sulfosuccinate, and nonionic emulsifiers such as polyoxyethylene alkyl ether and polyoxyethylene alkylphenyl ether are listed.
In addition to the above emulsifiers, radically polymerizable emulsifiers having a double bond in the molecule can also be used.
[0047]
A radically polymerizable emulsifier having a double bond in the molecule (hereinafter referred to as a polymerizable emulsifier) has a hydrophilic group and a hydrophobic group in the compound, and is a gas-liquid, liquid-liquid, solid-liquid interfacial tension. Among compounds having the ability to reduce the ionic properties of the conjugated diene rubber, aromatic vinyl compound, vinyl cyanide compound and / or (meth) acrylic acid ester compound. It means what can be radically copolymerized. The hydrophilic group of the polymerizable emulsifier may be any of anionic, nonionic, and cationic, but preferably has anionic, more preferably nonionic and anionic properties. Examples of the polymerizable emulsifier include those represented by the following chemical formulas 1 to 9, but are not limited thereto.
First, there is a polymerizable emulsifier represented by the following chemical formula 1.
[0048]
[Chemical 1]

[Where X⁶Represents a (meth) allyl group, a (meth) acryloyl group or a 1-propenyl group. Y⁶Is hydrogen or -SO_ThreeM⁶(M⁶Represents hydrogen, alkali metal, alkaline earth metal, ammonium, or hydroxyalkylammonium having 1 to 4 carbon atoms. Sulfate group forming group represented by the formula:₂COOM⁶(M⁶Represents hydrogen, alkali metal, alkaline earth metal, ammonium, or hydroxyalkylammonium having 1 to 4 carbon atoms. ) Or a phosphate monoester salt-forming group represented by the following chemical formula 2. R^{6 '}Is an alkyl group having 1 to 18 carbon atoms, an alkenyl group or an aralkyl group, R^{6 ''}Is hydrogen or an alkyl, alkenyl or aralkyl group having 1 to 18 carbon atoms, R^{6 '''}Is hydrogen or a propenyl group, A⁶Represents an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, and m represents an integer of 1 to 200. ]
[0049]
[Chemical formula 2]

(In the formula, each M^{6 '}Is hydrogen, alkali metal, alkaline earth metal, ammonium or hydroxyalkylammonium having 1 to 4 carbon atoms, and each M^{6 '}May be the same or different. )
[0050]
Other examples include (meth) allyl glyceryl ether derivatives and (meth) acryl glyceryl ester derivatives represented by the following chemical formula 3.
[0051]
[Chemical 3]

[Where X⁷Represents a (meth) allyl group or a (meth) acryloyl group. Y⁷Is hydrogen or -SO_ThreeM⁷(M⁷Represents hydrogen, an alkali metal, an alkaline earth metal, ammonium or a hydroxyalkylammonium having 1 to 4 carbon atoms. Sulfate group forming group represented by the formula:₂COOM^{7 '}(M^{7 '}Represents hydrogen, alkali metal, or alkaline earth metal. ), A phosphate monoester salt-forming group represented by Chemical Formula 2 above, or a group represented by Chemical Formula 4 below. Z⁷Represents an alkyl group having 8 to 30 carbon atoms, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkylaryl group, a substituted alkylaryl group, an aralkylaryl group, a substituted aralkylaryl group, an acyl group or a substituted acyl group. A⁷Represents an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, m represents an integer of 0 to 100, and n represents an integer of 0 to 50. ]
[0052]
[Formula 4]

(Where M^{6 ''}Is an alkyl group having 8 to 30 carbon atoms which may have hydrogen, an alkali metal, an alkaline earth metal, ammonium, a hydroxyalkyl ammonium having 1 to 4 carbon atoms or an alkylene oxide unit having 2 to 4 carbon atoms, M^{6 '''}Are hydrogen, alkali metal, alkaline earth metal, ammonium, and hydroxyalkylammonium having 1 to 4 carbon atoms. )
Another example is a succinic acid derivative represented by the following chemical formula 5.
[0053]
[Chemical formula 5]

[Where X⁸Represents a (meth) allyl group or a (meth) acryloyl group. B⁸, B^{8 '}Is represented by Y⁸Or Z⁸Indicates B⁸, B^{8 '}Is different. Y⁸Is M⁸Or -SO_ThreeM⁸(M⁸Represents hydrogen, alkali metal, alkaline earth metal, ammonium, or hydroxyalkylammonium having 1 to 4 carbon atoms. ) Represents a sulfate ester salt-forming group. Z⁸Represents an alkyl group or alkenyl group having 8 to 30 carbon atoms. A⁸Is an alkylene group having 2 to 4 carbon atoms and an alkylene group having a substituent, and m and n are integers of 0 to 50. ]
Another example is a compound represented by the following chemical formula (6).
[0054]
[Chemical 6]

[Where X⁹Represents a (meth) allyl group or a (meth) acryloyl group. Y⁹Is hydrogen or -SO_ThreeM⁹(M⁹Represents hydrogen, alkali metal, alkaline earth metal, ammonium, or hydroxyalkylammonium having 1 to 4 carbon atoms. Sulfate group forming group represented by the formula:₂COOM⁹(M⁹Represents a carboxylate represented by hydrogen, alkali metal, alkaline earth metal, ammonium or hydroxyalkylammonium having 1 to 4 carbon atoms. Each R⁹Are hydrogen or an alkyl group having 1 to 25 carbon atoms, which may be the same or different, and each R^{9 '}Represents an alkyl group having 1 to 25 carbon atoms, a benzyl group, or a styryl group, which may be the same or different, and p represents an integer of 0 to 2. A⁹Is an alkylene group having 2 to 4 carbon atoms and an alkylene group having a substituent, and m and n represent an integer of 0 to 50. ]
Furthermore, other examples include (meth) allyl ether derivatives and (meth) acrylic ester derivatives represented by the following chemical formula 7.
[0055]
[Chemical 7]

[Where X²⁷Represents a (meth) allyl group or a (meth) acryloyl group. Y²⁷Is hydrogen, a methyl group, or -SO_ThreeM²⁷(M²⁷Represents hydrogen, alkali metal, alkaline earth metal, ammonium, or hydroxyalkylammonium having 1 to 4 carbon atoms. Sulfate group forming group represented by the formula:₂COOM²⁷(M²⁷Represents hydrogen, an alkali metal, an alkaline earth metal, ammonium or a hydroxyalkylammonium having 1 to 4 carbon atoms. ) Or a phosphate monoester salt-forming group represented by Chemical Formula 2. Z²⁷Represents an alkyl group having 8 to 30 carbon atoms. A²⁷Represents an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, m represents an integer of 0 to 20, and n represents an integer of 0 to 50. ]
Furthermore, the diol compound represented by following Chemical formula 8 is mention | raise | lifted as another example.
[0056]
[Chemical 8]

(Where A³⁰Is an alkylene group having 2 to 4 carbon atoms and R³⁰Is a hydrocarbon group having 8 to 24 carbon atoms, and R^{30 '}Is a hydrogen or methyl group, m and n are each a number from 0 to 100 such that m + n is a value between 0 and 100;³⁰Is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or a hydroxyalkylammonium having 1 to 4 carbon atoms. )
Another example is a compound represented by the following chemical formula 9.
[0057]
[Chemical 9]

[Where X³²Represents (meth) allyl group, (meth) allyloxy group or (meth) acryloyl group, (meth) acryloyloxy group or Y³²Is hydrogen or -SO_ThreeM³²(M³²Represents hydrogen, an alkali metal, an alkaline earth metal, ammonium or a hydroxyalkylammonium having 1 to 4 carbon atoms. Sulfate group forming group represented by the formula:₂COOM³²(M³²Represents hydrogen, an alkali metal, an alkaline earth metal, ammonium or a hydroxyalkylammonium having 1 to 4 carbon atoms. ), A phosphate monoester salt-forming group represented by Chemical Formula 2, or a sulfosuccinic acid monoester salt-forming group represented by Chemical Formula 4. Z³²Represents an alkylene group which may have a substituent having 6 to 30 carbon atoms. A³²Represents an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, and n and m represent an integer of 0 to 50. ]
[0058]
Embedded image

(Where R^{32 '}, R^{32 ''}Represents hydrogen or a methyl group. )
[0059]
The polycarbonate resin (Ae) used in the present invention is an aromatic polycarbonate resin, which is a method based on a reaction in a homogeneous system or a heterogeneous two-phase interface reaction from an aromatic dihydroxy compound and phosgene, or again. An aromatic polycarbonate resin produced by any of the melt transesterification methods by the reaction of an aromatic dihydroxy compound and a carbonic acid diester can be used.
[0060]
As the aromatic dihydroxy compound, bisphenols are preferable, and 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A) is particularly preferable. Moreover, you may substitute a part or all of bisphenol A by another dihydric phenol compound. Examples of aromatic dihydroxy compounds other than bisphenol A include compounds such as hydroquinone, 4,4-dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, and bis (4-hydroxyphenyl) ketone. It is. It may be a homopolymer of these aromatic dihydroxy compounds, two or more types of copolymers, or a blend thereof.
[0061]
As the carbonic acid diester used in the melt transesterification method, diaryl carbonates, particularly diphenyl carbonate, are preferred.
[0062]
Aromatic polycarbonates can be branched by adding a small amount of 3 or 3 or more polyfunctional compounds as long as the object of the present invention is not impaired. Examples of the polyfunctional compound include polyhydric phenol.
[0063]
The polycarbonate resin (Ae) in the present invention preferably has a weight average molecular weight in the range of 5,000 to 300,000. When the weight average molecular weight is smaller than the above range, the mechanical strength is unfavorably low, and when the weight average molecular weight is larger than the above range, the fluidity is lowered. More preferably, the weight average molecular weight is in the range of 7000 to 100,000, more preferably in the range of 10,000 to 80,000.
[0064]
The terminal molecular structure of the polymer is not particularly limited, but can be one or more end groups selected from a hydroxyl group, an aryl carbonate group, and an alkyl carbonate group. The hydroxyl group is a terminal derived from the aromatic dihydroxy compound used, and the proportion thereof can be used from a substance which does not contain substantially to 50% of all terminals.
[0065]
As the thermoplastic resin (A), it is particularly preferable to use a resin composition composed of a polycarbonate resin (Ae) and a rubber reinforced resin (Ad). The preferable blending composition is 95 to 2 parts by weight of the rubber-reinforced resin (Ad) with respect to 5 to 98 parts by weight of the polycarbonate resin (Ae), and more preferably, the polycarbonate resin (Ae) 20 The rubber-reinforced resin (Ad) is 80 to 10 parts by weight with respect to 90 parts by weight, and more preferably the rubber-reinforced resin (Ad) is 60 to 80 parts by weight with respect to 40 to 85 parts by weight of the polycarbonate resin (Ae). 15 parts by weight.
[0066]
The fluororesin (B) used in the present invention has a fibril-like shape mainly having a thickness of 0.5 μm or less in the resin composition, and the fibrils are present in a network structure and / or branched form. The system resin is generally selected from perfluoroalkane resins such as polytetrafluoroethylene (PTFE) and fluorinated ethylene propylene (FEP) resin, and perfluoroalkoxy (PFA) resin, and PTFE is particularly preferable.
[0067]
As for the compounding quantity of a fluorine resin, 0.01-5 weight part is preferable with respect to 100 weight part of thermoplastic resins (A). When it is less than 0.01 part, the effect of preventing dripping is not sufficient, and when it exceeds 5 parts by weight, the mechanical strength and processing fluidity of the resin are lowered. More preferably, it is 0.02-2 weight part, Most preferably, it is 0.1-1 weight part.
[0068]
In the present invention, the dispersion form in the resin composition of the fluorinated resin (B) in the form of fibril is specifically observed by the following method. That is, a test piece for UL94 vertical combustion test of a resin composition is formed by injection molding, and then a tensile fracture surface obtained by a tensile test is observed with a scanning electron microscope (SEM), whereby a plurality of fluororesin fibrils are obtained. Confirm that it exists in the dispersed form described above. In the present invention, conditions other than those described above in SEM observation are not particularly limited. For example, a resin composition comprising a polycarbonate resin (Ae) and a rubber-reinforced resin (Ad) as the thermoplastic resin (A). When used, SEM observation is actually performed under the following conditions.
[0069]
(injection molding)
Molding machine: M-JEC10 (made by Modern Machinery, Japan)
Molding temperature: 260 ° C
Mold temperature: 60 ℃
Injection speed: 500 (setting value)
Test piece: 1/2 x 5 x 1/16 inch
(Preparation of sample for SEM observation)
Using a tensile tester (Autograph 5000D, manufactured by Shimadzu Corporation, Japan), the sample is pulled at a speed of 5 mm / min until it breaks.
[0070]
(SEM observation)
Pre-treatment: Gold vapor deposition is performed on the sample fracture surface so that the gold thickness is 200 angstroms or more. (Vapor deposition equipment: JFC 1500 QUICK AUTO COATER, manufactured by JEOL, Japan)
Observation device: JSM-5300 (made by JEOL, Japan)
Acceleration voltage: 15 kV
[0071]
Below, the dispersion | distribution form which has the network structure and / or branch structure which a fluorine-type resin dispersion | distribution fibril shows in this invention is demonstrated with reference to FIG. 1, FIG. FIG. 1 is a schematic diagram showing an example of the dispersion form of the fluororesin fibrils, and FIGS. 3 to 9 are SEM photographs showing various examples of the dispersion form. The fluororesin is a portion indicated by a solid line in FIG. 1 and is a portion that appears white in FIGS.
[0072]
  As described above, in the present invention, a fracture surface is formed by breaking a test piece of a resin composition prepared by an injection molding method for a flame retardant test by the vertical combustion method described in the UL-94 standard. 7 micron x 7 micron with fibrils dispersed throughout the fracture surface of the fragments obtained by applying sufficient tensile stress toAreaAnd the dispersion form exhibited by the dispersed fibrils has a diameter of 0.5 microns or less over a length corresponding to 50% or more of the total extension of the dispersed fibrils, and The plurality of fibrils are composed of a network structure having one or more intersections where at least two fibrils intersect each other and a branch structure having one or more branch points where one fibril branches into at least two fibrils. 5 or more points selected from the group consisting of the intersection and the branch point are 7 microns × 7 micronsAreaIt is necessary to exist.
[0073]
  The fluorinated resin fibrils need to have a diameter of 0.5 microns or less over a length corresponding to 50% or more of the total length of the fibrils. Although it is possible for fibrils having a thickness of more than 0.5 micron as shown by reference c in FIG. 1 to be present, for example, as seen in the SEM photograph of FIG.AreaIt is necessary to have a diameter of 0.5 microns or less over a length corresponding to 50% or more of the total length of fibrils present in the membrane, preferably 70% or more, more preferably 90% or more. If the ratio of the length of fibrils having a diameter of 0.5 microns or less to the total length of fibrils is less than 50%, an excellent drip prevention effect cannot be obtained.
[0074]
  Further, the network structure referred to in the present invention has one or more intersections where two or more fibrils intersect each other, as indicated by the symbol a in the schematic diagram of FIG. In addition, the branch structure referred to in the present invention has one or more branch points where one fibril branches into at least two fibrils, as indicated by a symbol b in the schematic diagram of FIG. Both the network structure and the branch structure have a three-dimensional extent. 5 or more points selected from the group consisting of this intersection and branch point are the 7 microns × 7 microns.AreaMust be present. If the number of points selected from the group consisting of the intersection and the branch point is less than 5, an excellent dripping prevention effect cannot be obtained.
[0075]
  7 micron x 7 micron observed by SEMAreaThe fact that the fluorine-based resin dispersed fibrils exhibit the above specific dispersion form reflects the dense presence of the fluorine-based resin dispersed fibrils in the resin composition. It is presumed that the presence of such dense fluorine-based resin-dispersed fibrils causes three-dimensional shrinkage of the fibrils during combustion, thereby achieving effective dripping prevention.
[0076]
The fluorine-based resin is produced by suspension polymerization or emulsion polymerization as described in, for example, “Fluorine Resin Handbook” (Japan, Nikkan Kogyo Shimbun, 1990). For the purpose of the present invention, a fluororesin synthesized by emulsion polymerization is preferred, a fluororesin latex is obtained by emulsion polymerization using water as a solvent, and the resulting latex is coagulated / dried fine powder, An aqueous dispersion obtained by concentrating and stabilizing the above fluororesin latex is used.
[0077]
A fluororesin aqueous dispersion is commercially available. Among the commercially available fluororesin aqueous dispersions, as an example of PTFE dispersion, “Teflon 30-J” (solid content concentration 60% by weight, particle size 0. 0%) commercially available from Mitsui DuPont Fluorochemical Co., Ltd., Japan. 23 micron, surfactant concentration is 6% by weight with respect to PTFE weight, pH value is 9 to 10), and “Polyflon TFE Dispersion D-1” (solid content concentration of about 60) available from Daikin Industries of Japan Weight%, particle diameter 0.20 to 0.40 micron, pH value 9 to 10) and the like.
[0078]
In the present invention, it is particularly preferable to use a fluororesin aqueous dispersion. The preferable solid content concentration of the fluororesin aqueous dispersion is 10 to 70% by weight. Usually, commercially available fluororesin aqueous dispersions are supplied at a solid content concentration of around 60% by weight, but if necessary, dilute with water or concentrate to adjust to the desired concentration. Can be used.
[0079]
In the resin composition, a resin having a fiber forming ability is used in the resin composition in order to form a network structure and / or a branched structure at the time of melt kneading with a thermoplastic resin or a flame retardant. USP 3,005,795, 3,671,487, 4,463,130 can be referred to for the resin.
[0080]
The flame retardant (C) in the present invention is a so-called general flame retardant. In addition to phosphorus compounds and halogen organic compounds, nitrogen-containing organic compounds such as melamine, magnesium hydroxide, aluminum hydroxide, antimony oxide, oxidation Inorganic compounds such as bismuth can be used. Moreover, metal oxides such as zinc oxide and tin oxide, inorganic phosphorus compounds such as red phosphorus, phosphine, hypophosphorous acid, phosphorous acid, metaphosphoric acid, pyrophosphoric acid and anhydrous phosphoric acid, carbon fiber, glass fiber, etc. Inorganic fibers, expanded graphite, silica, silica-based glass melts, and the like are used, and phosphorus compounds, halogen-based organic compounds, and combinations of halogen-based organic compounds and antimony oxide are preferable. Moreover, a phosphate ester type flame retardant and a condensed phosphate ester type flame retardant can be mentioned.
[0081]
The halogen-based organic compound refers to a halogen-based organic compound generally used as a flame retardant and a halogen-containing phosphate ester. 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 and the like, a halogen-based organic compound having a structure of the following chemical formula 11 is preferable, and a halogen-based organic compound of the following chemical formula 14 is particularly preferable.
[0082]
Embedded image

n = 0 or a natural number, X independently represents chlorine or bromine, i, j, k and p are each an integer of 1 to 4, R¹And R²Are each independently hydrogen, a methyl group,
[0083]
Embedded image

A phenyl group or the following chemical formula 13 (where m represents 0, 1, 2 or 3)
[0084]
Embedded image

A group that can be represented by
[0085]
Embedded image

n = 0 or natural number, R^ThreeAnd R^FourAre each independently
[0086]
Embedded image

A group that can be represented by the formula:
[0087]
Embedded image

A group that can be represented by
[0088]
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 (tri Bromoneopentyl phosphate) and condensed phosphate esters thereof, and the like. 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.
[0089]
Examples of phosphate ester flame retardants include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, There are phosphate esters such as dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate, and compounds obtained by modifying these with various substituents.
[0090]
As the condensed phosphate ester flame retardant, one represented by the following general formula 17 can be used.
[0091]
Embedded image

(In the formula, n is an integer of 1 to 10, Ar¹~ Ar^FourEach independently represents a phenyl group, a tolyl group or a xylyl group. When n is 2 or more, a plurality of Ar^FourMay be the same or different. R^FiveIs a group selected from A1 to A4 of the chemical formula 18 below. )
[0092]
Embedded image

Among the condensed phosphate ester flame retardants represented by the above chemical formula 17, preferred are the condensed phosphate ester compounds represented by the following chemical formulas 19 to 22, and these phosphate ester compounds have a flame-retardant effect. And heat resistance is particularly excellent.
[0093]
Embedded image

[0094]
Embedded image

[0095]
Embedded image

[0096]
Embedded image

(Wherein Ar^Five~ Ar⁷Are each independently a phenyl group, a tolyl group, or a xylyl group other than a 2,6-xylyl group, and R is R in the formula (5)^FiveIt is the same as A4 defined in. )
These can be used alone or in combination of two or more.
[0097]
The blending amount of the flame retardant is determined according to the desired level of flame retardancy, but it is necessary to be 0.1 to 30 parts by weight with respect to 100 parts by weight of the thermoplastic resin. If it is less than 0.1 part by weight, the desired 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.
[0098]
The flame retardant aid is preferably a compound containing an element belonging to Group V in the periodic table of elements, specifically, a nitrogen-containing compound, a phosphorus-containing compound, antimony oxide, or bismuth oxide. 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.
[0099]
The addition amount of the flame retardant aid is preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A). When the amount is less than 0.5 part by weight, the effect of the flame retardant aid is not sufficient, and when the amount exceeds 20 parts by weight, the mechanical strength and processing fluidity of the resin are lowered. More preferably, it is 1-15 weight part, Most preferably, it is 1-10 weight part.
[0100]
As a method for producing a resin composition having a desirable dispersion form of fluorine-based resin fibrils in the present invention, for example, when using fine powder as the fluorine-based resin, a fluorine-based resin pulverized in a state of not exceeding −20 ° C., and It can also be achieved by blending the cooled raw resin at a temperature of 10 ° C. or lower and melt-kneading. However, among the components constituting the resin composition of the present invention, a part or all of a desired amount of thermoplastic resin, excluding fluorine-based resins such as fine powder and dispersion, and a desired amount if desired. It is preferable to employ a production method in which a part or all of the flame retardant is melt-kneaded and then mixed with a fluororesin.
[0101]
Most preferably, it is preferable to use a dispersion as the fluorine-based resin and mix it with the molten thermoplastic resin. By this method, latex particles are uniformly dispersed in the molten resin, aggregation and the like are suppressed, and uniform fiberization is promoted by shearing in the resin composition, and a network structure and / or a branched structure of the fluororesin It is considered that is easily formed.
[0102]
Below, the preferable manufacturing method of the resin composition of this invention is demonstrated in detail.
As a preferable production method, for example, the target flame retardant resin composition includes 100 parts by weight of a thermoplastic resin, 0.01 to 5 parts by weight of a fluororesin, and 0.1 to 30 parts by weight of a flame retardant. If it is a composition, first, 10 to 100 parts by weight of the thermoplastic resin (A) and 0 to 30 parts by weight of the flame retardant (C) are melt-kneaded to form a melt-kneaded product. After adding 0.01 to 5 parts by weight of fluororesin (B) and melt-kneading together to form a fluororesin-containing thermoplastic resin composition, if thermoplastic resin (A) / flame retardant (C) When the weight ratio of 100 / 0.1 to 30 is not satisfied, the component (A) and / or the component (C) is added to the fluororesin-containing thermoplastic resin composition so as to satisfy this ratio. And a method of further melt-kneading.
[0103]
That is, in the present invention,
In the method for producing a flame retardant resin composition comprising 100 parts by weight of a thermoplastic resin, 0.01 to 5 parts by weight of a fluororesin, and 0.1 to 30 parts by weight of a flame retardant,
(1) 10-100 parts by weight of thermoplastic resin (A) and 0-30 parts by weight of flame retardant (C) are melt-kneaded to form a melt-kneaded product,
(2) 0.01 to 5 parts by weight of the fluororesin (B) is added to the melt-kneaded product and melt-kneaded together to form a fluororesin-containing thermoplastic resin composition.
In this case, the fluororesin (B) is used in the form of an aqueous dispersion in which the fluororesin is dispersed in an aqueous dispersion medium, and the aqueous dispersion has a fluororesin particle size of 0.05 to 0.5 micron, solid content is 10 to 70% by weight,
When the component (A) and the component (C) to be melt-kneaded in the step (1) do not satisfy the desired ratio in the range of the component (A) / component (C) weight ratio of 100 / 0.1-30, At least one component selected from the component (A) and the component (C) is added to the fluororesin-containing thermoplastic resin composition formed in the step (2) with a component (A) / component (C) weight ratio of 100 / An amount necessary to satisfy a desired ratio of 0.1 to 30, and then further melt-kneading in each step in at least one additional step;
A method for producing a flame retardant resin composition is provided.
[0104]
Melt-kneading can be performed by a conventionally known method. For example, components other than fluororesin are uniformly mixed with a Henschel mixer, super mixer, turntable mixer, ribbon blender, etc., and then melted and kneaded with a single screw extruder, twin screw extruder, Banbury mixer, etc. The resin composition of this invention can be manufactured by mix | blending the dispersion of a fluorine-type resin in a resin composition, and also melt-kneading.
[0105]
Moreover, as long as the effect of this invention is acquired, it is arbitrary to add additives, such as a well-known stabilizer (for example, antioxidant, a ultraviolet absorber, etc.), a lubricant, a mold release agent, an antistatic agent, a coloring agent, a filler. In particular, the combined use of phosphorus stabilizers (phosphorus antioxidants, heat stabilizers, etc.) is preferable, and the blending order may be either before or after blending the fluororesin.
[0106]
Examples of the filler that can be optionally used in the resin composition of the present invention include glass fiber, glass flake, carbon fiber, talc, and mica. These types may be determined according to the required mechanical strength, rigidity, molding processability, and heat resistance. A compounding quantity is the range of 0-50 weight part with respect to 100 weight part of thermoplastic resins (A).
[0107]
Specifically, when using an extruder for melt-kneading, a liquid addition nozzle is provided in the middle of the extruder after the resin is completely melted, and a pump is used. Dispersion can be injected from the nozzle. As the pump, a tube pump, a gear pump, a plunger pump, or the like can be used. The dispersion is preferably cooled in order to prevent aggregation of the fluororesin during feeding, and the pump is preferably a tube pump.
[0108]
As another preferable blending method of the dispersion of the fluororesin, as shown in FIG. 2, an opening (3) such as a vent port is provided in the middle of the extruder, and a pipe provided with a cooling jacket therefor There is a method of installing (2) and dropping the dispersion from this pipe. When this method is used, it is not necessary to apply pressure to the dispersion of the fluororesin, it is possible to prevent the dispersion of the dispersion of the fluororesin in the pump part (P), and the piping of the dripping part contacts the extruder Therefore, the temperature rise of the dispersion cooled by the cooling jacket is small, which is preferable because aggregation of the fluororesin can be suppressed. Furthermore, it is preferable because the aqueous dispersion medium of the dispersion is efficiently removed by evaporation as it is dropped from the vent port (3). A tube pump, a gear pump, a plunger pump, etc. can be used as a pump, and a tube pump is preferable.
[0109]
That is, according to still another aspect of the present invention, in the above-described production method of the highly flame-retardant resin composition of the present invention, an extruder having an opening portion in the middle is used, and the fluorine-based resin ( B) Aqueous dispersion is dropped and the aqueous dispersion medium of the fluororesin (B) aqueous dispersion is evaporated from the opening while melt-kneading together with the melt-kneaded product formed in the above step (1). A method is provided.
[0110]
FIG. 2 is a schematic diagram for explaining a method for producing the flame retardant resin composition of the present invention using the extruder having an opening in the middle according to the above embodiment of the present invention. The method is not limited by this figure. In addition, for example, another at least one further opening (not shown) is provided between the hopper 1 of the extruder shown in FIG. 2 and the opening 3 (for supplying the fluororesin dispersion), It is also possible to supply at least a part of the thermoplastic resin and at least a part of the flame retardant from the hopper 1 and the further opening. Further, when the supply of the thermoplastic resin and / or the flame retardant is not completed upstream (with respect to the extrusion direction) of the opening 3 in FIG. 2, another at least one further downstream of the opening 3 (downstream). An opening (not shown) can be provided to supply the remaining components from the further opening.
[0111]
A method for molding a molded article made of the thermoplastic resin composition thus obtained is not particularly limited, and examples thereof include extrusion molding, compression molding, injection molding, gas assist molding, and the like. Among these, injection molding is preferable.
Examples of molded articles include OA equipment housings such as notebook personal computers, copiers, and printer housings, OA equipment chassis, mobile phone housings, and the like.
[0112]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the embodiments of the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to these examples.
[0113]
Measurement and evaluation methods in Examples and Comparative Examples of the present invention are as follows.
(1) Weight average molecular weight
It measured by gel permeation chromatography (GPC).
Equipment: Japan, Tosoh HLC-8020
Solvent: THF
Column: Japan, Tosoh TSK gel (T5000HXL + T4000HXL)
[0114]
(2) It observed according to the method as described in the form observation specification of the fluororesin in a thermoplastic resin composition.
(Test piece injection molding)
  Molding machine:MJEC-10(Made by Modern Machinery, Japan)
  Molding temperature: 260 ° C
  Mold temperature: 60 ℃
  Injection speed: 500 (setting value)
  Test piece: 1/2 x 5 x 1/16 inch
[0115]
However, the molding temperature and the mold temperature were changed to 280 ° C. and 80 ° C., respectively, when (A-1) described later was used alone as a thermoplastic resin. Similarly, when (A-2), which will be described later, is used alone as the thermoplastic resin, it was changed to 290 ° C. and 80 ° C., respectively. Moreover, when using later mentioned (A-6) independently as a thermoplastic resin, it changed into 230 degreeC and 50 degreeC, respectively, and implemented.
[0116]
(Preparation of sample for SEM observation)
Using a tensile tester (Autograph 5000D, manufactured by Shimadzu Corporation, Japan), the test piece obtained by the above injection molding is pulled at a speed of 5 mm / min until it breaks.
[0117]
(SEM observation)
Pre-treatment: Gold vapor deposition is performed on the sample fracture surface so that the gold thickness is 200 angstroms or more. (Vapor deposition equipment: JFC 1500QUICKAUTOCOATER manufactured by JEOL, Japan)
Observation device: JSM-5300 (made by JEOL, Japan)
Acceleration voltage: 15 kV
  7 microns x 7 microns with fibrils dispersed throughoutAreaSEM is used to measure the percentage of the total fibril length of fibrils having a diameter of 0.5 microns or less and the number of fibril intersections and branch points in the dispersion form indicated by the dispersed fibrils. did.
[0118]
(3) Flame resistance
Evaluation was performed by a test based on the UL94 standard 20MM vertical combustion test (thickness 1/16 inch). In this test, when it is evaluated as V-0 or V-1, there is no dripping of a fire type, and when the fall of a fire type is recognized, it is evaluated as V-2.
[0119]
(4) Glossiness
A 10 cm × 10 cm × 2 mm flat plate injection-molded at a temperature suitable for each resin composition was injection-molded, and the surface gloss was measured with a gloss meter based on ASTM-D-523-62T with an incident angle and a reflection angle of 60 degrees. . (The higher the value obtained by measurement with a gloss meter, the smoother the surface and the higher the glossiness.)
[0120]
(5) Flow mark
A 10 cm × 10 cm × 2 mm flat plate was injection-molded at a temperature suitable for each resin composition, and the surface was visually examined for the presence or absence of a flow mark or silver, and determined as follows.
○: No flow mark or silver
×: Flow mark or silver is generated
[0121]
The compounding agent used for an Example below is demonstrated.
(Polycarbonate resin A-1)
Bisphenol A having a weight average molecular weight of 22,500
Aromatic polycarbonate resin derived from
[0122]
(Polyphenylene ether resin A-2)
According to the method described in US Pat. No. 4,788,277 (corresponding to Japanese Patent Application No. 62-77570), 2,6-xylenol was subjected to oxidative coupling polymerization in the presence of dibutylamine. Reduced viscosity is ηsp / c = 0.42 dl / g, 140 sec at 280 ° C.^-1A poly (2,6-dimethyl-1,4-phenylene) ether (hereinafter abbreviated as PPE) resin having a melt viscosity of 49,000 poise measured at a shear rate of 75 parts by weight and a general weight average molecular weight of 210,000 Modified PPE resin in which 25 parts by weight of polystyrene resin is previously melt-kneaded.
[0123]
(Rubber reinforced resin A-3)
40 parts by weight of butadiene rubber latex (the weight average particle diameter of the latex obtained from a transmission electron microscope is 0.28 microns), 100 parts by weight of ion-exchanged water, and 0.3 parts by weight of potassium rosinate are put into a 10 liter reactor. After the gas phase portion was replaced with nitrogen, the initial solution was heated to 70 ° C. The pH before polymerization was adjusted to about 7 by bubbling carbon dioxide in the reactor. Next, an aqueous solution 1 having a composition shown below, a monomer mixed solution 3, and an aqueous solution 2 containing potassium rosinate as an emulsifier were continuously added to the reactor over 5 hours. After completion of the addition, the temperature was maintained for 1 hour to complete the reaction.
[0124]
The composition of the aqueous solution 1 is as follows.
Ferrous sulfate 0.005 part by weight, sodium formaldehyde sulfoxylate (SFS) 0.1 part by weight, disodium ethylenediaminetetraacetate (EDTA) 0.04 part by weight, ion-exchanged water 50 part by weight.
The composition of the aqueous solution 2 is as follows.
Potassium rosinate 1.0 part by weight, ion-exchanged water 20 parts by weight.
The composition of the monomer mixture 3 is as follows.
18 parts by weight of acrylonitrile, 42 parts by weight of styrene, 0.6 part by weight of t-dodecyl mercaptan (t-DM), 0.1 part by weight of cumene hydroperoxide (CHP).
[0125]
Next, an antioxidant was added to the prepared graft polymer latex, and then salted out, washed with water, dehydrated and dried by heating to obtain a powder.
Further, an AS resin (acrylonitrile-styrene resin) having an acrylonitrile component ratio of 27% by weight and a weight average molecular weight of 120,000 was mixed with the powder obtained above, and ABS (acrylonitrile-butadiene-styrene) having the following composition was mixed. ) A resin was obtained.
[0126]
Acrylonitrile component 24% by weight
Butadiene component 10% by weight
Styrene component 66% by weight
(Rubber reinforced resin A-4)
In the same manner as the rubber-reinforced resin A-3, an ABS resin having the following composition was obtained.
Acrylonitrile component 18% by weight
Butadiene component 33% by weight
Styrene component 49% by weight
(Rubber reinforced resin A-5)
Acrylonitrile component 18% by weight
Butadiene component 20% by weight
Styrene component 50% by weight
N-phenylmaleimide component 12% by weight
Rubber reinforced resin consisting of
(Rubber reinforced resin A-6)
Butadiene component 10% by weight
Styrene component 90% by weight
HIPS resin (high impact polystyrene resin)
[0127]
(Dispersion of fluororesin PTFE B-1)
Polyflon TFE dispersion D-1 (solid content concentration: about 60% by weight, particle size: 0.20 to 0.40 micron, pH value: 9 to 10), manufactured by Daikin Industries, Ltd., Japan
(Dispersion of fluororesin PTFE B-2)
Teflon 30-J, manufactured by Mitsui DuPont Fluorochemicals, Japan (solid content concentration 60% by weight, particle size 0.23 microns, surfactant concentration is 6% by weight with respect to PTFE weight, pH value 9 to 10)
[0128]
(Fluorine resin PTFE fine powder B-3)
Made in Japan, Daikin Industries, Polyflon F-201L
(Fluorine resin PTFE fine powder B-4)
Teflon 62-J, made by Mitsui DuPont Fluorochemicals, Japan
[0129]
(Flame retardant C-1)
Represented by the formula (2) described in the specification,
n = 0 or a natural number, R and R ′ are compounds represented by the group described in Formula (4), and have a softening temperature of 105 ° C.
(Flame retardant C-2)
Triphenyl phosphate
[0130]
(Flame retardant C-3)
It is a condensed phosphate ester flame retardant mainly composed of the mixture of Chemical Formula 20 and Chemical Formula 21, and was synthesized by the following method.
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 and a reflux tube, and nitrogen was added. The reaction was carried out at 70 to 140 ° C. for 4 hours under an air stream. 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. .
[0131]
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 Toyo Co., Ltd., Japan]. It was vacuum dried to obtain a pale yellow transparent purified product.
As a result of HPLC analysis (LC-10A manufactured by Shimadzu, Japan, column: Japan, Tosoh TSKgel ODS-80T, solvent: methanol / water 90/10), the total purity of the chemical 20 and chemical 21 components is 75% by weight. there were.
[0132]
【Example】
Examples 1-7, Comparative Example 7
The resin excluding the fluororesin prepared as described above was cooled (3 ° C.) and pulverized with dry ice (sample mill, SK-M10 type, manufactured by Kyoritsu Riko Co., Ltd.) (B-3). B-4) are blended with the compositions listed in Tables 1 and 2 (units are parts by weight), kneaded and granulated with a twin screw extruder (ZSK-25, Germany, Werner & Pfleiderer) to obtain pellets. And evaluated. The extruder was set at temperatures of Examples 1 to 3, Comparative Example 7 at 290 ° C., Examples 4 and 6 at 250 ° C., and Examples 5 and 7 at 220 ° C. The observation results of the dispersion form of the fluororesin in the resin composition and the evaluation results of flame retardancy are shown in Tables 1 and 2.
[0133]
Comparative Examples 1-6, 8
The resin prepared as described above was batch-blended (room temperature, 25 ° C.) with the composition listed in Table 2 (unit is parts by weight), kneaded and granulated with a twin-screw extruder (ZSK-25) to obtain pellets, Evaluation was performed. The setting temperature of the extruder was 290 ° C. for Comparative Examples 1 and 6, 8 and 8, 250 ° C. for Comparative Examples 3 and 5, and 220 ° C. for Comparative Examples 2 and 4. Table 2 shows the observation results of the dispersion form of the fluororesin in the resin composition and the evaluation results of flame retardancy.
In Comparative Example 6, extrusion was difficult.
[0134]
Examples 8 to 15 and Comparative Example 17
According to the composition of Tables 3 and 4 (unit is parts by weight), the following was carried out.
Fig. 2 shows the dispersion of fluororesin blended with raw materials except for fluororesin and flame retardant, kneaded with a twin-screw extruder (ZSK-25), and cooled (3 ° C) from the middle of the extruder. Then, the mixture was dropped and kneaded into the melted raw material by a simple apparatus, and in the subsequent stage, the flame retardant was press-fitted into a molten resin and granulated to obtain pellets for evaluation. The extruder was set at a set temperature of 290 ° C. in Examples 8 to 11 and Comparative Example 17 and 250 ° C. in Examples 12 to 15. Tables 3 and 4 show the observation results of the dispersion form of the fluororesin in the resin composition and the evaluation results of flame retardancy, gloss and flow mark.
Comparative Example 17 was difficult to extrude.
[0135]
Examples 16-18
According to the composition shown in Table 3 (units are parts by weight), the test was carried out as follows.
Each raw material is blended except for the fluororesin, kneaded with a twin screw extruder (ZSK-25), and the fluororesin dispersion cooled (3 ° C) from the middle of the extruder is melted in the equipment shown in Fig. 2. It was dripped at the raw material, and pellets after further kneading were obtained and evaluated. The setting temperature of the extruder was 220 ° C. for Examples 16 and 18, and 250 ° C. for Example 17. Table 3 shows the observation results of the dispersion form of the fluororesin in the resin composition and the evaluation results of flame retardancy, gloss and flow mark.
[0136]
Comparative Examples 9-14, 18
According to the composition shown in Table 4 (units are parts by weight), the test was carried out as follows.
Excluding the flame retardant, each raw material is blended, kneaded with a twin-screw extruder (ZSK-25), pressed into a molten resin from the middle of the extruder with a pump and granulated to obtain pellets, Evaluation was performed. The extruder was set at a set temperature of 290 ° C. for Comparative Examples 9 to 12 and Comparative Example 18, and 250 ° C. for Comparative Examples 13 and 14. Table 4 shows the observation results of the dispersion form of the fluororesin in the resin composition and the evaluation results of flame retardancy, gloss, and flow mark.
[0137]
Comparative Examples 15 and 16
According to the composition shown in Table 4 (units are parts by weight), the test was carried out as follows.
All raw materials were blended together and kneaded with a twin screw extruder (ZSK-25) whose cylinder temperature was set to 250 ° C. for Comparative Example 15 and 220 ° C. for Comparative Example 16, and the pellets were Obtained and evaluated. Table 4 shows the observation results of the dispersion form of the fluororesin in the resin composition and the evaluation results of flame retardancy, gloss, and flow mark.
[0138]
Example 19
According to Table 3 (unit is part by weight), the following was carried out.
Each raw material is blended with the exception of fluororesin and flame retardant, and kneaded with a twin screw extruder (ZSK-25) with a cylinder temperature set at 250 ° C. First, the flame retardant is pressed into the molten resin with a pump. Then, the fluororesin dispersion cooled (3 ° C.) at the subsequent stage was dropped and kneaded into the melted raw material with an apparatus as shown in FIG. 2, granulated, and pellets were obtained for evaluation. Table 3 shows the observation results of the dispersion form of the fluororesin in the resin composition and the evaluation results of flame retardancy, gloss and flow mark.
[0139]
Comparative Example 19
After adding an antioxidant to the graft polymer latex described in the preparation of the rubber reinforced resin A-3, salting out, washing with water, dehydrating and drying by heating, 15 parts by weight of the powder Resin dispersion B-1 was uniformly blended with 0.5 part by weight and dried. This blend was blended with 80 parts by weight of polycarbonate resin A-1 and 5 parts by weight of AS resin (acrylonitrile-styrene resin) having an acrylonitrile component ratio of 27% by weight and a weight average molecular weight of 120,000, and the cylinder temperature was 250 ° C. Kneaded with a twin-screw extruder (ZSK-25) set to 1, and 8 parts by weight of flame retardant C-3 was melted into the melted resin by a pump and granulated to obtain pellets. Went. Table 4 shows the observation results of the dispersion form of the fluororesin in the resin composition and the evaluation results of flame retardancy, gloss, and flow mark.
[0140]
Example 20
80 parts by weight of polycarbonate resin A-1 was melted with a twin-screw extruder (ZSK-25) set at a cylinder temperature of 290 ° C., and first, 8 parts by weight of flame retardant C-3 was pumped into the melted resin. In the subsequent stage, the cylinder temperature was set to 250 ° C., and 0.5 parts by weight of the cooled fluororesin dispersion B-1 was kneaded into the melted raw material with an apparatus as shown in FIG. Further, 20 parts by weight of rubber reinforced resin A-4 was blended using a side feeder, granulated, and pellets were obtained for evaluation. Table 3 shows the observation results of the dispersion form of the fluororesin in the resin composition and the evaluation results of flame retardancy, gloss and flow mark.
[0141]
As can be seen by comparing Examples 1 to 7 and Comparative Examples 1 to 8, the thermoplastic resin composition containing the fluororesin in a dispersed form having a specific network structure and / or a specific branched structure of the present invention is It can be seen that it is superior in flame retardancy, particularly in dripping prevention during combustion, as compared with a thermoplastic resin composition including a fluorine-based resin composition not having such a network structure.
[0142]
Further, as can be seen by comparing Examples 8 to 20 and Comparative Examples 9 to 19, the method of the present invention in which a dispersion of a fluororesin is blended in a specific manner in a molten thermoplastic resin composition, and melt-kneaded, Compared to other methods, the resin composition is suitable for the production of a thermoplastic resin composition containing a fluororesin in a dispersed form having a specific network structure and / or a specific branched structure of the present invention. Is not only excellent in flame retardancy, particularly in dripping prevention during combustion, but also excellent in appearance of a molded product obtained by molding the resin composition.
[0143]
[Table 1]

[0144]
[Table 2]

[0145]
[Table 3]

[0146]
[Table 4]

[0147]
【The invention's effect】
The flame retardant resin composition of the present invention includes a fluororesin-dispersed fibril having a specific dispersion form together with a thermoplastic resin and a flame retardant, and is excellent in flame retardancy, particularly dripping prevention during combustion. In addition to this, the appearance of a molded product obtained by molding the resin composition is also excellent. In addition, the method of the present invention, in which a fluororesin aqueous dispersion is used and melt-kneaded with a thermoplastic resin and a flame retardant in a specific manner, is the above-described difficulty in containing the fluororesin dispersed fibril having a specific dispersion form. Suitable for the production of flammable resin compositions.
Therefore, the resin composition of the present invention and the production method thereof are used in fields where there is a strong demand for flame retardancy of materials from demands for improving safety in the case of fire, for example, OA equipment fields such as computers, word processors, printers, and copiers. In addition, it can be used particularly advantageously in the fields of general household electrical appliances such as TVs and game machines, and housing materials for mobile phones.
[Brief description of the drawings]
FIG. 1 is a schematic view showing a dispersion form of fluororesin fibrils on a tensile fracture surface of a molded product obtained from the flame retardant resin composition of the present invention. In addition, the part shown as the continuous line in FIG. 1 is a fluorine resin.
FIG. 2 is a schematic side view showing the internal structure of an example of an extruder that can be used in the present invention.
FIG. 3 is a scanning electron micrograph of the dispersion form of the fluororesin fibrils on the tensile fracture surface of the resin composition molded article of Example 4, which is observed as white in the photograph of FIG. The portion is a fluororesin.
4 is a scanning electron micrograph observing the dispersion form of the fluororesin fibrils on the tensile fracture surface of the resin composition molded article of Comparative Example 5, and is observed in white in the photograph of FIG. The portion is a fluororesin.
FIG. 5 is a scanning electron micrograph of the dispersion state of the fluororesin fibrils on the tensile fracture surface of the resin composition molded article of Example 8, which is observed as white in the photograph of FIG. The portion is a fluororesin.
6 is a scanning electron micrograph observing the dispersion form of the fluororesin fibrils on the tensile fracture surface of the resin composition molded article of Example 12, and is observed white in the photograph of FIG. The portion is a fluororesin.
FIG. 7 is a scanning electron micrograph of the dispersion state of the fluororesin fibrils on the tensile fracture surface of the resin composition molded article of Example 13, which is observed as white in the photograph of FIG. The portion is a fluororesin.
FIG. 8 is a scanning electron micrograph observing the dispersion form of the fluororesin fibrils on the tensile fracture surface of the resin composition molded article of Example 15, and is observed in white in the photograph of FIG. The portion is a fluororesin.
FIG. 9 is a scanning electron micrograph of the dispersion state of the fluororesin fibrils on the tensile fracture surface of the resin composition molded article of Comparative Example 14, and is observed white in the photograph of FIG. The portion is a fluororesin.
[Explanation of symbols]
a: Intersection of fibrils in the network structure (point where at least two fibrils cross each other)
b: Branch point of a fibril in a branched structure (a point where one fibril branches into at least two fibrils)
c: Fibrils having a thickness exceeding 0.5 microns
1: Extruder hopper
2: Jacketed piping (nozzle) for adding dispersion of fluororesin
3: Opening in the middle of the extruder
4: Extruder screw
P: Pump

Claims (7)

(A) A polycarbonate resin having a weight average molecular weight of 10,000 to 80,000, or 5 to 98 parts by weight of a polycarbonate resin having a weight average molecular weight of 10,000 to 80,000, and at least a rubber-like polymer that can be graft copolymerized with the rubber-like polymer. 100 parts by weight of a thermoplastic resin comprising 95 to 2 parts by weight of a rubber-reinforced resin containing a graft copolymer obtained by graft copolymerizing one kind of vinyl compound and a vinyl polymer, (B) 0.01% fluorine-based resin In the flame retardant resin composition containing -5 parts by weight and (C) 3-22 parts by weight of the flame retardant, the fluororesin (B) is present in the form of a plurality of fibrils, and the thermoplastic resin (A ) and the flame retardant (C) is present in the form of a mixture, is prepared by injection molding under the following conditions for flame retardancy test according to the vertical flame method according to UL-94 standard For fracture surface obtained by fracture of the test piece pulled at a speed 5 mm / min using a 1/2 × 5 × 1 / pulling a 16inch specimens tester fat composition, 7 fibrils dispersed throughout micron × 7 When the micron region is examined with a scanning electron microscope, the dispersion form exhibited by the dispersed fibrils has a diameter of 0.5 microns or less over a length corresponding to 50% or more of the total extension of the plurality of fibrils. And the plurality of fibrils have a network structure having one or more intersections where at least two fibrils cross each other, and a branch structure having one or more branch points where one fibril branches into at least two fibrils. And at least one structure selected from the group consisting of the intersection and the branch point is the 7 micron × 7 mix. A flame retardant resin composition, which is present in the Ron region .
(Test piece injection molding conditions)
Molding machine: MJEC-10 (made by Modern Machinery, Japan)
Molding temperature: 280 ° C. for polycarbonate resin alone, 260 ° C. for thermoplastic resin consisting of 5 to 98 parts by weight of polycarbonate resin and 95 to 2 parts by weight of rubber reinforced resin
Mold temperature: 80 ° C. for polycarbonate resin alone, 60 ° C. for thermoplastic resin consisting of 5 to 98 parts by weight of polycarbonate resin and 95 to 2 parts by weight of rubber reinforced resin
Injection speed: 500 (setting value) The plurality of fibrils have a diameter of 0.5 microns or less over a length corresponding to 70% or more of the total extension, and 10 or more points selected from the group consisting of the intersection and the branch point are the 7 microns The resin composition according to claim 1, which is present in a region of x7 microns.   The resin composition according to claim 1 or 2, wherein the fluororesin (B) is polytetrafluoroethylene (PTFE).   The resin composition according to claim 1 or 2, wherein the flame retardant (C) is a halogen-based flame retardant.   The resin composition according to claim 1 or 2, wherein the flame retardant (C) is a phosphate ester flame retardant.   The resin composition according to claim 1 or 2, wherein the flame retardant (C) is a condensed phosphate ester flame retardant.   The molded product obtained from the resin composition in any one of Claims 1-6.

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