JP3187142B2 - High refractive index, low birefringence polycarbonate resin - Google Patents
High refractive index, low birefringence polycarbonate resinInfo
- Publication number
- JP3187142B2 JP3187142B2 JP17979392A JP17979392A JP3187142B2 JP 3187142 B2 JP3187142 B2 JP 3187142B2 JP 17979392 A JP17979392 A JP 17979392A JP 17979392 A JP17979392 A JP 17979392A JP 3187142 B2 JP3187142 B2 JP 3187142B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- bis
- polycarbonate resin
- refractive index
- hydroxyphenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、屈折率及び複屈折の改
善されたポリカーボネート樹脂に関する。更に詳しく
は、特定量の９，９−ビス（４−オキシフェニレン）フ
ルオレン構成単位を有する高屈折率、低複屈折性で且つ
透明性に優れるポリカーボネート樹脂に関する。このよ
うな樹脂はその特性を生かしＣＤピックアップレンズ、
フレネルレンズのような光学レンズ、プロジェクション
テレビ用スクリーン、位相差フィルムのようなフィル
ム、ディスク用の素材として極めて有用なものである。The present invention relates to a polycarbonate resin having improved refractive index and birefringence. More particularly, the high refractive index having a specific amount of 9,9-bis (4-oxy-phenylene) fluorene configuration units relates polycarbonate resin having excellent and transparency at low birefringence. Such a resin takes advantage of its characteristics, such as a CD pickup lens,
It is extremely useful as a material for optical lenses such as Fresnel lenses, projection television screens, films such as retardation films, and discs.
【０００２】[0002]
【従来の技術】従来、２，２−ビス（４−ヒドロキシフ
ェニル）プロパンにカーボネート前駆体物質を反応させ
て得られるポリカーボネート樹脂は透明性、耐熱性、機
械的特性、寸法安定性が優れているがゆえにエンジニア
リングプラスチックとして多くの分野に広く使用されて
いる。特に透明性に優れることから光学材料としての用
途も多い。しかしながら、かかるポリカーボネート樹脂
は光学材料としては複屈折が大きいという難点を有して
いる。2. Description of the Related Art Conventionally, polycarbonate resins obtained by reacting a carbonate precursor with 2,2-bis (4-hydroxyphenyl) propane have excellent transparency, heat resistance, mechanical properties and dimensional stability. Therefore, it is widely used in many fields as engineering plastic. In particular, it has many uses as an optical material because of its excellent transparency. However, such a polycarbonate resin has a disadvantage that birefringence is large as an optical material.
【０００３】[0003]
【発明が解決しようとする課題】本発明者は、ポリカー
ボネート樹脂の透明性を損なわず高屈折率で且つ低複屈
折性のポリカーボネート樹脂を提供することを目的とす
る。SUMMARY OF THE INVENTION An object of the present invention is to provide a polycarbonate resin having a high refractive index and a low birefringence without impairing the transparency of the polycarbonate resin.
【０００４】本発明者は、この目的を達成せんとして鋭
意検討を重ねた結果、９，９−ビス（４−オキシフェニ
レン）フルオレン構成単位を特定割合導入したポリカー
ボネート共重合体が上記目的を達成することを見出し、
本発明に到達した。[0004] The present inventors have conducted intensive result of extensive investigations, 9,9-bis (4-oxy-phenylene) identifying fluorene configuration unit ratio introduced polycarbonate copolymer to achieve the above object this object as attained plugs Heading to do
The present invention has been reached.
【０００５】９，９−ビス（４−ヒドロキシフェニル）
フルオレンにカーボネート前駆体を反応させて得られる
芳香族ポリカーボネート樹脂は公知であり、このポリマ
ーが高屈折率で耐熱性が良好なことも知られている。し
かしながら、このホモポリマーを合成する際、溶剤に不
溶のゲル状物が多量に生成し、溶剤可溶成分の収率は高
々６０〜７０％で実用性に乏しいものであった。また、
このものを溶融成形しようとした場合、溶融粘度が高す
ぎて成形できないという問題があった。[0005] 9,9-bis (4-hydroxyphenyl)
Aromatic polycarbonate resins obtained by reacting fluorene with a carbonate precursor are known, and it is also known that this polymer has a high refractive index and good heat resistance. However, when synthesizing this homopolymer, a large amount of a gel-like substance insoluble in a solvent was generated, and the yield of the solvent-soluble component was at most 60 to 70%, which was not practical. Also,
When this was to be melt molded, there was a problem that the melt viscosity was too high to be molded.
【０００６】しかるに、９，９−ビス（４−オキシフェ
ニレン）フルオレン構成単位を特定量共重合した芳香族
ポリカーボネート樹脂が、このような欠点を有しないば
かりか、高屈折率で低複屈折性を示すことは驚くべきこ
とである。[0006] However, 9,9-bis (4-oxy-phenylene) amount identify fluorene configuration units copolymerized with the aromatic polycarbonate resin is not only does not have this disadvantage, a low birefringence at a high refractive index Is surprising.
【０００７】[0007]
【課題を解決するための手段】本発明は、下記一般式
［１］The present invention provides a compound represented by the following general formula [1]:
【０００８】[0008]
【化３】 Embedded image
【０００９】［式中Ｒ1 〜Ｒ4 は水素原子、ハロゲン原
子、フェニル基、炭素数１〜３のアルキル基であって、
同一又は異なっていてもよい。］で表される構成単位及
び下記一般式［２］Wherein R 1 to R 4 are a hydrogen atom, a halogen atom, a phenyl group, an alkyl group having 1 to 3 carbon atoms,
They may be the same or different. And the following general formula [2]:
【００１０】[0010]
【化４】 Embedded image
【００１１】［式中Ｗは単結合、アルキリデン基、シク
ロアルキリデン基、フェニル基置換アルキリデン基、ス
ルホン基、スルフィド基又はオキシド基であり、Ｒ5及
びＲ6は水素原子、ハロゲン原子、フェニル基、炭素数
１〜３のアルキル基であって、同一又は異なっていても
よく、ｍ及びｎは夫々１〜４の整数である。］で表され
る構成単位からなり、一般式［１］で表される構成単位
を４１〜９５モル％含有し、光弾性定数が５０×１０
-13ｃｍ2／ｄｙｎｅ以下で且つ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０．１
９以上であり、一価フェノールの末端停止剤を全二価フ
ェノールに対し、０．０１〜１０モル％用いた高屈折
率、低複屈折性ポリカーボネート樹脂。Wherein W is a single bond, an alkylidene group, a cycloalkylidene group, a phenyl-substituted alkylidene group, a sulfone group, a sulfide group or an oxide group, and R 5 and R 6 are a hydrogen atom, a halogen atom, a phenyl group, It is an alkyl group having 1 to 3 carbon atoms, which may be the same or different, and m and n are each an integer of 1 to 4. Consists of structural units represented by in], the configuration unit represented by the general formula [1] containing 41 to 95 mol%, photoelastic constant 50 × 10
-13 cm 2 / dyne or less and 0.7 g was dissolved in 100 ml of methylene chloride, and the specific viscosity measured at 20 ° C. was 0.1.
9 above der is, a terminating agent of the monohydric phenol full divalent off
A high-refractive-index, low-birefringent polycarbonate resin used in an amount of 0.01 to 10 mol% based on the phenol.
【００１２】本発明で対象とするのポリカーボネート樹
脂は、９，９−ビス（４−ヒドロキシフェニル）フルオ
レン類と一種以上の他の二価フェノール化合物類と末端
停止剤及びカーボネート前駆体物質の反応によって製造
される。通常ホスゲンを使用する界面重縮合法、又は炭
酸ジエステルを使用するエステル交換反応によって製造
される。The polycarbonate resins of interest in the present invention are prepared by reacting 9,9-bis (4-hydroxyphenyl) fluorenes with one or more other dihydric phenolic compounds, a terminator and a carbonate precursor material. Manufactured. It is usually produced by an interfacial polycondensation method using phosgene or a transesterification reaction using a carbonic acid diester.
【００１３】９，９−ビス（４−ヒドロキシフェニル）
フルオレン類としては、例えば９，９−ビス（４−ヒド
ロキシフェニル）フルオレン、９，９−ビス（３−メチ
ル−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
等があげられ、特に９，９−ビス（４−ヒドロキシフェ
ニル）フルオレンが好ましい。9,9-bis (4-hydroxyphenyl)
As fluorenes, for example, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, 9,9-bis (3-ethyl-4-hydroxyphenyl) ) Fluorene and the like, and 9,9-bis (4-hydroxyphenyl) fluorene is particularly preferred.
【００１４】他の二価フェノールとしては例えばビス
（４−ヒドロキシフェニル）メタン、２，２−ビス（４
−ヒドロキシフェニル）プロパン［通称ビスフェノール
Ａ］、２，２−ビス（４−ヒドロキシ−３−メチルフェ
ニル）プロパン、４，４−ビス（４ーヒドロキシフェニ
ル）ヘプタン、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−３，５−ジブロモフェニル）プロパン、ビス
（４−ヒドロキシフェニル）オキサイド、ビス（３，５
−ジクロロ−４−ヒドロキシフェニル）オキサイド、
４，４′−ジヒドロキシジフェニル、３，３′−ジクロ
ロ−４，４′−ジヒドロキシジフェニル、ビス（４−ヒ
ドロキシフェニル）スルホン、ビス（３，５−ジメチル
−４−ヒドロキシフェニル）スルホン、ビス（４−ヒド
ロキシフェニル）スルフィド、ビス（４−ヒドロキシフ
ェニル）スルホキシド等があげられ、特にビスフェノー
ルＡが好ましい。末端停止剤としては例えばp-tert−ブ
チルフェノールのような一価フェノールが使用される。
使用量は使用する二価フェノールに対し、通常０．０１
〜１０モル％、好ましくは０．０３〜８モル％である。Other dihydric phenols include, for example, bis (4-hydroxyphenyl) methane and 2,2-bis (4
-Hydroxyphenyl) propane [commonly known as bisphenol A], 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,4-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxy −3,5
-Dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, bis (4-hydroxyphenyl) oxide, bis (3,5
-Dichloro-4-hydroxyphenyl) oxide,
4,4'-dihydroxydiphenyl, 3,3'-dichloro-4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (4 -Hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide and the like, and bisphenol A is particularly preferred. As a terminal stopper, for example, a monohydric phenol such as p-tert-butylphenol is used.
The amount used is usually 0.01 to the dihydric phenol used.
10 to 10 mol%, preferably 0.03 to 8 mol%.
【００１５】ホスゲンを使用する界面重縮合反応では、
通常酸結合剤の水溶液に９，９−ビス（４−ヒドロキシ
フェニル）フルオレン類と他の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
金属の水酸化物等が使用され、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
が使用される。反応は通常０〜４０℃、好ましくは２０
〜３０℃で１０分〜１０時間程度で終了する。反応の進
行に伴い反応系のpHを１０以上に保持することが好まし
い。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あげられ
る。更に、必要に応じハイドロサルファイトのようなて
酸化防止剤を加えることもできる。In the interfacial polycondensation reaction using phosgene,
Usually, 9,9-bis (4-hydroxyphenyl) fluorenes and other dihydric phenols are dissolved in an aqueous solution of an acid binder and reacted in the presence of an organic solvent. As the acid binder, for example, a hydroxide of an alkali metal such as sodium hydroxide or potassium hydroxide is used, and as the organic solvent, for example, a halogenated hydrocarbon such as methylene chloride or chlorobenzene is used. The reaction is usually carried out at 0 to 40 ° C, preferably at 20 ° C.
It is completed in about 30 minutes at about 30 ° C. It is preferable to keep the pH of the reaction system at 10 or more as the reaction proceeds. Further, a catalyst may be used to promote the reaction. Examples of the catalyst include triethylamine and tetra-n.
Tertiary amines such as -butylammonium bromide and tetra-n-butylphosphonium bromide, quaternary ammonium compounds, quaternary phosphonium compounds and the like. Further, if necessary, an antioxidant such as hydrosulfite can be added.
【００１６】炭酸ジエステルを使用するエステル交換反
応では、不活性ガス雰囲気下９，９−ビス（４−ヒドロ
キシフェニル）フルオレン類と他の二価フェノール化合
物を炭酸ジエステルと加熱しながら撹拌して生成するア
ルコール又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又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。
反応後期には系を減圧にして生成するアルコール又はフ
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あげられる。これらのうち特に
ジフェニルカーボネートが好ましい。In a transesterification reaction using a carbonic acid diester, 9,9-bis (4-hydroxyphenyl) fluorenes and other dihydric phenol compounds are produced by stirring with a carbonic acid diester while heating under an inert gas atmosphere. It is carried out by distilling alcohol or phenol.
The reaction temperature varies depending on the boiling point of the alcohol or phenol to be formed, but is usually in the range of 120 to 350 ° C.
In the latter half of the reaction, the system is depressurized to facilitate the distillation of the alcohol or phenol produced, thereby completing the reaction. Examples of the carbonic acid diester include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like. Of these, diphenyl carbonate is particularly preferred.
【００１７】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、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。
触媒は一種だけを用いても二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０．０００
５〜０．５重量％の範囲で選ばれる。A polymerization catalyst may be used to increase the polymerization rate. Examples of the polymerization catalyst include hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide and potassium hydroxide, and hydroxides of boron and aluminum. Alkali metal salts, alkaline earth metal salts, quaternary ammonium salts, alkoxides of alkali metals and alkaline earth metals, organic acid salts of alkali metals and alkaline earth metals,
Zinc compounds, boron compounds, silicon compounds, germanium compounds, organotin compounds, lead compounds, antimony compounds, manganese compounds, titanium compounds,
Catalysts usually used for esterification reactions and transesterification reactions of zirconium compounds and the like can be used.
The catalyst may be used alone or in combination of two or more. These catalysts are used in an amount of 0.0001 to 1% by weight, preferably 0.000% by weight, based on the starting dihydric phenol.
It is selected in the range of 5 to 0.5% by weight.
【００１８】ポリカーボネート樹脂の分子量は、濃度
０．７g ／dlの塩化メチレン溶液にして２０℃で測定し
た比粘度で表して０．１９以上、好ましくは０．２６〜
０．４５のものである。０．１９未満のものでは得られ
る成形品が脆くなるので適当でない。The molecular weight of the polycarbonate resin is 0.19 or more, preferably 0.26 to less, expressed as a specific viscosity measured at 20 ° C. in a methylene chloride solution having a concentration of 0.7 g / dl.
0.45. If it is less than 0.19, the resulting molded article is not suitable because it becomes brittle.
【００１９】本発明のポリカーボネート樹脂は、前記一
般式［１］で表される構成単位と一般式［２］で表され
る構成単位の含有率が前者４１〜９５モル％に対し後者
５９〜５モル％である。一般式［１］で表される構成単
位の含有率が４１モル％未満では、複屈折が充分に低く
ならず、９５モル％を越えると複屈折は著しく低減する
が、透明性が悪くなる。The polycarbonate resin of the present invention, the latter general formula [1] Configuration units and the general formula represented by [2] in the content of the configuration unit represented Whereas the former 41-95 mol% 59 ~ 5 mol%. The formula below content of configuration single <br/> position represented by [1] is 41 mol%, not only the birefringence is sufficiently low, but birefringence is significantly reduced if it exceeds 95 mol%, Transparency worsens.
【００２０】本発明のポリカーボネート樹脂には、必要
に応じて例えばトリフェニルフォスファイト、トリス
（ノニルフェニル）フォスファイト、ジステアリルペン
タエリスリトールジフォスファイト、ジフェニルハイド
ロジェンフォスファイト、イルガノックス１０７６［ス
テアリル−β−（３，５−ジ−tert−ブチル−４−ヒド
ロキシフェニル）プロピオネート］等のような安定剤、
例えば２−（２′−ヒドロキシ−５′−メチルフェニ
ル）ベンゾトリアゾール、２−（２′−ヒドロキシ−
３′，５′−ジ−tert−アミルフェニル）ベンゾトリア
ゾール、２−（２′−ヒドロキシ−４′−オクトキシフ
ェニル）ベンゾトリアゾール、２−ヒドロキシ−４−オ
クトキシベンゾフェノン等のような耐候剤、着色剤、帯
電防止剤、離型剤、滑剤等の添加剤を加えてもよい。ま
た、本発明のポリカーボネート樹脂を成形するには射出
成形、押出成形、熱プレス成形等任意の方法が採用され
るが、透明性を高くするためには流延法で製膜する方法
が最適である。以上のようにして得られる本発明のポリ
カーボネート樹脂は高屈折率、低複屈折性で且つ優れた
透明性を示す。If necessary, the polycarbonate resin of the present invention may contain, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, diphenyl hydrogen phosphite, irganox 1076 [stearyl-β -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like;
For example, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-
Weathering agents such as 3 ', 5'-di-tert-amylphenyl) benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2-hydroxy-4-octoxybenzophenone, and the like; Additives such as a coloring agent, an antistatic agent, a release agent, and a lubricant may be added. In order to mold the polycarbonate resin of the present invention, any method such as injection molding, extrusion molding, and hot press molding is adopted. In order to increase transparency, a method of casting a film by a casting method is optimal. is there. The polycarbonate resin of the present invention obtained as described above has a high refractive index, low birefringence and excellent transparency.
【００２１】[0021]
【実施例】以下に実施例をあげて本発明を更に説明す
る。なお、実施例中の部及び％は特に断らない限り重量
部及び重量％である。また比粘度、全光線透過率、屈折
率及び光弾性係数は下記の方法で測定した。The present invention will be further described with reference to the following examples. Parts and% in Examples are parts by weight and% by weight unless otherwise specified. The specific viscosity, total light transmittance, refractive index and photoelastic coefficient were measured by the following methods.
【００２２】比粘度：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。 全光線透過率：ASTM D−１００３に準拠して日本電色
（株）製Σ８０により測定した。 屈折率：アタゴ（株）製アッベ屈折計により波長５９
８．３nmのＤ線を用いて２５℃で測定した。 光弾性係数（複屈折性）：３０mm×１０mm×１００μm
のフイルムを用い、理研計器（株）製光弾性測定装置 P
A-１５０により測定した。Specific viscosity: 0.7 g of the polymer was dissolved in 100 ml of methylene chloride and measured at 20.degree. Total light transmittance: Measured by Nippon Denshoku Co., Ltd. # 80 in accordance with ASTM D-1003. Refractive index: wavelength 59 by Abago refractometer manufactured by Atago Co., Ltd.
It was measured at 25 ° C. using a 8.3 nm D line. Photoelastic coefficient (birefringence): 30mm × 10mm × 100μm
Photoelasticity measuring device P manufactured by Riken Keiki Co., Ltd.
It was measured by A-150.
【００２３】[0023]
【実施例１】９，９−ビス（４−ヒドロキシフェニル）
フルオレン２１．５部、ビスフェノールＡ２．４７部、
４８．５％苛性ソーダ水溶液２３．８部及び蒸留水３６
１部を撹拌器付き反応器に仕込み溶解した。これに塩化
メチレン１６２部を加え、混合溶液が２０℃になるよう
に冷却し、ホスゲン１０．０部を４０分で吹込んだ。そ
の後反応液にp-tert−ブチルフェノール０．１０８部を
塩化メチレンに溶解した溶液で加え、４８．５％苛性ソ
ーダ水溶液２．９８部およびトリエチルアミン０．０５
部を加えて２時間撹拌を続けて反応を終了した。反応終
了後反応液から下層のポリカーボネートの塩化メチレン
溶液を分液し、この溶液を塩酸水溶液、蒸留水によって
洗浄した後、塩化メチレンを蒸発除去させてポリカーボ
ネートパウダーを得た。得られたパウダーの比粘度は
０．８５０であった。このパウダーを塩化メチレンに溶
解させてフイルムを製膜した。このものの全光線透過率
は８９％、屈折率は１．６３６、光弾性係数は２４×１
０-13 cm2 ／dyneであった。Example 1 9,9-bis (4-hydroxyphenyl)
21.5 parts of fluorene, 2.47 parts of bisphenol A,
23.8 parts of a 48.5% aqueous sodium hydroxide solution and 36 distilled water
One part was charged and dissolved in a reactor equipped with a stirrer. To this was added 162 parts of methylene chloride, the mixture was cooled to 20 ° C., and 10.0 parts of phosgene was blown in for 40 minutes. Thereafter, a solution of 0.108 parts of p-tert-butylphenol dissolved in methylene chloride was added to the reaction solution, and 2.98 parts of a 48.5% aqueous sodium hydroxide solution and 0.05% of triethylamine were added.
And stirring was continued for 2 hours to complete the reaction. After completion of the reaction, a methylene chloride solution of the lower layer polycarbonate was separated from the reaction solution, and this solution was washed with an aqueous hydrochloric acid solution and distilled water, and then methylene chloride was evaporated off to obtain a polycarbonate powder. The specific viscosity of the obtained powder was 0.850. This powder was dissolved in methylene chloride to form a film. It has a total light transmittance of 89%, a refractive index of 1.636, and a photoelastic coefficient of 24 × 1.
It was 0 -13 cm 2 / dyne.
【００２４】[0024]
【実施例２】９，９−ビス（４−ヒドロキシフェニル）
フルオレンを１９．０部及びビスフェノールＡを４．１
１部使用する以外は実施例１と同様にしてパウダーを得
た。このパウダーの比粘度は０．８６３であった。この
パウダーを実施例１と同様に成形し評価したところ全光
線透過率は８９％、屈折率は１．６３１、光弾性係数は
３０×１０-13 cm2 ／dyneであった。Example 2 9,9-bis (4-hydroxyphenyl)
19.0 parts of fluorene and 4.1 of bisphenol A
A powder was obtained in the same manner as in Example 1 except that one part was used. The specific viscosity of this powder was 0.863. When this powder was molded and evaluated in the same manner as in Example 1, the total light transmittance was 89%, the refractive index was 1.631, and the photoelastic coefficient was 30 × 10 −13 cm 2 / dyne.
【００２５】[0025]
【実施例３】９，９−ビス（４−ヒドロキシフェニル）
フルオレンを１２．６部及びビスフェノールＡを８．２
３部使用する以外は実施例１と同様にしてパウダーを得
た。このパウダーの比粘度は０．７５５であった。この
パウダーを実施例１と同様に成形し評価したところ全光
線透過率は９０％、屈折率は１．６１６、光弾性係数は
４８×１０-13 cm2 ／dyneであった。Example 3 9,9-bis (4-hydroxyphenyl)
12.6 parts of fluorene and 8.2 of bisphenol A
A powder was obtained in the same manner as in Example 1 except that three parts were used. The specific viscosity of this powder was 0.755. When this powder was molded and evaluated in the same manner as in Example 1, the total light transmittance was 90%, the refractive index was 1.616, and the photoelastic coefficient was 48 × 10 -13 cm 2 / dyne.
【００２６】[0026]
【比較例１】９，９−ビス（４−ヒドロキシフェニル）
フルオレンを２．５３部及びビスフェノールＡを１４．
８部使用する以外は実施例１と同様にしてパウダーを得
た。このパウダーの比粘度は１．０２４であった。この
パウダーを実施例１と同様に成形し評価したところ全光
線透過率は９０％、屈折率は１．５９２、光弾性係数は
７４×１０-13 cm2 ／dyneであった。Comparative Example 1 9,9-bis (4-hydroxyphenyl)
13. 2.53 parts of fluorene and 14 of bisphenol A.
A powder was obtained in the same manner as in Example 1 except that 8 parts were used. The specific viscosity of this powder was 1.024. When this powder was molded and evaluated in the same manner as in Example 1, the total light transmittance was 90%, the refractive index was 1.592, and the photoelastic coefficient was 74 × 10 −13 cm 2 / dyne.
【００２７】[0027]
【比較例２】比粘度が０．４５１のビスフェノールＡポ
リカーボネートパウダー［帝人化成（株）製パンライト
L−１２５０］を実施例１と同様に成形し評価したとこ
ろ全光線透過率は９０％、屈折率は１．５８９、光弾性
係数は８３×１０-13 cm2 ／dyneであった。Comparative Example 2 Bisphenol A polycarbonate powder having a specific viscosity of 0.451 [Panlite manufactured by Teijin Chemicals Ltd.]
L-1250] was molded and evaluated in the same manner as in Example 1. As a result, the total light transmittance was 90%, the refractive index was 1.589, and the photoelastic coefficient was 83 × 10 −13 cm 2 / dyne.
【００２８】[0028]
【発明の効果】本発明のポリカーボネート樹脂は高屈折
率、低複屈折で且つ透明性にも優れるので光学レンズ、
フイルム、ディスク等の高屈折率、低複屈折性、透明性
を要求される各種光学用途に極めて有用である。The polycarbonate resin of the present invention has a high refractive index, low birefringence and excellent transparency, so that an optical lens,
It is extremely useful for various optical applications requiring high refractive index, low birefringence, and transparency such as films and disks.
フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C08G 64/00 - 64/42 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)Continuation of the front page (58) Field surveyed (Int. Cl. 7 , DB name) C08G 64/00-64/42 CA (STN) REGISTRY (STN)
Claims (1)
基、炭素数１〜３のアルキル基であって、同一又は異な
っていてもよい。］で表される構成単位及び下記一般式
［２］ 【化２】 ［式中Ｗは単結合、アルキリデン基、シクロアルキリデ
ン基、フェニル基置換アルキリデン基、スルホン基、ス
ルフィド基又はオキシド基であり、Ｒ5及びＲ6は水素原
子、ハロゲン原子、フェニル基、炭素数１〜３のアルキ
ル基であって、同一又は異なっていてもよく、ｍ及びｎ
は夫々１〜４の整数である。］で表される構成単位から
なり、一般式［１］で表される構成単位を４１〜９５モ
ル％含有し、光弾性定数が５０×１０-13ｃｍ2／ｄｙｎ
ｅ以下で且つ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０．１９以上であり、一
価フェノールの末端停止剤を全二価フェノールに対し、
０．０１〜１０モル％用いた高屈折率、低複屈折性ポリ
カーボネート樹脂。[Claim 1] The following general formula [1] [Wherein R 1 to R 4 are a hydrogen atom, a halogen atom, a phenyl group, or an alkyl group having 1 to 3 carbon atoms, which may be the same or different. And a structural unit represented by the following general formula [2]: [Wherein W is a single bond, an alkylidene group, a cycloalkylidene group, a phenyl group-substituted alkylidene group, a sulfone group, a sulfide group or an oxide group, and R 5 and R 6 are a hydrogen atom, a halogen atom, a phenyl group, a carbon atom of 1; To 3 alkyl groups which may be the same or different, and m and n
Is an integer of 1 to 4, respectively. Consists of structural units represented by in], the configuration unit represented by the general formula [1] containing 41 to 95 mol%, photoelastic constant 50 × 10 -13 cm 2 / dyn
The and 0.7g in e less Ri der measured specific viscosity in dissolved 20 ° C. in methylene chloride 0.19 or more 100 ml, one
The terminating agent for the polyhydric phenol is
A high-refractive-index, low-birefringent polycarbonate resin used in an amount of 0.01 to 10 mol% .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17979392A JP3187142B2 (en) | 1992-07-07 | 1992-07-07 | High refractive index, low birefringence polycarbonate resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17979392A JP3187142B2 (en) | 1992-07-07 | 1992-07-07 | High refractive index, low birefringence polycarbonate resin |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001070133A Division JP3499838B2 (en) | 2001-03-13 | 2001-03-13 | Film for retardation film formed from high refractive index and low birefringence polycarbonate resin and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0625398A JPH0625398A (en) | 1994-02-01 |
| JP3187142B2 true JP3187142B2 (en) | 2001-07-11 |
Family
ID=16071996
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17979392A Expired - Fee Related JP3187142B2 (en) | 1992-07-07 | 1992-07-07 | High refractive index, low birefringence polycarbonate resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3187142B2 (en) |
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| WO2012102224A1 (en) | 2011-01-27 | 2012-08-02 | 三菱瓦斯化学株式会社 | Polycarbonate resin and process for production thereof |
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| US5486577A (en) * | 1995-03-21 | 1996-01-23 | The Dow Chemical Company | Blends of diaryl fluorene carbonate polymers with bisphenol A carbonate polymers |
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-
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|---|---|
| JPH0625398A (en) | 1994-02-01 |
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