JP4010673B2 - Resin composition - Google Patents

Description

【００２１】
（但し上記式中のＸは、ハイドロキノン、レゾルシノール、ビス（４−ヒドロキシジフェニル）メタン、ビスフェノールＡ、ジヒドロキシジフェニル、ジヒドロキシナフタレン、ビス（４−ヒドロキシフェニル）スルホン、ビス（４−ヒドロキシフェニル）ケトン、ビス（４−ヒドロキシフェニル）サルファイドから誘導されるものが挙げられ、ｊ、ｋ、ｌ、ｍはそれぞれ独立して０または１であり、ｎは０〜５の整数であり、またはｎ数の異なるリン酸エステルのブレンドの場合は０〜５の平均値であり、Ｒ₁、Ｒ₂、Ｒ₃、及びＲ₄はそれぞれ独立してフェノール、クレゾール、キシレノール、イソプロピルフェノール、ブチルフェノール、ｐ−クミルフェノールから誘導されるものである。）
【００２２】
この中で好ましくは、上記式中のＸは、ハイドロキノン、レゾルシノール、ビスフェノールＡから誘導されるものが挙げられ、ｊ、ｋ、ｌ、ｍはそれぞれ１であり、ｎは０〜３の整数であり、またはｎ数の異なるリン酸エステルのブレンドの場合は０〜３の平均値であり、Ｒ₁、Ｒ₂、Ｒ₃、及びＲ₄はそれぞれフェノール、クレゾール、キシレノールから誘導されるものである。
【００２３】
更に、特に好ましくは、Ｘはレゾルシノールから誘導されるものであり、ｊ、ｋ、ｌ、ｍはそれぞれ１であり、ｎは０または１であり、Ｒ₁、Ｒ₂、Ｒ₃、及びＲ₄はそれぞれ独立してフェノールまたはキシレノールから誘導されるものである。
【００２４】
かかるリン酸エステル系難燃剤の中でも、モノホスフェート化合物としてはトリフェニルホスフェート、縮合リン酸エステルとしてはレゾルシノールビス（ジキシレニルホスフェート）が、難燃性が良好でありかつ成形時の流動性が良好である等の理由により好ましく使用できる。
【００２５】
本発明においてｄ成分として使用するフィブリル形成能を有するポリテトラフルオロエチレンは、ＡＳＴＭ規格においてタイプ３に分類されているものであり、フィブリル形成能を有しないものでは本発明の目的が達成されない。フィブリル形成能を有するポリテトラフルオロエチレンは、ＵＬ規格の垂直燃焼テストにおいて試験片の燃焼テスト時に溶融滴下防止性能を有しており、かかるフィブリル形成能を有するポリテトラフルオロエチレンは、例えば三井・デュポンフロロケミカル（株）よりテフロン６Ｊとして、またはダイキン化学工業（株）よりポリフロンとして市販されており容易に入手できる。また、かかるフィブリル形成能を有するポリテトラフルオロエチレンは、固体状態のもの、及び分散媒中に分散混合させたディスパージョン形態のいずれの態様も使用可能であるが、分散剤成分が耐湿熱性に悪影響を与えやすいため、特に固体状態のものが好ましく使用できる。
【００２６】
上記ａ成分〜ｄ成分の配合割合は、ａ成分３８〜９１．９重量％、ｂ成分５〜４０重量％、ｃ成分３〜２０重量％、ｄ成分０．１〜２重量％である。ａ成分が３８重量％未満またはｂ成分が４０重量％を越える場合には、耐熱性（特に荷重撓み温度）や機械的強度が低下するようになる。また、ａ成分が９１．９重量％を越えるかまたはｂ成分が５重量％未満の場合には、流動性が低下し成形加工性が低下するようになる。ｃ成分が３重量％未満では十分な難燃性が得られず、２０重量％を越えると機械的強度や耐熱性（特に荷重撓み温度）が著しく低下するとともに、耐湿熱性も大きく低下する。更にｄ成分が０．１重量％未満では十分な溶融滴下防止性能が得られ難く、２重量％を越えると外観が悪化するようになる。
【００２７】
本発明おいてｅ成分として使用するケイ酸塩系充填剤とは、その化学組成上ＳｉＯ₂成分を３５重量％以上含有する無機充填剤、好ましくは４０重量％以上含有する無機充填剤をいう。かかるケイ酸塩系充填剤としては、カオリン、タルク、クレー、パイロフィライト、マイカ、モンモリロナイト、ベントナイト、ワラストナイト、セピオライト、ゾノトライト、天然シリカ、合成シリカ、各種ガラスフィラー、ゼオライト、ケイソウ土、ハロイサイト等を挙げることができる。
【００２８】
中でも、本発明においては、かかる充填剤が微分散することで加水分解を抑制する作用点を多くできること、及び難燃性付与の観点からは樹脂に対する補強効果も重要であること等の点から、タルク、マイカ等の鱗片状の無機充填剤を好ましい充填剤として挙げることができる。中でもタルクが最も好ましい。
【００２９】
本発明におけるタルクとしては、剛性確保の面から、平均粒径が０.５〜２０μｍの粉末状のものが好ましい。タルクはマイカに比較して厚みが厚いため、樹脂中の分散において同等とするのには、より小粒径である方が好ましい。ここでタルクの平均粒径とはマイクロトラックレーザー回折法により測定された値をいう。
【００３０】
本発明のタルクとしては、特に産地等を限定するものではないが、より好ましくは、ＳｉＯ₂成分がより高いもの、例えば６０重量％以上のものが好ましい。かかるＳｉＯ₂成分量の場合は、相対的に不純物であるＦｅ₂Ｏ₃の含有量も多くなりやすいため、かかるタルクは色相の点においても有利である。またかかるタルクを原石から粉砕する際の製法に関しては特に制限はなく、軸流型ミル法、アニュラー型ミル法、ロールミル法、ボールミル法、ジェットミル法、及び容器回転式圧縮剪断型ミル法等を利用することができる。更にかかるタルクは、その取り扱い性等の点で凝集状態であるものが好ましく、かかる製法としては脱気圧縮による方法、バインダー樹脂を使用し圧縮する方法等があり、特に脱気圧縮による方法が簡便かつ不要のバインダー樹脂成分を本発明の組成物中に混入させない点で好ましい。
【００３１】
本発明におけるマイカとしては、補強効果確保の面から、平均粒径が１〜８０μｍの粉末状のものが好ましい。マイカとは、アルミニウム、カリウム、マグネシウム、ナトリウム、鉄等を含んだケイ酸塩鉱物の粉砕物である。マイカには白雲母、金雲母、黒雲母、人造雲母等があり、本発明のマイカとしてはいずれのマイカも使用できるが、特に金雲母、黒雲母及び金雲母のＯＨ基がＦ原子に置換された人造雲母よりは、ＳｉＯ₂含有量のより高い白雲母が好ましい。また、マイカの製造に際しての粉砕法としては、マイカ原石を乾式粉砕機にて粉砕する乾式粉砕法とマイカ原石を乾式粉砕機にて粗粉砕した後、水を加えてスラリー状態にて湿式粉砕機で本粉砕し、その後脱水、乾燥を行う湿式粉砕法があり、乾式粉砕法の方が低コストで一般的であるがマイカを薄く細かく粉砕することが困難であるため本発明においては湿式粉砕法により製造されたマイカを使用するのが好ましい。
【００３２】
マイカの平均粒径としては、マイクロトラックレーザー回折法により測定した平均粒径が１〜８０μｍのものが好ましく使用できる。更に好ましくは平均粒径が２〜５０μｍのものである。１〜８０μｍの場合には、より難燃性に良好な作用を与えるとともに、樹脂中の微分散の条件も満足するため耐湿熱性も良好に維持できる。
【００３３】
マイカの厚みとしては、電子顕微鏡の観察により実測した厚みが０．０１〜１μｍのものを使用できる。好ましくは厚みが０．０３〜０．３μｍである。更にかかるマイカは、シランカップリング剤等で表面処理されていてもよく、更にエポキシ系、ウレタン系、アクリル系等の結合剤で造粒し顆粒状とされていてもよい。マイカの具体例としては、株式会社山口雲母工業所製雲母粉（マイカ粉）Ａ−４１、Ａ−２１、Ａ−１１等があり、これらは市場で容易に入手できるものである。
【００３４】
本発明においてｅ成分の配合割合は、ａ成分〜ｄ成分の合計１００重量部当り０．１〜３０重量部、好ましくは０．５〜２０重量部の範囲である。このｄ成分の配合割合が０．１重量部未満では、耐湿熱性の向上効果がなく、３０重量部を越えると耐湿熱性に対する効果が飽和する一方で、衝撃強度が低下したり、得られる成形品の表面外観が悪化するようになるため好ましくない。
【００３５】
本発明においてはｆ成分として、アクリル酸アルキルエステル６０〜９０重量％及びブタジエン１０〜４０重量％の合計１００重量％を含有するゴムラテックスからなるコア５０〜７５重量部に対して、芳香族モノビニル化合物、シアン化ビニル化合物、メタクリル酸エステルの中から選ばれたモノマーの１種または２種以上よりなる混合物を、１段または２段以上のグラフト重合によりグラフトさせてなるシェル２５〜５０重量部からなり、かかるコアとシェルの合計が１００重量部であるアクリル酸エステル系コア−シェルグラフト共重合体を使用する。
【００３６】
本発明のｆ成分に使用するアクリル酸エステルは、アルキル基の炭素数が２〜８であるアクリル酸エステルであり、例えば、エチルアクリレート、プロピルアクリレート、ブチルアクリレート、シクロヘキシルアクリレート、２−エチルヘキシルアクリレート等を挙げることができる。これらの中でもブチルアクリレートや２−エチルヘキシルアクリレートが好ましく用いられ、特に２−エチルヘキシルアクリレートが好ましい。
【００３７】
また、ｆ成分に使用する芳香族モノビニル化合物としては、スチレン、ビニルトルエン、α−メチルスチレンを挙げることができ、特にスチレンが好ましい。シアン化ビニル化合物としては、アクリロニトリル及びメタクリロニトリルを挙げることができ、特にアクリロニトリルが好ましい。
【００３８】
更に、ｆ成分のメタクリル酸エステルとは、メタクリル酸の炭素数１〜５のアルキルエステルをいい、例えば、メチルメタクリレートやプロピルメタクリレート、ブチルメタクリレートを挙げることができ、特にメチルメタクリレートが好ましい。
【００３９】
本発明で使用するｆ成分のアクリル酸エステル系コア−シェルグラフト共重合体は、乳化重合法により作成された、コア及びそれに１段または２段以上でグラフト重合したシェルからなるコア−シェルグラフト共重合体であり、コア及びシェルの合計１００重量部中コア５０〜７５重量部及びシェル５０〜２５重量部、好ましくはコア５０〜７０重量部及びシェル５０〜３０重量部からなるものである。更にかかるコアの平均粒径としては０．０８〜０．２５μｍ、より好ましくは０．１３〜０．２０μｍからなるものである。
【００４０】
更にかかるコアにおける、アクリル酸アルキルエステル及びブタジエンの割合はそれらの合計１００重量％中、アクリル酸アルキルエステルが６０〜９０重量％、好ましくは６０〜８０重量％であり、ブタジエンが１０〜４０重量％、好ましくは２０〜４０重量％である。
【００４１】
またかかるコアには、コア全量中２０重量％以下の範囲で、他の共重合可能なモノマー、好ましくはメチルメタクリレート及び／またはスチレン、特に好ましくはメチルメタクリレートの単位を共重合することもできる。
【００４２】
本発明のｆ成分におけるシェルは、芳香族モノビニル化合物、シアン化ビニル化合物、メタクリル酸エステルの中から選ばれたモノマーの１種または２種以上の混合物からなるものであるが、特に芳香族ビニル化合物及びメタクリル酸エステルを含むものが好ましい。ここでシェルにおける各モノマーの割合としては、該シェルの全量１００重量％中メタクリル酸エステルが４５〜８０重量％であることが好ましく、より好ましくは５５〜７０重量％である。したがって芳香族モノビニル化合物、またはシアン化ビニル化合物を含有する場合は芳香族モノビニル化合物及びシアン化ビニル化合物の合計が２０〜５５重量％が好ましく、より好ましくは３０〜４５重量％である。更にシアン化ビニル化合物を含有する場合はかかるシアン化ビニル化合物が芳香族モノビニル化合物との合計１００重量％中２０〜３５重量％が好ましく、より好ましくは２２〜３０重量％である。
【００４３】
更に本発明のｆ成分として好ましいものとしては、ｆ成分のシェルが２段のグラフト重合からなり、第１グラフト成分が芳香族モノビニル化合物及びメタクリル酸エステルの混合物、または芳香族モノビニル化合物、シアン化ビニル化合物及びメタクリル酸エステルの混合物のいずれかからなるものであり、更に第２グラフト成分がメタクリル酸エステルからなるものであって、かつシェル成分の合計１００重量％中第１グラフト成分が４０〜７５重量％及び第２グラフト成分が２５〜６０重量％であるものが好ましく使用できる。更に第１グラフト成分が４２〜７０重量％及び第２グラフト成分が３０〜５８重量％であるものがより好ましい。
【００４４】
更に本発明のｆ成分は、該ｆ成分のコア及び各段階のシェルを重合するに際し、上記に示したモノマー成分の他に、少量の架橋性モノマーを混合し重合してなるものである。ここで架橋性モノマーの量としては、コアの重合においてはかかるコアの重合に使用するモノマーの合計１００重量％に対し０．０１〜３重量％、各段階のシェルの重合においてはかかる各段階のモノマーの合計１００重量％に対し０．０１〜２重量％である。
【００４５】
ここでコアの重合の際に使用する架橋性モノマーとしては、好ましくは、分子内に二個以上の重合性エチレン性不飽和結合を有するモノマーが用いられる。具体例としては、例えば、ジビニルベンゼン等の芳香族ジビニルモノマー、エチレングリコールジ（メタ）アクリレート、ブチレングリコールジ（メタ）アクリレート、ヘキサンジオール（メタ）アクリレート、オリゴエチレングリコールジ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート等を挙げることができる。これらのなかではエチレングリコールジメタクリレート、ジビニルベンゼンが好ましく用いられる。
【００４６】
シェルの重合に使用する架橋性モノマーとしては、ジビニルベンゼン、ブチレングリコールジアクリレート、ヘキサンジオールジアクリレート等が好ましく用いられ、なかでも、特にエチレングリコールジメタクリレート、ジビニルベンゼンが好ましく用いられる。
【００４７】
更に本発明のｆ成分は、製造時の分散不良等を解消する目的で、耐ブロッキング性の改良の処理を施したものも使用でき、かかる処理方法として公知の手法を取ることができる。
【００４８】
かかる方法としては、グラフト共重合体ラテックスを噴霧乾燥し、粉末を球状化する方法、共重合体ラテックスの塩析条件を調整する方法及び滑剤などの添加剤を添加する方法が挙げられる。また、弾性幹重合体（ブタジエン、アクリル酸エステルよりなる）５〜４９重量％に硬質重合体を形成するモノマー（芳香族モノビニル化合物、シアン化ビニル化合物、アクリル酸エステル及びメタクリル酸エステルから選択された１種以上のモノマー）５１〜９５重量％をグラフト重合することによって得られた粉体特性改良グラフト共重合体０．１〜２５重量部をスラリー状態にて本発明のアクリル酸エステル系コア−シェルグラフト共重合体１００重量部に配合する方法も挙げられる。
【００４９】
あるいは、硬質非弾性重合体のエマルジョンを凝固させた本発明のアクリル酸エステル系コア−シェルグラフト共重合体のスラリーに加える方法も挙げられる。ここで硬質非弾性重合体としては、芳香族モノビニル化合物、シアン化ビニル化合物、及びメタクリル酸エステルから選択される１種以上のモノマーから重合されたものであり、特にメチルメタクリレートを８０重量％以上含有するものが好ましい。
【００５０】
以上の中でも粉体特性改良グラフト共重合体または硬質非弾性重合体をスラリー状態のアクリル酸エステル系グラフト共重合体に配合する方法が、簡便かつ、効果的にブロッキング性の低下を達成できるためより好ましい。
【００５１】
尚、粉体特性改良グラフト共重合体あるいは、硬質重合体の添加による耐ブロッキング性改良の方法は、本発明のアクリル酸エステル系コア−シェルグラフト共重合体における各成分量の範囲内にて行われる。
【００５２】
本発明のｆ成分として好ましいアクリル酸エステル系コア−シェルグラフト重合体としては、コアとシェルの合計が１００重量部中、アクリル酸アルキルエステル６０〜８０重量％及びブタジエン２０〜４０重量％の合計１００重量％を含有するゴムラテックスからなるコア５０〜７０重量部に対して、芳香族モノビニル化合物及びメタクリル酸エステル及び、必要に応じて更にシアン化ビニル化合物からなる混合物を、２段グラフト重合によりグラフトさせてなるシェル３０〜５０重量部からなり、かかるシェル１００重量％中メタクリル酸エステルが５５〜７０重量％であり、更にシアン化ビニル化合物を含有する場合はかかるシアン化ビニル化合物が芳香族モノビニル化合物との合計１００重量％中２２〜３０重量％であり、第１グラフト成分が芳香族モノビニル化合物及びメタクリル酸エステルの混合物、または芳香族モノビニル化合物、シアン化ビニル化合物及びメタクリル酸エステルの混合物のいずれかからなるものであり、更に第２グラフト成分がメタクリル酸エステルからなるものであって、かつシェル成分の合計１００重量％中第１グラフト成分が４２〜７０重量％及び第２グラフト成分が３０〜５８重量％であるものが挙げられ、具体的には呉羽化学工業（株）から商品名「ＨＩＡ−１５」、「ＨＩＡ−２８」、「ＨＩＡ−２８Ｓ」として市販されている樹脂を挙げることができる。
【００５３】
本発明においてｆ成分の配合割合は、ａ成分〜ｄ成分の合計１００重量部当り１〜１０重量部の範囲である。このｆ成分の配合割合が１重量部未満であると、十分な衝撃強度が得られず１０重量部を超えると十分な難燃性が付与できない。
【００５４】
本発明の樹脂組成物上記各成分をタンブラー、Ｖ型ブレンダー、ナウターミキサー、バンバリーミキサー、混錬ロール、押出機等の混合機により混合して製造することができる。更に、本発明の目的を損なわない範囲でポリエステル、ポリアミド、ポリフェニレンエーテル等の他の熱可塑性樹脂が混合されていてもよく、また必要に応じてその効果が発現する量の種々添加剤、例えば安定剤、離型剤、帯電防止剤、紫外線吸収剤、染顔料等を含ませても差し支えない。
【００５５】
熱安定剤としては、芳香族ポリカーボネートの熱安定剤として従来公知の亜リン酸、リン酸、亜ホスホン酸、ホスホン酸及びこれらのエステル等が挙げられ、具体的には、トリスノニルフェニルホスファイト、トリメチルホスフェート、トリス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ホスファイト及びベンゼンホスホン酸ジメチルが好ましく挙げることができる。これらの熱安定剤は、単独でもしくは２種以上混合して用いてもよい。
【００５６】
本発明の熱安定剤としては、上記以外に一般に酸化防止剤として知られるヒンダードフェノール系の化合物やイオウ系の化合物を配合することも好ましく行われる。かかる化合物は特にスチレン系樹脂の熱安定性を保持し、該樹脂の熱分解を抑制する点で好ましいものである。かかる化合物として具体的には、ｎ−オクタデシル−３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、４，４’−ブチリデンビス（３−メチル−６−ｔｅｒｔ−ブチルフェノール）、４，４’−チオビス（３−メチル−６−ｔｅｒｔ−ブチルフェノール）、２，２’−メチレンビス（４−メチル−６−ｔｅｒｔ−ブチルフェノール）、トリス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）イソシアヌレート、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール、２，４−ジ−ｔｅｒｔ−アミル−６−［１−（３，５−ジ−ｔｅｒｔ−アミル−２−ヒドロキシフェニル）エチル］フェニルアクリレート等、及びペンタエリスリチルテトラキス（３−ラウリルチオプロピオネート）、ジラウリル−３，３’−チオジプロピオネート、ジミリスチル−３，３’−チオジプロピオネート、ジステアリル−３，３’−チオジプロピオネート等を挙げることができる。
【００５７】
離型剤としては、脂肪酸と脂肪族アルコールとのエステル、脂肪酸と芳香族アルコールとのエステル、脂肪酸と多価アルコールとの部分エステルあるいは全エステル、脂肪酸とポリグリコールとの部分エステルあるいは全エステル、エポキシエステル、エステル系天然ワックス類等が挙げられる。更に上述のエステル系以外に、低分子量ポリエチレン、低分子量ポリプロピレン、パラフィンワックス等の炭化水素系、ステアリン酸アミド、ラウリン酸アミド等の脂肪酸アミド系内部離型剤等が挙げることができる。エステル系離型剤としては、例えば理研ビタミン（株）よりグリセリン脂肪酸エステル「リケマールＳ−１００Ａ」（商品名）として、あるいは、ヘキスト（株）よりモンタン酸エステル「ヘキストワックスＥ」（商品名）として、また低分子量ポリエチレンとしては三井化学（株）より「ハイワックス」（商品名）として市販されている。
【００５８】
また紫外線吸収剤としては、２−（２’−ヒドロキシ−５’−ｔｅｒｔ−オクチルフェニル）ベンゾトリアゾール、２−（３−ｔｅｒｔ−ブチル−５−メチル−２−ヒドロキシフェニル）−５−クロロベンゾトリアゾール、２−（５−メチル−２−ヒドロキシフェニル）ベンゾトリアゾール、２−［２−ヒドロキシ−３，５−ビス（α，α−ジメチルベンジル）フェニル］−２Ｈ−ベンゾトリアゾール、２，２’−メチレンビス（４−クミル−６−ベンゾトリアゾールフェニル）、２，２’−ｐ−フェニレンビス（１，３−ベンゾオキサジン−４−オン）、ポリアルキレンナフタレート等が挙げられる。
【００５９】
かくして得られる樹脂組成物は押出成形、射出成形、圧縮成形等の方法で容易に成形可能であり、またブロー成形、真空成形等にも適用できる。特にＵＬ９４Ｖ−０が要求される電気電子部品、ＯＡの外装用途等の材料として最適である。
【００６０】
【発明の実施の形態】
以下に実施例をあげて本発明を更に説明する。なお実施例中の部は重量部であり、評価は下記の方法によった。
【００６１】
（１）耐衝撃性：ＡＳＴＭ Ｄ２５６に従い、アイゾットノッチ付き耐衝撃値を測定した。
【００６２】
（２）難燃性：ＵＬ規格９４Ｖに従い厚み１．６ｍｍにおける燃焼試験を実施した。
【００６３】
（３）顔料着色性：５０ｍｍ×８０ｍｍ×２ｍｍの角板を日本電色工業(株)製測色色差計Ｚ−１００１ＤＰ型（Ｃ光源、２度視野）を用いて色相測定を行った。成形板の色相分析によりＬ^*値を求め、この値が低い、すなわち明度の低いものほど顔料着色性が良好であると判断する。一般的には、カーボンブラックを０．５重量部添加した時のＬ^*値が１２以下であれば良好な顔料着色性と判断され、濃色系に着色される用途に使用することができる。
【００６４】
（４）耐湿熱性−１：１／８”アイゾット衝撃用試験片をノッチ切削処理後環境試験機（タバイエスペック（株）製プラチナスサブゼロルシファー）で６５℃、８５％ＲＨの条件下で５００時間処理した後、ＡＳＴＭ Ｄ２５６に従ってアイゾットノッチ付き耐衝撃値を測定し、湿熱処理前のアイゾットノッチ付き耐衝撃値との比較を行った。
【００６５】
（５）耐湿熱性−２：（４）の湿熱処理後の試験片につき、芳香族ポリカーボネート樹脂の分子量を測定するのと同一の手法でみかけの粘度平均分子量を測定した。すなわち、試験片を塩化メチレンに溶解した後、不溶分をろ過により取り除いて溶液として得られたものの比粘度を、本文記載のポリカーボネート樹脂の粘度平均分子量測定と同様に測定し、更に同一の算出式を用いてみかけの粘度平均分子量の値を算出した。
【００６６】
［実施例１〜７、比較例１〜５］
表１及び表２に記載の各成分を表記載の量に基づいてＶ型ブレンダーで混合した後、径３０ｍｍφのベント式二軸押出機［（株）日本製鋼所製ＴＥＸ３０ＸＳＳＴ］によりシリンダー温度２４０℃でペレット化した。このペレットを１００℃で５時間乾燥した後、射出成形機［ＦＡＮＵＣ（株）製Ｔ−１５０Ｄ］でシリンダー温度２５０℃、金型温度７０℃で各種試験片を作成し評価した。評価結果を表１及び表２に示した。なお、表１及び表２に記載の各成分を示す記号は下記の通りである。
【００６７】
（ａ成分）
ＰＣ：ポリカーボネート樹脂（帝人化成(株)製 Ｌ−１２２５）
（ｂ成分）
ＡＢＳ：ＡＢＳ樹脂（三井化学(株)製 サンタックＵＴ−６１）
（ｃ成分）
ＦＲ−１：トリフェニルホスフェート［大八化学(株)製 ＴＰＰ］
ＦＲ−２：レゾルシノールビス（ジキシレニルホスフェート）［旭電化工業(株)製 アデカスタブＦＰ−５００］
（ｄ成分）
ＰＴＦＥ：ポリテトラフルオロエチレン［ダイキン工業(株)製 Ｆ−２０１Ｌ］
（ｅ成分）
タルク：タルク［日本タルク(株)製 タルクＰ−３、平均粒子径約３μｍ］
マイカ：マイカ粉［(株)山口雲母工業所製 Ａ−４１、平均粒子径約４０μｍ］
（ｅ成分以外の充填剤）
ＣＦ：炭素繊維［東邦レーヨン(株)製 ベスファイト ＨＴＡ−Ｃ６−Ｕ、ＰＡＮ系、ウレタン集束、繊維径７μｍ］
（ｆ成分）
ゴム−１：２−エチルヘキシルアクリレート・ブタジエン・メチルメタクリレート・スチレン多段グラフト共重合体（スチレン含有量：１５重量％）［呉羽化学工業(株)製 ＨＩＡ−１５］
（ｆ成分以外の重合体）
ゴム−２：アクリル−シリコン系衝撃改質剤[三菱レイヨン(株)製 Ｓ−２００１]
（その他）
ＣＢ：カーボンブラック[三菱化学(株)製 ＣＢ−９６０]
【００６８】
【表１】

【００６９】
【表２】

【００７０】
この表から明らかなように、実施例１と比較例１との比較より、本発明の特定のアクリル酸エステル系コア−シェルグラフト共重合体を使用した場合には、難燃性及び着色性の両立が図れていることが分かる。一方、実施例２と比較例３及び４との比較より、本発明のケイ酸塩化合物を配合した場合にのみ、耐湿熱性の改良が図られることが分かる。
【００７１】
【発明の効果】
本発明のポリカーボネート樹脂組成物は、難燃性、衝撃強度に優れ、かつ耐湿熱性及び着色性に優れることから、ＯＡ機器分野、電気電子機器分野等の各種工業用途に極めて有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a resin composition excellent in wet heat resistance and colorability as well as flame retardancy.
[0002]
[Prior art]
Polycarbonate resins are widely used industrially because they have excellent mechanical properties and thermal properties. However, due to inferior processability and moldability, many polymer alloys with other thermoplastic resins have been developed. Among them, polymer alloys with styrenic resins represented by ABS resins are used in the automotive field, OA equipment field, electronic Widely used in the field of electrical equipment. On the other hand, in recent years, there has been a strong demand for flame retardant resin materials used, mainly in applications such as OA equipment and home appliances. In order to meet these demands, the polymer alloy of polycarbonate resin and ABS resin is also flame retardant. Many studies have been made.
[0003]
Conventionally, in such polymer alloys, it has been common to use a halogen-based flame retardant having a bromine atom and a flame retardant aid such as antimony trioxide. Consideration of flame retardant not included has become active. For example, a method of blending polytetrafluoroethylene having triphenyl phosphate and fibril forming ability into a polymer alloy of polycarbonate resin and ABS resin (JP-A-2-32154), blending a phosphate oligomer which is a condensed phosphate ester A method (Japanese Patent Laid-Open No. 2-115262) has been proposed. On the other hand, in recent years, performance retention in long-term use has been regarded as extremely important from the viewpoints of product safety, reduction of environmental burden due to prolonged product life, and product warranty of manufacturers.
[0004]
However, the polycarbonate resin composition containing these phosphate ester-based flame retardants hydrolyzes the compounded phosphate ester-based flame retardant in its long-term use, and this decomposition product is a hydrolysis of the carbonate bond of the polycarbonate resin. And, for example, the impact strength is significantly reduced.
[0005]
In JP-A-7-126510, a specific inorganic filler and a specific impact modifier are blended into a resin composition in which a phosphate flame retardant is blended with a polymer alloy of a polycarbonate resin and an ABS resin. Although a method has been proposed, the resin composition obtained here has a problem in colorability.
[0006]
That is, in a resin composition in which a phosphate ester-based flame retardant is blended with a polymer alloy of a polycarbonate resin and an ABS resin, improvement in wet heat resistance and improvement in coloring properties are required, and a solution has been urgently required.
[0007]
[Problems to be solved by the invention]
An object of the present invention is to provide a resin composition in which a polymer alloy of a polycarbonate resin and an ABS resin is blended with a phosphate ester-based flame retardant and polytetrafluoroethylene having fibril-forming ability as an anti-drip agent. It is in providing the polycarbonate resin composition excellent in property.
[0008]
As a result of intensive studies to achieve the above object, the present inventor has found that a specific inorganic filler and a specific specific resin composition are made of a polycarbonate resin, an ABS resin, a phosphate ester flame retardant, and polytetrafluoroethylene. The inventors have found that a polycarbonate resin composition having excellent hydrolysis resistance in long-term use, that is, resistance to moist heat, and good colorability can be obtained by blending an impact modifier, and the present invention has been achieved.
[0009]
[Means for Solving the Problems]
The present invention relates to a polycarbonate resin (component a) 38 to 91.9% by weight, a thermoplastic graft copolymer (component b) 5 to 40% by weight obtained by grafting a vinyl cyanide compound and an aromatic vinyl compound to a diene rubber component. 100 parts by weight of a composition comprising a total of 100% by weight of 3 to 20% by weight of a phosphoric ester-based flame retardant (component c) and 0.1 to 2% by weight of polytetrafluoroethylene (component d) having a fibril-forming ability, The present invention relates to a resin composition comprising 0.1 to 30 parts by weight of a silicate filler (e component) and 1 to 10 parts by weight of an acrylate-based core-shell graft copolymer (f component).
[0010]
The polycarbonate resin in component a of the present invention refers to a polycarbonate resin obtained by reacting a dihydric phenol and a carbonate precursor, that is, an aromatic polycarbonate resin. As typical examples of the dihydric phenol used here, 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis ( 4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) Examples thereof include sulfide and bis (4-hydroxyphenyl) sulfone. Preferred dihydric phenols are 2,2-bis (4-hydroxyphenyl) alkanes, with bisphenol A being particularly preferred. Examples of the carbonate precursor include carbonyl halide, carbonic acid diester, bishaloformate, and the like. Specific examples include phosgene, diphenyl carbonate, dibischloroformate of dihydric phenol, and the like. In producing a polycarbonate resin by reacting the dihydric phenol and the carbonate precursor, the dihydric phenol may be used alone or in combination of two or more kinds, or a mixture of two or more kinds of polycarbonate resins may be used. .
[0011]
The molecular weight of the polycarbonate resin is usually 10,000 to 40,000 in terms of viscosity average molecular weight, and preferably 12,000 to 30,000. The viscosity average molecular weight (M) mentioned here is obtained by inserting the specific viscosity (ηsp) obtained from a solution obtained by dissolving 0.7 g of polycarbonate resin in 100 ml of methylene chloride at 20 ° C. into the following equation.
ηsp / C = [η] + 0.45 × [η] ² C
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
([Η] is the intrinsic viscosity, C is the polymer concentration of 0.7)
[0012]
The interfacial polymerization method for producing the polycarbonate resin will be briefly described. In the interfacial polymerization method using phosgene as a carbonate precursor, the reaction is usually carried out in the presence of an acid binder and an organic solvent. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, or amine compounds such as pyridine. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In order to accelerate the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used, and examples of the molecular weight regulator include alkyl-substituted phenols such as phenol and p-tert-butylphenol and 4- (2 It is desirable to use a terminal terminator such as an aralkyl-substituted phenol such as -phenylisopropyl) phenol. The reaction temperature is preferably 0 to 40 ° C., the reaction time is several minutes to 5 hours, and the pH during the reaction is preferably maintained at 10 or more. In addition, it is not necessary that all of the resulting molecular chain ends have a structure derived from a terminal terminator.
[0013]
In a transesterification reaction (melting method) using a carbonic acid diester as a carbonate precursor, a predetermined proportion of a dihydric phenol component and, if necessary, a branching agent, etc., are stirred and heated with a carbonic acid diester. It is carried out by a method of distilling off alcohols or phenols. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is completed while distilling off the alcohol or phenol produced under reduced pressure from the beginning. Moreover, in order to accelerate | stimulate reaction, the catalyst used for now well-known transesterification reactions, such as an alkali metal compound and a nitrogen-containing basic compound, can also be used. Examples of the carbonic acid diester used in the transesterification include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred. In addition, diphenyl carbonate, methyl (2-phenyloxycarbonyloxy) benzenecarboxylate or the like is added as an end terminator in the initial stage of the reaction or in the middle of the reaction, and various conventionally known catalyst deactivations immediately before the end of the reaction. It is also preferable to add an agent.
[0014]
The thermoplastic graft copolymer obtained by grafting a vinyl cyanide compound and an aromatic vinyl compound to the diene rubber component used as the component b in the present invention means a so-called ABS resin. As the diene rubber component forming such ABS resin, for example, rubber having a glass transition point of 10 ° C. or less such as polybutadiene, polyisoprene, styrene-butadiene copolymer, acrylonitrile-butadiene, etc., is used. It is 5-75 weight% in weight%, Preferably it is 8-50 weight%, More preferably, it is 10-30 weight%. Examples of the vinyl cyanide compound grafted on the diene rubber component include acrylonitrile and methacrylonitrile, and examples of the aromatic vinyl compound grafted on the diene rubber component include styrene and α-methylstyrene. And nucleus-substituted styrene such as p-methylstyrene. The content ratio of the vinyl cyanide compound and the aromatic vinyl compound is 5 to 50% by weight of the vinyl cyanide compound and 100% by weight of the total amount of the vinyl cyanide compound and aromatic vinyl compound. Is 95 to 50% by weight, preferably 10 to 35% by weight of vinyl cyanide compound and 65 to 90% by weight of aromatic vinyl compound. Further, methyl acrylate, methyl methacrylate, ethyl acrylate, maleic anhydride, N-substituted maleimide and the like can be mixed and used, but their content should be 15% by weight or less in the component b.
[0015]
In the component b of the present invention, the rubber particle diameter is preferably 0.1 to 5.0 μm, more preferably 0.3 to 3.0 μm, and particularly preferably 0.4 to 1.5 μm. As the distribution of the rubber particle diameter, either a single distribution or a rubber particle having two or more peaks can be used, and the rubber particles form a single phase in the morphology. Alternatively, it may have a salami structure by containing an occluded phase around the rubber particles, but preferably has a large proportion of rubber particles forming a single phase.
[0016]
In addition, it is well known that the ABS resin contains a vinyl cyanide compound and an aromatic vinyl compound that are not grafted to the diene rubber component, and the ABS resin of the present invention is free of the occurrence of such polymerization. The polymer component may be contained. The molecular weight of the copolymer comprising such free vinyl cyanide compound and aromatic vinyl compound is preferably 0.2 to 1.0, more preferably 0.3 to 0.7 in terms of intrinsic viscosity.
[0017]
The ratio of the grafted vinyl cyanide compound and aromatic vinyl compound is preferably 20 to 200%, more preferably 20 to 70%, based on the diene rubber component.
[0018]
The thermoplastic graft copolymer of the present invention may be produced by any polymerization method such as bulk polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method may be copolymerized in one stage or in multiple stages. Also good. Further, among these, those produced by the bulk polymerization method can be preferably used in that the heat and humidity resistance can be further improved. Although this cause has not been fully elucidated, metal salt components such as emulsifiers used in emulsion polymerization and suspension polymerization directly affect hydrolysis caused by phosphate esters or remain in polycarbonate resin. The possibility of acting on the chlorinated compounds to affect hydrolysis is considered.
[0019]
The phosphate ester flame retardant used as component c in the present invention is represented by the following formula (I).
[0020]
[Chemical 1]

[0021]
(However, X in the above formula is hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis And those derived from (4-hydroxyphenyl) sulfide, wherein j, k, l and m are each independently 0 or 1, n is an integer of 0 to 5, or n different phosphorus In the case of blends of acid esters, the average value is 0 to 5, and R ₁ , R ₂ , R ₃ , and R ₄ are independently from phenol, cresol, xylenol, isopropylphenol, butylphenol, and p-cumylphenol. It will be induced.)
[0022]
Among these, preferably, X in the above formula includes those derived from hydroquinone, resorcinol and bisphenol A, j, k, l and m are each 1, and n is an integer of 0 to 3. In the case of blends of phosphate esters having different n numbers, the average value is 0 to 3, and R ₁ , R ₂ , R ₃ , and R ₄ are derived from phenol, cresol, and xylenol, respectively.
[0023]
More particularly preferably, X is derived from resorcinol, j, k, l, m are each 1, n is 0 or 1, and R ₁ , R ₂ , R ₃ , and R ₄ Are each independently derived from phenol or xylenol.
[0024]
Among these phosphate ester flame retardants, triphenyl phosphate is used as the monophosphate compound, and resorcinol bis (dixylenyl phosphate) is used as the condensed phosphate ester, which has good flame retardancy and good fluidity during molding. It can be preferably used for reasons such as.
[0025]
The polytetrafluoroethylene having a fibril forming ability used as the d component in the present invention is classified as type 3 in the ASTM standard, and the object of the present invention is not achieved if it does not have a fibril forming ability. Polytetrafluoroethylene having a fibril forming ability has a melting and dripping preventing performance at the time of a combustion test of a test piece in a UL vertical combustion test. For example, a polytetrafluoroethylene having such a fibril forming ability is, for example, Mitsui DuPont. It is commercially available as Teflon 6J from Fluorochemical Co., Ltd. or as Polyflon from Daikin Chemical Industries, Ltd. In addition, the polytetrafluoroethylene having such fibril-forming ability can be used in a solid state or in a dispersion form dispersed and mixed in a dispersion medium, but the dispersant component has an adverse effect on moisture and heat resistance. In particular, those in a solid state can be preferably used.
[0026]
The blending ratio of the a component to the d component is 38 to 91.9% by weight of the a component, 5 to 40% by weight of the b component, 3 to 20% by weight of the c component, and 0.1 to 2% by weight of the d component. When the a component is less than 38% by weight or the b component exceeds 40% by weight, the heat resistance (particularly the load deflection temperature) and the mechanical strength are lowered. On the other hand, when the component a exceeds 91.9% by weight or the component b is less than 5% by weight, the fluidity is lowered and the moldability is lowered. If the component c is less than 3% by weight, sufficient flame retardancy cannot be obtained, and if it exceeds 20% by weight, the mechanical strength and heat resistance (particularly load deflection temperature) are remarkably reduced, and the heat and humidity resistance is also greatly reduced. Furthermore, if the d component is less than 0.1% by weight, it is difficult to obtain sufficient melting and dripping prevention performance, and if it exceeds 2% by weight, the appearance deteriorates.
[0027]
In the present invention, the silicate filler used as the e component refers to an inorganic filler containing 35 wt% or more, preferably 40 wt% or more of SiO ₂ component due to its chemical composition. Such silicate fillers include kaolin, talc, clay, pyrophyllite, mica, montmorillonite, bentonite, wollastonite, sepiolite, zonotlite, natural silica, synthetic silica, various glass fillers, zeolite, diatomaceous earth, halloysite. Etc. can be mentioned.
[0028]
Among them, in the present invention, the filler can be dispersed finely to increase the action point for suppressing hydrolysis, and from the viewpoint of imparting flame retardancy, the reinforcing effect on the resin is also important. Scale-like inorganic fillers such as talc and mica can be mentioned as preferred fillers. Of these, talc is most preferable.
[0029]
The talc in the present invention is preferably in the form of a powder having an average particle diameter of 0.5 to 20 μm from the viewpoint of securing rigidity. Since talc is thicker than mica, it is preferable to have a smaller particle diameter in order to make it equal in dispersion in the resin. Here, the average particle diameter of talc means a value measured by a microtrack laser diffraction method.
[0030]
The talc of the present invention is not particularly limited to the production area and the like, but more preferably one having a higher SiO ₂ component, for example, 60% by weight or more. In the case of such an amount of SiO ₂ component, the content of Fe ₂ O ₃ which is an impurity is relatively likely to increase, so that talc is advantageous in terms of hue. In addition, there is no particular limitation on the production method when pulverizing such talc from raw stone, and axial flow mill method, annular mill method, roll mill method, ball mill method, jet mill method, container rotary compression shearing mill method, etc. Can be used. Further, such talc is preferably in an agglomerated state in terms of its handleability, and such production methods include a method by degassing compression, a method of compression using a binder resin, etc., and a method by degassing compression is particularly simple. And it is preferable at the point which does not mix an unnecessary binder resin component in the composition of this invention.
[0031]
The mica in the present invention is preferably in the form of a powder having an average particle diameter of 1 to 80 μm from the viewpoint of securing the reinforcing effect. Mica is a pulverized product of silicate mineral containing aluminum, potassium, magnesium, sodium, iron and the like. Mica includes muscovite, phlogopite, biotite, artificial mica, etc., and any mica can be used as the mica of the present invention. In particular, the OH groups of phlogopite, biotite and phlogopite are replaced with F atoms. Preference is given to muscovite with a higher SiO ₂ content than artificial mica. In addition, as a pulverization method in the production of mica, a dry pulverization method in which mica rough is pulverized with a dry pulverizer, and mica rough is roughly pulverized in a dry pulverizer, then water is added and a wet pulverizer in a slurry state. There is a wet pulverization method in which the pulverization is followed by dehydration and drying, and the dry pulverization method is generally lower in cost, but it is difficult to pulverize mica thinly and finely in the present invention. It is preferable to use mica produced by
[0032]
As the average particle diameter of mica, those having an average particle diameter of 1 to 80 μm measured by a microtrack laser diffraction method can be preferably used. More preferably, the average particle diameter is 2 to 50 μm. In the case of 1 to 80 μm, the flame retardancy is more favorably exerted, and the condition of fine dispersion in the resin is also satisfied, so that the heat and humidity resistance can be maintained well.
[0033]
As the thickness of mica, one having a thickness measured by observation with an electron microscope of 0.01 to 1 μm can be used. The thickness is preferably 0.03 to 0.3 μm. Further, the mica may be surface-treated with a silane coupling agent or the like, and further granulated with a binder such as an epoxy, urethane, or acrylic, and may be granulated. Specific examples of mica include mica powder (mica powder) A-41, A-21, and A-11 manufactured by Yamaguchi Mica Industry Co., Ltd., which are easily available on the market.
[0034]
In the present invention, the blending ratio of the component e is in the range of 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight per 100 parts by weight in total of the components a to d. When the blending ratio of this d component is less than 0.1 part by weight, there is no effect of improving the heat and moisture resistance, and when it exceeds 30 parts by weight, the effect on the heat and humidity resistance is saturated, while the impact strength is reduced or the molded product obtained This is not preferable because the surface appearance of the surface deteriorates.
[0035]
In the present invention, the aromatic monovinyl compound is used as the component f with respect to 50 to 75 parts by weight of a rubber latex containing a total of 100% by weight of 60 to 90% by weight of acrylic acid alkyl ester and 10 to 40% by weight of butadiene. A shell composed of 25 to 50 parts by weight obtained by grafting a mixture of one or more monomers selected from vinyl cyanide compounds and methacrylates by one or two or more stages of graft polymerization. An acrylate-based core-shell graft copolymer having a total of 100 parts by weight of the core and the shell is used.
[0036]
The acrylic ester used in the f component of the present invention is an acrylic ester having 2 to 8 carbon atoms in the alkyl group. For example, ethyl acrylate, propyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, etc. Can be mentioned. Among these, butyl acrylate and 2-ethylhexyl acrylate are preferably used, and 2-ethylhexyl acrylate is particularly preferable.
[0037]
Examples of the aromatic monovinyl compound used for the component f include styrene, vinyltoluene, and α-methylstyrene, and styrene is particularly preferable. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and acrylonitrile is particularly preferable.
[0038]
Furthermore, the methacrylic ester of the component f refers to an alkyl ester of methacrylic acid having 1 to 5 carbon atoms, and examples thereof include methyl methacrylate, propyl methacrylate, and butyl methacrylate, and methyl methacrylate is particularly preferable.
[0039]
The acrylate-based core-shell graft copolymer of component f used in the present invention is a core-shell graft copolymer comprising a core and a shell graft-polymerized in one or more stages prepared by an emulsion polymerization method. It is a polymer and consists of 50 to 75 parts by weight of the core and 50 to 25 parts by weight of the shell, preferably 50 to 70 parts by weight of the core and 50 to 30 parts by weight of the shell, in a total of 100 parts by weight of the core and shell. Further, the average particle diameter of the core is 0.08 to 0.25 μm, more preferably 0.13 to 0.20 μm.
[0040]
Furthermore, the ratio of alkyl acrylate ester and butadiene in such a core is 60 to 90% by weight, preferably 60 to 80% by weight, and 10 to 40% by weight of butadiene in the total 100% by weight. It is preferably 20 to 40% by weight.
[0041]
Such a core may be copolymerized with other copolymerizable monomers, preferably methyl methacrylate and / or styrene, particularly preferably methyl methacrylate, within a range of 20% by weight or less based on the total amount of the core.
[0042]
The shell in the f component of the present invention is composed of one or a mixture of two or more monomers selected from aromatic monovinyl compounds, vinyl cyanide compounds, and methacrylic acid esters. And those containing methacrylic acid esters are preferred. Here, the proportion of each monomer in the shell is preferably 45 to 80% by weight, more preferably 55 to 70% by weight, based on 100% by weight of the total amount of the shell. Therefore, when an aromatic monovinyl compound or a vinyl cyanide compound is contained, the total of the aromatic monovinyl compound and the vinyl cyanide compound is preferably 20 to 55% by weight, more preferably 30 to 45% by weight. Further, when a vinyl cyanide compound is contained, the vinyl cyanide compound is preferably 20 to 35% by weight, more preferably 22 to 30% by weight, out of a total of 100% by weight with the aromatic monovinyl compound.
[0043]
Further preferably, the f component of the present invention is such that the shell of the f component comprises a two-stage graft polymerization, and the first graft component is a mixture of an aromatic monovinyl compound and a methacrylic acid ester, or an aromatic monovinyl compound, vinyl cyanide. A mixture of a compound and a methacrylic acid ester, the second graft component is a methacrylic acid ester, and the first graft component is 40 to 75% in a total of 100% by weight of the shell component. % And the second graft component is preferably 25 to 60% by weight. More preferably, the first graft component is 42 to 70% by weight and the second graft component is 30 to 58% by weight.
[0044]
Further, the f component of the present invention is obtained by polymerizing a small amount of a crosslinkable monomer in addition to the monomer components described above when polymerizing the core of the f component and the shell at each stage. Here, the amount of the crosslinkable monomer is 0.01 to 3% by weight with respect to 100% by weight of the total of the monomers used for the core polymerization in the polymerization of the core. It is 0.01 to 2 weight% with respect to 100 weight% of the total of a monomer.
[0045]
Here, as the crosslinkable monomer used in the polymerization of the core, a monomer having two or more polymerizable ethylenically unsaturated bonds in the molecule is preferably used. Specific examples include aromatic divinyl monomers such as divinylbenzene, ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol (meth) acrylate, oligoethylene glycol di (meth) acrylate, and trimethylol. Examples thereof include propanedi (meth) acrylate and trimethylolpropane tri (meth) acrylate. Of these, ethylene glycol dimethacrylate and divinylbenzene are preferably used.
[0046]
As the crosslinkable monomer used for the polymerization of the shell, divinylbenzene, butylene glycol diacrylate, hexanediol diacrylate and the like are preferably used, and ethylene glycol dimethacrylate and divinylbenzene are particularly preferably used.
[0047]
Furthermore, the component f of the present invention can be used for the purpose of eliminating poor dispersion during production, and the like, which has been subjected to a treatment for improving blocking resistance, and a known method can be used as such a treatment method.
[0048]
Examples of such methods include a method of spray-drying the graft copolymer latex to spheroidize the powder, a method of adjusting the salting-out conditions of the copolymer latex, and a method of adding additives such as a lubricant. In addition, the monomer (the aromatic monovinyl compound, the vinyl cyanide compound, the acrylic acid ester, and the methacrylic acid ester) selected from 5 to 49% by weight of the elastic trunk polymer (made of butadiene and acrylic acid ester). One or more types of monomers) 0.1 to 25 parts by weight of a powdery property-improved graft copolymer obtained by graft polymerization of 51 to 95% by weight of the acrylic acid ester core-shell of the present invention in a slurry state The method of mix | blending with 100 weight part of graft copolymers is also mentioned.
[0049]
Alternatively, there may be mentioned a method of adding a hard inelastic polymer emulsion to the coagulated acrylate-based core-shell graft copolymer slurry of the present invention. Here, the hard inelastic polymer is polymerized from at least one monomer selected from an aromatic monovinyl compound, a vinyl cyanide compound, and a methacrylic acid ester, and particularly contains 80% by weight or more of methyl methacrylate. Those that do are preferred.
[0050]
Among these, the method of blending the powder property-improved graft copolymer or the hard inelastic polymer into the acrylate-based graft copolymer in the slurry state is simple and effective because it can achieve a reduction in blocking properties. preferable.
[0051]
The method for improving the blocking resistance by adding a powder property-improved graft copolymer or a hard polymer is carried out within the range of each component amount in the acrylate-based core-shell graft copolymer of the present invention. Is called.
[0052]
As the acrylate-based core-shell graft polymer preferred as the f component of the present invention, the total of the core and shell is 100 parts by weight, and the total of 100 to 80% by weight of acrylic acid alkyl ester and 20 to 40% by weight of butadiene. A mixture of an aromatic monovinyl compound and a methacrylic acid ester and, if necessary, a vinyl cyanide compound is grafted to 50 to 70 parts by weight of a core made of rubber latex containing wt% by two-stage graft polymerization. 30 to 50 parts by weight of the shell, and when 100% by weight of the shell is 55 to 70% by weight of the methacrylic acid ester and further contains a vinyl cyanide compound, the vinyl cyanide compound is an aromatic monovinyl compound. 22 to 30% by weight of the total 100% by weight of the first And the second graft component is composed of a methacrylic ester, and the second graft component is composed of a mixture of an aromatic monovinyl compound and a methacrylic ester, or a mixture of an aromatic monovinyl compound, a vinyl cyanide compound and a methacrylic ester. And the first graft component is 42 to 70% by weight and the second graft component is 30 to 58% by weight among the total 100% by weight of the shell component. Resins commercially available as trade names “HIA-15”, “HIA-28”, and “HIA-28S” can be given.
[0053]
In the present invention, the blending ratio of the component f is in the range of 1 to 10 parts by weight per 100 parts by weight in total of the components a to d. If the blending ratio of the component f is less than 1 part by weight, sufficient impact strength cannot be obtained, and if it exceeds 10 parts by weight, sufficient flame retardancy cannot be imparted.
[0054]
Resin composition of the present invention The above-mentioned components can be produced by mixing them with a mixer such as a tumbler, V-type blender, Nauta mixer, Banbury mixer, kneading roll, or extruder. Furthermore, other thermoplastic resins such as polyester, polyamide, polyphenylene ether and the like may be mixed within a range not impairing the object of the present invention, and various additives such as stable ones exhibiting the effect as necessary, for example, stable An agent, a release agent, an antistatic agent, an ultraviolet absorber, a dye or pigment may be included.
[0055]
Examples of the heat stabilizer include conventionally known phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof as heat stabilizers for aromatic polycarbonates. Specifically, trisnonylphenyl phosphite, Trimethyl phosphate, tris (2,4-di-tert-butylphenyl) phosphite and dimethyl benzenephosphonate can be preferably mentioned. These heat stabilizers may be used alone or in admixture of two or more.
[0056]
In addition to the above, the heat stabilizer of the present invention is preferably mixed with a hindered phenol compound or sulfur compound generally known as an antioxidant. Such a compound is particularly preferable in that it maintains the thermal stability of the styrene resin and suppresses thermal decomposition of the resin. Specific examples of such compounds include n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), tris (3,5-di-tert-butyl-4- Hydroxybenzyl) isocyanurate, 2,6-di-tert-butyl-4-methylphenol, 2,4-di-tert-amyl-6- [1- (3,5-di-tert-amyl-2-hydroxy) Phenyl) ethyl] phenyl acrylate, etc., and pentaerythrityltetrakis (3-laurylthiopropionate), dilauryl 3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, it may be mentioned distearyl-3,3'-thiodipropionate and the like.
[0057]
Release agents include esters of fatty acids and aliphatic alcohols, esters of fatty acids and aromatic alcohols, partial esters or total esters of fatty acids and polyhydric alcohols, partial esters or total esters of fatty acids and polyglycols, and epoxies. Examples include esters and ester-based natural waxes. Further, in addition to the above-mentioned ester series, low molecular weight polyethylene, low molecular weight polypropylene, hydrocarbon series such as paraffin wax, and fatty acid amide series internal release agents such as stearic acid amide and lauric acid amide can be exemplified. Examples of the ester release agent include glycerin fatty acid ester “Riquemar S-100A” (trade name) from Riken Vitamin Co., Ltd. or montanic acid ester “Hoechst wax E” (trade name) from Hoechst Co., Ltd. Low molecular weight polyethylene is commercially available from Mitsui Chemicals as “High Wax” (trade name).
[0058]
Examples of the ultraviolet absorber include 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole and 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole. 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2′-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2′-p-phenylenebis (1,3-benzoxazin-4-one), polyalkylene naphthalate and the like.
[0059]
The resin composition thus obtained can be easily molded by methods such as extrusion molding, injection molding and compression molding, and can also be applied to blow molding, vacuum molding and the like. In particular, it is most suitable as a material for electrical and electronic parts and OA exterior applications that require UL94V-0.
[0060]
DETAILED DESCRIPTION OF THE INVENTION
The following examples further illustrate the present invention. In addition, the part in an Example is a weight part and evaluation was based on the following method.
[0061]
(1) Impact resistance: According to ASTM D256, an impact resistance value with an Izod notch was measured.
[0062]
(2) Flame retardancy: A combustion test at a thickness of 1.6 mm was performed according to UL standard 94V.
[0063]
(3) Pigment colorability: Hue measurement was performed on a square plate of 50 mm × 80 mm × 2 mm using a colorimetric color difference meter Z-1001DP type (C light source, 2-degree visual field) manufactured by Nippon Denshoku Industries Co., Ltd. The L ^* value is obtained by hue analysis of the molded plate, and the lower this value, that is, the lower the lightness, the better the pigment colorability. In general, if the L ^* value when 0.5 parts by weight of carbon black is added is 12 or less, it is judged that the pigment colorability is good, and it can be used for applications in which a dark color system is colored.
[0064]
(4) Moisture and heat resistance-1: 1/8 "Izod impact test piece was notched and treated with an environmental tester (Platinus Subzero Lucifer manufactured by Tabai Espec Co., Ltd.) for 500 hours under conditions of 65 ° C and 85% RH. Then, the impact resistance value with an Izod notch was measured according to ASTM D256, and compared with the impact resistance value with an Izod notch before wet heat treatment.
[0065]
(5) Moisture and heat resistance-2: The apparent viscosity average molecular weight of the test piece after the wet heat treatment of (4) was measured by the same method as that for measuring the molecular weight of the aromatic polycarbonate resin. That is, after dissolving the test piece in methylene chloride, the specific viscosity of the solution obtained by removing the insoluble matter by filtration was measured in the same manner as the viscosity average molecular weight measurement of the polycarbonate resin described in the text, and the same calculation formula Was used to calculate the apparent viscosity average molecular weight.
[0066]
[Examples 1-7, Comparative Examples 1-5]
After mixing each component described in Table 1 and Table 2 with a V-type blender based on the amounts listed in the table, the cylinder temperature was 240 ° C. using a vented twin screw extruder [TEX30XSST manufactured by Nippon Steel Works, Ltd.] with a diameter of 30 mmφ. And pelletized. After the pellets were dried at 100 ° C. for 5 hours, various test pieces were prepared and evaluated by an injection molding machine [T-150D manufactured by FANUC Corporation] at a cylinder temperature of 250 ° C. and a mold temperature of 70 ° C. The evaluation results are shown in Tables 1 and 2. In addition, the symbol which shows each component of Table 1 and Table 2 is as follows.
[0067]
(Component a)
PC: Polycarbonate resin (L-1225 manufactured by Teijin Chemicals Ltd.)
(Component b)
ABS: ABS resin (Santac UT-61 manufactured by Mitsui Chemicals, Inc.)
(Component c)
FR-1: Triphenyl phosphate [TPP manufactured by Daihachi Chemical Co., Ltd.]
FR-2: resorcinol bis (dixylenyl phosphate) [Adeka Stub FP-500 manufactured by Asahi Denka Kogyo Co., Ltd.]
(D component)
PTFE: polytetrafluoroethylene [F-201L, manufactured by Daikin Industries, Ltd.]
(E component)
Talc: Talc [Nippon Talc Co., Ltd. Talc P-3, average particle size of about 3 μm]
Mica: Mica powder [A-41, manufactured by Yamaguchi Mica Industry Co., Ltd., average particle size of about 40 μm]
(Fillers other than e component)
CF: carbon fiber [Tobe Rayon Co., Ltd. Beth Fight HTA-C6-U, PAN, urethane bundling, fiber diameter 7 μm]
(Component f)
Rubber-1: 2-ethylhexyl acrylate / butadiene / methyl methacrylate / styrene multistage graft copolymer (styrene content: 15% by weight) [HIA-15 manufactured by Kureha Chemical Industry Co., Ltd.]
(Polymer other than component f)
Rubber-2: Acrylic-silicone impact modifier [S-2001 manufactured by Mitsubishi Rayon Co., Ltd. ]
( Other)
CB: Carbon black [manufactured by Mitsubishi Chemical Corporation CB-960]
[0068]
[Table 1]

[0069]
[Table 2]

[0070]
As is apparent from this table, the comparison between Example 1 and Comparative Example 1 shows that when the specific acrylate-based core-shell graft copolymer of the present invention is used, flame retardancy and colorability are improved. It can be seen that compatibility is achieved . Hand, from comparison between Comparative Example 3 and 4 and Example 2, when formulated with silicate compounds of the present invention only, it can be seen that improvements in resistance to moist heat is achieved.
[0071]
【The invention's effect】
The polycarbonate resin composition of the present invention is extremely useful for various industrial applications such as the field of OA equipment and the field of electrical and electronic equipment because it is excellent in flame retardancy and impact strength, and is excellent in heat and moisture resistance and colorability.

Claims (2)

Polycarbonate resin (component a) 38-91.9% by weight, thermoplastic graft copolymer (component b) 5-40% by weight, grafted with vinyl cyanide compound and aromatic vinyl compound on diene rubber component, phosphate ester 100 parts by weight of a composition comprising a total of 100% by weight of 3 to 20% by weight of a flame retardant (c component) and 0.1 to 2% by weight of polytetrafluoroethylene (d component) having fibril-forming ability, silicate type filler (e component) 0.1 to 30 parts by weight, and in total 100 parts by weight of the core and shell, a rubber containing a total of 100 wt% of 60 to 80% by weight of acrylic acid alkyl esters, and butadiene 20 to 40 wt% Aromatic monovinyl compound and methacrylic acid ester and, if necessary, further vinyl cyanide for 50 to 70 parts by weight of the latex core It consists of 30 to 50 parts by weight of a shell obtained by grafting a mixture comprising a two-stage graft polymerization, and methacrylic acid ester is 55 to 70% by weight in 100% by weight of the shell, and further contains a vinyl cyanide compound. The vinyl cyanide compound is 22 to 30% by weight in a total of 100% by weight with the aromatic monovinyl compound, and the first graft component is a mixture of an aromatic monovinyl compound and a methacrylic acid ester, or an aromatic monovinyl compound, The mixture is composed of any of a mixture of a vinyl cyanide compound and a methacrylic acid ester, the second graft component is composed of a methacrylic acid ester, and the first graft component is 42% in a total of 100% by weight of the shell component. -70 wt% and the second graft component is 30-58 wt% Acrylic acid ester-based core - shell graft copolymer (f component) 1 to 10 parts by weight or Ranaru resin composition.   The resin composition according to claim 1, wherein the component e is a scaly silicate filler.