TW201920485A - Polyimide precursor resin composition, polyimide resin composition and film, production method for layered product and color filter, production method for liquid crystal element, and production method for organic el element - Google Patents

Abstract

（通式（1）中，R¹及R²分別獨立地表示碳數1～20的一價有機基；m表示3～200的整數） [化2]

（通式（2）中，R³表示二價有機基，R⁴表示四價有機基；Y¹及Y²分別獨立地表示氫原子、碳數1～10的一價有機基或碳數1～10的一價烷基矽烷基）The polyimide precursor resin composition includes a polyimide precursor (A) including a structure represented by the general formula (1) and a structural unit represented by the general formula (2), and a solvent (B). When the total amount of the polyimide precursor (A) is 100% by mass, the polyimide precursor (A) includes a structure represented by the general formula (1) of 5 to 30% by mass . The solvent (B) includes one or more solvents (B1) with an SP value of 7.7 or more and 9.0 or less, and a solvent (B2) with an SP value of more than 9.0 and 12.5 or less. [Chemical 1]

(In the general formula (1), R ¹ and R ² each independently represent a monovalent organic group having 1 to 20 carbon atoms; m represents an integer of 3 to 200)

(In the general formula (2), R ³ represents a divalent organic group, and R ⁴ represents a tetravalent organic group; Y ¹ and Y ² each independently represent a hydrogen atom, a monovalent organic group having 1 to 10 carbon atoms or a carbon number 1 ~ 10 monovalent alkyl silane group)

Description

Polyimide precursor resin composition, polyimide resin composition, polyimide resin film, method for manufacturing laminated body, method for manufacturing color filter, method for manufacturing liquid crystal element, and method for manufacturing organic EL element method

The present invention relates to a method for producing a polyimide precursor resin composition, a polyimide resin composition, a polyimide resin film, a laminate, a method for producing a color filter, and a method for producing a liquid crystal element. And a method for manufacturing an organic EL element.

Compared with glass, organic films have the following characteristics: they are flexible, hard to break, and lightweight. Recently, by changing the substrate of a flat panel display to an organic film, the dynamics of display flexibility have been activated.

Examples of the resin used in the organic film include polyester, polyimide, polyimide, polycarbonate, polyetherimide, acrylic acid, epoxy, and the like. Among these, polyimide resin is a highly heat-resistant resin, and is therefore suitable as a display substrate.

However, ordinary polyimide resins are colored brown or yellow due to high aromatic ring density, and thus have low transmittance in the visible light region, and are difficult to use in areas requiring transparency.

In order to improve the transparency of such polyimide resins, the following Patent Document 1 discloses a method of using 2,2-bis (trifluoromethyl) benzidine (hereinafter, also referred to as TFMB (2, 2'-bis (trifluoromethyl) benzidine)) to improve transmittance and transparency of hue, and then introduce silicone components such as silicon diamine to reduce residual stress.

In addition, Patent Document 2 below discloses a polyfluorene imide precursor resin composition having a low turbidity and excellent film productivity by using a non-fluorine-based solvent having a low boiling point as a main component. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 5948545 [Patent Document 2] Japanese Patent No. 5862674

[Problems to be Solved by the Invention] In Patent Document 1, a silicone-containing polyimide precursor resin using a single solvent of N-Methyl-2-Pyrrolidone (NMP) Although the composition is disclosed, the solubility of the silicone component in NMP is low, so that there is a problem that white turbidity easily occurs in the solution and the obtained cured film.

In addition, Patent Document 2 discloses a silicone-containing polyimide precursor resin composition containing a solvent having a low boiling point as a main solvent. However, if a solvent having a low boiling point is used as the main solvent, the coating liquid dries quickly. Therefore, there is a problem that unevenness tends to occur when the slit coating is performed, and the applicability is liable to decrease.

As described above, a polyimide precursor resin composition in which the coating property using the slit is good and the haze and residual stress of the obtained polyimide film are not known is unknown.

This invention is made in view of the said subject, and an object of this invention is to provide the polyimide precursor resin composition which has favorable slit coating property, and obtained the polyimide film, and which suppresses the turbidity and residual stress of the obtained polyimide film, and uses the same Polyimide resin composition, polyimide resin film, method of manufacturing laminated body, method of manufacturing color filter, method of manufacturing liquid crystal element, and method of manufacturing organic electroluminescence (EL) element. [Means for solving problems]

In order to solve the problems and achieve the object, the polyfluorene imide precursor resin composition of the present invention is a polyfluorene imide precursor including a structure represented by the general formula (1) and a structural unit represented by the general formula (2). The polyimide precursor resin composition of the polymer (A) and the solvent (B), wherein the total amount of the polyimide precursor (A) is 100% by mass The polyimide precursor (A) includes a structure represented by the general formula (1) in an amount of 5 to 30% by mass, and the solvent (B) includes one or more of a solubility parameter (SP) ) A solvent (B1) having a value of 7.7 or more and 9.0 or less, and a solvent (B2) having an SP value of more than 9.0 and 12.5 or less.

[Chemical 1] (In the general formula (1), R ¹ and R ² each independently represent a monovalent organic group having 1 to 20 carbon atoms; and m represents an integer of 3 to 200)

[Chemical 2] (In the general formula (2), R ³ represents a divalent organic group, R ⁴ represents a tetravalent organic group, and Y ¹ and Y ² each independently represent a hydrogen atom, a monovalent organic group having 1 to 10 carbon atoms, or 1 carbon number. ~ 10 monovalent alkyl silyl group)

In addition, as described in the present invention, the polyfluorene imide precursor resin composition of the present invention is characterized in that when the total amount of the solvent (B) is 100% by mass, the solvent (B) contains 5 mass% to 40 mass% of the solvent (B1), and 60 mass% to 95 mass% of the solvent (B2).

In addition, as described in the present invention, the polyfluorene imide precursor resin composition of the present invention is characterized in that when the total amount of the solvent (B) is 100% by mass, the solvent (B) contains 70% to 100% by mass of a solvent having a vapor pressure at 20 ° C of 10 Pa to 100 Pa.

In addition, as described in the invention, the polyimide precursor resin composition of the present invention is characterized in that, in the solvent (B), a vapor pressure difference between the solvent having the highest vapor pressure and the lowest solvent at 20 ° C is 100. Pa or less.

In addition, according to the invention, the polyimide precursor resin composition of the present invention is characterized in that the polyimide precursor is 100 mol% of the polyimide precursor (A). (A) An acid anhydride residue having a fluorene skeleton of 5 mol% or more and 55 mol% or less is included.

In addition, according to the invention, the polyimide precursor resin composition of the present invention is characterized in that the polyimide precursor is 100 mol% of the polyimide precursor (A). (A) Including 15 mol% or more and less than 60 mol% of diamine residues having a diphenylfluorenyl group in total.

In addition, according to the invention, the polyimide precursor resin composition of the present invention is characterized in that the polyimide precursor is 100 mol% of the polyimide precursor (A). (A) It contains the acid anhydride residue which has a diphenyl ether group, and the diamine residue which has a diphenyl ether group in total at 30 mol% or more.

In addition, according to the present invention, the polyfluorene imide precursor resin composition of the present invention is characterized in that the polyfluorene imine precursor (A) includes a triamine skeleton.

In addition, according to the present invention, the polyfluorene imide precursor resin composition of the present invention is characterized in that the polyfluorene imine precursor (A) includes a tetraamine skeleton.

In addition, as described in the present invention, the polyfluorene imide precursor resin composition of the present invention further includes a fluorene imidization accelerator, and the content of the fluorene imidization accelerator relative to the polyfluorene The amount of 100 parts by mass of the amine precursor (A) is 0.1 to 3 parts by mass.

In addition, the polyfluorene imide resin composition of the present invention is obtained by imidizing a polyfluorene imide precursor resin composition as described in any one of the inventions.

The polyimide resin film of the present invention is a polyimide resin film containing a structure represented by the general formula (1) for manufacturing a flexible display substrate, and the polyimide resin film is characterized in that: When the amount of the entire resin film is 100% by mass, the polyimide resin film includes a structure represented by the general formula (1) in an amount of 5% to 30% by mass, and has a tensile elastic coefficient of 1.5 GPa or more. It is 3.5 GPa or less, and the haze value is 1% or less.

[Chemical 3] (In the general formula (1), R ¹ and R ² each independently represent a monovalent organic group having 1 to 20 carbon atoms; and m represents an integer of 3 to 200)

The polyimide resin film of the present invention is a polyimide resin film containing a structure represented by the general formula (1) for manufacturing a flexible display substrate, and the polyimide resin film is characterized in that: When the amount of the entire resin film is 100% by mass, the polyimide resin film includes a structure represented by the general formula (1) in an amount of 5% to 30% by mass, and the haze value is 1% or less. The glass transition point is 380 ° C or higher.

[Chemical 4] (In the general formula (1), R ¹ and R ² each independently represent a monovalent organic group having 1 to 20 carbon atoms; and m represents an integer of 3 to 200)

Moreover, the manufacturing method of the laminated body of this invention is characterized by including the coating process of apply | coating the polyimide precursor resin composition as described in any one of said inventions to a support substrate; A removal step of removing the solvent of the coated polyimide precursor resin composition; the polyimide precursor resin composition from which the solvent is removed is imidized to obtain a polyimide resin composition A polyimide resin film forming step of a film of an object; and an inorganic film forming step of forming an inorganic film on the obtained film of the polyimide resin composition.

In addition, the method for manufacturing a color filter of the present invention is characterized by comprising: a step of forming a black matrix and a colored pixel on a multilayer body manufactured by the multilayer body manufacturing method described in the invention; And a peeling step of peeling the laminated body from the support substrate.

In addition, the method for manufacturing a liquid crystal element of the present invention is characterized by comprising the steps of forming a transparent electrode, an alignment film, and a liquid crystal layer on a multilayer body manufactured by the multilayer body manufacturing method described in the invention; and A step of peeling the support substrate from the laminated body.

In addition, the method for manufacturing an organic EL element of the present invention includes: a step of forming an organic EL light-emitting circuit on a multilayer body manufactured by the multilayer body manufacturing method described in the invention; and peeling off the support substrate. A step of peeling off the laminated body. [Effect of the invention]

According to the present invention, it is possible to provide a polyimide precursor resin composition having good coatability using a slit and suppressing white turbidity and residual stress of the obtained polyimide resin film. The polyimide resin composition obtained from the polyimide precursor resin composition of the present invention can be used as a support substrate for displays of electronic devices such as touch panels, color filters, liquid crystal elements, organic EL elements, and the like. Suitable for use. By using such a support substrate, it is possible to produce a display with high performance and high reliability.

Hereinafter, the form for implementing this invention is demonstrated in detail with drawing. The present invention is not limited to the following embodiments. In addition, each figure referred to in the following description merely shows the shape, size, and positional relationship to the extent that the content of the present invention can be understood. That is, the present invention is not limited to the shapes, sizes, and positional relationships illustrated in the drawings.

<Resin Composition> The polyimide precursor resin composition according to the embodiment of the present invention is a polyimide precursor including a structure represented by the general formula (1) and a structural unit represented by the general formula (2). (A) and the resin composition of the solvent (B). When the entire amount of the polyfluorene imide precursor (A) is 100% by mass, the polyfluorene imide precursor (A) includes a structure represented by the general formula (1) in an amount of 5 to 30% by mass. . The solvent (B) includes one or more solvents (B1) having an SP value of 7.7 or more and 9.0 or less, and a solvent (B2) having an SP value of more than 9.0 and 12.5 or less.

[Chemical 5]

In the general formula (1), R ¹ and R ² each independently represent a monovalent organic group having 1 to 20 carbon atoms. m represents an integer from 3 to 200.

[Chemical 6]

In the general formula (2), R ³ represents a divalent organic group, and R ⁴ represents a tetravalent organic group. Y ¹ and Y ² each independently represent a hydrogen atom, a monovalent organic group having 1 to 10 carbon atoms, or a monovalent alkylsilyl group having 1 to 10 carbon atoms.

In addition, “carbon number 1 to 10” means “carbon number 1 or more and carbon number 10 or less”. The same description in the present invention has the same meaning.

The polyimide precursor resin composition of the present invention includes the polyimide precursor (A) and a solvent (B) having an SP value in a better range, for example, two SP values in a better range, respectively. More than one type of solvent (B1) and solvent (B2), and the slit coatability is good. Furthermore, the polyfluorene imide resin composition obtained by the fluorene imidization has a high glass transition temperature, has less occurrence of warpage, has less white turbidity, and is excellent in mechanical strength.

<Polyimide precursor> The polyimide precursor (A) according to the embodiment of the present invention has a general formula (at least one of an acid dianhydride residue and a diamine residue constituting the polyimide). 1) Resin of the structure shown. The polyfluorene imide precursor (A) has a structural unit represented by the general formula (2). Since a part of the structural unit represented by the general formula (2) includes a soft structure represented by the general formula (1), it is considered that a rigid skeleton portion (a portion having no structure represented by the general formula (1)) is a sea portion, The soft skeleton part is a microlayer separation structure of the island part. As a result, it is possible to efficiently absorb the stress generated in the film formation step by using the soft skeleton portion, and to obtain a film having a small residual stress and suppressed generation of warpage.

Examples of the monovalent organic group having 1 to 20 carbon atoms in R ¹ and R ² include a hydrocarbon group, an amino group, an alkoxy group, and an epoxy group. Examples of the hydrocarbon group in R ¹ and R ² include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms.

The alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms. Specific examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tertiary. Butyl, pentyl, hexyl, etc. The cycloalkyl group having 3 to 20 carbon atoms is preferably a cycloalkyl group having 3 to 10 carbon atoms, and specific examples thereof include a cyclopentyl group and a cyclohexyl group. The aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms, and specific examples thereof include phenyl, tolyl, and naphthyl.

Examples of the alkoxy group in R ¹ and R ² include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, a phenoxy group, a propenyloxy group, and a cyclohexyloxy group. Wait.

R ¹ and R ² in the general formula (1) are preferably a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms or an aromatic group having 6 to 10 carbon atoms. The reason is that the obtained polyimide film has both high heat resistance and low residual stress. Here, the monovalent aliphatic hydrocarbon having 1 to 3 carbon atoms is preferably a methyl group, and the aromatic group having 6 to 10 carbon atoms is preferably a phenyl group.

At least one of R ¹ and R ² in the general formula (1) preferably contains an aromatic group. The reason is that the island portion including the soft skeleton portion has excellent affinity with the sea portion including the rigid skeleton portion, and it is easy to perform microlayer separation with a size of about 1 nm to 1 μm. In this case, among all of R ¹ and R ² in the structural unit represented by the general formula (1), the molar number M1 of the aliphatic hydrocarbon group of 1 to 3 carbons and the aromatic number of 6 to 10 carbons The ratio of the group-based Mohr number M2 (where M1 + M2 = 100) is preferably M1: M2 = 90 to 10:10 to 90, more preferably M1: M2 = 85 to 15:15 to 85, and further preferably M1: M2 = 85 ～ 65: 15 ～ 35. When the ratio is in the range, micro-layer separation can be performed at a skeleton portion including the structural unit in the structure represented by the general formula (1), low residual stress, and the like can be obtained, excellent transparency, and difficulty in turbidity Of the film.

In the polyimide precursor resin composition according to the embodiment of the present invention, when the entire amount of the polyimide precursor (A) is 100% by mass, 5% to 30% by mass of The structure represented by Formula (1). The structure represented by the general formula (1) is preferably contained in an amount of 6 to 23% by mass, more preferably 8 to 22% by mass, and even more preferably 10 to 21% by mass.

When the proportion of the structure represented by the general formula (1) contained in the polyfluorene imine precursor (A) is within the above range, the turbidity and glass transition temperature of the obtained polyfluorene imide resin composition can be suppressed. Reduction, residual stress, or increased substrate warpage.

M (that is, the degree of polymerization m) in the general formula (1) is an integer of 3 to 200. The polymerization degree m is preferably an integer of 10 to 200, more preferably an integer of 20 to 150, even more preferably an integer of 30 to 100, and particularly preferably an integer of 30 to 60. When the polymerization degree m is within the above range, the residual stress of polyimide can be reduced. In addition, it is possible to suppress the turbidity of the polyimide film or decrease in the mechanical strength of the polyimide film.

A polyimide precursor (A) containing a structure represented by the general formula (1) can be obtained by using a silicone compound represented by the following general formula (3) as a monomer component.

[Chemical 7]

In the general formula (3), a plurality of R ⁵ are each independently a single bond or a divalent organic group having 1 to 20 carbon atoms. A plurality of R ⁶ , R ^7, and R ⁸ are each independently a monovalent organic group having 1 to 20 carbon atoms. L ¹ , L ^2, and L ³ are each independently a group selected from the group consisting of an amine group, an acid anhydride group, a carboxyl group, a hydroxyl group, an epoxy group, a mercapto group, and R ⁹ . R ⁹ is a monovalent organic group having 1 to 20 carbon atoms. n is an integer from 3 to 200, and o is an integer from 0 to 197.

Examples of the divalent organic group having 1 to 20 carbon atoms in R ⁵ in the general formula (3) include an alkylene group having 1 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, and carbon number. 6-20 arylene and the like. The alkylene group having 1 to 20 carbon atoms is preferably an alkylene group having 1 to 10 carbon atoms, and examples thereof include methylene, dimethylene, trimethylene, tetramethylene, and pentamethylene. , Hexamethylene, etc. The cycloalkyl group having 3 to 20 carbon atoms is preferably a cycloalkyl group having 3 to 10 carbon atoms, and examples thereof include cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl. The arylene group having 6 to 20 carbon atoms is preferably an aromatic group having 3 to 20 carbon atoms, and examples thereof include a phenylene group and a naphthyl group. The divalent organic group having 1 to 20 carbon atoms in R ⁵ is preferably a divalent aliphatic hydrocarbon having 3 to 20 carbon atoms.

Preferred specific examples of each group in R ⁶ to R ⁸ include the same ones as R ¹ and R ² in the structure represented by the general formula (1).

The amine group in L ¹ , L ^2, and L ³ includes not only the amine group itself but also a reactive derivative thereof. Examples of the reactive derivative of an amine group include an isocyanate group and a bis (trialkylsilyl) amine group. Specific examples of the compound represented by the general formula (3) when L ¹ , L ^2, and L ³ are amine groups include X22-1660B-3 (a modified methylphenyl silicone at both terminal amino groups) Manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 4,400, degree of polymerization m = 41, phenyl: methyl = 25 mol%: 75 mol%, X22-9409 (made by Shin-Etsu Chemical Co., Ltd., number average molecular weight 1,300, degree of polymerization m = 12 , Phenyl: methyl = 25 mol%: 75 mol%), X22-161A (made by Shin-Etsu Chemical Co., Ltd., number average molecular weight 1,600, degree of polymerization m = 20) as a modified dimethyl silicone at both ends of the amino group, X22-161B (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,000, degree of polymerization m = 39), KF8012 (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 4,400, degree of polymerization m = 58), BY16-835U (Toray Dow Corning (Toray Dow Corning), number average molecular weight 900, degree of polymerization m = 11), Silaplane FM3311 (Chisso company, number average molecular weight 1000), etc.

The acid anhydride groups in L ¹ , L ^2, and L ³ include not only the acid anhydride group itself but also a reactive derivative thereof. Examples of the reactive derivative of the acid anhydride group include an acid ester of a carboxyl group, and fluorenyl chloride of the carboxyl group. Specific examples of L ¹ , L ^2, and L ³ as the acid anhydride group include a group represented by the following formula.

[Chemical 18]

The degree of polymerization m can be calculated using the following formula, for example. Here, the formula is satisfied if the following conditions are satisfied: a compound in which both ends are aminopropyl groups, and all R ⁵ in the general formula (3) are methyl groups or phenyl groups. m = (number average molecular weight-molecular weight of both terminal groups (aminopropyl)) / (74.15 × mol% of methyl × 0.01 + 198.29 × mol% of phenyl × 0.01) In this formula, aminopropyl The molecular weight is 116.2.

Specific examples of the compound represented by the general formula (3) when L ¹ , L ² and L ³ are acid anhydride groups include X22-168AS (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 1,000), and X22-168A (Shin-Etsu Chemical company, number average molecular weight 2,000), X22-168B (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,200), X22-168-P5-B (manufactured by Shin-Etsu chemical company, number average molecular weight 4,200), DMS-Z21 (Gali Manufactured by Gelest, with a number average molecular weight of 600 to 800 and a degree of polymerization of m = 4 to 7).

Specific examples of the compound represented by the general formula (3) when L ¹ , L ^2, and L ³ are hydroxyl groups include KF-6000 (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 900), and KF-6001 (Shin-Etsu Chemical Manufactured by the company with a number average molecular weight of 1,800), KF-6002 (manufactured by Shin-Etsu Chemical Co., Ltd. with a number average molecular weight of 3,200), KF-6003 (made by Shin-Etsu Chemical Co., Ltd. with a number average molecular weight of 5,000) and so on. The compound having this hydroxyl group is considered to react with other tetracarboxylic dianhydride monomers.

Specific examples of the compound represented by the general formula (3) when L ¹ , L ^2, and L ³ are epoxy groups include X22-163 (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight) of epoxy type at both ends. 400), KF-105 (made by Shin-Etsu Chemical Co., Ltd., number average molecular weight 980), X22-163A (made by Shin-Etsu Chemical Co., Ltd., number average molecular weight 2,000), X22-163B (made by Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,500), X22- 163C (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 5,400), X22-169AS (made by Shin-Etsu Chemical Co., Ltd., number average molecular weight 1,000), X22-169B (made by Shin-Etsu Chemical Co., Ltd., number average molecular weight) 3,400) and so on. The compound having this epoxy group is considered to react with other diamine monomers.

Specific examples of the compound represented by the general formula (3) when L ¹ , L ² and L ³ are a mercapto group include X22-167B (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,400), X22-167C (Shin-Etsu Chemical Manufactured by the company, the number average molecular weight is 4,600). The compound having this mercapto group is considered to react with other tetracarboxylic dianhydride monomers.

From the viewpoint of increasing the molecular weight of the polyimide precursor (A) or the heat resistance of the obtained polyimide, it is preferred that L ¹ , L ² and L ³ are each independently selected from amines. One of the group consisting of an amino group, an acid anhydride group, and R ⁹ . Furthermore, from the viewpoint of avoiding the turbidity of the varnish containing the polyimide precursor (A) and the solvent (B), or the viewpoint of cost, it is more preferable that L ¹ , L ^2, and L ³ are each independently an amine group. .

In the general formula (2), examples of the monovalent organic group having 1 to 10 carbon atoms in Y ¹ and Y ² include a monovalent hydrocarbon group having 1 to 10 carbon atoms. Examples of the hydrocarbon group having 1 to 10 carbon atoms include an alkyl group having 1 to 10 carbon atoms.

Specific examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, third butyl, pentyl, and hexyl.

Examples of the alkylsilyl group having 1 to 10 carbon atoms include a monovalent silyl group having an alkyl group having 1 to 10 carbon atoms bonded thereto. Specific examples of the alkylsilyl group having 1 to 10 carbon atoms include trimethylsilyl group and triethylsilyl group.

From the foregoing, it is considered that the polyimide obtained from the polyimide precursor (A) has a rigid skeleton portion and a soft skeleton portion including a structural unit represented by the general formula (1), and forms the rigid skeleton. The part becomes the sea part, and the soft skeleton part becomes the microphase separation structure of the island part. It is considered that a film having reduced residual stress can be obtained by forming the microphase separation structure with polyfluoreneimine.

In addition, in the present invention, the term “microphase separation” means that an island portion including a soft skeleton portion is dispersed in a sea portion including a rigid skeleton portion in a size of about 1 nm to 1 μm. In addition, in the present invention, the "warping" refers to the degree of curl of a film judged visually. The "residual stress" refers to the stress remaining in the film after the resin composition is applied to a substrate such as a glass substrate to form a film, and it is a criterion for "warping" that occurs in the film. Specifically, it can be measured by the method described in the following examples.

In the general formula (2), the divalent organic group in R ³ is preferably a divalent organic group having 1 to 40 carbon atoms. The divalent organic group having 1 to 40 carbon atoms is preferably a divalent aromatic hydrocarbon group or heterocyclic hydrocarbon group having 6 to 40 carbon atoms, and more preferably an aromatic hydrocarbon group from the viewpoint of heat resistance. When the organic group contains two or more kinds of ring structures, the ring may include a polycyclic structure, a spirohydrocarbon structure, and a single bond such as a biphenyl group. Structures bonded to a ring, etc.

Examples of the bonding group include an ether bond, a thioether group, a ketone group, an ester bond, a sulfonyl group, an alkylene group, a fluorenylamino group, and a siloxane group, in addition to a single bond. In the case where the divalent organic group contains a hydrogen atom, an arbitrary hydrogen atom may be substituted with a halogen atom.

Examples of the divalent organic group having 1 to 40 carbon atoms include an aromatic diamine compound, an alicyclic diamine compound, or an aliphatic diamine compound.

For example, the aromatic diamine compound is not particularly limited, and examples thereof include 1,4-bis (4-aminophenoxy) benzene, m-phenylenediamine, p-phenylenediamine, and 1,5-naphthalenediamine. , 2,6-naphthalenediamine, bis {4- (4-aminophenoxyphenyl)} fluorene, 4,4'-diaminodiphenylfluorene, 3,3'-diaminodiphenyl Hydrazone, bis {4- (3-aminophenoxyphenyl)} fluorene, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl} Ether, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4- Aminophenoxy) phenyl] hexafluoropropane, 3-aminophenyl-4-aminobenzenesulfonate, 4-aminophenyl-4-aminobenzenesulfonate, 2,2-bis (4- (4-Aminophenoxy) phenyl) propane, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diamine Diphenyl ether or a diamine compound in which these aromatic rings are substituted by an alkyl group, an alkoxy group, a halogen atom, or the like.

The alicyclic diamine compound is not particularly limited, and examples thereof include cyclobutanediamine, isophoronediamine, bicyclo [2.2.1] heptanedimethylamine, and tricyclo [3.3.1.13,7 ] Decane-1,3-diamine, 1,2-cyclohexyldiamine, 1,3-cyclohexyldiamine, 1,4-cyclohexyldiamine, 4,4'-diaminodicyclohexylmethane , 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-diethyl-4,4'-diaminodicyclohexylmethane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodicyclohexylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminodicyclohexylmethane, 3 , 5-diethyl-3 ', 5'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexyl ether, 3,3'-dimethyl -4,4'-diaminodicyclohexyl ether, 3,3'-diethyl-4,4'-diaminodicyclohexyl ether, 3,3 ', 5,5'-tetramethyl -4,4'-diaminodicyclohexyl ether, 3,3 ', 5,5'-tetraethyl-4,4'-diaminodicyclohexyl ether, 3,5-diethyl-3 ', 5'-dimethyl-4,4'-diaminodicyclohexyl ether, 2,2-bis (4-aminocyclohexyl) propane, 2,2-bis (3-methyl-4- Aminocyclohexyl) propane, 2,2-bis (3-ethyl-4-aminocyclohexyl) propane, 2,2-bis (3,5-dimethyl-4-aminocyclohexyl) propane, 2 , 2-bis (3,5-diethyl-4-aminocyclohexyl) propane, 2,2- (3,5-diethyl-3 ', 5'-dimethyl-4,4'- Diaminodicyclohexyl) propane, 2,2'-bis (4-aminocyclohexyl) hexafluoropropane, 2,2'-dimethyl-4,4'-diaminobicyclohexane, 2, 2'-bis (trifluoromethyl) -4,4'-diaminobicyclohexane, or a diamine compound in which these alicyclic rings are substituted by an alkyl group, an alkoxy group, a halogen atom, or the like.

The aliphatic diamine compound is not particularly limited, and examples thereof include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, and 1, 6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, etc. Glycol diamines, such as ethylenediamines, bis (aminomethyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, and 1,3-bis ( 3-aminopropyl) tetramethyldisilaxane, 1,3-bis (4-aminobutyl) tetramethyldisilaxane, α, ω-bis (3-aminopropyl) poly Siloxane diamines such as dimethylsiloxane.

These aromatic diamine compounds, alicyclic diamine compounds, or aliphatic diamine compounds can be used alone or in combination of two or more.

The divalent organic group is more preferably a group selected from the group consisting of compounds represented by the following chemical formulas (4) to (6), and further preferably selected from the following chemical formulas (4) to (6) Groups in the group of compounds represented. When the divalent organic group in R ³ is a group selected from the group of compounds represented by the following chemical formulas (4) to (6), the sea part has a structure having a more rigid skeleton. Therefore, it is preferable to obtain a film with small residual stress and suppressed generation of warpage.

[Chemical 9]

In the chemical formula (4) and the chemical formula (5), R ^{10 is} independently selected from the group consisting of an ether bond, a thioether bond, a ketone bond, an ester bond, a sulfonyl bond, a amide bond, and a siloxane bond. The base of more than one bond in the group. Alternatively, R ¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, a nitro group, a cyano group, or a sulfonyl group. Any hydrogen atom of the alkyl group may be substituted with a halogen atom. X ¹ is a straight bond, or an oxygen atom, a sulfur atom, a sulfonyl group, and a divalent organic group having 1 to 3 carbon atoms which may be substituted with a halogen atom. Alternatively, X ¹ is a divalent cross-linked structure selected from the group consisting of an ester bond, a amide bond, and a thioether bond. a ¹ represents an integer of 1 to 3. a ² means 1 or 2. a ³ each independently represents an integer of 0 to 4. e represents an integer from 0 to 3.

Examples of the group containing one or more types of bonds selected from the group consisting of an ether bond, a thioether bond, a ketone bond, an ester bond, a sulfonyl bond, a fluorene bond, and a siloxane bond, and examples include an ether bond. Organic group having 1 to 10 carbon atoms, a thioether bond, a ketone bond, an ester bond, a sulfonyl bond, a sulfonyl group, or a siloxane group.

In the chemical formula (4) and the chemical formula (5), R ^{10 is} preferably a hydrogen atom, a methyl group, or a trifluoromethyl group, and more preferably a methyl group or a trifluoromethyl group. When R ¹⁰ is a methyl group, the residual stress can be reduced, and the elastic modulus of the obtained polyimide resin composition can be increased. When R ¹⁰ is a trifluoromethyl group, the transparency of the obtained film can be improved.

X ^{1 is} preferably a straight bond or a sulfofluorenyl group. When X ¹ is a straight bond or a sulfofluorenyl group, the glass transition point (Tg) of the obtained polyfluorene imine resin composition can be increased.

e is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. a ^{1 is} preferably 1 or 3. a ^{2 is} preferably 2. a ^{3 is} preferably an integer of 0 to 2, and more preferably 0 or 1.

In the general formula (2), the divalent organic group in R ³ is preferably a group selected from the group of compounds represented by the following chemical formulas (7) to (10).

[Chemical 10]

In Chemical Formulas (7) to (10), R ¹⁰ has the same meaning as R ^{10 in} Chemical Formula (4) and Chemical Formula (5).

In the general formula (2), the divalent organic group in R ³ is more preferably a group selected from the group of compounds represented by the following chemical formulas (11) to (14).

[Chemical 11]

In the general formula (2), the tetravalent organic group in R ⁴ is preferably a tetravalent organic group having 1 to 40 carbon atoms. The tetravalent organic group having 1 to 40 carbon atoms is preferably a tetravalent alicyclic hydrocarbon group having 3 to 40 carbon atoms or a tetravalent aromatic hydrocarbon group having 6 to 40 carbon atoms. When the organic group includes two or more kinds of ring structures, the organic group may include a polycyclic structure in which the rings share one or more bonds, a spirohydrocarbon structure, and a bonding group such as a biphenyl group using a single bond or the like. A structure in which a ring is bonded to a ring. Examples of the bonding group include an ether bond, a thioether group, a keto group, an ester bond, a sulfonyl group, an alkylene group, a fluorenylamino group, and a siloxane group in addition to the single bond. Examples of the tetravalent organic group include an aromatic acid dianhydride, an alicyclic acid dianhydride, and an aliphatic acid dianhydride.

For example, the aromatic acid dianhydride is not particularly limited, and examples thereof include 2,2-bis (4- (3,4-dicarboxyphenoxy) phenyl) propane dianhydride and 2,2-bis (3 -(3,4-dicarboxyphenoxy) phenyl) propane dianhydride, 2,2-bis (4- (3,4-dicarboxyphenoxy) phenyl) hexafluoropropane dianhydride, 2,2 -Bis (3- (3,4-dicarboxyphenoxy) phenyl) hexafluoropropane dianhydride, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-terphenyltetracarboxylic acid Acid dianhydride, 4,4'-oxydiphthalic dianhydride, 3,4'-oxydiphthalic dianhydride, 3,3'-oxydiphthalic dianhydride, di Phenylhydrazone-3,3 ', 4,4'-tetracarboxylic dianhydride, benzophenone-3,3', 4,4'-tetracarboxylic dianhydride, 2,2-bis (3,4 -Dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-Dicarboxyphenyl) ether dianhydride, bis (1,3-dioxo-1,3-dihydroisobenzofuran-5- (Acid) 1,4-phenylene, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridine tetra Carboxylic dianhydride, 3,4,9,10-fluorenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis (4- ( 3,4-dicarboxybenzyloxy) phenyl) hexafluoropropane dianhydride, 1,6-difluoropyrellitic dianhydride, 1-trifluoromethyl pyromellitic dianhydride, 1, 6-di-trifluoromethyl pyromellitic dianhydride, 2,2'-bis (trifluoromethyl) -4,4'-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorenic dianhydride, 4,4 '-((9H-fluorenyl) bis (4,1-phenylphenyloxycarbonyl) )) Aromatic tetracarboxylic dianhydrides such as diphthalic dianhydride, "Rikacid" (registered trademark) TMEG-100 (trade name, manufactured by Nippon Rika Chemical Co., Ltd.), and derivatives thereof, etc. .

Examples of the alicyclic acid dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3 1,4-Cyclopentanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1 , 2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclo Heptane tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 2,3,5-tricarboxycyclopentane Glycolic dianhydride, 3,4-dicarboxyl-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, bicyclo [3,3,0] octane-2,4,6,8 -Tetracarboxylic dianhydride, bicyclic [4,3,0] nonane-2,4,7,9-tetracarboxylic dianhydride, bicyclic [4,4,0] decane-2,4,7,9 -Tetracarboxylic dianhydride, bicyclic [4,4,0] decane-2,4,8,10-tetracarboxylic dianhydride, tricyclic [6,3,0,0 <2,6 ＞] 11 Alkane-3,5,9,11-tetracarboxylic dianhydride, bicyclo [2,2,2] octane-2,3,5,6-tetracarboxylic dianhydride, bicyclic [2,2,2] octane -7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclic [2,2,1] heptane tetracarboxylic dianhydride, bicyclic [2,2,1] heptane-5-carboxymethyl -2,3,6-tricarboxylic dianhydride, 7-oxabicyclo [2,2,1] heptane-2,4,6,8-tetracarboxylic dianhydride, octahydrogen -1,2,6,7-tetracarboxylic dianhydride, tetrahydroanthracene-1,2,8,9-tetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopentanone-α ' -Spiro-2 ''-norbornane-5,5 '', 6,6 ''-tetracarboxylic dianhydride, 3,3 ', 4,4'-dicyclohexanetetracarboxylic dianhydride, 3 , 3 ', 4,4'-oxydicyclohexane tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexyl Ene-1,2-dicarboxylic anhydride, and "Rikacid" (registered trademark) BT-100 (above, trade name, manufactured by Nippon Rika Chemical Co., Ltd.) and derivatives thereof, or alkyl, An acid dianhydride compound in which these alicyclic rings are substituted by an alkoxy group, a halogen atom, or the like. The alicyclic acid dianhydride is not limited to these.

The aliphatic acid dianhydride is not particularly limited, and examples thereof include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride, and the like. Derivatives, etc.

The other acid dianhydrides can be used alone or in combination of two or more.

R ⁴ in the general formula (2) is more preferably a group selected from the group of compounds represented by the following chemical formulas (15) to (21).

[Chemical 12]

In the chemical formulas (15) to (21), R ^{11 is} independently selected from the group consisting of an ether bond, a thioether bond, a ketone bond, an ester bond, a sulfonyl bond, a amide bond, and a siloxane bond. The base of more than one bond in the group. Alternatively, R ¹¹ represents a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, a nitro group, a cyano group, or a sulfonyl group, and any halogen atom that may be an alkyl group is a halogenated alkyl group substituted with a halogen atom. X ¹ is a straight bond, or an oxygen atom, a sulfur atom, a sulfonyl group, and a divalent organic group having 1 to 3 carbon atoms which may be substituted with a halogen atom. Alternatively, X ¹ is a divalent cross-linked structure selected from the group consisting of an ester bond, a amide bond, and a thioether bond. b each independently represents 1 or 2. c each independently represents an integer of 1 to 3. f represents an integer of 0 to 3.

Examples of the group containing one or more types of bonds selected from the group consisting of an ether bond, a thioether bond, a ketone bond, an ester bond, a sulfonyl bond, a fluorene bond, and a siloxane bond, and examples include an ether bond. Organic group having 1 to 10 carbon atoms, a thioether bond, a ketone bond, an ester bond, a sulfonyl bond, a sulfonyl group, or a siloxane group.

In the chemical formulas (15) to (21), examples of the halogenated alkyl group in R ¹¹ include a methyl group substituted with a halogen atom or an alkyl group having 2 to 20 carbon atoms. The halogenated alkyl group having 2 to 20 carbon atoms is preferably an alkyl group having 2 to 10 carbon atoms substituted with a halogen atom. Examples of such a halogenated alkyl group include ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, and hexyl. Any hydrogen atom via a fluorine atom, a chlorine atom, a bromine atom, or A group substituted with an iodine atom.

In the chemical formulas (15) to (21), the halogenated alkyl group in R ¹¹ is preferably an alkyl group having 1 to 2 carbon atoms substituted with a halogen atom. Specific examples include methyl and ethyl groups. A group in which a hydrogen atom is substituted with a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

In the chemical formulas (15) to (21), the halogen atom in R ¹¹ and the halogen atom contained in the halogenated alkyl group are preferably a fluorine atom in terms of obtaining a film having excellent mechanical strength and good transparency. On the other hand, as R ¹¹ not containing a halogen atom, a hydrogen atom, an alkyl group, a fluorenyl group, a hydroxyl group, a nitro group, a cyano group, or a sulfo group is preferred, and a hydrogen atom or an alkyl group is preferred.

In the chemical formulas (15) to (21), the alkyl group in R ¹¹ is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms. Specific examples of such an alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, third butyl, pentyl, and hexyl.

The group selected from the group of compounds represented by Chemical Formulas (15) to (21) is preferably a group selected from the group of compounds represented by the following Chemical Formulas (22) to (25). When the group represented by the chemical formula (22) is contained, the turbidity of the obtained polyimide resin can be reduced, transparency can be improved, and residual stress can be reduced. When the group represented by the chemical formula (23) is included, the obtained polyimide resin has a structure having a rigid skeleton, and therefore, it is possible to increase the mechanical strength (the coefficient of elasticity) or the Tg. When the group represented by the chemical formula (24) is included, the turbidity of the polyimide resin can be reduced, and the in-plane / out-plane birefringence can be reduced. When the group represented by the chemical formula (25) is included, Tg can be increased. Among them, when the group represented by the chemical formula (24) is included, it is particularly preferable because it can exhibit characteristics of high Tg, low birefringence, and high transparency. In addition, in addition to high Tg, low birefringence, and high transparency, in order to increase the elongation at break, it is preferable to include 5 mol% or more and 55 mol% of 100 mol% of the polyimide precursor (A). The group exemplified in the structure of the chemical formula (24), which is less than or equal to mole%, that is, an acid anhydride residue having a fluorene skeleton, further preferably contains 10 mole% or more and 35 mole% or less.

[Chemical 13]

In the general formula (2), R ³ is a group selected from the group of compounds represented by the chemical formulas (4) to (6), and is particularly selected from the compounds represented by the chemical formulas (7) to (10). The group in the group, R ⁴ is a group selected from the group of compounds represented by the chemical formulas (15) to (21), particularly a group selected from the compounds represented by the chemical formulas (22) to (25) When m in the general formula (1) is 3 or more, the polyimide obtained from the polyimide precursor (A) is more likely to obtain a microphase separation structure, so the obtained It is particularly preferable in terms of reduction of the residual stress of the film.

The polyfluorene imide precursor (A) preferably contains a triamine skeleton. The triamine has three amine groups and forms a branched molecular chain by bonding to three tetracarboxylic dianhydride components. The triamine skeleton introduces a branched structure into the molecular chain of polyamidic acid to form a branched polyamidic acid. Thereby, the viscosity of the varnish in which the polyamic acid resin is dissolved can be increased, and the uniformity of the film thickness when the coating is performed through the slit can be improved. In addition, since the molecular weight of the polyimide resin obtained from the polyimide precursor (A) having a branched structure is larger than that of the polyimide resin having no branched structure, a cluster effect can be used to increase the Interaction of inorganic film on polyimide resin.

Specific examples of the triamine compound include those having no aliphatic group, and 2,4,4'-triaminodiphenyl ether (TAPE), 1,3 1,5-tris (4-aminophenoxy) benzene (1,3,5-tris (4-aminophenoxy) benzene, 1,3,5-TAPOB), 1,2,3-tris (4-amino group) Phenoxy) benzene (1,2,3-TAPOB), tris (4-aminophenyl) amine, 1,3,5-tris (4-aminophenyl) benzene, 3,4,4'- Triamino diphenyl ether and the like. Examples of those having an aliphatic group include tris (2-aminoethyl) amine (TAEA), and tris (3-aminopropyl). ) Amines and the like.

As described above, the triamine constitutes a branch of a crosslinked structure in the molecular chain of the polyfluoreneimide resin. When the triamine is thermally decomposed, the crosslinked structure of the polyfluorene imine resin disappears. Therefore, as the triamine component, it is preferred to use a component that does not have an aliphatic group and is difficult to thermally decompose. That is, it is preferable to use 2,4,4'-triaminodiphenyl ether (TAPE), 1,3,5-tris (4-aminophenoxy) benzene (1,3,5-TAPOB) , 1,2,3-tris (4-aminophenoxy) benzene (1,2,3-TAPOB), etc.

The polyfluorene imine precursor (A) preferably contains a tetraamine skeleton. Tetraamine has four amine groups and forms a branched molecular chain by bonding to four tetracarboxylic dianhydride components. The tetraamine skeleton introduces a branched structure into the molecular chain of polyamidic acid to form a branched polyamidic acid. Thereby, the viscosity of the varnish in which the polyamic acid resin is dissolved can be increased, and the uniformity of the film thickness when the coating is performed through the slit can be improved. In addition, since the molecular weight of the polyimide resin obtained from the polyimide precursor (A) having a branched structure is larger than that of a polyimide resin having no branched structure, a cluster effect can be used to improve the polyimide resin formation. Interaction of inorganic film on resin. Furthermore, by using tetraamine, the Tg of the polyfluoreneimide resin composition can be increased. The reason is considered to be that it is known that a benzimidazole having high heat resistance can be obtained by reacting a dicarboxylic acid with a tetramine. However, when a tetracarboxylic dianhydride is reacted with a tetraamine, a part of the benzimidazole is also formed. .

Specific examples of the tetraamine compound include 1,2,4,5-tetraaminobenzene, 3,3 ', 4,4'-tetraaminobiphenyl, 3,3', 4,4'- Tetraaminodiphenylphosphonium, 3,3 ', 4,4'-tetraaminodiphenyl ether, 3,3', 4,4'-tetraaminodiphenyl sulfide, 2,3,6 , 7-tetraaminonaphthalene, 1,2,5,6-tetraaminonaphthalene and the like. Alternatively, specific examples of the tetraamine compound include compounds obtained by substituting a part of hydrogen bonded to an aromatic ring contained in these polyamine compounds or diamine compounds with a hydrocarbon or a halogen.

As the tetraamine component, it is preferable to use a component which does not have an aliphatic group and which is difficult to thermally decompose, like the triamine, and further has an electron-withdrawing group in terms of improving transparency. That is, it is preferred to use 3,3 ', 4,4'-tetraaminodiphenylphosphonium and the like.

In the present invention, the substituent constant (paraposition, σp) of Hammett with an electron-drawing group is generally greater than 0, preferably 0.01 or more, further preferably 0.1 or more, and particularly preferably 0.5 or more. Hammett's substituent constants are described, for example, in the "Handbook of Chemistry" (Revised 5th Edition, Division II, Maruzen Co., Ltd., February 2004, p. 380) compiled by the Japanese Chemical Society. Examples of the electron-withdrawing group include a halogen atom, a cyano group, a hydrogen atom or a carbonyl group having a substituent, a nitro group, a perfluoroalkyl group such as a trifluoromethyl group, and a sulfonyl group. Examples of the halogen atom include a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom.

The polyfluorene imide precursor (A) preferably has a diphenyl ether group. Thereby, deterioration of the haze of the cured film due to layer separation can be suppressed. In addition, out of 100 mol% of the polyfluorene imide precursor (A), the polyfluorene imide precursor (A) preferably contains an acid anhydride residue having a diphenyl ether group in a total amount of 30 mol% or more. And a diamine residue or a triamine residue having a diphenyl ether group, and more preferably 40 mol% or more.

Examples of the acid anhydride containing a diphenyl ether group include 2,2-bis (4- (3,4-dicarboxyphenoxy) phenyl) propane dianhydride and 2,2-bis (3- (3 ( , 4-dicarboxyphenoxy) phenyl) propane dianhydride, 2,2-bis (4- (3,4-dicarboxyphenoxy) phenyl) hexafluoropropane dianhydride, 2,2-bis ( 3- (3,4-dicarboxyphenoxy) phenyl) hexafluoropropane dianhydride, 4,4'-oxydiphthalic dianhydride, 3,4'-oxydiphthalic acid di Anhydride, 3,3'-oxydiphthalic dianhydride.

Examples of the diamine containing a diphenyl ether group include 1,4-bis (4-aminophenoxy) benzene, bis {4- (4-aminophenoxyphenyl)} fluorene, and bis {4- (3-Aminophenoxyphenyl)} pyrene, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl} ether, 2, 2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis ( 4- (4-aminophenoxy) phenyl) propane, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diamine Diphenyl ether.

Examples of the triamine containing a diphenyl ether group include: 2,4,4'-triaminodiphenyl ether (TAPE), 1,3,5-tris (4-aminophenoxy) benzene (1,3,5-TAPOB), 1,2,3-tris (4-aminophenoxy) benzene (1,2,3-TAPOB), 3,4,4'-triaminodiphenyl ether.

The polyfluoreneimide precursor (A) preferably has a diphenylfluorenyl group. Thereby, the Tg of the polyfluorene imide resin can be increased, and further, the birefringence can be reduced. In addition, out of 100 mol% of the polyfluorene imide precursor (A), the polyfluorene imide precursor (A) preferably contains a diphenyl group having a total of 15 mol% or more and 60 mol% or less. The fluorenyl acid anhydride residue and the diamine, triamine residue, or tetraamine residue having a diphenyl fluorenyl group are more preferably 20 mol% or more and 50 mol% or less. The polyfluorene imide precursor (A) has a diphenylfluorenyl group within the above range, which can increase the Tg of the cured film, reduce the haze value, and further reduce the birefringence, and can increase the elastic coefficient of the cured film. Improves flexibility.

Examples of the acid anhydride containing a diphenylfluorenyl group include diphenylsulfo-3,3 ', 4,4'-tetracarboxylic dianhydride (diphenyl sulfone-3,3', 4,4'-tetracarboxylic dianhydride). , DSDA), diphenylfluorene-2,3,3 ', 4'-tetracarboxylic dianhydride, diphenylfluorene-2,2', 3 ', 3'-tetracarboxylic dianhydride, 4,4 '-[P-sulfofluorenylbis (phenylenethio)] diphthalic anhydride, 4,4'-[m-sulfofluorenylbis (phenylenethio)] diphthalic anhydride, and the like.

Examples of the diamine containing a diphenylfluorenyl group include bis {4- (4-aminophenoxyphenyl)} 碸, bis {4- (3-aminophenoxyphenyl)} 碸, 4,4'-diaminodiphenylphosphonium, 3,3'-diaminodiphenylphosphonium and the like. Examples of the tetraamine containing a diphenylphosphonium group include 3,3 ', 4,4'-tetraaminodiphenylphosphonium.

In addition, a part of the structural unit represented by the general formula (2) of the polyfluorene imide precursor (A) may be fluorinated. By imidizing a part of the polyfluorene imine precursor (A), the viscosity stability of the resin solution during storage at room temperature can be improved. The range of the fluorene imidization rate of the polyfluorene imine precursor (A) is preferably from 1% to 50% from the viewpoint of solubility and viscosity stability in a solution.

Specifically, as a polyimide precursor (A), the resin which has the repeating unit represented by General formula (26), General formula (27), and General formula (28) is mentioned, for example.

[Chemical 14]

In the general formulae (26) to (28), R ¹² represents a divalent organic group, and R ¹³ represents a tetravalent organic group. W ¹ and W ² each independently represent a hydrogen atom, a monovalent organic group having 1 to 10 carbon atoms, or a monovalent alkylsilyl group having 1 to 10 carbon atoms.

In the polyfluorene imine precursor (A), the number of the repeating units represented by the general formula (26), the general formula (27), and the general formula (28) is p, q, and r, respectively. p represents an integer of 1 or more. q and r each independently represent an integer of 0 or 1 or more. In addition, it is preferable that p, q, and r satisfy a relationship of 1% ≦ (2r + q) × 100 / (2p + 2q + 2r) ≦ 50%. p, q, and r preferably satisfy the relationship of 1% ≦ (2r + q) × 100 / (2p + 2q + 2r) ≦ 50%, and more preferably 2% ≦ (2r + q) × 100 / (2p + 2q + 2r) ≦ 30%.

Here, “(2r + q) × 100 / (2p + 2q + 2r)” is expressed in a bonding portion (a reaction portion between a tetracarboxylic dianhydride and a diamine compound) of a specific polyimide precursor, and The ratio of the number of bonded portions (2r + q) to the total number of bonded portions (2p + 2q + 2r). That is, "(2r + q) * 100 / (2p + 2q + 2r)" shows the fluorination rate of a specific polyfluorene imide precursor.

In addition, by setting the polyimide precursor (A) 's phosphonium imidization rate ("(2r + q) × 100 / (2p + 2q + 2r)") to 1% to 50%, more Ideally, it is 2% to 30%, and viscosity stability can be improved without deteriorating the solubility of the polyfluorene imine precursor (A) in the solution.

The fluorene imidation ratio ("(2r + q) × 100 / (2p + 2q + 2r)" value) of the polyfluorene imine precursor (A) was measured by the following method.

(Measurement of the fluorene imidation ratio of the polyfluorene imide precursor) First, a sample of the polyfluorene imine precursor (A) is prepared. Specifically, as the first step, a composition of a polyimide precursor (A) to be measured is applied on a silicon wafer in a range of a film thickness of 1 μm or more and 10 μm or less to prepare a coating film test. kind.

Next, as a second stage, the coating film sample was immersed in tetrahydrofuran (THF) for 20 minutes, and the solvent in the coating film sample was replaced with tetrahydrofuran (THF). The solvent to be impregnated is not limited to THF, and can be selected from solvents which do not dissolve the polyimide precursor (A) and which can be mixed with a solvent component contained in the composition of the polyimide precursor (A). . Specifically, alcohol solvents such as methanol and ethanol, and ether compounds such as dioxane can be used.

Then, as a third stage, the coating film sample was taken out of the THF, and N ₂ gas was blown on and removed from the THF adhering to the surface of the coating film sample. The coating film sample is dried under a reduced pressure of 10 mmHg or lower for 5 hours or more and 25 ° C or less for 12 hours to prepare a sample of polyimide precursor (A) (hereinafter, it is appropriately referred to as Polyimide precursor sample).

Next, a 100% ammonium imidization standard sample was made. Specifically, as the fourth stage immediately after the third stage, the composition of the polyimide precursor (A) to be measured is coated on a silicon wafer in the same manner as in the first stage. , Making coating film samples. Next, as a fifth step, the coating film sample was heated at 380 ° C. for 60 minutes to perform a fluorenimidization reaction to prepare a 100% fluorinated imidization standard sample.

Next, the determination and analysis of the fluorene imidization rate of the polyfluorene imine precursor (A) was performed. Specifically, as the sixth stage immediately after the fifth stage, a Fourier conversion infrared spectrophotometer (FT-730 manufactured by Horiba, Ltd.) was used to measure 100% fluorenimide standard samples, polyfluorene Infrared absorption spectrum of an amine precursor sample. (PEI) is obtained with 100% of the standard sample for the light absorption peak derived from aromatic ring ^-1 vicinity of 1500 cm (Ab '(1500 cm -1)) of, 1780 cm ^-1 originating from nearby (PEI) The ratio of the absorption peak (Ab '(1780 cm ^-1 )) of the bond to I' (100).

Then, as the first stage 7, where the same manner as the sixth stage of the polyimide precursor sample was measured with respect to obtaining a light absorption peak derived from an aromatic ring in the vicinity of 1500 cm ^-1 (Ab (1500 cm & lt ^-1)) of, 1780 cm light absorption peak (Ab (1780 cm ^-1)) originating from the vicinity of ^-1 acyl imine bond ratio I (x).

Then, based on the measured ratios I '(100) and ratios I (x) of the respective absorbance peaks, based on each of the following formulae 1 to 3, the imine of the polyimide precursor (A) was calculated.化 率。 The rate. Formula 1: Polyimide precursor imidization ratio (%) = I (x) × 100 / I '(100) Formula 2: I' (100) = (Ab '(1780 cm ^-1) )) / (Ab '(1500 cm ^-1 )) Formula 3: I (x) = (Ab (1780 cm ^-1 )) / (Ab (1500 cm ^-1 ))

The weight average molecular weight (Mw) of the polyimide precursor (A) is preferably 10,000 to 1,000,000, more preferably 10,000 to 500,000, and even more preferably 20,000 to 400,000. The number average molecular weight (Mn) of the polyimide precursor (A) is 5,000 to 1,000,000, preferably 5,000 to 500,000, and particularly preferably 15,000 to 300,000. When the weight average molecular weight and the number average molecular weight of the polyimide precursor (A) are within the above-mentioned ranges, the strength of the film obtained after curing can be increased without deteriorating the flatness of the obtained coating film.

The weight-average molecular weight, number-average molecular weight, and molecular weight distribution were measured using a DP-8020 GPC device (protection column: TSK guard colomn ALPHA column: TSK-GEL α-M, developing solvent) manufactured by Tosoh. N, N'-dimethyl acetamide (N, N'-dimethyl acetamide, DMAc), 0.05M-LiCl, 0.05% phosphoric acid) was added to determine the value.

In order to adjust the molecular weight to a preferable range, the polyfluorene imide precursor (A) may also be used to seal the ends with a capping agent. Examples of the terminal blocking agent that reacts with the acid dianhydride in the polyfluorene imine precursor (A) include a monoamine, a monohydric alcohol, and the like. Examples of the blocking agent that reacts with the diamine compound in the polyfluorene imide precursor (A) include acid anhydrides, monocarboxylic acids, monofluorene compounds, monoactive ester compounds, dicarbonates, and vinyl groups. Ethers, etc. In addition, by reacting the blocking agent, various organic groups can be introduced as terminal groups.

Examples of the monoamine used in the acid-anhydride-terminated sealant include 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, 1 -Hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, and the like are not limited thereto.

Examples of the monohydric alcohol used as the sealant of the acid anhydride group terminal include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3 -Pentanol, 1-hexanol, 2-hexanol, 3-hexanol, etc., but it is not limited to these.

Examples of the acid anhydride, monocarboxylic acid, monochloro compound, and monoactive ester compound used as the sealant for the amine group include phthalic anhydride, maleic anhydride, terradic anhydride, cyclohexanedicarboxylic anhydride, Monocarboxylic acids such as 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, and the like are chlorinated by chlorination of these carboxyl groups, and terephthalic acid and orthobenzene Dicarboxylic acids such as dicarboxylic acid, maleic acid, cyclohexanedicarboxylic acid, and 3-hydroxyphthalic acid are monochloride compounds obtained by sulfonation of only monocarboxyl groups. An active ester compound obtained by the reaction of hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboxyfluorene imine.

Examples of the dicarbonate compound used as the sealant at the amine end include di-tertiary butyl dicarbonate, dibenzyl dicarbonate, dimethyl dicarbonate, and diethyl dicarbonate. Examples of the vinyl ether compound used as the sealant at the amine end include chloroformates such as tertiary chloroformate, n-butyl chloroformate, isobutyl chloroformate, benzyl chloroformate, and isocyanate. Isocyanate compounds such as butyl ester and 1-naphthyl isocyanate; butyl vinyl ether, cyclohexyl vinyl ether, ethyl vinyl ether, and the like.

Examples of other compounds used as the sealant at the amine end include benzyl chloroformate, benzamidine chloride, fluorenyl methyl chloroformate, 2,2,2-trichloroethyl chloroformate, and allyl chloroformate. , Methanesulfonyl chloride, p-toluenesulfonyl chloride, phenyl isocyanate, etc.

With respect to the acid dianhydride component, the introduction ratio of the sealant at the end of the acid anhydride group is preferably in the range of 0.1 mol% to 60 mol%, and particularly preferably 5 mol% to 50 mol%. In addition, the introduction ratio of the amine-terminated sealant to the diamine component is preferably in the range of 0.1 mol% to 100 mol%, more preferably 0.5 mol% to 80 mol%, particularly preferably 1 mol. Ear% to 60 mole%. It is also possible to introduce a plurality of different terminal groups by reacting a plurality of end-capping agents.

The capping agent introduced into the polyfluorene imine precursor (A) can be easily detected by the following method. For example, a polymer introduced with a capping agent is dissolved in an acidic solution and decomposed into an amine component and an acid anhydride component as constituent units of the polymer, and gas chromatography (GC) or nuclear magnetic resonance (NMR) is performed on the polymer. Nuclear Magnetic Resonance (NMR) measurement, whereby the blocking agent can be easily detected. In addition, the polymer in which the end-capping agent is introduced can be easily detected by directly performing thermal decomposition gas chromatography (PGC) or infrared spectrum and ¹³ C NMR spectrum measurement.

<Solvent> The polyimide precursor resin composition of the embodiment of the present invention includes the polyimide precursor (A) and a solvent (B). The solvent (B) includes one or more solvents (B1) having an SP value of 7.7 or more and 9.0 or less, and a solvent (B2) having an SP value of more than 9.0 and 12.5 or less.

Here, the SP value is a parameter which is also called an solubility parameter and is an index of solubility and compatibility. There are generally a method of calculating a value of a solubility parameter based on physical properties such as heat of evaporation, and a method of estimating a value of a solubility parameter based on a molecular structure. Here, Fedors based on "Polymer Engineering And Science (Polym. Eng. Sci.)" (14 (2), 147-154 (1974)) are used. Method and the value calculated based on the molecular structure, the unit is (cal / cm ³ ) ^1/2 .

The polyimide precursor (A) has a structural unit represented by the general formula (2), and a part thereof includes a structure represented by the general formula (1). The SP value of the structural unit of the polyfluorene imide precursor (A) containing the structure of the general formula (1) is about 8.0, and the SP value of the structural unit of the polyfluorene imide precursor not containing the general formula (1) is about 8.0 11.0. In this case, when the solvent (B) contains at least one or more of the solvent (B1) and the solvent (B2), the polyimide precursor resin composition can be dissolved in the solvent (B) without turbidity. )in.

Examples of the solvent (B1) include 3-methoxy-3-methyl-1-butyl acetate (MMBAc (3-methoxy-3-methyl-1-butyl acetate), SP value: 8.85) 1, dipropylene glycol methyl ether acetate (DPMA, SP value: 8.99), dipropylene glycol dimethyl ether (DMM, dipropylene glycol dimethyl ether, SP value: 7.88), N, N-dimethylformaldehyde DMIB (N, N-dimethyl isobutyl amide, SP value: 8.81), etc.

Examples of the solvent (B2) include γ-butyrolactone (GBL (γ-butyrolactone), SP value: 10.52), N-methyl-2-pyrrolidone (NMP, SP value: 10.05), and cyclohexanone Ketone (SP value: 9.80), propylene glycol monomethyl ether (PGME, SP value: 11.27), propylene glycol monomethyl ether acetate (PGMEA, propylene glycol monomethyl ether acetate, SP value: 9.11), Dimethylacetamide (DMAc, SP value: 9.13), 1,3-dimethyl-2-imidazolidinone (DMI (1,3-dimethyl-2-imidazolidinone), SP value: 9.70), diethyl Diethylene glycol monobutyl ether acetate (BDGAc, SP value: 9.19), etc.

Since the polyimide precursor resin composition contains one or more of the solvent (B1) and the solvent (B2) as the solvent (B), the coating property using the slit is good, and the obtained Cloudiness and residual stress of polyimide film.

Of all the solvents (B) contained in the polyfluorene imide precursor resin composition according to the embodiment of the present invention, when the total amount of the solvent (B) is 100% by mass, it is preferable to include 5% by mass. % To 40% by mass of the solvent (B1) having an SP value of 7.7 or more and 9.0 or less, and 60% to 95% by mass of the solvent (B2) having an SP value of more than 9.0 and 12.5 or less. Moreover, from a viewpoint of reducing the haze of a cured film, it is more preferable that the solvent (B) contains 15 mass%-35 mass% of the solvent (B1) and 65 mass%-85 mass% of the solvent (B2).

Regarding the polyfluorene imide precursor resin composition according to the embodiment of the present invention, when the entire amount of the solvent (B) is 100% by mass, it is preferable that 70% by mass to all solvents (B) be contained. 100% by mass of the solvent having a vapor pressure at 20 ° C. of 10 Pa or more and 100 Pa or less, and more preferably 80 to 100% by mass. By including 70% to 100% by mass of all the solvents (B), the solvent having a vapor pressure of 100 Pa or less at 20 ° C can suppress the evaporation of the solvent (B). It is possible to suppress curing of the varnish generated in the vicinity of the coating portion of the metal port, and to suppress uneven coating and uneven coating such as streaks generated in the coating film. Furthermore, by including 70% to 100% by mass of all the solvents (B), a solvent having a vapor pressure of 10 Pa or more at 20 ° C can be uniformly removed from the entire coating film in the drying step of the coating film. Solvent (B). Therefore, it is possible to improve the film thickness uniformity of the film obtained after drying and suppress the haze of the film obtained.

Examples of the solvent having a vapor pressure of 10 Pa to 100 Pa at 20 ° C include NMP (39 Pa), DMI (100 Pa), MMBAc (53 Pa), DMM (80 Pa), and MMB ( 66 Pa), diethylene glycol monomethyl ether (20 Pa), diethylene glycol monoethyl ether (60 Pa), dipropylene glycol dimethyl ether (70 Pa), etc.

Among all the solvents (B) contained in the polyimide precursor resin composition according to the embodiment of the present invention, the difference between the vapor pressure of the solvent having the highest vapor pressure and the lowest solvent at 20 ° C. is preferably 100 Pa or less. It is further preferably 50 Pa or less. In this case, it is possible to prevent a phenomenon that, in the step of removing the solvent (B) from the coating film, only a specific solvent is removed first and the solvent composition in the coating film is partially polymerized. As a result, the increase in the haze of the cured film can be suppressed as a result. In addition, the polyimide precursor resin composition according to the embodiment of the present invention may include solvents other than those described above within a range that does not prevent the effect of the present invention.

<Concentration and viscosity of polyimide precursor resin composition> Although the viscosity of the polyimide precursor resin composition according to the embodiment of the present invention depends on the molecular weight or concentration of the polyimide precursor (A), However, it is usually 500 mPa · s to 10,000 mPa · s, and preferably 1,000 mPa · s to 6,000 mPa · s. In the case where the viscosity of the polyimide precursor resin composition is within the above range, the polyimide precursor resin composition in the film formation is excellent in retention property, and a coating film having excellent film thickness uniformity can be obtained. In the present invention, the viscosity of the polyimide precursor resin composition is a value measured at 25 ° C in the air using an E-type viscosity agent (manufactured by Toki Sangyo Co., Ltd., a viscosity meter MODEL RE100).

It is preferable that the density | concentration of the polyfluorene imide precursor (A) in the polyfluorene imide precursor resin composition of embodiment of this invention is performed so that the viscosity of a polyfluorene imide precursor resin composition may become the said range. The adjustment depends on the molecular weight of the polyimide precursor (A), but it is preferably 3% to 30% by mass, more preferably 5% to 25% by mass, and particularly preferably 10% to 20% by mass. %. When the concentration of the polyimide precursor (A) in the polyimide precursor resin composition is within the above-mentioned range, both thinning and thickening can be achieved, thereby making it difficult to generate pinholes and making it possible to A film having excellent surface smoothness is formed.

<Others> The polyfluorene imide precursor resin composition according to the embodiment of the present invention preferably contains a fluorene imine accelerator. For example, by adding a fluorene imidation accelerator when polymerizing the polyfluorene imine precursor (A), the fluorene imidization rate of the polyfluorene imine precursor (A) can be increased. In addition, it is possible to catalyze a thermal ammonium imidization reaction during curing to increase the elongation at break of the polyimide resin composition obtained after curing. The hydrazone imidization accelerator described herein is a compound having an effect of improving nucleophilicity and electrophilicity, and specific examples thereof include trimethylamine, triethylamine, tripropylamine, and tributyl. Tertiary amine compounds such as amines, carboxylic acid compounds such as 4-hydroxyphenylacetic acid, 3-hydroxybenzoic acid, polyphenol compounds such as 3,5-dihydroxyacetophenone, methyl 3,5-dihydroxybenzoate, and pyridine , Quinoline, isoquinoline, imidazole, benzimidazole, 2-ethyl-4-methylimidazole, 1,2,4-triazole and other heterocyclic compounds. It is preferably 0.1 to 5 parts by weight per 100 parts by weight of the polyimide precursor (A), more preferably 0.1 to 3 parts by weight, and particularly preferably Contains 0.3 to 3 parts by weight. By containing a fluorene imidization accelerator in the said range, the elongation at break of a polyfluorene imide resin composition can be improved, without deteriorating color tone, such as haze and transmittance, or degassing property in a high temperature region.

The polyimide precursor resin composition according to the embodiment of the present invention may contain a surfactant. Examples of the surfactant include Fluorad (trade name, manufactured by Sumitomo 3M), Megafac (trade name, manufactured by DIC), and Sulfuron (commodity Name, manufactured by Asahi Glass Co., Ltd.) and other fluorine-based surfactants. In addition, KP341 (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), DBE (trade name, manufactured by Chisso), Polyflow, Glano (trade name, co-prosperity) Co., Ltd.), BYK (BYK Chemie) and other organosiloxane surfactants. Examples: Emulmin (manufactured by Sanyo Chemical Industry Co., Ltd.) and other polyoxyalkylene lauryl ether, polyoxyethyl lauryl ether, polyoxyethyl oleyl alkenyl ether, and polyoxyethylene Cetyl ether surfactant. Furthermore, acrylic polymer surfactants such as Polyflow (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) can be cited. The surfactant is preferably contained in an amount of 0.001 to 1 part by weight based on 100 parts by weight of the polyfluorene imide precursor resin composition.

The polyimide precursor resin composition according to the embodiment of the present invention may contain an internal mold release agent. Examples of the internal mold release agent include long-chain fatty acids such as stearic acid and lauric acid.

The polyimide precursor resin composition according to the embodiment of the present invention may contain a thermal crosslinking agent. As the thermal crosslinking agent, an epoxy compound or a compound having at least two alkoxymethyl or methylol groups is preferable. By having at least two of these groups, a condensation reaction with a resin and the same molecule to form a crosslinked structure can improve the mechanical strength or chemical resistance of the cured film after heat treatment.

Preferred examples of the epoxy compound include bisphenol A epoxy resin, bisphenol F epoxy resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polymethyl (glycidyloxy group). Epoxy group-containing silicones such as propyl) and siloxane, but the present invention is not limited to any of them. Specific examples include: Epiclon 850-S, Epiclon HP-4032, Epiclon HP-7200, Epiclon HP-820, and Epiclon ( Epiclon) HP-4700, Epiclon EXA-4710, Epiclon HP-4770, Epiclon EXA-859CRP, Epiclon EXA-1514, Epiclon ( Epiclon) EXA-4880, Epiclon EXA-4850-150, Epiclon EXA-4850-1000, Epiclon EXA-4816, Epiclon EXA-4822 ( The above are trade names, manufactured by Dainippon Ink Chemical Industry Co., Ltd.), Rikaresin BEO-60E, Rikaresin BPO-20E, Rikaresin HBE-100, Rikaresin DME-100 ( The above are the trade names, manufactured by New Japan Physical and Chemical Corporation), EP-4003S, EP-4000S (the above are trade names, manufactured by ADEKA), PG-100, CG-500, EG-200 (the above are commodities Name, manufactured by Osaka Gas Chemicals), NC-3000, NC -6000 (the above are trade names, manufactured by Nippon Kayaku Co., Ltd.), EPOX-MK · R508, EPOX-MK · R540, EPOX-MK · R710, EPOX-MK · R1710, VG3101L, VG3101M80 (The above are trade names, Purin (Manufactured by Printec), Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085 (the above are trade names, Daicel Chemical Industry Co., Ltd.).

Examples of the compound having at least two alkoxymethyl or methylol groups include: DML-PC, DML-PEP, DML-OC, DMLOEP, DML-34X, DML-PTBP, DML-PCHP, DMLOHCP, DML -PFP, DML-PSBP, DML-POP, DLMMBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP , DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE , TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (the above are the trade names, manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark ) · MX-290, NIKALAC · MX-280, NIKALAC · MX-270, NIKALAC · MX-279, NIKALAC · MW-100LM, NIKALAC · MX-750LM (The above are the trade names, manufactured by Sanwa Chemical Co., Ltd.). The thermal crosslinking agent may contain two or more of these compounds.

The thermal crosslinking agent is preferably contained in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the polyfluorene imide precursor (A).

The polyimide precursor resin composition according to the embodiment of the present invention may contain a colorant. By adding a colorant, the color of the heat-treated film of the polyimide precursor resin composition can be adjusted.

As a colorant, a dye, an organic pigment, an inorganic pigment, etc. can be used, but an organic pigment is preferable in terms of heat resistance and transparency. Among them, those having high transparency, light resistance, heat resistance, and chemical resistance are preferred. When a specific index of a representative organic pigment is represented by a color index (CI) number, the following pigments can be preferably used, but are not limited to any of them.

As an example of a yellow pigment, Pigment Yellow (hereinafter referred to as PY) 12, 13, 17, 20, 24, 83, 86, 93, 95, 109, 110, 117, 125, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 168, 185, etc. In addition, as examples of orange pigments, Pigment Orange (hereinafter referred to as PO) 13, 36, 38, 43, 51, 55, 59, 61, 64, 65, 71, and the like can be used. In addition, as an example of a red pigment, Pigment Red (hereinafter referred to as PR) 9, 48, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 192, 209 can be used. , 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254, etc. In addition, as an example of a purple pigment, Pigment Violet (hereinafter referred to as PV) 19, 23, 29, 30, 32, 37, 40, 50, and the like can be used. In addition, as examples of the blue pigment, Pigment Blue (hereinafter referred to as PB) 15, 15: 3, 15: 4, 15: 6, 22, 60, 64, and the like can be used. In addition, as examples of the green pigment, Pigment Green (hereinafter referred to as PG) 7, 10, 36, 58 and the like can be used. These pigments may also be subjected to surface treatments such as rosin treatment, acid-based treatment, and alkaline treatment, if necessary.

The polyfluorene imide precursor resin composition according to the embodiment of the present invention may contain an inorganic filler. Examples of the inorganic filler include fine particles of silica, fine particles of alumina, fine particles of titania, and fine particles of zirconia.

The shape of the inorganic filler is not particularly limited, and examples thereof include a spherical shape, an oval shape, a flat shape, a rod shape, and a fibrous shape. In order to prevent light scattering, it is preferable that the inorganic filler contained has a small particle diameter. For example, the average particle diameter of the inorganic filler is in a range of 0.5 nm to 100 nm, and preferably in a range of 0.5 nm to 30 nm. When the entire amount of the polyfluorene imide precursor (A) is 100% by mass, the content of the inorganic filler is preferably 1 to 50% by weight, and more preferably 10 to 30% by weight.

Various well-known methods can be used for the method of making an inorganic filler in a polyimide precursor resin composition. For example, mixing an organic-inorganic filler sol with a polyfluorene imide precursor (A) is mentioned. The organic-inorganic filler sol is obtained by dispersing an inorganic filler in an organic solvent at a ratio of about 30% by mass. Examples of the organic solvent include methanol, isopropanol, n-butanol, ethylene glycol, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl acetate, propylene glycol monomethyl ether, and N, N. -Dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidone, γ-butyllactone, and the like.

In order to improve the dispersibility of the inorganic filler to the polyimide precursor (A), the organic-inorganic filler sol can also be treated with a silane coupling agent. In the case where the terminal functional group of the silane coupling agent has an epoxy group or an amine group, the carboxylic acid of the polyfluorene imide precursor (A) is bonded to the silane coupling agent, whereby the polyfluorene imide precursor (A ) Improved affinity with inorganic fillers for more effective dispersion.

Examples of the silane coupling agent having an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, and 3- Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and the like.

Examples of the silane coupling agent having an amino group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and N-2- (aminoethyl) -3- Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilane-N- (1,3-dimethyl -Butylene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and the like.

As a method for treating the organic-inorganic filler sol using a silane coupling agent, various known methods can be used. For example, the treatment can be performed by adding a silane coupling agent to the adjusted organic-inorganic filler sol and stirring at room temperature to 80 ° C. for 0.5 to 2 hours.

In order to improve the adhesion to the substrate, a coupling agent such as a silane coupling agent or a titanium coupling agent may be added to the polyfluorene imide precursor resin composition according to the embodiment of the present invention. The content of the coupling agent in the polyimide precursor resin composition is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the polyimide precursor (A).

In order to improve light resistance (resistance to light, especially ultraviolet light), the polyimide precursor resin composition according to the embodiment of the present invention may include an ultraviolet absorber. The content of the ultraviolet agent in the polyimide precursor resin composition is preferably from 0.01 to 10 parts by weight based on 100 parts by weight of the polyimide precursor (A).

<Polyimide resin composition> A polyimide resin composition according to an embodiment of the present invention is obtained by imidizing the polyamidine precursor resin composition. The method of fluorene imidization is not particularly limited, and examples thereof include heating fluorene imidization or chemical fluoridation. Among these, from the viewpoints of heat resistance of the obtained polyfluorene imine resin composition and transparency in the visible light region, fluorene imidization by heating is preferred. The polyimide precursor resin composition film is heated in a range of 180 ° C. to 650 ° C. to be converted into a polyimide resin composition. This is referred to as the thermal amidine process. In addition, the step of hot-liming may be performed after some steps after the step of evaporating the solvent from the coating film.

Regarding the step of evaporating the solvent from the coating film (also referred to as a drying step), specifically, the coating film may be vacuum-dried or heated. In consideration of the transparency of the imidized film, it is preferably The solvent was not evaporated without cloudiness. Drying uses a hot plate, oven, infrared, vacuum chamber, etc. Among them, vacuum drying is preferably performed using a vacuum chamber, and further, heating for drying is preferably performed after vacuum drying, or heating for drying is performed while performing vacuum drying. This can shorten the drying treatment time, and thus obtain a uniform coating film. The temperature for drying and heating varies depending on the type or purpose of the object to be heated, and it is preferably performed in a range from room temperature to 170 ° C. for 1 minute to several hours. The room temperature is usually 20 ° C to 30 ° C, but preferably 25 ° C. Furthermore, the drying step may be performed multiple times under the same conditions or different conditions.

The environment of the thermal arsine imidization step is not particularly limited, and may be air or an inert gas such as nitrogen or argon. Among them, since the polyfluorene imide resin composition of the present invention is required to be colorless and transparent, it is preferred to perform the thermal fluorination by heating in an environment having an oxygen concentration of 3% or less. Generally, lowering the oxygen concentration can reduce the oxidative coloration of the polyimide film during heating and maintain high transparency. On the other hand, it is often difficult to achieve an order-level oxygen concentration management at the manufacturing site. If the polyimide resin composition according to the embodiment of the present invention has an oxygen concentration of 3% or less during heating and curing, it is preferable to maintain higher transparency.

In addition, the time required to reach the heating temperature for thermal ammonium imidization is not particularly limited, and a heating method corresponding to the heating type of the manufacturing line can be selected. For example, the polyimide precursor resin composition formed on the substrate may be heated in an oven from room temperature to the heating temperature for thermal imidization from 5 minutes to 120 minutes, or may be formed in The polyfluorene imide precursor resin composition on the substrate is directly put into an oven heated in advance to a temperature range of 200 ° C. to 650 ° C. to perform a heat treatment. If necessary, heating may be performed under reduced pressure.

<Film of polyfluorene imine resin composition> The film of the polyfluorene imine resin composition according to the embodiment of the present invention is obtained by imidizing a polyfluorene imine precursor (A). Polyimide film, that is, polyimide resin film. The film of the polyfluorene imide resin composition (hereinafter, referred to as a polyfluorene imide resin film as appropriate) can be obtained, for example, by the following method. Examples of the method for forming the polyfluorene imide resin film include a method including the steps of: a coating film forming step of applying the polyfluorene imide precursor resin composition on a substrate to form a coating film, A drying step of evaporating a solvent (for example, the solvent (B)) from the coating film, and a step of imidizing a polyimide precursor (A). Hereinafter, a substrate coated with a polyimide precursor resin composition is suitably referred to as a support substrate, and may be distinguished from other substrates (for example, a flexible substrate using a polyimide resin film).

Regarding the method for forming a polyimide resin film, in the coating film forming step, the polyimide precursor resin composition is formed by coating the polyimide precursor resin composition on a support substrate. Coating film. Examples of the method for applying the polyimide precursor resin composition to a support substrate to form a coating film include a roll coating method, a spin coating method, a slit die coating method, and the use of a doctor blade, Coating method and the like. In addition, the thickness, surface smoothness, etc. of the coating film can be controlled by repeated coating. Among them, the slit die coating method is preferred from the viewpoint of surface smoothness and film thickness uniformity of the coating film.

The thickness of the coating film can be appropriately selected according to the required application, and is not particularly limited, and is, for example, 1 μm to 500 μm, preferably 2 μm to 250 μm, and particularly preferably 5 μm to 125 μm. Examples of the supporting substrate include a polyethylene terephthalate (PET) film, a polyethylene naphthalate (PEN) film, and a polybutylene terephthalate, PBT) film, silicon wafer, glass wafer, oxide wafer, glass substrate (including alkali-free glass substrate), Cu substrate and SUS plate, etc. Among them, an alkali-free glass substrate is preferred from the viewpoints of surface smoothness and dimensional stability during heating.

Then, in the drying step, the solvent is evaporated from the coating film on the support substrate, thereby drying the coating film. Specifically, in the drying step, the coating film may be dried by vacuum drying or heating. If the transparency of the film after the imidization is taken into consideration, it is preferable that the solvent is evaporated without turbidity. . Drying uses a hot plate, oven, infrared, vacuum chamber, etc.

Among them, it is preferable to vacuum-dry the coating film using a vacuum chamber, and it is more preferable to further heat the coating film after vacuum drying for drying, or to dry the coating film while vacuum drying. Of heating. This can shorten the drying treatment time of the coating film, thereby obtaining a uniform coating film. The temperature for heating for drying varies depending on the type or purpose of the object to be heated, such as a coating film, and it is preferably performed in a range from room temperature to 170 ° C. for 1 minute to several hours. The room temperature is usually 20 ° C to 30 ° C, but preferably 25 ° C. Furthermore, the drying step may be performed multiple times under the same conditions or different conditions.

Thereafter, in the fluorene imidization step, the fluorene imine precursor (A) in the coating film on the support substrate is fluorinated, thereby forming a polyfluorene resin film on the support substrate. The polyimide resin film formed on the support substrate through the above steps may be peeled from the support substrate and used, or may be used without peeling.

Examples of the method for peeling the polyimide resin film include a method of immersing in water, a method of immersing in a chemical liquid such as hydrochloric acid or hydrofluoric acid, and irradiating ultraviolet rays to the interface between the polyimide resin film and the support substrate A method of laser light in a wavelength range from light to infrared light, and the like. Among these, when the device is peeled off after the device is formed on the polyimide resin film, the device must be peeled off without damaging the device. Therefore, the laser light is preferably used for peeling. Moreover, in order to make peeling easy, before a polyimide precursor resin composition is apply | coated to a support substrate, you may apply | coat a mold release agent or a film formation sacrificial layer on a support substrate. Examples of the release agent include silicone-based, fluorine-based, aromatic polymer-based, alkoxysilane-based and the like. Examples of the sacrificial layer include a metal film, a metal oxide film, and an amorphous silicon film.

The thickness of the obtained polyfluorene imide resin film can be appropriately selected according to the required application, preferably 1 μm to 100 μm, more preferably 5 μm to 30 μm, and particularly preferably 7 μm to 20 μm. The polyfluorene imide resin film according to the embodiment of the present invention includes the structure represented by the general formula (1), and is preferably used for applications such as the production of a flexible display substrate. When the amount of the entire polyimide resin film is 100% by mass, it is preferable that such a polyimide resin film is represented by the general formula (1) containing 5% to 30% by mass. Structure.

The tensile elasticity coefficient of the polyimide resin film obtained from the polyimide precursor resin composition of the present invention is preferably 1.5 GPa or more, more preferably 2.0 GPa or more, and particularly preferably 2.5 GPa or more. When the polyimide resin film has a tensile elastic coefficient of 1.5 GPa or more, and preferably 2.0 GPa or more, it is possible to suppress the breakage when the film is peeled from the substrate, and to obtain a polyflex having sufficient flexibility. Amine resin film. The upper limit of the tensile modulus of elasticity of the polyfluoreneimide resin film is preferably 3.5 GPa or less.

The elongation at break of the polyimide resin film obtained from the polyimide precursor resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and particularly preferably 50% or more. In the case where the elongation at break of the polyimide resin film is 30% or more, the bending resistance is excellent and preferred.

The glass transition temperature of the polyfluorene imide resin film of this embodiment is 250 ° C or higher, preferably 350 ° C or higher, further preferably 380 ° C or higher, and particularly preferably 400 ° C or higher. The polyimide resin film is heated to 250 ° C or higher, preferably 350 ° C or higher during device fabrication. Therefore, if the glass transition temperature of the polyimide resin film is less than 350 ° C, the polyimide resin film is When used for such applications, the polyimide resin film may be deformed. On the other hand, if the glass transition temperature of the polyimide resin film is 380 ° C or higher, the surface roughness of the polyimide resin film after the gas barrier film is formed can be intentionally suppressed.

Furthermore, the haze value of the polyfluorene imide resin film of this embodiment is 1% or less, preferably 0.8% or less, and particularly preferably 0.5% or less. The polyfluorene imide precursor resin composition of the present invention can suppress phase separation caused by containing two or more solvents (for example, the solvent (B1) and the solvent (B2)) having SP values in a better range, respectively. Rising haze value.

<Laminate> A laminate according to an embodiment of the present invention includes a film (polyimide resin film) of the polyimide resin composition and an inorganic film.

Examples of the inorganic film include a gas barrier layer. The gas barrier layer is a layer that plays a role of preventing permeation of water vapor, oxygen, and the like. In order to suppress deterioration of the electronic device due to moisture or oxygen, it is preferable to provide a gas barrier property by providing a gas barrier layer on the polyimide resin film.

Examples of the material constituting the gas barrier layer include metal oxides, metal nitrides, metal oxynitrides, and metal carbonitrides. Examples of the metal elements included in these include aluminum (Al), silicon (Si), titanium (Ti), tin (Sn), zinc (Zn), zirconium (Zr), indium (In), and niobium. (Nb), molybdenum (Mo), tantalum (Ta), calcium (Ca), etc.

In particular, it is preferable that the gas barrier layer contains at least one of silicon oxide, silicon nitride, silicon oxynitride, and silicon carbonitride. The reason is that by using these materials, a uniform and dense film is easily obtained, and the oxygen barrier property of the gas barrier layer is further improved. From the viewpoint of further improving the oxygen barrier property, the gas barrier layer preferably contains a component represented by SiOxNy. x and y are values satisfying 0 <x ≦ 1, 0.55 ≦ y ≦ 1, 0 ≦ x / y ≦ 1.

In addition, the gas barrier layer is an inorganic film laminated with two or more layers. Among these inorganic films, the layer in contact with the polyimide resin film is preferably represented by SiOz (z is a value satisfying 0.5 ≦ z ≦ 2). The ingredients are formed. The reason is that, when the first layer of the inorganic film is formed, damage to the polyimide resin film is reduced, and therefore the deterioration of the surface smoothness of the polyimide resin film after the inorganic film is formed or the formation of inorganic Coloring of polyimide resin film at the time of film.

The manufacturing method of the laminated body of embodiment of this invention includes the following coating process, a removal process, a polyimide resin film formation process, and an inorganic film formation process and process, for example. In the method for manufacturing a laminated body, the coating step is a step of coating a polyimide precursor resin composition on a support substrate. The removing step is a step of removing a solvent from the coated polyimide precursor resin composition. The polyimide resin film forming step is a step of obtaining a film of a polyimide resin composition by imidizing the polyimide precursor resin composition from which the solvent has been removed. The inorganic film forming step is a step of forming an inorganic film on the film-like substance of the obtained polyfluorene imide resin composition. Among these steps, the coating step, the removing step, and the polyimide resin film forming step may be performed according to a method for producing a film of the polyimide resin composition. That is, the coating process in the manufacturing method of a laminated body is the same as the coating film formation process in the manufacturing method of a polyimide resin film. The removal step in the method for producing a laminated body is the same as the drying step in the method for producing a polyimide resin film. The polyimide resin film forming step in the method for producing a laminate is the same as the polyimide resin step in the method for producing a polyimide resin film. On the other hand, in the inorganic film forming step in the method of manufacturing a laminated body, the inorganic film is formed, for example, as follows.

The inorganic film can be produced by, for example, a sputtering method, a vacuum evaporation method, an ion plating method, a plasma chemical vapor deposition (CVD) method, or the like, and a vapor deposition method in which materials are deposited in a gas phase to form a film. . Among these, since a more uniform film with high oxygen barrier properties can be obtained, it is preferable to use a sputtering method or a plasma CVD method.

The number of layers of the inorganic film is not particularly limited, and may be only one layer or a multilayer of two or more layers. From the viewpoint of considering both bending resistance and gas barrier properties, a multilayer of two or more layers is preferred. Examples of the multilayer inorganic film include a gas barrier layer composed of SiN as the first layer and SiO as the second layer; a gas barrier layer composed of SiON as the first layer and SiO as the second layer.

From the viewpoint of improving the oxygen barrier property, the total thickness of the inorganic film is preferably 10 nm or more, and more preferably 50 nm or more. On the other hand, from the viewpoint of improving the bending resistance of the device, the total thickness of the inorganic film is preferably 1 μm or less, and more preferably 200 nm or less.

The laminated body formed on the substrate through the above steps may be used after being peeled from the substrate, or may be used without peeling. As an example of the method of peeling the laminated body, the same method as the method of peeling the polyfluoreneimide resin film from the substrate can be used.

<Use> The polyimide precursor resin composition of the embodiment of this invention, the polyimide resin composition obtained by using it, a polyimide resin film, and a laminated body can be used for an electronic device. More specifically, it can be used for display devices such as liquid crystal displays, organic EL displays, touch panels, electronic paper, color filters, light-emitting diode (Light-Emitting Diode, LED) displays, solar cells, and complementary metal oxidation. Light receiving devices such as Complementary Metal Oxide Semiconductor (CMOS). These electronic devices are preferably flexible devices. The polyimide resin film can be preferably used as a substrate in these electronic devices, especially a flexible substrate (such as a flexible display substrate).

The manufacturing steps of the flexible device include the steps of forming a circuit necessary for a display device or a light receiving device on a multilayer body formed on a substrate. For example, a thin film transistor (TFT) of amorphous silicon can be formed on a flexible substrate. Furthermore, a structure necessary for the device may be formed thereon by a known method. As described above, a known method such as laser irradiation can be used to peel a laminated body having a circuit or the like formed on its surface from the substrate, thereby obtaining a flexible device.

<Touch Panel> A touch panel according to an embodiment of the present invention includes the laminated body. An example of a configuration of a touch panel according to an embodiment of the present invention will be described with reference to the drawings.

FIG. 1A is a plan view showing a configuration example of a touch panel including a polyimide resin film according to an embodiment of the present invention. FIG. 1B is a cross-sectional view taken along a line II-II ′ of the touch panel shown in FIG. 1A. As shown in FIGS. 1A and 1B, the touch panel 7 includes a polyimide resin film 1, a gas barrier layer 2, a first wiring layer 3, a first insulating layer 4, a second wiring layer 5, and a second Insulation layer 6. That is, the touch panel 7 includes a polyimide resin film 1 as a flexible substrate, and includes a gas barrier layer 2 on the polyimide resin film 1. In addition, the touch panel 7 includes a first wiring layer 3 on the gas barrier layer 2, a first insulating layer 4 on the first wiring layer 3, a second wiring layer 5 on the first insulating layer 4, and a second The wiring layer 5 includes a second insulating layer 6.

The first wiring layer 3 and the second wiring layer 5 can be formed using a conductive composition. Examples of the components contained in the conductive composition include conductive particles, alkali-soluble resins, organic tin compounds, metal chelate compounds, dispersants, photopolymerization initiators, monomers, photoacid generators, At least one of a thermal acid generator, a solvent, a sensitizer, a pigment and a dye having absorption in visible light, an adhesion improver, a surfactant, or a polymerization inhibitor.

The conductive particles contained in the conductive composition preferably have a coating layer on at least a part of the surface. This can reduce the surface activity of the conductive particles, suppress at least one of the reactions between the conductive particles and the reaction between the conductive particles and the organic component, and improve the dispersibility of the conductive particles. Furthermore, even when photolithography is used in wiring processing, it is possible to pattern the wiring with high accuracy while suppressing the scattering of exposure light. On the other hand, in the presence of oxygen, by heating at a high temperature of about 150 ° C. to 350 ° C., it is possible to easily remove the coating layer and develop sufficient conductivity as wiring.

The coating layer preferably contains at least one of carbon and a carbon compound. When the coating layer contains at least one of carbon and a carbon compound, the dispersibility of the conductive particles in the conductive composition can be further improved.

Examples of a method for forming a coating layer containing at least one of carbon and a carbon compound on the surface of the conductive particles include a method in which a reactive gas having carbon, such as methane gas, is brought into contact with the conductive particles by a pyroplasma method ( For example, refer to Japanese Patent Laid-Open No. 2007-138287).

The first insulating layer 4 and the second insulating layer 6 can be formed using a photosensitive insulating composition containing an alkali-soluble resin. The content of the alkali-soluble resin contained in the insulating composition can be arbitrarily selected according to the required film thickness or use, and is usually set to 10 parts by mass or more and 70 parts by mass or less based on 100 parts by mass of the solid content.

The insulating composition may contain a hindered amine-based light stabilizer. By containing a hindered amine-based light stabilizer, the color of the first insulating layer 4 and the second insulating layer 6 can be further reduced, and the weather resistance can be improved. The insulating composition may further contain additives such as a polyfunctional monomer, a hardening agent, an ultraviolet absorber, a polymerization inhibitor, an adhesion improver, a solvent, a surfactant, a dissolution inhibitor, a stabilizer, and an antifoaming agent, if necessary.

The manufacturing method of the touch panel using the laminated body of embodiment of this invention includes the following layer formation process and peeling process, for example. In the method for manufacturing a touch panel, the layer forming step is a step of forming a wiring layer and an insulating layer on the laminated body. The peeling step is a step of peeling the laminated body from the support substrate. The peeling step in the manufacturing method of the touch panel can be performed according to the manufacturing method of the laminated body. On the other hand, in the layer forming step in the method of manufacturing a touch panel, for example, as described below, a laminate including a polyimide resin film 1 and a gas barrier layer 2 is laminated on the laminate (as shown in FIG. 1A and FIG. 1B). ) Forming a wiring layer (the first wiring layer 3 and the second wiring layer 5 in FIGS. 1A and 1B) and an insulating layer (the first insulating layer 4 and the second insulating layer 6 in FIGS. 1A and 1B).

(Step of Forming First Wiring Layer) The method for forming the first wiring layer (for example, the first wiring layer 3 shown in FIGS. 1A and 1B) preferably includes: coating a conductive composition on the gas barrier layer 2. A coating step, a pre-baking step of drying the coating film, a step of exposing and developing the pre-baking film to form a net pattern (exposure step and developing step), and a curing step of curing the pattern .

It is particularly preferred that the first wiring layer is formed using a conductive composition containing conductive particles having a coating layer on at least a part of the surface. The reason is that the conductive particles having a coating layer on at least a part of the surface can suppress the scattering of the exposure light in the exposure step and pattern the wiring with high accuracy.

As the light source used in the exposure step, for example, j-rays, i-rays, h-rays, and g-rays of a mercury lamp are preferred. As the developing solution used in the developing step, a known developing solution can be used. For example, an alkaline aqueous solution obtained by dissolving an alkaline substance such as sodium hydroxide, potassium hydroxide, tetramethyl ammonium hydroxide (TMAH) in water is mentioned.

The curing environment, temperature, and time can be appropriately determined depending on the composition of the conductive composition or the film thickness of the coating film. For example, the coating film is preferably heated in the air at a temperature range of 100 ° C to 300 ° C for 5 minutes to 120 minutes. In particular, when the first wiring layer contains conductive particles having a coating layer on the surface, in order to reliably remove the coating layer and develop sufficient conductivity, it is preferably in an environment having an oxygen concentration of 15% or more, The coating film is heated at a temperature of 100 ° C or higher and 300 ° C or lower.

In particular, in order to obtain a touch panel with less yellowing and excellent conductivity (such as the touch panel 7 shown in FIGS. 1A and 1B), it is preferable to include in its manufacturing steps: A step of forming a polyimide resin film by heating at a temperature of 300 ° C to 450 ° C in an environment, and heating at a temperature of 100 ° C to 300 ° C in an environment with an oxygen concentration of 15% or more The step of forming a first wiring layer.

(Step of Forming First Insulating Layer) A method of forming a first insulating layer (such as the first insulating layer 4 shown in FIGS. 1A and 1B) on the first wiring layer preferably includes: coating the first wiring layer A coating step of a cloth insulating composition, a pre-baking step of drying the coating film, a step of exposing and developing the pre-baking film to form a pattern (exposure step, developing step), and curing the pattern Curing step. Each step can be performed in the same manner as in the case of forming the first wiring layer.

(Step of Forming Second Wiring Layer and Second Insulating Layer) Next, a second wiring layer (for example, the second wiring layer 5 shown in FIGS. 1A and 1B) is formed on the first insulating layer. The second wiring layer can be formed by the same method as the first wiring layer. On the second wiring layer, for example, a second insulating layer may be formed as illustrated in the second insulating layer 6 in FIGS. 1A and 1B. By forming the second insulating layer, it is possible to suppress moisture in the atmosphere from reaching the second wiring layer and improve the moisture and heat resistance of the touch panel. The second insulating layer can be formed by the same method as the first insulating layer.

<Color filter> The color filter according to the embodiment of the present invention includes the laminated body. An example of a configuration of a color filter according to an embodiment of the present invention will be described with reference to the drawings.

FIG. 2 is a diagram showing a configuration example of a color filter including a laminated body according to an embodiment of the present invention. As shown in FIG. 2, the color filter 8 includes a polyimide resin film 1 and a gas barrier layer 2 in this order. That is, in the color filter 8, the laminated body is composed of a polyimide resin film 1 and a gas barrier layer 2 formed (laminated) thereon. In addition, the color filter 8 includes a black matrix 9, a red pixel 10R, a green pixel 10G, a blue pixel 10B, and an overcoat layer 11 on the gas barrier layer 2. The red pixel 10R is a red color pixel. The green pixel 10G is a green color pixel. The blue pixel 10B is a blue color pixel. The overcoat layer 11 is formed so as to cover the black matrix 9, the red pixels 10R, the green pixels 10G, and the blue pixels 10B.

The black matrix 9 is preferably a resin black matrix in which a black pigment is dispersed in a resin. Examples of the black pigment include carbon black, titanium black, titanium oxide, titanium oxide nitride, or titanium nitride. Particularly suitable are carbon black and titanium black. Moreover, a red pigment, a green pigment, and a blue pigment may be mixed and used as a black pigment.

As the resin used in the resin black matrix, a polyimide resin is preferable because it can easily form a fine pattern. The polyfluorene imine resin is preferably one obtained by thermally curing a polyfluorine acid synthesized from an acid anhydride and a diamine after pattern processing to form a polyfluorine resin. As examples of the acid anhydride, the diamine, and the solvent, those listed in the polyfluorene imine precursor (A) can be used.

The resin used in the resin black matrix is also preferably a photosensitive acrylic resin. The resin black matrix used therefor is preferably an alkali-soluble acrylic resin in which a black pigment is dispersed, a photopolymerizable monomer, a polymer dispersant, and an additive. Examples of the alkali-soluble acrylic resin include a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound.

The colored pixels usually include three colored pixels of red, green, and blue (that is, red pixels 10R, green pixels 10G, and blue pixels 10B). In addition to the three-color colored pixels, the brightness of white display of the display device can also be improved by forming colorless and transparent pixels or a fourth-color pixel that is extremely thinly attached. Examples of the resin used in the red pixel 10R, the green pixel 10G, and the blue pixel 10B include an acrylic resin, an epoxy resin, or a polyimide resin. The color filter 8 can be used. Since it is cheap to manufacture, a photosensitive acrylic resin is preferred. The photosensitive acrylic resin usually contains an alkali-soluble resin, a photopolymerizable monomer, and a photopolymerization initiator. Examples of the alkali-soluble resin include a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound.

The manufacturing method of the color filter using the laminated body of embodiment of this invention includes the following formation process and peeling process, for example. In the method for manufacturing a color filter, the forming step is a step of forming a black matrix and colored pixels on the laminated body. The peeling step is a step of peeling the laminated body from the support substrate. The peeling step in the method of manufacturing a color filter can be performed according to the method of manufacturing the laminated body. On the other hand, in the forming step in the method of manufacturing a color filter, a black matrix is formed, for example, as described below (black matrix 9 in FIG. 2).

In detail, in the forming step in the method for manufacturing a color filter, a spin coater or a die coater is used to form a cured film thickness on a laminated body (for example, on the gas barrier layer 2 shown in FIG. 2). A black resin composition for a black matrix containing a polyamino acid-containing resin in which a black pigment is dispersed is applied so as to be 1 μm. After drying under reduced pressure at 60 Pa or lower, semi-curing is performed using a hot air oven or a hot plate at 110 ° C to 140 ° C.

Next, using a spin coater or a die coater, a positive resist is applied so that the film thickness after the pre-baking is 1.2 μm. This was dried under reduced pressure at 80 Pa, and then pre-baked using a hot air oven or hot plate at 80 ° C to 110 ° C to form a resist film. Thereafter, the exposure is selectively performed with ultraviolet rays through a photomask using a proximity exposure machine, a projection exposure machine, or the like. Then, the exposed portion is removed by immersion in an alkaline developing solution such as potassium hydroxide or tetramethylammonium hydroxide at 1.5 to 3.0% by weight for 20 seconds to 300 seconds. After the positive resist is peeled off using a stripping solution, it is heated in a hot air oven or a hot plate at 200 ° C to 300 ° C for 10 to 60 minutes, thereby converting the polyamic acid to polyimide, and then on the resin film A resin black matrix (for example, black matrix 9 shown in FIG. 2) in which a black pigment is dispersed is formed. In the case of using a photosensitive resin, exposure and development can be performed without applying a positive resist.

Next, colored pixels are formed on the multilayer body after the resin black matrix is formed, for example, by the following method. In this embodiment, as the colored pixels, for example, red pixels 10R, green pixels 10G, and blue pixels 10B shown in FIG. 2 are formed.

The color pixels of the color filter are produced using a colorant and a resin. When a pigment is used as the colorant, a polymer dispersant and a solvent are mixed with the pigment and the dispersion treatment is performed, and then an alkali-soluble resin, a monomer, a photopolymerization initiator, and the like are added. On the other hand, when a dye is used as a colorant, a solvent, an alkali-soluble resin, a monomer, a photopolymerizable initiator, and the like are added to the dye. In this case, all the solid components are the total of the polymer dispersant, the alkali-soluble resin, the monomer, and the coloring agent as the resin component.

Next, the obtained colorant composition is applied on a transparent substrate on which a resin black matrix is formed by a spin coater or a die coater to a target film thickness of 0.8 μm to 3.0 μm after the heat treatment. Thing. After drying under reduced pressure at 80 Pa, it is pre-baked in a hot air oven or hot plate at 80 ° C to 110 ° C to form a coating film of a coloring agent.

Next, exposure is selectively performed using a proximity exposure machine, a projection exposure machine, or the like through a photomask. Thereafter, the unexposed portion is removed by immersing it in an alkaline developing solution such as a potassium hydroxide aqueous solution or a tetramethylammonium hydroxide aqueous solution for 0.02% to 1.0% by weight for 20 seconds to 300 seconds. The obtained coating film pattern is subjected to heat treatment for 5 to 40 minutes using a hot air oven or a hot plate at 180 ° C to 250 ° C to form colored pixels. Using a coloring agent composition prepared for each color of a coloring pixel, red coloring pixels (for example, red pixel 10R), green coloring pixels (for example, green pixel 10G), and blue coloring pixels (Eg, blue pixels 10B) sequentially perform the general patterning steps. The order of patterning the colored pixels is not particularly limited.

In the method for manufacturing a color filter according to this embodiment, a flattening layer may be provided on the color filter. Examples of the resin used in the formation of the planarization layer include epoxy resin, acrylic epoxy resin, acrylic resin, siloxane resin, or polyimide resin. The film thickness of the planarization layer is preferably a thickness having a flat surface, more specifically 0.5 μm to 5.0 μm, and still more preferably 1.0 μm to 3.0 μm.

<Liquid crystal element> A liquid crystal element according to an embodiment of the present invention includes the laminated body. An example of the structure of the liquid crystal element of embodiment of this invention is demonstrated using drawing.

FIG. 3 is a diagram showing a configuration example of a liquid crystal element including a laminated body according to an embodiment of the present invention. As shown in FIG. 3, the liquid crystal element 12 includes a polyimide resin film 1-1, a polyimide resin film 1-2, a gas barrier layer 2, a pixel electrode 13, a first alignment film 14, and a second The alignment film 15, the opposite electrode 16, the liquid crystal layer 17, and the polarizing plate 18.

In the liquid crystal element 12 shown in FIG. 3, the polyimide resin film 1-1 as a first base material and the polyimide resin film 1-2 as a second base material are arranged facing each other with a gap. A liquid crystal layer 17 is provided between these. A gas barrier layer 2 as an inorganic film is provided on the polyimide resin film 1-1, and an indium tin oxide (ITO), indium zinc oxide (IZO), or the like is provided thereon. A pixel electrode 13 as a transparent electrode formed by a transparent conductive film, and a first alignment film 14. As described above, by forming a laminate having the gas barrier layer 2 on the polyimide resin film 1-1, it is possible to impart gas barrier properties to the polyimide resin film 1-1, and to suppress an electrode caused by moisture or oxygen Degradation.

In addition, a gas barrier layer 2 as an inorganic film is provided on the facing surface of the polyimide resin film 1-2 (the surface facing the polyimide resin film 1-1). In this way, by forming a laminate having the polyimide resin film 1-2 and the gas barrier layer 2, it is possible to impart gas barrier properties to the polyimide resin film 1-2 and suppress the electrode caused by moisture or oxygen. Degradation. A counter electrode 16 as a transparent electrode is provided on a surface on the liquid crystal layer 17 side of the gas barrier layer 2 so as to face the pixel electrode 13. A second alignment film 15 is provided on a surface on the liquid crystal layer 17 side of the opposing electrode 16.

The manufacturing method of the liquid crystal element using the laminated body of embodiment of this invention includes the following formation process and peeling process, for example. In the method for manufacturing a liquid crystal element, the forming step is a step of forming a transparent electrode, an alignment film, and a liquid crystal layer on the laminated body. The peeling step is a step of peeling the laminated body from the support substrate. The peeling process in the manufacturing method of a liquid crystal element can be performed according to the manufacturing method of the said laminated body. On the other hand, the formation process in the manufacturing method of a liquid crystal element can be performed as follows, for example.

In detail, in the forming step in the method for manufacturing a liquid crystal element, first, a pixel electrode (for example, the pixel electrode 13 shown in FIG. 3) is formed on a multilayer body that becomes a first supporting substrate, and then a second support is formed. A counter electrode (for example, the counter electrode 16 shown in FIG. 3) is formed on the laminated body of the substrate. In this embodiment, the laminated body that becomes the first support base material includes the polyimide resin film 1-1 and the gas barrier layer 2 shown in FIG. 3. The laminated body to be the second supporting base material includes a polyimide resin film 1-2 and a gas barrier layer 2 shown in FIG. 3. The method of forming the pixel electrode and the opposite electrode may be any method as long as it can form a target film or pattern. For example, a sputtering method, a vacuum evaporation method, an ion plating method, and a plasma CVD method are suitable. A vapor deposition method in which a metal oxide is deposited in a gas phase to form a film. The film thicknesses of the pixel electrode and the opposite electrode are preferably 20 nm to 500 nm, and more preferably 50 nm to 300 nm.

Next, a first alignment film (for example, the first alignment film 14 shown in FIG. 3) is formed on the pixel electrode, and a second alignment film (for example, the second alignment film 15 shown in FIG. 3) is formed on the opposite electrode. A known material can be used as a material and a method for forming these alignment films. For example, it can be formed by applying an alignment film containing polyfluorene imide resin by a printing method, heating at 250 ° C. for 10 minutes using a hot plate, and subjecting the obtained film to a rubbing treatment. The thicknesses of the first alignment film and the second alignment film only need to be those that can align the liquid crystal of the liquid crystal layer (the liquid crystal layer 17 in FIG. 3), and are preferably 20 nm to 150 nm, respectively.

Next, a liquid crystal layer is formed. As for the formation of the liquid crystal layer, a known method can be used. For example, the liquid crystal layer can be formed by the following method. First, a sealant was applied to the second alignment film by a dispensing method, and heated at 90 ° C. for 10 minutes using a hot plate. On the other hand, a spherical spacer having a diameter of 5.5 μm was spread on the first alignment film. This was superimposed on a substrate (second alignment film) coated with a sealant, and heated at 160 ° C. for 90 minutes to harden the sealant while pressing in an oven to obtain a unit. Subsequently, the cell was left at a temperature of 120 ° C. and a pressure of 13.3 Pa for 4 hours, and then left under nitrogen for 0.5 hour, and then the liquid crystal compound was filled again under vacuum. The filling of the liquid crystal compound is performed by adding a cell to the chamber, decompressing it to a pressure of 13.3 Pa at room temperature, immersing the liquid crystal injection port in the liquid crystal, and returning to normal pressure using nitrogen. After filling the liquid crystal, the liquid crystal injection port is sealed with an ultraviolet curing resin. In this way, a liquid crystal layer (for example, the liquid crystal layer 17 shown in FIG. 3) is formed between the first alignment film and the second alignment film.

After these steps, the polyimide resin film (polyimide resin film 1-1, polyimide resin film 1-2) is peeled from the supporting substrate, and The polarizing plate 18 is attached to each of the fluorene imide resin film 1-1) and the second base material (polyimide resin film 1-2). Thereby, a liquid crystal element (for example, the liquid crystal element 12 shown in FIG. 3) can be obtained.

<Organic EL Element> An organic EL element according to an embodiment of the present invention includes the laminated body. An example of the configuration of the organic EL element according to the embodiment of the present invention will be described with reference to the drawings.

FIG. 4 is a diagram showing a configuration example of an organic EL element including a laminated body according to an embodiment of the present invention. As shown in FIG. 4, the organic EL element 19 includes a polyimide resin film 1, a gas barrier layer 2, a TFT layer 20, a planarization layer 21, a first electrode 22, an insulating layer 23, and a red organic EL light emitting layer 24R. , A green organic EL light-emitting layer 24G, a blue organic EL light-emitting layer 24B, and a second electrode 25.

In the organic EL element 19 shown in FIG. 4, a gas barrier layer 2 as an inorganic film is formed on the polyimide resin film 1. These polyimide resin films 1 and the gas barrier layer 2 constitute a laminated body included in the organic EL element 19. As shown in FIG. 4, a TFT layer 20 including an amorphous silicon, a low-temperature polycrystalline silicon, an oxide semiconductor, and the like, and a planarization layer 21 are provided on the gas barrier layer 2. Further, on the TFT layer 20 and the planarization layer 21, a first electrode 22 including Al / ITO and the like, and an insulating layer 23 covering an end portion of the first electrode 22 are provided. A red organic EL light emitting layer 24R, a green organic EL light emitting layer 24G, and a blue organic EL light emitting layer 24B are provided on the first electrode 22. The red organic EL light emitting layer 24R, the green organic EL light emitting layer 24G, and the blue organic EL light emitting layer 24B include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, respectively. A second electrode 25 including ITO or the like is formed on the insulating layers 23, the red organic EL light emitting layer 24R, the green organic EL light emitting layer 24G, and the blue organic EL light emitting layer 24B. As shown in FIG. 4, the second electrode 25 is sealed by the gas barrier layer 2. In the organic EL element 19, the TFT layer 20, the planarization layer 21, the first electrode 22, the insulating layer 23, the red organic EL light emitting layer 24R, the green organic EL light emitting layer 24G, the blue organic EL light emitting layer 24B, and the second electrode 25 And the gas barrier layer 2 as a sealing film constitute an organic EL light-emitting circuit on a laminated body.

The manufacturing method of the organic EL element using the laminated body of embodiment of this invention includes the following formation steps and peeling steps, for example. In the method for manufacturing an organic EL element, the forming step is a step of forming an organic EL light-emitting circuit on the laminated body. The peeling step is a step of peeling the laminated body from the support substrate. The peeling step in the manufacturing method of the organic EL element can be performed according to the manufacturing method of the laminated body. On the other hand, the formation step in the method of manufacturing an organic EL element can be performed, for example, as follows.

Specifically, in the forming step in the method of manufacturing an organic EL element, first, a TFT layer is formed on the laminated body. Examples of the semiconductor layer used to form the TFT layer include an amorphous silicon semiconductor, a polycrystalline silicon semiconductor, an oxide semiconductor represented by InGaZnO, and an organic semiconductor represented by pentacene or polythiophene. A specific method of forming the TFT layer is as follows. For example, using a multilayer body according to an embodiment of the present invention as a substrate, a gas barrier film, a gate electrode, a gate insulating film, a polycrystalline silicon semiconductor layer, an etching stopper layer, and a source / drain electrode are sequentially formed by a known method. Thereby, a TFT layer such as a bottom gate TFT (for example, the TFT layer 20 shown in FIG. 4) can be fabricated.

Next, a planarization layer (for example, the planarization layer 21 shown in FIG. 4) is formed on the TFT layer. Examples of the resin used in the formation of the planarization layer include epoxy resin, acrylic epoxy resin, acrylic resin, polysiloxane resin, and polyimide resin. Further, an electrode and an organic layer are formed on the planarization layer. Specifically, a first electrode (for example, the first electrode 22 shown in FIG. 4) including Al / ITO or the like is formed. Next, as the organic layer, an insulating layer (for example, insulating layer 23 shown in FIG. 4) covering the end portion of the first electrode is provided, and includes a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection. Layer of a white organic EL light emitting layer. In this embodiment, the white organic EL light emitting layer is composed of a red organic EL light emitting layer 24R, a green organic EL light emitting layer 24G, and a blue organic EL light emitting layer 24B. Further, a second electrode (for example, the second electrode 25 shown in FIG. 4) containing ITO or the like is formed on the white organic EL light-emitting layer, and a sealing film (the second electrode in FIG. 4) is formed to seal the second electrode. 25 on the gas barrier layer 2). In this way, an organic EL element (for example, the organic EL element 19 shown in FIG. 4) can be obtained. [Example]

Hereinafter, the present invention will be described with examples, but the present invention is not limited to the following examples and the like. First, the materials used in the following Examples and Comparative Examples, and the measurements and evaluations performed will be described.

<Material> As the acid dianhydride, the following is suitably used. BSAA: 2,2-bis (4- (3,4-dicarboxyphenoxy) phenyl) propane dianhydride ODPA: 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride PMDA: 1,2,4,5-benzenetetracarboxylic dianhydride PMDA-HS: 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride BPAF: 4,4 '-(fluorenyl) diphthalic acid Acid anhydride X-22-168-P5-B: modified methylphenyl silicone oil at both ends of carboxylic anhydride (manufactured by Shin-Etsu Chemical Co., Ltd.)

As a diamine compound, the following is suitably used. CHDA: trans-1,4-diaminocyclohexane TFMB: 2,2'-bis (trifluoromethyl) benzidine m-TB: 2,2'-dimethyl-4,4'-di Aminobiphenyl 4,4'-DDS: 4,4'-diaminodiphenylfluorene X22-1660B-3: Both terminal amines modified methylphenyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.)

As a triamine compound, the following is suitably used. 1,3,5-TAPOB: 1,3,5-tris (4-aminophenoxy) benzene In addition, as a tetraamine compound, the following is suitably used. TAB-S: 3,3 ', 4,4'-tetraaminodiphenylphosphonium

As a solvent (for example, the solvent (B1) and the solvent (B2) contained in the solvent (B)), the following are suitably used. NMP: N-methyl-2-pyrrolidone (SP value: 10.05, vapor pressure (20 ° C): 39 Pa) GBL: γ-butyrolactone (SP value: 10.52, vapor pressure (20 ° C): 150 Pa ) MMBAc: 3-methoxy-3-methyl-1-butyl acetate (SP value: 8.85, vapor pressure (20 ° C): 53 Pa) DPMA: dipropylene glycol methyl ether acetate (SP value: 8.99, Vapor pressure (20 ° C): 6.8 Pa) PGME: Propylene glycol monomethyl ether (SP value: 11.27, Vapor pressure (20 ° C): 1150 Pa) DMIB: N, N-dimethylisobutylamidamine (SP Value: 8.81, vapor pressure (20 ° C): 167 Pa) BDGAc: butyl diethylene glycol acetate (SP value: 9.19, vapor pressure (20 ° C): 5.3 Pa) n-octane (SP value: 7.55, vapor Pressure (20 ° C): 1330 Pa) 1,3-Butylene diethylene glycol (SP value: 12.75, Vapor pressure (20 ° C): 8 Pa)

As the alkali-soluble resin, those shown below are suitably used. Alkali soluble resin (AR): Add 0.4 equivalent of glycidyl methacrylate to the carboxyl group of a copolymer containing methacrylic acid / methyl methacrylate / styrene = 54/23/23 (mole%) Produced by reaction (weight average molecular weight (Mw): 29,000)

As the conductive particles, those shown below are suitably used. Conductive particles (A-1): Silver particles with an average thickness of 1 nm on the surface carbon coating layer and a primary particle diameter of 40 nm (manufactured by Nisshin Engineering Co., Ltd.) Conductive particles (A-2): Primary particle diameter of 0.7 μm silver particles (manufactured by Mitsui Metals)

<Evaluation> (Item 1: Appearance Evaluation of Varnish) In item 1, the appearance evaluation of a varnish containing a polyimide precursor resin composition and forming a polyimide resin film will be described. In the appearance evaluation of the varnish, the varnish added to the four-necked flask was irradiated with white LEDs, and the turbidity of the varnish was confirmed. As a result of the evaluation, those with no turbidity in the varnish were found to be excellent (EX). A person whose turbidity was hardly recognized under a fluorescent lamp but whose turbidity was confirmed by irradiation with a white LED was considered as good (G). Those with turbidity under fluorescent light or white turbidity were regarded as bad (NG). The "turbidity" referred to here refers to a phenomenon of layer separation due to insufficient affinity between a silicone component and a solvent. The term "white turbidity" refers to a phenomenon in which the polyimide precursor (A) obtained by polymerization is not completely dissolved in the solvent (B) and is precipitated.

(Item 2: Measurement of weight average molecular weight (Mw), number average molecular weight (Mn)) In item 2, the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polyimide precursor (A) The measurement will be described. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polyimide precursor (A) in the polyimide precursor resin composition obtained in the examples and comparative examples were obtained using TOSOH. The manufactured HLC-8220 GPC device (protection column: TSK guard colomn ALPHA column: TSKgel ALPHA-M, developing solvent: NMP) was used for measurement. The calibration curve used to calculate the weight-average molecular weight was prepared using standard polystyrene (manufactured by Tosoh Corporation).

(Item 3: Production of polyimide resin film (on the first glass substrate)) In item 3, a method of making a polyimide resin film (on the first glass substrate) will be described with reference to FIG. 5. . FIG. 5 is a diagram for explaining production of a polyimide resin film and evaluation of coatability in Examples. In the production of the polyimide resin film in item 3, a slit coater (Toray Engineering Co., Ltd.) was used on a glass substrate 26 (AN-100 manufactured by Asahi Glass Co., Ltd.) having a thickness of 300 mm × 350 mm × 0.5 mm. (Manufacturing) The varnish was applied in the direction shown by arrow 29 so that the cured film thickness was 10 μm ± 0.5 μm, and then pre-baking was performed using a heating vacuum dryer and a hot plate. The heating-type vacuum dryer was dried under the following conditions: the upper plate was heated to 60 ° C, the lower plate was heated to 40 ° C, and the internal pressure was lowered to 60 Pa over 150 seconds. The heating plate was dried by heating to 120 ° C for 6 minutes. The pre-baking film thus obtained was heated to 400 ° C. in an inert oven (INH-21CD manufactured by Koyo Thermo System) under a nitrogen gas flow (oxygen concentration of 100 ppm or less) over 80 minutes. It was held for 30 minutes and cooled to 50 ° C at 5 ° C / minute to 8 ° C / minute. Thereby, as shown in FIG. 5, a polyimide resin film 27 is produced on the glass substrate 26 (first glass substrate).

(Item 4: Applicability Evaluation) In item 4, the applicability evaluation of the polyimide resin film will be described with reference to FIG. 5. In this applicability evaluation, the polyimide resin film shown in the said 3rd item was used for each evaluation of the coating unevenness and in-plane uniformity as described below.

(Item 4-1: Number of sheets due to uneven coating) In the evaluation of uneven coating, the obtained polyimide resin film (10 sheets) was observed with a microscope at a magnification of 20 times at the peripheral portion and the central portion ( The central part of the polyimide resin film 27 shown in FIG. 5) is judged as “good” when there is no uneven coating, and is judged as “bad” when there is uneven coating. In the table described later, as a result of the evaluation of uneven coating, the number of pieces of samples which were determined to be defective due to uneven coating was described. The coating unevenness referred to here refers to unevenness (for example, uneven stripes) due to a difference in film thickness of the polyimide resin film.

(Item 4-2: In-Planar Uniformity of Film Thickness) In the in-plane uniformity evaluation of film thickness, the 10 portions of the polyimide resin film 27 (for example, the film thickness measurement portion shown in FIG. 5) Part 28) Measure the film thickness in the direction of the nozzle at a position 50 mm from the coating start portion except for the coating end portion (the portion 10 mm from the outer periphery of the polyimide resin film 27), and use the following calculation The in-plane uniformity of the film thickness is calculated by the formula. The maximum film thickness and the minimum film thickness in the calculation formula refer to the largest one and the smallest one among the ten measured locations. The average film thickness refers to the average of the film thicknesses of the 10 locations measured. The nozzle direction referred to here means a direction perpendicular to the application direction. In-plane uniformity (%) = ((maximum film thickness)-(minimum film thickness)) / (2 × (average film thickness)) × 100

(Item 5: Production of polyimide resin film (on the first silicon substrate)) In item 5, a method for producing a polyimide resin film (on the first silicon substrate) will be described. In the method for manufacturing a polyimide resin film in item 5, a coating and developing device made by Tokyo Electron Co., Ltd. Mark-7 was used on a 6-inch silicon substrate (the first silicon substrate). , Spin-coat the varnish with a film thickness of 10 μm ± 0.5 μm after curing. Thereafter, similarly, a preheating treatment at 120 ° C. for 6 minutes was performed using a Mark-7 hot plate. The obtained pre-baking film was heated to 400 ° C. at 4 ° C./min using an inert oven (INH-21CD manufactured by Koyo Thermo System) under a nitrogen gas flow (oxygen concentration of 100 ppm or less). It was held for 30 minutes and cooled to 50 ° C at 5 ° C / minute to 8 ° C / minute. Thereby, a polyimide resin film was produced on the first silicon substrate.

(Item 6: Production of polyimide resin film (on the second glass substrate)) In item 6, a method for producing a polyimide resin film (on the second glass substrate) will be described. In the method for producing a polyimide resin film in Item 6, a 50 mm × 50 mm × 1.1 mm thick glass substrate (Tampax) is used as the second glass substrate, and Mikasa is used. The spin coater MS-A200 manufactured by the company spin-coated the varnish so that the film thickness after curing was 10 μm ± 0.5 μm. Thereafter, a pre-baking treatment was performed at 120 ° C. for 6 minutes using a hot plate D-SPIN manufactured by Dainippon Screen. The obtained pre-baking film was heated to 400 ° C. at 4 ° C./min using an inert oven (INH-21CD manufactured by Koyo Thermo System) under a nitrogen gas flow (oxygen concentration of 100 ppm or less). It was held for 30 minutes and cooled to 50 ° C at 5 ° C / minute to 8 ° C / minute. Thereby, a polyimide resin film was produced on the second glass substrate.

(Item 7: Production of polyimide resin film (on the second silicon substrate)) In item 7, a method for producing a polyimide resin film (on the second silicon substrate) will be described. In the method for manufacturing a polyimide resin film in item 7, a spin coater MS-A200 made by Mikasa was used on a 4-inch silicon substrate (second silicon substrate) cut to 1/4. The varnish was spin-coated so that the film thickness after curing was 5 μm ± 0.5 μm. Thereafter, a pre-baking treatment was performed at 120 ° C. for 6 minutes using a hot plate D-SPIN manufactured by Dainippon Screen. The obtained pre-baking film was heated to 400 ° C. at 4 ° C./min using an inert oven (INH-21CD manufactured by Koyo Thermo System) under a nitrogen gas flow (oxygen concentration of 100 ppm or less). It was held for 30 minutes and cooled to 50 ° C at 5 ° C / minute to 8 ° C / minute. As a result, a polyimide resin film was produced on the second silicon substrate.

(Item 8: Measurement of Light Transmittance (T)) In Item 8, the measurement of the light transmittance (T) of the polyimide resin film will be described. In the measurement of the light transmittance (T) in the item 8, a UV-visible spectrophotometer (MultiSpec 1500 manufactured by Shimadzu Corporation) was used to measure the light transmittance of the polyimide resin film at 450 nm. In addition, the polyimide resin film shown in the said 6th item was used for this measurement.

(Item 9: Measurement of Haze Value) In item 9, the measurement of the haze value of the polyimide resin film will be described. In the measurement of the haze value in item 9, the direct reading haze computer (HGM2DP, C light source manufactured by suga test machine company) was used to measure the haze value on the second glass substrate shown in the above item 6. Haze value of polyimide resin film (%). In addition, as each value, the average value of 3 measurements was used.

(Item 10: Measurement of In-Plane / Out-Plane Birefringence) In Item 10, measurement of in-plane / out-plane birefringence of a polyimide resin film will be described. In the measurement of in-plane / out-plane birefringence in Item 10, a chirped coupler (manufactured by Metricon Corporation, PC2010) was used to measure the TE refractive index (n (TE)) and TM at a wavelength of 632.8 nm Refractive index (n (TM)). n (TE) and n (TM) are the refractive index in the parallel and vertical directions with respect to the polyimide resin film surface, respectively. In-plane / out-plane birefringence is calculated as the difference (n (TE) -n (TM)) between n (TE) and n (TM). In addition, the polyimide resin film shown in the said 7th item was used for this measurement.

(Item 11: Measurement of Glass Transition Temperature (Tg)) In Item 11, the measurement of the glass transition temperature of the polyimide resin film will be described. In the measurement of the glass transition temperature in item 11, a thermomechanical analysis device (EXII 6000TMA / SS6000 manufactured by SII NanoTechnology) was used for the measurement under a nitrogen gas flow. The heating method was performed under the following conditions. In the first stage, the sample was adsorbed with water at a temperature increase rate of 5 ° C / min to 150 ° C, and in the second stage, air was cooled to room temperature at a temperature decrease rate of 5 ° C / min. In the third stage, a formal measurement was performed at a heating rate of 5 ° C./minute, and the glass transition temperature was determined. In this measurement, the polyimide resin film shown in the fifth item is peeled from a silicon wafer (first silicon substrate) and used.

(Item 12: Measurement of 1% weight reduction temperature (Td1)) In Item 12, the measurement of the 1% weight reduction temperature of the polyimide resin film will be described. In the measurement of the 1% weight loss temperature in Item 12, the measurement was performed under a nitrogen gas flow using a thermogravimetric measuring device (TGA-50 manufactured by Shimadzu Corporation). The heating method was performed under the following conditions. In the first stage, the sample was adsorbed with water at a temperature rising rate of 3.5 ° C / min to 150 ° C, and in the second stage, it was cooled to room temperature at a cooling rate of 10 ° C / min. In the third stage, a formal measurement was performed at a heating rate of 10 ° C./minute, and a 1% thermal weight reduction temperature was determined. In this measurement, the polyimide resin film shown in the fifth item is peeled from a silicon wafer (first silicon substrate) and used.

(Item 13: Measurement of Elongation at Break and Coefficient of Elasticity) In item 13, measurement of the elongation at break and coefficient of elasticity of the polyimide resin film will be described. In the measurement of the elongation at break and the coefficient of elasticity in Item 13, Tensilon (RTM-100 manufactured by Orientec) was used for the measurement. The measurement was performed on 10 or more samples for each sample, and the JIS average was calculated using the Japanese Industrial Standards (JIS) number average (JIS K-6301). In this measurement, the polyimide resin film shown in the fifth item is peeled from a silicon wafer (first silicon substrate) and used.

(Item 14: Measurement of Residual Stress) In item 14, measurement of the residual stress of the polyimide resin film will be described. In the measurement of the residual stress in Item 14, the measurement was performed using a thin film stress measuring device FLX-3300-T manufactured by KLA-Tencor. In this measurement, the polyimide resin film shown in the above item 5 was used. At this time, the polyimide resin film was allowed to stand for 24 hours in a room having a room temperature of 23 ° C and a humidity of 55% before the measurement.

(Item 15: Evaluation of Arithmetic Mean Roughness (Ra)) In Item 15, the evaluation of arithmetic mean roughness (Ra) will be described. In the evaluation of the arithmetic average roughness (Ra) in Item 15, the surface of the polyimide resin film before the film formation of the gas barrier layer and the gas barrier layer were formed using an atomic force microscope (AFM) under the following conditions. The surface of the inorganic film after film formation was measured for arithmetic mean roughness (Ra). System: NanoScopeIII / MMAFM (manufactured by Digital Instruments) Scanner: AS-130 (J-Scanner) Probe: NCH-W type, monocrystalline silicon (manufactured by NanoWorld) Scanning mode: Tapping mode Scanning range: 10 μm × 10 μm Scanning speed: 0.5 Hz Measurement environment: temperature 23 ° C, relative humidity 65%, in the atmosphere

(Item 16: Evaluation of Bending Resistance of Laminated Body) In Item 16, the evaluation of bending resistance of the laminated body will be described. In the bending resistance evaluation in Item 16, the bending resistance of a laminate having an inorganic film on a polyimide resin film was measured by the following method. First, the laminated body peeled from the glass substrate was sampled to a size of 100 mm × 140 mm, and a metal cylinder with a diameter of 30 mm was fixed to the center of the surface. Along the metal cylinder, a metal cylinder with an angle of 0 ° A state in which the sample is flat) (refer to the laminated body 30 and the metal cylinder 31 shown in FIG. 6). Next, the laminated body was bent 100 times within a range of 180 ° for the metal cylinder (in a state where the metal cylinder is folded) (refer to the laminated body 30 and the metal cylinder 31 shown in FIG. 7). . Bending resistance was determined using the presence or absence of cracks in the inorganic film before and after the bending operation as an index. After the test, an optical microscope (manufactured by Nikon Corporation, OPTIPHOT300) was used to visually observe 100 laminates.

(Item 17: Production of Touch Panel and Evaluation of Humidity and Heat Resistance) In Item 17, production of touch panel and evaluation of humidity and heat resistance will be described. In the production of the touch panel and the evaluation of the moisture and heat resistance in Item 17, the following method was used to prepare a touch panel using a conductive composition and an insulating composition prepared in advance, and then the moisture and heat resistance of the touch panel was performed. test.

(Production Example 1: Production of Conductive Composition) In Production Example 1, a conductive composition (AE-1) was prepared. In detail, a mixture of 80 g of conductive particles (A-1) and 4.06 g of a surfactant ("DISPERBYK" (registered trademark) 21116: manufactured by DIC), A mixture of 98.07 g of PGMEA and 98.07 g of DPM was processed by a homogenizer at 1200 rpm for 30 minutes. Furthermore, the mixture was dispersed using a high-pressure wet-type medium-free micronization device nanomizer (manufactured by Nanomizer) to obtain a silver dispersion liquid having a silver content of 40% by mass.

20 g of an alkali-soluble resin (AR) as an organic compound and 0.6 g of ethyl acetoacetate diisopropoxide (ALCH: Kawaken Fine Chemicals) as a metal chelate compound (Manufactured), 2.4 g of photopolymerization initiator (NCI-831: manufactured by ADEKA), and 12.0 g of PE-3A were mixed, and 132.6 g of PGMEA and 52.6 g of DPM were added and stirred, Thereby, an organic I liquid for a conductive composition is obtained. The silver dispersion liquid and the organic I liquid were mixed at a mass ratio of 72.6 / 27.4 to obtain a conductive composition (AE-1).

(Production Example 2: Production of Insulating Composition) In Production Example 2, an insulating composition (OA-1) was prepared. Specifically, 50.0 g of cardo resin (V-259ME: manufactured by Nippon Steel Sumitomo Chemical Co., Ltd.), 18.0 g of crosslinkable monomer (TAIC: manufactured by Nihon Kasei Co., Ltd.) are added to a clean bottle, 10.0 g of crosslinkable monomer (M-315: manufactured by Toa Synthesis), 20.0 g of epoxy compound (PG-100: manufactured by Osaka Gas Chemicals), 0.2 g of photopolymerization initiation Agent (OXE-01: manufactured by BASF) and stirred for 1 hour to obtain an insulating composition (OA-1).

(Production of Touch Panel) In the production of the touch panel, the first wiring layer of the touch panel is formed by the following method. Specifically, on a polyimide resin film or a laminate including the polyimide resin film, a spin coater ("1H-360S (trade name)" manufactured by Mikasa Corporation) was used at 300 rpm. The conductive composition (AE-1) was spin-coated under the conditions of 10 seconds and 500 rpm for 2 seconds. Thereafter, a preheating film ("SCW-636 (trade name)" manufactured by Dainippon Screen Manufacturing Co., Ltd.) was prebaked at 100 ° C for 2 minutes to prepare a prebaked film. A pre-baking film was exposed using a parallel light mask aligner ("PLA-501F (trade name)" manufactured by Canon Corporation), using an ultra-high pressure mercury lamp as a light source, with a desired mask therebetween. Thereafter, using an automatic developing device ("AD-2000 (trade name)" manufactured by Takizawa Industries Co., Ltd.), a 0.045 mass% potassium hydroxide aqueous solution was used for 60 seconds of spray development, and then, water was rinsed for 30 seconds Pattern processing in seconds. The patterned substrate was cured in an air (oxygen concentration: 21%) at 250 ° C. for 30 minutes using an oven to form a first wiring layer.

Then, the following method is used to form the first insulating layer of the touch panel. Specifically, an insulating composition (OA-1) was spin-coated on a substrate on which the first wiring layer was formed using a spin coater at 650 rpm for 5 seconds. Thereafter, a pre-baking film was prepared by pre-baking at 100 ° C for 2 minutes using a hot plate. Using a parallel light mask aligner, use an ultra-high pressure mercury lamp as the light source and expose the pre-baked film through the required mask. After that, using an automatic developing device, spray development was performed with a 0.045 mass% potassium hydroxide aqueous solution for 60 seconds, and then water was rinsed for 30 seconds to perform pattern processing. The patterned substrate was cured in an air (oxygen concentration: 21%) at 250 ° C. for 60 minutes using an oven to form a first insulating layer.

Then, the second wiring layer is formed on the substrate on which the first insulating layer is formed by the same method as the first wiring layer. Then, the second insulating layer is formed on the substrate on which the second wiring layer is formed by the same method as the first insulating layer. Finally, the periphery of the area where the first wiring layer and the second wiring layer are formed is cut with a single-edged knife from above, and mechanical peeling is performed from the cut end surface, thereby obtaining a touch panel.

(Evaluation of Moisture and Heat Resistance) In the evaluation of the moisture and heat resistance of a touch panel, the moisture and heat resistance test of the touch panel was performed to measure the moisture and heat resistance of the touch panel. For the measurement of the humidity and heat resistance, an insulation deterioration characteristic evaluation system "ETAC SIR13" (manufactured by Kusumoto Chemical Co., Ltd.) was used. In detail, electrodes are respectively installed at the ends of the first wiring layer and the second wiring layer of the touch panel, and the touch panel is added to a high-temperature and high-humidity tank set to 85 ° C and 85% RH conditions. After 5 minutes have elapsed since the environment in the tank was stable, a voltage was applied between the electrodes of the first wiring layer and the second wiring layer to measure the change in insulation resistance over time. Using the first wiring layer as a positive electrode and the second wiring layer as a negative electrode, a voltage of 10 V was applied, and the resistance value was measured at intervals of 5 minutes for 500 hours. When the measured resistance value reaches 10 ⁵ or less, it is judged as a short circuit due to poor insulation, the embossing is stopped, and the test time thus far is set as the short circuit time. Thereafter, the humidity and heat resistance was evaluated in accordance with the following evaluation criteria, and a case where the evaluation level was 2 or more was determined to be acceptable. Evaluation level = 5: Short-circuit time is 1000 hours or more. Evaluation level = 4: Short-circuit time is 500 hours or more and less than 1000 hours. Evaluation level = 3: Short-circuit time is 300 hours or more and less than 500 hours. Evaluation level = 2: Short-circuit time is 100. Hours or more and less than 300 hours Evaluation level = 1: short circuit time is less than 100 hours

(Example 1) In Example 1, under a stream of dry nitrogen, ODPA (6.25 g (20.1 mmol)), PMDA (0.48 g (2.24 mmol)), m-TB (4.64) were added to a 200 mL four-necked flask. g (21.9 mmol)), X-22-1660B-3 (2.26 g (0.51 mmol)), NMP (75 g), and MMBAc (25 g), heat and stir at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyfluorene imide precursor were 70,000 and 33,000, respectively.

(Example 2) In Example 2, under a stream of dry nitrogen, ODPA (6.25 g (20.1 mmol)), PMDA (0.48 g (2.24 mmol)), and m-TB (4.64) were added to a 200 mL four-necked flask. g (21.9 mmol)), X-22-1660B-3 (2.26 g (0.51 mmol)), NMP (75 g), and DPMA (25 g). Heat and stir at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyfluorene imide precursor were 72,000 and 32,500, respectively.

(Example 3) In Example 3, under a stream of dry nitrogen, ODPA (6.25 g (20.1 mmol)), PMDA (0.48 g (2.24 mmol)), m-TB (4.64) were added to a 200 mL four-necked flask. g (21.9 mmol)), X-22-1660B-3 (2.26 g (0.51 mmol)), NMP (75 g), and DMM (25 g), heat and stir at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyfluorene imide precursor were 72,000 and 33,000, respectively.

(Example 4) In Example 4, under a stream of dry nitrogen, ODPA (6.25 g (20.1 mmol)), PMDA (0.48 g (2.24 mmol)), m-TB (4.64) were added to a 200 mL four-necked flask. g (21.9 mmol)), X-22-1660B-3 (2.26 g (0.51 mmol)), NMP (75 g), and DMIB (25 g), heat and stir at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyfluorene imide precursor were 69,000 and 33,000, respectively.

(Example 5) In Example 5, under a stream of dry nitrogen gas, ODPA (6.31 g (20.3 mmol)), PMDA (0.49 g (2.26 mmol)), m-TB (4.55 g (21.4 mmol)), X-22-1660B-3 (2.29 g (0.52 mmol)), 1,3,5-TAPOB (0.181 g (0.45 mmol)), NMP (75 g), and MMBAc (25 g ), Heat and stir at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyimide precursor were 202,000 and 54,000, respectively.

(Example 6) In Example 6, under a stream of dry nitrogen, ODPA (6.24 g (20.1 mmol)), PMDA (0.49 g (2.23 mmol)), m-TB (4.56) were added to a 200 mL four-necked flask. g (21.5 mmol)), X-22-1660B-3 (2.26 g (0.51 mmol)), 1,3,5-TAPOB (0.089 g (0.25 mmol)), NMP (75 g), and MMBAc (25 g ), Heat and stir at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyimide precursor were 152,000 and 48,000, respectively.

(Example 7) In Example 7, under a stream of dry nitrogen gas, ODPA (6.25 g (20.1 mmol)), PMDA (0.48 g (2.24 mmol)), m-TB (4.64) were added to a 200 mL four-necked flask. g (21.9 mmol)), X-22-1660B-3 (2.26 g (0.51 mmol)), GBL (75 g), and MMBAc (25 g), heat and stir at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 65,000 and 30,500, respectively.

(Example 8) In Example 8, under a stream of dry nitrogen gas, ODPA (6.25 g (20.1 mmol)), PMDA (0.48 g (2.24 mmol)), m-TB (4.64) were added to a 200 mL four-necked flask. g (21.9 mmol)), X-22-1660B-3 (2.26 g (0.51 mmol)), PGME (75 g), and MMBAc (25 g), heat and stir at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyimide precursor were 61,000 and 28,000, respectively.

(Example 9) In Example 9, under a stream of dry nitrogen gas, ODPA (7.37 g (23.8 mmol)), PMDA (0.58 g (2.64 mmol)), m-TB (4.35 g (20.5 mmol)), 4,4'-DDS (1.31 g (5.28 mmol)), X-22-1660B-3 (2.67 g (0.61 mmol)), NMP (75 g), and MMBAc (25 g) , Stirring at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyfluorene imide precursor were 68,000 and 31,500, respectively.

(Example 10) In Example 10, under a stream of dry nitrogen gas, ODPA (5.32 g (17.2 mmol)), PMDA (0.42 g (1.91 mmol)), TFMB (5.97 g ( 18.6 mmol)), X-22-1660B-3 (1.93 g (0.44 mmol)), NMP (75 g), and MMBAc (25 g), heat and stir at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyfluorene imide precursor were 68,000 and 31,500, respectively.

(Example 11) In Example 11, under a stream of dry nitrogen gas, ODPA (5.40 g (17.4 mmol)), PMDA (0.42 g (1.93 mmol)), TFMB (5.86 g ( 18.3 mmol)), X-22-1660B-3 (1.96 g (0.44 mmol)), 1,3,5-TAPOB (0.154 g (0.39 mmol)), NMP (75 g), and MMBAc (25 g), Heat and stir at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 198,000 and 52,000, respectively.

(Example 12) In Example 12, under a stream of dry nitrogen gas, ODPA (7.35 g (23.7 mmol)), PMDA (0.57 g (2.63 mmol)), m-TB (4.17) were added to a 200 mL four-necked flask. g (19.7 mmol)), 4,4'-DDS (1.31 g (5.26 mmol)), X-22-1660B-3 (2.66 g (0.61 mmol)), 1,3,5-TAPOB (0.21 g (0.53 mmol)), NMP (75 g), and MMBAc (25 g), and stirred with heating at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyfluorene imide precursor were 185,000 and 50,000, respectively.

(Example 13) In Example 13, under a stream of dry nitrogen gas, ODPA (6.16 g (19.8 mmol)), PMDA (0.49 g (2.26 mmol)), X-22-168 were added to a 200 mL four-necked flask. -P5-B (2.19 g (0.52 mmol)), m-TB (4.80 g (22.6 mmol)), NMP (75 g), and MMBAc (25 g), heat and stir at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyfluorene imide precursor were 67,000 and 32,000, respectively.

(Example 14) In Example 14, under a stream of dry nitrogen, ODPA (6.09 g (19.6 mmol)), BSAA (0.90 g (2.18 mmol)), and m-TB (4.53) were added to a 200 mL four-necked flask. g (21.3 mmol)), X-22-1660B-3 (2.12 g (0.49 mmol)), NMP (75 g), and MMBAc (25 g), heat and stir at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyimide precursor were 65,000 and 31,000, respectively.

(Example 15) In Example 15, under a stream of dry nitrogen gas, ODPA (7.18 g (23.2 mmol)), BPAF (1.18 g (2.57 mmol)), m-TB (5.34 g (25.1 mmol)), X-22-1660B-3 (2.58 g (0.59 mmol)), NMP (75 g), and MMBAc (25 g), heat and stir at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 66,000 and 31,000, respectively.

(Example 16) In Example 16, ODPA (7.74 g (25.0 mmol)), PMDA (0.61 g (2.77 mmol)), CHDA (0.63 g ( 5.55 mmol)), m-TB (4.58 g (21.6 mmol)), X-22-1660B-3 (2.81 g (0.64 mmol)), NMP (75 g), and MMBAc (25 g) at 80 ° C Heat and stir. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyimide precursor were 71,000 and 34,000, respectively.

(Example 17) In Example 17, BPDA (5.06 g (17.2 mmol)), PMDA (0.42 g (1.91 mmol)), TFMB (5.98 g ( 18.7 mmol)), X-22-1660B-3 (1.93 g (0.44 mmol)), NMP (75 g), and MMBAc (25 g), heat and stir at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyimide precursor were 85,000 and 46,000, respectively.

(Example 18) In Example 18, a 200 mL four-necked flask was charged with BPDA (5.06 g (17.2 mmol)), PMDA (0.42 g (1.91 mmol)), TFMB (3.98 g ( 12.4 mmol)), 4,4'-DDS (1.55 g (6.23 mmol)), X-22-1660B-3 (1.93 g (0.44 mmol)), NMP (75 g), and MMBAc (25 g), in Heat and stir at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 75,000 and 45,000, respectively.

(Example 19) In Example 19, BPDA (4.50 g (15.3 mmol)), PMDA (0.42 g (1.91 mmol)), BPAF (0.88 g ( 1.91 mmol)), TFMB (3.99 g (12.5 mmol)), 4,4'-DDS (1.55 g (6.25 mmol)), X-22-1660B-3 (1.94 g (0.44 mmol)), NMP (75 g ) And MMBAc (25 g), heat and stir at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyfluorene imide precursor were 73,500, and 40,000, respectively.

(Example 20) In Example 20, a 200 mL four-necked flask was charged with BPDA (3.38 g (11.5 mmol)), PMDA (0.42 g (1.91 mmol)), BPAF (2.64 g ( 5.75 mmol)), TFMB (4.00 g (12.5 mmol)), 4,4'-DDS (1.55 g (6.25 mmol)), X-22-1660B-3 (1.93 g (0.44 mmol)), NMP (75 g ) And MMBAc (25 g), heat and stir at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyfluorene imide precursor were 73,000 and 44,000, respectively.

(Example 21) In Example 21, BPDA (2.25 g (7.64 mmol)), PMDA (0.42 g (1.91 mmol)), BPAF (4.38 g ( 9.55 mmol)), TFMB (4.00 g (12.5 mmol)), 4,4'-DDS (1.55 g (6.23 mmol)), X-22-1660B-3 (1.93 g (0.44 mmol)), NMP (75 g ) And MMBAc (25 g), heat and stir at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyfluorene imide precursor were 70,000 and 42,500, respectively.

(Example 22) In Example 22, 0.12 g (corresponding to 0.1 part by mass of 100 parts by mass of polyimide precursor) was added to the varnish (100 g) obtained in Example 20 of 2 -Ethyl-4-methylimidazole to make the varnish of Example 22.

(Example 23) In Example 23, 0.36 g (corresponding to 0.3 parts by mass of the mass of polyimide precursor) was added to 2 (100 g) of the varnish (100 g) obtained in Example 20. 2 -Ethyl-4-methylimidazole to make the varnish of Example 23.

(Example 24) In Example 24, 0.12 g (corresponding to 0.1 part by mass of 100 parts by mass of polyimide precursor) was added to the varnish (100 g) obtained in Example 20 of 3 , 5-Dihydroxybenzoic acid to make the varnish of Example 24.

(Example 25) In Example 25, BPDA (3.38 g (11.5 mmol)), PMDA (0.42 g (1.92 mmol)), BPAF (2.64 g ( 5.75 mmol)), TFMB (3.90 g (12.2 mmol)), 4,4'-DDS (1.55 g (6.25 mmol)), 1,3,5-TAPOB (0.077 g (0.19 mmol)), X-22- 1660B-3 (1.94 g (0.44 mmol)), NMP (75 g), and MMBAc (25 g) were heated and stirred at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyfluorene imide precursor were 95,000 and 49,000, respectively.

(Example 26) In Example 26, BPDA (3.38 g (11.5 mmol)), PMDA (0.42 g (1.92 mmol)), BPAF (2.64 g ( 5.75 mmol)), TFMB (3.87 g (12.1 mmol)), 4,4'-DDS (1.55 g (6.25 mmol)), TAB-S (0.053 g (0.19 mmol)), X-22-1660B-3 ( 1.94 g (0.44 mmol)), NMP (75 g), and MMBAc (25 g), and stirred with heating at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyfluorene imide precursor were 96,000 and 49,500, respectively.

(Example 27) In Example 27, BPDA (3.38 g (11.5 mmol)), PMDA (0.42 g (1.92 mmol)), BPAF (2.64 g ( 5.75 mmol)), TFMB (3.00 g (9.36 mmol)), 4,4'-DDS (2.33 g (9.36 mmol)), X-22-1660B-3 (1.94 g (0.44 mmol)), NMP (75 g ) And MMBAc (25 g), heat and stir at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyfluorene imide precursor were 68,000 and 40,000, respectively.

(Example 28) In Example 28, BPDA (3.38 g (11.5 mmol)), PMDA (0.42 g (1.92 mmol)), BPAF (2.64 g ( 5.75 mmol)), TFMB (2.00 g (6.27 mmol)), 4,4'-DDS (3.09 g (12.46 mmol)), X-22-1660B-3 (1.94 g (0.44 mmol)), NMP (75 g ) And MMBAc (25 g), heat and stir at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 64,000 and 37,000, respectively.

(Example 29) In Example 29, under a stream of dry nitrogen gas, ODPA (7.37 g (23.8 mmol)), PMDA (0.58 g (2.64 mmol)), m-TB (4.35) were added to a 200 mL four-necked flask. g (20.5 mmol)), 4,4'-DDS (1.31 g (5.28 mmol)), X-22-1660B-3 (2.67 g (0.61 mmol)), NMP (90 g), and MMBAc (10 g) , Stirring at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyimide precursor were 70,000 and 32,500, respectively.

(Example 30) In Example 30, under a stream of dry nitrogen, ODPA (7.37 g (23.8 mmol)), PMDA (0.58 g (2.64 mmol)), m-TB (4.35 g (20.5 mmol)), 4,4'-DDS (1.31 g (5.28 mmol)), X-22-1660B-3 (2.67 g (0.61 mmol)), NMP (63 g), and MMBAc (37 g) , Stirring at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained polyimide precursor were 67,500 and 31,500, respectively.

(Example 31) In Example 31, under a stream of dry nitrogen, ODPA (6.25 g (20.1 mmol)), PMDA (0.48 g (2.24 mmol)), m-TB (4.64) were added to a 200 mL four-necked flask. g (21.9 mmol)), X-22-1660B-3 (2.26 g (0.51 mmol)), NMP (55 g), and MMBAc (45 g), heat and stir at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyfluorene imide precursor were 63,000 and 30,000, respectively.

(Example 32) In Example 32, under a stream of dry nitrogen, ODPA (6.25 g (20.1 mmol)), PMDA (0.48 g (2.24 mmol)), m-TB (4.64) were added to a 200 mL four-necked flask. g (21.9 mmol)), X-22-1660B-3 (2.26 g (0.51 mmol)), NMP (96 g), and MMBAc (4 g), heat and stir at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyfluorene imide precursor were 70,000 and 33,000, respectively.

(Example 33) In Example 33, under a stream of dry nitrogen gas, ODPA (6.25 g (20.1 mmol)), PMDA (0.48 g (2.24 mmol)), m-TB (4.64) were added to a 200 mL four-necked flask. g (21.9 mmol)), X-22-1660B-3 (2.26 g (0.51 mmol)), NMP (30 g), and MMBAc (70 g), heat and stir at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyimide precursor were 59,000 and 28,000, respectively.

(Example 34) In Example 34, under a stream of dry nitrogen gas, ODPA (4.41 g (14.2 mmol)), PMDA (0.62 g (2.84 mmol)), PMDA-HS (2.55 g (11.4 mmol)), m-TB (5.90 g (27.8 mmol)), X-22-1660B-3 (2.88 g (0.65 mmol)), NMP (75 g), and MMBAc (25 g), at 80 Heat and stir at ℃. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyimide precursor were 67,000 and 30,000, respectively.

(Example 35) In Example 35, PMDA-HS (6.20 g (27.7 mmol)), PMDA (0.67 g (3.07 mmol)), and m-TB were added to a 200 mL four-necked flask under a stream of dry nitrogen. (6.38 g (30.0 mmol)), X-22-1660B-3 (3.11 g (0.71 mmol)), NMP (75 g), and MMBAc (25 g), heat and stir at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyfluorene imide precursor were 55,000 and 25,000, respectively.

(Comparative Example 1) In Comparative Example 1, under a stream of dry nitrogen, ODPA (6.25 g (20.1 mmol)), PMDA (0.48 g (2.24 mmol)), m-TB (4.64) were added to a 200 mL four-necked flask. g (21.9 mmol)), X-22-1660B-3 (2.26 g (0.51 mmol)), NMP (75 g), and BDGAc (25 g), heat and stir at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyfluorene imide precursor were 70,000 and 32,000, respectively.

(Comparative Example 2) In Comparative Example 2, under a stream of dry nitrogen, ODPA (6.25 g (20.1 mmol)), PMDA (0.48 g (2.24 mmol)), m-TB (4.64) were added to a 200 mL four-necked flask. g (21.9 mmol)), X-22-1660B-3 (2.26 g (0.51 mmol)), NMP (75 g), and n-octane (25 g), heat and stir at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyfluorene imide precursor were 68,000 and 31,000, respectively.

(Comparative Example 3) In Comparative Example 3, under a stream of dry nitrogen, ODPA (6.25 g (20.1 mmol)), PMDA (0.48 g (2.24 mmol)), m-TB (4.64) were added to a 200 mL four-necked flask. g (21.9 mmol)), X-22-1660B-3 (2.26 g (0.51 mmol)), 1,3-butylene diethylene glycol (75 g), and MMBAc (25 g), heated at 80 ° C Stir. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyfluorene imide precursor were 53,000 and 24,000, respectively.

(Comparative Example 4) In Comparative Example 4, under a stream of dry nitrogen, ODPA (6.25 g (20.1 mmol)), PMDA (0.48 g (2.24 mmol)), m-TB (4.64) were added to a 200 mL four-necked flask. g (21.9 mmol)), X-22-1660B-3 (2.26 g (0.51 mmol)), DMIB (75 g), and MMBAc (25 g), heat and stir at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyimide precursor were 55,000 and 25,500, respectively.

(Comparative Example 5) In Comparative Example 5, ODPA (6.25 g (20.1 mmol)), PMDA (0.48 g (2.24 mmol)), m-TB (4.64) were added to a 200 mL four-necked flask under a stream of dry nitrogen. g (21.9 mmol)), X-22-1660B-3 (2.26 g (0.51 mmol)), NMP (100 g), and stir with heating at 80 ° C. After 8 hours, it was cooled to make a varnish. The obtained varnish was cloudy, and therefore it was not possible to measure the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyfluorene imide precursor.

(Comparative Example 6) In Comparative Example 6, under a stream of dry nitrogen gas, ODPA (6.25 g (20.1 mmol)), PMDA (0.48 g (2.24 mmol)), m-TB (4.64) were added to a 200 mL four-necked flask. g (21.9 mmol)), X-22-1660B-3 (2.26 g (0.51 mmol)), MMBAc (100 g), and stirred with heating at 80 ° C. After 8 hours, it was cooled to make a varnish. The obtained varnish had insoluble matter and became cloudy, so it was impossible to measure the weight average molecular weight (Mw) and number average molecular weight (Mn) of the polyfluorene imide precursor.

(Comparative Example 7) In Comparative Example 7, under a stream of dry nitrogen, ODPA (7.42 g (23.9 mmol)), PMDA (0.58 g (2.66 mmol)), and m-TB (5.64) were added to a 200 mL four-necked flask. g (26.6 mmol)), NMP (75 g), MMBAc (25 g), and stir with heating at 80 ° C. After 8 hours, it was cooled to make a varnish. The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained polyfluorene imide precursor were 73,000 and 36,000, respectively.

The composition of the varnishes synthesized in Examples 1 to 35 and Comparative Examples 1 to 7 and the evaluation results using these varnishes are shown in Tables 1A-1, 1A-2, 1B-1, and Tables. 1B-2, Table 1C, and Table 1D. The "SP" in the table refers to the SP value. The "VP" in the table refers to the vapor pressure at 20 ° C.

[Table 1A-1]

[Table 1A-2]

[Table 1B-1]

[Table 1B-2]

[Table 1C]

[Table 1D]

(Example 36) In Example 36, the varnish obtained in Example 1 was used, and the polyimide resin film was produced by the method shown in the said 3rd item. Thereafter, the method shown in the item 17 is used to manufacture a touch panel.

(Example 37) In Example 37, SiON (film formation temperature: 350 ° C, film thickness 200 nm) was formed on the polyimide resin film by plasma CVD. Except this film formation, it carried out similarly to Example 36, and produced the touch panel.

(Example 38) In Example 38, SiO ₂ (film formation temperature: 350 ° C, film thickness 100 nm) and SiN (film formation temperature: 350 ° C, film) were sequentially formed on a polyimide resin film by plasma CVD. 100 nm thick). Except this film formation, it carried out similarly to Example 36, and produced the touch panel.

(Example 39) In Example 39, SiN (film formation temperature: 350 ° C, film thickness 100 nm) and SiO ₂ (film formation temperature: 350 ° C, film) were sequentially formed on a polyimide resin film by plasma CVD. 100 nm thick). Except this film formation, it carried out similarly to Example 36, and produced the touch panel.

(Example 40) In Example 40, SiO ₂ (film forming temperature: 350 ° C., film thickness 200 nm) was formed on a polyimide resin film by plasma CVD. Except this film formation, it carried out similarly to Example 36, and produced the touch panel.

(Example 41) In Example 41, the varnish obtained in Example 5 was used, and the polyimide resin film was produced by the method shown in the said 3rd item. Thereafter, the method shown in the item 17 is used to manufacture a touch panel.

(Example 42) In Example 42, SiON (film formation temperature: 350 ° C., film thickness 200 nm) was formed on a polyimide resin film by plasma CVD. Except for this film formation, a touch panel was produced in the same manner as in Example 41.

(Example 43) In Example 43, SiO ₂ (film formation temperature: 350 ° C, film thickness 100 nm) and SiN (film formation temperature: 350 ° C, film) were sequentially formed on a polyimide resin film by plasma CVD. 100 nm thick). Except for this film formation, a touch panel was produced in the same manner as in Example 41.

(Example 44) In Example 44, SiN (film formation temperature: 350 ° C, film thickness 100 nm) and SiO ₂ (film formation temperature: 350 ° C, film) were sequentially formed on a polyimide resin film by plasma CVD. 100 nm thick). Except for this film formation, a touch panel was produced in the same manner as in Example 41.

(Example 45) In Example 45, SiO ₂ (film formation temperature: 350 ° C., film thickness 200 nm) was formed on the polyimide resin film by plasma CVD. Except for this film formation, a touch panel was produced in the same manner as in Example 41.

(Example 46) In Example 46, the varnish obtained in Example 14 was used, and the polyimide resin film was produced by the method shown in the said 3rd item. Thereafter, the method shown in the item 17 is used to manufacture a touch panel.

(Example 47) In Example 47, the varnish obtained in Example 4 was used, and the polyimide resin film was produced by the method shown in said 3rd item. Thereafter, the method shown in the item 17 is used to manufacture a touch panel.

(Example 48) In Example 48, the varnish obtained in Example 22 was used, and the polyimide resin film was produced by the method shown in the said 3rd item. Thereafter, the method shown in the item 17 is used to manufacture a touch panel.

(Example 49) In Example 49, the varnish obtained in Example 26 was used, and the polyimide resin film was produced by the method shown in said 3rd item. Thereafter, the method shown in the item 17 is used to manufacture a touch panel.

The structure of the laminated body obtained in Example 36- Example 49 and the evaluation result of a touch panel are shown in Table 2.

[Table 2] [Industrial availability]

As described above, the polyimide precursor resin composition, the polyimide resin composition, the polyimide resin film, the method for producing a laminate, the method for producing a color filter, and the production of a liquid crystal element of the present invention Method and method for manufacturing organic EL element are suitable for a polyimide precursor resin composition having a good slit coating property and obtaining a white turbidity of the polyimide film and suppressing residual stress, and a polyimide using the same A resin composition, a polyimide resin film, a method for manufacturing a laminate, a method for manufacturing a color filter, a method for manufacturing a liquid crystal element, and a method for manufacturing an organic EL element.

1.1-1, 1-2‧‧‧Polyimide resin film

2‧‧‧Gas barrier

3‧‧‧ the first wiring layer

4‧‧‧The first insulation layer

5‧‧‧Second wiring layer

6‧‧‧Second insulation layer

7‧‧‧ touch panel

8‧‧‧ color filter

9‧‧‧ Black Matrix

10R‧‧‧Red pixels

10G‧‧‧Green Pixel

10B‧‧‧Blue pixels

11‧‧‧ Outer coating

12‧‧‧LCD element

13‧‧‧pixel electrode

14‧‧‧first alignment film

15‧‧‧Second alignment film

16‧‧‧ Opposite electrode

17‧‧‧LCD layer

18‧‧‧ polarizing plate

19‧‧‧Organic EL element

20‧‧‧TFT layer

21‧‧‧ flattening layer

22‧‧‧first electrode

23‧‧‧ Insulation

24R‧‧‧Red organic EL light emitting layer

24G‧‧‧ green organic EL light emitting layer

24B‧‧‧Blue organic EL light emitting layer

25‧‧‧Second electrode

26‧‧‧ glass substrate

27‧‧‧Polyimide resin film

28‧‧‧ film thickness measurement site

29‧‧‧ arrow (indicating coating direction)

30‧‧‧Laminated body

31‧‧‧Metal Cylinder

I-I'‧‧‧ hatch

FIG. 1A is a plan view showing a configuration example of a touch panel including a polyimide resin film according to an embodiment of the present invention. FIG. 1B is a cross-sectional view taken along a line II-II ′ of the touch panel shown in FIG. 1A. 2 is a cross-sectional view showing a configuration example of a color filter including a laminated body according to an embodiment of the present invention. 3 is a cross-sectional view showing a configuration example of a liquid crystal element including a laminated body according to an embodiment of the present invention. 4 is a cross-sectional view showing a configuration example of an organic EL element including a laminated body according to an embodiment of the present invention. FIG. 5 is a plan view for explaining production of a polyimide resin film and evaluation of applicability in Examples. FIG. 6 is a schematic perspective view showing a state before bending when the laminated body is evaluated for bending resistance. FIG. 7 is a schematic perspective view showing a folded state when the laminated body is evaluated for bending resistance.

Claims (17)

A polyimide precursor resin composition comprising a polyimide precursor (A) including a structure represented by the general formula (1) and a structural unit represented by the general formula (2), and a solvent (B ) A polyimide precursor resin composition, and the polyimide precursor resin composition is characterized in that when the entire amount of the polyimide precursor (A) is 100% by mass, the polyimide precursor (A) contains a structure represented by the general formula (1) in an amount of 5 to 30% by mass, and the solvent (B) includes one or more solvents (B1) each having a solubility parameter value of 7.7 or more and 9.0 or less, and Solvent (B2) whose solubility parameter value is greater than 9.0 and less than 12.5; In the general formula (1), R ¹ and R ² each independently represent a monovalent organic group having 1 to 20 carbon atoms; m represents an integer of 3 to 200, In the general formula (2), R ³ represents a divalent organic group, and R ⁴ represents a tetravalent organic group; Y ¹ and Y ² each independently represent a hydrogen atom, a monovalent organic group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. A monovalent alkylsilyl group of 10. The polyimide precursor resin composition according to item 1 of the scope of the patent application, wherein when the total amount of the solvent (B) is set to 100% by mass, the solvent (B) contains 5 mass % To 40% by mass of the solvent (B1), and 60% to 95% by mass of the solvent (B2). According to the polyimide precursor resin composition according to item 1 or item 2 of the scope of the patent application, when the total amount of the solvent (B) is set to 100% by mass, the solvent (B ) Contains 70% to 100% by mass of a solvent having a vapor pressure at 20 ° C. of 10 Pa or more and 100 Pa or less. The polyimide precursor resin composition according to item 1 or item 2 of the patent application scope, wherein in the solvent (B), the vapor pressure difference between the solvent having the highest vapor pressure and the lowest solvent at 20 ° C It is 100 Pa or less. The polyimide precursor resin composition according to item 1 or 2 of the scope of the patent application, wherein the polyimide is 100 mol% of the polyimide precursor (A). The precursor (A) contains an acid anhydride residue having a fluorene skeleton of 5 mol% or more and 55 mol% or less. The polyimide precursor resin composition according to item 5 of the scope of patent application, wherein the polyimide precursor (A) is 100 mol% of the polyimide precursor (A). ) Contains a diamine residue having a diphenylfluorenyl group in a total amount of 15 mol% or more and less than 60 mol%. The polyimide precursor resin composition according to item 1 or 2 of the scope of the patent application, wherein the polyimide is 100 mol% of the polyimide precursor (A). The precursor (A) contains a total of 30 mol% or more of an acid anhydride residue having a diphenyl ether group and a diamine residue having a diphenyl ether group. The polyimide precursor resin composition according to item 1 or 2 of the scope of the patent application, wherein the polyimide precursor (A) includes a triamine skeleton. The polyimide precursor resin composition according to item 1 or 2 of the scope of application for a patent, wherein the polyimide precursor (A) includes a tetraamine skeleton. The polyimide precursor resin composition according to item 1 or 2 of the scope of the patent application, further comprising a fluorene imidization accelerator, and the content of the fluorene imidization accelerator relative to the polymer 100 parts by mass of the sulfonimide precursor (A) is 0.1 to 3 parts by mass. A polyimide resin composition is obtained by imidizing a polyimide precursor resin composition. The polyimide precursor resin composition includes a structure represented by the general formula (1). And a polyimide precursor (A) and a solvent (B) of the structural unit represented by the general formula (2), the polyimide resin composition is characterized in that the polyimide precursor is When the total amount of the substance (A) is 100% by mass, the polyfluorene imide precursor (A) includes a structure represented by the general formula (1) in an amount of 5 to 30% by mass, and the solvent ( B) Containing one or more solvents (B1) having a solubility parameter value of 7.7 or more and 9.0 or less and a solvent (B2) having a solubility parameter value of more than 9.0 and 12.5 or less; In the general formula (1), R ¹ and R ² each independently represent a monovalent organic group having 1 to 20 carbon atoms; m represents an integer of 3 to 200, In the general formula (2), R ³ represents a divalent organic group, and R ⁴ represents a tetravalent organic group; Y ¹ and Y ² each independently represent a hydrogen atom, a monovalent organic group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. A monovalent alkylsilyl group of 10. A polyimide resin film is a polyimide resin film containing a structure represented by the general formula (1) for manufacturing a flexible display substrate, and the polyimide resin film is characterized in that: When the entire amount is 100% by mass, the polyimide resin film includes a structure represented by the general formula (1) in an amount of 5% to 30% by mass, and the tensile elastic modulus is 1.5 GPa or more and 3.5 Below GPa, and the haze value is below 1%; In the general formula (1), R ¹ and R ² each independently represent a monovalent organic group having 1 to 20 carbon atoms; and m represents an integer of 3 to 200. A polyimide resin film is a polyimide resin film containing a structure represented by the general formula (1) for manufacturing a flexible display substrate, and the polyimide resin film is characterized in that: When the entire amount is 100% by mass, the polyimide resin film includes a structure represented by the general formula (1) in an amount of 5% to 30% by mass, a haze value of 1% or less, and glass The transfer point is above 380 ℃; In the general formula (1), R ¹ and R ² each independently represent a monovalent organic group having 1 to 20 carbon atoms; and m represents an integer of 3 to 200. A method for manufacturing a laminate, comprising: a coating step of coating a polyimide precursor resin composition on a support substrate, the polyimide precursor resin composition comprising a general formula (1 ) And the polyfluorene imide precursor (A) and the solvent (B) of the structure represented by the general formula (2) and the structural unit represented by the general formula (2); removed from the coated polyimide precursor resin composition A step of removing the solvent; a step of forming a polyimide resin film from the polyimide precursor resin composition from which the solvent has been removed, to obtain a film of the polyimide resin composition; And an inorganic film forming step of forming an inorganic film on the obtained film of the polyimide resin composition, and setting the entire amount of the polyimide precursor (A) to 100% by mass In the case, the polyfluorene imide precursor (A) includes a structure represented by the general formula (1) in an amount of 5-30% by mass, and the solvent (B) includes one or more solubility parameter values. Solvent (B1) above 7.7 and below 9.0, and dissolution Parameter values greater than 9.0 and less than 12.5 solvent (B2); In the general formula (1), R ¹ and R ² each independently represent a monovalent organic group having 1 to 20 carbon atoms; m represents an integer of 3 to 200, In the general formula (2), R ³ represents a divalent organic group, and R ⁴ represents a tetravalent organic group; Y ¹ and Y ² each independently represent a hydrogen atom, a monovalent organic group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. A monovalent alkylsilyl group of 10. A method for manufacturing a color filter, comprising: a step of forming a black matrix and colored pixels on a multilayer body produced on a support substrate; and a peeling step of peeling the multilayer body from the support substrate, The manufacturing method of the laminated body includes: a coating step of coating a polyimide precursor resin composition on the support substrate, the polyimide precursor resin composition including a general formula (1) Polyimide precursor (A) and solvent (B) of the structure and the structural unit represented by the general formula (2); the solvent is removed from the coated polyimide precursor resin composition A removing step; a polyimide resin film forming step of imidizing the polyimide precursor resin composition from which the solvent is removed to obtain a film of a polyimide resin composition; and An inorganic film forming step of forming an inorganic film on the obtained film of the polyimide resin composition, and setting the amount of the entire polyimide precursor (A) to 100% by mass Case, the poly The imine precursor (A) includes a structure represented by the general formula (1) in an amount of 5-30% by mass, and the solvent (B) includes one or more solvents each having a solubility parameter value of 7.7 or more and 9.0 or less ( B1), and the solvent (B2) whose solubility parameter value is greater than 9.0 and less than 12.5; In the general formula (1), R ¹ and R ² each independently represent a monovalent organic group having 1 to 20 carbon atoms; m represents an integer of 3 to 200, In the general formula (2), R ³ represents a divalent organic group, and R ⁴ represents a tetravalent organic group; Y ¹ and Y ² each independently represent a hydrogen atom, a monovalent organic group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. 10 is a monovalent alkylsilyl group. A method for manufacturing a liquid crystal element, comprising: forming a transparent electrode, an alignment film, and a liquid crystal layer on a laminated body produced on a supporting substrate; and a peeling step of peeling the laminated body from the supporting substrate, The manufacturing method of the laminated body includes: a coating step of coating a polyimide precursor resin composition on the support substrate, the polyimide precursor resin composition including a general formula (1) Polyimide precursor (A) and solvent (B) of the structure and the structural unit represented by the general formula (2); the solvent is removed from the coated polyimide precursor resin composition A removing step; a polyimide resin film forming step of imidizing the polyimide precursor resin composition from which the solvent is removed to obtain a film of a polyimide resin composition; and An inorganic film forming step of forming an inorganic film on the obtained film of the polyimide resin composition, and setting the amount of the entire polyimide precursor (A) to 100% by mass Case, all The polyfluorene imide precursor (A) contains 5 to 30% by mass of the structure represented by the general formula (1), and the solvent (B) contains one or more types of solubility parameter values of 7.7 or more and 9.0 or less, respectively. Solvent (B1) and solvent (B2) whose solubility parameter value is greater than 9.0 and less than 12.5; In the general formula (1), R ¹ and R ² each independently represent a monovalent organic group having 1 to 20 carbon atoms; m represents an integer of 3 to 200, In the general formula (2), R ³ represents a divalent organic group, and R ⁴ represents a tetravalent organic group; Y ¹ and Y ² each independently represent a hydrogen atom, a monovalent organic group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. A monovalent alkylsilyl group of 10. A method for manufacturing an organic electroluminescence element, comprising: a forming step of forming an organic electroluminescence light-emitting circuit on a laminated body produced on a supporting substrate; and a peeling step of peeling the laminated body from the supporting substrate. The manufacturing method of the laminated body includes: a coating step of coating a polyimide precursor resin composition on the support substrate, the polyimide precursor resin composition including a general formula (1 ) And the polyfluorene imide precursor (A) and the solvent (B) of the structure represented by the general formula (2) and the structural unit represented by the general formula (2); removed from the coated polyimide precursor resin composition A step of removing the solvent; a step of forming a polyimide resin film from the polyimide precursor resin composition from which the solvent has been removed, to obtain a film of the polyimide resin composition; And an inorganic film forming step of forming an inorganic film on the obtained film of the polyimide resin composition, and setting the entire amount of the polyimide precursor (A) to 100% by mass in the case of The polyimide precursor (A) includes a structure represented by the general formula (1) in an amount of 5% to 30% by mass, and the solvent (B) includes one or more kinds of solubility parameter values of 7.7 or more and 9.0, respectively. The following solvents (B1) and solvents (B2) with a solubility parameter value greater than 9.0 and 12.5 or less; In the general formula (1), R ¹ and R ² each independently represent a monovalent organic group having 1 to 20 carbon atoms; m represents an integer of 3 to 200, In the general formula (2), R ³ represents a divalent organic group, and R ⁴ represents a tetravalent organic group; Y ¹ and Y ² each independently represent a hydrogen atom, a monovalent organic group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. A monovalent alkylsilyl group of 10.