JP4571335B2 - Colored master pellets for optical molded products and optical disk substrates - Google Patents

Description

【００２８】
（式中、Ａは水素原子または炭素数１〜９の直鎖または分岐のアルキル基あるいはフェニル基置換アルキル基であり、ｒは１〜５、好ましくは１〜３の整数である。）
【００２９】
上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。
【００３０】
また、他の単官能フェノール類としては、長鎖のアルキル基ある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も示すことができる。これらのなかでは、下記一般式（２）および（３）で表される長鎖のアルキル基を置換基として有するフェノール類が好ましく使用される。
【００３１】
【化２】

【００３２】
【化３】

【００３３】
（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、ｎは１０〜５０の整数を示す。）
【００３４】
かかる一般式（２）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、テトラデシルフェノール、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等を挙げることができる。
【００３５】
また、一般式（３）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。
【００３６】
末端停止剤は、得られたポリカーボネート樹脂の全末端に対して少くとも５モル％、好ましくは少くとも１０モル％末端に導入されることが望ましい。より好ましくは全末端に対して末端停止剤が８０モル％以上導入されること、すなわち二価フェノールに由来する末端の水酸基（ＯＨ基）が２０モル％以下であることがより好ましく、特に好ましくは全末端に対して末端停止剤が９０モル％以上導入されること、すなわちＯＨ基が１０モル％以下の場合である。また、末端停止剤は単独でまたは２種以上混合して使用してもよい。
【００３７】
溶融エステル交換法による反応は、通常二価フェノールとカーボネートエステルとのエステル交換反応であり、不活性ガスの存在下に二価フェノールとカーボネートエステルとを加熱しながら混合して、生成するアルコールまたはフェノールを留出させる方法により行われる。反応温度は生成するアルコールまたはフェノールの沸点等により異なるが、通常１２０〜３５０℃の範囲である。反応後期には系を１．３３×１０³〜１３．３Ｐａ程度に減圧して生成するアルコールまたはフェノールの留出を容易にさせる。反応時間は通常１〜４時間程度である。
【００３８】
カーボネートエステルとしては、置換されていてもよい炭素数６〜１０のアリール基、アラルキル基あるいは炭素数１〜４のアルキル基などのエステルが挙げられる。具体的にはジフェニルカーボネート、ビス（クロロフェニル）カーボネート、ジナフチルカーボネート、ビス（ジフェニル）カーボネート、ジメチルカーボネート、ジエチルカーボネート、ジブチルカーボネートなどが挙げられ、なかでもジフェニルカーボネートが好ましい。
【００３９】
また、重合速度を速めるために重合触媒を用いることができ、かかる重合触媒としては、例えば水酸化ナトリウム、水酸化カリウム、二価フェノールのナトリウム塩、カリウム塩等のアルカリ金属化合物、水酸化カルシウム、水酸化バリウム、水酸化マグネシウム等のアルカリ土類金属化合物、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、トリメチルアミン、トリエチルアミン等の含窒素塩基性化合物、アルカリ金属やアルカリ土類金属のアルコキシド類、アルカリ金属やアルカリ土類金属の有機酸塩類、亜鉛化合物類、ホウ素化合物類、アルミニウム化合物類、珪素化合物類、ゲルマニウム化合物類、有機スズ化合物類、鉛化合物類、オスミウム化合物類、アンチモン化合物類マンガン化合物類、チタン化合物類、ジルコニウム化合物類などの通常エステル化反応、エステル交換反応に使用される触媒を用いることができる。触媒は単独で使用してもよいし、２種以上を組み合わせて使用してもよい。これらの重合触媒の使用量は、原料の二価フェノール１モルに対し、好ましくは１×１０^-8〜１×１０^-3当量、より好ましくは１×１０^-7〜５×１０^-4当量の範囲で選ばれる。
【００４０】
また、かかる重合反応において、フェノール性の末端基を減少するために、重縮反応の後期あるいは終了後に、例えばビス（クロロフェニル）カーボネート、ビス（ブロモフェニル）カーボネート、ビス（ニトロフェニル）カーボネート、ビス（フェニルフェニル）カーボネート、クロロフェニルフェニルカーボネート、ブロモフェニルフェニルカーボネート、ニトロフェニルフェニルカーボネート、フェニルフェニルカーボネート、メトキシカルボニルフェニルフェニルカーボネートおよびエトキシカルボニルフェニルフェニルカーボネート等の化合物を加えることが好ましい。なかでも２−クロロフェニルフェニルカーボネート、２−メトキシカルボニルフェニルフェニルカーボネートおよび２−エトキシカルボニルフェニルフェニルカーボネートが好ましく、特に２−メトキシカルボニルフェニルフェニルカーボネートが好ましく使用される。
【００４１】
さらにかかる重合反応において触媒の活性を中和する失活剤を用いることが好ましい。この失活剤の具体例としては、例えばベンゼンスルホン酸、ｐ−トルエンスルホン酸、ベンゼンスルホン酸メチル、ベンゼンスルホン酸エチル、ベンゼンスルホン酸ブチル、ベンゼンスルホン酸オクチル、ベンゼンスルホン酸フェニル、ｐ−トルエンスルホン酸メチル、ｐ−トルエンスルホン酸エチル、ｐ−トルエンスルホン酸ブチル、ｐ−トルエンスルホン酸オクチル、ｐ−トルエンスルホン酸フェニルなどのスルホン酸エステル；さらに、トリフルオロメタンスルホン酸、ナフタレンスルホン酸、スルホン化ポリスチレン、アクリル酸メチル‐スルホン化スチレン共重合体、ドデシルベンゼンスルホン酸−２−フェニル−２−プロピル、ドデシルベンゼンスルホン酸−２−フェニル−２−ブチル、オクチルスルホン酸テトラブチルホスホニウム塩、デシルスルホン酸テトラブチルホスホニウム塩、ベンゼンスルホン酸テトラブチルホスホニウム塩、ドデシルベンゼンスルホン酸テトラエチルホスホニウム塩、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、ドデシルベンゼンスルホン酸テトラヘキシルホスホニウム塩、ドデシルベンゼンスルホン酸テトラオクチルホスホニウム塩、デシルアンモニウムブチルサルフェート、デシルアンモニウムデシルサルフェート、ドデシルアンモニウムメチルサルフェート、ドデシルアンモニウムエチルサルフェート、ドデシルメチルアンモニウムメチルサルフェート、ドデシルジメチルアンモニウムテトラデシルサルフェート、テトラデシルジメチルアンモニウムメチルサルフェート、テトラメチルアンモニウムヘキシルサルフェート、デシルトリメチルアンモニウムヘキサデシルサルフェート、テトラブチルアンモニウムドデシルベンジルサルフェート、テトラエチルアンモニウムドデシルベンジルサルフェート、テトラメチルアンモニウムドデシルベンジルサルフェート等の化合物を挙げることができるが、これらに限定されない。これらの化合物を二種以上併用することもできる。
【００４２】
失活剤の中でもホスホニウム塩もしくはアンモニウム塩型のものが好ましい。
かかる失活剤の量としては、残存する触媒１モルに対して０．５〜５０モルの割合で用いるのが好ましく、また重合後のポリカーボネート樹脂に対し、０．０１〜５００ｐｐｍの割合、より好ましくは０．０１〜３００ｐｐｍ、特に好ましくは０．０１〜１００ｐｐｍの割合で使用する。
【００４３】
ポリカーボネート樹脂の分子量は、粘度平均分子量（Ｍ）で１０，０００〜２２，０００が好ましく、１２，０００〜２０，０００がより好ましく、１３，０００〜１８，０００が更に好ましく、１３，５００〜１６，５００が特に好ましい。かかる粘度平均分子量を有する芳香族ポリカーボネート樹脂は光学用材料として十分な強度が得られ、また成形時の溶融流動が良好であり、成形歪みが発生せず好ましい。また、芳香族ポリカーボネート樹脂の２種以上を混合しても差し支えない。本発明でいう粘度平均分子量は塩化メチレン１００ｍｌにポリカーボネート樹脂０．７ｇを２０℃で溶解した溶液から求めた比粘度（η_SP）を次式に挿入して求める。
η_SP／ｃ＝［η］＋０．４５×［η］²ｃ（但し［η］は極限粘度）
［η］＝１．２３×１０^-4Ｍ^0.83
ｃ＝０．７
【００４４】
本発明の光学成形品用着色マスターペレットには、本発明の目的を損なわない範囲で各種の熱安定剤、離型剤、帯電防止剤、光安定剤などを更に配合することが可能である。
【００４５】
離型剤としては、ポリカーボネート樹脂に使用される各種の離型剤が使用可能であるが、好ましくは高級脂肪酸エステルである。かかる高級脂肪酸エステルとしては、炭素数１０〜３４の脂肪族飽和一価カルボン酸と一価または二価以上の多価アルコールとのエステルを挙げることができる。かかる脂肪族飽和一価カルボン酸としては、カプリン酸、ウンデカン酸、ラウリン酸、トリデカン酸、ミリスチン酸、ペンタデカン酸、パルミチン酸、マーガリン酸、ステアリン酸、ノナデカン酸、アラキシン酸、ベヘン酸、およびモンタン酸などが挙げられる。
【００４６】
更に、好ましくは、炭素数１０〜２４、更に好ましくは炭素数１６〜２２の脂肪族飽和一価カルボン酸と二価以上の多価アルコールとの部分エステルを挙げることができる。ＤＶＤでは極めて高温での成形が必要とされるが、かかる部分エステルは高温時の成形における蛍光染料の特性の低下を抑制することが可能となる。二価以上の多価アルコールとしては、例えばエチレングリコール、グリセリン、ペンタエリスリトールなどを挙げることができる。特に好ましくはステアリン酸とグリセリンの部分エステルであり、これらは例えば理研ビタミン（株）よりリケマールＳ−１００Ａという商品名で市販されており、市場から容易に入手できる。かかる離型剤の組成割合としては、Ａ成分１００重量部に対して、０．００５〜０．５重量部が好ましく、より好ましくは０．０１〜０．２重量部である。
【００４７】
また本発明の着色マスターペレットには熱安定剤を含むことが好ましく、特により好ましくはリン系の安定剤を含有する場合である。かかるリン系安定剤としては、ホスファイト系、ホスホナイト系、およびホスフェート系のいずれも使用可能である。
【００４８】
本発明におけるホスファイト系安定剤としては、さまざまなものを用いることができる。具体的には例えば一般式（４）
【００４９】
【化４】

【００５０】
［式中Ｒ¹は、水素または炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基ないしアルカリール基、炭素数７〜３０のアラルキル基、またはこれらのハロ、アルキルチオ（アルキル基は炭素数１〜３０）またはヒドロキシ置換基を示し、３個のＲ¹は互いに同一または互いに異なるのいずれの場合も選択でき、また２価フェノール類から誘導されることにより環状構造も選択できる。］で表わされるホスファイト化合物である。
また、一般式（４）においてより好ましい態様としては、以下の一般式（５）
【００５１】
【化５】

【００５２】
［式中Ｒ²およびＲ³は、水素または炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基ないしアルキルアリール基、炭素数７〜３０のアラルキル基を示し、Ｒ²およびＲ³は同時に水素ではなく、互いに同一または互いに異なるのいずれの場合も選択できる。］で表わされるホスファイト化合物を挙げることができる。
【００５３】
また、一般式（６）
【００５４】
【化６】

【００５５】
［式中Ｒ⁴、Ｒ⁵はそれぞれ水素、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基ないしアルキルアリール基、炭素数７〜３０のアラルキル基、炭素数４〜２０のシクロアルキル基、炭素数１５〜２５の２−（４−オキシフェニル）プロピル置換アリール基を示す。尚、シクロアルキル基およびアリール基は、アルキル基で置換されていないもの、またはアルキル基で置換されているもののいずれも選択できる。］で表わされるホスファイト化合物を挙げることができる。
また、一般式（７）
【００５６】
【化７】

【００５７】
［式中Ｒ⁶、Ｒ⁷は炭素数１２〜１５のアルキル基である。尚、Ｒ⁶およびＲ⁷は互いに同一または互いに異なるのいずれの場合も選択できる。］で表わされるホスファイト化合物を挙げることができる。
【００５８】
ホスホナイト系安定剤としては下記一般式（８）で表わされるホスホナイト化合物、および下記一般式（９）で表わされるホスホナイト化合物を挙げることができる。
【００５９】
【化８】

【００６０】
【化９】

【００６１】
［式中、Ａｒ¹、Ａｒ²は炭素数６〜２０のアリール基ないしアルキルアリール基、または炭素数１５〜２５の２−（４−オキシフェニル）プロピル置換アリール基を示し、４つのＡｒ¹は互いに同一、または互いに異なるのいずれも選択できる。または２つのＡｒ²は互いに同一、または互いに異なるのいずれも選択できる。］
【００６２】
本発明においては、上記ホスファイト化合物およびホスホナイト化合物のうち、より好ましいリン系の安定剤として、上記一般式（５）で示されるホスファイト化合物（Ｅ１成分）、および上記一般式（８）（Ｅ２成分）および上記一般式（９）（Ｅ３成分）で示されるホスホナイト化合物を挙げることができ、これらは１種もしくは２種以上を併用することができ、より好ましくは上記一般式（１）で示されるホスファイト化合物をかかるＥ成分１００重量％中、少なくとも５重量％含む場合である。
【００６３】
上記一般式（４）に対応するホスファイト化合物における好ましい具体例としては、ジフェニルイソオクチルホスファイト、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、ジフェニルモノ（トリデシル）ホスファイト、フェニルジイソデシルホスファイト、フェニルジ（トリデシル）ホスファイトが挙げられる。より好ましい上記一般式（５）に対応する好ましい具体例としては、トリフェニルホスファイト、トリス（ジメチルフェニル）ホスファイト、トリス（ジエチルフェニル）ホスファイト、トリス（ジ−ｉｓｏ−プロピルフェニル）ホスファイト、トリス（ジ−ｎ−ブチルフェニル）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、トリス（２，６−ジ−ｔｅｒｔ−ブチルフェニル）ホスファイト等があげられ、トリス（ジアルキル置換フェニル）ホスファイトが好ましく、トリス（ジ−ｔｅｒｔ−ブチルフェニル）ホスファイトがより好ましく、トリス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）ホスファイトが特に好ましい。上記ホスファイト化合物は１種、または２種以上を併用することができる。
【００６４】
上記一般式（６）に対応するホスファイト化合物における好ましい具体例としては、ジステアリ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、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、フェニルビスフェノールＡペンタエリスリトールジホスファイト、ジシクロヘキシ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、好ましくはジステアリ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、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を挙げることができる。かかるホスファイト化合物は１種、または２種以上を併用することができる。
【００６５】
上記一般式（７）に対応するホスファイト化合物における好ましい具体例としては、４，４’−イソプロピリデンジフェノールジトリデシルホスファイトを挙げることができる。
【００６６】
上記一般式（８）に対応するホスホナイト化合物における好ましい具体例としては、テトラキス（２，４−ジ−ｉｓｏ−プロピルフェニル）−４，４’−ビフェニレンジホスホナイト、テトラキス（２，４−ジ−ｎ−ブチルフェニル）−４，４’−ビフェニレンジホスホナイト、テトラキス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−４，４’−ビフェニレンジホスホナイト、テトラキス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−４，３’−ビフェニレンジホスホナイト、テトラキス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−３，３’−ビフェニレンジホスホナイト、テトラキス（２，６−ジ−ｉｓｏ−プロピルフェニル）−４，４’−ビフェニレンジホスホナイト、テトラキス（２，６−ジ−ｎ−ブチルフェニル）−４，４’−ビフェニレンジホスホナイト、テトラキス（２，６−ジ−ｔｅｒｔ−ブチルフェニル）−４，４’−ビフェニレンジホスホナイト、テトラキス（２，６−ジ−ｔｅｒｔ−ブチルフェニル）−４，３’−ビフェニレンジホスホナイト、テトラキス（２，６−ジ−ｔｅｒｔ−ブチルフェニル）−３，３’−ビフェニレンジホスホナイト等があげられ、テトラキス（ジ−ｔｅｒｔ−ブチルフェニル）−ビフェニレンジホスホナイトが好ましく、テトラキス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−ビフェニレンジホスホナイトがより好ましい。このテトラキス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−ビフェニレンジホスホナイトは、２種以上の混合物が好ましく、具体的にはテトラキス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−４，４’−ビフェニレンジホスホナイト（Ｅ２−１成分）、テトラキス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−４，３’−ビフェニレンジホスホナイト（Ｅ２−２成分）および、テトラキス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−３，３’−ビフェニレンジホスホナイト（Ｅ２−３成分）の１種もしくは２種以上を併用して使用可能であるが、好ましくはかかる３種の混合物である。また、３種の混合物の場合その混合比は、Ｅ２−１成分、Ｅ２−２成分およびＥ２−３成分を重量比で１００：３７〜６４：４〜１４の範囲が好ましく、１００：４０〜６０：５〜１１の範囲がより好ましい。
【００６７】
上記一般式（９）に対応するホスホナイト化合物の好ましい具体例としては、ビス（２，４−ジ−ｉｓｏ−プロピルフェニル）−４−フェニル−フェニルホスホナイト、ビス（２，４−ジ−ｎ−ブチルフェニル）−３−フェニル−フェニルホスホナイト、ビス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−４−フェニル−フェニルホスホナイト、ビス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−３−フェニル−フェニルホスホナイトビス（２，６−ジ−ｉｓｏ−プロピルフェニル）−４−フェニル−フェニルホスホナイト、ビス（２，６−ジ−ｎ−ブチルフェニル）−３−フェニル−フェニルホスホナイト、ビス（２，６−ジ−ｔｅｒｔ−ブチルフェニル）−４−フェニル−フェニルホスホナイト、ビス（２，６−ジ−ｔｅｒｔ−ブチルフェニル）−３−フェニル−フェニルホスホナイト等があげられ、ビス（ジ−ｔｅｒｔ−ブチルフェニル）−フェニル−フェニルホスホナイトが好ましく、ビス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−フェニル−フェニルホスホナイトがより好ましい。このビス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−フェニル−フェニルホスホナイトは、２種以上の混合物が好ましく、具体的にはビス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−４−フェニル−フェニルホスホナイト（Ｅ３−１成分）および、ビス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−３−フェニル−フェニルホスホナイトの１種もしくは２種を併用して使用可能であるが、好ましくはかかる２種の混合物である。また、２種の混合物の場合その混合比は、重量比で５：１〜４の範囲が好ましく、５：２〜３の範囲がより好ましい。
【００６８】
一方ホスフェート系安定剤としては、トリブチルホスフェート、トリメチルホスフェート、トリクレジルホスフェート、トリフェニルホスフェート、トリクロルフェニルホスフェート、トリエチルホスフェート、ジフェニルクレジルホスフェート、ジフェニルモノオルソキセニルホスフェート、トリブトキシエチルホスフェート、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を挙げることができ、好ましくはトリメチルホスフェートである。
【００６９】
上記熱安定剤は、Ａ成分１００重量部あたり、０．０００１〜０．１重量部で含まれることが好ましく、より好ましくは０．０００５〜０．０５重量部、更に好ましくは０．００１〜０．０３重量部である。
【００７０】
本発明においては以下の方法により着色マスターペレットの粉末量の測定を実施する。着色マスターペレット５ｋｇを秤量した後、ペレットを円形振動篩機（特寿工作所製・ＴＭ−７０−２Ｓ）にかけ、２．０ｍｍの粉末および１．０ｍｍ以下の粉末を分離する。
【００７１】
かかる２．０ｍｍ以下の粉末の含有量は、本発明では５重量％以下である。この範囲であると光ディスク基板等の光学成形品を連続成形した際に色ムラ等が殆ど起らず外観が良好な光学成形品が得られる。好ましくは３重量％以下、より好ましくは１重量％以下、最も好ましくは０．５重量％以下である。
【００７２】
また１．０ｍｍ以下の粉末の含有量は、本発明では５００ｐｐｍ以下が好ましい。この範囲であると光ディスク基板等の光学成形品を成形した際に色ムラ、色スジ等が少なく、また電気特性の良好な光学成形品が得られる。更に好ましくは３００ｐｐｍ以下、最も好ましくは１００ｐｐｍ以下である。
【００７３】
本発明の着色マスターペレットでは着色剤を含有しているために更に粉末の影響が大きく、０．５ｍｍ以下の粉末の含有量が２００ｐｐｍ以下が好ましく、より好ましくは１００ｐｐｍ以下、最も好ましくは５０ｐｐｍ以下である。
【００７４】
本発明の粉末含有量の少ない着色マスターペレットを製造するには、ストランドのカッティング条件を調整して粉末の発生量を極力抑える。例えば樹脂を押出機で押出してストランドとし、これをカッターで切断してペレットを得る場合に、ペレットの断面形状は円形で凹凸が少ないものであることが望まれる。この断面形状の凹凸を減少させるためにストランドの冷却はストランドの周囲をできる限り均一な温度で冷却するのが望ましく、その際カッター切断時のストランドの温度が好ましくは１１０〜１４０℃、より好ましくは１２０〜１３０℃となるように冷却することが望ましい。かくしてストランドのねじれを僅少化することができ、表面の凹凸を少なくすることが可能となる。
【００７５】
また、一旦発生した粉末を篩いを用いて分離除去したり、風力を用いた重力分級機で粉末を分離除去する。
【００７６】
本発明における着色マスターペレットの形状は、成形用の着色マスターペレット、特に光学用成形材料用の着色マスターペレットとして使用されているものであればよく、大きさや形は特に制限されない。一般的には内径が２．０〜３．３ｍｍで長さが２．５〜３．５ｍｍのものが適当である。
【００７７】
【発明の実施の形態】
以下に、実施例をあげて本発明を具体的に説明するが、本発明はこれら実施例によって何ら限定されるものではない。また、実施例中の「部」は特に断りのない限り重量部を意味する。光ディスク共通の評価項目および方法は以下の通りである。
（１）粉末量の測定
着色マスターペレット５ｋｇを秤量した後、ペレットを円形振動篩機（特寿工作所製・ＴＭ−７０−２Ｓ）に２０分間かけ、２．０ｍｍおよび１．０ｍｍ以下の粉末を分離する。この粉末の重量を測定し、重量％およびｐｐｍ単位で表わした。
（２）色ムラの測定
表２記載のブレンドペレットを用い射出成形機［住友重機（株）Ｓ４８０／１５０］でシリンダー温度３５０℃、金型温度１２０℃で長さ５０ｍｍ×幅９０ｍｍ×厚さ０．６ｍｍの色ムラ評価成形板を連続成形で１００枚作成した。
【００７８】
この１００枚の成形板を分光光度計（ｄａｔａｃｏｌｏｒ社 ＳＦ５００）を用いて、Ｄ６５光源（相関色温度６５０４Ｋ）下での、Ｌ＊（明度）、ａ＊（赤味から緑味にかけての色度）、ｂ＊（黄味から青味にかけての色度）を測定し、その最大値と最小値より求められた値を（ｉ）式に挿入して、その色差（△Ｅ＊）を求め、３段階評価した。△Ｅ＊（色差）の値が０に近いほど色相が安定していることになる。
○：△Ｅ＊≦０．５
△：０．５＜△Ｅ＊＜１．０
×：△Ｅ＊≧１．０
【００７９】
【数１】

【００８０】
（３）色スジの測定
色ムラ評価成形板１００枚の中から成形１ショット目〜１０ショット目までの１０枚について、その外観を目視にて観察し、３段階評価した。
○：色スジが全くないもの
△：色スジが１個所あるもの
×：色スジが２個所以上あるもの
（４）光ディスクの外観観察
上記で得られた光ディスクについて、その外観観察を目視にて行った。
（５）ＢＬＥＲの測定
下記のブレンドペレットを用い射出成形機（住友重機（株）製ＤＩＳＫ３ＭＩＩＩ）で厚み１．２ｍｍ、１２０ｍｍφのＡｌ付基板に成形し、この基板のＢＬＥＲをＢＬＥＲ測定機（ＳＯＮＹ製・ＣＤｐｌａｙｅｒ ｃｏｔｒｏｌ ｕｎｉｔ ＣＤＳ−３０００）により測定した。なお、表４のＣ₁ＡＶＥとはＣ１エラー（Ｃ１コードで訂正出来るランダムエラー）の１秒間あたりの平均値である。
（６）光線透過特性
光線透過率測定用試験片は、得られたペレットを射出成形機［住友重機械工業Ｓ４８０／１５０］でシリンダー温度３５０℃、金型温度１２０℃で長さ５０ｍｍ×幅９０ｍｍ×厚さ０．６ｍｍの透過率評価用成形板を作成した。
【００８１】
この成形板を日立製作所（株）製自記分光光度計Ｕ−３２００型を用いて、光線透過特性を測定し、▲１▼３５０ｎｍ〜４００ｎｍの各波長における最大光線透過率、▲２▼４００ｎｍ〜６５０ｎｍにおける最小光線透過率、▲３▼６５０ｎｍにおける光線透過率を求めた。
（７）基板貼合せ試験
紫外線硬化型接着剤をスピンコート塗布、紫外線照射により硬化させ、データ基板２枚を貼合せてたＤＶＤディスクを得た。次いでその接着性を以下の手法により評価した。
○：手ではがすことはできず、十分な接着力を有する
×：手ではがすことができる
【００８２】
［実施例Ａ〜Ｒ、１〜２５および比較例Ａ、Ｂ、１〜３］
＜着色剤マスター組成物および添加剤マスター組成物の製造＞
まず表１記載の着色剤成分、添加剤成分を１０重量％の割合となるよう、Ａ成分の熱可塑性樹脂組成物で希釈し、ヘンシェルミキサーで均一に混合し着色剤マスター組成物および添加剤マスター組成物を得た。この着色剤マスター組成物および添加剤マスター組成物を表１記載組成になる様にブレンドした。
【００８３】
【表１】

【００８４】
＜着色剤マスターペレットおよび透明ペレットの製造＞
これらのマスター組成物を表１の組成割合となるよう残りの成分と混合し、タンブラーで均一に混合した。その後、径３０ｍｍφのベント付き２軸押出機［（株）神戸製鋼所ＫＴＸ−３０］でベントから真空排気させながらシリンダー温度２８０℃で溶融混練し、押出しペレット化（ペレット形状：径２．７ｍｍ×長さ３．０ｍｍ）した。押出機のダイス部分には、フィルターを設置し、５μｍ以上の異物が１ｇあたり２０個以下となるようにした。また上記の機器はすべてフィルターを通した清浄な空気が循環する１０１．８ｋＰａ（１．００５気圧）の雰囲気下に置き、冷却用の水はイオン交換水を使用した。
【００８５】
尚、着色剤マスターペレットＡ〜Ｑは、冷却方法としてストランドを冷却水を流した波板の上に通して冷却する方法（波板冷却方法）を用い、カッターで切断した直後のペレット温度は１３２℃とした。このペレットを矩形の導管中に落下させながらイオン化空気を向流に流してペレットに付着している微粉末を分離除去した。一方、着色剤マスターペレットＸは、表１記載の着色剤成分、添加剤成分、Ａ成分の熱可塑成樹脂を表１の組成割合となるよう直接タンブラーのみで混合した。また、冷却方法としてストランドを２７℃の水浴に５秒間通して冷却する方法を用い、カッターで切断した直後のペレット温度は８３℃とし、イオン化空気による微粉末除去を行わなかった。
【００８６】
また、別に希釈用の着色剤成分を含まない透明ペレット（ペレット形状：径２．７ｍｍ×長さ３．０ｍｍ）を上記着色剤マスターペレットＡ〜Ｑと同様な条件で製造した。
【００８７】
【表２】

【００８８】
＜ＣＤディスクの製造＞
表２記載の着色マスターペレットと透明ペレットを用いて射出成形機、住友重機械工業製ＤＩＳＫ３ Ｍ ＩＩＩにＣＤ専用の金型を取り付け、この金型にピットの入ったニッケル製のＣＤ用スタンパーを装着し、成形材料を自動搬送にて成形機のホッパーに投入し、シリンダー温度３４０℃、金型温度７５℃、射出速度１００ｍｍ／ｓｅｃ、保持圧力３９２０ｋＰａの条件で直径１２０ｍｍ、肉厚１．２ｍｍの基板を成形し、この基板を用いてＣＤディスクを得た。これらのＣＤディスクの評価結果を表３に示す。
【００８９】
【表３】

【００９０】
＜ＣＤ−Ｒディスクの製造＞
表２記載の着色マスターペレットと透明ペレットを用いてディスク基板を成形し、これに色素系記録層を形成してＣＤ−Ｒディスクを作成した。これらのＣＤ−Ｒディスクの評価結果を表４に示す。
【００９１】
【表４】

【００９２】
更に、ＣＤ−Ｒディスクの記録面にガラスを通して日光が当たる様にし、書込み・読出しに異常が起る日数を調べる耐候性試験を行った結果、比較例に対して実施例は倍以上の耐候性を有していた。
【００９３】
＜ＤＶＤディスクの製造＞
表２記載の着色マスターペレットと透明ペレットを用いて、射出成形機、住友重機械工業製ＤＩＳＫ３ Ｍ ＩＩＩにＤＶＤ専用の金型を取り付け、この金型にアドレス信号などの情報の入ったニッケル製のＤＶＤ用スタンパーを装着し、成形材料を自動搬送にて成形機のホッパーに投入し、シリンダー温度３８０℃、金型温度１１５℃、射出速度３００ｍｍ／ｓｅｃ、保持圧力３９２０ｋＰａの条件で直径１２０ｍｍ、肉厚０．６ｍｍのＤＶＤ基板を成形し、この基板を用いてＤＶＤディスクを得た。これらのＤＶＤディスクの評価結果を表５に示す。
【００９４】
【表５】

【００９５】
なお表１記載の各成分を示す記号および項目は下記の通りである。
（Ａ成分）
ＰＣ−１
粘度平均分子量が１５，２００のアミン触媒を用いないホスゲン法により得られたビスフェノールＡポリカーボネート樹脂パウダー（末端停止剤としてｐ−ｔｅｒｔ−ブチルフェノールを使用）
ＰＣ−２
粘度平均分子量が１４，８００のアミン触媒を用いてホスゲン法により得られた、全芳香族ジヒドロキシ成分のうち、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］が４５モル％、４，４’−（ｍ−フェニレンジイソプロピリデン）ジフェノール［ビスフェノールＭ］が５５モル％である芳香族ポリカーボネート共重合体パウダー（末端停止剤としてｐ−ｔｅｒｔ−ブチルフェノールを使用）
ＰＣ−３
末端水酸基濃度３４モル％、粘度平均分子量が１５，３００のエステル交換触媒として原料ビスフェノールＡ１モルに対してビスフェノールＡの２ナトリウム塩を２×１０^-7モルを用いた溶融エステル交換法により得られたビスフェノールＡポリカーボネート樹脂ペレット
【００９６】
（Ｂ成分）
赤染料−１：ペリノン系赤染料、有本化学（株）製 Ｐｌａｓｔ Ｒｅｄ ８３７０
赤染料−２：ペリレン系蛍光赤染料、ＢＡＳＦ社製 Ｌｕｍｏｇｅｎ Ｆ Ｒｅｄ ３０５
赤染料−３：クマリン系蛍光赤染料、バイエル社製 Ｍａｃｒｏｌｅｘ Ｆｌｕｏｒｅｓｃｅｎｔ Ｒｅｄ Ｇ
赤染料−４：チオインジゴ系蛍光赤染料、有本化学（株）製 Ｐｌａｓｔ Ｒｅｄ Ｄ５４
赤染料−５：ペリノン系赤染料、紀和化学（株）製 Ｋｐ Ｐｌａｓｔ ＲｅｄＨＧ
赤染料−６：ペリノン系赤染料、紀和化学（株）製 Ｋｐ Ｐｌａｓｔ ＲｅｄＨ２Ｇ
黄染料−１：キノリン系黄染料、有本化学（株）製 Ｐｌａｓｔ Ｙｅｌｌｏｗ８０１０
黄染料−２：クマリン系蛍光黄染料、バイエル社製 Ｍａｃｒｏｌｅｘ Ｆｌｕｏｒｅｓｃｅｎｔ Ｙｅｌｌｏｗ １０ＧＮ
黄染料−３：キノリン系黄染料、有本化学（株）製 Ｐｌａｓｔ Ｙｅｌｌｏｗ８０５０
緑染料：アンスラキノン系緑染料、有本化学（株）製 Ｏｉｌ Ｇｒｅｅｎ ５６０２
青染料：アンスラキノン系青染料、バイエル社製 Ｍａｃｒｏｌｅｘ ＢｌｕｅＲＲ
【００９７】
（添加剤成分）
ＳＴ：トリス（２，４−ジ−ｔｅｒｔ−ブチルフェニルホスファイト）、日本チバガイギー（株）製Ｉｒｇａｆｏｓ１６８
Ｌ１：グリセリンモノステアレート、理研ビタミン（株）製リケマールＳ−１００Ａ
【００９８】
【発明の効果】
意匠性に優れ、且つその種類、用途などが瞬時に判断しうると共に、光ディスク基板を成形した際に退色現象、色ムラ、色スジ等が少なく、また電気特性の良好な光学成形品用着色マスターペレットおよび光ディスク基板であり、本発明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 a colored master pellet for an optical molded article. More specifically, the present invention relates to a colored master pellet for an optical molded product that is excellent in design and can be instantly determined for its type and use, and has less color unevenness when an optical molded product such as an optical disk substrate is continuously formed. .
[0002]
[Prior art]
As a conventional method for coloring an optical recording medium, Japanese Patent Application Laid-Open No. 1-102505 using a full-colored pellet includes an orange optical recording medium made of a specific dye, Japanese Patent Application Laid-Open No. 2-33372 and Japanese Patent Application Laid-Open No. Hei. Japanese Patent No. 8-124212 proposes a black optical recording medium. Japanese Laid-Open Patent Publication No. 7-262606 proposes a colored optical disk using an extremely low concentration of colored master pellets.
[0003]
On the other hand, Japanese Patent Publication No. 6-18890 discloses a method for suppressing the generation of silver during the production of an optical disk by controlling the amount of fine powder in a pellet. Japanese Patent Application Laid-Open No. 11-342510 describes that an optical disc using pellets with a small amount of fine powder has good electrical characteristics.
[0004]
However, colored master pellets with a relatively high coloring density for optical molded products are used in combination with transparent pellets, so that classification of colored pellets, etc. can be performed more than transparent pellets, full-colored pellets, and extremely low-density colored master pellets. When the colored master pellets are classified in the hopper of the molding machine, there is a problem in that the color density varies from shot to shot when continuously molded.
[0005]
On the other hand, the transparent pellets, the full-colored pellets, and the extremely low-concentration colored master pellets described in the above publication are not sufficient to solve the above-described problems due to the coloring master.
[0006]
[Problems to be solved by the invention]
As a result of investigations to solve the above problems, the present inventors have determined that a relatively large powder in the colored master pellet is the cause of such problems. The inventors have found that the above problem can be solved by making the amount of the powder below a specific range, and have completed the present invention.
[0007]
[Means for Solving the Problems]
  The present inventionAromatic polycarbonateColored master pellets for optical molded products comprising resin (component A) and colorant (component B)And optical disk substrate molded from a mixture of aromatic polycarbonate resinThe pellets are characterized in that the content of powder having a particle size of 2.0 mm or less is 5% by weight or less.Optical disc substrateIt depends on.
[0008]
The optically molded product referred to in the present invention includes a lens, an optical card, an optical fiber, an optical disk, and the like, and an optical disk is particularly preferable. Such an optical disk is an optical disk on which information is recorded / reproduced by irradiation with a so-called laser beam. Specific examples include a digital audio disc (so-called compact disc: CD), a CD-ROM, an optical video disc (so-called laser disc), a DVD-ROM, a digital video disc (DVD-video), a DVD-R, and a CD. Various read-only discs such as -R, MO, MD-MO, PD, DVD-RAM, write-once discs, magneto-optical discs, phase change discs, etc. have been put into practical use. The colored master pellet of the present invention is particularly useful for producing a digital versatile disk which is a high-density optical disk represented by DVD-ROM, DVD-video, DVD-R, DVD-RAM and the like.
[0009]
The thermoplastic resin which is the component A of the present invention is a heat selected from aromatic polycarbonate resin, amorphous polyolefin resin, acrylic resin, hydrogenated polystyrene resin, amorphous polyester resin, amorphous polyarylate resin, and the like. A preferred example is a plastic resin, and more preferred is an aromatic polycarbonate resin or an amorphous polyolefin resin. Examples of the amorphous polyolefin resin include APO resin manufactured by Mitsui Chemicals, Arton manufactured by JSR, Zeonex manufactured by ZEON Corporation, and HPS resin manufactured by Dow. An aromatic polycarbonate resin is particularly preferable. The details of the aromatic polycarbonate resin will be described later.
[0010]
As the colorant used as the component B of the present invention, perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, Examples include organic colorants such as quinacridone dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes, and carbon black. Among these, transparent organic colorants are preferable. More preferable examples include anthraquinone dyes, perinone dyes, quinoline dyes, perylene dyes, coumarin dyes, and thioindigo dyes.
[0011]
Specific examples of B component dyes include CI Solvent Red 52, CI Solvent Red 149, CI Solvent Red 150, CI Solvent Red 191, CI Solvent Red 151, CI Solvent Blue 94, CI Solnt 97, CI Solvent 97, CI Solvent 97, CI Solvent 97 Anthraquinone dyes known as Violet 14, CI Solvent Green 3, CI Solvent Green 28, CI Vat Orange 9, CI Vat Orange 2, pyranthrones known as CI Vat Orange 4, anthraquinone dyes Anthraquinone dyes, CI Vat Orange , And the like di-benz pyrene quinone anthraquinone dyes known as CI Vat Yellow 4. Examples of thioindigo dyes include CI Vat Red 2, CI Vat Red 41, and CI Vat Red 47. Examples of perylene dyes include CI Vat Red 15, CI Vat Orange 7, and BASF's LUMOGEN series FORange 240, F Red 300, 305, F Yellow 083, F Red 339, and the like. As the coumarin dyes, Bayer's MACROLEX Fluorescent Yellow 10GN (Solvent Yellow 160: 1), MACROLEX Fluorescent Red G, and quinoline dyes as CI Solvent Yellow 33, CI Solvent Yellow 157V, CI Solvent Yellow 157C And so on. Examples of perinone dyes include CI Solvent Red 135, CI Solvent Red 179, CI Solvent Orange 60, and examples of phthalocyanine dyes include CI Pigment Blue 15: 3, CI Pigment Green 7, and CI Pigment Green. These can be used alone or in combination of two or more, and can be colored according to the purpose.
[0012]
The colorant preferably has a fine particle size in order to achieve sufficiently uniform dispersion, and more preferably has a particle size of 50 μm or less. Such a colorant can be obtained by sorting with various filters.
[0013]
As a ratio of A component and B component of this invention, Preferably B component is 0.005-10 weight part with respect to 100 weight part of A component. In such a range, when an optical recording medium is used, it has sufficient saturation and can be colored with a good design, and optical characteristics are good when an optical molded product such as an optical disk substrate is molded. A molded product is obtained. More preferably, it is 0.01-10 weight part with respect to 100 weight part of A component as a ratio of B component, Especially preferably, it is 0.05-5 weight part.
[0014]
The colored master pellet of the present invention can be produced by various methods. For example, colorants are preliminarily mixed together, (1) a method of uniformly kneading into a thermoplastic resin and then melt-kneading, (2) adding one or more colorants to the resin at a high concentration, such as a Henschel mixer A method of obtaining a master agent dry-blended using a mixer and then further premixing with the remaining thermoplastic resin and melt-kneading. (3) The colorant is independently added to a melt-kneader such as an extruder. A method of supplying and melt-kneading, (4) a method of supplying a colorant directly to a melt-kneader after dissolving the colorant in an organic solvent (the colorant solution is preferably filtered), (5) the coloration of (4) A method in which the agent solution is added to the resin at a high concentration and a master agent is prepared by a mixer such as a Henschel mixer, and then melted and kneaded with the remaining components. (6) The master agent in (5) is independently extruded. Supply to the melt kneader A method of melt-kneading, (7) a method of mixing the colorant solution and the thermoplastic resin solution (the solution is preferably filtered), and melt-extruding the powder from which the solvent has been removed with a spray drier, etc. Examples thereof include a method of directly supplying a mixed solution of a colorant solution and a thermoplastic resin solution to a melt kneader such as an extruder. After obtaining pellets by such melt-kneading, it is diluted with transparent pellets to a desired concentration to form an optical molded product. The dilution factor is preferably 2 to 30 times, more preferably 3 to 20 times, and most preferably 3 to 10 times.
[0015]
In the production of the above-mentioned colored master pellets for optical molded articles, since such colored master pellets are usually required to have high optical properties, it is preferable to minimize the presence of foreign substances that impede such optical properties. In order to obtain such a preferable colored master pellet, a material with a small amount of foreign matter is used as a raw material, and a manufacturing device such as an extruder or a pelletizer is installed in a clean air atmosphere obtained through a filter, and cooled. Also for the cooling water for the bath, use the one with a small amount of foreign matter such as metal ions obtained through ion exchange resin, etc. Furthermore, more about the raw material supply hopper, supply flow path, storage pellet tank etc. It is preferable to fill with clean air or the like.
[0016]
As the apparatus used for melt kneading, generally used ones such as a single screw extruder, a twin screw extruder, and a pressure kneader can be used, and a twin screw extruder with a vent is particularly preferable. Those that can be evacuated from are preferable. The raw materials to be used can be any of a method of pre-mixing with a tumbler, blender, nauter mixer, Banbury mixer, kneading roll, etc., or a method of supplying them independently using a measuring instrument. Is possible.
[0017]
As a method for obtaining a molded product from the colored master pellet of the present invention, various conventionally known methods can be used. For example, the molded product can be formed into a desired shape by a method such as injection molding, extrusion molding or compression molding. The colored master pellets for optical molded products of the present invention are suitable not only for disc-shaped optical recording media represented by DVD, but also for plate-shaped molded products such as optical cards, and for other bonding with optical recording media functions. This is suitable for various types of mold recording media. That is, the colored master pellet for an optical molded article of the present invention is excellent in fluidity, heat resistance, specific light transmittance, and excellent in designability and distinguishability. It is suitable for an optical recording medium substrate for software.
[0018]
Details of the aromatic polycarbonate resin suitable as the component A of the present invention will be described below. The aromatic polycarbonate resin used in the present invention is usually obtained by reacting a dihydric phenol and a carbonate precursor by an interfacial polycondensation method or a melt transesterification method, or a carbonate prepolymer by a solid phase transesterification method. Or obtained by polymerizing by a ring-opening polymerization method of a cyclic carbonate compound.
[0019]
Representative examples of the dihydric phenol used here 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 referred to as bisphenol A) ), 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) 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, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 9,9-bis (4 -Hydroxyphenyl) fluorene, 9,9-bis {(4-hydroxy-3-methyl) phenyl} fluorene, α, α'-bis ( -Hydroxyphenyl) -o-diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 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, and these can be used alone or in admixture of two or more.
[0020]
Among them, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3 -Methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) A homopolymer or copolymer obtained from at least one bisphenol selected from the group consisting of 3,3,5-trimethylcyclohexane and α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene In particular, a homopolymer of bisphenol A and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethyl Copolymers of rucyclohexane and bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane or α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene are preferably used. In particular, a homopolymer of bisphenol A, or 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene These copolymers are preferred.
[0021]
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.
[0022]
In producing polycarbonate resin by reacting the above dihydric phenol and carbonate precursor by interfacial polycondensation method or melt transesterification method, catalyst, terminal terminator, dihydric phenol antioxidant, etc., as necessary May be used. 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.
[0023]
Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, phloroglucid, or 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2, 2,4,6-trimethyl-2. , 4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1- Tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [1,1-bis (4- Hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol and other trisphenols, tetra (4-hydroxyphenyl) methane, bis (2,4-dihi And droxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof. Among these, 1,1 1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferable. Is preferred.
[0024]
When a polyfunctional compound that yields such a branched polycarbonate resin is included, the proportion is 0.001 to 1 mol%, preferably 0.005 to 0.5 mol%, particularly preferably 0.01, based on the total amount of the aromatic polycarbonate. -0.3 mol%. In particular, in the case of the melt transesterification method, a branched structure may occur as a side reaction. The amount of the branched structure is also 0.001 to 1 mol%, preferably 0.005 to 0.005% in the total amount of the aromatic polycarbonate. 5 mol%, particularly preferably 0.01 to 0.3 mol% is preferable. About this ratio¹It is possible to calculate by H-NMR measurement.
[0025]
The reaction by the interfacial polycondensation 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.
[0026]
In such a polymerization reaction, a terminal stopper is usually used. Monofunctional phenols can be used as such end terminators. Monofunctional phenols are commonly used as end terminators for molecular weight control, and the resulting polycarbonate resins are compared to those that do not because the ends are blocked by groups based on monofunctional phenols. Excellent thermal stability. Such monofunctional phenols are generally phenols or lower alkyl-substituted phenols, and can be monofunctional phenols represented by the following general formula (1).
[0027]
[Chemical 1]

[0028]
(In the formula, A is a hydrogen atom, a linear or branched alkyl group having 1 to 9 carbon atoms or a phenyl group-substituted alkyl group, and r is an integer of 1 to 5, preferably 1 to 3.)
[0029]
Specific examples of the monofunctional phenols include phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.
[0030]
In addition, 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 also be shown. Among these, phenols having a long-chain alkyl group represented by the following general formulas (2) and (3) as a substituent are preferably used.
[0031]
[Chemical 2]

[0032]
[Chemical Formula 3]

[0033]
Wherein 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 valent aliphatic hydrocarbon group, and n represents an integer of 10 to 50.)
[0034]
As the substituted phenols of the general formula (2), those having n of 10 to 30, particularly 10 to 26 are preferable. Specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, Examples include eicosylphenol, docosylphenol, and triacontylphenol.
[0035]
Further, as the substituted phenols of the general formula (3), those 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 decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate.
[0036]
It is desirable that the end terminator is introduced at the end of at least 5 mol%, preferably at least 10 mol%, based on the total end of the obtained polycarbonate resin. More preferably, the terminal terminator is introduced in an amount of 80 mol% or more with respect to all terminals, that is, the terminal hydroxyl group (OH group) derived from the dihydric phenol is more preferably 20 mol% or less, particularly preferably. This is the case where 90 mol% or more of the terminator is introduced with respect to all terminals, that is, the OH group is 10 mol% or less. Moreover, you may use a terminal terminator individually or in mixture of 2 or more types.
[0037]
The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and the alcohol or phenol produced by mixing the dihydric phenol and the carbonate ester with heating in the presence of an inert gas. Is carried out by distilling the water. 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. Later in the reaction, the system is 1.33 × 10^ThreeDistillation of alcohol or phenol produced by reducing the pressure to about ˜13.3 Pa is facilitated. The reaction time is usually about 1 to 4 hours.
[0038]
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, bis (chlorophenyl) carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Among them, diphenyl carbonate is preferable.
[0039]
A polymerization catalyst can be used to increase the polymerization rate. Examples of such polymerization catalyst include sodium hydroxide, potassium hydroxide, sodium salt of dihydric phenol, alkali metal compounds such as potassium salt, calcium hydroxide, Alkaline earth metal compounds such as barium hydroxide and magnesium hydroxide, nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine and triethylamine, alkoxides of alkali metals and alkaline earth metals, alkali metals And organic earth salts of alkaline earth metals, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organotin compounds, lead compounds, osmium compounds, antimony compounds manganese compounds, H Emission 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 type. The amount of these polymerization catalysts used is preferably 1 × 10 with respect to 1 mol of dihydric phenol as a raw material.^-8~ 1x10^-3Equivalent weight, more preferably 1 × 10^-7~ 5x10^-FourIt is selected in the range of equivalents.
[0040]
In the polymerization reaction, in order to reduce phenolic end groups, for example, bis (chlorophenyl) carbonate, bis (bromophenyl) carbonate, bis (nitrophenyl) carbonate, bis ( It is preferable to add compounds such as (phenylphenyl) carbonate, chlorophenylphenyl carbonate, bromophenylphenyl carbonate, nitrophenylphenyl carbonate, phenylphenyl carbonate, methoxycarbonylphenylphenyl carbonate and ethoxycarbonylphenylphenyl carbonate. Of these, 2-chlorophenyl phenyl carbonate, 2-methoxycarbonylphenyl phenyl carbonate and 2-ethoxycarbonylphenyl phenyl carbonate are preferable, and 2-methoxycarbonylphenyl phenyl carbonate is particularly preferably used.
[0041]
Furthermore, it is preferable to use a deactivator that neutralizes the activity of the catalyst in such a polymerization reaction. Specific examples of the deactivator include, for example, benzene sulfonic acid, p-toluene sulfonic acid, methyl benzene sulfonate, ethyl benzene sulfonate, butyl benzene sulfonate, octyl benzene sulfonate, phenyl benzene sulfonate, p-toluene sulfone. Sulfonic acid esters such as methyl acid, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, phenyl p-toluenesulfonate; trifluoromethanesulfonic acid, naphthalenesulfonic acid, sulfonated polystyrene , Methyl acrylate-sulfonated styrene copolymer, dodecylbenzenesulfonate-2-phenyl-2-propyl, dodecylbenzenesulfonate-2-phenyl-2-butyl, octylsulfonate tetrabutylphospho Salts, tetrabutylphosphonium decylsulfonate, tetrabutylphosphonium benzenesulfonate, tetraethylphosphonium dodecylbenzenesulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, tetrahexylphosphonium dodecylbenzenesulfonate, tetradecylbenzenesulfonate tetra Octyl phosphonium salt, decyl ammonium butyl sulfate, decyl ammonium decyl sulfate, dodecyl ammonium methyl sulfate, dodecyl ammonium ethyl sulfate, dodecyl methyl ammonium methyl sulfate, dodecyl dimethyl ammonium tetradecyl sulfate, tetradecyl dimethyl ammonium methyl sulfate, tetramethyl ammonium hexyl sulfate Over DOO, decyl trimethyl ammonium hexadecyl sulfate, tetrabutylammonium dodecylbenzyl sulfate, tetraethylammonium dodecylbenzyl sulfate, there may be mentioned compounds such as tetramethylammonium dodecylbenzyl sulfate, and the like. Two or more of these compounds can be used in combination.
[0042]
Among the quenching agents, those of phosphonium salt or ammonium salt type are preferred.
The amount of the deactivator is preferably 0.5 to 50 mol with respect to 1 mol of the remaining catalyst, and more preferably 0.01 to 500 ppm with respect to the polycarbonate resin after polymerization. Is used in a proportion of 0.01 to 300 ppm, particularly preferably 0.01 to 100 ppm.
[0043]
The molecular weight of the polycarbonate resin is preferably 10,000 to 22,000, more preferably 12,000 to 20,000, still more preferably 13,000 to 18,000, and 13,500 to 16 in terms of viscosity average molecular weight (M). , 500 is particularly preferred. An aromatic polycarbonate resin having such a viscosity average molecular weight is preferable because it has sufficient strength as an optical material, has good melt flow during molding, and does not cause molding distortion. Also, two or more aromatic polycarbonate resins may be mixed. The viscosity average molecular weight referred to in the present invention is a specific viscosity (η obtained from a solution of 0.7 g of polycarbonate resin dissolved in 100 ml of methylene chloride at 20 ° C._SP) Is inserted into the following equation.
η_SP/C=[η]+0.45×[η]²c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10^-FourM^0.83
c = 0.7
[0044]
In the colored master pellet for optical molded articles of the present invention, various heat stabilizers, mold release agents, antistatic agents, light stabilizers, and the like can be further blended within a range that does not impair the object of the present invention.
[0045]
As the release agent, various release agents used for polycarbonate resin can be used, and higher fatty acid esters are preferable. Examples of such higher fatty acid esters include esters of aliphatic saturated monocarboxylic acids having 10 to 34 carbon atoms and monohydric or dihydric or higher polyhydric alcohols. Such aliphatic saturated monovalent carboxylic acids include capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, araxic acid, behenic acid, and montanic acid Etc.
[0046]
In addition, a partial ester of an aliphatic saturated monovalent carboxylic acid having 10 to 24 carbon atoms, more preferably 16 to 22 carbon atoms, and a dihydric or higher polyhydric alcohol can be used. Although DVD requires molding at an extremely high temperature, such a partial ester can suppress deterioration of the properties of the fluorescent dye during molding at a high temperature. Examples of the dihydric or higher polyhydric alcohol include ethylene glycol, glycerin, pentaerythritol and the like. Particularly preferred are partial esters of stearic acid and glycerin, which are commercially available, for example, under the trade name Riquemar S-100A from Riken Vitamin Co., Ltd., and are easily available from the market. The composition ratio of the release agent is preferably 0.005 to 0.5 parts by weight, more preferably 0.01 to 0.2 parts by weight with respect to 100 parts by weight of component A.
[0047]
The colored master pellet of the present invention preferably contains a heat stabilizer, and more preferably contains a phosphorus-based stabilizer. As the phosphorus stabilizer, any of phosphite, phosphonite, and phosphate can be used.
[0048]
Various phosphite stabilizers can be used in the present invention. Specifically, for example, the general formula (4)
[0049]
[Formula 4]

[0050]
[Wherein R¹Is hydrogen or an alkyl group having 1 to 20 carbon atoms, an aryl group or alkaryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a halo or alkylthio thereof (the alkyl group has 1 to 30 carbon atoms). ) Or a hydroxy substituent and represents three R¹Can be selected to be the same or different from each other, and a cyclic structure can be selected by being derived from dihydric phenols. It is a phosphite compound represented by this.
Moreover, as a more preferable aspect in General formula (4), following General formula (5)
[0051]
[Chemical formula 5]

[0052]
[Wherein R²And R^ThreeRepresents hydrogen or an alkyl group having 1 to 20 carbon atoms, an aryl group or alkylaryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, and R²And R^ThreeAre not hydrogen at the same time, and can be selected either the same or different from each other. The phosphite compound represented by this can be mentioned.
[0053]
Further, the general formula (6)
[0054]
[Chemical 6]

[0055]
[Wherein R^Four, R^FiveAre each hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group or alkylaryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, and 15 to 25 carbon atoms. 2- (4-oxyphenyl) propyl-substituted aryl group. The cycloalkyl group and the aryl group can be selected from those not substituted with an alkyl group or those substituted with an alkyl group. The phosphite compound represented by this can be mentioned.
Further, the general formula (7)
[0056]
[Chemical 7]

[0057]
[Wherein R⁶, R⁷Is an alkyl group having 12 to 15 carbon atoms. R⁶And R⁷Can be selected to be the same or different from each other. The phosphite compound represented by this can be mentioned.
[0058]
Examples of the phosphonite stabilizer include phosphonite compounds represented by the following general formula (8) and phosphonite compounds represented by the following general formula (9).
[0059]
[Chemical 8]

[0060]
[Chemical 9]

[0061]
[Wherein Ar¹, Ar²Represents an aryl group or alkylaryl group having 6 to 20 carbon atoms, or a 2- (4-oxyphenyl) propyl-substituted aryl group having 15 to 25 carbon atoms, and 4 Ar¹Can be the same or different from each other. Or two Ar²Can be the same or different from each other. ]
[0062]
In the present invention, among the above phosphite compounds and phosphonite compounds, as a more preferable phosphorus stabilizer, the phosphite compound (E1 component) represented by the above general formula (5), and the above general formula (8) (E2) Component) and a phosphonite compound represented by the above general formula (9) (E3 component). These may be used alone or in combination of two or more, more preferably represented by the above general formula (1). The phosphite compound is contained in at least 5% by weight in 100% by weight of the E component.
[0063]
Preferred examples of the phosphite compound corresponding to the general formula (4) include diphenylisooctyl phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, diphenyl mono ( Tridecyl) phosphite, phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite. Preferable specific examples corresponding to the above general formula (5) include triphenyl phosphite, tris (dimethylphenyl) phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, Tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite Dialkyl-substituted phenyl) phosphite is preferred, tris (di-tert-butylphenyl) phosphite is more preferred, and tris (2,4-di-tert-butylphenyl) phosphite is particularly preferred. The said phosphite compound can use together 1 type, or 2 or more types.
[0064]
Preferred specific examples of the phosphite compound corresponding to the general formula (6) include distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite, etc., preferably distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite. That. Such phosphite compounds can be used alone or in combination of two or more.
[0065]
Preferable specific examples of the phosphite compound corresponding to the general formula (7) include 4,4'-isopropylidenediphenol ditridecyl phosphite.
[0066]
Preferred specific examples of the phosphonite compound corresponding to the general formula (8) include tetrakis (2,4-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-). n-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert- Butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-iso-propylphenyl) ) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-n-butylphenyl) -4,4'- Phenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylenedi Examples thereof include phosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite is preferred, and tetrakis ( 2,4-di-tert-butylphenyl) -biphenylenediphosphonite is more preferred. The tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite is preferably a mixture of two or more, specifically tetrakis (2,4-di-tert-butylphenyl) -4,4. '-Biphenylenediphosphonite (E2-1 component), tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite (E2-2 component) and tetrakis (2,4- One kind or two or more kinds of di-tert-butylphenyl) -3,3′-biphenylenediphosphonite (component E2-3) can be used in combination, but these three kinds of mixtures are preferable. In the case of three kinds of mixtures, the mixing ratio is preferably in the range of 100: 37 to 64: 4 to 14 by weight ratio of E2-1 component, E2-2 component and E2-3 component, and 100: 40 to 60 : The range of 5-11 is more preferable.
[0067]
Preferable specific examples of the phosphonite compound corresponding to the general formula (9) include bis (2,4-di-iso-propylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-n- Butylphenyl) -3-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -3- Phenyl-phenylphosphonite bis (2,6-di-iso-propylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) Nyl) -3-phenyl-phenylphosphonite and the like, bis (di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, bis (2,4-di-tert-butylphenyl) -phenyl-phenyl Phosphonite is more preferred. The bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite is preferably a mixture of two or more, specifically, bis (2,4-di-tert-butylphenyl) -4- Although it is possible to use one or two of phenyl-phenylphosphonite (E3-1 component) and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite in combination, A mixture of the two is preferred. In the case of two kinds of mixtures, the mixing ratio is preferably in the range of 5: 1 to 4 by weight, and more preferably in the range of 5: 2 to 3.
[0068]
On the other hand, as a phosphate stabilizer, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, Dioctyl phosphate, diisopropyl phosphate and the like can be mentioned, and trimethyl phosphate is preferred.
[0069]
The heat stabilizer is preferably contained in an amount of 0.0001 to 0.1 parts by weight per 100 parts by weight of component A, more preferably 0.0005 to 0.05 parts by weight, and still more preferably 0.001 to 0 parts. 0.03 part by weight.
[0070]
In the present invention, the powder amount of the colored master pellet is measured by the following method. After weighing 5 kg of the colored master pellets, the pellets are passed through a circular vibrating sieve (manufactured by Tokuju Kogyo Co., Ltd., TM-70-2S) to separate a 2.0 mm powder and a 1.0 mm or less powder.
[0071]
The content of the powder of 2.0 mm or less is 5% by weight or less in the present invention. Within this range, when an optical molded product such as an optical disk substrate is continuously molded, an optical molded product with good appearance can be obtained with little color unevenness. Preferably it is 3 weight% or less, More preferably, it is 1 weight% or less, Most preferably, it is 0.5 weight% or less.
[0072]
Further, the content of powder of 1.0 mm or less is preferably 500 ppm or less in the present invention. Within this range, when an optical molded product such as an optical disk substrate is molded, there is little color unevenness, color streaks, etc., and an optical molded product with good electrical characteristics can be obtained. More preferably, it is 300 ppm or less, and most preferably 100 ppm or less.
[0073]
Since the colored master pellet of the present invention contains a colorant, the influence of the powder is further large, and the content of the powder of 0.5 mm or less is preferably 200 ppm or less, more preferably 100 ppm or less, and most preferably 50 ppm or less. is there.
[0074]
In order to produce a colored master pellet having a low powder content of the present invention, the amount of powder generated is suppressed as much as possible by adjusting the cutting conditions of the strands. For example, when a resin is extruded with an extruder to form a strand, and this is cut with a cutter to obtain a pellet, it is desirable that the cross-sectional shape of the pellet is circular and has few irregularities. In order to reduce the unevenness of the cross-sectional shape, it is desirable that the strand is cooled as uniformly as possible around the strand. In this case, the temperature of the strand at the time of cutting the cutter is preferably 110 to 140 ° C, more preferably It is desirable to cool so that it may become 120-130 degreeC. Thus, twist of the strand can be reduced and surface irregularities can be reduced.
[0075]
The generated powder is separated and removed using a sieve, or the powder is separated and removed by a gravity classifier using wind power.
[0076]
The shape of the colored master pellet in the present invention is not particularly limited as long as it is used as a colored master pellet for molding, particularly a colored master pellet for optical molding materials. In general, an inner diameter of 2.0 to 3.3 mm and a length of 2.5 to 3.5 mm are suitable.
[0077]
DETAILED DESCRIPTION OF THE INVENTION
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” means parts by weight unless otherwise specified. Evaluation items and methods common to optical disks are as follows.
(1) Measurement of powder amount
After weighing 5 kg of the colored master pellets, the pellets are put on a circular vibrating sieve (manufactured by Tokuju Kogyo Co., Ltd., TM-70-2S) for 20 minutes to separate powders of 2.0 mm and 1.0 mm or less. The powder was weighed and expressed in weight% and ppm.
(2) Measurement of color unevenness
Using the blended pellets shown in Table 2, an injection molding machine [Sumitomo Heavy Industries, Ltd. S480 / 150] has a cylinder temperature of 350 ° C., a mold temperature of 120 ° C., and a color unevenness evaluation molding of length 50 mm × width 90 mm × thickness 0.6 mm. 100 plates were prepared by continuous molding.
[0078]
Using 100 spectrophotometers (datacolor, SF500), L * (brightness) and a * (chromaticity from red to green) under a D65 light source (correlated color temperature 6504K). , B * (chromaticity from yellow to blue) is measured, and the value obtained from the maximum and minimum values is inserted into the equation (i) to obtain the color difference (ΔE *). Graded. The closer the value of ΔE * (color difference) is to 0, the more stable the hue.
○: △ E * ≦ 0.5
Δ: 0.5 <ΔE * <1.0
×: ΔE * ≧ 1.0
[0079]
[Expression 1]

[0080]
(3) Measurement of color streaks
Color unevenness evaluation The appearance of 10 sheets from the 1st sheet to the 10th shot from among 100 molded sheets was visually observed and evaluated in three stages.
○: No color streaks
Δ: One color streak
×: Two or more color streaks
(4) Appearance observation of optical disc
The appearance of the optical disk obtained above was visually observed.
(5) BLER measurement
Using the blended pellets below, an injection molding machine (DISK3MIII manufactured by Sumitomo Heavy Industries, Ltd.) was used to mold a 1.2 mm thick, 120 mmφ Al-attached substrate, and the BLER of this substrate was measured using a BLER measuring machine (SONY, CD player control unit CDS- 3000). In Table 4, C₁AVE is an average value per second of C1 errors (random errors that can be corrected by C1 code).
(6) Light transmission characteristics
The test piece for measuring light transmittance was obtained by using an injection molding machine [Sumitomo Heavy Industries, Ltd. S480 / 150] to produce a pellet having a cylinder temperature of 350 ° C., a mold temperature of 120 ° C., length 50 mm × width 90 mm × thickness 0.6 mm. A molded plate for transmittance evaluation was prepared.
[0081]
The molded plate was measured for light transmission characteristics using a self-recording spectrophotometer U-3200 manufactured by Hitachi, Ltd., and (1) the maximum light transmittance at each wavelength of 350 nm to 400 nm, and (2) 400 nm to 650 nm. (3) The light transmittance at 650 nm was determined.
(7) Substrate bonding test
An ultraviolet curable adhesive was applied by spin coating and cured by ultraviolet irradiation to obtain a DVD disk having two data substrates bonded together. Subsequently, the adhesiveness was evaluated by the following method.
○: It cannot be peeled off by hand and has sufficient adhesive strength
×: Can be peeled off by hand
[0082]
[Examples A to R, 1 to 25 and Comparative Examples A, B, and 1 to 3]
<Manufacture of colorant master composition and additive master composition>
First, the colorant component and additive component shown in Table 1 are diluted with the thermoplastic resin composition of component A so as to have a ratio of 10% by weight, and uniformly mixed with a Henschel mixer, and the colorant master composition and additive master are mixed. A composition was obtained. The colorant master composition and additive master composition were blended so as to have the composition shown in Table 1.
[0083]
[Table 1]

[0084]
<Manufacture of colorant master pellets and transparent pellets>
These master compositions were mixed with the remaining components so as to have the composition ratios shown in Table 1, and mixed uniformly with a tumbler. Thereafter, the mixture was melt-kneaded at a cylinder temperature of 280 ° C. while being evacuated from the vent in a twin-screw extruder with a diameter of 30 mmφ [Kobe Steel Works KTX-30 Co., Ltd.], and extruded into pellets (pellet shape: diameter 2.7 mm × Length 3.0 mm). A filter was installed in the die portion of the extruder so that the number of foreign matters of 5 μm or more was 20 or less per 1 g. All the above devices were placed in an atmosphere of 101.8 kPa (1.005 atm) in which clean air passed through a filter circulated, and ion-exchanged water was used as cooling water.
[0085]
In addition, the coloring agent master pellets A to Q use a method (corrugated sheet cooling method) in which the strand is cooled by passing it over a corrugated sheet in which cooling water flows as a cooling method, and the pellet temperature immediately after cutting with a cutter is 132. C. While the pellets were dropped into a rectangular conduit, ionized air was allowed to flow countercurrently to separate and remove the fine powder adhering to the pellets. On the other hand, in the colorant master pellet X, the colorant component, the additive component, and the component A thermoplastic thermoplastic resin shown in Table 1 were directly mixed only by a tumbler so as to have the composition ratio shown in Table 1. Further, as a cooling method, a method was used in which the strand was cooled by passing it through a 27 ° C. water bath for 5 seconds. The pellet temperature immediately after cutting with a cutter was 83 ° C., and fine powder removal by ionized air was not performed.
[0086]
Separately, transparent pellets (pellet shape: diameter 2.7 mm × length 3.0 mm) not containing the colorant component for dilution were produced under the same conditions as the colorant master pellets A to Q.
[0087]
[Table 2]

[0088]
<Manufacture of CD disc>
Using the colored master pellets and transparent pellets listed in Table 2, a CD-only mold is attached to an injection molding machine, DISK3 M III manufactured by Sumitomo Heavy Industries, and a nickel CD stamper with pits is attached to this mold. Then, the molding material is automatically fed into the hopper of the molding machine, and the substrate is 120 mm in diameter and 1.2 mm in thickness under conditions of a cylinder temperature of 340 ° C., a mold temperature of 75 ° C., an injection speed of 100 mm / sec, and a holding pressure of 3920 kPa. And a CD disc was obtained using this substrate. Table 3 shows the evaluation results of these CD discs.
[0089]
[Table 3]

[0090]
<Manufacture of CD-R disc>
A disk substrate was formed using the colored master pellets and transparent pellets described in Table 2, and a dye-based recording layer was formed thereon to produce a CD-R disk. Table 4 shows the evaluation results of these CD-R discs.
[0091]
[Table 4]

[0092]
Furthermore, as a result of conducting a weather resistance test in which the recording surface of the CD-R disc was exposed to sunlight through glass and the number of days in which writing / reading abnormality occurred was conducted, the results of the comparative example were more than double the weather resistance. Had.
[0093]
<Manufacture of DVD discs>
Using the colored master pellets and transparent pellets listed in Table 2, a special mold for DVD is attached to an injection molding machine, DISK3 M III manufactured by Sumitomo Heavy Industries, Ltd., and this mold is made of nickel containing information such as address signals. A DVD stamper is installed, and the molding material is automatically fed into the hopper of the molding machine. The cylinder temperature is 380 ° C, the mold temperature is 115 ° C, the injection speed is 300 mm / sec, and the holding pressure is 3920 kPa. A 0.6 mm DVD substrate was molded, and a DVD disk was obtained using this substrate. Table 5 shows the evaluation results of these DVD disks.
[0094]
[Table 5]

[0095]
In addition, the symbol and item which show each component of Table 1 are as follows.
(Component A)
PC-1
Bisphenol A polycarbonate resin powder obtained by the phosgene method without using an amine catalyst having a viscosity average molecular weight of 15,200 (using p-tert-butylphenol as a terminal stopper)
PC-2
1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane [bisphenol among all aromatic dihydroxy components obtained by the phosgene method using an amine catalyst having a viscosity average molecular weight of 14,800 Aromatic polycarbonate copolymer powder having 45 mol% TMC] and 55 mol% 4,4 ′-(m-phenylenediisopropylidene) diphenol [bisphenol M] (p-tert-butylphenol was used as a terminal stopper). use)
PC-3
As a transesterification catalyst having a terminal hydroxyl group concentration of 34 mol% and a viscosity average molecular weight of 15,300, 2 × 10 of disodium salt of bisphenol A is used per 1 mol of raw material bisphenol A.^-7Bisphenol A polycarbonate resin pellets obtained by melt transesterification using moles
[0096]
(B component)
Red dye-1: Perinone red dye, Arimoto Chemical Co., Ltd. Plast Red 8370
Red dye-2: Perylene fluorescent red dye, Lumogen F Red 305 manufactured by BASF
Red dye-3: Coumarin fluorescent red dye, manufactured by Bayer, Macrolex Fluorescent Red G
Red dye-4: Thioindigo fluorescent red dye, Arimoto Chemical Co., Ltd., Red Red D54
Red dye-5: Perinone-based red dye, manufactured by Kiwa Chemical Co., Ltd. Kp Plas RedHG
Red dye-6: Perinone red dye, Kp Plastic RedH2G manufactured by Kiwa Chemical Co., Ltd.
Yellow dye-1: quinoline yellow dye, Arimoto Chemical Co., Ltd. Plast Yellow 8010
Yellow dye-2: Coumarin-based fluorescent yellow dye, manufactured by Bayer, Macrolex Fluorescent Yellow 10GN
Yellow dye-3: quinoline yellow dye, Arimoto Chemical Co., Ltd. Plast Yellow 8050
Green dye: Anthraquinone green dye, Oil Green 5602 manufactured by Arimoto Chemical Co., Ltd.
Blue dye: Anthraquinone blue dye, manufactured by Bayer, Macrolex BlueRR
[0097]
(Additive component)
ST: Tris (2,4-di-tert-butylphenyl phosphite), Irgafos 168 manufactured by Ciba Geigy Japan
L1: Glycerol monostearate, Rikenmar S-100A manufactured by Riken Vitamin Co., Ltd.
[0098]
【The invention's effect】
A coloring master for optical molded products that has excellent design properties, and can instantly determine its type and application, and has less fading, color unevenness, color streaks, etc. when optical disc substrates are molded, and has good electrical properties. It is a pellet and an optical disk substrate, and the industrial effect exhibited by the present invention is exceptional.

Claims (6)

An optical disk substrate molded from a mixture of a colored master pellet for an optical molded article comprising an aromatic polycarbonate resin (component A) and a colorant (component B) and an aromatic polycarbonate resin, the pellet having a particle size of 2 An optical disk substrate, wherein the content of powder of 0.0 mm or less is 5% by weight or less . 2. The optical disk substrate according to claim 1, wherein the pellet has an average length of 2.0 to 3.3 mm and an average major axis of the cross-sectional ellipse within a range of 2.5 to 3.5 mm . The optical disk substrate according to claim 1, wherein the component A is an aromatic polycarbonate resin having a viscosity average molecular weight of 10,000 to 22,000 . The optical disk substrate according to claim 1, wherein the A component is 90 to 99.995 wt% and the B component is 0.005 to 10 wt% . The optical disk substrate according to any one of claims 1 to 4, wherein the B component is an anthraquinone dye, perinone dye, quinoline dye, perylene dye, coumarin dye, or thioindigo dye . An optical disc formed from the optical disc substrate according to claim 1 .