JP4571285B2 - Colorant masterbatch for optical molded article and optical recording medium substrate - Google Patents

Description

【００５３】
（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。）
【００５４】
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。
【００５５】
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。
【００５６】
【化２】

【００５７】
【化３】

【００５８】
（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。）
【００５９】
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。
【００６０】
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。
【００６１】
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。
【００６２】
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。
【００６３】
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。
【００６４】
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。
【００６５】
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。
【００６６】
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。
【００６７】
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。
かかる触媒の量としては、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。
【００６８】
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樹脂成形品として十分な強度が得られ、また光学歪みや複屈折を極力低減することが可能となる。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
【００６９】
上記の如くポリカーボネート樹脂はその製造において触媒としてナトリウム化合物を使用することから、界面重縮合の場合は十分な水洗を行い、溶融エステル交換法の場合にはかかる触媒の配合量に十分に留意して、ポリカーボネート樹脂自体のナトリウム元素の含有量を０．５ｐｐｍ以下、好ましくは０．３ｐｐｍ以下、特に好ましくは０．２ｐｐｍ以下とすることが好ましい。
【００７０】
また芳香族ポリカーボネート樹脂を着色剤マスターバッチのＡ成分として使用する場合、かかる着色剤マスターバッチにおける粘度平均分子量は、主原料の芳香族ポリカーボネート樹脂の粘度平均分子量との差の絶対値として、１，０００以内の範囲にあることが好ましい。より好ましくは８００以内の範囲、更に好ましくは５００以内の範囲である。特に光記録媒体においてはかかる差が小さいことが好ましい。光記録媒体の場合には極めてその成形サイクルが短く、極限に近い可塑化工程を経ている場合が多い。したがって不均一な溶融可塑化挙動を取る成分の存在は、材料の不均一性を高める要因となり着色剤の分散不良などの問題を生ずる原因となる。
【００７１】
本発明の光学用樹脂成形品中には、各種の熱安定剤、離型剤、帯電防止剤、光安定剤などが含まれていてもよく、したがって本発明の着色剤マスターバッチに更にこれらの成分を高濃度に含むことも、本発明の目的を損なわない範囲で可能である。
【００７２】
離型剤としては、各種の離型剤が使用可能であるが、好ましくは脂肪酸エステルである。かかる脂肪酸エステルとしては、炭素数６〜３４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、カプロン酸、カプリル酸、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。
【００７３】
具体的には一価アルコールと飽和脂肪酸のエステルとして、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等が挙げられる。
【００７４】
具体的に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、ステアリン酸モノグリセリド、ステアリン酸ジグリセリド、ステアリン酸トリグリセリド、ステアリン酸モノソルビテート、ベヘ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、ペンタエリスリトールテトラペラルゴネート、プロピレングリコールモノステアレート、ビフェニルビフェネート、ソルビタンモノステアレート、２−エチルヘキシルステアレート、ジペンタエリスリトールヘキサステアレート等のジペンタエリスリトール全エステルまたは部分エステル等が挙げられる。
【００７５】
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。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る。
【００７６】
離型剤は、離型剤全量１００重量％に対して、上記脂肪酸エステルが９０重量％以上であることが好ましく、更に好ましくは９５重量％以上、特に好ましくは実質的に脂肪酸エステルのみからなる場合である。
【００７７】
更に上記脂肪酸エステルの酸価は３以下が好ましく、２以下がより好ましい。
グリセリンモノステアレートの場合には、酸価１．５以下、純度９５重量％以上が好ましい。更に好ましいグリセリンモノステアレートは酸価１．２以下、純度が９８重量％以上のものである。脂肪酸エステルの酸価の測定は、公知の方法を用いることができる。
【００７８】
かかる離型剤の組成割合としては、光学用樹脂成形品１００重量％中、０．００５〜０．５重量％が好ましく、より好ましくは０．０１〜０．２重量％である。
【００７９】
熱安定剤としてはリン系安定剤を好ましく挙げることができる。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。
【００８０】
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）
【００８１】
【化４】

【００８２】
［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。
【００８３】
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）
【００８４】
【化５】

【００８５】
［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。
【００８６】
また、一般式（６）
【００８７】
【化６】

【００８８】
［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。
【００８９】
また、一般式（７）
【００９０】
【化７】

【００９１】
［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。
【００９２】
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。
【００９３】
【化８】

【００９４】
【化９】

【００９５】
［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。］
【００９６】
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。
【００９７】
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。
【００９８】
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。
【００９９】
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テトラトリデシルホスファイトを挙げることができる。
【０１００】
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。
【０１０１】
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。
【０１０２】
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。
【０１０３】
本発明の光学用樹脂成形品中には、酸化防止の目的で通常知られた酸化防止剤が含まれていてもよい。かかる酸化防止剤としては、例えばペンタエリスリトールテトラキス（３−メルカプトプロピオネート）、ペンタエリスリトールテトラ（β−ラウリルチオプロピオネート）エステル、グリセロール−３−ステアリルチオプロピオネート、トリエチレングリコール−Ｎ−ビス−３−（３−ｔｅｒｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）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］、テトラキス［メチレン−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］メタン、ｎ−オクタデシル−３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、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−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−ヒドロシンナミド）、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。
【０１０４】
上記熱安定剤は、本発明の光学用樹脂成形品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。また上記酸化防止剤は、本発明の光学用樹脂成形品１００重量部あたり、０．００１〜０．０５重量部が好ましい。
【０１０５】
本発明の着色剤マスターバッチを使用して、光学用樹脂成形品を得る方法としては従来公知の種々の方法が使用でき、例えば射出成形、押出成形、圧縮成形などの方法で所望の形状に成形することができる。特に好ましいのは射出成形であり、本発明の着色剤マスターバッチはかかる射出成形に十分に対応したものである。すなわち光記録媒体等の極めて成形サイクルが短く、可塑化時間の短い成形加工方法に好適なものである。
【０１０６】
本発明の着色剤マスターバッチおよび主原料である光学用材料を、射出成形機等の成形加工機に供給する方法としては、それらの混合物として供給する方法、またはそれぞれを特定量独立に供給し、射出成形機等の中で混合する方法のいずれも行うことができる。混合物の作成は、バッチ方式で所定割合を混合する方法や、計量機でそれぞれ連続的にミキサーに供給し混合物を得る方法等により行うことができる。
【０１０７】
【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。評価項目および方法は以下の通りである。
【０１０８】
（１）光ディスクの外観観察
評価用サンプルとして製造した光ディスクを目視により外観観察を行い、以下の基準により区分した。
○：外観良好
×：色ムラ、色スジなどの外観不良あり
【０１０９】
（２）ＢＬＥＲの測定
ＣＤディスクサンプルに対して、各サンプルのＢＬＥＲをＢＬＥＲ測定機（ＳＯＮＹ製・ＣＤｐｌａｙｅｒ ｃｏｔｒｏｌ ｕｎｉｔ ＣＤＳ−３０００）により測定した。なお、表３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
【０１１０】
（３）ディスク基板サンプル中のナトリウム元素量の測定
ディスク基板サンプルから採取したポリマー０．５ｇを電子工業用１−メチル−２−ピロリドン２５ｇに溶解し、かかる溶液をセイコー電子工業（株）製ＩＣＰ−ＭＳ、ＳＰＱ−９０００にかけて測定を行った。
【０１１１】
［参考例１〜１９］
（着色剤マスターペレットの製造）
表１および表２記載の各成分を以下の要領で製造し、各種の評価を行った。表１記載の着色剤成分とＡ成分のうちのパウダー成分とをスーパーフローターで均一に混合しマスター剤を得た。かかるマスター剤を表１および表２の組成割合となるよう残りのＡ成分と混合し、櫛歯付きのＶ型ブレンダーで均一に混合した。
かかる混合物を径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２６０℃で溶融混練し、得られたストランドを冷却用の水で冷却した後ペレタイザーでペレット化した。尚、ペレタイズ直後のペレットの温度は約１２９℃であった。
【０１１２】
更に、押出機のダイス部分には、焼結金属の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。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１．００５気圧の雰囲気下に置き、ストランド冷却用の水は１μｍのフィルターを通し、更にイオン交換膜を通したイオン交換水を使用した。
【０１１３】
【表１】

【０１１４】
【表２】

【０１１５】
［実施例１〜８および比較例１］
上記で得られた着色剤マスターペレットおよび主原料である光学用材料のペレットを表３記載の割合となるようそれぞれのタンクから、計量機を通して自動搬送により成形機のホッパーに投入した。尚、着色剤マスターペレット搬送管の直後に混合ゾーンを設け、ここで均一な混合ペレットとしたのち成形機のホッパーに投入されるようにした。ペレットはタンク投入前にクリーンオーブン中で１２０℃、５時間の熱風乾燥を行った。
【０１１６】
一方、射出成形機（住友重機械工業（株）製ＤＩＳＫ３ Ｍ３）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３．９ＭＰａの条件で直径１２０ｍｍ、肉厚１．２ｍｍの基板を成形し、この基板にアルミニウム膜をスパッタし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。
【０１１７】
【表３】

【０１１８】
［実施例９〜１１および比較例２］
金型温度を１１５℃とした以外は実施例１と同様の方法で、着色剤マスターペレットと主原料のペレットとを射出成形機のホッパーに自動搬送し、ディスク基板を成形し、これに色素系記録層および金属反射膜を形成してＣＤ−Ｒディスクを作成した。得られたＣＤ−Ｒディスクの評価結果を表４に示す。
【０１１９】
【表４】

【０１２０】
更に、ＣＤ−Ｒディスクの記録面に基板を通して日光が当たるように窓ガラスに貼り付け、書き込み・読み出しに異常が生ずるまでの日数を調べる耐光試験を行った結果、本発明実施例の着色ディスクは通常の透明基板のディスクに比較して倍以上の耐光性を有していた。
【０１２１】
［実施例１２〜１６および比較例３］
実施例１と同様の方法で、着色剤マスターペレットと主原料のペレットとを射出成形機のホッパーに自動搬送した。
【０１２２】
一方、射出成形機に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が入ったニッケル製のＤＶＤ−ＲＯＭ用スタンパーを装着した。そして上記ペレットをシリンダー温度３８０℃、金型温度１１５℃、射出速度３００ｍｍ／ｓｅｃ、保持圧力３．９ＭＰａの条件で、直径１２０ｍｍ、肉厚０．６ｍｍの光ディスク基板を得た。その後基板にアルミニウム膜をスパッタし、ＵＶ硬化型接着剤をスピンコートにより塗布接着させて２枚貼り合わせ光ディスクを得た。得られたＤＶＤ−ＲＯＭディスクの評価結果を表５に示す。
【０１２３】
【表５】

【０１２４】
更に、かかるＤＶＤディスクについて、ＰＩエラーのエラー率の測定をデッキ（パルステック社製ＤＤＵ−１０００）で行ったところ、本発明の実施例で得られたＤＶＤディスクは、通常の透明基板のディスクと同等の特性を示した。
【０１２５】
なお表１〜表５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：光学記録媒体用ポリカーボネート樹脂ペレット（帝人化成（株）製、「パンライト ＡＤ−５５０３」、かかるポリカーボネート樹脂の粘度平均分子量は１５，３００であった）
ＰＣ−２：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し、安定剤としてトリス−２，４−ジ−ｔｅｒｔ−ブチルフェニルホスファイトを０．００２５重量％含有する）
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（離型剤として酸価０．８かつ純度９７．５％のステアリン酸モノグリセリドを０．０５５重量％、および安定剤としてトリス−２，４−ジ−ｔｅｒｔ−ブチルフェニルホスファィトを０．００２５重量％含有する）
ＰＣＣ−１：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し、安定剤としてトリス−２，４−ジ−ｔｅｒｔ−ブチルフェニルホスファイトを０．００２５重量％含有する）
ＰＣＣ−２：上記ＰＣＣ−１に、酸価０．８かつ純度９７．５％のステアリン酸モノグリセリドを０．０５５重量％およびトリメチルホスフェートを０．００５重量％の割合となるように配合し、ＰＣ−１を製造する場合と同様の装置および環境下で製造された芳香族ポリカーボネート共重合体ペレット
ＰＯ−１：非晶性ポリオレフィン樹脂（日本ゼオン（株）製「ゼオネックスＥ４８Ｒ」
ＰＯ−２：上記ＰＯ−１ををシクロへキサンに溶解した後、かかる溶液をメタノール中に滴下して得られた樹脂パウダー
【０１２６】
（Ｂ成分）
赤染料Ｆ−１：ペリレン系蛍光赤染料、ＢＡＳＦ社製 Ｌｕｍｏｇｅｎ Ｆ Ｒｅｄ３００
赤染料Ｆ−２：クマリン系蛍光赤染料、バイエル社製 Ｍａｃｒｏｌｅｘ Ｆｌｕｏｒｅｓｃｅｎｔ Ｒｅｄ Ｇ
赤染料Ｆ−３：チオインジゴ系蛍光赤染料、有本化学（株）製 Ｐｌａｓｔ Ｒｅｄ Ｄ５４
黄染料Ｆ−１：クマリン系蛍光黄染料、バイエル社製 Ｍａｃｒｏｌｅｘ Ｆｌｕｏｒｅｓｃｅｎｔ Ｙｅｌｌｏｗ １０ＧＮ
赤染料−４：ペリノン系赤染料、有本化学（株）製 Ｐｌａｓｔ Ｒｅｄ ８３１５
赤染料−５ペリノン系赤染料、紀和化学（株）製 Ｋｐ Ｐｌａｓｔ Ｒｅｄ ＨＧ
赤染料−６ペリノン系赤染料、紀和化学（株）製 Ｋｐ Ｐｌａｓｔ Ｒｅｄ Ｈ２Ｇ
赤染料−７：アンスラキノン系赤染料、有本化学（株）製 Ｐｌａｓｔ Ｒｅｄ８３２０
オレンジ染料−１：ペリノン系オレンジ染料、有本化学（株）製 Ｐｌａｓｔ Ｏｒａｎｇｅ ８１５０−２
黄染料−２：複素環系（含窒素キノリン系）黄染料、有本化学（株）製 Ｐｌａｓｔ Ｙｅｌｌｏｗ ８０１０
黄染料−３：複素環系（含窒素キノリン系）黄染料、有本化学（株）製 Ｐｌａｓｔ Ｙｅｌｌｏｗ ８０５０
青染料−１：アンスラキノン系青染料、バイエル社製 Ｍａｃｒｏｌｅｘ Ｂｌｕｅ ＲＲ
緑染料−１：アンスラキノン系緑染料、住友化学（株）製 ＳｕｍｉｐｌａｓｔＧｒｅｅｎ Ｇ
【０１２７】
【発明の効果】
本発明の着色剤マスターバッチを用いることにより、良好な着色された光学用樹脂成形品を得ることが可能となる。特にかかるマスターバッチは、高密度の光記録媒体である各種ＤＶＤまたは記録層の保護が重要なＣＤ−Ｒ等の光記録媒体に対する着色に対して好適である。かかる点から従来意匠性の乏しかった光学用樹脂成形品の分野、特に今後多大な需要が予想される高密度光記録媒体の分野において格別な工業的効果を奏するものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a colorant masterbatch used for producing a colored optical resin molded product. Specifically, the present invention relates to a colorant masterbatch that contains a colorant in a specific high concentration and is suitable for obtaining a colored optical resin molded product. More specifically, the present invention relates to a colorant masterbatch capable of imparting functions such as design properties and recording storability to a high-performance optical recording medium substrate such as DVD and CD-R.
[0002]
[Prior art]
Optical resin molded articles having various optical functions are usually colorless and transparent or nearly transparent. However, a colored molded product may be used depending on the application. In particular, recently colored products are increasing in optical recording media represented by CD (compact disc) and DVD (digital versatile disc). The purpose of such coloring is in design properties and long-term storage properties of the recording film.
[0003]
Regarding the coloring of such an optical recording medium, JP-A-8-124212 describes an optical recording medium colored using a liquid colorant in which a dye is dispersed in a dispersion medium. Further, in this publication, the coloring method using such a liquid colorant is superior in the dispersibility of the dye as compared with the coloring method using a masterbatch and the like, and is suitable for coloring an optical recording medium. Has been explained. That is, it is described that when a dye masterbatch is used, dilution problems and contamination problems are likely to occur.
[0004]
However, when more types of coloring are required, or when coloring various optical recording media such as various DVDs, which are high-density optical recording media, and CD-Rs where recording layer protection is important, liquid colorants are used. The method used is not necessarily the preferred method.
[0005]
The first reason for this is the stability of the liquid colorant. While the liquid colorant can maintain good dispersion of the dye, reflowing is likely to occur due to its high fluidity, and sufficient consideration is required for long-term storage. That is, the dispersion medium can be an unstable factor with respect to the stability of the dispersion form. Furthermore, when the colorant is diversified, the burden of cost and risk for such consideration becomes larger.
[0006]
The second reason is the heat resistance of the liquid colorant. Particularly in recent years, the temperature at which a recording medium is molded has become extremely high as the recording density of DVDs and the like increases.
Such a high temperature condition may cause decomposition of the dispersion medium, decomposition due to interaction between the dispersion medium and the dye, or the like. That is, the dispersion medium can be an unstable factor for the thermal stability of the material. Further, such decomposition components may induce deterioration of other components.
Such a point is not preferable in a CD-R or the like where it is desired to eliminate the deterioration factor of the recording layer as much as possible.
[0007]
As shown above, the coloring method using a liquid colorant always has a dispersion form derived from the dispersion medium and an unstable factor with respect to heat, and various coloring and high density optical recording which are future needs. It could not be said that it could sufficiently cope with coloring on the medium.
Therefore, from this point of view, the possibility of other coloring methods is conceivable, but there has been no proposal of this point sufficiently clearly.
[0008]
[Problems to be solved by the invention]
An object of the present invention is to provide a colorant masterbatch for obtaining an optical resin molded product suitable for producing a colored optical resin molded product such as a colored DVD substrate or a CD-R substrate. It is what. As a result of diligent studies to achieve the above object, the present inventor tried to obtain a colored optical resin molded product using a masterbatch containing a specific amount of a colorant at a high concentration. As a result, it has been found that the unstable factor of the dispersion medium in the liquid colorant can be removed, and that the problem of dilution unevenness and contamination can be sufficiently solved. Based on these findings, the present invention has been completed.
[0009]
[Means for Solving the Problems]
  The present inventionAromatic polycarbonateFrom resin (component A) and colorant (component B)RuColorant masterbatch for optical molded products,Optical recording medium substrate molded from mixture with aromatic polycarbonate resinAnd the B component content of the master batch isOptical recording medium substrate3 to 30 times the B component contained thereinOptical recording medium substrateIt depends on.
[0010]
Examples of the optical resin molded product of the present invention include an optical recording medium substrate, a lens, an optical filter, an optical fiber, an optical waveguide, an optical prism, and a microlens. In particular, an optical recording medium substrate is an object of the present invention. Is preferred.
[0011]
Further, the optical recording medium of the present invention includes compact discs (CD, CD-R, CD-RW, etc.), magneto-optical discs (MO, MD, etc.), digital versatile discs (DVD-ROM, DVD-Video, DVD-). An optical disk represented by Audio, DVD-R, DVD-RAM, etc.) and an optical card. In particular, an optical disk is a suitable target.
[0012]
The optical resin molded product of the present invention is colored with a colorant according to various purposes. Examples of such purposes include imparting design properties, protecting highly light-degradable portions (by cutting off harmful wavelength rays), identifying product types, and selecting light of a specific wavelength.
[0013]
The colorant masterbatch for optical molded products of the present invention comprises a thermoplastic resin (component A) and a colorant (component B), and the B component content of the masterbatch is in the optical resin molded product by weight ratio. It is characterized by being 3 to 30 times the B component contained in. The B component content is more preferably 3 to 25 times, still more preferably 3.5 to 20 times, and particularly preferably 4 to 18 times by weight.
[0014]
Therefore, the colorant master batch for optical molded articles of the present invention is diluted 3 to 30 times according to the colorant concentration. That is, generally, such a master batch and an uncolored optical material as a main raw material are mixed to obtain a colored optical resin molded product through a process such as melt molding. The main optical material is generally not colored, but it can be used even if it is colored.
[0015]
The colorant masterbatch for optical molded articles of the present invention does not have an adversely affecting dispersion medium component, and has no problem of reaggregation because the dye is dispersed in the solid. Further, it is important that a good optical resin molded product is formed when the concentration of the colorant in the colorant master batch, in other words, the dilution ratio of the optical resin material of the present invention is within a specific range.
[0016]
When the colorant contained in the colorant masterbatch for optical molded products of the present invention is less than 3 times the colorant in the obtained optical resin molded product, contamination problems are likely to occur, which is not preferable. . In the production of the colorant masterbatch, compared with the case of producing a conventional colorless and transparent optical resin material, the number of components increases and the production process also increases, so the probability of contamination is greatly increased. Therefore, the higher the concentration of the colorant master batch, the more preferable it is based on the point of contamination.
[0017]
On the other hand, when the colorant contained in the optical resin material of the present invention exceeds 30 times the colorant in the obtained optical resin molded product, a problem occurs in the function of the optical recording medium. This may be due to the possibility of uneven dilution at the micro level or the possibility that the dye itself tends to deteriorate at high temperatures because the concentration of the dye in the optical resin material increases.
[0018]
Examples of the thermoplastic resin forming the optical resin molded article of the present invention include various resins that can be used for optical applications. Specific examples include aromatic polycarbonate resins, amorphous polyolefin resins, acrylic resins, hydrogenated polystyrene resins, amorphous polyester resins, and amorphous polyarylate resins. Further preferred in the present invention are aromatic polycarbonate resins, amorphous polyolefin resins, and amorphous polyarylate resins that require a high molding temperature. Of these, an aromatic polycarbonate resin is suitable as a thermoplastic resin for forming the optical resin molded product of the present invention.
[0019]
As an amorphous polyolefin resin, Mitsui Chemicals Co., Ltd. APO resin, JSR Co., Ltd. Arton, Nippon Zeon Co., Ltd. ZEONEX etc. can be mentioned. An aromatic polycarbonate resin is particularly preferable. The details of the aromatic polycarbonate resin will be described later.
[0020]
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.
[0021]
Specific examples of the B component dye include CI Solvent Red 52, CI Solvent Red 149, CI Solvent Red 150, CI Solvent Red 191, CI Solvent Red 151, CI Solvent Red 135, CI Solvent Red 168C, CI Solvent Red 168 Solvent Blue 94, CI Solvent Blue 97, CI Solvent Violet 13, CI Solvent Violet 14, CI Disperse Violet 28, CI Solvent Green 3 and CI Solvent Green 3, CI Solvent Green ge 2, pyranthrone anthraquinone dyes known as CI Vat Orange 4, isodibenzanthrone anthraquinone dyes, dibenzpyrenequinones anthraquinone dyes known as CI Vat Orange 1, CI Vat Yellow 4, etc. Can be mentioned. Examples of thioindigo dyes include CI Vat Red 1, 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, CI Solvent Green 5, and BASF's LUMOGEN series, F Orange 240, F Red 300, F Yellow 083, and F Red 339. As the coumarin-based dyes, Bayer's MACROLEX Fluorescent Yellow 10GN, Solvent Yellow 160: 1, MACROLEX Fluorescent Red G, and the like as quinoline dyes, CI SolventYellow 33, CI Solvent Yellow 157D, CI Solvent Yellow 157D Can be mentioned. Examples of perinone dyes include CI Solvent Red 135, CI Solvent Red 179, and CI Solvent Orange 60. Examples of phthalocyanine dyes include CI Pigment Blue 15: 1, CI Pigment Green 7, and CI Pigment Green 36. These can be used alone or in combination of two or more, and can be colored according to the purpose.
[0022]
The colorant preferably has a small particle size in order to achieve sufficiently uniform dispersion, and more preferably has a particle size of 50 μm or less. Such colorant is purified and crystallized after selection by various filters. Can be obtained.
[0023]
The A component which is a thermoplastic resin that forms the colorant masterbatch of the present invention can include the thermoplastic resins listed above. As the component A, basically, the same kind of thermoplastic resin as that of the optical resin molded product is preferably used. However, if the component A is compatible and different in type, it becomes transparent (for example, an aromatic polycarbonate resin and an amorphous resin). A polymer alloy of a conductive polyarylate resin, etc., or when the same type is compatible and transparent (for example, a polymer alloy of a bisphenol A type polycarbonate polymer and a polycarbonate polymer or copolymer of another dihydric phenol). May be part of the resin.
[0024]
Further, when the thermoplastic resin used for the component A is the same as the thermoplastic resin in the optical resin molded article, it is preferable that the molecular weight and molecular weight distribution are close.
[0025]
Moreover, the coloring agent masterbatch which contained all the coloring agents contained in the obtained optical resin molding as a B component is the most preferable. This is because problems such as contamination can be avoided as much as possible. However, it is also possible to combine two or more master batches.
[0026]
The colored optical resin molded product of the present invention contains 0.005 to 10% by weight of a colorant, preferably 0.02 to 5% by weight, more preferably 0.02 to 2% by weight. The main target. With such a colorant content, it is usually recognized that the colorant has been clearly colored, and the functions required of the colorant can be sufficiently exhibited. When the colorant exceeds 10% by weight, the properties as an optical resin molded product are affected, which is not preferable.
[0027]
Various forms and methods can be used for the form of the colorant masterbatch of the present invention and the production method thereof. The form of the colorant masterbatch can take any form of a granular material and a pellet, but a pellet form is particularly preferable. In the case of granular materials, it is necessary to manufacture optical resin molded products in consideration of problems such as oxidative deterioration due to air contained in minute components and problems such as heat deterioration components that adhere to the supply ports of molding machines. There is.
[0028]
Pellets can be obtained by the most common method of cutting melt extruded strands. Accordingly, examples of the shape include a columnar shape and a prismatic shape. It is also possible to take a so-called hot cut method in which the molten extrudate is directly cut. In such a case, it is common to take a shape close to a sphere.
[0029]
As described above, the colorant master batch of the present invention can take any form or shape, but preferably has the same form and shape as the optical material of the main raw material. In such a case, the problem of classification during mixing hardly occurs. Therefore, the colorant master batch is in the form of pellets, and more preferably a cylindrical shape. This is because most of the main optical materials are cylindrical pellets. The size is preferably about the same as the main optical material from the viewpoint of classification. In general, an inner diameter of 2.0 to 3.3 mm and a length of 2.5 to 3.5 mm are suitable.
[0030]
Examples of a method for producing such a colorant master pellet include the following methods. For example, (1) a method in which necessary raw materials (A component, B component and other optional components) are premixed and then melt-kneaded, and (2) a master agent containing a colorant at a high concentration is prepared and other raw materials are used. A method of premixing and then melt-kneading, and (3) a method of independently supplying a master agent containing a colorant at a high concentration and other raw materials and melt-kneading.
[0031]
Specific examples of the premixing method of (1) above include a method in which each component is put into a mixer such as a super floater, a Henschel mixer, a Nauter mixer, and a tumbler and stirred and mixed. Moreover, after dissolving B component uniformly in the solution of A component, the method of removing a solvent can also be mentioned.
[0032]
In the method (2), the master agent and other raw materials are premixed and melt-kneaded using the same mixer as in (1).
[0033]
In the method (3), the master agent and other raw materials are independently supplied to the melt-kneader. In such a case, in addition to charging other raw materials into a melt kneader such as an extruder, in the case of a resin produced by melt polymerization, a method such as charging a master agent at any stage during the polymerization It can also be taken.
[0034]
Here, the master agent used to produce the above colored master pellets (hereinafter simply referred to as “master agent”) can take the form of pellets or particles, but such a master agent. Is preferably in the form of a granular material. This is because in the case of the pellet form, it is necessary to melt and mix a very high concentration of the colorant and the thermoplastic resin, which facilitates the thermal deterioration of the colorant. That is, in such a master agent, it can be said that a method capable of avoiding an excessive heat load as much as possible is more preferable.
[0035]
In order to prepare a powdery master agent, first, a method of mixing a colorant and other raw materials necessary for the preparation of the master agent using a powder mixer such as a Henschel mixer can be mentioned. A super floater is particularly preferable as the mixer.
Such a colorant may be in the form of a liquid that is dissolved or dispersed in another medium in addition to a normal solid form. In the case of a liquid, it is preferable to evaporate the medium by setting the heat generated during mixing and the jacket temperature of the mixer. In the case of a liquid, there is an advantage that such a liquid can be filtered to remove necessary foreign substances and poorly dispersed components at the same time.
[0036]
As a second method for preparing a granular master agent, a method of simultaneously removing a solvent component from a liquid higher concentration master agent and other raw material solution, or in a solution of other raw material Examples include a method of dissolving and removing a solvent component. The solution of the master agent and other raw materials can be mixed or independently fed into the solvent removal apparatus. For example, a master granule can be obtained using a spray dryer.
[0037]
The colorant master batch is preferably produced in an environment that minimizes the presence of foreign substances that hinder the optical characteristics. More specifically, it is necessary to be at the same level as in the case of producing an optical material for an optical recording medium. For example, use a material with a small amount of foreign material as a raw material, install a manufacturing device such as an extruder or pelletizer in an atmosphere of clean air obtained through a filter, etc. Use a material with a small amount of foreign matter such as metal ions obtained through the process, and fill the raw material supply hopper, supply flow path, and the obtained pellet storage tank with clean air. be able to. It is necessary to produce the colorant masterbatch of the present invention in an environment where the level of foreign matters and impurities obtained by these formulations is at the same level as when producing optical materials for optical recording media.
[0038]
Moreover, as an apparatus used for melt-kneading, a screw-type melt-kneading apparatus is preferable. For example, commonly used ones such as a single screw extruder and a twin screw extruder can be used. For the production of pellets, a twin-screw extruder with a vent is particularly preferred, and one that can be evacuated from the vent is preferable.
[0039]
Furthermore, as a more preferable aspect in the present invention, there can be mentioned one in which the content of sodium element contained in the colorant masterbatch is 1 ppm or less. In such a case, various properties required for optical resin molded products, particularly long-term reliability, are sufficiently satisfied. When the content of sodium element in the colorant masterbatch is 1 ppm or less, even when the colorant is included, optical foreign matter is less likely to be generated in long-term use, and better colored optical resin molding Product can be achieved. That is, since the colorant is sensitive to light stimulation, the colorant may cause a long-term generation of optical foreign matter. However, in the present invention, it has also been found that by making the amount of sodium element in the colorant masterbatch extremely small, the generation of optical foreign matters in such long-term use can be further reduced. Although the cause of this is not clear, a group reactive with a sodium atom contained in the colorant (hydroxyl group, halogen atom group, ester bond, etc.) produces a colorant masterbatch, and optical resin molded product It is thought that the deterioration factor is generated by passing through the process of molding the material and two thermal histories.
[0040]
In order to obtain such a colorant masterbatch, it is important to use raw materials used for optical resin molded products, in particular, thermoplastic resins as component A and colorants as component B that do not contain sodium element as much as possible. It is.
[0041]
In the case of a thermoplastic resin, a sodium compound is mixed mainly due to a polymerization catalyst, water used in a water washing process, and the like. In the case of a production method in which the catalyst cannot be removed, it is preferable to adjust the amount of the catalyst so that the sodium element is 1 ppm or less in order to obtain an optical resin molded article. On the other hand, when it can be removed by washing with water or the like, it is preferable to use water from which sodium ions have been removed with an ion exchange membrane or the like and to sufficiently remove sodium element by sufficient washing with water. In addition, when forming pellets, when cooling with water, it is preferable to sufficiently remove sodium ions from the water.
[0042]
As for the colorant, as in the case of the thermoplastic resin, when used as a catalyst, it is preferable to sufficiently reduce the amount of sodium element with careful consideration of the amount thereof. In the case where it can be removed by the purification step, it is preferable to carry out the purification step twice or more to eliminate the sodium element as the purity is improved. It is also important to use a colorant that does not substantially contain sodium as a constituent atom.
[0043]
Details of the aromatic polycarbonate resin suitable as the resin for forming the optical resin molded product 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.
[0044]
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.
[0045]
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 preferable. Furthermore, a homopolymer of bisphenol A, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) A copolymer with one or more monomers selected from phenyl} propane and α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene is preferably used, and 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 are preferred.
[0046]
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.
[0047]
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.
[0048]
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.
[0049]
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.
[0050]
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.
[0051]
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).
[0052]
[Chemical 1]

[0053]
(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.)
[0054]
Specific examples of the monofunctional phenols include phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.
[0055]
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.
[0056]
[Chemical 2]

[0057]
[Chemical Formula 3]

[0058]
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.)
[0059]
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.
[0060]
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.
[0061]
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.
[0062]
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.
[0063]
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.
[0064]
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.
[0065]
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.
[0066]
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.
[0067]
Among the quenching agents, those of phosphonium salt or ammonium salt type are preferred.
The amount of the catalyst is preferably 0.5 to 50 mol with respect to 1 mol of the remaining catalyst, and 0.01 to 500 ppm, more preferably 0 with respect to the polycarbonate resin after polymerization. 0.01 to 300 ppm, particularly preferably 0.01 to 100 ppm.
[0068]
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 has sufficient strength as an optical resin molded product, and can reduce optical distortion and birefringence as much as possible. 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
[0069]
As described above, the polycarbonate resin uses a sodium compound as a catalyst in the production thereof. Therefore, in the case of interfacial polycondensation, sufficient water washing is performed. The content of sodium element in the polycarbonate resin itself is 0.5 ppm or less, preferably 0.3 ppm or less, particularly preferably 0.2 ppm or less.
[0070]
When an aromatic polycarbonate resin is used as the component A of the colorant masterbatch, the viscosity average molecular weight in the colorant masterbatch is 1, as the absolute value of the difference from the viscosity average molecular weight of the aromatic polycarbonate resin as the main raw material. It is preferable to be in the range of 000 or less. More preferably, it is the range within 800, More preferably, it is the range within 500. In particular, it is preferable that such a difference is small in an optical recording medium. In the case of an optical recording medium, the molding cycle is extremely short, and the plasticizing process is almost complete. Therefore, the presence of a component having a non-uniform melt plasticization behavior increases the non-uniformity of the material and causes problems such as poor dispersion of the colorant.
[0071]
The optical resin molded product of the present invention may contain various heat stabilizers, mold release agents, antistatic agents, light stabilizers, and the like. Therefore, the colorant master batch of the present invention further includes these. It is possible to contain the component at a high concentration as long as the object of the present invention is not impaired.
[0072]
As the release agent, various release agents can be used, but fatty acid esters are preferable. Examples of the fatty acid ester include an ester of an aliphatic saturated monovalent carboxylic acid having 6 to 34 carbon atoms and a monohydric or dihydric or higher polyhydric alcohol. Such aliphatic saturated monovalent carboxylic acids include caproic acid, caprylic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, araxic acid, Examples include behenic acid and montanic acid.
[0073]
Specific examples of esters of monohydric alcohol and saturated fatty acid include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate and the like.
[0074]
Specifically, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetraester as partial ester or total ester of polyhydric alcohol and saturated fatty acid Dipentaerythritol total ester or partial ester such as stearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, dipentaerythritol hexastearate .
[0075]
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. Examples of the dihydric or higher polyhydric alcohol include ethylene glycol, glycerin, pentaerythritol and the like. Particularly preferred is a partial ester of stearic acid and glycerin.
[0076]
The release agent is preferably 90% by weight or more, more preferably 95% by weight or more, particularly preferably substantially only the fatty acid ester, based on 100% by weight of the release agent. It is.
[0077]
Further, the acid value of the fatty acid ester is preferably 3 or less, and more preferably 2 or less.
In the case of glycerin monostearate, an acid value of 1.5 or less and a purity of 95% by weight or more are preferred. More preferred glycerin monostearate has an acid value of 1.2 or less and a purity of 98% by weight or more. A known method can be used for measuring the acid value of the fatty acid ester.
[0078]
The composition ratio of the release agent is preferably 0.005 to 0.5% by weight, more preferably 0.01 to 0.2% by weight, in 100% by weight of the optical resin molded product.
[0079]
Preferable examples of the heat stabilizer include phosphorus stabilizers. As the phosphorus stabilizer, any of phosphite, phosphonite, and phosphate can be used.
[0080]
Various phosphite stabilizers can be used in the present invention. Specifically, for example, the general formula (4)
[0081]
[Formula 4]

[0082]
[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.
[0083]
Moreover, as a more preferable aspect in General formula (4), following General formula (5)
[0084]
[Chemical formula 5]

[0085]
[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.
[0086]
Further, the general formula (6)
[0087]
[Chemical 6]

[0088]
[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.
[0089]
Further, the general formula (7)
[0090]
[Chemical 7]

[0091]
[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.
[0092]
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).
[0093]
[Chemical 8]

[0094]
[Chemical 9]

[0095]
[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. ]
[0096]
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.
[0097]
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.
[0098]
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.
[0099]
Preferable specific examples of the phosphite compound corresponding to the general formula (7) include 4,4'-isopropylidenediphenol tetratridecyl phosphite.
[0100]
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.
[0101]
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.
[0102]
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.
[0103]
In the optical resin molded article of the present invention, an antioxidant generally known for the purpose of preventing oxidation may be contained. Examples of such antioxidants include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetra (β-lauryl thiopropionate) ester, glycerol-3-stearyl thiopropionate, triethylene glycol-N—. Bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] Tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane, n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) ) Propionate, 1,3,5-trimethyl-2 4,6-tris (3,5-di-tert-butyl-4-hydroxy-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydrocinnamide), 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 and the like.
[0104]
The heat stabilizer is preferably contained in an amount of 0.0001 to 0.1 parts by weight, more preferably 0.0005 to 0.05 parts by weight, even more preferably, per 100 parts by weight of the optical resin molded product of the present invention. Is 0.001 to 0.03 parts by weight. Moreover, 0.001-0.05 weight part of the said antioxidant is preferable per 100 weight part of optical resin molded products of this invention.
[0105]
Various methods known in the art can be used as a method for obtaining an optical resin molded product using the colorant masterbatch of the present invention. For example, it is molded into a desired shape by a method such as injection molding, extrusion molding or compression molding. can do. Particularly preferred is injection molding, and the colorant masterbatch of the present invention is fully compatible with such injection molding. That is, it is suitable for a molding method of an optical recording medium or the like that has a very short molding cycle and a short plasticization time.
[0106]
As a method of supplying the colorant masterbatch of the present invention and the optical material that is the main raw material to a molding processing machine such as an injection molding machine, a method of supplying them as a mixture thereof, or supplying a specific amount of each independently, Any method of mixing in an injection molding machine or the like can be performed. The preparation of the mixture can be performed by a method of mixing a predetermined ratio by a batch method, a method of continuously supplying each to a mixer with a weighing machine, and obtaining a mixture.
[0107]
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 are as follows.
[0108]
(1) Optical disk appearance observation
The optical disk produced as an evaluation sample was visually observed and classified according to the following criteria.
○: Appearance is good
×: Appearance defects such as color unevenness and color streaks
[0109]
(2) BLER measurement
The BLER of each sample was measured with respect to the CD disk sample with a BLER measuring device (manufactured by SONY, CD player control unit CDS-3000). In Table 3, C₁AVE is the average value per second of C1 errors (random errors that can be corrected with C1 code).
[0110]
(3) Measurement of sodium element content in disk substrate sample
0.5 g of the polymer collected from the disk substrate sample was dissolved in 25 g of 1-methyl-2-pyrrolidone for electronics industry, and the solution was subjected to measurement using ICP-MS, SPQ-9000 manufactured by Seiko Electronics Industry Co., Ltd.
[0111]
[Reference Examples 1 to 19]
(Manufacture of colorant master pellets)
Each component described in Table 1 and Table 2 was produced in the following manner, and various evaluations were performed. The colorant component described in Table 1 and the powder component of the A component were uniformly mixed with a super floater to obtain a master agent. Such a master agent was mixed with the remaining component A so as to have the composition ratios shown in Tables 1 and 2, and uniformly mixed with a V-type blender with comb teeth.
This mixture was melt kneaded at a cylinder temperature of 260 ° C. while being evacuated from the vent with a vented twin screw extruder (Kobe Steel Works KTX-30) with a diameter of 30 mmφ, and the resulting strand was cooled with cooling water. And pelletized with a pelletizer. The temperature of the pellet immediately after pelletizing was about 129 ° C.
[0112]
Further, a sintered metal 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 1.005 atm where clean air passed through a filter circulated, and water for strand cooling was passed through a 1 μm filter, and ion exchange water passed through an ion exchange membrane was used. .
[0113]
[Table 1]

[0114]
[Table 2]

[0115]
[Examples 1 to 8 and Comparative Example 1]
The colorant master pellets obtained above and the optical material pellets as the main raw material were put into the hopper of the molding machine by automatic conveyance from each tank through the measuring machine so as to have the ratio shown in Table 3. In addition, a mixing zone was provided immediately after the colorant master pellet conveyance tube, and after making a uniform mixed pellet, it was put into a hopper of a molding machine. The pellets were dried with hot air at 120 ° C. for 5 hours in a clean oven before being put into the tank.
[0116]
On the other hand, an injection molding machine (DISK3 M3 manufactured by Sumitomo Heavy Industries, Ltd.) is attached with a CD mold, and a nickel CD stamper with pits is attached to this mold to automatically convey the molding material. This was put into a hopper of a molding machine, and a substrate having a diameter of 120 mm and a thickness of 1.2 mm was formed under the 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 3.9 MPa. A CD disk was obtained by sputtering an aluminum film. Table 3 shows the evaluation results of these CD discs.
[0117]
[Table 3]

[0118]
[Examples 9 to 11 and Comparative Example 2]
The colorant master pellets and the main raw material pellets are automatically conveyed to the hopper of an injection molding machine in the same manner as in Example 1 except that the mold temperature is set to 115 ° C., and a disk substrate is molded. A recording layer and a metal reflective film were formed to produce a CD-R disc. Table 4 shows the evaluation results of the obtained CD-R disc.
[0119]
[Table 4]

[0120]
Furthermore, as a result of performing a light resistance test in which the recording surface of the CD-R disk is pasted on a window glass so that the sunlight hits through the substrate and the number of days until an abnormality occurs in writing / reading, the colored disk of the embodiment of the present invention is obtained. It had light resistance more than double that of a normal transparent substrate disk.
[0121]
[Examples 12 to 16 and Comparative Example 3]
In the same manner as in Example 1, the colorant master pellets and the main raw material pellets were automatically conveyed to a hopper of an injection molding machine.
[0122]
On the other hand, a DVD-only mold was attached to the injection molding machine, and a nickel DVD-ROM stamper containing information such as an address signal was mounted on the mold. An optical disk substrate having a diameter of 120 mm and a wall thickness of 0.6 mm was obtained from the pellets under the conditions of a cylinder temperature of 380 ° C., a mold temperature of 115 ° C., an injection speed of 300 mm / sec, and a holding pressure of 3.9 MPa. Thereafter, an aluminum film was sputtered onto the substrate, and a UV curable adhesive was applied and adhered by spin coating to obtain a bonded optical disk. Table 5 shows the evaluation results of the obtained DVD-ROM disc.
[0123]
[Table 5]

[0124]
Further, when the error rate of the PI error was measured with a deck (DDU-1000 manufactured by Pulse Tech Co., Ltd.) for such a DVD disk, the DVD disk obtained in the example of the present invention was a normal transparent substrate disk. Equivalent characteristics were shown.
[0125]
In addition, the symbol and item which show each component of Table 1-Table 5 are as follows.
(Component A)
PC-1: polycarbonate resin pellet for optical recording medium (manufactured by Teijin Chemicals Ltd., “Panlite AD-5503”, the viscosity average molecular weight of this polycarbonate resin was 15,300)
PC-2: Bisphenol A polycarbonate resin powder obtained by the phosgene method not using an amine catalyst having a viscosity average molecular weight of 15,200 (p-tert-butylphenol is used as a terminal stopper and Tris-2,4 is used as a stabilizer) -Containing 0.0025% by weight of di-tert-butylphenyl phosphite)
PC-3: 2 × 10 disodium salt of bisphenol A as a transesterification catalyst having a terminal hydroxyl group concentration of 34 mol% and a viscosity average molecular weight of 15,300 with respect to 1 mol of raw material bisphenol A^-7Bisphenol A polycarbonate resin pellets obtained by a melt transesterification method using a mole (0.055% by weight of stearic acid monoglyceride having an acid value of 0.8 and a purity of 97.5% as a release agent, and Tris as a stabilizer (Contains 0.0025% by weight of 2,4-di-tert-butylphenyl phosphate)
PCC-1: 1,1-bis (4-hydroxyphenyl) -3,3,5- of the wholly aromatic dihydroxy component obtained by the phosgene method using an amine catalyst having a viscosity average molecular weight of 14,800 Aromatic polycarbonate copolymer powder containing 45 mol% of trimethylcyclohexane [bisphenol TMC] and 55 mol% of 4,4 '-(m-phenylenediisopropylidene) diphenol [bisphenol M] (p- tert-butylphenol is used and 0.0025% by weight of tris-2,4-di-tert-butylphenyl phosphite is used as a stabilizer)
PCC-2: The above-mentioned PCC-1 was mixed with stearic acid monoglyceride having an acid value of 0.8 and a purity of 97.5% in a proportion of 0.055% by weight and trimethyl phosphate in a proportion of 0.005% by weight. Aromatic polycarbonate copolymer pellets produced under the same equipment and environment as in producing -1.
PO-1: Amorphous polyolefin resin ("Zeonex E48R" manufactured by Nippon Zeon Co., Ltd.)
PO-2: Resin powder obtained by dissolving the above PO-1 in cyclohexane and then dropping the solution into methanol.
[0126]
(B component)
Red dye F-1: Perylene-based fluorescent red dye, Lumogen F Red300 manufactured by BASF
Red dye F-2: Coumarin fluorescent red dye, Macrolex Fluorescent Red G, manufactured by Bayer
Red dye F-3: thioindigo fluorescent red dye, Arimoto Chemical Co., Ltd., Red Red D54
Yellow dye F-1: Coumarin-based fluorescent yellow dye, Macrolex Fluorescent Yellow 10GN, manufactured by Bayer
Red dye-4: Perinone red dye, Arimoto Chemical Co., Ltd. Plast Red 8315
Red dye-5 perinone red dye, Kp Plastic Red HG manufactured by Kiwa Chemical Co., Ltd.
Red Dye-6 Perinone Red Dye, manufactured by Kiwa Chemical Co., Ltd. Kp Plas Red H2G
Red dye-7: Anthraquinone red dye, Arimoto Chemical Co., Ltd. Plast Red 8320
Orange dye-1: Perinone-based orange dye, Aramoto Chemical Co., Ltd., Plas Orange 8150-2
Yellow dye-2: heterocyclic (nitrogen-containing quinoline) yellow dye, Arimoto Chemical Co., Ltd. Plast Yellow 8010
Yellow dye-3: heterocyclic (nitrogen-containing quinoline) yellow dye, Arimoto Chemical Co., Ltd. Plast Yellow 8050
Blue dye-1: Anthraquinone blue dye, manufactured by Bayer, Macrolex Blue RR
Green dye-1: Anthraquinone green dye, Sumitlast Green G manufactured by Sumitomo Chemical Co., Ltd.
[0127]
【The invention's effect】
By using the colorant masterbatch of the present invention, it becomes possible to obtain an excellent colored resin molded product for optics. In particular, such a master batch is suitable for coloring various optical recording media such as various DVDs that are high-density optical recording media or CD-Rs in which protection of the recording layer is important. From this point of view, the present invention has a remarkable industrial effect in the field of optical resin molded articles that have been poor in design, in particular in the field of high-density optical recording media, for which a great demand is expected in the future.

Claims (5)

An aromatic polycarbonate resin (A component) and the colorant (B component) Tona Ru optical moldings coloring agent master batch, an optical recording medium substrate which is molded from a mixture of an aromatic polycarbonate resin, said masterbatch an optical recording medium substrate, wherein the component B content is 3 to 30 times the B component contained in the optical recording medium substrate by weight. Colored optical recording medium substrate, the optical recording medium substrate according to claim 1 comprising a colorant 0.005 wt%. The optical recording according to claim 1, wherein the component B is at least one selected from anthraquinone dyes, perinone dyes, quinoline dyes, perylene dyes, coumarin dyes, and thioindigo dyes. Medium substrate . The optical recording medium substrate according to any one of claims 1 to 3 , wherein the content of the sodium element contained in the colorant master batch is 1 ppm or less. An optical recording medium formed from the optical recording medium substrate according to claim 1 .