JP2006232897A - Copolycarbonate resin - Google Patents
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- JP2006232897A JP2006232897A JP2005046285A JP2005046285A JP2006232897A JP 2006232897 A JP2006232897 A JP 2006232897A JP 2005046285 A JP2005046285 A JP 2005046285A JP 2005046285 A JP2005046285 A JP 2005046285A JP 2006232897 A JP2006232897 A JP 2006232897A
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- 0 *C(*)(CO)C(OC1)OCC11COC(C(*)(*)CO)OC1 Chemical compound *C(*)(CO)C(OC1)OCC11COC(C(*)(*)CO)OC1 0.000 description 1
- VKONPUDBRVKQLM-UHFFFAOYSA-N OC(CC1)CCC1O Chemical compound OC(CC1)CCC1O VKONPUDBRVKQLM-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は光学用途フィルムに好適な透明性、耐熱性、低い光弾性係数、機械強度を有するコポリカーボネート樹脂ならびにその製造方法に属する。 The present invention belongs to a copolycarbonate resin having transparency, heat resistance, low photoelastic coefficient, and mechanical strength suitable for an optical use film, and a method for producing the same.
近年、オプトエレクトロニクスの進歩に伴い、光学的に優れた等方性を有する光学用透明高分子に対する要請が高まっている。特に、液晶ディスプレイの位相差フィルム用に適用可能な光学特性の透明フィルムが切望されている。 In recent years, with the advancement of optoelectronics, there has been an increasing demand for optically transparent polymers having optically excellent isotropic properties. In particular, a transparent film having optical properties applicable to a retardation film for a liquid crystal display is desired.
2,2-ビス（4-ヒドロキシフェニル）プロパン（通称：ビスフェノールＡ）をホスゲンあるいは炭酸ジエステルと反応させて得られるポリカーボネート樹脂、殊にポリカーボネートフイルムは包装用途、光学装置、表示装置その他各種産業用途に使用されているが、最近液晶表示装置など光電子装置において位相差板、偏光板、プラスチック基板等の材料として注目され、その実用化が進められている。とりわけ、近年の液晶ディスプレーなかでも、進歩が著しいＴＦＴ型液晶ディスプレー素子においては画像の視認性を向上させるために液晶層と偏光板との間で使用する位相差フイルムとして注目される。 Polycarbonate resin obtained by reacting 2,2-bis (4-hydroxyphenyl) propane (common name: bisphenol A) with phosgene or carbonic acid diester, especially polycarbonate film is used for packaging, optical equipment, display and other various industrial uses. In recent years, it has been attracting attention as a material for retardation plates, polarizing plates, plastic substrates and the like in optoelectronic devices such as liquid crystal display devices, and its practical application has been promoted. In particular, among liquid crystal displays in recent years, TFT type liquid crystal display elements that have made remarkable progress are attracting attention as retardation films used between a liquid crystal layer and a polarizing plate in order to improve image visibility.
この位相差フイルムは、液晶層を透過した楕円偏光を直線偏光に変換する役割を担っている。そして、その材質は主としてビスフェノールＡからなるポリカーボネート樹脂の一軸延伸フイルムが用いられている。 This retardation film has a role of converting elliptically polarized light transmitted through the liquid crystal layer into linearly polarized light. A uniaxially stretched film of polycarbonate resin mainly composed of bisphenol A is used as the material.
しかし、ビスフェノールＡからなるポリカーボネート樹脂は、低流動性材料であり、また高い光弾性係数を有するため、溶融成形時の分子配向や残留応力に伴う複屈折が大きいという問題点を有している。このため均一性を維持するため、通常溶融押出成形ではなく、溶液状態からの塗膜を乾燥させるキャスト法が多く使用される。 However, the polycarbonate resin made of bisphenol A is a low fluid material and has a high photoelastic coefficient, and therefore has a problem that the birefringence associated with molecular orientation and residual stress during melt molding is large. For this reason, in order to maintain uniformity, a casting method for drying a coating film from a solution state is generally used instead of melt extrusion molding.
より生産性の高い溶融成形フィルムを得るにはビスフェノールＡからなるポリカーボネート樹脂では、複屈折の低減には限界があるため、近年の光学材料用途の広がりに伴い、さらなる低光弾性係数、高流動性材料の開発が強く求められている。 In order to obtain a melt-formed film with higher productivity, polycarbonate resin made of bisphenol A has a limit in reducing birefringence. Therefore, with the recent spread of optical materials, further lower photoelastic coefficient and higher fluidity There is a strong demand for the development of materials.
本出願人は従来の芳香族ポリカーボネートの上記のような問題を解決すべく、スピログリコール等の脂環式ジヒドロキシ化合物とビスフェノールＡに代表される芳香族ジヒドロキシ化合物及び炭酸ジエステルとを溶融状態で重縮合させるエステル交換法によって得られるポリカーボネート樹脂を提案した（特許文献１参照）。これにより得られるポリカーボネート樹脂は機械物性、耐熱性、透明性の面で優れている。しかしながら、脂環式ジヒドロキシ化合物を共重合させたポリカーボネートではビスフェノールＡからなるポリカーボネート樹脂と比較すれば光弾性係数は低いもののフィルム用途としては光弾性係数が大き過ぎるといった問題がある。 In order to solve the above-mentioned problems of conventional aromatic polycarbonates, the present applicant polycondenses an alicyclic dihydroxy compound such as spiroglycol with an aromatic dihydroxy compound typified by bisphenol A and a carbonic acid diester in a molten state. A polycarbonate resin obtained by a transesterification method was proposed (see Patent Document 1). The polycarbonate resin thus obtained is excellent in mechanical properties, heat resistance, and transparency. However, a polycarbonate copolymerized with an alicyclic dihydroxy compound has a problem that the photoelastic coefficient is too large for film use although the photoelastic coefficient is low as compared with a polycarbonate resin made of bisphenol A.
一方、色補償用の位相差フィルムとしては、１/２λ、１/４λ板の張り合わせ等が存在している（特許文献２参照）。この用途に用いられるフィルムとしては一枚の状態で複屈折の波長分散がないことが良好とされる。 On the other hand, as a retardation film for color compensation, there is a lamination of 1 / 2λ, 1 / 4λ plate, and the like (see Patent Document 2). As a film used for this purpose, it is preferable that there is no birefringence wavelength dispersion in a single sheet.
これらのフィルム原料として芳香環を持つジヒドロキシ化合物を原料に用いたポリカーボネートでは広範囲領域での補償がかなわず、もしくは光弾性係数が大きく張り合わせ時の歪が生じてしまうといった問題がある。またアモルファスポリオレフィンを用いた場合は脆いといった強度面での問題が生じる。 Polycarbonates using a dihydroxy compound having an aromatic ring as a raw material for these films have a problem that they cannot be compensated in a wide range, or have a large photoelastic coefficient and cause distortion at the time of bonding. When amorphous polyolefin is used, there is a problem in strength such as brittleness.
このため本出願人は、ペンタシクロペンタデカンジメタノールを必須成分とし、トリシクロ（５.２.１.０2,6）デカンジメタノール等の脂環式ジヒドロキシ化合物によりなる脂肪族ポリカーボネート共重合体を提案した（特許文献３参照）。これにより光弾性係数の低減を可能としたが、十分なものではなかった。 Therefore, the present applicant has proposed an aliphatic polycarbonate copolymer comprising pentacyclopentadecane dimethanol as an essential component and comprising an alicyclic dihydroxy compound such as tricyclo (5.2.1.0 2,6 ) decane dimethanol. (See Patent Document 3). This allowed a reduction in the photoelastic coefficient, but it was not sufficient.
本発明は上記課題を解決しようとするものであり、光弾性係数（Ｋ）がK≦１０×１０-１２ｍ2/Ｎであり、ガラス転移温度(Ｔｇ)がＴｇ≧１００℃を満たすものであり、延伸フィルム成形による薄膜化に十分耐えうる強度物性を与えるポリカーボネート樹脂及びその製造方法を提供することにある。 The present invention is intended to solve the above-mentioned problems, wherein the photoelastic coefficient (K) is K ≦ 10 × 10 −12 m 2 / N, and the glass transition temperature (Tg) satisfies Tg ≧ 100 ° C. It is another object of the present invention to provide a polycarbonate resin and a method for producing the same that give strength properties sufficient to withstand thinning by forming a stretched film.
本発明者らは、上記課題を解決するべく鋭意検討を重ねた結果、一般式（１）で表されるジヒドロキシ化合物と、一般式（２）、一般式（３）一般式（４）及び一般式（５）で表されるジヒドロキシ化合物からなる群から選ばれる少なくとも１種のジヒドロキシ化合物と、炭酸ジエステルとを反応させて得られるコポリカーボネート樹脂によって上記問題を解決できることを見いだした。
本発明により、優れた強度、透過性を持つ、複屈折波長分散が少なく、光弾性係数が低く、Ｔｇ≧１００℃と、位相差フィルム用途に好適なバランスのとれたポリカーボネート樹脂を提供することができる。 According to the present invention, it is possible to provide a polycarbonate resin having excellent strength and transparency, low birefringence wavelength dispersion, low photoelastic coefficient, Tg ≧ 100 ° C., and balanced balance suitable for retardation film use. it can.
以下、本発明に係わるポリカーボネート樹脂並びにこれらの製造方法を具体的に説明する。 Hereafter, the polycarbonate resin concerning this invention and these manufacturing methods are demonstrated concretely.
本発明に関わるポリカーボネート樹脂は一般式（１）で表されるジヒドロキシ化合物から誘導される構成単位と、一般式（２）、一般式（３）、一般式（４）及び一般式（５）で表されるジヒドロキシ化合物からなる群から選ばれる少なくとも１種のジヒドロキシ化合物から誘導される構成単位とからなり、ランダム、ブロック、或いは交互共重合体等を含むものである。 The polycarbonate resin according to the present invention includes a structural unit derived from a dihydroxy compound represented by the general formula (1), a general formula (2), a general formula (3), a general formula (4), and a general formula (5). It is composed of structural units derived from at least one dihydroxy compound selected from the group consisting of the represented dihydroxy compounds, and includes random, block, or alternating copolymers.
一般式（１）で表されるジヒドロキシ化合物として、3,9-ビス（2-ヒドロキシエチル）-2,4,8,10-テトラオキサスピロ（5.5）ウンデカン、3,9-ビス（2-ヒドロキシ-1,1-ジメチルエチル）-2,4,8,10-テトラオキサスピロ（5.5）ウンデカン、3,9-ビス（2-ヒドロキシ-1,1-ジエチルエチル）-2,4,8,10-テトラオキサスピロ（5.5）ウンデカン、3,9-ビス（2-ヒドロキシ-1,1-ジプロピルエチル）-2,4,8,10-テトラオキサスピロ（5.5）ウンデカンなどの脂環式ジヒドロキシ化合物があげられる。
好ましくは、3,9-ビス（2-ヒドロキシ-1,1-ジメチルエチル）-2,4,8,10-テトラオキサスピロ（5.5）ウンデカンが用いられる。
As the dihydroxy compound represented by the general formula (1), 3,9-bis (2-hydroxyethyl) -2,4,8,10-tetraoxaspiro (5.5) undecane, 3,9-bis (2-hydroxy) -1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5.5) undecane, 3,9-bis (2-hydroxy-1,1-diethylethyl) -2,4,8,10 -Cycloaliphatic dihydroxy compounds such as tetraoxaspiro (5.5) undecane and 3,9-bis (2-hydroxy-1,1-dipropylethyl) -2,4,8,10-tetraoxaspiro (5.5) undecane Can be given.
Preferably, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5.5) undecane is used.
一般式（２）、及び一般式（３）表されるジヒドロキシ化合物は、ペンタシクロペンタデカンジメタノールであり、種々の異性体を包含する。 The dihydroxy compound represented by the general formula (2) and the general formula (3) is pentacyclopentadecane dimethanol and includes various isomers.
一般式（４）でさ表れるジヒドロキシ化合物はイソマンニド及びイソソルビドであり、ラセミ体、キラル体等の光学活性異性体を包含する。 The dihydroxy compounds represented by the general formula (4) are isomannide and isosorbide, and include optically active isomers such as racemates and chiral isomers.
一般式（５）で表される脂環式ジヒドロキシ化合物は1,4-シクロヘキサンジオールであり、トランス体、シス体或いはその混合物を包含する。 The alicyclic dihydroxy compound represented by the general formula (5) is 1,4-cyclohexanediol and includes a trans isomer, a cis isomer or a mixture thereof.
本発明においては、一般式（１）で表されるジヒドロキシ化合物と、一般式（２）、一般式（３）、一般式（４）及び一般式（５）で表されるジヒドロキシ化合物からなる群から選ばれる少なくとも１種のジヒドロキシ化合物（２種以上の場合は、混合物を指す。）との使用割合が、モル比で８５：１５〜１５：８５の範囲であることが好ましく、さらに好ましくは８０：２０〜２０：８０であり、特に好ましくは７５：２５〜２５：７５である。一般式（１）で表されるジヒドロキシ化合物の使用割合が、モル比で８５より多くなると、樹脂製造時、もしくは延伸時もしくはその双方で、一部もしくは全体で結晶化してしまい、光線透過率が低下するか、極端に低下するため、望ましくない。 In the present invention, a group consisting of a dihydroxy compound represented by the general formula (1) and a dihydroxy compound represented by the general formula (2), the general formula (3), the general formula (4) and the general formula (5). The use ratio with at least one dihydroxy compound selected from the above (in the case of two or more types, a mixture) is preferably in the range of 85:15 to 15:85, more preferably 80. : 20 to 20:80, particularly preferably 75:25 to 25:75. If the use ratio of the dihydroxy compound represented by the general formula (1) is more than 85 in terms of molar ratio, it is partly or entirely crystallized at the time of resin production or at the time of stretching, or both, and the light transmittance is reduced. It is not desirable because it decreases or extremely decreases.
また、更に必要に応じて、二官能性カルボン酸を使用しても良い。
二官能性カルボン酸としては、例えば、テレフタル酸，イソテレフタル酸，ナフタレンジカルボン酸などの芳香族ジカルボン酸が挙げられる。この他の二官能性カルボン酸としては例えば、シュウ酸，マロン酸，アジピン酸，スベリン酸，アゼライン酸，セバシン酸，デカンジカルボン酸、1,4-シクロヘキサンジカルボン酸などの脂肪族ジカルボン酸が挙げられる。この中で、1,4-シクロヘキサンジカルボン酸が特に好ましい。
Further, if necessary, a bifunctional carboxylic acid may be used.
Examples of the bifunctional carboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isoterephthalic acid, and naphthalenedicarboxylic acid. Examples of other difunctional carboxylic acids include aliphatic dicarboxylic acids such as oxalic acid, malonic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. . Of these, 1,4-cyclohexanedicarboxylic acid is particularly preferred.
炭酸ジエステルとしては、ジフェニルカーボネート、ジトリールカーボネート、ビス（クロロフェニル）カーボネート、ｍ−クレジルカーボネート、ジメチルカーボネート、ジエチルカーボネート、ジブチルカーボネート、ジシクロヘキシルカーボネート等があげられる。これらの中でも特にジフェニルカーボネートが好ましい。炭酸ジエステルは、ジヒドロキシ化合物の合計１モルに対して０．９５〜１．１０モルの比率で用いられることが好ましく、更に好ましくは０．９８〜１．０５モルの比率である。 Examples of the carbonic acid diester include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate. Of these, diphenyl carbonate is particularly preferred. The carbonic acid diester is preferably used in a ratio of 0.95 to 1.10 mol, more preferably 0.98 to 1.05 mol, per 1 mol of the total dihydroxy compound.
一般式（１）で表されるジヒドロキシ化合物と、一般式（２）、一般式（３）、一般式（４）及び一般式（５）で表されるジヒドロキシ化合物からなる群から選ばれる少なくとも１種のジヒドロキシ化合物と炭酸ジエステルとを塩基性化合物触媒もしくはエステル交換触媒もしくはその双方からなる混合触媒の存在下反応させる公知の溶融重縮合法が好適に用いられる。塩基性化合物触媒としては、アルカリ金属化合物、アルカリ土類金属化合物、含窒素化合物等があげられる。 At least 1 selected from the group consisting of a dihydroxy compound represented by general formula (1) and a dihydroxy compound represented by general formula (2), general formula (3), general formula (4) and general formula (5). A known melt polycondensation method in which a seed dihydroxy compound and a carbonic acid diester are reacted in the presence of a mixed catalyst comprising a basic compound catalyst or a transesterification catalyst or both is suitably used. Examples of the basic compound catalyst include alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds and the like.
このような化合物としては、アルカリ金属および／またはアルカリ土類金属化合物等の有機酸塩、無機塩、酸化物、水酸化物、水素化物あるいはアルコキシド、４級アンモニウムヒドロキシドおよびそれらの塩、アミン類等が好ましく用いられ、これらの化合物は単独もしくは組み合わせて用いることができる。 Examples of such compounds include organic acid salts such as alkali metal and / or alkaline earth metal compounds, inorganic salts, oxides, hydroxides, hydrides or alkoxides, quaternary ammonium hydroxides and salts thereof, and amines. Etc. are preferably used, and these compounds can be used alone or in combination.
アルカリ金属化合物としては、具体的には、水酸化ナトリウム、水酸化カリウム、水酸化セシウム、水酸化リチウム、炭酸水素ナトリウム、炭酸水素カリウム、炭酸水素セシウム、炭酸水素リチウム、炭酸ナトリウム、炭酸カリウム、炭酸セシウム、炭酸リチウム、酢酸ナトリウム、酢酸カリウム、酢酸セシウム、酢酸リチウム、ステアリン酸ナトリウム、ステアリン酸カリウム、ステアリン酸セシウム、ステアリン酸リチウム、水素化ホウ素ナトリウム、フェニル化ホウ素ナトリウム、安息香酸ナトリウム、安息香酸カリウム、安息香酸セシウム、安息香酸リチウム、リン酸水素２ナトリウム、リン酸水素２カリウム、リン酸水素２リチウム、フェニルリン酸２ナトリウム、ビスフェノールＡの２ナトリウム塩、２カリウム塩、２セシウム塩、２リチウム塩、フェノールのナトリウム塩、カリウム塩、セシウム塩、リチウム塩等が用いられる。 Specific examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, lithium bicarbonate, sodium carbonate, potassium carbonate, carbonate Cesium, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium phenyl borohydride, sodium benzoate, potassium benzoate Cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenyl phosphate, disodium salt of bisphenol A, 2 potassium salt, 2 cesium , 2 lithium salt, sodium salt of phenol, potassium salt, cesium salt, lithium salt or the like is used.
アルカリ土類金属化合物としては、具体的には、水酸化マグネシウム、水酸化カルシウム、水酸化ストロンチウム、水酸化バリウム、炭酸水素マグネシウム、炭酸水素カルシウム、炭酸水素ストロンチウム、炭酸水素バリウム、炭酸マグネシウム、炭酸カルシウム、炭酸ストロンチウム、炭酸バリウム、酢酸マグネシウム、酢酸カルシウム、酢酸ストロンチウム、酢酸バリウム、ステアリン酸マグネシウム、ステアリン酸カルシウム、安息香酸カルシウム、フェニルリン酸マグネシウム等が用いられる。 Specific examples of the alkaline earth metal compound include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydrogen carbonate, calcium hydrogen carbonate, strontium hydrogen carbonate, barium hydrogen carbonate, magnesium carbonate, calcium carbonate. Strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, magnesium phenyl phosphate, and the like are used.
含窒素化合物としては、具体的には、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、トリメチルベンジルアンモニウムヒドロキシド等のアルキル、アリール、基等を有する４級アンモニウムヒドロキシド類、トリエチルアミン、ジメチルベンジルアミン、トリフェニルアミン等の３級アミン類、ジエチルアミン、ジブチルアミン等の２級アミン類、プロピルアミン、ブチルアミン等の１級アミン類、２−メチルイミダゾール、２−フェニルイミダゾール、ベンゾイミダゾール等のイミダゾール類、あるいは、アンモニア、テトラメチルアンモニウムボロハイドライド、テトラブチルアンモニウムボロハイドライド、テトラブチルアンモニウムテトラフェニルボレート、テトラフェニルアンモニウムテトラフェニルボレート等の塩基あるいは塩基性塩等が用いられる。 Specific examples of nitrogen-containing compounds include alkyl, aryl, groups, etc. such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide. Secondary ammoniums such as quaternary ammonium hydroxides, triethylamine, dimethylbenzylamine and triphenylamine, secondary amines such as diethylamine and dibutylamine, primary amines such as propylamine and butylamine, 2-methylimidazole, 2 -Imidazoles such as phenylimidazole and benzimidazole, or ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, Tetrabutylammonium tetraphenylborate, basic or basic salts such as tetraphenyl ammonium tetraphenylborate, or the like is used.
エステル交換触媒としては、亜鉛、スズ、ジルコニウム、鉛の塩が好ましく用いられ、これらは単独もしくは組み合わせて用いることができる。 As the transesterification catalyst, zinc, tin, zirconium and lead salts are preferably used, and these can be used alone or in combination.
エステル交換触媒としては、具体的には、酢酸亜鉛、安息香酸亜鉛、２−エチルヘキサン酸亜鉛、塩化スズ（ＩＩ）、塩化スズ（ＩＶ）、酢酸スズ（ＩＩ）、酢酸スズ（ＩＶ）、ジブチルスズジラウレート、ジブチルスズオキサイド、ジブチルスズジメトキシド、ジルコニウムアセチルアセトナート、オキシ酢酸ジルコニウム、ジルコニウムテトラブトキシド、酢酸鉛（ＩＩ）、酢酸鉛（ＩＶ）等が用いられる。 Specific examples of the transesterification catalyst include zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin (II) chloride, tin (IV) chloride, tin (II) acetate, tin (IV) acetate, and dibutyltin. Dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead (II) acetate, lead (IV) acetate and the like are used.
これらの触媒は、ジヒドロキシ化合物の合計１モルに対して、１０−９〜１０−３モルの比率で用いられ、好ましくは１０−７〜１０−４モルの比率で用いられる。 These catalysts are used in a ratio of 10 −9 to 10 −3 mol, preferably 10 −7 to 10 −4 mol, per 1 mol of the total of dihydroxy compounds.
本発明にかかわる溶融重縮合法は、前記の原料、および触媒を用いて、加熱下に常圧または減圧下にエステル交換反応により副生成物を除去しながら溶融重縮合を行うものである。反応は、一般には二段以上の多段行程で実施される。 The melt polycondensation method according to the present invention is a method in which melt polycondensation is carried out using the above-mentioned raw materials and catalyst while removing by-products by a transesterification reaction under normal pressure or reduced pressure. The reaction is generally carried out in a multistage process of two or more stages.
具体的には、第一段目の反応を１２０〜２６０℃、好ましくは１８０〜２４０℃の温度で０．１〜５時間、好ましくは０．５〜３時間反応させる。次いで反応系の減圧度を上げながら反応温度を高めてジヒドロキシ化合物と炭酸ジエステルとの反応を行い、最終的には１ｍｍＨｇ以下の減圧下、２００〜３００℃の温度で重縮合反応を行う。このような反応は、連続式で行っても良くまたバッチ式で行ってもよい。上記の反応を行うに際して用いられる反応装置は、錨型攪拌翼、マックスブレンド攪拌翼、ヘリカルリボン型攪拌翼等を装備した縦型であっても、パドル翼、格子翼、メガネ翼等を装備した横型であってもスクリューを装備した押出機型であってもよく、また、これらを重合物の粘度を勘案して適宜組み合わせた反応装置を使用することが好適に実施される。 Specifically, the reaction at the first stage is allowed to react at a temperature of 120 to 260 ° C., preferably 180 to 240 ° C. for 0.1 to 5 hours, preferably 0.5 to 3 hours. Next, the reaction temperature is raised while raising the degree of vacuum of the reaction system to carry out the reaction between the dihydroxy compound and the carbonic acid diester, and finally the polycondensation reaction is carried out at a temperature of 200 to 300 ° C. under a reduced pressure of 1 mmHg or less. Such a reaction may be carried out continuously or batchwise. The reaction apparatus used for carrying out the above reaction is equipped with paddle blades, lattice blades, glasses blades, etc. even with vertical types equipped with vertical stirring blades, Max blend stirring blades, helical ribbon stirring blades, etc. It may be a horizontal type or an extruder type equipped with a screw, and it is preferable to use a reaction apparatus in which these are appropriately combined in consideration of the viscosity of the polymer.
本発明にかかわるポリカーボネート樹脂は、重合反応終了後、熱安定性および加水分解安定性を保持するために、触媒を除去もしくは失活させる。一般的には、公知の酸性物質の添加による触媒の失活を行う方法が好適に実施される。これらの酸性物質またはその誘導体としては、具体的には、安息香酸ブチル等のエステル類、ｐ−トルエンスルホン酸等の芳香族スルホン酸類、ｐ−トルエンスルホン酸ブチル、ｐ−トルエンスルホン酸ヘキシル等の芳香族スルホン酸エステル類、亜リン酸、リン酸、ホスホン酸等のリン酸類、亜リン酸トリフェニル、亜リン酸モノフェニル、亜リン酸ジフェニル、亜リン酸モノエチル、亜リン酸ジエチル、亜リン酸モノブチル、亜リン酸ジブチル、亜リン酸ジオクチル、亜リン酸モノオクチル等の亜リン酸エステル類、リン酸トリフェニル、リン酸ジフェニル、リン酸モノフェニル、リン酸モノエチル、リン酸ジエチル、リン酸ジブチル、リン酸ジオクチル、リン酸モノオクチル等のリン酸エステル類、ジフェニルホスホン酸、ジオクチルホスホン酸、ジブチルホスホン酸等のホスホン酸類、フェニルホスホン酸ジエチル等のホスホン酸エステル類、トリフェニルホスフィン、ビス（ジフェニルホスフィノ）エタン等のホスフィン類、ホウ酸、フェニルホウ酸等のホウ酸類、ドデシルベンゼンスルホン酸テトラブチルホスホニウム塩等の芳香族スルホン酸塩類、ステアリン酸クロライド、塩化ベンゾイル、ｐ−トルエンスルホン酸クロライド等の有機ハロゲン化物、ジメチル硫酸等のアルキル硫酸、塩化ベンジル等の有機ハロゲン化物等が好適に用いられる。 In the polycarbonate resin according to the present invention, the catalyst is removed or deactivated after the polymerization reaction in order to maintain thermal stability and hydrolysis stability. In general, a method of deactivating a catalyst by adding a known acidic substance is preferably performed. Specific examples of these acidic substances or derivatives thereof include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, butyl p-toluenesulfonate, and hexyl p-toluenesulfonate. Aromatic sulfonic acid esters, phosphoric acids such as phosphorous acid, phosphoric acid, phosphonic acid, triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, monoethyl phosphite, diethyl phosphite, phosphorus phosphite Phosphorous esters such as monobutyl acid, dibutyl phosphite, dioctyl phosphite, monooctyl phosphite, triphenyl phosphate, diphenyl phosphate, monophenyl phosphate, monoethyl phosphate, diethyl phosphate, phosphoric acid Phosphate esters such as dibutyl, dioctyl phosphate, monooctyl phosphate, diphenylphosphonic acid, dioctyl Phosphonic acids such as sulfonic acid and dibutylphosphonic acid, phosphonic acid esters such as diethyl phenylphosphonate, phosphines such as triphenylphosphine and bis (diphenylphosphino) ethane, boric acids such as boric acid and phenylboric acid, dodecylbenzene Preferred are aromatic sulfonates such as tetrabutylphosphonium sulfonate, organic halides such as stearic acid chloride, benzoyl chloride, p-toluenesulfonic acid chloride, alkyl sulfuric acids such as dimethyl sulfate, and organic halides such as benzyl chloride. Used for.
触媒失活後、ポリマー中の低沸点化合物を０．１〜１ｍｍＨｇの圧力、２００〜３５０℃の温度で脱揮除去する工程を設けても良く、このためには、パドル翼、格子翼、メガネ翼等、表面更新能の優れた攪拌翼を備えた横型装置、あるいは薄膜蒸発器が好適に用いられる。 After deactivation of the catalyst, a step of devolatilizing and removing low-boiling compounds in the polymer at a pressure of 0.1 to 1 mmHg and a temperature of 200 to 350 ° C. may be provided. For this purpose, paddle blades, lattice blades, glasses A horizontal apparatus provided with a stirring blade having excellent surface renewability such as a blade or a thin film evaporator is preferably used.
本発明で製造されるポリカーボネート樹脂フィルムにおいて、本発明の目的および効果を損なわない範囲で、安定剤、着色剤、難燃剤等を配合してもよい。混練機としては、押出機、ラボプラストミル、ニーダー等が用いられるが、連続的に混練を行うなら押出機が、バッチ式で混練を行うならラボプラストミルあるいはニーダーが好適に使用される。 In the polycarbonate resin film produced according to the present invention, a stabilizer, a colorant, a flame retardant, and the like may be blended within a range that does not impair the object and effect of the present invention. As the kneader, an extruder, a lab plast mill, a kneader, or the like is used. An extruder is preferably used for continuous kneading, and a lab plast mill or kneader is preferably used for batch kneading.
本発明の樹脂のフィルム製造方法は押出機によって溶融し、ダイスから取り出すことによってなされても良いし、溶融キャスト法を用いても良い。押出機によって溶融される場合は２００℃〜３００℃で行われるのが望ましく、より望ましくは２１０℃〜２５０℃である。溶融キャスト法に使用する溶剤としては本発明の樹脂が溶解する有機溶剤ならば良いが、メチレンクロライドもしくはクロロホルム等のハロゲン系有機溶剤が望ましい。 The resin film production method of the present invention may be performed by melting with an extruder and taking it out of a die, or may use a melt casting method. When it is melted by an extruder, it is preferably carried out at 200 ° C to 300 ° C, more preferably 210 ° C to 250 ° C. The solvent used in the melt casting method may be an organic solvent in which the resin of the present invention is dissolved, but a halogen-based organic solvent such as methylene chloride or chloroform is desirable.
本発明に使用されるポリカーボネート樹脂の好ましいポリスチレン換算重量平均分子量（Ｍｗ）は、１５，０００〜２００，０００であり、より好ましくは２０，０００〜１００，０００である。Ｍｗが１５，０００より小さいと、脆くなるため好ましくない。Ｍｗが２００，０００より大きいと、押出成形が困難になる為望ましくない。 The preferred polystyrene-reduced weight average molecular weight (Mw) of the polycarbonate resin used in the present invention is 15,000 to 200,000, more preferably 20,000 to 100,000. If Mw is less than 15,000, it is not preferable because it becomes brittle. When Mw is larger than 200,000, extrusion molding becomes difficult, which is not desirable.
以下に本発明を実施例により説明するが、本発明はこれらの実施例に何らの制限を受けるものではない。なお、実施例中の測定値は以下の方法あるいは装置を用いて測定した。
１）ポリスチレン換算重量平均分子量（Ｍｗ）：ＧＰＣを用い、クロロホルムを展開溶媒として、既知の分子量（分子量分布＝１）の標準ポリスチレンを用いて検量線を作成した。この検量線に基づいて、ＧＰＣのリテンションタイムから算出した。
２）ガラス転移温度（Ｔｇ）：示差熱走査熱量分析計（ＤＳＣ）により測定した。
３）光弾性係数：エリプソメーターにより、厚さ１００μｍのキャストフィルムを用い、レーザー波長６３３ｎｍの光をあて、荷重変化に対する複屈折測定から算出した。
４）フィルム強度及び伸度：実施例で得られた厚み１００μｍのフィルムの引張強度及び引張伸度をASTM D８８２―６１Ｔに準拠して、島津製作所製島津オートグラフAGS-100Gを用いて測定した。
EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In addition, the measured value in an Example was measured using the following method or apparatus.
1) Polystyrene-converted weight average molecular weight (Mw): A calibration curve was prepared using standard polystyrene having a known molecular weight (molecular weight distribution = 1) using GPC and chloroform as a developing solvent. Based on this calibration curve, it was calculated from the retention time of GPC.
2) Glass transition temperature (Tg): measured by a differential thermal scanning calorimeter (DSC).
3) Photoelastic coefficient: It calculated from the birefringence measurement with respect to a load change, using a cast film with a thickness of 100 μm and applying light with a laser wavelength of 633 nm using an ellipsometer.
4) Film strength and elongation: The tensile strength and tensile elongation of the film having a thickness of 100 μm obtained in the examples were measured using Shimadzu Shimadzu Autograph AGS-100G according to ASTM D882-61T.
実施例１
スピログリコール８．５２３ｋｇ（２８．０モル）、ペンタシクロデカンジメタノール３．１４９ｋｇ（１２．００モル）、ジフェニルカーボネート８．９１２ｋｇ（４１．４モル）、および炭酸水素ナトリウム０．０２０１６ｇ（２．４×１０−４モル）を攪拌機および留出装置付きの５０リットル反応器に入れ、窒素雰囲気１５０Ｔｏｒｒの下１時間かけて２１５℃に加熱し撹拌した。
その後、２１５℃、１５０Ｔｏｒｒの条件下で２０分間保持しエステル交換反応を行った。さらに１０分かけて２３０℃まで昇温し、２３０℃、１５０Ｔｏｒｒの条件下で１時間保持し、エステル交換反応を進行させた。その後、１０分かけて２４０℃に昇温し、２４０℃で５０分間エステル交換反応を進行させた。その後、１０分かけて１００Ｔｏｒｒに調整し、２４０℃、１００Ｔｏｒｒで２０分間保持した。その後、１０分かけて４０Ｔｏｒｒに調整し、２４０℃、４０Ｔｏｒｒで３０分間保持した。更に２０分かけて１Ｔｏｒｒ以下とし、２４０℃、１Ｔｏｒｒ以下の条件下で1時間撹拌下重合反応を行った。反応終了後、反応器内に窒素を吹き込み加圧にし、生成したポリカーボネート樹脂をペレタイズしながら抜き出した。得られたポリカーボネート樹脂のＭｗ＝５３，０００、Ｔｇ＝１１１℃であった。
Example 1
Spiroglycol 8.523 kg (28.0 mol), pentacyclodecane dimethanol 3.149 kg (12.00 mol), diphenyl carbonate 8.912 kg (41.4 mol), and sodium bicarbonate 0.02016 g (2.4 × 10 −4 mol) was placed in a 50 liter reactor equipped with a stirrer and a distiller, heated to 215 ° C. over 1 hour under a nitrogen atmosphere of 150 Torr, and stirred.
Thereafter, the reaction was carried out for 20 minutes under the conditions of 215 ° C. and 150 Torr to conduct a transesterification reaction. The temperature was further raised to 230 ° C. over 10 minutes, and maintained for 1 hour under the conditions of 230 ° C. and 150 Torr to proceed the transesterification reaction. Thereafter, the temperature was raised to 240 ° C. over 10 minutes, and the transesterification reaction was allowed to proceed at 240 ° C. for 50 minutes. Thereafter, the pressure was adjusted to 100 Torr over 10 minutes and held at 240 ° C. and 100 Torr for 20 minutes. Thereafter, the pressure was adjusted to 40 Torr over 10 minutes and maintained at 240 ° C. and 40 Torr for 30 minutes. Furthermore, the polymerization reaction was carried out with stirring for 1 hour under conditions of 240 ° C. and 1 Torr or less at 20 ° C. over 1 minute. After completion of the reaction, nitrogen was blown into the reactor to increase the pressure, and the produced polycarbonate resin was extracted while being pelletized. It was Mw = 53,000 and Tg = 111 degreeC of the obtained polycarbonate resin.
上記樹脂をＴ字型ダイスをもつ溶融押出成形機で２４０℃で成形し厚さ１５０μｍのフィルムを得た。このフィルムの光弾性係数は３．９×１０−１２ｍ2/Ｎであった。得られたポリカーボネートの物性を表１に示す。 The resin was molded at 240 ° C. with a melt extrusion molding machine having a T-shaped die to obtain a film having a thickness of 150 μm. The photoelastic coefficient of this film was 3.9 × 10 −12 m 2 / N. Table 1 shows the physical properties of the obtained polycarbonate.
実施例２
スピログリコール８．５２３ｋｇ（２８．０モル）、イソソルビド１．７５４ｋｇ（１２．００モル）、ジフェニルカーボネート８．９１２ｋｇ（４１．４モル）、および炭酸水素ナトリウム０．０２０１６ｇ（２．４×１０−４モル）を攪拌機および留出装置付きの５０リットル反応器に入れ、窒素雰囲気１５０Ｔｏｒｒの下１時間かけて２１５℃に加熱し撹拌した。
その後、２１５℃、１５０Ｔｏｒｒの条件下で２０分間保持しエステル交換反応を行った。さらに１０分かけて２３０℃まで昇温し、２３０℃、１５０Ｔｏｒｒの条件下で１時間保持し、エステル交換反応を進行させた。その後、１０分かけて２４０℃に昇温し、２４０℃で５０分間エステル交換反応を進行させた。その後、１０分かけて１００Ｔｏｒｒに調整し、２４０℃、１００Ｔｏｒｒで２０分間保持した。その後、１０分かけて４０Ｔｏｒｒに調整し、２４０℃、４０Ｔｏｒｒで３０分間保持した。更に２０分かけて１Ｔｏｒｒ以下とし、２４０℃、１Ｔｏｒｒ以下の条件下で1時間撹拌下重合反応を行った。反応終了後、反応器内に窒素を吹き込み加圧にし、生成したポリカーボネート樹脂をペレタイズしながら抜き出した。得られたポリカーボネート樹脂のＭｗ＝５６，０００、Ｔｇ＝１１５℃であった。この共重合ポリカーボネートから得られたフィルムの光弾性係数は８．０×１０−１２ｍ2/Ｎであった。得られたポリカーボネートの物性を表１に示す。
Example 2
Spiroglycol 8.523 kg (28.0 mol), isosorbide 1.754 kg (12.00 mol), diphenyl carbonate 8.912 kg (41.4 mol), and sodium hydrogen carbonate 0.02016 g (2.4 × 10 −4) Mol) was placed in a 50 liter reactor equipped with a stirrer and a distillation apparatus, and heated to 215 ° C. over 1 hour under a nitrogen atmosphere of 150 Torr and stirred.
Thereafter, the reaction was carried out for 20 minutes under the conditions of 215 ° C. and 150 Torr to conduct a transesterification reaction. The temperature was further raised to 230 ° C. over 10 minutes, and maintained for 1 hour under the conditions of 230 ° C. and 150 Torr to proceed the transesterification reaction. Thereafter, the temperature was raised to 240 ° C. over 10 minutes, and the transesterification reaction was allowed to proceed at 240 ° C. for 50 minutes. Thereafter, the pressure was adjusted to 100 Torr over 10 minutes and held at 240 ° C. and 100 Torr for 20 minutes. Thereafter, the pressure was adjusted to 40 Torr over 10 minutes and maintained at 240 ° C. and 40 Torr for 30 minutes. Furthermore, the polymerization reaction was carried out with stirring for 1 hour under conditions of 240 ° C. and 1 Torr or less at 20 ° C. over 1 minute. After completion of the reaction, nitrogen was blown into the reactor to increase the pressure, and the produced polycarbonate resin was extracted while being pelletized. It was Mw = 56,000 and Tg = 115 degreeC of the obtained polycarbonate resin. The film obtained from this copolymer polycarbonate had a photoelastic coefficient of 8.0 × 10 −12 m 2 / N. Table 1 shows the physical properties of the obtained polycarbonate.
実施例３
SPG/CHDO＝60/40mol比
スピログリコール６．０８８ｋｇ（２４．０モル）、1,4-シクロヘキサンジオール１．８５９ｋｇ（１６．００モル）、ジフェニルカーボネート８．９１２ｋｇ（４１．４モル）、および炭酸水素ナトリウム０．０２０１６ｇ（２．４×１０−４モル）を攪拌機および留出装置付きの５０リットル反応器に入れ、窒素雰囲気１５０Ｔｏｒｒの下１時間かけて２１５℃に加熱し撹拌した。
その後、２１５℃、１５０Ｔｏｒｒの条件下で２０分間保持しエステル交換反応を行った。さらに１０分かけて２３０℃まで昇温し、２３０℃、１５０Ｔｏｒｒの条件下で１時間保持し、エステル交換反応を進行させた。その後、１０分かけて２４０℃に昇温し、２４０℃で５０分間エステル交換反応を進行させた。その後、１０分かけて１００Ｔｏｒｒに調整し、２４０℃、１００Ｔｏｒｒで２０分間保持した。その後、１０分かけて４０Ｔｏｒｒに調整し、２４０℃、４０Ｔｏｒｒで３０分間保持した。更に２０分かけて１Ｔｏｒｒ以下とし、２４０℃、１Ｔｏｒｒ以下の条件下で1時間撹拌下重合反応を行った。反応終了後、反応器内に窒素を吹き込み加圧にし、生成したポリカーボネート樹脂をペレタイズしながら抜き出した。得られたポリカーボネート樹脂のＭｗ＝５２，０００、Ｔｇ＝１０８℃であった。この共重合ポリカーボネートから得られたフィルムの光弾性係数は５．０×１０−１２ｍ2/Ｎであった。得られたポリカーボネートの物性を表１に示す。
Example 3
SPG / CHDO = 60/40 mol ratio Spiroglycol 6.088 kg (24.0 mol), 1,4-cyclohexanediol 1.859 kg (16.00 mol), diphenyl carbonate 8.912 kg (41.4 mol), and carbonic acid 0.02016 g (2.4 × 10 −4 mol) of sodium hydride was placed in a 50 liter reactor equipped with a stirrer and a distillation apparatus, and heated to 215 ° C. and stirred for 1 hour under a nitrogen atmosphere of 150 Torr.
Thereafter, the reaction was carried out for 20 minutes under the conditions of 215 ° C. and 150 Torr to conduct a transesterification reaction. The temperature was further raised to 230 ° C. over 10 minutes, and maintained for 1 hour under the conditions of 230 ° C. and 150 Torr to proceed the transesterification reaction. Thereafter, the temperature was raised to 240 ° C. over 10 minutes, and the transesterification reaction was allowed to proceed at 240 ° C. for 50 minutes. Thereafter, the pressure was adjusted to 100 Torr over 10 minutes and held at 240 ° C. and 100 Torr for 20 minutes. Thereafter, the pressure was adjusted to 40 Torr over 10 minutes and maintained at 240 ° C. and 40 Torr for 30 minutes. Furthermore, the polymerization reaction was carried out with stirring for 1 hour under conditions of 240 ° C. and 1 Torr or less at 20 ° C. over 1 minute. After completion of the reaction, nitrogen was blown into the reactor to increase the pressure, and the produced polycarbonate resin was extracted while being pelletized. It was Mw = 52,000 and Tg = 108 degreeC of the obtained polycarbonate resin. The photoelastic coefficient of the film obtained from this copolymer polycarbonate was 5.0 × 10 −12 m 2 / N. Table 1 shows the physical properties of the obtained polycarbonate.
比較例１
仕込みをペンタシクロペンタデカンジメタノールからトリシクロデカンジメタノール２．３５５ｋｇ（１２．００）ｍｏｌに替えた以外は実施例１と全く同じ方法で行った。Mw＝５７，０００の樹脂が得られた。この共重合ポリカーボネートから得られたフィルムの光弾性係数は４．５×１０−１２ｍ2/Ｎであったが、Ｔｇが９６℃となり、Ｔｇ≧１００℃を満たさず、耐熱性に劣ることが明らかであった。得られたポリカーボネートの物性を表１に示す。
Comparative Example 1
The procedure was exactly the same as in Example 1, except that the charge was changed from pentacyclopentadecane dimethanol to 2.355 kg (12.00) mol of tricyclodecane dimethanol. A resin with Mw = 57,000 was obtained. The photoelastic coefficient of the film obtained from this copolymerized polycarbonate was 4.5 × 10 −12 m 2 / N, but Tg was 96 ° C., Tg ≧ 100 ° C. was not satisfied, and heat resistance was inferior. It was clear. Table 1 shows the physical properties of the obtained polycarbonate.
比較例２
仕込みをペンタシクロペンタデカンジメタノールからビスフェノールＡ２．７３９ｋｇ（１２．００）ｍｏｌに替えた以外は実施例１と同じ方法を用いた。Mw＝５８，０００の樹脂が得られた。この樹脂は光弾性係数Ｋが３０×１０−１２ｍ2/Ｎと高くフィルム用途として本発明より劣ることが明らかであった。得られたポリカーボネートの物性を表１に示す。
Comparative Example 2
The same method as in Example 1 was used, except that the charge was changed from pentacyclopentadecane dimethanol to 2.739 kg (12.00) mol of bisphenol A. A resin with Mw = 58,000 was obtained. This resin had a high photoelastic coefficient K of 30 × 10 −12 m 2 / N, and was clearly inferior to the present invention as a film application. Table 1 shows the physical properties of the obtained polycarbonate.
Claims (8)
The optical film according to claim 7, wherein the optical film is a retardation film.
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