JP2011219639A - Resin composition and method for producing the same, and optical material and film using the resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aromatic polyester resin having a substituted aromatic ring and excelling in heat resistance and mechanical characteristics, and a method for successfully produce the aromatic polyester resin by melt polymerization or high temperature solution polymerization.SOLUTION: This method for producing the resin composition comprises: a step of adding a fatty acid anhydride to an aromatic diol expressed by general formula (I) for acylation; a step of adding at least one among a hindered phenol and an organic phosphorus compound; and a step of obtaining the aromatic polyester resin by ester exchange of the acylated product of the aromatic diol and an aromatic dicarboxylic acid by melt polymerization or high temperature solution polymerization. In the formula, R-Rare each independently represents hydrogen or a substituent, provided that at least one denotes a substituent; and X represents a single bond or a bivalent linking group.

Description

  The present invention relates to a production method of a resin composition by melt polymerization or high temperature solution polymerization, and a resin composition obtained by the production method. Specifically, the present invention relates to an aromatic polyester resin composition and a method for producing the same. The present invention also relates to an optical material or film using the resin composition.

  Inorganic glass materials are widely used as transparent materials because they are excellent in transparency and heat resistance and have small optical anisotropy. However, since inorganic glass is difficult to mold and has a large specific gravity and is brittle, the molded glass product is disadvantageous in that it is heavy and easily damaged. Due to such drawbacks, in recent years, development of resin materials that replace inorganic glass materials has been actively conducted.

  For example, polymethyl methacrylate, polycarbonate, polyethylene terephthalate, and the like are known as resin materials intended to replace such inorganic glass materials. Since these resin materials are lightweight, excellent in mechanical properties, and excellent in processability, they are recently used in various applications such as lenses and films.

  In recent years, it has been studied to replace the display substrate from glass to resin, and in particular, a resin substrate on which ITO (indium tin oxide) can be placed is required. This is because by using a resin, various advantages such as weight reduction, impact resistance, and reduction in thickness can be obtained. In order for such a resin substrate to replace glass, a certain degree of heat resistance (approximately 150 ° C. to 270 ° C.) is required. As resins having such heat resistance and various mechanical properties, aromatic polyester resins obtained by polycondensation of aromatic diols and aromatic dicarboxylic acids have been developed.

As a method for producing the aromatic polyester resin, a general polyester resin method is used. That is, for example, a solution polymerization method in which a divalent carboxylic acid halide and a divalent phenol are reacted in an organic solvent, a melt polymerization method in which the divalent carboxylic acid and the divalent phenol are heated in the presence of acetic anhydride, Melt polymerization method in which divalent carboxylic acid and divalent phenol are heated in the presence of diallyl carbonate, divalent carboxylic acid halide dissolved in water-incompatible organic solvent and divalent phenol dissolved in alkaline aqueous solution And interfacial polymerization. Among them, from the viewpoint of fast reaction, the interfacial polymerization method is advantageous when a polymer having a high degree of polymerization is obtained (see Patent Document 1).
On the other hand, it is required to produce an aromatic polyester resin by melt polymerization or high temperature solution polymerization from the viewpoint of reducing the production cost, the viewpoint of reducing the amount of solvent used, and the viewpoint of easily using the resin material for film applications. As an example of such a production method, in Patent Document 2, before the polymerization of the aromatic polyester is completed, a heat stabilizer is added in a state of being coated with the same or different kind of aromatic polyester, and is uniformly dispersed. Later, a process for producing an aromatic polyester composition that completes the polymerization is described. In addition, it is described that the aromatic polyester composition obtained by the method described in the document can improve the tensile strength retention due to coloring after heating and thermal degradation.

  In recent years, aromatic polyester resins having a substituted aromatic ring have been developed for the purpose of further improving the properties of the aromatic polyester resin. For example, Patent Document 1 discloses a polyarylate using a biphenol having a substituted aromatic ring as an aromatic diol. However, an example in which an aromatic polyester resin having an aromatic ring substituted by melt polymerization or high temperature solution polymerization using biphenol having an actual substituent was not described. Also, Patent Document 2 which is considering melt polymerization does not describe an example of producing an aromatic polyester resin having a substituted aromatic ring, and melts an aromatic polyester resin having a substituted aromatic ring. No mention was made of a description suggesting that it can be produced by polymerization or a problem when using an aromatic polyester resin having a substituted aromatic ring.

Japanese Patent Laid-Open No. 10-17658 Japanese Patent Publication No. 6-84428

  The present inventors have studied for the purpose of producing an aromatic polyester resin having a substituted aromatic ring satisfactorily by melt polymerization or high temperature solution polymerization. That is, the problem to be solved by the present invention is that an aromatic polyester resin having a substituted aromatic ring excellent in heat resistance and mechanical properties, and producing the aromatic polyester resin satisfactorily by melt polymerization or high-temperature solution polymerization It is to provide a method.

  When the present inventors melt polymerized or high-temperature solution polymerized aromatic polyester resin having a substituted aromatic ring by the usual method introduced in Patent Document 1, such a heat-resistant resin is polymerized by heating. It was found that a certain high temperature condition is necessary. In addition, when polymerizing at a high temperature, it is not bound by any theory, but a substituent on an aromatic ring, which is generally considered to be highly reactive, is involved in crosslinking, etc. It has been found that there is a problem of gelation during polymerization due to the heat of. Such a gelled resin may cause insoluble matter when dissolved in a solvent, or may deteriorate in stretchability when formed into a film, so that it has mechanical properties when applied to optical materials and films. It was found that there was a dissatisfaction. Moreover, it turned out that the substituted aromatic diol which has the substituted aromatic ring used as a raw material also has the problem that a polymerization reaction rate is inferior compared with unsubstituted aromatic diol.

  However, the problems of the gelation and the polymerization reaction rate are not described in Patent Documents 1 and 2, and it has been found that they cannot be produced by the methods described in these documents. Specifically, in Patent Document 1, various raw materials of an aromatic polyester resin having a substituted aromatic ring are dissolved in an aqueous phase and an organic phase, respectively, and interfacial polymerization is performed without heating. The problem caused by the problem did not occur. In addition, in Patent Document 2, an aromatic polyester resin having an unsubstituted aromatic ring is produced. However, there is a problem of gelation due to cross-linking between substituents on the aromatic ring or a problem of a decrease in polymerization reaction rate. It did not happen.

  On the other hand, the inventors of the present invention have made extensive studies for the purpose of solving the gelation problem and the polymerization reaction rate. As a result, when a substituted aromatic diol having an aromatic ring is acylated using a specific acylating agent, and a specific additive is added, it is unique in producing an aromatic polyester resin having a substituted aromatic ring. We have found that these problems can be solved. That is, an aromatic polyester resin having a substituted aromatic ring excellent in heat resistance and mechanical properties and a method for producing the aromatic polyester resin satisfactorily by melt polymerization or high-temperature solution polymerization have been found, and the present invention has been completed. It was.

（一般式（Ｉ）中、Ｒ¹¹〜Ｒ¹⁸はそれぞれ独立に水素原子または置換基を表し、少なくとも一つは置換基を表す。Ｘは単結合または二価の連結基を表す。）
［２］ 前記一般式（Ｉ）で表わされる芳香族ジオールが、下記一般式（ＩＩ）で表わされることを特徴とする［１］に記載の樹脂組成物の製造方法。

（一般式（ＩＩ）中、Ｒ²¹〜Ｒ²⁸はそれぞれ独立に水素原子または置換基を表し、少なくとも一つは置換基を表す。）
［３］ アルカリ金属塩、アルカリ土類金属塩、アミン化合物からなる群より選ばれる少なくとも一種の化合物を添加することを特徴とする［１］または［２］に記載の樹脂組成物の製造方法。
［４］ 少なくとも一種のオニウム塩を添加することを特徴とする［１］〜［３］のいずれか一項に記載の樹脂組成物の製造方法。
［５］ 前記アシル化工程が終了した後に、前記エステル交換工程を行うことを特徴とする［１］〜［４］のいずれか一項に記載の樹脂組成物の製造方法。
［６］ 前記アシル化工程が終了した後に、前記ヒンダードフェノールおよび有機リン化合物のうち少なくとも一種を添加する工程を行い、その後に前記エステル交換工程を行うことを特徴とする［１］〜［５］のいずれか一項に記載の樹脂組成物の製造方法。
［７］ 前記エステル交換工程開始時における、前記芳香族ポリエステル樹脂の重合に用いられる全ての芳香族ジオールのフェノール性ヒドロキシル基の平均アシル化率が９６％以上であることを特徴とする［６］に記載の樹脂組成物の製造方法。
［８］ 前記芳香族ポリエステル樹脂に対する、前記ヒンダードフェノールおよび有機リン化合物のうち少なくとも一種の添加量が２質量％を超え、５質量％以下であることを特徴とする［１］〜［７］のいずれか一項に記載の樹脂組成物の製造方法。
［９］ ［１］〜［８］のいずれか一項に記載の樹脂組成物の製造方法により製造されたことを特徴とする樹脂組成物。
［１０］ Ａ）下記一般式（１）で表わされる構造と芳香族ジカルボン酸由来の構造を有する芳香族ポリエステルと、Ｂ）ヒンダードフェノールおよび有機リン化合物のうち少なくとも一種とを含むことを特徴とする樹脂組成物。

（一般式（１）中、Ｒ¹¹¹〜Ｒ¹¹⁸はそれぞれ独立に水素原子または置換基を表し、少なくとも一つは置換基を表す。Ｘは単結合または二価の連結基を表す。）
［１１］ 重量平均分子量が７０００〜１０００００であることを特徴とする［９］または［１０］に記載の樹脂組成物。
［１２］ ［９］〜［１１］のいずれか一項に記載の樹脂組成物を製膜したことを特徴とするフィルム。
［１３］ ［９］〜［１１］のいずれか一項に記載の樹脂組成物で作製したことを特徴とする光学材料。 That is, the present inventors have found that the above problem can be achieved by the following configuration.
[1] A step of adding a fatty acid anhydride to an aromatic diol represented by the following general formula (I) for acylation, a step of adding at least one of hindered phenols and organophosphorus compounds, and the aromatic diol And a process for obtaining an aromatic polyester resin by transesterifying the acylated product and aromatic dicarboxylic acid by melt polymerization or high temperature solution polymerization.

(In the general formula (I), R ^{11 to} R ¹⁸ each independently represents a hydrogen atom or a substituent, and at least one represents a substituent. X represents a single bond or a divalent linking group.)
[2] The method for producing a resin composition according to [1], wherein the aromatic diol represented by the general formula (I) is represented by the following general formula (II).

(In general formula (II), R ^{21 to} R ²⁸ each independently represents a hydrogen atom or a substituent, and at least one represents a substituent.)
[3] The method for producing a resin composition according to [1] or [2], wherein at least one compound selected from the group consisting of alkali metal salts, alkaline earth metal salts, and amine compounds is added.
[4] The method for producing a resin composition according to any one of [1] to [3], wherein at least one onium salt is added.
[5] The method for producing a resin composition according to any one of [1] to [4], wherein the transesterification step is performed after the acylation step is completed.
[6] After the acylation step is completed, a step of adding at least one of the hindered phenol and the organophosphorus compound is performed, and then the transesterification step is performed. [1] to [5] ] The manufacturing method of the resin composition as described in any one of.
[7] The average acylation rate of phenolic hydroxyl groups of all aromatic diols used for polymerization of the aromatic polyester resin at the start of the transesterification step is 96% or more [6] The manufacturing method of the resin composition as described in any one of.
[8] The amount of at least one of the hindered phenol and the organic phosphorus compound added to the aromatic polyester resin is more than 2% by mass and 5% by mass or less. [1] to [7] The manufacturing method of the resin composition as described in any one of these.
[9] A resin composition produced by the method for producing a resin composition according to any one of [1] to [8].
[10] A) comprising an aromatic polyester having a structure represented by the following general formula (1) and a structure derived from an aromatic dicarboxylic acid, and B) at least one of a hindered phenol and an organophosphorus compound. Resin composition.

(In general formula (1), R ^{111 to} R ¹¹⁸ each independently represents a hydrogen atom or a substituent, and at least one represents a substituent. X represents a single bond or a divalent linking group.)
[11] The resin composition as described in [9] or [10], wherein the weight average molecular weight is 7,000 to 100,000.
[12] A film obtained by forming the resin composition according to any one of [9] to [11].
[13] An optical material produced by using the resin composition according to any one of [9] to [11].

  According to the present invention, an aromatic polyester resin having a substituted aromatic ring excellent in heat resistance and mechanical properties, a method for producing the aromatic polyester resin satisfactorily by melt polymerization or high-temperature solution polymerization, and use thereof It is possible to provide an optical component, a film, and an image display device using the film. Furthermore, the resin composition of the present invention is excellent in transparency at the time of molding, and can be suitably used for optical parts, films and image display devices.

  Hereinafter, the polyester resin, film, and image display device included in the resin composition of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

[Method for Producing Resin Composition]
A method for producing a resin composition of the present invention (hereinafter also referred to as a production method of the present invention) comprises a step of acylating an aromatic diol represented by the following general formula (I) by adding a fatty acid anhydride, hindered A step of adding at least one of phenol and an organophosphorus compound, and a step of obtaining an aromatic polyester resin by transesterification of the acylated product of the aromatic diol and the aromatic dicarboxylic acid by melt polymerization or high-temperature solution polymerization. It is characterized by that. Hereinafter, the manufacturing method of the resin composition of this invention is demonstrated.

一般式（Ｉ）中、Ｒ¹¹〜Ｒ¹⁸はそれぞれ独立に水素原子または置換基を表し、少なくとも一つは置換基を表す。Ｘは単結合または二価の連結基を表す。

In the general formula (I), R ^{11 to} R ¹⁸ each independently represent a hydrogen atom or a substituent, and at least one represents a substituent. X represents a single bond or a divalent linking group.

<Order of each process>
The production method of the present invention is not particularly limited with respect to the order of performing the acylation step, the step of adding at least one of the hindered phenol and the organophosphorus compound, and the transesterification step. It may be performed in the order or simultaneously.
In the production method of the present invention, it is preferable to perform the transesterification step after the acylation step is completed from the viewpoint of preventing the obtained aromatic polyester resin from being gelled. In the present specification, the completion of the acylation step means a state where the equilibrium of the acylation reaction has been substantially reached.
In the production method of the present invention, the step of adding at least one of the hindered phenol and the organophosphorus compound is performed, and then the transesterification step is performed so as not to gel the resulting aromatic polyester resin. From the viewpoint, it is more preferable.
In the production method of the present invention, it is particularly preferable that after the acylation step is completed, a step of adding at least one of the hindered phenol and the organic phosphorus compound is performed, and then the transesterification step is performed.

<Melt polymerization method, high temperature solution polymerization method>
In the production method of the present invention, an aromatic polyester resin is obtained by transesterification of an acylated diol represented by the general formula (I) and an aromatic dicarboxylic acid by melt polymerization or high-temperature solution polymerization. In the production method of the present invention, the production cost can be reduced as compared with the conventional method by using the melt polymerization method or the high temperature solution polymerization method. Further, in the production method of the present invention, when the aromatic diol has a substituent, it is found that the gelation problem occurs when the usual melt polymerization method or high temperature solution polymerization method is used, and the gelation problem is solved. can do.

  In the present invention, melt polymerization refers to a method in which polymerization is carried out in a state that does not substantially contain a solvent (other than the elimination component) in any step of the polymerization. Moreover, high temperature solution polymerization means the method of adding a solvent intentionally in any process of superposition | polymerization.

In the production method of the present invention, the solvent preferably used when performing high-temperature solution polymerization is described in page 92 of “New Polymer Experiments Vol. 3, Synthesis and Reaction of Polymers (2)” (Kyoritsu Shuppan). In addition, compounds described in the paragraph [0012] of JP-A-7-188405 can be exemplified, and among these, diphenyl ether is particularly preferable.
As the content of the solvent, at least one of aromatic diol, fatty acid anhydride, hindered phenol and organophosphorus compound represented by the general formula (I), all raw materials and additives such as aromatic dicarboxylic acid, It is preferable that it is 50 mass% or less with respect to the sum total of a solvent, It is more preferable that it is 30 mass% or less, It is especially preferable that it is 20 mass% or less.
The solvent may be added from the start of production, but an amount within the above range may be added at any time in the production process. That is, the solvent may be added only in the acylation step, or the solvent may be added only in the transesterification step, or the solvent may be added throughout the production process.

  Hereinafter, although the manufacturing method of the resin composition of this invention is further demonstrated, unless otherwise indicated, these apply also to the case of any method of melt polymerization and high temperature solution polymerization.

<Acylation step>
The manufacturing method of the resin composition of this invention includes the process of adding a fatty acid anhydride to the aromatic diol represented by the said general formula (I), and acylating. That is, it includes a step of acylating the phenolic hydroxyl group of the aromatic diol with a fatty acid anhydride.

(Aromatic diol represented by general formula (I))
The method for producing the resin composition of the present invention uses the aromatic diol represented by the general formula (I).

In the general formula (I), R ^{11 to} R ¹⁸ each independently represent a hydrogen atom or a substituent, but at least one is a substituent. Examples of preferable substituents include an alkyl group (having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group), a halogen atom (for example, a chlorine atom, a bromine atom, and an iodine atom). An aryl group (preferably having 6 to 20 carbon atoms, such as a phenyl group, a biphenyl group or a naphthyl group), an alkoxy group (preferably having 1 to 10 carbon atoms, such as a methoxy group, an ethoxy group or an isopropoxy group), An acyl group (preferably having 2 to 10 carbon atoms, for example, acetyl group, propionyl group, butyryl group, etc.), acylamino group (preferably having 1 to 10 carbon atoms, such as formylamino group, acetylamino group, etc.), nitro group, And a cyano group and a combination thereof. Among these, an alkyl group, a halogen atom, an aryl group, an alkoxy group, a cyano group, and a nitro group are particularly preferable, and a halogen atom, an alkyl group, an aryl group, a cyano group, and an alkoxy group are particularly preferable. More preferably, they are a fluorine atom, a chlorine atom, an alkyl group (preferably a methyl group or an ethyl group), a phenyl group or a methoxy group.
Among them, since the gelation is likely to occur when the melt polymerization or hot solution polymerization when R ¹¹ to R ¹⁸ are particularly alkyl group, a manufacturing method of the present invention when R ¹¹ to R ¹⁸ is an alkyl group It can be preferably used.

In the general formula (I), particularly when R ^{15 to} R ¹⁸ have at least one substituent, gelation is likely to occur during melt polymerization or high-temperature solution polymerization, and the number of substituents out of R ^{15 to} R ^18. Increases, the gelation is likely to occur. In particular, the gelation is more likely to occur as the number of alkyl groups among R ^{15 to} R ¹⁸ increases.
That is, the production method of the present invention can be preferably used when R ^{15 to} R ¹⁸ have at least one substituent, and can be more preferably used as the number of substituents among R ^{15 to} R ¹⁸ increases. , R ^{15 to} R ¹⁸ can be particularly preferably used when all are substituents. Furthermore, it can be particularly preferably used as the number of alkyl groups among R ^{15 to} R ¹⁸ increases.

In the general formula (I), X represents a single bond or a divalent linking group. Preferred examples of the divalent linking group include an alkylene group, an alkylidene group, a perfluoroalkylidene group, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, —NR ′ — (R ′ represents a hydrogen atom or a carbon number of 1 to 6). An alkylidene group, an oxygen atom, a sulfur atom, a carbonyl group, an imino group, and a sulfonyl group. Among these, particularly preferred examples of X are a single bond, isopropylidene and an oxygen atom.
X may be a part of a ring structure, that is, X itself may be a linking group containing a ring, and the benzene is linked to both sides of X together with at least one of R ^{11 to} R ¹⁴ . It means that a fused ring may be made with one and / or both of the rings. Examples of the linking group in which X itself includes a ring include a fluorene ring, an indandione ring, an indanone ring, an indene ring, an indan ring, a tetralone ring, an anthrone ring, a cyclohexane ring, a cyclopentane ring, a chroman ring, and 2,3-dihydro Examples thereof include a benzofuran ring, an indoline ring, a tetrahydropyran ring, a tetrahydrofuran ring, and a dioxane ring. Among them, X is preferably an alkylidene group, oxygen atom, sulfur atom, ketone group, amino group or sulfonyl group, and particularly preferably isopropylidene or oxygen atom.

  In the general formula (I), the two hydroxyl groups may be located anywhere on the benzene ring. Among them, the positions of the two hydroxyl groups are preferably the 4th and 4 'positions of the benzene ring.

  In the production method of the present invention, the aromatic diol represented by the general formula (I) is preferably represented by the following general formula (II).

一般式（ＩＩ）中、Ｒ²¹〜Ｒ²⁸はそれぞれ独立に水素原子または置換基を表し、少なくとも一つは置換基を表す。
前記一般式（ＩＩ）におけるＲ²¹〜Ｒ²⁸の好ましい例としては、前記一般式（Ｉ）におけるＲ¹¹〜Ｒ¹⁸の好ましい例と同様である。

In the general formula (II), R ^{21 to} R ²⁸ each independently represent a hydrogen atom or a substituent, and at least one represents a substituent.
Preferred examples of R ^{21 to} R ²⁸ in the general formula (II) are the same as the preferred examples of R ^{11 to} R ¹⁸ in the general formula (I).

Two or more aromatic diols represented by the general formula (I) may be used.
When 2 or more types of aromatic diol represented by the said general formula (I) are contained, it is preferable to contain at least the aromatic biphenol represented by the said general formula (II). Further, two or more aromatic biphenols represented by the general formula (II) may be included.

Moreover, it is also preferable to use together the aromatic biphenol represented by the said general formula (II), and the aromatic diol represented by the said general formula (I) other than represented by the said general formula (II).
Here, as the aromatic diol represented by the general formula (I) other than that represented by the general formula (II), known diols can be used, and among them, the aromatic bisphenol is used. For example, bisphenol C is preferably used.

  Specific examples of the aromatic diol represented by the general formula (I) are shown below, but the aromatic diol represented by the general formula (I) that can be used in the present invention is not limited thereto. Absent.

(Other aromatic diols)
The aromatic polyester resin may be produced using other aromatic diols in addition to the aromatic diol having a substituted aromatic ring represented by the general formula (I). Preferable examples of the other aromatic diols include aromatic diols having an unsubstituted aromatic ring represented by the following general formula (III).

前記一般式（ＩＩＩ）中、 Ｙは単結合または２価の連結基を表す。２価の連結基の好ましい例としては、アルキレン基、アルキリデン基、パーフルオロアルキリデン基、酸素原子、硫黄原子、カルボニル基、スルホニル基、−ＮＲ'−（Ｒ'は水素原子または炭素数１〜６のアルキル基）、−ＣＯ−ＮＨ−が挙げられ、より好ましくはアルキリデン基、酸素原子、硫黄原子、カルボニル基、イミノ基、スルホニル基である。これらのうちＹの特に好ましい例は、単結合、イソプロピリデン、酸素原子である。

In the general formula (III), Y represents a single bond or a divalent linking group. Preferred examples of the divalent linking group include an alkylene group, an alkylidene group, a perfluoroalkylidene group, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, —NR ′ — (R ′ represents a hydrogen atom or a carbon number of 1 to 6). An alkylidene group, an oxygen atom, a sulfur atom, a carbonyl group, an imino group, and a sulfonyl group. Among these, particularly preferred examples of Y are a single bond, isopropylidene, and oxygen atom.

  In the general formula (III), the two hydroxyl groups may be located anywhere on the benzene ring. Among them, the positions of the two hydroxyl groups are preferably the 4th and 4 'positions of the benzene ring.

  Two or more types of structures represented by the general formula (III) may be included.

  Specific examples of the aromatic diol having an unsubstituted aromatic ring represented by the general formula (III) are shown below. The unsubstituted aromatic ring represented by the general formula (III) that can be used in the present invention are shown below. However, the aromatic diol having the above is not limited thereto.

(Fatty acid anhydride)
In the method for producing a resin composition of the present invention, a fatty acid anhydride is added to the aromatic diol represented by the general formula (I) in the acylation step. With such a configuration, in the production method of the present invention, the fatty acid liberated from the fatty acid anhydride after the acylation reaction is heated and removed out of the system to move the equilibrium of the acylation reaction in the traveling direction, and the general formula The acylation rate of the aromatic diol represented by (I) can be increased. As a result, gelation of the aromatic polyester resin obtained by melt polymerization or high temperature solution polymerization can be suppressed.

  Examples of the fatty acid anhydride include acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, pivalic anhydride, 2-ethylhexanoic anhydride, monochloroacetic anhydride, dichloroacetic anhydride, trichloroacetic anhydride, Examples include monobromoacetic anhydride, dibromoacetic anhydride, tribromoacetic anhydride, monofluoroacetic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, glutaric anhydride, maleic anhydride, succinic anhydride, and β-bromopropionic anhydride. There is no particular limitation. You may use these in mixture of 2 or more types. From the viewpoints of economy and handleability, acetic anhydride, propionic anhydride, butyric anhydride, and isobutyric anhydride are preferable, and acetic anhydride is more preferable.

  The amount of the fatty acid anhydride used relative to the phenolic hydroxyl group of all aromatic diols used for the polymerization of the aromatic polyester resin is preferably 1.0 to 1.4 times equivalent, and 1.0 to 1.30 times equivalent. Is more preferable, and 1.03 to 1.15 times equivalent is particularly preferable. When the amount of the fatty acid anhydride used is 1.0 times equivalent or more with respect to the phenolic hydroxyl group, the acylation reaction proceeds sufficiently, and the degree of polymerization of the aromatic polyester resin is easily increased. It is preferable because an unreacted aromatic diol or aromatic dicarboxylic acid does not sublime at the time of polymerization and the reaction system tends not to be blocked. Moreover, when it is 1.4 times equivalent or less, there exists a tendency for the polymerization degree of the said aromatic polyester resin obtained to rise easily, and it is preferable.

  In the production method of the present invention, it is preferable to carry out the acylation step in an open system (under atmospheric pressure) from the viewpoint of heating the fatty acid liberated from the fatty acid anhydride after the acylation reaction to facilitate removal from the system.

(Acylation accelerator (additive 3))
In the production method of the present invention, at least one compound selected from the group consisting of alkali metal salts, alkaline earth metal salts, and amine compounds (hereinafter, these compounds may be referred to as “additive 3”) is added. It is preferable. By adding the additive 3, the addition rate of the acylation reaction of the aromatic diol is improved, and the polymerization degree of the resin can be increased. The additive 3 can be added at any time during the production process, and in particular in the production method of the present invention, at least one compound selected from the group consisting of the alkali metal salts, alkaline earth metal salts, and amine compounds. Is preferably added at least in the acylation step from the viewpoint of shortening the heating time so that the reaction rate of the acylation reaction is accelerated and the resin composition is not gelled.
That is, the resin composition of the present invention described later preferably contains at least one compound selected from the group consisting of alkali metal salts, alkaline earth metal salts, and amine compounds.

  Examples of the alkali metal salts include alkali metal inorganic acid salts, fatty acid salts, carbonate salts, phosphate salts, silicate salts, and borate salts. Among these, lithium, sodium, potassium inorganic acid salts, fatty acid salts, Carbonate, phosphate, phosphite, hypophosphite are preferred, lithium, sodium, potassium inorganic acid salt, fatty acid salt, carbonate metal carboxylate are more preferred, sodium acetate, potassium acetate Lithium acetate and magnesium acetate are particularly preferred from the viewpoints of versatility and economy.

  Examples of the alkaline earth metal salt include inorganic acid salts, fatty acid salts, carbonates, phosphates, silicates, and borate salts of alkaline earth metals, and among these, inorganic salts of magnesium, calcium, and barium. Fatty acid salts, carbonates, phosphates, phosphites and hypophosphites are preferred, and inorganic salts of magnesium and calcium, fatty acid salts and carboxylates of carbonated metals are particularly preferred.

The amine compound may be a primary amine, a secondary amine, or a tertiary amine, and may be an aliphatic amine or an aromatic amine. Specific examples thereof include alkanolamines represented by triethanolamine, diisopropanolamine, triisopropanolamine, 2-N- (2-aminoethyl) ethanolamine, cyclopentylamine, cyclohexylamine, cycloheptylamine, and dicyclohexyl. Amine, 1,3-bisaminomethylcyclohexane, metaxylenediamine, laurylamine, oleylamine, and pyridine compounds, quinoline compounds, imidazole compounds, triazole compounds, dipyridylyl compounds, phenanthroline compounds, diazaphenanthrene compounds 1,5-diazabicyclo [4.3.0] non-5-ene, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] un 7-Sen, N, N- dimethylaminopyridine, and the like. Of these, quinoline compounds, pyridine compounds, and imidazole compounds are preferable, and 1-methylimidazole is more preferable from the viewpoint of reactivity.
Preferable examples of the quinoline compounds include isoquinoline and the like.
Preferred examples of the pyridine compounds include β-picoline, γ-picoline, 3-ethylpyridine, 4-ethylpyridine, 4-propylpyridine, 4-butylpyridine, 4-isobutylpyridine, 3,4-lutidine, 3 , 5-lutidine, 3-methyl-4-ethylpyridine, 3-ethyl-4-methylpyridine, 3,4-diethylpyridine, 3,5-diethylpyridine, 4- (5-nonyl) pyridine and the like alkylpyridines Alkyloxypyridines such as 3-methoxypyridine and 4-methoxypyridine.
Preferred examples of the imidazole compounds include imidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 1-ethylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 1-methyl-2- Ethyl imidazole, 1-methyl-4 ethyl imidazole, 1-ethyl-2-methyl imidazole, 1-ethyl-2-ethyl imidazole, 1-ethyl-2-phenyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl Examples include imidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1-benzyl-2-methylimidazole, and 2-phenyl-4-methylimidazole.

  At least one compound selected from the group consisting of the alkali metal salt, alkaline earth metal salt, and amine compound may be used alone or in combination of two or more.

  At least one compound selected from the group consisting of the alkali metal salts, alkaline earth metal salts, and amine compounds is composed of all monomers (all aromatic diols, all aromatics used for polymerization of the aromatic polyester resin). It is preferable to add 0.0001-2.0 mass% with respect to dicarboxylic acid etc.), it is more preferable to add 0.001-1.0 mass%, and 0.01-0.5 mass% is added. It is particularly preferred.

(Reaction conditions for the acylation reaction)
The acylation reaction is preferably performed at 130 ° C. to 180 ° C. for 30 minutes to 20 hours, and more preferably at 140 to 160 ° C. for 1 to 5 hours.

ここで、本明細書中、前記平均アシル化率とは、前記芳香族ポリエステル樹脂の重合に用いられる全ての芳香族ジオールのアシル化工程前のフェノール性ヒドロキシル基に対する、アシル化工程後にアシル化されている全ての芳香族ジオール由来のフェノール性ヒドロキシル基の割合（百分率）のことを言う。 (Acylation rate)
The production method of the present invention preferably has a high average acylation rate of phenolic hydroxyl groups of all aromatic diols used for polymerization of the aromatic polyester resin at the start of the transesterification step. Specifically, it is preferably 96% or more, more preferably 98% or more, and particularly preferably 99% or more. By setting it within this range, the reaction point concentration in the reaction system increases, the reaction rate in the transesterification (polycondensation) step increases, and the degree of polymerization can be improved in a shorter time.
That is, the end point of the acylation step in the production method of the present invention can be arbitrarily determined by quantifying the amount of (introduced) acyl group relative to the amount of aromatic diol. That is, it is preferable that the conversion rate of the acylation reaction is calculated from the following formula (1), and the end point of the acylation reaction is the time when this conversion rate (average acylation rate) reaches a certain value.

Here, in the present specification, the average acylation rate refers to acylation after the acylation step with respect to the phenolic hydroxyl group before the acylation step of all aromatic diols used for the polymerization of the aromatic polyester resin. The ratio (percentage) of phenolic hydroxyl groups derived from all aromatic diols.

The acylation rate can be measured by the following method for determining the amount of acyl groups.
As a method for quantifying the amount of acyl groups, any known method may be used. As a preferred example, a part of the solution in the reaction system is collected and quantified by measuring a nuclear magnetic resonance spectrum (NMR). Is mentioned.

  The acylation rate of each aromatic diol is similarly the phenolic hydroxyl group derived from each aromatic diol acylated after the acylation step with respect to the phenolic hydroxyl group before the acylation step of each aromatic diol. As a percentage (percentage).

<Step of adding hindered phenol / organic phosphorus compound>
The method for producing a resin composition of the present invention includes a step of adding at least one of the hindered phenol and the organic phosphorus compound. That is, it is characterized in that a hindered phenol compound and / or an organophosphorus compound is added during the production process. By adding these compounds to produce the resin composition of the present invention, it is possible to suppress the gelation of the resin by heating at the time of production, or the reproducibility of the degree of polymerization is remarkably improved and the production is stable. Can do. Such gelation and destabilization of polymerization are characteristic of an aromatic polyester resin obtained when melt polymerization or high-temperature melt film formation is performed using the aromatic diol represented by the general formula (I). . That is, the hindered phenol compound and / or the organophosphorus compound is added for the purpose of improving the thermal stability of the aromatic polyester resin. The relationship between the aromatic diol represented by the general formula (I) and the destabilization (or gelation) of the polymerization is not limited to any theory, but in the general formula (I) It is presumed that the aromatic diol represented is susceptible to the influence of thermal radicals generated during the reaction (eg, a radical is generated at the benzyl position).

(Hindered phenol (additive 1))
The said hindered phenol used in the manufacturing method of this invention is demonstrated. In the production method of the present invention, any known hindered phenol compound can be used (hereinafter, these compounds may be referred to as “additive 1”). Preferred examples include 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (trade name: IRGANOX 1330), pentaerythrityl-tetrakis. [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 1010), 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5- Methylbenzyl) -4-methylphenyl acrylate (trade name: Sumilizer GM), 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentyl Phenyl acrylate (trade name: Sumilizer GS), N, N′-hexamethylenebis (3,5-di -Tert-butyl-4-hydroxy-hydrocinnamamide) (trade name: IRGANOX 1098), 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ] (Trade name: IRGANOX 259), 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] 1,1-dimethylethyl] 2,4, 8,10-tetraoxaspiro [5.5] undecane (trade name: Sumilizer GA-80), tris- (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: IRGANOX 3114) , Isooctyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ( Product name: IRGANOX 1135), 4,4'-thiobis (6-tert-butyl-3-methylphenol) (trade name: Sumilizer WX-R), 6- [3- (3-tert-butyl-4-hydroxy-) 5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine (trade name: Sumilizer GP).
The hindered phenol used in the production method of the present invention preferably has a large molecular weight and is less likely to volatilize from the viewpoint of obtaining a sufficient effect even when heated in the transesterification step described later. The molecular weight of the hindered phenol is preferably 200 to 10000, more preferably 500 to 5000, and particularly preferably 600 to 2000.
Among these, it is more preferable to use IRGANOX 1010 or IRGANOX 1098.

(Phosphorus compound (additive 2))
As the organophosphorus compound used in the production method of the present invention, any known organophosphorus compound can be used (hereinafter, these compounds may be referred to as “additive 2”). Preferred examples include trilauryl phosphite, trioctadecyl phosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-). tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bisisodecyloxy-pentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4′-biphenylene-diphosphonite, 6-Isooctyloxy-2,4,8,10-tetra-tert-butyl-dibenzo [d, f] [1,3,2] dioxaphosphine, 6-fluoro-2,4,8,10 Tetra-tert-butyl-12-methyl-dibenzo [d, g] [1,3,2] dioxaphosphocin, bis (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, Bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, bis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4'-diylbisphos Phyto, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (trade name: SANKO-HCA), triethyl phosphite (trade name: JP302), tri-n- Till phosphite (trade name: JP304), triphenyl phosphite (trade name: ADK STAB TPP), diphenyl monooctyl phosphite (trade name: ADK STAB C), tri (p-cresyl) phosphite (trade name: Chelex-PC ), Diphenyl monodecyl phosphite (trade name: Adeka Stub 135A), diphenyl mono (tridecyl) phosphite (trade name: JPM313), tris (2-ethylhexyl) phosphite (trade name: JP308), phenyl didecyl phosphite ( Product name: ADK STAB 517), tridecyl phosphite (trade name: ADK STAB 3010), tetraphenyldipropylene glycol diphosphite (trade name: JPP100), bis (2,4-di-tert-butylphenyl) pentaerythris Tall diphosphite (trade name: ADK STAB PEP-24G), Tris (tridecyl) phosphite (trade name: JP333E), bis (nonylphenyl) pentaerythritol diphosphite (trade name: ADK STAB PEP-4C), bis (2 , 6-Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (trade name: ADK STAB PEP-36), bis [2,4-di (1-phenylisopropyl) phenyl] pentaerythritol diphosphite ( Trade name: ADK STAB PEP-45), trilauryl trithiophosphite (trade name: JPS312), tris (2,4-di-tert-butylphenyl) phosphite (trade name IRGAFOS 168), tris (nonylphenyl) phosphite (Product name: A Castab 1178), distearyl pentaerythritol diphosphite (trade name: Adeka Stub PEP-8), tris (mono, dinonylphenyl) phosphite (trade name: Adekastab 329K), trioleyl phosphite (trade name: Chelex-OL) ), Tristearyl phosphite (trade name: JP318E), 4,4'-butylidenebis (3-methyl-6-tert-butylphenylditridecyl) phosphite (trade name: JPH1200), tetra (C12-C15 mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite (trade name: Adekastab 1500), tetra (tridecyl) -4,4'-butylidenebis (3-methyl-6-tert-butylphenol) diphosphite (trade name: Adekastab 26 0), hexa (tridecyl) -1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane-triphosphite (trade name: ADK STAB 522A), hydrogenated bisphenol A phosphite polymer (HBP), tetrakis (2,4-di-tert-butylphenyloxy) 4,4'-biphenylene-di-phosphine (trade name: IRGAFOS P-EPQ), tetrakis (2,4-di-tert-butyl- 5-methylphenyloxy) 4,4'-biphenylene-di-phosphine (trade name: GSY-101P), 2-[[2,4,8,10-tetrakis (1,1-dimethylether) dibenzo [d, f] [1,3,2] dioxaphosphin 6-yl] oxy] -N, N-bis [2-[[2,4,8,10-teto] Lakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] -ethyl] ethanamine (trade name: IRGAFOS 12), 2,2 ′ -Methylenebis (4,6-di-tert-butylphenyl) octyl phosphite (trade name: Adekasab HP-10) and the like.
The organophosphorus compound used in the production method of the present invention preferably has a large molecular weight and is less likely to volatilize from the viewpoint of obtaining a sufficient effect even when heated in the transesterification step described below. The molecular weight of the organic phosphorus compound is preferably 200 to 10,000, more preferably 500 to 5,000, and particularly preferably 600 to 2,000.
Among these, it is more preferable to use Irgafos 12, Irgafos 168 or Adekastab PEP-36.

In the production method of the present invention, the addition amount of at least one of the hindered phenol and the organic phosphorus compound with respect to the aromatic polyester resin is preferably more than 2% by mass and 5% by mass or less, preferably 2% by mass. It is more preferably 4% by mass or less, more preferably 2% by mass or more and 3% by mass or less, and particularly preferably 2% by mass or more and 2.5% by mass or less.
Further, the total addition amount of the hindered phenol and the organophosphorus compound with respect to the aromatic polyester resin is preferably more than 2% by mass and not more than 5% by mass, more than 2% by mass and not more than 4% by mass. More preferably, it is more than 2 mass% and 3 mass% or less, particularly preferably more than 2 mass% and 2.5 mass% or less.
Addition of the hindered phenol and / or the organophosphorus compound in such a range is preferable from the viewpoint of suppressing deterioration (such as gelation) of the resin during heating.

<Transesterification process>
The production method of the present invention includes a step of obtaining an aromatic polyester resin by transesterification of the acylated diol and the aromatic dicarboxylic acid by melt polymerization or high temperature solution polymerization. Hereinafter, the process of transesterifying the acylated diol and the aromatic dicarboxylic acid will be described.

前記一般式（４）中、Ｒ⁴¹はそれぞれ独立に置換基を表し、ｍは０〜３の整数を表す。 (Aromatic dicarboxylic acid)
Although there is no restriction | limiting in particular as said aromatic dicarboxylic acid, It is preferable that the said aromatic dicarboxylic acid is represented by following General formula (4) at least.

In the general formula (4), R ⁴¹ each independently represents a substituent, m represents an integer of 0 to 3.

The preferred range of the substituent represented by R ⁴¹ are the same as the preferred substituents represented by R ¹¹ to R ^18.
The m represents an integer of 0 to 3, preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0.

  As another aromatic dicarboxylic acid, in addition to the aromatic dicarboxylic acid represented by the general formula (4), the aromatic dicarboxylic acid represented by the following general formula (5) and / or the following general formula (6) It is preferable to use the aromatic dicarboxylic acid represented, and it is preferable to use either the aromatic dicarboxylic acid represented by the following general formula (5) or the aromatic dicarboxylic acid represented by the following general formula (6). More preferred.

前記一般式（５）中、Ｒ⁵¹およびＲ⁵²はそれぞれ独立に置換基を表し、ｎおよびｋはそれぞれ独立に０〜３の整数を表す。

In the general formula (5), R ⁵¹ and R ⁵² each independently represent a substituent, and n and k each independently represent an integer of 0 to 3.

Preferred examples of the substituent represented by R ⁵¹ and R ⁵² in the general formula (5), an alkyl group (having 1 to 10 carbon atoms are preferred, for example, a methyl group, an ethyl group, an isopropyl group, tert- butyl group, etc. ), Halogen atoms (for example, chlorine atom, bromine atom, iodine atom and the like), aryl groups (preferably having 6 to 20 carbon atoms, for example, phenyl group, biphenyl group, naphthyl group and the like), alkoxy groups (having 1 to 10 carbon atoms). For example, methoxy group, ethoxy group, isopropoxy group and the like), acyl group (preferably having 2 to 10 carbon atoms, for example, acetyl group, propionyl group, butyryl group and the like), acylamino group (having 1 to 10 carbon atoms). Preferable examples include formylamino group and acetylamino group), nitro group, cyano group and the like. More preferred are an alkyl group, a halogen atom, an aryl group, an alkoxy group, and a nitro group, and particularly preferred are an alkyl group and a halogen atom.

In the general formula (5), the carbonyl group may be linked to any carbon of the naphthalene ring, and two carbonyl groups may be linked to one ring. The carbonyl group is preferably bonded at the 2nd or 3rd position and preferably at the 6th or 7th position, and more preferably at the 2nd or 6th position.
N and k each independently represents an integer of 0 to 3, n is preferably an integer of 0 to 2, and k is preferably an integer of 0 to 2.

  Specific examples of the structure represented by the general formula (5) are shown below, but the structure represented by the general formula (5) that can be used in the present invention is not limited thereto.

In the general formula (6), R ^{61 to} R ⁶⁴ each independently represents a hydrogen atom or a substituent. )
Preferred substituents represented by R ^{61 to} R ⁶⁴ are the same as the preferred substituents represented by R ^{11 to} R ¹⁸ . R ^{61 to} R ⁶⁴ are preferably hydrogen atoms.

  The amount of the aromatic dicarboxylic acid used relative to the acylated product obtained by acylating the aromatic diol with the fatty acid anhydride is preferably 0.8 to 1.2 times equivalent.

(Reaction conditions for transesterification reaction)
The transesterification (polycondensation) reaction is preferably performed in the range of 130 to 400 ° C. for 2 hours to 16 hours, more preferably in the range of 140 ° C. to 350 ° C. for 4 hours to 8 hours, and more preferably 150 to 320 The reaction is particularly preferably carried out in the range of 4 ° C. for 4 to 6 hours. It is also preferable to raise the temperature stepwise during the reaction. In this case, the temperature is preferably raised at a rate of 0.1 to 50 ° C./min, and the temperature is raised at a rate of 0.3 to 5 ° C./min. More preferred.

In transesterification of the acylated acylated diol (fatty acid ester) and carboxylic acid, the by-product fatty acid and the unreacted fatty acid anhydride are evaporated to leave the system. It is preferable to distill off.
If necessary, evaporation may be promoted by reducing the pressure inside the reaction system. In this case, the pressure in the reaction system is preferably 750 Torr to 0.1 Torr, more preferably 300 Torr to 0.1 Torr, and particularly preferably 120 Torr to 1 Torr. Further, when reducing the pressure, it is preferable to reduce the pressure stepwise within the above range.
By refluxing a part of the distilled fatty acid and returning it to the reactor, it is possible to condense or reverse sublimate the raw material that evaporates or sublimates with the fatty acid and returns it to the reactor. In this case, the precipitated aromatic dicarboxylic acid can be returned to the reactor together with the fatty acid.

(Onium salt (additive 4))
In the production method of the present invention, it is preferable to add at least one onium salt. In particular, it is preferable to add at least one onium salt in the transesterification step from the viewpoint of shortening the heating time so as not to gel the resin composition by increasing the reaction rate of the transesterification reaction.
Examples of the onium salt include ammonium salts, oxonium salts, sulfonium salts, phosphonium salts, and selenonium salts. Of these, ammonium salts or phosphonium salts are preferred.
Preferable examples of the ammonium salt include trimethylbenzylammonium halide, tributylbenzylammonium halide, triethylbenzylammonium halide, tetra (n-butyl) ammonium halide, bis (triphenylphosphoranylidene) ammonium halide and the like.
Preferable examples of the phosphonium salt include trimethylbenzylphosphonium halide, tributylbenzylphosphonium halide, triethylbenzylphosphonium halide, tetra (n-butyl) phosphonium halide, triphenylbenzylphosphonium halide, tetraphenylphosphonium halide and the like.
Among them, it is preferable to use tetra (n-butyl) ammonium halide.

  In the production method of the present invention, the amount of the onium salt added to the aromatic dicarboxylic acid is preferably 0.001 to 3.0% by mass, and preferably 0.01 to 2.0% by mass. More preferred is 0.1 to 1.0% by mass.

  Additives 1 to 4 in the present invention may be added to the reaction system as they are, but in the case of solids or powders, it may be added in a form dissolved or dispersed in a solvent from the viewpoint of uniformity of the reaction system. To preferred. As the solvent, it is preferable to use a fatty acid anhydride used in the reaction or a fatty acid produced from the fatty acid anhydride. In the case of synthesis by high-temperature solution polymerization, the same type of solvent used in the reaction is used. It is also preferable. In the present invention, the ratio of the additives 1 to 4 and the solvent is preferably 100 to 0 to 1 to 50, more preferably 10 to 1 to 1 and 20, more preferably 1 to 1 to 1 on a mass basis. It is particularly preferred that the number is 10.

<Solid-state polymerization>
The degree of polymerization of the aromatic polyester resin obtained by the transesterification process can be further increased by solid phase polymerization as necessary. Specifically, after the aromatic polyester resin obtained by melt polycondensation or high-temperature solution polymerization is solidified and pulverized, the aromatic polyester resin powder is heated in an atmosphere under normal pressure or reduced pressure. Is. For example, a method of removing the high boiling point solvent after stirring the aromatic polyester resin powder in a high boiling point solvent such as a mixture of diphenyl and diphenyl ether or diphenyl sulfone under heating, or granulating the aromatic polyester resin powder Examples of the method include a method of heat-treating in an inert gas atmosphere or under reduced pressure after changing the shape such as pelletization by a machine. The heating temperature and the heat treatment temperature are usually about 200 to 350 ° C., and the treatment time is usually about 1 to 20 hours. Examples of the heat treatment apparatus include known dryers, reactors, inert ovens, mixers, and electric furnaces.

（一般式（１）中、Ｒ¹¹¹〜Ｒ¹¹⁸はそれぞれ独立に水素原子または置換基を表し、少なくとも一つは置換基を表す。Ｘは単結合または二価の連結基を表す。）
以下、本発明の樹脂組成物について説明する。 [Resin composition]
The resin composition of the present invention is produced by the method for producing a resin composition of the present invention.
Specifically, the resin composition of the present invention comprises A) an aromatic polyester having a structure represented by the following general formula (1) and a structure derived from an aromatic dicarboxylic acid, and B) a hindered phenol and an organic phosphorus compound. It contains at least one of them. The resin composition of this invention has the characteristic that resin contained in a resin composition at the time of a heating hardly deteriorates by taking such a structure.

(In general formula (1), R ^{111 to} R ¹¹⁸ each independently represents a hydrogen atom or a substituent, and at least one represents a substituent. X represents a single bond or a divalent linking group.)
Hereinafter, the resin composition of the present invention will be described.

<Aromatic polyester resin structure>
The aromatic polyester resin contained in the resin composition of the present invention has A) a structure represented by the general formula (1) and a structure derived from an aromatic dicarboxylic acid.
In the general formula (1), R ^{111 to} R ¹¹⁸ each independently represents a hydrogen atom or a substituent, and at least one represents a substituent. X represents a single bond or a divalent linking group.
A preferable range of R ¹¹¹ to R ¹¹⁸ in the general formula (1) is the same as the preferred ranges of R ¹¹ to R ¹⁸ in the general formula (I).
The aromatic polyester resin contained in the resin composition of the present invention preferably has a structure derived from the aromatic diol or the aromatic dicarboxylic acid, which is preferably used in the production method of the present invention.

In the aromatic polyester resin, the content of the structure derived from the aromatic diol having a substituent on the aromatic ring represented by the general formula (I) is 10 to 99 mol% of all the structures derived from the aromatic diol. Is preferable, 20-99 mol% is more preferable, and 30-90 mol% is especially preferable.
In the aromatic polyester resin, the content of the structure derived from the aromatic biphenol having a substituent on the aromatic ring represented by the general formula (II) is 10 to 99 mol% of the structures derived from all aromatic diols. Is preferable, 10 to 80 mol% is more preferable, and 10 to 60 mol% is particularly preferable.
In the aromatic polyester resin, the content of the structure derived from the unsubstituted aromatic diol represented by the general formula (III) is preferably 0 to 80 mol% among all the structures derived from the aromatic diol. -70 mol% is more preferable, and 1-60 mol% is especially preferable.
In the aromatic polyester resin, the content of the structure derived from the aromatic dicarboxylic acid represented by the general formula (4) is preferably 20 to 99 mol%, and preferably 30 to 95 mol among all the structures derived from the dicarboxylic acid. % Is more preferable, and 40 to 95 mol% is particularly preferable.
In the aromatic polyester resin, the content of the structure derived from the aromatic dicarboxylic acid represented by the general formula (5) is preferably 0 to 90 mol%, and 0 to 70 mol among all the structures derived from the dicarboxylic acid. % Is more preferable, and 1 to 50 mol% is particularly preferable.
In the aromatic polyester resin, the content of the structure derived from the aromatic dicarboxylic acid represented by the general formula (6) is preferably 0 to 90 mol%, and 0 to 70 mol among all the structures derived from the dicarboxylic acid. % Is more preferable, and 1 to 50 mol% is particularly preferable.

(Other structures)
The aromatic polyester resin is a structure derived from an aromatic diol or aromatic dicarboxylic acid, as long as it does not contradict the gist of the present invention, and the structure represented by the general formula (1) or the general formula (4) to You may have structures other than the structure derived from the aromatic dicarboxylic acid represented by the said General formula (6).

  In addition to the ester bond, the aromatic polyester resin may contain one or more of an ether bond, a carbonate bond, a sulfone bond, a ketone bond, an imide bond, an amide bond, a urethane bond, and a urea bond. Good. Other structures that form these bonds include known structures that are known to be able to be included in the polyester resin, as long as they do not contradict the spirit of the present invention.

(Specific examples of aromatic polyester resin)
Although the specific example of the aromatic polyester resin contained in the resin composition of this invention is shown below, the polyester resin which can be used by this invention is not limited to these. In P-1 to P-14, the numbers on the lower right of the parenthesis represent the mol% of each structure in the polyester resin.

(Resin characteristics)
The aromatic polyester resin contained in the resin composition of the present invention preferably has a weight average molecular weight of 7,000 to 200,000, more preferably 10,000 to 150,000, and particularly preferably 13,000 to 100,000.

  In addition, the aromatic polyester resin contained in the resin composition of the present invention is a copolymer, and the polymerization mode is random copolymerization, block copolymerization, or any other polymerization format. Also good.

  The glass transition temperature (Tg) of the aromatic polyester resin contained in the resin composition of the present invention is preferably in a range suitable for melt film formation. Specifically, the temperature is preferably 160 to 270 ° C, particularly preferably 165 ° C to 260 ° C, and more preferably 170 ° C to 260 ° C. The transparency of the film obtained can be improved more because Tg of the aromatic polyester resin contained in the resin composition of this invention is said range. Further, when Tg is 170 ° C. or higher, dimensional stability when performing a process of laminating with ITO using the aromatic polyester resin contained in the resin composition of the present invention as an optical film (a process involving heating). The performance of the image display device of the present invention can be improved.

(Other composition of resin composition)
The resin composition of the present invention contains at least one of B) a hindered phenol and an organic phosphorus compound. Among the B) hindered phenols and organophosphorus compounds, preferred compounds as at least one are the same as the hindered phenols and organophosphorus compounds used in the production method of the present invention.
Further, other additives used in the production method of the present invention may also be included in the resin composition of the present invention.

(Use of resin composition)
The resin composition of the present invention is useful, for example, for optical materials, films of the present invention described later, and the like. As the optical material, for example, an optical film such as a polarizing plate protective film, a retardation film, an antireflection film, an electromagnetic wave shielding film, a pickup lens, a microlens array, a light guide plate, an optical fiber, an optical waveguide and the like can be preferably exemplified.

[the film]
(Film production method)
The resin composition of the present invention can be preferably used as a film. As a method for producing the film of the present invention, a solution casting method and an extrusion molding method (melt molding method) are preferably used, and a solution casting method is more preferably used.
Regarding the casting and drying methods in the solution casting method, U.S. Pat. No. 2,336,310, U.S. Pat. No. 2,367,603, U.S. Pat. No. 2,429,078, U.S. Pat. No. 2,429,297, U.S. Pat. Specification, US Pat. No. 2,607,704, US Pat. No. 2,739,069, US Pat. No. 2,739,070, British Patent No. 6,407,731, British Patent No. 7,36892, Japanese Patent Publication No. 45-4554 JP-B-49-5614, JP-A-60-176834, JP-A-60-203430, JP-A-62-115035.

  As a solution casting method preferably used when forming the film of the present invention, a known method in this field can be adopted, and there is no particular limitation. Particularly preferable conditions for the solution casting method include the conditions described in JP-A 2007-145950, [0060] to [0066].

  As the extrusion molding method, a known method in this field can be adopted, and there is no particular limitation.

  As a production apparatus for producing the film of the present invention using the extrusion molding method, a known production apparatus in this field can be employed. However, the manufacturing apparatus that can be used in the present invention is not limited to these.

Although there is no restriction | limiting in particular in the said extrusion molding method, It is preferable to shape | mold once the resin composition containing the polyester resin etc. which are contained in the resin composition of this invention before film forming. In the case of molding into a pallet shape, it is preferable that the resin composition is first melt-kneaded with a kneader, taken out in a noodle shape and then cut to prepare a pellet-shaped resin composition.
In addition to the polyester resin contained in the resin composition of the present invention described above, the resin composition may contain a stabilizer such as an anti-coloring agent and other additives that do not contradict the gist of the present invention. .
The melt kneading temperature is preferably 250 ° C to 350 ° C, more preferably 260 ° C to 350 ° C, and particularly preferably 270 ° C to 340 ° C.

Next, the pellet-shaped resin composition is introduced into a melt extruder, the resin composition is supplied to a die installed at the outlet of the melt extruder, the resin composition is melt-extruded from the die, and this is cast. It is preferable to produce a film by extruding onto a roll.
There is no restriction | limiting in particular as said melt extruder, A well-known melt extruder can be used, For example, a melt extruder can be used. Among these, a biaxial extruder is preferable. The shape of the die is not particularly limited, and a known die can be used. A T die, a hanger coat die, or the like can be used, and a hanger coat die is preferably used.
The temperature of the resin composition in the melt extruder is preferably 250 ° C to 350 ° C, more preferably 260 ° C to 350 ° C, and particularly preferably 270 ° C to 340 ° C.
The time for melt kneading is not particularly limited.

  There is no restriction | limiting in particular as said cast roll, A well-known cast roll can be used. The temperature of the cast roll is not particularly limited.

  The film of the present invention can also be stretched. As the stretching method, known methods can be used. For example, JP-A-62-115035, JP-A-4-152125, JP-A-4-284221, JP-A-4-298310, JP-A-11-48271. The film can be stretched by a roll uniaxial stretching method, a tenter uniaxial stretching method, a simultaneous biaxial stretching method, a sequential biaxial stretching method, an inflation method, or a rolling method described in a publication. Hereinafter, a stretching method using a tenter will be described as an example.

Stretching of the film is performed at room temperature or under heating conditions. It is preferable to carry out under heating conditions from the viewpoint of uniform and sufficient stretching. The film of the present invention using the resin composition of the present invention contains additive 1 and / or additive 2 even when it is stretched at high temperature under heating conditions, and therefore has excellent stretchability, and The mechanical properties (particularly dimensional stability) of the resin of the present invention having the structure represented by the general formula (1) are not impaired.
The film may be stretched uniaxially or biaxially, but biaxial stretching is preferred. The film can be stretched by a treatment during drying, and is particularly effective when the solvent remains. For example, the film is stretched by adjusting the speed of the film transport roller so that the film winding speed is higher than the film peeling speed. The film can also be stretched by conveying the film while holding it with a tenter and gradually widening the width of the tenter. Further, after the film is dried, it can be stretched using a stretching machine (preferably uniaxial stretching using a long stretching machine). The stretch ratio of the film (the ratio of the increase due to stretching relative to the original length) is preferably 0.5 to 300%, more preferably 1 to 200%, particularly 1 to 100%. Is preferred.

  The stretching speed is preferably 5% / min to 1000% / min, and more preferably 10% / min to 500% / min. The stretching is preferably performed by a heat roll or / and a radiant heat source (such as an IR heater) or warm air. Moreover, you may provide a thermostat in order to improve the uniformity of temperature.

  The stretching temperature is preferably (Tg-100 ° C) to (Tg + 25 ° C), more preferably (Tg-80 ° C) to (Tg + 20 ° C), based on the glass transition temperature of the polyester resin contained in the resin composition of the present invention. Preferably, (Tg−70 ° C.) to (Tg + 15 ° C.) are particularly preferable.

  The film of the present invention may be heat-treated after stretching. The heat treatment temperature is preferably (Tg-100 ° C) to (Tg + 25 ° C), more preferably (Tg-80 ° C) to (Tg + 20 ° C), and (Tg-70 ° C) to (Tg + 15) based on the glass transition temperature Tg. C) is particularly preferred. By performing heat treatment, shrinkage stress due to stretching can be relieved and shrinkage during heating can be reduced.

(Film physical properties)
Moreover, it is preferable that the change of the length measured by the thermomechanical analysis shows the maximum point in the film of this invention in the temperature more than a glass transition temperature (Tg). Here, the thermomechanical analysis means an analysis method described in JIS K7197, which is a JIS standard. Further, that the change in length measured by thermomechanical analysis shows a maximum point means the behavior when the length contracts, expands, and further contracts.

(Elongation at break)
The film of the present invention preferably has a breaking elongation of 10% or more from the viewpoint of stretchability. The breaking elongation is more preferably 15% or more, and particularly preferably 20% or more.

(Functional layer)
Other layers may be formed on the film surface of the present invention depending on the application. Further, for the purpose of improving the adhesion to other parts, the film surface may be subjected to treatment such as saponification, corona treatment, flame treatment, glow discharge treatment and the like. Further, an anchor layer may be provided on the film surface.

-Gas barrier layer-
In the film of the present invention, a gas barrier layer can be laminated on at least one surface in order to suppress gas permeability. As a preferable gas barrier layer, for example, a metal oxide mainly composed of one or more metals selected from the group consisting of silicon, aluminum, magnesium, zinc, zirconium, titanium, yttrium and tantalum, silicon, aluminum, Mention may be made of films formed of metal nitrides of boron or mixtures thereof. Among these, the main component is silicon oxide having a ratio of the number of oxygen atoms to the number of silicon atoms of 1.5 to 2.0 in terms of gas barrier properties, transparency, surface smoothness, flexibility, film stress, cost, and the like. A film formed of a metal oxide is good. The gas barrier layer made of these inorganic compounds is formed by vapor deposition such as sputtering, vacuum deposition, ion plating, plasma CVD, Cat-CVD, etc., by depositing a material from the vapor phase to form a film. Can be made. Among these, the sputtering method and the Cat-CVD method that can provide particularly excellent gas barrier properties are preferable. Further, the temperature may be raised to 50 to 250 ° C. while the gas barrier layer is provided.

  The thickness of the gas barrier layer is preferably 10 to 300 nm, and more preferably 30 to 200 nm.

  The gas barrier layer may be provided on the same side or the opposite side to the transparent conductive layer described later.

  The film of the present invention may be provided with an inorganic barrier layer, an organic barrier layer, an organic-inorganic hybrid barrier layer, etc. for the purpose of imparting chemical resistance.

-Transparent conductive layer-
A transparent conductive layer may be laminated on at least one side of the film of the present invention. A known metal film, metal oxide film, or the like can be applied as the transparent conductive layer. Among these, a metal oxide film having excellent transparency, conductivity, and mechanical properties is preferably used as the transparent conductive layer. The metal oxide film is, for example, a metal oxide film of indium oxide, cadmium oxide or tin oxide to which tin, tellurium, cadmium, molybdenum, tungsten, fluorine, zinc, germanium or the like is added as an impurity; an oxide to which aluminum is added as an impurity Examples thereof include metal oxide films such as zinc and titanium oxide. Among them, an indium oxide thin film mainly composed of tin oxide and containing 2 to 15% by mass of zinc oxide is excellent in transparency and conductivity, and is preferably used.

<Use of the film of the present invention>
(Image display device)
The film of the present invention described above can be used for an image display device. Here, the type of the image display device is not particularly limited, and conventionally known ones can be exemplified. Moreover, the flat panel display excellent in display quality can be produced using the film of this invention as a board | substrate. Examples of the flat panel display include a liquid crystal display device, a plasma display, organic electroluminescence (EL), inorganic electroluminescence, a fluorescent display tube, a light emitting diode, and a field emission type. Besides these, a conventional glass substrate has been used. It can be used as a substrate instead of a display-type glass substrate. Furthermore, the film of the present invention can be applied to uses such as solar cells and touch panels in addition to flat panel displays. The touch panel can be applied to, for example, those described in JP-A-5-127822, JP-A-2002-48913, and the like.

  In addition, a thin film transistor TFT can be formed on the film of the present invention. The TFT can be manufactured by a known method disclosed in Japanese Patent Application Laid-Open No. 11-102867, Japanese Patent Application Laid-Open No. 10-512104, and Japanese Patent Application Laid-Open No. 2001-68681. Further, these substrates may have a color filter for color display. The color filter may be manufactured using any method, but is preferably manufactured using a photolithography technique.

  The TFT manufactured in the present invention may be an amorphous silicon TFT or a polycrystalline silicon TFT. An annealing method by laser irradiation is preferably used for polycrystallizing amorphous silicon.

  Examples of the method for forming silicon of the semiconductor layer of the TFT include a sputtering method, a plasma CVD method, an ICP-CVD method, a Cat-CVD method, and the like, but the sputtering method is preferable. By manufacturing by a sputtering method, the hydrogen concentration in the silicon thin film can be reduced, and peeling of the silicon layer due to laser irradiation for polycrystallization can be prevented.

  An intrinsic silicon thin film, an impurity silicon thin film, a silicon nitride thin film, a silicon oxide thin film and the like necessary for TFT production can be formed on the film of the present invention by plasma CVD, but the substrate temperature at that time is preferably 250 ° C. or lower. .

  ITO and IZO can be formed on the pixel electrode by sputtering. The heat treatment temperature for lowering the resistivity is preferably 250 ° C. or lower.

  The structure of the TFT manufactured in the present invention may be any structure such as a channel etching type, an etching stopper type, a top gate type, and a bottom gate type.

  When the film of the present invention is used as a substrate for a liquid crystal display device or the like, the resin composition constituting the film is preferably an amorphous polymer in order to achieve optical uniformity. Furthermore, for the purpose of controlling retardation (Re) and its wavelength dispersion, resins having different signs of intrinsic birefringence can be combined, or resins having a large (or small) wavelength dispersion can be combined.

  The film of the present invention is preferably laminated by combining different resin compositions from the viewpoint of controlling retardation (Re) and improving gas permeability and mechanical properties. A preferred combination of different resin compositions is not particularly limited, and any of the above-described resin compositions can be used.

  The film of the present invention can be suitably used for organic EL display applications. The specific layer structure of the organic EL display device includes anode / light emitting layer / transparent cathode, anode / light emitting layer / electron transport layer / transparent cathode, anode / hole transport layer / light emitting layer / electron transport layer / transparent cathode, Anode / hole transport layer / light emitting layer / transparent cathode, anode / light emitting layer / electron transport layer / electron injection layer / transparent cathode, anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection Examples include layer / transparent cathode.

  In the organic EL display device in which the film of the present invention can be used, a direct current (which may include an alternating current component if necessary) voltage (usually 2 to 40 V) or a direct current is applied between the anode and the cathode. Thus, light emission can be obtained. Regarding driving of these light emitting elements, for example, JP-A-2-148687, JP-A-6-301355, JP-A-5-290080, JP-A-7-134558, JP-A-8-234665, and JP-A-8-240447. US Pat. Nos. 5,828,429 and 6023308, Japanese Patent No. 2784615, and the like can be used.

  As a full color display method of the organic EL display device, any method such as a color filter method, a three-color independent light emission method, a color conversion method, or the like may be used.

  Either a passive matrix or an active matrix may be used as a driving method for the liquid crystal display device and the organic EL display device.

(Other uses)
The film of the present invention is an optical film, retardation film, polarizing plate protective film, transparent conductive film, substrate for display device, substrate for flexible display, substrate for flat panel display, substrate for solar cell, substrate for touch panel, for flexible circuit It can be used for a substrate, an optical disk protective film and the like.

  The features of the present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

(Example 1)
<Synthesis example>
Synthesis example 1 of resin composition P-1
In a reaction vessel equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 18.26 g of bisphenol A (hereinafter also referred to as BisA), 8.56 g of 3,3′-dimethyl-4,4 ′ -Dihydroxybiphenyl (hereinafter also referred to as OCBP), 19.38 g of 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl (hereinafter also referred to as 2,6X-BP), 26.58 g Terephthalic acid (hereinafter also referred to as TPA), 8.65 g of naphthalenedicarboxylic acid (hereinafter also referred to as NDA), 44.92 g of acetic anhydride, 28.60 g of diphenyl ether, and 75.3 mg of N-methylimidazole A solution dissolved in 0.2 g acetic acid was added. After sufficiently replacing the inside of the reaction vessel with nitrogen gas, the temperature was raised to 150 ° C. under a nitrogen gas stream, and the reaction was carried out for 2 hours in a reflux state with stirring. The acylation reaction was performed under atmospheric pressure. After sampling a part of the reaction product, 1.46 g of Irganox 1098 (manufactured by BASF Japan) slurried with 0.17 g of tetrabutylammonium chloride, 10 g of diphenyl ether, 1.46 g of ADK STAB PEP-36 (stock) (Manufactured by ADEKA) was added, the temperature was raised to 280 ° C. over 2 hours and held for 7 hours. The temperature was further raised to 300 ° C. and held for 2 hours, and then the contents were taken out to obtain a resin composition P-1 of the present invention. The transesterification reaction was performed under atmospheric pressure.
It was 400 mPa * S as a result of measuring the viscosity of 2 mass% of pentafluorophenol with the vibration type viscometer about the resin composition P-1. In addition, the obtained polymer was dissolved in methylene chloride, cast on a glass plate, and dried to obtain a 100 μm-thick film using TMA8310 (manufactured by Rigaku Corporation, Thermo Plus series). It was 165 degreeC when temperature was measured.

(Example 2)
Synthesis of Resin Composition P-2 15.38 g of bisphenol C (hereinafter also referred to as BisC), 30.00 g of OCBP, 16 in a reaction vessel equipped with a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser. .61 g of terephthalic acid, 16.61 g of isophthalic acid (hereinafter also referred to as IPA) and 44.92 g of acetic anhydride were charged, and 117.9 mg of sodium acetate was added. After sufficiently replacing the inside of the reaction vessel with nitrogen gas, the temperature was raised to 150 ° C. under a nitrogen gas stream, and the reaction was carried out for 2 hours in a reflux state with stirring. The acylation reaction was performed under atmospheric pressure. After sampling a part of the reaction product, 0.16 g of tetrabutylammonium chloride, 1.43 g of Irganox 1098, 1.43 g of Adekastab PEP-36 were added, and the temperature was raised to 280 ° C. over 2 hours. Retained. The temperature was further raised to 300 ° C. and held for 2 hours, and then the contents were taken out to obtain a resin composition P-2 of the present invention. The transesterification reaction was performed under atmospheric pressure.

(Examples 3 to 8, Comparative Example 1)
The same operations as in Example 1 were performed except that the amount of each monomer and additive charged in Example 1 was changed to the amount described in Table 1 below, and the resin compositions P-2 to P-8 of the present invention and The resin composition C-1 of the comparative example was obtained. In Table 1 below, MDHB is 2,2′-dimethyl-4,4′-dihydroxybiphenyl, OPP-BP is 3,3′-diphenyl-4,4′-bishydroxybiphenyl, and TPP is ADK STAB TPP (trivalent). Phenyl phosphate, manufactured by BASF Japan Ltd.), and Irganox 1010 represents a trade name (manufactured by BASF Japan Ltd.).

<Evaluation>
<Ac conversion rate>
A part of the reaction product sampled in the synthesis example and the comparative example was dissolved in deuterated dimethyl sulfoxide and measured by 400 MHz ¹ HNMR.

<Weight average molecular weight>
By GPC measurement using polystyrene conversion using N-methylpyrrolidone as a solvent, GPC (manufactured by Tosoh Corporation, HLC-8120GPC) was used for comparison with a molecular weight standard product of polystyrene.

In Tables 1 and 2, * 1) indicates the value based on the amount of polymer produced, * 2) indicates the value based on the total amount of monomer, and * 3) indicates the total amount of aromatic dicarboxylic acid monomer. Represents a numerical value based on.
As shown in Table 1, the resin composition of the comparative example gelled during production, whereas the resin composition of the present invention contains a thermal stabilizer and can be produced by melt polycondensation. It became.

(Production and evaluation of film samples)
<Adjustment of Resin Composition S-1>
Resin composition P-1 was pulverized and passed through a mesh with a mesh opening of 2 mm, and heated (solid phase polymerization) at 140 ° C. for 8 hours and 230 ° C. for 9 hours under a nitrogen stream to obtain resin composition S-1 Obtained. The weight average molecular weight of the resin in the obtained resin composition was 62,000.

<Synthesis of Resin C-2>
A 300 ml three-necked flask equipped with a stirrer was charged with 10.56 g of 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl and 3,3′-dimethyl-4,4′-dihydroxy. 4.68 g of biphenyl, 9.96 g of bisphenol A, 360 mg of hydrosulfite sodium, 1600 mg of tetra-n-butylammonium chloride, 390 ml of methylene chloride, and 450 ml of distilled water were added and dissolved by stirring under a nitrogen stream. A solution prepared by dissolving 17.8 g of terephthalic acid chloride and 5.36 g of 2,6-naphthalenedicarboxylic acid chloride in 180 ml of methylene chloride was added to the solution.
Furthermore, a mixed solution of a solution obtained by dissolving 0.278 g of t-butylphenol in 114 ml of a 2 mol / L sodium hydroxide aqueous solution and 30 ml of water was added dropwise at 15 to 20 ° C. over 1 hour. After stirring for 3 hours after completion of the dropwise addition, the reaction solution was transferred to a 3-liter three-necked flask, and 1.8 ml of acetic acid and 1800 ml of ethyl acetate were slowly added. The obtained polymer powder was collected by filtration, washed successively with 1 L of ethyl acetate, 1 L of water, and 1 L of methanol and dried to obtain 35.8 g of Resin C-2. The weight average molecular weight of the obtained resin was 61000.

<Synthesis of Resin Composition C-3>
In a reaction vessel equipped with a stirrer, a nitrogen gas inlet tube, a thermometer and a reflux condenser, 45.66 g of bisphenol A, 16.61 g of terephthalic acid, 16.61 g of isophthalic acid, 44.92 g of acetic anhydride, 28.60 g of diphenyl ether. And a solution of 75.3 mg of N-methylimidazole dissolved in 0.2 g of acetic acid was added. After sufficiently replacing the inside of the reaction vessel with nitrogen gas, the temperature was raised to 150 ° C. under a nitrogen gas stream, and the reaction was carried out for 2 hours in a reflux state with stirring. After sampling a portion of the reaction, 1.46 g of Irganox 1098 slurried with 10 g of diphenyl ether, 1.46 g of Irganox 1098, 1.46 g of ADK STAB PEP-36 were added and 280 over 2 hours. The temperature was raised to 0 ° C. and held for 7 hours. The temperature was further raised to 300 ° C. and held for 2 hours, and then the contents were taken out.
The obtained resin composition was pulverized and passed through a mesh with a mesh opening of 2 mm, and then heated (solid-phase polymerization) at 140 ° C. for 8 hours and 230 ° C. for 9 hours under a nitrogen stream, and the resin composition C of Comparative Example -3 was obtained. The weight average molecular weight of the resin in the obtained resin composition was 84500.

<Creation of film sample>
Resin compositions S-1, C-2 and C-3 were each dissolved at a concentration such that the solution viscosity after dissolution in methylene chloride was in the range of 500 to 1500 mPa · s. The solution was filtered through a 5 μm filter and cast on a glass substrate using a doctor blade. After casting, after heating and drying at room temperature for 20 minutes, 35 ° C. for 10 minutes, 200 ° C. for 2 hours, and 230 ° C. for 50 hours, the film was peeled from the glass substrate to produce film samples F-1 to F-3. .

<Creation of stretched film>
Film samples F-1 to F-3 were cut into a size of 120 mm × 120 mm and stretched by a simultaneous biaxial stretching machine. The stretching conditions for the first stage were a chuck distance of 100 mm (both longitudinal and lateral), a resin temperature of 250 ° C., a stretching speed of 100 mm / min, and a stretching distance of 15 mm (both longitudinal and lateral stretching ratios of 15%). Here, since the film sample F-2 was broken, it could not be used for the subsequent evaluation.
The stretched film samples F-1 and F-3 were heated to 240 ° C. while being held in a biaxial stretching machine, and heat-treated until the stress became substantially constant. Thereafter, the film temperature was cooled to 100 ° C. or lower and taken out from the biaxial stretching machine. The stretched film was set in a 120 mm square inner metal frame, and heat-treated for 24 hours in a nitrogen atmosphere at 230 ° C. to obtain stretched films of Example 9 and Comparative Example 3.

<Evaluation>
The following evaluation was implemented about the obtained film sample.

<Linear thermal expansion coefficient>
A film sample (19 mm × 5 mm) was prepared and measured using TMA (manufactured by Rigaku Corporation, TMA8310). The measurement speed was 3 ° C./min. Three samples were measured and the average value was used. The measurement was performed in a temperature range of 25 ° C. to 300 ° C., and the linear thermal expansion coefficient was calculated in the range of 25 ° C. to 200 ° C. at the time of temperature increase.

  The obtained results are shown in Table 2 below.

On the other hand, since the film sample of Comparative Example 2 was prepared from a resin (composition) that did not contain a heat stabilizer, the film obtained using the film deteriorated by heating and the stretchability was lowered. Since the film sample of Comparative Example 3 does not contain the structure represented by the general formula (1), the linear thermal expansion coefficient cannot be reduced.
From Table 2, it was found that the resin composition of the present invention was not easily deteriorated by the heating process when formed into a film, and exhibited good stretchability. Moreover, since it has the structure represented by General formula (1), it turned out that the linear thermal expansion coefficient of a film sample can be reduced (it is excellent in thermal dimensional stability).
In contrast to these examples, it was found that the film sample of Comparative Example 2 was deteriorated by heating and the stretchability was lowered. Since the film sample of Comparative Example 3 did not contain the structure represented by the general formula (1), it was found that the linear thermal expansion coefficient could not be reduced.

Claims (13)

A step of acylating an aromatic diol represented by the following general formula (I) by adding a fatty acid anhydride;
Adding at least one of hindered phenols and organophosphorus compounds;
A process for producing an aromatic polyester resin by transesterification of the acylated product of the aromatic diol and an aromatic dicarboxylic acid by melt polymerization or high-temperature solution polymerization.

(In the general formula (I), R ^{11 to} R ¹⁸ each independently represents a hydrogen atom or a substituent, and at least one represents a substituent. X represents a single bond or a divalent linking group.) The method for producing a resin composition according to claim 1, wherein the aromatic diol represented by the general formula (I) is represented by the following general formula (II).

(In general formula (II), R ^{21 to} R ²⁸ each independently represents a hydrogen atom or a substituent, and at least one represents a substituent.)   The method for producing a resin composition according to claim 1 or 2, wherein at least one compound selected from the group consisting of alkali metal salts, alkaline earth metal salts, and amine compounds is added.   At least 1 type of onium salt is added, The manufacturing method of the resin composition as described in any one of Claims 1-3 characterized by the above-mentioned.   The method for producing a resin composition according to any one of claims 1 to 4, wherein the transesterification step is performed after the acylation step is completed.   6. The transesterification step is performed after the acylation step is completed, and a step of adding at least one of the hindered phenol and the organophosphorus compound is performed, and then the transesterification step is performed. The manufacturing method of the resin composition as described in claim | item.   The average acylation rate of phenolic hydroxyl groups of all aromatic diols used for polymerization of the aromatic polyester resin at the start of the transesterification step is 96% or more, according to claim 6, A method for producing a resin composition.   The addition amount of at least one of the hindered phenol and the organic phosphorus compound with respect to the aromatic polyester resin is more than 2% by mass and 5% by mass or less. The manufacturing method of the resin composition as described in any one of.   A resin composition produced by the method for producing a resin composition according to claim 1. A) an aromatic polyester having a structure represented by the following general formula (1) and a structure derived from an aromatic dicarboxylic acid;
B) A resin composition comprising at least one of hindered phenols and organophosphorus compounds.

(In general formula (1), R ^{111 to} R ¹¹⁸ each independently represents a hydrogen atom or a substituent, and at least one represents a substituent. X represents a single bond or a divalent linking group.)   The resin composition according to claim 9 or 10, wherein the weight average molecular weight is 7,000 to 200,000.   A film comprising the resin composition according to any one of claims 9 to 11 formed into a film.   An optical material made of the resin composition according to any one of claims 9 to 11.