JP5001110B2 - Polycarbonate resin and method for producing the same - Google Patents

Description

  The present invention relates to a novel polycarbonate resin and a method for producing the same. More specifically, it is a polycarbonate resin that contains a part that can be derived from a carbohydrate that is a biogenic substance, has both good heat resistance and heat stability, and excellent hue, and is a material for various molding materials and polymer alloy materials. The present invention relates to a polycarbonate resin useful as a method and a production method thereof.

  The polycarbonate resin is a polymer in which an aromatic or aliphatic dioxy compound is linked by a carbonic acid ester, and among them, a polycarbonate resin obtained from 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A) (hereinafter “PC-”). A ”(sometimes referred to as“ A ”) is excellent in transparency and heat resistance, and has excellent mechanical properties such as impact resistance and is used in many fields.

  Polycarbonate resins are generally produced using raw materials obtained from petroleum resources. However, there is a concern about the exhaustion of petroleum resources, and there is a demand for production of polycarbonate resins using raw materials obtained from biological materials such as plants. ing.

  A typical example of a biomass material that uses biogenic materials as raw materials is polylactic acid. Among biomass plastics, it has relatively high heat resistance and mechanical properties, so its application is expanding to tableware, packaging materials, general merchandise, etc. However, the possibility as an industrial material has been studied. However, polylactic acid has insufficient heat resistance when used as an industrial material, and when it is attempted to obtain a molded product by injection molding with high productivity, the crystalline polymer is low in crystallinity, so that the moldability is low. Is inferior. From this point of view, considering the development of biomass materials into industrial materials, there is a demand for amorphous biomass materials such as polycarbonate resins.

  As a polycarbonate resin using a biogenic material as a raw material, a polycarbonate resin using a raw material obtained from an ether diol residue that can be produced from a saccharide in addition to a polylactic acid resin has been studied.

に示したエーテルジオールは、たとえば糖類およびでんぷんなどから容易に作られ、３種の立体異性体が知られているが、具体的には下記式（ｂ）

に示す、１，４：３，６ージアンヒドローＤーソルビトール（本明細書では以下「イソソルビド」と呼称する）、下記式（ｃ）

に示す、１，４：３，６ージアンヒドローＤーマンニトール（本明細書では以下「イソマンニド」と呼称する）、下記式（ｄ）

に示す、１，４：３，６ージアンヒドローＬーイジトール（本明細書では以下「イソイディッド」と呼称する）である。 For example, the following formula (a)

The ether diol shown in Fig. 2 is easily made from, for example, sugars and starch, and three stereoisomers are known. Specifically, the following formula (b)

1,4: 3,6-dianhydro-D-sorbitol (hereinafter referred to as “isosorbide”), represented by the following formula (c)

1,4: 3,6-dianhydro-D-mannitol (hereinafter referred to as “isomannide”), represented by the following formula (d):

1,4: 3,6-dianhydro-L-iditol (hereinafter referred to as “isoidid” in the present specification).

  Isosorbide, isomannide, and isoidide are obtained from D-glucose, D-mannose, and L-idose, respectively. For example, isosorbide can be obtained by hydrogenating D-glucose and then dehydrating it using an acid catalyst.

  So far, among the above-mentioned ether diols, in particular, incorporation into polycarbonate using isosorbide as a monomer has been studied. Among them, isosorbide homopolycarbonate is described in Patent Documents 1 and 2 and Non-Patent Documents 1 and 2.

  Of these, Patent Document 1 reports a homopolycarbonate resin having a melting point of 203 ° C. using a melt transesterification method. However, this polymer has insufficient mechanical properties. In Non-Patent Document 1, a homopolycarbonate resin having a glass transition temperature of 166 ° C. is obtained in a melt transesterification method using zinc acetate as a catalyst, but a thermal decomposition temperature (5% weight loss temperature) is 283 ° C. Stability is not enough. In Non-Patent Document 2, homopolycarbonate resin is obtained by interfacial polymerization using bischloroformate of isosorbide, but the glass transition temperature is 144 ° C. and the heat resistance is not sufficient. On the other hand, as an example of high heat resistance, Patent Document 2 reports a polycarbonate having a glass transition temperature of 170 ° C. or higher by differential calorimetry at a heating rate of 10 ° C./min. However, when an ether diol that can be produced from such a saccharide is used as a raw material for the polymer, the polymer is likely to be colored, causing a problem in practical use.

British Patent Application No. 1079686 International Publication No. 2007/013463 Pamphlet International Publication No. 2004/008648 Pamphlet “Journal of Applied Polymer Science”, 2002, Vol. 86, p. 872-880 “Macromolecules”, 1996, Vol. 29, p. 8077-8082

  The present invention solves the above problems, and provides a polycarbonate resin useful as an industrial material exhibiting high biogenic substance content, good heat resistance and thermal stability, and excellent in hue. Objective.

で表されるカーボネート構成単位を含有するポリカーボネート樹脂中に含まれる炭素−炭素二重結合成分がポリマーの着色に深く関わりがある事を見出した。更に、重合触媒として含窒素塩基性化合物およびアルカリ金属化合物を使用し、上記式（ａ）で表されるエーテルジオールを含むジオール成分と炭酸ジエステルとを、加熱減圧下で溶融重縮合させる該ポリカーボネート樹脂の製造方法において、重合触媒を特定の量および比率とすることで、その二重結合成分含有量が低減し、色相が改善されることを見出した。さらに、溶融重合の際に特定の有機リン化合物を存在させることにより、さらに色相に優れたポリカーボネート樹脂を得られることを見出し、本発明に至った。 As a result of intensive studies to achieve the above object, the present inventor has found that the following formula (1)

It was found that the carbon-carbon double bond component contained in the polycarbonate resin containing the carbonate structural unit represented by the formula is deeply related to the coloring of the polymer. Further, the polycarbonate resin, which uses a nitrogen-containing basic compound and an alkali metal compound as a polymerization catalyst, and melt polycondensates the diol component containing the ether diol represented by the above formula (a) and a carbonic acid diester under heating and reduced pressure. In the production method, it was found that the content of the double bond component is reduced and the hue is improved by setting the polymerization catalyst to a specific amount and ratio. Furthermore, the present inventors have found that a polycarbonate resin having further excellent hue can be obtained by the presence of a specific organophosphorus compound during melt polymerization.

２．樹脂０．７ｇを塩化メチレン１００ｍｌに溶解した溶液の２０℃における比粘度が０．１４〜０．５５である前項１記載のポリカーボネート樹脂、
３．樹脂０．７ｇを塩化メチレン１００ｍｌに溶解した溶液の２０℃における比粘度が０．２０〜０．４５である前項１記載のポリカーボネート樹脂、
４．２５０℃におけるキャピラリーレオメータで測定した溶融粘度が、シェアレート６００ｓｅｃ^ー１の条件下で０．２×１０^３〜４．０×１０^３Ｐａ・ｓの範囲にある前項１記載のポリカーボネート樹脂、
５．ガラス転移温度（Ｔｇ）が１２０℃〜１７５℃であり、かつ５％重量減少温度（Ｔｄ）が３２０〜４００℃である前項１記載のポリカーボネート樹脂、
６．ガラス転移温度（Ｔｇ）が１４５℃〜１７０℃であり、かつ５％重量減少温度（Ｔｄ）が３２０〜４００℃である前項１記載のポリカーボネート樹脂、
７．上記式（１）で表されるカーボネート構成単位がイソソルビド（１，４：３，６ージアンヒドローＤーソルビトール）由来のカーボネート構成単位である前項１記載のポリカーボネート樹脂、
８．全カーボネート構成単位中、前記式（１）で表わされる構成単位は６０モル％以上である前項１記載のポリカーボネート樹脂、
９．重合触媒として含窒素塩基性化合物およびアルカリ金属化合物を使用し、下記式（ａ）で表されるエーテルジオールを含むジオール成分と炭酸ジエステルとを、加熱減圧下で溶融重縮合させるポリカーボネート樹脂の製造方法において、ジオール成分と炭酸ジエステルとを常圧で加熱溶融させた時のアルカリ金属の濃度を溶融溶液中０．１〜１．０ｐｐｍで、かつ含窒素塩基性化合物とアルカリ金属との割合が重量比で５０／１〜２０００／１（含窒素塩基性化合物／アルカリ金属）の範囲となるように重合触媒量を調整することを特徴とする前項１記載のポリカーボネート樹脂の製造方法、

１０．上記式（ａ）で表されるエーテルジオールを含むジオール成分と炭酸ジエステルとを、常圧で加熱溶融する際に、下記式（４）で表される有機リン化合物を炭酸ジエステルに対して２００〜３０００ｐｐｍ添加する前項９記載のポリカーボネート樹脂の製造方法、および

（上記式（４）において、Ｒ^１は水素原子または炭素原子数１〜１０のアルキル基であり、Ｒ^２は炭素原子数４〜１０のアルキル基であり、Ｒ^３は水素原子、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数６〜２０のシクロアルキル基、炭素原子数６〜２０のシクロアルコキシ基、炭素原子数２〜１０のアルケニル基、炭素原子数６〜１０のアリール基、炭素原子数６〜１０のアリールオキシ基、炭素原子数７〜２０のアラルキル基および炭素原子数７〜２０のアラルキルオキシ基からなる群から選ばれる少なくとも１種の基である。）
１１．前項１記載のポリカーボネート樹脂から形成された成形品、
が提供される。 That is, according to the present invention: A polycarbonate resin containing a carbonate constituent unit represented by the following formula (1), wherein the polymer terminal contains a carbon-carbon double bond component represented by the following formula (2) and the following formula (3). The total value of the above-mentioned carbonate constituent unit is 0.3% or less, and the b value of a 15% by weight methylene chloride solution of polycarbonate resin measured at an optical path length of 30 mm is 5.0 or less. Polycarbonate resin,

2. The polycarbonate resin according to item 1 above, wherein a specific viscosity at 20 ° C. of a solution obtained by dissolving 0.7 g of resin in 100 ml of methylene chloride is 0.14 to 0.55;
3. The polycarbonate resin according to the above item 1, wherein the specific viscosity at 20 ° C. of a solution prepared by dissolving 0.7 g of resin in 100 ml of methylene chloride is 0.20 to 0.45;
4. The polycarbonate resin according to item ¹ above, wherein the melt viscosity measured with a capillary rheometer at 250 ° C. is in the range of 0.2 × 10 ^{3 to} 4.0 × 10 ³ Pa · s under the condition of a shear rate of 600 sec ^-1 .
5. 2. The polycarbonate resin according to item 1, wherein the glass transition temperature (Tg) is 120 ° C. to 175 ° C. and the 5% weight loss temperature (Td) is 320 to 400 ° C.
6). 2. The polycarbonate resin according to item 1, wherein the glass transition temperature (Tg) is 145 ° C. to 170 ° C., and the 5% weight loss temperature (Td) is 320 to 400 ° C.
7). The polycarbonate resin according to item 1, wherein the carbonate constituent unit represented by the formula (1) is a carbonate constituent unit derived from isosorbide (1,4: 3,6-dianhydro-D-sorbitol).
8). The polycarbonate resin according to item 1, wherein the structural unit represented by the formula (1) is 60 mol% or more in all carbonate structural units;
9. A method for producing a polycarbonate resin, wherein a nitrogen-containing basic compound and an alkali metal compound are used as a polymerization catalyst, and a diol component containing an ether diol represented by the following formula (a) and a carbonic diester are melt polycondensed under heating and reduced pressure In the above, the concentration of the alkali metal when the diol component and the carbonic acid diester are heated and melted at normal pressure is 0.1 to 1.0 ppm in the molten solution, and the ratio of the nitrogen-containing basic compound and the alkali metal is the weight ratio. The method for producing a polycarbonate resin according to item 1 above, wherein the polymerization catalyst amount is adjusted to be in the range of 50/1 to 2000/1 (nitrogen-containing basic compound / alkali metal),

10. When the diol component containing the ether diol represented by the above formula (a) and the carbonic acid diester are heated and melted at normal pressure, the organic phosphorus compound represented by the following formula (4) is 200 to 200 carbonic acid diesters. The method for producing a polycarbonate resin according to 9 above, wherein 3000 ppm is added, and

(In the above formula (4), R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² is an alkyl group having 4 to 10 carbon atoms, and R ³ is a hydrogen atom or the number of carbon atoms. An alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, carbon At least one selected from the group consisting of an aryl group having 6 to 10 atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aralkyloxy group having 7 to 20 carbon atoms. Group.)
11. A molded product formed from the polycarbonate resin according to the preceding item 1,
Is provided.

Hereinafter, the present invention will be described in detail.
The polycarbonate resin (component A) used in the present invention is a polycarbonate resin containing a carbonate constituent unit represented by the formula (1), and among all the carbonate constituent units, the constituent unit represented by the formula (1) is 60. It is preferably at least mol%, more preferably at least 70 mol%, further preferably at least 80 mol%, particularly preferably at least 90 mol%. Most preferably, it is a homopolycarbonate resin consisting only of the carbonate structural unit of the formula (1).

The polycarbonate resin of the present invention is a polycarbonate resin containing a carbonate constituent unit represented by the above formula (1), and a carbon-carbon double represented by the above formula (2) and the above formula (3) at the polymer terminal. The total amount of the binder component is 0.3% or less, preferably 0.2% or less, particularly preferably 0.15% or less with respect to the carbonate structural unit. The ratio was determined from the integral value of ¹ HNMR of the polycarbonate as follows.

That is, in ¹ HNMR (heavy solvent: CDCl ₃ ) of the polycarbonate resin containing the carbonate structural unit represented by the above formula (1), when the integral intensity of the proton represented by H ^h in FIG. When the integrated intensity of the carbon-carbon double bond component (peak of 6.5 to 6.7 ppm: see FIG. 2) is L, the ratio is represented by the following formula (A).

  The polycarbonate resin of the present invention has a solution b value of not more than 5.0, preferably not more than 4.5, particularly preferably not more than 4.0, when measured at an optical path length of 30 mm in a 15% by weight methylene chloride solution of the polycarbonate resin. . The solution b value was measured using a Nippon Denshoku Co., Ltd. color difference meter 300A with the above solution placed in a sample tube with an optical path length of 30 mm.

In the polycarbonate resin of the present invention, the lower limit of the specific viscosity at 20 ° C. of a solution obtained by dissolving 0.7 g of resin in 100 ml of methylene chloride is preferably 0.14 or more, more preferably 0.20 or more, and further Preferably it is 0.22 or more. The upper limit of the specific viscosity is preferably 0.55 or less, more preferably 0.45 or less, and still more preferably 0.37 or less. When the specific viscosity is lower than 0.14, it becomes difficult to give the molded product obtained from the polycarbonate resin of the present invention sufficient mechanical strength. On the other hand, if the specific viscosity is higher than 0.55, the melt fluidity becomes too high, and the melting temperature having the fluidity necessary for molding becomes higher than the decomposition temperature, which is not preferable. The polycarbonate resin of the present invention has a melt viscosity measured with a capillary rheometer at 250 ° C. in the range of 0.2 × 10 ^{3 to} 4.0 × 10 ³ Pa · s under the condition of a shear rate of 600 sec ^−1. Preferably, it is in the range of 0.4 × 10 ^{3 to} 3.0 × 10 ³ Pa · s, more preferably in the range of 0.4 × 10 ^{3 to} 2.4 × 10 ³ Pa · s. Is more preferable. When the melt viscosity is in this range, the mechanical strength is excellent, and the moldability is good without the occurrence of silver during molding.

  The polycarbonate resin of the present invention has a glass transition temperature (Tg) of preferably 120 to 175 ° C, more preferably 145 to 170 ° C, and further preferably 145 to 165 ° C. When Tg is less than 120 ° C, the heat resistance (particularly heat resistance due to moisture absorption) is poor, and when it exceeds 175 ° C, the melt fluidity during molding is poor. Tg is measured by DSC (model DSC2910) manufactured by TA Instruments.

  Further, the polycarbonate resin of the present invention has a 5% weight reduction temperature of preferably 320 to 400 ° C, more preferably 330 to 400 ° C. A 5% weight loss temperature within the above range is preferable because there is almost no decomposition of the resin during melt molding. The 5% weight loss temperature is measured by TA Instruments TGA (model TGA2950).

で表されるイソソルビド、イソマンニド、イソイディッドなどが挙げられる。 The polycarbonate resin of the present invention can be produced by a melt polymerization method from a diol component containing an ether diol represented by the above formula (a) and a carbonic acid diester. As the ether diol, specifically, the following formulas (b), (c) and (d)

And isosorbide, isomannide, and isoidide represented by the formula:

  These saccharide-derived ether diols are substances obtained from natural biomass and are one of so-called renewable resources. Isosorbide is obtained by hydrogenating D-glucose obtained from starch and then dehydrating it. Other ether diols can be obtained by the same reaction except for the starting materials.

  In particular, a polycarbonate resin in which the carbonate structural unit includes a carbonate structural unit derived from isosorbide (1,4: 3,6-dianhydro-D-sorbitol) is preferable. Isosorbide is an ether diol that can be easily made from starch, etc., and can be obtained in abundant resources. In addition, it is superior in terms of ease of manufacture, properties, and versatility compared to isomannide and isoidide. .

  As a method for producing the polycarbonate resin of the present invention, a melt weight in which the ether diol represented by the above formula (a) and a carbonic acid diester are mixed and the alcohol or phenol produced by the transesterification reaction is distilled under high temperature and reduced pressure. Legal methods are preferably used.

  The reaction temperature is preferably as low as possible in order to suppress decomposition of the ether diol and obtain a highly viscous resin with little coloration, but the polymerization temperature is 180 ° C. to 280 ° C. in order to proceed the polymerization reaction appropriately. It is preferably in the range of ° C, more preferably in the range of 180 ° C to 270 ° C.

In the initial stage of the reaction, ether diol and carbonic acid diester are heated at normal pressure and pre-reacted, and then gradually reduced in pressure, and the system is changed to 1.3 × 10 ^{−3 to} 1.3 × 10 ^{− in the} late stage of the reaction. A method of facilitating the distillation of alcohol or phenol produced by reducing the pressure to about ⁵ MPa is preferred. The reaction time is usually about 0.5 to 4 hours.

  Examples of the carbonic acid diester used in the production of the polycarbonate resin of the present invention include esters such as optionally substituted aryl groups having 6 to 20 carbon atoms, aralkyl groups, or alkyl groups having 1 to 18 carbon atoms. Specific examples include diphenyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (p-butylphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. preferable.

  The carbonic acid diester is preferably mixed so as to have a molar ratio of 1.02 to 0.98 with respect to the total diol compound, more preferably 1.01 to 0.98, still more preferably 1.01 to 0. .99. If the molar ratio of the carbonic acid diester is more than 1.02, the carbonic acid diester residue acts as a terminal block and a sufficient degree of polymerization cannot be obtained, which is not preferable. Even when the molar ratio of carbonic acid diester is less than 0.98, a sufficient degree of polymerization cannot be obtained, which is not preferable.

  A polymerization catalyst can be used to increase the polymerization rate. Examples of the polymerization catalyst include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, alkali metal compounds such as sodium salt or potassium salt of dihydric phenol, tetramethylammonium hydroxide, tetraethylammonium hydroxide, Examples thereof include nitrogen-containing basic compounds such as tetrabutylammonium hydroxide, trimethylamine, and triethylamine. As a method for obtaining the polycarbonate resin of the present invention, it is preferable to use a combination of a nitrogen-containing basic compound and an alkali metal compound. In order to obtain a polycarbonate resin having a good hue, it is important to adjust the alkali metal concentration. Come. In addition to being added as a catalyst, the alkali metal may be contained in the ether diol represented by the above formula (a), which is a raw material (see JP 2005-509667 A), and is therefore contained in the ether diol. It is preferable to adjust the alkali metal concentration in consideration of the alkali metal content.

  In the present invention, the alkali metal concentration in the molten solution when melted by heating at normal pressure is preferably 0.1 to 1.0 ppm, more preferably 0.1 to 0.7 ppm, and still more preferably 0.1. It is adjusted to ˜0.5 ppm, particularly preferably 0.1 to 0.3 ppm. When the alkali metal concentration is less than 0.1 ppm, it is not possible to obtain a polycarbonate resin having a sufficiently low polymerization catalyst activity and having a target specific viscosity. This will cause the hue to deteriorate. The molten solution is defined as a molten solution when ether diol and carbonic acid diester are mixed and melted.

  The amount of the nitrogen-containing basic compound used in combination with the alkali metal compound is such that the ratio of the nitrogen-containing basic compound and the alkali metal is 50/1 to 2000/1 by weight ratio (nitrogen-containing basic compound / alkali metal). It is preferable to mix | blend so that it may become this range. This ratio is more preferably 100/1 to 2000/1, and particularly preferably 100/1 to 1000/1. When the ratio of the nitrogen-containing basic compound and the alkali metal is within this range, a polycarbonate resin having a good hue can be obtained.

  Further, the reaction system is preferably maintained in an atmosphere of a gas inert to raw materials such as nitrogen, reaction mixture, and reaction product. Examples of inert gases other than nitrogen include argon. Furthermore, an additive such as an antioxidant may be added as necessary, but an organic phosphorus compound represented by the following formula (4), which is an antioxidant, is particularly preferable.

In the above formula (4), R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, particularly a hydrogen atom, a methyl group, or an isopropyl group. , An isobutyl group, a tert-butyl group, or a tert-pentyl group is preferable.

R ² is an alkyl group having 4 to 10 carbon atoms, preferably an alkyl group having 4 to 6 carbon atoms, and particularly preferably an isobutyl group, a tert-butyl group, a tert-pentyl group, or a cyclohexyl group.

R ³ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, or a carbon atom. From an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aralkyloxy group having 7 to 20 carbon atoms At least one group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, particularly a hydrogen atom or 1 to 10 carbon atoms. Are preferred.

  Preferred examples of the above formula (4) include bis (2-tert-butylphenyl) pentaerythritol diphosphite, bis (2-tert-pentylphenyl) pentaerythritol diphosphite, bis (2-cyclohexylphenyl) pentaerythritol diphosphite. Phyto, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphos And bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is preferable. Such an antioxidant may be one kind or a mixture of two or more kinds.

  The addition amount of the antioxidant is preferably 200 to 3000 ppm, more preferably 500 to 3000 ppm, and particularly preferably 500 to 2500 ppm with respect to the carbonic acid diester. When the antioxidant is within this range, it is possible to suppress a decrease in molecular weight or a deterioration in hue due to thermal decomposition when the polycarbonate resin of the present invention is produced.

  A catalyst deactivator can also be added to the polycarbonate resin obtained by the above production method. As the catalyst deactivator, known catalyst deactivators are effectively used. Among them, ammonium salts and phosphonium salts of sulfonic acid are preferable, and further, dodecylbenzenesulfonic acid such as tetrabutylphosphonium salt of dodecylbenzenesulfonic acid is preferable. The salts of paratoluenesulfonic acid such as the above-mentioned salts and paratoluenesulfonic acid tetrabutylammonium salt are preferred. As esters of sulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl paratoluenesulfonate, ethyl paratoluenesulfonate, butyl paratoluenesulfonate, para Octyl toluenesulfonate, phenyl p-toluenesulfonate and the like are preferably used, and among them, tetrabutylphosphonium dodecylbenzenesulfonate is most preferably used. These catalyst deactivators are used in an amount of 0.5 to 50 mol, preferably 0.5 to 10 mol, per mol of the polymerization catalyst selected from alkali metal compounds and / or alkaline earth metal compounds. It can be used in a proportion, more preferably in a proportion of 0.8 to 5 mol.

  In addition, the polycarbonate resin used in the present invention may be copolymerized with aliphatic diols and / or aromatic bisphenols within a range that does not impair the properties thereof. The proportion of the aliphatic diols and / or aromatic bisphenols in the total diol component is preferably 40 mol% or less, more preferably 30 mol% or less, further preferably 20 mol% or less, and particularly preferably 10 mol% or less. .

（式中、ｍは１〜２０の整数） As the aliphatic diol, an aliphatic diol represented by the following formula (α) is preferably used.

(Where m is an integer from 1 to 20)

  Specifically, linear diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanediol, cyclohexanedimethanol, etc. Among these, 1,3-propanediol, 1,4-butanediol, hexanediol, and cyclohexanedimethanol are preferable.

  As aromatic bisphenols, 2,2-bis (4-hydroxyphenyl) propane (commonly known as “bisphenol A”), 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4 '-(m-phenylenediisopropylidene) diphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 2,2-bis (4 -Hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) decane, 1,3-bis {2- (4 -Hydroxyphenyl) propyl} benzene and the like.

  In addition to the ether diol represented by the above formula (1), the aliphatic diol represented by the above formula (2) and the aromatic bisphenol, other diol residues can also be contained. Other diols include aromatic diols such as dimethanolbenzene and diethanolbenzene.

で表される末端基が好ましい。 Furthermore, the polycarbonate resin of this invention can also introduce | transduce an end group in the range which does not impair the characteristic. Such end groups can be introduced by adding the corresponding hydroxy compound during polymerization. As the terminal group, the following formula (5) or (6)

The terminal group represented by these is preferable.

であり、好ましくは炭素原子数４〜２０のアルキル基、炭素原子数４〜２０のパーフルオロアルキル基、または上記式（７）であり、特に炭素原子数８〜２０のアルキル基、または上記式（７）が好ましい。Ｘは単結合、エーテル結合、チオエーテル結合、エステル結合、アミノ結合およびアミド結合からなる群より選ばれる少なくとも一種の結合が好ましいが、より好ましくは単結合、エーテル結合およびエステル結合からなる群より選ばれる少なくとも一種の結合であり、なかでも単結合、エステル結合が好ましい。ａは１〜５の整数であり、好ましくは１〜３の整数であり、特に１が好ましい。 In the above formulas (5) and (6), R ⁴ represents an alkyl group having 4 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, a perfluoroalkyl group having 4 to 30 carbon atoms, or the following formula ( 7)

Preferably an alkyl group having 4 to 20 carbon atoms, a perfluoroalkyl group having 4 to 20 carbon atoms, or the above formula (7), particularly an alkyl group having 8 to 20 carbon atoms, or the above formula. (7) is preferred. X is preferably at least one bond selected from the group consisting of a single bond, ether bond, thioether bond, ester bond, amino bond and amide bond, more preferably selected from the group consisting of a single bond, ether bond and ester bond. It is at least one kind of bond, and among them, a single bond and an ester bond are preferable. a is an integer of 1 to 5, preferably an integer of 1 to 3, and 1 is particularly preferable.

In the above formula (7), R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, It is at least one group selected from the group consisting of an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, preferably each independently a carbon atom. And at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 10 carbon atoms, particularly at least one group independently selected from the group consisting of a methyl group and a phenyl group. Is preferred. b is an integer of 0 to 3, an integer of 1 to 3 is preferable, and an integer of 2 to 3 is particularly preferable. c is an integer of 4 to 100, preferably an integer of 4 to 50, and particularly preferably an integer of 8 to 50.

  Since the polycarbonate resin of the present invention has a carbonate structural unit in the main chain structure using a raw material obtained from renewable resources such as plants, these hydroxy compounds are also raw materials obtained from renewable resources such as plants. It is preferable. Examples of hydroxy compounds obtained from plants include long-chain alkyl alcohols having 14 or more carbon atoms (cetanol, stearyl alcohol, behenyl alcohol) obtained from vegetable oils.

  In addition, various additives (function-imparting agents) may be added to the polycarbonate resin of the present invention, for example, plasticizers, light stabilizers, heavy metal deactivators, impact absorbers, flame retardants. , Lubricants, antistatic agents, UV absorbers and the like. Furthermore, various organic and inorganic fillers, fibers and the like can be used in combination in the polycarbonate resin of the present invention depending on the application. Examples of the filler include carbon, talc, mica, wollastonite, montmorillonite, and hydrotalcite. Examples of the fibers include natural fibers such as kenaf, various synthetic fibers, glass fibers, quartz fibers, and carbon fibers.

  Further, the polycarbonate resin of the present invention includes, for example, aliphatic polyester, aromatic polyester, aromatic polycarbonate, polyamide, polystyrene, polyolefin, polyacryl, ABS, polyurethane, and various biological origins including polylactic acid. It can also be used by mixing with a polymer made of a substance and forming an alloy.

  The polycarbonate resin of the present invention contains a part derived from a biogenic material, has both good heat resistance and heat stability, excellent moldability, and good hue, so that it is an optical sheet and optical disk. It can be widely used in various applications including optical parts such as information discs, optical lenses and prisms, various machine parts, building materials, automobile parts, various resin trays, tableware and the like.

  The following examples further illustrate the present invention. However, the present invention is not limited to these examples. Moreover, the part in an Example is a weight part and% is weight%. The evaluation was based on the following method.

(1) Specific viscosity η _sp
The pellet was dissolved in methylene chloride, the concentration was about 0.7 g / dL, and the temperature was measured at 20 ° C. using an Ostwald viscometer (device name: RIGO AUTO VISCOSIMETER TYPE VMR-0525 · PC). The specific viscosity η _sp is obtained from the following formula.
η _sp = t / t _o −1
t: Flow time of sample solution t _o : Flow time of solvent only

(2) Melt viscosity Obtained as a result of measurement using a capillary rheometer (Capillograph model 1D) manufactured by Toyo Seiki Co., Ltd. with a capillary length of 10.0 mm, a capillary diameter of 1.0 mm, and a measurement temperature of 250 ° C. The melt viscosity at 600 sec ⁻¹ was read from the obtained Shear Rate / Viscosity curve.

(3) Glass transition temperature Measured by DSC (model DSC2910) manufactured by TA Instruments.

(4) 5% weight loss temperature Measured with TGA (Model TGA2950) manufactured by TA Instruments.

(5) Hue (solution b value)
The pellet was dissolved in methylene chloride and the concentration was set to 15% by weight and placed in a sample tube having an optical path length of 30 mm. Subsequently, it measured using the Nippon Denshoku Co., Ltd. color difference meter 300A at 20 degreeC. The b value is derived from the Hunter's color difference formula from the tristimulus values X, Y, and Z specified in JIS Z8722. The lower the value, the closer the hue is to colorless.

(6) Ratio of carbon-carbon double bond component The pellet is dissolved in a heavy solvent (CDCl ₃ ), ¹ HNMR measurement is performed, and the integrated value of the specific proton in the carbonate constituent unit represented by the above formula (1) and the above The ratio of the carbon-carbon double bond component was calculated from the ratio with the integral value of the specific proton derived from the carbon-carbon double bond component represented by the formula (2) or (3). About the method of calculating this ratio, Example 1 is shown below as a specific example. The NMR used is JNM-AL400 manufactured by JEOL.

(7) Alkali metal content ICP emission analyzer VISTA MP-X (multi type) (manufactured by Varian) was used.

Reference Example 1 Production of Isosorbide 1930 parts by weight of a 70% aqueous solution of sorbitol (Sorbit (registered trademark) D-70 (manufactured by Towa Kasei Kogyo Co., Ltd.)) in a vacuum reactor equipped with a glass stirrer with a capacity of 2 L and under reduced pressure of 40 Torr The mixture was heated to 120 ° C. to distill water, 32 parts by weight of 98% concentrated sulfuric acid was added, and the mixture was reacted for 24 hours under reduced pressure to distill 262 parts by weight of water. The reaction mixture was neutralized with 40% aqueous sodium hydroxide to pH 7.2 (1% aqueous solution) The reaction was heated to 130 ° C. under reduced pressure and the water was distilled off to remove crude isosorbide. The crude isosorbide was charged into a vacuum still and heated to a bath temperature of 210 ° C. under a reduced pressure of 9 Torr to obtain 788 parts by weight of a distillate over about 3 hours. 760 parts by weight of pure water was added to the distillate and diluted and dissolved, 146 parts by weight of powdered activated carbon was added, and the mixture was stirred at 60 ° C. for 6 hours. 1434 parts by weight of this aqueous solution was placed in a vacuum distillation apparatus, and water was distilled off at 130 ° C. and 50 Torr, followed by distillation at 190 ° C. and 9 Torr to obtain 734 parts by weight of white isosorbide. The metal content was 1.1 ppm.

Reference Example 2 Preparation of Isosorbide with Different Alkali Metal Concentration Isosorbide obtained in Reference Example 1 was purified by recrystallization (recrystallization solvent: methanol). The alkali metal content of this recrystallized isosorbide was 0.2 ppm.
Further, the recrystallized isosorbide was distilled and purified again at 190 ° C. and 9 Torr. The alkali metal content of this distilled and purified isosorbide was 0 ppm.
On the other hand, when the alkali metal content of isosorbide (POLYSORB-P) manufactured by Rocket Corporation was measured, it was 4.6 ppm.

Reference Example 3 Production of diphenyl carbonate 330.8 parts of ion exchanged water, 106.0 parts of 48.6% caustic soda aqueous solution and phenol (special reagent grade) 118 in a reaction vessel provided with a stirring blade, a thermometer, a condenser and a gas blowing pipe .1 part was added to prepare an aqueous sodium phenolate solution, and the internal temperature was cooled to 20 ° C. in a water bath. While stirring, 64.16 parts of phosgene gas was blown into the reaction vessel over 40 minutes. During this period, the reaction vessel was cooled with a water bath and the internal temperature was maintained at about 30 ° C. After completion of the phosgene gas blowing, stirring was continued at room temperature for 3 hours to complete the reaction. The produced diphenyl carbonate was collected by filtration, washed 5 times with 400 parts of ion exchange water, and then dried under reduced pressure at 50 ° C. for 10 hours. 127.7 parts of diphenyl carbonate having a melting point of 80 to 81 ° C. (yield based on 95% phenol) was obtained. The alkali metal content of this diphenyl carbonate was measured and found to be 0 ppm (below the detection limit).

  In the following examples, polymers were synthesized using isosorbide obtained in Reference Examples 1 and 2 and diphenyl carbonate obtained in Reference Example 3.

Example 1
1608 parts by weight (11 mol) of isosorbide having an alkali metal (sodium) content of 0 ppm (hereinafter referred to as “ISS-1”) and 2356 parts by weight of diphenyl carbonate (hereinafter referred to as “DPC”) obtained in Reference Example 4 ( 11 moles) as a polymerization catalyst, 0.31 part by weight of tetramethylammonium hydroxide (hereinafter referred to as “TMAH”) (3 × 10 ⁻⁴ moles per mole of DPC component), and water 6.6 × 10 ⁻⁴ parts by weight of sodium oxide (hereinafter referred to as “NaOH”) (1.5 × 10 ⁻⁶ mol per 1 mol of DPC component) is charged, and bis (2,6-di-tert) is used as a stabilizer. -Butyl-4-methylphenyl) pentaerythritol diphosphite (hereinafter referred to as “P-1”) was added at 500 ppm with respect to DPC, and nitrogen was added. It was heated to 180 ° C. were melted at 囲気 under normal pressure.

When the concentration of the alkali metal and the ratio of the nitrogen-containing basic compound / alkali metal compound in the molten solution is calculated from the charged amount, the concentration of the alkali metal is 0.1 ppm, and the concentration of the nitrogen-containing basic compound / alkali metal compound is The ratio is 828/1.
After the charged components were completely melted, the pressure in the reaction vessel was gradually reduced over 30 minutes with stirring, and the pressure was reduced to 13.3 × 10 ⁻³ MPa while distilling off the produced phenol. After reacting in this state for 20 minutes, the temperature was raised to 200 ° C., then the pressure was gradually reduced over 20 minutes, and the reaction was carried out at 4.00 × 10 ⁻³ MPa for 20 minutes while distilling off the phenol. The mixture was heated to 250 ° C. for 30 minutes and reacted for 30 minutes.

Next, the pressure was gradually reduced, and the reaction was continued at 2.67 × 10 ⁻³ MPa for 10 minutes and 1.33 × 10 ⁻³ MPa for 10 minutes, and further reduced in pressure to reach 4.00 × 10 ⁻⁵ MPa. The temperature was gradually raised to 260 ° C., and the reaction was finally carried out at 260 ° C. and 6.66 × 10 ⁻⁵ MPa for 1 hour. As a result, a polymer having a specific viscosity of 0.41 was obtained. The melt viscosity at 250 ° C. and 600 sec ⁻¹ of this polymer was 2.58 × 10 ³ Pa · s, the glass transition temperature was 166 ° C., the 5% weight loss temperature was 360 ° C., and the solution b value was 3.7.

[Measurement of proportion of carbon-carbon double bond component]
The ¹ HNMR (heavy solvent: CDCl ₃ ) measurement result of the polymer obtained in Example 1 is shown in FIG. In FIG. 1, the peak attributed to the carbon-carbon double bond component (chemical shift 6.5 to 6.6) when the integrated intensity of the peak attributed to H ^h of isosorbide (around 4.9 ppm in chemical shift) is 1. The integrated intensity of 7 ppm was 0.0015. Since these peaks all correspond to one proton, the ratio of the carbon-carbon double bond component is
It is calculated as 0.0015 / (1 + 0.0015) × 100 = 0.15 (%).

Example 2
Isosorbide (hereinafter referred to as “ISS-2”) having an alkali metal (sodium) content of 0.2 ppm was used in place of ISS-1, and 0.11 part by weight of TMAH as a polymerization catalyst (based on 1 mol of DPC component) 1.0 × 10 ⁻⁴ mol) and 1.1 × 10 ⁻⁴ parts by weight of NaOH (0.25 × 10 ⁻⁶ mol with respect to 1 mol of DPC component), and stabilizer P-1 with respect to DPC The polymer was polymerized in the same manner as in Example 1 except that 1000 ppm was added to obtain a polymer having a specific viscosity of 0.36. Other evaluation results are shown in Table 1.

Example 3
Isosorbide having an alkali metal (sodium) content of 1.1 ppm (hereinafter referred to as “ISS-3”) was used instead of ISS-1, and 0.21 part by weight of TMAH as a polymerization catalyst (based on 1 mol of DPC component) 2.0 × 10 ⁻⁴ mol) was added and polymerized in the same manner as in Example 1 except that 1000 ppm of stabilizer P-1 was added to DPC to obtain a polymer having a specific viscosity of 0.32. Other evaluation results are shown in Table 1.

Comparative Example 1
Isosorbide having an alkali metal (sodium) content of 4.6 ppm (hereinafter referred to as “ISS-4”) was used instead of ISS-1, and 0.21 part by weight of TMAH as a polymerization catalyst (with respect to 1 mol of DPC component). 2.0 × 10 ⁻⁴ mol) was added and polymerized in the same manner as in Example 1 except that 500 ppm of stabilizer P-1 was added to DPC to obtain a polymer having a specific viscosity of 0.23. Other evaluation results are shown in Table 1.

Comparative Example 2
ISS-2 was used instead of ISS-1, 0.63 parts by weight of TMAH as a polymerization catalyst (8.0 × 10 ⁻⁴ mol with respect to 1 mol of DPC component), and NaOH of 1.1 × 10 ⁻⁴ The polymer was polymerized in the same manner as in Example 1 except that a weight part (0.25 × 10 ⁻⁶ mol per 1 mol of DPC component) was added and 500 ppm of stabilizer P-1 was added to DPC. A polymer was obtained. Other evaluation results are shown in Table 1.

Comparative Example 3
As a polymerization catalyst, 0.11 part by weight of TMAH (1.0 × 10 ⁻⁴ mole relative to 1 mole of DPC component) and 1.1 × 10 ⁻⁴ part by weight of NaOH (0.1 mole per 1 mole of DPC component) 25 × 10 ⁻⁶ mol) Polymerization was carried out in the same manner as in Example 1 except that the stabilizer P-1 was not added and a polymer having a specific viscosity of 0.12 was obtained. Other evaluation results are shown in Table 1.

It is a figure of the integral value 0-8 ppm which measured ¹ HNMR of the polycarbonate resin of this invention. It is an enlarged view of the peak of the integral value 6-7 ppm in FIG.

Claims (11)

A polycarbonate resin containing a carbonate constituent unit represented by the following formula (1), wherein the polymer terminal contains a carbon-carbon double bond component represented by the following formula (2) and the following formula (3). The total value of the above-mentioned carbonate constituent unit is 0.3% or less, and the b value of a 15% by weight methylene chloride solution of polycarbonate resin measured at an optical path length of 30 mm is 5.0 or less. Polycarbonate resin.

  The polycarbonate resin according to claim 1, wherein the specific viscosity at 20 ° C of a solution prepared by dissolving 0.7 g of the resin in 100 ml of methylene chloride is 0.14 to 0.55.   The polycarbonate resin according to claim 1, wherein the specific viscosity at 20 ° C of a solution prepared by dissolving 0.7 g of the resin in 100 ml of methylene chloride is 0.20 to 0.45. 2. The polycarbonate resin according to claim 1, wherein the melt viscosity measured with a capillary rheometer at 250 ° C. is in the range of 0.2 × 10 ^{3 to} 4.0 × 10 ³ Pa · s under the condition of a shear rate of 600 sec ^-1 .   The polycarbonate resin according to claim 1, wherein the glass transition temperature (Tg) is 120 ° C to 175 ° C, and the 5% weight loss temperature (Td) is 320 to 400 ° C.   The polycarbonate resin according to claim 1, wherein the glass transition temperature (Tg) is 145 ° C to 170 ° C and the 5% weight loss temperature (Td) is 320 to 400 ° C.   The polycarbonate resin according to claim 1, wherein the carbonate constituent unit represented by the formula (1) is a carbonate constituent unit derived from isosorbide (1,4: 3,6-dianhydro-D-sorbitol).   The polycarbonate resin according to claim 1, wherein the structural unit represented by the formula (1) is 60 mol% or more in all carbonate structural units. A method for producing a polycarbonate resin, wherein a nitrogen-containing basic compound and an alkali metal compound are used as a polymerization catalyst, and a diol component containing an ether diol represented by the following formula (a) and a carbonic diester are melt polycondensed under heating and reduced pressure In the above, the concentration of the alkali metal when the diol component and the carbonic acid diester are heated and melted at normal pressure is 0.1 to 1.0 ppm in the molten solution, and the ratio of the nitrogen-containing basic compound and the alkali metal is the weight ratio. The method for producing a polycarbonate resin according to claim 1, wherein the amount of the polymerization catalyst is adjusted so as to be in the range of 50/1 to 2000/1 (nitrogen-containing basic compound / alkali metal).

When the diol component containing the ether diol represented by the above formula (a) and the carbonic acid diester are heated and melted at normal pressure, the organic phosphorus compound represented by the following formula (4) is 200 to 200 carbonic acid diesters. The method for producing a polycarbonate resin according to claim 9, wherein 3000 ppm is added.

(In the above formula (4), R ¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ² is an alkyl group having 4 to 10 carbon atoms, and R ³ is a hydrogen atom or the number of carbon atoms. An alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, carbon At least one selected from the group consisting of an aryl group having 6 to 10 atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aralkyloxy group having 7 to 20 carbon atoms. Group.)   A molded article formed from the polycarbonate resin according to claim 1.

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