WO2022054766A1 - Polymer composition, varnish, and polyimide film - Google Patents

Abstract

A polymer composition containing: a polymer (X) that includes at least one repeating unit selected from the group consisting of repeating units represented by general formula (1) and repeating units represented by general formula (2); and a compound (Y) that is represented by general formula (3) (In formula (1), X1 is a tetravalent group having an alicyclic structure or an aromatic ring, and X is a single bond or the like. In formula (2), X2 is a tetravalent group having an alicyclic structure or an aromatic ring, R1 and R2 each independently represents hydrogen, a C1-6 alkyl group, or the like, and X represents a single bond or the like. In formula (3), R3 is a C1-30 alkyl group or the like, and n is 0-2.).

Description

Polymer composition, varnish, and polyimide film

The present invention relates to a polymer composition, a varnish, and a polyimide film.

Since the polyimide resin has excellent mechanical properties and heat resistance, various uses are being studied in the fields of electric and electronic parts and the like. For example, it is desired to replace a glass substrate used in an image display device such as a liquid crystal display or an OLED display with a polyimide film substrate, and a polyimide resin satisfying the performance as an optical material is being developed.
However, in recent years, with the increasing functionality of electronic devices, it has become necessary for electronic components to simultaneously satisfy various required performances. Therefore, with respect to the polyimide resin used for the display, attempts have been made to add new properties to the original properties of the resin or to enhance the original properties by blending various additives.

For example, Patent Document 1 contains a specific polyamic acid and a specific phosphorus compound for the purpose of preventing crystallization and shortening the layer formation time in addition to heat resistance and mechanical properties. However, there is disclosed a polyimide precursor composition capable of producing a polyimide film having a large water vapor permeability coefficient by heat treatment under a condition where the maximum heating temperature is 300 to 500 ° C.
Further, Patent Document 2 contains a polyimide precursor having a specific repeating unit and a phosphorus atom for the purpose of obtaining a polyimide having transparency, heat resistance, and a low coefficient of linear thermal expansion, and has a boiling point at 1 atm. A polyimide precursor composition containing a phosphorus compound having a decomposition temperature lower than the decomposition temperature and 350 ° C. or lower is disclosed.

International Publication No. 2016/121817 International Publication No. 2015/08139

As described above, the polyimide film is required to replace the glass substrate, and is required to have not only mechanical properties and heat resistance but also high colorless transparency. Further, when manufacturing an image display device, for example, since heat treatment is performed in a state where an inorganic film is laminated on polyimide in the TFT step, outgas generated from the polyimide accumulates between the polyimide and the inorganic film, which causes yellowing. May occur, and it is required that there is no change in hue by heat treatment in a state where the inorganic films are laminated. However, it is difficult to achieve both of these performances, and it is difficult to prevent yellowing even if the heat resistance is improved by adding an additive.
Further, in order to exhibit colorless transparency in the polyimide itself, an aliphatic diamine or a fluorine-containing diamine is generally used in order to suppress the formation of an intramolecular or intramolecular charge transfer complex. However, under harsh conditions such as 350 ° C. or higher in the process of manufacturing a TFT when manufacturing a display, the aliphatic diamine lacks rigidity as compared with the aromatic diamine, so that it is difficult to develop heat resistance, and it also contains. Fluorodiamine also has a problem that yellowing occurs at high temperatures. Therefore, there has been a demand for a polyimide film having particularly excellent heat resistance, little change in hue after heat treatment, and a low yellowness.
The present invention has been made in view of such a situation, and the subject of the present invention is a polymer composition capable of obtaining a polyimide film having excellent heat resistance, little change in hue after heat treatment, and a low yellowness. It is an object of the present invention to provide a product, a varnish containing the composition, and a polyimide film having excellent heat resistance and a low yellowness.

The present inventors have determined that a polymer composition containing a specific fluorine-containing diamine and a repeating unit derived from a tetracarboxylic acid having an alicyclic structure or an aromatic ring and a specific phosphorus compound can solve the above-mentioned problems. I found it and came to complete the invention.

（式（１）中、Ｘ¹は脂環構造あるいは芳香族環を有する４価の基であり、Ｘは単結合、－ＮＨＣＯ－、－ＣＯＮＨ－、－ＣＯＯ－及び－ＯＣＯ－からなる群より選ばれる少なくとも１つである。
　式（２）中、Ｘ²は脂環構造あるいは芳香族環を有する４価の基であり、Ｒ¹及びＲ²はそれぞれ独立に水素、炭素数１～６のアルキル基、または炭素数３～９のアルキルシリル基であり、Ｘは単結合、－ＮＨＣＯ－、－ＣＯＮＨ－、－ＣＯＯ－及び－ＯＣＯ－からなる群より選ばれる少なくとも１つである。
　式（３）中、Ｒ³は、炭素数１～３０のアルキル基、フェニル基、アルコキシ基、アクリロイル基、メタクリロイル基、アクリロイルオキシエチル基、及びメタクリロイルオキシエチル基からなる群より選ばれる少なくとも１つであり、ｎは０～２である。）
［２］重合体（Ｘ）が、下記一般式（１－２）で表される繰り返し単位及び下記一般式（２－２）で表される繰り返し単位からなる群より選ばれる少なくとも１つを含む、前記［１］に記載の重合体組成物。

（式（１－２）中、Ｘ¹は脂環構造あるいは芳香族環を有する４価の基であり、Ｘは単結合、－ＮＨＣＯ－、－ＣＯＮＨ－、－ＣＯＯ－及び－ＯＣＯ－からなる群より選ばれる少なくとも１つである。式（２－２）中、Ｘ²は脂環構造あるいは芳香族環を有する４価の基であり、Ｒ¹及びＲ²はそれぞれ独立に水素、炭素数１～６のアルキル基、または炭素数３～９のアルキルシリル基であり、Ｘは単結合、－ＮＨＣＯ－、－ＣＯＮＨ－、－ＣＯＯ－及び－ＯＣＯ－からなる群より選ばれる少なくとも１つである。）
［３］前記式（１）及び前記式（２）におけるＸが単結合である、前記［１］に記載の重合体組成物。
［４］重合体（Ｘ）が、下記一般式（１－２－１）で表される繰り返し単位及び下記一般式（２－２－１）で表される繰り返し単位からなる群より選ばれる少なくとも１つを含む、前記［１］～［３］のいずれか１つに記載の重合体組成物。

（式（１－２－１）中、Ｘ¹は脂環構造あるいは芳香族環を有する４価の基である。式（２－２－１）中、Ｘ²は脂環構造あるいは芳香族環を有する４価の基であり、Ｒ¹及びＲ²はそれぞれ独立に水素、炭素数１～６のアルキル基、または炭素数３～９のアルキルシリル基である。）
［５］前記式（１）で表される繰り返し単位が、前記重合体（Ｘ）の全繰り返し単位に対して１０モル％以上である、前記［１］～［４］のいずれか１つに記載の重合体組成物。
［６］前記式（２）で表される繰り返し単位が、前記重合体（Ｘ）の全繰り返し単位に対して１０モル％以上である、前記［１］～［５］のいずれか１つに記載の重合体組成物。
［７］化合物（Ｙ）の含有量が、重合体（Ｘ）に対して１０ｐｐｍ以上１０，０００ｐｐｍ以下である、前記［１］～［６］のいずれか１つに記載の重合体組成物。
［８］前記［１］～［７］のいずれか１つに記載の重合体組成物が有機溶媒に溶解してなるワニス。
［９］前記［８］に記載のワニスを支持体上に塗布し、加熱して得られる、ポリイミドフィルム。
［１０］前記［８］に記載のワニスを支持体上に塗布し、加熱する、ポリイミドフィルムの製造方法。 That is, the present invention relates to the following [1] to [10].
[1] A polymer (X) containing at least one selected from the group consisting of a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), and the following general formula ( A polymer composition containing the compound (Y) represented by 3).

(In formula (1), X ¹ is a tetravalent group having an alicyclic structure or an aromatic ring, and X is a group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-. At least one chosen.
In formula (2), X ² is a tetravalent group having an alicyclic structure or an aromatic ring, and R ¹ and R ² are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 3 to 3 carbon atoms, respectively. It is an alkylsilyl group of 9, and X is at least one selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-.
In the formula (3), R ³ is at least one selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, a phenyl group, an alkoxy group, an acryloyl group, a methacryloyl group, an acryloyloxyethyl group, and a methacryloyloxyethyl group. And n is 0 to 2. )
[2] The polymer (X) contains at least one selected from the group consisting of the repeating unit represented by the following general formula (1-2) and the repeating unit represented by the following general formula (2-2). , The polymer composition according to the above [1].

(In formula (1-2), X ¹ is a tetravalent group having an alicyclic structure or an aromatic ring, and X is composed of a single bond, -NHCO-, -CONH-, -COO- and -OCO-. At least one selected from the group. In formula (2-2), X ² is a tetravalent group having an alicyclic structure or an aromatic ring, and R ¹ and R ² are independently hydrogen and carbon atoms, respectively. It is an alkyl group of 1 to 6 or an alkylsilyl group having 3 to 9 carbon atoms, and X is at least one selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-. be.)
[3] The polymer composition according to the above [1], wherein X in the formula (1) and the formula (2) is a single bond.
[4] At least the polymer (X) is selected from the group consisting of a repeating unit represented by the following general formula (1-2-1) and a repeating unit represented by the following general formula (2-2-1). The polymer composition according to any one of the above [1] to [3], which comprises one.

(In the formula (1-2-1), X ¹ is a tetravalent group having an alicyclic structure or an aromatic ring. In the formula (2-2-1), X ² is an alicyclic structure or an aromatic ring. R ¹ and R ² are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms, respectively.)
[5] One of the above [1] to [4], wherein the repeating unit represented by the formula (1) is 10 mol% or more with respect to all the repeating units of the polymer (X). The polymer composition according to the above.
[6] One of the above [1] to [5], wherein the repeating unit represented by the formula (2) is 10 mol% or more with respect to all the repeating units of the polymer (X). The polymer composition according to the above.
[7] The polymer composition according to any one of the above [1] to [6], wherein the content of the compound (Y) is 10 ppm or more and 10,000 ppm or less with respect to the polymer (X).
[8] A varnish in which the polymer composition according to any one of the above [1] to [7] is dissolved in an organic solvent.
[9] A polyimide film obtained by applying the varnish according to the above [8] onto a support and heating it.
[10] A method for producing a polyimide film, wherein the varnish according to the above [8] is applied onto a support and heated.

According to the present invention, a polymer composition having excellent heat resistance, little change in hue after heat treatment, and a polyimide film having a low yellowness can be obtained, a varnish containing the composition, and heat treatment having excellent heat resistance. It is possible to provide a polyimide film having a low degree of yellowness with little change in hue afterwards.

（式（１）中、Ｘ¹は脂環構造あるいは芳香族環を有する４価の基であり、Ｘは単結合、－ＮＨＣＯ－、－ＣＯＮＨ－、－ＣＯＯ－及び－ＯＣＯ－からなる群より選ばれる少なくとも１つである。
　式（２）中、Ｘ²は脂環構造あるいは芳香族環を有する４価の基であり、Ｒ¹及びＲ²はそれぞれ独立に水素、炭素数１～６のアルキル基、または炭素数３～９のアルキルシリル基であり、Ｘは単結合、－ＮＨＣＯ－、－ＣＯＮＨ－、－ＣＯＯ－及び－ＯＣＯ－からなる群より選ばれる少なくとも１つである。
　式（３）中、Ｒ³は、炭素数１～３０のアルキル基、フェニル基、アルコキシ基、アクリロイル基、メタクリロイル基、アクリロイルオキシエチル基、及びメタクリロイルオキシエチル基からなる群より選ばれる少なくとも１つであり、ｎは０～２である。） [Polymer composition]
The polymer composition of the present invention contains at least one selected from the group consisting of a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2) (X). And the compound (Y) represented by the following general formula (3).

(In formula (1), X ¹ is a tetravalent group having an alicyclic structure or an aromatic ring, and X is a group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-. At least one chosen.
In formula (2), X ² is a tetravalent group having an alicyclic structure or an aromatic ring, and R ¹ and R ² are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 3 to 3 carbon atoms, respectively. It is an alkylsilyl group of 9, and X is at least one selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-.
In the formula (3), R ³ is at least one selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, a phenyl group, an alkoxy group, an acryloyl group, a methacryloyl group, an acryloyloxyethyl group, and a methacryloyloxyethyl group. And n is 0 to 2. )

The reason why the polymer composition of the present invention is excellent as a raw material for a polyimide film, and the obtained polyimide film has excellent heat resistance, little change in hue after heat treatment, and low yellowness. Is not clear, but it can be thought of as follows.
The polymer composition of the present invention contains a specific phosphorus compound, but the phosphorus compound is coordinated to the end of the polyimide obtained by imidizing the polymer, or the end of the polyimide reacts with the phosphorus compound. In particular, it is considered that side reactions or decomposition deterioration of the terminal at high temperature can be suppressed, and further, desorption of fluorine derived from fluorine-containing diamine can be suppressed, thereby achieving both heat resistance and low yellowness. It is considered that the color change can be suppressed even if the heat treatment is further performed.

（式（１）中、Ｘ¹は脂環構造あるいは芳香族環を有する４価の基であり、Ｘは単結合、－ＮＨＣＯ－、－ＣＯＮＨ－、－ＣＯＯ－及び－ＯＣＯ－からなる群より選ばれる少なくとも１つである。
　式（２）中、Ｘ²は脂環構造あるいは芳香族環を有する４価の基であり、Ｒ¹及びＲ²はそれぞれ独立に水素、炭素数１～６のアルキル基、または炭素数３～９のアルキルシリル基であり、Ｘは単結合、－ＮＨＣＯ－、－ＣＯＮＨ－、－ＣＯＯ－及び－ＯＣＯ－からなる群より選ばれる少なくとも１つである。） <Polymer (X)>
The polymer (X) contained in the polymer composition of the present invention is at least one selected from the group consisting of a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2). Including one.

(In formula (1), X ¹ is a tetravalent group having an alicyclic structure or an aromatic ring, and X is a group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-. At least one chosen.
In formula (2), X ² is a tetravalent group having an alicyclic structure or an aromatic ring, and R ¹ and R ² are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 3 to 3 carbon atoms, respectively. It is an alkylsilyl group of 9, and X is at least one selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-. )

X in the formula (1) is preferably a single bond from the viewpoint of heat resistance. Further, X in the formula (2) is preferably a single bond from the viewpoint of heat resistance. It is more preferable that both X in the formula (1) and the formula (2) are single bonds.

（式（１－１）中、Ｘ¹は脂環構造あるいは芳香族環を有する４価の基である。
　式（２－１）中、Ｘ²は脂環構造あるいは芳香族環を有する４価の基であり、Ｒ¹及びＲ²はそれぞれ独立に水素、炭素数１～６のアルキル基、または炭素数３～９のアルキルシリル基である。） That is, the polymer (X) contained in the polymer composition of the present invention comprises a repeating unit represented by the following general formula (1-1) and a repeating unit represented by the following general formula (2-1). It is preferable to include at least one selected from the group.

(In formula (1-1), X ¹ is a tetravalent group having an alicyclic structure or an aromatic ring.
In formula (2-1), X ² is a tetravalent group having an alicyclic structure or an aromatic ring, and R ¹ and R ² are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or a carbon number of carbon atoms, respectively. It is an alkylsilyl group of 3-9. )

（式（１－２）中、Ｘ¹は脂環構造あるいは芳香族環を有する４価の基であり、Ｘは単結合、－ＮＨＣＯ－、－ＣＯＮＨ－、－ＣＯＯ－及び－ＯＣＯ－からなる群より選ばれる少なくとも１つである。） The repeating unit represented by the general formula (1) contained in the polymer (X) is preferably a repeating unit represented by the following general formula (1-2).

(In formula (1-2), X ¹ is a tetravalent group having an alicyclic structure or an aromatic ring, and X is composed of a single bond, -NHCO-, -CONH-, -COO- and -OCO-. At least one selected from the group.)

（式（１－２－１）～（１－２－５）中、Ｘ¹は脂環構造あるいは芳香族環を有する４価の基である。） Examples of the repeating unit represented by the formula (1-2) contained in the polymer (X) include repeating units represented by the following formulas (1-2-1) to (1-2-5). From the viewpoint of heat resistance, the repeating unit represented by the formula (1-2-1) is preferable.
That is, in the above formula (1-2), X is at least one selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-, but from the viewpoint of heat resistance. X is preferably a single bond.

(In formulas (1-2-1) to (1-2-5), X ¹ is a tetravalent group having an alicyclic structure or an aromatic ring.)

（式（２－２）中、Ｘ²は脂環構造あるいは芳香族環を有する４価の基であり、Ｒ¹及びＲ²はそれぞれ独立に水素、炭素数１～６のアルキル基、または炭素数３～９のアルキルシリル基であり、Ｘは単結合、－ＮＨＣＯ－、－ＣＯＮＨ－、－ＣＯＯ－及び－ＯＣＯ－からなる群より選ばれる少なくとも１つである。） The repeating unit represented by the general formula (2) contained in the polymer (X) is preferably a repeating unit represented by the following general formula (2-2).

(In formula (2-2), X ² is a tetravalent group having an alicyclic structure or an aromatic ring, and R ¹ and R ² are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or carbon. It is an alkylsilyl group of number 3-9, where X is at least one selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-).

（式（２－２－１）～（２－２－５）中、Ｘ²は脂環構造あるいは芳香族環を有する４価の基であり、Ｒ¹及びＲ²はそれぞれ独立に水素、炭素数１～６のアルキル基、または炭素数３～９のアルキルシリル基である。） Examples of the repeating unit represented by the formula (2-2) contained in the polymer (X) include repeating units represented by the following formulas (2-2-1) to (2-2-5). From the viewpoint of heat resistance, the repeating unit represented by the formula (2-2-1) is preferable.
That is, in the above formula (2-2), X is at least one selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-, but from the viewpoint of heat resistance. X is preferably a single bond.

(In formulas (2-2-1) to (2-2-5), X ² is a tetravalent group having an alicyclic structure or an aromatic ring, and R ¹ and R ² are independently hydrogen and carbon, respectively. It is an alkyl group having 1 to 6 or an alkylsilyl group having 3 to 9 carbon atoms.)

（式（１－２）中、Ｘ¹は脂環構造あるいは芳香族環を有する４価の基であり、Ｘは単結合、－ＮＨＣＯ－、－ＣＯＮＨ－、－ＣＯＯ－及び－ＯＣＯ－からなる群より選ばれる少なくとも１つである。式（２－２）中、Ｘ²は脂環構造あるいは芳香族環を有する４価の基であり、Ｒ¹及びＲ²はそれぞれ独立に水素、炭素数１～６のアルキル基、または炭素数３～９のアルキルシリル基であり、Ｘは単結合、－ＮＨＣＯ－、－ＣＯＮＨ－、－ＣＯＯ－及び－ＯＣＯ－からなる群より選ばれる少なくとも１つである。式（１－２－１）中、Ｘ¹は脂環構造あるいは芳香族環を有する４価の基である。式（２－２－１）中、Ｘ²は脂環構造あるいは芳香族環を有する４価の基であり、Ｒ¹及びＲ²はそれぞれ独立に水素、炭素数１～６のアルキル基、または炭素数３～９のアルキルシリル基である。） From the above, the polymer (X) contained in the polymer composition of the present invention is a repeating unit represented by the following general formula (1-2) and a repeating unit represented by the following general formula (2-2). It is preferable to include at least one selected from the group consisting of units, from the repeating unit represented by the following general formula (1-2-1) and the repeating unit represented by the following general formula (2-2-1). It is more preferable to include at least one selected from the group.

(In formula (1-2), X ¹ is a tetravalent group having an alicyclic structure or an aromatic ring, and X is composed of a single bond, -NHCO-, -CONH-, -COO- and -OCO-. At least one selected from the group. In formula (2-2), X ² is a tetravalent group having an alicyclic structure or an aromatic ring, and R ¹ and R ² are independently hydrogen and carbon atoms, respectively. It is an alkyl group of 1 to 6 or an alkylsilyl group having 3 to 9 carbon atoms, and X is at least one selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-. In the formula (1-2-1), X ¹ is a tetravalent group having an alicyclic structure or an aromatic ring. In the formula (2-2-1), X ² is an alicyclic structure or an aromatic ring. It is a tetravalent group having a ring, and R ¹ and R ² are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms, respectively.)

（式（１）中、Ｘ¹は脂環構造あるいは芳香族環を有する４価の基であり、Ｘは単結合、－ＮＨＣＯ－、－ＣＯＮＨ－、－ＣＯＯ－及び－ＯＣＯ－からなる群より選ばれる少なくとも１つである。式（３）中、Ｒ³は、炭素数１～３０のアルキル基、フェニル基、アルコキシ基、アクリロイル基、メタクリロイル基、アクリロイルオキシエチル基、及びメタクリロイルオキシエチル基からなる群より選ばれる少なくとも１つであり、ｎは０～２である。）
　下記一般式（２）で表される繰り返し単位を含むポリアミド酸と、下記一般式（３）で表される化合物（Ｙ）とを含む、ポリアミド酸組成物であってもよい。

（式（２）中、Ｘ²は脂環構造あるいは芳香族環を有する４価の基であり、Ｒ¹及びＲ²はそれぞれ独立に水素、炭素数１～６のアルキル基、または炭素数３～９のアルキルシリル基であり、Ｘは単結合、－ＮＨＣＯ－、－ＣＯＮＨ－、－ＣＯＯ－及び－ＯＣＯ－からなる群より選ばれる少なくとも１つである。式（３）中、Ｒ³は、炭素数１～３０のアルキル基、フェニル基、アルコキシ基、アクリロイル基、メタクリロイル基、アクリロイルオキシエチル基、及びメタクリロイルオキシエチル基からなる群より選ばれる少なくとも１つであり、ｎは０～２である。） The polymer (X) contains at least one selected from the group consisting of the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2). It may contain only one of the repeating unit represented by 1) or the repeating unit represented by the general formula (2), or may contain both.
That is, the polymer composition of the present invention is a polyimide composition containing a polyimide containing a repeating unit represented by the following general formula (1) and a compound (Y) represented by the following general formula (3). May be

(In formula (1), X ¹ is a tetravalent group having an alicyclic structure or an aromatic ring, and X is a group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-. At least one selected. In formula (3), R ³ is from an alkyl group having 1 to 30 carbon atoms, a phenyl group, an alkoxy group, an acryloyl group, a methacryloyl group, an acryloyloxyethyl group, and a methacryloyloxyethyl group. It is at least one selected from the group consisting of, and n is 0 to 2.)
It may be a polyamic acid composition containing a polyamic acid containing a repeating unit represented by the following general formula (2) and a compound (Y) represented by the following general formula (3).

(In the formula (2), X ² is a tetravalent group having an alicyclic structure or an aromatic ring, and R ¹ and R ² are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or 3 carbon atoms, respectively. 9 to 9 alkylsilyl groups, X is at least one selected from the group consisting of single bond, -NHCO-, -CONH-, -COO- and -OCO-. In formula (3), R ³ is. , At least one selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, a phenyl group, an alkoxy group, an acryloyl group, a methacryloyl group, an acryloyloxyethyl group, and a methacryloyloxyethyl group, and n is 0 to 2. be.)

The polymer (X) preferably contains the repeating unit represented by the general formula (1), and more preferably the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2). Includes both repeating units.

In the formula (1), X ¹ is a tetravalent group having an alicyclic structure or an aromatic ring. X ¹ is obtained by removing two dicarboxylic acid anhydride portions (four carboxy group portions) from the tetracarboxylic acid dianhydride which is a raw material of the constituent unit A derived from the tetracarboxylic acid dianhydride described later. Is preferable.
Similarly, Eq. (1-1), Eq. (1-2), Eq. (1-2-1), Eq. (1-2-2), Eq. (1-2-3), Eq. (1-2-2). In both 4) and the formula (1-2-5), X ¹ is a tetravalent group having an alicyclic structure or an aromatic ring. X ¹ is obtained by removing two dicarboxylic acid anhydride portions (four carboxy group portions) from the tetracarboxylic acid dianhydride which is a raw material of the constituent unit A derived from the tetracarboxylic acid dianhydride described later. Is preferable.

In the formula (2), X ² is a tetravalent group having an alicyclic structure or an aromatic ring. X ² is obtained by removing two dicarboxylic acid anhydride portions (four carboxy group portions) from the tetracarboxylic acid dianhydride which is a raw material of the constituent unit A derived from the tetracarboxylic acid dianhydride described later. Is preferable.
In the formula (2), R ¹ and R ² are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms, and are preferably hydrogen.
Similarly, Eq. (2-1), Eq. (2-2), Eq. (2-2-1), Eq. (2-2-2), Eq. (2-2-3), Eq. (2-2-2). In both 4) and the formula (2-2-5), X ¹ is a tetravalent group having an alicyclic structure or an aromatic ring. X ¹ is obtained by removing two dicarboxylic acid anhydride portions (four carboxy group portions) from the tetracarboxylic acid dianhydride which is a raw material of the constituent unit A derived from the tetracarboxylic acid dianhydride described later. Is preferable.

(Structure of polymer (X))
As described above, the polymer (X) contains at least one selected from the group consisting of the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2). It may contain only one of the repeating unit represented by the general formula (1) or the repeating unit represented by the general formula (2), and may contain both, but in particular, yellowness. From the viewpoint of reduction and improvement of transparency, the repeating unit represented by the formula (1) is preferably 10 mol% or more, more preferably 30 mol, based on all the repeating units of the polymer (X). % Or more, more preferably 50 mol% or more, still more preferably 70 mol% or more, still more preferably 90 mol% or more, and 100 mol% or less.
Further, from the viewpoint of maintaining low yellowness and improving heat resistance, the repeating unit represented by the formula (2) is preferably 10 mol% with respect to all the repeating units of the polymer (X). More preferably, it is 30 mol% or more, further preferably 50 mol% or more, further preferably 70 mol% or more, still more preferably 90 mol% or more, and 100 mol% or less. Is.
Further, when both the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) are included, the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (1) are included. The molar ratio [(1) / (2)] of the repeating unit represented by 2) is preferably 10/90 to 70/30, more preferably 20/80 to 60/40, and even more preferably 20/80 to 60/40. It is 25/75 to 55/45.

<Each structural unit of polymer (X)>
The polymer (X) contains at least one selected from the group consisting of the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2), and constitutes the polymer. The structural unit to be used will be described below.

The polymer (X) has a structural unit A derived from tetracarboxylic dianhydride and a structural unit B derived from diamine.
In the repeating unit represented by the general formula (1), the constituent unit A and the constituent unit B form an imide structure, and in the repeating unit represented by the general formula (2), the constituent unit A and the constituent unit B are formed. The structural unit B forms an amic acid structure, and the structural unit derived from tetracarboxylic dianhydride is collectively referred to as the structural unit A, and the structural unit derived from the diamine is collectively referred to as the structural unit B.

(Constituent unit A)
The structural unit A is a structural unit derived from tetracarboxylic acid dianhydride, and is a group consisting of a structural unit derived from the alicyclic tetracarboxylic acid dianhydride and a structural unit derived from aromatic tetracarboxylic acid dianhydride. At least one selected from the above, preferably a structural unit derived from alicyclic tetracarboxylic acid dianhydride from the viewpoint of low yellowness and transparency, and preferably aromatic tetracarboxylic from the viewpoint of heat resistance. It is a structural unit derived from acid dianhydride.

　式（ａ１）で表される化合物は、ノルボルナン－２－スピロ－α－シクロペンタノン－α’－スピロ－２’’－ノルボルナン－５，５’’，６，６’’－テトラカルボン酸二無水物である。 Examples of the alicyclic tetracarboxylic acid dianhydride giving a structural unit derived from the alicyclic tetracarboxylic acid dianhydride include 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 1,2,3. 4-Cyclobutanetetracarboxylic acid dianhydride, norbornan-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornan-5,5'', 6,6''-tetracarboxylic acid dianhydride Bicyclo [2.2.2] octa-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, dicyclohexyltetracarboxylic acid dianhydride, 5,5'-(1,4-phenylene) )-Bis [hexahydro-4,7-Methanoisobenzofuran-1,3-dione], 5,5'-bis-2-norbornen-5,5', 6,6'-tetracarboxylic acid-5,5', 6 , 6'-dianhydride, or their positional isomers and the like.
Among these, from the viewpoint of low yellowness and transparency, the compound is preferably represented by the following formula (a1), and the constituent unit A is preferably a constituent unit derived from the compound represented by the formula (a1). (A1) is included.

The compound represented by the formula (a1) is norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic dianhydride. It is an anhydride.

Examples of the aromatic tetracarboxylic acid dianhydride giving a structural unit derived from the aromatic tetracarboxylic acid dianhydride include biphenyltetracarboxylic acid dianhydride (BPDA) and 9,9-bis (3,4-dicarboxyphenyl). ) Fluolene dianhydride (BPAF), pyromellitic acid dianhydride, 3,3', 4,4'-(hexafluoroisopropylidene) diphthalic acid anhydride, 3,3', 4,4'-diphenylsulfone tetra Examples thereof include carboxylic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2', 3,3'-benzophenone tetracarboxylic acid dianhydride and the like.
Among these, at least one selected from the group consisting of the compound represented by the following formula (a2) and the compound represented by the following formula (a3) is preferably selected from the viewpoint of achieving both heat resistance and low yellowness. Yes, more preferably a compound represented by the following formula (a2).
That is, the structural unit A is preferably selected from the group consisting of the structural unit (A2) derived from the compound represented by the following formula (a2) and the structural unit (A3) derived from the compound represented by the following formula (a3). It contains at least one of the constituent units (A2) derived from the compound represented by the following formula (a2).

The compound represented by the formula (a2) is biphenyltetracarboxylic acid dianhydride (BPDA), and specific examples thereof are 3,3', 4,4'-biphenyl represented by the following formula (a2s). Tetracarboxylic acid dianhydride (s-BPDA), 2,3,3', 4'-biphenyltetracarboxylic acid dianhydride (a-BPDA) represented by the following formula (a2a), the following formula (a2i) Examples thereof include 2,2', 3,3'-biphenyltetracarboxylic acid dianhydride (i-BPDA) represented. Of these, 3,3', 4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) represented by the following formula (a2s) is preferable.

The compound represented by the formula (a3) is 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride (BPAF).

When the polymer (X) contained in the polymer composition of the present invention contains both the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2), the general formula is described above. The repeating unit (polyimide unit) represented by the formula (1) includes at least one selected from the group consisting of the constituent unit (A1) and the constituent unit (A3), and is represented by the general formula (2). The repeating unit (polyimide unit) preferably contains a structural unit (A2).

The structural unit A may contain a structural unit other than the aromatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride. The tetracarboxylic acid dianhydride giving such a structural unit is not particularly limited, and examples thereof include aliphatic tetracarboxylic acid dianhydrides such as 1,2,3,4-butanetetracarboxylic acid dianhydride.
The structural unit arbitrarily included in the structural unit A may be one type or two or more types.
In the present specification, the aromatic tetracarboxylic acid dianhydride means a tetracarboxylic acid dianhydride containing one or more aromatic rings, and the alicyclic tetracarboxylic acid dianhydride has one alicyclic ring. The tetracarboxylic acid dianhydride containing the above and containing no aromatic ring is meant, and the aliphatic tetracarboxylic acid dianhydride means a tetracarboxylic acid dianhydride containing neither an aromatic ring nor an alicyclic ring.

（式（ｂ１）中、Ｘは単結合、－ＮＨＣＯ－、－ＣＯＮＨ－、－ＣＯＯ－及び－ＯＣＯ－からなる群より選ばれる少なくとも１つである。） (Structural unit B)
The structural unit B is a structural unit derived from a diamine, and includes a structural unit (B1) derived from the compound represented by the formula (b1).
By including the structural unit (B1) in the structural unit B, it is excellent in heat resistance, and particularly excellent in the effect of reducing the yellowness when combined with the compound (Y).
The ratio of the structural unit (B1) in the structural unit B is preferably 45 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99 mol% or more. The upper limit of the ratio is not particularly limited and is 100 mol% or less.

(In formula (b1), X is at least one selected from the group consisting of single bond, -NHCO-, -CONH-, -COO- and -OCO-.)

The structural unit (B1) preferably includes a structural unit (B11) derived from the compound represented by the following formula (b11).

（式（１）中、Ｘは単結合、－ＮＨＣＯ－、－ＣＯＮＨ－、－ＣＯＯ－及び－ＯＣＯ－からなる群より選ばれる少なくとも１つである。） Further, the structural unit (B1) preferably contains a structural unit (B12) derived from the compound represented by the following formula (b12).

(In formula (1), X is at least one selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-.)

The structural unit (B12) is a structural unit (B121) derived from a compound represented by the following formula (b121), a structural unit (B122) derived from a compound represented by the following formula (b122), and the following formula (b123). ) Contains at least one selected from the group consisting of the structural unit (B123) derived from the compound represented by the following formula (b121), and more preferably from the viewpoint of heat resistance. It is a structural unit (B121) containing a unit (B121) and more preferably derived from a compound represented by the following formula (b121).

The compound represented by the formula (b121) is 2,2'-bis (trifluoromethyl) benzidine (TFMB).
By including the structural unit (B1) in the structural unit B, it is excellent in heat resistance, and particularly excellent in the effect of reducing the yellowness when combined with the compound (Y).

The structural unit B may include a structural unit other than the structural unit (B1). The diamine that gives such a constituent unit is not particularly limited, but is 3,5-diaminobenzoic acid (3,5-DABA), 9,9-bis (4-aminophenyl) fluorene (BAFL), 4-amino. Phenyl-4-aminobenzoate (4-BAAB), 1,4-phenylenediamine, p-xylylene diamine, 1,5-diaminonaphthalene, 2,2'-dimethylbiphenyl-4,4'-diamine, 2,2 '-Dimethylbiphenyl-4,4'-diamine, 4,4'-diaminodiphenylmethane, 1,4-bis [2- (4-aminophenyl) -2-propyl] benzene, 2,2-bis (4-amino) Phenyl) Hexafluoropropane, 4,4'-diaminobenzanilide, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine, α, α' -Bis (4-aminophenyl) -1,4-diisopropylbenzene, N, N'-bis (4-aminophenyl) terephthalamide, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, And aromatic diamines such as 1,4-bis (4-aminophenoxy) benzene; alicyclic diamines such as 1,3-bis (aminomethyl) cyclohexane and 1,4-bis (aminomethyl) cyclohexane; and ethylenediamine. And aliphatic diamines such as hexamethylene diamine.

　式（ｂ２１）で表される化合物は、３，５－ジアミノ安息香酸（３，５－ＤＡＢＡ）である。
　式（ｂ２２）で表される化合物は、９，９－ビス（４－アミノフェニル）フルオレン（ＢＡＦＬ）である。
　構成単位Ｂが、構成単位（Ｂ２）を含む場合、構成単位（Ｂ１）と構成単位（Ｂ２）のモル比［（Ｂ１）／（Ｂ２）］は、好ましくは２０／８０～９５／５であり、より好ましくは５０／５０～９０／１０であり、更に好ましくは７０／３０～９０／１０である。 Among these, at least one selected from the group consisting of a compound represented by the following formula (b21), a compound represented by the following formula (b22), and a compound represented by the following formula (b3) is preferable. From the viewpoint of improving low yellowness, transparency, and heat resistance, the compound is more preferably represented by the following formula (b21).
That is, the structural unit B is preferably selected from the group consisting of the structural unit (B21) derived from the compound represented by the following formula (b21) and the structural unit (B22) derived from the compound represented by the following formula (b22). It contains at least one selected from the group consisting of the structural unit (B2) which is at least one and the structural unit (B3) derived from the compound represented by the following formula (b3), and more preferably the following formula (b21). ) And at least one constituent unit (B2) selected from the group consisting of the constituent unit (B21) derived from the compound represented by the following formula (b22) and the constituent unit (B22) derived from the compound represented by the following formula (b22). It contains, more preferably, a structural unit (B21) derived from the compound represented by the following formula (b21).

The compound represented by the formula (b21) is 3,5-diaminobenzoic acid (3,5-DABA).
The compound represented by the formula (b22) is 9,9-bis (4-aminophenyl) fluorene (BAFL).
When the constituent unit B includes the constituent unit (B2), the molar ratio [(B1) / (B2)] of the constituent unit (B1) to the constituent unit (B2) is preferably 20/80 to 95/5. , More preferably 50/50 to 90/10, and even more preferably 70/30 to 90/10.

　式（ｂ３）で表される化合物は、４－アミノフェニル－４－アミノベンゾエート（４－ＢＡＡＢ）である。

The compound represented by the formula (b3) is 4-aminophenyl-4-aminobenzoate (4-BAAB).

In the present specification, the aromatic diamine means a diamine containing one or more aromatic rings, and the alicyclic diamine means a diamine containing one or more alicyclic rings and does not contain an aromatic ring, and is a fat. The group diamine means a diamine that does not contain an aromatic ring or an alicyclic ring.
The structural unit arbitrarily included in the structural unit B may be one type or two or more types.

(Method for producing polymer (X))
The polymer (X) may be produced by any method, but the following method is preferable.
As described above, the polymer (X) has a repeating unit represented by the general formula (1) (that is, an imide moiety) and a repeating unit represented by the general formula (2) (that is, an amide acid moiety). ), But these can be adjusted by changing the manufacturing method.
Specifically, in the production method (method for producing an imide-amidic acid copolymer) in which both the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) are included, the formula ( By using only the step of manufacturing the portion (polyamide portion) mainly containing the repeating unit represented by 1), the polymer (X) (polyamide) substantially composed of the repeating unit represented by the formula (1) can be obtained. By using only the step of producing the obtained portion (polyamic acid moiety) mainly containing the repeating unit represented by the formula (2), the polymer (2) substantially composed of the repeating unit represented by the formula (2). X) (polyamic acid) can be obtained.

The polymer (X) (hereinafter, also referred to as an imido-amide acid copolymer) containing both the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) is described in the following step 1 and the following steps 1. It is preferable to use the method having step 2.
Step 1: Reacting the tetracarboxylic acid component constituting the imide moiety with the diamine component to obtain an imide oligomer Step 2: The imide oligomer obtained in Step 1 and the tetracarboxylic acid component constituting the amic acid moiety and Step of reacting diamine component to obtain imid-amide acid copolymer

By reacting all the tetracarboxylic acid components with the diamine components in step 1, a polymer (X) (polyimide) consisting of a repeating unit substantially represented by the formula (1) can be obtained. Specifically, the method for producing the polymer (X) (polyimide) substantially composed of the repeating unit represented by the formula (1) is described in the above step 1 as "a tetracarboxylic acid component constituting the polyimide and a diamine component". It is read as "the process of obtaining polyimide by reacting with".
Further, by reacting all the tetracarboxylic acid components and the diamine components in the step 2 without performing the step 1, the polymer (X) (polyamic acid) composed of the repeating unit substantially represented by the formula (2). ) Is obtained. Specifically, the method for producing the polymer (X) (polyamic acid), which is substantially composed of the repeating unit represented by the formula (2), describes the step 2 as "a tetracarboxylic acid component constituting the polyamic acid and a diamine." It should be read as "the process of reacting the components to obtain polyamic acid".

[Step 1]
Step 1 is a step of reacting the tetracarboxylic acid component constituting the imide moiety with the diamine component to obtain an imide oligomer.
The tetracarboxylic acid component used in step 1 preferably contains a compound that gives a structural unit (A1), and it is preferable that the entire amount thereof is used in step 1, and tetracarboxylic dians other than the compound that gives the structural unit (A1). It may contain an acid component. As the tetracarboxylic acid component other than the compound giving the structural unit (A1), a compound giving the structural unit (A2) or a compound giving the structural unit (A3) is preferable, and a compound giving the structural unit (A3) is more preferable.
The diamine component used in step 1 preferably contains a compound that gives the constituent unit (B1), and contains a diamine component other than the compound that gives the constituent unit (B1) as long as the effect of the present invention is not impaired. May be good. As the tetracarboxylic acid component other than the compound giving the structural unit (B1), a compound giving the structural unit (B2) or a compound giving the structural unit (B3) is preferable.
In step 1, the diamine component with respect to the tetracarboxylic acid component is preferably 1.01 to 2 mol, more preferably 1.05 to 1.9 mol, and 1.1 to 1.7 mol. Is even more preferable.
When a polymer (X) (polyimide) consisting of a repeating unit represented by the formula (1) is obtained, the diamine component with respect to the tetracarboxylic acid component is 0.9 to 1.1 mol. Is preferable.

The method for reacting the tetracarboxylic acid component and the diamine component for obtaining the imide oligomer in step 1 is not particularly limited, and a known method can be used.
As a specific reaction method, (1) a tetracarboxylic acid component, a diamine component, and a reaction solvent are charged in a reactor, stirred at 10 to 110 ° C. for 0.5 to 30 hours, and then heated to imidize. Method of carrying out the reaction, (2) The diamine component and the reaction solvent are charged into a reactor and dissolved, then the tetracarboxylic acid component is charged, and if necessary, the mixture is stirred at 10 to 110 ° C. for 0.5 to 30 hours, and then. Examples thereof include a method of carrying out an imidization reaction by raising the temperature to (3) a method of charging a tetracarboxylic acid component, a diamine component and a reaction solvent into a reactor and immediately raising the temperature to carry out the imidization reaction.

In the imidization reaction, it is preferable to carry out the reaction while removing water generated during production using a Dean-Stark apparatus or the like. By performing such an operation, the degree of polymerization and the imidization rate can be further increased.

In the above imidization reaction, a known imidization catalyst can be used. Examples of the imidization catalyst include a base catalyst or an acid catalyst.
Base catalysts include pyridine, quinoline, isoquinoline, α-picoline, β-picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine, triethylenediamine, imidazole, N, N. -Examples include organic base catalysts such as dimethylaniline and N, N-diethylaniline, and inorganic base catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogencarbonate and sodium hydrogencarbonate.
Examples of the acid catalyst include crotonic acid, acrylic acid, trans-3-hexenoic acid, cinnamic acid, benzoic acid, methylbenzoic acid, oxybenzoic acid, terephthalic acid, benzenesulfonic acid, paratoluenesulfonic acid, naphthalenesulfonic acid and the like. Can be mentioned. The above imidization catalyst may be used alone or in combination of two or more.
Of the above, from the viewpoint of handleability, a base catalyst is preferable, an organic base catalyst is more preferable, one or more selected from triethylamine and triethylenediamine is further preferable, and triethylamine is further preferable.

The temperature of the imidization reaction is preferably 120 to 250 ° C., more preferably 160 to 200 ° C. from the viewpoint of suppressing the reaction rate and gelation. The reaction time is preferably 0.5 to 10 hours after the start of distillation of the produced water.

The imide oligomer obtained in step 1 preferably has an imide repeating structural unit formed from a compound giving a structural unit (A1) and a compound giving a structural unit (B1).
By the above method, a solution containing an imide oligomer dissolved in a solvent can be obtained. The solution containing the imide oligomer obtained in step 1 contains at least a part of the components used as the tetracarboxylic acid component and the diamine component in step 1 as unreacted monomers as long as the effects of the present invention are not impaired. You may.

[Step 2]
Step 2 in the production method of the present invention is a step of reacting the imide oligomer obtained in step 1 with the tetracarboxylic acid component and the diamine component constituting the amic acid moiety to obtain an imide-amide acid copolymer. ..

The tetracarboxylic dian component used in step 2 preferably contains a compound that gives a structural unit (A1), and may contain a tetracarboxylic acid component other than the compound that gives the structural unit (A1). As the tetracarboxylic acid component other than the compound giving the structural unit (A1), a compound giving the structural unit (A2) or a compound giving the structural unit (A3) is preferable.
When the production method of the present invention has both step 1 and step 2, the tetracarboxylic dian component used in step 2 is preferably a compound giving a structural unit (A2).
The diamine component used in step 2 preferably contains a compound that gives the constituent unit (B1), and contains a diamine component other than the compound that gives the constituent unit (B1) as long as the effect of the present invention is not impaired. May be good. As the tetracarboxylic acid component other than the compound giving the structural unit (B1), a compound giving the structural unit (B2) or a compound giving the structural unit (B3) is preferable.
When the production method of the present invention has both step 1 and step 2, the diamine component used in step 2 is preferably a compound giving a structural unit (B3).
When a polymer (X) (polyamic acid) consisting of a repeating unit represented by the formula (2) is obtained by performing only step 2, the diamine component with respect to the tetracarboxylic acid component is set to 0. It is preferably 9.9 to 1.1 mol.

The method for reacting the tetracarboxylic acid component and the diamine component in step 2 with the imide oligomer obtained in step 1 is not particularly limited, and a known method can be used.
As a specific reaction method, (1) the imide oligomer, the tetracarboxylic acid component, the diamine component and the solvent obtained in step 1 are charged into the reactor, and 1 in the range of 0 to 120 ° C, preferably 5 to 80 ° C. A method of stirring for about 72 hours, (2) the imide oligomer and the solvent obtained in step 1 are charged into a reactor and dissolved, and then the tetracarboxylic acid component and the diamine component are charged, and the temperature is 0 to 120 ° C., preferably 5 to. Examples thereof include a method of stirring at 80 ° C. for 1 to 72 hours.
When the reaction is carried out at 80 ° C. or lower, the molecular weight of the copolymer obtained in step 2 does not fluctuate depending on the temperature history at the time of polymerization, and the progress of thermal imidization can be suppressed. Can be manufactured stably.

By the above method, a copolymer solution containing an imide-amide acid copolymer dissolved in a solvent can be obtained. Further, by performing only step 1, a polyimide solution containing polyimide can be obtained, and by performing only step 2, a polyamic acid solution containing polyamic acid can be obtained.
The concentration of the copolymer in the obtained solution is usually 1 to 50% by mass, preferably 3 to 35% by mass, and more preferably 5 to 30% by mass.
The concentration of polyimide in the obtained solution is usually 1 to 50% by mass, preferably 3 to 35% by mass, and more preferably 5 to 30% by mass.
Further, the concentration of the polyamic acid in the obtained solution is usually 1 to 50% by mass, preferably 3 to 35% by mass, and more preferably 5 to 30% by mass.

The number average molecular weight of the imide-amidoic acid copolymer obtained by the above-mentioned production method is preferably 5,000 to 500,000 from the viewpoint of the mechanical strength of the obtained polyimide film. Further, the weight average molecular weight (Mw) is preferably 10,000 to 800,000, more preferably 100,000 to 300,000 from the same viewpoint. The number average molecular weight and the weight average molecular weight of the copolymer can be obtained from, for example, standard polymethylmethacrylate (PMMA) conversion values measured by gel filtration chromatography.
The number average molecular weight of the polyimide obtained by the above-mentioned production method is preferably 5,000 to 500,000 from the viewpoint of the mechanical strength of the obtained polyimide film. Further, the weight average molecular weight (Mw) is preferably 10,000 to 800,000, more preferably 100,000 to 300,000 from the same viewpoint.
The number average molecular weight of the polyamic acid obtained by the above-mentioned production method is preferably 5,000 to 500,000 from the viewpoint of the mechanical strength of the obtained polyimide film. Further, the weight average molecular weight (Mw) is preferably 10,000 to 800,000, more preferably 100,000 to 300,000 from the same viewpoint.
Next, the raw materials and the like used in this production method will be described.

[Tetracarboxylic acid component]
Examples of the compound that gives the structural unit (A1) as the tetracarboxylic acid component used as a raw material in the present production method include, but are not limited to, the compound represented by the formula (a1), as long as the same structural unit is given. It may be the derivative. Examples of the derivative include a tetracarboxylic acid corresponding to the compound represented by the formula (a1) and an alkyl ester of the tetracarboxylic acid. As the compound that gives the structural unit (A1), the compound represented by the formula (a1) is preferable.
Similarly, the compound giving the structural unit (A2) includes a compound represented by the formula (a2), but the compound is not limited to this, and may be a derivative thereof as long as the same structural unit is given. Examples of the derivative include a tetracarboxylic acid corresponding to the compound represented by the formula (a2) and an alkyl ester of the tetracarboxylic acid. As the compound that gives the structural unit (A2), the compound represented by the formula (a2) is preferable.
Further, the compound giving the structural unit (A3) includes, but is not limited to, the compound represented by the formula (a3), and may be a derivative thereof as long as the same structural unit is given. Examples of the derivative include a tetracarboxylic acid corresponding to the compound represented by the formula (a3) and an alkyl ester of the tetracarboxylic acid. As the compound that gives the structural unit (A3), the compound represented by the formula (a3) is preferable.

[Diamine component]
Examples of the compound that gives a structural unit (B1) as a diamine component used as a raw material in the present production method include diamine, but the compound is not limited to this, and may be a derivative thereof as long as the same structural unit is given. Examples of the derivative include diisocyanates corresponding to diamines. Diamine is preferable as the compound that gives the structural unit (B1).
Similarly, the compound that gives the structural unit (B2) includes, but is not limited to, a derivative thereof as long as the same structural unit is given. Examples of the derivative include diisocyanates corresponding to diamines. Diamine is preferable as the compound that gives the structural unit (B2).
Further, the compound that gives the structural unit (B3) includes, but is not limited to, a derivative thereof as long as the same structural unit is given. Examples of the derivative include diisocyanates corresponding to diamines. Diamine is preferable as the compound that gives the structural unit (B3).

In the present invention, the ratio of the amount of the tetracarboxylic acid component to the diamine component charged in all the steps of producing the copolymer including the steps 1 and 2 is 0.9 for the diamine component with respect to 1 mol of the tetracarboxylic acid component. It is preferably ~ 1.1 mol.

[End sealant]
Further, in the production of the polymer (X), an end-capping agent may be used in addition to the above-mentioned tetracarboxylic acid component and diamine component. The terminal encapsulant is preferably used in step 2 when both steps 1 and 2 are performed.
As the terminal encapsulant, monoamines or dicarboxylic acids are preferable. The amount of the terminal encapsulant to be introduced is preferably 0.0001 to 0.1 mol, particularly preferably 0.001 to 0.06 mol, based on 1 mol of the tetracarboxylic acid component. Examples of the monoamine terminal encapsulant include methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3-methylbenzylamine, 3-. Ethylbenzylamine, aniline, 3-methylaniline, 4-methylaniline and the like are recommended. Of these, benzylamine and aniline can be preferably used. As the dicarboxylic acid terminal encapsulant, dicarboxylic acids are preferable, and a part thereof may be ring-closed. For example, phthalic acid, phthalic acid anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2,3-benzophenonedicarboxylic acid, 3,4-benzophenonedicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, 4-cyclohexene-1. , 2-Dicarboxylic acid, etc. are recommended. Of these, phthalic acid and phthalic anhydride can be preferably used.

〔solvent〕
The solvent used in the method for producing the polymer (X) may be any solvent as long as it can dissolve the imide-amidoic acid copolymer to be produced. For example, an aprotic solvent, a phenol solvent, an ether solvent, a carbonate solvent and the like can be mentioned.

Specific examples of the aprotonic solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactum, 1,3-dimethylimidazolidinone, tetramethylurea and the like. Amide-based solvent, lactone-based solvent such as γ-butyrolactone and γ-valerolactone, phosphorus-containing amide-based solvent such as hexamethylphosphoric amide and hexamethylphosphintriamide, and sulfur-containing solvent such as dimethylsulfone, dimethylsulfoxide, and sulfolane. Examples thereof include a system solvent, a ketone solvent such as acetone, methyl ethyl ketone, cyclohexanone and methylcyclohexanone, and an ester solvent such as acetic acid (2-methoxy-1-methylethyl).

Specific examples of the phenolic solvent include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4. -Xylenol, 3,5-xylenol and the like can be mentioned.
Specific examples of the ether solvent include 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, and bis [2- (2-methoxyethoxy) ethyl]. Examples include ether, tetrahydrofuran, 1,4-dioxane and the like.
Specific examples of the carbonate solvent include diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate and the like.
Among the above reaction solvents, an amide solvent or a lactone solvent is preferable, an amide solvent is more preferable, and N-methyl-2-pyrrolidone is further preferable. The above reaction solvent may be used alone or in combination of two or more.

（式（３）中、Ｒ³は、炭素数１～３０のアルキル基、フェニル基、アルコキシ基、アクリロイル基、メタクリロイル基、アクリロイルオキシエチル基、及びメタクリロイルオキシエチル基からなる群より選ばれる少なくとも１つであり、ｎは０～２である。）
　化合物（Ｙ）を含むことで、耐熱性を有しつつ、低黄色度のフィルムを得ることができ、更にフィルムの透明性も向上させることができる。 <Compound (Y)>
The compound (Y) contained in the polymer composition of the present invention is represented by the following general formula (3).

In the formula (3), R ³ is at least one selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, a phenyl group, an alkoxy group, an acryloyl group, a methacryloyl group, an acryloyloxyethyl group, and a methacryloyloxyethyl group. And n is 0 to 2.)
By containing the compound (Y), a film having a low yellowness can be obtained while having heat resistance, and the transparency of the film can be further improved.

In the formula (3), R ³ is at least one selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, a phenyl group, an alkoxy group, an acryloyl group, a methacryloyl group, an acryloyloxyethyl group, and a methacryloyloxyethyl group. It is preferably an alkyl group having 1 to 30 carbon atoms.
The plurality of R ^3s may be the same or different, but are preferably the same.
n is 0 to 2, preferably 1 to 2.

The compound (Y) is a phosphorus compound, and specific examples of the compound (Y) include at least one selected from the group consisting of an acidic phosphoric acid ester and a phosphoric acid, and an acidic phosphoric acid ester is preferable.
Examples of the acidic phosphoric acid ester include isotridecyl acid phosphate, dibutyl phthalate and the like, and isotridecyl acid phosphate is preferable.

The content of the compound (Y) is preferably 10 ppm or more and 10,000 ppm or less, more preferably 100 ppm or more and 5,000 ppm or less, and further preferably 500 ppm or more and 2,000 ppm or less with respect to the polymer (X). Is. When the amount of the compound (Y) is in this range, a film having a low yellowness can be obtained while having heat resistance, and the transparency of the film can be further improved. In this specification, "ppm" indicates parts per million by mass.

[varnish]
The varnish of the present invention is obtained by dissolving the above-mentioned polymer composition in an organic solvent. That is, the varnish of the present invention is formed by dissolving the polymer (X) and the compound (Y) in an organic solvent, and the varnish of the present invention contains the polymer (X), the compound (Y) and the organic solvent. The polymer (X) and the compound (Y) are dissolved in the organic solvent.
The organic solvent may be any one that dissolves the polymer (X) and the compound (Y), and is not particularly limited, but the above-mentioned compound may be used alone or in combination of two or more as the solvent used for producing the polymer (X). It is preferable to mix and use.
The varnish of the present invention may be one in which compound (Y) is mixed and dissolved in the above-mentioned polymer (X) solution, or one in which a diluting solvent is further added.

When the polymer (X) contained in the varnish of the present invention contains a repeating unit (amidoic acid moiety) represented by the formula (2), further imidization is performed from the viewpoint of efficiently advancing the imidization of the amidic acid moiety. A catalyst and a dehydration catalyst can be contained. The imidization catalyst may be any imidization catalyst having a boiling point of 40 ° C. or higher and 180 ° C. or lower, and an amine compound having a boiling point of 180 ° C. or lower is preferable. If the imidization catalyst has a boiling point of 180 ° C. or lower, the film will be colored when dried at a high temperature after the film is formed, and the appearance will not be impaired. Further, if the imidization catalyst has a boiling point of 40 ° C. or higher, the possibility of volatilization before the imidization proceeds sufficiently can be avoided.
Examples of the amine compound preferably used as an imidization catalyst include pyridine and picoline. The above imidization catalyst may be used alone or in combination of two or more.
Examples of the dehydration catalyst include acid anhydrides such as acetic anhydride, propionic acid anhydride, n-butyric acid anhydride, benzoic acid anhydride and trifluoroacetic anhydride; and carbodiimide compounds such as dicyclohexylcarbodiimide. These may be used alone or in combination of two or more.

Since the polymer (X) contained in the varnish of the present invention has solvent solubility, it can be made into a high-concentration varnish. The varnish of the present invention preferably contains the polymer (X) in an amount of 3 to 40% by mass, more preferably 5 to 40% by mass, and even more preferably 10 to 30% by mass. The viscosity of the varnish is preferably 0.1 to 100 Pa · s, more preferably 0.1 to 20 Pa · s. The viscosity of the varnish is a value measured at 25 ° C. using an E-type viscometer.
Further, the varnish of the present invention has an inorganic filler, an adhesion accelerator, a release agent, a flame retardant, an ultraviolet stabilizer, a surfactant, a leveling agent, an antifoaming agent, and a fluorescent whitening agent as long as the required characteristics of the polyimide film are not impaired. It may contain various additives such as an agent, a cross-linking agent, a polymerization initiator, and a photosensitizer.
The method for producing the varnish of the present invention is not particularly limited, and a known method can be applied.

[Manufacturing method of polyimide film and polyimide film]
When the polymer (X) contains a repeating unit (amido acid moiety) represented by the formula (2), the polyimide film of the present invention comprises a polyimide resin obtained by imidizing the amid acid moiety of the polymer (X). Contains compound (Y). When the polymer (X) is polyimide, it contains the polyimide, a polyimide resin whose molecular weight has been further adjusted by heating, and compound (Y). Therefore, the polyimide film of the present invention has excellent heat resistance and low yellowness.
The polyimide film of the present invention can be produced by using the above-mentioned varnish.

The method for producing a polyimide film using the varnish of the present invention is not particularly limited, but the following method is preferable.
That is, the method of applying the above-mentioned varnish on the support and heating is preferable, and specifically, the varnish in which the polymer (X) and the compound (Y) are dissolved in an organic solvent is applied on the support. , The method of heating is preferable.
Further, as the polyimide film of the present invention, a polyimide film obtained by applying the above-mentioned varnish on a support and heating it is preferable, and specifically, the polymer (X) and the compound (Y) are organic solvents. A polyimide film obtained by applying a varnish dissolved in a varnish on a support and heating it is preferable.

Examples of the support include a smooth glass plate, a metal plate, a plastic, and the like.
After the varnish is applied onto the support or molded into a film, the organic solvent such as the reaction solvent and the diluting solvent contained in the varnish is removed by heating to obtain a polymer film, which is then contained in the polymer film. If the polymer contained has an amic acid moiety, the polyimide film can be produced by imidizing (dehydrating and ring-closing) the polymer by heating and then peeling it from the support.
The weight average molecular weight (Mw) of the polyimide resin contained in the polyimide film of the present invention is preferably 10,000 to 800,000, more preferably 30,000 to 500,000 from the viewpoint of the mechanical strength of the film. It is more preferably 50,000 to 400,000, and even more preferably 100,000 to 300,000. The weight average molecular weight of the copolymer can be obtained from, for example, a standard polymethylmethacrylate (PMMA) conversion value measured by gel filtration chromatography.

The heating temperature for drying the varnish of the present invention to obtain a polymer film is preferably 50 to 150 ° C. The heating temperature for imidizing the polymer by heating is preferably 200 to 500 ° C, more preferably 250 to 450 ° C, and even more preferably 300 to 430 ° C. The heating time is usually 1 minute to 6 hours, preferably 5 minutes to 2 hours, and more preferably 15 minutes to 1 hour.
Examples of the heating atmosphere include air gas, nitrogen gas, oxygen gas, hydrogen gas, and nitrogen / hydrogen mixed gas. In order to suppress the coloring of the obtained polyimide resin, nitrogen gas and hydrogen concentration having an oxygen concentration of 100 ppm or less are used. A nitrogen / hydrogen mixed gas having a gas content of 0.5% or less is preferable.
The imidization method is not limited to thermal imidization, and chemical imidization can also be applied.

The thickness of the polyimide film of the present invention can be appropriately selected depending on the intended use and the like, but is preferably 1 to 250 μm, more preferably 5 to 100 μm, and further preferably 5 to 50 μm. When the thickness is 1 to 250 μm, it can be practically used as a self-supporting film.
The thickness of the polyimide film can be easily controlled by adjusting the solid content concentration and the viscosity of the varnish.

By using the polymer composition of the present invention, it is possible to obtain a polyimide film having excellent heat resistance, little change in hue after heat treatment, and a low yellowness, and the obtained polyimide film of the present invention has heat resistance. Excellent, little change in hue after heat treatment, and low yellowness. The suitable physical property values of the film are as follows.
The total light transmittance is preferably 84% or more, more preferably 87% or more, and further preferably 90% or more when the film has a thickness of 10 μm.
The yellow index (YI) is preferably 16 or less, more preferably 12 or less, and preferably 6 or less, more preferably 4 or less from the viewpoint of excellent colorlessness, when a film having a thickness of 10 μm is formed. be.
The 1% weight loss temperature is preferably 430 ° C. or higher, more preferably 480 ° C. or higher, still more preferably 500 ° C. or higher, and even more preferably 510 ° C. or higher. Here, the 1% weight loss temperature is the temperature at which the polyimide film is heated to 40 to 550 ° C. at a heating rate of 10 ° C./min and the weight is reduced by 1% as compared with the weight at 300 ° C. ..
The above-mentioned physical property values in the present invention can be specifically measured by the method described in Examples.

The polyimide film of the present invention is suitably used as a film for various members such as color filters, flexible displays, semiconductor parts, and optical members. The polyimide film of the present invention is particularly preferably used as a substrate for an image display device such as a liquid crystal display or an OLED display.

Hereinafter, the present invention will be specifically described with reference to Examples. However, the present invention is not limited to these examples.
The physical characteristics of the films obtained in Examples and Comparative Examples were measured by the methods shown below.

(1) Film thickness The film thickness was measured using a micrometer manufactured by Mitutoyo Co., Ltd.
The film thicknesses of Examples 9 to 10 and Comparative Examples 8 to 9 were measured using a film thickness measuring device Filmtrics F20 (manufactured by Filmometrics Co., Ltd.).

(2) Total light transmittance, yellow index (YI)
Total light transmittance conforms to JIS K7105: 1981, YI conforms to ASTM D1925 (C light source, 2 °), and is measured using a color and turbidity simultaneous measuring instrument "COH7700" manufactured by Nippon Denshoku Industries Co., Ltd. did.

(3) 1% weight loss temperature (Td1%)
A differential thermogravimetric simultaneous measuring device "NEXTA STA200RV" manufactured by Hitachi High-Tech Science Corporation was used. The temperature of the sample was raised to 40 to 150 ° C. at a heating rate of 10 ° C./min, held at 150 ° C. for 30 minutes, and after removing water, the temperature was raised to 550 ° C. The temperature at which the weight was reduced by 1% as compared with the weight after holding at 150 ° C. for 30 minutes was defined as the 1% weight loss temperature. The larger the value, the better the weight reduction temperature.

(4) Evaluation of laminated film A laminated film was manufactured, heat-treated, and the hue change after the heat treatment was visually evaluated, imitating the manufacturing process of a display for an image display device. The laminated film was prepared as follows.
The polyimide films obtained in Examples and Comparative Examples were not peeled off, a SiO 2 film having a thickness of 300 nm was formed on the polyimide film by sputtering, and an ITO (indium tin oxide) film having a thickness of 1230 nm was formed on the SiO ₂ film. , Annie ring (heating) was performed for 1 hour. The annealing (heating) temperature was 360 ° C. for Examples 1 to 8 and Comparative Examples 1 to 7, and 400 ° C. for Examples 9 to 10 and Comparative Examples 8 to 9.
The presence or absence of yellowing (increase in yellowish color density) of the laminated film before and after annealing was visually evaluated according to the following criteria.
No (no yellowing): No yellowing is seen in the laminated film before and after annealing (no change in hue)
Yes (with yellowing): Yellowing is seen in the laminated film before and after annealing (with hue change)
If there is no yellowing (no yellowing), there is little change in hue after heat treatment, which is good.

The tetracarboxylic acid component and diamine component used in Examples and Comparative Examples, and their abbreviations and the like are as follows.
<Tetracarboxylic acid component>
CpODA: Norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic dianhydride (represented by formula (a1)) Compounds to be used)
s-BPDA: 3,3', 4,4'-biphenyltetracarboxylic dianhydride (manufactured by Mitsubishi Chemical Corporation, compound represented by formula (a2s))
BPAF: 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride (manufactured by JFE Chemical Co., Ltd .; compound represented by formula (a3))
<Diamine component>
TFMB: 2,2'-bis (trifluoromethyl) benzidine (compound represented by the formula (b121))
3,5-DABA: 3,5-diaminobenzoic acid (compound represented by the formula (b21))
4-BAAB: 4-Aminophenyl-4-aminobenzoate (manufactured by Nippon Pure Chemical Industries, Ltd .; compound represented by formula (b3))
<Phosphorus compound>
JP-513: Isotridecyl acid phosphate (manufactured by Johoku Chemical Industry Co., Ltd., in formula (3), R ³ is an isotridecyl group and n is 1, and R ³ is an isotridecyl group and n is. 1: 1 mixture of compounds that are 2)
DBP: Dibutyl phosphate (manufactured by Johoku Chemical Industry Co., Ltd., a compound in which R ³ is a butyl group and n is 2 in formula (3)).
Phosphoric acid: A compound in which n is 0 in the formula (3) trimethyl phosphate: A compound in which R ³ is a methyl group and n is 3 in the formula (3) Triphenylphosphine: R in the formula (3) Compounds in which ³ is a phenyl group and n is 3 <Other compounds>
Ilganox 1010 (antioxidant): Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan Ltd.)
<Surface conditioner>
BYK-378: Silicone-based surface conditioner (manufactured by Big Chemie Japan Co., Ltd.)

The abbreviations of the solvent and the catalyst used in the examples and comparative examples are as follows.
NMP: N-methyl-2-pyrrolidone (manufactured by Tokyo Junyaku Kogyo Co., Ltd.)
GBL: γ-Butyrolactone (manufactured by Mitsubishi Chemical Corporation)
TEA: Triethylamine (manufactured by Kanto Chemical Co., Inc.)

<Example 1>
32.024g (0.100mol) of TFMB in a 1L 5-necked round-bottom flask equipped with a stainless half-moon stirring blade, a nitrogen inlet tube, a Dean Stark with a cooling tube, a thermometer, and a glass end cap. And NMP was added in an amount of 196.627 g, and the mixture was stirred at a system temperature of 50 ° C. and a nitrogen atmosphere at a rotation speed of 150 rpm to obtain a solution.
29.422 g (0.100 mol) of s-BPDA and 49.157 g of NMP were collectively added to this solution, and the mixture was stirred with a mantle heater at 50 ° C. for 7 hours.
Then, 307.230 g of NMP was added, and the mixture was further stirred for about 3 hours to homogenize to obtain a polyamic acid varnish having a solid content concentration of 10.0% by mass.

To 100 g of the obtained varnish, 0.01 g of JP-513 (1000 ppm with respect to polyamic acid) and 0.01 g of BYK-378 (1000 ppm with respect to polyamic acid) were added and stirred for 30 minutes to homogenize the composition. I got a varnish.
Subsequently, the obtained polyamic acid composition varnish was applied onto a glass plate by spin coating, held at 80 ° C. for 20 minutes on a hot plate, and then transferred to a hot air dryer at a heating rate of 5 ° C. under a nitrogen atmosphere. The temperature was raised to 420 ° C. at / min and heated in a hot air dryer at 420 ° C. for 60 minutes in a nitrogen atmosphere to evaporate the solvent and thermally imidize it to obtain a polyimide film. The results are shown in Table 1.

<Examples 2 to 3 and Comparative Examples 2 to 4>
Example 1 except that 0.01 g (1000 ppm with respect to polyamic acid) of each of the phosphorus compounds or other compounds shown in Table 1 was used instead of 0.01 g (1000 ppm with respect to polyamic acid) of JP-513. A polyimide film was obtained by the same method as in the above. The results are shown in Table 1.

<Comparative Example 1>
A polyimide film was obtained by the same method as in Example 1 except that JP-513 was not used. The results are shown in Table 1.

<Example 4>
26.644 g (0.083 mol) of TFMB in a 1 L 5-necked round-bottom flask equipped with a stainless half-moon agitator, a nitrogen inlet tube, a Dean Stark with a cooling tube, a thermometer, and a glass end cap. , 3,5-DABA (3.165 g (0.021 mol)) and GBL (163.792 g) were added, and the mixture was stirred at a system temperature of 70 ° C. and a nitrogen atmosphere at a rotation speed of 150 rpm to obtain a solution.
To this solution, 38.438 g (0.100 mol) of CpODA and 40.948 g of GBL were added in a batch, then 0.506 g of TEA as an imidization catalyst and triethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0. .056 g was added and heated with a mantle heater, and the temperature inside the reaction system was raised to 190 ° C. over about 20 minutes. The components to be distilled off were collected, and the temperature inside the reaction system was maintained at 190 ° C. and refluxed for 3 hours while adjusting the rotation speed according to the increase in viscosity.
Then, GBL was added so that the solid content concentration became 10% by mass, the temperature in the reaction system was cooled to 120 ° C., and then the mixture was further stirred for about 1 hour to homogenize to obtain a polyimide varnish.

To 100 g of the obtained varnish, 0.01 g of JP-513 (1000 ppm with respect to polyimide) and 0.01 g of BYK-378 (1000 ppm with respect to polyimide) were added and stirred for 30 minutes to homogenize the polyimide composition varnish. Obtained.
Subsequently, the obtained polyimide composition varnish was applied onto a glass plate by spin coating, held at 80 ° C. for 20 minutes on a hot plate, and then transferred to a hot air dryer to raise the temperature at 5 ° C./ The temperature was raised to 420 ° C. in min, and the mixture was heated in a hot air dryer at 420 ° C. for 60 minutes under a nitrogen atmosphere to evaporate the solvent to obtain a polyimide film. The results are shown in Table 1.

<Examples 5 and 6>
The same method as in Example 4 except that 0.01 g (1000 ppm with respect to polyamic acid) of each of the phosphorus compounds shown in Table 1 was used instead of 0.01 g (1000 ppm with respect to polyamic acid) of JP-513. To obtain a polyimide film. The results are shown in Table 1.

<Comparative Example 5>
A polyimide film was obtained by the same method as in Example 4 except that JP-513 was not used. The results are shown in Table 1.

<Example 7>
25.619 g (0.080 mol) of TFMB in a 1 L 5-necked round-bottom flask equipped with a stainless half-moon agitator, a nitrogen inlet tube, a Dean Stark with a cooling tube, a thermometer, and a glass end cap. , 3,5-DABA (3.043 g (0.020 mol)) and GBL (156.713 g) were added, and the mixture was stirred at a system temperature of 70 ° C. and a nitrogen atmosphere at a rotation speed of 150 rpm to obtain a solution.
To this solution, 30.750 g (0.080 mol) of CpODA, 5.884 g (0.020 mol) of s-BPDA and 39.178 g of GBL were added in a batch, and then TEA was 0 as an imidization catalyst. .506 g and 0.056 g of triethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and heated with a mantle heater to raise the temperature inside the reaction system to 190 ° C. over about 20 minutes. The components to be distilled off were collected, and the temperature inside the reaction system was maintained at 190 ° C. and refluxed for 2 hours while adjusting the rotation speed according to the increase in viscosity.
Then, GBL was added so that the solid content concentration became 10% by mass, the temperature in the reaction system was cooled to 120 ° C., and then the mixture was further stirred for about 1 hour to homogenize to obtain a polyimide varnish having a solid content concentration of 10% by mass. rice field.

To 100 g of the obtained varnish, 0.01 g of JP-513 (1000 ppm with respect to polyimide) and 0.01 g of BYK-378 (1000 ppm with respect to polyimide) were added and stirred for 30 minutes to homogenize the polyimide composition varnish. Obtained.
Subsequently, the obtained polyimide composition varnish was applied onto a glass plate by spin coating, held at 80 ° C. for 20 minutes on a hot plate, and then transferred to a hot air dryer to raise the temperature at 5 ° C./ The temperature was raised to 420 ° C. in min, and the mixture was heated in a hot air dryer at 420 ° C. for 60 minutes under a nitrogen atmosphere to evaporate the solvent to obtain a polyimide film. The results are shown in Table 1.

<Comparative Example 6>
A polyimide film was obtained by the same method as in Example 7 except that JP-513 was not used. The results are shown in Table 1.

<Example 8>
32.024g (0.100mol) of TFMB in a 1L 5-necked round-bottom flask equipped with a stainless half-moon stirring blade, a nitrogen inlet tube, a Dean Stark with a cooling tube, a thermometer, and a glass end cap. And 169.109 g of NMP were added, and the mixture was stirred at a system temperature of 70 ° C. and a nitrogen atmosphere at a rotation speed of 150 rpm to obtain a solution.
After adding 38.438 g (0.100 mol) of CpODA and 42.277 g of NMP to this solution in a batch, 0.506 g of TEA as an imidization catalyst and triethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0. .056 g was added and heated with a mantle heater, and the temperature inside the reaction system was raised to 190 ° C. over about 20 minutes. The components to be distilled off were collected, and the temperature inside the reaction system was maintained at 190 ° C. and refluxed for 2 hours while adjusting the rotation speed according to the increase in viscosity.
Then, NMP was added so that the solid content concentration became 10% by mass, the temperature in the reaction system was cooled to 120 ° C., and then the mixture was further stirred for about 1 hour to homogenize to obtain a polyimide varnish.

To 100 g of the obtained varnish, 0.01 g of JP-513 (1000 ppm with respect to polyimide) and 0.01 g of BYK-378 (1000 ppm with respect to polyimide) were added and stirred for 30 minutes to homogenize the polyimide composition varnish. Obtained.
Subsequently, the obtained polyimide composition varnish was applied onto a glass plate by spin coating, held at 80 ° C. for 20 minutes on a hot plate, and then transferred to a hot air dryer to raise the temperature at 5 ° C./ The temperature was raised to 420 ° C. in min, and the mixture was heated in a hot air dryer at 420 ° C. for 60 minutes under a nitrogen atmosphere to evaporate the solvent to obtain a polyimide film. The results are shown in Table 1.

<Comparative Example 7>
A polyimide film was obtained by the same method as in Example 8 except that JP-513 was not used. The results are shown in Table 1.

<Example 9>
TFMB 12.810 g (0.040 mol) in a 500 mL five-necked round-bottom flask equipped with a stainless half-moon stirring blade, a nitrogen inlet tube, a Dean Stark with a cooling tube, a thermometer, and a glass end cap. And 44.603 g of NMP was added, and the mixture was stirred at a system temperature of 70 ° C. and a nitrogen atmosphere at a rotation speed of 200 rpm to obtain a solution.
To this solution, 11.531 g (0.030 mol) of CpODA and 11.151 g of NMP were added in a batch, then 0.152 g of TEA was added as an imidization catalyst, and the mixture was heated by a mantle heater over about 20 minutes. The temperature inside the reaction system was raised to 190 ° C. The components to be distilled off were collected, and the temperature inside the reaction system was maintained at 190 ° C. and refluxed for 1 hour while adjusting the rotation speed according to the increase in viscosity. Then, 92.605 g of NMP was added to cool the temperature inside the reaction system to 50 ° C. to obtain a solution containing an oligomer having an imide repeating structural unit.
To the obtained solution, 20.595 g (0.070 mol) of s-BPDA, 13.695 g (0.060 mol) of 4-BAAB and 16.199 g of NMP were collectively added, and the mixture was stirred at 50 ° C. for 5 hours. .. Then, by adding NMP so that the solid content concentration becomes about 15% by mass and homogenizing it, a varnish containing a copolymer having an imide repeating structural unit and an amic acid structural unit (imide-amide acid copolymer). Alligator) was obtained.

To 100 g of the obtained varnish, 0.015 g of JP-513 (1000 ppm with respect to the imide-amide acid copolymer) and 0.015 g of BYK-378 (1000 ppm with respect to the imide-amide acid copolymer) were added 30 Stirring for 1 minute was homogenized to obtain an imide-amidoic acid copolymer composition varnish.
Subsequently, the obtained imide-amidoic acid copolymer composition varnish was applied onto a glass plate by spin coating, held at 80 ° C. for 20 minutes on a hot plate, and then transferred to a hot air dryer under a nitrogen atmosphere. The temperature was raised to 420 ° C. at a heating rate of 5 ° C./min, and the mixture was heated in a hot air dryer at 420 ° C. for 60 minutes in a nitrogen atmosphere to evaporate the solvent and thermally imidize it to obtain a polyimide film. The results are shown in Table 1.

<Comparative Example 8>
A polyimide film was obtained by the same method as in Example 9 except that JP-513 was not used. The results are shown in Table 1.
Since the polyimide film obtained in Comparative Example 8 could not be peeled off from the glass plate, the total light transmittance and the yellow index (YI) of Example 9 and Comparative Example 8 were measured including the glass plate. Further, for the polyimide film obtained in Comparative Example 8, the 1% weight loss temperature (Td1%) was not measured.

<Example 10>
TFMB 9.607 g (0.030 mol) in a 500 mL five-necked round-bottom flask equipped with a stainless half-moon stirring blade, a nitrogen inlet tube, a Dean Stark with a cooling tube, a thermometer, and a glass end cap. And 46.380 g of NMP were added, and the mixture was stirred at a system temperature of 70 ° C. and a nitrogen atmosphere at a rotation speed of 200 rpm to obtain a solution.
After adding 9.169 g (0.020 mol) of BPAF and 11.595 g of NMP to this solution in a batch, 0.152 g of TEA as an imidization catalyst was added, and the mixture was heated by a mantle heater over about 20 minutes. The temperature inside the reaction system was raised to 190 ° C. The components to be distilled off were collected, and the temperature inside the reaction system was maintained at 190 ° C. and refluxed for 1 hour while adjusting the rotation speed according to the increase in viscosity. Then, 95.849 g of NMP was added to cool the temperature inside the reaction system to 50 ° C. to obtain a solution containing an oligomer having an imide repeating structural unit.
To the obtained solution, 23.538 g (0.080 mol) of s-BPDA, 15.978 g (0.070 mol) of 4-BAAB and 16.858 g of NMP were added in a batch, and the mixture was stirred at 50 ° C. for 5 hours. .. Then, by adding NMP so that the solid content concentration becomes about 15% by mass and homogenizing it, a varnish containing a copolymer having an imide repeating structural unit and an amic acid structural unit (imide-amide acid copolymer). Alligator) was obtained.

To 100 g of the obtained varnish, 0.015 g of JP-513 (1000 ppm with respect to the imide-amide acid copolymer) and 0.015 g of BYK-378 (1000 ppm with respect to the imide-amide acid copolymer) were added 30 Stirring for 1 minute was homogenized to obtain an imide-amidoic acid copolymer composition varnish.
Subsequently, the obtained imide-amidoic acid copolymer composition varnish was applied onto a glass plate by spin coating, held at 80 ° C. for 20 minutes on a hot plate, and then transferred to a hot air dryer under a nitrogen atmosphere. The temperature was raised to 430 ° C. at a heating rate of 5 ° C./min, and the mixture was heated in a hot air dryer at 430 ° C. for 60 minutes in a nitrogen atmosphere to evaporate the solvent and thermally imidize it to obtain a polyimide film. The results are shown in Table 1.

<Comparative Example 9>
A polyimide film was obtained by the same method as in Example 10 except that JP-513 was not used. The results are shown in Table 1.
Since the polyimide film obtained in Comparative Example 9 could not be peeled off from the glass plate, the total light transmittance and the yellow index (YI) of Examples 10 and 9 were measured including the glass plate. Further, for the polyimide film obtained in Comparative Example 9, the 1% weight loss temperature (Td1%) was not measured.

As shown in Table 1, it can be seen that the polyimide film obtained from the polymer composition of the present invention is excellent in heat resistance and colorlessness after heat treatment, and has a low yellowness. Further, it can be seen that the polyimide film of the example is also excellent in transparency as compared with the polyimide film of the corresponding comparative example.

Claims (10)

A polymer (X) containing at least one selected from the group consisting of the repeating unit represented by the following general formula (1) and the repeating unit represented by the following general formula (2).
A polymer composition containing the compound (Y) represented by the following general formula (3).

(In formula (1), X ¹ is a tetravalent group having an alicyclic structure or an aromatic ring, and X is a group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-. At least one chosen.
In formula (2), X ² is a tetravalent group having an alicyclic structure or an aromatic ring, and R ¹ and R ² are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 3 to 3 carbon atoms, respectively. It is an alkylsilyl group of 9, and X is at least one selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-.
In the formula (3), R ³ is at least one selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, a phenyl group, an alkoxy group, an acryloyl group, a methacryloyl group, an acryloyloxyethyl group, and a methacryloyloxyethyl group. And n is 0 to 2. ) Claimed that the polymer (X) contains at least one selected from the group consisting of a repeating unit represented by the following general formula (1-2) and a repeating unit represented by the following general formula (2-2). The polymer composition according to 1.

(In formula (1-2), X ¹ is a tetravalent group having an alicyclic structure or an aromatic ring, and X is composed of a single bond, -NHCO-, -CONH-, -COO- and -OCO-. At least one selected from the group. In formula (2-2), X ² is a tetravalent group having an alicyclic structure or an aromatic ring, and R ¹ and R ² are independently hydrogen and carbon atoms, respectively. It is an alkyl group of 1 to 6 or an alkylsilyl group having 3 to 9 carbon atoms, and X is at least one selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-. be.) The polymer composition according to claim 1, wherein X in the formula (1) and the formula (2) is a single bond. The polymer (X) is at least one selected from the group consisting of a repeating unit represented by the following general formula (1-2-1) and a repeating unit represented by the following general formula (2-2-1). The polymer composition according to any one of claims 1 to 3, which comprises.

(In the formula (1-2-1), X ¹ is a tetravalent group having an alicyclic structure or an aromatic ring. In the formula (2-2-1), X ² is an alicyclic structure or an aromatic ring. R ¹ and R ² are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms, respectively.) The polymer composition according to any one of claims 1 to 4, wherein the repeating unit represented by the formula (1) is 10 mol% or more with respect to all the repeating units of the polymer (X). .. The polymer composition according to any one of claims 1 to 5, wherein the repeating unit represented by the formula (2) is 10 mol% or more with respect to all the repeating units of the polymer (X). .. The polymer composition according to any one of claims 1 to 6, wherein the content of the compound (Y) is 10 ppm or more and 10,000 ppm or less with respect to the polymer (X). A varnish in which the polymer composition according to any one of claims 1 to 7 is dissolved in an organic solvent. A polyimide film obtained by applying the varnish according to claim 8 onto a support and heating it. A method for producing a polyimide film, wherein the varnish according to claim 8 is applied onto a support and heated.