Photosensitive resin composition, cured product, organic el display device, display device and phenol compound

Abstract

The present invention addresses the problem of providing a photosensitive resin composition capable of forming a film having a low transmittance at a wavelength near 450 nm after curing even when a heating atmosphere during curing is at a low oxygen concentration of less than 5%. This photosensitive resin composition contains an alkali-soluble resin (a), a phenol compound (b) having a structure represented by formula (1), and a photosensitive compound (c). (In formula (1), n represents an integer of 2-4, and * represents a linking bond. > # imgabs0 #

Description

Technical Field

[0001] The invention relates to a photosensitive resin composition suitable for use in a planarization layer, an insulating layer, etc. of a display device such as an organic EL display device, and a phenolic compound that may be contained in the photosensitive resin composition. Background Art

[0002] In display devices having thin displays such as smartphones, tablet computers, and televisions, many products using organic electroluminescence (hereinafter referred to as "organic EL") display devices have been developed. Generally, an organic EL display device has a driving circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate, and can emit light by applying a voltage between the opposed first electrode and second electrode. Among them, as a material for the planarization layer and the insulating layer, a photosensitive resin composition capable of forming a pattern by ultraviolet light irradiation is usually used. Among them, the photosensitive resin composition using a polyimide-based resin is preferably used because the resin has high heat resistance and few gas components generated from the cured product, and thus a highly reliable organic EL display device can be obtained.

[0003] In recent years, with the application of a driving thin film transistor (Thin Film Transistor: hereinafter referred to as TFT) using an oxide semiconductor layer to an organic EL display device, in order to prevent malfunction caused by light entering the TFT, etc., it is required to reduce the transmittance near a wavelength of 450 nm of the insulating layer and the planarization layer. On the other hand, a high transmittance of ultraviolet light is required when patterning the photosensitive resin composition. As a technique for reducing the transmittance near a wavelength of 450 nm of the cured product by heat curing after pattern formation, there is a method of adding a Novolac resin, a photosensitizer, and a polymer other than the Novolac resin (see Patent Document 1).

[0004] In addition, as a technique for reducing the transmittance near a wavelength of 450 nm and the overall transmittance of visible light and improving the blackness, there is a method of adding a quinone diazide compound and a thermochromic compound that colors by heating and shows a maximum absorption at 350 nm or more and 700 nm or less, and a compound that does not have a maximum absorption at 350 nm or more and less than 500 nm and has a maximum absorption at 500 nm or more and 750 nm or less to an alkali-soluble resin (see Patent Document 2).

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: International Publication No. 2015 / 129092

[0008] Patent Document 2: Japanese Patent Application Laid-Open No. 2004-326094 Summary of the Invention

[0009] Problems to be Solved by the Invention

[0010] The applicant has conducted research. As a result, the heated resin compositions described in Patent Documents 1 and 2 utilize oxidation caused by oxygen in the atmosphere to reduce the transmittance near a wavelength of 450 nm during heat curing. Therefore, at a low oxygen concentration of less than 5%, the transmittance does not decrease, and there are limitations in the curing conditions.

[0011] On the other hand, it has been found that when these resin compositions are used in an organic EL display device or the like, if heat curing is performed in an atmosphere with an oxygen concentration of 5% or more, the electrode is contaminated by the outgassing components during heat curing, and the current-voltage characteristics deteriorate.

[0012] Therefore, an object of the present invention is to provide a photosensitive resin composition that can form a film having a reduced transmittance near a wavelength of 450 nm after curing even when the heating atmosphere during curing is at a low oxygen concentration of less than 5%.

[0013] Means for Solving the Problems

[0014] To solve the above problems, the photosensitive resin composition of the present invention has the following constitution.

[0015] [1] A photosensitive resin composition containing an alkali-soluble resin (a), a phenolic compound (b) having a structure represented by formula (1), and a photosensitive compound (c).

[0016] [Chemical Formula 1]

[0017]

[0018] In formula (1), n represents an integer of 2 to 4, and * represents a bonding site.

[0019] [2] The photosensitive resin composition according to [1], wherein the component (b) contains a phenolic compound satisfying the following condition (b1): for any phenolic hydroxyl group in the aforementioned formula (1), the substitution position of at least one of the other phenolic hydroxyl groups is the para position.

[0020] [3] The photosensitive resin composition according to [1], wherein the component (b) contains a phenolic compound satisfying the following condition (b2): the substituent bonded to the benzyl site in the aforementioned formula (1) is an optionally substituted amino group.

[0021] [4] The photosensitive resin composition according to [1], wherein the component (b) contains at least one selected from the group consisting of a phenolic compound having a structure represented by formula (b3), a phenolic compound having a structure represented by formula (b4), and a phenolic compound having a structure represented by formula (b5).

[0022] [Chemical formula 2]

[0023]

[0024] In formula (b3), formula (b4), and formula (b5), n and m each independently represent an integer of 2 to 4, p represents an integer of 0 to 2, q represents an integer of 0 to 4, and 2 ≤ p + m ≤ 4 is satisfied. X represents -NR 32 -, -O-, -S-, R 32 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R 33 each independently represents a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R 34 and R 35 each independently represents -OR 36 , -SR 36 , -N(R 36 )2, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R 36 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

[0025] [5] The photosensitive resin composition according to any one of [1] to [4], further comprising a colorant (d).

[0026] [6] The photosensitive resin composition according to [5], wherein the component (d) includes: a colorant (d-1) having a maximum absorption wavelength at any position in the range of 490 nm or more and less than 580 nm in 300 to 800 nm; and / or a colorant (d-2) having a maximum absorption wavelength at any position in the range of 580 nm or more and less than 800 nm in 300 to 800 nm.

[0027] [7] The photosensitive resin composition according to [6], wherein the components (d-1) and (d-2) have a xanthene structure.

[0028] [8] The photosensitive resin composition according to any one of [1] to [7], wherein the content of the component (b) is 1 to 60 parts by mass relative to 100 parts by mass of the component (a).

[0029] [9] The photosensitive resin composition according to any one of [1] to [8], wherein the component (a) contains one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole precursor, and their copolymers.

[0030]

[10] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to [9].

[0031]

[11] An organic EL display device having a driving circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate.

[0032] The planarization layer and / or the insulating layer has the cured product described in

[10] .

[0033]

[12] The organic EL display device according to

[11] , wherein the planarization layer and / or the insulating layer has the cured product, and the transmittance at a wavelength of 450 nm of the planarization layer and / or the insulating layer is less than 30%.

[0034]

[13] The organic EL display device according to

[11] or

[12] , wherein the planarization layer and / or the insulating layer has the cured product, and the OD value under visible light per 1 μm film thickness of the planarization layer and / or the insulating layer is 0.5 to 1.5.

[0035]

[14] The organic EL display device according to any one of

[11] to

[13] , wherein the organic EL display device further includes a color filter having a black matrix.

[0036]

[15] A display device having at least metal wirings, the cured product described in

[10] , and a plurality of light-emitting elements, wherein each of the light-emitting elements has a pair of electrode terminals on any one surface, and the pair of electrode terminals are connected to a plurality of the metal wirings extending and existing in the cured product, and the plurality of the metal wirings are configured to maintain electrical insulation by the cured product.

[0037]

[16] A phenol compound having a structure represented by formula (b2).

[0038] [Chemical formula 3]

[0039]

[0040] In formula (b2), n represents an integer of 2 to 4, and * represents a connecting bond.

[0041]

[17] The phenolic compound according to

[16] , wherein the phenolic compound having the structure represented by the formula (b2) satisfies the following condition (b1): with respect to any phenolic hydroxyl group in the formula (b2), the substitution position of at least one of the other phenolic hydroxyl groups is the para position.

[0042]

[18] The phenolic compound according to

[16] or

[17] , having a molecular weight of 1000 or less.

[0043]

[19] A phenolic compound having the structure represented by the formula (b3), a phenolic compound having the structure represented by the formula (b4), or a phenolic compound having the structure represented by the formula (b5).

[0044] [Chemical formula 4]

[0045]

[0046] In the formula (b3), the formula (b4) and the formula (b5), n and m each independently represent an integer of 2 to 4, p represents an integer of 0 to 2, q represents an integer of 0 to 4, and 2 ≤ p + m ≤ 4 is satisfied, and X represents -NR 32 -, -O-, -S-, R 32 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R 33 each independently represents a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R 34 and R 35 each independently represents -OR 36 -, -SR 36 -, -N(R 36 )2, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R 36 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.

[0047]

[20] A phenolic compound having the structure represented by any of the following chemical formulas.

[0048] [Chemical formula 5]

[0049]

[0050] Advantages of the Invention

[0051] The photosensitive resin composition of the present invention can form a film having a low transmittance near a wavelength of 450 nm after curing even when the heating atmosphere during curing is a low oxygen concentration of less than 5%. Brief Description of the Drawings

[0052] Figure 1 ​Cross-sectional view of an example of an organic EL display device.

[0053] Figure 2 Cross-sectional view of an example of a display device.

[0054] Figure 3 Schematic diagram of the manufacturing steps of an organic EL display device. Detailed Description of the Invention

[0055] The embodiments of the present invention will be described in detail.

[0056] The photosensitive resin composition of the present invention contains an alkali-soluble resin (a), a phenolic compound (b) having a structure represented by formula (1), and a photosensitive compound (c).

[0057] [Chemical formula 6]

[0058]

[0059] In formula (1), n represents an integer of 2 to 4, and * represents a linking bond.

[0060] <Alkali-soluble resin (a)>

[0061] The photosensitive resin composition of the present invention contains an alkali-soluble resin (a) (hereinafter, sometimes referred to as component (a)). Alkali-solubility means that a solution obtained by dissolving the resin in γ-butyrolactone is coated on a silicon wafer, pre-baked at 120 °C for 4 minutes to form a pre-baked film with a film thickness of 10 μm ± 0.5 μm, the pre-baked film is immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 23 ± 1 °C for 1 minute, and then rinsed with pure water. The dissolution rate calculated from the reduction of the film thickness at this time is 50 nm / minute or more.

[0062] Component (a) has alkali-solubility, and thus has a hydroxyl group and / or an acidic group in the structural unit of the resin and / or at the end of its main chain. As the acidic group, for example, it may have a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, etc.

[0063] As component (a), it may contain known components such as polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamide, acrylic resin, a polymer of a radically polymerizable monomer having an acidic group such as polyhydroxystyrene resin, silicone resin, Cardo resin, phenolic resin, etc., but is not limited thereto. Component (a) may also contain two or more of these alkali-soluble resins.

[0064] ​​Among these (a) components, in terms of high development adhesion, excellent heat resistance, and low outgassing amount at high temperatures, resulting in high long-term reliability when the cured product is used in an organic EL display device, the (a) component preferably contains one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and their copolymers, and more preferably contains polyimide, polyimide precursor, polybenzoxazole precursor, or their copolymers. In addition, from the viewpoint of further improving sensitivity, the (a) component is further preferably a polyimide precursor or a polybenzoxazole precursor. On the other hand, from the viewpoints of promoting the color development of the phenolic compound (b) having the structure represented by the formula (1) by heating and reducing the transmittance at a wavelength of 450 nm after curing, the (a) component preferably contains one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and polyamide.

[0065] Here, the polyimide precursor refers to a resin that is converted into polyimide by heat treatment or chemical treatment, such as polyamic acid, polyamic acid ester, etc.

[0066] The polybenzoxazole precursor refers to a resin that is converted into polybenzoxazole by heat treatment or chemical treatment, such as polyhydroxyamide, etc.

[0067] The above polyimide precursor, polybenzoxazole precursor, and polyamide have a structural unit represented by the following formula (3), and the polyimide has a structural unit represented by the following formula (4).

[0068] In the (a) component, for each of the resin having the structural unit represented by the formula (3) and the resin having the structural unit represented by the formula (4), two or more kinds can be contained, or a resin obtained by copolymerizing the structural unit represented by the formula (3) and the structural unit represented by the formula (4) can be contained.

[0069] [Chemical formula 7]

[0070]

[0071] In the formula (3), X represents an organic group having 4 to 40 carbon atoms and a valence of 2 to 8, and Y represents an organic group having 6 to 40 carbon atoms and a valence of 2 to 11. R 11 and R 13 each independently represents a hydroxyl group or a sulfonic acid group. R 12 and R 14Each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. t, u, and w represent integers from 0 to 3, and v represents an integer from 0 to 6. Among them, when the structural unit represented by the formula (3) represents the structural unit of the polyimide precursor, u ≥ 2, and when the structural unit represented by the formula (3) represents the structural unit of the polybenzoxazole precursor, v ≥ 2, and at least two of the plurality of R 13 Among them, at least two are hydroxyl groups, u ≥ 2 and v ≥ 2, and at least two of the plurality of R 13 Among them, the component with at least two being hydroxyl groups is the polyimide precursor. The component having the structural unit represented by the formula (3) that neither belongs to the above polyimide precursor nor belongs to the polybenzoxazole precursor is a polyamide.

[0072] [Chemical formula 8]

[0073]

[0074] In the formula (4), E represents an organic group having 4 to 40 carbon atoms and 4 to 10 valences, and G represents an organic group having 6 to 40 carbon atoms and 2 to 8 valences. R 15 and R 16 Each independently represents a carboxyl group, a sulfonic acid group, or a hydroxyl group. x and y each independently represent an integer from 0 to 6. Among them, x + y > 0.

[0075] The polyimide, polyimide precursor, polybenzoxazole precursor, or their copolymer preferably has 5 to 100,000 structural units represented by the formula (3) or the formula (4). In addition, it may also have other structural units in addition to the structural units represented by the formula (3) or the formula (4). In this case, it is preferred to have the structural units represented by the formula (3) or the formula (4) in an amount of 50 mol% or more based on 100 mol% of all the structural units.

[0076] In the above formula (3), X(R 11 ) t (COOR 12 ) u represents the residue of an acid. X is an organic group having 4 to 40 carbon atoms and 2 to 8 valences, and among them, an organic group having 2 to 8 valences containing an aromatic ring or a cycloaliphatic group is preferred.

[0077] As residues of acids, residues of dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, triphenyl dicarboxylic acid, residues of tricarboxylic acids such as trimellitic acid, pyromellitic acid, diphenyl ether trimellitic acid, biphenyl trimellitic acid, residues of tetracarboxylic acids such as pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, 2,2',3,3'-benzophenone tetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)ether, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid and aromatic tetracarboxylic acids having the structures shown below, aliphatic tetracarboxylic acids such as butanetetracarboxylic acid, aliphatic tetracarboxylic acids containing a cycloaliphatic group such as 1,2,3,4-cyclopentanetetracarboxylic acid, etc., residues of tetracarboxylic acids, etc. In the component (a), as X(R 11 ) t (COOR 12 )u in the formula (3), two or more of these residues may be included.

[0078] [Chemical formula 9]

[0079]

[0080] R 20 represents an oxygen atom, C(CF3)2 or C(CH3)2. R 21 and R 22 each independently represent a hydrogen atom or a hydroxyl group.

[0081] Among the residues of the above acids, in the case of residues of tricarboxylic acids or tetracarboxylic acids, one or two carboxyl groups correspond to (COOR 12 ) in the formula (3).

[0082] In the above formula (4), E(R 15 ) x represents a residue of an acid dianhydride. E is an organic group having 4 to 40 carbon atoms and being tetravalent to decavalent, and among them, an organic group containing an aromatic ring or a cycloaliphatic group is preferred.

[0083] As residues of acid dianhydrides, specifically, examples include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy)phenyl}fluorene dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, and acid dianhydrides such as those having the structures shown below, etc., aromatic tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride, and residues of aliphatic tetracarboxylic dianhydrides containing a cycloaliphatic group such as 1,2,3,4-cyclopentanetetracarboxylic dianhydride, etc. In the component (a), as E(R 15 ) x in the formula (4), two or more of these residues may be present.

[0084] [Chemical formula 10]

[0085]

[0086] R 20 represents an oxygen atom, C(CF3)2 or C(CH3)2. R 21 and R 22 each independently represent a hydrogen atom or a hydroxyl group.

[0087] Y(R 13 ) v (COOR 14 ) w in the above formula (3) and G(R 16 ) y in the above formula (4) represent residues of diamines. Y is an organic group having 6 to 40 carbon atoms and a valence of 2 to 11, and among them, an organic group having 2 to 11 valences containing an aromatic ring or a cycloaliphatic group is preferred. G is an organic group having 6 to 40 carbon atoms and a valence of 2 to 8, and among them, an organic group having 2 to 8 valences containing an aromatic ring or a cycloaliphatic group is preferred.

[0088] Specific examples of the residue of the diamine may include residues of aromatic diamines such as 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether, 1,4-bis(4-aminophenoxy)benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2',3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3',4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene, 2,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine, 3,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, compounds obtained by substituting at least a part of the hydrogen atoms of their aromatic rings with alkyl groups or halogen atoms, etc.; residues of aliphatic diamines containing alicyclic groups such as cyclohexanediamine and methylenebis(cyclohexylamine); and residues of diamines having the structures shown below. In the component (a), as Y(R 13 ) v (COOR 14 ) w in the formula (3) and G(R 16 ) y in the formula (4), two or more of these residues may be present.

[0089] [Chemical formula 11]

[0090]

[0091] R 20 represents an oxygen atom, C(CF3)2 or C(CH3)2. R 21 to R 24 each independently represents a hydrogen atom or a hydroxyl group.

[0092] In addition, the terminals of these resins may be blocked with known monoamines having acidic groups, acid anhydrides, acyl chlorides, monocarboxylic acids, and active ester compounds.

[0093] The component (a) can be synthesized by known methods.

[0094] Examples of polymers of radically polymerizable monomers having acidic groups include acrylic resins and polyhydroxystyrene resins. As the radically polymerizable monomers having acidic groups, known materials can be used. For example, o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene, and their alkyl and alkoxy substituents, methacrylic acid and acrylic acid, and their α-haloalkyl, alkoxy, halogen, nitro, and cyano substituents can be mentioned.

[0095] Examples of Cardo resins include resins having a Cardo structure, that is, a skeletal structure in which two cyclic structures are bonded to a quaternary carbon atom constituting a cyclic structure. A typical Cardo structure is a structure in which a benzene ring is bonded to a fluorene ring.

[0096] Examples of phenolic resins include known Novolac phenolic resins, Resol phenolic resins, etc. obtained by polycondensing various phenols alone or a mixture of multiple of them using aldehydes such as formaldehyde.

[0097] Examples of silicone resins include known silicone resins obtained by hydrolyzing and dehydrating and condensing one or more selected from tetrafunctional organosilanes, trifunctional organosilanes, difunctional organosilanes, and monofunctional organosilanes.

[0098] <Phenolic compound (b) having the structure represented by formula (1)>

[0099] The photosensitive resin composition of the present invention contains a phenolic compound (b) having the structure represented by formula (1) (hereinafter, sometimes referred to as component (b)).

[0100] [Chemical formula 12]

[0101]

[0102] In formula (1), n represents an integer of 2 to 4, and * represents a linking bond.

[0103] Since the photosensitive resin composition of the present invention contains the component (b), even when the atmosphere during curing is a low oxygen concentration of less than 5% oxygen concentration, it can be colored by heating, and the transmittance at a wavelength of 450 nm is reduced after curing. Although the coloring mechanism is not clear, it is considered that the component (b) forms a quinone structure by heating, thereby generating a coloring body having absorption at 300 nm to 500 nm. Generally, oxygen is necessary for a phenol compound to become a quinone structure by heating. However, since the component (b) has three or more phenolic hydroxyl groups in the same aromatic ring and is electron-rich, it is easily converted into a quinone structure by heating even at a low oxygen concentration of less than 5% oxygen concentration, and the transmittance at 450 nm can be reduced after curing. In addition, in the state before heating, the component (b) does not have absorption at 300 nm to 500 nm. Therefore, the exposure wavelength region of a mercury lamp, which is usually used as an exposure light source, i.e., 350 nm to 450 nm, is not blocked before curing, and a pattern can be formed with high sensitivity. By further containing a colorant (d) described later, a film having high visible light shielding properties after curing can be obtained.

[0104] In the formula (1), n represents an integer of 2 to 4. From the viewpoint of obtaining raw materials, n is preferably 2 to 3, and n is more preferably 2.

[0105] In addition, the component (b) may have a plurality of structures represented by the formula (1) in one molecule. From the viewpoint of further reducing the transmittance at a wavelength of 450 nm after curing, the component (b) preferably has two or more structures represented by the formula (1) in one molecule. For the number of structures represented by (1) contained in one molecule, the upper limit is not particularly limited, and is preferably 10 or less, and more preferably 5 or less.

[0106] From the viewpoint of further reducing the transmittance at a wavelength of 450 nm after curing, the component (b) preferably contains a phenol compound satisfying the following condition (b1): with respect to any one of the phenolic hydroxyl groups in the formula (1), the substitution position of at least one of the other phenolic hydroxyl groups is the para position. By making the component (b) contain a phenol compound satisfying the condition (b1) (hereinafter, sometimes referred to as the (b1) component), the transmittance at a wavelength of 450 nm after curing can be further reduced. It is inferred that this is because the (b1) component has phenolic hydroxyl groups in a para position relationship with respect to the position relationship of the phenolic hydroxyl groups in the formula (1), and thus, a p-quinone structure can be formed by heating, and the coloring property of the (b1) component is further increased. Specifically, the (b1) component preferably contains a phenol compound having the following structure, and particularly preferably contains a phenol compound having the structure represented by the formula (b1a).

[0107] [Chemical formula 13]

[0108]

[0109] In the formula, each * represents a linking bond.

[0110] In the partial structure represented by formula (1), with respect to the substituent bonded to the benzyl site, an optionally substituted amino group, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkenyl group, an optionally substituted alkenyl ether group, an optionally substituted aryl group, an optionally substituted aryloxy group, or an optionally substituted heteroaryl group, etc. may be adjacent. From the viewpoint of further reducing the transmittance at a wavelength of 450 nm after curing, as the substituent bonded to the benzyl site, an optionally substituted amino group, an optionally substituted aryl group, or an optionally substituted heteroaryl group is preferred, and an optionally substituted amino group and an optionally substituted aryl group are more preferred. Examples of the substituent include a phenolic hydroxyl group, a sulfo group, a carboxyl group, an alkoxy group, a hydrocarbon group having 1 to 10 carbon atoms, etc., and a phenolic hydroxyl group is preferred. Hereinafter, examples of the (b) component in which the substituent bonded to the benzyl site in the partial structure represented by formula (1) is an optionally substituted aryl group are shown, but are not limited thereto.

[0111] [Chemical formula 14]

[0112]

[0113] n each independently represents an integer of 2 to 4, and R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. L represents a single bond, an oxygen atom, C(CF3)2, C(CH3)2, SO2, or CO. M represents a nitrogen atom, CH, or CCH3.

[0114] As the (b) component in which the substituent bonded to the benzyl site in the partial structure represented by formula (1) has an optionally substituted aryl group, from the viewpoint of further reducing the transmittance at a wavelength of 450 nm after curing, it is preferred to satisfy condition (b1). Specifically, the (b) component more preferably contains at least one phenolic compound selected from the group consisting of the following phenolic compounds.

[0115] [Chemical formula 15]

[0116]

[0117] From the viewpoint of reducing the transmittance at a wavelength of 500 nm after curing in addition to the transmittance at a wavelength of 450 nm after curing, the component (b) preferably contains a phenolic compound satisfying the following condition (b2): the substituent bonded to the benzyl site in the formula (1) is an optionally substituted amino group. As the component (b) satisfying the condition (b2) (hereinafter, sometimes referred to as the component (b2)), specifically, a phenolic compound having a structure represented by the formula (b2) is preferably contained.

[0118] [Chemical formula 16]

[0119]

[0120] In the formula (b2), n represents an integer of 2 to 4, and * represents a linking bond.

[0121] The phenolic compound having the structure represented by the formula (b2) more preferably satisfies the following condition (b1): with respect to any one of the phenolic hydroxyl groups in the formula (b2), the substitution position of at least one of the other phenolic hydroxyl groups is the para position.

[0122] By making the component (b) have the structure represented by the formula (b2), in addition to being able to reduce the transmittance at a wavelength of 450 nm after curing, it is also possible to reduce the transmittance at a wavelength of 500 nm after curing. Although the mechanism is not clear, it is considered that the reason is that since the substituent bonded to the benzyl site in the formula (1) is an optionally substituted amino group, electrons are supplied from the amino group to the quinone structure generated by heating of the component (b), whereby the absorption band of the quinone structure is shifted to a longer wavelength.

[0123] In the partial structure represented by the formula (b2), with respect to the substituent adjacent to the nitrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, etc. may be adjacent, and phenolic compounds having the structures shown below can be cited, but are not limited thereto.

[0124] [Chemical formula 17]

[0125]

[0126] n each independently represents an integer of 2 to 4, R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. L represents a single bond, an oxygen atom, C(CF3)2, C(CH3)2, SO2 or CO. M represents a nitrogen atom, CH or CCH3.

[0127] From the viewpoint of further reducing the transmittance at a wavelength of 500 nm after curing in addition to the transmittance at a wavelength of 450 nm after curing, as the substituent adjacent to the nitrogen atom in the formula (b2), at least one of an optionally substituted aryl group or an optionally substituted heteroaryl group adjacent to the nitrogen atom is preferred.

[0128] From the viewpoint of further reducing the transmittance at a wavelength of 450 nm after curing and further reducing the transmittance at a wavelength of 500 nm after curing, the component (b) preferably contains a phenolic compound satisfying the condition (b1) and the condition (b2). Specifically, the component (b) preferably contains one or more selected from the group consisting of phenolic compounds having a structure represented by any one of the following formulas (b12a) to (b12d), and particularly preferably contains a phenolic compound having a structure represented by the formula (b12a).

[0129] [Chemical formula 18]

[0130]

[0131] From the viewpoint of further reducing the transmittance at a wavelength of 550 nm after curing in addition to reducing the transmittance at a wavelength of 500 nm after curing, the component (b) preferably contains one or more selected from the group consisting of a phenolic compound having a structure represented by the formula (b3) (hereinafter sometimes referred to as the (b3) component), a phenolic compound having a structure represented by the formula (b4) (hereinafter sometimes referred to as the (b4) component), and a phenolic compound having a structure represented by the formula (b5) (hereinafter sometimes referred to as the (b5) component).

[0132] [Chemical formula 19]

[0133]

[0134] In the formulas (b3), (b4) and (b5), n and m each independently represent an integer of 2 to 4, p represents an integer of 0 to 2, q represents an integer of 0 to 4, and 2 ≤ p + m ≤ 4 is satisfied, and X represents -NR 32 -, -O-, -S-, and R 32 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R 33 each independently represents a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R 34 and R 35 each independently represents -OR 36 -, -SR 36 -, -N(R 36 )2, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R 36Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

[0135] Although the mechanism for further reducing the transmittance at a wavelength of 550 nm after curing is not clear, it is considered that when the component (b) forms a quinone structure by heating, a broad conjugated structure can be formed over the entire molecule, and thus the absorption band of the quinone structure is shifted to a longer wavelength.

[0136] From the viewpoint of reducing the transmittance at a wavelength of 550 nm after curing, the component (b) preferably contains the component (b3) and / or the component (b4), and more preferably contains the component (b3).

[0137] From the viewpoint of reducing the transmittance at a wavelength of 550 nm after curing, the component (b3) preferably contains a phenolic compound in which X in the formula (b3) satisfies -NR 32 -, -O-, and more preferably contains a phenolic compound in which X satisfies -O-.

[0138] From the viewpoint of reducing the transmittance at a wavelength of 550 nm after curing, it is preferable that in one or more selected from the group consisting of the component (b3), the component (b4), and the component (b5), there are two structures satisfying the condition (b1) in the same molecule.

[0139] As a specific example thereof, there can be mentioned a component containing at least two structures represented by any one of the above formulas (b1a) to (b1d) in the same molecule among the components (b3) to (b5), and particularly preferably a component containing at least two structures represented by the formula (b1a) in the same molecule.

[0140] Preferred specific examples of the component (b3), the component (b4), and the component (b5) are shown below, but are not limited thereto.

[0141] [Chemical formula 20]

[0142]

[0143] n each independently represents an integer of 2 to 4. Me represents a methyl group.

[0144] The component (b3) preferably contains one or more selected from the group consisting of phenolic compounds having a structure represented by any one of the formulas (b3a) to (b3f), and particularly preferably contains a phenolic compound having a structure represented by the formula (b3a).

[0145] [Chemical formula 21]

[0146]

[0147] n independently represents an integer from 2 to 4, p represents an integer from 0 to 2, and X represents -NR 32 -, -O-, -S-, R 32 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, R 33 each independently represents a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, R 37 represents a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

[0148] (b) component, (b1) component, (b2) component, (b3) component, (b4) component, and (b5) component have no particular limitation on the upper limit of the molecular weight, preferably 1000 or less, more preferably 800 or less, and still more preferably 600 or less. The lower limit of the molecular weight of the (b) component is 126 or more.

[0149] (b) component can use a component synthesized by a known method. As a known method, for example, a method of reacting a compound substituted with hydroxymethyl or alkoxymethyl under acidic conditions with a polyphenol compound selected from trihydroxybenzene, tetrahydroxybenzene, and pentahydroxybenzene can be cited.

[0150] As trihydroxybenzene, phloroglucinol, pyrogallol, 1,2,4-trihydroxybenzene can be cited. As tetrahydroxybenzene, 1,2,3,4-tetrahydroxybenzene, 1,2,3,5-tetrahydroxybenzene can be cited. By using any one of 1,2,4-trihydroxybenzene, 1,2,3,4-tetrahydroxybenzene, 1,2,3,5-tetrahydroxybenzene, and pentahydroxybenzene as the polyphenol compound, the (b) component satisfying the condition (b1) can be obtained.

[0151] On the other hand, by using a compound substituted with hydroxymethyl or alkoxymethyl on the nitrogen atom, the (b) component satisfying the condition (b2) can be obtained. By further using any one of 1,2,4-trihydroxybenzene, 1,2,3,4-tetrahydroxybenzene, 1,2,3,5-tetrahydroxybenzene, and pentahydroxybenzene as the polyphenol compound, the (b) component satisfying the condition (b1) and the condition (b2) can be obtained.

[0152] A compound substituted with hydroxymethyl on the nitrogen atom can be obtained, for example, by reacting a compound containing a primary amino group or a secondary amino group with formaldehyde under basic conditions. Further, a compound substituted with alkoxymethyl on the nitrogen atom can be obtained by reacting it with an alcohol under acidic conditions.

[0153] In addition, the component (b3) can be obtained by substituting at least two hydroxymethyl groups for one or more members selected from the group consisting of a pyrrole ring, a furan ring, and a thiophene ring. The component (b4) can be obtained by substituting hydroxymethyl groups for the 1,4-positions or 1,2-positions of a benzene skeleton, and the component (b5) can be obtained by substituting hydroxymethyl groups for the 1,4-positions or 1,2-positions of a benzene skeleton. By further using any one of 1,2,4-trihydroxybenzene, 1,2,3,4-tetrahydroxybenzene, 1,2,3,5-tetrahydroxybenzene, and pentahydroxybenzene as a polyphenol compound, the components (b3) to (b5) having a structure represented by any one of formulas (b1a) to (b1d) can be introduced.

[0154] In the present invention, relative to 100 parts by mass of the component (a), the content of the component (b) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and still more preferably 10 parts by mass or more. By making the content of the component (b) 1 part by mass or more relative to 100 parts by mass of the component (a), the transmittance at a wavelength of 450 nm can be reduced after curing. In addition, relative to 100 parts by mass of the component (a), the content of the component (b) is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, still more preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less. By making the content of the component (b) 60 parts by mass or less relative to 100 parts by mass of the component (a), the chemical resistance of the cured product can be maintained.

[0155] <Photosensitive compound (c)>

[0156] The photosensitive resin composition of the present invention further contains a photosensitive compound (c) (hereinafter, sometimes referred to as component (c)).

[0157] From the viewpoint of high sensitivity, relative to 100 parts by mass of the component (a), the content of the component (c) is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and still more preferably 10 parts by mass or more. On the other hand, from the viewpoint of long-term reliability when the cured product of the present invention is used as a planarization layer and / or an insulating layer of an organic EL display device, relative to 100 parts by mass of the component (a), the content of the component (c) is preferably 100 parts by mass or less.

[0158] As the component (c), a photoacid generator (c1), a photopolymerization initiator (c2), etc. can be contained. The photoacid generator (c1) is a compound that generates an acid upon light irradiation, and the photopolymerization initiator (c2) is a compound that undergoes bond cleavage and / or reaction upon exposure to light and generates free radicals.

[0159] By containing a photoacid generator (c1), an acid is generated in the light-irradiated part, and the solubility of the light-irradiated part in an alkaline aqueous solution increases, and a positive relief pattern in which the light-irradiated part is dissolved can be obtained. In addition, by containing a photoacid generator (c1) and an epoxy compound or a thermal crosslinking agent described later, the acid generated in the light-irradiated part promotes the crosslinking reaction of the epoxy compound and the thermal crosslinking agent, and a negative relief pattern in which the light-irradiated part is insolubilized can be obtained. On the other hand, by containing a photopolymerization initiator (c2) and a radical polymerizable compound described later, radical polymerization occurs in the light-irradiated part, and a negative relief pattern in which the light-irradiated part is insolubilized can be obtained. From the viewpoint of being able to form a fine pattern when the cured product of the present invention is used as a planarization layer and / or an insulating layer of an organic EL display device, as the component (c), it is preferable to contain a photoacid generator (c1) that can obtain a positive relief pattern.

[0160] As the photoacid generator (c1), for example, a quinone diazide compound can be contained. The photosensitive resin composition of the present invention preferably contains two or more photoacid generators (c1). When two or more photoacid generators (c1) are contained, a photosensitive resin composition with higher sensitivity can be obtained.

[0161] As the quinone diazide compound, a compound formed by ester-bonding a sulfonic acid of diazoquinone with a polyhydroxy compound, a compound formed by sulfonamide-bonding a sulfonic acid of diazoquinone with a polyamino compound, a compound formed by ester-bonding and / or sulfonamide-bonding a sulfonic acid of diazoquinone with a polyhydroxy polyamino compound, etc. can be contained.

[0162] As the diazoquinone structure, it is preferable to use either diazoquinonaphthalene-5-sulfonyl or diazoquinonaphthalene-4-sulfonyl. A diazoquinone sulfonate compound having diazoquinonaphthalene-4-sulfonyl and diazoquinonaphthalene-5-sulfonyl in the same molecule can be contained, or a diazoquinonaphthalene-4-sulfonate compound and a diazoquinonaphthalene-5-sulfonate compound can be contained. The diazoquinonaphthalene-4-sulfonate compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The absorption of the diazoquinonaphthalene-5-sulfonate compound extends to the g-line region of a mercury lamp and is suitable for g-line exposure.

[0163] It is preferable to select the diazoquinonaphthalene-4-sulfonate compound and the diazoquinonaphthalene-5-sulfonate compound according to the wavelength of exposure, but from the viewpoint of high sensitivity, it is preferable to contain the diazoquinonaphthalene-4-sulfonate compound.

[0164] The above-mentioned quinone diazide compound can be synthesized from a compound having a phenolic hydroxyl group and a diazoquinone sulfonic acid compound by an arbitrary esterification reaction. By using these quinone diazide compounds, the resolution, sensitivity, and residual film rate are further improved.

[0165] From the viewpoint of high-sensitivity improvement, the content of the photoacid generator (c1) is preferably 0.1 part by mass or more, more preferably 10 parts by mass or more, and still more preferably 25 parts by mass or more with respect to 100 parts by mass of the component (a). On the other hand, from the viewpoint of long-term reliability when the cured product of the present invention is used as a planarization layer and / or an insulating layer of an organic EL display device, the content of the photoacid generator (c1) is preferably 100 parts by mass or less with respect to 100 parts by mass of the component (a).

[0166] As the photopolymerization initiator (c2), for example, it may contain a benzoyl ketal-based photopolymerization initiator, an α-hydroxy ketone-based photopolymerization initiator, an α-amino ketone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, an oxime ester-based photopolymerization initiator, an acridine-based photopolymerization initiator, a titanocene-based photopolymerization initiator, a benzophenone-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, an aromatic ketone acid ester-based photopolymerization initiator, a benzoate-based photopolymerization initiator, etc. The photosensitive resin composition of the present invention may contain two or more kinds of photopolymerization initiators (c2). From the viewpoint of further improving sensitivity, the photopolymerization initiator (c2) more preferably contains an α-amino ketone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, or an oxime ester-based photopolymerization initiator.

[0167] As the α-amino ketone-based photopolymerization initiator, for example, it may contain 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-butan-1-one, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-octyl-9H-carbazole, etc.

[0168] As the acylphosphine oxide-based photopolymerization initiator, for example, it may contain 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide, etc.

[0169] As an oxime ester-based photoinitiator, for example, it may contain 1-phenylpropane-1,2-dione-2-(O-ethoxycarbonyl)oxime, 1-phenylbutane-1,2-dione-2-(O-methoxycarbonyl)oxime, 1,3-diphenylpropane-1,2,3-trione-2-(O-ethoxycarbonyl)oxime, 1-[4-(phenylthio)phenyl]octane-1,2-dione-2-(O-benzoyl)oxime, 1-[4-[4-(carboxyphenyl)thio]phenyl]propane-1,2-dione-2-(O-acetyl)oxime, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime, 1-[9-ethyl-6-[2-methyl-4-[1-(2,2-dimethyl-1,3-dioxolan-4-yl)methyloxy]benzoyl]-9H-carbazol-3-yl]ethanone-1-(O-acetyl)oxime, or 1-(9-ethyl-6-nitro-9H-carbazol-3-yl)-1-[2-methyl-4-(1-methoxypropan-2-yloxy)phenyl]methanone-1-(O-acetyl)oxime, etc.

[0170] From the viewpoint of high-sensitivity improvement, the content of the photoinitiator (c2) is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, and further preferably 10 parts by mass or more, based on 100 parts by mass in total of the component (a) and the radical polymerizable compound described later. On the other hand, from the viewpoint of further improving the resolution and reducing the taper angle, the content of the photoinitiator (c2) is preferably 50 parts by mass or less, based on 100 parts by mass in total of the component (a) and the radical polymerizable compound described later.

[0171] <Colorant (d)>

[0172] The photosensitive resin composition of the present invention preferably further contains a colorant (d) (hereinafter, sometimes referred to as component (d)). By including the component (b) and the component (d) in the photosensitive resin composition of the present invention, a film having high visible light shielding property after curing can be obtained.

[0173] As the component (d), it is preferably to contain a dye (d1) and / or a pigment (d2). The component (d) preferably contains at least 1 type or more. For example, it is preferably to contain 1 type of dye (d1) or pigment (d2), or to contain 2 types or more of dyes (d1) or pigments (d2), or to contain 1 type or more of dyes (d1) and 1 type or more of pigments (d2).

[0174] From the viewpoint of solvent solubility, as the component (d), it is preferable to contain a dye (d1). Further, from the viewpoints of high-sensitization and reduction of residue, as the dye (d1), an ionic dye in which organic ions form an ion pair with each other is preferable. On the other hand, from the viewpoint of suppressing the fading of the colorant in the heat treatment step of the photosensitive resin composition described later, it is preferable to contain a pigment (d2).

[0175] Further, from the viewpoints of high-sensitization and reduction of residue, the component (d) preferably has a sulfonic acid group and / or a sulfonate group.

[0176] (d) component preferably contains a colorant (d-1) having a maximum absorption wavelength in any range of 490 nm or more and less than 580 nm in 300 to 800 nm (hereinafter, sometimes referred to as the (d-1) component); and / or a colorant (d-2) having a maximum absorption wavelength in any range of 580 nm or more and less than 800 nm in 300 to 800 nm (hereinafter, sometimes referred to as the (d-2) component). Here, the so-called in 300 to 800 nm means that the maximum absorption wavelength is measured in the region of 300 to 800 nm. Specifically, as the (d-1) component, it is preferable to contain a dye (d1-1) having a maximum absorption wavelength in any range of 490 nm or more and less than 580 nm in 300 to 800 nm; and / or a pigment (d2-1) having a maximum absorption wavelength in any range of 490 nm or more and less than 580 nm in 300 to 800 nm. Specifically, as the (d-2) component, it is preferable to contain a dye (d1-2) having a maximum absorption wavelength in any range of 580 nm or more and less than 800 nm in 300 to 800 nm; and / or a pigment (d2-2) having a maximum absorption wavelength in any range of 580 nm or more and less than 800 nm in 300 to 800 nm. When the photosensitive resin composition of the present invention contains the (d-1) component and the (d-2) component, from the viewpoint of improving heat resistance, it is preferable that either the (d-1) component or the (d-2) component has a xanthene structure, and more preferably the (d-1) component and the (d-2) component have a xanthene structure. Hereinafter, they are sometimes simply referred to as the (d1-1) component, the (d2-1) component, the (d1-2) component, and the (d2-2) component, respectively.

[0177] In the present invention, from the viewpoints of storage stability, fading during curing, and fading during light irradiation, the dye (d1) preferably contains a dye that is soluble in the solvent for dissolving the component (a) and compatible with the resin, and has high heat resistance and light resistance. Since the component (d1-1) has a maximum absorption wavelength in the range of 300 to 800 nm and in any range of 490 nm or more and less than 580 nm, for example, red dyes, purple dyes, etc. can be contained. Since the component (d1-2) has a maximum absorption wavelength in the range of 300 to 800 nm and in any range of 580 nm or more and 800 nm or less, for example, blue dyes, green dyes, etc. can be cited. When the photosensitive resin composition of the present invention contains the component (d1-1) and the component (d1-2), from the viewpoint of improving heat resistance, it is preferable that either the component (d1-1) or the component (d1-2) has a xanthene structure, and more preferably both the component (d1-1) and the component (d1-2) have a xanthene structure.

[0178] Examples of the skeleton structure of the dye (d1) include, but are not limited to, anthraquinone-based, azo-based, phthalocyanine-based, methine-based, oxazine-based, quinoline-based, triarylmethane-based, xanthene-based, etc. Among them, from the viewpoints of solubility in the solvent and heat resistance, anthraquinone-based, azo-based, methine-based, triarylmethane-based, and xanthene-based are preferred. In addition, from the viewpoint of improving heat resistance, xanthene-based is further preferred. In addition, each of the above dyes can be used alone or in the form of a metal-containing complex salt system. Specifically, Sumi lan, Lanyl dyes (manufactured by Sumitomo Chemical Co., Ltd.), Orasol, Oracet, Filamid, Irgasperse dyes (manufactured by Ciba Specialty Chemicals Co., Ltd.), Zapo n, Neozapon, Neptune, Acidol dyes (manufactured by BASF Co., Ltd.), Kayaset, Kayakalan dyes (manufactured by Nippon Kayaku Co., Ltd.), ValifastColors dyes (manufactured by Orient Chemical Industries Ltd.), Savinyl, Sandoplast, Polysynthren, Lanasyn dyes (manufactured by Clariant Japan K.K.), Aizen Spilon dyes (manufactured by Hodogaya Chemical Co., Ltd.), functional pigments (manufactured by Yamada Chemical Industry Co., Ltd.), Plast Color dyes, Oil Color dyes (manufactured by Arimoto Chemical Industry Co., Ltd.), etc. can be obtained, but are not limited to these. These dyes can be used alone or in a mixed manner.

[0179] In the present invention, the dye (d1) preferably contains an ionic dye (d1a) which forms an ion pair of an organic anion part and an organic cation part (hereinafter, sometimes referred to as the (d1a) component). The (d1a) component refers to a salt compound containing an organic anion part and a non-dye organic cation part, a salt compound containing an organic cation part of a basic dye and a non-dye organic anion part, or a salt compound containing an organic anion part of an acidic dye and an organic cation part of a basic dye. From the viewpoint of improving the sensitivity by increasing the proportion of the coloring component per molecule and reducing the addition amount of the ionic dye, the ionic dye of the present invention preferably contains a salt compound containing an organic anion part of an acidic dye and an organic cation part of a basic dye. That is, preferably, the aforementioned (d) component contains an ionic dye which forms an ion pair of an organic anion part and an organic cation part, and the organic anion part and the organic cation part are respectively composed of an organic anion part of an acidic dye and an organic cation part of a basic dye.

[0180] A salt compound containing an organic anion part of an acidic dye and a non-dye organic cation part can be produced by using an acidic dye as a raw material and replacing the counter cation with a non-dye organic cation by a known method. A salt compound containing an organic cation part of a basic dye and a non-dye organic anion part can be produced by using a basic dye as a raw material and replacing the counter anion with a non-dye organic anion by a known method. A salt compound containing an organic anion part of an acidic dye and an organic cation part of a basic dye can be produced by using an acidic dye and a basic dye as raw materials and replacing their respective counter ions by a known method.

[0181] The acidic dye which is the raw material of the (d1a) component is a compound having an acidic substituent such as a sulfo group or a carboxyl group in the molecule of the pigment, or an anionic water-soluble dye which is a salt thereof. It should be noted that as the acidic dye, a dye having an acidic substituent such as a sulfo group or a carboxyl group and classified as a direct dye is included.

[0182] As acid dyes, for example, the following can be cited: C.I. Acid Yellow 1, 17, 18, 23, 25, 36, 38, 42, 44, 54, 59, 72, 78, 151; C.I. Acid Orange 7, 10, 12, 19, 20, 22, 28, 30, 52, 56, 74, 127; C.I. Acid Red 1, 3, 4, 6, 8, 11, 12, 14, 18, 26, 27, 33, 37, 53, 57, 88, 106, 108, 111, 114, 131, 137, 138, 151, 154, 158, 159, 173, 184, 186, 215, 257, 266, 296, 337; C.I. Acid Brown 2, 4, 13, 248; C.I. Acid Violet 11, 56, 58; C.I. Acid Blue 92, 102, 113, 117 and other azo acid dyes; C.I. Acid Yellow 2, 3, 5 and other quinoline acid dyes; C.I. Acid Red 50, 51, 52, 87, 91, 92, 93, 94, 289 and other xanthene acid dyes; C.I. Acid Red 82, 92; C.I. Acid Violet 41, 42, 43; C.I. Acid Blue 14, 23, 25, 27, 40, 45, 78, 80, 127:1, 129, 145, 167, 230; C.I. Acid Green 25, 27 and other anthraquinone acid dyes; C.I. Acid Violet 49; C.I. Acid Blue 7, 9, 22, 83, 90; C.I. Acid Green 9, 50; C.I. Food Green 3 and other triarylmethane acid dyes; C.I. Acid Blue 249 and other phthalocyanine acid dyes; C.I. Acid Blue 74 and other indigo acid dyes. Among them, from the aspect of high heat resistance, the acid dye preferably contains xanthene acid dyes. The xanthene acid dye more preferably contains rhodamine acid dyes such as C.I. Acid Red 50, 52, 289, etc.

[0183] As the non-dye organic cation part that is the raw material of the (d1a) component, ammonium ion [N(R)4] can be cited + , phosphonium ion [P(R)4] + , iminium ion [(R)2-N=C(R)2]+, arsonium ion [As(R)4] + , stibonium ion [Sb(R)4] + , oxonium ion [O(R)3]+, sulfonium ion [S(R)3] + , selenonium ion [Se(R)3] + , stannonium ion [Sn(R)3] + , iodonium ion [I(R)2] + , diazonium ion [R-N +≡N], etc. From the viewpoint of insulation when using the cured product formed from the photosensitive resin composition of the present invention, ammonium ions [N(R)4] are preferred. + , phosphonium ions [P(R)4] + , iminium ions [(R)2-N=C(R)2] + . It should be noted that each R in the ionic formula independently represents a hydrocarbon group having 1 to 20 carbon atoms which may optionally have a substituent and may also have a heteroatom in the carbon chain. From the viewpoint of increasing the sensitivity by increasing the proportion of the coloring component per molecule and reducing the content of the ionic dye in the photosensitive resin composition, the molecular weight of the non-dye organic cation moiety is preferably 1000 or less, more preferably 700 or less, and still more preferably 400 or less. The lower limit of the molecular weight of the non-dye organic cation moiety is not particularly limited, preferably 1 or more, and still more preferably 100 or more.

[0184] The basic dye that is a raw material for the (d1a) component is a compound having a basic group such as an amino group or an imino group in the molecule, or a salt thereof, and is a dye that forms a cation in an aqueous solution.

[0185] Examples of basic dyes include: C.I. Basic Red 17, 22, 23, 25, 29, 30, 38, 39, 46, 46:1, 82; C.I. Basic Orange 2, 24, 25; C.I. Basic Violet 18; C.I. Basic Yellow 15, 24, 25, 32, 36, 41, 73, 80; C.I. Basic Brown 1; C.I. Basic Blue 41, 54, 64, 66, 67, 129 and other azo-based basic dyes; C.I. Basic Red 1, 2; C.I. Basic Violet 10, 11 and other xanthene-based basic dyes; C.I. Basic Yellow 11, 13, 21, 23, 28; C.I. Basic Orange 21; C.I. Basic Red 13, 14; C.I. Basic Violet 16, 39; and other methine-based basic dyes; C.I. Basic Blue 22, 35, 45, 47 and other anthraquinone-based basic dyes; C.I. Basic Violet 1, 2, 3, 4, 13, 14, 23; C.I. Basic Blue 1, 5, 7, 8, 11, 15, 18, 21, 24, 26; C.I. Basic Green 1, 4 and other triarylmethane-based basic dyes and xanthene-based basic dyes having the structures shown below.

[0186] [Chemical formula 22]

[0187]

[0188] R 25 ~R 31 Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms which may optionally have a substituent.

[0189] Among them, regarding basic dyes, from the aspect of being able to improve the blackness of the cured product, it is preferable to contain xanthene-based basic dyes and triarylmethane-based basic dyes. From the aspect of high heat resistance, it is preferable to contain xanthene-based acid dyes.

[0190] As the organic anion part of the non-dye that is the raw material of the (d1a) component, in addition to aliphatic or aromatic sulfonate ions and aliphatic or aromatic carboxylate ions, sulfimide anions [(RSO2)2N] can also be cited. - 、borate anions (BR4) - and the like. From the viewpoint of suppressing the deterioration of the electrodes and the light-emitting layer of the organic EL display device when applying the cured product formed from the photosensitive resin composition of the present invention, the organic anion part of the non-dye is preferably an aliphatic or aromatic sulfonate ion or an aliphatic or aromatic carboxylate ion. In addition, from the viewpoints of high sensitivity and reduction of residues, the organic anion part of the non-dye is preferably an aliphatic or aromatic sulfonate ion. It should be noted that R in the ionic formula of the organic anion part of the non-dye is independently an optionally substituted hydrocarbon group having 1 to 20 carbon atoms and may have a heteroatom in the carbon chain. From the viewpoint of increasing the sensitivity by increasing the proportion of the coloring component in each molecule and reducing the content of the ionic dye in the photosensitive resin composition, the molecular weight of the organic anion part of the non-dye is preferably 1000 or less, more preferably 700 or less, and further preferably 400 or less. There is no particular limitation on the lower limit of the molecular weight of the non-dye anion part, and it is preferably 1 or more, and more preferably 100 or more.

[0191] From the viewpoint of high heat resistance, the organic anion part and / or the organic cation part of the (d1a) component preferably have a xanthene skeleton. As the organic anion having a xanthene skeleton, the above-mentioned xanthene-based acid dyes can be cited, and as the organic cation having a xanthene skeleton, the above-mentioned xanthene-based basic dyes can be cited.

[0192] From the viewpoints of increasing the alkali solubility during development and improving the sensitivity, the (d1a) component preferably has an acidic group. As the acidic group, for example, it can have a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a sulfonate group, etc., and particularly preferably a sulfonic acid group and a sulfonate group.

[0193] The salt-forming compound obtained by ion exchange of an acidic dye and a basic dye can be produced by known methods. For example, an aqueous solution of an acidic dye and an aqueous solution of a basic dye are separately prepared, and while stirring both, they are slowly mixed. As a precipitate, a salt-forming compound containing the organic anion part of the acidic dye and the organic cation part of the basic dye is formed. It can be recovered by filtration, and thus the salt-forming compound is obtained. The obtained salt-forming compound is preferably dried at about 60 to 70 °C.

[0194] The photosensitive resin composition of the present invention may contain two or more (d1a) components. When the photosensitive resin composition of the present invention contains n (d1a) components, the organic ions contained in the photosensitive resin composition are preferably (n + 1) types. Here, n represents an integer of 2 to 10. The organic ions contained in the photosensitive resin composition herein refer not only to the organic ions constituting the ionic dye, but also to all the organic ions contained in the photosensitive resin composition. For example, when the photosensitive resin composition contains n (d1a) components with different organic anion parts and different organic cation parts from each other, the organic ions contained in the photosensitive resin composition become (n × 2) types. In this case, since there are various organic anions and organic cations in the photosensitive resin composition, the following problem occurs: during frozen storage, foreign matters increase due to ion exchange between the ionic dyes, and the storage stability deteriorates. On the other hand, when the photosensitive resin composition contains n (d1a) components and the organic ions contained in the photosensitive resin composition are (n + 1) types, the storage stability during frozen storage is improved. It is presumed that the reason is that since the types of organic ions for the (d1a) components are limited, ion exchange between the ionic dyes is suppressed in the photosensitive resin composition.

[0195] As a first mode in which the photosensitive resin composition contains n (d1a) components and the organic ions contained in the photosensitive resin composition satisfy (n + 1) types, the case where all of the organic anion parts or organic cation parts of the n (d1a) components are the same can be cited. For example, when n is 3, it means that any one of the organic anion parts or organic cation parts in ionic dye 1, ionic dye 2, and ionic dye 3 is all the same. In addition, when n ≥ 3, as a second mode, the case where the organic anion parts and organic cation parts of the n (d1a) components are the same in two or more types each can be cited. For example, when n is 3, it means that the organic anion parts of ionic dye 1 and ionic dye 2 are the same, and the organic cation parts of ionic dye 1 and ionic dye 3 are the same. From the viewpoint of suppressing ion exchange between the ionic dyes and improving the storage stability during frozen storage, the first mode is preferred. From the viewpoint of improving the storage stability, n is preferably 2 to 5, more preferably 2 to 3, and further preferably 2.

[0196] In the present invention, from the viewpoint of fading during curing and light irradiation, the pigment (d2) is preferably a pigment having high heat resistance and light resistance. Since the component (d2-1) has a maximum absorption wavelength in the range of 300 to 800 nm and in any range of 490 nm or more and less than 580 nm, for example, red pigments, purple pigments, etc. can be contained. Since the component (d2-2) has a maximum absorption wavelength in the range of 300 to 800 nm and in any range of 580 nm or more and 800 nm or less, for example, blue pigments, green pigments, etc. can be cited.

[0197] Specific examples of the organic pigment are represented by the dye index (C.I.) number. As examples of the component (d2-1), red pigments such as Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, etc., and purple pigments such as Pigment Violet 19, 23, 29, 32, 33, 36, 37, 38, etc. can be cited. As examples of the component (d2-2), blue pigments such as Pigment Blue 15 (15:3, 15:4, 15:6, etc.), 21, 22, 60, 64, etc., and green pigments such as Pigment Green 7, 10, 36, 47, 58, etc. can be cited. In addition, pigments other than these can also be contained.

[0198] In the present invention, the organic pigment used as the pigment (d2) may contain an organic pigment that has been surface-treated as needed, such as rosin treatment, acidic group treatment, basic group treatment, etc. In addition, a dispersant can be contained as the case may be. The dispersant can contain, for example, cationic, anionic, nonionic, amphoteric, silicone-based, fluorine-based surfactants, etc.

[0199] With respect to 100 parts by mass of the component (a), the content of the component (d) is preferably 0.1 to 300 parts by mass, more preferably 0.2 to 200 parts by mass, and particularly preferably 1 to 200 parts by mass. By making the content of the component (d) 0.1 part by mass or more with respect to 100 parts by mass of the component (a), light of the corresponding wavelength can be absorbed. In addition, by making it 300 parts by mass or less, the adhesion strength between the photosensitive colored resin film and the substrate, the heat resistance of the film after heat treatment, and the mechanical properties can be maintained, and light of the corresponding wavelength can be absorbed.

[0200] In addition, the photosensitive resin composition of the present invention may contain a colorant other than the component (d). By containing other colorants in addition to the component (d), light-shielding properties can be imparted, that is, light having wavelengths that can be absorbed by other colorants is shielded against light passing through the film of the photosensitive resin composition or light reflected from the film of the photosensitive resin composition. By imparting light-shielding properties, when the cured product of the present invention described later is formed into a planarization layer and / or an insulating layer of an organic EL display device, deterioration, malfunction, leakage current, etc. caused by the intrusion of light into the TFT can be prevented. In addition, the suppression of reflection of external light from wirings and TFTs and the contrast between the light-emitting region and the non-light-emitting region can be improved.

[0201] <Free-radical polymerizable compound>

[0202] The photosensitive resin composition of the present invention may contain a free-radical polymerizable compound. In particular, when the above photosensitive resin composition contains a photoinitiator (c2), a free-radical polymerizable compound must be contained. A free-radical polymerizable compound refers to a compound having a plurality of ethylenically unsaturated double bonds in the molecule. During exposure, free-radical polymerization of the free-radical polymerizable compound is carried out using the free radicals generated by the aforementioned photoinitiator (c2), and the light-irradiated portion becomes insoluble, whereby a negative-type pattern can be obtained. In addition, by containing a free-radical polymerizable compound, the photocuring of the light-irradiated portion is promoted, and the sensitivity can be further improved. In addition, the crosslinking density after thermal curing is increased, so that the hardness of the cured product can be increased.

[0203] As the free-radical polymerizable compound, a compound having a (meth)acrylic group, which is easily subjected to free-radical polymerization, is preferred. From the viewpoints of improving the sensitivity during exposure and the hardness of the cured product, a compound having two or more (meth)acrylic groups in the molecule is more preferred. As the double bond equivalent of the free-radical polymerizable compound, from the viewpoints of improving the sensitivity during exposure and the hardness of the cured product, it is preferably 80 to 400 g / mol.

[0204] Regarding the content of the free-radical polymerizable compound, from the viewpoints of further improving the sensitivity and reducing the taper angle, it is preferably 15 parts by mass or more, more preferably 30 parts by mass or more, based on 100 parts by mass in total of the component (a) and the free-radical polymerizable compound. On the other hand, from the viewpoints of further improving the heat resistance of the cured product and reducing the taper angle, it is preferably 65 parts by mass or less, more preferably 50 parts by mass or less, based on 100 parts by mass in total of the component (a) and the free-radical polymerizable compound.

[0205] <Thermal crosslinking agent>

[0206] The resin composition of the present invention may contain a thermal crosslinking agent. The so-called thermal crosslinking agent refers to a compound having at least two known thermally reactive functional groups such as alkoxymethyl, hydroxymethyl, epoxy group, oxetanyl, etc. in the molecule. By containing the thermal crosslinking agent, crosslinking occurs between the thermal crosslinking agent and the alkali-soluble resin (a) or between the thermal crosslinking agents, and the heat resistance, chemical resistance, and bend resistance of the cured product after thermal curing can be improved. From the viewpoint of reducing the transmittance at 300 nm to 500 nm after curing, as the thermal crosslinking agent, a compound having low reactivity with phenolic hydroxyl groups is preferred, and alkoxymethyl is preferred. It is presumed that this is because if the phenolic hydroxyl group of the component (b) reacts with the thermal crosslinking agent, it becomes difficult for the crosslinked body to form a quinone structure.

[0207] When containing the thermal crosslinking agent, the content is preferably 1% by mass or more and 30% by mass or less based on 100% by mass of the total amount of the resin composition excluding the solvent. If the content of the thermal crosslinking agent is 1% by mass or more, the chemical resistance and bend resistance of the cured product can be further improved. In addition, if the content of the thermal crosslinking agent is 30% by mass or less, the gas evolution amount from the cured product can be further reduced, the long-term reliability of the organic EL display device can be further improved, and the storage stability of the resin composition is also excellent.

[0208] <Solvent>

[0209] The photosensitive resin composition of the present invention may contain a solvent. By containing the solvent, it can be made into a varnish state, and the coatability can be improved.

[0210] As the solvent, it may contain polar aprotic solvents such as γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tetrahydrofuran, dioxane and other ethers, acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol and other ketones, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate and other esters, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate and other esters, toluene, xylene and other aromatic hydrocarbons, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, N,N-dimethylpropanamide, N,N-dimethylisobutyramide and other amides, 3-methyl-2-oxazolidinone, etc. The solvent may contain two or more of them.

[0211] The content of the solvent is not particularly limited, and is preferably 100 to 3000 parts by mass, more preferably 150 to 2000 parts by mass, based on 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent. In addition, the proportion of the solvent having a boiling point of 180 °C or higher in 100 parts by mass of the total amount of the solvent is preferably 20 parts by mass or less, more preferably 10 parts by mass or less. By making the proportion of the solvent having a boiling point of 180 °C or higher 20 parts by mass or less, the outgassing amount after thermal curing can be further reduced, and the long-term reliability of the organic EL device can be further improved.

[0212] <Sealing improver>

[0213] The photosensitive resin composition of the present invention may contain an adhesion improver. As the adhesion improver, known silane coupling agents, titanium chelating agents, aluminum chelating agents, compounds obtained by reacting an aromatic amine compound with a silicon compound containing an alkoxy group, etc. may be contained. Two or more of them may be contained. By containing these adhesion improvers, the development adhesion to substrate materials such as silicon wafers, indium tin oxide (ITO), SiO2, and silicon nitride can be improved when developing the resin film or the like. In addition, the resistance to oxygen plasma and UV ozone treatment used in cleaning or the like can be improved. The content of the adhesion improver is preferably 0.01 to 10 parts by mass in 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent.

[0214] <Surfactant>

[0215] The photosensitive resin composition of the present invention may contain a surfactant, which can improve the wettability with the substrate. As the surfactant, known silicone surfactants, fluorosurfactants, acrylic and / or methacrylic surfactants, etc. may be contained.

[0216] When containing a surfactant, the content is preferably 0.001 to 1 part by mass in 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent.

[0217] <Inorganic particles>

[0218] The photosensitive resin composition of the present invention may contain inorganic particles. As preferred specific examples of the inorganic particles, for example, silica, titanium oxide, barium titanate, alumina, talc, etc. may be contained. The primary particle size of the inorganic particles is preferably 100 nm or less, more preferably 60 nm or less.

[0219] The content of the inorganic particles is preferably 5 to 90 parts by mass in 100 parts by mass of the total amount of the photosensitive resin composition excluding the solvent.

[0220] <All chlorine atoms, all bromine atoms>

[0221] Regarding the photosensitive resin composition of the present invention, with respect to the total mass of the solid components obtained by removing the solvent from the photosensitive resin composition, the total mass of all chlorine atoms and all bromine atoms contained in the photosensitive resin composition is preferably 150 mass ppm or less, more preferably 100 mass ppm or less, and further preferably less than 2 mass ppm (which is the detection limit of combustion ion chromatography).

[0222] By making the total amount of all chlorine atoms and all bromine atoms contained in the photosensitive resin composition 150 mass ppm or less based on the solid content of the photosensitive resin composition, deterioration of the electrodes and light-emitting layer of an organic EL display device having a cured product obtained by curing the photosensitive resin composition can be suppressed, and long-term reliability can be improved.

[0223] In addition, by making the total amount of all chlorine atoms and all bromine atoms contained in the photosensitive resin composition 150 mass ppm or less based on the solid content obtained by removing the solvent from the photosensitive resin composition, the storage stability during frozen storage of the photosensitive resin composition of the present invention can be improved.

[0224] The total mass of all chlorine atoms and all bromine atoms contained in the photosensitive resin composition can be measured, for example, by combustion ion chromatography using the photosensitive resin composition.

[0225] <Method for manufacturing a photosensitive resin composition>

[0226] Next, a method for manufacturing the photosensitive resin composition of the present invention will be described. For example, the components (a), (b), and (c) and, if necessary, the component (d), a radical polymerizable compound, a thermal crosslinking agent, a solvent, an adhesion improver, a surfactant, inorganic particles, etc. can be dissolved to obtain the photosensitive resin composition of the present invention.

[0227] Examples of the dissolution method include stirring and heating. When heating is performed, the heating temperature is preferably set within a range that does not impair the performance of the photosensitive resin composition, usually from room temperature to 80°C. In addition, the dissolution order of each component is not particularly limited. For example, a method of dissolving in order from the compound with low solubility can be cited. In addition, for components such as surfactants and some adhesion improvers that are likely to generate bubbles during stirring and dissolution, they can be added last after dissolving other components, thereby preventing poor dissolution of other components caused by the generation of bubbles.

[0228] The obtained photosensitive resin composition is preferably filtered using a filter to remove dirt and particles. Examples of the filter pore size include 0.5 μm, 0.2 μm, 0.1 μm, 0.07 μm, 0.05 μm, 0.02 μm, etc., but are not limited thereto. Examples of the filter material include polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc. Among them, polyethylene and nylon are preferred.

[0229] <Method for manufacturing a cured product>

[0230] The method for manufacturing a cured product of the present invention is a method for manufacturing a cured product including the following steps: a step of forming a resin film containing the photosensitive resin composition of the present invention on a substrate; a step of exposing the resin film; a step of developing the exposed resin film; and a step of heat-treating the developed resin film.

[0231] The step of forming a resin film containing the photosensitive resin composition of the present invention on a substrate will be described. In the present invention, the resin film can be obtained by the following method: coating the photosensitive resin composition of the present invention to obtain a coated film of the photosensitive resin composition, and drying it.

[0232] As the substrate, a known substrate such as a glass substrate can be used.

[0233] As a method for coating the photosensitive resin composition of the present invention, for example, spin coating method, slit coating method, dip coating method, spraying method, printing method, etc. can be cited. Among them, from the aspect of being able to coat with a small amount of coating liquid and being advantageous for cost reduction, the slit coating method is preferred. The amount of the coating liquid required for the slit coating method is, for example, about 1 / 5 to 1 / 10 compared to the spin coating method. As the slit nozzle used in the coating, for example, "Linearcoater" manufactured by Da inippon Screen Mfg.Co.,Ltd., "Spinless" manufactured by Tokyo Ohka Kogyo Co., Ltd., "TSCoater" manufactured by Toray Engineering Co., Ltd., "Tabel Coater" manufactured by Chugai Ro Co., Ltd., "CS series" and "CL series" manufactured by Tokyo Electron Co., Ltd., "Inline type slit coater" manufactured by CERMA TRONICS Trading Co., Ltd., "Head Coater HC series" manufactured by Hirata Kiko Co., Ltd., etc., slit nozzles marketed by multiple manufacturers can be selected. The coating speed is usually in the range of 10 mm / second to 400 mm / second. The film thickness of the coated film varies depending on the solid content concentration, viscosity, etc. of the photosensitive resin composition, and is usually coated so that the film thickness after drying becomes 0.1 to 10 μm, preferably 0.3 to 5 μm.

[0234] Before coating, the substrate for coating the photosensitive resin composition can be pretreated with the aforementioned adhesion improver. As the pretreatment method, for example, the following method can be cited: using a solution obtained by dissolving 0.5 to 20% by mass of the adhesion improver in a solvent such as isopropyl alcohol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, etc., to treat the surface of the substrate. As the treatment method for the substrate surface, spin coating method, slot die coating method, bar coating method, dip coating method, spraying method, vapor treatment method, etc. can be cited.

[0235] After coating, a reduced-pressure drying treatment is carried out as required.

[0236] Although the reduced-pressure drying rate also depends on the vacuum chamber volume, the vacuum pump capacity, the piping diameter between the chamber and the pump, etc., for example, it is preferably set under the condition that the pressure in the vacuum chamber is reduced to 40 Pa after 60 seconds in the state of no-coated substrate. Usually, the reduced-pressure drying time is mostly about 30 seconds to 100 seconds, and the pressure reached in the vacuum chamber at the end of the reduced-pressure drying is usually 100 Pa or less in the state of having a coated substrate. By making the reached pressure 100 Pa or less, a drying state with reduced stickiness on the surface of the coating film can be achieved, and thus, surface contamination and generation of particles during subsequent substrate handling can be suppressed.

[0237] After coating or after reduced-pressure drying, the coating film is usually heated and dried. This process is also called pre-baking. Heating is performed using a hot plate, an oven, infrared rays, etc. In the case of using a hot plate, the coating film is directly held on the plate and heated, or the coating film is held on jigs such as fixed pins provided on the plate and heated. The heating time is preferably 1 minute to several hours. The heating temperature varies depending on the type and purpose of the coating film, but from the viewpoint of promoting solvent drying during pre-baking, it is preferably 80°C or higher, more preferably 90°C or higher. On the other hand, from the viewpoint of reducing curing during pre-baking, it is preferably 150°C or lower, more preferably 140°C or lower.

[0238] Next, the process of exposing the above resin film will be described.

[0239] The resin film of the present invention can form a pattern. For example, chemical rays can be irradiated onto the resin film through a photomask having a desired pattern, thereby performing exposure, and a desired pattern can be formed by developing.

[0240] Examples of the chemical rays used in the exposure include ultraviolet light, visible light, electron beams, X-rays, etc. In the present invention, i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp are preferably used. In the case of having positive photosensitivity, the exposed portion dissolves in the developer. In the case of having negative photosensitivity, the exposed portion cures and is insoluble in the developer.

[0241] Next, the process of developing the exposed resin film will be described.

[0242] After exposure, in the case of a positive type, the exposed portion is removed with a developer, and in the case of a negative type, the unexposed portion is removed with a developer, thereby forming a desired pattern. As the developer, an aqueous solution of a basic compound such as 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. is preferred. One or more of polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, alcohols such as methanol, ethanol, isopropyl alcohol, esters such as ethyl lactate, propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, methyl isobutyl ketone, etc. can also be added to these basic aqueous solutions. As the developing method, spraying, spin coating immersion, dipping, ultrasonic wave, etc. can be cited.

[0243] Next, it is preferable to perform a rinsing treatment on the pattern formed by development with distilled water. Alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, etc. can also be added to distilled water for the rinsing treatment.

[0244] Next, the step of heat-treating the developed resin film will be described.

[0245] After development, the developed resin film is heat-treated to obtain a cured product.

[0246] From the viewpoint of further reducing the outgassing amount generated by the cured product, the heat treatment temperature is preferably 180 °C or higher, more preferably 200 °C or higher, further preferably 230 °C or higher, and particularly preferably 250 °C or higher. On the other hand, from the viewpoint of improving the film toughness of the cured product, it is preferably 500 °C or lower, more preferably 450 °C or lower. Within this temperature range, the temperature can be raised stepwise or continuously. From the viewpoint of further reducing the outgassing amount, the heat treatment time is preferably 30 minutes or longer. In addition, from the viewpoint of improving the film toughness of the cured product, it is preferably 3 hours or shorter. For example, the following methods can be cited: a method of performing heat treatment at 150 °C and 250 °C for 30 minutes each; a method of performing heat treatment while linearly raising the temperature from room temperature to 300 °C over 2 hours; and so on.

[0247] From the viewpoint of preventing the electrode from being contaminated by outgassing components during heat curing when the photosensitive resin composition of the present invention is used in an organic EL display device or the like and the current-voltage characteristics from deteriorating, the atmosphere during the heat treatment is preferably a low oxygen concentration of less than 5% oxygen concentration. By preventing the deterioration of the current-voltage characteristics, the driving voltage of the organic EL display device can be further reduced, and the luminous efficiency and durability can be further improved. Specific examples of the inert gas used to make the oxygen concentration less than 5% include nitrogen, argon, etc. The oxygen concentration in the inert gas atmosphere is preferably less than 5%, more preferably less than 1%, further preferably less than 0.5%, and particularly preferably less than 0.01%.

[0248] <Cured product>

[0249] The cured product of the present invention is a cured product obtained by curing the photosensitive resin composition of the present invention. By performing a heat treatment on the photosensitive resin composition of the present invention, components with low heat resistance can be removed, so the heat resistance and chemical resistance can be further improved. Especially when the photosensitive resin composition of the present invention contains a polyimide precursor, a polybenzoxazole precursor, a copolymer thereof, or a copolymer of them and polyimide, imide rings and oxazole rings are formed by heat treatment, so the heat resistance and chemical resistance can be further improved.

[0250] In addition, by making the photosensitive resin composition of the present invention contain component (b), the ultraviolet light transmittance of the cured product can be reduced. Further, in the present invention, by using component (b) and component (d) in combination, the visible light transmittance of the cured product can be reduced to obtain a black cured product. From the viewpoint of further reducing the outgassing amount generated by the cured product, the heat treatment temperature is preferably 180 °C or higher, more preferably 200 °C or higher, further preferably 230 °C or higher, and particularly preferably 250 °C or higher. On the other hand, from the viewpoint of improving the film toughness of the cured product, it is preferably 500 °C or lower, more preferably 450 °C or lower. Within this temperature range, the temperature can be raised stepwise or continuously. From the viewpoint of further reducing the outgassing amount, the heat treatment time is preferably 30 minutes or longer. In addition, from the viewpoint of improving the film toughness of the cured product, it is preferably 3 hours or shorter. For example, the following methods can be cited: a method of performing heat treatment at 150 °C and 250 °C for 30 minutes each; a method of performing heat treatment while linearly raising the temperature from room temperature to 300 °C over 2 hours; and so on.

[0251] <Application examples of the photosensitive resin composition and the cured product>

[0252] The photosensitive resin composition and cured product of the present invention are suitable for use as surface protective layers of semiconductor elements, interlayer insulating layers, insulating layers of organic electroluminescence (hereinafter referred to as EL) elements, planarization layers of driving thin film transistors (hereinafter referred to as TFT) substrates of display devices using organic EL elements, wiring protective insulating layers of circuit boards, on-chip microlenses of solid-state imaging devices, and planarization layers for various display devices and solid-state imaging devices. For example, it is suitable as a surface protective layer and an interlayer insulating layer for MRAM with low heat resistance, polymer memory (Polymer Ferro electric RAM: PFRAM), which is expected to be the next-generation memory, phase change memory (Phase Change RAM: PCR AM, Ovonics Unified Memory: OUM), etc. In addition, it can also be used for insulating layers of display devices including a first electrode formed on a substrate and a second electrode disposed opposite to the first electrode, such as LCD, ECD, ELD, and display devices using organic field-emission elements (organic field-emission devices). Hereinafter, an organic EL display device, a semiconductor device, and a semiconductor electronic component will be taken as examples for description.

[0253] <Organic EL display device>

[0254] The organic EL display device of the present invention is an organic EL display device having a driving circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate, and the planarization layer and / or the insulating layer has the cured product of the present invention.

[0255] When the planarization layer and / or the insulating layer has the cured product of the present invention, the transmittance at a wavelength of 450 nm of the planarization layer and / or the insulating layer is preferably less than 30%. If the transmittance at a wavelength of 450 nm is less than 30%, in an organic EL display device using an oxide semiconductor layer TFT, malfunction and the like caused by the entry of ultraviolet light into the TFT can be prevented. In order to prevent the entry of ultraviolet light into the TFT, the transmittance at a wavelength of 450 nm is preferably less than 30%, more preferably less than 20%, and further preferably less than 10%. The lower limit of the transmittance at a wavelength of 450 nm is not particularly limited, but is 0.01% or more.

[0256] In addition, when the aforementioned planarization layer and / or insulating layer contains the cured product of the present invention, the OD value (optical density) of the planarization layer and / or insulating layer per 1 μm film thickness under visible light is preferably 0.5 to 1.5. If the OD value is 0.5 or more, the light shielding property can be improved by the cured product. Therefore, in a display device such as an organic EL display device or a liquid crystal display device, external light reflection can be further reduced, and the contrast during image display can be improved. From the viewpoint of reducing reflection, the OD value is preferably 0.5 or more, more preferably 0.6 or more, further preferably 0.7 or more, and particularly preferably 0.8 or more. In addition, if the OD value is 1.5 or less, the sensitivity during exposure when forming a photosensitive resin composition containing a photosensitive compound can be improved. From the viewpoint of achieving high sensitivity, the OD value is 1.5 or less, more preferably 1.0 or less.

[0257] When the aforementioned insulating layer is a black film, the film thickness of the insulating layer is preferably 1.0 to 5.0 μm, more preferably 1.5 μm or more, and further preferably 2.0 μm or more. By making the black insulating layer within the aforementioned range, even a black film with a low OD value per 1 μm film thickness under visible light can increase the OD value of the entire film, and the effect of reducing external light reflection can be improved.

[0258] When taking an active matrix type display device as an example, a TFT is provided on a substrate such as glass or various plastics, and wirings located on the side portions of the TFT and connected to the TFT are provided. A planarization layer is provided thereon in a manner covering the unevenness, and a display element is further provided on the planarization layer. The display element is connected to the wiring via a contact hole formed in the planarization layer. In particular, in recent years, the flexibility of organic EL display devices has become mainstream. Therefore, it is preferred that the aforementioned substrate having a driving circuit is an organic EL display device including a resin film. If a cured product obtained by curing the photosensitive resin composition of the present invention is used as the insulating layer and planarization layer of such a flexible display device, the bend resistance is excellent, and thus it is particularly preferably used. From the viewpoint of improving the adhesion to the cured product obtained by curing the photosensitive resin composition of the present invention, as the resin film, polyimide is particularly preferred.

[0259] In order to improve the effect of reducing external light reflection, an organic EL display device preferably further includes a color filter having a black matrix. The black matrix preferably contains a resin such as an epoxy resin, an acrylic resin, a urethane resin, a polyester resin, a polyimide resin, a polyolefin resin, or a silicone resin.

[0260] The black matrix contains a colorant. As the colorant, for example, black organic pigments, mixed-color organic pigments, inorganic pigments, etc. can be contained. As the black organic pigment, for example, carbon black, perylene black, aniline black, benzofuranone-based pigments, etc. can be contained. As the mixed-color organic pigment, for example, a mixed-color organic pigment obtained by mixing two or more pigments such as red, blue, green, purple, yellow, magenta, and / or cyan to approximate black can be contained. As the black inorganic pigment, for example, it can contain: graphite; fine particles of metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, silver, etc.; metal oxides; metal composite oxides; metal sulfides; metal nitrides; metal oxynitrides; metal carbides, etc. Among them, carbon black, titanium nitride, titanium carbide, and composite particles of them and metals such as silver having high light-shielding properties are preferred.

[0261] As the OD value of the black matrix, it is preferably 1.5 or more, more preferably 2.5 or more, and further preferably 4.5 or more.

[0262] Figure 1 FIG. shows a cross-sectional view of an example of an organic EL display device. On a substrate 6, bottom-gate type or top-gate type TFTs (thin film transistors) 1 are arranged in a row-and-column pattern, and a TFT insulating layer 3 is formed in a state of covering the TFTs 1. In addition, wirings 2 connected to the TFTs 1 are provided on the TFT insulating layer 3. Further, on the TFT insulating layer 3, a planarization layer 4 is provided in a state of burying the wirings 2. In the planarization layer 4, contact holes 7 reaching the wirings 2 are provided. Then, via the contact holes 7, an ITO (transparent electrode) 5 is formed on the planarization layer 4 in a state of being connected to the wirings 2. Here, the ITO 5 becomes an electrode of a display element (for example, an organic EL element). Then, an insulating layer 8 is formed so as to cover the periphery of the ITO 5. The organic EL element can be a top-emission type that emits light released from the side opposite to the substrate 6, or a bottom-emission type that extracts light from the substrate 6 side. As described above, an active matrix type organic EL display device in which TFTs 1 for driving are connected to each organic EL element can be obtained.

[0263] The TFT insulating layer 3, the planarization layer 4, and / or the insulating layer 8 can be formed by the following steps as described above: a step of forming a resin film containing the photosensitive resin composition of the present invention; a step of exposing the aforementioned resin film; a step of developing the exposed resin film; and a step of heat-treating the developed resin film. An organic EL display device can be obtained by a manufacturing method having these steps.

[0264] <Display devices other than organic EL display devices>

[0265] The display device other than the organic EL display device of the present invention is a display device having at least a metal wiring, a cured product of the present invention, and a plurality of light-emitting elements, and the display device is configured such that: the light-emitting elements have a pair of electrode terminals on any one surface, the pair of electrode terminals are connected to a plurality of the metal wirings extending in the cured product, and the plurality of the metal wirings are kept electrically insulated by the cured product.

[0266] Regarding the above display device, Figure 2 it will be described as an example of one mode.

[0267] In Figure 2 , in the display device 9, a plurality of light-emitting elements 10 are arranged on the counter substrate 15, and a cured product 11 is arranged on the light-emitting elements 10. By the light-emitting elements, it means not only the surface of the light-emitting elements but also any position above the support substrate and the light-emitting elements. Figure 2 In the mode shown, an example is illustrated in which a plurality of cured products 11 are further laminated on the cured product 11 arranged in contact with at least a part of the light-emitting element 10 to form a total of three laminated layers, but the cured product 11 may be a single layer. The light-emitting element 10 has a pair of electrode terminals 14 on the opposite surface of the surface in contact with the counter substrate 13, and each electrode terminal 14 is connected to a metal wiring 12 extending in the cured product 11. It should be noted that if the plurality of metal wirings 12 extending in the cured product 11 are covered by the cured product 11, the cured product 11 also functions as an insulating layer, and thus a configuration for maintaining electrical insulation is formed. The so-called metal wiring forms a configuration for maintaining electrical insulation means that the portion of the metal wiring that requires electrical insulation is covered with a cured product obtained by curing a photosensitive resin composition containing an alkali-soluble resin (a). In addition, in the present invention, the state in which the insulating layer has electrical insulation means that the volume resistivity of the insulating layer is 10 12 Ω·cm or more. In addition, the light-emitting element 10 is electrically connected to a driving element 16 attached to a light-emitting element driving substrate 15 provided at a position opposite to the counter substrate 13 through metal wirings 12 and 12c, and the light emission of the light-emitting element 10 can be controlled. In addition, the light-emitting element driving substrate 15 is electrically connected to the metal wiring 12 via, for example, solder bumps 18. In addition, a barrier metal 17 may be arranged to prevent the diffusion of metals such as the metal wiring 12.

[0268] The aforementioned cured product 11 is preferably black, and the OD value under visible light per 1 μm film thickness of the insulating layer is 0.5 to 1.5. If the OD value is 0.5 or more, the light-shielding property can be improved by the cured product. Therefore, in a display device such as an organic EL display device or a liquid crystal display device, the visualization of electrode wirings and external light reflection can be further reduced, and the contrast during image display can be improved. In addition, if the OD value is 1.5 or less, the sensitivity during exposure when producing a photosensitive resin composition containing a photosensitive compound can be improved.

[0269] The phenolic compound of the present invention is a phenolic compound having a structure represented by formula (b2).

[0270] [Chemical formula 23]

[0271]

[0272] In formula (b2), n represents an integer of 2 to 4, and * represents a linking bond.

[0273] By including the aforementioned phenolic compound having a structure represented by formula (b2) in the photosensitive resin composition, the transmittances at wavelengths of 450 nm and 500 nm of the cured product of the photosensitive resin composition can be reduced.

[0274] The aforementioned phenolic compound having a structure represented by formula (b2) more preferably satisfies the following condition (b1): with respect to any phenolic hydroxyl group in formula (b2), the substitution position of at least one of the other phenolic hydroxyl groups is the para position.

[0275] There is no particular limitation on the upper limit of the molecular weight of the phenolic compound having a structure represented by formula (b2), and it is preferably 1000 or less, preferably 800 or less, and more preferably 600 or less. The lower limit of the molecular weight of the phenolic compound having a structure represented by formula (b2) is 126 or more.

[0276] Other preferred modes of the phenolic compound having a structure represented by formula (b2) are the same as those of the aforementioned component (b2).

[0277] The phenolic compound of the present invention is a phenolic compound containing one or more selected from the group consisting of structures represented by component (b3), component (b4), or component (b5).

[0278] [Chemical formula 24]

[0279]

[0280] In formula (b3), formula (b4), and formula (b5), n and m each independently represent an integer of 2 to 4, p represents an integer of 0 to 2, q represents an integer of 0 to 4, and 2 ≤ p + m ≤ 4 is satisfied. X represents -NR 32-, -O-, -S-, R 32 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R 33 each independently represents a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R 34 and R 35 each independently represents -OR 36 , -SR 36 , -N(R 36 )2, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R 36 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.

[0281] By making the photosensitive resin composition contain a phenolic compound represented by one or more selected from the group consisting of the component (b3), the component (b4) and the component (b5) as the component (b), the transmittance at a wavelength of 550 nm after curing of the photosensitive resin composition can be further reduced.

[0282] From the viewpoint of further reducing the transmittance at a wavelength of 550 nm after curing when contained in the photosensitive resin composition, it is preferable to make the photosensitive resin composition contain the component (b3) and / or the component (b4), and it is more preferable to make the photosensitive resin composition contain the component (b3).

[0283] From the viewpoint of further reducing the transmittance at a wavelength of 550 nm after curing when contained in the photosensitive resin composition, the aforementioned component (b3), component (b4) and component (b5) more preferably satisfy the following condition (b1): with respect to the phenolic hydroxyl group represented in the formula (b3), the formula (b4) or the formula (b5), the substitution position of at least one of the other phenolic hydroxyl groups is the p-position.

[0284] The phenolic compound of the present invention is a phenolic compound having a structure represented by any of the following chemical formulas.

[0285] [Chemical formula 25]

[0286]

[0287] By making the photosensitive resin composition contain the above phenolic compound, the transmittance at a wavelength of 450 nm of the cured product of the photosensitive resin composition can be further reduced.

[0288] Examples

[0289] Hereinafter, the present invention will be described by giving examples and the like, but the present invention is not limited by these examples. It should be noted that each evaluation in the examples is carried out by the following method.

[0290] (1) Evaluation of light-shielding properties at 450 nm and 500 nm (transmittance at 450 nm and 500 nm)

[0291] On a 5 cm square glass substrate, the varnishes obtained from each example and comparative example were spin-coated so that the film thickness after heat treatment (curing) became 2.0 μm, and pre-baked at 120 °C for 120 seconds to produce a pre-baked film. Then, using a high-temperature clean oven INH-9CD-S manufactured by Koyo Thermo Systems Co., Ltd., curing was performed at 250 °C for 60 minutes in a nitrogen atmosphere with an oxygen concentration of about 1% or in an air atmosphere (in the curing atmospheres in Tables 1 to 3, they are "nitrogen" and "air" respectively) to produce a cured film (hereinafter sometimes referred to as a cured film). It should be noted that the film thickness of the cured film was measured using a stylus profilometer (P-15; manufactured by KLA Corporation). For the cured film obtained as described above, the transmission spectrum from 300 nm to 800 nm was measured using a UV-visible spectrophotometer MultiSpec-1500 (manufactured by Shimadzu Corporation), and the transmittance at a wavelength of 450 nm (hereinafter referred to as T%) 450 ) and the transmittance at 500 nm (hereinafter referred to as T%) 500 ) were obtained. When the T% 450 and T% 500 at a cured film thickness of 2.0 μm were both less than 15%, it was judged as "S". When T% 450 was less than 15% and T% 500 was 15% or more and less than 25%, it was judged as "A". When T% 450 was less than 15% and T% 500 was 25% or more and less than 35%, and when T% 450 was 15% or more and less than 20% and T% 500 was less than 35%, it was judged as "B". When it was not related to T% 500 and T% 450 was 20% or more, and when it was not related to T% 450 and T% 500 was 35% or more, it was judged as "C".

[0292] (2) Evaluation of light-shielding properties at 550 nm (transmittance at 550 nm)

[0293] For the cured film obtained in the same manner as (1), the transmission spectrum in the wavelength range of 300 nm to 800 nm was measured using a UV-visible spectrophotometer MultiSpec-1500 (manufactured by Shimadzu Corporation), and the transmittance at a wavelength of 550 nm when the film thickness after curing was 2.0 μm was determined (hereinafter referred to as T%). 550 ) When the T% 550 is less than 5% when the film thickness after curing is 2.0 μm, it is judged as "S". When the T% 550 is 5% or more and less than 20%, it is judged as "A". When the T% 550 is 20% or more and less than 35%, it is judged as "B". When the T% 550 is 35% or more, it is judged as "C".

[0294] (3) Evaluation of visible light shielding property (OD value per 1 μm, transmittance at 450 nm)

[0295] For the cured film obtained in the same manner as (1), the OD value was measured using a densitometer (361T; manufactured by X-Rite Inc.), and the transmission spectrum in the wavelength range of 300 nm to 800 nm was measured using a UV-visible spectrophotometer MultiSpec-1500 (manufactured by Shimadzu Corporation), and the T% 450 when the film thickness after curing was 2.0 μm was determined. The obtained OD value was divided by the film thickness of the cured film, thereby obtaining the OD value per 1 μm (hereinafter referred to as OD / μm) (OD value per 1 μm = OD value / film thickness of the cured film).

[0296] When the OD / μm is 0.70 or more and the T% 450 is less than 10%, it is judged as "S".

[0297] When the OD / μm is 0.70 or more and the T% 450 is 10% or more and less than 20%, it is judged as "A".

[0298] When the OD / μm is 0.70 or more and the T% 450 is 20% or more and less than 30%, it is judged as "B".

[0299] When the OD / μm is less than 0.70 and 0.50 or more and the T% 450 is less than 10%, it is judged as "A".

[0300] When the OD / μm is less than 0.70 and 0.50 or more and the T% 450 is 10% or more and less than 20%, it is judged as "B".

[0301] When OD / μm is less than 0.70 and not less than 0.50 and T% 450 is not less than 20% and less than 30%, it is determined as "C".

[0302] Regardless of OD / μm, when T% 450 is not less than 30% and in the case where OD / μm is less than 0.50 regardless of T% 450 it is determined as "D".

[0303] (4) Chemical resistance

[0304] After measuring the film thickness of the cured film obtained in the same manner as in (1), the cured film is immersed in a mixed solution of N-methylformamide / ethylene glycol = 55 / 45 (mass ratio) at 60°C for 3 minutes. After washing the cured film taken out from the mixed solution with pure water, it is baked at 100°C for 1 minute to dehydrate it. The film thickness is measured again, and the absolute value (μm) of the change in film thickness before and after the solution immersion is calculated. It should be noted that the film thickness of the cured film is measured using a stylus profilometer (P-15; manufactured by KLA Corporation). When the absolute value of the change in film thickness is less than 0.3 μm, it is determined as "S", when the absolute value of the change in film thickness is not less than 0.3 μm and less than 0.6 μm, it is determined as "A", when the absolute value of the change in film thickness is not less than 0.6 μm and less than 1.0 μm, it is determined as "B", and when the absolute value of the change in film thickness is not less than 1.0 μm, it is determined as "C".

[0305] (5) Evaluation of current-voltage characteristics of organic EL display device

[0306] The schematic diagrams of the manufacturing steps of the organic EL display devices using the photosensitive resin compositions obtained in each of the examples and comparative examples are shown in Figure 3First, on a 38 mm × 46 mm non-alkali glass substrate 19, a 10-nm ITO transparent conductive film is formed over the entire surface of the substrate by sputtering and etched into a first electrode (transparent electrode) 20. Additionally, an auxiliary electrode 21 for extracting the second electrode is also formed. After subjecting the obtained substrate to ultrasonic cleaning for 10 minutes using Semico Clean 56 (trade name, manufactured by Furuuchi Chemical Co., Ltd.), it is cleaned with ultrapure water. Next, on the entire surface of this substrate, the photosensitive resin composition obtained in each example and comparative example is coated by spin coating and pre-baked on a hot plate at 120°C for 2 minutes. Through a photomask, using a high-pressure mercury lamp as a light source, the film is exposed at the minimum exposure amount of each photosensitive resin composition, developed using a 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution to dissolve the unnecessary portions, and rinsed with pure water. Using a high-temperature clean oven INH-9CD-S manufactured by Koyo Thermo Systems Co., Ltd., the obtained resin pattern is heat-treated at 230°C for 60 minutes in an air atmosphere or a nitrogen atmosphere. As described above, an insulating layer 22 with openings having a width of 70 μm and a length of 260 μm is arranged at intervals of 155 μm in the width direction and at intervals of 465 μm in the length direction, and each opening is shaped to expose the first electrode, and is formed within the effective area of the substrate. As described above, an insulating layer with an insulating layer opening ratio of 25% is formed within a substrate effective area in the shape of a quadrilateral with a side length of 16 mm. The thickness of the insulating layer is approximately 1.5 μm.

[0307] Next, an organic EL layer 23 including a light-emitting layer is formed by vacuum evaporation. It should be noted that the degree of vacuum during evaporation is 1 × 10 -3 Pa or less, and the substrate is rotated relative to the evaporation source during evaporation. First, a 10-nm compound (HT-1) as a hole injection layer and a 50-nm compound (HT-2) as a hole transport layer are evaporated. Next, a compound (GH-1) as a host material and a compound (GD-1) as a dopant material are evaporated onto the light-emitting layer to a thickness of 40 nm such that the doping concentration becomes 10%. Next, a compound (ET-1) as an electron transport material and a compound (LiQ) are laminated in a volume ratio of 1:1 to a thickness of 40 nm. The structures of the compounds used in the organic EL layer are shown below.

[0308] [Chemical formula 26]

[0309]

[0310] Next, after vapor-depositing a 2-nm compound (LiQ), Mg and Ag are vapor-deposited at a volume ratio of 10:1 for 10 nm to form the second electrode (non-transparent electrode) 24. Finally, in a low-humidity nitrogen atmosphere, a cap-shaped glass plate is bonded using an epoxy resin-based adhesive, thereby performing sealing, and four top-emission organic EL display devices (which are quadrilaterals with a side length of 5 mm) are fabricated on one substrate. It should be noted that the film thickness here refers to the value displayed by a quartz oscillator film thickness monitor.

[0311] at 10 mA / cm 2 The organic EL display device fabricated by the above method is driven with direct current, and the driving voltage at this time is measured. The case where the average value of the driving voltages of the four organic EL display devices fabricated on one substrate is less than 4.0 V is determined as "A", the case where it is 4.0 V or more and less than 4.2 V is determined as "B", and the case where it is 4.2 V or more is determined as "C".

[0312] Synthesis of diamine compound (α) containing a hydroxyl group in Synthesis Example 1

[0313] Dissolve 18.3 g (0.05 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as BAHF) in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide, and cool to -15°C. A solution obtained by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride in 100 mL of acetone is added dropwise thereto. After the addition is completed, the reaction is carried out at -15°C for 4 hours, and then the temperature is restored to room temperature. The precipitated white solid is separated by filtration and vacuum-dried at 50°C.

[0314] Charge 30 g of the solid into a 300-mL stainless-steel autoclave, disperse it in 250 mL of methyl cellosolve, and add 2 g of 5 mass% palladium-carbon. Hydrogen is introduced into it using a balloon, and a reduction reaction is carried out at room temperature. After about 2 hours, when it is confirmed that the balloon no longer deflates, the reaction is terminated. After the reaction is completed, the palladium compound as a catalyst is removed by filtration, and concentration is carried out using a rotary evaporator to obtain a diamine compound (α) containing a hydroxyl group represented by the following formula.

[0315] [Chemical formula 27]

[0316]

[0317] Synthesis of quinone diazide compound (c-1) in Synthesis Example 2

[0318] Under a dry nitrogen stream, 21.22 g (0.05 mol) of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) and 26.87 g (0.10 mol) of diazonaphthoquinone-5-sulfonyl chloride were dissolved in 450 g of 1,4-dioxane at room temperature. 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise thereto in such a manner that the temperature inside the system did not exceed 35 °C. After the addition, the mixture was stirred at 30 °C for 2 hours. The triethylamine salt was filtered off, and the filtrate was poured into water. Then, the precipitated solid was collected by filtration. The solid was dried using a vacuum dryer to obtain a quinone diazide compound (c-1) represented by the following formula.

[0319] [Chemical formula 28]

[0320]

[0321] Synthesis Example 3 Synthesis of alkali-soluble resin (a-1)

[0322] Under a dry nitrogen stream, 31.0 g (0.10 mol) of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride (hereinafter referred to as ODPA) was dissolved in 500 g of N-methylpyrrolidone (hereinafter referred to as NMP). 45.35 g (0.075 mol) of the hydroxyl group-containing diamine compound (α) obtained in Synthesis Example 1 and 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (hereinafter referred to as SiDA) were added thereto together with 50 g of NMP, and the reaction was carried out at 40 °C for 2 hours. Next, 4.36 g (0.04 mol) of 3-aminophenol (hereinafter referred to as MAP) as a capping agent was added thereto together with 5 g of NMP, and the reaction was carried out at 50 °C for 2 hours. Then, a solution obtained by diluting 32.39 g (0.22 mol) of N,N-dimethylformamide diethyl acetal with 50 g of NMP was added. After the addition, the mixture was stirred at 50 °C for 3 hours. After completion of the stirring, the solution was cooled to room temperature and then poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and dried using a vacuum dryer at 80 °C for 24 hours to obtain a polyimide precursor (a-1) as an alkali-soluble resin.

[0323] Synthesis Example 4 Synthesis of alkali-soluble resin (a-2)

[0324] Under a dry nitrogen stream, 29.3 g (0.08 mol) of BAHF, 1.24 g (0.005 mol) of SiDA, and 2.18 g (0.02 mol) of MAP as a capping agent were dissolved in 150 g of NMP. 31.0 g (0.10 mol) of ODPA was added thereto together with 50 g of NMP, and the mixture was stirred at 60 °C for 1 hour and then at 180 °C for 5 hours. After completion of stirring, the solution was poured into 3 L of water, and a white precipitate was collected. The precipitate was collected by filtration, washed three times with water, and dried using a vacuum dryer at 80 °C for 24 hours to obtain polyimide (a-2) as an alkali-soluble resin.

[0325] Synthesis Example 5 Synthesis of alkali-soluble resin (a-3)

[0326] Under a dry nitrogen stream, 31.1 g (0.085 mol) of BAHF and 2.18 g (0.02 mol) of MAP were dissolved in 150 g of NMP and 52.8 g (0.6 mol) of glycidyl methyl ether, and the temperature of the solution was cooled to -15 °C. A solution obtained by dissolving 29.5 g (0.10 mol) of diphenyl ether dicarbonyl chloride (manufactured by Nippon Nohyaku Co., Ltd.) in 50 g of NMP was added dropwise thereto so that the internal temperature did not exceed 0 °C. After completion of the dropwise addition, stirring was continued at -15 °C for 6 hours. After completion of the reaction, the solution was poured into 3 L of water containing 10 wt% of methanol, and a white precipitate was collected. The precipitate was collected by filtration, washed three times with water, and dried using a vacuum dryer at 80 °C for 24 hours to obtain polyhydroxyamide (a-3) as an alkali-soluble resin.

[0327] Synthesis Example 6 Synthesis of alkali-soluble resin (a-4)

[0328] Under a dry nitrogen stream, 8 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 220 g of propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA). Next, 15 g of methacrylic acid, 25 g of glycidyl methacrylate, 10 g of p-isopropenylphenol, 25 g of methyl methacrylate, 5 g of lauryl methacrylate, and 20 g of N-(cyclohexyl)maleimide were added, and the mixture was stirred at 70 °C for 5 hours. After completion of stirring, PGMEA was added to the resin solution until the solid content concentration became 30 mass%, to obtain a 30 mass% solution of acrylic resin (a-4) as an alkali-soluble resin.

[0329] Synthesis Example 7 Synthesis of phenolic compound (b1-1)

[0330] Under a dry nitrogen stream, at room temperature, 1.68 g (0.01 mol) of 2,6-bis(hydroxymethyl)-p-cresol (hereinafter referred to as 26DPMC), 12.61 g (0.10 mol) of 1,2,4-trihydroxybenzene (hereinafter referred to as 124THB), and 0.29 g of p-toluenesulfonic acid monohydrate were dissolved in 40 g of water, and the reaction was carried out at 65 °C for 4 hours. Then, the precipitate formed by cooling with an ice bath was collected by filtration, washed 3 times with water, and dried using a vacuum dryer at 50 °C for 24 hours to obtain a phenolic compound (b1-1) that satisfies condition (b1).

[0331] The obtained compound was subjected to LC-MS analysis using LC-MS2020 (manufactured by Shimadzu Corporation) to confirm that it was the target compound.

[0332] LC-MS (ESI, nega): m / z 383 [M-H] -

[0333] [Chemical formula 29]

[0334]

[0335] Synthesis of phenolic compound (b1-2) in Synthesis Example 8

[0336] 1.68 g (0.01 mol) of 26DPMC was changed to 2.88 g (0.01 mol) of 3,3'-methylenebis(2-hydroxy-5-methylbenzyl alcohol), and otherwise, the same operations as in Synthesis Example 7 were carried out to obtain a phenolic compound (b1-2) that satisfies condition (b1).

[0337] The obtained compound was subjected to LC-MS analysis using LC-MS2020 (manufactured by Shimadzu Corporation) to confirm that it was the target compound.

[0338] LC-MS (ESI, nega): m / z 503 [M-H] -

[0339] [Chemical formula 30]

[0340]

[0341] Synthesis of phenolic compound (b12-1) in Synthesis Example 9

[0342] Under a dry nitrogen stream, at room temperature, 16.72 g (0.10 mol) of carbazole and 12.99 g (0.16 mol) of 37% aqueous formaldehyde solution were dissolved in 120 g of tetrahydrofuran. 0.5 g of 50% aqueous sodium hydroxide solution was added, and the reaction was carried out at room temperature for 8 hours. Then, the solution was poured into 1 L of water to obtain a yellowish-white precipitate. The precipitate was collected by filtration, washed three times with water, and dried using a vacuum dryer at 40 °C for 24 hours to obtain the N-hydroxymethylated product of carbazole.

[0343] Next, 1.68 g (0.01 mol) of 26DPMC was changed to 3.94 g (0.02 mol) of the obtained N-hydroxymethylated product of carbazole. Otherwise, the same operation as in Synthesis Example 7 was carried out to obtain a phenolic compound (b12-1) that satisfies condition (b1) and condition (b2).

[0344] The obtained compound was subjected to LC-MS analysis using LC-MS2020 (manufactured by Shimadzu Corporation), and it was confirmed that it was the target compound.

[0345] LC-MS (ESI, nega): m / z 304 [M-H] -

[0346] [Chemical formula 31]

[0347]

[0348] Synthesis of phenolic compound (b12-2) in Synthesis Example 10

[0349] 1.68 g (0.01 mol) of 26DPMC was changed to 4.56 g (0.01 mol) of the dimethylol derivative of bisindolylfluorene synthesized with reference to JP-A-2004-145320. Otherwise, the same operation as in Synthesis Example 7 was carried out to obtain a phenolic compound (b12-2) that satisfies condition (b1) and condition (b2).

[0350] The obtained compound was subjected to LC-MS analysis using LC-MS2020 (manufactured by Shimadzu Corporation), and it was confirmed that it was the target compound.

[0351] LC-MS (ESI, nega): m / z 671 [M-H] -

[0352] [Chemical formula 32]

[0353]

[0354] Synthesis of phenolic compound (b13-1) in Synthesis Example 11

[0355] Under a dry nitrogen stream, 27.64 g (0.20 mol) of potassium carbonate was dissolved in 63 g of water, and nitrogen bubbling was carried out for 30 minutes. Then, 8.11 g (0.1 mol) of 1-methylpyrrole and 17.86 g (0.22 mol) of 37% aqueous formaldehyde solution were added, and the reaction was carried out for 7 days at room temperature under a nitrogen atmosphere. Then, the solution was filtered, the obtained solid was dissolved in acetone, dehydrated by adding anhydrous sodium sulfate, concentrated using a rotary evaporator, and dried using a vacuum dryer at 50 °C for 24 hours to obtain the 2,5-dihydroxymethylated product of 1-methylpyrrole.

[0356] Next, 1.68 g (0.01 mol) of 26DPMC was changed to 1.41 g (0.01 mol) of the 2,5-dihydroxymethylated product of 1-methylpyrrole obtained, and otherwise, the operation was the same as in Synthesis Example 7 to obtain a phenolic compound (b13-1) satisfying conditions (b1) and (b3).

[0357] The obtained compound was subjected to LC-MS analysis using LC-MS2020 (manufactured by Shimadzu Corporation) to confirm that it was the target compound.

[0358] LC-MS (ESI, nega): m / z 356 [M-H] -

[0359] [Chemical formula 33]

[0360]

[0361] Synthesis of phenolic compound (b13-2) in Synthesis Example 12

[0362] 1.68 g (0.01 mol) of 26DPMC was changed to 1.28 g (0.01 mol) of 2,5-bis(hydroxymethyl)furan, and otherwise, the operation was the same as in Synthesis Example 7 to obtain a phenolic compound (b13-2) satisfying condition (b1) and having the structure represented by formula (b3).

[0363] The obtained compound was subjected to LC-MS analysis using LC-MS2020 (manufactured by Shimadzu Corporation) to confirm that it was the target compound.

[0364] LC-MS (ESI, nega): m / z 343 [M-H] -

[0365] [Chemical formula 34]

[0366]

[0367] Synthesis of phenolic compound (b12-3) in Synthesis Example 13

[0368] 16.72 g (0.10 mol) of carbazole was converted to 24.83 g (0.10 mol) of 4,4'-diaminodiphenyl sulfone and 38.97 g (0.48 mol) of 37% aqueous formaldehyde solution. Except for this, the same operation as in Synthesis Example 9 was carried out to obtain a tetrahydroxymethylated product of 4,4'-diaminodiphenyl sulfone.

[0369] Next, 1.68 g (0.01 mol) of 26DPMC was converted to 1.84 g (0.005 mol) of the obtained tetrahydroxymethylated product of 4,4'-diaminodiphenyl sulfone. Except for this, the same operation as in Synthesis Example 7 was carried out to obtain a phenolic compound (b12-3) that satisfies condition (b1) and condition (b2).

[0370] The obtained compound was subjected to LC-MS analysis using LC-MS2020 (manufactured by Shimadzu Corporation), and it was confirmed that it was the target compound.

[0371] LC-MS (ESI, nega): m / z 799 [M-H]-

[0372] [Chemical formula 35]

[0373]

[0374] Synthesis of Quinone Diazide Compound (c-2) in Synthesis Example 14

[0375] 21.22 g (0.05 mol) of TrisP-PA was converted to 9.61 g (0.025 mol) of the phenolic compound (b-1) described below. Except for this, the same operation as in Synthesis Example 2 was carried out to obtain a quinone diazide compound (c-2) represented by the following formula.

[0376] [Chemical formula 36]

[0377]

[0378] The names of the compounds used in each of the following Examples and Comparative Examples are shown below. It should be noted that the phenolic compounds b-1 and b-2 were synthesized with reference to the specification of US Patent No. 4,992,596, and the other compounds other than commercially available products were synthesized by known methods.

[0379] GBL: γ-butyrolactone

[0380] EL: Ethyl lactate

[0381] PGME: Propylene glycol monomethyl ether

[0382] [Chemical formula 37]

[0383]

[0384] Example 1

[0385] 10.0 g of polyimide precursor (a-1), 2.0 g of phenolic compound (b1-1), and 2.0 g of photosensitive compound (c-1) were dissolved in a mixed solution of 10 g of GBL, 20 g of EL, and 70 g of PGME. Then, the solution was filtered through a 0.2-μm polytetrafluoroethylene filter to obtain a positive photosensitive resin composition AA. Using the obtained varnish, the light-shielding properties at 450 nm and 500 nm, chemical resistance, and current-voltage characteristics of the organic EL display device were evaluated as described above. In each evaluation, a cured film obtained by curing in a nitrogen atmosphere with an oxygen concentration of about 1% was used.

[0386] Examples 2 to 16, Comparative Examples 1 to 5 and 7

[0387] As described in Tables 1 to 3, the components (a), (b), (c), other components, and solvents were changed. Otherwise, the same operations as in Example 1 were carried out to obtain a varnish of a positive photosensitive resin composition. Using the obtained varnish, the light-shielding properties at 450 nm and 500 nm, chemical resistance, and current-voltage characteristics of the organic EL display device were evaluated as described above. In each evaluation, a cured film obtained by curing in a nitrogen atmosphere with an oxygen concentration of about 1% was used.

[0388] Comparative Example 6

[0389] Using the varnish obtained in Comparative Example 5, the light-shielding properties at 450 nm and 500 nm, chemical resistance, and current-voltage characteristics of the organic EL display device were evaluated as described above. In each evaluation, a cured film obtained by curing in an air atmosphere was used.

[0390] Examples 17 to 22

[0391] Using the positive photosensitive resin compositions AD to AI obtained in Examples 4 to 9, the light-shielding property at 550 nm was evaluated as described above. In each evaluation, a cured film obtained by curing in a nitrogen atmosphere with an oxygen concentration of about 1% was used.

[0392] Example 23

[0393] 10.0 g of a polyimide precursor (a-1), 4.0 g of a phenolic compound (b12-1), 2.0 g of a photosensitive compound (c-1), 1.0 g of a colorant (d1-1-1), 0.8 g of a colorant (d1-2-1), and 2.0 g of a crosslinking agent (e-1) were dissolved in a mixed solution of 10 g of GBL, 20 g of EL, and 70 g of PGME. Then, the solution was filtered through a 0.2-μm polytetrafluoroethylene filter to obtain a varnish of a positive photosensitive resin composition. Using the obtained varnish, evaluations of visible light shielding properties, chemical resistance, and current-voltage characteristics of an organic EL display device were carried out as described above. In each evaluation, a cured film obtained by curing in a nitrogen atmosphere with an oxygen concentration of about 1% was used.

[0394] Examples 24 to 27, Comparative Examples 8 and 9

[0395] As described in Table 5, the components (a), (b), (c), (d), other components, and solvents were changed, and otherwise, the same operations as in Example 23 were carried out to obtain a varnish of a positive photosensitive resin composition. Using the obtained varnish, evaluations of visible light shielding properties, chemical resistance, and current-voltage characteristics of an organic EL display device were carried out as described above. In each evaluation, a cured film obtained by curing in a nitrogen atmosphere with an oxygen concentration of about 1% was used.

[0396] The compositions and evaluation results of each example and comparative example are shown in Tables 1 to 5.

[0397] [Table 1]

[0398]

[0399] [Table 2]

[0400] [Table 2]

[0401]

[0402] [Table 3]

[0403] [Table 3]

[0404]

[0405] [Table 4]

[0406] [Table 4]

[0407]

[0408] [Table 5]

[0409] [Table 5]

[0410]

[0411] Description of the reference numerals

[0412] 1: TFT (Thin Film Transistor)

[0413] 2: Wiring

[0414] 3: TFT insulating layer

[0415] 4: Planarization layer

[0416] 5: ITO (Indium Tin Oxide, transparent electrode)

[0417] 6: Substrate

[0418] 7: Contact hole

[0419] 8: Insulating layer

[0420] 9: Display device

[0421] 10: Light-emitting element

[0422] 11: Cured product

[0423] 12, 12c: Metal wiring

[0424] 13: Counter substrate

[0425] 14: Electrode terminal

[0426] 15: Light-emitting element driving substrate

[0427] 16: Driving element

[0428] 17: Barrier metal

[0429] 18: Solder bump

[0430] 19: Alkali-free glass substrate

[0431] 20: First electrode (transparent electrode)

[0432] 21: Auxiliary electrode

[0433] 22: Insulating layer

[0434] 23: Organic EL layer

[0435] 24: Second electrode (non-transparent electrode)

Claims

1. A photosensitive resin composition comprising an alkali-soluble resin (a), a phenolic compound (b) having a structure represented by formula (1), and a photosensitive compound (c). [Chemical formula 1] In formula (1), n represents an integer of 2 to 4, and * represents a connecting bond.

2. The photosensitive resin composition according to claim 1, wherein The component (b) contains a phenolic compound satisfying the following condition (b1): with respect to any phenolic hydroxyl group in formula (1), the substitution position of at least one of the other phenolic hydroxyl groups is the para position.

3. The photosensitive resin composition according to claim 1, wherein, The component (b) contains a phenolic compound satisfying the following condition (b2): the substituent bonded to the benzyl site in formula (1) is an optionally substituted amino group.

4. The photosensitive resin composition according to claim 1, wherein, The component (b) contains one or more selected from the group consisting of a phenolic compound having a structure represented by formula (b3), a phenolic compound having a structure represented by formula (b4), and a phenolic compound having a structure represented by formula (b5). [Chemical formula 2] In formula (b3), formula (b4) and formula (b5), n and m each independently represent an integer of 2 to 4, p represents an integer of 0 to 2, q represents an integer of 0 to 4, and 2 ≤ p + m ≤ 4 is satisfied. X represents -NR 32 -, -O-, -S-, R 32 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R 33 each independently represents a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R 34 and R 35 each independently represents -OR 36 -, -SR 36 -, -N(R 36 )2, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R 36 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.

5. The photosensitive resin composition according to any one of claims 1 to 4, further comprising a colorant (d).

6. The photosensitive resin composition according to claim 5, wherein, The component (d) includes: a colorant (d-1) having a maximum absorption wavelength at any point in the range of 490 nm or more and less than 580 nm in the range of 300 to 800 nm; and / or a colorant (d-2) having a maximum absorption wavelength at any point in the range of 580 nm or more and less than 800 nm in the range of 300 to 800 nm.

7. The photosensitive resin composition according to claim 6, wherein, The components (d-1) and (d-2) have a xanthene structure.

8. The photosensitive resin composition according to any one of claims 1 to 4, wherein, With respect to 100 parts by mass of the component (a), the content of the component (b) is 1 to 60 parts by mass.

9. The photosensitive resin composition according to any one of claims 1 to 4, wherein The component (a) includes one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole precursor, and their copolymers.

10. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 4.

11. An organic EL display device having a driving circuit, a planarization layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate. The planarization layer and / or the insulating layer has the cured product according to claim 10.

12. The organic EL display device according to claim 11, wherein, The planarization layer and / or the insulating layer has the cured product, and the transmittance of the planarization layer and / or the insulating layer at a wavelength of 450 nm is less than 30%.

13. The organic EL display device according to claim 11, wherein, The planarization layer and / or the insulating layer has the cured product, and the OD value of the planarization layer and / or the insulating layer under visible light per 1 μm film thickness is 0.5 to 1.

5.

14. The organic EL display device according to claim 11, wherein, The organic EL display device further includes a color filter having a black matrix.

15. A display device having at least metal wirings, the cured product according to claim 10, and a plurality of light-emitting elements. The light-emitting elements have a pair of electrode terminals on any one surface, and the pair of electrode terminals are connected to a plurality of the metal wirings extending and existing in the cured product. The plurality of metal wirings are configured to maintain electrical insulation by the cured product.

16. A phenolic compound having a structure represented by formula (b2). [Chemical formula 3] In formula (b2), n represents an integer of 2 to 4, and * represents a connecting bond.

17. The phenolic compound according to claim 16, wherein, The phenolic compound having the structure represented by the formula (b2) satisfies the following condition (b1): with respect to any phenolic hydroxyl group in the formula (b2), the substitution position of at least one of the other phenolic hydroxyl groups is the para position.

18. The phenolic compound according to claim 16 or claim 17, having a molecular weight of 1000 or less.

19. A phenolic compound having the structure represented by the formula (b3), a phenolic compound having the structure represented by the formula (b4), or a phenolic compound having the structure represented by the formula (b5), [Chemical formula 4] In formula (b3), formula (b4) and formula (b5), n and m each independently represent an integer from 2 to 4, p represents an integer from 0 to 2, q represents an integer from 0 to 4, and 2 ≤ p + m ≤ 4 is satisfied, and X represents -NR 32 -, -O-, -S-, R 32 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R 33 each independently represents a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R 34 and R 35 each independently represents -OR 36 -, -SR 36 -, -N(R 36 )2, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R 36 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.

20. A phenolic compound having the structure represented by any of the following chemical formulas, [Chemical formula 5]

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