JP3918357B2 - Flame retardant resin composition and molded article - Google Patents

Description

【００３５】
本発明に使用されるシリコーンオイルとは、下記一般式（５）で表されるものである（ここで、Ｒはアルキル基またはフェニル基を表し、なかでもメチル基および／またはフェニル基であることが好ましい。ｎは１以上の整数である。）。使用するシリコーンオイルは、０．６５〜１０００００センチトークスの粘度のものが好ましいが、上記のシリコーンオイルである限り、それに限定されるものではない。
【００３６】
【化２】

【００３７】
本発明ではシリコーン系化合物として、シリコーン樹脂および／またはシリコーンオイルを使用することができるが、難燃性、耐熱性、耐ブリードアウト特性、耐接点汚染性、湿熱処理後の電気特性低下の面から、シリコーン樹脂が好ましい。
【００３８】
シリコーン系化合物の添加量は機械物性、成形性の面からポリブチレンテレフタレート樹脂（Ａ）１００重量部に対して通常０．０１〜１０重量部であり、好ましくは０．１〜５重量部、さらに好ましくは０．２〜３重量部である。
【００３９】
フッ素系樹脂およびシリコーン系化合物は併用することが可能であり、その場合のフッ素系樹脂およびシリコーン系化合物の合計の添加量は機械物性、成形性の面からポリブチレンテレフタレート樹脂（Ａ）１００重量部に対して０．０１〜１０重量部であることが好ましく、より好ましくは０．１〜５重量部、さらに好ましくは０．２〜３重量部である。
【００４０】
本発明の難燃性樹脂組成物はさらにヒンダードフェノール系の安定剤を併用すると長期間高温にさらされても極めて良好な耐加水分解性が維持されることが見いだされた。このような安定剤としては例えば、トリエチレングリコール−ビス［３−（３−ｔ−ブチル−５−メチル−４−ヒドロキシフェニル）プロピオネート］、１，６−ヘキサンジオール−ビス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、ペンタエリスリチル−テトラキス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、２，２−チオ−ジエチレンビス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、オクタデシル−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジルホスホネート ジエチルエステル、１，３，５−トリメチル−２，４，６−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）ベンゼン、ビスもしくはトリス（３−ｔ−ブチル−６−メチル−４−ヒドロキシフェニル）プロパン、Ｎ，Ｎ’−ヘキサメチレンビス（３，５−ジ−ｔ−ブチル−４−ヒドロキシ−ヒドロシンナマミド）、Ｎ，Ｎ’−トリメチレンビス（３，５−ジ−ｔ−ブチル−４−ヒドロキシ−ヒドロシンナマミド）などが挙げられる。
【００４１】
本発明においては、このようなヒンダードフェノール系安定剤を必要に応じて添加することができるが、その際のヒンダードフェノール系安定剤の添加量は通常、ポリブチレンテレフタレート樹脂（Ａ）１００重量部に対し０．０１〜３重量部、好ましくは０．０２〜２重量部、更に好ましくは０．０３〜０．５重量部である。
【００４２】
本発明で使用されるトリアジン系化合物とシアヌール酸またはイソシアヌール酸の塩とは、シアヌール酸またはイソシアヌール酸とトリアジン系化合物との付加物であり、通常は１対１（モル比）、場合により１対２（モル比）の組成を有する付加物である。トリアジン系化合物のうち、シアヌール酸またはイソシアヌール酸と塩を形成しないものは除外される。
【００４３】
上記トリアジン系化合物としては下記一般式（６）で表される化合物等が挙げられる。
【００４４】
【化３】

【００４５】
前記一般式（６）においてＲ¹、Ｒ²、Ｒ³、Ｒ⁴は同一または相異なる水素、アリール基、アルキル基、アラルキル基、シクロアルキル基、または−ＣＯＮＨ₂ である。ここでアリール基としては炭素数６〜１５のもの、アルキル基としては炭素数１〜１０のもの、アラルキル基としては炭素数７〜１６のもの、シクロアルキル基としては炭素数４〜１５のものが好ましい。また、Ｒ⁵は上式中の−ＮＲ¹Ｒ²または−ＮＲ³Ｒ⁴と同一の基、またはこれらと独立に水素、アリール基、アルキル基、アラルキル基、シクロアルキル基、−ＮＨ₂、または−ＣＯＮＨ₂ から選ばれた基であり、ここでアリール基としては炭素数６〜１５のもの、アルキル基としては炭素数１〜１０のもの、アラルキル基としては炭素数７〜１６のもの、シクロアルキル基としては炭素数４〜１５のものが好ましい。
【００４６】
Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴の具体的な例としては水素、フェニル基、ｐ−トルイル基、α−ナフチル基、β−ナフチル基、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ヒドロキシメチル基、メトキシメチル基、ベンジル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、２−メチル−１−ペンチル基、４−メチル−１−シクロヘキシル基、アミド基などが挙げられるが、中でも水素、フェニル基、メチル基、ヒドロキシメチル基、メトキシメチル基、ベンジル基、アミド基が好ましい。
【００４７】
また、Ｒ⁵の具体的な例としてはアミノ基、アミド基、メチルアミノ基、ジメチルアミノ基、エチルアミノ基、ジエチルアミノ基、モノ（ヒドロキシメチル）アミノ基、ジ（ヒドロキシメチル）アミノ基、モノ（メトキシメチル）アミノ基、ジ（メトキシメチル）アミノ基、フェニルアミノ基、ジフェニルアミノ基、水素、フェニル基、ｐ−トルイル基、α−ナフチル基、β−ナフチル基、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ベンジル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、２−メチル−１−ペンチル基、４−メチル−１−シクロヘキシル基などが挙げられるが、中でも水素、アミノ基、アミド基、メチル基、モノ（ヒドロキシメチル）アミノ基、ジ（ヒドロキシメチル）アミノ基、モノ（メトキシメチル）アミノ基、ジ（メトキシメチル）アミノ基、フェニル基、ベンジル基が好ましい。
【００４８】
前記一般式（６）で表わされる化合物とシアヌール酸またはイソシアヌール酸との塩のうち、特にメラミン、ベンゾグアナミン、アセトグアナミン、２−アミド−４，６−ジアミノ−１，３，５−トリアジン、モノ（ヒドロキシメチル）メラミン、ジ（ヒドロキシメチル）メラミン、トリ（ヒドロキシメチル）メラミンの塩が好ましく、とりわけメラミン、ベンゾグアナミン、アセトグアナミンの塩が好ましい。
【００４９】
トリアジン系化合物とシアヌール酸またはイソシアヌール酸との塩は、トリアジン系化合物とシアヌール酸またはイソシアヌール酸の混合物を水スラリーとなし、良く混合して両者の塩を微粒子状に形成させた後、このスラリーを濾過、乾燥して得られる粉末であり、単なる混合物とは異なる。この塩は完全に純粋である必要は無く、多少未反応のトリアジン系化合物ないしシアヌール酸、イソシアヌール酸が残存していても良い。
【００５０】
また、樹脂に配合される前の塩の平均粒径は、成形品の難燃性、機械的強度や表面性の点から１００〜０．０１μｍが好ましく、さらに好ましくは８０〜１０μｍである。また、上記塩の分散性が悪い場合には、トリス（β−ヒドロキシエチル）イソシアヌレートなどの分散剤を併用してもかまわない。
【００５１】
上記塩の使用量はポリブチレンテレフタレート樹脂（Ａ）１００重量部に対して通常、０．０１〜５０重量部、好ましくは０．１〜４０重量部、さらに好ましくは０．５〜３０重量部である。
【００５２】
また本発明の難燃性樹脂組成物および成形品はエラストマーを配合することにより、難燃性を低下させることなく、耐湿熱特性、機械特性、リサイクル性を向上させることができる。
【００５３】
このようなエラストマーとしては、ガラス転移温度が室温以下のものであれば特に制限はないが、例えば、ポリプロピレン、ポリエチレンなどのポリオレフィン系重合体、エチレン／プロピレン共重合体、エチレン／１−ブテン共重合体、エチレン／プロピレン／非共役ジエン共重合体、エチレン／アクリル酸エチル共重合体、エチレン／メタクリル酸グリシジル共重合体、エチレン／酢酸ビニル／メタクリル酸グリシジル共重合体、エチレン／プロピレン−ｇ−無水マレイン酸共重合体、スチレン樹脂、スチレン／アクリロニトリル共重合体、アクリロニトリル／ブタジエン／スチレン共重合体（ＡＢＳ樹脂）などのスチレン系樹脂などのポリオレフィン系共重合体、ポリエステルポリエーテルエラストマー、ポリエステルポリエステルエラストマー等のエラストマー、あるいはこれら合成樹脂の２種以上の混合物が挙げられるが、なかでもエチレン／１−ブテン共重合体、エチレン／プロピレン／非共役ジエン共重合体、エチレン／アクリル酸エチル共重合体、エチレン／メタクリル酸グリシジル共重合体、エチレン／酢酸ビニル／メタクリル酸グリシジル共重合体、エチレン／プロピレン−ｇ−無水マレイン酸共重合体が好ましく用いることができる。
【００５４】
上記エラストマーの添加量は、最終的に得られる難燃性樹脂組成物および成形品中に含有されるポリブチレンテレフタレート樹脂１００重量部に対して０．１〜１００重量部、好ましくは０．５〜８０重量部、より好ましくは１〜７０重量部である。
【００５５】
さらに、本発明の難燃性樹脂組成物および成形品は、本発明の目的を損なわない範囲でヒンダードフェノール系以外のリン系、イオウ系などの酸化防止剤や熱安定剤、紫外線吸収剤、滑剤、離型剤、および染料・顔料を含む着色剤などの通常の添加剤を１種以上添加することができる。
【００５６】
これらの添加量は最終的に得られる難燃性樹脂組成物および成形品に含有されるポリブチレンテレフタレート樹脂１００重量部に対し０．０１〜３重量部、好ましくは０．０２〜２重量部、更に好ましくは０．０３〜０．５重量部である。
【００５７】
本発明の難燃性樹脂組成物は通常公知の方法で製造される。例えば、ポリブチレンテレフタレート樹脂（Ａ）、ポリカーボネート樹脂（Ｂ）、赤リン（Ｃ）およびその他の必要な添加剤を予備混合して、またはせずに押出機などに供給して十分溶融混練することにより調製されるが、好ましくは、ハンドリング性や生産性の面から、ポリブチレンテレフタレート樹脂（Ａ）の一部、ポリカーボネート樹脂（Ｂ）の一部および赤リン（Ｃ）を一旦溶融混練して実際に難燃性樹脂組成物に配合されるべき赤リン量よりも赤リン濃度の高い樹脂組成物（Ｄ）を製造し、残りのポリブチレンテレフタレート樹脂（Ａ）、ポリカーボネート樹脂（Ｂ）に赤リン濃度の高い樹脂組成物（Ｄ）およびその他の任意に用いることができる添加剤を溶融混練することにより調製される。
【００５８】
あるいはポリブチレンテレフタレート樹脂（Ａ）の一部、ポリカーボネート樹脂（Ｂ）の一部、赤リン（Ｃ）およびその他の任意に用いることができる添加剤を一旦溶融混練して、実際に難燃性樹脂組成物に配合されるべき赤リン量よりも赤リン濃度の高い樹脂組成物（Ｄ）を製造し、残りの（Ａ）ポリブチレンテレフタレート樹脂（Ａ）、（Ｂ）ポリカーボネート樹脂に赤リン高濃度樹脂組成物（Ｄ）および赤リン濃度の高い樹脂組成物（Ｄ）の段階で添加した任意に用いることができる添加剤以外の添加剤を溶融混練することにより調製される。
【００５９】
上記のように実際に難燃性樹脂組成物に配合されるべき赤リン量よりも赤リン濃度の高い樹脂組成物（Ｄ）を製造する段階で、その他の任意に用いることができる添加剤を配合する場合、これらの任意に用いることができる添加剤はあらかじめ赤リンと混合しておくことが好ましい。
【００６０】
特に任意に用いることができる添加剤の中でも、赤リンの安定剤として使用される金属酸化物、特に酸化チタンを添加する場合、酸化チタンは赤リン高濃度品（Ｄ）を製造する段階で配合することが好ましく、さらにあらかじめ赤リンと酸化チタンをヘンシェルミキサー等の機械的な混合装置を用いて混合しておくと、赤リンの安定性、赤リンの分散性や得られる樹脂組成物の非着色性を向上することができる。
【００６１】
かかる赤リン高濃度品（Ｄ）の赤リン配合量は、赤リン高濃度品製造時の製造性の面、赤リンの分散性の面、および最終的に得られる樹脂組成物の難燃性、機械物性、成形性の面からポリカーボネート樹脂（Ｂ）１００重量部に対して３０〜２００重量部が好ましく、特に好ましくは３５〜１５０重量部である。
【００６２】
また赤リン高濃度品中のポリブチレンテレフタレート樹脂（Ａ）とポリカーボネート樹脂（Ｂ）の配合量は、赤リン（Ｃ）との相溶性、赤リンの分散性、赤リン高濃度品の生産性および最終的に得られる樹脂組成物の難燃性、薄肉衝撃特性の面から、ポリカーボネート樹脂（Ｂ）１００重量部に対して、ポリブチレンテレフタレート樹脂（Ａ）を０〜２００重量部、好ましくは１〜１５０重量部、さらに好ましくは５〜１００重量部である。
ポリカーボネート樹脂のみからなる赤リン高濃度品（Ｄ）でも、本効果を発現するが、ポリブチレンテレフタレート樹脂（Ｂ）と併用すると、ポリカーボネート樹脂（Ｂ）とポリブチレンテレフタレート樹脂（Ａ）と赤リン（Ｄ）の相乗効果により、さらに相溶性が向上し、
赤リンの分散性、最終的に得られる樹脂組成物の難燃性、薄肉衝撃特性が向上する。
【００６３】
かかる赤リン濃度の高い樹脂組成物（Ｄ）は、いわゆるマスターペレットの形態で好ましく用いられるが、それに限定されず、いわゆるチップ状、粉末状、あるいはそれらの混合物の形態であってもよい。またかかる（Ｄ）成分と配合するポリブチレンテレフタレート樹脂、ポリエチレンテレフタレート樹脂はペレット状であることが好ましいが、それに限定されず、いわゆるチップ状、粉末状あるいは、チップ状と粉末状の混合物であってもよい。さらに（Ｄ）成分と、それと配合するポリブチレンテレフタレート樹脂、ポリカーボネート樹脂の形態、大きさ、形状はほぼ同等、あるいは互いに似通っていることが均一に混合し得る点で好ましい。樹脂組成物を製造するに際し、例えば“ユニメルト”タイプのスクリューを備えた単軸押出機、二軸、三軸押出機およびニーダタイプの混練機などを用いることができる。
【００６４】
また本発明の赤リン濃度の高い樹脂組成物（Ｄ）はポリブチレンテレフタレート樹脂に難燃性を付与するものであり、そのためポリブチレンテレフタレート樹脂用難燃剤として使用することができる。
【００６５】
かくして得られる難燃性樹脂組成物および成形品は通常公知の方法で成形することができ、射出成形、押出成形、圧縮成形などの成形品、シート、フィルムなどのあらゆる形状の成形物品とすることができる。なかでも射出成形品用途に特に好適である。またウエルド部やヒンジ部を有する成形品やインサート成形品など複雑な形状の成形加工品、薄肉成形品にも好適であり、各種機械機構部品、電気電子部品または自動車部品に好適である。
【００６６】
例えば、各種ギヤー、各種ケース、センサー、ＬＥＤランプ、コネクター、ソケット、抵抗器、リレーケース、スイッチ、コイルボビン、コンデンサー、バリコンケース、光ピックアップ、発振子、各種端子板、変成器、プラグ、プリント配線板、チューナー、スピーカー、マイクロフォン、ヘッドフォン、小型モーター、磁気ヘッドベース、パワーモジュール、ハウジング、半導体、液晶ディスプレー部品、ＦＤＤキャリッジ、ＦＤＤシャーシ、ＨＤＤ部品、モーターブラッシュホルダー、パラボラアンテナ、コンピューター関連部品などに代表される電気・電子部品；ＶＴＲ部品、テレビ部品、アイロン、ヘアードライヤー、炊飯器部品、電子レンジ部品、音響部品、オーディオ・レーザーディスク・コンパクトディスクなどの音声機器部品、照明部品、冷蔵庫部品、エアコン部品、タイプライター部品、ワードプロセッサー部品などに代表される家庭、事務電気製品部品、オフィスコンピューター関連部品、電話機関連部品、ファクシミリ関連部品、複写機関連部品、洗浄用治具、オイルレス軸受、船尾軸受、水中軸受、などの各種軸受、モーター部品、ライター、タイプライターなどに代表される機械関連部品、顕微鏡、双眼鏡、カメラ、時計などに代表される光学機器、精密機械関連部品、オルタネーターターミナル、オルタネーターコネクター、ＩＣレギュレーター、ライトディヤー用ポテンショメーターベース、排気ガスバルブなどの各種バルブ、燃料関係・排気系・吸気系各種パイプ、エアーインテークノズルスノーケル、インテークマニホールド、燃料ポンプ、エンジン冷却水ジョイント、キャブレターメインボディー、キャブレタースペーサー、排気ガスセンサー、冷却水センサー、油温センサー、ブレーキパットウェアーセンサー、スロットルポジションセンサー、クランクシャフトポジションセンサー、エアーフローメーター、ブレーキバット磨耗センサー、エアコン用サーモスタットベース、暖房温風フローコントロールバルブ、ラジエーターモーター用ブラッシュホルダー、ウォーターポンプインペラー、タービンべイン、ワイパーモーター関係部品、デュストリビュター、スタータースィッチ、スターターリレー、トランスミッション用ワイヤーハーネス、ウィンドウオッシャーノズル、エアコンパネルスィッチ基板、燃料関係電磁気弁用コイル、ヒューズ用コネクター、ホーンターミナル、電装部品絶縁板、ステップモーターローター、ランプソケット、ランプリフレクター、ランプハウジング、ブレーキピストン、ソレノイドボビン、エンジンオイルフィルター、点火装置ケースなどの各種用途に有用であるが、上記の中で特に本発明の特徴、すなわち薄肉成形品の難燃性および衝撃特性、耐湿熱特性や低接点汚染性を活かした部品として、コネクター、コイルボビン、リレー、スイッチに好適に用いることができる。
【００６７】
【実施例】
以下実施例により本発明の効果を更に詳細に説明する。ここで部とはすべて重量部をあらわす。各特性の測定方法は以下の通りである。
【００６８】
（１）機械特性
射出成形により得たダンベル試験片についてＡＳＴＭ Ｄ−６３８に従い引張降伏強度を測定した。
【００６９】
（２）衝撃特性
ＡＳＴＭ Ｄ−２５６に従い、厚さ１／４インチ（ノッチ付）のアイゾッド衝撃強度を測定した。
【００７０】
（３）耐熱性（荷重たわみ温度）
ＡＳＴＭ−Ｄ６４８に従って、荷重１．８２ＭＰａにおける荷重たわみ温度を測定した。
【００７１】
（４）難燃性
射出成形により得た難燃性評価用試験片についてＵＬ９４に定められている評価基準に従い難燃性を評価した。難燃性レベルはＶ−０＞Ｖ−１＞Ｖ−２＞ＨＢの順に低下する。また５本のサンプルの燃焼時間の合計を難燃性の指標とした。
【００７２】
（５）耐湿熱ブリードアウト特性
射出成形により得られた難燃性評価用試験片を用い、温度１２１℃、湿度１００％ＲＨの条件下で２４時間処理した後の表面状態を光学顕微鏡で観察した。○：ブリード物は認められない、○：多少観察される、×：かなり観察されるの三段階で耐湿熱ブリードアウト特性を評価した。
【００７３】
（６）耐湿熱接点汚染性
５００ｍｌの三角フラスコ中に、厚さ１ｍｍ、１ｃｍ四方の銅板を樹脂組成物ペレット１００ｇで覆い、密閉し、温度１２１℃、湿度１００％ＲＨの条件下で２４時間処理した後の銅板の変色状態を観察した。○：変色しない、○：多少変色する、×：かなり変色するの三段階で接点汚染性を評価した。
【００７４】
（７）リサイクル評価
射出成形品を粉砕／成形を繰り返し行い、最終的に３回目に成形した燃焼試験片を用い、耐湿熱ブリードアウト特性、耐湿熱接点汚染性を評価した。
【００７５】
参考例１ 赤リン高濃度品（Ｄ−１）の製造
ポリカーボネート樹脂（以下ＰＣと略す）である”ユーピロン”Ｓ３０００（三菱エンジニアリングプラスチック（株）製）１００重量部に対して、赤リン（燐化学工業社製”ノーバエクセル”１４０：平均粒径２９．７μ、赤リン５ｇに純水１００ｍＬを加え、オートクレーブ中、１２１℃で１００時間抽出処理し、赤リンをろ過した後ろ液を２５０ｍＬに希釈し導電率計（横河電機社製、パーソナルＳＣメーター）を用いて測定した時の導電率２００μm Ｓ／ｃｍ）を、赤リン高濃度品中の赤リン量が３０重量％となるように、４３重量部混合し、窒素フローを行いながら、スクリュ径３０ｍｍ、Ｌ／Ｄ＝４５．５の同軸方向回転２軸押出機（日本精鋼社製、ＴＥＸ−３０）を用いて樹脂温度２８０℃で溶融押出し、ＰＣの赤リン高濃度品（Ｄ−１）を製造した。得られた赤リン高濃度品を１１０℃で乾燥後、射出成形（シリンダー温度２８０℃、金型温度８０℃）により燃焼試験片を調製し、耐湿熱ブリードアウト、耐湿熱接点汚染性を評価した。結果はブリードアウト：○、接点汚染：○、リサイクルブリードアウト：○、リサイクル接点汚染：△であった。
【００７６】
参考例２ 赤リン高濃度品（Ｄ−２）
ＰＣ樹脂である”ユーピロン”Ｓ３０００（三菱エンジニアリングプラスチック（株）製）１００重量部に対して、ポリブチレンテレフタレート樹脂（以下ＰＢＴと略す）である東レＰＢＴ１１００Ｓ（東レ（株）製）１００重量部、および赤リン（燐化学工業社製”ノーバエクセル”１４０）を８６重量部混合し（赤リン高濃度品中赤リン量３０重量％）、窒素フローを行いながら、スクリュ径３０ｍｍ、Ｌ／Ｄ＝４５．５の同軸方向回転２軸押出機（日本精鋼社製、ＴＥＸ−３０）を用いて樹脂温度２８０℃で溶融押出し、ＰＣ樹脂の赤リン高濃度品（Ｄ−２）を製造した。該赤リン高濃度品を用い、上記参考例１と同様に耐湿熱ブリードアウト、耐湿熱接点汚染性を評価した。結果はブリードアウト：○、接点汚染：○、リサイクルブリードアウト：○、リサイクル接点汚染：△であった。
【００７７】
参考例３ 赤リン高濃度品（Ｄ−３）
ポリブチレンテレフタレート樹脂（以下ＰＢＴと略す）である東レＰＢＴ１１００Ｓ（東レ（株）製）１００重量部に対して、赤リン（燐化学工業社製”ノーバエクセル”１４０）を４３重量部混合し（赤リン高濃度品中赤リン量３０重量％）、窒素フローを行いながら、スクリュ径３０ｍｍ、Ｌ／Ｄ＝４５．５の同軸方向回転２軸押出機（日本精鋼社製、ＴＥＸ−３０）を用いて樹脂温度２８０℃で溶融押出し、ＰＣ樹脂の赤リン高濃度品（Ｄ−２）を製造した。該赤リン高濃度品を用い、参考例１と同様に行った。結果はブリードアウト：○、接点汚染：○、リサイクルブリードアウト：○、リサイクル接点汚染：△であった。
【００７８】
参考例４ 赤リン高濃度品（Ｄ−４）の製造
ポリカーボネート樹脂（以下ＰＣと略す）である”ユーピロン”Ｓ３０００（三菱エンジニアリングプラスチック（株）製）１００重量部に対して、赤リンとして燐化学工業社製、“ノーバレッド”１２０（平均粒径３８μｍ、導電率１２００μＳ／ｃｍ、粒径７５μｍ以上の赤リン含量１５％）を用いた以外は参考例１と同様に行った。
ブリードアウト：×、接点汚染：×。リサイクル性は行わず。
【００７９】
以上の参考例に示した赤リン高濃度品の製造より、特定の導電率の赤リンを用いることにより、耐湿熱ブリードアウト特性、耐接点汚染性、リサイクルによる耐湿熱ブリードアウト特性、耐接点汚染性に優れた赤リン高濃度品を得ることができる。
【００８７】
実施例１〜５、比較例１〜３（ガラス強化系ＰＢＴ）
ＰＢＴ樹脂に対して表２に示す配合割合で、ＰＣ、参考例で製造した赤リン高濃度品、ガラス繊維、およびその他の添加剤を混合し、スクリュ径３０ｍｍ、Ｌ／Ｄ４５．５の同方向回転２軸押出機（日本製鋼社製、ＴＥＸ−３０：スクリュは２条ネジで相互の噛み合い３．５ｍｍの２本のスクリュを使用し、Ｌ／Ｄ＝４の４５度に傾いた１０枚のニーディングディスクからなるスクリュエレメントを順逆の順番で設け、さらに逆フルフライトエレメントを設けた混練力の強いスクリュ形状）を用いて樹脂温度２８０℃で溶融押出した。得られたペレットを乾燥後、射出成形（シリンダー温度２８０℃、金型温度８０℃）によりＡＳＴＭＤ−６３８、Ｄ−２５６、Ｄ−６４８に規定されている引張試験片、衝撃試験片、荷重たわみ試験片に規定されている引張試験片、衝撃試験片およびＵＬ９４に基く難燃性評価用試験片（１／３２”）を調製した。またリサイクル評価用サンプルは燃焼試験片を粉砕し、成形した。この操作を繰り返し最終的に３回目の成形により得られた燃焼試験片をリサイクル性評価用サンプルとした。
【００８８】
なお実施例５では赤リン高濃度品を使用せずに、窒素フローしながら、上記装置を用い溶融押出しした以外は、上記方法と同様に行った。
【００８９】
各サンプルの難燃性、引張強度、衝撃強度、耐湿熱ブリードアウト、耐湿熱接点汚染、およびリサイクルによる耐湿熱ブリードアウト、耐湿熱接点汚染の測定を行った。結果を表２に示す。
【００９０】
尚、ガラス繊維強化系については樹脂組成物中のガラス繊維重量％は全樹脂組成物１００重量％に対して３０重量％になるように配合した。
【００９１】
また、表中の、ＧＦはガラス繊維（日東紡績社製“ＣＳ３ＰＥ９４１Ｓ”）、フッ素系樹脂はポリテトラフルオロエチレン（三井・デュポン・フロロケミカル社製“テフロン（登録商標）６Ｊ”）、シアヌール酸塩はメラミンシアヌレート（日産化学社製“ＭＣ４４０”）、安定剤とはペンタエリスルチル−テトラキス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］（チバ・ガイギー社製”ＩＲ−１０１０”）のことを表わす。一連の結果を表１に示す。
【００９２】
【表２】

【００９３】
実施例１〜５と比較例１〜３の評価結果より、ＰＢＴに特定量のＰＣ樹脂と特定導電率の赤リンを配合することにより特異的に高度な難燃性を有し、かつ機械特性や耐熱性に優れ、耐湿熱ブリードアウト、耐湿熱接点汚染、およびリサイクルによる耐湿熱ブリードアウト、耐湿熱接点汚染性が向上することがわかる。
【００９４】
比較例１よりＰＣ樹脂を配合しないと難燃性が得られないばかりか、耐湿熱ブリードアウト、耐湿熱接点汚染、およびリサイクルによる耐湿熱ブリードアウト、耐湿熱接点汚染性が低下する。
【００９５】
また比較例３に示したようにＰＣ量が多いと、難燃性ランクはＶ−０ではあるが、燃焼時間が長くなる傾向が認められ、また耐湿熱ブリードアウト、耐湿熱接点汚染、およびリサイクルによる耐湿熱ブリードアウト、耐湿熱接点汚染性が低下する。またガラス繊維強化系においては、ＰＣの量が多いと耐熱性が顕著に低下することがわかる。
【００９６】
実施例１と比較例３の比較から、ＰＣと特定の導電率の赤リンを配合することにより、高度な難燃性、機械特性、耐熱性、耐湿熱ブリードアウト、耐湿熱接点汚染、およびリサイクルによる耐湿熱ブリードアウト、耐湿熱接点汚染性を有した難燃性樹脂組成物が得られることがわかる。一方、ＰＣを本発明の範囲以上に使用すると、燃焼時が長くなり、ガラス繊維強化系においては、耐熱性が顕著に低下すると同時に、耐湿熱ブリードアウト、耐湿熱接点汚染、およびリサイクルによる耐湿熱ブリードアウト、耐湿熱接点汚染性が低下することがわかる。
【００９７】
また実施例１と実施例４の比較から、さらにＭＣ塩を配合すると、他の特性を低下させることなく、燃焼時間はさらに短縮され、高度な難燃性を付与することができる。
【００９８】
また実施例１と実施例３の比較から、赤リン高濃度品を用いることにより、同じ難燃性ランクＶ−０でも燃焼時間が短く、さらに機械特性、耐リサイクルによる耐湿熱ブリードアウト、耐湿熱接点汚染性が向上することがわかる。
【００９９】
実施例１、２の比較から、ＰＣからなる赤リン高濃度品を使用した場合とＰＣとＰＢＴからなる赤リン高濃度品を使用した場合、後者の方が燃焼時間が短く、機械特性も若干優れる。
【０１００】
本発明の難燃性樹脂組成物は、高度な難燃性を有するだけでなく、優れた機械特性（強度、衝撃）、耐熱性を有しており、耐湿熱ブリードアウト、耐湿熱接点汚染、およびリサイクルによる耐湿熱ブリードアウト、耐湿熱接点汚染性を有しており、機械機構部品、電気電子部品または自動車部品の要求特性を満足する材料である。特に金属との接触面を有しかつ過酷な条件下で使用されることから、コネクター、コイルボビン、リレー、スイッチ部品は高度な難燃性、機械特性、耐熱性、リサイクル性が要求されるが、本発明の難燃性樹脂組成物はこれらの用途に好適である。
【０１０１】
【発明の効果】
（１）本発明の特定量のＰＣ樹脂と特定導電率の赤リンを含有した難燃性ＰＢＴ樹脂組成物は、従来公知の他の赤リン含有難燃性樹脂組成物に比べ、高度な難燃性を有するだけでなく、優れた機械特性（強度、衝撃）、耐熱性を有しており、耐湿熱ブリードアウト、耐湿熱接点汚染、およびリサイクルによる耐湿熱ブリードアウト、耐湿熱接点汚染性を示す。
（２）本発明で得られる難燃性樹脂組成物はこれらの特徴を活かした機械部品、電気電子部品、自動車部品に有用であり、特にコネクター、コイルボビン、リレー、スイッチ部品に好適である[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a flame retardant resin composition using a non-halogen flame retardant. More specifically, thin-walled molded products are excellent in flame retardancy, heat resistance and mechanical properties (tensile strength, impact properties), bleed-out by wet heat treatment, contact contamination resistance and recyclability, mechanical mechanism parts, electrical The present invention relates to a flame retardant resin composition suitable for electronic parts and automobile parts.
[0002]
[Prior art]
Polyester resins typified by polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycyclohexanedimethylene terephthalate, etc., or thermoplastic resins such as polycarbonate resin, polyamide resin, polyphenylene oxide resin, etc. It is being used as a molding material in a wide range of fields such as mechanical mechanism parts, electrical and electronic parts, and automobile parts. On the other hand, since these thermoplastic resins are inherently flammable, safety against flames, that is, flame retardancy is required in addition to the balance of general chemical and physical properties for use as industrial materials. There are many cases.
[0003]
As a method for imparting flame retardancy to a thermoplastic resin, a method in which a halogen-based organic compound as a flame retardant and an antimony compound as a flame retardant aid are compounded into a resin is common. However, this method has a tendency to generate a large amount of smoke during combustion.
[0004]
Therefore, in recent years, it has been strongly desired to use a flame retardant containing no halogen.
[0005]
Until now, as a method for flame-retarding a thermoplastic resin without using a halogen-based flame retardant, adding a hydrated metal compound such as aluminum hydroxide or magnesium hydroxide is widely known. In order to obtain flame retardancy, it is necessary to add a large amount of the hydrated metal compound, which has the disadvantage of losing the original properties of the resin.
[0006]
On the other hand, as a method for making a thermoplastic resin flame retardant without using such a hydrated metal compound, Japanese Patent Application Laid-Open No. 51-150553, Japanese Patent Application Laid-Open No. 58-108248, Disclosure in Japanese Utility Model Laid-Open Nos. 59-81351, 5-78560, 5-287119, 5-295164, 5-320486, and 5-339417 Has been. However, although any resin composition is a useful flame-retardant resin material that does not use a halogen-based flame retardant, white precipitates are generated on the surface of the molded product when these molded products are processed in a high-temperature and high-humidity state. There has been a problem that the heat-and-moisture resistance is deteriorated such that a bleed-out phenomenon is observed and mechanical properties are remarkably impaired.
[0007]
[Problems to be solved by the invention]
That is, the present invention uses a non-halogen flame retardant, has excellent flame retardancy and excellent bleed-out and contact contamination when processed in a high-temperature and high-humidity state in a thin-walled molded article, excellent mechanical properties, An object is to obtain a flame retardant resin composition having recyclability.
[0008]
[Means for Solving the Problems]
In light of the above situation, the present inventors have conducted extensive studies, and as a result, blended with a specific amount of polycarbonate resin and a specific conductivity of red phosphorus in a polybutylene terephthalate resin, Not only thick molded products (1/16 ") but also thin molded products (1/32") have a highly excellent flame retardancy, and also have a flame retardance rank V-0 defined by UL-94. In particular, a flame-retardant resin material that has an extremely short combustion time, can suppress the generation of bleeds due to wet heat treatment, can suppress contact contamination with metal parts due to wet heat treatment, and has superior mechanical properties and heat resistance. And the present invention has been achieved.
[0009]
  That is, the present invention
(A) For 100 parts by weight of polybutylene terephthalate resin,
(B) 0.1-80 parts by weight of polycarbonate resin,
(C) 0.01 to 30 parts by weight of red phosphorus having a conductivity of 0.1 to 1000 μS / cmAnd 0.01 to 3 parts by weight of a hindered phenol stabilizerA flame retardant resin composition containing
(However, the conductivity is 100 g of pure water added to 5 g of red phosphorus, extracted at 121 ° C. for 100 hours, and the back solution obtained by filtering red phosphorus is the conductivity of the extracted water diluted to 250 mL.)
  A flame retardant resin composition in which red phosphorus (C) is red phosphorus coated with a thermosetting resin, further containing 5-140 parts by weight of a filler with respect to 100 parts by weight of polybutylene terephthalate resin (A) A flame retardant resin composition,
  The flame retardant resin composition as described above, wherein the filler is glass fiber.,
PoA flame retardant resin composition further comprising 0.01 to 10 parts by weight of a fluororesin with respect to 100 parts by weight of the ribylene terephthalate resin (A),
  A salt composed of a triazine compound and cyanuric acid or isocyanuric acid is used in an amount of 0.01 to 100 parts by weight of the polybutylene terephthalate resin (A).2A flame retardant resin composition further comprising 0 part by weight,
  Polybutylene terephthalate resin (A), polycarbonate resin (B),Red phosphorus (C) having a conductivity of 0.1 to 1000 μS / cmAnd hindered phenol stabilizersA method for producing a flame retardant resin composition, characterized in that the flame retardant resin composition is produced by melt-kneading with an extruder.
  Part of polybutylene terephthalate resin (A),A part of the polycarbonate resin (B) and red phosphorus (C) having a conductivity of 0.1 to 1000 μS / cm are once melt-kneaded to produce a resin composition (D) having a high red phosphorus concentration, and the remaining poly Butylene terephthalate resin (A),The remaining polycarbonate resin (B),Hindered phenol stabilizerAnd a method for producing a flame retardant resin composition, comprising producing the flame retardant resin composition by melt-kneading a resin composition (D) having a high red phosphorus concentration with an extruder,
  Furthermore, the present invention provides
  Molded product comprising the flame retardant resin composition,
  Molded parts are mechanical mechanism parts,
  Molded products are electrical and electronic parts,
  Molded parts are auto parts,
  The molded product is a connector,
  The molded product is a coil bobbin,
  The above molded product, wherein the molded product is a relay or a switchIt is.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The flame retardant resin composition of the present invention will be specifically described below. Examples of the polybutylene terephthalate resin (A) of the present invention include a high molecular weight thermoplastic polyester having an ester bond in the main chain, using terephthalic acid as an acid component and 1,4-butanediol as a glycol component. It is also possible to copolymerize other copolymerizable components. For example, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, oxalic acid, adipic acid, 1,4-cyclohexanedicarboxylic acid and the like as the acid component, and ethylene glycol, propylene glycol, 1,6-hexanediol, 1 , 4-Cyclohexanedimethanol, bisphenol A, ethylene oxide adducts of bisphenol A, and the like can also be used.
[0011]
The amount of copolymerization in the case of copolymerizing other components as described above is not particularly limited as long as it does not significantly impair the characteristics of polybutylene terephthalate, but it is 0 with respect to the total number of moles of dicarboxylic acid units and glycol units. It is preferable that it is about -30 mol%, More preferably, it is about 0-25 mol%, More preferably, it is about 0-20 mol%.
[0012]
The polybutylene terephthalate used in the present invention preferably has an intrinsic viscosity of 0.36 to 1.60, particularly 0.52 to 1.25, measured at 25 ° C. using an o-chlorophenol solvent. .
[0013]
The polycarbonate resin (B) used in the present invention is obtained by reacting an aromatic dihydric phenol compound with phosgene or a carbonic acid diester. The aromatic homo- or copolycarbonate resin has a viscosity average molecular weight of 10,000. Is in the range of ~ 1000000. Here, as the dihydric phenol compound, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4-hydroxyphenyl) methane 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy-3,5-diphenyl) butane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-diethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1-phenyl- 1,1-bis (4-hydroxyphenyl) ethane or the like can be used, and these can be used alone or as a mixture.
[0014]
The addition amount of the polycarbonate resin (B) in the present invention is 0.1 to 80 parts by weight, preferably 0.5 to 70 parts by weight, more preferably 1 to 60 parts by weight, based on 100 parts by weight of the polybutylene terephthalate resin. Particularly preferred is 5 to 50 parts by weight.
[0015]
The red phosphorus (C) used in the present invention is unstable as it is, and has a property of gradually dissolving in water or reacting slowly with water, and therefore has been treated to prevent this. Is preferably used. As a method for treating red phosphorus, red phosphorus is not pulverized as described in JP-A-5-229806, and red phosphorus is formed without forming a crushed surface highly reactive with water or oxygen on the surface of red phosphorus. A method of making phosphorus fine particles, a method of adding a small amount of aluminum hydroxide or magnesium hydroxide to red phosphorus to catalytically suppress oxidation of red phosphorus, and covering red phosphorus with paraffin or wax to suppress contact with moisture A method of stabilizing by mixing with ε-caprolactam or trioxane, a method of stabilizing red phosphorus by coating it with a thermosetting resin such as phenol, melamine, epoxy, or unsaturated polyester, Red phosphorus is treated with an aqueous solution of a metal salt such as copper, nickel, silver, iron, aluminum and titanium to precipitate the metal phosphorus compound on the surface of red phosphorus and stabilize it. Stable by coating red phosphorus with aluminum hydroxide, magnesium hydroxide, titanium hydroxide, zinc hydroxide, etc., and electroless plating coating with iron, cobalt, nickel, manganese, tin, etc. on the surface of red phosphorus And a method combining these, preferably, a method of forming red phosphorus into fine particles without pulverizing red phosphorus without forming a crushing surface on the surface of red phosphorus, Method of stabilizing by coating with thermosetting resin such as melamine, epoxy, unsaturated polyester, etc., by coating red phosphorus with aluminum hydroxide, magnesium hydroxide, titanium hydroxide, zinc hydroxide, etc. The method of stabilizing, particularly preferably, the method of making red phosphorus fine particles without forming a crushing surface on the surface of red phosphorus, It is a method of stabilizing by coating with a thermosetting resin such as a resin type, a melamine type, an epoxy type or an unsaturated polyester type. Among these thermosetting resins, phenolic thermosetting resins and red phosphorus coated with epoxy thermosetting resins can be preferably used from the viewpoint of moisture resistance, and phenolic thermosetting is particularly preferable. Red phosphorus coated with resin.
[0016]
Further, the average particle size of red phosphorus before blending with the resin is 35 to 0. 5 in terms of flame retardancy, mechanical properties, heat and humidity resistance, and suppression of chemical and physical deterioration of red phosphorus due to grinding during recycling. The thing of 01 micrometer is preferable, More preferably, it is 30-0.1 micrometer.
[0017]
The average particle size of red phosphorus can be measured with a general laser diffraction particle size distribution analyzer. The particle size distribution measuring apparatus includes a wet method and a dry method, and any of them may be used. In the case of a wet method, water can be used as a dispersion solvent for red phosphorus. At this time, the surface of red phosphorus may be treated with alcohol or a neutral detergent. Moreover, it is also possible to use phosphates, such as sodium hexametaphosphate and sodium pyrophosphate, as a dispersing agent. It is also possible to use an ultrasonic bus as a dispersing device.
[0018]
The average particle size of red phosphorus used in the present invention is as described above, but red phosphorus having a large particle size contained in red phosphorus, that is, red phosphorus having a particle size of 75 μm or more is flame retardant, Red phosphorus having a particle size of 75 μm or more is preferably removed by classification because it tends to significantly reduce mechanical properties, heat and humidity resistance, and recyclability. The content of red phosphorus having a particle size of 75 μm or more is preferably 10% by weight or less, more preferably 8% by weight or less, particularly preferably 5% by weight or less from the viewpoint of flame retardancy, mechanical properties, heat and humidity resistance, and recyclability. It is. Although there is no restriction | limiting in particular in a minimum, It is so preferable that it is near 0.
[0019]
Here, the content of red phosphorus having a particle size of 75 μm or more contained in red phosphorus can be measured by classification using a 75 μm mesh. That is, the content of red phosphorus having a particle size of 75 μm or more can be calculated from A / 100 × 100 (%) from the residual amount A (g) when 100 g of red phosphorus is classified with a 75 μm mesh.
[0020]
Further, the conductivity of red phosphorus (B) used in the present invention when extracted in hot water (here, the conductivity is 100 g of pure phosphorus added to 5 g of red phosphorus at 121 ° C. in an autoclave, for example. Measure the conductivity of the extracted water after extracting with red phosphorus after 250 hours of red phosphorus filtration) in terms of moisture resistance, mechanical strength, tracking resistance, and recyclability of the resulting molded product Usually, it is 0.1 to 1000 μS / cm, preferably 0.1 to 800 μS / cm, and more preferably 0.1 to 500 μS / cm.
[0021]
Examples of such a commercially available red phosphorus product include “Nova Excel 140”, “Nova Excel F5” manufactured by Rin Kagaku Kogyo Co., Ltd., and equivalents thereof.
[0022]
The addition amount of red phosphorus (C) having an electrical conductivity of 0.1 to 1000 μS / cm in the present invention is 0.1 to 30 parts by weight, preferably 0.1 to 25 parts by weight with respect to 100 parts by weight of the polybutylene terephthalate resin. More preferably, it is 1-20 weight part, More preferably, it is 2-20 weight part. Among these, 4 to 15 parts by weight is particularly preferable.
[0023]
The flame retardant resin composition of the present invention can further improve stability, strength, heat resistance, and the like during extrusion and molding by adding a metal oxide as a stabilizer for red phosphorus. Specific examples of such metal oxides include cadmium oxide, zinc oxide, cuprous oxide, cupric oxide, ferrous oxide, ferric oxide, cobalt oxide, manganese oxide, molybdenum oxide, tin oxide and Examples thereof include titanium oxide, among which cadmium oxide, cuprous oxide, cupric oxide, and titanium oxide are preferable, more preferably cuprous oxide, cupric oxide, and titanium oxide, and particularly preferably titanium oxide. is there.
[0024]
In particular, titanium oxide not only serves as a stabilizer for red phosphorus but also has an effect of improving the non-coloring property and the dispersibility of red phosphorus in the resulting resin composition.
[0025]
The addition amount of the metal oxide is preferably 0.01 to 20 parts by weight, particularly preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the polybutylene terephthalate resin (A) in terms of mechanical properties and moldability. .
[0026]
The flame retardant resin composition of the present invention can be greatly improved in strength, rigidity, heat resistance and the like by further adding a filler. The shape of the filler may be any of non-fibrous, such as fibrous and granular, and these can be used as one or more kinds.
[0027]
Specific examples of such fillers include glass fibers, carbon fibers, metal fibers, aramid fibers, asbestos, potassium titanate whiskers, wollastonite, glass flakes, glass beads, talc, mica, clay, calcium carbonate, barium sulfate. , Titanium oxide, aluminum oxide, and the like. Among them, chopped strand type glass fibers are preferably used.
[0028]
These addition amounts are preferably 5 to 140 parts by weight, particularly preferably 5 to 100 parts by weight, per 100 parts by weight of the polybutylene terephthalate resin (A).
[0029]
When the fluorine-based resin is further added to the flame-retardant resin composition of the present invention, the drop (drip) of the droplets during combustion is suppressed. Such fluororesins include polytetrafluoroethylene, polyhexafluoropropylene, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene) / Ethylene) copolymer, (hexafluoropropylene / propylene) copolymer, polyvinylidene fluoride, (vinylidene fluoride / ethylene) copolymer, and the like. Among them, polytetrafluoroethylene, (tetrafluoroethylene / Perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / ethylene) copolymer, and polyvinylidene fluoride are preferred. Polytetrafluoroethylene, (tetrafluoroethylene / ethylene) copolymer are preferable.
[0030]
Moreover, even if a silicone type compound is further added to the flame-retardant resin composition of this invention, the fall (drip) of the droplet at the time of combustion is suppressed.
[0031]
The silicone compound is a silicone resin and / or silicone oil.
[0032]
The addition amount of the fluorine-based resin is usually 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the polybutylene terephthalate resin (A) in terms of mechanical properties and moldability. Preferably it is 0.2-3 weight part.
[0033]
The silicone resin used in the present invention is a chemically bonded siloxane unit selected from units represented by the following general formulas (1) to (4) and mixtures thereof (wherein R is saturated or Represents a group selected from an unsaturated monovalent hydrocarbon group, a hydrogen atom, a hydroxyl group, an alkoxyl group, an aryl group, a vinyl group or an allyl group, preferably a methyl group and / or a phenyl group. An organosiloxane having a viscosity of about 200 to 300,000,000 centipoise at room temperature is preferred, but is not limited thereto as long as it is the above silicone resin.
[0034]
[Chemical 1]

[0035]
The silicone oil used in the present invention is represented by the following general formula (5) (where R represents an alkyl group or a phenyl group, and in particular, a methyl group and / or a phenyl group). N is an integer of 1 or more. The silicone oil to be used preferably has a viscosity of 0.65 to 100,000 centistokes, but is not limited thereto as long as it is the above-described silicone oil.
[0036]
[Chemical 2]

[0037]
In the present invention, a silicone resin and / or silicone oil can be used as the silicone compound, but in terms of flame retardancy, heat resistance, bleed-out resistance, contact contamination resistance, and electrical property degradation after wet heat treatment. A silicone resin is preferred.
[0038]
The addition amount of the silicone compound is usually 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the polybutylene terephthalate resin (A) in terms of mechanical properties and moldability. Preferably it is 0.2-3 weight part.
[0039]
The fluororesin and the silicone compound can be used in combination. The total addition amount of the fluororesin and the silicone compound in that case is 100 parts by weight of the polybutylene terephthalate resin (A) from the viewpoint of mechanical properties and moldability. The amount is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and still more preferably 0.2 to 3 parts by weight.
[0040]
It has been found that the flame retardant resin composition of the present invention maintains extremely good hydrolysis resistance even when exposed to high temperatures for a long period of time when a hindered phenol stabilizer is used in combination. Examples of such a stabilizer include triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylene Bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3,5-di Tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di- -Butyl-4-hydroxybenzyl) benzene, bis or tris (3-t-butyl-6-methyl-4-hydroxyphenyl) propane, N, N'-hexamethylenebis (3,5-di-t-butyl- 4-hydroxy-hydrocinnamide), N, N′-trimethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide) and the like.
[0041]
In the present invention, such a hindered phenol-based stabilizer can be added as necessary. The amount of the hindered phenol-based stabilizer at that time is usually 100 weight of polybutylene terephthalate resin (A). It is 0.01-3 weight part with respect to a part, Preferably it is 0.02-2 weight part, More preferably, it is 0.03-0.5 weight part.
[0042]
The triazine compound and the salt of cyanuric acid or isocyanuric acid used in the present invention are an adduct of cyanuric acid or isocyanuric acid and a triazine compound, usually one to one (molar ratio), depending on the case. An adduct having a composition of 1: 2 (molar ratio). Of the triazine compounds, those that do not form a salt with cyanuric acid or isocyanuric acid are excluded.
[0043]
Examples of the triazine-based compound include compounds represented by the following general formula (6).
[0044]
[Chemical Formula 3]

[0045]
In the general formula (6), R¹, R², R^Three, R^FourAre the same or different hydrogen, aryl group, alkyl group, aralkyl group, cycloalkyl group, or -CONH₂It is. Here, the aryl group has 6 to 15 carbon atoms, the alkyl group has 1 to 10 carbon atoms, the aralkyl group has 7 to 16 carbon atoms, and the cycloalkyl group has 4 to 15 carbon atoms. Is preferred. R^FiveIs -NR in the above formula¹R²Or -NR^ThreeR^FourThe same group as or independently of these, hydrogen, aryl group, alkyl group, aralkyl group, cycloalkyl group, -NH₂Or -CONH₂Wherein the aryl group has 6 to 15 carbon atoms, the alkyl group has 1 to 10 carbon atoms, the aralkyl group has 7 to 16 carbon atoms, and the cycloalkyl group Preferably has 4 to 15 carbon atoms.
[0046]
R¹, R², R^Three, R^FourSpecific examples of hydrogen, phenyl group, p-toluyl group, α-naphthyl group, β-naphthyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group Tert-butyl group, hydroxymethyl group, methoxymethyl group, benzyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 2-methyl-1-pentyl group, 4-methyl-1-cyclohexyl group, amide group, etc. Of these, hydrogen, phenyl group, methyl group, hydroxymethyl group, methoxymethyl group, benzyl group, and amide group are preferable.
[0047]
R^FiveSpecific examples of are amino group, amide group, methylamino group, dimethylamino group, ethylamino group, diethylamino group, mono (hydroxymethyl) amino group, di (hydroxymethyl) amino group, mono (methoxymethyl) amino. Group, di (methoxymethyl) amino group, phenylamino group, diphenylamino group, hydrogen, phenyl group, p-toluyl group, α-naphthyl group, β-naphthyl group, methyl group, ethyl group, n-propyl group, isopropyl Group, n-butyl group, sec-butyl group, tert-butyl group, benzyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 2-methyl-1-pentyl group, 4-methyl-1-cyclohexyl group and the like. Among them, hydrogen, amino group, amide group, methyl group, mono (hydroxymethyl) amino group, di (Hydroxymethyl) amino group, mono (methoxymethyl) amino group, di (methoxymethyl) amino group, phenyl group and benzyl group are preferred.
[0048]
Of the salts of the compound represented by the general formula (6) and cyanuric acid or isocyanuric acid, melamine, benzoguanamine, acetoguanamine, 2-amido-4,6-diamino-1,3,5-triazine, mono Salts of (hydroxymethyl) melamine, di (hydroxymethyl) melamine, and tri (hydroxymethyl) melamine are preferable, and salts of melamine, benzoguanamine, and acetoguanamine are particularly preferable.
[0049]
The salt of the triazine compound and cyanuric acid or isocyanuric acid is prepared by forming a mixture of the triazine compound and cyanuric acid or isocyanuric acid into a water slurry and mixing them well to form both salts in the form of fine particles. It is a powder obtained by filtering and drying the slurry, and is different from a simple mixture. This salt does not have to be completely pure, and some unreacted triazine compound, cyanuric acid or isocyanuric acid may remain.
[0050]
Moreover, the average particle diameter of the salt before blending with the resin is preferably 100 to 0.01 μm, more preferably 80 to 10 μm from the viewpoint of flame retardancy, mechanical strength and surface property of the molded product. Further, when the dispersibility of the salt is poor, a dispersant such as tris (β-hydroxyethyl) isocyanurate may be used in combination.
[0051]
The amount of the salt used is usually 0.01 to 50 parts by weight, preferably 0.1 to 40 parts by weight, more preferably 0.5 to 30 parts by weight with respect to 100 parts by weight of the polybutylene terephthalate resin (A). is there.
[0052]
In addition, the flame-retardant resin composition and molded article of the present invention can improve moisture and heat resistance, mechanical properties, and recyclability without reducing flame retardancy by blending an elastomer.
[0053]
Such an elastomer is not particularly limited as long as it has a glass transition temperature of room temperature or lower, and examples thereof include polyolefin polymers such as polypropylene and polyethylene, ethylene / propylene copolymers, ethylene / 1-butene copolymer. Polymer, ethylene / propylene / non-conjugated diene copolymer, ethylene / ethyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer, ethylene / propylene-g-anhydrous Maleic acid copolymer, styrene resin, styrene / acrylonitrile copolymer, polyolefin copolymer such as styrene resin such as acrylonitrile / butadiene / styrene copolymer (ABS resin), polyester polyether elastomer, polyester polyester elastomer Examples include elastomers such as stomers, and mixtures of two or more of these synthetic resins. Among them, ethylene / 1-butene copolymers, ethylene / propylene / nonconjugated diene copolymers, ethylene / ethyl acrylate copolymers Ethylene / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer, and ethylene / propylene-g-maleic anhydride copolymer can be preferably used.
[0054]
The addition amount of the elastomer is 0.1 to 100 parts by weight, preferably 0.5 to 100 parts by weight with respect to 100 parts by weight of the polybutylene terephthalate resin contained in the finally obtained flame retardant resin composition and molded product. 80 parts by weight, more preferably 1 to 70 parts by weight.
[0055]
Furthermore, the flame retardant resin composition and molded product of the present invention are phosphorous other than hindered phenols, sulfur-based antioxidants and heat stabilizers, ultraviolet absorbers, and the like within a range that does not impair the object of the present invention. One or more usual additives such as lubricants, mold release agents, and colorants including dyes and pigments can be added.
[0056]
These addition amounts are 0.01-3 weight part with respect to 100 weight part of polybutylene terephthalate resin contained in the flame-retardant resin composition and molded article finally obtained, Preferably 0.02-2 weight part, More preferably, it is 0.03-0.5 weight part.
[0057]
  The flame retardant resin composition of the present invention is usually produced by a known method. For example, polybutylene terephthalate resin (A), polycarbonate resin (B), red phosphorus (C) and other necessary additives are premixed or supplied to an extruder or the like and sufficiently melt-kneaded. Preferably, a part of the polybutylene terephthalate resin (A) is preferable from the viewpoint of handleability and productivity.ThePart of the carbonate resin (B)andRed phosphorus (C) is once melt-kneaded to produce a resin composition (D) having a red phosphorus concentration higher than the amount of red phosphorus to be actually blended in the flame retardant resin composition, and the remaining polybutylene terephthalate resin (A),The polycarbonate resin (B) is prepared by melt-kneading a resin composition (D) having a high red phosphorus concentration and other optional additives.
[0058]
  Or part of polybutylene terephthalate resin (A)ThePart of the carbonate resin (B),A resin composition (red phosphorus concentration higher than the amount of red phosphorus to be actually blended in the flame-retardant resin composition) once melt-kneaded red phosphorus (C) and other optional additives. D) and the remaining (A) polybutylene terephthalate resin (A),(B) Melting and kneading additives other than the additive that can be arbitrarily added to the polycarbonate resin at the stage of the red phosphorus high concentration resin composition (D) and the high red phosphorus concentration resin composition (D). It is prepared by.
[0059]
As described above, other additives that can be arbitrarily used at the stage of manufacturing the resin composition (D) having a higher red phosphorus concentration than the amount of red phosphorus to be actually blended into the flame retardant resin composition. When blending, it is preferable to mix these optional additives with red phosphorus in advance.
[0060]
Among the additives that can be used arbitrarily, when adding a metal oxide used as a stabilizer of red phosphorus, particularly titanium oxide, titanium oxide is blended at the stage of producing a high concentration red phosphorus product (D). Further, when red phosphorus and titanium oxide are mixed in advance using a mechanical mixing device such as a Henschel mixer, the stability of red phosphorus, the dispersibility of red phosphorus, and the non-removability of the resulting resin composition Colorability can be improved.
[0061]
The amount of red phosphorus contained in the high red phosphorus product (D) is such that the production of red high concentration product, the dispersibility of red phosphorus, and the flame retardancy of the resin composition finally obtained are as follows. From the viewpoint of mechanical properties and moldability, the amount is preferably 30 to 200 parts by weight, particularly preferably 35 to 150 parts by weight, per 100 parts by weight of the polycarbonate resin (B).
[0062]
The blending amount of polybutylene terephthalate resin (A) and polycarbonate resin (B) in high-phosphorus high-concentration products is compatible with red phosphorus (C), dispersibility of red phosphorus, and productivity of high-red phosphorus products. From the viewpoint of the flame retardancy and thin impact characteristics of the finally obtained resin composition, the polybutylene terephthalate resin (A) is 0 to 200 parts by weight, preferably 1 with respect to 100 parts by weight of the polycarbonate resin (B). -150 weight part, More preferably, it is 5-100 weight part.
The red phosphorus high-concentration product (D) consisting only of the polycarbonate resin exhibits this effect, but when used in combination with the polybutylene terephthalate resin (B), the polycarbonate resin (B), the polybutylene terephthalate resin (A) and the red phosphorus ( The synergistic effect of D) further improves the compatibility,
The dispersibility of red phosphorus, the flame retardancy of the finally obtained resin composition, and the thin impact characteristics are improved.
[0063]
The resin composition (D) having a high red phosphorus concentration is preferably used in the form of a so-called master pellet, but is not limited thereto, and may be in the form of a so-called chip, powder, or a mixture thereof. The polybutylene terephthalate resin and polyethylene terephthalate resin to be blended with the component (D) are preferably in the form of pellets, but are not limited thereto, so-called chips, powders, or a mixture of chips and powders. Also good. Furthermore, it is preferable that the component (D) and the polybutylene terephthalate resin and polycarbonate resin to be blended with the component (D) are substantially the same in shape, size and shape, or similar to each other in that they can be uniformly mixed. In producing the resin composition, for example, a single screw extruder, a twin screw, a triple screw extruder, a kneader type kneader, or the like equipped with a “unimelt” type screw can be used.
[0064]
Further, the resin composition (D) having a high red phosphorus concentration of the present invention imparts flame retardancy to the polybutylene terephthalate resin, and can therefore be used as a flame retardant for the polybutylene terephthalate resin.
[0065]
The flame-retardant resin composition and molded product thus obtained can be molded by a generally known method, and molded articles of any shape such as molded products such as injection molding, extrusion molding, compression molding, sheets, films, etc. Can do. Among these, it is particularly suitable for injection molded product applications. It is also suitable for molded products having complicated shapes such as molded products having welds and hinges, insert molded products, and thin-walled molded products, and is suitable for various mechanical mechanism parts, electrical / electronic parts, and automobile parts.
[0066]
For example, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed wiring boards , Tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, housings, semiconductors, LCD display parts, FDD carriages, FDD chassis, HDD parts, motor brush holders, parabolic antennas, computer-related parts, etc. Audio equipment such as VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio / laser discs / compact discs Products, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, home appliances, office electrical parts, office computer parts, telephone parts, facsimile parts, copier parts, cleaning equipment Various kinds of bearings such as tools, oil-less bearings, stern bearings, underwater bearings, motor-related parts such as motor parts, lighters and typewriters, optical instruments such as microscopes, binoculars, cameras and watches, precision machines Related parts, alternator terminal, alternator connector, IC regulator, light meter potentiometer base, various valves such as exhaust gas valve, fuel-related / exhaust / intake system pipes, air intake nozzle snorkel, intake manifold, fuel pump, Engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake butt wear sensor, air conditioner thermostat Base, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, dust distributor, starter switch, starter relay, transmission wire harness, window washer nozzle, air conditioner panel switch Board, fuel-related electromagnetic valve coil, fuse connector, horn terminal It is useful for various applications such as electrical component insulation plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, etc. It can be suitably used for connectors, coil bobbins, relays, and switches as parts utilizing the characteristics, that is, flame retardancy and impact characteristics of thin-walled molded products, moisture and heat resistance characteristics, and low contact contamination.
[0067]
【Example】
The effects of the present invention will be described in more detail with reference to the following examples. Here, all parts represent parts by weight. The measuring method of each characteristic is as follows.
[0068]
(1) Mechanical properties
The tensile yield strength of the dumbbell specimen obtained by injection molding was measured according to ASTM D-638.
[0069]
(2) Impact characteristics
According to ASTM D-256, Izod impact strength of 1/4 inch thickness (notched) was measured.
[0070]
(3) Heat resistance (deflection temperature under load)
In accordance with ASTM-D648, the deflection temperature under load at 1.82 MPa was measured.
[0071]
(4) Flame resistance
The test piece for flame retardancy evaluation obtained by injection molding was evaluated for flame retardancy in accordance with the evaluation criteria defined in UL94. The flame retardancy level decreases in the order of V-0> V-1> V-2> HB. The total of the burning times of the five samples was used as an indicator of flame retardancy.
[0072]
(5) Humidity and heat bleed-out characteristics
Using a test piece for flame retardancy evaluation obtained by injection molding, the surface state after treatment for 24 hours under conditions of a temperature of 121 ° C. and a humidity of 100% RH was observed with an optical microscope. ◯: No bleed material was observed, ◯: Somewhat observed, X: Much observed, and the wet heat bleed-out characteristics were evaluated.
[0073]
(6) Moisture and heat contact contamination resistance
In a 500 ml Erlenmeyer flask, a 1 mm thick, 1 cm square copper plate was covered with 100 g of resin composition pellets, sealed, and the discolored state of the copper plate after being treated for 24 hours under conditions of a temperature of 121 ° C. and a humidity of 100% RH. Observed. ○: No discoloration, ○: Some discoloration, ×: Quite discoloration, contact contamination was evaluated in three stages.
[0074]
(7) Recycling evaluation
The injection molded product was repeatedly pulverized / molded, and finally the combustion test piece molded for the third time was used to evaluate moisture and heat bleed-out characteristics and moisture and heat contact contamination resistance.
[0075]
Reference Example 1 Production of high concentration red phosphorus product (D-1)
For 100 parts by weight of “Iupilon” S3000 (manufactured by Mitsubishi Engineering Plastics), which is a polycarbonate resin (hereinafter abbreviated as “PC”), red phosphorus (“NOVA EXCEL” 140 manufactured by Rin Chemical Industry Co., Ltd.): average particle size 29.7 μm Add 100 mL of pure water to 5 g of red phosphorus, extract in an autoclave at 121 ° C. for 100 hours, dilute the back solution obtained by filtering red phosphorus to 250 mL, and use a conductivity meter (Personal SC meter, manufactured by Yokogawa Electric Corporation). The conductivity when measured using 200 μm S / cm) was mixed with 43 parts by weight so that the amount of red phosphorus in the red phosphorus high-concentration product would be 30% by weight, and while flowing nitrogen, the screw diameter was 30 mm, L / D = 45.5 coaxial rotating twin screw extruder (manufactured by Nippon Seiko Co., Ltd., TEX-30), melt extrusion at a resin temperature of 280 ° C. D-1) was produced. The obtained red phosphorus high-concentration product was dried at 110 ° C., and then a combustion test piece was prepared by injection molding (cylinder temperature 280 ° C., mold temperature 80 ° C.) to evaluate moisture heat bleed out resistance and moisture heat contact contamination resistance. . The results were bleed out: ◯, contact contamination: ◯, recycled bleed out: ◯, recycled contact contamination: △.
[0076]
Reference Example 2 Red phosphorus high concentration product (D-2)
Toray PBT1100S (manufactured by Toray Industries, Inc.) 100 parts by weight, which is polybutylene terephthalate resin (hereinafter abbreviated as PBT), with respect to 100 parts by weight of “Iupilon” S3000 (manufactured by Mitsubishi Engineering Plastics), which is a PC resin, and 86 parts by weight of red phosphorus (“NOVA EXCEL” 140 manufactured by Rin Chemical Industry Co., Ltd.) is mixed (the amount of red phosphorus in the high concentration product of red phosphorus is 30% by weight), and while performing nitrogen flow, the screw diameter is 30 mm, L / D = 45 .5 coaxial direction rotating twin screw extruder (manufactured by Nippon Seiko Co., Ltd., TEX-30) was melt-extruded at a resin temperature of 280 ° C. to produce a PC resin red phosphorus high-concentration product (D-2). Using the red phosphorus high-concentration product, the moisture and heat bleed-out and moisture and heat contact contamination resistance were evaluated in the same manner as in Reference Example 1 above. The results were bleed out: ◯, contact contamination: ◯, recycled bleed out: ◯, recycled contact contamination: △.
[0077]
Reference Example 3 High concentration red phosphorus product (D-3)
To 100 parts by weight of Toray PBT1100S (manufactured by Toray Industries, Inc.), which is a polybutylene terephthalate resin (hereinafter abbreviated as PBT), 43 parts by weight of red phosphorus (“Nova Excel” 140 manufactured by Rin Chemical Industry Co., Ltd.) is mixed (red (Red phosphorus amount 30 wt% in high phosphorus concentration product), while using nitrogen flow, using a screw diameter 30 mm, L / D = 45.5 coaxial rotating twin-screw extruder (manufactured by Nippon Seiko Co., Ltd., TEX-30) The resin was melt-extruded at a temperature of 280 ° C. to produce a PC resin red phosphorus high-concentration product (D-2). The same procedure as in Reference Example 1 was performed using the red phosphorus high-concentration product. The results were bleed out: ◯, contact contamination: ◯, recycled bleed out: ◯, recycled contact contamination: △.
[0078]
Reference Example 4 Production of red phosphorus high-concentration product (D-4)
For 100 parts by weight of “Iupilon” S3000 (Mitsubishi Engineering Plastics Co., Ltd.), which is a polycarbonate resin (hereinafter abbreviated as “PC”), Phosphorus Chemical Industries, Ltd., “Novared” 120 (average particle size 38 μm, It was carried out in the same manner as in Reference Example 1 except that a conductivity of 1200 μS / cm and a red phosphorus content of 15 μm or more were used.
Bleed out: x, contact contamination: x. Not recyclable.
[0079]
By using red phosphorus with a specific conductivity from the production of high-phosphorus phosphorus products shown in the above reference examples, moisture and heat bleed-out characteristics, contact contamination resistance, moisture and heat bleed-out characteristics due to recycling, and contact resistance contamination It is possible to obtain a red phosphorus high-concentration product having excellent properties.
[0087]
  Example1-5Comparative example1-3(Glass reinforced PBT)
  PC, high red phosphorus concentration product manufactured in Reference Example, glass fiber, and other additives are mixed in the blending ratio shown in Table 2 with respect to the PBT resin, and the screw diameter is 30 mm and the L / D is 45.5 in the same direction. Rotating twin-screw extruder (manufactured by Nippon Steel Co., Ltd., TEX-30: Two screws with two threads and 3.5mm meshing with each other, 10 screws inclined at 45 degrees of L / D = 4 A screw element composed of a kneading disk was provided in the reverse order, and a melt shape with a strong kneading force provided with a reverse full flight element was melt extruded at a resin temperature of 280 ° C. After drying the obtained pellets, tensile test pieces, impact test pieces and load deflection tests specified in ASTM D-638, D-256, D-648 by injection molding (cylinder temperature 280 ° C., mold temperature 80 ° C.) A tensile test piece, an impact test piece specified for the piece, and a flame retardant evaluation test piece (1/32 ″) based on UL94 were prepared. A recycle evaluation sample was formed by pulverizing a combustion test piece. This operation was repeated, and finally the combustion test piece obtained by the third molding was used as a sample for evaluating recyclability.
[0088]
In Example 5, the same procedure as in the above method was performed except that the high-phosphorus high-concentration product was not used and melt extrusion was performed using the above apparatus while flowing nitrogen.
[0089]
Each sample was measured for flame retardancy, tensile strength, impact strength, moisture and heat bleed out, moisture and heat contact contamination, and moisture and heat contact bleed out by recycling and moisture and heat contact contamination. The results are shown in Table 2.
[0090]
In addition, about the glass fiber reinforced system, the glass fiber weight% in a resin composition was mix | blended so that it might be 30 weight% with respect to 100 weight% of all the resin compositions.
[0091]
  In the table, GF is glass fiber (“CS3PE941S” manufactured by Nitto Boseki Co., Ltd.), and the fluororesin is polytetrafluoroethylene (“Teflon manufactured by Mitsui, DuPont, Fluorochemicals, Inc.).(Registered trademark)6J "), cyanurate is melamine cyanurate (" MC440 "manufactured by Nissan Chemical Co., Ltd.), and stabilizer is pentaerythryl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate ] ("IR-1010" manufactured by Ciba Geigy))ofRepresents. Table of results1Shown in
[0092]
[Table 2]

[0093]
  Example1-5And comparative examples1-3From the above evaluation results, by blending PBT with a specific amount of PC resin and specific conductivity red phosphorus, it has high flame retardance specifically, excellent mechanical properties and heat resistance, moisture heat bleed out, It can be seen that moisture-resistant contact contamination, moisture-resistant bleed-out by recycling, and moisture-resistant contact contamination are improved.
[0094]
  Comparative example1If the PC resin is not further blended, not only flame retardancy is obtained, but also moisture and heat bleed-out, moisture and heat-resistant contact contamination, and moisture and heat-resistant bleed-out by recycling and moisture and heat-resistant contact contamination are reduced.
[0095]
  Comparative example3As shown in Fig. 4, when the amount of PC is large, the flame retardancy rank is V-0, but a tendency to increase the combustion time is recognized, and moisture and heat bleed out, moisture and heat contact contamination, and moisture and heat bleed due to recycling Out, moist and heat contact contamination is reduced. In the glass fiber reinforced system, it can be seen that the heat resistance is remarkably lowered when the amount of PC is large.
[0096]
  Example1And comparative examples3By comparing PC and red phosphorus of specific conductivity, advanced flame retardancy, mechanical properties, heat resistance, moisture and heat bleed out, moisture and heat contact contamination, and moisture and heat bleed out by recycling, moisture resistance It can be seen that a flame retardant resin composition having thermal contact contamination is obtained. On the other hand, if the PC is used beyond the range of the present invention, the combustion time becomes longer, and in the glass fiber reinforced system, heat resistance is remarkably reduced, and at the same time, moisture heat bleed out, moisture heat contact contamination, and heat resistance due to recycling. It can be seen that the bleed-out and moisture-resistant contact resistance are reduced.
[0097]
  Examples1And examples4From the above comparison, when MC salt is further blended, the combustion time can be further shortened and high flame retardancy can be imparted without lowering other properties.
[0098]
  Examples1And examples3From the above comparison, the use of high red phosphorus concentration products can shorten the combustion time even with the same flame retardancy rank V-0, and further improve the mechanical properties, moisture-resistant bleed-out due to recycling resistance, and moisture-resistant contact contamination resistance. Recognize.
[0099]
  Example1,2From the above comparison, when the high-phosphorus red high-concentration product made of PC is used and when the high-phosphorus high-phosphorus concentration product made of PC and PBT is used, the latter has a shorter burning time and slightly better mechanical properties.
[0100]
The flame retardant resin composition of the present invention has not only high flame retardancy but also excellent mechanical properties (strength, impact), heat resistance, moisture heat bleed out, moisture heat contact contamination, It is a material that has moisture and heat bleed-out by recycling and moisture and heat contact contamination resistance, and satisfies the required characteristics of mechanical mechanism parts, electrical and electronic parts or automobile parts. In particular, since it has a contact surface with metal and is used under severe conditions, connectors, coil bobbins, relays, and switch parts are required to have high flame resistance, mechanical properties, heat resistance, and recyclability. The flame retardant resin composition of the present invention is suitable for these uses.
[0101]
【The invention's effect】
(1) The flame-retardant PBT resin composition containing the specific amount of the PC resin and the specific conductivity of red phosphorus according to the present invention is more difficult than other conventionally known red phosphorus-containing flame-retardant resin compositions. Not only is it flammable, it also has excellent mechanical properties (strength, impact) and heat resistance. Show.
(2) The flame retardant resin composition obtained by the present invention is useful for mechanical parts, electrical and electronic parts, and automobile parts taking advantage of these characteristics, and particularly suitable for connectors, coil bobbins, relays, and switch parts.

Claims (15)

(A) For 100 parts by weight of polybutylene terephthalate resin ,
(B) 0.1 to 80 parts by weight of polycarbonate resin ,
(C) A flame retardant resin composition containing 0.01 to 30 parts by weight of red phosphorus having an electrical conductivity of 0.1 to 1000 μS / cm and 0.01 to 3 parts by weight of a hindered phenol stabilizer .
(However, the conductivity is 100 g of pure water added to 5 g of red phosphorus, extracted at 121 ° C. for 100 hours, and the back solution obtained by filtering red phosphorus is the conductivity of the extracted water diluted to 250 mL.) The flame retardant resin composition according to claim 1, wherein the red phosphorus (C) is red phosphorus coated with a thermosetting resin. The flame-retardant resin composition according to claim 1, further comprising 5 to 140 parts by weight of a filler per 100 parts by weight of the polybutylene terephthalate resin (A). The flame retardant resin composition according to claim 3, wherein the filler is glass fiber. The flame-retardant resin composition according to any one of claims 1 to 4, further comprising 0.01 to 10 parts by weight of a fluororesin with respect to 100 parts by weight of the polybutylene terephthalate resin (A). Against polybutylene terephthalate resin (A) 100 parts by weight of a triazine-based compound and cyanuric acid or even a salt 0.01-20 parts by weight of the isocyanuric acid comprising claims 1 to 5 in any one Flame retardant resin composition. The polybutylene terephthalate resin (A), the polycarbonate resin (B) , red phosphorus (C) having an electrical conductivity of 0.1 to 1000 μS / cm, and a hindered phenol stabilizer are melt-kneaded with an extruder. A method for producing a flame retardant resin composition, comprising producing the flame retardant resin composition according to any one of items 6 to 6 . A resin composition having a high red phosphorus concentration by once melting and kneading part of the polybutylene terephthalate resin (A), part of the polycarbonate resin (B), and red phosphorus (C) having a conductivity of 0.1 to 1000 μS / cm. The product (D) is produced, and the remaining polybutylene terephthalate resin (A) , the remaining polycarbonate resin (B), the hindered phenol stabilizer and the resin composition (D) having a high red phosphorus concentration are melt-kneaded with an extruder. A method for producing a flame retardant resin composition, comprising producing the flame retardant resin composition according to any one of claims 1 to 6 . The molded article which consists of a flame-retardant resin composition in any one of Claims 1-6. Molded article is mechanical section product according to claim 9 molded article according. The molded product according to claim 9, wherein the molded product is an electrical / electronic component. The molded article according to claim 9, wherein the molded article is an automobile part. 9. The molded article according moldings are connector. The molded product according to claim 9, wherein the molded product is a coil bobbin. The molded article according to claim 9, wherein the molded article is a relay or a switch.