TW201531526A - Polyimide precursor and resin composition containing same - Google Patents

Abstract

The present invention is related to a polyimide precursor, which is characterized in containing the structure derived from 2,2'-bis (trifluoromethyl) benzidine to be used as the diamine structure, the structure derived from the specific alicyclic tetracarboxylic dianhydride and the structure of aromatic tetracarboxylic dianhydride to be used as the structure of tetracarboxylic dianhydride, wherein the imidization rate of the amide bond derived from the above-mentioned alicyclic tetracarboxylic dianhydride is 10~100%.

Description

Polyimine precursor and resin composition containing the same

The present invention relates to a polyimide precursor and a resin composition containing the same. The polyimine precursor can be used, for example, as a substrate for a flexible device.

The present invention also provides a polyimide film, a method for producing the same, and a laminate and a method for producing the same.

In general, the polyimide film comprises a film of a polyimide resin. Polyimide resin is a high heat resistant resin produced by solution polymerization of an aromatic tetracarboxylic dianhydride and an aromatic diamine to produce a polyimide precursor, followed by thermal imidization or chemical hydrazine imidization. . The above thermal sulfiliation is carried out by closed-loop dehydration at a high temperature, and the above chemical ruthenium is carried out by ring-closing dehydration using a catalyst.

The polyimide resin is an insoluble and non-fusible super heat resistant resin, and has excellent properties such as heat resistance, heat resistance, radiation resistance, low temperature resistance, and chemical resistance. Therefore, the polyimide resin is used for, for example, an insulating coating agent, an insulating film, a semiconductor, an electrode protective film of a TFT-LCD (Thin Film Transistor-Liquid Crystal Display), and the like, including an electronic material. A wide range of areas. Recently, it has also been used for display materials such as liquid crystal alignment films, optical fibers, and the like.

However, the polyimide resin is colored brown or yellow due to its higher aromatic ring density, so that the transmittance in the visible light region is low, and thus it is difficult to use in the field requiring transparency.

In this regard, Patent Document 1 reports that it has been manufactured to have specific use by use. A novel structure of polyimine which has a structure of tetracarboxylic dianhydride and a diamine to improve transparency and hue transparency.

Further, in Patent Document 2 and Patent Document 3, a polyimide film having an alicyclic structure introduced to impart transparency is disclosed.

Further, in Patent Document 4, it is reported that a specific degree of yellowness can be obtained by using a specific aromatic tetracarboxylic dianhydride and an alicyclic tetracarboxylic dianhydride as a tetracarboxylic dianhydride (hereinafter, also referred to as "YI value". ") Lower polyimine resin.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-198843

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2005-336243

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2003-155342

[Patent Document 4] Korean Patent Publication No. 10-2013-0077946

However, the mechanical properties and thermal properties of the polyimide disclosed in Patent Document 1 are not sufficient for use as, for example, a semiconductor insulating film, a TFT-LCD insulating film, an electrode protective film, and a flexible display substrate.

In particular, the polyimine disclosed in Patent Document 1 is characterized by a high coefficient of linear expansion (hereinafter also referred to as "CTE"). Regarding the resin having a higher CTE, when it is used as a film, the degree of expansion and contraction of the film caused by the temperature change is increased. Therefore, when a film having a high CTE is used in, for example, a TFT step, damage to the inorganic film as a device material is caused, resulting in a decrease in device capability. Therefore, the polyimide film used for forming the TFT substrate, the color filter substrate, the alignment film, and the transparent substrate for a flexible display must be colorless and transparent, and have a low CTE.

Further, the polyimine disclosed in Patent Document 2 has the following disadvantages: although it is transparent Sex, but the CTE is higher, and the elongation at break is lower. When the elongation at break is low, when the flexible device is operated, the flexible substrate is damaged, and thus it cannot be used as a device.

In the case of the polyimine disclosed in Patent Document 3, toughness is imparted by using a polycyclic aromatic diamine. However, since the polyethylenimine has a high CTE, it is not suitable as a semiconductor insulating film, a TFT-LCD insulating film, an electrode protective film or a flexible display substrate.

Further, in the case of the polyimine disclosed in Patent Document 4, the YI value is indeed low. However, the inventors of the present invention have studied that the CTE is high and the elongation is small, so that there is room for improvement in application to the display process (see Comparative Examples 22 to 24 below).

The present invention has been developed in view of the above-described problems, and an object thereof is to provide a polyimine precursor which can produce a polyimide film which is colorless and transparent, has a low CTE and excellent elongation, and a resin composition containing the same. And a polyimide film, a method for producing the same, and a laminate and a method for producing the same.

The inventors of the present invention have diligently studied and repeated experiments in order to solve the above problems. As a result, it was found that the resin composition (varnish) containing the polyimine precursor of a specific structure is excellent in storage stability; the polyimide film obtained by hardening the composition has excellent transparency and low linear expansion coefficient. And a high elongation; and a laminate having an inorganic film formed on the polyimide film, which has a small Haze and excellent water vapor transmission rate, and has completed the present invention based on these findings.

That is, the present invention is as follows.

[1] A polyimine precursor having a structure represented by the following formula (A) and having a structure derived from a diamine derived from 2,2'-bis (three) Fluoromethyl)benzidine (TFMB), 2,2'-dimethylbiphenyl-4,4'-diamine, 4,4'-diaminobenzoquinone and 4-aminobenzoic acid 4- The structure of at least one diamine in the aminophenyl ester derived from the structure derived from tetracarboxylic dianhydride derived from 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), 1, 2,4,5-cyclohexanetetracarboxylic dianhydride (H-PMDA), 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-bicyclohexane tetracarboxylic acid Acid dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid 2,3:5,6-dianhydride, bicyclo[2.2.2]oct-7-ene-2,3 ,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentaacetic acid-1,4:2,3-dianhydride, 1,3,3a,4,5,9b-hexahydro-5 -(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]furan-1,3-dione and bicyclo[3,3,0]octane-2 a structure of at least one alicyclic tetracarboxylic dianhydride of 4,6,8-tetracarboxylic dianhydride, and a structure derived from an aromatic tetracarboxylic dianhydride, and derived from the above alicyclic tetracarboxylic acid The imidization ratio of the guanamine bond of dianhydride is 10~100%

{X ₁ is derived from 2,2'-bis(trifluoromethyl)benzidine (TFMB), 2,2'-dimethylbiphenyl-4,4'-diamine, 4,4'- a structure of at least one diamine of diaminophenylbenzophenone and 4-aminophenyl 4-aminobenzoate; X ₂ is derived from a 1,2,3,4-cyclobutanetetracarboxylic acid Desic anhydride (CBDA), 1,2,4,5-cyclohexanetetracarboxylic dianhydride (H-PMDA), 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4 , 5-bicyclohexanetetracarboxylic dianhydride, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid 2,3:5,6-dianhydride, bicyclo[2.2.2] octane -7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentaacetic acid-1,4:2,3-dianhydride, 1,3,3a,4, 5,9b-hexahydro-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]furan-1,3-dione and bicyclo[3, 3,0] Structure of at least one tetracarboxylic dianhydride of octane-2,4,6,8-tetracarboxylic dianhydride}.

[2] The polyimine precursor according to [1], wherein the polyimine precursor has a structure of the following formula (B),

{X ₁ is the same as in the above formula (A), and X ₃ is a structure derived from the above aromatic tetracarboxylic dianhydride}.

[3] The polyimine precursor of [1] or [2], wherein the guanidine linkage derived from the alicyclic bond of the alicyclic tetracarboxylic dianhydride is from 20 to 100%.

[4] The polyimine precursor of any one of [1] to [3], wherein the guanidinium linkage derived from the alicyclic bond of the alicyclic tetracarboxylic dianhydride is from 30 to 100%.

[5] The polyiminamide precursor according to any one of [1] to [4] wherein the aromatic tetracarboxylic dianhydride comprises, as the aromatic tetracarboxylic dianhydride 1, a pyromellitic acid At least one of anhydride (PMDA) and 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 4,4'-oxydi-phthalic acid as aromatic tetracarboxylic dianhydride 2 At least one of formic acid dianhydride (ODPA), 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and 4,4'-biphenylbis(trimellitic acid monoester anhydride) One.

[6] The polyiminamide precursor according to any one of [1] to [5] wherein the above aromatic tetracarboxylic acid Acid dianhydride 1 is pyromellitic dianhydride (PMDA).

[7] The polyimine precursor of any one of [1] to [5] wherein the aromatic tetracarboxylic dianhydride 2 is selected from the group consisting of 4,4'-oxydiphthalic dianhydride ( At least one of ODPA) and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA).

[8] The polyimine precursor of any one of [1] to [7] wherein the structure derived from the diamine is derived from 2,2'-bis(trifluoromethyl)benzidine (TFMB) ) structure.

[9] The polyimine precursor of any one of [1] to [8] wherein the alicyclic tetracarboxylic dianhydride is selected from 1,2,3,4-cyclobutanetetracarboxylic acid Desic anhydride (CBDA), 1,2,4,5-cyclohexanetetracarboxylic dianhydride (H-PMDA), 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4 , 5-bicyclohexane tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid 2,3:5,6-dianhydride and bicyclo [2.2.2] octane At least one of -7-ene-2,3,5,6-tetracarboxylic dianhydride.

[10] The polyiminamide precursor according to any one of [1] to [9] wherein the alicyclic tetracarboxylic dianhydride is selected from 1,2,3,4-cyclobutanetetracarboxylic acid At least one of dianhydride (CBDA) and 1,2,4,5-cyclohexanetetracarboxylic dianhydride (H-PMDA).

[11] The polyimine precursor according to any one of [1] to [10], which comprises a structure derived from the above TFMB in a total of 60 mol% or more of the structure derived from the diamine, comprising At least one tetracarboxylic dianhydride derived from the above PMDA, the above ODPA, the above 6FDA, the above CBDA, and the above H-PMDA in a total of 60 mol% or more of the total structure derived from the tetracarboxylic dianhydride The structure.

[12] The polyimine precursor according to any one of [1] to [11], which comprises from 1 to 70 mol% of the total structure derived from tetracarboxylic dianhydride derived from the above PMDA The structure is composed of a structure derived from at least one tetracarboxylic dianhydride selected from the above ODPA and 6FDA, which accounts for 1 to 50 mol% of the total structure derived from tetracarboxylic dianhydride.

[13] The polyimine precursor of any one of [1] to [11], wherein the molar number of the structure derived from the above PMDA, the above ODPA, the above 6FDA, the above CBDA, and the above H-PMDA The ratio of the sum to the molar number derived from the structure of the above TFMB {PMDA+ODPA+6FDA+CBDA+H-PMDA)/TFMB} is 100/99.9 to 100/95.

[14] The polyimine precursor of any one of [1] to [13], which is obtained by dissolving in a solvent and developing on the surface of the support, and then performing imidization by heating under a nitrogen atmosphere. The polyimide film has a yellowness of 10 or less, a linear expansion coefficient of 25 ppm or less, and an elongation of the film of 15% or more at a film thickness of 20 μm.

[15] The polyimine precursor of any one of [1] to [14], which is used in the manufacture of a flexible device.

[16] A resin composition comprising the polyimine precursor of any one of [1] to [15] and a solvent.

[17] The resin composition according to [16], which further contains an alkoxydecane compound.

[18] The resin composition according to [16] or [17] which further contains a surfactant.

[19] A polyimide film according to any one of [16] to [18], which is developed on a surface of a support to form a coating film, and then the support and the above The coating film is heated to form the polyimine imide precursor by hydrazine imidization.

[20] A method for producing a polyimide film, comprising: a coating film forming step of forming a resin composition according to any one of [16] to [18] on a surface of a support. a coating film; a heating step of heating the support and the coating film to imidize the polyimine precursor to form a polyimide film; and a peeling step of the polyimine The film was peeled off from the above support to obtain a polyimide film.

[21] A laminate comprising: a support and a polyimide film formed on the support, and The laminated system is formed by laminating a resin composition according to any one of [16] to [18] on the surface of the support to form a coating film, and then heating the support and the coating film to form the polyimine The precursor is obtained by ruthenium imidization to form a polyimide film.

[22] A method for producing a laminate comprising a support and a polyimide film formed on the support, the method comprising: a coating film forming step of expanding on a surface of the support a resin composition according to any one of [16] to [18], wherein a coating film is formed; and a heating step of heating the support and the coating film to imidize the polyimine precursor A polyimide film is formed.

[23] A polyimine film, which is produced by a copolymer of a diamine and a tetracarboxylic dianhydride, wherein the diamine is selected from 2,2'-bis(trifluoromethyl). Benzidine (TFMB), 2,2'-dimethylbiphenyl-4,4'-diamine, 4,4'-diaminobenzophenidine and 4-aminophenyl 4-aminobenzoate In at least one of the above, the above tetracarboxylic dianhydride comprises, as an alicyclic tetracarboxylic dianhydride, 2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), 1,2,4,5- Cyclohexane tetracarboxylic dianhydride (H-PMDA), 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-bicyclohexanetetracarboxylic dianhydride, bicyclo [ 2.2.1] heptane-2,3,5,6-tetracarboxylic acid 2,3:5,6-dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetra Carboxylic dianhydride, 2,3,5-tricarboxycyclopentaacetic acid-1,4:2,3-dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2 ,5-di-oxy-3-furanyl)-naphtho[1,2-c]furan-1,3-dione and bicyclo[3,3,0]octane-2,4,6,8 At least one of tetracarboxylic dianhydrides selected from the group consisting of pyromellitic dianhydride (PMDA) and 3,3',4,4'-biphenyltetracarboxylic dianhydride as aromatic tetracarboxylic dianhydride 1 At least one of them, and 4,4'-oxydi-orthobenzene selected from aromatic tetracarboxylic dianhydride 2 Acid dianhydride (ODPA), 4,4 '- (hexafluoro isopropylidene) diphthalic anhydride (6FDA) and 4,4'-bis At least one of (trimellitic acid monoester anhydride), and an inorganic film is formed on the polyimine film by a CVD method at 350 ° C, and the surface of the inorganic film is measured by atomic force microscopy (AFM) The surface roughness is 0.01 to 50 nm.

[24] The polyimine film according to [23], wherein the above diamine is 2,2'-bis(trifluoromethyl)benzidine (TFMB), and the above tetracarboxylic dianhydride is contained as an alicyclic tetracarboxylic acid. The acid dianhydride is at least one selected from the group consisting of 2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) and 1,2,4,5-cyclohexanetetracarboxylic dianhydride (H-PMDA). As the aromatic tetracarboxylic dianhydride 1, at least one selected from the group consisting of pyromellitic dianhydride (PMDA) and 3,3',4,4'-biphenyltetracarboxylic dianhydride, and as an aromatic tetracarboxylic acid The acid dianhydride 2 is at least one selected from the group consisting of 4,4'-oxydiphthalic dianhydride (ODPA) and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA). .

[25] A flexible device comprising a polyimine film such as [23] or [24].

[26] A method of producing a flexible device comprising the method for producing a polyimide film according to [20].

[27] A method of producing a flexible device comprising the method of producing a laminate according to [22].

The resin composition (varnish) containing the polyimine precursor of the present invention is excellent in storage stability. Further, the polyimide film obtained from the composition is colorless and transparent, has a low coefficient of linear expansion, and is excellent in elongation. The laminate having an inorganic film formed on the polyimide film has a small Haze and excellent water vapor transmission rate.

Hereinafter, an embodiment (hereinafter, simply referred to as "the embodiment") of the present invention will be described in detail. The present invention is not limited to the embodiments described below, and various modifications can be made without departing from the spirit and scope of the invention.

<Polyimine precursor>

The polyimine precursor of the present embodiment is characterized by having a structure represented by the following formula (A) and having a structure derived from a diamine derived from 2,2'-bis(trifluoro) Methyl)benzidine (TFMB), 2,2'-dimethylbiphenyl-4,4'-diamine and 4,4'-diaminobenzoquinone, 4-aminobenzoic acid 4-amine The structure of at least one diamine in the phenyl ester is derived from a structure derived from tetracarboxylic dianhydride derived from 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), 1,2 , 4,5-cyclohexanetetracarboxylic dianhydride (H-PMDA), 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-bicyclohexanetetracarboxylic acid Dihydride, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid 2,3:5,6-dianhydride, bicyclo[2.2.2]oct-7-ene-2,3, 5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentaacetic acid-1,4:2,3-dianhydride, 1,3,3a,4,5,9b-hexahydro-5- (tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]furan-1,3-dione and bicyclo[3,3,0]octane-2, a structure of at least one alicyclic tetracarboxylic dianhydride of 4,6,8-tetracarboxylic dianhydride, and a structure derived from an aromatic tetracarboxylic dianhydride, and derived from the above alicyclic tetracarboxylic acid The hydrazine imidization ratio of the anhydride amine bond is 10~10 0%,

{X ₁ is derived from 2,2'-bis(trifluoromethyl)benzidine (TFMB), 2,2'-dimethylbiphenyl-4,4'-diamine, 4,4'- a structure of at least one diamine of diaminophenylbenzophenone and 4-aminophenyl 4-aminobenzoate; X ₂ is derived from a 1,2,3,4-cyclobutanetetracarboxylic acid Desic anhydride (CBDA), 1,2,4,5-cyclohexanetetracarboxylic dianhydride (H-PMDA), 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4 , 5-bicyclohexanetetracarboxylic dianhydride, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid 2,3:5,6-dianhydride, bicyclo[2.2.2] octane -7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentaacetic acid-1,4:2,3-dianhydride, 1,3,3a,4, 5,9b-hexahydro-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]furan-1,3-dione and bicyclo[3, 3,0] Structure of at least one tetracarboxylic dianhydride of octane-2,4,6,8-tetracarboxylic dianhydride}.

Preferably, the polyimine precursor of the present embodiment has a structure of the following formula (B).

{X ₁ is the same as the above formula (A), and X ₃ is a structure derived from the above aromatic tetracarboxylic dianhydride}.

Further, as described above, the polyimine precursor of the present embodiment has a ruthenium imidization ratio of from 10 to 100% by the indole bond of the alicyclic tetracarboxylic dianhydride. That is, it is derived from at least a part of the guanidine imidized ruthenium imine polyamine of the alicyclic bond of the alicyclic tetracarboxylic dianhydride.

In order to obtain a ruthenium imidized polyamine structure derived from a hydrazine imine bond of an alicyclic tetracarboxylic dianhydride, for example, the following method may be employed: First, an alicyclic tetracarboxylic dianhydride is carried out. After obtaining the polyamine acid by the reaction of the diamine, or obtaining the poly-proline acid, the indoleamine bond of the poly-proline is subjected to hydrazylation, and then the other tetracarboxylic dianhydride is continued. In the case of this embodiment, it is aroma The reaction of a tetracarboxylic dianhydride with a diamine.

From the viewpoint of increasing the molecular weight of the polyimine precursor and improving the transparency of the obtained polyimide film, it is preferred to first react the alicyclic tetracarboxylic dianhydride. Further, in order to increase the molecular weight of the polyimine (precursor) having a structure derived from an alicyclic tetracarboxylic dianhydride, it is necessary to increase the synthesis temperature of usually 60 to 100 ° C to 150 to 210 ° C. By thus increasing the synthesis temperature, the result is a ruthenium imidization derived from the indole bond of the alicyclic tetracarboxylic dianhydride, thereby causing the concentration of the quinone imine group derived from the alicyclic acid dianhydride (醯亚The amination rate) increases. Here, the alicyclic tetracarboxylic acid is derived from the viewpoint of the storage stability of the composition (varnish) containing the polyimide precursor, and the elongation of the obtained polyimide film and YI. The imidization ratio of the guanamine bond of the anhydride is preferably from 10 to 100%, more preferably from 20 to 100%, still more preferably from 30 to 100%.

The reason why the alicyclic tetracarboxylic dianhydride is first reacted is to add an alicyclic tetracarboxylic dianhydride and an aromatic tetracarboxylic dianhydride, or to add an alicyclic ring after adding an aromatic tetracarboxylic dianhydride. When a tetracarboxylic dianhydride is synthesized at a temperature of 150 to 210 ° C, it causes a strong imidization of a guanamine bond derived from a portion of an aromatic tetracarboxylic dianhydride, resulting in a polymer. It is not suitable because it is precipitated.

The detailed synthesis method of the polyimine precursor in the present embodiment will be described below.

Hereinafter, each structure will be described in detail.

<Structure derived from tetracarboxylic dianhydride>

The polyimine precursor of the present embodiment has a structure derived from tetracarboxylic dianhydride derived from 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), 1, 2, 4,5-cyclohexanetetracarboxylic dianhydride (H-PMDA), 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-bicyclohexanetetracarboxylic acid Anhydride, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid 2,3:5,6-dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5 ,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentaacetic acid-1,4:2,3-dianhydride, 1,3,3a,4,5,9b-hexahydro-5-( Tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]furan- a structure of at least one tetracarboxylic dianhydride of 1,3-diketone and bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride, and derived from aromatic tetracarboxylic acid The structure of acid dianhydride.

Here, as the alicyclic tetracarboxylic dianhydride, it is preferably selected from 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) and 1,2,4,5-cyclohexane. Tetracarboxylic dianhydride (H-PMDA), 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-bicyclohexanetetracarboxylic dianhydride, bicyclo [2.2.1 Heptane-2,3,5,6-tetracarboxylic acid 2,3:5,6-dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid Anhydride, 2,3,5-tricarboxycyclopentaacetic acid-1,4:2,3-dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5- Bis-oxy-3-furanyl)-naphtho[1,2-c]furan-1,3-dione and bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylate At least one of acid dianhydrides. Among them, from the viewpoint of the CTE of the obtained polyimide film, it is preferably selected from the group consisting of CBDA, H-PMDA, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2, 4,5-bicyclohexanetetracarboxylic dianhydride, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid 2,3:5,6-dianhydride and bicyclo [2.2.2] At least one of oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, and more preferably in terms of cost and YI and transparency of the obtained polyimide film At least one selected from the group consisting of CBDA and H-PMDA is further preferably H-PMDA from the viewpoint of cost.

The above 1,2,4,5-cyclohexanetetracarboxylic dianhydride (H-PMDA) may be the following formula (1) to (3)

Any one of the isomers represented by each may be a mixture containing two or more of these.

The aromatic tetracarboxylic dianhydride preferably contains, as the aromatic tetracarboxylic dianhydride 1, pyromellitic dianhydride (PMDA) and 3,3',4,4'-biphenyltetracarboxylic acid. At least one of dianhydrides and 4,4'-oxydiphthalic dianhydride (ODPA), 4,4'-(hexafluoroisopropylidene) as aromatic tetracarboxylic dianhydride 2 At least one of diphthalic anhydride (6FDA) and 4,4'-biphenyl bis(trimellitic acid monoester anhydride).

Here, the aromatic tetracarboxylic dianhydride 1 is mainly used to contribute to improvement of thermal properties, mechanical properties, and the like of the obtained polyimide film, and the aromatic tetracarboxylic dianhydride 2 is useful. It is used by improving the transparency and the like of the polyimide film.

As the aromatic tetracarboxylic dianhydride 1, it is more preferable to use PMDA from the viewpoint of the CTE of the obtained polyimide film.

As the aromatic tetracarboxylic dianhydride 2, from the viewpoint of YI and transparency of the obtained polyimide film, it is more preferable to use at least one selected from the group consisting of ODPA and 6FDA, and it is a polyimide film. From the viewpoint of CTE, it is further preferred to use 6FDA.

The polyimine precursor of the present embodiment preferably has a structure derived from the above alicyclic tetracarboxylic dianhydride in an amount of from 5 to 60 mol% based on the total structure derived from the tetracarboxylic dianhydride. 40 to 95% by mole of the structure derived from the aromatic tetracarboxylic dianhydride in all of the structures derived from the tetracarboxylic dianhydride; more preferably A structure derived from the above alicyclic tetracarboxylic dianhydride in an amount of from 5 to 60 mol% based on all of the structure derived from tetracarboxylic dianhydride, having a structure derived from all of the tetracarboxylic dianhydride 20 to 80 mol% of the structure derived from the above aromatic tetracarboxylic dianhydride 1 having 5 to 60 mol% of the total structure derived from the tetracarboxylic dianhydride derived from the above aromatic tetra The structure of carboxylic acid dianhydride 2.

Further, it is preferable that the polyimine precursor of the present embodiment contains 60 or more moles of the total of the structure derived from the tetracarboxylic dianhydride, and is derived from the above-mentioned PMDA, the above ODPA, the above 6FDA, and the above. The structure of at least one tetracarboxylic dianhydride of CBDA and the above H-PMDA.

Further, from the viewpoint of obtaining a preferable yellowness, CTE and breaking strength of the polyimide film, it is particularly preferable to have 1 to 70 mol% of the structure derived from all of the tetracarboxylic dianhydride. a structure derived from pyromellitic dianhydride (PMDA) having a content of from 1 to 50 mol% in a structure derived entirely from tetracarboxylic dianhydride derived from 4,4'-oxydi-phthalene A structure of at least one of formic acid dianhydride (ODPA) and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA).

<Structure derived from diamine>

The polyimine precursor of the present embodiment has a structure derived from a diamine derived from 2,2'-bis(trifluoromethyl)benzidine (TFMB), 2,2'-dimethyl linking. A structure of at least one diamine of benzene-4,4'-diamine, 4,4'-diaminobenzoquinone and 4-aminophenyl 4-aminobenzoate. Among them, from the viewpoint of YI and transparency of the obtained polyimide film, TFMB is preferred.

More preferably, it is a structure derived from the above TFMB, which accounts for 60 mol% or more of the total diamine-derived structure.

<The ratio of the structure derived from tetracarboxylic dianhydride to the structure derived from diamine>

Regarding the ratio of the sum of the molar numbers of the structure derived from the tetracarboxylic dianhydride to the sum of the molar numbers of the structure derived from the diamine, the viewpoint of the transparency, thermal properties and mechanical properties of the polyimide film In terms of, it is preferably from 100/99.9 to 100/95. More specifically, the ratio of the sum of the molar numbers of the structures derived from each of PMDA, ODPA, 6FDA, CBDA, and H-PMDA to the molar number of the structure derived from TFMB {(PMDA+ODPA+6FDA+CBDA) +H-PMDA)/TFMB} is preferably from 100/99.9 to 100/95 from the viewpoint of obtaining a polyimide film having a better yellowness, CTE and breaking strength.

<weight average molecular weight of polyimine precursor>

The weight average molecular weight of the polyimide precursor of the present embodiment is preferably 5,000 or more and 1,000,000 or less, more preferably 50,000 or more and 500,000 or less, and still more preferably 70,000 or more and 250,000 or less. When the weight average molecular weight is 5,000 or more, the obtained polyethyleneimine film has a high elongation and mechanical properties. Particularly, from the viewpoint of obtaining low CTE and low yellowness (YI value), the molecular weight is more preferably 50,000 or more. By making the weight average molecular weight Mw 1,000,000 or less, the resin composition containing the polyimide precursor can be non-permeablely coated to a desired film thickness.

Here, the weight average molecular weight means the sum of the values obtained by multiplying the molecular weight of each molecule by the molecular mass thereof by the molecular weight distribution measured by gel permeation chromatography using monodisperse polystyrene as a standard. The value obtained from the total mass of the molecule.

<Synthesis method of polyimine precursor>

The polyimine precursor of the present embodiment can be reacted by dissolving the tetracarboxylic dianhydride component and the diamine component in a solvent, and in the form of a solution containing a polyimide precursor and a solvent. Manufacturing. The conditions at the time of the reaction are not particularly limited, and examples thereof include a reaction temperature of -20 to 250 ° C and a reaction time of 2 to 48 hours. The ambient gas atmosphere during the reaction is preferably an inert gas atmosphere such as argon or nitrogen.

The solvent is not particularly limited as long as it is a solvent capable of dissolving the produced polymer. As a known reaction solvent, for example, it is useful to select m-cresol, N-methyl-2-pyridyl Roridone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl hydrazine (DMSO), acetone, diethyl acetate, Equamide M100 (trade name: light One or more polar solvents in the production of Equamide B100 (trade name: manufactured by Idemitsu Kosan Co., Ltd.). Among them, one or more selected from the group consisting of NMP, DMAc, Equamide M100, and Equamide B100 are preferred. Further, instead of the above solvent, a low boiling point solvent such as tetrahydrofuran (THF) or chloroform or a low absorption solvent such as γ-butyrolactone may be used together with the above solvent.

The at least a portion of the indoleamine bond derived from the alicyclic tetracarboxylic dianhydride of the polyamidene precursor system polyamine is subjected to ring closure dehydration of the ruthenium imine polyamine.

The step of subjecting the indoleamine bond to ring-opening dehydration is not particularly limited, and a known method can be applied. For example, thermal hydrazylation or chemical hydrazylation can be employed.

More specifically, the heat imidization can be carried out, for example, by the following method. First, the diamine is dissolved and/or dispersed in a suitable polymerization solvent, tetracarboxylic dianhydride is added thereto, and a solvent (for example, toluene or the like) which azeotropes with water is added. Then, using a mechanical stirrer, the side-generated water is azeotropically removed and heated and stirred for 0.5 to 96 hours, preferably 0.5 to 30 hours. The heating temperature is preferably more than 100 ° C and not more than 250 ° C, preferably from 130 to 230 ° C, more preferably from 150 to 210 ° C. In this case, the monomer concentration is preferably 0.5% by mass or more and 95% by mass or less, more preferably 1% by mass or more and 90% by mass or less.

The chemical imidization can be carried out using a known ruthenium imidization catalyst. The ruthenium imidization catalyst is not particularly limited, and examples thereof include acid anhydrides such as acetic anhydride; γ-valerolactone, γ-butyrolactone, γ-tero window acid, γ-decalactone, and γ- a lactone compound such as coumarin or γ-caprolactone; a tertiary amine such as pyridine, quinoline, N-methylmorpholine or triethylamine. The ruthenium-based catalyst may be used singly or in combination of two or more. Among them, a mixed system of γ-valerolactone and pyridine is particularly preferable from the viewpoint of high reactivity.

The amount of the ruthenium-imiding catalyst to be added is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less based on 100 parts by mass of the polyamic acid.

The closed-loop dehydration of the indoleamine bond is preferably carried out by thermal hydrazyl imidization without a catalyst from the viewpoint of minimizing the influence of the subsequent reaction.

The polyimine precursor of the present embodiment is preferably synthesized by the following method: First, a reaction of an alicyclic tetracarboxylic dianhydride with a diamine is carried out under the conditions of the above thermal hydrazylation to obtain a The ruthenium imidized polyamine acid is then additionally added with an aromatic tetracarboxylic dianhydride and a diamine, and it is preferred to continue the reaction at 100 ° C or lower.

As described above, a solution containing a polyimide precursor can be obtained.

The solution may be directly supplied to the preparation of the resin composition, or may be subjected to isolation and purification of the polyimine precursor contained in the solution for the preparation of the resin composition.

<Other additives>

The resin composition of the present embodiment contains the polyimine precursor described above and a solvent, and may further contain other additives as needed.

Examples of such other additives include alkoxydecane compounds, surfactants, leveling agents, and the like.

(alkoxydecane compound)

When the polyimine obtained by the resin composition of the present embodiment forms an element such as a TFT, the resin composition may contain a polyimide precursor 100 in order to sufficiently adhere the adhesion to the support. The alkoxydecane compound having a mass % of 0.001 to 2% by mass.

The content of the alkoxydecane compound in an amount of 100% by mass based on the polyimine precursor is 0.01% by mass or more, whereby good adhesion to the support can be obtained. Moreover, from the viewpoint of storage stability of the resin composition, the content of the alkoxydecane compound is preferably 2% by mass or less. The content of the alkoxydecane compound is preferably higher than that of the polyimide precursor It is 0.02 to 2% by mass, more preferably 0.05 to 1% by mass, still more preferably 0.05 to 0.5% by mass, still more preferably 0.1 to 0.5% by mass.

Examples of the alkoxydecane compound include 3-mercaptopropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name KBM803, manufactured by Chisso Co., Ltd.: trade name Sila-Ace S810), 3-mercaptopropyl propyl Triethoxy decane (manufactured by Azmax Co., Ltd.: trade name SIM6475.0), 3-mercaptopropylmethyldimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS1375, manufactured by Azmax Co., Ltd. : trade name SIM6474.0), mercaptomethyltrimethoxydecane (manufactured by Azmax Co., Ltd.: trade name SIM6473.5C), mercaptomethylmethyldimethoxydecane (manufactured by Azmax Co., Ltd.: trade name SIM6473. 0), 3-mercaptopropyldiethoxymethoxydecane, 3-mercaptopropylethoxydimethoxydecane, 3-mercaptopropyltripropoxydecane, 3-mercaptopropyldiethoxylate Propyloxydecane, 3-mercaptopropylethoxydipropoxydecane, 3-mercaptopropyldimethoxypropoxydecane, 3-mercaptopropylmethoxydipropoxydecane, 2- Mercaptoethyltrimethoxydecane, 2-mercaptoethyldiethoxymethoxydecane 2-mercaptoethylethoxydimethoxydecane, 2-mercaptoethyltripropoxydecane, 2-mercaptoethyltripropoxydecane, 2-mercaptoethylethoxydipropoxydecane, 2-mercaptoethyldimethoxypropoxydecane, 2-mercaptoethylmethoxydipropoxydecane, 4-mercaptobutyltrimethoxydecane, 4-mercaptobutyltriethoxydecane, 4 - mercaptobutyl tripropoxydecane, N-(3-triethoxydecylpropyl)urea (manufactured by Shin-Etsu Chemical Co., Ltd.: trade name LS3610, manufactured by Azmax Co., Ltd.: trade name SIU9055.0) N-(3-trimethoxydecylpropyl)urea (manufactured by Azmax Co., Ltd.: trade name SIU9058.0), N-(3-diethoxymethoxydecylpropyl)urea, N- (3-ethoxydimethoxydecylpropyl)urea, N-(3-tripropoxydecylpropyl)urea, N-(3-diethoxypropoxydecylpropyl) Urea, N-(3-ethoxydipropoxydecylpropyl)urea, N-(3-dimethoxypropoxydecylpropyl)urea, N-(3-methoxydipropyl) Oxidylalkylpropyl)urea, N-(3-trimethoxydecylethyl)urea, N-(3-ethoxydimethoxy Alkylethyl)urea, N-(3-tripropoxydecylethyl)urea, N-(3-tripropoxydecylethyl)urea, N-(3-ethoxydipropyl Oxidylalkylethyl)urea, N-(3-dimethoxypropoxydecylethyl)urea, N-(3-methoxydipropoxydecylethyl)urea, N-( 3-trimethoxydecylbutyl)urea, N-(3-triethoxydecylbutyl)urea, N-(3-tripropoxydecylbutyl)urea, 3-(m-amino group) Phenoxy)propyltrimethoxydecane (manufactured by Azmax Co., Ltd.: trade name SLA0598.0), m-aminophenyltrimethoxydecane (manufactured by Azmax Co., Ltd.: trade name SLA0599.0), and amino group Phenyltrimethoxydecane (manufactured by Azmax Co., Ltd.: trade name SLA0599.1), aminophenyltrimethoxydecane (manufactured by Azmax Co., Ltd.: trade name SLA0599.2), 2-(trimethoxydecylalkyl) Ethyl)pyridine (manufactured by Azmax Co., Ltd.: trade name SIT8396.0), 2-(triethoxydecylethylethyl)pyridine, 2-(dimethoxydecylmethylethyl)pyridine, 2- (diethoxydecylmethylethyl)pyridine, (3-triethoxydecylpropyl)-t-butylamino Ester, (3-glycidoxypropyl) triethoxy decane, tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, tetra-isopropoxy decane, tetra-n-butyl Oxydecane, tetra-isobutoxydecane, tetra-t-butoxydecane, tetrakis(methoxyethoxydecane), tetrakis(methoxy-n-propoxydecane), tetra(ethoxy) Ethoxy decane), tetrakis(methoxyethoxyethoxy decane), bis(trimethoxydecyl)ethane, bis(trimethoxydecyl)hexane, bis(triethoxydecylalkyl) Methane, bis(triethoxydecyl)ethane, bis(triethoxydecyl)ethylene, bis(triethoxydecyl)octane, bis(triethoxydecyl)octadiene , bis[3-(triethoxydecyl)propyl]disulfide, bis[3-(triethoxydecyl)propyl]tetrasulfide, di-t-butoxydiethyloxy Base decane, di-isobutoxyaluminum triethoxy decane, bis(glutarate) titanium-O, O'-bis(oxyethyl)-aminopropyltriethoxy decane, Phenyl decane triol, methyl phenyl decane diol, ethyl phenyl decane diol, n-propyl phenyl decane diol, isopropyl phenyl decane , n-butylphenyl decane diol, isobutyl phenyl decane diol, tert-butyl phenyl decane diol, diphenyl decane diol, dimethoxy diphenyl decane, diethoxy bis Phenyl decane, dimethoxy bis-p-tolyl decane, B Methyl phenyl decyl alcohol, n-propyl methyl phenyl stanol, isopropyl methyl phenyl stanol, n-butyl methyl phenyl stanol, isobutyl methyl phenyl stanol, third butyl methyl phenyl Hydranol, ethyl n-propyl phenyl decyl alcohol, ethyl isopropyl phenyl stanol, n-butyl ethyl phenyl stanol, isobutyl ethyl phenyl stanol, tert-butyl ethyl benzene Base alkanol, methyl diphenyl stanol, ethyl diphenyl stanol, n-propyl diphenyl stanol, isopropyl diphenyl stanol, n-butyl diphenyl stanol, isobutyl Diphenyl decyl alcohol, tert-butyl diphenyl decyl alcohol, triphenyl decyl alcohol, 3-ureidopropyl triethoxy decane, bis (2-hydroxyethyl)-3-aminopropyl three Ethoxy decane, 3-glycidoxypropyl trimethoxy decane, phenyl trimethoxy decane, γ-aminopropyl triethoxy decane, γ-aminopropyl trimethoxy decane, γ- Aminopropyl tripropoxydecane, γ-aminopropyl tributoxy decane, γ-aminoethyl triethoxy decane, γ-aminoethyl trimethoxy decane, γ-amino group B Tripropoxy Alkane, γ-aminoethyl tributoxydecane, γ-aminobutyl triethoxy decane, γ-aminobutyl trimethoxy decane, γ-aminobutyl tripropoxy decane, γ - aminobutyl tributoxy decane, etc., but is not limited to these. These may be used alone or in combination of plural kinds.

As the decane coupling agent, among the above decane coupling agents, from the viewpoint of ensuring storage stability of the resin composition, it is preferably selected from the group consisting of phenyldecanetriol, trimethoxyphenylnonane, and trimethoxy (pair). Tolyl) decane, diphenyl decane diol, dimethoxy diphenyl decane, diethoxy diphenyl decane, dimethoxy bis-p-tolyl decane, triphenyl decyl alcohol and the following structure One or more of the decane coupling agents represented by each.

(surfactant or leveling agent)

Further, by adding a surfactant or a leveling agent to the resin composition, the coatability can be improved. Specifically, shrinkage after coating can be prevented.

As such a surfactant or leveling agent, for example, an organic siloxane polymer KF-640, 642, 643, KP341, X-70-092, X-70-093, KBM303, KBM403, KBM803 (above, Trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (above, trade name, manufactured by Dow Corning Toray Silicone) , SILWET L-77, L-7001, FZ-2105, FZ-2120, FZ-2154, FZ-2164, FZ-2166, L-7604 (above, trade name, manufactured by Nippon Unicar) , DBE-814, DBE-224, DBE-621, CMS-626, CMS-222, KF-352A, KF-354L, KF-355A, KF-6020, DBE-821, DBE-712 (Gelest), BYK- 307, BYK-310, BYK-378, BYK-333 (above, trade name, manufactured by BYK-Chemie Japan), Glanol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), as polyoxyethylene lauryl ether, polyoxyethylene hard Megafacs F171, F173, R-08, such as aliphatic ether, polyoxyethylene ether ether, polyoxyethylene octylphenol ether, etc., manufactured by Dainippon Ink Chemical Industry Co., Ltd. Manufacture, trade name), Fluorad FC430, FC431 (Sumitomo 3M Co., Ltd., trade name).

In the case of using a surfactant or a leveling agent, the total amount thereof is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 3 parts by mass based on 100 parts by mass of the polyimine precursor in the resin composition. Share.

<Resin composition>

The resin composition of the present embodiment is used as a solution composition (varnish) obtained by dissolving the above-mentioned polyimine precursor and other components used arbitrarily in a solvent.

Here, as the solvent, the same solvent as that which has been used as a solvent for synthesizing a polyimide precursor can be used.

The amount of the solvent used is preferably such that the solid content concentration of the resin composition is from 3 to 50% by mass.

The varnish of the resin composition of the present embodiment is excellent in room temperature storage stability, and the viscosity change rate of the varnish when stored at room temperature for 4 weeks is 10% or less with respect to the initial viscosity. If it is excellent in storage stability at room temperature, it does not need to be stored frozen, so it is easy to handle.

<Laminated body>

The laminate of the present embodiment includes a support and a polyimide film formed on the support. Further, the laminate may further include an inorganic film on the polyimide film.

The laminated body is formed by a coating film forming step of developing the resin composition of the present embodiment on the surface of the support to form a coating film, and a heating step of performing the support and the coating film The polyimine precursor is subjected to hydrazine imidization by heating to form a polyimide film.

The inorganic film is used as a gas barrier layer for preventing penetration of moisture or oxygen from the polyimide film of the present invention into an organic EL (electroluminescence) light-emitting layer or the like, and is preferably exemplified by cerium oxide or aluminum oxide. Tantalum carbide, oxidized tantalum carbide, tantalum carbide, An inorganic oxide film such as tantalum nitride or tantalum oxide. This inorganic film is formed by a plasma CVD method (Chemical Vapor Deposition) or the like.

The support is, for example, an inorganic substrate such as a glass substrate such as an alkali-free glass substrate, but is not particularly limited.

As the development method, for example, a known coating method such as spin coating, slit coating, or doctor blade coating can be mentioned.

More specifically, the resin composition is developed on the support (or formed on the adhesive layer on the main surface thereof), and after removing the solvent, it is preferred to heat the polyimide precursor in an inert gas atmosphere. The ruthenium imidization is carried out, whereby a polyimide film can be formed on the above support.

The solvent removal can be carried out, for example, by heat treatment at a temperature of not more than 250 ° C, preferably 50 to 200 ° C for 1 minute to 300 minutes. The above hydrazine imidation can be carried out, for example, by heat treatment at a temperature of from 250 ° C to 550 ° C for from 1 minute to 300 minutes. The ambient gas atmosphere during the imidization of hydrazine is preferably an inert gas atmosphere such as nitrogen.

The thickness of the polyimide film obtained by the present embodiment is not particularly limited, but is preferably in the range of 10 to 50 μm, more preferably 15 to 25 μm.

This laminate is used, for example, to manufacture a flexible device. More specifically, a semiconductor device is formed on the polyimide film, and thereafter, the support is peeled off to obtain a flexible device including a flexible transparent substrate including a polyimide film.

<Polyimide film>

The polyimide film of the present embodiment is formed by a coating film forming step of developing a resin composition containing the polyimine precursor of the present embodiment and a solvent on the surface of the support. Forming a coating film; heating step of heating the support and the coating film to imidize the polyimine precursor to form a polyimide film; and a stripping step of the polyazide The amine film is peeled off from the support to obtain polyfluorene Imine film.

The polyimide film is used, for example, to manufacture a flexible device. Specifically, the polyimide film can be used for a substrate on which a TFT is formed, a substrate on which a color filter is formed, an alignment film, a transparent substrate for a flexible display, or the like.

<Advantages of the Invention>

As described above, the polyimine precursor of the present embodiment preferably has (1) at least one alicyclic ring derived from CBDA, H-PMDA or the like as a structure derived from tetracarboxylic dianhydride. a structure of a tetracarboxylic dianhydride; a structure derived from an aromatic tetracarboxylic dianhydride 1 selected from PMDA or the like; and a structure derived from an aromatic tetracarboxylic dianhydride selected from OPDA, 6FDA, etc.; (2) A structure derived from TFMB or the like as a structure derived from a diamine. The polyimide film produced by using such a polyimide precursor is colorless and transparent, has a low CTE, and is excellent in elongation. The laminate formed by forming an inorganic film on the polyimide film has a small surface roughness, a small Haze value, and a small water vapor transmission rate, and is therefore suitable for use in a transparent substrate of a flexible display.

Specifically, the details are as follows.

In the case of forming a flexible display, a glass substrate is used as a support, a flexible substrate is formed thereon, and an inorganic film such as a TFT is formed thereon. The step of forming the inorganic film on the substrate is typically carried out at a temperature ranging from 150 to 650 °C. In order to achieve the actual performance required, the temperature range of 250 ° C to 400 ° C is mainly used. Examples of the inorganic film include a TFT-IGZO (InGaZnO) oxide semiconductor, a TFT (a-Si-TFT, a poly-Si-TFT), and the like.

At this time, if the CTE of the flexible substrate is higher than the CTE of the glass substrate, the shrinkage occurs during cooling after expansion in the high-temperature inorganic film forming step, and warpage, breakage, and flexibility of the glass substrate occur at this time. Problems such as peeling of the substrate from the glass substrate. Usually, the glass substrate The coefficient of thermal expansion is smaller than that of the resin. Therefore, the lower the linear expansion coefficient of the flexible substrate, the better.

In the polyimine film of the present embodiment, in consideration of the above aspect, the average line measured by the TMA method (thermomechanical analysis) at 100 to 300 ° C can be used based on the thickness of the film of 15 to 25 μm. The coefficient of expansion (CTE) is set to 25.0 ppm/° C. or less.

Further, in the polyimide film of the present embodiment, the yellowness (YI value) is 10 or less, and the thickness of the film is 15 to 25 μm, and the transmittance can be measured by the ultraviolet spectrophotometer at 550 nm. The transmittance is set to 85% or more.

In the laminate in which the inorganic film is formed on the polyimide film of the present embodiment, the surface roughness of the inorganic film is small, the Haze value is small, and the water vapor transmission rate is small.

In the case of an organic EL display, an inorganic film is formed on the polyimide film as a gas barrier layer. At this time, if the surface roughness of the inorganic film is large and the Haze value is large, turbidity and stains are caused in the laminated body, and thus it is not suitable for use as a display. Moreover, if the water vapor transmission rate is large, the function as a gas barrier layer cannot be exhibited, and it is not suitable.

It is considered that the heat resistance of the polyimide film is related to the surface roughness, the Haze value, and the water vapor transmission rate of the laminate. The reason for this is that when an inorganic film is formed by a CVD method on a polyimide film, the laminate containing the polyimide film is exposed to a temperature higher than the temperature at which the polyimide film is formed. High temperature. The laminate preferably has a surface roughness of 25 nm or less, Haze of 15 or less, and a water vapor transmission rate of 0.1 g/(m ² ‧24 h) or less.

Further, the polyimide film of the present embodiment preferably has an elongation of 15% or more based on the thickness of the film of 15 to 25 μm. By having such an elongation, the breaking strength is excellent when the flexible substrate is operated, so that the yield can be improved.

The polyimide film of the present embodiment which satisfies the above physical properties can be used for applications in which the yellow color of the polyimide film is known to be limited, and the use of transparency is required. In particular, in addition to being preferably used as a transparent substrate for a flexible display; For example, it can also be used for a diffusing film and a coating film (for example, an intermediate layer of a TFT-LCD, a gate insulating film, and a liquid crystal alignment film) in a protective film or a TFT-LCD. When the polyimine of this embodiment is used as a liquid crystal alignment film, a TFT-LCD which contributes to an increase in aperture ratio and a high contrast ratio can be manufactured.

The polyimide film and the laminate produced by using the polyimide precursor of the present embodiment can be preferably used, for example, for producing a semiconductor insulating film, a TFT-LCD insulating film, an electrode protective film, and a flexible device. In particular, it is suitable for manufacturing substrates. Here, examples of the flexible device include a flexible display, a flexible solar cell, a flexible illumination, and a flexible battery.

[Examples]

Hereinafter, the present invention will be specifically described based on examples. These are described for the sake of explanation, and the scope of the present invention is not limited to the following examples.

The various evaluations in the examples and comparative examples were carried out as follows.

(Measurement of weight average molecular weight)

The weight average molecular weight was measured by gel permeation chromatography (GPC) under the following conditions. A calibration curve for calculating the weight average molecular weight was produced using standard polystyrene (manufactured by Tosoh Corporation).

Solvent: N,N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., for high-speed liquid chromatography) was added, and 24.8 mmol/L of lithium bromide monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added before the measurement. 99.5% purity) and 63.2 mmol/L phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd., for high-speed liquid chromatography)

Pipe column: Shodex KD-806M (made by Showa Denko)

Flow rate: 1.0mL/min

Column temperature: 40 ° C

Pump: PU-2080Plus (manufactured by JASCO)

Detector: RI-2031Plus (RI: differential refractometer, manufactured by JASCO), UV- 2075Plus (UV-VIS: UV-visible absorbometer, manufactured by JASCO)

(calculation of the concentration of the quinone imine group derived from the portion of the alicyclic tetracarboxylic dianhydride)

The concentration of the quinone imine group derived from the alicyclic acid dianhydride was calculated from the integral value of the ¹³ C-NMR (Nuclear Magnetic Resonance) signal measured on the polyimide precursor varnish. ^{The 13} C-NMR measurement was carried out under the following conditions.

Measuring device: JNM-GSX400 manufactured by JEOL

Measuring temperature: 23 ° C

Determination of solvent: deuterated dimethyl hydrazine solvent (DMSO-d ₆ )

The signal system of each of the quinone imine bond, the guanamine bond, and the carboxylic acid derived from the alicyclic tetracarboxylic dianhydride is represented by the following magnetic field strength: The signal of the quinone imine bonded carbon derived from the part of the alicyclic tetracarboxylic dianhydride: near 177 ppm (A)

The signal of the amine-bonded carbon derived from the part of the alicyclic tetracarboxylic dianhydride: near 172 ppm (B)

The signal of the carboxyl group derived from the part of the alicyclic tetracarboxylic dianhydride: near 177 ppm (C)

Here, the integral value of B and C is the same value with respect to the proline (not ruthenium) site. The integral value of the yttrium-immobilized carbon in the site of the ruthenium imidization and the integral value of the guanamine-bonded carbon in the site where the oxime imidization is carried out are represented by the following formula: 醯imino bond The integral value of carbon: the integral value of A - the integral value of B

Integral value of guanamine bonded carbon and carboxyl carbon: integral value of B × 2

Thereby, the quinone imine group concentration is represented by the following formula: 醯imino group concentration (%) = 100 × (integral value of A - integral value of B) / (integral value of A - integral value of B + The integral value of B × 2) = 100 × (the integral value of A - the integral value of B) / (the integral value of A + the integral value of B)

(Evaluation of varnish preservation stability)

The sample varnish prepared in each of the following examples and comparative examples was placed at room temperature for 3 days, and the sample was prepared, and the viscosity was measured at 23 ° C. Thereafter, the sample which was further left at room temperature for 4 weeks was set as a sample after 4 weeks, and the viscosity measurement at 23 ° C was again performed.

The viscosity measurement described above was carried out using a viscometer (TV-22 manufactured by Toki Sangyo Co., Ltd.) equipped with a thermostat.

Using the above measured values, the room temperature 4 week viscosity change rate was calculated by the following formula.

The change rate of viscosity at room temperature for 4 weeks (%) = [(viscosity of sample after 4 weeks) - (viscosity of sample after preparation)] / (viscosity of sample after preparation) × 100

The viscosity change rate at room temperature for 4 weeks was evaluated according to the following criteria. The results are shown in Table 2.

◎: The viscosity change rate is 5% or less (storage stability is "excellent")

○: The viscosity change rate is 10% or less (storage stability is "good")

×: The viscosity change rate is more than 10% (storage stability is "poor")

(Production of laminated body and single film)

The varnish of the polyimide precursor obtained in each of the examples and the comparative examples was coated on an alkali-free glass substrate (thickness: 0.7 mm) by a bar coater. Then, after leveling at room temperature for 5 minutes to 10 minutes, the film was heated at 140 ° C for 60 minutes in a hot air oven, and further heated at a predetermined temperature for 60 minutes in a nitrogen atmosphere to prepare a coating film on the substrate. Laminated body. The film thickness of the coating film in the laminate was set so that the film thickness after curing became 20 μm. Then, curing (hardening treatment) is carried out at a predetermined temperature to carry out oxime imidization of the coating film. After the cured laminate was allowed to stand at room temperature for 24 hours, the polyimide film was peeled off from the glass to thereby separate the film.

The polyimine film which was cured at a predetermined temperature was used as a sample in the evaluation of the breaking strength, yellowness, and coefficient of linear expansion below.

(Evaluation of elongation)

The width of curing at a specified temperature is 5 mm, length 50 mm, thickness 20 μm A sample of the polyimide film was subjected to tensile measurement at a speed of 100 mm/min using a tensile tester (manufactured by A&D Co., Ltd.: RTG-1210). The case where the breaking elongation was 20% or more was evaluated as ◎ (the elongation was "excellent"), and when 15% or more was less than 20%, it was evaluated as ○ (elongation "good"), and 10% or more was less than 15 The case of % was evaluated as Δ (elongation "bad"), and the case where it was less than 10% was evaluated as × (elongation "bad").

(Evaluation of yellowness (YI value))

The polyimine film having a thickness of 20 μm which was cured at a predetermined temperature was measured by a D65 light source manufactured by Nippon Denshoku Industries Co., Ltd. (Spectrophotometer: SE600). When the YI value was 8.0 or less, it was evaluated as ◎ (yellowness is "excellent"), and when it is more than 8.0 and 10.0 or less, it is evaluated as ○ (yellowness is "good"), and when it is more than 10.0 and 15.0 or less, it is evaluated as Δ ( The yellowness is "poor", and the case where it exceeds 15.0 is evaluated as × (yellowness is "bad").

(Evaluation of coefficient of linear expansion (CTE))

The polyimine film which was cured at a predetermined temperature was subjected to thermomechanical analysis using a thermomechanical analyzer (TMA-50) manufactured by Shimadzu Corporation, and the elongation of the test piece was measured under the following conditions.

Load: 5g

Heating rate: 10 ° C / min

Measuring gas environment: nitrogen environment

Nitrogen flow rate: 20ml/min

Measuring temperature range: 50~450°C

The CTE of the polyimine film in the temperature range of 100 to 300 ° C at this time was determined, and the case where the CTE was 20 ppm/° C. or less was evaluated as ◎ (CTE "excellent"), and it was more than 20 ppm/° C. and 25 ppm/° C. In the following cases, it was evaluated as ○ (CTE "good"), and when it was more than 25 ppm/°C and 30 ppm/°C or less, it was evaluated as Δ (CTE "poor"), and when it exceeded 30 ppm/°C, it was evaluated as × (CTE "bad" ).

(Measurement of surface roughness of inorganic film formed on polyimide film)

Using the composition varnish prepared in the above examples and comparative examples, a laminate of a polyimide film and an inorganic film was sequentially formed on a 6-inch wafer substrate having an aluminum vapor-deposited layer on the surface as described below. Body wafer.

First, each composition varnish was spin-coated on the above substrate, and then heated at 140 ° C for 60 minutes in a hot air oven, and further heated at 320 ° C for 60 minutes in a nitrogen atmosphere, thereby obtaining a polyfluorene having a film thickness of 20 μm. A film of an imide film.

Thereafter, on the polyimide film formed above, a tantalum nitride (SiN _x ) film as an inorganic film was formed by a CVD method at a thickness of 100 nm at 350 °C. Next, the surface roughness of the formed tantalum nitride was measured on a scale of 100 μm × 100 μm using Nanopics 2100 (manufactured by SII Nanotechnology Co., Ltd.) as an AFM (Atomic Force Microscopy). The test was carried out with N = 5, and the average value was obtained to set the surface roughness Ra.

The results are shown in Table 2.

(Haze's review)

The laminate wafer obtained above is immersed in a dilute hydrochloric acid aqueous solution, and the inorganic film and the polyimide film are peeled off from the wafer as a unit, thereby obtaining a polyimide film having an inorganic film formed on the surface thereof. A sample of the membrane. Using this sample, Haze was measured in accordance with the JIS K7105 transparency test method using an SC-3H type mist meter manufactured by Suga Test Machine Co., Ltd.

The measurement results were evaluated based on the following criteria.

◎: Haze is 5 or less (Haze "Excellent")

○: Haze is greater than 5 and 15 or less (Haze "good")

×: Haze is greater than 15 (Haze "bad")

The results are shown in Table 2.

(Evaluation of water vapor transmission rate)

For the water vapor transmission rate of the polyimide film having an inorganic film formed on the surface obtained above, a water vapor transmission rate measuring device manufactured by MOCON Co., Ltd. (model name: PERMATRAN (registered trademark) W3/31 was used. ), at a temperature of 40 ° C, a humidity of 90% RH and a measurement area of 80 mm The measurement was carried out under the conditions. The number of times of measurement was set to 5 times each, and the average value was set to the water vapor transmission rate, and it evaluated based on the following criteria.

◎: The water vapor transmission rate is 0.01 g/(m ² ‧24 h) or less (the water vapor transmission rate is "excellent")

○: The water vapor transmission rate is more than 0.01 g/(m ² ‧24 h) and 0.1 g/(m ² ‧24 h) or less (the water vapor transmission rate is "good")

×: The water vapor transmission rate is more than 0.1 g/(m ² ‧24 h) (the water vapor transmission rate is "poor")

The results are shown in Table 2.

[Reference Example 1]

2,2'-bis(trifluoromethyl)benzidine (TFMB) 15.69 g (49.00 mmol) and N-methyl-2-pyrrolidone (NMP) were placed in a 500 ml separable flask under a nitrogen atmosphere. 178.95 g, TFMB was dissolved under stirring. Thereafter, pyromellitic dianhydride (PMDA) 1.09 g (5.0 mmol), 4,4'-oxydiphthalic dianhydride (ODPA) 3.10 g (10.0 mmol) and 1,2,3,4 were added. - 6.68 g (35.0 mmol) of cyclobutane tetracarboxylic dianhydride (CBDA), and stirred at 80 ° C for 4 hours, thereby obtaining a polyacrylic acid NMP solution (hereinafter also referred to as "varnish"). The weight average molecular weight (Mw) of the obtained polyamic acid was 116,500. The CTE, YI value and elongation of the film cured at 330 ° C are shown in Table 2 below.

[Reference Example 2]

The feedstock was changed to TFMB 15.69 g (49.0 mmol), NMP 180.42 g, PMDA 3.27 g (15.0 mmol), ODPA 3.10 g (10.0 mmol), and CBDA 4.90 g (25.0 mmol), and the others were A varnish was obtained in the same manner as in Reference Example 1. The weight average molecular weight (Mw) of the obtained polyamic acid was 120,000. The CTE, YI value and elongation of the film cured at 330 ° C are shown in Table 2 below.

[Reference Example 3]

The feedstock was changed to TFMB 15.69 g (49.0 mmol), NMP 186.58 g, PMDA 1.09 g (5.00 mmol), ODPA 6.20 g (20.0 mmol), and CBDA 4.90 g (25.0 mmol), except for A varnish was obtained in the same manner as in Reference Example 1. The weight average molecular weight (Mw) of the obtained polyamic acid was 128,000. The CTE, YI value and elongation of the film cured at 330 ° C are shown in Table 2 below.

[Example 4]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 2.24 g (10.0 mmol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (H-PMDA) was added, and after refluxing at 180 ° C for 2 hours, it was removed as an azeotropic solvent for 3 hours. Toluene. Then, after cooling the contents of the flask to 40 ° C, 12.55 g (39.2 mmol) of TFMB, 16.43 g of NMP, 6.54 g (30.0 mmol) of PMDA, and 3.10 g (10.0 mmol) of ODPA were added, and the mixture was stirred at 80 ° C for 4 hours. A varnish of the polyimine-polyamide polymer was thus obtained. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 82,000. The CTE, YI value and elongation of the film which was cured at 350 ° C are shown in Table 2 below.

[Reference Example 5]

The feeding of the raw materials was changed to TFMB 15.69 g (49.0 mmol), NMP 178.14 g, PMDA 5.45 g (25.0 mmol), ODPA 1.55 g (5.0 mmol), and CBDA 3.92 g (20 mmol), and the rest was used for reference. A varnish was obtained in the same manner as in Example 1. The weight average molecular weight (Mw) of the obtained polyamic acid was 119,000. The CTE, YI value and elongation of the film cured at 330 ° C are shown in Table 2 below.

[Reference Example 6]

The feedstock was changed to TFMB 15.69 g (49.0 mmol), NMP 187.38 g, PMDA 2.18 g (10.0 mmol), ODPA 6.20 g (20.0 mmol), and CBDA 3.92 g (20.0 mmol), and the others were A varnish was obtained in the same manner as in Reference Example 1. Obtained The polyamine has a weight average molecular weight (Mw) of 123,000. The CTE, YI value and elongation of the film cured at 330 ° C are shown in Table 2 below.

[Reference Example 7]

The feedstock was changed to TFMB 15.69 g (49.0 mmol), NMP 175.19 g, PMDA 1.09 g (5.0 mmol), ODPA 1.55 g (5.0 mmol), and CBDA 7.84 g (40.0 mmol), except for A varnish was obtained in the same manner as in Reference Example 1. The weight average molecular weight (Mw) of the obtained polyamic acid was 123,000. The CTE, YI value and elongation of the film cured at 330 ° C are shown in Table 2 below.

[Reference Example 8]

The feeding of the raw materials was changed to TFMB 15.69 g (49.0 mmol), NMP 189.59 g, PMDA 5.45 g (25.0 mmol), ODPA 6.20 g (20.0 mmol), and CBDA 0.98 g (5.0 mmol), and the others were A varnish was obtained in the same manner as in Reference Example 1. The weight average molecular weight (Mw) of the obtained polyamic acid was 103,000. The CTE, YI value and elongation of the film cured at 330 ° C are shown in Table 2 below.

[Embodiment 9]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 2.24 g (10.0 mmol) of H-PMDA was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. After cooling the contents of the flask to 40 ° C, 12.55 g (39.2 mmol) of TFMB, 171.51 g of NMP, 5.45 g (25.0 mmol) of PMDA, and 4.65 g (15.0 mmol) of ODPA were added, and the mixture was stirred at 80 ° C for 4 hours. This gave a varnish of a polyamidene-polyaminic acid polymer. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 123,000. The CTE, YI value and elongation of the film which was cured at 350 ° C are shown in Table 2 below.

[Embodiment 10]

In a separable flask equipped with a Dean Stark unit and a reflux unit, in a nitrogen ring Under the conditions, TFMB 3.14 g (9.8 mmol), NMP 16.14 g and toluene 50 g were placed, and TFMB was dissolved under stirring. Here, 2.24 g (10.0 mmol) of H-PMDA was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. After cooling the contents of the flask to 40 ° C, 12.55 g (39.2 mmol) of TFMB, 174.59 g of NMP, 4.36 g (20.0 mmol) of PMDA, and 6.20 g (20.0 mmol) of ODPA were added, and the mixture was stirred at 80 ° C for 4 hours. This gave a varnish of a polyamidene-polyaminic acid polymer. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 81,000. The CTE, YI value and elongation of the film which was cured at 350 ° C are shown in Table 2 below.

[Example 11]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 6.28 g (19.6 mmol), NMP 32.28 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, H-PMDA 4.48 g (20.0 mmol) was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. After cooling the contents of the flask to 40 ° C, TFMB 9.42 g (29.4 mmol), NMP 76.44 g, PMDA 5.45 g (25.0 mmol) and ODPA 1.55 g (5.0 mmol) were added, and the mixture was stirred at 80 ° C for 4 hours. This gave a varnish of a polyamidene-polyaminic acid polymer. The obtained polyamidene-polyglycine polymerization composition had a weight average molecular weight (Mw) of 68,000. The CTE, YI value and elongation of the film which was cured at 350 ° C are shown in Table 2 below.

[Embodiment 12]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 6.28 g (19.6 mmol), NMP 32.28 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, H-PMDA 4.48 g (20.0 mmol) was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. After cooling the contents of the flask to 40 ° C, TFMB 9.42 g (29.4 mmol), NMP 78.28 g, PMDA 4.36 g (20.0 mmol) and ODPA 3.10 g (10.0 mmol) were added, and the mixture was stirred at 80 ° C for 4 hours. This gave a varnish of a polyamidene-polyaminic acid polymer. Polyimine obtained - The polyamine polymer had a weight average molecular weight (Mw) of 68,000. The CTE, YI value and elongation of the film which was cured at 350 ° C are shown in Table 2 below.

[Example 13]

In a separable flask equipped with a Dean Stark apparatus and a reflux apparatus, TFMB 0.63 g (1.96 mmol), NMP 3.22 g, and toluene 30 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 0.45 g (2.00 mmol) of H-PMDA was added, and the mixture was refluxed at 180 ° C for 2 hours, and then toluene as an azeotropic solvent was removed over 3 hours. After cooling the contents of the flask to 40 ° C, 15.06 g (47.0 mmol) of TFMB, 186.57 g of NMP, 6.33 g (29.0 mmol) of PMDA, and 5.89 g (19.0 mmol) of ODPA were added, and the mixture was stirred at 80 ° C for 4 hours. This gave a varnish of a polyamidene-polyaminic acid polymer. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 112,000. The CTE, YI value and elongation of the film which was cured at 350 ° C are shown in Table 2 below.

[Embodiment 14]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 2.24 g (10.0 mmol) of H-PMDA was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. After cooling the contents of the flask to 40 ° C, 12.55 g (39.2 mmol) of TFMB, 166.88 g of NMP, 7.09 g (32.5 mmol) of PMDA, and 2.33 g (7.5 mmol) of ODPA were added, and the mixture was stirred at 80 ° C for 4 hours. This gave a varnish of a polyamidene-polyaminic acid polymer. The obtained polyamidene-polyglycine polymerization composition had a weight average molecular weight (Mw) of 79,000. The CTE, YI value and elongation of the film which was cured at 350 ° C are shown in Table 2 below.

[Example 15]

In a separable flask equipped with a Dean Stark apparatus and a reflux apparatus, TFMB 9.42 g (29.4 mmol), NMP 48.42 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, H-PMDA 6.78g (30.0mmol) was added at 180 ° C After refluxing for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. After cooling the contents of the flask to 40 ° C, TFMB 6.28 g (19.6 mmol), NMP 60.54 g, PMDA 3.27 g (15.0 mmol) and ODPA 1.55 g (5.0 mmol) were added, and the mixture was stirred at 80 ° C for 4 hours. This gave a varnish of a polyamidene-polyaminic acid polymer. The obtained polyamidene-polyglycine polymerization composition had a weight average molecular weight (Mw) of 56,000. The CTE, YI value and elongation of the film which was cured at 350 ° C are shown in Table 2 below.

[Example 16]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.80 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 2.24 g (10.0 mmol) of H-PMDA was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. After cooling the contents of the flask to 40 ° C, 12.55 g (39.2 mmol) of TFMB, 16.43 g of NMP, 4.36 g (20.0 mmol) of PMDA, 3.10 g (10.0 mmol) of ODPA, and 1.96 g (10.0 mmol) of CBDA were added. The mixture was stirred at 80 ° C for 4 hours to obtain a varnish of a polyamidene-polyaminic acid polymer. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 71,000. The CTE, YI value and elongation of the film which was cured at 350 ° C are shown in Table 2 below.

[Reference Example 17]

The feedstock was changed to TFMB 15.69g (49.0mmol), NMP162.24g, PMDA6.54g (30.0mmol), 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) 4.44. A varnish was obtained in the same manner as in Reference Example 1, except that g (10.0 mmol) and CBDA 1.96 g (10 mmol) were used. The weight average molecular weight (Mw) of the obtained polyamic acid was 159,000. The CTE, YI value and elongation of the film cured at 330 ° C are shown in Table 2 below.

[Embodiment 18]

In a separable flask equipped with a Dean Stark unit and a reflux unit, in a nitrogen ring Under the conditions, TFMB 3.14 g (9.8 mmol), NMP 16.14 g and toluene 50 g were placed, and TFMB was dissolved under stirring. Here, 2.24 g (10.0 mmol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (H-PMDA) was added, and after refluxing at 180 ° C for 2 hours, it was removed as an azeotropic solvent for 3 hours. Toluene. After cooling the contents of the flask to 40 ° C, 12.55 g (39.2 mmol) of TFMB, 147.70 g of NMP, 6.54 g (30.0 mmol) of PMDA, and 4.44 g (10.0 mmol) of 6FDA were added, and the mixture was stirred at 80 ° C for 4 hours. This gave a varnish of a polyamidene-polyaminic acid polymer. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 85,000. The CTE, YI value and elongation of the film which was cured at 350 ° C are shown in Table 2 below.

[Embodiment 19]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 2.24 g (10.0 mmol) of H-PMDA was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. The contents of the flask were cooled to 40 ° C, and it was confirmed by infrared spectroscopic analysis (IR) that the absorption (C=O) near 1,650 cm ^-1 derived from the indole bond disappeared. Thereafter, 12.55 g (39.2 mmol) of TFMB, 153.4 g of NMP, 15.4 g (25.0 mmol) of PMDA, and 6.660 g (15.0 mmol) of 6FDA were added to the flask, and the mixture was stirred at 80 ° C for 4 hours to obtain a polyimine. - varnish of polyaminic acid polymer. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 88,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Example 20]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 2.24 g (10.0 mmol) of H-PMDA was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. The contents of the flask were cooled to 40 ° C, and it was confirmed by IR that the absorption (C=O) near 1,650 cm ^-1 derived from the indole bond disappeared. Thereafter, 12.55 g (39.2 mmol) of TFMB, 159.8 g of NMP, 4.36 g (20.0 mmol) of PMDA, and 8.FDA (80.0 mmol) of 6FDA were added, and the mixture was stirred at 80 ° C for 4 hours to obtain a polyimine-polyfluorene. A varnish of aminic acid polymer. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 86,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Example 21]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 6.28 g (19.6 mmol), NMP 32.28 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, H-PMDA 4.48 g (20.0 mmol) was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. The contents of the flask were cooled to 40 ° C, and it was confirmed by IR that the absorption (C=O) near 1,650 cm ^-1 derived from the indole bond disappeared. Thereafter, TFMB 9.42 g (29.4 mmol), NMP 124.9 g, PMDA 5.45 g (25.0 mmol), and 6FDA 2.22 g (5.0 mmol) were added, and the mixture was stirred at 80 ° C for 4 hours to obtain a polyimine-polyfluorene. A varnish of aminic acid polymer. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 76,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Example 22]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 6.28 g (19.6 mmol), NMP 32.28 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, H-PMDA 4.48 g (20.0 mmol) was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. The contents of the flask were cooled to 40 ° C, and it was confirmed by IR that the absorption (C=O) near 1,650 cm ^-1 derived from the indole bond disappeared. Thereafter, TFMB 9.42 g (29.4 mmol), NMP 131.3 g, PMDA 4.36 g (20.0 mmol), and 6FDA 4.44 g (10.0 mmol) were added, and the mixture was stirred at 80 ° C for 4 hours to obtain a polyimine-polyfluorene. A varnish of aminic acid polymer. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 77,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Example 23]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 0.45 g (2.00 mmol) of H-PMDA was added, and the mixture was refluxed at 180 ° C for 2 hours, and then toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ° C, and it was confirmed by IR that the absorption (C=O) near 1,650 cm ^-1 derived from the indole bond disappeared. Thereafter, 12.55 g (39.2 mmol) of TFMB, 158.3 g of NMP, 6.33 g (29.0 mmol) of PMDA, and 8.84 g (19.0 mmol) of 6FDA were added, and the mixture was stirred at 80 ° C for 4 hours to obtain a polyimine-polyfluorene. A varnish of aminic acid polymer. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 89,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Example 24]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 2.24 g (10.0 mmol) of H-PMDA was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. The contents of the flask were cooled to 40 ° C, and it was confirmed by IR that the absorption (C=O) in the vicinity of 1650 cm ^-1 derived from the indole bond disappeared. Thereafter, 12.55 g (39.2 mmol) of TFMB, 143.9 g of NMP, 7.09 g (32.5 mmol) of PMDA, and 3.33 g (7.5 mmol) of 6FDA were added, and the mixture was stirred at 80 ° C for 4 hours to obtain a polyimine-polyfluorene. A varnish of aminic acid polymer. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 89,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Example 25]

In a separable flask equipped with a Dean Stark apparatus and a reflux apparatus, TFMB 9.42 g (29.4 mmol), NMP 48.42 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, H-PMDA 6.78 g (30.0 mmol) was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. The contents of the flask were cooled to 40 ° C, and it was confirmed by IR that the absorption (C=O) near 1,650 cm ^-1 derived from the indole bond disappeared. Thereafter, TFMB 6.28 g (19.6 mmol), NMP 109.5 g, PMDA 3.27 g (15.0 mmol), and 6FDA 2.22 g (5.0 mmol) were added, and the mixture was stirred at 80 ° C for 4 hours to obtain a polyimine-polyfluorene. A varnish of aminic acid polymer. The obtained polyamidene-polyglycine polymer had a weight average molecular weight (Mw) of 75,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Example 26]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 2.24 g (10.0 mmol) of H-PMDA was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. The contents of the flask were cooled to 40 ° C, and it was confirmed by IR that the absorption (C=O) near 1,650 cm ^-1 derived from the indole bond disappeared. Thereafter, TFMB 12.55 g (39.2 mmol), NMP 153.5 g, PMDA 3.27 g (15.0 mmol), BPDA 4.41 g (15.0 mmol), and 6FDA 4.44 g (10.0 mmol) were added, and the mixture was stirred at 80 ° C for 4 hours. A varnish of a polyamidene-polyaminic acid polymer is obtained. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 87,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Example 27]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 2.24 g (10.0 mmol) of H-PMDA was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. The contents of the flask were cooled to 40 ° C, and it was confirmed by IR that the absorption (C=O) near 1,650 cm ^-1 derived from the indole bond disappeared. Thereafter, TFMB 12.55 g (39.2 mmol), NMP 143.3 g, PMDA 6.54 g (30.0 mmol), ODPA 1.55 g (5.0 mmol), and 6FDA 2.22 g (5.0 mmol) were added, and the mixture was stirred at 80 ° C for 4 hours. This gave a varnish of a polyamidene-polyaminic acid polymer. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 86,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Example 28]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, H-PMDA 1.12 g (5.0 mmol) and CBDA 0.98 g (5.0 mmol) were added, and the mixture was refluxed at 180 ° C for 2 hours, and then toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ° C, and it was confirmed by IR that the absorption (C=O) near 1,650 cm ^-1 derived from the indole bond disappeared. Thereafter, TFMB 12.55 g (39.2 mmol), NMP 146.3 g, PMDA 6.54 g (30.0 mmol), and 6FDA 4.44 g (10.0 mmol) were added, and the mixture was stirred at 80 ° C for 4 hours to obtain a polyimine-polyfluorene. A varnish of aminic acid polymer. The obtained polyimine-polyamide polymer had a weight average molecular weight (Mw) of 90,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Example 29]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 0.34 g (1.5 mmol) of H-PMDA was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. The contents of the flask were cooled to 40 ° C, and it was confirmed by IR that the absorption (C=O) near 1,650 cm ^-1 derived from the indole bond disappeared. Thereafter, 12.55 g (39.2 mmol) of TFMB, 147 g of NMP, 6.54 g (30.0 mmol) of PMDA, 4.44 g (10.0 mmol) of 6FDA, and 1.9 g (8.5 mmol) of H-PMDA were added, and the mixture was stirred at 80 ° C for 4 hours. A varnish of a polyamidene-polyaminic acid polymer is obtained. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 71,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Example 30]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 0.56 g (2.5 mmol) of H-PMDA was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. The contents of the flask were cooled to 40 ° C, and it was confirmed by IR that the absorption (C=O) near 1,650 cm ^-1 derived from the indole bond disappeared. Thereafter, 12.55 g (39.2 mmol) of TFMB, 147 g of NMP, 6.54 g (30.0 mmol) of PMDA, 4.44 g (10.0 mmol) of 6FDA, and 1.68 g (7.5 mmol) of H-PMDA were added, and the mixture was stirred at 80 ° C for 4 hours. A varnish of a polyamidene-polyaminic acid polymer is obtained. The obtained polyamidene-polyglycine polymer had a weight average molecular weight (Mw) of 75,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Example 31]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 0.78 g (3.5 mmol) of H-PMDA was added, and the mixture was refluxed at 180 ° C for 2 hours, and then toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ° C, and it was confirmed by IR that the absorption (C=O) near 1,650 cm ^-1 derived from the indole bond disappeared. Thereafter, 12.55 g (39.2 mmol) of TFMB, 147 g of NMP, 6.54 g (30.0 mmol) of PMDA, 4.44 g (10.0 mmol) of 6FDA, and 1.46 g (6.5 mmol) of H-PMDA were added, and the mixture was stirred at 80 ° C for 4 hours. A varnish of a polyamidene-polyaminic acid polymer is obtained. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 78,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Example 32]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 0.62 g (2.75 mmol) of H-PMDA was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. The contents of the flask were cooled to 40 ° C, and it was confirmed by IR that the absorption (C=O) near 1,650 cm ^-1 derived from the indole bond disappeared. Thereafter, TFMB 12.55 g (39.2 mmol), NMP 153.3 g, PMDA 6.54 g (30.0 mmol), 6FDA 6.66 g (15.0 mmol), and H-PMDA 0.5 g (2.25 mmol) were added, and the mixture was stirred at 80 ° C for 4 hours. A varnish of the polyimine-polyamide polymer was thus obtained. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 80,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Example 33]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 1.68 g (7.5 mmol) of H-PMDA was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. The contents of the flask were cooled to 40 ° C, and it was confirmed by IR that the absorption (C=O) near 1,650 cm ^-1 derived from the indole bond disappeared. Thereafter, 12.55 g (39.2 mmol) of TFMB, 160.1 g of NMP, 6.54 g (30.0 mmol) of PMDA, 2.12 g (5.0 mmol) of FDA, and 5.1 g (22.5 mmol) of H-PMDA were added, and the mixture was stirred at 80 ° C for 4 hours. A varnish of the polyimine-polyamide polymer was thus obtained. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 71,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Example 34]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, CBDA 1.96 g (10.0 mmol) was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. The contents of the flask were cooled to 40 ° C, and it was confirmed by IR that the absorption (C=O) near 1,650 cm ^-1 derived from the indole bond disappeared. Thereafter, 12.55 g (39.2 mmol) of TFMB, 166.5 g of NMP, 6.54 g (30.0 mmol) of PMDA, and 3.10 g (10.0 mmol) of ODPA were added, and the mixture was stirred at 80 ° C for 4 hours to obtain a polyimine-polyfluorene. A varnish of aminic acid polymer. The obtained polyamidene-polyaminic acid polymer had a weight average molecular weight (Mw) of 120,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Example 35]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 0.98 g (5.0 mmol) of CBDA was added, and the mixture was refluxed at 180 ° C for 2 hours, and then toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ° C, and it was confirmed by IR that the absorption (C=O) near 1,650 cm ^-1 derived from the indole bond disappeared. Thereafter, TFMB 12.55 g (39.2 mmol), NMP 191.3 g, PMDA 5.45 g (25.0 mmol), and 6FDA 8.88 g (20.0 mmol) were added, and the mixture was stirred at 80 ° C for 4 hours to obtain a polyimine-polyfluorene. A varnish of aminic acid polymer. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 95,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Example 36]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, CBDA 1.96 g (10.0 mmol) was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. The contents of the flask were cooled to 40 ° C, and it was confirmed by IR that the absorption (C=O) near 1,650 cm ^-1 derived from the indole bond disappeared. Thereafter, TFMB 12.55 g (39.2 mmol), NMP 175.5 g, PMDA 6.54 g (30.0 mmol), and 6FDA 4.44 g (10.0 mmol) were added, and the mixture was stirred at 80 ° C for 4 hours to obtain a polyimine-polyfluorene. A varnish of aminic acid polymer. The obtained polyamidene-polyamide polymer had a weight average molecular weight (Mw) of 100,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Example 37]

In a separable flask equipped with a Dean Stark apparatus and a reflux apparatus, TFMB 9.42 g (29.4 mmol), NMP 48.42 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 5.88 g (30.0 mmol) of CBDA was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. The contents of the flask were cooled to 40 ° C, and it was confirmed by IR that the absorption (C=O) near 1,650 cm ^-1 derived from the indole bond disappeared. Thereafter, TFMB 6.28 g (19.6 mmol), NMP 169.5 g, PMDA 6.54 g (30.0 mmol), and 6FDA 4.44 g (10.0 mmol) were added, and the mixture was stirred at 80 ° C for 4 hours to obtain a polyimine-polyfluorene. A varnish of aminic acid polymer. The obtained polyamidene-polyamide polymer had a weight average molecular weight (Mw) of 100,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Example 38]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 0.29 g (1.5 mmol) of CBDA was added, and the mixture was refluxed at 180 ° C for 2 hours, and then toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ° C, and it was confirmed by IR that the absorption (C=O) near 1,650 cm ^-1 derived from the indole bond disappeared. Thereafter, 12.55 g (39.2 mmol) of TFMB, 175.5 g of NMP, 6.54 g (30.0 mmol) of PMDA, 4.44 g (10.0 mmol) of 6FDA, and 1.67 g (8.5 mmol) of CBDA were added, and the mixture was stirred at 80 ° C for 4 hours. A varnish of a polyamidene-polyaminic acid polymer is obtained. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 95,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Example 39]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 0.53 g (2.75 mmol) of CBDA was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. The contents of the flask were cooled to 40 ° C, and it was confirmed by IR that the absorption (C=O) near 1,650 cm ^-1 derived from the indole bond disappeared. Thereafter, 12.55 g (39.2 mmol) of TFMB, 183.8 g of NMP, 6.54 g (30.0 mmol) of PMDA, 6.66 g (15.0 mmol) of 6FDA, and 0.45 g (2.25 mmol) of CBDA were added, and the mixture was stirred at 80 ° C for 4 hours. A varnish of a polyamidene-polyaminic acid polymer is obtained. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 80,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Embodiment 40]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 1.47 g (7.5 mmol) of CBDA was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ° C, and it was confirmed by IR that the absorption (C=O) near 1,650 cm ^-1 derived from the indole bond disappeared. Thereafter, TFMB 12.55 g (39.2 mmol), NMP 186.8 g, PMDA 6.54 g (30.0 mmol), 6FDA 2.22 g (5.0 mmol), and CBDA 4.41 g (22.5 mmol) were added, and the mixture was stirred at 80 ° C for 4 hours. A varnish of a polyamidene-polyaminic acid polymer is obtained. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 91,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Example 41]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 2.24 g (10.0 mmol) of H-PMDA was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. The contents of the flask were cooled to 40 ° C, and it was confirmed by IR that the absorption (C=O) near 1,650 cm ^-1 derived from the indole bond disappeared. Thereafter, TFMB 12.55 g (39.2 mmol), NMP 160 g, BPDA 8.83 g (30.0 mmol), and 6FDA 4.44 g (10.0 mmol) were added, and the mixture was stirred at 80 ° C for 4 hours to obtain a polyimine-polyproline. Polymer varnish. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 86,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Example 42]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 2.24 g (10.0 mmol) of H-PMDA was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. The content of the flask was cooled to 40° C., and it was confirmed by IR that the absorption (C=O) in the vicinity of 1,650 cm ⁻¹ derived from the indole bond disappeared, and then TFMB 12.55 g (39.2 mmol) and NMP 147.8 g were placed. PMDA 6.54 g (30.0 mmol) and 4,4'-biphenyl bis(trimellitic acid monoester anhydride) (TAHQ) 4.58 g (10.0 mmol) were placed at 80 ° C for 4 hours, thereby obtaining polyazide. A varnish of an amine-polyaminic acid polymer. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 84,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Example 43]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 2.1 g (10.0 mmol) of CPDA was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. The contents of the flask were cooled to 40 ° C, and it was confirmed by IR that the absorption (C=O) near 1,650 cm ^-1 derived from the indole bond disappeared. Thereafter, TFMB 12.55 g (39.2 mmol), NMP 146.3 g, PMDA 6.54 g (30.0 mmol), and 6FDA 4.44 g (10.0 mmol) were added, and the mixture was stirred at 80 ° C for 4 hours to obtain a polyimine-polyfluorene. A varnish of aminic acid polymer. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 71,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Example 44]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 3.06 g (10.0 mmol) of H-BPDA was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. The contents of the flask were cooled to 40 ° C, and it was confirmed by IR that the absorption (C=O) near 1,650 cm ^-1 derived from the indole bond disappeared. Thereafter, 12.55 g (39.2 mmol) of TFMB, 151.7 g of NMP, 15.4 g (30.0 mmol) of PMDA, and 4. 4 g (10.0 mmol) of 6FDA were added, and the mixture was stirred at 80 ° C for 4 hours to obtain a polyimine-polyfluorene. A varnish of aminic acid polymer. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 73,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Example 45]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, BCDA 2.36 g (10.0 mmol) was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. The contents of the flask were cooled to 40 ° C, and it was confirmed by IR that the absorption (C=O) near 1,650 cm ^-1 derived from the indole bond disappeared. Thereafter, TFMB 12.55 g (39.2 mmol), NMP 147.7 g, PMDA 6.54 g (30.0 mmol), and 6FDA 4.44 g (10.0 mmol) were added, and the mixture was stirred at 80 ° C for 4 hours to obtain a polyimine-polyfluorene. A varnish of aminic acid polymer. The obtained polyamidene-polyglycine polymer had a weight average molecular weight (Mw) of 75,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Example 46]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BOTDA) 2.48 g (10.0 mmol) was added, and after refluxing at 180 ° C for 2 hours, 3 The toluene as an azeotropic solvent was removed in an hour. The contents of the flask were cooled to 40 ° C, and it was confirmed by IR that the absorption (C=O) near 1,650 cm ^-1 derived from the indole bond disappeared. Thereafter, 12.55 g (39.2 mmol) of TFMB, 148.4 g of NMP, 6.54 g (30.0 mmol) of PMDA, and 4. 4 g (10.0 mmol) of 6FDA were added, and the mixture was stirred at 80 ° C for 4 hours to obtain a polyimine-polyfluorene. A varnish of aminic acid polymer. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 74,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Example 47]

2,2'-Dimethylbiphenyl-4,4'-diamine (mTB) 2.08 g (9.8 mmol) was placed in a separable flask equipped with a Dean Stark apparatus and a reflux apparatus under a nitrogen atmosphere. NMP16.14g and toluene 50g were dissolved in mTB under stirring. Here, 2.24 g (10.0 mmol) of H-PMDA was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. The contents of the flask were cooled to 40 ° C, and it was confirmed by IR that the absorption (C=O) near 1,650 cm ^-1 derived from the indole bond disappeared. Thereafter, mTB 8.32 g (39.2 mmol), NMP 117.2 g, PMDA 6.54 g (30.0 mmol), and 6FDA 4.44 g (10.0 mmol) were added, and the mixture was stirred at 80 ° C for 4 hours to obtain a polyimine-polyfluorene. A varnish of aminic acid polymer. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 82,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Example 48]

4,4'-diaminophenyl benzoanilide (DABA) 2.23 g (9.8 mmol), NMP 16.14 g and toluene were placed in a separable flask equipped with a Dean Stark apparatus and a reflux apparatus under a nitrogen atmosphere. 50 g, dissolved DABA with stirring. Here, 2.24 g (10.0 mmol) of H-PMDA was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. The contents of the flask were cooled to 40 ° C, and it was confirmed by IR that the absorption (C=O) near 1,650 cm ^-1 derived from the indole bond disappeared. Thereafter, DABA 8.91 g (39.2 mmol), NMP 121.4 g, PMDA 6.54 g (30.0 mmol), and 6FDA 4.44 g (10.0 mmol) were added, and the mixture was stirred at 80 ° C for 4 hours to obtain a polyimine-polyfluorene. A varnish of aminic acid polymer. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 83,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Example 49]

In a separable flask equipped with a Dean Stark apparatus and a reflux reactor, 4-aminophenyl 4-aminobenzoate (APAB) 2.24 g (9.8 mmol), NMP 16.14 g and toluene were placed under a nitrogen atmosphere. 50 g, APAB was dissolved under stirring. Here, 2.24 g (10.0 mmol) of H-PMDA was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. The contents of the flask were cooled to 40 ° C, and it was confirmed by IR that the absorption (C=O) near 1,650 cm ^-1 derived from the indole bond disappeared. Thereafter, 8.75 g (39.2 mmol) of APAB, 12.6 g of NMP, 12.6 g of NMP (30.0 mmol), and 6.FDA (40.0 mmol) of 6FDA were added, and the mixture was stirred at 80 ° C for 4 hours to obtain a polyimine-polyfluorene. A varnish of aminic acid polymer. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 82,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Example 50]

In the varnish of the polyimine-polyamide polymer obtained in Example 9, the alkoxydecane compound 1 (ROSi1) was dissolved in an amount of 0.5 part by weight based on 100 parts by weight of the resin, and 0.1 μm was used. The filter was filtered to thereby prepare a resin composition. The characteristics of the composition and the cured film thereof were measured in accordance with the above evaluation method. The results obtained are shown in Table 2.

[Example 51]

In the varnish of the polyimine-polyamide polymer obtained in Example 19, the alkoxydecane compound 1 was dissolved in an amount of 0.5 part by weight based on 100 parts by weight of the resin, and was filtered using a 0.1 μm filter. Filtration, thereby preparing a resin composition. The characteristics of the composition and the cured film thereof were measured in accordance with the above evaluation method. The results obtained are shown in Table 2.

[Example 52]

In the varnish of the polyimine-polyamide polymer obtained in Example 9, the surfactant 1 (Surf1) was dissolved in an amount of 0.05 part by weight based on 100 parts by weight of the resin, and a filter of 0.1 μm was used. Filtration was carried out to thereby prepare a resin composition. The characteristics of the composition and the cured film thereof were measured in accordance with the above evaluation method. The results obtained are shown in Table 2.

[Example 53]

In the varnish of the polyimine-polyamide polymer obtained in Example 19, the surfactant 1 was dissolved in an amount of 0.05 part by weight based on 100 parts by weight of the resin, and filtered using a 0.1 μm filter. The resin composition was thus prepared. The characteristics of the composition and the cured film thereof were measured in accordance with the above evaluation method. The results obtained are shown in Table 2.

[Comparative Example 1]

The feed was changed to TFMB 14.39 g (44.9 mmol), NMP 163.23 g, PMDA 10.0 g (45.8 mmol), ODPA0g (0 mmol), and CBDA0g (0 mmol), except for the same manner as Reference Example 1. Get varnish. The weight average molecular weight (Mw) of the polyamic acid in the obtained varnish was 47,000. The CTE, YI value and elongation of the film which was cured at 350 ° C are shown in Table 2 below.

[Comparative Example 2]

The feed was changed to TFMB 10.12 g (31.6 mmol), NMP 134.65 g, PMDA0g (0 mmol), ODPA 10.0 g (32.2 mmol), and CBDA0g (0 mmol), except for the same manner as Reference Example 1. Get varnish. The weight average molecular weight (Mw) of the polyamic acid in the obtained varnish was 65,500. The CTE, YI value and elongation of the film which was cured at 350 ° C are shown in Table 2 below.

[Comparative Example 3]

The feed was changed to TFMB of 16.00 g (50.0 mmol), NMP of 174.00 g, PMDA0g (0 mmol), ODPA0g (0 mmol), and CBDA of 10.00 g (51.0 mmol), except for the same manner as in Reference Example 1. Get varnish. The weight average molecular weight (Mw) of the polyamic acid in the obtained varnish was 221,000. Will cure at 330 ° C The CTE, YI value and elongation of the film are shown in Table 2 below.

[Comparative Example 4]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 14.00 g (43.7 mmol), NMP 160.62 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. 10.00 g (44.6 mmol) of H-PMDA was added thereto, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. Thereafter, the contents of the flask were cooled to room temperature, whereby a varnish of polyimine was obtained. The weight average molecular weight (Mw) of the polyimine in the obtained varnish was 50,600. The CTE, YI value and elongation of the film which was cured at 350 ° C are shown in Table 2 below.

[Comparative Example 5]

A varnish was obtained in the same manner as in Reference Example 1, except that the feed was changed to TFMB 8.79 g (27.4 mmol), NMP 60.6 g, PMDA 5.50 g (25.2 mmol), and ODPA 0.87 g (2.8 mmol). . The weight average molecular weight (Mw) of the polymer contained in the obtained varnish was 47,000. The CTE, YI value and breaking strength of the film which was cured at 350 ° C are shown in Table 2 below.

[Comparative Example 6]

The feeding of the raw materials was changed to TFMB 16.44 g (51.3 mmol), NMP 184.18 g, PMDA 8.00 g (36.7 mmol), ODPA0g (0 mmol), and CBDA 3.08 g (15.7 mmol), except for the reference example 1 The varnish is obtained in the same manner. The weight average molecular weight (Mw) of the polymer contained in the obtained varnish was 121,900. The CTE, YI value and breaking strength of the film cured at 330 ° C are shown in Table 2 below.

[Comparative Example 7]

The feeding of the raw materials was changed to TFMB 14.17 g (44.2 mmol), NMP 171.31 g, PMDA0g (0 mmol), ODPA 7.00 g (22.6 mmol), and CBDA 4.43 g (22.6 mmol), except for the reference example 1 The varnish is obtained in the same manner. The obtained varnish had a weight average molecular weight (Mw) of 105,000. Film that will cure at 330 ° C The CTE, YI value and breaking strength are shown in Table 2 below.

[Comparative Example 8]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 2.24 g (10.0 mmol) of H-PMDA was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. After cooling the contents of the flask to 40° C., 12.55 g (39.2 mmol) of TFMB, 186.91 g of NMP, and 12.41 g (40.0 mmol) of ODPA were added, and the mixture was stirred at 80° C. for 4 hours to obtain a polyimine-poly. A varnish of a proline polymer. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 66,700. The CTE, YI value and elongation of the film which was cured at 350 ° C are shown in Table 2 below.

[Comparative Example 9]

The feeding of the raw materials was changed to TFMB 15.69 g (49.0 mmol), NMP 175.05 g, PMDA 6.54 g (30.0 mmol), ODPA0g (0 mmol), and CBDA 3.92 g (20.0 mmol), except for the reference example 1 The varnish is obtained in the same manner. The weight average molecular weight (Mw) of the polymer contained in the obtained varnish was 91,200. The CTE, YI value and breaking strength of the film cured at 330 ° C are shown in Table 2 below.

[Comparative Example 10]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 2.24 g (10.0 mmol) of H-PMDA was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. After cooling the contents of the flask to 40° C., 12.55 g (39.2 mmol) of TFMB, 162.26 g of NMP, and 8.72 g (40.0 mmol) of PMDA were added, and the mixture was stirred at 80° C. for 4 hours to obtain a polyimine-poly. A varnish of a proline acid polymerized composition. The obtained polyamidene-polyglycine polymerization composition had a weight average molecular weight (Mw) of 226,000. Cured film at 350 ° C The CTE, YI values and elongation are shown in Table 2 below.

[Comparative Example 11]

The feeding of the raw materials was changed to TFMB 15.69 g (49.0 mmol), NMP 193.54 g, PMDA0g (0 mmol), ODPA 9.31 g (30.0 mmol), and CBDA 3.92 g (20.0 mmol), except for the reference example 1 The varnish is obtained in the same manner. The weight average molecular weight (Mw) of the polymer contained in the obtained varnish was 125,100. The CTE, YI value and breaking strength of the film cured at 330 ° C are shown in Table 2 below.

[Comparative Example 12]

The feeding of the raw materials was changed to TFMB 15.69 g (49.0 mmol), NMP 178.27 g, PMDA0g (0 mmol), ODPA 3.10 g (10.0 mmol), and CBDA 7.84 g (40.0 mmol), except for the reference example 1 The varnish is obtained in the same manner. The weight average molecular weight (Mw) of the polymer contained in the obtained varnish was 120,900. The CTE, YI value and breaking strength of the film cured at 330 ° C are shown in Table 2 below.

[Comparative Example 13]

In a separable flask equipped with a Dean Stark apparatus and a reflux apparatus, TFMB 12.55 g (39.2 mmol), NMP 64.56 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, H-PMDA 8.97 g (40.0 mmol) was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. After cooling the contents of the flask to 40° C., TFMB 3.14 g (9.8 mmol), NMP 46.48 g, and ODPA 3.1 g (10.0 mmol) were added, and the mixture was stirred at 80° C. for 4 hours to obtain a polyimine-poly. A varnish of a proline polymer. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 49,800. The CTE, YI value and elongation of the film which was cured at 350 ° C are shown in Table 2 below.

[Comparative Example 14]

The feedstock was changed to TFMB7.06g (22.0mmol), NMP96.67g, PMDA0g (0mmol) and 6FDA10.00g (22.5mmol), except for A varnish was obtained in the same manner as in Reference Example 1. The weight average molecular weight (Mw) of the polyamic acid in the obtained varnish was 110,000. The CTE, YI value and elongation of the film which was cured at 350 ° C are shown in Table 2 below.

[Comparative Example 15]

Under a nitrogen atmosphere, 15.69 g (49.00 mmol) of TFMB and 203.4 g of NMP were placed in a 500 ml separable flask, and TFMB was dissolved under stirring. Then, 14.71 g (50.0 mmol) of BPDA was added, and the mixture was stirred at 80 ° C for 4 hours, thereby obtaining a NMP solution (varnish) of polyglycine. The weight average molecular weight (Mw) of the obtained polyamic acid was 49,000. The evaluation results of the film which was cured at 330 ° C are shown in Table 2.

[Comparative Example 16]

Under a nitrogen atmosphere, 15.69 g (49.00 mmol) of TFMB and 258.4 g of NMP were placed in a 500 ml separable flask, and TFMB was dissolved under stirring. Then, 22.92 g (50.0 mmol) of TAHQ was added, and the mixture was stirred at 80 ° C for 4 hours to obtain a NMP solution (varnish) of polylysine. The weight average molecular weight (Mw) of the obtained polyamic acid was 64,000. The evaluation results of the film which was cured at 330 ° C are shown in Table 2.

[Comparative Example 17]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, 15.69 g (49.0 mmol) of TFMB, 175.3 g of NMP, and 50 g of toluene were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 10.51 g (100.0 mmol) of CPDA was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. Thereafter, the contents of the flask were cooled to room temperature, whereby a varnish of polyimine was obtained. The weight average molecular weight (Mw) of the polyimine in the obtained varnish was 51,600. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Comparative Example 18]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, 15.69 g (49.0 mmol) of TFMB, 175.3 g of NMP and 50 g of toluene were placed under a nitrogen atmosphere. Dissolve TFMB under mixing. Here, 15.32 g (100.0 mmol) of H-BPDA was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. Thereafter, the contents of the flask were cooled to room temperature, whereby a varnish of polyimine was obtained. The weight average molecular weight (Mw) of the polyimine in the obtained varnish was 54,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Comparative Example 19]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, 15.69 g (49.0 mmol) of TFMB, 175.3 g of NMP, and 50 g of toluene were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 11.82 g (100.0 mmol) of BCDA was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. Thereafter, the contents of the flask were cooled to room temperature, whereby a varnish of polyimine was obtained. The weight average molecular weight (Mw) of the polyimine in the obtained varnish was 50,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Comparative Example 20]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, 15.69 g (49.0 mmol) of TFMB, 175.3 g of NMP, and 50 g of toluene were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 12.41 g (100.0 mmol) of BOTDA was added, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed for 3 hours. Thereafter, the contents of the flask were cooled to room temperature, whereby a varnish of polyimine was obtained. The weight average molecular weight (Mw) of the polyimine in the obtained varnish was 54,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Comparative Example 21]

In a separable flask equipped with a Dean Stark apparatus and a reflux vessel, TFMB 3.14 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and TFMB was dissolved under stirring. Here, 0.16 g (0.7 mmol) of H-PMDA was added, and the mixture was refluxed at 180 ° C for 2 hours, and then toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ° C, and it was confirmed by IR that the absorption (C=O) near 1,650 cm ^-1 derived from the indole bond disappeared. Thereafter, 12.55 g (39.2 mmol) of TFMB, 147 g of NMP, 6.54 g (30.0 mmol) of PMDA, 4.44 g (10.0 mmol) of 6FDA, and 2.08 g (9.3 mmol) of H-PMDA were added, and the mixture was stirred at 80 ° C for 4 hours. A varnish of a polyamidene-polyaminic acid polymer is obtained. The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 51,000. The evaluation results of the film which was cured at 350 ° C are shown in Table 2.

[Comparative Example 22]

A varnish is prepared in accordance with the method disclosed in Korean Patent Publication No. 10-2013-0077946.

Under a nitrogen atmosphere, 270 ml of dimethylacetamide (DMAc) was placed in a 1,000 ml separable flask, and TFMB 32.02 g (100.0 mmol) was completely dissolved at room temperature. Then, 6FDA 111.1 g (25.0 mmol), PMDA 109.1 g (50.0 mmol), and H-PMDA 56.04 g (25.0 mmol) were sequentially added, and the mixture was stirred at room temperature for 12 hours. Thereafter, the mixture was heated in an oil bath at 120 ° C for 20 minutes, and then stirred at normal temperature for 12 hours to obtain a polyamidonic acid solution (varnish). The weight average molecular weight (Mw) of the obtained polyamic acid was 32,000.

The evaluation results of the polyimide film obtained by slowly cooling after heating to 80 ° C from 80 ° C for 8 hours using the above varnish are shown in Table 2.

[Comparative Example 23]

A varnish is prepared in accordance with the method disclosed in Korean Patent Publication No. 10-2013-0077946.

The same procedure as in Comparative Example 22 was carried out, except that the feed was changed to 6FDA 88.85 g (20.0 mmol), PMDA 87.25 g (40.0 mmol), and H-PMDA 89.67 g (40.0 mmol). The evaluation results of the obtained polyimide film were shown in Table 2.

[Comparative Example 24]

A varnish is prepared in accordance with the method disclosed in Korean Patent Publication No. 10-2013-0077946.

The same procedure as in Comparative Example 22 was carried out except that the feed was changed to 6FDA 177.7 g (40.0 mmol), PMDA 87.25 g (40.0 mmol), and H-PMDA 44.83 g (20.0 mmol). The evaluation results of the obtained polyimide film were shown in Table 2.

The abbreviations of the components disclosed in Table 1 are respectively the following meanings.

[Aromatic tetracarboxylic dianhydride 1]

PMDA: pyromellitic dianhydride

BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride

[Aromatic tetracarboxylic dianhydride 2]

ODPA: 4,4'-oxydiphthalic dianhydride

6FDA: 4,4'-(hexafluoroisopropylidene)diphthalic anhydride

TAHQ: 4,4'-biphenyl bis(trimellitic acid monoester anhydride)

[alicyclic tetracarboxylic dianhydride]

CBDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

H-PMDA: 1,2,4,5-cyclohexanetetracarboxylic dianhydride

CPDA: 1,2,3,4-cyclopentane tetracarboxylic dianhydride

H-BPDA: 1,2,4,5-bicyclohexanetetracarboxylic dianhydride

BCDA: bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic acid 2,3:5,6-dianhydride

BOTDA: Bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride

[diamine]

TFMB: 2,2'-bis(trifluoromethyl)benzidine

mTB: 2,2'-dimethylbiphenyl-4,4'-diamine

DABA: 4,4'-diaminobenzoquinone

APAB: 4-aminophenyl 4-aminobenzoate

[Other additives]

ROSi1: alkoxydecane compound 1, a compound of the following structural formula

Surf1: surfactant 1, polyfluorene type nonionic surfactant DBE224 (trade name, manufactured by Gelest)

As shown in the table, it was confirmed that the structure derived from the alicyclic tetracarboxylic dianhydride, the structure derived from the above aromatic tetracarboxylic dianhydride 1, and the structure derived from the above aromatic tetracarboxylic dianhydride 2 were all included. The resin composition (varnish) of the polyimide precursor: (0) The viscosity change rate at the time of storage at room temperature for 4 weeks is 10% or less; the polyimide film obtained by hardening the above composition is on the film property At the same time, the following conditions are satisfied: (1) CTE is 25 ppm or less, (2) YI value is 10 or less, and (3) elongation is 15% or more; and a laminate of an inorganic film is formed on the above polyimine film simultaneously It satisfies: (4) Haze is 15 or less, and (5) water vapor transmission rate is 0.1 g/(m ² ‧24 h) or less.

Further, according to the evaluation results of Comparative Examples 1 to 4, 14 and 15 to 20, it was confirmed that the polyimide film having only the polyimine precursor having a structure derived from one type of tetracarboxylic dianhydride cannot simultaneously satisfy the above. All the film properties of (0) to (5); according to the evaluation results of Comparative Examples 5 to 13, it was confirmed that even if a polyimine precursor having two structures derived from each of two kinds of tetracarboxylic dianhydrides was used, The polyimide film does not give sufficient performance to all of the above film properties (0) to (5). and then, According to the evaluation results of Comparative Examples 21 to 25, it was confirmed that a polyimine film having a polyimine precursor having three structures derived from each of the above three tetracarboxylic dianhydrides was used. When the imidization ratio of the amine precursor derived from the alicyclic bond of the alicyclic tetracarboxylic dianhydride exceeds 10 to 100%, the film properties of the above (0) to (5) cannot be obtained. Give full performance.

From the above results, it was confirmed that the polyimine precursor has a structure derived from an alicyclic tetracarboxylic dianhydride, a structure derived from the above aromatic tetracarboxylic dianhydride 1, and a derived from the above aromatic tetracarboxylic acid. When the dianhydride 2 has the entire structure and the sulfhydryl imidization ratio of the alicyclic bond of the alicyclic tetracarboxylic dianhydride is in the range of 10 to 100%, the composition containing the polyimine precursor The polyimine film obtained by curing the composition is colorless and transparent, has a low coefficient of linear expansion, and is excellent in elongation, and a laminate of an inorganic film is formed on the polyimide film. The Haze is small and has excellent water vapor transmission rate.

[Industrial availability]

The polyimide precursor of the present invention can be preferably used, for example, for producing a semiconductor insulating film, a TFT-LCD insulating film, an electrode protective film, and a flexible display, and can be particularly preferably used for manufacturing a substrate.

Claims (27)

A polyimine precursor having a structure represented by the following formula (A) and having a structure derived from a diamine derived from 2,2'-bis(trifluoromethyl) Benzylamine (TFMB), 2,2'-dimethylbiphenyl-4,4'-diamine, 4,4'-diaminobenzophenidine and 4-aminobenzoic acid 4-aminobenzene The structure of at least one diamine in the ester derived from the structure derived from tetracarboxylic dianhydride derived from 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), 1, 2, 4 , 5-cyclohexanetetracarboxylic dianhydride (H-PMDA), 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-bicyclohexanetetracarboxylic dianhydride Bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid 2,3:5,6-dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5, 6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentaacetic acid-1,4:2,3-dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(four Hydrogen-2,5-di-oxy-3-furanyl-naphtho[1,2-c]furan-1,3-dione and bicyclo[3,3,0]octane-2,4, a structure of at least one alicyclic tetracarboxylic dianhydride of 6,8-tetracarboxylic dianhydride, and a structure derived from an aromatic tetracarboxylic dianhydride; and derived from the above alicyclic tetracarboxylic dianhydride The imidization ratio of the indoleamine bond is 10 to 100%. {X ₁ is derived from 2,2'-bis(trifluoromethyl)benzidine (TFMB), 2,2'-dimethylbiphenyl-4,4'-diamine, 4,4'- a structure of at least one diamine of diaminophenylbenzophenone and 4-aminophenyl 4-aminobenzoate; X ₂ is derived from a 1,2,3,4-cyclobutanetetracarboxylic acid Desic anhydride (CBDA), 1,2,4,5-cyclohexanetetracarboxylic dianhydride (H-PMDA), 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,4 , 5-bicyclohexanetetracarboxylic dianhydride, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid 2,3:5,6-dianhydride, bicyclo[2.2.2] octane -7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentaacetic acid-1,4:2,3-dianhydride, 1,3,3a,4, 5,9b-hexahydro-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphtho[1,2-c]furan-1,3-dione and bicyclo[3, 3,0] Structure of at least one tetracarboxylic dianhydride of octane-2,4,6,8-tetracarboxylic dianhydride}. The polyimine precursor of claim 1, wherein the polyimine precursor has a structure of the following formula (B), {X ₁ is the same as in the above formula (A), and X ₃ is a structure derived from the above aromatic tetracarboxylic dianhydride}. The polyamidene precursor of claim 1 or 2, wherein the guanidinium linkage derived from the alicyclic bond of the alicyclic tetracarboxylic dianhydride is from 20 to 100%. The polyimine precursor according to any one of claims 1 to 3, wherein the guanidinium linkage derived from the alicyclic bond of the alicyclic tetracarboxylic dianhydride is from 30 to 100%. The polyimine precursor according to any one of claims 1 to 4, wherein the aromatic tetracarboxylic dianhydride comprises: pyromellitic dianhydride (PMDA) as aromatic tetracarboxylic dianhydride 1 And at least one of 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 4,4'-oxydiphthalic dianhydride as aromatic tetracarboxylic dianhydride 2 ( ODPA), 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and 4,4'-biphenyl At least one of bis(trimellitic acid monoester anhydride). The polyimine precursor according to any one of claims 1 to 5, wherein the aromatic tetracarboxylic dianhydride 1 is pyromellitic dianhydride (PMDA). The polyimine precursor according to any one of claims 1 to 5, wherein the aromatic tetracarboxylic dianhydride 2 is selected from the group consisting of 4,4'-oxydiphthalic dianhydride (ODPA) and 4, At least one of 4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA). The polyimine precursor according to any one of claims 1 to 7, wherein the structure derived from the diamine is a structure derived from 2,2'-bis(trifluoromethyl)benzidine (TFMB). The polyamidiamine precursor according to any one of claims 1 to 8, wherein the alicyclic tetracarboxylic dianhydride is selected from the group consisting of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) 1,2,4,5-cyclohexanetetracarboxylic dianhydride (H-PMDA), 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-bicyclohexane Alkanetetracarboxylic dianhydride, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid 2,3:5,6-dianhydride and bicyclo[2.2.2]oct-7-ene- At least one of 2,3,5,6-tetracarboxylic dianhydride. The polyimine precursor according to any one of claims 1 to 9, wherein the alicyclic tetracarboxylic dianhydride is selected from the group consisting of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) And at least one of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (H-PMDA). The polyimine precursor according to any one of claims 1 to 10, which comprises 60% by mole or more of the structure derived from the above-mentioned TFMB in all of the structures derived from the diamine, and is contained in all The structure of the tetracarboxylic dianhydride is a structure of at least 60 mol% or more of at least one tetracarboxylic dianhydride derived from the above PMDA, the above ODPA, the above 6FDA, the above CBDA, and the above H-PMDA. The polyimine precursor according to any one of claims 1 to 11, which comprises from 1 to 70 mol% of the structure derived from the above-mentioned PMDA in a structure derived from all of the tetracarboxylic dianhydride, and A structure derived from at least one tetracarboxylic dianhydride selected from the above ODPA and 6FDA, which accounts for 1 to 50 mol% of the total structure derived from tetracarboxylic dianhydride. The polyimine precursor according to any one of claims 1 to 11, wherein the sum of the molar numbers derived from the structures of the above PMDA, the above ODPA, the above 6FDA, the above CBDA, and the above H-PMDA is derived from The ratio of the molar number of the structure of the above TFMB {PMDA+ODPA+6FDA+CBDA+H-PMDA)/TFMB} is 100/99.9 to 100/95. The polyimine precursor obtained according to any one of claims 1 to 13, wherein the polyimine obtained by hydrazine imidization by heating under a nitrogen atmosphere after dissolving in a solvent and developing on the surface of the support The yellowness of the film was 10 or less, the coefficient of linear expansion was 25 ppm or less, and the elongation of the film at a film thickness of 20 μm was 15% or more. The polyimine precursor of any one of claims 1 to 14 for use in the manufacture of a flexible device. A resin composition comprising the polyimine precursor according to any one of claims 1 to 15, and a solvent. The resin composition of claim 16, which further contains an alkoxydecane compound. The resin composition of claim 16 or 17, which further comprises a surfactant. A polyimine film, which is characterized in that a resin composition according to any one of claims 16 to 18 is developed on a surface of a support to form a coating film, and then the support and the coating film are heated. The polyimine precursor is formed by imidization of ruthenium. A method for producing a polyimide film, comprising: a coating film forming step of developing a resin composition according to any one of claims 16 to 18 on a surface of a support to form a coating film; and heating step Heating the support and the coating film to imidize the polyimine precursor to form a polyimide film; A peeling step of peeling the polyimine film from the support to obtain a polyimide film. A laminate comprising a support and a polyimide film formed on the support, and the laminate system spreads the resin composition according to any one of claims 16 to 18 on the surface of the support A coating film is formed, and then the support and the coating film are heated, and the polyimine precursor is obtained by hydrazine imidization to form a polyimide film. A method for producing a laminate comprising a support and a polyimide film formed on the support, the method comprising: a coating film forming step of expanding on a surface of the support as claimed in claim 16 a resin composition according to any one of 18 to form a coating film; and a heating step of heating the support and the coating film to imidize the polyimine precursor to form a polyimine membrane. A polyimine film characterized by being a copolymer of a diamine and a tetracarboxylic dianhydride, wherein the diamine is selected from the group consisting of 2,2'-bis(trifluoromethyl)benzidine ( At least one of TFMB), 2,2'-dimethylbiphenyl-4,4'-diamine, 4,4'-diaminobenzoquinone and 4-aminophenyl 4-aminobenzoate In one embodiment, the tetracarboxylic dianhydride comprises, as an alicyclic tetracarboxylic dianhydride, 2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA), 1,2,4,5-cyclohexane. Tetracarboxylic dianhydride (H-PMDA), 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-bicyclohexanetetracarboxylic dianhydride, bicyclo [2.2.1 Heptane-2,3,5,6-tetracarboxylic acid 2,3:5,6-dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid Anhydride, 2,3,5-tricarboxycyclopentaacetic acid-1,4:2,3-dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5- Bis-oxy-3-furanyl)-naphtho[1,2-c]furan-1,3-dione and bicyclic At least one of [3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride, which is selected from pyromellitic dianhydride (PMDA) as aromatic tetracarboxylic dianhydride 1 and At least one of 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 4,4'-oxydiphthalic dianhydride (ODPA) as aromatic tetracarboxylic dianhydride 2 At least one of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and 4,4'-biphenylbis(trimellitic acid monoester anhydride), and When an inorganic film was formed by a CVD method at 350 ° C on a polyimide film, the surface roughness of the surface of the inorganic film measured by atomic force microscopy (AFM) was 0.01 to 50 nm. The polyimine film according to claim 23, wherein the diamine is 2,2'-bis(trifluoromethyl)benzidine (TFMB), and the tetracarboxylic dianhydride comprises alicyclic tetracarboxylic dianhydride. At least one selected from the group consisting of 2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) and 1,2,4,5-cyclohexanetetracarboxylic dianhydride (H-PMDA) as an aromatic The tetracarboxylic dianhydride 1 is at least one selected from the group consisting of pyromellitic dianhydride (PMDA) and 3,3',4,4'-biphenyltetracarboxylic dianhydride, and as an aromatic tetracarboxylic dianhydride. 2 is at least one selected from the group consisting of 4,4'-oxydiphthalic dianhydride (ODPA) and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA). A flexible device comprising the polyimide film of claim 23 or 24. A method of producing a flexible device comprising the method of producing a polyimide film according to claim 20. A method of manufacturing a flexible device comprising the method of manufacturing a laminate according to claim 22.