JP6861569B2 - Polycarbonate resin, its manufacturing method and optical molded product - Google Patents

Description

The present invention relates to a polycarbonate resin, a method for producing the same, and an optically molded product.

Optical glass or optical resin is used as the material of the optical lens used in the optical system of various cameras such as cameras, film-integrated cameras, and video cameras. Optical glass is excellent in heat resistance, transparency, dimensional stability, chemical resistance, etc., and there are various kinds of materials having various refractive indexes and Abbe numbers. However, it has problems that the material cost is high, the molding processability is poor, and the productivity is low.

On the other hand, an optical lens made of an optical resin has an advantage that it can be mass-produced by injection molding. For example, a polycarbonate resin or the like is used in a camera lens. However, in recent years, the development of a resin having a high refractive index has been required due to the miniaturization of products. Generally, when the refractive index of an optical material is high, a lens element having the same refractive index can be realized on a surface having a smaller curvature, so that the amount of aberration generated on this surface can be reduced. As a result, it is possible to reduce the number of lenses, reduce the eccentric sensitivity of the lens, and reduce the thickness and weight of the lens.

Examples of the technique related to the optical resin include those described in Patent Documents 1 and 2.
Patent Document 1 (Japanese Unexamined Patent Publication No. 2005-241962) describes an optical lens made of a polycarbonate resin having a fluorene structure.
Patent Document 2 (Japanese Unexamined Patent Publication No. 2005-187661) describes a method for easily improving the refractive index by blending (mixing and adding) a sulfur-containing compound with a fluorene-containing polyester.

Japanese Unexamined Patent Publication No. 2005-241962 Japanese Unexamined Patent Publication No. 2005-187661

However, the polycarbonate resin as described in Patent Document 1 has a low refractive index and is not sufficiently satisfactory.
Further, as described in Patent Document 2, when a sulfur-containing compound is blended with a fluorene-containing polyester, the refractive index is improved, but the thermal stability is lowered due to the addition of a low molecular weight component, and the compatibility of the two components to be blended is reduced. If it is bad, the transparency will decrease.

The present invention has been made in view of the above circumstances, and provides a polycarbonate resin capable of realizing an optically molded product having a high refractive index and excellent transparency.

The present inventors have diligently studied to provide a polycarbonate resin capable of realizing an optical molded product having a high refractive index and excellent transparency. As a result, when a polycarbonate resin having a structural unit (A) represented by the following formula (A) and a structural unit (B) represented by the following formula (B) is used, it has a high refractive index and We have found that an optical molded product having excellent transparency can be realized, and have reached the present invention.

According to the present invention, the following polycarbonate resin, a method for producing the same, and an optically molded product are provided.

（上記式（Ａ）中、Ｒ_１〜Ｒ_４は水素原子、ハロゲン原子、炭素数６〜２０のアリール基、炭素数１〜２０のアルキル基または炭素数５〜２０のシクロアルキル基を表し、それぞれ同一または異なっていてもよい。）

（上記式（Ｂ）中、Ｒ_５〜Ｒ_１２は水素原子、ハロゲン原子、炭素数６〜２０のアリール基、炭素数１〜２０のアルキル基または炭素数５〜２０のシクロアルキル基を表し、それぞれ同一または異なっていてもよく、Ｘは炭素数２〜１０のアルキレン基を表し、それぞれ同一または異なっていてもよく、Ｗは−Ｓ−、−ＳＯ−または−ＳＯ_２−を表し、ｎおよびｍはそれぞれ独立に０〜６の整数を表す。ただし、ｎ＋ｍは０ではない。）
［２］
上記［１］に記載のポリカーボネート樹脂において、
上記ポリカーボネート樹脂中の全ての構成単位の合計を１００モル％としたとき、上記ポリカーボネート樹脂中の上記構成単位（Ａ）と上記構成単位（Ｂ）の合計含有量が５０モル％以上１００モル％以下であるポリカーボネート樹脂。
［３］
上記［１］または［２］に記載のポリカーボネート樹脂において、
上記ポリカーボネート樹脂中の上記構成単位（Ａ）と上記構成単位（Ｂ）のモル比（（Ａ）／（Ｂ））が、２／９８以上９８／２以下であるポリカーボネート樹脂。
［４］
上記［１］乃至［３］いずれか一つに記載のポリカーボネート樹脂において、
上記式（Ａ）中、Ｒ_１〜Ｒ_４が水素原子または炭素数１〜３のアルキル基であり、
上記式（Ｂ）中、Ｒ_５〜Ｒ_１２が水素原子または炭素数１〜３のアルキル基であり、Ｘが１，２−エチレン基であり、ｎおよびｍが１または０であるポリカーボネート樹脂。
［５］
上記［１］乃至［４］いずれか一つに記載のポリカーボネート樹脂において、
ＪＩＳ Ｋ−７１４２に準拠して測定される２３℃、波長５８９ｎｍにおける屈折率が１．６３０以上１．６９５以下であるポリカーボネート樹脂。
［６］
上記［１］乃至［５］いずれか一つに記載のポリカーボネート樹脂において、
示差走査熱量により測定されるガラス転移温度が８０℃以上１９０℃以下であるポリカーボネート樹脂。
［７］
上記［１］乃至［６］いずれか一つに記載のポリカーボネート樹脂において、
ＪＩＳ Ｋ−７３６１−１に準拠して測定される全光線透過率が８５％以上であるポリカーボネート樹脂。
［８］
上記［１］乃至［７］いずれか一つに記載のポリカーボネート樹脂において、
ポリスチレン換算の重量平均分子量（Ｍｗ）が１．５×１０^４以上２．０×１０^５以下であるポリカーボネート樹脂。
［９］
上記［１］乃至［８］いずれか一つに記載のポリカーボネート樹脂において、
アッベ数が２７以下であるポリカーボネート樹脂。
［１０］
上記［１］乃至［９］いずれか一つに記載のポリカーボネート樹脂を製造するための製造方法であって、
下記式（Ｉ）で表されるジヒドロキシ化合物（Ｉ）および下記式（ＩＩ）で表されるジヒドロキシ化合物（ＩＩ）を、炭酸ジエステルと反応させることにより、上記ポリカーボネート樹脂を合成する工程を含み、
反応系内に含まれる全てのジヒドロキシ化合物の合計を１００モル％としたとき、上記ジヒドロキシ化合物（Ｉ）と上記ジヒドロキシ化合物（ＩＩ）の合計が５０モル％以上であるポリカーボネート樹脂の製造方法。

（上記式（Ｉ）中、Ｒ_１〜Ｒ_４は水素原子、ハロゲン原子、炭素数６〜２０のアリール基、炭素数１〜２０のアルキル基または炭素数５〜２０のシクロアルキル基を表し、それぞれ同一または異なっていてもよい。）

（上記式（ＩＩ）中、Ｒ_５〜Ｒ_１２は水素原子、ハロゲン原子、炭素数６〜２０のアリール基、炭素数１〜２０のアルキル基または炭素数５〜２０のシクロアルキル基を表し、それぞれ同一または異なっていてもよく、Ｘは炭素数２〜１０のアルキレン基を表し、それぞれ同一または異なっていてもよく、Ｗは−Ｓ−、−ＳＯ−または−ＳＯ_２−を表し、ｎおよびｍはそれぞれ独立に０〜６の整数を表す。ただし、ｎ＋ｍは０ではない。）
［１１］
上記［１０］に記載のポリカーボネート樹脂の製造方法において、
上記ジヒドロキシ化合物（Ｉ）と上記ジヒドロキシ化合物（ＩＩ）のモル比（（Ｉ）／（ＩＩ））が、２／９８以上９８／２以下であるポリカーボネート樹脂の製造方法。
［１２］
上記［１］乃至［９］いずれか一つに記載のポリカーボネート樹脂を含む光学成形体。［１３］
光学レンズである上記［１２］に記載の光学成形体。
［１４］
光学フィルムである上記［１２］に記載の光学成形体。 [1]
A polycarbonate resin having a structural unit (A) represented by the following formula (A) and a structural unit (B) represented by the following formula (B).

(In the above formula (A), R _{1 to} R ₄ represent a hydrogen atom, a halogen atom, an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms. They may be the same or different.)

(In the above formula (B), R _{5 to} R ₁₂ represent a hydrogen atom, a halogen atom, an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms. may be the same or different, X represents an alkylene group having 2 to 10 carbon atoms, may be the same or different, W is -S -, - SO- or -SO ₂ - represents, n and m independently represents an integer of 0 to 6. However, n + m is not 0.)
[2]
In the polycarbonate resin according to the above [1],
When the total of all the structural units in the polycarbonate resin is 100 mol%, the total content of the structural units (A) and the structural units (B) in the polycarbonate resin is 50 mol% or more and 100 mol% or less. Polycarbonate resin.
[3]
In the polycarbonate resin according to the above [1] or [2],
A polycarbonate resin in which the molar ratio ((A) / (B)) of the structural unit (A) to the structural unit (B) in the polycarbonate resin is 2/98 or more and 98/2 or less.
[4]
In the polycarbonate resin according to any one of the above [1] to [3],
In the above formula (A), R _{1 to} R ₄ are hydrogen atoms or alkyl groups having 1 to 3 carbon atoms.
In the above formula (B), R _{5 to} R ₁₂ are hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, X is a 1,2-ethylene group, and n and m are 1 or 0.
[5]
In the polycarbonate resin according to any one of the above [1] to [4],
A polycarbonate resin having a refractive index of 1.630 or more and 1.695 or less at 23 ° C. and a wavelength of 589 nm, which is measured according to JIS K-7142.
[6]
In the polycarbonate resin according to any one of the above [1] to [5],
A polycarbonate resin having a glass transition temperature of 80 ° C. or higher and 190 ° C. or lower as measured by differential scanning calorimetry.
[7]
In the polycarbonate resin according to any one of the above [1] to [6],
A polycarbonate resin having a total light transmittance of 85% or more measured in accordance with JIS K-7361-1.
[8]
In the polycarbonate resin according to any one of the above [1] to [7],
The weight average molecular weight (Mw) in terms of polystyrene 1.5 × 10 ⁴ or more 2.0 × 10 ⁵ or less is a polycarbonate resin.
[9]
In the polycarbonate resin according to any one of the above [1] to [8],
Polycarbonate resin having an Abbe number of 27 or less.
[10]
The production method for producing the polycarbonate resin according to any one of the above [1] to [9].
Including a step of synthesizing the above-mentioned polycarbonate resin by reacting the dihydroxy compound (I) represented by the following formula (I) and the dihydroxy compound (II) represented by the following formula (II) with a carbonic acid diester.
A method for producing a polycarbonate resin, wherein the total of the dihydroxy compound (I) and the dihydroxy compound (II) is 50 mol% or more, assuming that the total of all the dihydroxy compounds contained in the reaction system is 100 mol%.

(In the above formula (I), R _{1 to} R ₄ represent a hydrogen atom, a halogen atom, an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms. They may be the same or different.)

(In the above formula (II), R _{5 to} R ₁₂ represent a hydrogen atom, a halogen atom, an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms. may be the same or different, X represents an alkylene group having 2 to 10 carbon atoms, may be the same or different, W is -S -, - SO- or -SO ₂ - represents, n and m independently represents an integer of 0 to 6. However, n + m is not 0.)
[11]
In the method for producing a polycarbonate resin according to the above [10],
A method for producing a polycarbonate resin in which the molar ratio ((I) / (II)) of the dihydroxy compound (I) to the dihydroxy compound (II) is 2/98 or more and 98/2 or less.
[12]
An optical molded product containing the polycarbonate resin according to any one of the above [1] to [9]. [13]
The optically molded product according to the above [12], which is an optical lens.
[14]
The optically molded product according to the above [12], which is an optical film.

According to the present invention, it is possible to provide a polycarbonate resin capable of realizing an optically molded product having a high refractive index and excellent transparency.

Hereinafter, embodiments of the present invention will be described. Unless otherwise specified, the "~" between the numbers in the sentence indicates the following from the above.

[Polycarbonate resin]
First, the polycarbonate resin according to this embodiment will be described.
The polycarbonate resin according to the present embodiment has a structural unit (A) represented by the following formula (A) and a structural unit (B) represented by the following formula (B).
According to the polycarbonate resin according to the present embodiment, by having the structural unit (A) and the structural unit (B), it is possible to realize an optically molded product having a high refractive index and excellent transparency. Further, according to the polycarbonate resin according to the present embodiment, by having the structural unit (A) and the structural unit (B), there is also an effect that the balance of low Abbe number, high heat resistance, good injection moldability, etc. is excellent. Obtainable. Further, when the polycarbonate resin according to the present embodiment is used, a molded product in which optical distortion is suppressed can be obtained, and as a result, an excellent optical lens having substantially no optical distortion can be provided.

In the above formula (A), R _{1 to} R ₄ represent a hydrogen atom, a halogen atom, an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms, respectively. It may be the same or different.

In the above formula (A), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
In the above formula (A), examples of the aryl group having 6 to 20 carbon atoms include a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group and the like.

In the above formula (A), examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group and an n-pentyl group. Group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group. Examples thereof include a group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecil group, an eikosyl group and the like.

In the above formula (A), examples of the cycloalkyl group having 5 to 20 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cycloundecyl group, a cyclododecyl group and a cyclotridecyl group. , Cyclotetradecyl group, cyclopentadecyl group, cyclohexadecyl group, cycloheptadecyl group, cyclooctadecyl group, cyclononadecil group, cycloeicosyl group and the like.

In the above formula (A), R _{1 to} R ₄ are preferably independently selected from a hydrogen atom and an alkyl group having 1 to 3 carbon atoms, respectively, and R _{1 to} R ₄ are independently selected from a hydrogen atom and a methyl group, respectively. It is more preferable that R _{1 to} R ₄ are hydrogen atoms.

上記式（Ｂ）中、Ｒ_５〜Ｒ_１２は水素原子、ハロゲン原子、炭素数６〜２０のアリール基、炭素数１〜２０のアルキル基または炭素数５〜２０のシクロアルキル基を表し、それぞれ同一または異なっていてもよく、Ｘは炭素数２〜１０のアルキレン基を表し、それぞれ同一または異なっていてもよく、Ｗは−Ｓ−、−ＳＯ−または−ＳＯ_２−を表し、ｎおよびｍはそれぞれ独立に０〜６の整数を表す。ただし、ｎ＋ｍは０ではない。

In the above formula (B), R _{5 to} R ₁₂ represent a hydrogen atom, a halogen atom, an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms, respectively. may be the same or different, X represents an alkylene group having 2 to 10 carbon atoms, may be the same or different, W is -S -, - SO- or -SO ₂ - represents, n and m Represent each independently an integer from 0 to 6. However, n + m is not 0.

In the above formula (B), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
In the above formula (B), examples of the aryl group having 6 to 20 carbon atoms include a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group and the like.

In the above formula (B), examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group and an n-pentyl group. Group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group. Examples thereof include a group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecil group, an eikosyl group and the like.

In the above formula (B), examples of the cycloalkyl group having 5 to 20 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cycloundecyl group, a cyclododecyl group and a cyclotridecyl group. , Cyclotetradecyl group, cyclopentadecyl group, cyclohexadecyl group, cycloheptadecyl group, cyclooctadecyl group, cyclononadecil group, cycloeicosyl group and the like.

In the above formula (B), R _{5 to} R ₁₂ are preferably independently selected from a hydrogen atom and an alkyl group having 1 to 3 carbon atoms, respectively, and R _{5 to} R ₁₂ are independently selected from a hydrogen atom and a methyl group, respectively. It is more preferable that R _{5 to} R ₁₂ are hydrogen atoms.

In the above formula (B), X represents an alkylene group having 2 to 10 carbon atoms, which may be the same or different from each other. Examples of the alkylene group having 2 to 10 carbon atoms include a 1,2-ethylene group, a 1,2-propylene group, a 1,3-propylene group, a 1,2-butylene group, a 1,3-butylene group, and 1, 4-butylene group, 1,4-pentylene group, 1,5-pentylene group, 1,5-hexylene group, 1,6-hexylene, 1,7-heptylene group, 1,8-octylene group, 1,9- Examples thereof include a nonylene group and a 1,10-decylene group. Of these, 1,2-ethylene groups are preferable as X.

In the above formula (B), n and m each independently represent an integer of 0 to 6. However, n + m is not 0. n + m preferably represents an integer of 1 to 6, more preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and particularly preferably 1 or 2. Further, it is more preferable that n and m are 1 or 0.
When n + m is within the above range, a glass transition temperature more suitable for injection molding can be obtained while maintaining excellent optical characteristics such as high refractive index, low Abbe number, and high transparency, and injection moldability is further improved. be able to.

In the above formula (B), W represents -S-, -SO- or -SO _2- , preferably -S- or -SO _2- , and more preferably -S-.

The polycarbonate resin according to this embodiment may further have a structural unit (C) represented by the following formula (C).

上記式（Ｃ）中、Ｚは炭素数２〜２０のアルキレン基、炭素数３〜２０のシクロアルキレン基、炭素数６〜３０の２価の芳香族基および／または炭素数８〜４０の芳香族基含有アルキレン基を表す。ただし、上記式（Ｃ）で表される構成単位（Ｃ）は、上記式（Ａ）または（Ｂ）で表される構成単位とは異なる。
Ｚは好ましくは、下記式（Ｃ１）〜（Ｃ５）で表される基を表す。

In the above formula (C), Z is an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, a divalent aromatic group having 6 to 30 carbon atoms, and / or an aromatic group having 8 to 40 carbon atoms. Represents a group-containing alkylene group. However, the structural unit (C) represented by the above formula (C) is different from the structural unit represented by the above formula (A) or (B).
Z preferably represents a group represented by the following formulas (C1) to (C5).

上記式（Ｃ１）中、ｎ１は２〜２０の整数を表す。

In the above formula (C1), n1 represents an integer of 2 to 20.

上記式（Ｃ２）中、ｎ２およびｎ３は１〜４の整数を表し、Ｗ_２は炭素数５〜１５のシクロアルキレン基を表す。Ｗ_２は、好ましくはシクロペンチレン基、シクロヘキシレン基、デカヒドロナフチレン基、ノルボニレン基、トリシクロデシレン基、およびペンタシクロペンタデシレン基から選択されるシクロアルキレン基を表す。

In the above formula (C2), n2 and n3 represent integers of 1 to 4, and W ₂ represents a cycloalkylene group having 5 to 15 carbon atoms. W ₂ preferably represents a cycloalkylene group selected from a cyclopentylene group, a cyclohexylene group, a decahydronaphthylene group, a norbonylene group, a tricyclodecylene group, and a pentacyclopentadecylene group.

上記式（Ｃ３）中、Ａｒ_２は炭素数６〜３０の２価の芳香族基を表す。
Ａｒ_２は、好ましくは置換または無置換の１，４−フェニレン基、置換または無置換の１，３−フェニレン基、置換または無置換の２，６−ナフチレン基、および置換または無置換の２，７−ナフチレン基から選択される芳香族基を表す。

In the above formula (C3), Ar ₂ represents a divalent aromatic group having 6 to 30 carbon atoms.
Ar ₂ is preferably a substituted or unsubstituted 1,4-phenylene group, a substituted or unsubstituted 1,3-phenylene group, a substituted or unsubstituted 2,6-naphthylene group, and a substituted or unsubstituted 2, Represents an aromatic group selected from 7-naphthylene groups.

上記式（Ｃ４）中、Ａｒ_３およびＡｒ_４は炭素数６〜１０の２価の芳香族基を表し、Ｗ_２は炭素数２〜１５の２価の炭化水素基、−Ｏ−基、−ＣＯ−基を表す。Ａｒ_３およびＡｒ_４は、好ましくは置換または無置換の１，４−フェニレン基、置換または無置換の１，３−フェニレン基、置換または無置換の２，６−ナフチレン基、および置換または無置換の２，７−ナフチレン基から選択される芳香族基を表す。
Ｗ_２は好ましくは、２，２−プロピリデン基、１，１−シクロヘキシレン基、１，１，−（３，３，５−トリメチル）シクロヘキシレン基、１，１−フェニルエチレン基、および９，９−フルオレン基から選択される有機基を表す。

In the above formula (C4), Ar ₃ and Ar ₄ represent a divalent aromatic group having 6 to 10 carbon atoms, and W ₂ is a divalent hydrocarbon group having 2 to 15 carbon atoms, an −O− group, − Represents a CO- group. Ar ₃ and Ar ₄ are preferably substituted or unsubstituted 1,4-phenylene group, substituted or unsubstituted 1,3-phenylene group, substituted or unsubstituted 2,6-naphthylene group, and substituted or unsubstituted 1,6-naphthylene group. Represents an aromatic group selected from the 2,7-naphthylene group of.
W ₂ is preferably a 2,2-propylidene group, a 1,1-cyclohexylene group, a 1,1,- (3,3,5-trimethyl) cyclohexylene group, a 1,1-phenylethylene group, and 9, Represents an organic group selected from 9-fluorene groups.

上記式（Ｃ５）中、ｎ４およびｎ５は１〜１０の整数を表し、Ａｒ_５は上記式（Ｃ３）または上記式（Ｃ４）を表す。

In the above formula (C5), n4 and n5 represent integers of 1 to 10, and Ar ₅ represents the above formula (C3) or the above formula (C4).

In the polycarbonate resin according to the present embodiment, when the total of all the structural units in the polycarbonate resin is 100 mol%, the content of the structural unit (C) represented by the above formula (C) is preferably 50 mol. % Or less, more preferably 40 mol% or less, still more preferably 30 mol% or less.

In the polycarbonate resin according to the present embodiment, when the total of all the structural units in the polycarbonate resin is 100 mol%, the total content of the structural units (A) and the structural units (B) in the polycarbonate resin is preferable. Is 50 mol% or more and 100 mol% or less, more preferably 60 mol% or more and 100 mol% or less, still more preferably 70 mol% or more and 100 mol% or less, still more preferably 80 mol% or more and 100 mol% or less. It is particularly preferably 90 mol% or more and 100 mol% or less.
When the total of the structural unit (A) and the structural unit (B) is equal to or greater than the above lower limit value, the balance of characteristics such as moldability, high refractive index, low birefringence, and heat resistance of the polycarbonate resin according to the present embodiment is balanced. Can be better.

In the polycarbonate resin according to the present embodiment, the molar ratio ((A) / (B)) of the structural unit (A) to the structural unit (B) in the polycarbonate resin is preferably 2/98 or more and 98/2 or less. Yes, more preferably 5/95 or more and 95/5 or less, still more preferably 10/90 or more and 90/10 or less, and even more preferably 20/80 or more and 90/10 or less.
The polycarbonate resin according to the present embodiment may contain any of a random copolymer structure, a block copolymer structure and an alternating copolymer structure.

The polycarbonate resin according to the present embodiment is a polycarbonate resin containing a structural unit (A) and a structural unit (B). The polycarbonate resin according to the present embodiment uses, for example, the dihydroxy compound (I) represented by the following formula (I) and the dihydroxy compound (II) represented by the following formula (II) as the dihydroxy component, as will be described later. , These dihydroxy components can be obtained by reacting with a carbonate precursor such as a carbonic acid diester.

上記式（Ｉ）中、Ｒ_１〜Ｒ_４としては、上記式（Ａ）におけるＲ_１〜Ｒ_４と同じものを挙げることができる。

In the above formula _(I), the R 1 to R _4, may include the same as the _R 1 to R ₄ in the formula (A).

上記式（ＩＩ）中、Ｒ_５〜Ｒ_１２、Ｗ、Ｘ、ｎおよびｍとしては、上記式（Ｂ）におけるＲ_５〜Ｒ_１２、Ｗ、Ｘ、ｎおよびｍと同じものを挙げることができる。

In the above formula (II), _{examples of R 5 to} R ₁₂ , W, X, n and m are the same as those of _{R 5 to} R ₁₂ , W, X, n and m in the above formula (B). ..

The polycarbonate resin according to the present embodiment is basically a polycarbonate resin having no ester bond in the main chain and does not contain polyester carbonate.

Examples of the dihydroxy compound (I) represented by the above formula (I) include 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and 9. , 9-bis (4-hydroxy-3-ethylphenyl) fluorene, 9,9-bis (4-hydroxy-3-n-propylphenyl) fluorene, 9,9-bis (4-hydroxy-3-isopropylphenyl) Fluorene, 9,9-bis (4-hydroxy-3-n-butylphenyl) fluorene, 9,9-bis (4-hydroxy-3-sec-butylphenyl) fluorene, 9,9-bis (4-hydroxy- 3-tert-Butylphenyl) fluorene, 9,9-bis (4-hydroxy-3-cyclohexylphenyl) fluorene, 9,9-bis (4-hydroxy-2-phenylphenyl) fluorene, 9,9-bis (4) Examples thereof include −hydroxy-3-phenylphenyl) fluorene and 9,9-bis [4-hydroxy-3- (3-methylphenyl) phenyl] fluorene.
Among these, preferably 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-phenyl) Phenyl) fluorene can be mentioned.
These may be used alone or in combination of two or more.

Examples of the dihydroxy compound (II) represented by the above formula (II) include bis [4- (2'-hydroxyethoxy) phenyl] sulfide and bis [4- (2'-hydroxyethoxy) -3-methylphenyl. ] Sulfide, bis [4- (2'-hydroxyethoxy) phenyl] sulfone, bis [4- (2'-hydroxyethoxy) -3-methylphenyl] sulfone, bis [4- (2'-hydroxyethoxy) phenyl] Examples thereof include sulfoxide, bis [4- (2'-hydroxyethoxy) phenyl] sulfoxide and the like.
These may be used alone or in combination of two or more.

The dihydroxy compound (II) represented by the above formula (II) can be produced, for example, by the following methods [(1) to (3)].
(1) Reaction of the dihydroxy compound (II-1) represented by the following formula (II-1) with an alkylene carbonate such as ethylene carbonate or propylene carbonate.

上記式（ＩＩ−１）において、Ｒ_５〜Ｒ_１２、Ｗとしては、上記式（Ｂ）におけるＲ_５〜Ｒ_１２、Ｗと同じものを挙げることができる。

In the above formula _(II-1), examples of _R 5 ~R _12, W, may include the same ones as _R 5 _{~R 12,} W in the formula (B).

That is, the dihydroxy compound (II-1) represented by the above formula (II-1) and an alkylene carbonate such as ethylene carbonate or propylene carbonate are used as a solvent (for example, potassium iodide, sodium iodide, triphenylphosphine, imidazole, etc.). In the presence of sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, etc.), solvents (eg, aromatic hydrocarbon solvents such as xylene, mesityrene, N, N-dimethylformamide, N, N-dimethylacetamide, etc.) It can be produced by heating in the presence or absence of an amide-based solvent such as N, N'-dimethylimidazolidinone).

(2) Reaction of dihydroxy compound (II-1) represented by the above formula (II-1) with halogenoalcohol Bases (for example, sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, sodium carbonate) , Inorganic bases such as potassium carbonate, sodium hydride, potassium hydride, sodium ethoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium-tert-butoxide, metal alkoxides such as potassium-tert-butoxide, etc.) and In the presence of a solvent (for example, an aliphatic alcohol such as ethanol or isopropanol, an amide solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, N, N'-dimethylimidazolidinone, etc.), the above formula The dihydroxy compound (II-1) represented by (II-1) and a halogeno alcohol (for example, 2-chloroethanol, 2-bromoethanol, 3-chloropropanol, 3-bromopropanol, 4-chlorobutanol, 4-bromo). Butanol, 5-chloropentanol, 5-bromopentanol, 6-chlorohexanol, 6-bromohexanol, 7-chloroheptanol, 7-bromoheptanol, 8-chlorooctanol, 8-bromooctanol, 9-chloronona It can be produced by reacting with a solvent, 9-bromononanol, 10-chlorodecanol, 10-bromodecanol, etc.).

(3) Reaction of the dihydroxy compound (II-1) represented by the above formula (II-1) with an alkylene oxide such as ethylene oxide or propylene oxide The dihydroxy compound (II-1) represented by the above formula (II-1) -1) and an alkylene oxide such as ethylene oxide or propylene oxide in the presence of a base (for example, sodium hydroxide, potassium hydroxide, diethylamine hydrochloride, ion exchange resin, etc.) and a solvent (for example, ethylene glycol dimethyl ether, It can be produced by reacting under normal pressure or pressure in an ether solvent such as 2-methoxyethanol, water, etc.).

As the dihydroxy component, in addition to the compounds of the above formula (I) and the above formula (II), for example, aromatic dihydroxy compounds, aliphatic dihydroxy compounds and the like can be used in combination.
Examples of the aromatic dihydroxy compound include bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) ethane, and 1,1-bis (4). -Hydroxyphenyl) Phenylethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxy-3,5) Bis (4-hydroxyaryl) alkanes such as −dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 4,4-dihydroxyphenyl-1,1-m-diisopropylbenzene 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2 , 2,2,2-Tetrahydro-3,3,3,3-Tetramethyl-1,1-spirobis [1H inden] -6,6-diol and other bis (hydroxyaryl) cycloalkanes; bis (4- Dihydroxyaryl ethers such as hydroxyphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether; 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4) -(2-Hydroxyethoxy) -3-methylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butylphenyl) fluorene, 9,9-bis (4- (2-) Hydroxyethoxy) -3-isopropylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3- Phenylphenyl) fluorene and the like are exemplified.
These may be used alone or in combination of two or more.

Examples of the aliphatic dihydroxy compound include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 2, 2-Dimethyl-1,3-propanediol, 1,10-decanediol, diethylene glycol, tetraethylene glycol, norbornane dimethanol, decahydronaphthalenediethanol, tricyclo [5.2.1.0 ^2,6 ] decandimethanol , Pentacyclopentadecanedimethanol, cyclopentane-1,3-dimethanol, spiroglycol and the like.
These may be used alone or in combination of two or more.

The polycarbonate resin according to the present embodiment is preferably a polycarbonate resin composed of only the structural unit (A) represented by the above formula (A) and the structural unit (B) represented by the above formula (B).

Polystyrene-reduced weight average molecular weight of the polycarbonate resin according to the present embodiment (Mw) of preferably not 1.5 × 10 ⁴ or more 2.0 × 10 ⁵ or less, more preferably 2.0 × 10 ⁴ or more 1. it is 2 × 10 ⁵ or less.
When Mw is at least the above lower limit value, it is preferable because it is possible to further suppress the obtained molded product from becoming brittle. When Mw is not more than the above upper limit value, the melt viscosity becomes more appropriate, so that the resin after production becomes easier to take out, the fluidity becomes better, and injection molding becomes easier in the molten state, which is preferable.

The refractive index (nD) of the polycarbonate resin according to the present embodiment at 23 ° C. and a wavelength of 589 nm is preferably 1.630 or more and 1.695 or less, more preferably 1.635 or more and 1.690 or less, and further preferably 1.640. It is 1.685 or more, particularly preferably 1.645 or more and 1.685 or less.
The polycarbonate resin according to this embodiment has a high refractive index (nD) and is suitable as an optical lens material. The refractive index of a 0.1 mm thick film can be measured by the method of JIS-K-7142 using an Abbe refractometer.

The Abbe number (ν) of the polycarbonate resin according to the present embodiment is preferably 27 or less, more preferably 26 or less, still more preferably 25 or less, and particularly preferably 24 or less.
The Abbe number can be calculated from the refractive indexes of wavelengths of 486 nm, 589 nm and 656 nm at 23 ° C. using the following formula.
ν = (nD-1) / (nF-nC)
nD: Refractive index at wavelength 589 nm nC: Refractive index at wavelength 656 nm nF: Refractive index at wavelength 486 nm

The polycarbonate resin according to the present embodiment can be blended with another resin and used for producing a molded product. Examples of other resins include polyamide, polyacetal, polycarbonate, modified polyphenylene ether, polyethylene terephthalate, polybutylene terephthalate and the like.

Further, an antioxidant, a mold release agent, an ultraviolet absorber, a fluidity modifier, a crystal nucleating agent, a strengthening agent, a dye, an antistatic agent, an antibacterial agent and the like may be added to the polycarbonate resin according to the present embodiment. it can.

Examples of the molding method include, but are not limited to, compression molding, casting, roll processing, extrusion molding, stretching, and the like, in addition to injection molding.
When the polycarbonate resin according to the present embodiment is used for injection molding, the glass transition temperature (Tg) is preferably 80 ° C. or higher and 190 ° C. or lower, more preferably 85 ° C. or higher and 180 ° C. or lower, and further preferably 90 ° C. or higher. It is 170 ° C. or lower. When Tg is at least the above lower limit value, the operating temperature range becomes wider, which is preferable. Further, when Tg is not more than the above upper limit value, the melting temperature of the resin becomes lower, and decomposition and coloring of the resin are less likely to occur, which is preferable. Further, when Tg is not more than the above upper limit value, the difference between the mold temperature and the resin glass transition temperature can be reduced even with a general-purpose mold temperature controller. Therefore, it is easy to use and preferable in applications where strict surface accuracy is required for the product.

The optical molded product obtained by using the polycarbonate resin according to the present embodiment has a total light transmittance of preferably 85% or more, more preferably 88%, as measured in accordance with JIS K-7361-1. It is comparable to bisphenol A type polycarbonate resin and the like.

[Manufacturing method of polycarbonate resin]
The polycarbonate resin according to the present embodiment can be produced by using the dihydroxy compound (I) represented by the above formula (I) and the dihydroxy compound (II) represented by the above formula (II) as raw materials. Specifically, carbonate precursors such as dihydroxy compound (I), dihydroxy compound (II) and carbonic acid diester are mixed in the presence of a basic compound catalyst, a transesterification catalyst, or a mixed catalyst consisting of both, or in the absence of a catalyst. , Can be produced by reacting by a melt transesterification method.

Further, in the polycarbonate resin according to the present embodiment, the dihydroxy compound (I) represented by the above formula (I) is used as an aryl carbonate derivative, and then the dihydroxy compound (II) represented by the above formula (II) and a base are used. It can be produced by reacting by a melt polycondensation method in the presence of a mixed catalyst consisting of a sex compound catalyst and / or transesterified color, or in the absence of a catalyst.

The method for using the dihydroxy compound (I) represented by the above formula (I) as an aryl carbonate derivative is not particularly limited, but for example, aryl halohomet and a base are used in the presence or absence of a solvent as required. It can be produced by acting on the dihydroxy compound (I) represented by the formula (I).
Here, examples of the aryl halohomet include phenyl chlorohomet, p-tolyl chlorohomet, m-tolyl chlorohomet, o-tolyl chlorohomet, p-chlorophenyl chlorohomet, and m-chlorophenyl chlorohoe. Mates, o-chlorophenylchlorohomates and the like can be mentioned.
Examples of the base include inorganic bases and organic bases, and specific examples thereof include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate; and organic bases such as triethylamine, diisopropylethylamine and pyridine. be able to.
Examples of the solvent used as necessary include aromatic hydrocarbon solvents such as benzene, toluene and xylene, and halogen solvents such as dichloromethane and chloroform.

When the total of all the dihydroxy compounds contained in the reaction system is 100 mol%, the dihydroxy compound (I) represented by the above formula (I) and the dihydroxy compound (II) represented by the above formula (II) The total amount is 50 mol% or more and 100 mol% or less, more preferably 60 mol% or more and 100 mol% or less, still more preferably 70 mol% or more and 100 mol% or less, still more preferably 80 mol% or more and 100. It is mol% or less, and particularly preferably 90 mol% or more and 100 mol% or less.

The molar ratio ((I) / (II)) of the dihydroxy compound (I) to the dihydroxy compound (II) contained in the reaction system is preferably 2/98 or more and 98/2 or less, more preferably 5. It is / 95 or more and 95/5 or less, and more preferably 20/80 or more and 90/10 or less.

Examples of the carbonic acid diester according to the present embodiment include diphenyl carbonate, di-p-tolyl carbonate, di-m-tolyl carbonate, di-o-tolyl carbonate, bis (p-chlorophenyl) carbonate, and bis (m-chlorophenyl) carbonate. Examples thereof include bis (o-chlorophenyl) carbonate, m-cresyl carbonate, dimethyl carbonate, diethyl carbonate, di-n-butyl carbonate, dicyclohexyl carbonate and the like. Among these, diphenyl carbonate is preferable. The diphenyl carbonate is preferably used in a ratio of 0.97 to 1.20 mol, more preferably 0.98 to 1.10 mol, based on a total of 1 mol of the dihydroxy compound.
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 such as alkali metals and alkaline earth metal compounds, inorganic salts, oxides, hydroxides, hydrides or alkoxides, or quaternary ammonium hydroxides and salts thereof, amines and the like. Are preferably used, and these compounds can be used alone or in combination.

Examples of the alkali metal compound according to the present embodiment include organic acid salts of alkali metals, inorganic salts, oxides, hydroxides, hydrides, alkoxides and the like. Specifically, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogencarbonate, sodium carbonate, potassium hydrogencarbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, Lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium boron hydride, sodium phenylated, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate , 2 potassium hydrogen phosphate, 2 lithium hydrogen phosphate, 2 sodium phenyl phosphate, 2 sodium salt of bisphenol A, 2 potassium salt, 2 cesium salt or 2 lithium salt, sodium phenol salt, potassium salt, cesium salt or lithium Salt or the like is used.

Examples of the alkaline earth metal compound include organic acid salts, inorganic salts, oxides, hydroxides, hydrides and alkoxides of alkaline earth metal compounds. Specifically, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydrogencarbonate, calcium hydrogencarbonate, strontium hydrogencarbonate, barium hydrogencarbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, acetic acid. Magnesium, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, magnesium phenylphosphate and the like are used.

Examples of the nitrogen-containing compound include quaternary ammonium hydroxide and salts thereof, amines and the like. Specifically, quaternary ammonium having an alkyl group such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetran-propylammonium hydroxide, tetran-butylammonium hydroxide, trimethylbenzylammonium hydroxide, or an aryl group. Hydroxides; Tertiary amines such as triethylamine, dimethylbenzylamine, triphenylamine; Secondary amines such as diethylamine and dibutylamine; Primary amines such as n-propylamine and n-butylamine; 2-Methylimidazole , 2-Phenylimidazoles, imidazoles such as benzoimidazole; or bases such as ammonia, tetramethylammonium borohydride, tetra n-butylammonium borohydride, tetra n-butylammonium tetraphenylborate, tetraphenylammonium tetraphenylborate or Basic salts and the like are used.

As the transesterification catalyst, salts of zinc, tin, zirconium, lead and the like are preferably used, and these can be used alone or in combination.
Specific examples of the ester exchange catalyst include zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin (II) chloride, tin (IV) chloride, tin (II) acetate, tin (IV) acetate, and tin dibutyltin. Dilaurate, dibutyltin oxide, dibutyltin dimethoxyde, 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, relative to a total of 1 mol of the dihydroxy compound.

In the melt polycondensation method, the melt polycondensation is carried out using the above-mentioned raw materials and catalyst under heating under normal pressure or reduced pressure while removing by-products by a transesterification reaction.
The melt polycondensation method according to the present embodiment is the dihydroxy compound (I) represented by the above formula (I), the dihydroxy compound (II) and the carbonic acid diester represented by the above formula (II), or the above formula (I). ) And the aryl carbonate derivative of the dihydroxy compound (I) and the dihydroxy compound (II) represented by the above formula (II) are melted in a reaction vessel, and then the monohydroxy compound produced as a by-product is retained. It is desirable to carry out the reaction.
The pressure can be controlled by closing the reactor, reducing the pressure, pressurizing, etc. in order to retain the reaction device. The reaction time of this step is preferably 20 minutes or more and 240 minutes or less, more preferably 40 minutes or more and 180 minutes or less, and particularly preferably 60 minutes or more and 150 minutes or less. At this time, if the by-produced monohydroxy compound is distilled off immediately after being produced, the finally obtained polycarbonate resin has a small content of high molecular weight material. However, when the by-produced monohydroxy compound is allowed to stay in the reaction vessel for a certain period of time, the finally obtained polycarbonate resin can be obtained in which the content of the high molecular weight substance is high.

Generally, the melt polycondensation reaction is carried out in a multi-step process of two or more steps. Specifically, the first-stage reaction is preferably carried out at a temperature of 120 to 260 ° C., more preferably 180 to 240 ° C., preferably under normal pressure or pressure for 0.1 to 5 hours, more preferably 0. Allow to react for 5 to 3 hours. Next, the reaction temperature was raised while increasing the decompression degree of the reaction system to carry out the reaction between the dihydroxy compound and the carbonic acid diester, and finally the decompression degree of 133 Pa (1 mmHg) or less and the temperature of 200 to 350 ° C. It is preferable to carry out a time polycondensation reaction.

The melt polycondensation reaction may be carried out continuously or in a batch manner.
The reactor used for carrying out the reaction is a vertical type equipped with an anchor type stirring blade, a max blend stirring blade, a helical ribbon type stirring blade, etc., but a horizontal type equipped with a paddle blade, a lattice blade, a glasses blade, etc. It may be an extruder type equipped with a screw. Further, it is preferably carried out to use a reaction device in which these reaction devices are appropriately combined in consideration of the viscosity of the polymer.

After the polycondensation reaction is completed, the polycarbonate resin according to the present embodiment may have the catalyst removed or deactivated in order to maintain thermal stability and hydrolysis stability. Generally, a method of deactivating the catalyst by adding a known acidic substance can be preferably carried out. Specific examples of the acidic substance include esters such as butyl benzoate; aromatic sulfonic acids such as p-toluenesulfonic acid; aromatic sulfonic acid esters such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate. Kind: Phosphonates such as phosphite, phosphoric acid, phosphonic acid; triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-propyl phosphate, di-propyl phosphite Subphosphorates such as n-butyl, din-hexyl phosphite, din-octyl phosphate, mono n-octyl phosphate; triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, phosphorus Phosphonates such as din-butyl acid, din-octyl phosphate, mono n-octyl phosphate; phosphonic acids such as diphenylphosphonic acid, din-octylphosphonic acid, din-butylphosphonic acid; phenylphosphon Phosphonate esters such as diethyl acid; phosphinates such as triphenylphosphine and bis (diphenylphosphino) ethane; boric acids such as boric acid and phenylboric acid; aromatics such as tetra n-butylphosphonium salt of n-dodecylbenzenesulfonic acid. Group sulfonates; organic halides such as chloride chloride, benzoyl chloride, p-toluenesulfonic acid chloride; alkyl sulfates such as dimethylsulfate; organic halides such as benzyl chloride are preferably used. These deactivators are preferably used in an amount of 0.01 to 50 times, more preferably 0.3 to 20 times, the amount of the catalyst. If it is less than 0.01 times the amount of the catalyst, the deactivating effect becomes insufficient, which is not preferable. Further, if the amount is more than 50 times the amount of the catalyst, the heat resistance of the resin is lowered and the molded product is easily colored, which is not preferable.

After the catalyst is deactivated, a step of volatilizing and removing the low boiling point compound in the polymer at a pressure of 13 to 133 Pa (0.1 to 1 mmHg) and a temperature of 200 to 350 ° C. may be provided. For this step, a horizontal device equipped with a stirring blade having excellent surface renewal ability, such as a paddle blade, a lattice blade, and a glasses blade, or a thin film evaporator is preferably used.

The polycarbonate resin according to the present embodiment is desired to have as little foreign matter content as possible, and filtration of the molten raw material, filtration of the catalyst solution, and the like are preferably performed. The mesh of the filter is preferably 5 μm or less, more preferably 1 μm or less. Further, filtration of the produced resin with a polymer filter is preferably performed. The mesh of the polymer filter is preferably 100 μm or less, more preferably 30 μm or less. Further, the step of collecting the resin pellets is naturally preferably a low dust environment, and more preferably a class 1000 or less cleanliness.

[Optical molded product]
The optical molded product according to the present embodiment contains the polycarbonate resin according to the present embodiment, and the optical molded product can be manufactured using the polycarbonate resin according to the present embodiment.
For example, it is molded by an arbitrary method such as an injection molding method, a compression molding method, an injection compression molding method, an extrusion molding method, or a solution casting method.
Since the polycarbonate resin according to the present embodiment is excellent in moldability and heat resistance, it can be used particularly advantageously in an optical lens that requires injection molding. At the time of molding, the polycarbonate resin according to the present embodiment can be mixed with other resins such as other polycarbonate resins and polyester resins and used.
In addition, various additives can be used in order to impart various properties within a range that does not impair the object of the present embodiment. Additives include antioxidants, processing stabilizers, mold release agents, UV absorbers, brewing agents, elastomeric metal deactivators, flame retardants, lubricants, antistatic agents, heat ray shields, and fluorescent dyes (enhanced fluorescence). (Including white agents), pigments, light scatterers, strengthening fillers, surfactants, antibacterial agents, plasticizers, compatibilizers, other resins and elastomers.

Examples of the antioxidant include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] and 1,6-hexanediol-bis [3- (3,5). -Di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-) Di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N- Hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di) -Tert-Butyl-4-hydroxybenzyl) isocyanurate and 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl } -2,4,8,10-Tetraoxaspiro (5,5) undecane and the like.
The content of the antioxidant in the polycarbonate resin is preferably 0.001 to 0.3 parts by mass with respect to 100 parts by mass of the polycarbonate resin.

Examples of the processing stabilizer include a phosphorus-based processing heat stabilizer and a sulfur-based processing heat stabilizer.

Examples of the phosphorus-based processing heat stabilizer include phosphorous acid, phosphoric acid, phosphonic acid, phosphonic acid and esters thereof. Specifically, triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, Tri-n-decylphosphite, tri-n-octylphosphite, tri-n-octadecylphosphite, din-decylmonophenylphosphite, din-octylmonophenylphosphite, diisopropylmonophenylphosphite, mono-n-butyldiphenyl Phosphite, monodecyldiphenylphosphite, monon-octyldiphenylphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-methylenebis) Di-tert-butylphenyl) octylphosphite, bis (n-nonylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert- Butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tri-n-butyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, di n-butyl phosphate, din-octyl Phenyl phosphate, diisopropyl phosphate, dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-) Di-t-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,4-di-t-butylphenyl) -3,3'-biphenylenediphosphonite, bis (2,4-di-) Examples thereof include tert-butylphenyl) -4-phenyl-phenylphosphonite and bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite.
The content of the phosphorus-based processing heat stabilizer in the polycarbonate resin is preferably 0.001 to 0.2 parts by mass with respect to 100 parts by mass of the polycarbonate resin.

Examples of the sulfur-based processing heat stabilizer include pentaerythritol-tetrakis (3-laurylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), and pentaerythritol-tetrakis (3-stearylthiopropionate). Nate), dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate and the like.
The content of the sulfur-based processing heat stabilizer in the polycarbonate resin is preferably 0.001 to 0.2 parts by mass with respect to 100 parts by mass of the polycarbonate resin.

The release agent preferably comprises 90% by mass or more of an ester of alcohol and fatty acid. Specific examples of the ester of the alcohol and the fatty acid include an ester of a monohydric alcohol and a fatty acid, a partial ester of a polyhydric alcohol and a fatty acid, or a total ester. As the ester of the monohydric alcohol and the fatty acid, an ester of a monohydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms is preferable. Further, as the partial ester or total ester of the polyhydric alcohol and the fatty acid, a partial ester or total ester of the polyhydric alcohol having 1 to 25 carbon atoms and the saturated fatty acid having 10 to 30 carbon atoms is preferable.
Examples of the ester of the monohydric alcohol and the saturated fatty acid include stearyl stearate, palmityl palmitate, n-butyl stearate, methyl laurate, and isopropyl palmitate. Examples of partial or total esters of polyhydric alcohol and saturated fatty acid include stearic acid monoglyceride, stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitate, behenic acid monoglyceride, capric acid monoglyceride, and laurate Monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenylbiphenate, sorbitan monostearate, 2-ethylhexyl stearate, dipentaerythritol hexastearate, etc. Examples thereof include full ester or partial ester of dipentaerythritol.
The content of these release agents is preferably in the range of 0.005 to 2.0 parts by mass, more preferably in the range of 0.01 to 0.6 parts by mass, and 0.02 to 0.02 to 100 parts by mass of the polycarbonate resin. The range of 0.5 parts by mass is more preferable.

The UV absorber is at least one UV absorber selected from the group consisting of benzotriazole-based UV absorbers, benzophenone-based UV absorbers, triazine-based UV absorbers, cyclic iminoester-based UV absorbers, and cyanoacrylate-based UV absorbers. Absorbents are preferred. One of the following ultraviolet absorbers may be used alone, or two or more thereof may be used in combination.

Examples of the benzotriazole-based ultraviolet absorber include 2- (2-hydroxy-5-methylphenyl) benzotriazol, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazol, and 2- (2- (2-). Hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis [4- (1) , 1,3,3-Tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazol, 2 -(2-Hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazol, 2- (2) -Hydroxy-5-tert-octylphenyl) benzotriazol, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazol, 2- (2-hydroxy-4-n-octyloxyphenyl) benzotriazol , 2,2'-Methylenebis (4-cumyl-6-benzotriazolphenyl), 2,2'-p-phenylenebis (1,3-benzoxazine-4-one), 2- [2-hydroxy-3-one) (3,4,5,6-Tetrahydrophthalimidemethyl) -5-methylphenyl] Bentriazol and the like can be mentioned.

Examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, and 2-. Hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxitrihydrate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2', 4,4' -Tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis (5-benzoyl-4-) Hydroxy-2-methoxyphenyl) methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like can be mentioned.

Examples of the triazine-based ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-[(n-hexyl) oxy] -phenol and 2- (4,4). Examples thereof include 6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl) -5-[(n-octyl) oxy] -phenol.

Examples of the cyclic iminoester-based ultraviolet absorber include 2,2'-bis (3,1-benzoxazine-4-one) and 2,2'-p-phenylenebis (3,1-benzoxazine-4-one). On), 2,2'-m-phenylene bis (3,1-benzoxazine-4-one), 2,2'-(4,4'-diphenylene) bis (3,1-benzoxazine-4-one) ), 2,2'-(2,6-naphthalene) bis (3,1-benzoxazine-4-one), 2,2'-(1,5-naphthalene) bis (3,1-benzoxazine-4) -On), 2,2'-(2-methyl-p-phenylene) bis (3,1-benzoxazine-4-one), 2,2'-(2-nitro-p-phenylene) bis (3, 1-benzoxazine-4-one) and 2,2'-(2-chloro-p-phenylene) bis (3,1-benzoxazine-4-one) and the like can be mentioned.

Examples of the cyanoacrylate-based ultraviolet absorber include 1,3-bis-[(2'-cyano-3', 3'-diphenylacryloyl) oxy] -2,2-bis [(2-cyano-3,3). -Diphenylacryloyl) oxy] methyl) propane, 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene and the like can be mentioned.

The content of the ultraviolet absorber is preferably 0.01 to 3.0 parts by mass, more preferably 0.02 to 1.0 parts by mass, and further preferably 0 with respect to 100 parts by mass of the polycarbonate resin. .05 to 0.8 parts by mass. Within the range of such a blending amount, it is possible to impart sufficient weather resistance to the polycarbonate resin depending on the application.

Examples of the bluing agent include Bayer's Macrolex Violet B and Macrolex Blue RR, and Clariant's Polysynthslen Blue RLS.
The bluing agent is effective for eliminating the yellowish tint of the polycarbonate resin. In particular, in the case of polycarbonate resin with weather resistance, a certain amount of UV absorber is mixed, so the polycarbonate resin molded product tends to be yellowish depending on the "action and color of the UV absorber", especially on sheets and sheets. In order to give the lens a natural transparency, it is effective to add a brewing agent.
The blending amount of the bluing agent is, for example, preferably 0.05 to 1.5 ppm, more preferably 0.1 to 1.2 ppm, based on the polycarbonate resin.

The polycarbonate resin according to the present embodiment exhibits a high refractive index and excellent heat resistance, and has a fluidity suitable for molding. Furthermore, since optical distortion is unlikely to occur due to low birefringence, in addition to optical lenses, transparent conductive substrates, optical disks, liquid crystal panels, optical cards, sheets, films used for liquid crystal displays, organic EL displays, solar cells, etc. , Optical fibers, connectors, vapor-deposited plastic reflectors, structural materials for optical components such as displays, or functional materials. It can be advantageously used as an optical molded body suitable for applications.

A coat layer such as an antireflection layer or a hard coat layer may be provided on the surface of the optical molded product, if necessary. The antireflection layer may be a single layer or a multi-layer structure, and may be an organic substance or an inorganic substance, but is preferably an inorganic substance. Specific examples thereof include oxides or fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, magnesium oxide and magnesium fluoride.

(Optical lens)
Since the optical lens manufactured by using the polycarbonate resin according to the present embodiment has a high refractive index and excellent heat resistance, an expensive high refractive index glass lens such as a telescope, binoculars, or a television projector has been conventionally used. It can be used in various fields and is extremely useful. If necessary, it is preferably used in the form of an aspherical lens. Since it is possible to eliminate spherical aberration with a single lens in an aspherical lens, it is not necessary to remove spherical aberration by combining a plurality of spherical lenses, resulting in weight reduction and reduction in production cost. It will be possible. Therefore, the aspherical lens is particularly useful as a camera lens among optical lenses.
The optical lens according to this embodiment is molded by an arbitrary method such as an injection molding method, a compression molding method, or an injection compression molding method. According to this embodiment, it is possible to more easily obtain a high refractive index low birefringence aspherical lens which is technically difficult to process with a glass lens.

(Optical film)
The optical film produced by using the polycarbonate resin according to the present embodiment is excellent in transparency and heat resistance, and is therefore suitably used for a film for a liquid crystal substrate, an optical memory card, and the like.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted.

Hereinafter, the present embodiment will be described in detail with reference to Examples and Comparative Examples. The present embodiment is not limited to the description of these examples.

1. 1. Measurement / Evaluation Method In the following Examples / Comparative Examples, the measurement and evaluation of each physical property was performed by the following method.

1) Polystyrene-equivalent weight average molecular weight (Mw): Using a gel permeation chromatograph (GPC: 1515, 2414 and 2489 manufactured by Waters), using chloroform as an eluate, a standard polystyrene having a known molecular weight (molecular weight distribution = 1) is used. A calibration curve was created using. Based on this calibration curve, Mw was calculated from the retention time of GPC.

2) Refractive index (nD): A 0.1 mm thick film made of the polycarbonate resin produced in the examples was measured by the method of JIS-K-7142 using an Abbe refractometer.

3) Abbe number (ν): With respect to the 0.1 mm thick film made of the polycarbonate resin produced in the examples, the refractive indexes at wavelengths of 486 nm, 589 nm and 656 nm at 23 ° C. were measured using an Abbe refractometer, and further. The Abbe number was calculated using the following formula.
ν = (nD-1) / (nF-nC)
nD: Refractive index at wavelength 589 nm nC: Refractive index at wavelength 656 nm nF: Refractive index at wavelength 486 nm

4) Glass transition temperature (Tg): Measured by a differential thermal scanning calorimeter (DSC: DSC-60 manufactured by Shimadzu Corporation).

5) Pyrolysis start temperature (Td): Using a differential thermal balance (TG-DTA: DTG-60 manufactured by Shimadzu Corporation), the temperature at which the weight was reduced by 5% was measured under an air flow. The heating rate is 10 ° C./min.

6) Total light transmittance: A 0.1 mm thick film made of the polycarbonate resin produced in the example was measured by the method of JIS-K-7361-1 using a turbidity meter NDH2000 manufactured by Nippon Denshoku Kogyo Co., Ltd. did.

2. Synthesis of raw materials (Synthesis Example 1) Production of 9,9-bis (4'-phenoxycarbonyloxyphenyl) fluorene In a 2 liter flask equipped with a stirrer, 9,9-bis (4'-hydroxyphenyl) fluorene 175. 27 g (0.50 mol), 178.62 g (1.14 mol) of phenylchlorohomet and 600 g of chloroform were charged and cooled by an ice bath.
After dropping 115.22 g (1.14 mol) of triethylamine over an hour and a half, the mixture was stirred overnight at room temperature. Then, 200 mL of chloroform was added, and the mixture was washed three times with 300 mL of ion-exchanged water, and then the chloroform layer was dried over magnesium sulfate and concentrated under reduced pressure.
The obtained solid was washed with 350 mL of methanol, filtered, and then recrystallized from 598 g of methylcellosolve by heating to obtain 264.32 g (yield 89%) of 9,9-bis (4'-phenoxycarbonyloxyphenyl) fluorene. Obtained.

(Synthesis Example 2) Production of 9,9-bis (3'-methyl-4'-phenoxycarbonyloxyphenyl) fluorene In Synthesis Example 1, 175.27 g (0) of 9,9-bis (4'-hydroxyphenyl) fluorene The operation according to Synthesis Example 1, except that 189.23 g (0.50 mol) of 9,9-bis (3'-methyl-4'-hydroxyphenyl) fluorene was used instead of .50 mol). Therefore, 278.40 g (90% yield) of 9,9-bis (3'-methyl-4'-phenoxycarbonyloxyphenyl) fluorene was obtained.

(Synthesis Example 3) Production of Bis [4- (2'-Hydroxyethoxy) Penyl] Sulfide 109.14 g (0.50 mol) of bis (4-hydroxyphenyl) sulfide, ethylene in a 1 liter flask equipped with a stirrer. 92.46 g (1.05 mol) of carbonate and 345 mg (2.5 mmol) of potassium carbonate were charged, and the mixture was heated and stirred at 160 ° C. for 24 hours. Then, the reaction mixture was cooled to 60 ° C., 250 mL of methanol was added, 75 g of a 1N-NaOH aqueous solution was further added, and the mixture was heated and stirred at 60 ° C. for 2 hours. After cooling the reaction solution to room temperature, 250 mL of ion-exchanged water was added, the produced solid was filtered off, and the obtained solid was suspended and washed with a 1N-HCl aqueous solution. The solid was dissolved in ethyl acetate and washed with ion-exchanged water until the conductivity of the aqueous phase became 10 μS / cm or less. Then, the ethyl acetate layer was dried over sodium sulfate and concentrated under reduced pressure, and the obtained solid was recrystallized from chloroform to obtain 108.76 g of bis [4- (2'-hydroxyethoxy) phenyl] sulfide (yield 71%). Got

(Synthesis Example 4) Production of 4-Hydroxyphenyl-4'-(2 "-Hydroxyethoxy) phenyl sulfide 109.14 g (0.50 mol) of bis (4-hydroxyphenyl) sulfide in a 1 liter flask equipped with a stirrer. ), 44.03 g (0.50 mol) of ethylene carbonate and 345 mg (2.5 mmol) of potassium carbonate were charged, and the mixture was heated and stirred at 160 ° C. for 24 hours. Then, the reaction solution was cooled to 60 ° C. and cooled. 250 mL of methanol was added, 75 g of a 1N-NaOH aqueous solution was further added, and the mixture was heated and stirred at 60 ° C. for 2 hours. Then, the reaction solution was cooled to room temperature, 250 mL of ion-exchanged water was added, and the produced solid was filtered off. The obtained solid was suspended and washed with 1N-HCl, the solid was filtered off, dissolved in ethyl acetate, and washed with ion-exchanged water until the conductivity of the aqueous layer became 10 μS / cm or less. Then, the ethyl acetate layer was dried with sodium sulfate and concentrated under reduced pressure, and the obtained solid was recrystallized twice from chloroform to achieve 60.33 g of 4-hydroxyphenyl-4'-(2 "-hydroxyethoxy) phenylsulfide. (Yield 46%) was obtained.

(Synthesis Example 5) Production of Bis [4- (2'-Hydroxyethoxy) -3-methylphenyl] Sulfide In Synthesis Example 3, 109.14 g (0.50 mol) of bis (4-hydroxyphenyl) sulfide and potassium carbonate Other than using 123.16 g (0.50 mol) of bis (4-hydroxy-3-methylphenyl) sulfide and 1.0 g (6.02 mmol) of potassium iodide instead of using 345 mg (2.5 mmol) Obtained 122.07 g (73% yield) of bis [4- (2'-hydroxyethoxy) -3-methylphenyl] sulfide according to the procedure described in Synthesis Example 3.

3. 3. Production of Polycarbonate Resin (Example 1)
9,9-Bis (4'-hydroxyphenyl) fluorene (hereinafter, may be abbreviated as "BPFL") 14.54 g (41.5 mmol), the bis produced in Synthesis Example 3 [4- (2'-) Hydroxyethoxy) phenyl] sulfide (hereinafter sometimes abbreviated as "HETDP") 12.71 g (41.5 mmol), diphenyl carbonate (hereinafter sometimes abbreviated as "DPC") 17.78 g (83. ^{90 μL (1.8 × 10-6} mol) of 0.02 M-sodium hydrogen carbonate aqueous solution (0 mmol) was placed in a reactor equipped with a distiller and reacted at 215 ° C. and 100 kPa for 1 hour. Then, the degree of decompression was adjusted to 19 kPa and reacted for 20 minutes, then the temperature was raised to 240 ° C., and the reaction was carried out at the same temperature and pressure for 70 minutes. Next, the degree of decompression was adjusted to 16 kPa and reacted for 20 minutes, the degree of decompression was further adjusted to 13 kPa and reacted for 20 minutes, then the degree of decompression was adjusted to 130 Pa over 40 minutes, and the reaction was carried out at the same pressure for 30 minutes to give a predetermined value. When the torque was reached, the vacuum was released with nitrogen gas to extract the polycarbonate resin.

The weight average molecular weight (Mw) of the obtained polycarbonate resin was 52300, and the Tg was 129 ° C. The thermal decomposition start temperature Td was 368 ° C.
This polycarbonate resin was preheated at 200 ° C. for 3 minutes and then pressed at 10 MPa for 1 minute to prepare a press sheet (optical film) having a thickness of 0.1 mm. The refractive index (nD) of this press sheet (optical film) was 1.647 and the Abbe number was 22.6.

After further scaling up and manufacturing this polycarbonate resin, 500 ppm of an antioxidant (trade name "Adecastab PEP-45"; manufactured by Asahi Denka Kogyo Co., Ltd.) and glycerin monostearylate were added to the obtained polycarbonate resin. 300 ppm was added and kneaded at 250 ° C. with an extruder and pelletized to obtain pellets.
The pellets are vacuum dried at 100 ° C. for 24 hours, then injection molded at a cylinder temperature of 250 ° C. and a mold temperature of 120 ° C., and a biconvex lens having a diameter of 9.4 mm and a radius of curvature of both convex surfaces of 5.0 mm (center of the lens). Thickness; 9.0 mm) was obtained. Observation under Cross Nicol confirmed that the lens had no optical distortion. Moreover, when the total light transmittance was measured, it was 90%. In addition, the injection moldability was good, and the lens could be molded without any problem.

(Example 2)
9,9-bis (4'-phenoxycarbonyloxyphenyl) fluorene 24.51 g (41.5 mmol) produced in Synthesis Example 1, bis [4- (2'-hydroxyethoxy) phenyl] produced in Synthesis Example 3 12.71 g (41.5 mmol) of sulfide and 90 μL (1.8 × ^10-6 mol) of 0.02 M-sodium hydrogen carbonate aqueous solution were placed in a reactor equipped with a distiller, and 1 at 215 ° C. and 100 kPa. Reacted for time. Then, the degree of decompression was adjusted to 19 kPa and reacted for 20 minutes, then the temperature was raised to 240 ° C., and the reaction was carried out at the same temperature and pressure for 70 minutes. Next, the degree of decompression was adjusted to 16 kPa and reacted for 20 minutes, the degree of decompression was further adjusted to 13 kPa and reacted for 20 minutes, then the degree of decompression was adjusted to 130 Pa over 40 minutes, and the reaction was carried out at the same pressure for 30 minutes to give a predetermined value. When the torque was reached, the vacuum was released with nitrogen gas to extract the polycarbonate resin.

The weight average molecular weight (Mw) of the obtained polycarbonate resin was 50600, and the Tg was 128 ° C. The thermal decomposition start temperature Td was 370 ° C.
This polycarbonate resin was preheated at 200 ° C. for 3 minutes and then pressed at 10 MPa for 1 minute to prepare a press sheet (optical film) having a thickness of 0.1 mm. The refractive index (nD) of this press sheet (optical film) was 1.647 and the Abbe number was 23.3.

After further scaling up and manufacturing this polycarbonate resin, 500 ppm of an antioxidant (trade name "Adecastab PEP-45"; manufactured by Asahi Denka Kogyo Co., Ltd.) and glycerin monostearylate were added to the obtained polycarbonate resin. 300 ppm was added and kneaded at 250 ° C. with an extruder and pelletized to obtain pellets.
The pellets are vacuum dried at 100 ° C. for 24 hours, then injection molded at a cylinder temperature of 250 ° C. and a mold temperature of 120 ° C., and a biconvex lens having a diameter of 9.4 mm and a radius of curvature of both convex surfaces of 5.0 mm (center of the lens). Thickness; 9.0 mm) was obtained. Observation under Cross Nicol confirmed that the lens had no optical distortion. Moreover, when the total light transmittance was measured, it was 90%. In addition, the injection moldability was good, and the lens could be molded without any problem.

(Example 3)
In Example 1, instead of using 14.54 g (41.5 mmol) of BPFL, 12.71 g (41.5 mmol) of HETDP, 20.36 g (58.1 mmol) of BPFL and 7.63 g (24.9 mmol) of HETDP. A polycarbonate resin was produced according to the operation described in Example 1 except that it was used.

The weight average molecular weight (Mw) of the obtained polycarbonate resin was 28,500, and the Tg was 143 ° C. The thermal decomposition start temperature (Td) was 365 ° C.
This polycarbonate resin was preheated at 200 ° C. for 3 minutes and then pressed at 10 MPa for 1 minute to prepare a press sheet (optical film) having a thickness of 0.1 mm. The refractive index (nD) of this press sheet (optical film) was 1.654 and the Abbe number was 22.9.

After further scaling up and manufacturing this polycarbonate resin, 500 ppm of an antioxidant (trade name "Adecastab PEP-45"; manufactured by Asahi Denka Kogyo Co., Ltd.) and glycerin monostearylate were added to the obtained polycarbonate resin. 300 ppm was added and kneaded at 250 ° C. with an extruder and pelletized to obtain pellets.
The pellets are vacuum dried at 100 ° C. for 24 hours, then injection molded at a cylinder temperature of 250 ° C. and a mold temperature of 120 ° C., and a biconvex lens having a diameter of 9.4 mm and a radius of curvature of both convex surfaces of 5.0 mm (center of the lens). Thickness; 9.0 mm) was obtained. Observation under Cross Nicol confirmed that the lens had no optical distortion. Moreover, when the total light transmittance was measured, it was 89%. In addition, the injection moldability was good, and the lens could be molded without any problem.

(Example 4)
In Example 1, instead of using 14.54 g (41.5 mmol) of BPFL, 12.71 g (41.5 mmol) of HETDP, 8.73 g (24.9 mmol) of BPFL and 17.80 g (58.1 mmol) of HETDP. A polycarbonate resin was produced according to the operation described in Example 1 except that it was used.

The weight average molecular weight (Mw) of the obtained polycarbonate resin was 39400, and the Tg was 88 ° C. The thermal decomposition start temperature (Td) was 372 ° C.
This polycarbonate resin was preheated at 200 ° C. for 3 minutes and then pressed at 10 MPa for 1 minute to prepare a press sheet (optical film) having a thickness of 0.1 mm. The refractive index (nD) of this press sheet (optical film) was 1.635 and the Abbe number was 27.0.

After further scaling up and manufacturing this polycarbonate resin, 500 ppm of an antioxidant (trade name "Adecastab PEP-45"; manufactured by Asahi Denka Kogyo Co., Ltd.) and glycerin monostearylate were added to the obtained polycarbonate resin. 300 ppm was added and kneaded at 230 ° C. with an extruder and pelletized to obtain pellets.
The pellets are vacuum dried at 80 ° C. for 24 hours, then injection molded at a cylinder temperature of 230 ° C. and a mold temperature of 80 ° C., and a biconvex lens having a diameter of 9.4 mm and a radius of curvature of both convex surfaces of 5.0 mm (center of the lens). Thickness; 9.0 mm) was obtained. Observation under Cross Nicol confirmed that the lens had no optical distortion. Moreover, when the total light transmittance was measured, it was 90%. In addition, the injection moldability was good, and the lens could be molded without any problem.

(Example 5)
Instead of using 12.71 g (41.5 mmol) of HETDP in Example 1, 10.89 g (41.5 mmol) of 4-hydroxyphenyl-4'-(2 "-hydroxyethoxy) phenylsulfide prepared in Synthesis Example 4 ) A polycarbonate resin was produced according to the operation described in Example 1 except that it was used.

The weight average molecular weight (Mw) of the obtained polycarbonate resin was 46000, and Tg was 160 ° C. The thermal decomposition start temperature (Td) was 368 ° C.
This polycarbonate resin was preheated at 200 ° C. for 3 minutes and then pressed at 10 MPa for 1 minute to prepare a press sheet (optical film) having a thickness of 0.1 mm. The refractive index (nD) of this press sheet (optical film) was 1.651 and the Abbe number was 21.9.

After further scaling up and manufacturing this polycarbonate resin, 500 ppm of an antioxidant (trade name "Adecastab PEP-45"; manufactured by Asahi Denka Kogyo Co., Ltd.) and glycerin monostearylate were added to the obtained polycarbonate resin. 300 ppm was added and kneaded at 280 ° C. with an extruder and pelletized to obtain pellets.
The pellets are vacuum dried at 100 ° C. for 24 hours, then injection molded at a cylinder temperature of 280 ° C. and a mold temperature of 140 ° C., and a biconvex lens having a diameter of 9.4 mm and a radius of curvature of both convex surfaces of 5.0 mm (center of the lens). Thickness; 9.0 mm) was obtained. Observation under Cross Nicol confirmed that the lens had no optical distortion. Moreover, when the total light transmittance was measured, it was 88%. In addition, the injection moldability was good, and the lens could be molded without any problem.

(Example 6)
Instead of using 24.51 g (41.5 mmol) of 9,9-bis (4'-phenoxycarbonyloxyphenyl) fluorene in Example 2, the 9,9-bis (3'-methyl) produced in Synthesis Example 2 A polycarbonate resin was produced according to the procedure described in Example 2 except that 25.67 g (41.5 mmol) of -4'-phenoxycarbonyloxyphenyl) fluorene was used.

The weight average molecular weight (Mw) of the obtained polycarbonate resin was 81300, and the Tg was 133 ° C. The thermal decomposition start temperature (Td) was 364 ° C.
This polycarbonate resin was preheated at 200 ° C. for 3 minutes and then pressed at 10 MPa for 1 minute to prepare a press sheet (optical film) having a thickness of 0.1 mm. The refractive index (nD) of this press sheet (optical film) was 1.639 and the Abbe number was 24.6.

After further scaling up and manufacturing this polycarbonate resin, 500 ppm of an antioxidant (trade name "Adecastab PEP-45"; manufactured by Asahi Denka Kogyo Co., Ltd.) and glycerin monostearylate were added to the obtained polycarbonate resin. 300 ppm was added and kneaded at 250 ° C. with an extruder and pelletized to obtain pellets.
The pellets are vacuum dried at 100 ° C. for 24 hours, then injection molded at a cylinder temperature of 250 ° C. and a mold temperature of 120 ° C., and a biconvex lens having a diameter of 9.4 mm and a radius of curvature of both convex surfaces of 5.0 mm (center of the lens). Thickness; 9.0 mm) was obtained. Observation under Cross Nicol confirmed that the lens had no optical distortion. Moreover, when the total light transmittance was measured, it was 89%. In addition, the injection moldability was good, and the lens could be molded without any problem.

(Example 7)
Example 1 except that 14.04 g (41.5 mmol) of bis [4- (2'-hydroxyethoxy) phenyl] sulfone was used instead of 12.71 g (41.5 mmol) of HETDP. Polycarbonate was produced according to the operation described in 1.

The weight average molecular weight (Mw) of the obtained polycarbonate resin was 15400, and the Tg was 166 ° C. The thermal decomposition start temperature (Td) was 363 ° C.
This polycarbonate resin was preheated at 200 ° C. for 3 minutes and then pressed at 10 MPa for 1 minute to prepare a press sheet (optical film) having a thickness of 0.1 mm. The refractive index (nD) of this press sheet (optical film) was 1.631 and the Abbe number was 23.7.

After further scaling up and manufacturing this polycarbonate resin, 500 ppm of an antioxidant (trade name "Adecastab PEP-45"; manufactured by Asahi Denka Kogyo Co., Ltd.) and glycerin monostearylate were added to the obtained polycarbonate resin. 300 ppm was added and kneaded at 250 ° C. with an extruder and pelletized to obtain pellets.
The pellet is vacuum dried at 100 ° C. for 24 hours, then injection molded at a cylinder temperature of 270 ° C. and a mold temperature of 140 ° C., and a biconvex lens having a diameter of 9.4 mm and a radius of curvature of both convex surfaces of 5.0 mm (center of the lens). Thickness; 9.0 mm) was obtained. Observation under Cross Nicol confirmed that the lens had no optical distortion. Moreover, when the total light transmittance was measured, it was 90%. In addition, the injection moldability was good, and the lens could be molded without any problem.

( Reference example 1 )
In Example 1, instead of using 12.71 g (41.5 mmol) of HETDP, 6.36 g (20.75 mmol) of HETDP and 9,9-bis [4'-(2 "-hydroxyethoxy) phenyl] fluorene 9 A polycarbonate resin was produced according to the procedure described in Example 1 except that 10 g (20.75 mmol) was used.

The weight average molecular weight (Mw) of the obtained polycarbonate resin was 25,400, and the Tg was 164 ° C. The thermal decomposition start temperature (Td) was 369 ° C.
This polycarbonate resin was preheated at 200 ° C. for 3 minutes and then pressed at 10 MPa for 1 minute to prepare a press sheet (optical film) having a thickness of 0.1 mm. The refractive index (nD) of this press sheet (optical film) was 1.648 and the Abbe number was 23.0.

After further scaling up and manufacturing this polycarbonate resin, 500 ppm of an antioxidant (trade name "Adecastab PEP-45"; manufactured by Asahi Denka Kogyo Co., Ltd.) and glycerin monostearylate were added to the obtained polycarbonate resin. 300 ppm was added and kneaded at 250 ° C. with an extruder and pelletized to obtain pellets.
The pellet is vacuum dried at 100 ° C. for 24 hours, then injection molded at a cylinder temperature of 270 ° C. and a mold temperature of 140 ° C., and a biconvex lens having a diameter of 9.4 mm and a radius of curvature of both convex surfaces of 5.0 mm (center of the lens). Thickness; 9.0 mm) was obtained. Observation under Cross Nicol confirmed that the lens had no optical distortion. Moreover, when the total light transmittance was measured, it was 88%. In addition, the injection moldability was good, and the lens could be molded without any problem.

(Example 9)
In Example 1, instead of using 12.71 g (41.5 mmol) of HETDP, 13.88 g (41. 41.) of the bis [4- (2'-hydroxyethoxy) -3-methylphenyl] sulfide produced in Synthesis Example 5. A polycarbonate resin was produced according to the procedure described in Example 1 except that 5 mmol) was used.

The weight average molecular weight (Mw) of the obtained polycarbonate resin was 36,500, and Tg was 128 ° C. The thermal decomposition start temperature (Td) was 378 ° C.
This polycarbonate resin was preheated at 200 ° C. for 3 minutes and then pressed at 10 MPa for 1 minute to prepare a press sheet (optical film) having a thickness of 0.1 mm. The refractive index (nD) of this press sheet (optical film) was 1.634 and the Abbe number was 24.1.

After further scaling up and manufacturing this polycarbonate resin, 500 ppm of an antioxidant (trade name "Adecastab PEP-45"; manufactured by Asahi Denka Kogyo Co., Ltd.) and glycerin monostearylate were added to the obtained polycarbonate resin. 300 ppm was added and kneaded at 250 ° C. with an extruder and pelletized to obtain pellets.
The pellets are vacuum dried at 100 ° C. for 24 hours, then injection molded at a cylinder temperature of 250 ° C. and a mold temperature of 110 ° C., and a biconvex lens having a diameter of 9.4 mm and a radius of curvature of both convex surfaces of 5.0 mm (center of the lens). Thickness; 9.0 mm) was obtained. Observation under Cross Nicol confirmed that the lens had no optical distortion. Moreover, when the total light transmittance was measured, it was 89%. In addition, the injection moldability was good, and the lens could be molded without any problem.

( Reference example 2 )
In Example 1, instead of using 14.54 g (41.5 mmol) of BPFL, 12.71 g (41.5 mmol) of HETDP, 17.45 g (49.8 mmol) of BPFL, 9,9-bis [4'-( 2 "-Hydroxyethyl) Phenyl] A polycarbonate resin was produced according to the procedure described in Example 1 except that 9.83 g (22.4 mmol) of fluorene and 3.30 g (10.79 mmol) of HEDTP were used.

The weight average molecular weight (Mw) of the obtained polycarbonate resin was 54,600, and the Tg was 185 ° C. The thermal decomposition start temperature (Td) was 372 ° C.
This polycarbonate resin was preheated at 240 ° C. for 3 minutes and then pressed at 10 MPa for 1 minute to prepare a press sheet (optical film) having a thickness of 0.1 mm. The refractive index (nD) of this press sheet (optical film) was 1.648 and the Abbe number was 23.0.

After further scaling up and manufacturing this polycarbonate resin, 500 ppm of an antioxidant (trade name "Adecastab PEP-45"; manufactured by Asahi Denka Kogyo Co., Ltd.) and glycerin monostearylate were added to the obtained polycarbonate resin. 300 ppm was added and kneaded at 250 ° C. with an extruder and pelletized to obtain pellets.
The pellets are vacuum dried at 100 ° C. for 24 hours, then injection molded at a cylinder temperature of 280 ° C. and a mold temperature of 160 ° C., and a biconvex lens having a diameter of 9.4 mm and a radius of curvature of both convex surfaces of 5.0 mm (center of the lens). Thickness; 9.0 mm) was obtained. Observation under Cross Nicol confirmed that the lens had no optical distortion. Moreover, when the total light transmittance was measured, it was 90%. In addition, the injection moldability was good, and the lens could be molded without any problem.

(Comparative Example 1)
As the polycarbonate resin made of bisphenol A, the trade name "Panlite L-1225Y" (manufactured by Teijin Chemicals Ltd .: Mw = 45000, Tg: 154 ° C., refractive index: 1.585) was used.
The pellet made of this polycarbonate resin is vacuum dried at 100 ° C. for 24 hours and then injection molded at a cylinder temperature of 280 ° C. and a mold temperature of 120 ° C., and has a diameter of 9.4 mm and a radius of curvature of both convex surfaces of 5.0 mm. A biconvex lens (thickness at the center of the lens; 9.0 mm) was obtained. Observation under Cross Nicol confirmed that the lens had a large birefringence and a large optical distortion. Moreover, when the total light transmittance was measured, it was 90%.

The above results are shown in Table 1. In the evaluation of optical distortion, a lens having no optical distortion was evaluated as ◯, and a lens having a large optical distortion was evaluated as x.

From Table 1, the polycarbonate resin according to the present embodiment has an excellent balance of high refractive index, high transparency, low Abbe number, and good injection moldability, and can further suppress optical distortion of the obtained molded product. Understandable.

Claims (14)

A polycarbonate resin having a structural unit (A) represented by the following formula (A) and a structural unit (B) represented by the following formula (B).

(In the above formula (A), R _{1 to} R ₄ represent a hydrogen atom, a halogen atom, an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms. They may be the same or different.)

(In the above formula (B), R _{5 to} R ₁₂ represent a hydrogen atom, a halogen atom, an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms. may be the same or different, X represents an alkylene group having 2 to 10 carbon atoms, may be the same or different, W is -S -, - SO- or -SO ₂ - represents, n and m independently represents an integer of 0 to 6. However, n + m is not 0.) In the polycarbonate resin according to claim 1,
When the total of all the structural units in the polycarbonate resin is 100 mol%, the total content of the structural units (A) and the structural units (B) in the polycarbonate resin is 50 mol% or more and 100 mol% or less. Polycarbonate resin. In the polycarbonate resin according to claim 1 or 2.
A polycarbonate resin in which the molar ratio ((A) / (B)) of the structural unit (A) to the structural unit (B) in the polycarbonate resin is 2/98 or more and 98/2 or less. In the polycarbonate resin according to any one of claims 1 to 3.
In the formula (A), R _{1 to} R ₄ are hydrogen atoms or alkyl groups having 1 to 3 carbon atoms.
In the formula (B), R _{5 to} R ₁₂ are hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, X is a 1,2-ethylene group, and n and m are 1 or 0. In the polycarbonate resin according to any one of claims 1 to 4.
A polycarbonate resin having a refractive index of 1.630 or more and 1.695 or less at 23 ° C. and a wavelength of 589 nm, which is measured according to JIS K-7142. In the polycarbonate resin according to any one of claims 1 to 5,
A polycarbonate resin having a glass transition temperature of 80 ° C. or higher and 190 ° C. or lower as measured by differential scanning calorimetry. In the polycarbonate resin according to any one of claims 1 to 6.
A polycarbonate resin having a total light transmittance of 85% or more measured in accordance with JIS K-7361-1. In the polycarbonate resin according to any one of claims 1 to 7.
The weight average molecular weight (Mw) in terms of polystyrene 1.5 × 10 ⁴ or more 2.0 × 10 ⁵ or less is a polycarbonate resin. In the polycarbonate resin according to any one of claims 1 to 8.
Polycarbonate resin having an Abbe number of 27 or less. A production method for producing the polycarbonate resin according to any one of claims 1 to 9.
A step of synthesizing the polycarbonate resin by reacting the dihydroxy compound (I) represented by the following formula (I) and the dihydroxy compound (II) represented by the following formula (II) with a carbonic acid diester is included.
A method for producing a polycarbonate resin, wherein the total amount of the dihydroxy compound (I) and the dihydroxy compound (II) is 50 mol% or more, assuming that the total amount of all the dihydroxy compounds contained in the reaction system is 100 mol%.

(In the above formula (I), R _{1 to} R ₄ represent a hydrogen atom, a halogen atom, an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms. They may be the same or different.)

(In the above formula (II), R _{5 to} R ₁₂ represent a hydrogen atom, a halogen atom, an aryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 5 to 20 carbon atoms. may be the same or different, X represents an alkylene group having 2 to 10 carbon atoms, may be the same or different, W is -S -, - SO- or -SO ₂ - represents, n and m independently represents an integer of 0 to 6. However, n + m is not 0.) In the method for producing a polycarbonate resin according to claim 10,
A method for producing a polycarbonate resin in which the molar ratio ((I) / (II)) of the dihydroxy compound (I) to the dihydroxy compound (II) is 2/98 or more and 98/2 or less. An optically molded product containing the polycarbonate resin according to any one of claims 1 to 9. The optically molded body according to claim 12, which is an optical lens. The optically molded product according to claim 12, which is an optical film.