JP3964557B2 - Aromatic polycarbonate resin composition and optical molded article - Google Patents

Description

［式中、Ａは水素原子または炭素数１〜９、好ましくは１〜８の脂肪族炭化水素基を示し、ｒは１〜５、好ましくは１〜３の整数を示す。］
【００２１】
前記単官能フェノール類の具体例としては、例えばフェノール、ｐ−ｔｅｒｔ−ブチルフェノール、ｐ−クミルフェノールおよびイソオクチルフェノールが挙げられる。
【００２２】
また、他の単官能フェノール類としては、長鎖のアルキル基或いは脂肪族ポリエステル基を置換基として有するフェノール類または安息香酸クロライド類、もしくは長鎖のアルキルカルボン酸クロライド類を使用することができ、これらを用いて芳香族ポリカーボネート共重合体の末端を封鎖すると、これらは末端停止剤または分子量調節剤として機能するのみならず、樹脂の溶融流動性が改良され、成形加工が容易となるばかりでなく、基板としての物性も改良される。特に樹脂の吸水率を低くする効果があり、好ましく使用される。これらは下記一般式［Ｉ−ａ］〜［Ｉ−ｈ］で表される。
【００２３】
【化２】

［各式中、Ｘは−Ｒ−Ｏ−、−Ｒ−ＣＯ−Ｏ−または−Ｒ−Ｏ−ＣＯ−である、ここでＲは単結合または炭素数１〜１０、好ましくは１〜５の二価の脂肪族炭化水素基を示し、Ｔは単結合または上記Ｘと同様の結合を示し、ｎは１０〜５０の整数を示す。
【００２４】
Ｑはハロゲン原子または炭素数１〜１０、好ましくは１〜５の一価の脂肪族炭化水素基を示し、ｐは０〜４の整数を示し、Ｙは炭素数１〜１０、好ましくは１〜５の二価の脂肪族炭化水素基を示し、Ｗ¹は水素原子、−ＣＯ−Ｒ¹³、−ＣＯ−Ｏ−Ｒ¹⁴またはＲ¹⁵である、ここでＲ¹³、Ｒ¹⁴およびＲ¹⁵は、それぞれ炭素数１〜１０、好ましくは１〜５の一価の脂肪族炭化水素基、炭素数４〜８、好ましくは５〜６の一価の脂環族炭化水素基または炭素数６〜１５、好ましくは６〜１２の一価の芳香族炭化水素基を示す。
【００２５】
ｌは４〜２０、好ましくは５〜１０の整数を示し、ｍは１〜１００、好ましくは３〜６０、特に好ましくは４〜５０の整数を示し、Ｚは単結合または炭素数１〜１０、好ましくは１〜５の二価の脂肪族炭化水素基を示し、Ｗ²は水素原子、炭素数１〜１０、好ましくは１〜５の一価の脂肪族炭化水素基、炭素数４〜８、好ましくは５〜６の一価の脂環族炭化水素基または炭素数６〜１５、好ましくは６〜１２の一価の芳香族炭化水素基を示す。］
【００２６】
これらのうち好ましいのは、［Ｉ−ａ］および［Ｉ−ｂ］の置換フェノール類である。この［Ｉ−ａ］の置換フェノール類としては、ｎが１０〜３０、特に１０〜２６のものが好ましく、その具体例としては、例えばデシルフェノール、ドデシルフェノール、テトデシルフェノール、ヘキサデシルフェノール、オクタデシルフェノール、エイコシルフェノール、ドコシルフェノールおよびトリアコンチルフェノールなどを挙げることができる。
【００２７】
また、［Ｉ−ｂ］の置換フェノール類としてはＸが−Ｒ−ＣＯ−Ｏ−であり、Ｒが単結合である化合物が適当であり、ｎが１０〜３０、特に１０〜２６のものが好適であって、その具体例としては、例えばヒドロキシ安息香酸デシル、ヒドロキシ安息香酸ドデシル、ヒドロキシ安息香酸テトラデシル、ヒドロキシ安息香酸ヘキサデシル、ヒドロキシ安息香酸エイコシル、ヒドロキシ安息香酸ドコシルおよびヒドロキシ安息香酸トリアコンチルが挙げられる。
【００２８】
前記一般式［Ｉ−ａ］〜［Ｉ−ｇ］で示される置換フェノール類または置換安息香酸クロライドにおいて置換基の位置は、ｐ位またはｏ位が一般的に好ましく、その両者の混合物が好ましい。
【００２９】
前記単官能フェノール類は、得られた芳香族ポリカーボネート樹脂組成物の全末端に対して少なくとも５モル％、好ましくは少なくとも１０モル％末端に導入されることが望ましく、また単官能フェノール類は単独でもしくは２種以上混合して使用してもよい。
【００３０】
また、本発明のポリマーＡとしての芳香族ポリカーボネート共重合体において、成分ａ−１の１,１−ビス（４−ヒドロキシフェニル）−３,３,５−トリメチルシクロヘキサンが、全二価フェノール成分の８０モル％以上である場合は、樹脂の流動性が低下することがあり、そのため前記一般式［Ｉ−ａ］〜［Ｉ−ｇ］で示される置換フェノール類または置換安息香酸クロライド類を末端停止剤として使用することが好ましい。
【００３１】
本発明の組成物の調整において、ポリマーＡとポリマーＢとの混合は、ポリマー溶液、粉粒体、ペレット等の成形品の段階が考えられるが、特に規制するものではない。また混合の方法については、ポリマー溶液の段階では、例えば、攪拌機付き容器が主として考えられ、また、粉粒体、ペレット等の成形品の段階では、例えばタンブラー、Ｖ型ブレンダー、ナウターミキサー、バンバリーミキサー、混練ロール、押出機などで混合する方法が用いられる。いずれの場合も任意の方法で使用され、特に規制はないが、混合操作中の異物混入に対する除去方法の簡便さからポリマー溶液状態での混合後、任意の目開きのフィルターを通過させるという方法が好ましい。
【００３２】
本発明の芳香族ポリカーボネート樹脂組成物はそのポリマー０.７ｇを１００ｍｌの塩化メチレンに溶解し、２０℃で測定した比粘度が０.２〜０.５のものが好ましく、０.２５〜０.４の範囲のものがより好ましい。比粘度が０.２未満では成形品が脆くなり、０.５より高くなると溶融流動性が悪く、成形不良を生じ、光学的に良好な成形品が得られ難くなる。
【００３３】
本発明の芳香族ポリカーボネート樹脂組成物は、ＡSＴＭ Ｄ−０５７０によって測定した吸水率が０.３重量％以下であり、０.２５重量％以下であることが好ましく、０.２０重量％以下であることがより好ましい。吸水率が０.３重量％を超えると、本発明の芳香族ポリカーボネート樹脂組成物が好適に用いられる光ディスク基板の表面上に金属膜を形成させた光ディスクが吸水によって反りを生じ易くなり、トラッキングエラーを起こし易くなるので好ましくない。特に好ましい吸水率は０.１８重量％以下である。
【００３４】
本発明の芳香族ポリカーボネート樹脂組成物は、オリゴマー含量が１０％以下であることが好ましく、７％以下がより好ましく、特に５％以下が好ましい。このオリゴマー含量の値は下記方法およびカラムを使用して測定された値である。すなわち、東ソー（株）製、ＴＳＫｇｅｌＧ２０００ＨＸＬとＧ３０００ＨＸＬカラム各１本づつ直列に繋いで溶離液としてクロロホルムを用い、流量０.７ｍｌ／分で安定化した後、該芳香族ポリカーボネート樹脂組成物のクロロホルム溶液を注入する方法で測定したＧＰＣチャートのリテンションタイムが２３分以降のオリゴマーピーク面積の合計の全ピーク面積に対する割合がオリゴマー含量であり、この値が１０％以下であることが好ましく、７％以下であることがより好ましい。オリゴマー含量が７％、殊に１０％を越えると、成形時に金型表面を汚染することがあるので望ましくなく、その汚染はオリゴマー含量が多くなる程顕著になる傾向がある。一方、オリゴマーは芳香族ポリカーボネート樹脂組成物の製造過程で生じるものであり、完全に零（０）にすることはできない。
【００３５】
オリゴマーは、前記した含量以下であればよく、その値を満足する限り、少割合含有されていても差支えない。０.１％以上、より好ましくは０.１５％以上の少割合の含量でオリゴマーが存在すると、それ以下のものと比べて溶融流動性が向上する。そのため、特に好ましくはオリゴマー含量は０.１５〜４％の範囲である。
【００３６】
芳香族ポリカーボネート樹脂組成物中のオリゴマー含量を前記範囲に制御するには、大量のオリゴマーが共重合体中に含まれないように重合を充分に完結することが必要であり、また触媒および重合条件を適宣選択することが要求される。もしオリゴマー含量が前記範囲を越えている場合には、例えばオリゴマーを抽出などの手段により除去する処置が採用される。この抽出は芳香族ポリカーボネート樹脂組成物の溶液（例えば塩化メチレン溶液）を、その共重合体の貧溶剤または非溶剤（例えばアセトンまたはメタノール）中に滴下する方法、或いはその組成物を貧溶媒または非溶媒に浸漬して、オリゴマーを抽出する方法などの手段によって実施することができる。
【００３７】
本発明の芳香族ポリカーボネート樹脂組成物は、光学的材料、殊に光ディスク基板として好適に使用されるため、その中に未溶解粒子が或る一定量以上存在しないことが望ましい。
【００３８】
すなわち、かかる芳香族ポリカーボネート樹脂組成物は、その２０ｇを塩化メチレン１Ｌに溶解した溶液をハイアックロイコ社製液体パーティクルカウンターモデル４１００を用いたレーザーセンサー法にて、散乱光をラテックス粒子の散乱光に換算する方法で求めた径０.５μｍ以上の未溶解粒子が、該芳香族ポリカーボネート樹脂組成物１ｇ当り２５,０００個以下、且つ１μｍ以上の未溶解粒子が５００個以下であることが好ましい。０.５μｍ以上の未溶解粒子が２５,０００個を超えるか、または１μｍ以上の未溶解粒子が５００個を超えると光ディスクに書き込まれた情報ピットに悪影響を及ぼしエラーレートが大きくなるので好ましくない。さらに好ましくは、０.５μｍ以上の未溶解粒子が２０,０００個以下、且つ１μｍ以上の未溶解粒子が２００個以下である。また、１０μｍ以上の未溶解粒子は実質的に存在すべきでない。また５μｍ以上の未溶解粒子は３０個／ｇ以下であるのが好ましい。
【００３９】
芳香族ポリカーボネート樹脂組成物中における未溶解粒子の量を前記範囲とするためには、重合過程および造粒過程において、未溶解粒子が混入しないか或いは除去し得る手段を採用すべきである。
【００４０】
そのような手段としては、例えば操作をクリーンルームで行うこと、未溶解粒子の除去装置の付いた造粒装置を使用すること（具体的例としては、軸受け部に異物取り出し口を有する隔離室を設けたニーダーなど）或いは摺動部分に樹脂粒子が触れない構造の装置（例えばスプレードライヤー形式の造粒機）で造粒することなどがある。
【００４１】
また、未溶解粒子を除去する他の手段として、樹脂の溶液を目開きの小さいフィルター（０.５〜１μｍ）によりろ過する方法或いは樹脂を溶融して後、金属フィルター（１０〜４０μｍ）により固体粒子を除去する方法などが採用される。
【００４２】
本発明の芳香族ポリカーボネート樹脂組成物は、その光弾性定数の値が６０×１０^-13ｃｍ²／ｄｙｎ以下、好ましくは５５×１０^-13ｃｍ²／ｄｙｎ以下のものが有利に利用される。光弾性定数の値が前記値よりも大きい場合、光学用材料、殊に光ディスクとして適さなくなる。
【００４３】
芳香族ポリカーボネート樹脂組成物は、そのガラス転移点が１２０℃以上が好ましく、１３０℃以上がより好ましく、１４５℃以上がさらに好ましい。ガラス転移点が低くなると光学用材料、殊にディスク基板としての耐熱性が不足する。
【００４４】
本発明の芳香族ポリカーボネート樹脂組成物は、カーボネート前駆物質としてホスゲンを使用し、また溶媒として塩化メチレンなどの塩素系溶媒を使用した場合、塩素が少なからず残存している。この塩素の含有量が多いと成形金型が腐食したり、芳香族ポリカーボネート樹脂組成物の熱安定性が低下したり、また光ディスク基板として用いた場合、その金属膜の腐食が起こったりするので望ましくない。従って、塩素の含量は１０ｐｐｍ以下、好ましくは７ｐｐｍ以下、特に好ましくは５ｐｐｍ以下であるのが推奨される。ここで云う塩素含量とは、芳香族ポリカーボネート共重合体を三菱化学製全有機ハロゲン分析装置ＴＯＸ１０型を用いて燃焼法により測定された値を意味するものとする。
【００４５】
本発明の芳香族ポリカーボネート樹脂組成物は、溶融成形における流動性に優れかつ成形条件の大幅な制限が改善されている。従って成形条件にその巾が広くなるので成形の操作が容易となる。すなわち、本発明の樹脂組成物は溶融時（２８０℃）における流動性（ＭＦＲ値）が５２〜７０ｇ／１０ｍｉｎ、好ましくは５３〜６７ｇ／１０ｍｉｎであって、流動特性に優れている。またディスク基板に成形した場合、シリンダー温度を次第に低下させ、ある温度になると基板内に成形による不良個所が発生するが、この時の最低シリンダー温度が高いほど、成形操作条件の巾が小さくなり成形操作性が低くなる。本発明の樹脂組成物は、前記最低シリンダー温度が低く、従って成形操作条件の巾を大きく取ることができるメリットがある。この最低シリンダー温度を成形操作性の目安として実施例に示した。本発明の樹脂組成物はポリマーＡ単独の樹脂よりも１０℃以上、好適条件では１５℃以上低い最低シリンダー温度を有している。
【００４６】
さらに本発明の樹脂組成物から形成された成形品、殊に光ディスク基板は、優れた光学特性値を有している。すなわち、本発明の樹脂組成物は光弾性定数が４７×１０^-13〜６０×１０^-13ｃｍ²／ｄｙｎｅ、好適には４８×１０^-13〜５９×１０^-13ｃｍ²／ｄｙｎｅの範囲であり、また複屈折率が２５〜４５ｎｍ、好適には２７〜４２ｎｍの範囲であって、光ディスク基板としての目的に優れた特性を有している。
【００４７】
本発明において、前記芳香族ポリカーボネート樹脂組成物に、リン酸、亜リン酸、ホスホン酸、亜ホスホン酸およびこれらのエステルよりなる群から選択された少なくとも１種のリン化合物が、その共重合体に対して０.０００１〜０.０５重量％の割合で配合することができる。
このリン化合物を配合することにより、かかる芳香族ポリカーボネート樹脂組成物の熱安定性が向上し、成形時における分子量の低下や色相の悪化が防止される。
【００４８】
かかるリン化合物としては、リン酸、亜リン酸、ホスホン酸、亜ホスホン酸およびこれらのエステルよりなる群から選択される少なくとも１種のリン化合物であり、好ましくは下記一般式（１）〜（４）よりなる群から選択された少なくとも１種のリン化合物である。
【００４９】
【化３】

【００５０】
ここで、Ｒ¹〜Ｒ¹²は、それぞれ独立して、水素原子、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｔｅｒｔ−ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ドデシル、ヘキサデシル、オクタデシルなどの炭素数１〜２０のアルキル基、フェニル、トリル、ナフチルなどの炭素数６〜１５のアリール基またはベンジル、フェネチルなどの炭素数７〜１８のアラルキル基を表している。また１つの化合物中に２つのアルキル基が存在する場合は、その２つのアルキル基は互いに結合して環を形成していてもよい。
【００５１】
上記（１）式で示されるリン化合物としては、例えばトリフェニルホスファイト、トリスノニルフェニルホスファイト、トリス（２,４−ジ−ｔｅｒｔ−ブチルフェニル）ホスファイト、トリデシルホスファイト、トリオクチルホスファイト、トリオクタデシルホスファイト、ジデシルモノフェニルホスファイト、ジオクチルモノフェニルホスファイト、ジイソプロピルモノフェニルホスファイト、モノブチルジフェニルホスファイト、モノデシルジフェニルホスファイト、モノオクチルジフェニルホスファイト、ビス（２,６−ジ−ｔｅｒｔ−ブチル−４−メチルフェニル）ペンタエリスリトールジホスファイト、２,２−メチレンビス（４,６−ジ−ｔｅｒｔ−ブチルフェニル）オクチルホスファイト、ビス（ノニルフェニル）ペンタエリスリトールジホスファイト、ビス（２,４−ジ−ｔｅｒｔ−ブチルフェニル）ペンタエリスリトールジホスファイト、ジステアリルペンタエリスリトールジホスファイトなどが挙げられ、上記（２）式で示されるリン化合物としては、例えばトリブチルホスフェート、トリメチルホスフェート、トリフェニルホスフェート、トリエチルホスフェート、ジフェニルモノオルソキセニルホスフェート、ジブチルホスフェート、ジオクチルホスフェート、ジイソプロピルホスフェートなどが挙げられ、上記（３）式で示されるリン化合物としては、テトラキス（２,４−ジ−ｔｅｒｔ−ブチルフェニル）−４,４−ジフェニレンホスホナイトなどが挙げられ、また上記（４）式で示される化合物としては、ベンゼンホスホン酸ジメチル、ベンゼンホスホン酸ジエチル、ベンゼンホスホン酸ジプロピルなどが挙げれる。なかでも、ジステアリルペンタエリスリトールジホスファイト、トリエチルホスフェート、ベンゼンホスホン酸ジメチルが好ましく使用される。
【００５２】
かかるリン化合物の配合量は、該芳香族ポリカーボネート樹脂組成物に対して０.０００１〜０.０５重量％であり、０.０００５〜０.０２重量％が好ましく、０.００１〜０.０１重量％が特に好ましい。配合量が０.０００１重量％未満では上記効果が得られ難く、０.０５重量％を超えると、逆に該芳香族ポリカーボネート樹脂組成物の熱安定性に悪影響を与え、また耐加水分解性も低下するので好ましくない。
【００５３】
本発明の芳香族ポリカーボネート樹脂組成物には、酸化防止の目的で通常知られた酸化防止剤を添加することができる。その例としてはフェノール系酸化防止剤を示すことができ、具体的には例えばトリエチレングリコール−ビス（３−（３−ｔｅｒｔ−ブチル−５−メチル−４−ヒドロキシフェニル）プロピオネート）、１,６−ヘキサンジオール−ビス（３−（３,５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート）、ペンタエリスリトール−テトラキス（３−（３,５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート）、オクタデシル−３−（３,５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、１,３,５−トリメチル−２,４,６−トリス（３,５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）ベンゼン、Ｎ,Ｎ−ヘキサメチレンビス（３,５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシ−ヒドロシンナマイド）、３,５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシ−ベンジルホスホネート−ジエチルエステル、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、３,９−ビス｛１,１−ジメチル−２−［β−（３−ｔｅｒｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ］エチル｝−２,４,８,１０−テトラオキサスピロ（５,５）ウンデカンなどが挙げられる。これら酸化防止剤の好ましい添加量の範囲は芳香族ポリカーボネート樹脂組成物に対して、０.０００１〜０.０５重量％である。
【００５４】
さらに本発明の芳香族ポリカーボネート樹脂組成物には、必要に応じて一価または多価アルコールの高級脂肪酸エステルを加えることもできる。この一価または多価アルコールの高級脂肪酸エステルを配合することにより、前記芳香族ポリカーボネート樹脂組成物の成形時の金型からの離型性が改良され、ディスク基板の成形においては、離型荷重が少なく離型不良によるディスク基板の変形、ピットずれを防止できる。また、芳香族ポリカーボネート樹脂組成物の溶融流動性が改善される利点もある。
【００５５】
かかる高級脂肪酸エステルとしては、炭素原子数１〜２０の一価または多価アルコールと炭素原子数１０〜３０の飽和脂肪酸との部分エステルまたは全エステルであるのが好ましい。
【００５６】
また、かかる一価または多価アルコールと飽和脂肪酸との部分エステルまたは全エステルとしては、ステアリン酸モノグリセリド、ステアリン酸モノソルビテート、ベヘニン酸モノグリセリド、ペンタエリスリトールモノステアレート、ペンタエリスリトールテトラステアレート、プロピレングリコールモノステアレート、ステアリルステアレート、パルミチルパルミテート、ブチルステアレート、メチルラウレート、イソプロピルパルミテート、２−エチルヘキシルステアレートなどが挙げられ、なかでも、ステアリン酸モノグリセリド、ペンタエリスリトールテトラステアレートが好ましく用いられる。
【００５７】
かかるアルコールと高級脂肪酸とのエステルの配合量は、該芳香族ポリカーボネート樹脂組成物に対して０.０１〜２重量％であり、０.０１５〜０.５重量％が好ましく、０.０２〜０.２重量％がより好ましい。配合量が０.０１重量％未満では上記効果が得られず、２重量％を越えると金型表面の汚れの原因ともなる。
【００５８】
本発明の芳香族ポリカーボネート樹脂組成物には、さらに光安定剤、着色剤、帯電防止剤、滑剤などの添加剤を透明性を損なわない範囲で加えることができる。本発明の芳香族ポリカーボネート樹脂組成物を上記添加剤を混合するには、任意の方法で行うことができる。例えばタンブラー、Ｖ型ブレンダー、ナウターミキサー、バンバリーミキサー、混練ロール、押出機などで混合する方法が適宜用いられる。この芳香族ポリカーボネート樹脂組成物は、例えば射出成形法、圧縮成形法、押出成形法、溶液キャスティング法など任意の方法により成形される。
【００５９】
本発明の芳香族ポリカーボネート樹脂組成物は、成形性および熱安定性に優れているので種々の成形品として利用することができる。殊に光学ディスク、光学レンズ、液晶パネル、光カード、シート、フィルム、光ファイバー、コネクター、蒸着プラスチック反射鏡、ディスプレーなどの光学部品の構造材料または機能材料用途に適した光学用成形品として有利に使用することができる。これらのうち、光ディスク基板として特に有利に使用することができる。
【００６０】
かかる光ディスク基板としては、コンパクトディスク（ＣＤ）、ＣＤ−Ｒ、ＭＯ、ＭＤ−ＭＯ等や、更にはデジタルバーサタイルディスク（ＤＶＤ−ＲＯＭ、ＤＶＤ−ｖｉｄｅｏ、ＤＶＤ−Ｒ、ＤＶＤ−ＲＡＭ等）で代表される高密度光ディスクが挙げられる。
【００６１】
【実施例】
以下に実施例を挙げて本発明をさらに説明する。なお実施例中の部は重量部であり、％は重量％である。なお、評価は下記の方法によった。
（１）比粘度
ポリマー０.７ｇを１００ｍｌの塩化メチレンに溶解し２０℃の温度で測定した。
（２）ガラス転移点（Ｔｇ）
デュポン社製９１０型ＤＳＣにより測定した。
（３）流動性（ＭＦＲ）
ＪＩＳ Ｋ−７２１０に準拠して、東洋精機製セミオートメルトインデクサーを用いて、２８０℃、荷重２.１６ｋｇで１０分間に流出したポリマー量（ｇ）で示した。
【００６２】
（４）オリゴマー含量
東ソー製ＧＰＣカラムＴＳＫｇｅｌＧ２０００ＨＸＬとＴＳＫｇｅｌＧ３０００ＨＸＬを用い、溶離液としてクロロホルムを流量０.７ｍｌ／分で流しながら試料５０ｍｇをクロロホルム５ｍｌに溶解した溶液を２０μｌ注入する方法で求めたＧＰＣチャートのリテンションタイムが２３分以降のオリゴマー成分のピーク面積の全ピーク面積に対する割合を％で示した。
【００６３】
（５）吸水率
ＡＳＴＭ Ｄ−０５７０によって測定した。
（６）塩化メチレン未溶解粒子
該芳香族ポリカーボネート樹脂２０ｇを塩化メチレン１Ｌに溶解した溶液をハイアックロイコ社製液体パーティクルカウンターモデル４１００を用いたレーザーセンサー法にて散乱光をラテックス粒子の散乱光に換算する方法で求めた。
【００６４】
（７）光線透過率
ＡＳＴＭ Ｄ−１００３に準拠して日立製作所（株）製分光光度計Ｕ−３４００を用いて測定した。
（８）光弾性定数
理研計器（株）製の光弾性測定装置ＰＡ−１５０により測定した。
（９）リターデーション値
名機製作所（株）製Ｍ３５Ｂ−Ｄ−ＤＭを用いて、直径１２０ｍｍ、厚さ１.２ｍｍのディスクを加熱筒温度３３０℃、金型温度８５℃、冷却時間５秒にて成形し、オ−ク製ＡＤＲ２００Ｂ自動複屈折測定装置を用い、ディスクの中心から半径３０ｍｍ部分について測定した。
【００６５】
（１０）熱安定性
試料のペレットを１２０℃で５時間乾燥した後、射出成形機（住友重機（株）製ＳＧ−１５０）を用い、シリンダー温度３４０℃で１０分間滞留させたものとさせないものの試験片（縦７０ｍｍ、横５０ｍｍ,厚み２ｍｍ）をそれぞれ作成し、その比粘度の変化（△η_sp）および色相の変化（△Ｅ）を測定した。色相の変化は、ＪＩＳ Ｚ ８７３０に従い、日本電色（株）モデルＺ−１００１ＤＰを用い、それぞれのＬ、ａ、ｂ値を測定して、次式により算出した。
【００６６】
【数１】

（Ｌ₁、ａ₁およびｂ₁は、滞留させない組成物の値、Ｌ₂、ａ₂およびｂ₂は１０分間滞留させた組成物の値）
【００６７】
（１１）成形操作性
名機製作所（株）製Ｍ３５Ｂ−Ｄ−ＤＭを用いて１２０ｍｍφ、１.２ｍｍ厚みのディスク基板を１００枚射出成形する際に、ディスク基板内に不良個所（ボイド、クラウド、コールド、シルバー等によって記録ミスの原因となる不良箇所）が発生しないような最低シリンダー温度を測定した。この温度が低い方が、同温度では溶融粘度が低く成形温度巾が広いメリットがある。
【００６８】
（１２）引張り試験法
ＡＳＴＭ Ｄ−６３８に準拠して、東洋ボールドウィン社製ＵＴＭ２.５Ｔを用いて測定した。
【００６９】
実施例１
［Ａ］ ポリマーＡの共重合体の合成；
温度計、撹拌機、還流冷却器付き反応器にイオン交換水９２９.２部、４８％水酸化ナトリウム水溶液６１.３部を入れ、１,１−ビス（４−ヒドロキシフェニル）−３,３,５−トリメチルシクロヘキサン（成分ａ−１：以下“ビスフェノールＴＭＣ”と略称することがある）３９部、４,４’−（ｍ−フェニレンジイソプロピリデン）ジフェノール（成分ａ−２：以下“ビスフェノールＭ”と略称することがある）４３.６部およびハイドロサルファイト０.１７部を溶解した後、ｐ−ｔｅｒｔ−ブチルフェノール１.５１部と塩化メチレン６３７.９部を加えトリエチルアミン０.０９部を添加した後撹拌下１５〜２５℃でホスゲン３２.４部を４０分を要して吹き込んだ。ホスゲン吹き込み終了後、４８％水酸化ナトリウム水溶液１５.６部を加え、２８〜３３℃で１時間撹拌して反応を終了した。反応終了後、生成物を塩化メチレンで希釈して水洗したのち塩酸酸性にして水洗し、水相の導電率がイオン交換水と殆ど同じになったところで、軸受け部に異物取り出し口を有する隔離室を設けたニーダーにて塩化メチレンを蒸発して、ビスフェノールＴＭＣとビスフェノールＭの比がモル比で５０：５０の比粘度が０.２７１である無色のポリマー８６.４部を得た（収率９７％）。
【００７０】
［Ｂ］ ビスフェノールＡからのポリカーボネート単独重合体（ポリマーＢ）の合成；
温度計、攪拌機及び還流冷却器付き反応器にイオン交換水１１０５７.０部、４８％水酸化ナトリウム水溶液１５５９.９部を仕込み、これにビスフェノールＡ２１３３.９部及びハイドロサルファイト２.１２部を溶解した後、塩化メチレン６４４５.３部を加え、攪拌下１５〜２０℃でホスゲン１００５.６部を６０分要して吹込んだ。ホスゲン吹込み終了後ｐ−ｔｅｒｔ−ブチルフェノール９２.３部及び４８％水酸化ナトリウム水溶液８２９.９部を加え、撹拌して乳化させた後トリエチルアミン０.０９部を加え、２８〜３３℃で１時間攪拌して反応を終了した。反応終了後生成物溶液を多孔板付遠心抽出機［（株）日立製作所製ウルトレックスＥＰ−０２］にてイオン交換水流量１,０００ｍｌ／分、反応生成物溶液流量１,５００ｍｌ／分、回転数３,５００ｒｐｍの条件で遠心分離した後、塩化メチレン相を塩酸酸性にし、更に同様の条件で遠心分離操作を繰返し、水相の導電率がイオン交換水と殆ど同じになったところで、軸受部に異物取出口を有する隔離室を設けたニーダーにより塩化メチレンを蒸発して、比粘度が０.２６９である粉粒状の無色のポリカーボネート樹脂２,４００部（収率９２％）を得た。
［Ｃ］ 樹脂組成物の調整；
【００７１】
［Ａ］で合成したポリマーＡの共重合体溶液と［Ｂ］で合成したビスフェノールＡの単独重合体（ポリマーＢ）溶液とを溶液中のポリマー重量比（ポリマーＡ：ポリマーＢ）が９５：５となるようにそれぞれ攪拌機付容器に投入した後、攪拌して混合した。混合後、目開き０.３μｍのフィルターを通過させた後、軸受部に異物取出口を有する隔離室を設けたニーダーにこの混合溶液を投入して塩化メチレンを蒸発することにより該ポリカーボネート樹脂粉粒体を得た。
【００７２】
このポリカーボネート樹脂粉粒体にジステアリルペンタエリスリトールジホスファイトを０.００３％、トリエチルホスフェートを０.００５％、ステアリン酸モノグリセリドを０.０４５％加えて、ベント付きφ３０ｍｍ二軸押出機を用いて、ペレット化した後、名機製作所（株）製Ｍ３５Ｂ−Ｄ−ＤＭを用いて１２０ｍｍφ、１.２ｍｍ厚みのディスク基板に射出成形した。このものの塩化メチレン未溶解粒子は０.５μｍ以上が１５,０００個／ｇ、１μｍ以上が１９０個／ｇであった。結果を表１に示す。
【００７３】
実施例２
［Ａ］で合成したポリマーＡの共重合体溶液と［Ｂ］で合成したビスフェノールＡの単独重合体（ポリマーＢ）溶液とを溶液中のポリマーＡ：ポリマーＢの重量比が９０：１０となるようにそれぞれ攪拌機付容器に投入した以外は実施例１と同様の操作をおこなった。結果を表１に示す。
【００７４】
実施例３
［Ａ］で合成した成分Ａの共重合体溶液と［Ｂ］で合成したビスフェノールＡの単独重合体溶液とを溶液中のポリマーＡ：ポリマーＢの重量比が６０：４０となるようにそれぞれ攪拌機付容器に投入した以外は実施例１と同様の操作をおこなった。結果を表１に示す。
【００７５】
実施例４
成分Ａについては実施例１と同様の操作をおこなった。ポリマーＢの合成方法として溶融法を使用した。すなわち、攪拌機及び蒸留塔を備えた反応器に２,２−ビス（４−ヒドロキシフェニル）プロパン５０.２部（０.２２モル）、ジフェニルカーボネート（バイエル社製）４９.２部（０.２３モル）及び触媒として水酸化ナトリウム０.０００００５部とテトラメチルアンモニウムヒドロキシド０.００１６部を仕込み、窒素置換した。この混合物を２００℃まで加熱して攪拌しながら溶解させた。次いで、減圧度を３０Ｔｏｒｒとして加熱しながら１時間で大半のフェノールを留去し、更に２７０℃まで温度を上げ、減圧度を１Ｔｏｒｒとして２時間重合反応を行ったところで、末端停止剤として２−メトキシカルボニルフェニルフェニルカーボネート２.３部を添加した。その後２７０℃、１Ｔｏｒｒ以下で５分間末端封鎖反応を行った。次に溶融状態のままで、触媒中和剤としてドデシルベンゼンスルホン酸テトラブチルホスホニウム塩を０.００２３部（４×１０-5モル／ビスフェノール１モル）添加して２７０℃、１０Ｔｏｒｒ以下で１０分間反応を継続し、比粘度が０.２７１のポリマーを得た。このポリマーをギアポンプでエクストルーダーに送った。エクストルーダー途中において、あらかじめ溶融状態にしておいたポリマーＡ：ポリマーＢとを重量比で９０：１０となるように併設のサイドフィーダーより添加混合した。さらにトリスノニルフェニルホスファイトを０.００３重量％、トリメチルホスフェートを０.００５重量％、グリセリンモノステアレートを０.０４５重量％加え、ポリカーボネートペレットを得た。
【００７６】
比較例１
実施例１において、［Ａ］で合成した成分Ａの共重合体溶液のみを、目開き０.３μｍのフィルターを通過させた後、軸受部に異物取出口を有する隔離室を設けたニーダーにこの混合溶液を投入して塩化メチレンを蒸発することにより該ポリカーボネート樹脂粉粒体を得た以外は実施例１と同様の操作をおこなった。結果を表１に示す。
【００７７】
比較例２
実施例１において、［Ｂ］で合成したビスフェノールＡの単独重合体（ポリマーＢ）溶液のみを、目開き０.３μｍのフィルターを通過させた後、軸受部に異物取出口を有する隔離室を設けたニーダーにこの混合溶液を投入して塩化メチレンを蒸発することにより該ポリカーボネート樹脂粉粒体を得た以外は実施例１と同様の操作をおこなった。結果を表１に示す。
【００７８】
比較例３
実施例１において、［Ａ］で合成した共重合体（ポリマーＡ）溶液と［Ｂ］で合成したビスフェノールＡの単独重合体（ポリマーＢ）溶液とを溶液中のポリマーＡ：ポリマーＢとの重量比が３０：７０となるようにそれぞれ攪拌機付容器に投入した以外は実施例１と同様の操作をおこなった。結果を表１に示す。
【００７９】
【表１】

【００８０】
実施例５
［Ａ］ 成分ａ−１と成分ａ−２からの共重合体（ポリマーＡ）の合成；
温度計、攪拌機、還流冷却器付き反応器にイオン交換水９２９.２部、４８％水酸化ナトリウム水溶液６１.３部を入れ、１,１−ビス（４−ヒドロキシフェニル）−３,３,５−トリメチルシクロヘキサン（“ビスフェノールＴＭＣ”）４３.３部、２,２−ビス(３−メチル−４−ヒドロキシフェニル)プロパン（以下“ビスフェノールＣ”と略称することがある）２９.５部およびハイドロサルファイト０.１７部を溶解した後、ｐ−ｔｅｒｔ−ブチルフェノール１.５１部と塩化メチレン６３７.９部を加えトリエチルアミン０.０９部を添加した後攪拌下１５〜２５℃でホスゲン３２.４部を４０分を要して吹き込んだ。ホスゲン吹き込み終了後、４８％水酸化ナトリウム水溶液１５.６部を加え、２８〜３３℃で１時間攪拌して反応を終了した。反応終了後、生成物を塩化メチレンで希釈して水洗したのち塩酸酸性にして水洗し、水相の導電率がイオン交換水と殆ど同じになったところで、軸受け部に異物取り出し口を有する隔離室を設けたニーダーにて塩化メチレンを蒸発して、ビスフェノールＴＭＣとビスフェノールＣの比がモル比で５５：４５の比粘度が０.２７６である無色のポリマー７９.0部を得た（収率９７％）。
【００８１】
［Ｂ］ ビスフェノールＡからのポリカーボネート単独重合体（ポリマーＢ）の合成；
温度計、攪拌機及び還流冷却器付き反応器にイオン交換水１１０５７.０部、４８％水酸化ナトリウム水溶液１５５９.９部を仕込み、これにビスフェノールＡ２１３３.９部及びハイドロサルファイト２.１２部を溶解した後、塩化メチレン６４４５.３部を加え、攪拌下１５〜２０℃でホスゲン１００５.６部を６０分要して吹込んだ。ホスゲン吹込み終了後ｐ−ｔｅｒｔ−ブチルフェノール９２.３部及び４８％水酸化ナトリウム水溶液８２９.９部を加え、撹拌して乳化させた後トリエチルアミン０.０９部を加え、２８〜３３℃で１時間攪拌して反応を終了した。反応終了後生成物溶液を多孔板付遠心抽出機［（株）日立製作所製ウルトレックスＥＰ−０２］にてイオン交換水流量１,０００ｍｌ／分、反応生成物溶液流量１,５００ｍｌ／分、回転数３,５００ｒｐｍの条件で遠心分離した後、塩化メチレン相を塩酸酸性にし、更に同様の条件で遠心分離操作を繰返し、水相の導電率がイオン交換水と殆ど同じになったところで、軸受部に異物取出口を有する隔離室を設けたニーダーにより塩化メチレンを蒸発して、比粘度が０.２６９である粉粒状の無色のポリカーボネート樹脂２,４００部（収率９２％）を得た。
【００８２】
［Ｃ］樹脂組成物の調整；
［Ａ］で合成したポリマーＡの共重合体溶液と［Ｂ］で合成したビスフェノールＡの単独重合体（ポリマーＢ）溶液とを溶液中のポリマー重量比（ポリマーＡ：ポリマーＢ）が９５：５となるようにそれぞれ攪拌機付容器に投入した後、攪拌して混合した。混合後、目開き０.３μｍのフィルターを通過させた後、軸受部に異物取出口を有する隔離室を設けたニーダーにこの混合溶液を投入して塩化メチレンを蒸発することにより該ポリカーボネート樹脂粉粒体を得た。
【００８３】
このポリカーボネート樹脂粉粒体にジステアリルペンタエリスリトールジホスファイトを０.００３％、トリエチルホスフェートを０.００５％、ステアリン酸モノグリセリドを０.０４５％加えて、ベント付きφ３０ｍｍ二軸押出機を用いて、ペレット化した後、名機製作所（株）製Ｍ３５Ｂ−Ｄ−ＤＭを用いて１２０ｍｍφ、１.２ｍｍ厚みのディスク基板に射出成形した。このものの塩化メチレン未溶解粒子は０.５μｍ以上が１５,０００個／ｇ、１μｍ以上が１９０個／ｇであった。結果を表２に示す。
【００８４】
実施例６
前記実施例５の［Ａ］で合成したポリマーＡの共重合体溶液と［Ｂ］で合成したビスフェノールＡの単独重合体（ポリマーＢ）溶液とを溶液中のポリマーＡ：ポリマーＢの重量比が９０：１０となるようにそれぞれ攪拌機付容器に投入した以外は実施例５と同様の操作をおこなった。結果を表２に示す。
【００８５】
実施例７
前記実施例５の［Ａ］で合成したポリマーＡの共重合体溶液と［Ｂ］で合成したビスフェノールＡの単独重合体溶液（ポリマーＢ）とを溶液中のポリマーＡ：ポリマーＢの重量比が６５：３５なるようにそれぞれ攪拌機付容器に投入した以外は実施例５と同様の操作をおこなった。結果を表２に示す。
【００８６】
実施例８
成分Ａについては実施例１（Ａ）と同様の操作をおこなった。成分Ｂの合成方法として溶融法を使用した。すなわち、攪拌機及び蒸留塔を備えた反応器に２,２−ビス（４−ヒドロキシフェニル）プロパン５０.２部（０.２２モル）、ジフェニルカーボネート（バイエル社製）４９.２部（０.２３モル）及び触媒として水酸化ナトリウム０.０００００５部とテトラメチルアンモニウムヒドロキシド０.００１６部を仕込み、窒素置換した。この混合物を２００℃まで加熱して攪拌しながら溶解させた。次いで、減圧度を３０Ｔｏｒｒとして加熱しながら１時間で大半のフェノールを留去し、更に２７０℃まで温度を上げ、減圧度を１Ｔｏｒｒとして２時間重合反応を行ったところで、末端停止剤として２−メトキシカルボニルフェニルフェニルカーボネート２.３部を添加した。その後２７０℃、１Ｔｏｒｒ以下で５分間末端封鎖反応を行った。次に溶融状態のままで、触媒中和剤としてドデシルベンゼンスルホン酸テトラブチルホスホニウム塩を０.００２３部（４×１０^-5モル／ビスフェノール１モル）添加して２７０℃、１０Ｔｏｒｒ以下で１０分間反応を継続し、比粘度が０.２７１のポリマーを得た。このポリマーをギアポンプでエクストルーダーに送った。エクストルーダー途中において、あらかじめ溶融状態にしておいた成分Ａを成分Ａ／成分Ｂ＝９０／１０となるように併設のサイドフィーダーより添加混合した。さらにトリスノニルフェニルホスファイトを０.００３重量％、トリメチルホスフェートを０.００５重量％、グリセリンモノステアレートを０.０４５重量％加え、ポリカーボネートペレットを得た。
【００８７】
比較例４
実施例５において、［Ａ］で合成した成分ａ−１と成分ａ−２の共重合体（ポリマーＡ）溶液のみを、目開き０.３μｍのフィルターを通過させた後、軸受部に異物取出口を有する隔離室を設けたニーダーにこの混合溶液を投入して塩化メチレンを蒸発することにより該ポリカーボネート樹脂粉粒体を得た以外は実施例１と同様の操作をおこなった。結果を表２に示す。
【００８８】
比較例５
実施例５の［Ａ］で合成した成分ａ−１と成分ａ−２の共重合体（ポリマーＡ）溶液と［Ｂ］で合成したビスフェノールＡの単独重合体（ポリマーＢ）溶液とを溶液中のポリマーＡ：ポリマーＢの重量比が３０：７０となるようにそれぞれ攪拌機付容器に投入した以外は実施例５と同様の操作をおこなった。結果を表２に示す。
【００８９】
【表２】

【００９０】
【発明の効果】
本発明によれば、１,１−ビス（４−ヒドロキシフェニル）−３,３,５−トリメチルシクロヘキサンと４,４’−（ｍ−フェニレンジイソプロピリデン）ジフェノールおよび／または２,２−ビス（３−メチル−４−ヒドロキシフェニル）プロパンと二価フェノール成分とする芳香族ポリカーボネート共重合において、成形不良や成形条件の大幅な制限、また熱安定性、機械特性を改善することによって、本発明の芳香族ポリカーボネート樹脂組成物は、吸水性、光弾性定数、複屈折、成形性および熱安定性に優れているので種々の成形品として利用することができる。殊に光学ディスク、光学レンズ、液晶パネル、光カード、シート、フィルム、光ファイバー、コネクター、蒸着プラスチック反射鏡、ディスプレーなどの光学部品の構造材料または機能材料用途に適した光学用成形品として有利に使用することができる。これらのうち、光ディスク基板として特に有利に使用することができ、その奏する工業的効果は格別なものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an aromatic polycarbonate resin composition. More particularly, the present invention relates to an aromatic polycarbonate resin composition having improved moldability, mechanical properties and thermal stability, and a molded product therefrom having a low retardation value.
[0002]
[Prior art]
Conventionally, polycarbonate resins obtained by reacting 2,2-bis (4-hydroxyphenyl) propane with a carbonate precursor material have excellent transparency, heat resistance, mechanical properties, and dimensional stability. Widely used in many fields. Since it is particularly excellent in transparency, it is often used as an optical material. However, such a polycarbonate resin has a drawback that the photoelastic constant is large due to the optical anisotropy of the benzene ring, and thus the retardation value of the molded product is large, and this improvement is required. There is also a need for a resin that is more excellent in melt fluidity and better in thermal stability.
[0003]
On the other hand, JP-A-2-88634 describes a dihydroxydiphenylalkane having a specific structure and a novel aromatic polycarbonate therefrom. A typical example disclosed in this publication is an aromatic polycarbonate using 1,2-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane in an amount of 100 to 2 mol% of the total dihydric phenol component. is there. Specifically, a homo- or co-polycarbonate using 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane in a proportion of 100 to 30 mol% is shown, As a copolymerization component, 30, 50, 65 or 70 mol% of bisphenol A is used. The above publication discloses that the obtained aromatic polycarbonate is used in conventional polycarbonate applications from bisphenol A, for example, in the fields of electric field, coating and transparent glass, and is excellent in high heat resistance. Yes. However, such aromatic polycarbonates have poor melt fluidity and it is difficult to obtain good molded products. Therefore, as an example of improving the fluidity, as shown in JP-A-8-293128, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and 4,4 It is conceivable to use a copolymer polycarbonate containing '-(m-phenylenediisopropylidene) diphenol as a dihydric phenol component. However, with this copolymer, although melt flowability is improved, molding defects are likely to occur due to the severe temperature dependence of the extensional viscosity change in the viscoelastic region. In addition, there is a tendency that the thermal stability and mechanical properties do not exhibit satisfactory values.
[0004]
[Problems to be solved by the invention]
The object of the present invention is (1) 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and (2) 4,4 ′-(m-phenylenediisopropylidene) diphenol and / or Or, in copolymerized polycarbonate containing 2,2-bis (3-methyl-4-hydroxyphenyl) propane as a dihydric phenol component, it improves molding defects, greatly restricts molding conditions, and improves thermal stability and mechanical properties. Thus, an object of the present invention is to provide an aromatic polycarbonate resin composition and a molded article made thereof which are well-balanced with respect to flow characteristics and optical characteristics.
[0005]
Another object of the present invention is to provide an aromatic polycarbonate resin composition having various excellent properties as a material for optical molded articles, particularly optical disk substrates.
[0006]
[Means for Solving the Problems]
According to the studies by the present inventors, the object of the present invention is that (A) the dihydric phenol component is (a-1) 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane. (Component a-1) and (a-2) 4,4 ′-(m-phenylenediisopropylidene) diphenol and / or 2,2-bis (3-methyl-4-hydroxyphenyl) propane (Component a- 2) Yo Rina And an aromatic polycarbonate copolymer (polymer A) composed of a dihydric phenol component in which the ratio of component a-1: component a-2 is 99: 1 to 20:80 in molar ratio;
(B) An aromatic polycarbonate (polymer B) in which the dihydric phenol component is composed of dihydric phenol components (component b) other than the components a-1 and a-2. Rina The ratio of polymer A: polymer B is 99.9: 0.1-40: 60 by weight, and is achieved by the aromatic polycarbonate resin composition.
[0007]
Hereinafter, the present invention will be described in more detail.
The resin composition of the present invention is substantially formed from the polymers A and B, and the ratio of the polymer A to the polymer B is in the range of 99.9: 0.1 to 40:60 by weight. The range of 5: 0.5 to 75:25 is preferred, and the range of 99: 1 to 90:10 is more preferred. This ratio is most preferably in the range of 96: 4 to 90:10. When the ratio of the polymer B exceeds 60%, it becomes difficult to maintain the characteristics of the low photoelastic constant and the low water absorption that the copolymer of the polymer A has.
[0008]
In the aromatic polycarbonate resin composition of the present invention, the ratio of the component a-1 to the component a-2 in the dihydric phenol component in the polymer A is in the range of 99: 1 to 20:80 by molar ratio, and 80: The range of 20-20: 80 is preferable, and the range of 80: 20-30: 70 is more preferable. When the proportion of component a-1 is more than 99 mol% and the proportion of component a-2 is less than 1 mol%, the resulting copolymer has poor melt fluidity, resulting in poor molding and optically good molding. It becomes difficult to obtain goods. Moreover, when the ratio of component a-1 is less than 20 mol% and the ratio of component a-2 is more than 80 mol%, the photoelastic constant of the obtained copolymer increases and the glass transition temperature tends to decrease. Therefore, it is not preferable. Here, as the dihydric phenol component of component a-2, 4,4 ′-(m-phenylenediisopropylidene) diphenol or 2,2-bis (3-methyl-4-hydroxyphenyl) propane or a mixture thereof However, 4,4 ′-(m-phenylenediisopropylidene) diphenol is preferred.
[0009]
Representative examples of the dihydric phenol used for the polymer B in the aromatic polycarbonate resin composition of the present invention include hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-dimethyl) phenyl} methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2- Bis (4-hydroxyphenyl) propane (commonly called bisphenol A), 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(3,5-dibromo-4- Hydroxy) phenyl} propane, 2,2-bis {(3-isopropyl-4-hydroxy) phenyl} propane, 2,2-bis {(4-hydroxy) -3-phenyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl)- 3,3-dimethylbutane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4- Methylpentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9- Bis {(4-hydroxy-3-methyl) phenyl} fluorene, 4,4 '-(o-phenylenediisopropylidene) diphenol, 4,4'-( -Phenylenediisopropylidene) diphenol, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4 ' -Dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ester and the like can be mentioned, and these can be used alone or in admixture of two or more.
[0010]
Among them, as polymer B, bisphenol A, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane and 2,2-bis (4-hydroxyphenyl) -3 A homopolymer or copolymer obtained from at least one dihydric phenol selected from the group consisting of 1,3-dimethylbutane is preferred, and a homopolymer from bisphenol A is most preferably used.
[0011]
The aromatic polycarbonate copolymer as the polymer A and the aromatic polycarbonate resin as the polymer B of the present invention are each a reaction means known per se for producing a normal aromatic polycarbonate resin, for example, dihydric phenol component with phosgene or carbonic acid. Produced by a method of reacting a carbonate precursor such as a diester. Next, basic means for these manufacturing methods will be briefly described.
[0012]
As the carbonate precursor, carbonyl halide, carbonate ester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.
[0013]
In producing a polycarbonate resin by reacting the dihydric phenol and the carbonate precursor by a solution method or a melting method, a catalyst, a terminal terminator, a dihydric phenol antioxidant, etc. are used as necessary. Also good. The polycarbonate resin may be a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, or may be a polyester carbonate resin copolymerized with an aromatic or aliphatic difunctional carboxylic acid, Moreover, the mixture which mixed 2 or more types of the obtained polycarbonate resin may be sufficient.
[0014]
The reaction by the solution method is usually a reaction between a dihydric phenol and phosgene, and is reacted in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. 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 such as triethylamine, tetra-n-butylammonium bromide or tetra-n-butylphosphonium bromide, a quaternary ammonium compound or a quaternary phosphonium compound may be used. it can. At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9 or more.
[0015]
The reaction by the melting method is usually a transesterification reaction between a dihydric phenol and a carbonate ester. The dihydric phenol and the carbonate ester are mixed with heating in the presence of an inert gas, and the resulting alcohol or phenol is distilled. It is done by the method of making it come out. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 350 ° C. In the latter stage of the reaction, the system is evacuated to about 10 to 0.1 Torr to facilitate the distillation of the alcohol or phenol produced. The reaction time is usually about 1 to 4 hours.
[0016]
Examples of the carbonate ester include esters such as an optionally substituted aryl group having 6 to 10 carbon atoms, an aralkyl group, or an alkyl group having 1 to 4 carbon atoms. Specific examples include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Is preferred.
[0017]
In addition, a polymerization catalyst can be used to increase the polymerization rate in the melting method. Examples of such a polymerization catalyst include alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium salt of dihydric phenol, potassium salt, water Alkaline earth metal compounds such as calcium oxide, barium hydroxide and magnesium hydroxide, nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine and triethylamine, alkali metal and alkaline earth metal alkoxides , Organic acid salts of alkali metals and alkaline earth metals, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organotin compounds, lead compounds, osmium compounds, antimony compounds Manga Compounds, titanium compounds, usually the esterification reaction, such as zirconium compounds, there can be used a catalyst used in the transesterification reaction. A catalyst may be used independently and may be used in combination of 2 or more types. The amount of these polymerization catalysts used is 1 × 10 to 1 mol of dihydric phenol as a raw material. ^-8 ~ 1x10 ^-3 Equivalent weight, preferably 1 × 10 ^-7 ~ 1x10 ^-3 Equivalent, more preferably 1 × 10 ^-6 ~ 5x10 ^-Four It is selected in the range of equivalents.
[0018]
As the aromatic polycarbonate resin (polymer A and polymer B), monofunctional phenols that are usually used as a terminal terminator can be used in the polymerization reaction. Especially in the case of reactions using phosgene as a carbonate precursor, monofunctional phenols are generally used as end-capping agents for molecular weight control, and the polymers obtained are based on groups based on monofunctional phenols. Since it is blocked by, it is superior in thermal stability compared to other cases.
[0019]
Such monofunctional phenols only need to be used as a terminal terminator for aromatic polycarbonate resins, and are generally phenols or lower alkyl-substituted phenols, and monofunctional phenols represented by the following general formula: Can show.
[0020]
[Chemical 1]

[Wherein, A represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 9 carbon atoms, preferably 1 to 8 carbon atoms, and r represents an integer of 1 to 5, preferably 1 to 3. ]
[0021]
Specific examples of the monofunctional phenols include phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.
[0022]
Further, as other monofunctional phenols, phenols or benzoic acid chlorides having a long chain alkyl group or an aliphatic polyester group as a substituent, or long chain alkyl carboxylic acid chlorides can be used, When these are used to block the ends of the aromatic polycarbonate copolymers, they not only function as end terminators or molecular weight regulators, but also improve the melt fluidity of the resin and facilitate molding processes. The physical properties as a substrate are also improved. In particular, it has the effect of lowering the water absorption rate of the resin and is preferably used. These are represented by the following general formulas [Ia] to [Ih].
[0023]
[Chemical formula 2]

[In each formula, X is —R—O—, —R—CO—O— or —R—O—CO—, wherein R is a single bond or a carbon number of 1 to 10, preferably 1 to 5. A divalent aliphatic hydrocarbon group, T represents a single bond or a bond similar to the above X, and n represents an integer of 10 to 50.
[0024]
Q represents a halogen atom or a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, p represents an integer of 0 to 4, Y represents 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms. 5 represents a divalent aliphatic hydrocarbon group, W ¹ Is a hydrogen atom, -CO-R ¹³ , -CO-O-R ¹⁴ Or R ¹⁵ Where R ¹³ , R ¹⁴ And R ¹⁵ Are each a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 8 carbon atoms, preferably 5 to 6 carbon atoms, or 6 to 6 carbon atoms. 15 represents a monovalent aromatic hydrocarbon group, preferably 6-12.
[0025]
l represents an integer of 4 to 20, preferably 5 to 10, m represents an integer of 1 to 100, preferably 3 to 60, particularly preferably 4 to 50, Z represents a single bond or a carbon number of 1 to 10, Preferably it represents a divalent aliphatic hydrocarbon group of 1 to 5, W ² Is a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 8 carbon atoms, preferably 5 to 6 carbon atoms, or 6 carbon atoms. -15, preferably 6-12 monovalent aromatic hydrocarbon groups. ]
[0026]
Of these, the substituted phenols of [Ia] and [Ib] are preferable. As the substituted phenols of [Ia], those having n of 10 to 30, particularly 10 to 26 are preferable. Specific examples thereof include decylphenol, dodecylphenol, tetodecylphenol, hexadecylphenol, and octadecyl. Phenol, eicosylphenol, docosylphenol and triacontylphenol can be mentioned.
[0027]
Further, as the substituted phenols of [Ib], compounds in which X is —R—CO—O— and R is a single bond are suitable, and those in which n is 10 to 30, particularly 10 to 26. Specific examples thereof include, for example, decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate.
[0028]
In the substituted phenols or substituted benzoic acid chlorides represented by the above general formulas [Ia] to [Ig], the position of the substituent is generally preferably the p-position or the o-position, and a mixture of both is preferable.
[0029]
The monofunctional phenols are desirably introduced into at least 5 mol%, preferably at least 10 mol%, of the total terminal of the obtained aromatic polycarbonate resin composition. Or you may use it in mixture of 2 or more types.
[0030]
In addition, in the aromatic polycarbonate copolymer as the polymer A of the present invention, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane as the component a-1 is an all dihydric phenol component. If it is 80 mol% or more, the fluidity of the resin may be lowered, and therefore, the substituted phenols or substituted benzoic acid chlorides represented by the general formulas [Ia] to [Ig] are terminated. It is preferable to use it as an agent.
[0031]
In the preparation of the composition of the present invention, the mixing of the polymer A and the polymer B may be in the stage of a molded product such as a polymer solution, a granular material, or a pellet, but is not particularly restricted. Regarding the mixing method, for example, a container with a stirrer is mainly considered at the stage of the polymer solution, and at the stage of a molded product such as a granular material or a pellet, for example, a tumbler, V-type blender, Nauta mixer, Banbury, etc. A method of mixing with a mixer, a kneading roll, an extruder or the like is used. In any case, any method can be used, and there is no particular restriction, but after mixing in a polymer solution state, it is allowed to pass through a filter with an arbitrary opening because of the simplicity of the removal method for contamination by foreign matters during the mixing operation. preferable.
[0032]
In the aromatic polycarbonate resin composition of the present invention, 0.7 g of the polymer is dissolved in 100 ml of methylene chloride, and the specific viscosity measured at 20 ° C. is preferably 0.2 to 0.5, preferably 0.25 to 0.5. The range of 4 is more preferable. When the specific viscosity is less than 0.2, the molded product becomes brittle. When the specific viscosity is higher than 0.5, the melt fluidity is poor and molding failure occurs, making it difficult to obtain an optically good molded product.
[0033]
The aromatic polycarbonate resin composition of the present invention has a water absorption measured by ASTM D-0570 of 0.3% by weight or less, preferably 0.25% by weight or less, and 0.20% by weight or less. It is more preferable. When the water absorption exceeds 0.3% by weight, the optical disk in which the metal film is formed on the surface of the optical disk substrate on which the aromatic polycarbonate resin composition of the present invention is suitably used is likely to warp due to water absorption, resulting in a tracking error. It is not preferable because it is easy to cause. A particularly preferred water absorption is 0.18% by weight or less.
[0034]
The aromatic polycarbonate resin composition of the present invention preferably has an oligomer content of 10% or less, more preferably 7% or less, and particularly preferably 5% or less. The value of this oligomer content is a value measured using the following method and column. That is, each of the TSKgel G2000HXL and G3000HXL columns manufactured by Tosoh Corporation was connected in series, and chloroform was used as an eluent. After stabilizing at a flow rate of 0.7 ml / min, a chloroform solution of the aromatic polycarbonate resin composition was prepared. The ratio of the sum of the oligomer peak areas with a retention time of the GPC chart measured by the injection method of 23 minutes or later to the total peak area is the oligomer content, and this value is preferably 10% or less, preferably 7% or less. It is more preferable. If the oligomer content exceeds 7%, especially 10%, the mold surface may be contaminated during molding, which is undesirable. The contamination tends to become more prominent as the oligomer content increases. On the other hand, the oligomer is produced in the process of producing the aromatic polycarbonate resin composition, and cannot be completely zero (0).
[0035]
The oligomer should just be below the above-mentioned content, and as long as the value is satisfied, it may be contained in a small proportion. When the oligomer is present in a small content of 0.1% or more, more preferably 0.15% or more, the melt fluidity is improved as compared with the content of the oligomer. Therefore, the oligomer content is particularly preferably in the range of 0.15 to 4%.
[0036]
In order to control the oligomer content in the aromatic polycarbonate resin composition within the above range, it is necessary to complete the polymerization sufficiently so that a large amount of oligomer is not contained in the copolymer, and the catalyst and polymerization conditions It is required to properly select. If the oligomer content exceeds the above range, for example, a treatment for removing the oligomer by means of extraction or the like is adopted. In this extraction, a solution of the aromatic polycarbonate resin composition (for example, methylene chloride solution) is dropped into a poor solvent or non-solvent (for example, acetone or methanol) of the copolymer, or the composition is washed with a poor solvent or non-solvent. It can be carried out by means such as a method of immersing in a solvent and extracting an oligomer.
[0037]
Since the aromatic polycarbonate resin composition of the present invention is suitably used as an optical material, particularly as an optical disk substrate, it is desirable that there are no more than a certain amount of undissolved particles.
[0038]
That is, in the aromatic polycarbonate resin composition, a solution obtained by dissolving 20 g in 1 L of methylene chloride is converted into a scattered light of latex particles by a laser sensor method using a liquid particle counter model 4100 manufactured by Hiac Leuco. The number of undissolved particles having a diameter of 0.5 μm or more determined by the conversion method is preferably 25,000 or less per 1 g of the aromatic polycarbonate resin composition and 500 or less undissolved particles of 1 μm or more. If the number of undissolved particles of 0.5 μm or more exceeds 25,000 or the number of undissolved particles of 1 μm or more exceeds 500, the information pits written on the optical disk are adversely affected and the error rate increases, which is not preferable. More preferably, the number of undissolved particles of 0.5 μm or more is 20,000 or less, and the number of undissolved particles of 1 μm or more is 200 or less. Moreover, the undissolved particle | grains 10 micrometers or more should not exist substantially. Further, the number of undissolved particles of 5 μm or more is preferably 30 particles / g or less.
[0039]
In order to make the amount of the undissolved particles in the aromatic polycarbonate resin composition within the above range, means for preventing the undissolved particles from being mixed or removed in the polymerization process and the granulation process should be adopted.
[0040]
As such means, for example, the operation is performed in a clean room, or a granulating apparatus with a device for removing undissolved particles is used (specifically, an isolation chamber having a foreign matter outlet is provided in the bearing portion). Or a device having a structure in which the resin particles do not touch the sliding portion (for example, a spray dryer type granulator).
[0041]
In addition, as another means for removing undissolved particles, a method of filtering a resin solution with a filter having a small opening (0.5 to 1 μm) or melting a resin and then solidifying with a metal filter (10 to 40 μm) A method of removing particles is employed.
[0042]
The aromatic polycarbonate resin composition of the present invention has a photoelastic constant value of 60 × 10 6. ^-13 cm ² / Dyn or less, preferably 55 × 10 ^-13 cm ² Those below / dyn are advantageously used. When the value of the photoelastic constant is larger than the above value, it is not suitable as an optical material, particularly as an optical disk.
[0043]
The aromatic polycarbonate resin composition has a glass transition point of preferably 120 ° C. or higher, more preferably 130 ° C. or higher, and further preferably 145 ° C. or higher. When the glass transition point is lowered, the heat resistance as an optical material, particularly as a disk substrate is insufficient.
[0044]
In the aromatic polycarbonate resin composition of the present invention, when phosgene is used as a carbonate precursor and a chlorinated solvent such as methylene chloride is used as a solvent, not a little chlorine remains. If the chlorine content is high, the molding die is corroded, the thermal stability of the aromatic polycarbonate resin composition is lowered, and the metal film is corroded when used as an optical disk substrate. Absent. Therefore, it is recommended that the chlorine content is 10 ppm or less, preferably 7 ppm or less, particularly preferably 5 ppm or less. The chlorine content mentioned here means a value obtained by measuring an aromatic polycarbonate copolymer by a combustion method using an all organic halogen analyzer TOX10 manufactured by Mitsubishi Chemical.
[0045]
The aromatic polycarbonate resin composition of the present invention is excellent in fluidity in melt molding and has greatly improved limitations on molding conditions. Therefore, the width of the molding condition becomes wide, and the molding operation becomes easy. That is, the resin composition of the present invention has a fluidity (MFR value) at melting (280 ° C.) of 52 to 70 g / 10 min, preferably 53 to 67 g / 10 min, and has excellent flow characteristics. Also, when molding on a disk substrate, the cylinder temperature gradually decreases, and when it reaches a certain temperature, defective parts due to molding occur in the substrate, but the higher the minimum cylinder temperature at this time, the smaller the range of molding operation conditions and the molding Usability is reduced. The resin composition of the present invention has a merit that the minimum cylinder temperature is low, and therefore a wide range of molding operation conditions can be obtained. This minimum cylinder temperature is shown in the examples as a guide for molding operability. The resin composition of the present invention has a minimum cylinder temperature which is 10 ° C. or more lower than that of the polymer A alone, and 15 ° C. or less under suitable conditions.
[0046]
Furthermore, a molded article formed from the resin composition of the present invention, particularly an optical disk substrate, has excellent optical characteristic values. That is, the resin composition of the present invention has a photoelastic constant of 47 × 10 6. ^-13 ~ 60 × 10 ^-13 cm ² / Dyne, preferably 48 × 10 ^-13 ~ 59 × 10 ^-13 cm ² / Dyne, and the birefringence is 25 to 45 nm, preferably 27 to 42 nm, and has excellent characteristics for the purpose of an optical disk substrate.
[0047]
In the present invention, the aromatic polycarbonate resin composition contains at least one phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid and esters thereof in the copolymer. On the other hand, it can be blended at a ratio of 0.0001 to 0.05% by weight.
By blending this phosphorus compound, the thermal stability of the aromatic polycarbonate resin composition is improved, and a decrease in molecular weight and a deterioration in hue during molding are prevented.
[0048]
The phosphorus compound is at least one phosphorus compound selected from the group consisting of phosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid, and esters thereof, and preferably the following general formulas (1) to (4) At least one phosphorus compound selected from the group consisting of:
[0049]
[Chemical 3]

[0050]
Where R ¹ ~ R ¹² Are each independently a hydrogen atom, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, octadecyl, etc. And an alkyl group having 6 to 15 carbon atoms such as phenyl, tolyl and naphthyl, or an aralkyl group having 7 to 18 carbon atoms such as benzyl and phenethyl. When two alkyl groups are present in one compound, the two alkyl groups may be bonded to each other to form a ring.
[0051]
Examples of the phosphorus compound represented by the above formula (1) include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, and trioctyl phosphite. , Trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di -Tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol Tall diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite and the like can be mentioned. Examples of the phosphorus compound represented by the above formula (2) include Examples include tributyl phosphate, trimethyl phosphate, triphenyl phosphate, triethyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, and the like. As the phosphorus compound represented by the above formula (3), tetrakis (2, 2, 4-di-tert-butylphenyl) -4,4-diphenylenephosphonite, and the compounds represented by the above formula (4) include dimethyl benzenephosphonate and benzenephosphonic acid. Ethyl, etc. dipropyl benzene phosphonate is mentioned. Of these, distearyl pentaerythritol diphosphite, triethyl phosphate, and dimethyl benzenephosphonate are preferably used.
[0052]
The amount of the phosphorus compound is 0.0001 to 0.05% by weight, preferably 0.0005 to 0.02% by weight, and 0.001 to 0.01% by weight based on the aromatic polycarbonate resin composition. % Is particularly preferred. When the blending amount is less than 0.0001% by weight, it is difficult to obtain the above effect. When the blending amount exceeds 0.05% by weight, the thermal stability of the aromatic polycarbonate resin composition is adversely affected, and the hydrolysis resistance is also reduced. Since it falls, it is not preferable.
[0053]
In the aromatic polycarbonate resin composition of the present invention, an antioxidant generally known for the purpose of antioxidant can be added. Examples thereof include phenolic antioxidants, specifically, for example, triethylene glycol-bis (3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate), 1,6 -Hexanediol-bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), pentaerythritol-tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl) -4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydride) Cinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 3,9-bis {1 , 1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5,5) undecane, etc. Is mentioned. The range of the preferable addition amount of these antioxidants is 0.0001 to 0.05 weight% with respect to an aromatic polycarbonate resin composition.
[0054]
Furthermore, a higher fatty acid ester of a monohydric or polyhydric alcohol can be added to the aromatic polycarbonate resin composition of the present invention as necessary. By compounding the higher fatty acid ester of monohydric or polyhydric alcohol, the release property from the mold at the time of molding the aromatic polycarbonate resin composition is improved, and in the molding of the disk substrate, the mold release load is improved. The deformation of the disk substrate and the pit shift due to a poor mold release can be prevented. There is also an advantage that the melt fluidity of the aromatic polycarbonate resin composition is improved.
[0055]
The higher fatty acid ester is preferably a partial ester or a total ester of a monovalent or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms.
[0056]
Further, partial esters or total esters of such monohydric or polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, propylene glycol. Examples thereof include monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, 2-ethylhexyl stearate, among which stearic acid monoglyceride and pentaerythritol tetrastearate are preferably used. It is done.
[0057]
The blending amount of the alcohol and higher fatty acid ester is 0.01 to 2% by weight, preferably 0.015 to 0.5% by weight, and 0.02 to 0% with respect to the aromatic polycarbonate resin composition. More preferred is 2% by weight. If the blending amount is less than 0.01% by weight, the above effect cannot be obtained, and if it exceeds 2% by weight, the mold surface may become dirty.
[0058]
To the aromatic polycarbonate resin composition of the present invention, additives such as a light stabilizer, a colorant, an antistatic agent, and a lubricant can be added as long as transparency is not impaired. In order to mix the said additive with the aromatic polycarbonate resin composition of this invention, it can carry out by arbitrary methods. For example, a method of mixing with a tumbler, a V-type blender, a Nauter mixer, a Banbury mixer, a kneading roll, an extruder, or the like is appropriately used. This aromatic polycarbonate resin composition is molded by an arbitrary method such as an injection molding method, a compression molding method, an extrusion molding method, or a solution casting method.
[0059]
Since the aromatic polycarbonate resin composition of the present invention is excellent in moldability and thermal stability, it can be used as various molded articles. In particular, it is advantageously used as an optical molding suitable for structural or functional material applications of optical components such as optical discs, optical lenses, liquid crystal panels, optical cards, sheets, films, optical fibers, connectors, vapor-deposited plastic reflectors, and displays. can do. Among these, it can be used particularly advantageously as an optical disk substrate.
[0060]
Such optical disk substrates are typified by compact disks (CD), CD-R, MO, MD-MO, etc., and digital versatile disks (DVD-ROM, DVD-video, DVD-R, DVD-RAM, etc.). High density optical disc.
[0061]
【Example】
The following examples further illustrate the present invention. In addition, the part in an Example is a weight part and% is weight%. The evaluation was based on the following method.
(1) Specific viscosity
0.7 g of the polymer was dissolved in 100 ml of methylene chloride and measured at a temperature of 20 ° C.
(2) Glass transition point (Tg)
Measured with a DuPont 910 DSC.
(3) Fluidity (MFR)
Based on JIS K-7210, the amount of polymer (g) that flowed out for 10 minutes at 280 ° C. under a load of 2.16 kg using a semi-auto melt indexer manufactured by Toyo Seiki.
[0062]
(4) Oligomer content
Retention time of GPC chart determined by a method of injecting 20 μl of a solution in which 50 mg of sample was dissolved in 5 ml of chloroform while flowing chloroform as an eluent at a flow rate of 0.7 ml / min using GPC columns TSKgelG2000HXL and TSKgelG3000HXL made by Tosoh The ratio of the peak area of the oligomer component to the total peak area was expressed in%.
[0063]
(5) Water absorption rate
Measured according to ASTM D-0570.
(6) Methylene chloride undissolved particles
A solution obtained by dissolving 20 g of the aromatic polycarbonate resin in 1 L of methylene chloride was obtained by a method of converting scattered light into scattered light of latex particles by a laser sensor method using a liquid particle counter model 4100 manufactured by Hiac Leuco.
[0064]
(7) Light transmittance
Measurement was performed using a spectrophotometer U-3400 manufactured by Hitachi, Ltd. in accordance with ASTM D-1003.
(8) Photoelastic constant
This was measured with a photoelasticity measuring device PA-150 manufactured by Riken Keiki Co., Ltd.
(9) Retardation value
Using M35B-D-DM manufactured by Meiki Seisakusho Co., Ltd., a disk having a diameter of 120 mm and a thickness of 1.2 mm was molded at a heating cylinder temperature of 330 ° C., a mold temperature of 85 ° C., and a cooling time of 5 seconds. Using an ADR200B automatic birefringence measuring apparatus manufactured by Kuh, a portion having a radius of 30 mm from the center of the disk was measured.
[0065]
(10) Thermal stability
After drying the sample pellets at 120 ° C. for 5 hours, using an injection molding machine (SG-150 manufactured by Sumitomo Heavy Industries, Ltd.), a test piece (70 mm length, Each with a width of 50 mm and a thickness of 2 mm). _sp ) And hue change (ΔE). The change in hue was calculated according to the following equation by measuring each L, a, b value according to JIS Z 8730 using Nippon Denshoku Co., Ltd. Model Z-1001DP.
[0066]
[Expression 1]

(L ₁ , A ₁ And b ₁ Is the value of the composition that is not retained, L ₂ , A ₂ And b ₂ Is the value of the composition retained for 10 minutes)
[0067]
(11) Molding operability
When injection molding 100 sheets of 120mmφ, 1.2mm thickness disk substrate using M35B-D-DM manufactured by Meiki Seisakusho Co., Ltd., recorded in the disk substrate by defective parts (void, cloud, cold, silver, etc.) The minimum cylinder temperature was measured so that no defective part) was generated. This lower temperature has the advantage that the melt viscosity is low and the molding temperature range is wide at the same temperature.
[0068]
(12) Tensile test method
Based on ASTM D-638, measurement was performed using UTM2.5T manufactured by Toyo Baldwin.
[0069]
Example 1
[A] Synthesis of copolymer of polymer A;
In a reactor equipped with a thermometer, a stirrer and a reflux condenser, 929.2 parts of ion-exchanged water and 61.3 parts of a 48% aqueous sodium hydroxide solution are placed, and 1,1-bis (4-hydroxyphenyl) -3,3, 5-trimethylcyclohexane (component a-1: hereinafter sometimes abbreviated as “bisphenol TMC”) 39 parts, 4,4′- ( m-phenylenediisopropylidene) diphenol (Component a-2: 43.6 parts and 0.17 part of hydrosulfite are dissolved, and 1.51 parts of p-tert-butylphenol and 637.9 parts of methylene chloride are added. After adding 09 parts, 32.4 parts of phosgene was blown in for 40 minutes at 15-25 ° C. with stirring. After completion of the phosgene blowing, 15.6 parts of a 48% aqueous sodium hydroxide solution was added, and the reaction was terminated by stirring at 28 to 33 ° C. for 1 hour. After completion of the reaction, the product is diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and when the conductivity of the aqueous phase becomes almost the same as that of ion-exchanged water, a separation chamber having a foreign matter outlet at the bearing portion. Methylene chloride was evaporated using a kneader equipped with a bisphenol TMC to obtain 86.4 parts of a colorless polymer having a molar ratio of bisphenol TMC to bisphenol M of 50:50 and a specific viscosity of 0.271 (yield 97). %).
[0070]
[B] Synthesis of polycarbonate homopolymer (polymer B) from bisphenol A;
A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 11057.0 parts of ion-exchanged water and 1559.9 parts of a 48% aqueous sodium hydroxide solution, and 2133.9 parts of bisphenol A and 2.12 parts of hydrosulfite were dissolved therein. After that, 6445.3 parts of methylene chloride was added, and 1005.6 parts of phosgene was blown in for 60 minutes at 15 to 20 ° C. with stirring. After completion of the phosgene blowing, 92.3 parts of p-tert-butylphenol and 829.9 parts of 48% aqueous sodium hydroxide solution were added, and the mixture was emulsified by stirring, 0.009 parts of triethylamine was added, and 28-33 ° C for 1 hour. The reaction was terminated by stirring. After completion of the reaction, the product solution was subjected to ion exchange water flow rate of 1,000 ml / min, reaction product solution flow rate of 1,500 ml / min, rotation speed with a centrifugal extractor with a perforated plate [Hultrex EP-02, manufactured by Hitachi, Ltd.] After centrifuging at 3,500 rpm, the methylene chloride phase is made acidic with hydrochloric acid, and the centrifuging operation is repeated under the same conditions. When the conductivity of the aqueous phase is almost the same as that of ion-exchanged water, Methylene chloride was evaporated by a kneader provided with an isolation chamber having a foreign matter outlet, to obtain 2,400 parts (yield 92%) of a granular colorless polycarbonate resin having a specific viscosity of 0.269.
[C] Adjustment of resin composition;
[0071]
The polymer weight ratio (polymer A: polymer B) in the solution of the copolymer solution of polymer A synthesized in [A] and the homopolymer (polymer B) solution of bisphenol A synthesized in [B] is 95: 5. Then, each was put into a container with a stirrer and stirred and mixed. After mixing, after passing through a filter having a mesh size of 0.3 μm, the mixed solution is put into a kneader provided with an isolation chamber having a foreign matter outlet in the bearing portion, and the methylene chloride is evaporated to evaporate the polycarbonate resin particles. Got the body.
[0072]
To this polycarbonate resin granule, 0.003% of distearyl pentaerythritol diphosphite, 0.005% of triethyl phosphate and 0.045% of stearic acid monoglyceride were added, and a φ30 mm twin screw extruder with a vent was used. After being pelletized, it was injection molded onto a 120 mmφ, 1.2 mm thick disk substrate using M35B-D-DM manufactured by Meiki Seisakusho. The methylene chloride undissolved particles of this product were 15,000 particles / g at 0.5 μm or more and 190 particles / g at 1 μm or more. The results are shown in Table 1.
[0073]
Example 2
The weight ratio of polymer A: polymer B in the solution of the copolymer solution of polymer A synthesized in [A] and the homopolymer (polymer B) solution of bisphenol A synthesized in [B] is 90:10. Thus, the same operation as in Example 1 was performed except that each was put into a container with a stirrer. The results are shown in Table 1.
[0074]
Example 3
The copolymer solution of component A synthesized in [A] and the homopolymer solution of bisphenol A synthesized in [B] were stirred so that the weight ratio of polymer A: polymer B in the solution was 60:40. The same operation as in Example 1 was carried out except that it was put in an attached container. The results are shown in Table 1.
[0075]
Example 4
For Component A, the same operation as in Example 1 was performed. The melting method was used as a method for synthesizing polymer B. That is, in a reactor equipped with a stirrer and a distillation column, 50.2 parts (0.22 mol) of 2,2-bis (4-hydroxyphenyl) propane, 49.2 parts of diphenyl carbonate (manufactured by Bayer) (0.23) Mol) and 0.0005 part of sodium hydroxide and 0.0016 part of tetramethylammonium hydroxide as a catalyst were substituted with nitrogen. This mixture was heated to 200 ° C. and dissolved with stirring. Next, most of the phenol was distilled off in 1 hour while heating at a reduced pressure of 30 Torr, the temperature was further raised to 270 ° C., and the polymerization reaction was carried out for 2 hours at a reduced pressure of 1 Torr. 2.3 parts of carbonylphenyl phenyl carbonate were added. Thereafter, end-capping reaction was carried out at 270 ° C. and 1 Torr or less for 5 minutes. Next, in a molten state, 0.0023 part (4 × 10 −5 mol / bisphenol 1 mol) of dodecylbenzenesulfonic acid tetrabutylphosphonium salt is added as a catalyst neutralizing agent and reacted at 270 ° C. and 10 Torr or less for 10 minutes. And a polymer having a specific viscosity of 0.271 was obtained. This polymer was sent to the extruder with a gear pump. In the middle of the extruder, polymer A: polymer B, which had been melted in advance, was added and mixed from the side feeder provided at a weight ratio of 90:10. Further, 0.003 wt% of trisnonylphenyl phosphite, 0.005 wt% of trimethyl phosphate and 0.045 wt% of glycerin monostearate were added to obtain polycarbonate pellets.
[0076]
Comparative Example 1
In Example 1, after passing only the copolymer solution of component A synthesized in [A] through a filter having a mesh opening of 0.3 μm, this kneader was provided with an isolation chamber having a foreign matter outlet in the bearing portion. The same operation as in Example 1 was performed except that the polycarbonate resin powder was obtained by adding the mixed solution and evaporating methylene chloride. The results are shown in Table 1.
[0077]
Comparative Example 2
In Example 1, only the bisphenol A homopolymer (polymer B) solution synthesized in [B] is passed through a filter having a mesh opening of 0.3 μm, and then an isolation chamber having a foreign matter outlet is provided in the bearing portion. The mixed solution was put into a kneader and the same procedure as in Example 1 was performed except that the polycarbonate resin particles were obtained by evaporating methylene chloride. The results are shown in Table 1.
[0078]
Comparative Example 3
In Example 1, the copolymer A (polymer A) solution synthesized in [A] and the bisphenol A homopolymer (polymer B) solution synthesized in [B] were mixed with the weight of polymer A: polymer B in the solution. The same operation as in Example 1 was performed except that the mixture was put into a container with a stirrer so that the ratio was 30:70. The results are shown in Table 1.
[0079]
[Table 1]

[0080]
Example 5
[A] Synthesis of copolymer (polymer A) from component a-1 and component a-2;
In a reactor equipped with a thermometer, a stirrer and a reflux condenser, 929.2 parts of ion-exchanged water and 61.3 parts of 48% aqueous sodium hydroxide solution were placed, and 1,1-bis (4-hydroxyphenyl) -3,3,5. -43.3 parts of trimethylcyclohexane ("bisphenol TMC"), 29.5 parts of 2,2-bis (3-methyl-4-hydroxyphenyl) propane (hereinafter sometimes abbreviated as "bisphenol C") and hydrosal After dissolving 0.17 parts of phyto, 1.51 parts of p-tert-butylphenol and 637.9 parts of methylene chloride were added, 0.09 part of triethylamine was added, and then 32.4 parts of phosgene was added at 15 to 25 ° C. with stirring. It took 40 minutes to blow. After completion of the phosgene blowing, 15.6 parts of a 48% aqueous sodium hydroxide solution was added, and the reaction was terminated by stirring at 28 to 33 ° C. for 1 hour. After completion of the reaction, the product is diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and when the conductivity of the aqueous phase is almost the same as that of ion-exchanged water, a separation chamber having a foreign matter outlet at the bearing portion. Methylene chloride was evaporated using a kneader equipped with a bisphenol TMC to obtain 79.0 parts of a colorless polymer having a molar ratio of bisphenol TMC to bisphenol C of 55:45 and a specific viscosity of 0.276 (yield 97). %).
[0081]
[B] Synthesis of polycarbonate homopolymer (polymer B) from bisphenol A;
A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 11057.0 parts of ion-exchanged water and 1559.9 parts of a 48% aqueous sodium hydroxide solution, and 2133.9 parts of bisphenol A and 2.12 parts of hydrosulfite were dissolved therein. After that, 6445.3 parts of methylene chloride was added, and 1005.6 parts of phosgene was blown in for 60 minutes at 15 to 20 ° C. with stirring. After completion of the phosgene blowing, 92.3 parts of p-tert-butylphenol and 829.9 parts of 48% aqueous sodium hydroxide solution were added, and the mixture was emulsified by stirring, 0.009 parts of triethylamine was added, and 28-33 ° C for 1 hour. The reaction was terminated by stirring. After completion of the reaction, the product solution was subjected to ion exchange water flow rate of 1,000 ml / min, reaction product solution flow rate of 1,500 ml / min, rotation speed with a centrifugal extractor with a perforated plate [Hultrex EP-02, manufactured by Hitachi, Ltd.] After centrifuging at 3,500 rpm, the methylene chloride phase is made acidic with hydrochloric acid, and the centrifuging operation is repeated under the same conditions. When the conductivity of the aqueous phase is almost the same as that of ion-exchanged water, Methylene chloride was evaporated by a kneader provided with an isolation chamber having a foreign matter outlet, to obtain 2,400 parts (yield 92%) of a granular colorless polycarbonate resin having a specific viscosity of 0.269.
[0082]
[C] Adjustment of resin composition;
The polymer weight ratio (polymer A: polymer B) in the solution of the copolymer solution of polymer A synthesized in [A] and the homopolymer (polymer B) solution of bisphenol A synthesized in [B] is 95: 5. Then, each was put into a container with a stirrer and stirred and mixed. After mixing, after passing through a filter having a mesh size of 0.3 μm, the mixed solution is put into a kneader provided with an isolation chamber having a foreign matter outlet in the bearing portion, and the methylene chloride is evaporated to evaporate the polycarbonate resin particles. Got the body.
[0083]
To this polycarbonate resin granule, 0.003% of distearyl pentaerythritol diphosphite, 0.005% of triethyl phosphate and 0.045% of stearic acid monoglyceride were added, and a φ30 mm twin screw extruder with a vent was used. After being pelletized, it was injection molded onto a 120 mmφ, 1.2 mm thick disk substrate using M35B-D-DM manufactured by Meiki Seisakusho. The methylene chloride undissolved particles of this product were 15,000 particles / g at 0.5 μm or more and 190 particles / g at 1 μm or more. The results are shown in Table 2.
[0084]
Example 6
The polymer A copolymer solution synthesized in [A] of Example 5 and the bisphenol A homopolymer (polymer B) solution synthesized in [B] have a weight ratio of polymer A: polymer B in the solution. The same operation as in Example 5 was performed except that the mixture was put into a container with a stirrer so that the ratio was 90:10. The results are shown in Table 2.
[0085]
Example 7
The polymer A copolymer solution synthesized in [A] of Example 5 and the bisphenol A homopolymer solution (polymer B) synthesized in [B] had a weight ratio of polymer A: polymer B in the solution. The same operation as in Example 5 was performed except that the mixture was put into a container with a stirrer so that the ratio was 65:35. The results are shown in Table 2.
[0086]
Example 8
For Component A, the same operation as in Example 1 (A) was performed. The melting method was used as the synthesis method of component B. That is, in a reactor equipped with a stirrer and a distillation column, 50.2 parts (0.22 mol) of 2,2-bis (4-hydroxyphenyl) propane, 49.2 parts of diphenyl carbonate (manufactured by Bayer) (0.23) Mol) and 0.0005 part of sodium hydroxide and 0.0016 part of tetramethylammonium hydroxide as a catalyst were substituted with nitrogen. This mixture was heated to 200 ° C. and dissolved with stirring. Next, most of the phenol was distilled off in 1 hour while heating at a reduced pressure of 30 Torr, the temperature was further raised to 270 ° C., and the polymerization reaction was carried out for 2 hours at a reduced pressure of 1 Torr. 2.3 parts of carbonylphenyl phenyl carbonate were added. Thereafter, end-capping reaction was carried out at 270 ° C. and 1 Torr or less for 5 minutes. Next, in the molten state, 0.0023 part (4 × 10 4) of tetrabutylphosphonium dodecylbenzenesulfonate was used as a catalyst neutralizing agent. ^-Five Mol / bisphenol 1 mol) was added and the reaction was continued at 270 ° C. and 10 Torr or less for 10 minutes to obtain a polymer having a specific viscosity of 0.271. This polymer was sent to the extruder with a gear pump. In the middle of the extruder, component A, which had been melted in advance, was added and mixed from the side feeder provided so that component A / component B = 90/10. Further, 0.003 wt% of trisnonylphenyl phosphite, 0.005 wt% of trimethyl phosphate and 0.045 wt% of glycerin monostearate were added to obtain polycarbonate pellets.
[0087]
Comparative Example 4
In Example 5, after passing only the copolymer (polymer A) solution of component a-1 and component a-2 synthesized in [A] through a filter having a mesh size of 0.3 μm, foreign matters are removed from the bearing portion. The same operation as in Example 1 was performed except that the mixed solution was put into a kneader provided with an isolation chamber having an outlet and the methylene chloride was evaporated to obtain the polycarbonate resin particles. The results are shown in Table 2.
[0088]
Comparative Example 5
The solution of the copolymer (polymer A) of component a-1 and component a-2 synthesized in [A] of Example 5 and the homopolymer (polymer B) solution of bisphenol A synthesized in [B] The same operation as in Example 5 was performed, except that the polymer A: polymer B weight ratio was 30:70, and the mixture was placed in a vessel with a stirrer. The results are shown in Table 2.
[0089]
[Table 2]

[0090]
【The invention's effect】
According to the invention, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and 4,4 ′-(m-phenylenediisopropylidene) diphenol and / or 2,2-bis In the aromatic polycarbonate copolymerization using (3-methyl-4-hydroxyphenyl) propane and a dihydric phenol component, the present invention is improved by greatly reducing molding defects, molding conditions, thermal stability, and mechanical properties. Since this aromatic polycarbonate resin composition is excellent in water absorption, photoelastic constant, birefringence, moldability and thermal stability, it can be used as various molded articles. In particular, it is advantageously used as an optical molding suitable for structural or functional material applications of optical components such as optical discs, optical lenses, liquid crystal panels, optical cards, sheets, films, optical fibers, connectors, vapor-deposited plastic reflectors, and displays. can do. Among these, it can be used particularly advantageously as an optical disk substrate, and the industrial effect produced is particularly remarkable.

Claims (11)

(A) The dihydric phenol component is (a-1) 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (component a-1) and (a-2) 4,4′- (m-phenylene) diphenol and / or 2,2-bis (3-methyl-4-hydroxyphenyl) propane (component a-2) good Rina Li Kui component a-1: the ratio of the components a-2 Aromatic polycarbonate copolymer (Polymer A) composed of a dihydric phenol component having a molar ratio of 99: 1 to 20:80 and (B) the dihydric phenol component are the components a-1 and a-2. other dihydric phenol component (component b) than configured aromatic polycarbonate (polymer B) good Rina is, polymer a: 99.9 at a ratio weight of the polymer B: 0.1 to 40: it is a 60 Special Aromatic polycarbonate resin composition.   Component b is 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2- 2. At least one dihydric phenol selected from the group consisting of bis (4-hydroxyphenyl) -3,3-dimethylbutane, 4,4′-dihydroxydiphenyl ether and 4,4′-dihydroxydiphenyl sulfide. The aromatic polycarbonate resin composition described.   The aromatic polycarbonate resin composition according to claim 1, wherein component b is 2,2-bis (4-hydroxyphenyl) propane.   The aromatic polycarbonate resin composition according to claim 1, wherein the ratio of component a-1: component a-2 is 80:20 to 20:80 in molar ratio.   The aromatic polycarbonate resin composition according to claim 1, wherein the ratio of the polymer A to the polymer B is 99.5: 0.5 to 75:25 by weight. The aromatic polycarbonate resin composition has the following characteristics (1) to (4):
(1) The specific viscosity measured at 20 ° C. of a solution obtained by dissolving 0.7 g in 100 ml of methylene chloride is in the range of 0.2 to 0.5,
(2) The water absorption is 0.3% by weight or less,
(3) The oligomer content is 10% or less, and (4) 25,000 undissolved particles measured in the methylene chloride solution have a particle conversion diameter of 0.5 μm or more per 1 g of the aromatic polycarbonate resin composition. 1 or less, and 500 or less.
The aromatic polycarbonate resin composition according to claim 1, comprising:   The aromatic polycarbonate resin composition according to claim 1, wherein the MFR value is 52 to 70 g / 10 min. The aromatic polycarbonate resin composition according to claim 1, wherein the photoelastic constant is 47 × 10 ^{−13 to} 60 × 10 ⁻¹³ cm ² / dyne.   The aromatic polycarbonate resin composition according to claim 1, wherein the retardation value is 25 to 45 nm.   An optical molded article formed from the aromatic polycarbonate resin composition according to claim 1.   An optical disk substrate formed from the aromatic polycarbonate resin composition according to claim 1.