Photosensitive resin composition, cured product, display device, and electronic component

Abstract

The purpose of the present invention is to provide: a photosensitive resin composition which has good solubility in a thinner, which can suppress tainting of an opening part after being cured and suppress foaming during lamination, and from which a cured product having good light emission characteristics even after being subjected to a reliability test is obtained; a cured product obtained by curing the photosensitive resin composition; and a display device and an electronic component equipped with a cured product of the resin composition.　A photosensitive resin composition according to the present invention contains: a resin (A) including a specific structural unit (hereinafter referred to as resin (A)); a photosensitive agent (B); and a solvent (C). When the total amount of diamine residues in the resin (A) is defined as 100 mol%, the total of the content of a specific diamine residue is 30-100 mol%.

Description

Photosensitive resin composition, cured product, display device, and electronic component

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

[0002] Conventionally, photosensitive polyimides and / or photosensitive polybenzoxazoles, which have excellent heat resistance, electrical insulation properties, mechanical properties, etc. and can be patterned by photolithography, have been widely used for bank layers of organic EL display devices, planarizing layers of TFT substrates, surface protective films of semiconductor elements, and interlayer insulating films of electronic components, and many of these have been proposed (see, for example, Patent Documents 1 and 2).

[0003] To obtain a thin film with excellent heat resistance and mechanical properties by thermally dehydrating and cyclizing a polyimide resin or polybenzoxazole resin coating, high-temperature baking at approximately 350°C is usually required. The process of thermally dehydrating and cyclizing a polyimide resin or polybenzoxazole resin coating to obtain a thin film with excellent heat resistance and mechanical properties is sometimes called baking (cure), and the change in the coating is sometimes called hardening. However, in view of the fact that recently used memory devices and molding resins used in semiconductor package fabrication are susceptible to high-temperature processes, and in view of semiconductor package reliability, there is a demand for polyimide-based resins, polybenzoxazole-based resins, and polyamide-imide-based resins that can be cured by baking at 250°C or less for surface protection films and interlayer insulating films and that have even better mechanical properties, chemical resistance, and adhesion.

[0004] Furthermore, demands for higher reliability for organic EL display devices are becoming stricter every year, and materials that can maintain high light-emitting properties even after reliability tests under accelerated conditions such as light irradiation are being sought for planarizing layer materials and insulating layer materials.

[0005]

[0003] Conventionally, polyimides, polybenzoxazoles, and precursors thereof used in photosensitive polyimides and / or photosensitive polybenzoxazoles generally have a fluorine-containing group such as a trifluoromethyl group in the resin structure, but there has been a problem in that fluorine-containing residues generated during curing or dry etching adhere to the electrode in the opening, increasing the contact resistance of the electrode. In response to this problem, a method using a fluorine-free organic insulating film (see, for example, Patent Document 3) and a method using a fluorine-free polyimide precursor having a specific structure introduced into the main chain, which achieves both suppression of electrode contamination and high sensitivity (see, for example, Patent Document 4) have been disclosed.

[0006] On the other hand, for example, there has been disclosed a method for providing an organic EL display device having excellent long-term reliability by using a photosensitive resin composition in which the molar ratio S / C of sulfur to carbon obtained when a cross section of a cured film is measured with an electron probe microanalyzer falls within a specific range (see, for example, Patent Document 5), and a method for providing a photosensitive resin composition that is highly sensitive and soluble in a γ-butyrolactone solvent by using a resin with a specific structure that does not contain halogen atoms in the molecule (see, for example, Patent Document 6).

[0007] JP 2002-91343 A JP 2002-116715 A JP 2009-177113 A JP 2003-76007 A WO 2016 / 047483 WO 2009 / 081950

[0008] However, conventional polyimides, polybenzoxazoles, and precursors thereof that do not have a fluorine-containing group such as a trifluoromethyl group have poor solubility in organic solvents, and although they are soluble in some aprotic polar solvents such as N-methyl-2-pyrrolidone and γ-butyrolactone, they have a problem of insufficient solubility in propylene glycol monomethyl ether, which is widely used as a thinner in photolithography processes. The resins disclosed in Patent Documents 3 and 4 have a problem with solubility in propylene glycol monomethyl ether.

[0009] Patent Document 5 discloses a photosensitive resin composition containing a polyimide precursor having a fluorine-containing group. However, our investigations have revealed a problem: contamination of openings after curing. Additionally, during the organic EL display device fabrication process, there is a problem of foaming-induced defects easily occurring when forming a pixel dividing layer on top of a planarization layer. Furthermore, our investigations of the photosensitive resin composition described in Patent Document 6 revealed a problem with its solubility in propylene glycol monomethyl ether. Furthermore, when an organic EL display device was fabricated using the photosensitive resin composition described in Patent Document 6 and reliability evaluation was performed, there was a problem of the light-emitting characteristics not being maintained after reliability testing under accelerated conditions such as light irradiation. As described above, there are currently no known photosensitive resin compositions that satisfy all of the following requirements: thinner solubility, suppression of opening contamination after curing, suppression of foaming during lamination, and good light-emitting characteristics after reliability testing.

[0010] Therefore, an object of the present invention is to provide a photosensitive resin composition that has good solubility in thinner, is capable of suppressing contamination of openings after curing, and is capable of suppressing foaming during lamination, and the cured product has good light-emitting properties even after reliability testing; a cured product obtained by curing the photosensitive resin composition; and a display device and an electronic component that include the cured product of the photosensitive resin composition.

[0011] In order to solve the above-mentioned problems, the present invention has the following configuration: [1] A photosensitive resin composition comprising a resin (A) (hereinafter referred to as resin (A)) containing at least one of a structural unit represented by formula (1), a structural unit represented by formula (19), and a structural unit represented by formula (70), a photosensitizer (B), and a solvent (C), in which the total content of diamine residues represented by any one of formulas (2) to (4) is 30 to 100 mol % when the total amount of diamine residues in the resin (A) is taken as 100 mol %.

[0012]

[0013] (In formula (1), formula (19) and formula (70), Y １each independently represents an acid dianhydride residue having 2 to 40 carbon atoms, which has any one of an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 40 carbon atoms, and an aromatic structure having 6 to 40 carbon atoms. １ R each independently represents a diamine residue represented by any one of formulas (2) to (4). １ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a monovalent group having 2 to 20 carbon atoms and an ethylenically unsaturated double bond. * represents a bonding site.

[0014]

[0015] (In formulas (2), (3) and (4), X １ are each independently a direct bond or a divalent group represented by formula (5), and R ２ each independently represents an alkyl group having 1 to 4 carbon atoms; X ２ is a divalent group represented by formula (6) or (7), each k independently represents 0 or 1, and * represents a bonding point to bond to the imide structure, amide structure, amic acid ester structure, or amic acid structure.

[0016]

[0017] (In formula (5), * represents the point of attachment to the nitrogen atom, and ** represents the point of attachment to the aromatic ring.)

[0018]

[0019] (In formulas (6) and (7), R ３ each independently represents an alkyl group having 1 to 4 carbon atoms, a represents 1 or 2, b represents an integer of 1 to 3, R ４ and R ５ each independently represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and * represents the point of attachment to the aromatic ring. ４ and R ５ do not have the same structure.) [2] The resin (A) contains a diamine residue represented by formula (2), and in formula (6), the R ３ The total number of carbon atoms in the formula (7) is 1 or more and 5 or less, and ４and the number of carbon atoms in R ５ [3] The photosensitive resin composition according to [1], wherein the resin (A) contains a diamine residue represented by formula (2), and when formula (6-1) is defined as when a = 1 in formula (6), and formula (6-2) is defined as when a = 2 in formula (6), conditions 1 and 2 are satisfied, and when formula (7) is defined as when R ４ and the number of carbon atoms in R ５ The photosensitive resin composition according to [1] or [2], wherein the number of carbon atoms in R is different from that in R １１ ~R １４ The total number of carbon atoms in R １５ ~R １８ Condition 2: In formula (6-2), the total number of carbon atoms in R １９ ~R ２２ The total number of carbon atoms in R ２５ ~R ２８ The total number of carbon atoms is different.

[0020]

[0021] (In formula (6-1) and formula (6-2), R １１ ~R ２８ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, provided that both formula (6-1) and formula (6-2) satisfy the condition of formula (6). [4] The resin (A) contains a diamine residue represented by formula (2), and the X ２ is a divalent group represented by any one of formulas (8) to (13) and (76) to (83). The photosensitive resin composition according to any one of [1] to [3].

[0022]

[0023] (In formulas (8) to (13), (76) to (83), * represents a bonding point to the aromatic ring.) [5] In the formulas (1), (19) and (70), Y １ [6] The photosensitive resin composition according to any one of [1] to [5], wherein each independently represents an acid dianhydride residue having 8 to 40 carbon atoms and a diphenyl ether structure. [7] The photosensitive resin composition according to any one of [1] to [5], wherein the resin (A) has a structure represented by formula (84).

[0024]

[0025] (In formula (84), R ２９ represents a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms. * represents a bonding site with a nitrogen atom.) [7] The photosensitive resin composition according to any one of [1] to [6], wherein the resin (A) contains a structural unit (a) and / or a structural unit (b), and the resin (A) contains a structural unit (c) and / or a structural unit (d), and the resin (A) contains at least one of the structural unit (a) and the structural unit (c).

[0026] Structural unit (a): Z in formula (1), formula (19) and formula (70) １ is expressed by formula (2), and the two X １ and Z are direct bonds. Structural unit (b): In formula (48), formula (49) and formula (71), Z ３ is expressed by the formula (45), and the two X １ and (c) a structural unit represented by the formula (1), (19) or (70), wherein Z １ is expressed by formula (2), and the two X １ At least one of the X １ is a divalent group represented by formula (5). Structural unit (d): In formula (48), formula (49) and formula (71), Z ３ is expressed by the formula (45), and the two X １ At least one of the X １ is a divalent group represented by formula (5),

[0027]

[0028] (In formula (48), formula (49) and formula (71), Y １ and R １is in the same range as that explained in Equation (1), Equation (19) and Equation (70). ３ each independently represents a diamine residue represented by formula (45). * represents a bond.

[0029]

[0030] (In formula (45), X １ are each independently a direct bond or a divalent group represented by formula (5), and R ２ and k are in the same range as described in formula (2). ３ represents a divalent organic group represented by any one of formulas (64) to (69). * represents a bonding point to an imide structure, an amide structure, an amic acid ester structure, or an amic acid structure.

[0031]

[0032] (* represents a bonding point bonding to an aromatic ring.) [8] The photosensitive resin composition according to [7], wherein, when the total amount of structural units of polyimide contained in the resin (A) is taken as 100 mol%, the total content of the structural units (a) and (b) is 20 to 95 mol%, and the total content of the structural units (c) and (d) is 5 mol% to 80 mol%. [9] The photosensitive resin composition according to any of [1] to [8], wherein the resin (A) further contains at least one of a structural unit represented by formula (50), a structural unit represented by formula (51), and a structural unit represented by formula (72).

[0033]

[0034] (In formula (50), formula (51) and formula (72), Y １ and R １ is in the same range as that described in Equation (1), Equation (19) and Equation (70). ５ each independently represents a diamine residue represented by formula (46) or formula (47). * represents a bond.

[0035]

[0036] (In formula (46) and formula (47), X４ is a direct bond or -C(CH ３ ) ２ -. t represents an integer of 0 to 2. * represents a bonding point bonding to an imide structure, an amide structure, an amic acid ester structure, or an amic acid structure.)

[10] The photosensitive resin composition according to [9], wherein, when the total amount of polyimide structural units contained in the resin (A) is taken as 100 mol %, the total content of the structural unit represented by formula (50), the structural unit represented by formula (51), and the structural unit represented by formula (72) is 1 to 30 mol %.

[11] The photosensitive resin composition according to any one of [1] to

[10] , wherein the resin (A) contains an acid dianhydride residue having 4 to 20 carbon atoms and an alicyclic structure.

[12] The photosensitive resin composition according to

[11] , wherein, when the total amount of acid dianhydride residues in the resin (A) is taken as 100 mol %, the total content of the acid dianhydride residues having 4 to 20 carbon atoms and an alicyclic structure is 20 to 100 mol %.

[13] The photosensitive resin composition according to

[11] or

[12] , wherein the resin (A) contains one or more acid dianhydride residues selected from the group consisting of formulas (15), (16), and (85) to (94):

[0037]

[0038] (In formulas (15), (16), and (85) to (94), * represents a bonding point bonding to an imide structure, an amide structure, an amic acid ester structure, or an amic acid structure.)

[14] The photosensitive resin composition according to any one of [1] to

[13] , wherein the resin (A) has an imide ring closure rate of 50% or less.

[15] The photosensitive resin composition according to any one of [1] to

[14] , wherein the resin (A) has an esterification rate of 10% or more and 100% or less.

[16] The photosensitive resin composition according to any one of [1] to

[15] , wherein the solvent (C) contains a solvent represented by formula (17) and / or a solvent (C1) represented by formula (18).

[0039]

[0040] (In formulas (17) and (18), R ６ each independently represents an alkyl group having 1 to 6 carbon atoms; R ７represents an alkyl group having 2 to 6 carbon atoms.)

[17] The photosensitive resin composition according to any one of [1] to

[16] , wherein the solvent (C) contains a solvent (C2) having a hydroxyl group and a boiling point at atmospheric pressure of 100°C or more and 200°C or less.

[18] The photosensitive resin composition according to any one of [1] to

[17] , wherein the photosensitive resin composition contains both a solvent (C1) represented by formula (17) and / or a solvent (C1) represented by formula (18) (hereinafter referred to as solvent (C1)) and a solvent (C2) having a hydroxyl group and a boiling point at atmospheric pressure of 100°C or more and 200°C or less (hereinafter referred to as solvent (C2)), and wherein the content ratio Y / X, where X is the content of the solvent (C1) and Y is the content of the solvent (C2) in the photosensitive resin composition, is 1 or more and 1,000 or less.

[19] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to

[18] .

[20] A display device comprising the cured product according to

[19] .

[21] An electronic component comprising the cured product according to

[19] .

[0041] According to the present invention, it is possible to obtain a photosensitive resin composition that has good solubility in thinner, that can suppress contamination of openings after curing, that can suppress foaming during lamination, and that has good light-emitting properties even after a reliability test when cured, a cured product obtained by curing the photosensitive resin composition, and a display device and an electronic component that include the cured product of the photosensitive resin composition.

[0042] 1 is a cross-sectional view of a sample for evaluating flatness. 2 is a schematic diagram illustrating a method for producing an organic EL display device including a flattening layer and a pixel dividing layer in an example.

[0043] The present invention will be described in detail below.

[0044] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0045] In this specification, polyimide is intended to form an imide ring after curing, and therefore also includes those having a structure before ring closure to form an imide ring, i.e., an amide acid (or amic acid) or an ester structure of such an acid, and polybenzoxazole is intended to form a benzoxazole ring after curing, and therefore also includes those having a structure before ring closure to form an oxazole ring, i.e., a hydroxyamide structure.

[0046] The photosensitive resin composition of the present invention contains a resin (A) (hereinafter referred to as resin (A)) containing at least one of a structural unit represented by formula (1), a structural unit represented by formula (19), and a structural unit represented by formula (70).

[0047]

[0048] In formula (1), formula (19) and formula (70), Y １ each independently represents an acid dianhydride residue having 2 to 40 carbon atoms, which has any one of an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 40 carbon atoms, and an aromatic structure having 6 to 40 carbon atoms. １ R each independently represents a diamine residue represented by any one of formulas (2) to (4). １ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a monovalent group having 2 to 20 carbon atoms and an ethylenically unsaturated double bond. * represents a bonding site.

[0049]

[0050] In formulas (2), (3) and (4), X １ are each independently a direct bond or a divalent group represented by formula (5), and R ２ each independently represents an alkyl group having 1 to 4 carbon atoms; X ２ is a divalent group represented by formula (6) or (7), each k independently represents 0 or 1, and * represents a bonding point to bond to the imide structure, amide structure, amic acid ester structure, or amic acid structure.

[0051]

[0052] In formula (5), * represents the point of attachment to the nitrogen atom, and ** represents the point of attachment to the aromatic ring.

[0053]

[0054] In formulas (6) and (7), R ３ each independently represents an alkyl group having 1 to 4 carbon atoms, a represents 1 or 2, b represents an integer of 1 to 3, R ４ and R ５ each independently represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and * represents the point of attachment to the aromatic ring. ４ and R ５ do not have the same structure.

[0055] Formula (1), Formula (19), and Formula (70) are all structural units of polyimide. Formula (1) represents a structural unit in which the amic acid structures or amic acid ester structures in the structural unit do not close, and all are amic acid structures or amic acid ester structures. The structural unit represented by Formula (19) represents a structural unit in which all of the amic acid structures or amic acid ester structures in the structural unit are closed and imidized. The structural unit represented by Formula (70) represents a structural unit in which one amic acid structure or amic acid ester structure in the structural unit does not close, and the other amic acid structure or amic acid ester structure is closed and imidized. When Resin (A) has the structural unit of Formula (1) or Formula (70), it has good thinner solubility and can reduce residue. Furthermore, when Resin (A) has the structural unit of Formula (19), it is possible to reduce the amount of outgassing at high temperatures of the cured product obtained by curing the photosensitive resin composition and suppress foaming during lamination. When the number of structural units represented by formula (1), structural units represented by formula (19), and structural units represented by formula (70) in resin (A) is defined as p, q, and r, respectively, p + q + r is an integer of 1 or greater, and it is preferable that p ≧ 1 or r ≧ 1. Furthermore, when the total number of polyimide structural units constituting resin (A) is 100 mol%, the sum of the structural units represented by formula (1), structural units represented by formula (19), and structural units represented by formula (70) is preferably 30 to 100 mol%, more preferably 40 to 100 mol%, even more preferably 50 to 100 mol%, and particularly preferably 60 to 100 mol%. By having the ratios of the structural units of formula (1), formula (19), and formula (70) within the above ranges, it is possible to obtain a photosensitive resin composition that has good solvent solubility, suppresses contamination of openings after curing, and is capable of suppressing foaming during lamination. The polyimide structural unit referred to here refers to a structural unit that is expected to form an imide ring after curing. The polyimide structural unit includes a structure before the imide ring is closed, i.e., an amide acid (or amic acid) or an ester thereof. Specifically, in the present application, the polyimide structural unit is represented by formula (73), formula (74), or formula (75).

[0056]

[0057] In formula (73), formula (74) and formula (75), Y １０ each independently represents an acid dianhydride residue. １０ R each independently represents a diamine residue. １０ each independently represents a hydrogen atom or a monovalent group. * represents a bonding site.

[0058] When the resin (A) has a structural unit other than polyimide, it is preferable that the resin (A) has a structural unit of polybenzoxazole, since a cured product having good heat resistance can be obtained. When the resin (A) contains a structural unit of polybenzoxazole, it is preferable that the resin (A) has at least one selected from the group consisting of a structural unit represented by formula (38), a structural unit represented by formula (39), and a structural unit represented by formula (40).

[0059]

[0060] In formula (38), formula (39) and formula (40), Y ３ , Y ４ , Y ５ represents a dicarboxylic acid residue, Z ３ , Z ４ , Z ５ represents a bisaminophenol residue. A dicarboxylic acid residue is a residue obtained by removing two carboxyl groups from a dicarboxylic acid compound. A bisaminophenol residue is a residue obtained by removing two amino groups and two hydroxyl groups from a bisaminophenol compound.

[0061] The structural unit represented by formula (38) represents a structural unit in which all of the hydroxyamide structures in the structural unit have been ring-closed to form oxazoles. Formula (39) represents a structural unit in which some of the hydroxyamide structures in the structural unit have been ring-closed to form oxazoles, leaving some as hydroxyamide structures. Formula (40) represents a structural unit in which the hydroxyamide structures in the structural unit have not been ring-closed, leaving all as hydroxyamide structures.

[0062] When resin (A) contains structural units other than polyimide, the total amount of polyimide structural units is preferably 50 to 100 mol %, more preferably 65 to 100 mol %, and even more preferably 80 to 100 mol %, based on 100 mol % of the total amount of all structural units contained in resin (A). By containing polyimide structural units in the above ratio, a cured product with good reliability and excellent heat resistance can be obtained.

[0063] The imide ring closure rate of the resin (A) is preferably 90% or less, more preferably 80% or less, and even more preferably 50% or less. When the imide ring closure rate is within the above range, residue can be reduced and the alkaline development rate can be set within a preferred range, making it possible to obtain a good pattern shape. In particular, when the imide ring closure rate of the resin (A) is 50% or less, the solvent solubility of the resin (A) is improved and aggregation of the resin (A) during storage is suppressed. As a result, the storage stability of the photosensitive resin composition can be improved, which is preferable. The imide ring closure rate of the resin (A) can be determined by the method described below.

[0064] The esterification rate of resin (A) is preferably 10% or more and 100% or less, more preferably 20% or more and 98% or less, even more preferably 30% or more and 95% or less, and particularly preferably 35% or more and 90% or less. When the esterification rate is within the above range, residue can be reduced and a photosensitive resin composition with excellent thinner solubility can be obtained. The esterification rate of resin (A) can be determined by the method described below.

[0065] Furthermore, R in formula (1) １ are each independently preferably an alkyl group having 1 to 10 carbon atoms or a monovalent organic group having an ethylenically unsaturated double bond, and more preferably an alkyl group having 1 to 3 carbon atoms or a monovalent organic group having an ethylenically unsaturated double bond. １ is an alkyl group having 1 to 10 carbon atoms or a monovalent organic group having an ethylenically unsaturated double bond, it is possible to adjust the solubility in the developer to a preferred range, and therefore it is possible to obtain a good pattern shape. １is a monovalent organic group having an ethylenically unsaturated double bond, which is preferable because, in addition to the above, the progress of a crosslinking reaction during heat curing can improve the breaking elongation and chemical resistance. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, and a hexyl group, and examples of the monovalent organic group having an ethylenically unsaturated double bond include structures obtained by removing a hydroxyl group from 2-hydroxyethyl methacrylate (hereinafter referred to as HEMA) and 2-hydroxyethyl acrylate.

[0066] In formula (1), formula (19) and formula (70), Y １ each independently represents an acid dianhydride residue having 2 to 40 carbon atoms, which has any one of an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 40 carbon atoms, and an aromatic structure having 6 to 40 carbon atoms. The acid dianhydride residue refers to a residue obtained by removing two acid anhydride structures from an acid dianhydride compound.

[0067] Y １Specific examples of the above include 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, residues of alicyclic tetracarboxylic dianhydrides such as 3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 3,5,6-tricarboxy-2-norbornane acetic dianhydride, 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione, and 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride; 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, Residues of aromatic tetracarboxylic dianhydrides such as 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, and 3,4,9,10-perylenetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 4,4'-oxydiphthalic anhydride, 3,4'-oxydiphthalic anhydride, 3,3'-oxydiphthalic anhydride, 2,2-bis(3,Examples of the dianhydride include 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, 2,2-bis(3-(3,4-dicarboxyphenoxy)phenyl)hexafluoropropane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 4,4'-(1,4-phenylenedioxy)bisphthalic anhydride, and compounds in which the aromatic rings of these compounds are substituted with alkyl groups or halogen atoms, and residues of aromatic acid dianhydrides such as acid dianhydrides having an amide group.

[0068] Among them, in the formula (1), formula (19) and formula (70), Y １ are preferably each independently a residue of an acid dianhydride having 8 to 40 carbon atoms and a diphenyl ether structure. By satisfying the above conditions, it becomes possible for the cured product obtained by curing the photosensitive resin composition to have good light-emitting properties even after reliability testing. １ Specific examples of the above include residues of 4,4'-oxydiphthalic anhydride, 3,4'-oxydiphthalic anhydride, 3,3'-oxydiphthalic anhydride, 2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl)propane dianhydride, 4,4'-(1,4-phenylenedioxy)bisphthalic anhydride, and the like.

[0069] In particular, it is preferable that the resin (A) contains an acid dianhydride residue having 4 to 20 carbon atoms and containing an alicyclic structure. １ is preferably an acid dianhydride residue containing an alicyclic structure and having 4 to 20 carbon atoms. １ is an acid dianhydride residue having 4 to 20 carbon atoms and containing an alicyclic structure, a photosensitive resin composition can be obtained which has good sensitivity, is less colored in the visible light region, and is capable of producing a cured product with high transmittance.

[0070] When the total amount of acid dianhydride residues in the resin (A) is taken as 100 mol %, the total content of acid dianhydride residues having 4 to 20 carbon atoms and containing an alicyclic structure is preferably 20 to 100 mol %, and more preferably 30 to 100 mol %.

[0071] Furthermore, the acid dianhydride residue having 4 to 20 carbon atoms and containing an alicyclic structure preferably contains one or more acid dianhydride residues selected from the group consisting of formulae (15), (16), and (85) to (94). Among these, it is particularly preferred to contain an acid dianhydride residue represented by formula (15) and / or formula (16). The acid dianhydride residue represented by formula (15) is a residue obtained by removing two acid anhydride structures from 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione, and the acid dianhydride residue represented by formula (16) is a residue obtained by removing two acid anhydride structures from 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride. By including these acid anhydride residues, it is possible to obtain a photosensitive resin composition that is particularly excellent in solubility in thinner and leaves little residue.

[0072]

[0073] In formulas (15), (16), and (85) to (94), * represents a bonding point to the imide structure, amide structure, amic acid ester structure, or amic acid structure.

[0074] When the total amount of diamine residues in resin (A) containing at least one of the structural units represented by formula (1), the structural unit represented by formula (19), and the structural unit represented by formula (70) is taken as 100 mol %, the total content of diamine residues represented by any one of formulas (2) to (4) is 30 to 100 mol %. That is, in formulas (1), (19), and (70), Z １each independently represents a diamine residue represented by any one of formulas (2) to (4). A diamine residue refers to a structure obtained by removing two amino groups from a diamine compound. Since both diamine residues represented by any one of formulas (2) to (4) contain a phenolic hydroxyl group, they can impart solubility in alkaline developers and reduce development residues. Furthermore, the presence of a diamine residue represented by any one of formulas (2) to (4) suppresses intermolecular packing, improving thinner solubility. In addition, the fluorine-free structure can suppress contamination of openings after curing and foaming during lamination.

[0075] Although the detailed mechanism by which the inclusion of a diamine residue represented by any one of formulas (2) to (4) can suppress opening contamination after curing and foaming during lamination is unknown, the following is hypothesized as the principle behind the above effects. For example, when using a polyimide containing a fluorine-containing diamine, as described in International Publication No. 2016 / 047483, it is believed that the hexafluoroisopropylidene group thermally decomposes during the heat curing process, resulting in fluorine-containing hydrocarbon groups adhering to the openings and causing opening contamination. On the other hand, since all of the diamine residues represented by formulas (2) to (4) have a fluorine-free structure, opening contamination caused by fluorine-containing hydrocarbon groups does not occur, and as a result, opening contamination after curing is believed to be suppressed. Furthermore, when using a polyimide containing a fluorine-containing diamine, fluorine is an electron-withdrawing group, which is believed to suppress the progression of the imide ring-closing reaction during heat curing. As a result, the imide ring-closing reaction is not completed during the specified heat curing process, and an amic acid structure remains in the film. This remaining amic acid structure gradually undergoes imide ring closure during the additional heating process, generating water, which is thought to cause foaming during laminate formation and reduce the reliability of organic EL display devices. On the other hand, because the diamine residues represented by any of formulas (2) to (4) have a structure that does not contain fluorine, the imide ring closure reaction proceeds quickly during the heat curing process, and almost no amic acid structure remains in the film after the heat curing process. As a result, it is thought that foaming and reduced reliability are suppressed.

[0076] In formula (2), formula (3) and formula (4), X １ are each independently a direct bond or a divalent group represented by formula (5). １ By using a direct bond, the hydroxyl group concentration of the resin (A) can be increased, which is preferable because it is possible to reduce residues after development. １ is a divalent organic group represented by formula (5), a hydroxyamide structure, which is a benzoxazole precursor, is formed in the structure of formula (2), and the hydroxyamide undergoes ring closure to form an oxazole ring in the curing step, making it possible to obtain a cured product with low water absorption, which is preferable. ２ each independently represents an alkyl group having 1 to 4 carbon atoms. Among these, R ２ In formula (2), X is preferably a methyl group. ２ is a divalent group represented by formula (6) or (7), and in formulas (6) and (7), R ３ each independently represents an alkyl group having 1 to 4 carbon atoms, a represents 1 or 2, b represents an integer of 1 to 3, R ４ and R ５ each independently represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. ４ and R ５ do not have the same structure. By containing a structure such as that represented by formula (6) or formula (7), intermolecular packing is suppressed, and thinner solubility can be improved. In particular, it is preferable to contain a structure represented by formula (7) in order to further improve the chemical resistance of the cured product obtained by curing the photosensitive resin composition. R ３ are each independently an alkyl group having 1 to 4 carbon atoms, but are preferably a methyl group from the viewpoints of being able to enhance the heat resistance of the resin (A) and reducing development residues. It is preferable that a represents 1 or 2 and b represents an integer of 1 to 3, since this allows the resin (A) to have both good heat resistance and solubility in thinner. ４ and R ５each independently represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and from the viewpoint of being able to increase the heat resistance of the resin (A) and to reduce development residues, R ４ , R ５ are each independently preferably a saturated hydrocarbon group having 1 to 10 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 8 carbon atoms. ４ and R ５ The term "does not have the same structure" used here means that R ４ and R ５ In addition to the relationship where the composition formula is different, the relationship also includes structural isomers where the composition formula is the same but the bonding state between atoms is different. ４ and R ５ When the structures of the resins (A) and (B) are different, the thinner solubility of the resin (A) can be improved. In formula (2), k each independently represents 0 or 1. When k is 0, development residue can be reduced, which is preferable. Furthermore, when k = 1, a photosensitive resin composition having good thinner solubility can be obtained, and the dielectric constant of the cured product obtained by curing the photosensitive resin composition can be reduced, which is preferable.

[0077] When the total amount of diamine residues in the resin (A) is taken as 100 mol%, the total content of diamine residues represented by any one of formulas (2) to (4) is 30 to 100 mol%, preferably 40 to 100 mol%, more preferably 50 to 100 mol%, and even more preferably 60 to 100 mol%. In particular, it is preferable that the total content of diamine residues represented by formula (2) is within the above range. By having the total content of diamine residues represented by any one of formulas (2) to (4) within the above range, it is possible to obtain a photosensitive resin composition that has little development residue and good sensitivity.

[0078] Specific examples of the diamine residue represented by any one of formulas (2) to (4) include residues of diamines represented by formulas (20) to (37).

[0079]

[0080] Among these, the resin (A) contains a diamine residue represented by formula (2), and in formula (6), the R ３ The total number of carbon atoms in the formula (7) is 1 or more and 5 or less, and ４ and the number of carbon atoms in R ５ In the formula (6), the total number of carbon atoms in the R ３ The total number of carbon atoms in the formula (6) is 1 or more and 5 or less. ３ If there are multiple R ３ The total number of carbon atoms in the R ４ and the number of carbon atoms in R ５ The total number of carbon atoms in R is 3 or more and 10 or less. ４ and R ５ The total number of carbon atoms in each of the R groups is 3 or more and 10 or less. ３ , R ４ , R ５ When the number of carbon atoms is within the above range, a photosensitive resin composition having good thinner solubility can be obtained without leaving development residues or deteriorating sensitivity, which is preferable.

[0081] Among them, when the resin (A) contains a diamine residue represented by formula (2), and when formula (6) is formula (6-1) when a=1 and formula (6-2) when a=2 in formula (6), conditions 1 and 2 are satisfied, and when formula (7) is formula (7), the R ４ and the number of carbon atoms in R ５ Condition 1: In formula (6-1), it is preferable that the number of carbon atoms in R １１ ~R １４ The total number of carbon atoms in R １５ ~R １８ Condition 2: In formula (6-2), the total number of carbon atoms in R １９ ~R ２２ The total number of carbon atoms in R ２５ ~R ２８ The total number of carbon atoms is different.

[0082]

[0083] In formula (6-1) and formula (6-2), R １１ ~R ２８ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, provided that both formula (6-1) and formula (6-2) satisfy the conditions of formula (6).

[0084] When formula (6) and formula (7) satisfy the above conditions, it is possible to suppress packing of the resins (A) with each other, and it is therefore possible to obtain a photosensitive resin composition having particularly good thinner solubility, which is preferable.

[0085] Among them, the resin (A) contains a diamine residue represented by formula (2), and the X ２ is preferably a divalent group represented by any one of formulas (8) to (13) and (76) to (83).

[0086]

[0087] In formulae (8) to (13) and (76) to (83), * represents the point of attachment to the aromatic ring.

[0088] Specifically, in the formula (1), the formula (19) and the formula (70), Z １ is preferably a residue of a diamine represented by any one of formulas (20) to (25) and formulas (29) to (34). By including the residue of the diamine, it is possible to further increase the solubility in thinner.

[0089] It is also preferred that the resin (A) contains a diamine residue represented by formula (2) and k = 1. When k = 1, a photosensitive resin composition having good thinner solubility can be obtained, and the dielectric constant of the cured product obtained by curing the photosensitive resin composition can be reduced. Specifically, in formulas (1), (19), and (70), Z １ is preferably a residue of a diamine of formula (26) or formula (35).

[0090] The resin (A) contains a diamine residue represented by formula (2), and R 2 is preferably a methyl group. ２When Z is a methyl group, it is possible to obtain a photosensitive resin composition with good sensitivity and little residue. In addition, it is possible to reduce the dielectric constant of the cured product obtained by curing the photosensitive resin composition. Specifically, in formula (1), formula (19), and formula (70), Z １ is preferably a residue of a diamine of formula (26) or formula (35).

[0091] Furthermore, the resin (A) may contain other diamine residues in addition to the above-mentioned diamine residues.

[0092] Specific examples of the other diamine residues include aliphatic diamine residues and aromatic diamine residues. The aliphatic diamine residue refers to a residue of a diamine that does not have an aromatic ring. Examples of the aliphatic diamine residue include residues of aliphatic alkyldiamines containing alkylene groups, polyethylene ether groups, polyoxypropylene groups, tetramethylene ether groups, etc., alicyclic diamines, and aliphatic diamines having a siloxane structure.

[0093] Examples of the aliphatic alkylenediamine residue include polymethylenediamines such as tetramethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, dodecamethylenediamine, 7-ethylhexadecanediamine, 7,12-dimethyloctadecanediamine, 8,13-dimethyloctadecanediamine, 8-methylnonadecanediamine, 9-methylnonadecanediamine, 7,12-dimethyloctadecanediamine-7,11-ene, 8,13-dimethyloctadecanediamine-8,12-ene, and Diamine H20 (trade name, manufactured by Okamura Oil Mills Co., Ltd.); diamines containing a polyethylene ether group such as Jeffamine KH-511, Jeffamine ED-600, Jeffamine ED-900, Jeffamine ED-2003, Jeffamine EDR-148, and Jeffamine EDR-176; Examples of the residue include polyoxypropylene diamines such as D-200, D-400, D-2000, D-4000, RP-409, and RP-2009; diamines containing a tetramethylene ether group such as RT-1000 and HT-1100; amino group-containing alkylene ether diamines such as HT-1000 and HE-1000 (all trade names, manufactured by HUNTSMAN Corporation); and dimer diamines such as "VERSAMINE (registered trademark) 551," "VERSAMINE (registered trademark) 552" (manufactured by BASF Corporation), "PRIAMINE (registered trademark) 1073," "PRIAMINE (registered trademark) 1074," and "PRIAMINE (registered trademark) 1075" (manufactured by Cargill).

[0094] Examples of the alicyclic diamine residue include residues of cyclohexyldiamine, methylenebiscyclohexylamine, norbornanediamine, PRO-NBDA (trade name, manufactured by Mitsui Chemicals Fine Co., Ltd.), and the like.

[0095] Examples of aliphatic diamine residues having a siloxane structure include residues of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (hereinafter, SiDA), bis(p-aminophenyl)octamethylpentasiloxane, etc. When an aliphatic group having a siloxane structure is copolymerized within a range that does not decrease heat resistance, adhesion to a substrate can be improved.

[0096] Other aromatic diamine residues include, for example, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (BAHF), bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl) bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl, bis(3-amino-4-hydroxyphenyl)fluorene, 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]propane (HB), 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]-1,1,1-trifluoroethane, bis(3-amino-4-hydroxyphenyl)sulfone, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene (AZ-FDA), 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP), and other diamine residues are also included.Among these, from the viewpoint of solubility in an alkaline developer, residues of hydroxyl group-containing diamines such as BAHF, BAP, AZ-FDA, 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]propane (HB), and 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane, residues of sulfonic acid-containing diamines such as 3-sulfonic acid-4,4'-diaminodiphenyl ether, residues of thiol group-containing diamines such as dimercaptophenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, benzine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis Examples include residues of aromatic diamines such as (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, and 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, and residues of compounds in which some of the hydrogen atoms of these aromatic rings have been substituted with alkyl groups or fluoroalkyl groups having 1 to 10 carbon atoms.

[0097] These diamine residues can be used as they are or as the corresponding diisocyanate compounds or trimethylsilylated diamines, which can be used alone or in combination of two or more.

[0098] The resin (A) may be end-capping with an end-capping agent such as a monoamine, an acid anhydride, a monoacid chloride, a monocarboxylic acid, or a monoactive ester. Capping the ends of the resin with an end-capping agent allows the dissolution rate of the resin in an alkaline aqueous solution to be easily adjusted within a preferred range. Among these, it is preferable to use an end-capping agent having a phenolic hydroxyl group or a crosslinkable group. The use of an end-capping agent having a phenolic hydroxyl group imparts alkali solubility to the resin, thereby reducing residue. The use of an end-capping agent having a crosslinkable group also allows a crosslinking reaction to proceed during the heat curing process, making it possible to obtain a cured film with excellent chemical resistance and elongation at break.

[0099] Specific examples of the monoamines having a phenolic hydroxyl group include 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 (hereinafter referred to as OAP), 3-aminophenol (hereinafter referred to as MAP), and 4-aminophenol (hereinafter referred to as PAP). Furthermore, examples of those having a photocrosslinkable group include 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 2-aminostyrene, 3-aminostyrene, 4-aminostyrene, and others include 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. Two or more of these may be used.

[0100] Among the acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds, those having a phenolic hydroxyl group include 3-hydroxyphthalic anhydride, 3-carboxyphenol, 4-carboxyphenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, etc. Furthermore, those having a photocrosslinkable group include maleic anhydride, 5-norbornene-2,3-dicarboxylic anhydride (hereinafter, NA), itaconic anhydride, itaconic acid, maleic acid, acrylic acid, methacrylic acid, 3-phenylacrylic acid, crotonic acid, 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, and 3-methyl-4-cyclohexene-1,2-dicarboxylic anhydride. Other examples include acetic anhydride, succinic anhydride, phthalic anhydride, cyclohexanedicarboxylic anhydride, 3-carboxythiophenol, 4-carboxythiophenol, 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, trimellitic anhydride, and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride. Furthermore, with respect to the above monocarboxylic acids, monoacid chloride compounds in which the carboxyl group of these monocarboxylic acids is converted to acid chloride may be used, or monoacid chloride compounds in which only one carboxyl group of the above dicarboxylic acids is converted to acid chloride may be used, or activated ester compounds obtained by reacting a monoacid chloride compound with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide may be used. Two or more of these may also be used.

[0101] Furthermore, a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

[0102] In particular, the resin (A) preferably has a structure represented by formula (84).

[0103]

[0104] In formula (84), R ２９ indicates a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms. * indicates the bonding site with the nitrogen atom.

[0105] Here, the resin (A) having the structure represented by formula (84) means that the ends of the resin (A) are capped with an end-capping agent which is a monoamine represented by formula (95).

[0106]

[0107] In formula (95), R ２９ represents a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms.

[0108] The resin (A) having the structure represented by formula (84) is preferred because it can enhance the storage stability of the photosensitive resin composition. ２９ is preferably a hydroxyl group, an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, or an alkynyl group having 2 to 3 carbon atoms.

[0109] When a monoamine is used as the end-capping agent, the introduction ratio thereof is preferably 1 mol% or more and 60 mol% or less, based on 100 mol% of all amine compounds contained in the resin (A). By making the introduction ratio of the monoamine preferably 1 mol% or more, more preferably 5 mol% or more, the effect of reducing residue after development can be effectively obtained. Furthermore, by making the introduction ratio of the monoamine preferably 60 mol% or less, more preferably 50 mol% or less, the molecular weight of the resin can be maintained high, and high chemical resistance and breaking elongation can be maintained.

[0110] When an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound is used as the end-capping agent, the total introduction ratio thereof is preferably 1 mol part or more and 100 mol parts or less relative to 100 mol parts of all amine compounds contained in the resin (A). By setting the introduction ratio to preferably 1 mol part or more, more preferably 5 mol parts or more, the effect of reducing residue after development can be effectively obtained. On the other hand, by setting the introduction ratio to preferably 100 mol parts or less, more preferably 90 mol parts or less, the molecular weight of the resin can be maintained high, and high chemical resistance and elongation at break can be maintained.

[0111] The term "total amine compounds" as used herein refers to the total content of compounds having an amino group, such as monoamines, diamines, and triamines.

[0112] Preferably, the resin (A) contains the structural unit (a) and / or the structural unit (b) and also contains the structural unit (c) and / or the structural unit (d), and the resin (A) contains at least one of the structural unit (a) and the structural unit (c). The structural units (a) to (d) are as follows:

[0113] Structural unit (a): Z in formula (1), formula (19) and formula (70) １ is expressed by formula (2), and the two X １ and Z are direct bonds. Structural unit (b): In formula (48), formula (49) and formula (71), Z ３is expressed by the formula (45), and the two X １ and (c) a structural unit represented by the formula (1), (19) or (70), wherein Z １ is expressed by formula (2), and the two X １ At least one of the X １ is a divalent group represented by formula (5). Structural unit (d): In formula (48), formula (49) and formula (71), Z ３ is expressed by the formula (45), and the two X １ At least one of the X １ is a divalent group represented by formula (5),

[0114]

[0115] In formula (48), formula (49) and formula (71), Y １ and R １ is in the same range as that explained in Equation (1), Equation (19) and Equation (70). ３ each independently represents a diamine residue represented by formula (45). * represents a bond.

[0116]

[0117] In formula (45), X １ are each independently a direct bond or a divalent group represented by formula (5), and R ２ and k are in the same range as described in formula (2). ３ represents a divalent organic group represented by any one of formulas (64) to (69). * represents a bonding point to an imide structure, an amide structure, an amic acid ester structure, or an amic acid structure.

[0118]

[0119] * denotes the point of attachment to the aromatic ring.

[0120] Specific examples of the diamine residue represented by formula (45) include residues of diamines represented by formulas (52) to (63).

[0121]

[0122] The structural unit (a) and the structural unit (b) are represented by the two X １ Since both are direct bonds, the resin (A) containing the structural unit (a) and / or the structural unit (b) can reduce residues. １ At least one of the X １ Since is a divalent group represented by formula (5), sensitivity can be improved by including the structural unit (c) and / or the structural unit (d) in the resin (A). Furthermore, since the structural unit (a) and the structural unit (c) contain a diamine residue represented by formula (2), the solvent solubility of the resin (A) can be improved by including at least one of the structural unit (a) and the structural unit (c). Therefore, when the resin (A) includes the structural unit (a) and / or the structural unit (b), and the resin (A) includes the structural unit (c) and / or the structural unit (d), and the resin (A) includes at least one of the structural unit (a) and the structural unit (c), it is possible to achieve all of the properties of improved sensitivity, reduced residue, and excellent solvent solubility. In addition, by including multiple structural units with different structures as described above, aggregation of the resins when formed into a photosensitive resin composition is suppressed, thereby improving the storage stability of the photosensitive resin composition.

[0123] When the total amount of the polyimide structural units contained in the resin (A) is taken as 100 mol%, it is preferable that the total content of the structural units (a) and (b) is 20 to 95 mol%, and the total content of the structural units (c) and (d) is 5 mol% to 80 mol%. Furthermore, the total content of the structural units (a) and (b) is more preferably 25 to 95 mol%, and even more preferably 30 to 95 mol%. Additionally, the total content of the structural units (c) and (d) is more preferably 5 mol% to 75 mol%, and even more preferably 5 mol% to 70 mol%. By including each structural unit in the resin (A) within the above ranges, it is possible to achieve preferred ranges for all of the properties, including sensitivity, residue reduction, solvent solubility, and storage stability. As described above, the polyimide structural units are represented by formulas (73), (74), and (75).

[0124] In the present invention, the content of the structural unit is defined as follows: Here, the calculation method for the structural unit (a) will be explained as an example.

[0125] The structural unit (a) is a structural unit represented by formula (1), formula (19), or formula (70) (Y １ are each independently a C2-C40 acid dianhydride residue having any one of an aliphatic structure having C2-C20, an alicyclic structure having C4-C40, and an aromatic structure having C6-C40, and Z １ is expressed by formula (2), and the two X １ are both direct bonds). In other words, the acid dianhydride residue Y １ and Z, a diamine residue １ (However, there are two X １ The structural unit (a) is a structure in which Y is bonded to the carboxylic acid dianhydride residues (both of which are direct bonds). １ When the total amount of the acid dianhydride residues corresponding to the formula (I) is α mol %, and the total amount of the diamine residues contained in the resin (A) is 100 mol %, Z １When the total amount of diamine residues corresponding to the formula (I) is β mol %, and the total amount of structural units of the polyimide is 100 mol %, the content of structural unit (a) is calculated as follows: Content (mol %) of structural unit (a) = α (mol %) / 100 (mol %) × β (mol %) / 100 (mol %) × 100 (mol %). For example, when α is 70 mol % and β is 80 mol %, the ratio of structural unit (a) is 70 mol % / 100 (mol %) × 80 mol % / 100 (mol %) × 100 (mol %) = 56 mol %.

[0126] The resin (A) preferably further contains at least one of a structural unit represented by formula (50), a structural unit represented by formula (51), and a structural unit represented by formula (72).

[0127]

[0128] In formula (50), formula (51) and formula (72), Y １ and R １ is in the same range as that explained in Equation (1), Equation (19) and Equation (70). ５ each independently represents a diamine residue represented by formula (46) or formula (47). * represents a bond.

[0129]

[0130] In formula (46) and formula (47), X ４ is a direct bond or -C(CH ３ ) ２ - represents an integer of 0 to 2. * represents a bonding point to bond to the imide structure, amide structure, amic acid ester structure, or amic acid structure.

[0131] Since the diamine residue represented by formula (46) or formula (47) has a phenyl ether partial structure, the inclusion of the diamine residue represented by formula (46) or formula (47) makes it possible to impart flexibility to resin (A), and as a result, it is possible to improve the breaking elongation of the cured product of the photosensitive resin composition. Examples of the diamine residue represented by formula (46) or formula (47) include residues of diamines such as 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 1,4-bis(4-aminophenoxy)benzene (TPE-Q), 1,3-bis(3-aminophenoxy)benzene (APB), 1,3-bis(4-aminophenoxy)benzene (TPE-R), 2,2-bis[4-(4-aminophenoxy)phenyl]propane, and 2,2-bis[4-(3-aminophenoxy)phenyl]propane. Among these, from the viewpoint of improving the breaking elongation of the cured product and reducing residues of the photosensitive resin composition, it is preferable to contain a residue of any one of diamines TPE-Q, TPE-R, and APB.

[0132] When the total amount of the polyimide structural units contained in the resin (A) is taken as 100 mol%, the total content of the structural units represented by formula (50), the structural units represented by formula (51), and the structural units represented by formula (72) is preferably 1 to 30 mol%, more preferably 1 to 25 mol%. By having the total content of the structural units represented by formula (50), the structural units represented by formula (51), and the structural units represented by formula (72) within the above range, the breaking elongation of the cured product obtained by curing the photosensitive resin composition can be improved without causing deterioration in the residue or sensitivity of the photosensitive resin composition. As described above, the polyimide structural units are represented by formulas (73), (74), and (75).

[0133] The weight-average molecular weight (Mw) of the resin (A) is preferably 3,000 to 100,000, as determined by gel permeation chromatography (GPC) in terms of polystyrene. By setting the Mw to 100,000 or less, more preferably 80,000 or less, and even more preferably 60,000 or less, good solvent solubility and good solubility in a developer can be effectively achieved. Furthermore, by setting the weight-average molecular weight to 3,000 or more, more preferably 5,000 or more, and even more preferably 7,000 or more, high elongation at break can be effectively achieved. In the present invention, Mw is determined by the method described below.

[0134] The total amount of components with a molecular weight of 1,000 or less contained in the resin (A) is preferably 0.5 to 5.0% by mass, more preferably 0.7 to 4.5% by mass, and even more preferably 1.0 to 4.0% by mass. By ensuring that the total amount of components with a molecular weight of 1,000 or less contained in the resin (A) is within the above range, development residue can be reduced without impairing the heat resistance of the cured product obtained by curing the photosensitive resin composition containing the resin (A). While the detailed mechanism of development residue reduction is unknown, it is believed that components with a molecular weight of 1,000 or less have better alkali solubility than molecules with a molecular weight greater than 1,000, and therefore the components with a molecular weight of 1,000 or less act as dissolution-promoting components during development, contributing to the reduction of development residue. In the present invention, the total amount of components with a molecular weight of 1,000 or less is determined by the method described below.

[0135] Resin (A) can be synthesized by a known method. Examples of methods for producing resin (A) include reacting a tetracarboxylic dianhydride with a diamine compound in a polymerization solvent at low temperature, obtaining a diester from a tetracarboxylic dianhydride with an alcohol and then reacting it with an amine in the presence of a condensing agent, and obtaining a diester from a tetracarboxylic dianhydride with an alcohol and then converting the remaining dicarboxylic acid into an acid chloride and reacting it with an amine. Alternatively, the resin obtained by the above method may be dehydrated and cyclized by heating or a chemical treatment with an acid or base.

[0136] The resin (A) polymerized by the above method is preferably introduced into a large amount of deionized water or a mixture of methanol and deionized water, precipitated, filtered, dried, and isolated. This precipitation procedure removes unreacted monomers and oligomer components such as dimers and trimers, improving the film properties and chemical resistance after thermal curing.

[0137] The polymerization solvent is not particularly limited as long as it can dissolve the raw material monomers, such as acid dianhydrides and diamines. Examples of the polymerization solvent include amides such as N,N-dimethylformamide (hereinafter referred to as DMF), N,N-diethylformamide (hereinafter referred to as DEF), N,N-dimethylacetamide (hereinafter referred to as DMAc), N-methyl-2-pyrrolidone (hereinafter referred to as NMP), N-ethyl-2-pyrrolidone (hereinafter referred to as NEP), 1,3-dimethyl-2-imidazolidinone (hereinafter referred to as DMI), 3-methoxy-N,N-dimethylpropanamide (hereinafter referred to as MPA), 3-butoxy-N,N-dimethylpropanamide (hereinafter referred to as BPA), N,N'-dimethylpropyleneurea (hereinafter referred to as DMPU), N,N-dimethylisobutyramide (hereinafter referred to as DMIB), N,N-dimethylpropionamide (hereinafter referred to as DMPA), and 3-methyl-2-oxazolidinone; γ-butyrolactone; Examples of suitable polymerization solvents include cyclic esters such as α-methyl-γ-butyrolactone (hereinafter, GBL), γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, and α-methyl-γ-butyrolactone, carbonates such as ethylene carbonate and propylene carbonate, glycols such as triethylene glycol, phenols such as m-cresol and p-cresol, esters such as methyl levulinate, ethyl levulinate, propyl levulinate, butyl levulinate, ethyl levulinate propylene glycol ketal, and ethyl levulinate glycerol ketal, acetophenone, sulfolane, dimethyl sulfoxide (hereinafter, DMSO), and dihydrolevoglucosenone (Cyrene, manufactured by Circa). The amount of the polymerization solvent used is preferably 100 to 1,900 parts by mass, more preferably 150 to 950 parts by mass, per 100 parts by mass of the resin (A).

[0138] The photosensitive resin composition of the present invention contains a photosensitizer (B). The inclusion of the photosensitizer (B) can impart photosensitivity to the resin composition. Examples of the photosensitizer (B) include a photoacid generator (B1) and a photopolymerization initiator (B2). The inclusion of the photoacid generator (B1) generates acid in the light-irradiated areas, increasing the solubility of the light-irradiated areas in an alkaline aqueous solution, thereby producing a positive-tone relief pattern in which the light-irradiated areas are dissolved. Furthermore, the inclusion of the photoacid generator (B1) and the crosslinking agent (E) allows the acid generated in the light-irradiated areas to promote the crosslinking reaction of the crosslinking agent (E), thereby producing a negative-tone relief pattern in which the light-irradiated areas are insolubilized. Furthermore, the inclusion of the photopolymerization initiator (B2) and the radically polymerizable compound (H) allows the active radicals generated in the light-irradiated areas to proceed with radical polymerization of the ethylenically unsaturated bonds in the radically polymerizable compound, thereby producing a negative-tone relief pattern in which the light-irradiated areas are insolubilized. In the photosensitive resin composition of the present invention, it is preferable that the photosensitizer (B) contains the photoacid generator (B1) and exhibits positive photosensitivity. When the photosensitizer (B) contains the photoacid generator (B1) and exhibits positive photosensitivity, it becomes easier to reduce variations in pattern opening dimensions due to processing, and residues are reduced. Furthermore, when the photosensitizer (B) contains the photopolymerization initiator (B2) and the radical polymerizable compound (H) and exhibits negative photosensitivity, it becomes possible to increase the sensitivity of the photosensitive resin composition.

[0139] Examples of the photoacid generator (B1) include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts.

[0140] Examples of the quinone diazide compound include a polyhydroxy compound to which a sulfonic acid of quinone diazide is bonded via an ester bond, a polyamino compound to which a sulfonic acid of quinone diazide is bonded via a sulfonamide bond, and a polyhydroxypolyamino compound to which a sulfonic acid of quinone diazide is bonded via an ester bond and / or a sulfonamide bond. It is preferred that 50 mol% or more of the functional groups of these polyhydroxy compounds or polyamino compounds are substituted with quinone diazide. It is also preferred that the photoacid generator (B1) contains two or more types, thereby enabling the production of a highly sensitive photosensitive resin composition.

[0141] The quinone diazide is preferably one having a 5-naphthoquinone diazide sulfonyl group or one having a 4-naphthoquinone diazide sulfonyl group. 4-naphthoquinone diazide sulfonyl ester compounds have absorption in the i-line region of a mercury lamp and are suitable for i-line exposure. 5-naphthoquinone diazide sulfonyl ester compounds have absorption extending to the g-line region of a mercury lamp and are suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength of exposure. Furthermore, a naphthoquinone diazide sulfonyl ester compound having both a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule may be contained, or both a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound may be contained.

[0142] Of the photoacid generators (B1), sulfonium salts, phosphonium salts, and diazonium salts are preferred because they appropriately stabilize the acid component generated by exposure, and sulfonium salts are particularly preferred.

[0143] Specific examples of the photopolymerization initiator (B2) include the photopolymerization initiators described in paragraphs

[0223] to

[0276] of WO 2019 / 087985 and paragraphs

[0047] to

[0048] of WO 2019 / 194286. Among these, from the viewpoint of achieving high sensitivity, it is preferable that the photopolymerization initiator (B2) contains an oxime ester photopolymerization initiator (B2-1) and / or a titanocene photopolymerization initiator (B2-2). Two or more of these may be contained.

[0144] The content of the photosensitizer (B) is preferably 0.5 to 50 parts by mass per 100 parts by mass of the resin (A).

[0145] From the viewpoint of achieving high sensitivity, the content of the photoacid generator (B1) in the photosensitizer (B) is preferably 0.5 to 50 parts by mass per 100 parts by mass of the component (A). Of these, the content of the quinone diazide compound is preferably 3 to 40 parts by mass. The total amount of the sulfonium salt, phosphonium salt, and diazonium salt is preferably 0.5 to 20 parts by mass.

[0146] The content of the photopolymerization initiator (B2) in the photosensitizer (B) is preferably 0.5 to 20 parts by mass relative to 100 parts by mass of the resin (A). If the content is 0.5 parts by mass or more, sufficient radicals are generated by light irradiation, improving sensitivity. If the content is 20 parts by mass or less, curing of the unexposed areas due to excessive radical generation does not occur, improving alkaline developability.

[0147] The photosensitive resin composition of the present invention contains a solvent (C). In the photosensitive resin composition of the present invention, the solvent (C) preferably contains a solvent represented by formula (17) and / or a solvent (C1) represented by formula (18).

[0148]

[0149] In formulas (17) and (18), R ６ each independently represents an alkyl group having 1 to 6 carbon atoms; R ７ represents an alkyl group having 2 to 6 carbon atoms.

[0150] The inclusion of the solvent (C1) promotes the ring-closing reaction of the resin (A), and improves the mechanical properties and chemical resistance of the cured product obtained by curing the photosensitive resin composition. Furthermore, since the solvent (C1) strongly interacts with the resin (A) component and the metal material, the inclusion of the solvent (C1) can improve adhesion to the metal material.

[0151] The β-alkoxypropionamide, which is a compound represented by formula (17), is preferably MPA or BPA from the viewpoints of solubility of resin (A), promoting the ring-closing reaction of resin (A), and improving the mechanical properties and chemical resistance of the cured product.

[0152] In the present invention, the content of the β-alkoxypropionamide is preferably 0.1 parts by mass or more, and more preferably 1 part by mass or more, relative to 100 parts by mass of the resin (A) from the viewpoint of accelerating the ring-closing reaction of the resin (A) and improving the breaking elongation and chemical resistance of the cured film, while the content is preferably 15 parts by mass or less, and more preferably 10 parts by mass or less, from the viewpoint of being able to form a desired patterned film when used as a developed film.

[0153] The compound represented by formula (18) is preferably DMPA or DMIB, from the viewpoint of accelerating the ring-closing reaction of the resin (A) and improving the mechanical properties and chemical resistance of the cured product.

[0154] In the present invention, the content of the compound represented by formula (18) is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, relative to 100 parts by mass of resin (A) from the viewpoint of accelerating the ring-closing reaction of resin (A) and improving the mechanical properties and chemical resistance of the cured product, while it is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, from the viewpoint of being able to form a desired patterned film when used as a developed film.

[0155] The photosensitive resin composition of the present invention preferably contains a solvent (C2) that is a compound having a hydroxyl group and a boiling point at atmospheric pressure of 100° C. or more and 200° C. or less. Inclusion of the solvent (C2) not only makes it possible to improve flatness but also improve developability, thereby making it possible to suppress the generation of development residues and improve sensitivity.

[0156] Specific examples of the solvent (C2) include propylene glycol monomethyl ether (hereinafter, PGME; boiling point 120°C), methyl lactate (boiling point 145°C), ethyl lactate (boiling point 154°C), propyl lactate (boiling point 169°C), 1-butanol (boiling point 117°C), 1-pentanol (boiling point 138°C), 1-hexanol (boiling point 157°C), cyclohexanol (boiling point 161°C), 3-methoxybutanol (boiling point 161°C), ethylene glycol monomethyl ether (boiling point 124°C), diacetone alcohol (boiling point 166°C), tetrahydrofurfuryl alcohol (boiling point 176°C), and diethylene glycol monomethyl ether (boiling point 194°C).

[0157] The content of the solvent (C2) contained in the photosensitive resin composition of the present invention is preferably 5 to 3,000 parts by mass, more preferably 10 to 1,000 parts by mass, per 100 parts by mass of the total amount of the resin (A).

[0158] The photosensitive resin composition of the present invention contains both the solvent (C1) and the solvent (C2), and when the content of the solvent (C1) in the photosensitive resin composition is X (mass) and the content of the solvent (C2) is Y (mass), the content ratio Y / X is preferably 1 or more and 1000 or less, more preferably 10 or more and 800 or less. When the ratio Y / X is within the above range, it is possible to satisfy all of the properties of improved adhesion to metal materials, improved flatness, suppression of development residues, and improved sensitivity.

[0159] The photosensitive resin composition of the present invention may contain a solvent (C3) other than the solvent (C1) and the solvent (C2). Examples of the solvent (C3) include ethers such as ethylene glycol monoethyl 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 lactate, methyl levulinate, ethyl levulinate, propyl levulinate, and butyl levulinate; alcohols such as methanol, ethanol, and isopropanol; 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, GBL, DMSO, 1,3-dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidone, and dihydrolevoglucosenone (Cyrene, manufactured by Circa); and aromatic hydrocarbons such as toluene and xylene. Two or more of these may be contained.

[0160] The content of the solvent (C3) is preferably 1,500 parts by mass or less, and more preferably 1,000 parts by mass or less, based on 100 parts by mass of the resin (A).

[0161] The photosensitive resin composition of the present invention preferably further contains a dissolution promoter (D), and the photosensitizer (B) preferably contains a photoacid generator (B1) to form a positive-type photosensitive resin composition. The dissolution promoter (D) supplements the alkaline developability of the photosensitive resin composition, and can reduce residue and improve sensitivity in the positive-type photosensitive resin composition. The dissolution promoter (D) is preferably a compound having a phenolic hydroxyl group, such as 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, or BisOIPP- CP, Bis26X-IPZ, BisOTBP-CP, TekP4HBPA (tetrakisP-DO-BPA), TrisP-HAP, TrisP-PA, TrisP-PHBA, TrisP-SA, TrisOCRPA (trade names, manufactured by Honshu Chemical Industry Co., Ltd.), Mirex HBPX, Mirex PIRM, Mirex MDPR (trade names, manufactured by Mitsui Chemicals, Inc.), BIR-OC, BIP-PC, BIR-P Examples of compounds having a phenolic hydroxyl group include bisphenol C, BIR-PTBP, BIR-PCHP, BIP-BIOCF, 4PC, BIR-BIPC-F, TEP-BIP-A (trade names, manufactured by Asahi Organic Chemicals Co., Ltd.), bisphenol A, bisphenol AF (hereinafter referred to as BPAF), bisphenol B, bisphenol C, bisphenol S, 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, and 8-quinolinol. The content of the dissolution promoter (D) is preferably 1 to 40 parts by mass per 100 parts by mass of the resin (A) in order to improve sensitivity while maintaining a good pattern shape.

[0162] The photosensitive resin composition of the present invention preferably contains a crosslinking agent (E). A crosslinking agent refers to a compound having a crosslinkable group capable of bonding with a resin. By including the crosslinking agent (E), the breaking elongation and chemical resistance of the cured film can be improved. This is presumably because the crosslinking agent (E) component can introduce a new crosslinked structure into the cured product of the photosensitive resin composition, thereby improving the crosslink density.

[0163] The crosslinking agent (E) is preferably a compound having two or more thermally crosslinkable groups in the molecule, such as alkoxymethyl groups, methylol groups, epoxy groups, or oxetanyl groups.

[0164] Specific examples of the crosslinking agent (E) that can be used include the crosslinking agents described in paragraphs

[0407] to

[0412] of WO 2019 / 087985.

[0165] The content of the crosslinking agent (E) is preferably 0.5 to 50 parts by mass relative to 100 parts by mass of the resin (A). When the content is 0.5 to 50 parts by mass, the breaking elongation and chemical resistance of the cured film can be improved without deteriorating the storage stability of the photosensitive resin composition or the transparency of the cured film.

[0166] The photosensitive resin composition of the present invention preferably contains a surfactant (F). A surfactant refers to a compound having a hydrophilic structure and a hydrophobic structure. By incorporating an appropriate amount of the surfactant (F), the surface tension of the photosensitive resin composition can be adjusted as desired, improving leveling during application and improving the thickness uniformity of the coating film. The surfactant (F) is preferably a fluororesin-based surfactant, a silicone-based surfactant, a polyoxyalkylene ether-based surfactant, or an acrylic resin-based surfactant. Among these, it is more preferable to include a silicone-based surfactant, a polyoxyalkylene ether-based surfactant, or an acrylic resin-based surfactant as the surfactant (F) in order to suppress contamination of openings after curing. Specific examples of the surfactant (F) include the surfactants described in paragraphs

[0419] to

[0420] of WO 2019 / 087985.

[0167] The content of the surfactant (F) 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, of the total photosensitive resin composition. When the content is 0.001% by mass or more, leveling properties during application can be improved. On the other hand, the content of the surfactant is preferably 1% by mass or less, more preferably 0.5% by mass or less. When the content is 1% by mass or less, defects occurring during application can be reduced, and a cured product with high heat resistance can be obtained.

[0168] The photosensitive resin composition of the present invention preferably contains an adhesion improver (G). Examples of the adhesion improver (G) include silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane; titanium chelating agents; aluminum chelating agents; and compounds obtained by reacting an aromatic amine compound with an alkoxy group-containing silicon compound. Two or more of these may be contained. By containing these adhesion improvers, when the photosensitive resin composition is developed, the adhesion improver can be easily applied to silicon wafers, ITO, SiO ２ , and can improve adhesion to the underlying substrate such as silicon nitride. In particular, it is preferable to contain a silane coupling agent as the adhesion improver (G) in order to improve the storage stability of the photosensitive resin composition. The content of the adhesion improver (G) is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, relative to 100 parts by mass of the resin (A). Also, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less. By containing the adhesion improver (G) in the above range, it is possible to achieve both storage stability of the photosensitive resin composition and adhesion to the underlying substrate.

[0169] The photosensitive resin composition of the present invention may further contain a radically polymerizable compound (H), and the photosensitizer (B) may contain a photopolymerization initiator (B2). By adopting such a configuration, as described above, active radicals generated in the light-irradiated areas promote radical polymerization of ethylenically unsaturated bonds in the radically polymerizable compound, thereby obtaining a negative relief pattern in which the light-irradiated areas are insolubilized. As a result, the photosensitive resin composition becomes a negative-tone photosensitive resin composition.

[0170] Specific examples of the radically polymerizable compound (H) include the radically polymerizable compounds described in paragraphs

[0189] to

[0222] of WO 2019 / 087985. Among these, it is preferable to contain a flexible-chain-containing aliphatic radically polymerizable compound. The flexible-chain-containing aliphatic radically polymerizable compound refers to a compound having, in the molecule, multiple ethylenically unsaturated double bond groups and a flexible skeleton such as an aliphatic chain or an oxyalkylene chain.

[0171] By incorporating the flexible chain-containing aliphatic radical polymerizable compound, the curing reaction upon light irradiation can proceed efficiently, improving sensitivity upon light irradiation. Furthermore, the change in pattern opening width between before and after thermal curing can be suppressed. The content of the radical polymerizable compound (H) is preferably 5 to 50 parts by mass per 100 parts by mass of the resin (A).

[0172] The photosensitive resin composition of the present invention may contain an additive (I) other than those described above (hereinafter referred to as additive (I)). Examples of the additive (I) include polyfunctional thiol compounds described in

[0386] to

[0398] of WO 2019 / 087985, colorants described in

[0281] to

[0370] of WO 2019 / 087985, dispersants described in

[0371] to

[0385] of WO 2019 / 087985, sensitizers described in

[0399] to

[0402] of WO 2019 / 087985, polymerization inhibitors described in

[0403] to

[0406] of WO 2019 / 087985, and inorganic particles described in

[0127] to

[0130] of WO 2016 / 052268 and WO 2019 / 167461

[0024] to

[0025] .

[0173] Examples of methods for producing the photosensitive resin composition of the present invention include a method in which the resin (A), photosensitizer (B), solvent (C), and other components, as required, are placed in a glass flask or a stainless steel container, and stirred and dissolved using a mechanical stirrer or the like, an ultrasonic dissolving method, or a method in which the composition is stirred and dissolved using a planetary stirring and degassing device.

[0174] The obtained photosensitive resin composition is preferably filtered through a leak filter to remove dust and particles. The pore size of the leak 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 to these. The material of the leak filter includes polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc., with polyethylene and nylon being preferred. When the photosensitive resin composition contains inorganic particles, pigments, etc., it is preferable to use a leak filter with a pore size larger than these.

[0175] The cured product of the present invention is obtained by curing the photosensitive resin composition of the present invention. Examples of methods for curing the photosensitive resin composition include a method of curing the photosensitive resin composition by heating it or a method of irradiating it with actinic rays. Curing the photosensitive resin composition of the present invention can improve the heat resistance and chemical resistance of the cured product. The cured product is preferably in the form of a film, i.e., a cured film.

[0176] Next, the method for producing the cured product of the present invention will be described.

[0177] The method for producing a cured product of the present invention preferably includes the following steps: (1) applying the above-described photosensitive resin composition to a substrate to form a photosensitive resin film, (2) drying the photosensitive resin film, (3) exposing the dried photosensitive resin film through a photomask, (4) developing the exposed photosensitive resin film, and (5) heat-treating the developed photosensitive resin film.

[0178] In the above step (1), the photosensitive resin composition of the present invention is applied to a substrate by spin coating, slit coating, dip coating, spray coating, printing, or the like to obtain a photosensitive resin film of the photosensitive resin composition. Prior to application, the substrate to which the photosensitive resin composition is to be applied may be pretreated with an adhesion improver. For example, a method of treating the substrate surface using a solution in which 0.5 to 20% by mass of an adhesion improver is dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, or diethyl adipate is used. Examples of substrate surface treatment methods include spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment. Specific examples of adhesion improvers include the adhesion improvers described in paragraph

[0127] of International Publication No. 2019 / 065351.

[0179] In the above step (2), the applied photosensitive resin film is subjected to a reduced pressure drying treatment as necessary, and then subjected to a heat treatment at a temperature in the range of 50°C to 180°C for 1 minute to several hours using a hot plate, an oven, infrared rays, or the like, to obtain a photosensitive resin film.

[0180] In the above step (3), the photosensitive resin film is irradiated with actinic radiation through a photomask having a desired pattern. Actinic radiation used for exposure includes ultraviolet light, visible light, electron beams, and X-rays. In the present invention, however, it is preferable to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) from a mercury lamp. After irradiation with actinic radiation, post-exposure baking may be performed. Post-exposure baking can be expected to improve the resolution after development or increase the tolerance for development conditions. Post-exposure baking can be performed using an oven, hot plate, infrared light, a flash annealing device, or a laser annealing device. The post-exposure baking temperature is preferably 50 to 180°C, more preferably 60 to 150°C. The post-exposure baking time is preferably 10 seconds to several hours. When the post-exposure baking time is within the above range, the reaction proceeds smoothly, and the development time may be shortened.

[0181] In the above step (4), the exposed resin film is developed using a developer to remove areas other than the exposed area. The developer is preferably a good solvent for the photosensitive resin composition, or a combination of the good solvent and a poor solvent. For example, in the case of a photosensitive resin composition that is not soluble in an alkaline aqueous solution, good solvents such as NMP, N-cyclohexyl-2-pyrrolidone, DMAc, cyclopentanone, cyclohexanone, GBL, and α-acetyl-γ-butyrolactone are preferred, while poor solvents such as toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water are preferred. When a mixture of a good solvent and a poor solvent is used, it is preferable to adjust the ratio of the poor solvent to the good solvent depending on the solubility of the polymer in the photosensitive resin composition. Two or more types of each solvent can also be used, for example, in combination. On the other hand, in the case of a photosensitive resin composition that is soluble in an alkaline aqueous solution, the developer used for development dissolves and removes the alkaline aqueous solution-soluble polymer, and is typically an alkaline aqueous solution containing an alkaline compound dissolved therein. Examples of alkaline compounds include tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine. In some cases, polar solvents such as NMP, DMF, DMAc, DMSO, GBL, and dimethylacrylamide, alcohols such as methanol, ethanol, and isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added alone or in combination to these aqueous alkaline solutions. Possible development methods include spray, paddle, immersion, and ultrasonic development.

[0182] Next, the pattern formed by development is preferably rinsed with deionized water. Here, too, alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to the deionized water for rinsing.

[0183] Next, the above step (5) is carried out. Heat treatment can remove residual solvents and components with low heat resistance, thereby improving heat resistance and chemical resistance. The photosensitive resin composition of the present invention can improve heat resistance and chemical resistance because the resin (A) can form imide rings and oxazole rings through heat treatment. Furthermore, when a crosslinking agent (E) is contained, heat treatment can promote a thermal crosslinking reaction, improving mechanical properties, heat resistance, and chemical resistance. This heat treatment is carried out by selecting a temperature and gradually increasing the temperature, or by selecting a temperature range and continuously increasing the temperature for 5 minutes to 5 hours. One example is heat treatment at 150°C and 250°C for 30 minutes each. Another method includes linearly increasing the temperature from room temperature to 300°C over 2 hours. Heat treatment conditions in the present invention are preferably 180°C or higher, more preferably 200°C or higher, even more preferably 230°C or higher, and particularly preferably 240°C or higher. The heat treatment conditions are preferably 400° C. or less, more preferably 350° C. or less, and even more preferably 300° C. or less.

[0184] Next, as an example of a method for producing the cured product of the present invention, a method for producing a cured film, which is one form of the cured product, using a photosensitive sheet obtained by forming the photosensitive resin composition of the present invention into a sheet will be described. Here, the photosensitive sheet refers to a sheet-like photosensitive resin composition obtained by applying the photosensitive resin composition onto a release film and drying it.

[0185] When using a photosensitive sheet formed from the photosensitive resin composition of the present invention in a sheet form, if any protective film is present on the photosensitive sheet, the protective film is peeled off, the photosensitive sheet is placed opposite a substrate, and the two are bonded together by thermocompression to obtain a photosensitive resin film. The photosensitive sheet can be obtained by applying the photosensitive resin composition of the present invention to a support film made of a peelable film such as polyethylene terephthalate, and drying the coated film.

[0186] Thermocompression bonding can be performed by heat pressing, heat lamination, thermal vacuum lamination, etc. The lamination temperature is preferably 40°C or higher in terms of adhesion to the substrate and embeddability. Furthermore, if the photosensitive sheet has photosensitivity, the lamination temperature is preferably 140°C or lower to prevent the photosensitive sheet from curing during lamination, which would reduce the resolution of pattern formation in the exposure and development steps.

[0187] The photosensitive resin film obtained by laminating a photosensitive sheet to a substrate can be formed into a cured film by following the steps of exposing the photosensitive resin film, developing the exposed photosensitive resin film, and heat curing.

[0188] The display device of the present invention comprises the cured product of the present invention. Specific examples of the display device of the present invention include LED displays, liquid crystal displays, and organic EL display devices. The cured product formed from the photosensitive resin composition of the present invention can be used in a display device including a first electrode formed on a substrate and a second electrode provided opposite the first electrode, and specifically can be used, for example, as an insulating film constituting an LED display, a planarizing layer in a liquid crystal display device, or a planarizing layer and / or pixel dividing layer in an organic EL display device.

[0189] The organic EL display device of the present invention comprises the cured product of the present invention. Preferably, the organic EL display device of the present invention comprises the cured product of the present invention as one or more layers selected from the group consisting of a pixel dividing layer, an electrode insulating layer, a wiring insulating layer, an interlayer insulating layer, a TFT planarizing layer, an electrode planarizing layer, a wiring planarizing 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. The organic EL display device of the present invention can be suitably used in various electronic devices. Examples of electronic devices include smartphones, tablet PCs, and smart glasses.

[0190] The electronic component of the present invention comprises the cured product of the present invention.

[0191] The cured product formed from the photosensitive resin composition of the present invention can be used as an insulating film or a protective film that constitutes an electronic component.

[0192] Here, examples of electronic components include active components having semiconductors such as transistors, diodes, integrated circuits (ICs), and memories, as well as passive components such as resistors, capacitors, and inductors. Electronic components using semiconductors are also called semiconductor devices or semiconductor packages.

[0193] Specific examples of the cured product in electronic components include passivation films for semiconductors, surface protective films for semiconductor elements, TFTs (Thin Film Transistors), and the like, interlayer insulating films such as interlayer insulating films between rewirings in multilayer wiring for high-density packaging of 2 to 10 layers, insulating films and protective films for touch panel displays, and insulating layers for organic electroluminescent devices; however, the cured product is not limited to these and can have a variety of structures.

[0194] Furthermore, the electronic component of the present invention preferably comprises the cured product of the present invention on a substrate. The surface of the substrate on which the cured product is formed can be appropriately selected depending on the application and process. Examples of the substrate include a silicon substrate, a silicon carbide substrate, a gallium nitride substrate, ceramics, gallium arsenide, metal, and epoxy resin. A silicon substrate, a silicon carbide substrate, or a gallium nitride substrate is preferred.

[0195] The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0196] The names of the compounds used, for which abbreviations are used, are shown below. ODPA: 4,4'-oxydiphthalic anhydride TDA: 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione (manufactured by New Japan Chemical Co., Ltd.) MCTC: 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) HBPDA: dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) BAHF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (manufactured by Central Glass Co., Ltd.) BAP: 2,2-bis(3-amino-4-hydroxyphenyl)propane (manufactured by Wakayama Seika Kogyo Co., Ltd.) 3,4'-ODA: 3,4'-diaminodiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) TPE-R: 1,3-bis(4-aminophenoxy)benzene SiDA: 1,3-bis(3-aminopropyl)tetramethyldisiloxane (manufactured by Tokyo Chemical Industry Co., Ltd.) MAP: 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) 4-APA: 4-aminophenylacetylene (manufactured by Tokyo Chemical Industry Co., Ltd.) MPA: 3-methoxy-N,N-dimethylpropanamide (manufactured by KJ Chemicals Co., Ltd.) DMIB: N,N-dimethylisobutyramide DMPA: N,N-dimethylpropionamide PGME: propylene glycol monomethyl ether GBL: γ-butyrolactone DMSO: dimethyl sulfoxide ITO: indium tin oxide TMAH: tetramethylammonium hydroxide DMFDMA: N,N-dimethylformamide dimethyl acetal.

[0197] [Common Processing Conditions] In the following measurement and evaluation methods, and in the examples and comparative examples, the following processing was carried out under the following conditions unless otherwise specified.

[0198] (1) Pretreatment of ITO Substrate A glass substrate (manufactured by Geomatec Co., Ltd.; hereinafter referred to as "ITO substrate") on which a 100 nm ITO film was formed by sputtering was treated with a tabletop optical surface treatment device (PL16-110; manufactured by Sen Special Light Sources Co., Ltd.) for 100 seconds under UV-O ３ The Si wafer (manufactured by Electronics and Materials Corporation) was used after being dehydrated and baked by heating it at 130°C for 2 minutes using a hot plate (HP-1SA; manufactured by AS ONE Corporation).

[0199] (2) Heat Treatment (Cure) The developed film was heated in a high-temperature inert gas oven (INH-9CD-S manufactured by Koyo Thermo Systems Co., Ltd.) at 250°C for 1 hour in a nitrogen atmosphere to form a cured film, which is a form of a cured product.

[0200] [Measurement and Evaluation Methods] (1) Weight-average molecular weight (Mw) of resin (A) The resin obtained in each synthesis example was measured for polystyrene-equivalent weight-average molecular weight (Mw) using a gel permeation chromatography (GPC) analyzer under the following conditions. Measuring device: Waters 2695 (manufactured by Waters) Column temperature: 50 ° C. Flow rate: 0.4 mL / min Detector: 2489 UV / Vis Detector (measurement wavelength 260 nm) Developing solvent: NMP (containing 0.21 mass% lithium chloride and 0.48 mass% phosphoric acid) Guard column: TOSOH TSK guard column (manufactured by Tosoh Corporation) Column: TOSOH TSK-GEL a-2500 and TOSOH TSK-GEL a-4000 (both manufactured by Tosoh Corporation) in series. Number of measurements: 2 (average value was taken as the weight average molecular weight of the polyimide).

[0201] (2) Measurement of the amount of components with a molecular weight of 1,000 or less contained in resin (A) The same method as for measuring the weight average molecular weight was used to calculate the area % of peaks with molecular weights of 1,000 or less in polystyrene equivalent values, and the area % of peaks with molecular weights of 1,000 or less was regarded as the mass % of components with a molecular weight of 1,000 or less contained in resin (A).

[0202] (3) Esterification Rate Using a nuclear magnetic resonance (NMR) apparatus (EX-270 manufactured by JEOL Ltd.), the esterification rate of a mixed solution of 10 mg of the resin obtained in each synthesis example and 0.8 g of deuterated DMSO (DMSO-d6) was measured. １ H-NMR was measured, and the integrated value of the peak derived from the aromatic protons of the resin was determined. The esterification rate of the polyamic acid ester was calculated from the area ratio to the peak derived from the methyl protons of the carboxylic acid ester. Since resins other than polyamic acid ester do not contain carboxylic acid esters, the esterification rate is indicated as "-" because it is not measurable.

[0203] (4) Imide ring closure rate (R ＩＭ (%)) The resin obtained in each synthesis example was dissolved in GBL to a concentration of 35% by mass. This solution was applied to a 4-inch silicon wafer by spin coating using a spinner (1H-DX manufactured by Mikasa Co., Ltd.), and then baked on a hot plate at 120°C for 3 minutes to produce a resin film 4 to 5 μm thick. This wafer with the resin film was divided into two, and one was cured in a clean oven (CLH-21CD-S manufactured by Koyo Thermo Systems Co., Ltd.) under a nitrogen stream (oxygen concentration 20 ppm or less) at 140°C for 30 minutes, then further heated to 320°C for 1 hour to completely close the imide ring. The transmission infrared absorption spectra of the resin film before and after curing were measured using an infrared spectrophotometer (FT-720 manufactured by Horiba, Ltd.), and the absorption peak (1,780 cm) of the imide structure due to polyimide was observed. －１ Near 1,377 cm －１ After confirming the existence of the 1,377 cm －１ The peak intensity ratio (before curing: S, after curing: T) around the peak intensity (S) was calculated by dividing the peak intensity (S) by the peak intensity (T) using the following formula, and this was taken as the content of imide groups in the polymer before heat treatment, i.e., the imide ring closure rate. ＩＭ (%) = (S / T) x 100. Resins other than polyimide (including polyamic acid ester) do not have polyimide structural units, and therefore the imide ring closure rate is not measurable and is indicated by "-".

[0204] (5) Evaluation of the Content of Compounds Represented by Formula (17) and Formula (18) in Resin (A) 0.03 g of Resin (A) obtained in each Synthesis Example and 0.01 g of methyl 3-nitrobenzoate as an internal standard substance were dissolved in 0.7 g of deuterated DMSO and analyzed by NMR (GX-270, manufactured by JEOL Ltd.). Using the area of ​​the peak at around 3.9 ppm derived from methyl 3-nitrobenzoate as a reference, the content [parts by mass] of the compounds represented by Formula (17) and Formula (18) per 100 parts by mass of the Resin (A) component was measured from each peak area.

[0205] (6) Film Thickness Measurement Using a surface roughness and contour shape measuring instrument (SURFCOM1400D; manufactured by Tokyo Seimitsu Co., Ltd.), the film thickness was measured at a measurement magnification of 10,000 times, a measurement length of 1.0 mm, and a measurement speed of 0.30 mm / s.

[0206] (7) Thinner Solubility The photosensitive resin composition of each Example and Comparative Example was applied to a 4-inch silicon wafer by spin coating using a spinner (1H-DX manufactured by Mikasa Co., Ltd.), and then baked on a hot plate at 120°C for 2 minutes to produce a resin film with a thickness of 2 μm. This wafer with resin film was divided into two, and one was immersed in 100 g of PGME at 23°C for 2 minutes and rinsed with pure water. The other divided wafer with resin film was similarly immersed in 100 g of PGME at 23°C for 5 minutes and rinsed with pure water. Dissolution of the resin film was confirmed by visual inspection and film thickness measurement. The results were judged as follows, with A, B, and C being considered acceptable. A being the most preferable result. A: Completely dissolved after 2 minutes of static immersion. B: Not completely dissolved after 2 minutes of static immersion, but completely dissolved after 5 minutes of static immersion. C: Film thickness after 5 minutes of static immersion is less than 1.0 μm. D: Film thickness after 5 minutes of static immersion is 1.0 μm or more.

[0207] (8) Flatness Evaluation A cross-sectional view of a flatness evaluation sample is shown in Figure 1. The photosensitive resin composition of each example and comparative example, which is a sample, was applied by spin coating using a spin coater (MS-A100; manufactured by Mikasa Co., Ltd.) to a 100 mm square stepped substrate 1 having five parallel line patterns with a thickness (height) of 1.2 μm, a width of 5 μm, and a length of 15 mm at 5 μm intervals in the central part of the substrate, and prebaked at 110 ° C. for 120 seconds to prepare a prebaked film such that the film thickness h0 at a flat portion of the substrate where the pattern was not provided, away from the pattern and not affected by the pattern (for convenience, the point where the measurement was performed is referred to as "measurement point A"), was 3.7 μm. The resulting substrate with the film was then subjected to a curing process in which the temperature was raised to 250°C at a rate of 5°C / min in an oxygen concentration of 20 ppm or less using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.), and the temperature was then increased to 250°C at a rate of 5°C / min, and the substrate was then heated at 250°C for 1 hour, producing a cured film with a film thickness of approximately 2.5 μm at measurement point A. The surface step of the resulting cured film was measured using a surface profiler (P-15; manufactured by KLA Tencor Corporation), and the average value of heights h1 to h3 from baseline 3 of the film present on the line patterns for three of the five line patterns, excluding the outermost two, was defined as the surface step h. Note that baseline 3 was defined as the line connecting the points at which the film thickness of the recesses on the left and right of each mountain-like resin film portion where h1 to h3 were measured was smallest, as viewed from Figure 1. Specific examples are described below. In Figure 1, the straight line connecting the bottoms a1 and a2 of the step shape is used as the baseline, and the length from the top b1 of the step shape to the intersection of a line drawn perpendicular to the substrate surface with the baseline is defined as h1. h2 is defined as the length from b2 to the intersection of a line drawn perpendicular to the substrate surface with the baseline, with the line connecting a2 and a3 being the baseline, and h3 is defined as the length from b3 to the intersection of a line drawn perpendicular to the substrate surface with the baseline, with the line connecting a3 and a4 being the baseline. Flatness was evaluated based on the surface step h as follows, and A, B, and C, which have a surface step h of less than 0.4 μm, were rated as passing. Note that A is the most preferable result.A: The surface step h is less than 0.2 μm. B: The surface step h is 0.2 μm or more and less than 0.3 μm. C: The surface step h is 0.3 μm or more and less than 0.4 μm. D: The surface step h is 0.4 μm or more.

[0208] (9) Sensitivity Evaluation The photosensitive resin composition obtained in each Example and Comparative Example was applied by spin coating onto a 100 mm x 100 mm ITO substrate using a spin coater (MS-A100; manufactured by Mikasa Co., Ltd.) by adjusting the rotation speed so that the thickness of the prebaked film would be approximately 1.8 μm. The resulting film was then prebaked at 110°C for 120 seconds using a buzzer hot plate (HPD-3000BZN; manufactured by AS ONE Corporation) to produce a prebaked film with a thickness of approximately 1.8 μm. The resulting prebaked film was exposed to ultraviolet light at 150 mJ / cm using a manual exposure machine (MA-1200; manufactured by Nippon Kaken Co., Ltd.) through a positive mask (manufactured by HOYA Corporation, stripe design line width 20 μm). ２ (value of i-line illuminometer) as the maximum exposure, and 5 mJ / cm ２ The exposure dose was reduced for each exposure, followed by development, rinsing, and drying to obtain a patterned substrate with a photosensitive resin film formed in a predetermined pattern. Sensitivity was evaluated using the patterned substrates with each exposure dose. Development was carried out by shower development using a small automatic photolithography developing device (AD-2000 manufactured by Takizawa Sangyo Co., Ltd.) with an alkaline developer of 2.38% by mass TMAH aqueous solution. The development time was adjusted so that the film loss in the unexposed areas was 0.5 μm, and rinsing was carried out with deionized water.

[0209] The openings in the resulting developed film were observed using an FPD / LSI inspection microscope (OPTIPHOT-300; manufactured by Nikon Corporation), and the minimum exposure dose at which the opening width became the same line width (20 μm) as the mask design was taken as the sensitivity. The sensitivity was determined as follows, and the sensitivity was 110 mJ / cm ２ AA, A, B and C, which are less than 65 mJ / cm, were rated as passing. AA is the most preferable result. ２ A: Sensitivity is less than 65 mJ / cm ２ More than 80mJ / cm ２ B: Sensitivity is less than 80 mJ / cm ２ 95mJ / cm or more ２C: Sensitivity is less than 95 mJ / cm ２ 110mJ / cm or more ２ D: Sensitivity is less than 110 mJ / cm ２ That's all.

[0210] (10) Evaluation of Development Residues In the same manner as in (9) above, the photosensitive resin composition was applied onto an ITO substrate and prebaked to form a prebaked film having a thickness of about 1.8 μm. The obtained prebaked film was exposed to the i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) of an ultra-high pressure mercury lamp at an exposure dose of 150 mJ / cm using a manual exposure machine (MA-1200; manufactured by Japan Science Research Institute Co., Ltd.) through a grayscale mask for sensitivity measurement (MDRM MODEL 4000-5-FS; manufactured by Opto-Line International, Inc., having a 2-50 μm, 1:1 line and space pattern, with areas of transmittance of 1%, 5%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 25%, 30%, 35%, 40%, 50%, and 60%, respectively). ２ After patterning exposure at 1000 kJ / cm2 (value measured by an i-line illuminometer), the film was developed, rinsed, and dried to produce a developed film of the photosensitive resin composition. The development time was adjusted so that the film thickness loss in the unexposed areas was 0.5 μm, and rinsing was performed using deionized water.

[0211] Using an FPD / LSI inspection microscope (OPTIPHOT-300; manufactured by Nikon Corporation), the resolved pattern of the prepared developed film was observed to check for the presence or absence of residue in the openings of a 20 μm line-and-space pattern at the location of the minimum exposure dose where the opening width became the same line width (20 μm) as the mask design. The results were judged as follows, and grades A, B, and C, where the area of ​​residue in the openings was less than 10%, were judged to be acceptable. Grade A was the most favorable result. A: No residue in the openings (less than 1%) B: The area of ​​residue in the openings was 1% or more but less than 5% C: The area of ​​residue in the openings was 5% or more but less than 10% D: The area of ​​residue in the openings was 10% or more.

[0212] (11) Measurement of the depth from the substrate surface at which carbon components are no longer detected (X-ray photoelectron spectroscopy (XPS)) (penetration depth of carbon components) A 4-inch silicon wafer with aluminum vapor deposition was used instead of the 100 mm x 100 mm ITO substrate, and the sample photosensitive resin composition was applied so that the thickness of the pre-baked film was 3.6 μm. The wafer was developed, rinsed, and dried in the same manner as in (9) above to obtain a patterned substrate that had undergone the development process. The openings in the obtained patterned substrate were observed using an FPD / LSI inspection microscope (OPTIPHOT-300; manufactured by Nikon Corporation), and the minimum exposure dose at which the opening width became the same line width (20 μm) as the mask design was confirmed. Next, the patterned substrate was thermally cured at 250 ° C. using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.) to obtain a cured film. The thermal curing conditions were as follows: the patterned substrate was placed in an oven regulated at 250°C under a nitrogen atmosphere and thermally cured for 60 minutes. The sample was then exposed at the minimum exposure dose that resulted in the opening width being the same line width (20 μm) as the mask design. The chemical state of the surface at the opening was then measured using an SSI SSX-100 X-ray photoelectron spectrometer. Furthermore, a depth profile analysis was performed using Ar ion etching on the substrate portion between the lines that appeared after development. The depth at which carbon components were no longer detectable was measured to determine the degree of contamination of the substrate by carbon components (organic matter). The results were evaluated as follows: A, B, and C were deemed acceptable, as carbon components were no longer detectable at depths of less than 10.0 nm from the substrate surface. Grade A was the most favorable result. A: Carbon components are no longer detected at a depth of less than 5.0 nm from the substrate surface. B: Carbon components are no longer detected at a depth of 5.0 nm or more but less than 7.5 nm from the substrate surface. C: Carbon components are no longer detected at a depth of 7.5 nm or more but less than 10.0 nm from the substrate surface. D: Carbon components are no longer detected at a depth of 10.0 nm or more from the substrate surface.

[0213] (12) Breaking Elongation Evaluation The resin compositions obtained in each example and comparative example were applied to an 8-inch silicon wafer by spin coating using an ACT-8 coating and developing apparatus so that the film thickness after pre-baking at 120°C for 3 minutes was 15 μm. After pre-baking, the wafer was heated to 250°C at a rate of 4.0°C / min using an inert oven CLH-21CD-S (manufactured by Koyo Thermo Systems Co., Ltd.) at an oxygen concentration of 20 ppm or less, and then heat-treated at 250°C for 1 hour. When the temperature reached 50°C or less, the silicon wafer was removed and immersed in 45% by mass hydrofluoric acid for 3 minutes to peel off the cured film of the resin composition from the wafer. This film was cut into strips 1 cm wide and 9 cm long, and the breaking elongation was measured using a Tensilon RTM-100 (manufactured by Orientec Co., Ltd.) at room temperature of 23.0°C, humidity of 45.0% RH, and a pulling rate of 50 mm / min. Measurements were performed on 10 strips per specimen, and the average of the top five scores was calculated from the results. The evaluation was carried out as follows, and AA, A, B, and C, which had a breaking elongation value of 5% or more, were deemed to be passing. AA is the most preferable result. AA: Breaking elongation value of 20% or more A: Breaking elongation value of 15% or more but less than 20% B: Breaking elongation value of 10% or more but less than 15% C: Breaking elongation value of 5% or more but less than 10% D: Breaking elongation value less than 5%.

[0214] (13) Storage Stability (Change in Sensitivity After Storage) The photosensitive resin compositions obtained in each Example and Comparative Example were left to stand at 23°C and 45% RH for 5 days, and then the sensitivity was evaluated in the same manner as in (9) to determine the sensitivity. When the sensitivity before standing was Eop(B) and the sensitivity after standing was Eop(A), the change in sensitivity x (%) was calculated using the following formula. The evaluation was performed as follows, and A, B, and C, which had an x ​​value of less than 125, were rated as passing. Note that A was the most preferable result. Change in sensitivity x (%) = Eop(A) / Eop(B) × 100 A: x is less than 105 B: x is 105 or more but less than 115 C: x is 115 or more but less than 125 D: x is 125 or more.

[0215] (14) Transmittance of Cured Film The photosensitive resin composition obtained in each example and each comparative example was applied by spin coating onto a Tempax glass substrate (manufactured by AGC Technoglass Co., Ltd.) using a spin coater (MS-A100; manufactured by Mikasa Co., Ltd.) with the rotation speed adjusted so that the thickness of the prebaked film was approximately 2.8 μm. The resulting film was then prebaked at 110 ° C. for 120 seconds using a buzzer hot plate (HPD-3000BZN; manufactured by AS ONE Corporation) to produce a prebaked film with a thickness of approximately 3.0 μm. The film was then developed, rinsed, and dried to obtain a substrate with a post-development film. Development was carried out using a small automatic photolithography developing apparatus (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.) by shower development using an alkaline developer of 2.38% by mass TMAH aqueous solution, and the development time was adjusted so that the film loss in the unexposed areas was 0.5 μm. Rinsing was carried out using deionized water. Subsequently, the substrate with the developed film obtained was subjected to a curing process in which the temperature was raised to 250°C at a rate of 5°C / min in an oxygen concentration of 20 ppm or less using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.), and the substrate was then heated at 250°C for 1 hour to obtain a substrate with a cured film having a film thickness of 2.0 μm. The transmittance of the substrate with the cured film thus obtained at a wavelength of 400 nm was measured using a UV-visible spectrophotometer (Shimadzu Corporation, MultiSpec-1500). The results were evaluated as follows, and A, B, and C, which indicate a transmittance of 60% or more at a wavelength of 400 nm through a 2.0 μm cured film, were evaluated as passing. Note that A is the most preferable result. A: transmittance of 90% or more B: transmittance of 75% or more but less than 90% C: transmittance of 60% or more but less than 75% D: transmittance of less than 60%.

[0216] (15) Evaluation of Appearance and Light-Emitting Reliability of Organic EL Display Devices Figure 2 shows the fabrication process for an organic EL display device, including the steps of forming a planarizing layer and a pixel dividing layer. First, the photosensitive resin composition obtained in each Example and Comparative Example was applied to a 38 x 46 mm alkali-free glass substrate (4) by spin coating, adjusting the rotation speed so that the final planarizing layer thickness was 2.0 μm, to obtain a coating film. Next, using a hot plate (HPD-3000BZN, manufactured by AS ONE Corporation), the coating film was prebaked at 120°C under atmospheric pressure for 120 seconds to obtain a prebaked film. This film was exposed to UV light through a photomask, developed with a 2.38% TMAH aqueous solution, and only the exposed portions were dissolved, followed by rinsing with pure water. The resulting developed film was cured. The curing was performed using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.) under conditions of an oxygen concentration of 20 ppm or less, heating at 250°C at a rate of 5°C / min, and heat treatment at 250°C for 1 hour. In this way, a planarization layer (5) without an opening was formed in an area of ​​16 mm length x 16 mm width at the center of the substrate. The planarization layer had a thickness of 2.0 μm. Next, a 10 nm thick thin film of silver / copper alloy (volume ratio 10:1) was formed on the entire surface by sputtering, and then etched to form a patterned metal reflective layer (6). Next, a 10 nm thick ITO transparent conductive film was formed on the entire surface by sputtering, and then etched to form a second electrode (7) and an auxiliary electrode (8) with the same pattern as the lead electrode. The substrate was then ultrasonically cleaned for 10 minutes using "Semicoclean" (registered trademark) 56 (manufactured by Furuuchi Chemical Co., Ltd.) and washed with deionized water to obtain an electrode-formed substrate. The photosensitive composition was applied to the surface of the electrode-formed substrate using a spin coater, adjusting the rotation speed so that the final thickness of the pixel division layer would be 2.0 μm, to obtain a coating film. Next, the coating film was prebaked at 120° C. under atmospheric pressure for 120 seconds using a hot plate (HPD-3000BZN, manufactured by AS ONE Corporation) to obtain a prebaked film.

[0217] A positive exposure mask with openings (30 μm wide x 165 μm long rectangles) arranged at a 50 μm pitch was set on the coating film so that the vertical and horizontal edges of the patterned light-shielding portion of the positive exposure mask were parallel to the vertical and horizontal edges of the alkali-free glass substrate (4), respectively. Using a manual exposure machine (MA-1200; manufactured by Dai-Nippon Kaken Co., Ltd.), the prebaked film was pattern-irradiated with exposure light using a mixture of j-line (313 nm), i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) from an ultra-high pressure mercury lamp at the minimum required exposure dose, thereby obtaining an exposed film. The positive exposure mask was then developed and rinsed to obtain a developed film. The positive exposure mask used was a mask with a patterned light-shielding portion made of chromium formed on the surface of a soda glass substrate.

[0218] Furthermore, the developed film was subjected to a heat treatment (curing) to form a cured film, and a patterned cured film-formed substrate having a thickness of 2.0 μm and a patterned cured film (9) with openings (rectangles measuring 30 μm wide x 165 μm long) arranged at a pitch of 50 μm within a 16 mm long x 16 mm wide area in the center of the electrode-formed substrate was obtained, with an aperture ratio of 18%. The curing was carried out using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.) under conditions of an oxygen concentration of 20 ppm or less, heating to 250°C at a rate of 5°C / min, and heat treatment at 250°C for 1 hour. In the organic EL display device obtained after the process described below, the openings referred to here are the portions that will ultimately become the light-emitting pixel portions, and the patterned cured film is the portion corresponding to the pixel dividing layer.

[0219] Next, an organic EL display device was produced using the patterned cured film-formed substrate. To form the organic EL layer (10) including the light-emitting layer by vacuum deposition, a vacuum of 1×10 －３The patterned cured film-formed substrate was rotated relative to the evaporation source under evaporation conditions of 0.1 Pa or less, and first, a 10 nm thick film of compound HT-1 was formed as a hole injection layer, and a 50 nm thick film of compound HT-2 was formed as a hole transport layer. Next, compound GH-1 as a host material and compound GD-1 as a dopant material were evaporated onto the light-emitting layer to a thickness of 40 nm. Thereafter, compound ET-1 and compound LiQ were laminated as electron transport materials at a volume ratio of 1:1 to a thickness of 40 nm.

[0220] Next, the compound LiQ was vapor-deposited to a thickness of 2 nm, and then a silver / magnesium alloy (volume ratio 10 / 1) was vapor-deposited to a thickness of 10 nm to form a first electrode (11).

[0221] The chemical structures of the compounds (HT-1, HT-2, GH-1, GD-1, ET-1, and LiQ) used to form the organic EL layer are shown below.

[0222]

[0223] The thickness referred to here is the value displayed on a quartz crystal oscillation type film thickness monitor.

[0224] Thereafter, a cap-shaped glass plate was adhered and sealed in a low humidity / nitrogen atmosphere using an epoxy resin adhesive to obtain an organic EL display device.

[0225] Observation of Appearance of Organic EL Display Device The surface of the pixel division layer of the obtained organic EL display device was observed using an FPD / LSI inspection microscope (OPTIPHOT-300; manufactured by Nikon Corporation). Those in which swelling of the film due to air bubbles was observed were judged as NG, and those in which the pixel division layer surface was flat and no swelling due to air bubbles was observed were judged as OK.

[0226] Light-emitting reliability test of organic EL display device The obtained organic EL display device was placed on a hot plate heated to 80°C with the display section (light-emitting surface) facing up, and a current of 10 mA / cm ２ The pixel light emitting area ratio (the ratio of the area of ​​the actual light emitting portion to the area of ​​the light emitting pixel) was evaluated one hour after the device was driven to emit light by DC current at 1000 V. Thereafter, the power supply was temporarily turned off to turn off the light.

[0227] Then, the sample was placed on a hot plate heated to 80°C and irradiated with a xenon lamp as a light source for simulated sunlight at a wavelength of 420 nm with an illuminance of 3.0 W / m ２ The display was continuously irradiated with light of 10 ...

[0228] In each evaluation, A to C, where the pixel light-emitting area ratio was 65% or more, were rated as passing, and D was rated as failing. Note that A was the most preferable result.

[0229] Synthesis Example 1: Synthesis of quinone diazide compound QD-a 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 5-naphthoquinone diazide sulfonyl chloride were dissolved in 450 g of 1,4-dioxane and the solution was allowed to reach room temperature. A solution of 15.18 g of triethylamine dissolved in 50 g of 1,4-dioxane was added dropwise to the system so that the temperature was 35°C or less. After the dropwise addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. The mixture was then filtered, and the precipitate was collected. This precipitate was dried in a vacuum dryer to obtain quinone diazide compound QD-a represented by formula (41).

[0230]

[0231] In formula (41), * represents a bonding site with an oxygen atom.

[0232] Synthesis Example 2: Synthesis of quinone diazide compound QD-b> A quinone diazide compound QD-b represented by formula (42) was obtained by the same method as in the synthesis example for quinone diazide compound QD-a, except that 36.27 g (0.135 mol) of 4-naphthoquinone diazide sulfonyl chloride was used instead of 36.27 g (0.135 mol) of 5-naphthoquinone diazide sulfonyl chloride.

[0233]

[0234] In formula (42), * represents the bonding site with the oxygen atom.

[0235] Synthesis Example 3: Synthesis of diamine (DAP-A) A 500 ml four-neck flask equipped with a stirrer, thermocouple, and dropping funnel was charged with 24.28 g (0.086 mol) of BisP-3MZ (4,4'-(3-methylcyclohexane-1,1-diyl)diphenol, manufactured by Honshu Chemical Industry Co., Ltd.) and 100 ml of glacial acetic acid, and the mixture was stirred. The internal temperature was raised to 50°C in a water bath. To this mixture, 2 ml (0.026 mol) of concentrated nitric acid was added dropwise over 1 hour. The mixture was then cooled with ice to lower the internal temperature to 13°C, and 13.3 ml (0.149 mol) of concentrated nitric acid was added dropwise over 1 hour. Stirring was continued for 3 hours, and 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 the dinitro form.

[0236] Next, 50.27 g (0.135 mol) of the dinitro compound, 180 ml (3.71 mol) of hydrazine monohydrate, and 900 ml of ethanol were placed in a 2 L four-neck flask equipped with a stirrer, thermocouple, Dimroth condenser, and dropping funnel, and the mixture was stirred under ice cooling. 0.9 g of 5% palladium-carbon (Wako Pure Chemical Industries, Ltd.) suspended in 30 ml of ethanol was added dropwise over 1 hour. The solution was then refluxed for 2 hours, and the palladium-carbon was removed by filtration while washing with 300 ml of ethanol. All of the solvent was removed by heating under reduced pressure, and the residue was washed with 75 ml of ice-cold ethanol, filtered, and then washed with 75 ml of deionized water and 150 ml of diethyl ether, followed by drying under reduced pressure, to obtain diamine (DAP-A).

[0237] Synthesis Example 4: Synthesis of diamine (DAP-B) A dinitro product was synthesized using 26.70 g (0.086 mol) of BisP-HTG (manufactured by Honshu Chemical Industry Co., Ltd.; 4,4′-(3,3,5-trimethylcyclohexylidene)bisphenol) instead of BisP-3MZ (manufactured by Honshu Chemical Industry Co., Ltd.), and diamine (DAP-B) was obtained in the same manner as in Synthesis Example 3, except that 54.06 g (0.135 mol) of the dinitro product was used.

[0238] Synthesis Example 5: Synthesis of diamine (DAP-C) A dinitro product was synthesized using 23.25 g (0.086 mol) of 4,4′-(1,3-dimethylbutylidene)diphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of BisP-3MZ (manufactured by Honshu Chemical Industry Co., Ltd.), and diamine (DAP-C) was obtained in the same manner as in Synthesis Example 3, except that 48.65 g (0.135 mol) of the dinitro product was used.

[0239] Synthesis Example 6: Synthesis of diamine (DAP-D) A dinitro compound was synthesized using 20.84 g (0.086 mol) of 2,2-bis(4-hydroxyphenyl)butane (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of BisP-3MZ (manufactured by Honshu Chemical Industry Co., Ltd.), and diamine (DAP-D) was obtained in the same manner as in Synthesis Example 3, except that 44.86 g (0.135 mol) of the dinitro compound was used.

[0240] Synthesis Example 7: Synthesis of diamine (DAP-E) A dinitro product was synthesized using 25.66 g (0.086 mol) of BisP-IOTD (manufactured by Honshu Chemical Industry Co., Ltd.; 4,4′-(2-ethylhexylidene)diphenol) instead of BisP-3MZ (manufactured by Honshu Chemical Industry Co., Ltd.), and diamine (DAP-E) was obtained in the same manner as in Synthesis Example 3, except that 52.44 g (0.135 mol) of the dinitro product was used.

[0241] Synthesis Example 8: Synthesis of diamine (DAP-F) A dinitro product was synthesized using 22.13 g (0.086 mol) of BisP-IBTD (manufactured by Honshu Chemical Industry Co., Ltd.; 4,4′-(2-methylpropane-1,1-diyl)diphenol) instead of BisP-3MZ (manufactured by Honshu Chemical Industry Co., Ltd.), and diamine (DAP-F) was obtained in the same manner as in Synthesis Example 3, except that 46.89 g (0.135 mol) of the dinitro product was used.

[0242] Synthesis Example 9: Synthesis of diamine (DAP-G) A dinitro compound was synthesized using 20.84 g (0.086 mol) of BIOC-E (manufactured by Asahi Organic Chemicals Co., Ltd.; 1,1′-bis(4-hydroxy-3-methylphenyl)ethane) instead of BisP-3MZ (manufactured by Honshu Chemical Industry Co., Ltd.), and diamine (DAP-G) was obtained in the same manner as in Synthesis Example 3, except that 44.86 g (0.135 mol) of the dinitro compound was used.

[0243] Synthesis Example 10: Synthesis of diamine (DAP-H) A dinitro compound was synthesized using 26.52 g (0.086 mol) of SPI (3,3,3′,3′-tetramethyl-1,1′-spirobiindan-6,6′-diol, manufactured by JFE Chemical Corporation) instead of BisP-3MZ (manufactured by Honshu Chemical Industry Co., Ltd.), and diamine (DAP-H) was obtained in the same manner as in Synthesis Example 3, except that 53.79 g (0.135 mol) of the dinitro compound was used.

[0244] Synthesis Example 11: Synthesis of diamine (DAP-I) A dinitro compound was synthesized using 23.08 g (0.086 mol) of TMHI (manufactured by JFE Chemical Corporation; 3-(4-hydroxyphenyl)-1,1,3-trimethyl-5-indanol) instead of BisP-3MZ (manufactured by Honshu Chemical Industry Co., Ltd.), and diamine (DAP-H) was obtained in the same manner as in Synthesis Example 3, except that 48.38 g (0.135 mol) of the dinitro compound was used.

[0245] Synthesis Example 12: Synthesis of 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane (HA) 18.3 g (0.05 mol) of BAHF was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide (manufactured by Tokyo Chemical Industry Co., Ltd.), and the solution was cooled to −15°C. To this solution, a solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 mL of acetone was added dropwise. After completion of the dropwise addition, the mixture was stirred at −15°C for 4 hours and then returned to room temperature. The precipitated white solid was filtered and dried in vacuo at 50°C.

[0246] 30 g of the obtained white solid was placed in a 300 mL stainless steel autoclave and dispersed in 250 mL of methyl cellosolve, and 2.0 g of 5% palladium-carbon (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Hydrogen was introduced into the autoclave using a balloon, and the reduction reaction was carried out at room temperature. After approximately 2 hours, the reaction was terminated when it was confirmed that the balloon no longer deflated. After the reaction was completed, the palladium compound catalyst was removed by filtration, and the mixture was concentrated using a rotary evaporator to obtain a diamine compound (HA) represented by the following formula:

[0247] Synthesis Example 13: Synthesis of diamine compound (HB) A diamine compound (HB) was obtained in the same manner as in Synthesis Example 12, except that 12.9 g (0.05 mol) of BAP was used instead of BAHF.

[0248] Synthesis Example 14: Synthesis of diamine compound (HC) A diamine compound (HC) was obtained in the same manner as in Synthesis Example 12, except that 17.0 g (0.05 mol) of DAP-B obtained in Synthesis Example 4 was used instead of BAHF.

[0249] Synthesis Example 15: Synthesis of diamine compound (HD) A diamine compound (HD) was obtained in the same manner as in Synthesis Example 12, except that 15.0 g (0.05 mol) of DAP-C obtained in Synthesis Example 5 was used instead of BAHF.

[0250] Synthesis Example 16: Synthesis of diamine compound (HE) A diamine compound (HE) was obtained in the same manner as in Synthesis Example 12, except that 13.6 g (0.05 mol) of DAP-D obtained in Synthesis Example 6 was used instead of BAHF.

[0251] Synthesis Example 17: Synthesis of diamine compound (DAP-J) A dinitro compound was synthesized using 23.08 g (0.086 mol) of 4,4′-cyclohexylidenebisphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of BisP-3MZ (manufactured by Honshu Chemical Industry Co., Ltd.), and diamine compound (DAP-J) was obtained in the same manner as in Synthesis Example 3, except that 48.38 g (0.135 mol) of the dinitro compound was used.

[0252] Synthesis Example 18: Synthesis of diamine compound (DAP-K) A dinitro compound was synthesized using 27.90 g (0.086 mol) of 4,4′-(p-menthane-2,8-diyl)diphenol (manufactured by Chemieliva Pharmaceuticals), a type of terpene diphenol, instead of BisP-3MZ (manufactured by Honshu Chemical Industry Co., Ltd.), and diamine compound (DAP-K) was obtained in the same manner as in Synthesis Example 3, except that 55.95 g (0.135 mol) of the dinitro compound was used.

[0253] The structures of the diamine compounds obtained in Synthesis Examples 3 to 18 are shown below.

[0254]

[0255] Synthesis Example 51: Synthesis of Polyamic Acid (a-1) Under a dry nitrogen stream, 13.0 g (0.042 mol) of the diamine compound (DAP-A) obtained in Synthesis Example 3 and 0.62 g (0.0025 mol) of SiDA were dissolved in 95 g of MPA. To this solution, 7.51 g (0.025 mol) of TDA and 7.76 g (0.025 mol) of ODPA were added along with 10 g of MPA, and the mixture was stirred at 60°C for 2 hours. Then, 1.09 g (0.010 mol) of MAP was added as an end-capping agent along with 10 g of MPA, and the mixture was allowed to react at 60°C for 1 hour. The mixture was then stirred at 140°C for 4 hours. After stirring, the solution was poured into 2 L of deionized water, and the polymer solid precipitate was collected by filtration. The polymer solid was then washed three times with 2 L of deionized water and dried in a vacuum dryer at 50° C. for 72 hours to obtain polyamic acid (a-1), which is a form of polyimide.

[0256] Synthesis Example 52: Synthesis of polyamic acid (a-2) Polyamic acid (a-2), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 51, except that 14.13 g (0.042 mol) of the diamine compound (DAP-B) obtained in Synthesis Example 4 was used instead of the diamine compound (DAP-A).

[0257] Synthesis Example 53: Synthesis of polyamic acid (a-3) Polyamic acid (a-3), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 51, except that 12.47 g (0.042 mol) of the diamine compound (DAP-C) obtained in Synthesis Example 5 was used instead of the diamine compound (DAP-A).

[0258] Synthesis Example 54: Synthesis of polyamic acid (a-4) Polyamic acid (a-4), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 51, except that 11.30 g (0.042 mol) of the diamine compound (DAP-D) obtained in Synthesis Example 6 was used instead of the diamine compound (DAP-A).

[0259] Synthesis Example 55: Synthesis of polyamic acid (a-5) Polyamic acid (a-5), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 51, except that 13.63 g (0.042 mol) of the diamine compound (DAP-E) obtained in Synthesis Example 7 was used instead of the diamine compound (DAP-A).

[0260] Synthesis Example 56: Synthesis of polyamic acid (a-6) Polyamic acid (a-6), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 51, except that 11.30 g (0.042 mol) of the diamine compound (DAP-F) obtained in Synthesis Example 8 was used instead of the diamine compound (DAP-A).

[0261] Synthesis Example 57: Synthesis of polyamic acid (a-7) Polyamic acid (a-7), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 51, except that 11.30 g (0.042 mol) of the diamine compound (DAP-G) obtained in Synthesis Example 9 was used instead of the diamine compound (DAP-A).

[0262] Synthesis Example 58: Synthesis of polyamic acid (a-8) Polyamic acid (a-8), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 51, except that 14.05 g (0.042 mol) of the diamine compound (DAP-H) obtained in Synthesis Example 10 was used instead of the diamine compound (DAP-A).

[0263] Synthesis Example 59: Synthesis of polyamic acid (a-9) Polyamic acid (a-9), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 51, except that 12.38 g (0.042 mol) of the diamine compound (DAP-I) obtained in Synthesis Example 11 was used instead of the diamine compound (DAP-A).

[0264] Synthesis Example 60: Synthesis of polyamic acid (a-10) Polyamic acid (a-10), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 52, except that 6.61 g (0.025 mol) of MCTC (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of TDA.

[0265] Synthesis Example 61: Synthesis of polyamic acid (a-11) Polyamic acid (a-11), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 52, except that 10.72 g (0.032 mol) of diamine compound (DAP-B) and 2.00 g (0.010 mol) of 3,4′-ODA (3,4′-diaminodiphenyl ether, manufactured by Tokyo Chemical Industry Co., Ltd.) were used instead of 14.13 g (0.042 mol) of diamine compound (DAP-B).

[0266] Synthesis Example 62: Synthesis of polyamic acid (a-12) Polyamic acid (a-12), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 52, except that 7.32 g (0.022 mol) of diamine compound (DAP-B) and 4.00 g (0.020 mol) of 3,4′-ODA (3,4′-diaminodiphenyl ether, manufactured by Tokyo Chemical Industry Co., Ltd.) were used instead of 14.13 g (0.042 mol) of diamine compound (DAP-B).

[0267] Synthesis Example 63: Synthesis of Polyamic Acid Ester (a-13) Under a dry nitrogen stream, 24.02 g (0.042 mol) of the diamine compound (HC) obtained in Synthesis Example 13 and 0.62 g (0.0025 mol) of SiDA were dissolved in 95 g of MPA. To this solution, 15.0 g (0.050 mol) of TDA was added along with 10 g of MPA, and the mixture was stirred at 60°C for 2 hours. Then, 1.09 g (0.010 mol) of MAP was added as an end-capping agent along with 10 g of MPA, and the mixture was allowed to react at 60°C for 1 hour. After the temperature was lowered from 60°C to 40°C, a solution prepared by diluting 11.9 g (0.010 mol) of DMFDMA with 10 g of MPA was added dropwise. After the dropwise addition, stirring was continued for 2 hours at 40°C. After stirring was completed, the solution was poured into 2 L of deionized water, and the polymer solid precipitate was collected by filtration. The polymer solid was then washed three times with 2 L of deionized water and dried in a vacuum dryer at 50° C. for 72 hours to obtain a polyamic acid ester (a-13), which is a form of polyimide.

[0268] Synthesis Example 64: Synthesis of polyamic acid ester (a-14) Polyamic acid ester (a-14), which is one form of polyimide, was obtained in the same manner as in Synthesis Example 63, except that 22.35 g (0.042 mol) of diamine compound (HD) was used instead of 24.02 g (0.042 mol) of diamine compound (HC).

[0269] Synthesis Example 65: Synthesis of polyamic acid ester (a-15) Polyamic acid ester (a-15), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 63, except that 21.19 g (0.042 mol) of diamine compound (HE) was used instead of 24.02 g (0.042 mol) of diamine compound (HC).

[0270] Synthesis Example 66: Synthesis of polyamic acid ester (a-16) A polyamic acid ester (a-16), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 63, except that 13.21 g (0.050 mol) of MCTC was used instead of 15.01 g (0.050 mol) of TDA.

[0271] Synthesis Example 67: Synthesis of polyamic acid ester (a-17) A polyamic acid ester (a-17), which is one form of polyimide, was obtained in the same manner as in Synthesis Example 66, except that DMIB was used instead of MPA as the solvent.

[0272] Synthesis Example 68: Synthesis of polyamic acid ester (a-18) A polyamic acid ester (a-18), which is one form of polyimide, was obtained in the same manner as in Synthesis Example 66, except that DMPA was used as the solvent instead of MPA.

[0273] Synthesis Example 69: Synthesis of polyamic acid ester (a-19) A polyamic acid ester (a-19), which is one form of polyimide, was obtained in the same manner as in Synthesis Example 66, except that GBL was used instead of MPA as the solvent.

[0274] Synthesis Example 70: Synthesis of polyamic acid (a-20) Polyamic acid (a-20), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 52, except that 15.51 g (0.050 mol) of ODPA (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 7.51 g (0.025 mol) of TDA and 7.76 g (0.025 mol) of ODPA.

[0275] Synthesis Example 71: Synthesis of Polyimide (a-21) Under a dry nitrogen stream, 13.0 g (0.042 mol) of the diamine compound (DAP-A) obtained in Synthesis Example 3 and 0.62 g (0.0025 mol) of SiDA were dissolved in 95 g of MPA. To this solution, 7.51 g (0.025 mol) of TDA and 7.76 g (0.025 mol) of ODPA were added along with 10 g of MPA, and the mixture was stirred at 60°C for 2 hours. Then, 1.09 g (0.010 mol) of MAP was added as an end-capping agent along with 10 g of MPA, and the mixture was allowed to react at 60°C for 1 hour. The mixture was then stirred at 180°C for 4 hours. After stirring, the solution was poured into 2 L of deionized water, yielding a white precipitate. The precipitate was collected by filtration, washed three times with deionized water, and then dried in a vacuum dryer at 50° C. for 72 hours to obtain a powder of polyimide (a-21).

[0276] Synthesis Example 72: Synthesis of polyamic acid (a-22) Polyamic acid (a-22), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 51, except that 10.72 g (0.042 mol) of BAP was used instead of the diamine compound (DAP-A).

[0277] Synthesis Example 73: Synthesis of polyamic acid ester (a-23) Polyamic acid ester (a-23), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 63, except that 25.09 g (0.042 mol) of diamine compound (HA) was used instead of 24.02 g (0.042 mol) of diamine compound (HC).

[0278] Synthesis Example 74: Synthesis of polyamic acid ester (a-24) Polyamic acid ester (a-24), which is one form of polyimide, was obtained in the same manner as in Synthesis Example 63, except that 20.86 g (0.042 mol) of diamine compound (HB) was used instead of 24.02 g (0.042 mol) of diamine compound (HC).

[0279] Synthesis Example 75: Synthesis of polyamic acid ester (a-25) A polyamic acid ester (a-25), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 63, except that 15.5 g (0.050 mol) of ODPA was used instead of 15.0 g (0.050 mol) of TDA.

[0280] Synthesis Example 76: Synthesis of polyamic acid ester (a-26) Polyamic acid ester (a-26), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 75, except that 13.4 g (0.039 mol) of diamine compound (DAP-B) and 1.46 g (0.0025 mol) of diamine compound (HC) were used instead of 24.02 g (0.042 mol) of diamine compound (HC).

[0281] Synthesis Example 77: Synthesis of polyamic acid ester (a-27) Polyamic acid ester (a-27), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 75, except that 12.6 g (0.037 mol) of diamine compound (DAP-B) and 2.93 g (0.0051 mol) of diamine compound (HC) were used instead of 24.02 g (0.042 mol) of diamine compound (HC).

[0282] Synthesis Example 78: Synthesis of polyamic acid ester (a-28) Polyamic acid ester (a-28), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 75, except that 10.0 g (0.029 mol) of diamine compound (DAP-B) and 7.32 g (0.013 mol) of diamine compound (HC) were used instead of 24.02 g (0.042 mol) of diamine compound (HC).

[0283] Synthesis Example 79: Synthesis of polyamic acid ester (a-29) Polyamic acid ester (a-29), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 75, except that 7.41 g (0.022 mol) of diamine compound (DAP-B) and 11.7 g (0.020 mol) of diamine compound (HC) were used instead of 24.02 g (0.042 mol) of diamine compound (HC).

[0284] Synthesis Example 80: Synthesis of polyamic acid ester (a-30) Polyamic acid ester (a-30), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 75, except that 5.17 g (0.015 mol) of diamine compound (DAP-B) and 15.5 g (0.027 mol) of diamine compound (HC) were used instead of 24.02 g (0.042 mol) of diamine compound (HC).

[0285] Synthesis Example 81: Synthesis of polyamic acid ester (a-31) Polyamic acid ester (a-31), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 75, except that 3.45 g (0.010 mol) of diamine compound (DAP-B) and 18.4 g (0.032 mol) of diamine compound (HC) were used instead of 24.02 g (0.042 mol) of diamine compound (HC).

[0286] Synthesis Example 82: Synthesis of polyamic acid ester (a-32) Polyamic acid ester (a-32), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 75, except that 8.80 g (0.029 mol) of diamine compound (DAP-C) and 7.35 g (0.013 mol) of diamine compound (HC) were used instead of 24.02 g (0.042 mol) of diamine compound (HC).

[0287] Synthesis Example 83: Synthesis of polyamic acid ester (a-33) Polyamic acid ester (a-33), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 75, except that 9.98 g (0.029 mol) of diamine compound (DAP-B) and 6.84 g (0.013 mol) of diamine compound (HD) were used instead of 24.02 g (0.042 mol) of diamine compound (HC).

[0288] Synthesis Example 84: Synthesis of polyamic acid ester (a-34) Polyamic acid ester (a-34), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 75, except that 8.80 g (0.029 mol) of diamine compound (DAP-C) and 6.31 g (0.013 mol) of diamine compound (HB) were used instead of 24.02 g (0.042 mol) of diamine compound (HC).

[0289] Synthesis Example 85: Synthesis of polyamic acid ester (a-35) Polyamic acid ester (a-35), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 75, except that 7.57 g (0.029 mol) of BAP and 7.35 g (0.013 mol) of the diamine compound (HC) were used instead of 24.02 g (0.042 mol) of the diamine compound (HC).

[0290] Synthesis Example 86: Synthesis of polyamic acid ester (a-36) Polyamic acid ester (a-36), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 78, except that 1.17 g (0.010 mol) of 4-APA was used instead of 1.09 g (0.010 mol) of MAP.

[0291] Synthesis Example 87: Synthesis of polyamic acid ester (a-37) Polyamic acid ester (a-37), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 75, except that 9.98 g (0.029 mol) of diamine compound (DAP-B), 7.00 g (0.012 mol) of diamine compound (HC), and 0.15 g (0.00051 mol) of TPE-R were used instead of 24.02 g (0.042 mol) of diamine compound (HC).

[0292] Synthesis Example 88: Synthesis of polyamic acid ester (a-38) Polyamic acid ester (a-38), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 75, except that 9.98 g (0.029 mol) of diamine compound (DAP-B), 5.84 g (0.010 mol) of diamine compound (HC), and 0.74 g (0.0025 mol) of TPE-R were used instead of 24.02 g (0.042 mol) of diamine compound (HC).

[0293] Synthesis Example 89: Synthesis of polyamic acid ester (a-39) Polyamic acid ester (a-39), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 75, except that 9.12 g (0.027 mol) of diamine compound (DAP-B), 4.39 g (0.0076 mol) of diamine compound (HC), and 2.22 g (0.0076 mol) of TPE-R were used instead of 24.02 g (0.042 mol) of diamine compound (HC).

[0294] Synthesis Example 90: Synthesis of polyamic acid ester (a-40) Polyamic acid ester (a-40), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 75, except that 7.42 g (0.022 mol) of diamine compound (DAP-B), 4.39 g (0.0076 mol) of diamine compound (HC), and 3.71 g (0.013 mol) of TPE-R were used instead of 24.02 g (0.042 mol) of diamine compound (HC).

[0295] Synthesis Example 91: Synthesis of polyamic acid ester (a-41) Polyamic acid ester (a-41), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 75, except that 6.54 g (0.019 mol) of diamine compound (DAP-B), 4.39 g (0.0076 mol) of diamine compound (HC), and 4.44 g (0.015 mol) of TPE-R were used instead of 24.02 g (0.042 mol) of diamine compound (HC).

[0296] Synthesis Example 92: Synthesis of polyamic acid ester (a-42) Polyamic acid ester (a-42), a form of polyimide, was obtained in the same manner as in Synthesis Example 88, except that 0.74 g (0.0025 mol) of TPE-R was replaced with 0.51 g (0.0025 mol) of 3,4′-ODA.

[0297] Synthesis Example 93: Synthesis of polyamic acid ester (a-43) Polyamic acid (a-43), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 70, except that 9.98 g (0.029 mol) of diamine compound (DAP-B) and 7.35 g (0.013 mol) of HC were used instead of 14.13 g (0.042 mol) of diamine compound (DAP-B).

[0298] Synthesis Example 94: Synthesis of polyamic acid ester (a-44) Polyamic acid ester (a-44), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 78, except that DMIB was used as the solvent instead of MPA.

[0299] Synthesis Example 95: Synthesis of polyamic acid ester (a-45) A polyamic acid ester (a-45), which is one form of polyimide, was obtained in the same manner as in Synthesis Example 78, except that GBL was used instead of MPA as the solvent.

[0300] Synthesis Example 96: Synthesis of polyamic acid ester (a-46) After stirring was completed, the solution was poured into 2 L of a mixed solution of deionized water and methanol (1 / 1, weight ratio), and the precipitate of a polymer solid was collected by filtration. The precipitate was further washed three times with 2 L of a mixed solution of deionized water and methanol (1 / 1, weight ratio), and the collected polymer solid was dried in a vacuum dryer at 50°C for 72 hours in the same manner as in Synthesis Example 63, to obtain polyamic acid ester (a-46), which is a form of polyimide.

[0301] Synthesis Example 97: Synthesis of polyamic acid ester (a-47) Polyamic acid ester (a-47), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 63, except that 24.60 g (0.043 mol) of diamine compound (HC) was used and MAP, which was an end-capping agent, was not used.

[0302] Synthesis Example 98: Synthesis of polyamic acid (a-48) Polyamic acid (a-48), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 52, except that 7.66 g (0.025 mol) of HBPDA was used instead of 7.51 g (0.025 mol) of TDA.

[0303] Synthesis Example 99: Synthesis of polyamic acid (a-49) Polyamic acid (a-49), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 51, except that 12.53 g (0.042 mol) of the diamine compound (DAP-J) obtained in Synthesis Example 17 was used instead of the diamine compound (DAP-A).

[0304] Synthesis Example 100: Synthesis of polyamic acid (a-50) Polyamic acid (a-50), which is a form of polyimide, was obtained in the same manner as in Synthesis Example 51, except that 14.89 g (0.042 mol) of the diamine compound (DAP-K) obtained in Synthesis Example 18 was used instead of the diamine compound (DAP-A).

[0305] Tables 1-1 to 1-4 show the measurement results of the constituent components (molar ratio), molecular weight (Mw), esterification rate [%], imide ring closure rate [%], amount of components with a molecular weight of 1,000 or less, and content [parts by mass] of the compounds represented by formula (17) and formula (18) in Synthesis Examples 51 to 100.

[0306]

[0307]

[0308]

[0309]

[0310] [Example 1] Under yellow light, 4.07 g of polyamic acid ester (a-1) as the resin (A) component, 0.488 g of QD-a and 0.488 g of QD-b as the photoacid generator (B1) as the photosensitizer (B), 0.814 g of HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.; a compound represented by the following formula (44)) as the crosslinker (E), and 0.004 g of BYK-302 (manufactured by BYK Japan KK) as the surfactant (F) were added to 28.6 g of a mixed solvent in which the mass ratio of PGME, ethyl lactate, and GBL, which is the solvent (C2), was 35:35:30, and the mixture was stirred for 30 minutes to dissolve the mixture, resulting in a homogeneous solution with a solid content of 18.0% by mass.

[0311]

[0312] Thereafter, the obtained solution was filtered through a 0.45 μmφ filter to obtain a photosensitive resin composition 1. Next, using the obtained photosensitive resin composition 1, various evaluations were carried out by each of the measurement and evaluation methods (6) to (14).

[0313] [Examples 2 to 46 and Comparative Examples 1 to 5] Photosensitive resin compositions 2 to 51, cured films, and organic EL display devices were produced in the same manner as in Example 1, except that photosensitive resin compositions were prepared according to the formulations shown in Tables 2-1 to 2-4. The evaluation results are summarized in Tables 3-1 to 3-4.

[0314]

[0315]

[0316]

[0317]

[0318] The ingredients listed in the table above are as follows: Resin (A) (a-1) to (a-12), (a-20), (a-22), (a-43), (a-48) to (a-50): the polyamic acid resin described above (a-13) to (a-19), (a-23) to (a-42), (a-44) to (a-47): the polyamic acid ester resin described above (a-21): the polyimide resin described above Photosensitizer (B) (b-1): QD-a (compound described in Synthesis Example 1) (b-2): QD-b (compound described in Synthesis Example 2) Solvent (C) (c-1): MPA (c-2): DMIB (c-3): DMPA (c-4): PGME (solvent having a hydroxyl group and a boiling point of 120 ° C. at atmospheric pressure) (c-5): ethyl lactate (solvent having a hydroxyl group and a boiling point of 154 ° C. at atmospheric pressure) (c-6): GBL Crosslinking agent (E) (e-1): HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.) Surfactant (F) (f-1): BYK-302 (manufactured by BYK Japan KK).

[0319]

[0320]

[0321]

[0322]

[0323] The above results indicate that the photosensitive resin compositions of the examples have excellent thinner solubility, high sensitivity, little development residue, and reduced contamination of openings after curing, resulting in excellent reliability of the organic EL display devices. Comparative Examples 1, 3, 4, and 5 showed poor thinner solubility because the resin (A) did not contain a diamine residue represented by any of formulas (2) to (4). Comparative Example 2 showed contamination of openings after curing because the resin (A) did not contain a diamine residue represented by any of formulas (2) to (4) but contained a fluorine-containing diamine residue. Furthermore, when a pixel division layer was formed on top of a planarization layer to fabricate an organic EL display device, bubbles were observed between the planarization layer and the pixel division layer. This is believed to be due to the generation of gases, such as water, from the planarization layer during the heat-curing process of the pixel division layer.

[0324] DESCRIPTION OF SYMBOLS 1: Stepped substrate 2: Cured product 3: Base line 4: Alkali-free glass substrate 5: Planarizing layer 6: Metal reflective layer 7: First electrode 8: Auxiliary electrode 9: Patterned cured film 10: Organic EL layer 11: Second electrode

Claims

1. A photosensitive resin composition comprising a resin (A) (hereinafter referred to as resin (A)) containing at least one of a structural unit represented by formula (1), a structural unit represented by formula (19), and a structural unit represented by formula (70), a photosensitizer (B), and a solvent (C), wherein the total content of diamine residues represented by any of formulas (2) to (4) is 30 to 100 mol % when the total amount of diamine residues in the resin (A) is taken as 100 mol %. (In formula (1), formula (19) and formula (70), Y １ each independently represents an acid dianhydride residue having 2 to 40 carbon atoms, which has any one of an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 40 carbon atoms, and an aromatic structure having 6 to 40 carbon atoms. １ R each independently represents a diamine residue represented by any one of formulas (2) to (4). １ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a monovalent group having 2 to 20 carbon atoms and an ethylenically unsaturated double bond. * represents a bonding site. (In formulas (2), (3) and (4), X １ are each independently a direct bond or a divalent group represented by formula (5), and R ２ each independently represents an alkyl group having 1 to 4 carbon atoms; X ２ is a divalent group represented by formula (6) or (7), each k independently represents 0 or 1, and * represents a bonding point to bond to the imide structure, amide structure, amic acid ester structure, or amic acid structure. (In formula (5), * represents the point of attachment to the nitrogen atom, and ** represents the point of attachment to the aromatic ring.) (In formulas (6) and (7), R ３ each independently represents an alkyl group having 1 to 4 carbon atoms, a represents 1 or 2, b represents an integer of 1 to 3, R ４ and R ５ each independently represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and * represents the point of attachment to the aromatic ring. ４ and R ５ do not have the same structure.) 2. The resin (A) contains a diamine residue represented by formula (2), and in formula (6), the R ３ The total number of carbon atoms in the formula (7) is 1 or more and 5 or less, and ４ and the number of carbon atoms in R ５ The photosensitive resin composition according to claim 1 , wherein the total number of carbon atoms in the group is 3 or more and 10 or less.

3. The resin (A) contains a diamine residue represented by formula (2), and satisfies conditions 1 and 2 when formula (6) is formula (6-1) when a = 1 and formula (6-2) when a = 2 in formula (6), and satisfies conditions 1 and 2 when formula (7) is formula (7-1) when a = 1 and formula (6-2) when a = 2 in formula (6). ４ and the number of carbon atoms in R ５ The photosensitive resin composition according to claim 1 or 2, wherein the number of carbon atoms in R １１ ~R １４ The total number of carbon atoms in R １５ ~R １８ Condition 2: In formula (6-2), the total number of carbon atoms in R １９ ~R ２２ The total number of carbon atoms in R ２５ ~R ２８ The total number of carbon atoms is different. (In formula (6-1) and formula (6-2), R １１ ~R ２８ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, both formula (6-1) and formula (6-2) satisfy the conditions of formula (6).

4. The resin (A) contains a diamine residue represented by formula (2), and the X ２ is a divalent group represented by any one of formulas (8) to (13) and (76) to (83). (In formulas (8) to (13) and (76) to (83), * represents the point of attachment to the aromatic ring.) 5. In the formula (1), formula (19) and formula (70), Y １ each independently represent an acid dianhydride residue having a diphenyl ether structure and having 8 to 40 carbon atoms.

6. The photosensitive resin composition according to claim 1 or 2, wherein the resin (A) has a structure represented by formula (84). (In formula (84), R ２９ indicates a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms. * indicates the bonding site with the nitrogen atom.) 7. The photosensitive resin composition according to claim 1 or 2, wherein the resin (A) contains the structural unit (a) and / or the structural unit (b), and the resin (A) contains the structural unit (c) and / or the structural unit (d), and the resin (A) contains at least one of the structural unit (a) and the structural unit (c). Structural unit (a): Z in formula (1), formula (19), and formula (70). １ is expressed by formula (2), and the two X １ and Z are both direct bonds. Structural unit (b): In formula (48), formula (49) and formula (71), Z ３ is expressed by the formula (45), and the two X １ and (c) a structural unit represented by the formula (1), (19) or (70), wherein Z １ is expressed by formula (2), and the two X １ At least one of the X １ is a divalent group represented by formula (5). Structural unit (d): In formula (48), formula (49) and formula (71), Z ３ is expressed by the formula (45), and the two X １ At least one of the X １ is a divalent group represented by formula (5), (In formula (48), formula (49) and formula (71), Y １ and R １ is in the same range as that explained in Equation (1), Equation (19) and Equation (70). ３ each independently represents a diamine residue represented by formula (45). * represents a bond. (In formula (45), X １ are each independently a direct bond or a divalent group represented by formula (5), and R ２ and k are in the same range as described in formula (2). ３ represents a divalent organic group represented by any one of formulas (64) to (69). * represents a bonding point that bonds to an imide structure, an amide structure, an amic acid ester structure, or an amic acid structure. (* represents the point of attachment to the aromatic ring.) 8. The photosensitive resin composition according to claim 7, wherein, when the total amount of polyimide structural units contained in said resin (A) is taken as 100 mol %, the total content of said structural units (a) and said structural units (b) is 20 to 95 mol %, and the total content of said structural units (c) and said structural units (d) is 5 mol % to 80 mol %.

9. The photosensitive resin composition according to claim 1 or 2, wherein the resin (A) further contains at least one of a structural unit represented by formula (50), a structural unit represented by formula (51), and a structural unit represented by formula (72). (In formula (50), formula (51) and formula (72), Y １ and R １ is in the same range as that described in Equation (1), Equation (19) and Equation (70). ５ each independently represents a diamine residue represented by formula (46) or formula (47). * represents a bond. (In formula (46) and formula (47), X ４ is a direct bond or -C(CH ３ ) ２ -. t represents an integer of 0 to 2. * represents a bonding point to bond to an imide structure, an amide structure, an amic acid ester structure, or an amic acid structure.

10. The photosensitive resin composition according to claim 9, wherein the total content of the structural unit represented by formula (50), the structural unit represented by formula (51), and the structural unit represented by formula (72) is 1 to 30 mol %, when the total amount of the polyimide structural units contained in the resin (A) is 100 mol %.

11. The photosensitive resin composition according to claim 1 or 2, wherein the resin (A) contains an acid dianhydride residue having 4 to 20 carbon atoms and containing an alicyclic structure.

12. The photosensitive resin composition according to claim 11, wherein the total content of acid dianhydride residues having 4 to 20 carbon atoms and containing an alicyclic structure is 20 to 100 mol % when the total amount of acid dianhydride residues in the resin (A) is taken as 100 mol %.

13. The photosensitive resin composition according to claim 11, wherein the resin (A) contains one or more acid dianhydride residues selected from the group consisting of formulae (15), (16), and (85) to (94). (In formulas (15), (16), and (85) to (94), * represents a bonding point to the imide structure, amide structure, amic acid ester structure, or amic acid structure.) 14. The photosensitive resin composition according to claim 1 or 2, wherein the imide ring closure rate of the resin (A) is 50% or less.

15. The photosensitive resin composition according to claim 1 or 2, wherein the esterification rate of the resin (A) is 10% or more and 100% or less.

16. The photosensitive resin composition according to claim 1 or 2, wherein the solvent (C) contains a solvent represented by formula (17) and / or a solvent (C1) represented by formula (18). (In formulas (17) and (18), R ６ each independently represents an alkyl group having 1 to 6 carbon atoms; R ７ represents an alkyl group having 2 to 6 carbon atoms.

17. The photosensitive resin composition according to claim 1 or 2, wherein the solvent (C) includes a solvent (C2) having a hydroxyl group and a boiling point at atmospheric pressure of 100°C or higher and 200°C or lower.

18. The photosensitive resin composition according to claim 1 or 2, wherein the photosensitive resin composition contains both a solvent represented by formula (17) and / or a solvent (C1) represented by formula (18) (hereinafter referred to as solvent (C1)), and a solvent (C2) having a hydroxyl group and having a boiling point at atmospheric pressure of 100°C or more and 200°C or less (hereinafter referred to as solvent (C2)), and wherein the content ratio Y / X, where X (mass) is the content of solvent (C1) and Y (mass) is the content of solvent (C2) in the photosensitive resin composition, is 1 or more and 1,000 or less.

19. A cured product obtained by curing the photosensitive resin composition according to claim 1 or 2.

20. A display device comprising the cured product according to claim 19.

21. An electronic component comprising the cured product according to claim 19.

Images