JPWO2014054710A1 - Thermoplastic resin composition having fluorene skeleton and optical member - Google Patents

Abstract

An object of the present invention is to provide a thermoplastic resin composition having high transparency and excellent molding fluidity, molding stability, and heat-and-moisture resistance, and an optical member comprising the same. The present invention has 100 parts by weight of a thermoplastic resin having a fluorene skeleton containing a repeating unit composed of a carbonate unit or an ester unit derived from a monomer composed of the following general formula (1) and a portion composed of the following general formula (2). It is a thermoplastic resin composition having a fluorene skeleton containing 0.1 to 10 parts by weight of an aliphatic epoxy compound.

Description

  The present invention relates to a thermoplastic resin composition having a fluorene skeleton having high transparency and excellent molding fluidity, molding stability, and heat-and-moisture resistance, and an optical member comprising the same.

Optical glass or optical transparent resin is used as a material for optical lenses used in optical systems of various cameras such as cameras, film-integrated cameras, and video cameras. Optical glass has excellent heat resistance, transparency, dimensional stability, chemical resistance, etc., and there are many types of materials with various refractive indexes and Abbe numbers. The problem is that the productivity is low and the productivity is low.
On the other hand, optical transparent resins, in particular thermoplastic optical transparent resins, have the advantage that they can be mass-produced by injection molding, and polycarbonate resins and the like are currently used as materials for camera lenses. However, in recent years, the optical performance required for lens resins has become higher as products become lighter and thinner and cameras have higher pixels. In particular, in recent years, an optical lens with higher imaging performance and lower birefringence has been demanded as the resolution is increased by increasing the number of pixels.
Resins using 9,9-biscresol fluorene derivatives and 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene derivatives have high refractive index and low birefringence and have excellent optical properties. Used in optical lenses.
These optical lenses are used in various applications, but the shapes and sizes vary greatly depending on the applications. For example, a camera lens for a mobile phone is very small and thin with a diameter of about 5 mm and a thickness of about 0.3 mm. In recent years, the size and thickness of the camera lens have been further reduced. When injection molding such a small thin lens, if the molding fluidity of the resin is insufficient, a lens having a desired shape cannot be obtained, and the molding fluidity is a very important characteristic.
Generally, a plasticizer is used as a method for modifying the molding fluidity of a thermoplastic resin.
As plasticizers, phthalate ester plasticizers, trimellitic ester plasticizers, phosphate triester plasticizers, and the like are widely used.
As another modification method of fluidity, Patent Document 1 proposes a method of adding a polycarbonate oligomer and polycaprolactone to a polycarbonate resin.
Further, Patent Documents 2 and 3 propose a method of adding a polyether ester resin or a styrene oligomer resin as a method for modifying the molding fluidity of a thermoplastic resin having a fluorene structure.
In addition to the optical characteristics and molding fluidity, the characteristics required for optical lenses are difficult to use as a lens when the focal length and chromatic aberration are affected by the environment in which the lens is used. It is also an important characteristic for heat and humidity resistance. Further, molding stability such as a low yield during molding is also a very important characteristic.
However, the method using a plasticizer and the compositions of Patent Documents 1 to 3 have problems in high transparency, molding stability, and wet heat resistance.
That is, a thermoplastic resin using a fluorene derivative has not been obtained which has a high degree of transparency and sufficiently satisfies the moist heat resistance while maintaining the molding fluidity and molding stability.
JP 2011-63812 A JP 2006-104322 A JP 2006-143831 A

（式中、Ｒ１、Ｒ２、Ｒ３およびＲ４は、それぞれ独立に水素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシル基、炭素数５〜２０のシクロアルキル基、炭素数５〜２０のシクロアルコキシル基、炭素数６〜２０のアリール基または炭素数６〜２０のアリールオキシ基である。Ｘは炭素数２〜８のアルキレン基、炭素数５〜１２のシクロアルキレン基または炭素数６〜２０のアリーレン基である。ｎおよびｍは０〜１０の整数である。）で表わされるモノマーから誘導されるカーボネート単位またはエステル単位からなる繰り返し単位を含む熱可塑性樹脂（以下、フルオレン骨格を有する熱可塑性樹脂と称することがある）１００重量部および
下記一般式（２）

（式中、ＲはＣＨ_３またはＨであり、ｏは１〜２０であり、ｐは１〜１０であり、Ｉは１〜２０である。）で表される部位を有する脂肪族系エポキシ化合物を０．１〜１０重量部含有するフルオレン骨格を有する熱可塑性樹脂組成物。
２．脂肪族系エポキシ化合物が、グリセリン骨格を有するエポキシ化合物である前記１に記載のフルオレン骨格を有する熱可塑性樹脂組成物。
３．グリセリン骨格を有するエポキシ化合物が、エポキシ化植物油である前記２に記載のフルオレン骨格を有する熱可塑性樹脂組成物。
４．エポキシ化植物油がエポキシ化大豆油、エポキシあまに油である前記３に記載のフルオレン骨格を有する熱可塑性樹脂組成物
５．エポキシ化大豆油、エポキシ化あまに油のエポキシ基の数が、２〜８である前記４に記載のフルオレン骨格を有する熱可塑性樹脂組成物。
６．熱可塑性樹脂は、一般式（１）で表わされるモノマーから誘導されるカーボネート単位からなる繰り返し単位及び下記一般式（３）

（式中、Ｒ５〜Ｒ８は夫々独立して水素原子、炭素原子数１〜９の芳香族基を含んでもよい炭化水素基又はハロゲン原子であり、Ｗは単結合、炭素原子数１〜２０の芳香族基を含んでよい炭水素基、Ｏ、Ｓ、ＳＯ、ＳＯ_２、ＣＯ又はＣＯＯ基である。）
で表されるモノマーから誘導されるカーボネート単位からなる繰り返し単位よりなり、式（１）と式（３）の割合がモル比で（１）：（３）＝１００：０〜５０：５０の範囲のポリカーボネートであり、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０．１２〜０．５５である前記１〜５のいずれかに記載のフルオレン骨格を有する熱可塑性樹脂組成物。
７．熱可塑性樹脂は、下記一般式（４）

（式中、Ｒ１３およびＲ１４は、それぞれ独立に水素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシル基、炭素数６〜２０のアリール基または炭素数６〜２０のアリールオキシ基である。）で表わされるモノマーから誘導されるエステル系の単位および／または、
一般式（５）

（式中、Ｒ１５およびＲ１６は、それぞれ独立に水素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシル基、炭素数６〜２０のアリール基または炭素数６〜２０のアリールオキシ基である。）で表されるモノマーから誘導されるエステル系の単位を含有し、式（１）と式（４）および式（５）の合計との割合がモル比で（１）：（（４）＋（５））＝５０：５０〜９５：５の範囲のポリエステルカーボネートであり、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０．１２〜０．５５である前記１〜５のいずれかに記載のフルオレン骨格を有する熱可塑性樹脂組成物。
８．一般式（１）で表されるモノマーが、９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレンもしくは、９，９−ビス（４−（２−ヒドロキシエトキシ）フェニル）フルオレンである前記１〜７のいずれかに記載のフルオレン骨格を有する熱可塑性樹脂組成物。
９．前記１〜８のいずれかに記載のフルオレン骨格を有する熱可塑性樹脂組成物からなる光学部材。
１０．光学部材が、カメラレンズ、ピックアップレンズ、マイクロアレーレンズ、プロジェクターレンズ又はフレネルレンズの光学レンズである前記９記載の光学部材。
１１．光学レンズの厚さが厚さ０．５ｍｍ以下である前記１０に記載の光学部材。Accordingly, an object of the present invention is to provide a thermoplastic resin composition having a fluorene skeleton having high transparency, molding fluidity, molding stability, and moist heat resistance, and an optical member comprising the same.
The present inventors have intensively studied to achieve this purpose. As a result, the inventors have found that the thermoplastic resin having a fluorene skeleton is excellent in high transparency, molding fluidity, molding stability, and moist heat resistance by mixing an appropriate amount of an aliphatic epoxy compound. .
That is, the present invention
1. The following general formula (1)

(In the formula, R1, R2, R3 and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or 5 carbon atoms. A cycloalkoxyl group having 20 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, X is an alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or carbon. A thermoplastic resin containing a repeating unit consisting of a carbonate unit or an ester unit derived from a monomer represented by the following formula: n and m are integers of 0 to 10. 100 parts by weight and the following general formula (2)

(Wherein R is CH ₃ or H, o is 1 to 20, p is 1 to 10, and I is 1 to 20). A thermoplastic resin composition having a fluorene skeleton containing 0.1 to 10 parts by weight.
2. 2. The thermoplastic resin composition having a fluorene skeleton as described in 1 above, wherein the aliphatic epoxy compound is an epoxy compound having a glycerin skeleton.
3. 3. The thermoplastic resin composition having a fluorene skeleton as described in 2 above, wherein the epoxy compound having a glycerin skeleton is an epoxidized vegetable oil.
4). 4. The thermoplastic resin composition having a fluorene skeleton as described in 3 above, wherein the epoxidized vegetable oil is epoxidized soybean oil or epoxy linseed oil. 5. The thermoplastic resin composition having a fluorene skeleton as described in 4 above, wherein the number of epoxy groups in the epoxidized soybean oil and epoxidized sesame oil is 2 to 8.
6). The thermoplastic resin includes a repeating unit composed of a carbonate unit derived from a monomer represented by the general formula (1) and the following general formula (3).

(Wherein R5 to R8 are each independently a hydrogen atom, a hydrocarbon group or a halogen atom which may contain an aromatic group having 1 to 9 carbon atoms, and W is a single bond, having 1 to 20 carbon atoms. A hydrocarbon group, O, S, SO, SO ₂ , CO or COO group which may contain an aromatic group.)
The ratio of the formula (1) and the formula (3) is a molar ratio of (1) :( 3) = 100: 0 to 50:50. A thermoplastic having a fluorene skeleton according to any one of 1 to 5 above, wherein 0.7 g is dissolved in 100 ml of methylene chloride and the specific viscosity measured at 20 ° C. is 0.12 to 0.55. Resin composition.
7). The thermoplastic resin is represented by the following general formula (4).

(In the formula, R13 and R14 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms. An ester-based unit derived from a monomer represented by:
General formula (5)

(In the formula, R15 and R16 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms. The ratio of the formula (1) and the sum of the formula (4) and the formula (5) is a molar ratio of (1) :( (4) + (5)) = polyester carbonate in the range of 50:50 to 95: 5, 0.7 g is dissolved in 100 ml of methylene chloride, and the specific viscosity measured at 20 ° C. is 0.12 to 0.4. 55. The thermoplastic resin composition having a fluorene skeleton according to any one of 1 to 5, which is 55.
8). The monomer represented by the general formula (1) is 9,9-bis (4-hydroxy-3-methylphenyl) fluorene or 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene. A thermoplastic resin composition having a fluorene skeleton according to any one of 1 to 7.
9. An optical member comprising a thermoplastic resin composition having the fluorene skeleton according to any one of 1 to 8 above.
10. 10. The optical member according to 9, wherein the optical member is an optical lens of a camera lens, a pickup lens, a microarray lens, a projector lens, or a Fresnel lens.
11 11. The optical member as described in 10 above, wherein the thickness of the optical lens is 0.5 mm or less.

式中、ＲはＣＨ_３またはＨであり、ｏは１〜２０あり、ｐは１〜１０であり、Ｉは１〜２０である。）で表わされる部位を有する脂肪族系エポキシ系化合物である。
式中におけるｏが１〜２０である場合は、アルキレン基の効果により、透明性を保持したまま、成形流動性を向上させる事ができる。ｏが１より少ない場合は、成形流動性が不足し、２０より大きい場合は、樹脂との相溶性が悪化し透明性が保持できない。
式中におけるｐが１〜１０である場合は、水分をエポキシ基がトラップし、熱可塑性樹脂の加水分解を抑制することで、耐湿熱安定性が良好となる。ｐが１より少ない場合、耐湿熱安定性が低下する。１０より多い場合は、脂肪族系エポキシ化合物同士が反応し多量体を形成することで、耐湿熱安定性が低下する。さらに好ましくは、２〜８であり、より好ましくは、３〜８である。
式中におけるＩが１〜２０である場合、高度な透明性、耐湿熱安定性を保持した成形流動性が向上する。Ｉが１より少ない場合は、成形流動性が不足・耐湿熱性が劣化する。さらに、樹脂からのブリードアウトの生じる可能性がある。又、Ｉが２０より大きい場合、樹脂との相溶性が悪化し透明性が保持できない。
本発明に使用される上記の脂肪族系エポキシ化合物は、分子骨格中に１個以上のエポキシ基を有する化合物である。エポキシ基が１個以上有すると、エポキシ基が水と反応し、樹脂の加水分解を抑制する事で耐湿熱安定性が向上する。
本発明に使用される上記の脂肪族系エポキシ化合物は、グリセリン骨格とエポキシ基を有する脂肪鎖とがエステルを介して結合している化合物であって、特に、上記式（２）のカルボニル基を除いた脂肪鎖のメチレン基の数が２〜２０であることが、高透明性、成形流動性、耐湿熱安定性、および成形時ガス発生抑制等の成形安定性の観点から好ましい。
かかるグリセリン骨格を有する脂肪族系エポキシ化合物の中でも、エポキシ化植物油が好ましくエポキシ化大豆油、エポキシ化あまに油がさらに好ましい。特に、エポキシ基の数が２〜６個であるエポキシ化大豆油、エポキシ化あまに油が耐湿熱安定性の観点から好ましい。
かかる脂肪族系エポキシ化合物は、後述するフルオレン骨格を有する熱可塑性樹脂１００重量部に対して、０．１〜１０重量部含有する事が必要である。含有量が、０．１重量部より少ない場合は、成形流動性に劣る。一方、１０重量部より多い場合、樹脂と相溶せず透明性を保持できなくなり、さらに高温高湿度下で使用した際に、フルオレン骨格を有する熱可塑性樹脂の分子量が低下し、樹脂色相、強度が低下するなど、耐湿熱安定性が低下する。
本発明に使用される上記の脂肪族系エポキシ化合物の含有量は、フルオレン骨格を有する熱可塑性樹脂１００重量部に対し、好ましくは、０．１〜８重量部であり、さらに好ましくは、０．１〜５重量部である。
＜フルオレン化合物＞
本発明に使用される下記式（１）

（式中、Ｒ１、Ｒ２、Ｒ３およびＲ４は、それぞれ独立に水素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシル基、炭素数５〜２０のシクロアルキル基、炭素数５〜２０のシクロアルコキシル基、炭素数６〜２０のアリール基または炭素数６〜２０のアリールオキシ基である。Ｘは炭素数２〜８のアルキレン基、炭素数５〜１２のシクロアルキレン基または炭素数６〜２０のアリーレン基である。ｎおよびｍは０〜１０の整数である。）で表されるモノマーは、フルオレン化合物である。
Ｒ１、Ｒ２、Ｒ３およびＲ４は、それぞれ独立に水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシル基、炭素数５〜１０のシクロアルキル基、炭素数５〜１０のシクロアルコキシル基である事が好ましい。
具体的に表わされるフルオレン化合物は、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、９，９−ビス（４−ヒドロキシ−３−フェニルフェニル）フルオレン、９，９−ビス（４−ヒドロキシエトキシフェニル）フルオレン、９，９−ビス（４−ヒドロキシプロポキシフェニル）フルオレン、９，９−ビス−（４−ヒドロキシブトキシフェニル）フルオレン等が好ましい。中でもフルオレン化合物は９，９−ビス（４−ヒドロキシ−３−メチルフェニル）フルオレンもしくは、９，９−ビス（４−（２−ヒドロキシエトキシ）フェニル）フルオレンであることがより好ましい。
＜熱可塑性樹脂＞
本発明に使用される熱可塑性樹脂は、上記式（１）のフルオレン化合物から誘導されるカーボネート単位またはエステル単位からなる繰り返し単位を含むものであって、例えばポリカーボネート、ポリエステルカーボネート等が挙げられる。
［ポリカーボネート］
本発明に使用されるポリカーボネートは、上記式（１）で表されるフルオレン化合物と共重合可能な、下記一般式（３）で表されるジヒドロキシ化合物から誘導されるカーボネート単位からなる繰り返し単位を有していてもよい。

（式中、Ｒ５〜Ｒ８は夫々独立して水素原子、炭素原子数１〜９の芳香族基を含んでもよい炭化水素基又はハロゲン原子であり、Ｗは単結合、炭素原子数１〜２０の芳香族基を含んでもよい炭化水素基、Ｏ、Ｓ、ＳＯ、ＳＯ_２、ＣＯ又はＣＯＯ基である。）
本発明に使用されるポリカーボネートにおいて一般式（３）のＷは、下記式（６）で表わされる基であることが好ましい。

（式中、Ｒ９、Ｒ１０は同一または異なり、水素原子または炭素数１〜１０の炭化水素基、Ｒ１１およびＲ１２は夫々独立して水素原子または炭素数１〜３のアルキル基を表わし、ｎは４〜７の整数である。）
好ましく用いられるジヒドロキシ化合物としては、例えば４，４′−ビフェノール、１，１−ビス（４−ヒドロキシフェニル）エタン（ビスフェノールＥ）、２，２−ビス（４−ヒドロキシフェニル）プロパン（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（ビスフェノールＣ）、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）−１−フェニルエタン、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン（ビスフェノールＺ）、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、２，２−ビス（４−ヒドロキシフェニル）ペンタン、４，４′−（ｐ−フェニレンジイソプロピリデン）ジフェノール、α，α′−ビス（４−ヒドロキシフェニル）−ｍ−ジイソプロピルベンゼン（ビスフェノールＭ）、１，１−ビス（４−ヒドロキシフェニル）−４−イソプロピルシクロヘキサン等の芳香族ジオールが挙げられ、なかでもビスフェノールＡ、ビスフェノールＺ、ビスフェノールＣ、ビスフェノールＥ、ビスフェノールＭが好ましい。特にビスフェノールＡが好ましい。これらは単独または二種以上組み合わせて用いてもよい。
なお、光学特性を阻害しない範囲で、ハイドロキノン、レゾルシノール等の一般式（３）に該当しない芳香族ジヒドロキシ化合物、エチレングリコール等の脂肪族ジオール、トリシクロ［５．２．１．０２，６］デカンジメタノール、シクロヘキサン−１，４−ジメタノール、デカリン−２， ６−ジメタノール、ノルボルナンジメタノール、ペンタシクロペンタデカンジメタノール、シクロペンタン−１，３−ジメタノール、スピログリコール、１，４：３，６−ジアンヒドロ−Ｄ−ソルビトール、１，４：３，６−ジアンヒドロ−Ｄ−マンニトール、１，４：３，６−ジアンヒドロ−Ｌ−イジトール等の脂環式ジオールに由来するカーボネート単位を含んでもよい。これらは、１種を単独で使用しても、２種類以上を組み合わせて用いてもよい。
式（１）と式（３）の割合がモル比で（１）：（３）＝１００：０〜５０：５０の範囲のポリカーボネートであり、９８：２〜５０：５０の範囲が好ましく、９５：５〜５０：５０の範囲がより好ましい。
［ポリカーボネートの製造方法］
かかるポリカーボネート樹脂は、通常のポリカーボネート樹脂を製造するそれ自体公知の反応手段、例えばジヒドロキシ化合物にホスゲンや炭酸ジエステルなど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。
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、通常酸結合剤および溶媒の存在下に反応を行う。酸結合剤としては、例えばピリジンなどのアミン化合物が用いられる。溶媒としては、例えば塩化メチレン、クロロベンゼンなどのハロゲン化炭化水素が用いられる。その際、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。
本発明のポリカーボネート樹脂は、その重合反応において、末端停止剤として通常使用される単官能フェノール類を使用することができる。殊にカーボネート前駆物質としてホスゲンを使用する反応の場合、単官能フェノール類は末端停止剤として分子量調節のために一般的に使用され、また得られた芳香族ポリカーボネート樹脂は、末端が単官能フェノール類に基づく基によって封鎖されているので、そうでないものと比べて熱安定性に優れている。
カーボネート前駆物質として炭酸ジエステルを用い、塩基性化合物触媒、エステル交換触媒もしくはその双方からなる混合触媒の存在下、反応させる公知の溶融重縮合法（エステル交換反応）により製造することもできる。
炭酸ジエステルとしては、ジフェニルカーボネート、ジトリールカーボネート、ビス（クロロフェニル）カーボネート、ｍ−クレジルカーボネート、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、ジシクロヘキシルカーボネート等が挙げられる。これらの中でも特にジフェニルカーボネートが好ましい。炭酸ジエステルは、ジオール成分１モルに対して０．９７〜１．２０モルの比率で用いられることが好ましく、更に好ましくは０．９８〜１．１０モルの比率である。
塩基性化合物触媒としては、アルカリ金属化合物、アルカリ土類金属化合物、および含窒素化合物等があげられる。
このような化合物としては、アルカリ金属およびアルカリ土類金属の有機酸塩、無機塩、酸化物、水酸化物、水素化物あるいはアルコキシド等、および４級アンモニウムヒドロキシドおよびそれらの塩、アミン類等の含窒素化合物が好ましく用いられ、これらの化合物は単独もしくは組み合わせて用いることができる。
かかるアルカリ金属化合物としては、具体的には、水酸化ナトリウム、水酸化カリウム、炭酸水素ナトリウム、炭酸ナトリウム、炭酸カリウム、酢酸ナトリウム、安息香酸ナトリウム、ビスフェノールＡの２ナトリウム塩、フェノールのナトリウム塩等が用いられる。
アルカリ土類金属化合物としては、具体的には、水酸化マグネシウム、水酸化カルシウム等が用いられる。
含窒素化合物としては、具体的には、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド等のアルキル、アリール、基等を有する４級アンモニウムヒドロキシド類、トリエチルアミン、ジメチルベンジルアミン、トリフェニルアミン等の３級アミン類、ジエチルアミン、ジブチルアミン等の２級アミン類、プロピルアミン、ブチルアミン等の１級アミン類、２−メチルイミダゾール、２−フェニルイミダゾール、ベンゾイミダゾール等のイミダゾール類、等が用いられる。
エステル交換触媒としては、亜鉛、スズ、ジルコニウム、鉛の塩が好ましく用いられ、これらは単独もしくは組み合わせて用いることができる。
エステル交換触媒としては、具体的には、酢酸亜鉛、安息香酸亜鉛、２−エチルヘキサン酸亜鉛、塩化スズ（ＩＩ）、塩化スズ（ＩＶ）、酢酸スズ（ＩＩ）、酢酸スズ（ＩＶ）、ジブチルスズジラウレート、ジブチルスズオキサイド、ジブチルスズジメトキシド、ジルコニウムアセチルアセトナート、オキシ酢酸ジルコニウム、ジルコニウムテトラブトキシド、酢酸鉛（ＩＩ）、酢酸鉛（ＩＶ）等が用いられる。
これらの触媒は、ジヒドロキシ化合物の合計１モルに対して、１０^−９〜１０^−３モルの比率で、好ましくは１０^−７〜１０^−４モルの比率で用いられる。
溶融重縮合法は、前記の原料、および触媒を用いて、加熱下に常圧または減圧下にエステル交換反応により副生成物を除去しながら溶融重縮合を行うものである。反応は、一般には二段以上の多段行程で実施される。
具体的には、第一段目の反応を１２０〜２６０℃、好ましくは１８０〜２４０℃の温度で０．１〜５時間、好ましくは０．５〜３時間反応させる。次いで反応系の減圧度を上げながら反応温度を高めてジヒドロキシ化合物と炭酸ジエステルとの反応を行い、最終的には１ｍｍＨｇ以下の減圧下、２００〜３５０℃の温度で０．０５〜２時間重縮合反応を行う。このような反応は、連続式で行っても良くまたバッチ式で行ってもよい。上記の反応を行うに際して用いられる反応装置は、錨型攪拌翼、マックスブレンド攪拌翼、ヘリカルリボン型攪拌翼等を装備した縦型であっても、パドル翼、格子翼、メガネ翼等を装備した横型であってもスクリューを装備した押出機型であってもよい。特に、これらを重合物の粘度を勘案して適宜組み合わせた反応装置を使用することが好適である。
得られたポリカーボネート樹脂は、重合反応終了後、熱安定性および加水分解安定性を保持するために、触媒を除去もしくは失活させる。一般的には、公知の失活剤の添加による触媒の失活を行う方法が好適に実施される。これらの物質としては、具体的には、安息香酸ブチル等のエステル類、ｐ−トルエンスルホン酸等の芳香族スルホン酸類、ｐ−トルエンスルホン酸ブチル、ｐ−トルエンスルホン酸ヘキシル等の芳香族スルホン酸エステル類、亜リン酸、リン酸、ホスホン酸等のリン酸類、塩化ベンゾイル、ｐ−トルエンスルホン酸クロライド等が好適に用いられる。これらの失活剤は、触媒量に対して０．０１〜５０倍モル、好ましくは０．３〜２０倍モル使用される。触媒量に対して０．０１倍モルより少ないと、失活効果が不充分となる。また、触媒量に対して５０倍モルより多いと、耐熱性が低下し、成形体が着色しやすくなる。
触媒失活後、ポリマー中の低沸点化合物を１３．３〜１１３３．３Ｐａの圧力、２００〜３５０℃の温度で脱揮除去する工程を設けても良く、このためには、パドル翼、格子翼、メガネ翼等、表面更新能の優れた攪拌翼を備えた横型装置、あるいは薄膜蒸発器が好適に用いられる。
本発明におけるポリカーボネート樹脂はそのポリマー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０．１２〜０．５５の範囲のものが好ましく、０．１５〜０．４５の範囲のものがより好ましい。比粘度が０．１２未満では成形品が脆くなり、０．５５より高くなると溶融粘度および溶液粘度が高くなる。
＜ポリエステルカーボネート＞
本発明に使用されるポリエステルカーボネートは、エステル単位を形成する酸成分が前記一般式（４）および／または一般式（５）で表されるジカルボン酸成分であり、一般式（１）で表されるモノマー成分と、一般式（４）および／または一般式（５）で表されるジカルボン酸成分の合計との割合が、モル比で（１）：（（４）＋（５））＝５０：５０〜９５：５、好ましくは７０：３０〜９５：５、さらに好ましくは７５：２５〜９０：１０である。後者の割合が５０：５０を超えると光学用材料としての性能が低下する場合がある。
かかるポリエステルカーボネートには、上記式（１）で表されるフルオレン化合物と共重合可能な、前記一般式（３）で表されるジヒドロキシ化合物を共重合していてもよい。
一般式（３）で表されるジヒドロキシ化合物の割合は、一般式（１）で表されるフルオレン化合物とのモル比で、式（１）：式（３）＝８０〜１００：２０〜０が好ましく、さらに好ましくは９０〜１００：１０〜０である。
好ましく用いられる一般式（３）で表されるジヒドロキシ化合物は、前記のポリカーボネートで説明したものと同様である。また、同様に、光学特性を阻害しない範囲で他のジヒドロキシ化合物を併用してもよい。
［ジカルボン酸］
エステル単位を形成する酸成分は、下記一般式（４）

（式中、Ｒ１３およびＲ１４は、それぞれ独立に水素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシル基、炭素数６〜２０のアリール基または炭素数６〜２０のアリールオキシ基である。）で表されるジカルボン酸、および／または下記一般式（５）

（式中、Ｒ１５およびＲ１６は、それぞれ独立に水素原子、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシル基、炭素数６〜２０のアリール基または炭素数６〜２０のアリールオキシ基である。）で表されるジカルボン酸である。
好ましい一般式（４）で表されるジカルボン酸としては、テレフタル酸、イソフタル酸が挙げられ、特にテレフタル酸が好ましい。また、好ましく用いられる一般式（５）で表されるジカルボン酸としては、２，６−ナフタレンジカルボン酸、２，７−ナフタレンジカルボン酸、１，８−ナフタレンジカルボン酸等が挙げられ、特に２，６−ナフタレンジカルボン酸が好ましい。なかでも、ジカルボン酸としては、テレフタル酸、イソフタル酸、特にテレフタル酸が好ましい。
なお、光学特性を阻害しない範囲で、一般式（４）または一般式（５）で表されるジカルボン酸以外のジカルボン酸成分を含んでいてもよい。
［ポリエステルカーボネートの製造方法］
かかるポリエステルカーボネート樹脂の製造に用いるカーボネート前駆物質は、例えばホスゲン、ジフェニルカーボネート、上記二価フェノール類のビスクロロホーメート、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等が挙げられ、なかでもジフェニルカーボネートが好ましい。
ポリエステルカーボネート樹脂を製造する方法は、通常のポリエステルカーボネート樹脂の製造に用いる方法が、任意に採用される。例えばジオールとジカルボン酸又はジカルボン酸クロライドとホスゲンとの反応、又はジオールとジカルボン酸またはジカルボン酸ジアルキルエステルとビスアリールカーボネートとのエステル交換反応が好ましく採用される。
ジオール、ジカルボン酸又はその酸クロライドとホスゲンとの反応では、非水系で酸結合剤及び溶媒の存在下に反応を行う。酸結合剤としては例えばピリジン、ジメチルアミノピリジン、第三級アミン等が用いられる。溶媒としては例えば塩化メチレンやクロロベンゼン等のハロゲン化炭化水素が用いられる。分子量調節剤として例えばフェノールやｐ−ｔｅｒｔ−ブチルフェノール等の末端停止剤を用いることが望ましい。反応温度は通常０〜４０℃、反応時間は数分〜５時間が好ましい。
エステル交換反応では、不活性ガス存在下にジオールとジカルボン酸又はそのジエステルとビスアリールカーボネートを混合し、減圧下通常１２０〜３５０℃、好ましくは１５０〜３００℃で反応させる。減圧度は段階的に変化させ、最終的には１ｍｍＨｇ以下にして生成したアルコール類を系外に留去させる。反応時間は通常１〜４時間程度である。しかしながら、重合温度が、３５０℃以上ではフェニルビニルエーテルやアセトアルデヒドが副生し易くなり、好ましくない。
また、エステル交換反応では反応促進のために重合触媒を用いることができる。このような重合触媒としてはアルカリ金属化合物又はアルカリ土類金属化合物又は重金属化合物を主成分として用い、必要に応じて含窒素塩基性化合物を従成分として用いても良い。
アルカリ金属化合物としては水酸化ナトリウム、水酸化カリウム、ビスフェノールＡのナトリウム塩等が挙げられる。アルカリ土類金属化合物としては水酸化カルシウム、水酸化マグネシウム、炭酸カルシウム等が挙げられる。
含窒素塩基性化合物としてはテトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、トリメチルベンジルアンモニウムヒドロキシド、トリメチルアミン、トリエチルアミン、ジメチルベンジルアミン、トリフェニルアミン、ジメチルアミノピリジン等が挙げられる。
その他のエステル交換触媒としては亜鉛、スズ、ジルコニウム、鉛、チタン、ゲルマニウム、アンチモン、オスミウム、アルミニウムの塩が挙げられ、例えば、酢酸亜鉛、安息香酸亜鉛、２−エチルヘキサン酸亜鉛、塩化スズ（ＩＩ）、塩化スズ（ＩＶ）、酢酸スズ（ＩＩ）、酢酸スズ（ＩＶ）、ジブチルスズジラウレート、ジブチルスズオキサイド、ジブチルスズジメトキシド、ジルコニウムアセチルアセトナート、オキシ酢酸ジルコニウム、ジルコニウムテトラブトキシド、酢酸鉛（ＩＩ）、酢酸鉛（ＩＶ）チタンテトラブトキシド（ＩＶ）等が用いられる。
これらの触媒は単独で用いても、二種以上併用してもよく、これらの重合触媒の使用量はジオールとジカルボン酸の合計１モルに対して、１０^−９〜１０^−３モルの比率で用いられる。これらは単独で用いても、二種以上併用してもよい。また、エステル交換反応ではヒドロキシ末端基を減少するために重縮合反応の後期又は終了後に電子吸引性の置換基を持ったジアリールカーボネートを加えても良い。更に、色相改善のために酸化防止剤や熱安定剤等を加えてもよい。
また、重合反応終了後、熱安定性および加水分解安定性を保持するために、触媒を除去もしくは失活させてもよい。アルカリ金属化合物又はアルカリ土類金属化合物については、一般的に、公知の失活剤の添加による触媒の失活を行う方法が好適に実施される。これらの物質としては、具体的には、安息香酸ブチル等のエステル類、ｐ−トルエンスルホン酸等の芳香族スルホン酸類、ｐ−トルエンスルホン酸ブチル等の芳香族スルホン酸エステル類、亜リン酸、リン酸、ホスホン酸等のリン酸類、亜リン酸トリフェニル、亜リン酸モノフェニル、亜リン酸ジフェニル、亜リン酸ジエチル、亜リン酸ジｎ−プロピル、亜リン酸ジｎ−ブチル、リン酸トリフェニル等のリン酸エステル類、ジフェニルホスホン酸のホスホン酸類、フェニルホスホン酸ジエチル等のホスホン酸エステル類、トリフェニルホスフィン、等のホスフィン類、ドデシルベンゼンスルホン酸テトラブチルホスホニウム塩等の芳香族スルホン酸塩類、が好適に用いられる。これらの失活剤は、触媒量に対して０．０１〜５０倍モル、好ましくは０．３〜２０倍モル使用される。触媒量に対して０．０１倍モルより少ないと、失活効果が不充分となる。また、触媒量に対して５０倍モルより多いと、耐熱性が低下し、成形体が着色しやすくなる。
触媒失活後、樹脂中の低沸点化合物を１３３〜１３．３Ｐａの圧力、２００〜３２０℃の温度で脱揮除去する工程を設けても良い。
本発明におけるポリエステルカーボネート樹脂は、そのポリマー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、０．１２〜０．５５の範囲のものが好ましく、０．１５〜０．４５の範囲のものがより好ましい。比粘度が０．１２未満では成形品が脆くなり、０．５５より高くなると溶融粘度および溶液粘度が高くなり、取扱いが困難になる。
＜添加剤＞
本発明の熱可塑性樹脂組成物には、本発明の目的を損なわない範囲で各種特性を付与するために、各種添加剤を含有してもよい。添加剤とし、離型剤、熱安定剤、紫外線吸収剤、ブルーイング剤、帯電防止剤、難燃剤、熱線遮蔽剤、蛍光染料（蛍光増白剤を含む）、光拡散剤、他の樹脂やエラストマー等を配合することができる。
離型剤としては、その９０重量％以上がアルコールと脂肪酸のエステルからなるものが好ましい。アルコールと脂肪酸のエステルとしては、具体的には一価アルコールと脂肪酸のエステルおよび／または多価アルコールと脂肪酸との部分エステルあるいは全エステルが挙げられる。これらのエステルのなかでも、ステアリン酸モノグリセリド、ステアリン酸トリグリセリド、ペンタエリスリトールテトラステアレート、ステアリン酸トリグリセリドとステアリルステアレートの混合物が好ましく用いられる。
離型剤中の前記エステルの量は、離型剤を１００重量％とした時、９０重量％以上が好ましく、９５重量％以上がより好ましい。
熱安定剤としては、リン系熱安定剤、硫黄系熱安定剤およびヒンダードフェノール系熱安定剤が挙げられる。リン系熱安定剤としては、亜リン酸、リン酸、亜ホスホン酸、ホスホン酸およびこれらのエステル等が挙げられ、好ましくはテトラキス（２，４−ジ−ｔｅｒｔ−ブチルフェニル）−４，４’−ビフェニレンジホスホナイトが使用される。
熱可塑性樹脂組成物中のリン系熱安定剤の含有量としては、熱可塑性樹脂組成物１００重量部に対して０．００１〜０．２重量部が好ましい。
紫外線吸収剤としては、ベンゾトリアゾール系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤、トリアジン系紫外線吸収剤、環状イミノエステル系紫外線吸収剤およびシアノアクリレート系からなる群より選ばれた少なくとも１種の紫外線吸収剤が好ましい。
紫外線吸収剤の配合量は、熱可塑性樹脂組成物中１００重量部に対して好ましくは０．０１〜３．０重量部であり、より好ましくは０．０２〜１．０重量部であり、さらに好ましくは０．０５〜０．８重量部である。かかる配合量の範囲であれば、用途に応じ、熱可塑性樹脂組成物中に十分な耐候性を付与することが可能である。
ブルーイング剤としては、バイエル社のマクロレックスバイオレットＢおよびマクロレックスブルーＲＲ並びにクラリアント社のポリシンスレンブル−ＲＬＳ等が挙げられる。
ブルーイング剤の配合量は、熱可塑性樹脂組成物中に対して好ましくは０．０５〜１．５ｐｐｍであり、より好ましくは０．１〜１．２ｐｐｍである。
＜熱可塑性樹脂組成物の製造方法＞
本発明のフルオレン骨格を有する熱可塑性樹脂組成物は、フルオレン骨格を有する熱可塑性樹脂、脂肪族系エポキシ化合物および各種添加剤を任意の配合方法により配合することにより得ることができる。各成分は、その全部もしくは一部を、同時にあるいは別々に、例えばブレンダー、ニーダー、バンバリーミキサー、ロール、押出機等の混合機で混合して、均質に分散させることが好ましい。
更に、予めドライブレンドされた組成物を、加熱した押出機で溶融混練して均質化した後針金状に押出し、次いで所望の長さに切断して粒状化する方法を用いることもできる。
＜熱可塑性樹脂組成物の物性値＞
本発明に使用する熱可塑性樹脂は、昇温速度２０℃／ｍｉｎにて測定したガラス転移温度（Ｔｇ）が１３０℃以上、２００℃未満であることが好ましい。Ｔｇが１３０℃未満では、熱可塑性樹脂組成物を用いて形成した光学部材の使用する用途によっては耐熱性が十分でなく、一方Ｔｇが２００℃以上の場合では溶融粘度が高くなり、成形体を形成する上での取扱いが困難となる。
本発明の熱可塑性樹脂組成物は、該熱可塑性樹脂組成物より得られる厚さ０．１ｍｍの成形板のヘイズが２％以下であることが好ましく、さらには１％以下であることがより好ましい。
本発明の熱可塑性樹脂組成物は、３００℃、加重１．２ｋｇｆ、１０分間で押し出される樹脂の量が３０ｇ以上である事が好ましく、４０ｇ以上であることがより好ましい。
本発明の熱可塑性樹脂組成物は、８５℃、８５％ＲＨの条件下で４００時間放置した後の分子量保持率が９５％以上であり、色相変化も全くないことが好ましい。より好ましくは、分子量保持率が９７％以上である。
＜光学部材の製造方法＞
本発明の光学部材は、本発明のフルオレン骨格を有する熱可塑性樹脂組成物を例えば、射出成形、圧縮成形、射出圧縮成形、キャスティングして成形することができる。
（光学レンズ）
本発明の熱可塑性樹脂組成物からなる光学レンズを射出成形で製造する場合、シリンダー温度２６０〜３５０℃、金型温度９０〜１７０℃の条件にて成形することが好ましい。さらに好ましくは、シリンダー温度２７０〜３２０℃、金型温度１００〜１６０℃の条件にて成形することが好ましい。シリンダー温度が３５０℃より高い場合では、樹脂が分解着色し、２３０℃より小さい場合では、溶融粘度が高く成形できない。また金型温度が１７０℃より高い場合では、樹脂が硬化せず金型から成形片を取り出せない。一方、９０℃未満では、成形時に金型内で樹脂が早く固まり成形片を得ることができない、もしくは、金型賦型を転写できない。
本発明の光学レンズは、必要に応じて非球面レンズの形で用いることが好適に実施される。非球面レンズは、１枚のレンズで球面収差を実質的にゼロとすることが可能であるため、複数の球面レンズの組み合わせで球面収差を取り除く必要がなく、軽量化および生産コストの低減化が可能になる。従って、非球面レンズは、光学レンズの中でも特にカメラレンズとして有用である。
また、本発明の熱可塑性樹脂組成物は、成形流動性が高いため、薄肉小型で複雑な形状である光学レンズの材料として特に有用である。
具体的なレンズサイズとして、中心部の厚みの上限は、０．５ｍｍ以下が好ましく、０．４ｍｍ以下がより好ましい。また、レンズの中心部の厚みの下限は、０．０５ｍｍ以上が好ましく、０．１ｍｍ以上がより好ましい。
また、直径が１．０ｍｍ〜２０．０ｍｍ、より好ましくは１．０〜１０．０ｍｍ、さらに好ましくは３．０〜１０．０ｍｍである。
また、その形状として片面が凸、片面が凹であるメニスカスレンズであることが好ましい。<Aliphatic epoxy compound>
The aliphatic epoxy compound of the present invention has the following general formula (2)

In the formula, R is CH ₃ or H, o is 1 to 20, p is 1 to 10, and I is 1 to 20. ) Is an aliphatic epoxy compound having a moiety represented by
When o in the formula is 1 to 20, the molding fluidity can be improved while maintaining transparency due to the effect of the alkylene group. If o is less than 1, the molding fluidity is insufficient, and if it is greater than 20, the compatibility with the resin deteriorates and the transparency cannot be maintained.
When p in the formula is 1 to 10, the epoxy group traps moisture and suppresses hydrolysis of the thermoplastic resin, thereby improving the heat and moisture resistance. When p is less than 1, the heat-and-moisture stability decreases. When the number is more than 10, the aliphatic epoxy compounds react with each other to form a multimer, and thus the heat and humidity resistance decreases. More preferably, it is 2-8, More preferably, it is 3-8.
When I in the formula is 1 to 20, the molding fluidity while maintaining high transparency and moist heat stability is improved. When I is less than 1, the molding fluidity is insufficient and the heat and humidity resistance deteriorates. Furthermore, bleed out from the resin may occur. On the other hand, when I is larger than 20, the compatibility with the resin is deteriorated and the transparency cannot be maintained.
The aliphatic epoxy compound used in the present invention is a compound having one or more epoxy groups in the molecular skeleton. When one or more epoxy groups are present, the epoxy groups react with water, and the hydrothermal stability is improved by suppressing the hydrolysis of the resin.
The aliphatic epoxy compound used in the present invention is a compound in which a glycerin skeleton and an aliphatic chain having an epoxy group are bonded via an ester, and in particular, a carbonyl group of the above formula (2) The number of methylene groups in the excluded fatty chain is preferably 2 to 20 from the viewpoint of molding stability such as high transparency, molding fluidity, heat and humidity resistance, and suppression of gas generation during molding.
Among the aliphatic epoxy compounds having a glycerin skeleton, epoxidized vegetable oil is preferable, and epoxidized soybean oil and epoxidized sesame oil are more preferable. In particular, an epoxidized soybean oil having 2 to 6 epoxy groups and an epoxidized sesame oil are preferred from the viewpoint of moist heat resistance.
Such an aliphatic epoxy compound needs to be contained in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of a thermoplastic resin having a fluorene skeleton described later. When the content is less than 0.1 parts by weight, the molding fluidity is inferior. On the other hand, when the amount is more than 10 parts by weight, it is incompatible with the resin and cannot maintain transparency, and when used under high temperature and high humidity, the molecular weight of the thermoplastic resin having a fluorene skeleton decreases, and the resin hue and strength The heat-and-moisture stability decreases.
The content of the aliphatic epoxy compound used in the present invention is preferably 0.1 to 8 parts by weight, more preferably 0.1 to 8 parts by weight with respect to 100 parts by weight of the thermoplastic resin having a fluorene skeleton. 1 to 5 parts by weight.
<Fluorene compound>
The following formula (1) used in the present invention

(In the formula, R1, R2, R3 and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or 5 carbon atoms. A cycloalkoxyl group having 20 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, X is an alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or carbon. The monomer represented by the formula (6) to (20) is an arylene group, and n and m are integers of 0 to 10.) is a fluorene compound.
R1, R2, R3 and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or a cyclohexane having 5 to 10 carbon atoms. An alkoxyl group is preferred.
Specific examples of the fluorene compound include 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, and 9,9-bis (4-hydroxy-3). -Phenylphenyl) fluorene, 9,9-bis (4-hydroxyethoxyphenyl) fluorene, 9,9-bis (4-hydroxypropoxyphenyl) fluorene, 9,9-bis- (4-hydroxybutoxyphenyl) fluorene, etc. preferable. Among them, the fluorene compound is more preferably 9,9-bis (4-hydroxy-3-methylphenyl) fluorene or 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene.
<Thermoplastic resin>
The thermoplastic resin used in the present invention includes a repeating unit composed of a carbonate unit or an ester unit derived from the fluorene compound of the above formula (1), and examples thereof include polycarbonate and polyester carbonate.
[Polycarbonate]
The polycarbonate used in the present invention has a repeating unit composed of a carbonate unit derived from a dihydroxy compound represented by the following general formula (3) and copolymerizable with the fluorene compound represented by the above formula (1). You may do it.

(Wherein R5 to R8 are each independently a hydrogen atom, a hydrocarbon group or a halogen atom which may contain an aromatic group having 1 to 9 carbon atoms, and W is a single bond, having 1 to 20 carbon atoms. A hydrocarbon group which may contain an aromatic group, an O, S, SO, SO ₂ , CO or COO group.)
In the polycarbonate used in the present invention, W in the general formula (3) is preferably a group represented by the following formula (6).

(Wherein R9 and R10 are the same or different, a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R11 and R12 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n is 4 It is an integer of ~ 7.)
Examples of the dihydroxy compound preferably used include 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane (bisphenol E), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane (bisphenol C), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z), 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) Pentane, 4,4 '-(p-phenylenediisopropylidene) diphenol, α, α'-bi Aromatic diols such as bis (4-hydroxyphenyl) -m-diisopropylbenzene (bisphenol M) and 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, among which bisphenol A, bisphenol Z, Bisphenol C, bisphenol E, and bisphenol M are preferred. Bisphenol A is particularly preferable. You may use these individually or in combination of 2 or more types.
As long as the optical properties are not impaired, aromatic dihydroxy compounds such as hydroquinone and resorcinol that do not fall under the general formula (3), aliphatic diols such as ethylene glycol, tricyclo [5.2.1.02,6] decandi Methanol, cyclohexane-1,4-dimethanol, decalin-2,6-dimethanol, norbornane dimethanol, pentacyclopentadecanedimethanol, cyclopentane-1,3-dimethanol, spiroglycol, 1,4: 3,6 Carbonate units derived from alicyclic diols such as -dianhydro-D-sorbitol, 1,4: 3,6-dianhydro-D-mannitol, 1,4: 3,6-dianhydro-L-iditol may be included. These may be used alone or in combination of two or more.
The ratio of the formula (1) to the formula (3) is a polycarbonate having a molar ratio of (1) :( 3) = 100: 0 to 50:50, preferably 98: 2 to 50:50, 95 : The range of 5-50: 50 is more preferable.
[Production method of polycarbonate]
Such a polycarbonate resin is produced by a reaction means known per se for producing an ordinary polycarbonate resin, for example, a method of reacting a dihydroxy compound with a carbonate precursor such as phosgene or carbonic acid diester.
In a reaction using, for example, phosgene as a carbonate precursor, the reaction is usually performed in the presence of an acid binder and a solvent. As the acid binder, for example, an amine compound such as pyridine is used. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In that case, reaction temperature is 0-40 degreeC normally, and reaction time is several minutes-5 hours.
In the polycarbonate resin of the present invention, monofunctional phenols that are usually used as a terminal terminator can be used in the polymerization reaction. Particularly in the case of a reaction using phosgene as a carbonate precursor, monofunctional phenols are generally used as a terminator for controlling the molecular weight, and the resulting aromatic polycarbonate resin has a terminal monofunctional phenol. Since it is blocked by a group based on, it is superior in thermal stability as compared to those not.
It can also be produced by a known melt polycondensation method (ester exchange reaction) in which a carbonic acid diester is used as the carbonate precursor and the reaction is carried out in the presence of a mixed catalyst comprising a basic compound catalyst, a transesterification catalyst or both.
Examples of the carbonic acid diester include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate. Of these, diphenyl carbonate is particularly preferred. The carbonic acid diester is preferably used in a ratio of 0.97 to 1.20 mol, more preferably 0.98 to 1.10 mol, relative to 1 mol of the diol component.
Examples of the basic compound catalyst include alkali metal compounds, alkaline earth metal compounds, and nitrogen-containing compounds.
Examples of such compounds include organic acid salts, inorganic salts, oxides, hydroxides, hydrides or alkoxides of alkali metals and alkaline earth metals, and quaternary ammonium hydroxides and salts thereof, amines, and the like. Nitrogen-containing compounds are preferably used, and these compounds can be used alone or in combination.
Specific examples of such alkali metal compounds include sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, sodium acetate, sodium benzoate, disodium salt of bisphenol A, sodium salt of phenol, and the like. Used.
Specific examples of the alkaline earth metal compound include magnesium hydroxide and calcium hydroxide.
Specific examples of nitrogen-containing compounds include quaternary ammonium hydroxides having alkyl, aryl, groups, etc. such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, Tertiary amines such as triethylamine, dimethylbenzylamine and triphenylamine, secondary amines such as diethylamine and dibutylamine, primary amines such as propylamine and butylamine, 2-methylimidazole, 2-phenylimidazole and benzimidazole Imidazoles such as are used.
As the transesterification catalyst, zinc, tin, zirconium and lead salts are preferably used, and these can be used alone or in combination.
Specific examples of the transesterification catalyst include zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin (II) chloride, tin (IV) chloride, tin (II) acetate, tin (IV) acetate, and dibutyltin. Dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead (II) acetate, lead (IV) acetate and the like are used.
These catalysts are used in a ratio of 10 ⁻⁹ to 10 ⁻³ mol, preferably 10 ⁻⁷ to 10 ⁻⁴ mol, per 1 mol of the total of dihydroxy compounds.
The melt polycondensation method is a method in which melt polycondensation is performed using the above-described raw materials and catalyst while removing by-products by a transesterification reaction under normal pressure or reduced pressure. The reaction is generally carried out in a multistage process of two or more stages.
Specifically, the reaction at the first stage is allowed to react at a temperature of 120 to 260 ° C., preferably 180 to 240 ° C. for 0.1 to 5 hours, preferably 0.5 to 3 hours. Next, the reaction temperature is raised while raising the degree of vacuum of the reaction system to react the dihydroxy compound and the carbonic acid diester, and finally polycondensation is carried out at a temperature of 200 to 350 ° C. under a reduced pressure of 1 mmHg or less for 0.05 to 2 hours. Perform the reaction. Such a reaction may be carried out continuously or batchwise. The reaction apparatus used for carrying out the above reaction is equipped with paddle blades, lattice blades, glasses blades, etc. even with vertical types equipped with vertical stirring blades, Max blend stirring blades, helical ribbon stirring blades, etc. It may be a horizontal type or an extruder type equipped with a screw. In particular, it is preferable to use a reactor in which these are appropriately combined in consideration of the viscosity of the polymer.
In the obtained polycarbonate resin, the catalyst is removed or deactivated after the polymerization reaction in order to maintain thermal stability and hydrolysis stability. In general, a method of deactivating a catalyst by adding a known deactivator is preferably performed. Specific examples of these substances include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, and aromatic sulfonic acids such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate. Preference is given to esters, phosphoric acids such as phosphorous acid, phosphoric acid, phosphonic acid, benzoyl chloride, p-toluenesulfonic acid chloride and the like. These deactivators are used in an amount of 0.01 to 50 times mol, preferably 0.3 to 20 times mol for the amount of catalyst. When the amount is less than 0.01 times the amount of the catalyst, the deactivation effect is insufficient. Moreover, when it is more than 50 times mole with respect to the amount of catalyst, heat resistance will fall and it will become easy to color a molded object.
After deactivation of the catalyst, a step of devolatilizing and removing the low-boiling compounds in the polymer at a pressure of 13.3 to 1133.3 Pa and a temperature of 200 to 350 ° C. may be provided. A horizontal apparatus equipped with a stirring blade excellent in surface renewability, such as a glasses blade, or a thin film evaporator is preferably used.
The polycarbonate resin in the present invention is preferably one having 0.7 g of the polymer dissolved in 100 ml of methylene chloride and having a specific viscosity in the range of 0.12 to 0.55 measured at 20 ° C. A range is more preferable. If the specific viscosity is less than 0.12, the molded product becomes brittle, and if it exceeds 0.55, the melt viscosity and the solution viscosity become high.
<Polyester carbonate>
In the polyester carbonate used in the present invention, the acid component forming the ester unit is a dicarboxylic acid component represented by the general formula (4) and / or the general formula (5), and is represented by the general formula (1). The ratio of the monomer component and the total of the dicarboxylic acid components represented by the general formula (4) and / or the general formula (5) is (1): ((4) + (5)) = 50 in molar ratio. : 50 to 95: 5, preferably 70:30 to 95: 5, and more preferably 75:25 to 90:10. When the latter ratio exceeds 50:50, the performance as an optical material may deteriorate.
Such a polyester carbonate may be copolymerized with a dihydroxy compound represented by the above general formula (3) that can be copolymerized with the fluorene compound represented by the above formula (1).
The ratio of the dihydroxy compound represented by the general formula (3) is a molar ratio with the fluorene compound represented by the general formula (1), and the formula (1): the formula (3) = 80 to 100: 20 to 0 More preferably, it is 90-100: 10-0.
The dihydroxy compound represented by the general formula (3) preferably used is the same as that described for the polycarbonate. Similarly, other dihydroxy compounds may be used in combination as long as the optical properties are not impaired.
[Dicarboxylic acid]
The acid component forming the ester unit is represented by the following general formula (4)

(In the formula, R13 and R14 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms. And / or the following general formula (5):

(In the formula, R15 and R16 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms. A dicarboxylic acid represented by the following formula:
Preferred dicarboxylic acids represented by general formula (4) include terephthalic acid and isophthalic acid, with terephthalic acid being particularly preferred. Examples of the dicarboxylic acid represented by the general formula (5) preferably used include 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 6-Naphthalenedicarboxylic acid is preferred. Of these, terephthalic acid and isophthalic acid, particularly terephthalic acid are preferred as the dicarboxylic acid.
In addition, in the range which does not inhibit an optical characteristic, dicarboxylic acid components other than the dicarboxylic acid represented by General formula (4) or General formula (5) may be included.
[Production method of polyester carbonate]
Examples of the carbonate precursor used for producing the polyester carbonate resin include phosgene, diphenyl carbonate, bischloroformate of the above dihydric phenols, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, and di-p-chlorophenyl carbonate. And dinaphthyl carbonate. Among them, diphenyl carbonate is preferable.
As a method for producing a polyester carbonate resin, a method used for producing a normal polyester carbonate resin is arbitrarily employed. For example, a reaction between a diol and a dicarboxylic acid or dicarboxylic acid chloride and phosgene, or a transesterification reaction between a diol and a dicarboxylic acid or dicarboxylic acid dialkyl ester and a bisaryl carbonate is preferably employed.
In the reaction of diol, dicarboxylic acid or its acid chloride with phosgene, the reaction is carried out in the presence of an acid binder and a solvent in a non-aqueous system. Examples of the acid binder include pyridine, dimethylaminopyridine, tertiary amine and the like. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. It is desirable to use a terminal terminator such as phenol or p-tert-butylphenol as the molecular weight regulator. The reaction temperature is usually 0 to 40 ° C., and the reaction time is preferably several minutes to 5 hours.
In the transesterification reaction, a diol and a dicarboxylic acid or diester thereof and a bisaryl carbonate are mixed in the presence of an inert gas, and the reaction is usually performed at 120 to 350 ° C., preferably 150 to 300 ° C. under reduced pressure. The degree of vacuum is changed stepwise, and finally the alcohols produced at 1 mmHg or less are distilled out of the system. The reaction time is usually about 1 to 4 hours. However, when the polymerization temperature is 350 ° C. or higher, phenyl vinyl ether and acetaldehyde are easily produced as by-products, which is not preferable.
In the transesterification reaction, a polymerization catalyst can be used to promote the reaction. As such a polymerization catalyst, an alkali metal compound, an alkaline earth metal compound or a heavy metal compound may be used as a main component, and a nitrogen-containing basic compound may be used as a subsidiary component if necessary.
Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium salt of bisphenol A, and the like. Examples of the alkaline earth metal compound include calcium hydroxide, magnesium hydroxide, calcium carbonate and the like.
Examples of the nitrogen-containing basic compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylamine, triethylamine, dimethylbenzylamine, triphenylamine, dimethylaminopyridine and the like.
Other transesterification catalysts include zinc, tin, zirconium, lead, titanium, germanium, antimony, osmium, and aluminum salts, such as zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin chloride (II ), Tin (IV) chloride, tin (II) acetate, tin (IV) acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead (II) acetate, acetic acid Lead (IV) titanium tetrabutoxide (IV) or the like is used.
These catalysts may be used alone or in combination of two or more. The amount of these polymerization catalysts used is a ratio of 10 ⁻⁹ to 10 ⁻³ mol with respect to 1 mol of the diol and the dicarboxylic acid in total. Used. These may be used alone or in combination of two or more. In the transesterification reaction, a diaryl carbonate having an electron-withdrawing substituent may be added at a later stage or after completion of the polycondensation reaction in order to reduce the hydroxy end group. Furthermore, an antioxidant or a heat stabilizer may be added to improve the hue.
Further, after completion of the polymerization reaction, the catalyst may be removed or deactivated in order to maintain thermal stability and hydrolysis stability. For alkali metal compounds or alkaline earth metal compounds, generally, a method of deactivating a catalyst by adding a known deactivator is preferably carried out. Specific examples of these substances include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, aromatic sulfonic acid esters such as butyl p-toluenesulfonate, phosphorous acid, Phosphoric acids such as phosphoric acid and phosphonic acid, triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, phosphoric acid Phosphoric esters such as triphenyl, phosphonic acids such as diphenylphosphonic acid, phosphonic acid esters such as diethyl phenylphosphonate, phosphines such as triphenylphosphine, aromatic sulfonic acids such as tetrabutylphosphonium dodecylbenzenesulfonate Salts are preferably used. These deactivators are used in an amount of 0.01 to 50 times mol, preferably 0.3 to 20 times mol for the amount of catalyst. When the amount is less than 0.01 times the amount of the catalyst, the deactivation effect is insufficient. Moreover, when it is more than 50 times mole with respect to the amount of catalyst, heat resistance will fall and it will become easy to color a molded object.
After catalyst deactivation, a step of devolatilizing and removing low-boiling compounds in the resin at a pressure of 133 to 13.3 Pa and a temperature of 200 to 320 ° C may be provided.
The polyester carbonate resin in the present invention is preferably such that 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 0.12 to 0.55. A range of .45 is more preferable. When the specific viscosity is less than 0.12, the molded product becomes brittle, and when it exceeds 0.55, the melt viscosity and the solution viscosity become high, and handling becomes difficult.
<Additives>
The thermoplastic resin composition of the present invention may contain various additives in order to impart various characteristics within a range that does not impair the object of the present invention. Additives such as mold release agents, heat stabilizers, UV absorbers, bluing agents, antistatic agents, flame retardants, heat ray shielding agents, fluorescent dyes (including fluorescent whitening agents), light diffusing agents, other resins and An elastomer or the like can be blended.
As a mold release agent, that whose 90 weight% or more consists of ester of alcohol and a fatty acid is preferable. Specific examples of the ester of alcohol and fatty acid include monohydric alcohol and fatty acid ester and / or partial ester or total ester of polyhydric alcohol and fatty acid. Among these esters, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and a mixture of stearic acid triglyceride and stearyl stearate are preferably used.
The amount of the ester in the release agent is preferably 90% by weight or more, and more preferably 95% by weight or more when the release agent is 100% by weight.
Examples of the heat stabilizer include a phosphorus heat stabilizer, a sulfur heat stabilizer, and a hindered phenol heat stabilizer. Examples of the phosphorus-based heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Tetrakis (2,4-di-tert-butylphenyl) -4,4 ′ is preferable. -Biphenylene diphosphonite is used.
As content of the phosphorus-type heat stabilizer in a thermoplastic resin composition, 0.001-0.2 weight part is preferable with respect to 100 weight part of thermoplastic resin compositions.
As the UV absorber, at least one UV absorber selected from the group consisting of benzotriazole UV absorbers, benzophenone UV absorbers, triazine UV absorbers, cyclic imino ester UV absorbers, and cyanoacrylates Is preferred.
The blending amount of the ultraviolet absorber is preferably 0.01 to 3.0 parts by weight, more preferably 0.02 to 1.0 parts by weight with respect to 100 parts by weight in the thermoplastic resin composition. Preferably it is 0.05-0.8 weight part. If it is the range of this compounding quantity, it is possible to provide sufficient weather resistance in a thermoplastic resin composition according to a use.
Examples of the bluing agent include Macrolex Violet B and Macrolex Blue RR manufactured by Bayer and polysynthremble-RLS manufactured by Clariant.
The blending amount of the bluing agent is preferably 0.05 to 1.5 ppm, more preferably 0.1 to 1.2 ppm with respect to the thermoplastic resin composition.
<Method for producing thermoplastic resin composition>
The thermoplastic resin composition having a fluorene skeleton of the present invention can be obtained by blending a thermoplastic resin having a fluorene skeleton, an aliphatic epoxy compound, and various additives by any blending method. It is preferable that all or a part of each component is mixed at the same time or separately, for example, with a blender such as a blender, kneader, Banbury mixer, roll, or extruder, and uniformly dispersed.
Further, it is also possible to use a method in which a composition previously dry blended is melt-kneaded with a heated extruder, homogenized, extruded into a wire shape, and then cut into a desired length and granulated.
<Physical properties of thermoplastic resin composition>
The thermoplastic resin used in the present invention preferably has a glass transition temperature (Tg) measured at a heating rate of 20 ° C./min of 130 ° C. or more and less than 200 ° C. If the Tg is less than 130 ° C., the heat resistance is not sufficient depending on the use of the optical member formed using the thermoplastic resin composition. On the other hand, if the Tg is 200 ° C. or more, the melt viscosity becomes high, Handling in forming becomes difficult.
In the thermoplastic resin composition of the present invention, the haze of a molded plate having a thickness of 0.1 mm obtained from the thermoplastic resin composition is preferably 2% or less, and more preferably 1% or less. .
In the thermoplastic resin composition of the present invention, the amount of resin extruded in 300 ° C., a load of 1.2 kgf for 10 minutes is preferably 30 g or more, and more preferably 40 g or more.
The thermoplastic resin composition of the present invention preferably has a molecular weight retention of 95% or more after being left for 400 hours under conditions of 85 ° C. and 85% RH, and has no hue change. More preferably, the molecular weight retention is 97% or more.
<Method for producing optical member>
The optical member of the present invention can be molded by, for example, injection molding, compression molding, injection compression molding, or casting of the thermoplastic resin composition having the fluorene skeleton of the present invention.
(Optical lens)
When manufacturing the optical lens which consists of the thermoplastic resin composition of this invention by injection molding, it is preferable to shape | mold on conditions with a cylinder temperature of 260-350 degreeC and a mold temperature of 90-170 degreeC. More preferably, molding is preferably performed under conditions of a cylinder temperature of 270 to 320 ° C and a mold temperature of 100 to 160 ° C. When the cylinder temperature is higher than 350 ° C., the resin is decomposed and colored. When the cylinder temperature is lower than 230 ° C., the melt viscosity is too high to be molded. When the mold temperature is higher than 170 ° C., the resin is not cured and the molded piece cannot be taken out from the mold. On the other hand, if it is less than 90 ° C., the resin quickly hardens in the mold during molding, and a molded piece cannot be obtained, or the mold molding cannot be transferred.
The optical lens of the present invention is preferably used in the form of an aspheric lens as necessary. Since an aspheric lens can substantially eliminate spherical aberration with a single lens, there is no need to remove spherical aberration with a combination of a plurality of spherical lenses, thus reducing weight and reducing production costs. It becomes possible. Therefore, the aspherical lens is particularly useful as a camera lens among optical lenses.
Moreover, since the thermoplastic resin composition of the present invention has high molding fluidity, it is particularly useful as a material for an optical lens having a thin, small and complicated shape.
As a specific lens size, the upper limit of the thickness of the central portion is preferably 0.5 mm or less, and more preferably 0.4 mm or less. Further, the lower limit of the thickness of the central portion of the lens is preferably 0.05 mm or more, and more preferably 0.1 mm or more.
Moreover, a diameter is 1.0 mm-20.0 mm, More preferably, it is 1.0-10.0 mm, More preferably, it is 3.0-10.0 mm.
In addition, it is preferably a meniscus lens having a convex surface on one side and a concave surface on the other side.

表１に示す実施例１〜７は、ヘイズ、耐湿熱安定性を保持したまま、成形流動性を向上する事ができ、光学レンズの成形性も良好であり、光学部材に有用に利用できる。一方、比較例１は、脂肪族系エポキシ化合物未添加であり、流動性に劣る為、薄肉なレンズを成形できない。比較例２は、添加量が少なく流動性に乏しく薄肉なレンズの成形ができない。又、比較例４は、添加剤がエポキシ基を有しないため耐湿熱安定性に劣る。比較例５は、脂環式エポキシ化合物であり、成形流動性に劣り、成形時の成形不良が多い。比較例６は、芳香族エポキシ化合物であり、成形流動性に劣る。比較例７は、成形流動性は向上しているが、成形時に添加剤が揮発し成形不良が多く、さらに、耐湿熱安定性に劣り、光学部材として使用する環境が限られ、汎用性に乏しい。比較例８，９は、添加剤の分解により成形性・耐湿熱性に劣る。比較例３は添加量が多く透明性を維持する事が出来ない為、光学部材に使用できない。
発明の効果
本発明のフルオレン骨格を有する熱可塑性樹脂組成物は、高度な透明性、成形流動性、成形安定性、及び耐湿熱安定性を有するので、従来射出成形困難であった薄肉光学部材の成形が可能となり、より薄物の光学部材を提供する事ができる。このフルオレン骨格を有する熱可塑性樹脂組成物は、携帯カメラ用等のカメラレンズ、ピックアップレンズマイクロアレーレンズ、プロジェクターレンズ及びフレネルレンズなどのレンズ等に特に好適である。The following examples further illustrate the present invention.
Examples 1-7, Comparative Examples 1-9
Evaluation was based on the following method.
(Evaluation method)
(1) Specific viscosity of resin: The resin obtained after completion of polymerization was dried at 120 ° C. for 4 hours, and a solution in which 0.35 g of the resin was dissolved in 50 cc of methylene chloride was used as a measurement sample. In the measurement, the passage time between the marked lines of the Oswald viscosity tube was measured in a constant temperature bath of 20 ± 0.01 ° C., and the specific viscosity (η _sp ) of the solution at 20 ° C. was obtained from the following formula.
η _sp = (t ₁ −t ₀ ) / t ₀
Here, t _{1 is a} passage time between marked lines of the resin solution, and t ₀ is a passage time between marked lines of methylene chloride.
(2) Copolymerization ratio: The resin after polymerization was measured using proton NMR of JNM-AL400 manufactured by JEOL Ltd.
(3) Glass transition point (Tg): measured by DuPont 910 DSC.
(4) Molding fluidity (Melting viscosity (MVR)): Melted in a quantity of resin extruded at 300 ° C. under a load of 1.2 kgf for 10 minutes using a nozzle with a diameter of 1 mm and a length of 10 mm by Capirograh 1D manufactured by Toyo Seiki The viscosity was measured.
(5) Haze: Haze was measured on a molded plate having a thickness of 1 mm using Nippon Denshoku Industries Co., Ltd. Haze Meter NDH2000.
(6) Moisture and heat stability Molecular weight retention: After a molded piece having a thickness of 1 mm is allowed to stand for 2000 hours under the conditions of 85 ° C. and 85% RH, the specific viscosity retention is retained by the change in specific viscosity described below. Rated as a rate.
From a solution obtained by dissolving 0.7 g of the molded piece in 100 ml of methylene chloride, the specific viscosity (η _sp ) of the solution at 20 ° C. was measured, and the specific viscosity retention rate (molecular weight retention rate) after the wet heat test was determined. The specific viscosity retention rate (molecular weight retention rate) was used as an index of moisture and heat resistance.
Δη _sp = (η _sp 1 / η _sp 0) × 100
* Δη _sp : specific viscosity retention, η _sp 0: specific viscosity before test, η _sp 1: specific viscosity after test (7) Optical lens molding stability: poor filling of aspherical lens after molding, each molding Defects, insufficient lens strength, etc. were confirmed visually. Evaluation was performed by performing 100-shot molding, and the probability of being a defective product was less than 1% (◎), 1 to 5% (）), 5 to 20% (Δ), and 20% or less (x).
Filling failure is defined as a filling failure due to insufficient resin to form a lens shape. Molding failure is caused by one or more silver stripes / bubbles in one lens, or additive bleeding out. Shall be. Further, the insufficient strength of the lens means that the lens part and the sprue / runner part are broken from the mold during molding and cannot be taken out.
(Synthesis)
PC (1): Polycarbonate 21540 parts by weight of ion-exchanged water and 4930 parts by weight of a 48% aqueous sodium hydroxide solution were placed in a reactor equipped with a thermometer, a stirrer, and a reflux condenser. , 9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “BCF”) 3231 parts by weight, 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as “BPA”) 1949 parts by weight and 15 parts by weight of hydrosulfite were dissolved, 14530 parts by weight of methylene chloride was added, and then 2200 parts by weight of phosgene was blown in at 15 to 25 ° C. for 60 minutes with stirring. After the completion of phosgene blowing, 163.1 parts by weight of cumylphenol and 705 parts by weight of a 48% aqueous sodium hydroxide solution were added. After emulsification, 5.9 parts by weight of triethylamine was added and the reaction was stirred at 28-33 ° C. for 1 hour. finished. After completion of the reaction, the product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and when the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, the methylene chloride was evaporated with a kneader, A white polymer having a molar ratio of BCF to BPA of 50:50, a specific viscosity of 0.297, and a Tg of 197 ° C. was obtained.
PC (2)
In a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 21540 parts by weight of ion-exchanged water and 4930 parts by weight of a 48% aqueous sodium hydroxide solution were added, and 9,9-bis (4 -Hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “BCF”) 3231 parts by weight, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene (hereinafter abbreviated as “BPM”) 2958 parts by weight and 15 parts by weight of hydrosulfite were dissolved, 14530 parts by weight of methylene chloride was added, and then 2200 parts by weight of phosgene was blown in at 15 to 25 ° C. for 60 minutes with stirring. After the completion of phosgene blowing, 163.1 parts by weight of cumylphenol and 705 parts by weight of a 48% aqueous sodium hydroxide solution were added. After emulsification, 5.9 parts by weight of triethylamine was added and the reaction was stirred at 28-33 ° C. for 1 hour. finished. After completion of the reaction, the product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and when the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, the methylene chloride was evaporated with a kneader, A white polymer having a molar ratio of BCF to BPM of 50:50, a specific viscosity of 0.297, and a Tg of 156 ° C. was obtained.
PC (3)
9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (hereinafter abbreviated as “BPEF”) 1403.2 parts by weight, BPA 182.7 parts by weight, diphenyl carbonate (hereinafter abbreviated as “DPC”) 878.0 parts by weight and sodium hydrogen carbonate 5.0 × 10 ⁻³ parts by weight were placed in a reactor equipped with a stirrer and a distillation apparatus, and after nitrogen substitution three times, a nitrogen atmosphere 101.3 It heated at 215 degreeC under * 10 < ³ > Pa, and stirred for 20 minutes. After complete dissolution, it was adjusted to 20 × 10 ³ Pa over 15 minutes, and kept for 20 minutes under the conditions of 215 ° C. and × 10 ³ Pa, to conduct a transesterification reaction. Furthermore, it heated up to 240 degreeC at the speed | rate of 37.5 degreeC / hr, and hold | maintained for 10 minutes at 240 degreeC and 20.0 * 10 < ³ > Pa. Then, it adjusted to 16.0 * 10 < ³ > Pa over 10 minutes, and hold | maintained for 70 minutes at 240 degreeC and * 10 < ³ > Pa. Then, over a period of 10 minutes was adjusted to ^{13.3 × 10 3 Pa, 240 ℃} , held for 10 minutes at 13.3 × ¹⁰ 3 Pa. Furthermore, it was set to 133.3 Pa or less over 40 minutes, and the polymerization reaction was carried out with stirring for 10 minutes under the conditions of 240 ° C. and 133.3 Pa or less. After completion of the reaction, nitrogen was blown into the reactor to increase the pressure, and the produced resin was extracted while pelletizing. A colorless transparent pellet having a molar ratio of BPEF to BPA of 80:20, a specific viscosity of 0.192, and Tg of 145 ° C. was obtained.
PEC (1): Polyester carbonate BPEF 1403.2 parts by weight, dimethyl terephthalate (hereinafter sometimes abbreviated as “DMT”) 155.4 parts by weight, DPC 548.4 parts by weight, titanium tetrabutoxide 13.6 × 10 ⁻⁴ A part by weight was placed in a reaction kettle equipped with a stirrer and a distillation apparatus, heated to 180 ° C. under a nitrogen atmosphere of 101.3 × 10 ³ Pa, and stirred for 20 minutes. Thereafter, the degree of vacuum was adjusted to 20 × 10 ³ Pa over 20 minutes, and the temperature was raised to 250 ° C. at a rate of 60 ° C./hr to conduct a transesterification reaction. Thereafter, while maintaining the temperature at 250 ° C., the pressure was reduced to 133.3 Pa or less over 120 minutes, and the polymerization reaction was performed with stirring for 1 hour under the conditions of 250 ° C. and 133.3 Pa or less. Thereafter, the produced resin was extracted while pelletizing. A colorless transparent pellet having a molar ratio of BPEF to terephthalic acid of 80:20, a specific viscosity of 0.201, and Tg of 150 ° C. was obtained.
(Molded piece)
The pelletized resin composition was heat-dried at 120 ° C. for 8 hours. Then, using a SE30DU injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. at a molding temperature of Tg + 110 ° C. and a mold temperature of Tg−10 ° C., a molded piece having a width of 2.5 cm, a length of 5 cm, and a thickness of 1 mm was injected. Molded. Table 1 shows the evaluation results of haze and heat-and-moisture resistance.
(Optical lens)
Using a SE30DU injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., using resin molding temperature Tg + 170 ° C., mold temperature Tg-5 ° C., thickness 0.3 mm, convex curvature radius 5 mm, concave curvature radius 4 mm, diameter A 5 mm aspheric lens was injection molded. Table 1 shows the evaluation of molding stability of the optical lens.
(Additive)
Additive 1: Epoxidized soybean oil (number of epoxy groups: 4) Kapox S-6 manufactured by Kao Corporation
Additive 2: Epoxidized linseed oil (number of epoxy groups 6) Adeka Sizer O-180A manufactured by ADEKA
Additive 3: Alkyl monoester, alkyl triglyceride mixture Rikenmar SL-900 manufactured by RIKEN
Additive 4: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate Additive 5: Bisphenoxyethanol full orange glycidyl ether Additive 6: Trioctyl trimellitic acid Additive 7: Polyether ester resin Eastman Chemical Company ECDEL 9966
Additive 8: Styrene oligomer FTR2140 manufactured by Mitsui Chemicals, Inc.
Stabilizer: Tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite Mold release agent: Glycerol monostearate The unit of Table 1 is parts by weight with respect to the amount.
[Examples 1-7 and Comparative Examples 1-9]
After the various components were previously dry-blended uniformly in the proportions shown in Table 1, the KZ-W15-30MG twin-screw extruder manufactured by Technobel Co., Ltd. and manufactured by Technobel Co. were used under the conditions described in Table 1 below. It was melted and pelletized, and a molded product was appropriately prepared and evaluated.

Examples 1 to 7 shown in Table 1 can improve molding fluidity while maintaining haze and heat-and-moisture resistance stability, have good moldability of optical lenses, and can be usefully used for optical members. On the other hand, Comparative Example 1 is not added with an aliphatic epoxy compound and is inferior in fluidity, so a thin lens cannot be molded. In Comparative Example 2, the addition amount is small, the fluidity is poor, and a thin lens cannot be molded. Further, Comparative Example 4 is inferior in heat-and-moisture stability because the additive does not have an epoxy group. Comparative Example 5 is an alicyclic epoxy compound that is inferior in molding fluidity and has many molding defects during molding. Comparative Example 6 is an aromatic epoxy compound and is inferior in molding fluidity. In Comparative Example 7, the molding fluidity is improved, but the additive is volatilized at the time of molding, and there are many molding defects. Further, the heat and heat resistance is poor, the environment for use as an optical member is limited, and the versatility is poor. . Comparative Examples 8 and 9 are inferior in moldability and moist heat resistance due to the decomposition of the additive. Since Comparative Example 3 has a large amount of addition and cannot maintain transparency, it cannot be used as an optical member.
Effects of the Invention The thermoplastic resin composition having a fluorene skeleton of the present invention has high transparency, molding fluidity, molding stability, and heat-and-moisture stability. Molding is possible, and a thinner optical member can be provided. The thermoplastic resin composition having a fluorene skeleton is particularly suitable for a camera lens for a portable camera, a lens such as a pickup lens microarray lens, a projector lens, and a Fresnel lens.

  The optical member using the thermoplastic resin composition having a fluorene skeleton of the present invention can be used for various cameras such as digital video cameras, telescopes, binoculars, television projectors, prisms, and the like. In particular, it is effective as a thin and small lens such as a camera lens for a mobile phone, a digital camera lens, an in-vehicle camera lens, and a web camera lens.

  The present invention relates to a thermoplastic resin composition having a fluorene skeleton having high transparency and excellent molding fluidity, molding stability, and heat-and-moisture resistance, and an optical member comprising the same.

  Optical glass or optical transparent resin is used as a material for optical lenses used in optical systems of various cameras such as cameras, film-integrated cameras, and video cameras. Optical glass has excellent heat resistance, transparency, dimensional stability, chemical resistance, etc., and there are many types of materials with various refractive indexes and Abbe numbers. The problem is that the productivity is low and the productivity is low.

  On the other hand, optical transparent resins, in particular thermoplastic optical transparent resins, have the advantage that they can be mass-produced by injection molding, and polycarbonate resins and the like are currently used as materials for camera lenses. However, in recent years, the optical performance required for lens resins has become higher as products become lighter and thinner and cameras have higher pixels. In particular, in recent years, an optical lens with higher imaging performance and lower birefringence has been demanded as the resolution is increased by increasing the number of pixels.

  Resins using 9,9-biscresol fluorene derivatives and 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene derivatives have high refractive index and low birefringence and have excellent optical properties. Used in optical lenses.

These optical lenses are used in various applications, but the shapes and sizes vary greatly depending on the applications. For example, a camera lens for a mobile phone is very small and thin with a diameter of about 5 mm and a thickness of about 0.3 mm. In recent years, the size and thickness of the camera lens have been further reduced. When injection molding such a small thin lens, if the molding fluidity of the resin is insufficient, a lens having a desired shape cannot be obtained, and the molding fluidity is a very important characteristic.
Generally, a plasticizer is used as a method for modifying the molding fluidity of a thermoplastic resin.
As plasticizers, phthalate ester plasticizers, trimellitic ester plasticizers, phosphate triester plasticizers, and the like are widely used.
As another modification method of fluidity, Patent Document 1 proposes a method of adding a polycarbonate oligomer and polycaprolactone to a polycarbonate resin.

  Further, Patent Documents 2 and 3 propose a method of adding a polyether ester resin or a styrene oligomer resin as a method for modifying the molding fluidity of a thermoplastic resin having a fluorene structure.

  In addition to the optical characteristics and molding fluidity, the characteristics required for optical lenses are difficult to use as a lens when the focal length and chromatic aberration are affected by the environment in which the lens is used. It is also an important characteristic for heat and humidity resistance. Further, molding stability such as a low yield during molding is also a very important characteristic.

  However, the method using a plasticizer and the compositions of Patent Documents 1 to 3 have problems in high transparency, molding stability, and wet heat resistance.

  That is, a thermoplastic resin using a fluorene derivative has not been obtained which has a high degree of transparency and sufficiently satisfies the moist heat resistance while maintaining the molding fluidity and molding stability.

JP 2011-63812 A JP 2006-104322 A JP 2006-143831 A

  Accordingly, an object of the present invention is to provide a thermoplastic resin composition having a fluorene skeleton having high transparency, molding fluidity, molding stability, and moist heat resistance, and an optical member comprising the same.

  The present inventors have intensively studied to achieve this purpose. As a result, the inventors have found that the thermoplastic resin having a fluorene skeleton is excellent in high transparency, molding fluidity, molding stability, and moist heat resistance by mixing an appropriate amount of an aliphatic epoxy compound. .

That is, the present invention
1. The following general formula (1)

(In the formula, R1, R2, R3 and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or 5 carbon atoms. A cycloalkoxyl group having 20 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, X is an alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or carbon. An arylene group of 6 to 20. n and m are integers of 0 to 10.) 100 parts by weight of a thermoplastic resin containing a repeating unit composed of a carbonate unit or an ester unit derived from a monomer represented by General formula (2)

(Wherein R is CH ₃ or H, o is 1 to 20, p is 1 to 10, and I is 1 to 20). Is a thermoplastic resin composition having a fluorene skeleton containing 0.1 to 10 parts by weight , wherein the thermoplastic resin is (i) a repeating unit consisting of carbonate units derived from the monomer represented by the general formula (1) Unit and the following general formula (3)

(Wherein R5 to R8 are each independently a hydrogen atom, a hydrocarbon group or a halogen atom which may contain an aromatic group having 1 to 9 carbon atoms, and W is a single bond having 1 to 20 carbon atoms. Hydrocarbon groups that may contain aromatic groups, O, S, SO, SO ₂ , CO or COO groups. )
The ratio of the formula (1) and the formula (3) is a molar ratio of (1) :( 3) = 100: 0 to 50:50. A thermoplastic resin having a specific viscosity of 0.12 to 0.55 measured at 20 ° C., or 0.7 g dissolved in 100 ml of methylene chloride, or (ii) the following general formula (4)

(In the formula, R13 and R14 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms. An ester-based unit derived from a monomer represented by:
General formula (5)

(In the formula, R15 and R16 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms. The ratio of the formula (1) and the sum of the formula (4) and the formula (5) is a molar ratio of (1) :( (4) + (5)) = polyester carbonate in the range of 50:50 to 95: 5, 0.7 g is dissolved in 100 ml of methylene chloride, and the specific viscosity measured at 20 ° C. is 0.12 to 0.4. A thermoplastic resin composition which is 55, a thermoplastic resin.

2. 2. The thermoplastic resin composition having a fluorene skeleton as described in 1 above, wherein the aliphatic epoxy compound is an epoxy compound having a glycerin skeleton.
3. 3. The thermoplastic resin composition having a fluorene skeleton as described in 2 above, wherein the epoxy compound having a glycerin skeleton is an epoxidized vegetable oil.
4). 4. The thermoplastic resin composition having a fluorene skeleton as described in 3 above, wherein the epoxidized vegetable oil is epoxidized soybean oil or epoxy linseed oil.
5. 5. The thermoplastic resin composition having a fluorene skeleton as described in 4 above, wherein the number of epoxy groups in the epoxidized soybean oil and epoxidized sesame oil is 2 to 8.
6). The monomer represented by the general formula (1) is 9,9-bis (4-hydroxy-3-methylphenyl) fluorene or 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene. A thermoplastic resin composition having a fluorene skeleton according to any one of 1 to 5 .
7). An optical member comprising the thermoplastic resin composition having the fluorene skeleton according to any one of 1 to 6 above.
8). 8. The optical member according to 7 , wherein the optical member is an optical lens of a camera lens, a pick-up lens, a microarray lens, a projector lens, or a Fresnel lens.
9. 9. The optical member according to 8 above, wherein the optical lens has a thickness of 0.5 mm or less.

<Aliphatic epoxy compound>
The aliphatic epoxy compound of the present invention has the following general formula (2)

In the formula, R is CH ₃ or H, o is 1 to 20, p is 1 to 10, and I is 1 to 20. ) Is an aliphatic epoxy compound having a moiety represented by

  When o in the formula is 1 to 20, the molding fluidity can be improved while maintaining transparency due to the effect of the alkylene group. If o is less than 1, the molding fluidity is insufficient, and if it is greater than 20, the compatibility with the resin deteriorates and the transparency cannot be maintained.

  When p in the formula is 1 to 10, the epoxy group traps moisture and suppresses hydrolysis of the thermoplastic resin, thereby improving the heat and moisture resistance. When p is less than 1, the heat-and-moisture stability decreases. When the number is more than 10, the aliphatic epoxy compounds react with each other to form a multimer, and thus the heat and humidity resistance decreases. More preferably, it is 2-8, More preferably, it is 3-8.

  When I in the formula is 1 to 20, the molding fluidity while maintaining high transparency and moist heat stability is improved. When I is less than 1, the molding fluidity is insufficient and the heat and humidity resistance deteriorates. Furthermore, bleed out from the resin may occur. On the other hand, when I is larger than 20, the compatibility with the resin is deteriorated and the transparency cannot be maintained.

  The aliphatic epoxy compound used in the present invention is a compound having one or more epoxy groups in the molecular skeleton. When one or more epoxy groups are present, the epoxy groups react with water, and the hydrothermal stability is improved by suppressing the hydrolysis of the resin.

  The aliphatic epoxy compound used in the present invention is a compound in which a glycerin skeleton and an aliphatic chain having an epoxy group are bonded via an ester, and in particular, a carbonyl group of the above formula (2) The number of methylene groups in the excluded fatty chain is preferably 2 to 20 from the viewpoint of molding stability such as high transparency, molding fluidity, heat and humidity resistance, and suppression of gas generation during molding.

  Among the aliphatic epoxy compounds having a glycerin skeleton, epoxidized vegetable oil is preferable, and epoxidized soybean oil and epoxidized sesame oil are more preferable. In particular, an epoxidized soybean oil having 2 to 6 epoxy groups and an epoxidized sesame oil are preferred from the viewpoint of moist heat resistance.

  Such an aliphatic epoxy compound needs to be contained in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of a thermoplastic resin having a fluorene skeleton described later. When the content is less than 0.1 parts by weight, the molding fluidity is inferior. On the other hand, when the amount is more than 10 parts by weight, it is incompatible with the resin and cannot maintain transparency, and when used under high temperature and high humidity, the molecular weight of the thermoplastic resin having a fluorene skeleton decreases, and the resin hue and strength The heat-and-moisture stability decreases.

The content of the aliphatic epoxy compound used in the present invention is preferably 0.1 to 8 parts by weight, more preferably 0.1 to 8 parts by weight with respect to 100 parts by weight of the thermoplastic resin having a fluorene skeleton. 1 to 5 parts by weight.
<Fluorene compound>
The following formula (1) used in the present invention

(In the formula, R1, R2, R3 and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or 5 carbon atoms. A cycloalkoxyl group having 20 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, X is an alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or carbon. The monomer represented by the formula (6) to (20) is an arylene group, and n and m are integers of 0 to 10.) is a fluorene compound.

  R1, R2, R3 and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or a cyclohexane having 5 to 10 carbon atoms. An alkoxyl group is preferred.

  Specific examples of the fluorene compound include 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, and 9,9-bis (4-hydroxy-3). -Phenylphenyl) fluorene, 9,9-bis (4-hydroxyethoxyphenyl) fluorene, 9,9-bis (4-hydroxypropoxyphenyl) fluorene, 9,9-bis- (4-hydroxybutoxyphenyl) fluorene, etc. preferable. Among them, the fluorene compound is more preferably 9,9-bis (4-hydroxy-3-methylphenyl) fluorene or 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene.

<Thermoplastic resin>
The thermoplastic resin used in the present invention includes a repeating unit composed of a carbonate unit or an ester unit derived from the fluorene compound of the above formula (1), and examples thereof include polycarbonate and polyester carbonate.
[Polycarbonate]
The polycarbonate used in the present invention has a repeating unit composed of a carbonate unit derived from a dihydroxy compound represented by the following general formula (3) and copolymerizable with the fluorene compound represented by the above formula (1). You may do it.

(Wherein R5 to R8 are each independently a hydrogen atom, a hydrocarbon group or a halogen atom which may contain an aromatic group having 1 to 9 carbon atoms, and W is a single bond, having 1 to 20 carbon atoms. A hydrocarbon group which may contain an aromatic group, an O, S, SO, SO ₂ , CO or COO group.)
In the polycarbonate used in the present invention, W in the general formula (3) is preferably a group represented by the following formula (6).

(Wherein R9 and R10 are the same or different, a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R11 and R12 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n is 4 It is an integer of ~ 7.)
Examples of the dihydroxy compound preferably used include 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane (bisphenol E), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane (bisphenol C), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z), 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) Pentane, 4,4 '-(p-phenylenediisopropylidene) diphenol, α, α'-bi Aromatic diols such as bis (4-hydroxyphenyl) -m-diisopropylbenzene (bisphenol M) and 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, among which bisphenol A, bisphenol Z, Bisphenol C, bisphenol E, and bisphenol M are preferred. Bisphenol A is particularly preferable. You may use these individually or in combination of 2 or more types.

  As long as the optical properties are not impaired, aromatic dihydroxy compounds such as hydroquinone and resorcinol that do not fall under the general formula (3), aliphatic diols such as ethylene glycol, tricyclo [5.2.1.02,6] decandi Methanol, cyclohexane-1,4-dimethanol, decalin-2,6-dimethanol, norbornane dimethanol, pentacyclopentadecanedimethanol, cyclopentane-1,3-dimethanol, spiroglycol, 1,4: 3,6 Carbonate units derived from alicyclic diols such as -dianhydro-D-sorbitol, 1,4: 3,6-dianhydro-D-mannitol, 1,4: 3,6-dianhydro-L-iditol may be included. These may be used alone or in combination of two or more.

  The ratio of the formula (1) to the formula (3) is a polycarbonate having a molar ratio of (1) :( 3) = 100: 0 to 50:50, preferably 98: 2 to 50:50, 95 : The range of 5-50: 50 is more preferable.

[Production method of polycarbonate]
Such a polycarbonate resin is produced by a reaction means known per se for producing an ordinary polycarbonate resin, for example, a method of reacting a dihydroxy compound with a carbonate precursor such as phosgene or carbonic acid diester.

  In a reaction using, for example, phosgene as a carbonate precursor, the reaction is usually performed in the presence of an acid binder and a solvent. As the acid binder, for example, an amine compound such as pyridine is used. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In that case, reaction temperature is 0-40 degreeC normally, and reaction time is several minutes-5 hours.

  In the polycarbonate resin of the present invention, monofunctional phenols that are usually used as a terminal terminator can be used in the polymerization reaction. Particularly in the case of a reaction using phosgene as a carbonate precursor, monofunctional phenols are generally used as a terminator for controlling the molecular weight, and the resulting aromatic polycarbonate resin has a terminal monofunctional phenol. Since it is blocked by a group based on, it is superior in thermal stability as compared to those not.

  It can also be produced by a known melt polycondensation method (ester exchange reaction) in which a carbonic acid diester is used as the carbonate precursor and the reaction is carried out in the presence of a mixed catalyst comprising a basic compound catalyst, a transesterification catalyst or both.

  Examples of the carbonic acid diester include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate. Of these, diphenyl carbonate is particularly preferred. The carbonic acid diester is preferably used in a ratio of 0.97 to 1.20 mol, more preferably 0.98 to 1.10 mol, relative to 1 mol of the diol component.

  Examples of the basic compound catalyst include alkali metal compounds, alkaline earth metal compounds, and nitrogen-containing compounds.

  Examples of such compounds include organic acid salts, inorganic salts, oxides, hydroxides, hydrides or alkoxides of alkali metals and alkaline earth metals, and quaternary ammonium hydroxides and salts thereof, amines, and the like. Nitrogen-containing compounds are preferably used, and these compounds can be used alone or in combination.

  Specific examples of such alkali metal compounds include sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, sodium acetate, sodium benzoate, disodium salt of bisphenol A, sodium salt of phenol, and the like. Used.

  Specific examples of the alkaline earth metal compound include magnesium hydroxide and calcium hydroxide.

  Specific examples of nitrogen-containing compounds include quaternary ammonium hydroxides having alkyl, aryl, groups, etc. such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, Tertiary amines such as triethylamine, dimethylbenzylamine and triphenylamine, secondary amines such as diethylamine and dibutylamine, primary amines such as propylamine and butylamine, 2-methylimidazole, 2-phenylimidazole and benzimidazole Imidazoles such as are used.

  As the transesterification catalyst, zinc, tin, zirconium and lead salts are preferably used, and these can be used alone or in combination.

  Specific examples of the transesterification catalyst include zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin (II) chloride, tin (IV) chloride, tin (II) acetate, tin (IV) acetate, and dibutyltin. Dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead (II) acetate, lead (IV) acetate and the like are used.

These catalysts are used in a ratio of 10 ⁻⁹ to 10 ⁻³ mol, preferably 10 ⁻⁷ to 10 ⁻⁴ mol, per 1 mol of the total of dihydroxy compounds.

  The melt polycondensation method is a method in which melt polycondensation is performed using the above-described raw materials and catalyst while removing by-products by a transesterification reaction under normal pressure or reduced pressure. The reaction is generally carried out in a multistage process of two or more stages.

  Specifically, the reaction at the first stage is allowed to react at a temperature of 120 to 260 ° C., preferably 180 to 240 ° C. for 0.1 to 5 hours, preferably 0.5 to 3 hours. Next, the reaction temperature is raised while raising the degree of vacuum of the reaction system to react the dihydroxy compound and the carbonic acid diester, and finally polycondensation is carried out at a temperature of 200 to 350 ° C. under a reduced pressure of 1 mmHg or less for 0.05 to 2 hours. Perform the reaction. Such a reaction may be carried out continuously or batchwise. The reaction apparatus used for carrying out the above reaction is equipped with paddle blades, lattice blades, glasses blades, etc. even with vertical types equipped with vertical stirring blades, Max blend stirring blades, helical ribbon stirring blades, etc. It may be a horizontal type or an extruder type equipped with a screw. In particular, it is preferable to use a reactor in which these are appropriately combined in consideration of the viscosity of the polymer.

  In the obtained polycarbonate resin, the catalyst is removed or deactivated after the polymerization reaction in order to maintain thermal stability and hydrolysis stability. In general, a method of deactivating a catalyst by adding a known deactivator is preferably performed. Specific examples of these substances include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, and aromatic sulfonic acids such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate. Preference is given to esters, phosphoric acids such as phosphorous acid, phosphoric acid, phosphonic acid, benzoyl chloride, p-toluenesulfonic acid chloride and the like. These deactivators are used in an amount of 0.01 to 50 times mol, preferably 0.3 to 20 times mol for the amount of catalyst. When the amount is less than 0.01 times the amount of the catalyst, the deactivation effect is insufficient. Moreover, when it is more than 50 times mole with respect to the amount of catalyst, heat resistance will fall and it will become easy to color a molded object.

  After deactivation of the catalyst, a step of devolatilizing and removing the low-boiling compounds in the polymer at a pressure of 13.3 to 1133.3 Pa and a temperature of 200 to 350 ° C. may be provided. A horizontal apparatus equipped with a stirring blade excellent in surface renewability, such as a glasses blade, or a thin film evaporator is preferably used.

  The polycarbonate resin in the present invention is preferably one having 0.7 g of the polymer dissolved in 100 ml of methylene chloride and having a specific viscosity in the range of 0.12 to 0.55 measured at 20 ° C. A range is more preferable. If the specific viscosity is less than 0.12, the molded product becomes brittle, and if it exceeds 0.55, the melt viscosity and the solution viscosity become high.

<Polyester carbonate>
In the polyester carbonate used in the present invention, the acid component forming the ester unit is a dicarboxylic acid component represented by the general formula (4) and / or the general formula (5), and is represented by the general formula (1). The ratio of the monomer component and the total of the dicarboxylic acid components represented by the general formula (4) and / or the general formula (5) is (1): ((4) + (5)) = 50 in molar ratio. : 50 to 95: 5, preferably 70:30 to 95: 5, and more preferably 75:25 to 90:10. When the latter ratio exceeds 50:50, the performance as an optical material may deteriorate.
Such a polyester carbonate may be copolymerized with a dihydroxy compound represented by the above general formula (3) that can be copolymerized with the fluorene compound represented by the above formula (1).
The ratio of the dihydroxy compound represented by the general formula (3) is a molar ratio with the fluorene compound represented by the general formula (1), and the formula (1): the formula (3) = 80 to 100: 20 to 0 More preferably, it is 90-100: 10-0.

The dihydroxy compound represented by the general formula (3) preferably used is the same as that described for the polycarbonate. Similarly, other dihydroxy compounds may be used in combination as long as the optical properties are not impaired.
[Dicarboxylic acid]
The acid component forming the ester unit is represented by the following general formula (4)

(In the formula, R13 and R14 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms. And / or the following general formula (5):

(In the formula, R15 and R16 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms. A dicarboxylic acid represented by the following formula:

Preferred dicarboxylic acids represented by general formula (4) include terephthalic acid and isophthalic acid, with terephthalic acid being particularly preferred. Examples of the dicarboxylic acid represented by the general formula (5) preferably used include 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 6-Naphthalenedicarboxylic acid is preferred. Of these, terephthalic acid and isophthalic acid, particularly terephthalic acid are preferred as the dicarboxylic acid.
In addition, in the range which does not inhibit an optical characteristic, dicarboxylic acid components other than the dicarboxylic acid represented by General formula (4) or General formula (5) may be included.

[Production method of polyester carbonate]
Examples of the carbonate precursor used for producing the polyester carbonate resin include phosgene, diphenyl carbonate, bischloroformate of the above dihydric phenols, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, and di-p-chlorophenyl carbonate. And dinaphthyl carbonate. Among them, diphenyl carbonate is preferable.

  As a method for producing a polyester carbonate resin, a method used for producing a normal polyester carbonate resin is arbitrarily employed. For example, a reaction between a diol and a dicarboxylic acid or dicarboxylic acid chloride and phosgene, or a transesterification reaction between a diol and a dicarboxylic acid or dicarboxylic acid dialkyl ester and a bisaryl carbonate is preferably employed.

  In the reaction of diol, dicarboxylic acid or its acid chloride with phosgene, the reaction is carried out in the presence of an acid binder and a solvent in a non-aqueous system. Examples of the acid binder include pyridine, dimethylaminopyridine, tertiary amine and the like. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. It is desirable to use a terminal terminator such as phenol or p-tert-butylphenol as the molecular weight regulator. The reaction temperature is usually 0 to 40 ° C., and the reaction time is preferably several minutes to 5 hours.

  In the transesterification reaction, a diol and a dicarboxylic acid or diester thereof and a bisaryl carbonate are mixed in the presence of an inert gas, and the reaction is usually performed at 120 to 350 ° C., preferably 150 to 300 ° C. under reduced pressure. The degree of vacuum is changed stepwise, and finally the alcohols produced at 1 mmHg or less are distilled out of the system. The reaction time is usually about 1 to 4 hours. However, when the polymerization temperature is 350 ° C. or higher, phenyl vinyl ether and acetaldehyde are easily produced as by-products, which is not preferable.

  In the transesterification reaction, a polymerization catalyst can be used to promote the reaction. As such a polymerization catalyst, an alkali metal compound, an alkaline earth metal compound or a heavy metal compound may be used as a main component, and a nitrogen-containing basic compound may be used as a subsidiary component if necessary.

  Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium salt of bisphenol A, and the like. Examples of the alkaline earth metal compound include calcium hydroxide, magnesium hydroxide, calcium carbonate and the like.

  Examples of the nitrogen-containing basic compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylamine, triethylamine, dimethylbenzylamine, triphenylamine, dimethylaminopyridine and the like.

  Other transesterification catalysts include zinc, tin, zirconium, lead, titanium, germanium, antimony, osmium, and aluminum salts, such as zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin chloride (II ), Tin chloride (IV), tin acetate (II), tin acetate (IV), dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead (II) acetate, acetic acid Lead (IV) titanium tetrabutoxide (IV) or the like is used.

These catalysts may be used alone or in combination of two or more. The amount of these polymerization catalysts used is a ratio of 10 ⁻⁹ to 10 ⁻³ mol with respect to 1 mol of the diol and the dicarboxylic acid in total. Used. These may be used alone or in combination of two or more. In the transesterification reaction, a diaryl carbonate having an electron-withdrawing substituent may be added at a later stage or after completion of the polycondensation reaction in order to reduce the hydroxy end group. Furthermore, an antioxidant or a heat stabilizer may be added to improve the hue.

  Further, after completion of the polymerization reaction, the catalyst may be removed or deactivated in order to maintain thermal stability and hydrolysis stability. For alkali metal compounds or alkaline earth metal compounds, generally, a method of deactivating a catalyst by adding a known deactivator is preferably carried out. Specific examples of these substances include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, aromatic sulfonic acid esters such as butyl p-toluenesulfonate, phosphorous acid, Phosphoric acids such as phosphoric acid and phosphonic acid, triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, phosphoric acid Phosphoric esters such as triphenyl, phosphonic acids such as diphenylphosphonic acid, phosphonic acid esters such as diethyl phenylphosphonate, phosphines such as triphenylphosphine, aromatic sulfonic acids such as tetrabutylphosphonium dodecylbenzenesulfonate Salts are preferably used. These deactivators are used in an amount of 0.01 to 50 times mol, preferably 0.3 to 20 times mol for the amount of catalyst. When the amount is less than 0.01 times the amount of the catalyst, the deactivation effect is insufficient. Moreover, when it is more than 50 times mole with respect to the amount of catalyst, heat resistance will fall and it will become easy to color a molded object.

  After catalyst deactivation, a step of devolatilizing and removing low-boiling compounds in the resin at a pressure of 133 to 13.3 Pa and a temperature of 200 to 320 ° C may be provided.

  The polyester carbonate resin in the present invention is preferably such that 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 0.12 to 0.55. A range of .45 is more preferable. When the specific viscosity is less than 0.12, the molded product becomes brittle, and when it exceeds 0.55, the melt viscosity and the solution viscosity become high, and handling becomes difficult.

<Additives>
The thermoplastic resin composition of the present invention may contain various additives in order to impart various characteristics within a range that does not impair the object of the present invention. Additives such as mold release agents, heat stabilizers, UV absorbers, bluing agents, antistatic agents, flame retardants, heat ray shielding agents, fluorescent dyes (including fluorescent whitening agents), light diffusing agents, other resins and An elastomer or the like can be blended.

As a mold release agent, that whose 90 weight% or more consists of ester of alcohol and a fatty acid is preferable. Specific examples of the ester of alcohol and fatty acid include monohydric alcohol and fatty acid ester and / or partial ester or total ester of polyhydric alcohol and fatty acid. Among these esters, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and a mixture of stearic acid triglyceride and stearyl stearate are preferably used.
The amount of the ester in the release agent is preferably 90% by weight or more, and more preferably 95% by weight or more when the release agent is 100% by weight.

  Examples of the heat stabilizer include a phosphorus heat stabilizer, a sulfur heat stabilizer, and a hindered phenol heat stabilizer. Examples of the phosphorus-based heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Tetrakis (2,4-di-tert-butylphenyl) -4,4 ′ is preferable. -Biphenylene diphosphonite is used.

As content of the phosphorus-type heat stabilizer in a thermoplastic resin composition, 0.001-0.2 weight part is preferable with respect to 100 weight part of thermoplastic resin compositions.
As the UV absorber, at least one UV absorber selected from the group consisting of benzotriazole UV absorbers, benzophenone UV absorbers, triazine UV absorbers, cyclic imino ester UV absorbers, and cyanoacrylates Is preferred.

  The blending amount of the ultraviolet absorber is preferably 0.01 to 3.0 parts by weight, more preferably 0.02 to 1.0 parts by weight with respect to 100 parts by weight in the thermoplastic resin composition. Preferably it is 0.05-0.8 weight part. If it is the range of this compounding quantity, it is possible to provide sufficient weather resistance in a thermoplastic resin composition according to a use.

Examples of the bluing agent include Macrolex Violet B and Macrolex Blue RR manufactured by Bayer and polysynthremble-RLS manufactured by Clariant.
The blending amount of the bluing agent is preferably 0.05 to 1.5 ppm, more preferably 0.1 to 1.2 ppm with respect to the thermoplastic resin composition.

<Method for producing thermoplastic resin composition>
The thermoplastic resin composition having a fluorene skeleton of the present invention can be obtained by blending a thermoplastic resin having a fluorene skeleton, an aliphatic epoxy compound, and various additives by any blending method. It is preferable that all or a part of each component is mixed at the same time or separately, for example, with a blender such as a blender, kneader, Banbury mixer, roll, or extruder, and uniformly dispersed.

  Further, it is also possible to use a method in which a composition previously dry blended is melt-kneaded with a heated extruder, homogenized, extruded into a wire shape, and then cut into a desired length and granulated.

<Physical properties of thermoplastic resin composition>
The thermoplastic resin used in the present invention preferably has a glass transition temperature (Tg) measured at a heating rate of 20 ° C./min of 130 ° C. or more and less than 200 ° C. If the Tg is less than 130 ° C., the heat resistance is not sufficient depending on the use of the optical member formed using the thermoplastic resin composition. On the other hand, if the Tg is 200 ° C. or more, the melt viscosity becomes high, Handling in forming becomes difficult.

In the thermoplastic resin composition of the present invention, the haze of a molded plate having a thickness of 0.1 mm obtained from the thermoplastic resin composition is preferably 2% or less, and more preferably 1% or less. .
In the thermoplastic resin composition of the present invention, the amount of resin extruded in 300 ° C., a load of 1.2 kgf for 10 minutes is preferably 30 g or more, and more preferably 40 g or more.
The thermoplastic resin composition of the present invention preferably has a molecular weight retention of 95% or more after being left for 400 hours under conditions of 85 ° C. and 85% RH, and has no hue change. More preferably, the molecular weight retention is 97% or more.

<Method for producing optical member>
The optical member of the present invention can be molded by, for example, injection molding, compression molding, injection compression molding, or casting of the thermoplastic resin composition having the fluorene skeleton of the present invention.
(Optical lens)
When manufacturing the optical lens which consists of the thermoplastic resin composition of this invention by injection molding, it is preferable to shape | mold on conditions with a cylinder temperature of 260-350 degreeC and a mold temperature of 90-170 degreeC. More preferably, molding is preferably performed under conditions of a cylinder temperature of 270 to 320 ° C and a mold temperature of 100 to 160 ° C. When the cylinder temperature is higher than 350 ° C., the resin is decomposed and colored. When the cylinder temperature is lower than 230 ° C., the melt viscosity is too high to be molded. When the mold temperature is higher than 170 ° C., the resin is not cured and the molded piece cannot be taken out from the mold. On the other hand, if it is less than 90 ° C., the resin quickly hardens in the mold during molding, and a molded piece cannot be obtained, or the mold molding cannot be transferred.

The optical lens of the present invention is preferably used in the form of an aspheric lens as necessary. Since an aspheric lens can substantially eliminate spherical aberration with a single lens, there is no need to remove spherical aberration with a combination of a plurality of spherical lenses, thus reducing weight and reducing production costs. It becomes possible. Therefore, the aspherical lens is particularly useful as a camera lens among optical lenses.
Moreover, since the thermoplastic resin composition of the present invention has high molding fluidity, it is particularly useful as a material for an optical lens having a thin, small and complicated shape.

As a specific lens size, the upper limit of the thickness of the central portion is preferably 0.5 mm or less, and more preferably 0.4 mm or less. Further, the lower limit of the thickness of the central portion of the lens is preferably 0.05 mm or more, and more preferably 0.1 mm or more.
Moreover, a diameter is 1.0 mm-20.0 mm, More preferably, it is 1.0-10.0 mm, More preferably, it is 3.0-10.0 mm.
In addition, it is preferably a meniscus lens having a convex surface on one side and a concave surface on the other side.

The following examples further illustrate the present invention.
[Examples 1-7, Comparative Examples 1-9]
Evaluation was based on the following method.
(Evaluation method)
(1) Specific viscosity of resin: The resin obtained after completion of polymerization was dried at 120 ° C. for 4 hours, and a solution in which 0.35 g of the resin was dissolved in 50 cc of methylene chloride was used as a measurement sample. In the measurement, the passage time between the marked lines of the Oswald viscosity tube was measured in a constant temperature bath of 20 ± 0.01 ° C., and the specific viscosity (η _sp ) of the solution at 20 ° C. was obtained from the following formula.
η _sp = (t ₁ −t ₀ ) / t ₀
Here, t _{1 is a} passage time between marked lines of the resin solution, and t ₀ is a passage time between marked lines of methylene chloride.
(2) Copolymerization ratio: The resin after polymerization was measured using proton NMR of JNM-AL400 manufactured by JEOL Ltd.
(3) Glass transition point (Tg): Measured by DuPont 910 DSC.
(4) Molding fluidity (Melting viscosity (MVR)): Melted in a quantity of resin extruded at 300 ° C. under a load of 1.2 kgf for 10 minutes using a nozzle with a diameter of 1 mm and a length of 10 mm by Capirograh 1D manufactured by Toyo Seiki The viscosity was measured.
(5) Haze: Haze was measured on a molded plate having a thickness of 1 mm using Nippon Denshoku Industries Co., Ltd. Haze Meter NDH2000.
(6) Moisture and heat stability Molecular weight retention: After a molded piece having a thickness of 1 mm is allowed to stand for 2000 hours under the conditions of 85 ° C. and 85% RH, the specific viscosity retention is retained by the change in specific viscosity described below. Rated as a rate.

From a solution obtained by dissolving 0.7 g of the molded piece in 100 ml of methylene chloride, the specific viscosity (η _sp ) of the solution at 20 ° C. was measured, and the specific viscosity retention rate (molecular weight retention rate) after the wet heat test was determined. The specific viscosity retention rate (molecular weight retention rate) was used as an index of moisture and heat resistance.
Δη _sp = (η _sp 1 / η _sp 0) × 100
* Δη _sp : specific viscosity retention, η _sp 0: specific viscosity before test, η _sp 1: specific viscosity after test (7) Optical lens molding stability: poor filling of aspherical lens after molding, each molding Defects, insufficient lens strength, etc. were confirmed visually. Evaluation was performed by performing 100-shot molding, and the probability of being a defective product was less than 1% (◎), 1 to 5% (）), 5 to 20% (Δ), and 20% or less (x).

  Filling failure is defined as a filling failure due to insufficient resin to form a lens shape. Molding failure is caused by one or more silver stripes / bubbles in one lens, or additive bleeding out. Shall be. Further, the insufficient strength of the lens means that the lens part and the sprue / runner part are broken from the mold during molding and cannot be taken out.

(Synthesis)
PC (1): Polycarbonate 21540 parts by weight of ion-exchanged water and 4930 parts by weight of a 48% aqueous sodium hydroxide solution were placed in a reactor equipped with a thermometer, a stirrer, and a reflux condenser. , 9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “BCF”) 3231 parts by weight, 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as “BPA”) 1949 parts by weight and 15 parts by weight of hydrosulfite were dissolved, 14530 parts by weight of methylene chloride was added, and then 2200 parts by weight of phosgene was blown in at 15 to 25 ° C. for 60 minutes with stirring. After the completion of phosgene blowing, 163.1 parts by weight of cumylphenol and 705 parts by weight of a 48% aqueous sodium hydroxide solution were added. After emulsification, 5.9 parts by weight of triethylamine was added and the reaction was stirred at 28-33 ° C. for 1 hour. finished. After completion of the reaction, the product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and when the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, the methylene chloride was evaporated with a kneader, A white polymer having a molar ratio of BCF to BPA of 50:50, a specific viscosity of 0.297, and a Tg of 197 ° C. was obtained.

PC (2)
In a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 21540 parts by weight of ion-exchanged water and 4930 parts by weight of a 48% aqueous sodium hydroxide solution were added, and 9,9-bis (4 -Hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “BCF”) 3231 parts by weight, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene (hereinafter abbreviated as “BPM”) 2958 parts by weight and 15 parts by weight of hydrosulfite were dissolved, 14530 parts by weight of methylene chloride was added, and then 2200 parts by weight of phosgene was blown in at 15 to 25 ° C. for 60 minutes with stirring. After the completion of phosgene blowing, 163.1 parts by weight of cumylphenol and 705 parts by weight of a 48% aqueous sodium hydroxide solution were added. After emulsification, 5.9 parts by weight of triethylamine was added and the reaction was stirred at 28-33 ° C. for 1 hour. finished. After completion of the reaction, the product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and when the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, the methylene chloride was evaporated with a kneader, A white polymer having a molar ratio of BCF to BPM of 50:50, a specific viscosity of 0.297, and a Tg of 156 ° C. was obtained.

PC (3)
9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (hereinafter abbreviated as “BPEF”) 1403.2 parts by weight, BPA 182.7 parts by weight, diphenyl carbonate (hereinafter abbreviated as “DPC”) 878.0 parts by weight and sodium hydrogen carbonate 5.0 × 10 ⁻³ parts by weight were placed in a reactor equipped with a stirrer and a distillation apparatus, and after nitrogen substitution three times, a nitrogen atmosphere 101.3 It heated at 215 degreeC under * 10 < ³ > Pa, and stirred for 20 minutes. After complete dissolution, it was adjusted to 20 × 10 ³ Pa over 15 minutes, and kept for 20 minutes under the conditions of 215 ° C. and × 10 ³ Pa, to conduct a transesterification reaction. Furthermore, it heated up to 240 degreeC at the speed | rate of 37.5 degreeC / hr, and hold | maintained for 10 minutes at 240 degreeC and 20.0 * 10 < ³ > Pa. Then, it adjusted to 16.0 * 10 < ³ > Pa over 10 minutes, and hold | maintained for 70 minutes at 240 degreeC and * 10 < ³ > Pa. Then, over a period of 10 minutes was adjusted to ^{13.3 × 10 3 Pa, 240 ℃} , held for 10 minutes at 13.3 × ¹⁰ 3 Pa. Furthermore, it was set to 133.3 Pa or less over 40 minutes, and the polymerization reaction was carried out with stirring for 10 minutes under the conditions of 240 ° C. and 133.3 Pa or less. After completion of the reaction, nitrogen was blown into the reactor to increase the pressure, and the produced resin was extracted while pelletizing. A colorless and transparent pellet having a molar ratio of BPEF to BPA of 80:20, a specific viscosity of 0.192, and Tg of 145 ° C. was obtained.

PEC (1): Polyester carbonate BPEF 1403.2 parts by weight, dimethyl terephthalate (hereinafter sometimes abbreviated as “DMT”) 155.4 parts by weight, DPC 548.4 parts by weight, titanium tetrabutoxide 13.6 × 10 ⁻⁴ A part by weight was placed in a reaction kettle equipped with a stirrer and a distillation apparatus, heated to 180 ° C. under a nitrogen atmosphere of 101.3 × 10 ³ Pa, and stirred for 20 minutes. Thereafter, the degree of vacuum was adjusted to 20 × 10 ³ Pa over 20 minutes, and the temperature was raised to 250 ° C. at a rate of 60 ° C./hr to conduct a transesterification reaction. Thereafter, while maintaining the temperature at 250 ° C., the pressure was reduced to 133.3 Pa or less over 120 minutes, and the polymerization reaction was performed with stirring for 1 hour under the conditions of 250 ° C. and 133.3 Pa or less. Thereafter, the produced resin was extracted while pelletizing. A colorless transparent pellet having a molar ratio of BPEF to terephthalic acid of 80:20, a specific viscosity of 0.201, and a Tg of 150 ° C. was obtained.

(Molded piece)
The pelletized resin composition was heat-dried at 120 ° C. for 8 hours. Then, using a SE30DU injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. at a molding temperature of Tg + 110 ° C. and a mold temperature of Tg−10 ° C., a molded piece having a width of 2.5 cm, a length of 5 cm, and a thickness of 1 mm was injected. Molded. Table 1 shows the evaluation results of haze and heat-and-moisture resistance.

(Optical lens)
Using a SE30DU injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., using resin molding temperature Tg + 170 ° C., mold temperature Tg-5 ° C., thickness 0.3 mm, convex curvature radius 5 mm, concave curvature radius 4 mm, diameter A 5 mm aspheric lens was injection molded. Table 1 shows the evaluation of molding stability of the optical lens.

(Additive)
Additive 1: Epoxidized soybean oil (number of epoxy groups: 4) Kapox S-6 manufactured by Kao Corporation
Additive 2: Epoxidized linseed oil (number of epoxy groups 6) Adeka Sizer O-180A manufactured by ADEKA
Additive 3: Alkyl monoester, alkyl triglyceride mixture Rikenmar SL-900 manufactured by RIKEN
Additive 4: 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate Additive 5: Bisphenoxyethanol full orange glycidyl ether Additive 6: Trioctyl trimellitic acid Additive 7: Polyether ester resin Eastman Chemical Company ECDEL 9966
Additive 8: Styrene oligomer FTR 2140 manufactured by Mitsui Chemicals, Inc.
Stabilizer: Tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite Mold release agent: Glycerol monostearate The unit of Table 1 is parts by weight with respect to the amount.

[Examples 1-7 and Comparative Examples 1-9]
After the various components were previously dry-blended uniformly in the proportions shown in Table 1, the KZ-W15-30MG twin-screw extruder manufactured by Technobel Co., Ltd. and manufactured by Technobel Co. were used under the conditions described in Table 1 below. It was melted and pelletized, and a molded product was appropriately prepared and evaluated.

  Examples 1 to 7 shown in Table 1 can improve molding fluidity while maintaining haze and heat-and-moisture resistance stability, have good moldability of optical lenses, and can be usefully used for optical members. On the other hand, Comparative Example 1 is not added with an aliphatic epoxy compound and is inferior in fluidity, so a thin lens cannot be molded. In Comparative Example 2, the addition amount is small, the fluidity is poor, and a thin lens cannot be molded. Further, Comparative Example 4 is inferior in heat-and-moisture stability because the additive does not have an epoxy group. Comparative Example 5 is an alicyclic epoxy compound that is inferior in molding fluidity and has many molding defects during molding. Comparative Example 6 is an aromatic epoxy compound and is inferior in molding fluidity. In Comparative Example 7, the molding fluidity is improved, but the additive is volatilized at the time of molding, and there are many molding defects. Further, the heat and heat resistance is poor, the environment for use as an optical member is limited, and the versatility is poor. . Comparative Examples 8 and 9 are inferior in moldability and wet heat resistance due to the decomposition of the additive. Since Comparative Example 3 has a large amount of addition and cannot maintain transparency, it cannot be used as an optical member.

[Effect of the invention]
The thermoplastic resin composition having a fluorene skeleton of the present invention has high transparency, molding fluidity, molding stability, and heat-and-moisture stability, so that it is possible to mold a thin optical member that has been difficult to injection molding in the past. Thus, a thinner optical member can be provided. The thermoplastic resin composition having a fluorene skeleton is particularly suitable for a camera lens for a portable camera, a lens such as a pickup lens microarray lens, a projector lens, and a Fresnel lens.

  The optical member using the thermoplastic resin composition having a fluorene skeleton of the present invention can be used for various cameras such as digital video cameras, telescopes, binoculars, television projectors, prisms, and the like. In particular, it is effective as a thin and small lens such as a camera lens for a mobile phone, a digital camera lens, an in-vehicle camera lens, and a web camera lens.

Claims (11)

The following general formula (1)

(In the formula, R1, R2, R3 and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or 5 carbon atoms. A cycloalkoxyl group having 20 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, X is an alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or carbon. An arylene group of 6 to 20. n and m are integers of 0 to 10.) 100 parts by weight of a thermoplastic resin containing a repeating unit composed of a carbonate unit or an ester unit derived from a monomer represented by General formula (2)

(Wherein R is CH ₃ or H, o is 1 to 20, p is 1 to 10, and I is 1 to 20). A thermoplastic resin composition having a fluorene skeleton containing 0.1 to 10 parts by weight. The thermoplastic resin composition having a fluorene skeleton according to claim 1, wherein the aliphatic epoxy compound is an epoxy compound having a glycerin skeleton. The thermoplastic resin composition having a fluorene skeleton according to claim 2, wherein the epoxy compound having a glycerin skeleton is an epoxidized vegetable oil. The thermoplastic resin composition having a fluorene skeleton according to claim 3, wherein the epoxidized vegetable oil is epoxidized soybean oil or epoxy linseed oil. The thermoplastic resin composition having a fluorene skeleton according to claim 4, wherein the number of epoxy groups in the epoxidized soybean oil and epoxidized sesame oil is 2 to 8. The thermoplastic resin includes a repeating unit composed of a carbonate unit derived from a monomer represented by the general formula (1) and the following general formula (3).

(Wherein R5 to R8 are each independently a hydrogen atom, a hydrocarbon group or a halogen atom which may contain an aromatic group having 1 to 9 carbon atoms, and W is a single bond, having 1 to 20 carbon atoms. A hydrocarbon group, O, S, SO, SO ₂ , CO or COO group which may contain an aromatic group.)
The ratio of the formula (1) and the formula (3) is a molar ratio of (1) :( 3) = 100: 0 to 50:50. Heat having a fluorene skeleton according to any one of claims 1 to 5, wherein 0.7 g is dissolved in 100 ml of methylene chloride and the specific viscosity measured at 20 ° C is 0.12 to 0.55. Plastic resin composition. The thermoplastic resin is represented by the following general formula (4).

(In the formula, R13 and R14 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms. An ester-based unit derived from a monomer represented by:
General formula (5)

(In the formula, R15 and R16 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms. The ratio of the formula (1) and the sum of the formula (4) and the formula (5) is a molar ratio of (1) :( (4) + (5)) = polyester carbonate in the range of 50:50 to 95: 5, 0.7 g is dissolved in 100 ml of methylene chloride, and the specific viscosity measured at 20 ° C. is 0.12 to 0.4. The thermoplastic resin composition having a fluorene skeleton according to any one of claims 1 to 5, which is 55. The monomer represented by the general formula (1) is 9,9-bis (4-hydroxy-3-methylphenyl) fluorene or 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene. Item 8. A thermoplastic resin composition having a fluorene skeleton according to any one of Items 1 to 7. The optical member which consists of a thermoplastic resin composition which has a fluorene skeleton in any one of Claims 1-8. The optical member according to claim 9, wherein the optical member is an optical lens of a camera lens, a pickup lens, a microarray lens, a projector lens, or a Fresnel lens. The optical member according to claim 10, wherein the optical lens has a thickness of 0.5 mm or less.