TW201718714A - Polyimide precursor, resin composition, and method for producing resin film - Google Patents

Abstract

Provided is a polyimide precursor comprising a structural unit L represented by formula (1) (in the formula, X1 represents a tetravalent group having 4-32 carbon atoms, each of R1, R2, and R3 independently represents a monovalent organic group having 1-20 carbon atoms, n represents 0 or 1, and each of a, b, and c is an integer of 0-4) and a structural unit M represented by formula (2) (in the formula, X2 represents a tetravalent group having 4-32 carbon atoms) such that 1/99 ≤ (number of moles of structural unit L/number of moles of structural unit M) ≤ 99/1 is satisfied.

Description

Polyimine precursor, resin composition and method for producing resin film

The present invention relates to, for example, a method for producing a polyimide precursor, a resin composition, and a resin film used in the production of a substrate for a flexible device.

Generally, a film of a polyimide resin is used as a resin film in applications requiring high heat resistance. A typical polyimine resin is obtained by solution polymerization of an aromatic carboxylic dianhydride and an aromatic diamine to produce a polyimide precursor, which is then thermally imidized or used at a high temperature. A high heat resistant resin produced by chemical hydrazine imidization. The polyimide resin is an insoluble and non-fusible super heat resistant resin, and has excellent properties such as heat oxidation resistance, heat resistance, radiation resistance, low temperature resistance, and chemical resistance. Therefore, polyimine resins are used in a wide range of fields including electronic materials. Examples of the application of the polyimide resin in the field of electronic materials include an insulating coating agent, an insulating film, a protective film for a semiconductor, and a TFT-LCD (Thin film transistor-liquid crystal display). Electrode protective film, etc. Recently, a glass substrate which has been previously used in the field of display materials has been studied and used as a colorless and transparent flexible substrate using its lightness and flexibility. In the case of producing a polyimide film of a flexible substrate, a composition containing a polyimide precursor is applied onto a suitable support to form a coating film, and then heat-treated to imidize the film. A polyimide film was obtained. As the support, for example, glass, ruthenium, tantalum nitride, ruthenium oxide, metal, or the like is used. In the case of a laminate having a polyimide film produced on such a support, in order to dry and ruthenium the polyimide precursor, heat treatment at a high temperature of 250 ° C or higher is required. By this heat treatment, residual stress is generated in the laminate, and serious problems such as warpage and peeling occur. The reason for this is that the linear thermal expansion coefficient of the polyimine is larger than that of the material constituting the above support. As the polyimine material having a small coefficient of thermal expansion, the most well-known polyimine formed from 3,3',4,4'-biphenyltetracarboxylic dianhydride and p-phenylenediamine. Although the film thickness and the production conditions are reported, it is reported that the polyimide film exhibits a very low linear thermal expansion coefficient (Non-Patent Document 1). Further, it has been reported that a polyimine having an ester structure in a molecular chain has a moderate linearity and a straightness, and thus exhibits a low coefficient of thermal expansion (Patent Document 1). However, in the case of the usual polyimine resin containing the polyimine described in the above document, the color is brown or yellow due to the higher aromatic ring density, so the light transmittance in the visible light region is low. It is therefore difficult to use in areas where transparency is required. For example, the yellowness (YI value) of the polyimide film of the above non-patent document 1 obtained from 3,3',4,4'-biphenyltetracarboxylic dianhydride and p-phenylenediamine is as high as 10 μm. 40 or more, it is insufficient in transparency. Regarding the yellowness of the film, for example, it is known that a polyimide having a monomer having a fluorine atom exhibits an extremely low yellowness (Patent Document 2). [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent No. 4627297 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-538103 [Patent Document 3] Japanese Patent No. 3079867 [Non-Patent Document] [Non-Patent Document 1] Latest Polyimine Japan Polyimine Research Association NTS

[Problems to be Solved by the Invention] However, in order to use a polyimide resin as a colorless transparent flexible substrate, mechanical properties such as excellent elongation and breaking strength are required in addition to transparency. In particular, recently, a device type of TFT (thin-film transistor) has become LTPS (Low Temperature Poly-silicon) (low-temperature polysilicon), and it is desired to exhibit the above even if it exceeds the previous thermal history. Physical film. However, the physical properties of the known transparent polyimides are not sufficient for use as a heat-resistant colorless transparent substrate for displays. Furthermore, the inventors of the present invention have confirmed that the polyimine resin described in Patent Document 1 exhibits a low coefficient of thermal expansion, but the yellowness (YI value) of the polyimide film after peeling is large. In addition, the residual stress is high, the elongation is low, and the fracture strength is low. Regarding the yellowness, it is understood that the polyimide film described in Patent Document 2 exhibits a low yellowness in a temperature region of about 300 ° C, but the yellowness (YI value) is significantly deteriorated in a high temperature region of 400 ° C or higher. . Further, as a polyimine having a reduced linear expansion coefficient, a polyimine containing 4,4'-diaminodiphenyl ether and 4,4'-diaminodiphenyl ester is disclosed (Patent Document 3) . However, the inventors of the present invention confirmed that the polyimide resin described in Patent Document 3 is very brittle in use as a flexible substrate, and there is room for improvement in yellowness at a high temperature. The present invention has been accomplished in view of the above-described problems. Accordingly, an object of the present invention is to provide a polyimide film having a low residual stress, less warpage, a small yellowness (YI value), and a high elongation, and a method for producing the same. [Technical means for solving the problem] The present invention is as follows. [1] A polyimine precursor, characterized in that it is a (a1) polyimine precursor, which is 1/99 ≦ (the number of moles of structural unit L / the number of moles of structural unit M) ≦ 99/1 contains: a structural unit represented by the following general formula (1): [Chemical Formula 1] Wherein X ₁ represents a tetravalent group having a carbon number of 4 to 32; and R ₁ , R ₂ and R ₃ each independently represent an organic group having a carbon number of 1 to 20; n represents 0 or 1; b and c are integers of 0 to 4}; and structural unit M represented by the following general formula (2): [Chemical 2] In the formula, X ₂ represents a tetravalent group having a carbon number of 4 to 32; and Y is at least one selected from the group consisting of the following general formulae (3), (4), and (5)}, [Chemical 3 ] [Chemical 4] [Chemical 5] In the formula, R ₄ to R ₁₁ each independently represent an organic group having a carbon number of 1 to 20; and d to k are an integer of 0 to 4}. [2] The polyimine precursor according to [1], wherein n in the above formula (1) is 0. [3] The polyimine precursor of [1] or [2], wherein Y of the above formula (2) is the formula (3). [4] The polyimine precursor of [1] or [2], wherein Y of the above formula (2) is the formula (4). [5] The polyimine precursor of [1] or [2], wherein Y of the above formula (2) is the formula (5). [6] A polyimine precursor, characterized in that it is a (a2) polyimine precursor comprising a structural unit represented by the following formula (10): [Chem. 6] Further, the weight average molecular weight is 30,000 or more and 300,000 or less, wherein X ₃ represents a source derived from 4,4'-oxydiphthalic dianhydride (ODPA), biphenyltetracarboxylic dianhydride (BPDA). And a tetravalent group of at least one of the group consisting of 4,4'-biphenyl bis(trimellitic acid monoester anhydride) (TAHQ); R ₁ , R ₂ and R ₃ each independently represent a carbon number of 1 to 20 an organic group of one valence; n represents 0 or 1; and a, b and c are integers of 0 to 4}. [7] The polyimine precursor according to [6], wherein the content of the molecule having a weight average molecular weight of less than 1,000 in the (a2) polyamidene precursor is less than 5% by mass. [8] The polyimine precursor of [6] or [7], wherein n in the formula (10) is 0. [9] The polyimine precursor according to any one of [1] to [5] wherein the above X _{1 ,} X ₂ are derived from pyromellitic dianhydride (PMDA), 4, 4'- At least one of a group consisting of oxydiphthalic dianhydride (ODPA), biphenyltetracarboxylic dianhydride (BPDA), and 4,4'-biphenyl bis(trimellitic acid monoester anhydride) (TAHQ) A tetravalent organic group. [10] A resin composition comprising the polyimine precursor of any one of [1] to [9] and (b) an organic solvent. [11] The resin composition according to [10], which further contains at least one selected from the group consisting of (c) a surfactant and (d) an alkoxydecane compound. [12] A polyimine which is characterized by containing a structural unit represented by the following formula (11): [Chem. 7] Wherein X ₁ and X ₂ represent a tetravalent group having a carbon number of 4 to 32; and R ₁ , R ₂ and R ₃ each independently represent an organic group having a carbon number of 1 to 20; n represents 0 or 1; And a, b and c are integers of 0 to 4; Y is at least one selected from the group consisting of the following general formulae (3), (4) and (5); and l and m each independently represent 1 or more. Integer, satisfying 0.01≦l/(l+m)≦0.99}, [Chem. 8] [Chemistry 9] [化10] In the formula, R ₄ to R ₁₁ each independently represent an organic group having a carbon number of 1 to 20; and d to k are an integer of 0 to 4}. [13] A polyimine which is characterized by containing a structural unit represented by the following formula (12): [Chem. 11] Wherein X ₃ represents a source derived from 4,4'-oxydiphthalic dianhydride (ODPA), biphenyltetracarboxylic dianhydride (BPDA), and 4,4'-biphenyl bis(phenylene) a tetravalent group of at least one of the group consisting of tricarboxylic acid monoester anhydride) (TAHQ); R ₁ , R ₂ , and R ₃ each independently represent an organic group having one carbon number of 1 to 20; n represents 0 or 1; and a, b, and c are integers of 0 to 4}, and the elongation is 15% or more. [14] A method for producing a resin film, comprising the steps of: forming a coating film by coating a resin composition such as [10] or [11] on a surface of a support; a step of heating the above-mentioned support and the coating film to imidize the polyamidene precursor contained in the coating film to form a polyimide film; and the above-mentioned polyimide film from the above The step of support stripping. [15] The method for producing a resin film according to [14], wherein the step of irradiating the laser from the support side is performed before the step of peeling the polyimine resin film from the support. [16] A method for producing a laminate, comprising the steps of: forming a coating film by coating a resin composition such as [10] or [11] on a surface of a support; The step of heating the above-mentioned support and the above-mentioned coating film to imidize the polyimine precursor precursor contained in the coating film to form a polyimide film. [17] A method of manufacturing a display substrate, comprising the steps of: forming a coating film by coating a resin composition such as [10] or [11] on a surface of a support; a step of heating the above-mentioned support and the coating film to imidize the polyamidene precursor contained in the coating film to form a polyimide film; forming a component on the polyimide film Or a step of a circuit; and a step of peeling the polyimine resin film on which the element or the circuit is formed from the support. [18] A polyimide film for display, which comprises a polyimine represented by the following formula (12): [Chem. 12] Wherein X ₃ is selected from the group consisting of 4,4'-oxydiphthalic dianhydride (ODPA), biphenyltetracarboxylic dianhydride (BPDA), and 4,4'-biphenyl bis(trimellitic acid). At least one of the group consisting of monoester anhydrides (TAHQ), R ₁ , R ₂ , and R ₃ each independently represent an organic group having one carbon number of 1 to 20; n represents 0 or 1; and a, b and c is an integer from 0 to 4. [19] A laminate comprising a polyimide film layer and a low temperature polysilicon TFT layer, wherein the polyimide film layer comprises a polyimine represented by the following formula (13): ] Wherein X ₁ represents a tetravalent group having a carbon number of 4 to 32; and R ₁ , R ₂ and R ₃ each independently represent an organic group having a carbon number of 1 to 20; n represents 0 or 1; b and c are integers from 0 to 4}. [20] A polyimide film having a film thickness of 10 μm and a yellowness of 20 or less after heating at 400 ° C or higher, and an absorbance at 308 nm of a film thickness of 1 μm of 0.6 or more and 2.0 or less, and The elongation is 15% or more. [21] A resin composition comprising: (a) a polyimine precursor represented by the following formula (1), (b) an organic solvent, and a surfactant selected from the group consisting of (c) a surfactant and (d) at least one of the group consisting of alkoxydecane compounds, [Chem. 14] Wherein X ₁ represents a tetravalent group having a carbon number of 4 to 32; and R ₁ , R ₂ and R ₃ each independently represent an organic group having a carbon number of 1 to 20; n represents 0 or 1; b and c are integers from 0 to 4}. [Effects of the Invention] The polyimine film obtained from the polyimine precursor of the present invention and the resin composition have low residual stress, less warpage, less yellowness (YI value), and high elongation. .

Hereinafter, an exemplary embodiment of the present invention (hereinafter simply referred to as "embodiment") will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made without departing from the spirit and scope of the invention. Moreover, the characteristic value described in the present invention means a value measured by the method described in the item of [Example] or the method which the manufacturer understands by the same method unless otherwise specified. <Resin Composition> The resin composition provided in one aspect of the present invention contains (a) a polyimine precursor and (b) an organic solvent. Hereinafter, each component will be described in order. [Polyimine precursor] The polyimine precursor system as the first aspect of the present embodiment has a polyimine precursor having the following characteristics: the (a1) polyimine precursor, which is 1/1 99≦ (the number of moles of the structural unit L/the number of moles of the structural unit M) ≦99/1 contains: the structural unit L represented by the following general formula (1): [Chem. 15] {式,X ₁ It represents the four-valent base of carbon number 4 to 32. R ₁ , R ₂ , R ₃ Each of the organic groups having a carbon number of 1 to 20 is independently represented. n represents 0 or 1. And a, b, and c are integers of 0 to 4}; and the structural unit M represented by the following general formula (2): [Chem. 16] {式,X ₂ It represents the four-valent base of carbon number 4 to 32. Y is at least one selected from the group consisting of the following general formulae (3), (4), and (5)}. [化17] [化18] [Chemistry 19] {式,R ₄ ~R ₁₁ Each of the organic groups having a carbon number of 1 to 20 is independently represented. d to k is an integer of 0 to 4} The first aspect of the polyimine precursor system of the present embodiment has lower residual stress, less warpage, and yellowness (YI value) when formed into a polyimide film. Small, high elongation. Further, in the first aspect of the present embodiment, the polyimine precursor system has a small yellowness (YI value) in a high temperature region when it is formed into a polyimide film. Here, R ₁ ~R ₃ There is no limitation as long as it is independently an organic group having one carbon number of 1 to 20 carbon atoms. Examples of such an organic group include an alkyl group such as a methyl group, an ethyl group or a propyl group; a halogen-containing group such as a trifluoromethyl group; an alkoxy group such as a methoxy group or an ethoxy group; and the like. Among them, from the viewpoint of YI in a high temperature region, a methyl group is preferred. Here, a, b, c, and d are not limited as long as they are integers of 0 to 4. Among them, from the viewpoint of YI and residual stress, an integer of 0 to 2 is preferable, and it is particularly preferably 0 from the viewpoint of YI in a high temperature region. Here, n is 0 or 1. Among them, from the viewpoint of YI in the high temperature region, it is preferably 0. Moreover, the lower limit of the molar ratio of the structural unit L to the structural unit M (the number of moles of the structural unit L / the number of moles of the structural unit M) may be 5/95, may be 10/90, or may be 20/ 80, can also be 30/70, or 40/60. The upper limit of the molar ratio of the structural unit L to the structural unit M (the number of moles of the structural unit L / the number of moles of the structural unit M) may be 95/5, or may be 90/10 or 80/20. It can also be 70/30 or 60/40. X ₁ , X ₂ They are independently the basis of the four valences of carbon numbers 4 to 32, which may be the same or different. A tetravalent organic group derived from the following tetracarboxylic dianhydride can be exemplified. Specific examples of the tetracarboxylic dianhydride include an aromatic tetracarboxylic dianhydride having a carbon number of 8 to 36, an aliphatic tetracarboxylic dianhydride having a carbon number of 6 to 36, and a carbon number of 6 to 36. A compound of 36 alicyclic tetracarboxylic dianhydride. Among them, from the viewpoint of the yellowness in the high temperature region, an aromatic tetracarboxylic dianhydride having a carbon number of 8 to 36 is preferred. The carbon number here also includes the number of carbons contained in the carboxyl group. More specifically, as the aromatic tetracarboxylic dianhydride having a carbon number of 8 to 36, for example, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (hereinafter also referred to as 6FDA) , 5-(2,5-di-oxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2-dicarboxylic anhydride, pyromellitic dianhydride (hereinafter also referred to as PMDA) ), 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-diphenyl Ketotetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride (hereinafter also referred to as BPDA), 3,3',4,4'-diphenylphosphonium tetracarboxylic acid Anhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylene-4,4'- Diphthalic dianhydride, 2,2-propylene-4,4'-diphthalic dianhydride, 1,2-extended ethyl-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-penta Base-4,4'-diphthalic dianhydride, 4,4'-oxydiphthalic dianhydride (hereinafter also referred to as ODPA), p-phenylene bis(trimellitic anhydride) (hereinafter also Recorded as TAHQ), thio-4,4'-diphthalic dianhydride Sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)phthalic anhydride, 1,3-bis(3,4-dicarboxyphenoxyl) Phthalic anhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)-2-propyl] Phthalic anhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl] Methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane II Anhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethyl phthalane dianhydride, 1,3 - bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldioxanane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4, 5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-decanetetracarboxylic dianhydride, 2,3,6,7-anthracene Tetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, and the like. Examples of the aliphatic tetracarboxylic dianhydride having 6 to 50 carbon atoms include ethyltetracarboxylic dianhydride and 1,2,3,4-butanetetracarboxylic dianhydride; and the carbon number is Examples of the alicyclic tetracarboxylic dianhydride of 6 to 36 include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, and cyclohexane-1,2. , 3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride (hereinafter referred to as CHDA), 3,3',4,4'-bicyclohexyltetracarboxylic acid Acid dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid a dianhydride, 1,2-extended ethyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylene-4,4'-bis (cyclic) Hexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4 '-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4, 4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, rel- [1S,5R,6R]-3-oxabicyclo[3,2,1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 4-(2,5-di-side oxytetrahydrofuran-3-yl)-1,2,3,4- Decalin-1,2-dicarboxylic acid anhydride, ethylene glycol - bis - (3,4-dicarboxylic anhydride) ether and the like. From the viewpoint of the balance between CTE (Coefficient of Thermal Expansion), chemical resistance, Tg (Glass Transition Temperature) and yellowness in a high temperature region, PMDA, BPDA, TAHQ, ODPA, more preferably BPDA, TAHQ. The polyimine precursor of the embodiment can also be made into a polyamidoximine precursor by using a dicarboxylic acid in addition to the above tetracarboxylic dianhydride without damaging its properties. By using such a precursor, the obtained film can be adjusted in various properties such as an increase in mechanical elongation, an increase in glass transition temperature, and a decrease in yellowness. Examples of such a dicarboxylic acid include a dicarboxylic acid having an aromatic ring and an alicyclic dicarboxylic acid. More preferably, it is at least one compound selected from the group consisting of an aromatic dicarboxylic acid having 8 to 36 carbon atoms and an alicyclic dicarboxylic acid having 6 to 34 carbon atoms. The carbon number here also includes the number of carbons contained in the carboxyl group. Among these, a dicarboxylic acid having an aromatic ring is preferred. Specific examples thereof include isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid, 3,4'-biphenyldicarboxylic acid, and 3,3'-biphenyldicarboxylic acid. , 1,4-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-sulfonyl bisbenzoic acid, 3 , 4'-sulfonyl bisbenzoic acid, 3,3'-sulfonyl bisbenzoic acid, 4,4'-oxybisbenzoic acid, 3,4'-oxybisbenzoic acid, 3,3'- Oxydibenzoic acid, 2,2-bis(4-carboxyphenyl)propane, 2,2-bis(3-carboxyphenyl)propane, 2,2'-dimethyl-4,4'-biphenyl Dicarboxylic acid, 3,3'-dimethyl-4,4'-biphenyldicarboxylic acid, 2,2'-dimethyl-3,3'-biphenyldicarboxylic acid, 9,9-bis ( 4-(4-carboxyphenoxy)phenyl)anthracene, 9,9-bis(4-(3-carboxyphenoxy)phenyl)anthracene, 4,4'-bis(4-carboxyphenoxy) Biphenyl, 4,4'-bis(3-carboxyphenoxy)biphenyl, 3,4'-bis(4-carboxyphenoxy)biphenyl, 3,4'-bis(3-carboxyphenoxy Biphenyl, 3,3'-bis(4-carboxyphenoxy)biphenyl, 3,3'-bis(3-carboxyphenoxy)biphenyl, 4,4'-bis(4-carboxyphenoxyl) ())-P-triphenyl, 4,4'-bis(4-carboxyphenoxy)-m-triphenyl, 3,4'-bis(4-carboxyphenoxy)-para-triphenyl, 3,3' - double (4-carboxyl Phenyloxy)-terphenyl, 3,4'-bis(4-carboxyphenoxy)-m-triphenyl, 3,3'-bis(4-carboxyphenoxy)-m-triphenyl, 4,4'-bis(3-carboxyphenoxy)-para-triphenyl, 4,4'-bis(3-carboxyphenoxy)-m-triphenyl, 3,4'-bis(3-carboxybenzene Oxy))-p-triphenyl, 3,3'-bis(3-carboxyphenoxy)-para-triphenyl, 3,4'-bis(3-carboxyphenoxy)-m-triphenyl, 3,3 '-bis(3-carboxyphenoxy)-m-triphenyl, 1,1-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4,4'-benzophenone dicarboxylic acid, 1,3-phenylenediacetic acid, 1,4-phenylenediacetic acid, and the like; and 5-amino group described in International Publication No. 2005/068535 Isophthalic acid derivatives and the like. When the dicarboxylic acid is actually copolymerized into a synthetic polymer, it may be used in the form of a ruthenium chloride or an active ester derived from sulfonium chloride or the like. The weight average molecular weight (Mw) of the polyimide precursor of the present embodiment is preferably 10,000 to 300,000, particularly preferably 30,000 to 200,000. When the weight average molecular weight is more than 10,000, mechanical properties such as elongation and breaking strength are excellent, residual stress is low, and YI is low. When the weight average molecular weight is less than 300,000, the weight average molecular weight can be easily controlled at the time of synthesis of polyamic acid, and a resin composition having a moderate viscosity can be obtained, and the coatability of the resin composition becomes good. In the present invention, the weight average molecular weight is a value obtained by gel permeation chromatography (hereinafter also referred to as GPC) in the form of a standard polystyrene equivalent value. In the polyimine precursor of the present embodiment, the content of the molecule having a molecular weight of less than 1,000 is preferably less than 5% by mass, more preferably less than 1% by mass, based on the total amount of the polyimide intermediate. The residual stress of the polyimide film formed from the resin composition obtained by using such a polyimide precursor is lowered, and the haze of the inorganic film formed on the polyimide film is changed. It is better from a low point of view. The content of the molecule having a molecular weight of less than 1,000 relative to the total amount of the polyimide intermediate precursor can be calculated from the peak area obtained by GPC measurement using a solution in which the polyimide precursor is dissolved. The diamine represented by the following formula (6) can be exemplified as the diamine used in the structural unit represented by the formula (1) of the present embodiment. [Chemistry 20] (where, R ₁ , R ₂ , R ₃ Each of the organic groups having a carbon number of 1 to 20 is independently represented. n represents 0 or 1. And a, b, and c are integers from 0 to 4) as R ₁ , R ₂ Examples thereof include an alkyl group such as a methyl group, an ethyl group or a propyl group; a halogen-containing group such as a trifluoromethyl group; an alkoxy group such as a methoxy group or an ethoxy group; and the like. Among them, from the viewpoint of YI in a high temperature region, a methyl group is preferred. Here, a and b are not limited as long as they are integers of 0 to 4. Among them, from the viewpoint of YI and residual stress, an integer of 0 to 2 is preferable, and it is particularly preferably 0 from the viewpoint of YI in a high temperature region. More specifically, in the case where n is 0, 4-aminophenyl-4-aminobenzoic acid ester (APAB), 2-methyl-4-aminophenyl-4-amine can be exemplified Benzobenzoate (ATAB), 4-aminophenyl-3-aminobenzoate (4,3-APAB), and the like. In the case where n is 1, [4-(4-aminobenzimidyl)oxyphenyl]4-aminobenzoate or the like can be exemplified. The diamine represented by the following formula (7) is exemplified as the diamine used in the structural unit represented by the formula (3) of the present embodiment. [Chem. 21] (where, R ₄ , R ₅ Each of the organic groups having a carbon number of 1 to 20 is independently represented. d, e is an integer from 0 to 4) Here, R ₄ , R ₅ There is no limitation as long as it is independently an organic group having one carbon number of 1 to 20 carbon atoms. Examples of such an organic group include an alkyl group such as a methyl group, an ethyl group or a propyl group; a halogen-containing group such as a trifluoromethyl group; an alkoxy group such as a methoxy group or an ethoxy group; and the like. Among them, from the viewpoint of YI in a high temperature region, a methyl group is preferred. Here, c and d are not limited as long as they are integers of 0 to 4. Among them, from the viewpoint of YI and residual stress, an integer of 0 to 2 is preferable, and it is particularly preferably 0 from the viewpoint of YI in a high temperature region. More specifically, 4,4'-diaminodiphenylanthracene and 3,3'-diaminodiphenylphosphonium can be exemplified. The diamine represented by the following formula (8) can be exemplified as the diamine used in the structural unit represented by the formula (4) of the present embodiment. [化22] Here, R ₆ And R ₇ There is no limitation as long as it is independently an organic group having one carbon number of 1 to 20 carbon atoms. Examples of such an organic group include an alkyl group such as a methyl group, an ethyl group or a propyl group; a halogen-containing group such as a trifluoromethyl group; an alkoxy group such as a methoxy group or an ethoxy group; and the like. Among them, from the viewpoint of YI in a high temperature region, a methyl group is preferred. R ₈ With R ₉ There is no limitation as long as it is independently an organic group having one carbon number of 1 to 20, a hydroxyl group or a halogen atom. Examples of the organic group include an alkyl group such as a methyl group, an ethyl group or a propyl group; a halogen-containing group such as a trifluoromethyl group; an alkoxy group such as a methoxy group or an ethoxy group; and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. f, g, h, and i are not limited as long as they are independently integers of 0 to 4. Among them, from the viewpoint of YI and residual stress, an integer of 0 to 2 is preferable, and it is particularly preferably 0 from the viewpoint of YI in a high temperature region. Z may, for example, be a single bond, a methylene group, an ethyl group, an ether, a ketone or the like. Among them, from the viewpoint of YI in the high temperature region, it is more preferably a single bond. More specifically, it can be exemplified: 9,9-bis(aminophenyl)anthracene, 9,9-bis(4-amino-3-methylphenyl)anthracene, 9,9-bis(4-amino group 3-fluorophenyl)anthracene, 9,9-bis(4-hydroxy-3-aminophenyl)anthracene, 9,9-bis[4-(4-aminophenoxy)phenyl]anthracene, etc. Preferably, one or more selected from the group consisting of these are used. The diamine represented by the following formula (9) can be exemplified as the diamine used in the structural unit represented by the formula (5) of the present embodiment. [化23] Here, R ₁₀ And R ₁₁ There is no limitation as long as it is independently an organic group having one carbon number of 1 to 20 carbon atoms. Examples of such an organic group include an alkyl group such as a methyl group, an ethyl group or a propyl group; a halogen-containing group such as a trifluoromethyl group; an alkoxy group such as a methoxy group or an ethoxy group; and the like. Among them, from the viewpoint of YI in a high temperature region, a methyl group is preferred. Further, j and k are not limited as long as they are each independently an integer of 0 to 4. Among them, from the viewpoint of YI and residual stress, an integer of 0 to 2 is preferable, and it is particularly preferably 0 from the viewpoint of YI in a high temperature region. More specifically, 2,2'-bis(trifluoromethyl)benzidine or the like can be exemplified. The polyimine film formed by the polyimide precursor of the first aspect of the present embodiment has a low residual stress, less warpage, a small yellowness (YI value) in a high temperature region, and a high elongation. As a second aspect of the present invention, there may be provided a polyimine precursor which is a (a2) polyimine precursor comprising a structural unit represented by the following formula (10): ] Further, the weight average molecular weight is 30,000 or more and 300,000 or less. {式,X ₃ Indicated from 4,4'-oxydiphthalic dianhydride (ODPA), biphenyltetracarboxylic dianhydride (BPDA) and 4,4'-biphenyl bis(trimellitic acid monoester anhydride) A tetravalent base of at least one of (TAHQ). R ₁ , R ₂ , R ₃ Each of the organic groups having a carbon number of 1 to 20 is independently represented. n represents 0 or 1. And a, b, and c are integers from 0 to 4} Here, X ₃ The tetravalent organic group derived from at least one selected from the group consisting of ODPA, BPDA, and TAHQ is not limited, and from the viewpoints of CTE and Tg, BPDA and TAHQ are preferred. Here, R ₁ ~R ₃ There is no limitation as long as it is independently an organic group having one carbon number of 1 to 20 carbon atoms. Examples of such an organic group include an alkyl group such as a methyl group, an ethyl group or a propyl group; a halogen-containing group such as a trifluoromethyl group; an alkoxy group such as a methoxy group or an ethoxy group; and the like. Among them, from the viewpoint of YI in a high temperature region, a methyl group is preferred. Here, a, b, c, and d are not limited as long as they are integers of 0 to 4. Among them, from the viewpoint of YI and residual stress, an integer of 0 to 2 is preferable, and it is particularly preferably 0 from the viewpoint of YI in a high temperature region. Here, n is 0 or 1. Among them, from the viewpoint of YI in the high temperature region, it is preferably 0. As the diamine used in the structure represented by the above formula (10), a diamine used in the above formula (6) can be used. The second aspect of the polyimide precursor has a weight average molecular weight (Mw) of 30,000 to 300,000. When the weight average molecular weight is more than 30,000, mechanical properties such as elongation and breaking strength are excellent, residual stress is low, and YI is low. When the weight average molecular weight is less than 300,000, the weight average molecular weight can be easily controlled at the time of synthesis of polyamic acid, and a resin composition having a moderate viscosity can be obtained, and the coatability of the resin composition becomes good. Among them, the weight average molecular weight (Mw) is more preferably 35,000 or more and 250,000 or less, and particularly preferably 40,000 or more and 230,000 or less. In the second aspect of the present invention, the content of the molecule having a molecular weight of less than 1,000 is preferably less than 5% by mass, more preferably less than the total amount of the polyimide precursor. 1% by mass. The residual stress of the polyimide film formed from the resin composition obtained by using the polyimide precursor is low, and the haze of the inorganic film formed on the polyimide film is lowered. It is better. The content of the molecule having a molecular weight of less than 1,000 relative to the total amount of the polyimide intermediate precursor can be calculated from the peak area obtained by GPC measurement using a solution in which the polyimide precursor is dissolved. The polyimide precursor of the second aspect of the present embodiment is excellent in storage stability and excellent in coatability. Moreover, the polyimine film formed by the polyimide precursor of the second aspect of the present embodiment has low residual stress, less warpage, small yellowness (YI value), high elongation, and relatively high breaking strength. high. In the first aspect and the second aspect of the polyimide precursor, the above formula (6) to (9) can be used without impairing the elongation, strength, stress, and yellowness. Other diamines other than the diamines indicated. Examples of the other diamines include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, and 3,3'-. Diaminodiphenyl sulfide, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminodi Benzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diamine Diphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene , 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]anthracene, 4,4-bis(4-aminophenoxy) Benzene, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy) Phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)benzene Propyl, 2,2-bis[4-(4-aminophenoxy)phenyl)hexafluoropropane, 1,4-bis(3-aminopropyldimethylmethylalkyl)benzene, etc. good Use of one or more of those selected. The content of the above other diamine in all the diamines is preferably 20 mol% or less, and more preferably 10 mol% or less. [Production of Polyimine Precursor] The polyimine precursor (polylysine) of the present invention can be used for the tetracarboxylic dianhydride and the structural unit represented by the above formula (1) An amine (for example, APAB) and a diamine (for example, 4,4'-DAS) used for the structural unit represented by the above formula (2) are synthesized by a polycondensation reaction. The reaction is preferably carried out in a suitable solvent. Specifically, for example, a method in which a specific amount of APAB and 4,4′-DAS are dissolved in a solvent, and a specific amount of tetracarboxylic dianhydride is added to the obtained diamine solution, followed by stirring. In the diamine component, the molar ratio of the diamine used for the structural unit represented by the general formula (1) to the diamine used for the structural unit represented by the general formula (2) is from 99/1 to 1/99. Yes, there is no limit. In the diamine component, when the diamine used in the structural unit represented by the formula (2) is 1 mol% or more, the yellowness tends to be good, and it is used in the structural unit represented by the formula (1). When the amount of the diamine is 1 mol% or more, the warpage after the formation of the inorganic film on the obtained polyimide film tends to be good. The molar amount of the diamine used for the structural unit represented by the general formula (1) and the diamine used for the structural unit represented by the general formula (2) is preferably 95/5 to 50/50, more preferably 90/. 10 to 50/50. The molar ratio of the diamine used for the structural unit represented by the general formula (1) to the diamine used for the structural unit represented by the general formula (2) may be 80/20 to 50/50 or 70. /30~50/50. It is preferred that the molar ratio of the diamine used for the structural unit represented by the general formula (1) is set to be higher than the molar ratio of the diamine used for the structural unit represented by the general formula (2). Further, the second aspect of the present invention may be obtained by using a tetracarboxylic dianhydride (for example, TAHQ) with a diamine (for example, APAB) used for the structural unit represented by the above formula (6). The polycondensation reaction is carried out to synthesize. The reaction is preferably carried out in a suitable solvent. Specifically, for example, a method in which a specific amount of APAB is dissolved in a solvent, and a specific amount of TAHQ is added to the obtained diamine solution, followed by stirring. Regarding the ratio (mol ratio) of the tetracarboxylic dianhydride component to the diamine component in synthesizing the above polyimine precursor, the coefficient of thermal linear expansion, residual stress, elongation, and yellowness of the obtained resin film (hereinafter also From the viewpoint that YI) is controlled within a desired range, it is preferably set to tetracarboxylic dianhydride: diamine = 100: 90 to 100: 110 (relative to 1 mole of tetracarboxylic dianhydride, The range of the diamine is from 0.90 to 1.10 mole parts, more preferably from 100:95 to 100:105 (relative to 1 part of the acid dianhydride and 0.95 to 1.05 mole parts of the diamine). In the present embodiment, in synthesizing polyglycolic acid which is a preferred polyimine precursor, the molecular weight can be controlled by adjusting the ratio of the tetracarboxylic dianhydride component to the diamine component and adding a blocking agent. The closer the ratio of the acid dianhydride component to the diamine component is 1:1, and the smaller the amount of the terminal blocking agent used, the larger the molecular weight of the polyamic acid. As a tetracarboxylic dianhydride component and a diamine component, it is recommended to use a high purity product. The purity is preferably 98% by mass or more, more preferably 99% by mass or more, and still more preferably 99.5% by mass or more. When a plurality of acid dianhydride components or diamine components are used in combination, the acid dianhydride component or the diamine component may have the above-mentioned purity as a whole, but it is preferably all kinds of acid dianhydride components and diamine components used. Each has the above purity. The solvent for the reaction is not particularly limited as long as it is a solvent capable of dissolving the tetracarboxylic dianhydride component and the diamine component and the produced polyglycolic acid and obtaining a polymer having a high molecular weight. Specific examples of such a solvent include an aprotic solvent, a phenol solvent, an ether, and an alcohol solvent. Specific examples of the aprotic solvent include N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), and N-methyl. -2-pyrrolidone (NMP), N-methyl caprolactam, 1,3-dimethylimidazolidinone, tetramethylurea, the following formula (13): [Chem. 25] Where R ₁₂ = Equamide M100 (trade name: manufactured by Idemitsu Kosan Co., Ltd.) and R ₁₂ = a guanamine solvent such as Equamide B100 (trade name: manufactured by Idemitsu Kosan Co., Ltd.) represented by n-butyl group; a lactone solvent such as γ-butyrolactone or γ-valerolactone; hexamethylphosphonium, six a phosphorus-containing guanamine-based solvent such as methylphosphonium triamine; a sulfur-containing solvent such as dimethyl hydrazine, dimethyl hydrazine or cyclobutyl hydrazine; a ketone solvent such as cyclohexanone or methylcyclohexanone; A tertiary amine solvent such as a pyridine or a pyridine; an ester solvent such as an acetic acid (2-methoxy-1-methylethyl) ester; and the phenol solvent: phenol, o-cresol, and phenol. Cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5 - xylenol or the like; examples of the ether and the alcohol-based solvent include 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, and 1,2-bis(2-methyl) Oxyethoxyethoxy)ethane, bis[2-(2-methoxyethoxy)ethyl]ether, tetrahydrofuran, 1,4-two Alkane, etc. The boiling point of the solvent used in the synthesis of the polyamic acid is preferably from 60 to 300 ° C, more preferably from 140 to 280 ° C, still more preferably from 170 to 270 ° C. If the boiling point of the solvent is higher than 300 ° C, the drying step takes a long time. On the other hand, when the boiling point of the solvent is less than 60 ° C, the surface of the resin film is rough in the drying step, and bubbles or the like are mixed in the resin film, so that a uniform film cannot be obtained. Thus, from the viewpoint of solubility and edge shrinkage at the time of coating, a solvent having a boiling point of preferably 170 to 270 ° C, more preferably a vapor pressure of 20 ° C or less at 20 ° C is preferably used. More specifically, it is preferred to use one or more selected from the group consisting of N-methyl-2-pyrrolidone, γ-butyrolactone, and a compound represented by the above formula (11). The moisture content in the solvent is preferably 3,000 ppm by mass or less. These solvents may be used singly or in combination of two or more. In the (a) polyimine precursor of the present embodiment, the content of the molecule having a molecular weight of less than 1,000 is preferably less than 5% by mass. The reason why the molecule having a molecular weight of less than 1,000 is present in the (a) polyimine precursor is that it is related to the moisture content of the solvent used in the synthesis. In other words, it is considered that the acid anhydride group of a part of the acid dianhydride monomer is hydrolyzed to a carboxyl group by water, and it is not polymerized and remains in a low molecular state. Therefore, the amount of water of the solvent used in the above polymerization reaction is preferably as small as possible. The water content of the solvent is preferably 3,000 ppm by mass or less, and more preferably 1,000 ppm by mass or less. It is considered that the moisture content of the solvent is related to the following factors: the grade of the solvent to be used (dehydration grade, general grade, etc.), the solvent container (bottle, 18 L can, canister, etc.), and the storage state of the solvent (whether or not the rare gas is enclosed) Etc.), the time from the opening to the use (used immediately after opening, or after use after opening), etc. Further, it is considered to be related to the replacement of the rare gas in the reactor before the synthesis, the presence or absence of the distribution of the rare gas in the synthesis, and the like. Therefore, it is recommended to use a high-purity product as a raw material, use a solvent having a small amount of water, and take measures before the reaction and in the reaction to prevent moisture from the environment from being mixed into the (a) polyimide imide precursor. Within the system. When each monomer component is dissolved in a solvent, it can be heated as needed. (a) The reaction temperature at the time of synthesis of the polyimide precursor is preferably from 0 ° C to 120 ° C, more preferably from 40 ° C to 100 ° C, still more preferably from 60 to 100 ° C. By carrying out the polymerization reaction at this temperature, a polyimide intermediate precursor having a high degree of polymerization can be obtained. The polymerization time is preferably from 1 to 100 hours, more preferably from 2 to 10 hours. A polyimine precursor which can be a uniform polymerization degree can be obtained by setting the polymerization time to 1 hour or more, and a polyimine precursor having a high degree of polymerization can be obtained by setting it to 100 hours or less. In a preferred embodiment of the present embodiment, the (a1) polyimine precursor and the (a2) polyimine precursor have the following characteristics. After the solution obtained by dissolving the (a) polyimine precursor in a solvent (for example, N-methyl-2-pyrrolidone) is applied onto the surface of the support, the solution is placed under a nitrogen atmosphere ( For example, in a nitrogen gas having an oxygen concentration of 2,000 ppm or less, heated at 300 to 550 ° C (for example, 430 ° C) (for example, 1 hour) to imidize the polyimine precursor oxime, 10 μm The yellowness of the film thickness is 30 or less. After the solution obtained by dissolving the (a) polyimine precursor in a solvent (for example, N-methyl-2-pyrrolidone) is applied onto the surface of the support, the solution is placed under a nitrogen atmosphere ( For example, in a nitrogen gas having an oxygen concentration of 2,000 ppm or less, heated at 300 to 550 ° C (for example, 430 ° C) (for example, 1 hour) to imidize the polyimine precursor ruthenium, residual stress It is 25 MPa or less. The polyimine precursor of the present embodiment may further contain a polyimine precursor having a structure represented by the following formula (14), as long as it does not impair the desired properties of the present invention: [Chem. 26] {In the general formula (14), there are a plurality of R ₁₃ Each is independently a hydrogen atom, an aliphatic hydrocarbon having a carbon number of 1 to 20, or a monovalent aromatic group, X ₄ It is a tetravalent organic group having 4 to 32 carbon atoms, and Y is a divalent organic group having 4 to 32 carbon atoms. However, the structural unit corresponding to the above formula (1) and the above formula (6) is excluded. In the general formula (14), R ₁₃ It is preferably a hydrogen atom. Also, in terms of heat resistance, reduction in YI value, and total light transmittance, X ₃ It is preferably a tetravalent aromatic group. Further, Y is preferably a divalent aromatic group or an alicyclic group from the viewpoint of heat resistance, reduction in YI value, and total light transmittance. The mass ratio of the polyimine precursor containing the structural unit represented by the general formula (14) in the (a) polyfluorene precursor of the present embodiment is relative to (a) the polyimine precursor All of them are preferably 80% by mass or less, and more preferably 70% by mass or less from the viewpoint of a decrease in the YI value and the oxygen dependency of the total light transmittance. In a preferred embodiment of the present embodiment, a portion of the (a1) polyimine precursor and the (a2) polyimine precursor system may be imidized by hydrazine. In this case, the imidization ratio is preferably 80% or less, and more preferably 50% or less. The partial ruthenium imidization can be obtained by heating the above (a) polyimine precursor to perform dehydration ring closure. The heating may be carried out at a temperature of preferably from 120 to 200 ° C, more preferably from 150 to 180 ° C, preferably from 15 minutes to 20 hours, more preferably from 30 minutes to 10 hours. Further, N,N-dimethylformamide dimethyl acetal or N,N-dimethylformamide diethyl acetal is added to the polylysine obtained by the above reaction, and heated. After partially or completely esterifying one of the carboxylic acids, it is used as the (a) polyimine precursor of the present embodiment, whereby a resin composition having improved viscosity stability at room temperature storage can be obtained. The ester-modified polylysine may also be obtained by additionally obtaining the above-mentioned acid dianhydride component, and one equivalent of one alcohol and sulfoxide, dicyclohexylcarbazide relative to the acid anhydride group. The dehydration condensing agent such as an amine is reacted in this order, and then subjected to a condensation reaction with the diamine component. The ratio of the (a) polyimine precursor (preferably poly-proline) in the resin composition of the present embodiment is preferably from 3 to 50% by mass, more preferably from the viewpoint of film formability. It is 5 to 40% by mass, and particularly preferably 10 to 30% by mass. <Resin Composition> Another aspect of the present invention provides a resin composition comprising the above (a) polyimine precursor and (b) an organic solvent. The resin composition is typically a varnish. [(b) Organic solvent] The organic solvent (b) of the present embodiment is not particularly limited as long as it can dissolve the (a) polyimine precursor and any other components used arbitrarily. As such an organic solvent (b), those which are described above as a solvent which can be used in the synthesis of the (a) polyimine precursor can be used. Preferred organic solvents are also the same as described above. The (b) organic solvent in the resin composition of the present embodiment may be the same as or different from the solvent used in the synthesis of the (a) polyimine precursor. (b) The organic solvent is preferably an amount of the solid content of the resin composition of from 3 to 50% by mass. In addition, it is preferable to adjust (b) the composition and amount of the organic solvent so that the viscosity (25 ° C) of the resin composition is 500 mPa·s to 100,000 mPa·s. [Other components] The resin composition of the present embodiment may further contain (c) a surfactant, (d) an alkoxydecane compound, etc., in addition to the above components (a) and (b). The resin composition of the present embodiment contains at least one selected from the group consisting of (a) a polyimide intermediate, (b) an organic solvent, (c) a surfactant, and (d) an alkoxydecane compound. . The skeleton of the polyimide precursor is not limited to the skeleton described in the first aspect and the second aspect above. In other words, the skeleton of the polyimide precursor is not particularly limited as long as it is a skeleton represented by the following formula (1). [化27] {式,X ₁ It represents the four-valent base of carbon number 4 to 32. R ₁ , R ₂ , R ₃ Each of the organic groups having a carbon number of 1 to 20 is independently represented. n represents 0 or 1. Further, a, b and c are integers of 0 to 4} ((c) Surfactant) The resin composition of the present embodiment can improve the coatability of the resin composition by adding a surfactant. Specifically, generation of streaks of the coating film can be prevented. Examples of such a surfactant include a polyfluorene-based surfactant, a fluorine-based surfactant, and other nonionic surfactants. As such an example, examples of the polyoxymethylene-based surfactant include an organic silicone polymer (KG-640, 642, 643, KP341, X-70-092, and X-70-093). (The above is the trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (the above is the trade name, Toray Dow Corning Poly Manufactured by the company, SILWET L-77, L-7001, FZ-2105, FZ-2120, FZ-2154, FZ-2164, FZ-2166, L-7604 (above, trade name, manufactured by Nippon Unicar), DBE-814, DBE-224, DBE-621, CMS-626, CMS-222, KF-352A, KF-354L, KF-355A, KF-6020, DBE-821, DBE-712 (Gelest), BYK-307 , BYK-310, BYK-378, BYK-333 (the above is a trade name, manufactured by BYK-Chemie Japan), Glanol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), etc.; as a fluorine-based surfactant, for example, MEGAFAC F171, F173, R-08 (manufactured by Dainippon Ink and Chemicals Co., Ltd., trade name), Fluorad FC4430, FC4432 (Sumitomo 3M Co., Ltd., trade name), etc.; as a nonionic surfactant other than these Examples thereof include: polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether and the like. Among these surfactants, from the viewpoint of coating properties (streak suppression) of the resin composition, a polyfluorene-based surfactant or a fluorine-based surfactant is preferred, and the oxygen concentration in the curing step is YI. From the viewpoint of the influence of the value and the total light transmittance, a polyfluorene-based surfactant is preferred. In the case of using (c) a surfactant, the amount thereof is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 3 parts by mass based on 100 parts by mass of the (a) polyimine precursor in the resin composition. Parts by mass. (d) alkoxy decane compound The resin composition can be made to have sufficient adhesion to the support in the production process of the flexible device or the like in the resin film of the present embodiment. a) The polyamidene precursor is contained in an amount of from 0.01 to 20% by mass based on 100% by mass of the alkoxydecane compound. By setting the content of the alkoxydecane compound in an amount of 100% by mass based on the polyimine precursor to 0.01% by mass or more, good adhesion to the support can be obtained. Moreover, from the viewpoint of storage stability of the resin composition, the content of the alkoxydecane compound is preferably 20% by mass or less. The content of the alkoxydecane compound is more preferably 0.02 to 15% by mass, still more preferably 0.05 to 10% by mass, even more preferably 0.1 to 8% by mass, based on 100 parts by mass of the polyimide intermediate. By using an alkoxydecane compound as an additive of the resin composition of the present embodiment, in addition to improving the adhesion, the coating property of the resin composition can be improved (strip unevenness is suppressed), and the obtained cured film can be lowered. The oxygen concentration dependence of the YI value during curing. Examples of the alkoxydecane compound include 3-ureidopropyltriethoxydecane, bis(2-hydroxyethyl)-3-aminopropyltriethoxydecane, and 3-glycidyloxy group. Propyltrimethoxydecane, γ-aminopropyltrimethoxydecane, γ-aminopropyltripropoxydecane, γ-aminopropyltributoxydecane, γ-aminoethyltriethyl Oxy decane, γ-aminoethyl tripropoxy decane, γ-aminoethyl tributoxy decane, γ-aminobutyl triethoxy decane, γ-aminobutyl trimethoxy decane , γ-aminobutyl tripropoxy decane, γ-aminobutyl tributoxy decane, phenyl decane triol, trimethoxy phenyl decane, trimethoxy (p-tolyl) decane, diphenyl Alkane diol, dimethoxydiphenyl decane, diethoxydiphenyl decane, dimethoxydi-p-tolyl decane, triphenyl decyl alcohol, and alkoxy decane represented by the following structures, respectively The compound or the like is preferably one or more selected from the group consisting of these. [化28] The method for producing the resin composition of the present embodiment is not particularly limited. For example, the following methods can be utilized. When the solvent used in the synthesis of the (a) polyimine precursor is the same as (b) the organic solvent, the synthesized polyimide intermediate precursor solution can be directly used as the resin composition. Further, if necessary, one or more organic solvents and other components may be added to the polyimide precursor in a temperature range from room temperature (25 ° C) to 80 ° C, and the mixture may be used as a resin composition after stirring and mixing. . As the stirring and mixing, a suitable device such as a Sany motor (manufactured by Shinto Chemical Co., Ltd.) equipped with a stirring blade, a rotary revolution mixer, or the like can be used. Further, heat of 40 to 100 ° C can be applied as needed. On the other hand, when the solvent used in the synthesis of the (a) polyimine precursor is different from the (b) organic solvent, the synthesized polymer can be synthesized by a suitable method such as reprecipitation or solvent distillation. After separating the (a) polyimine precursor by solvent removal in the quinone imine precursor solution, add (b) an organic solvent and other components as needed, and stir and mix at a temperature ranging from room temperature to 80 °C. Thereby, a resin composition was prepared. After preparing the resin composition in the above manner, the composition solution is heated, for example, at 130 to 200 ° C for, for example, 5 minutes to 2 hours, whereby one part of the polyimide precursor can be dehydrated to the extent that the polymer is not precipitated.醯imination. Here, the hydrazine imidation ratio can be controlled by controlling the heating temperature and the heating time. By partially imidating the polyimine precursor, the viscosity stability of the resin composition at the time of storage at room temperature can be improved. The range of the imidization ratio is preferably from 5% to 70% from the viewpoint of the balance between the solubility of the polyimide precursor in the resin composition solution and the storage stability of the solution. The resin composition of the present embodiment preferably has a water content of 3,000 ppm by mass or less. The water content of the resin composition is preferably 1,000 ppm by mass or less, and more preferably 500 ppm by mass or less from the viewpoint of the viscosity stability in the case of preserving the resin composition. The solution viscosity of the resin composition of the present embodiment is preferably 500 to 200,000 mPa·s at 25 ° C, more preferably 2,000 to 100,000 mPa·s, and particularly preferably 3,000 to 30,000 mPa·s. The viscosity of the solution can be measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., VISCONICEHD). When the viscosity of the solution is less than 300 mPa·s, coating at the time of film formation is difficult, and if it is higher than 200,000 mPa·s, there is a problem that stirring at the time of synthesis becomes difficult. When the (a) polyimine precursor is synthesized, even if the solution becomes a high viscosity, a resin composition having a more handleable viscosity can be obtained by adding a solvent and stirring it after completion of the reaction. The resin composition of the present embodiment has the following characteristics in a preferred embodiment. After coating the resin composition on the surface of the support to form a coating film, the coating film is heated at 300 ° C to 550 ° C in a nitrogen atmosphere (for example, nitrogen gas having an oxygen concentration of 2,000 ppm or less). The resin film obtained by the imidization of the polyimine precursor contained in the coating film has a yellowness YI of 10 μm or less. After coating the resin composition on the surface of the support to form a coating film, the coating film is heated at 300 ° C to 550 ° C in a nitrogen atmosphere (for example, nitrogen gas having an oxygen concentration of 2,000 ppm or less). The resin film-based residual stress obtained by imidization of the polyimine precursor precursor contained in the coating film is 25 MPa or less. The resin composition of the present embodiment can be preferably used, for example, as a transparent substrate for forming a display device such as a liquid crystal display, an organic electroluminescence display, a field emission display, or an electronic paper. Specifically, it can be used for forming a substrate of a thin film transistor (TFT), a substrate of a color filter, a substrate of a transparent conductive film (ITO, Indium Thin Oxide), or the like. The resin precursor of the present embodiment can form a polyimide film having a residual stress of 25 MPa or less, and thus can be easily applied to a display manufacturing step including a TFT element device on a colorless transparent polyimide substrate. <Resin film> Another aspect of the present invention provides a resin film formed of the above resin precursor. Moreover, still another aspect of the present invention provides a method of producing a resin film from the above resin composition. The resin film of the present embodiment is characterized by comprising: a step of forming a coating film by applying the resin composition on the surface of the support (coating step); and heating the support and the coating film a step of imidizing the polyimine precursor contained in the coating film to form a polyimide film (heating step); and a step of peeling the polyimine resin film from the support (peeling) step). Here, the support is not particularly limited as long as it has heat resistance to the heating temperature in the subsequent step and the peeling property is good. For example, glass: (for example, alkali-free glass) substrate; germanium wafer; PET (polyethylene terephthalate), OPP (stretch polypropylene), polyethylene glycol terephthalate, polyethylene Alcohol naphthalate, polycarbonate, polyimine, polyamidimide, polyether phthalimide, polyether ether ketone, polyether oxime, polyphenylene fluorene, polyphenylene sulfide and other resins Substrate; metal substrates such as stainless steel, aluminum oxide, copper, and nickel. In the case of forming a film-shaped polyimine molded article, for example, a glass substrate, a ruthenium wafer or the like is preferably used, and in the case of forming a film-like or sheet-like polyimide film, for example, it is preferable to contain A support such as PET (polyethylene terephthalate) or OPP (extended polypropylene). As the coating method, for example, application by a knife coater, an air knife coater, a roll coater, a spin coater, a flow coater, a die coater, a bar coater, or the like can be applied. Methods, coating methods such as spin coating, spray coating, dip coating, etc.; printing techniques such as screen printing and gravure printing. The coating thickness is appropriately adjusted depending on the thickness of the desired resin film and the content of the polyimide precursor in the resin composition, and is preferably about 1 to 1,000 μm. The coating step may be carried out at room temperature. However, if the viscosity is to be lowered to improve the workability, the resin composition may be heated at a temperature of from 40 to 80 ° C. The drying step may be carried out after the coating step, or the subsequent heating step may be directly performed by omitting the drying step. This drying step is carried out for the purpose of removing the organic solvent. In the case of performing the drying step, for example, a suitable apparatus such as a hot plate, a box dryer, or a conveyor type dryer can be used. The drying step is preferably carried out at 80 to 200 ° C, more preferably at 100 to 150 ° C. The execution time of the drying step is preferably from 1 minute to 10 hours, more preferably from 3 minutes to 1 hour. A coating film containing a polyimide precursor is formed on the support in the above manner. Then, a heating step is performed. The heating step is a step of removing the organic solvent remaining in the coating film in the drying step, and performing a hydrazine imidization reaction of the polyimide precursor in the coating film to obtain a film comprising polyimine. This heating step can be carried out, for example, using an apparatus such as an inert gas oven, a hot plate, a box dryer, or a transport dryer. This step can be carried out simultaneously with the above drying step, or two steps can be carried out one by one. The heating step can be carried out in an air atmosphere, but it is recommended to carry out in an inert gas atmosphere from the viewpoint of safety and transparency and YI value of the obtained polyimide film. Examples of the inert gas include nitrogen gas, argon gas, and the like. The heating temperature can be appropriately set depending on the kind of the organic solvent (b), and is preferably from 250 ° C to 550 ° C, more preferably from 300 to 450 ° C. When it is 250 ° C or more, the ruthenium imidization is sufficient, and when it is 550 ° C or less, the transparency of the obtained polyimide film is not lowered, and the heat resistance is deteriorated. The heating time is preferably set to about 0.5 to 3 hours. In the present embodiment, the oxygen concentration of the surrounding environment of the heating step is preferably 2,000 ppm by mass or less, and more preferably 100 ppm by mass or less from the viewpoint of transparency and YI value of the obtained polyimide film. Further, it is preferably 10 ppm by mass or less. By heating in an environment having an oxygen concentration of 2,000 ppm by mass or less, the YI value of the obtained polyimide film can be made 30 or less. Depending on the use and purpose of the polyimide film, the peeling step of peeling the resin film from the support may be required after the above heating step. This peeling step is preferably carried out after cooling the resin film on the support to room temperature to about 50 °C. Examples of the peeling step include the following aspects (1) to (4). (1) After the structure comprising the polyimide film/support is produced by the above method, the laser is irradiated from the support side of the structure to etch the interface between the support and the polyimide film. A method of processing, thereby peeling off the polyimide resin. Examples of the type of the laser include a solid (YAG (Yttrium Aluminum Garnet)) laser, a gas (UV (ultraviolet) excimer) laser, and the like. It is preferable to use a spectrum having a wavelength of 308 nm or the like (refer to Japanese Patent Laid-Open Publication No. 2007-512568, Japanese Patent Laid-Open Publication No. 2012-511173, and the like). (2) A release layer is formed on the support before the application of the resin composition on the support, and thereafter, a composition comprising a polyimide film/release layer/support is obtained, and the polyimide film is peeled off. method. Examples of the release layer include a method of using Parylene (registered trademark, manufactured by Japan's Parylene Contract Co., Ltd.), tungsten oxide, and a method of using a release agent such as a vegetable oil, a polyoxygen, a fluorine or an alkyd. (Japanese Patent Laid-Open Publication No. 2010-67957, Japanese Patent Laid-Open Publication No. 2013-179306, etc.). The method (2) may also be used in combination with the laser irradiation of the above (1). (3) A method of obtaining a polyimine resin film by etching a metal with an etchant using an etchable metal substrate as a support and obtaining a constituent comprising a polyimide film/support. As the metal, for example, copper (specifically, electrolytic copper foil "DFF" manufactured by Mitsui Mining Co., Ltd.), aluminum, or the like can be used. As the etchant, ferric chloride or the like is used for copper, and dilute hydrochloric acid or the like is used for aluminum. (4) After obtaining a constituent comprising a polyimide film/support by the above method, an adhesive film is attached to the surface of the polyimide film, and the adhesive film/polyimine resin film is separated from the support. And a method of separating the polyimide film from the adhesive film. In the above-mentioned peeling method, from the viewpoints of the refractive index difference, the YI value and the elongation of the front and back sides of the obtained polyimide film, it is suitable for the method (1) or (2). From the viewpoint of the difference in refractive index between the front side and the back side of the imide resin film, the method (1) is more suitable. Further, in the case of using the copper as the support in the method (3), the YI value of the obtained polyimide film is increased, and the elongation tends to be small. It is believed to be due to the influence of copper ions. The thickness of the resin film obtained by the above method is not particularly limited, but is preferably in the range of 1 to 200 μm, more preferably 5 to 100 μm. The yellowness YI of the 10 μm film thickness of the resin film of the present embodiment may be 30 or less. Further, the residual stress can be 25 MPa or less. In particular, the yellowness YI of the film thickness of 10 μm is 30 or less and the residual stress is 25 MPa or less. Such a property can be obtained, for example, by subjecting the resin precursor of the present invention to a nitrogen atmosphere (for example, nitrogen having an oxygen concentration of 2,000 ppm or less), preferably 300 to 550 ° C, more preferably 350 to 450 ° C. It is well achieved by imidization. The resin film of the present embodiment may have a tensile elongation of 15% or more. The tensile elongation of the resin film may further be 20% or more, and particularly 30% or more. The tensile elongation can be measured by using a resin film having a film thickness of 10 μm as a sample using a commercially available tensile tester. The resin film of the present embodiment includes a film of a polyimine imide obtained by thermally imidating (a1) a polyimide precursor contained in the resin composition. Therefore, it contains a structural unit represented by the following formula (11): [Chem. 29] {式,X ₁ , X ₂ It represents the four-valent base of carbon number 4 to 32. R ₁ , R ₂ , R ₃ Each of the organic groups having a carbon number of 1 to 20 is independently represented. n represents 0 or 1. And a, b and c are integers of 0-4. Y is at least one selected from the group consisting of the above formulas (3), (4), and (5). l, m independently represent an integer of 1 or more, satisfying 0.01≦l/(l+m)≦0.99}. The lower limit of l/(l+m) may be 0.05, may be 0.10, may be 0.20, may be 0.30, or may be 0.40. The upper limit of l/(l+m) may be 0.95, may be 0.90, may be 0.80, may be 0.70, or may be 0.60. As described above, the residual stress is preferably 25 MPa or less, the YI is 30 or less, the glass transition temperature is 400 ° C or higher, the elongation is 15% or more, and the breaking strength is 250 MPa or more. Further, the second aspect is a film comprising a polyimine imide obtained by thermally imidating the (a2) polyfluorene imide precursor contained in the resin composition. Therefore, it contains a structural unit represented by the following formula (12): [Chem. 30] {式,X ₃ Indicated from 4,4'-oxydiphthalic dianhydride (ODPA), biphenyltetracarboxylic dianhydride (BPDA) and 4,4'-biphenyl bis(trimellitic acid monoester anhydride) A tetravalent base of at least one of (TAHQ). R ₁ , R ₂ , R ₃ Each of the organic groups having a carbon number of 1 to 20 is independently represented. n represents 0 or 1. Further, the resin film in which a, b, and c are integers of 0 to 4} and the elongation is 15% or more preferably has a residual stress of 25 MPa or less, a YI of 30 or less, a glass transition temperature of 400 ° C or more, and a breaking strength. It is 250 MPa or more. <Laminate> Another aspect of the present invention provides a laminate comprising a support and a polyimide film formed of the above resin composition on the surface of the support. Still another aspect of the present invention provides a method of producing the above laminated body. The laminate of the present embodiment can be obtained by a method for producing a laminate comprising the following steps: a step of forming a coating film by coating the resin composition on the surface of the support (coating step); The support and the coating film are heated, and the polyimine precursor precursor contained in the coating film is imidized to form a polyimide film (heating step). The method for producing the laminated body can be carried out in the same manner as the method for producing the resin film, for example, except that the peeling step is not performed. The laminate can be preferably used, for example, for the manufacture of a flexible device. If it is described in further detail, it is as follows. In the case of forming a flexible display, a glass substrate is used as a support, a soft substrate is formed thereon, and a TFT or the like is formed thereon. The step of forming a TFT or the like on a flexible substrate is typically carried out at a temperature ranging from 150 to 650 °C. However, in order to achieve the desired performance in reality, an inorganic material must be used at a high temperature in the vicinity of 250 ° C to 450 ° C to form a TFT-IGZO (InGaZnO) oxide semiconductor or TFT (a-Si-TFT, poly-Si- TFT). On the other hand, due to these thermal history, various physical properties (especially yellowness or elongation) of the polyimide film tend to decrease, and if it exceeds 400 ° C, the yellowness or elongation is particularly lowered. However, the polyimide film obtained from the polyimine precursor of the present invention has a small decrease in yellowness or elongation even in a high temperature region of 400 ° C or higher, and can be favorably used in this region. Further, in the present embodiment, a laminate comprising a polyimide film layer and an LTPS (low temperature polycrystalline TFT) layer containing a polyfluorene represented by the following formula (13) can be provided. Imine. [化31] {式,X ₁ It represents the four-valent base of carbon number 4 to 32. R ₁ , R ₂ , R ₃ Each of the organic groups having a carbon number of 1 to 20 is independently represented. n represents 0 or 1. And a, b, and c are integers of 0 to 4} As a method for producing the laminate, the polyimide and the polyimide resin film formed of the resin composition on the surface of the support are produced. After the laminate is formed, an amorphous Si layer is formed, and after dehydrogenation annealing at 400 to 450 ° C for about 0.5 to 3 hours, it is crystallized by excimer laser or the like to form an LTPS layer. Thereafter, the glass and the polyimide film are peeled off by laser peeling or the like, whereby the laminate can be obtained. The layered system comprising the polyimine film layer containing the polyimine and the LTPS (low temperature polycrystalline ruthenium TFT) layer represented by the general formula (13) has less peeling or squeezing after the thermal cycle test, and the substrate warpage is less. Further, when the residual stress generated in the flexible substrate and the polyimide film is high, the laminate containing both of them may be warped in the high-temperature TFT step, and may shrink when the film is shrunk at room temperature. And problems such as damage and peeling of the flexible substrate from the glass substrate. Usually, the glass substrate has a thermal expansion coefficient smaller than that of the resin, so that residual stress is generated between the glass substrate and the flexible substrate. As described above, the resin film of the present embodiment can be preferably used for the formation of a flexible display because the residual stress generated between the glass substrate and the glass substrate can be 25 MPa or less. Further, in the polyimide film of the present embodiment, the yellowness YI of the film thickness of 10 μm can be made 30 or less, and the tensile elongation can be 15% or more. As a result, the resin film of the present embodiment is excellent in breaking strength when the flexible substrate is processed, so that the yield when manufacturing a flexible display can be improved. Further, as another aspect, it is possible to provide an absorbance at 308 nm of 0.6 or less and a thickness of 0.1 or less at a film thickness of 0.1 μm after heating at 400 ° C or higher, and an elongation ratio of 0.6 or more and 2.0 or less. More than 15% of the polyimide film. By setting YI to 20 or less, a flexible substrate can be produced without deteriorating the image quality when the display is formed. More preferably 18 or less, and particularly preferably 16 or less. When the absorbance at 308 nm when the film thickness is 0.1 μm is 0.6 or more and 2.0 or less and the elongation is 15% or more, for example, the polyimide film can be easily peeled off from the glass substrate by laser irradiation. From the viewpoint of suppressing the dust after the laser peeling, it is preferably 0.6 or more and 1.5 or less and the elongation is 20% or more. For example, from the viewpoint of not lowering the performance of the organic EL element, it is preferably 0.6 or more and 1.0. Hereinafter, the elongation is 20% or more. The upper limit of the elongation is not particularly limited, and may be 80% or less, 70% or less, 60% or less, 50% or less, or 40% or less. Furthermore, when the laser is peeled off, the polyimide film may be burned due to the laser light, and the combustion residue is dust. Accordingly, another aspect of the present invention is to provide a display substrate. Still another aspect of the present invention provides a method of manufacturing the above display substrate. The method for producing a display substrate according to the present embodiment includes the steps of: forming a coating film by applying the resin composition on the surface of the support (coating step); by using the support and the coating described above a step of heating the film to imidize the polyamidene precursor contained in the coating film to form a polyimide film (heating step); forming a component or circuit on the polyimide film a step (component, circuit forming step); and a step of peeling the polyimine resin film on which the element or the circuit is formed from the support (peeling step). In the above method, the coating step, the heating step, and the peeling step can be carried out in the same manner as the above-described method of producing the resin film. The component and circuit forming steps can be carried out by methods known to those skilled in the art. The resin film of the present embodiment which satisfies the above physical properties can be preferably used for applications in which the use of the yellow color of the existing polyimide film is limited, especially for a colorless transparent substrate for a display or a color filter. Protective film and other uses. Further, it can also be used for, for example, a protective film, a astigmatic sheet such as a TFT-LCD, and a coating film (for example, an intermediate layer of a TFT-LCD, a gate insulating film, a liquid crystal alignment film, etc.), an ITO substrate for a touch panel, and a smart phone. It is used in place of a resin substrate covering a glass or the like which requires colorless transparency and low birefringence. When the polyimine of the present embodiment is applied as a liquid crystal alignment film, a TFT-LCD having a high aperture ratio and a high contrast ratio can be produced. The resin film and the laminate which are produced by using the polyimide precursor of the present embodiment and the resin precursor can be used as a semiconductor insulating film, a TFT-LCD insulating film, an electrode protective film, or the like, for example, in a soft device. It is particularly preferably used as a substrate in manufacturing. Here, examples of the soft device to which the resin film and the laminate of the present embodiment can be applied include a flexible display, a flexible solar cell, a flexible touch panel electrode substrate, a soft illumination, and a flexible battery. [Examples] Hereinafter, the present invention will be described in more detail with reference to the accompanying Examples. The various evaluations of the examples and comparative examples were carried out as follows. <Measurement of Weight Average Molecular Weight> The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) under the following conditions. As a solvent, N,N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatography, and added 24.8 mmol/L of lithium bromide monohydrate before the measurement (manufactured by Wako Pure Chemical Industries, Ltd.) , purity of 99.5%) and 63.2 mmol / L of phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatography) and dissolved). A calibration curve for calculating the weight average molecular weight was prepared using standard polystyrene (manufactured by Tosoh Corporation). Column: Shodex KD-806M (manufactured by Showa Denko Co., Ltd.) Flow rate: 1.0 mL/min Column temperature: 40 °C Pump: PU-2080Plus (manufactured by JASCO) Detector: RI-2031Plus (RI: differential refractometer, JASCO Manufactured and UV-2075Plus (UV-VIS: UV-Visible Absorber, manufactured by JASCO) <Evaluation of the molecular weight (low molecular weight content) of less than 1,000 molecular weight > The molecular weight of the resin in the resin of less than 1,000 Using the measurement results of the GPC obtained above, the peak area occupied by the component having a molecular weight of less than 1,000 was calculated as a ratio (percentage) occupied by the peak area of the entire molecular weight distribution. <Evaluation of the amount of water> The water content of the synthetic solvent and the resin composition (varnish) was measured using a Karl Fischer moisture measuring device (manual moisture measuring device AQ-300, manufactured by Hiranuma Sangyo Co., Ltd.). <Evaluation of Viscosity Stability of Resin Composition> For the resin compositions prepared in the examples and the comparative examples, a sample which was allowed to stand at room temperature for 3 days after preparation was used as a sample after preparation, and the viscosity at 23 ° C was carried out. The measurement was carried out, and the sample which was further allowed to stand at room temperature for 2 weeks was used as a sample after 2 weeks, and the viscosity measurement at 23 ° C was again performed. These viscosity measurements were carried out using a viscometer with a thermostat (TV-22 manufactured by Toki Machinery Co., Ltd.). Using the above measured values, the room temperature 2 week viscosity change rate was calculated by the following formula. 2 week viscosity change rate (%) = [(viscosity of sample after 2 weeks) - (viscosity of sample after preparation)] / (viscosity of sample after preparation) × 100 room temperature 2 weeks viscosity change rate It is evaluated according to the following criteria. ◎: The viscosity change rate is 5% or less (the storage stability is "excellent") ○: The viscosity change rate is more than 5 and 10% or less (storage stability is "good") ×: The viscosity change rate is more than 10% (storage stability) (Evaluation of varnish coating property) The resin composition prepared in each of the examples and the comparative examples was applied to an alkali-free glass substrate (size 37) after curing to a film thickness of 15 μm using a bar coater. ×47 mm, thickness 0.7 mm), pre-baked at 140 ° C for 60 minutes. The coating property of the varnish was evaluated by measuring the step of the surface of the coating film using a surface profiler (manufactured by Tencor Corporation, model name P-15). ◎: The step of the surface is 0.1 μm or less (the coating property is "excellent") ○: The step of the surface is more than 0.1 and 0.5 μm or less (the coating property is "good") ×: The step of the surface is more than 0.5 μm (coating) Cloth "bad") <Evaluation of residual stress> Each of the resin compositions was applied by a spin coater on a 6-inch wafer having a thickness of 625 μm ± 25 μm in which the amount of warpage was measured in advance. Pre-bake at 100 ° C for 7 minutes. Thereafter, a vertical curing oven (manufactured by Koyo Lindberg Co., Ltd., model name VF-2000B) was used, and the oxygen concentration in the chamber was adjusted to 10 ppm by mass or less, and the heat curing treatment was performed at 430 ° C for 1 hour. Treatment) A tantalum wafer with a polyimide film having a film thickness of 10 μm after hardening was produced. The amount of warpage of the wafer was measured using a residual stress measuring device (manufactured by Tencor Corporation, model name FLX-2320), and the residual stress generated between the tantalum wafer and the resin film was evaluated. ◎: The residual stress exceeds -5 and is 15 MPa or less (the evaluation of residual stress is "excellent") ○: The residual stress exceeds 15 and is 25 MPa or less (the evaluation of residual stress is "good") ×: The residual stress exceeds 25 MPa (residual Evaluation of stress "Poor") <Evaluation of warpage of polyimide film formed with inorganic film> The resin composition prepared in each of the examples and the comparative examples was spin-coated so that the film thickness after hardening became 10 μm. It was pre-baked at 100 ° C for 7 minutes on a 6-inch wafer substrate provided with an aluminum vapor-deposited layer. Then, using a vertical curing oven (manufactured by Koyo Lindberg Co., Ltd., model name VF-2000B), the oxygen concentration in the chamber was adjusted to 10 ppm by mass or less, and the heat curing treatment was performed at 430 ° C for 1 hour. A wafer in which a polyimide film is formed. Using the wafer, a tantalum nitride (SiNx) film as an inorganic film was formed on a polyimide film by a CVD (chemical vapor deposition) method at 350 ° C at a thickness of 100 nm. A laminate wafer having an inorganic film/polyimine resin is formed. The laminate wafer obtained above is immersed in a dilute hydrochloric acid aqueous solution, and two layers of the inorganic film and the polyimide film are integrally peeled off from the wafer, thereby obtaining a polyimide film having an inorganic film formed on the surface thereof. Sample. Using this sample, the warpage of the polyimide film was evaluated. ◎: No warp (warp "excellent") ○: only a small amount of warp (warp "good") ×: film curl due to warpage (warpage "bad") <yellowness (YI) Evaluation of Values> Wafers were produced in the same manner as in the above <Evaluation of warpage of the polyimide film formed with an inorganic film> (in which an inorganic film was not formed). The wafer was immersed in a dilute hydrochloric acid aqueous solution, and the polyimide film was peeled off, whereby a resin film was obtained. With respect to the obtained polyimine resin film, a YI value (converted to a film thickness of 10 μm) was measured by a D65 light source manufactured by Nippon Denshoku Industries Co., Ltd. (Spectrophotometer: SE600). <Evaluation of Elongation and Breaking Strength> A wafer was produced in the same manner as in the above <Evaluation of Warpage of Polyimide Resin Film Formed with Inorganic Film> (in which an inorganic film was not formed). Using a wafer dicing machine (DAD3350 manufactured by DISCO Co., Ltd.), a 3 mm wide cut was cut into the polyimide film of the wafer, and then immersed in a dilute hydrochloric acid aqueous solution to peel off the resin film. dry. It was cut to a length of 50 mm as a sample. For the above samples, elongation and breaking strength were measured using TENSILON (UTM-II-20 manufactured by Orientec Co., Ltd.) at a test speed of 40 mm/min and an initial weighting of 0.5 fs. <Measurement of Absorbance at 308 nm of Polyimide Resin Film> The varnish was spin-coated on a quartz glass substrate, and heated at 430 ° C for 1 hour under a nitrogen atmosphere, thereby obtaining a polyimide having a film thickness of 0.1 μm. Amine resin film. For these polyimide membranes, the absorbance at 308 nm was measured using UV-1600 (manufactured by Shimadzu Corporation). [Example 1] A nitrogen-substituted 500 ml separable flask was charged with 96 g of N-methyl-2-pyrrolidone (NMP), and charged with 4-aminophenyl-4-aminobenzoic acid. The ester (APAB) 17.71 g (77.6 mmol) and 4,4'-diaminodiphenylphosphonium (DAS) 4.82 g (19.4 mmol) were stirred to dissolve APAB and DAS. Thereafter, 29.42 g (100 mmol) of biphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA) was added, and polymerization was carried out under a nitrogen gas flow and stirring at 80 ° C for 3 hours. Thereafter, the mixture was cooled to room temperature, and the above-mentioned NMP was added to adjust the viscosity of the solution to 51,000 mPa·s, thereby obtaining a polyacrylic acid NMP solution (hereinafter also referred to as varnish) P-1. The obtained polyaminic acid had a weight average molecular weight (Mw) of 65,000. [Examples 2 to 21 and Comparative Examples 1 to 5] In the above-described Example 1, except that the amount of the raw material (the molar ratio), the type of the solvent to be used, the polymerization temperature, and the polymerization time were changed as described in Table 1, respectively. Varnishes P-2 to P-26 were obtained in the same manner as in Example 1. The weight average molecular weight (Mw) of the polyamic acid contained in each varnish is collectively shown in Table 1. [Table 1] The abbreviations of the components in Table 1 respectively mean the following meanings. BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride PMDA: pyromellitic dianhydride TAHQ: p-phenylene bis(trimellitic anhydride) APAB: 4-aminophenyl-4 -Aminobenzoate ATAB: 2-methyl-4-aminophenyl-4-aminobenzoic acid BABB: [4-(4-Aminobenzylidene)oxyphenyl]4 -Aminobenzoate BAFL: 9,9-bis(aminophenyl)anthracene BFAF: 9,9-bis(4-amino-3-fluorophenyl)anthracene TFMB: 2,2'-double ( Trifluoromethyl)benzidine DAS: 4,4'-diaminodiphenylhydrazine NMP: N-methyl-2-pyrrolidone DMF: N,N-dimethylformamide DMAc: N, N -Dimethylacetamide The varnishes P-1 to P-26 obtained in the above Examples and Comparative Examples were directly used as a resin composition, and evaluated according to the above method. The evaluation results are shown in Table 2. [Table 2] * indicates that the film is brittle and cannot be measured. ** indicates that it is impossible to measure due to film whitening. As shown in Tables 1 and 2, the polyphenylene obtained in Comparative Examples 1 and 2 containing only the structural unit represented by the general formula (1) The amine film is brittle, and physical properties such as elongation cannot be evaluated. Moreover, the residual stress also becomes a higher result. Further, the polyimine film obtained in Comparative Example 3 containing only the structural unit represented by the general formula (2) had a high residual stress, and warpage occurred after the formation of the inorganic film, and the elongation was also low. On the other hand, the polyimine obtained in Examples 1 to 21 in which the structural unit represented by the formula (1) and the structural unit represented by the formula (2) are contained in the molar ratio of 99/1 to 1/99 The film system has a yellowness of less than 20, a residual stress of 25 MPa or less, and an elongation of 20% or more. Further, warpage after the formation of the inorganic film was not caused, or even if it occurred, it was only a small amount. As a result of the above-mentioned Table 2, it was confirmed that the polyimine resin film obtained from the resin composition of the present invention is a resin film having a small yellowness, a low residual stress, and excellent mechanical properties. Specifically, in the present invention, a resin film having a residual stress of 25 MPa or less, a yellowness YI of 30 or less, and an elongation of 15% or more can be obtained. [Example 22] N-methyl-2-pyrrolidone (NMP) (water content: 250 mass ppm) was added to nitrogen gas immediately after opening from a 18 L tank in an amount equivalent to 17 wt% of the solid content. In a 500 ml separable flask, a 5-aminophenyl-4-aminobenzoate (APAB, purity: 99.5%, manufactured by Nippon Pure Pharmaceutical Co., Ltd.), 5.71 g (25.0 mmol) was added. Stir and dissolve APAB. Thereafter, biphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA, purity 99.5%, manufactured by MANAC Co., Ltd.) 7.36 g (25.0 mmol) was added, and the mixture was passed under nitrogen at 80 ° C. The polymerization was carried out under stirring for 3 hours. Thereafter, the mixture was cooled to room temperature, and the above-mentioned NMP was added so as to adjust the viscosity of the solution to 51,000 mPa·s to obtain a polyphosphonic acid NMP solution (hereinafter also referred to as varnish) P-27. The obtained polyaminic acid had a weight average molecular weight (Mw) of 128,000 and a molecular weight of less than 1,000. The content of the molecule was 0.01% by mass. [Examples 23 to 33 and Comparative Examples 6 to 11] In the above-described Example 22, the types of the raw materials, the amount of the raw materials, the type of the solvent to be used, the polymerization temperature, and the polymerization time were changed as described in Table 3, respectively. Varnishes P-28 to P-44 were obtained in the same manner as in Synthesis Example 1. The weight average molecular weight (Mw) of the polyamic acid contained in each varnish is shown together in Table 3. [table 3] The abbreviations of the components in Table 3 respectively mean the following meanings. BPDA: biphenyltetracarboxylic dianhydride, purity 99.5%, manufactured by Mitsubishi Chemical Corporation TAHQ: p-phenylene bis(trimellitic anhydride), purity 99.5%, manufactured by MANAC Co., Ltd. PMDA: pyromellitic acid II Anhydride APAB: 4-aminophenyl-4-aminobenzoate, purity 99.5% 4,3-APAB: 4-aminophenyl-3-aminobenzoate, purity 99.5% ATAB: 2 -Methyl-4-aminophenyl-4-aminobenzoate BABB: [4-(4-Aminobenzylidene)oxyphenyl]4-aminobenzoate NMP1:18 Immediately after the L can is opened, the user will have a water content of 250 ppm. NMP2: After opening the 500 ml bottle for one month, the water content is 3,070 ppm DMF: the 500 ml bottle is opened, the water is 3510 ppm DMAc: 500 ml bottle The latter was opened, and the amount of water was 3,430 ppm. [Examples 22 to 33 and Comparative Examples 6 to 11] The varnishes P-27 to P-44 obtained in the above Examples and Comparative Examples were directly used as a resin composition, and were subjected to the above method. Evaluation. The evaluation results are shown in Table 4. [Table 4] As shown in Tables 3 and 4, Comparative Example 6 (P-39), Comparative Example 7 (P-40), and Comparative Example 8 in which the weight average molecular weight of the polyimide intermediate (varnish) was 3,000 or less. In (P-41), Comparative Example 10 (P-43), and Comparative Example 11 (P-44), the residual stress was large and the warpage was large. Also, the yellowness is large, and the elongation and breaking strength are also small. In Comparative Examples 10 and 11 in which the amount of water was large, the film was very brittle. On the other hand, in Comparative Example 9 (P-42) in which the weight average molecular weight of the polyimide intermediate precursor was 30,000 or more, residual stress, warpage was small, yellowness was low, and elongation and breaking strength were also Larger, but the coating properties are worse. On the other hand, in Examples 22 to 33 in which the polyiminoimine precursors P-27 to P-38 having a weight average molecular weight of 30,000 or more and 300,000 or less were used, the residual stress was low and the warpage was small, yellow. The degree is low, the elongation and the breaking strength are also large, and excellent results are obtained for any of the characteristics. As a result of the above-mentioned Table 4, it was confirmed that the polyimine resin film obtained from the resin composition of the present invention is a resin film having a small yellowness, a low residual stress, and excellent mechanical properties. Specifically, in the present invention, a resin film having a residual stress of 25 MPa or less, a yellowness YI of 20 or less, a glass transition temperature of 400 ° C or more, an elongation of 15% or more, and a breaking strength of 250 MPa or more can be obtained. In the examples 34 to 45 which were disclosed, an experiment was conducted in which the effect of adding at least one selected from the group consisting of a surfactant and an alkoxysilane compound to the resin composition was carried out. [Example 34] First, the varnish P-27 obtained in the above Example 22 was directly used as a resin composition, and evaluation of coating streaks was carried out in the following order. <Evaluation of Coating Stripe (Coating Property)> The above resin composition was applied to an alkali-free glass substrate (size 37 × 47 mm, thickness 0.7 mm) by a bar coater so as to have a film thickness of 15 μm after curing. )on. After the application, the mixture was allowed to stand at room temperature for 10 minutes, and it was visually confirmed whether or not coating streaks were formed on the obtained coating film. The coating was performed three times using the same resin composition, and the number of the coating stripes was examined for each coating film, and the average value was used and evaluated based on the following criteria. ◎: The number of continuous application stripes of 1 mm or more and 1 mm or more in length was 0 (the evaluation of the coating stripe was "excellent") ○: The coating stripe was 1 or 2 (the evaluation of the coating stripe was "good") △: The number of the application stripes was 3 to 5 (the evaluation of the coating stripe was "may"). The evaluation results are shown in Table 5. [Examples 35 to 45] After adding the surfactant and alkoxydecane compound of the type and amount shown in Table 5 as an additional additive to the varnish P-27 obtained in the above Example 22, respectively, 0.1 The filter of μm was filtered to prepare a resin composition. Evaluation of coating streaks was carried out in the same manner as in Example 34 using the above resin composition. The results are shown in Table 5. [table 5] The abbreviations of the components in Table 5 respectively mean the following meanings. The amounts of the components used in Table 5 are respectively based on the amount (usage amount) of 100 parts by mass of the polyimine precursor contained in the varnish. In Examples 39 and 45, Surfactant 1 was used in combination with alkoxydecane compound 1. Surfactant 1: DBE-821, product name, polyoxo-based surfactant, Gelest manufacture surfactant 2: MEGAFAC F171, product name, fluorine-based surfactant, DIC to manufacture alkoxydecane compound 1: Alkoxydecane compound 2 represented by the formula (AS-1): a compound represented by the following formula (AS-2) [Chem. 32] As shown in Table 5, in Examples 35 to 39 and Examples 41 to 45 containing a surfactant or alkoxydecane compound, the production of coating stripes was compared with Examples 34 and 40 which were not contained. When it is suppressed, the polyimine resin film excellent in surface smoothness can be obtained. [Example 46] After applying varnish P-27 to a non-alkali glass substrate (size: 37 × 47 mm, thickness: 0.7 mm) by a bar coater at a film thickness of 10 μm after curing, at 140 ° C Pre-bake for 60 minutes. Then, a vertical curing oven (manufactured by Koyo Lindberg Co., Ltd., model name VF-2000B) was used, and the oxygen concentration in the chamber was adjusted to 10 ppm by mass or less, and the heat curing treatment was performed at 430 ° C for 1 hour. A glass substrate of a polyimide film. An amorphous germanium layer was formed on the polyimide film, and dehydrogenation annealing was performed at 430 ° C for 1 hour, followed by irradiation of an excimer laser, thereby forming an LTPS layer. The glass substrate was peeled off by an excimer laser (wavelength 308 nm, repetition frequency 300 Hz) to obtain a laminate including a polyimide film and an LTPS layer. The laminate has no warpage and the yellowness is also 20 or less. [Example 47] A laminate was obtained in the same manner as in Example 46 except that varnish P-1 was used. The laminate has no warpage and the yellowness is also 20 or less. [Comparative Example 12] A laminate was obtained in the same manner as in Example 46 except that varnish P-24 was used. The laminate has a large warpage and a part of the polyimide film is cracked. [Synthesis Example] In a separable flask equipped with a Dean-Stark apparatus and a reflux vessel, APAB 2.24 g (9.8 mmol), NMP 16.14 g, and toluene 50 g were placed under a nitrogen atmosphere, and stirred under stirring. APAB is dissolved. H-PMDA 2.24 g (10.0 mmol) was added thereto, and after refluxing at 180 ° C for 2 hours, toluene as an azeotropic solvent was removed over 3 hours. The contents of the flask were cooled to 40 ° C and confirmed by IR to be 1,650 cm derived from the indole bond. ^-1 The nearby absorption (C=O) disappears. Thereafter, APAB 8.95 g (39.2 mmol), NMP 121.6 g, PMDA 6.54 g (30.0 mmol) and 6FDA 4.44 g (10.0 mmol) were added and stirred at 80 ° C for 4 hours, thereby obtaining polyimine-polyamide. Acid polymer varnish (P-45). The weight average molecular weight (Mw) of the obtained polyimine-polyamide polymer was 82,000. [Examples 48 to 53 and Comparative Example 13] An organic EL substrate shown in Fig. 1 was produced. The polytheneimide precursor varnish (P-1, P-11, P-20, P-22, P-27, P-33, P-45) was cured to a thickness of 10 by a bar coater. After coating on a plain glass substrate (thickness 0.7 mm) in a manner of μm, it was prebaked at 140 ° C for 60 minutes. Then, a vertical curing oven (manufactured by Koyo Lindberg Co., Ltd., model name VF-2000B) was used, and the oxygen concentration in the chamber was adjusted to 10 ppm by mass or less, and the heat curing treatment was performed at 430 ° C for 1 hour. A glass substrate of a polyimide film. The SiN layer was then formed into a film by a CVD (Chemical Vapor Deposition) method at a thickness of 100 nm. Titanium is then formed by sputtering, and then patterned by photolithography to form a scanning signal line. Next, the SiN layer was formed into a film by a CVD method at a thickness of 100 nm over the entire glass substrate on which the scanning signal lines were formed. (The lower substrate 2a is thus regarded as the lower substrate 2a.) Next, an amorphous germanium layer 256 is formed on the lower substrate 2a, and dehydrogenation annealing is performed at 430 ° C for 1 hour, followed by irradiation of an excimer laser to form an LTPS layer. Thereafter, a photosensitive acrylic resin is applied onto the entire surface of the lower substrate 2a by a spin coating method, and exposed and developed by photolithography to form 258 having a plurality of contact holes 257. A state in which one of the LTPSs 256 is partially exposed by the contact hole 257 is obtained. Next, an ITO film is formed on the entire surface of the lower substrate 2a on which the interlayer insulating film 258 is formed by sputtering, and exposed and developed by photolithography, and patterned by etching to form LTPS. The lower electrode 259 is formed in a paired manner. Further, in each of the contact holes 257, the lower electrode 252 of the interlayer insulating film 258 is electrically connected to the LTPS 256. Next, after the partition walls 251 are formed, the hole transport layer 253 and the light-emitting layer 254 are formed in the respective spaces partitioned by the partition walls 251. Further, the upper electrode 255 is formed to cover the light-emitting layer 254 and the partition wall 251. The organic EL substrate 25 was produced by the above steps. Next, the ultraviolet curable resin is applied to the periphery of the sealing substrate 2b in which the glass substrate, the polyimide film of the present embodiment and the SiN layer are sequentially formed, and the sealing substrate 2b and the organic EL substrate are bonded in an argon atmosphere. This encapsulates the organic EL element. Thereby, the hollow portion 261 is formed between each of the organic EL elements and the sealing substrate 2b. The excimer laser (wavelength 308 nm, repetition frequency 300 Hz) was irradiated to the side of the lower substrate 2a and the side of the sealing substrate 2b thus formed, and the minimum energy required to peel off the entire surface was peeled off. Evaluation of the presence or absence of the substrate warpage, the lighting test, and the white turbidity evaluation of the laminate after peeling the laminate. In addition, a thermal cycle test was also carried out. The results are shown in Table 6. <Base warpage> ◎: No warp ○: Only a small amount of warpage △: Curl due to warpage <Lighting test> ○: Lighted person ×: Unlit person < Evaluation of white matter of laminated body> Formation After the laminate is formed, the whole device is regarded as transparent as ○, the slightly opaque person is regarded as Δ, and the white opaque person is regarded as ×. <Thermal Cycle Test> Using a thermal cycle tester manufactured by Espec, 1000 cycles of each of -5 ° C and 60 ° C for 30 minutes (the movement time of the groove was 1 minute) were subjected to an appearance observation. Those who did not peel or bulge were regarded as ○, and only a part of the peeling or bulging was observed as Δ after the test, and the whole peeling or bulging was observed as × after the test. [Table 6] [Examples 54 to 58 and Comparative Example 14] The above was carried out using a polyimide polyimide precursor varnish (P-1, P-11, P-20, P-22, P-27, P-33, P-45). In the production of the laminate, the above test was carried out except that the laminate was produced by changing the LTPS to IGZO. The results are shown in Table 7. [Table 7] [Examples 59 to 63 and Comparative Example 15] A polyimide film varnish having an absorbance at 308 nm of not less than 20 and a film thickness of 0.1 μm of 0.6 or more and 2.0 or less and an elongation of 15% or more was provided ( P-1, P-11, P-20, P-27, P-33, P-45), the minimum energy required for laser stripping when the above laser is peeled off and the minimum energy plus 10 mJ/cm ² The obtained energy was evaluated for dust (ash) at the time of irradiation. A person who does not generate dust at all is regarded as ○, a person who observes a small amount of dust is regarded as Δ, and a person who observes dust as a whole is regarded as ×. The results are shown in Table 8. [Table 8] The present invention is not limited to the above-described embodiments, and various modifications may be made without departing from the spirit and scope of the invention. [Industrial Applicability] The resin film formed of the polyimide precursor of the present invention can be used for the manufacture of a flexible display, for example, in addition to a semiconductor body insulating film, a TFT-LCD insulating film, an electrode protective film, or the like. The substrate for a touch panel ITO electrode or the like is particularly preferably used as a substrate.

2a‧‧‧lower substrate
2b‧‧‧Seal substrate
25‧‧‧Organic EL substrate
251‧‧‧ partition wall
252‧‧‧ lower electrode
253‧‧‧ hole transport layer
254‧‧‧Lighting layer
255‧‧‧Upper electrode
256‧‧‧Amorphous layer
257‧‧‧Contact hole
258‧‧‧Interlayer insulating film
259‧‧‧lower electrode
261‧‧‧ Hollow

Fig. 1 is a view showing the structure of an organic EL (Electroluminescence) substrate produced in Examples and Comparative Examples.

no

Claims (21)

A polybendimimine precursor characterized by being a (a1) polyimine precursor having a molar ratio of 1/99 ≦ (molar number of structural unit L / molar number of structural unit M) ≦ 99/1 Contains: Structural unit L represented by the following general formula (1): [Chemical Formula 1] Wherein X ₁ represents a tetravalent group having a carbon number of 4 to 32; and R ₁ , R ₂ and R ₃ each independently represent an organic group having a carbon number of 1 to 20; n represents 0 or 1; b and c are integers of 0 to 4}; and structural unit M represented by the following general formula (2): [Chemical 2] In the formula, X ₂ represents a tetravalent group having a carbon number of 4 to 32; and Y is at least one selected from the group consisting of the following general formulae (3), (4), and (5)}, [Chemical 3 ] [Chemical 4] [Chemical 5] In the formula, R ₄ to R ₁₁ each independently represent an organic group having a carbon number of 1 to 20; and d to k are an integer of 0 to 4}. The polyimine precursor of claim 1, wherein n in the above formula (1) is 0. The polyimine precursor of claim 1 or 2, wherein Y of the above formula (2) is the formula (3). The polyimine precursor of claim 1 or 2, wherein Y of the above formula (2) is the formula (4). The polyimine precursor of claim 1 or 2, wherein Y of the above formula (2) is a formula (5). A polyimine precursor which is characterized in that it is a (a2) polyimine precursor comprising a structural unit represented by the following formula (10): [Chem. 6] Further, the weight average molecular weight is 30,000 or more and 300,000 or less, wherein X ₃ represents a source derived from 4,4'-oxydiphthalic dianhydride (ODPA), biphenyltetracarboxylic dianhydride (BPDA). And a tetravalent group of at least one of the group consisting of 4,4'-biphenyl bis(trimellitic acid monoester anhydride) (TAHQ); R ₁ , R ₂ and R ₃ each independently represent a carbon number of 1 to 20 an organic group of one valence; n represents 0 or 1; and a, b and c are integers of 0 to 4}. The polyamidiamine precursor according to claim 6, wherein the content of the molecule having a weight average molecular weight of less than 1,000 in the (a2) polyamidene precursor is less than 5% by mass. The polyamidiene precursor of claim 6 or 7, wherein n in the formula (10) is 0. The polyimine precursor according to any one of claims 1 to 5, wherein the above X ₁ , X ₂ are derived from pyromellitic dianhydride (PMDA), 4,4′-oxydi-phthalic acid Tetravalent at least one of a group consisting of formic acid dianhydride (ODPA), biphenyltetracarboxylic dianhydride (BPDA), and 4,4'-biphenyl bis(trimellitic acid monoester anhydride) (TAHQ) Organic base. A resin composition characterized by containing the polyimine precursor of any one of claims 1 to 9 and (b) an organic solvent. The resin composition of claim 10, which further contains at least one selected from the group consisting of (c) a surfactant and (d) an alkoxydecane compound. A polyimine which is characterized by containing a structural unit represented by the following formula (11): [Chem. 7] Wherein X ₁ and X ₂ represent a tetravalent group having a carbon number of 4 to 32; and R ₁ , R ₂ and R ₃ each independently represent an organic group having a carbon number of 1 to 20; n represents 0 or 1; And a, b and c are integers of 0 to 4; Y is at least one selected from the group consisting of the following general formulae (3), (4) and (5); and l and m each independently represent 1 or more. Integer, satisfying 0.01≦l/(l+m)≦0.99}, [Chem. 8] [Chemistry 9] [化10] In the formula, R ₄ to R ₁₁ each independently represent an organic group having a carbon number of 1 to 20; and d to k are an integer of 0 to 4}. A polyimine which is characterized by containing a structural unit represented by the following formula (12): [Chem. 11] Wherein X ₃ represents a source derived from 4,4'-oxydiphthalic dianhydride (ODPA), biphenyltetracarboxylic dianhydride (BPDA), and 4,4'-biphenyl bis(phenylene) a tetravalent group of at least one of the group consisting of tricarboxylic acid monoester anhydride) (TAHQ); R ₁ , R ₂ , and R ₃ each independently represent an organic group having one carbon number of 1 to 20; n represents 0 or 1; and a, b, and c are integers of 0 to 4}, and the elongation is 15% or more. A method for producing a resin film, comprising the steps of: forming a coating film by coating a resin composition of claim 10 or 11 on a surface of a support; by using the above support and the above a step of heating the coating film to imidize the polyamidene precursor contained in the coating film to form a polyimide film; and removing the polyimine resin film from the support . The method for producing a resin film according to claim 14, wherein the step of irradiating the laser from the support side is performed before the step of peeling the polyimide film from the support. A method for producing a laminate, comprising the steps of: forming a coating film by coating a resin composition as claimed in claim 10 or 11 on a surface of a support; and by using the above support and The coating film is heated to imidize the polyimine precursor precursor contained in the coating film to form a polyimide film. A method of manufacturing a display substrate, comprising the steps of: forming a coating film by coating a resin composition as claimed in claim 10 or 11 on a surface of a support; by using the above support and the above a step of heating the coating film to imidize the polyimine precursor precursor contained in the coating film to form a polyimide film; forming a component or a circuit on the polyimide film; And a step of peeling the polyimine resin film on which the element or the circuit is formed from the support. A polyimide film for display, which comprises a polyimine represented by the following formula (12): [Chemical 12] Wherein X ₃ is selected from the group consisting of 4,4'-oxydiphthalic dianhydride (ODPA), biphenyltetracarboxylic dianhydride (BPDA), and 4,4'-biphenyl bis(trimellitic acid). At least one of the group consisting of monoester anhydrides (TAHQ), R ₁ , R ₂ , and R ₃ each independently represent an organic group having one carbon number of 1 to 20; n represents 0 or 1; and a, b and c is an integer from 0 to 4. A laminate comprising a polyimide film layer and a low temperature polysilicon TFT layer, wherein the polyimide film layer comprises a polyimine represented by the following formula (13): [Chem. 13] Wherein X ₁ represents a tetravalent group having a carbon number of 4 to 32; and R ₁ , R ₂ and R ₃ each independently represent an organic group having a carbon number of 1 to 20; n represents 0 or 1; b and c are integers from 0 to 4}. A polyimide film having a film thickness of 10 μm and a yellowness of 20 or less after heating at 400 ° C or higher, and an absorbance at 308 nm of a film thickness of 1 μm of 0.6 or more and 2.0 or less, and an elongation ratio. More than 15%. A resin composition comprising: (a) a polyimine precursor represented by the following formula (1), (b) an organic solvent, and selected from the group consisting of (c) a surfactant and (d) At least one of the group consisting of alkoxydecane compounds, [Chem. 14] Wherein X ₁ represents a tetravalent group having a carbon number of 4 to 32; and R ₁ , R ₂ and R ₃ each independently represent an organic group having a carbon number of 1 to 20; n represents 0 or 1; b and c are integers from 0 to 4}.