TWI650349B - Polyimide resin film and electronic device substrate comprising polyimide resin film - Google Patents

Abstract

An object of the present invention is to provide a polyimide film having a heat resistance, a low coefficient of linear expansion, and high transparency.

The solution of the present invention is a polyimine resin film comprising a polyimine resin containing a structural unit represented by the following formula (1); (wherein A represents at least one selected from the group consisting of a divalent organic group represented by the following formula (2) or (3), and R ¹ to R ³ each independently represent a hydrogen atom and an alkyl group having 1 to 10 carbon atoms; Or a haloalkyl group having 1 to 10 carbon atoms, m represents a natural number);

Description

Polyimide resin film and substrate for electronic device made of polyimide film

The present invention relates to a polyimide film for electronic device materials and a substrate for an electronic device made of a polyimide film.

In recent years, in the fields of displays such as liquid crystal (TFT), solar cells, and lighting fixtures, substrates used for these are required to be thinner, lighter, and flexible, and thus are used instead of the prior art. A rigid film substrate such as a glass substrate used in the field is expected to be thinner, lighter, and flexible.

Generally, the substrate used for a display, a solar cell, and a lighting fixture is required to have characteristics such as heat resistance, transparency, dimensional stability (low linear expansion coefficient, etc.).

For example, in the field of displays, in the past, in high-definition displays, active matrix driven panels were used. In addition to the matrix-shaped pixel electrode, when an active matrix layer containing a thin film active device is formed, it is required at the time of manufacture. High temperature program above 200 °C, and must be exactly aligned. However, when the substrate is changed from glass to plastic material in order to reduce the thickness, weight, and flexibility of the display, it is more difficult to satisfy heat resistance and dimensional stability than in the past, and it is extremely difficult to form the active element directly therein. on. Further, when light emitted from the display element is emitted through the plastic substrate (for example, a bottom emission type organic EL or the like), the plastic film substrate must have high transparency comparable to that of the glass substrate.

At present, materials for plastic film substrates that can satisfy the above requirements are still unknown and are under discussion.

Nowadays, as a material that satisfies the above requirements, a polyimine resin film has been examined. Among the polyimine resins proposed in the past, those who are considered to be suitable for the use of the material are, for example, the following examples.

In Patent Document 1 and Patent Document 2, a polyimine resin for a liquid crystal alignment film of a diamine component using trifluoromethylbenzidine (hereinafter also referred to as TFMB) as a raw material is described.

Further, Patent Document 3 describes an acid dianhydride component using 3,3',4,4'-biphenyltetracarboxylic dianhydride as a raw material, and TFMB as a diamine component.

Further, Patent Document 4 describes a polyimine which uses an alicyclic monomer as an acid dianhydride component.

Prior technical literature Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2004-252373

Patent Document 2: Japanese Laid-Open Patent Publication No. 2004-46065

Patent Document 3: Japanese Laid-Open Patent Publication No. 2007-046054

Patent Document 4: International Publication No. 2009/093711

However, in the polyimine disclosed in Patent Document 1 and Patent Document 2, solubility, coloring property, and birefringence are clearly described. However, it is assumed that the liquid crystal alignment film is used, and other heat resistance, linear expansion coefficient, and the like are used. The characteristics are not clearly stated.

In the polyimine film described in Patent Document 3, in a polyimide film obtained by general thermal imidization, a light transmittance of 380 nm at a film thickness of 3 mils (=75 μm) is relatively Preferably, 78% has a coefficient of linear expansion of 38 ppm/K. On the other hand, in the polyimide film obtained by chemical imidization, the coefficient of linear expansion is a low -3 ppm/K, light. The penetration (380 nm) was a lower 76% (film thickness 3 mils).

Further, in the polyimine disclosed in Patent Document 4, the polyaminic acid as a polyimide precursor is inferior in polymerization reactivity, and it is difficult to obtain a high molecular weight body which exhibits sufficient film toughness, and thus it is difficult to obtain. Polyimine with high heat resistance and dimensional stability.

Thus, it has been previously proposed that either or both of the acid dianhydride and the diamine of the starting material use various alicyclic imines of the alicyclic monomer or the fluorine-containing monomer, but in the prior poly-imine Among them, those who can sufficiently satisfy all the required characteristics of heat resistance, low linear expansion coefficient, and transparency have not been found.

The present invention has been made in view of the above circumstances, and an object of the invention is to provide a substrate for a display such as a liquid crystal (TFT) for thinning, weight reduction, and flexibility, a substrate for a solar cell, and a substrate for a lighting fixture. A polyimine resin film which is a heat resistance and a low coefficient of linear expansion which is necessary, and a polyimine resin film which further has high transparency in addition to the desired characteristics, and the polyimine A substrate for an electronic device made of a resin film, a method for producing a substrate for an electronic device, a resin solution for coating used in a method for producing a substrate for an electronic device, and a polysiloxane comprising the polyimide film. amine.

The inventors of the present invention have conducted intensive studies to achieve the above object, and have found that a film composed of the following polyimide resin has sufficient film strength and has heat resistance required in a TFT forming process, and can be realized. Surprisingly high transparency, low linear expansion coefficient, low warpage and softness, thus completing the present invention, the polyimine is used in the field of display substrates due to problems of reactivity or heat resistance so far. An alicyclic tetracarboxylic dianhydride to be avoided, particularly bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride (hereinafter also referred to as BODA) as an acid The anhydride component and the divalent aromatic diamine, in particular, a halogenated alkyl group in the phenyl ring, particularly an aromatic diamine having a trifluoromethyl group as a diamine component.

That is, the first aspect of the present invention relates to a polyimine resin film comprising a polyimine resin containing a structural unit represented by the following formula (1); (wherein A represents at least one selected from the group consisting of a divalent organic group represented by the following formula (2) or (3), and R ¹ to R ³ each independently represent a hydrogen atom and an alkyl group having 1 to 10 carbon atoms; Or a haloalkyl group having 1 to 10 carbon atoms, m represents a natural number);

The second aspect is the polyimine resin film according to the first aspect, wherein the R ¹ to R ³ each independently represent a haloalkyl group having 1 to 10 carbon atoms.

The third aspect is the polyimine resin film according to the second aspect, wherein the A represents at least one selected from the group consisting of the divalent organic groups represented by the following formulas (4) to (6);

The fourth aspect is the polyimine resin film according to the third aspect, wherein the A represents a divalent organic group represented by the above formula (4).

The polyimine resin film according to any one of the first aspect to the fourth aspect, wherein the polyimine resin further contains a structural unit represented by the following formula (7); (wherein A' represents at least one selected from the group consisting of divalent organic groups represented by the following formula (8) or formula (9), and R ⁴ to R ⁶ independently of each other represent a hydrogen atom or an alkane having 1 to 10 carbon atoms; Base, m' represents a natural number);

The sixth aspect of the invention relates to the polyimine resin film according to the fifth aspect, wherein the A' represents a divalent organic group represented by the above formula (9).

The seventh aspect of the present invention relates to the polyimine resin film according to any one of the first aspect to the sixth aspect, which further comprises a structural unit represented by the following formula (10); (In the formula, B represents a divalent aromatic group or an aliphatic group, and n represents a natural number).

The eighth aspect of the invention relates to the polyimine resin film according to the seventh aspect, wherein the B represents at least one selected from the group consisting of a divalent aromatic group represented by the following formula (11) or (12); (wherein R ⁷ to R ⁹ independently of each other represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms).

The ninth aspect is the polyimine resin film according to the eighth aspect, wherein the aforementioned R ⁷ to R ⁹ represent a haloalkyl group having 1 to 10 carbon atoms.

The tenth aspect is the polyimine resin film according to the ninth aspect, wherein the B represents at least one selected from the group consisting of divalent aromatic groups represented by the following formulas (13) to (15);

The eleventh aspect is the polyimine resin film according to the tenth aspect, wherein the B represents a divalent aromatic group selected from the formula (13).

The twelfth point is about any one of the first to eleventh points. The polyimine resin film, wherein the polyimine resin is formed by chemically imidating a polyimide precursor.

The polyimine resin film according to any one of the first aspect to the twelfth aspect, wherein the light transmittance at a wavelength of 400 nm is 70% or more.

The 14th aspect of the present invention relates to the polyimide film of any one of the first aspect to the twelfth aspect, wherein the linear expansion coefficient is 60 ppm/K or less.

The fifteenth aspect is the polyimine resin film according to the fourteenth aspect, wherein the coefficient of linear expansion is from 5 ppm/K to 35 ppm/K.

The sixteenth aspect relates to a substrate for an electronic device, which is obtained from the polyimide film of any one of the first aspect to the fifteenth aspect.

The substrate for an electronic device according to the sixteenth aspect, wherein the substrate is for a TFT, a display, a solar cell, or a lighting fixture.

The ninth aspect is the substrate for an electronic device according to the seventeenth aspect, wherein the substrate is a display.

The ninth aspect relates to a resin solution for coating, comprising: a polyimine resin containing a structural unit represented by the formula (1) of the first aspect; and an organic solvent, the solid of the polyimine resin The component concentration is 1% by weight or more.

The twentieth aspect relates to a method for producing a polyimide film, characterized in that a resin solution for coating according to the nineteenth aspect is applied to The substrate is produced by separating from the substrate after drying.

The twenty-first aspect relates to a polyimine which contains a structural unit represented by the following formula (16); (wherein A" represents at least one selected from the group consisting of divalent organic groups represented by the following formulas (17) to (19), and m" represents a natural number);

The 22nd aspect relates to the polyimine of the 21st aspect, which further comprises a structural unit represented by the formula (7) of the fifth aspect.

The present invention relates to the polyimine of the twenty-first aspect or the twenty-second aspect, which further comprises a structural unit represented by the formula (10) of the seventh aspect.

The twenty-fourth aspect relates to the polyimine of the twenty-fourth aspect or the twenty-third aspect, which is produced by chemically imidating a polyimine precursor.

The polyimide film of the present invention has a substrate for a display such as a liquid crystal (TFT) for thinning, weight reduction, and flexibility, a substrate for a solar cell, and a substrate for a lighting fixture. necessary The heat resistance and the low coefficient of linear expansion, in addition to the properties of the polyimide film of the present invention, also have high transparency.

In addition, the substrate for an electronic device of the present invention can be suitably used for a substrate for a display such as a liquid crystal (TFT), a substrate for a solar cell, or a substrate for a lighting fixture.

In addition, the resin solution for coating of the present invention can be suitably used for the production of the substrate for an electronic device of the present invention, and the substrate for an electronic device of the present invention can be suitably produced according to the production method of the present invention.

Further, the polyimine resin containing the polyimine of the present invention has heat resistance and a low coefficient of linear expansion.

Fig. 1 is a graph showing the results of measuring the light transmittance of the coating film of Example 2.

Fig. 2 is a graph showing the results of measuring the light transmittance of the coating film of Example 3.

Fig. 3 is a graph showing the results of measuring the light transmittance of the coating film of Example 7.

Fig. 4 is a graph showing the results of measuring the light transmittance of the coating film of Comparative Example 2.

The present invention relates to a polyimide film comprising a polyimine resin containing a structural unit represented by the following formula (1).

(wherein A represents a divalent organic group, and m represents a natural number).

Polyimine containing a structural unit represented by the above formula (1), which is a bicyclo[3,3,0]octane-2,4,6,8- as a tetracarboxylic dianhydride component in an organic solvent. The tetracarboxylic dianhydride is obtained by polymerizing a diamine represented by the following formula (20) as a diamine component to obtain a polyamic acid, and then imidating the polyphosphonium amide.

H ₂ NA-NH ₂ (20) (wherein A represents a divalent organic group).

Examples of the diamine represented by the formula (20) include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2-methyl-1,4-phenylenediamine, and 2,5-dimethyl- 1,4-phenylenediamine, 2,3-dimethyl-1,4-phenylenediamine, 2,6-dimethyl-1,4-phenylenediamine, tetramethyl-1,4-benzenediene Amine, 5-methyl-1,3-phenylenediamine, 4-methyl-1,3-phenylenediamine, 2-(trifluoromethyl)-1,4-phenylenediamine, 2,5-double (trifluoromethyl)-1,4-phenylenediamine, 2,3-bis(trifluoromethyl)-1,4-phenylenediamine, 2,6-bis(trifluoromethyl)-1,4 -phenylenediamine, tetrakis(trifluoromethyl)-1,4-phenylenediamine, 2-(trifluoromethyl)-1,3-phenylenediamine, 4-(trifluoromethyl)-1,3 -phenylenediamine, 2-methoxy-1,4-phenylenediamine, 2,5-dimethoxy-1,4-phenylenediamine, 2-hydroxy-1,4-phenylenediamine, 2, 5-dihydroxy-1,4-phenylenediamine, 2-fluoro-1,4-phenylenediamine, 2,5-difluoro-1,4-phenylenediamine, 2-chloro-1,4-phenylene Amine, 2,5-dichloro-1,4-phenylenediamine, benzidine, 2-methylbenzidine, 3-methylbenzidine, 2-(trifluoromethyl)benzidine, 3-(trifluoro Methyl)benzidine, 2,2'-dimethyl Benzoaniline (m-toluidine), 3,3'-dimethylbenzidine (o-tolidine), 2,3'-dimethylbenzidine, 2,2'-bis(trifluoromethyl) Benzidine, 3,3'-bis(trifluoromethyl)benzidine, 2,3'-bis(trifluoromethyl)benzidine, 2,2'-dimethoxybenzidine, 3,3'- Dimethoxybenzidine, 2,3'-dimethoxybenzidine, 2,2'-dihydroxybenzidine, 3,3'-dihydroxybenzidine, 2,3'-dihydroxybenzidine, 2 , 2'-difluorobenzidine, 3,3'-difluorobenzidine, 2,3'-difluorobenzidine, 2,2'-dichlorobenzidine, 3,3'-dichlorobenzidine, 2 , 3'-dichlorobenzidine, 4,4'-diaminobenzimidamide, 4-aminephenyl-4'-aminobenzylate, octafluorobenzidine, 2,2',5, 5'-tetramethylbenzidine, 3,3',5,5'-tetramethylbenzidine, 2,2',5,5'-tetrakis(trifluoromethyl)benzidine, 3,3', 5,5'-tetrakis(trifluoromethyl)benzidine, 2,2',5,5'-tetrachlorobenzidine, and the like.

From the viewpoint of having a low linear expansion coefficient of the polyimine resin film of the present invention, the diamine represented by the formula (20) preferably has the above formula (2) or (3). A structurally rigid diamine of the molecular structure.

(wherein R ¹ to R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms).

A diamine represented by the formula (20) represented by the formula (2) or the formula (3), and examples thereof include p-phenylenediamine, 2-methyl-1,4-phenylenediamine, 2,5- two Methyl-1,4-phenylenediamine, 2,3-dimethyl-1,4-phenylenediamine, 2,6-dimethyl-1,4-phenylenediamine, tetramethyl-1,4 -phenylenediamine, 2-(trifluoromethyl)-1,4-phenylenediamine, 2,5-bis(trifluoromethyl)-1,4-phenylenediamine, 2,3-bis(trifluoro Methyl)-1,4-phenylenediamine, 2,6-bis(trifluoromethyl)-1,4-phenylenediamine, tetrakis(trifluoromethyl)-1,4-phenylenediamine, benzidine , 2-methylbenzidine, 3-methylbenzidine, 2-(trifluoromethyl)benzidine, 3-(trifluoromethyl)benzidine, 2,3'-dimethylbenzidine, 2, 2'-bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine, 2,3'-bis(trifluoromethyl)benzidine, 2,2',5, 5'-tetramethylbenzidine, 3,3',5,5'-tetramethylbenzidine, 2,2',5,5'-tetrakis(trifluoromethyl)benzidine, 3,3', 5,5'-(trifluoromethyl)benzidine, and the like.

Further, the diamine can be exemplified by 2,2'-bis(trifluoromethyl)benzidine from the viewpoint of further reducing the linear expansion coefficient of the polyimide film of the present invention and further improving the transparency. (Formula (21)), 3,3'-bis(trifluoromethyl)benzidine (Formula (22)), 2-(Trifluoromethyl)-1,4-phenylenediamine (Formula (23)) Particularly preferred is 2,2'-bis(trifluoromethyl)benzidine.

In the polyimine resin of the present invention, in addition to the above diamine, a diamine component represented by the following formula (24) can be used.

H ₂ N-A'-NH ₂ (24) (wherein A' represents a divalent organic group).

The diamine represented by the formula (24) is, for example, the diamine exemplified as the diamine represented by the formula (20).

The diamine represented by the formula (24) is preferably a structure represented by the following formula (8) or formula (9).

(wherein R ⁴ to R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms).

A' of the diamine represented by the formula (24) represented by the following formula (8) or formula (9), and p-phenylenediamine, 2-methyl-1,4-phenylenediamine, 2, 5-dimethyl-1,4-phenylenediamine, 2,3-dimethyl-1,4-phenylenediamine, 2,6-dimethyl-1,4-phenylenediamine, tetramethyl- 1,4-phenylenediamine, benzidine, 2-methylbenzidine, 3-methylbenzidine, 2,3'-dimethylbenzidine, 2,2',5,5'-tetramethyl Aniline, 3,3',5,5'-tetramethylbenzidine, and the like.

Further, the polyimide film of the present invention may further comprise a polyimine resin containing a structural unit represented by the following formula (10).

(In the formula, B represents a divalent aromatic group or an aliphatic group, and n represents a natural number).

The polyimine resin containing the structural unit represented by the above formula (10) is a 1,2,3,4-cyclobutanetetracarboxylic dianhydride as a tetracarboxylic dianhydride component in an organic solvent. The diamine component is obtained by polymerizing a diamine represented by the following formula (25) to obtain a polyamic acid, and then imidating the polyphosphonium hydrazide.

H ₂ NB-NH ₂ (25) (wherein B represents a divalent aromatic group or an aliphatic group).

The aromatic diamine represented by the formula (25), for example, the diamine exemplified as the diamine represented by the formula (20).

Examples of the aliphatic diamine represented by the formula (25) include 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(3-methylcyclohexylamine), and different Buddhas. Ketone diamine, trans-1,4-cyclohexanediamine, cis-1,4-cyclohexanediamine, 1,4-cyclohexanebis(methylamine), 2,5-double ( Amine methyl)bicyclo[2.2.1]heptane, 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane, 3,8-bis(aminomethyl)tricyclo[5.2.1.0]癸Alkane, 1,3-diamine adamantane, 2,2-bis(4-aminocyclohexyl)propane, 2,2-bis(4-aminocyclohexyl)hexafluoropropane, 1,3-propane II Amine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptethylenediamine, 1,8-octaethylene Amine, 1,9-non-methylenediamine, and the like.

In the diamine represented by the formula (25), the above B is preferably at least one selected from the group consisting of a divalent organic group represented by the following formula (11) or formula (12).

(wherein R ⁷ to R ⁹ independently of each other represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms).

The diamine represented by the formula (25) in which the structure represented by the formula (11) or the formula (12) is represented by the formula (2) or the formula (3). 20) A diamine exemplified as the diamine.

The diamine represented by the formula (25) is particularly preferably 2,2'-bis(trifluoroethylene) from the viewpoint that the linear expansion coefficient of the polyimine resin film of the present invention is low and the transparency is higher. Methyl)benzidine (the above formula (21)), 3,3'-bis(trifluoromethyl)benzidine (the above formula (22)), 2-(trifluoromethyl)-1,4-benzene The amine (the above formula (23)) is particularly preferably 2,2'-bis(trifluoromethyl)benzidine.

The reaction of such a tetracarboxylic dianhydride component with a diamine compound can be carried out relatively easily in an organic solvent, and is advantageous from the viewpoint of not generating by-products.

The organic solvent to be used in this case is not particularly limited as long as it can dissolve the produced polyamic acid. This specific example is listed below.

For example, there are N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethyl azine, Tetramethylurea, pyridine, dimethyl hydrazine, hexamethylarylene, γ-butyrolactone, isopropyl Alcohol, methoxymethylpentane, dipentene, ethyl pentanone, methyl fluorenone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropanone, methyl cellosolve, ethyl cellosolve, A Cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, B Glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol tertiary butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol II Methyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3 -methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentanyl acetate, butyl Butyl acrylate, dibutyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate Propylene carbonate , methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3-ethyl Methyl ethyl oxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, 3-methoxy Butyl propionate, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, and the like. These can be used alone or in combination. Further, even a solvent in which polylysine cannot be dissolved can be used in the above solvent without being precipitated in a range in which the produced polyamine acid is not precipitated. Further, since the water in the organic solvent is a cause of hindering the polymerization reaction and hydrolyzing the produced polylysine, the organic solvent is preferably one which is dehydrated and dried as much as possible.

As a method of reacting a tetracarboxylic dianhydride and a diamine compound in an organic solvent, the solution which disperse|dissolves or melt|dissolves a diamine compound in an organic solvent, and a tetracarboxylic-acid dianhydride, or a dispersion or a method of adding after dissolving in an organic solvent, and conversely, adding a diamine compound to a solution for dispersing or dissolving a tetracarboxylic dianhydride in an organic solvent, and mutually reacting a tetracarboxylic dianhydride with a diamine compound Method, etc., any of these methods can be used. Further, when the tetracarboxylic dianhydride or the diamine compound is composed of a plurality of compounds, it may be reacted in a state of being premixed, or may be sequentially reacted individually, or a mixture of low molecular weight molecules after individual reaction may be mixed. It constitutes a high molecular weight body.

The temperature of the above polyamic acid at the time of synthesis may be selected from any temperature of from -20 ° C to 150 ° C, preferably from -5 ° C to 100 ° C. Further, the reaction can be carried out at any concentration, but when the concentration is too low, it is difficult to obtain a polymer having a high molecular weight, and when the concentration is too high, the viscosity of the reaction liquid becomes too high and it is difficult to uniformly stir, so tetracarboxylic acid The total concentration of the dianhydride and the diamine component in the reaction solution is preferably from 1 to 50% by mass, particularly preferably from 5 to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.

In the synthesis reaction of polyamic acid, the ratio of the molar number of the diamine component to the molar number of the tetracarboxylic dianhydride component is preferably from 0.8 to 1.2. As with the usual polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polylysine.

In the polyimine resin used in the present invention, the dehydration ring closure ratio (the imidization ratio) of the valine group is not necessarily required to be 100%, and can be arbitrarily adjusted depending on the use or purpose.

The method for imidizing polyphosphonium hydrazide may be exemplified by thermal imidization of a solution in which polyamic acid is directly heated, and catalytic ruthenium imidization of a solution in which a catalyst is added to polylysine.

The temperature at which the polyglycine is thermally imidized in the solution is from 100 ° C to 400 ° C, preferably from 120 ° C to 250 ° C, preferably by removing water formed by the hydrazine imidization reaction to the system. The outside side is carried out.

The chemical (catalytic) ruthenium imidization of polylysine can be carried out by adding a basic catalyst and an acid anhydride to a solution of polyamic acid and stirring at -20 ° C to 250 ° C, preferably 0 to 180 ° C. Come on. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, and the amount of the acid anhydride is 1 to 50 moles, preferably 3, of the amidino group. Up to 30 moles.

The basic catalyst may, for example, be pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine is preferred because it has a moderate basicity for allowing the reaction to proceed. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyrogallic acid dianhydride. Among them, when acetic anhydride is used, the purification after the completion of the reaction is easily carried out, which is preferable. The ruthenium imidization rate of the ruthenium imidization can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

In the polyimine resin of the present invention, the dehydration ring closure ratio (the imidization ratio) of the proline group is not necessarily required to be 100%, and can be arbitrarily adjusted depending on the use or purpose. Very good for more than 50%.

When the polymer component is recovered from the reaction solution of polyperuric acid or polyimine, the reaction solution may be introduced into a poor solvent to precipitate. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, and butyl cellosolve. Agent, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. The polymer which has been deposited in a poor solvent and precipitated can be dried under normal pressure or reduced pressure at normal temperature or under heating. Further, when the operation of reprecipitating and recovering the precipitate-recovered polymer in the organic solvent is repeated 2 to 10 times, the impurities in the polymer can be reduced. When the poor solvent at this time is used, for example, when three or more kinds of poor solvents such as alcohols, ketones, and hydrocarbons are used, the efficiency of purification can be further improved, which is preferable.

The organic solvent in which the resin component is dissolved is not particularly limited. Specific examples thereof include N,N'-dimethylformamide, N,N'-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl caprolactam, and 2 - pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethyl fluorene, γ-butyrolactone , 1,3-dimethyl-imidazolidinone, dipentene, ethyl pentanone, methyl fluorenone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropanone, cyclohexanone, ethylene carbonate, carbonic acid Propylene ester, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, and the like. These solvents may be used in combination of two or more kinds.

In the polyimine resin of the present invention, the number m of structural units represented by the formula (1), the number m' of the unit structure represented by the formula (7), and the number of unit structures represented by the formula (10) n The ratio is preferably 0.1 ≦ m + m' ≦ 1.0 and 0.0 ≦ n ≦ 0.9.

Further, the polyimine resin used in the present invention takes into consideration the strength of the polyimide film, the workability of coating film formation when forming a polyimide film, the uniformity of the coating film, etc., gel permeation. Chromatography (GPC) The weight average molecular weight after conversion in terms of polystyrene is preferably 5,000 to 200,000.

(Preparation, film formation, solvent drying step of polyimine resin solution)

Another aspect of the present invention is a resin solution for coating comprising a polyimine resin containing a structural unit represented by the above formula (1) and an organic solvent.

Further, the resin solution for coating of the present invention is characterized in that the solid content concentration is 1% by weight or more. When the solid content concentration is less than 1% by weight, the film forming efficiency is lowered, and since the viscosity of the polyimide film solution is lowered, it is difficult to obtain a coating film having a uniform surface. Here, the solid component weight is a component other than the organic solvent, and is contained as a solid component in the weight even if it is a liquid monomer.

The solid content concentration is preferably 1% by weight or more and 35% by weight or less.

In order to impart processing characteristics or various functionalities, various other organic or inorganic low molecular or high molecular compounds may be formulated in the resin solution for coating of the present invention. For example, an antifoaming agent, a planarizing agent, a surfactant, a dye, a plasticizer, fine particles, a sensitizer, or the like can be used. The polyimine resin solution of the present invention can be obtained by dissolving the polyimine resin obtained by the above method in the above organic solvent. The polyimine resin can be obtained by dissolving it in an organic solvent or by dissolving the polyimide film.

Next, a method for producing the polyimide film of the present invention will be described. The resin solution for coating of the present invention is applied onto a predetermined substrate, and then dried to form a polyimide film. In this manual, sometimes it will be manufactured by this The polyimine resin film obtained by the method is called a coating film. As the substrate to be coated, glass, SUS, ruthenium wafer, plastic film or the like can be used, but it is not limited thereto. In particular, when applied as a substrate material for an electronic device, the coated substrate is preferably a glass or a tantalum wafer, more preferably glass, from the viewpoint of using an existing device. Further, the linear thermal expansion coefficient of the coated substrate is preferably 30 ppm/K or less, and more preferably 20 ppm/K or less from the viewpoint of warpage of the substrate after coating.

The coating method of the resin solution for coating of the present invention is not particularly limited, and industrially, a general method is carried out by a method using a doctor blade, screen printing, lithography, quick-drying printing, or inkjet. Other coating methods include immersion, roll coating, slit coating, spin coating, etc., which can be used for the purpose.

Next, the step of removing the organic solvent from the resin solution for coating applied to the substrate will be described. Regarding the film forming temperature, the conditions of the compounding process can be selected without particular limitation. In order to exhibit a low coefficient of thermal expansion, it is preferred to form a film at a temperature of 280 ° C or higher. However, when heated at a temperature of 250 ° C or more in a state in which a large amount of solvent remains, the polyiminimide causes molecular motion in a state of retaining plasticity, which is not preferable. . The film forming temperature for exhibiting a low coefficient of thermal expansion is preferably formed at a temperature of two or more stages of the stage of drying the solvent and the stage of promoting molecular alignment. When it is set to one stage and then set to two stages, the first stage is preferably in the range of 50 ° C to 200 ° C, particularly preferably 80 ° C to 180 ° C. The second stage is preferably higher than the temperature of the first stage, and specifically, it is preferably in the range of 200 ° C to 350 ° C, particularly preferably 250 ° C to 300 ° C.

In addition, the removal of the organic solvent by the heating can be large Under pressure or under inert gas such as nitrogen or under reduced pressure, different pressures can be applied in each stage of heating.

The method of peeling the polyimide film formed as described above from the substrate is not particularly limited, and a method in which the polyimide film is cooled, a slit is formed in the film, and then peeled off, or a roll is imparted thereto. The method of peeling by tension and the like.

The thickness of the polyimide film of the present invention is not particularly limited, but is usually 1 to 50 μm, preferably 5 to 40 μm.

The polyimine resin film thus produced can achieve high transparency of a light transmittance of 70% or more at a wavelength of 400 nm.

Further, the polyimide film has a linear expansion coefficient of from 60 ° C to less than 60 ppm/K at 100 ° C to 220 ° C, especially from 5 ppm / K to 35 ppm / K, so that dimensional stability during heating is good. .

Since the polyimide film of the present invention has the above characteristics, it can be suitably used for a substrate for a display such as a TFT, a substrate for a solar cell, or a substrate for a lighting fixture.

Further, the present invention also targets a polyimine having a structural unit represented by the following formula (16).

(wherein A" represents at least one selected from the group consisting of divalent organic groups represented by the following formulas (17) to (19), and m" represents a natural number)

Example

The invention is illustrated in more detail below by way of examples, but the invention is not limited to the following examples.

[Acronym used in the examples]

The meanings of the abbreviations used in the following examples are as follows.

<acid dianhydride>

BODA: bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride

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

<Diamine>

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

p-PDA: p-phenylenediamine

m-PDA: m-phenylenediamine

m-BAPS: bis[4-(3-aminophenoxy)phenyl]indole

<organic solvent>

DMAc: N,N-dimethylacetamide

NMP: N-methyl-2-pyrrolidone

MeOH: methanol

DMF: N,N-dimethylformamide

evaluation method (1) Determination of number average molecular weight and weight average molecular weight

The number average molecular weight (hereinafter abbreviated as Mn) and the weight average molecular weight (hereinafter abbreviated as Mw) of the polymer were obtained by using a GPC apparatus (HLC-8220GPC) manufactured by Tosoh Corporation and a column made by Shodex (joining SB803HQ, SB804HQ). Further, DMF (additive lithium bromide monohydrate 30 mM, phosphoric acid ‧ anhydrous crystals (orthophosphoric acid) 30 mM, tetrahydrofuran 10 ml / L) was used as an elution solvent, and the measurement was carried out at a column temperature of 50 ° C and a flow rate of 0.9 ml/min.

(2) 醯 imidization rate

The oxime imidization ratio of the solvent-soluble polyimine in the examples was measured in the following manner. The polyimine powder was completely dissolved in deuterated dimethyl hydrazine (DMSO-d6, containing 0.05% TMS), and a proton NMR of 300 MHz was measured by an NMR measuring instrument manufactured by JEOL. The imidization ratio of ruthenium is determined by using protons derived from structures that do not change before and after imidization as a reference proton, and the integrated value of the protons, and the NH group of proline which occurs near 9.5 to 10.0 ppm. The proton peak is calculated.

(3) Linear thermal expansion coefficient of coated film

The linear thermal expansion coefficient of 100 to 220 ° C was measured by using TMA-60 manufactured by Bruker AXS Co., Ltd., and the film was cut into a size of 4 mm in width and 17 mm in length, and heated at 10 ° C/min under a load of 10.0 g, and at 50 ° C. It was determined by measurement in 260 °C.

(4) 5% weight loss temperature of the coated film

The 5% weight loss temperature was determined by using TG/DTA2000SA manufactured by Bruker AXS Co., Ltd., and measuring about 5 mg of the film at a temperature of 10 ° C/min and measuring at 50 to 500 ° C.

(5) Light transmittance of the coated film (transparency)

The light transmittance of 400 nm was measured using UV-3600 manufactured by Shimadzu Corporation and using air as a reference value.

(6) Evaluation of heat-resistant yellowing

After the coated film was exposed to air at 220 ° C for 3 hours, the light transmittance at 400 nm was measured and the transparency was evaluated.

<Synthesis of Polyimine Resin] <Synthesis Example 1>

After dissolving TFMB 2.105 g (6.57 mmol) in DMAc 9.0 g, BODA 1.645 g (6.57 mmol) was added, and the reaction was carried out at 70 ° C for 3 hours under nitrogen atmosphere, and then reacted at 50 ° C for 24 hours to form polylysine. . Dilute the polyaminic acid solution to 10 mass by DMAc %, 1.560 g of pyridine and 2.685 g of acetic anhydride were added as a ruthenium amide catalyst, and the reaction was carried out at 100 ° C for 4 hours in a nitrogen atmosphere. The reaction solution was added dropwise to 200.0 g of MeOH to carry out precipitation purification, and after filtration, it was subjected to solid-liquid washing in 100.0 g of MeOH, and after filtration, it was dried at 150 ° C under reduced pressure to obtain a white poly Amine powder. The molecular weight of the obtained polyimine resin was Mw = 71,500, Mn = 31,500, and the sulfhydrylation ratio was 84.2%.

<Synthesis Example 2>

After dissolving TFMB 12.875 g (40.21 mmol) in 44.625 g of DMAc, BODA 8.048 g (32.17 mmol) was added, and the reaction was carried out at 70 ° C for 3 hours under nitrogen atmosphere, then CBDA 1.577 g (8.04 mmol) and DMAc 7.875 g were added. The reaction was carried out at 60 ° C for 4 hours and then at 50 ° C for 24 hours to form polylysine. The polyamic acid solution was diluted to 11% by mass by DMAc, and 9.541 g of pyridine and 16.419 g of acetic anhydride were added as a ruthenium amide catalyst, and the mixture was reacted at 100 ° C for 4 hours in a nitrogen atmosphere. The reaction solution was added dropwise to 1050.0 g of MeOH to carry out precipitation purification, and after filtration, it was subjected to solid-liquid washing in 400.0 g of MeOH, and after filtration, it was dried at 150 ° C under reduced pressure to obtain a white poly Amine powder. The molecular weight of the obtained polyimine resin was Mw = 47, 100, Mn = 23, 100, and the oxime imidization ratio was 84.8%.

<Synthesis Example 3>

2. TFMB 2.617g (6.77mmol) was dissolved in DMAc 9.00g After that, BODA 1.185 g (4.74 mmol) was added, and the mixture was reacted at 70 ° C for 3 hours under a nitrogen atmosphere, then 0.38 g (2.03 mmol) of CBDA was added, reacted at 60 ° C for 4 hours, and then reacted at room temperature for 24 hours. Produce polylysine. The polyamic acid solution was diluted to 11% by mass by DMAc, and 1.606 g of pyridine and 2.763 g of acetic anhydride were added as a ruthenium amide catalyst, and the mixture was reacted at 100 ° C for 4 hours in a nitrogen atmosphere. The reaction solution was added dropwise to 200.0 g of MeOH to carry out precipitation purification, and after filtration, it was subjected to solid-liquid washing in 100.0 g of MeOH, and after filtration, it was dried at 150 ° C under reduced pressure to obtain a white poly Amine powder. The molecular weight of the obtained polyimine resin was Mw = 61,500, Mn = 25,000, and the sulfhydrylation ratio was 85.1%.

<Synthesis Example 4>

After dissolving TFMB 2.210 g (6.90 mmol) in 9.00 g of DMAc, adding BODA 0.863 g (3.45 mmol), reacting at 70 ° C for 3 hours under nitrogen atmosphere, then adding CBDA 0.677 g (3.45 mmol), and reacting at 60 ° C After 4 hours, it was then reacted at room temperature for 24 hours to form polylysine. The polyamic acid solution was diluted to 11% by mass by DMAc, and 1.638 g of pyridine and 2.818 g of acetic anhydride were added as a ruthenium amide catalyst, and the mixture was reacted at 100 ° C for 4 hours in a nitrogen atmosphere. The reaction solution was added dropwise to 200.0 g of MeOH to carry out precipitation purification, and after filtration, it was subjected to solid-liquid washing in 100.0 g of MeOH, and after filtration, it was dried at 150 ° C under reduced pressure to obtain a white poly Amine powder. The molecular weight of the obtained polyimine resin, Mw=42,500, Mn=22,300, In addition, the oxime imidization ratio was 88.5%.

<Synthesis Example 5>

After dissolving 1.293 g (4.04 mmol) of TFMB and 0.437 g (4.04 mmol) of p-PDA in 9.00 g of DMAc, BODA 2.020 g (8.08 mmol) was added, and the reaction was carried out at 70 ° C for 8 hours under nitrogen atmosphere, then at room temperature. The reaction was carried out for 24 hours to form polyamic acid. The polyamic acid solution was diluted to 11% by mass by DMAc, and 1.916 g of pyridine and 3.298 g of acetic anhydride were added as a ruthenium amide catalyst, and the mixture was reacted at 100 ° C for 4 hours in a nitrogen atmosphere. The reaction solution was added dropwise to 250.0 g of MeOH to carry out precipitation purification, and after filtration, it was solid-liquid washed in 150.0 g of MeOH, and after filtration, it was dried at 150 ° C under reduced pressure to obtain a white poly Amine powder. The molecular weight of the obtained polyimine resin was Mw = 42,000, Mn = 16,300, and the sulfhydrylation ratio was 72.2%.

<Synthesis Example 6>

After dissolving 1.877 g (5.86 mmol) of TFMB and 0.158 g (1.58 mmol) of p-PDA in 9.00 g of DMAc, adding 1.283 g (5.13 mmol) of BODA, reacting at 70 ° C for 3 hours under nitrogen atmosphere, and then adding CBDA 0.431 g (2.20 mmol) was reacted at 60 ° C for 4 hours, and then reacted at room temperature for 24 hours to form polylysine. The polyamic acid solution was diluted to 11% by mass by DMAc, and 1.739 g of pyridine and 2.992 g of acetic anhydride were added as a ruthenium amide catalyst, and the mixture was reacted at 100 ° C for 4 hours in a nitrogen atmosphere. The reaction solution was dropped into MeOH Precipitation purification was carried out in 200.0 g, and after filtration, it was subjected to solid-liquid washing in 100.0 g of MeOH, and after filtration and filtration, it was dried at 150 ° C under reduced pressure to obtain a white polyimine powder. The molecular weight of the obtained polyimine resin was Mw = 48,800, Mn = 22,900, and the oxime imidization ratio was 83.7%.

<Synthesis Example 7>

After dissolving 1.877 g (5.86 mmol) of TFMB and 0.158 g (1.58 mmol) of m-PDA in 9.00 g of DMAc, adding 1.283 g (5.13 mmol) of BODA, reacting at 70 ° C for 3 hours under nitrogen atmosphere, and then adding CBDA 0.431 g (2.20 mmol) was reacted at 60 ° C for 4 hours, and then reacted at room temperature for 24 hours to form polylysine. The polyamic acid solution was diluted to 11% by mass by DMAc, and 1.739 g of pyridine and 2.992 g of acetic anhydride were added as a ruthenium amide catalyst, and the mixture was reacted at 100 ° C for 4 hours in a nitrogen atmosphere. The reaction solution was added dropwise to 200.0 g of MeOH to carry out precipitation purification, and after filtration, it was subjected to solid-liquid washing in 100.0 g of MeOH, and after filtration, it was dried at 150 ° C under reduced pressure to obtain a white poly Amine powder. The molecular weight of the obtained polyimine resin was Mw = 48,400, Mn = 19,700, and the oxime imidization ratio was 85.7%.

<Comparative Synthesis Example 1>

After dissolving 1.293 g (4.04 mmol) of TFMB and 0.437 g (4.04 mmol) of p-PDA in 9.00 g of DMAc, BODA 2.020g was added. (8.08 mmol), reacted at 70 ° C for 8 hours in a nitrogen atmosphere, and then reacted at room temperature for 24 hours to form polylysine.

<Comparative Synthesis Example 2>

1.536 g (4.24 mmol) of TFMB, 0.366 g (3.39 mmol) of p-PDA, and 0.366 g (0.85 mmol) of m-BAPS were dissolved in 11.25 g of NMP, and 1.661 g (8.47 mmol) of CBDA was added, and it was added to a nitrogen atmosphere. The reaction was carried out for 24 hours at room temperature to form polylysine.

<Production of coated film> Example 1

The polyetherimide resin synthesized in Synthesis Example 1 was used, and DMAc was used as a solvent to prepare a resin solution for coating of 22% by mass. The coating solution was uniformly applied to a glass plate by applying a doctor blade having a thickness of 200 μm, and then subjected to air at 120 ° C for 10 minutes, in vacuum at 180 ° C for 30 minutes, and at 250 ° C for 60 minutes. Baking was carried out at 300 ° C for 60 minutes to obtain a coated film. The evaluation results of the coated film are as described in Table 1.

Example 2

A coated film was produced in the same manner as in Example 1 using the polyimine resin synthesized in Synthesis Example 2. The evaluation results of the coated film are as described in Table 1.

Example 3

The polyetherimide resin synthesized in Synthesis Example 2 was used, and DMAc was used as a solvent to prepare a 30% by mass resin solution for coating. The coating solution was uniformly applied to a glass plate by applying a doctor blade having a thickness of 300 μm, and then carried out in air at 90 ° C for 20 minutes, at 120 ° C for 20 minutes, and in vacuum at 180 ° C for 30 minutes. The film was baked at 220 ° C for 60 minutes and baked at 250 ° C for 60 minutes to obtain a coated film. The evaluation results of the coated film are as described in Table 1.

Example 4

The polyetherimide resin synthesized in Synthesis Example 2 was used, and DMAc was used as a solvent to prepare a 30% by mass resin solution for coating. The coating solution was uniformly applied to a glass plate by applying a doctor blade having a thickness of 400 μm, and then carried out in air at 90 ° C for 20 minutes, at 120 ° C for 20 minutes, and in vacuum at 180 ° C for 30 minutes. The film was baked at 220 ° C for 60 minutes and baked at 250 ° C for 60 minutes to obtain a coated film. The evaluation results of the coated film are as described in Table 1.

Example 5

A coated film was produced in the same manner as in Example 1 using the polyimine resin synthesized in Synthesis Example 3. The evaluation results of the coated film are as described in Table 1.

Example 6

A coated film was produced in the same manner as in Example 1 using the polyimine resin synthesized in Synthesis Example 4. The evaluation results of the coated film are as described in Table 1.

Example 7

A coated film was produced in the same manner as in Example 1 using the polyimine resin synthesized in Synthesis Example 5. The evaluation results of the coated film are as described in Table 1.

Example 8

A coated film was produced in the same manner as in Example 1 using the polyimine resin synthesized in Synthesis Example 6. The evaluation results of the coated film are as described in Table 1.

Example 9

A coated film was produced in the same manner as in Example 1 using the polyimine resin synthesized in Synthesis Example 7. The evaluation results of the coated film are as described in Table 1.

Comparative example 1

The polylysine solution synthesized in Comparative Synthesis Example 1 was directly used as a coating resin solution, uniformly coated on a glass plate with a doctor blade having a thickness of 200 μm, and then subjected to air at 120 ° C for 10 minutes. It is carried out in vacuum at 180 ° C for 30 minutes and at 250 ° C for 60 minutes. Baking was carried out at 300 ° C for 60 minutes to obtain a coated film. The evaluation results of the coated film are as described in Table 1.

Comparative example 2

The polyphthalic acid solution synthesized in Comparative Synthesis Example 2 was directly used as a coating resin solution, uniformly coated on a glass plate with a doctor blade having a thickness of 200 μm, and then subjected to air at 120 ° C for 10 minutes. The film was coated in a vacuum at 180 ° C for 30 minutes, at 220 ° C for 60 minutes, and at 250 ° C for 60 minutes to obtain a coated film. The evaluation results of the coated film are as described in Table 1.

As shown in Table 1, the coating film of Examples 1 to 9 of the polyimide film produced by chemically imidating the polyimide precursor, the linear expansion coefficient [ppm/K] ] (100 to 200 ° C) is low, and the light transmittance [%] at 400 nm is high after hardening. On the other hand, the coating film of Comparative Example 1 produced by thermally imidating a polyimide precursor with a polyamidene precursor has a linear expansion coefficient [ppm/K] and is hardened. The light transmittance [%] at 400 nm is low.

<heat resistance yellow test> Example 12

After the coating film prepared in Example 2 was exposed to air at 220 ° C for 3 hours, the light transmittance of the coating film before and after the test was measured. The results are as shown in Fig. 1.

Example 13

After the coating film prepared in Example 3 was exposed to air at 220 ° C for 3 hours, the light transmittance of the coating film before and after the test was measured. The results are as shown in Fig. 2.

Example 14

After the coating film prepared in Example 7 was exposed to air at 220 ° C for 3 hours, the light transmittance of the coating film before and after the test was measured. Knot As shown in Figure 3.

Comparative example 3

The coating film prepared in Comparative Example 2 was exposed to air at 220 ° C for 3 hours, and the light transmittance of the coating film before and after the test was measured. The results are as shown in Fig. 4.

As shown in FIGS. 1 to 4, Example 2, Example 3, and implementation of a polyimide resin produced by chemically hydrazating a polyfluorene precursor with BODA as an acid dianhydride The coated film of Example 4 did not observe a decrease in light transmittance even after exposure to air at 220 ° C for 3 hours. On the other hand, the coated film of Comparative Example 2, which was produced by the thermal hydrazine imidization of the polydiimide precursor without BODA as the acid dianhydride, was exposed to air at 220 ° C. After 3 hours, the light transmittance was greatly reduced.

Claims (18)

A polyimine resin film comprising a polyimine resin produced by chemically imidating a polyimine precursor and containing a formula (1) Structural unit; (wherein A represents at least one selected from the group consisting of a divalent organic group represented by the following formula (2) or (3), and R ¹ to R ³ each independently represent a haloalkyl group having 1 to 10 carbon atoms, m Represents a natural number); The polyimine resin film according to claim 1, wherein the aforementioned A represents at least one selected from the group consisting of divalent organic groups represented by the following formulas (4) to (6); The polyimine resin film according to claim 2, wherein the aforementioned A represents a divalent organic group represented by the above formula (4). The polyimine resin film according to any one of claims 1 to 3, wherein the polyimine resin further contains a structural unit represented by the following formula (7); (wherein A' represents at least one selected from the group consisting of divalent organic groups represented by the following formula (8) or formula (9), and R ⁴ to R ⁶ independently of each other represent a hydrogen atom or an alkane having 1 to 10 carbon atoms; Base, m' represents a natural number); The polyimine resin film according to claim 4, wherein the aforementioned A' represents a divalent organic group represented by the above formula (9). The polyimine resin film according to any one of claims 1 to 3, wherein the polyimine resin further contains a structural unit represented by the following formula (10); (In the formula, B represents a divalent aromatic group or an aliphatic group, and n represents a natural number). The polyimine resin film according to claim 6, wherein the above B represents at least one selected from the group consisting of a divalent aromatic group represented by the following formula (11) or (12); (wherein R ⁷ to R ⁹ independently of each other represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms). The polyimine resin film according to claim 7, wherein the aforementioned R ⁷ to R ⁹ represent a haloalkyl group having 1 to 10 carbon atoms. The polyimine resin film according to claim 8, wherein the above B represents at least one selected from the group consisting of divalent aromatic groups represented by the following formulas (13) to (15); The polyimine resin film according to claim 9, wherein the above B represents a divalent aromatic group represented by the above formula (13). The polyimine resin film according to any one of claims 1 to 3, wherein the light transmittance at a wavelength of 400 nm is 70%. on. The polyimine resin film according to any one of claims 1 to 3, wherein the linear expansion coefficient is 60 ppm/K or less. The polyimine resin film of claim 12, wherein the linear expansion coefficient is from 5 ppm/K to 35 ppm/K. A substrate for an electronic device, which is obtained by a film of a polyimide film according to any one of claims 1 to 13. The substrate for an electronic device according to claim 14, wherein the substrate is for a TFT, a display, a solar cell, or a lighting fixture. The substrate for an electronic device according to claim 15, wherein the substrate is a display. A resin solution for coating, comprising: a polyimine resin containing a structural unit represented by the formula (1) of the first aspect of the patent application; and an organic solvent, and a solid concentration of the polyimine resin It is 1% by weight or more. A method for producing a substrate for an electronic device, which comprises applying a resin solution for coating according to item 17 of the patent application to a substrate, and drying it, and then separating it from the substrate.