JP3871477B2 - Flame retardant resin composition - Google Patents

Description

【００５９】
（式中、Ｒ³〜Ｒ⁶は置換基を有していてもよいアリール基を、Ｚは二価の芳香族性基を示す。ａは１〜５の整数を示す）
式（２）において、Ｒ³〜Ｒ⁶で示されるアリール基としては、フェニル、ナフチル基などのＣ_6-20アリール基が挙げられ、アリール基の置換基としては、メチル基、エチル基などのアルキル基が挙げられる。また、二価の芳香族性基としては、アリーレン基（例えば、フェニレン、ナフチレン基などのＣ_6-20アリーレン基など）、複数の前記アリーレン基を有する基［ビスフェノール残基（ビスフェノールＡ残基、ビスフェノールＤ残基、ビスフェノールＡＤ残基）などのビスフェノール類からヒドロキシル基が除かれた基、ビフェニレン基など］であってもよい。
【００６０】
上記式（２）で表される縮合物としては、例えば、レゾルシノールビス（ジフェニルホスフェート）、レゾルシノールビス（ジクレジルホスフェート）、レゾルシノールビス（ジキシリルホスフェート）、ハイドロキノンビス（ジフェニルホスフェート）、ハイドロキノンビス（ジクレジルホスフェート）、ハイドロキノンビス（ジキシリルホスフェート）、ビスフェノール−Ａビス（ジフェニルホスフェート、ビスフェノール−Ａビス（ジクレジルホスフェート）、ビスフェノール−Ａビス（ジキシリルホスフェート）などが挙げられる。
【００６１】
また、前記ポリマー型有機リン化合物は、ヒドロキシル基を有するポリマー（フェノール樹脂など）のリン酸エステルであってもよい。このようなポリマーのリン酸エステルとしては、例えば、下記式（３）で表される構造単位を有するポリマーが挙げられる。
【００６２】
【化４】

【００６３】
（式中、Ｒ⁷及びＲ⁸は置換基を有していてもよいアリール基を示す）
前記アリール基としては、Ｃ_6-20アリール基、特にフェニル基、メチルフェニル基、ジメチルフェニル基などが挙げられ、アリール基の置換基としては、メチル基、エチル基などのアルキル基が挙げられる。
【００６４】
さらに、前記ポリマー型有機リン化合物には、ポリホスフィニコカルボン酸エステル、ポリホスホン酸アミドも含まれる。ポリホスホン酸アミドとしては、例えば、下記式（４）で表される構造単位を有するポリマーが例示できる。
【００６５】
【化５】

【００６６】
（式中、Ｒ⁹はアルキル基、シクロアルキル基、アリール基、アラルキル基を示し、Ｒ¹⁰はアルキレン基、アリーレン基、又はアラルキレン基を示す。Ｒ¹¹及びＲ¹²は、同一又は異なって、水素原子、アルキル基、又はアリール基を示す。また、Ｒ¹¹及びＲ¹²は、直結して環を形成してもよい）
前記無機リン化合物としては、例えば、赤リン、リン酸塩などが含まれる。リン酸には、オルトリン酸の他に、亜リン酸、ポリリン酸（メタリン酸、ピロリン酸など）、ポリ亜リン酸（メタ亜リン酸、ピロ亜リン酸など）なども含まれる。塩としては、アルカリ金属塩（リチウム塩、ナトリウム塩、カリウム塩など）、アルカリ土類金属塩（マグネシウム塩、カルシウム塩など）、周期表３Ｂ族金属の塩（アルミニウム塩など）、アンモニウム塩などが例示できる。また、前記塩には、アミン塩、例えば、グアニジン塩又はトリアジン系化合物の塩（例えば、メラミン塩、メレム塩など）なども含まれる。
【００６７】
なお、無機リン化合物は、アルキル基又はアリール基が置換していてもよい亜リン酸、次亜リン酸、ホスホノカルボン酸、ホスフィニコカルボン酸（例えば、３−メチルホスフィニコプロピオン酸、３−フェニルホスフィニホスフィニコプロピオン酸など）、含窒素リン酸などの酸の金属塩などであってもよい。
【００６８】
好ましいリン酸塩は、ポリリン酸の塩、特にポリリン酸アンモニウム及びポリリン酸メラミンである。
【００６９】
好ましいリン含有化合物としては、リン酸エステル（脂肪族リン酸エステル、芳香族リン酸エステルなど）、無機リン化合物[（ポリリン酸アンモニウム、ポリリン酸メラミンなどの（ポリ）リン酸塩、赤リンなど）など、特に赤リンが挙げられる。
【００７０】
赤リンは、難燃効果が高く、少量であっても樹脂に難燃性を付与できる。また、少量で効果が得られるため、樹脂の特性（例えば、機械的特性や電気的特性）を損うことなく難燃化できる。赤リンとしては、特に、安定化処理を施したもの（安定化赤リン）が好ましく用いられる。特に、赤リンの粉砕を行わず、赤リン表面に水や酸素との反応性が高い破砕面を形成せずに赤リンを微粒子化する方法、さらには、赤リンの表面が、樹脂（例えば、熱硬化性樹脂、熱可塑性樹脂）、金属、金属化合物（例えば、金属水酸化物、金属酸化物など）などにより単独で又は二種以上組み合わせて被覆された赤リンが好ましい。
【００７１】
熱硬化性樹脂としては、フェノール樹脂、メラミン系樹脂、尿素系樹脂、アルキッド樹脂、不飽和ポリエステル樹脂、エポキシ樹脂、シリコーン系樹脂などが挙げられ、熱可塑性樹脂としては、ポリエステル系樹脂、ポリアミド系樹脂、アクリル系樹脂、オレフィン系樹脂などが挙げられる。金属水酸化物としては、水酸化アルミニウム、水酸化マグネシウム、水酸化カルシウム、水酸化亜鉛、水酸化チタンなどが挙げられ、金属酸化物としては、酸化アルミニウム、酸化マグネシウム、酸化亜鉛、酸化チタン、酸化ジルコニウム、酸化銅、酸化鉄、酸化モリブデン、酸化タングステン、酸化マンガン、酸化スズなどが挙げられる。
【００７２】
さらに、赤リンの表面を金属で被覆し安定化する方法としては、無電解メッキ法により、金属（鉄、ニッケル、銅、アルミニウム、亜鉛、マンガン、スズ、チタン、ジルコニウムなど）又はこれらの合金で被覆する方法が挙げられる。その他の赤リン表面の被覆方法として、金属塩（アルミニウム、マグネシウム、亜鉛、チタン、銅、銀、鉄、ニッケルなどの塩）の溶液で赤リンを処理し、赤リンの表面に金属リン化合物を形成させて安定化する方法も含まれる。
【００７３】
特に、赤リン表面に破砕面を形成させずに赤リンを微粒子化する方法を用い、金属成分（金属水酸化物や金属酸化物）の被膜と樹脂の皮膜とを組み合わせて複数層で被覆処理、特に金属成分の被膜で被覆した上に樹脂被覆で多重に被覆処理した赤リンが好ましい。これらの安定化赤リンは、耐熱安定性、耐加水分解性に優れており、水分の存在下や高温下での分解反応によりホスフィンの生成が著しく少なく、本発明の樹脂組成物を製造する際、また、成形品を製造する際の安全上及び成形体の品質上の観点から使用が好ましい。
【００７４】
これらの安定化赤リンの調製は、特開平５−２２９８０６号公報、特開平３−２５９９５６号公報、特開平２−２０９９９１号公報、特開平１−１５０３０９号公報、特開昭６２−２１７０４号公報、特開昭５２−１２５４８９号公報、ＥＰ２９６５０１Ａ１号公報、ＥＰ２４９７２３Ａ２号公報などを参照できる。
【００７５】
赤リンとしては、通常、安定化赤リンを粉粒状で使用できる。安定化赤リンの粒子径としては、例えば、０．０１〜１００μｍ、好ましくは０．１〜７０μｍ、さらに好ましくは０．１〜５０μｍ程度である。
【００７６】
また、安定化赤リンは、エポキシ系化合物、シラン系化合物、チタネート系化合物、クロム系化合物などの表面改質剤によって処理されていてもよい。
【００７７】
前記安定化赤リンは、単独又は２種以上を組み合わせて用いてもよい。例えば、被覆処理の異なるもの、粒径の異なるものを任意に組み合わせることができる。
（側鎖にヒドロキシル基含有芳香族環を有する樹脂）
側鎖にヒドロキシル基含有芳香族環を有する樹脂（以下、単に芳香族環樹脂という）としては、例えば、下記式（１）で表される構造単位を有する樹脂が使用できる。
【００７８】
【化６】

【００７９】
（式中、Ｒ¹は水素原子又はＣ_1-3のアルキル基、Ｒ²は芳香族環を示し、ｎは１〜３の整数である）
式（１）において、芳香族環としては、例えば、ベンゼン、ナフタレン環などのＣ_6-20芳香族環があげられる。また、芳香族環は、置換基（例えば、ヒドロキシル基；メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｓ−ブチル、ｔ−ブチル基などのアルキル基；メトキシ、エトキシ、プロポキシ基などのアルコキシ基など）を有していてもよい。
【００８０】
式（１）において、ヒドロキシル基の水素原子は、金属イオン、シリル基もしくはアルコキシ基、アルキル基、アルカノイル基、ベンゾイル基などの有機基（保護基）で保護されていてもよい。
【００８１】
このような誘導体から得られる樹脂は、例えば、下記式（５）に示される構造単位を有する。
【００８２】
【化７】

【００８３】
（式中、Ｒ¹は水素原子又はＣ_1-3のアルキル基であり、Ｒ¹³は−ＯＨ,−ＯＳi（Ｒ¹⁴）₃及び−ＯＭ（Ｍは金属カチオン、ＯＲ¹⁴及びＯＣＯＲ¹⁴であり、Ｒ¹⁴は炭素原子１〜５個のアルキル基又はアリール基である）からなる群より選ばれる基である。また、ｎは１〜３の整数である。）
前記式において、Ｍは一価のアルカリ金属カチオン（ナトリウム、リチウム、カリウムなど）、又は二価のアルカリ土類金属カチオン（マグネシウム、カルシウムなど）もしくは遷移金属カチオンのいずれかであってもよい。
【００８４】
前記式の置換基Ｒ¹³は、オルト位、パラ位及びメタ位のいずれか一つに位置していればよい。さらに、置換基Ｒ¹³に加えて、ペンダント芳香族環はＣ_1-4のアルキル基で置換されていてもよい。
【００８５】
芳香族環樹脂には、前記構造単位（１）に対応するヒドロキシル基を有する芳香族環ビニルモノマー（以下、単に芳香族環ビニルモノマーという）の単独又は共重合体、または他の共重合性モノマーとの共重合体などが含まれる。
【００８６】
芳香族環ビニルモノマーとしては、例えば、ビニルフェノール、ジヒドロキシスチレン、ビニルナフトールなどのヒドロキシル基含有芳香族ビニルモノマーなどが含まれる。
【００８７】
芳香族環ビニルモノマーとしては、例えば、ビニルフェノール、ジヒドロキシスチレン、ビニルナフトールなどのヒドロキシル基含有芳香族ビニルモノマーなどが含まれる。
【００８８】
共重合性モノマーとしては、例えば、（メタ）アクリル系モノマー[（メタ）アクリル酸、（メタ）アクリル酸エステル（例えば、（メタ）アクリル酸メチル、(メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸２−エチルへキシル、（メタ）アクリル酸２−ヒドロキシエチルなど）、（メタ）アクリルアミド、（メタ）アクリロニトリルなど]、スチレン系モノマー（例えば、スチレン、ビニルトルエン、α−メチルスチレン、クロロスチレン、ビニルナフタリン、ビニルシクロヘキサンなど ）、重合性多価カルボン酸（フマル酸、マレイン酸など）、マレイミド系モノマー（フェニルマレイミドなど）、ジエン系モノマー（イソプレン、1,3−ブタジエン、1,4−ヘキサジエン、ジシクロペンタジエンなど）、ビニル系モノマー（例えば、酢酸ビニル、プロピオン酸ビニルなどのビニルエステル類；メチルビニルケトン、メチルイソプロペニルケトンなどのビニルケトン類；塩化ビニル、フルオロエチレン、クロロプレンなどのハロゲン含有ビニルモノマー；ビニルイソブチルエーテル、ビニルメチルエーテルなどのビニルエーテル類；Ｎ−ビニルカルバゾール、Ｎ−ビニルピロリドン、Ｎ−ビニルイミダゾールなどのビニルアミン類など）などが挙げられる。好ましい共重合性モノマーには、スチレン系モノマー、（メタ）アクリル系モノマー、及びビニル系モノマーなどが含まれる。
【００８９】
これらの共重合性モノマーは１種又は２種以上使用できる。
【００９０】
芳香族環樹脂は必要により一部を水素添加してもよい。
【００９１】
芳香族環ビニルモノマーと共重合性モノマーとの割合は、例えば、１０／９０〜１００／０（重量％）、好ましくは３０／７０〜１００／０（重量％）程度である。
【００９２】
好ましい芳香族環樹脂は、ビニルフェノール単独重合体（ポリヒドロキシスチレン）、及びビニルフェノール共重合体（ヒドロキシスチレン−スチレン共重合体など）であり、特にｐ−ビニルフェノール単独重合体が好ましい。
【００９３】
芳香族環樹脂の数平均分子量は、特に制限されず、例えば、３００〜５０×１０⁴、好ましくは４００〜３０×１０⁴、さらに好ましくは５００〜５×１０⁴程度の範囲から選択できる。特に、５００〜１００００の範囲の芳香族樹脂が好ましく用いられる。分子量が３００未満では樹脂組成物の耐熱性を低下させる。
（リン含有化合物と芳香族環樹脂の割合）
難燃剤中のリン含有化合物の使用量は、難燃性を付与できる範囲で選択され、前記芳香族環樹脂１００重量部に対して、リン含有化合物１〜１００重量部、好ましくは５〜８０重量部、さらに好ましくは１０〜６０重量部程度である。
（難燃剤の使用割合）
本発明の難燃剤は、リン含有化合物と芳香族環樹脂を組み合わせることにより、熱可塑性樹脂に対して、少量の添加であっても高い難燃性を付与できる。前記熱可塑性樹脂中に含まれる前記難燃剤の割合は、樹脂の特性を損わない限り特に制限されず、熱可塑性樹脂１００重量部に対して、難燃剤０．１〜１００重量部、好ましくは１〜８０重量部、さらに好ましくは５〜６０重量部（特に５〜４０重量部）程度である。難燃剤が０．１重量部未満では、難燃化が困難であり、１００重量部を超えると、樹脂の機械的強度を低下させる。
［添加剤］
なお、本発明の難燃性樹脂組成物は、必要に応じて種々の添加剤（例えば、他の難燃剤、ドリップ防止剤、酸化防止剤又は安定剤など）を含んでいてもよく、これら添加剤の全体の含有量は、熱可塑性樹脂１００重量部に対して、０．０１〜５０重量部、好ましくは、０．１〜３０重量部、さらに好ましくは０．５〜２０重量部程度である。
［その他の難燃剤］
本発明の難燃性樹脂組成物は、さらに高度な難燃性を付与するため、他の難燃剤、例えば，窒素含有難燃剤、硫黄含有難燃剤、ケイ素含有難燃剤、アルコール系難燃剤、無機系難燃剤（金属酸化物、金属水酸化物など）などを含んでいてもよい。
【００９４】
窒素含有難燃剤としては、アミン類、例えば、尿素類、グアニジン類、トリアジン系化合物（例えば、グアナミン、メラミン、メラム、メレム、アンメリン、メラミンホルムアルデヒド樹脂、ベンゾグアナミンなど）、トリアジン系化合物とシアヌール酸又はイソシアヌール酸との塩（前者：後者（モル比）＝１：１〜１：２程度の塩、例えば、メラミンシアヌレート、グアナミンシアヌレート、アセトグアナミンシアヌレート、ベンゾグアナミンシアヌレートなど）などが挙げられる。
【００９５】
硫黄含有難燃剤としては、硫酸エステルの他に、有機スルホン酸、スルファミン酸、及びそれらの塩、エステル、アミドなどが挙げられる。
【００９６】
ケイ素含有難燃剤には、（ポリ）オルガノシロキサンが含まれる。（ポリ）オルガノシロキサンとしては、ジアルキルシロキサン（例えば、ジメチルシロキサンなど）、アルキルアリールシロキサン（フェニルメチルシロキサンなど）、ジアリールシロキサンなどのモノオルガノシロキサン及びこれらの単独重合体（例えば、ポリジメチルシロキサン、ポリフェニルメチルシロキサンなど）、又は共重合体などが含まれる。また、（ポリ）オルガノシロキサンとしては、分子末端や主鎖に、エポキシ基、水酸基、カルボキシル基、アミノ基、エーテル基などの置換基を有する変性（ポリ）オルガノシロキサン（例えば、変性シリコーンなど）なども使用できる。
【００９７】
アルコール系難燃剤としては、多価アルコール、オリゴマーの多価アルコール、エステル化された多価アルコール、置換されたアルコール、糖類（単糖類、多糖類など）などが挙げられる。
【００９８】
無機系難燃剤のうち、金属酸化物としては、例えば、酸化モリブデン、酸化タングステン、酸化チタン、酸化ジルコニウム、酸化スズ、酸化銅、酸化亜鉛、酸化アルミニウム、酸化ニッケル、酸化鉄、三酸化アンチモン、四酸化アンチモン、五酸化アンチモンなどが挙げられる。また、金属水酸化物としては、例えば、水酸化アルミニウム、水酸化マグネシウム、水酸化スズ、水酸化ジルコニウムなどが挙げられる。
【００９９】
また、前記無機系難燃剤には、金属スズ酸塩（例えば、スズ酸亜鉛など）、金属ホウ酸塩（例えば、四ホウ酸ナトリウム、ホウ酸亜鉛など）、膨張性黒鉛なども含まれる。
【０１００】
これら他の難燃剤は、一種又は二種以上組み合わせて使用できる。
【０１０１】
他の難燃剤の含有量は、例えば、熱可塑性樹脂１００重量部に対して、０．０１〜５０重量部程度、好ましくは０．０５〜３０重量部程度、特に０．１〜２０重量部程度の範囲から選択できる。
［ドリップ防止剤］
さらに、本発明の難燃性樹脂組成物は、フッ素系樹脂などのドリップ防止剤を添加してもよい。ドリップ防止剤により、燃焼時の火種及び融液の滴下（ドリップ）を抑制できる。フッ素系樹脂には、テトラフルオロエチレン、クロロトリフルオロエチレン、ビニリデンフルオライド、ヘキサフルオロプロピレン、パーフルオロアルキルビニルエーテルなどのフッ素含有モノマーの単独又は共重合体；前記フッ素含有モノマーと、エチレン、プロピレン、アクリレートなどの共重合性モノマーとの共重合体が含まれる。このようなフッ素系樹脂としては、例えば、ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、ポリビニリデンフルオライドなどの単独重合体；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−パーフルオロアルキルビニルエーテル共重合体、エチレン−テトラフルオロエチレン共重合体、エチレン−クロロトリフルオロエチレン共重合体などの共重合体が例示される。これらのフッ素系樹脂は、一種又は二種以上混合して使用できる。
【０１０２】
前記フッ素系樹脂は、粒子状で使用してもよく、平均粒径は、例えば、１０〜５０００μｍ程度、好ましくは１００〜１０００μｍ程度、さらに好ましくは２００〜７００μｍ程度であってもよい。
【０１０３】
フッ素系樹脂は、単独で又は二種以上使用できる。フッ素系樹脂の含有量は、例えば、熱可塑性樹脂１００重量部に対して、０．０１〜１０重量部程度、好ましくは０．１〜５重量部程度、さらに好ましくは０．１〜３重量部程度である。［酸化防止剤又は安定剤］
また、本発明の難燃性樹脂組成物は、長期間安定に耐熱性を維持するために酸化防止剤又は安定剤を含んでいてもよい。酸化防止剤又は安定剤には、例えば、フェノール系（ヒンダードフェノール類など）、アミン系（ヒンダードアミン類など）、リン系、イオウ系、ヒドロキノン系、キノリン系酸化防止剤などが含まれる。
【０１０４】
フェノール系酸化防止剤には、ヒンダードフェノール類、例えば、２，２′−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）、４，４′−メチレンビス（２，６−ジ−ｔ−ブチルフェノール）、４，４′−ブチリデンビス（３−メチル−６−ｔ−ブチルフェノール）、２，６−ジ−ｔ−ブチル−ｐ−クレゾール、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、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］、ペンタエリスリトールテトラキス［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］、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］、ｎ−オクタデシル−３−（４′，５′−ジ−ｔ−ブチルフェノール）プロピオネート、ｎ−オクタデシル−３−（４′−ヒドロキシ−３′，５′−ジ−ｔ−ブチルフェノール）プロピオネート、ステアリル−２−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェノール）プロピオネート、ジステアリル−３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジルホスホネート、２−ｔ−ブチル−６−（３−ｔ−ブチル−５−メチル−２−ヒドロキシベンジル）−４−メチルフェニルアクリレート、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）、３，９−ビス｛２−［３−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ］−１，１−ジメチルエチル｝−２，４，８，１０−テトラオキサスピロ［５，５］ウンデカン、４，４′−チオビス（３−メチル−６−ｔ−ブチルフェノール）、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔ−ブチルフェノール）ブタンなどが含まれる。
【０１０５】
ヒンダードフェノール類の中でも、特に、例えば、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］などのＣ_2-10アルキレンジオール−ビス［３−（３，５−ジ−分岐Ｃ_3-6アルキル−４−ヒドロキシフェニル）プロピオネート］；例えば、トリエチレングリコール−ビス［３−（３−ｔ−ブチル−５−メチル−４−ヒドロキシフェニル）プロピオネート］などのジ又はトリオキシＣ_2-4アルキレンジオール−ビス［３−（３，５−ジ−分岐Ｃ_3-6アルキル−４−ヒドロキシフェニル）プロピオネート］；例えば、グリセリントリス［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］などのＣ_3-8アルキレントリオール−ビス［３−（３，５−ジ−分岐Ｃ_3-6アルキル−４−ヒドロキシフェニル）プロピオネート］；例えば、ペンタエリスリトールテトラキス［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］などのＣ_4-8アルキレンテトラオールテトラキス［３−（３，５−ジ−分岐Ｃ_3-6アルキル−４−ヒドロキシフェニル）プロピオネート］などが好ましい。
【０１０６】
アミン系酸化防止剤には、ヒンダードアミン類、例えば、トリ又はテトラＣ_1-3アルキルピペリジン又はその誘導体[例えば、４−メトキシ−２，２，６，６−テトラメチルピペリジン、４−ベンゾイルオキシ−２，２，６，６−テトラメチルピペリジン、４−フェノキシ−２，２，６，６−テトラメチルピペリジンなど]、ビス（トリ、テトラ又はペンタＣ_1-3アルキルピペリジン）Ｃ_2-20アルキレンジカルボン酸エステル[例えば、ビス（２，２，６，６−テトラメチル−４−ピペリジル）オギサレート、ビス（２，２，６，６−テトラメチル−４−ピペリジル）マロネート、ビス（２，２，６，６−テトラメチル−４−ピペリジル）アジペート、ビス（２，２，６，６−テトラメチル−４−ピペリジル）セバケート、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）セバケート、ビス（２，２，６，６−テトラメチル−４−ピペリジル）テレフタレート]、１，２−ビス（２，２，６，６−テトラメチル−４−ピペリジルオキシ）エタン、フェニル−１−ナフチルアミン、フェニル−２−ナフチルアミン、Ｎ，Ｎ′−ジフェニル−１，４−フェニレンジアミン、Ｎ−フェニル−Ｎ′−シクロヘキシル−１，４−フェニレンジアミンなどが含まれる。
【０１０７】
リン系安定剤（又は酸化防止剤）には、例えば、トリイソデシルホスファイト、トリスノニルフェニルホスファイト、ジフェニルイソデシルホスファイト、フェニルジイソデシルホスファイト、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、４，４′−ブチリデンビス（３−メチル−６−ｔ−ブチルフェニル）ジトリデシルホスファイト、トリス（分岐Ｃ_3-6アルキルフェニル）ホスファイト[例えば、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト、トリス（２−ｔ−ブチル−４−メチルフェニル）ホスファイト、トリス（２，４−ジ−ｔ−アミルフェニル）ホスファイト、トリス（２−ｔ−ブチルフェニル）ホスファイト、トリス［２−（１，１−ジメチルプロピル）−フェニル］ホスファイト、トリス［２，４−（１，１−ジメチルプロピル）−フェニル］ホスファイトなど]、ビス（２−ｔ−ブチルフェニル）フェニルホスファイト、、トリス（２−シクロヘキシルフェニル）ホスファイト、トリス（２−ｔ−ブチル−４−フェニルフェニル）ホスファイト、ビス（Ｃ_3-9アルキルアリール）ペンタエリスリトールジホスファイト［例えば、ビス（２，４−ジ−ｔ−ブチル−４−メチルフェニル）ペンタエリスリトールジホスファイト、ビス（２，６−ジ−ｔ−ブチル−４−メチルフェニル）ペンタエリスリトールジホスファイト、ビス（ノニルフェニル）ペンタエリスリトールジホスファイト、ビス（ノニルフェニル）ペンタエリスリトールジホスファイトなど］、トリフェニルホスフェート系安定剤（例えば、４−フェノキシ−９−α−（４−ヒドロキシフェニル）−ｐ−クメニルオキシ−３，５，８，１０−テトラオキサ−４，９−ジホスファピロ[５，５]ウンデカン、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスフェートなど）、ジホスフォナイト系安定剤（例えば、テトラキス（２，４−ジ−ｔ−ブチル）−４，４'−ビフェニレンジホスフォナイトなど）などが含まれる。リン系安定剤は、通常、分岐Ｃ_3-6アルキルフェニル基（特に、ｔ−ブチルフェニル基）を有している。
【０１０８】
ヒドロキノン系酸化防止剤には、例えば、２，５−ジ−ｔ−ブチルヒドロキノンなどが含まれ、キノリン系酸化防止剤には、例えば、６−エトキシ−２，２，４−トリメチル−１，２−ジヒドロキノリンなどが含まれ，イオウ系酸化防止剤には、例えば、ジラウリルチオジプロピオネート、ジステアリルチオジプロピオネートなどが含まれる。
【０１０９】
これらの酸化防止剤は単独で、又は二種以上使用できる。酸化防止剤の含有量は、例えば、熱可塑性樹脂１００重量部に対して、０．０１〜５重量部、好ましくは０．０５〜２．５重量部、特に０．１〜１重量部程度の範囲から選択できる。
【０１１０】
なお、熱可塑性樹脂としてポリエステル系樹脂又はポリカーボネート系樹脂を用いる場合、無機リン化合物を添加すると、熱安定性がさらに向上する。無機リン化合物としては、例えば、無機リン酸（リン酸、亜リン酸、ホスフォン酸、ホスフィン酸、ポリリン酸、ポリ亜リン酸、ホスホノカルボン酸、含窒素リン酸など）及びそれらの酸性金属塩などが挙げられる。
【０１１１】
無機リン酸の酸性金属塩には、例えば、無機リン酸水素アルカリ金属類（例えば、ＮａＨ₂ＰＯ₄、Ｎａ₂ＨＰＯ₄、ＫＨ₂ＰＯ₄、Ｋ₂ＨＰＯ₄などのリン酸水素アルカリ金属類）、無機リン酸水素アルカリ土類金属類（例えば、ＣａＨＰＯ₄、Ｃａ（Ｈ₂ＰＯ₄）₂、ＭｇＨＰＯ₄、Ｍｇ（Ｈ₂ＰＯ₄）₂、などのリン酸水素アルカリ土類金属類など）、無機リン酸水素アルミニウム（例えば、Ａｌ（Ｈ₂ＰＯ₄）₃などが挙げられる。
【０１１２】
さらに、本発明の難燃性樹脂組成物は、目的に応じて他の添加剤を含んでいてもよい。他の添加剤としては、安定剤（紫外線吸収剤、耐熱安定剤、耐候安定剤など）、滑剤、離型剤、着色剤、可塑剤、核剤、衝撃改良剤、摺動剤などが挙げられる。
【０１１３】
本発明の難燃剤は、燃焼時に樹脂表面の炭化を促進するためか、樹脂を高度に難燃化できる。また、リン含有化合物と、芳香族環樹脂とを組み合わせることにより、少量であっても熱可塑性樹脂を効果的に難燃化でき、ブリードアウトや耐熱性を低下させることもない。特に、難燃剤成分としてポリヒドロキシスチレンを使用した場合、付加縮合反応により製造される一般的なフェノールノボラック樹脂などに比べて樹脂変性の自由度が高く、また基本特性（安定性、相溶性）において通常のフェノール樹脂などより優れている。
［充填剤］
また、本発明の難燃性樹脂組成物は、機械的強度、剛性、耐熱性及び電気的性質などをさらに向上させるため、充填剤により改質されていてもよい。充填剤には、繊維状充填剤、非繊維状充填剤（板状充填剤、粉粒状充填剤など）が含まれる。
【０１１４】
繊維状充填剤としては、ガラス繊維、アスベスト繊維、カーボン繊維、シリカ繊維、シリカ・アルミナ繊維、ジルコニア繊維、チタン酸カリウム繊維、金属繊維、高融点有機質繊維（例えば、脂肪族又は芳香族ポリアミド、芳香族ポリエステル、フッ素系樹脂、ポリアクリロニトリルなどのアクリル樹脂など）などが例示できる。
【０１１５】
非繊維状充填剤のうち、粉粒状充填剤には、シリカ、石英粉末、ガラスビーズ、ガラス粉、ミルドファイバー（ミルドガラスファイバーなど）、ケイ酸カルシウム、ケイ酸アルミニウム、カオリン、タルク、クレー、ケイ藻土、ウォラストナイトなどのケイ酸塩；酸化鉄、酸化チタン、酸化亜鉛、アルミナなどの金属酸化物；炭酸カルシウム、炭酸マグネシウムなどの金属の炭酸塩；硫酸カルシウム、硫酸バリウムなどの金属の炭酸塩；硫酸カルシウム、硫酸バリウムなどの金属の硫酸塩、炭化ケイ素などの金属粉末が含まれる。
【０１１６】
板状充填剤には、例えば、ガラスフレーク、マイカ、グラファイト、各種金属箔などが挙げられる。
【０１１７】
好ましい繊維状充填剤としては、ガラス繊維、カーボン繊維が挙げられ、好ましい非繊維状充填剤としては、粉粒状又は板状充填剤、特に、ガラスフレーク、ガラスビーズ、ミルドファイバー、タルク、マイカ及びカオリンが挙げられる。
【０１１８】
また、特に好ましい充填剤には、高い強度及び剛性を有するガラス繊維が含まれる。
【０１１９】
充填剤を用いる場合、難燃性樹脂組成物中の充填剤の割合は、例えば、５〜６０重量％程度、好ましくは５〜５０重量％程度、さらに好ましくは５〜３５重量％程度である。
【０１２０】
また、これらの充填剤の使用にあたっては、必要ならば収束剤又は表面処理剤を使用することが望ましい。このような収束剤または表面処理剤としては、例えば、エポキシ系化合物、シラン系化合物、チタネート系化合物等の官能性化合物が用いられる。好ましくは、エポキシ系化合物、特に、ビスフェノールＡ型又はノボラック型エポキシ樹脂などが挙げられる。
【０１２１】
充填剤は、前記収束剤又は表面処理剤により、表面処理又は収束処理されていてもよい。処理の時期については、充填剤の添加と同時に処理してもよく、添加前に予め処理していてもよい。
【０１２２】
表面処理を行う場合、官能性表面処理剤の使用量は、例えば、充填剤に対して５重量％以下、好ましくは０．０５〜２重量％程度である。
【０１２３】
[難燃性樹脂組成物の製造方法]
本発明の難燃性樹脂組成物は、粉粒体混合物や溶融混合物であってもよく、熱可塑性樹脂と、難燃剤と、必要によりドリップ防止剤や他の添加剤などとを慣用の方法で混合することにより調製できる。例えば、▲１▼各成分を混合して、一軸又は二軸の押出機により混練し押出してペレットを調製した後、成形する方法、▲２▼一旦、組成の異なるペレット（マスターバッチ）を調製し、そのペレットを所定量混合（希釈）して成形に供し、所定の組成の成形品を得る方法、▲３▼成形機に各成分の１又は２以上を直接仕込む方法などが採用できる。また、成形品に用いられる組成物の調製において、熱可塑性樹脂の粉粒体（例えば、ポリエステル系樹脂の一部又は全部を粉砕した粉粒体）と、他の成分（難燃剤など）とを混合して溶融混練すると、他の成分の分散を向上させるのに有利である。
【０１２４】
なお、ハンドリングの観点から、熱可塑性樹脂、芳香族環樹脂及びリン含有化合物から選ばれた少なくとも二種の成分を一旦溶融混合することにより、マスターバッチを調製すると便利である。特に、リン含有化合物として赤リンを用いる場合、マスターバッチを調製する場合が多い。なお、マスターバッチを構成する成分のうち、少なくとも一種の成分は樹脂成分である。また、樹脂成分でマスターバッチを構成する場合、熱可塑性樹脂の一部をマスターバッチに用いることが多い。
【０１２５】
前記マスターバッチとしては、例えば、（１）熱可塑性樹脂の一部とリン含有化合物とで構成されたマスターバッチ、（２）芳香族環樹脂とリン含有化合物とで構成されたマスターバッチ、（３）熱可塑性樹脂の一部と、芳香族環樹脂とリン化合物とで構成されたマスターバッチなどが挙げられる。
【０１２６】
なお、前記マスターバッチは、必要に応じて、種々の添加剤、例えば、フッ素系樹脂、酸化防止剤、リン系安定剤、充填剤などを含有していてもよい。
【０１２７】
このようにして得られたマスターバッチと、熱可塑性樹脂と必要に応じて残りの成分とを溶融混合することにより、難燃性樹脂組成物を製造できる。
【０１２８】
また、本発明の難燃性樹脂組成物を溶融混練したのち、押出成形、射出成形、圧縮成形などの慣用の方法で形成された成形品は、難燃性および成形加工性に優れているため、種々の用途に使用できる。例えば、機械機構部品、電気・電子部品、自動車部品、包装材料やケースなどに好適に用いることができる。
【０１２９】
【発明の効果】
本発明では、熱可塑性樹脂と、リン含有化合物および側鎖にヒドロキシル基含有芳香族環を有する樹脂で構成された難燃剤とを組み合わせるので、ハロゲン系難燃剤を使用することなく、少量であっても難燃化できる。さらに、本発明の難燃性樹脂組成物は、ブリードアウトを抑制でき、特別な化合物を使用することなく機械的特性を高いレベルで維持できる。
【０１３０】
【実施例】
以下に、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。
【０１３１】
なお、下記の試験により樹脂組成物の難燃性、物性などを評価した。
（燃焼性試験）
ＵＬ ９４に準拠して、試験片の厚み０．８ｍｍで燃焼性を評価した。
（引張り試験）
ＡＳＴＭ Ｄ−６３８に準拠して、引張り特性を評価した。
（成形外観）
燃焼試験片をギヤーオーブン中、１２０℃で２４時間処理した後、外観の評価を行った。評価基準を以下に示す。
【０１３２】
○＝ブリードアウトはほとんど認められない
△＝ブリードアウトがわずかに認められる
×＝ブリードアウトが多量に認められる
実施例及び比較例では、下記の熱可塑性樹脂、難燃剤などを使用した。
[熱可塑性樹脂Ａ]
Ａ−１：ポリブチレンテレフタレート（ジュラネックス、固有粘度＝０．８３、ポリプラスチックス（株）製）
Ａ−２：１２．５モル％イソフタル酸変性ポリブチレンテレフタレート
Ａ−３：ポリエチレンテレフタレート（ベルペット ＥＦＧ１０、鐘紡（株）製）
Ａ−４：ＰＢＴエラストマー（ＰＢＴセグメント６０重量％、ポリ（テトラメチレンオキサイドグリコール）テレフタレートセグメント４０重量％）
Ａ−５：ＰＥＴ系液晶ポリマー
ポリエチレンテレフタレート（ＰＥＴ）とｐ−アセトキシ安息香酸とを溶融混合してアシドリシス反応によりポリエステルフラグメントを形成させた後、重縮合反応を行って高重合度化した液晶ポリエステル。下記の構造単位を有する。
【０１３３】
【化８】

【０１３４】
なお、ｋとｌとｍとの割合は、ｋ／ｌ／ｍ＝８０／２０／２０（モル比）である。
【０１３５】
Ａ−６：ポリカーボネート（パンライトＬ１２５０、帝人化成（株）製）
Ａ−７：ナイロン−６,６（ポリプラナイロン６６、ポリプラスチックス（株）製）
Ａ−８：ＡＢＳ樹脂（スチレン４１重量％、アクリロニトリル１４重量％、ブタジエン４５重量％）
Ａ−９：ポリブチレンテレフタレート（ジュラネックス、固有粘度＝１．０、ポリプラスチックス（株）製）
Ａ−１０：ポリブチレンテレフタレート（ジュラネックス、固有粘度＝０．７５、ポリプラスチックス（株）製）
[難燃剤]
（リン含有化合物Ｂ）
Ｂ−１：赤リン（ノーバエクセル１４０、燐化学工業（株）製）
Ｂ−２：赤リン（ノーバエクセルＦ５、燐化学工業（株）製）
Ｂ−３：赤リンマスターバッチ
ベント付き２軸押出機を用いて、赤リン（Ｂ−１）とポリブチレンテレフタレート（Ａ−１）から調製した（Ｂ−１）／（Ａ−１）＝３０／７０（重量比）の赤リンマスターバッチ。
【０１３６】
Ｂ−４：赤リンマスターバッチ
ベント付き２軸押出機を用いて、赤リン（Ｂ−２）とポリブチレンテレフタレート（Ａ−１）から調製した（Ｂ−２）／（Ａ−１）＝３０／７０（重量比）の赤リンマスターバッチ。
【０１３７】
Ｂ−５：縮合リン酸エステル（ＰＸ−２００、大八化学工業（株）製）
Ｂ−６：ポリリン酸アンモニウム（テラージュＣ６０、チッソ（株）製）
Ｂ−７：縮合リン酸エステル（ＰＸ−２０１、大八化学工業（株）製）
Ｂ−８：縮合リン酸エステル（ファイロールフレックスＲＤＰ、アクゾノーベル（株）製）
Ｂ−９：縮合リン酸エステル（ファイロールフレックスＢＤＰ、アクゾノーベル（株）製）
Ｂ−１０：ビスフェノールＡビス（ジクレジルホスフェート）
Ｂ−１１：ポリリン酸メラミン（ＭＰＰ−Ａ、（株）三和ケミカル製）
（芳香族環樹脂Ｃ）
Ｃ−１：ポリｐ−ビニルフェノール（マルカリンカーＭ Ｓ-１Ｐ、数平均分子量＝１１００、丸善石油化学（株）製）
Ｃ−２：ポリｐ−ビニルフェノール（マルカリンカーＭ Ｓ-４Ｐ、数平均分子量＝４３００、丸善石油化学（株）製）
Ｃ−３：ｐ−ビニルフェノール−スチレン共重合体（マルカリンカーＣＳＴ５０、ｐ−ビニルフェノールの共重合比：約５０モル％、数平均分子量２１００、丸善石油化学（株）製）
Ｃ−４：ｐ−ビニルフェノール−スチレン共重合体（マルカリンカーＣＳＴ１５、ｐ−ビニルフェノールの共重合比：約１５モル％、丸善石油化学（株）製）
Ｃ−５：ｐ−ビニルフェノール−メタクリル酸 ２−ヒドロキシエチル共重合体（マルカリンカーＣＨＭ、ｐ−ビニルフェノールの共重合比：約５０モル％、数平均分子量＝３６００、丸善石油化学（株）製）
Ｃ’−１：フェノールノボラック樹脂（スミライトレジンＰＲ−５３１９５、住友デュレズ（株）製）
[窒素含有難燃剤Ｄ]
Ｄ−１：メラミンシアヌレート（ＭＣ６１０、日産化学工業（株）製）
[酸化防止剤Ｅ]
Ｅ−１：ペンタエリスリトール−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]（イルガノックス１０１０、チバガイギー（株）製）
[リン系安定剤Ｆ]
Ｆ−１：テトラキス（２，４−ジ−ｔ−ブチルフェニル）−４，４'−ビフェニレンジホスフォナイト（サンドスタブＰ−ＥＰＱ、サンド（株）製）
Ｆ−２：第一リン酸カルシウム
Ｆ−３：ビス（２，６−ジ−ｔ−ブチル−４−メチルフェニル）ペンタエリスリトールジホスファイト（アデカスタブＰＥＰ３６、アデカア−ガス（株）製）
［ドリップ防止剤Ｇ］
Ｇ−１：ポリテトラフルオロエチレン
［充填剤Ｈ（ガラス繊維）］
Ｈ−１：直径１０μｍ、長さ３ｍｍのチョップドストランド
実施例１〜１４、参考例１および比較例１〜５
ポリブチレンテレフタレート（Ａ−１）に、上記成分を表１〜３の割合で混合し、押出機により混練し、押出して樹脂組成物を調製した。この樹脂組成物を射出成形し、試験用成形品を作製し、燃焼性、引張り特性および成形外観（ブリードアウト）を評価した。
【０１３８】
結果を表１〜３に示す。
【０１３９】
【表１】

【０１４０】
【表２】

【０１４１】
【表３】

【０１４２】
実施例１５〜１９、参考例２〜５および比較例６〜１９
熱可塑性樹脂Ａに、上記成分を表４〜６の割合で混合し、押出機により混練し、押出して樹脂組成物を調製した。この樹脂組成物を射出成形し、試験用成形品を作製し、燃焼性及び成形外観（ブリードアウト）を評価した。
【０１４３】
結果を表４〜６に示す。
【０１４４】
【表４】

【０１４５】
【表５】

【０１４６】
【表６】

【０１４７】
実施例２０〜２４、参考例６〜１０および比較例２０〜２８
熱可塑性樹脂Ａに、上記成分を表７及び表８の割合で混合し、押出機により混練し、押出して樹脂組成物を調製した。この樹脂組成物を射出成形し、試験用成形品を作成し、燃焼性及び成形外観（ブリードアウト）を評価した。
【０１４８】
結果を表７及び表８に示す。
【０１４９】
【表７】

【０１５０】
【表８】

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a flame retardant resin composition comprising a thermoplastic resin, a phosphorus-containing compound and a flame retardant composed of a resin having a hydroxyl group-containing aromatic ring in the side chain, a method for producing the same, and the flame retardant The present invention relates to a molded body formed of a conductive resin composition.
[0002]
[Prior art]
Among thermoplastic resins, polyester resins such as polybutylene terephthalate and styrene resins have excellent mechanical properties, electrical properties, weather resistance, water resistance, chemical resistance, and solvent resistance. It is used for various applications such as electronic parts and automobile parts. On the other hand, as the application field expands, improvement of flame retardancy is being studied.
[0003]
Therefore, a method for making a thermoplastic resin flame retardant by adding a flame retardant using a halogen compound or an antimony compound has been proposed. For example, JP-A-63-150349 discloses glass fiber, organic halogen flame retardant, antimony trioxide, and alkali metal or alkaline earth metal hydroxide in a mixed resin composed of polyamide resin and nylon 66. A resin composition that has been blended and made flame retardant is disclosed. Moreover, brominated polycarbonate, brominated polystyrene, brominated poly p-vinylphenol and the like are commercially available as high molecular weight flame retardants as brominated polymers. However, halogen flame retardants may generate dioxin compounds during combustion decomposition, which is not preferable in terms of environmental problems. In view of this, a flame retardant method using a phosphorus-based, nitrogen-containing compound or the like as a non-halogen flame retardant has been proposed.
[0004]
In JP-A-6-25506, a phosphorus compound is added to a thermoplastic resin comprising a copolymer of an aromatic vinyl compound and a vinyl monomer, a graft copolymer of a rubbery polymer, and a novolac resin. An added flame retardant resin composition is disclosed. JP-A-9-111059 discloses a flame retardant resin composition comprising a polyolefin resin and a specific amount of a phenol resin, a phosphorus-containing compound (red phosphorus), and expansive graphite. Japanese Patent Application Laid-Open No. 10-195283 discloses a polyester made flame-retardant by combining a phosphate having a specific structure with a specific compound (a novolac-type phenol resin and an oxide of iron, cobalt, nickel or copper). A resin composition is disclosed.
[0005]
However, although non-halogen flame retardants do not contain harmful halogens, they are inferior in flame retardancy compared with halogen flame retardants, and therefore require a large amount of flame retardants. Addition of a large amount of flame retardant causes bleed out and deterioration of mechanical properties of the resin. Therefore, the mechanical properties cannot be improved together with the flame retardancy. For example, when expansive graphite is used in combination, the appearance during molding is significantly reduced. In particular, when a phosphoric acid ester is used as the phosphorus-containing compound, bleeding out and a decrease in heat resistance are caused.
[0006]
Thus, with the conventional method, it is difficult to impart high flame retardancy without deteriorating the properties of the resin. Moreover, although the above flame retardant can be flame retardant with respect to a specific resin, the flame retardant effect is not sufficient with respect to thermoplastic resins in general.
[0007]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide a non-halogen-containing flame-retardant resin composition that is flame-retardant at a high level even with a small amount of flame retardant and a method for producing the same.
[0008]
Another object of the present invention is to provide a flame retardant resin composition which has been made flame retardant without deteriorating the properties of the thermoplastic resin, and a method for producing the same.
[0009]
Still another object of the present invention is to provide a molded article having improved flame retardancy.
[0010]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that flame retardancy can be achieved at a high level by adding a specific non-halogen flame retardant composition to a thermoplastic resin. Was completed.
[0011]
That is, the flame retardant resin composition of the present invention is a flame retardant resin composition containing a thermoplastic resin and a flame retardant, The thermoplastic resin is a polyester resin; The flame retardant , Phosphorus-containing compounds and resins having a hydroxyl group-containing aromatic ring in the side chain As a homopolymer or copolymer of vinylphenol Consists of And the ratio of the said phosphorus containing compound is 1-100 weight part with respect to 100 weight part of resin which has a hydroxyl group containing aromatic ring in the said side chain. . This composition may contain 0.1-100 weight part of flame retardants with respect to 100 weight part of thermoplastic resins.
[0013]
Phosphorus-containing compounds include red phosphorus, (poly) phosphates, phosphate esters, and the like.
[0016]
The In addition, the flame retardant resin composition of the present invention is a single or a combination of two or more additives such as fluororesins, hindered phenol antioxidants, phosphorus stabilizers, nitrogen-containing flame retardants and fillers. May be used.
[0017]
The present invention also includes a method for producing a flame retardant resin composition by mixing a thermoplastic resin and a flame retardant, and a molded body formed from the flame retardant resin composition.
[0018]
In addition, this specification also discloses the flame retardant (or flame retardant composition) comprised by the combination of the said phosphorus compound and resin which has a hydroxyl group containing aromatic ring in a side chain.
[0019]
DETAILED DESCRIPTION OF THE INVENTION
[Thermoplastic resin]
As the thermoplastic resin, various resins used for molding, for example, olefin resin, acrylic resin, styrene resin, polyamide resin, polyester resin, polycarbonate resin, polyphenylene oxide resin, vinyl resin. Etc.
(1) Olefin resin
Examples of the olefin resin include α-olefins such as ethylene, propylene, 1-butene, 3-methyl-1-pentene, 4-methyl-1-butene, 1-hexene, 1-octene (in particular, α-C _2-10 Olefin) homopolymer or copolymer. Preferred olefin-based resins include ethylene-based resins (for example, polyethylene, ethylene-propylene copolymer, ethylene- (meth) acrylic acid copolymer, etc.) containing an ethylene unit as a main component (for example, 75 to 100% by weight). ), And propylene-based resins (for example, polypropylene, propylene-ethylene copolymer, propylene- (meth) acrylic acid copolymer, etc.) containing a propylene unit as a main component (for example, 75 to 100% by weight). . Olefin resins can be used alone or in combination of two or more.
[0020]
(2) Acrylic resin
Examples of the acrylic resin include (meth) acrylic acid C such as (meth) acrylic acid and methyl (meth) acrylate. _1-10 A homo- or copolymer of a (meth) acrylic monomer such as an alkyl ester, (meth) acrylamide, or (meth) acrylonitrile, or a copolymer of a (meth) acrylic monomer with another copolymerizable monomer. Polymers (for example, acrylonitrile-styrene copolymer, acrylonitrile-styrene- (meth) acrylic acid ester copolymer, etc.) are included. Preferred acrylic resins include poly (meth) acrylate methyl, acrylic acid alkyl ester-methyl methacrylate copolymer, (meth) acrylic acid-styrene copolymer, (meth) methyl acrylate-styrene copolymer, etc. Is mentioned. These acrylic resins can be used alone or in combination of two or more.
[0021]
(3) Styrenic resin
Examples of the styrene resin include a styrene monomer (for example, styrene, vinyl toluene, α-methyl styrene, chlorostyrene, etc.) or a copolymer; a styrene monomer and a vinyl monomer (for example, Copolymers with unsaturated nitriles such as acrylonitrile, (meth) acrylic acid esters, (meth) acrylic acid, α, β-monoolefinic unsaturated carboxylic acids such as maleic anhydride, acid anhydrides or esters thereof, etc.) A styrene-based graft copolymer, a styrene-based block copolymer, and the like.
[0022]
Preferred styrenic resins include polystyrene (GPPS), styrene-methyl methacrylate copolymer, styrene- (meth) acrylic acid copolymer, styrene-maleic anhydride copolymer, styrene-acrylonitrile copolymer (AS resin). ), Impact-resistant polystyrene (HIPS), polystyrene-based graft or block copolymer in which a styrene monomer is polymerized in the rubber component. Polystyrene-based graft copolymers include copolymers in which at least a styrene monomer and a copolymerizable monomer are graft-polymerized on a rubber component (for example, ABS resin obtained by graft-polymerizing styrene and acrylonitrile on polybutadiene, acrylic rubber) AAS resin obtained by graft polymerization of styrene and acrylonitrile, ACS resin obtained by graft polymerization of styrene and acrylonitrile on chlorinated polyethylene, polymer obtained by graft polymerization of styrene and acrylonitrile on ethylene-vinyl acetate copolymer, styrene and acrylonitrile on ethylene-propylene rubber A graft polymerized polymer, MBS resin grafted with styrene and methyl methacrylate on polybutadiene, and styrene / acrylonitrile grafted onto styrene-butadiene copolymer rubber. Examples of the block copolymer include copolymers composed of a polystyrene block and a diene or olefin block (for example, a styrene-butadiene-styrene (SBS) block copolymer, a styrene-isoprene block copolymer). Polymer, styrene-isoprene-styrene (SIS) block copolymer, hydrogenated styrene-butadiene-styrene (SEBS) block copolymer, hydrogenated styrene-isoprene-styrene (SEPS) block copolymer), and the like. .
[0023]
(4) Polyamide resin
Polyamides include polyamides derived from diamines and dicarboxylic acids; aminocarboxylic acids, polyamides obtained by using diamines and / or dicarboxylic acids in combination; lactams, and optionally diamines and / or dicarboxylic acids; Polyamide derived by the combined use of. Polyamide also includes copolyamides formed by at least two different polyamide-forming components.
[0024]
Examples of the diamine include fats such as trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, and octamethylenediamine. Aromatic diamines such as phenylenediamine and metaxylylenediamine; and alicyclic diamines such as bis (4-aminocyclohexyl) methane and bis (4-amino-3-methylcyclohexyl) methane. These diamines can be used alone or in combination.
[0025]
Examples of the dicarboxylic acid include aromatic dicarboxylic acids such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, and naphthalenecarboxylic acid; and fats such as cyclohexane-1,4-dicarboxylic acid and cyclohexane-1,3-dicarboxylic acid. Cyclic dicarboxylic acid; C such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, octadecanedioic acid _4-20 Aliphatic dicarboxylic acids; dimerized fatty acids (dimer acids) and the like.
[0026]
Examples of the aminocarboxylic acid include C, such as aminoheptanoic acid, aminononanoic acid, and aminoundecanoic acid. _4-20 Aminocarboxylic acids are exemplified. Aminocarboxylic acids can be used alone or in combination of two or more.
Examples of the lactam include C such as butyrolactam, bivalolactam, caprolactam, capryllactam, enantolactam, undecanolactam, and dodecalactam. _4-20 Examples include lactams. These lactams can also be used alone or in combination.
[0027]
Examples of polyamide resins include aliphatic polyamides such as nylon 46, nylon 6, nylon 66, nylon 610, nylon 612, nylon 11 and nylon 12, aromatic dicarboxylic acids (for example, terephthalic acid and / or isophthalic acid) and aliphatics. Polyamides obtained from diamines (eg hexamethylenediamine), polyamides obtained from aliphatic dicarboxylic acids (eg adipic acid) and aromatic diamines (eg metaxylylenediamine), aromatic and aliphatic dicarboxylic acids ( For example, a polyamide obtained from terephthalic acid and adipic acid and an aliphatic diamine (for example, hexamethylenediamine) can be used. These polyamides can be used alone or in combination. Preferred polyamides include nylon 6, nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, a polyamide in which at least one of the diamine component and dicarboxylic acid component is an aromatic compound.
[0028]
(5) Polyester resin
The polyester-based resin is a homopolyester or a copolyester obtained by polycondensation of a dicarboxylic acid component and a diol component, polycondensation of oxycarboxylic acid or lactone, or polycondensation of these components. Preferred polyester resins usually include saturated polyester resins, particularly aromatic saturated polyester resins.
[0029]
Examples of the dicarboxylic acid component include aliphatic dicarboxylic acids (for example, dicarboxylic acids having about 6 to 40 carbon atoms such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, hexadecanedicarboxylic acid, and dimer acid. Acid, preferably a dicarboxylic acid having about 1 to 14 carbon atoms), an alicyclic dicarboxylic acid (for example, a dicarboxylic acid having about 8 to 12 carbon atoms such as hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, and hymic acid Acid), aromatic dicarboxylic acid (for example, naphthalenecarboxylic acid such as phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenylcarboxylic acid, 4,4′-diphenoxyethercarboxylic acid) Acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'- And dicarboxylic acids having about 8 to 16 carbon atoms such as diphenyl ketone dicarboxylic acid) or derivatives thereof (for example, derivatives capable of forming an ester such as lower alkyl ester and acid anhydride).
[0030]
Furthermore, you may use together polyvalent carboxylic acids, such as a trimet acid and a pyromellitic acid, as needed.
[0031]
Preferred dicarboxylic acid components include aromatic dicarboxylic acids such as terephthalic acid and naphthalenedicarboxylic acid.
[0032]
Examples of the diol component include aliphatic alkylene diols (for example, ethylene glycol, trimethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, hexanediol, octanediol, decanediol. An aliphatic glycol having about 2 to 12 carbon atoms, preferably an aliphatic glycol having about 2 to 10 carbon atoms), a polyoxyalkylene glycol (a plurality of oxyalkylene units having an alkylene group having about 2 to 4 carbon atoms) Such as diethylene glycol, dipropylene glycol, ditetramethylene glycol, triethylene glycol, tripropylene glycol, polytetramethylene glycol, etc.], alicyclic diols (for example, 1,4-cyclo Xanthdiol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.), aromatic diol [eg, biphenol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis- (4- (2 -Hydroxyethoxy) phenyl) propane, xylylene glycol, etc.].
[0033]
Furthermore, you may use together polyols, such as glycerol, a trimethylol propane, a trimethylol ethane, a pentaerythritol, as needed.
[0034]
Preferred diol components include C _2-6 Alkylene glycol (linear alkylene glycol such as ethylene glycol, propylene glycol, 1,4-butanediol), polyoxyalkylene glycol having an oxyalkylene unit having a repeat number of about 2 to 4 [poly (oxy-C such as diethylene glycol) _2-4 Glycol) containing alkylene) units], 1,4-cyclohexanedimethanol and the like.
[0035]
Examples of the oxycarboxylic acid include oxycarboxylic acids such as oxybenzoic acid, hydroxynaphthoic acid, hydroxyphenylacetic acid, glycolic acid, and oxycaproic acid, or derivatives thereof.
[0036]
The lactone includes C, such as propiolactone, butyrolactone, valerolactone, caprolactone (eg, ε-caprolactone, etc.). _3-12 Lactone and the like are included.
[0037]
Preferred polyester resins include homopolyesters or copolyesters having an alkylene arylate such as alkylene terephthalate or alkylene naphthalate as a main component (for example, about 50 to 100% by weight, preferably about 75 to 100% by weight), such as polyalkylene. Terephthalate (for example, poly C such as poly 1,4-cyclohexanedimethylene terephthalate (PCT), polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polybutylene terephthalate (PBT), etc. _2-4 Alkylene terephthalate), polyalkylene naphthalate (for example, poly C such as polyethylene naphthalate, polybutylene naphthalate) _2-4 Homopolyesters such as alkylene naphthalate); copolyesters containing alkylene terephthalate and / or alkylene naphthalate units as a main component (for example, 50% by weight or more); both dicarboxylic acid component and diol component are aromatic compounds Certain fully aromatic polyesters such as polyarylate are included. Particularly preferred polyester resins include polybutylene terephthalate resins containing a butylene terephthalate unit as a main component (for example, polybutylene terephthalate, polybutylene terephthalate copolyester). In addition, these polyester-type resin can be used individually or in combination of 2 or more types.
[0038]
In the copolyester, the copolymerizable monomer is C _2-6 Alkylene glycol (e.g., linear alkylene glycol such as ethylene glycol, propylene glycol, 1,4-butanediol), polyoxyalkylene glycol having an oxyalkylene unit having about 2 to 4 repetitions (poly (oxy-) such as diethylene glycol) C _2-4 Alkylene) glycols containing units), C _6-12 Aliphatic dicarboxylic acids (adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc.), aromatic dicarboxylic acids (phthalic acid, isophthalic acid, etc.) and the like can be mentioned.
[0039]
The polyester resin may have not only a straight chain but also a branched chain structure as long as melt moldability is not impaired, and may be crosslinked. Moreover, liquid crystal polyester may be sufficient.
[0040]
The polyester resin can be produced by a conventional method such as transesterification or direct esterification.
[0041]
(6) Polycarbonate resin
The polycarbonate resin includes a polymer obtained by a reaction between a dihydroxy compound and a carbonate such as phosgene or diphenyl carbonate. The dihydroxy compound may be an alicyclic compound or the like, but is preferably a bisphenol compound.
[0042]
Examples of the bisphenol compound include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis ( 4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) ) Bis (hydroxyaryl) C such as hexane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane _1-6 Alkanes; bis (hydroxyaryl) C such as 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane _4-10 4,4'-dihydroxydiphenyl ether; 4,4'-dihydroxydiphenyl sulfone; 4,4'-dihydroxydiphenyl sulfide; 4,4'-dihydroxydiphenyl ketone and the like.
[0043]
Preferred polycarbonate-based resins include bisphenol A type polycarbonate.
[0044]
(7) Polyphenylene oxide resin
The polyphenylene oxide resin includes a homopolymer and a copolymer. Homopolymers include poly (2,6-dimethyl-1,4-phenylene) oxide, poly (2-methyl-6-ethyl-1,4-phenylene) oxide, poly (2,6-di-n- Propyl-1,4-phenylene) oxide, poly (2-ethyl-6-isopropyl-1,4-phenylene) oxide, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) oxide, poly (2 -Methyl-6-chloroethyl-1,4-phenylene) oxide and the like.
[0045]
As a copolymer of polyphenylene oxide, an alkylphenol-modified benzeneformaldehyde resin block obtained by reacting a benzeneformaldehyde resin or an alkylbenzeneformaldehyde resin with an alkylphenol such as cresol or p-tert-butylphenol, a polyphenyleneoxide block as a main structure, and And a modified graft copolymer in which a styrene polymer is grafted to polyphenylene oxide or a copolymer thereof.
[0046]
(8) Vinyl resin
Examples of vinyl resins include vinyl monomers (for example, vinyl esters such as vinyl acetate, vinyl propionate, vinyl crotonate, and vinyl benzoate); chlorine-containing vinyl monomers (for example, vinyl chloride); Monomers (for example, fluoroethylene, chloroprene, etc.); vinyl ketones such as methyl vinyl ketone and methyl isopropenyl ketone; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; vinyl amines such as N-vinylcarbazole and N-vinylpyrrolidone And the like, or copolymers with other copolymerizable monomers.
[0047]
Derivatives of the vinyl resins (for example, polyvinyl acetals such as polyvinyl alcohol, polyvinyl formal, and polyvinyl butyral, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, etc.) can also be used.
[0048]
Preferred vinyl resins include halogen-containing vinyl resins, for example, vinyl chloride resins such as polyvinyl chloride; polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, tetrafluoroethylene-hexa. Fluorine resins such as fluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, and tetrafluoroethylene-ethylene copolymer can be exemplified.
[0049]
(9) Other resins
Other resins include polyacetal resins, aliphatic polyketone resins (ketone resins); polyphenylene sulfide resins (eg, polyphenylene sulfide, polyphenylene sulfide ketone, polybiphenylene sulfide, polyphenylene sulfide sulfone, etc.); polysulfones (eg, thermoplastic) Polysulfone, poly (ether sulfone), poly (4,4′-bisphenol ether sulfone, etc.); polyetherimide; polyether ketone; poly (ether ether ketone); thermoplastic polyurethane resin (eg, diisocyanate such as tolylene diisocyanate) Polymers obtained by the reaction of the compound with the glycol and / or the diamine, and a segment such as polytetramethylene glycol may be included. Urethane elastomers); thermoplastic polyimide; polyoxyethylene benzylidene alkylene; and thermoplastic elastomers can be exemplified.
[0050]
These polymer compounds may be used alone or in combination of two or more.
[0051]
Preferred thermoplastic resins include styrene resins, polyamide resins, polyester resins that may be liquid crystalline polyesters, polycarbonate resins, polyphenylene oxide resins, polyphenylene sulfide resins, vinyl resins, and the like. Examples thereof include polyester resins, polycarbonate resins, polyamide resins, and styrene resins, and PBT resins are particularly preferable.
[0052]
The number average molecular weight of the thermoplastic resin is not particularly limited and is appropriately selected depending on the type and use of the resin. For example, 5 × 10 ^Three ~ 200 × 10 ^Four , Preferably 1 × 10 ^Four ~ 150 × 10 ^Four More preferably 1 × 10 ^Four ~ 100 × 10 ^Four You can choose from a range of degrees. When the thermoplastic resin is a polyester resin, the number average molecular weight is, for example, 5 × 10 ^Three ~ 100 × 10 ^Four , Preferably 1 × 10 ^Four ~ 70x10 ^Four More preferably 1.2 × 10 ^Four ~ 30x10 ^Four It may be a degree.
[0053]
[Flame retardants]
The flame retardant of the present invention is composed of a phosphorus-containing compound and a resin having a hydroxyl group-containing aromatic ring in the side chain.
(Phosphorus-containing compound)
Examples of the phosphorus-containing compound include organic phosphorus compounds (monomer type organic phosphorus compounds, polymer type organic phosphorus compounds, etc.), inorganic phosphorus compounds, and the like.
[0054]
Among the organophosphorus compounds, monomeric organophosphorus compounds include phosphate esters, phosphite esters, hypophosphite esters, phosphine oxides (such as triphenylphosphine oxide and tricresylphosphine oxide), phosphate amides, Phosphorous amide, hypophosphorous amide and the like are included. Examples of phosphate esters include aliphatic phosphate esters such as trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate, and triisobutyl phosphate. _1-10 Alkyl esters; di-C phosphates such as dimethyl phosphate, diethyl phosphate, dipropyl phosphate, dibutyl phosphate, di (2-ethylhexyl) phosphate _1-10 Alkyl ester; phosphate mono-C _1-10 Alkyl esters, etc.], aromatic phosphate esters [triphenyl phosphate, tricresyl phosphate, trixylyl phosphate, diphenyl cresyl phosphate, tri (isopropylphenyl) phosphate, diphenylethyl cresyl phosphate, etc. _6-20 Aryl esters and the like], and aliphatic-aromatic phosphate esters (such as methyldiphenyl phosphate and phenyldiethyl phosphate).
[0055]
Examples of phosphites include aromatic phosphites (triphenyl phosphite, tricresyl phosphite, trixyl phosphite, diphenyl cresyl phosphite, etc.) _6-20 Aryl esters, etc., aliphatic phosphites (trimethyl phosphite, triethyl phosphite, tripropyl phosphite, triisopropyl phosphite, tributyl phosphite, triisobutyl phosphite, etc.) _1-10 Alkyl esters; di-C phosphites such as dimethyl phosphite, diethyl phosphite, dipropyl phosphite, dibutyl phosphite _1-10 Alkyl ester; phosphorous acid mono-C _1-10 Alkyl ester, etc.), aliphatic-aromatic phosphites (alkylphosphonic acid aryl esters such as diphenyl methanephosphonate, alkylphosphonic acid alkyl esters such as diethyl methanephosphonate), and the like.
[0056]
The monomeric organophosphorus compound also includes hypophosphite, phosphonocarboxylic acid ester, phosphinicocarboxylic acid ester, nitrogen-containing phosphoric acid ester which may be substituted with an alkyl group or aryl group. .
[0057]
As the polymer type organic phosphorus compound, a condensate of the monomer type organic phosphorus compound can be used. The condensate may have a structural unit represented by the following formula (2).
[0058]
[Chemical 3]

[0059]
(Wherein R ^Three ~ R ⁶ Represents an aryl group which may have a substituent, and Z represents a divalent aromatic group. a represents an integer of 1 to 5)
In formula (2), R ^Three ~ R ⁶ Examples of the aryl group represented by C include phenyl and naphthyl groups. _6-20 An aryl group is mentioned, As a substituent of an aryl group, alkyl groups, such as a methyl group and an ethyl group, are mentioned. The divalent aromatic group includes an arylene group (for example, C such as phenylene and naphthylene groups). _6-20 Arylene groups, etc.), groups having a plurality of said arylene groups [groups obtained by removing hydroxyl groups from bisphenols such as bisphenol residues (bisphenol A residues, bisphenol D residues, bisphenol AD residues), biphenylene groups, etc.] It may be.
[0060]
Examples of the condensate represented by the above formula (2) include resorcinol bis (diphenyl phosphate), resorcinol bis (dicresyl phosphate), resorcinol bis (dixylyl phosphate), hydroquinone bis (diphenyl phosphate), hydroquinone bis (dicure). Zil phosphate), hydroquinone bis (dixyl phosphate), bisphenol-A bis (diphenyl phosphate), bisphenol-A bis (dicresyl phosphate), bisphenol-A bis (dixyl phosphate) and the like.
[0061]
The polymer-type organic phosphorus compound may be a phosphate ester of a polymer having a hydroxyl group (such as a phenol resin). Examples of the phosphoric acid ester of such a polymer include a polymer having a structural unit represented by the following formula (3).
[0062]
[Formula 4]

[0063]
(Wherein R ⁷ And R ⁸ Represents an aryl group which may have a substituent)
As the aryl group, C _6-20 An aryl group, particularly a phenyl group, a methylphenyl group, a dimethylphenyl group, and the like can be mentioned, and examples of the substituent of the aryl group include alkyl groups such as a methyl group and an ethyl group.
[0064]
Further, the polymer type organic phosphorus compound includes polyphosphinicocarboxylic acid ester and polyphosphonic acid amide. Examples of the polyphosphonic acid amide include a polymer having a structural unit represented by the following formula (4).
[0065]
[Chemical formula 5]

[0066]
(Wherein R ⁹ Represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and R ^Ten Represents an alkylene group, an arylene group, or an aralkylene group. R ¹¹ And R ¹² Are the same or different and each represents a hydrogen atom, an alkyl group, or an aryl group. R ¹¹ And R ¹² May be directly connected to form a ring)
Examples of the inorganic phosphorus compound include red phosphorus and phosphate. In addition to orthophosphoric acid, phosphoric acid includes phosphorous acid, polyphosphoric acid (metaphosphoric acid, pyrophosphoric acid, etc.), polyphosphorous acid (metaphosphorous acid, pyrophosphorous acid, etc.) and the like. Examples of the salt include alkali metal salts (lithium salts, sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, calcium salts, etc.), periodic table group 3B metal salts (aluminum salts, etc.), ammonium salts, and the like. It can be illustrated. The salts also include amine salts such as guanidine salts or salts of triazine compounds (for example, melamine salts and melem salts).
[0067]
The inorganic phosphorus compound may be phosphorous acid, hypophosphorous acid, phosphonocarboxylic acid, phosphinicocarboxylic acid (for example, 3-methylphosphinicopropionic acid, which may be substituted with an alkyl group or an aryl group, 3-phenylphosphiniphosphinicopropionic acid and the like, and metal salts of acids such as nitrogen-containing phosphoric acid.
[0068]
Preferred phosphates are salts of polyphosphoric acid, in particular ammonium polyphosphate and melamine polyphosphate.
[0069]
Preferred phosphorus-containing compounds include phosphate esters (aliphatic phosphate esters, aromatic phosphate esters, etc.), inorganic phosphorus compounds (((poly) phosphates such as ammonium polyphosphate and melamine polyphosphate, red phosphorus, etc.) In particular, red phosphorus is mentioned.
[0070]
Red phosphorus has a high flame retardant effect and can impart flame retardancy to the resin even in a small amount. In addition, since the effect can be obtained in a small amount, flame retardancy can be achieved without impairing the resin properties (for example, mechanical properties and electrical properties). As red phosphorus, in particular, those subjected to stabilization treatment (stabilized red phosphorus) are preferably used. In particular, the method of atomizing red phosphorus without pulverizing red phosphorus without forming a crushing surface having high reactivity with water or oxygen on the surface of red phosphorus, and further, the surface of red phosphorus is a resin (for example, , Thermosetting resin, thermoplastic resin), metal, metal compound (for example, metal hydroxide, metal oxide, etc.) and the like, and red phosphorus coated alone or in combination of two or more thereof are preferable.
[0071]
Examples of thermosetting resins include phenolic resins, melamine resins, urea resins, alkyd resins, unsaturated polyester resins, epoxy resins, and silicone resins. Thermoplastic resins include polyester resins and polyamide resins. , Acrylic resins, olefin resins, and the like. Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, zinc hydroxide, and titanium hydroxide. Examples of the metal oxide include aluminum oxide, magnesium oxide, zinc oxide, titanium oxide, and oxide. Examples include zirconium, copper oxide, iron oxide, molybdenum oxide, tungsten oxide, manganese oxide, and tin oxide.
[0072]
Furthermore, as a method of stabilizing the surface of red phosphorus by coating with metal, it is possible to use metal (iron, nickel, copper, aluminum, zinc, manganese, tin, titanium, zirconium, etc.) or an alloy thereof by electroless plating. The method of coating is mentioned. As another method for coating the surface of red phosphorus, red phosphorus is treated with a solution of a metal salt (aluminum, magnesium, zinc, titanium, copper, silver, iron, nickel, etc.), and a metal phosphorus compound is applied to the surface of red phosphorus. Also included are methods of forming and stabilizing.
[0073]
In particular, using a method that makes red phosphorus into fine particles without forming a crushing surface on the surface of red phosphorus, coating with multiple layers by combining a metal component (metal hydroxide or metal oxide) coating and a resin coating In particular, red phosphorus coated with a coating of a metal component and multiple coated with a resin coating is preferred. These stabilized red phosphorus is excellent in heat resistance stability and hydrolysis resistance, and phosphine is remarkably produced by the decomposition reaction in the presence of moisture or at high temperature. When the resin composition of the present invention is produced, In addition, it is preferably used from the viewpoint of safety when producing a molded product and the quality of the molded product.
[0074]
Preparation of these stabilized red phosphorus is disclosed in JP-A-5-229806, JP-A-3-259756, JP-A-2-209991, JP-A-1-150309, JP-A-62-27044. JP-A-52-125489, EP296501A1, EP249723A2 and the like can be referred to.
[0075]
As red phosphorus, stabilized red phosphorus can usually be used in powder form. The particle diameter of the stabilized red phosphorus is, for example, 0.01 to 100 μm, preferably 0.1 to 70 μm, and more preferably about 0.1 to 50 μm.
[0076]
The stabilized red phosphorus may be treated with a surface modifier such as an epoxy compound, a silane compound, a titanate compound, or a chromium compound.
[0077]
The stabilized red phosphorus may be used alone or in combination of two or more. For example, those having different coating treatments and those having different particle sizes can be arbitrarily combined.
(Resin having a hydroxyl group-containing aromatic ring in the side chain)
As a resin having a hydroxyl group-containing aromatic ring in the side chain (hereinafter simply referred to as an aromatic ring resin), for example, a resin having a structural unit represented by the following formula (1) can be used.
[0078]
[Chemical 6]

[0079]
(Wherein R ¹ Is a hydrogen atom or C _1-3 An alkyl group of R ² Represents an aromatic ring, and n is an integer of 1 to 3)
In the formula (1), examples of the aromatic ring include C such as benzene and naphthalene ring. _6-20 An aromatic ring is mentioned. The aromatic ring is a substituent (for example, a hydroxyl group; an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, or t-butyl group; an alkoxy group such as methoxy, ethoxy, or propoxy group). Etc.).
[0080]
In the formula (1), the hydrogen atom of the hydroxyl group may be protected with an organic group (protecting group) such as a metal ion, a silyl group or an alkoxy group, an alkyl group, an alkanoyl group, or a benzoyl group.
[0081]
A resin obtained from such a derivative has, for example, a structural unit represented by the following formula (5).
[0082]
[Chemical 7]

[0083]
(Wherein R ¹ Is a hydrogen atom or C _1-3 An alkyl group of R ¹³ Is -OH, -OSi (R ¹⁴ ) _Three And -OM (M is a metal cation, OR ¹⁴ And OCOR ¹⁴ And R ¹⁴ Is a group selected from the group consisting of an alkyl group having 1 to 5 carbon atoms or an aryl group. N is an integer of 1 to 3. )
In the above formula, M may be a monovalent alkali metal cation (sodium, lithium, potassium, etc.), or a divalent alkaline earth metal cation (magnesium, calcium, etc.) or a transition metal cation.
[0084]
Substituent R in the above formula ¹³ May be located at any one of the ortho, para and meta positions. Furthermore, the substituent R ¹³ In addition, the pendant aromatic ring is C _1-4 The alkyl group may be substituted.
[0085]
The aromatic ring resin includes an aromatic ring vinyl monomer having a hydroxyl group corresponding to the structural unit (1) (hereinafter simply referred to as an aromatic ring vinyl monomer), a copolymer, or other copolymerizable monomer. And a copolymer thereof.
[0086]
Examples of the aromatic ring vinyl monomer include hydroxyl group-containing aromatic vinyl monomers such as vinyl phenol, dihydroxystyrene, and vinyl naphthol.
[0087]
Examples of the aromatic ring vinyl monomer include hydroxyl group-containing aromatic vinyl monomers such as vinyl phenol, dihydroxystyrene, and vinyl naphthol.
[0088]
Examples of copolymerizable monomers include (meth) acrylic monomers [(meth) acrylic acid, (meth) acrylic acid esters (for example, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid). Butyl, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, etc.), (meth) acrylamide, (meth) acrylonitrile, etc.], styrenic monomers (for example, styrene, vinyltoluene, α- Methyl styrene, chlorostyrene, vinyl naphthalene, vinyl cyclohexane, etc.), polymerizable polycarboxylic acids (fumaric acid, maleic acid, etc.), maleimide monomers (phenyl maleimide, etc.), diene monomers (isoprene, 1,3-butadiene, 1,4-hexadiene, dicyclopentadiene, etc.), vinyl Nomers (for example, vinyl esters such as vinyl acetate and vinyl propionate; vinyl ketones such as methyl vinyl ketone and methyl isopropenyl ketone); halogen-containing vinyl monomers such as vinyl chloride, fluoroethylene and chloroprene; vinyl isobutyl ether and vinyl methyl ether Vinyl ethers such as N-vinyl carbazole, N-vinyl pyrrolidone, N-vinyl imidazole, etc.). Preferred copolymerizable monomers include styrene monomers, (meth) acrylic monomers, vinyl monomers, and the like.
[0089]
These copolymerizable monomers can be used alone or in combination of two or more.
[0090]
If necessary, a part of the aromatic ring resin may be hydrogenated.
[0091]
The ratio of the aromatic ring vinyl monomer and the copolymerizable monomer is, for example, about 10/90 to 100/0 (wt%), preferably about 30/70 to 100/0 (wt%).
[0092]
Preferred aromatic ring resins are vinylphenol homopolymers (polyhydroxystyrene) and vinylphenol copolymers (such as hydroxystyrene-styrene copolymers), with p-vinylphenol homopolymers being particularly preferred.
[0093]
The number average molecular weight of the aromatic ring resin is not particularly limited, and is, for example, 300 to 50 × 10. ^Four , Preferably 400-30 × 10 ^Four , More preferably 500-5 × 10 ^Four You can choose from a range of degrees. In particular, an aromatic resin in the range of 500 to 10,000 is preferably used. When the molecular weight is less than 300, the heat resistance of the resin composition is lowered.
(Ratio of phosphorus-containing compound and aromatic ring resin)
The usage-amount of the phosphorus containing compound in a flame retardant is selected in the range which can provide a flame retardance, 1-100 weight part of phosphorus containing compounds with respect to 100 weight part of said aromatic ring resin, Preferably it is 5-80 weight. Part, more preferably about 10 to 60 parts by weight.
(Use ratio of flame retardant)
The flame retardant of the present invention can impart high flame retardancy to a thermoplastic resin even when added in a small amount by combining a phosphorus-containing compound and an aromatic ring resin. The ratio of the flame retardant contained in the thermoplastic resin is not particularly limited as long as the properties of the resin are not impaired, and the flame retardant is 0.1 to 100 parts by weight, preferably 100 parts by weight of the thermoplastic resin. The amount is about 1 to 80 parts by weight, more preferably about 5 to 60 parts by weight (particularly 5 to 40 parts by weight). When the flame retardant is less than 0.1 parts by weight, it is difficult to make the flame retardant, and when it exceeds 100 parts by weight, the mechanical strength of the resin is lowered.
[Additive]
In addition, the flame retardant resin composition of the present invention may contain various additives (for example, other flame retardants, anti-drip agents, antioxidants or stabilizers) as necessary. The total content of the agent is 0.01 to 50 parts by weight, preferably 0.1 to 30 parts by weight, and more preferably about 0.5 to 20 parts by weight with respect to 100 parts by weight of the thermoplastic resin. .
[Other flame retardants]
The flame retardant resin composition of the present invention provides other flame retardants, for example, a nitrogen-containing flame retardant, a sulfur-containing flame retardant, a silicon-containing flame retardant, an alcohol-based flame retardant, an inorganic flame retardant, in order to impart higher flame retardancy. A flame retardant (such as a metal oxide or a metal hydroxide) may be included.
[0094]
Nitrogen-containing flame retardants include amines such as ureas, guanidines, triazine compounds (eg, guanamine, melamine, melam, melem, ammelin, melamine formaldehyde resin, benzoguanamine), triazine compounds and cyanuric acid or isocyanate. Salts with nouric acid (the former: the latter (molar ratio)) of about 1: 1 to 1: 2, such as melamine cyanurate, guanamine cyanurate, acetoguanamine cyanurate, benzoguanamine cyanurate, etc.
[0095]
Examples of the sulfur-containing flame retardant include organic sulfonic acid, sulfamic acid, and salts, esters and amides thereof in addition to sulfate ester.
[0096]
Silicon-containing flame retardants include (poly) organosiloxanes. Examples of the (poly) organosiloxane include dialkylsiloxanes (for example, dimethylsiloxane), alkylarylsiloxanes (for example, phenylmethylsiloxane), monoorganosiloxanes such as diarylsiloxane, and homopolymers thereof (for example, polydimethylsiloxane, polyphenyl). Methyl siloxane), or a copolymer. The (poly) organosiloxane includes a modified (poly) organosiloxane having a substituent such as an epoxy group, a hydroxyl group, a carboxyl group, an amino group or an ether group at the molecular terminal or main chain (for example, a modified silicone). Can also be used.
[0097]
Examples of alcohol-based flame retardants include polyhydric alcohols, oligomeric polyhydric alcohols, esterified polyhydric alcohols, substituted alcohols, and saccharides (monosaccharides, polysaccharides, and the like).
[0098]
Among the inorganic flame retardants, examples of the metal oxide include molybdenum oxide, tungsten oxide, titanium oxide, zirconium oxide, tin oxide, copper oxide, zinc oxide, aluminum oxide, nickel oxide, iron oxide, antimony trioxide, and four. Examples include antimony oxide and antimony pentoxide. Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, tin hydroxide, and zirconium hydroxide.
[0099]
The inorganic flame retardant also includes metal stannate (eg, zinc stannate), metal borate (eg, sodium tetraborate, zinc borate), expandable graphite, and the like.
[0100]
These other flame retardants can be used singly or in combination.
[0101]
The content of the other flame retardant is, for example, about 0.01 to 50 parts by weight, preferably about 0.05 to 30 parts by weight, particularly about 0.1 to 20 parts by weight with respect to 100 parts by weight of the thermoplastic resin. You can choose from a range of
[Anti-drip agent]
Furthermore, you may add anti-drip agents, such as a fluorine resin, to the flame-retardant resin composition of this invention. With the anti-drip agent, it is possible to suppress the fire type and melt dripping (drip) during combustion. Fluorine-based resins include tetrafluorethylene, chlorotrifluoroethylene, vinylidene fluoride, hexafluoropropylene, perfluoroalkyl vinyl ether and other fluorine-containing monomers, or copolymers; the fluorine-containing monomers and ethylene, propylene, acrylate And copolymers with copolymerizable monomers such as Examples of such a fluororesin include homopolymers such as polytetrafluoroethylene, polychlorotrifluoroethylene, and polyvinylidene fluoride; tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl. Examples of the copolymer include vinyl ether copolymers, ethylene-tetrafluoroethylene copolymers, and ethylene-chlorotrifluoroethylene copolymers. These fluororesins can be used alone or in combination.
[0102]
The fluororesin may be used in the form of particles, and the average particle size may be, for example, about 10 to 5000 μm, preferably about 100 to 1000 μm, and more preferably about 200 to 700 μm.
[0103]
The fluororesin can be used alone or in combination of two or more. The content of the fluororesin is, for example, about 0.01 to 10 parts by weight, preferably about 0.1 to 5 parts by weight, and more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the thermoplastic resin. Degree. [Antioxidant or stabilizer]
In addition, the flame retardant resin composition of the present invention may contain an antioxidant or a stabilizer in order to maintain heat resistance stably for a long period of time. Examples of the antioxidant or stabilizer include phenol-based (such as hindered phenols), amine-based (such as hindered amines), phosphorus-based, sulfur-based, hydroquinone-based, and quinoline-based antioxidants.
[0104]
Phenol antioxidants include hindered phenols such as 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4'-methylenebis (2,6-di-t-butylphenol). 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-p-cresol, 1,3,5-trimethyl-2,4,6-tris (3 , 5-di-t-butyl-4-hydroxybenzyl) benzene, 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythritol tetrakis [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4) Hydroxyphenyl) propionate], n-octadecyl-3- (4 ′, 5′-di-t-butylphenol) propionate, n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenol) ) Propionate, stearyl-2- (3,5-di-t-butyl-4-hydroxyphenol) propionate, distearyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, 2-t-butyl- 6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenyl acrylate, N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocin Namamide), 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenol) butane and the like are included.
[0105]
Among hindered phenols, in particular, C such as 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], for example. _2-10 Alkylenediol-bis [3- (3,5-di-branched C _3-6 Alkyl-4-hydroxyphenyl) propionate]; di- or trioxy C such as, for example, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] _2-4 Alkylenediol-bis [3- (3,5-di-branched C _3-6 Alkyl-4-hydroxyphenyl) propionate]; for example, glycerol tris [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] _3-8 Alkylenetriol-bis [3- (3,5-di-branched C _3-6 Alkyl-4-hydroxyphenyl) propionate]; for example C such as pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] _4-8 Alkylenetetraol tetrakis [3- (3,5-di-branched C _3-6 Alkyl-4-hydroxyphenyl) propionate] and the like.
[0106]
Amine-based antioxidants include hindered amines such as tri- or tetra-C _1-3 Alkyl piperidines or derivatives thereof [eg 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6 , 6-tetramethylpiperidine etc.], bis (tri, tetra or penta C _1-3 Alkyl piperidine) C _2-20 Alkylene dicarboxylic acid esters [for example, bis (2,2,6,6-tetramethyl-4-piperidyl) ogisalate, bis (2,2,6,6-tetramethyl-4-piperidyl) malonate, bis (2,2 , 6,6-tetramethyl-4-piperidyl) adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) ) Sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate], 1,2-bis (2,2,6,6-tetramethyl-4-piperidyloxy) ethane, phenyl-1 -Naphthylamine, phenyl-2-naphthylamine, N, N'-diphenyl-1,4-phenylenediamine, N-phenyl-N'-cyclohexyl-1,4-phen Such as diamine are included.
[0107]
Examples of the phosphorus stabilizer (or antioxidant) include triisodecyl phosphite, trisnonyl phenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, 2,2-methylene bis (4,6-di-). t-butylphenyl) octyl phosphite, 4,4′-butylidenebis (3-methyl-6-tert-butylphenyl) ditridecyl phosphite, tris (branched C _3-6 Alkylphenyl) phosphite [e.g., tris (2,4-di-t-butylphenyl) phosphite, tris (2-t-butyl-4-methylphenyl) phosphite, tris (2,4-di-t- Amylphenyl) phosphite, tris (2-t-butylphenyl) phosphite, tris [2- (1,1-dimethylpropyl) -phenyl] phosphite, tris [2,4- (1,1-dimethylpropyl) -Phenyl] phosphite, etc.], bis (2-t-butylphenyl) phenyl phosphite, tris (2-cyclohexylphenyl) phosphite, tris (2-t-butyl-4-phenylphenyl) phosphite, bis ( C _3-9 Alkylaryl) pentaerythritol diphosphite [e.g., bis (2,4-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) ) Pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, etc.], triphenyl phosphate stabilizers (for example, 4-phenoxy-9-α- (4 -Hydroxyphenyl) -p-cumenyloxy-3,5,8,10-tetraoxa-4,9-diphosphapyro [5,5] undecane, tris (2,4-di-t-butylphenyl) phosphate, etc.), diphosphonites Stabilizers such as tetrakis (2,4-di-t-butyl Chill) -4,4′-biphenylenediphosphonite and the like. Phosphorus stabilizers are usually branched C _3-6 It has an alkylphenyl group (particularly a t-butylphenyl group).
[0108]
Examples of the hydroquinone antioxidant include 2,5-di-t-butylhydroquinone, and examples of the quinoline antioxidant include 6-ethoxy-2,2,4-trimethyl-1,2. -Dihydroquinoline and the like are included, and sulfur-based antioxidants include, for example, dilauryl thiodipropionate, distearyl thiodipropionate, and the like.
[0109]
These antioxidants can be used alone or in combination of two or more. The content of the antioxidant is, for example, about 0.01 to 5 parts by weight, preferably 0.05 to 2.5 parts by weight, particularly about 0.1 to 1 part by weight with respect to 100 parts by weight of the thermoplastic resin. You can select from a range.
[0110]
In addition, when using a polyester-type resin or a polycarbonate-type resin as a thermoplastic resin, when an inorganic phosphorus compound is added, thermal stability will improve further. Examples of inorganic phosphorus compounds include inorganic phosphoric acid (phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, polyphosphoric acid, polyphosphorous acid, phosphonocarboxylic acid, nitrogen-containing phosphoric acid, etc.) and acidic metal salts thereof. Etc.
[0111]
The acidic metal salt of inorganic phosphoric acid includes, for example, inorganic alkali metal hydrogen phosphates (for example, NaH ₂ PO _Four , Na ₂ HPO _Four , KH ₂ PO _Four , K ₂ HPO _Four Alkali metal hydrogen phosphates such as, alkaline earth metal hydrogen phosphates (for example, CaHPO) _Four , Ca (H ₂ PO _Four ) ₂ , MgHPO _Four , Mg (H ₂ PO _Four ) ₂ , Etc.), inorganic aluminum hydrogen phosphate (eg, Al (H ₂ PO _Four ) _Three Etc.
[0112]
Furthermore, the flame retardant resin composition of the present invention may contain other additives depending on the purpose. Examples of other additives include stabilizers (ultraviolet absorbers, heat stabilizers, weather stabilizers, etc.), lubricants, mold release agents, colorants, plasticizers, nucleating agents, impact modifiers, sliding agents, and the like. .
[0113]
The flame retardant of the present invention can make the resin highly flame retardant because of promoting carbonization of the resin surface during combustion. Further, by combining the phosphorus-containing compound and the aromatic ring resin, the thermoplastic resin can be effectively flame-retardant even in a small amount, and bleed-out and heat resistance are not reduced. In particular, when polyhydroxystyrene is used as a flame retardant component, the degree of freedom of resin modification is high compared to general phenol novolac resins produced by addition condensation reaction, and in basic characteristics (stability and compatibility). It is superior to ordinary phenol resin.
[filler]
In addition, the flame retardant resin composition of the present invention may be modified with a filler in order to further improve mechanical strength, rigidity, heat resistance, electrical properties, and the like. Fillers include fibrous fillers and non-fibrous fillers (plate-like fillers, granular fillers, etc.).
[0114]
Examples of the fibrous filler include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica / alumina fiber, zirconia fiber, potassium titanate fiber, metal fiber, high melting point organic fiber (for example, aliphatic or aromatic polyamide, aromatic Acrylic resins such as aromatic polyester, fluorine resin, polyacrylonitrile, etc.).
[0115]
Among non-fibrous fillers, granular fillers include silica, quartz powder, glass beads, glass powder, milled fiber (such as milled glass fiber), calcium silicate, aluminum silicate, kaolin, talc, clay, silica Silicates such as algae and wollastonite; metal oxides such as iron oxide, titanium oxide, zinc oxide and alumina; carbonates of metals such as calcium carbonate and magnesium carbonate; carbonates of metals such as calcium sulfate and barium sulfate Salts: Metal sulfates such as calcium sulfate and barium sulfate, and metal powders such as silicon carbide are included.
[0116]
Examples of the plate-like filler include glass flakes, mica, graphite, and various metal foils.
[0117]
Preferred fibrous fillers include glass fibers and carbon fibers, and preferred non-fibrous fillers include granular or plate-like fillers, particularly glass flakes, glass beads, milled fibers, talc, mica and kaolin. Is mentioned.
[0118]
Particularly preferred fillers include glass fibers having high strength and rigidity.
[0119]
When the filler is used, the proportion of the filler in the flame retardant resin composition is, for example, about 5 to 60% by weight, preferably about 5 to 50% by weight, and more preferably about 5 to 35% by weight.
[0120]
Moreover, when using these fillers, it is desirable to use a sizing agent or a surface treatment agent if necessary. As such a sizing agent or surface treatment agent, for example, a functional compound such as an epoxy compound, a silane compound, or a titanate compound is used. Preferably, an epoxy compound, in particular, a bisphenol A type or novolac type epoxy resin is used.
[0121]
The filler may be surface-treated or converged by the sizing agent or surface treatment agent. About the time of a process, you may process simultaneously with the addition of a filler, and you may process beforehand before addition.
[0122]
When performing surface treatment, the usage-amount of a functional surface treating agent is 5 weight% or less with respect to a filler, for example, Preferably it is about 0.05 to 2 weight%.
[0123]
[Method for producing flame retardant resin composition]
The flame retardant resin composition of the present invention may be a powder mixture or a molten mixture, and a thermoplastic resin, a flame retardant, and, if necessary, an anti-drip agent or other additives are used in a conventional manner. It can be prepared by mixing. For example, (1) mixing each component, kneading and extruding with a single or twin screw extruder to prepare pellets, and (2) once preparing pellets (master batches) with different compositions. A method of mixing (diluting) a predetermined amount of the pellet and subjecting it to molding to obtain a molded product having a predetermined composition, or (3) a method of directly charging one or more of each component into a molding machine can be employed. Further, in the preparation of a composition used for a molded article, a thermoplastic resin granule (for example, a granule obtained by pulverizing a part or all of a polyester-based resin) and other components (a flame retardant, etc.) Mixing and melt-kneading is advantageous in improving dispersion of other components.
[0124]
From the viewpoint of handling, it is convenient to prepare a master batch by once melt-mixing at least two components selected from a thermoplastic resin, an aromatic ring resin, and a phosphorus-containing compound. In particular, when red phosphorus is used as the phosphorus-containing compound, a master batch is often prepared. In addition, at least 1 type of components which comprise a masterbatch is a resin component. Moreover, when comprising a masterbatch with a resin component, a part of thermoplastic resin is often used for a masterbatch.
[0125]
Examples of the master batch include (1) a master batch composed of a part of a thermoplastic resin and a phosphorus-containing compound, (2) a master batch composed of an aromatic ring resin and a phosphorus-containing compound, (3 ) A master batch composed of a part of a thermoplastic resin, an aromatic ring resin, and a phosphorus compound.
[0126]
In addition, the said masterbatch may contain various additives, for example, a fluorine resin, antioxidant, phosphorus stabilizer, a filler, etc. as needed.
[0127]
Thus, a flame retardant resin composition can be manufactured by melt-mixing the masterbatch obtained in this way, a thermoplastic resin, and the remaining component as needed.
[0128]
In addition, after melt-kneading the flame-retardant resin composition of the present invention, a molded product formed by a conventional method such as extrusion molding, injection molding, or compression molding is excellent in flame retardancy and molding processability. Can be used for various purposes. For example, it can be suitably used for mechanical mechanism parts, electrical / electronic parts, automobile parts, packaging materials, cases, and the like.
[0129]
【The invention's effect】
In the present invention, since a thermoplastic resin and a flame retardant composed of a phosphorus-containing compound and a resin having a hydroxyl group-containing aromatic ring in the side chain are combined, a small amount can be obtained without using a halogen-based flame retardant. Can also be flame retardant. Furthermore, the flame retardant resin composition of the present invention can suppress bleed-out and maintain mechanical properties at a high level without using a special compound.
[0130]
【Example】
Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.
[0131]
In addition, the flame retardance, physical property, etc. of the resin composition were evaluated by the following test.
(Flammability test)
In accordance with UL 94, the flammability was evaluated with a test piece thickness of 0.8 mm.
(Tensile test)
Tensile properties were evaluated according to ASTM D-638.
(Molded appearance)
After the combustion test piece was treated in a gear oven at 120 ° C. for 24 hours, the appearance was evaluated. The evaluation criteria are shown below.
[0132]
○ = Almost no bleed out
Δ = Slight bleed out
× = A large amount of bleed out is observed
In the examples and comparative examples, the following thermoplastic resins and flame retardants were used.
[Thermoplastic resin A]
A-1: Polybutylene terephthalate (Duranex, intrinsic viscosity = 0.83, manufactured by Polyplastics Co., Ltd.)
A-2: 12.5 mol% isophthalic acid modified polybutylene terephthalate
A-3: Polyethylene terephthalate (Belpet EFG10, manufactured by Kanebo Co., Ltd.)
A-4: PBT elastomer (PBT segment 60% by weight, poly (tetramethylene oxide glycol) terephthalate segment 40% by weight)
A-5: PET-based liquid crystal polymer
A liquid crystal polyester obtained by melting and mixing polyethylene terephthalate (PET) and p-acetoxybenzoic acid and forming a polyester fragment by an acidolysis reaction, followed by a polycondensation reaction to increase the degree of polymerization. It has the following structural units.
[0133]
[Chemical 8]

[0134]
In addition, the ratio of k, l, and m is k / l / m = 80/20/20 (molar ratio).
[0135]
A-6: Polycarbonate (Panlite L1250, manufactured by Teijin Chemicals Ltd.)
A-7: Nylon-6,6 (Polyplastic nylon 66, manufactured by Polyplastics Co., Ltd.)
A-8: ABS resin (styrene 41% by weight, acrylonitrile 14% by weight, butadiene 45% by weight)
A-9: Polybutylene terephthalate (Duranex, intrinsic viscosity = 1.0, manufactured by Polyplastics Co., Ltd.)
A-10: Polybutylene terephthalate (Duranex, intrinsic viscosity = 0.75, manufactured by Polyplastics Co., Ltd.)
[Flame retardants]
(Phosphorus-containing compound B)
B-1: Red phosphorus (Nova Excel 140, manufactured by Rin Chemical Industry Co., Ltd.)
B-2: Red phosphorus (Nova Excel F5, manufactured by Rin Chemical Industry Co., Ltd.)
B-3: Red phosphorus master batch
(B-1) / (A-1) = 30/70 (weight ratio) red prepared from red phosphorus (B-1) and polybutylene terephthalate (A-1) using a biaxial extruder with a vent Rin masterbatch.
[0136]
B-4: Red phosphorus masterbatch
(B-2) / (A-1) = 30/70 (weight ratio) red prepared from red phosphorus (B-2) and polybutylene terephthalate (A-1) using a biaxial extruder with a vent Rin masterbatch.
[0137]
B-5: Condensed phosphate ester (PX-200, manufactured by Daihachi Chemical Industry Co., Ltd.)
B-6: Ammonium polyphosphate (Terrage C60, manufactured by Chisso Corporation)
B-7: Condensed phosphate ester (PX-201, manufactured by Daihachi Chemical Industry Co., Ltd.)
B-8: Condensed phosphate ester (Philol Flex RDP, manufactured by Akzo Nobel Co., Ltd.)
B-9: Condensed phosphate ester (Phyrol Flex BDP, manufactured by Akzo Nobel Co., Ltd.)
B-10: Bisphenol A bis (dicresyl phosphate)
B-11: Melamine polyphosphate (MPP-A, manufactured by Sanwa Chemical Co., Ltd.)
(Aromatic ring resin C)
C-1: Poly p-vinylphenol (Marcalinker MS-1P, number average molecular weight = 1100, manufactured by Maruzen Petrochemical Co., Ltd.)
C-2: Poly p-vinylphenol (Marcalinker MS-4P, number average molecular weight = 4300, manufactured by Maruzen Petrochemical Co., Ltd.)
C-3: p-vinylphenol-styrene copolymer (Marcalinker CST50, copolymerization ratio of p-vinylphenol: about 50 mol%, number average molecular weight 2100, manufactured by Maruzen Petrochemical Co., Ltd.)
C-4: p-vinylphenol-styrene copolymer (Marcalinker CST15, copolymerization ratio of p-vinylphenol: about 15 mol%, manufactured by Maruzen Petrochemical Co., Ltd.)
C-5: p-vinylphenol-methacrylic acid 2-hydroxyethyl copolymer (Marcalinker CHM, copolymerization ratio of p-vinylphenol: about 50 mol%, number average molecular weight = 3600, manufactured by Maruzen Petrochemical Co., Ltd. )
C′-1: phenol novolac resin (Sumilite Resin PR-53195, manufactured by Sumitomo Durez Co., Ltd.)
[Nitrogen-containing flame retardant D]
D-1: Melamine cyanurate (MC610, manufactured by Nissan Chemical Industries, Ltd.)
[Antioxidant E]
E-1: Pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Irganox 1010, manufactured by Ciba Geigy Corp.)
[Phosphorus stabilizer F]
F-1: Tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite (Sand Stub P-EPQ, manufactured by Sand Corp.)
F-2: Monocalcium phosphate
F-3: Bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (Adeka Stub PEP36, manufactured by Adeka-Gas Co., Ltd.)
[Anti-drip agent G]
G-1: Polytetrafluoroethylene
[Filler H (glass fiber)]
H-1: Chopped strand having a diameter of 10 μm and a length of 3 mm
Example 1 14, Reference Example 1 And Comparative Examples 1-5
The above components were mixed with polybutylene terephthalate (A-1) in the ratios shown in Tables 1 to 3, kneaded with an extruder, and extruded to prepare a resin composition. This resin composition was injection-molded to produce a test molded product, and the flammability, tensile properties, and molded appearance (bleed out) were evaluated.
[0138]
The results are shown in Tables 1-3.
[0139]
[Table 1]

[0140]
[Table 2]

[0141]
[Table 3]

[0142]
Example 15-19, Reference Examples 2-5 And Comparative Examples 6-19
The above components were mixed with the thermoplastic resin A in the ratios shown in Tables 4 to 6, kneaded with an extruder, and extruded to prepare a resin composition. This resin composition was injection-molded to produce a test molded product, and the flammability and molded appearance (bleed out) were evaluated.
[0143]
The results are shown in Tables 4-6.
[0144]
[Table 4]

[0145]
[Table 5]

[0146]
[Table 6]

[0147]
Example 20-24, Reference Examples 6-10 And Comparative Examples 20 to 28
The above components were mixed with the thermoplastic resin A at the ratios shown in Tables 7 and 8, kneaded with an extruder, and extruded to prepare a resin composition. This resin composition was injection-molded to produce a test molded product, and the flammability and molded appearance (bleed out) were evaluated.
[0148]
The results are shown in Table 7 and Table 8.
[0149]
[Table 7]

[0150]
[Table 8]

Claims (17)

A resin composition comprising a thermoplastic resin and a flame retardant, and said thermoplastic resin is polyester resin, the flame retardant, the phosphorus-containing compound and the side chain as a resin having a hydroxyl group-containing aromatic ring A flame retardant comprising 1 or 100 parts by weight of a vinylphenol homopolymer or a copolymer , and the proportion of the phosphorus-containing compound is 100 parts by weight of a resin having a hydroxyl group-containing aromatic ring in the side chain Resin composition.   The flame-retardant resin composition according to claim 1, comprising 0.1 to 100 parts by weight of a flame retardant with respect to 100 parts by weight of the thermoplastic resin.   The flame retardant resin composition according to claim 1, wherein the thermoplastic resin is a homo- or copolyester having at least one unit selected from alkylene terephthalate and alkylene naphthalate.   The thermoplastic resin is a homo- or copolyester having at least one unit selected from 1,4-cyclohexanedimethylene terephthalate, ethylene terephthalate, butylene terephthalate, propylene terephthalate, ethylene naphthalate and butylene naphthalate. The flame-retardant resin composition as described.   The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin is polybutylene terephthalate or a copolyester mainly composed of butylene terephthalate.   The flame retardant resin composition according to claim 1, wherein the phosphorus-containing compound is at least one selected from red phosphorus, (poly) phosphate, and phosphate.   The flame-retardant resin composition according to claim 1, wherein the phosphorus-containing compound is stabilized red phosphorus.   Furthermore, the flame-retardant resin composition of Claim 1 containing a nitrogen-containing flame retardant.   Furthermore, the flame-retardant resin composition of Claim 1 containing a fluorine resin.   Furthermore, the flame-retardant resin composition of Claim 1 containing a hindered phenolic antioxidant.   Furthermore, the flame-retardant resin composition of Claim 1 containing a phosphorus stabilizer.   The flame retardant resin composition according to claim 1, further comprising a salt of a triazine compound and cyanuric acid or isocyanuric acid.   Furthermore, the flame-retardant resin composition of Claim 1 containing a filler. A method for producing a flame retardant resin composition according to claim 1 by mixing a thermoplastic resin and the flame retardant according to claim 1 . A master batch composed of at least two components selected from a resin having a hydroxyl group-containing aromatic ring in the side chain according to claim 1, a phosphorus-containing compound and a thermoplastic resin, and a thermoplastic resin are melt-mixed. The method to manufacture the flame-retardant resin composition of Claim 14 .   The molded object formed with the flame-retardant resin composition of Claim 1. The molded body according to claim 16 , wherein the molded body is a mechanical mechanism part, an electric / electronic part, or an automobile part.