Resin film, method for producing the same, resin composition, display and method for producing the same

Abstract

The present invention addresses the problem of providing a resin film which is capable of suppressing the occurrence of wrinkles or separation of a film superposed thereon in a high temperature process in the production of a device, and which is suitable for applications where transparency is required.　A resin film which contains a resin that has a repeating unit represented by chemical formula (1), wherein: the light transmittance at the wavelength of 400 nm is 68% or more; the glass transition temperature is 370°C or more; and the weight loss initiation temperature is 440°C or more. (In chemical formula (1), A represents a tetravalent tetracarboxylic acid residue having 2 or more carbon atoms; and B represents a divalent diamine residue having 2 or more carbon atoms.)

Description

[Technical Field]

[0001] The present invention relates to a resin film, a method for producing the same, a resin composition, a display, and a method for producing the same. [Background technology]

[0002] Due to its excellent electrical insulation, heat resistance, and mechanical properties, polyimide is used as a material for various electronic devices, such as semiconductors and displays. Recently, the use of polyimide films as substrates for displays such as organic electroluminescence (EL) displays, electronic paper, and color filters has enabled the production of shock-resistant, flexible displays.

[0003] Materials used in electronic devices must have high heat resistance to withstand the high-temperature processes used in device manufacturing. In particular, for applications requiring transparency, materials that can achieve both heat resistance and transparency are required.

[0004] For example, Patent Document 1 discloses an example of manufacturing an organic EL display using a highly heat-resistant polyimide as a substrate. Patent Document 2 discloses an example of manufacturing electronic devices such as color filters, organic EL displays, and touch panels using a highly transparent polyimide as a substrate. Patent Document 3 reports an example of manufacturing a polyimide film using an alkoxysilane-modified polyimide precursor and using it for transparent substrate applications. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2017 / 099183 [Patent Document 2] International Publication No. 2017 / 221776 [Patent Document 3] Japanese Patent Application Laid-Open No. 2016-188367 Summary of the Invention [Problem to be solved by the invention]

[0006] The polyimide resin film described in Patent Document 1 has an insufficient light transmittance, making it unsuitable for applications requiring transparency. The polyimide resin films described in Patent Documents 2 and 3 have an issue in that films stacked on the polyimide resin film peel off or wrinkles occur during high-temperature processes in electronic device manufacturing. Therefore, an object of the present invention is to provide a transparent resin film that can suppress peeling or wrinkles in films stacked on the resin film during high-temperature processes. [Means for solving the problem]

[0007] The present invention relates to a resin film containing a resin having a repeating unit represented by chemical formula (1), which has a light transmittance of 68% or more at a wavelength of 400 nm, a glass transition temperature (hereinafter referred to as Tg) of 370°C or more, and a weight loss initiation temperature (hereinafter referred to as Td0) of 440°C or more.

[0008] [ka]

[0009] In chemical formula (1), A represents a tetravalent tetracarboxylic acid residue having two or more carbon atoms, and B represents a divalent diamine residue having two or more carbon atoms.

[0010] The present invention also provides a resin composition containing a resin having a repeating unit represented by chemical formula (4) and a solvent, wherein the resin composition is applied and baked at 410°C to produce a 10 μm-thick resin film, which has a light transmittance of 68% or more at a wavelength of 400 nm, a Tg of 370°C or more, and a Td0 of 440°C or more.

[0011] [ka]

[0012] In chemical formula (4), A represents a tetravalent tetracarboxylic acid residue having two or more carbon atoms, and B represents a divalent diamine residue having two or more carbon atoms. 1 and R 2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, an alkali metal ion, an ammonium ion, an imidazolium ion, or a pyridinium ion. [Effects of the Invention]

[0013] The resin film of the present invention can suppress the phenomenon of films stacked on the resin film peeling off or wrinkles forming in the stacked films during high-temperature processes in electronic device manufacturing, and can be suitably used in applications requiring transparency. DETAILED DESCRIPTION OF THE INVENTION

[0014] Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be implemented with various modifications depending on the purpose and application.

[0015] <Resin film> The resin film according to an embodiment of the present invention is a resin film containing a resin having a repeating unit represented by chemical formula (1), and has a light transmittance of 68% or more at a wavelength of 400 nm, a glass transition temperature of 370°C or more, and a weight loss initiation temperature of 440°C or more.

[0016] [ka]

[0017] In chemical formula (1), A represents a tetravalent tetracarboxylic acid residue having two or more carbon atoms, and B represents a divalent diamine residue having two or more carbon atoms.

[0018] Examples of resins having a repeating unit represented by chemical formula (1) include polyimide resins, polyetherimide resins, and polyamideimide resins.

[0019] The resin film according to the embodiment of the present invention has a light transmittance of 68% or more at a wavelength of 400 nm, making it suitable for use in applications requiring transparency. The thickness of the resin film is not particularly limited as long as it is within a range that achieves the light transmittance of 68% or more. However, from the viewpoint of the mechanical properties of the resin film, it is preferably 4 μm or more, more preferably 5 μm or more, and even more preferably 6 μm or more. Furthermore, the thickness of the resin film is preferably 40 μm or less, more preferably 30 μm or less, and even more preferably 25 μm or less. If the thickness of the resin film is 4 μm or more and 40 μm or less, the mechanical properties of the resin film will be good. Furthermore, from the viewpoint of further improving the light transmittance of the resin film, the thickness is preferably 0.5 μm or more and 4 μm or less, and even more preferably 1 μm or more and 3 μm or less.

[0020] It is particularly preferable that the resin film according to the embodiment of the present invention has a light transmittance of 68% or more at a wavelength of 400 nm when converted to a film thickness of 10 μm. The light transmittance when converted to a film thickness of 10 μm is calculated from the light transmittance value obtained by measuring a resin film of a certain film thickness, assuming that absorbance is proportional to film thickness.

[0021] The resin film according to the embodiment of the present invention has a glass transition temperature (Tg) of 370°C or higher, which can prevent the resin film from deforming and causing wrinkles in the film formed thereon during high-temperature processes in the manufacture of electronic devices. A higher Tg of the resin film is preferable because it allows for higher process temperatures in the manufacture of electronic devices. For example, a Tg of 380°C or higher is more preferable.

[0022] In the present invention, Tg is measured using a thermomechanical analyzer by heating a sample to 150°C at a heating rate of 5°C / min in a first step, air-cooling the sample to room temperature at a cooling rate of 5°C / min in a second step, and heating the sample at a heating rate of 5°C / min in a third step.

[0023] The resin film according to the embodiment of the present invention has a weight loss starting temperature Td0 of 440°C or higher, which can prevent the film formed on the resin film from peeling off due to gas generation from the resin film during high-temperature processes in the manufacture of electronic devices. A higher Td0 of the resin film is preferable because it allows the process temperature in the manufacture of electronic devices to be increased. For example, a Td0 of 450°C or higher is more preferable.

[0024] In the present invention, Td0 is measured using a thermogravimetric analyzer by heating a sample to 150°C at a heating rate of 10°C / min in a first step, air-cooling the sample to room temperature at a cooling rate of 10°C / min in a second step, and heating the sample at a heating rate of 10°C / min in a third step.

[0025] In chemical formula (1), A represents a tetravalent tetracarboxylic acid residue having two or more carbon atoms, and this tetracarboxylic acid residue is preferably a tetravalent hydrocarbon group having 2 to 80 carbon atoms. Alternatively, A may be a tetravalent organic group having 2 to 80 carbon atoms, containing hydrogen and carbon as essential components and containing one or more atoms selected from boron, oxygen, sulfur, nitrogen, phosphorus, silicon, and halogen. The number of each of the boron, oxygen, sulfur, nitrogen, phosphorus, silicon, and halogen atoms contained in this organic group is preferably 20 or less, and more preferably 10 or less, independently.

[0026] The tetracarboxylic acid that provides A is not particularly limited, and known tetracarboxylic acids can be used. Examples include pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid having a structure represented by chemical formula (32), 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)ether, 9,9-bis(3,4-dicarboxyphenyl)fluorene, cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, and tetracarboxylic acids described in International Publication No. 2017 / 099183. Other examples include tetracarboxylic acids having a structure represented by chemical formula (33) or a structure represented by chemical formula (34).

[0027] [ka]

[0028] In the chemical formula (33), p represents an integer of 0 to 3. In the chemical formula (34), q represents an integer of 1 to 4.

[0029] These tetracarboxylic acids can be used as raw materials to give A either as they are or in the form of an acid anhydride, an activated ester or an activated amide, and two or more of these may also be used.

[0030] From the viewpoint of further improving the heat resistance of the resin film, it is preferable that A in chemical formula (1) does not contain a fluorine atom.

[0031] From the viewpoint of further improving the heat resistance and transparency of the resin film, in chemical formula (1), A preferably has a tetracarboxylic acid residue having a structure represented by chemical formula (33) or a structure represented by chemical formula (34), or a 3,3',4,4'-biphenyltetracarboxylic acid residue represented by chemical formula (32), and particularly preferably has a 3,3',4,4'-biphenyltetracarboxylic acid residue.

[0032] Furthermore, silicon-containing tetracarboxylic acids such as dimethylsilane diphthalic acid and 1,3-bis(phthalic acid)tetramethyldisiloxane may be used as the tetracarboxylic acid that provides A in order to improve the coating properties on a support when producing a resin film and the resistance to oxygen plasma and UV ozone treatments used for cleaning when forming elements on the resin film. When using these silicon-containing tetracarboxylic acids, it is preferable to use them in an amount of 1 to 30 mol % of the total tetracarboxylic acids.

[0033] In the tetracarboxylic acids exemplified above, some of the hydrogen atoms contained in the residue of the tetracarboxylic acid may be substituted with a hydrocarbon group having 1 to 10 carbon atoms such as a methyl group or an ethyl group, a fluoroalkyl group having 1 to 10 carbon atoms such as a trifluoromethyl group, or a group such as F, Cl, Br, or I. Furthermore, if some of the hydrogen atoms contained in the residue are substituted with an acidic group such as OH, COOH, SO3H, CONH2, or SO2NH2, the solubility of the resin precursor in an alkaline aqueous solution is improved, and therefore this is preferred when the resin is used as a photosensitive resin composition described below.

[0034] In chemical formula (1), B represents a divalent diamine residue having two or more carbon atoms, and this diamine residue is preferably a divalent hydrocarbon group having 2 to 80 carbon atoms. Alternatively, B may be a divalent organic group having 2 to 80 carbon atoms, which contains hydrogen and carbon as essential components and one or more atoms selected from boron, oxygen, sulfur, nitrogen, phosphorus, silicon, and halogen. The number of each of the boron, oxygen, sulfur, nitrogen, phosphorus, silicon, and halogen atoms contained in this organic group is preferably 20 or less, and more preferably 10 or less, independently.

[0035] The diamine that provides B is not particularly limited, and known diamines can be used. Examples include m-phenylenediamine, p-phenylenediamine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-di(trifluoromethyl)-4,4'-diaminobiphenyl, bis(4-aminophenoxyphenyl)sulfone, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, bis(3-amino-4-hydroxyphenyl)hexafluoropropane, ethylenediamine, propylenediamine, butanediamine, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, cyclohexanediamine, 4,4'-methylenebis(cyclohexylamine), 9,9-bis(4-aminophenyl)fluorene, and diamines described in WO 2017 / 099183. Further, diamines having a structure represented by chemical formula (31) are also included.

[0036] [ka]

[0037] In the chemical formula (31), C represents an ether group, an ester group, an amide group, or a sulfonyl group. Examples of diamines having a structure represented by chemical formula (31) include 4,4'-diaminobenzanilide, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, and 4-aminophenyl 4-aminobenzoate.

[0038] These diamines can be used as they are or as the corresponding trimethylsilylated diamines to give B, and two or more of these may be used in combination.

[0039] From the viewpoint of further improving the heat resistance of the resin film, it is preferable that B in chemical formula (1) does not contain a fluorine atom. It is particularly preferable that neither A nor B contains a fluorine atom.

[0040] From the viewpoint of further improving the heat resistance and transparency of the resin film, in chemical formula (1), B preferably has a diamine residue having a structure represented by chemical formula (31), and more preferably has a 3,3'-diaminodiphenylsulfone residue or a 4,4'-diaminodiphenylsulfone residue. Particularly preferred is a case where A has a tetracarboxylic acid residue having a structure represented by chemical formula (33) or a structure represented by chemical formula (34), or a 3,3',4,4'-biphenyltetracarboxylic acid residue, and B has a diamine residue having a structure represented by chemical formula (31). Most preferred is a case where A has a 3,3',4,4'-biphenyltetracarboxylic acid residue, and B has a 3,3'-diaminodiphenylsulfone residue or a 4,4'-diaminodiphenylsulfone residue.

[0041] When A and B have these structures, a resin film having excellent heat resistance and transparency is easily obtained.

[0042] Furthermore, silicon-containing diamines such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane and 1,3-bis(4-anilino)tetramethyldisiloxane may be used as the diamine that provides B in order to improve the coating properties of the resin film on the support when it is produced and the resistance to oxygen plasma and UV ozone treatments used for cleaning when forming elements on the resin film. When using these silicon-containing diamine compounds, it is preferable to use them in an amount of 1 to 30 mol % of the total diamine compounds.

[0043] In the diamine compounds exemplified above, some of the hydrogen atoms contained in the diamine compound may be substituted with a hydrocarbon group having 1 to 10 carbon atoms, such as a methyl group or an ethyl group, a fluoroalkyl group having 1 to 10 carbon atoms, such as a trifluoromethyl group, or a group such as F, Cl, Br, or I. Furthermore, if some of the hydrogen atoms contained in the diamine compound are substituted with an acidic group, such as OH, COOH, SO3H, CONH2, or SO2NH2, the solubility of the resin precursor in an alkaline aqueous solution is improved, and therefore this is preferred when the diamine compound is used as a photosensitive resin composition, which will be described later.

[0044] The value obtained by dividing the number of moles of diamine residues contained in the resin by the number of moles of tetracarboxylic acid residues (hereinafter referred to as the "divided value Ka") is not particularly limited, but is preferably 0.4 or more, more preferably 0.6 or more. The divided value Ka is preferably 0.95 or less, more preferably 0.9 or less, and even more preferably 0.8 or less. If the divided value Ka is 0.4 or more, the mechanical properties of the resin film will be good. If the divided value Ka is 0.95 or less, it is preferable because it can contain more of the structure represented by chemical formula (2) described below.

[0045] The closer the division value Ka is to 1, the closer the number of moles of diamine residues and tetracarboxylic acid residues become to equimolar values, and therefore the greater the number of repeating units represented by chemical formula (1). If the division value Ka is smaller than 1, the polymer structure having the repeating unit represented by chemical formula (1) will likely have a terminal tetracarboxylic acid, whereas if it is greater than 1, the polymer structure having the repeating unit represented by chemical formula (1) will likely have a terminal diamine.

[0046] The resin preferably has a structure represented by chemical formula (2).

[0047] [ka]

[0048] In chemical formula (2), A represents a tetravalent tetracarboxylic acid residue having two or more carbon atoms, B represents a divalent diamine residue having two or more carbon atoms, Z represents an aminosilane residue having 1 to 10 carbon atoms, and R 3 represents a hydrocarbon group having 1 to 20 carbon atoms. n represents 2 or 3. X represents a structure represented by chemical formula (3), in which the oxygen atom in chemical formula (3) and the Si atom in chemical formula (2) are bonded.

[0049] [ka]

[0050] A resin film containing a resin having a structure represented by chemical formula (2) tends to have favorably high light transmittance, Tg, and Td0. The structure represented by chemical formula (2) defines the terminal structure of a resin having a repeating unit represented by chemical formula (1). When the terminal of the resin is a tetracarboxylic acid terminal of a repeating unit represented by chemical formula (1), the structure can be considered to be an imide bond of an aminosilane compound having a siloxane structure to the tetracarboxylic acid structure at the terminal. The siloxane bond site has excellent heat resistance and light transmittance, resulting in higher light transmittance and Td0 of the resin film. Furthermore, in a resin having a structure represented by chemical formula (2), the terminal of the polymer structure having a repeating unit represented by chemical formula (1) is fixed by a siloxane bond, which limits the thermal motion of the resin, and therefore it is presumed that the Tg of the resin film will be higher.

[0051] In chemical formula (2), Z represents an aminosilane residue having 1 to 10 carbon atoms. Examples of Z include an aliphatic hydrocarbon group having 1 to 10 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms. These hydrocarbon groups may have a linear, branched, or cyclic structure. From the viewpoint of further improving the heat resistance of the resin film, Z is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and more preferably a phenyl group.

[0052] In chemical formula (2), R 3 represents a hydrocarbon group having 1 to 20 carbon atoms, while R 3Examples of R include aliphatic hydrocarbon groups having 1 to 20 carbon atoms and aromatic hydrocarbon groups having 6 to 20 carbon atoms. These hydrocarbon groups may have any of a linear, branched, or cyclic structure. From the viewpoint of further improving the heat resistance of the resin film, R 3 is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and more preferably a methyl group or a phenyl group.

[0053] In chemical formula (2), n represents 2 or 3, preferably 3. When n is 3, the siloxane bond site has a three-dimensional structure, which makes it easier to improve the Tg of the resin film.

[0054] The value obtained by dividing the number of moles of aminosilane residues contained in the resin by the number of moles of tetracarboxylic acid residues (hereinafter referred to as the "divided value Kb") is preferably 0.1 or more, more preferably 0.2 or more, and even more preferably 0.4 or more. Furthermore, the divided value Kb is preferably 1.2 or less, and more preferably 0.9 or less. If the divided value Kb is 0.1 or more, the resin contains a large amount of the structure represented by chemical formula (2), and therefore the transparency and heat resistance of the resin film are more likely to be improved. If the divided value Kb is 1.2 or less, the mechanical properties of the resin film are good.

[0055] In chemical formula (2), X represents the structure represented by the above chemical formula (3), and the oxygen atom in chemical formula (3) is bonded to the Si atom in chemical formula (2). An example of a bond to the Si atom in chemical formula (3) is R in chemical formula (2). 3 the carbon atoms constituting Z in chemical formula (2), hydrogen atoms, and hydroxyl groups. Furthermore, the Si atom in chemical formula (3) may be bonded to an Si atom in another chemical formula (2) or (3) via an oxygen atom, forming a chain or network structure of a repeating siloxane structure. The Si atom in chemical formula (3) may be an Si atom in another chemical formula (2), or some of the Si atoms in the repeating structure represented by chemical formula (3) may be an Si atom in another chemical formula (2). A structure in which the Si atom in chemical formula (3) is an Si atom in another chemical formula (2) can be considered as a structure in which resins having the structure of chemical formula (2) are crosslinked by a siloxane structure, and is preferred because it makes it easier to improve the Tg of the resin film.

[0056] <Resin composition> The resin composition according to an embodiment of the present invention includes a resin having a repeating unit represented by chemical formula (4) and a solvent. The resin composition is applied and baked at 410°C to produce a 10-μm-thick resin film, which exhibits a light transmittance of 68% or higher at a wavelength of 400 nm, a glass transition temperature of 370°C or higher, and a weight loss onset temperature of 440°C or higher. Baking at 410°C refers to baking at 410°C for 30 minutes. The properties of the 10-μm-thick resin film obtained by baking at 410°C are specified here because temperatures of 410°C or higher are typically used to produce resin films with heat resistance sufficient to withstand high-temperature processes in the manufacture of electronic devices, and because a thickness of approximately 10 μm is typically used for applications requiring mechanical properties (e.g., display substrates).

[0057] [ka]

[0058] In chemical formula (4), A represents a tetravalent tetracarboxylic acid residue having two or more carbon atoms, and B represents a divalent diamine residue having two or more carbon atoms. 1 and R 2are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, an alkali metal ion, an ammonium ion, an imidazolium ion, or a pyridinium ion.

[0059] The resin composition according to the embodiment of the present invention can produce a resin film with a light transmittance of 68% or more, and therefore the resin composition can be suitably used in applications requiring transparency.

[0060] Furthermore, the resin composition according to the embodiment of the present invention provides a resin film having a Tg of 370°C or higher, which can prevent wrinkles from forming on the film formed on the resin film during high-temperature processes in the manufacture of electronic devices. Therefore, the resin composition is suitable for use in electronic devices that undergo high-temperature processes during manufacture. Furthermore, a higher Tg of the resin film is preferable because it allows for higher process temperatures in the manufacture of electronic devices. For example, it is more preferable for the Tg of the resin film to be 380°C or higher.

[0061] Furthermore, the resin composition according to the embodiment of the present invention provides a resin film having a Td0 of 440°C or higher, which can prevent the film formed on the resin film from peeling off during high-temperature processes in the manufacture of electronic devices. Therefore, the resin composition is suitable for use in electronic devices that undergo high-temperature processes during manufacture. Furthermore, a higher Td0 of the resin film is preferable because it allows for higher process temperatures in the manufacture of electronic devices. For example, it is more preferable for the Td0 of the resin film to be 450°C or higher.

[0062] A resin having a repeating unit represented by chemical formula (4) can be converted into a resin having a repeating unit represented by chemical formula (1) by heat treatment, chemical treatment, or the like. Hereinafter, such a resin having a repeating unit represented by chemical formula (4) and a resin having a structure represented by chemical formula (5) below will be referred to as a "precursor resin." Furthermore, a resin composition containing a precursor resin will be referred to as a "precursor resin composition." Examples of precursor resins include polyimide precursor resins, polyetherimide precursor resins, and polyamideimide precursor resins.

[0063] Specific and preferred examples of A in chemical formula (4) include the structures described as specific and preferred examples of A in the above-mentioned chemical formula (1). Specific and preferred examples of B in chemical formula (4) include the structures described as specific examples of B in the above-mentioned chemical formula (1).

[0064] Furthermore, the value obtained by dividing the number of moles of diamine residues contained in the precursor resin by the number of moles of tetracarboxylic acid residues (hereinafter referred to as the "divided value Kc") is preferably 0.4 or more, more preferably 0.6 or more. Furthermore, the divided value Kc is preferably 0.9 or less, more preferably 0.8 or less. If the divided value Kc is 0.4 or more, the mechanical properties of the resulting resin film will be good. If the divided value Kc is 0.9 or less, it is preferable because it can contain more of the structure represented by the following chemical formula (5).

[0065] The precursor resin preferably has a structure represented by chemical formula (5).

[0066] [ka]

[0067] In chemical formula (5), A represents a tetravalent tetracarboxylic acid residue having two or more carbon atoms, and B represents a divalent diamine residue having two or more carbon atoms. 1 and R 2R each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, an alkali metal ion, an ammonium ion, an imidazolium ion, or a pyridinium ion. 3 and R 4 are each independently a hydrocarbon group having 1 to 20 carbon atoms, and n is 2 or 3.

[0068] A precursor resin composition containing a precursor resin having a structure represented by chemical formula (5) tends to have higher light transmittance, Tg, and Td0 in a 10 μm-thick resin film obtained by applying the resin composition and baking it at 410°C. When the precursor resin has a terminal tetracarboxylic acid end of a repeating unit represented by chemical formula (4), the precursor resin having a structure represented by chemical formula (5) can be considered to have a structure in which an aminosilane compound having a hydrolyzable silyl group is bonded to the terminal tetracarboxylic acid structure to form an amic acid. The amic acid structure is converted to an imide structure by baking, and the hydrolyzable silyl group is converted to a siloxane structure by baking. In other words, the structure represented by chemical formula (5) is a structure that can be converted to a structure represented by chemical formula (2) by heating. Therefore, a resin film obtained by baking a precursor resin composition containing a precursor resin having a structure represented by chemical formula (5) contains a resin having a structure represented by chemical formula (2), and therefore, it is believed that the resin film obtained by baking as described above will have higher light transmittance, Tg, and Td0.

[0069] Specific and preferred examples of Z in the chemical formula (5) include the structures described above as specific and preferred examples of Z in the chemical formula (2).

[0070] R in chemical formula (5) 3 Specific and preferred examples of include the structures described as specific and preferred examples of R3 in the aforementioned chemical formula (2).

[0071] In chemical formula (5), R 4Examples of the hydrocarbon group include an aliphatic hydrocarbon group having 1 to 20 carbon atoms and an aromatic hydrocarbon group having 6 to 20 carbon atoms. These hydrocarbon groups may have any of a linear, branched or cyclic structure.

[0072] In chemical formula (5), n represents 2 or 3, but is preferably 3. When n is 3, the siloxane bond sites after baking have a three-dimensional structure, which makes it easier to improve the Tg of the resin film.

[0073] Examples of aminosilane compounds that give the chemical formula (5) include 4-aminophenyltrimethoxysilane, 4-aminophenyltriethoxysilane, 4-aminophenylmethyldimethoxysilane, 4-aminophenylmethyldiethoxysilane, 3-aminophenyltrimethoxysilane, 3-aminophenyltriethoxysilane, 3-aminophenylmethyldimethoxysilane, 3-aminophenylmethyldiethoxysilane, 2-aminophenyltrimethoxysilane, 2-aminophenyltriethoxysilane, 2-aminophenylmethyldimethoxysilane, 2-aminophenylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, etc. Among these, aminosilane compounds selected from 3-aminophenyltrimethoxysilane, 3-aminophenyltriethoxysilane, 4-aminophenyltrimethoxysilane, and 4-aminophenyltriethoxysilane are preferred.

[0074] The value obtained by dividing the number of moles of aminosilane residues contained in the precursor resin by the number of moles of tetracarboxylic acid residues (hereinafter referred to as the "divided value Kd") is preferably 0.1 or more, more preferably 0.2 or more, and even more preferably 0.4 or more. Furthermore, the divided value Kd is preferably 1.2 or less, and more preferably 0.9 or less. If the divided value Kd is 0.1 or more, the precursor resin contains a large amount of the structure represented by chemical formula (5), and therefore the transparency and heat resistance of the resulting resin film are more likely to be improved. If the divided value Kd is 1.2 or less, the mechanical properties of the resulting resin film are good.

[0075] In the present invention, the precursor resin may further contain, in addition to the repeating unit represented by the above-mentioned chemical formula (4), at least one of a repeating unit represented by the chemical formula (61), a repeating unit represented by the chemical formula (62), and a repeating unit represented by the chemical formula (1).

[0076] [ka]

[0077] A, B, and R in the above chemical formulas (61), (62), and chemical formula (1) 1 and R 2 is as explained above. The repeating unit represented by chemical formula (61), the repeating unit represented by chemical formula (62), and the repeating unit represented by chemical formula (1) each have a structure in which the repeating unit represented by chemical formula (4) is subjected to imide ring closure by heat treatment, chemical treatment, or the like. In other words, a precursor resin that contains a repeating unit represented by chemical formula (4) and at least one of the repeating unit represented by chemical formula (61), the repeating unit represented by chemical formula (62), and the repeating unit represented by chemical formula (1) can also be considered as a partially imidized precursor resin.

[0078] The molar ratios of the repeating units represented by chemical formula (4), the repeating units represented by chemical formula (61), the repeating units represented by chemical formula (62), and the repeating units represented by chemical formula (1) contained in the precursor resin are denoted by s, t, u, and v, respectively. The imidization ratio of the polyimide precursor is expressed as (t + u + 2v) / (2s + 2t + 2u + 2v) × 100. In other words, the imidization ratio indicates the ratio of the number of imide-ring-closed bonds (t + u + 2v) to the total number of bonds (2s + 2t + 2u + 2v) at the bonds (reaction sites between tetracarboxylic dianhydride and diamine compound) of the polyimide precursor.

[0079] From the viewpoint of improving the storage stability of the precursor resin composition, the imidization rate of the precursor resin is preferably 5 to 30%, more preferably 10% or more, and even more preferably 13% or more, and more preferably 27% or less, and even more preferably 25% or less.

[0080] The imidization rate of the precursor resin is measured as follows. 1 1H-NMR spectrum is measured. 1 The integral value (ε) of the H peak and the molar ratio of the repeating units represented by the chemical formula (4), the chemical formula (61) or the chemical formula (62), and the chemical formula (1) contained in the precursor resin were 100:0:0. 1 The integral value (β) of the peak of H is calculated. In other words, the integral value of the amide group when the precursor resin is assumed to be a completely unimidized amic acid resin is calculated. 1 The integral value of the peak of H is calculated. Using these β and ε, the imidization rate can be calculated by the following formula.

[0081] Imidization rate = (β-ε) / β×100 In addition, β can be calculated by the following formula: In the formula, α is the sum of all the values ​​included in A and B in chemical formula (4), chemical formula (61), chemical formula (62), and chemical formula (1). 1 H or specific 1is the integral value of the H peak. ω is the number of hydrogen atoms considered when α is calculated.

[0082] β=α / ω×2 1 The sample for H-NMR measurement is preferably the precursor resin alone, but may contain other resin components or solvents. 1 The H peak is an index for calculating the imidization rate. 1 It is preferable that the peak does not overlap with the peak of H.

[0083] The solvent contained in the precursor resin composition can be any solvent that dissolves the precursor resin without any particular limitation. Examples of such solvents include aprotic polar solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N,N-dimethylisobutyramide, 1,3-dimethyl-2-imidazolidinone, N,N'-dimethylpropyleneurea, and dimethyl sulfoxide; tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monomethyl ether. Examples of the solvent include ethers such as ethylene glycol monoethyl ether, diethylene glycol ethyl methyl ether, and diethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, diacetone alcohol, and cyclohexanone, esters such as ethyl acetate, propylene glycol monomethyl ether acetate, ethyl lactate, 3-methyl-3-methoxybutyl acetate, ethylene glycol ethyl ether acetate, and 3-methoxybutyl acetate, aromatic hydrocarbons such as toluene and xylene, and the solvents described in International Publication No. 2017 / 099183. As the solvent, any of these can be used alone, or two or more of these can be used in combination.

[0084] The precursor resin composition may contain a silane compound (h), which is preferably a compound having a structure represented by chemical formula (7).

[0085] [ka]

[0086] In chemical formula (7), R 5 and R 6 each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and m represents 3 or 4.

[0087] When the precursor resin composition contains a silane compound (h), the silane compound (h) condenses to form a siloxane bond during baking of the precursor resin composition. Therefore, siloxane moieties are formed in the resin film obtained by baking, which can further improve the light transmittance of the resin film. In particular, when the precursor resin composition contains a precursor resin having a structure represented by chemical formula (5), the silane compound (h) and the hydrolyzable silyl group in chemical formula (5) condense to form a siloxane bond during baking, which suppresses phase separation between the resin and the siloxane moieties contained in the resin film, making it easier to obtain a resin film with superior light transmittance.

[0088] In chemical formula (7), R 5 Examples of R include aliphatic hydrocarbon groups having 1 to 20 carbon atoms and aromatic hydrocarbon groups having 6 to 20 carbon atoms. These hydrocarbon groups may have any of a linear, branched, or cyclic structure. From the viewpoint of further improving the heat resistance of the resin film, R 5 is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably a methyl group or a phenyl group, and particularly preferably a phenyl group.

[0089] In chemical formula (7), R 6 Examples of the hydrocarbon group include an aliphatic hydrocarbon group having 1 to 20 carbon atoms and an aromatic hydrocarbon group having 6 to 20 carbon atoms. These hydrocarbon groups may have any of a linear, branched or cyclic structure.

[0090] Examples of compounds having a structure represented by chemical formula (7) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane.

[0091] The content of the silane compound (h) is preferably 15 parts by mass or more and 100 parts by mass or less relative to 100 parts by mass of the precursor resin composition. If the content of the silane compound (h) is 15 parts by mass or more, the light transmittance of the resin film is likely to be improved. If the content is 100 parts by mass or less, a resin film with good mechanical properties is likely to be obtained.

[0092] The precursor resin composition may optionally contain at least one additive selected from the group consisting of a photoacid generator (a), a thermal crosslinker (b), a thermal acid generator (c), a compound containing a phenolic hydroxyl group (d), an adhesion improver (e), a surfactant (f), and inorganic particles (g). Specific examples of these additives include those described in International Publication No. 2017 / 099183.

[0093] The concentration of the precursor resin in the precursor resin composition is preferably 3% by mass or more, more preferably 5% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, relative to 100% by mass of the precursor resin composition.

[0094] The viscosity of the precursor resin composition is preferably 20 to 20,000 mPa·s, and more preferably 50 to 10,000 mPa·s.

[0095] (Method of producing precursor resin composition) Next, a method for producing a precursor resin composition will be described. In the method for producing a precursor resin composition, a precursor resin, and optionally a silane compound (h), a photoacid generator (a), a thermal crosslinker (b), a thermal acid generator (c), a compound containing a phenolic hydroxyl group (d), an adhesion improver (e), a surfactant (f), and inorganic particles (g) are dissolved or dispersed in a solvent. This allows a varnish, which is one of the precursor resin compositions, to be obtained.

[0096] The precursor resin having the repeating unit represented by chemical formula (4) can be polymerized by known methods. For example, it can be obtained by polymerizing a tetracarboxylic acid or a corresponding acid dianhydride, activated ester, activated amide, or the like as an acid component and a diamine or a corresponding trimethylsilylated diamine, or the like as a diamine component in a reaction solvent. Furthermore, the precursor resin may be one in which the carboxyl group forms a salt with an alkali metal ion, ammonium ion, or imidazolium ion, or is esterified with a hydrocarbon group having 1 to 10 carbon atoms or an alkylsilyl group having 1 to 10 carbon atoms.

[0097] As the reaction solvent, for example, the solvents described above as specific examples of the solvent contained in the precursor resin composition can be used alone or in combination of two or more. The amount of the reaction solvent used is preferably adjusted so that the total amount of the tetracarboxylic acid and diamine compound is 0.1 to 50 mass% of the entire reaction solution. The reaction temperature is preferably -20°C to 150°C, more preferably 0 to 100°C. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

[0098] The precursor resin having the structure represented by chemical formula (5) is produced by the method described below.

[0099] Manufacturing method 1: The first production method is a production method in which, in the first step, a tetracarboxylic dianhydride is reacted with an aminosilane compound to produce a compound represented by chemical formula (9), and in the second step, the compound represented by chemical formula (9), a diamine compound, and a tetracarboxylic dianhydride are reacted to produce a precursor resin having a structure represented by chemical formula (5).

[0100] [ka]

[0101] In the chemical formula (9), A represents a tetracarboxylic acid residue having two or more carbon atoms. 3 and R 4 are each independently a hydrocarbon group having 1 to 20 carbon atoms, and n is 2 or 3.

[0102] Manufacturing method 2: The second production method is a production method in which, in the first step, a diamine compound is reacted with a tetracarboxylic dianhydride to produce a precursor resin having a repeating unit represented by chemical formula (4), and in the second step, a resin having a structure represented by chemical formula (10) is reacted with an aminosilane compound to produce a precursor resin having a structure represented by chemical formula (5).

[0103] [ka]

[0104] In chemical formula (10), A represents a tetravalent tetracarboxylic acid residue having two or more carbon atoms, and B represents a divalent diamine residue having two or more carbon atoms. 2 represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, an alkali metal ion, an ammonium ion, an imidazolium ion, or a pyridinium ion.

[0105] Furthermore, the precursor resin having the structure represented by chemical formula (5) may be produced by combining production methods 1 and 2.

[0106] In the above-described production method, the corresponding tetracarboxylic acid may be a corresponding acid dianhydride, an activated ester, an activated amide, or the like. The corresponding diamine compound may be a corresponding trimethylsilylated diamine. The carboxyl group of the resulting resin may be a salt formed with an alkali metal ion, an ammonium ion, or an imidazolium ion, or may be esterified with a hydrocarbon group having 1 to 10 carbon atoms or an alkylsilyl group having 1 to 10 carbon atoms.

[0107] The obtained precursor resin solution may be used as it is as the precursor resin composition according to the embodiment of the present invention. In this case, the target precursor resin composition can be obtained without isolating the precursor resin by using the same solvent as that used for the precursor resin composition as the reaction solvent or by adding a solvent after the reaction is completed.

[0108] The resulting precursor resin may be further subjected to imidization or esterification of a portion of the repeating units of the amic acid. In this case, the precursor resin solution obtained by polymerization of the precursor resin may be used directly in the next reaction, or the precursor resin may be isolated and then used in the next reaction.

[0109] In the esterification reaction and imidization reaction of the precursor resin, the target precursor resin composition can be obtained without isolating the precursor resin by using the same solvent as that used for the precursor resin composition as the reaction solvent or by adding a solvent after completion of the reaction.

[0110] (Method of manufacturing resin film) Next, a method for producing a resin film according to an embodiment of the present invention will be described. This method is an example of a method for producing a resin film according to an embodiment of the present invention from the precursor resin composition described above.

[0111] First, a varnish, which is one of the precursor resin compositions according to the embodiment of the present invention, is applied to a support. Examples of the support include a wafer substrate such as silicon or gallium arsenide, a glass substrate such as sapphire glass, soda-lime glass, or alkali-free glass, a metal substrate or metal foil such as stainless steel or copper, or a ceramic substrate. Among these, alkali-free glass is preferred from the viewpoints of surface smoothness and dimensional stability during heating.

[0112] Examples of methods for applying the varnish include spin coating, slit coating, dip coating, spray coating, printing, etc., and these methods may be combined. When the resin film is used as a display substrate, it is necessary to apply the film onto a large-sized support, and therefore, the slit coating method is particularly preferably used.

[0113] After application, the varnish coating is generally dried. Drying methods include vacuum drying, heat drying, or a combination of these. Examples of vacuum drying methods include placing a substrate with a coating film formed thereon in a vacuum chamber and drying the coating film by reducing the pressure inside the vacuum chamber. Examples of heat drying methods include drying the coating film using a hot plate, oven, infrared rays, or the like. When using a hot plate, the substrate with the coating film formed thereon is held directly on the plate or on a jig such as a proxy pin placed on the plate, and the coating film is heated and dried. The heating temperature varies depending on the type and purpose of the solvent used in the varnish, and it is preferable to heat the substrate at room temperature to 180°C for 1 minute to several hours.

[0114] When the resin composition to be coated contains a photoacid generator (a), a pattern can be formed from the dried coating film by the method described below. For example, in this method, the coating film is exposed to actinic radiation through a mask having a desired pattern. Actinic radiation used for exposure includes ultraviolet light, visible light, electron beams, and X-rays. In the present invention, it is preferable to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) from a mercury lamp. When the coating film has positive photosensitivity, the exposed portions of the coating film dissolve in the developer. When the coating film has negative photosensitivity, the exposed portions of the coating film harden and become insoluble in the developer.

[0115] After exposure, a developer is used to remove the exposed areas in the case of a positive-tone film, or the unexposed areas in the case of a negative-tone film, thereby forming a desired pattern in the coating film. For both positive-tone and negative-tone films, the developer is preferably an aqueous solution of an alkaline compound such as tetramethylammonium. In some cases, polar solvents such as N-methyl-2-pyrrolidone, alcohols, esters, ketones, etc., may be added alone or in combination to these alkaline aqueous solutions.

[0116] Then, a heating step is carried out in which the coating film on the support is heat-treated to produce a resin film. In this heating step, the coating film is heat-treated at a temperature of 370°C or higher and 600°C or lower, preferably 400°C or higher and 490°C or lower, and more preferably 410°C or higher and 470°C or lower, to bake the coating film. This allows a resin film to be produced on the support. If the heating temperature (baking temperature) of the coating film in the heating step is 370°C or higher, imidization proceeds sufficiently, resulting in a resin film with excellent mechanical properties. If the heating temperature is 400°C or higher, a resin film with excellent heat resistance is obtained. Furthermore, if the heating temperature is 490°C or lower, thermal decomposition of the resin is suppressed, resulting in a resin film with high transmittance.

[0117] The resin film obtained through the above coating and heating steps can be used after being peeled off from the support, or can be used as it is without being peeled off from the support.

[0118] Examples of the peeling method include a mechanical peeling method, a method of immersion in water, a method of immersion in a chemical solution such as hydrochloric acid or hydrofluoric acid, a method of irradiating the interface between the resin film and the support with laser light in the wavelength range from ultraviolet light to infrared light, etc. In particular, when peeling is performed after a device has been formed on the resin film, peeling using an ultraviolet laser is preferred because peeling must be performed without damaging the device.

[0119] To facilitate peeling, a release agent may be applied to the support or a sacrificial layer may be formed on the support before applying the resin composition to the support. Examples of the release agent include silicone-based, fluorine-based, aromatic polymer-based, and alkoxysilane-based agents. Examples of the sacrificial layer include a metal film, a metal oxide film, and an amorphous silicon film.

[0120] The resin film according to the embodiment of the present invention is suitable for use as a display substrate such as an organic EL display substrate, a color filter substrate, a touch panel substrate, an electronic paper substrate, or a μLED display substrate, and is particularly suitable for use as a flexible display substrate. It can also be used as a flexible printed circuit board, a solar cell substrate, a surface protection film or interlayer insulating film for semiconductor elements, an insulating layer or spacer layer for organic electroluminescence elements (organic EL elements), a planarizing film for thin-film transistor substrates, an insulating layer for organic transistors, a binder for electrodes in lithium-ion secondary batteries, or an adhesive for semiconductors.

[0121] (display) Next, a display according to an embodiment of the present invention will be described. The display according to the embodiment of the present invention includes the resin film according to the embodiment of the present invention.

[0122] In the following, a method for manufacturing a display according to an embodiment of the present invention will be described.

[0123] An example of a configuration of a display according to an embodiment of the present invention includes a resin film and a display element formed on the resin film.

[0124] The resin film is a resin film according to an embodiment of the present invention, and functions as a substrate for a display. Display elements are formed on the resin film.

[0125] This display manufacturing method includes a film manufacturing process in which a resin film is manufactured on a support by the above-described resin film manufacturing method, a process in which a display element is formed on the resin film, and a peeling process in which the resin film is peeled off from the support.

[0126] First, the resin film according to the embodiment of the present invention is produced on a support according to the above-mentioned method for producing a resin film.

[0127] If necessary, an inorganic film may be provided on the resin film. The provision of an inorganic film can prevent external moisture or oxygen from penetrating the resin film and causing deterioration of the display element. Examples of inorganic films include silicon oxide (SiOx), silicon nitride (SiNy), and silicon oxynitride (SiOxNy). These films can be used as a single layer or by laminating multiple types. These inorganic films are preferably formed using a vapor deposition method such as chemical vapor deposition (CVD) or physical vapor deposition (PVD). These inorganic films can also be used by alternately laminating multiple resin films and inorganic films. The resin film laminated with the inorganic film is preferably a resin film according to an embodiment of the present invention. Alternatively, another resin film can be formed on a support, and then an inorganic film and a resin film according to an embodiment of the present invention can be alternately laminated on the resin film.

[0128] Next, a display element corresponding to the intended display is formed on the obtained resin film or the laminate of the resin film and the inorganic film. For example, when the display is an organic EL display, the display elements, TFT, first electrode, light-emitting element, second electrode, and sealing film, are sequentially formed to form the intended display element, an organic EL element. When the display is a liquid crystal display, a liquid crystal cell is formed using a first substrate on which TFT, first electrode, and first alignment film, which are image driving elements, are formed, and a second substrate on which a second electrode and second alignment film are formed, and liquid crystal is then injected to form the intended display element, a liquid crystal display element. When the display is a display including a color filter, a black matrix is ​​formed as needed, and then colored pixels, such as red, green, and blue, are formed to form the intended display element, a color filter element. When the display is a display including a touch panel, a wiring layer and an insulating layer are formed to form the intended display element, a touch panel element.

[0129] Finally, the resin film is peeled from the support, and the peeled resin film (on which the desired display element is formed) is used to obtain a display containing the resin film of the present invention. Methods for peeling at the interface between the support and the resin film include a method using a laser, a mechanical peeling method, and a method of etching the support. In the method using a laser, peeling can be performed without damaging the element by irradiating the support, such as a glass substrate, with a laser from the side on which the element is not formed. In addition, a primer layer may be provided between the support and the resin film to facilitate peeling. [Example]

[0130] The present invention will be described below with reference to examples, but the present invention is not limited to the following examples. First, the measurements, evaluations, tests, etc. performed in the following examples and comparative examples will be described. Note that unless otherwise specified, the number of measurements (n) is 1.

[0131] (Item 1: Measurement of viscosity change rate of precursor resin composition) The resin composition (varnish) obtained in each synthesis example was placed in a clean bottle (manufactured by Aicello Co., Ltd.) and stored at 23°C for 10 days. The viscosity of the resin composition (varnish) before and after storage was measured, and the viscosity change rate was calculated according to the following formula. The viscosity was measured at 25°C using a viscometer (manufactured by Toki Sangyo Co., Ltd., TVE-22H). Viscosity change rate (%) = (viscosity after storage - viscosity before storage) / viscosity before storage × 100.

[0132] (Item 2: Measurement of the imidization rate of the precursor resin) The precursor resins obtained in each synthesis example were analyzed using a nuclear magnetic resonance spectrometer (JEOL EX-270). 1 The H-NMR spectrum was measured. The measurement sample was prepared by diluting the resin composition (varnish) obtained in each synthesis example with a heavy solvent (deuterated dimethyl sulfoxide). Next, all of the diamine residues and tetracarboxylic acid residues contained in the precursor resin composition components were analyzed. 1 The integral value (α) of the H peak was calculated. 1 The integral value (referred to as ε) of the peak of H was determined. Using these values, the imidization rate of the precursor resin contained in the precursor resin composition components was measured.

[0133] Imidization rate = (β-ε) / β×100 Here, β = α / ω × 2, and ω is the number of hydrogen atoms considered when α was calculated.

[0134] (Item 3: Measurement of light transmittance of resin film) For each resin film obtained in each example, a laminate of the resin film and a glass substrate was prepared, and the light transmittance of the resin film at a wavelength of 400 nm was measured for each prepared laminate using an ultraviolet-visible spectrophotometer (Shimadzu Corporation, MultiSpec1500).

[0135] (Item 4: Measurement of Tg of resin film) The Tg of the resin film (sample) obtained in each example was measured using a thermomechanical analyzer (EXSTAR6000TMA / SS6000, manufactured by SII NanoTechnology Inc.). In the first step, the sample was heated to 150°C at a heating rate of 5°C / min, thereby removing the adsorbed water from the sample. In the subsequent second step, the sample was air-cooled to room temperature at a cooling rate of 5°C / min. In the subsequent third step, the sample was heated at a heating rate of 5°C / min, and the Tg of the sample was measured.

[0136] (Item 5: Measurement of Td0 of resin film) The resin films (samples) obtained in each example were subjected to Td0 measurement using a thermogravimetric analyzer (Shimadzu Corporation, TGA-50). In the first stage, the sample was heated to 150°C at a heating rate of 10°C / min, thereby removing adsorbed water from the sample. In the subsequent second stage, the sample was air-cooled to room temperature at a cooling rate of 10°C / min. In the subsequent third stage, the sample's Td0 was measured at a heating rate of 10°C / min.

[0137] (Item 6: Measurement of tensile elongation and maximum tensile stress of resin film) Using the resin film obtained in each example, measurements were carried out using a Tensilon universal material testing machine (RTM-100 manufactured by Orientec Co., Ltd.) in accordance with the Japanese Industrial Standards (JIS K 7127: 1999). The measurement conditions were a test piece width of 10 mm, a chuck spacing of 50 mm, a test speed of 50 mm / min, and the number of measurements (n = 10).

[0138] (Item 7: Wrinkle evaluation) For the laminates consisting of the resin film and glass substrate obtained in each example, a 50 nm thick SiO film was formed on the resin film by CVD, and then heat-treated at 425°C or 450°C for 30 minutes. The presence or absence of wrinkles in the SiO film on the resin film was then determined by visual inspection and observation with an optical microscope. Those that wrinkled at 425°C were rated "C," those that wrinkled only at 450°C were rated "B," and those that did not wrinkle were rated "A."

[0139] (Item 8: Film floating evaluation) For the laminates consisting of the resin film and glass substrate obtained in each example, a 50 nm thick SiO film was formed on the resin film by CVD, and then heat-treated at 450°C for 120 minutes. The number of SiO film floating areas from the resin film was then determined by visual inspection and observation with an optical microscope. The evaluation range was the entire surface (350 mm long x 300 mm wide), and the observation magnification was 50x.

[0140] (compound) In the examples and comparative examples, the following compounds are used as appropriate. Each compound and its abbreviation are as follows: DDS: 4,4'-diaminodiphenyl sulfone PDA: p-phenylenediamine TFMB: 2,2'-di(trifluoromethyl)-4,4'-diaminobiphenyl DABA: 4,4'-diaminobenzanilide DAE: 4,4'-diaminodiphenyl ether BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride DNDA: a compound with a structure represented by chemical formula (35) CpODA: a compound with a structure represented by chemical formula (36) 3APhTMS: 3-aminophenyltrimethoxysilane 3APTMS: 3-aminopropyltrimethoxysilane 3APhDMS: 3-aminophenyldimethoxymethylsilane PTMS: Phenyltrimethoxysilane NMP: N-methyl-2-pyrrolidone.

[0141] [ka]

[0142] (Synthesis Example 1) A thermometer and a stirring rod with a stirring blade were installed in a 300 mL four-neck flask. Next, under a dry nitrogen stream, NMP (140 g) and DDS (17.5 g (70.5 mmol)) were added and the temperature was raised to 50 °C. After the temperature was raised, BPDA (29.6 g (100.7 mmol)) was added while stirring. After stirring for 2 hours, 3APhTMS (12.9 g (60.4 mmol)) was added. After stirring for 2 hours, molecular sieves 4A (10 g) were added, the temperature was raised to 70 °C, and the mixture was stirred for 6 hours. The reaction solution was cooled to room temperature, diluted with NMP to a viscosity of approximately 2000 cP, and filtered through a filter with a pore size of 0.2 μm to obtain a resin composition (varnish).

[0143] (Synthesis Example 2) A thermometer and a stirring rod with a stirring blade were installed in a 300 mL four-neck flask. Next, under a dry nitrogen stream, NMP (140 g) and DDS (25.7 g (103.4 mmol)) were added and the temperature was raised to 50 °C. After the temperature was raised, BPDA (32.0 g (108.8 mmol)) was added while stirring. After stirring for 2 hours, 3APhTMS (2.3 g (10.9 mmol)) was added. After stirring for 2 hours, molecular sieves 4A (10 g) were added, the temperature was raised to 70 °C, and the mixture was stirred for 6 hours. The reaction solution was cooled to room temperature, diluted with NMP to a viscosity of approximately 2000 cP, and filtered through a filter with a pore size of 0.2 μm to obtain a resin composition (varnish).

[0144] (Synthesis Example 3) A thermometer and a stirring rod with a stirring blade were installed in a 300 mL four-neck flask. Next, under a dry nitrogen stream, NMP (140 g) and DDS (20.6 g (83.0 mmol)) were added and the temperature was raised to 50 °C. After the temperature was raised, BPDA (30.5 g (103.8 mmol)) was added while stirring. After stirring for 2 hours, 3APhTMS (8.9 g (41.5 mmol)) was added. After stirring for 2 hours, molecular sieves 4A (10 g) were added, the temperature was raised to 70 °C, and the mixture was stirred for 6 hours. The reaction solution was cooled to room temperature, diluted with NMP to a viscosity of approximately 2000 cP, and filtered through a filter with a pore size of 0.2 μm to obtain a resin composition (varnish).

[0145] (Synthesis Example 4) A thermometer and a stirring rod with a stirring blade were installed in a 300 mL four-neck flask. Next, under a dry nitrogen stream, NMP (140 g) and DDS (16.0 g (64.5 mmol)) were added and the temperature was raised to 50 °C. After the temperature was raised, BPDA (29.2 g (99.2 mmol)) was added while stirring. After stirring for 2 hours, 3APhTMS (14.8 g (69.4 mmol)) was added. After stirring for 2 hours, molecular sieves 4A (10 g) were added, the temperature was raised to 70 °C, and the mixture was stirred for 6 hours. The reaction solution was cooled to room temperature, diluted with NMP to a viscosity of approximately 2000 cP, and filtered through a filter with a pore size of 0.2 μm to obtain a resin composition (varnish).

[0146] (Synthesis Example 5) A thermometer and a stirring rod with a stirring blade were installed in a 300 mL four-neck flask. Next, under a dry nitrogen stream, NMP (140 g) and DDS (25.8 g (104.0 mmol)) were added and the temperature was raised to 50 °C. After the temperature was raised, BPDA (32.2 g (109.5 mmol)) was added while stirring. After stirring for 2 hours, 3APTMS (2.0 g (10.9 mmol)) was added. After stirring for 2 hours, molecular sieves 4A (10 g) were added, the temperature was raised to 70 °C, and the mixture was stirred for 6 hours. The reaction solution was cooled to room temperature, diluted with NMP to a viscosity of approximately 2000 cP, and filtered through a filter with a pore size of 0.2 μm to obtain a resin composition (varnish).

[0147] (Synthesis Example 6) A thermometer and a stirring rod with a stirring blade were installed in a 300 mL four-neck flask. Next, under a dry nitrogen stream, NMP (140 g) and DDS (17.5 g (70.5 mmol)) were added, and the temperature was raised to 50 °C. After the temperature was raised, BPDA (29.6 g (100.7 mmol)) was added while stirring. After stirring for 2 hours, 3APhTMS (12.9 g (60.4 mmol)) was added. After stirring for 2 hours, the reaction solution was cooled to room temperature. Thereafter, it was diluted with NMP to a viscosity of approximately 2000 cP, and filtered through a filter with a pore size of 0.2 μm to obtain a resin composition (varnish).

[0148] (Synthesis Example 7) A thermometer and a stirring rod with a stirring blade were installed in a 300 mL four-neck flask. Next, under a dry nitrogen stream, NMP (140 g) and DDS (17.5 g (70.5 mmol)) were added and the temperature was raised to 50 °C. After the temperature was raised, BPDA (29.6 g (100.7 mmol)) was added while stirring. After stirring for 2 hours, 3APhTMS (12.9 g (60.4 mmol)) was added. After stirring for 2 hours, molecular sieves 4A (10 g) were added, the temperature was raised to 90 °C, and the mixture was stirred for 6 hours. The reaction solution was cooled to room temperature, diluted with NMP to a viscosity of approximately 2000 cP, and filtered through a filter with a pore size of 0.2 μm to obtain a resin composition (varnish).

[0149] (Synthesis Example 8) A 300 mL four-neck flask was equipped with a thermometer and a stirring rod with a stirring blade. Next, under a dry nitrogen stream, NMP (140 g) and DDS (17.5 g (70.5 mmol)) were added and the temperature was raised to 50 °C. After the temperature was raised, BPDA (29.6 g (100.7 mmol)) was added while stirring. After stirring for 2 hours, 3APhTMS (12.9 g (60.4 mmol)) was added. After stirring for 2 hours, molecular sieves 4A (10 g) were added, the temperature was raised to 70 °C, and the mixture was stirred for 6 hours. The reaction solution was cooled to room temperature, and then PTMS (36 g) was added and stirred until uniformly mixed. After stirring was completed, the mixture was diluted with NMP to a viscosity of approximately 2000 cP and filtered through a filter with a pore size of 0.2 μm to obtain a resin composition (varnish).

[0150] (Synthesis Example 9) A thermometer and a stirring rod with a stirring blade were installed in a 300 mL four-neck flask. Next, under a dry nitrogen stream, NMP (140 g) and DDS (27.2 g (109.4 mmol)) were added and the temperature was raised to 50 °C. After the temperature was raised, BPDA (32.8 g (111.6 mmol)) was added while stirring. After stirring for 4 hours, molecular sieves 4A (10 g) were added, the temperature was raised to 70 °C, and the mixture was stirred for 6 hours. The reaction solution was cooled to room temperature, diluted with NMP to a viscosity of approximately 2000 cP, and filtered through a filter with a pore size of 0.2 μm to obtain a resin composition (varnish).

[0151] (Synthesis Example 10) A 300 mL four-neck flask was equipped with a thermometer and a stirring rod with a stirring blade. Next, under a dry nitrogen stream, NMP (140 g) and TFMB (20.8 g (65.1 mmol)) were added and the temperature was raised to 50 °C. After the temperature was raised, BPDA (27.3 g (92.9 mmol)) was added while stirring. After stirring for 2 hours, 3APhTMS (11.9 g (55.8 mmol)) was added. After stirring for 2 hours, molecular sieves 4A (10 g) were added, the temperature was raised to 70 °C, and the mixture was stirred for 6 hours. The reaction solution was cooled to room temperature, diluted with NMP to a viscosity of approximately 2000 cP, and filtered through a filter with a pore size of 0.2 μm to obtain a resin composition (varnish).

[0152] (Synthesis Example 11) A 300 mL four-neck flask was equipped with a thermometer and a stirring rod with a stirring blade. Next, under a dry nitrogen stream, NMP (140 g) and PDA (9.1 g (84.4 mmol)) were added and the temperature was raised to 50 °C. After the temperature was raised, BPDA (35.5 g (120.5 mmol)) was added while stirring. After stirring for 2 hours, 3APhTMS (15.4 g (72.3 mmol)) was added. After stirring for 2 hours, molecular sieves 4A (10 g) were added, the temperature was raised to 70 °C, and the mixture was stirred for 6 hours. The reaction solution was cooled to room temperature, diluted with NMP to a viscosity of approximately 2000 cP, and filtered through a filter with a pore size of 0.2 μm to obtain a resin composition (varnish).

[0153] (Synthesis Example 12) A thermometer and a stirring rod with a stirring blade were installed in a 300 mL four-neck flask. Next, under a dry nitrogen stream, NMP (140 g) and DAE (15.0 g (74.7 mmol)) were added and the temperature was raised to 50 °C. After the temperature was raised, BPDA (31.4 g (106.7 mmol)) was added while stirring. After stirring for 2 hours, 3APhTMS (15.7 g (64.0 mmol)) was added. After stirring for 2 hours, molecular sieves 4A (10 g) were added, the temperature was raised to 70 °C, and the mixture was stirred for 6 hours. The reaction solution was cooled to room temperature, diluted with NMP to a viscosity of approximately 2000 cP, and filtered through a filter with a pore size of 0.2 μm to obtain a resin composition (varnish).

[0154] (Synthesis Example 13) A thermometer and a stirring rod with a stirring blade were installed in a 300 mL four-neck flask. Next, under a dry nitrogen stream, NMP (140 g) and DDS (18.1 g (73.0 mmol)) were added and the temperature was raised to 50 °C. After the temperature was raised, BPDA (30.7 g (104.2 mmol)) was added while stirring. After stirring for 2 hours, 3APTMS (11.2 g (62.5 mmol)) was added. After stirring for 2 hours, molecular sieves 4A (10 g) were added, the temperature was raised to 70 °C, and the mixture was stirred for 6 hours. The reaction solution was cooled to room temperature, diluted with NMP to a viscosity of approximately 2000 cP, and filtered through a filter with a pore size of 0.2 μm to obtain a resin composition (varnish).

[0155] (Synthesis Example 14) A thermometer and a stirring rod with a stirring blade were installed in a 300 mL four-neck flask. Next, under a dry nitrogen stream, NMP (140 g) and DDS (7.9 g (31.9 mmol)) were added and the temperature was raised to 50 °C. After the temperature was raised, BPDA (26.8 g (91.1 mmol)) was added while stirring. After stirring for 2 hours, 3APhTMS (25.3 g (118.5 mmol)) was added. After stirring for 2 hours, molecular sieves 4A (10 g) were added, the temperature was raised to 70 °C, and the mixture was stirred for 6 hours. The reaction solution was cooled to room temperature, diluted with NMP to a viscosity of approximately 2000 cP, and filtered through a filter with a pore size of 0.2 μm to obtain a resin composition (varnish).

[0156] (Synthesis Example 15) A thermometer and a stirring rod with a stirring blade were installed in a 300 mL four-neck flask. Next, under a dry nitrogen stream, NMP (140 g) and DABA (16.2 g (71.3 mmol)) were added and the temperature was raised to 50 °C. After the temperature was raised, DNDA (30.8 g (101.8 mmol)) was added while stirring. After stirring for 2 hours, 3APhTMS (13.0 g (61.1 mmol)) was added. After stirring for 2 hours, molecular sieves 4A (10 g) were added, the temperature was raised to 70 °C, and the mixture was stirred for 6 hours. The reaction solution was cooled to room temperature, diluted with NMP to a viscosity of approximately 2000 cP, and filtered through a filter with a pore size of 0.2 μm to obtain a resin composition (varnish).

[0157] (Synthesis Example 16) A 300 mL four-neck flask was equipped with a thermometer and a stirring rod with a stirring blade. Next, under a dry nitrogen stream, NMP (140 g), DABA (7.2 g (31.7 mmol)), and DAE (6.4 g (31.7 mmol)) were added and the temperature was raised to 50 °C. After the temperature was raised, CpODA (34.8 g (90.6 mmol)) was added while stirring. After stirring for 2 hours, 3APhTMS (11.6 g (54.4 mmol)) was added. After stirring for 2 hours, molecular sieves 4A (10 g) were added, the temperature was raised to 70 °C, and the mixture was stirred for 6 hours. The reaction solution was cooled to room temperature, diluted with NMP to a viscosity of approximately 2000 cP, and filtered through a filter with a pore size of 0.2 μm to obtain a resin composition (varnish).

[0158] (Synthesis Example 17) A thermometer and a stirring rod with a stirring blade were installed in a 300 mL four-neck flask. Next, under a dry nitrogen stream, NMP (140 g) and DABA (25.5 g (112.0 mmol)) were added and the temperature was raised to 50 °C. After the temperature was raised, DNDA (34.5 g (114.3 mmol)) was added while stirring. After stirring for 4 hours, molecular sieves 4A (10 g) were added, the temperature was raised to 70 °C, and the mixture was stirred for 6 hours. After cooling the reaction solution to room temperature, it was diluted with NMP to a viscosity of approximately 2000 cP and filtered through a filter with a pore size of 0.2 μm to obtain a resin composition (varnish).

[0159] (Synthesis Example 18) A thermometer and a stirring rod with a stirring blade were installed in a 300 mL four-neck flask. Next, under a dry nitrogen stream, NMP (140 g), DABA (11.3 g (49.5 mmol)), and DAE (9.9 g (49.5 mmol)) were added and the temperature was raised to 50 °C. After the temperature was raised, CpODA (38.8 g (101.0 mmol)) was added while stirring. After stirring for 4 hours, molecular sieves 4A (10 g) were added, the temperature was raised to 70 °C, and the mixture was stirred for 6 hours. The reaction solution was cooled to room temperature, diluted with NMP to a viscosity of approximately 2000 cP, and filtered through a filter with a pore size of 0.2 μm to obtain a resin composition (varnish).

[0160] (Synthesis Example 19) A thermometer and a stirring rod with a stirring blade were installed in a 300 mL four-neck flask. Next, under a dry nitrogen stream, NMP (140 g) and DDS (17.8 g (71.6 mmol)) were added and the temperature was raised to 50 °C. After the temperature was raised, BPDA (30.1 g (102.3 mmol)) was added while stirring. After stirring for 2 hours, 3APhDMS (12.1 g (61.4 mmol)) was added. After stirring for 2 hours, molecular sieves 4A (10 g) were added, the temperature was raised to 70 °C, and the mixture was stirred for 6 hours. The reaction solution was cooled to room temperature, diluted with NMP to a viscosity of approximately 2000 cP, and filtered through a filter with a pore size of 0.2 μm to obtain a resin composition (varnish).

[0161] Table 1 shows the composition of each of the resin compositions (varnishes) obtained in Synthesis Examples 1 to 19.

[0162] [Table 1]

[0163] Example 1 Using the resin composition (varnish) obtained in Synthesis Example 1, the viscosity change rate of the resin precursor composition was measured by the method in the first item above, and the imidization rate of the resin precursor was measured by the method in the second item above.

[0164] Next, using a slit coater (manufactured by Toray Engineering Co., Ltd.), the resin composition (varnish) of Synthesis Example 1 was applied to an area 5 mm inward from the edge of an alkali-free glass substrate (AN-100, manufactured by Asahi Glass Co., Ltd.) measuring 350 mm long x 300 mm wide x 0.5 mm thick. The glass substrate was then vacuum dried at 40°C using the same apparatus. Finally, a gas oven (INH-21CD, manufactured by Koyo Thermo Systems Co., Ltd.) was used to heat the glass substrate at 410°C for 30 minutes under a nitrogen atmosphere (oxygen concentration 100 ppm or less), forming a 10 μm-thick resin film on the glass substrate. The light transmittance of the resulting resin film on the substrate was measured using the method described in Section 3 above.

[0165] Next, the glass substrate was irradiated with a laser (wavelength: 308 nm) from the side where the resin film was not formed, and peeling was performed at the interface with the resin film. For the obtained resin film, Tg was measured by the method in item 4 above, Td0 was measured by the method in item 5 above, and tensile elongation and maximum tensile stress were measured by the method in item 6 above.

[0166] Next, using the laminate of the resin film and glass before peeling from the glass substrate, wrinkle evaluation was performed by the method of item 7 above, and film lifting evaluation was performed by the method of item 8 above.

[0167] (Examples 2 to 11, Comparative Examples 1 to 9) In Examples 2 to 11, Comparative Examples 1 to 6, and Comparative Examples 8 and 9, the resin compositions (varnishes) of Synthesis Examples 2 to 19 shown in Table 1 were used and evaluated in the same manner as in Example 1.

[0168] In Comparative Example 7, the same evaluation as in Example 1 was carried out, except that the heating condition was changed from 410°C to 350°C.

[0169] The evaluation results for Examples 1 to 11 and Comparative Examples 1 to 9 are shown in Table 2.

[0170] [Table 2]

[0171] Example 12 A resin film was produced in the same manner as in Example 1, except that the film thickness was changed from 10 μm to 2 μm. The light transmittance of the resin film was measured by the method in item 3 above, Tg was measured by the method in item 4 above, and Td0 was measured by the method in item 5 above. The light transmittance was 83%, Tg was 378°C, and Td0 was 450°C.

[0172] Next, a resin film was formed on a glass substrate using the same method as in Example 1. Subsequently, a 50 nm thick SiO film was formed on the resin film by CVD, and then a 2 μm thick resin film was formed on the SiO film using the same method. Using the resulting laminate, a wrinkle evaluation was performed using the method in item 7 above, and a film lifting evaluation was performed using the method in item 8 above. The wrinkle evaluation result was "A," and the film lifting evaluation result showed a good result of 0 film lifting.

Claims

1. A resin film used as a display substrate, the resin film comprising a resin having a repeating unit of a structure represented by chemical formula (1) and a terminal end thereof having a structure represented by chemical formula (2), wherein the value obtained by dividing the number of moles of aminosilane residues contained in the resin by the number of moles of tetracarboxylic acid residues is 0.2 to 1.2, the resin film has a light transmittance of 68% or more at a wavelength of 400 nm when converted into a film thickness of 10 μm, a glass transition temperature of 370°C or more, and a weight loss initiation temperature of 440°C or more. 【Chemistry 1】 (In chemical formula (1), A represents a tetracarboxylic acid residue having a structure represented by chemical formula (32), a structure represented by chemical formula (33), or a structure represented by chemical formula (34), and B represents a 3,3'-diaminodiphenylsulfone residue or a 4,4'-diaminodiphenylsulfone residue.) 【Chemistry 2】 (In chemical formula (2), A represents a tetracarboxylic acid residue having a structure represented by chemical formula (32), a structure represented by chemical formula (33), or a structure represented by chemical formula (34), B represents a 3,3'-diaminodiphenylsulfone residue or a 4,4'-diaminodiphenylsulfone residue, Z represents an aromatic hydrocarbon group having 6 to 10 carbon atoms as an aminosilane residue. R ３ represents a hydrocarbon group having 1 to 20 carbon atoms. n represents 2 or 3. X represents a structure represented by chemical formula (3), in which the oxygen atom in chemical formula (3) and the Si atom in chemical formula (2) are bonded. 【Transformation 3】 【Chemistry 4】 (In chemical formula (33), p represents an integer of 0 to 3. In chemical formula (34), q represents an integer of 1 to 4.)

2. A resin film used as a display substrate, the resin film comprising a resin having a repeating unit of a structure represented by chemical formula (1) and a terminal end thereof having a structure represented by chemical formula (2), wherein the value obtained by dividing the number of moles of diamine residues contained in the resin film by the number of moles of tetracarboxylic acid residues is 0.4 to 0.9, the resin film has a light transmittance of 68% or more at a wavelength of 400 nm when converted into a film thickness of 10 μm, a glass transition temperature of 370° C. or more, and a weight loss initiation temperature of 440° C. or more. 【Transformation 5】 (In chemical formula (1), A represents a tetracarboxylic acid residue having a structure represented by chemical formula (32), a structure represented by chemical formula (33), or a structure represented by chemical formula (34), and B represents a 3,3'-diaminodiphenylsulfone residue or a 4,4'-diaminodiphenylsulfone residue.) 【Transformation 6】 (In chemical formula (2), A represents a tetracarboxylic acid residue having a structure represented by chemical formula (32), a structure represented by chemical formula (33), or a structure represented by chemical formula (34), B represents a 3,3'-diaminodiphenylsulfone residue or a 4,4'-diaminodiphenylsulfone residue, Z represents an aromatic hydrocarbon group having 6 to 10 carbon atoms as an aminosilane residue. R ３ represents a hydrocarbon group having 1 to 20 carbon atoms. n represents 2 or 3. X represents a structure represented by chemical formula (3), in which the oxygen atom in chemical formula (3) and the Si atom in chemical formula (2) are bonded. 【Transformation 7】 【Transformation 8】 (In chemical formula (33), p represents an integer of 0 to 3. In chemical formula (34), q represents an integer of 1 to 4.)

3. 3. The resin film according to claim 2, wherein the value obtained by dividing the number of moles of aminosilane residues contained in the resin by the number of moles of tetracarboxylic acid residues is 0.2 to 1.

2.

4. 4. The resin film according to claim 1, wherein A does not contain a fluorine atom.

5. The resin film according to any one of claims 1 to 4, wherein A has a 3,3',4,4'-biphenyltetracarboxylic acid residue.

6. A display comprising the resin film according to any one of claims 1 to 5.

7. A resin composition used to obtain a display substrate, the resin composition comprising a resin having a repeating unit of a structure represented by chemical formula (4) and a terminal end having a structure represented by chemical formula (5), a silane compound, and a solvent, wherein the resin composition is applied and baked at 410°C to obtain a resin film having a thickness of 10 μm, which has a light transmittance at a wavelength of 400 nm of 68% or more, a glass transition temperature of 370°C or more, and a weight loss initiation temperature of 440°C or more. 【Chemistry 9】 (In chemical formula (4), A represents a tetracarboxylic acid residue having a structure represented by chemical formula (32), a structure represented by chemical formula (33), or a structure represented by chemical formula (34), and B represents a 3,3'-diaminodiphenylsulfone residue or a 4,4'-diaminodiphenylsulfone residue. R １ and R ２ each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, an alkali metal ion, an ammonium ion, an imidazolium ion, or a pyridinium ion. 【Chemistry 10】 (In chemical formula (5), A represents a tetracarboxylic acid residue having a structure represented by chemical formula (32), a structure represented by chemical formula (33), or a structure represented by chemical formula (34), B represents a 3,3'-diaminodiphenylsulfone residue or a 4,4'-diaminodiphenylsulfone residue, Z represents an aromatic hydrocarbon group having 6 to 10 carbon atoms as an aminosilane residue. R １ and R ２ R each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, an alkali metal ion, an ammonium ion, an imidazolium ion, or a pyridinium ion. ３ and R ４ each independently represents a hydrocarbon group having 1 to 20 carbon atoms; and n represents 2 or 3. 【Chemistry 11】 (In chemical formula (33), p represents an integer of 0 to 3. In chemical formula (34), q represents an integer of 1 to 4.)

8. The resin composition according to claim 7, wherein the silane compound has a structure represented by chemical formula (7). 【Chemistry 12】 (In chemical formula (7), R ５ and R ６ each independently represents a hydrocarbon group having 1 to 20 carbon atoms; and m represents 3 or 4.

9. The resin composition according to claim 7 or 8, wherein the imidization rate of the resin is 5 to 30%.

10. A method for producing a resin film, comprising the steps of applying the resin composition according to any one of claims 7 to 9 to a support and baking the composition at 400°C to 490°C.

11. A method for manufacturing a display, comprising the steps of: forming a resin film on a support by the resin film manufacturing method according to claim 10; forming a display element on the resin film; and peeling the resin film from the support.

Images