JP3856115B2 - Polycarbonate resin - Google Patents

Description

【００１２】
（式中、Ｒ₁ 〜Ｒ₈ は、各々独立して水素原子、炭素数１〜５のアルキル基、炭素数６〜１２のアリール基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基、又は炭素数７〜１７のアラルキル基を表す。これらの基に炭素原子を有する場合には置換基として、炭素数１〜５のアルキル基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基を有することもできる。）
【００１３】
【化７】

【００１４】
（式中、Ｒ₉ 〜Ｒ₁₄は、各々独立して水素、炭素数１〜５のアルキル基、炭素数６〜１２のアリール基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基、又は炭素数７〜１７のアラルキル基、これらの基に炭素原子を有する場合には置換基として、炭素数１〜５のアルキル基、炭素数２〜５のアルケニル基、又は炭素数１〜５のアルコキシ基を有することもできる。Ｘは、−SiO(Ｒ₁₅)(Ｒ₁₆) −および／または−SiO(Ｒ₁₇)(Ｒ₁₈) −の単独重合体またはランダム共重合体を表し、平均重合度は 3〜200 であり、Ｒ₁₅〜Ｒ₁₈は、各々独立して水素、炭素数１〜５のアルキル基、炭素数６〜１２のアリール基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基、炭素数７〜１７のアラルキル基、又はヒドロフェニル基（Ｍ）であり、これらの基に炭素原子を有する場合には置換基として、炭素数１〜５のアルキル基、炭素数２〜５のアルケニル基、又は炭素数１〜５のアルコキシ基を有することもできる。ただし、Ｒ₁₅〜Ｒ₁₈の合計の内、ヒドロキシフェニル基を有する有機基(M) を平均で１〜３個含むものである。）
【００１５】
【化８】

【００１６】
（Ｒ₁₉〜Ｒ₂₀は、各々独立して、水素、フッ素、塩素、臭素、炭素数１〜１０のアルキル基、炭素数６〜１２のアリール基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基、炭素数７〜１７のアラルキル基を表すか、Ｒ₁₉およびＲ₂₀が任意に結合して、炭素環または複素環を形成する基を表し、これらの基に炭素原子を有する場合には置換基として、フッ素、塩素、臭素、炭素数１〜５のアルキル基、炭素数２〜５のアルケニル基、または炭素数１〜５のアルコキシ基を有することもできる。Ｙは、
【００１７】
【化９】

【００１８】
であり、ここにＲ₂₁〜Ｒ₂₄はそれぞれ、水素、フッ素、塩素、臭素、炭素数１〜１０のアルキル基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基又は炭素数６〜１２アリール基を表すか、Ｒ₂₁〜Ｒ₂₄が任意に結合して、炭素数３〜６の炭素環または複素環を形成する基を表し、これらの基に炭素原子を有する場合には置換基として、フッ素、塩素、臭素、炭素数１〜５のアルキル基、炭素数２〜５のアルケニル基、又は炭素数１〜５のアルコキシ基を有することもできる。a は０〜２０の整数を表す。）
【００１９】
本発明のポリカーボネート樹脂は、前記一般式（Ａ）と一般式（Ｂ）または、前記一般式（Ａ）と一般式（Ｂ）と一般式（Ｃ）の化合物とを炭酸エステル形成化合物を反応させることによって、製造することができるものであり、ビスフェノールＡから誘導されるポリカーボネートを製造する際に用いられている公知の方法、例えばビスフェノール類とホスゲンとの直接反応（ホスゲン法）、あるいはビスフェノール類とビスアリールカーボネートとのエステル交換反応（エステル交換法）などの方法を採用することができる。
【００２０】
ホスゲン法とエステル交換法では、一般式（Ａ）の化合物および一般式（Ｂ）の化合物の反応性を考慮した場合、ホスゲン法の方が好ましい。
【００２１】
前者のホスゲン法においては、通常酸結合剤および溶媒の存在下において、本発明における一般式（Ａ）と一般式（Ｂ）、または一般式（Ａ）と一般式（Ｂ）と一般式（Ｃ）の化合物とをホスゲンと反応させる。酸結合剤としては、例えばピリジンや、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属の水酸化物などが用いられ、また溶媒としては、例えば塩化メチレン、クロロホルム、クロロベンゼン、キシレンなどが用いられる。さらに、縮重合反応を促進するために、トリエチルアミンのような第三級アミン触媒などの触媒を、また重合度調節には、フェノール、ｐ−ｔ−ブチルフェノール、p-クミルフェノール、アルキル置換フェノール類、ヒドロキシ安息香酸アルキル類やアルキルオキシフェノール類などの一官能基化合物を分子量調節剤として加える。さらに、所望に応じ亜硫酸ナトリウム、ハイドロサルファイトなどの酸化防止剤や、フロログルシン、イサチンビスフェノール、1,1,1-トリス（4-ヒドロキシフェニル）エタン、α，α',α"-トリス（4-ヒドロキシフェニル)-1,3,5-トリイソプロピルベンゼンなど分岐化剤を小量添加してもよい。反応は通常０〜１５０℃、好ましくは５〜４０℃の範囲とするのが適当である。反応時間は反応温度によって左右されるが、通常０．５分〜１０時間、好ましくは１分〜２時間である。また、反応中は、反応系のpHを１０以上に保持することが望ましい。
【００２２】
一方後者のエステル交換法においては、本発明における一般式（Ａ）と一般式（Ｂ）、または一般式（Ａ）と一般式（Ｂ）と一般式（Ｃ）の化合物とをビスアリールカーボネートと混合し、減圧下で高温において反応させる。この時、フェノール、ｐ−ｔ−ブチルフェノール、p-クミルフェノール、アルキル置換フェノール類、ヒドロキシ安息香酸アルキル類やアルキルオキシフェノール類などの一官能基化合物を分子量調節剤として加えてもよい。反応は通常１５０〜３５０℃、好ましくは２００〜３００℃の範囲の温度において行われ、また減圧度は最終で好ましくは１mmHg以下にして、エステル交換反応により生成した該ビスアリールカーボネートから由来するフェノール類を系外へ留去させる。反応時間は反応温度や減圧度などによって左右されるが、通常１〜６時間程度である。反応は窒素やアルゴンなどの不活性ガス雰囲気下で行うことが好ましく。また、所望に応じ、酸化防止剤や分岐化剤を添加して反応を行ってもよい。
【００２３】
本発明に用いられる一般式（Ａ）の化合物としては、具体的には９，９−ビス（４−ヒドロキシ−２−メチルフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレン、９，９−ビス（４−ヒドロキシフェニル）フルオレン、３，６−ジメチル−９，９−ビス（４−ヒドロキシフェニル）フルオレン、９，９−ビス（３−メトキシ−４−ヒドロキシフェニル）フルオレン、９，９−ビス（３−エトキシ−４−ヒドロキシフェニル）フルオレン、９，９−ビス（３−エチル−４−ヒドロキシフェニル）フルオレン、４，５−ジメチル−９，９−ビス（４−ヒドロキシフェニル）フルオレン、９，９−ビス（３−フェニル−４−ヒドロキシフェニル）フルオレン、３，６−ジメチル−９，９−ビス（３−メチル−４−ヒドロキシフェニル）フルオレン及び３，６−ジフェニル−９，９−ビス（４−ヒドロキシフェニル）フルオレン等を挙げることができる。中でも特に、９，９−ビス（４−ヒドロキシフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレン、９，９−ビス（４−ヒドロキシ−２−メチルフェニル）フルオレンが好ましい。これらの化合物は２種類以上併用して使用することも可能である。
【００２４】
前記一般式（Ｂ）で表されるポリシロキサン化合物は、公知のヒドロシリル化反応による製造法、例えば不飽和基を有するフェノールとSi-H基を有するポリシロキサンをヒドロシリル化触媒下で付加反応させる方法にて製造される。
【００２５】
ヒドロシリル化に使用される触媒は、均一系、不均一系のいずれでもよく、具体的には、塩化白金酸などに代表される白金錯体、金属白金、オクタカルボニル２コバルト、パラジウム錯体、ロジウム錯体等が挙げられる。反応は、本発明に使用される不飽和基含有フェノール類が溶解する溶媒中で行われる。具体的には、四塩化炭素、クロロホルム、１，２−ジクロロエタン等のハロゲン化炭化水素、ベンゼン、トルエン、キシレン等の芳香族炭化水素、モノクロルベンゼン、ジクロロベンゼン等の芳香族ハロゲン化物、メチルエチルケトン、酢酸エチル、１，４−ジオキサン、シクロヘキサノン等を挙げる事ができるが、溶解性や触媒との相性より、ベンゼン、トルエン、キシレン等の芳香族炭化水素が望ましい。反応温度は６０〜１５０℃が好ましい。
【００２６】
上記Si-H基含有ポリシロキサンは、ポリアルキルハイドロジェンシロキサン、ポリアリールハイドロジェンシロキサン、ポリアルキルアリールハイドロジェンシロキサン等より誘導することができ、具体的にはポリメチルハイドロジェンシロキサン、ポリエチルハイドロジェンシロキサン、ポリフェニルハイドロジェンシロキサン、ポリメチルフェニルハイドロジェンシロキサン等が挙げられる。これらは２種類以上併用しても良い。
【００２７】
また、本発明における一般式（Ｂ）のポリシロキサン化合物には、前記の反応にて付加されたフェノール（ヒドロキシフェニル基）がポリシロキサン１分子当たり平均１〜３個付加されている。この付加されたヒドロキシフェニル基が、炭酸エステル形成化合物と反応しカーボネート結合を形成する。ヒドロキシフェニル基がポリシロキサン１分子当たり平均１未満であると、ヒドロキシフェニル基の全く付加されていない非反応性ポリシロキサンが増加する。また平均３を越えると、ポリシロキサンが強力な分岐化剤となり、ゴム状３次元網目構造の溶媒不溶性ポリカーボネート共重合体が生成しやすく、成形性や取扱いが困難となる。更に、一般式（Ｂ）のＸの平均重合度は 3〜200 が好ましく、特に 5〜100 が好適である。平均重合度が 3未満では十分にポリシロキサンの特性が得られないし、200 を超えると他のフェノール類との反応性が悪くなり好ましくない。
【００２８】
上記Si-H基を有するポリシロキサンと反応する不飽和基を有するフェノールとしては、具体的には、o-アリルフェノール、オイゲノール、イソオイゲノール、p-イソプロペニルフェノール、p-ヒドロキシスチレン、p-アリルフェノール、2,6-ジメチル-4- アリルフェノール、2-t-ブチル-6-(3-t-ブチル−2-ヒドロキシ-5- メチルベンジル)-4-メチルフェニルアクリレート、2-[1-(2-ヒドロキシ-3,5-ジ-t- ペンチルフェニル)エチル]-4,6-ジ-t- ペンチルフェニルアクリレート、p-ヒドロキシケイ皮酸メチル、2-ヒドロキシスチルベン、4-(1- ブテニル) フェノール等が挙げられる。なかでも、取扱いの容易さ、工業的有用性や反応性からo-アリルフェノール、オイゲノールが好ましい。
【００２９】
前記一般式（Ｂ）で表されるポリシロキサン化合物は、具体的には、以下の化学式の化合物などが挙げられるが、これらに限定されるものではない。
【００３０】
【化１０】

【００３１】
また、これらポリシロキサン化合物を２種類以上併用して使用することも可能である。これらのポリシロキサンに付加しているヒドロキシフェニル基は、あくまで理論上ポリシロキサン１分子当たり平均１〜３個付加しているだけであり、例えば付加が０のものもあれば１０個のものも存在する可能性がある。すなわち、本発明におけるポリシロキサン１分子当たり平均１〜３個ヒドロキシフェニル基が付加するという意味は、そのヒドロキシフェニル基付加数の分布の中心値が１〜３であることを示す。また、ヒドロキシフェニル基の付加位置も特定できるものではなく、一般式（Ｂ）のＸ中の側鎖のいずれにヒドロキシフェニル基が付加しても良い。
【００３２】
本発明における一般式（Ｃ）で表されるビスフェノール類としては、具体的には4,4'−ビフェニルジオール、ビス（4-ヒドロキシフェニル）メタン、ビス（4-ヒドロキシフェニル）エーテル、ビス（4-ヒドロキシフェニル）スルホン、ビス（4-ヒドロキシ−3-メチルフェニル）スルホン、ビス（4-ヒドロキシフェニル）スルホキシド、ビス（4-ヒドロキシフェニル）スルファイド、ビス（4-ヒドロキシフェニル）ケトン、1,1-ビス（4-ヒドロキシフェニル）エタン、2,2-ビス（4-ヒドロキシフェニル）プロパン（ビスフェノ−ルＡ；BPA ）、2,2-ビス（4-ヒドロキシフェニル）ブタン、1,1-ビス（4-ヒドロキシフェニル）シクロヘキサン（ビスフェノ−ルＺ；BPZ ）、2,2-ビス（4-ヒドロキシ−3-メチルフェニル）プロパン（ジメチルビスフェノールＡ）、2,2-ビス（4-ヒドロキシ−3,5-ジメチルフェニル）プロパン、1,1-ビス（4-ヒドロキシフェニル）−1-フェニルエタン（ビスフェノールＡＰ；BPAP）、ビス（4-ヒドロキシフェニル）ジフェニルメタン、2,2-ビス（4-ヒドロキシ−3-アリルフェニル）プロパン、3,3,5-トリメチル−1,1-ビス（4-ヒドロキシフェニル）シクロヘキサン、2,2-ビス（4-ヒドロキシ−3,5-ジブロモフェニル）プロパン、2,2-ビス（4-ヒドロキシ−3,5-ジクロロフェニル）プロパン、2,2-ビス（4-ヒドロキシ−3-ブロモフェニル）プロパン、2,2-ビス（4-ヒドロキシ−3-クロロフェニル）プロパン、2,2-ビス（4-ヒドロキシフェニル）ヘキサフルオロプロパン、4,4'-[1,3-フェニレン（1-メチルエチリデン）] ビスフェノール、4,4'-[1,4-フェニレン（1-メチルエチリデン）] ビスフェノール、1,1'−ビ−2-ナフトールなどが例示される。これらは、２種類以上併用して用いてもよい。また、これらの中でも特に2,2-ビス（4-ヒドロキシフェニル）プロパンが好ましい。
【００３３】
また本発明中の炭酸エステル形成性化合物としては、例えばホスゲンや、ジフェニルカーボネート、ジ−ｐ−トリルカーボネート、フェニル−ｐ−トリルカーボネート、ジ−ｐ−クロロフェニルカーボネート、ジナフチルカーボネートなどのビスアリルカーボネートが挙げられる。これらの化合物は２種類以上併用して使用することも可能である。
【００３４】
本発明においてホスゲン法を採用する場合は、反応を効率よく行うため第四級アンモニウム塩を少量添加してもよい。具体的には、テトラメチルアンモニウムクロライド、トリメチルベンジルアンモニウムクロライド、トリエチルベンジルアンモニウムクロライド、テトラエチルアンモニウムブロマイド、テトラ−ｎ−ブチルアンモニウムアイオダイドなどが例示され、これらのうちトリメチルベンジルアンモニウムクロライド、トリエチルベンジルアンモニウムクロライドが好ましい。この第四級アンモニウム塩は、使用される全ビスフェノール類に対して、一般に0.0005〜５mol%使用されることが好ましい。
【００３５】
更に本発明に分子量調節剤を用いる場合には特に一価フェノールが好ましく、具体的にはフェノールやブチルフェノール、オクチルフェノール、ノニルフェノール、デカニルフェノール、テトラデカニルフェノール、ヘプタデカニルフェノール、オクタデカニルフェノール等のアルキル置換フェノール；ヒドロキシ安息香酸ブチル、ヒドロキシ安息香酸オクチル、ヒドロキシ安息香酸ノニル、ヒドロキシ安息香酸デカニル、ヒドロキシ安息香酸ヘプタデカニル等のヒドロキシ安息香酸アルキルエステル；ブトキシフェノール、オクチルオキシフェノール、ノニルオキシフェノール、デカニルオキシフェノール、テトラデカニルオキシフェノール、ヘプタデカニルオキシフェノール、オクタデカニルオキシフェノール等のアルキルオキシフェノール類が例示される。この分子量調節剤の添加量は全ビスフェノール類に対して0.1 〜50mol%である。好ましくは、0.5 〜10mol%である。
【００３６】
これらの反応で合成された本発明のポリカーボネート樹脂は、押出成形、射出成形、ブロ−成形、圧縮成形、湿式成形など公知の成形法で成形可能であるが、耐摩耗性を有するフィルムやシートを成形するには湿式成形や押出〜ロール成形されることが好ましく、容易に成形ができる範囲としては、極限粘度が０．２〜２．０dl/gの範囲であることが好ましい。特に押出〜ロール成形される場合は流動性の観点から０．２〜１．０dl/gの範囲にあることが好ましい。
【００３７】
湿式成形法が選択される場合は、溶媒として本発明のポリカーボネート樹脂を溶解し、適度の揮発性を有するものであれば使用可能であり、テトラヒドロフランや１，４−ジオキサン等の環状エーテル系溶媒、トルエン、キシレン等の炭化水素系溶媒、シクロペンタノン、シクロヘキサノン等の環状ケトン溶媒、ジクロロメタン、クロロホルム等のハロゲン系溶媒などを用いることが出来る。最近では、環境問題の観点から非ハロゲン系溶媒を用いることが多く、中でも比較的安全で沸点も低いテトラヒドロフランが良く使用される。本発明のポリカーボネート樹脂および樹脂組成物においてもテトラヒドロフランに良溶である特徴を示す。
【００３８】
また、前記一般式（Ｂ）の使用量は成形品の強度や透明性などを考慮した場合、前記一般式（Ａ）及び一般式（Ｂ）及び一般式（Ｃ）の合計量に対して１０〜５０重量％が好ましい。前記一般式（Ａ）が１０重量％未満では、耐摩耗性の効果は劣り、５０重量％を越えると強度が低下しゴム状の成形体になる。
【００３９】
前記一般式（Ｃ）を使用する場合は、要求性能を著しく低下させない範囲で使用することができ、前記一般式（Ａ）と一般式（Ｃ）の合計量に対して５０重量％以下が好ましい。
【００４０】
本発明のポリカーボネート樹脂は、従来の光ディスク用ポリカーボネートと同様に高度に精製されたものが好ましい。具体的には、直径５０μｍ以上のダストが実質上検出されず、直径０．５〜５０μｍのダストが３×１０⁴ 以下、無機および有機残留塩素が２ｐｐｍ以下、残留アルカリ金属が２ｐｐｍ以下、残存水酸基２００ｐｐｍ以下、残存窒素量５ｐｐｍ以下、残存モノマー２０ｐｐｍ以下等の基準を可能な限り満たすように精製される。また、低分子量体除去や溶媒除去のため抽出等の後処理が行われる場合もある。また、原材料の一般式（Ａ）、一般式（Ｂ）および一般式（Ｃ）の化合物や炭酸エステル形成化合物等についても不純物や異性体などを極力低減した材料を用いることが好ましい。
【００４１】
本発明のポリカーボネート樹脂は成型時に必要な安定性や離型性を確保するため、所望に応じて、ヒンダードフェノール系やホスファイト系酸化防止剤；脂肪酸エステル系、脂肪酸系、脂肪酸グリセリド系、密ろう等天然油脂などの滑剤や離型剤；ベンゾトリアゾール系、ベンゾフェノン系、ジベンゾイルメタン系、サリチレート系等の光安定剤；ポリアルキレングリコール、脂肪酸グリセリド等帯電防止剤などを適宜併用してよい。
【００４２】
さらにはコスト低減や物性改良のため、他のポリマーと性能を損なわない範囲で任意に混合して使用する事も可能である。特に、ジオルガノポリシロキサンを0.1 〜30wt% 添加することによって、さらに耐摩耗性が改善される場合もある。
【００４３】
本発明における樹脂組成物のうち、本発明のポリカーボネート樹脂に添加されるジオルガノポリシロキサンは、具体的には、ポリジアルキルシロキサン、ポリジアリールシロキサン、ポリアルキルアリールシロキサン等が挙げられる。さらに具体的には、下記一般式（Ｄ）で表されるジオルガノポリシロキサンが例示される。これらは２種類以上併用しても良い。
【００４４】
【化１１】

【００４５】
（式中、Ｒ₃₀〜Ｒ₃₅は、各々独立して水素、炭素数１〜５のアルキル基、炭素数６〜１２のアリール基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基、炭素数７〜１７のアラルキル基であり、これらの基に炭素原子を有する場合には置換基として、炭素数１〜５のアルキル基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基を有することもできる。Ｗは、−SiO(Ｒ₃₆)(Ｒ₃₇）−および／または−SiO(Ｒ₃₈)(Ｒ₃₉）−の単独重合体またはランダム共重合体を表し、平均重合度は 3〜200 であり、Ｒ₃₆〜Ｒ₃₉は、各々独立して水素、炭素数１〜５のアルキル基、炭素数６〜１２のアリール基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基、または炭素数７〜１７のアラルキル基であり、これらの基に炭素原子を有する場合には置換基として、炭素数１〜５のアルキル基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基を有することもできる。）
【００４６】
ただし、本発明におけるジオルガノポリシロキサンは、単独のものを意味し、ポリカーボネートと共重合したようなものは本発明におけるジオルガノポリシロキサンには含めない。
【００４７】
本発明におけるジオルガノポリシロキサンは、数平均分子量が200 〜100,000 の範囲のものであり、数平均分子量が350〜10,000のものが好ましい。
【００４８】
本発明のポリカーボネート樹脂にジオルガノポリシロキサンをブレンドする方法として、ポリカーボネート樹脂製造時にブレンドする方法、ポリカーボネート樹脂液にブレンドする方法、ポリカーボネート樹脂粉体にブレンドする方法、ポリカーボネート樹脂熱溶融体にブレンドする方法等が選択できるが、特にポリカーボネート樹脂の製造（重合）時にジオルガノポリシロキサンをブレンドする方法が分散性がよく、透明性向上に最も効果があるため好ましい。
【００４９】
【実施例】
次に実施例により、本発明をさらに詳細に説明するが、本発明はこれらの例によってなんら限定されるものではない。
【００５０】
実施例１
8.8%(w/v) の水酸化ナトリウム水溶液600ml に、９，９−ビス（4-ヒドロキシ−3-メチルフェニル）フルオレン76ｇ（以下BCFLと略記）とハイドロサルファイト0.1gを加え溶解した。これにメチレンクロライド400ml リットルとトリエチルベンジルアンモニウムクロライドを0.1g加え、１５℃に保ちながら撹拌しつつ、ホスゲン34g を1g／分の速度で吹き込んだ。
吹き込み終了後、下記構造を主成分とする化合物51g （以下Si1 と略記）を加え、１０分間激しく撹拌し続け、さらに0.2ml のトリエチルアミンを加え、さらに約１時間撹拌し重合させた。
【００５１】
【化１２】

【００５２】
重合液を水相と有機相に分離し、有機相をリン酸で中和し、洗液の導電率が１０μＳ/cm 以下になるまで水洗を繰り返した後、精製樹脂液を得た。得られた精製樹脂液を、強攪拌されている６０℃の温水に樹脂液をゆっくり滴下し、溶媒を除去しつつ重合物を固形化した。固形物を濾過後、乾燥して白色粉末状重合体を得た。
この重合体は、塩化メチレンを溶媒とする濃度0.5g/dl の溶液の温度 20℃における極限粘度［η］は0.45dl/gであった。
得られた上記重合体を赤外線吸収スペクトルより分析した結果、1770cm^-1付近の位置にカルボニル基による吸収、1240cm^-1付近の位置にエーテル結合による吸収が認められ、カーボネート結合を有することが確認された。また、3650〜3200cm^-1の位置に水酸基由来の吸収はほとんど認められなかった。
これらを総合した結果、この重合体は下記構造を主成分とするポリカーボネート重合体と認められた。
【００５３】
【化１３】

【００５４】
得られたポリカーボネート粉末の一部をテトラヒドロフラン(THF) に溶解し15w/v%溶液にした後、キャストフィルムを作成した。また、残りのポリカーボネート粉末は、延伸ロール付き混練押出機にて320 ℃で押出し、ストランドを得た後、延伸ロールにて圧延フィルムを作成した。得られたフィルムは微黄色の透明フィルムであった。
得られたフィルム成形品をスガ試験機製サンシャインウエザーメーターWEL-SUN-DCで４８時間耐候試験を行い、耐候試験前後の耐摩耗性を評価した。
【００５５】
実施例２
Si1 の代わりに下記構造を主成分とする化合物51ｇ（以下Si2 と略記）を用い、さらにSi2 投入時にp-t-ブチルフェノール2.0g（以下PTBPと略記）を投入した以外は、実施例１と同様に行った。
【００５６】
【化１４】

【００５７】
得られた重合体の極限粘度［η］は0.58dl/gで、赤外吸収スペクトル分析等よりこの重合体は下記構造を主成分とするポリカーボネート重合体と認められた。
【００５８】
【化１５】

【００５９】
実施例３
Si1 の代わりに、下記構造を主成分とする化合物51ｇ（以下Si3 と略記）を用い、さらにSi3 投入時にPTBP 4.8ｇを投入した以外は、実施例１と同様に重合に行った。
【００６０】
【化１６】

【００６１】
得られた重合体の極限粘度［η］は0.54dl/gで、赤外吸収スペクトル分析等よりこの重合体は下記構造を主成分とするポリカーボネート重合体と認められた。
【００６２】
【化１７】

【００６３】
実施例４
BCFLを63.5ｇ、Si1 を38.1ｇに変更し、2,2-ビス（4-ヒドロキシフェニル）プロパン25.4ｇ（以下をBPA と略記）をBCFLと同時に添加し、さらにPTBP 0.7ｇをSi1 と同時添加した以外は、実施例１と同様に行った。
得られた重合体の極限粘度［η］は0.44dl/gで、赤外吸収スペクトル等より下記構造を主成分とするポリカーボネート重合体と認められた。
【００６４】
【化１８】

【００６５】
実施例５
BCFLを89ｇ、Si1 を38ｇに変更し、Si1 と同時に下記構造のジオルガノポリシロキサン3.8g（以下SD1 と略記）を添加した以外は実施例１と同様に行った。
【００６６】
【化１９】

【００６７】
得られた重合体混合物の極限粘度［η］は0.53dl/gで、赤外吸収スペクトル等より共重合比以外は実施例１の同等の構造を主成分とするポリカーボネート重合体とSD1の混合物と認められた。
【００６８】
実施例６
BCFLを82.6ｇに変更し、Si1 の代わりに下記構造を主成分とするの化合物（以下Si4 と略記：化２０）を44.4ｇを用い、Si4 と同時に下記構造のジオルガノポリシロキサン8.9g（以下SD2 と略記：化２１）を添加した以外は実施例１と同様に行った。
【００６９】
【化２０】

【００７０】
【化２１】

【００７１】
得られた重合体混合物の極限粘度［η］は0.75dl/gで、赤外吸収スペクトル等より下記構造を主成分とするポリカーボネート重合体とSD2 の混合物と認められた。
【００７２】
【化２２】

【００７３】
実施例７
Si1 の代わりに下記構造を主成分とする化合物51ｇ（以下Si5 と略記：化２３）を用い、Si5 と同時に下記構造のジオルガノポリシロキサン3.8g（以下SD3 と略記：化２４）を添加した以外は実施例１と同様に行った。
【００７４】
【化２３】

【００７５】
【化２４】

【００７６】
得られた重合体混合物の極限粘度［η］は0.39dl/gで、赤外吸収スペクトル等より下記構造を主成分とするポリカーボネート重合体とSD3 の混合物と認められた。
【００７７】
【化２５】

【００７８】
比較例１
実施例１のポリカーボネートの代わりに、市販の２，２−ビス（４−ヒドロキシフェニル）プロパン(BPA) 型ポリカーボネート樹脂（三菱瓦斯化学（株）製ユーピロンS-3000、極限粘度0.49dl/g）を用いて実施例１と同様の成形、評価を行った。
このポリカーボネートはTHF15w/v% 溶液にした時、白濁し未溶解が多くキャストフィルムは作成できなかった。
【００７９】
比較例２
実施例１の代わりに、市販のS-3000ポリカーボネート樹脂にSD2 のジオルガノポリシロキサンを6.3wt%(BPAモノマー換算で7wt%）添加した以外は、実施例１と同様の成形、評価を行った。
このポリカーボネートはTHF15w/v% 溶液にした時、白濁し未溶解が多くキャストフィルムは作成できなかった。また耐候試験後の圧延フィルム成形品は、摩耗試験を始めるとすぐ亀裂が生じ測定不能であった。
【００８０】
比較例３
ホスゲンを50ｇに変更し、Si1 の代わりに、BPA を51ｇ用い、BCFLと同時にBPA を投入し、PTBP2.0gをホスゲン吹き込み終了後に加えた以外は実施例１と同様に行った。
得られた重合体の極限粘度［η］は0.46dl/gで、赤外吸収スペクトル分析等よりこの重合体は、下記構造単位からなるポリカーボネート重合体と認められた。
【００８１】
【化２６】

【００８２】
比較例４
Si1 の代わりに、α，ω−ビス［３−（ｏ−ヒドロキシフェニル）プロピル］ポリジメチルシロキサン（以下SC1 と略記）を51ｇ用い、PTBP0.7gをホスゲン吹き込み終了後に加えた以外は実施例１と同様に行った。
得られた粉末の極限粘度［η］は0.45dl/gで、赤外吸収スペクトル等よりこの重合体は下記構造を主成分とするポリカーボネート重合体と認められた。
【００８３】
【化２７】

【００８４】
比較例５
BCFLを51ｇ、Si1 を76ｇに変更した以外が実施例１と同様に行った。
得られた重合体の極限粘度［η］は0.30dl/gで、赤外吸収スペクトル分析等よりこの重合体は重合比以外は実施例１と同等のポリカーボネート重合体構造を有することが認められた。
実施例１と同様の圧延フィルムを作成したところ、柔らかく押出機内で発泡し良好な成形品は得られなかった。
【００８５】
比較例６
BCFLの代わりにBPA を76ｇ用いた以外は、実施例１と同様に行った。
得られた重合体の極限粘度［η］は0.70dl/gで、赤外吸収スペクトル分析等よりこの重合体は下記構造を主成分とするポリカーボネート重合体と認められた。
【００８６】
【化２８】

【００８７】
実施例１と同様のTHF15w/v%溶液にした時、やや透明なゲル状物が残存し、良好なキャストフィルムは作成できなかった。
【００８８】
比較例７
Si1 を用いず、BCFLのみ76ｇ用い、ホスゲン吹き込み終了後PTBPを0.6g投入した以外は、実施例１と同様に行った。
得られた重合体の極限粘度［η］は0.43dl/gで、赤外吸収スペクトル分析等よりこの重合体は下記構造単位からなるポリカーボネート重合体と認められた。
【００８９】
【化２９】

【００９０】
実施例１と同様の圧延フィルムを作成を試みたが、320 ℃で溶融せず圧延フィルムは得られなかった。
【００９１】
比較例８
BCFLの代わりにSi1 を76ｇ用い、ホスゲンを5gに変更し、ホスゲン吹き込み終了後にはSi1 を用いなかった以外は、実施例１と同様に行った。
得られた重合体は液状で極限粘度［η］は0.13dl/gで、赤外吸収スペクトル分析等よりこの重合体は下記構造を主成分とするポリカーボネート重合体と認められた。
【００９２】
【化３０】

【００９３】
なお実施例１と同様の成形品は、重合体は液状のため得られなかった。
【００９４】
実施例１〜７及び比較例１〜８の組成と摩耗試験結果について表１に示す。
【００９５】
【表１】

【００９６】
〔表中の記号の説明〕
（Ａ）共重合比：一般式（Ａ）、一般式（Ｂ）、一般式（Ｃ）の合計量に対する一般式（Ａ）の重量比（重量％）
（Ｂ）共重合比：一般式（Ａ）、一般式（Ｂ）、一般式（Ｃ）の合計量に対する一般式（Ｂ）の重量比（重量％）
（Ｃ）共重合比：一般式（Ａ）、一般式（Ｂ）、一般式（Ｃ）の合計量に対する一般式（Ｃ）の重量比（重量％）
（Ｄ）ブレンド比：一般式（Ａ）、一般式（Ｂ）、一般式（Ｃ）の合計量に対する一般式（Ｄ）の添加量（重量％）
極限粘度：0.5g/100ccジクロロメタン樹脂溶液を20℃、ハギンズ定数0.45で極限粘度［η］(dl/g)を求めた。
キャストフィルム：15w/v %THF溶液でガラス基板上に均一な塗膜を形成させ、溶液を乾燥後、約150 μｍ厚のフィルムを得た。
圧延フィルム：井元製作所製圧延ロール付き混練微小量押出機にて 320℃で溶融押出後、 100℃加熱ロールにて圧延フィルム作成。厚さ約250 μｍ。
耐候試験：スガ試験機製サンシャインウエザーメーターWEL-SUN-DC中で70℃、120 分サイクルにて４８時間耐候試験を行った。
摩耗量：テーバー摩耗試験（荷重1000ｇ、CS-17 輪、24時間）後の摩耗量(mg)。
【００９７】
【発明の効果】
本発明の新規ポリカーボネート樹脂は、医療用機器部品、食品容器、飲料ボトル、ガス透過膜、染顔料バインダー、玩具、窓・建築部材、安全保護具部材、ＯＡ機器・携帯電話等各種部材や筐体などの一般成形加工用途に用いることが可能で、特にコンパクトディスク、レーザーディスク、光カード、ＭＯディスク、デジタルバーサブルディスク、近接場記録光ディスク等の光ディスク、ピックアップレンズ、メガネレンズ、カメラレンズ等の光学レンズ、近接場光記録媒体用カバー層、光学フィルター等の光学フィルムや光学シート、光ファイバー、光導波路等の光情報伝達媒体、導光板などの光学用部材を製造するのに好適な成形性、透明性を有すると共に、耐摩耗性と耐候性に優れたポリカーボネート樹脂を提供する事が出来る。また、シリコーンや従来のポリカーボネート樹脂等との相溶性も良く、各種ポリマーアロイ材料や添加剤としても有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention is a general molding of medical equipment parts, food containers, beverage bottles, gas permeable membranes, dye / pigment binders, toys, windows / architectural members, safety protective equipment members, office automation equipment / cell phones, etc. It can be used for processing applications, especially compact discs, laser discs, optical cards, MO discs, digital versatile discs, optical discs such as near-field recording optical discs, optical lenses such as pickup lenses, spectacle lenses, camera lenses, and near-fields. It has moldability and transparency suitable for producing optical members such as optical recording media cover layers, optical films such as optical filters, optical sheets, optical information transmission media such as optical fibers and optical waveguides, and light guide plates. The present invention relates to a polycarbonate resin excellent in wear resistance and weather resistance.
[0002]
[Prior art]
Currently, most of the polycarbonate resins produced are bisphenol A type polycarbonates made from 2,2-bis (4-hydroxyphenyl) propane (abbreviation: bisphenol A). Bisphenol A-type polycarbonate is a polycarbonate resin with a balance of cost, heat resistance, mechanical strength, etc. However, as the use of polycarbonate has expanded in recent years, polycarbonates with better physical properties have been desired and have various structures. Polycarbonate has been developed. However, there is a demand from the market for polycarbonates having better physical properties or unique physical properties, and the development of new polycarbonates is required.
[0003]
As one of them, a siloxane copolymer polycarbonate which is a modified polycarbonate having improved releasability and fluidity has been developed (Japanese Patent Laid-Open Nos. 50-29695, 3-079626, 5-155999, and 7-258398, JP-A-7-165897).
[0004]
Furthermore, graft type siloxane copolymer polycarbonates and resin compositions having higher abrasion resistance than these siloxane copolymer polycarbonates have been developed. (JP 10-158379, JP 10-158499)
[0005]
On the other hand, polycarbonate having improved wear resistance and contamination resistance by a polycarbonate having a special fluorene structure instead of the sliding property of the silicone chain has been developed. (Japanese Patent Laid-Open No. 8-134198)
[0006]
These are excellent in wear resistance under normal conditions, but are not sufficient in wear resistance after severe environmental tests such as outdoor exposure, and there is room for improvement.
[0007]
Further, when such a polycarbonate is used for wet molding, a non-halogen solvent is used as a solvent due to environmental problems, and there is a demand for a polycarbonate having good solubility in a non-halogen solvent such as tetrahydrofuran. .
[0008]
[Problems to be solved by the invention]
In view of the above circumstances, an object of the present invention is to provide an excellent polycarbonate resin that dissolves in a non-halogen solvent, has excellent weather resistance, and maintains abrasion resistance.
[0009]
[Means for Solving the Problems]
As a result of intensive studies to solve the conventional problems, the present inventors have found that a polycarbonate polymer having a specific fluorene structure and a specific graft polysiloxane structure in a repeating unit is a novel polycarbonate not described in any literature. Thus, the present invention has been found to be a polycarbonate resin that is well soluble in non-halogen solvents and excellent in weather resistance and abrasion resistance, and based on this finding, the present invention has been completed.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
That is, a polycarbonate obtained by reacting a compound represented by the general formula (A) and the general formula (B) or the general formula (A), the general formula (B), and the general formula (C) with a carbonate-forming compound. The general formula (B) is 10 to 50 wt% with respect to all monomer components (general formula (A) + general formula (B) + general formula (C)), and the intrinsic viscosity [η] is A polycarbonate resin of 0.2 to 2.0 [dl / g] is provided.
[0011]
[Chemical 6]

[0012]
(Wherein R ₁ ~ R ₈ Are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or 7 to 7 carbon atoms. 17 aralkyl groups are represented. When these groups have a carbon atom, the substituent may have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. )
[0013]
[Chemical 7]

[0014]
(Wherein R ₉ ~ R ₁₄ Are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or 7 to 17 carbon atoms. In the case where these groups have a carbon atom, the substituent may have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. it can. X is -SiO (R ₁₅ ) (R ₁₆ )-And / or -SiO (R ₁₇ ) (R ₁₈ )-Represents a homopolymer or a random copolymer, the average degree of polymerization is 3 to 200, and R ₁₅ ~ R ₁₈ Are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 7 to 17 carbon atoms. An aralkyl group or a hydrophenyl group (M), and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 1 carbon atom It can also have ~ 5 alkoxy groups. However, R ₁₅ ~ R ₁₈ Of 1 to 3 organic groups (M) having a hydroxyphenyl group on the average. )
[0015]
[Chemical 8]

[0016]
(R ₁₉ ~ R ₂₀ Are each independently hydrogen, fluorine, chlorine, bromine, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. Represents an aralkyl group having 7 to 17 carbon atoms, or R ₁₉ And R ₂₀ Represents a group which is optionally bonded to form a carbocycle or a heterocycle, and when these groups have a carbon atom, as a substituent, fluorine, chlorine, bromine, an alkyl group having 1 to 5 carbon atoms, carbon It can also have a C2-C5 alkenyl group or a C1-C5 alkoxy group. Y is
[0017]
[Chemical 9]

[0018]
And here R _{twenty one} ~ R _{twenty four} Each represents hydrogen, fluorine, chlorine, bromine, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms, or R _{twenty one} ~ R _{twenty four} Are optionally bonded to form a carbocyclic or heterocyclic ring having 3 to 6 carbon atoms, and when these groups have a carbon atom, as a substituent, fluorine, chlorine, bromine, 1 to 1 carbon atoms It can also have a 5 alkyl group, a C2-C5 alkenyl group, or a C1-C5 alkoxy group. a represents an integer of 0 to 20. )
[0019]
In the polycarbonate resin of the present invention, the general formula (A) and the general formula (B) or the general formula (A), the general formula (B), and the compound of the general formula (C) are reacted with a carbonate ester-forming compound. Known methods used in producing polycarbonates derived from bisphenol A, such as direct reaction of bisphenols with phosgene (phosgene method), or bisphenols Methods such as transesterification with bisaryl carbonate (transesterification method) can be employed.
[0020]
In the phosgene method and the transesterification method, the phosgene method is preferred in consideration of the reactivity of the compound of the general formula (A) and the compound of the general formula (B).
[0021]
In the former phosgene method, the general formula (A) and the general formula (B) or the general formula (A), the general formula (B), and the general formula (C) in the present invention are usually used in the presence of an acid binder and a solvent. ) With a compound of phosgene. Examples of the acid binder include pyridine and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. Examples of the solvent include methylene chloride, chloroform, chlorobenzene, and xylene. Furthermore, in order to accelerate the polycondensation reaction, a catalyst such as a tertiary amine catalyst such as triethylamine is used. For adjusting the degree of polymerization, phenol, pt-butylphenol, p-cumylphenol, alkyl-substituted phenols are used. Monofunctional compounds such as alkyl hydroxybenzoates and alkyloxyphenols are added as molecular weight regulators. In addition, antioxidants such as sodium sulfite and hydrosulfite, phloroglucin, isatin bisphenol, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ', α "-tris (4 A small amount of a branching agent such as -hydroxyphenyl) -1,3,5-triisopropylbenzene may be added, and the reaction is usually in the range of 0 to 150 ° C., preferably 5 to 40 ° C. Although the reaction time depends on the reaction temperature, it is usually 0.5 minutes to 10 hours, preferably 1 minute to 2 hours, and it is desirable to maintain the pH of the reaction system at 10 or more during the reaction. .
[0022]
On the other hand, in the latter transesterification method, the general formula (A) and the general formula (B) in the present invention, or the compounds of the general formula (A), the general formula (B), and the general formula (C) are combined with bisaryl carbonate. Mix and react at elevated temperature under reduced pressure. At this time, monofunctional compounds such as phenol, pt-butylphenol, p-cumylphenol, alkyl-substituted phenols, alkyl hydroxybenzoates and alkyloxyphenols may be added as molecular weight regulators. The reaction is usually carried out at a temperature in the range of 150 to 350 ° C., preferably 200 to 300 ° C., and the degree of vacuum is preferably 1 mmHg or less at the end, and phenols derived from the bisaryl carbonate produced by the transesterification reaction Is distilled out of the system. The reaction time depends on the reaction temperature and the reduced pressure, but is usually about 1 to 6 hours. The reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon. Moreover, you may react by adding antioxidant and a branching agent as needed.
[0023]
Specific examples of the compound of the general formula (A) used in the present invention include 9,9-bis (4-hydroxy-2-methylphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl). ) Fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, 3,6-dimethyl-9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methoxy-4-hydroxyphenyl) Fluorene, 9,9-bis (3-ethoxy-4-hydroxyphenyl) fluorene, 9,9-bis (3-ethyl-4-hydroxyphenyl) fluorene, 4,5-dimethyl-9,9-bis (4- Hydroxyphenyl) fluorene, 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene, 3,6-dimethyl-9,9-bis (3-methyl-) - hydroxyphenyl) fluorene and 3,6-diphenyl-9,9-bis (4-hydroxyphenyl) can be given fluorene. Among these, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and 9,9-bis (4-hydroxy-2-methylphenyl) fluorene are particularly preferable. preferable. Two or more of these compounds can be used in combination.
[0024]
The polysiloxane compound represented by the general formula (B) is produced by a known hydrosilylation reaction, for example, a method in which a phenol having an unsaturated group and a polysiloxane having an Si-H group are subjected to an addition reaction in the presence of a hydrosilylation catalyst. Manufactured by.
[0025]
The catalyst used for hydrosilylation may be either homogeneous or heterogeneous. Specifically, platinum complexes represented by chloroplatinic acid, platinum metal, octacarbonyl dicobalt, palladium complexes, rhodium complexes, etc. Is mentioned. The reaction is carried out in a solvent in which the unsaturated group-containing phenols used in the present invention are dissolved. Specifically, halogenated hydrocarbons such as carbon tetrachloride, chloroform and 1,2-dichloroethane, aromatic hydrocarbons such as benzene, toluene and xylene, aromatic halides such as monochlorobenzene and dichlorobenzene, methyl ethyl ketone and acetic acid Ethyl, 1,4-dioxane, cyclohexanone and the like can be mentioned, but aromatic hydrocarbons such as benzene, toluene and xylene are preferable from the viewpoint of solubility and compatibility with the catalyst. The reaction temperature is preferably 60 to 150 ° C.
[0026]
The Si-H group-containing polysiloxane can be derived from polyalkyl hydrogen siloxane, polyaryl hydrogen siloxane, polyalkyl aryl hydrogen siloxane, etc., specifically, polymethyl hydrogen siloxane, polyethyl hydrogen siloxane. Examples thereof include siloxane, polyphenylhydrogensiloxane, and polymethylphenylhydrogensiloxane. Two or more of these may be used in combination.
[0027]
In addition, an average of 1 to 3 phenols (hydroxyphenyl groups) added by the above reaction are added to the polysiloxane compound of the general formula (B) in the present invention per molecule of polysiloxane. This added hydroxyphenyl group reacts with the carbonate ester forming compound to form a carbonate bond. If the average number of hydroxyphenyl groups is less than 1 per molecule of polysiloxane, non-reactive polysiloxanes to which no hydroxyphenyl groups are added increase. On the other hand, if the average exceeds 3, polysiloxane becomes a strong branching agent, and a solvent-insoluble polycarbonate copolymer having a rubbery three-dimensional network structure is likely to be produced, making moldability and handling difficult. Further, the average degree of polymerization of X in the general formula (B) is preferably 3 to 200, and more preferably 5 to 100. If the average degree of polymerization is less than 3, sufficient characteristics of polysiloxane cannot be obtained, and if it exceeds 200, the reactivity with other phenols deteriorates.
[0028]
Specific examples of the phenol having an unsaturated group that reacts with the polysiloxane having the Si-H group include o-allylphenol, eugenol, isoeugenol, p-isopropenylphenol, p-hydroxystyrene, and p-allyl. Phenol, 2,6-dimethyl-4-allylphenol, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- ( 2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, methyl p-hydroxycinnamate, 2-hydroxystilbene, 4- (1-butenyl) Phenol etc. are mentioned. Of these, o-allylphenol and eugenol are preferred from the viewpoint of ease of handling, industrial utility and reactivity.
[0029]
Specific examples of the polysiloxane compound represented by the general formula (B) include, but are not limited to, compounds having the following chemical formulas.
[0030]
[Chemical Formula 10]

[0031]
Also, two or more of these polysiloxane compounds can be used in combination. The number of hydroxyphenyl groups added to these polysiloxanes is theoretically only 1 to 3 on average per polysiloxane molecule. For example, there are 0 additions and 10 additions. there's a possibility that. That is, the meaning that 1 to 3 hydroxyphenyl groups are added on average per polysiloxane molecule in the present invention indicates that the center value of the distribution of the number of added hydroxyphenyl groups is 1 to 3. Further, the addition position of the hydroxyphenyl group cannot be specified, and the hydroxyphenyl group may be added to any side chain in X of the general formula (B).
[0032]
Specific examples of the bisphenols represented by the general formula (C) in the present invention include 4,4′-biphenyldiol, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, and bis (4 -Hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1- Bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A; BPA), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4 -Hydroxyphenyl) cyclohexane (bisphenol Z; BPZ), 2,2-bis (4-hydroxy-3-methylphenyl) propane (dimethylbisphenol A), 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane (bisphenol AP; BPAP), bis (4-hydroxyphenyl) diphenylmethane, 2,2- Bis (4-hydroxy-3-allylphenyl) propane, 3,3,5-trimethyl-1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) ) Propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3-) Chlorophenyl) propane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4 '-[1,3-phenylene (1-methylethylidene)] bisphenol, 4,4'-[1,4-phenylene (1-methylethylidene)] bisphenol, 1,1'-bi-2-naphtho Etc. are exemplified. Two or more of these may be used in combination. Of these, 2,2-bis (4-hydroxyphenyl) propane is particularly preferred.
[0033]
Examples of the carbonate ester-forming compound in the present invention include phosgene, bisallyl carbonate such as diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate. Can be mentioned. Two or more of these compounds can be used in combination.
[0034]
When employing the phosgene method in the present invention, a small amount of a quaternary ammonium salt may be added in order to carry out the reaction efficiently. Specific examples include tetramethylammonium chloride, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tetraethylammonium bromide, and tetra-n-butylammonium iodide. Among these, trimethylbenzylammonium chloride and triethylbenzylammonium chloride are exemplified. preferable. This quaternary ammonium salt is generally preferably used in an amount of 0.0005 to 5 mol% based on the total bisphenols used.
[0035]
Further, when a molecular weight regulator is used in the present invention, monohydric phenol is particularly preferable, specifically, phenol, butylphenol, octylphenol, nonylphenol, decanylphenol, tetradecanylphenol, heptadecanylphenol, octadecanylphenol, etc. Alkyl-substituted phenols of the following: hydroxybenzoic acid alkyl esters such as butyl hydroxybenzoate, octyl hydroxybenzoate, nonyl hydroxybenzoate, decanyl hydroxybenzoate, heptadecanyl hydroxybenzoate; butoxyphenol, octyloxyphenol, nonyloxyphenol, decanyl Alkyloxyphenols such as oxyphenol, tetradecanyloxyphenol, heptadecanyloxyphenol, and octadecanyloxyphenol Le acids are exemplified. The addition amount of this molecular weight regulator is 0.1 to 50 mol% with respect to all bisphenols. Preferably, it is 0.5 to 10 mol%.
[0036]
The polycarbonate resin of the present invention synthesized by these reactions can be molded by known molding methods such as extrusion molding, injection molding, blow molding, compression molding, and wet molding. For molding, wet molding or extrusion to roll molding is preferable, and the range in which the molding can be easily performed is preferably in the range of 0.2 to 2.0 dl / g. In particular, when extrusion to roll molding, it is preferably in the range of 0.2 to 1.0 dl / g from the viewpoint of fluidity.
[0037]
When a wet molding method is selected, it can be used as long as it dissolves the polycarbonate resin of the present invention as a solvent and has appropriate volatility, such as cyclic ether solvents such as tetrahydrofuran and 1,4-dioxane, Hydrocarbon solvents such as toluene and xylene, cyclic ketone solvents such as cyclopentanone and cyclohexanone, and halogen solvents such as dichloromethane and chloroform can be used. Recently, non-halogen solvents are often used from the viewpoint of environmental problems, and tetrahydrofuran, which is relatively safe and has a low boiling point, is often used. The polycarbonate resin and the resin composition of the present invention also have a characteristic of being well soluble in tetrahydrofuran.
[0038]
The amount of the general formula (B) used is 10 with respect to the total amount of the general formula (A), the general formula (B), and the general formula (C) in consideration of the strength and transparency of the molded product. -50% by weight is preferred. When the general formula (A) is less than 10% by weight, the effect of wear resistance is inferior, and when it exceeds 50% by weight, the strength is lowered and a rubber-like molded product is obtained.
[0039]
When using the said general formula (C), it can be used in the range which does not reduce a required performance remarkably, and 50 weight% or less is preferable with respect to the total amount of the said general formula (A) and general formula (C). .
[0040]
The polycarbonate resin of the present invention is preferably highly purified as in the conventional polycarbonate for optical disks. Specifically, dust having a diameter of 50 μm or more is not substantially detected, and dust having a diameter of 0.5 to 50 μm is 3 × 10. ^Four Thereafter, the inorganic and organic residual chlorine is refined so as to satisfy as much as possible the criteria such as 2 ppm or less of residual chlorine, 2 ppm or less of residual alkali metal, 200 ppm or less of residual hydroxyl group, 5 ppm or less of residual nitrogen, and 20 ppm or less of residual monomer. In some cases, post-treatment such as extraction is performed to remove low molecular weight substances or solvents. Moreover, it is preferable to use a material in which impurities, isomers, and the like are reduced as much as possible for the compounds of the general formula (A), the general formula (B), the general formula (C), and the carbonic acid ester forming compound.
[0041]
The polycarbonate resin of the present invention ensures hindered phenolic and phosphite antioxidants; fatty acid ester-based, fatty acid-based, fatty acid glyceride-based, dense, as required, in order to ensure the stability and releasability required during molding. Lubricants such as waxes and other natural oils and mold release agents; benzotriazole-based, benzophenone-based, dibenzoylmethane-based, salicylate-based light stabilizers; anti-static agents such as polyalkylene glycols and fatty acid glycerides may be used in combination as appropriate.
[0042]
Furthermore, in order to reduce the cost and improve the physical properties, it can be arbitrarily mixed with other polymers as long as the performance is not impaired. In particular, the wear resistance may be further improved by adding 0.1 to 30 wt% of diorganopolysiloxane.
[0043]
Specific examples of the diorganopolysiloxane added to the polycarbonate resin of the present invention in the resin composition of the present invention include polydialkylsiloxane, polydiarylsiloxane, and polyalkylarylsiloxane. More specifically, a diorganopolysiloxane represented by the following general formula (D) is exemplified. Two or more of these may be used in combination.
[0044]
Embedded image

[0045]
(Wherein R ₃₀ ~ R ₃₅ Are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 7 to 17 carbon atoms. It is an aralkyl group, and when these groups have a carbon atom, the substituent may have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. it can. W is -SiO (R ₃₆ ) (R ₃₇ )-And / or -SiO (R ₃₈ ) (R ₃₉ )-Represents a homopolymer or a random copolymer, the average degree of polymerization is 3 to 200, and R ₃₆ ~ R ₃₉ Are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or 7 to 17 carbon atoms. When these groups have carbon atoms, they have a C 1-5 alkyl group, a C 2-5 alkenyl group, or a C 1-5 alkoxy group as substituents. You can also. )
[0046]
However, the diorganopolysiloxane in the present invention means a single one, and those which are copolymerized with polycarbonate are not included in the diorganopolysiloxane in the present invention.
[0047]
The diorganopolysiloxane in the present invention has a number average molecular weight in the range of 200 to 100,000, and preferably has a number average molecular weight of 350 to 10,000.
[0048]
As a method of blending the diorganopolysiloxane with the polycarbonate resin of the present invention, a method of blending at the time of producing the polycarbonate resin, a method of blending with the polycarbonate resin liquid, a method of blending with the polycarbonate resin powder, a method of blending with the polycarbonate resin hot melt In particular, a method of blending diorganopolysiloxane at the time of production (polymerization) of a polycarbonate resin is preferable because it has good dispersibility and is most effective in improving transparency.
[0049]
【Example】
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
[0050]
Example 1
To 600 ml of an aqueous 8.8% (w / v) sodium hydroxide solution, 76 g of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter abbreviated as BCFL) and 0.1 g of hydrosulfite were added and dissolved. To this, 400 ml of methylene chloride and 0.1 g of triethylbenzylammonium chloride were added, and 34 g of phosgene was blown at a rate of 1 g / min while stirring at 15 ° C.
After completion of the blowing, 51 g of a compound having the following structure as a main component (hereinafter abbreviated as Si1) was added, and stirring was continued vigorously for 10 minutes, and further 0.2 ml of triethylamine was added, followed by further stirring for about 1 hour for polymerization.
[0051]
Embedded image

[0052]
The polymerization liquid was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washed repeatedly with water until the washing liquid had a conductivity of 10 μS / cm 2 or less to obtain a purified resin liquid. The obtained purified resin solution was slowly added dropwise to 60 ° C. hot water that was vigorously stirred to solidify the polymer while removing the solvent. The solid was filtered and dried to obtain a white powdery polymer.
This polymer had an intrinsic viscosity [η] at a temperature of 20 ° C. of a solution having a concentration of 0.5 g / dl in methylene chloride as a solvent and was 0.45 dl / g.
As a result of analyzing the obtained polymer from the infrared absorption spectrum, 1770 cm ^-1 Absorption by carbonyl group in the vicinity, 1240cm ^-1 Absorption by an ether bond was observed at a nearby position, and it was confirmed to have a carbonate bond. Also, 3650-3200cm ^-1 Absorption derived from a hydroxyl group was hardly observed at the position.
As a result of combining these, this polymer was recognized as a polycarbonate polymer having the following structure as a main component.
[0053]
Embedded image

[0054]
A part of the obtained polycarbonate powder was dissolved in tetrahydrofuran (THF) to form a 15 w / v% solution, and then a cast film was prepared. The remaining polycarbonate powder was extruded at 320 ° C. with a kneading extruder with a drawing roll to obtain a strand, and then a rolled film was formed with the drawing roll. The obtained film was a slightly yellow transparent film.
The obtained film molded product was subjected to a weather resistance test for 48 hours with a sunshine weather meter WEL-SUN-DC manufactured by Suga Test Instruments, and the wear resistance before and after the weather resistance test was evaluated.
[0055]
Example 2
The same procedure as in Example 1 was performed except that 51 g (hereinafter abbreviated as Si2) of a compound having the following structure as a main component was used instead of Si1, and 2.0 g of pt-butylphenol (hereinafter abbreviated as PTBP) was added at the time of addition of Si2. It was.
[0056]
Embedded image

[0057]
The intrinsic viscosity [η] of the obtained polymer was 0.58 dl / g, and this polymer was recognized as a polycarbonate polymer having the following structure as a main component by infrared absorption spectrum analysis or the like.
[0058]
Embedded image

[0059]
Example 3
Polymerization was carried out in the same manner as in Example 1 except that 51 g of a compound having the following structure as a main component (hereinafter abbreviated as Si3) was used in place of Si1, and 4.8 g of PTBP was added when Si3 was added.
[0060]
Embedded image

[0061]
The obtained polymer had an intrinsic viscosity [η] of 0.54 dl / g. From infrared absorption spectrum analysis and the like, this polymer was recognized as a polycarbonate polymer having the following structure as a main component.
[0062]
Embedded image

[0063]
Example 4
BCFL changed to 63.5g, Si1 changed to 38.1g, 2,2-bis (4-hydroxyphenyl) propane 25.4g (hereinafter abbreviated as BPA) was added simultaneously with BCFL, and PTBP 0.7g was added simultaneously with Si1 The procedure was the same as in Example 1 except that.
The obtained polymer had an intrinsic viscosity [η] of 0.44 dl / g and was recognized as a polycarbonate polymer having the following structure as a main component from infrared absorption spectra and the like.
[0064]
Embedded image

[0065]
Example 5
The same procedure as in Example 1 was conducted except that BCFL was changed to 89 g, Si1 was changed to 38 g, and diorganopolysiloxane 3.8 g (hereinafter abbreviated as SD1) having the following structure was added simultaneously with Si1.
[0066]
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[0067]
The obtained polymer mixture had an intrinsic viscosity [η] of 0.53 dl / g. From the infrared absorption spectrum and the like, except for the copolymerization ratio, a mixture of a polycarbonate polymer having the same structure as that of Example 1 and SD1 Admitted.
[0068]
Example 6
BCFL was changed to 82.6g, and instead of Si1, 44.4g of a compound having the following structure as the main component (hereinafter abbreviated as Si4) was used together with Si4 and 8.9g of diorganopolysiloxane having the following structure (hereinafter referred to as Si4) Abbreviated as SD2: The same procedure as in Example 1 was performed except that Chemical Formula 21) was added.
[0069]
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[0070]
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[0071]
The obtained polymer mixture had an intrinsic viscosity [η] of 0.75 dl / g and was recognized as a mixture of a polycarbonate polymer having the following structure as a main component and SD2 from an infrared absorption spectrum or the like.
[0072]
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[0073]
Example 7
Instead of Si1, 51 g of a compound having the following structure as a main component (hereinafter abbreviated as Si5: Chemical Formula 23) was used, except that 3.8 g of diorganopolysiloxane having the following structure (hereinafter abbreviated as SD3: Chemical Formula 24) was added simultaneously with Si5. Was carried out in the same manner as in Example 1.
[0074]
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[0075]
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[0076]
The obtained polymer mixture had an intrinsic viscosity [η] of 0.39 dl / g, and was confirmed to be a mixture of a polycarbonate polymer having the following structure as a main component and SD3 from an infrared absorption spectrum or the like.
[0077]
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[0078]
Comparative Example 1
Instead of the polycarbonate of Example 1, a commercially available 2,2-bis (4-hydroxyphenyl) propane (BPA) type polycarbonate resin (Iupilon S-3000 manufactured by Mitsubishi Gas Chemical Co., Inc., intrinsic viscosity 0.49 dl / g) was used. The same molding and evaluation as in Example 1 were performed.
When this polycarbonate was converted to a THF 15 w / v% solution, it was cloudy and undissolved, and a cast film could not be produced.
[0079]
Comparative Example 2
Instead of Example 1, molding and evaluation were performed in the same manner as in Example 1 except that 6.3 wt% of SD2 diorganopolysiloxane was added to a commercially available S-3000 polycarbonate resin (7 wt% in terms of BPA monomer). .
When this polycarbonate was converted to a THF 15 w / v% solution, it was cloudy and undissolved, and a cast film could not be produced. Further, the rolled film molded product after the weather resistance test was cracked immediately after the wear test was started, and measurement was impossible.
[0080]
Comparative Example 3
The same procedure as in Example 1 was carried out except that phosgene was changed to 50 g, 51 g of BPA was used instead of Si1, BPA was added simultaneously with BCFL, and 2.0 g of PTBP was added after the completion of phosgene blowing.
The intrinsic viscosity [η] of the obtained polymer was 0.46 dl / g, and this polymer was recognized as a polycarbonate polymer composed of the following structural units by infrared absorption spectrum analysis and the like.
[0081]
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[0082]
Comparative Example 4
Example 1 was used except that 51 g of α, ω-bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane (hereinafter abbreviated as SC1) was used instead of Si1, and PTBP 0.7 g was added after the completion of phosgene blowing. The same was done.
The intrinsic viscosity [η] of the obtained powder was 0.45 dl / g, and this polymer was recognized as a polycarbonate polymer having the following structure as a main component from the infrared absorption spectrum and the like.
[0083]
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[0084]
Comparative Example 5
The same procedure as in Example 1 was performed except that BCFL was changed to 51 g and Si1 was changed to 76 g.
The intrinsic viscosity [η] of the obtained polymer was 0.30 dl / g, and it was confirmed by infrared absorption spectrum analysis etc. that this polymer had a polycarbonate polymer structure equivalent to Example 1 except for the polymerization ratio. .
When a rolled film similar to Example 1 was prepared, it was soft and foamed in an extruder, and a good molded product could not be obtained.
[0085]
Comparative Example 6
The same procedure as in Example 1 was performed except that 76 g of BPA was used instead of BCFL.
The intrinsic viscosity [η] of the obtained polymer was 0.70 dl / g, and this polymer was recognized as a polycarbonate polymer mainly composed of the following structure by infrared absorption spectrum analysis and the like.
[0086]
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[0087]
When the same THF 15 w / v% solution as in Example 1 was used, a slightly transparent gel remained and a good cast film could not be produced.
[0088]
Comparative Example 7
The same procedure as in Example 1 was carried out except that 76 g of BCFL alone was used without Si1, and 0.6 g of PTBP was added after the completion of phosgene blowing.
The intrinsic viscosity [η] of the obtained polymer was 0.43 dl / g, and this polymer was recognized as a polycarbonate polymer comprising the following structural units by infrared absorption spectrum analysis and the like.
[0089]
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[0090]
An attempt was made to produce a rolled film similar to that of Example 1, but the film was not melted at 320 ° C. and a rolled film was not obtained.
[0091]
Comparative Example 8
The same procedure as in Example 1 was carried out except that 76 g of Si1 was used instead of BCFL, phosgene was changed to 5 g, and Si1 was not used after the completion of phosgene blowing.
The obtained polymer was liquid and had an intrinsic viscosity [η] of 0.13 dl / g. From infrared absorption spectrum analysis and the like, this polymer was recognized as a polycarbonate polymer having the following structure as a main component.
[0092]
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[0093]
In addition, the molded article similar to Example 1 was not obtained because the polymer was liquid.
[0094]
It shows in Table 1 about the composition and abrasion test result of Examples 1-7 and Comparative Examples 1-8.
[0095]
[Table 1]

[0096]
[Explanation of symbols in the table]
(A) Copolymerization ratio: Weight ratio of general formula (A) to the total amount of general formula (A), general formula (B), and general formula (C) (% by weight)
(B) Copolymerization ratio: Weight ratio of general formula (B) to the total amount of general formula (A), general formula (B), and general formula (C) (% by weight)
(C) Copolymerization ratio: Weight ratio of general formula (C) to the total amount of general formula (A), general formula (B), and general formula (C) (% by weight)
(D) Blend ratio: Addition amount (% by weight) of general formula (D) with respect to the total amount of general formula (A), general formula (B), and general formula (C)
Intrinsic viscosity: The intrinsic viscosity [η] (dl / g) was determined from a 0.5 g / 100 cc dichloromethane resin solution at 20 ° C. and a Huggins constant of 0.45.
Cast film: A uniform coating film was formed on a glass substrate with a 15 w / v% THF solution, and after drying the solution, a film having a thickness of about 150 μm was obtained.
Rolled film: Melted and extruded at 320 ° C with a kneading micro-volume extruder with a rolling roll manufactured by Imoto Seisakusho, and then a rolled film was created with a 100 ° C heated roll. Thickness about 250 μm.
Weather resistance test: A weather resistance test was performed for 48 hours at 70 ° C. and 120 minutes cycle in a sunshine weather meter WEL-SUN-DC manufactured by Suga Test Instruments.
Amount of wear: Amount of wear (mg) after the Taber abrasion test (load 1000g, CS-17 wheel, 24 hours).
[0097]
【The invention's effect】
The novel polycarbonate resin of the present invention includes medical equipment parts, food containers, beverage bottles, gas permeable membranes, dye / pigment binders, toys, windows / construction members, safety protective equipment members, OA equipment / mobile phones and other various members and casings. It can be used for general molding applications such as compact discs, laser discs, optical cards, MO discs, digital versatile discs, optical discs such as near-field recording optical discs, optical lenses such as pickup lenses, eyeglass lenses, camera lenses, etc. Formability and transparency suitable for manufacturing optical members such as lenses, optical films such as optical field filters, optical films such as lenses, cover layers for optical recording media, optical filters, optical fibers, optical waveguides, and light guide plates It is possible to provide a polycarbonate resin having excellent wear resistance and weather resistance. In addition, it has good compatibility with silicone and conventional polycarbonate resin, and is useful as various polymer alloy materials and additives.

Claims (9)

A polycarbonate obtained by reacting a compound represented by the general formula (A) and the general formula (B) or the general formula (A), the general formula (B), and the general formula (C) with a carbonate-forming compound. The general formula (B) is 10 to 50 wt% with respect to all monomer components (general formula (A) + general formula (B) + general formula (C)), and the intrinsic viscosity [η] is 0 Polycarbonate resin of .2 to 2.0 [dl / g].

Wherein R _{1 to} R ₈ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 1 to 5 carbon atoms. Or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, carbon (Also have an alkoxy group of 1 to 5)

(Wherein R _{9 to} R ₁₄ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. An alkoxy group or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or carbon It may have an alkoxy group of 1 to 5. X is a homopolymer or a random copolymer of —SiO (R ₁₅ ) (R ₁₆ ) — and / or —SiO (R ₁₇ ) (R ₁₈ ) —. The average degree of polymerization is 3 to 200, and R _{15 to} R ₁₈ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 2 to 5 carbon atoms. An alkenyl group, an alkoxy group having 1 to 5 carbon atoms, an aralkyl group having 7 to 17 carbon atoms, or hydroxyphenyl An organic group (M) having a group, and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a carbon atom having 1 to 5 carbon atoms. (Although it can also have an alkoxy group, it contains 1 to 3 organic groups (M) having a hydroxyphenyl group on average out of the total of R _{15 to} R _18. )

(R ₁₉ to R ₂₀ are each independently hydrogen, fluorine, chlorine, bromine, alkyl groups having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, carbon atoms An alkoxy group having 1 to 5 carbon atoms, an aralkyl group having 7 to 17 carbon atoms, or a group in which R ₁₉ and R ₂₀ are optionally bonded to form a carbocyclic or heterocyclic ring; When it has, it can also have a fluorine, chlorine, bromine, a C1-C5 alkyl group, a C2-C5 alkenyl group, or a C1-C5 alkoxy group as a substituent.

Where R _{21 to} R ₂₄ are each hydrogen, fluorine, chlorine, bromine, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or the number of carbon atoms represent a 6-12 aryl group and in the case of any bound R ₂₁ to R ₂₄ may represent a group forming a carbon ring or a heterocyclic ring having 3 to 6 carbon atoms, having a carbon atom in these groups As a substituent, it can also have fluorine, chlorine, bromine, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. a represents an integer of 0 to 20. ) The general formula (A) is 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and 9,9-bis (4-hydroxy-2- The polycarbonate resin according to claim 1, which is at least one selected from the group of (methylphenyl) fluorene. The polycarbonate resin according to claim 1, wherein the carbonic acid ester forming compound is phosgene. Formula (B) at least one kind of claim 1, wherein the polycarbonate resin R ₁₅ to R ₁₈ is selected from methyl and phenyl groups. The polycarbonate resin according to claim 1, wherein the general formula (C) is 2,2-bis (4-hydroxyphenyl) propane. 2. The polycarbonate resin according to claim 1, wherein the ratio of the general formula (C) is, by weight ratio, general formula (C) / (general formula (A) + general formula (C)) ≦ 0.5. A polycarbonate resin composition comprising the polycarbonate resin according to claim 1 mixed with a diorganopolysiloxane. The polycarbonate resin composition of Claim 7 which mixed the diorganopolysiloxane of general formula (D).

(Wherein R _{30 to} R ₃₅ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. An alkoxy group, an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 1 carbon atom It may also have an alkoxy group of ˜5, W represents a homopolymer or a random copolymer of —SiO (R ₃₆ ) (R ₃₇ ) — and / or —SiO (R ₃₈ ) (R ₃₉ ) —. The average degree of polymerization is 3 to 200, and R _{36 to} R ₃₉ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms. , An alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms. When it has a child, it can also have a C1-C5 alkyl group, a C2-C5 alkenyl group, and a C1-C5 alkoxy group as a substituent.) The polycarbonate resin composition according to claim 7, wherein the mixing ratio of diorganopolysiloxane is 0.1 to 30 wt%.