JP4457592B2 - Flame retardant resin composition and molded article - Google Patents

Description

【化２】

【化３】

【化４】

【００３１】
上記一般式（４）で表されるリン酸塩化合物において、式中Ｒ₁、Ｒ₂、Ｒ₃及びＲ₄で表されるアルキル基としては、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、第二ブチル、第三ブチル、ペンチルが挙げられる。
本発明で用いられる上記一般式（４）で表されるリン酸塩化合物としては、ジアミンとトリアジン誘導体及び（ポリ又はピロ）リン酸から得られるリン酸アミン塩であり、該リン酸アミン塩は、例えば次ぎの方法によって得ることができる。すなわち、反応容器に、不活性溶剤を添加もしくは溶剤を添加することなしに、所定のリン酸もしくは縮合度約２〜１００の縮合リン酸を仕込む。次いで、〔Ｒ₁Ｒ₂Ｎ（ＣＨ₂）ｍＮＲ₃Ｒ₄〕で表されるジアミン（ここでＲ₁、Ｒ₂、Ｒ₃及びＲ₄はそれぞれＨ もしくは炭素数１〜５の直鎖もしくは分岐のアルキル基であり、Ｒ₁、 Ｒ₂、Ｒ₃及びＲ₄は同一の基であっても異なってもよい。また、ｍは１ 〜１０の整数である。）、ピペラジンもしくはピペラジン環を含むジアミンである化合物（以下これらを総称してジアミン類という。）を直接あるいは水等に溶解または溶剤で希釈して添加し、―１０〜１００℃で反応させる。反応は中和反応であり、速やかに進行する。次にここで生成した反応物を単離し、もしくは単離することなく、アンモニアもしくは上記一般式（５）で表されるトリアジン誘導体を水等の溶媒で希釈あるいは希釈することなしに添加、加熱反応させることによりリン酸アミン塩が得られる。反応に関与するジアミン類、アンモニア及びトリアジン誘導体の量は、使用するリン酸もしくは縮合リン酸のリン濃度によって変化する。即ち、ジアミン類は、リン酸もしくは縮合リン酸中に含まれる水酸基の数の２分の１よりも少ないモル数、好ましくはリン酸もしくは縮合リン酸とほぼ等モル量を添加し、反応させ、中間生成物を得る。次いで該中間生成物に残留している水酸基に相当する量のアンモニアもしくはトリアジン誘導体を添加し、反応させる。
上記ジアミン類の具体的な例としては、Ｎ、Ｎ、Ｎ′、Ｎ′―テトラメチルジアミノメタン、エチレンジアミン、Ｎ、Ｎ′―ジメチルエチレンジアミン、Ｎ、Ｎ′―ジエチルエチレンジアミン、Ｎ、Ｎ―ジメチルエチレンジアミン、Ｎ、Ｎ―ジエチルエチレンジアミン、Ｎ、Ｎ、Ｎ′、Ｎ′―テトラメチルエチレンジアミン、Ｎ、Ｎ、Ｎ′、Ｎ′―ジエチルエチレンジアミン、１，２―プロパンジアミン、１，３−プロパンジアミン、テトラメチレンジアミン、ペンタメチレンジアミン、ヘキサメチレンジアミン、１，７−ジアミノヘプタン、１，８−ジアミノオクタン、１，９−ジアミノノナン、１，１０−ジアミノデカン、ピペラジン、ｔｒａｎｓ―２，５−ジメチルピペラジン、１，４−ビス（２−アミノエチル）ピペラジン、１，４―ビス（３−アミノプロピル）ピペラジン等が挙げられる。
【００３２】
また、上記トリアジン誘導体の具体的な例としては、メラミン、アセトグアナミン、ベンゾグアナミン、アクリルグアナミン、２，４―ジアミノー６−ノニルー１，３，５―トリアジン、２，４−ジアミノー６―ハシドロキノンー１，３，５−トリアジン、２−アミノー４，６―ジハイドロキシー１，３，５−トリアジン、２，４−ジアミノー６−メトキシー１，３，５−トリアジン、２，４−ジアミノー６−エトキシー１，３，５−トリアジン、２，４−ジアミノー６−プロポキシー１，３，５−トリアジン、２，４−ジアミノー６−イソプロポキシー１，３，５―トリアジン、２，４−ジアミノー６−メルカプトー１，３，５−トリアジン、２−アミノー４，６−ジメルカプトー１，３，５−トリアジン等が挙げられる。
【００３３】
上記一般式（６）で表されるリン酸塩化合物は、（ポリ又はピロ）リン酸とジアミンの塩であり、任意の反応比率で反応させて得ることができる。例えばピロリン酸ピペラジン塩の場合は、ピペラジン塩酸塩とピロリン酸ナトリウムとを水溶液中で反応させて、水難性沈殿として容易に得られる。本発明で使用される好ましいリン酸・ジアミン塩としては、リン酸ピペラジン塩が挙げられ、具体的にはオルトリン酸ピペラジン塩、ピロリン酸ピペラジン塩、ポリリン酸ピペラジン塩等が挙げられる。
【００３４】
上記一般式（７）で表されるリン酸塩化合物はリン酸・トリアジン誘導体塩であり、次の方法によって得ることができる。例えばリン酸メラミン塩の場合は、リン酸とメラミンを任意の反応比率で反応させて得られる。本発明で好ましく使用されるリン酸メラミン塩の具体的な例としては、例えばオルトリン酸メラミン塩、ピロリン酸メラミン塩、ポリリン酸メラミン塩等が挙げられる。
【００３５】
上記一般式（６）で表されるリン酸塩化合物と上記一般式（７）で表されるリン酸塩化合物との組み合わせ割合（前者／後者）は、好ましくは５〜９５／９５〜５（質量％）、更に好ましくは１０〜９０／９０〜１０（質量％）、特に好ましくは３０〜７０／７０〜３０（質量％）である。この範囲にあると優れた難燃性効果が得られる。
【００３６】
本発明で使用する（Ｄ）成分のリン酸塩化合物は、平均粒子径４０μｍ以下、更に好ましくは１０μｍ以下のものが好適である。リン酸塩化合物の平均粒径が４０μｍより大きい場合には、本発明の樹脂組成物への分散性が悪くなり、難燃性、耐衝撃性、及び成形品表面外観が劣る場合がある。
【００３７】
本発明の難燃性樹脂組成物を構成する（Ａ）、（Ｂ）及び（Ｃ）の合計を１００質量部とした場合、成分（Ｄ）の含有量は５〜７０質量部であり、好ましくは５〜５０質量部、更に好ましくは１０〜５０質量部、特に好ましくは１０〜４０質量部であり、その使用量が５質量部未満では、難燃性が劣り、７０質量を超えると耐衝撃性、及び成形品表面外観が劣る。
【００３８】
本発明の難燃性樹脂組成物の難燃性を向上させる目的から、ドリッピング防止剤、多価水酸基含有化合物、金属・半金属酸化物、遷移金属酸化物、シリコーン化合物、有機酸の金属塩、及び金属水酸化物等を配合することができ、これらは１種単独で、または２種以上を組み合わせて用いることができる。ここで使用されるドリッピング防止剤としては、ポリテトラフルオロエチレン、ポリフッ化ビニリデン、ポリヘキサフルオロプロピレン等のフッ素系樹脂、パーフルオロメタンスルホン酸、パープルオローｎ―ブタンスルホン酸、パーフルオロオクタンスルホン酸、パーフルオロー２−エチルヘキサンスルホン酸等のパーフルオロアルカンスルホン酸のナトリウム、カリウム、カルシウム塩等のアルカリ金属塩及びアルカリ土類金属塩、リン酸化合物、スルホン酸化合物のアルカリ金属塩及びアルカリ土類金属塩等が挙げられ、これらは、１種単独で、または２種以上を組み合わせて用いることが出来る。これらのドリッピング防止剤は、本発明の難燃性樹脂組成物１００質量部に対して０．０１〜３質量部の範囲で用いることが好ましい。
【００３９】
多価水酸基含有化合物としては、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、ポリペンタエリスリトール、トリスヒドロキシエチルイソシアネート、ポリエチレングリコール、グリセリン、デンプン、ブドウ糖、セルロース、ソルビトール等がある。これらの多価水酸基含有化合物のうち多価アルコール化合物は樹脂との馴染みがよく、低水溶性及び低吸湿性の点で好ましく、とりわけジペンタエリスリトール、トリペンタエリスリトール、ポリペンタエリスリトール（縮合度≧４）は、水溶性、吸湿性が特に低いため本発明に適している。これらの多価水酸基含有化合物は、本発明の難燃性樹脂組成物１００質量部に対して１〜１５質量部の範囲で使用することが好ましい。
【００４０】
金属・半金属酸化物は、典型金属元素及び半金属元素の酸化物であり、酸化アルミニウム、酸化リチウム、酸化マグネシウム、酸化カルシウム、酸化バリウム、酸化ホウ素、酸化アルミニウム、酸化珪素、酸化錫、酸化燐、酸化ビスマス等があり、これらは１種単独で、または２種以上を組み合わせて用いることができる。また、遷移金属酸化物は、遷移金属元素の酸化物であり、例えば、酸化チタン、酸化鉄、酸化コバルト、酸化ニッケル、酸化銅、酸化亜鉛、酸化ジルコニウム等があり、これらは１種単独で、または２種以上を組み合わせて用いることができる。上記金属酸化物は、本発明の難燃性樹脂組成物１００質量部に対して２０質量部以下で使用することが、耐衝撃性から好ましい。
【００４１】
上記シリコーン化合物としては、任意の割合でＭ単位、Ｄ単位、Ｔ単位、Ｑ単位を含むポリオルガノシロキサンが好ましく、液状、粉体、ゴム状のものの何れも使用可能であるが、Ｍ単位、Ｄ単位、及びＴ単位からなり、置換アルキル基がメチル基とフェニル基からなるポリメチル・フェニルシロキサンが特に好ましい。またこれらのポリオルガノシロキサンには、アルコキシ基、ビニル基等、水酸基、水素基等が付加されていても良い。シリコーン化合物は、本発明の難燃性樹脂組成物１００質量部に対して０．５〜２０質量部の範囲で使用することが好ましい。
【００４２】
有機酸の金属塩としては、ステアリン酸バリウム、ステアリン酸リチウム、ステアリン酸カルシウム、ステアリン酸亜鉛等の有機酸のアルカリ金属塩、及びアルカリ土類金属塩等があり、これらは本発明の難燃性樹脂組成物１００質量部に対して、０．１〜１０重量部の範囲で使用することが好ましい。
【００４３】
本発明の難燃性樹脂組成物には、公知の無機充填材を配合することができる。ここで使用される無機充填材としては、ガラス繊維、ミルドガラス、ガラスビーズ、ガラスフレーク、中空ガラス、炭素繊維、炭素繊維のミルドファイバー、タルク、炭酸カルシウムウイスカー、ワラストナイト、マイカ、カオリン、モンモリロナイト、ヘクトライト、酸化亜鉛ウイスカー、チタン酸カリウムウイスカー、ホウ酸アルミニウムウイスカー、板状アルミナ、及び有機酸処理されたスメクタイト等があり、これらは１種単独で、または２種以上組み合わせて用いることができ。又、上記無機充填材の分散性を向上させる目的から、公知のカップリング剤で表面処理したものを用いることもできる。公知のカップリング剤としては、シラン系カップリング剤、チタネート系カップリング剤等がある。上記無機充填材は、本発明の難燃性樹脂組成物１００質量部に対して、１〜１００質量部の範囲で通常使用される。
【００４４】
本発明の難燃性樹脂組成物には、公知の耐候（光）剤、帯電防止剤、酸化防止剤、滑剤、可塑剤、着色剤、染料、結晶造核剤、抗菌剤、防黴剤、発泡剤等を配合することができる。更に、本発明の難燃性樹脂組成物には、他の公知の熱可塑性重合体である、ポリアミド樹脂、ポリアミドエラストマー、ポリエステル樹脂、ポリエステルエラストマー、ポリカーボネート、ポリオキシメチレン、エポキシ樹脂、フェノール樹脂、ＬＣＰ、熱可塑性ポリウレタン等を適宜配合できる。
【００４５】
本発明の難燃性樹脂組成物は、各種押出機、バンバリーミキサー、ニーダー、連続ニーダー等により、各成分を混練することにより調製することができる。好ましい製造法は、押出機（好ましくは二軸押出機）またはバンバリーミキサーを用いる方法である。
更に、各々の成分を混練するに際して、それらの成分を一括して混練してもよく、押出機、バンバリーミキサー等を用いて、多段、分割配合し混練してもよい。尚、バンバリーミキサー、ニーダー等で混練したあと、押出機により更に分割添加、混練、脱気等を行いペレット化することもできる。
このようにして調製された本発明の難燃性樹脂組成物は、射出成形、プレス成形、シート押出成形、真空成形、異形押出成形、発泡成形等の公知の成形法により、成形品を得ることができる。これらの成形法で得られた成形品としては、下記のものが例示される。
【００４６】
各種ギア、各種ケース、センサー、ＬＥＰランプ、コネクター、ソケット、抵抗器、リレーケース、スイッチ、コイルボビン、コンデンサー、バリコンケース、光ピックアップ部品、発振子、各種端子板、変成器、プラグ、プリント配線板、チューナー、スピーカー、マイクロフォン、ヘッドフォン、小型モーター、磁気ヘッドベース、パワーモジュール、ハウジング、半導体、液晶ＦＤＤキャリッジ、ＦＤＤシャーシー、モーターブラッシュホルダー、パラボラアンテナ、コンピューター関連部品等に代表される電気・電子部品。ＶＴＲ部品、テレビ部品、アイロン、ヘアードライヤー、炊飯器部品、電子レンジ部品、音響部品、オーデイオ・レーザーディスク・コンパクトディスクなどの音声器部品、照明部品、冷蔵庫部品などに代表される家庭・事務電気製品部品。オフィスコンピューター関連部品、電話機器関連部品、ファクシミリー関連部品、複写機関連部品、洗浄用治具関連部品。便座、タンクカバー、ケーシング、台所回りの部品、洗面台関連部品、浴室関連パーツ等のサニタリー関連部品。窓枠、家具、床材、壁材等の住宅・住設関連部品。顕微鏡、双眼鏡、カメラ、時計などに代表される光学機器、精密機器関連部品。オルタネーターターミナル、オルタネーターコネクター、ＩＣレギュレーター、排気ガスバルブなどの各種バルブ、燃料関係・排気系・吸気系各種バルブ。エアーインテークノズルスノーケル、インテークマニホールド、燃料ポンプ、エンジン冷却水ジョイント、キャブレターメインボディー、キャブレタースペーサー、排気ガスセンサー、冷却水センサー、油温センサー、ブレーキパットウェアーセンサー、スロットルポジションセンサー、クランクシャフトポジションセンサー、エアーフローメーター、エアコン用サーモスタットベース、暖房温風フローコントロールバルブ、ラジエーターモーター用ブラッシュホルダー、ウオーターポンプインペラー、タービンベイン、ワイパーモーター関係部品、ディストリビューター、スタータースイッチ、スターターリレー、トランスミッション用ワイパーハーネス、ウインドウォッシャーノズル、エアコンパネルスイッチ基板、燃料関係電磁弁用コイルボビン、ヒューズ用コネクター、ホーンターミナル、電装部品絶縁板、ステップモーターローラー、ランプソケット、ランプリフレクター、ランプハウジング、ブレーキピストン、ソレノイドボビン、エンジンオイルフィルター、点火装置ケース。パソコン、プリンター、ディスプレイ、ＣＲＴディスプレイ、ノートパソコン、携帯電話、ＰＨＳ、ＤＶＤドライブ、ＰＤドライブ、フレキシブルディスクドライブ等の記憶装置のハウジング、シャーシー、リレー、スイッチ、ケース部材、トランス部材、コイルボビン等の電気・電子機器部品。バンパー、フェンダー等の車両用外装部材、その他各種用途。
【００４７】
【実施例】
以下に実施例を挙げ、本発明をさらに詳細に説明するが、本発明の主旨を越えない限り、本発明はかかる実施例に限定されるものではない。尚、実施例中において部及び％は、特に断らない限り質量基準である。また、実施例、比較例中の各種測定は、下記の方法に拠った。
【００４８】
１）評価方法
（１）ゴム質重合体のゲル含率：前記したため省略する。
（２）（Ａ）成分中に分散しているゴム質重合体成分の平均粒子径： （Ａ）成分の形成に用いるゴム質重合体ラテックスの平均粒子径は、光散乱法で測定した。測定機は、大塚電子社製ＬＰＡ―３１００型を使用し、７０回積算でミュムラント法を用いた。尚、（Ａ）成分中に分散しているゴム質重合体成分の平均粒子径は、ゴム質重合体ラテックスの平均粒子径とほぼ同じであることを電子顕微鏡で確認した。
（３）（Ａ）成分のグラフト率：前記したため省略する。
（４）（Ａ）成分のアセトン可溶分の極限粘度〔η〕：前記したため省略する。
（５）（Ｃ）成分の（水素添加）ジエン系重合体の結合スチレン量、数平均分子量、ビニル結合量及び水素添加率等の測定方法について
（５−１）結合スチレン量；水素添加前の重合体で測定した。６９９ｃｍ―１のフェニル基の吸収に基づいた赤外法による検量線から求めた。
（５−２）数平均分子量；水素添加前の重合体で測定した。ゲルパーミエーションクロマトグラフィー（ＧＰＣ）から求めた。
（５−３）ビニル結合量；水素添加前の重合体で測定した。赤外法（モレロ法）によって求めた。
（５−４）水素添加率；水素添加後の重合体で測定した。四塩化エチレンを溶媒として用い、１５％濃度で測定した１００ＭＨｚの¹Ｈ―ＮＭ Ｒスペクトルの不飽和二重結合部のスペクトル減少から算出した。
（６）難燃性；ＵＬ９４規格に準拠して、１．６ｍｍ肉厚試験片のＶ試験を行った。Ｖ試験の規格外のものはＮＲと記載した。
（７）耐衝撃性；ＩＳＯ試験法１７９に準して、ノッチ付きシャルピー衝撃強さ（ＫＪ／ｍ²）を測定した。
（８）耐薬品性；肉厚３．２ｍｍ×巾１２．７ｍｍ×長さ１２７ｍｍの試験片に１％の歪みをかけ、エチルアルコールを塗布したあと、２３℃で２４時間放置したあとの、成形品の状態を下記評価基準に基づき目視評価した。
○；変化無し
×；クラック発生または破断
（９）成形品表面外観；肉厚２．０ｍｍ×巾５０ｍｍ×長さ７０ｍｍの平板を成形し、下記評価基準で、目視評価した。
○；成形品表面が滑らかであり、ヒケも無い。
×；成形品表面が滑らかで無い、及び／または成形品表面にヒケがある。
【００４９】
２）難燃性樹脂組成物の成分
（１）（Ａ）成分；
（１−１）製造例Ａ１；ＡＢＳ樹脂
撹拌機を備えた内容積７Ｌのガラス製フラスコに窒素気流中で、イオン交換水７５部、ロジン酸カリウム０．５部、ｔ―ドデシルメルカプタン０．１部、ポリブタジエンラテックス（平均粒子径；３５００Å、ゲル含率；８５％）４０部（固形分）、スチレン１５部、アクリロニトリル５部を加え、撹拌しながら昇温した。内温が４５℃に達した時点で、ピロリン酸ナトリウム０．２部、硫酸第一鉄７水和物０．０１部及びブドウ糖０．２部をイオン交換水２０部に溶解した溶液を加えた。その後、クメンハイドロパーオキサイド０．０７部を加えて重合を開始した。１時間重合させた後、更にイオン交換水５０部、ロジン酸カリウム０．７部、スチレン３０部、アクリロニトリル１０部、ｔ―ドデシルメルカプタン０．０５部及びクメンハイドロパーオキサイド０．０１部を３時間かけて連続的に添加し、更に１時間重合を継続させた後、２、２′―メチレンービス（４−エチルー６−ｔ―ブチルフェノール）０．２部を添加し重合を完結させた。反応生成物のラテックスを硫酸水溶液で凝固、水洗した後、乾燥してスチレン系樹脂Ａ１を得た。この共重合樹脂Ａ１のグラフト率は６８％、アセトン可溶部の極限粘度〔η〕は、０．４５ｄｌ／ｇであった。
【００５０】
（１−２）製造例Ａ２；ＡＳ樹脂
内容積３０Ｌにリボン翼を備えたジャケット付き重合反応容器を２基連結し、窒素置換したあと、１基目の反応容器にスチレン７６部、アクリロニトリル２４部、トルエン２０部を連続的に添加した。分子量調節剤とてｔ―ドデシルメルカプタン０．１２部及びトルエン５部の溶液、及び重合開始剤として、１，１′―アゾビス（シクロヘキサンー１−カーボニトリル）０．１部及びトルエン５部の溶液を連続的に供給した。１基目の重合温度は、１１０℃にコントロールし平均滞留時間２．０時間、重合転化率５７％であった。得られた重合体溶液は、１基目の反応容器の外部に設けられたポンプにより、スチレン、アクリロニトリル、トルエン、分子量調節剤、及び重合開始剤の供給量と同量を連続的に取り出し２基目の反応容器に供給した。２基目の反応容器の重合温度は、１３０℃、平均滞留時間２．０時間、重合転化率７５％であった。２基目の反応容器で得られた共重合体溶液は、２軸３段ベント付き押出機を用いて、直接未反応単量体と溶剤を脱揮し、極限粘度〔η〕０．４８のスチレン系樹脂Ａ２を得た。
【００５１】
（２）（Ｃ）成分；
（２−１）製造例Ｃ１；スチレンーブタジエンブロック共重合体の部分水添物
撹拌機及びジャケット付きの内容積５０Ｌのオートクレーブを乾燥、窒素置換し、スチレン３０部を含むシクロヘキサン溶液を投入した。ついで、ｎ―ブチルリチウムを添加し、７０℃で１時間重合した後、ブタジエン４０部を含むシクロヘキサン溶液を加えて１時間、更にスチレン３０部を含むシクロヘキサン溶液を加えて１時間重合した。得られたブロック共重合体溶液の一部をサンプリングし、２，６−ジーｔｅｒｔ―ブチルカテコールをブロック共重合体１００部に対して０．３部添加し、その後、溶媒を加熱除去した。このものの、スチレン含量は６０％、ポリブタジエン部分の１，２―ビニル結合量は３５％、数平均分子量は５６０００であった。残りのブロック共重合体溶液にチタノセンジクロライドとトリエチルアルミニウムをシクロヘキサン中で反応させた溶液を加え、５０℃、５０ｋｇｆ／ｃｍ²に水素圧下、４０分水素化反応を 行った。
その後、脱触媒処理を行い、２，６―ジーｔｅｒｔ―ブチルカテコールを加えて減圧乾燥を行った。得られた重合体Ｃ１の水素添加率は６９％であった。
（２−２）製造例Ｃ２；スチレンーブタジエンブロック共重合体の部分水添物
製造例Ｃ１において、水素化反応時間を短くして、水素添加率５％の重合体Ｃ２を得た。
（２−３）製造例Ｃ３；スチレンーブタジエンブロック共重合体の水素化物
撹拌機及びジャケット付きの内容積５０Ｌのオートクレーブを乾燥、窒素置換し、シクロヘキサンとブタジエン２０部溶液を投入した。ついで、ｎ―ブチルリチウム０．０２５部を加えて、５０℃の等温重合を行った。添加率１００％になった時点で、テトラヒドロフラン０．７５部、ブタジエン６５部を添加し、５０℃から８０℃に昇温重合を行った。転化率が１００％になった時点でスチレン１５部を加え、更に重合反応を行い、水素添加前Ｓ―Ｂ１―Ｂ２トリブロック共重合体を得た。製造例Ｃ１同様にサンプリングし分析した結果、スチレンブロック１５％ （Ｓブロック）、１，２―ビニル含量３５％のブタジエンブロック（Ｂ１ブロック）、１，２―ビニル含量１０％のブタジエンブロック（Ｂ２ブロック）からなる数平均分子量２０万の重合体であった。
別の容器でチタノセンジクロライド１部をシクロヘキサンに分散させ、室温でトリエチルアルミニウム０．５部と反応させた。得られた均一溶液を上記ポリマー溶液に加え、５０℃で、５０ｋｇｆ／ｃｍ²の水素圧 力下、２時間水素化反応を行い、Ｃ１同様に重合体を回収した。本重合体Ｃ３の水素添加率は９９％であった。
【００５２】
（２−４）（Ｃ４）；変性スチレンーブタジエンブロック共重合体水素化物
リボン型撹拌翼を備えた内容積１０Ｌのステンレス製オートクレーブを窒素置換した後、窒素気流中で予めトルエンを溶媒として均一溶液にした上記（２−３）で得た重合体Ｃ３を３０部（固形分）、スチレン５２．５部、アクリロニトリル１７．５部、トルエン１２０部及びｔｅｒｔ―ドデシルメルカプタン０．１部を仕込み、撹拌しながら昇温し、５０℃にてベンゾイルパーオキサイド０．５部、ジクミルパーオキサイド０．１部を添加し、更に昇温し、８０℃に達した後は、８０℃一定で制御しながら重合反応を行わせた。反応開始後６時間目から１時間を要して１２０℃まで昇温し、更に２時間反応を行って終了した。重合転化率は、９７％であった。
１００℃まで冷却後、２，２−メチレンビスー４−メチルー６−ｔｅｒｔ―ブチルフェノール０．２部を添加した後、反応混合物をオートクレーブより抜き出し、水蒸気蒸留により未反応物と溶媒を留去し、粉砕したのちベント付き押出機（２２０℃、７００ｍｍＨｇ真空）にて実質的に揮発分を留去するとともに、重合体をペレット化し、重合体Ｃ４を得た。このもののグラフト率は、４５％、アセトン可溶分の極限粘度〔η〕は、０．４５ｄｌ／ｇであった。
【００５３】
（３）（Ｂ）成分；
（３−１）Ｂ１；プロピレン樹脂
日本ポリケム社製ブロックタイプポリプロピレン“ノバテックＢＣ６Ｃ”を用いた。
（３−２）Ｂ２；プロピレン樹脂
日本ポリケム社製ブロックタイプポリプロピレン“ノバテックＢＣ０６Ｃ”を用いた。
【００５４】
（４）（Ｄ）成分
（３−１）Ｄ１；ピロリン酸メラミン塩
メラミン２モルとピロリン酸１モルを反応させて得たものを用いた。
（３−２）Ｄ２；ピロリン酸ピペラジン塩
ピペラジン１モルとピロリン酸１モルを反応させて得たものを用いた。
（３−３）Ｄ３；ピロリン酸メラミンピペラジン塩
メラミン１モル、ピペラジン１モルとピロリン酸１モルを反応させて得たものを用いた。
【００５５】
（５）（Ｅ）その他の成分
（５−１）Ｅ１；ポリテトラフルオロエチレン
住友スリーエム社製“ホスタフロンＴＦ１６２０”を用いた。
（５−２）Ｅ２；ジペンタエリスリトール
和光純薬工業社製試薬を用いた。
【００５６】
３）実施例１〜９ 、比較例１〜７
表１記載の配合割合で、ヘンシエルミキサーにより混合した後、二軸押出機（シリンダー設定温度２００℃）を用いて溶融混練し、ペレット化した。
得られたペレットを十分に乾燥したのち、射出成形機（シリンダー設定温度２００℃）により評価用試験片を作製した。
この試験片を用い、前記の方法で、難燃性、耐衝撃性、耐薬品性及び成形品表面外観を評価した。評価結果を表１に示した。
【００５７】
【表１】

【００５８】
表１から、比較例１は、本発明の（Ａ）成分の使用量が発明の範囲外で少なく、（Ｂ）成分の使用量が発明の範囲外で多い例であり、耐衝撃性が劣る。比較例２は、本発明の（Ａ）成分の使用量が発明の範囲外で多く、（Ｂ）成分の使用量が発明の範囲外で少ない例であり、難燃性及び耐薬品性が劣る。比較例３は、本発明の（Ｃ）成分の使用量が発明の範囲外で多い例であり、難燃性、耐薬品性及び成形品表面外観が劣る。比較例４は、本発明の（Ｃ）成分の使用量が発明の範囲外で少ない例であり、難燃性、耐衝撃性、耐薬品性、及び成形品表面外観が劣る。比較例５は、本発明の（Ｃ）成分の共役ジエン部分の水素添加率が発明の範囲外で少ない例であり、難燃性、耐衝撃性、耐薬品性、及び成形品表面外観が劣る。
比較例６は、本発明の（Ｄ）成分の使用量が、発明の範囲外で少ない例であり、難燃性が劣る。比較例７は、本発明の（Ｄ）成分の使用量が、発明の範囲外で多い例であり、耐衝撃性及び成形品表面外観が劣る。
【００５９】
【発明の効果】
本発明の難燃性樹脂組成物は、（Ａ）スチレン系樹脂、（Ｂ）オレフィン系樹脂、（Ｃ）共役ジエン系重合体の水素添加物、（Ｄ）リン酸塩化合物のそれぞれを特定範囲含有しているため、特に難燃性、耐衝撃性、耐薬品性、及び成形品表面外観に優れた成形品を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a flame retardant resin composition excellent in flame retardancy, impact resistance, chemical resistance, and molded product surface appearance, and further to a molded product comprising the flame retardant resin composition.
[0002]
[Prior art]
Molded products of rubber-reinforced styrene resin such as ABS resin are excellent in impact resistance, moldability, mechanical strength, molded product surface appearance, secondary processability, etc. Widely used in fields such as sanitary fields. These materials are required to be flame retardant depending on the application, and materials that are highly flame retardant by using a halogen-based flame retardant are used. However, the halogen-based flame retardant has a problem that a harmful gas may be generated at the time of combustion, and further, a halogen compound coming from the flame retardant corrodes a processing device or the like. Further, the flame-retardant material of styrene resin is required to further improve chemical resistance depending on the intended use.
On the other hand, molded products of olefin resins such as polypropylene are excellent in chemical resistance, heat resistance, fluidity, etc., and thus, like the above styrene resins, electrical / electronic field, OA / home appliance field, vehicle field, sanitary field. Although it is widely used in fields, there are problems such as inferior appearance of molded product surface and impact resistance. These olefin resins are also required to be flame retardant materials depending on the intended use. The method of flame-retarding an olefin resin is difficult. For example, when using a halogen-based flame retardant used in the above-mentioned styrene-based resin or the like, a larger amount of blending is required compared to a halogen-based flame retardant used in a styrene-based resin. The mechanical strength and the like are greatly reduced.
In Patent Document 1, when a metal hydroxide such as aluminum hydroxide or magnesium hydroxide is blended with polyolefin to make it flame retardant, the mechanical strength is fragile because a large amount of metal hydroxide is required. It has been proposed to blend high density polyethylene as a defect improvement. Patent Document 2 proposes that when a metal hydroxide is blended with the above-mentioned polyolefin, a polymer in which polybutene and polypropylene are alloyed at a specific ratio is blended to improve mechanical strength. The improvement in mechanical strength was not sufficient. Further, Patent Document 3 proposes that specific amounts of red phosphorus, titanium oxide, and carbon black are added for the purpose of reducing the amount of metal hydrate, but a considerable amount of metal hydrate is necessary. In addition, the use of red phosphorus and carbon black may cause problems in coloring. Red phosphorus may also generate harmful gases.
As described above, for the purpose of improving the chemical resistance, which is a problem of rubber-modified styrene resins such as ABS resins, and for the purpose of improving the impact resistance of olefin-based resins and the surface appearance of molded products, Although a method of alloying a styrene resin and an olefin resin has been considered, both materials have poor compatibility, and only a very brittle material can be obtained simply by melt mixing.
The present inventors have already applied for a patent on a method for compatibilizing a styrene resin such as ABS resin and a polyolefin resin such as PP (Patent Documents 4 and 5), but these alloy materials are made of non-halogen flame retardants. There was no way to make it flame retardant while maintaining a sufficient balance of physical properties.
[0003]
[Patent Document 1]
JP-A-5-301996
[Patent Document 2]
Japanese Patent Laid-Open No. 10-29736
[Patent Document 3]
JP-A-10-251466
[Patent Document 4]
Japanese Patent Application No. 2002-379817
[Patent Document 5]
Japanese Patent Application No. 2003-106263
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a flame retardant resin composition excellent in flame retardancy, impact resistance, chemical resistance, and molded product surface appearance. Another object of the present invention is to provide the molded article.
[0005]
[Means for Solving the Problems]
The present inventors diligently studied to achieve the above object, and as a result, by blending a phosphate compound into the composition comprising the components (A), (B) and (C), flame retardancy, The present inventors have found a flame retardant resin composition capable of obtaining a molded product excellent in impact resistance, chemical resistance, and molded product surface appearance, and completed the present invention.
That is, the present invention provides the following flame retardant resin composition and a molded product using the same.
(1) (A) It contains a rubber-reinforced styrene resin obtained by graft copolymerization of an aromatic vinyl compound, a vinyl cyanide compound and / or a (meth) acrylic acid ester compound in the presence of a diene (co) polymer. 5 to 94% by mass of styrene-based resin, (B) 5 to 94% by mass of olefin-based resin, (C) a polymer block composed of at least one aromatic vinyl compound and a polymer block composed of at least one conjugated diene compound 1 to 60% by mass of a hydrogenated block copolymer in which the hydrogenation rate of the conjugated diene moiety is 10% or more, the above (A) component, (B) component, and (C) component total 100 mass. Against the department
(D) A polyphosphate compound and / or a pyrophosphate compound A flame retardant resin composition comprising 5 to 70 parts by mass of a phosphate compound.
(2) The flame-retardant resin composition according to the above (1) or (2), wherein the hydrogenation rate of the conjugated diene moiety of the component (C) is in the range of 10% to 80%.
(3) (1) Or (2) A molded product comprising the flame-retardant resin composition described above.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
The styrenic resin according to the present invention is an aromatic vinyl compound or other monomer copolymerizable with an aromatic vinyl compound and an aromatic vinyl compound in the presence or absence of the rubbery polymer (a). Obtained by (co) polymerizing a vinyl monomer (b) containing Be It is a polymer, and is obtained by graft copolymerization of the above vinyl monomer (b) in the presence of a rubbery polymer, preferably from the viewpoint of impact resistance. Rugo It is preferable that the content of the rubber polymer (a) is 3 to 80% by mass, more preferably 5 to 70% by mass, and particularly preferably 10 to 60% by mass. %.
As the rubbery polymer (a) Is Polybutadiene, butadiene / styrene copolymer, butadiene / acrylonitrile copolymer, butadiene / acrylic acid ester copolymer, styrene / butadiene / styrene block copolymer, styrene / butadiene block copolymer, styrene / isoprene / styrene block copolymer Diene-based (co) polymerization such as polymers and isobutylene / isoprene copolymers Body is These may be used alone or in combination of two or more.
Of these, polybutadiene, butadiene / styrene copolymer, styrene / butadiene / styrene block copolymer, and styrene / butadiene block copolymer. Body A hydrogenated product of a diene (co) polymer is preferred.
[0007]
The gel content of the rubbery polymer (a) is usually 98% by mass or less, preferably 40 to 98% by mass, more preferably 50 to 95% by mass, and particularly preferably 60 to 90% by mass. . When the gel content is in this range, a flame-retardant resin composition that gives a molded product excellent in flame retardancy, impact resistance, and surface appearance can be obtained.
In addition, the said gel content rate can be calculated | required by the method shown below. That is, 1 g of a rubbery polymer was put into 100 ml of toluene, allowed to stand at room temperature for 48 hours, and then the toluene-insoluble matter and the wire mesh filtered through a 100-mesh wire mesh (with a mass of W1 gram) were vacuumed at 80 ° C. for 6 hours. Dry and weigh (weigh W2 grams).
Gel content (%) = [{W2 (g) −W1 (g)} / 1 (g)] × 100
The gel content is adjusted by appropriately setting the type and amount of the molecular weight adjusting agent, the polymerization time, the polymerization temperature, the polymerization conversion rate, and the like during the production of the rubbery polymer.
[0008]
Examples of the aromatic vinyl compound constituting the vinyl monomer (b) include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinyltoluene, methyl-α-methylstyrene, brominated styrene, hydroxy Styrene etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types. Of these, styrene and α-methylstyrene are preferred.
Other monomers copolymerizable with the aromatic vinyl compound include vinyl cyanide, (meth) acrylic acid ester, maleimide compound, unsaturated acid, epoxy group-containing unsaturated compound, hydroxyl group-containing unsaturated compound, Examples include oxazoline group-containing unsaturated compounds, acid anhydride group-containing unsaturated compounds, amino group / substituted amino group-containing unsaturated compounds, and the like. These may be used alone or in combination of two or more. Can do.
[0009]
Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. These may be used alone or in combination of two or more.
Examples of (meth) acrylic acid esters include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and the like. These may be used alone or in combination of two or more. They can be used in combination.
Examples of the maleimide compound include maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like. These can be used singly or in combination of two or more. Further, in order to introduce a maleimide unit, a method of (co) polymerizing maleic anhydride and then imidizing may be used.
Examples of the unsaturated acid include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and the like. These may be used alone or in combination of two or more. be able to.
Examples of the epoxy group-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether, and these can be used alone or in combination of two or more.
Examples of the hydroxyl group-containing unsaturated compounds include 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl-1-propene, 2 -Hydroxyethyl methacrylate, N- (4-hydroxyphenyl) maleimide and the like can be mentioned, and these can be used alone or in combination of two or more.
[0010]
Examples of the oxazoline group-containing unsaturated compound include vinyl oxazoline and the like. These can be used alone or in combination of two or more.
Examples of the acid anhydride group-containing unsaturated compound include maleic anhydride, itaconic anhydride, citraconic anhydride and the like, and these can be used alone or in combination of two or more.
Examples of unsaturated compounds containing amino groups and substituted amino groups include aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, phenylaminoethyl methacrylate, N-vinyldiethylamine, N-acetylvinylamine, acrylic There are amine, methacrylamine, N-methylacrylamine, acrylamide, N-methylacrylamide, p-aminostyrene and the like, and these can be used alone or in combination of two or more.
[0011]
The amount of the other monomer copolymerizable with the aromatic vinyl compound is preferably 80% by mass or less, more preferably 60% by mass, when the total amount of the vinyl monomer (b) is 100% by mass. Hereinafter, it is particularly preferably 40% by mass or less.
Preferred monomer combinations are styrene / acrylonitrile, styrene / methyl methacrylate, styrene / acrylonitrile / methyl methacrylate, styrene / acrylonitrile / glycidyl methacrylate, styrene / acrylonitrile / 2-hydroxyethyl methacrylate, styrene / acrylonitrile / (meth). Acrylic acid.
The (A) styrenic resin can be produced by a known polymerization method, for example, emulsion polymerization, bulk polymerization, solution polymerization, suspension polymerization, or a polymerization method combining these. Of these, emulsion polymerization and solution polymerization are particularly preferred.
[0012]
When manufacturing by emulsion polymerization, a polymerization initiator, a chain transfer agent, an emulsifier, and the like are used, and known ones can be used.
As polymerization initiators, cumene hydroperoxide, diisopropylbenzene hydroperoxide, potassium persulfate, azobisisobutyronitrile, benzoyl peroxide, lauroyl peroxide, t-butylperoxylaurate, t-butylperoxymono And carbonate. Further, as the polymerization initiation aid, redox systems such as various reducing agents, sugar-containing pyrophosphate / iron formulations, sulfoxylate formulations, and the like can be used.
Examples of the chain transfer agent include octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexyl mercaptan, tetraethylthiuram sulfide, acrolein, methacrolein, allyl alcohol, 2-ethylhexylthioglycol, and terpinolenes.
Emulsifiers include higher alcohol sulfates, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, aliphatic sulfonates such as sodium lauryl sulfate, higher aliphatic carboxylates, rosinates, phosphates and other anions. Surfactant, and also known nonionic surfactants can be used.
[0013]
In the emulsion polymerization, the rubber polymer (a) and the vinyl monomer (b) are used by adding the vinyl monomer (b) at once in the presence of the total amount of the rubber polymer (a). May be polymerized, or may be polymerized in divided or continuous addition. Further, in the presence of a part of the rubber polymer (a), the vinyl monomer (b) is added all at once and polymerized, and the remainder of the rubber polymer (a) is added and polymerized during the polymerization. Alternatively, the vinyl monomer (b) may be polymerized by dividing or continuously adding, and the remainder of the rubbery polymer (a) may be added during the polymerization.
After the emulsion polymerization, the obtained latex is usually coagulated with a coagulant, washed with water and dried to obtain the (A) styrene resin powder of the present invention. At this time, two or more types of latexes of (A) styrene resin obtained by emulsion polymerization may be appropriately blended before coagulation and then coagulated. As the coagulant used here, inorganic salts such as calcium chloride, magnesium sulfate and magnesium chloride, or acids such as sulfuric acid, hydrochloric acid, acetic acid and citric acid can be used.
The styrene resin (A) obtained by polymerizing the vinyl monomer (b) in the presence of the rubbery polymer (a) by emulsion polymerization usually contains the vinyl monomer (b). ) Grafted onto the rubber polymer (a) and the vinyl monomer (b) not grafted onto the rubber polymer (a) (the vinyl monomer (b) ) (Co) polymers).
[0014]
In the case of producing the (A) styrene resin by solution polymerization, the solvent that can be used is an inert polymerization solvent used in ordinary radical polymerization, for example, aromatic hydrocarbons such as ethylbenzene and toluene, methyl ethyl ketone, Examples include ketones such as acetone, halogenated hydrocarbons such as dichloromethylene and carbon tetrachloride, acetonitrile, dimethylformamide, N-methylpyrrolidone, and the like. The polymerization temperature is preferably 80 to 140 ° C, more preferably 85 to 130 ° C, and particularly preferably 90 to 120 ° C.
In the polymerization, a polymerization initiator may be used, or polymerization may be performed by thermal polymerization without using a polymerization initiator. As the polymerization initiator, organic peroxides such as ketone peroxide, dialkyl peroxide, diacyl peroxide, peroxy ester, hydroperoxide and the like are preferably used.
When a chain transfer agent is used, for example, mercaptans, α-methylstyrene dimer, terpinolenes and the like can be used.
[0015]
In the case of producing by bulk polymerization or suspension polymerization, the polymerization initiator, chain transfer agent, etc. described in the solution polymerization can be used.
[0016]
The amount of monomer remaining in the (A) styrenic resin obtained by each polymerization method is preferably 10,000 ppm or less, more preferably 5,000 ppm or less.
The graft ratio of the (A) styrene resin is preferably 20 to 200% by mass, more preferably 30 to 150% by mass, and particularly preferably 40 to 120% by mass.
The graft ratio (% by mass) is determined by the following formula.
Graft ratio (mass%) = {(TS) / S} × 100
In the above formula, T is (A) 1 g of styrene resin is added to 20 ml of acetone, shaken for 2 hours with a shaker, then centrifuged for 60 minutes with a centrifuge (rotation speed: 23,000 rpm), insoluble Is the mass (g) of the insoluble matter obtained by separating the component and soluble component, and S is the mass (g) of the rubbery polymer contained in 1 g of (A) styrene resin.
[0017]
The intrinsic viscosity [η] of the acetone-soluble component of the (A) styrene resin of the present invention [η] (measured at 30 ° C. using methyl ethyl ketone as a solvent) is preferably 0.2 to 1.2 dl / g, more preferably It is 0.2-1 dl / g, Most preferably, it is 0.3-0.8 dl / g.
The average particle size of the rubbery polymer component dispersed in the component (A) dispersed in the (A) styrene resin of the present invention is preferably 500 to 3,000 kg, more preferably 1,000 to It is in the range of 20,000 kg, particularly preferably 1,500 to 8,000 kg. The average particle diameter of the rubbery polymer component dispersed in the component (A) can be measured by a known method using electron microscopy.
[0018]
When the total of (A), (B) and (C) constituting the flame retardant resin composition of the present invention is 100% by mass, the content of (A) styrenic resin is 5 to 94% by mass. The content is preferably 5 to 80% by mass, more preferably 10 to 60% by mass, and particularly preferably 10 to 50% by mass. If the amount used is less than 5% by mass, the impact resistance is inferior and exceeds 94% by mass. Inferior flame resistance and chemical resistance.
[0019]
The (B) olefin resin of the present invention is a polymer of a monomer composed of at least one α-olefin having 2 to 10 carbon atoms. As this olefin resin, those showing a crystallinity at room temperature by X-ray diffraction are preferred, more preferably those having a crystallinity of 20% or more and a melting point of 40 ° C. or more. In addition, this olefin resin must have a sufficient molecular weight as a molding resin at room temperature. For example, when propylene is the main component, the melt flow rate measured according to JIS K-6758 is preferably 0.01 to 500 g / 10 min, more preferably 0.05 to 100 g / 10 min. Of molecular weight.
Examples of the α-olefin which is a monomer of the (B) olefin resin include ethylene, propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, 3,3- Dimethylpentene-1, 3-methylhexene-1, 4-methylhexene-1, 4,4-dimethylhexene-1, 5-methylhexene-1, vinylcyclohexane, 2-vinylcyclo (2.2.1) heptane, heptene-1, octene-1, etc. Is mentioned. These can be used singly or in combination of two or more.
Preferred among the α-olefins are ethylene, propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, 3-methylhexene-1, and the like. Particularly preferred are ethylene, propylene, butene-1, 3-methylbutene-1, 4-methylpentene-1.
In addition, non-conjugated dienes such as 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 1,9-decadiene are used as part of the polymer component. can do.
[0020]
As the (B) olefin resin of the present invention, one modified with an epoxy group, an amino / substituted amino group, a carboxyl group, an acid anhydride group, a hydroxyl group or the like may be used. By blending the olefin resin component modified with the functional group into the olefin resin in the range of 1 to 30% by mass, the flame retardancy is further improved.
[0021]
When the total of (A), (B) and (C) constituting the flame retardant resin composition of the present invention is 100% by mass, the content of (B) olefin resin is 5 to 94% by mass. , Preferably 17 to 94% by mass, more preferably 35 to 90% by mass, particularly preferably 40 to 90% by mass. When the amount used is less than 5% by mass, the flame retardancy and chemical resistance are inferior. If it exceeds mass%, the impact resistance is poor.
[0022]
The (C) hydrogenated block copolymer of the present invention is a polymer comprising a polymer block comprising at least one aromatic vinyl compound and a polymer block comprising at least one conjugated diene compound. A hydrogenated block copolymer having a hydrogenation rate of 10% or more, specifically, a hydrogenated block copolymer represented by the following structural formula is preferable.
(SB) m General formula (1)
(SB) mY General formula (2)
S- (B-S) n General formula (3)
(In Structural Formulas 1 to 3, S is a polymer block mainly composed of an aromatic vinyl compound, and a conjugated diene compound may be partially included as long as it is a polymer block substantially composed of an aromatic vinyl compound. Preferably, it is a polymer block containing 90% by mass or more, preferably 95% by mass or more, particularly preferably 99% by mass or more of an aromatic vinyl compound, and B is a homopolymer or aromatic vinyl of a conjugated diene compound. It is a copolymer of 20% by mass or less of another monomer such as a compound and a conjugated diene compound, Y is a residue of a coupling agent, m is an integer of 1 to 5, and n is an integer of 1 to 5. Each represents an integer.)
Furthermore, other polymers such as a polymer block having a different vinyl bond content derived from the conjugated diene compound of the polymer block (B), a tapered block in which an aromatic vinyl compound is gradually increased, other than the above polymer block, for example. One or two or more blocks may be copolymerized in the polymer terminal or in the polymer chain.
[0023]
The ratio of the aromatic vinyl compound in the block copolymer (bonded aromatic vinyl compound content) is 10 to 90% by mass, preferably 20 to 80% by mass, and particularly preferably 30 to 70% by mass.
The hydrogenation rate of the double bond derived from the conjugated diene compound of the block copolymer needs to be 10% or more, preferably 20% or more, more preferably 30% or more, particularly preferably 50. % Or more.
From the low temperature impact property of the flame retardant resin composition of the present invention, the hydrogenation rate was in the range of 50 to 80%, and was blended at a ratio of 50% by mass or more of the total (C) hydrogenated block copolymer. Those are preferred. When the hydrogenation rate is less than 10%, flame retardancy, impact resistance, chemical resistance, and molded product surface appearance are poor.
The vinyl bond (1,2- and 3,4-bond) content derived from the conjugated diene compound of the block copolymer is preferably in the range of 5 to 80%.
The number average molecular weight of the (C) hydrogenated block copolymer of the present invention is preferably 5,000 to 1,000,000, more preferably 10,000 to 300,000, particularly preferably 20,000 to 200,000. 000.
[0024]
(C) As the aromatic vinyl compound used in the hydrogenated block copolymer, all of those exemplified above can be used. That is, there are styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, divinylbenzene and the like, and these can be used alone or in combination of two or more. Of these, styrene is particularly preferable. Examples of the conjugated diene compound used here include butadiene, isoprene, methylpentadiene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3-octadiene, and the like. These can be used singly or in combination of two or more. Preferred are butadiene and isoprene, and particularly preferred is butadiene.
[0025]
The manufacturing method of the (C) hydrogenated block copolymer of this invention is not specifically limited, A well-known method is employable. For example, it can be produced by polymerizing an aromatic vinyl compound and a conjugated diene compound in an inert solvent using the technique of living anion polymerization using an organolithium catalyst described in Japanese Patent Publication No. 36-19286. it can. Examples of the organic lithium compound include monolithium compounds such as n-butyllithium, sec-butyllithium, and tert-butyllithium. Adjustment of the vinyl bond amount of the conjugated diene compound is possible by adjusting amines such as N, N, N ′, N′-tetramethylethylenediamine, trimethylamine, triethylamine, diazobicyclo (2,2,2) octane, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol. Examples include ethers such as dibutyl ether, thioethers, phosphines, phosphoamides, alkylbenzene sulfonates, and alkoxides of potassium and sodium.
[0026]
After obtaining a polymer by the above method, a polymer in which a polymer molecular chain is extended or branched via a coupling agent residue using a coupling agent may be used. Examples of the coupling agent used at this time include diethyl adipate, divinylbenzene, methyldichlorosilane, silicon tetrachloride, butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, dimethylchlorosilicon, tetrachlorogermanium, 1,2- Examples include dibromoethane, 1,4-chloromethylbenzene, bis (trichlorosilyl) ethane, epoxidized linseed oil, tolylene diisocyanate, 1,2,4-benzene triisocyanate, and the like.
The target polymer can be obtained by hydrogenating the polymer obtained above by a known method, and adjusting the hydrogenation rate by a known method. Specific methods include JP-B-42-8704, JP-B-43-6636, JP-B-63-4841, JP-B-63-5401, JP-A-2-133406, JP-A-1 There is a method disclosed in Japanese Patent No. 297413.
[0027]
In addition, the component (C) of the present invention can be used as a modified polymer by introducing a functional group such as an amino group, an alkoxy group, a hydroxyl group, an acid anhydride group, or an epoxy group. ) A polymer modified by graft polymerization of a vinyl monomer in the presence of the component can also be used. Examples of such a modified polymer include the following polymers.
(A) A polymer obtained by polymerizing an aromatic vinyl compound and a conjugated diene compound in the presence of an organic alkali metal compound, and reacting an epoxy compound or a ketone compound with the active point of the obtained polymer. A polymer obtained by hydrogenating the coalescence.
(B) An aromatic vinyl compound and a conjugated diene compound are polymerized in the presence of an organic alkali metal compound, and the polymer is hydrogenated from a (meth) acryloyl group-containing compound, an epoxy group-containing compound or maleic anhydride. A polymer obtained by reacting at least one selected in a solution or a kneader such as an extruder.
(C) Aromatic vinyl compound and conjugated diene compound are polymerized in the presence of an organic alkali metal compound, and epoxidized 1,2-polybutadiene, epoxidized soybean oil, epoxidized linseed oil, benzene-1,2, By using 4-triisocyanate, diethyl oxalate, diethyl malonate, diethyl adipate, dioctyl adipate, dimethyl phthalate, diethyl phthalate, diethyl terephthalate, pyromellitic dicyanhydride, etc., the center of the molecular chain A polymer in which a functional group such as OH group, NHCO group, NH group or the like is introduced.
(D) A polymer obtained by graft polymerization of a vinyl monomer in the presence of a block copolymer having a hydrogenation rate of 10% or more of a conjugated diene moiety comprising an aromatic vinyl compound and a conjugated diene compound. As the vinyl monomer used here, all of the vinyl monomers (b) described in the component (A) can be used. Preferably, the aromatic vinyl compound, the vinyl cyanide compound and the (meth) acrylic are used. It is 1 or more types chosen from acid ester, The preferable range of the said hydrogenated block copolymer amount in the said graft body is 10-60 mass%. These preferable production methods are the solution polymerization.
[0028]
When the total of (A), (B) and (C) constituting the flame retardant resin composition of the present invention is 100% by mass, the content of component (C) is 1 to 60% by mass, preferably Is 3 to 50% by mass, more preferably 5 to 50% by mass, and particularly preferably 10 to 40% by mass. When the amount used is less than 1% by mass, flame retardancy, impact resistance, chemical resistance and molding are used. The product surface appearance is inferior, and if it exceeds 60% by mass, the flame retardancy, chemical resistance and molded product surface appearance are inferior.
[0029]
The component (D) of the present invention is a phosphate compound represented by the following general formula (4) or a combination of phosphate compounds represented by the following general formula (6) and the following general formula (7). is there.
[0030]
[Chemical 1]

[Chemical formula 2]

[Chemical 3]

[Formula 4]

[0031]
In the phosphate compound represented by the general formula (4), R in the formula ₁ , R ₂ , R _Three And R _Four Examples of the alkyl group represented by the formula include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, and pentyl.
The phosphate compound represented by the general formula (4) used in the present invention is a phosphoric acid amine salt obtained from diamine, a triazine derivative and (poly or pyro) phosphoric acid. For example, it can be obtained by the following method. That is, a predetermined phosphoric acid or condensed phosphoric acid having a condensation degree of about 2 to 100 is charged into a reaction vessel without adding an inert solvent or adding a solvent. Next, [R ₁ R ₂ N (CH ₂ ) MNR _Three R _Four A diamine represented by the formula: ₁ , R ₂ , R _Three And R _Four Are each H 1 or a linear or branched alkyl group having 1 to 5 carbon atoms; ₁ , R ₂ , R _Three And R _Four May be the same or different. Moreover, m is an integer of 1-10. ), Piperazine or a compound that is a diamine containing a piperazine ring (hereinafter collectively referred to as diamines) is added directly or dissolved in water or diluted with a solvent and reacted at −10 to 100 ° C. The reaction is a neutralization reaction and proceeds rapidly. Next, the reaction product produced here is isolated or added without heating or diluting the triazine derivative represented by the general formula (5) without diluting or diluting with a solvent such as water. To obtain an amine phosphate. The amounts of diamines, ammonia and triazine derivatives involved in the reaction vary depending on the phosphorus concentration of the phosphoric acid or condensed phosphoric acid used. That is, the diamines are reacted by adding less than half the number of hydroxyl groups contained in phosphoric acid or condensed phosphoric acid, preferably approximately equimolar amounts with phosphoric acid or condensed phosphoric acid, An intermediate product is obtained. Next, an amount of ammonia or a triazine derivative corresponding to the hydroxyl group remaining in the intermediate product is added and reacted.
Specific examples of the diamines include N, N, N ′, N′-tetramethyldiaminomethane, ethylenediamine, N, N′-dimethylethylenediamine, N, N′-diethylethylenediamine, N, N-dimethylethylenediamine. N, N-diethylethylenediamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-diethylethylenediamine, 1,2-propanediamine, 1,3-propanediamine, tetra Methylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, piperazine, trans-2,5-dimethylpiperazine, 1 , 4-Bis (2-aminoethyl) piperazine, 1,4 Bis (3-aminopropyl) piperazine, and the like.
[0032]
Specific examples of the triazine derivative include melamine, acetoguanamine, benzoguanamine, acrylic guanamine, 2,4-diamino-6-nonyl-1,3,5-triazine, 2,4-diamino-6-hadidoquinone-1,3. , 5-triazine, 2-amino-4,6-dihydroxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-ethoxy-1,3 , 5-triazine, 2,4-diamino-6-propoxy-1,3,5-triazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-mercapto-1,3 , 5-triazine, 2-amino-4,6-dimercapto-1,3,5-triazine and the like.
[0033]
The phosphate compound represented by the general formula (6) is a salt of (poly or pyro) phosphoric acid and diamine, and can be obtained by reacting at an arbitrary reaction ratio. For example, in the case of piperazine pyrophosphate, piperazine hydrochloride and sodium pyrophosphate are reacted in an aqueous solution to easily obtain a water-insoluble precipitate. Preferable phosphoric acid / diamine salts used in the present invention include piperazine phosphates, and specific examples include orthophosphoric acid piperazine salts, pyrophosphoric acid piperazine salts, and polyphosphoric acid piperazine salts.
[0034]
The phosphate compound represented by the general formula (7) is a phosphoric acid / triazine derivative salt and can be obtained by the following method. For example, in the case of a melamine phosphate, it can be obtained by reacting phosphoric acid and melamine at an arbitrary reaction ratio. Specific examples of the melamine phosphate preferably used in the present invention include, for example, melamine orthophosphate, melamine pyrophosphate, and melamine polyphosphate.
[0035]
The combination ratio (the former / the latter) of the phosphate compound represented by the general formula (6) and the phosphate compound represented by the general formula (7) is preferably 5 to 95/95 to 5 ( Mass%), more preferably 10 to 90/90 to 10 (mass%), and particularly preferably 30 to 70/70 to 30 (mass%). When in this range, an excellent flame retardant effect is obtained.
[0036]
The phosphate compound (D) used in the present invention has an average particle size of 40 μm or less, more preferably 10 μm or less. When the average particle size of the phosphate compound is larger than 40 μm, the dispersibility in the resin composition of the present invention is deteriorated, and the flame retardancy, impact resistance, and molded product surface appearance may be inferior.
[0037]
When the total of (A), (B) and (C) constituting the flame retardant resin composition of the present invention is 100 parts by mass, the content of component (D) is preferably 5 to 70 parts by mass, Is from 5 to 50 parts by weight, more preferably from 10 to 50 parts by weight, particularly preferably from 10 to 40 parts by weight. When the amount used is less than 5 parts by weight, the flame retardancy is inferior. And the molded product surface appearance are poor.
[0038]
For the purpose of improving the flame retardancy of the flame retardant resin composition of the present invention, an anti-dripping agent, a polyvalent hydroxyl group-containing compound, a metal / semi-metal oxide, a transition metal oxide, a silicone compound, a metal salt of an organic acid , And metal hydroxides can be blended, and these can be used alone or in combination of two or more. Anti-dripping agents used here include fluororesins such as polytetrafluoroethylene, polyvinylidene fluoride, polyhexafluoropropylene, perfluoromethane sulfonic acid, purple o-n-butane sulfonic acid, perfluorooctane sulfonic acid Alkali metal salts such as sodium, potassium and calcium salts of perfluoroalkanesulfonic acid such as perfluoro-2-ethylhexanesulfonic acid, alkaline earth metal salts such as phosphoric acid compounds, alkaline metal salts of alkaline acid metals and alkaline earth metals A salt etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types. These anti-dripping agents are preferably used in the range of 0.01 to 3 parts by mass with respect to 100 parts by mass of the flame retardant resin composition of the present invention.
[0039]
Examples of the polyvalent hydroxyl group-containing compound include pentaerythritol, dipentaerythritol, tripentaerythritol, polypentaerythritol, trishydroxyethyl isocyanate, polyethylene glycol, glycerin, starch, glucose, cellulose, sorbitol and the like. Of these polyhydric hydroxyl group-containing compounds, polyhydric alcohol compounds are well-suited with resins and are preferable in terms of low water solubility and low hygroscopicity. Dipentaerythritol, tripentaerythritol, polypentaerythritol (condensation degree ≧ 4) ) Is suitable for the present invention because of its particularly low water solubility and hygroscopicity. These polyvalent hydroxyl group-containing compounds are preferably used in the range of 1 to 15 parts by mass with respect to 100 parts by mass of the flame retardant resin composition of the present invention.
[0040]
Metal and metalloid oxides are oxides of typical metal elements and metalloid elements, and include aluminum oxide, lithium oxide, magnesium oxide, calcium oxide, barium oxide, boron oxide, aluminum oxide, silicon oxide, tin oxide, and phosphorus oxide. Bismuth oxide and the like, and these can be used alone or in combination of two or more. The transition metal oxide is an oxide of a transition metal element, and includes, for example, titanium oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, zinc oxide, zirconium oxide, and the like. Alternatively, two or more kinds can be used in combination. The metal oxide is preferably used in an amount of 20 parts by mass or less with respect to 100 parts by mass of the flame-retardant resin composition of the present invention, from the viewpoint of impact resistance.
[0041]
As the silicone compound, polyorganosiloxane containing M units, D units, T units, and Q units at an arbitrary ratio is preferable, and any of liquid, powder, and rubber-like compounds can be used. Polymethyl phenylsiloxane comprising a unit and a T unit, wherein the substituted alkyl group comprises a methyl group and a phenyl group is particularly preferred. These polyorganosiloxanes may have an alkoxy group, vinyl group, hydroxyl group, hydrogen group or the like added thereto. It is preferable to use a silicone compound in 0.5-20 mass parts with respect to 100 mass parts of flame-retardant resin compositions of this invention.
[0042]
Examples of metal salts of organic acids include alkali metal salts of organic acids such as barium stearate, lithium stearate, calcium stearate, and zinc stearate, and alkaline earth metal salts. These are the flame-retardant resin of the present invention. It is preferable to use in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the composition.
[0043]
A well-known inorganic filler can be mix | blended with the flame-retardant resin composition of this invention. Examples of the inorganic filler used here are glass fiber, milled glass, glass beads, glass flake, hollow glass, carbon fiber, carbon fiber milled fiber, talc, calcium carbonate whisker, wollastonite, mica, kaolin, and montmorillonite. Hectorite, zinc oxide whisker, potassium titanate whisker, aluminum borate whisker, plate-like alumina, smectite treated with organic acid, etc., and these can be used alone or in combination of two or more. . In addition, for the purpose of improving the dispersibility of the inorganic filler, a surface treated with a known coupling agent can also be used. Known coupling agents include silane coupling agents and titanate coupling agents. The said inorganic filler is normally used in the range of 1-100 mass parts with respect to 100 mass parts of flame-retardant resin compositions of this invention.
[0044]
The flame retardant resin composition of the present invention includes known weather resistance (light) agents, antistatic agents, antioxidants, lubricants, plasticizers, colorants, dyes, crystal nucleating agents, antibacterial agents, antifungal agents, A foaming agent etc. can be mix | blended. Further, the flame retardant resin composition of the present invention includes other known thermoplastic polymers such as polyamide resin, polyamide elastomer, polyester resin, polyester elastomer, polycarbonate. The Lioxymethylene, epoxy resin, phenol resin, LCP, thermoplastic polyurethane and the like can be appropriately blended.
[0045]
The flame-retardant resin composition of the present invention can be prepared by kneading each component with various extruders, Banbury mixers, kneaders, continuous kneaders, and the like. A preferable production method is a method using an extruder (preferably a twin screw extruder) or a Banbury mixer.
Furthermore, when each component is kneaded, these components may be kneaded all at once, or may be kneaded in multiple stages, divided and blended using an extruder, a Banbury mixer, or the like. In addition, after knead | mixing with a Banbury mixer, a kneader, etc., it can also be pelletized by further dividing addition, kneading | mixing, deaeration, etc. with an extruder.
The flame-retardant resin composition of the present invention prepared in this way is used to obtain a molded product by a known molding method such as injection molding, press molding, sheet extrusion molding, vacuum molding, profile extrusion molding, foam molding or the like. Can do. Examples of molded products obtained by these molding methods include the following.
[0046]
Various gears, various cases, sensors, LEP lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, optical pickup parts, oscillators, various terminal boards, transformers, plugs, printed wiring boards, Electrical and electronic parts such as tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, housings, semiconductors, liquid crystal FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts. Household and office appliances represented by VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, sound parts, audio equipment parts such as audio / laser discs / compact discs, lighting parts, refrigerator parts, etc. parts. Office computer related parts, telephone equipment related parts, facsimile related parts, copying machine related parts, cleaning jig related parts. Sanitary-related parts such as toilet seats, tank covers, casings, kitchen parts, washstand-related parts, bathroom-related parts. Housing and housing related parts such as window frames, furniture, flooring, and wall materials. Optical equipment and precision equipment related parts such as microscopes, binoculars, cameras and watches. Various valves such as alternator terminals, alternator connectors, IC regulators, exhaust gas valves, various valves related to fuel, exhaust systems, and intake systems. Air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air Flow meter, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, distributor, starter switch, starter relay, wiper harness for transmission, window washer nozzle , Air conditioner panel switch board, fuel related solenoid valve co Rubobin, fuse connector, horn terminal, insulating plates for electric equipment, step motor roller, a lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device case. PC, printer, display, CRT display, notebook computer, mobile phone, PHS, DVD drive, PD drive, flexible disk drive and other storage device housing, chassis, relay, switch, case member, transformer member, coil bobbin, etc. Electronic equipment parts. Automotive exterior members such as bumpers and fenders, and other various uses.
[0047]
【Example】
EXAMPLES The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to such examples unless it exceeds the gist of the present invention. In the examples, parts and% are based on mass unless otherwise specified. Various measurements in the examples and comparative examples were based on the following methods.
[0048]
1) Evaluation method
(1) Gel content of rubbery polymer: omitted as described above.
(2) Average particle diameter of rubber polymer component dispersed in component (A): The average particle diameter of rubber polymer latex used for forming the component (A) was measured by a light scattering method. The measuring machine used was LPA-3100 manufactured by Otsuka Electronics Co., Ltd., and the Mummant method was used with 70 times integration. The average particle size of the rubber polymer component dispersed in the component (A) was confirmed by an electron microscope to be almost the same as the average particle size of the rubber polymer latex.
(3) Graft ratio of component (A): As described above, description thereof is omitted.
(4) Intrinsic viscosity [η] of the acetone-soluble component of component (A): omitted as described above.
(5) Measurement methods for the amount of bonded styrene, number average molecular weight, vinyl bond, hydrogenation rate, etc. of the (hydrogenated) diene polymer of component (C)
(5-1) Amount of bound styrene: measured with a polymer before hydrogenation. It calculated | required from the analytical curve by the infrared method based on absorption of a 699 cm-1 phenyl group.
(5-2) Number average molecular weight: measured with a polymer before hydrogenation. It calculated | required from the gel permeation chromatography (GPC).
(5-3) Amount of vinyl bond; measured with a polymer before hydrogenation. It calculated | required by the infrared method (Morello method).
(5-4) Hydrogenation rate: Measured with the polymer after hydrogenation. 100MHz measured at 15% concentration using ethylene tetrachloride as solvent ¹ It calculated from the spectrum reduction | decrease of the unsaturated double bond part of a H-NMR spectrum.
(6) Flame retardancy: A V test was performed on a 1.6 mm thickness test piece in accordance with the UL94 standard. Those outside the standard of the V test were described as NR.
(7) Impact resistance: Notched Charpy impact strength according to ISO test method 179 (KJ / m ² ) Was measured.
(8) Chemical resistance: Molding after applying a strain of 1% to a test piece having a thickness of 3.2 mm, a width of 12.7 mm, and a length of 127 mm, applying ethyl alcohol, and leaving it at 23 ° C. for 24 hours. The state of the product was visually evaluated based on the following evaluation criteria.
○: No change
×: Crack generation or breakage
(9) Molded product surface appearance: A flat plate having a thickness of 2.0 mm, a width of 50 mm and a length of 70 mm was molded and visually evaluated according to the following evaluation criteria.
○: The surface of the molded product is smooth and there is no sink.
X: The surface of the molded product is not smooth and / or there is a sink on the surface of the molded product.
[0049]
2) Components of flame retardant resin composition
(1) component (A);
(1-1) Production Example A1; ABS resin
In a 7 L glass flask equipped with a stirrer, in a nitrogen stream, ion exchange water 75 parts, potassium rosinate 0.5 part, t-dodecyl mercaptan 0.1 part, polybutadiene latex (average particle size: 3500 kg, Gel content: 85%) 40 parts (solid content), 15 parts of styrene, and 5 parts of acrylonitrile were added, and the temperature was increased while stirring. When the internal temperature reached 45 ° C., a solution in which 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate heptahydrate and 0.2 parts of glucose were dissolved in 20 parts of ion-exchanged water was added. . Thereafter, 0.07 part of cumene hydroperoxide was added to initiate polymerization. After polymerizing for 1 hour, 50 parts of ion exchange water, 0.7 parts of potassium rosinate, 30 parts of styrene, 10 parts of acrylonitrile, 0.05 part of t-dodecyl mercaptan and 0.01 part of cumene hydroperoxide for 3 hours. Then, the polymerization was continued for another hour, and then 0.2 part of 2,2'-methylene-bis (4-ethyl-6-t-butylphenol) was added to complete the polymerization. The reaction product latex was coagulated with an aqueous sulfuric acid solution, washed with water, and then dried to obtain a styrene resin A1. The graft ratio of this copolymer resin A1 was 68%, and the intrinsic viscosity [η] of the acetone soluble part was 0.45 dl / g.
[0050]
(1-2) Production Example A2: AS resin
Two jacketed polymerization reaction vessels equipped with ribbon blades with an internal volume of 30 L were connected and purged with nitrogen, and then 76 parts of styrene, 24 parts of acrylonitrile and 20 parts of toluene were continuously added to the first reaction vessel. A solution of 0.12 part of t-dodecyl mercaptan and 5 parts of toluene as a molecular weight regulator, and a solution of 0.1 part of 1,1′-azobis (cyclohexane-1-carbonitrile) and 5 parts of toluene as a polymerization initiator Was fed continuously. The polymerization temperature of the first group was controlled at 110 ° C., the average residence time was 2.0 hours, and the polymerization conversion rate was 57%. The obtained polymer solution was continuously taken out with the same amount of styrene, acrylonitrile, toluene, molecular weight regulator, and polymerization initiator supplied by a pump provided outside the first reaction vessel. Supplied to the eye reaction vessel. The polymerization temperature of the second reaction vessel was 130 ° C., the average residence time was 2.0 hours, and the polymerization conversion was 75%. The copolymer solution obtained in the second reaction vessel was directly devolatilized from the unreacted monomer and solvent using a twin-screw, three-stage vented extruder, and had an intrinsic viscosity [η] of 0.48. Styrene resin A2 was obtained.
[0051]
(2) Component (C);
(2-1) Production Example C1; Partially hydrogenated product of styrene-butadiene block copolymer
An autoclave with an internal volume of 50 L with a stirrer and a jacket was dried and purged with nitrogen, and a cyclohexane solution containing 30 parts of styrene was added. Then, n-butyllithium was added and polymerized at 70 ° C. for 1 hour, then a cyclohexane solution containing 40 parts of butadiene was added for 1 hour, and a cyclohexane solution containing 30 parts of styrene was further added and polymerized for 1 hour. A part of the obtained block copolymer solution was sampled, 0.3 part of 2,6-di-tert-butylcatechol was added to 100 parts of the block copolymer, and then the solvent was removed by heating. The styrene content was 60%, the 1,2-vinyl bond content of the polybutadiene portion was 35%, and the number average molecular weight was 56000. A solution obtained by reacting titanocene dichloride and triethylaluminum in cyclohexane was added to the remaining block copolymer solution, and the solution was added at 50 ° C. and 50 kgf / cm. ² The hydrogenation reaction was conducted for 40 minutes under hydrogen pressure.
Thereafter, a catalyst removal treatment was performed, 2,6-di-tert-butylcatechol was added, and drying under reduced pressure was performed. The resulting polymer C1 had a hydrogenation rate of 69%.
(2-2) Production Example C2: Partially hydrogenated product of styrene-butadiene block copolymer
In Production Example C1, the hydrogenation reaction time was shortened to obtain a polymer C2 having a hydrogenation rate of 5%.
(2-3) Production Example C3: Hydride of styrene-butadiene block copolymer
An autoclave with an internal volume of 50 L equipped with a stirrer and a jacket was dried and purged with nitrogen, and a solution of cyclohexane and 20 parts of butadiene was added. Next, 0.025 part of n-butyllithium was added, and isothermal polymerization at 50 ° C. was performed. When the addition rate reached 100%, 0.75 part of tetrahydrofuran and 65 parts of butadiene were added, and the temperature rising polymerization was performed from 50 ° C to 80 ° C. When the conversion reached 100%, 15 parts of styrene was added, and a polymerization reaction was further performed to obtain a S-B1-B2 triblock copolymer before hydrogenation. As a result of sampling and analysis in the same manner as in Production Example C1, styrene block 15% (S block), 1,2-vinyl content 35% butadiene block (B1 block), 1,2-vinyl content 10% butadiene block (B2 block) The number average molecular weight was 200,000.
In a separate container, 1 part of titanocene dichloride was dispersed in cyclohexane and reacted with 0.5 part of triethylaluminum at room temperature. The obtained homogeneous solution was added to the polymer solution, and 50 kgf / cm at 50 ° C. ² The hydrogenation reaction was carried out for 2 hours under the hydrogen pressure, and the polymer was recovered in the same manner as C1. The hydrogenation rate of this polymer C3 was 99%.
[0052]
(2-4) (C4); Modified styrene-butadiene block copolymer hydride
A stainless steel autoclave having an internal volume of 10 L equipped with a ribbon type stirring blade was purged with nitrogen, and then 30 parts (solid) of the polymer C3 obtained in the above (2-3) in which toluene was used as a solvent in advance in a nitrogen stream. ), 52.5 parts of styrene, 17.5 parts of acrylonitrile, 120 parts of toluene, and 0.1 part of tert-dodecyl mercaptan were added, and the temperature was raised with stirring. After adding 0.1 part of milperoxide, the temperature was further raised, and after reaching 80 ° C., the polymerization reaction was carried out while controlling at a constant 80 ° C. It took 1 hour from the 6th hour after the start of the reaction, the temperature was raised to 120 ° C., and the reaction was further completed for 2 hours. The polymerization conversion rate was 97%.
After cooling to 100 ° C., 0.2 part of 2,2-methylenebis-4-methyl-6-tert-butylphenol was added, the reaction mixture was extracted from the autoclave, unreacted substances and solvent were distilled off by steam distillation, and pulverized. After that, the volatile matter was substantially distilled off with a vented extruder (220 ° C., 700 mmHg vacuum), and the polymer was pelletized to obtain a polymer C4. The graft ratio of this product was 45%, and the intrinsic viscosity [η] of the acetone-soluble component was 0.45 dl / g.
[0053]
(3) (B) component;
(3-1) B1; propylene resin
A block type polypropylene “Novatech BC6C” manufactured by Nippon Polychem was used.
(3-2) B2: propylene resin
A block type polypropylene “Novatech BC06C” manufactured by Nippon Polychem Co., Ltd. was used.
[0054]
(4) Component (D)
(3-1) D1; Melamine pyrophosphate
What was obtained by reacting 2 mol of melamine and 1 mol of pyrophosphate was used.
(3-2) D2: Piperazine pyrophosphate salt
What was obtained by reacting 1 mol of piperazine and 1 mol of pyrophosphoric acid was used.
(3-3) D3; Melamine piperazine salt of pyrophosphate
A product obtained by reacting 1 mol of melamine, 1 mol of piperazine and 1 mol of pyrophosphate was used.
[0055]
(5) (E) Other ingredients
(5-1) E1; polytetrafluoroethylene
“Hostaflon TF1620” manufactured by Sumitomo 3M Limited was used.
(5-2) E2: Dipentaerythritol
A reagent manufactured by Wako Pure Chemical Industries, Ltd. was used.
[0056]
3) Examples 1-9, Comparative Examples 1-7
After mixing with a Henschel mixer at the blending ratio shown in Table 1, the mixture was melt-kneaded using a twin-screw extruder (cylinder setting temperature 200 ° C.) and pelletized.
After the obtained pellets were sufficiently dried, test pieces for evaluation were produced by an injection molding machine (cylinder setting temperature 200 ° C.).
Using this test piece, flame retardancy, impact resistance, chemical resistance and molded product surface appearance were evaluated by the above-described methods. The evaluation results are shown in Table 1.
[0057]
[Table 1]

[0058]
From Table 1, Comparative Example 1 is an example in which the amount of component (A) used in the present invention is small outside the scope of the invention, and the amount of component (B) used is large outside the scope of the invention, and the impact resistance is poor. . Comparative Example 2 is an example in which the amount of component (A) used in the present invention is large outside the scope of the invention and the amount of component (B) used is small outside the scope of the invention, and the flame retardancy and chemical resistance are poor. . Comparative Example 3 is an example in which the amount of component (C) used in the present invention is large outside the scope of the invention, and the flame retardancy, chemical resistance, and molded product surface appearance are poor. Comparative Example 4 is an example in which the amount of the component (C) used in the present invention is small outside the scope of the invention, and the flame retardancy, impact resistance, chemical resistance, and molded product surface appearance are inferior. Comparative Example 5 is an example in which the hydrogenation rate of the conjugated diene portion of the component (C) of the present invention is small outside the scope of the invention, and the flame retardancy, impact resistance, chemical resistance, and molded product surface appearance are inferior. .
Comparative Example 6 is an example in which the amount of component (D) used in the present invention is small outside the scope of the invention, and the flame retardancy is poor. Comparative Example 7 is an example in which the amount of the component (D) used in the present invention is large outside the scope of the invention, and the impact resistance and the molded product surface appearance are inferior.
[0059]
【The invention's effect】
The flame-retardant resin composition of the present invention includes (A) a styrene resin, (B) an olefin resin, (C) a hydrogenated product of a conjugated diene polymer, and (D) a phosphate compound in a specific range. Since it contains, the molded article which was excellent in especially a flame retardance, impact resistance, chemical resistance, and the molded article surface appearance can be obtained.

Claims (3)

(A) containing a rubber-reinforced styrene resin obtained by graft copolymerization of an aromatic vinyl compound, a vinyl cyanide compound and / or a (meth) acrylic acid ester compound in the presence of a diene (co) polymer. 5 to 94% by mass of a styrene resin,
(B) Olefin resin 5 to 94% by mass,
(C) In a polymer comprising a polymer block comprising at least one aromatic vinyl compound and a polymer block comprising at least one conjugated diene compound, hydrogenation in which the hydrogenation rate of the conjugated diene moiety is 10% or more 1 to 60% by mass of a block copolymer,
Containing 5 to 70 parts by mass of the phosphate compound (D) which is a polyphosphate compound and / or a pyrophosphate compound with respect to 100 parts by mass as a total of the above component (A), component (B) and component (C) A flame retardant resin composition characterized by comprising: (C) the hydrogenation ratio of the conjugated diene portion of the component, the flame-retardant resin composition according to claim 1 Symbol mounting, characterized in that in the range of 10% to 80%. Molded article characterized by using the claim 1 or 2 flame retardant resin composition.