JP2014185325A5

JP2014185325A5 -

Info

Publication number: JP2014185325A5
Application number: JP2014022428A
Authority: JP
Filing date: 2014-02-07
Publication date: 2014-11-13
Anticipated expiration: 2034-02-07

Description

すなわち、本発明は、
１．５０〜２モル％の下記式（Ｉ）で表される構成単位及び５０〜９８モル％で表される
下記式（ＩＩ）で表される構成単位を含有し、比粘度０．１２〜０．４０であるポリカーボネート共重合体。

（式中のＲ_１〜Ｒ_８は、それぞれ水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素数１〜６のアルキル基、炭素数６〜１２のアリール基、炭素数２〜６のアルケニル基、炭素数１〜６のアルコキシ基又は炭素数７〜１７のアラルキル基を示す。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は０の整数である。）

（式中、Ｒ_９、Ｒ_１０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。Ｙ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。ｍは０〜１０の整数である。）
２．式（ＩＩ）中のＹは、エチレン基であり、Ｒ_９、Ｒ_１０が水素原子である前記１に記載のポリカーボネート共重合体。
３．式（Ｉ）中のＲ_１〜Ｒ_８が、水素原子である前記１に記載のポリカーボネート共重合体。
４．式（Ｉ）中のｎが０である前記１に記載のポリカーボネート共重合体。
５．式（Ｉ）に記載の構成単位が、１，１−ビ−２−ナフチル構造である前記１に記載のポリカーボネート共重合体。
６．屈折率が１．６４０〜１．６６５である前記１〜５のいずれかに記載のポリカーボネ
ート共重合体。
７．配向複屈折が０〜６×１０^−３である前記１〜６のいずれかに記載のポリカーボネー
ト共重合体。
８．ガラス転移温度が、１４０〜１７０℃である前記１〜７のいずれかに記載のポリカー
ボネート共重合体。
９．５０〜２０モル％の上記式（Ｉ）で表される構成単位及び５０〜８０モル％で表され
る上記式（ＩＩ）で表される構成単位を含有し、比粘度０．１２〜０．４０である前記１
〜８のいずれかに記載のポリカーボネート共重合体。
１０．フェノール含有量が１〜５００ｐｐｍである前記１〜９のいずれかに記載のポリカーボネート共重合体。
１１．下記式（ＩＩＩ）で表されるジオール成分の含有量が５〜５００ｐｐｍである前記
１〜１０のいずれかに記載のポリカーボネート共重合体。

（式中、Ｒ_１１、Ｒ_１２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。Ｚ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。ｏは０〜１０の整数である。）
１２．前記１〜１１のいずれかに記載のポリカーボネート共重合体からなる光学部材。
１３．前記１〜１１のいずれかに記載のポリカーボネート共重合体からなる光学レンズ。
１４．中心部の厚みが０．０５〜３．０ｍｍ、レンズ部の直径が１．０〜２０．０ｍｍである前記１３に記載の光学レンズ。 That is, the present invention
It contains a structural unit represented by the following formula (I) of 1.50 to 2 mol% and a structural unit represented by the following formula (II) represented by 50 to 98 mol%, and has a specific viscosity of 0.12 to 0.12 Polycarbonate copolymer which is 0.40.

(In the formula, R _{1 to} R ₈ are each a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or 2 to 6 carbon atoms. An alkenyl group, an alkoxy group having 1 to 6 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, X is an alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or 6 to 20 carbon atoms. (Wherein n is an integer of 0 )

(In formula, R <_9> , R < ₁₀ > is respectively independently a hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxyl group, a C5-C20 cycloalkyl group, and C5-C20. A cycloalkoxyl group, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, Y is an alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or 6 carbon atoms. An arylene group of ˜20, m is an integer of 0-10.)
2. Y in Formula (II) is an ethylene group, The polycarbonate copolymer of said 1 whose R <_9> , R < ₁₀ > is a hydrogen atom.
3. 2. The polycarbonate copolymer as described in 1 above, wherein R _{1 to} R ₈ in formula (I) are hydrogen atoms.
4). 2. The polycarbonate copolymer according to 1 above, wherein n in the formula (I) is 0 .
5. Structural units according to formula (I), polycarbonate copolymer according to the 1 is 1,1-bi-2-naphthyl structure.
6). 6. The polycarbonate copolymer according to any one of 1 to 5 above, which has a refractive index of 1.640 to 1.665.
7). 7. The polycarbonate copolymer according to any one of 1 to 6 above, wherein the orientation birefringence is 0 to 6 × 10 ⁻³ .
8). The polycarbonate copolymer according to any one of 1 to 7 above, which has a glass transition temperature of 140 to 170 ° C.
9. Containing a structural unit represented by the above formula (I) of 50 to 20 mol% and a structural unit represented by the above formula (II) represented by 50 to 80 mol%, and having a specific viscosity of 0.12 to 0.12 Said 1 which is 0.40
The polycarbonate copolymer in any one of -8.
10. The polycarbonate copolymer according to any one of 1 to 9 above, wherein the phenol content is 1 to 500 ppm.
11. The polycarbonate copolymer according to any one of 1 to 10 above, wherein the content of the diol component represented by the following formula (III) is 5 to 500 ppm.

(In formula, R <_11> , R < ₁₂ > is respectively independently a hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxyl group, a C5-C20 cycloalkyl group, and C5-C20. A cycloalkoxyl group, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, Z is an alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or 6 carbon atoms. An arylene group of ˜20, o is an integer of 0-10.)
12 The optical member which consists of a polycarbonate copolymer in any one of said 1-11.
13. An optical lens comprising the polycarbonate copolymer according to any one of 1 to 11 above.
14 14. The optical lens according to 13, wherein the thickness of the central part is 0.05 to 3.0 mm and the diameter of the lens part is 1.0 to 20.0 mm.

参考例５
ＢＰＥＦ１４０．３２重量部、１，１−ビ（２−（２−ヒドロキシエトキシ）ナフタレ
ン（以下“ＢＬ−２ＥＯ”と省略することがある）２９．９６重量部、ＤＰＣ８９．９７
重量部、及びテトラメチルアンモニウムヒドロキシド１．８２×１０^−２重量部を攪拌機
および留出装置付きの反応釜に入れ、窒素雰囲気常圧下、１８０℃に加熱し、２０分間撹
拌した。その後、２０分かけて減圧度を２０〜３０ｋＰａに調整し、６０℃／ｈｒの速度
で２６０℃まで昇温し、エステル交換反応を行った。その後、２６０℃に保持したまま、
１２０分かけて０．１３ｋＰａ以下まで減圧し、２６０℃、０．１３ｋＰａ以下の条件下
で１時間攪拌下重合反応を行った。該ポリカーボネート共重合体はＢＰＥＦとＢＬ−２
ＥＯとのモル比が８０：２０であり、比粘度は０．２１８、Ｔｇは１４０℃、未反応ＢＰ
ＥＦ１５０ｐｐｍ、残存ＰｈＯＨ３００ｐｐｍであった。
作成したポリマーを１２０℃で４時間真空乾燥した後、得られる樹脂組成物の重量を基
準としてビス（２，４−ジクミルフェニル）ペンタエリスリトールジホスファイト０．０
５０％、ペンタエリスリトールテトラステアレートを０．１０％加えて、ベント付きφ３
０ｍｍ単軸押出機を用いてペレット化した。耐湿熱性は、良好で湿熱試験後の比粘度保持
率は、９５％であった。また、耐熱性も良好で耐熱性試験後の比粘度保持率は、８５％で
あった。 Reference Example 5
BPEF 140.32 parts by weight, 1,1-bi (2- (2-hydroxyethoxy) naphthalene (hereinafter sometimes abbreviated as “BL-2EO”) 29.96 parts by weight, DPC 89.97
Part by weight and 1.82 × 10 ⁻² parts by weight of tetramethylammonium hydroxide were placed in a reaction kettle equipped with a stirrer and a distillation apparatus, heated to 180 ° C. under nitrogen atmosphere and normal pressure, and stirred for 20 minutes. Thereafter, the degree of vacuum was adjusted to 20 to 30 kPa over 20 minutes, and the temperature was raised to 260 ° C. at a rate of 60 ° C./hr to conduct a transesterification reaction. After that, while maintaining at 260 ° C.
The pressure was reduced to 0.13 kPa or less over 120 minutes, and the polymerization reaction was carried out with stirring for 1 hour under the conditions of 260 ° C. and 0.13 kPa or less. The polycarbonate copolymer is BPEF and BL-2.
The molar ratio with EO is 80:20, specific viscosity is 0.218, Tg is 140 ° C., unreacted BP
The EF was 150 ppm and the residual PhOH was 300 ppm.
The prepared polymer was vacuum-dried at 120 ° C. for 4 hours, and then bis (2,4-dicumylphenyl) pentaerythritol diphosphite 0.0 based on the weight of the resulting resin composition.
50%, 0.10% pentaerythritol tetrastearate, φ3 with vent
Pelletized using a 0 mm single screw extruder. The wet heat resistance was good, and the specific viscosity retention after the wet heat test was 95%. Moreover, heat resistance was also favorable, and the specific viscosity retention after the heat resistance test was 85%.

参考例６
ＢＰＥＦ８７．７０重量部、ＢＬ−２ＥＯと７４．８９重量部とする以外は、実施例５
と同様に重合した。
該ポリカーボネート共重合体はＢＰＥＦとＢＬ−２ＥＯとのモル比が５０：５０であり
、比粘度は０．２０２、Ｔｇは１３４℃、未反応ＢＰＥＦ１００ｐｐｍ、残存ＰｈＯＨ６
０ｐｐｍであった。
作成したポリマーを１２０℃で４時間真空乾燥した後、得られる樹脂組成物の重量を基
準としてビス（２，４−ジクミルフェニル）ペンタエリスリトールジホスファイト０．０
５０％、ペンタエリスリトールテトラステアレートを０．１０％加えて、ベント付きφ３
０ｍｍ単軸押出機を用いてペレット化した。耐湿熱性は、良好で湿熱試験後の比粘度保持
率は、９５％であった。また、耐熱性も良好で耐熱性試験後の比粘度保持率は、９０％
であった。 Reference Example 6
Example 5 with the exception of 87.70 parts by weight of BPEF and 74.89 parts by weight of BL-2EO.
Was polymerized in the same manner.
The polycarbonate copolymer has a molar ratio of BPEF to BL-2EO of 50:50, a specific viscosity of 0.202, Tg of 134 ° C., unreacted BPEF of 100 ppm, and residual PhOH 6.
It was 0 ppm.
The prepared polymer was vacuum-dried at 120 ° C. for 4 hours, and then bis (2,4-dicumylphenyl) pentaerythritol diphosphite 0.0 based on the weight of the resulting resin composition.
50%, 0.10% pentaerythritol tetrastearate, φ3 with vent
Pelletized using a 0 mm single screw extruder. The wet heat resistance was good, and the specific viscosity retention after the wet heat test was 95%. In addition, the heat resistance is good and the specific viscosity retention after the heat resistance test is 90%.
Met.

参考例７
ビスフェノールフルオレン（以下“ＢＰＦＬ”と省略することがある）７０．０８重量
部、ＢＬ−２ＥＯと７４．８９重量部とする以外は、実施例５と同様に重合した。
該ポリカーボネート共重合体はＢＰＦＬとＢＬ−２ＥＯとのモル比が５０：５０であり
、比粘度は０．２３０、Ｔｇは１５９℃、未反応ＢＰＦＬ２００ｐｐｍ、残存ＰｈＯＨ２
５０ｐｐｍであった。
作成したポリマーを１２０℃で４時間真空乾燥した後、得られる樹脂組成物の重量を基
準としてビス（２，４−ジクミルフェニル）ペンタエリスリトールジホスファイト０．０
５０％、ペンタエリスリトールテトラステアレートを０．１０％加えて、ベント付きφ３
０ｍｍ単軸押出機を用いてペレット化した。耐湿熱性は、良好で湿熱試験後の比粘度保持
率は、９０％であった。また、耐熱性も良好で耐熱性試験後の比粘度保持率は、８０％で
あった。 Reference Example 7
Polymerization was conducted in the same manner as in Example 5 except that 70.08 parts by weight of bisphenol fluorene (hereinafter sometimes abbreviated as “BPFL”) and 74.89 parts by weight of BL-2EO were used.
The polycarbonate copolymer has a molar ratio of BPFL to BL-2EO of 50:50, a specific viscosity of 0.230, Tg of 159 ° C., unreacted BPFL of 200 ppm, and residual PhOH 2.
It was 50 ppm.
The prepared polymer was vacuum-dried at 120 ° C. for 4 hours, and then bis (2,4-dicumylphenyl) pentaerythritol diphosphite 0.0 based on the weight of the resulting resin composition.
50%, 0.10% pentaerythritol tetrastearate, φ3 with vent
Pelletized using a 0 mm single screw extruder. The heat and humidity resistance was good, and the specific viscosity retention after the wet heat test was 90%. Moreover, heat resistance was also favorable, and the specific viscosity retention after the heat resistance test was 80%.

Claims

It contains 50 to 2 mol% of a structural unit represented by the following formula (I) and 50 to 98 mol% of a structural unit represented by the following formula (II), and has a specific viscosity of 0.12 to 0. 40, a polycarbonate copolymer.

(In formula, R <_9> , R < ₁₀ > is respectively independently a hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxyl group, a C5-C20 cycloalkyl group, and C5-C20. A cycloalkoxyl group, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, wherein Y is an alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or 6 to 6 carbon atoms. 20 is an arylene group, and m is an integer of 0 to 10.)

2. The polycarbonate copolymer according to claim 1, wherein Y in the formula (II) is an ethylene group, and R _{9 and} R ₁₀ are hydrogen atoms.

The polycarbonate copolymer according to claim 1, wherein R _{1 to} R ₈ in formula (I) are hydrogen atoms.

The polycarbonate copolymer according to claim 1, wherein n in the formula (I) is 0 .

Structural units according to formula (I), polycarbonate copolymer according to claim 1 which is 1,1-bi-2-naphthyl structure.

The polycarbonate copolymer according to any one of claims 1 to 5, having a refractive index of 1.640 to 1.665.

The polycarbonate copolymer according to any one of claims 1 to 6, wherein the orientation birefringence is 0 to 6 x ^10-3 .

Glass transition temperature is 140-170 degreeC, The polycarbonate copolymer in any one of Claims 1-7.

It contains 50 to 20 mol% of the structural unit represented by the above formula (I) and 50 to 80 mol% of the structural unit represented by the above formula (II), and has a specific viscosity of 0.12 to 0. 40.
The polycarbonate copolymer in any one of -8.

The polycarbonate copolymer according to any one of claims 1 to 9, wherein the phenol content is 1 to 500 ppm.

The content of the diol component represented by the following formula (III) is 5 to 500 ppm.
The polycarbonate copolymer in any one of -10.

(In formula, R <_11> , R < ₁₂ > is respectively independently a hydrogen atom, a C1-C20 alkyl group, a C1-C20 alkoxyl group, a C5-C20 cycloalkyl group, and C5-C20. A cycloalkoxyl group, 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 6 carbon atoms. An arylene group of ˜20, o is an integer of 0-10.)

The optical member which consists of a polycarbonate copolymer as described in any one of Claims 1-11.

The optical lens which consists of a polycarbonate copolymer as described in any one of Claims 1-11.

The optical lens according to claim 13, wherein the thickness of the central portion is 0.05 to 3.0 mm, and the diameter of the lens portion is 1.0 to 20.0 mm.