JP6941412B2 - Polyimide with fluorene skeleton - Google Patents

Description

The present invention relates to a polyimide having a fluorene skeleton, and polyamic acids, amines, and nitro compounds for producing the polyimide.

Polyimide has excellent mechanical properties, electrical properties, heat resistance, and chemical resistance, and is widely used as a flexible printed wiring board, interlayer insulating film, protective film, etc. in the field of electrical and electronic materials, especially electronic materials for semiconductors. Has been done.

As described above, among the polyimides used for various purposes, for example, the following formula (5):

で表されるアミン（２，７−ジアミノフルオレン）から製造されるフルオレン骨格を有するポリイミドは、高耐熱性等の特徴を有することから、電子基板材料、層間絶縁膜及びフレキシブルプリント基板（ＦＰＣ）等の基板材料、ポリイミド接着剤等、広範な用途に使用されている（例えば特許文献１）。

A polyimide having a fluorene skeleton produced from an amine (2,7-diaminofluorene) represented by (2,7-diaminofluorene) has characteristics such as high heat resistance. It is used in a wide range of applications such as substrate materials and polyimide adhesives (for example, Patent Document 1).

Therefore, when the inventors of the present application produced the polyimide in order to confirm the characteristics of the polyimide produced from the amine represented by the above formula (5), it was found that the polyimide had a large birefringence. When a material having a large birefringence is used for a substrate for various displays such as a liquid crystal display and an organic EL display, a large amount of polyimide may occur, which may cause deterioration of display quality (for example, Patent Document 2). In applying the polyimide produced from the amine represented by the above formula (5), which can exhibit excellent heat resistance, it was necessary to further reduce birefringence.

Japanese Patent Publication "Japanese Patent Laid-Open No. 2006-213799" International Publication No. 2011/149018 Pamphlet

An object of the present invention is to provide a polyimide having a fluorene skeleton, which has lower birefringence than a conventionally known polyimide having a fluorene skeleton.

As a result of diligent research by the present inventors to solve the above problems, the polyimide produced from amines represented by the following general formula (1) has a lower birefringence than the polyimide having a conventionally known fluorene skeleton. I found that it was a refringence. Specifically, the following inventions are included.

（上記一般式（１）中、Ｒ_１及びＲ_２はそれぞれ独立して炭素数１〜１２のアルキル基、ハロゲン原子、ヒドロキシル基、炭素数４〜１２の置換基を有してもよいシクロアルキル基、又は炭素数６〜１２の置換基を有してもよい芳香族基を表し、ｍ及びｎは０〜４の整数を表す。なお、Ｒ_１及び／又はＲ_２が複数存在する場合、それぞれは同一でも異なっていてもよい。）
〔２〕下記一般式（１）：

（上記一般式（１）中、Ｒ_１及びＲ_２はそれぞれ独立して炭素数１〜１２のアルキル基、ハロゲン原子、ヒドロキシル基、炭素数４〜１２の置換基を有してもよいシクロアルキル基、又は炭素数６〜１２の置換基を有してもよい芳香族基を表し、ｍ及びｎは０〜４の整数を表す。なお、Ｒ_１及び／又はＲ_２が複数存在する場合、それぞれは同一でも異なっていてもよい。）
で表されるアミン類由来の構成単位、及び酸二無水物由来の構成単位を主鎖に含むポリアミック酸。
〔３〕下記一般式（１）で表されるアミン類。

（上記一般式（１）中、Ｒ_１及びＲ_２はそれぞれ独立して炭素数１〜１２のアルキル基、ハロゲン原子、ヒドロキシル基、炭素数４〜１２の置換基を有してもよいシクロアルキル基、又は炭素数６〜１２の置換基を有してもよい芳香族基を表し、ｍ及びｎは０〜４の整数を表す。なお、Ｒ_１及び／又はＲ_２が複数存在する場合、それぞれは同一でも異なっていてもよい。）
〔４〕下記一般式（２）：

（上記一般式（２）中、Ｒ_１及びＲ_２はそれぞれ独立して炭素数１〜１２のアルキル基、ハロゲン原子、ヒドロキシル基、炭素数４〜１２の置換基を有してもよいシクロアルキル基、又は炭素数６〜１２の置換基を有してもよい芳香族基を表し、ｍ及びｎは０〜４の整数を表す。なお、Ｒ_１及び／又はＲ_２が複数存在する場合、それぞれは同一でも異なっていてもよい。）
で表されるキサンテンニトロ化合物を還元する、下記一般式（１）：

（上記一般式（１）中、Ｒ_１及びＲ_２はそれぞれ独立して炭素数１〜１２のアルキル基、ハロゲン原子、ヒドロキシル基、炭素数４〜１２の置換基を有してもよいシクロアルキル基、又は炭素数６〜１２の置換基を有してもよい芳香族基を表し、ｍ及びｎは０〜４の整数を表す。なお、Ｒ_１及び／又はＲ_２が複数存在する場合、それぞれは同一でも異なっていてもよい。）
で表されるアミン類の製造方法。
〔５〕酸存在下、下記一般式（３）：

で表されるジニトロフルオレノン類と下記一般式（４）：

（上記一般式（４）中、Ｒ_３は炭素数１〜１２のアルキル基、ハロゲン原子、ヒドロキシル基、炭素数４〜１２の置換基を有してもよいシクロアルキル基、又は炭素数６〜１２の置換基を有してもよい芳香族基を表し、ｍ_２は０〜４の整数を表す。）
で表されるフェノール類とを反応させる、下記一般式（２）：

（上記一般式（２）中、Ｒ_１及びＲ_２はそれぞれ独立して炭素数１〜１２のアルキル基、ハロゲン原子、ヒドロキシル基、炭素数４〜１２の置換基を有してもよいシクロアルキル基、又は炭素数６〜１２の置換基を有してもよい芳香族基を表し、ｍ及びｎは０〜４の整数を表す。なお、Ｒ_１及び／又はＲ_２が複数存在する場合、それぞれは同一でも異なっていてもよい。）
で表されるキサンテンニトロ化合物の製造方法。
〔６〕下記一般式（２）で表されるキサンテンニトロ化合物。

（上記一般式（２）中、Ｒ_１及びＲ_２はそれぞれ独立して炭素数１〜１２のアルキル基、ハロゲン原子、ヒドロキシル基、炭素数４〜１２の置換基を有してもよいシクロアルキル基、又は炭素数６〜１２の置換基を有してもよい芳香族基を表し、ｍ及びｎは０〜４の整数を表す。なお、Ｒ_１及び／又はＲ_２が複数存在する場合、それぞれは同一でも異なっていてもよい。） [1] A polyimide having a constituent unit derived from amines represented by the following general formula (1) and a constituent unit derived from acid dianhydride in the main chain.

(In the above general formula (1), R ₁ and R ₂ may independently have an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxyl group, and a substituent having 4 to 12 carbon atoms, respectively. It represents a group or an aromatic group which may have a substituent having 6 to 12 carbon atoms, and m and n represent an integer of 0 to _{4. When a plurality of R 1} and / or R ₂ are present, Each may be the same or different.)
[2] The following general formula (1):

(In the above general formula (1), R ₁ and R ₂ may independently have an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxyl group, and a substituent having 4 to 12 carbon atoms, respectively. It represents a group or an aromatic group which may have a substituent having 6 to 12 carbon atoms, and m and n represent an integer of 0 to _{4. When a plurality of R 1} and / or R ₂ are present, Each may be the same or different.)
A polyamic acid having a constituent unit derived from amines represented by and a constituent unit derived from acid dianhydride in the main chain.
[3] Amines represented by the following general formula (1).

(In the above general formula (1), R ₁ and R ₂ may independently have an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxyl group, and a substituent having 4 to 12 carbon atoms, respectively. It represents a group or an aromatic group which may have a substituent having 6 to 12 carbon atoms, and m and n represent an integer of 0 to _{4. When a plurality of R 1} and / or R ₂ are present, Each may be the same or different.)
[4] The following general formula (2):

(In the above general formula (2), R ₁ and R ₂ may independently have an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxyl group, and a substituent having 4 to 12 carbon atoms, respectively. It represents a group or an aromatic group which may have a substituent having 6 to 12 carbon atoms, and m and n represent an integer of 0 to _{4. When a plurality of R 1} and / or R ₂ are present, Each may be the same or different.)
The following general formula (1): which reduces the xanthene nitro compound represented by

(In the above general formula (1), R ₁ and R ₂ may independently have an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxyl group, and a substituent having 4 to 12 carbon atoms, respectively. It represents a group or an aromatic group which may have a substituent having 6 to 12 carbon atoms, and m and n represent an integer of 0 to _{4. When a plurality of R 1} and / or R ₂ are present, Each may be the same or different.)
A method for producing amines represented by.
[5] In the presence of acid, the following general formula (3):

Dinitrofluorenones represented by and the following general formula (4):

(In the above general formula (4), R ₃ is an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxyl group, a cycloalkyl group which may have a substituent having 4 to 12 carbon atoms, or 6 to 6 carbon atoms. It represents an aromatic group which may have 12 substituents, and m ₂ represents an integer of 0-4.)
The following general formula (2): to react with phenols represented by

(In the above general formula (2), R ₁ and R ₂ may independently have an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxyl group, and a substituent having 4 to 12 carbon atoms, respectively. It represents a group or an aromatic group which may have a substituent having 6 to 12 carbon atoms, and m and n represent an integer of 0 to _{4. When a plurality of R 1} and / or R ₂ are present, Each may be the same or different.)
A method for producing a xanthene nitro compound represented by.
[6] A xanthene nitro compound represented by the following general formula (2).

(In the above general formula (2), R ₁ and R ₂ may independently have an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxyl group, and a substituent having 4 to 12 carbon atoms, respectively. It represents a group or an aromatic group which may have a substituent having 6 to 12 carbon atoms, and m and n represent an integer of 0 to _{4. When a plurality of R 1} and / or R ₂ are present, Each may be the same or different.)

According to the present invention, a polyimide having a fluorene skeleton and having a low birefringence despite being a polyimide produced from an amine having a structure similar to that of the amine represented by the above formula (5). It will be possible to provide. Furthermore, the total light transmittance and the degree of coloration (yellowness), which are one of the indexes indicating the transparency of the polyimide, are also reduced as compared with the polyimide produced from the amine represented by the above formula (5), and are also reduced. Since the heat resistance (glass transition temperature) is about the same as or higher than that of the polyimide produced from the amine represented by the above formula (5), the electronic substrate material, the interlayer insulating film, the flexible printed substrate (FPC), and the like can be used. Of course, it can be used as a substrate material, a polyimide adhesive, or the like, and in particular, it can be suitably used as a substrate material for various displays such as liquid crystal displays and organic EL displays.

Furthermore, polyimide having a specific repeating unit (repeating unit represented by the above general formula (P-1)) has excellent solvent solubility and a low coefficient of thermal expansion (linear thermal expansion coefficient) in addition to the above-mentioned characteristics. Is small). If the polyimide has excellent solvent solubility, when the polyamic acid is imidized into a polyimide, it can be carried out not only by the thermal imidization method but also by the chemical imidization method. The imidization method can be selected. Furthermore, it is also possible to obtain a polyimide molded product (film or the like) by a method that is easy to carry out industrially, such as a solvent casting method. Further, if the coefficient of linear thermal expansion is small, the dimensions are unlikely to change during the manufacture or use of a device using polyimide, and therefore, it is particularly suitable for devices that require a high degree of dimensional stability.

^{It is a 1} H-NMR spectrum of the xanthene nitro compound represented by the following formula (2-1) among the xanthene nitro compounds represented by the general formula (2) produced in Example 1. ^{It is a 1} H-NMR spectrum of the amine represented by the following formula (1-1) among the amines represented by the above general formula (1) produced in Example 2. ^{It is a 1} H-NMR spectrum of the xanthene nitro compound represented by the following formula (2-2) among the xanthene nitro compounds represented by the general formula (2) produced in Example 3. ^{It is a 1} H-NMR spectrum of the amine represented by the following formula (1-2) among the amines represented by the above general formula (1) produced in Example 4. ^{It is a 1} H-NMR spectrum of the xanthene nitro compound represented by the following formula (2-3) among the xanthene nitro compounds represented by the general formula (2) produced in Example 5. ^{It is a 1} H-NMR spectrum of the amine represented by the following formula (1-3) among the amines represented by the above general formula (1) produced in Example 6. It is a mass spectrum of the xanthene nitro compound represented by the following formula (2-1) among the xanthene nitro compounds represented by the general formula (2) produced in Example 1. It is a mass spectrum of the amine represented by the following formula (1-1) among the amines represented by the above general formula (1) produced in Example 2. It is a mass spectrum of the xanthene nitro compound represented by the following formula (2-2) among the xanthene nitro compounds represented by the general formula (2) produced in Example 3. It is a mass spectrum of the amine represented by the following formula (1-2) among the amines represented by the above general formula (1) produced in Example 4. It is a mass spectrum of the xanthene nitro compound represented by the following formula (2-3) among the xanthene nitro compounds represented by the general formula (2) produced in Example 5. It is a mass spectrum of the amine represented by the following formula (1-3) among the amines represented by the above general formula (1) produced in Example 6.

<Polyimide of the present invention>
Hereinafter, the present invention will be described together with the embodiments thereof. The polyimide of the present invention has the following general formula (1):

（上記一般式（１）中、Ｒ_１及びＲ_２はそれぞれ独立して炭素数１〜１２のアルキル基、ハロゲン原子、ヒドロキシル基、炭素数４〜１２の置換基を有してもよいシクロアルキル基、又は炭素数６〜１２の置換基を有してもよい芳香族基を表し、ｍ及びｎは０〜４の整数を表す。なお、Ｒ_１及び／又はＲ_２が複数存在する場合、それぞれは同一でも異なっていてもよい。）
で表されるアミン類由来の構成単位、及び酸二無水物由来の構成単位を主鎖に含むポリイミドである（以下、本発明のポリイミドと称することがある）。本発明のポリイミドは、耐熱性に優れ、かつ、複屈折が小さいとの特徴を有する。なお、本発明における複屈折とは、ポリイミドフィルムの面内屈折と面外屈折との差から求められる「厚み方向複屈折」のことを意味し、後述する実施例に記載する測定方法により得られた値を示す。

(In the above general formula (1), R ₁ and R ₂ may independently have an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxyl group, and a substituent having 4 to 12 carbon atoms, respectively. It represents a group or an aromatic group which may have a substituent having 6 to 12 carbon atoms, and m and n represent an integer of 0 to _{4. When a plurality of R 1} and / or R ₂ are present, Each may be the same or different.)
It is a polyimide containing a structural unit derived from amines represented by (2) and a structural unit derived from acid dianhydride in the main chain (hereinafter, may be referred to as the polyimide of the present invention). The polyimide of the present invention is characterized by having excellent heat resistance and small birefringence. The birefringence in the present invention means "birefringence in the thickness direction" obtained from the difference between the in-plane refraction and the out-of-plane refraction of the polyimide film, and can be obtained by the measurement method described in Examples described later. Indicates the value.

Further, the amines represented by the above general formula (1) constituting the polyimide of the present invention have the following general formula (6):

（上記一般式（６）中、Ｒ_１及びＲ_２はそれぞれ独立して炭素数１〜１２のアルキル基、ハロゲン原子、ヒドロキシル基、炭素数４〜１２の置換基を有してもよいシクロアルキル基、又は炭素数６〜１２の置換基を有してもよい芳香族基を表し、ｍ及びｎは０〜４の整数を表す。なお、Ｒ_１及び／又はＲ_２が複数存在する場合、それぞれは同一でも異なっていてもよい。）
で表されるアミン類であることが好ましい。

(In the above general formula (6), R ₁ and R ₂ may independently have an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxyl group, and a substituent having 4 to 12 carbon atoms, respectively. It represents a group or an aromatic group which may have a substituent having 6 to 12 carbon atoms, and m and n represent an integer of 0 to _{4. When a plurality of R 1} and / or R ₂ are present, Each may be the same or different.)
It is preferably amines represented by.

In the general formula (1) or (6), for example, the alkyl group having 1 to 12 carbon atoms in the substituents _{R 1} and _{R 2,} a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, Examples thereof include a linear or branched alkyl group such as an s-butyl group, a t-butyl group, a pentyl group, and a hexyl group, and a linear or branched alkyl group having 1 to 8 carbon atoms is preferable. A linear or branched alkyl group having 1 to 6 carbon atoms is more preferable, and a linear or branched alkyl group having 1 to 3 carbon atoms is more preferable. Examples of the cycloalkyl group which may have a substituent having 4 to 12 carbon atoms include a cyclopentyl group, a cyclohexyl group, an alkyl (for example, an alkyl having 1 to 4 carbon atoms) substituted cyclopentyl group, and an alkyl (for example, 1 to 4 carbon atoms). A cycloalkyl group or an alkyl-substituted cycloalkyl group represented by 4 to 12 carbon atoms (preferably 5 to 8 carbon atoms) such as an alkyl) substituted cyclohexyl group of 4 can be mentioned, preferably a cyclopentyl group or a cyclohexyl group. be. Examples of the aromatic group which may have a substituent having 6 to 12 carbon atoms include a phenyl group, an alkyl (for example, an alkyl having 1 to 4 carbon atoms) substituted phenyl group, and a naphthyl group, and phenyl is preferable. It is a group or an alkyl-substituted phenyl group (for example, a methylphenyl group, a dimethylphenyl group, an ethylphenyl group, etc.), and more preferably a phenyl group. Examples of the halogen atom include fluorine, chlorine, bromine and the like, and chlorine or bromine is preferable. Substituents R ₁ and R ₂ are independent of each other because the xanthene nitro compound described later, which is a raw material for amines represented by the above general formula (1) or (6) of the present invention, can be produced at low cost. It is preferably an alkyl group having 1 to 12 carbon atoms.

In the above general formula (1) or (6), _{m and n representing the number of substituents of R 1} and R ₂ are integers of 0 to 4, and are represented by the above general formula (1) or (6) of the present invention. Since the xanthene nitro compound described later, which is a raw material for amines, can be produced at low cost, it is preferably 1 or 2.

Hereinafter, specific examples of amines represented by the above general formula (1) will be listed, but the present invention is not limited thereto.

The amines represented by the above general formula (1) constituting the polyimide of the present invention may be used alone or in combination of two or more.

Among the polyimides of the present invention, the following general formula (P-1):

（上記一般式（Ｐ−１）中、Ｒ_１及びＲ_２並びにｍ及びｎは上述の通りである。Ｘ_１は４価の脂肪族基を表す。）
で表される繰り返し単位を有するポリイミドは、溶媒溶解性に優れると共に、線熱膨張係数が小さいといった特徴も兼ね備えることから好ましい。

(In the above general formula (P-1), R ₁ and R ₂ and m and n are as described above. X ₁ represents a tetravalent aliphatic group.)
Polyimide having a repeating unit represented by is preferable because it has excellent solvent solubility and also has a feature of a small coefficient of linear thermal expansion.

Further, among the polyimides of the present invention, the following general formula (P-2):

（上記一般式（Ｐ−２）中、Ｘ_１は上述の通りであり、Ｘ_２はフッ素原子を有する２価の芳香族基である。）
で表される繰り返し単位を有するポリイミドとすることにより、線熱膨張係数をより小さくすることが可能となる。本発明のポリイミドが上記一般式（Ｐ−２）で表される繰り返し単位を有する場合、該繰り返し単位の含有比率は、ポリイミドの全繰り返し単位に対し１〜６７％であり、好ましくは１〜５０％である。上記一般式（Ｐ−２）で表される繰り返し単位の含有比率を６７％より低くすることにより、より低複屈折を示すポリイミドを得ることが可能となる。なお、フッ素原子を有する２価の芳香族基とは、Ｘ_２中に少なくとも１つのフッ素原子があればよく、具体的に例えば、芳香環の水素原子の一部がフッ素原子に置換された構造、芳香環上の置換基であるアルキル基の水素原子の一部又は全部がフッ素原子に置換された構造等が挙げられる。

(In the above general formula (P-2), X ₁ is as described above, and X ₂ is a divalent aromatic group having a fluorine atom.)
By using a polyimide having a repeating unit represented by, the coefficient of linear thermal expansion can be made smaller. When the polyimide of the present invention has a repeating unit represented by the above general formula (P-2), the content ratio of the repeating unit is 1 to 67% with respect to all the repeating units of the polyimide, preferably 1 to 50. %. By lowering the content ratio of the repeating unit represented by the general formula (P-2) to less than 67%, it becomes possible to obtain a polyimide showing lower birefringence. The divalent aromatic group having a fluorine atom may have _{at least one fluorine atom in X 2.} Specifically, for example, a structure in which a part of the hydrogen atom of the aromatic ring is replaced with a fluorine atom. , A structure in which a part or all of the hydrogen atom of the alkyl group which is a substituent on the aromatic ring is substituted with a fluorine atom and the like can be mentioned.

Examples of the acid dianhydride constituting the polyimide of the present invention include pyromellitic anhydride, 4,4'-oxydiphthalic hydride, biphenyl-3,4,3', 4'-tetracarboxylic hydride, and benzophenone. -3,4,3', 4'-tetracarboxylic acid dianhydride, diphenylsulfone-3,4,3', 4'-tetracarboxylic acid dianhydride, 4,4'-(2,2-hexafluoro) Isopropylidene) diphthalic acid dianhydride, m-ta-phenyl-3,4,3', 4'-tetracarboxylic acid dianhydride, p-ta-phenyl-3,4,3', 4'-tetracarboxylic Aromatic tetracarboxylic acid such as acid dianhydride, or 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid Dianhydride, Bicyclo [2.2.2] Oct-7-en-2,3,5,6-tetracarboxylic acid dianhydride, 5- (dioxotetrahydrofuryl-3-methyl) -3-cyclohexene- 1,2-Dicarboxylic Acid Anhydride, 4- (2,5-dioxo tetrahydrofuran-3-yl) -Tetraline-1,2-dicarboxylic Acid Anhydride, tetrahydrofuran-2,3,4,5-Tetracarboxylic Acid Di Anhydride, bicyclohexyl-3,3', 4,4'-tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic hydride, 1,2,3,4-cyclobutanetetra Caroic acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,4-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, etc. The aliphatic tetracarboxylic dianhydride of the above is exemplified. These acid dianhydrides may be used alone or in combination of two or more, if necessary. Incidentally, tetravalent aliphatic group represented by X ₁ in the above general formula (P-1) and (P-2) is derived from an aliphatic group constituting the aliphatic tetracarboxylic dianhydride.

Among the above acid dianhydrides, benzophenone-3,4,3', 4'-tetracarboxylic dianhydride, 4,4'-oxydiphthalic acid dianhydride and Cyclobutane-1,2,3,4-tetracarboxylic dianhydride is preferred. When the obtained polyimide requires solvent solubility, low linear thermal expansion and / or transparency, an aliphatic tetracarboxylic acid dianhydride is preferable, and 1,2,3,4-cyclobutanetetracarboxylic acid is particularly preferable. Dianhydrides (1,2,3,4-cyclobutanetetracarboxylic acid 1,2: 3,4-dianhydride) are preferred.

Further, if necessary, the main chain contains structural units derived from amines other than the amines represented by the above general formula (1), such as other aromatic amines, aliphatic amines, and alicyclic amines. You may be. Examples of amines that can be used in combination include 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, and 3,4'-diamino. Diphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diamino Biphenyl, 3,7-diamino-dimethyldibenzothiophene-5,5-dioxide, 4,4-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-bis (4-aminophenyl) sulfide, 4,4 '-Diaminodiphenylsulfone, 4,4'-diaminobenzanilide, 1,3-bis (4-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,5-bis (4-amino) Phenoxy) pentane, 1,3-bis (4-aminophenoxy) -2,2-dimethylpropane, 1,2-bis [2- (4-aminophenoxy) ethoxy] ethane, 9,9-bis (4-amino) Phenyl) fluorene, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine, 1,4-bis (4-aminophenoxy) benzene, 1, 3-Bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) Biphenyl, 2,2-bis (4-aminophenoxyphenyl) propane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [ 4- (4-Aminophenoxy) phenyl] hexafluoropropane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 4,6-dihydroxy-1,3-phenylenediamine, 3,3'-dihydroxy- 4,4'-Diaminobiphenyl, 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 3,3', 4,4'-tetraaminobiphenyl, 1,6-diaminohexane, 1 , 3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 4,4'-methylenebis ( Cyclohexylamine), 1,4-diaminocyclohexane, 2,5-bicyclo [2.2.1] heptambis (methylamine), tricyclo [3.3.1.13.7] decane-1,3-diamine, 4 −Aminobenzoic acid-4-aminophenyl, 2- (4-aminophenyl) -5-aminobenzoxazole, 9,9-bis [4- (4-aminophenoxy) phenyl] fluorene, 2,2'-bis ( 3-sulfopropoxy) -4,4'-diaminobiphenyl, 4,4'-bis (4-aminophenoxy) biphenyl-3,3'-disulfonic acid, 1,4-diamino-2-fluorobenzene, 1,4 -Diamino-2,3-difluorobenzene, 1,4-diamino-2,5-difluorobenzene, 1,4-diamino-2,6-difluorobenzene, 1,4-diamino-2,3,5-trifluoro Benzidine, 1,4-diamino-2,3,5,6-tetrafluorobenzene, 1,4-diamino-2- (trifluoromethyl) benzene, 1,4-diamino-2,3-bis (trifluoromethyl) ) Benzidine, 1,4-diamino-2,5-bis (trifluoromethyl) benzene, 1,4-diamino-2,6-bis (trifluoromethyl) benzene, 1,4-diamino-2,3,5 -Tris (trifluoromethyl) benzene, 1,4-diamino-2,3,5,6-tetrakis (trifluoromethyl) benzene, 2-fluorobenzidine, 3-fluorobenzidine, 2,3-difluorobenzidine, 2, 5-difluorobenzidine, 2,6-difluorobenzidine, 2,3,5-trifluorobenzidine, 2,3,6-trifluorobenzidine, 2,3,5,6-tetrafluorobenzidine, 2,2'-difluoro Benzidine, 3,3'-difluorobenzidine, 2,3'-difluorobenzidine, 2,2', 3-trifluorobenzidine, 2,3,3'-trifluorobenzidine, 2,2', 5-trifluorobenzidine , 2,2', 6-trifluorobenzidine, 2,3', 5-trifluorobenzidine, 2,3', 6,-trifluorobenzidine, 2,2', 3,3'-tetrafluorobenzidine, 2 , 2', 5,5'-tetrafluorobenzidine, 2,2', 6,6'-tetrafluorobenzidine, 2,2', 3,3', 6,6'-hexafluorobenzidine, 2,2' , 3,3', 5,5', 6,6'-octafluorobenzidine, 2- Refluoromethyl) benzidine, 3- (trifluoromethyl) benzidine, 2,3-bis (trifluoromethyl) benzidine, 2,5-bis (trifluoromethyl) benzidine, 2,6-bis (trifluoromethyl) benzidine , 2,3,5-tris (trifluoromethyl) benzidine, 2,3,6-tris (trifluoromethyl) benzidine, 2,3,5,6-tetrakis (trifluoromethyl) benzidine, 2,3'- Bis (trifluoromethyl) benzidine, 2,2', 3-bis (trifluoromethyl) benzidine, 2,3,3'-tris (trifluoromethyl) benzidine, 2,2', 5-tris (trifluoromethyl) ) Benzidine, 2,2', 6-tris (trifluoromethyl) benzidine, 2,3', 5-tris (trifluoromethyl) benzidine, 2,3', 6-tris (trifluoromethyl) benzidine, 2, 2', 3,3'-tetrakis (trifluoromethyl) benzidine, 2,2', 5,5'-tetrakis (trifluoromethyl) benzidine, 2,2', 6,6'-tetrakis (trifluoromethyl) Examples thereof include benzidine, and these amines can be used alone, and if necessary, two or more thereof can be used in combination.

Among the above-mentioned amines that can be used in combination, it is preferable to use aromatic diamines having a fluorine atom in combination because the coefficient of linear thermal expansion of the polyimide of the present invention can be reduced. Further, among aromatic diamines having a fluorine atom, in particular, by using an aromatic diamine having a trifluoromethyl group in combination, it is possible to further improve the solvent solubility of polyimide, and a trifluoromethyl group can be used. Among the aromatic diamines contained, 2,2'-bis (trifluoromethyl) benzidine is particularly preferable from the viewpoint of availability. Incidentally, the divalent aromatic group having a fluorine atom represented by X ₂ in the above general formula (P-2) is derived from an aromatic group constituting the aromatic diamines having fluorine atoms.

The polyimide of the present invention may further contain other structural units that can be contained in the polyimide (for example, a structural unit derived from a compound having an amide group or an ester group).

<Physical characteristics of the polyimide of the present invention>
(1) Weight Average Molecular Weight The weight average molecular weight of the polyimide of the present invention is preferably in the range of 5,000 to 500,000 and preferably in the range of 10,000 to 300,000, although it depends on the intended use. Is more preferable, and the range is further preferably in the range of 30,000 to 200,000. When the weight average molecular weight is 5,000 or more, sufficient strength can be obtained when polyimide is used as a coating film or a film. On the other hand, when the weight average molecular weight is 500,000 or less, the increase in viscosity is small and good solubility can be maintained, so that a coating film or film having a smooth surface and a uniform film thickness can be obtained. can. The molecular weight in the present invention refers to a polystyrene-equivalent value obtained by gel permeation chromatography (GPC) analyzed under the conditions described below.

(2) Glass Transition Temperature The polyimide of the present invention preferably has a glass transition temperature of 300 ° C. or higher, more preferably 320 ° C. or higher. The method for measuring the glass transition temperature will be described in detail in the section of Examples. The upper limit of the glass transition temperature is not particularly limited, but may be 500 ° C. or lower.

(3) Birefringence The polyimide of the present invention preferably has a birefringence of 0.04 or less, more preferably 0.02 or less. In general, although a polyimide having a small coefficient of linear thermal expansion tends to have a large double refraction, among the polyimides of the present invention, a polyimide having a repeating unit represented by the general formula (P-1) is a double. The polyimide has the characteristics of having a small coefficient of linear thermal expansion as well as the characteristics of having a small coefficient of linear thermal expansion. The method for measuring birefringence will be described in detail in the section of Examples.

(4) Total light transmittance The polyimide of the present invention tends to have an improved total light transmittance as compared with the polyimide produced from the amine represented by the above formula (5). In particular, among the polyimides of the present invention, the polyimide having a repeating unit represented by the above general formula (P-1) can have a total light transmittance of 80% or more when the film thickness is 5 to 30 μm. .. The upper limit of the total light transmittance is theoretically 100%, and is not particularly limited. Further, the "film thickness" in the present invention means the film thickness of the film when the polyimide of the present invention is formed into a film, and can be measured using, for example, a contact type film thickness meter. The method for measuring the total light transmittance will be described in detail in the section of Examples.

(5) Yellowness (Yellowness Index, YI)
The polyimide of the present invention tends to have a lower yellowness than the polyimide produced from the amine represented by the above formula (5), but among the polyimides of the present invention, it is represented by the above general formula (P-1). The polyimide having the repeating unit can have a yellowness of 10 or less when the film thickness is 5 to 30 μm. The method for measuring yellowness will be described in detail in the section of Examples.

(6) Linear thermal expansion coefficient When the length (L) of the sample changes from L _{1 to L 2 by changing the temperature (T) of the sample from T 1} to T ₂ (T ₁ <T ₂ ), the length The ratio of the amount of change (ΔL = L _2- L ₁ ) to the length (L ₀ ) of the sample at room temperature (T ₀ ) is called thermal expansion between _{temperatures T 1} and T _2. The value obtained by dividing the thermal expansion in a temperature difference ΔT = T ₂ -T _1, called the average linear thermal expansion coefficient between the temperatures T ₁ and T ₂ (alpha), represented by the following formula (It should be noted that the present In the present invention, the coefficient of linear thermal expansion (hereinafter, also referred to as "CTE") means the average coefficient of linear thermal expansion (α) unless otherwise specified).
α = (ΔL / L ₀ ) / ΔT

Among the polyimides of the present invention, the polyimide having a repeating unit represented by the above general formula (P-1) has a CTE of 25 ppm / K or less when the temperature of the polyimide is changed from 100 ° C. to 200 ° C. be able to. Since CTE may show a negative value, CTE of 25 ppm / K or less means that the absolute value of CTE is 25 ppm / K or less. The specific measurement method of CTE will be described in detail in the section of Examples.

<Polyamic acid of the present invention>
The polyamic acid of the present invention is a polyamic acid containing a constituent unit derived from amines represented by the above general formula (1) and a constituent unit derived from acid dianhydride in the main chain. The specific embodiments of the amines represented by the general formula (1) and the specific embodiments derived from the acid dianhydride are the same as those of the polyimide of the present invention described above. Further, as with the polyimide of the present invention, other structural units that can be contained in the polyimide (for example, structural units derived from compounds having an amide group or an ester group) may be contained, if necessary.

The molecular weight of the polyamic acid of the present invention depends on its use, but its weight average molecular weight is preferably 10,000 to 500,000, more preferably 10,000 to 300,000, and 20,000 to 200,000. Is even more preferable. If the molecular weight of the polyamic acid is 10,000 or more, it can be molded and it is easy to maintain good mechanical properties. Further, when the molecular weight of the polyamic acid is 200,000 or less, it is easy to control the molecular weight at the time of synthesis, and it is easy to obtain a solution having an appropriate viscosity and it is easy to handle in many cases. The molecular weight of the polyamic acid can be based on the viscosity of the polyamic acid solution.

<Amines of the present invention>
The amines of the present invention are amines represented by the above general formula (1). The specific embodiment of the amines represented by the general formula (1) is as described in the section of the polyimide.

<Method for producing amines of the present invention>
The amines represented by the above general formula (1) of the present invention are, for example, in the presence of an acid, the following general formula (3):

で表されるジニトロフルオレノン類と下記一般式（４）：

Dinitrofluorenones represented by and the following general formula (4):

（上記一般式（４）中、Ｒ_３は炭素数１〜１２のアルキル基、ハロゲン原子、ヒドロキシル基、炭素数４〜１２の置換基を有してもよいシクロアルキル基、又は炭素数６〜１２の置換基を有してもよい芳香族基を表し、ｍ_２は０〜４の整数を表す。）
で表されるフェノール類とを反応させて、下記一般式（２）：

(In the above general formula (4), R ₃ is an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxyl group, a cycloalkyl group which may have a substituent having 4 to 12 carbon atoms, or 6 to 6 carbon atoms. It represents an aromatic group which may have 12 substituents, and m ₂ represents an integer of 0-4.)
By reacting with phenols represented by, the following general formula (2):

（上記一般式（２）中、Ｒ_１及びＲ_２並びにｍ及びｎは上述の通りである。）
で表されるキサンテンニトロ化合物を得た後、該キサンテンニトロ化合物を還元することで本発明の上記一般式（１）で表されるアミン類を得ることができる。以下、上記製造方法について詳述する。

(In the above general formula (2), R ₁ and R ₂ and m and n are as described above.)
After obtaining the xanthene nitro compound represented by, the amines represented by the above general formula (1) of the present invention can be obtained by reducing the xanthene nitro compound. Hereinafter, the above manufacturing method will be described in detail.

<Method for producing xanthene nitro compound represented by the above general formula (2)>
As a method for producing a xanthene nitro compound represented by the general formula (2), for example, in the presence of an acid, dinitrofluorenones represented by the general formula (3) and phenols represented by the general formula (4) are used. It is obtained by reacting with. (Hereinafter, it may be referred to as a xanthene conversion step.)

The dinitrofluorenones represented by the general formula (3) can be produced by a conventionally known method such as nitration of 9-fluorenone, or a commercially available product can also be used. Among the dinitrofluorenones represented by the general formula (3), 2,7-dinitro-9-fluorenone is preferable from the viewpoint of availability.

In the general formula (4), for example, the alkyl group having 1 to 12 carbon atoms in the substituent _{R 3,} a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, s- butyl, t- A linear or branched alkyl group such as a butyl group, a pentyl group, or a hexyl group can be mentioned, preferably a linear or branched alkyl group having 1 to 8 carbon atoms, and more preferably 1 to 8 carbon atoms. It is a linear or branched alkyl group of No. 6, and more preferably a linear or branched alkyl group having 1 to 3 carbon atoms. Examples of the cycloalkyl group which may have a substituent having 4 to 12 carbon atoms include a cyclopentyl group, a cyclohexyl group, an alkyl (for example, an alkyl having 1 to 4 carbon atoms) substituted cyclopentyl group, and an alkyl (for example, 1 to 4 carbon atoms). A cycloalkyl group or an alkyl-substituted cycloalkyl group represented by 4 to 12 carbon atoms (preferably 5 to 8 carbon atoms) such as an alkyl) substituted cyclohexyl group of 4 can be mentioned, preferably a cyclopentyl group or a cyclohexyl group. be. Examples of the aromatic group which may have a substituent having 6 to 12 carbon atoms include a phenyl group, an alkyl (for example, an alkyl having 1 to 4 carbon atoms) substituted phenyl group, and a naphthyl group, and phenyl is preferable. It is a group or an alkyl-substituted phenyl group (for example, a methylphenyl group, a dimethylphenyl group, an ethylphenyl group, etc.), and more preferably a phenyl group. From the viewpoint of easy production of xanthene nitro compounds, substituent R ₃ in the general formula (4) are preferably each independently an alkyl group having 1 to 12 carbon atoms. _{Further, m 2} representing the number of substituents is preferably 1 or 2 from the viewpoint of ease of production of the xanthennitro compound, and the substitution position is when the number of substituents is 1 (m ₂ = 1). It is preferably in the meta position with respect to the hydroxyl group, and when the number of substituents is 2 (m ₂ = 2), it is preferably in the ortho position and the meta position with respect to the hydroxyl group.

The acid used in the xanthening step may be either an inorganic acid or an organic acid, and examples of the inorganic acid include sulfuric acid, hydrochloric acid and phosphoric acid, and examples of the organic acid include paratoluenesulfonic acid, methanesulfonic acid and acetic acid. Among these acids, sulfuric acid, hydrochloric acid, and p-toluenesulfonic acid are preferably used. These acids may be used alone or in combination of two or more as required. The amount of the acid used is, for example, 0.01 to 10 mol, preferably 0.1 to 7 mol, more preferably 0.4 to 5 mol, based on 1 mol of the dinitrofluorenones represented by the above general formula (3). be. By using 10 mol or less, it becomes easy to improve the purity of the obtained xanthene nitro compound and reduce the coloring. Further, by increasing the amount used to be more than 0.01 mol, a sufficient reaction rate can be obtained.

When carrying out the xantheneization step, an inert organic solvent can be used, if desired. Examples of usable organic solvents include aromatic hydrocarbons, halogenated aromatic hydrocarbons, and halogenated aliphatic hydrocarbons. Examples of aromatic hydrocarbons include toluene, xylene, mesitylene and the like, examples of aliphatic hydrocarbons include pentane, hexane and heptane, and examples of halogenated aromatic hydrocarbons include chlorobenzene and dichlorobenzene. Examples of the halogenated aliphatic hydrocarbons include dichloromethane, 1,2-dichloroethane and the like. Among these organic solvents, aromatic hydrocarbons and halogenated aromatic hydrocarbons are preferable, and toluene and xylene are particularly preferable. The organic solvent may be used alone or in combination of two or more as required.

The amount of the organic solvent used is usually 1 to 15 parts by weight, preferably 1.5 to 10 parts by weight, more preferably 1.5 to 10 parts by weight, based on 1 part by weight of the dinitrofluorenones represented by the general formula (3). It is 1.5 to 4 parts by weight. When the amount of the organic solvent used is 1 part by weight or more, the xanthene nitro compound can be produced more efficiently, and when the amount used is 15 parts by weight or less, xanthene nitro is more economical and productive. Compounds can be produced.

The xanthene step is usually carried out at 80 ° C. or higher, preferably 80 to 140 ° C., more preferably 100 to 120 ° C. By setting the reaction temperature to 80 ° C. or higher, the cyclization reaction after the condensation reaction between the dinitrofluorenones represented by the general formula (3) and the phenols represented by the general formula (4) proceeds efficiently. As a result, a sufficient reaction rate can be obtained. Further, by setting the temperature to 140 ° C. or lower, the formation of a multimer of a dimer or more can be suppressed, and the coloring of the obtained xanthene nitro compound can be reduced.

When carrying out the xantheneization step, a thio compound may be used in combination if necessary. Examples of thio compounds that can be used in combination include thioacetic acid, β-mercaptopropionic acid, α-mercaptopropionic acid, thioglycolic acid, thiosuccinic acid, mercaptosuccinic acid, mercaptobenzoic acid and other mercaptocarboxylic acids, methyl mercaptan, ethyl mercaptan, and propyl. Examples thereof include alkyl mercaptans such as mercaptan, isopulpil mercaptan, butyl mercaptan, octyl mercaptan, decyl mercaptan, dodecyl mercaptan, aralkyl mercaptans such as benzyl mercaptan, and alkali metal salts thereof. The thio compound may be used alone or in combination of two or more as required. Among these thio compounds, alkyl mercaptans are preferable, and alkyl mercaptans having an alkyl group having 6 or more carbon atoms are preferable, and dodecyl mercaptan is particularly preferable, because they have less odor and are easy to handle. The amount of the thio compound used is, for example, 0.01 to 0.3 mol, preferably 0.01 to 0.1 mol, based on 1 mol of the dinitrofluorenones represented by the above general formula (3).

After the xanthene conversion step, the obtained reaction solution may be directly subjected to a reduction step described later, or if necessary, after performing conventional purification operations such as washing with water and adsorption, crystals of the xanthene nitro compound are taken out by crystallization. You may. The obtained crystals may be further subjected to operations such as washing and drying if necessary, and further, if necessary, ordinary purification operations such as adsorption, steam distillation, recrystallization and column purification may be repeated. ..

<Method for producing amines represented by the above general formula (1)>
The amines represented by the general formula (1) can be obtained, for example, by reducing the nitro group of the xanthene nitro compound represented by the general formula (2) (hereinafter, may be referred to as a reduction step). ). The reduction step is, for example, a method in which the xanthennitro compound represented by the above general formula (2) is dissolved in a protonic solvent such as methanol or ethanol and then reduced using a reducing agent such as tin chloride, or the above general formula. A method in which the xanthene nitro compound represented by (2) is dissolved in an inert organic solvent, hydrogenated, and reduced using a catalyst in which transition metal atoms such as palladium and platinum are supported on activated carbon (hereinafter, catalytic reduction method). (Sometimes referred to as). In industrial practice, catalytic reduction is performed from the viewpoint of the type of solvent for dissolving the xanthene nitro compound represented by the above general formula (2), the wide range of application of the reaction temperature, or the ease of post-treatment. The method is preferably used. Hereinafter, the catalytic reduction method will be described in detail.

As the catalyst used in the reduction step, a catalyst in which a transition metal atom such as palladium or platinum is supported on the activated carbon is used, and among these, a catalyst in which palladium is supported on the activated carbon (palladium / carbon) or platinum is supported on the activated carbon. The catalyst (platinum / carbon) is preferably used because it can easily improve the reaction rate. The amount of these catalysts used is usually 0.001 to 0.1 times by weight, preferably 0 times by weight of the xanthene nitro compound represented by the above general formula (2), as the weight of the transition metal atom in the catalyst. It is 0.01 to 0.05 times by weight.

As the organic solvent used when carrying out the reduction step, the xanthene nitro compound represented by the above general formula (2) or the amines represented by the above general formula (1) which is a product does not react and is contacted. Anything that does not undergo a reaction during reduction may be used. Examples of such organic solvents include alcohols, ethers, esters, halogenated aliphatic hydrocarbons, aromatic hydrocarbons, phenols, amides, and other picolines, pyridines, dimethylsulfoxides, and 1,3-dimethyl. -2-Imidazolidinone and the like are exemplified. Alcohols such as methanol and ethanol, ethers such as tetrahydrofuran, 1,4-dioxane, jiglime and triglime, esters such as ethyl acetate and γ-butyrolactone, and halogenated aliphatic hydrocarbons such as chloroform. , Dichloromethane, chloroform, 1,2-dichloroethane and the like, aromatic hydrocarbons such as toluene and xylene, and amides such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethyl. Examples thereof include acetamide, N, N-dimethylformamide and the like. These organic solvents may be used alone or in combination of two or more, if necessary. Among these organic solvents, amides such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and N, N-dimethylformamide are preferably used. As the amount of these organic solvents used, for example, 2 to 10 parts by weight are usually used with respect to 1 part by weight of the xanthene nitro compound represented by the above general formula (2).

The temperature at which the reduction step is carried out is usually 20 to 160 ° C., preferably 20 to 100 ° C. from the viewpoint of improving the reaction rate and suppressing the formation of impurities.

When carrying out the reduction step, the pressure of hydrogen in the reaction vessel is usually 101.3 kPa to 1013 kPa. A sufficient reduction rate can be obtained by setting the value to 101.3 kPa or more, and the reaction rate can be controlled by setting the value to 1013 kPa or less, and unnecessary side reactions and gelation can be suppressed.

After carrying out the reduction step, the catalyst used in the reaction is removed by filtration, for example, a part or all of the organic solvent is distilled off, and then a poor solvent is added as necessary for crystallization. The amines represented by 1) can be separated.

The amines represented by the above general formula (1) thus obtained may be used as they are in the polyamic acid or polyimide production step described later, and if necessary, conventional purification operations such as washing with water and adsorption may be performed. After that, the amine crystals may be taken out by crystallization. The obtained crystals may be further subjected to operations such as washing and drying if necessary, and further, if necessary, ordinary purification operations such as adsorption, steam distillation, recrystallization and column purification may be repeated. ..

<Method for producing polyamic acid containing a constituent unit derived from amines represented by the above general formula (1) and a constituent unit derived from acid dianhydride in the main chain>
As a method for producing a polyamic acid of the present invention, for example, after dissolving the amines represented by the general formula (1) and the above-mentioned commonly usable amines in a polymerization solvent described later, the above-mentioned acid is usually at 10 to 30 ° C. The polyamic acid of the present invention can be obtained as a solution of a polymerization solvent (hereinafter, also referred to as a polyamic acid solution) by adding dianhydride and stirring at 10 to 100 ° C., preferably 10 to 30 ° C. can.

Examples of the polymerization solvent used in producing polyamic acids include amides, chain esters, cyclic esters, carbonates, glycols, phenols, ethers, ketones, alcohols, aromatic hydrocarbons, and the like. Sulfones are exemplified. Examples of amides include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-pyrrolidone and the like, and examples of chain esters include butyl acetate, ethyl acetate, isobutyl acetate and the like, and cyclic esters. Examples include γ-butyrolactone, γ-caprolactone, ε-caprolactone and the like, examples of carbonates include ethylene carbonate and propylene carbonate, and examples of glycols include triethylene glycol, ethyl cellosolve, butyl cellosolve, propylene glycol methyl acetate and 2 -Methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, dimethoxyethane, diethoxy ethane, diethylene glycol and the like are exemplified, and examples of phenols include phenol, o-cresol, m-cresol, p-cresol and 3-chlorophenol. , 4-Chlorophenol, etc., examples of ethers include tetrahydrofuran, dibutyl ether, diethyl ether, etc., examples of ketones include methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, methyl ethyl ketone, acetone, acetophenone, etc. Examples of the class include butanol, ethanol and the like, examples of aromatic hydrocarbons include xylene, toluene and chlorobenzene, and examples of sulfones include dimethyl sulfoxide and sulfolane. Among these polymerization solvents, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-pyrrolidone are preferably used. These solvents may be used alone or in combination of two or more, if necessary.

The amount of the polymerization solvent used is such that the total concentration of the monomer components (acid dianhydride + amines) in the reaction system is usually 5 to 40% by weight, preferably 10 to 30% by weight. By carrying out the polymerization in the above-mentioned monomer concentration range, a uniform polyamic acid solution having a high degree of polymerization can be obtained. If the polymerization is carried out at a concentration lower than the above-mentioned monomer concentration range, the degree of polymerization of the polyamic acid may not be sufficiently high, and the finally obtained polyimide film may become fragile, and the concentration is higher than the above-mentioned monomer concentration range. When polymerization is carried out in, the monomer may not be sufficiently dissolved, or the reaction solution may become non-uniform and gel. The polyamic acid solution obtained by the above method and containing the constituent unit derived from amines represented by the above general formula (1) and the constituent unit derived from acid dianhydride in the main chain is usually used as it is by the method described later. Used for the polyimideization process to be carried out.

<Method for producing polyimide containing a constituent unit derived from amines represented by the above general formula (1) and a constituent unit derived from acid dianhydride in the main chain>
The polyimide of the present invention dehydrates and rings-closes a polyamic acid solution containing a structural unit derived from amines represented by the above general formula (1) and a structural unit derived from acid dianhydride in the main chain obtained by the above method. It can be produced by a reaction (imidization reaction). The imidization reaction can be carried out by using a conventionally known method, for example, a thermal imidization method or a chemical imidization method. Hereinafter, an example of the thermal imidization method and the chemical imidization method will be shown.

In the thermal imidization method, first, a polyamic acid polymerization solution is cast on a support such as a glass plate and heated in a vacuum, in an inert gas such as nitrogen, or in air to obtain the polyamic acid. Get the film. For example, a polyamic acid film can be obtained by drying in an oven, usually at 50-190 ° C., preferably 100-180 ° C.

Subsequently, the obtained polyamic acid film is heated on a support at usually 200 to 400 ° C., preferably 230 to 350 ° C. to carry out an imidization reaction. By setting the heating temperature to 200 ° C. or higher, the imidization reaction can proceed sufficiently, and by setting the heating temperature to 400 ° C. or lower, more stable polyimide can be obtained. The imidization reaction is preferably carried out in vacuum or in an inert gas, but may be carried out in air as long as the imidization reaction temperature is less than 300 ° C.

In the chemical imidization method, at the time of polymerization in a polyamic acid solution containing a structural unit derived from amines represented by the above general formula (1) and a structural unit derived from acid dianhydride obtained by the above method in the main chain. After adding the same solvent as above to obtain an appropriate solution viscosity that is easy to stir, a dehydration ring-closing agent (chemical imidizing agent) consisting of an anhydride of an organic acid and a tertiary amine as a basic catalyst is added dropwise while stirring. Further, the imidization can be completed chemically by stirring at a temperature of 0 to 100 ° C., preferably 10 to 50 ° C.

Examples of the organic acid anhydride that can be used in the chemical imidization method include acetic anhydride and propionic anhydride. Among these organic acid anhydrides, acetic anhydride is preferable because of its ease of handling and separation. Examples of the basic catalyst that can be used in chemical imidization include pyridine, triethylamine, quinoline and the like. Among these basic catalysts, pyridine is preferable because of its ease of handling and separation. The amount of the organic acid anhydride in the chemical imidizing agent is 1 to 10 times by mole, more preferably 2 to 5 times by mole, based on 1 mol of the theoretical dehydration amount of the polyamic acid. The amount of the basic catalyst is 0.1 to 2 times mol, more preferably 0.2 to 1 times mol, with respect to 1 mol of the organic acid anhydride amount.

Since the reaction solution obtained by the above chemical imidization method contains bases, unreacted chemical imidizing agents, organic acids, by-products, etc. (hereinafter referred to as impurities), these are removed. The polyimide may be isolated and purified. A known method can be used for purification. For example, the imidized reaction solution is dropped into a large amount of poor solvent while stirring to precipitate polyimide, and then the polyimide powder is recovered, washed repeatedly until impurities are removed, dried under reduced pressure, and the polyimide powder is dried. There is a way to obtain.

The poor solvent that can be used in the above method may be any solvent that can precipitate polyimide, efficiently remove impurities, and is easy to dry. For example, water and alcohols such as methanol, ethanol, and isopropanol are suitable. These may be used together.

If the concentration of the polyimide solution when dropping into a poor solvent to precipitate polyimide is too high, the precipitated polyimide becomes a granular mass and impurities remain in the coarse particles, or the obtained polyimide powder is used as a solvent. It may take a long time to redissolve. Therefore, the concentration of the polyimide solution when added dropwise to the poor solvent is usually 20% by weight or less, more preferably 10% by weight or less. The amount of the poor solvent used is preferably 1 times by weight or more, more preferably 1.5 to 10 times by weight, based on the polyimide solution.

The temperature at which the obtained polyimide powder is recovered and the residual solvent is removed by vacuum drying, hot air drying, or the like is not limited as long as the polyimide does not deteriorate, and is preferably 30 to 150 ° C.

In the chemical imidization reaction, for example, a polyamic acid is applied onto a support such as a glass plate to form a film, and the film is subjected to an organic acid anhydride such as acetic anhydride in the presence of a tertiary amine such as pyridine or triethylamine. It can also be done by immersing in the contained solution. By the above operation, a partially or almost completely imidized polyimide film can be prepared, and further, the film is dried in an oven, for example, usually at 200 to 400 ° C, preferably 250 to 350 ° C. It can also be a more completely imidized polyimide film.

<Polyimide solution of the present invention>
The polyimide of the present invention obtained by the above method can be dissolved in an arbitrary organic solvent to obtain a polyimide solution.

Examples of the organic solvent used for preparing the polyimide solution of the present invention include amides, esters, carbonates, glycols, phenols, ketones and ethers, and examples of amides include N, N-dimethylformamide. N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like are used as esters such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone and α-methyl-γ-butyrolactone. , Butyl acetate, ethyl acetate, isobutyl acetate, etc., as carbonates, ethylene carbonate, propylene carbonate, etc., as glycols, diethylene glycol dimethyl ether, triethylene glycol, triethylene glycol dimethyl ether, etc., as phenols, phenol, m- Cresol, p-cresol, o-cresol, 3-chlorophenol, 4-chlorophenol and the like, cyclopentanone, cyclohexanone, acetone, methyl ethyl ketone, diisobutyl ketone, methyl isobutyl ketone and the like as ketones, tetrahydrofuran as ethers , 1,4-Dioxane, Dimethoxyethane, Diethoxyethane, Dibutyl ether, Methyl monoglyme (1,2-dimethoxyethane), Methyl diglime (bis (2-methoxyethyl) ether) and Methyl triglime (1, 2) -Bis (2-methoxyethoxy) ethane) and other general-purpose solvents include acetphenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethylsulfoxide, propylene glycol methyl acetate, ethyl cellosolve, butyl cellosolve, 2-methyl. Cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, xylene, toluene, chlorobenzene, turpen, mineral spirit, petroleum naphtha and the like can be used. These organic solvents may be used alone or in combination of two or more, if necessary.

Among the above organic solvents, the amide solvent is N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc) and N-methyl-2-pyrrolidone (NMP), and the ketone solvent is methyl ethyl ketone. (MEK), methylisobutylketone (MIBK), cyclopentanone and cyclohexanone, methylmonoglime (1,2-dimethoxyethane) as ether solvent, methyldiglime (bis (2-methoxyethyl) ether) and methyltri Glyme (1,2-bis (2-methoxyethoxy) ethane) and the like are particularly preferable. The concentration of the polyimide solution of the present invention is preferably 5 to 40% by weight, and more preferably 5 to 20% by weight from the viewpoint of ensuring the smoothness of the film when the polyimide film is prepared by the method described later.

<Manufacturing method of polyimide film>
The polyimide of the present invention obtained by the above method can be formed into a film by any method. As a method for forming a film, for example, in addition to a method of preparing a polyamic acid film by the above-mentioned method and then forming a polyimide film by thermal imidization or chemical imidization, the above-mentioned polyimide solution of the present invention is applied onto a support ( It can also be manufactured by a method of peeling from the support after drying (also referred to as coating).

As the support for coating the polyimide solution, a glass substrate or a metal substrate such as stainless steel, or a metal belt, a plastic film such as polyethylene terephthalate, polycarbonate, polyacrylate, polyethylene naphthalate or triacetyl cellulose is used. , Not limited to these. In order to adapt to the current batch type device manufacturing process, it is preferable to use a glass substrate.

The conditions for drying the polyimide film after applying the polyimide solution on the support can be appropriately selected according to the process. Specific examples thereof include a method in which a polyimide solution is applied onto a support, then heat-treated at 150 ° C. for 1 hour, and then further heat-treated at 250 ° C. for 1 hour.

<Use of Polyimide of the Present Invention>
The polyimide of the present invention can be used, for example, in a substrate, a color filter, a printed matter, an optical material, an electronic device, an image display device, or the like. Furthermore, it can be used as an alternative material for parts where glass or transparent materials are currently used.

Examples of the substrate include a TFT substrate, a flexible display substrate, a transparent conductive film substrate, and the like. Examples of the electronic device include a touch panel and a solar cell. Further, examples of the image display device include a flexible display, a liquid crystal display device, an organic EL, an electronic paper, a 3D display, and the like.

The present invention can also be expressed as follows.

（上記一般式（１）中、Ｒ_１及びＲ_２はそれぞれ独立して炭素数１〜１２のアルキル基、ハロゲン原子、ヒドロキシル基、炭素数４〜１２の置換基を有してもよいシクロアルキル基、又は炭素数６〜１２の置換基を有してもよい芳香族基を表し、ｍ及びｎは０〜４の整数を表す。なお、Ｒ_１及び／又はＲ_２が複数存在する場合、それぞれは同一でも異なっていてもよい。）
〔２〕下記一般式（Ｐ−１）で表される繰り返し単位を有する、〔１〕に記載のポリイミド。

（上記一般式（Ｐ−１）中、Ｒ_１及びＲ_２並びにｍ及びｎは上述の通りである。Ｘ_１は４価の脂肪族基を表す。）
〔３〕更に下記一般式（Ｐ−２）で表される繰り返し単位を有する、〔１〕または２に記載のポリイミド。

（上記一般式（Ｐ−２）中、Ｘ_１は上述の通りであり、Ｘ_２はフッ素原子を有する２価の芳香族基である。）
〔４〕下記一般式（Ｐ−２）：

（上記一般式（Ｐ−２）中、Ｘ_１及びＸ_２は上述の通りである。）
において、Ｘ_２が下記一般式（Ｐ−３）：

[1] A polyimide having a constituent unit derived from amines represented by the following general formula (1) and a constituent unit derived from acid dianhydride in the main chain.

(In the above general formula (1), R ₁ and R ₂ may independently have an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxyl group, and a substituent having 4 to 12 carbon atoms, respectively. It represents a group or an aromatic group which may have a substituent having 6 to 12 carbon atoms, and m and n represent an integer of 0 to _{4. When a plurality of R 1} and / or R ₂ are present, Each may be the same or different.)
[2] The polyimide according to [1], which has a repeating unit represented by the following general formula (P-1).

(In the above general formula (P-1), R ₁ and R ₂ and m and n are as described above. X ₁ represents a tetravalent aliphatic group.)
[3] The polyimide according to [1] or 2, further having a repeating unit represented by the following general formula (P-2).

(In the above general formula (P-2), X ₁ is as described above, and X ₂ is a divalent aromatic group having a fluorine atom.)
[4] The following general formula (P-2):

(In the above general formula (P-2), X ₁ and X ₂ are as described above.)
In, _{X 2} is represented by the following general formula (P-3):

（上記一般式（１）中、Ｒ_１及びＲ_２はそれぞれ独立して炭素数１〜１２のアルキル基、ハロゲン原子、ヒドロキシル基、炭素数４〜１２の置換基を有してもよいシクロアルキル基、又は炭素数６〜１２の置換基を有してもよい芳香族基を表し、ｍ及びｎは０〜４の整数を表す。なお、Ｒ_１及び／又はＲ_２が複数存在する場合、それぞれは同一でも異なっていてもよい。）
で表されるアミン類由来の構成単位、及び酸二無水物由来の構成単位を主鎖に含むポリアミック酸。
〔６〕下記一般式（１）で表されるアミン類。

（上記一般式（１）中、Ｒ_１及びＲ_２はそれぞれ独立して炭素数１〜１２のアルキル基、ハロゲン原子、ヒドロキシル基、炭素数４〜１２の置換基を有してもよいシクロアルキル基、又は炭素数６〜１２の置換基を有してもよい芳香族基を表し、ｍ及びｎは０〜４の整数を表す。なお、Ｒ_１及び／又はＲ_２が複数存在する場合、それぞれは同一でも異なっていてもよい。）
〔７〕下記一般式（２）：

（上記一般式（２）中、Ｒ_１及びＲ_２はそれぞれ独立して炭素数１〜１２のアルキル基、ハロゲン原子、ヒドロキシル基、炭素数４〜１２の置換基を有してもよいシクロアルキル基、又は炭素数６〜１２の置換基を有してもよい芳香族基を表し、ｍ及びｎは０〜４の整数を表す。なお、Ｒ_１及び／又はＲ_２が複数存在する場合、それぞれは同一でも異なっていてもよい。）
で表されるキサンテンニトロ化合物を還元する、下記一般式（１）：

（上記一般式（１）中、Ｒ_１及びＲ_２はそれぞれ独立して炭素数１〜１２のアルキル基、ハロゲン原子、ヒドロキシル基、炭素数４〜１２の置換基を有してもよいシクロアルキル基、又は炭素数６〜１２の置換基を有してもよい芳香族基を表し、ｍ及びｎは０〜４の整数を表す。なお、Ｒ_１及び／又はＲ_２が複数存在する場合、それぞれは同一でも異なっていてもよい。）
で表されるアミン類の製造方法。
〔８〕酸存在下、下記一般式（３）：

で表されるジニトロフルオレノン類と下記一般式（４）：

（上記一般式（４）中、Ｒ_３は炭素数１〜１２のアルキル基、ハロゲン原子、ヒドロキシル基、炭素数４〜１２の置換基を有してもよいシクロアルキル基、又は炭素数６〜１２の置換基を有してもよい芳香族基を表し、ｍ_２は０〜４の整数を表す。）
で表されるフェノール類とを反応させる、下記一般式（２）：

（上記一般式（２）中、Ｒ_１及びＲ_２はそれぞれ独立して炭素数１〜１２のアルキル基、ハロゲン原子、ヒドロキシル基、炭素数４〜１２の置換基を有してもよいシクロアルキル基、又は炭素数６〜１２の置換基を有してもよい芳香族基を表し、ｍ及びｎは０〜４の整数を表す。なお、Ｒ_１及び／又はＲ_２が複数存在する場合、それぞれは同一でも異なっていてもよい。）
で表されるキサンテンニトロ化合物の製造方法。
〔９〕下記一般式（２）で表されるキサンテンニトロ化合物。

（上記一般式（２）中、Ｒ_１及びＲ_２はそれぞれ独立して炭素数１〜１２のアルキル基、ハロゲン原子、ヒドロキシル基、炭素数４〜１２の置換基を有してもよいシクロアルキル基、又は炭素数６〜１２の置換基を有してもよい芳香族基を表し、ｍ及びｎは０〜４の整数を表す。なお、Ｒ_１及び／又はＲ_２が複数存在する場合、それぞれは同一でも異なっていてもよい。）
〔１０〕〔１〕〜〔４〕のいずれかに記載のポリイミドと有機溶媒とを含有する、ポリイミド溶液。
〔１１〕〔１〕〜〔４〕のいずれかに記載のポリイミドを含有する、ポリイミドフィルム。
〔１２〕〔１〕〜〔４〕のいずれかに記載のポリイミドを含有する、プラスチック基板材料。 (In the above general formula (P-3), * represents the coupling position.)
The polyimide according to [3], which is an aromatic group represented by.
[5] The following general formula (1):

(In the above general formula (1), R ₁ and R ₂ may independently have an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxyl group, and a substituent having 4 to 12 carbon atoms, respectively. It represents a group or an aromatic group which may have a substituent having 6 to 12 carbon atoms, and m and n represent an integer of 0 to _{4. When a plurality of R 1} and / or R ₂ are present, Each may be the same or different.)
A polyamic acid having a constituent unit derived from amines represented by and a constituent unit derived from acid dianhydride in the main chain.
[6] Amines represented by the following general formula (1).

(In the above general formula (1), R ₁ and R ₂ may independently have an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxyl group, and a substituent having 4 to 12 carbon atoms, respectively. It represents a group or an aromatic group which may have a substituent having 6 to 12 carbon atoms, and m and n represent an integer of 0 to _{4. When a plurality of R 1} and / or R ₂ are present, Each may be the same or different.)
[7] The following general formula (2):

(In the above general formula (2), R ₁ and R ₂ may independently have an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxyl group, and a substituent having 4 to 12 carbon atoms, respectively. It represents a group or an aromatic group which may have a substituent having 6 to 12 carbon atoms, and m and n represent an integer of 0 to _{4. When a plurality of R 1} and / or R ₂ are present, Each may be the same or different.)
The following general formula (1): which reduces the xanthene nitro compound represented by

(In the above general formula (1), R ₁ and R ₂ may independently have an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxyl group, and a substituent having 4 to 12 carbon atoms, respectively. It represents a group or an aromatic group which may have a substituent having 6 to 12 carbon atoms, and m and n represent an integer of 0 to _{4. When a plurality of R 1} and / or R ₂ are present, Each may be the same or different.)
A method for producing amines represented by.
[8] In the presence of acid, the following general formula (3):

Dinitrofluorenones represented by and the following general formula (4):

(In the above general formula (4), R ₃ is an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxyl group, a cycloalkyl group which may have a substituent having 4 to 12 carbon atoms, or 6 to 6 carbon atoms. It represents an aromatic group which may have 12 substituents, and m ₂ represents an integer of 0-4.)
The following general formula (2): to react with phenols represented by

(In the above general formula (2), R ₁ and R ₂ may independently have an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxyl group, and a substituent having 4 to 12 carbon atoms, respectively. It represents a group or an aromatic group which may have a substituent having 6 to 12 carbon atoms, and m and n represent an integer of 0 to _{4. When a plurality of R 1} and / or R ₂ are present, Each may be the same or different.)
A method for producing a xanthene nitro compound represented by.
[9] A xanthene nitro compound represented by the following general formula (2).

(In the above general formula (2), R ₁ and R ₂ may independently have an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxyl group, and a substituent having 4 to 12 carbon atoms, respectively. It represents a group or an aromatic group which may have a substituent having 6 to 12 carbon atoms, and m and n represent an integer of 0 to _{4. When a plurality of R 1} and / or R ₂ are present, Each may be the same or different.)
[10] A polyimide solution containing the polyimide according to any one of [1] to [4] and an organic solvent.
[11] A polyimide film containing the polyimide according to any one of [1] to [4].
[12] A plastic substrate material containing the polyimide according to any one of [1] to [4].

The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the claims, and the embodiments obtained by appropriately combining the technical means disclosed in the different embodiments. Is also included in the technical scope of the present invention. Furthermore, new technical features can be formed by combining the technical means disclosed in each embodiment.

Examples of the present invention are shown below, but the present invention is not limited thereto. Moreover, the values shown in each Example / Comparative Example are the values by the following analysis method.

[1] HPLC Purity HPLC measurement was performed under the following measurement conditions, and the area percentage value obtained by the measurement was used as the purity of each compound described in each example.
・ Equipment: LC-2010C manufactured by Shimadzu Corporation
-Column: "ODS A-211" manufactured by Sumika Chemical Analysis Service Co., Ltd.
(5 μm, 4.6 mm φ × 250 mm)
-Column temperature: 40 ° C
-Detection wavelength: UV 254 nm
-Mobile phase: Liquid A = water, liquid B = acetonitrile-Mobile phase flow rate: 1.0 ml / min-Mobile phase gradient: Liquid B concentration: 50% (0 minutes) → 100% (25 minutes later) → 100% ( 35 minutes later)

[2] NMR measurement
^{1 1} H-NMR was recorded by a JEOL-ESC400 spectrometer using tetramethylsilane as an internal standard and deuterated dimethyl sulfoxide (DMSO) as a solvent.

[3] LC-MS measurement LC-MS was separated and mass spectrometrically analyzed under the following measurement conditions to identify the target product.
-Device: "Xevo G2 Q-Tof" manufactured by Waters Corp.
-Column: "ACQUITY CSH C18" manufactured by Waters Corp.
(1.7 μm, 2.1 mmφ x 100 mm)
-Column temperature: 40 ° C
-Detection wavelength: UV 210-500 nm
-Mobile phase: Solution A = 5 mM ammonium acetate water, Solution B = methanol-Mobile phase flow rate: 0.3 ml / min-Mobile phase gradient: Solution B concentration: 50% (0 minutes) → 100% (10 minutes later) → 100% (after 15 minutes)
-Detection method: Q-Tof
-Sampling Cone: Voltage 30V, Gas flow 50L / h
-Desolution Gas: Temperature 500 ° C, gas flow 1000 L / h
-Ionization method: ESI (+) method or APCI (-) method-Ion Source: ESI (+) method
Voltage (+) 2.0 kV, temperature 120 ° C
In the case of APCI (-) method
Temperature 120 ° C

[4] Weight average molecular weight The weight average molecular weight was measured under the following measurement conditions.
・ Equipment: HLC-8200 manufactured by Tosoh Corporation
-Column: TSK-GEL Super AWM-H (6.0 mm ID x 15 cm)
-Mobile phase: N, N-dimethylformamide, flow rate: 1.0 ml / min
-Column temperature: 40 ° C
・ Molecular weight standard substance: polystyrene

[5] Glass transition temperature (Tg)
Measurement was performed at a heating rate of 30 ° C./min using a differential scanning calorimeter (“EXSTAR DSC 7020” manufactured by SII Nanotechnology Co., Ltd.). Since it is not possible to measure at 400 ° C. or higher, when the glass transition temperature exceeds 400 ° C., it is described as “400 ° C. or higher”.

[6] Measurement of double refraction Using an Abbe refractometer (“Multi-wavelength Abbe refractometer DR-2M” manufactured by Atago Co., Ltd.), refraction in the direction parallel to the polyimide film (n _in ) and refraction in the direction perpendicular to the direction. The rate (n _out ) was measured at a wavelength of 589 nm, and the double refractometer (Δn = n _{in −} n _out ) in the thickness direction was determined from the difference between these refractive indexes. If the measured polyimide n _in is greater than 1.71, the refractive index of a value greater than 1.71 cannot be measured accurately, so the birefringence value calculated assuming that _{n in is 1.71 is used.} Described with the wording "more than".

[7] Measurement of yellowness (YI) Yellowness (YI) was calculated in accordance with ASTM D1925 using an ultraviolet-visible spectrophotometer SE-6000 (manufactured by JASCO Corporation) (hereinafter, the calculated values are YI). Sometimes referred to as a value).

[8] Total light transmittance (Tt) and haze (Haze)
The total light transmittance and haze (turbidity) of the polyimide film were measured using a haze meter (“HGM-2DP” manufactured by Suga Test Instruments Co., Ltd.).

[9] Coefficient of linear thermal expansion (CTE)
The polyimide film obtained in each example has a width of 5 mm and a length of 40 mm, and the load (static load) is the film thickness (μm) × 0.5 g weight, and is measured using “TMA7100” manufactured by Hitachi High-Tech Science Co., Ltd. bottom. The coefficient of linear thermal expansion of the polyimide film was calculated from the TMA curve at the time of raising the temperature of the polyimide film to 400 ° C. at 5 ° C./min. The coefficient of linear thermal expansion was determined as an average value between 100 and 200 ° C.

1. 1. Production example of amines represented by the above general formula (1)

<Example 1>
Among the xanthene nitro compounds represented by the general formula (2), a production example of the xanthene nitro compound represented by the following formula (2-1).

A four-necked flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 25.00 g (0.093 mol) of 2,7-dinitro-9-fluorenone and 100.00 g (0.925 mol) of m-cresol, 98%. After dropping 3.70 g (0.037 mol) of sulfuric acid, the reaction was carried out at 110 ° C. for 5 hours. After completion of the reaction, the reaction solution was neutralized with a 24% sodium hydroxide solution, methanol was further added, the temperature was raised to 60 ° C., and the mixture was stirred at the same temperature for 1 hour. After cooling to room temperature, the crystals are filtered, and the crystals are washed with 50% methanol water and then dried to obtain 41.42 g (purity) of yellow crystals of the xanthene nitro compound represented by the above formula (2-1). 96.9%, crude yield 99.4%) was obtained. The analysis results of the xanthene nitro compound represented by the above formula (2-1) are shown below.

^{1 1} H-NMR (DMSO-d6)
δ = 2.33 ppm (6H, s), 6.22 (2H, d), 6.71 (2H, d), 7.19 (2H, s), 7.84 (2H, s), 8.41 (2H, d), 8.48 (2H, d)
Mass spectral ^values: (M) - · 450.12 (ionization method: APCI (-))

<Example 2>
Among the amines represented by the general formula (1), an example of producing an amine represented by the above formula (1-1).

Palladium / carbon powder containing 25.00 g of the xanthene nitro compound represented by the above formula (2-1) obtained in Example 1 and 50% by weight of water in an autoclave having a hydrogen introduction tube (palladium content: dry weight conversion). 1.25 g (5% by weight) was added, and 250.00 g of N, N-dimethylformamide was further added, and the temperature was raised to 80 ° C. to dissolve the xanthene nitro compound. Next, after replacing the reaction vessel with hydrogen, the mixture was stirred at 80 ° C. for 1.5 hours while maintaining the internal pressure of the autoclave with hydrogen at 506.7 kPa. After the reaction, the palladium / carbon powder was removed by hot filtration, the obtained filtrate was cooled to room temperature, and the filtrate was added dropwise to 600.00 g of water to precipitate crystals. The precipitated crystals are filtered, washed with water, and then dried to obtain 20.50 g of white crystals of amine represented by the above formula (1-1) (purity 99.0%, crude yield 94.7%). Got The analysis results of the amine represented by the above formula (1-1) are shown below.

^{1 1} H-NMR (DMSO-d6)
δ = 2.25ppm (6H, s), 4.92ppm (4H, s), 6.16 (2H, s), 6.23 (2H, d), 6.48 (2H, d), 6.65 (2H, d), 7.01 (2H, s), 7.32 (2H, d)
Mass spectral ^values: (M) + · 390.17 (ionization method: ESI (+))

<Example 3>
Among the xanthene nitro compounds represented by the general formula (2), a production example of the xanthene nitro compound represented by the following formula (2-2).

2,7-Dinitro-9-fluorenone 25.00 g (0.093 mol), 2,3-xylenol 28.22 g (0.231 mol), toluene 35 in a four-necked flask equipped with a stirrer, thermometer and reflux condenser. .75 g was charged, 3.70 g (0.037 mol) of 98% sulfuric acid was added dropwise, and the mixture was reacted at 110 ° C. for 6 hours. After completion of the reaction, the reaction solution was neutralized with a 24% sodium hydroxide solution, methanol was further added, the temperature was raised to 60 ° C., and the mixture was stirred at the same temperature for 1 hour. After cooling to room temperature, the crystals are filtered, and the crystals are washed with 50% methanol water and then dried to obtain 42.12 g (purity) of yellow crystals of the xanthene nitro compound represented by the above formula (2-2). 97.7%, crude yield 95.1%) was obtained. The analysis results of the xanthene nitro compound represented by the above formula (2-2) are shown below.

^{1 1} H-NMR (DMSO-d6)
δ = 2.24ppm (6H, s), 2.46ppm (6H, s), 6.08 (2H, d), 6.70 (2H, d), 7.81 (2H, s), 8.40 (2H, d), 8.48 (2H, d)
Mass spectrum value: (M) ^{− ·} 478.15 (ionization method: APCI (−))

<Example 4>
Among the amines represented by the general formula (1), an example of producing an amine represented by the above formula (1-2).

Palladium / carbon powder (palladium content: dry weight conversion) containing 41.00 g of the xanthene nitro compound represented by the above formula (2-2) obtained in Example 3 and 50% by weight of water in an autoclave having a hydrogen introduction tube. The xanthene nitro compound was dissolved by adding 2.05 g (5% by weight) and adding 410.00 g of N, N-dimethylformamide and raising the temperature to 80 ° C. Next, after replacing the reaction vessel with hydrogen, the mixture was stirred at 80 ° C. for 7.5 hours while maintaining the internal pressure of the autoclave with hydrogen at 506.7 kPa. After the reaction, the palladium / carbon powder was removed by hot filtration, the obtained filtrate was cooled to room temperature, and the filtrate was added dropwise to 984.00 g of water to precipitate crystals. The precipitated crystals are filtered, washed with water, and dried to obtain 34.70 g of white crystals of amine represented by the above formula (1-2) (purity 98.1%, crude yield 96.8%). Got The analysis results of the amine represented by the above formula (1-2) are shown below.

^{1 1} H-NMR (DMSO-d6)
δ = 2.21 ppm (6H, s), 2.38 ppm (6H, s), 4.89 ppm (4H, s), 6.07 (2H, d), 6.14 (2H, s), 6.47 (2H, d), 6.64 (2H, d), 7.30 (2H, d)
Mass spectrum value: (M) ^{+ ·} 418.20 (ionization method: ESI (+))

<Example 5>
Among the xanthene nitro compounds represented by the general formula (2), a production example of the xanthene nitro compound represented by the following formula (2-3).

2,7-Dinitro-9-fluorenone 65.00 g (0.241 mol), m-ethylphenol 293.87 g (2.406 mol), paratoluenesulfon in a four-necked flask equipped with a stirrer, thermometer and reflux condenser. 18.30 g (0.096 mol) of acid monohydrate was charged and reacted at 110 ° C. for 8 hours. After completion of the reaction, the reaction solution was neutralized with a 24% sodium hydroxide solution, methanol was further added, the temperature was raised to 60 ° C., and the mixture was stirred at the same temperature for 1 hour. After cooling to room temperature, the crystals are filtered, and the crystals are washed with 50% methanol water and then dried to obtain 109.95 g (purity) of yellow crystals of the xanthene nitro compound represented by the above formula (2-3). 97.0%, crude yield 95.5%) was obtained. The analysis results of the xanthene nitro compound represented by the above formula (2-3) are shown below.

^{1 1} H-NMR (DMSO-d6)
δ = 1.15ppm (6H, t), 2.57ppm (4H, dd), 6.23 (2H, d), 6.70 (2H, d), 7.19 (2H, s), 7.85 (2H, s), 8.42 (2H, d), 8.51 (2H, d)
Mass spectrum value: (M) ^{− ·} 478.15 (ionization method: APCI (−))

<Example 6>
Among the amines represented by the general formula (1), an example of producing an amine represented by the above formula (1-3).

Palladium / carbon powder containing 105.00 g of the xanthene nitro compound represented by the above formula (2-3) obtained in Example 5 and 50% by weight of water in an autoclave having a hydrogen introduction tube (palladium content: dry weight conversion). (5% by weight) was added, and 315.00 g of N, N-dimethylformamide was further added, and the temperature was raised to 80 ° C. to dissolve the xanthene nitro compound. Next, after replacing the reaction vessel with hydrogen, the mixture was stirred at 80 ° C. for 3 hours while maintaining the internal pressure of the autoclave with hydrogen at 506.7 kPa. After the reaction, the palladium / carbon powder was removed by hot filtration, the obtained filtrate was cooled to room temperature, and the filtrate was added dropwise to 840.00 g of water to precipitate crystals. The precipitated crystals are filtered, washed with water, and dried to obtain 89.41 g of white crystals of amine represented by the above formula (1-3) (purity 97.4%, crude yield 97.4%). Got
By recrystallizing 87.00 g of the obtained white crystals of amine represented by the above formula (1-3) with 261.00 g of toluene, the amine represented by the above formula (1-3) is performed. 75.55 g (purity 99.1%) of white crystals was obtained. The analysis results of the amine represented by the above formula (1-3) are shown below.

^{1 1} H-NMR (DMSO-d6)
δ = 1.15ppm (6H, t), 2.55ppm (4H, dd),
4.93ppm (4H, s), 6.17 (2H, s), 6.26 (2H, d), 6.48 (2H, d), 6.68 (2H, d), 7.03 (2H) , S), 7.33 (2H, d)
Mass spectrum value: (M) ^{+ ·} 418.20 (ionization method: ESI (+))

2. A production example of a polyimide containing a structural unit derived from amines represented by the general formula (1) and a structural unit derived from acid dianhydride in the main chain.

<Example 7>
(Amine represented by the above formula (1-1), 4,4'-diaminodiphenyl ether (hereinafter, also referred to as 4,4'-DPE), and 3,3', 4,4'-benzophenonetetra. Production of polyimide containing a constituent unit derived from carboxylic acid dianhydride (hereinafter sometimes referred to as BTDA) in the main chain)
1.00 g (2.56 mmol) of amine represented by the above formula (1-1) and 0.51 g (2.56 mmol) of 4,4′-DPE obtained in Example 2 were dehydrated N, N-dimethylacetamide 7 Dissolved in 0.8 g. Then, 1.65 g (5.12 mmol) of BTDA was slowly added and reacted at room temperature for 16 hours, and the constituent unit derived from amine represented by the above formula (1-1), the constituent unit derived from 4,4'-DPE, And a polyamic acid containing a constituent unit derived from BTDA in the main chain was synthesized. The weight average molecular weight (Mw) of the polyamic acid was 65,966.

Then, the polyamic acid solution was diluted by adding 4.80 g of N, N-dimethylacetamide, and then stirred for 1 hour. After applying the obtained polyamic acid solution on a glass plate, it is heated at 150 ° C. for 1 hour and 250 ° C. for 1 hour to form an amine-derived structural unit represented by the above formula (1-1), 4, 4'. A polyimide thin film containing a constituent unit derived from -DPE and a constituent unit derived from BTDA in the main chain was obtained. The film thickness of the thin film was about 26 μm.

<Example 8>
(Production of polyimide containing an amine represented by the above formula (1-2), 4,4'-DPE, and a structural unit derived from BTDA in the main chain)
1.00 g (2.39 mmol) of amine represented by the above formula (1-2) and 0.48 g (2.39 mmol) of 4,4′-DPE obtained in Example 4 were dehydrated N, N-dimethylacetamide 7 After dissolving in .50 g, 1.54 g (4.78 mmol) of BTDA was slowly added and reacted at room temperature for 16 hours, and the constituent unit derived from amine represented by the above formula (1-2), 4,4'-. A polyamic acid containing a constituent unit derived from DPE and a constituent unit derived from BTDA in the main chain was synthesized. The weight average molecular weight (Mw) of the polyamic acid was 109,775.

Then, the polyamic acid solution was diluted by adding 4.60 g of N, N-dimethylacetamide, and then stirred for 1 hour. After applying the obtained polyamic acid solution on a glass plate, it is heated at 150 ° C. for 1 hour and 250 ° C. for 1 hour to form an amine-derived structural unit represented by the above formula (1-2), 4, 4'. A polyimide thin film containing a constituent unit derived from -DPE and a constituent unit derived from BTDA in the main chain was obtained. The film thickness of the thin film was about 24 μm.

<Example 9>
(Production of polyimide containing an amine represented by the above formula (1-3), 4,4'-DPE, and a structural unit derived from BTDA in the main chain)
1.00 g (2.39 mmol) of amine represented by the above formula (1-3) and 0.48 g (2.39 mmol) of 4,4′-DPE obtained in Example 6 were dehydrated N, N-dimethylacetamide 7 After dissolving in .50 g, 1.54 g (4.78 mmol) of BTDA was slowly added and reacted at room temperature for 16 hours, and the constituent unit derived from amine represented by the above formula (1-3), 4,4'-. A polyamic acid containing a constituent unit derived from DPE and a constituent unit derived from BTDA in the main chain was synthesized. The weight average molecular weight (Mw) of the polyamic acid was 257,582.

Then, the polyamic acid solution was diluted by adding 4.60 g of N, N-dimethylacetamide, and then stirred for 1 hour. After applying the obtained polyamic acid solution on a glass plate, it is heated at 150 ° C. for 1 hour and 250 ° C. for 1 hour to form an amine-derived structural unit represented by the above formula (1-3), 4, 4'. A polyimide thin film containing a constituent unit derived from -DPE and a constituent unit derived from BTDA in the main chain was obtained. The film thickness of the thin film was about 22 μm.

<Comparative example 1>
(Production of polyimide containing a constituent unit derived from amine (2,7-diaminofluorene, hereinafter sometimes referred to as DAF) represented by the above formula (5), 4,4'-DPE, and BTDA in the main chain)
After dissolving 0.50 g (2.55 mmol) of DAF and 0.51 g (2.55 mmol) of 4,4'-DPE in 6.40 g of dehydrated N, N-dimethylacetamide, 1.64 g (5.10 mmol) of BTDA is slowly added. Then, the reaction was carried out at room temperature for 16 hours to synthesize a polyamic acid containing a DAF-derived constituent unit, a 4,4'-DPE-derived constituent unit, and a BTDA-derived constituent unit in the main chain. The weight average molecular weight (Mw) of the polyamic acid was 40,865.

Then, the polyamic acid solution was diluted by adding 4.00 g of N, N-dimethylacetamide, and then the mixture was stirred for 1 hour. After applying the obtained polyamic acid solution on a glass plate, it is heated at 150 ° C. for 1 hour and 250 ° C. for 1 hour to form a DAF-derived constituent unit, a 4,4'-DPE-derived constituent unit, and a BTDA-derived constituent unit. A polyimide thin film containing a constituent unit in the main chain was obtained. The film thickness of the thin film was about 22 μm.

<Example 10>
(Polyimide containing a structural unit derived from an amine represented by the above formula (1-1), 4,4'-DPE, and 4,4'-oxydiphthalic anhydride (hereinafter, also referred to as ODPA) in the main chain. Manufacturing of)
1.00 g (2.56 mmol) of amine represented by the above formula (1-1) and 0.51 g (2.56 mmol) of 4,4′-DPE obtained in Example 2 were dehydrated N, N-dimethylacetamide 7 Dissolved in 6 g. Then, 1.58 g (5.12 mmol) of ODPA was slowly added and reacted at room temperature for 16 hours, and the constituent unit derived from amine represented by the above formula (1-1), the constituent unit derived from 4,4'-DPE, And a polyamic acid containing a constituent unit derived from ODPA in the main chain was synthesized. The weight average molecular weight (Mw) of the polyamic acid was 136,737.

Then, the polyamic acid solution was diluted by adding 4.7 g of N, N-dimethylacetamide, and then the mixture was stirred for 1 hour. After applying the obtained polyamic acid solution on a glass plate, it is heated at 150 ° C. for 1 hour and 250 ° C. for 1 hour to form an amine-derived structural unit represented by the above formula (1-1), 4, 4'. A polyimide thin film containing a constituent unit derived from -DPE and a constituent unit derived from ODPA in the main chain was obtained. The film thickness of the thin film was about 28 μm.

<Example 11>
(Production of polyimide containing an amine represented by the above formula (1-2), 4,4'-DPE, and a structural unit derived from ODPA in the main chain)
1.00 g (2.39 mmol) of amine represented by the above formula (1-2) and 0.48 g (2.39 mmol) of 4,4′-DPE obtained in Example 4 were dehydrated N, N-dimethylacetamide 7 Dissolved in 30 g. Then, 1.48 g (4.78 mmol) of ODPA was slowly added and reacted at room temperature for 16 hours, and the constituent unit derived from amine represented by the above formula (1-2), the constituent unit derived from 4,4'-DPE, And a polyamic acid containing a constituent unit derived from OPDA in the main chain was synthesized. The weight average molecular weight (Mw) of the polyamic acid was 287,493.

Then, the polyamic acid solution was diluted by adding 4.50 g of N, N-dimethylacetamide, and then stirred for 1 hour. After applying the obtained polyamic acid solution on a glass plate, it is heated at 150 ° C. for 1 hour and 250 ° C. for 1 hour to form an amine-derived structural unit represented by the above formula (1-2), 4, 4'. A polyimide thin film containing a constituent unit derived from -DPE and a constituent unit derived from OPDA in the main chain was obtained. The film thickness of the thin film was about 28 μm.

<Example 12>
(Production of polyimide containing an amine represented by the above formula (1-3), 4,4'-DPE, and a structural unit derived from ODPA in the main chain)
1.00 g (2.39 mmol) of amine represented by the above formula (1-3) and 0.48 g (2.39 mmol) of 4,4′-DPE obtained in Example 6 were dehydrated N, N-dimethylacetamide 7 Dissolved in 30 g. Then, 1.48 g (4.78 mmol) of ODPA was slowly added and reacted at room temperature for 16 hours, and the constituent unit derived from amine represented by the above formula (1-3), the constituent unit derived from 4,4'-DPE, And a polyamic acid containing a constituent unit derived from OPDA in the main chain was synthesized. The weight average molecular weight (Mw) of the polyamic acid was 140,899.

Then, the polyamic acid solution was diluted by adding 4.50 g of N, N-dimethylacetamide, and then stirred for 1 hour. After applying the obtained polyamic acid solution on a glass plate, it is heated at 150 ° C. for 1 hour and 250 ° C. for 1 hour to form an amine-derived structural unit represented by the above formula (1-3), 4, 4'. A polyimide thin film containing a constituent unit derived from -DPE and a constituent unit derived from OPDA in the main chain was obtained. The film thickness of the thin film was about 24 μm.

<Comparative example 2>
(Manufacture of polyimide containing constituent units derived from DAF, 4,4'-DPE, and ODPA in the main chain)
After dissolving 0.50 g (2.55 mmol) of DAF and 0.51 g (2.55 mmol) of 4,4'-DPE in 6.40 g of dehydrated N, N-dimethylacetamide, 1.58 g (5.10 mmol) of ODPA is slowly added. Then, the reaction was carried out at room temperature for 16 hours to synthesize a polyamic acid having a DAF-derived constituent unit, a 4,4'-DPE-derived constituent unit, and an ODPA-derived constituent unit in the main chain. The weight average molecular weight (Mw) of the polyamic acid was 366,237.

Then, the polyamic acid solution was diluted by adding 4.00 g of N, N-dimethylacetamide, and then the mixture was stirred for 1 hour. After applying the obtained polyamic acid solution on a glass plate, it is heated at 150 ° C. for 1 hour and 250 ° C. for 1 hour to obtain DAF-derived constituent units, 4,4'-DPE-derived constituent units, and ODPA-derived constituent units. A polyimide thin film containing a constituent unit in the main chain was obtained. The film thickness of the thin film was about 24 μm.

<Example 13>
(Manufacture of a polyimide containing an amine represented by the above formula (1-1) and a structural unit derived from BTDA in the main chain)
1.00 g (2.56 mmol) of the amine represented by the above formula (1-1) obtained in Example 2 was dissolved in 4.50 g of dehydrated N, N-dimethylacetamide. Next, 0.83 g (2.56 mmol) of BTDA is slowly added and reacted at room temperature for 16 hours to contain the amine-derived structural unit represented by the above formula (1-1) and the BTDA-derived structural unit in the main chain. Polyamic acid was synthesized. The weight average molecular weight (Mw) of the polyamic acid was 47,595.

Then, the polyamic acid solution was diluted by adding 2.80 g of N, N-dimethylacetamide, and then stirred for 1 hour. After applying the obtained polyamic acid solution on a glass plate, it is heated at 150 ° C. for 1 hour and 250 ° C. for 1 hour to form an amine-derived structural unit represented by the above formula (1-1) and BTDA-derived. A polyimide thin film containing a constituent unit in the main chain was obtained. The film thickness of the thin film was about 25 μm.

<Example 14>
(Manufacture of a polyimide containing an amine represented by the above formula (1-2) and a structural unit derived from BTDA in the main chain)
After dissolving 1.00 g (2.39 mmol) of the amine represented by the above formula (1-2) obtained in Example 4 in 4.40 g of dehydrated N, N-dimethylacetamide, 0.77 g of BTDA (2. 39 mmol) was slowly added and reacted at room temperature for 16 hours to synthesize a polyamic acid having an amine-derived structural unit represented by the above formula (1-2) and a BTDA-derived structural unit in the main chain. The weight average molecular weight (Mw) of the polyamic acid was 85,643.

Then, the polyamic acid solution was diluted by adding 2.70 g of N, N-dimethylacetamide, and then the mixture was stirred for 1 hour. After applying the obtained polyamic acid solution on a glass plate, it is heated at 150 ° C. for 1 hour and 250 ° C. for 1 hour to form an amine-derived structural unit represented by the above formula (1-2), and a BTDA-derived component. A polyimide thin film containing a constituent unit in the main chain was obtained. The film thickness of the thin film was about 27 μm.

<Example 15>
(Manufacture of a polyimide containing an amine represented by the above formula (1-3) and a structural unit derived from BTDA in the main chain)
After dissolving 1.00 g (2.39 mmol) of the amine represented by the above formula (1-3) obtained in Example 6 in 4.40 g of dehydrated N, N-dimethylacetamide, 0.77 g of BTDA (2. 39 mmol) was slowly added and reacted at room temperature for 16 hours to synthesize a polyamic acid having an amine-derived structural unit represented by the above formula (1-3) and a BTDA-derived structural unit in the main chain. The weight average molecular weight (Mw) of the polyamic acid was 149,432.

Then, the polyamic acid solution was diluted by adding 2.70 g of N, N-dimethylacetamide, and then the mixture was stirred for 1 hour. After applying the obtained polyamic acid solution on a glass plate, it is heated at 150 ° C. for 1 hour and 250 ° C. for 1 hour to form an amine-derived structural unit represented by the above formula (1-3) and BTDA-derived. A polyimide thin film containing a constituent unit in the main chain was obtained. The film thickness of the thin film was about 23 μm.

<Comparative example 3>
(Manufacture of polyimide containing DAF and BTDA-derived structural units in the main chain)
After dissolving 1.00 g (5.10 mmol) of DAF in 6.50 g of dehydrated N, N-dimethylacetamide, 1.64 g (5.10 mmol) of BTDA was slowly added and reacted at room temperature for 16 hours to form a constituent unit derived from DAF. And a polyamic acid containing a constituent unit derived from BTDA in the main chain was synthesized. The weight average molecular weight (Mw) of the polyamic acid was 64,690.

Then, 4.1 g of N, N-dimethylacetamide was added to dilute the polyamic acid solution, and the mixture was stirred for 1 hour. After applying the obtained polyamic acid solution on a glass plate, it is heated at 150 ° C. for 1 hour and 250 ° C. for 1 hour to form a polyimide thin film containing a DAF-derived structural unit and a BTDA-derived structural unit in the main chain. Obtained. The film thickness of the thin film was about 23 μm.

<Example 16>
(Amine represented by the above formula (1-1), 2,2'-bis (trifluoromethyl) benzidine (hereinafter referred to as TFMB) and 1,2,3,4-cyclobutanetetracarboxylic acid 1,2: Production of polyimide containing a structural unit derived from 3,4-dianhydride (hereinafter, also referred to as CBDA) in the main chain)
1.00 g (2.56 mmol) of amine represented by the above formula (1-1) and 0.82 g (2.56 mmol) of TFMB obtained in Example 2 were dissolved in 6.60 g of dehydrated N, N-dimethylacetamide. bottom. Then, 1.00 g (5.10 mmol) of CBDA was slowly added and reacted at room temperature for 24 hours to synthesize a polyamic acid. The weight average molecular weight (Mw) of the polyamic acid was 132,685.

Then, after diluting the polyamic acid solution by adding 47.1 g of N, N-dimethylacetamide, a mixed solution of 2.61 g (25.61 mmol) of acetic anhydride and 1.01 g (12.80 mmol) of pyridine was added. The mixture was added slowly at room temperature and stirred at room temperature for 24 hours. The obtained polyimide solution was added to a large amount of methanol to form a precipitate. The obtained precipitate was thoroughly washed with methanol and vacuum dried at 80 ° C. to obtain a white polyimide powder.
The obtained polyimide powder was dissolved in N, N-dimethylacetamide so that the powder concentration became a solution of 5% by weight at room temperature to prepare a polyimide solution. The obtained polyimide solution was applied onto a glass plate and then heated at 150 ° C. for 1 hour and 250 ° C. for 1 hour to obtain a polyimide thin film. The film thickness of the thin film was about 25 μm.

<Comparative example 4>
(Manufacture of polyimide containing structural units derived from DAF, TFMB and CBDA in the main chain)
After dissolving 0.50 g (2.55 mmol) of DAF and 0.82 g (2.56 mmol) of TFMB in 5.70 g of dehydrated N, N-dimethylacetamide, 1.00 g (5.10 mmol) of CBDA was slowly added to 16 at room temperature. After a time reaction, a polyamic acid containing a DAF-derived constituent unit, a TFMB-derived constituent unit, and a CBDA-derived constituent unit in the main chain was synthesized. The weight average molecular weight (Mw) of the polyamic acid was 231 and 372.

Then, the polyamic acid solution was diluted by adding 3.60 g of N, N-dimethylacetamide, and then the mixture was stirred for 1 hour. After applying the obtained polyamic acid solution on a glass plate, the main chain is heated at 150 ° C. for 1 hour and 250 ° C. for 1 hour to form a DAF-derived structural unit, a TFMB-derived structural unit, and a CBDA-derived structural unit. A thin film of polyimide contained in was obtained. The film thickness of the thin film was about 24 μm.

<Physical characteristics of the polyimides produced in Examples 7 to 16 and Comparative Examples 1 to 4>
Table 1 below shows the measurement results of each physical property value measured according to the above method.

Claims (8)

A polyimide having a constituent unit derived from amines represented by the following general formula (1) and a constituent unit derived from acid dianhydride in the main chain.

(In the above general formula (1), R ₁ and R ₂ may independently have an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxyl group, and a substituent having 4 to 12 carbon atoms, respectively. It represents a group or an aromatic group which may have a substituent having 6 to 12 carbon atoms, and m and n represent an integer of 0 to _{4. When a plurality of R 1} and / or R ₂ are present, Each may be the same or different.) The polyimide according to claim 1, which has a repeating unit represented by the following general formula (P-1).

(In the above general formula (P-1), R ₁ and R ₂ and m and n are as described above. X ₁ represents a tetravalent aliphatic group.) The polyimide according to claim 1 or 2, further having a repeating unit represented by the following general formula (P-2).

(In the above general formula (P-2), X ₁ is as described above, and X ₂ is a divalent aromatic group having a fluorine atom.) The following general formula (P-2):

(In the above general formula (P-2), X ₁ and X ₂ are as described above.)
In, _{X 2} is represented by the following general formula (P-3):

(In the above general formula (P-3), * represents the coupling position.)
The polyimide according to claim 3, which is an aromatic group represented by. The following general formula (1):

(In the above general formula (1), R ₁ and R ₂ may independently have an alkyl group having 1 to 12 carbon atoms, a halogen atom, a hydroxyl group, and a substituent having 4 to 12 carbon atoms, respectively. It represents a group or an aromatic group which may have a substituent having 6 to 12 carbon atoms, and m and n represent an integer of 0 to _{4. When a plurality of R 1} and / or R ₂ are present, Each may be the same or different.)
A polyamic acid having a constituent unit derived from amines represented by and a constituent unit derived from acid dianhydride in the main chain. A polyimide solution containing the polyimide according to any one of claims 1 to 4 and an organic solvent. A polyimide film containing the polyimide according to any one of claims 1 to 4. A plastic substrate material containing the polyimide according to any one of claims 1 to 4.

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