JP5296452B2 - Terminal-modified polycarbonate and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarbonate with high surface energy, having a high content of biogenic materials, and being excellent in heat resistance, thermal stability, molding processability, and hygroscopic resistance. <P>SOLUTION: The polycarbonate includes &ge;50 mol% and &lt;95 mol% of a repeating unit having a main chain represented by formula (1) and has specific viscosity of 0.2-0.5 at 20&deg;C in a methylene chloride solution. The terminal groups are represented by formulae (2) and (3). <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a terminal-modified polycarbonate. More specifically, the present invention relates to a polycarbonate that contains a repeating unit derived from a carbohydrate that is a biogenic substance and has excellent thermal stability, heat resistance, molding processability, and moisture absorption resistance.

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

  Polycarbonate is generally produced using raw materials from petroleum resources. However, there is concern about the exhaustion of petroleum resources, and polycarbonates using raw materials from biogenic substances such as plants are required. Thus, polycarbonates using ether diols that can be produced from carbohydrates have been studied.

で表されるエーテルジオールは、生物起源物質、例えば、糖類、でんぷんなどから容易に作られる。このエーテルジオールには３種の立体異性体があることが知られている。具体的には下記式（９）

に示す、１，４：３，６−ジアンヒドロ−Ｄ−ソルビトール（以下「イソソルビド」と呼称する）、下記式（１０）

に示す、１，４：３，６−ジアンヒドロ−Ｄ−マンニトール（以下「イソマンニド」と呼称する）、下記式（１１）

に示す、１，４：３，６−ジアンヒドロ−Ｌ−イジトール（以下「イソイディッド」と呼称する）である。 For example, the following formula (5)

The ether diol represented by is easily made from a biogenic material such as sugars and starch. This ether diol is known to have three types of stereoisomers. Specifically, the following formula (9)

1,4: 3,6-dianhydro-D-sorbitol (hereinafter referred to as “isosorbide”), represented by the following formula (10)

1,4: 3,6-dianhydro-D-mannitol (hereinafter referred to as “isomannide”), represented by the following formula (11)

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

  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 ether diols represented by the formula (5), it has been particularly studied to incorporate isosorbide into polycarbonate (Patent Documents 1 to 5).
However, isosorbide-containing polycarbonates are more polar than polycarbonates obtained from diols that contain many oxygen atoms and do not have an ether moiety such as PC-A. Therefore, isosorbide-containing polycarbonate has a higher hygroscopicity than PC-A, and has a drawback that it tends to cause a decrease in dimensional stability of a molded product due to moisture absorption and a decrease in heat resistance during wet heat. In addition, isosorbide-containing polycarbonate has the disadvantages that the surface energy is low, the molded product is easily soiled, and is susceptible to wear. This surface energy can be evaluated by the contact angle with water.

  As described above, isosorbide-containing polycarbonate has room for further improvement in thermal stability and moldability. In addition, isosorbide-containing polycarbonate has a drawback associated with low surface energy and room for improving moisture absorption resistance.

JP-A-56-055425 Japanese Patent Laid-Open No. 56-110723 JP 2003-292603 A International Publication No. 2004/111106 Pamphlet Japanese Patent Laid-Open No. 2006-232897

  Accordingly, an object of the present invention is to provide a polycarbonate having a high content of biogenic substances, excellent heat resistance, thermal stability, molding processability and moisture absorption resistance, and high surface energy. Another object of the present invention is to provide a film having a low photoelastic constant, good retardation development and retardation controllability, excellent viewing angle characteristics, and excellent heat resistance and thermal stability. .

  The present inventor has disclosed that a polycarbonate having a main chain containing a repeating unit represented by the following formula (1) has a high biogenic substance content, a heat resistant, The present invention has been completed by finding that it has excellent stability, molding processability and moisture absorption resistance and high surface energy.

で表される繰り返し単位を全繰り返し単位中５０モル％以上９５モル％未満含んでなり、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０．２〜０．５であり、下記式（２）または（３）

｛上記式（２）、（３）において、Ｒ^１は炭素原子数４〜３０のアルキル基、炭素原子数７〜３０のアラルキル基、炭素原子数４〜３０のパーフルオロアルキル基、フェニル基、または下記式（４）

（上記式（４）中、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は夫々独立に、炭素原子数１〜１０のアルキル基、炭素原子数６〜２０のシクロアルキル基、炭素原子数２〜１０のアルケニル基、炭素原子数６〜１０のアリール基および炭素原子数７〜２０のアラルキル基からなる群より選ばれる少なくとも１種の基を表し、ｂは０〜３の整数、ｃは４〜１００の整数である）で表される基であり、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１種の結合を表わし、ａは１〜５の整数である。｝
で表される末端基を主鎖に対して０．０１〜７モル％含有する末端変性ポリカーボネートである。 That is, in the present invention, the main chain is represented by the following formula (1).

The specific viscosity at 20 ° C. of a solution in which 0.7 g is dissolved in 100 ml of methylene chloride is 0.2 to 0.5. The following formula (2) or (3)

{In the above formulas (2) and (3), R ¹ is 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, a phenyl group, Or the following formula (4)

(In the above formula (4), R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or a carbon atom. Represents 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, b is an integer of 0 to 3, c Is an integer of 4 to 100), and X represents at least one bond selected from the group consisting of a single bond, an ether bond, a thioether bond, an ester bond, an amino bond, and an amide bond, a is an integer of 1-5. }
Is a terminal-modified polycarbonate containing 0.01 to 7 mol% of terminal groups represented by the formula (1).

で表されるエーテルジオール（Ａ成分）、該エーテルジオール以外のジオールおよび／またはジフェノール化合物（Ｂ成分）、炭酸ジエステル（Ｃ成分）およびＡ成分及びＢ成分の合計モルに対して０．０１〜７モル％の下記式（６）または（７）

｛上記式（６）、（７）において、Ｒ^１は炭素原子数４〜３０のアルキル基、炭素原子数７〜３０のアラルキル基、炭素原子数４〜３０のパーフルオロアルキル基、フェニル基、または下記式（４）

（上記式（４）中、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は夫々独立に、炭素原子数１〜１０のアルキル基、炭素原子数６〜２０のシクロアルキル基、炭素原子数２〜１０のアルケニル基、炭素原子数６〜１０のアリール基および炭素原子数７〜２０のアラルキル基からなる群より選ばれる少なくとも１種の基を表し、ｂは０〜３の整数、ｃは４〜１００の整数である）で表される基であり、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１種の結合を表わし、ａは１〜５の整数である。｝
で表されるヒドロキシ化合物（Ｄ成分）を反応させることを特徴とする末端変性ポリカーボネートの製造方法である。 Further, the present invention provides the following formula (5)

0.01 to the total moles of the ether diol (component A), diol other than the ether diol and / or diphenol compound (component B), carbonic acid diester (component C), component A and component B 7 mol% of the following formula (6) or (7)

{In the above formulas (6) and (7), R ¹ is 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, a phenyl group, Or the following formula (4)

(In the above formula (4), R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or a carbon atom. Represents 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, b is an integer of 0 to 3, c Is an integer of 4 to 100), and X represents at least one bond selected from the group consisting of a single bond, an ether bond, a thioether bond, an ester bond, an amino bond, and an amide bond, a is an integer of 1-5. }
A terminal-modified polycarbonate is produced by reacting a hydroxy compound (component D) represented by the formula:

で表されるエーテルジオール（Ａ成分）、該エーテルジオール以外のジオールおよび／またはジフェノール化合物（Ｂ成分）とホスゲン（Ｅ成分）とを、不活性溶媒中で、酸結合剤の存在下に反応させるポリカーボネートの製造方法であって、末端停止剤として下記式（６）または（７）

｛上記式（６）、（７）において、Ｒ^１は炭素原子数４〜３０のアルキル基、炭素原子数７〜３０のアラルキル基、炭素原子数４〜３０のパーフルオロアルキル基、フェニル基、または下記式（４）

（上記式（４）中、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は夫々独立に、炭素原子数１〜１０のアルキル基、炭素原子数６〜２０のシクロアルキル基、炭素原子数２〜１０のアルケニル基、炭素原子数６〜１０のアリール基および炭素原子数７〜２０のアラルキル基からなる群より選ばれる少なくとも１種の基を表し、ｂは０〜３の整数、ｃは４〜１００の整数である）で表される基であり、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１種の結合を表わし、ａは１〜５の整数である。｝で表されるヒドロキシ化合物（Ｃ成分）を反応させることを特徴とする末端変性ポリカーボネートの製造方法である。 Furthermore, the present invention provides the following formula (5)

A diol other than the ether diol and / or a diphenol compound (B component) and phosgene (E component) are reacted in an inert solvent in the presence of an acid binder. A polycarbonate production method comprising the following formula (6) or (7) as a terminator:

{In the above formulas (6) and (7), R ¹ is 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, a phenyl group, Or the following formula (4)

(In the above formula (4), R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or a carbon atom. Represents 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, b is an integer of 0 to 3, c Is an integer of 4 to 100), and X represents at least one bond selected from the group consisting of a single bond, an ether bond, a thioether bond, an ester bond, an amino bond, and an amide bond, a is an integer of 1-5. } Is reacted with a hydroxy compound (C component) represented by the following formula:

Hereinafter, the present invention will be described in detail.
<Terminal modified polycarbonate>
(Main chain)
The terminal-modified polycarbonate of the present invention comprises a repeating unit whose main chain is represented by the following formula (1). That is, the content of the repeating unit represented by the following formula (1) in the main chain is 50 mol% or more and less than 95 mol%, preferably 55 mol% or more and 90 mol% or less.

  The repeating unit represented by the formula (1) is preferably a unit derived from isosorbide, isomannide, or isoidide. In particular, a unit derived from isosorbide (1,4; 3,6-dianhydro-D-sorbitol) is preferable.

(Specific viscosity)
The terminal-modified polycarbonate of the present invention has a specific viscosity at 20 ° C. of 0.2 to 0.5, preferably 0.2 to 0.45, more preferably 0.22 of a solution obtained by dissolving 0.7 g in 100 ml of methylene chloride. ~ 0.4. When the specific viscosity is lower than 0.2, it is difficult to give the obtained molded article sufficient mechanical strength. Further, when the specific viscosity is higher than 0.5, the ratio of terminal groups is inevitably lowered, and not only a sufficient terminal modification effect cannot be exhibited, but the melt fluidity becomes too high, and the melting temperature necessary for molding becomes the decomposition temperature. It becomes higher and is not preferable.

(Terminal group)
The terminal-modified polycarbonate of the present invention contains a terminal group represented by the following formula (2) or (3).

で表される基である。 In the formulas (2) and (3), R ¹ is 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, a phenyl group, or the following Formula (4)

It is group represented by these.

The number of carbon atoms of the alkyl group for R ¹ is preferably 4-22, more preferably 8-22. Examples of the alkyl group include hexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, pentadecyl group, hexadecyl group, octadecyl group and the like.

The number of carbon atoms of the aralkyl group of R ¹ is preferably 8-20, more preferably 10-20. Examples of the aralkyl group include a benzyl group, a phenethyl group, a methylbenzyl group, a 2-phenylpropan-2-yl group, and a diphenylmethyl group.

The number of carbon atoms of the perfluoroalkyl group for R ¹ is preferably 2-20. 4,4,5,5,6,6,7,7,7-nonafluoroheptyl group as a perfluoroalkyl group, 4,4,5,5,6,6,7,7,8,8,9, 9,9-tridecafluorononyl group, 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoroundecyl group Etc.

In formula (4), R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or the number of carbon atoms. It represents 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.

  Examples of the alkyl group having 1 to 10 carbon atoms in the formula (4) include a methyl group, an ethyl group, a propyl group, a butyl group, and a heptyl group. Examples of the cycloalkyl group having 6 to 20 carbon atoms include a cyclohexyl group, a cyclooctyl group, a cyclohexyl group, and a cyclodecyl group. Examples of the alkenyl group having 2 to 10 carbon atoms include ethenyl group, propenyl group, butenyl group and heptenyl group. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, a dimethylphenyl group, and a naphthyl group. Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, phenethyl group, methylbenzyl group, 2-phenylpropan-2-yl group, diphenylmethyl group and the like.

In formula (4), R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently 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. It is preferable that it is at least one kind of group. In particular, at least one group selected from the group consisting of a methyl group and a phenyl group is preferable.

  b is an integer of 0-3, preferably an integer of 1-3, more preferably an integer of 2-3. c is an integer of 4 to 100, more preferably an integer of 4 to 50, and still more preferably an integer of 8 to 50.

  X in Formula (3) represents at least one bond selected from the group consisting of a single bond, an ether bond, a thioether bond, an ester bond, an amino bond, and an amide bond. X is preferably at least one bond selected from the group consisting of a single bond, an ether bond and an ester bond. Of these, a single bond and an ester bond are preferable.

  a is an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1.

  The terminal group represented by the above formula (2) or (3) is preferably derived from a biological material. Examples of biogenic substances include long-chain alkyl alcohols having 14 or more carbon atoms, such as cetanol, stearyl alcohol, and behenyl alcohol.

  The content of the terminal group represented by the formula (2) or (3) is 0.01 to 7 mol%, preferably 0.05 to 7 mol%, more preferably 0.1 to 0.1 mol% with respect to the polymer main chain. 6.8 mol%. When the terminal group represented by the formula (2) or (3) is within the above range, effects (molding processability, high contact angle and moisture absorption resistance) due to terminal modification are suitably expressed.

(Contact angle to water)
The contact angle of the end-modified polycarbonate of the present invention with respect to water is preferably in the range of 70 to 180 °, more preferably 72 to 180 °. When the contact angle with respect to water is within the above range, it is preferable in terms of antifouling property, abrasion resistance and releasability.

(Water absorption rate)
The water absorption after 24 hours of the terminal-modified polycarbonate of the present invention is preferably 0.75% or less, more preferably 0.7% or less. A water absorption rate in the above range is preferable in terms of moisture and heat resistance and a low dimensional change rate.

で表されるエーテルジオール（Ａ成分）、該エーテルジオール以外のジオールおよび／またはジフェノール化合物（Ｂ成分）、炭酸ジエステル（Ｃ成分）およびＡ成分とＢ成分の合計に対して０．０１〜７モル％の下記式（６）または（７）

で表されるヒドロキシ化合物（Ｄ成分）を反応させ製造することができる（製造方法（Ｉ））。 <Method for producing terminal-modified polycarbonate (I)>
The terminal-modified polycarbonate of the present invention has the following formula (5):

0.01 to 7 with respect to the ether diol (component A) represented by the formula, diol other than the ether diol and / or diphenol compound (component B), carbonic acid diester (component C) and the total of components A and B The following formula (6) or (7)

Can be produced by reacting the hydroxy compound (component D) represented by the formula (Production method (I)).

(Ether diol: component A)
The ether diol (component A) is preferably isosorbide, isomannide, or isoidide. These saccharide-derived ether diols are substances obtained from natural biomass and are one of so-called renewable resources. Isosorbide can be produced 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. The component A is particularly preferably isosorbide (1,4; 3,6-dianhydro-D-sorbitol). Isosorbide is an ether diol that can be easily made from starch, and can be obtained in abundant resources, and is superior in all ease of manufacture, properties, and versatility of use compared to isomannide and isoidide. .

(Diols other than the ether diol, diphenol compounds (component B))
The terminal-modified polycarbonate of the present invention is composed of a diol other than the component A and / or a diphenol compound (component B) in addition to the carbonate constituent unit formed from the ether diol (component A) represented by the above formula (1). The carbonate structural unit to be formed is contained in an amount of 5 mol% to 50 mol%. Preferably it contains 10 mol% or more and 45 mol% or less.

As the diol other than the ether diol, an aliphatic diol having 2 to 20 carbon atoms is preferable, and an aliphatic diol having 3 to 15 carbon atoms is more preferable. Specifically, linear diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol, and alicyclic rings such as cyclohexanediol and cyclohexanedimethanol Among them, 1,3-propanediol, 1,4-butanediol, hexanediol, spiroglycol, and cyclohexanedimethanol are preferable.
These ether diols may be used alone or in combination of two or more.

  Specifically, the diphenol compound is preferably a bisphenol that forms a carbonate structural unit represented by the following formula (12).

In the above formula (12), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkyl group having 6 to 20 carbon atoms. A cycloalkyl group, a C6-C20 cycloalkoxy group, a C2-C10 alkenyl group, a C6-C10 aryl group, a C6-C10 aryloxy group, a C7 Represents at least one group selected from the group consisting of -20 aralkyl groups, aralkyloxy groups having 7 to 20 carbon atoms, nitro groups, aldehyde groups, cyano groups, and carboxyl groups, A group that may be different.

Among them, R ¹ and R ² are each independently a hydrogen atom, a halogen 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, C6-C20 cycloalkoxy group, C6-C10 aryl group, C6-C10 aryloxy group, C7-C20 aralkyl group, and C7-C20 aralkyl It represents at least one group selected from the group consisting of oxy groups, and when there are plural groups, they are preferably the same or different groups.
a and b are integers of 1 to 4, respectively.

  W is at least one linking group selected from the group consisting of a single bond and a linking group represented by the following formula (13).

(In the above formula (13), R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a carbon atom. Represents at least one group selected from the group consisting of an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 20 carbon atoms, and when there are plural groups, they may be the same or different, and R ¹¹ and R ¹² are Each independently a hydrogen atom, a halogen 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, or a cycloalkoxy having 6 to 20 carbon atoms Group, alkenyl group having 2 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, aryloxy group having 6 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, 7 to 20 carbon atoms Represents at least one group selected from the group consisting of an aralkyloxy group, a nitro group, an aldehyde group, a cyano group, and a carboxyl group, and each of R ¹³ , R ¹⁴ , R ^15, and R ¹⁶ independently represents 1 to Selected from the group consisting of 10 alkyl groups, cycloalkyl groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms At least one group which may be the same or different, c is an integer of 1 to 10, d is an integer of 4 to 7, e is an integer of 1 to 3, and f is 1 to It is an integer of 100.)

  Among these, W is preferably a single bond or at least one linking group selected from the group consisting of a linking group represented by the following formula (14).

(In the above formula (14), R ¹⁷ and R ¹⁸ are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ¹⁹ and R ²⁰ each independently represent a hydrogen atom or 1 carbon atom. In the case where there are a plurality of them, they may be the same or different, and R ²¹ and R ²² each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, They may be the same or different and d is an integer from 4 to 7.)

  In particular, W is preferably at least one linking group selected from the group consisting of linking groups represented by the following formula (15).

（上記式（１５）において、Ｒ^１７，Ｒ^１８，Ｒ^１９，Ｒ^２０，Ｒ^２１，Ｒ^２２およびｄは、式（１４）の定義と同じである。）

(In the above formula (15), R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and d are the same as defined in formula (14).)

  Specific examples of bisphenols include 4,4′-biphenol, 3,3 ′, 5,5′-tetrafluoro-4,4′-biphenol, α, α′-bis (4-hydroxyphenyl) -o-. Diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene (usually referred to as “bisphenol M”), 2,2-bis (4-hydroxyphenyl) -4-methylpentane, α , Α′-bis (4-hydroxyphenyl) -p-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -m-bis (1,1,1,3,3,3-hexafluoroisopropyl) Benzene, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (3-phenyl) Fluoro-4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-trifluoromethylphenyl) fluorene, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy) Phenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 1,1- Bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (3-fluoro-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) perfluorocyclohexane, 4,4′-dihydroxydiphenyl ester -Tell, 4,4'-dihydroxy-3,3'-dimethyl Diphenyl ether, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfide, 3,3′-dimethyl-4,4′-dihydroxydiphenyl sulfide, 3, 3'-dimethyl-4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-diphenyl sulfide, 4,4'-dihydroxy-3,3'- Diphenyl sulfoxide, 4,4′-dihydroxy-3,3′-diphenyl sulfone, 1,1-bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis ( 4-hydroxyphenyl) propane (usually referred to as “bisphenol A”) 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane (usually referred to as “bisphenol C”), 2,2- Bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxy-3-phenylphenyl) propane, 2,2-bis (3-isopropyl-4-) Hydroxyphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 4,4-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxyphenyl) octane, 1,1-bis (4-hydroxyphenyl) decane, 1,1-bis (3-methyl-4-hydroxy) Droxyphenyl) decane, 1,1-bis (2,3-dimethyl-4-hydroxyphenyl) decane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) diphenylmethane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane (usually “bisphenol AF”) 2,2-bis (4-hydroxy-3-methylphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3,5-dimethyl- 4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (3-fluoro-4-hydroxyphenyl) -1,1, , 3,3,3-hexafluoropropane and 2,2-bis (3,5-difluoro-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2- Bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, And 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane.

Among the above, bisphenol M, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3 , 3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 3,3′-dimethyl-4,4′-dihydroxydiphenyl sulfide, bisphenol A, bisphenol C, bisphenol AF, And 1,1-bis (4-hydroxyphenyl) decane are preferred.
These bisphenols may be used alone or in combination of two or more.

(Carbonate diester: component C)
Examples of the carbonic acid diester (component C) include carbonic acid diesters such as an optionally substituted aryl group having 6 to 12 carbon atoms, an aralkyl group, or an alkyl group having 1 to 4 carbon atoms. Specific examples include diphenyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Of these, diphenyl carbonate is preferred.

  The amount of carbonic acid diester (C component) is the molar ratio of carbonic acid diester (C component) to the total amount of ether diol (A component) and diol other than ether diol and diphenol compound (B component) (C component / (A component + B component)), preferably 1.05 to 0.97, more preferably 1.03 to 0.97, and still more preferably 1.03 to 0.99. When the component C exceeds 1.05 mol, a sufficient degree of polymerization cannot be obtained. When the component C is less than 0.97 mol, not only polymerization does not proceed, but also unreacted ether diol and hydroxy compound remain.

(Hydroxy compound: component D)
In the hydroxy compound (component D) represented by the following formula (6) or (7), R ¹ , X, a, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , b, c are represented by the formula ( Same as 2) and (3). Hydroxy compounds (component D) may be used alone or in admixture of two or more. When using 2 or more types, you may use combining the hydroxy compound (D component) represented by Formula (6) or (7), and other hydroxy compounds. The hydroxy compound (component D) improves the heat resistance, thermal stability, molding processability, and water absorption resistance of the polycarbonate.

  Since the terminal-modified polycarbonate of the present invention has a repeating unit using a raw material obtained from renewable resources such as plants in the main chain structure, these hydroxy compounds (component D) constituting the terminal structure are also used for plants and the like. It is preferably derived from a biogenic material. Examples of the hydroxy compound obtained from plants include long-chain alkyl alcohols having 14 or more carbon atoms (cetanol, stearyl alcohol, behenyl alcohol) obtained from vegetable oils.

  The amount of the hydroxy compound (component D) is preferably 0.01 to 7 mol%, more preferably the total amount of ether diol (component A), diol other than the ether diol and diphenol compound (component B). Is 0.05-7 mol%, more preferably 0.1-6.8 mol%. If the hydroxy compound is less than 0.01 mol%, the effect of terminal modification cannot be obtained. If the amount of the hydroxy compound exceeds 7 mol%, the amount of the end terminator is too large to obtain a terminal-modified polycarbonate having a degree of polymerization sufficient for molding. The timing of adding the hydroxy compound (component D) may be either the initial reaction stage or the late reaction stage.

  The reaction can be carried out by melt polymerization. The melt polymerization can be carried out by distilling alcohol or phenol produced by the transesterification reaction of the A component to D component under high temperature and reduced pressure.

(Reaction temperature)
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 to 280 ° C. in order to proceed the polymerization reaction appropriately. It is preferable that it is the range of this, More preferably, it is the range of 180-270 degreeC.

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 1 to 4 hours.

(Polymerization catalyst)
A polymerization catalyst can be used to increase the polymerization rate. Examples of the polymerization catalyst include alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, sodium salt of dihydric phenol, potassium salt of dihydric phenol, and the like. Moreover, alkaline-earth metal compounds, such as calcium hydroxide, barium hydroxide, magnesium hydroxide, are mentioned.

  Moreover, nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylamine, and triethylamine are listed.

  Alkali metals and alkaline earth metal alkoxides, alkali metal and alkaline earth metal organic acid salts, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organotin compounds, lead Examples thereof include compounds, osmium compounds, antimony compounds, manganese compounds, titanium compounds, and zirconium compounds. These may be used alone or in combination of two or more.

  As the polymerization catalyst, it is preferable to use at least one compound selected from the group consisting of nitrogen-containing basic compounds, alkali metal compounds, and alkaline earth metal compounds. Among these, it is preferable to use a nitrogen-containing basic compound and an alkali metal compound in combination.

The amount of these polymerization catalysts used is preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻³ equivalent, more preferably 1 × 10 ^{−8 to} 5 × 10 ^{−4, with respect} to 1 mol of carbonic acid diester (component C). It is selected in the range of equivalents.

  The reaction system is preferably maintained in an atmosphere of a gas such as nitrogen that is inert to the raw materials, the reaction mixture, and the reaction product. Examples of inert gases other than nitrogen include argon. Furthermore, you may add additives, such as antioxidant, as needed.

(Catalyst deactivator)
A catalyst deactivator can also be added to the terminal-modified polycarbonate of the present invention. A known catalyst deactivator can be used as the catalyst deactivator. Of these, ammonium salts and phosphonium salts of sulfonic acids are preferred. Furthermore, ammonium salts and phosphonium salts of dodecylbenzenesulfonic acid such as tetrabutylphosphonium salt of dodecylbenzenesulfonic acid are preferable. Ammonium salts and phosphonium salts of paratoluenesulfonic acid such as 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 paratoluenesulfonate, and the like are preferably used. Of these, dodecylbenzenesulfonic acid tetrabutylphosphonium salt is most preferably used. The amount of the catalyst deactivator used is preferably 0.5 to 50 mol, more preferably 0.5 to 10 mol, per mol of the polymerization catalyst selected from alkali metal compounds and / or alkaline earth metal compounds. More preferably, the proportion is 0.8 to 5 mol.

  Therefore, in the presence of a polymerization catalyst, ether diol (component A), diol other than the ether diol, diphenol compound (component B), carbonic acid diester (component C) and hydroxy compound (component D) are heated at normal pressure. Next, it is preferable to perform melt polycondensation while heating at a temperature of 180 to 280 ° C. under reduced pressure.

で表されるエーテルジオール（Ａ成分）と該エーテルジオール以外のジオールおよび／またはジフェノール化合物（Ｂ成分）とホスゲン（Ｅ成分）とを、不活性溶媒中で、酸結合剤の存在下に反応させ、末端停止剤として下記式（６）または（７）

で表されるヒドロキシ化合物（Ｄ成分）を用いることにより製造することができる（製造方法（ＩＩ））。 <Method for producing terminal-modified polycarbonate (II)>
The terminal-modified polycarbonate of the present invention comprises an ether diol (component A), a diol other than the ether diol and / or a diphenol compound (component B) and phosgene (in an inert solvent in the presence of an acid binder such as pyridine). E component) can be reacted. That is, the terminal-modified polycarbonate of the present invention has the following formula (5):

A diol other than the ether diol and / or a diphenol compound (B component) and phosgene (E component) are reacted in an inert solvent in the presence of an acid binder. As a terminal terminator, the following formula (6) or (7)

It can manufacture by using the hydroxy compound (D component) represented by (Manufacturing method (II)).

  A component, B component, and D component are the same as the manufacturing method (I). The ether diol (component A) is preferably isosorbide (1,4; 3,6-dianhydro-D-sorbitol). The hydroxy compound (component D) is preferably derived from a biogenic substance. Thermal stability improves by using the hydroxy compound (D component) represented by Formula (6) or (7) as a terminal terminator.

(Acid binder)
The acid binder is preferably at least one selected from the group consisting of pyridine, quinoline and dimethylaniline. Pyridine is particularly preferred as the acid binder. The amount of the acid binder used is preferably 2 to 100 mol, more preferably 2 to 50 mol, per 1 mol of phosgene (component E).

(Inert solvent)
Examples of the inert solvent include hydrocarbons such as benzene, toluene and xylene, and halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, chlorobenzene and dichlorobenzene. Of these, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, chlorobenzene and dichlorobenzene are preferred. Most preferred is methylene chloride. The reaction temperature is preferably 0 to 40 ° C, more preferably 5 to 30 ° C. The reaction time is usually several minutes to several days, preferably 10 minutes to 5 hours.

<Molding>
The present invention includes a molded article such as a film made of the above-mentioned terminal-modified polycarbonate. The film can be used for optics.
The film of the present invention can be produced by a solution casting method in which a solution obtained by dissolving the terminal-modified polycarbonate of the present invention in a solvent is cast, or a melt film-forming method in which the terminal-modified polycarbonate of the present invention is melted and cast as it is. it can.

  When producing a film by the solution casting method, it is preferable to use a halogen-based solvent, particularly methylene chloride, from the viewpoint of versatility and production cost as a solvent to be used. As the solution composition (dope), a solution in which 10 parts by weight of the end-modified polycarbonate of the present invention is dissolved in 15 to 90 parts by weight of a solvent containing 60% by weight or more of methylene chloride is preferable. If the amount of solvent is more than 90 parts by weight, it may be difficult to obtain a cast film having a large film thickness and excellent surface smoothness. If the amount of solvent is less than 15 parts by weight, the solution viscosity is too high and the film is too high. Manufacturing can be difficult.

  In addition to methylene chloride, other solvents may be added as necessary as long as film formation is not hindered. For example, alcohols such as methanol, ethanol, 1-propanol and 2-propanol, chloroform, 1,2 -Halogen solvents such as dichloroethane, aromatic solvents such as toluene and xylene, ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, ester solvents such as ethyl acetate and butyl acetate, and ether solvents such as ethylene glycol dimethyl ether It is done.

  In the present invention, a film can be obtained by casting a dope on a supporting substrate and then evaporating the solvent by heating. A glass substrate, a metal substrate such as stainless steel or ferrotype, a plastic substrate such as PET, or the like is used as the support substrate, and the dope is uniformly cast on the support substrate with a doctor blade or the like. Industrially, a method of continuously extruding a dope from a die onto a belt-like or drum-like support substrate is common.

  It is preferable that the dope cast on the support substrate is gradually heated and dried from a low temperature so that foaming does not occur. The dope is peeled off from the support substrate after removing most of the solvent by heating to form a self-supporting film. Further, it is preferable to remove the remaining solvent by heating and drying from both sides of the film. In the drying process after peeling from the substrate, there is a high possibility that stress will be applied to the film due to dimensional changes due to thermal shrinkage. Therefore, a product that requires precise control of optical properties like an optical film used in liquid crystal display devices is required. In the membrane, it is necessary to pay attention to the drying temperature, film fixing conditions, and the like. In general, in drying after peeling, it is preferable to take a method of drying while raising the temperature stepwise in the range of (Tg-100 ° C.) to Tg of the polycarbonate to be used. Drying at Tg or higher is not preferable because thermal deformation of the film occurs, and (Tg-100 ° C.) or lower is not preferable because the drying temperature is remarkably slowed.

  The amount of residual solvent in the film obtained by the solution casting method is preferably 2% by weight or less, more preferably 1% by weight or less. When the amount of residual solvent is 2% by weight or more, the glass transition point of the film is remarkably lowered, which is not preferable.

  When a film is produced by a melt film forming method, the melt is generally extruded from a T die to form a film. The film forming temperature is determined from the molecular weight, Tg, melt flow characteristics, etc. of the polycarbonate, but is usually in the range of 180 to 350 ° C, more preferably in the range of 200 to 320 ° C. If the temperature is too low, the viscosity may increase and polymer orientation and stress strain may remain. On the other hand, if the temperature is too high, problems such as thermal deterioration, coloring, and die lines (stripe) from the T-die are likely to occur. Sometimes.

  The film thickness of the unstretched film thus obtained is not particularly limited and is determined according to the purpose, but is preferably 10 to 300 μm, more preferably 20 to 200 μm from the viewpoint of film production, physical properties such as toughness, and cost. .

The terminal-modified polycarbonate of the present invention constituting the film preferably has a photoelastic constant of 60 × 10 ⁻¹² Pa ⁻¹ or less, more preferably 50 × 10 ⁻¹² Pa ⁻¹ or less. When the photoelastic constant is higher than 60 × 10 ⁻¹² Pa ⁻¹ , a phase difference is caused by the tension at the time of laminating the optical film, or a stress is generated due to a difference in dimensional stability with other materials. A phase difference is likely to occur, and as a result, phenomena such as light leakage and a decrease in contrast may occur, resulting in poor long-term stability.

Further, the film of the present invention has a wavelength dispersion of the retardation value represented by the following formula (i):
1.010 <R (450) / R (550) <1.070 (i)
Preferably satisfying the following formula (ii)
1.010 <R (450) / R (550) <1.060 (ii)
Is more preferable.

  Here, R (450) and R (550) are in-plane retardation values at wavelengths of 450 nm and 550 nm, respectively. When such a retardation film having a small wavelength dispersion of retardation values is used, a film having excellent viewing angle characteristics and contrast can be obtained particularly in a VA (vertical alignment) mode of a liquid crystal display device.

In the film of the present invention, the value obtained by dividing the retardation by the film thickness (Δn = R (550) / film film thickness (μm)) is in the unstretched state, the following formula (iii)
Δn <0.3 (iii)
Preferably satisfying the following formula (iv)
Δn <0.25 (iv)
Is more preferable. The lower limit is not particularly limited as long as it is in a range larger than 0 (zero).

  As the film of the present invention, an unstretched film obtained by orienting a polymer by a known stretching method such as uniaxial stretching or biaxial stretching is also suitable. Such stretching can be used, for example, as a retardation film of a liquid crystal display device. The stretching temperature is usually in the range of (Tg−20 ° C.) to (Tg + 20 ° C.) near the Tg of the polymer, and the stretching ratio is usually 1.02 to 3 times in the case of longitudinal uniaxial stretching. The film thickness of the stretched film is preferably in the range of 20 to 200 μm.

As one of the preferable retardation films obtained in the present invention, the in-plane retardation R (550) at a wavelength of 550 nm is in the range of the following formula (1),
100 nm <R (550) <2000 nm (1)
In addition, a retardation film having a film thickness of 10 to 150 μm is exemplified. Here, the phase difference R is defined by the following formula (5), and is a characteristic representing a phase delay of light transmitted in a direction perpendicular to the film.
_{R = (n x -n y)} × d ··· (5)
Wherein, n _x is that the refractive index of the slow axis in the film plane (highest refractive index axis), n _y is a refractive index of n _x and the vertical direction in the film plane, d is It is the film thickness. ]

  Here, R (550) is more preferably 100 to 600 nm. Moreover, as for a film thickness, 30-120 micrometers is more preferable, More preferably, it is 30-100 micrometers. Such a retardation film can be prepared by uniaxial stretching or biaxial stretching, and is suitably used for a 1 / 4λ plate, a 1 / 2λ plate, a λ plate, and the like.

As another preferable retardation film, the retardation R (550) in the film plane at a wavelength of 550 nm and the retardation K (550) in the film thickness direction are in the ranges of the following formulas (2) and (3),
0 nm <R (550) <150 nm (2)
100 nm <Rth (550) <400 nm (3)
(In the formula, Rth (550) is a retardation value in the film thickness direction at a wavelength of 550 nm, and is defined by the following formula (4).
Rth = {(n _x + _ny ) / 2−n _z } × d (4)
(Wherein, n _x, n _y is x-axis in the film plane, the y-axis, n _z is a refractive index in a thickness direction perpendicular to the x-axis and y-axis, d is the thickness of the film.)
Moreover, the film thickness is 10-150 micrometers, The retardation film of Claim 1 is also mentioned.

Such a film can be produced by biaxial stretching.
A film using the resin of the present invention having characteristics satisfying the above-mentioned range of Δn easily develops a retardation after stretching, has good retardation controllability, and is industrially suitable.

  The film of the present invention has a total light transmittance of preferably 80% or more, and more preferably 85% or more. Further, the haze value is preferably 5% or less, more preferably 3% or less. The film of the present invention is suitable as an optical film because of its excellent transparency.

  One film of the present invention may be used alone, or two or more films may be laminated and used. Moreover, you may use in combination with the optical film which consists of another raw material. You may use as a protective film of a polarizing plate, and may be used as a transparent substrate of a liquid crystal display device.

  In the terminal-modified polycarbonate of the present invention, the main chain includes a repeating unit derived from a biogenic material, and the content of the biogenic material is high. The terminal-modified polycarbonate of the present invention is excellent in heat resistance and heat stability. In addition, the terminal-modified polycarbonate of the present invention has a low melt viscosity for a high content of a biogenic substance, and is excellent in moldability. The terminal-modified polycarbonate of the present invention contains a highly polar ether diol component, but is excellent in moisture absorption resistance and excellent in dimensional stability and wet heat stability of a molded product. Further, the terminal-modified polycarbonate of the present invention has high surface energy, hardly stains, and is excellent in wear resistance.

According to the production method of the present invention, it is possible to obtain a terminal-modified polycarbonate having a portion derived from a biogenic substance, excellent in heat resistance, thermal stability, molding processability and moisture absorption resistance, and having high surface energy. Can do.
The optical film of the present invention has a low photoelastic constant, good retardation development and retardation controllability, excellent viewing angle characteristics, and excellent heat resistance and thermal stability.

  The following examples further illustrate the present invention. However, the present invention is not limited to these examples. In addition, 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 0.7 g / dL, and the temperature was measured at 20 ° C. using an Ostwald viscometer (device name: RIGO AUTO VISOSIMETER TYPE VMR-0525 · PC). In addition, specific viscosity (eta) _sp was calculated | required from the following formula.
η _sp = t / t _o −1
t: Flow time of sample solution t _o : Flow time of solvent only

(2) Terminal modification group content rate ¹ H-NMR in the heavy chloroform solution of the pellet was measured using JNM-JNM-AL400, and the specific proton derived from the main chain carbonate constituent unit and the specific proton derived from the terminal hydroxy compound The terminal modification group content was determined from the integration ratio. The terminal modified group content is the ratio (mol%) of the terminal hydroxy compound to the main chain carbonate constituent unit.

(3) Glass transition temperature (Tg)
It measured by DSC (model DSC2910) made from TA Instruments using the pellet.

(4) 5% weight loss temperature (Td)
It measured with TGA (model TGA2950) made from TA Instruments using the pellet.
5

(5) Molding processability The pellets were injection molded using JSWJ-75EIII manufactured by Nippon Steel Works, Ltd., and the shape of a 2 mm thick molded plate was visually evaluated (mold temperature: 70 to 90 ° C., molding) Temperature: 220-260 ° C).
Moldability ○: Turbidity, cracks, sink marks, silver due to decomposition, etc. are not seen.
X: Turbidity, cracks, sink marks, silver due to decomposition, etc. are observed.

(6) Contact angle The contact angle with respect to pure water was measured for a 2 mm-thick molded plate using a drop-type contact angle meter manufactured by Kyowa Interface Science Co., Ltd.

(7) Water absorption rate A 2 mm-thick molded plate previously dried at 100 ° C for 24 hours was immersed in water at 25 ° C, the weight after 24 hours was measured, and the water absorption rate was calculated from the following formula.

(8) Film thickness The film thickness was measured with a film thickness meter manufactured by Mitutoyo Corporation.

(9) Photoelastic constant A film having a width of 1 cm and a length of 6 cm is prepared, and the phase difference of the film in an unloaded state is set to the phase difference of light having a wavelength of 550 nm when loaded with 1N, 2N, and 3N, manufactured by JASCO Corporation. It was obtained by measuring with a spectroscopic ellipsometer “M220” and calculating (phase difference) × (film width) / (load).

(10) Total light transmittance and haze value of film The film was measured using a turbidimeter NDH-2000 type manufactured by Nippon Denshoku Industries Co., Ltd.

(11) Retardation value (R (450), R (550)) and its chromatic dispersion (R (450) / R (550))
Measurement was performed at a wavelength of 450 nm and a wavelength of 550 nm using a spectroscopic ellipsometer “M220” manufactured by JASCO Corporation. The retardation value was measured by measuring the retardation value with respect to the normal incident light with respect to the film surface.

(12) Thickness direction retardation value Rth
Using a spectroscopic ellipsometer M220 manufactured by JASCO Corporation, measurement was performed at a light wavelength of 550 nm. The in-plane retardation value R is measured in a state where the incident light beam is perpendicular to the film surface. The film thickness direction retardation value Rth is obtained by changing the angle between the incident light beam and the film surface little by little, measuring the phase difference value at each angle, and performing curve fitting with a known refractive index ellipsoid equation to obtain the three-dimensional refraction. seek _{n x, n y, n z} is the rate was determined by substituting the _{Rth = {(n x + n} y) / 2-n z} × d. In this case, the average refractive index of the film is required, but it was separately measured using an Abbe refractometer (trade name “Abbe refractometer 2-T” manufactured by Atago Co., Ltd.).

Example 1
731 parts by weight (5.00 mol) of isosorbide, 2206 parts by weight (10.30 mol) of diphenyl carbonate, 1141 parts by weight (5.00 mol) of 2,2-bis (4-hydroxyphenyl) propane, and 81 parts by weight of stearyl alcohol (0.30 mol) in a reactor, 1.0 part by weight of tetramethylammonium hydroxide as a polymerization catalyst (1 × 10 ⁻⁴ mol relative to 1 mol of diphenyl carbonate component), and 0% of sodium hydroxide .9 × 10 ⁻³ parts by weight (0.2 × 10 ⁻⁶ mol relative to 1 mol of the diphenyl carbonate component) was charged and melted at 180 ° C. in a nitrogen atmosphere.

Under stirring, the pressure in the reaction vessel was gradually reduced over 30 minutes, and the pressure was reduced to 13.3 × 10 ⁻³ MPa while the produced phenol was distilled off. 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 250 ° C., and the reaction was finally carried out at 250 ° C. and 6.66 × 10 ⁻⁵ MPa for 1 hour. The polymer after the reaction was pelletized to obtain a pellet having a specific viscosity of 0.26. The other evaluation results of this pellet are shown in Table 1.

Example 2
906 parts by weight (6.20 mol) of isosorbide, 868 parts by weight (3.80 mol) of 2,2-bis (4-hydroxyphenyl) propane and 122 parts by weight (0.40 mol) of pentadecylphenol were thermometers, After charging in a reactor equipped with a stirrer and purging with nitrogen, 8900 parts by weight of pyridine and 32700 parts by weight of methylene chloride which had been well dried in advance were added and dissolved. Under stirring at 20 ° C., 1420 parts by weight (14.30 mol) of phosgene was blown in for 100 minutes. After the completion of phosgene blowing, the reaction was terminated by stirring for about 20 minutes. After completion of the reaction, the product was diluted with methylene chloride, pyridine was neutralized and removed with hydrochloric acid, and then repeatedly washed with water until the conductivity was almost the same as that of ion-exchanged water, and then methylene chloride was evaporated to obtain a powder. The obtained powder was melt-extruded and the strand was cut to obtain pellets. The pellet had a specific viscosity of 0.27. Other evaluation results are shown in Table 1.

Example 3
1242 parts by weight (8.50 mol) of isosorbide, 402 parts by weight of 1,1-bis (4-hydroxyphenyl) cyclohexane (1.5 mol), 2185 parts by weight of diphenyl carbonate (10.20 mol), and 61 parts by weight of 1-hexanol A pellet was obtained by polymerizing in the same manner as in Example 1 except that a part (0.60 mol) was used. The obtained pellet had a specific viscosity of 0.32. Other evaluation results are shown in Table 1.

（式中、ｎ＝９）で表わされる片末端反応性ポリジメチルシロキサン１１重量部（０．０１モル）とを使用した以外は実施例１と同様に重合させてペレットを得た。このペレットは比粘度が０．３４であった。その他の評価結果については表１に示した。 Example 4
1374 parts by weight (9.4 mol) of isosorbide, 196 parts by weight (0.6 mol) of 1,1-bis (4-hydroxyphenyl) decane, 2164 parts by weight (10.10 mol) of diphenyl carbonate, and the following formula (16)

Pellets were obtained by polymerization in the same manner as in Example 1 except that 11 parts by weight (0.01 mol) of one-terminal reactive polydimethylsiloxane represented by the formula (n = 9) was used. This pellet had a specific viscosity of 0.34. Other evaluation results are shown in Table 1.

１９重量部（０．０３モル）とを使用した以外は実施例１と同様に重合させてペレットを得た。このペレットは比粘度が０．３９であった。その他の評価結果については表１に示した。 Example 5
1242 parts by weight (8.50 mol) of isosorbide, 405 parts by weight (1.5 mol) of 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2164 parts by weight of diphenyl carbonate (10.10 mol) and 4 -Hydroxybenzoic acid-4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11-heptadecafluoroundecyl ester (formula (17 ))

Pellets were obtained by polymerizing in the same manner as in Example 1 except that 19 parts by weight (0.03 mol) was used. This pellet had a specific viscosity of 0.39. Other evaluation results are shown in Table 1.

Example 6
1023 parts by weight (7.00 mol) of isosorbide, 228 parts by weight (3.00 mol) of 1,3-propanediol, 2185 parts by weight (10.20 mol) of diphenyl carbonate, and 81 parts by weight (0.30 mol) of stearyl alcohol Except that, pellets were obtained by polymerization in the same manner as in Example 1. This pellet had a specific viscosity of 0.31. Other evaluation results are shown in Table 1.

Example 7
1374 parts by weight (9.40 mol) of isosorbide, 85 parts by weight (0.60 mol) of 1,4-cyclohexanedimethanol, 2185 parts by weight (10.20 mol) of diphenyl carbonate, and 122 parts by weight of pentadecylphenol (0.4 Molten) was used in the same manner as in Example 1 to obtain pellets. This pellet had a specific viscosity of 0.31. Other evaluation results are shown in Table 1.

Comparative Example 1
1461 parts by weight (10 moles) of isosorbide and 2142 parts by weight (10 moles) of diphenyl carbonate were placed in a reactor, and 1.0 part by weight of tetramethylammonium hydroxide was used as a polymerization catalyst (1 × with respect to 1 mole of diphenyl carbonate component). ^10-4 mol), and 5.4 × 10 ⁻³ parts by weight of 2,2-bis (4-hydroxyphenyl) propane disodium salt (0.2 × 10 ⁻⁶ mol with respect to 1 mol of diphenyl carbonate component) The mixture was charged and melted at 180 ° C. in a nitrogen atmosphere.

Under stirring, the pressure in the reaction vessel was gradually reduced over 30 minutes, and the pressure was reduced to 13.3 × 10 ⁻³ MPa while the produced phenol was distilled off. 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 2 hours. The polymer after the reaction was pelletized to obtain a pellet having a specific viscosity of 0.36. In this case, since no hydroxy compound that can be terminally modified is added, the content of the terminally modified group is 0% by weight. Other evaluation results are shown in Table 1.

Comparative Example 2
The pellets were polymerized in the same manner as in Example 1 except that 1608 parts by weight (11 moles) of isosorbide, 2474 parts by weight (11.55 moles) of diphenyl carbonate, and 268 parts by weight (0.88 moles) of 3-pentadecylphenol were used. Obtained. This pellet had a specific viscosity of 0.16 and a terminal modified group content of 9.1% by weight. Other evaluation results are shown in Table 1.

Comparative Example 3
1366 parts by weight (9.35 moles) of isosorbide, 195 parts by weight of 1,6-hexanediol (1.65 moles) and 2356 parts by weight (11 moles) of diphenyl carbonate were placed in a reactor, and tetramethylammonium hydroxy was used as a polymerization catalyst. 1.0 part by weight (1 × 10 ⁻⁴ moles per mole of diphenyl carbonate component) and 5.4 × 10 ⁻³ parts by weight of 2,2-bis (4-hydroxyphenyl) propane disodium salt (0.2 × 10 ⁻⁶ mol per 1 mol of the diphenyl carbonate component) was charged and melted at 180 ° C. in a nitrogen atmosphere.

Under stirring, the pressure in the reaction vessel was gradually reduced over 30 minutes, and the pressure was reduced to 13.3 × 10 ⁻³ MPa while the produced phenol was distilled off. 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 240 ° C., and the reaction was finally carried out at 240 ° C. and 6.66 × 10 ⁻⁵ MPa for 1 hour. The polymer after the reaction was pelletized to obtain a pellet having a specific viscosity of 0.26. In this case, since no hydroxy compound that can be terminally modified is added, the content of the terminally modified group is 0% by weight. Other evaluation results are shown in Table 1.

Example 8
The terminal-modified polycarbonate resin obtained in Example 7 was melted using a KZW15-30MG film forming apparatus (manufactured by Technobell) and a KYA-2H-6 roll temperature controller (manufactured by Kato Riki Seisakusho). A membrane film was obtained. The extruder cylinder temperature was maintained within the range of 220 ° C to 260 ° C, and the roll temperature was 140 to 160 ° C. The physical properties of the obtained film are shown in Table 2.

Comparative Example 4
Using Panlite (registered trademark) L1225 manufactured by Teijin Chemicals Limited, which is a polycarbonate resin composed of bisphenol A, a KZW15-30MG film forming apparatus (manufactured by Technobell Co., Ltd.) and a KYA-2H-6 roll temperature controller (( A melt film-forming film was obtained using Kato Riki Seisakusho Co., Ltd. The extruder cylinder temperature was maintained in the range of 260 ° C to 300 ° C, and the roll temperature was 140 to 160 ° C. The physical properties of the obtained film are shown in Table 2. It can be seen that the photoelastic constant is high and the wavelength dispersion of the retardation value is large compared to the polycarbonate film of Example 7.

Examples 9-11
The unstretched end-modified polycarbonate film obtained in Example 8 was uniaxially stretched at a stretching temperature of 150 to 160 ° C. at three stretching ratios using a stretching machine to obtain a stretched film. Table 3 shows the retardation values of these stretched films and their physical properties of wavelength dispersion.

Example 12
The unstretched end-modified polycarbonate film obtained in Example 8 was subjected to simultaneous biaxial stretching using a batch-type simultaneous biaxial stretching machine. The magnification was 1.3 times in one direction, 1.4 times in the other direction, and the stretching temperature was 140 ° C. The physical properties of the obtained biaxially oriented film are shown in Table 4.

Comparative Examples 5 and 6
The polycarbonate film obtained in Comparative Example 4 was uniaxially stretched at two stretching ratios at a stretching temperature of 120 ° C. using a stretching machine to obtain a stretched film. Table 3 shows the retardation values of these stretched films and their physical properties of wavelength dispersion. Compared to the terminal-modified polycarbonate films of Examples 9 to 11, the retardation after stretching is less likely to be exhibited, the wavelength dispersion of the retardation value is large, and the retardation controllability is poor.

Claims (17)

The main chain is represented by the following formula (1)

And a specific viscosity at 20 ° C. of a solution prepared by dissolving 0.7 g in 100 ml of methylene chloride. 2 to 0.5, and the following formula (2) or (3)

{In the above formulas (2) and (3), R ¹ is 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, a phenyl group, Or the following formula (4)

(In the above formula (4), R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or a carbon atom. Represents 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, b is an integer of 0 to 3, c Is an integer of 4 to 100), and X represents at least one bond selected from the group consisting of a single bond, an ether bond, a thioether bond, an ester bond, an amino bond, and an amide bond, a is an integer of 1-5. }
The terminal modified polycarbonate which contains 0.01-7 mol% with respect to the principal chain in the terminal group represented by these.   The terminal-modified polycarbonate according to claim 1, comprising 0.05 to 7 mol% of the terminal group represented by the formula (2) or (3) with respect to the main chain.   The terminal-modified polycarbonate according to claim 1, wherein the water absorption after 24 hours at 23 ° C is 0.75% or less.   The terminal-modified polycarbonate according to claim 1, wherein the repeating unit represented by the formula (1) is a unit derived from isosorbide (1,4; 3,6-dianhydro-D-sorbitol).   The terminal-modified polycarbonate according to claim 1, wherein the terminal group represented by the formula (2) or (3) is derived from a biogenic substance. Following formula (5)

0.01 to 7 with respect to the ether diol (component A) represented by the formula, diol other than the ether diol and / or diphenol compound (component B), carbonic acid diester (component C) and the total of components A and B The following formula (6) or (7)

{In the above formulas (6) and (7), R ¹ is 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, a phenyl group, Or the following formula (4)

(In the above formula (4), R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or a carbon atom. Represents 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, b is an integer of 0 to 3, c Is an integer of 4 to 100), and X represents at least one bond selected from the group consisting of a single bond, an ether bond, a thioether bond, an ester bond, an amino bond, and an amide bond, a is an integer of 1-5. }
The manufacturing method of the terminal modified polycarbonate characterized by making the hydroxy compound (D component) represented by these react.   The amount of the carbonic acid diester (C component) is a molar ratio (C component / (A component) with respect to the total of the ether diol (A component) and the diol other than the ether diol and / or the diphenol compound (B component). The manufacturing method according to claim 6, wherein the component (B) is 1.05 to 0.97.   In the presence of a polymerization catalyst, ether diol (component A), diol other than the ether diol and / or diphenol compound (component B), carbonic acid diester (component C) and hydroxy compound (component D) are heated at normal pressure. And then melt polycondensation while heating at a temperature of 180 ° C. to 280 ° C. under reduced pressure.   The production method according to claim 6, wherein at least one compound selected from the group consisting of a nitrogen-containing basic compound, an alkali metal compound, and an alkaline earth metal compound is used as the polymerization catalyst.   The production method according to claim 6, wherein the ether diol (component C) is isosorbide (1,4; 3,6-dianhydro-D-sorbitol).   The production method according to claim 6, wherein the hydroxy compound (component D) is derived from a biogenic substance. Following formula (5)

An diol other than the ether diol and / or a diphenol compound (B component) and phosgene (E component) are reacted in an inert solvent in the presence of an acid binder. A process for producing a polycarbonate, wherein the terminal terminator is represented by the following formula (6) or (7):

{In the above formulas (6) and (7), R ¹ is 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, a phenyl group, Or the following formula (4)

(In the above formula (4), R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or a carbon atom. Represents 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, b is an integer of 0 to 3, c Is an integer of 4 to 100), and X represents at least one bond selected from the group consisting of a single bond, an ether bond, a thioether bond, an ester bond, an amino bond, and an amide bond, a is an integer of 1-5. }
The manufacturing method of the terminal modified polycarbonate characterized by making the hydroxy compound (D component) represented by these react.   The production method according to claim 12, wherein the acid binder is at least one selected from the group consisting of pyridine, quinoline and dimethylaniline.   The production method according to claim 12, wherein the ether diol (component A) is isosorbide (1,4; 3,6-dianhydro-D-sorbitol).   The production method according to claim 12, wherein the hydroxy compound (component D) is derived from a biogenic substance.   A molded article comprising the terminal-modified polycarbonate according to claim 1.   The molded article according to claim 16, which is a film.