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 diluent, can suppress contamination of an opening after curing, can suppress foaming during lamination, and can provide a cured product having good light-emitting characteristics even after a reliability test; a cured product obtained by curing the photosensitive resin composition; and a display device and an electronic component including a cured product of the resin composition. This photosensitive resin composition contains a resin (A) (hereinafter referred to as resin (A)) containing a specific structural unit, a photosensitizer (B), and a solvent (C), and the total content of specific diamine residues is 30-100 mol% when the total amount of the diamine residues in the resin (A) is 100 mol%.

Description

Technical Field

[0001] This invention relates to a photosensitive resin composition, a cured material, a display device, and electronic components. Background Technology

[0002] Previously, photosensitive polyimide and / or photosensitive polybenzoxazole, which have excellent heat resistance, electrical insulation, mechanical properties, etc., and can be patterned by photolithography, have been widely used in the stacked layers of organic electroluminescence (EL) display devices, planarization layers of thin film transistor (TFT) substrates, surface protective films of semiconductor elements, or interlayer insulating films of electronic components. Many solutions have been proposed to date (for example, see Patent Document 1 and Patent Document 2).

[0003] In obtaining films with excellent heat resistance and mechanical properties by thermally dehydrating and closing the ring-chain of polyimide or polybenzoxazole resin coatings, a high-temperature calcination of around 350°C is typically required. Furthermore, the process of thermally dehydrating and closing the ring-chain of polyimide or polybenzoxazole resin coatings to obtain films with excellent heat resistance and mechanical properties is sometimes referred to as calcination (curing), and the change in the coating is called hardening. Moreover, from the perspective of high-temperature resistant processes and semiconductor packaging reliability, the molding resins used in memory devices or semiconductor packaging in recent years, particularly in surface protective films or interlayer insulating films, require polyimide, polybenzoxazole, or polyamide-imide resins that can be hardened by calcination at temperatures below 250°C. This necessitates high mechanical properties, chemical resistance, and adhesion.

[0004] In addition, the requirements for high reliability of organic EL display devices are becoming increasingly stringent year by year. Materials used for planarization layers and insulating layers are required to maintain high luminous properties even after reliability tests under accelerated conditions such as light irradiation.

[0005] Existing photosensitive polyimides and / or photosensitive polybenzoxazoles generally use polyimides, polybenzoxazoles, and their precursors that contain fluorine-containing groups such as trifluoromethyl groups in the resin structure. However, there is a problem that fluorine-containing residues generated during curing or dry etching adhere to the electrodes at the openings, increasing the contact resistance of the electrodes. To address this, methods have been disclosed such as using a fluorine-free organic insulating film (e.g., see Patent Document 3) or using a fluorine-free polyimide precursor with a specific structure introduced into the main chain to balance suppress electrode contamination and increase sensitivity (e.g., see Patent Document 4).

[0006] On the other hand, methods have been disclosed, for example, for providing an organic EL display device with excellent long-term reliability by using a photosensitive resin composition with a sulfur to carbon molar ratio (S / C) within a specific range obtained by measuring the profile of the hardened film using an electron beam microanalyzer (see, for example, Patent Document 5), or for providing a photosensitive resin composition with high sensitivity and soluble in γ-butyrolactone solvent by using a resin with a specific structure that does not contain halogen atoms in its molecule (see, for example, Patent Document 6).

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 2002-91343

[0010] Patent Document 2: Japanese Patent Application Publication No. 2002-116715

[0011] Patent Document 3: Japanese Patent Application Publication No. 2009-177113

[0012] Patent Document 4: Japanese Patent Application Publication No. 2003-76007

[0013] Patent Document 5: International Publication No. 2016 / 047483

[0014] Patent Document 6: International Publication No. 2009 / 081950 Summary of the Invention

[0015] The problem that the invention aims to solve

[0016] However, existing polyimides, polybenzoxazoles, and their precursors that do not contain fluorine-containing groups such as trifluoromethyl have the following problems: poor solubility in organic solvents; even when dissolved in some aprotic polar solvents such as N-methyl-2-pyrrolidone or γ-butyrolactone, their solubility in propylene glycol monomethyl ether, which is widely used in photolithography diluents, is insufficient. The resins disclosed in Patent Documents 3 and 4 also have problems regarding the solubility of propylene glycol monomethyl ether.

[0017] Patent Document 5 discloses a photosensitive resin composition containing a fluorinated polyimide precursor. Our research revealed an issue where contamination was observed at the opening after curing. Furthermore, during the fabrication of an organic EL display device, anomalies caused by foaming easily occurred when forming a pixel segmentation layer on top of the planarization layer. Additionally, our research on the photosensitive resin composition described in Patent Document 6 revealed issues with its solubility in propylene glycol monomethyl ether. Moreover, when fabricating an organic EL display device using the photosensitive resin composition described in Patent Document 6 and conducting reliability evaluations, it was found that the luminescence characteristics could not be maintained after reliability tests under accelerated conditions such as light irradiation. As described above, in reality, a photosensitive resin composition that satisfies all the requirements of diluent solubility, suppression of opening contamination after curing, suppression of foaming during lamination, and good luminescence characteristics after reliability tests is not yet known.

[0018] Therefore, the objective of this invention is to provide a photosensitive resin composition that has good diluent solubility, can suppress contamination at the opening after curing, suppress foaming during lamination, and has good luminescent properties after reliability testing; a cured product formed by curing the photosensitive resin composition; and a display device and electronic component comprising the cured product of the photosensitive resin composition.

[0019] Technical means to solve the problem

[0020] To address the aforementioned issues, the present invention has the following structure.

[0021] [1] A photosensitive resin composition comprising a resin (A) (hereinafter referred to as resin (A)) containing at least one of the structural units represented by formula (1), formula (19), and formula (70), a photosensitizer (B), and a solvent (C).

[0022] When the total amount of diamine residues in the resin (A) is set to 100 mol%, the total content of diamine residues represented by any one of formulas (2) to (4) is 30 mol% to 100 mol%.

[0023] [Chemistry 1]

[0024]

[0025] (In equations (1), (19) and (70), Y) 1 Each of the following can be independently represented: an aliphatic structure with 2–20 carbon atoms, an alicyclic structure with 4–40 carbon atoms, and an aromatic structure with 6–40 carbon atoms, representing an acid dianhydride residue with 2–40 carbon atoms; Z 1Each of the formulas (2) to (4) represents a diamine residue independently; R 1 Each of the following can be independently represented: a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a monovalent group having 2 to 20 carbon atoms with an ethylene-like unsaturated double bond; (Indicates the bonding part)

[0026] [Chemistry 2]

[0027]

[0028] (In equations (2), (3) and (4), X) 1 R is independently a direct bond or a divalent base represented by equation (5). 2 Each of the alkyl groups having 1 to 4 carbon atoms is represented independently, X 2 Let k be the divalent base represented by equation (6) or equation (7), where k independently represents 0 or 1, respectively. (This indicates a bond point that is bonded to an imide structure, amide structure, amide ester structure, or amide acid structure)

[0029] [Chemistry 3]

[0030]

[0031] (in formula (5), Indicates the bond node that bonds with a nitrogen atom; (Represents the bond node with an aromatic ring bond)

[0032] [Chemistry 4]

[0033]

[0034] (In equations (6) and (7), R) 3 Each of the following groups independently represents an alkyl group having 1 to 4 carbon atoms, where a represents 1 or 2, b represents an integer from 1 to 3, and R 4 and R 5 Each can independently represent a hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms. Represents the bond node with an aromatic ring bond; where R 4 With R 5 (Not using the same structure)

[0035] [2] According to the photosensitive resin composition of [1], wherein the resin (A) comprises a diamine residue represented by formula (2), and R in formula (6) 3 The total number of carbons is more than 1 and less than 5, and R in equation (7) is... 4 The number of carbons and the R 5 The total number of carbon atoms is 3 or more and less than 10.

[0036] [3] According to the photosensitive resin composition of [1] or [2], wherein the resin (A) comprises the diamine residue represented by formula (2), and in formula (6) when a=1 is set as formula (6-1) and a=2 is set as formula (6-2), conditions 1 and 2 are satisfied, and in formula (7) the R 4 The number of carbons and the R 5 The number of carbon atoms is different.

[0037] Condition 1: In formula (6-1), R 11 ~R 14 The total number of carbons and R 15 ~R 18 The total number of carbons is different.

[0038] Condition 2: In formula (6-2), R 19 ~R 22 The total number of carbons and R 25 ~R 28 The total number of carbons is different.

[0039] [Chemistry 5]

[0040]

[0041] (In equations (6-1) and (6-2), R) 11 ~R 28 Each of the above can independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; wherein formulas (6-1) and (6-2) both satisfy the conditions of formula (6).

[0042] [4] The photosensitive resin composition according to any one of [1] to [3], wherein the resin (A) comprises a diamine residue represented by formula (2), and the X 2 It is a divalent base represented by any one of equations (8) to (13) and (76) to (83).

[0043] [Chemistry 6]

[0044]

[0045] (In equations (8) to (13) and equations (76) to (83), (Represents the bond node with an aromatic ring bond)

[0046] [5] The photosensitive resin composition according to any one of [1] to [4], wherein, in the formulas (1), (19) and (70), Y 1 Each of the following can be independently represented as an anhydride residue with 8 to 40 carbon atoms having a diphenyl ether structure.

[0047] [6] The photosensitive resin composition according to any one of [1] to [5], wherein the resin (A) has the structure represented by formula (84).

[0048] [Chemistry 7]

[0049]

[0050] (In equation (84), R) 29 It can represent hydroxyl, alkyl with 1 to 3 carbons, alkoxy with 1 to 3 carbons, alkenyl with 2 to 5 carbons, or alkynyl with 2 to 5 carbons; (Indicates the bonding site with the nitrogen atom)

[0051] [7] The photosensitive resin composition according to any one of [1] to [6], wherein the resin (A) comprises structural unit (a) and / or structural unit (b), and the resin (A) comprises structural unit (c) and / or structural unit (d).

[0052] The resin (A) comprises at least one of structural unit (a) and structural unit (c).

[0053] Structural unit (a): Z in equations (1), (19) and (70) 1 The expression is represented by equation (2), and there are two X's in equation (2). 1 All structural units are represented by equations (1), (19), or (70) with direct keys.

[0054] Structural unit (b): Z in equations (48), (49) and (71) 3 The two X's represented by equation (45) and existing in equation (45) 1 All are structural units represented by direct keys, as shown in equations (48), (49), or (71).

[0055] Structural unit (c): Z in equations (1), (19) and (70) 1 The expression is represented by equation (2), and there are two X's in equation (2). 1 At least one X in 1 The structural unit represented by equation (1), equation (19) or equation (70) of the divalent base represented by equation (5)

[0056] Structural unit (d): Z in equations (48), (49) and (71) 3 The two X's represented by equation (45) and existing in equation (45) 1 At least one X in 1 The structural unit represented by equation (48), equation (49) or equation (71) of the divalent base represented by equation (5)

[0057] [Chemistry 8]

[0058]

[0059] (In equations (48), (49) and (71), Y) 1 and R 1 The same range as that described in equations (1), (19), and (70); Z 3 The diamine residues represented by formula (45) are expressed independently; (Indicates the bonding part)

[0060] [Chemistry 9]

[0061]

[0062] (In equation (45), X) 1 R is independently a direct bond or a divalent base represented by equation (5). 2 and k is the same range as that described in equation (2); X 3 The divalent organic group represented by any one of formulas (64) to (69); (This indicates a bond point that is bonded to an imide structure, amide structure, amide ester structure, or amide acid structure)

[0063] [Chemistry 10]

[0064]

[0065] ( (Represents the bond node with an aromatic ring bond)

[0066] [8] According to the photosensitive resin composition of [7], wherein, when the total amount of polyimide structural units contained in the resin (A) is set to 100 mol%, the total content of the structural unit (a) and the structural unit (b) is 20 mol% to 95 mol%, and the total content of the structural unit (c) and the structural unit (d) is 5 mol% to 80 mol%.

[0067] [9] The photosensitive resin composition according to any one of [1] to [8], wherein the resin (A) further comprises at least one of the structural unit represented by formula (50), the structural unit represented by formula (51), and the structural unit represented by formula (72).

[0068] [Chemistry 11]

[0069]

[0070] (In equations (50), (51) and (72), Y)1 and R 1 The same range as that described in equations (1), (19), and (70); Z 5 The diamine residues represented by formula (46) or formula (47) are represented independently, respectively; (Indicates the bonding part)

[0071] [Chemistry 12]

[0072]

[0073] (In equations (46) and (47), X) 4 Indicates a direct bond or -C(CH3)2-; t represents any integer from 0 to 2; (This indicates a bond point that is bonded to an imide structure, amide structure, amide ester structure, or amide acid structure)

[0074]

[10] According to the photosensitive resin composition of [9], wherein when the total amount of polyimide structural units contained in the resin (A) is set to 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 1 mol% to 30 mol.

[0075]

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

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

[0076]

[12] According to the photosensitive resin composition of

[11] , wherein, when the total amount of dianhydride residues of the resin (A) is set to 100 mol%, the total content of dianhydride residues containing alicyclic structures with carbon numbers of 4 to 20 is 20 mol% to 100 mol%.

[0077]

[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 formula (15), formula (16), formula (85) to formula (94).

[0078] [Chemistry 13]

[0079]

[0080] (In equations (15), (16), (85) to (94),) (This indicates a bond point that is bonded to an imide structure, amide structure, amide ester structure, or amide acid structure)

[0081]

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

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

[0082]

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

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

[0083]

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

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

[0084] [Chemistry 14]

[0085]

[0086] (In equations (17) and (18), R) 6 Each alkyl group having 1 to 6 carbon atoms is represented independently.

[0087] R 7 (Indicates alkyl groups having 2 to 6 carbon atoms)

[0088]

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

[16] , wherein the solvent (C) comprises a solvent (C2) having hydroxyl groups and a boiling point of 100°C or higher and 200°C or lower at atmospheric pressure.

[0089]

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

[17] , wherein the photosensitive resin composition comprises a solvent represented by formula (17) and / or a solvent represented by formula (18) (hereinafter referred to as solvent (C1)), and a solvent (C2) having hydroxyl groups and a boiling point of 100°C or higher and 200°C or lower at atmospheric pressure (hereinafter referred to as solvent (C2)).

[0090] The content ratio of solvent (C1) in the photosensitive resin composition to X (mass) and solvent (C2) to Y (mass) is Y / X, where Y / X is 1 or more and 1000 or less.

[0091]

[19] A hardened material is formed by hardening a photosensitive resin composition according to any one of [1] to

[18] .

[0092]

[20] A display device comprising the hardened material according to

[19] .

[0093]

[21] An electronic component comprising the hardened material according to

[19] .

[0094] The effects of the invention

[0095] According to the present invention, a photosensitive resin composition with good diluent solubility, capable of suppressing opening contamination after curing, suppressing foaming during lamination, and exhibiting good luminescent properties after reliability testing, a cured product obtained by curing the photosensitive resin composition, and a display device and electronic component comprising the cured product of the photosensitive resin composition can be obtained. Attached Figure Description

[0096] [ Figure 1 [ ] is a cross-sectional view of the sample used for flatness evaluation.

[0097] [ Figure 2 [Illustration] is a schematic diagram illustrating a method for manufacturing an organic EL display device including a planarization layer and a pixel segmentation layer in an embodiment. Detailed Implementation

[0098] The present invention will now be described in detail.

[0099] In this specification, the numerical range indicated by “~” refers to the range of values ​​recorded before and after “~” as the lower and upper limits.

[0100] In addition, in this specification, polyimide is intended to form an imide ring after the curing operation, and therefore also includes structures that are before the ring is closed into an imide ring, i.e., structures of amic acid (or amic acid) or esters of said acid; polybenzoxazole is intended to form a benzoxazole ring after the curing operation, and therefore also includes structures that are before the ring is closed into an oxazole ring, i.e., structures of hydroxyamide.

[0101] The photosensitive resin composition of the present invention contains a resin (A) (hereinafter referred to as resin (A)) comprising at least one of the structural units represented by formula (1), the structural units represented by formula (19) and the structural units represented by formula (70).

[0102] [Chemistry 15]

[0103]

[0104] In equations (1), (19), and (70), Y 1 Each of the following can be independently represented: an aliphatic structure with 2–20 carbon atoms, an alicyclic structure with 4–40 carbon atoms, or an aromatic structure with 6–40 carbon atoms, representing an acid dianhydride residue with 2–40 carbon atoms. 1 Each of the formulas (2) to (4) represents a diamine residue independently. 1 Each of the following can be independently represented: a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a monovalent group having 2 to 20 carbon atoms with an ethylene-like unsaturated double bond. Indicates the bonding section.

[0105] [Chemistry 16]

[0106]

[0107] In equations (2), (3), and (4), X 1 R is independently a direct bond or a divalent base represented by equation (5). 2 Each of the alkyl groups having 1 to 4 carbon atoms is represented independently, X 2 Let k be the divalent base represented by equation (6) or equation (7), where k independently represents 0 or 1, respectively. This indicates a bond point that is bonded to an imide, amide, amide ester, or amide acid structure.

[0108] [Chemistry 17]

[0109]

[0110] In equation (5), This indicates the bond point that bonds with a nitrogen atom. This indicates the bond node that is bonded to an aromatic ring.

[0111] [Chemistry 18]

[0112]

[0113] In equations (6) and (7), R 3 Each of the following groups independently represents an alkyl group having 1 to 4 carbon atoms, where a represents 1 or 2, b represents an integer from 1 to 3, and R 4 and R 5 Each can independently represent a hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms. This represents the bond node with an aromatic ring bond. Where R... 4 With R 5 They do not use the same structure.

[0114] Formulas (1), (19), and (70) are all structural units of polyimide. Formula (1) represents a structural unit in which the amic acid structure or amic acid ester structure is not closed and all of them are amic acid structures or amic acid ester structures. Formula (19) represents a structural unit in which the amic acid structure or amic acid ester structure is closed and imidized. Formula (70) represents a structural unit in which one amic acid structure or amic acid ester structure is not closed and the other amic acid structure or amic acid ester structure is closed and imidized. By having structural units of formulas (1) and (70) in resin (A), the diluent has good solubility and can reduce residue. In addition, by having structural units of formula (19) in resin (A), the amount of gas escaped from the hardened product obtained by hardening the photosensitive resin composition at high temperature can be reduced, or foaming during lamination can be suppressed. When the number of structural units represented by formula (1), formula (19), and formula (70) in resin (A) is set to p, q, and r respectively, p+q+r is an integer of 1 or more, preferably p≧1 or r≧1. In addition, when the total number of structural units of polyimide constituting resin (A) is set to 100 mol%, the total number of structural units represented by formula (1), formula (19), and formula (70) is preferably 30 mol% to 100 mol%, more preferably 40 mol% to 100 mol%, and even more preferably 50 mol% to 100 mol%, particularly preferably 60 mol% to 100 mol%. By using the ratio of structural units of formula (1), formula (19), and formula (70) within the range described, a photosensitive resin composition with good solvent solubility, capable of suppressing opening contamination after curing, and suppressing foaming during lamination can be obtained. The structural unit of polyimide referred to herein is a structural unit that is intended to form an imide ring after the curing operation. It also includes structures that are before the ring is closed into an imide ring, i.e., structures of amic acid (or amic acid) or esters of said acid. Specifically, in this application, the structural unit of polyimide is represented by formulas (73), (74) and (75).

[0115] [Chemistry 19]

[0116]

[0117] In equations (73), (74), and (75), Y 10 Each represents an acid dianhydride residue independently. Z 10 Each residue represents a diamine residue independently. R 10 Each can be used to independently represent a hydrogen atom or a monovalent group. Indicates the bonding section.

[0118] In terms of obtaining a heat-resistant cured product, it is preferable to have a polybenzoxazole structural unit when the resin (A) has a structural unit other than polyimide. When the structural unit includes polybenzoxazole, it is preferable to have one or more of the group consisting of, for example, the structural unit represented by formula (38), the structural unit represented by formula (39), and the structural unit represented by formula (40).

[0119] [Chemistry 20]

[0120]

[0121] In equations (38), (39), and (40), Y 3 Y 4 Y 5 Z represents a dicarboxylic acid residue. 3 Z 4 Z 5 This indicates a diaminophenol residue. A dicarboxylic acid residue is a residue obtained by removing two carboxyl groups from a dicarboxylic acid compound. A diaminophenol residue is a residue obtained by removing two amino groups and two hydroxyl groups from a diaminophenol compound.

[0122] Equation (38) represents a structural unit in which all hydroxyamide structures are closed-loop and oxazoleized. Equation (39) represents a structural unit in which some hydroxyamide structures are closed-loop and oxazoleized, and some become hydroxyamide structures. Equation (40) represents a structural unit in which all hydroxyamide structures are not closed-loop and become hydroxyamide structures.

[0123] When resin (A) contains structural units other than polyimide, the total amount of polyimide structural units in resin (A) is preferably 50 mol% to 100 mol%, more preferably 65 mol% to 100 mol%, and even more preferably 80 mol% to 100 mol% of the total amount of all structural units contained in resin (A). By including polyimide structural units in the aforementioned ratio, a cured material with good reliability and excellent heat resistance can be obtained.

[0124] The imide ring closure rate of resin (A) is preferably 90% or less, more preferably 80% or less, and even more preferably 50% or less. Within this range, residue can be reduced, and the alkaline development rate can be within a preferred range, thus enabling the acquisition of a good pattern shape. In particular, when the imide ring closure rate of resin (A) is 50% or less, the solvent solubility of resin (A) becomes good, suppressing the aggregation of resin (A) during storage. As a result, the storage stability of the photosensitive resin composition is improved, which is therefore preferred. The imide ring closure rate of resin (A) is determined by a method described later.

[0125] 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. By maintaining the esterification rate within the aforementioned range, residue can be reduced, and a photosensitive resin composition with excellent diluent solubility can be obtained. The esterification rate of resin (A) is determined by the method described later.

[0126] In addition, R in equation (1) 1 Preferably, each is an alkyl group having 1 to 10 carbon atoms, or a monovalent organogroup having an ethylene-unsaturated double bond; more preferably, it is an alkyl group having 1 to 3 carbon atoms, or a monovalent organogroup having an ethylene-unsaturated double bond. Through R 1 The alkyl group having 1 to 10 carbon atoms, or a monovalent organic group having an ethylene-like unsaturated double bond, allows for adjustment of solubility in the developer to a preferred range, thus enabling the acquisition of good pattern shapes. Furthermore, in R... 1 In the case of a monovalent organic group having an ethylene-unsaturated double bond, in addition to the above, crosslinking during heat curing can improve elongation at break and chemical resistance, and is therefore preferred. Specifically, examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, and hexyl. Examples of monovalent organic groups having an ethylene-unsaturated double bond include 2-hydroxyethyl methacrylate (hereinafter HEMA) or the structure of 2-hydroxyethyl acrylate after removing the hydroxyl group.

[0127] In equations (1), (19), and (70), Y 1 Each of these terms independently represents an acid dianhydride residue with 2 to 40 carbon atoms in any of the following structures: aliphatic (2-20 carbons), alicyclic (4-40 carbons), or aromatic (6-40 carbons). An acid dianhydride residue refers to the residue remaining after removing two acid anhydride structures from an acid dianhydride compound.

[0128] As Y 1Specific examples 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-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, 2,3,5-tricarboxy-2-cyclopentaneacetic dianhydride, and bicyclo[2.2.2]oct-7-ene-2, Residues of alicyclic tetracarboxylic dianhydrides such as 3,5,6-tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 3,5,6-tricarboxy-2-norborneneacetic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)naphthalene[1,2-c]furan-1,3-dione, and 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride,

[0129] Pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1 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.

[0130] Or bis(3,4-dicarboxyphenyl)sulfone dianhydride, 4,4'-oxyphthalic anhydride, 3,4'-oxyphthalic anhydride, 3,3'-oxyphthalic anhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 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)propane dianhydride Residues of aromatic acid dianhydrides, such as 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, or compounds in which the aromatic rings of these compounds are substituted with alkyl or halogen atoms, and acid dianhydrides having amide groups.

[0131] In equations (1), (19), and (70), Y 1 Preferably, each residue represents an 8-40 carbon atom of an acid dianhydride having a diphenyl ether structure. By satisfying these conditions, the cured product obtained by curing the photosensitive resin composition also exhibits good luminescent properties after reliability testing. Ya is an 8-40 carbon atom of an acid dianhydride having a diphenyl ether structure. 1 Specific examples 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, and 4,4'-(1,4-phenylenedioxy)diphthalic anhydride.

[0132] The resin (A) is preferably composed of dianhydride residues with 4 to 20 carbon atoms that have an alicyclic structure. That is, Y 1 Preferably, it contains 4-20 carbon alicyclic dianhydride residues. (The text abruptly ends here, likely due to an incomplete sentence or missing information.) 1 It is a photosensitive resin composition containing 4 to 20 carbon dianhydride residues with an alicyclic structure, which can produce a hardened material with good sensitivity, small coloration in the visible light region, and high transmittance.

[0133] Furthermore, when the total amount of dianhydride residues in the resin (A) is set to 100 mol%, the total content of dianhydride residues containing alicyclic structures with 4 to 20 carbon atoms is preferably 20 mol% to 100 mol%, more preferably 30 mol% to 100 mol.

[0134] Furthermore, it is preferable to include one or more dianhydride residues selected from the group consisting of formulas (15), (16), and (85) to (94) as the dianhydride residues containing an alicyclic structure with 4 to 20 carbon atoms. Preferably, it includes dianhydride residues represented by formula (15) and / or formula (16). The dianhydride residues represented by formula (15) are residues obtained by removing two anhydride structures from 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)naphthalene[1,2-c]furan-1,3-dione, and the dianhydride residues represented by formula (16) are residues obtained by removing two anhydride structures from 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride. By including these anhydride residues, a photosensitive resin composition with particularly excellent diluent solubility and low residue can be obtained.

[0135] [Chemistry 21]

[0136]

[0137] In equations (15), (16), and (85) to (94), This indicates a bond point that is bonded to an imide, amide, amide ester, or amide acid structure.

[0138] When the total amount of diamine residues in a resin (A) containing at least one of the structural units represented by formula (1), formula (19), and formula (70) is set to 100 mol%, the total content of diamine residues represented by any one of formulas (2) to (4) is 30 mol% to 100 mol%. That is, in formulas (1), (19), and (70), Z 1 Each of the diamine residues represented by any one of formulas (2) to (4) is represented independently. A diamine residue refers to the structure after removing two amino groups from a diamine compound. Each of the diamine residues represented by any one of formulas (2) to (4) has a phenolic hydroxyl group, which can impart solubility to alkaline developing solutions and reduce developing residue. In addition, by having diamine residues represented by any one of formulas (2) to (4), intermolecular stacking can be suppressed, and the solubility of the diluent can be improved. Furthermore, since it is a fluorine-free structure, it can suppress contamination at the opening after curing and suppress foaming during lamination.

[0139] While the detailed mechanism by which opening contamination after curing and foaming during lamination can be suppressed by including diamine residues represented by any of formulas (2) to (4) is not clear, the principle by which the aforementioned effects can be obtained is speculated as follows. For example, in the case of using a polyimide containing a fluorinated diamine as described in International Publication No. 2016 / 047483, it is believed that during the heat curing process, the hexafluoroisopropylidene undergoes thermal decomposition, and the fluorinated hydrocarbon group adheres to the opening, causing opening contamination. On the other hand, the diamine residues represented by any of formulas (2) to (4) are all fluorine-free structures, and therefore do not cause opening contamination caused by the fluorinated hydrocarbon group, resulting in the suppression of opening contamination after curing. In addition, in the case of using a polyimide containing a fluorinated diamine, since fluorine is an electron-attracting group, it is believed that the imide ring-closing reaction is suppressed during heat curing. As a result, it is believed that during the specified heat curing process, the imide ring-closing reaction is not completed, and the amic acid structure remains in the film. Since the remaining amyl acid structure gradually undergoes imide ring closure during the additional heating process, producing water, it is believed to cause foaming during the formation of the laminate and to contribute to the reduced reliability of the organic EL display device. On the other hand, the diamine residues represented by any of formulas (2) to (4) are all non-fluorinated structures, thus undergoing rapid imide ring closure during the heat curing process, leaving almost no amyl acid structure remaining in the film after the heat curing process. As a result, it is speculated that foaming or reduced reliability can be suppressed.

[0140] In equations (2), (3), and (4), X 1 Each is independently a direct bond or a divalent base represented by equation (5). Through X 1 The direct bond allows for an increase in the hydroxyl concentration of resin (A), thus reducing residue after development, and is therefore preferred. Furthermore, through X... 1 The divalent organic group represented by formula (5) forms a hydroxyamide structure as a precursor of benzoxazole in the structure of formula (2). Therefore, during the curing process, the hydroxyamide closes its ring to become an oxazole ring, resulting in a cured product with low water absorption, which is therefore preferred. In formulas (2), (3), and (4), R 2 Each alkyl group has 1 to 4 carbon atoms and can be represented independently. Among these, R... (The sentence is incomplete and requires more context to translate accurately.) 2 Preferably, it is methyl. In formula (2), X 2 R is the divalent base represented by equation (6) or equation (7), where R is the base in equation (6) and equation (7). 3 Each of the following groups independently represents an alkyl group having 1 to 4 carbon atoms, where a represents 1 or 2, b represents an integer from 1 to 3, and R 4 and R 5 Each of these groups independently represents a hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms. Wherein, R... 4 With R 5 The same structure is not used. By including the structure represented by formula (6) or formula (7), intermolecular stacking can be suppressed and the solubility of the diluent can be improved. Among them, the structure represented by formula (7) is preferred in terms of further improving the chemical resistance of the cured product obtained by curing the photosensitive resin composition. R 3 The alkyl group, having 1 to 4 carbon atoms, is preferably methyl, as it improves the heat resistance of resin (A) and reduces developer residue. The use of 'a' to represent 1 or 2 and 'b' to represent an integer of 1 to 3 allows for a balance between the heat resistance of resin (A) and the solubility in the diluent, thus making it preferable. 4 and R 5 Representing hydrocarbon groups or hydrogen atoms with 1 to 10 carbon atoms independently can improve the heat resistance of resin (A) and reduce developing residue. 4 R 5 Preferably, each group is an independently saturated hydrocarbon group having 1 to 10 carbon atoms, more preferably an saturated hydrocarbon group having 1 to 8 carbon atoms. Wherein, R 4 With R 5 Do not use the same structure. The "do not use the same structure" shown here, besides including R... 4 With R 5 Besides those with different compositional formulas, the relationship also includes structural isomers with the same compositional formula but different bonding states between atoms. (Through R...)4 With R 5 By not using the same structure, the diluent solubility of resin (A) can be improved. In formula (2), k independently represents 0 or 1. It is preferred that k is 0, which can reduce developing residue. In addition, it is preferred that k=1, which can obtain a photosensitive resin composition with good diluent solubility and reduce the dielectric constant of the hardened product obtained by curing the photosensitive resin composition.

[0141] When the total amount of diamine residues in the resin (A) is set to 100 mol%, the total content of diamine residues represented by any one of formulas (2) to (4) is 30 mol% to 100 mol%, preferably 40 mol% to 100 mol%, more preferably 50 mol% to 100 mol%, and even more preferably 60 mol% to 100 mol%. The total content of diamine residues represented by formula (2) is preferably within the range described above. By ensuring that the total content of diamine residues represented by any one of formulas (2) to (4) is within the range described above, a photosensitive resin composition with low developing residue and good sensitivity can be obtained.

[0142] As a specific example of a diamine residue represented by any of formulas (2) to (4), for example, residues of diamines represented by formulas (20) to (37) can be listed.

[0143] [Chemistry 22]

[0144]

[0145] Preferably, the resin (A) contains the diamine residue represented by formula (2), and R in formula (6) 3 The total number of carbons is more than 1 and less than 5, and R in equation (7) is... 4 The number of carbons and the R 5 The total number of carbon atoms is 3 or more and 10 or less. The R mentioned in equation (6) here refers to... 3 The total number of carbons is more than 1 and less than 5, which means, for example, that there are multiple Rs in equation (6). 3 In this case, there will be multiple R 3 The sum of the carbon numbers of each is more than 1 and less than 5. Furthermore, the R mentioned in equation (7) here refers to... 4 The number of carbons and the R 5 The total number of carbons is 3 or more but less than 10, meaning that for each R 4 With R 5 The number of carbon atoms is counted, and the sum of these is greater than 3 and less than 10. This is achieved through the R... 3 R 4 R5 When the carbon number is within the aforementioned range, a photosensitive resin composition with good diluent solubility can be obtained without causing developing residue or deterioration of sensitivity, and is therefore preferred.

[0146] Preferably, the resin (A) contains the diamine residue represented by formula (2), and in formula (6), when a=1 is set as formula (6-1) and a=2 is set as formula (6-2), conditions 1 and 2 are satisfied, and in formula (7), R 4 The number of carbons and the R 5 The number of carbon atoms is different.

[0147] Condition 1: In formula (6-1), R 11 ~R 14 The total number of carbons and R 15 ~R 18 The total number of carbons is different.

[0148] Condition 2: In formula (6-2), R 19 ~R 22 The total number of carbons and R 25 ~R 28 The total number of carbons is different.

[0149] [Chemistry 23]

[0150]

[0151] In equations (6-1) and (6-2), R 11 ~R 28 Each of the above can be represented independently as a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Formulas (6-1) and (6-2) both satisfy the conditions of formula (6).

[0152] By satisfying the conditions described in formulas (6) and (7), the accumulation of resins (A) can be suppressed, and a photosensitive resin composition with particularly good diluent solubility can be obtained, which is therefore preferred.

[0153] Preferably, the resin (A) contains the diamine residue represented by formula (2), and the X 2 It is a divalent base represented by any one of equations (8) to (13) and (76) to (83).

[0154] [Chemistry 24]

[0155]

[0156] In equations (8) to (13) and equations (76) to (83), This indicates the bond node that is bonded to an aromatic ring.

[0157] Specifically, in equations (1), (19), and (70), Z 1 Preferably, it contains residues of diamines from any of formulas (20) to (25) and (29) to (34). By including the residues of said diamines, the solubility of the diluent can be further improved.

[0158] Furthermore, the resin (A) preferably contains the diamine residue represented by formula (2) and k=1. By setting k=1, a photosensitive resin composition with good diluent 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 Preferably, it is a residue of the diamine of any of formulas (26) and (35).

[0159] Additionally, the resin (A) preferably contains a diamine residue represented by formula (2) and R in formula (2) is preferred. 2 It is methyl. (By R) 2 As a methyl group, it is possible to obtain a photosensitive resin composition with good sensitivity and low residue. Furthermore, it is possible to reduce the dielectric constant of the cured product obtained by curing the photosensitive resin composition. Specifically, in formulas (1), (19), and (70), Z... 1 Preferably, it is a residue of the diamine of any of formulas (26) and (35).

[0160] In addition, resin (A) may contain other diamine residues besides the aforementioned diamine residues.

[0161] Specific examples of the other diamine residues may include aliphatic or aromatic diamine residues. An aliphatic diamine residue refers to a residue of a diamine that does not have an aromatic ring. Examples of aliphatic diamine residues include, for example, aliphatic alkyl diamines containing alkylene groups, or alkylene ether groups such as poly(ethylene ether), polyoxypropylene, or tetramethylene ether; alicyclic diamines; and aliphatic diamines having a siloxane structure.

[0162] Examples of aliphatic alkylene diamine residues include:

[0163] 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, Diamine H20 (trade name, manufactured by Okamura Oils, Inc.), and other polymethylenediamines.

[0164] JEFFAMINE KH-511, JEFFAMINE ED-600, JEFFAMINE ED-900, JEFFAMINE ED-2003, JEFFAMINE EDR-148, JEFFAMINE EDR-176, etc., contain diamines with polyethylene ether groups.

[0165] Polyoxypropylene diamines such as D-200, D-400, D-2000, D-4000, RP-409, and RP-2009 are also available.

[0166] RT-1000, HT-1100, and other diamines containing tetramethylene ether groups; HT-1000, HE-1000 (trade names, manufactured by Huntsman Corporation), and other amino-containing alkylene ether diamines.

[0167] Dimeric diamines such as "'versamine' (registered trademark) 551", "'versamine' (registered trademark) 552" (manufactured by BASF), "'priamine' (registered trademark) 1073", "'priamine' (registered trademark) 1074", and "'priamine' (registered trademark) 1075" (manufactured by Cargill)

[0168] Residues such as...

[0169] Examples of alicyclic diamine residues include residues from cyclohexyldiamine, methylene dicyclohexylamine, norbornene diamine, and PRO-NBDA (trade name, manufactured by Mitsui Chemicals, Inc.).

[0170] Examples of aliphatic diamine residues with a siloxane structure include residues such as 1,3-bis(3-aminopropyl)tetramethyldisiloxane (hereinafter, SiDA) and bis(p-aminophenyl)octamethylpentasiloxane. Copolymerizing aliphatic residues with a siloxane structure without reducing heat resistance can improve adhesion to the substrate.

[0171] In addition, other aromatic diamine residues can be listed as follows:

[0172] 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 ... Residues of diamines such as 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-aminobenzamide)-4-hydroxyphenyl]propane (HB), 2,2-bis[3-(3-aminobenzamide)-4-hydroxyphenyl]-1,1,1-trifluoroethane, bis(3-amino-4-hydroxyphenyl) sulfone, 9,9-bis(3-amino-4-hydroxyphenyl)fluorene (AZ-FDA), and 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAP). Regarding solubility in alkaline developing solutions, examples include: BAHF, BAP, AZ-FDA, 2,2-bis[3-(3-aminobenzamide)-4-hydroxyphenyl]propane (HB), and hydroxyl-containing diamine residues such as 2,2-bis[3-(3-aminobenzamide)-4-hydroxyphenyl]hexafluoropropane.

[0173] 3-Sulfonic acid-4,4'-diaminodiphenyl ether and other sulfonic acid-containing diamine residues,

[0174] Residues of thiol-containing diamines such as dimercaptophenylenediamine,

[0175] 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, petroleum ether (benzine), m-phenylenediamine, p-phenylenediamine, 1,5-naphthylenediamine, 2,6-naphthylenediamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy) Residues of aromatic diamines such as 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

[0176] Or residues of compounds in which a portion of the hydrogen atom of these aromatic rings is substituted with alkyl or fluoroalkyl groups having 1 to 10 carbon atoms.

[0177] These diamine residues can be used directly or formulated into corresponding diisocyanate compounds or trimethylsilyl diamines. They can be used alone or in combination of two or more.

[0178] Alternatively, resin (A) can also be end-sealed using end-capping agents such as monoamines, acid anhydrides, monoacyl chlorides, monocarboxylic acids, and monoactive esters. By using end-capping agents to seal the ends of the resin, the dissolution rate of the resin in alkaline aqueous solutions can be easily adjusted to a preferred range. Among these, end-capping agents having phenolic hydroxyl groups or crosslinking groups are preferred. By using end-capping agents with phenolic hydroxyl groups, the resin is given alkali solubility, thus reducing residue. Furthermore, by using end-capping agents with crosslinking groups, a crosslinking reaction occurs during the heat curing process, thus obtaining a cured film with excellent chemical resistance or elongation at break.

[0179] Specific examples of the monoamines containing phenolic hydroxyl groups 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, OAP), 3-aminophenol (hereinafter, MAP), 4-aminophenol (hereinafter, PAP), etc. In addition, examples of substances with photocrosslinking groups include: 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 2-aminostyrene, 3-aminostyrene, and 4-aminostyrene. Other examples 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, and 4-aminobenzenesulfonic acid. Two or more of these can also be used.

[0180] Examples of compounds containing a phenolic hydroxyl group in the aforementioned anhydride, monocarboxylic acid, monoacyl chloride compound, or monoactive ester compound include: 3-hydroxyphthalic anhydride, 3-carboxyphenol, 4-carboxyphenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, etc. Additionally, examples of compounds containing a photocrosslinking 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, butenoic 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, 3-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, etc. 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. Additionally, for the aforementioned monocarboxylic acids, monoacyl chloride compounds whose carboxyl groups are acyl-chlorinated can be used, as can monoacyl chloride compounds whose carboxyl groups are acyl-chlorinated only for the dicarboxylic acids, or active ester compounds obtained by reacting monoacyl chloride compounds with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboxylimide. Two or more of these can also be used.

[0181] Alternatively, multiple different end groups can be introduced by reacting multiple end capping agents.

[0182] Preferably, the resin (A) has the structure represented by formula (84).

[0183] [Chemistry 25]

[0184]

[0185] In equation (84), R 29 It can represent hydroxyl, alkyl with 1 to 3 carbons, alkoxy with 1 to 3 carbons, alkenyl with 2 to 5 carbons, or alkynyl with 2 to 5 carbons. This indicates the bonding site with the nitrogen atom.

[0186] The statement that the resin (A) mentioned herein has the structure represented by formula (84) means that the resin (A) is sealed at the end by a capping agent that is a monoamine represented by formula (95).

[0187] [Chemistry 26]

[0188]

[0189] In equation (95), R 29 It can represent hydroxyl, alkyl with 1 to 3 carbons, alkoxy with 1 to 3 carbons, alkenyl with 2 to 5 carbons, or alkynyl with 2 to 5 carbons.

[0190] The storage stability of the photosensitive resin composition can be improved by the resin (A) having the structure represented by formula (84), and is therefore preferred. In terms of particularly improving the storage stability of the photosensitive resin composition, R... 29 Preferably, it is a hydroxyl group, an alkyl group with 1 to 2 carbon atoms, an alkoxy group with 1 to 2 carbon atoms, or an alkynyl group with 2 to 3 carbon atoms.

[0191] When using a monoamine as the capping agent, its introduction ratio is preferably 1 mol% or more and 60 mol% or less relative to 100 mol% of all amine compounds contained in the resin (A). By setting the introduction ratio of the monoamine to preferably 1 mol% or more, and more preferably 5 mol% or more, the effect of reducing residue after development can be effectively obtained. In addition, by setting the introduction ratio of the monoamine to preferably 60 mol% or less, and more preferably 50 mol% or less, the molecular weight of the resin can be maintained at a high level, and high chemical resistance or elongation at break can be maintained.

[0192] When using anhydrides, monocarboxylic acids, monoacyl chlorides, or monoactive ester compounds as the capping agent, the total proportion of these compounds introduced is preferably 1 mol or more and 100 mol or less relative to 100 mol parts of all amine compounds contained in the resin (A). By setting the introduction proportion preferably to 1 mol or more, and more preferably 5 mol or more, the effect of reducing residue after development can be effectively obtained. On the other hand, by setting the introduction proportion preferably to 100 mol or less, and more preferably 90 mol or less, a high molecular weight of the resin can be maintained, as well as high chemical resistance or elongation at break.

[0193] The term "all amine compounds" as used here refers to the total content of compounds containing amino groups, such as monoamines, diamines, and triamines.

[0194] The resin (A) comprises structural unit (a) and / or structural unit (b), and the resin (A) comprises structural unit (c) and / or structural unit (d).

[0195] The resin (A) is preferably composed of at least one of structural unit (a) and structural unit (c). Structural unit (a) to structural unit (d) are as follows.

[0196] Structural unit (a): Z in equations (1), (19) and (70) 1 The expression is represented by equation (2), and there are two X's in equation (2). 1 All structural units are represented by equations (1), (19), or (70) with direct keys.

[0197] Structural unit (b): Z in equations (48), (49) and (71) 3 The two X's represented by equation (45) and existing in equation (45) 1 All are structural units represented by direct keys, as shown in equations (48), (49), or (71).

[0198] Structural unit (c): Z in equations (1), (19) and (70) 1 The expression is represented by equation (2), and there are two X's in equation (2). 1 At least one X in 1 The structural unit represented by equation (1), equation (19) or equation (70) of the divalent base represented by equation (5)

[0199] Structural unit (d): Z in equations (48), (49) and (71) 3 The two X's represented by equation (45) and existing in equation (45) 1 At least one X in 1 The structural unit represented by equation (48), equation (49) or equation (71) of the divalent base represented by equation (5)

[0200] [Chemistry 27]

[0201]

[0202] In equations (48), (49), and (71), Y 1 and R 1 The same range as that described in equations (1), (19), and (70). Z 3 The diamine residues represented by formula (45) are expressed independently. Indicates the bonding section.

[0203] [Chemistry 28]

[0204]

[0205] In equation (45), X 1 R is independently a direct bond or a divalent base represented by equation (5). 2 And k is the same range as that described in equation (2). X 3 The divalent organic group represented by any one of formulas (64) to (69). This indicates a bond point that is bonded to an imide, amide, amide ester, or amide acid structure.

[0206] [Chemistry 29]

[0207]

[0208] This indicates the bond node that is bonded to an aromatic ring.

[0209] As specific examples of diamine residues represented by formula (45), for example, residues of diamines represented by formulas (52) to (63) can be listed.

[0210] [Chemistry 30]

[0211]

[0212] The two X values ​​existing in the formula for structural units (a) and (b) are structural units (b). 1 All are direct bonds, therefore, by including structural units (a) and / or (b) in the resin (A), residue can be reduced. Furthermore, structural units (c) and (d) contain two X's in the formula. 1 At least one X in 1 Since the divalent group represented by formula (5) is present, the sensitivity can be improved by including structural unit (c) and / or structural unit (d) in the resin (A). Furthermore, since structural units (a) and (c) contain diamine residues represented by formula (2), the solvent solubility of the resin (A) can be improved by including at least one of structural units (a) and (c). Therefore, by including structural units (a) and / or (b) in the resin (A), and by including structural units (c) and / or (d) in the resin (A), and by including at least one of structural units (a) and (c), all the characteristics of improved sensitivity, reduced residue, and excellent solvent solubility can be achieved. Moreover, as described above, by including multiple structural units with different structures, the aggregation of resins during the preparation of the photosensitive resin composition can be suppressed, thus improving the storage stability of the photosensitive resin composition.

[0213] When the total amount of polyimide structural units contained in the resin (A) is set to 100 mol%, it is preferable that the total content of structural unit (a) and structural unit (b) is 20 mol% to 95 mol%, and the total content of structural unit (c) and structural unit (d) is 5 mol% to 80 mol%. Furthermore, the total content of structural unit (a) and structural unit (b) is more preferably 25 mol% to 95 mol%, and even more preferably 30 mol% to 95 mol%. Moreover, the total content of structural unit (c) and structural unit (d) is more preferably 5 mol% to 75 mol%, and even more preferably 5 mol% to 70 mol%. By including each structural unit within the range described above, the resin (A) can achieve a range that is ideal for all characteristics including sensitivity, residue reduction, solvent solubility, and storage stability. As described above, the structural units of polyimide are represented by formulas (73), (74), and (75).

[0214] Furthermore, in this invention, the content of structural units is defined as follows. Here, the calculation method for structural unit (a) will be described as an example.

[0215] Structural unit (a) is the structural unit represented by equation (1), equation (19) or equation (70) (Y in equation (1), equation (19) and equation (70) 1 Z is an acid dianhydride residue with 2 to 40 carbon atoms, which is independently formed by any of the following structures: aliphatic structure with 2 to 20 carbon atoms, alicyclic structure with 4 to 40 carbon atoms, and aromatic structure with 6 to 40 carbon atoms. 1 Equation (2) indicates that there are two X's in equation (2). 1 All are direct bonds). That is, Y, as an acid dianhydride residue. 1 With Z as a diamine residue 1 (where there are two X's) 1 The structure formed by direct bonds is structural unit (a). Therefore, when the total amount of dianhydride residues contained in the resin (A) is 100 mol%, it is equivalent to Y 1 The total amount of diamine residues is set as α mol%, and the total amount of diamine residues contained in the resin (A) is 100 mol%, which is equivalent to Z. 1 When the total amount of diamine residues is set to β mol%, the content of structural unit (a) when the total amount of polyimide structural units is set to 100 mol% can be calculated as follows.

[0216] The content (mol%) of structural unit (a) = α (mol%) / 100 (mol%) × β (mol%) / 100 (mol%) × 100 (mol%)

[0217] As an 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%.

[0218] The resin (A) preferably further comprises at least one of the structural units represented by formula (50), formula (51), and formula (72).

[0219] [Chemistry 31]

[0220]

[0221] In equations (50), (51), and (72), Y 1 and R 1 The same range as that described in equations (1), (19), and (70). Z 5 The diamine residues represented by formula (46) or formula (47) are expressed independently, respectively. Indicates the bonding section.

[0222] [Chemistry 32]

[0223]

[0224] In equations (46) and (47), X 4 This indicates a direct bond or -C(CH3)2-. t represents any integer from 0 to 2. This indicates a bond point that is bonded to an imide, amide, amide ester, or amide acid structure.

[0225] Since the diamine residues represented by formula (46) or formula (47) have a partial structure of phenyl ether, the resin (A) can be made flexible by including the diamine residues represented by formula (46) or formula (47), thereby improving the elongation at break of the cured photosensitive resin composition. Examples of diamine residues 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. From the viewpoint of improving the elongation at break of the cured material and reducing the residue of the photosensitive resin composition, it is preferable to contain the residue of a diamine of any one of TPE-Q, TPE-R, and APB.

[0226] When the total amount of polyimide structural units contained in the resin (A) is set to 100 mol%, the total content of the structural units represented by formula (50), formula (51), and formula (72) is preferably 1 mol% to 30 mol%, more preferably 1 mol% to 25 mol%. By having the total content of the structural units represented by formula (50), formula (51), and formula (72) within the aforementioned range, the elongation at break of the cured product obtained by curing the photosensitive resin composition can be improved without causing residue or deterioration of the sensitivity of the photosensitive resin composition. As described above, the structural units of polyimide are represented by formulas (73), (74), and (75).

[0227] The weight-average molecular weight (Mw) of the resin (A) is preferably 3,000 to 100,000, converted to polystyrene based on gel permeation chromatography (GPC). By setting 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 the developer can be effectively obtained. 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 obtained. In this invention, Mw is determined by the method described later.

[0228] 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 this range, developer residue can be reduced without deteriorating the heat resistance of the cured product obtained by hardening the photosensitive resin composition containing the resin (A). While the detailed mechanism for reducing developer residue is not fully understood, components with a molecular weight of 1,000 or less have better alkali solubility than molecules with a molecular weight greater than 1,000. Therefore, it is believed that components with a molecular weight of 1,000 or less act as dissolution-promoting components during development, thus contributing to the reduction of developer residue. In this invention, the total amount of components with a molecular weight of 1,000 or less is determined by the method described later.

[0229] Resin (A) can be synthesized by known methods. Methods for manufacturing resin (A) include, for example, reacting a tetracarboxylic acid dianhydride with a diamine compound at low temperature in a polymerization solvent; obtaining a diester from a tetracarboxylic acid dianhydride and an alcohol, followed by reacting the diester in the presence of an amine and a condensing agent; obtaining a diester from a tetracarboxylic acid dianhydride and an alcohol, followed by acyl chloride of the remaining dicarboxylic acid and reaction with an amine. Alternatively, the resin obtained by the aforementioned methods can be dehydrated and ring-closed by heating or chemical treatment with acids or alkalis.

[0230] The resin (A) polymerized by the method is ideally added to a large amount of deionized water or a methanol / deionized water mixture, allowing it to precipitate, which is then filtered, dried, and separated. Through this precipitation process, unreacted monomers, or oligomers such as dimers or trimers, are removed, improving the properties or chemical resistance of the thermosetting film.

[0231] The polymerization solvent can be any solvent capable of dissolving the acid dianhydrides or diamines used as raw material monomers; there is no particular limitation on its type. Examples include: N,N-dimethylformamide (hereinafter DMF), N,N-diethylformamide (hereinafter DEF), N,N-dimethylacetamide (hereinafter DMAc), N-methyl-2-pyrrolidone (hereinafter NMP), N-ethyl-2-pyrrolidone (hereinafter NEP), 1,3-dimethyl-2-imidazolium ketone (hereinafter DMI), 3-methoxy-N,N-dimethylpropionamide (hereinafter MPA), 3-butoxy-N,N-dimethylpropionamide (hereinafter BPA), N,N'-dimethylacrylamide (hereinafter DMPU), N,N-dimethylisobutylamide (hereinafter DMIB), N,N-dimethyl... Amides such as propionamide (hereinafter DMPA), 3-methyl-2-oxazolidinone, cyclic esters such as 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, ethyl levulinate glycerol ketal, acetophenone, sulfolane, dimethyl sulfoxide (hereinafter DMSO), dihydro-L-glucanone (Cyrene, manufactured by Circa), etc. The amount of the polymerization solvent used is preferably 100 to 1,900 parts by weight relative to 100 parts by weight of resin (A), and more preferably 150 to 950 parts by weight.

[0232] The photosensitive resin composition of the present invention contains a photosensitizer (B). By including the photosensitizer (B), the resin composition can be endowed with photosensitivity. Examples of photosensitizers (B) include a photoacid generator (B1) or a photopolymerization initiator (B2). By including the photoacid generator (B1), acid is generated in the light-irradiated area, increasing the solubility of the light-irradiated area relative to the alkaline aqueous solution, thus obtaining a positive embossed pattern that dissolves in the light-irradiated area. Furthermore, by including the photoacid generator (B1) and a crosslinking agent (E), the acid generated in the light-irradiated area promotes the crosslinking reaction of the crosslinking agent (E), thus obtaining a negative embossed pattern that does not dissolve in the light-irradiated area. Additionally, by including the photopolymerization initiator (B2) and a free radical polymerizable compound (H), the active free radicals generated in the light-irradiated area cause the vinyl unsaturated bonds in the free radical polymerizable compound to undergo free radical polymerization, thus obtaining a negative embossed pattern that does not dissolve in the light-irradiated area. In the photosensitive resin composition of the present invention, it is preferable that the photosensitizer (B) includes the photoacid generator (B1), exhibiting positive photosensitivity. The photosensitizer (B) contains the photoacid generator (B1), exhibiting positive photosensitivity, thereby easily reducing deviations in the opening size of the pattern caused by the processing technology and reducing residue. Additionally, the photosensitizer (B) contains the photopolymerization initiator (B2) and a free radical polymerizable compound (H), exhibiting negative photosensitivity, thereby enabling high sensitivity of the photosensitizing resin composition.

[0233] Examples of photoacid generators (B1) include: quinone diazide compounds, sulfonium salts, phosphonium salts, diazonium salts, monazite salts, etc.

[0234] Examples of the quinone diazide compounds include: quinone diazide sulfonic acid formed by ester bonding to a polyhydroxy compound; quinone diazide sulfonic acid formed by sulfonamide bonding to a polyamino compound; and quinone diazide sulfonic acid formed by ester bonding and / or sulfonamide bonding to a polyhydroxy-polyamino compound. Preferably, at least 50 mol% of the functional groups of these polyhydroxy or polyamino compounds are substituted with quinone diazide. Furthermore, it is preferable to contain two or more of the aforementioned photoacid generators (B1), thereby obtaining a highly sensitive photosensitive resin composition.

[0235] The quinone diazide can preferably be either a 5-naphthoquinone diazidesulfonyl group or a 4-naphthoquinone diazidesulfonyl group. The 4-naphthoquinone diazidesulfonyl ester compound has absorption in the i-ray region of a mercury lamp, making it suitable for i-ray exposure. The absorption of the 5-naphthoquinone diazidesulfonyl ester compound extends to the g-ray region of a mercury lamp, making it suitable for g-ray exposure. In this invention, the 4-naphthoquinone diazidesulfonyl ester compound and the 5-naphthoquinone diazidesulfonyl ester compound are preferably selected according to the wavelength of exposure. Alternatively, a naphthoquinone diazidesulfonyl ester compound may contain both 4-naphthoquinone diazidesulfonyl and 5-naphthoquinone diazidesulfonyl groups in the same molecule, or both 4-naphthoquinone diazidesulfonyl and 5-naphthoquinone diazidesulfonyl ester compounds may be present.

[0236] In the photoacid generator (B1), sulfonium salt, phosphonium salt, and diazoium salt are preferred as they moderately stabilize the acid components generated by exposure. Among them, sulfonium salt is preferred.

[0237] As a specific example of the photopolymerization initiator (B2), photopolymerization initiators described in International Publication No. 2019 / 087985

[0223] to

[0276] or International Publication No. 2019 / 194286

[0047] to

[0048] may be used. From the viewpoint of high sensitivity, the photopolymerization initiator (B2) is preferably composed of an oxime ester type photopolymerization initiator (B2-1) and / or a diaceticolide type photopolymerization initiator (B2-2). Two or more of these may be present.

[0238] The content of the photosensitizer (B) is preferably 0.5 to 50 parts by weight relative to 100 parts by weight of resin (A).

[0239] From the viewpoint of high sensitivity, the content of the photoacid generator (B1) in the photosensitizer (B) is preferably 0.5 to 50 parts by mass relative to 100 parts by mass of component (A). The quinone diazide compound is preferably 3 to 40 parts by mass. Furthermore, the total amount of sulfonium salt, phosphonium salt, and diazonium salt is preferably 0.5 to 20 parts by mass.

[0240] 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 resin (A). If it is 0.5 parts by mass or more, sufficient free radicals are generated by light irradiation, thus improving sensitivity. Furthermore, if it is 20 parts by mass or less, hardening of the unirradiated portion due to excessive free radical generation will not occur, thus improving alkaline developability.

[0241] The photosensitive resin composition of the present invention contains a solvent (C). Preferably, the photosensitive resin composition of the present invention contains a solvent represented by formula (17) and / or a solvent represented by formula (18) (C1).

[0242] [Chemistry 33]

[0243]

[0244] In equations (17) and (18), R 6 Each of the alkyl groups having 1 to 6 carbon atoms is represented independently, R 7 It refers to alkyl groups having 2 to 6 carbon atoms.

[0245] By including a solvent (C1), the ring-closing reaction of the resin (A) can be promoted, thereby improving the mechanical properties and chemical resistance of the cured product obtained by curing the photosensitive resin composition. Furthermore, the solvent (C1) interacts strongly with both the resin (A) component and the metal material, thus improving adhesion to the metal material.

[0246] From the viewpoint of promoting the solubility of resin (A) and the ring-closing reaction of resin (A), and improving the mechanical properties and chemical resistance of the cured product, β-alkoxypropionamide, which is the compound represented by formula (17), is preferably MPA or BPA.

[0247] In this invention, from the viewpoint of promoting the ring-closing reaction of resin (A) and improving the elongation at break and chemical resistance of the hardened film, the content of β-alkoxypropionamide 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). On the other hand, from the viewpoint of forming a desired patterned film during the preparation of the developing film, it is preferably 15 parts by mass or less, more preferably 10 parts by mass or less.

[0248] From the viewpoint of promoting the ring-closing reaction of resin (A) and improving the mechanical properties and chemical resistance of the cured material, the compound represented by formula (18) is preferably DMPA or DMIB.

[0249] In this invention, from the viewpoint of promoting the ring-closing reaction of resin (A) and improving the mechanical properties and chemical resistance of the cured product, 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). On the other hand, from the viewpoint of forming a desired patterned film during the preparation of the developing film, it is preferably 15 parts by mass or less, more preferably 10 parts by mass or less.

[0250] The photosensitive resin composition of the present invention preferably includes a solvent (C2), which is a compound having hydroxyl groups and a boiling point of 100°C or higher and 200°C or lower at atmospheric pressure. By including the solvent (C2), not only can flatness be improved, but also developability can be improved, the generation of developing residue can be suppressed, and sensitivity can be increased.

[0251] 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), diethylene glycol monomethyl ether (boiling point 194°C), etc.

[0252] The content of the solvent (C2) in the photosensitive resin composition of the present invention is preferably 5 to 3,000 parts by mass relative to 100 parts by mass of the total amount of resin (A), and more preferably 10 to 1,000 parts by mass.

[0253] The photosensitive resin composition of the present invention comprises both the solvent (C1) and the solvent (C2). When the content of the solvent (C1) in the photosensitive resin composition is set to X (mass) and the content of the solvent (C2) is set to 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. By having the Y / X ratio within this range, all the characteristics of improved adhesion to metallic materials, improved flatness, suppression of developing residue, and improved sensitivity can be achieved.

[0254] The photosensitive resin composition of the present invention may also contain a solvent other than the solvent (C1) and the solvent (C2), namely solvent (C3). Examples of solvent (C3) include:

[0255] Ethers such as ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol dimethyl ether, and diethylene glycol ethyl methyl ether.

[0256] Esters such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, butyl lactate, methyl levulinate, ethyl levulinate, propyl levulinate, and butyl levulinate.

[0257] Alcohols such as methanol, ethanol, and isopropanol

[0258] Ketones such as methyl ethyl ketone, methyl isobutyl ketone, methyl pentanyl ketone, diisobutyl ketone, cyclopentanone, and diacetone alcohol.

[0259] Polar aprotic solvents such as N-methyl-2-pyrrolidone, GBL, DMSO, 1,3-dimethyl-2-imidazolidineone, 3-methyl-2-oxazolidineone, and dihydro-L-glucanone (manufactured by Cyrene and Circa) are also mentioned.

[0260] Aromatic hydrocarbons such as toluene and xylene. It may also contain two or more of these.

[0261] The content of the solvent (C3) is preferably 1,500 parts by weight or less, more preferably 1,000 parts by weight or less, relative to 100 parts by weight of resin (A).

[0262] The photosensitive resin composition of the present invention is preferably a positive photosensitive resin composition that further comprises a solubility promoter (D) and the photosensitive agent (B) comprises a photoacid generator (B1). The solubility promoter (D) can supplement the alkaline developability of the photosensitive resin composition, reduce residue and improve sensitivity in a positive photosensitive resin composition. The solubility accelerator (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, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP4HBPA (TetrakisP-DO-BPA), TrisP-HAP, TrisP-PA, TrisP-PHBA, TrisP-SA, TrisOCRPA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), Milex HBP. X, Milex PIRM, Milex MDPR (trade name, manufactured by Mitsui Chemicals), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOCF, 4PC, BIR-BIPC-F, TEP-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.), Bisphenol A, Bisphenol AF (hereinafter, Compounds containing phenolic hydroxyl groups, such 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-hydroxyquinoline. In terms of maintaining the pattern shape well while improving sensitivity, the content of the solubility accelerator (D) is preferably 1 to 40 parts by weight relative to 100 parts by weight of resin (A).

[0263] The photosensitive resin composition of the present invention preferably includes a crosslinking agent (E). A crosslinking agent is a compound having crosslinking groups capable of bonding with a resin. By including the crosslinking agent (E), the elongation at break and chemical resistance of the cured film can be improved. This is presumably because the crosslinking agent (E) component allows new crosslinking structures to be introduced into the cured form of the photosensitive resin composition, thus increasing the crosslinking density.

[0264] The preferred crosslinking agent (E) is a compound having two or more thermally crosslinking properties such as alkoxymethyl, hydroxymethyl, epoxy, or oxetyl groups in its molecule.

[0265] As a specific example of the crosslinking agent (E), the crosslinking agent described in International Publication No. 2019 / 087985,

[0407] to

[0412] , may be used.

[0266] The content of the crosslinking agent (E) is preferably 0.5 to 50 parts by weight relative to 100 parts by weight of resin (A). If the content is 0.5 to 50 parts by weight, the elongation at break and chemical resistance of the hardened film can be improved without deteriorating the storage stability of the photosensitive resin composition or the transparency of the hardened film.

[0267] The photosensitive resin composition of the present invention preferably contains a surfactant (F). A surfactant is a compound having both hydrophilic and hydrophobic structures. By containing an appropriate amount of the surfactant (F), the surface tension of the photosensitive resin composition can be adjusted arbitrarily, improving leveling properties during coating and enhancing the uniformity of film thickness. The surfactant (F) is preferably a fluoropolymer surfactant, a silicone surfactant, a polyoxyalkylene ether surfactant, or an acrylic surfactant. More preferably, the surfactant (F) contains a silicone surfactant, a polyoxyalkylene ether surfactant, or an acrylic surfactant, in order to suppress contamination at the opening after curing. As a specific example of the surfactant (F), surfactants described in International Publication Nos. 2019 / 087985,

[0419] to

[0420] , can be used.

[0268] The surfactant (F) in the photosensitive resin composition of the present invention preferably comprises 0.001% by mass or more, more preferably 0.005% by mass or more of the total photosensitive resin composition. A content of 0.001% by mass or more improves leveling properties during coating. On the other hand, the surfactant content is preferably 1% by mass or less, more preferably 0.5% by mass or less. A content of 1% by mass or less reduces defects generated during coating and allows for the acquisition of a cured product with high heat resistance.

[0269] The photosensitive resin composition of the present invention preferably contains a adhesion modifier (G). Examples of adhesion modifiers (G) include: vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, silane coupling agents, titanium chelating agents, aluminum chelating agents, and compounds obtained by reacting aromatic amine compounds with alkoxy-containing silicon compounds. Two or more of these may be included. By including these adhesion modifiers, adhesion to substrates such as silicon wafers, ITO, SiO2, and silicon nitride can be improved when the photosensitive resin composition is developed. From the perspective of good storage stability of the photosensitive resin composition, it is preferable to include a silane coupling agent as the adhesion modifier (G). The content of the adhesion modifier (G) relative to 100 parts by weight of resin (A) is preferably 0.1 parts by weight or more, more preferably 0.3 parts by weight or more. Furthermore, it is preferably 10 parts by weight or less, more preferably 5 parts by weight or less. By including the adhesion modifier (G) within the above range, both the storage stability of the photosensitive resin composition and its adhesion to the substrate can be achieved.

[0270] The photosensitive resin composition of the present invention may further comprise a free radical polymerizable compound (H), and the photosensitizer (B) comprises a photopolymerization initiator (B2). By employing the aforementioned structure, as described, the active free radicals generated in the light-irradiated portion cause the vinyl unsaturated bonds in the free radical polymerizable compound to undergo free radical polymerization, thereby obtaining a negative embossed pattern that is insoluble in the light-irradiated portion. As a result, the photosensitive resin composition becomes a negative photosensitive resin composition.

[0271] Specific examples of the free radical polymerizable compound (H) component include, for example, the free radical polymerizable compounds described in International Publication Nos. 2019 / 087985,

[0189] to

[0222] . Preferably, it contains an aliphatic free radical polymerizable compound with a flexible chain. An aliphatic free radical polymerizable compound with a flexible chain refers to a compound having multiple vinyl unsaturated double bonds and a flexible backbone such as an aliphatic chain or an oxoalkylene chain in its molecule.

[0272] By using the aliphatic free radical polymerizable compound containing the aforementioned soft chain, the curing reaction under light irradiation can be carried out efficiently, improving the sensitivity under light irradiation. Furthermore, changes in the pattern opening size width before and after thermosetting can be suppressed. The content of the free radical polymerizable compound (H) is preferably 5 to 50 parts by mass relative to 100 parts by mass of resin (A).

[0273] The photosensitive resin composition of the present invention may also contain additives (I) other than those described above (hereinafter referred to as additives (I)). Examples of additives (I) include, for example: the polyfunctional thiol compounds described in International Publication No. 2019 / 087985

[0386] to

[0398] , the colorants described in International Publication No. 2019 / 087985

[0281] to

[0370] , the dispersants described in International Publication No. 2019 / 087985

[0371] to

[0385] , and the additives described in International Publication No. 2019 / 087985

[0371] to

[0385] . Sensitizers described in

[0399] to

[0402] of International Publication No. 19 / 087985, polymerization inhibitors described in

[0403] to

[0406] of International Publication No. 2019 / 087985, or inorganic particles described in

[0127] to

[0130] of International Publication No. 2016 / 052268 or

[0024] to

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

[0274] As a method for manufacturing the photosensitive resin composition of the present invention, examples include: placing the resin (A), photosensitizer (B), solvent (C), and other components as needed into a glass flask or stainless steel container, and dissolving them by stirring with a mechanical stirrer or the like; dissolving by ultrasonication; and dissolving by stirring with a planetary stirring degassing device.

[0275] The obtained photosensitive resin composition is preferably filtered using a leak filter to remove dust or particles. The leak filter has a pore size of 0.5 μm 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 leak filter is made of materials such as polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc., but polyethylene or nylon is preferred. When the photosensitive resin composition contains inorganic particles or pigments, a leak filter with a larger pore size than these is preferred.

[0276] The cured product of the present invention is formed by curing the photosensitive resin composition of the present invention. Methods for curing the photosensitive resin composition include, for example, heating and curing the photosensitive resin composition, or irradiating it with active chemical rays. By curing the photosensitive resin composition of the present invention, the heat resistance or chemical resistance of the cured product can be improved. Preferably, the cured product is a cured product having a film shape, i.e., a cured film.

[0277] Next, the method for manufacturing the hardened material of the present invention will be described.

[0278] The preferred method for manufacturing the hardened material of the present invention includes the following steps.

[0279] (1) The process of coating the photosensitive resin composition onto a substrate to form a photosensitive resin film;

[0280] (2) The process of drying the photosensitive resin film;

[0281] (3) The process of exposing the dried photosensitive resin film with a photomask;

[0282] (4) The process of developing the exposed photosensitive resin film; and

[0283] (5) The process of heat-treating the developed photosensitive resin film.

[0284] In step (1), the photosensitive resin composition of the present invention is coated onto a substrate using spin coating, slot coating, dip coating, spray coating, printing, or other methods to obtain a photosensitive resin film of the photosensitive resin composition. Before coating, the substrate to be coated with the photosensitive resin composition may be pretreated with a bonding modifier. For example, the following methods can be used: the substrate surface is treated with a solution prepared by dissolving the bonding modifier at 0.5% to 20% by mass in solvents such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate. As methods for treating the substrate surface, spin coating, slot coating, rod coating, dip coating, spray coating, steam treatment, and other methods can be used. Specific examples of contact improvers include the contact improvers described in International Publication No. 2019 / 065351

[0127] .

[0285] In step (2), the coated photosensitive resin film is subjected to reduced pressure drying treatment as needed, and then heat treatment is performed for 1 minute to several hours in the range of 50°C to 180°C using a heating plate, oven, infrared radiation, etc., thereby obtaining the photosensitive resin film.

[0286] In step (3), a photomask with the desired pattern is irradiated with chemical rays onto a photosensitive resin film. Chemical rays used in the exposure include ultraviolet light, visible light, electron beams, and X-rays, but in this invention, mercury lamp i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) are preferred. Post-exposure baking may also be performed after irradiation with chemical rays. By performing post-exposure baking, effects such as improved resolution after development or an increased tolerance range for development conditions can be expected. Post-exposure baking can be performed using an oven, a heated plate, infrared radiation, a flash annealing device, or a laser annealing device. The post-exposure baking temperature is preferably 50°C to 180°C, more preferably 60°C to 150°C. The post-exposure baking time is preferably 10 seconds to several hours. If the post-exposure baking time is within the aforementioned range, the reaction proceeds well, and the development time can sometimes be shortened.

[0287] In step (4), the exposed resin film is developed using a developing solution to remove the portion other than the exposed portion. The developing solution is preferably a good solvent relative to the photosensitive resin composition, or a combination of a good solvent and a poor solvent. For example, in the case of a photosensitive resin composition that does not dissolve in an alkaline aqueous solution, a good solvent is preferably NMP, N-cyclohexyl-2-pyrrolidone, DMAc, cyclopentanone, cyclohexanone, GBL, α-acetyl-γ-butyrolactone, etc., and a poor solvent is preferably toluene, xylene, methanol, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, and water, etc. When a good solvent and a poor solvent are used in combination, it is preferable to adjust the ratio of the poor solvent to the good solvent by the solubility of the polymer in the photosensitive resin composition. Alternatively, two or more solvents may be used, for example, in combination. On the other hand, in the case of a photosensitive resin composition dissolved in an alkaline aqueous solution, the developing solution used in development is a developing solution that dissolves and removes the alkaline aqueous solution-soluble polymer; typically, it is an alkaline aqueous solution containing a dissolved alkaline compound. 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, hexamethylenediamine, etc. Furthermore, depending on the circumstances, polar solvents such as NMP, DMF, DMAc, DMSO, GBL, and dimethacrylamide, alcohols such as methanol, ethanol, and isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone, or combinations thereof, may be added to these alkaline aqueous solutions. As for the developing method, it can be spraying, coating, immersion, ultrasonication, etc.

[0288] Next, the pattern formed by development is preferably rinsed with deionized water. Alternatively, alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to the deionized water for rinsing.

[0289] Next, the process described in (5) is performed. Since residual solvents or components with low heat resistance can be removed by heat treatment, heat resistance and chemical resistance can be improved. In the photosensitive resin composition of the present invention, resin (A) can form imide rings and oxazole rings by heat treatment, thus improving heat resistance and chemical resistance. In addition, when a crosslinking agent (E) is contained, a thermal crosslinking reaction can be carried out by heat treatment, which can improve mechanical properties, heat resistance and chemical resistance. The heat treatment is performed by selecting a temperature, gradually increasing the temperature, or continuously increasing the temperature within a certain temperature range for 5 minutes to 5 hours. As an example, heat treatment is performed at 150°C and 250°C for 30 minutes each. Alternatively, methods such as linearly increasing the temperature from room temperature to 300°C over 2 hours can be used. As the heat treatment conditions in the present invention, 180°C or higher is preferred, more preferably 200°C or higher, and even more preferably 230°C or higher, and particularly preferably 240°C or higher. In addition, the heat treatment conditions are preferably 400°C or lower, more preferably 350°C or lower, and even more preferably 300°C or lower.

[0290] Next, as an example of a method for manufacturing a cured product of the present invention, a method for manufacturing a cured film as a form of cured product will be described. This method involves forming a photosensitive sheet from the photosensitive resin composition of the present invention into a sheet shape. Furthermore, the term "photosensitive sheet" here refers to a sheet-shaped photosensitive resin composition obtained by coating a release liner with the photosensitive resin composition and then drying it.

[0291] When using a photosensitive sheet formed from the photosensitive resin composition of the present invention, if a protective film is present on the photosensitive sheet, it is peeled off, and the photosensitive sheet is placed facing a substrate and bonded together by thermoforming to obtain a photosensitive resin film. Regarding the photosensitive sheet, it can be obtained by coating the photosensitive resin composition of the present invention onto a support film containing polyethylene terephthalate or the like as a peelable film and then drying it.

[0292] Hot bonding can be performed through hot pressing, hot lamination, or hot vacuum lamination. Regarding the adhesion and embedding properties of the substrate, the bonding temperature is preferably 40°C or higher. Furthermore, when the photosensitive film is photosensitive, to prevent hardening of the photosensitive film during bonding and a decrease in the resolution of pattern formation during the exposure / development process, the bonding temperature is preferably 140°C or lower.

[0293] A photosensitive resin film obtained by bonding a photosensitive film to a substrate can be cured by a process of exposing the photosensitive resin film, developing the exposed photosensitive resin film, and heating and curing the film.

[0294] The display device of the present invention includes the cured material of the present invention. Specific examples of the display device of the present invention include: light-emitting diode (LED) displays, liquid crystal displays, organic EL displays, etc. The cured material formed from the photosensitive resin composition of the present invention can be used in display devices including a first electrode formed on a substrate and a second electrode disposed opposite to the first electrode. Specifically, it can be used, for example, to constitute an insulating film for an LED display, a planarization layer for a liquid crystal display, a planarization layer and / or a pixel dividing layer for an organic EL display, etc.

[0295] The organic EL display device of the present invention includes the cured material of the present invention. Preferably, the organic EL display device of the present invention includes the cured material of the present invention as one or more selected from the group consisting of a pixel dividing layer, an electrode insulating layer, a wiring insulating layer, an interlayer insulating layer, a TFT planarization layer, an electrode planarization layer, a wiring planarization layer, a TFT protective layer, an electrode protective layer, a wiring protective layer, a gate insulating layer, a color filter, a black matrix, and black pillar spacers. The organic EL display device of the present invention can be preferably used in various electronic devices. Examples of television devices include smartphones, personal computers (PCs), and smart glasses.

[0296] The electronic components of this invention include the hardened material of this invention.

[0297] The cured product formed from the photosensitive resin composition of the present invention can be used as an insulating film or protective film for electronic components.

[0298] Here, electronic components include: active components containing semiconductors such as transistors, diodes, integrated circuits (ICs), and memory; and passive components such as resistors, capacitors, and inductors. Additionally, electronic components using semiconductors are also referred to as semiconductor devices or semiconductor packages.

[0299] As a specific example of a hardened material in electronic components, it can be preferably used as a passivation film for semiconductors, a surface protective film for semiconductor elements, thin film transistors (TFTs), an interlayer insulating film between rewiring in multilayer wiring for high-density mounting of two to ten layers, an insulating film for touch panel displays, a protective film, an insulating layer for organic electric field light-emitting elements, etc., but is not limited to these uses, and can take various structures.

[0300] Furthermore, the electronic components of the present invention preferably include the curing material of the present invention on a substrate. The surface of the substrate on which the curing material is formed can be appropriately selected according to the application and process, and examples include: silicon substrate, silicon carbide substrate, gallium nitride substrate, ceramic, gallium arsenide, metal, epoxy resin, etc., preferably silicon substrate, silicon carbide substrate or gallium nitride substrate.

[0301] Example

[0302] The present invention will be described in more detail below with examples and comparative examples, but the present invention is not limited to these forms.

[0303] In addition, for compounds that use abbreviations in their compounding process, the names are shown below.

[0304] ODPA: 4,4'-oxyphthalic anhydride

[0305] 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 Shin Nippon Rikka Co., Ltd.)

[0306] MCTC: 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0307] HBPDA: Dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0308] BAHF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (manufactured by Central Glass Co., Ltd.)

[0309] BAP: 2,2-bis(3-amino-4-hydroxyphenyl)propane (manufactured by Wakayama Seika Kogyo Co., Ltd.)

[0310] 3,4'-ODA: 3,4'-Diaminodiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0311] TPE-R: 1,3-Bis(4-aminophenoxy)benzene

[0312] SiDA: 1,3-bis(3-aminopropyl)tetramethyldisiloxane (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0313] MAP: 3-Aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0314] 4-APA: 4-Aminophenylacetylene (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0315] MPA: 3-Methoxy-N,N-Dimethylpropionamide (manufactured by KJ Chemicals, Inc.)

[0316] DMIB: N,N-Dimethylisobutylamide

[0317] DMPA: N,N-Dimethylpropionamide

[0318] PGME: Propylene Glycol Monomethyl Ether

[0319] GBL: γ-Butyrolactone

[0320] DMSO: Dimethyl sulfoxide

[0321] ITO: Indium Tin Oxide

[0322] TMAH: Tetramethylammonium hydroxide

[0323] DMFDMA: N,N-dimethylformamide dimethyl acetal.

[0324] [Common processing conditions]

[0325] Unless otherwise specified, the following treatments in the measurement / evaluation methods and examples / comparative examples are performed under the following conditions.

[0326] (1) Pretreatment of ITO substrate

[0327] The glass substrate (manufactured by Geomatec Corporation; hereinafter referred to as "ITO substrate") with a 100 nm ITO film sputtered onto glass is used for a 100-second UV-O3 cleaning process using a desktop optical surface treatment apparatus (PL16-110; manufactured by SEN Special Light Source Co., Ltd.). The Si wafer (manufactured by Electronic Terminal Materials Co., Ltd.) is used for a dehydration baking process by heating at 130°C for 2 minutes using a hot plate (HP-1SA; manufactured by ASONE Co., Ltd.).

[0328] (2) Heat treatment (curing)

[0329] For the developing film, a high-temperature inert gas oven (INH-9CD-S manufactured by Koyo Heating Systems, Inc.) is used to heat it at 250°C for 1 hour in a nitrogen environment, thereby producing a hardened film as a hardened material.

[0330] [Measurement and Evaluation Methods]

[0331] (1) Weight average molecular weight (Mw) of resin (A)

[0332] For the resins obtained in each synthesis example, the weight-average molecular weight (Mw) of polystyrene was determined using a gel permeation chromatography (GPC) analyzer under the following conditions.

[0333] Measuring apparatus: Waters 2695 (manufactured by Waters Corporation)

[0334] Column temperature: 50℃

[0335] Flow rate: 0.4 mL / min

[0336] Detector: 2489 UV / Vis detector (measurement wavelength 260 nm)

[0337] Developing solvent: NMP (containing 0.21% by mass lithium chloride and 0.48% by mass phosphoric acid)

[0338] Guard column: TOSOH TSK guard column (manufactured by TOSOH)

[0339] Tubing: TOSOH TSK-GEL a-2500 and TOSOH TSK-GEL a-4000 (both manufactured by Tosoh Corporation) in series.

[0340] Number of measurements: 2 (the average value is taken as the weight average molecular weight of polyimide).

[0341] (2) Determination of the amount of components with a molecular weight of less than 1,000 contained in resin (A)

[0342] The same procedure as for determining the weight average molecular weight was followed, and the area percentage of peaks with a molecular weight of 1,000 or less was calculated using polystyrene conversion. This area percentage of peaks with a molecular weight of 1,000 or less was considered as the mass of the component with a molecular weight of 1,000 or less contained in resin (A).

[0343] (3) Esterification rate

[0344] Using a nuclear magnetic resonance (NMR) apparatus (EX-270 manufactured by NEC Corporation), the concentrations of 10 mg of resin and 0.8 g of deuterated DMSO (DMSO-d6) in each synthesis example were determined. 1 H-NMR is used to determine the integral value of the peak originating from aromatic protons in the resin. The esterification rate of the polyamide ester is calculated based on the area ratio of the peak originating from the methyl protons in the carboxylic acid ester. Resins other than polyamide esters do not contain carboxylic acid esters, therefore their esterification rate cannot be determined and is indicated by "-".

[0345] (4) Imidene ring closure rate (R IM(%)

[0346] The resins obtained in each synthesis example were dissolved in GBL at a concentration of 35% by mass. The solution was spin-coated onto a 4-inch silicon wafer using a spin coater (Mikasa Corporation 1H-DX), and then baked at 120°C for 3 minutes to create a resin film with a thickness of 4 μm to 5 μm. The wafer with the resin film was divided into two parts. One part was cured in a cleanroom oven (Koyo Heating Systems Corporation CLH-21CD-S) at 140°C for 30 minutes under a nitrogen atmosphere (oxygen concentration below 20 ppm), and then further cured at 320°C for 1 hour to completely close the imide ring. The transmitted infrared absorption spectra of the resin film before and after curing were measured using an infrared spectrophotometer (Horiba Corporation FT-720), confirming the absorption peak (1,780 cm⁻¹) of the imide structure caused by polyimide. -1 Nearby, 1,377 cm -1 The existence of (nearby) was determined, and then 1,377 cm was calculated. -1 Nearby peak intensities (before curing: S, after curing: T). The peak intensity ratio obtained by dividing the peak intensity (S) by the peak intensity (T) according to the following formula is set as the content of imide groups in the polymer before heat treatment, i.e., the imide ring closure rate.

[0347] R IM (%) = (S / T) × 100.

[0348] Resins other than polyimides (including polyamic acid esters) do not have the structural unit of polyimides, so the ring closure rate of the imide ring cannot be determined and is indicated by "-".

[0349] (5) Evaluation of the content of the compounds represented by formulas (17) and (18) relative to resin (A)

[0350] 0.03 g of resin (A) obtained in each synthesis example and 0.01 g of methyl 3-nitrobenzene as an internal standard were dissolved in 0.7 g of deuterated DMSO and analyzed by NMR (GX-270 manufactured by NEC). Based on the area of ​​the peak near 3.9 ppm from methyl 3-nitrobenzene, the content of the compound represented by formulas (17) and (18) relative to 100 parts by mass of resin (A) was determined according to the peak area.

[0351] (6) Film thickness measurement

[0352] The film thickness was measured using a surface roughness-profile shape measuring machine (SURFCOM1400D; manufactured by Tokyo Seimitsu Co., Ltd.), with the measurement magnification set to 10,000x, the measurement length set to 1.0 mm, and the measurement speed set to 0.30 mm / s.

[0353] (7) Solubility of diluent

[0354] Using a spin coater (Mikasa Corporation 1H-DX), the photosensitive resin compositions of each example and comparative example were coated onto a 4-inch silicon wafer by spin coating, followed by baking at 120°C for 2 minutes to create a resin film with a thickness of 2 μm. The wafer with the resin film was divided into two parts. One part was immersed in 100 g of PGME at 23°C for 2 minutes and then rinsed with pure water. The other part of the wafer with the resin film was similarly immersed in 100 g of PGME at 23°C for 5 minutes and then rinsed with pure water. The dissolution of the resin film was confirmed by visual inspection and film thickness measurement. A, B, and C were deemed acceptable as follows. Furthermore, A was the most preferred result.

[0355] A: Let it soak for 2 minutes until completely dissolved.

[0356] B: Let it stand for 2 minutes without completely dissolving, and let it stand for 5 minutes until completely dissolved.

[0357] C: The film thickness after standing immersion for 5 minutes is less than 1.0 μm.

[0358] D: The film thickness after standing immersion for 5 minutes is greater than 1.0 μm.

[0359] (8) Flatness evaluation

[0360] Figure 1A cross-sectional view of the flatness evaluation sample. Using a spin coater (MS-A100; manufactured by Mikasa), the photosensitive resin compositions of each example and comparative example, which served as samples, were coated by spin coating onto a 100 mm square stepped substrate 1 with a thickness (height) of 1.2 μm, a width of 5 μm, and a length of 15 mm. The pattern was patterned in parallel with five lines at 5 μm intervals in the central part of the substrate. The substrate was pre-baked at 110°C for 120 seconds to produce a pre-baked film in such a way that the film thickness h0 of the flat portion of the substrate without the pattern (the part where the measurement was performed is referred to as "measurement point A" for convenience) was 3.7 μm. Subsequently, the obtained substrate with the film was cured using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermal Systems, Ltd.) at an oxygen concentration below 20 ppm, with the temperature increased to 250°C at a rate of 5°C / min, and then cured at 250°C for 1 hour, thereby producing a hardened film with a thickness of approximately 2.5 μm at measurement point A. The surface step difference of the obtained hardened film was measured using a surface profilometer (P-15; manufactured by KLA-Tencor, Ltd.). The average value of the height h1 to h3 of the film on the three line patterns (excluding the outermost two of the five line patterns) from the baseline 3 was defined as the surface step difference h. Furthermore, from... Figure 1 Baseline 3 is defined as the line connecting the points where the thickness of the film is minimum at the concave portions existing on the left and right sides of the mountain-shaped resin films measured (h1 to h3). Specific examples are described below. Figure 1 In this design, the straight line connecting the bottom a1 and bottom a2 of the stepped shape is defined as the baseline, and the length from the top b1 of the stepped shape to the intersection of the descending line perpendicular to the substrate surface and the baseline is defined as h1. h2 is defined as the length from b2 to the intersection of the descending line perpendicular to the substrate surface and the baseline, using the line connecting a2 and a3 as the baseline, and h3 is defined as the length from b3 to the intersection of the descending line perpendicular to the substrate surface and the baseline, using the line connecting a3 and a4 as the baseline. Flatness is determined based on the surface step h as described below, and A, B, and C with a surface step h less than 0.4 μm are considered acceptable. Furthermore, A is the most preferred result.

[0361] A: The surface step height h is less than 0.2 μm.

[0362] B: Surface step h is greater than 0.2 μm but less than 0.3 μm

[0363] C: Surface step h is greater than 0.3 μm but less than 0.4 μm

[0364] D: The surface step difference h is greater than 0.4 μm.

[0365] (9) Sensitivity evaluation

[0366] Using a spin coater (MS-A100; manufactured by Mikasa, Inc.), the spin speed was adjusted to achieve a pre-baked film thickness of approximately 1.8 μm. The photosensitive resin compositions obtained in each example and comparative example were coated onto a 100 mm × 100 mm ITO substrate using spin coating. A pre-baked film with a thickness of approximately 1.8 μm was then pre-baked at 110°C for 120 seconds using a buzzer-heated plate (HPD-3000BZN; manufactured by ASONE, Inc.) to produce a pre-baked film. The obtained pre-baked film was then exposed using a manual exposure machine (MA-1200; manufactured by Dai Nippon Research, Inc.) with a septum positive mask (manufactured by HOYA, Inc., with a stripe design linewidth of 20 μm) at 150 mJ / cm². 2 (The value from the i-ray illuminometer) is the maximum exposure, expressed as 5 mJ / cm². 2 Exposure is performed at progressively lower exposure levels, followed by development / rinsing and drying to obtain a patterned substrate with a photosensitive resin film forming a predetermined pattern. The sensitivity of the patterned substrates at various exposure levels is evaluated. Furthermore, development is performed using a small automatic photolithography developing apparatus (AD-2000 manufactured by Takizawa Sangyo Co., Ltd.) with an alkaline developing solution of 2.38% (w / w) TMAH aqueous solution. The development time is adjusted to reduce the film thickness of unexposed areas to 0.5 μm, and rinsing is performed using deionized water.

[0367] Using an FPD / LSI inspection microscope (OPTIPHOT-300; Nikon), observe the opening of the developed film. Set the sensitivity to the lowest exposure where the opening width is the same as the linewidth (20 μm) of the mask design. Judge as follows: sensitivity less than 110 mJ / cm² is considered acceptable. 2 AA, A, B, and C are set as qualified. Furthermore, A is the optimal result.

[0368] AA: Sensitivity less than 65 mJ / cm 2

[0369] A: Sensitivity is 65 mJ / cm 2 Above but below 80 mJ / cm 2

[0370] B: Sensitivity is 80 mJ / cm 2 Above but less than 95 mJ / cm 2

[0371] C: Sensitivity is 95 mJ / cm 2 Above but less than 110 mJ / cm2

[0372] D: Sensitivity is 110 mJ / cm 2 above.

[0373] (10) Evaluation of developing residue

[0374] Using the same method as described in (9), the photosensitive resin composition was coated onto an ITO substrate and pre-baked to produce a pre-baked film with a thickness of approximately 1.8 μm. For the obtained pre-baked film, a manual exposure machine (MA-1200; manufactured by Dai Nippon Research, Ltd.) was used, along with a grayscale mask for dielectric sensitivity measurement (MDRM MODEL 4000-5-FS; manufactured by Opto-Line International; featuring a 1:1 line and space pattern of 2 μm to 50 μm; with areas having transmittances of 1%, 5%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 25%, 30%, 35%, 40%, 50%, and 60%). The exposure was set to 150 mJ / cm² using i-rays (wavelength 365 nm), h-rays (wavelength 405 nm), and g-rays (wavelength 436 nm) from an ultra-high pressure mercury lamp. 2 After patterned exposure (using i-ray illuminance meter values), development / rinsing and drying are performed to create a post-developed film of the photosensitive resin composition. Furthermore, the development time is adjusted to reduce the film thickness of the unexposed areas to 0.5 μm, and rinsing is performed using deionized water.

[0375] Using an FPD / LSI inspection microscope (OPTIPHOT-300; Nikon), the analytical pattern of the developed film was observed. The area with the lowest exposure and an opening width matching the mask design (20 μm) was examined for residue at the opening of the 20 μm line and spatial pattern. Judgments were made as follows: A, B, and C, where the area of ​​residue presence at the opening was less than 10%, were considered acceptable. Furthermore, A was the most preferred result.

[0376] A: No residue at the opening (less than 1%)

[0377] B: The area of ​​residue present in the opening is more than 1% but less than 5%.

[0378] C: The area of ​​residue present in the opening is more than 5% but less than 10%.

[0379] D: The area of ​​residue in the opening is more than 10%.

[0380] (11) Determine the depth of the substrate surface from which no carbon component was detected (X-ray photoelectron spectroscopy (XPS)) (the penetration depth of carbon component)

[0381] A 4-inch silicon wafer with aluminum vapor deposition was used instead of a 100 mm × 100 mm ITO substrate. The photosensitive resin composition of the sample was coated with a pre-baked film to a thickness of 3.6 μm. Otherwise, development / washing was performed using the same method as described in (9), followed by drying to obtain a patterned substrate for the development process. The opening of the obtained patterned substrate was observed using an FPD / LSI inspection microscope (OPTIPHOT-300; manufactured by Nikon Corporation) to confirm that the opening width was the minimum exposure of the same linewidth (20 μm) as the mask design. Subsequently, the patterned substrate was heat-cured at 250°C using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermal Systems Co., Ltd.) to obtain a cured film. The heat curing conditions were carried out under nitrogen atmosphere, with the patterned substrate placed in an oven at 250°C and heat-cured for 60 minutes. Subsequently, the chemical state of the surface of the opening portion of the sample exposed with the lowest exposure dose (20 μm), the same as the linewidth of the mask design, was determined using an SSX-100 X-ray photoelectron spectrometer manufactured by SSI. Furthermore, the substrate portion between the developed lines was analyzed for depth distribution based on Ar ion etching. To investigate the degree of carbon (organic) contamination of the substrate, the depth at which no carbon component was detected was measured. The results were judged as described below, with A, B, and C, where no carbon component was detected at a depth of less than 10.0 nm from the substrate surface, being considered acceptable. Furthermore, A was the most preferred result.

[0382] A: No carbon component was detected at a depth of less than 5.0 nm from the substrate surface.

[0383] B: No carbon was detected at a depth of 5.0 nm or more but less than 7.5 nm from the substrate surface.

[0384] C: No carbon was detected at a depth of 7.5 nm or more but less than 10.0 nm from the substrate surface.

[0385] D: No carbon component was detected at a depth of 10.0 nm or more from the substrate surface.

[0386] (12) Evaluation of elongation at break

[0387] The resin compositions obtained in the various examples and comparative examples were coated onto 8-inch silicon wafers using a coating and developing apparatus ACT-8 and a spin coating method, with a film thickness of 15 μm after pre-baking at 120°C for 3 minutes. After pre-baking, the wafers were heated to 250°C at 4.0°C / min with an oxygen concentration of less than 20 ppm using an inert oven CLH-21CD-S (manufactured by Koyo Thermal Systems, Inc.), and subjected to heat treatment at 250°C for 1 hour. The silicon wafers were removed when the temperature dropped below 50°C and immersed in 45% by mass hydrofluoric acid for 3 minutes, thereby peeling off the hardened film of the resin composition from the wafers. The films were cut into strips with a width of 1 cm and a length of 9 cm, and stretched at a tensile speed of 50 mm / min using a Tensilon RTM-100 (manufactured by Orientech, Inc.) at a room temperature of 23.0°C and a humidity of 45.0%RH to determine the elongation at break. The test is performed on 10 strips from one specimen, and the average of the top 5 scores is calculated. Judgment is made as follows: AA, A, B, and C, where the elongation at break is 5% or higher, are considered acceptable. Furthermore, AA is the most preferred result.

[0388] AA: The elongation at break is 20% or more.

[0389] A: The elongation at break is 15% or more but less than 20%.

[0390] B: The elongation at break is 10% or more but less than 15%.

[0391] C: Elongation at break is 5% or more but less than 10%.

[0392] D: The elongation at break is less than 5%.

[0393] (13) Storage stability (sensitivity change after placement)

[0394] The photosensitive resin compositions obtained through the various examples and comparative examples were placed at 23°C and 45%RH for 5 days, and then the sensitivity was evaluated in the same order as in (9) to determine the sensitivity. The sensitivity before placement was set as Eop(B), and the sensitivity after placement was set as Eop(A). The sensitivity change x (%) was calculated using the following formula. As described below, A, B, and C, where the value of x was less than 125, were considered acceptable. Furthermore, A was the most preferred result.

[0395] Sensitivity change x (%) = Eop(A) / Eop(B) × 100

[0396] A: x is under 105

[0397] B: x is 105 or higher but less than 115

[0398] C: x is 115 or higher but less than 125

[0399] D: x is 125 or higher.

[0400] (14) Permeability of the hardened membrane

[0401] Using a spin coater (MS-A100; manufactured by Mikasa, Inc.), the spin speed was adjusted so that the pre-baked film thickness was approximately 2.8 μm. The photosensitive resin compositions obtained in each example and comparative example were then coated onto a Tempax glass substrate (manufactured by AGC Technoglass, Inc.) using a buzzer-heated plate (HPD-3000BZN; manufactured by ASONE, Inc.) at 110°C for 120 seconds to produce a pre-baked film with a thickness of approximately 3.0 μm. Subsequently, development / rinsing and drying were performed to obtain a substrate with the developed film. Furthermore, development was performed using the following method: a small automatic photolithography developing unit (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.) was used for spray development with an alkaline developing solution of 2.38% TMAH aqueous solution. The development time was adjusted to reduce the film thickness of the unexposed areas to 0.5 μm, followed by rinsing with deionized water. Then, the substrate with the developed film was cured using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermal Systems Co., Ltd.) at an oxygen concentration of 20 ppm or less, with the temperature increased to 250°C at 5°C / min, and then cured at 250°C for 1 hour, thereby obtaining a substrate with a cured film thickness of 2.0 μm. The transmittance of the substrate with the cured film obtained in this way was measured at a wavelength of 400 nm using a UV-Vis spectrophotometer (MultiSpec-1500 manufactured by Shimadzu Corporation). The following criteria were used to determine whether films A, B, and C, with a transmittance of 60% or higher at a wavelength of 400 nm for a 2.0 μm hardened film, were qualified. Furthermore, A was the most preferred result.

[0402] A: Transmittance is over 90%.

[0403] B: Transmittance is 75% or higher but less than 90%.

[0404] C: Transmittance is above 60% but below 75%.

[0405] D: Transmittance is less than 60%.

[0406] (15) Evaluation of the appearance and luminous reliability of organic EL display devices

[0407] Figure 2This describes the fabrication process of an organic EL display device, including the formation of a planarization layer and a pixel segmentation layer. First, the rotation speed is adjusted so that the final thickness of the planarization layer is 2.0 μm, and the photosensitive resin compositions obtained in each embodiment and comparative example are coated onto a 38 mm × 46 mm alkali-free glass substrate (4) using a spin coating method to obtain a coated film. Next, the coated film is pre-baked at 120°C for 120 seconds under atmospheric pressure using a heating plate (HPD-3000BZN manufactured by ASONE). After exposing the film to ultraviolet light using a photomask, it is developed using a 2.38% TMAH aqueous solution, dissolving only the exposed portion, and then rinsed with pure water. The obtained developed film is then cured. Furthermore, curing was performed using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermal Systems, Ltd.), with the temperature increased to 250°C at a rate of 5°C / min and maintained at 250°C for 1 hour at an oxygen concentration of less than 20 ppm. This resulted in a planarization layer (5) without openings being formed in a 16 mm × 16 mm area at the center of the substrate. The thickness of the planarization layer was 2.0 μm. Subsequently, a 10 nm thick silver / copper alloy film (volume ratio 10:1) was deposited over the entire surface using sputtering, and then etched to form a patterned metallic reflective layer (6). Subsequently, an ITO transparent conductive film with a thickness of 10 nm was formed by sputtering, and the patterned second electrode (7) and auxiliary electrode (8) serving as lead-out electrodes were formed by etching. The substrate was then ultrasonically cleaned for 10 minutes using Semico Clean (registered trademark) 56 (manufactured by Furuuchi Chemical Co., Ltd.), and rinsed with deionized water to obtain the electrode forming substrate. Using a spin coater, the rotation speed was adjusted so that the final pixel segmentation layer thickness was 2.0 μm, and the photosensitive composition was coated onto the surface of the electrode forming substrate to obtain a coated film. The coated film was then pre-baked for 120 seconds at 120°C under atmospheric pressure using a heating plate (HPD-3000BZN manufactured by ASONE Co., Ltd.) to obtain a pre-baked film.

[0408] A positive exposure mask with a patterned light-shielding portion arranged with openings (30 μm wide / 165 μm long) at 50 μm intervals between openings was placed on a coated film. The longitudinal and transverse edges of the patterned light-shielding portion of the mask were parallel to the longitudinal and transverse edges of the alkali-free glass substrate (4). Using a manual exposure machine (MA-1200; manufactured by Dai Nippon Research, Ltd.), the mask was irradiated with a mixed beam of J-rays (313 nm), I-rays (365 nm wavelength), H-rays (405 nm wavelength), and G-rays (436 nm wavelength) from an ultra-high pressure mercury lamp at the minimum required exposure level to obtain an exposed film. Subsequently, development / rinsing was performed to obtain a developed film. In addition, a mask with a chromium-plated patterned light-shielding portion formed on the surface of a sodium glass substrate was used as the positive exposure mask.

[0409] Furthermore, the developing film is heat-treated (cured) to form a hardened film, resulting in a patterned hardened film forming substrate with an aperture ratio of 18% for a patterned hardened film (9) with a thickness of 2.0 μm, comprising openings (a rectangle with a width of 30 μm x 165 μm) arranged at an opening spacing of 50 μm in a 16 mm x 16 mm area in the center of the electrode forming substrate. Curing is performed using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermal Systems, Ltd.), with the temperature increased to 250°C at a rate of 5°C / min and maintained at 250°C for 1 hour at an oxygen concentration of 20 ppm or less. In the organic EL display device obtained after the process described later, the openings mentioned here are the portions that ultimately become light-emitting pixels, and the patterned hardened film is the portion equivalent to a pixel segmentation layer.

[0410] Next, a patterned hardening film is used to form a substrate for fabricating the organic EL display device. To form the organic EL layer (10) containing the light-emitting layer via vacuum evaporation, a vacuum degree of 1×10⁻⁶ is used. -3 Under evaporation conditions below Pa, the patterned hardened film forming substrate is rotated relative to the evaporation source. First, compound HT-1 with a thickness of 10 nm is used as a hole injection layer, and compound HT-2 with a thickness of 50 nm is used as a hole transport layer. Next, compound GH-1 as the host material and compound GD-1 as the dopant material are deposited on the light-emitting layer with a thickness of 40 nm. Then, compound ET-1 and compound LiQ as electron transport materials are stacked in a volume ratio of 1:1 with a thickness of 40 nm.

[0411] Next, after depositing 2 nm of compound LiQ, 10 nm of silver / magnesium alloy (volume ratio 10 / 1) was deposited as the first electrode (11).

[0412] The chemical structures of the compound groups (HT-1, HT-2, GH-1, GD-1, ET-1, LiQ) used to form the organic EL layer are shown below.

[0413] [Chemistry 34]

[0414]

[0415] Furthermore, the thickness mentioned here refers to the value displayed by a quartz oscillating film thickness monitor.

[0416] Subsequently, under low humidity / nitrogen conditions, an epoxy resin adhesive is used to bond the cover glass plate, thereby sealing it to obtain an organic EL display device.

[0417] Appearance observation of organic EL display devices

[0418] Using an FPD / LSI inspection microscope (OPTIPHOT-300; manufactured by Nikon), the surface of the pixel segmentation layer of the obtained organic EL display device was observed. The condition in which film expansion accompanied by bubbles was marked as defective (NG), and the condition in which the pixel segmentation layer surface was flat and no expansion accompanied by bubbles was marked as good (OK).

[0419] Reliability test of light emission of organic EL display device

[0420] The obtained organic EL display device was placed with the display section (light-emitting surface) facing upwards on a heating plate heated to 80°C, at a pressure of 10 mA / cm². 2 The device was then driven to emit light via DC, and the pixel luminous area ratio (the ratio of the actual luminous area to the area of ​​the luminous pixel) was evaluated after one hour. Afterward, the power was temporarily turned off, and the device was extinguished.

[0421] Subsequently, while placed on a heating plate heated to 80°C, an illuminance of 3.0 W / m² was applied using a xenon lamp (simulating sunlight) at a wavelength of 420 nm. 2 Light is continuously irradiated onto the display unit. After 100 hours, 500 hours, and 1000 hours of initial irradiation, the area of ​​the 10 emitting pixels located in the center is measured. The ratio of the area of ​​the emitting pixels after a specified time (pixel emitting area ratio) to the area of ​​the emitting pixels after one hour of heating and irradiation is calculated, and its average value is determined. A higher pixel emitting area ratio indicates better irradiation reliability, and this is evaluated based on the following criteria.

[0422] A: The pixel luminous area ratio is over 95%.

[0423] B: Pixel luminous area ratio is 80% or higher but less than 95%.

[0424] C: Pixel luminous area ratio is 65% or higher but less than 80%.

[0425] D: The pixel luminous area ratio is less than 65%.

[0426] In each evaluation, A through C, with a pixel luminous area ratio of 65% or higher, were rated as qualified, while D was rated as unqualified. Furthermore, A was the optimal result.

[0427] <Synthetic Example 1: Synthesis of the quinone diazide compound QD-a>

[0428] 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 diazidesulfonate chloride were dissolved in 450 g of 1,4-dioxane, and the mixture was kept at room temperature. A liquid containing 15.18 g of triethylamine dissolved in 50 g of 1,4-dioxane was added dropwise to the mixture, keeping the system at a temperature below 35°C. After the addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was added to water. The precipitate was then collected by filtration. The precipitate was dried using a vacuum dryer to obtain the quinone diazide compound QD-a represented by formula (41).

[0429] [Chemistry 35]

[0430]

[0431] In equation (41), This indicates the bonding site with the oxygen atom.

[0432] <Synthetic Example 2: Synthesis of the quinone diazide compound QD-b>

[0433] The quinone diazide compound QD-b represented by formula (42) was synthesized by using 36.27 g (0.135 mol) of 4-naphthoquinone diazidesulfonate chloride instead of 36.27 g (0.135 mol) of 5-naphthoquinone diazidesulfonate chloride, except that the synthesis was carried out by the same method as the synthesis example of quinone diazide compound QD-a.

[0434] [Chemistry 36]

[0435]

[0436] In equation (42), This indicates the bonding site with the oxygen atom.

[0437] <Synthetic Example 3: Synthesis of Diamine (DAP-A)>

[0438] 24.28 g (0.086 mol) of BisP-3MZ (manufactured by Honshu Chemical Industry Co., Ltd.; 4,4'-(3-methylcyclohexane-1,1-diyl)diphenol) and 100 ml of glacial acetic acid were added to a 500 ml four-necked flask containing a stirrer, thermocouple, and dropping funnel. The mixture was stirred, and the internal temperature was raised to 50°C using a hot water bath. 2 ml (0.026 mol) of concentrated nitric acid was added dropwise over 1 hour. The mixture was then cooled in an ice bath to lower the internal temperature to 13°C, and 13.3 ml (0.149 mol) of concentrated nitric acid was added dropwise over another 1 hour. The mixture was then stirred continuously for 3 hours. The precipitated yellow crystals were filtered, washed sequentially with 40 ml of glacial acetic acid and 80 ml of deionized water, and dried under reduced pressure to obtain the dinitrocellulose.

[0439] Subsequently, 50.27 g (0.135 mol) of the dinitromatrix, 180 ml (3.71 mol) of hydrazine monohydrate, and 900 ml of ethanol were added to a 2 L four-necked flask containing a stirrer, thermocouple, Dimroth cooling tube, and dropping funnel. The mixture was stirred under ice bath cooling, and 0.9 g of 5% palladium-carbon (manufactured by 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, washed with 300 ml of ethanol, and the palladium-carbon was removed by filtration. All solvent was removed by heating under reduced pressure. The residue was washed with 75 ml of ice-bath cooled ethanol and filtered, followed by washing with 75 ml of deionized water and 150 ml of diethyl ether, and then dried under reduced pressure to obtain diamine (DAP-A).

[0440] <Synthetic Example 4: Synthesis of Diamine (DAP-B)>

[0441] The dinitro compound was synthesized using 26.70 g (0.086 mol) of BisP-HTG (manufactured by Honshu Chemical Industry Co., Ltd.; 4,4'-(3,3,5-trimethylcyclohexylene)bisphenol) instead of BisP-3MZ (manufactured by Honshu Chemical Industry Co., Ltd.), and 54.06 g (0.135 mol) of the dinitro compound was used. Otherwise, the diamine (DAP-B) was obtained in the same manner as in Synthesis Example 3.

[0442] <Synthetic Example 5: Synthesis of Diamine (DAP-C)>

[0443] The dinitro compound was synthesized by using 23.25 g (0.086 mol) of 4,4'-(1,3-dimethylbutylene)diphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of BisP-3MZ (manufactured by Honshu Chemical Industry Co., Ltd.), and the diamine (DAP-C) was obtained in the same manner as in Synthesis Example 3.

[0444] <Synthetic Example 6: Synthesis of Diamine (DAP-D)>

[0445] The dinitro compound was synthesized by 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 the diamine (DAP-D) was obtained in the same manner as in Synthesis Example 3, except that 44.86 g (0.135 mol) of dinitro compound was used.

[0446] <Synthetic Example 7: Synthesis of Diamine (DAP-E)>

[0447] The dinitro compound was synthesized by using 25.66 g (0.086 mol) of BisP-IOTD (manufactured by Honshu Chemical Industry Co., Ltd.; 4,4'-(2-ethylhexylene)diphenol) instead of BisP-3MZ (manufactured by Honshu Chemical Industry Co., Ltd.), and 52.44 g (0.135 mol) of the dinitro compound was used. Otherwise, the diamine (DAP-E) was obtained in the same manner as in Synthesis Example 3.

[0448] <Synthetic Example 8: Synthesis of Diamine (DAP-F)>

[0449] The dinitro compound was synthesized by 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 46.89 g (0.135 mol) of dinitro compound was used. Otherwise, the diamine (DAP-F) was obtained in the same manner as in Synthesis Example 3.

[0450] <Synthetic Example 9: Synthesis of Diamine (DAP-G)>

[0451] The dinitro compound was synthesized by using 20.84 g (0.086 mol) of BIOC-E (manufactured by Asahi Organics Co., Ltd.; 1,1'-bis(4-hydroxy-3-methylphenyl)ethane) instead of BisP-3MZ (manufactured by Honshu Chemical Industry Co., Ltd.), and the diamine (DAP-G) was obtained by using 44.86 g (0.135 mol) of the dinitro compound. Otherwise, the diamine (DAP-G) was obtained in the same manner as in Synthesis Example 3.

[0452] <Synthetic Example 10: Synthesis of Diamine (DAP-H)>

[0453] The dinitro group was synthesized using 26.52 g (0.086 mol) of SPI (manufactured by JFE Chemical Co., Ltd.; 3,3,3',3'-tetramethyl-1,1'-spirodiindane-6,6'-diol) instead of BisP-3MZ (manufactured by Honshu Chemical Industry Co., Ltd.), and the diamine (DAP-H) was obtained using 53.79 g (0.135 mol) of the dinitro group, otherwise, the same method as in Synthesis Example 3 was used.

[0454] <Synthetic Example 11: Synthesis of Diamine (DAP-I)>

[0455] The dinitro group was synthesized using 23.08 g (0.086 mol) of TMHI (manufactured by JFE Chemical Co., Ltd.; 3-(4-hydroxyphenyl)-1,1,3-trimethyl-5-indanol) instead of BisP-3MZ (manufactured by Honshu Chemical Industry Co., Ltd.), and 48.38 g (0.135 mol) of dinitro group was used. Otherwise, the diamine (DAP-H) was obtained in the same manner as in Synthesis Example 3.

[0456] <Synthetic Example 12: Synthesis of 2,2-bis[3-(3-aminobenzamide)-4-hydroxyphenyl]hexafluoropropane (HA)>

[0457] Dissolve 18.3 g (0.05 mol) of BAHF in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide (manufactured by Tokyo Chemical Industry Co., Ltd.), and cool to -15°C. Add dropwise a solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 mL of acetone. After the addition is complete, stir at -15°C for 4 hours, then allow to return to room temperature. Filter the precipitated white solid and dry it under vacuum at 50°C.

[0458] 30 g of the obtained white solid was placed in a 300 mL stainless steel autoclave and dispersed in 250 mL of methyl cellosolve. 2.0 g of 5% palladium-carbon (manufactured by Washikari Pure Chemicals) was added. Hydrogen was introduced into the autoclave using a balloon, and a reduction reaction was carried out at room temperature. The reaction was considered complete after approximately 2 hours, when the balloon was confirmed to have stopped shrinking. After the reaction, the palladium compound acting as a catalyst was removed by filtration, and the mixture was concentrated using a rotary evaporator to obtain the diamine compound (HA) represented by the following formula.

[0459] <Synthetic Example 13: Synthesis of Diamine Compound (HB)>

[0460] The 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.

[0461] <Synthetic Example 14: Synthesis of Diamine Compound (HC)>

[0462] The 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.

[0463] <Synthetic Example 15: Synthesis of Diamine Compound (HD)>

[0464] The 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.

[0465] <Synthetic Example 16: Synthesis of Diamine Compound (HE)>

[0466] The 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.

[0467] <Synthetic Example 17: Synthesis of the diamine compound (DAP-J)>

[0468] The dinitro compound was synthesized by using 23.08 g (0.086 mol) of 4,4'-cyclohexylene bisphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of BisP-3MZ (manufactured by Honshu Chemical Industry Co., Ltd.), and the diamine compound (DAP-J) was obtained by using 48.38 g (0.135 mol) of dinitro compound. Otherwise, the same method as in Synthesis Example 3 was used.

[0469] <Synthetic Example 18: Synthesis of the Diamine Compound (DAP-K)>

[0470] The dinitro compound was synthesized by using 27.90 g (0.086 mol) of 4,4'-(p-mentane-2,8-diyl)diphenol (manufactured by Chemieliva Pharmaceutical) as a terpene diphenol instead of BisP-3MZ (manufactured by Honshu Chemical Industry Co., Ltd.), and 55.95 g (0.135 mol) of dinitro compound was used. Otherwise, the diamine compound (DAP-K) was obtained in the same manner as in Synthesis Example 3.

[0471] The structures of the diamine compounds obtained in Synthetic Examples 3 to 18 are shown below.

[0472] [Chemistry 37]

[0473]

[0474] <Synthetic Example 51: Synthesis of Polyamic Acid (a-1)>

[0475] 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. 7.51 g (0.025 g) of TDA and 7.76 g (0.025 mol) of ODPA were added to the solution 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 as a capping agent was added along with 10 g of MPA, and the reaction was carried out at 60°C for 1 hour. The mixture was then stirred at 140°C for 4 hours. After stirring, the solution was added to 2 L of deionized water, and the polymer solid precipitate was collected by filtration. The precipitate was then washed three times with 2 L of deionized water, and the collected polymer solid was dried in a vacuum dryer at 50°C for 72 hours to obtain polyamic acid (a-1) as a form of polyimide.

[0476] <Synthetic Example 52: Synthesis of Polyamic Acid (a-2)>

[0477] Using 14.13 g (0.042 mol) of the diamine compound (DAP-B) obtained in Synthesis Example 4 instead of the diamine compound (DAP-A), polyamic acid (a-2) as a form of polyimide was obtained in the same manner as in Synthesis Example 51.

[0478] <Synthetic Example 53: Synthesis of Polyamic Acid (a-3)>

[0479] Using 12.47 g (0.042 mol) of the diamine compound (DAP-C) obtained in Synthesis Example 5 instead of the diamine compound (DAP-A), polyamic acid (a-3) as a form of polyimide was obtained in the same manner as in Synthesis Example 51.

[0480] <Synthetic Example 54: Synthesis of Polyamic Acid (a-4)>

[0481] Using 11.30 g (0.042 mol) of the diamine compound (DAP-D) obtained in Synthesis Example 6 instead of the diamine compound (DAP-A), polyamic acid (a-4) as a form of polyimide was obtained in the same manner as in Synthesis Example 51.

[0482] <Synthetic Example 55: Synthesis of Polyamic Acid (a-5)>

[0483] Using 13.63 g (0.042 mol) of the diamine compound (DAP-E) obtained in Synthesis Example 7 instead of the diamine compound (DAP-A), polyamic acid (a-5) as a form of polyimide was obtained in the same manner as in Synthesis Example 51.

[0484] <Synthetic Example 56: Synthesis of Polyamic Acid (a-6)>

[0485] Using 11.30 g (0.042 mol) of the diamine compound (DAP-F) obtained in Synthesis Example 8 instead of the diamine compound (DAP-A), polyamic acid (a-6) as a form of polyimide was obtained in the same manner as in Synthesis Example 51.

[0486] <Synthetic Example 57: Synthesis of Polyamic Acid (a-7)>

[0487] Using 11.30 g (0.042 mol) of the diamine compound (DAP-G) obtained in Synthesis Example 9 instead of the diamine compound (DAP-A), polyamic acid (a-7) as a form of polyimide was obtained in the same manner as in Synthesis Example 51.

[0488] <Synthetic Example 58: Synthesis of Polyamic Acid (a-8)>

[0489] Using 14.05 g (0.042 mol) of the diamine compound (DAP-H) obtained in Synthesis Example 10 instead of the diamine compound (DAP-A), polyamic acid (a-8) as a form of polyimide was obtained in the same manner as in Synthesis Example 51.

[0490] <Synthetic Example 59: Synthesis of Polyamic Acid (a-9)>

[0491] Using 12.38 g (0.042 mol) of the diamine compound (DAP-I) obtained in Synthesis Example 11 instead of the diamine compound (DAP-A), polyamic acid (a-9) as a form of polyimide was obtained in the same manner as in Synthesis Example 51.

[0492] <Synthetic Example 60: Synthesis of Polyamic Acid (a-10)>

[0493] Using 6.61 g (0.025 mol) of MCTC (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of TDA, polyamic acid (a-10) as a polyimide was obtained in the same manner as in Synthesis Example 52.

[0494] <Synthetic Example 61: Synthesis of Polyamic Acid (a-11)>

[0495] Using 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.), instead of 14.13 g (0.042 mol) of diamine compound (DAP-B), polyamic acid (a-11) as a form of polyimide was obtained in the same manner as in Synthesis Example 52.

[0496] <Synthetic Example 62: Synthesis of Polyamic Acid (a-12)>

[0497] Using 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.), instead of 14.13 g (0.042 mol) of diamine compound (DAP-B), polyamic acid (a-12) as a form of polyimide was obtained in the same manner as in Synthesis Example 52.

[0498] <Synthetic Example 63: Synthesis of Polyamic Acid Ester (a-13)>

[0499] 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. 15.0 g (0.050 mol) of TDA was added to this solution 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 as a capping agent was added to this solution along with 10 g of MPA, and the reaction was carried out at 60°C for 1 hour. After lowering the temperature from 60°C to 40°C, a solution diluted with 10 g of MPA containing 11.9 g (0.010 mol) of DMFDMA was added dropwise. The mixture was stirred continuously at 40°C for 2 hours after the addition. After stirring, the solution was added to 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 ester (a-13) as a form of polyimide.

[0500] <Synthetic Example 64: Synthesis of Polyamate (a-14)>

[0501] Using 22.35 g (0.042 mol) of diamine compound (HD) instead of 24.02 g (0.042 mol) of diamine compound (HC), a polyamic ester (a-14) as a form of polyimide was obtained in the same manner as in Synthesis Example 63.

[0502] <Synthetic Example 65: Synthesis of Polyamic Acid Ester (a-15)>

[0503] Using 21.19 g (0.042 mol) of diamine compound (HE) instead of 24.02 g (0.042 mol) of diamine compound (HC), a polyamic ester (a-15) as a polyimide was obtained in the same manner as in Synthesis Example 63.

[0504] <Synthetic Example 66: Synthesis of Polyamic Acid Ester (a-16)>

[0505] Using 13.21 g (0.050 mol) of MCTC instead of 15.01 g (0.050 mol) of TDA, a polyamic ester (a-16) as a polyimide was obtained in the same manner as in Synthesis Example 63.

[0506] <Synthetic Example 67: Synthesis of Polyamate (a-17)>

[0507] For the solvent, DMIB was used instead of MPA, otherwise, a polyamic ester (a-17) as a polyimide was obtained in the same manner as in Synthesis Example 66.

[0508] <Synthetic Example 68: Synthesis of Polyamic Acid Ester (a-18)>

[0509] For the solvent, DMPA was used instead of MPA, otherwise, a polyamic ester (a-18) as a polyimide was obtained in the same manner as in Synthesis Example 66.

[0510] <Synthetic Example 69: Synthesis of Polyamate (a-19)>

[0511] For the solvent, GBL was used instead of MPA, and otherwise, a polyamic ester (a-19) as a polyimide was obtained in the same manner as in Synthesis Example 66.

[0512] <Synthetic Example 70: Synthesis of Polyamic Acid (a-20)>

[0513] Using 15.51 g (0.050 mol) of ODPA (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of 7.51 g (0.025 mol) of TDA and 7.76 g (0.025 mol) of ODPA, polyamic acid (a-20) as a form of polyimide was obtained in the same manner as in Synthesis Example 52.

[0514] <Synthetic Example 71: Synthesis of Polyimide (a-21)>

[0515] 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. 7.51 g (0.025 mol) of TDA and 7.76 g (0.025 mol) of ODPA were added to the solution 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 as a capping agent was added along with 10 g of MPA, and the reaction was carried out at 60°C for 1 hour. The mixture was then stirred at 180°C for 4 hours. After stirring, the solution was added to 2 L of deionized water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with deionized water, and dried in a vacuum dryer at 50°C for 72 hours to obtain polyimide (a-21) powder.

[0516] <Synthetic Example 72: Synthesis of Polyamic Acid (a-22)>

[0517] Using 10.72 g (0.042 mol) of BAP instead of the diamine compound (DAP-A), polyamic acid (a-22) as a polyimide was obtained in the same manner as in Synthesis Example 51.

[0518] <Synthetic Example 73: Synthesis of Polyamate (a-23)>

[0519] Using 25.09 g (0.042 mol) of diamine compound (HA) instead of 24.02 g (0.042 mol) of diamine compound (HC), a polyamic ester (a-23) as a form of polyimide was obtained in the same manner as in Synthesis Example 63.

[0520] <Synthetic Example 74: Synthesis of Polyamate (a-24)>

[0521] Using 20.86 g (0.042 mol) of diamine compound (HB) instead of 24.02 g (0.042 mol) of diamine compound (HC), a polyamic ester (a-24) as a polyimide was obtained in the same manner as in Synthesis Example 63.

[0522] <Synthetic Example 75: Synthesis of Polyamate (a-25)>

[0523] Using 15.5 g (0.050 mol) of ODPA instead of 15.0 g (0.050 mol) of TDA, a polyamic ester (a-25) as a polyimide was obtained in the same manner as in Synthesis Example 63.

[0524] <Synthetic Example 76: Synthesis of Polyamic Acid Ester (a-26)>

[0525] Using 13.4 g (0.039 mol) of diamine compound (DAP-B) and 1.46 g (0.0025 mol) of diamine compound (HC) instead of 24.02 g (0.042 mol) of diamine compound (HC), a polyamic ester (a-26) as a polyimide was obtained in the same manner as in Synthesis Example 75.

[0526] <Synthetic Example 77: Synthesis of Polyamate (a-27)>

[0527] Using 12.6 g (0.037 mol) of diamine compound (DAP-B) and 2.93 g (0.0051 mol) of diamine compound (HC) instead of 24.02 g (0.042 mol) of diamine compound (HC), a polyamic ester (a-27) as a polyimide was obtained in the same manner as in Synthesis Example 75.

[0528] <Synthetic Example 78: Synthesis of Polyamate (a-28)>

[0529] Using 10.0 g (0.029 mol) of diamine compound (DAP-B) and 7.32 g (0.013 mol) of diamine compound (HC) instead of 24.02 g (0.042 mol) of diamine compound (HC), a polyamic ester (a-28) as a polyimide was obtained in the same manner as in Synthesis Example 75.

[0530] <Synthetic Example 79: Synthesis of Polyamate (a-29)>

[0531] Using 7.41 g (0.022 mol) of diamine compound (DAP-B) and 11.7 g (0.020 mol) of diamine compound (HC) instead of 24.02 g (0.042 mol) of diamine compound (HC), a polyamic ester (a-29) as a polyimide was obtained in the same manner as in Synthesis Example 75.

[0532] <Synthetic Example 80: Synthesis of Polyamate (a-30)>

[0533] Using 5.17 g (0.015 mol) of diamine compound (DAP-B) and 15.5 g (0.027 mol) of diamine compound (HC) instead of 24.02 g (0.042 mol) of diamine compound (HC), a polyamic ester (a-30) as a polyimide was obtained in the same manner as in Synthesis Example 75.

[0534] <Synthetic Example 81: Synthesis of Polyamate (a-31)>

[0535] Using 3.45 g (0.010 mol) of diamine compound (DAP-B) and 18.4 g (0.032 mol) of diamine compound (HC) instead of 24.02 g (0.042 mol) of diamine compound (HC), a polyamic ester (a-31) as a polyimide was obtained in the same manner as in Synthesis Example 75.

[0536] <Synthetic Example 82: Synthesis of Polyamic Acid Ester (a-32)>

[0537] Using 8.80 g (0.029 mol) of diamine compound (DAP-C) and 7.35 g (0.013 mol) of diamine compound (HC) instead of 24.02 g (0.042 mol) of diamine compound (HC), a polyamic ester (a-32) as a polyimide was obtained in the same manner as in Synthesis Example 75.

[0538] <Synthetic Example 83: Synthesis of Polyamic Acid Ester (a-33)>

[0539] Using 9.98 g (0.029 mol) of diamine compound (DAP-B) and 6.84 g (0.013 mol) of diamine compound (HD) instead of 24.02 g (0.042 mol) of diamine compound (HC), a polyamic ester (a-33) as a polyimide was obtained in the same manner as in Synthesis Example 75.

[0540] <Synthetic Example 84: Synthesis of Polyamate (a-34)>

[0541] Using 8.80 g (0.029 mol) of diamine compound (DAP-C) and 6.31 g (0.013 mol) of diamine compound (HB) instead of 24.02 g (0.042 mol) of diamine compound (HC), a polyamic ester (a-34) as a polyimide was obtained in the same manner as in Synthesis Example 75.

[0542] <Synthetic Example 85: Synthesis of Polyamic Acid Ester (a-35)>

[0543] Using 7.57 g (0.029 mol) of BAP and 7.35 g (0.013 mol) of diamine compound (HC) instead of 24.02 g (0.042 mol) of diamine compound (HC), a polyamic ester (a-35) as a form of polyimide was obtained in the same manner as in Synthesis Example 75.

[0544] <Synthetic Example 86: Synthesis of Polyamic Acid Ester (a-36)>

[0545] Using 1.17 g (0.010 mol) of 4-APA instead of 1.09 g (0.010 mol) of MAP, a polyamic ester (a-36) as a polyimide was obtained in the same manner as in Synthesis Example 78.

[0546] <Synthetic Example 87: Synthesis of Polyamate (a-37)>

[0547] Using 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 instead of 24.02 g (0.042 mol) of diamine compound (HC), a polyamic ester (a-37) as a polyimide was obtained in the same manner as in Synthesis Example 75.

[0548] <Synthetic Example 88: Synthesis of Polyamic Acid Ester (a-38)>

[0549] Using 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 instead of 24.02 g (0.042 mol) of diamine compound (HC), a polyamic ester (a-38) as a polyimide was obtained in the same manner as in Synthesis Example 75.

[0550] <Synthetic Example 89: Synthesis of Polyamic Acid Ester (a-39)>

[0551] Using 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 instead of 24.02 g (0.042 mol) of diamine compound (HC), a polyamic ester (a-39) as a polyimide was obtained in the same manner as in Synthesis Example 75.

[0552] <Synthetic Example 90: Synthesis of Polyamate (a-40)>

[0553] Using 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 instead of 24.02 g (0.042 mol) of diamine compound (HC), a polyamic ester (a-40) of polyimide was obtained in the same manner as in Synthesis Example 75.

[0554] <Synthetic Example 91: Synthesis of Polyamate (a-41)>

[0555] Using 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 instead of 24.02 g (0.042 mol) of diamine compound (HC), a polyamic ester (a-41) as a polyimide was obtained in the same manner as in Synthesis Example 75.

[0556] <Synthetic Example 92: Synthesis of Polyamic Acid Ester (a-42)>

[0557] Using 0.51 g (0.0025 mol) of 3,4'-ODA instead of 0.74 g (0.0025 mol) of TPE-R, a polyamic ester (a-42) as a polyimide was obtained in the same manner as in Synthesis Example 88.

[0558] <Synthetic Example 93: Synthesis of Polyamic Acid Ester (a-43)>

[0559] Using 9.98 g (0.029 mol) of diamine compound (DAP-B) and 7.35 g (0.013 mol) of HC instead of 14.13 g (0.042 mol) of diamine compound (DAP-B), polyamic acid (a-43) as a form of polyimide was obtained in the same manner as in Synthesis Example 70.

[0560] <Synthetic Example 94: Synthesis of Polyamate (a-44)>

[0561] For the solvent, DMIB was used instead of MPA, otherwise, a polyamic ester (a-44) as a polyimide was obtained in the same manner as in Synthesis Example 78.

[0562] <Synthetic Example 95: Synthesis of Polyamic Acid Ester (a-45)>

[0563] For the solvent, GBL was used instead of MPA, and otherwise, a polyamic ester (a-45) as a polyimide was obtained in the same manner as in Synthesis Example 78.

[0564] <Synthetic Example 96: Synthesis of Polyamic Acid Ester (a-46)>

[0565] After stirring, the solution was added to a 2 L mixture of deionized water and methanol (1 / 1, by weight). The polymer solid precipitate was collected by filtration and then washed three times with a 2 L mixture of deionized water and methanol (1 / 1, by weight). The collected polymer solid was dried in a vacuum dryer at 50°C for 72 hours. Otherwise, a polyamic acid ester (a-46) as a form of polyimide was obtained in the same manner as in Synthesis Example 63.

[0566] <Synthetic Example 97: Synthesis of Polyamate (a-47)>

[0567] Using 24.60 g (0.043 mol) of the diamine compound (HC), without using MAP as a capping agent, a polyamic ester (a-47) as a polyimide was obtained in the same manner as in Synthesis Example 63.

[0568] <Synthetic Example 98: Synthesis of Polyamic Acid (a-48)>

[0569] Using 7.66 g (0.025 mol) of HBPDA instead of 7.51 g (0.025 mol) of TDA, polyamic acid (a-48) as a polyimide was obtained in the same manner as in Synthesis Example 52.

[0570] <Synthetic Example 99: Synthesis of Polyamic Acid (a-49)>

[0571] Using 12.53 g (0.042 mol) of the diamine compound (DAP-J) obtained in Synthesis Example 17 instead of the diamine compound (DAP-A), polyamic acid (a-49) as a form of polyimide was obtained in the same manner as in Synthesis Example 51.

[0572] <Synthetic Example 100: Synthesis of Polyamic Acid (a-50)>

[0573] Using 14.89 g (0.042 mol) of the diamine compound (DAP-K) obtained in Synthesis Example 18 instead of the diamine compound (DAP-A), polyamic acid (a-50) as a form of polyimide was obtained in the same manner as in Synthesis Example 51.

[0574] Tables 1-1 to 1-4 show the results of determination of the constituent components (molar ratio), molecular weight (Mw), esterification rate [%], imide ring closure rate [%], amount of components with a molecular weight of less than 1000, and content [parts by mass] of compounds represented by formulas (17) and (18) for synthetic examples 51 to 100.

[0575] [Table 1-1]

[0576]

[0577] [Table 1-2]

[0578]

[0579] [Table 1-3]

[0580]

[0581] [Table 1-4]

[0582]

[0583] [Example 1]

[0584] Under a yellow light, 4.07 g of polyamic acid ester (a-1) as resin (A), 0.488 g of photoacid generator (B-1) as photosensitizer (B), namely 0.488 g of QD-a and 0.488 g of QD-b, 0.814 g of HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.; the compound represented by formula (44) below) as crosslinking agent (E), and 0.004 g of BYK-302 (manufactured by BYK-Chemie Japan Co., Ltd.) as surfactant (F) were added to 28.6 g of a mixed solvent (C2) containing PGME, ethyl lactate and GBL in a mass ratio of 35:35:30. The mixture was stirred for 30 minutes to dissolve the solids and prepare a homogeneous solution with a solid content of 18.0% by mass.

[0585] [Chemistry 38]

[0586]

[0587] The obtained solution was then filtered using a 0.45 μm φ filter to obtain photosensitive resin composition 1. Subsequently, the obtained photosensitive resin composition 1 was subjected to various evaluations by determination / evaluation methods (6) to determination / evaluation methods (14).

[0588] [Examples 2 to 46 and Comparative Examples 1 to 5]

[0589] The photosensitive resin compositions were prepared using the compositions described in Tables 2-1 to 2-4. Except as in Example 1, photosensitive resin compositions 2 to 51, a hardened film, and an organic EL display device were also prepared. The evaluation results are shown in Tables 3-1 to 3-4.

[0590] [Table 2-1]

[0591]

[0592] [Table 2-2]

[0593]

[0594] [Table 2-3]

[0595]

[0596] [Table 2-4]

[0597]

[0598] The ingredients listed in the table are as follows.

[0599] Resin (A)

[0600] (a-1)~(a-12), (a-20), (a-22), (a-43), (a-48)~(a-50): the polyamic acid resin

[0601] (a-13)~(a-19), (a-23)~(a-42), (a-44)~(a-47): the polyaminate resin

[0602] (a-21): The polyimide resin

[0603] Photosensitive agent (B)

[0604] (b-1): QD-a (the compound described in Synthesis Example 1)

[0605] (b-2): QD-b (the compound described in Synthesis Example 2)

[0606] Solvent (C)

[0607] (c-1): MPA

[0608] (c-2): DMIB

[0609] (c-3): DMPA

[0610] (c-4): PGME (a solvent with hydroxyl groups and a boiling point of 120°C at atmospheric pressure)

[0611] (c-5): Ethyl lactate (a solvent with hydroxyl groups and a boiling point of 154°C at atmospheric pressure)

[0612] (c-6): GBL

[0613] Crosslinking agent (E)

[0614] (e-1): HMOM-TPHAP (manufactured by Honshu Chemical Industries, Ltd.)

[0615] Surfactant (F)

[0616] (f-1): BYK-302 (manufactured by BYK-Chemie Japan).

[0617] [Table 3-1]

[0618]

[0619] [Table 3-2]

[0620]

[0621] [Table 3-3]

[0622]

[0623] [Table 3-4]

[0624]

[0625] The results show that the photosensitive resin composition of the embodiments exhibits excellent diluent solubility, high sensitivity, low development residue, and suppressed contamination at the openings after curing, resulting in excellent reliability for the organic EL display device. In Comparative Examples 1, 3, 4, and 5, since resin (A) does not contain any of the diamine residues represented by formulas (2) to (4), the diluent solubility is poor. In Comparative Example 2, since resin (A) does not contain any of the diamine residues represented by formulas (2) to (4) but contains diamine residues containing fluorine, contamination was observed at the openings after curing. Furthermore, when a pixel dividing layer is formed on top of the planarization layer for manufacturing an organic EL display device, foaming was observed between the planarization layer and the pixel dividing layer. This is believed to be due to the generation of gas, such as water, from the planarization layer during the heat curing process of the pixel dividing layer.

[0626] Explanation of icon numbers

[0627] 1: Step substrate

[0628] 2: Hardened material

[0629] 3: Baseline

[0630] 4: Alkali-free glass substrate

[0631] 5: Planarization layer

[0632] 6: Metal reflective layer

[0633] 7: First electrode

[0634] 8: Auxiliary electrode

[0635] 9: Patterned hardened film

[0636] 10: Organic EL layer

[0637] 11: Second electrode

Claims

1. A photosensitive resin composition comprising a resin (A) (hereinafter referred to as resin (A)) containing at least one of the structural units represented by formula (1), formula (19), and formula (70), a photosensitizer (B), and a solvent (C). When the total amount of diamine residues in the resin (A) is set to 100 mol%, the total content of diamine residues represented by any one of formulas (2) to (4) is 30 mol% to 100 mol%. [Chemistry 1] (In equations (1), (19) and (70), Y) 1 Each of the following can be independently represented: an aliphatic structure with 2–20 carbon atoms, an alicyclic structure with 4–40 carbon atoms, and an aromatic structure with 6–40 carbon atoms, representing an acid dianhydride residue with 2–40 carbon atoms; Z 1 Each of the formulas (2) to (4) represents a diamine residue independently; R 1 Each of the following can be independently represented: a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a monovalent group having 2 to 20 carbon atoms with an ethylene-like unsaturated double bond; (Indicates the bonding part) [Chemistry 2] (In equations (2), (3) and (4), X) 1 R is independently a direct bond or a divalent base represented by equation (5). 2 Each of the alkyl groups having 1 to 4 carbon atoms is represented independently, X 2 Let k be the divalent base represented by equation (6) or equation (7), where k independently represents 0 or 1, respectively. (This indicates a bond point that is bonded to an imide structure, amide structure, amide ester structure, or amide acid structure) [Chemistry 3] (in formula (5), Indicates the bond node that bonds with a nitrogen atom; (Represents the bond node with an aromatic ring bond) [Chemistry 4] (In equations (6) and (7), R) 3 Each of the following groups independently represents an alkyl group having 1 to 4 carbon atoms, where a represents 1 or 2, b represents an integer from 1 to 3, and R 4 and R 5 Each can independently represent a hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms. This represents the bond node with an aromatic ring bond; where, R 4 With R 5 (Do not use the same structure).

2. The photosensitive resin composition according to claim 1, wherein, The resin (A) contains the diamine residue represented by formula (2), and R in formula (6) 3 The total number of carbons is more than 1 and less than 5, and R in equation (7) is... 4 The number of carbons and the R 5 The total number of carbon atoms is 3 or more and less than 10.

3. The photosensitive resin composition according to claim 1 or claim 2, wherein, The resin (A) contains the diamine residue represented by formula (2), and in formula (6), when a=1 is set as formula (6-1) and a=2 is set as formula (6-2), conditions 1 and 2 are satisfied, and the R in formula (7) 4 The number of carbons and the R 5 The number of carbon atoms is different; Condition 1: In formula (6-1), R 11 ~R 14 The total number of carbons and R 15 ~R 18 The total number of carbons is different; Condition 2: In formula (6-2), R 19 ~R 22 The total number of carbons and R 25 ~R 28 The total number of carbons is different; [Chemistry 5] (In equations (6-1) and (6-2), R) 11 ~R 28 Each of the above can independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; wherein formulas (6-1) and (6-2) both satisfy the conditions of formula (6).

4. The photosensitive resin composition according to claim 1 or claim 2, wherein, The resin (A) contains the diamine residue represented by formula (2), and the X 2 The divalent base represented by any one of equations (8) to (13) and (76) to (83); [Chemistry 6] (In equations (8) to (13) and equations (76) to (83), (This indicates the bond node with the aromatic ring bond).

5. The photosensitive resin composition according to claim 1 or claim 2, wherein, In equations (1), (19), and (70), Y 1 Each of the following can be independently represented as an anhydride residue with 8 to 40 carbon atoms having a diphenyl ether structure.

6. The photosensitive resin composition according to claim 1 or claim 2, wherein, The resin (A) has the structure represented by formula (84); [Chemistry 7] (In equation (84), R) 29 It can represent hydroxyl, alkyl with 1 to 3 carbons, alkoxy with 1 to 3 carbons, alkenyl with 2 to 5 carbons, or alkynyl with 2 to 5 carbons; (This indicates the bonding site with the nitrogen atom).

7. The photosensitive resin composition according to claim 1 or claim 2, wherein, The resin (A) comprises structural unit (a) and / or structural unit (b), and the resin (A) comprises structural unit (c) and / or structural unit (d). The resin (A) comprises at least one of structural unit (a) and structural unit (c); Structural unit (a): Z in equations (1), (19) and (70) 1 The expression is represented by equation (2), and there are two X's in equation (2). 1 All are structural units represented by direct keys, as shown in equations (1), (19), or (70). Structural unit (b): Z in equations (48), (49) and (71) 3 The two X's represented by equation (45) and existing in equation (45) 1 All are structural units represented by direct keys, as shown in equations (48), (49), or (71). Structural unit (c): Z in equations (1), (19) and (70) 1 The expression is represented by equation (2), and there are two X's in equation (2). 1 At least one X in 1 The structural unit represented by equation (1), equation (19), or equation (70) of the divalent base represented by equation (5) is... Structural unit (d): Z in equations (48), (49) and (71) 3 The two X's represented by equation (45) and existing in equation (45) 1 At least one X in 1 The structural unit represented by equations (48), (49), or (71) of the divalent base represented by equation (5) is... [Chemistry 8] (In equations (48), (49) and (71), Y) 1 and R 1 The same range as that described in equations (1), (19), and (70); Z 3 The diamine residues represented by formula (45) are expressed independently; (Indicates the bonding part) [Chemistry 9] (In equation (45), X) 1 R is independently a direct bond or a divalent base represented by equation (5). 2 and k is the same range as that described in equation (2); X 3 The divalent organic group represented by any one of formulas (64) to (69); (This indicates a bond point that is bonded to an imide structure, amide structure, amide ester structure, or amide acid structure) [Chemistry 10] ( (This indicates the bond node with the aromatic ring bond).

8. The photosensitive resin composition according to claim 7, wherein, When the total amount of polyimide structural units contained in the resin (A) is set to 100 mol%, the total content of structural unit (a) and structural unit (b) is 20 mol% to 95 mol%, and the total content of structural unit (c) and structural unit (d) is 5 mol% to 80 mol%.

9. The photosensitive resin composition according to claim 1 or claim 2, wherein, The resin (A) further comprises at least one of the structural unit represented by formula (50), the structural unit represented by formula (51), and the structural unit represented by formula (72); [Chemistry 11] (In equations (50), (51) and (72), Y) 1 and R 1 The same range as that described in equations (1), (19), and (70); Z 5 The diamine residues represented by formula (46) or formula (47) are represented independently, respectively; (Indicates the bonding part) [Chemistry 12] (In equations (46) and (47), X) 4 Indicates a direct bond or -C(CH3)2-; t represents any integer from 0 to 2; (This indicates a bond point that is bonded to an imide, amide, amide ester, or amide acid structure).

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

11. The photosensitive resin composition according to claim 1 or claim 2, wherein, The resin (A) contains dianhydride residues with 4 to 20 carbon atoms that have an alicyclic structure.

12. The photosensitive resin composition according to claim 11, wherein, When the total amount of dianhydride residues in the resin (A) is set to 100 mol%, the total content of dianhydride residues with carbon numbers of 4 to 20 in the alicyclic structure is 20 mol% to 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 formulas (15), (16), (85) to (94); [Chemistry 13] (In equations (15), (16), (85) to (94),) (This indicates a bond point that is bonded to an imide, amide, amide ester, or amide acid structure).

14. The photosensitive resin composition according to claim 1 or claim 2, wherein, The imide ring closure rate of the resin (A) is less than 50%.

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

16. The photosensitive resin composition according to claim 1 or claim 2, wherein, The solvent (C) contains the solvent represented by formula (17) and / or the solvent (C1) represented by formula (18). [Chemistry 14] (In equations (17) and (18), R) 6 Each alkyl group having 1 to 6 carbon atoms is represented independently. R 7 (Refers to alkyl groups having 2 to 6 carbon atoms).

17. The photosensitive resin composition according to claim 1 or claim 2, wherein, The solvent (C) includes a solvent (C2) having hydroxyl groups 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 claim 2, wherein, The photosensitive resin composition comprises a solvent represented by formula (17) and / or a solvent represented by formula (18) (hereinafter referred to as solvent (C1)), and a solvent (C2) having hydroxyl groups and a boiling point of 100°C or higher and 200°C or lower at atmospheric pressure (hereinafter referred to as solvent (C2)). The content ratio of solvent (C1) in the photosensitive resin composition to X (mass) and solvent (C2) to Y (mass) is Y / X, where Y / X is 1 or more and 1000 or less.

19. A cured material, formed by curing the photosensitive resin composition as described in claim 1 or claim 2.

20. A display device comprising the hardened material as claimed in claim 19.

21. An electronic component comprising the hardened material as claimed in claim 19.

Images