Polyimide resin, photosensitive resin composition, cured product, organic EL display device, and electronic component

Abstract

The present invention addresses the problem of providing a polyimide resin which, when used in a photosensitive resin composition, has high sensitivity and can achieve high planarization of the surface of an object having a rugged surface, has a low dielectric constant of a cured product obtained by curing, has high reliability when used in an organic EL display device, and can be used in an organic EL display device. As a means for solving the problem, the present invention provides a polyimide resin which has an acid dianhydride residue and diamine residues, contains an acid dianhydride residue having 8-40 carbon atoms and containing an alicyclic structure, and contains two specific diamine residues at a specific ratio.

Description

Technical Field

[0001] The present invention relates to a polyimide resin, a photosensitive resin composition, a cured product, an organic EL display device, and an electronic component. Background Art

[0002] Heat-resistant resins such as polyimide and polybenzoxazole have excellent mechanical properties, heat resistance, chemical resistance, and electrical insulation properties, and are therefore used for surface protective films, interlayer insulating films of semiconductor devices such as LSIs, insulating layers of organic EL display devices, planarization films of TFT substrates for display devices, and the like.

[0003] Generally, an organic EL display device has a driving circuit, a planarization layer, a first electrode, a pixel division layer, a light-emitting layer, and a second electrode on a substrate, and can emit light by applying a voltage between the opposed first electrode and second electrode, or by passing a current therethrough. Among them, as a material for the planarization layer and a material for the pixel division layer, a photosensitive resin composition that can be patterned by ultraviolet irradiation is usually used. Among them, a photosensitive resin composition using a polyimide-based or polybenzoxazole-based resin is preferably used because the resin has high heat resistance and few gas components generated from the cured product, and thus a highly reliable organic EL display device can be obtained (see, for example, Patent Document 1).

[0004] On the other hand, the requirements for the high reliability of organic EL display devices have become increasingly strict year by year. Even for materials for the planarization layer and the pixel division layer, materials that do not cause a decrease in emission luminance or pixel shrinkage after a reliability test under accelerated conditions such as high temperature, high humidity, and light irradiation are required. Here, the so-called pixel shrinkage refers to a phenomenon in which the emission luminance decreases or the pixel does not light up from the end of the pixel.

[0005] In addition, for reasons such as the increase in the size of the substrate and the improvement in productivity, in order to shorten the exposure time, higher sensitivity is required for the photosensitive resin composition.

[0006] Furthermore, in organic EL display devices and semiconductor devices, the high density of pixels and wirings is constantly developing, and materials suitable for fine processing of patterns and planarization of the surface of an object having an uneven surface are required.

[0007] Moreover, for the purpose of improving the high-speed display response of organic EL display devices and the like, a cured product obtained by curing a photosensitive resin composition is required to have a low dielectric constant.

[0008] Based on such a background, there is a strong expectation for the development of a photosensitive resin composition that can be patterned with high sensitivity, can achieve planarization of the surface of an object having an uneven surface, and can obtain a cured product having a low relative dielectric constant and excellent reliability.

[0009] Regarding such a problem, as a photosensitive resin composition capable of obtaining a cured product with a low dielectric constant, a negative photosensitive resin composition containing a resin obtained by introducing an alicyclic structure and a hydrocarbon structure into a polyimide precursor has been studied (for example, see Patent Document 2). In addition, as a photosensitive resin composition capable of flattening the surface of an object having an uneven surface, a phenolic resin having a fluorene structure has been studied (for example, see Patent Document 3).

[0010] Prior Art Documents

[0011] Patent Documents

[0012] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2002-91343

[0013] Patent Document 2: International Publication No. 2021 / 020344

[0014] Patent Document 3: Japanese Unexamined Patent Application Publication No. 2022-34533 Summary of the Invention

[0015] Problems to be Solved by the Invention

[0016] As described above, the requirements for the high reliability of organic EL display devices have become increasingly strict year by year. For example, if the photosensitive resin composition described in Patent Document 1 is used as a material for a flattening layer and an insulating layer, there is a problem that the light emission characteristics after a reliability test under accelerated conditions such as light irradiation cannot be maintained.

[0017] Although Patent Document 2 discloses a negative photosensitive resin composition that can be developed using an organic solvent, when the present inventors studied a developing method using an aqueous solution of tetramethylammonium hydroxide (TMAH) commonly used in the production of organic EL display devices, it was found that an opening pattern could not be obtained due to low solubility of the unexposed portion, or the sensitivity was low.

[0018] Although Patent Document 3 describes that the flatness can be improved by using a phenolic resin, when the present inventors conducted research, it was found that the dielectric constant of the obtained cured product was high.

[0019] In view of the above problems, an object of the present invention is to provide a polyimide resin that has high sensitivity when used in a photosensitive resin composition, can achieve high flatness of the surface of an object having an uneven surface, has a low dielectric constant of a cured product obtained by curing the photosensitive resin composition, and has high reliability when the cured product is used in an organic EL display device.

[0020] Means for Solving the Problems

[0021] In order to solve the above problems and achieve the above objects, the present invention has the following constitution.

[0022] [1] A polyimide resin, which is a polyimide resin having an acid dianhydride residue and a diamine residue,

[0023] All or part of the acid dianhydride residues in the polyimide resin are acid dianhydride residues having an alicyclic structure and 8 to 40 carbon atoms,

[0024] Moreover, when the total amount of diamine residues in the polyimide resin is set to 100 mol%, the total content of the diamine residues represented by formula (41) and the diamine residues represented by formula (42) is 60 mol% or more and 98 mol% or less,

[0025] The total content of the diamine residues represented by formula (16) and the diamine residues represented by formula (17) is 2 mol% or more and 40 mol% or less.

[0026] [Chemical formula 1]

[0027]

[0028] (X 3 represents a direct bond or a divalent organic group having 2 to 15 carbon atoms in which a part of hydrogen atoms is optionally substituted by fluorine atoms. R 11 represents a methyl group, and k each independently represents 0 or 1. * represents a bonding site bonded to an imide structure or an amic acid structure.)

[0029] [Chemical formula 2]

[0030]

[0031] (In formula (16), a, b, c and d are each independently natural numbers satisfying a + b = 7 to 17 and c + d = 6 to 16, and the dotted line part refers to a carbon-carbon single bond or a carbon-carbon double bond. In formula (17), e, f, g and h are each independently natural numbers satisfying e + f = 10 to 20 and g + h = 12 to 22, and the dotted line part refers to a carbon-carbon single bond or a carbon-carbon double bond. * represents a bonding site bonded to an imide structure or an amic acid structure.)

[0032] [2] The polyimide resin according to [1], wherein, when the total amount of acid dianhydride residues in the polyimide resin is set to 100 mol%, the ratio of the acid dianhydride residues having an alicyclic structure and 8 to 40 carbon atoms is 51 mol% to 100 mol%.

[0033] [3] The polyimide resin according to [1] or [2], wherein the aforementioned X 3is a direct bonding key, -C(CH3)2-, -CH(CF3)-, or -C(CF3)2-, and the aforementioned k is 0.

[0034] [4] The polyimide resin according to [1] or [2], wherein the aforementioned X 3 is a divalent saturated hydrocarbon group having 2 to 15 carbon atoms that does not contain a fluorine atom.

[0035] [5] The polyimide resin according to [1] or [2], wherein the aforementioned X 3 is any one of the divalent saturated hydrocarbon groups represented by Formula (43) to Formula (51).

[0036] [Chemical Formula 3]

[0037]

[0038] * represents the bonding site bonded to the aromatic ring.

[0039] [6] The polyimide resin according to [5], wherein the aforementioned X 3 is a group selected from the divalent saturated hydrocarbon groups represented by Formula (44), Formula (45), Formula (49), Formula (50), and Formula (51).

[0040] [7] The polyimide resin according to any one of the aforementioned [1] to [6], wherein the acid dianhydride residue having 8 to 40 carbon atoms containing an alicyclic structure is an acid dianhydride residue having 10 to 40 carbon atoms containing both an alicyclic structure and an aromatic ring.

[0041] [8] The polyimide resin according to any one of the aforementioned [1] to [7], wherein the acid dianhydride residue having 10 to 40 carbon atoms containing both an alicyclic structure and an aromatic ring is one or more acid dianhydride residues selected from the group consisting of acid dianhydride residues represented by any one of Formula (3) to Formula (6).

[0042] [Chemical Formula 4]

[0043]

[0044] (X in Formula (5) 2 represents a divalent organic group represented by Formula (7) or Formula (8). X in Formula (6) 3 represents an ether bond or an ester bond, and i represents an integer from 0 to 6. In Formula (3) to Formula (6), * represents the bonding site bonded to any one of a carboxyl group, a carboxyl ester group, an amide group, or a carbonyl group constituting an imide ring.)

[0045] [Chemical Formula 5]

[0046]

[0047] (X in Formula (7) 4 represents a direct bonding key or an ether key. In Formula (7) and Formula (8), * represents a bonding site bonded to the nitrogen atom of Formula (5).)

[0048] [9] The polyimide resin according to any one of the foregoing [1] to [8], wherein, when the total amount of diamine residues in the foregoing polyimide resin is set to 100 mol%, the content of diamine residues represented by Formula (41) is 60 mol% or more and 98 mol% or less.

[0049]

[10] A photosensitive resin composition comprising the polyimide resin according to any one of the foregoing [1] to [9], a photosensitizer, and a solvent.

[0050]

[11] The photosensitive resin composition according to the foregoing

[10] , wherein all or part of the foregoing photosensitizer is a photoacid generator.

[0051]

[12] The photosensitive resin composition according to the foregoing

[10] or

[11] , further comprising a thermal acid generator.

[0052]

[13] A cured product formed by curing the photosensitive resin composition according to any one of the foregoing

[10] to

[12] .

[0053]

[14] An organic EL display device comprising the cured product according to the foregoing

[13] .

[0054]

[15] An electronic component comprising the cured product according to the foregoing

[13] .

[0055] Advantages of the Invention

[0056] According to the present invention, the following polyimide resin can be obtained. When used in a photosensitive resin composition, the polyimide resin has high sensitivity and can achieve high planarization of the surface of an object having an uneven surface. The cured product obtained by curing the photosensitive resin composition has a low dielectric constant, and when the cured product is used in an organic EL display device, the reliability is high. Brief Description of the Drawings

[0057] Figure 1 is a cross-sectional view of a flatness evaluation sample.

[0058] Figure 2 is a schematic diagram showing a method for manufacturing an organic EL display device including a pixel division layer in an example. Detailed Description of the Invention

[0059] Hereinafter, the present invention will be described in detail.

[0060] ​​In the present specification, a numerical range expressed using "to" means a range including the numerical values described before and after "to" as the lower limit and the upper limit, respectively.

[0061] The polyimide resin of the present invention (hereinafter, sometimes referred to as "polyimide resin (a)" or simply "component (a)") is a polyimide resin having an acid dianhydride residue and a diamine residue, wherein all or part of the acid dianhydride residues in the polyimide resin are acid dianhydride residues having 8 to 40 carbon atoms and containing an alicyclic structure, and when the total amount of diamine residues in the polyimide resin is 100 mol%, the total content of the diamine residue represented by formula (41) and the diamine residue represented by formula (42) is 60 mol% or more and 98 mol% or less,

[0062] The total content of the diamine residue represented by the formula (16) and the diamine residue represented by the formula (17) is 2 mol% or more and 40 mol% or less.

[0063] [Chemical formula 6]

[0064]

[0065] In formula (41) and formula (42), X 3 represents a direct bond, or a divalent organic group having 2 to 15 carbon atoms in which a part of the hydrogen atoms are optionally substituted with fluorine atoms, R 11 represents a methyl group, and k each independently represents 0 or 1. * represents a bonding site to an imide structure or an amic acid structure.

[0066] [Chemical formula 7]

[0067]

[0068] In formula (16), a, b, c and d are each independently a natural number satisfying a+b=7 to 17, c+d=6 to 16, and the dotted line portion refers to a carbon-carbon single bond or a carbon-carbon double bond. In formula (17), e, f, g and h are each independently a natural number satisfying e+f=10 to 20, g+h=12 to 22, and the dotted line portion refers to a carbon-carbon single bond or a carbon-carbon double bond. * represents a bonding site to an imide structure or an amic acid structure.

[0069] The polyimide resin (a) of the present invention is intended to form a polyimide ring after the curing operation, and therefore includes a resin having a structure before the imide ring is closed, that is, a structure of an amic acid or an ester of the acid.

[0070] Regarding the polyimide resin (a), it is preferable that all or part of the acid dianhydride residues in the polyimide resin are acid dianhydride residues having an alicyclic structure and 8 to 40 carbon atoms, and when the total amount of diamine residues in the polyimide resin is set to 100 mol%, the total content of the diamine residues represented by formula (41) and the diamine residues represented by formula (42) is 60 mol% or more and 98 mol% or less, and the total of the diamine residues represented by formula (16) and the diamine residues represented by formula (17) is 2 mol% or more and 40 mol% or less, and it has, for example, one or more selected from the group consisting of the structural unit represented by formula (9), the structural unit represented by formula (10), and the structural unit represented by formula (11).

[0071] [Chemical formula 8]

[0072]

[0073] In formula (9), formula (10), and formula (11), R 1 represents an acid dianhydride residue, and R 2 represents a diamine residue. When the total amount of R 2 is set to 100 mol%, the total content of the diamine residues represented by formula (41) and the diamine residues represented by formula (42) is 60 mol% or more and 98 mol% or less, and the total content of the diamine residues represented by formula (16) and the diamine residues represented by formula (17) is 2 mol% or more and 40 mol% or less. R 3 each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. * represents a bonding site bonded to R 2 or a nitrogen atom.

[0074] When the total of all the structural units contained in the polyimide resin (a) of the present invention is set to 100 mol%, the total content of the structural unit represented by formula (9), the structural unit represented by formula (10), and the structural unit represented by formula (11) is preferably 70 mol% or more, more preferably 80 mol% or more, and particularly preferably 90 mol% or more.

[0075] The structural unit represented by formula (9) represents a structural unit in which all the amic acid structures or amic acid ester structures in the structural unit are cyclized to form imide structures. The structural unit represented by formula (10) represents a structural unit in which a part of the amic acid structures or amic acid ester structures in the structural unit is cyclized to form imide structures and a part is an amic acid structure or an amic acid ester structure. The structural unit represented by formula (11) represents a structural unit in which the amic acid structures or amic acid ester structures in the structural unit are not cyclized and are all amic acid structures or amic acid ester structures.

[0076] When the numbers of the structural unit represented by the formula (9), the structural unit represented by the formula (10), and the structural unit represented by the formula (11) in the polyimide resin (a) of the present invention are p, q, and r, respectively, p, q, and r are integers of 0 or more, and p≥r is preferred.

[0077] The ring closure rate of the imide ring of the polyimide resin (a) is preferably 40% or more and 100% or less, more preferably 50% or more and 100% or less, further preferably 60% or more and 100% or less, and further preferably 80% or more and 100% or less. By setting the ring closure rate of the imide ring within the above range, the alkali development rate can be within a preferred range. Therefore, the shape of the pattern obtained after development can be good, and the development residue can be reduced.

[0078] The ring closure rate of the imide ring of the polyimide resin (a) can be determined by the method described later.

[0079] In the formula (10) and the formula (11), as R 3 the monovalent organic group having 1 to 20 carbon atoms, a monovalent hydrocarbon group having 1 to 20 carbon atoms can be cited. As the monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms can be cited. Specifically, as the alkyl group having 1 to 20 carbon atoms, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, etc. can be cited. In order to reduce the generation of residues of the photosensitive composition, each R 3 is independently preferably any one of a hydrogen atom, a methyl group, or an ethyl group.

[0080] In addition, the polyimide resin (a) may also be a resin that contains structural units other than the structural unit represented by the formula (9), the structural unit represented by the formula (10), and the structural unit represented by the formula (11) and other than the imide structure derived from a tetracarboxylic acid and the amic acid structure derived from a tetracarboxylic acid within the range not hindering the object of the present invention. As such structural units, as the structural units that can be contained in the polyimide resin (a), a benzoxazole structural unit can be cited. In the case of containing a benzoxazole structural unit, the heat resistance and chemical resistance can sometimes be improved. A copolymer resin having the structural unit of the polyimide resin (a) and the structural unit of polybenzoxazole can be obtained, for example, by reacting the raw materials of the above polyimide resin (a) and the raw materials of the polybenzoxazole resin at one time to obtain a random copolymer, or by reacting each repeating unit after separately synthesizing the repeating unit of the polyimide resin (a) and the repeating unit of polybenzoxazole to obtain a block copolymer having the repeating unit of polyimide (a) and the repeating unit of polybenzoxazole.

[0081] In the polyimide resin (a), all or part of the acid dianhydride residues contained in the polyimide resin (a) are acid dianhydride residues having 8 to 40 carbon atoms containing an alicyclic structure. Thus, the i-line transmittance of the resin is improved, and therefore high-sensitivity of the photosensitive resin composition can be achieved. Moreover, more preferably, the acid dianhydride residue having 8 to 40 carbon atoms containing an alicyclic structure is an acid dianhydride residue having 10 to 40 carbon atoms containing both an alicyclic structure and an aromatic ring. By having a structure containing both an alicyclic structure and an aromatic ring, stacking between molecules of the polyimide resin (a) can be suppressed, and the solvent solubility of the resin and the solubility in an alkaline developer can be improved. Therefore, development residues can be reduced. When the total amount of the acid dianhydride residues in the polyimide resin (a) is 100 mol%, the ratio of the acid dianhydride residues having 8 to 40 carbon atoms containing an alicyclic structure contained in the polyimide resin (a) is preferably 51 mol% to 100 mol%, more preferably 60 mol% to 100 mol%, and further preferably 70 mol% to 100 mol%.

[0082] In the polyimide resin (a) of the present invention, from the aspects of being able to improve the i-line transmittance of the polyimide resin (a), having good solvent solubility of the polyimide resin (a), and being able to reduce the relative dielectric constant of the cured product obtained by curing the photosensitive resin composition containing the polyimide resin (a), the acid dianhydride residue having 10 to 40 carbon atoms containing both an alicyclic structure and an aromatic ring is preferably one or more acid dianhydride residues selected from the group consisting of acid dianhydride residues represented by any one of Formula (3) to Formula (6).

[0083] [Chemical Formula 9]

[0084]

[0085] (X in Formula (5) 2 represents a divalent organic group represented by any one of Formula (7) or Formula (8). X in Formula (6) 3 represents an ether bond or an ester bond, and i represents an integer of 0 to 6. In Formula (3) to Formula (6), * represents a bonding site bonded to any one of a carboxyl group, a carboxyl ester group, an amide group, or a carbonyl group constituting an imide ring.)

[0086] [Chemical Formula 10]

[0087]

[0088] (X in Formula (7) 4 represents a direct bonding bond or an ether bond. In Formula (7) and Formula (8), * represents a bonding site bonded to the nitrogen atom of Formula (5).)

[0089] Examples of the acid anhydride or its derivative that can supply the acid anhydride residue represented by any one of Formula (3) to Formula (6) include BzDA (Formula (12), manufactured by ENEOS Corporation), TDA-100 (Formula (13), manufactured by Shin Nippon Rika Co., Ltd.), PPHT (Formula (14), manufactured by Nippon Fine Chemical Co., Ltd.), and TBIS-DMPN (Formula (15), manufactured by Taoka Chemical Industry Co., Ltd.).

[0090] [Chemical Formula 11]

[0091]

[0092] In addition, the polyimide resin (a) may also contain an acid anhydride residue having a diphenyl ether structure. Thereby, it is possible to lower the glass transition temperature without reducing the i-line transmittance of the polyimide resin (a), and obtain a cured pattern having a low taper shape. Moreover, it is possible to improve the mechanical strength of the polyimide resin (a) and improve the bending resistance and elongation at break of the cured product obtained by curing the photosensitive resin composition.

[0093] Specific examples of the acid anhydride or its derivative that can supply an acid anhydride residue having a diphenyl ether structure include 3,4'-oxybisphthalic anhydride, 4,4'-oxybisphthalic anhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzoic anhydride, 2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl)propane dianhydride, 2,2-bis(3-(3,4-dicarboxyphenoxy)phenyl)propane dianhydride, 2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl)hexafluoropropane dianhydride, and 2,2-bis(3-(3,4-dicarboxyphenoxy)phenyl)hexafluoropropane dianhydride.

[0094] When the polyimide resin (a) contains an acid anhydride residue having a diphenyl ether structure, when the total amount of the acid anhydride residues is 100 mol%, its content is preferably 1 mol% to 40 mol%, more preferably 1 mol% to 30 mol%.

[0095] The polyimide resin (a) may have other acid anhydride residues in addition to the aforementioned acid anhydride residues.

[0096] As the acid anhydride or its derivative capable of supplying other acid anhydride residues, specifically, alicyclic tetracarboxylic dianhydrides such as 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 3,5,6-tricarboxy-2-norbornaneacetic dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride; aromatic tetracarboxylic dianhydrides such as pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride; aromatic acid anhydrides such as bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride or compounds obtained by substituting the aromatic rings of these compounds with an alkyl group or a halogen atom, and acid anhydrides having an amide group. They can be used in combination of two or more with an acid anhydride or its derivative capable of supplying an acid anhydride having 8 to 40 carbon atoms including an alicyclic structure.

[0097] Regarding the polyimide resin (a), when the total amount of diamine residues in the polyimide resin is set to 100 mol%, the total content of the diamine residues represented by the formula (41) and the diamine residues represented by the formula (42) is 60 mol% or more and 98 mol% or less.

[0098] [Chemical formula 12]

[0099]

[0100] In the formula (41) and the formula (42), X 3represents a divalent organic group having 2 to 15 carbon atoms in which a part of a direct bond or a hydrogen atom is optionally substituted with a fluorine atom, R 11 represents a methyl group, and each k independently represents 0 or 1. * represents a bonding site bonded to an imide structure or an amic acid structure.

[0101] X in formula (41) and formula (42) 3 is a direct bond, or a divalent organic group having 2 to 15 carbon atoms in which a part of a hydrogen atom is optionally substituted with a fluorine atom. As the divalent organic group having 2 to 15 carbon atoms, for example, an alkylene group in which a hydrogen atom in the group is optionally substituted with an aryl group, a heteroaryl group, a halogen group, or an oxyalkylene group can be cited. Moreover, from the viewpoints of improving the sensitivity of the photosensitive resin composition and improving the reliability of the organic EL display device, it is preferable that the aforementioned X 3 is a direct bond, -C(CH3)2-, -CH(CF3)-, or -C(CF3)2-, and the aforementioned k is 0, and more preferably the aforementioned X 3 is -C(CH3)2-, -CH(CF3)-, or -C(CF3)2-, and the aforementioned k is 0. Moreover, when the diamine residue represented by formula (41) or formula (42) contains a structure having a trifluoromethyl group, intermolecular stacking can be suppressed, and solvent solubility and solubility in an alkaline developer can be improved. Therefore, from the viewpoint of being able to reduce residues when used in a photosensitive resin composition, X 3 is particularly preferably -CH(CF3)- or -C(CF3)2-.

[0102] In addition, from the viewpoints of suppressing contamination of the opening after curing and improving the reliability of the organic EL display device, X in the aforementioned formula (41) and formula (42) 3 is preferably a divalent saturated hydrocarbon group having 2 to 15 carbon atoms that does not contain a fluorine atom. This is because, by making the aforementioned X 3 not contain a fluorine atom, contamination of the opening caused by an organic compound containing a fluorine atom during curing can be suppressed.

[0103] Moreover, from the viewpoints of being able to suppress intermolecular stacking and improving solvent solubility and solubility in an alkaline developer, the aforementioned X 3 is preferably any one of the divalent saturated hydrocarbon groups represented by formula (43) to formula (51).

[0104] [Chemical formula 13]

[0105]

[0106] * represents a bonding site bonded to an aromatic ring.

[0107] Among them, from the aspects of low structural symmetry, particularly excellent solvent solubility and solubility in an alkaline developer, and from the aspect of enabling high-sensitization of the photosensitive resin composition, X in the aforementioned formulas (41) and (42) 3 is more preferably a group selected from divalent saturated hydrocarbon groups represented by formula (44), formula (45), formula (49), formula (50), and formula (51). The groups represented by formula (44), formula (45), formula (49), formula (50), and formula (51) include groups that are asymmetric left and right on the paper surface, and the target aromatic ring bonded to the bonding site of the aromatic ring can be arbitrarily selected. In addition, the groups represented by formula (44), formula (45), formula (49), formula (50), and formula (51) include all optical isomers.

[0108] Since the diamine residues represented by formula (41) or formula (42) each have a phenolic hydroxyl group, solubility in an alkaline developer can be imparted, and development residues can be reduced. In addition, the phenolic hydroxyl group strongly interacts with the quinonediazide compound as a photoacid generator to exhibit an anti-dissolution effect. Therefore, in a positive-type photosensitive resin composition containing a photoacid generator, a photosensitive resin composition with high contrast can be obtained.

[0109] The diamine residue represented by formula (41) or formula (42) is a structure derived from a diamine or a diamine derivative. As its structural formula, it is a structure obtained by removing two amino groups from the diamine. Specific examples of diamines or their derivatives that can provide the diamine residue represented by formula (41) or formula (42) include 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane (HA), 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]propane, 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]-1,1,1-trifluoroethane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAP), 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP), 1,1,1-trifluoro-2,2-bis(3-amino-4-hydroxyphenyl)ethane (BIS-AP-EF), 3,3'-dihydroxybenzidine (HAB), and diamines represented by formula (52) to formula (61) as preferred specific examples. It should be noted that diamines having optical isomers among the diamines represented by formula (52) to formula (61) include all optical isomers.

[0110] [Chemical formula 14]

[0111]

[0112] Among them, from the viewpoints of solubility in an alkaline developer, sensitivity, and reduction of the relative dielectric constant of a cured product obtained by curing the photosensitive resin composition, it is preferable to contain diamine residues derived from 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane (HA), 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]-1,1,1-trifluoroethane, diamines represented by formula (57) to formula (61), or their derivatives. From the viewpoint of being able to suppress contamination of the opening after curing in addition to solubility in an alkaline developer, sensitivity, and the effect of reducing the relative dielectric constant of a cured product obtained by curing the photosensitive resin composition, it is more preferable to contain diamine residues derived from diamines represented by formula (57) to formula (61), or their derivatives.

[0113] When the total amount of diamine residues is set to 100 mol%, the content of the diamine residue represented by formula (41) and the diamine residue represented by formula (42) is 60 mol% to 98 mol%. From the viewpoints of sensitivity and the ability to reduce the relative dielectric constant of a cured product obtained by curing the photosensitive resin composition, it is preferable that when the total amount of diamine residues is set to 100 mol%, the content of the diamine residue represented by formula (41) is 60 mol% to 98 mol%. In addition, the content of the diamine residue represented by formula (41) is preferably 60 mol% or more and 98 mol% or less, more preferably 65 mol% to 97 mol%, and even more preferably 70 mol% to 95 mol%.

[0114] Regarding the polyimide resin (a), when the total amount of diamine residues in the polyimide resin is set to 100 mol%, the total content of the diamine residue represented by formula (16) and the diamine residue represented by formula (17) is 2 mol% or more and 40 mol% or less.

[0115] [Chemical formula 15]

[0116]

[0117] In formula (16), a, b, c, and d are each independently natural numbers satisfying a + b = 7 to 17 and c + d = 6 to 16, and the dotted line portion represents a carbon-carbon single bond or a carbon-carbon double bond. In formula (17), e, f, g, and h are each independently natural numbers satisfying e + f = 10 to 20 and g + h = 12 to 22, and the dotted line portion represents a carbon-carbon single bond or a carbon-carbon double bond. * represents a bonding site bonded to an imide structure or an amic acid structure.

[0118] The diamine residues represented by Formula (16) and Formula (17) are structures derived from diamines or diamine derivatives. As their structural formulas, they can be described as structures obtained by removing two amino groups from a compound obtained by converting the carboxyl groups of dimers of unsaturated fatty acids such as linoleic acid and oleic acid (i.e., dimer acids, note that it is not limited to dimer acids with 36 carbon atoms) into amino groups, namely dimer diamines. From the viewpoints of the reliability of the obtained cured product, reducing the relative dielectric constant, improving the solvent solubility of the polyimide resin, and achieving high planarization of the surface of an object with an uneven surface, a structure without double bonds is preferred. From the viewpoints that the planarization of the surface of an object with an uneven surface is particularly good and the relative dielectric constant and water absorption rate of the obtained cured product can be reduced, a diamine residue derived from the diamine or its derivative represented by Formula (18) is preferred.

[0119] [Chemical Formula 16]

[0120]

[0121] Although the detailed mechanism by which the polyimide resin (a) can achieve high planarization of the surface of an object with an uneven surface due to containing the diamine residues shown in Formula (16) and Formula (17) is not clear, it is considered that since the polyimide resin (a) contains diamine residues with high flexibility and motility such as those in Formula (16) and Formula (17), the stacking of polyimide resins with each other can be inhibited, the glass transition temperature of the polyimide resin decreases, and thus, in the process of heat-curing the photosensitive resin composition, the fluidity increases and the height difference on the film surface decreases (i.e., the planarization improves).

[0122] Regarding specific examples of diamines or their derivatives that can provide the diamine residues represented by Formula (16) and Formula (17), as commercially available products of dimer diamines, there can be mentioned "Versamine (registered trademark) 551", "Versamine (registered trademark) 552" manufactured by BASF Co., Ltd., "Priamine (registered trademark) 1073", "Priamine (registered trademark) 1074", "Priamine (registered trademark) 1075" manufactured by Claude Japan Co., Ltd., etc. Here, both "Versamine (registered trademark) 551" and "Priamine (registered trademark) 1074" are dimer diamine compounds containing the compound represented by Formula (19), and both "Versamine (registered trademark) 552", "Priamine (registered trademark) 1073", and "Priamine (registered trademark) 1075" are dimer diamine compounds containing the compound represented by Formula (18).

[0123] [Chemical Formula 17]

[0124]

[0125] In addition, a mixture of a trimer triamine and a dimer diamine can also be used. As a commercially available product of the mixture of a trimer triamine and a dimer diamine, “Priamine (registered trademark) 1071” manufactured by Claude Japan Co., Ltd. etc. can be cited.

[0126] Regarding the polyimide resin (a), when the total amount of diamine residues in the polyimide resin is set to 100 mol%, the total content of the diamine residues represented by the formula (16) and the diamine residues represented by the formula (17) is 2 mol% or more and 40 mol% or less, preferably 3 mol% or more and 35 mol% or less, more preferably 5 mol% or more and 30 mol% or less. By setting it to 2 mol% or more, the relative dielectric constant and water absorption rate of the cured product can be reduced. In addition, by setting it to 40 mol% or less, the development residue can be reduced.

[0127] In addition, the polyimide resin (a) may have other diamine residues in addition to the aforementioned diamine residues.

[0128] As a specific example of other diamine residues, for example, an aliphatic diamine residue and an aromatic diamine residue that do not belong to any of the diamine residues of the formula (41), the formula (42), the formula (16), and the formula (17) can be cited. The so-called aliphatic diamine residue refers to the residue of a diamine that does not have an aromatic ring. As the aliphatic diamine residue, residues of aliphatic alkyl diamines, alicyclic diamines, and aliphatic diamines having a siloxane structure containing an alkylene ether group such as an alkylene group, a polyethylene ether group, a polyoxypropylene group, and a tetramethylene ether group can be cited.

[0129] As specific examples of the diamine or its derivative that can supply such an aliphatic alkylene diamine residue, tetramethylene diamine, hexamethylene diamine, octamethylene diamine, decamethylene diamine, dodecamethylene diamine as polymethylene diamine, Jeffamine KH-511, Jeffamine ED-600, Jeffamine ED-900, Jeffamine ED-2003, Jeffamine EDR-148, Jeffamine EDR-176 as diamines containing a polyethylene ether group, D-200, D-400, D-2000, D-4000, RP-409, RP-2009 as polyoxypropylene diamine, RT-1000, HT-1100 as diamines containing a tetramethylene ether group, HT-1000, HE-1000 (the above are trade names, manufactured by HUNTSMAN Co., Ltd.) and their derivatives can be cited.

[0130] In addition, as the diamine or its derivative that can supply an alicyclic diamine residue, cyclohexyl diamine, methylene bis(cyclohexylamine) and their derivatives can be cited.

[0131] In addition, as the diamine or its derivative that can supply an aliphatic diamine residue having a siloxane structure, bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane and their derivatives can be cited.

[0132] In addition, as the diamine or its derivative that can supply an aliphatic diamine residue having a secondary amino group and a tertiary amino group, 3,3'-(methylimino)bis(1-propanamine), 3,3'-diaminodipropylamine and their derivatives can be cited.

[0133] From the viewpoint of not reducing the heat resistance, when introducing the above-mentioned other diamine residues, among 100 mol% of all the diamine residues, the aliphatic alkylene diamine residue that does not belong to either of the diamine residues of formula (16) and formula (17) is preferably 10 mol% or less, more preferably 5 mol% or less.

[0134] In addition, when an aliphatic group having a siloxane structure is copolymerized within a range that does not reduce the heat resistance, the adhesiveness to the substrate can be improved. From the viewpoint of not reducing the heat resistance, at the time of introduction, among 100 mol% of all the diamine residues, it is preferably 1 mol% or more and 10 mol% or less, more preferably 2 mol% or more and 8 mol% or less.

[0135] In addition, the so-called aromatic diamine residue refers to the residue of a diamine having an aromatic ring. Specific examples of the diamine or its derivative capable of supplying the aromatic diamine residue include diamines containing a hydroxyl group such as bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl, bis(3-amino-4-hydroxyphenyl)fluorene; diamines containing a sulfonic acid such as 3-sulfonic acid-4,4'-diaminodiphenyl ether; diamines containing a mercapto group such as dimercaptobenzene diamine; 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl methane, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl and other aromatic diamines, and compounds and their derivatives obtained by substituting a part of the hydrogen atoms of their aromatic rings with an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, a halogen atom, etc. These diamines and their derivatives can be used directly, or in the form of corresponding diisocyanate compounds or trimethylsilylated diamines. They can be used alone or in combination of two or more kinds.

[0136] In addition, the polyimide resin (a) may contain a triamine residue. The triamine has three amino groups and forms a branched molecular chain by bonding with three acid dianhydride components. The triamine introduces a branched structure into the molecular chain of the polyimide resin (a), thereby forming a branched polyimide resin. As a result, the polyimide resin (a) has a three-dimensional network structure. Therefore, the entanglement of the molecules of the polyimide resins increases, and a polyimide resin film having excellent mechanical strength can be obtained as compared with a resin having no branched structure. Such a polyimide resin (a) having a triamine residue can be obtained by using a triamine compound as one of the polymerization components.

[0137] Among specific examples of triamine compounds having a structure capable of supplying triamine residues, as triamine compounds not having an aliphatic group, 2,4,4'-triaminodiphenyl ether (TAPE), 1,3,5-tris(4-aminophenoxy)benzene (1,3,5-TAPOB), 1,2,3-tris(4-aminophenoxy)benzene (1,2,3-TAPOB), tris(4-aminophenyl)amine, 1,3,5-tris(4-aminophenyl)benzene, 3,4,4'-triaminodiphenyl ether, etc. can be cited. In addition, as specific examples of triamine compounds having an aliphatic group, tris(2-aminoethyl)amine (TAEA), tris(3-aminopropyl)amine, etc. can be cited.

[0138] In order to simultaneously achieve the mechanical strength of the obtained polyimide resin (a) and a reduction in development residue of the photosensitive resin composition containing the polyimide resin (a), when the total amount of diamine residues is set to 100 mol parts, the content of triamine residues is preferably 0.1 to 20 mol parts.

[0139] In addition, for the polyimide resin (a), the terminal can be blocked with a terminator such as a monoamine, an acid anhydride, a monoacyl chloride, a monocarboxylic acid, a monoactive ester, etc. By blocking the terminal of the polyimide resin (a) with a terminator, the dissolution rate of the polyimide resin (a) in an alkaline aqueous solution can be easily adjusted to a preferred range. Among them, a terminator having a phenolic hydroxyl group and a photocrosslinkable group is preferably used. By using a terminator having a phenolic hydroxyl group, the residue can be reduced, and in addition, the sensitivity is improved. In addition, by using a terminator having a photocrosslinkable group, the chemical resistance and mechanical strength of the cured product can be improved.

[0140] When using a monoamine as a terminator, when the total amount of all amine compounds contained in the polyimide resin (a) is set to 100 mol%, its introduction ratio is preferably 0.1 mol% or more, particularly preferably 5 mol% or more. In addition, when the total amount of all amine compounds contained in the polyimide resin (a) is set to 100 mol%, the introduction ratio of the monoamine is preferably 60 mol% or less, particularly preferably 50 mol% or less. When using an acid anhydride, a monocarboxylic acid, a monoacyl chloride compound or a monoactive ester compound as a terminator, when the total amount of all amine compounds contained in the polyimide resin (a) is set to 100 mol parts, its introduction ratio is preferably 0.1 mol part or more, particularly preferably 5 mol parts or more. On the other hand, from the aspect of maintaining the molecular weight of the resin at a high level, when the total amount of all amine compounds contained in the polyimide resin (a) is set to 100 mol parts, the introduction ratio of the terminator is preferably 100 mol parts or less, particularly preferably 90 mol parts or less. It is also possible to introduce a plurality of different terminal groups by reacting a plurality of terminators. Herein, the so-called all amine compounds refer to the total content of compounds having an amino group such as a monoamine, a diamine, and a triamine.

[0141] Among specific examples of monoamines, as monoamines having a phenolic hydroxyl group, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, etc. can be mentioned. Further, as monoamines having a photocrosslinkable group, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 2-aminostyrene, 3-aminostyrene, 4-aminostyrene, etc. can be mentioned.

[0142] As other monoamines, aniline, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, etc. can be mentioned. Two or more of them can also be used.

[0143] Among acid anhydrides, monocarboxylic acids, monochloroacyl compounds or monoactive ester compounds, as compounds having a phenolic hydroxyl group, 3-hydroxyphthalic anhydride, 3-carboxyphenol, 4-carboxyphenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene can be mentioned. Further, as compounds having a photocrosslinkable group, maleic anhydride, nadic anhydride, itaconic anhydride can be mentioned. As other compounds, phthalic anhydride, cyclohexanedicarboxylic anhydride, 3-carboxybenzenethiol, 4-carboxybenzenethiol, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, terephthalic acid, phthalic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2,6-dicarboxynaphthalene can be mentioned. Further, for the above monocarboxylic acids, monochloroacyl compounds obtained by acyl chlorination of their carboxyl groups can be used, monochloroacyl compounds obtained by acyl chlorination of only one carboxyl group of the above dicarboxylic acids can be used, and active ester compounds obtained by the reaction of monochloroacyl compounds with N-hydroxybenzotriazole, N-hydroxy-5-norbornene-2,3-dicarboximide can be used. Two or more of them can also be used.

[0144] In the polyimide resin (a), Z obtained by the following formula (Z) is preferably 0.900 or more and 1.100 or less, more preferably 0.950 or more and 1.050 or less.

[0145] Z = (A + 0.5B) / (1.5C + D + 0.5E) ··· Equation (Z)

[0146] In Equation (Z), A represents the number of moles of the dianhydride used in the synthesis of the polyimide resin (a), B represents the number of moles of the capping agent that reacts with amino groups, such as monoanhydride, monochloroformate, monocarboxylic acid, and monoactive ester, used in the synthesis of the polyimide resin (a), C represents the number of moles of the triamine compound used in the synthesis of the polyimide resin (a), D represents the number of moles of the diamine compound used in the synthesis of the polyimide resin (a), and E represents the number of moles of the capping agent that reacts with the dianhydride, such as monoamine, used in the synthesis of the polyimide resin (a).

[0147] By making the value of Z obtained from Equation (Z) within the above range, a polyimide resin (a) with good mechanical strength and suppressed thermal decomposition during heat treatment can be obtained.

[0148] The weight-average molecular weight of the polyimide resin (a), measured by gel permeation chromatography and converted to polystyrene equivalent, is preferably 3,000 to 50,000, more preferably 5,000 to 30,000. By making the weight-average molecular weight within the above range, it is possible to easily satisfy all of good solvent solubility, good solubility in the developer, and high mechanical strength. In the present invention, the weight-average molecular weight can be determined by the method described below.

[0149] The polyimide resin (a) can be obtained, for example, in the following manner: After obtaining a polyimide precursor by a known method for manufacturing a polyimide precursor, a known imidization reaction is carried out. As the method for manufacturing the polyimide precursor, for example, the following methods can be cited: Method (I), reacting a dianhydride with a diamine compound and a monoamino compound as a capping agent under low-temperature conditions; Method (II), obtaining a diester using a dianhydride and an alcohol, and then reacting it with a diamine compound and a monoamino compound as a capping agent in the presence of a condensing agent; Method (III), obtaining a diester using a dianhydride and an alcohol, then acyl chlorinating the remaining two carboxyl groups, and reacting it with a diamine compound and a monoamino compound as a capping agent; and so on. As the imidization method, for example, a method of heating the polyimide precursor to carry out dehydration ring closure, a method of chemically carrying out dehydration ring closure by the action of acetic anhydride, phosphoric anhydride, a base, carbodiimide, etc. can be cited. For the polyimide resin (a) polymerized by the above methods, it is desirable to pour it into a large amount of water, a mixed solution of methanol / water, etc., precipitate it, filter it out and dry it for separation. By this precipitation operation, low-molecular-weight components such as unreacted monomers, dimers, and trimers are removed, and the film properties after thermal curing are improved.

[0150] The polymerization solvent only needs to be able to dissolve acid anhydrides, diamines, etc. that are raw material monomers, and there is no particular limitation on its type. For example, amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 3-methyl-2-oxazolidinone, etc., cyclic esters such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, etc., carbonates such as ethylene carbonate, propylene carbonate, etc., glycols such as triethylene glycol, phenols such as m-cresol, p-cresol, etc., acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide, etc. can be cited.

[0151] With respect to 100 parts by mass of the obtained polyimide resin (a), the amount of the polymerization solvent used is preferably 100 to 1900 parts by mass, more preferably 150 to 950 parts by mass.

[0152] The photosensitive resin composition of the present invention contains at least a photosensitizer (hereinafter, sometimes referred to as "photosensitizer (b)" or simply as "(b) component") and a solvent (hereinafter, sometimes referred to as "solvent (c)" or simply as "(c) component") in the polyimide resin (a).

[0153] In the photosensitive resin composition of the present invention, in 100% by mass of the entire photosensitive resin composition, the total content of the (a) component, the (b) component, and the (c) component is preferably 60% by mass or more and 99% by mass or less, more preferably 65% by mass or more and 98% or less, and particularly preferably 70% by mass or more and 97% by mass or less. By making the total content of the (a) component, the (b) component, and the (c) component within the above range and the content ratio of each component within the range described below, it is easy to obtain a photosensitive resin composition with good coatability, less residue, and a cured product having a low relative dielectric constant after heat curing.

[0154] The viscosity of the photosensitive resin composition of the present invention is preferably 1 to 10,000 mPa·s, and more preferably 2 to 1,000 mPa·s. By making the viscosity of the photosensitive resin composition within the above range, it is easy to suppress defects and unevenness generated during coating. The viscosity here is the value measured using an E-type viscometer (cone-plate viscometer) in the atmosphere at 25°C.

[0155] Photosensitizer

[0156] The photosensitive resin composition of the present invention contains a photosensitizer (photosensitizer (b)). As the photosensitizer (b), a photoacid generator (hereinafter, sometimes referred to as "photoacid generator (b-1)" or simply as "(b-1) component") and a photopolymerization initiator (hereinafter, sometimes referred to as "photopolymerization initiator (b-2)" or simply as "(b-2) component") can be mentioned. By containing the (b-1) component, an acid is generated in the light-irradiated portion, the solubility of the light-irradiated portion in an alkaline aqueous solution increases, and a positive relief pattern in which the light-irradiated portion is dissolved can be obtained. In addition, by containing a photoacid generator and a crosslinking agent, the acid generated in the light-irradiated portion promotes the crosslinking reaction of the crosslinking agent, and a negative relief pattern in which the light-irradiated portion becomes insoluble can be obtained. In addition, by containing a photopolymerization initiator and a radically polymerizable compound, the active radicals generated in the light-irradiated portion cause radical polymerization of the ethylenically unsaturated bond in the radically polymerizable compound to proceed, and a negative relief pattern in which the light-irradiated portion becomes insoluble can be obtained. In the photosensitive resin composition of the present invention, it is preferable that all or part of the photosensitizer (b) is a photoacid generator (b-1) and exhibits positive photosensitivity. By using the (b-1) component as the photosensitizer (b), positive photosensitivity is exhibited, whereby it is easy to reduce the deviation of the opening size of the pattern caused by the processing process, and it is also easy to achieve high resolution.

[0157] Specific examples of the photoacid generator (b-1) include quinone diazide compounds, oxime sulfonate compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts, and the like.

[0158] Examples of the quinone diazide compound include a compound formed by ester-bonding quinone diazidosulfonic acid with a polyhydroxy compound, a compound formed by sulfonamide-bonding quinone diazidosulfonic acid with a polyamino compound, and a compound formed by ester-bonding and / or sulfonamide-bonding quinone diazidosulfonic acid with a polyhydroxy polyamino compound. It is preferable that 50 mol% or more of the entire functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinone diazide groups. In addition, it is preferable to contain two or more photoacid generators to obtain a photosensitive resin composition with high sensitivity.

[0159] In the present invention, the quinone diazide group is preferably any one of naphthoquinone diazide-5-sulfonyl and naphthoquinone diazide-4-sulfonyl. The naphthoquinone diazide-4-sulfonate compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The absorption of the naphthoquinone diazide-5-sulfonate compound extends to the g-line region of the mercury lamp and is suitable for g-line exposure. In the present invention, it is preferable to select the naphthoquinone diazide-4-sulfonate compound and the naphthoquinone diazide-5-sulfonate compound according to the wavelength of exposure. In addition, a naphthoquinone diazide sulfonate compound having a naphthoquinone diazide-4-sulfonyl group and a naphthoquinone diazide-5-sulfonyl group in the same molecule may be contained, or a naphthoquinone diazide-4-sulfonate compound and a naphthoquinone diazide-5-sulfonate compound may be contained. Among the photoacid generators, sulfonium salts, phosphonium salts, and diazonium salts moderately stabilize the acid component generated by exposure, and thus are preferable. Among them, sulfonium salts are preferable. In addition, a sensitizer or the like may be used as needed.

[0160] As a specific example of the photopolymerization initiator (b-2), for example, the photopolymerization initiator described in paragraphs

[0223] to

[0276] of International Publication No. 2019 / 087985 can be used. Among them, from the viewpoint of achieving high sensitization, an oxime ester-based photopolymerization initiator is preferably used. Two or more of them may also be used.

[0161] In the photosensitive resin composition of the present invention, from the viewpoint of high sensitization, the content of the component (b-1) is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the component (a). Among them, the quinone diazide compound is preferably 3 to 40 parts by mass. In addition, the total amount of the sulfonium salt, phosphonium salt, and diazonium salt is preferably 0.5 to 20 parts by mass.

[0162] In the photosensitive resin composition of the present invention, the content of the component (b-2) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (a). If it is 0.1 part by mass or more, sufficient radicals are generated by light irradiation, and the sensitivity is improved. In addition, if it is 20 parts by mass or less, there is no curing of the non-irradiated portion due to excessive generation of radicals, and the alkali developability is improved.

[0163] Solvent

[0164] The photosensitive resin composition of the present invention contains a solvent. Examples of the solvent (c) include ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol dimethyl ether, and diethylene glycol ethyl methyl ether; esters such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, and butyl lactate; alcohols such as ethanol, isopropyl alcohol, butanol, pentanol, 3-methyl-2-butanol, and 3-methyl-3-methoxybutanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisobutyl ketone, cyclopentanone, and diacetone alcohol; polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolidinone; and aromatic hydrocarbons such as toluene and xylene. Two or more of them may also be contained. The content of the solvent (c) is preferably 50 parts by mass or more, more preferably 100 parts by mass or more, and preferably 2000 parts by mass or less, more preferably 1500 parts by mass or less, based on 100 parts by mass of the component (a).

[0165] Thermal acid generator

[0166] The photosensitive resin composition of the present invention preferably contains a thermal acid generator (hereinafter, sometimes referred to as "thermal acid generator (d)" or simply as "(d) component"). The thermal acid generator does not include a compound having a function of generating an acid using light such as ultraviolet rays, but refers to a compound that generates an acid by heating. The thermal decomposition start temperature of the thermal acid generator (d) is preferably 120 °C or higher, more preferably 130 °C or higher, and further preferably 140 °C or higher. By setting the thermal decomposition temperature to 120 °C or higher, it is possible to prevent the generation of an acid during the pre-baking process in pattern processing. In addition, the thermal decomposition start temperature of the thermal acid generator (d) is preferably 250 °C or lower, more preferably 240 °C or lower, and further preferably 230 °C or lower. By setting the thermal decomposition temperature to 250 °C or lower, it is possible to generate a sufficient amount of acid during the heating process. In the present invention, by generating an acid during the heating process, when the polyimide resin (a) contains a diamine residue represented by the formula (41), the following ring-closing reaction can be promoted. As a result, the phenolic hydroxyl groups contained in the cured product can be greatly reduced. As described above, phenolic hydroxyl groups play an important role in improving sensitivity and reducing development residues during the exposure and development processes. However, if phenolic hydroxyl groups remain in the cured product, it will lead to an increase in the relative dielectric constant and water absorption of the cured product, which is not preferred. It should be noted that if the water absorption of the cured product is high, when an organic EL display device containing the cured product is manufactured, moisture volatilizes from the cured product, causing deterioration of the electrodes and light-emitting layer in the organic EL display device, and thus leading to a reduction in reliability.

[0167] [Chemical formula 18]

[0168]

[0169] The acid generated by the heat - generating acid agent (d) is preferably a strong acid. For example, it is preferably an arylsulfonic acid such as p - toluenesulfonic acid and benzenesulfonic acid, an alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid, or camphorsulfonic acid, etc.

[0170] Examples of the heat - generating acid agent (d) include sulfonium salts and sulfonic acid esters shown below. Two or more of them may also be contained. Among the sulfonium salts, from the viewpoint of generating heat by heating, compounds selected from the group consisting of mono - arylsulfonium salts and tri - alkylsulfonium salts are preferably used.

[0171] As the sulfonium salt, a sulfonium salt having the structure represented by the formula (31) is preferably used.

[0172] [Chemical formula 19]

[0173]

[0174] In the formula (31), R 4 ~R 6 each independently represents a monovalent organic group having 1 to 20 carbon atoms. As the above R 4 ~R 6 Examples of the monovalent organic group having 1 to 20 carbon atoms that can be used include a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms optionally having a substituent, and an aryl group having 6 to 20 carbon atoms optionally having a substituent. Here, as the aforementioned substituent, a hydroxyl group, a halogen atom, a cyano group, a vinyl group, an ethynyl group, or a linear or cyclic alkyl group having 1 to 10 carbon atoms can be cited. The number of carbon atoms of the aforementioned alkyl group and aryl group includes the substituent and is 1 to 10 carbon atoms and 6 to 20 carbon atoms, respectively. Z - represents an anion selected from R 7 SO3 - 、R 7 SO4 - 、R 7 COO - and SbF6 - . R 7 represents a monovalent organic group having 1 to 20 carbon atoms. As the above R 7 Examples of the monovalent organic group having 1 to 20 carbon atoms that can be used include CF3, an alkyl group, an aryl group, a perfluoroalkyl group, a structure represented by the formula (32), etc.

[0175] [Chemical formula 20]

[0176]

[0177] In Formula (32), * represents a bonding portion.

[0178] As the sulfonic acid ester, for example, a structure represented by Formula (33) can be cited.

[0179] [Chemical Formula 21]

[0180]

[0181] In Formula (33), R 7 and R 8 each independently represent a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may optionally have a substituent, or an aryl group having 6 to 20 carbon atoms which may optionally have a substituent. It should be noted that, here, as the aforementioned substituent, a hydroxyl group, a halogen atom, a cyano group, a vinyl group, an ethynyl group, a linear or cyclic alkyl group having 1 to 10 carbon atoms can be cited.

[0182] Among the thermal acid generators (d), from the aspect of high effect of improving the reliability of the organic EL display device, a thermal acid generator having a sulfonic acid ester structure is preferably used. As examples of the compound described in the aforementioned Formula (33), methyl methanesulfonate, ethyl methanesulfonate, propyl methanesulfonate, butyl methanesulfonate, phenyl methanesulfonate, methyl ethanesulfonate, ethyl ethanesulfonate, propyl ethanesulfonate, butyl ethanesulfonate, phenyl ethanesulfonate, methyl propanesulfonate, ethyl propanesulfonate, propyl propanesulfonate, butyl propanesulfonate, phenyl propanesulfonate, methyl butanesulfonate, ethyl butanesulfonate, propyl butanesulfonate, butyl butanesulfonate, phenyl butanesulfonate, methyl octanesulfonate, ethyl octanesulfonate, propyl octanesulfonate, butyl octanesulfonate, phenyl octanesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, butyl p-toluenesulfonate, phenyl p-toluenesulfonate, methoxyphenyl methanesulfonate, methoxyethyl methanesulfonate, 1,4-butanediol dimethanesulfonate, methoxyethyl p-toluenesulfonate, 1,3-propanediol di-p-toluenesulfonate, etc. can be cited.

[0183] In addition, as the thermal acid generator (d), the compound represented by the formula (34) is particularly preferably used. In the research of the inventors of the present application, it has been found that by using the compound of the formula (34) as the thermal acid generator (d), the effects of improving the exposure sensitivity and the reliability of the organic EL display device are high. Although the reason is not clear, it is speculated that the improvement of the exposure sensitivity is because, by using the compound represented by the formula (34), the solubility in the alkaline developer is more easily increased compared with the case where the compound of the formula (34) is not used. On the other hand, regarding the high effect of improving the reliability of the organic EL display device, it is considered that by using the compound represented by the formula (34), the volatility of the thermal acid generator (d) during curing (heat treatment) is reduced, and the acid can be efficiently generated from the thermal acid generator (d) during the curing process, and the ring-closing reaction of the structure represented by the formula (41) can be efficiently carried out, thus improving the reliability of the organic EL display device.

[0184] [Chemical formula 22]

[0185]

[0186] In the formula (34), R 9 is a divalent to tetravalent group having 1 to 10 carbon atoms. R 10 each independently represents an optionally substituted alkyl group having 1 to 10 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms. Examples of the aforementioned substituent include a hydroxyl group, a halogen atom, a cyano group, a vinyl group, an ethynyl group, or a linear or cyclic alkyl group having 1 to 10 carbon atoms. k represents an integer of 2 to 4.

[0187] From the viewpoint of making the exposure sensitivity higher, preferably, in the formula (34), R 9 is a divalent to tetravalent group having 1 to 6 carbon atoms, and R 10 each independently is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms or an optionally substituted aryl group having 6 to 10 carbon atoms.

[0188] Regarding the content of the compound represented by the formula (34), from the viewpoint of easily obtaining the effects of improving the exposure sensitivity and the reliability of the organic EL display device, in 100% by mass of the component (d), it is preferably contained in an amount of 20% by mass or more. More preferably, it is 50% by mass or more, further preferably 70% by mass or more, and particularly preferably 100% by mass.

[0189] In the photosensitive resin composition of the present invention, from the viewpoints of further improving the reliability of the organic EL display device and reducing the relative dielectric constant of the cured product, the content of the component (d) is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and further preferably 3 parts by mass or more, relative to 100 parts by mass of the component (a). In addition, from the viewpoint of imparting high heat resistance to the cured product, the content of the component (d) is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 8 parts by mass or less, relative to 100 parts by mass of the component (a).

[0190] The photosensitive resin composition of the present invention may further contain a radically polymerizable compound (hereinafter, sometimes referred to as "radically polymerizable compound (e)" or simply as "(e) component"), and the photosensitizer (b) may contain a photoinitiator (b-2). By adopting such a configuration, as described above, the radical polymerization of the ethylenically unsaturated bond in the radically polymerizable compound is carried out by the active radicals generated in the light irradiation portion, and a negative relief pattern in which the light irradiation portion becomes insoluble can be obtained. As a result, the photosensitive resin composition becomes a negative photosensitive resin composition.

[0191] Specific examples of the radically polymerizable compound (e) include, for example, the radically polymerizable compounds described in paragraphs

[0189] to

[0222] of International Publication No. 2019 / 087985. Among them, an aliphatic radically polymerizable compound containing a soft chain is preferably included. The aliphatic radically polymerizable compound containing a soft chain refers to a compound having a plurality of ethylenically unsaturated double bond groups and a soft skeleton such as an aliphatic chain or an oxyalkylene chain in the molecule. By including the above-mentioned aliphatic radically polymerizable compound containing a soft chain, the curing reaction during light irradiation is efficiently carried out, and the sensitivity during light irradiation can be improved. The content of the component (e) is preferably 5 to 50 parts by mass relative to 100 parts by mass of the component (a).

[0192] The photosensitive resin composition of the present invention preferably contains a crosslinking agent (hereinafter, sometimes referred to as "crosslinking agent (f)" or simply as "(f) component"). The crosslinking agent (f) refers to a compound having a crosslinkable group capable of bonding to a resin. By containing the crosslinking agent (f), the hardness and chemical resistance of the cured product can be improved. It is presumed that this is because a new crosslinked structure can be introduced into the cured product of the photosensitive resin composition by the crosslinking agent (f), so the crosslinking density is increased.

[0193] In addition, by containing the crosslinking agent (f), a pattern having a low taper shape can be formed after heat curing. It is considered that this is because a crosslinked structure is formed between polymers by the crosslinking agent (f), thereby hindering the close orientation of polymer chains with each other, maintaining the flowback property of the pattern during heat curing, and thus a pattern having a low taper shape can be formed. As the crosslinking agent (f), a compound having two or more thermally crosslinkable groups such as alkoxymethyl, hydroxymethyl, epoxy group or oxetanyl group in the molecule is preferred.

[0194] As a specific example of the crosslinking agent (f), the crosslinking agent described in paragraphs

[0407] to

[0412] of International Publication No. 2019 / 087985 can be used.

[0195] In the photosensitive resin composition of the present invention, the content of the component (f) is preferably 0.5 to 50 parts by mass with respect to 100 parts by mass of the component (a). If the content of the component (f) is within the above range, the hardness and chemical resistance of the cured product can be improved, and a pattern having a low taper shape can be formed after heat curing.

[0196] The photosensitive resin composition of the present invention can be made into a positive photosensitive resin composition further containing a dissolution accelerator (hereinafter, sometimes referred to as "dissolution accelerator (g)" or simply as "(g) component"), and the photosensitizer (b) contains a photoacid generator (b-1). The dissolution accelerator (g) compensates for the alkali developability of the photosensitive resin composition and can improve the sensitivity in the positive photosensitive resin composition. The dissolution accelerator (g) is preferably a compound having a phenolic hydroxyl group. For example, Bis-z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP-EZ, Bis26X-CP, BisP-Pz, BisP-IPZ, BisCRIPZ, BisOCP-IPZ, Bis OIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP4HBPA (Tetrakis P-DO-BPA), TrisPHAP, TrisP-PA, TrisP-PHBA, TrisP-SA, TrisOCRPA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOCF, 4PC, BIR-BIPC-F, TEP-BIP-A (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,4-dihydroxyquinoline, 2,6-dihydroxyquinoline, 2,3-dihydroxyquinoxaline, anthracene-1,2,10-triol, anthracene-1,8,9-triol, 8-hydroxyquinoline and other compounds having a phenolic hydroxyl group can be cited.

[0197] In the photosensitive resin composition of the present invention, the content of the (g) component is preferably 1 to 40 parts by mass with respect to 100 parts by mass of the (a) component.

[0198] The photosensitive resin composition of the present invention may further contain a surfactant (hereinafter, sometimes referred to as "surfactant (h)" or simply as "(h) component"). The so-called surfactant (h) refers to a compound having a hydrophilic structure and a hydrophobic structure. By appropriately containing the surfactant (h), the surface tension of the resin composition can be arbitrarily adjusted, the leveling property during coating is improved, and the film thickness uniformity of the coating film can be improved. As the aforementioned surfactant (h), a fluororesin-based surfactant, a silicone-based surfactant, a polyoxyalkylene ether-based surfactant, or an acrylic resin-based surfactant is preferred.

[0199] The content ratio of component (h) in the photosensitive resin composition of the present invention is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, based on the whole photosensitive resin composition. When the content ratio is 0.001% by mass or more, the leveling property during coating can be improved. On the other hand, the content ratio of component (h) is preferably 1% by mass or less, more preferably 0.5% by mass or less. When the content ratio is 1% by mass or less, defects generated during coating can be reduced.

[0200] The photosensitive resin composition of the present invention may also contain additives other than those described above. Examples of the aforementioned additives include polyfunctional thiol compounds described in paragraphs

[0386] to

[0398] of International Publication No. 2019 / 087985, sensitizers described in paragraphs

[0399] to

[0402] of International Publication No. 2019 / 087985, polymerization inhibitors described in paragraphs

[0403] to

[0406] of International Publication No. 2019 / 087985, silane coupling agents described in paragraphs

[0413] to

[0418] of International Publication No. 2019 / 087985, colorants described in paragraphs

[0225] to

[0252] of Japanese Patent Application Laid-Open No. 2022-136981, dispersants described in paragraphs

[0253] to

[0259] of Japanese Patent Application Laid-Open No. 2022-136981, inorganic particles described in paragraphs

[0127] to

[0130] of International Publication No. 2016 / 052268, paragraphs

[0024] to

[0025] of International Publication No. 2019 / 167461, etc.

[0201] As a method for producing the photosensitive resin composition of the present invention, for example, there are methods of charging each of the above components (a), (b), and (c), and other components used as needed into a glass flask, a stainless-steel container, etc. and stirring and dissolving them using a mechanical stirrer, etc., a method of dissolving them using ultrasonic waves, a method of stirring and dissolving them using a planetary stirring and defoaming device, etc.

[0202] For the obtained photosensitive resin composition, it is preferable to filter it using a filter to remove waste and particles. The pore diameter of the aforementioned filter is 0.5 to 0.02 μm, for example, 0.5 μm, 0.2 μm, 0.1 μm, 0.05 μm, 0.02 μm, etc., but is not limited thereto. The materials of the aforementioned filter are polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc., but polyethylene and nylon are preferred. When the photosensitive resin composition contains inorganic particles, pigments, etc., it is preferable to use a filter with a pore diameter larger than them.

[0203] The cured product of the present invention is formed by curing the photosensitive resin composition of the present invention. As a method for curing the photosensitive resin composition, for example, a method of curing by heating the photosensitive resin composition, a method of irradiating active chemical rays, etc. can be cited. By curing the photosensitive resin composition of the present invention, the heat resistance and chemical resistance of the cured product can be improved. As the aforementioned cured product, a cured product having a film shape, that is, a cured film, is preferred.

[0204] Next, a method for manufacturing the cured product of the present invention will be described.

[0205] The method for manufacturing the cured product of the present invention preferably includes the following steps.

[0206] Step (1): Coating the above-mentioned photosensitive resin composition on a substrate to form a photosensitive resin film;

[0207] Step (2): Drying the photosensitive resin film;

[0208] Step (3): Exposing the dried photosensitive resin film through a photomask;

[0209] Step (4): Developing the exposed photosensitive resin film; and

[0210] Step (5): Heat-treating the developed photosensitive resin film.

[0211] In the above step (1), the photosensitive resin composition of the present invention is coated by a spin coating method, a slit coating method, a dip coating method, a spraying method, a printing method, etc. to obtain a photosensitive resin film of the photosensitive resin composition. Before coating, the substrate to be coated with the photosensitive resin composition can also be pretreated with an adhesion improver. For example, the following methods can be cited: using a solution obtained by dissolving 0.5 to 20% by mass of the adhesion improver in a solvent such as isopropyl alcohol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, etc. to treat the surface of the substrate. As a method for treating the surface of the substrate, methods such as spin coating, slot die coating, bar coating, dip coating, spraying, vapor treatment, etc. can be cited. As a specific example of the adhesion improver, for example, the adhesion improver described in paragraph

[0127] of International Publication No. 2019 / 065351 can be cited.

[0212] In the above step (2), if necessary, a reduced-pressure drying treatment is performed on the coated photosensitive resin film, and then, using a hot plate, an oven, infrared rays, etc., a heat treatment is performed in the range of 50°C to 180°C for 1 minute to several hours to obtain a photosensitive resin film.

[0213] In the above step (3), actinic rays are irradiated onto the photosensitive resin film through a photomask having a desired pattern. As the actinic rays used in the exposure, there are ultraviolet rays, visible light, electron beams, X-rays, etc. However, in the present invention, i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp are preferably used. After irradiating the actinic rays, post-exposure baking may be performed. By performing post-exposure baking, effects such as improved resolution after development or an increased allowable range of development conditions can be expected. For post-exposure baking, an oven, a hot plate, infrared rays, a rapid annealing device, a laser annealing device, etc. can be used. As the post-exposure baking temperature, it is preferably 50 to 180°C, more preferably 60 to 150°C. The post-exposure baking time is preferably 10 seconds to several hours. If the post-exposure baking time is within the above range, the reaction proceeds well, and sometimes the development time can be shortened.

[0214] In the above step (4), the exposed photosensitive resin film is developed using a developer to remove the portions other than the exposed portions. As the developer, an aqueous solution of a basic compound such as tetramethylammonium hydroxide (TMAH), diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine, etc. is preferred. Additionally, depending on the situation, polar solvents such as N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone (GBL), dimethylacrylamide, etc., alcohols such as methanol, ethanol, isopropyl alcohol, etc., esters such as ethyl lactate, propylene glycol monomethyl ether acetate, etc., ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, methyl isobutyl ketone, etc. may be added alone or in combination to these basic aqueous solutions. As the development method, it can be spray, spin coating immersion, dipping, ultrasonic wave, etc.

[0215] Next, it is preferable to perform a rinsing treatment on the pattern formed by development using deionized water. Here, alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, etc. may be added to the deionized water for the rinsing treatment.

[0216] Next, the above-mentioned step (5) is carried out. Through the heat treatment, residual solvents and components with low heat resistance can be removed, so that the heat resistance and chemical resistance can be improved. Since the photosensitive resin composition of the present invention contains a polyimide resin, an imide ring can be formed through the heat treatment, thereby improving the heat resistance and chemical resistance. In addition, in the case of containing a thermal crosslinking agent, a thermal crosslinking reaction can be carried out through the heat treatment, thereby improving the heat resistance and chemical resistance. Regarding this heat treatment, while selecting a temperature and raising the temperature step by step, or selecting a certain temperature range and raising the temperature continuously, it is carried out for 5 minutes to 5 hours. As an example, heat treatments are carried out at 150 °C and 250 °C for 30 minutes each. Or, methods such as linearly raising the temperature from room temperature to 300 °C over 2 hours can be cited. As the heat treatment conditions in the present invention, it is preferably 180 °C or higher, more preferably 200 °C or higher, further preferably 230 °C or higher, and particularly preferably 240 °C or higher. In addition, the heat treatment conditions are preferably 400 °C or lower, more preferably 350 °C or lower, and further preferably 300 °C or lower.

[0217] Next, as an example of a method for manufacturing the cured product of the present invention, a method for manufacturing a cured film using a photosensitive sheet obtained by forming the photosensitive resin composition of the present invention into a sheet will be described. It should be noted that here, the photosensitive sheet refers to a sheet-like photosensitive resin composition obtained by coating the photosensitive resin composition on a peelable substrate and drying it.

[0218] In the case of using a photosensitive sheet obtained by forming the photosensitive resin composition of the present invention into a sheet, when there is a protective film on the photosensitive sheet, it is peeled off, the photosensitive sheet is opposed to the substrate, and they are bonded by thermocompression bonding to obtain a photosensitive resin film. The photosensitive sheet can be obtained by coating the photosensitive resin composition of the present invention on a support film made of polyethylene terephthalate or the like as a peelable substrate and drying it.

[0219] The thermocompression bonding can be carried out by thermocompression treatment, thermal lamination treatment, thermal vacuum lamination treatment, etc. From the aspects of adhesion and embedding property to the substrate, the bonding temperature is preferably 40 °C or higher. In addition, in the case where the photosensitive sheet has photosensitivity, in order to prevent the photosensitive sheet from curing during bonding and resulting in a decrease in the resolution of pattern formation in the exposure and development processes, the bonding temperature is preferably 140 °C or lower.

[0220] Regarding the photosensitive resin film obtained by bonding the photosensitive sheet to the substrate, a cured film can be formed according to the steps of exposing the above-mentioned photosensitive resin film, developing the exposed photosensitive resin film, and performing heat curing.

[0221] The organic EL display device of the present invention includes the cured product of the present invention. Preferably, the organic EL display device of the present invention includes the cured product of the present invention as one or more selected from the group consisting of a pixel division layer, an electrode insulating layer, a wiring insulating layer, an interlayer insulating layer, a TFT planarization layer, an electrode planarization layer, a wiring planarization layer, a TFT protective layer, an electrode protective layer, a wiring protective layer, a gate insulating layer, a color filter, a black matrix, and a black column spacer.

[0222] The electronic component of the present invention includes the cured product of the present invention. Preferably, the electronic component of the present invention includes the cured product of the present invention as an insulating film or a protective film constituting the electronic component.

[0223] Here, as the electronic component, active components having semiconductors such as transistors, diodes, integrated circuits (ICs), memories, etc., and passive components such as resistors, capacitors, inductors, etc. can be cited. In addition, an electronic component using a semiconductor is also called a semiconductor device.

[0224] As a specific example of the cured film in the electronic component, preferably, a passivation film for a semiconductor, a surface protective film for a semiconductor element, a TFT (Thin Film Transistor), etc., an interlayer insulating film such as an interlayer insulating film between rewiring layers in a 2- to 10-layer high-density mounting multilayer wiring, an insulating film of a touch panel display, a protective film, an insulating layer of an organic electroluminescent element, etc. are used, but it is not limited thereto, and various structures can be adopted.

[0225] Examples

[0226] Hereinafter, examples and comparative examples are given to more specifically illustrate the present invention, but the present invention is not limited to these ranges. It should be noted that for the compounds using abbreviations in the compounds used, the names are shown below.

[0227] (Acid dianhydride)

[0228] TDA-100: 1,3,3a,4,5,9b-Hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione (compound represented by formula (13))

[0229] PPHT: Compound represented by formula (14)

[0230] BzDA: Compound represented by formula (12)

[0231] TBIS-DMPN: Compound represented by formula (15)

[0232] BNBDA: Compound represented by formula (35)

[0233] MCTC: 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (compound represented by formula (36))

[0234] ODPA: 4,4'-oxybisphthalic anhydride.

[0235] [Chemical formula 23]

[0236]

[0237] (diamine compound)

[0238] HA: 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane

[0239] 6FAP: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane

[0240] Priamine 1075: Dimer diamine compound containing the compound represented by formula (18) (trade name, manufactured by Claude Japan Co., Ltd.) (average amine value: 205).

[0241] (capping agent that reacts with the diamine compound)

[0242] NA: 5-norbornene-2,3-dicarboxylic anhydride

[0243] MA: Maleic anhydride

[0244] IA: Itaconic anhydride.

[0245] (solvent)

[0246] NMP: N-methyl-2-pyrrolidone

[0247] MPA: 3-methoxy-N,N-dimethylpropanamide

[0248] DMI: 1,3-dimethyl-2-imidazolidinone

[0249] PGME: Propylene glycol monomethyl ether

[0250] EL: Ethyl lactate

[0251] GBL: γ-butyrolactone.

[0252] (others)

[0253] ITO: Indium tin oxide

[0254] TMAH: Tetramethylammonium hydroxide

[0255] BTS: Butyl p-toluenesulfonate (manufactured by FUJIFILM Wako Pure Chemical Corporation)

[0256] BPAF: Bisphenol AF

[0257] The evaluation methods in each of the examples and comparative examples are shown below.

[0258] Note that in the evaluation of the photosensitive resin composition, the pretreatment of the ITO substrate when using the ITO substrate was carried out under the following conditions.

[0259] Pretreatment of ITO Substrate

[0260] For a glass substrate (manufactured by Geomatec Co., Ltd.; hereinafter referred to as "ITO substrate") on which ITO was formed by sputtering to a thickness of 100 nm on glass, a bench-top optical surface treatment apparatus (PL16-110; manufactured by SEN Special Light Source Co., Ltd.) was used, and after performing a UV-O3 washing treatment for 100 seconds, it was used. For a Si wafer (manufactured by Electronics And Materials Corporation Limited), a hot plate (HP-1SA; manufactured by AS ONE Co., Ltd.) was used, and after performing a dehydration baking treatment by heating at 130 °C for 2 minutes, it was used.

[0261] [Measurement and Evaluation Methods]

[0262] (1) Film Thickness Measurement

[0263] Using a surface roughness and profile shape measuring machine (SURFCOM1400D; manufactured by Tokyo Seimitsu Co., Ltd.), the measurement magnification was set to 10,000 times, the measurement length was set to 1.0 mm, and the measurement speed was set to 0.30 mm / s to measure the film thickness.

[0264] (2) Weight-Average Molecular Weight of Polyimide Resin

[0265] Using a GPC analysis device, the weight-average molecular weight (Mw) in terms of polystyrene conversion was measured and determined. Note that the weight-average molecular weight of the polyimide resin was measured under the following conditions.

[0266] Measurement Device: Waters2695 (manufactured by Waters Corporation)

[0267] Column Temperature: 50 °C

[0268] Flow Rate: 0.4 mL / min

[0269] Detector: 2489 UV / Vis Detector (measurement wavelength 260 nm)

[0270] Developing solvent: NMP (containing 0.21% by mass of lithium chloride and 0.48% by mass of phosphoric acid)

[0271] Guard column: TOSOH TSK guard column (manufactured by TOSOH CORPORATION)

[0272] Column: TOSOH TSK-GELa-2500,

[0273] TOSOH TSK-GELa-4000 in series (both manufactured by TOSOH CORPORATION)

[0274] Number of measurements: 2 times (the average value is taken as the weight-average molecular weight of the polyimide).

[0275] (3) Imide ring closure rate (R IM (%))

[0276] Dissolve the polyimide resin in GBL so that the concentration becomes 35% by mass. Using a spin coater (1H-DX manufactured by MIKASA CORPORATION), coat this solution on a 4-inch silicon wafer by spin coating method. Then, bake it on a hot plate at 120 °C for 3 minutes to produce a resin film with a thickness of 4 - 5 μm. Divide the wafer with the resin film into 2 pieces. For one of them, use a clean oven (CLH-21CD-S manufactured by Koyo Thermo Systems Co., Ltd.), under a nitrogen flow (oxygen concentration is 20 ppm or less), cure it at 140 °C for 30 minutes, then further raise the temperature and cure it at 320 °C for 1 hour to completely close the imide ring. Use an infrared spectrophotometer (FT-720 manufactured by Horiba, Ltd.) to measure the infrared absorption spectra of the resin films before and after curing respectively, confirm the presence of absorption peaks (near 1780 cm -1 near, 1377 cm -1 near) due to the imide structure of the polyimide. After that, find the peak intensity near 1377 cm -1 (before curing: X, after curing: Y). Calculate the peak intensity ratio obtained by dividing the peak intensity (X) by the peak intensity (Y), and find the content of imide groups in the polymer before heat treatment, that is, the imide ring closure rate (R IM )(R IM = X / Y × 100 (%))

[0277] (4) Solvent solubility

[0278] The powder of the polyimide resin of the specimen and EL were respectively put into polypropylene vials with a capacity of 32 mL such that the polyimide resin concentration became 35% by mass, 25% by mass, and 15% by mass, and mixed under the conditions of stirring for 10 minutes and defoaming for 1 minute using a stirring and defoaming device (ARE-310 manufactured by Thinky Corporation). Then, the vials after the mixing operation were visually confirmed and judged according to the following evaluation criteria. It should be noted that the above operations were carried out in a room where the temperature was adjusted to room temperature of 23 ± 2°C. A, B, and C where there was no remaining part of undissolved matter when the concentration was 15% by mass or more were regarded as qualified. It should be noted that A was the most preferred result.

[0279] A: There was no remaining part of undissolved matter in the vial with a concentration of 35% by mass

[0280] B: There was a remaining part of undissolved matter in the vial with a concentration of 35% by mass, and there was no remaining part of undissolved matter in the vial with a concentration of 25% by mass

[0281] C: There was a remaining part of undissolved matter in the vial with a concentration of 25% by mass, and there was no remaining part of undissolved matter in the vial with a concentration of 15% by mass

[0282] D: There was a remaining part of undissolved matter in the vial with a concentration of 15% by mass.

[0283] (5) Sensitivity evaluation and development residue evaluation of the photosensitive resin composition

[0284] Using a spin coater (MS-A100; manufactured by MIKASA Co., Ltd.), the rotation speed was adjusted so that the film thickness of the pre-baked film became about 1.8 μm, and the photosensitive resin composition as a specimen was coated on a 100 mm × 100 mm ITO substrate by spin coating. Then, using a heating plate with a buzzer (HPD-3000BZN; manufactured by AS ONE Co., Ltd.), pre-baking was carried out at 110°C for 120 seconds to produce a pre-baked film with a film thickness of about 1.8 μm. For the obtained pre-baked film, using a manual exposure machine (MA-1200; manufactured by Dainippon Kagaku Kenkyusho Co., Ltd.), through a positive mask (manufactured by HOYA Corporation, the stripe design line width was 20 μm), using ultraviolet rays, the maximum exposure amount was 150 mJ / cm 2 (value of the i-line illuminometer), every 5 mJ / cm 2Exposure is carried out by reducing the exposure amount, development and rinsing are performed, and drying is carried out, whereby a patterned substrate in which a photosensitive resin film forms a specified pattern is obtained. Using the patterned substrates with various exposure amounts, evaluation of sensitivity and development residues is performed. It should be noted that development is carried out by a method of spray development using an alkaline developer of 2.38 mass% TMAH aqueous solution with a small-sized automatic lithographic developing apparatus (AD-2000 manufactured by Takizawa Sangyo Co., Ltd.). In addition, the development time is adjusted so that the film loss amount of the unexposed portion becomes 0.5 μm, and rinsing is carried out using deionized water.

[0285] (5-1) Sensitivity evaluation

[0286] Using an FPD / LSI inspection microscope (OPTIPHOT-300; manufactured by Nikon Corporation), the opening portions of the developed film obtained are observed, and the lowest exposure amount at which the opening width becomes the same line width (20 μm) as the mask design is taken as the sensitivity. Judgment is made as follows, and A, B, and C with a sensitivity less than 100 mJ / cm 2 are regarded as qualified. It should be noted that A is the most preferable result.

[0287] A: Sensitivity is less than 80 mJ / cm 2

[0288] B: Sensitivity is 80 mJ / cm 2 or more and less than 90 mJ / cm 2

[0289] C: Sensitivity is 90 mJ / cm 2 or more and less than 100 mJ / cm 2

[0290] D: Sensitivity is 100 mJ / cm 2 or more.

[0291] (5-2) Development residue evaluation

[0292] Using an FPD / LSI inspection microscope (OPTIPHOT-300; manufactured by Nikon Corporation), the opening portions of the developed film obtained are observed, and the generation amount of residues at the opening portions at the lowest exposure amount at which the opening width becomes the same line width (20 μm) as the mask design is evaluated. Judgment is made as follows, and A, B, and C with the existence area of residues at the opening portions less than 10% are regarded as qualified. It should be noted that A is the most preferable result.

[0293] A: No residues at the opening portions (less than 1%)

[0294] B: The area of the residue at the opening is 1% or more and less than 5%.

[0295] C: The area of the residue at the opening is 5% or more and less than 10%.

[0296] D: The area of the residue at the opening is 10% or more.

[0297] (6) Relative dielectric constant measurement

[0298] Using a spin coater (MS-A100; manufactured by MIKASA Co., Ltd.), adjust the rotation speed so that the film thickness of the pre-baked film becomes approximately 2.0 μm. By spin coating, coat the entire surface of an aluminum substrate with an area of 6 cm × 6 cm and a thickness of 0.3 mm with the photosensitive resin composition as a sample. Then, using a heating plate with a buzzer (HPD-3000BZN; manufactured by AS ONE Co., Ltd.), perform pre-baking at 110 °C for 120 seconds to produce a pre-baked film with a film thickness of approximately 2.0 μm. For the obtained pre-baked film, using a small automatic developing device for lithography (AD-2000 manufactured by Tak izawa Sangyo Co., Ltd.), perform spray development for 20 seconds using an alkaline developer of 2.38 mass% TMAH aqueous solution, and then rinse with deionized water. Next, using a high-temperature inert gas oven (INH-9CD-S manufactured by Koyo Thermo Systems Co., Ltd.), heat the developed film obtained at 250 °C for 1 hour in a nitrogen atmosphere to obtain a sample in which a cured product formed by curing the photosensitive composition is laminated on an aluminum substrate. Then, on this cured product, form an aluminum electrode by evaporation. The aluminum electrode is a measurement electrode with a circular pattern having a diameter of 10 mm and a protective electrode with an annular pattern having an inner diameter of 11.5 mm. The portion sandwiched between the measurement electrode and the aluminum substrate becomes the measurement target area. The measurement sample is left standing in a room at room temperature of 23 ± 1 °C and humidity of 45 ± 5% for 24 hours before measurement. The measurement is performed for the capacitance at a frequency of 1 kHz in the measurement target area using an impedance analyzer (Impedance Analyzer) 4294A and a sample holder (Sample Holder) 16451B (both manufactured by Agilent Technologies Inc.). The relative dielectric constant is calculated from the capacitance and the film thickness of the measurement target area. The results of the relative dielectric constant are judged as follows, and A, B, and C with a relative dielectric constant less than 3.60 are regarded as qualified. It should be noted that A is the most preferable result.

[0299] A: The relative dielectric constant at 1 kHz is less than 3.40

[0300] B: The relative dielectric constant at 1 kHz is 3.40 or more and less than 3.50

[0301] C: The relative dielectric constant at 1 kHz is 3.50 or more and less than 3.60

[0302] D: The relative dielectric constant at 1 kHz is 3.60 or more.

[0303] (7) Measurement of water absorption rate

[0304] On a 6-inch silicon wafer whose weight has been previously measured (weight: W0 (g)), a photosensitive resin composition as a sample is coated by spin coating to obtain a substrate with a photosensitive resin film. As a drying process, pre-baking is performed on a hot plate at 110 °C for 120 seconds to produce a pre-baked film with a film thickness of 3.5 μm. Then, for the pre-baked film, an automatic developing device (AD-2000 manufactured by Takizawa Sangyo Co., Ltd.) is used to spray with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide for 60 seconds, and then rinsed with deionized water for 30 seconds. Next, in a nitrogen atmosphere, the substrate with the photosensitive resin film after rinsing is cured (heat-treated) in an oven at 250 °C for 60 minutes to obtain a substrate with a cured film. After measuring the weight W1 (g) of the obtained substrate with the cured film, it is immersed in deionized water at 23 °C for 24 hours. After taking it out from the deionized water, the water attached to the substrate with the cured film is wiped off sufficiently, and then the weight W2 (g) is measured. Then, the water absorption rate (%) is calculated using the following formula (X).

[0305] Water absorption rate = (W2 - W1) / (W1 - W0) × 100 ··· Formula (X).

[0306] The results of the water absorption rate are judged according to the following criteria, and A, B, and C with a water absorption rate less than 2.8% are regarded as qualified. It should be noted that A is the most preferred result.

[0307] A: Water absorption rate is less than 2.0%

[0308] B: Water absorption rate is 2.0% or more and less than 2.4%

[0309] C: Water absorption rate is 2.4% or more and less than 2.8%

[0310] D: Water absorption rate is 2.8% or more.

[0311] (8) Planarity evaluation

[0312] In Figure 1A cross-sectional view of the flatness evaluation sample is shown. Using a spin coater (MS-A100; manufactured by MIKASA Co., Ltd.), on a 100 mm square step substrate 1 on which 5 line patterns with a thickness (height) of 1.2 μm, a width of 5 μm, and a length of 15 mm were patterned in parallel at intervals of 5 μm in the central part of the substrate, a photosensitive composition as a sample was coated by spin coating, pre-baked at 110 °C for 120 seconds, and a pre-baked film was produced such that the film thickness h0 of the flat part on the substrate where the foregoing pattern was not provided (for convenience, the measured part is referred to as "measurement point A") was 3.7 μm in a manner not affected by the foregoing pattern. Then, using a small automatic developing device for lithography (AD-2000 manufactured by Takizawa Sangyo Co., Ltd.), an aqueous solution of 2.38 mass% TMAH was used, and treatment was performed such that the film thickness after rinsing and drying at measurement point A was 3.2 μm. Then, rinsing was performed using deionized water, and spin drying was performed. Next, with respect to the obtained substrate with a film, a curing step was carried out using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.), heating to 250 °C at a rate of 5 °C / minute under the condition that the oxygen concentration was 20 ppm or less and heating at 250 °C for 1 hour to produce a cured film with a film thickness of approximately 2.5 μm at measurement point A. The surface roughness of the obtained cured film was measured using a surface profiler (P-15; manufactured by KLA-Tencor Corporation), and the average value of the heights h1 to h3 of 3 out of the foregoing 5 line patterns starting from the baseline 10 of the film existing on the line pattern was taken as the surface roughness h. It should be noted that, from Figure 1 viewpoint, the baseline 10 is defined as the line connecting the points with the minimum film thickness of the concave parts existing on the left and right of each part of the mountain-shaped resin film where h1 to h3 are measured. Specific examples are described below. Figure 1 In, the straight line connecting the bottoms a1 and a2 of the step shape is taken as the baseline, and the length from the top b1 of the step shape to the intersection of the line extending vertically downward with respect to the substrate surface and the baseline is defined as h1. h2 is defined as the length from b2 to the intersection of the line extending vertically downward with respect to the substrate surface and the baseline, taking the line connecting a2 and a3 as the baseline, and h3 is defined as the length distance from b3 to the intersection of the line extending vertically downward with respect to the substrate surface and the baseline, taking the line connecting a3 and a4 as the baseline. Based on the surface roughness h, the planarization property is determined as follows, and A, B, and C with a surface roughness h less than 0.4 μm are regarded as qualified. It should be noted that A is the most preferred result.

[0313] A: The surface roughness h is less than 0.2 μm

[0314] B: The surface height difference h is 0.2 μm or more and less than 0.3 μm.

[0315] C: The surface height difference h is 0.3 μm or more and less than 0.4 μm.

[0316] D: The surface height difference h is 0.4 μm or more.

[0317] (9) Chemical resistance evaluation

[0318] Using a spin coating method, the photosensitive resin composition as a sample was coated on an alkali-free glass plate (OA-10 manufactured by Nippon Electric Glass Co., Ltd.) to obtain a photosensitive resin film. As a drying process, pre-baking was performed on a hot plate at 110 °C for 120 seconds to produce a pre-baked film with a film thickness of about 2.0 μm. For the obtained pre-baked film, using a small automatic developing device for lithography (AD-2000 manufactured by Takizawa Sangyo Co., Ltd.), after spray developing for 20 seconds using an alkaline developer of 2.38 mass% TMAH aqueous solution, rinsing was performed using deionized water. Then, using a high-temperature inert gas oven (INH-9CD-S manufactured by Koyo ThermoSystems Co., Ltd.), in a nitrogen atmosphere, the developed film was heated at 250 °C for 1 hour, whereby a sample having a cured product formed by curing the photosensitive composition laminated on an alkali-free glass substrate was obtained. Then, the film thickness of the cured product was measured to obtain the film thickness before the dipping treatment. Next, the cured film was dipped in the stripping solution 106 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 60 °C for 10 minutes for chemical solution treatment. After the chemical solution treatment, rinsing was performed using deionized water, and after wiping off the deionized water, the film thickness after the treatment was measured to obtain the film loss amount caused by the dipping treatment. The determination was made as follows, and A, B, and C with a film loss amount less than 0.10 μm were regarded as qualified. It should be noted that A is the most preferred result.

[0319] A: The film loss amount is less than 0.03 μm

[0320] B: The film loss amount is 0.03 μm or more and less than 0.06 μm

[0321] C: The film loss amount is 0.06 μm or more and less than 0.10 μm

[0322] D: The film loss amount is 0.10 μm or more.

[0323] (10) Measurement of the depth from the substrate surface where no carbon component is detected (X-ray photoelectron spectroscopy (XPS)) (penetration depth of carbon component)

[0324] Instead of using a 100 mm × 100 mm ITO substrate, a 4-inch silicon wafer coated with aluminum was used. In addition, a photosensitive resin composition as a sample was coated so that the film thickness of the pre-baked film became 3.6 μm. Except for this, development, rinsing, and drying were performed in the same manner as in the above (5), and a patterned substrate up to the development process was obtained. Using an FPD / LSI inspection microscope (OPTIPHOT-300; manufactured by Nikon Corporation), the openings of the obtained patterned substrate were observed, and the minimum exposure amount at which the opening width became the same line width (20 μm) as the mask design was confirmed. Next, using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.), the above patterned substrate was thermally cured at 250°C to obtain a cured film. Regarding the thermal curing conditions, the following conditions were implemented: In a nitrogen atmosphere, the patterned substrate was put into an oven whose temperature had been adjusted to 250°C, and thermal curing was performed for 60 minutes. Then, using an X-ray photoelectron spectrometer SSX-100 manufactured by SSI, the surface of the opening of the sample exposed at the minimum exposure amount at which the opening width became the same line width (20 μm) as the mask design was measured. Further, taking the substrate part between the lines that appeared after development as the object, depth distribution analysis based on Ar ion etching was performed, and in order to investigate the degree of contamination of the substrate by the carbon component (organic matter), the depth at which the carbon component could not be detected was measured. The results were judged as follows, and A, B, and C with a depth from the substrate surface where the carbon component could not be detected of less than 10.0 nm were regarded as qualified. It should be noted that A is the most preferable result.

[0325] A: The depth from the substrate surface where the carbon component could not be detected is less than 7.5 nm

[0326] B: The depth from the substrate surface where the carbon component could not be detected is 7.5 nm or more and less than 10.0 nm

[0327] C: The depth from the substrate surface where the carbon component could not be detected is 10.0 nm or more and less than 12.5 nm

[0328] D: The depth from the substrate surface where the carbon component could not be detected is 12.5 nm or more.

[0329] (11) Evaluation of the emission reliability of the organic EL display device

[0330] The organic EL display device as a sample was placed on a hot plate heated to 80°C with the display part (light-emitting surface) facing up, and it was driven by direct current at 10 mA / cm 2The luminous area ratio of the pixels (the area ratio of the light-emitting part with respect to the area of the light-emitting pixels) is evaluated 1 hour after making it emit light, and then the power supply is temporarily turned off to make it go out. Then, as simulated sunlight, light with an illuminance of 3.0 W / m at a wavelength of 420 nm from a xenon lamp is continuously irradiated onto the display unit. After 100 hours and 500 hours since the start of irradiation, it is made to emit light again, and the pixel luminous area ratio is measured for 10 light-emitting pixel parts located in the central part, and the average value is calculated. The more capable of maintaining a high pixel luminous area ratio, the more excellent the light-emitting reliability is considered, and it is evaluated based on the following judgment criteria. A to C with a light-emitting part area ratio of 65% or more with respect to the area of the light-emitting pixels are regarded as qualified. It should be noted that A is the most preferred result. 2 After continuously irradiating the display unit with light having an illuminance of 3.0 W / m² at a wavelength of 420 nm from a xenon lamp as simulated sunlight for 100 hours and 500 hours, it is made to emit light again, and the pixel luminous area ratio is measured for 10 light-emitting pixel parts located in the central part, and the average value is calculated. The more capable of maintaining a high pixel luminous area ratio, the more excellent the light-emitting reliability is considered, and it is evaluated based on the following judgment criteria. A to C with a light-emitting part area ratio of 65% or more with respect to the area of the light-emitting pixels are regarded as qualified. It should be noted that A is the most preferred result.

[0331] A: The area ratio of the light-emitting part with respect to the area of the light-emitting pixels is 95% or more

[0332] B: The area ratio of the light-emitting part with respect to the area of the light-emitting pixels is 80% or more and less than 95%

[0333] C: The area ratio of the light-emitting part with respect to the area of the light-emitting pixels is 65% or more and less than 80%

[0334] D: The area ratio of the light-emitting part with respect to the area of the light-emitting pixels is less than 65%.

[0335] [Manufacturing / Synthesis / Preparation Examples]

[0336] Synthesis Example 1: Synthesis of Quinonediazide Compound a (QD-a)

[0337] Under a dry nitrogen stream, 21.22 g (0.05 mol) of TrisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) and 36.27 g (0.135 mol) of diazoquinonaphthalenesulfonyl chloride are dissolved in 450 g of 1,4-dioxane at room temperature. A liquid obtained by dissolving 15.18 g of triethylamine in 50 g of 1,4-dioxane is added dropwise thereto so that the temperature inside the system is 35°C or lower. After the addition, it is stirred at 30°C for 2 hours. The triethylamine salt is filtered, and the filtrate is poured into water. Then, it is filtered, and the precipitated solid is collected. The solid is dried using a vacuum dryer to obtain the quinonediazide compound a represented by the formula (38).

[0338] [Chemical Formula 24]

[0339]

[0340] In the formula (38), * represents the bonding site with the oxygen atom.

[0341] Synthesis Example 2: Synthesis of Quinonediazide Compound b (QD-b)

[0342] Using 36.27 g (0.135 mol) of diazoquinonaphthalene-4-sulfonyl chloride in place of 36.27 g (0.135 mol) of diazoquinonaphthalene-5-sulfonyl chloride, the quinonediazide compound b represented by the formula (39) was obtained by synthesis in the same manner as in Synthesis Example 2.

[0343] [Chemical formula 25]

[0344]

[0345] In the formula (39), * represents the bonding site with the oxygen atom.

[0346] Synthesis Example 3: Synthesis of Diamine (DAP-B)

[0347] 26.70 g (0.086 mol) of BisP-HTG (manufactured by Honshu Chemical Industry Co., Ltd.; 4,4'-(3,3,5-trimethylcyclohexylidene)bisphenol) and 100 ml of glacial acetic acid were placed in a 500 ml four-necked flask equipped with a stirrer, a thermocouple, and a dropping funnel, and stirred. The internal temperature was raised to 50 °C using a water bath. 2 ml (0.026 mol) of concentrated nitric acid was added dropwise thereto over 1 hour, and then ice-cooled to lower the internal temperature to 13 °C. 13.3 ml (0.149 mol) of concentrated nitric acid was further added dropwise over 1 hour. Then, stirring was continued for 3 hours, the precipitated yellow crystals were filtered, washed successively with 40 ml of glacial acetic acid and 80 ml of deionized water, and dried under reduced pressure to obtain a dinitro body.

[0348] Next, 50.27 g (0.135 mol) of the above dinitro body, 180 ml (3.71 mol) of hydrazine monohydrate, and 900 ml of ethanol were placed in a 2 L four-necked flask equipped with a stirrer, a thermocouple, a Dimroth condenser, and a dropping funnel, and stirred under ice-cooling. 0.9 g of 5% palladium-carbon (manufactured by Wako Pure Chemical Industries, Ltd.) suspended in 30 ml of ethanol was added dropwise thereto over 1 hour. Then, the solution was refluxed for 2 hours, and the palladium-carbon was filtered off while washing with 300 ml of ethanol. All the solvents were removed by heating under reduced pressure, the residue was washed with 75 ml of ice-cooled ethanol, filtered, and further washed successively with 75 ml of deionized water and 150 ml of diethyl ether, and dried under reduced pressure to obtain the diamine (DAP-B) represented by the following formula.

[0349] [Chemical formula 26]

[0350]

[0351] Synthesis Example 4: Synthesis of Diamine (DAP-C)

[0352] Instead of using BisP-HTG (manufactured by Honshu Chemical Industry Co., Ltd.), 23.25 g (0.086 mol) of 4,4'-(1,3-dimethylbutylene) diphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used to synthesize the dinitro body. In the next step, 48.65 g (0.135 mol) of this dinitro body was used. Otherwise, the operation was the same as in Synthesis Example 3 to obtain the diamine (DAP-C) represented by the following formula.

[0353] [Chemical formula 27]

[0354]

[0355] Synthesis Example 5: Synthesis of Diamine (DAP-G)

[0356] Instead of using BisP-HTG (manufactured by Honshu Chemical Industry Co., Ltd.), 20.84 g (0.086 mol) of BIOC-E (manufactured by Asahi Organic Materials Co., Ltd.; 1,1'-bis(4-hydroxy-3-methylphenyl)ethane) was used to synthesize the dinitro body. 44.86 g (0.135 mol) of the dinitro body was used. Otherwise, the operation was the same as in Synthesis Example 3 to obtain the diamine (DAP-G) represented by the following formula.

[0357] [Chemical formula 28]

[0358]

[0359] Synthesis Example 6: Synthesis of 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane (HA)

[0360] Dissolve 18.3 g (0.05 mol) of 6FAP in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide (manufactured by Tokyo Chemical Industry Co., Ltd.), and cool to -15°C. Dropwise add a solution obtained by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 mL of acetone. After the dropwise addition is completed, stir at -15°C for 4 hours, and then return to room temperature. Filter out the precipitated white solid and perform vacuum drying at 50°C.

[0361] Put 30 g of the obtained white solid into a 300 mL stainless steel autoclave, disperse it in 250 mL of methyl cellosolve, and add 2.0 g of 5% palladium-carbon (manufactured by Wako Pure Chemical Industries, Ltd.). Introduce hydrogen into it using a balloon and carry out a reduction reaction at room temperature. After about 2 hours, confirm that the balloon no longer deflates and end the reaction. After the reaction is completed, filter to remove the palladium compound as a catalyst, and concentrate using a rotary evaporator to obtain the diamine compound (HA) represented by the following formula.

[0362] [Chemical formula 29]

[0363]

[0364] Synthesis Example 7: Synthesis of diamine compound (HC)

[0365] Using 17.0 g (0.05 mol) of DAP-B obtained in Synthesis Example 3 instead of 6FAP, and performing the same operations as in Synthesis Example 6, a diamine compound (HC) represented by the following formula was obtained.

[0366] [Chemical formula 30]

[0367]

[0368] Synthesis Example 8: Synthesis of diamine compound (HD)

[0369] Using 15.0 g (0.05 mol) of DAP-C obtained in Synthesis Example 4 instead of 6FAP, and performing the same operations as in Synthesis Example 6, a diamine compound (HD) represented by the following formula was obtained.

[0370] [Chemical formula 31]

[0371]

[0372] Synthesis Example 9: Synthesis of diamine compound (HI)

[0373] Using 13.6 g (0.05 mol) of DAP-G obtained in Synthesis Example 5 instead of 6FAP, and performing the same operations as in Synthesis Example 6, a diamine compound (HI) represented by the following formula was obtained.

[0374] [Chemical formula 32]

[0375]

[0376] Example 1 Synthesis of polyimide resin (P1)

[0377] Under a dry nitrogen stream, 7.34 g (13.4 mmol) of Priamine 1075, 32.2 g (53.3 mmol) of HA, and 140 g of NMP were weighed in a three-necked flask and dissolved. 17.1 g (57.0 mmol) of TDA-100 and 20 g of NMP were added thereto, and the mixture was stirred at 70 °C for 1 hour. Then, it was stirred at 160 °C for 4 hours, and then cooled to 80 °C. After cooling to 85 °C, 3.30 g (20.1 mmol) of NA and 20 g of NMP were added, and the mixture was stirred at 85 °C for 2 hours. After the stirring was completed, the solution was cooled to 30 °C, and then poured into 3 L of deionized water to obtain a white precipitate. The precipitate was collected by filtration, washed 3 times with deionized water, and then dried in a vacuum dryer at 50 °C for 72 hours to obtain a powder of polyimide resin (P1). The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0378] Synthesis of Polyimide Resin (P2) in Example 2

[0379] Instead of TDA-100, PPHT was used. 23.0 g (49.2 mmol) of PPHT, 2.85 g (17.3 mmol) of NA, 6.33 g (16.55 mmol) of Priamine 1075, and 27.8 g (46.0 mmol) of HA were used. Otherwise, a powder of polyimide resin (P2) was obtained in the same manner as in Example 1. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0380] Synthesis of Polyimide Resin (P3) in Example 3

[0381] Instead of TDA-100, BzDA was used. 21.1 g (51.8 mmol) of BzDA, 3.00 g (18.3 mmol) of NA, 6.67 g (12.2 mmol) of Priamine 1075, and 29.3 g (48.4 mmol) of HA were used. Otherwise, a powder of polyimide resin (P3) was obtained in the same manner as in Example 1. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0382] Synthesis of Polyimide Resin (P4) in Example 4

[0383] Instead of using TDA-100, TBIS-DMPN was used. 29.5 g (40.5 mmol) of TBIS-DMPN, 2.35 g (14.3 mmol) of NA, 5.22 g (9.55 mmol) of Priamine 1075, and 22.9 g (37.9 mmol) of HA were used. Except for this, the powder of polyimide resin (P4) was obtained by the same method as in Example 1. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0384] Synthesis of Polyimide Resin (P5) in Example 5

[0385] Instead of using TDA-100, BNBDA was used. 18.3 g (55.4 mmol) of BNBDA, 3.21 g (19.6 mmol) of NA, 7.14 g (13.05 mmol) of Priamine 1075, and 31.3 g (51.8 mmol) of HA were used. Except for this, the powder of polyimide resin (P5) was obtained by the same method as in Example 1. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0386] Synthesis of Polyimide Resin (P6) in Example 6

[0387] ODPA was also used. 15.1 g (50.2 mmol) of TDA-100, 2.08 g (6.70 mmol) of ODPA, 3.30 g (20.1 mmol) of NA, 7.33 g (13.4 mmol) of Priamine 1075, and 32.2 g (53.3 mmol) of HA were used. Except for this, the powder of polyimide resin (P6) was obtained by the same method as in Example 1. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0388] Synthesis of Polyimide Resin (P7) in Example 7

[0389] 13.1 g (43.5 mmol) of TDA-100 and 4.16 g (13.4 mmol) of ODPA were used. Except for this, the powder of polyimide resin (P7) was obtained by the same method as in Example 6. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0390] Synthesis of Polyimide Resin (P8) in Example 8

[0391] Instead of using NA, MA was used. 17.1 g (57.0 mmol) of TDA-100, 1.97 g (20.1 mmol) of MA, 7.34 g (13.4 mmol) of Priamine 1075, and 32.2 g (53.3 mmol) of HA were used. Otherwise, the powder of polyimide resin (P8) was obtained by the same method as in Example 1. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0392] Synthesis of Polyimide Resin (P9) in Example 9

[0393] Instead of using NA, IA was used. 17.4 g (58.0 mmol) of TDA-100, 2.30 g (20.5 mmol) of IA, 7.47 g (13.65 mmol) of Priamine 1075, and 32.8 g (54.3 mmol) of HA were used. Otherwise, the powder of polyimide resin (P9) was obtained by the same method as in Example 1. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0394] Synthesis of Polyimide Resin (P10) in Example 10

[0395] Instead of using HA, 6FAP was used. 21.7 g (72.3 mmol) of TDA-100, 4.19 g (25.5 mmol) of NA, 9.32 g (17.0 mmol) of Priamine 1075, and 24.8 g (67.6 mmol) of 6FAP were used. Otherwise, the powder of polyimide resin (P10) was obtained by the same method as in Example 1. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0396] Synthesis of Polyimide Resin (P11) in Example 11

[0397] 17.3 g (57.6 mmol) of TDA-100, 3.34 g (20.3 mmol) of NA, 13.0 g (23.7 mmol) of Priamine 1075, and 26.4 g (43.7 mmol) of HA were used. Otherwise, the powder of polyimide resin (P11) was obtained by the same method as in Example 1. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0398] Synthesis of Polyimide Resin (P12) in Example 12

[0399] Using 17.2 g (57.2 mmol) of TDA-100, 3.31 g (20.2 mmol) of NA, 9.21 g (16.8 mmol) of Priamine 1075, 30.3 g (50.1 mmol) of HA, in addition, a powder of polyimide resin (P12) was obtained in the same manner as in Example 1. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0400] Synthesis of Polyimide Resin (P13) in Example 13

[0401] Using 17.1 g (56.8 mmol) of TDA-100, 3.29 g (20.1 mmol) of NA, 5.49 g (10.05 mmol) of Priamine 1075, 34.2 g (56.5 mmol) of HA, in addition, a powder of polyimide resin (P13) was obtained in the same manner as in Example 1. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0402] Synthesis of Polyimide Resin (P14) in Example 14

[0403] Using 17.0 g (56.7 mmol) of TDA-100, 3.28 g (20.0 mmol) of NA, 3.65 g (6.65 mmol) of Priamine 1075, 36.1 g (59.7 mmol) of HA, in addition, a powder of polyimide resin (P14) was obtained in the same manner as in Example 1. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0404] Synthesis of Polyimide Resin (P15) in Example 15

[0405] Using 17.0 g (56.5 mmol) of TDA-100, 3.27 g (19.9 mmol) of NA, 1.82 g (3.32 mmol) of Priamine 1075, 38.0 g (62.8 mmol) of HA, in addition, a powder of polyimide resin (P15) was obtained in the same manner as in Example 1. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0406] Synthesis of Polyimide Resin (P16) in Example 16

[0407] The solvent was changed from NMP to MPA, and in addition, a powder of polyimide resin (P16) was obtained in the same manner as in Example 1. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0408] Synthesis of Polyimide Resin (P17) in Example 17

[0409] The solvent was changed from NMP to DMI, and in other respects, the powder of polyimide resin (P17) was obtained in the same manner as in Example 1. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0410] Synthesis of Polyimide Resin (P18) in Example 18

[0411] Under a dry nitrogen stream, 7.34 g (13.4 mmol) of Priamine 1075, 32.2 g (53.3 mmol) of HA, and 140 g of NMP were weighed and dissolved in a three-necked flask. 17.1 g (57.0 mmol) of TDA-100 and 20 g of NMP were added thereto, and the mixture was stirred at 70 °C for 1 hour. Then, 3.30 g (20.1 mmol) of NA and 20 g of NMP were added thereto, and the mixture was stirred at 85 °C for 2 hours. Then, it was stirred at 180 °C for 4 hours. After the stirring was completed, the solution was cooled to 30 °C, and then poured into 3 L of deionized water to obtain a white precipitate. This precipitate was collected by filtration, washed 3 times with deionized water, and then dried in a vacuum dryer at 50 °C for 72 hours to obtain the powder of polyimide resin (P18). The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0412] Synthesis of Polyimide Resin (P22) in Example 19

[0413] MCTC was used instead of TDA-100, and 15.1 g (57.0 mmol) of MCTC was used. In other respects, the powder of polyimide resin (P22) was obtained in the same manner as in Example 16. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0414] Synthesis of Polyimide Resin (P23) in Example 20

[0415] The solvent was changed from NMP to MPA, HC was used instead of HA, and 25.3 g (43.7 mmol) of HC was used. In other respects, the powder of polyimide resin (P23) was obtained in the same manner as in Example 11. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0416] Synthesis of Polyimide Resin (P24) in Example 21

[0417] The solvent was changed from NMP to MPA, HC was used instead of HA, and 30.9 g (53.3 mmol) of HC was used. Otherwise, the powder of polyimide resin (P24) was obtained in the same manner as in Example 1. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0418] Example 22 Synthesis of Polyimide Resin (P25)

[0419] The solvent was changed from NMP to MPA, HC was used instead of HA, and 34.5 g (59.7 mmol) of HC was used. Otherwise, the powder of polyimide resin (P25) was obtained in the same manner as in Example 14. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0420] Example 23 Synthesis of Polyimide Resin (P26)

[0421] The solvent was changed from NMP to MPA, HC was used instead of HA, and 36.3 g (62.8 mmol) of HC was used. Otherwise, the powder of polyimide resin (P25) was obtained in the same manner as in Example 15. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0422] Example 24 Synthesis of Polyimide Resin (P27)

[0423] Instead of 17.1 g (57.0 mmol) of TDA-100, 15.1 g (50.3 mmol) of TDA-100 and 2.08 g (6.71 mmol) of ODPA were used. Otherwise, the powder of polyimide resin (P27) was obtained in the same manner as in Example 21. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0424] Example 25 Synthesis of Polyimide Resin (P28)

[0425] Instead of 17.1 g (57.0 mmol) of TDA-100, 4.03 g (13.4 mmol) of TDA-100 and 13.5 g (43.6 mmol) of ODPA were used. Otherwise, the powder of polyimide resin (P28) was obtained in the same manner as in Example 21. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0426] Example 26 Synthesis of Polyimide Resin (P29)

[0427] MCTC was used instead of TDA-100, and 15.1 g (57.0 mmol) of MCTC was used. Otherwise, the powder of polyimide resin (P29) was obtained in the same manner as in Example 21. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0428] Synthesis of Polyimide Resin (P30) in Example 27

[0429] HD was used instead of HC, and 23.5 g (43.7 mmol) of HD was used. Otherwise, the powder of polyimide resin (P30) was obtained in the same manner as in Example 20. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0430] Synthesis of Polyimide Resin (P31) in Example 28

[0431] HD was used instead of HC, and 28.7 g (53.3 mmol) of HD was used. Otherwise, the powder of polyimide resin (P31) was obtained in the same manner as in Example 21. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0432] Synthesis of Polyimide Resin (P32) in Example 29

[0433] HD was used instead of HC, and 32.1 g (59.7 mmol) of HD was used. Otherwise, the powder of polyimide resin (P32) was obtained in the same manner as in Example 22. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0434] Synthesis of Polyimide Resin (P33) in Example 30

[0435] HD was used instead of HC, and 33.8 g (62.8 mmol) of HD was used. Otherwise, the powder of polyimide resin (P33) was obtained in the same manner as in Example 23. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0436] Synthesis of Polyimide Resin (P34) in Example 31

[0437] HI was used instead of HC, and 27.2 g (53.3 mmol) of HI was used. Otherwise, the powder of polyimide resin (P34) was obtained in the same manner as in Example 21. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0438] Synthesis of Polyimide Resin (P35) in Example 32

[0439] Instead of using HC, DAP-B was used, and 18.2 g (53.3 mmol) of DAP-B was used. Except for this, powders of polyimide resin (P35) were obtained by the same method as in Example 21. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0440] Synthesis of Polyimide Resin (P36) in Example 33

[0441] Instead of using HC, DAP-C was used, and 16.0 g (53.3 mmol) of DAP-C was used. Except for this, powders of polyimide resin (P36) were obtained by the same method as in Example 21. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0442] Synthesis of Polyimide Resin (P37) in Example 34

[0443] Instead of using HC, DAP-G was used, and 14.5 g (53.3 mmol) of DAP-G was used. Except for this, powders of polyimide resin (P37) were obtained by the same method as in Example 21. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0444] Synthesis of Polyimide Resin (P19) in Comparative Example 1

[0445] Instead of using TDA-100, ODPA was used. 17.5 g (56.5 mmol) of ODPA, 3.27 g (19.9 mmol) of NA, 7.27 g (13.3 mmol) of Priamine 1075, and 31.9 g (52.8 mmol) of HA were used. Except for this, powders of polyimide resin (P19) were obtained by the same method as in Example 1. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0446] Synthesis of Polyimide Resin (P20) in Comparative Example 2

[0447] Instead of using Priamine 1075, 16.9 g (56.3 mmol) of TDA-100, 3.26 g (19.9 mmol) of NA, and 39.8 g (65.9 mmol) of HA were used. Except for this, powders of polyimide resin (P20) were obtained by the same method as in Example 1. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0448] Synthesis of Polyimide Resin (P21) in Comparative Example 3

[0449] Using 17.4 g (57.9 mmol) of TDA-100, 3.36 g (20.4 mmol) of NA, 16.8 g (30.65 mmol) of Priamine 1075, and 22.5 g (37.1 mmol) of HA, in addition, powders of polyimide resin (P21) were obtained in the same manner as in Example 1. The composition of the polyimide resin is shown in Table 1. In addition, the physical properties are shown in Table 2.

[0450] [Example 51]

[0451] Under a yellow light, to 17.0 g of a mixed solvent with a mass ratio of PGME, EL, and GBL of 40:40:20, 2.04 g of polyimide resin P1 as polyimide resin (a), 0.163 g of QD-a and 0.122 g of QD-b as photoacid generators (b-1), 0.204 g of BPAF as a dissolution accelerator (g), 0.408 g of HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.; the compound represented by formula (40)) as a crosslinking agent (f), 0.061 g of BTS as a thermal acid generator (d), and 0.002 g of BYK-333 (manufactured by BYK Chemie Japan Co., Ltd.) as a surfactant (h) were added and stirred for 30 minutes to dissolve them, and a uniform solution with a solid content of 15.0 mass% was prepared.

[0452] [Chemical formula 33]

[0453]

[0454] Then, the obtained solution was filtered through a 0.45 μmφ filter to obtain a positive photosensitive resin composition 1. Next, using the positive photosensitive resin composition 1, various evaluations were carried out respectively using the measurement and evaluation methods (5) to (10).

[0455] Next, using the following method, a substrate having a patterned cured film formed by curing the positive photosensitive composition 1 and an organic EL display device for evaluating luminous reliability having the patterned cured film as a pixel partition layer were fabricated.

[0456] In Figure 2 the manufacturing process of an organic EL display device including the formation process of a pixel partition layer is shown.

[0457] On the surface of a non-alkali glass substrate 3 (a square with a horizontal length of 46 mm and a vertical length of 46 mm), a thin film of silver / copper alloy (volume ratio 10:1) with a thickness of 10 nm is formed over the entire surface by sputtering, and then etched to form a patterned metal reflective layer 4. Next, an ITO transparent conductive film with a thickness of 10 nm is formed over the entire surface by sputtering, and then etched to form a second electrode 5 with the same pattern as the metal reflective layer and an auxiliary electrode 6 as a lead-out electrode. Then, ultrasonic washing is performed for 10 minutes using "Semico Clean" (registered trademark) 56 (manufactured by Furuuchi Chemical Co., Ltd.), and washing is performed using deionized water to obtain a substrate with electrodes formed thereon.

[0458] Using a spin coater, the rotation speed is adjusted so that the thickness of the finally obtained pixel dividing layer becomes 2.0 μm, and a positive photosensitive composition 1 is coated on the surface of the substrate with electrodes formed thereon to obtain a coated film. Next, using a hot plate (HPD-3000BZN manufactured by AS ONE Co., Ltd.), the coated film is pre-baked at 110°C for 120 seconds under atmospheric pressure to obtain a pre-baked film.

[0459] The positive exposure mask is arranged on the coated film such that the longitudinal / lateral edge portions of the patterned light-shielding portion of the positive exposure mask arranged at an opening interval of 50 μm in accordance with the openings (rectangles with a horizontal length of 30 μm and a vertical length of 165 μm) are parallel to the longitudinal / lateral edge portions of the non-alkali glass substrate 3. Using a manual exposure machine (MA-1200; manufactured by Dainippon Scientific Co., Ltd.), through the positive exposure mask, the exposure light is pattern-irradiated onto the pre-baked film using a mixed line of i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of an ultra-high pressure mercury lamp with the minimum necessary exposure amount to obtain an exposed film. Next, development and rinsing are performed to obtain a developed film. It should be noted that as the positive exposure mask, a mask obtained by forming a patterned light-shielding portion made of chromium on the surface of a quartz substrate is used.

[0460] Furthermore, for the developed film, using a high-temperature inert gas oven (INH-9CD-S manufactured by Koyo Thermo Systems Co., Ltd.), heating (curing) is performed at 250°C for 1 hour in a nitrogen atmosphere to obtain a cured film, and a substrate with a patterned cured film having a patterned cured film 7 with a thickness of 2.0 μm and an aperture ratio of 18% is obtained. In the region of 16 mm in length and 16 mm in width at the center of the substrate with electrodes formed thereon, openings (rectangles with a horizontal length of 30 μm and a vertical length of 165 μm) are arranged at an opening interval of 50 μm. In the organic EL display device obtained after the processes described below, the openings here are the portions that finally become the light-emitting pixel portions, and the patterned cured film is the portion corresponding to the pixel dividing layer.

[0461] Next, a substrate with a patterned cured film is used to fabricate an organic EL display device. In order to form an organic EL layer 8 including a light-emitting layer by vacuum evaporation, under the evaporation conditions with a degree of vacuum of 1×10 -3 Pa or less, the substrate with a patterned cured film is rotated relative to the evaporation source. First, as a hole injection layer, compound HT-1 is formed into a film with a thickness of 10 nm, and as a hole transport layer, compound HT-2 is formed into a film with a thickness of 50 nm. Next, on the light-emitting layer, compound GH-1 as a host material and compound GD-1 as a dopant material are evaporated with a thickness of 40 nm. Then, as an electron transport material, compound ET-1 and compound LiQ are laminated with a thickness of 40 nm at a volume ratio of 1:1.

[0462] Next, after evaporating 2 nm of compound LiQ, 10 nm is evaporated using a silver / magnesium alloy (volume ratio of 10 / 1) to form a first electrode 9.

[0463] The chemical structures of the compound groups (HT-1, HT-2, GH-1, GD-1, ET-1, LiQ) used to form the organic EL layer are shown below, respectively.

[0464] [Chemical formula 34]

[0465]

[0466] It should be noted that the so-called thickness here is the display value of a quartz oscillator film thickness monitor.

[0467] Then, in a low-humidity / nitrogen atmosphere, a cover-shaped glass plate is bonded using an epoxy resin-based adhesive, and thus sealed to obtain an organic EL display device. The results obtained by evaluating the light emission reliability of the organic EL display device using the method described in the measurement / evaluation method (11) are shown in Table 4.

[0468] [Examples 52 to 85 and Comparative Examples 51 to 54]

[0469] Positive photosensitive compositions are prepared according to the compositions described in Table 3, and except for this, the same operations as in Example 51 are performed to fabricate positive photosensitive resin compositions 2 to 39, cured films, and organic EL display devices. The evaluation results thereof are summarized in Table 4.

[0470] [Table 1-1]

[0471]

[0472] [Table 1-2]

[0473]

[0474] [Table 2-1]

[0475] Table 2

[0476]

[0477] [Table 2-2]

[0478] Table 2 (continued)

[0479]

[0480] [Table 3-1]

[0481]

[0482] [Table 3-2]

[0483]

[0484] [Table 3-3]

[0485]

[0486] [Table 4-1]

[0487]

[0488] [Table 4-2]

[0489]

[0490] Description of the reference numerals

[0491] 1: High-low difference substrate

[0492] 2: Solidified product

[0493] 3: E-glass substrate

[0494] 4: Metal reflective layer

[0495] 5: Second electrode

[0496] 6: Auxiliary electrode

[0497] 7: Patterned solidified film

[0498] 8: Organic EL layer

[0499] 9: First electrode

[0500] 10: Baseline

Claims

1. A polyimide resin, which is a polyimide resin having an acid dianhydride residue and a diamine residue, wherein all or part of the acid dianhydride residues in the polyimide resin are acid dianhydride residues having an alicyclic structure and 8 to 40 carbon atoms, and, when the total amount of the diamine residues in the polyimide resin is set to 100 mol%, the total content of the diamine residues represented by formula (41) and the diamine residues represented by formula (42) is 60 mol% or more and 98 mol% or less, and the total content of the diamine residues represented by formula (16) and the diamine residues represented by formula (17) is 2 mol% or more and 40 mol% or less, [Chemical formula 1] X 3 represents a divalent organic group having 2 to 15 carbon atoms in which a part of the direct bonding key or hydrogen atom is optionally substituted with a fluorine atom; R 11 represents a methyl group, k each independently represents 0 or 1; * represents a bonding site bonded to an imide structure or an amic acid structure; [Chemical formula 2] In formula (16), a, b, c, and d are each independently natural numbers satisfying a + b = 7 to 17 and c + d = 6 to 16, and the dotted line portion refers to a carbon-carbon single bond or a carbon-carbon double bond; in formula (17), e, f, g, and h are each independently natural numbers satisfying e + f = 10 to 20 and g + h = 12 to 22, and the dotted line portion refers to a carbon-carbon single bond or a carbon-carbon double bond; * represents a bonding site bonded to an imide structure or an amic acid structure.

2. The polyimide resin according to claim 1, wherein When the total amount of the acid dianhydride residues in the polyimide resin is set to 100 mol%, the ratio of the acid dianhydride residues having an alicyclic structure and 8 to 40 carbon atoms is 51 mol% to 100 mol%.

3. The polyimide resin according to claim 1 or 2, wherein The said X 3 is a direct connecting key, -C(CH3)2-, -CH(CF3)-, or -C(CF3)2-, and k is 0.

4. The polyimide resin according to claim 1 or 2, wherein, The X 3 is a divalent saturated hydrocarbon group having 2 to 15 carbon atoms and not containing a fluorine atom.

5. The polyimide resin according to claim 1 or 2, wherein, The above-mentioned X 3 is any one of the divalent saturated hydrocarbon groups represented by Formula (43) to Formula (51), [Chemical formula 3] * represents a bonding site bonded to an aromatic ring.

6. The polyimide resin according to claim 5, wherein, The X 3 is a group selected from divalent saturated hydrocarbon groups represented by formula (44), formula (45), formula (49), formula (50) and formula (51).

7. The polyimide resin according to claim 1 or 2, wherein, The acid dianhydride residues having an alicyclic structure and 8 to 40 carbon atoms are acid dianhydride residues having 10 to 40 carbon atoms and simultaneously containing an alicyclic structure and an aromatic ring.

8. The polyimide resin according to claim 1 or 2, wherein, The acid dianhydride residues having 10 to 40 carbon atoms and simultaneously containing an alicyclic structure and an aromatic ring are one or more acid dianhydride residues selected from the group consisting of acid dianhydride residues represented by any one of formula (3) to formula (6), [Chemical formula 4] X in formula (5) 2 represents a divalent organic group represented by formula (7) or formula (8); X in formula (6) 3 represents an ether bond or an ester bond, and i represents an integer from 0 to 6; in formulas (3) to (6), * represents a bonding site bonded to any one of a carboxyl group, a carboxyl ester group, an amide group, or a carbonyl group constituting an imide ring. [Chemical formula 5] X in formula (7) 4 represents a direct bonding key or an ether bond; in formula (7) and formula (8), * represents a bonding site bonded to the nitrogen atom of formula (5).

9. The polyimide resin according to claim 1 or 2, wherein, When the total amount of the diamine residues in the polyimide resin is set to 100 mol%, the content of the diamine residues represented by formula (41) is 60 mol% or more and 98 mol% or less.

10. A photosensitive resin composition, which comprises the polyimide resin according to claim 1 or 2, a photosensitizer, and a solvent.

11. The photosensitive resin composition according to claim 10, wherein, All or part of the photosensitizer is a photoacid generator.

12. The photosensitive resin composition according to claim 10, which further comprises a thermal acid generator.

13. A cured product, which is obtained by curing the photosensitive resin composition according to claim 10.

14. An organic EL display device, which comprises the cured product according to claim 13.

15. An electronic component, which comprises the cured product according to claim 13.

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