JP2004075868A - Flame-retardant polybutylene terephthalate resin composition and molding prepared therefrom - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retardant polybutylene terephthalate resin composition which can give a molding specifically improved in mechanical properties, heat cycle resistance, and hue and being resistant to bleedout and good in appearance by compounding a polybutylene terephthalate resin with a non-halogen flame retardant and to provide a molding prepared therefrom. <P>SOLUTION: The flame-retardant polybutylene terephthalate resin composition is prepared by compounding 100pts.wt. (A) polybutylene terephthalate resin or (A) mixture containing 99-1wt.% polybutylene terephthalate resin and 1-99 wt.% polyethylene terephthalate resin with 1-50pts.wt. (B) multilayer polymer and 1-70pts.wt. (C) phosphoric ester. <P>COPYRIGHT: (C)2004,JPO

Description

【００４９】
（上式において、Ａｒ^１、Ａｒ^２、Ａｒ^３、Ａｒ^４は、同一または相異なるフェニル基あるいはハロゲンを含有しない有機残基で置換されたフェニル基を表す。また、Ｘは下記の（２）〜（４）式から選択される１種を示し、Ｒ^１〜Ｒ^８は同一または相異なる水素原子または炭素数１〜５のアルキル基を表し、Ｙは直接結合、Ｏ、Ｓ、ＳＯ２、Ｃ（ＣＨ３）２、ＣＨ２、ＣＨＰｈを表し、Ｐｈはフェニル基を表す。また、（１）式のｎは０以上の整数であり、異なるｎの混合物でもよい。また、（１）式のｋ、ｍはそれぞれ０以上２以下の整数であり、かつ（ｋ＋ｍ）は０以上２以下の整数である。
【００５０】
【化６】

【００５１】
【化７】

【００５２】
【化８】

【００５３】
なかでも下記化合物が好ましい。
【００５４】
【化９】

【００５５】
また、（Ｃ）燐酸エステルの添加量は、難燃性と機械特性の点から（Ａ）ポリブチレンテレフタレート樹脂１００重量部または、ポリブチレンテレフタレート樹脂９９〜１重量％、ポリエチレンテレフタレート樹脂１〜９９重量％からなる樹脂１００重量部に対して、１〜７０重量部であることが必要であり、好ましくは２〜６５重量部、より好ましくは３〜６０重量部である。
【００５６】
本発明における（Ｄ）繊維強化材とは、（Ｄ）繊維強化材をポリブチレンテレフタレート樹脂に配合することによって、高い強度の樹脂を得ることができるものであり、限定されるものではないが、ガラス繊維、アラミド繊維、炭素繊維、チタン酸カリ繊維、セラミックス繊維、およびスチール繊維などが挙げられ、ガラス繊維と炭素繊維が好ましく用いられる。前記の好ましく用いられるガラス繊維と炭素繊維としては、通常のＰＢＴの強化材に使用されるチョップドストランドタイプやロービングタイプのガラス繊維と炭素繊維などが挙げられ、表面処理剤としてアミノシラン化合物やエポキシシラン化合物などのシランカップリング剤および／またはウレタン、酢酸ビニル、ビスフェノールＡジグリシジルエーテル、ノボラック系エポキシ化合物などの一種以上のエポキシ化合物などを含有した集束剤で処理されたガラス繊維が好ましく用いられる。また、前記のシランカップリング剤および／または集束剤はエマルジョン液で使用されていても良い。
【００５７】
また、前記の（Ｄ）繊維強化材の繊維径は、５μｍ〜２０μｍが好ましく、特に好ましくは６μｍ〜１５μｍである。
【００５８】
また、（Ｄ）繊維状強化材の一部に無機充填剤を配合することができ、本発明組成物の結晶化特性、耐トラッキング性、耐アーク性、異方性、機械強度、難燃性あるいは熱変形温度などの一部を改良するものであり、かかる無機充填剤としては、限定されるものではないが針状、粒状、粉末状および層状の無機充填剤が挙げられ、具体例としては、ガラスビーズ、ミルドファイバー、チタン酸カリウィスカー、ワラステナイト、シリカ、カオリナイト、タルク、スメクタイト系粘土鉱物（モンモリロナイト、ヘクトライト）、バーミキュライト、マイカ、フッ素テニオライト、燐酸ジルコニウム、燐酸チタニウム、およびドロマイトなどが挙げられ、一種以上で用いられる。また、上記の無機充填剤には、カップリング剤処理、エポキシ化合物、あるいはイオン化処理などの表面処理が行われていても良い。また、粒状、粉末状および層状の無機充填剤の平均粒径は衝撃強度の点から０．１μｍ〜２０μｍであることが好ましく、特に０．２μｍ〜１０μｍであることが好ましい。また、無機充填剤の配合量は、繊維強化剤の配合量を越えない量が好ましい。
【００５９】
とくに無機充填剤として、ガラス繊維に対し、ガラスフレークを配合した組成物は、ソリの少ない成形品の製造に有用、あるいは珪酸塩化合物のタルクを配合した組成物は、射出成形性に優れたポリブチレンテレフタレート樹脂成形品の製造に有用である。
【００６０】
また、前記の（Ｄ）繊維強化材をチョップドストランドタイプとして用いる際の繊維長さは、１ｍｍ〜１０ｍｍが好ましく、特に好ましくは２ｍｍ〜７ｍｍである。
【００６１】
また、前記の（Ｄ）繊維強化材の配合量は難燃性、成形時の流動性の点から（Ａ）ポリブチレンテレフタレート樹脂１００重量部または、ポリブチレンテレフタレート樹脂９９〜１重量％、ポリエチレンテレフタレート樹脂１〜９９重量％からなる樹脂１００重量部に対して、１〜１５０重量部であることが好ましく、より好ましくは２５〜１４０重量部、特に好ましくは５０〜１２５重量部である。
【００６２】
また、前記の（Ｄ）繊維強化材の配合方法は、限定されるものではないが、他の本発明組成物あるいは一部の組成物と混合後に溶融混合する方法、溶融混練機である押出機の途中あるいは吐出口付近から投入して他の本発明組成物と溶融混合する方法などが挙げられる。
【００６３】
本発明における（Ｅ）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が好ましく、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。また、（Ｅ）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のうち、とくにメラミン、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く、公知の方法で製造されるが、例えば、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、乾燥後に一般には粉末状で得られる。また、上記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。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、機械的強度や耐湿熱特性、滞留安定性、表面性の点から１００〜０．０１μｍが好ましく、更に好ましくは８０〜１μｍである。また、上記の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や公知の表面処理剤、シリカ、ポリビニルアルコールなどを併用してもかまわない。
【００６４】
また、（Ｅ）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の配合量は、難燃性と機械特性の点から（Ａ）ポリブチレンテレフタレート樹脂１００重量部または、ポリブチレンテレフタレート樹脂９９〜１重量％、ポリエチレンテレフタレート樹脂１〜９９重量％からなる樹脂１００重量部に対して、１〜１５０重量部であることが好ましく、より好ましくは５〜１２０重量部、更に好ましくは１５〜８０重量部である。
【００６５】
本発明における（Ｆ）フッ素系化合物とは、さらにフッ素系樹脂を配合することにより、燃焼時の難燃性樹脂組成物が溶融落下することを抑制し、さらに難燃性を向上させることができる。前記の（Ｆ）フッ素系化合物とは、物質分子中にフッ素を含有する樹脂であり、具体的には、ポリテトラフルオロエチレン、ポリヘキサフルオロプロピレン、（テトラフルオロエチレン／ヘキサフルオロプロピレン）共重合体、（テトラフルオロエチレン／パーフルオロアルキルビニルエーテル）共重合体、（テトラフルオロエチレン／エチレン）共重合体、（ヘキサフルオロプロピレン／プロピレン）共重合体、ポリビニリデンフルオライド、（ビニリデンフルオライド／エチレン）共重合体などが挙げられるが、中でもポリテトラフルオロエチレン、（テトラフルオロエチレン／パーフルオロアルキルビニルエーテル）共重合体、（テトラフルオロエチレン／ヘキサフルオロプロピレン）共重合体、（テトラフルオロエチレン／エチレン）共重合体、ポリビニリデンフルオライドが好ましく、特にポリテトラフルオロエチレン、（テトラフルオロエチレン／エチレン）共重合体が好ましい。また、（Ｆ）フッ素系化合物の配合量は、難燃性と機械特性の点から（Ａ）ポリブチレンテレフタレート樹脂１００重量部、または、ポリブチレンテレフタレート樹脂９９〜１重量％、ポリエチレンテレフタレート樹脂１〜９９重量％からなる樹脂１００重量部に対して、０．０２〜１０重量部であることが好ましく、より好ましくは０．１〜８重量部、更に好ましくは０．２〜６重量部である。
【００６６】
本発明の（Ｇ）アルカリ土類金属塩とは、アルカリ土類金属に属するマグネシウム、カルシウム、およびバリウムの塩が好ましく、具体例としては水酸化マグネシウム、水酸化カルシウム、水酸化バリウム、酸化マグネシウム、酸化カルシウム、酸化バリウム、炭酸マグネシウム、炭酸カルシウム、炭酸バリウム、硫酸マグネシウム、硫酸カルシウム、硫酸バリウム、リン酸マグネシウム、リン酸カルシウム、リン酸バリウム、酢酸マグネシウム、酢酸カルシウム、酢酸バリウム、乳酸マグネシウム、乳酸カルシウム、乳酸バリウム、さらにはオレイン酸、パルミチン酸、ステアリン酸およびモンタン酸などの有機酸のマグネシウム塩、カルシウム塩、およびバリウム塩などが挙げられ、水酸化マグネシウムおよび炭酸カルシウムが好ましく用いられ、より好ましくは炭酸カルシウムが用いられる。また、上記の炭酸カルシウムは製造方法により、コロライド炭酸カルシウム、軽質炭酸カルシウム、重質炭酸カルシウム、湿式粉砕微粉重質炭酸カルシウム、湿式重質炭酸カルシウム（白亜）などが知られており、いずれも本発明に包含される。また、上記の炭酸カルシウムおよびアルカリ土類金属塩は、シランカップリング剤、有機物および無機物などの一種以上の表面処理剤で処理されていても良く、形状は粉末状、板状あるいは繊維状であっても構わないが、１０μｍ以下の粉末状で用いることが分散性などから好ましい。
【００６７】
（Ｇ）アルカリ土類金属塩を添加することにより、加水分解特性を著しく向上させることができる。非ハロゲン難燃剤として有効な燐酸エステル系化合物は燐酸エステル結合が加水分解され易いため、加水分解性に劣るという欠点を有している。本発明では、ビニル系樹脂によるブリードアウト防止と本アルカリ土類金属塩による酸トラップの相乗作用により大きく加水分解性が改良されているものと推察される。
【００６８】
また（Ｇ）アルカリ土類金属塩の配合量は、機械特性と加水分解性の点から（Ａ）ポリブチレンテレフタレート樹脂１００重量部、または、ポリブチレンテレフタレート樹脂９９〜１重量％、ポリエチレンテレフタレート樹脂１〜９９重量％からなる樹脂１００重量部に対して、０．０５〜５重量部であることが好ましく、より好ましくは０．１〜４．５重量部、更に好ましくは０．１５〜４重量部である。
【００６９】
本発明で使用される（Ｈ）エポキシ化合物とは、グリシジルエステル化合物、グリシジルエーテル化合物、およびグリシジルエステルエーテル化合物の少なくとも一種以上を用いたエポキシ化合物である。
【００７０】
また、ＰＢＴの加水分解性に優れた改善効果を発現するには、エポキシ当量５００未満のエポキシ化合物が好ましく、さらにはエポキシ当量４００未満のエポキシ化合物が特に好ましい。ここで、エポキシ当量とは、１グラム当量のエポキシ基を含むエポキシ化合物のグラム数が５００未満のエポキシ化合物であり、エポキシ当量の測定例を示すと、エポキシ化合物をピリジンに溶解し、０．０５Ｎ塩酸を加え４０〜４５℃で加熱後、指示薬にチモールブルーとクレゾールレツドの混合液を用い、０．０５Ｎ苛性ソーダで逆滴定する方法などが知られている。
【００７１】
また、上記のエポキシ化合物としては、単官能のグリシジルエステル化合物とグリシジルエーテル化合物を併用したエポキシ化合物あるいは単官能のグリシジルエステル化合物が好ましく用いられ、とくに、得られる組成物の粘度安定性と加水分解性のバランスから単官能のグリシジルエステル化合物がより好ましい。
【００７２】
また、上記のグリシジルエステル化合物としては、限定されるものではないが、具体例として、安息香酸グリシジルエステル、ｔＢｕ−安息香酸グリシジルエステル、Ｐ−トルイル酸グリシジルエステル、シクロヘキサンカルボン酸グリシジルエステル、ペラルゴン酸グリシジルエステル、ステアリン酸グリシジルエステル、ラウリン酸グリシジルエステル、パルミチン酸グリシジルエステル、ベヘン酸グリシジルエステル、バーサティク酸グリシジルエステル、オレイン酸グリシジルエステル、リノール酸グリシジルエステル、リノレイン酸グリシジルエステル、ベヘノール酸グリシジルエステル、ステアロール酸グリシジルエステル、テレフタル酸ジグリシジルエステル、イソフタル酸ジグリシジルエステル、フタル酸ジグリシジルエステル、ナフタレンジカルボン酸ジグリシジルエステル、ビ安息香酸ジグリシジルエステル、メチルテレフタル酸ジグリシジルエステル、ヘキサヒドロフタル酸ジグリシジルエステル、テトラヒドロフタル酸ジグリシジルエステル、シクロヘキサンジカルボン酸ジグリシジルエステル、アジピン酸ジグリシジルエステル、コハク酸ジグリシジルエステル、セバシン酸ジグリシジルエステル、ドデカンジオン酸ジグリシジルエステル、オクタデカンジカルボン酸ジグリシジルエステル、トリメリット酸トリグリシジルエステル、ピロメリット酸テトラグリシジルエステルなどが挙げられ、これらは１種または２種以上を用いることができる。
【００７３】
また、前記のグリシジルエ−テル化合物としては、限定されるものではないが、具体例として、フェニルグリシジルエ−テル、Ｏ−フェニルフェニルグリシジルエ−テル、１，４−ビス（β，γ−エポキシプロポキシ）ブタン、１，６−ビス（β，γ−エポキシプロポキシ）ヘキサン、１，４−ビス（β，γ−エポキシプロポキシ）ベンゼン、１−（β，γ−エポキシプロポキシ）−２−エトキシエタン、１−（β，γ−エポキシプロポキシ）−２−ベンジルオキシエタン、２，２−ビス−［р−（β，γ−エポキシプロポキシ）フェニル］プロパンおよび２，２−ビス−（４−ヒドロキシフェニル）プロパンや２，２−ビス−（４−ヒドロキシフェニル）メタンなどのビスフェノールとエピクロルヒドリンの反応で得られるビスグリシジルポリエーテルなどが挙げられ、これらは１種または２種以上を用いることができる。
【００７４】
また、（Ｈ）エポキシ化合物の配合量は機械特性と加水分解性の面から（Ａ）ポリブチレンテレフタレート１００重量部、または、ポリブチレンテレフタレート樹脂９９〜１重量％、ポリエチレンテレフタレート樹脂１〜９９重量％からなる樹脂１００重量部に対して０．０５〜５重量部であることが好ましく、より、好ましくは０．１〜４．５重量部である。
【００７５】
一般に、エポキシ化合物を使用することでポリブチレンテレフタレート樹脂の末端カルボキシル基を封鎖し、ポリブチレンテレフタレート樹脂の耐加水分解性を向上させることは知られているが、本発明では、ビニル系樹脂、アルカリ土類金属塩、および本エポキシ化合物を併用すると、相乗的に耐加水分解性が向上し、単なるエポキシ化合物の添加では到底達成しえない高度の加水分解性を付与することが可能となる。
【００７６】
本発明においては、さらにポリカーボネート樹脂を配合することにより、さらに難燃性を向上させることができる。上記のポリカーボネート樹脂とは、芳香族二価フェノール系化合物とホスゲン、または炭酸ジエステルとを反応させることにより得られる芳香族ホモまたはコポリカーボネートが挙げられる。該芳香族ホモまたはコポリカーボネート樹脂は、粘度平均分子量が通常、１００００〜１００００００の範囲のものであり、粘度平均分子量が１００００〜１００００００の範囲であれば、粘度平均分子量の異なるポリカーボネート樹脂を併用しても良い。ここで二価フェノール系化合物としては、２，２−ビス（４−ヒドロキシフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３，５−ジメチルフェニル）プロパン、ビス（４−ヒドロキシフェニル）メタン、１，１−ビス（４−ヒドロキシフェニル）エタン、２，２−ビス（４−ヒドロキシフェニル）ブタン、２，２−ビス（４−ヒドロキシ−３，５−ジフェニル）ブタン、２，２−ビス（４−ヒドロキシ−３，５−ジエチルフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３，５−ジエチルフェニル）プロパン、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン、１−フェニル−１，１−ビス（４−ヒドロキシフェニル）エタン等が使用でき、これら単独あるいは混合物として使用することができる。また、ポリカーボネート樹脂の配合量は、難燃性と機械特性の点から（Ａ）ポリブチレンテレフタレート樹脂１００重量部に対して、１〜１００重量部が好ましく、特に好ましくは２〜９０重量部である。
【００７７】
本発明においては、さらにシリコーン化合物、フェノール樹脂、ホスホニトリル化合物、ポリ燐酸アンモニウム、ポリ燐酸メラミンおよび無機水和物などの難燃性向上や燃焼時の発生ガスを抑制する難燃助剤を配合でき、１種以上で用いられる。また、上記の難燃助剤の配合量は、難燃性と機械特性の点から（Ａ）ポリブチレンテレフタレート樹脂１００重量部に対して、０．１〜５０重量部が好ましく、特に好ましくは０．５〜３０重量部である。
【００７８】
前記のシリコーン化合物としては、シリコーン樹脂、シリコーンオイルおよびシリコーンパウダーが挙げられる。
【００７９】
上記のシリコーン樹脂としては、飽和または不飽和一価炭化水素基、水素原子、ヒドロキシル基、アルコキシル基、アリール基、ビニルまたはアリル基から選ばれる基とシロキサンが化学的に結合されたポリオルガノシロキサンが挙げられ、室温で約２００〜３００００００００センチポイズの粘度を有するものが好ましいが、上記のシリコーン樹脂である限り、それに限定されるものではなく、製品形状がオイル状、パウダー状およびガム状であっても良く、官能基としてエポキシ基、メタクル基およびアミノ基が導入されていても良く、２種以上のシリコーン樹脂との混合物であっても良い。
【００８０】
また、シリコーンオイルとしては、飽和または不飽和一価炭化水素基、水素原子、ヒドロキシル基、アルコキシル基、アリール基、ビニルまたはアリル基から選ばれる基とシロキサンが化学的に結合されたポリオルガノシロキサンが挙げられ、室温で約０．６５〜１０００００センチストークスの粘度を有するものが好ましいが、上記のシリコーンオイル樹脂である限り、それに限定されるものではなく、製品形状がオイル状、パウダー状およびガム状であっても良く、官能基としてエポキシ基、メタクル基およびアミノ基が導入されていても良く、２種以上のシリコーンオイルあるいはシリコーン樹脂との混合物であっても良い。
【００８１】
また、シリコーンパウダーとは、上記のシリコーン樹脂および／またはシリコーンオイルに無機充填剤を配合したものであり、無機充填剤としてはシリカなどが好ましく用いられる。
【００８２】
前記のフェノール樹脂としては、フェノール性水酸基を複数有する高分子であれば任意であり、例えばノボラック型、レゾール型および熱反応型の樹脂、あるいはこれらを変性した樹脂が挙げられる。これらは硬化剤未添加の未硬化樹脂、半硬化樹脂、あるいは硬化樹脂であってもよい。中でも、硬化剤未添加で、非熱反応性であるノボラック型フェノール樹脂が難燃性、機械特性、経済性の点で好ましい。
【００８３】
また、フェノール樹脂の形状は特に制限されず、粉砕品、粒状、フレーク状、粉末状、針状、液状などいずれも使用でき、必要に応じ、１種または２種以上使用することができる。また、フェノール系樹脂は特に限定するものではなく市販されているものなどが用いられる。例えば、ノボラック型フェノール樹脂の場合、フェノール類とアルデヒド類のモル比を１：０．７〜１：０．９となるような比率で反応槽に仕込み、更にシュウ酸、塩酸、硫酸、トルエンスルホン酸等の触媒を加えた後、加熱し、所定の時間還流反応を行う。生成した水を除去するため真空脱水あるいは静置脱水し、更に残っている水と未反応のフェノール類を除去する方法により得ることができる。これらの樹脂あるいは複数の原料成分を用いることにより得られる共縮合フェノール樹脂は単独あるいは二種以上用いることができる。レゾール型フェノール樹脂の場合、フェノール類とアルデヒド類のモル比を１：１〜１：２となるような比率で反応槽に仕込み、水酸化ナトリウム、アンモニア水、その他の塩基性物質などの触媒を加えた後、ノボラック型フェノール樹脂と同様の反応および処理をして得ることができる。
【００８４】
ここで、フェノール類としてはフェノール、ｏ−クレゾール、ｍ−クレゾール、ｐ−クレゾール、チモール、ｐ−ｔｅｒｔ−ブチルフェノール、ｔｅｒｔ−ブチルカテコール、カテコール、イソオイゲノール、ｏ−メトキシフェノール、４，４’−ジヒドロキシフェニル−２，２−プロパン、サルチル酸イソアミル、サルチル酸ベンジル、サルチル酸メチル、２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール等が挙げられる。これらのフェノール類は一種または二種以上用いることができる。一方、アルデヒド類としてはホルムアルデヒド、パラホルムアルデヒド、ポリオキシメチレン、トリオキサン等が挙げられる。これらのアルデヒド類は必要に応じて一種または二種以上用いることができる。
【００８５】
フェノール系樹脂の分子量は、特に限定されないが好ましくは数平均分子量で２００〜２，０００であり、特に４００〜１，５００の範囲のものが機械的物性、流動性、経済性に優れ好ましい。なおフェノール系樹脂の分子量は、テトラヒドラフラン溶液、ポリスチレン標準サンプルを使用することによりゲルパーミエションクロマトグラフィ法で測定できる。
【００８６】
前記のホスホニトリル化合物としては、ホスホニトリル線状ポリマー及び／または環状ポリマーを主成分とするホスホニトリル化合物が挙げられ、直鎖状、環状のいずれかあるいは混合物であってもかまわない。前記ホスホニトリル線状ポリマー及び／または環状ポリマーは、著者梶原『ホスファゼン化合物の合成と応用』などに記載されている公知の方法で合成することができ、例えば、りん源として五塩化リンあるいは三塩化リン、窒素源として塩化アンモニウムあるいはアンモニアガスを公知の方法で反応させて（環状物を精製してもよい）、得られた物質をアルコール、フェノールおよびアミン類で置換することで合成することができる。
【００８７】
前記のポリ燐酸アンモニウムとしては、ポリ燐酸アンモニウム、メラミン変性ポリ燐酸アンモニウム、およびカルバミルポリ燐酸アンモニウムなどが挙げられ、熱硬化性を示すフェノール樹脂、ウレタン樹脂、メラミン樹脂、尿素樹脂、エポキシ樹脂、およびユリア樹脂などの熱硬化性樹脂などによって被覆されていてもいなくても良く、１種で用いても２種以上で用いても良い。
【００８８】
前記の燐酸メラミンとしては、ポリ燐酸メラミンやピロ燐酸メラミンなどの燐酸塩が挙げられ、１種で用いても２種以上で用いても良い。
【００８９】
前記の無機水和物類としては、限定されるものではないが、例えば、水酸化アルミニウム、ハイドロタルサイト、硼酸、硼酸カルシウム、硼酸カルシウム水和物、硼酸亜鉛、硼酸亜鉛水和物、水酸化亜鉛、水酸化亜鉛水和物、亜鉛錫水酸化物、亜鉛錫水酸化物水和物、赤リン、加熱膨張黒鉛およびドーソナイトなどが挙げられ、熱硬化性メラミン樹脂、熱硬化性フェノール樹脂、熱硬化性エポキシ樹脂などの熱硬化性樹脂が混合あるいは表面に被覆されていても良い。また、カップリング剤、エポキシ化合物、あるいはステアリン酸などの油脂類などが混合あるいは表面に被覆されていても良い。
【００９０】
本発明においては、さらに加水分解性を改良する目的でフェノキシ樹脂、オキサゾリン化合物、およびカルボジイミド化合物などを配合でき、とくにフェノキシ樹脂が好ましく用いられる。また、上記の加水分解性改良材の添加量は、得られる組成物の加水分解性と難燃性の点から（Ａ）ポリブチレンテレフタレート樹脂１００重量部、または、ポリブチレンテレフタレート樹脂９９〜１重量％、ポリエチレンテレフタレート樹脂１〜９９重量％からなる樹脂１００重量部に対して、０．１〜５０重量部が好ましく、とくに好ましくは０．５〜３０重量部である。
【００９１】
また、前記のフェノキシ樹脂とは、芳香族二価フェノール系化合物とエピクロルヒドリンとを各種の配合割合で反応させることにより得られ、フェノキシ樹脂またはフェノキシ共重合体の分子量は特に制限はないが、粘度平均分子量が１０００〜１０００００の範囲のものでである。ここで、芳香族二価フェノール系化合物　の例としては、２，２−ビス（４−ヒドロキシフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３，５−ジメチルフェニル）プロパン、ビス（４−ヒドロキシフェニル）メタン、１，１−ビス（４−ヒドロキシフェニル）エタン、２，２−ビス（４−ヒドロキシ−３，５ジエチルフェニル）プロパン、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン、１−フェニル−１、１−ビス（４−ヒドロキシフェニル）エタン、２，２−ビス（４−ヒドロキシフェニル）メタン等が使用でき、これら単独あるいは混合物として使用することができる。また、形状は特に制限されず、粉砕品、粒状、フレーク状、粉末状、液状などいずれも使用できる。これらのフェノキシ樹脂は必要に応じて一種または二種以上用いることができる。
【００９２】
本発明においては、さらに本発明の組成物が長期間高温にさらされても極めて良好な耐熱エージング性を与える安定剤としてヒンダードフェノール系酸化防止剤および／またはホスファイト系酸化防止剤を配合でき、ヒンダードフェノール系酸化防止剤および／またはホスファイト系酸化防止剤の配合量は、耐熱エージング性と難燃性の点から（Ａ）ポリブチレンテレフタレート樹脂１００重量部、または、ポリブチレンテレフタレート樹脂９９〜１重量％、ポリエチレンテレフタレート樹脂１〜９９重量％からなる樹脂１００重量部に対して、０．１〜１５重量部が好ましく、特に好ましくは０．２〜１０重量部である。
【００９３】
また、前記のヒンダードフェノール系酸化防止剤の具体例としては、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。
【００９４】
また、前記のホスファイト系安定剤との例としては、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト、２，２−メチレンビス（４，６−ジ−ｔ−ブチルフェニル）オクチルホスファイト、トリスノニルフェニルホスファイト、アルキルアリル系ホスファイト、トリアルキルホスファイト、トリアリルホスファイト、ペンタエリスリトール系ホスファイト化合物などが挙げられる。
【００９５】
本発明においては、さらに滑剤を一種以上添加することにより成形時の流動性、離型性、および摩耗性や摺動特性を改良することが可能である。かかる滑剤としては、ステアリン酸カルウシム、ステアリン酸バリウムなどの金属石鹸、脂肪酸エステル、脂肪酸エステルの塩（一部を塩にした物も含む）、エチレンビスステアロアマイドなどの脂肪酸アミド、エチレンジアミンとステアリン酸およびセバシン酸からなる重縮合物あるいはフェニレンジアミンとステアリン酸およびセバシン酸の重縮合物からなる脂肪酸アミド、ポリアルキレンワックス、酸無水物変性ポリアルキレンワックスおよび上記の滑剤とフッ素系樹脂やフッ素系化合物の混合物が挙げられるがこれに限定されるものではない。滑剤の添加量は、（Ａ）ポリブチレンテレフタレート樹脂１００重量部、または、ポリブチレンテレフタレート樹脂９９〜１重量％、ポリエチレンテレフタレート樹脂１〜９９重量％からなる樹脂１００重量部に対して、０．０５〜１０重量部であることが好ましく、より好ましくは０．１〜５重量部である。
【００９６】
本発明においては、さらに、カーボンブラック、酸化チタン、および種々の色の顔料や染料を１種以上配合することにより色調を改良あるいは調色することも可能であり、配合量は、得られる組成物の機械特性の点から（Ａ）ポリブチレンテレフタレート樹脂１００重量部、または、ポリブチレンテレフタレート樹脂９９〜１重量％、ポリエチレンテレフタレート樹脂１〜９９重量％からなる樹脂１００重量部に対して０．１〜３０重量部が好ましく、より好ましくは０．１〜２０重量部、さらに好ましくは０．１〜１５重量部である。
【００９７】
また、前記のカーボンブラックとしては、限定されるものではないが、チャンネルブラック、ファーネスブラック、アセチレンブラック、アントラセンブラック、油煙、松煙、および、黒鉛などが挙げられ、平均粒径５００ｎｍ以下、ジブチルフタレート吸油量５０〜４００ｃｍ^３／１００ｇのカーボンブラックが好ましく用いられ、処理剤として酸化アルミニウム、酸化珪素、酸化亜鉛、酸化ジルコニウム、ポリオール、シランカップリング剤などで処理されていても良い。また、上記の酸化チタンとしては、ルチル形、あるいはアナターゼ形などの結晶形を持ち、平均粒子径５μｍ以下の酸化チタンが好ましく用いられ、処理剤として酸化アルミニウム、酸化珪素、酸化亜鉛、酸化ジルコニウム、ポリオール、シランカップリング剤などで処理されていても良い。また、上記のカーボンブラック、酸化チタン、および種々の色の顔料や染料は、本発明の難燃性樹脂組成物との分散性向上や製造時のハンドリング性の向上のため、種々の熱可塑性樹脂と溶融ブレンドあるいは単にブレンドした混合材料として用いても良い。とくに、前記の熱可塑性樹脂としては、ポリアルキレンテレフタレートが好ましく用いられる。
【００９８】
さらに、本発明の難燃性ポリブチレレンテレフタレート樹脂組成物および成形品に対して本発明の目的を損なわない範囲で、イオウ系酸化防止剤、紫外線吸収剤、可塑剤、および帯電防止剤などの公知の添加剤を１種以上配合された材料も用いることができる。
【００９９】
本発明の難燃性ポリブチレンテレフタレート樹脂組成物および成形品は通常公知の方法で製造される。例えば、（Ａ）ポリブチレンテレフタレート樹脂、（Ｂ）多層構造重合体、（Ｃ）燐酸エステル、必要に応じて（Ｄ）繊維強化材、（Ｅ）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、（Ｆ）アルカリ土類金属塩、および必要に応じて、フッ素系化合物、難燃助剤、エチレン（共）重合体、加水分解性改良材、ヒンダードフェノール系酸化防止剤および／またはホスファイト系酸化防止剤、顔料や染料の着色剤、滑剤、およびさらに必要に応じてその他の必要な添加剤を予備混合して、または混合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難燃性ポリブチレンテレフタレート樹脂組成物が調製される。
【０１００】
前記の予備混合の例として、ドライブレンドするだけでも本発明の効果が発揮できるが、タンブラー、リボンミキサーおよび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することが挙げられる。また、繊維強化材は、二軸押出機などの多軸押出機の元込め部とベント部の途中にサイドフィダーを設置して添加する方法であっても良い。また、液体の添加剤の場合は、二軸押出機などの多軸押出機の元込め部とベント部の途中に液添ノズルを設置してプランジャーポンプによる添加方法や元込め部などから定量ポンプで供給する方法などであっても良い。また、難燃性ポリブチレンテレフタレート樹脂組成物を製造する方法とては、限定されるものではないが、例えば“ユニメルト”あるいは“ダルメージ”タイプのスクリューを備えた単軸押出機、二軸押出機、三軸押出機およびニーダータイプの混練機などを用いて溶融混練して製造することができる。
【０１０１】
かくして得られる難燃性ポリブチレンテレフタレート樹脂組成物は、通常公知の方法で成形することができ、例えば射出成形、押出成形、圧縮成形、シート成形、フィルム成形などによって、あらゆる形状の成形品とすることができ、なかでも射出成形が好適であり、金属部品の一部を直接成形品と一体化させるインサート成形による射出成形方法で得られる成形品であっても良い。
【０１０２】
また、本発明の難燃性ポリブチレンテレフタレート樹脂組成物からなる成形品は、機器内部の電気火炎に対する安全性や成形品自体の火災に対する安全性が高く、さらに成形品外観に優れ任意の色調が可能で、機械特性とヒートサイクル性などに優れているため、電気・電子部品、機械機構部品、および自動車部品に有用である。具体的には、一般家庭電化製品、ＯＡ機器などのハウジング、コイルボビン、コネクター、リレー、ディスクドライブシャーシー、トランス、電磁開閉器、スイッチ部品、コンセント部品、モーター部品、ソケット、プラグ、コンデンサー、各種ケース類、抵抗器、金属端子や導線が組み込まれる電気・電子部品、コンピューター関連部品、音響部品、レーザーディスクなどの音声部品、照明部品、電信・電話機器関連部品、エアコン部品、洗濯機部品、ＶＴＲやテレビなどの家電部品、複写機用部品、ファクシミリ用部品、光学機器用部品、自動車点火装置部品、自動車用コネクター、および各種自動車用電装部品などが挙げられる。
【０１０３】
本発明においては、特に高度な難燃性、優れた成形品外観と機械特性を持ちながら、ヒートサイクル性に優れる成形品が得られることから、製品を使用すると内部温度が変化する樹脂部品や温度により線膨張係数が大きく異なる金属や熱硬化性樹脂部品と接触する樹脂部品として用いれば、耐久性が大きく向上することが期待できる。
【０１０４】
前記から、製品内部の温度変化が大きい電気・電子部品、および自動車用電装部品などへの使用が耐久性向上が期待できることからとりわけ有用である。
【０１０５】
【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％および部とはすべて重量％および重量部をあらわす。各特性の測定方法は以下の通りである。
【０１０６】
参考例１（Ａ）ポリブチレンテレフタレート樹脂（以下、ＰＢＴと略す）
＜Ａ−１＞東レＰＢＴー１１００Ｓ（東レ社製）。
【０１０７】
参考例２　ポリエチレンテレフタレート樹脂（以下、ＰＥＴと略す）
＜Ａ−２＞三井ＰＥＴＪ００５（三井ペット樹脂社製、固有粘度０．６５）。
【０１０８】
参考例３（Ｂ）多層構造重合体（コアシェルゴム）
＜Ｂ−１＞コア：シリコーン／アクリル重合体、シェル：メタクリル酸メチル重合体“メタブレン”Ｓ２００１（三菱レイヨン社製）
＜Ｂ−２＞コア：シリコーン／アクリル重合体、シェル：アクリロニトリル／スチレン重合体“メタブレン”ＳＸ００６（三菱レイヨン社製）
＜Ｂ−３＞コア：シリコーン／アクリル重合体、シェル：メタクリル酸メチル／メタクリル酸グリシジル重合体“メタブレン”ＫＳ０２０５（三菱レイヨン社製）。
【０１０９】
参考例４（Ｃ）燐酸エステル
＜Ｃ−１＞下記の（５）式の芳香族燐酸エステル“ＰＸ−２００”（大八化学社製）
【０１１０】
【化１０】

【０１１１】
＜Ｃ−２＞下記の（６）式の芳香族燐酸エステル“ＣＲ７４１”（大八化学社製）。
【０１１２】
【化１１】

【０１１３】
参考例５（Ｄ）繊維強化材（以下、ＧＦと略す）
＜Ｇ−１＞繊維径約１０μｍのチョップドストランド状のガラス繊維“ＣＳ３Ｊ９４８”（日東紡績社製）。
【０１１４】
参考例６（Ｅ）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（以下、ＭＣ塩と略す）
＜Ｅ−１＞メラミンシアヌレート“ＭＣＡ”（三菱化学社製）。
【０１１５】
参考例７　フッ素系化合物
＜Ｆ−１＞ポリテトラフルオロエチレン“テフロン（登録商標）６Ｊ”（三井デュポンフロロケミカル社製）。
【０１１６】
参考例８（Ｇ）アルカリ土類金属塩
＜Ｇ−１＞水酸化マグネシウム“キスマ６Ｅ”（共和化学工業社製）（以下、水マグと略す）
＜Ｇ−２＞炭酸カルシウム“ＫＳＳ１０００”（同和カルファイン社製）（以下、炭カルと略す）。
【０１１７】
参考例９（Ｈ）エポキシ化合物
＜Ｈ−１＞ビスフェノールＡジグリシジルエーテルを主成分とする“エピコート８１９”（ジャパンエポキシレジン社製）。
【０１１８】
参考例１０　難燃助剤
＜Ｉ−１＞ポリカーボネート樹脂（以下、ＰＣと略す）“ユーピロン”Ｓ３０００（三菱エンジニアリングプラスチックス社製）。
【０１１９】
＜Ｉ−２＞シリコーン化合物、シリコーンパウダー“ＤＣ４−７１０５”（東レ・ダウコーニングシリコーン社製）（以下、シリコーンと略す）。
【０１２０】
＜Ｉ−３＞ノボラック型フェノール樹脂“スミライトレジン”ＰＲ５３１９　　５（住友デュレズ社製）（以下、フェノール樹脂と略す）。
【０１２１】
＜Ｉ−４＞ホスホニトリル化合物、ヘキサクロロシクロトリホスファゼン（環状３量体）とフェノールをトリエチルアミンの存在下で反応させ、得られた反応液を蒸発・乾固させ、残査を水で洗浄して塩を除去した。さらに、アセトン、続いてエタノールで洗浄して精製し、ホスホニトリル環状ポリマーを得た。（以下、ホスホニトリルと略す）。
【０１２２】
参考例１１　エチレン共重合体およびビニル樹脂
＜Ｊ−１＞エチレンエチルアクリート共重合体（以下、ＥＥＡと略す）“Ａ−７０９”（三井・デュポンポリケミカル社製）。
【０１２３】
＜Ｊ−２＞エチレン／メタクリル酸グリシジル／アクリル酸メチル共重合体　（以下、ＢＦ−７Ｍと略す）“ＢＦ−７Ｍ”（住友化学工業社製）。
＜Ｊ−３＞アクリロニトリル／スチレン共重合体（共重合比率３０／７０重量％、のポリマーを公知の懸濁重合で得た。以下、ＡＳと略す）。
＜Ｊ−４＞ポリメタクリル酸メチル重合体（以下、ＰＭＭＡと略す）“アクリペットＭＤ”（三菱レーヨン社製）。
【０１２４】
参考例１２　繊維強化材以外の無機充填剤
＜Ｋ−１＞珪酸塩のタルク“ＬＭＳ３００”（富士タルク社製）（以下、タルクと略す）。
【０１２５】
参考例１３　ヒンダードフェノール系酸化防止剤および／またはホスファイト系酸化防止剤
＜Ｌ−１＞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］のヒンダードフェノール系酸化防止剤“ＩＲー１０１０”（日本チバガイギー社製）（以下、ＩＲ１０１０と略す）
＜Ｌ−２＞ペンタエリスリトール系ホスファイト化合物のホスファイト系酸化防止剤“Ｍａｒｋ　ＰＥＰ−３６”（旭電化社製）（以下ＰＥＰ３６と略す）。
実施例１〜２７、比較例１〜１３
スクリュ径３０ｍｍ、Ｌ／Ｄ３５の同方向回転ベント付き２軸押出機（日本製鋼所製、ＴＥＸ−３０α）を用いて、（Ａ）ＰＢＴ、ＰＥＴ、（Ｂ）多層構造重合体、（Ｃ）燐酸エステル、（Ｅ）ＭＣ塩、（Ｆ）フッ素系化合物、（Ｇ）アルカリ土類金属塩、および（Ｈ）エポキシ化合物、必要に応じて、その他の添加剤＜Ｉ＞、＜Ｋ＞、および＜Ｌ＞を表１〜表３に示した配合組成で混合し、元込め部から添加した。また、（Ｄ）成分のＧＦは、元込め部とベント部の途中にサイドフィダーを設置して添加した他は上記と同じ方法で表１に示す添加量の配合物を元込め部から添加した。なお、混練温度２７０℃、スクリュ回転１５０ｒｐｍの押出条件で溶融混合を行い、ストランド状に吐出し、冷却バスを通し、ストランドカッターによりペレット化した。
【０１２６】
得られたペレットを乾燥後、次いで射出成形機により、それぞれの試験片を成形し、次の条件で物性を測定し、同じく表１〜表３にその結果を示した。
【０１２７】
（１）難燃性
東芝機械製ＩＳ５５ＥＰＮ射出成形機を用いて、成形温度２７０℃、金型温度８０℃の条件で難燃性評価用試験片の射出成形を行い、ＵＬ９４垂直試験に定められている評価基準に従い、難燃性を評価した。難燃性はＶ−０＞Ｖ−１＞Ｖ−２の順に難燃性が低下しランク付けされる。また、試験片の厚みは１／１６インチ（約１．５９ｍｍ、以下１／１６”と略す）厚み、１／３２インチ（約０．７９ｍｍ、以下１／３２”と略す）厚み、および１／６４インチ（約０．４０ｍｍ、以下１／６４”と略す）厚みを用い、厚みが薄いほど難燃性は厳しい判定となる。また、燃焼性に劣り上記の難燃性ランクに該当しなかった材料は規格外と記録した。
【０１２８】
（２）機械特性
（２−１）引張強度
東芝機械製ＩＳ５５ＥＰＮ射出成形機を用いて、成形温度２７０℃、金型温度８０℃の条件で３ｍｍ厚みのＡＳＴＭ１号ダンベル射出成形品を得た。ＡＳＴＭＤ６３８に準じて引張強度を測定した。
【０１２９】
（２−２）アイゾット衝撃強度
東芝機械製ＩＳ５５ＥＰＮ射出成形機を用いて、成形温度２７０℃、金型温度８０℃の条件で３ｍｍ厚みのアイゾット衝撃試験片の射出成形品を得た。ＡＳＴＭＤ２５６に準じてノッチ無しアイゾット衝撃強度を測定した。ここで、ＮＢと記載されている試験結果は、試験片が破壊しないことを示す。
【０１３０】
（３）ヒートサイクル性
東芝機械製ＩＳ５５ＥＰＮ射出成形機を用いて、成形温度２７０℃、金型温度８０℃の条件で一辺および高さがいずれも５０ｍｍの４角形の鉄製角柱を１．５ｍｍ厚みの試料で包み込める形状の金型を用い、タバイ社製“ＥＳＰＥＣ”サーマルショックチャンバーＴＳＡ−７０Ｌに投入した。冷熱試験条件として、−３０℃×２ｈ、１２０℃×２ｈを１サイクルとした。ヒートサイクル性の判定は、何サイクルで試料にクラックが発生するかを随時試料の観察を行い、記録した。
【０１３１】
（４）ブリードアウト試験
東芝機械製ＩＳ５５ＥＰＮ射出成形機を用いて、成形温度２７０℃、金型温度８０℃の条件で射出成形された８０ｍｍ×８０ｍｍ×厚み３ｍｍの角板を試料とし、１５０℃に温調されたタバイ社製熱風乾燥機“ＨｉｇｈＴｅｍｐＯｖｅｎ”ＰＶＨ２１０に１００時間投入した。
【０１３２】
前記の乾燥機投入前後の角板の外観を目視観察し、次の基準でブリードアウトの有無を判定した。
【０１３３】
ここで、ブリードアウトとは、成形品組成物中の配合物の一部が成形品の表面にしみでてくる現象である。
【０１３４】
○　：乾燥機投入前後の成形品にブリードアウトが観察されない
△　：乾燥機投入前の成形品にブリードアウトが観察されないものの、乾燥機投入後の成形品にブリードアウトが観察される
×　：乾燥機投入前後の成形品にブリードアウトが観察される。
【０１３５】
（５）加水分解性
東芝機械製ＩＳ５５ＥＰＮ射出成形機を用いて、成形温度２７０℃、金型温度８０℃の条件で３ｍｍ厚みのＡＳＴＭ１号ダンベル片の射出成形を行い、得られたＡＳＴＭ１号ダンベル片を温度１２１℃、湿度１００％ＲＨの条件下で１００時間湿熱処理した後、ＡＳＴＭ　Ｄ６４８に準じて引張強度を測定し、測定値は未処理品の引張強度で割った値の百分率である引張強度保持率（％）で示した。
【０１３６】
（６）半結晶化時間
難燃性の評価に用いた１／３２”厚み燃焼試験片からサンプル約１５ｍｇを採取し、パーキングエルマー社製ＤＳＣ−７示差熱量計にセットした。２７０℃×５分間サンプルを溶融後、最大の降温スピードで１９０℃まで冷却させ、１９０℃を保持させ結晶化ピークの出る時間を記録した。なお、結晶化ピークまでの時間は、結晶の半分に相当することから、半結晶化時間として表した。この時間が短い程、射出成形時の固化速度も速いものと推定されることから、結晶化速度の目安となる測定値である。
【０１３７】
（７）耐熱性
東芝機械製ＩＳ５５ＥＰＮ射出成形機を用いて、成形温度２７０℃、金型温度８０℃の条件で３ｍｍ厚みのＡＳＴＭ１号ダンベル片の射出成形を行い、得られたＡＳＴＭ１号ダンベル片を温度１８０℃に温調されたタバイ製パーフェクトオーブンに２００時間投入した後、ＡＳＴＭ　Ｄ６４８に準じて引張強度を測定し、測定値は未処理品の引張強度で割った値の百分率である引張強度保持率（％）で示した。
【０１３８】
【表１】

【０１３９】
【表２】

【０１４０】
【表３】

【０１４１】
比較例１、（Ａ）成分として、ＰＢＴを混合していないＰＥＴを用いたところ、前記記載の射出成形条件では固化が遅いため、評価用の成形品を得ることができなかった。
【０１４２】
表１に本発明組成物の（Ａ）ＰＢＴ、およびＰＢＴとＰＥＴの混合物、（Ｂ）多層構造重合体、および（Ｃ）リン酸エステルの効果について述べる。
【０１４３】
比較例２〜比較例４から、（Ａ）ＰＢＴに（Ｃ）リン酸エステルを配合することによって、１／１６”厚みＶ−２の燃焼性を示した。しかし、成形品表面にブリードアウトが生じるため、商品価値のない成形品と言える。
【０１４４】
しかし、本発明組成物の実施例１〜実施例６から、（Ａ）ＰＢＴ、およびＰＢＴとＰＥＴの混合物に（Ｂ）多層構造重合体、（Ｃ）リン酸エステルを配合することによって、Ｖ−２の難燃性を維持しながら前記のブリードアウトが生じない、優れた成形品外観を持つ成形品が得られる効果があると言える。
【０１４５】
また、さらに（Ｄ）繊維強化材を配合した実施例７〜実施例９においても、Ｖ−２の難燃性を維持しながらブリードアウトが生じない、優れた成形品外観を持つ高強度の成形品が得られる効果があると言える。
【０１４６】
しかし、（Ｂ）多層構造重合体、および（Ｃ）リン酸エステルのいずれかを配合していない（Ｄ）繊維強化材を配合した比較例５〜比較例６は、燃焼性が認められないか、もしくは、成形品表面にブリードアウトが生じるため、商品価値のない成形品と言える。
【０１４７】
また、（Ｂ）多層構造重合体、および（Ｃ）リン酸エステルが本発明の範囲以上に配合された比較例７〜比較例８の場合も、燃焼性が認められないか、もしくは、成形品表面にブリードアウトが生じるため、商品価値のない成形品と言える。
【０１４８】
また、実施例７の（Ｂ）多層構造重合体に替えて、エチレン共重合体あるいはビニル樹脂を配合した比較例９〜比較例１２の組成物は、難燃性と衝撃強度の低下およびＡＳ以外の材料はブリードアウトも生じさせ、好ましくない組成物と言える。　さらに、実施例７と比較例７〜比較例８衝撃強度とヒートサイクル性の物性を比較すると、（Ｂ）多層構造重合体が難燃性に悪影響を与えずブリードアウト防止効果を持つ他に、機械特性とヒートサイクル性に優れる効果があると言える。
【０１４９】
表２には、本発明において必要に応じて配合する（Ｅ）ＭＣ塩、（Ｆ）フッ素系化合物（Ｇ）アルカリ土類金属塩、および（Ｈ）エポキシ化合物を配合組成物の効果を示した。
【０１５０】
実施例１０〜実施例１３から、（Ｅ）ＭＣ塩と（Ｆ）フッ素系化合物を配合した場合は、難燃性が１／１６”厚みＶ−０、１／３２”厚みＶ−２〜Ｖ−０を示し、難燃性が大きく向上し、機械特性とヒートサイクル性に優れ、かつブリードアウトの生じない成形品が得られる効果があると言える。
【０１５１】
しかし、（Ｅ）ＭＣ塩と（Ｆ）フッ素系化合物を配合した組成物においても（Ｂ）多層構造重合体を配合しない比較例８の場合は、ブリードアウト防止の効果がないばかりか衝撃強度とヒートサイクル性にも劣る成形品と言える。
【０１５２】
また、実施例１４〜１７から、本発明において必要に応じて配合する（Ｇ）アルカリ土類金属塩と（Ｈ）エポキシ化合物を配合した場合は、実施例１０の難燃性と優れた物性を維持しながら、加水分解性が向上し、とくに（Ｇ）アルカリ土類金属塩と（Ｈ）エポキシ化合物を併用配合した場合は飛躍的に加水分解性が向上する効果があると言える。
【０１５３】
表３には、実施例１３の組成物に、さらに本発明において必要に応じて配合する難燃助剤、無機充填剤、および酸化防止剤の効果を示した。
【０１５４】
実施例１８〜実施例２１から、難燃助剤のＰＣ、フェノール樹脂、シリコーン、およびホスホニトリルを配合した組成物は、優れた物性を維持しながら、１／６４”厚みにおいても高度な難燃性を与える効果があると言える。
【０１５５】
また、実施例２２から、タルクを配合することによって、優れた物性と難燃性を維持しながら、結晶化速度に優れる組成物が得られる効果があると言える。
【０１５６】
また、実施例２３〜実施例２４から、酸化防止剤を配合することによって、優れた物性と難燃性を維持しながら、耐熱性に優れる組成物が得られる効果があると言える。
【０１５７】
また、実施例２５〜実施例２７の組成物は、ＰＢＴよりも難燃性に優れる他の樹脂を本発明組成物に配合した材料であり、難燃性、機械特性、およびヒートサイクル性の本発明効果を損なうことはないと言える。
【０１５８】
【発明の効果】ＰＢＴに、特定量の多層構造重合体、燐酸エステル、および繊維強化材、必要に応じて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、フッ素系化合物、アルカリ土類金属塩およびエポキシ化合物、およびさらに必要に応じて、難燃助剤、無機充填剤、および酸化防止剤などを配合することで、高度な難燃性を保持しつつ、特異的に機械特性、ヒートサイクル性、および成形品色調に優れ、さらにブリードアウトが生じ難く優れた成形品外観を有する信頼性の高い非ハロゲンの難燃性ポリブチレンテレフタレート樹脂組成物および成形品を得ることでき、自動車部品、電気・電子部品および機械部品の市場拡大に大きく寄与することが期待できる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a flame-retardant resin composition in which a non-halogen flame retardant is blended with a polybutylene terephthalate resin, and a molded article. More specifically, it has high flame retardancy, mechanical properties, heat cycling properties, and excellent surface appearance of molded products, and uses a non-halogen flame retardant suitable for mechanical mechanism parts, electric / electronic parts or automobile parts. The present invention relates to a flame-retardant polybutylene terephthalate resin composition and a molded article.
[0002]
[Prior art]
BACKGROUND ART Polybutylene terephthalate resin (PBT) is utilized in a wide range of fields such as mechanical mechanism parts, electric / electronic parts, and automobile parts by making use of its excellent properties such as injection moldability and mechanical properties.
[0003]
Further, by compounding a fiber reinforced material with PBT, it is widely used as a material having further excellent mechanical properties and heat resistance. Among the fiber reinforcements, glass fibers are particularly used.
[0004]
Because PBT is inherently flammable, it can be used as an industrial material for mechanical and mechanical components, electrical and electronic components, and automotive components as described above, as well as a general balance of chemical and physical properties as well as safety against flame. , That is, flame retardancy is required, and in many cases, a high degree of flame retardancy showing V-0 of UL-94 standard is required.
[0005]
In addition, there is a demand for a molded article that can have various colors with pigments and dyes, as well as high flame retardancy.
[0006]
As a method of imparting flame retardancy to PBT, a method of compounding a resin with a halogen-based organic compound as a flame retardant and an antimony compound as a flame retardant auxiliary is generally used. However, this method tends to generate a large amount of smoke during combustion.
[0007]
In addition, there is a movement to raise concerns about the effect of halogen-based flame-retardant materials on the environment due to increasing environmental awareness.
[0008]
Therefore, in recent years, it has been strongly desired to use a flame retardant containing no halogen at all.
[0009]
Heretofore, as a method of making a thermoplastic resin flame-retardant without using a halogen-based flame retardant, it is widely known to add a hydrated metal compound such as aluminum hydroxide and magnesium hydroxide. In order to obtain flame retardancy, it is necessary to add a large amount of the above-mentioned hydrated metal compound, which has a disadvantage that the inherent properties of the resin are lost.
[0010]
On the other hand, as a method of making a thermoplastic resin flame-retardant without using such a hydrated metal compound, addition of red phosphorus has been disclosed in JP-A-51-150553 and JP-A-58-108248. JP-A-59-81351, JP-A-5-78560, JP-A-5-287119, JP-A-5-295164, JP-A-5-320486, JP-A-5-339417, etc. Have been.
[0011]
However, although it is a useful flame-retardant resin material that does not use a halogen-based flame retardant, it has a problem in that it is peculiarly colored and its use is restricted because the color tone of the product is restricted.
[0012]
Further, JP-A-3-281652, JP-A-5-70671, JP-A-7-233331 and JP-A-8-73713 disclose that a phosphate ester and melamine cyanurate are blended. I have.
[0013]
However, although this is a useful flame-retardant resin material that does not use a halogen-based flame retardant, it has a problem that bleed-out of the phosphate ester on the surface of the molded product occurs, greatly deteriorating the value of the appearance of the molded product.
[0014]
Further, JP-A-10-147699, JP-A-10-182555, JP-A-10-182965, and JP-A-2000-26710 disclose a composition containing PBT, polyphenylene ether, phosphate ester, and the like. On the other hand, it is disclosed that a styrene resin is blended.
[0015]
However, although it is a useful flame-retardant resin material that does not use a halogen-based flame retardant, the incorporation of polyphenylene ether causes a decrease in mechanical strength, a decrease in fluidity during injection molding, and a molded article colored yellow. There was a problem that the value of the color tone of the molded article was greatly impaired.
[0016]
Further, JP-A-8-73692 and JP-A-9-235559 disclose that an ethylene acrylate copolymer is blended with a composition containing PBT, a phosphate and the like.
[0017]
However, although it is a useful flame-retardant resin material that does not use a halogen-based flame retardant, the addition of an ethylene acrylate copolymer greatly reduces the flame retardancy and mechanical strength. There is a problem that it is difficult to obtain a molded product having properties and mechanical strength.
[0018]
[Problems to be solved by the invention]
That is, the present invention provides a polybutylene terephthalate resin blended with a non-halogen flame retardant to provide excellent flame retardancy, mechanical properties, heat cycle properties, and a flame-retardant polymer having an excellent appearance of a molded article which is less likely to cause bleed-out. An object is to obtain a butylene terephthalate resin composition and a molded product.
[0019]
[Means for Solving the Problems]
In view of the above situation, the present inventors have conducted intensive studies, and as a result, it has been found that a high level of flame retardancy is obtained by blending a polybutylene terephthalate resin with a specific amount of a multilayer structure polymer, a phosphate ester, and a fiber reinforcing material. Flame-retardant polybutylene terephthalate resin composition and molded article having excellent mechanical properties, heat cycle properties, and molded article color tone while maintaining the property, and having an excellent appearance of the molded article with less bleed-out. And arrived at the present invention.
[0020]
In the present invention, a molded article free from bleed-out, in which the phosphate ester is stained on the surface of the molded article, which has been regarded as a drawback of the phosphate flame retardant system, has been successfully obtained.
[0021]
Further, in a heat cycle test in which the low-temperature atmosphere and the high-temperature atmosphere are one cycle and the low-temperature atmosphere and the high-temperature atmosphere are repeated many times, it was found that a molded article in which appearance abnormality such as cracks is unlikely to occur for a long time can be obtained.
[0022]
That is, the present invention relates to (B) a multilayer comprising: (A) a polybutylene terephthalate resin or 100 parts by weight of a mixture of (A) a polybutylene terephthalate resin of 99 to 1% by weight and a polyethylene terephthalate resin of 1 to 99% by weight; A flame-retardant polybutylene terephthalate resin composition comprising 1 to 50 parts by weight of a structural polymer and 1 to 70 parts by weight of a phosphoric ester (C);
and
Another object of the present invention is to provide a molded article for a mechanical mechanism part, an electric / electronic part or an automobile part, comprising the flame-retardant polybutylene terephthalate resin composition.
[0023]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the flame-retardant polybutylene terephthalate resin composition and the molded article of the present invention will be specifically described.
[0024]
The polybutylene terephthalate resin (A) in the present invention is a polymer obtained by a polycondensation reaction between terephthalic acid or its ester-forming derivative and 1,4-butanediol or its ester-forming derivative. As acid components, isophthalic acid, naphthalenedicarboxylic acid, adipic acid, sebacic acid, dodecandic acid, oxalic acid, etc., and as glycol components, ethylene glycol, propylene glycol, neopentyl glycol, 1,5-pentanediol, 1,6 -Hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, or the like, or a long-chain glycol having a molecular weight of 400 to 6000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethyl Such as glycol to may be copolymerized than 20 mol%. Preferred examples of these polymers or copolymers include polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decane dicarboxylate), and polybutylene. (Terephthalate / naphthalate) and the like, and may be used alone or as a mixture of two or more. Here, “/” means copolymerization.
[0025]
In addition, a polymer or copolymer having an intrinsic viscosity of 0.36 to 1.60, particularly 0.42 to 1.25, measured at 25 ° C. using an O-chlorophenol solvent is obtained. It is suitable from the viewpoints of impact strength and moldability of the composition. The polybutylene terephthalate resin (A) may be a combination of polybutylene terephthalate resins having different intrinsic viscosities, and it is preferable to use a polybutylene terephthalate resin having an intrinsic viscosity in the range of 0.36 to 1.60.
[0026]
Further, the polybutylene terephthalate resin and the m-cresol solution having a COOH terminal group amount determined by potentiometric titration with an alkali solution in the range of 1 to 50 eq / t (terminal group amount per ton of polymer) are those having durability. , Can be preferably used from the viewpoint of the effect of suppressing anisotropy. Furthermore, those having a small number of COOH terminal groups can be preferably used because they have excellent hydrolysis resistance.
[0027]
The (A) polyethylene terephthalate resin constituting a mixture of 99 to 1% by weight of polybutylene terephthalate resin and 1 to 99% by weight of polyethylene terephthalate resin in the present invention means that terephthalic acid is used as an acid component and ethylene glycol is used as a glycol component. Polycondensed, refers to a high molecular weight thermoplastic polyester resin having an ester bond in the main chain, in addition to the acid component, such as isophthalic acid, adipic acid, oxalic acid, glycol component, propylene glycol, 1, 4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, etc., or a long-chain glycol having a molecular weight of 400 to 6000, that is, poly Ji glycol, poly-1,3-propylene glycol, polytetramethylene glycol and the like may also be copolymerized than 20 mol%. In addition, the polyethylene terephthalate resin is a composition having an intrinsic viscosity of 0.36 to 1.60, particularly 0.45 to 1.15, measured at 25 ° C. using an O-chlorophenol solvent. It is suitable in terms of impact strength and moldability.
[0028]
The mixing ratio of the polyethylene terephthalate resin to (A) the polybutylene terephthalate resin is preferably 1 to 99% by weight, more preferably 5 to 90% by weight, from the viewpoint of flame retardancy and crystallinity.
[0029]
Also, (A) polybutylene terephthalate and a mixture of polybutylene terephthalate resin and polyethylene terephthalate resin may be used in combination with polyester elastomer, polyarylate resin, wholly aromatic liquid crystal polyester, semi-aromatic liquid crystal polyester and polycyclohexane dimethylene terephthalate resin. One or more polyester resins may be blended, and the blending amount is within a range that does not significantly reduce the effects of the present invention.
[0030]
In the present invention, the (B) multilayered polymer is composed of an innermost layer (core layer) and one or more layers (shell layers) covering the innermost layer. It is a polymer having a so-called core-shell structure.
[0031]
The number of layers constituting the multilayer polymer (B) of the present invention is not particularly limited, and may be two or more, and may be three or more or four or more.
[0032]
The (B) multilayer polymer of the present invention is preferably a multilayer polymer having at least one or more rubber layers inside.
[0033]
In the multilayer polymer (B) of the present invention, the type of the rubber layer is not particularly limited, and may be any as long as it is composed of a polymer component having rubber elasticity. For example, a rubber composed of a polymer obtained by polymerizing an acrylic component, a silicone component, a styrene component, a nitrile component, a conjugated diene component, a urethane component, an ethylene propylene component, or the like can be used. Preferred rubbers include, for example, acrylic components such as ethyl acrylate units and butyl acrylate units, silicone components such as dimethylsiloxane units and phenylmethylsiloxane units, styrene components such as styrene units and α-methylstyrene units, and acrylonitrile units. It is a rubber formed by polymerizing a nitrile component such as a methacrylonitrile unit and a conjugated diene component such as a butanediene unit and an isoprene unit. Further, a rubber composed of a copolymer obtained by combining two or more of these components is also preferable. For example, (1) an acrylic component such as an ethyl acrylate unit or a butyl acrylate unit and a dimethylsiloxane unit or a phenylmethylsiloxane Rubber composed of components obtained by copolymerizing silicone components such as units, (2) components obtained by copolymerizing acrylic components such as ethyl acrylate units and butyl acrylate units and styrene components such as styrene units and α-methylstyrene units (3) rubber composed of a component obtained by copolymerizing an acrylic component such as ethyl acrylate unit or butyl acrylate unit and a conjugated diene component such as butanediene unit or isoprene unit; and (4) acrylic acid Acrylic components such as ethyl units and butyl acrylate units And rubber, and the like composed of silicone component and styrene component copolymerized with components such as styrene units or α- methylstyrene units such as dimethylsiloxane units or phenylmethylsiloxane units. In addition to these components, a rubber obtained by copolymerizing and crosslinking a crosslinkable component such as a divinylbenzene unit, an allyl acrylate unit and a butylene glycol diacrylate unit is also preferable.
[0034]
In the multilayer polymer (B) of the present invention, the type of the layer other than the rubber layer is not particularly limited as long as it is composed of a polymer component having thermoplasticity. It is preferable that the polymer component has a high transition temperature. Examples of the polymer having thermoplasticity include unsaturated carboxylic acid alkyl ester-based units, unsaturated glycidyl group-containing units, unsaturated dicarboxylic anhydride-based units, aliphatic vinyl-based units, aromatic vinyl-based units, and vinyl cyanide-based units. Polymer containing at least one unit selected from a unit, a maleimide-based unit, an unsaturated dicarboxylic acid-based unit, and other vinyl-based units. Among them, an unsaturated carboxylic acid alkyl ester-based unit, an unsaturated A polymer containing at least one unit selected from a glycidyl group-containing unit and an unsaturated dicarboxylic anhydride-based unit is preferable, and is further selected from an unsaturated glycidyl group-containing unit and an unsaturated dicarboxylic anhydride-based unit. Polymers containing at least one or more units are more preferred.
[0035]
The unsaturated carboxylic acid alkyl ester-based unit is not particularly limited, but alkyl (meth) acrylate is preferably used. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, (meth) acrylic N-hexyl acid, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, octadecyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, Chloromethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2,3,4,5,6 (meth) acrylate Pentahydroxyhexyl, 2,3,4,5-tetrahydroxypentyl (meth) acrylate, acrylate Ethyl, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, ethylaminopropyl methacrylate, phenylaminoethyl methacrylate, cyclohexylaminoethyl methacrylate, and the like, and from the viewpoint of having a large effect of improving impact resistance, Methyl (meth) acrylate is preferably used. These units may be used alone or in combination of two or more.
[0036]
The unsaturated glycidyl group-containing unit is not particularly limited, and includes glycidyl (meth) acrylate, glycidyl itaconate, diglycidyl itaconate, allyl glycidyl ether, styrene-4-glycidyl ether, 4-glycidyl styrene, and the like. Glycidyl (meth) acrylate is preferably used from the viewpoint that the effect of improving impact resistance is large. These units may be used alone or in combination of two or more.
[0037]
Examples of the unsaturated dicarboxylic anhydride-based unit include maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, aconitic anhydride, and the like.From the viewpoint that the effect of improving impact resistance is large, anhydrous Maleic acid is preferably used. These units may be used alone or in combination of two or more.
[0038]
Further, as the aliphatic vinyl-based unit, ethylene, propylene, butadiene and the like, and as the aromatic vinyl-based unit, styrene, α-methylstyrene, 1-vinylnaphthalene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexyl styrene, 4-dodecyl styrene, 2-ethyl-4-benzyl styrene, 4- (phenylbutyl) styrene, halogenated styrene and the like, and the above-mentioned vinyl cyanide-based units include acrylonitrile, methacrylonitrile and ethacryloyl. Examples of the maleimide-based unit such as nitrile include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and N- (p-bromophenyl). Nyl) maleimide and N- (chlorophenyl) maleimide; unsaturated dicarboxylic acid-based units such as maleic acid, monoethyl maleate, itaconic acid and phthalic acid; and the other vinyl-based units acrylamide , Methacrylamide, N-methylacrylamide, butoxymethylacrylamide, N-propylmethacrylamide, N-vinyldiethylamine, N-acetylvinylamine, allylamine, methallylamine, N-methylallylamine, p-aminostyrene, 2-isopropenyl- Oxazoline, 2-vinyl-oxazoline, 2-acryloyl-oxazoline, 2-styryl-oxazoline and the like can be exemplified, and these units can be used alone or in combination of two or more.
[0039]
In the (B) multilayered polymer of the present invention, the type of the outermost layer is not particularly limited, and may be an unsaturated carboxylic acid alkyl ester-based unit, an unsaturated glycidyl group-containing unit, an aliphatic vinyl-based unit, or an aromatic unit. At least one selected from polymers containing vinyl units, vinyl cyanide units, maleimide units, unsaturated dicarboxylic acid units, unsaturated dicarboxylic anhydride units, and other vinyl units; And at least one selected from polymers containing an unsaturated carboxylic acid alkyl ester-based unit, an unsaturated glycidyl group-containing unit and an unsaturated dicarboxylic anhydride-based unit, among which unsaturated carboxylic acid Polymers containing alkyl ester units are more preferred.
[0040]
The unsaturated carboxylic acid alkyl ester-based unit here is not particularly limited, but alkyl (meth) acrylate is preferred, and methyl (meth) acrylate is more preferably used.
[0041]
Preferred examples of the multi-layered polymer (B) of the present invention are those in which the core layer is a dimethylsiloxane / butyl acrylate polymer and the outermost layer is a methyl methacrylate polymer, and the core layer is a butanediene / styrene polymer. Examples include those in which the outer layer is a methyl methacrylate polymer and those in which the core layer is a butyl acrylate polymer and the outermost layer is a methyl methacrylate polymer. Further, it is more preferable that one or both of the rubber layer and the outermost layer is a polymer containing a glycidyl methacrylate unit.
[0042]
The particle diameter of the multilayer polymer (B) of the present invention is not particularly limited, but is preferably 0.01 μm or more and 1000 μm or less, and more preferably 0.02 μm or more and 100 μm or less. Is more preferable, and in particular, it is most preferably not less than 0.05 μm and not more than 10 μm.
[0043]
In the multilayer structure polymer (B) of the present invention, the weight ratio of the core and the shell is not particularly limited, but the core layer is 10 parts by weight or more and 90 parts by weight or less with respect to the whole multilayer structure polymer. Is more preferable, and it is more preferable that it is 30 parts by weight or more and 80 parts by weight or less.
[0044]
As the multilayer structure polymer (B) of the present invention, a commercially available product satisfying the above-mentioned conditions may be used, or it may be prepared and used by a known method.
[0045]
(B) Commercially available multi-layered polymers include, for example, "METABLEN" manufactured by Mitsubishi Rayon Co., Ltd., "Kane Ace" manufactured by Kaneka Chemical Industry Co., Ltd., "PARALOID" manufactured by Kureha Chemical Industry Co., Ltd., and "Acryloid" manufactured by Rohm and Haas Co., Ltd. And "Parapet SA" manufactured by Kuraray Co., Ltd., and these can be used alone or in combination of two or more.
[0046]
In addition, (B) 100 parts by weight of a polybutylene terephthalate resin or 99 to 1% by weight of a polybutylene terephthalate resin in view of flame retardancy and fluidity at the time of molding. It is necessary to use 1 to 50 parts by weight, preferably 2 to 45 parts by weight, more preferably 5 to 40 parts by weight, per 100 parts by weight of the resin composed of 1 to 99% by weight of the terephthalate resin.
[0047]
As the phosphoric ester (C) in the present invention, commercially available phosphoric esters and any synthesized phosphoric esters can be used. Specific examples include tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, triphenyl phosphate, tris-isopropylbiphenyl phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, octyl diphenyl Phosphate, orthophenylphenol phosphate, pentaerythritol phosphate, neopetyl glycol phosphate, substituted neopentyl glycol phosphonate, nitrogen-containing phosphate, and aromatic phosphate of the following formula (1) Particularly preferred are the aromatic phosphates of the following formula (1).
[0048]
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[0049]
(In the above formula, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ Represents a phenyl group which is the same or different, or a phenyl group substituted with a halogen-free organic residue. X represents one selected from the following formulas (2) to (4); ¹ ~ R ⁸ Represents the same or different hydrogen atom or an alkyl group having 1 to 5 carbon atoms, Y represents a direct bond, O, S, SO2, C (CH3) 2, CH2, CHPh, and Ph represents a phenyl group. Further, n in the formula (1) is an integer of 0 or more, and may be a mixture of different n. In the formula (1), k and m are each an integer of 0 or more and 2 or less, and (k + m) is an integer of 0 or more and 2 or less.
[0050]
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[0051]
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[0052]
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[0053]
Among them, the following compounds are preferred.
[0054]
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[0055]
The amount of the phosphoric acid ester (C) is 100 parts by weight of the polybutylene terephthalate resin (A), 99 to 1% by weight of the polybutylene terephthalate resin, and 1 to 99% by weight of the polyethylene terephthalate resin in view of flame retardancy and mechanical properties. % To 100 parts by weight of the resin, preferably 2 to 65 parts by weight, more preferably 3 to 60 parts by weight.
[0056]
The (D) fiber reinforced material in the present invention is a material which can obtain a high-strength resin by blending the (D) fiber reinforced material with a polybutylene terephthalate resin, and is not limited. Examples include glass fiber, aramid fiber, carbon fiber, potassium titanate fiber, ceramic fiber, and steel fiber, and glass fiber and carbon fiber are preferably used. Examples of the glass fibers and carbon fibers preferably used include chopped strand type or roving type glass fibers and carbon fibers used in ordinary PBT reinforcing materials, and aminosilane compounds and epoxysilane compounds as surface treatment agents. Glass fibers treated with a silane coupling agent and / or a sizing agent containing one or more epoxy compounds such as urethane, vinyl acetate, bisphenol A diglycidyl ether, and novolak epoxy compound are preferably used. Further, the silane coupling agent and / or the sizing agent may be used in an emulsion liquid.
[0057]
The fiber diameter of the fiber reinforcing material (D) is preferably 5 μm to 20 μm, and particularly preferably 6 μm to 15 μm.
[0058]
In addition, (D) an inorganic filler can be added to a part of the fibrous reinforcing material, and the crystallization characteristics, tracking resistance, arc resistance, anisotropy, mechanical strength, and flame retardancy of the composition of the present invention. Alternatively, it is to improve a part such as heat deformation temperature.Examples of such an inorganic filler include, but are not limited to, acicular, granular, powdery and layered inorganic fillers, and specific examples include , Glass beads, milled fiber, potassium whisker, wollastenite, silica, kaolinite, talc, smectite clay minerals (montmorillonite, hectorite), vermiculite, mica, fluorine teniolite, zirconium phosphate, titanium phosphate, and dolomite. And used in one or more types. The inorganic filler may be subjected to a surface treatment such as a coupling agent treatment, an epoxy compound, or an ionization treatment. The average particle size of the granular, powdery and layered inorganic filler is preferably from 0.1 μm to 20 μm, particularly preferably from 0.2 μm to 10 μm, from the viewpoint of impact strength. Further, the amount of the inorganic filler is preferably not more than the amount of the fiber reinforcing agent.
[0059]
In particular, a composition in which glass flakes are blended with glass fibers as an inorganic filler is useful for the production of a molded product with less warpage, or a composition in which talc of a silicate compound is blended is a material having excellent injection moldability. It is useful for producing butylene terephthalate resin molded products.
[0060]
In addition, the fiber length when the above-mentioned (D) fiber reinforcement is used as a chopped strand type is preferably 1 mm to 10 mm, particularly preferably 2 mm to 7 mm.
[0061]
The amount of the fiber reinforcing material (D) is 100 parts by weight of polybutylene terephthalate resin or 99 to 1% by weight of polybutylene terephthalate resin in view of flame retardancy and fluidity during molding, and polyethylene terephthalate. The amount is preferably from 1 to 150 parts by weight, more preferably from 25 to 140 parts by weight, particularly preferably from 50 to 125 parts by weight, per 100 parts by weight of the resin composed of 1 to 99% by weight of the resin.
[0062]
Further, the method of blending the fiber reinforcing material (D) is not limited, but it is a method of melt-mixing after mixing with another composition of the present invention or a part of the composition, and an extruder which is a melt kneader. In the middle of the process or near the discharge port and melt-mixing with the other composition of the present invention.
[0063]
In the present invention, the (E) triazine compound and a salt of cyanuric acid or isocyanuric acid are preferably an adduct of cyanuric acid or isocyanuric acid with a triazine compound, usually 1 to 1 (molar ratio), and in some cases. It is 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. (E) Among salts of a triazine compound with cyanuric acid or isocyanuric acid, particularly, melamine, benzoguanamine, acetoguanamine, 2-amide-4,6-diamino-1,3,5-triazine, mono (hydroxy Methyl) melamine, di (hydroxymethyl) melamine, and tri (hydroxymethyl) melamine salts are preferred, and melamine, benzoguanamine, and acetoguanamine salts are particularly preferred, and are produced by known methods. A mixture of an acid or isocyanuric acid is made into a water slurry, mixed well to form both salts into fine particles, and then the slurry is filtered, dried and generally obtained in powder form. Further, the above salt does not need to be completely pure, and a somewhat unreacted triazine-based compound, cyanuric acid, or isocyanuric acid may remain. The average particle size of the salt before being mixed with the resin is preferably 100 to 0.01 μm, more preferably 100 to 0.01 μm, from the viewpoint of flame retardancy, mechanical strength and wet heat resistance of the molded product, retention stability, and surface properties. Is 80 to 1 μm. When the dispersibility of the above salt is poor, a dispersant such as tris (β-hydroxyethyl) isocyanurate, a known surface treating agent, silica, polyvinyl alcohol, or the like may be used in combination.
[0064]
The amount of the (E) triazine compound and the salt of cyanuric acid or isocyanuric acid is preferably 100 parts by weight of (A) polybutylene terephthalate resin or 99 to 1 in terms of flame retardancy and mechanical properties. 1 to 150 parts by weight, preferably 5 to 120 parts by weight, more preferably 15 to 80 parts by weight, based on 100 parts by weight of a resin consisting of 1 to 99% by weight of a polyethylene terephthalate resin. is there.
[0065]
The (F) fluorine compound in the present invention can further suppress the melt-down of the flame-retardant resin composition at the time of combustion by further blending a fluorine-based resin, and further improve the flame retardancy. . The (F) fluorine-based compound is a resin containing fluorine in a substance molecule, and specifically, polytetrafluoroethylene, polyhexafluoropropylene, (tetrafluoroethylene / hexafluoropropylene) copolymer , (Tetrafluoroethylene / perfluoroalkylvinyl ether) copolymer, (tetrafluoroethylene / ethylene) copolymer, (hexafluoropropylene / propylene) copolymer, polyvinylidene fluoride, (vinylidene fluoride / ethylene) copolymer Polymers and the like can be mentioned. Among them, polytetrafluoroethylene, (tetrafluoroethylene / perfluoroalkylvinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / ethylene) Copolymers, polyvinylidene fluoride are preferable, polytetrafluoroethylene, (tetrafluoroethylene / ethylene) copolymer are preferable. The amount of the fluorine compound (F) is 100 parts by weight of the polybutylene terephthalate resin (A) or 99 to 1% by weight of the polybutylene terephthalate resin, and the polyethylene terephthalate resin 1 to 100 parts by weight in view of flame retardancy and mechanical properties. The amount is preferably 0.02 to 10 parts by weight, more preferably 0.1 to 8 parts by weight, and still more preferably 0.2 to 6 parts by weight, based on 100 parts by weight of the 99% by weight resin.
[0066]
The (G) alkaline earth metal salt of the present invention is preferably a salt of magnesium, calcium and barium belonging to alkaline earth metals, and specific examples include magnesium hydroxide, calcium hydroxide, barium hydroxide, magnesium oxide, Calcium oxide, barium oxide, magnesium carbonate, calcium carbonate, barium carbonate, magnesium sulfate, calcium sulfate, barium sulfate, magnesium phosphate, calcium phosphate, barium phosphate, magnesium acetate, calcium acetate, barium acetate, magnesium lactate, calcium lactate, lactic acid Barium, and further include magnesium salts, calcium salts, and barium salts of organic acids such as oleic acid, palmitic acid, stearic acid and montanic acid, and magnesium hydroxide and calcium carbonate are preferred. Irare, more preferably calcium carbonate is used. Depending on the production method, the above calcium carbonate is known as calcium chloride carbonate, light calcium carbonate, heavy calcium carbonate, wet-pulverized fine powder heavy calcium carbonate, wet heavy calcium carbonate (chalk) and the like. Included in the invention. Further, the above-mentioned calcium carbonate and alkaline earth metal salt may be treated with one or more surface treatment agents such as a silane coupling agent, an organic substance and an inorganic substance, and may be in the form of powder, plate or fiber. It may be used, but it is preferable to use it in a powder form of 10 μm or less from the viewpoint of dispersibility.
[0067]
(G) By adding an alkaline earth metal salt, the hydrolysis characteristics can be significantly improved. Phosphate-based compounds that are effective as non-halogen flame retardants have the drawback that they are poorly hydrolyzable because the phosphate bond is easily hydrolyzed. In the present invention, it is presumed that the prevention of bleed-out by the vinyl resin and the synergistic action of the acid trap by the alkaline earth metal salt greatly improve the hydrolyzability.
[0068]
The amount of the alkaline earth metal salt (G) is 100 parts by weight of the polybutylene terephthalate resin (A) or 99 to 1% by weight of the polybutylene terephthalate resin and the polyethylene terephthalate resin 1 in terms of mechanical properties and hydrolyzability. It is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 4.5 parts by weight, and still more preferably 0.15 to 4 parts by weight, based on 100 parts by weight of the resin consisting of 100 to 99% by weight. It is.
[0069]
The (H) epoxy compound used in the present invention is an epoxy compound using at least one of a glycidyl ester compound, a glycidyl ether compound, and a glycidyl ester ether compound.
[0070]
In order to exhibit an excellent effect of improving the hydrolyzability of PBT, an epoxy compound having an epoxy equivalent of less than 500 is preferable, and an epoxy compound having an epoxy equivalent of less than 400 is particularly preferable. Here, the epoxy equivalent is an epoxy compound in which the number of grams of an epoxy compound containing one gram equivalent of an epoxy group is less than 500. In the measurement example of the epoxy equivalent, the epoxy compound is dissolved in pyridine and 0.05N There is known a method in which hydrochloric acid is added and heated at 40 to 45 ° C., and then a back titration with 0.05N caustic soda is performed using a mixed solution of thymol blue and cresol red as an indicator.
[0071]
Further, as the epoxy compound, an epoxy compound using a monofunctional glycidyl ester compound and a glycidyl ether compound in combination or a monofunctional glycidyl ester compound is preferably used, and in particular, the viscosity stability and hydrolyzability of the resulting composition are preferably used. From the balance of the above, a monofunctional glycidyl ester compound is more preferable.
[0072]
Examples of the glycidyl ester compound include, but are not limited to, glycidyl benzoate, tBu-glycidyl benzoate, glycidyl P-toluate, glycidyl cyclohexanecarboxylate, and glycidyl pelargonate. Esters, glycidyl stearate, glycidyl laurate, glycidyl palmitate, glycidyl behenate, glycidyl versatate, glycidyl oleate, glycidyl linoleate, glycidyl linoleate, glycidyl behenol, stearolic acid Glycidyl ester, terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, phthalic acid diglycidyl ester Diglycidyl naphthalenedicarboxylate, diglycidyl bibenzoate, diglycidyl methyl terephthalate, diglycidyl hexahydrophthalate, diglycidyl tetrahydrophthalate, diglycidyl cyclohexanedicarboxylate, diglycidyl adipate , Succinic acid diglycidyl ester, sebacic acid diglycidyl ester, dodecandionic acid diglycidyl ester, octadecanedicarboxylic acid diglycidyl ester, trimellitic acid triglycidyl ester, pyromellitic acid tetraglycidyl ester, and the like. Two or more types can be used.
[0073]
Examples of the glycidyl ether compound include, but are not limited to, phenylglycidyl ether, O-phenylphenylglycidyl ether, 1,4-bis (β, γ-epoxypropoxy). ) Butane, 1,6-bis (β, γ-epoxypropoxy) hexane, 1,4-bis (β, γ-epoxypropoxy) benzene, 1- (β, γ-epoxypropoxy) -2-ethoxyethane, 1 -(Β, γ-epoxypropoxy) -2-benzyloxyethane, 2,2-bis- [р- (β, γ-epoxypropoxy) phenyl] propane and 2,2-bis- (4-hydroxyphenyl) propane Glycidyl polyether obtained by the reaction of epichlorohydrin with bisphenols such as and 2,2-bis- (4-hydroxyphenyl) methane Le and the like, which can be used either alone or in combination.
[0074]
The amount of the epoxy compound (H) is 100 parts by weight of polybutylene terephthalate (A) or 99 to 1% by weight of polybutylene terephthalate resin and 1 to 99% by weight of polyethylene terephthalate resin in view of mechanical properties and hydrolyzability. It is preferably from 0.05 to 5 parts by weight, more preferably from 0.1 to 4.5 parts by weight, based on 100 parts by weight of the resin consisting of
[0075]
In general, it is known that the use of an epoxy compound blocks a terminal carboxyl group of a polybutylene terephthalate resin and improves the hydrolysis resistance of the polybutylene terephthalate resin. When the earth metal salt and the present epoxy compound are used in combination, the hydrolysis resistance is synergistically improved, and it is possible to impart a high degree of hydrolysis that cannot be achieved by simply adding an epoxy compound.
[0076]
In the present invention, flame retardancy can be further improved by further blending a polycarbonate resin. Examples of the polycarbonate resin include an aromatic homo- or copolycarbonate 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 usually in the range of 10,000 to 1,000,000, and if the viscosity-average molecular weight is in the range of 10,000 to 1,000,000, a polycarbonate resin having a different viscosity-average molecular weight is used in combination. Is also good. 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 and the like can be used, and these can be used alone or as a mixture. Further, the blending amount of the polycarbonate resin is preferably from 1 to 100 parts by weight, particularly preferably from 2 to 90 parts by weight, based on 100 parts by weight of the polybutylene terephthalate resin (A) from the viewpoint of flame retardancy and mechanical properties. .
[0077]
In the present invention, a flame retardant auxiliary such as a silicone compound, a phenol resin, a phosphonitrile compound, ammonium polyphosphate, melamine polyphosphate and an inorganic hydrate can be compounded to improve the flame retardancy and suppress a gas generated during combustion. Used in one or more types. The amount of the flame retardant aid is preferably 0.1 to 50 parts by weight, particularly preferably 0 to 100 parts by weight of (A) the polybutylene terephthalate resin in view of flame retardancy and mechanical properties. 0.5 to 30 parts by weight.
[0078]
Examples of the silicone compound include silicone resin, silicone oil, and silicone powder.
[0079]
Examples of the silicone resin include a polyorganosiloxane in which a siloxane is chemically bonded to a group selected from a saturated or unsaturated monovalent hydrocarbon group, a hydrogen atom, a hydroxyl group, an alkoxyl group, an aryl group, and a vinyl or allyl group. Although those having a viscosity of about 200 to 300,000,000 centipoise at room temperature are preferable, as long as the above silicone resin is used, the present invention is not limited thereto, and even if the product shape is oily, powdery or gummy, Further, an epoxy group, a methacle group and an amino group may be introduced as a functional group, or a mixture with two or more silicone resins may be used.
[0080]
As the silicone oil, a polyorganosiloxane in which a siloxane is chemically bonded to a group selected from a saturated or unsaturated monovalent hydrocarbon group, a hydrogen atom, a hydroxyl group, an alkoxyl group, an aryl group, a vinyl or allyl group and a siloxane is used. Preferred are those having a viscosity of about 0.65 to 100,000 centistokes at room temperature, but are not limited thereto as long as the above silicone oil resin is used, and the product shape is oily, powdery and gummy. The epoxy group, the methacle group and the amino group may be introduced as functional groups, and a mixture with two or more kinds of silicone oils or silicone resins may be used.
[0081]
The silicone powder is obtained by blending the above-mentioned silicone resin and / or silicone oil with an inorganic filler. As the inorganic filler, silica or the like is preferably used.
[0082]
The phenol resin is not particularly limited as long as it is a polymer having a plurality of phenolic hydroxyl groups, and examples thereof include novolak-type, resol-type, and heat-reactive resins, or resins modified from these. These may be an uncured resin, a semi-cured resin, or a cured resin without a curing agent added. Above all, a novolak-type phenol resin that is non-thermally reactive without adding a curing agent is preferred in terms of flame retardancy, mechanical properties, and economic efficiency.
[0083]
Further, the shape of the phenol resin is not particularly limited, and any of pulverized products, granules, flakes, powders, needles, and liquids can be used, and one or more of them can be used as necessary. The phenolic resin is not particularly limited, and a commercially available phenolic resin is used. For example, in the case of a novolak type phenol resin, phenols and aldehydes are charged into a reaction tank at a molar ratio of 1: 0.7 to 1: 0.9, and oxalic acid, hydrochloric acid, sulfuric acid, toluene sulfone are further added. After adding a catalyst such as an acid, the mixture is heated and a reflux reaction is performed for a predetermined time. Vacuum dehydration or static dehydration in order to remove the generated water can be obtained by a method of removing remaining water and unreacted phenols. These resins or co-condensed phenol resins obtained by using a plurality of raw material components can be used alone or in combination of two or more. In the case of a resole type phenol resin, a molar ratio of phenols and aldehydes is charged into a reaction tank at a ratio of 1: 1 to 1: 2, and a catalyst such as sodium hydroxide, aqueous ammonia, or another basic substance is added. After the addition, it can be obtained by performing the same reaction and treatment as for the novolak type phenol resin.
[0084]
Here, phenols include phenol, o-cresol, m-cresol, p-cresol, thymol, p-tert-butylphenol, tert-butylcatechol, catechol, isoeugenol, o-methoxyphenol, 4,4′-dihydroxy Phenyl-2,2-propane, isoamyl salicylate, benzyl salicylate, methyl salicylate, 2,6-di-tert-butyl-p-cresol and the like can be mentioned. One or more of these phenols can be used. On the other hand, examples of the aldehydes include formaldehyde, paraformaldehyde, polyoxymethylene, and trioxane. One or two or more of these aldehydes can be used as necessary.
[0085]
The molecular weight of the phenolic resin is not particularly limited, but is preferably 200 to 2,000 in number average molecular weight, and particularly preferably 400 to 1,500 in terms of mechanical properties, fluidity, and economy. The molecular weight of the phenolic resin can be measured by gel permeation chromatography using a tetrahydrafuran solution and a polystyrene standard sample.
[0086]
Examples of the phosphonitrile compound include a phosphonitrile compound having a phosphonitrile linear polymer and / or a cyclic polymer as a main component, and may be a linear or cyclic compound or a mixture. The phosphonitrile linear polymer and / or cyclic polymer can be synthesized by a known method described in the author, “Synthesis and Application of Phosphazene Compounds” by Kajiwara, for example, phosphorus pentachloride or trichloride as a phosphorus source. It can be synthesized by reacting ammonium chloride or ammonia gas as a phosphorus or nitrogen source by a known method (cyclic substances may be purified), and substituting the obtained substance with alcohols, phenols and amines. .
[0087]
Examples of the ammonium polyphosphate include ammonium polyphosphate, melamine-modified ammonium phosphate, and ammonium carbamyl polyphosphate, and include a thermosetting phenol resin, a urethane resin, a melamine resin, a urea resin, an epoxy resin, and a urea resin. It may or may not be coated with a thermosetting resin or the like, and may be used alone or in combination of two or more.
[0088]
Examples of the melamine phosphate include phosphates such as melamine polyphosphate and melamine pyrophosphate, and may be used alone or in combination of two or more.
[0089]
Examples of the inorganic hydrate include, but are not limited to, aluminum hydroxide, hydrotalcite, boric acid, calcium borate, calcium borate hydrate, zinc borate, zinc borate hydrate, and hydroxide. Zinc, zinc hydroxide hydrate, zinc tin hydroxide, zinc tin hydroxide hydrate, red phosphorus, heat-expanded graphite, dawsonite, etc .; thermosetting melamine resin, thermosetting phenol resin, heat A thermosetting resin such as a curable epoxy resin may be mixed or coated on the surface. Further, a coupling agent, an epoxy compound, or a fat or oil such as stearic acid may be mixed or coated on the surface.
[0090]
In the present invention, a phenoxy resin, an oxazoline compound, a carbodiimide compound and the like can be blended for the purpose of further improving the hydrolyzability, and a phenoxy resin is particularly preferably used. The amount of the above-mentioned hydrolyzability-improving material is preferably 100 parts by weight of the polybutylene terephthalate resin (A) or 99 to 1 parts by weight of the polybutylene terephthalate resin in view of the hydrolyzability and flame retardancy of the resulting composition. %, Preferably 0.1 to 50 parts by weight, particularly preferably 0.5 to 30 parts by weight, based on 100 parts by weight of the resin composed of 1 to 99% by weight of the polyethylene terephthalate resin.
[0091]
Further, the phenoxy resin is obtained by reacting an aromatic dihydric phenol compound and epichlorohydrin at various mixing ratios, and the molecular weight of the phenoxy resin or phenoxy copolymer is not particularly limited, but the viscosity average It has a molecular weight in the range of 1,000 to 100,000. Here, examples of the aromatic dihydric phenol compound include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, and bis (4 -Hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3,5 diethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) methane and the like can be used, and these can be used alone or as a mixture. The shape is not particularly limited, and any of pulverized products, granules, flakes, powders, and liquids can be used. One or two or more of these phenoxy resins can be used as necessary.
[0092]
In the present invention, a hindered phenol-based antioxidant and / or a phosphite-based antioxidant can be further blended as a stabilizer that gives extremely good heat aging resistance even when the composition of the present invention is exposed to a high temperature for a long period of time. The amount of the hindered phenol-based antioxidant and / or the phosphite-based antioxidant is determined based on 100 parts by weight of the polybutylene terephthalate resin (A) or the polybutylene terephthalate resin 99 in view of heat aging resistance and flame retardancy. 0.1 to 15 parts by weight, particularly preferably 0.2 to 10 parts by weight, based on 100 parts by weight of a resin composed of 1 to 99% by weight of a polyethylene terephthalate resin.
[0093]
Specific examples of the hindered phenol-based antioxidants include triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] and 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-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) ) Propionate, 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, 1,3,5-trimethyl-2, 4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, bis or tris (3-tert-butyl-6-methyl-4-hydroxyphenyl) propane, N, N'-hexa Methylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), N, N′-trimethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide) ).
[0094]
Examples of the phosphite-based stabilizer include tris (2,4-di-t-butylphenyl) phosphite and 2,2-methylenebis (4,6-di-t-butylphenyl) octylphospho. Phyto, trisnonylphenyl phosphite, alkyl allyl phosphite, trialkyl phosphite, triallyl phosphite, pentaerythritol phosphite compound, and the like.
[0095]
In the present invention, it is possible to improve fluidity, mold release, abrasion, and sliding characteristics during molding by further adding one or more lubricants. Examples of such a lubricant include metal soaps such as calcium stearate and barium stearate, fatty acid esters, salts of fatty acid esters (including partially salted ones), fatty acid amides such as ethylenebisstearamide, ethylenediamine and stearic acid. And fatty acid amides comprising polycondensates of sebacic acid or polycondensates of phenylenediamine with stearic acid and sebacic acid, polyalkylene waxes, acid anhydride-modified polyalkylene waxes and the above lubricants and fluororesins or fluorine compounds. Mixtures include, but are not limited to. The amount of the lubricant to be added is 0.05 to 100 parts by weight of (A) a polybutylene terephthalate resin or 100 parts by weight of a resin composed of 99 to 1% by weight of a polybutylene terephthalate resin and 1 to 99% by weight of a polyethylene terephthalate resin. It is preferably from 10 to 10 parts by weight, more preferably from 0.1 to 5 parts by weight.
[0096]
In the present invention, the color tone can be improved or toned by blending carbon black, titanium oxide, and one or more kinds of pigments and dyes of various colors. From the viewpoint of the mechanical properties of (A) 0.1 to 100 parts by weight of polybutylene terephthalate resin, or 0.1 to 100 parts by weight of a resin composed of 99 to 1% by weight of polybutylene terephthalate resin and 1 to 99% by weight of polyethylene terephthalate resin The amount is preferably 30 parts by weight, more preferably 0.1 to 20 parts by weight, even more preferably 0.1 to 15 parts by weight.
[0097]
Examples of the carbon black include, but are not limited to, channel black, furnace black, acetylene black, anthracene black, oil smoke, pine smoke, and graphite, and have an average particle diameter of 500 nm or less, and dibutyl phthalate. Oil absorption 50-400cm ³ / 100 g of carbon black is preferably used, and may be treated with aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, polyol, silane coupling agent or the like as a treating agent. Further, as the above titanium oxide, a titanium oxide having a crystal form such as a rutile form or an anatase form and having an average particle diameter of 5 μm or less is preferably used, and as a treating agent, aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, It may be treated with a polyol, a silane coupling agent or the like. In addition, the above carbon black, titanium oxide, and pigments and dyes of various colors are used for improving the dispersibility of the flame-retardant resin composition of the present invention and improving the handling property during production. And may be used as a melt blended or simply blended mixed material. In particular, polyalkylene terephthalate is preferably used as the thermoplastic resin.
[0098]
Furthermore, as long as the object of the present invention is not impaired with respect to the flame-retardant polybutylene terephthalate resin composition and the molded article of the present invention, a sulfur-based antioxidant, an ultraviolet absorber, a plasticizer, and an antistatic agent. A material containing one or more known additives can also be used.
[0099]
The flame-retardant polybutylene terephthalate resin composition and molded article of the present invention are usually produced by a known method. For example, (A) a polybutylene terephthalate resin, (B) a multilayer structure polymer, (C) a phosphoric ester, if necessary (D) a fiber reinforcing material, and (E) a triazine compound and cyanuric acid or isocyanuric acid. Salt, (F) an alkaline earth metal salt, and, if necessary, a fluorine compound, a flame retardant aid, an ethylene (co) polymer, a hydrolytic improver, a hindered phenolic antioxidant and / or Premixing the phyto-based antioxidant, coloring agent for pigments and dyes, lubricants, and other necessary additives as necessary, or supplying them to an extruder or the like without mixing them and sufficiently kneading them. Thus, a flame-retardant polybutylene terephthalate resin composition is prepared.
[0100]
As an example of the premixing, the effect of the present invention can be exhibited only by dry blending, but mixing using a mechanical mixing device such as a tumbler, a ribbon mixer, and a Henschel mixer can be mentioned. Further, the fiber reinforcing material may be added by installing a side feeder in the middle of the filling portion and the vent portion of a multi-screw extruder such as a twin-screw extruder. In the case of liquid additives, a liquid addition nozzle is installed in the middle of the base and vent of a multi-screw extruder, such as a twin-screw extruder. A method of supplying with a pump may be used. Further, the method for producing the flame-retardant polybutylene terephthalate resin composition is not limited. For example, a single-screw extruder or a twin-screw extruder equipped with a “Unimelt” or “Dalmage” type screw And melt kneading using a triaxial extruder and a kneader type kneader.
[0101]
The flame-retardant polybutylene terephthalate resin composition thus obtained can be molded by a generally known method, for example, by injection molding, extrusion molding, compression molding, sheet molding, film molding, etc., to give a molded article of any shape. In particular, injection molding is preferable, and a molded product obtained by an injection molding method by insert molding in which a part of a metal component is directly integrated with a molded product may be used.
[0102]
Further, the molded article made of the flame-retardant polybutylene terephthalate resin composition of the present invention has high safety against electric flame inside the device and safety against fire of the molded article itself, and further has excellent appearance of the molded article and any color tone. Since it is possible and has excellent mechanical properties and heat cycle properties, it is useful for electric / electronic parts, mechanical mechanism parts, and automobile parts. Specifically, housing for general home appliances, OA equipment, coil bobbins, connectors, relays, disk drive chassis, transformers, electromagnetic switches, switch parts, outlet parts, motor parts, sockets, plugs, capacitors, various cases Type, resistors, electrical and electronic parts incorporating metal terminals and conductors, computer related parts, audio parts, audio parts such as laser discs, lighting parts, telecommunications and telephone equipment related parts, air conditioner parts, washing machine parts, VTRs and Examples include home appliance parts such as televisions, copier parts, facsimile parts, optical equipment parts, automobile ignition device parts, automobile connectors, and various automobile electrical parts.
[0103]
In the present invention, since a molded article excellent in heat cycle property is obtained while having particularly high flame retardancy, excellent molded article appearance and mechanical properties, when a product is used, a resin component or a temperature which changes in internal temperature is used. When used as a resin component that comes into contact with a metal or a thermosetting resin component having a significantly different coefficient of linear expansion, the durability can be expected to be greatly improved.
[0104]
From the above, it is particularly useful for use in electric / electronic parts having a large temperature change inside the product, electric parts for automobiles, and the like, because the improvement in durability can be expected.
[0105]
【Example】
Hereinafter, the effects of the present invention will be described in more detail with reference to examples. Here, all “%” and “part” represent “% by weight” and “part by weight”. The measuring method of each characteristic is as follows.
[0106]
Reference Example 1 (A) Polybutylene terephthalate resin (hereinafter abbreviated as PBT)
<A-1> Toray PBT-1100S (manufactured by Toray Industries, Inc.).
[0107]
Reference Example 2 Polyethylene terephthalate resin (hereinafter abbreviated as PET)
<A-2> Mitsui PETJ005 (Mitsui Pet Resin Co., Ltd., intrinsic viscosity 0.65).
[0108]
Reference Example 3 (B) Multilayer structure polymer (core-shell rubber)
<B-1> Core: silicone / acrylic polymer, shell: methyl methacrylate polymer “METABLEN” S2001 (manufactured by Mitsubishi Rayon Co., Ltd.)
<B-2> Core: silicone / acrylic polymer, shell: acrylonitrile / styrene polymer “METABLEN” SX006 (manufactured by Mitsubishi Rayon Co., Ltd.)
<B-3> Core: silicone / acrylic polymer, shell: methyl methacrylate / glycidyl methacrylate polymer “METABLEN” KS0205 (manufactured by Mitsubishi Rayon Co., Ltd.).
[0109]
Reference Example 4 (C) Phosphate
<C-1> Aromatic phosphate ester “PX-200” of the following formula (5) (manufactured by Daihachi Chemical Co., Ltd.)
[0110]
Embedded image

[0111]
<C-2> An aromatic phosphate ester “CR741” of the following formula (6) (manufactured by Daihachi Chemical Co., Ltd.).
[0112]
Embedded image

[0113]
Reference Example 5 (D) Fiber reinforced material (hereinafter abbreviated as GF)
<G-1> Chopped strand glass fiber “CS3J948” having a fiber diameter of about 10 μm (manufactured by Nitto Boseki Co., Ltd.).
[0114]
Reference Example 6 (E) Salt of triazine compound and cyanuric acid or isocyanuric acid (hereinafter abbreviated as MC salt)
<E-1> Melamine cyanurate “MCA” (manufactured by Mitsubishi Chemical Corporation).
[0115]
Reference Example 7 Fluorine compound
<F-1> Polytetrafluoroethylene “Teflon (registered trademark) 6J” (manufactured by DuPont-Mitsui Fluorochemicals).
[0116]
Reference Example 8 (G) Alkaline earth metal salt
<G-1> Magnesium hydroxide "Kisuma 6E" (manufactured by Kyowa Chemical Industry Co., Ltd.) (hereinafter abbreviated as water mug)
<G-2> Calcium carbonate “KSS1000” (manufactured by Dowa Calfine) (hereinafter abbreviated as charcoal).
[0117]
Reference Example 9 (H) Epoxy compound
<H-1>"Epicoat819" (manufactured by Japan Epoxy Resin Co.) containing bisphenol A diglycidyl ether as a main component.
[0118]
Reference Example 10 Flame retardant aid
<I-1> Polycarbonate resin (hereinafter abbreviated as PC) "Iupilon" S3000 (manufactured by Mitsubishi Engineering-Plastics Corporation).
[0119]
<I-2> Silicone compound, silicone powder "DC4-7105" (manufactured by Dow Corning Toray Silicone Co., Ltd.) (hereinafter abbreviated as silicone).
[0120]
<I-3> Novolak type phenol resin “Sumilite Resin” PR53195 (manufactured by Sumitomo Durez) (hereinafter abbreviated as phenol resin).
[0121]
<I-4> A phosphonitrile compound, hexachlorocyclotriphosphazene (cyclic trimer), and phenol are reacted in the presence of triethylamine, the obtained reaction solution is evaporated and dried, and the residue is washed with water. The salt was removed. Further, the product was purified by washing with acetone and then with ethanol to obtain a phosphonitrile cyclic polymer. (Hereinafter abbreviated as phosphonitrile).
[0122]
Reference Example 11 Ethylene copolymer and vinyl resin
<J-1> Ethylene ethyl acrylate copolymer (hereinafter abbreviated as EEA) "A-709" (manufactured by DuPont-Mitsui Polychemicals).
[0123]
<J-2> Ethylene / glycidyl methacrylate / methyl acrylate copolymer (hereinafter abbreviated as BF-7M) "BF-7M" (manufactured by Sumitomo Chemical Co., Ltd.).
<J-3> An acrylonitrile / styrene copolymer (a copolymer having a copolymerization ratio of 30/70% by weight was obtained by known suspension polymerization; hereinafter, abbreviated as AS).
<J-4> Polymethyl methacrylate polymer (hereinafter abbreviated as PMMA) “Acrypet MD” (manufactured by Mitsubishi Rayon Co., Ltd.).
[0124]
Reference Example 12 Inorganic filler other than fiber reinforcement
<K-1> Silicate talc “LMS300” (manufactured by Fuji Talc) (hereinafter abbreviated as talc).
[0125]
Reference Example 13 Hindered phenol antioxidant and / or phosphite antioxidant
<L-1> Hindered phenolic antioxidant “IR-1010” of pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by Nippon Ciba Geigy) (Hereinafter abbreviated as IR1010)
<L-2> A phosphite-based antioxidant “Mark PEP-36” of a pentaerythritol-based phosphite compound (manufactured by Asahi Denka Co., Ltd.) (hereinafter abbreviated as PEP36).
Examples 1-27, Comparative Examples 1-13
(A) PBT, PET, (B) multilayer polymer, (C) phosphoric acid, using a twin-screw extruder (TEX-30α, manufactured by Nippon Steel Works) having a screw diameter of 30 mm and L / D35 with a co-rotating vent. Ester, (E) MC salt, (F) fluorinated compound, (G) alkaline earth metal salt, and (H) epoxy compound, if necessary, other additives <I>, <K>, and <L> were mixed in the composition shown in Tables 1 to 3 and added from the main filling portion. In addition, GF of the component (D) was added in the same manner as described above, except that the side feeder was provided in the middle of the filling section and the vent section, and the compound having the amount shown in Table 1 was added from the filling section. . In addition, melt-mixing was performed under the extrusion conditions of a kneading temperature of 270 ° C. and a screw rotation of 150 rpm, and the mixture was discharged in a strand shape, passed through a cooling bath, and pelletized by a strand cutter.
[0126]
After drying the obtained pellets, each test piece was molded by an injection molding machine, and the physical properties were measured under the following conditions. The results are shown in Tables 1 to 3 in the same manner.
[0127]
(1) Flame retardancy
Using a Toshiba Machine's IS55EPN injection molding machine, injection molding of a test piece for flame retardancy evaluation was performed at a molding temperature of 270 ° C and a mold temperature of 80 ° C. The flammability was evaluated. The flame retardancy is reduced and ranked in the order of V-0>V-1> V-2. The thickness of the test piece is 1/16 inch (about 1.59 mm, hereinafter abbreviated as 1/16 "), 1/32 inch (about 0.79 mm, abbreviated as 1/32"), and A thickness of 64 inches (approximately 0.40 mm, hereinafter abbreviated as 1/64 ") was used, and the thinner the thickness, the more severely the flame retardancy was judged. The material was recorded as out of specification.
[0128]
(2) Mechanical properties
(2-1) Tensile strength
Using an IS55EPN injection molding machine manufactured by Toshiba Machine Co., a 3 mm thick ASTM No. 1 dumbbell injection molded product was obtained at a molding temperature of 270 ° C. and a mold temperature of 80 ° C. The tensile strength was measured according to ASTM D638.
[0129]
(2-2) Izod impact strength
Using an IS55EPN injection molding machine manufactured by Toshiba Machine Co., an Izod impact test specimen having a thickness of 3 mm was obtained at a molding temperature of 270 ° C. and a mold temperature of 80 ° C. The notched Izod impact strength was measured according to ASTM D256. Here, the test result described as NB indicates that the test piece does not break.
[0130]
(3) Heat cycle properties
Using a Toshiba Machine's IS55EPN injection molding machine, a metal with a shape that can wrap a square iron prism of 50 mm on both sides and height with a 1.5 mm thick sample at a molding temperature of 270 ° C and a mold temperature of 80 ° C. Using a mold, the product was put into an "ESPEC" thermal shock chamber TSA-70L manufactured by Tabai. As a cooling / heating test condition, -30 ° C. × 2 h and 120 ° C. × 2 h were one cycle. The heat cycle property was determined by observing the sample at any time to determine the number of cycles in which the crack occurred in the sample and recording the result.
[0131]
(4) Bleed-out test
Using a Toshiba Machine's IS55EPN injection molding machine, a 80 mm x 80 mm x 3 mm square plate injection-molded at a molding temperature of 270 ° C and a mold temperature of 80 ° C was used as a sample, and the temperature was adjusted to 150 ° C. The hot air dryer "HighTempOven" PVH210 was charged for 100 hours.
[0132]
The appearance of the square plate before and after the dryer was charged was visually observed, and the presence or absence of bleed-out was determined based on the following criteria.
[0133]
Here, the bleed-out is a phenomenon in which a part of the compound in the molded article composition is stained on the surface of the molded article.
[0134]
○: Bleed-out is not observed in the molded product before and after the dryer is put
Δ: Bleed-out was not observed in the molded product before the dryer was input, but bleed-out was observed in the molded product after the dryer was input.
X: Bleed-out is observed in the molded article before and after the dryer is introduced.
[0135]
(5) Hydrolytic properties
Using a Toshiba Machine's IS55EPN injection molding machine, a 3 mm thick ASTM No. 1 dumbbell piece was injection molded at a molding temperature of 270 ° C. and a mold temperature of 80 ° C., and the obtained ASTM No. 1 dumbbell piece was subjected to a temperature of 121 ° C. and humidity. After the wet heat treatment under the condition of 100% RH for 100 hours, the tensile strength is measured according to ASTM D648, and the measured value is a tensile strength retention (%) which is a percentage of a value obtained by dividing by a tensile strength of an untreated product. Indicated.
[0136]
(6) Semi-crystallization time
About 15 mg of a sample was collected from a 1/32 "thickness combustion test piece used for the evaluation of flame retardancy, and set on a DSC-7 differential calorimeter manufactured by Parking Elmer Co., Ltd. The temperature was lowered to 190 ° C. at a temperature lowering speed, and the time at which a crystallization peak appeared was recorded while maintaining the temperature at 190 ° C. Since the time until the crystallization peak corresponds to half of the crystal, it was expressed as a half crystallization time. Since it is estimated that the shorter this time is, the faster the solidification rate during injection molding is, the measured value is a measure of the crystallization rate.
[0137]
(7) Heat resistance
Using a Toshiba Machine's IS55EPN injection molding machine, a 3 mm thick ASTM No. 1 dumbbell piece was injection-molded at a molding temperature of 270 ° C. and a mold temperature of 80 ° C., and the obtained ASTM No. 1 dumbbell piece was heated to a temperature of 180 ° C. After 200 hours into a conditioned perfection oven made of Tabi, the tensile strength was measured according to ASTM D648, and the measured value was the tensile strength retention (%), which is a percentage of the value obtained by dividing the tensile strength of the untreated product. Indicated.
[0138]
[Table 1]

[0139]
[Table 2]

[0140]
[Table 3]

[0141]
Comparative Example 1 When PET containing no PBT was used as the component (A), solidification was slow under the above-described injection molding conditions, and a molded product for evaluation could not be obtained.
[0142]
Table 1 describes the effects of (A) PBT, a mixture of PBT and PET, (B) a multilayer structure polymer, and (C) a phosphate ester of the composition of the present invention.
[0143]
From Comparative Examples 2 to 4, (A) PBT was blended with (C) phosphate ester to show a combustibility of 1/16 ″ thickness V-2. However, bleed out on the surface of the molded product was observed. Therefore, it can be said that the molded article has no commercial value.
[0144]
However, according to Examples 1 to 6 of the composition of the present invention, by blending (A) PBT and a mixture of PBT and PET with (B) a multilayer structure polymer and (C) a phosphate, V- It can be said that there is an effect of obtaining a molded product having excellent appearance of the molded product, in which the bleed-out does not occur while maintaining the flame retardancy of No. 2.
[0145]
Further, also in Examples 7 to 9 in which (D) a fiber reinforcing material was blended, high-strength molding having an excellent appearance of a molded product without causing bleed-out while maintaining the flame retardancy of V-2. It can be said that there is an effect of obtaining a product.
[0146]
However, in Comparative Examples 5 and 6 in which (B) a multilayer structure polymer and (C) a fiber reinforced material which does not contain any of the phosphate esters are blended, is there any flammability observed? Alternatively, since the bleed out occurs on the surface of the molded product, it can be said that the molded product has no commercial value.
[0147]
Also, in the case of Comparative Examples 7 to 8 in which (B) the multilayer structure polymer and (C) the phosphoric acid ester were blended beyond the scope of the present invention, no flammability was observed or the molded article was not formed. Since bleeding occurs on the surface, it can be said that the molded article has no commercial value.
[0148]
Further, the compositions of Comparative Examples 9 to 12 in which an ethylene copolymer or a vinyl resin was blended instead of (B) the multilayer structure polymer of Example 7 were the compositions other than the flame retardancy and impact strength reduction and AS. This material also causes bleed-out, and can be said to be an undesirable composition. Further, when comparing the impact strength and the heat cycle property of Example 7 with Comparative Examples 7 to 8, it is found that (B) the multi-layer structure polymer has a bleed-out preventing effect without adversely affecting the flame retardancy. It can be said that there is an effect excellent in mechanical properties and heat cycle properties.
[0149]
Table 2 shows the effect of the composition containing (E) an MC salt, (F) a fluorine compound, (G) an alkaline earth metal salt, and (H) an epoxy compound, as required in the present invention. .
[0150]
From Examples 10 to 13, when the (E) MC salt and the (F) fluorine compound are blended, the flame retardancy is 1/16 "thickness V-0, 1/32" thickness V-2 to V −0, indicating that there is an effect of obtaining a molded article having significantly improved flame retardancy, excellent mechanical properties and heat cycle properties, and having no bleed-out.
[0151]
However, even in the composition containing (E) an MC salt and (F) a fluorine compound, in the case of Comparative Example 8 in which (B) a multilayer polymer was not added, not only the effect of preventing bleed out but also the impact strength and It can be said that it is a molded article having poor heat cycle properties.
[0152]
Further, from Examples 14 to 17, when (G) an alkaline earth metal salt and (H) an epoxy compound are blended as required in the present invention, the flame retardancy and excellent physical properties of Example 10 are obtained. While maintaining, the hydrolyzability is improved, and it can be said that there is an effect that the hydrolyzability is dramatically improved, especially when (G) an alkaline earth metal salt and (H) an epoxy compound are used in combination.
[0153]
Table 3 shows the effects of the flame retardant aid, the inorganic filler, and the antioxidant, which are further blended as needed in the present invention with the composition of Example 13.
[0154]
From Examples 18 to 21, it was found that the composition containing PC, phenolic resin, silicone, and phosphonitrile, which are flame retardant auxiliaries, shows excellent flame retardancy even at 1/64 ″ thickness while maintaining excellent physical properties. It can be said that there is an effect of giving the property.
[0155]
Also, from Example 22, it can be said that blending talc has an effect of obtaining a composition having an excellent crystallization rate while maintaining excellent physical properties and flame retardancy.
[0156]
From Examples 23 to 24, it can be said that the addition of an antioxidant has an effect of obtaining a composition having excellent heat resistance while maintaining excellent physical properties and flame retardancy.
[0157]
Further, the compositions of Examples 25 to 27 are materials in which another resin having better flame retardancy than PBT is blended with the composition of the present invention. It can be said that the invention effect is not spoiled.
[0158]
According to the present invention, a specific amount of a polymer having a multilayer structure, a phosphate ester, and a fiber reinforcing material, a salt of a triazine compound and a cyanuric acid or isocyanuric acid, a fluorine compound, an alkaline earth metal are added to PBT, if necessary. By combining salts and epoxy compounds, and if necessary, flame retardant aids, inorganic fillers, antioxidants, etc., while maintaining high flame retardancy, specific mechanical properties, heat cycle A highly reliable non-halogen flame-retardant polybutylene terephthalate resin composition and a molded article having excellent moldability, color tone of the molded article, and excellent bleed-out and excellent appearance of the molded article can be obtained. -It can be expected to greatly contribute to market expansion of electronic parts and mechanical parts.

Claims (12)

Flame-retardant polybutylene terephthalate resin obtained by blending (B) 1 to 50 parts by weight of a multilayer structure polymer and (C) 1 to 70 parts by weight of a phosphoric ester with respect to 100 parts by weight of (A) polybutylene terephthalate resin. Composition. (B) 1 to 50 parts by weight of a multilayer structure polymer and (C) 1 to 70 parts by weight of a phosphoric ester are mixed with 100 parts by weight of a mixture composed of a polybutylene terephthalate resin and a polyethylene terephthalate resin. Flame retardant polybutylene terephthalate resin composition. The flame-retardant polybutylene terephthalate resin composition according to claim 2, wherein the polybutylene terephthalate resin constituting the mixture is 1 to 99% by weight and the polyethylene terephthalate resin is 99 to 1% by weight. The flame-retardant poly according to any one of claims 1 to 3, further comprising 1 to 150 parts by weight of (D) a fiber reinforcing material with respect to 100 parts by weight of (A) component. Butylene terephthalate resin composition. The multilayer polymer (B) is a multilayer polymer in which the outermost layer is composed of a polymer containing an unsaturated carboxylic acid alkyl ester-based unit. Item 10. The flame-retardant polybutylene terephthalate resin composition according to item 8. (B) a multilayer structure polymer having a layer composed of a polymer containing at least one or more units selected from unsaturated glycidyl group-containing units and unsaturated dicarboxylic anhydride-based units The flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 5, wherein (A) 100 parts by weight of a polybutylene terephthalate resin, or 100 parts by weight of a resin composed of 99 to 1% by weight of a polybutylene terephthalate resin and 1 to 99% by weight of a polyethylene terephthalate resin, (E) a triazine compound and cyanuric acid The flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 8, further comprising 1 to 150 parts by weight of a salt with isocyanuric acid. (A) 100 parts by weight of a polybutylene terephthalate resin or 100 parts by weight of a resin composed of 99 to 1% by weight of a polybutylene terephthalate resin and 1 to 99% by weight of a polyethylene terephthalate resin, and (F) a fluorine-based compound, 8. The flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 7, which is blended with 0.02 to 10 parts by weight. (A) 100 parts by weight of a polybutylene terephthalate resin or 100 parts by weight of a resin composed of 99 to 1% by weight of a polybutylene terephthalate resin and 1 to 99% by weight of a polyethylene terephthalate resin, and (G) an alkaline earth metal salt The flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 8, further comprising 0.05 to 5 parts by weight. (A) 100 parts by weight of a polybutylene terephthalate resin, or 100 parts by weight of a resin composed of 99 to 1% by weight of a polybutylene terephthalate resin and 1 to 99% by weight of a polyethylene terephthalate resin; The flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 9, which is contained in an amount of from 0.5 to 5 parts by weight. The flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 10, wherein the phosphate of (C) is an aromatic phosphate of the following formula (1).

(In the above formula, Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ represent the same or different phenyl groups or phenyl groups substituted with halogen-free organic residues. X represents the following (2) And R ^{1 to} R ⁸ represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, and Y represents a direct bond, O, S, SO ₂ , C (CH ₃ ) ₂ , CH ₂ , CHPh, Ph represents a phenyl group, n in the formula (1) is an integer of 0 or more, and may be a mixture of different n. Are each an integer of 0 or more and 2 or less, and (k + m) is an integer of 0 or more and 2 or less.

A molded article for a mechanical mechanism part, an electric / electronic part or an automobile part, comprising the flame-retardant polybutylene terephthalate resin composition according to any one of claims 1 to 11.