JP4209164B2 - Flame retardant polyamide resin composition - Google Patents

Description

【００２０】
２）Ｄ単位（二官能性）
【化６】

【００２１】
３）Ｔ単位（三官能性）
【化７】

【００２２】
４）Ｑ単位（四官能性）
【化８】

【００２３】
（但し、Ｒは、それぞれ同一又は異なる置換基で、アルキル基、アリール基、ベンジル基、ビニル基、アリル基、アルコキシ基、ヒドロキシ基、アミノ基、メチルエステル基およびエチルエステル基から選択される。）
この内、特にＴ単位及び／又はＱ単位を含有すると分岐状構造となる。そして、本発明の（ｄ）シリコーン化合物の構造は特に規定が無く、分岐状でも直鎖状でも良く、液状でも固体状でも良い。
【００２４】
この様なものとしては、例えば以下のものが挙げられる。直鎖状のオルガノポリシロキサンとしては、ジメチルポリシロキサン、メチルフェニルポリシロキサン、ビニルメチルオルガノポリシロキサン、ビニルフェニルメチルポリシロキサン等が挙げられ、分岐状のオルガノポリシロキサンとしてはメチルポリシロキサンレジン、メチルフェニルポリシロキサンレジン、フェニルポリシロキサンレジン、ビニルメチルオルガノポリシロキサンレジン、ビニルフェニルメチルポリシロキサンレジン等が挙げられる。更に変性したオルガノポリシロキサン（レジン）として、アミノ変性オルガノポリシロキサン（レジン）、エポキシ変性オルガノポリシロキサン（レジン）、カルボキシル変性オルガノポリシロキサン（レジン）、カルビノール変性オルガノポリシロキサン（レジン）、メタクリル変性オルガノポリシロキサン（レジン）、メルカプト変性オルガノポリシロキサン（レジン）、ポリエーテル変性オルガノポリシロキサン（レジン）、メチルスチリル変性オルガノポリシロキサン（レジン）、高級アルキル変性オルガノポリシロキサン（レジン）、高級アルキル脂肪酸エステル変性オルガノポリシロキサン（レジン）、アルキルアラルキル変性オルガノポリシロキサン（レジン）、ヒドロキシル変性オルガノポリシロキサン（レジン）、アルコキシ変性オルガノポリシロキサン（レジン）、アルコール変性オルガノポリシロキサン（レジン）、フッ素変性オルガノポリシロキサン（レジン）、シラノール変性オルガノポリシロキサン（レジン）等が挙げられ、これらの有機置換基の導入位置はオルガノポリシロキサンの主鎖末端や側鎖が挙げられ、導入率は一部又は全部でも良い。
【００２５】
ポリアミド分子中には極性の高いアミド結合が存在するが、シリコーン分子中にはさほど高い極性の官能基はないために、両者の相溶性は乏しい。そのために多量にシリコーンを含む場合には、成形片に剥離などによって外観が悪化するときがあるので、このことを回避するために、使用するシリコーン化合物の主鎖末端や側鎖の一部又は全部をここに挙げたアミノ基、エポキシ基、カルボキシル基、カルビノール基、メルカプト基、高級アルキル脂肪酸エステル基、アルコキシ基、ヒドロキシル基等のような極性官能基によって変性されたシリコーンを用いことができる。
【００２６】
シリコーンは配合されることによって、燃焼時に生成する不燃層（又は炭化層）が、一層大きく膨らみ断熱能力に富んだものになり、より一層大きな難燃効果が得られる。また、良流動性や耐衝撃性も付与することができる。
これらシリコーンの有機置換基の内にビニル基を含有するものが好ましい。また、ビニル基が直接ケイ素原子に結合したシリコーン化合物が高い難燃性を発現するので特に好ましく、末端基（トリメチルシリル基やアルコキシ基等）を除くケイ素原子に結合している全有機置換基の内、ビニル基率がモル比で２％以上であるシリコーンが一層高い難燃性を発現するので、更に好ましい。理由は明らかではないが、燃焼時に反応性の高いビニル基を含有するシリコーンが不燃層を形成し易くし、その形成された不燃層を強化材が強化する両者の相乗効果によって、優れた難燃効果即ち燃焼時のドリップ抑制効果を発揮すると思われる。
【００２７】
また、シリコーン化合物の添加方法は特に限定せず、一度シリコーン化合物と芳香族成分を含むポリアミド樹脂等の樹脂を押出機等で混練させて、シリコーン化合物含有の樹脂組成物を得た後に、これとホウ酸金属化合物、強化材等とを混練させる二段法でも、一度に、シリコーン化合物、ホウ酸金属化合物、強化材、芳香族成分を含むポリアミド樹脂等の樹脂を混練する一段法でも構わず、シリコーン化合物が液状である場合は、液添ポンプなどの液添装置で、押出機中の溶融樹脂への添加でも、樹脂のペレットなどに外潤でブレンドした後に、押出機などで混練する方法などが挙げられる。この内、液添装置を用いる場合には、シリコーン化合物のタンクやシリコーン化合物の流路をヒーターなどで加熱し粘度を下げても構わない。また、固体状の時には、押出機のトップの供給口（トップフィーダー）や押出機途中の供給口（サイドフィーダー）等からの供給や樹脂のペレットなどとブレンドした後に、押出機などで混練する方法などが挙げられる。
【００２８】
本発明において用いられる（ｅ）ポリフェニレンエーテル樹脂は任意成分であり、本成分が無くとも、本発明の目的は達成されるが、更なる難燃性、機械特性の向上を図る際には、本成分を添加することができる。
（ｅ）ポリフェニレンエーテル樹脂とは、繰り返し単位構造
【００２９】
【化９】

【００３０】
（Ｒ₁、Ｒ₄は、それぞれ独立して、水素、第一級もしくは第二級の低級アルキル、フェニル、アミノアルキルまたは炭化水素オキシを表す。Ｒ₂、Ｒ₃は、それぞれ独立して、水素、第一級もしくは第二級の低級アルキルまたはフェニルを表す。）
からなり、還元粘度（０．５ｇ／ｄｌ、クロロホルム溶液、３０℃測定）が、０．１５ｄｌ／ｇ以上１．０ｄｌ／ｇ以下の範囲にあるホモ重合体及び／または共重合体である。さらに好ましい還元粘度は、０．２０ｄｌ／ｇ以上０．７０ｄｌ／ｇ以下の範囲、最も好ましくは０．４０ｄｌ／ｇ以上０．６０ｄｌ／ｇ以下の範囲である。また、流動性や成形性を改良するために低い還元粘度のものを併用することもでき、低い還元粘度のものとしては０．０３ｄｌ／ｇ以上０．４０ｄｌ／ｇ以下の範囲であり、好ましくは、０．０６ｄｌ／ｇ以上０．３０ｄｌ／ｇ以下の範囲である。
【００３１】
具体例としては、ポリ（２，６−ジメチル−１，４−フェニレンエーテル）、ポリ（２−メチル−６−エチル−１，４−フェニレンエーテル）、ポリ（２−メチル−６−フェニル−１，４−フェニレンエーテル）、ポリ（２，６−ジクロロ−１，４−フェニレンエーテル）等が挙げられ、さらに、２，６−ジメチルフェノールと他のフェノール類（例えば、２，３，６−トリメチルフェノールや２−メチル−６−ブチルフェノール）との共重合体のようなポリフェニレンエーテル共重合体も挙げられる。中でもポリ（２，６−ジメチル−１，４−フェニレンエーテル）、２，６−ジメチルフェノールと２，３，６−トリメチルフェノールとの共重合体が好ましく、さらにポリ（２，６−ジメチル−１，４−フェニレンエーテル）が好ましい。
【００３２】
本発明で使用するポリフェニレンエーテルの製造方法の例として、米国特許第３３０６８７４号明細書記載の第一銅塩とアミンのコンプレックスを触媒として用い、２，６−キシレノールを酸化重合する方法がある。米国特許第３３０６８７５号、同第３２５７３５７号および同第３２５７３５８号の明細書、特公昭５２−１７８８０号および特開昭５０−５１１９７号および同６３−１５２６２８号の各公報等に記載された方法もポリフェニレンエーテルの製造方法として好ましい。
【００３３】
さらに、ポリフェニレンエーテル樹脂の内、一部又は全部を無水マレイン酸などの相溶化剤で変性したものであると、ポリアミド樹脂との相溶性を高めることによって、物性や外観などが向上し好ましい。また、この際の方法は特に限定せず、一度相溶化剤とポリフェニレンエーテル樹脂等を押出機中で反応させて、変性されたポリフェニレンエーテル等を得た後に、これとポリアミド等とを混練させる二段法でも、一度に相溶化剤、ポリフェニレンエーテル樹脂、ポリアミド樹脂等を混練する一段法でも構わない。
【００３４】
本発明の好ましい態様として、成分（ａ）及び（ｂ）が必須成分であり、このニ成分により、本発明の目的は達成させることができる。そして、成分（ｃ）、（ｄ）及び（ｅ）は任意成分であり、添加することによって更なる難燃性の付与、機械特性の向上、流動性の向上等の効果が追加される。
本発明の難燃性ポリアミド樹脂組成物において、（ｂ）ホウ酸金属化合物の割合は、特に定めない。しかし、成型加工性、機械物性、難燃性をさらに一層向上させる際には（ａ）芳香族成分を含むポリアミド樹脂１００重量部に対して、０．１重量部以上２００重量部以下が好ましい。２００重量部より多いと成形加工性、機械的物性の向上が少し不十分で、０．１重量部より少ないと難燃性の向上が少し不十分である。より好ましくは１重量部以上１５０重量部以下であり、更に好ましくは２重量部以上１２０重量部以下であり、最も好ましくは、５重量部以上１００重量部以下である。
【００３５】
（ｃ）強化材は、任意成分であるが、添加する際の割合は、（ａ）芳香族成分を含むポリアミド樹脂１００重量部に対して、５重量部以上２００重量部以下が好ましい。２００重量部より多いと押出時や射出成形時に成形加工性が著しく低下し、５重量部より少ないと添加しない場合と比べて、引張強度や剛性など機械的性質の向上があまりみられない。より好ましくは１０重量部以上１８０重量部以下であり、更に好ましくは１５重量部以上１５０重量部以下である。
【００３６】
（ｄ）シリコーン化合物は、任意成分であるが、添加する際の割合は、（ａ）芳香族成分を含むポリアミド樹脂１００重量部に対して、０．０１重量部以上１００重量部以下が好ましい。１００重量部より多いと混練時に分解ガスが発生したり、成形加工時に成形金型に汚染性物質が付着したりするなどの問題が発生し、０．０１重量部より少ないと添加しない場合と比べて、難燃性の向上、流動性の向上や耐衝撃性の向上があまりみられない。より好ましくは０．０５重量部以上８０重量部以下であり、更に好ましくは０．１重量部以上６０重量部以下である。
【００３７】
（ｅ）ポリフェニレンエーテル樹脂は、任意成分であるが、添加する際の割合は、（ａ）芳香族成分を含むポリアミド樹脂１００重量部に対して、０．１重量部以上１００重量部以下が好ましい。１００重量％より多いとポリアミド樹脂がもつ成形加工性、機械的物性が低下し、０．１重量部以下だと流動性の向上はほとんど見られない。より好ましくは、１重量部以上８０重量部以下であり、更に好ましくは３重量部以上６０重量部以下である。
【００３８】
本明細書中でのハロゲン系難燃剤、アンチモン系難燃助剤、リン系難燃剤とは、ハロゲン化合物、アンチモン化合物、リン化合物の中で難燃性を高めることを目的とした化合物に該当する。しかし、本願の難燃性に影響を与えない範囲で、難燃性以外の耐熱安定性など性質を高めるため等の目的のハロゲン化合物、アンチモン化合物、リン化合物はこの表現からは外れる。
【００３９】
難燃性を高めることを目的とした化合物として、まずハロゲン化合物として、例として、塩素系難燃剤として塩素化パラフィン、塩素化ポリエチレン、ドデカクロロペンタシクロオクタデカ−７，１５−ジエン（オキシデンタルケミカル社製デクロランプラス２５<登録商標>）、無水ヘット酸等、臭素系難燃剤としてヘキサブロモシクロドデカン（ＨＢＣＤ）、デカブロモジフェニルオキサイド（ＤＢＤＰＯ）、オクタブロモジフェニルオキサイド、テトラブロモビスフェノールＡ（ＴＢＢＡ）、ビス（トリブロモフェノキシ）エタン、ビス（ペンタブロモフェノキシ）エタン（ＢＰＢＰＥ）、テトラブロモビスフェノールＡエポキシ樹脂（ＴＢＢＡエポキシ）、テトラブロモビスフェノールＡカーボネート（ＴＢＢＡ−ＰＣ）、エチレン（ビステトラブロモフタル）イミド（ＥＢＴＢＰＩ）、エチレンビスペンタブロモジフェニル、トリス（トリブロモフェノキシ）トリアジン（ＴＴＢＰＴＡ）、ビス（ジブロモプロピル）テトラブロモビスフェノールＡ（ＤＢＰ−ＴＢＢＡ）、ビス（ジブロモプロピル）テトラブロモビスフェノールＳ（ＤＢＰ−ＴＢＢＳ）、臭素化ポリフェニレンエーテル（ポリジプロモフェニレンエーテル等を含む）（ＢｒＰＰＥ）、臭素化ポリスチレン（ポリジブロモスチレン等を含む）（ＢｒＰＳ）、臭素化架橋芳香族重合体、臭素化エポキシ樹脂、臭素化フェノキシ樹脂、臭素化スチレン−無水マレイン酸重合体、テトラブロモビスフェノールＳ（ＴＢＢＳ）、トリス（トリブロモネオペンチル）フォスフェート（ＴＴＢＮＰＰ）、ポリブロモトリメチルフェニルインダン（ＰＢＰＩ）、トリス（ジブロモプロピル）−イソシアヌレート（ＴＤＢＰＩＣ）等、反応型難燃剤としてテトラブロモビスフェノールＡ（ＴＢＢＡ）（臭素系難燃剤にも記載）、テトラブロモフタレート、テトラブロモフタレートジオール、テトラブロモフタレートエステル、テトラブロモフタレートジソジウム、テトラクロロ無水フタル酸、テトラブロモ無水フタル酸、トリブロモフェノール（ＴＢＰ）、ジブロモフェノール、ジブロモメタクレゾール、ジブロモネオペンチルグリコール、ポリ（ペンタブロモベンジルポリアクリレート）（ＰＰＢＢＡ）、クロレント酸、無水クロレント酸、臭素化フェノール、ジブロモクレジルグリシジルエーテル、ビニルブロマイド、ジブロモスチレン、トリブロモスチレン等が挙げられる。
【００４０】
次に、アンチモン化合物としては、例として、三酸化アンチモン、四酸化アンチモン、五酸化アンチモン等の酸化アンチモン類やアンチモン酸ソーダ等が挙げられる。
三番目に、リン化合物としては、例として、赤リン系難燃剤として赤リン、リン酸エステル系難燃剤として、トリフェニルフォスフェート（ＴＰＰ）、トリクレジルフォスフェート（ＴＣＰ）、トリキシレニルフォスフェート（ＴＸＰ）、トリエチルフォスフェート、トリブチルフォスフェート（ＴＢＰ）、トリオクチルフォスフェート（ＴＯＰ）、トリス（ブトキシエチル）フォスフェート、クレジルジフェニルフォスフェート（ＣＤＰ）、キシレニルジフェニルフォスフェート、ビス（ノニルフェニル）フェニルフォスフェート（ＤＮＰ）、クレジルビス（ジ２，６−キシレニル）フォスフェート、２−エチルヘキシルジフェニルフォスフェート、レゾルシノールビス（ジフェニル）フォスフェート（ＲＤＰ）、ビスフェノールＡビス（ジフェニル）フォスフェート（ＢＰＡ−ＤＰ）、ビスフェノールＡビス（ジクレジル）フォスフェート（ＢＰＡ−ＤＣ）、レゾルシノールビス（ジ２，６−キシレニル）フォスフェート、ジエチルーＮ，Ｎ−ビス（２−ヒドロキシエチル）アミノメチルホスフォネート、ジメチルメチルフォスフォネート等、ハロゲン化リン酸エステル系難燃剤として、トリス（クロロエチル）フォスフェート、トリス（クロロプロピル）フォスフェート、トリス（ジクロロプロピル）フォスフェート、トリス（トリブロモネオペンチル）フォスフェート等、リン酸アミド系難燃剤として、トリフェニルフォスフォルアミド等、リン酸塩系難燃剤として、ポリリン酸アンモニウム（ＡＰＰ）、リン酸メラミン、リン酸グアニジン、ピロリン酸メラミン、ポリリン酸メラミン等、フォスフィン系難燃剤としては、トリフェニルフォスフィン、トリフェニルフォスフィンオキサイド、テトラキス（ヒドロキシメチル）フォスフォニウムクロライド、テトラキス（ヒドロキシメチル）サルフェイト等、フォスファゼン系難燃剤としては、プロポキシフォスファゼン、フェノキシフォスファゼン、アミノフォスファゼン、ポリ（フロロアルキルフォスファゼン）、ジプロポキシフォスファゼン等のリン化合物が挙げられる。
【００４１】
一方、本願の難燃性に影響を与えない範囲で、耐熱安定性向上や変色防止等のための化合物として一般的に用いられているもの、例えば、ハロゲンを含むものとしては、ヨウ化カリウム、臭化カルウム、塩化銅、臭化銅、ヨウ化銅等のハロゲン化合物、リン系の熱安定剤、リン酸銅、テトラキス（２，４−ジ−ｔ−ブチルフェニル）−４，４'−ビフェニレンフォスフォナイト、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、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、トリフェニルホスファイト、トリス（２，４−ジ−ｔ−ブチルフェニル）フォスファイト、ジフェニルイソデシルフォスファイト、フェニルジイソデシルフォスファイト、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）フォスファイト、サイクリックネオペンタンテトライルビス（オクタデシルホスファイト）、サイクリックネオペンタンテトライルビス（２，６−ジ−ｔ−ブチル−４−メチルフェニル）ホスファイト、トリス（ノニル・フェニル）ホスファイト、ジイソデシルペンタエリスリトールジフォスファイト、９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキサイド、１０−（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）−９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキサイド、１０−デシロキシ−９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン、リン酸トリメチル、次亜リン酸ナトリウム等のリン化合物等が挙げられる。
【００４２】
本発明の組成物に、難燃性を更に一層向上させるために、芳香族を含む熱可塑性樹脂を加えることができる。例えば、ポリスチレン樹脂、シンジオタクチックポリスチレン樹脂、ポリフェニレンエーテル樹脂、ポリフェニレンスルフィド樹脂、ポリアミドイミド樹脂、ポリアリルエーテルケトン樹脂、ポリエーテルエーテルケトン樹脂、ポリエーテルイミド樹脂、ポリエーテルケトン樹脂、ポリエーテルケトンケトン樹脂、ポリエーテルサルホン樹脂、ポリフタルアミド樹脂、ポリサルホン樹脂等が挙げられる。
【００４３】
更に、ポリフェニレンエーテル樹脂、ポリフェニレンスルフィド樹脂が燃焼時に生成する不燃層（又は炭化層）が多く、難燃性に優れ、そしてまた、外観に優れるので好ましい。そして特に、ポリフェニレンエーテル樹脂が最も好ましい。本発明の強化された難燃性ポリアミド樹脂組成物の製造方法は、特に限定はなく、ポリアミド樹脂、ホウ酸金属化合物、強化材（任意成分）、シリコーン化合物（任意成分）、ポリフェニレンエーテル樹脂（任意成分）を常用の単軸または２軸の押出機やニーダー等の混練機を用いて、２００〜３５０℃の温度で溶融混練する方法等であればよい。
【００４４】
本発明の難燃性ポリアミド樹脂組成物には、本発明の目的を損なわない範囲で、他の成分、例えば難燃剤、フィブリル化剤、顔料、染料等の着色剤や、熱可塑性樹脂の一般的な熱安定剤である銅系熱安定剤（例えばヨウ化銅、酢酸銅等とヨウ化カリウム、臭化カルウムとの併用）、ヒンダードフェノール系酸化劣化防止剤に代表される有機系耐熱剤、耐候性改良剤、核剤、可塑剤、帯電防止剤等の添加剤等を添加することができる。また、不燃層（又は炭化層）の発泡を促進し、断熱効果を増大し、高難燃性を発現するために、燃焼時に水蒸気、窒素、二酸化炭素等のガス成分を発生させる成分、例えば水酸化アルミニウム、水酸化マグネシウム等の水酸化金属化合物、メラミン、メレム、メロン、メラミンシアヌレート等の窒素化合物、炭酸カルシウム等の炭酸金属化合物を添加させることもできる。
本発明の組成物は、射出成形、押出成形、ブロー成形など公知の方法によってコネクター、コイルボビン、ブレーカー、電磁開閉器、ホルダー、プラグ、スイッチ等の電気、電子、自動車用途の各種成形品に成形される。
【００４５】
【発明の実施の形態】
以下の実施例により本発明をさらに詳しく説明するが、本発明はこれに限定されるものではない。
なお、実施例及び比較例に用いた原材料及び測定方法を以下に示す。
［原材料］
（ａ）芳香族成分を含むポリアミド樹脂
（ａ−１）：ポリアミドＭＸＤ６ 三菱エンジニアリングプラスチックス（株）製 商品名 レニー６００２
（ａ−２）：製造例１のポリアミド６６／６Ｉ （共重合成分のモル比 ６６：６Ｉ＝８５：１５）
【００４６】
（ｂ）ホウ酸金属化合物
（ｂ−１）：ホウ酸亜鉛（水和物）２ＺｎＯ・３Ｂ₂Ｏ₃・３．５Ｈ₂Ｏ Ｕ．Ｓ． Ｂｏｒａｘ社製 商品名 Ｆｉｒｅｂｒａｋｅ ＺＢ
（ｂ−２）：ホウ酸亜鉛（無水物）２ＺｎＯ・３Ｂ₂Ｏ₃ Ｕ．Ｓ． Ｂｏｒａｘ社製 商品名 Ｆｉｒｅｂｒａｋｅ ５００
（ｃ）強化材
（ｃ−１）：ガラス繊維 日本電気硝子（株）製 商品名 ＥＣＴ０３Ｔ２７５Ｈ／ＰＬ（平均繊維径１０μｍ）
【００４７】
（ｄ）シリコーン化合物
（ｄ−１）：ビニル基含有シリコーン（２０℃において液状） 信越化学工業（株）製 商品名 Ｘ−４０−９２４３
このシリコーン化合物を重クロロホルムに溶解させ、²⁹Ｓｉ−ＮＭＲ及び¹Ｈ−ＮＭＲ測定し、シリコーン化合物の構造解析を行い、ビニル基の有無を確認した。また、この測定で得られた積分比よりこのシリコーン化合物は末端基（トリメチルシリル基やアルコキシ基等）を除くケイ素上の全有機置換基の内、ビニル基率はモル比で１０％であった。
（ｄ−２）：製造例３のビニル基含有シリコーン化合物（２０℃において液状）
ｄ−１と同様に測定を行い、ビニル基率はモル比で８％であった。
（ｄ−３）：ジメチルシリコーンオイル（２０℃において液状） 信越化学工業（株）製 商品名 ＫＦ９６−１００
（ｄ−４）：シリコーンレジン（無溶剤メチル系ワニス）（２０℃において固体状） ＧＥ東芝シリコーン（株）製 商品名 ＹＲ３３７０
（ｅ）ポリフェニレンエーテル樹脂
（ｅ−１）：製造例２の無水マレイン酸変性ポリフェニレンエーテル
【００４８】
【製造例１】
アジピン酸とヘキサメチレンジアミンの等モル塩２．００ｋｇとイソフタル酸とヘキサメチレンジアミンの等モル塩０．３５ｋｇ、アジピン酸０．１ｋｇ、および純水２．５ｋｇを５Ｌのオートクレーブの中に仕込み良く撹拌した。充分窒素置換した後、撹拌しながら温度を室温から２２０℃まで約１時間かけて昇温した。この際、オートクレーブ内の水蒸気による自然圧で内圧はゲージ圧で１．７６ＭＰａになるが、１．７６ＭＰａ以上の圧にならないよう水を反応系外に除去しながら加熱を続けた。更に２時間後内温が２６０℃に到達した時点で加熱を止め、オートクレーブのバルブを閉止し、約８時間かけて室温まで冷却した。冷却後オートクレーブを開け、約２ｋｇのポリマーを取りだし粉砕した。得られた粉砕ポリマーを、１０Ｌのエバポレーターに入れ窒素気流下、２００℃で１０時間固相重合した。固相重合によって得られたポリアミドは、融点２４５℃、硫酸相対粘度２．３８であった。
【００４９】
【製造例２】
２，６−ジメチルフェノールを酸化重合して得られた還元粘度（０．５ｇ／ｄｌクロロホルム溶液、３０℃測定）０．５２のポリ（２，６−ジメチル−１，４−フェニレンエーテル）（以下ポリフェニレンエーテルと略記）を１００重量部と、相溶化剤として無水マレイン酸を１．０重量部とを上流側に１ヶ所（以下ｔｏｐ−Ｆと略記）と、押出機中央部並びにダイに近い下流側の２ヶ所に供給口（以下押出機中央部をｓｉｄｅ−１、ダイに近い下流側をｓｉｄｅ−２とそれぞれ略記）を有する二軸押出機（Ｗｅｒｎｅｒ＆Ｐｆｌｅｉｄｅｒｅｒ社製：ＺＳＫ−４０）のｓｉｄｅ−１とｓｉｄｅ−２は塞いだ状態にして、シリンダー設定温度３２０℃、スクリュー回転３００ｒｐｍ、吐出量２０．１５ｋｇ／ｈｒの条件下で、ポリフェニレンエーテルと無水マレイン酸をドライブレンドしたものをｔｏｐ−Ｆより供給し、溶融混練してストランド状に取り出し、ストランドバス（水槽）で冷却後、カッターで造粒し無水マレイン酸変性ポリフェニレンエーテルのペレットを得た。
【００５０】
【製造例３】
トリクロロフェニルシラン４２．３ｇ、ジクロロメチルビニルシラン４２．３ｇ、ジクロロメチルフェニルシラン３８．２ｇ、ジクロロジメチルシラン１６７．８ｇの混合液を水４５０．８ｇ、トルエン１４３ｇの混合液中にゆっくり滴下し加水分解した後、８０℃で１時間熟成した。そして、過剰量のクロロトリメチルシランを反応液に滴下し、さらに８０℃で１時間熟成した。分液ロートで水相を捨て、有機（トルエン）相を中性になるまで１０％硫酸ナトリウム水溶液で数回抽出した。
その後、蒸留装置に有機相を移して、ある程度溶媒のトルエンを除去し、最後にエバポレーターを用いて溶媒を完全に減圧留去を行い、ビニル基含有シリコーン約１８０ｇを得た。
この一連の操作を必要な量に達するまで繰り返した。
【００５１】
［測定方法］
（１）ＵＬ−９４ＶＢ
ＵＬ９４（米国Ｕｎｄｅｒ Ｗｒｉｔｅｒｓ Ｌａｂｏｒａｔｏｒｉｅｓ Ｉｎｃで定められた規格）の方法を用いて１サンプル当たりそれぞれ１０本づつ測定を行った。なお試験片は長さが１２７ｍｍ、幅が１２．７ｍｍ、厚みが１／８インチとし、射出成形機（日精工業（株）製：ＰＳ４０Ｅ）を用いて成形して得た。また厚みが１／８インチの試験片でＶ−０又はＶ−１であったサンプルについてはより厳しい条件となる厚さが１／１６インチについても射出成形機（日精工業（株）製：ＰＳ４０Ｅ）を用いて成形して得た。
ドリップには、各試料の試験中に綿着火の原因となるドリップをしたサンプル数を示した。平均時間（ｓ）には、各試料１０秒間を２回即ち計２０回接炎後の消炎時間の平均燃焼時間を示した。最大時間（ｓ）には、同じく計２０回接炎後の消炎時間の最大燃焼時間を示した。しかし、試験片が燃え尽きてしまった場合や消炎時間が長すぎて、明らかにＶ−０、Ｖ−１、Ｖ−２のいずれのも該当しない場合のサンプルについては平均時間、最大時間には値を記載しない。評価にはＵＬ９４垂直燃焼試験によって分類される難燃性のクラスを示した。分類方法の概要は以下の通り。詳細はＵＬ９４規格に準じる。
【００５２】
Ｖ−０
綿着火無し 平均燃焼時間５秒以下 最大燃焼時間１０秒以下
Ｖ−１
綿着火無し 平均燃焼時間２５秒以下 最大燃焼時間３０秒以下
Ｖ−２
綿着火有り 平均燃焼時間２５秒以下 最大燃焼時間３０秒以下
Ｖ−２ｏｕｔ
上記３項目に該当しない
【００５３】
（２）成形性
射出成形機（日精工業（株）製：ＰＳ４０Ｅ）を用いて、それぞれのサンプルの短冊試験片（３．２×１２．７×１２７ｍｍ）を成形した際に、射出成形機のペレットホッパーから成形機スクリューへの樹脂の供給効率を評価した。全く問題なくペレットがスクリュー部へ供給されるものを合格（◎）、合格よりも多少供給に問題（具体的には、ペレットがスクリューに食い込みにくい等）があり、可塑化時間が長くなるが、射出サイクルにはほとんど問題ないものをやや合格（○）、供給に問題があり、全サンプル中半分以下のサンプルで射出サイクルが遅れてしまうものをやや不合格（△）、供給にかなり問題があり、全サンプル中半分以上のサンプルで射出サイクルが遅れてしまうものを不合格（×）とした。
【００５４】
（３）ＭＤ
上記の成形性評価と同時にそれぞれのサンプル成形でのモールドデポジット（ＭＤ）の付着も目視で判断した。評価は各サンプル３０ショット成形後の金型への付着物を判断し、ＭＤが全く無いものを合格（◎）、ＭＤが少量あるがほとんど問題なしのものをやや合格（○）、ＭＤが多く少し問題になるものをやや不合格（△）、ＭＤがかなり多く問題になるものを不合格（×）とした。
【００５５】
（４）燃焼挙動（コーンカロリーメーター試験）
サンプルの燃焼の様子を調べるために、燃焼中の発熱速度の経時変化が観測できるコーンカロリーメーターを用いて、燃焼挙動を調べた。
装置は、（株）東洋精機製作所製コーンカロリーメーターＩＩＩをもちいた。燃焼させるサンプルは、５．０ｍｍ×３２．５ｍｍ×１１４ｍｍの厚肉試験片を射出成形機（東芝機械製：ＩＳ１５０）で成形したものを切削し、５．０ｍｍ×３２．５ｍｍ×１００ｍｍの形状のサンプルを得た。このサンプルをアルミ箔を用いて測定時に上面となる３２．５ｍｍ×１００ｍｍの一面を残して、他の５面（側面及び下面）を覆った。
測定条件としては、コーンヒーターの輻射量を５０ｋＷ／ｍ²、排気流量を０．０２４ｍ³／ｓｅｃ、オリフィスタイプをラージ、サンプルの上面とコーンヒーターとの距離を２５ｍｍ、測定までサンプルを輻射熱遮断するためにシャッターとイグナイタ（試料から発生した可燃性ガスに着火させるための１０ｋＶの高電圧スパーク）を用いる設定で行った。シャッターを開け、コーンヒーターの輻射熱による加熱が始まると同時に試験開始とし、試料が加熱で分解し、その分解ガスにイグナイタで着火し、サンプルが燃焼し、燃えなくなるまで続けた。
【００５６】
評価は、単位面積あたりの発熱速度＝Ｈ．Ｒ．Ｒ．（ｋＷ／ｍ²）を燃焼の激しさの指標として行った。
最大Ｈ．Ｒ．Ｒ．は、サンプルに着火してから消えるまでの間のＨ．Ｒ．Ｒ．の最大値を示した。
平均Ｈ．Ｒ．Ｒ．は、サンプルに着火してから消えるまでの間のＨ．Ｒ．Ｒ．の平均値を示した。
不燃層の厚みは、サンプル燃焼中に形成される不燃層（又は炭化層）の厚みを測ることを目的に、試験後の燃え残ったサンプルの高さの最大値をノギスを用いて測定した。ちなみに試験前の高さは５ｍｍである。
そして、この不燃層の厚みが、厚いものほど未燃焼の樹脂（燃料）と炎（熱源）の距離が大きく、即ち断熱効果が大きくなり、燃焼の継続を抑制できるので、高い難燃性を発現できる。
不燃層の硬さは、サンプル燃焼中に形成される不燃層（又は炭化層）の強さを測ることを目的に、試験後の燃え残ったサンプルを指で突いた際の抵抗より判断した。硬いものは◎、やや硬いものは○、脆いものは×とした。
【００５７】
（５）グローワイヤー発火性試験（ＧＷＩ）
ＩＥＣ６０６９５−２−１規格の方法で、日立化成工業（株）製 グローワイヤー燃焼性試験機 ＨＡＴ−２１４の装置を用いて、燃焼性（ＧＷＦＩ）、着火性（ＧＷＩＴ）の試験項目について試験を行った。なお試験片は６５ｍｍ×９０ｍｍ×１．０ｍｍ（厚み１．０ｍｍ）とし、射出成形機（東芝機械製：ＩＳ１５０）を用いて成形して得た。
【００５８】
（６）電気特性（ＣＴＩ）
ＩＥＣ Ｐｕｂｌｉｃａｔｉｏｎ １１２規格の方法で、日立化成工業（株）製耐トラッキング試験機 ＨＡＴ−５００−３型の装置を用いて、耐トラッキング試験を行った。なお試験片は１３０ｍｍ×１３０ｍｍ×３．０ｍｍ（厚み３．０ｍｍ）とし、射出成形機（東芝機械製：ＩＳ１５０）を用いて成形して得た。測定の概要は試験片を装置にセットし、試験片表面に二本の電極によって１００〜６００Ｖの電圧を印加し、その電極間に０．１％塩化アンモニウム水溶液を３０秒毎に滴下し、試験片がトラッキングを起こすことなく、５０滴で破壊しない最大電圧（ＣＴＩ）を測定し、その値を示した。この値が高いほど耐トラッキング性に優れる。
【００５９】
【実施例１】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（７２．０重量％）、ホウ酸金属化合物ｂ−１が１１．１重量部（８．０重量％）、強化材ｃ−１が２７．８（２０．０重量％）からなるポリアミド組成物を得た。
原材料（即ち、押出機への投入速度の設定）は芳香族成分を含むポリアミド樹脂ａ−１が７２．０重量％、ホウ酸金属化合物ｂ−１が８．０重量％、強化材ｃ−１が２０．０重量％となるように用意し、上流側に１ヶ所（以下ｔｏｐ−Ｆと略記）と、押出機中央部並びにダイに近い下流側の２ヶ所に供給口（以下押出機中央部をｓｉｄｅ−１、ダイに近い下流側をｓｉｄｅ−２とそれぞれ略記）を有する二軸押出機（東芝機械製：ＴＥＭ３５）を用いてシリンダー設定温度２４０℃、スクリュー回転２００ｒｐｍ、吐出量３０ｋｇ／ｈｒの条件下で、芳香族成分を含むポリアミド樹脂ａ−１はｔｏｐ−Ｆから、ホウ酸金属化合物ｂ−１はｓｉｄｅ−１から、強化材ｃ−１はｓｉｄｅ−２から合計の吐出量が３０ｋｇ／ｈｒになるようにそれぞれ調節して供給し、溶融混練してストランド状に取り出し、ストランドバス（水槽）で冷却後、カッターで造粒しポリアミド樹脂組成物ペレットを得た。
得られたペレットを前記した測定方法にてＵＬ−９４ＶＢ、成形性、ＭＤ、燃焼挙動（コーンカロリーメーター試験）、グローワイヤー発火性試験（ＧＷＩ）、電気特性（ＣＴＩ）を調べた。その結果を表１と表２に示す。
【００６０】
【実施例２】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（６４．０重量％）、ホウ酸金属化合物ｂ−１が２５．０重量部（１６．０重量％）、強化材ｃ−１が３１．３重量部（２０．０重量％）からなるポリアミド組成物を得た。
用意する原材料（即ち、押出機への投入速度の設定）を芳香族成分を含むポリアミド樹脂ａ−１が６４．０重量％、ホウ酸金属化合物ｂ−１が１６．０重量％とした以外は実施例１と同様にしてペレットを得て、ＵＬ−９４ＶＢ、成形性、ＭＤ、燃焼挙動（コーンカロリーメーター試験）、グローワイヤー発火性試験（ＧＷＩ）、電気特性（ＣＴＩ）を調べた。その結果を表１と表２に示す。
【００６１】
【製造例４】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（９０．０重量％）、シリコーン化合物ｄ−１が１１．１重量部（１０．０重量％）からなる１０重量％シリコーン含有ポリアミド樹脂組成物を得た。
上流側に１ヶ所（以下ｔｏｐ−Ｆと略記）と、押出機中央部に１ヶ所に供給口（以下押出機中央部をｓｉｄｅ−１と略記）を有する二軸押出機（Ｗｅｒｎｅｒ＆Ｐｆｌｅｉｄｅｒｅｒ社製：ＺＳＫ−２５）のシリンダーの中央付近（トップフィード用ホッパーから１０ブロック中６ブロック目）に液添装置を取り付け、ｓｉｄｅ−１を塞いだものを用いて、シリンダー設定温度２４０℃、スクリュー回転３００ｒｐｍ、吐出量１０ｋｇ／ｈｒの条件下で、芳香族成分を含むポリアミド樹脂ａ−１を添加量９．０ｋｇ／ｈｒでｔｏｐ−Ｆより供給し、シリコーン化合物ｄ−１は液添装置を用いて添加量１．０ｋｇ／ｈｒでシリンダー系中に直接添加し、両者を混練してストランド状に取り出し、ストランドバス（水槽）で冷却後、カッターで造粒し１０重量％シリコーン含有ポリアミド樹脂組成物ペレットを得た。
【００６２】
【実施例３】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（７０．０重量％）、ホウ酸金属化合物ｂ−１が１１．４重量部（８．０重量％）、強化材ｃ−１が２８．６重量部（２０．０重量％）、シリコーン化合物ｄ−１が２．９重量部（２．０重量％）からなるポリアミド組成物を得た。
原材料（即ち、押出機への投入速度の設定）は芳香族成分を含むポリアミド樹脂ａ−１が５２．０重量％、製造例４の１０重量％シリコーン含有ポリアミド樹脂が２０．０重量％、ホウ酸金属化合物ｂ−１が８．０重量％、強化材ｃ−１が２０．０重量％となるように用意し、上流側に１ヶ所と、押出機中央部並びにダイに近い下流側の２ヶ所に供給口を有する二軸押出機（東芝機械製：ＴＥＭ３５）を用いてシリンダー設定温度２４０℃、スクリュー回転２００ｒｐｍ、吐出量３０ｋｇ／ｈｒの条件下で、芳香族成分を含むポリアミド樹脂ａ−１と製造例４の１０重量％シリコーン含有ポリアミド樹脂はｔｏｐ−Ｆから、ホウ酸金属化合物ｂ−１はｓｉｄｅ−１から、強化材ｃ−１はｓｉｄｅ−２から合計の吐出量が３０ｋｇ／ｈｒになるようにそれぞれ調節して供給し、溶融混練してストランド状に取り出し、ストランドバス（水槽）で冷却後、カッターで造粒しポリアミド樹脂組成物ペレットを得た。
得られたペレットを前記した測定方法にてＵＬ−９４ＶＢ、成形性、ＭＤ、燃焼挙動（コーンカロリーメーター試験）、グローワイヤー発火性試験（ＧＷＩ）、電気特性（ＣＴＩ）を調べた。その結果を表１と表２に示す。
【００６３】
【実施例４】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（６８．０重量％）、ホウ酸金属化合物ｂ−１が１１．８重量部（８．０重量％）、強化材ｃ−１が２９．４重量部（２０．０重量％）、シリコーン化合物ｄ−１が５．９重量部（４．０重量％）からなるポリアミド組成物を得た。
用意する原材料（即ち、押出機への投入速度の設定）を芳香族成分を含むポリアミド樹脂ａ−１が３２．０重量％、製造例４の１０重量％シリコーン含有ポリアミド樹脂が４０．０重量％とした以外は実施例３と同様にしてペレットを得て、ＵＬ−９４ＶＢ、成形性、ＭＤ、燃焼挙動（コーンカロリーメーター試験）、グローワイヤー発火性試験（ＧＷＩ）、電気特性（ＣＴＩ）を調べた。その結果を表１と表２に示す。
【００６４】
【実施例５】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（６４．８重量％）、ホウ酸金属化合物ｂ−１が１２．３重量部（８．０重量％）、強化材ｃ−１が３０．９重量部（２０．０重量％）、シリコーン化合物ｄ−１が１１．１重量部（７．２重量％）からなるポリアミド組成物を得た。
用意する原材料（即ち、押出機への投入速度の設定）を芳香族成分を含むポリアミド樹脂ａ−１が０重量％、製造例４の１０重量％シリコーン含有ポリアミド樹脂が７２．０重量％とした以外は実施例３と同様にしてペレットを得て、ＵＬ−９４ＶＢ、成形性、ＭＤ、燃焼挙動（コーンカロリーメーター試験）、グローワイヤー発火性試験（ＧＷＩ）、電気特性（ＣＴＩ）を調べた。その結果を表１と表２に示す。
【００６５】
【実施例６】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（６４．８重量％）、ホウ酸金属化合物ｂ−２が１２．３重量部（８．０重量％）、強化材ｃ−１が３０．９重量部（２０．０重量％）、シリコーン化合物ｄ−１が１１．１重量部（７．２重量％）からなるポリアミド組成物を得た。
用意する原材料（即ち、押出機への投入速度の設定）を芳香族成分を含むポリアミド樹脂ａ−１が０重量％、製造例４の１０重量％シリコーン含有ポリアミド樹脂が７２．０重量％、ホウ酸金属化合物ｂ−２が８．０重量％とした以外は実施例３と同様にしてペレットを得て、ＵＬ−９４ＶＢ、成形性、ＭＤ、燃焼挙動（コーンカロリーメーター試験）、グローワイヤー発火性試験（ＧＷＩ）、電気特性（ＣＴＩ）を調べた。その結果を表１と表２に示す。
【００６６】
【製造例５】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（９０．０重量％）、シリコーン化合物ｄ−２が１１．１重量部（１０．０重量％）からなる１０重量％シリコーン含有ポリアミド樹脂組成物を得た。
シリコーン化合物をｄ−２にした以外は、製造例４と同様にして、１０重量％シリコーン含有ポリアミド樹脂組成物ペレットを得た。
【００６７】
【実施例７】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（６４．８重量％）、ホウ酸金属化合物ｂ−１が１２．３重量部（８．０重量％）、強化材ｃ−１が３０．９重量部（２０．０重量％）、シリコーン化合物ｄ−２が１１．１重量部（７．２重量％）からなるポリアミド組成物を得た。
用意する原材料（即ち、押出機への投入速度の設定）を芳香族成分を含むポリアミド樹脂ａ−１が０重量％、製造例５の１０重量％シリコーン含有ポリアミド樹脂が７２．０重量％とした以外は実施例３と同様にしてペレットを得て、ＵＬ−９４ＶＢ、成形性、ＭＤ、燃焼挙動（コーンカロリーメーター試験）、グローワイヤー発火性試験（ＧＷＩ）、電気特性（ＣＴＩ）を調べた。その結果を表１と表２に示す。
【００６８】
【比較例１】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（８０．０重量％）、強化材ｃ−１が２５．０重量部（２０．０重量％）からなるポリアミド組成物を得た。
用意する原材料（即ち、押出機への投入速度の設定）を芳香族成分を含むポリアミド樹脂ａ−１が８０．０重量％、ホウ酸金属化合物ｂ−１が０重量％とした以外は実施例１と同様にしてペレットを得て、ＵＬ−９４ＶＢ、成形性、ＭＤ、燃焼挙動（コーンカロリーメーター試験）、グローワイヤー発火性試験（ＧＷＩ）、電気特性（ＣＴＩ）を調べた。その結果を表１と表２に示す。
【００６９】
【比較例２】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（９０．０重量％）、シリコーン化合物ｄ−１が１１．１重量部（１０．０重量％）からなるポリアミド組成物を得た。
製造例４の１０重量％シリコーン含有ポリアミド樹脂ペレットをそのまま利用し、ＵＬ−９４ＶＢ、成形性、ＭＤ、燃焼挙動（コーンカロリーメーター試験）を調べた。その結果を表１と表２に示す。
【００７０】
【比較例３】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（７２．０重量％）、強化材ｃ−１が２７．８重量部（２０．０重量％）、シリコーン化合物ｄ−１が１１．１重量部（８．０重量％）からなるポリアミド組成物を得た。
用意する原材料（即ち、押出機への投入速度の設定）を芳香族成分を含むポリアミド樹脂ａ−１が０重量％、製造例４の１０重量％シリコーン含有ポリアミド樹脂が８０．０重量％、ホウ酸金属化合物ｂ−１が０重量%とした以外は実施例３と同様にしてペレットを得て、ＵＬ−９４ＶＢ、成形性、ＭＤ、燃焼挙動（コーンカロリーメーター試験）、グローワイヤー発火性試験（ＧＷＩ）、電気特性（ＣＴＩ）を調べた。その結果を表１と表２に示す。
【００７１】
【製造例６】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（９０．０重量％）、シリコーン化合物ｄ−３が１１．１重量部（１０．０重量％）からなる１０重量％シリコーン含有ポリアミド樹脂組成物を得た。
シリコーン化合物をｄ−３にした以外は、製造例４と同様にして、１０重量％シリコーン含有ポリアミド樹脂組成物ペレットを得た。
【００７２】
【実施例８】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（７０．０重量％）、ホウ酸金属化合物ｂ−１が１１．４重量部（８．０重量％）、強化材ｃ−１が２８．６（２０．０重量％）、シリコーン化合物ｄ−３が２．９重量部（２．０重量％）からなるポリアミド組成物を得た。
原材料（即ち、押出機への投入速度の設定）は芳香族成分を含むポリアミド樹脂ａ−１が５２．０重量％、製造例６の１０重量％シリコーン含有ポリアミド樹脂が２０．０重量％、ホウ酸金属化合物ｂ−１が８．０重量％、強化材ｃ−１が２０．０重量％となるように用意し、上流側に１ヶ所と、押出機中央部並びにダイに近い下流側の２ヶ所に供給口を有する二軸押出機（東芝機械製：ＴＥＭ３５）を用いてシリンダー設定温度２４０℃、スクリュー回転２００ｒｐｍ、吐出量３０ｋｇ／ｈｒの条件下で、芳香族成分を含むポリアミド樹脂ａ−１と製造例６の１０重量％シリコーン含有ポリアミド樹脂はｔｏｐ−Ｆから、ホウ酸金属化合物ｂ−１はｓｉｄｅ−１から、強化材ｃ−１はｓｉｄｅ−２から合計の吐出量が３０ｋｇ／ｈｒになるようにそれぞれ調節して供給し、溶融混練してストランド状に取り出し、ストランドバス（水槽）で冷却後、カッターで造粒しポリアミド樹脂組成物ペレットを得た。
得られたペレットを前記した測定方法にてＵＬ−９４ＶＢ、成形性、ＭＤを調べた。その結果を表３に示す。
【００７３】
【実施例９】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（６８．０重量％）、ホウ酸金属化合物ｂ−１が１１．８重量部（８．０重量％）、強化材ｃ−１が２９．４重量部（２０．０重量％）、シリコーン化合物ｄ−３が５．９重量部（４．０重量％）からなるポリアミド組成物を得た。
用意する原材料（即ち、押出機への投入速度の設定）を芳香族成分を含むポリアミド樹脂ａ−１が３２．０重量％、製造例６の１０重量％シリコーン含有ポリアミド樹脂が４０．０重量％とした以外は実施例８と同様にしてペレットを得て、ＵＬ−９４ＶＢ、成形性、ＭＤを調べた。その結果を表３に示す。
【００７４】
【実施例１０】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（６４．８重量％）、ホウ酸金属化合物ｂ−１が１２．３重量部（８．０重量％）、強化材ｃ−１が３０．９重量部（２０．０重量％）、シリコーン化合物ｄ−３が１１．１重量部（７．２重量％）からなるポリアミド組成物を得た。
用意する原材料（即ち、押出機への投入速度の設定）を芳香族成分を含むポリアミド樹脂ａ−１が０重量％、製造例６の１０重量％シリコーン含有ポリアミド樹脂が７２．０重量％とした以外は実施例８と同様にしてペレットを得て、ＵＬ−９４ＶＢ、成形性、ＭＤを調べた。その結果を表３に示す。
【００７５】
【実施例１１】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（６４．８重量％）、ホウ酸金属化合物ｂ−１が１２．３重量部（８．０重量％）、強化材ｃ−１が３０．９重量部（２０．０重量％）、シリコーン化合物ｄ−４が１１．１重量部（７．２重量％）からなるポリアミド組成物を得た。
原材料（即ち、押出機への投入速度の設定）は芳香族成分を含むポリアミド樹脂ａ−１が６４．８重量％、ホウ酸金属化合物ｂ−１が８．０重量％、強化材ｃ−１が２０．０重量％、細かく粉砕して粉末にしたシリコーン化合物ｄ−４が７．２重量％となるように用意し、上流側に１ヶ所と、押出機中央部並びにダイに近い下流側の２ヶ所に供給口を有する二軸押出機（東芝機械製：ＴＥＭ３５）を用いてシリンダー設定温度２４０℃、スクリュー回転２００ｒｐｍ、吐出量３０ｋｇ／ｈｒの条件下で、芳香族成分を含むポリアミド樹脂ａ−１とシリコーン化合物ｄ−４はｔｏｐ−Ｆから、ホウ酸金属化合物ｂ−１はｓｉｄｅ−１から、強化材ｃ−１はｓｉｄｅ−２から合計の吐出量が３０ｋｇ／ｈｒになるようにそれぞれ調節して供給し、溶融混練してストランド状に取り出し、ストランドバス（水槽）で冷却後、カッターで造粒しポリアミド樹脂組成物ペレットを得た。
得られたペレットを前記した測定方法にてＵＬ−９４ＶＢ、成形性、ＭＤを調べた。その結果を表３に示す。
【００７６】
【比較例４】
芳香族成分を含むポリアミド樹脂ａ−１が１００．０重量部（７２．０重量％）、強化材ｃ−１が２７．８重量部（２０．０重量％）、シリコーン化合物ｄ−３が１１．１重量部（８．０重量％）からなるポリアミド組成物を得た。
用意する原材料（即ち、押出機への投入速度の設定）を芳香族成分を含むポリアミド樹脂ａ−１が０重量％、製造例６の１０重量％シリコーン含有ポリアミド樹脂が８０．０重量％、ホウ酸金属化合物ｂ−１が０重量％とした以外は実施例８と同様にしてペレットを得て、ＵＬ−９４ＶＢ、成形性、ＭＤ、燃焼挙動（コーンカロリーメーター試験）を調べた。その結果を表３に示す。
【００７７】
【実施例１２】
芳香族成分を含むポリアミド樹脂ａ−２が熱可塑性樹脂中の１００．０重量部（５０．４重量％）、ホウ酸金属化合物ｂ−１が１５．９重量部（８．０重量％）、強化材ｃ−１が３９．７重量部（２０．０重量％）、ポリフェニレンエーテル樹脂ｅ−１が４２．９重量部（２１．６重量％）からなるポリアミド組成物を得た。
原材料（即ち、押出機への投入速度の設定）は芳香族成分を含むポリアミド樹脂ａ−２が５０．４重量％、ポリフェニレンエーテル樹脂ｅ−１が２１．６重量％、ホウ酸金属化合物ｂ−１が８．０重量％、強化材ｃ−１が２０．０重量％となるように用意し、上流側に１ヶ所と、押出機中央部並びにダイに近い下流側の２ヶ所に供給口を有する二軸押出機（東芝機械製：ＴＥＭ３５）を用いてシリンダー設定温度２８０℃、スクリュー回転２００ｒｐｍ、吐出量３０ｋｇ／ｈｒの条件下で、芳香族成分を含むポリアミド樹脂ａ−１とポリフェニレンエーテル樹脂ｅ−１はｔｏｐ−Ｆから、ホウ酸金属化合物ｂ−１はｓｉｄｅ−１から、強化材ｃ−１はｓｉｄｅ−２から合計の吐出量が３０ｋｇ／ｈｒになるようにそれぞれ調節して供給し、溶融混練してストランド状に取り出し、ストランドバス（水槽）で冷却後、カッターで造粒しポリアミド樹脂組成物ペレットを得た。
得られたペレットを前記した測定方法にてＵＬ−９４ＶＢ、成形性、ＭＤを調べた。その結果を表３に示す。
【００７８】
【比較例５】
芳香族成分を含むポリアミド樹脂ａ−２が１００．０重量部（８０．０重量％）、強化材ｃ−１が２５．０重量部（２０．０重量％）からなるポリアミド組成物を得た。
用意する原材料（即ち、押出機への投入速度の設定）を芳香族成分を含むポリアミド樹脂ａ−２が８０．０重量％、ホウ酸金属化合物ｂ−１が０重量％とした以外は実施例１と同様にしてペレットを得て、ＵＬ−９４ＶＢ、成形性、ＭＤを調べた。その結果を表３に示す。
表１〜３の実施例１〜１２と比較例１〜５から分かるように、ハロゲン系難燃剤、アンチモン系難燃助剤、リン系難燃剤を含まないポリアミド樹脂組成物であって、芳香族成分を含むポリアミド樹脂に非ハロゲン、非アンチモン、非リンの難燃剤であるホウ酸金属化合物を添加することによって、ポリアミド樹脂がもつ電気特性を低下させること無く、難燃性を向上させることができ、電気特性、難燃性の両特性のバランスを持たせることができた。
結果は、ホウ酸金属化合物により難燃性は大きく向上し、また電気特性は、ホウ酸金属化合物を添加しても、高い値を維持した非常に難燃性、電気特性の両特性のバランスの取れた材料が得られた。
【００７９】
【表１】

【００８０】
【表２】

【００８１】
【表３】

【００８２】
【発明の効果】
本発明の組成物は、塩素、臭素等のハロゲン系難燃剤、アンチモン系助難燃剤並びリン系難燃剤を含有しない難燃性ポリアミド樹脂材料であり、ポリアミド樹脂が本来有する機械的特性、耐薬品性、良成形性、電気特性を損なうことなく、難燃性、電気特性を向上させ、金型腐食を低減でき、家電部品、電子部品、自動車部品等の用途に好適に用いることが出来る。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a flame retardant polyamide resin composition. In particular, the present invention relates to a flame retardant polyamide resin composition suitably used for parts materials such as electrical / electronic field connectors, breakers, magnet switches, and other parts, and automotive parts. In particular, the present invention improves the flame retardancy without impairing the mechanical properties and electrical properties inherent in the polyamide resin, and also includes halogen flame retardants such as chlorine and bromine, antimony auxiliary flame retardants and phosphorus flame retardants. The present invention relates to a flame retardant polyamide resin composition not contained.
[0002]
[Prior art]
Conventionally, polyamide resins have been used in a wide range of fields such as automobile parts, mechanical parts, and electric / electronic parts because they are excellent in mechanical properties, molding processability, electrical insulation and the like. However, polyamide resins are flammable, and various flame retardant techniques have been proposed due to safety issues. And generally, the method of mix | blending halogen-type flame retardants, such as a bromine compound with a high flame-retarding effect, and antimony oxide with a polyamide resin is taken.
[0003]
For example, addition of a chlorine-substituted polycyclic compound to a polyamide resin (for example, see Patent Document 1), addition of a brominated flame retardant, for example, decabromodiphenyl ether (for example, see Patent Document 2), and brominated polystyrene Addition (for example, refer to Patent Document 3 and Patent Document 4), addition of brominated polyphenylene ether (for example, refer to Patent Document 5), addition of brominated crosslinked aromatic polymer (for example, refer to Patent Document 6), Addition of brominated styrene-maleic anhydride polymer (for example, see Patent Document 7) is known. In particular, compositions containing these halogen-based flame retardants in polyamide resins reinforced with glass fibers, etc. are mounted on or connected to printed laminates, especially for electrical and electronic parts due to their high flame resistance and high rigidity. It has been used extensively for connector applications. However, while the halogen flame retardant improves flame retardancy, there is a problem that corrosive hydrogen halide is generated during heat processing such as injection molding and corrodes the mold and the like. In addition, the antimony compound used in combination with the halogen-based flame retardant also has a problem of greatly reducing the electrical properties (tracking resistance) necessary for electrical and electronic applications while improving the flame retardancy.
[0004]
For this reason, halogen-free phosphorus-based flame retardants have attracted attention and many studies have been made. For example, halogen-free flame retardant technology using melamine phosphate, melamine pyrophosphate, or melamine polyphosphate for glass fiber reinforced polyamide resin (for example, see Patent Document 8), adding melamine polyphosphate to inorganic reinforced polyamide resin, A flame retardant technique (see, for example, Patent Document 9) using a charring catalyst and / or a char forming agent has been proposed, and it is known that a 1/16 inch molded product satisfies the flame retardant standard UL94V-0 standard. ing. However, in these technologies, it is necessary to use a large amount of melamine phosphate flame retardant in order to satisfy the UL94V-0 standard for thin molded products that are particularly required for connector applications of electrical and electronic parts. Further, not only the mechanical properties of the glass fiber reinforced polyamide resin composition were greatly reduced, but also the electrical properties, particularly the tracking resistance required for electrical components used in a high voltage environment, was greatly reduced. Furthermore, the releasability at the time of molding was inferior, and it was not always satisfied as a molding material for electric / electronic parts.
[0005]
Moreover, as a technique for achieving the flame retardancy standard UL94V-0 for thin-walled molded products, a technique in which melamine sulfate, which is an intumescent flame retardant, is applied to a glass fiber reinforced semi-aromatic polyamide resin (see, for example, Patent Document 10). ) Is also disclosed, but it is necessary to add a large amount of flame retardant to the amount of the polyamide resin component in this technique, and there is a problem similar to the above. Furthermore, as a technology to provide high tracking resistance while achieving the flame retardant standard UL94V-0 for thin-walled molded products, in addition to melamine phosphate composite flame retardant and inorganic earth reinforced polyamide resin, alkaline earth metal salt is blended Although the technique (for example, refer patent document 11) to do is proposed, the molded article obtained by this technique had the problem that it was very weak. Furthermore, the molding processability is not satisfactory, and when the molded product is left for a long time in a high-temperature and high-humidity environment such as 60 ° C. and 95% RH, a polyamide oligomer or a flame retardant precipitates on the surface of the molded product. There were problems such as the occurrence of a bleedout phenomenon, which was not satisfactory.
[0006]
In contrast, development of flame retardants using zinc borate compounds as flame retardants has also been carried out. A flame-retarding technique using a zinc borate compound as an alternative to an antimony compound comprising a polyamide resin, an inorganic filler, a brominated flame retardant, zinc borate, and a heat stabilizer is disclosed (for example, see Patent Document 12). Yes. However, a halogen compound as a flame retardant is an essential component, and it is difficult to impart flame retardancy without using it. In addition, as a technology that does not use a halogen compound, at least 20% of a polyphenylene ether resin, a polycarbonate resin, a polyetherimide resin, a polyethersulfone resin, a polyphenylene sulfide resin, or the like contains a polymer component containing an aromatic main chain, fluorine as a flame retardant Flame retardant technology using a compound and a boron compound (see, for example, Patent Document 13), a polycarbonate resin containing a polydiorganosiloxane fluid, and a poly (diorganosiloxane) mixed in a poly (ester carbonate) resin as a free-flowing powder Flame retardant polycarbonate technology containing an effective amount of fibrous polytetrafluoroethylene and an effective amount of anhydrous zinc borate in a flame retardant polymer blend including a fluid-filler blend (see, for example, Patent Document 14), polycarbonate system Technology of flame retardant thermoplastic resin composition consisting of zinc borate and / or zinc borate hydrate, alcohol-modified silicone oil for thermoplastic resin consisting of fat and polyester resin (see, for example, Patent Document 15) However, these techniques are mainly performed with polycarbonate resins, etc., and when applied to polyamide resins and other resins, they do not exhibit sufficient flame retardancy or reduce other physical properties. Sometimes. In addition, in these techniques, when a reinforcing agent such as glass fiber is added, drip is generated during combustion, and sufficient flame retardancy may not be exhibited. In addition, polycarbonate may not be used for applications that are inferior in physical properties such as moldability, tensile strength, electrical properties, and chemical resistance and may come into contact with organic solvents.
[0007]
[Patent Document 1]
JP-A-48-29846
[Patent Document 2]
JP 47-7134 A
[Patent Document 3]
JP 51-47044 A
[Patent Document 4]
JP-A-4-175371
[Patent Document 5]
JP 54-1116054 A
[Patent Document 6]
Japanese Unexamined Patent Publication No. Sho 63-317552
[Patent Document 7]
Japanese Patent Laid-Open No. 3-168246
[Patent Document 8]
Japanese National Patent Publication No. 10-505875
[Patent Document 9]
WO 98/45364 pamphlet
[Patent Document 10]
JP 2000-119512 A
[Patent Document 11]
International Publication No. 00/09606 Pamphlet
[Patent Document 12]
Special table 2002-506905 gazette
[Patent Document 13]
JP-A-2-180969
[Patent Document 14]
JP-A-5-202280
[Patent Document 15]
JP 11-343400 A
[0008]
[Problems to be solved by the invention]
The object of the present invention is to contain the mechanical properties, chemical resistance, good moldability inherent in the polyamide resin without containing halogen-based flame retardants such as chlorine and bromine, antimony-based flame retardant aids and phosphorus-based flame retardants. An object of the present invention is to provide a flame retardant polyamide resin composition that greatly improves flame retardancy without impairing electrical characteristics, and suppresses heat generation rate and drip generation during combustion.
[0009]
[Means for Solving the Problems]
  As a result of extensive research, the present inventors have found that a polyamide resin containing an aromatic component and a composition containing three components of a polyamide resin, a halogen compound, and a metal borate compound when the metal borate compound is an essential component. The problem of corrosive hydrogen halide, etc. generated during heat processing such as injection molding, which was a problem, was able to solve the problem of corroding the mold etc., and the heat generation rate and drip generation during combustion were suppressed It has been found that a flame retardant polyamide resin composition can be provided. Furthermore, when combining a reinforcing material, a silicone compound, and a polyphenylene ether resin as optional components, it is possible to further improve flame retardancy such as a decrease in heat generation rate during combustion in UL test evaluation and corn calorimeter test, Furthermore, it has been found that further improvement of properties such as improvement of physical properties and fluidity can be realized, and the present invention has been completed based on this finding.
Moreover, this invention succeeded in achieving a flame retardance using only a polyamide boric acid zinc borate as a flame retardant.
  That is, the present invention
  [1](A)(1) Copolymers comprising poly (hexamethylene adipamide) units and poly (hexamethylene isophthalamide) units, (2) poly (hexamethylene adipamide) units, poly (hexamethylene isophthalamide) units and poly A terpolymer comprising (hexamethylene terephthalamide) units, (3) a terpolymer comprising poly (hexamethylene adipamide) units, poly (hexamethylene isophthalamide) units and poly (caprolactam) units, (4) selected from the group consisting of poly (nonamethylene terephthalamide), (5) poly (hexamethylene isophthalamide) and (6) a polyamide containing an aromatic component derived from a xylylenediamine componentPolyamide resin containing aromatic component and (b) metal borate compoundHaveFlame retardant polyamide resin composition,
  [2] The flame-retardant polyamide resin composition according to [1], comprising (a) 100 parts by weight of a polyamide resin containing an aromatic component, and (b) 0.1 to 200 parts by weight of a metal borate compound.
  [3] (1) having 100 parts by weight of a polyamide resin containing an aromatic component, (b) 0.1 to 200 parts by weight of a metal borate compound, and (c) 5 to 200 parts by weight of a reinforcing material ] The flame-retardant polyamide resin composition of description,
  [4] The flame-retardant polyamide resin composition according to any one of [1] to [3], further comprising (d) 0.01 to 100 parts by weight of a silicone compound,
  [5] (a) The aromatic component of the polyamide resin containing the aromatic component is derived from the isophthalic acid component [1] to [4] ] A flame retardant polyamide resin composition according to any one of
  [6] The flame-retardant polyamide resin composition according to any one of [1] to [4], wherein the polyamide resin containing (a) an aromatic component is a poly (metaxylylene adipamide) resin,
  [7] (b) The metal borate compound is xZnO · yB ₂ O ₃ ・ ZH ₂ The flame-retardant polyamide resin composition according to any one of [1] to [6], which is a zinc borate compound represented by O (x> 0, y> 0, z ≧ 0),
  [8] (b) The metal borate compound is 2ZnO.3B ₂ O ₃ ・ 3.5H ₂ O, 4ZnO · B ₂ O ₃ ・ H ₂ O, 2ZnO · 3B ₂ O ₃ The flame retardant polyamide resin composition according to [7], which is a compound represented by:
  [9] (b) The metal borate compound is 2ZnO.3B ₂ O ₃ ・ 3.5H ₂ The flame-retardant polyamide resin composition according to [8], which is a compound represented by O,
  [10] (c) The flame retardant polyamide resin composition according to any one of [3] to [9], wherein the reinforcing material is a fibrous filler,
  [11] (c) The flame retardant polyamide resin composition according to [10], wherein the reinforcing material is glass fiber,
  [12] The flame-retardant polyamide resin composition according to any one of [4] to [11], wherein the (d) silicone compound is a silicone compound comprising at least one selected from the group having the following siloxane units:
1) M units (monofunctional)
2) D unit (bifunctional)
3) T unit (trifunctional)
4) Q unit (tetrafunctional)
  [13] The flame-retardant polyamide resin composition according to any one of [4] to [12], wherein the (d) silicone compound is a silicone compound containing a vinyl group.
  [14] The (d) silicone compound has a vinyl group ratio of 2% or more in a molar ratio among all organic substituents bonded to a silicon atom excluding a trimethylsilyl group, an alkoxy group and a hydroxyl group. The flame-retardant polyamide resin composition according to any one of [4] to [13],
  [15] The flame retardant polyamide resin composition according to any one of [1] to [14], further comprising (e) 0.1 to 100 parts by weight of a polyphenylene ether resin.
  [16] A molded article comprising the flame-retardant polyamide resin composition according to any one of [1] to [15],
It is.
[0010]
The present invention will be specifically described below.
Examples of the polyamide resin containing an aromatic component (a) of the present invention include polycondensates of dicarboxylic acids and diamines, ring-opening polymers of cyclic lactams, polycondensates of aminocarboxylic acids, and the like. Are poly (metaxylylene adipamide) (hereinafter abbreviated as polyamide MXD6), poly (hexamethylene terephthalamide) (hereinafter abbreviated as polyamide 6T), poly (hexamethylene isophthalamide) (hereinafter abbreviated as polyamide 6I), poly And aliphatic-aromatic polyamides such as (nonamethylene terephthalamide) (hereinafter abbreviated as polyamide 9T), poly (tetramethylene isophthalamide) (hereinafter abbreviated as polyamide 4I), and copolymers and mixtures thereof. Further, the aliphatic-aromatic polyamide and poly (caprolactam) (hereinafter referred to as polyamide 6) ), Poly (hexamethylene adipamide) (hereinafter abbreviated as polyamide 66), poly (tetramethylene adipamide) (hereinafter abbreviated as polyamide 46), poly (hexamethylene sebacamide) (hereinafter abbreviated as polyamide 610) , Poly (hexamethylene dodecamide) (hereinafter abbreviated as polyamide 612), poly (undecamethylene adipamide) (hereinafter referred to as polyamide 116), poly (undecalactam) (hereinafter abbreviated as polyamide 11), poly (dodecalactam) Copolymers and mixtures with aliphatic polyamides such as (hereinafter abbreviated as polyamide 12) can also be mentioned.
[0011]
First, as a polyamide containing an aromatic component which is preferable in the present invention, a polyamide polymerized from an aromatic diacid such as isophthalic acid or a terephthalic acid component is particularly preferable because it exhibits high flame retardancy. Examples thereof include polyamide 6T, polyamide 6I, polyamide 9T, polyamide 4I, and copolymers and mixtures thereof. More preferably, 66 / 6I copolymer polyamide, 66 / 6I / 6T terpolymer polyamide, 66 / 6I / 6 terpolymer polyamide, polyamide 9T, and polyamide 6I satisfy both high flame retardancy and moldability. This is preferable.
[0012]
Specifically, (1) a copolymer comprising 60 to 95% by weight of poly (hexamethylene adipamide) units and 5 to 40% by weight of poly (hexamethylene isophthalamide) units; (2) poly (hexamethylene adipamide) A ternary copolymer comprising 50 to 94% by weight of a pamide) unit, 5 to 40% by weight of a poly (hexamethylene isophthalamide) unit, and 1 to 10% by weight of an aliphatic polyamide unit other than poly (hexamethylene adipamide). (3) mixed polyamide containing 60 to 95% by weight of poly (hexamethylene adipamide) component and 5 to 40% by weight of poly (hexamethylene isophthalamide) component; (4) poly (hexamethylene adipamide) component Fats other than 50-94% by weight, poly (hexamethylene isophthalamide) component 5-40% by weight and poly (hexamethylene adipamide) Include mixed polyamides containing 1 to 10 wt% family polyamide component, a polyamide containing these aromatic components is more preferred. The aliphatic polyamide unit other than poly (hexamethylene adipamide) in (2) and the aliphatic polyamide component other than poly (hexamethylene adipamide) in (4) include poly (caprolactam), Examples include units and components of polyamide 6.
[0013]
Next, as a polyamide containing an aromatic component, a polyamide polymerized from a diamine containing a xylylenediamine component (including metaxylylenediamine and paraxylylenediamine) is a non-combustible layer (or carbonized layer) production amount. Is particularly preferable since it exhibits a high flame retardancy. Specific examples thereof include polyamide MXD6, which is preferable because it forms an incombustible layer (or a carbonized layer) during combustion when used in combination with a metal borate compound and exhibits excellent flame retardancy. .
[0014]
Specific examples of the (b) metal borate compound used in the present invention include zinc borate compounds, magnesium borate compounds, calcium borate compounds, and aluminum borate compounds. As a preferred borate metal compound for the present invention, by blocking the heat from the flame which is a heat source during combustion to the resin (heat insulation ability), the generation of gas serving as fuel by decomposition of the resin is suppressed, and flame retardancy is reduced. Since the formation efficiency of the non-combustible layer (or carbonized layer) necessary for the enhancement is high, that is, excellent in flame retardancy, xZnO · yB₂O_Three・ ZH₂Examples thereof include zinc borate compounds represented by O (x> 0, y> 0, z ≧ 0). Preferably, 2ZnO · 3B₂O_Three・ 3.5H₂O, 4ZnO · B₂O_Three・ H₂O, 2ZnO · 3B₂O_ThreeZinc borate compound represented by the formula, more preferably, water vapor is generated by dehydration during combustion, the non-combustible layer can be further foamed, and the heat insulating ability of the non-combustible layer can be further increased, and at the same time, the vaporization of water 2ZnO · 3B that can cool the combustion system with heat₂O_Three・ 3.5H₂O, 4ZnO · B₂O_Three・ H₂Zinc borate hydrate represented by O, and most preferably 2ZnO.3B having a high ratio of water contained₂O_Three・ 3.5H₂O is mentioned.
[0015]
Further, these metal borate compounds may be treated with a surface treatment agent such as a silane coupling agent or a titanate coupling agent. The average particle size is preferably 30 μm or less, more preferably 15 μm or less, and particularly preferably 7 μm or less.
The reinforcing material (c) used in the present invention is an optional component, and even if this component is not present, the object of the present invention can be achieved. However, when further improving flame retardancy and mechanical properties, this component is added. Can be added.
[0016]
(C) As reinforcing material, glass fiber, carbon fiber, potassium titanate fiber, gypsum fiber, brass fiber, stainless steel fiber, steel fiber, ceramic fiber, boron whisker fiber, mica, talc, silica, calcium carbonate, kaolin, fired Examples thereof include fiber-like, granular, plate-like, or needle-like inorganic reinforcing materials such as kaolin, wollastonite, glass beads, glass flakes, and titanium oxide. Two or more of these reinforcing materials may be used in combination. In particular, fibrous reinforcing agents such as glass fibers have a high drip-suppressing effect during combustion, and strengthen the incombustible layer (or carbonized layer) generated during combustion to maintain the shape of the foamed incombustible layer (or carbonized layer). It is preferably used because it can achieve high flame retardancy.
[0017]
Further, the glass fiber can be selected from long fiber type roving, short fiber type chopped strand, milled fiber and the like. It is preferable to use a surface-treated glass fiber. In particular, the use of glass fiber is particularly preferable because it is particularly excellent in physical properties and flame retardancy. Among these, the average fiber diameter of the glass fiber is preferably 5 to 30 μm. Moreover, since the surface treatment of glass fiber gives the outstanding physical property, it is still more preferable.
[0018]
By blending the reinforcing material, the strength of the incombustible layer (or carbonized layer) generated at the time of combustion can be further improved, and the incombustible layer (or carbonized layer) is less likely to be damaged at the time of combustion. It will be possible to exert a greater flame retardant effect. Furthermore, high rigidity can also be provided.
The silicone compound (d) used in the present invention is an optional component, and even without this component, the object of the present invention can be achieved. However, when further improving flame retardancy, fluidity and mechanical properties, , This component can be added
(D) The structure of the silicone compound is a polymer obtained by polymerizing at least one of the following four siloxane units (M unit, D unit, T unit, Q unit).
[0019]
1) M units (monofunctional)
[Chemical formula 5]

[0020]
2) D unit (bifunctional)
[Chemical 6]

[0021]
3) T unit (trifunctional)
[Chemical 7]

[0022]
4) Q unit (tetrafunctional)
[Chemical 8]

[0023]
(However, R is the same or different substituent, and is selected from an alkyl group, aryl group, benzyl group, vinyl group, allyl group, alkoxy group, hydroxy group, amino group, methyl ester group and ethyl ester group. )
Among these, when a T unit and / or a Q unit are contained, a branched structure is obtained. The structure of the (d) silicone compound of the present invention is not particularly defined, and may be branched or linear, and may be liquid or solid.
[0024]
As such a thing, the following are mentioned, for example. Examples of linear organopolysiloxanes include dimethylpolysiloxane, methylphenylpolysiloxane, vinylmethylorganopolysiloxane, and vinylphenylmethylpolysiloxane. Examples of branched organopolysiloxane include methylpolysiloxane resin and methylphenyl. Examples thereof include polysiloxane resin, phenyl polysiloxane resin, vinylmethylorganopolysiloxane resin, and vinylphenylmethylpolysiloxane resin. Further modified organopolysiloxanes (resins) include amino-modified organopolysiloxanes (resins), epoxy-modified organopolysiloxanes (resins), carboxyl-modified organopolysiloxanes (resins), carbinol-modified organopolysiloxanes (resins), and methacrylic modifications. Organopolysiloxane (resin), mercapto modified organopolysiloxane (resin), polyether modified organopolysiloxane (resin), methylstyryl modified organopolysiloxane (resin), higher alkyl modified organopolysiloxane (resin), higher alkyl fatty acid ester Modified organopolysiloxane (resin), alkyl aralkyl modified organopolysiloxane (resin), hydroxyl modified organopolysiloxane (resin), alcohol Si-modified organopolysiloxane (resin), alcohol-modified organopolysiloxane (resin), fluorine-modified organopolysiloxane (resin), silanol-modified organopolysiloxane (resin), etc. The main chain terminal and side chain of polysiloxane are mentioned, and the introduction rate may be part or all.
[0025]
The polyamide molecule has a highly polar amide bond, but the silicone molecule does not have a highly polar functional group, so the compatibility between the two is poor. Therefore, when a large amount of silicone is contained, the appearance may deteriorate due to peeling or the like on the molded piece. To avoid this, a part or all of the main chain ends and side chains of the silicone compound to be used are used. Can be used silicones modified with polar functional groups such as amino groups, epoxy groups, carboxyl groups, carbinol groups, mercapto groups, higher alkyl fatty acid ester groups, alkoxy groups, hydroxyl groups and the like.
[0026]
By blending silicone, the non-combustible layer (or carbonized layer) produced during combustion swells larger and has a higher heat insulation capability, and a greater flame retardant effect is obtained. Also, good fluidity and impact resistance can be imparted.
Among these organic substituents of silicone, those containing a vinyl group are preferred. In addition, a silicone compound in which a vinyl group is directly bonded to a silicon atom is particularly preferable because it exhibits high flame retardancy, and among all organic substituents bonded to a silicon atom excluding a terminal group (such as a trimethylsilyl group or an alkoxy group) Silicone having a vinyl group ratio of 2% or more in terms of a molar ratio is more preferable because it exhibits higher flame retardancy. The reason is not clear, but the silicone containing the vinyl group, which is highly reactive during combustion, makes it easy to form a non-combustible layer, and the reinforcing material strengthens the formed non-combustible layer. It seems that the effect, that is, the drip suppression effect during combustion is exhibited.
[0027]
Further, the method for adding the silicone compound is not particularly limited, and once a resin such as a polyamide resin containing a silicone compound and an aromatic component is kneaded with an extruder or the like to obtain a silicone compound-containing resin composition, Even a two-stage method of kneading a borate metal compound, a reinforcing material or the like, or a one-stage method of kneading a resin such as a silicone compound, a metal borate compound, a reinforcing material, a polyamide resin containing an aromatic component at a time, When the silicone compound is in a liquid state, it can be added to the molten resin in the extruder with a liquid addition device such as a liquid addition pump, or after being blended externally with resin pellets, etc., and then kneaded with an extruder, etc. Is mentioned. Among these, when a liquid addition apparatus is used, the viscosity of the silicone compound tank or the silicone compound flow path may be lowered by heating with a heater or the like. In addition, when solid, a method of kneading with an extruder or the like after blending with a supply from the top supply port (top feeder) of the extruder or a supply port (side feeder) in the middle of the extruder or resin pellets Etc.
[0028]
The (e) polyphenylene ether resin used in the present invention is an optional component, and even without this component, the object of the present invention can be achieved. However, when further improving flame retardancy and mechanical properties, Ingredients can be added.
(E) Polyphenylene ether resin is a repeating unit structure
[0029]
[Chemical 9]

[0030]
(R₁, R_FourEach independently represents hydrogen, primary or secondary lower alkyl, phenyl, aminoalkyl or hydrocarbonoxy. R₂, R_ThreeEach independently represents hydrogen, primary or secondary lower alkyl or phenyl. )
And a reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.) is a homopolymer and / or copolymer having a range of 0.15 dl / g to 1.0 dl / g. A more preferred reduced viscosity is in the range of 0.20 dl / g to 0.70 dl / g, most preferably in the range of 0.40 dl / g to 0.60 dl / g. Moreover, in order to improve fluidity and moldability, those having a low reduced viscosity can be used in combination, and those having a low reduced viscosity are in the range of 0.03 dl / g to 0.40 dl / g, preferably 0.06 dl / g or more and 0.30 dl / g or less.
[0031]
Specific examples include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-phenyl-1). , 4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like, and 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethyl). And a polyphenylene ether copolymer such as a copolymer with phenol or 2-methyl-6-butylphenol). Of these, poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and poly (2,6-dimethyl-1 , 4-phenylene ether).
[0032]
As an example of the method for producing polyphenylene ether used in the present invention, there is a method of oxidative polymerization of 2,6-xylenol using a complex of cuprous salt and amine described in US Pat. No. 3,306,874 as a catalyst. The methods described in U.S. Pat. Nos. 3,306,875, 3,257,357 and 3,257,358, JP-B-52-17880, JP-A-50-51197, and JP-A-63-152628 are also polyphenylene. This is preferred as a method for producing ether.
[0033]
Furthermore, it is preferable that some or all of the polyphenylene ether resin is modified with a compatibilizing agent such as maleic anhydride to improve the compatibility with the polyamide resin, thereby improving the physical properties and appearance. In addition, the method in this case is not particularly limited. After the compatibilizer and polyphenylene ether resin are reacted once in an extruder to obtain a modified polyphenylene ether, etc., this is kneaded with polyamide and the like. The step method may be a single step method in which a compatibilizing agent, polyphenylene ether resin, polyamide resin and the like are kneaded at a time.
[0034]
In a preferred embodiment of the present invention, the components (a) and (b) are essential components, and the object of the present invention can be achieved by these two components. Components (c), (d), and (e) are optional components, and effects such as further imparting flame retardancy, improving mechanical properties, and improving fluidity are added by adding them.
In the flame-retardant polyamide resin composition of the present invention, the ratio of (b) the metal borate compound is not particularly defined. However, when further improving the molding processability, mechanical properties, and flame retardancy, (a) 100 parts by weight or more and 200 parts by weight or less is preferable with respect to 100 parts by weight of the polyamide resin containing the aromatic component. When the amount is more than 200 parts by weight, the molding processability and mechanical properties are slightly improved, and when the amount is less than 0.1 parts by weight, the flame retardancy is slightly improved. More preferably, they are 1 weight part or more and 150 weight parts or less, More preferably, they are 2 weight parts or more and 120 weight parts or less, Most preferably, they are 5 weight parts or more and 100 weight parts or less.
[0035]
(C) The reinforcing material is an optional component, but the proportion when added is preferably 5 parts by weight or more and 200 parts by weight or less with respect to 100 parts by weight of the polyamide resin containing (a) the aromatic component. When the amount is more than 200 parts by weight, the molding processability is remarkably lowered at the time of extrusion or injection molding, and when the amount is less than 5 parts by weight, mechanical properties such as tensile strength and rigidity are not so much improved as compared with the case where it is not added. More preferably, it is 10 to 180 weight part, More preferably, it is 15 to 150 weight part.
[0036]
(D) Although a silicone compound is an arbitrary component, the ratio when it is added is preferably 0.01 parts by weight or more and 100 parts by weight or less with respect to 100 parts by weight of the polyamide resin containing (a) the aromatic component. When the amount is more than 100 parts by weight, problems such as generation of decomposition gas at the time of kneading and adhesion of contaminating substances to the molding die at the time of molding occur. Therefore, there is little improvement in flame retardancy, fluidity and impact resistance. More preferably, it is 0.05 to 80 weight part, More preferably, it is 0.1 to 60 weight part.
[0037]
(E) The polyphenylene ether resin is an optional component, but the ratio when it is added is preferably 0.1 parts by weight or more and 100 parts by weight or less with respect to 100 parts by weight of the polyamide resin containing the aromatic component (a). . If the amount is more than 100% by weight, the molding processability and mechanical properties of the polyamide resin are lowered, and if it is 0.1 parts by weight or less, the improvement in fluidity is hardly observed. More preferably, they are 1 weight part or more and 80 weight parts or less, More preferably, they are 3 weight parts or more and 60 weight parts or less.
[0038]
The halogen-based flame retardant, antimony-based flame retardant auxiliary, and phosphorus-based flame retardant in the present specification correspond to compounds intended to increase flame retardancy among halogen compounds, antimony compounds, and phosphorus compounds. . However, the objective halogen compound, antimony compound, and phosphorus compound for enhancing properties such as heat stability other than flame retardancy are not included in this expression as long as they do not affect the flame retardancy of the present application.
[0039]
As a compound aiming at enhancing flame retardancy, first as a halogen compound, for example, as a chlorinated flame retardant, chlorinated paraffin, chlorinated polyethylene, dodecachloropentacyclooctadeca-7,15-diene (oxydental chemical) Hexabromocyclododecane (HBCD), decabromodiphenyl oxide (DBDPO), octabromodiphenyl oxide, tetrabromobisphenol A (TBBA) as brominated flame retardants such as Dechlorane Plus 25 (registered trademark), manufactured by the company Bis (tribromophenoxy) ethane, bis (pentabromophenoxy) ethane (BPBPE), tetrabromobisphenol A epoxy resin (TBBA epoxy), tetrabromobisphenol A carbonate (TBBA-PC), ethylene ( Stetrabromophthal) imide (EBTBPI), ethylenebispentabromodiphenyl, tris (tribromophenoxy) triazine (TTBPTA), bis (dibromopropyl) tetrabromobisphenol A (DBP-TBBA), bis (dibromopropyl) tetrabromobisphenol S (DBP-TBBS), brominated polyphenylene ether (including polydipromophenylene ether) (BrPPE), brominated polystyrene (including polydibromostyrene, etc.) (BrPS), brominated crosslinked aromatic polymer, brominated epoxy Resin, brominated phenoxy resin, brominated styrene-maleic anhydride polymer, tetrabromobisphenol S (TBBS), tris (tribromoneopentyl) phosphate (TTBNPP), polybromotrimethy Ruphenylindane (PBPI), tris (dibromopropyl) -isocyanurate (TDBPIC), etc., as reactive flame retardants, tetrabromobisphenol A (TBBA) (also described in brominated flame retardants), tetrabromophthalate, tetrabromophthalate diol , Tetrabromophthalate ester, tetrabromophthalate disodium, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, tribromophenol (TBP), dibromophenol, dibromometacresol, dibromoneopentyl glycol, poly (pentabromobenzyl polyacrylate) (PPBBA), chlorent acid, chlorent anhydride, brominated phenol, dibromocresyl glycidyl ether, vinyl bromide, dibromostyrene, tribromostyrene, etc. It is below.
[0040]
Next, examples of the antimony compound include antimony oxides such as antimony trioxide, antimony tetroxide, and antimony pentoxide, and sodium antimonate.
Thirdly, as phosphorus compounds, for example, red phosphorus flame retardant as red phosphorus, phosphate ester flame retardant as triphenyl phosphate (TPP), tricresyl phosphate (TCP), trixylenyl phosphate Fate (TXP), triethyl phosphate, tributyl phosphate (TBP), trioctyl phosphate (TOP), tris (butoxyethyl) phosphate, cresyl diphenyl phosphate (CDP), xylenyl diphenyl phosphate, bis ( Nonylphenyl) phenyl phosphate (DNP), cresyl bis (di2,6-xylenyl) phosphate, 2-ethylhexyl diphenyl phosphate, resorcinol bis (diphenyl) phosphate (RDP), bisphenol A bis ( Phenyl) phosphate (BPA-DP), bisphenol A bis (dicresyl) phosphate (BPA-DC), resorcinol bis (di2,6-xylenyl) phosphate, diethyl-N, N-bis (2-hydroxyethyl) amino Tris (chloroethyl) phosphate, tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate, tris (tribromoneo) as halogenated phosphate flame retardants such as methyl phosphonate and dimethyl methyl phosphonate Pentyl) phosphate, phosphate amide flame retardant, triphenyl phosphate, etc., phosphate flame retardant, ammonium polyphosphate (APP), melamine phosphate, guanidine phosphate, melamine pyrophosphate, polyphosphate Examples of phosphine flame retardants such as melamine acid include triphenyl phosphine, triphenyl phosphine oxide, tetrakis (hydroxymethyl) phosphonium chloride, tetrakis (hydroxymethyl) sulfate, and other phosphazene flame retardants. Examples thereof include phosphorus compounds such as phazenes, phenoxyphosphazenes, aminophosphazenes, poly (fluoroalkylphosphazenes), and dipropoxyphosphazenes.
[0041]
On the other hand, as long as it does not affect the flame retardancy of the present application, compounds generally used as compounds for improving heat stability and preventing discoloration, for example, those containing halogen include potassium iodide, Halogen compounds such as carium bromide, copper chloride, copper bromide, copper iodide, phosphorous heat stabilizers, copper phosphate, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene Phosphonite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, Triphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, 4,4- Butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, cyclic neopentanetetrayl bis (octadecyl phosphite), cyclic neopentanetetrayl bis (2,6-di-t -Butyl-4-methylphenyl) phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol diphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- ( 3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa- 10-phosphaphenanthrene, trimethyl phosphate, hypophosphorous acid Phosphorus compounds such as sodium and the like.
[0042]
In order to further improve the flame retardancy, an aromatic-containing thermoplastic resin can be added to the composition of the present invention. For example, polystyrene resin, syndiotactic polystyrene resin, polyphenylene ether resin, polyphenylene sulfide resin, polyamideimide resin, polyallyl ether ketone resin, polyether ether ketone resin, polyetherimide resin, polyether ketone resin, polyether ketone ketone resin , Polyethersulfone resin, polyphthalamide resin, polysulfone resin and the like.
[0043]
Further, polyphenylene ether resins and polyphenylene sulfide resins are preferable because they have many non-combustible layers (or carbonized layers) produced during combustion, are excellent in flame retardancy, and are excellent in appearance. In particular, polyphenylene ether resin is most preferable. The method for producing the reinforced flame-retardant polyamide resin composition of the present invention is not particularly limited, and is a polyamide resin, a boric acid metal compound, a reinforcing material (optional component), a silicone compound (optional component), a polyphenylene ether resin (optional). Any method may be used as long as the component is melt kneaded at a temperature of 200 to 350 ° C. using a kneader such as a conventional single or twin screw extruder or kneader.
[0044]
In the flame-retardant polyamide resin composition of the present invention, other components, for example, colorants such as flame retardants, fibrillating agents, pigments and dyes, and general thermoplastic resins can be used without departing from the object of the present invention. Heat stabilizers such as copper-based heat stabilizers (for example, combined use of copper iodide, copper acetate, etc., and potassium iodide, carium bromide), organic heat-resistant agents represented by hindered phenol-based oxidative degradation inhibitors, Additives such as a weather resistance improver, a nucleating agent, a plasticizer, and an antistatic agent can be added. In addition, in order to promote foaming of the incombustible layer (or the carbonized layer), increase the heat insulation effect, and exhibit high flame retardancy, components that generate gas components such as water vapor, nitrogen, carbon dioxide during combustion, such as water Metal hydroxide compounds such as aluminum oxide and magnesium hydroxide, nitrogen compounds such as melamine, melem, melon, and melamine cyanurate, and metal carbonate compounds such as calcium carbonate can also be added.
The composition of the present invention is molded into various molded products for electrical, electronic and automotive applications such as connectors, coil bobbins, breakers, electromagnetic switches, holders, plugs, switches, etc. by known methods such as injection molding, extrusion molding, blow molding. The
[0045]
DETAILED DESCRIPTION OF THE INVENTION
The following examples further illustrate the present invention, but the present invention is not limited thereto.
In addition, the raw material and the measuring method which were used for the Example and the comparative example are shown below.
[raw materials]
(A) Polyamide resin containing an aromatic component
(A-1): Polyamide MXD6 manufactured by Mitsubishi Engineering Plastics Co., Ltd. Product name Reny 6002
(A-2): Polyamide 66 / 6I of Production Example 1 (Molar ratio of copolymerization component 66: 6I = 85: 15)
[0046]
(B) Metal borate compound
(B-1): Zinc borate (hydrate) 2ZnO.3B₂O_Three・ 3.5H₂O U. S. Borax brand name Firebrake ZB
(B-2): Zinc borate (anhydride) 2ZnO.3B₂O_Three  U. S. Product name Firebrake 500 made by Borax
(C) Reinforcement material
(C-1): Glass fiber Product name ECT03T275H / PL (average fiber diameter 10 μm) manufactured by Nippon Electric Glass Co., Ltd.
[0047]
(D) Silicone compound
(D-1): Vinyl group-containing silicone (liquid at 20 ° C.) manufactured by Shin-Etsu Chemical Co., Ltd. Trade name X-40-9243
This silicone compound is dissolved in deuterated chloroform,²⁹Si-NMR and¹H-NMR measurement was performed, the structure of the silicone compound was analyzed, and the presence or absence of a vinyl group was confirmed. Further, from the integration ratio obtained by this measurement, this silicone compound had a vinyl group ratio of 10% in terms of a molar ratio among all organic substituents on silicon excluding terminal groups (trimethylsilyl group, alkoxy group, etc.).
(D-2): Vinyl group-containing silicone compound of Production Example 3 (liquid at 20 ° C.)
Measurement was performed in the same manner as for d-1, and the vinyl group ratio was 8% in terms of molar ratio.
(D-3): dimethyl silicone oil (liquid at 20 ° C.) manufactured by Shin-Etsu Chemical Co., Ltd. Product name KF96-100
(D-4): Silicone resin (solvent-free methyl varnish) (solid state at 20 ° C.) GE Toshiba Silicones Co., Ltd. Product name YR3370
(E) Polyphenylene ether resin
(E-1): Maleic anhydride-modified polyphenylene ether of Production Example 2
[0048]
[Production Example 1]
2.00 kg of equimolar salt of adipic acid and hexamethylenediamine, 0.35 kg of equimolar salt of isophthalic acid and hexamethylenediamine, 0.1 kg of adipic acid, and 2.5 kg of pure water were charged into a 5 L autoclave and stirred well. did. After sufficiently purging with nitrogen, the temperature was raised from room temperature to 220 ° C. over about 1 hour with stirring. Under the present circumstances, although the internal pressure became 1.76 MPa by the natural pressure by the water vapor | steam in an autoclave, it continued heating, removing water out of a reaction system so that it might not become a pressure of 1.76 MPa or more. After 2 hours, when the internal temperature reached 260 ° C., the heating was stopped, the autoclave valve was closed, and the system was cooled to room temperature over about 8 hours. After cooling, the autoclave was opened, and about 2 kg of polymer was taken out and pulverized. The obtained pulverized polymer was placed in a 10 L evaporator and subjected to solid phase polymerization at 200 ° C. for 10 hours under a nitrogen stream. The polyamide obtained by solid phase polymerization had a melting point of 245 ° C. and a sulfuric acid relative viscosity of 2.38.
[0049]
[Production Example 2]
Poly (2,6-dimethyl-1,4-phenylene ether) having a reduced viscosity (0.5 g / dl chloroform solution, measured at 30 ° C.) of 0.52 obtained by oxidative polymerization of 2,6-dimethylphenol 100 parts by weight of polyphenylene ether), 1.0 part by weight of maleic anhydride as a compatibilizer, one upstream (hereinafter abbreviated as top-F), the central part of the extruder, and the downstream near the die Side-1 of a twin-screw extruder (manufactured by Werner & Pfleiderer: ZSK-40) having supply ports (hereinafter abbreviated as side-1 at the central portion of the extruder and side-2 at the downstream side close to the die). And side-2 in a closed state, under conditions of a cylinder set temperature of 320 ° C., a screw rotation of 300 rpm, and a discharge rate of 20.15 kg / hr. Supply dry blend of ether and maleic anhydride from top-F, melt knead and take out into strand form, cool in strand bath (water tank), granulate with cutter, and pellet of maleic anhydride modified polyphenylene ether Obtained.
[0050]
[Production Example 3]
Hydrolysis was performed by slowly dropping a mixed solution of 42.3 g of trichlorophenylsilane, 42.3 g of dichloromethylvinylsilane, 38.2 g of dichloromethylphenylsilane, and 167.8 g of dichlorodimethylsilane into a mixed solution of 450.8 g of water and 143 g of toluene. Thereafter, aging was performed at 80 ° C. for 1 hour. Then, an excessive amount of chlorotrimethylsilane was dropped into the reaction solution, and further aged at 80 ° C. for 1 hour. The aqueous phase was discarded with a separatory funnel and the organic (toluene) phase was extracted several times with a 10% aqueous sodium sulfate solution until neutral.
Thereafter, the organic phase was transferred to a distillation apparatus to remove toluene as a solvent to some extent. Finally, the solvent was completely distilled off under reduced pressure using an evaporator to obtain about 180 g of vinyl group-containing silicone.
This series of operations was repeated until the required amount was reached.
[0051]
[Measuring method]
(1) UL-94VB
Ten samples were measured for each sample using the method of UL94 (standard defined by Under Writers Laboratories Inc., USA). The test piece had a length of 127 mm, a width of 12.7 mm, a thickness of 1/8 inch, and was molded by using an injection molding machine (manufactured by Nissei Kogyo Co., Ltd .: PS40E). In addition, for a sample having a thickness of 1/8 inch and V-0 or V-1, a more severe condition of an injection molding machine (manufactured by Nissei Kogyo Co., Ltd .: PS40E) ) To obtain.
The drip indicates the number of samples that drip that caused cotton ignition during the test of each sample. In the average time (s), the average burning time of the flame extinction time after flame contact for 2 times, ie, 20 times in total for each sample for 10 seconds is shown. In the maximum time (s), the maximum combustion time of the extinguishing time after 20 times of flame contact was also shown. However, if the specimen is burned out or the flame extinguishing time is too long and clearly any of V-0, V-1, and V-2 is not applicable, the average time and the maximum time are values. Is not described. In the evaluation, the flame retardance class classified by the UL94 vertical combustion test is shown. The outline of the classification method is as follows. Details conform to the UL94 standard.
[0052]
V-0
No cotton ignition Average burning time 5 seconds or less Maximum burning time 10 seconds or less
V-1
No cotton ignition Average burning time 25 seconds or less Maximum burning time 30 seconds or less
V-2
With cotton ignition Average burning time 25 seconds or less Maximum burning time 30 seconds or less
V-2out
Does not fall under the above three items
[0053]
(2) Formability
When a strip test piece (3.2 × 12.7 × 127 mm) of each sample was molded using an injection molding machine (manufactured by Nissei Kogyo Co., Ltd .: PS40E), a molding machine was formed from the pellet hopper of the injection molding machine. The efficiency of resin supply to the screw was evaluated. Passing pellets supplied to the screw part without any problem (◎), there are some problems in supply than the pass (specifically, pellets are difficult to bite into the screw, etc.), and the plasticization time becomes longer, The injection cycle has almost no problems (○), there is a problem with the supply, the sample with less than half of all the samples has a delay in the injection cycle (△), there is a problem with the supply. A sample in which more than half of all the samples were delayed in the injection cycle was regarded as rejected (x).
[0054]
(3) MD
Simultaneously with the above-described moldability evaluation, the adhesion of mold deposit (MD) in each sample molding was also judged visually. Evaluation is to determine the deposits on the mold after 30 shots of each sample, pass (◎) if there is no MD at all, pass a little MD but almost no problem (○), many MD Some of the problems were slightly rejected (△), and those that caused a significant amount of MD were rejected (x).
[0055]
(4) Combustion behavior (cone calorimeter test)
In order to examine the state of combustion of the sample, the combustion behavior was examined using a cone calorimeter capable of observing the temporal change of the heat generation rate during combustion.
The apparatus used was a corn calorimeter III manufactured by Toyo Seiki Seisakusho. The sample to be burned is a 5.0 mm × 32.5 mm × 114 mm thick test piece molded by an injection molding machine (Toshiba Machine: IS150) and cut into a shape of 5.0 mm × 32.5 mm × 100 mm. A sample was obtained. This sample was covered with the other five surfaces (side surface and lower surface) using an aluminum foil, leaving one surface of 32.5 mm × 100 mm as the upper surface during measurement.
As a measurement condition, the radiation amount of the cone heater is 50 kW / m.², Exhaust flow rate is 0.024m^Three/ Sec, the orifice type is large, the distance between the upper surface of the sample and the cone heater is 25 mm, and the shutter and igniter (10 kV high voltage spark for igniting the flammable gas generated from the sample) to cut off the radiant heat until the measurement. ) Was used. The shutter was opened and the test was started at the same time as the heating by the radiant heat of the cone heater was started. The sample was decomposed by heating, the decomposed gas was ignited by an igniter, and the sample was burned and continued until it did not burn.
[0056]
Evaluation is based on the rate of heat generation per unit area = H. R. R. (KW / m²) As an indicator of the intensity of combustion.
Maximum H. R. R. Is the H.O. between the sample igniting and disappearing. R. R. The maximum value of was shown.
Average H. R. R. Is the H.O. between the sample igniting and disappearing. R. R. The average value was shown.
The thickness of the incombustible layer was measured using a caliper with the maximum height of the unburned sample after the test for the purpose of measuring the thickness of the incombustible layer (or carbonized layer) formed during the sample combustion. Incidentally, the height before the test is 5 mm.
And as the thickness of this incombustible layer is thicker, the distance between the unburned resin (fuel) and the flame (heat source) is larger, that is, the heat insulation effect is increased and the continuation of combustion can be suppressed, so that high flame retardancy is expressed it can.
The hardness of the incombustible layer was determined from the resistance when the unburned sample after the test was struck with a finger for the purpose of measuring the strength of the incombustible layer (or carbonized layer) formed during sample combustion. Hard materials were marked with ◎, slightly hard materials were marked with ○, and brittle materials were marked with ×.
[0057]
(5) Glow wire ignitability test (GWI)
Tested for test items of flammability (GWFI) and ignitability (GWIT) using the equipment of the glow wire flammability tester HAT-214 manufactured by Hitachi Chemical Co., Ltd., using the method of IEC60695-2-1 standard. It was. The test piece was 65 mm × 90 mm × 1.0 mm (thickness 1.0 mm), and was obtained by molding using an injection molding machine (Toshiba Machine: IS150).
[0058]
(6) Electrical characteristics (CTI)
The tracking resistance test was performed by the method of IEC Publication 112 standard using the apparatus of the tracking resistance tester HAT-500-3 manufactured by Hitachi Chemical Co., Ltd. The test piece was 130 mm × 130 mm × 3.0 mm (thickness 3.0 mm) and was obtained by molding using an injection molding machine (Toshiba Machine: IS150). The outline of the measurement is that a test piece is set in the apparatus, a voltage of 100 to 600 V is applied to the surface of the test piece with two electrodes, and a 0.1% ammonium chloride aqueous solution is dropped between the electrodes every 30 seconds. The maximum voltage (CTI) at which the piece did not track and destroyed with 50 drops was measured and indicated. The higher this value, the better the tracking resistance.
[0059]
[Example 1]
Polyamide resin a-1 containing an aromatic component is 100.0 parts by weight (72.0% by weight), borate metal compound b-1 is 11.1 parts by weight (8.0% by weight), reinforcing material c-1 A polyamide composition comprising 27.8 (20.0 wt%) was obtained.
The raw materials (that is, the setting of the charging speed into the extruder) were 72.0% by weight of polyamide resin a-1 containing an aromatic component, 8.0% by weight of metal borate compound b-1, and reinforcing material c-1. Prepared at 20.0% by weight, one on the upstream side (hereinafter abbreviated as “top-F”), and at the center of the extruder and at two locations on the downstream side near the die (hereinafter referred to as the center of the extruder). Side-1 and the downstream side close to the die is abbreviated as side-2) using a twin screw extruder (manufactured by Toshiba Machine: TEM35) with a cylinder set temperature of 240 ° C., screw rotation of 200 rpm, and a discharge rate of 30 kg / hr Under the conditions, the polyamide resin a-1 containing an aromatic component is from top-F, the borate metal compound b-1 is from side-1, and the reinforcing material c-1 is from side-2 with a total discharge amount of 30 kg / It will be like hr Adjusted by supplying, by melt-kneading extraction in a strand shape, cooled in a strand bath (water bath) to give a granulated polyamide resin composition pellets with a cutter.
The obtained pellets were examined for UL-94VB, moldability, MD, combustion behavior (cone calorimeter test), glow wire ignition test (GWI), and electrical characteristics (CTI) by the measurement methods described above. The results are shown in Tables 1 and 2.
[0060]
[Example 2]
Polyamide resin a-1 containing an aromatic component is 100.0 parts by weight (64.0% by weight), metal borate compound b-1 is 25.0 parts by weight (16.0% by weight), and reinforcing material c-1 A polyamide composition comprising 31.3 parts by weight (20.0% by weight) was obtained.
Except that the raw materials to be prepared (that is, the setting of the feeding speed to the extruder) were 64.0% by weight of the polyamide resin a-1 containing an aromatic component and 16.0% by weight of the metal borate compound b-1. Pellets were obtained in the same manner as in Example 1, and UL-94VB, moldability, MD, combustion behavior (cone calorimeter test), glow wire ignition test (GWI), and electrical characteristics (CTI) were examined. The results are shown in Tables 1 and 2.
[0061]
[Production Example 4]
10% by weight silicone-containing polyamide comprising 100.0 parts by weight (90.0% by weight) of polyamide resin a-1 containing an aromatic component and 11.1 parts by weight (10.0% by weight) of silicone compound d-1. A resin composition was obtained.
A twin screw extruder (manufactured by Werner & Pfleiderer: ZSK) having one location on the upstream side (hereinafter abbreviated as top-F) and one supply port at the central portion of the extruder (hereinafter, the central portion of the extruder is abbreviated as side-1). -25) Cylinder set temperature of 240 ° C, screw rotation of 300rpm, discharge using a liquid addition device attached near the center of the cylinder (6th block out of 10 blocks from the top feed hopper) and clogging side-1 Polyamide resin a-1 containing an aromatic component is supplied from top-F at an addition amount of 9.0 kg / hr under the condition of an amount of 10 kg / hr, and silicone compound d-1 is added at an addition amount of 1 using a liquid addition apparatus. Add directly into the cylinder system at 0.0 kg / hr, knead the two together, take them out into strands, cool them in a strand bath (water tank), and then make them with a cutter. To obtain a 10 wt% silicone-containing polyamide resin composition pellets.
[0062]
[Example 3]
The polyamide resin a-1 containing an aromatic component is 100.0 parts by weight (70.0% by weight), the metal borate compound b-1 is 11.4 parts by weight (8.0% by weight), and the reinforcing material c-1 Of 28.6 parts by weight (20.0% by weight) and a silicone compound d-1 of 2.9 parts by weight (2.0% by weight) was obtained.
The raw materials (that is, the setting of the charging speed to the extruder) were 52.0% by weight of the polyamide resin a-1 containing an aromatic component, 20.0% by weight of the 10% silicone-containing polyamide resin of Production Example 4, Prepared so that the acid metal compound b-1 is 8.0% by weight and the reinforcing material c-1 is 20.0% by weight, one on the upstream side, 2 on the downstream side near the center of the extruder and the die. Polyamide resin a-1 containing an aromatic component under conditions of a cylinder set temperature of 240 ° C., a screw rotation of 200 rpm, and a discharge rate of 30 kg / hr using a twin screw extruder (Toshiba Machine: TEM35) having a supply port at a location And 10 wt% silicone-containing polyamide resin of Production Example 4 from top-F, borate metal compound b-1 from side-1, and reinforcing material c-1 from side-2 to a total discharge rate of 30 kg / hr. Become Uni adjusted to supply respectively, and melt-kneaded extraction in a strand shape, cooled in a strand bath (water bath) to give a granulated polyamide resin composition pellets with a cutter.
The obtained pellets were examined for UL-94VB, moldability, MD, combustion behavior (cone calorimeter test), glow wire ignition test (GWI), and electrical characteristics (CTI) by the measurement methods described above. The results are shown in Tables 1 and 2.
[0063]
[Example 4]
The polyamide resin a-1 containing an aromatic component is 100.0 parts by weight (68.0% by weight), the metal borate compound b-1 is 11.8 parts by weight (8.0% by weight), and the reinforcing material c-1 Was 29.4 parts by weight (20.0% by weight) and silicone compound d-1 was 5.9 parts by weight (4.0% by weight).
The raw materials to be prepared (that is, the setting of the feeding speed into the extruder) are 32.0% by weight of the polyamide resin a-1 containing an aromatic component, and 40.0% by weight of the 10% by weight silicone-containing polyamide resin of Production Example 4. Except that, pellets were obtained in the same manner as in Example 3, and UL-94VB, moldability, MD, combustion behavior (corn calorimeter test), glow wire ignition test (GWI), and electrical characteristics (CTI) were examined. It was. The results are shown in Tables 1 and 2.
[0064]
[Example 5]
The polyamide resin a-1 containing an aromatic component is 100.0 parts by weight (64.8% by weight), the metal borate compound b-1 is 12.3 parts by weight (8.0% by weight), and the reinforcing material c-1 30.9 parts by weight (20.0% by weight), and a silicone compound d-1 of 11.1 parts by weight (7.2% by weight) was obtained.
The raw materials to be prepared (that is, the setting of the feeding speed to the extruder) were 0% by weight for the polyamide resin a-1 containing an aromatic component, and 72.0% by weight for the 10% by weight silicone-containing polyamide resin of Production Example 4. Except for the above, pellets were obtained in the same manner as in Example 3, and UL-94VB, moldability, MD, combustion behavior (cone calorimeter test), glow wire ignition test (GWI), and electrical characteristics (CTI) were examined. The results are shown in Tables 1 and 2.
[0065]
[Example 6]
Polyamide resin a-1 containing an aromatic component is 100.0 parts by weight (64.8% by weight), borate metal compound b-2 is 12.3 parts by weight (8.0% by weight), reinforcing material c-1 30.9 parts by weight (20.0% by weight), and a silicone compound d-1 of 11.1 parts by weight (7.2% by weight) was obtained.
The raw materials to be prepared (that is, the setting of the feeding speed to the extruder) are 0% by weight of the polyamide resin a-1 containing an aromatic component, 72.0% by weight of the 10% by weight silicone-containing polyamide resin of Production Example 4, A pellet was obtained in the same manner as in Example 3 except that the acid metal compound b-2 was 8.0% by weight, and UL-94VB, moldability, MD, combustion behavior (corn calorimeter test), glow wire ignition property. Test (GWI) and electrical characteristics (CTI) were examined. The results are shown in Tables 1 and 2.
[0066]
[Production Example 5]
10% by weight silicone-containing polyamide comprising 100.0 parts by weight (90.0% by weight) of polyamide resin a-1 containing an aromatic component and 11.1 parts by weight (10.0% by weight) of silicone compound d-2 A resin composition was obtained.
Except having changed the silicone compound into d-2, it carried out similarly to manufacture example 4, and obtained the 10 weight% silicone containing polyamide resin composition pellet.
[0067]
[Example 7]
The polyamide resin a-1 containing an aromatic component is 100.0 parts by weight (64.8% by weight), the metal borate compound b-1 is 12.3 parts by weight (8.0% by weight), and the reinforcing material c-1 30.9 parts by weight (20.0% by weight) and a silicone compound d-2 of 11.1 parts by weight (7.2% by weight) was obtained.
The raw materials to be prepared (that is, the setting of the feeding speed to the extruder) were 0% by weight of the polyamide resin a-1 containing an aromatic component, and 72.0% by weight of the 10% by weight silicone-containing polyamide resin of Production Example 5. Except for the above, pellets were obtained in the same manner as in Example 3, and UL-94VB, moldability, MD, combustion behavior (cone calorimeter test), glow wire ignition test (GWI), and electrical characteristics (CTI) were examined. The results are shown in Tables 1 and 2.
[0068]
[Comparative Example 1]
A polyamide composition comprising 100.0 parts by weight (80.0% by weight) of polyamide resin a-1 containing an aromatic component and 25.0 parts by weight (20.0% by weight) of reinforcing material c-1 was obtained. .
Examples except that the raw materials to be prepared (that is, the setting of the charging speed into the extruder) were 80.0 wt% for the polyamide resin a-1 containing an aromatic component and 0 wt% for the metal borate compound b-1 The pellets were obtained in the same manner as in Example 1, and UL-94VB, moldability, MD, combustion behavior (corn calorimeter test), glow wire ignition test (GWI), and electrical characteristics (CTI) were examined. The results are shown in Tables 1 and 2.
[0069]
[Comparative Example 2]
A polyamide composition comprising 100.0 parts by weight (90.0% by weight) of polyamide resin a-1 containing an aromatic component and 11.1 parts by weight (10.0% by weight) of silicone compound d-1 was obtained. .
The 10 wt% silicone-containing polyamide resin pellets of Production Example 4 were used as they were, and UL-94VB, moldability, MD, and combustion behavior (cone calorimeter test) were examined. The results are shown in Tables 1 and 2.
[0070]
[Comparative Example 3]
Polyamide resin a-1 containing an aromatic component is 100.0 parts by weight (72.0% by weight), reinforcing material c-1 is 27.8 parts by weight (20.0% by weight), and silicone compound d-1 is 11 A polyamide composition comprising 1 part by weight (8.0% by weight) was obtained.
The raw materials to be prepared (that is, the setting of the feeding speed into the extruder) were 0% by weight of the polyamide resin a-1 containing an aromatic component, 80.0% by weight of the 10% silicone-containing polyamide resin of Production Example 4, A pellet was obtained in the same manner as in Example 3 except that the acid metal compound b-1 was changed to 0% by weight, and UL-94VB, moldability, MD, combustion behavior (cone calorimeter test), glow wire ignition test ( GWI) and electrical characteristics (CTI) were examined. The results are shown in Tables 1 and 2.
[0071]
[Production Example 6]
10% by weight silicone-containing polyamide comprising 100.0 parts by weight (90.0% by weight) of polyamide resin a-1 containing an aromatic component and 11.1 parts by weight (10.0% by weight) of silicone compound d-3 A resin composition was obtained.
Except having changed the silicone compound into d-3, it carried out similarly to manufacture example 4, and obtained the 10 weight% silicone containing polyamide resin composition pellet.
[0072]
[Example 8]
The polyamide resin a-1 containing an aromatic component is 100.0 parts by weight (70.0% by weight), the metal borate compound b-1 is 11.4 parts by weight (8.0% by weight), and the reinforcing material c-1 Of 28.6 (20.0% by weight), and a silicone compound d-3 of 2.9 parts by weight (2.0% by weight) was obtained.
The raw materials (that is, the setting of the charging speed into the extruder) were 52.0% by weight of the polyamide resin a-1 containing an aromatic component, 20.0% by weight of the 10% silicone-containing polyamide resin of Production Example 6, and boron Prepared so that the acid metal compound b-1 is 8.0% by weight and the reinforcing material c-1 is 20.0% by weight, one on the upstream side, 2 on the downstream side near the center of the extruder and the die. Polyamide resin a-1 containing an aromatic component under conditions of a cylinder set temperature of 240 ° C., a screw rotation of 200 rpm, and a discharge rate of 30 kg / hr using a twin screw extruder (Toshiba Machine: TEM35) having a supply port at a location And the 10 wt% silicone-containing polyamide resin of Production Example 6 is from top-F, the borate metal compound b-1 is from side-1, and the reinforcing material c-1 is from side-2 to a total discharge amount of 30 kg / hr. Become Uni adjusted to supply respectively, and melt-kneaded extraction in a strand shape, cooled in a strand bath (water bath) to give a granulated polyamide resin composition pellets with a cutter.
The obtained pellets were examined for UL-94VB, moldability and MD by the measurement method described above. The results are shown in Table 3.
[0073]
[Example 9]
The polyamide resin a-1 containing an aromatic component is 100.0 parts by weight (68.0% by weight), the metal borate compound b-1 is 11.8 parts by weight (8.0% by weight), and the reinforcing material c-1 Was 29.4 parts by weight (20.0% by weight) and silicone compound d-3 was 5.9 parts by weight (4.0% by weight).
The raw materials to be prepared (that is, the setting of the feeding speed into the extruder) are 32.0% by weight of the polyamide resin a-1 containing an aromatic component, and 40.0% by weight of the 10% by weight silicone-containing polyamide resin of Production Example 6. Except that, pellets were obtained in the same manner as in Example 8, and UL-94VB, moldability, and MD were examined. The results are shown in Table 3.
[0074]
[Example 10]
The polyamide resin a-1 containing an aromatic component is 100.0 parts by weight (64.8% by weight), the metal borate compound b-1 is 12.3 parts by weight (8.0% by weight), and the reinforcing material c-1 Was a polyamide composition comprising 30.9 parts by weight (20.0% by weight) and 11.1 parts by weight (7.2% by weight) of silicone compound d-3.
The raw materials to be prepared (that is, the setting of the feeding speed into the extruder) were 0% by weight for the polyamide resin a-1 containing an aromatic component, and 72.0% by weight for the 10% by weight silicone-containing polyamide resin in Production Example 6. Except for the above, pellets were obtained in the same manner as in Example 8, and UL-94VB, moldability, and MD were examined. The results are shown in Table 3.
[0075]
Example 11
The polyamide resin a-1 containing an aromatic component is 100.0 parts by weight (64.8% by weight), the metal borate compound b-1 is 12.3 parts by weight (8.0% by weight), and the reinforcing material c-1 30.9 parts by weight (20.0% by weight), and a silicone compound d-4 of 11.1 parts by weight (7.2% by weight) was obtained.
The raw materials (that is, the setting of the charging speed to the extruder) were 64.8% by weight of the polyamide resin a-1 containing an aromatic component, 8.0% by weight of the metal borate compound b-1, and the reinforcing material c-1. 20.0% by weight, and finely pulverized silicone compound d-4 was prepared so as to be 7.2% by weight, one on the upstream side, the central part of the extruder and the downstream side near the die Polyamide resin a- containing an aromatic component under the conditions of a cylinder setting temperature of 240 ° C., a screw rotation of 200 rpm, and a discharge rate of 30 kg / hr using a twin-screw extruder having two supply ports (Toshiba Machine: TEM35) 1 and the silicone compound d-4 are adjusted from top-F, the borate metal compound b-1 is adjusted from side-1 and the reinforcing material c-1 is adjusted from side-2 so that the total discharge amount is 30 kg / hr. And supply Melt kneading a strand shape taken out and cooled in a strand bath (water bath) to give a granulated polyamide resin composition pellets with a cutter.
The obtained pellets were examined for UL-94VB, moldability and MD by the measurement method described above. The results are shown in Table 3.
[0076]
[Comparative Example 4]
The polyamide resin a-1 containing an aromatic component is 100.0 parts by weight (72.0% by weight), the reinforcing material c-1 is 27.8 parts by weight (20.0% by weight), and the silicone compound d-3 is 11 A polyamide composition comprising 1 part by weight (8.0% by weight) was obtained.
The raw materials to be prepared (that is, the setting of the feeding speed into the extruder) were 0% by weight of the polyamide resin a-1 containing an aromatic component, 80.0% by weight of the 10% silicone-containing polyamide resin of Production Example 6, Except that the acid metal compound b-1 was 0% by weight, pellets were obtained in the same manner as in Example 8, and UL-94VB, moldability, MD, and combustion behavior (corn calorimeter test) were examined. The results are shown in Table 3.
[0077]
Example 12
Polyamide resin a-2 containing an aromatic component is 100.0 parts by weight (50.4% by weight) in the thermoplastic resin, 15.9 parts by weight (8.0% by weight) of metal borate compound b-1; A polyamide composition comprising 39.7 parts by weight (20.0% by weight) of the reinforcing material c-1 and 42.9 parts by weight (21.6% by weight) of the polyphenylene ether resin e-1 was obtained.
The raw materials (that is, the setting of the feeding speed to the extruder) were 50.4% by weight of polyamide resin a-2 containing an aromatic component, 21.6% by weight of polyphenylene ether resin e-1, and metal borate compound b- Prepare 1 so that the weight is 8.0 wt% and the reinforcing material c-1 is 20.0 wt%, and supply ports at one location on the upstream side and two locations on the downstream side near the center of the extruder and the die. Polyamide ether resin e-1 containing aromatic components and polyphenylene ether resin e under the conditions of a cylinder set temperature of 280 ° C., a screw rotation of 200 rpm, and a discharge rate of 30 kg / hr using a twin screw extruder (Toshiba Machine: TEM35) -1 is supplied from top-F, the borate metal compound b-1 is supplied from side-1, and the reinforcing material c-1 is supplied from side-2 while adjusting the total discharge amount to 30 kg / hr. Melting Kneading a strand shape taken out and cooled in a strand bath (water bath) to give a granulated polyamide resin composition pellets with a cutter.
The obtained pellets were examined for UL-94VB, moldability and MD by the measurement method described above. The results are shown in Table 3.
[0078]
[Comparative Example 5]
A polyamide composition comprising 100.0 parts by weight (80.0% by weight) of polyamide resin a-2 containing an aromatic component and 25.0 parts by weight (20.0% by weight) of reinforcing material c-1 was obtained. .
Examples except that the raw materials to be prepared (that is, the setting of the feeding speed to the extruder) were 80.0 wt% for the polyamide resin a-2 containing an aromatic component and 0 wt% for the metal borate compound b-1 The pellets were obtained in the same manner as in Example 1, and UL-94VB, moldability, and MD were examined. The results are shown in Table 3.
As can be seen from Examples 1 to 12 and Comparative Examples 1 to 5 in Tables 1 to 3, the polyamide resin composition does not contain a halogen flame retardant, an antimony flame retardant aid, and a phosphorus flame retardant, and is aromatic. By adding a metal borate that is a non-halogen, non-antimony, non-phosphorus flame retardant to a polyamide resin containing components, flame retardancy can be improved without degrading the electrical properties of the polyamide resin. It was possible to achieve a balance between both electrical characteristics and flame retardancy.
The result shows that the flame retardancy is greatly improved by the metal borate compound, and the electrical characteristics are very high even if the metal borate compound is added. A stripped material was obtained.
[0079]
[Table 1]

[0080]
[Table 2]

[0081]
[Table 3]

[0082]
【The invention's effect】
The composition of the present invention is a flame retardant polyamide resin material that does not contain halogen-based flame retardants such as chlorine and bromine, antimony-based auxiliary flame retardants, and phosphorus-based flame retardants. The flame retardancy and electrical characteristics can be improved without impairing the properties, good moldability, and electrical characteristics, mold corrosion can be reduced, and it can be suitably used for applications such as home appliance parts, electronic parts, and automobile parts.

Claims (16)

(A) Kaori the aromatic components have a 100 parts by weight containing Mupo polyamide resin and (b) boric acid metal compound from 11.1 to 200 parts by weight, flame retardant containing no halogen-based flame retardant, a phosphorus-based flame retardant Polyamide resin composition. (A) (1) a copolymer comprising poly (hexamethylene adipamide) units and poly (hexamethylene isophthalamide) units, (2) poly (hexamethylene adipamide) units, poly (hexamethylene isophthalamide) Ternary copolymer consisting of units and poly (hexamethylene terephthalamide) units, (3) ternary copolymer consisting of poly (hexamethylene adipamide) units, poly (hexamethylene isophthalamide) units and poly (caprolactam) units Aromatic components selected from the group consisting of polymers, (4) poly (nonamethylene terephthalamide), (5) poly (hexamethylene isophthalamide) and (6) polyamides containing aromatic components derived from xylylenediamine components 100 parts by weight of a polyamide resin containing a and (b) boric acid metal compound 11.1-2 0 parts by weight have a halogen-based flame retardant, it does not contain a phosphorus-based flame retardant The flame retardant polyamide resin composition. (A) 100 parts by weight of a polyamide resin containing an aromatic component, (b) boric acid metal compound from 11.1 to 200 parts by weight and (c) a flame retardant of claim 1 or 2, wherein a reinforcement 5 to 200 parts by weight -Soluble polyamide resin composition. Furthermore, (d) The flame-retardant polyamide resin composition of any one of Claims 1-3 formed by containing 0.01-100 weight part of silicone compounds. (A) The flame retardant polyamide resin composition according to any one of claims 1 to 4, wherein the aromatic component of the polyamide resin containing an aromatic component is derived from an isophthalic acid component. The flame retardant polyamide resin composition according to any one of claims 1 to 4, wherein (a) the polyamide resin containing an aromatic component is a poly (metaxylylene adipamide) resin. (B) boric acid metal compound, any one of claims 1 to 6 is _{xZnO · yB 2 O 3 · zH} 2 O (x> 0, y> 0, z ≧ 0) zinc borate compound represented by The flame-retardant polyamide resin composition according to item 1. (B) boric acid metal compound, according to claim 7 which is a compound represented by _{2ZnO · 3B 2 O 3 · 3.5H} 2 O, 4ZnO · B 2 O 3 · H 2 O, or 2ZnO · _3B 2 _{O 3} The flame-retardant polyamide resin composition described in 1. (B) boric acid metal compound, flame-retardant polyamide resin composition according to claim 8 which is a compound represented by _{2ZnO · 3B 2 O 3 · 3.5H} 2 O. (C) A reinforcing material is a fibrous filler, The flame-retardant polyamide resin composition of any one of Claims 3-9. The flame retardant polyamide resin composition according to claim 10, wherein (c) the reinforcing material is glass fiber. The flame-retardant polyamide resin composition according to any one of claims 4 to 11, wherein (d) the silicone compound is a silicone compound comprising at least one selected from the group having the following siloxane units.
1) M units (monofunctional)

2) D unit (bifunctional)

3) T unit (trifunctional)

4) Q unit (tetrafunctional)

(However, R is the same or different substituent, and is selected from an alkyl group, aryl group, benzyl group, vinyl group, allyl group, alkoxy group, hydroxy group, amino group, methyl ester group and ethyl ester group. ) (D) The flame retardant polyamide resin composition according to any one of claims 4 to 12, wherein the silicone compound is a silicone compound containing a vinyl group. (D) The silicone group has a vinyl group ratio of 2% or more in a molar ratio among all organic substituents bonded to silicon atoms excluding trimethylsilyl group, alkoxy group and hydroxyl group. The flame-retardant polyamide resin composition according to any one of 4 to 13. The flame retardant polyamide resin composition according to any one of claims 1 to 14, further comprising (e) 0.1 to 100 parts by weight of a polyphenylene ether resin. A molded article comprising the flame retardant polyamide resin composition according to any one of claims 1 to 15.