JP6254197B2 - Polyimide precursor and resin composition containing the same - Google Patents

Description

The present invention relates to a polyimide precursor and a resin composition containing the same. The polyimide precursor can be used as a substrate for a flexible device, for example.
This invention also provides a polyimide film and its manufacturing method, and a laminated body and its manufacturing method.

  The polyimide film is generally a film made of a polyimide resin. A 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 imidization. The thermal imidization is performed by ring closure dehydration at a high temperature, and the chemical imidization is performed by catalyst ring closure dehydration.

  The polyimide resin is an insoluble and infusible super heat resistant resin, and has excellent characteristics such as heat oxidation resistance, heat resistance characteristics, radiation resistance, low temperature resistance, and chemical resistance. Accordingly, polyimide resins are used in a wide range of fields including electronic materials such as insulating coating agents, insulating films, semiconductors, and electrode protection films for TFT-LCDs. Recently, it is also used for display materials such as liquid crystal alignment films and optical fibers.

  However, the polyimide resin is colored brown or yellow due to its high aromatic ring density and has low transmittance in the visible light region, so that it is difficult to use it in fields where transparency is required.

  In this regard, Patent Document 1 reports that a polyimide having a novel structure, in which transmittance and hue transparency are improved by using a tetracarboxylic dianhydride and a diamine containing a specific structure, has been reported. is there.

Patent Document 2 and Patent Document 3 each disclose a polyimide film into which an alicyclic structure is introduced in order to impart transparency.
Further, in Patent Document 4, as a tetracarboxylic dianhydride, a specific aromatic tetracarboxylic dianhydride and an alicyclic tetracarboxylic dianhydride are used in combination, whereby yellowness (hereinafter referred to as “YI”). There is a report that a polyimide resin having a low value is also obtained.

JP 2000-198843 A JP 2005-336243 A JP 2003-155342 A Korean Patent Publication No. 10-2013-0077946

  However, the mechanical characteristics and thermal characteristics of polyimide described 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 polyimide described in Patent Document 1 is characterized by a high coefficient of linear expansion (hereinafter also referred to as “CTE”). When a resin having a high CTE is used as a film, the degree of expansion and contraction of the film caused by temperature change increases. Therefore, for example, when a film having a high CTE is used for the TFT process or the like, the inorganic film as the element material is damaged, and the element capability is reduced. Therefore, a polyimide resin used for a substrate for forming a TFT, a substrate for forming a color filter, an alignment film, a flexible display transparent substrate, and the like must be colorless and transparent and have a low CTE.

In addition, the polyimide described in Patent Document 2 has the disadvantages that it has transparency but high CTE and low elongation at break. When the elongation at break is low, the flexible substrate is damaged when the flexible device is handled, and therefore cannot be used as a device.
In the case of the polyimide described in Patent Document 3, toughness is imparted by using a polycyclic aromatic diamine. However, since this polyimide also has a high CTE, it is not suitable for use as a semiconductor insulating film, TFT-LCD insulating film, electrode protective film or flexible display substrate.
And in the case of the polyimide described in patent document 4, YI value is certainly low. However, when the present inventors examined, since CTE is high and elongation is small, there exists room for improvement in applying to a display process (refer comparative examples 22-24 mentioned later).

  The present invention has been made in view of the above-described problems, and includes a polyimide precursor that can produce a polyimide film that is colorless and transparent, has a low CTE, and is excellent in elongation, and contains it. An object of the present invention is to provide a resin composition, a polyimide film and a production method thereof, and a laminate and a production method thereof.

In order to solve the above-mentioned problems, the present inventors have intensively studied and repeated experiments. as a result,
A resin composition (varnish) containing a polyimide precursor having a specific structure is excellent in storage stability;
A polyimide film obtained by curing the composition has excellent transparency, a low linear expansion coefficient, and a high elongation; and a laminate in which an inorganic film is formed on the polyimide film has a small haze and water vapor. It has been found that the transmittance is excellent, and the present invention has been made based on these findings.
That is, the present invention is as follows.

[1]
It has a structure represented by the following general formula (A), and as a diamine-derived structure, 2,2′-bis (trifluoromethyl) benzidine (TFMB), 2,2′-dimethylbiphenyl-4,4′- A structure derived from at least one diamine selected from diamine, 4,4′-diaminobenzanilide and 4-aminophenyl-4-aminobenzoate;
As a structure derived from tetracarboxylic dianhydride,
1,2,3,4-cyclobutanetetracarboxylic dianhydride (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] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid-1,4 : 2,3-dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C] furan-1 , 3-dione and bicyclo [3,3,0] octa 2,4,6,8 and structure derived from at least one alicyclic tetracarboxylic dianhydride selected from tetracarboxylic acid dianhydride;
A structure derived from an aromatic tetracarboxylic dianhydride;
And a polyimide precursor having an imidation ratio of an amide bond derived from the alicyclic tetracarboxylic dianhydride of 10 to 100%.

{X ₁ is 2,2′-bis (trifluoromethyl) benzidine (TFMB), 2,2′-dimethylbiphenyl-4,4′-diamine, 4,4′-diaminobenzanilide and 4-aminophenyl- A structure derived from at least one diamine selected from 4-aminobenzoate;
X ₂ represents 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-tricarboxycyclopentylacetic acid 1,4: 2,3-dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C ] Furan-1,3-dione and bicyclo [3,3,0 ] A structure derived from at least one tetracarboxylic dianhydride selected from octane-2,4,6,8-tetracarboxylic dianhydride. }
[2]
The polyimide precursor according to [1], wherein the polyimide precursor has a structure represented by the following general formula (B).

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

[3]
The polyimide precursor as described in [1] or [2] whose imidation ratio of the amide bond derived from an alicyclic tetracarboxylic dianhydride is 20 to 100%.

[4]
The polyimide precursor as described in any one of [1] to [3] whose imidation ratio of the amide bond derived from an alicyclic tetracarboxylic dianhydride is 30 to 100%.

[5]
The aromatic tetracarboxylic dianhydride is
As the aromatic tetracarboxylic dianhydride 1, at least one selected from pyromellitic dianhydride (PMDA) and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride,
As aromatic tetracarboxylic dianhydride 2, 4,4'-oxydiphthalic dianhydride (ODPA), 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 4,4'-biphenyl At least one selected from bis (trimellitic acid monoester anhydride);
The polyimide precursor according to any one of [1] to [4].

[6]
The polyimide precursor according to any one of [1] to [5], wherein the aromatic tetracarboxylic dianhydride 1 is pyromellitic dianhydride (PMDA).

[7]
The aromatic tetracarboxylic dianhydride 2 is at least one selected from 4,4′-oxydiphthalic dianhydride (ODPA) and 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA). The polyimide precursor according to any one of [1] to [5].

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

[9]
The alicyclic tetracarboxylic dianhydride is
1,2,3,4-cyclobutanetetracarboxylic dianhydride (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 and bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, [1] to [1] 8] The polyimide precursor according to any one of the above.

[10]
The alicyclic tetracarboxylic dianhydrides are 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) and 1,2,4,5-cyclohexanetetracarboxylic dianhydride (H-PMDA). The polyimide precursor according to any one of [1] to [9], which is at least one selected from.

[11]
The TFMB-derived structure contains 60 mol% or more of the total diamine-derived structure,
The structure derived from at least one tetracarboxylic dianhydride selected from the PMDA, the ODPA, the 6FDA, the CBDA, and the H-PMDA is combined to be 60 mol% or more in the total tetracarboxylic dianhydride-derived structure. Including,
The polyimide precursor according to any one of [1] to [10].

[12]
The structure derived from PMDA contains 1 to 70 mol% of the structure derived from all tetracarboxylic dianhydrides, and the structure derived from at least one tetracarboxylic dianhydride selected from ODPA and 6FDA 1-50 mol% in the structure derived from dianhydride,
The polyimide precursor according to any one of [1] to [11].

[13]
The ratio {PMDA + ODPA + 6FDA + CBDA + H-PMDA) / TFMB of the sum of the number of moles of the structure derived from each of the PMDA, the ODPA, the 6FDA, the CBDA, and the H-PMDA and the number of moles of the structure derived from the TFMB, The polyimide precursor according to any one of [1] to [11], which is 100 / 99.9 to 100/95.

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

[15]
The polyimide precursor according to any one of [1] to [14], which is used for manufacturing a flexible device.

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

[17]
Furthermore, the resin composition as described in [16] containing an alkoxysilane compound.

[18]
Furthermore, the resin composition as described in [16] or [17] containing surfactant.

[19]
[16] to [18] The resin composition according to any one of [18] is spread on the surface of a support to form a coating film, and then the support and the coating film are heated to form the polyimide precursor. A polyimide film characterized by being formed by imidization.

[20]
[16] to [18] A coating film forming step of developing the resin composition according to any one of the above on the surface of a support to form a coating film;
A heating step of heating the support and the coating film to imidize the polyimide precursor to form a polyimide film;
A peeling step of peeling the polyimide film from the support to obtain a polyimide film;
The manufacturing method of a polyimide film characterized by including.

[21]
A support and a polyimide film formed on the support are provided, and a coating film is formed by developing the resin composition according to any one of [16] to [18] on the surface of the support Then, the laminate is obtained by heating the support and the coating film to imidize the polyimide precursor to form a polyimide film.

[22]
A coating film forming step of developing a coating film by developing the resin composition according to any one of [16] to [18] on the surface of the support;
A heating step of heating the support and the coating film to imidize the polyimide precursor to form a polyimide film;
The manufacturing method of the laminated body which comprises the support body containing this and the polyimide film | membrane formed on this support body.

[23]
A polyimide film produced from a diamine and a copolymer of tetracarboxylic dianhydride,
The diamine is 2,2′-bis (trifluoromethyl) benzidine (TFMB), 2,2′-dimethylbiphenyl-4,4′-diamine, 4,4′-diaminobenzanilide and 4-aminophenyl-4. -At least one selected from aminobenzoates;
The tetracarboxylic dianhydride is
As alicyclic tetracarboxylic dianhydride, 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 -Tricarboxycyclopentylacetic acid-1,4: 2,3-dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 1,2-C] furan-1,3-dio At least a one selected from and bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride,
As the aromatic tetracarboxylic dianhydride 1, at least one selected from pyromellitic dianhydride (PMDA) and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride,
As aromatic tetracarboxylic dianhydride 2, 4,4'-oxydiphthalic dianhydride (ODPA), 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 4,4'-biphenyl At least one selected from bis (trimellitic acid monoester anhydride);
Consists of
When an inorganic film is formed on the polyimide film using a CVD method at 350 ° C.,
The said polyimide film characterized by the surface roughness which measured this inorganic film surface using the atomic force microscope (AFM) being 0.01-50 nm.

[24]
The diamine is 2,2′-bis (trifluoromethyl) benzidine (TFMB);
The tetracarboxylic dianhydride is
Select from 2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) and 1,2,4,5-cyclohexanetetracarboxylic dianhydride (H-PMDA) as the alicyclic tetracarboxylic dianhydride And at least one
As the aromatic tetracarboxylic dianhydride 1, at least one selected from pyromellitic dianhydride (PMDA) and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride,
As aromatic tetracarboxylic dianhydride 2, at least one selected from 4,4′-oxydiphthalic dianhydride (ODPA) and 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA); Consist of,
[23] The polyimide film according to [23].
[25]
The flexible device containing the polyimide film as described in [23] or [24].
[26]
The manufacturing method of a flexible device including the manufacturing method of the polyimide film as described in [20].
[27]
The manufacturing method of a flexible device including the manufacturing method of the laminated body as described in [22].

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

  Hereinafter, an embodiment of the present invention (hereinafter abbreviated as “embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

<Polyimide precursor>
The polyimide precursor according to the present embodiment is
2,2'-bis (trifluoromethyl) benzidine (TFMB), 2,2'-dimethylbiphenyl-4,4'- as a diamine-derived structure having a structure represented by the following general formula (A) A structure derived from at least one diamine selected from diamine and 4,4′-diaminobenzanilide, 4-aminophenyl-4-aminobenzoate;
As a structure derived from tetracarboxylic dianhydride,
1,2,3,4-cyclobutanetetracarboxylic dianhydride (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] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid-1,4 : 2,3-dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C] furan-1 , 3-dione and bicyclo [3,3,0] octa 2,4,6,8 and structure derived from at least one alicyclic tetracarboxylic dianhydride selected from tetracarboxylic acid dianhydride;
A structure derived from an aromatic tetracarboxylic dianhydride;
And an imidation ratio of an amide bond derived from the alicyclic tetracarboxylic dianhydride is 10 to 100%.

{X ₁ is 2,2′-bis (trifluoromethyl) benzidine (TFMB), 2,2′-dimethylbiphenyl-4,4′-diamine, 4,4′-diaminobenzanilide and 4-aminophenyl- A structure derived from at least one diamine selected from 4-aminobenzoate;
X ₂ represents 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-tricarboxycyclopentylacetic acid 1,4: 2,3-dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C ] Furan-1,3-dione and bicyclo [3,3,0 ] A structure derived from at least one tetracarboxylic dianhydride selected from octane-2,4,6,8-tetracarboxylic dianhydride. }

  The polyimide precursor according to the present embodiment preferably has a structure represented by the following general formula (B).

{X ₁ is the same as the formula (A),
X ₃ is a structure derived from the aromatic tetracarboxylic dianhydride. }
And the polyimide precursor which concerns on this Embodiment has the imidation ratio of the amide bond derived from an alicyclic tetracarboxylic dianhydride as 10-100% as above-mentioned. That is, it is an imidized polyamic acid in which at least a part of the amide bond derived from the alicyclic tetracarboxylic dianhydride is imidized.
In order to take an imidized polyamic acid structure in which an amide bond derived from an alicyclic tetracarboxylic dianhydride is imidized, for example,
First, after reacting an alicyclic tetracarboxylic dianhydride with a diamine to obtain a polyamic acid, or simultaneously with obtaining a polyamic acid, the amide bond of the polyamic acid is imidized,
Then, it can be based on the method of continuing reaction of other tetracarboxylic dianhydrides (in this embodiment, aromatic tetracarboxylic dianhydride) and diamine.

First, reacting the alicyclic tetracarboxylic dianhydride is preferable from the viewpoint of increasing the molecular weight of the polyimide precursor and increasing the transparency of the resulting polyimide film. And, in order to increase the molecular weight of the polyimide (precursor) having a structure derived from alicyclic tetracarboxylic dianhydride, the synthesis temperature is usually 60 to 100 ° C. up to 150 to 210 ° C. It is necessary to raise. Raising the synthesis temperature in this way results in imidation of the amide bond derived from the alicyclic tetracarboxylic dianhydride, and the imide group concentration (imidation rate) of the portion derived from the alicyclic dianhydride Becomes larger. Here, the imidation ratio of the amide bond derived from the alicyclic tetracarboxylic dianhydride is determined from the viewpoint of the storage stability of the composition (varnish) containing the polyimide precursor, and the elongation and YI of the obtained polyimide film. 10 to 100% is preferable, 20 to 100% is more preferable, and 30 to 100% is more preferable.
Thus, the alicyclic tetracarboxylic dianhydride is first reacted with the alicyclic tetracarboxylic dianhydride and the aromatic tetracarboxylic dianhydride at the same time, or the aromatic tetracarboxylic dianhydride. When the alicyclic tetracarboxylic dianhydride is added and then synthesized at a temperature of 150 to 210 ° C., imidation of the amide bond in the portion derived from the aromatic tetracarboxylic dianhydride is abrupt. This is because the polymer precipitates and is not suitable.
A detailed method for synthesizing the polyimide precursor in the present embodiment will be described later.

Hereinafter, each structure will be described in detail.
<Tetracarboxylic dianhydride-derived structure>
The polyimide precursor according to the present embodiment is a tetracarboxylic dianhydride-derived structure,
1,2,3,4-cyclobutanetetracarboxylic dianhydride (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] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid-1,4 : 2,3-dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C] furan-1 , 3-dione and bicyclo [3,3,0] octa A structure derived from at least one tetracarboxylic dianhydride selected from 2,4,6,8-tetracarboxylic dianhydride;
A structure derived from an aromatic tetracarboxylic dianhydride;
Have

  Here, as the alicyclic tetracarboxylic dianhydride, 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-tricarboxycyclopentylacetic acid-1,4: 2,3-dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo- 3-furanyl) -naphtho [1,2-C] It is preferred from the down-1,3-dione and bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride is at least one selected. Among them, 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] oct-7-ene-2,3,5,6-tetracarboxylic At least one selected from acid dianhydrides is preferable from the viewpoint of CTE of the obtained polyimide film, and at least one selected from CBDA and H-PMDA is obtained as well as cost. It is more preferable from the viewpoint of YI and transparency of the polyimide film, and H-PMDA is more preferable from the viewpoint of cost.

  The 1,2,4,5-cyclohexanetetracarboxylic dianhydride (H-PMDA) is represented by the following formulas (1) to (3).

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

The aromatic tetracarboxylic dianhydride is
As the aromatic tetracarboxylic dianhydride 1, at least one selected from pyromellitic dianhydride (PMDA) and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride,
As aromatic tetracarboxylic dianhydride 2, 4,4'-oxydiphthalic dianhydride (ODPA), 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 4,4'-biphenyl It is preferably composed of at least one selected from bis (trimellitic acid monoester anhydride).
Here, the aromatic tetracarboxylic dianhydride 1 is mainly used to contribute to improvement of thermal characteristics, mechanical characteristics, etc. of the obtained polyimide film,
The aromatic tetracarboxylic dianhydride 2 is used to contribute to improving the transparency and the like of the polyimide film.

As aromatic tetracarboxylic dianhydride 1, it is more preferable to use PMDA from the viewpoint of CTE of the obtained polyimide film.
As the aromatic tetracarboxylic dianhydride 2, it is more preferable to use at least one selected from ODPA and 6FDA from the viewpoint of YI and transparency of the obtained polyimide film, and it is preferable to use 6FDA. It is further preferable from the viewpoint of CTE.

The polyimide precursor according to the present embodiment is
The structure derived from the alicyclic tetracarboxylic dianhydride has 5 to 60 mol% in the structure derived from all tetracarboxylic dianhydrides,
It is preferable to have a structure derived from aromatic tetracarboxylic dianhydride in an amount of 40 to 95 mol% in the structure derived from all tetracarboxylic dianhydrides;
The structure derived from the alicyclic tetracarboxylic dianhydride has 5 to 60 mol% in the structure derived from all tetracarboxylic dianhydrides,
The structure derived from the aromatic tetracarboxylic dianhydride 1 has 20 to 80 mol% in the structure derived from all tetracarboxylic dianhydrides,
It is more preferable that the structure derived from the aromatic tetracarboxylic dianhydride 2 has 5 to 60 mol% in the structure derived from all tetracarboxylic dianhydrides.
In the polyimide precursor according to the present embodiment, the structure derived from at least one tetracarboxylic dianhydride selected from the PMDA, the ODPA, the 6FDA, the CBDA, and the H-PMDA is combined with all tetracarboxylic acids. More preferably, the acid dianhydride-derived structure contains 60 mol% or more.

And from the viewpoint of obtaining suitable yellowness, CTE and breaking strength of the polyimide film,
The structure derived from pyromellitic dianhydride (PMDA) has 1 to 70 mol% in the structure derived from all tetracarboxylic dianhydrides,
A structure derived from at least one selected from 4,4′-oxydiphthalic dianhydride (ODPA) and 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) It is particularly preferable to have 1 to 50 mol% in the anhydride-derived structure.

<Diamine-derived structure>
The polyimide precursor according to the present embodiment has 2,2′-bis (trifluoromethyl) benzidine (TFMB), 2,2′-dimethylbiphenyl-4,4′-diamine, 4,4 as a diamine-derived structure. It has a structure derived from at least one diamine selected from '-diaminobenzanilide and 4-aminophenyl-4-aminobenzoate. Among these, TFMB is preferable from the viewpoint of YI and transparency of the obtained polyimide film.
Particularly preferably, the TFMB-derived structure is contained in an amount of 60 mol% or more in the total diamine-derived structure.

<Ratio of tetracarboxylic dianhydride-derived structure to diamine-derived structure>
The ratio of the sum of the number of moles of the tetracarboxylic dianhydride-derived structure and the sum of the number of moles of the diamine-derived structure is 100 / 99.9 to 100/95. And from the viewpoint of mechanical properties. More specifically, the ratio of the sum of the number of moles of structures derived from PMDA, ODPA, 6FDA, CBDA and H-PMDA to the number of moles of structures derived from TFMB {(PMDA + ODPA + 6FDA + CBDA + H-PMDA) / TFMB} However, it is preferable that it is 100 / 99.9-100 / 95 from a viewpoint of obtaining the polyimide film which has more suitable yellowness, CTE, and breaking strength.

<Weight average molecular weight of polyimide precursor>
The weight average molecular weight of the polyimide precursor according to 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 70,000 or more. More preferably, it is 250,000 or less. When the weight average molecular weight is 5,000 or more, the high elongation of the resulting polyimide film is improved, and the mechanical properties are excellent. In particular, from the viewpoint of obtaining low CTE and low yellowness (YI value), the molecular weight is more preferably 50,000 or more. When the weight average molecular weight Mw is 1,000,000 or less, the resin composition containing the polyimide precursor can be applied without bleeding at a desired film thickness.
Here, the weight average molecular weight is the sum of the values obtained by multiplying the molecular weight of each molecule by the mass of the molecule in the molecular weight distribution measured by gel permeation chromatography using monodisperse polystyrene as a standard. The value divided by the sum of.

<Synthesis Method of Polyimide Precursor>
The polyimide precursor according to the present embodiment is manufactured as a solution containing the polyimide precursor and the solvent, preferably by dissolving the tetracarboxylic dianhydride component and the diamine component in a solvent and reacting them. Can do. Although the conditions at the time of reaction are not specifically limited, For example, reaction temperature is -20-250 degreeC, Reaction time can illustrate 2-48 hours conditions. The ambient atmosphere during the reaction is preferably an inert atmosphere such as argon or nitrogen.

  The solvent is not particularly limited as long as it is a solvent that dissolves the polymer to be produced. Known reaction solvents include, for example, m-cresol, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), acetone, diethyl acetate, ecamide M100 (trade names) : One or more polar solvents selected from Idemitsu Kosan Co., Ltd.) and Ecamide B100 (trade name: Idemitsu Kosan Co., Ltd.) are useful. Among these, Preferably, it is 1 or more types chosen from NMP, DMAc, Ecamide M100, and Ecamide B100. In addition, a low-boiling solvent such as tetrahydrofuran (THF) or chloroform, or a low-absorbing solvent such as γ-butyrolactone may be used instead of or together with the above-mentioned solvent.

The polyimide precursor is imidized polyamic acid in which at least a part of an amide bond derived from alicyclic tetracarboxylic dianhydride of polyamic acid is subjected to ring-closing dehydration.
The step of ring-closing dehydration of the amide bond is not particularly limited, and a known method can be applied. For example, thermal imidization or chemical imidization can be employed.
More specifically, the thermal imidization can be performed, for example, by the following method. First, diamine is dissolved and / or dispersed in a suitable polymerization solvent, tetracarboxylic dianhydride is added thereto, and a solvent azeotroped with water (such as toluene) is added. Then, using a mechanical stirrer, the mixture is heated and stirred for 0.5 to 96 hours, preferably 0.5 to 30 hours, while removing by-product water azeotropically. The heating temperature is preferably more than 100 ° C. and 250 ° C. or less, preferably 130 to 230 ° C., more preferably 150 to 210 ° C. At this time, the monomer concentration is preferably 0.5% by mass or more and 95% by mass or less, and more preferably 1% by mass or more and 90% by mass or less.

Chemical imidization can be performed using a known imidization catalyst. Although it does not restrict | limit especially as an imidation catalyst, For example, acid anhydrides, such as acetic anhydride;
Lactone compounds such as γ-valerolactone, γ-butyrolactone, γ-tetronic acid, γ-phthalide, γ-coumarin, and γ-phthalido acid;
Examples thereof include tertiary amines such as pyridine, quinoline, N-methylmorpholine, and triethylamine. As the imidation catalyst, only one kind may be used as necessary, or a mixture of two or more kinds may be used. Among these, a mixed system of γ-valerolactone and pyridine is particularly preferable from the viewpoint of high reactivity.
The amount of the imidization catalyst added is preferably 50 parts by mass or less and more preferably 30 parts by mass or less with respect to 100 parts by mass of the polyamic acid.

The ring closure dehydration of the amide bond is particularly preferably performed by thermal imidization performed without a catalyst from the viewpoint of minimizing the influence on the next reaction.
The polyimide precursor according to the present embodiment is
First, the reaction between the alicyclic tetracarboxylic dianhydride and the diamine is performed under the above-mentioned thermal imidization conditions to obtain an imidized polyamic acid,
Next, it is most preferable to synthesize by a method in which an aromatic tetracarboxylic dianhydride and a diamine are additionally added and the reaction is continued preferably at 100 ° C. or lower.

As described above, a solution containing a polyimide precursor is obtained.
The solution may be used for the preparation of the resin composition as it is, or may be used for the preparation of the resin composition after isolating and purifying the polyimide precursor contained in the solution.

<Other additives>
Although the resin composition which concerns on this Embodiment contains the above polyimide precursors and a solvent, you may further contain another additive as needed.
Examples of such other additives include alkoxysilane compounds, surfactants, and leveling agents.

(Alkoxysilane compound)
When the polyimide obtained from the resin composition according to the present embodiment forms an element such as a TFT, the resin composition contains a polyimide precursor 100 in order to ensure sufficient adhesion with the support. 0.001-2 mass% of alkoxysilane compounds can be contained with respect to mass%.

  When the content of the alkoxysilane compound with respect to 100% by mass of the polyimide precursor is 0.01% by mass or more, good adhesion to the support can be obtained. Moreover, it is preferable from a viewpoint of the storage stability of a resin composition that content of an alkoxysilane compound is 2 mass% or less. As for content of an alkoxysilane compound, it is more preferable that it is 0.02-2 mass% with respect to a polyimide precursor, It is further more preferable that it is 0.05-1 mass%, 0.05-0.5 It is more preferable that it is mass%, and it is especially preferable that it is 0.1-0.5 mass%.

  As an alkoxysilane compound, for example, 3-mercaptopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name KBM803, manufactured by Chisso Corporation: trade name: Silaace S810), 3-mercaptopropyltriethoxysilane (manufactured by Azmax Corporation): Trade name SIM6475.0), 3-mercaptopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name LS1375, manufactured by Azumax Co., Ltd .: trade name SIM6474.0), mercaptomethyltrimethoxysilane (manufactured by Azumax Corporation: product) Name SIM6473.5C), mercaptomethylmethyldimethoxysilane (manufactured by AZMAX Co., Ltd .: trade name SIM6473.0), 3-mercaptopropyldiethoxymethoxysilane, 3-mercaptopro Luethoxydimethoxysilane, 3-mercaptopropyltripropoxysilane, 3-mercaptopropyldiethoxypropoxysilane, 3-mercaptopropylethoxydipropoxysilane, 3-mercaptopropyldimethoxypropoxysilane, 3-mercaptopropylmethoxydipropoxysilane, 2- Mercaptoethyltrimethoxysilane, 2-mercaptoethyldiethoxymethoxysilane, 2-mercaptoethylethoxydimethoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethylethoxydipropoxysilane, 2- Mercaptoethyldimethoxypropoxysilane, 2-mercaptoethylmethoxydipropoxysilane, 4-mercaptobutyltrimethoxysilane Lan, 4-mercaptobutyltriethoxysilane, 4-mercaptobutyltripropoxysilane, N- (3-triethoxysilylpropyl) urea (manufactured by Shin-Etsu Chemical Co., Ltd .: trade name LS3610, manufactured by Azmax Corporation: trade name SIU9055. 0), N- (3-trimethoxysilylpropyl) urea (manufactured by Azmax Co., Ltd .: trade name SIU9058.0), N- (3-diethoxymethoxysilylpropyl) urea, N- (3-ethoxydimethoxysilylpropyl) Urea, N- (3-tripropoxysilylpropyl) urea, N- (3-diethoxypropoxysilylpropyl) urea, N- (3-ethoxydipropoxysilylpropyl) urea, N- (3-dimethoxypropoxysilylpropyl) urea Urea, N- (3-methoxydi Roxyxypropyl) urea, N- (3-trimethoxysilylethyl) urea, N- (3-ethoxydimethoxysilylethyl) urea, N- (3-tripropoxysilylethyl) urea, N- (3-tripropoxy) Silylethyl) urea, N- (3-ethoxydipropoxysilylethyl) urea, N- (3-dimethoxypropoxysilylethyl) urea, N- (3-methoxydipropoxysilylethyl) urea, N- (3-trimethoxy Silylbutyl) urea, N- (3-triethoxysilylbutyl) urea, N- (3-tripropoxysilylbutyl) urea, 3- (m-aminophenoxy) propyltrimethoxysilane (manufactured by Azmax Co., Ltd .: trade name SLA0598 0.0), m-aminophenyltrimethoxysilane (AZMAC) Product name SLA0599.0), p-aminophenyltrimethoxysilane (Azmax Co., Ltd. product name: SLA0599.1) Aminophenyltrimethoxysilane (Azmax Co., Ltd. product name: SLA0599.2), 2 -(Trimethoxysilylethyl) pyridine (manufactured by Azmax Co., Ltd .: Trade name SIT83396), 2- (triethoxysilylethyl) pyridine, 2- (dimethoxysilylmethylethyl) pyridine, 2- (diethoxysilylmethylethyl) Pyridine, (3-triethoxysilylpropyl) -t-butylcarbamate, (3-glycidoxypropyl) triethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, Tet -N-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane, tetrakis (methoxyethoxysilane), tetrakis (methoxy-n-propoxysilane), tetrakis (ethoxyethoxysilane), tetrakis (methoxyethoxyethoxysilane) ), Bis (trimethoxysilyl) ethane, bis (trimethoxysilyl) hexane, bis (triethoxysilyl) methane, bis (triethoxysilyl) ethane, bis (triethoxysilyl) ethylene, bis (triethoxysilyl) octane, Bis (triethoxysilyl) octadiene, bis [3- (triethoxysilyl) propyl] disulfide, bis [3- (triethoxysilyl) propyl] tetrasulfide, di-t-butoxydiacetoxysilane, di-i-butoxya Luminoxytriethoxysilane, bis (pentadionate) titanium-O, O'-bis (oxyethyl) -aminopropyltriethoxysilane, phenylsilanetriol, methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol , Isopropylphenylsilanediol, n-butylsiphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylme Ruphenylsilanol, tert-butylmethylphenylsilanol, ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol, n-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, triphenylsilanol, 3-ureidopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyl Triethoxysilane, 3-glycidoxypropyltrimethoxysilane, phenyl Limethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltripropoxysilane, γ-aminopropyltributoxysilane, γ-aminoethyltriethoxysilane, γ-aminoethyltrimethoxy Silane, γ-aminoethyltripropoxysilane, γ-aminoethyltributoxysilane, γ-aminobutyltriethoxysilane, γ-aminobutyltrimethoxysilane, γ-aminobutyltripropoxysilane, γ-aminobutyltributoxysilane, etc. However, it is not limited to these. These may be used alone or in combination of two or more.

  As the silane coupling agent, among the above-described silane coupling agents, from the viewpoint of ensuring the storage stability of the resin composition, phenylsilanetriol, trimethoxyphenylsilane, trimethoxy (p-tolyl) silane, diphenylsilanediol, One or more selected from dimethoxydiphenylsilane, diethoxydiphenylsilane, dimethoxydi-p-tolylsilane, triphenylsilanol and a silane coupling agent represented by each of the following structures is preferable.

(Surfactant or leveling agent)
Moreover, applicability | paintability can be improved by adding surfactant or a leveling agent to a resin composition. Specifically, repelling after application can be prevented.
Examples of such surfactants or leveling agents include organosiloxane polymers KF-640, 642, 643, KP341, X-70-092, X-70-093, KBM303, KBM403, KBM803 (above, trade names, Shin-Etsutsu). Chemical Industry Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (above, trade name, manufactured by Toray Dow Corning Silicone), SILWET L-77, L-7001, FZ-2105, FZ-2120, FZ-2154, FZ-2164, FZ-2166, L-7604 (above, trade name, manufactured by Nihon Unicar), DBE-814, DBE-224 , DBE-621, CMS-626, CMS-222, KF-352A, KF-354L, K F-355A, KF-6020, DBE-821, DBE-712 (Gelest), BYK-307, BYK-310, BYK-378, BYK-333 (above, trade name, manufactured by Big Chemie Japan), granol (trade name) (Made by Kyoeisha Chemical Co., Ltd.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, etc. Product name), Fluorado FC430, FC431 (Sumitomo 3M Co., Ltd., product name), and the like.

  When using a surfactant or a leveling agent, the total blending amount is preferably 0.001 to 5 parts by mass, and 0.01 to 3 parts by mass with respect to 100 parts by mass of the polyimide precursor in the resin composition. More preferred.

<Resin composition>
The resin composition according to the present embodiment is used as a solution composition (varnish) obtained by dissolving the polyimide precursor and other optional components in a solvent.
Here, as the solvent, the same solvent as described above can be used as a solvent that can be used when the polyimide precursor is synthesized.
The amount of the solvent used is preferably such that the solid content concentration of the resin composition is 3 to 50% by mass.
The varnish of the resin composition according to the present embodiment has excellent room temperature storage stability, and the viscosity change rate of the varnish when stored for 4 weeks at room temperature is 10% or less with respect to the initial viscosity. If the storage stability at room temperature is excellent, frozen storage becomes unnecessary and handling becomes easy.

<Laminated body>
The laminate according to the present embodiment includes a support and a polyimide film formed on the support. The laminate may further include an inorganic film on the polyimide film.
The laminate is
A coating film forming step of developing the resin composition according to the present embodiment on the surface of the support to form a coating film; and
It forms by passing through the heating process of heating the said support body and the said coating film, imidating the said polyimide precursor, and forming a polyimide film.
The inorganic film is used as a gas barrier layer for preventing moisture and oxygen from entering the organic EL light emitting layer or the like from the polyimide film according to the present invention, and includes silicon oxide, aluminum oxide, silicon carbide, silicon oxide carbide, Preferred examples include inorganic oxide films such as silicon nitride, silicon nitride, and silicon nitride oxide. The inorganic film is formed using a plasma CVD method 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.
Examples of the developing method include known coating methods such as spin coating, slit coating, and blade coating.
More specifically, after spreading the resin composition on the support (or on the adhesive layer formed on the main surface thereof) and removing the solvent, the polyimide precursor is preferably heated by heating in an inert atmosphere. By imidizing, a polyimide film can be formed on the support.
The solvent removal can be performed, for example, by heat treatment at a temperature of less than 250 ° C., preferably 50 to 200 ° C. for 1 minute to 300 minutes. The imidization can be performed, for example, by a heat treatment at a temperature of 250 ° C. to 550 ° C. for 1 minute to 300 minutes. The ambient atmosphere at the time of imidation is preferably an inert atmosphere such as nitrogen.
Although the thickness of the polyimide film obtained by this Embodiment is not specifically limited, It is preferable that it is the range of 10-50 micrometers, More preferably, it is 15-25 micrometers.

  This laminated body is used for manufacturing a flexible device, for example. More specifically, a semiconductor device can be formed on a polyimide film, and then a support can be peeled off to obtain a flexible device including a flexible transparent substrate made of a polyimide film.

<Polyimide film>
The polyimide film according to the present embodiment is a coating film forming step in which the resin composition containing the polyimide precursor and the solvent according to the above-described embodiment is spread on the surface of the support to form a coating film. ,
A heating step of heating the support and the coating film to imidize the polyimide precursor to form a polyimide film;
It forms by passing through the peeling process which peels the said polyimide film from the said support body, and obtains a polyimide film.
This polyimide film is used for manufacturing a flexible device, for example. Specifically, this polyimide film can be used for a substrate for forming TFTs, a substrate for forming color filters, an alignment film, a transparent substrate for flexible displays, and the like.

<Advantages of the present invention>
As described above, the polyimide precursor according to the present embodiment is preferably (1) as a structure derived from tetracarboxylic dianhydride,
A structure derived from at least one alicyclic tetracarboxylic dianhydride selected from CBDA, H-PMDA, and the like;
A structure derived from aromatic tetracarboxylic dianhydride 1 selected from PMDA and the like,
Having a structure derived from an aromatic tetracarboxylic dianhydride selected from OPDA, 6FDA, etc.
(2) It has a structure derived from TFMB or the like as a diamine-derived structure. A polyimide film manufactured using such a polyimide precursor is colorless and transparent, has a low CTE, and is excellent in elongation. A 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 on a transparent substrate of a flexible display.

More specifically, it is as follows.
When 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 further formed thereon. The step of forming the inorganic film on the substrate is typically performed at a wide temperature range of 150 to 650 ° C. In order to actually exhibit the desired performance, a temperature range of 250 ° C. to 400 ° C. is mainly employed. Examples of the inorganic film include a TFT-IGZO (InGaZnO) oxide semiconductor and a TFT (a-Si-TFT, poly-Si-TFT).

At this time, if the CTE of the flexible substrate is higher than the CTE of the glass substrate, the glass substrate warps and breaks when they shrink during cooling after being expanded in the high-temperature inorganic film forming process. This causes problems such as peeling. In general, the thermal expansion coefficient of a glass substrate is smaller than that of a resin. Therefore, the lower the linear expansion coefficient of the flexible substrate, the better.
In consideration of the above points, the polyimide film according to the present embodiment has an average coefficient of linear expansion (CTE) measured at 100 to 300 ° C. according to the TMA method on the basis of a film thickness of 15 to 25 μm, 0.0 ppm / ° C. or less.
Further, the polyimide film according to the present embodiment has a yellowness (YI value) of 10 or less, and 550 nm when the transmittance is measured with an ultraviolet spectrophotometer on the basis of the film thickness of 15 to 25 μm. The transmittance at 85 can be 85% or more.

The laminate in which the inorganic film is formed on the polyimide film according to the present embodiment has a small surface roughness of the inorganic film, a small haze value, and a small water vapor transmission rate.
In the case of an organic EL display, an inorganic film is formed on a 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, the laminate is turbid and cloudy and is not suitable as a display. Moreover, since the water vapor transmission rate does not fulfill the function as a gas barrier layer, it is not appropriate.
It is considered that the heat resistance of the polyimide film is related to the surface roughness, haze value, and water vapor transmission rate of these laminates. This is because when an inorganic film is formed on a polyimide film by a CVD method, the laminate including the polyimide film is exposed to a temperature higher than the curing (imidization) temperature at the time of forming the polyimide film. . The laminate preferably has a surface roughness of 25 nm or less, a haze of 15 or less, and a water vapor transmission rate of 0.1 g / (m ² · 24 h) or less.

Moreover, it is preferable that the polyimide film which concerns on this Embodiment is 15% or more of elongation with the film thickness of 15-25 micrometers as a reference | standard. By having such elongation, when handling a flexible substrate, it will be excellent in breaking strength, and therefore the yield can be improved.
The polyimide film according to the present embodiment that satisfies the above physical properties can be used for applications in which use is limited by the yellow color of existing polyimide films and applications where transparency is required. Especially suitable as a transparent substrate for flexible displays;
For example, it can also be used for a protective film or a light-diffusing sheet and a coating film (for example, TFT-LCD interlayer, gate insulating film and liquid crystal alignment film) in TFT-LCD. When the polyimide according to this embodiment is applied as the liquid crystal alignment film, it contributes to an increase in the aperture ratio, and a TFT-LCD with a high contrast ratio can be manufactured.

  The polyimide film and laminate manufactured using the polyimide precursor according to the present embodiment can be suitably used for manufacturing, for example, a semiconductor insulating film, a TFT-LCD insulating film, an electrode protective film, and a flexible device. . In particular, it is suitable for manufacturing a substrate. Here, examples of the flexible device include a flexible display, a flexible solar cell, flexible lighting, and a flexible battery.

  Hereinafter, the present invention will be specifically described based on examples. These are described for illustrative purposes, and the scope of the present invention is not limited by the following examples.

Various evaluations in Examples and Comparative Examples were performed as follows.
(Measurement of weight average molecular weight)
The weight average molecular weight was measured under the following conditions using gel permeation chromatography (GPC). A calibration curve for calculating the weight average molecular weight was prepared using standard polystyrene (manufactured by Tosoh Corporation).
Solvent: 24.8 mmol / L lithium bromide monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity) using N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph) 99.5%) and 63.2 mmol / L phosphoric acid (Wako Pure Chemical Industries, high performance liquid chromatograph) added Column: Shodex KD-806M (Showa Denko)
Flow rate: 1.0 mL / min Column temperature: 40 ° C
Pump: PU-2080 Plus (manufactured by JASCO)
Detector: RI-2031Plus (RI: differential refractometer, manufactured by JASCO), UV-2075Plus (UV-VIS: UV-visible light spectrometer, manufactured by JASCO)

(Calculation of imide group concentration of the part derived from alicyclic tetracarboxylic dianhydride)
The imide group concentration in the portion derived from the alicyclic acid dianhydride was calculated from the integrated value of ¹³ C-NMR signal measured for the polyimide precursor varnish. ^{The 13} C-NMR measurement was performed under the following conditions.
Measuring device: JNM-GSX400 type manufactured by JEOL Ltd. Measuring temperature: 23 ° C
Measurement solvent: heavy dimethyl sulfoxide solvent (DMSO-d ₆ )
Signals attributed to the imide bond, amide bond, and carboxylic acid carbon of the portion derived from the alicyclic tetracarboxylic dianhydride appear in the following magnetic field strengths:
Signal attributed to imide-bonded carbon of a portion derived from alicyclic tetracarboxylic dianhydride: around 177 ppm (A)
Signal attributed to the amide bond carbon of the part derived from alicyclic tetracarboxylic dianhydride: around 172 ppm (B)
Signal attributed to the carboxyl group carbon of the portion derived from the alicyclic tetracarboxylic dianhydride: around 177 ppm (C)
Here, for the amic acid (not imidized) site, the integrated values of B and C are the same value. The integral value of the imide bond carbon at the imidized site and the integral value of the amide bond carbon at the non-imidated site are respectively represented by the following formulas:
Integral value of imide bond carbon: integral value of A-integral value of B Integral value of amide bond carbon and carboxyl group carbon: integral value of B × 2
Therefore, the imide group concentration is expressed by the following formula:
Imide group concentration (%) = 100 × (A integrated value−B integrated value) / (A integrated value−B integrated value + B integrated value × 2) = 100 × (A integrated value−B integrated) Value) / (integral value of A + integral value of B)

(Evaluation of varnish storage stability)
Viscosity measurement at 23 ° C. was performed using a sample obtained by leaving the composition varnish prepared in each of the following Examples and Comparative Examples at room temperature for 3 days. Thereafter, the sample which was allowed to stand at room temperature for 4 weeks was used as a sample after 4 weeks, and the viscosity was measured again at 23 ° C.
Said viscosity measurement was performed using the temperature controller viscometer (TV-22 by Toki Sangyo Co., Ltd.).
Using the above measured values, the viscosity change rate at room temperature for 4 weeks was calculated according to the following formula.
Viscosity change rate (%) 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.
A: Viscosity change rate is 5% or less (storage stability “excellent”)
○: Viscosity change rate is 10% or less (storage stability “good”)
×: Viscosity change rate is greater than 10% (storage stability “bad”)

(Production of laminate and isolated film)
The polyimide precursor varnish obtained in each Example and Comparative Example was coated on a non-alkali glass substrate (thickness 0.7 mm) using a bar coater. Subsequently, after 5 minutes to 10 minutes of leveling at room temperature, the film was heated in a hot air oven at 140 ° C. for 60 minutes, and further heated at a predetermined temperature in a nitrogen atmosphere for 60 minutes to form a coating film on the substrate. The laminated body which has this was produced. The film thickness of the coating film in the laminate was adjusted to 20 μm after curing. Subsequently, the coating film was imidized by curing (curing treatment) at a predetermined temperature. After the cured laminate was allowed to stand at room temperature for 24 hours, the polyimide film was peeled from the glass to isolate the film.
In the following evaluation of breaking strength, yellowness and linear expansion coefficient, a polyimide film cured at the predetermined temperature was used as a sample.

(Evaluation of elongation)
A sample of a polyimide film having a width of 5 mm, a length of 50 mm, and a thickness of 20 μm cured at a predetermined temperature was subjected to tensile measurement at a speed of 100 mm / min using a tensile tester (manufactured by A & D Co., Ltd .: RTG-1210). . When the breaking elongation was 20% or more, ◎ (elongation “excellent”), when 15% or more and less than 20%, ○ (elongation “good”), 10% or more and less than 15%. △ (elongation “bad”) and less than 10% were evaluated as (elongation “poor”) x.

(Evaluation of yellowness (YI value))
A polyimide film having a thickness of 20 μm cured at a predetermined temperature was measured with a D65 light source by Nippon Denshoku Industries Co., Ltd. (Spectrophotometer: SE600). When the YI value is 8.0 or less, ◎ (yellowness “excellent”), when the YI value is more than 8.0 and 10.0 or less, ○ (yellowness “good”); The case where it was below was evaluated as Δ (yellowness “bad”) and the case where it was over 15.0 as x (yellowness “poor”).

(Evaluation of linear expansion coefficient (CTE))
The polyimide film cured at a predetermined temperature was measured for specimen elongation under the following conditions by thermomechanical analysis using a thermomechanical analyzer (TMA-50) manufactured by Shimadzu Corporation.
Load: 5g
Temperature rising rate: 10 ° C / min Measurement atmosphere: Nitrogen atmosphere Nitrogen flow rate: 20ml / min)
Measurement temperature range: 50-450 ° C
In this case, the CTE of the polyimide film in the temperature range of 100 to 300 ° C. is obtained. ○ (CTE “good”), the case of 25 ppm / ° C. over 30 ppm / ° C. was evaluated as Δ (CTE “poor”), and the case of over 30 ppm / ° C. was evaluated as x (CTE “poor”).

(Measurement of surface roughness of inorganic film formed on polyimide film)
Using the composition varnishes prepared in each of the above examples and comparative examples, a laminated wafer in which a polyimide film and an inorganic film were laminated in this order on a 6-inch silicon wafer substrate provided with an aluminum vapor deposition layer on the surface, Formed as follows.
First, after spin-coating each composition varnish on the said board | substrate, it heats at 140 degreeC for 60 minute (s) with a hot-air oven, and also heats at 320 degreeC for 60 minutes under nitrogen atmosphere, The polyimide film with a film thickness of 20 micrometers is obtained. A wafer was obtained.
Thereafter, a silicon nitride (SiN _x ) film, which is an inorganic film, was formed to a thickness of 100 nm on the polyimide film formed above at 350 ° C. using a CVD method. Next, the surface roughness of the formed silicon nitride was measured on a scale of 100 μm × 100 μm using Nanopics 2100 (trade name, manufactured by SII Nanotechnology), which is AFM. The test was performed at N = 5, and the average value was taken as the surface roughness Ra.
The results are shown in Table 2.

(Evaluation of Haze)
The laminate wafer obtained above was immersed in a dilute hydrochloric acid aqueous solution, and two layers of the inorganic film and the polyimide film were integrally peeled from the wafer to obtain a polyimide film sample having an inorganic film formed on the surface. Using this sample, Haze was measured based on the JIS K7105 transparency test method using an SC-3H haze meter manufactured by Suga Test Instruments Co., Ltd.
The measurement results were evaluated according to the following criteria.
A: Haze is 5 or less (Haze “excellent”)
○: Haze is greater than 5 and 15 or less (Haze “good”)
X: Haze is greater than 15 (Haze “bad”)
The results are shown in Table 2.

(Evaluation of water vapor transmission rate)
The water vapor transmission rate of the polyimide film having an inorganic film formed on the surface obtained above was measured using a water vapor transmission rate measuring device (model name: PERMATRAN (registered trademark) W3 / 31) manufactured by MOCON. The measurement was performed under the conditions of a temperature of 40 ° C., a humidity of 90% RH, and a measurement area of 80 mmφ. The number of measurements was 5 each, and the average value was regarded as the water vapor transmission rate and evaluated according to the following criteria.
A: Water vapor transmission rate is 0.01 g / (m ² · 24 h) or less (water vapor transmission rate “excellent”)
○: Water vapor transmission rate is larger than 0.01 g / (m ² · 24 h) and 0.1 g / (m ² · 24 h) or less (water vapor transmission rate “good”)
X: Water vapor transmission rate is greater than 0.1 g / (m ² · 24 h) (water vapor transmission rate “poor”)
The results are shown in Table 2.

[Reference Example 1]
In a 500 ml separable flask under nitrogen, 15.69 g (49.00 mmol) of 2,2′-bis (trifluoromethyl) benzidine (TFMB) and 178.95 g of N-methyl-2-pyrrolidone (NMP) were placed. TFMB was dissolved under stirring. Thereafter, 1.09 g (5.0 mmol) of pyromellitic dianhydride (PMDA), 3.10 g (10.0 mmol) of 4,4′-oxydiphthalic dianhydride (ODPA), and 1,2,3, 6.86 g (35.0 mmol) of 4-cyclobutanetetracarboxylic dianhydride (CBDA) was added and stirred at 80 ° C. for 4 hours to obtain an NMP solution of polyamic acid (hereinafter also referred to as “varnish”). It was. The obtained polyamic acid had a weight average molecular weight (Mw) of 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 raw material charge 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), A varnish was obtained in the same manner as in Reference Example 1. The resulting polyamic acid had a weight average molecular weight (Mw) of 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 raw material charge 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), A varnish was obtained in the same manner as in Reference Example 1. The obtained polyamic acid had a weight average molecular weight (Mw) of 128,000. The CTE, YI value and elongation of the film cured at 330 ° C. are shown in Table 2 below.

[Example 4]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 2.24 g (10.0 mmol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (H-PMDA) was added and refluxed at 180 ° C. for 2 hours, followed by azeotropy over 3 hours. The solvent toluene was removed. The flask contents were then cooled to 40 ° C., followed by 12.55 g (39.2 mmol) of TFMB, 168.43 g of NMP, 6.54 g (30.0 mmol) of PMDA, and 3.10 g (10.0 mmol) of ODPA. In addition, a varnish of polyimide-polyamic acid polymer was obtained by stirring at 80 ° C. for 4 hours. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 82,000. The CTE, YI value and elongation of the film cured at 350 ° C. are shown in Table 2 below.

[Reference Example 5]
Reference Example except that the raw material charge 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) A varnish was obtained in the same manner as in 1. The obtained polyamic acid had a weight average molecular weight (Mw) of 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 raw material charge 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), A varnish was obtained in the same manner as in Reference Example 1. The resulting polyamic acid had 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 raw material charge 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), A varnish was obtained in the same manner as in Reference Example 1. The resulting polyamic acid had 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 8]
The raw material charge 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), A varnish was obtained in the same manner as in Reference Example 1. The resulting polyamic acid had a weight average molecular weight (Mw) of 103,000. The CTE, YI value and elongation of the film cured at 330 ° C. are shown in Table 2 below.

[Example 9]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 2.24 g (10.0 mmol) of H-PMDA was added and refluxed at 180 ° C. for 2 hours, and then toluene as an azeotropic solvent was removed over 3 hours. After the flask contents were cooled 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. In addition, a varnish of polyimide-polyamic acid polymer was obtained by stirring at 80 ° C. for 4 hours. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 123,000. The CTE, YI value and elongation of the film cured at 350 ° C. are shown in Table 2 below.

[Example 10]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 2.24 g (10.0 mmol) of H-PMDA was added and 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., 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 In addition, a varnish of polyimide-polyamic acid polymer was obtained by stirring at 80 ° C. for 4 hours. The resulting polyimide-polyamic acid polymer had a weight average molecular weight (Mw) of 81,000. The CTE, YI value and elongation of the film cured at 350 ° C. are shown in Table 2 below.

[Example 11]
Under a nitrogen atmosphere, 6.28 g (19.6 mmol) of TFMB, 32.28 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. To this, 4.48 g (20.0 mmol) of H-PMDA was added and 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., 9.42 g (29.4 mmol) of TFMB, 76.44 g of NMP, 5.45 g (25.0 mmol) of PMDA and 1.55 g (5.0 mmol) of ODPA In addition, a varnish of polyimide-polyamic acid polymer was obtained by stirring at 80 ° C. for 4 hours. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymerization composition was 68,000. The CTE, YI value and elongation of the film cured at 350 ° C. are shown in Table 2 below.

[Example 12]
Under a nitrogen atmosphere, 6.28 g (19.6 mmol) of TFMB, 32.28 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. To this, 4.48 g (20.0 mmol) of H-PMDA was added and 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., 9.42 g (29.4 mmol) of TFMB, 78.28 g of NMP, 4.36 g (20.0 mmol) of PMDA and 3.10 g (10.0 mmol) of ODPA In addition, a varnish of polyimide-polyamic acid polymer was obtained by stirring at 80 ° C. for 4 hours. The resulting polyimide-polyamic acid polymer had a weight average molecular weight (Mw) of 68,000. The CTE, YI value and elongation of the film cured at 350 ° C. are shown in Table 2 below.

[Example 13]
Under a nitrogen atmosphere, 0.63 g (1.96 mmol) of TFMB, 3.22 g of NMP and 30 g of toluene were added to a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. To this, 0.45 g (2.00 mmol) of H-PMDA was added and 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 In addition, a varnish of polyimide-polyamic acid polymer was obtained by stirring at 80 ° C. for 4 hours. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 112,000. The CTE, YI value and elongation of the film cured at 350 ° C. are shown in Table 2 below.

[Example 14]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 2.24 g (10.0 mmol) of H-PMDA was added and refluxed at 180 ° C. for 2 hours, and then toluene as an azeotropic solvent was removed over 3 hours. After the flask contents were cooled to 40 ° C., 12.55 g (39.2 mmol) TFMB, 166.88 g NMP, 7.09 g (32.5 mmol) PMDA, and 2.33 g (7.5 mmol) ODPA In addition, a varnish of polyimide-polyamic acid polymer was obtained by stirring at 80 ° C. for 4 hours. The obtained polyimide-polyamic acid polymerization composition had a weight average molecular weight (Mw) of 79,000. The CTE, YI value and elongation of the film cured at 350 ° C. are shown in Table 2 below.

[Example 15]
Under a nitrogen atmosphere, 9.42 g (29.4 mmol) of TFMB, 48.42 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 6.78 g (30.0 mmol) of H-PMDA was added and 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., 6.28 g (19.6 mmol) of TFMB, 60.54 g of NMP, 3.27 g (15.0 mmol) of PMDA, and 1.55 g (5.0 mmol) of ODPA. In addition, a varnish of polyimide-polyamic acid polymer was obtained by stirring at 80 ° C. for 4 hours. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymerization composition was 56,000. The CTE, YI value and elongation of the film cured at 350 ° C. are shown in Table 2 below.

[Example 16]
Under a nitrogen atmosphere, 3.14 g (9.80 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 2.24 g (10.0 mmol) of H-PMDA was added and refluxed at 180 ° C. for 2 hours, and then toluene as an azeotropic solvent was removed over 3 hours. After the flask contents were cooled to 40 ° C., 12.55 g (39.2 mmol) of TFMB, 168.43 g of NMP, 4.36 g (20.0 mmol) of PMDA, and 3.10 g (10.0 mmol) of ODPA And 1.96 g (10.0 mmol) of CBDA were added and stirred at 80 ° C. for 4 hours to obtain a polyimide-polyamic acid polymer varnish. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 71,000. The CTE, YI value and elongation of the film cured at 350 ° C. are shown in Table 2 below.

[Reference Example 17]
TFMB 15.69 g (49.0 mmol), NMP 162.24 g, PMDA 6.54 g (30.0 mmol), 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) 4.44 g (10 0.0 mmol) and CBDA 1.96 g (10 mmol), except that the varnish was obtained in the same manner as in Reference Example 1. The resulting polyamic acid had a weight average molecular weight (Mw) of 159,000. The CTE, YI value and elongation of the film cured at 330 ° C. are shown in Table 2 below.

[Example 18]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 2.24 g (10.0 mmol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (H-PMDA) was added and refluxed at 180 ° C. for 2 hours, followed by azeotropy over 3 hours. The solvent toluene was removed. After the flask contents were cooled to 40 ° C., 12.55 g (39.2 mmol) TFMB, 147.70 g NMP, 6.54 g (30.0 mmol) PMDA, and 4.44 g (10.0 mmol) 6FDA. In addition, a varnish of polyimide-polyamic acid polymer was obtained by stirring at 80 ° C. for 4 hours. The resulting polyimide-polyamic acid polymer had a weight average molecular weight (Mw) of 85,000. The CTE, YI value and elongation of the film cured at 350 ° C. are shown in Table 2 below.

[Example 19]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 2.24 g (10.0 mmol) of H-PMDA was added and 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 infrared spectroscopic analysis (IR) that absorption (C═O) in the vicinity of 1,650 cm ⁻¹ derived from the amide bond had disappeared. Thereafter, 12.55 g (39.2 mmol) of TFMB, 153.4 g of NMP, 5.45 g (25.0 mmol) of PMDA, and 6.66 g (15.0 mmol) of 6FDA were added to the flask, and then at 80 ° C. for 4 hours. By stirring, a polyimide-polyamic acid polymer varnish was obtained. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 88,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Example 20]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 2.24 g (10.0 mmol) of H-PMDA was added and 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 absorption (C═O) in the vicinity of 1,650 cm ⁻¹ derived from the amide bond had disappeared. Then, add 12.55 g (39.2 mmol) of TFMB, 159.8 g of NMP, 4.36 g (20.0 mmol) of PMDA and 8.88 g (20.0 mmol) of 6FDA, and stir at 80 ° C. for 4 hours. Thus, a varnish of a polyimide-polyamic acid polymer was obtained. The resulting polyimide-polyamic acid polymer had a weight average molecular weight (Mw) of 86,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Example 21]
Under a nitrogen atmosphere, 6.28 g (19.6 mmol) of TFMB, 32.28 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. To this, 4.48 g (20.0 mmol) of H-PMDA was added and 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 absorption (C═O) in the vicinity of 1,650 cm ⁻¹ derived from the amide bond had disappeared. Then, 9.42 g (29.4 mmol) of TFMB, 124.9 g of NMP, 5.45 g (25.0 mmol) of PMDA, and 2.22 g (5.0 mmol) of 6FDA are added and stirred at 80 ° C. for 4 hours. Thus, a varnish of a polyimide-polyamic acid polymer was obtained. The resulting polyimide-polyamic acid polymer had a weight average molecular weight (Mw) of 76,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Example 22]
Under a nitrogen atmosphere, 6.28 g (19.6 mmol) of TFMB, 32.28 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. To this, 4.48 g (20.0 mmol) of H-PMDA was added and 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 absorption (C═O) in the vicinity of 1,650 cm ⁻¹ derived from the amide bond had disappeared. Then, 9.42 g (29.4 mmol) of TFMB, 131.3 g of NMP, 4.36 g (20.0 mmol) of PMDA and 4.44 g (10.0 mmol) of 6FDA are added and stirred at 80 ° C. for 4 hours. Thus, a varnish of a polyimide-polyamic acid polymer was obtained. The resulting polyimide-polyamic acid polymer had a weight average molecular weight (Mw) of 77,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Example 23]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. To this, 0.45 g (2.00 mmol) of H-PMDA was added and 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 absorption (C═O) in the vicinity of 1,650 cm ⁻¹ derived from the amide bond had disappeared. Then, 12.55 g (39.2 mmol) of TFMB, 158.3 g of NMP, 6.33 g (29.0 mmol) of PMDA, and 8.44 g (19.0 mmol) of 6FDA are added and stirred at 80 ° C. for 4 hours. Thus, a varnish of a polyimide-polyamic acid polymer was obtained. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 89,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Example 24]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 2.24 g (10.0 mmol) of H-PMDA was added and 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 absorption (C═O) in the vicinity of 1650 cm ⁻¹ derived from the amide bond had disappeared. Then, add 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, and stir at 80 ° C. for 4 hours. Thus, a varnish of a polyimide-polyamic acid polymer was obtained. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 89,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Example 25]
Under a nitrogen atmosphere, 9.42 g (29.4 mmol) of TFMB, 48.42 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 6.78 g (30.0 mmol) of H-PMDA was added and 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 absorption (C═O) in the vicinity of 1,650 cm ⁻¹ derived from the amide bond had disappeared. Then, 6.28 g (19.6 mmol) of TFMB, 109.5 g of NMP, 3.27 g (15.0 mmol) of PMDA and 2.22 g (5.0 mmol) of 6FDA were added and stirred at 80 ° C. for 4 hours. A polyimide-polyamic acid polymer varnish was obtained. The resulting polyimide-polyamic acid polymer had a weight average molecular weight (Mw) of 75,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Example 26]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 2.24 g (10.0 mmol) of H-PMDA was added and 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 absorption (C═O) in the vicinity of 1,650 cm ⁻¹ derived from the amide bond had disappeared. Then, 12.55 g (39.2 mmol) of TFMB, 153.5 g of NMP, 3.27 g (15.0 mmol) of PMDA, 4.41 g (15.0 mmol) of BPDA and 4.44 g (10.0 mmol) of 6FDA In addition, by stirring for 4 hours at 80 ° C., a polyimide-polyamic acid polymer varnish was obtained. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 87,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Example 27]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 2.24 g (10.0 mmol) of H-PMDA was added and 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 absorption (C═O) in the vicinity of 1,650 cm ⁻¹ derived from the amide bond had disappeared. Then, 12.55 g (39.2 mmol) of TFMB, 143.3 g of NMP, 6.54 g (30.0 mmol) of PMDA, 1.55 g (5.0 mmol) of ODPA and 2.22 g (5.0 mmol) of 6FDA In addition, by stirring for 4 hours at 80 ° C., a polyimide-polyamic acid polymer varnish was obtained. The resulting polyimide-polyamic acid polymer had a weight average molecular weight (Mw) of 86,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Example 28]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 1.12 g (5.0 mmol) of H-PMDA and 0.98 g (5.0 mmol) of CBDA were added and refluxed at 180 ° C. for 2 hours, and then toluene as an azeotropic solvent was removed over 3 hours. did. The contents of the flask were cooled to 40 ° C., and it was confirmed by IR that absorption (C═O) in the vicinity of 1,650 cm ⁻¹ derived from the amide bond had disappeared. Then, add 12.55 g (39.2 mmol) of TFMB, 146.3 g of NMP, 6.54 g (30.0 mmol) of PMDA, and 4.44 g (10.0 mmol) of 6FDA, and stir at 80 ° C. for 4 hours. Thus, a varnish of a polyimide-polyamic acid polymer was obtained. The resulting polyimide-polyamic acid polymer had a weight average molecular weight (Mw) of 90,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Example 29]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 0.34 g (1.5 mmol) of H-PMDA was added and 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 absorption (C═O) in the vicinity of 1,650 cm ⁻¹ derived from the amide bond had disappeared. Then, TFMB 12.55 g (39.2 mmol), NMP 147 g, PMDA 6.54 g (30.0 mmol), 6FDA 4.44 g (10.0 mmol) and H-PMDA 1.9 g (8.5 mmol) In addition, by stirring for 4 hours at 80 ° C., a polyimide-polyamic acid polymer varnish was obtained. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 71,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Example 30]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 0.56 g (2.5 mmol) of H-PMDA was added and 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 absorption (C═O) in the vicinity of 1,650 cm ⁻¹ derived from the amide bond had disappeared. Then, TFMB 12.55 g (39.2 mmol), NMP 147 g, PMDA 6.54 g (30.0 mmol), 6FDA 4.44 g (10.0 mmol), and H-PMDA 1.68 g (7.5 mmol) In addition, by stirring for 4 hours at 80 ° C., a polyimide-polyamic acid polymer varnish was obtained. The resulting polyimide-polyamic acid polymer had a weight average molecular weight (Mw) of 75,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Example 31]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 0.78 g (3.5 mmol) of H-PMDA was added and 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 absorption (C═O) in the vicinity of 1,650 cm ⁻¹ derived from the amide bond had disappeared. Then, 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 In addition, by stirring for 4 hours at 80 ° C., a polyimide-polyamic acid polymer varnish was obtained. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 78,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Example 32]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 0.62 g (2.75 mmol) of H-PMDA was added and 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 absorption (C═O) in the vicinity of 1,650 cm ⁻¹ derived from the amide bond had disappeared. Then, 12.55 g (39.2 mmol) of TFMB, 153.3 g of NMP, 6.54 g (30.0 mmol) of PMDA, 6.66 g (15.0 mmol) of 6FDA and 0.5 g (2 of H-PMDA) .25 mmol) was added and stirred at 80 ° C. for 4 hours to obtain a polyimide-polyamic acid polymer varnish. The resulting polyimide-polyamic acid polymer had a weight average molecular weight (Mw) of 80,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Example 33]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 1.68 g (7.5 mmol) of H-PMDA was added and 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 absorption (C═O) in the vicinity of 1,650 cm ⁻¹ derived from the amide bond had disappeared. Then, 12.55 g (39.2 mmol) of TFMB, 160.1 g of NMP, 6.54 g (30.0 mmol) of PMDA, 2.22 g (5.0 mmol) of 6FDA, and 5.1 g (22 of H-PMDA) 0.5 mmol) and stirring at 80 ° C. for 4 hours to obtain a polyimide-polyamic acid polymer varnish. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 71,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Example 34]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 1.96 g (10.0 mmol) of CBDA was added and 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 absorption (C═O) in the vicinity of 1,650 cm ⁻¹ derived from the amide bond had disappeared. Then, add 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, and stir at 80 ° C. for 4 hours. Thus, a varnish of a polyimide-polyamic acid polymer was obtained. The resulting polyimide-polyamic acid polymer had a weight average molecular weight (Mw) of 120,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Example 35]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 0.98 g (5.0 mmol) of CBDA was added and 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 absorption (C═O) in the vicinity of 1,650 cm ⁻¹ derived from the amide bond had disappeared. Then, add 12.55 g (39.2 mmol) of TFMB, 191.3 g of NMP, 5.45 g (25.0 mmol) of PMDA and 8.88 g (20.0 mmol) of 6FDA, and stir at 80 ° C. for 4 hours. Thus, a varnish of a polyimide-polyamic acid polymer was obtained. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 95,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Example 36]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 1.96 g (10.0 mmol) of CBDA was added and 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 absorption (C═O) in the vicinity of 1,650 cm ⁻¹ derived from the amide bond had disappeared. Then, add 12.55 g (39.2 mmol) of TFMB, 175.5 g of NMP, 6.54 g (30.0 mmol) of PMDA, and 4.44 g (10.0 mmol) of 6FDA, and stir at 80 ° C. for 4 hours. Thus, a varnish of a polyimide-polyamic acid polymer was obtained. The resulting polyimide-polyamic acid polymer had a weight average molecular weight (Mw) of 100,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Example 37]
Under a nitrogen atmosphere, 9.42 g (29.4 mmol) of TFMB, 48.42 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Then, 5.88 g (30.0 mmol) of CBDA was added and 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 absorption (C═O) in the vicinity of 1,650 cm ⁻¹ derived from the amide bond had disappeared. Then, 6.28 g (19.6 mmol) of TFMB, 169.5 g of NMP, 6.54 g (30.0 mmol) of PMDA and 4.44 g (10.0 mmol) of 6FDA are added and stirred at 80 ° C. for 4 hours. Thus, a varnish of a polyimide-polyamic acid polymer was obtained. The resulting polyimide-polyamic acid polymer had a weight average molecular weight (Mw) of 100,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Example 38]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 0.29 g (1.5 mmol) of CBDA was added and 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 absorption (C═O) in the vicinity of 1,650 cm ⁻¹ derived from the amide bond had disappeared. Then, 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 In addition, by stirring for 4 hours at 80 ° C., a polyimide-polyamic acid polymer varnish was obtained. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 95,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Example 39]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 0.53 g (2.75 mmol) of CBDA was added and 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 absorption (C═O) in the vicinity of 1,650 cm ⁻¹ derived from the amide bond had disappeared. Then, 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. In addition, by stirring for 4 hours at 80 ° C., a polyimide-polyamic acid polymer varnish was obtained. The resulting polyimide-polyamic acid polymer had a weight average molecular weight (Mw) of 80,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Example 40]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 1.47 g (7.5 mmol) of CBDA was added and 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 absorption (C═O) in the vicinity of 1,650 cm ⁻¹ derived from the amide bond had disappeared. Then, 12.55 g (39.2 mmol) of TFMB, 186.8 g of NMP, 6.54 g (30.0 mmol) of PMDA, 2.22 g (5.0 mmol) of 6FDA and 4.41 g (22.5 mmol) of CBDA In addition, by stirring for 4 hours at 80 ° C., a polyimide-polyamic acid polymer varnish was obtained. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 91,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Example 41]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 2.24 g (10.0 mmol) of H-PMDA was added and 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 absorption (C═O) in the vicinity of 1,650 cm ⁻¹ derived from the amide bond had disappeared. Then, 12.55 g (39.2 mmol) of TFMB, 160 g of NMP, 8.83 g (30.0 mmol) of BPDA, and 4.44 g (10.0 mmol) of 6FDA were added and stirred at 80 ° C. for 4 hours. A varnish of polyimide-polyamic acid polymer was obtained. The resulting polyimide-polyamic acid polymer had a weight average molecular weight (Mw) of 86,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Example 42]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 2.24 g (10.0 mmol) of H-PMDA was added and 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. and confirming that the absorption (C═O) around 1,650 cm ⁻¹ derived from the amide bond disappeared by IR, 12.55 g (39. 2mmol), 147.8 g of NMP, 6.54 g (30.0 mmol) of PMDA and 4.58 g (10.0 mmol) of 4,4′-biphenylbis (trimellitic acid monoester anhydride (TAHQ)) A varnish of a polyimide-polyamic acid polymer was obtained by stirring at 4 ° C. for 4 hours, and a weight-average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 84,000. The evaluation results are shown in Table 2.

[Example 43]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 2.1 g (10.0 mmol) of CPDA was added and 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 absorption (C═O) in the vicinity of 1,650 cm ⁻¹ derived from the amide bond had disappeared. Then, add 12.55 g (39.2 mmol) of TFMB, 146.3 g of NMP, 6.54 g (30.0 mmol) of PMDA, and 4.44 g (10.0 mmol) of 6FDA, and stir at 80 ° C. for 4 hours. Thus, a varnish of a polyimide-polyamic acid polymer was obtained. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 71,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Example 44]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 3.06 g (10.0 mmol) of H-BPDA was added and 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 absorption (C═O) in the vicinity of 1,650 cm ⁻¹ derived from the amide bond had disappeared. Then, add 12.55 g (39.2 mmol) of TFMB, 151.7 g of NMP, 6.54 g (30.0 mmol) of PMDA, and 4.44 g (10.0 mmol) of 6FDA, and stir at 80 ° C. for 4 hours. Thus, a varnish of a polyimide-polyamic acid polymer was obtained. The resulting polyimide-polyamic acid polymer had a weight average molecular weight (Mw) of 73,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Example 45]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Then, 2.36 g (10.0 mmol) of BCDA was added and 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 absorption (C═O) in the vicinity of 1,650 cm ⁻¹ derived from the amide bond had disappeared. Then, add 12.55 g (39.2 mmol) of TFMB, 147.7 g of NMP, 6.54 g (30.0 mmol) of PMDA, and 4.44 g (10.0 mmol) of 6FDA, and stir at 80 ° C. for 4 hours. According to the above, a varnish of a polyimide-polyamic acid polymer was obtained. The resulting polyimide-polyamic acid polymer had a weight average molecular weight (Mw) of 75,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Example 46]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 2.48 g (10.0 mmol) of bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BOTDA) was added, and 2 at 180 ° C. After refluxing for a period of time, 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 absorption (C═O) in the vicinity of 1,650 cm ⁻¹ derived from the amide bond had disappeared. Then, add 12.55 g (39.2 mmol) of TFMB, 148.4 g of NMP, 6.54 g (30.0 mmol) of PMDA, and 4.44 g (10.0 mmol) of 6FDA, and stir at 80 ° C. for 4 hours. Thus, a varnish of a polyimide-polyamic acid polymer was obtained. The resulting polyimide-polyamic acid polymer had a weight average molecular weight (Mw) of 74,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Example 47]
In a separable flask equipped with a Dean Stark apparatus and a refluxer, in a nitrogen atmosphere, 2.02 g (9.8 mmol) of 2,2′-dimethylbiphenyl-4,4′-diamine (mTB) and 16.14 g of NMP were added. And 50 g of toluene were added, and mTB was dissolved under stirring. Thereto, 2.24 g (10.0 mmol) of H-PMDA was added and 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 absorption (C═O) in the vicinity of 1,650 cm ⁻¹ derived from the amide bond had disappeared. Then, 8.32 g (39.2 mmol) of mTB, 117.2 g of NMP, 6.54 g (30.0 mmol) of PMDA and 4.44 g (10.0 mmol) of 6FDA are added and stirred at 80 ° C. for 4 hours. Thus, a varnish of a polyimide-polyamic acid polymer was obtained. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 82,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Example 48]
In a separable flask equipped with a Dean Stark apparatus and a refluxer, 2.23 g (9.8 mmol) of 4,4′-diaminobenzanilide (DABA), 16.14 g of NMP and 50 g of toluene were placed under a nitrogen atmosphere. DABA was dissolved under stirring. Thereto, 2.24 g (10.0 mmol) of H-PMDA was added and 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 absorption (C═O) in the vicinity of 1,650 cm ⁻¹ derived from the amide bond had disappeared. Thereafter, 8.91 g (39.2 mmol) of DABA, 121.4 g of NMP, 6.54 g (30.0 mmol) of PMDA and 4.44 g (10.0 mmol) of 6FDA are added and stirred at 80 ° C. for 4 hours. Thus, a varnish of a polyimide-polyamic acid polymer was obtained. The resulting polyimide-polyamic acid polymer had a weight average molecular weight (Mw) of 83,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Example 49]
In a separable flask equipped with a Dean Stark apparatus and a refluxer, under a nitrogen atmosphere, 2.24 g (9.8 mmol) of 4-aminophenyl-4-aminobenzoate (APAB), 16.14 g of NMP and 50 g of toluene were placed. The APAB was dissolved under stirring. Thereto, 2.24 g (10.0 mmol) of H-PMDA was added and 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 absorption (C═O) in the vicinity of 1,650 cm ⁻¹ derived from the amide bond had disappeared. Then, 8.95 g (39.2 mmol) of APAB, 121.6 g of NMP, 6.54 g (30.0 mmol) of PMDA, and 4.44 g (10.0 mmol) of 6FDA are added and stirred at 80 ° C. for 4 hours. Thus, a varnish of a polyimide-polyamic acid polymer was obtained. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 82,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Example 50]
In the varnish of the polyimide-polyamic acid polymer obtained in Example 9, 0.5 part by weight of alkoxysilane compound 1 (ROSi1) is dissolved with respect to 100 parts by weight of the resin, and filtered through a 0.1 μm filter. By doing so, the resin composition was prepared. The properties of this composition and its cured film were measured according to the evaluation method described above. The obtained results are shown in Table 2.
[Example 51]
By dissolving 0.5 parts by weight of the alkoxysilane compound 1 in 100 parts by weight of the resin in the polyimide-polyamic acid polymer varnish obtained in Example 19, and filtering through a 0.1 μm filter. The resin composition was prepared. The properties of this composition and its cured film were measured according to the evaluation method described above. The obtained results are shown in Table 2.
[Example 52]
Surfactant 1 (Surf1) in terms of 0.05 parts by weight is dissolved in 100 parts by weight of the resin in the polyimide-polyamic acid polymer varnish obtained in Example 9, and filtered through a 0.1 μm filter. By doing so, the resin composition was prepared. The properties of this composition and its cured film were measured according to the evaluation method described above. The obtained results are shown in Table 2.
[Example 53]
By dissolving 0.05 part by weight of surfactant 1 in 100 parts by weight of resin in the polyimide-polyamic acid polymer varnish obtained in Example 19, and filtering through a 0.1 μm filter. The resin composition was prepared. The properties of this composition and its cured film were measured according to the evaluation method described above. The obtained results are shown in Table 2.
[Comparative Example 1]
The varnish was prepared in the same manner as in Reference Example 1 except that the raw material charge was changed to TFMB 14.39 g (44.9 mmol), NMP 163.23 g, PMDA 10.0 g (45.8 mmol), ODPA 0 g (0 mmol) and CBDA 0 g (0 mmol). Got. 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 cured at 350 ° C. are shown in Table 2 below.

[Comparative Example 2]
Varnish as in Reference Example 1 except that the raw material charge was changed to TFMB 10.12 g (31.6 mmol), NMP 134.65 g, PMDA 0 g (0 mmol), ODPA 10.0 g (32.2 mmol) and CBDA 0 g (0 mmol). Got. 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 cured at 350 ° C. are shown in Table 2 below.

[Comparative Example 3]
Varnish similar to Reference Example 1 except that the raw material charge was changed to TFMB 16.00 g (50.0 mmol), NMP 174.00 g, PMDA 0 g (0 mmol), ODPA 0 g (0 mmol) and CBDA 10.00 g (51.0 mmol). Got. The weight average molecular weight (Mw) of the polyamic acid in the obtained varnish was 221,000. The CTE, YI value and elongation of the film cured at 330 ° C. are shown in Table 2 below.

[Comparative Example 4]
Under a nitrogen atmosphere, 14.00 g (43.7 mmol) of TFMB, 160.62 g of NMP, and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 10.00 g (44.6 mmol) of H-PMDA was added and refluxed at 180 ° C. for 2 hours, and then toluene as an azeotropic solvent was removed over 3 hours. Thereafter, the contents of the flask were cooled to room temperature to obtain a polyimide varnish. The weight average molecular weight (Mw) of the polyimide in the obtained varnish was 50,600. The CTE, YI value and elongation of the film cured at 350 ° C. are shown in Table 2 below.

[Comparative Example 5]
The varnish was changed in the same manner as in Reference Example 1 except that the raw material charge 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). Obtained. 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 cured at 350 ° C. are shown in Table 2 below.

[Comparative Example 6]
Reference Example 1 except that the raw material charge was changed to TFMB 16.44 g (51.3 mmol), NMP 184.18 g, PMDA 8.00 g (36.7 mmol), ODPA 0 g (0 mmol) and CBDA 3.08 g (15.7 mmol). A varnish was 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]
Reference Example 1 except that the raw material charge was changed to TFMB 14.17 g (44.2 mmol), NMP 171.31 g, PMDA 0 g (0 mmol), ODPA 7.00 g (22.6 mmol) and CBDA 4.43 g (22.6 mmol). A varnish was obtained in the same manner. The weight average molecular weight (Mw) of the obtained varnish was 105,000. The CTE, YI value and breaking strength of the film cured at 330 ° C. are shown in Table 2 below.

[Comparative Example 8]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 2.24 g (10.0 mmol) of H-PMDA was added and 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., 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 stirred at 80 ° C. for 4 hours. A polyimide-polyamic acid polymer varnish was obtained. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 66,700. The CTE, YI value and elongation of the film cured at 350 ° C. are shown in Table 2 below.

[Comparative Example 9]
Reference Example, except that raw material charge was changed to TFMB 15.69 g (49.0 mmol), NMP 175.05 g, PMDA 6.54 g (30.0 mmol), ODPA 0 g (0 mmol) and CBDA 3.92 g (20.0 mmol) A varnish was obtained in the same manner as in 1. 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]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 2.24 g (10.0 mmol) of H-PMDA was added and 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., 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 stirred at 80 ° C. for 4 hours. A varnish of a polyimide-polyamic acid polymerization composition was obtained. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymerization composition was 226,000. The CTE, YI value and elongation of the film cured at 350 ° C. are shown in Table 2 below.

[Comparative Example 11]
Reference Example 1 except that the raw material charge was changed to TFMB 15.69 g (49.0 mmol), NMP 193.54 g, PMDA 0 g (0 mmol), ODPA 9.31 g (30.0 mmol) and CBDA 3.92 g (20.0 mmol). A varnish was obtained in the same manner. The polymer contained in the obtained varnish had a weight average molecular weight (Mw) of 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]
Reference Example 1 except that the raw material charge was changed to TFMB 15.69 g (49.0 mmol), NMP 178.27 g, PMDA 0 g (0 mmol), ODPA 3.10 g (10.0 mmol) and CBDA 7.84 g (40.0 mmol). A varnish was 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]
Under a nitrogen atmosphere, 12.55 g (39.2 mmol) of TFMB, 64.56 g of NMP, and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. To this, 8.97 g (40.0 mmol) of H-PMDA was added and 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., 3.14 g (9.8 mmol) of TFMB, 46.48 g of NMP and 3.1 g (10.0 mmol) of ODPA were added and stirred at 80 ° C. for 4 hours. A polyimide-polyamic acid polymer varnish was obtained. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 49,800. The CTE, YI value and elongation of the film cured at 350 ° C. are shown in Table 2 below.

[Comparative Example 14]
A varnish was obtained in the same manner as in Reference Example 1 except that the raw material charge was changed to TFMB 7.06 g (22.0 mmol), NMP 96.67 g, PMDA 0 g (0 mmol) and 6FDA 10.00 g (22.5 mmol). . 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 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. Next, 14.71 g (50.0 mmol) of BPDA was added and stirred at 80 ° C. for 4 hours to obtain an NMP solution of polyamic acid (varnish). The resulting polyamic acid had a weight average molecular weight (Mw) of 49,000. The evaluation results of the film 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. Next, 22.92 g (50.0 mmol) of TAHQ was added and stirred at 80 ° C. for 4 hours to obtain an NMP solution of polyamic acid (varnish). The resulting polyamic acid had a weight average molecular weight (Mw) of 64,000. The evaluation results of the film cured at 330 ° C. are shown in Table 2.

[Comparative Example 17]
Under a nitrogen atmosphere, 15.69 g (49.0 mmol) of TFMB, 175.3 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 10.51 g (100.0 mmol) of CPDA was added and refluxed at 180 ° C. for 2 hours, and then toluene as an azeotropic solvent was removed over 3 hours. Thereafter, the contents of the flask were cooled to room temperature to obtain a polyimide varnish. The weight average molecular weight (Mw) of the polyimide in the obtained varnish was 51,600. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Comparative Example 18]
Under a nitrogen atmosphere, 15.69 g (49.0 mmol) of TFMB, 175.3 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 15.32 g (100.0 mmol) of H-BPDA was added and refluxed at 180 ° C. for 2 hours, and then toluene as an azeotropic solvent was removed over 3 hours. Thereafter, the contents of the flask were cooled to room temperature to obtain a polyimide varnish. The weight average molecular weight (Mw) of the polyimide in the obtained varnish was 54,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Comparative Example 19]
Under a nitrogen atmosphere, 15.69 g (49.0 mmol) of TFMB, 175.3 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. BCDA (11.82 g, 100.0 mmol) was added thereto and refluxed at 180 ° C. for 2 hours, and then toluene as an azeotropic solvent was removed over 3 hours. Thereafter, the contents of the flask were cooled to room temperature to obtain a polyimide varnish. The weight average molecular weight (Mw) of the polyimide in the obtained varnish was 50,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Comparative Example 20]
Under a nitrogen atmosphere, 15.69 g (49.0 mmol) of TFMB, 175.3 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 12.41 g (100.0 mmol) of BOTDA was added and refluxed at 180 ° C. for 2 hours, and then toluene as an azeotropic solvent was removed over 3 hours. Thereafter, the contents of the flask were cooled to room temperature to obtain a polyimide varnish. The weight average molecular weight (Mw) of the polyimide in the obtained varnish was 54,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Comparative Example 21]
Under a nitrogen atmosphere, 3.14 g (9.8 mmol) of TFMB, 16.14 g of NMP and 50 g of toluene were placed in a separable flask equipped with a Dean Stark apparatus and a refluxer, and TFMB was dissolved under stirring. Thereto, 0.16 g (0.7 mmol) of H-PMDA was added and 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 absorption (C═O) in the vicinity of 1,650 cm ⁻¹ derived from the amide bond had disappeared. Then, 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 In addition, by stirring for 4 hours at 80 ° C., a polyimide-polyamic acid polymer varnish was obtained. The weight average molecular weight (Mw) of the obtained polyimide-polyamic acid polymer was 51,000. The evaluation results of the film cured at 350 ° C. are shown in Table 2.

[Comparative Example 22]
The varnish was prepared according to the method described 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 32.02 g (100.0 mmol) of TFMB was completely dissolved at room temperature. Next, 111.1 g (25.0 mmol) of 6FDA, 109.1 g (50.0 mmol) of PMDA and 56.04 g (25.0 mmol) of H-PMDA were sequentially added, and the mixture was stirred at room temperature for 12 hours. Then, after heating for 20 minutes with a 120 degreeC oil bath, it stirred at normal temperature for 12 hours, and the polyamic-acid solution (varnish) was obtained. The obtained polyamic acid had a weight average molecular weight (Mw) of 32,000.
Table 2 shows the evaluation results of the polyimide film obtained by heating from 80 ° C. to 250 ° C. over 8 hours using the above varnish and then gradually cooling.

[Comparative Example 23]
The varnish was prepared according to the method described in Korean Patent Publication No. 10-2013-0077946.
The operation was performed in the same manner as in Comparative Example 22 except that the raw material charge 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 are shown in Table 2.

[Comparative Example 24]
The varnish was prepared according to the method described in Korean Patent Publication No. 10-2013-0077946.
The operation was performed in the same manner as in Comparative Example 22 except that the raw materials were 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 are shown in Table 2.

Abbreviations of the components listed in Table 1 have the following meanings, respectively.
[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′-biphenylbis (trimellitic acid monoester anhydride)
[Alicyclic tetracarboxylic dianhydride]
CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride H-PMDA: 1,2,4,5-cyclohexanetetracarboxylic dianhydride CPDA: 1,2,3,4-cyclopentanetetracarboxylic Acid 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′-diaminobenzanilide APAB: 4-aminophenyl-4-amino Benzoate [other additives]
ROSi1: alkoxysilane compound 1, compound of the following structural formula

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

As shown in the table, a structure derived from an alicyclic tetracarboxylic dianhydride, a structure derived from the aromatic tetracarboxylic dianhydride 1, and a structure derived from the aromatic tetracarboxylic dianhydride 2 A resin composition (varnish) containing a polyimide precursor having all of
(0) The viscosity change rate at room temperature storage for 4 weeks is 10% or less,
The polyimide film obtained by curing the composition has the following conditions in film properties:
(1) CTE is 25 ppm or less (2) YI value is 10 or less (3) Elongation satisfies 15% or more simultaneously,
A laminate in which an inorganic film is formed on the polyimide film,
(4) Haze is 15 or less (5) It was confirmed that the water vapor transmission rate satisfies 0.1 g / (m ² · 24 h) or less simultaneously.

Also,
From the evaluation results of Comparative Examples 1 to 4, 14 and 15 to 20, the polyimide films using the polyimide precursor having only a structure derived from one kind of tetracarboxylic dianhydride are (0) to (5 ) Not all film properties can be met simultaneously;
From the evaluation results of Comparative Examples 5 to 13, the polyimide films using the polyimide precursors having two types of structures respectively derived from the two types of tetracarboxylic dianhydrides are the above (0) to (5 ) For all film properties, it may not give sufficient performance.
Each was confirmed. further,
From the evaluation results of Comparative Examples 21 to 25, even the polyimide film using the polyimide precursors having the three types of structures respectively derived from the three types of tetracarboxylic dianhydrides, When the imidation rate of the amide bond derived from the cyclic tetracarboxylic dianhydride is outside the range of 10 to 100%, sufficient performance is imparted for all the film properties (0) to (5) above. It was confirmed that this was not possible.
From the above results, the polyimide precursor is derived from the alicyclic tetracarboxylic dianhydride, the structure derived from the aromatic tetracarboxylic dianhydride 1, and the aromatic tetracarboxylic dianhydride 2 And the composition containing the polyimide precursor only when the imidation ratio of the amide bond derived from the alicyclic tetracarboxylic dianhydride is in the range of 10 to 100%. A polyimide film that is excellent in storage stability and obtained by curing the composition is colorless and transparent, has a low coefficient of linear expansion, is excellent in elongation, and a laminate in which an inorganic film is formed on the polyimide film is Haze. The water vapor transmission rate was confirmed to be small.

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

Claims (26)

A resin composition containing a polyimide precursor and a solvent,
The polyimide precursor has a structure represented by the following general formula (A), and 2,2′-bis (trifluoromethyl) benzidine (TFMB), 2,2′-dimethylbiphenyl as a diamine-derived structure. A structure derived from at least one diamine selected from -4,4'-diamine, 4,4'-diaminobenzanilide and 4-aminophenyl-4-aminobenzoate;
As a structure derived from tetracarboxylic dianhydride,
1,2,3,4-cyclobutanetetracarboxylic dianhydride (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] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid-1,4 : 2,3-dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C] furan-1 , 3-dione and bicyclo [3,3,0] octa 2,4,6,8 and structure derived from at least one alicyclic tetracarboxylic dianhydride selected from tetracarboxylic acid dianhydride;
A structure derived from an aromatic tetracarboxylic dianhydride;
Have
The imidation ratio of the amide bond derived from the alicyclic tetracarboxylic dianhydride is 10 to 100%, the solid content concentration in the resin composition is 3 to 50% by mass,
The aromatic tetracarboxylic dianhydride is:
As the aromatic tetracarboxylic dianhydride 1, pyromellitic dianhydride (PMDA) and 3,3 ', at least one selected from 4,4'-biphenyltetracarboxylic acid dianhydride;
As aromatic tetracarboxylic dianhydride 2, 4,4'-oxydiphthalic dianhydride (ODPA), 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 4,4'-biphenyl A resin composition comprising at least one selected from bis (trimellitic acid monoester anhydride).

{X ₁ is 2,2′-bis (trifluoromethyl) benzidine (TFMB), 2,2′-dimethylbiphenyl-4,4′-diamine, 4,4′-diaminobenzanilide and 4-aminophenyl- A structure derived from at least one diamine selected from 4-aminobenzoate;
X ₂ represents 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-tricarboxycyclopentylacetic acid 1,4: 2,3-dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C ] Furan-1,3-dione and bicyclo [3,3,0 ] A structure derived from at least one tetracarboxylic dianhydride selected from octane-2,4,6,8-tetracarboxylic dianhydride. } The resin composition according to claim 1, wherein the polyimide precursor has a structure represented by the following general formula (B).

{X ₁ is the same as in formula (A) above;
X ₃ is a structure derived from the aromatic tetracarboxylic dianhydride. }   The resin composition of Claim 1 or 2 whose imidation ratio of the amide bond derived from alicyclic tetracarboxylic dianhydride is 20 to 100%.   The resin composition as described in any one of Claim 1 to 3 whose imidation ratio of the amide bond derived from alicyclic tetracarboxylic dianhydride is 30 to 100%.   The resin composition according to any one of claims 1 to 4, wherein the aromatic tetracarboxylic dianhydride 1 is pyromellitic dianhydride (PMDA).   The aromatic tetracarboxylic dianhydride 2 is at least one selected from 4,4′-oxydiphthalic dianhydride (ODPA) and 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA). The resin composition according to any one of claims 1 to 4, wherein   The resin composition according to any one of claims 1 to 6, wherein the diamine-derived structure is a structure derived from 2,2'-bis (trifluoromethyl) benzidine (TFMB). The alicyclic tetracarboxylic dianhydride is
1,2,3,4-cyclobutanetetracarboxylic dianhydride (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 and bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride. The resin composition as described in any one.   The alicyclic tetracarboxylic dianhydrides are 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) and 1,2,4,5-cyclohexanetetracarboxylic dianhydride (H-PMDA). The resin composition according to any one of claims 1 to 8, which is at least one selected from. The polyimide precursor is
The TFMB-derived structure contains 60 mol% or more of the total diamine-derived structure,
The structure derived from at least one tetracarboxylic dianhydride selected from the PMDA, the ODPA, the 6FDA, the CBDA, and the H-PMDA is combined to be 60 mol% or more in the total tetracarboxylic dianhydride-derived structure. Including,
The resin composition according to any one of claims 1 to 9. The polyimide precursor is
The structure derived from PMDA contains 1 to 70 mol% of the structure derived from all tetracarboxylic dianhydrides, and the structure derived from at least one tetracarboxylic dianhydride selected from ODPA and 6FDA 1-50 mol% in the structure derived from dianhydride,
The resin composition according to any one of claims 1 to 10.   The ratio {PMDA + ODPA + 6FDA + CBDA + H-PMDA) / TFMB} of the sum of the number of moles of the structure derived from each of the PMDA, the ODPA, the 6FDA, the CBDA and the H-PMDA and the number of moles of the structure derived from the TFMB, The resin composition according to any one of claims 1 to 10, which is 100 / 99.9 to 100/95.   After the polyimide precursor is dissolved in a solvent and spread on the surface of the support, the polyimide film obtained by imidization by heating in a nitrogen atmosphere has a yellowness of 10 or less, a linear expansion coefficient of 25 ppm or less, and 20 μm. The resin composition according to any one of claims 1 to 12, wherein an elongation of the film in the film thickness is 15% or more.   The resin composition as described in any one of Claim 1 to 13 used for manufacture of a flexible device.   The resin composition according to any one of claims 1 to 14, further comprising an alkoxysilane compound.   Furthermore, the resin composition as described in any one of Claim 1 to 15 containing surfactant. A resin composition containing a polyimide precursor and a solvent is developed on the surface of a support to form a coating film, and then the support and the coating film are heated to imidize the polyimide precursor. A method for producing a polyimide film,
The polyimide precursor has a structure represented by the following general formula (A), and 2,2′-bis (trifluoromethyl) benzidine (TFMB), 2,2′-dimethylbiphenyl as a diamine-derived structure. A structure derived from at least one diamine selected from -4,4'-diamine, 4,4'-diaminobenzanilide and 4-aminophenyl-4-aminobenzoate;
As a structure derived from tetracarboxylic dianhydride,
1,2,3,4-cyclobutanetetracarboxylic dianhydride (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] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid-1,4 : 2,3-dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C] furan-1 , 3-dione and bicyclo [3,3,0] octa 2,4,6,8 and structure derived from at least one alicyclic tetracarboxylic dianhydride selected from tetracarboxylic acid dianhydride;
A structure derived from an aromatic tetracarboxylic dianhydride;
Have
The alicyclic tetracarboxylic acid derived anhydrides amide bond imidization rate Ri 10-100% der,
The aromatic tetracarboxylic dianhydride is:
As aromatic tetracarboxylic dianhydride 1, at least one selected from pyromellitic dianhydride (PMDA) and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride;
As aromatic tetracarboxylic dianhydride 2, 4,4'-oxydiphthalic dianhydride (ODPA), 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 4,4'-biphenyl A method comprising at least one selected from bis (trimellitic acid monoester anhydride) .

{X ₁ is 2,2′-bis (trifluoromethyl) benzidine (TFMB), 2,2′-dimethylbiphenyl-4,4′-diamine, 4,4′-diaminobenzanilide and 4-aminophenyl- A structure derived from at least one diamine selected from 4-aminobenzoate;
X ₂ represents 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-tricarboxycyclopentylacetic acid 1,4: 2,3-dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C ] Furan-1,3-dione and bicyclo [3,3,0 ] A structure derived from at least one tetracarboxylic dianhydride selected from octane-2,4,6,8-tetracarboxylic dianhydride. }   The method according to claim 17, wherein the resin composition further contains an alkoxysilane compound.   The method according to claim 17 or 18, wherein the resin composition further contains a surfactant. A coating film forming step of forming a coating film by spreading a resin composition containing a polyimide precursor and a solvent on the surface of the support;
A heating step of heating the support and the coating film to imidize the polyimide precursor to form a polyimide film;
A peeling step of peeling the polyimide film from the support to obtain a polyimide film;
A method for producing a polyimide film comprising:
The polyimide precursor has a structure represented by the following general formula (A), and 2,2′-bis (trifluoromethyl) benzidine (TFMB), 2,2′-dimethylbiphenyl as a diamine-derived structure. A structure derived from at least one diamine selected from -4,4'-diamine, 4,4'-diaminobenzanilide and 4-aminophenyl-4-aminobenzoate;
As a structure derived from tetracarboxylic dianhydride,
1,2,3,4-cyclobutanetetracarboxylic dianhydride (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] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid-1,4 : 2,3-dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C] furan-1 , 3-dione and bicyclo [3,3,0] octa 2,4,6,8 and structure derived from at least one alicyclic tetracarboxylic dianhydride selected from tetracarboxylic acid dianhydride;
A structure derived from an aromatic tetracarboxylic dianhydride;
Have
The alicyclic tetracarboxylic acid derived anhydrides amide bond imidization rate Ri 10-100% der,
The aromatic tetracarboxylic dianhydride is:
As aromatic tetracarboxylic dianhydride 1, at least one selected from pyromellitic dianhydride (PMDA) and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride;
As aromatic tetracarboxylic dianhydride 2, 4,4'-oxydiphthalic dianhydride (ODPA), 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 4,4'-biphenyl A method comprising at least one selected from bis (trimellitic acid monoester anhydride) .

{X ₁ is 2,2′-bis (trifluoromethyl) benzidine (TFMB), 2,2′-dimethylbiphenyl-4,4′-diamine, 4,4′-diaminobenzanilide and 4-aminophenyl- A structure derived from at least one diamine selected from 4-aminobenzoate;
X ₂ represents 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-tricarboxycyclopentylacetic acid 1,4: 2,3-dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C ] Furan-1,3-dione and bicyclo [3,3,0 ] A structure derived from at least one tetracarboxylic dianhydride selected from octane-2,4,6,8-tetracarboxylic dianhydride. } A method for producing a laminate comprising a support and a polyimide film formed on the support,
In the method, on the surface of the support, a resin composition containing a polyimide precursor and a solvent is developed to form a coating film, and then the support and the coating film are heated to imide the polyimide precursor. Comprising forming a polyimide film,
The polyimide precursor has a structure represented by the following general formula (A), and 2,2′-bis (trifluoromethyl) benzidine (TFMB), 2,2′-dimethylbiphenyl as a diamine-derived structure. A structure derived from at least one diamine selected from -4,4'-diamine, 4,4'-diaminobenzanilide and 4-aminophenyl-4-aminobenzoate;
As a structure derived from tetracarboxylic dianhydride,
1,2,3,4-cyclobutanetetracarboxylic dianhydride (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] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid-1,4 : 2,3-dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C] furan-1 , 3-dione and bicyclo [3,3,0] octa 2,4,6,8 and structure derived from at least one alicyclic tetracarboxylic dianhydride selected from tetracarboxylic acid dianhydride;
A structure derived from an aromatic tetracarboxylic dianhydride;
Have
The alicyclic tetracarboxylic acid derived anhydrides amide bond imidization rate Ri 10-100% der,
The aromatic tetracarboxylic dianhydride is:
As aromatic tetracarboxylic dianhydride 1, at least one selected from pyromellitic dianhydride (PMDA) and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride;
As aromatic tetracarboxylic dianhydride 2, 4,4'-oxydiphthalic dianhydride (ODPA), 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 4,4'-biphenyl A method comprising at least one selected from bis (trimellitic acid monoester anhydride) .

{X ₁ is 2,2′-bis (trifluoromethyl) benzidine (TFMB), 2,2′-dimethylbiphenyl-4,4′-diamine, 4,4′-diaminobenzanilide and 4-aminophenyl- A structure derived from at least one diamine selected from 4-aminobenzoate;
X ₂ represents 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-tricarboxycyclopentylacetic acid 1,4: 2,3-dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C ] Furan-1,3-dione and bicyclo [3,3,0 ] A structure derived from at least one tetracarboxylic dianhydride selected from octane-2,4,6,8-tetracarboxylic dianhydride. } A polyimide film comprising an imidized product of a copolymer of diamine and tetracarboxylic dianhydride,
The diamine is 2,2′-bis (trifluoromethyl) benzidine (TFMB), 2,2′-dimethylbiphenyl-4,4′-diamine, 4,4′-diaminobenzanilide and 4-aminophenyl-4. -At least one selected from aminobenzoates;
The tetracarboxylic dianhydride is
As alicyclic tetracarboxylic dianhydride, 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 -Tricarboxycyclopentylacetic acid-1,4: 2,3-dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 1,2-C] furan-1,3-dio At least a one selected from and bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride,
As the aromatic tetracarboxylic dianhydride 1, at least one selected from pyromellitic dianhydride (PMDA) and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride,
As aromatic tetracarboxylic dianhydride 2, 4,4'-oxydiphthalic dianhydride (ODPA), 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 4,4'-biphenyl At least one selected from bis (trimellitic acid monoester anhydride);
Consists of
When an inorganic film is formed on the polyimide film using a CVD method at 350 ° C.,
The said polyimide film characterized by the surface roughness which measured this inorganic film surface using the atomic force microscope (AFM) being 0.01-50 nm. The diamine is 2,2′-bis (trifluoromethyl) benzidine (TFMB);
The tetracarboxylic dianhydride is
Select from 2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) and 1,2,4,5-cyclohexanetetracarboxylic dianhydride (H-PMDA) as the alicyclic tetracarboxylic dianhydride And at least one
As the aromatic tetracarboxylic dianhydride 1, pyromellitic dianhydride (PMDA) and 3,3 ', at least one selected from 4,4'-biphenyltetracarboxylic acid dianhydride,
As aromatic tetracarboxylic dianhydride 2, at least one selected from 4,4′-oxydiphthalic dianhydride (ODPA) and 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA); Consist of,
The polyimide film according to claim 22.   A flexible device comprising the polyimide film according to claim 22 or 23.   The manufacturing method of a flexible device containing the manufacturing method of the polyimide film of Claim 20.   The manufacturing method of a flexible device including the manufacturing method of the laminated body of Claim 21.