JP3867930B2 - Aromatic polycarbonate composition - Google Patents

Description

【０００９】
で表される繰返し単位［Ｉ］の芳香族ポリカーボネートであって、その芳香族ポリカーボネート０．７ｇを１００ｍｌの塩化メチレンに溶解した２０℃における溶液の比粘度が０．２〜０．４である芳香族ポリカーボネート（ＰＣ−Ｉ）および下記一般式［ＩＩ］
【００１０】
【化４】

【００１１】
で表される繰返し単位［ＩＩ］の芳香族ポリカーボネートであって、その芳香族ポリカーボネート０．７ｇを１００ｍｌの塩化メチレンに溶解した２０℃における溶液の比粘度が０．２〜０．４である芳香族ポリカーボネート（ＰＣ−ＩＩ）より実質的になり、前記芳香族ポリカーボネート（ＰＣ−Ｉ）と前記芳香族ポリカーボネート（ＰＣ−ＩＩ）の割合が重量比で８０：２０〜３０：７０の範囲である芳香族ポリカーボネート組成物が提供される。
【００１２】
本発明の芳香族ポリカーボネート樹脂組成物を形成するＰＣ−ＩおよびＰＣ−ＩＩの製造に用いる二価フェノールとしての２,２−ビス（３−メチル−４−ヒドロキシフェニル）プロパンおよび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はその合成時に副生する不純物を極力除去した９９.０％以上の高純度のものが好ましい。本発明の組成物を形成するＰＣ−Ｉは８０〜３０重量％でありＰＣ−ＩＩは２０〜７０重量％である。ＰＣ−Ｉは７５〜３５重量％、ＰＣ−ＩＩは２５〜６５重量％が好ましい。ＰＣ−Ｉが８０重量％より多くＰＣ−ＩＩが２０重量％より少なくなると得られた樹脂の光弾性定数が大きくなりかつガラス転移点も低くなるので好ましくない。また、ＰＣ−Ｉが３０重量％より少なく、ＰＣ−ＩＩが７０重量％より多くなると得られた樹脂の溶融流動性が悪く成形不良を生じ、光学的に良好な成形品が得られ難くなる。
【００１３】
本発明の芳香族ポリカーボネート樹脂組成物を形成するそれぞれの樹脂は通常の芳香族ポリカーボネート樹脂を製造する際に用いる公知の方法、例えば二価フェノールにホスゲンや炭酸ジエステル等のカーボネート前駆物質を反応させる方法により製造される。
【００１４】
カーボネート前駆物質として例えばホスゲンを使用する反応では、通常酸結合剤の水溶液に上記二価フェノールを溶解し、有機溶媒の存在下に反応させる。酸結合剤としては例えば水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物が用いられ、有機溶媒としては例えば塩化メチレン、クロロベンゼン等のハロゲン化炭化水素が用いられる。反応温度は通常０〜４０℃であり、反応時間は数分〜５時間である。
【００１５】
また、反応を促進させるために触媒を用いてもよく、触媒としては例えばトリエチルアミン、テトラ−ｎ−ブチルアンモニウムブロマイド、テトラ−ｎ−ブチルホスホニウムブロマイドのような三級アミン、四級アンモニウム化合物、四級ホスホニウム化合物等が挙げられる。更に、必要に応じハイドロサルファイトのような酸化防止剤を加えることもできる。
【００１６】
さらに末端停止剤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、イソオクチルフェノール等の単官能フェノール類を用いる。また溶融流動性をさらに向上するためには炭素原子数１０〜５０のアルキルフェノールを全末端停止剤の少なくとも５モル％以上用いると良い。その際用いられる炭素原子数１０〜５０のアルキルフェノールのアルキル基の置換位置は通常水酸基のオルソ位またはパラ位のものが用いられ、中でもオルソ位とパラ位の混合物が好ましく用いられる。
【００１７】
カーボネート前駆物質として炭酸ジエステルを用いるエステル交換反応では、不活性ガス雰囲気下所定割合の上記二価フェノールを炭酸ジエステルと加熱しながら攪拌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ことで行われる。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１２０〜３００℃の範囲である。反応後期には系を減圧に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て反応を完結させる。炭酸ジエステルとしては例えばジ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等が挙げられる。このらのうち特にジフェニルカーボネートが好ましい。
【００１８】
重合速度を速めるために重合触媒を使用することもでき、重合触媒としては水酸化ナトリウムや水酸化カリウム等のアルカリ金属及びアルカリ土類金属の水酸化物類、ホウ素やアルミニウムの水酸化物のアルカリ金属塩、アルカリ土類金属塩、第４級アンモニウム塩類、アルカリ金属及びアルカリ土類金属のアルコキシド類、アルカリ金属及び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、ケイ素化合物類、ゲルマニウム化合物類、有機スズ化合物類、鉛化合物類、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等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使用することができる。触媒は１種だけを用いても２種以上を組合わせて用いてもよい。これらの触媒の使用量は原料の二価フェノールに対し０.０００１〜１重量％、好ましくは０.０００５〜０.５重量％の範囲で選ばれる。
【００１９】
かくして得られるＰＣ−ＩおよびＰＣ−ＩＩのポリマーはいずれもポリマー０.７ｇを１００ｍｌの塩化メチレンに溶解し、２０℃で測定した比粘度が０.２〜０.４の範囲のものが好ましく、０.２５〜０.３５の範囲のものがさらに好ましい。比粘度が０.２未満では成形品が脆くなり、一方、０.４より高くなると溶融流動性が悪く、成形不良を生じ、光学的に良好な成形品が得られ難くなる。
【００２０】
本発明の芳香族ポリカーボネート樹脂組成物は、例えば射出成形法、圧縮成形法、押出成形法、溶液キャスティング法等任意の方法で成形することができる。
なお、本発明の芳香族ポリカーボネート樹脂組成物には、必要に応じてりん系の熱安定剤、フェノール系の酸化防止剤等を加えることができる。りん系の安定剤としては例えばトリフェニルホスファイト、トリスノニルフェニルホスファイト、トリス（２,４−ジ−ｔｅｒｔ−ブチルフェニル）ホスファイト、トリデシルホスファイト、トリオクチルホスファイト、トリオクタデシルホスファィト、ジデシルモノフェニルホスファイト、ジオクチルモノフェニルホスファイト、ジイソプロピルモノフェニルホスファイト、モノブチルジフェニルホスファイト、モノデシルジフェニルホスファイト、モノオクチルジフェニルホスファイト、ビス（２,６−ジ−ｔｅｒｔ−ブチル−４−メチルフェニル）ペンタエリスリトールジホスファイト、２,２−メチレンビス（４,６−ジ−ｔｅｒｔ−ブチルフェニル）オクチルホスファイト、ビス（ノニルフェニル）ペンタエリスリトールジホスファイト、ビス（２,４−ジ−ｔｅｒｔ−ブチルフェニル）ペンタエリスリトールジホスファイト、テトラキス（２,４−ジ−ｔｅｒｔ−ブチルフェニル）−４,４−ジフェニレンホスホナイト等の亜りん酸のトリエステル、ジエステル、モノエステルでありこれらは単独で使用してもまたは２種以上を併用してもよい。添加量としては０.０００１〜０.０５重量％が好ましい。
【００２１】
フェノール系酸化防止剤としては例えばトリエチレングリコール−ビス（３−（３−ｔｅｒｔ−ブチル−５−メチル−４−ヒドロキシフェニル）プロピオネート）、１,６−ヘキサンジオール−ビス（３−（３,５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、ペンタエリスリトール−テトラキス（３−（３,５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート）、オクタデシル−３−（３,５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、１,３,５−トリメチル−２,４,６−トリス（３,５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）ベンゼン、Ｎ,Ｎ−ヘキサメチレンビス（３,５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシ−ヒドロシンナマイド）、３,５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシ−ベンジルホスホネート−ジエチルエステル、トリス（３,５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）イソシアヌレート、３,９−ビス｛１,１−ジメチル−２［β−（３−ｔｅｒｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ］エチル｝−２,４,８,１０−テトラオキサスピロ（５,５）ウンデカン等が挙げられる。好ましい添加量の範囲は０.０００１〜０.０５％である。
【００２２】
また必要に応じて多価アルコールの高級脂肪酸エステルを加える事もできる。
好ましい脂肪酸エステルとしては炭素原子数８〜２２の飽和脂肪族モノカルボン酸とグリコール類、グリセロール、ペンタエリスリトール等との全エステル、部分エステルで、好ましい添加量は０.００１〜０.５重量％である。また光安定剤、着色剤、帯電防止剤、滑剤等の添加剤を透明性を損なわない範囲で加えることができる。また他のポリカーボネート樹脂、あるいは熱可塑性樹脂を少割合ブレンドして用いることもできる。
【００２３】
また本発明の芳香族ポリカーボネート樹脂に含まれる塩素（Ｃｌ）は１.０ｐｐｍ以下が好ましい。また平均径０.５μｍ以上の異物は１００００個／ｇ以下が好ましい。
【００２４】
本発明の芳香族ポリカーボネート組成物は、複屈折性および成形性に特に優れているので種々の成形品として利用することができる。殊に光学ディスク、光学レンズ、液晶パネル、光カード、シート、フィルム、光ファイバー、コネクター、蒸着プラスチック反射鏡、ディスプレー等の光学部品の構造材料または機能材料用途に適した光学用成形品として有利に使用することができる。これらのうち、光ディスク用基板として特に有利に使用することができる。
【００２５】
【実施例】
以下に実施例を挙げて本発明をさらに説明する。なお合成例および実施例中の部は重量部であり％は重量％である。なお、評価は下記の方法によった。
比粘度；
ポリマー０.７ｇを１００ｍｌの塩化メチレンに溶解し２０℃の温度で測定した。
ガラス転移点（Ｔｇ）；
デュポン社製９１０型ＤＳＣにより測定した。
流動性（ＭＦＲ）；
ＪＩＳ Ｋ−７２１０に準拠して、東洋精機製セミオートメルトインデクサーを用いて、２８０℃、荷重２.１６ｋｇで１０分間に流出したポリマー量（ｇ）で示した。
全光線透過率；
ＡＳＴＭ Ｄ−１００３に準拠して日本電色シグマ８０を用いて測定した。
光弾性定数；
理研計器（株）製の光弾性測定装置ＰＡ−１５０により測定した。
斜め入射複屈折位相差；
オーク製エリプソメータＡＤＲ−２００Ｂ自動複屈折測定装置を用い、入射角３０度で測定した。
反り；
８０℃、８５％ＲＨの恒温恒湿機中に光ディスクを１０００時間放置した後、小野測器製ＬＭ−１２００光ディスク検査装置を用いて基板の反りを測定した。
【００２６】
合成例１（ＰＣ−Ｉの合成）
温度計、攪拌機、還流冷却器付き反応器にイオン交換水４３５.４部と４８％カセイソーダ水溶液５５.６部を入れ、２,２−ビス（３−メチル−４−ヒドロキシフェニル）プロパン５７.５部およびハイドロサルファイト０.２部を溶解した後、塩化メチレン４３５.４部を加え、攪拌下１５〜２５℃でホスゲン２９部を４０分を要して吹き込み反応せしめた。ホスゲン吹き込み終了後、ｐ−ｔｅｒｔ−ブチルフェノール１.５部および４８％カセイソーダ水溶液１８.５部を加えて乳化後トリエチルアミン０.１６部を加えて２８〜３３℃で約１時間攪拌して反応を終了した。反応終了後、生成物を塩化メチレンで希釈して水洗したのち塩酸酸性にして水洗し、水相の導電率がイオン交換水と殆ど同じになったところで塩化メチレンを蒸発してポリマー６１.４部を得た（収率９７％）。このポリマーの比粘度は０.３２４、Ｔｇは１２０℃であった。
【００２７】
合成例２（ＰＣ−ＩＩの合成）
合成例１と同様の装置にイオン交換水１１３７.３部、４８％カセイソーダ水溶液２３８.５部を入れ、１,１−ビス（４−ヒドロキシフェニル）−３,３,５−トリメチルシクロヘキサン２００.１部、およびハイドロサルファイト０.２部を溶解した後、塩化メチレン７０９.９部を加えて、合成例１と同様にしてホスゲン８３.１部を４０分を要して吹き込み反応せしめた。ホスゲン吹き込み終了後、ｐ−ｔｅｒｔ−ブチルフェノール５.８部を加え乳化後、トリエチルアミン０.２部を加えて合成例１と同様にしてポリマー２０８.２部を得た（収率９６％）。
このポリマーの比粘度は０.２５８、Ｔｇは２２６℃であった。
【００２８】
合成例３（ＰＣ−ＩＩの合成）
合成例２のｐ−ｔｅｒｔ−ブチルフェノールの代わりに炭素原子数２０のアルキルフェノール（オルソ置換体７０％とパラ置換体３０％の混合物）１４.５部を用いる以外は合成例２と同様にしてポリマー２１７.５部を得た（収率９４％）。このものの比粘度は０.２７２、Ｔｇは１８２℃であった。
【００２９】
実施例１
合成例１で合成したポリカーボネート７０部、合成例２で合成したポリカーボネート３０部、トリス（２,４−ジ−ｔｅｒｔ−ブチルフェニル）ホスファイト０.００５部、トリメチルホスフェート０.００５部、ステアリン酸モノグリセライド０.０４５部を塩化メチレンに均一に溶解した後、塩化メチレンを蒸発してポリマー組成物を得た。このものを２５０℃で溶融押出ししてペレット化した。このもののＴｇは１５０℃、ＭＦＲは５２ｇ／１０分であった。このものを住友重機製ＤＩＳＫ５Ｍｌｌｌを用いて１２０ｍｍφ、１.２ｍｍ厚みのディスク基板に射出成形した。このものの全光線透過率は８９％、光弾性定数は４９×１０^-13ｃｍ²／ｄｙｎ、斜め入射複屈折位相差は２６ｎｍ、反りは０.２ｍｍであった。
【００３０】
実施例２
合成例１で合成したポリマー４０部、合成例３で合成したポリマー６０部を実施例１と同様の添加剤組成で実施例１と同様にしてペレット化した。このもののＴｇは１５５℃、ＭＦＲは４３ｇ／１０分であった。このものを実施例１と同様にしてディスク基板を成形し評価したところ、全光線透過率は８９％、光弾性定数は４３×１０^-13ｃｍ²／ｄｙｎ、斜め入射複屈折位相差は２６ｎｍ、反りは０.２ｍｍであった。
【００３１】
比較例１
通常のビスフェノールＡポリカーボネート（帝人化成製パンライトＡＤ−５５０３）を実施例１と同様のディスク基板を成形し実施例１と同様にして評価したところ全光線透過率は８９％、光弾性定数は８２×１０^-13ｃｍ²／ｄｙｎ、斜め入射複屈折位相差は６８ｎｍ、反りは０.３ｍｍであった。
【００３２】
比較例２
合成例１で合成したポリマー９０部、合成例２で合成したポリマー１０部とした以外は実施例１と同様にしてペレットおよびディスク基板を得た。このもののＴｇは１３０℃と低く、光弾性定数は５６×１０^-13ｃｍ²／ｄｙｎ、斜め入射複屈折位相差は５５ｎｍと大きかった。
【００３３】
比較例３
合成例１で合成したポリマー１０部、合成例２で合成したポリマー９０部とした以外は実施例１と同様にしてペレット化した。このもののＴｇは２２０℃と高くＭＦＲは測定不可能で良好な成形品は得られなかった。
【００３４】
【発明の効果】
本発明の芳香族ポリカーボネート組成物は、低複屈折で溶融流動性が良くかつ透明性にも優れるので、光学ディスク、光学レンズ、光カード等の各種光学用成形品として好適に用いられる。[0001]
[Industrial application fields]
The present invention relates to an aromatic polycarbonate composition. More particularly, the present invention relates to a composition having improved birefringence and moldability formed from two kinds of aromatic polycarbonates, and a molded article therefrom.
[0002]
[Prior art]
Conventionally, polycarbonate resins obtained by reacting 2,2-bis (4-hydroxyphenyl) propane with a carbonate precursor material have excellent transparency, heat resistance, mechanical properties, and dimensional stability. Widely used in many fields. Since it is particularly excellent in transparency, it is often used as an optical material.
[0003]
However, such a polycarbonate resin has a disadvantage that the photoelastic constant is large due to the optical anisotropy of the benzene ring, and therefore the birefringence of the molded product is large, and this improvement is demanded. Further, there is a demand for a resin having a short molding cycle and a better transferability with better melt fluidity.
[0004]
On the other hand, JP-A-2-88634 discloses an aromatic polycarbonate resin obtained from 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane. It is also known that the heat resistance is good with refraction, but the melt flowability is poor and it is difficult to obtain a good molded product.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide an aromatic polycarbonate composition having improved oblique incident birefringence, moldability, warpage and the like while maintaining the excellent transparency and mechanical properties of a polycarbonate suitable for an optical material.
[0006]
As a result of intensive research aimed at achieving this object, the present inventor has found that a composition in which two specific aromatic polycarbonates are mixed at a specific ratio is suitable as an optical material, and has reached the present invention. .
[0007]
[Means for Solving the Problems]
That is, according to the present invention, the following general formula [I]
[0008]
[Chemical 3]

[0009]
An aromatic polycarbonate having a specific viscosity of 0.2 to 0.4 at 20 ° C. in which 0.7 g of the aromatic polycarbonate is dissolved in 100 ml of methylene chloride. Group polycarbonate (PC-I) and the following general formula [II]
[0010]
[Formula 4]

[0011]
An aromatic polycarbonate having a repeating unit [II] represented by the following formula, wherein the specific viscosity of the solution at 20 ° C. obtained by dissolving 0.7 g of the aromatic polycarbonate in 100 ml of methylene chloride is 0.2 to 0.4: A fragrance substantially comprising an aromatic polycarbonate (PC-II), wherein the ratio of the aromatic polycarbonate (PC-I) to the aromatic polycarbonate (PC-II) is in the range of 80:20 to 30:70 by weight ratio. Group polycarbonate compositions are provided.
[0012]
2,2-bis (3-methyl-4-hydroxyphenyl) propane and 1,1-bis as dihydric phenols used in the production of PC-I and PC-II to form the aromatic polycarbonate resin composition of the present invention (4-Hydroxyphenyl) -3,3,5-trimethylcyclohexane preferably has a high purity of 99.0% or more in which impurities generated as a by-product during synthesis are removed as much as possible. PC-I forming the composition of the present invention is 80-30% by weight and PC-II is 20-70% by weight. PC-I is preferably 75 to 35% by weight, and PC-II is preferably 25 to 65% by weight. When PC-I is more than 80% by weight and PC-II is less than 20% by weight, the resulting resin has a large photoelastic constant and a low glass transition point. On the other hand, if PC-I is less than 30% by weight and PC-II is more than 70% by weight, the resulting resin has poor melt fluidity, resulting in poor molding, making it difficult to obtain an optically good molded product.
[0013]
Each of the resins forming the aromatic polycarbonate resin composition of the present invention is a known method used for producing a normal aromatic polycarbonate resin, for example, a method in which a dihydric phenol is reacted with a carbonate precursor such as phosgene or carbonic acid diester. Manufactured by.
[0014]
For example, in a reaction using phosgene as a carbonate precursor, the dihydric phenol is usually dissolved in an aqueous solution of an acid binder and reacted in the presence of an organic solvent. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and examples of the organic solvent include halogenated hydrocarbons such as methylene chloride and chlorobenzene. The reaction temperature is usually 0 to 40 ° C., and the reaction time is several minutes to 5 hours.
[0015]
A catalyst may be used to promote the reaction. Examples of the catalyst include tertiary amines such as triethylamine, tetra-n-butylammonium bromide, tetra-n-butylphosphonium bromide, quaternary ammonium compounds, quaternary compounds. Examples include phosphonium compounds. Furthermore, an antioxidant such as hydrosulfite can be added as necessary.
[0016]
Further, as the terminal terminator, for example, monofunctional phenols such as phenol, p-tert-butylphenol, p-cumylphenol, and isooctylphenol are used. In order to further improve the melt fluidity, it is preferable to use an alkylphenol having 10 to 50 carbon atoms in an amount of at least 5 mol% of the total terminal terminator. In this case, the substitution position of the alkyl group of the alkylphenol having 10 to 50 carbon atoms is usually the ortho-position or para-position of the hydroxyl group, and among them, a mixture of ortho-position and para-position is preferably used.
[0017]
The transesterification reaction using a carbonic acid diester as a carbonate precursor is carried out by distilling off the alcohol or phenol produced by stirring the dihydric phenol in a predetermined ratio while heating with the carbonic acid diester under an inert gas atmosphere. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. In the latter stage of the reaction, the reaction is completed by facilitating the distillation of the alcohol or phenol produced by reducing the system pressure. Examples of the carbonic acid diester include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred.
[0018]
A polymerization catalyst can also be used to accelerate the polymerization rate. Examples of the polymerization catalyst include alkali metal and alkaline earth metal hydroxides such as sodium hydroxide and potassium hydroxide, and boron and aluminum hydroxide alkalis. Metal salts, alkaline earth metal salts, quaternary ammonium salts, alkali metal and alkaline earth metal alkoxides, alkali metal and alkaline earth metal organic acid salts, zinc compounds, boron compounds, silicon compounds, A catalyst usually used for esterification reaction and transesterification reaction of germanium compounds, organotin compounds, lead compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds and the like can be used. The catalyst may be used alone or in combination of two or more. The amount of these catalysts used is selected in the range of 0.0001 to 1% by weight, preferably 0.0005 to 0.5% by weight, based on the dihydric phenol of the raw material.
[0019]
The PC-I and PC-II polymers thus obtained are preferably those in which 0.7 g of the polymer is dissolved in 100 ml of methylene chloride and the specific viscosity measured at 20 ° C. is in the range of 0.2 to 0.4. The range of 0.25 to 0.35 is more preferable. If the specific viscosity is less than 0.2, the molded product becomes brittle. On the other hand, if the specific viscosity is higher than 0.4, the melt fluidity is poor, a molding failure occurs, and an optically good molded product is difficult to obtain.
[0020]
The aromatic polycarbonate resin composition of the present invention can be molded by an arbitrary method such as an injection molding method, a compression molding method, an extrusion molding method, or a solution casting method.
The aromatic polycarbonate resin composition of the present invention may contain a phosphorus-based heat stabilizer, a phenol-based antioxidant, or the like as necessary. Examples of phosphorus stabilizers include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, Didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4 -Methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite Triesters of phosphorous acid such as bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite and tetrakis (2,4-di-tert-butylphenyl) -4,4-diphenylenephosphonite , Diesters and monoesters, which may be used alone or in combination of two or more. The addition amount is preferably 0.0001 to 0.05% by weight.
[0021]
Examples of phenolic antioxidants include triethylene glycol-bis (3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate), 1,6-hexanediol-bis (3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol-tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di -Tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexa Methylenebis (3,5-di-tert-butyl-4-hydroxy-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, etc. The preferred range of the addition amount is 0. 0001 to 0.05%.
[0022]
Moreover, the higher fatty acid ester of polyhydric alcohol can also be added as needed.
Preferred fatty acid esters are all esters and partial esters of saturated aliphatic monocarboxylic acids having 8 to 22 carbon atoms and glycols, glycerol, pentaerythritol, etc., and the preferred addition amount is 0.001 to 0.5% by weight. is there. Further, additives such as a light stabilizer, a colorant, an antistatic agent, and a lubricant can be added within a range not impairing transparency. Further, other polycarbonate resins or thermoplastic resins can be blended in a small proportion.
[0023]
The chlorine (Cl) contained in the aromatic polycarbonate resin of the present invention is preferably 1.0 ppm or less. Further, the number of foreign matters having an average diameter of 0.5 μm or more is preferably 10,000 / g or less.
[0024]
Since the aromatic polycarbonate composition of the present invention is particularly excellent in birefringence and moldability, it can be used as various molded articles. In particular, it is advantageously used as an optical molded product suitable for structural materials or functional materials of optical components such as optical disks, optical lenses, liquid crystal panels, optical cards, sheets, films, optical fibers, connectors, vapor-deposited plastic reflectors, displays, etc. can do. Among these, it can be used particularly advantageously as an optical disk substrate.
[0025]
【Example】
The following examples further illustrate the present invention. In the synthesis examples and examples, parts are parts by weight and% is% by weight. The evaluation was based on the following method.
Specific viscosity;
0.7 g of the polymer was dissolved in 100 ml of methylene chloride and measured at a temperature of 20 ° C.
Glass transition point (Tg);
Measured with a DuPont 910 DSC.
Fluidity (MFR);
Based on JIS K-7210, the amount of polymer (g) that flowed out for 10 minutes at 280 ° C. under a load of 2.16 kg using a semi-auto melt indexer manufactured by Toyo Seiki.
Total light transmittance;
Measurement was performed using Nippon Denshoku Sigma 80 according to ASTM D-1003.
Photoelastic constant;
This was measured with a photoelasticity measuring device PA-150 manufactured by Riken Keiki Co., Ltd.
Oblique incidence birefringence phase difference;
Using an oval ellipsometer ADR-200B automatic birefringence measuring apparatus, measurement was performed at an incident angle of 30 degrees.
warp;
The optical disk was allowed to stand for 1000 hours in a constant temperature and humidity machine at 80 ° C. and 85% RH, and then the warpage of the substrate was measured using an LM-1200 optical disk inspection apparatus manufactured by Ono Sokki.
[0026]
Synthesis Example 1 (Synthesis of PC-I)
A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 435.4 parts of ion-exchanged water and 55.6 parts of a 48% sodium hydroxide aqueous solution, and 57.5 2,2-bis (3-methyl-4-hydroxyphenyl) propane. And 0.24 parts of hydrosulfite were dissolved, 435.4 parts of methylene chloride was added, and 29 parts of phosgene was blown in at a temperature of 15 to 25 ° C. with stirring for 40 minutes. After the completion of phosgene blowing, 1.5 parts of p-tert-butylphenol and 18.5 parts of 48% aqueous caustic soda solution were added, and after emulsification, 0.16 part of triethylamine was added and stirred at 28 to 33 ° C. for about 1 hour to complete the reaction. did. After completion of the reaction, the product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid and washed with water. When the conductivity of the aqueous phase was almost the same as that of ion-exchanged water, the methylene chloride was evaporated to 61.4 parts of polymer. (Yield 97%). This polymer had a specific viscosity of 0.324 and a Tg of 120 ° C.
[0027]
Synthesis Example 2 (Synthesis of PC-II)
In the same apparatus as in Synthesis Example 1, 1137.3 parts of ion-exchanged water and 238.5 parts of 48% aqueous sodium hydroxide solution were placed, and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane 20.1. Then, 709.9 parts of methylene chloride was added, and 83.1 parts of phosgene was blown in over 40 minutes in the same manner as in Synthesis Example 1. After completion of the phosgene blowing, 5.8 parts of p-tert-butylphenol was added and emulsified, and 0.2 part of triethylamine was added to obtain 208.2 parts of a polymer in the same manner as in Synthesis Example 1 (yield 96%).
This polymer had a specific viscosity of 0.258 and a Tg of 226 ° C.
[0028]
Synthesis Example 3 (Synthesis of PC-II)
Polymer 217 was prepared in the same manner as in Synthesis Example 2 except that 14.5 parts of an alkylphenol having 20 carbon atoms (mixture of 70% ortho-substituted product and 30% para-substituted product) was used instead of p-tert-butylphenol in Synthesis Example 2. 0.5 part was obtained (94% yield). This product had a specific viscosity of 0.272 and Tg of 182 ° C.
[0029]
Example 1
70 parts of the polycarbonate synthesized in Synthesis Example 1, 30 parts of the polycarbonate synthesized in Synthesis Example 2, 0.005 part of tris (2,4-di-tert-butylphenyl) phosphite, 0.005 part of trimethyl phosphate, monoglyceride stearate After 0.045 part was uniformly dissolved in methylene chloride, the methylene chloride was evaporated to obtain a polymer composition. This was melt extruded at 250 ° C. and pelletized. This had a Tg of 150 ° C. and an MFR of 52 g / 10 min. This was injection-molded onto a disk substrate having a thickness of 120 mmφ and a thickness of 1.2 mm using DISK5Mlll manufactured by Sumitomo Heavy Industries. This had a total light transmittance of 89%, a photoelastic constant of 49 × 10 ⁻¹³ cm ² / dyn, an oblique incidence birefringence phase difference of 26 nm, and a warpage of 0.2 mm.
[0030]
Example 2
40 parts of the polymer synthesized in Synthesis Example 1 and 60 parts of the polymer synthesized in Synthesis Example 3 were pelletized in the same manner as in Example 1 with the same additive composition as in Example 1. This had a Tg of 155 ° C. and an MFR of 43 g / 10 min. When this was molded and evaluated in the same manner as in Example 1, the total light transmittance was 89%, the photoelastic constant was 43 × 10 ⁻¹³ cm ² / dyn, the oblique incident birefringence phase difference was 26 nm, The warpage was 0.2 mm.
[0031]
Comparative Example 1
A conventional bisphenol A polycarbonate (Panlite AD-5503 manufactured by Teijin Chemicals Ltd.) was molded in the same manner as in Example 1 and evaluated in the same manner as in Example 1. As a result, the total light transmittance was 89%, and the photoelastic constant was 82. × 10 ⁻¹³ cm ² / dyn, the oblique incident birefringence phase difference was 68 nm, and the warpage was 0.3 mm.
[0032]
Comparative Example 2
A pellet and a disk substrate were obtained in the same manner as in Example 1 except that 90 parts of the polymer synthesized in Synthesis Example 1 and 10 parts of the polymer synthesized in Synthesis Example 2 were used. This had a low Tg of 130 ° C., a photoelastic constant of 56 × 10 ⁻¹³ cm ² / dyn, and a large oblique incident birefringence phase difference of 55 nm.
[0033]
Comparative Example 3
Pelletization was performed in the same manner as in Example 1 except that 10 parts of the polymer synthesized in Synthesis Example 1 and 90 parts of the polymer synthesized in Synthesis Example 2 were used. The Tg of this product was as high as 220 ° C., and the MFR was not measurable and a good molded product could not be obtained.
[0034]
【The invention's effect】
Since the aromatic polycarbonate composition of the present invention has low birefringence, good melt fluidity and excellent transparency, it is suitably used as various optical molded articles such as optical disks, optical lenses, and optical cards.

Claims (7)

The following general formula [I]

An aromatic polycarbonate having a specific viscosity of 0.2 to 0.4 at 20 ° C. in which 0.7 g of the aromatic polycarbonate is dissolved in 100 ml of methylene chloride. Group polycarbonate (PC-I)
And the following general formula [II]

An aromatic polycarbonate having a repeating unit [II] represented by the following formula, wherein the specific viscosity of the solution at 20 ° C. obtained by dissolving 0.7 g of the aromatic polycarbonate in 100 ml of methylene chloride is 0.2 to 0.4: A fragrance substantially comprising an aromatic polycarbonate (PC-II), wherein the ratio of the aromatic polycarbonate (PC-I) to the aromatic polycarbonate (PC-II) is in the range of 80:20 to 30:70 by weight ratio. Group polycarbonate composition. Polymers of the PC-I and PC-II is specific viscosity of the solution at 20 ° C. obtained by dissolving each polymer 0.7g in 100ml of methylene chloride from 0.25 to 0. Aromatic according to claim 1, which is 35 Polycarbonate composition.   The aromatic polycarbonate composition according to claim 1, comprising 0.0001 to 0.05% by weight of a phosphorus-based heat stabilizer and / or 0.0001 to 0.05% by weight of a phenolic antioxidant.   The aromatic polycarbonate composition according to claim 1, wherein the PC-I polymer has at least 5 mol% or more of alkylphenyloxy groups having 10 to 50 carbon atoms as terminal groups per terminal.   2. The aromatic polycarbonate composition according to claim 1, wherein the PC-II polymer has at least 5 mol% or more of alkylphenyloxy groups having 10 to 50 carbon atoms as terminal groups.   An optical material formed from the aromatic polycarbonate composition according to claim 1.   An optical disk substrate formed from the aromatic polycarbonate composition according to claim 1.