JP3724860B2 - Resin composition with excellent appearance of molded product - Google Patents

Description

（式中、Ｘ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）ビニル基を示す。Ｙは水素、または−ＳＯ₃Ｍ（Ｍ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）で表される硫酸エステル塩、または−ＣＨ₂ＣＯＯＭ（Ｍ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、または下記（１’）式で表されるリン酸モノエステル塩を示す。
【００１６】
【化２】

Ｒ₁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、Ｒ₂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、Ｒ₃は水素またはプロペニル基、Ａ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は１〜２００の整数を示す。）
【００１７】
一般式（１）で示される具体的な化合物としては、次の一般式（２）〜（６）で表される化合物を用いることができる。
【化３】

【００１８】
これらの乳化剤は単独でも、２種類以上組み合わせてもよい。
ゴム強化樹脂（Ｂ）中のゴム状重合体の含有量は、好ましくは５〜６０重量％で、より好ましくは１０〜５０重量％の範囲である。５重量％未満では耐衝撃性が劣り、また６０重量％を越えると成形加工時の流動性や光沢値が低下してしまい好ましくない。
【００１９】
本発明のゴム強化樹脂（Ｂ）は、グラフト重合体を製造する過程で生成する、ゴム状重合体にグラフトしていない成分を含んでもよい。また、ゴム強化樹脂（Ｂ）の製造方法は特に限定されないが、例えば、乳化重合により、グラフト重合体とグラフトしない共重合体を同時に作る方法、また乳化重合によりゴム状重合体の割合の高い、グラフト共重合体とビニル共重合体の混合物（以下ＧＲＣと略することがある）をあらかじめ製造し、別に塊状重合、乳化重合や懸濁重合等で製造したビニル共重合体を配合して目的のゴム含有量にする方法もとられる。
【００２０】
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等の無機化合物、酸化アンチモン、酸化ビスマス等が挙げられ、また、酸化亜鉛、酸化スズなどの金属酸化物、赤リン、ホスフィン、次亜リン酸、亜リン酸、メタリン酸、ピロリン酸、無水リン酸などの無機系リン化合物、カーボンファイバー、グラスファイバー、などの繊維、膨張黒鉛、シリカ、シリカ系ガラス溶融物などが用いられるが、好ましくはリン系化合物、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等が挙げられる。
【００２１】
ハロゲン系有機化合物としては、一般のハロゲン系難燃剤および含ハロゲンリン酸エステル全般を挙げることができる。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挙げられるが、好ましくは、下記一般式（７）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一般式（８）のハロゲン系有機化合物である。
【００２２】
【化４】

【００２３】
【化５】

【００２４】
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。
【００２５】
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ポ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成した化合物が挙げられる。
本発明の組成物中における縮合リン酸エステル系難燃剤は、一般式（１１）で表される化合物である。
【００２６】
【化６】

（式中、ｎは１〜１０の正数であり、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以上の場合には複数あるＡｒ４は各々同一でも異なってもよい。）
該化合物の具体例として好ましくは、下記一般式（１２）〜（１５）で表される化合物である。
【００２７】
【化７】

（式中、Ａｒ１〜Ａｒ３は各々同一または異なっており、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は前記一般式（１１）におけるＡ４である。）
上記で表される化合物はリン酸エステル化合物であり、こ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よい。
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。
【００２８】
難燃剤の配合量は必要な難燃性のレベルに応じて決められるが、樹脂組成物の合計が１００重量部に対して、０．１〜３０重量部の範囲であることが必要である。０．１重量部未満では必要な難燃効果が発揮されない。３０重量部を超えると樹脂の機械的強度を低下させる。好ましくは１〜２８重量部であり、特に好ましい範囲としては３〜２５重量部の範囲である。難燃剤としてハロゲン系化合物を用いる場合には、難燃効果を高める為に難燃助剤を用いることが出来る。難燃助剤として好ましくは、元素周期律表におけるＶＢ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、酸化ビスマスであり、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に用いられる。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挙げられる。これらの難燃助剤は樹脂中への分散を改善する目的及び／又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。
【００２９】
難燃助剤の添加量は、０．５〜２０重量部の範囲が好ましく、０．５部未満の場合には、難燃助剤の効果が十分でなく、２０重量部を越える場合には、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重量部であり、特に好ましくは１〜１０重量部の範囲である。
【００３０】
ポリカーボネート系樹脂（Ａ）とゴム強化熱可塑性樹脂組成物（Ｂ）の割合は、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られ、成分（Ａ）が５〜９８重量部、成分（Ｂ）が２〜９５重量部の範囲にあることが必要である。好ましくは、成分（Ａ）が２０〜９０重量部、成分（Ｂ）が２０〜８０重量部であり、さらに好ましくは、成分（Ａ）が２５〜８５重量部、成分（Ｂ）が１５〜７５重量部の範囲である。
本発明の滴下防止剤のポリテトラフルオロエチレンには特に限定はないが、ファインパウダーあるいはディスパージョン等が好ましい。樹脂への配合量としては０．０１〜３重量部の範囲にあることが好ましい。
【００３１】
本発明の充填剤としては、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。また、配合量は、（Ａ）と（Ｂ）と（Ｃ）の合計１００重量部に対して１〜５０重量部の範囲であればよい。
【００３２】
また、本発明の樹脂組成物に対し、公知の酸化防止剤、紫外線吸収剤、滑剤、離型剤、帯電防止剤、着色剤、シリコーンオイル、オレフィン系オイル、等を加えることは任意である。
本発明の樹脂組成物の製造方法は特に限定されないが、通常の方法、例えば、押出機混練、バンバリーミキサー、ニーダー等によるメルトブレンド、ゴム強化樹脂の重合途中に他の成分を添加する方法、溶媒ブレンド等により製造することができる。
【００３３】
さらに、これらの熱可塑性樹脂組成物からなる成形品の成型方法は、押し出し成形、圧縮成型、射出成形、シート成形、真空成形、ガスアシスト成形等があり、特に限定されない。成形品の例としては、パーソナルコンピュータ（パソコン）、携帯用パソコン、ファクシミリ、ＣＲＴ、テレビ等の各種ＯＡ機器および家庭用電化製品のハウジングとして、また携帯用電話やパーソナルハンディーホンシステム（ＰＨＳ）、ホイールキャップ、スポイラー、自動車のインパネ等が挙げられる。
【００３４】
【実施例】
以下、実施例に基づき本発明を更に詳細に説明する。なお、本発明はこれら実施例により何ら限定されるものではない。以下に用いる部数は重量部とする。
なお、本発明の実施例における測定方法は以下の通りである。
【００３５】
（表面グラフト被覆率）
ゴム強化熱可塑性樹脂組成物を、そのゾル分が可溶な溶媒（例えば、ＡＢＳ樹脂ではアセトン）を用いて溶解後、遠心分離し、ゲル分を取り出す。ゲル分をアセトン中に超音波ホモジナイザーを用いて分散させた後、エポキシ樹脂系接着剤主剤中に加え、再度分散させる。アセトンを真空乾燥にて除去した後、エポキシ樹脂系接着剤の硬化剤を加え、混合、加熱し固化させる。これにより、エポキシ樹脂中に分散したグラフト重合体が得られる。
得られたグラフト重合体含有のエポキシ樹脂は、例えばＡＢＳ樹脂の場合には、四酸化オスミウムで染色しウルトラミクロトームにて超薄切片作成後、透過型電子顕微鏡にて観察、撮影した。超薄切片の厚さは６０ｎｍとした。
【００３６】
グラフト重合体の電子顕微鏡写真の解析には、画像解析装置ＩＰ−１０００（旭化成工業（株）社製）を用い、表面グラフト被覆率を測定した。具体的には、グラフト重合体中のゴム状重合体とこのゴム状重合体の表面にグラフトしているビニル化合物成分とを分離した画像を作成し、前述のように、図１において、ａ₁ 〜ａ_n 及びｂ₁ 〜ｂ_n のそれぞれの長さを測定し、Ｒ＝（ａ₁ ＋ａ₂＋・・・・＋ａ_n-1 ＋ａ_n ）＋（ｂ₁ ＋ｂ₂ ＋・・・・＋ｂ_n-1 ＋ｂ_n ）とｒ＝（ａ₁ ＋ａ₂ ＋・・・・＋ａ_n-1 ＋ａ_n ）とから下記（ロ）式で表面グラフト被覆率を求める。
表面グラフト被覆率（％）＝（ｒ／Ｒ）×１００ （ロ）
なお、実施例の表面グラフト被覆率の測定にあたっては、ゴム状重合体の粒径×０．９以上の粒径をもつグラフト重合体のみを選び測定に供した。測定個数は１０である。表中の単位は％で記した。
【００３７】
（ビニル化合物の平均厚さ）
ゴム状重合体の表面にグラフトしているビニル化合物の厚さは、上記の表面グラフト被覆率と同様、得られたゴム強化熱可塑性樹脂組成物を四酸化オスミウムで染色しウルトラミクロトームにて超薄切片作成後、透過型電子顕微鏡にて観察、撮影した。グラフト重合体の電子顕微鏡写真の解析には、画像解析装置ＩＰ−１０００（旭化成工業（株）社製）を用いた。具体的には、グラフト重合体中のゴム状重合体とこのゴム状重合体粒子表面にグラフトしているビニル化合物とを分離した画像を作成し、図１においてゴム状重合体の表面積に相当する周囲長（Ｒ）、すなわちＲ＝（ａ₁ ＋ａ₂ ＋・・・・＋ａ_n-1 ＋ａ_n ）＋（ｂ₁ ＋ｂ₂ ＋・・・・＋ｂ_n-1 ＋ｂ_n ）を測定し、次いでゴム状重合体表面にグラフトしているビニル化合物の体積に相当する面積（ｔ）、即ち、ｔ＝（ｃ₁ ＋ｃ₂ ＋・・・・＋ｃ_n-1 ＋ｃ_n ）とから下記（ハ）式でビニル化合物の平均厚さを求める。
ビニル化合物の平均厚さ＝（ｔ／Ｒ） （ハ）
なお、測定個数は１０である。表中の単位はｎｍで記した。
【００３８】
（ゴム状重合体の重量平均粒子径）
ゴム状重合体の希薄液を透過型電子顕微鏡測定用金属メッシュ上に１滴とり、四酸化オスミウムあるいは四酸化ルテニウムの蒸気で染色した。染色されたサンプルを透過型電子顕微鏡にて撮影し、粒子の重量平均粒子径を上記の画像解析装置ＩＰ−１０００を用いて求めた。測定個数は１００である。
【００３９】
（物性評価方法）
各種物性の評価方法については以下に示す通りである。
（１）メルトフローレート（ＭＦＲ）
ＪＩＳ Ｋ７２１０に基づき測定した。測定条件は２４０℃、１０ｋｇ荷重で単位はｇ／１０ｍｉｎである。
（２）光沢度
ペレットを成形温度２６０℃、金型温度６５℃で１０ｃｍ×１０ｃｍ×２ｍｍの平板を成形し、ＡＳＴＭ Ｄ−５２３−６２Ｔに基づき、光沢計（Ｇｌｏｓｓｍｅｔｅｒ）により、入射角、反射角を６０度として表面光沢を求めた。
【００４０】
（３）フローマーク
ペレットを成形温度２６０℃、金型温度６５℃で１０ｃｍ×１０ｃｍ×２ｍｍの平板を成形し、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た。
○：フローマークの発生無し
×：フローマークの発生有り
（４）難燃性
ＵＬ９４規格垂直燃焼試験（厚み１／１２インチ）に基づく試験により測定した。
【００４１】
（ポリカーボネート樹脂 ＰＣ−１）
重量平均分子量２４５００のポリカーボネート樹脂
（共役ジエン系ゴムＳの製法）
（ゴムラテックス Ｓ−１）
以下の組成の物質（固形分基準）を、内部を真空に脱気した５０リットルオートクレーブに投入し、６５℃にて重合を行った。
【００４２】
１，３−ブタジエン ９７．０ 部
アクリロニトリル ３．０ 部
ｔ−ドデシルメルカプタン ０．２ 部
ロジン酸カリウム ０．７ 部
牛脂ケン化石ケン ０．３ 部
過硫酸ナトリウム ０．２５部
水酸化ナトリウム ０．１ 部
炭酸水素ナトリウム ０．３５部
脱イオン水 ６０．０ 部
【００４３】
重合開始後１０時間目から２０時間目の間に、以下の組成の溶液をオートクレーブに連続添加しながら重合を継続した。
ロジン酸カリウム ０．３ 部
牛脂ケン化石ケン ０．１ 部
過硫酸ナトリウム ０．１ 部
水酸化ナトリウム ０．０５部
炭酸水素ナトリウム ０．１５部
脱イオン水 ５０．０ 部
【００４４】
連続添加終了後、重合系を８０℃に昇温し、重合開始後２６時間目に冷却し重合を終了した。重合後、未反応ブタジエンを除去した。電子顕微鏡写真により求めたラテックスの重量平均粒子径は０．２８ミクロンであった。また、ラテックスのｐＨは１０．１であった。
（Ｓ−２）
表１に記載した以外はＳ−１と同様に実施した。
結果をまとめて表１に記す。
【００４５】
【表１】

【００４６】
（グラフト共重合体とビニル共重合体の混合物Ｇの製造）
（Ｇ−１の製造）
ゴムラテックスＳ−１（固形分）４０部、イオン交換水１００部を１０リットル反応器に入れ、気相部を窒素置換した後、この初期分散液を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２を反応器に５時間にわたり連続的に添加し、重合初期の乳化剤使用量が極めて少ない処方にて重合した。添加終了後、１時間温度を保ち反応を完結させた。
【００４７】
水溶液１の組成は次の通りである。
硫酸第一鉄 ０．００５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部
エチレンジアミンテトラ酢酸二ナトリウム（ＥＤＴＡ） ０．０５部
イオン交換水 ５０部
【００４８】
単量体混合液２の組成は次の通りである。
アクリロニトリル １８部
スチレン ４２部
ｔ−ドデシルメルカプタン（ｔ−ＤＭ） ０．８部
クメンハイドロパーオキサイド（ＣＨＰ） ０．１部
このようにして得られたＧＲＣラテックスに、酸化防止剤を添加した後、硫酸アルミニウムを加え凝固させ、水洗浄、脱水した後、加熱乾燥し、ＧＲＣ粉末を得た。
（Ｇ−２〜７の製造）
表２に示す組成および条件以外はＧ−１と同様にして得た。
【００４９】
【表２】

【００５０】
（ビニル共重合体 Ｔ−１）
（１）ビニル共重合体（Ｔ−１）
共重合体Ｔ−１中の組成は、ＩＲスペクトルより、アクリロニトリル３０重量％、スチレン７０重量％、また、極限粘度（共重合体Ｔ−１：０．５ｇ、メチルエチルケトン：１００ミリリットル、３０℃）は０．３９であった。
（難燃剤ＦＲ−１）
明細書記載の一般式（８）で表され、ｎ＝０又は自然数、ＲとＲ’は一般式（１０）で示される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ＦＲ−２）
以下の方法で合成した、一般式（１２）を主成分とする縮合リン酸エステル系難燃剤。
【００５１】
ビスフェノールＡ１１４ｇ（０．５モル）、オキシ塩化リン１５４ｇ（１．０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６１ｇ（０．５モル）、及び無水塩化アルミニウム２．０ｇ（０．０１５モル）を加え、１００〜１５０℃に加熱して４時間反応させた。ついでフラスコを室温まで冷却し、フェノール１４１ｇ（１．５モル）を加え、１００〜１５０℃に加熱して４時間保持し、反応を完結させた。そのままの温度で１ｍｍＨｇまで減圧し、未反応のフェノール類を溜去した。反応時に発生する塩化水素ガスは水酸化ナトリウム水溶液にて捕集し、中和滴定によりその発生量を測定して反応の進行をモニターした。生成した粗リン酸エステルを蒸留水で洗浄した後、濾紙（アドバンテック社製＃１３１）により固形分を除去した。真空乾燥して淡黄色透明な精製物を得た。
ＧＰＣ測定（島津製ＬＣ−１０Ａ、カラム：東ソーＴＳＫｇｅｌ ＯＤＳ−８０Ｔ、溶媒：メタノール／水 ９０／１０）の結果、一般式（１２）で表される成分の純度は６３重量％であった。
【００５２】
（難燃剤ＦＲ−３）
以下の方法で合成した、一般式（１３）を主成分とするリン酸エステル系難燃剤。
第１反応工程でオキシ塩化リン１９２ｇ（１．２５モル）、第２反応工程で、２，６−キシレノール１２２ｇ（１．０モル）、第３反応工程で、フェノール９４（１．０モル）を用いる以外は難燃剤ＦＲ−２と同じ方法で、淡黄色透明な精製物を得た。
ＧＰＣ測定（島津製ＬＣ−１０Ａ、カラム：東ソーＴＳＫｇｅｌ ＯＤＳ−８０Ｔ、溶媒：メタノール／水 ９０／１０）の結果、式（１３）成分の純度は７５重量％であった。
【００５３】
（滴下防止剤）−ＰＴＦＥ（ポリテトラフルオロエチレン）
平均粒度（ＡＳＴＭ−Ｄ１４５７に準拠して測定）が５００μｍ、融点（ＪＩＳ−Ｋ６８９１に準拠して測定）が３２７℃であるもの。
（ガラスファイバー）
シランカップリング処理された、直径１３ミクロンのガラスファイバー。
（難燃助剤）
三酸化アンチモン。
（その他の添加剤）
ＥＢＳは、エチレンビスステアリルアミドである。
【００５４】
（実施例１〜２６、比較例１〜１２）
以上のように調製した樹脂を表３〜５に掲げる組成（単位は重量部）でブレンドし、シリンダー温度が２４０℃に設定された２軸押出機（ＺＳＫ−２５、Ｗ＆Ｐ社製）で混練造粒し、ペレットを得て、上記の評価を行った。
【００５５】
（実施例２７〜３２、比較例１３、１４）
以上のように調製した樹脂を表３〜５に掲げる組成（単位は重量部）でブレンドし、シリンダー温度が２４０℃に設定された２軸押出機（ＺＳＫ−２５、Ｗ＆Ｐ社製）で混練造粒した。ただし、ガラスファイバーは押出機先端付近よりサイドフィードした。これによって得られたペレットで、上記の評価を行った。
以上の結果を表３〜５にまとめて示す。
【００５６】
【表３】

【００５７】
【表４】

【００５８】
【表５】

【００５９】
実施例および比較例から以下のことが明らかである。
実施例の組成物は、表面グラフト被覆率およびグラフト厚みが請求項記載の範囲にあるため、加工流動性、表面外観、難燃性に優れる。比較例の組成物は、グラフト被覆率もしくは、グラフト厚みが請求項記載の範囲を越えるため、加工流動性および、表面外観に劣る。
【００６０】
【発明の効果】
本発明の樹脂組成物は、加工流動性、表面外観に優れる。さらに難燃性も優れる。この効果は、ゴム強化樹脂と難燃剤の組み合わせによる組成物において、ビニル共重合体による表面グラフト被覆率が８０％以上であり、かつ上記ゴム状重合体表面にグラフト重合しているビニル化合物の平均厚みが５〜２５ｎｍであることを特徴とするグラフト重合体をゴム強化樹脂の成分とすることで達成しうる。
【図面の簡単な説明】
【図１】本発明の表面グラフト被覆率およびビニル化合物の被覆厚さを求めるための具体的解析例を示す図であり、図中黒色部はゴム状重合体であり、斜線部はビニル化合物のグラフト成分である。
【符号の説明】
ａ₁ 〜ａ_n ；ビニル化合物のグラフト部分のゴム状重合体上での周方向の長さ
ｂ₁ 〜ｂ_n ；ビニル化合物がグラフトされていない部分のゴム状重合体上での周方向の長さ
ｃ₁ 〜ｃ_n はビニル化合物のグラフト部分の断面積[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a resin composition excellent in processing fluidity, surface appearance of a molded product, mechanical strength, and excellent in flame retardancy.
[0002]
[Prior art]
A resin composition of a polycarbonate resin and a rubber reinforced resin such as an ABS resin has excellent mechanical characteristics, appearance, molding processability, and the like. Therefore, the OA field such as a computer, a word processor, a copying machine, Widely used in the field of general home appliances such as TVs and game machines. In recent years, downsizing and thinning have been demanded in such fields, and problems such as low fluidity, generation of flow marks, and poor surface appearance have occurred during molding. Furthermore, with the intensification of flame retardant regulations, flame retardant technology for resins has become an important technology.
[0003]
[Problems to be solved by the invention]
In order to improve the appearance of molded products, it is known to increase fluidity and make the rubber particles of rubber-reinforced resin uniform, but it is difficult to control them and it is extremely difficult to achieve the effect. .
[0004]
[Means for Solving the Problems]
As a result of intensive investigations in solving the above problems, the present inventors have found that when a rubber-reinforced resin composed of a graft polymer having a high surface graft coverage is made into a composition with a polycarbonate resin, the processing fluidity is good, and It has been found that the surface appearance is excellent, and the present invention has been completed.
[0005]
That is, the present invention
Polycarbonate resin (A) 25 -98 parts by weight,
A graft polymer obtained by graft-polymerizing one or more vinyl compounds that can be graft copolymerized with a rubber-like polymer, wherein the vinyl compound is graft-polymerized to the rubber-like polymer. The surface graft coverage defined by the following formula (a) is 80% or more, and the average thickness of the vinyl compound graft-polymerized on the surface of the rubbery polymer is 5 to 25 nm. Manufactured by emulsion graft polymerization Rubber reinforced resin (B) 2 containing graft polymer 75 Superposition part,
The resin composition which consists of.
Surface graft coverage (%) = (s / S) × 100 (A)
(Where S is the surface area of the rubber-like polymer, s is the surface area of the vinyl compound grafted and coated on the surface of the rubber-like polymer)
[0006]
First, the surface graft coverage in the present invention refers to the following (a) when S is the surface area of a rubber-like polymer and s is the surface area of a vinyl compound that is grafted onto the surface of a rubber-like polymer particle. In summary, this is a measure of how much vinyl compound is grafted and coated on the surface of the rubbery polymer dispersed in the rubber-reinforced thermoplastic resin composition.
Surface graft coverage (%) = (s / S) × 100 (A)
[0007]
As will be described later, this surface graft coverage (%) is specifically determined by observing an ultra-thin section of the graft polymer dispersed in the rubber-reinforced thermoplastic resin composition with an electron microscope, and analyzing and measuring the photograph taken. Can be obtained. FIG. 1 is a schematic diagram of this electron micrograph. In FIG. ₁ ~ A _n And b ₁ ~ B _n , And measure R = (a ₁ + A ₂ + ...... a _n-1 + A _n ) + (B ₁ + B ₂ + ...... b _n-1 + B _n ), R = (a ₁ + A ₂ + ...... a _n-1 + A _n ) Where R is the length corresponding to the surface area of the S = rubbery polymer, and r is the length corresponding to the surface area of the vinyl compound grafted onto the surface of the s = rubbery polymer. The surface graft coverage can be determined by the following equation (b).
Surface graft coverage (%) = (r / R) × 100 (b)
[0008]
In the present invention, the surface graft coverage is required to be 80% or more, preferably 90% or more. If it is less than 80%, a gel-like substance is undesirably produced due to impact resistance and deterioration of processing fluidity during high-temperature molding, coloring due to thermal deterioration, and particularly retention during extrusion or molding.
[0009]
Next, the composition of the present invention will be described.
The polycarbonate resin (A) used in the present invention is produced by a reaction of dihydric phenol and phosgene or carbonic acid diester. As the dihydric phenol, 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 dihydric phenol compounds other than bisphenol A include hydroquinone, 4,4 dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, and bis (4-hydroxyphenyl) ketone. is there. It may be a homopolymer of these dihydric phenols, two or more kinds of copolymers, or a blended product thereof.
[0010]
Next, the rubber reinforced resin (B) of the present invention will be described.
The rubber-reinforced resin (B) in the present invention contains, as a component, a graft polymer obtained by graft copolymerizing one or more vinyl compounds with a rubber-like polymer.
The rubbery polymer used in the present invention includes conjugated diene rubbers such as polybutadiene, polyisoprene, polychloroprene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, ethylene-propylene rubber, ethyl acrylate, acrylic Acrylic rubber such as butyl acid is preferable, but conjugated diene rubber polybutadiene, butadiene-styrene copolymer and butadiene-acrylonitrile copolymer are preferable. Moreover, these can be used in combination of 2 or more types.
[0011]
Examples of the vinyl compound to be grafted to the rubbery polymer used in the present invention include aromatic vinyl compounds such as styrene, main chain or side chain substituted styrene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, methyl acrylate, and ethyl acrylate. Acrylates such as butyl acrylate, methacrylic acid esters of the same substitution, acrylic acids such as acrylic acid and methacrylic acid, maleimide monomers such as N-phenylmaleimide and N-methylmaleimide, glycidyl methacrylate A glycidyl group-containing monomer such as is also used. These can be used in combination. Of these monomers, aromatic vinyl compounds and vinyl cyanide compounds are preferred. Particularly preferred are styrene and acrylonitrile.
[0012]
The proportion of the components grafted to the rubbery polymer produced during the production of the graft copolymer is measured by dissolving the polymer produced by the polymerization reaction in acetone and separating and removing the insoluble matter with a centrifuge. Can do. The component that dissolves in acetone is the component that has not undergone graft reaction (non-grafted component) in the copolymer that has undergone polymerization reaction, and the value obtained by subtracting the amount of rubber-like polymer from the acetone insoluble content is defined as the value of the graft component. The The proportion of the graft reaction component is preferably 10 to 80 parts by weight, more preferably 20 to 60 parts by weight, based on 100 parts by weight of the rubbery polymer.
[0013]
The method for producing the graft polymer is not particularly limited, but an emulsion graft polymerization method in which a vinyl compound is graft-polymerized to a rubber-like polymer latex produced by emulsion polymerization is preferable, and any of continuous, batch, and semi-batch methods is used. This method is also possible. In the present invention, an emulsion graft method in which a vinyl compound is continuously added to a rubbery polymer produced by emulsion polymerization together with an initiator, a molecular weight regulator and the like is particularly preferable. When using the emulsion graft polymerization method, in order to achieve a surface graft coverage of 80% or more, the amount of emulsifier used in emulsion graft polymerization should be extremely small. It is particularly preferable to add them little by little during the polymerization time. The pH at the time of polymerization can be any of alkaline, neutral and acidic conditions, but is preferably neutral.
[0014]
The emulsifier used in the emulsion polymerization is not particularly limited, but an emulsifier generally used for emulsion polymerization (hereinafter sometimes abbreviated as non-polymerizable emulsifier), for example, rosin acid salt, higher fatty acid salt, alkyl sulfate ester salt Anionic emulsifiers such as alkylbenzene sulfonate, alkyl diphenyl ether disulfonate, polyoxyethylene alkyl phenyl ether sulfate, dialkyl sulfosuccinate, and nonionic emulsifiers such as polyoxyethylene alkyl ether and polyoxyethylene alkyl phenyl ether. can give. In addition, an emulsifier having at least one double bond in the compound and capable of radical polymerization with a conjugated diene rubber, an aromatic vinyl compound, a vinyl cyanide compound and / or a (meth) acrylate compound (hereinafter, polymerizable) (May be abbreviated as emulsifier). Examples of these polymerizable emulsifiers include polymerizable emulsifiers represented by the following general formula (1).
[0015]
[Chemical 1]

(In the formula, X represents a (meth) allyl group, a (meth) acryloyl group or a (1-propenyl) vinyl group. Y represents hydrogen or —SO. _Three A sulfate ester salt represented by M (M is hydrogen, alkali metal, alkaline earth metal, ammonium or hydroxyalkylammonium having 1 to 4 carbon atoms), or -CH ₂ A carboxylate represented by COOM (M is hydrogen, an alkali metal, an alkaline earth metal, ammonium, or a hydroxyalkylammonium having 1 to 4 carbon atoms) or a phosphoric acid monoester salt represented by the following formula (1 ′) Indicates.
[0016]
[Chemical formula 2]

R ₁ Is an alkyl group having 1 to 18 carbon atoms, an alkenyl group or an aralkyl group, R ₂ Is hydrogen or an alkyl, alkenyl or aralkyl group having 1 to 18 carbon atoms, R _Three Represents hydrogen or a propenyl group, A represents an alkylene group having 2 to 4 carbon atoms or a substituted alkylene group, and n represents an integer of 1 to 200. )
[0017]
As specific compounds represented by the general formula (1), compounds represented by the following general formulas (2) to (6) can be used.
[Chemical 3]

[0018]
These emulsifiers may be used alone or in combination of two or more.
The content of the rubbery polymer in the rubber reinforced resin (B) is preferably 5 to 60% by weight, more preferably 10 to 50% by weight. If it is less than 5% by weight, the impact resistance is inferior, and if it exceeds 60% by weight, the fluidity and gloss value at the time of molding are lowered, which is not preferable.
[0019]
The rubber-reinforced resin (B) of the present invention may contain a component that is generated in the process of producing a graft polymer and is not grafted on the rubber-like polymer. Further, the production method of the rubber reinforced resin (B) is not particularly limited. For example, a method of simultaneously producing a graft polymer and a non-grafted copolymer by emulsion polymerization, or a high proportion of the rubbery polymer by emulsion polymerization, A mixture of a graft copolymer and a vinyl copolymer (hereinafter sometimes abbreviated as GRC) is produced in advance, and a vinyl copolymer produced by bulk polymerization, emulsion polymerization, suspension polymerization or the like is blended separately to obtain the desired The method of making the rubber content is taken.
[0020]
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, inorganic compounds such as magnesium hydroxide and aluminum hydroxide, Antimony oxide, bismuth oxide and the like, and metal oxides such as zinc oxide and tin oxide, and inorganic systems such as red phosphorus, phosphine, hypophosphorous acid, phosphorous acid, metaphosphoric acid, pyrophosphoric acid and phosphoric anhydride Fibers such as phosphorus compounds, carbon fibers, glass fibers, etc., expanded graphite, silica, silica-based glass melts, etc. are used, but preferably phosphorus-based compounds or halogen-based organic compounds, and halogen-based organic compounds and antimony oxides. Combination use etc. are mentioned.
[0021]
Examples of the halogen-based organic compound include general halogen-based flame retardants and all halogen-containing phosphate esters. For example, the halogen-based organic compounds include hexachloropentadiene, hexabromodiphenyl, octabromodiphenyl oxide, tribromophenoxymethane, decabromodiphenyl, decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromobisphenol A, tetrabromophthalimide, hexa Examples include bromobutene, hexabromocyclododecane, etc., preferably halogen organic compounds having the structure of the following general formula (7), particularly preferably halogen organic compounds of the following general formula (8) .
[0022]
[Formula 4]

[0023]
[Chemical formula 5]

[0024]
On the other hand, halogen-containing phosphate esters include tris-chloroethyl phosphate, tris-dichloropropyl phosphate, tris-β-chloropropyl phosphate, tris (tribromophenyl) phosphate, tris (dibromophenyl) phosphate, tris (tribromoneo Pentyl phosphate) and condensed phosphoric acid esters thereof. Tris (tribromoneopentyl phosphate), tris (tribromophenyl) phosphate, and tris (dibromophenyl) phosphate are preferable. These halogen organic compounds can be used alone or in combination of two or more.
[0025]
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, Examples thereof include 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.
The condensed phosphate ester flame retardant in the composition of the present invention is a compound represented by the general formula (11).
[0026]
[Chemical 6]

(In the formula, n is a positive number of 1 to 10, and Ar1 to Ar4 are each independently a phenyl group, a tolyl group, or a xylyl group. When n is 2 or more, a plurality of Ar4s are the same. But it may be different.)
Preferable examples of the compound are compounds represented by the following general formulas (12) to (15).
[0027]
[Chemical 7]

(In the formula, Ar1 to Ar3 are the same or different and each is a phenyl group, a tolyl group, or a xylyl group other than a 2,6-xylyl group, and R is A4 in the general formula (11).)
The compound represented above is a phosphoric acid ester compound, and this phosphoric acid ester compound has particularly good flame retardancy and heat resistance.
These can be used alone or in combination of two or more.
[0028]
Although the compounding quantity of a flame retardant is determined according to the level of a required flame retardance, it is necessary for the sum total of a resin composition to be the range of 0.1-30 weight part with respect to 100 weight part. If it is less than 0.1 part by weight, the necessary flame retardant effect is not exhibited. If it exceeds 30 parts by weight, the mechanical strength of the resin is lowered. The amount is preferably 1 to 28 parts by weight, and particularly preferably 3 to 25 parts by weight. When a halogen compound is used as the flame retardant, a flame retardant aid can be used to enhance the flame retardant effect. The flame retardant aid is preferably a compound containing an element belonging to VB in the periodic table of elements, specifically, a nitrogen-containing compound, a phosphorus-containing compound, antimony oxide, bismuth oxide, and iron oxide, zinc oxide. Metal oxides such as tin oxide are also effectively used. Of these, antimony oxide is particularly preferable, and specific examples include antimony trioxide and antimony pentoxide. These flame retardant aids may be those subjected to surface treatment for the purpose of improving dispersion in the resin and / or improving the thermal stability of the resin.
[0029]
The addition amount of the flame retardant aid is preferably in the range of 0.5 to 20 parts by weight. When the amount is less than 0.5 parts, the effect of the flame retardant aid is not sufficient. The mechanical strength and processing fluidity of the resin are reduced. More preferably, it is 1-15 weight part, Especially preferably, it is the range of 1-10 weight part.
[0030]
The ratio of the polycarbonate resin (A) and the rubber-reinforced thermoplastic resin composition (B) is determined according to the required mechanical strength, rigidity, molding processability, and heat resistance, and the component (A) is 5 to 98. It is necessary that the parts by weight and component (B) are in the range of 2 to 95 parts by weight. Preferably, component (A) is 20 to 90 parts by weight, component (B) is 20 to 80 parts by weight, and more preferably, component (A) is 25 to 85 parts by weight and component (B) is 15 to 75 parts by weight. The range is parts by weight.
There is no particular limitation on the polytetrafluoroethylene of the anti-dripping agent of the present invention, but fine powder or dispersion is preferred. The blending amount in the resin is preferably in the range of 0.01 to 3 parts by weight.
[0031]
Examples of the filler of the present invention include glass fiber, glass flake, carbon fiber, talc, mica and the like. These types may be determined according to the required mechanical strength, rigidity, molding processability, and heat resistance. Moreover, the compounding quantity should just be the range of 1-50 weight part with respect to a total of 100 weight part of (A), (B), and (C).
[0032]
Moreover, it is optional to add a known antioxidant, ultraviolet absorber, lubricant, mold release agent, antistatic agent, colorant, silicone oil, olefin oil, etc. to the resin composition of the present invention.
The method for producing the resin composition of the present invention is not particularly limited, but a usual method, for example, melt blending by an extruder kneading, a Banbury mixer, a kneader, etc., a method of adding other components during polymerization of a rubber reinforced resin, a solvent It can be produced by blending or the like.
[0033]
Furthermore, there are no particular limitations on the method of molding a molded article comprising these thermoplastic resin compositions, including extrusion molding, compression molding, injection molding, sheet molding, vacuum molding, gas assist molding, and the like. Examples of molded products include personal computers (personal computers), portable personal computers, facsimiles, CRTs, televisions and other OA equipment and household appliance housings, portable telephones, personal handyphone systems (PHS), wheels Examples include caps, spoilers, and instrument panels of automobiles.
[0034]
【Example】
Hereinafter, the present invention will be described in more detail based on examples. In addition, this invention is not limited at all by these Examples. The parts used below are parts by weight.
In addition, the measuring method in the Example of this invention is as follows.
[0035]
(Surface graft coverage)
The rubber-reinforced thermoplastic resin composition is dissolved using a solvent in which the sol content is soluble (for example, acetone in the case of ABS resin) and then centrifuged to take out the gel content. After the gel content is dispersed in acetone using an ultrasonic homogenizer, it is added to the epoxy resin adhesive main agent and dispersed again. After acetone is removed by vacuum drying, a curing agent for an epoxy resin adhesive is added, mixed, heated and solidified. Thereby, the graft polymer dispersed in the epoxy resin is obtained.
For example, in the case of an ABS resin, the obtained graft polymer-containing epoxy resin was dyed with osmium tetroxide, prepared an ultrathin section with an ultramicrotome, and then observed and photographed with a transmission electron microscope. The thickness of the ultrathin section was 60 nm.
[0036]
For the analysis of the electron micrograph of the graft polymer, an image analyzer IP-1000 (manufactured by Asahi Kasei Kogyo Co., Ltd.) was used to measure the surface graft coverage. Specifically, an image is prepared by separating the rubber-like polymer in the graft polymer and the vinyl compound component grafted on the surface of the rubber-like polymer, and as described above, in FIG. ₁ ~ A _n And b ₁ ~ B _n , And measure R = (a ₁ + A ₂ + ...... a _n-1 + A _n ) + (B ₁ + B ₂ + ...... b _n-1 + B _n ) And r = (a ₁ + A ₂ + ...... a _n-1 + A _n ) And the surface graft coverage by the following formula (b).
Surface graft coverage (%) = (r / R) × 100 (b)
In the measurement of the surface graft coverage of the examples, only the graft polymer having a particle size of rubbery polymer × 0.9 or more was selected for measurement. The number of measurements is 10. The unit in the table is expressed in%.
[0037]
(Average thickness of vinyl compound)
The thickness of the vinyl compound grafted on the surface of the rubber-like polymer is the same as the surface graft coverage mentioned above, and the obtained rubber-reinforced thermoplastic resin composition is dyed with osmium tetroxide and ultrathin with an ultramicrotome. After preparing the section, it was observed and photographed with a transmission electron microscope. An image analyzer IP-1000 (Asahi Kasei Kogyo Co., Ltd.) was used for the analysis of the electron micrograph of the graft polymer. Specifically, an image obtained by separating the rubber-like polymer in the graft polymer and the vinyl compound grafted on the surface of the rubber-like polymer particles is prepared, and corresponds to the surface area of the rubber-like polymer in FIG. Perimeter (R), ie R = (a ₁ + A ₂ + ...... a _n-1 + A _n ) + (B ₁ + B ₂ + ...... b _n-1 + B _n ) And then the area (t) corresponding to the volume of the vinyl compound grafted onto the rubbery polymer surface, ie t = (c ₁ + C ₂ + .... + c _n-1 + C _n ) And the average thickness of the vinyl compound is determined by the following formula (c).
Average thickness of vinyl compound = (t / R) (c)
The number of measurements is 10. The unit in the table is expressed in nm.
[0038]
(Weight average particle diameter of rubbery polymer)
One drop of a dilute solution of a rubber-like polymer was placed on a metal mesh for transmission electron microscope measurement and dyed with osmium tetroxide or ruthenium tetroxide vapor. The dyed sample was photographed with a transmission electron microscope, and the weight average particle diameter of the particles was determined using the above-described image analyzer IP-1000. The number of measurements is 100.
[0039]
(Physical property evaluation method)
The evaluation methods for various physical properties are as follows.
(1) Melt flow rate (MFR)
It measured based on JIS K7210. The measurement conditions are 240 ° C., 10 kg load, and the unit is g / 10 min.
(2) Glossiness
The pellet was molded at a molding temperature of 260 ° C. and a mold temperature of 65 ° C. and a 10 cm × 10 cm × 2 mm flat plate was molded. Gloss was sought.
[0040]
(3) Flow mark
The pellet was molded into a flat plate of 10 cm × 10 cm × 2 mm at a molding temperature of 260 ° C. and a mold temperature of 65 ° C., and the surface was visually inspected for the presence of flow marks or silver.
○: No flow mark
×: Flow mark is generated
(4) Flame resistance
It measured by the test based on UL94 standard vertical combustion test (thickness 1/12 inch).
[0041]
(Polycarbonate resin PC-1)
Polycarbonate resin with a weight average molecular weight of 24,500
(Production method of conjugated diene rubber S)
(Rubber latex S-1)
A substance having the following composition (based on solid content) was put into a 50 liter autoclave deaerated inside and subjected to polymerization at 65 ° C.
[0042]
1,3-butadiene 97.0 parts
Acrylonitrile 3.0 parts
t-dodecyl mercaptan 0.2 part
Potassium rosinate 0.7 parts
Beef tallow ken fossil ken 0.3 parts
0.25 parts sodium persulfate
Sodium hydroxide 0.1 part
Sodium bicarbonate 0.35 parts
60.0 parts deionized water
[0043]
Polymerization was continued during 10 to 20 hours after the start of polymerization while continuously adding a solution having the following composition to the autoclave.
Potassium rosinate 0.3 parts
Beef tallow ken fossil ken 0.1 parts
Sodium persulfate 0.1 part
Sodium hydroxide 0.05 parts
Sodium bicarbonate 0.15 parts
Deionized water 50.0 parts
[0044]
After completion of the continuous addition, the polymerization system was heated to 80 ° C. and cooled at 26 hours after the start of polymerization to complete the polymerization. After the polymerization, unreacted butadiene was removed. The weight average particle diameter of the latex determined by electron micrograph was 0.28 microns. The pH of the latex was 10.1.
(S-2)
Except as described in Table 1, the same procedure as in S-1 was performed.
The results are summarized in Table 1.
[0045]
[Table 1]

[0046]
(Production of Graft Copolymer and Vinyl Copolymer G)
(Production of G-1)
40 parts of rubber latex S-1 (solid content) and 100 parts of ion exchange water were placed in a 10 liter reactor, and the gas phase part was purged with nitrogen, and then the initial dispersion was heated to 70 ° C. The pH before the polymerization was adjusted by bubbling carbon dioxide in the reactor. Next, an aqueous solution 1 and a monomer mixed solution 2 having the following composition were continuously added to the reactor over 5 hours, and polymerization was carried out with a formulation in which the amount of emulsifier used at the initial stage of polymerization was extremely small. After completion of the addition, the temperature was maintained for 1 hour to complete the reaction.
[0047]
The composition of the aqueous solution 1 is as follows.
Ferrous sulfate 0.005 parts
Sodium formaldehyde sulfoxylate (SFS) 0.1 part
Ethylenediaminetetraacetic acid disodium (EDTA) 0.05 parts
50 parts of ion exchange water
[0048]
The composition of the monomer mixture 2 is as follows.
18 parts of acrylonitrile
42 parts of styrene
0.8 part of t-dodecyl mercaptan (t-DM)
Cumene hydroperoxide (CHP) 0.1 part
After adding an antioxidant to the thus obtained GRC latex, aluminum sulfate was added for coagulation, water washing, dehydration, and heat drying to obtain a GRC powder.
(Production of G-2 to 7)
The composition and conditions other than those shown in Table 2 were obtained in the same manner as G-1.
[0049]
[Table 2]

[0050]
(Vinyl copolymer T-1)
(1) Vinyl copolymer (T-1)
From the IR spectrum, the composition in the copolymer T-1 is 30% by weight of acrylonitrile, 70% by weight of styrene, and the intrinsic viscosity (copolymer T-1: 0.5 g, methyl ethyl ketone: 100 ml, 30 ° C.) 0.39.
(Flame retardant FR-1)
It is represented by the general formula (8) described in the specification, n = 0 or a natural number, R and R ′ are compounds represented by the group represented by the general formula (10), and the softening temperature is 105 ° C. Flame retardant.
(Flame retardant FR-2)
A condensed phosphate ester flame retardant synthesized by the following method and having the general formula (12) as a main component.
[0051]
Bisphenol A (114 g, 0.5 mol), phosphorus oxychloride (154 g, 1.0 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 a nitrogen stream It was made to react at 70-140 degreeC below for 4 hours. After completion of the reaction, while maintaining the reaction temperature, the flask was decompressed to 200 mmHg or less with a vacuum pump, and unreacted phosphorus oxychloride was recovered with a trap. Next, the flask was cooled to room temperature, 61 g (0.5 mol) of 2,6 xylenol and 2.0 g (0.015 mol) of anhydrous aluminum chloride were added, and the mixture was heated to 100 to 150 ° C. and reacted for 4 hours. The flask was then cooled to room temperature, 141 g (1.5 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 by an aqueous sodium hydroxide solution, and the amount of the generated hydrogen chloride was measured by neutralization titration to monitor the progress of the reaction. The produced crude phosphate ester was washed with distilled water, and then the solid content was removed with a filter paper (# 131 manufactured by Advantech). It was vacuum dried to obtain a pale yellow transparent purified product.
As a result of GPC measurement (LC-10A manufactured by Shimadzu, column: Tosoh TSKgel ODS-80T, solvent: methanol / water 90/10), the purity of the component represented by the general formula (12) was 63% by weight.
[0052]
(Flame retardant FR-3)
A phosphoric ester-based flame retardant composed mainly of general formula (13) synthesized by the following method.
192 g (1.25 mol) of phosphorus oxychloride in the first reaction step, 122 g (1.0 mol) of 2,6-xylenol in the second reaction step, and phenol 94 (1.0 mol) in the third reaction step A pale yellow transparent purified product was obtained in the same manner as the flame retardant FR-2 except that it was used.
As a result of GPC measurement (LC-10A manufactured by Shimadzu, column: Tosoh TSKgel ODS-80T, solvent: methanol / water 90/10), the purity of the component of formula (13) was 75% by weight.
[0053]
(Anti-dripping agent) -PTFE (polytetrafluoroethylene)
The average particle size (measured according to ASTM-D1457) is 500 μm, and the melting point (measured according to JIS-K6891) is 327 ° C.
(Glass fiber)
Silane-coupled glass fibers with a diameter of 13 microns.
(Flame retardant aid)
Antimony trioxide.
(Other additives)
EBS is ethylene bisstearylamide.
[0054]
(Examples 1 to 26, Comparative Examples 1 to 12)
The resins prepared as described above were blended with the compositions listed in Tables 3 to 5 (units are parts by weight), and kneaded with a twin-screw extruder (ZSK-25, manufactured by W & P) whose cylinder temperature was set to 240 ° C. Granules were obtained and pellets were obtained and evaluated as described above.
[0055]
(Examples 27 to 32, Comparative Examples 13 and 14)
The resins prepared as described above were blended with the compositions listed in Tables 3 to 5 (units are parts by weight), and kneaded with a twin-screw extruder (ZSK-25, manufactured by W & P) whose cylinder temperature was set to 240 ° C. Grained. However, the glass fiber was side-fed from the vicinity of the extruder tip. The above evaluation was performed on the pellets thus obtained.
The above results are summarized in Tables 3 to 5.
[0056]
[Table 3]

[0057]
[Table 4]

[0058]
[Table 5]

[0059]
The following is apparent from the examples and comparative examples.
The compositions of the examples are excellent in processing fluidity, surface appearance, and flame retardance because the surface graft coverage and graft thickness are within the scope of the claims. The composition of the comparative example is inferior in processing fluidity and surface appearance because the graft coverage or graft thickness exceeds the range of the claims.
[0060]
【The invention's effect】
The resin composition of the present invention is excellent in processing fluidity and surface appearance. In addition, it has excellent flame retardancy. This effect is obtained in the composition comprising a combination of a rubber reinforced resin and a flame retardant, in which the surface graft coverage by the vinyl copolymer is 80% or more, and the average of the vinyl compounds graft-polymerized on the surface of the rubber-like polymer. This can be achieved by using a graft polymer having a thickness of 5 to 25 nm as a component of the rubber-reinforced resin.
[Brief description of the drawings]
FIG. 1 is a diagram showing a specific analysis example for determining the surface graft coverage and vinyl compound coating thickness of the present invention, where the black part is a rubber-like polymer and the hatched part is a vinyl compound. Graft component.
[Explanation of symbols]
a ₁ ~ A _n The circumferential length of the graft portion of the vinyl compound on the rubber-like polymer
b ₁ ~ B _n ; The length in the circumferential direction on the rubber-like polymer where the vinyl compound is not grafted
c ₁ ~ C _n Is the cross-sectional area of the graft part of the vinyl compound

Claims (8)

25 to 98 parts by weight of polycarbonate resin (A),
A graft polymer obtained by graft-polymerizing one or more vinyl compounds that can be graft copolymerized with a rubber-like polymer, wherein the vinyl compound is graft-polymerized to the rubber-like polymer. An emulsification characterized in that the surface graft coverage defined by the following formula (a) is 80% or more and the average thickness of the vinyl compound graft-polymerized on the surface of the rubbery polymer is 5 to 25 nm. Rubber-reinforced resin (B) 2 to 75 polymer parts containing a graft polymer produced by a graft polymerization method ,
A resin composition comprising:
Surface graft coverage (%) = (s / S) × 100 (A)
(Where S is the surface area of the rubber-like polymer, s is the surface area of the vinyl compound grafted and coated on the surface of the rubber-like polymer) The resin composition of Claim 1 which consists of a total of 100 weight part of a component (A) and a component (B), and a flame retardant (C) 0.1-30 weight part. The resin composition according to claim 2, wherein the flame retardant is a halogen flame retardant. The resin composition according to claim 2, wherein the flame retardant is a phosphate ester flame retardant. The resin composition according to claim 2, wherein the flame retardant is a condensed phosphate ester flame retardant. The resin composition according to claim 2, comprising 100 parts by weight of a flame retardant thermoplastic resin composition and 0.01 to 3 parts by weight of polytetrafluoroethylene. The resin composition according to claim 2, comprising 100 parts by weight of a flame retardant thermoplastic resin composition and 1 to 50 parts by weight of a filler. A molded article comprising the flame retardant thermoplastic resin composition according to claim 2.

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