Photosensitive resin composition, cured product, and display device

Abstract

To provide a photosensitive resin composition that has high sensitivity and enables the formation of a film with low transmittance after curing, irrespective of the heating atmosphere during curing.SOLUTION: Provided is a photosensitive resin composition that includes (A) an alkali-soluble resin, (B) a 4-naphthoquinone diazide sulfonyl ester compound, and (C) a compound represented by formula (1).SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a photosensitive resin composition, a cured product using the same, and a display device. More specifically, the present invention relates to a cured product suitable for surface protection films for semiconductor elements, interlayer insulating films, pixel division layers for organic electroluminescence (EL) elements, planarizing films for thin film transistor (TFT) substrates for driving display devices using organic EL elements, wiring protection insulating films for circuit boards, on-chip microlenses for solid-state imaging elements, planarizing films for various displays and solid-state imaging elements, and solder resists for circuit boards, and a photosensitive resin composition for forming the same. [Background technology]

[0002] Cured products obtained by curing compositions containing polyimide or polybenzoxazole are widely used as insulating films, protective films, and planarizing films for semiconductor elements and display devices. When used in display devices, for example, in applications such as pixel division layers for organic electroluminescence displays and black matrices for liquid crystal displays, it is required to reduce the light transmittance of the cured products in order to improve contrast. In addition, in order to prevent deterioration, malfunction, and leakage current caused by the intrusion of light into the driving TFT of the display device, it is also required to reduce the transmittance of the pixel division layers of organic electroluminescence displays and planarizing films provided on the TFT substrates of organic electroluminescence displays.

[0003] A technique for reducing the transmittance of ultraviolet light in a cured product is a method of adding dihydroxynaphthalene and a thermal crosslinking agent having a specific structure to an alkali-soluble resin made of polyimide and / or a polyimide precursor (see Patent Document 1). A technique for reducing the transmittance of visible light in a cured product and increasing the blackness is a method of adding a colorant such as carbon black, organic or inorganic pigment, or dye to a resin composition, as seen in black matrix materials for liquid crystal display devices and RGB paste materials. For example, there is a method of adding an esterified quinone diazide compound and at least one colorant selected from dyes, inorganic pigments, and organic pigments to an alkali-soluble heat-resistant resin (see Patent Document 2), and a method of adding a photosensitizer and a yellow, red, or blue dye and / or pigment to an alkali-soluble resin made of polyimide and / or a polyimide precursor (see Patent Document 3).

[0004] However, the resin composition prepared by the method described in Patent Document 1 does not have sufficient ultraviolet light blocking properties, and the resin compositions prepared by the methods described in Patent Documents 2 and 3 contain a colorant that has absorption in the exposure wavelength range of 350 nm to 450 nm of a mercury lamp that is generally used as an exposure light source, and therefore have the problem of deteriorating exposure sensitivity.

[0005] In response to this, there is a method of adding a novolac resin, a photosensitizer, and a polymer other than the novolac resin as a technique for reducing the transmittance of ultraviolet light in a cured product (see Patent Document 4), and there is a method of adding, to an alkali-soluble resin, a quinone diazide compound and a thermochromic compound that develops color upon heating and has an absorption maximum in the range of 350 nm to 700 nm, or a compound that has no absorption maximum in the range of 350 nm to less than 500 nm and has an absorption maximum in the range of 500 nm to 750 nm (see Patent Document 5). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2010 / 087238 [Patent Document 2] JP 2004-145320 A [Patent Document 3] JP 2018-63433 A [Patent Document 4] International Publication No. 2015 / 129092 [Patent Document 5] JP 2004-326094 A Summary of the Invention [Problem to be solved by the invention]

[0007] However, the applicant's investigations revealed that the resin compositions described in Patent Documents 4 and 5 reduce their transmittance by utilizing oxidation by oxygen in the air during heat curing, and therefore the transmittance does not decrease in an inert gas atmosphere, which places limitations on the curing conditions. [Means for solving the problem]

[0008] The present invention is as follows. [1] A photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a 4-naphthoquinone diazide sulfonyl ester compound, and (C) a compound represented by formula (1). [ka] In formula (1), R 1 and R 2 R each independently represents a monovalent hydrocarbon group or alkoxy group having 1 to 10 carbon atoms. 3 ~R 8 R each independently represents a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group having 1 to 5 carbon atoms. 9 ~R 12 are each independently a hydrogen atom, a halogen atom, -SO3H, -SO3 - (Z 1 ) + , -SO3NR 13 R 14 , -COOH, -COO - (Z 1 ) + , -COOR 15, -CONR 16 R 17 , -OR 18 , -NR 19 R 20 or a monovalent hydrocarbon group having 1 to 20 carbon atoms. 13 ~R 20 each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. (Z 1 ) + represents an alkali metal cation or a quaternary ammonium cation having a monovalent hydrocarbon group having 1 to 20 carbon atoms. X represents -CO- or -SO2-. [2] The photosensitive resin composition according to [1], wherein the (B) 4-naphthoquinone diazide sulfonyl ester compound contains a structure represented by formula (2). [ka] In formula (2), R 21 ~R 35 R each independently represents a hydrogen atom, a hydroxyl group, a structure represented by formula (3), or a structure represented by formula (4). 36 R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 21 ~R 35 At least one of these contains or is a structure represented by formula (3). [ka] [ka] In formula (4), R 37 ~R 38 R each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 39 ~R 43 each independently represents a hydrogen atom, a hydroxyl group, or a structure represented by formula (3). [3] In equation (2), R 21 , R 26 , and R 31 At least one of the above is a structure represented by formula (4). [4] In formula (1), R1 and R 2 each independently represents a monovalent hydrocarbon group having 1 to 10 carbon atoms. [5] In formula (1), R 1 and R 2 are each independently a structure represented by formula (5). [ka] In formula (5), R 44 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 9 carbon atoms. [6] The photosensitive resin composition according to any one of [1] to [5], further comprising (D) a colorant having a maximum absorption wavelength in the range of more than 500 nm and not more than 700 nm in the region of 350 nm or more and not more than 700 nm (hereinafter referred to as "(D) colorant"). [7] The photosensitive resin composition according to [6], wherein the (D) colorant contains a compound represented by formula (6). [ka] In formula (6), R 45 ~R 48 R each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. 49 ~R 54 R each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. 55 ~R 59 are each independently a hydrogen atom, a halogen atom, -SO3H, -SO3 - , -SO3NR 60 R 61 , -COOH, -COO - , -COOR 62 , -CONR 63 R 64 , -OR 65 , -NR 66 R 67 or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. 60 ~R67 each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent; Z is a counter ion; R 45 ~R 67 Contains -SO3 - -COO - If the total number of elements is a (where a is an integer greater than or equal to 0), then if a=0, then m=-1, n=1; if a=1, then n=0; if a≧2, then m=1, n=a-1. [8] The photosensitive resin composition according to any one of [1] to [7], wherein the (A) alkali-soluble resin contains one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and copolymers thereof. [9] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to [8].

[10] A display device comprising the cured product according to [9]. Effect of the Invention

[0009] The photosensitive resin composition of the present invention has high sensitivity and can form a film having low transmittance after curing, regardless of the heating atmosphere during curing. [Brief description of the drawings]

[0010] [Figure 1] FIG. 2 is a schematic diagram of a substrate of an organic EL display device. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The present invention will be described in detail below. <(A) Alkali-soluble resin> The photosensitive resin composition of the present invention contains (A) an alkali-soluble resin. The alkali-soluble resin is a resin having a dissolution rate of 50 nm / min or more, as defined below. In detail, the alkali-soluble resin is a resin having a dissolution rate of 50 nm / min or more, which is calculated from the reduction in film thickness when a solution of a resin dissolved in γ-butyrolactone is applied onto a silicon wafer and prebaked at 120° C. for 4 minutes to form a prebaked film having a film thickness of 10 μm±0.5 μm, the prebaked film is immersed in a 2.38 mass % tetramethylammonium hydroxide aqueous solution at 23±1° C. for 1 minute, and then rinsed with pure water.

[0012] In order to impart alkali solubility to the (A) alkali-soluble resin, it is preferable that the resin has an acidic group in the structural unit and / or at the end of the main chain thereof. Preferred acidic groups include a carboxyl group, a hydroxyl group, a sulfonic acid group, and a thiol group.

[0013] Specific examples of the (A) alkali-soluble resin include polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, phenol resin, polymer of radical polymerizable monomer having an alkali-soluble group, siloxane polymer, cyclic olefin polymer, and cardo resin. The (A) alkali-soluble resin may contain two or more of these resins. The (A) alkali-soluble resin preferably contains one having high heat resistance. In addition, in order to obtain excellent properties as a planarization film, pixel division layer, partition wall, and protective film used in organic light-emitting devices, display devices, and semiconductor elements, the (A) alkali-soluble resin preferably contains one having a small amount of outgassing at a high temperature of 200°C or higher after heat treatment. Specifically, the (A) alkali-soluble resin preferably contains one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and copolymers thereof.

[0014] Polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor and copolymers thereof will be described. In the case of polyimide, there is no particular limitation as long as it has an imide ring, and in the case of polybenzoxazole, there is no particular limitation as long as it has a benzoxazole ring. In addition, the polyimide precursor is not particularly limited as long as it has a structure that becomes a polyimide having an imide ring by dehydration ring closure, and the polybenzoxazole precursor is also not particularly limited as long as it has a structure that becomes a polybenzoxazole having a benzoxazole ring by dehydration ring closure.

[0015] More preferably used as the (A) alkali-soluble resin are polyimide, polyimide precursors, polybenzoxazole, and polybenzoxazole precursors.

[0016] Polyimide has a structural unit represented by formula (7). [ka] In formula (7), R 68 is a 4-10 valent organic group, R 69 R represents a divalent to decavalent organic group. 70 and R 71 each independently represents a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, or a substituent represented by formula (8) or formula (9), where p represents an integer of 0 to 6, q represents an integer of 0 to 8, and p+q>0. [ka] In formula (8) and formula (9), R 72 ~R 74 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms. The above alkyl groups, acyl groups, and aryl groups may be unsubstituted or substituted.

[0017] The polyimide precursor has a structural unit represented by formula (10). [ka] In formula (10), R 75 is a 4-10 valent organic group, R 76 R represents a divalent to decavalent organic group. 77 represents a substituent represented by the formula (8) or (9), R 78 represents a hydroxyl group, a sulfonic acid group, or a thiol group, and R 79 represents a hydroxyl group, a sulfonic acid group, a thiol group, or a substituent represented by formula (8) or formula (9), in which r represents an integer of 2 to 8, s represents an integer of 0 to 6, and t represents an integer of 0 to 8, and 2≦r+s≦8.

[0018] Polybenzoxazole has a structural unit represented by formula (11). [ka] In formula (11), R 80 is a divalent to decavalent organic group, R 81 R represents a 4-10 valent organic group having an aromatic structure. 82 and R 83 each independently represents a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, or a substituent represented by formula (8) or formula (9), where u represents an integer of 0 to 8, v represents an integer of 0 to 6, and u+v>0.

[0019] The polybenzoxazole precursor has a structural unit represented by formula (12). [ka] In formula (12), R 84 is a divalent to decavalent organic group having an aromatic structure, R 85 R represents a 4-10 valent organic group. 86 represents a sulfonic acid group, a thiol group, or a substituent represented by formula (8) or formula (9), R 87 represents a hydroxyl group, a carboxyl group, a sulfonic acid group, a thiol group, or a substituent represented by formula (8) or formula (9). w represents an integer of 2 to 8, x represents an integer of 0 to 8, and y represents an integer of 0 to 6, and 2≦w+y≦8.

[0020] At least one selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and copolymers thereof preferably has 5 to 100,000 structural units represented by the above formula (7), formula (10), formula (11), or formula (12). At least one selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and copolymers thereof may have other structural units in addition to the structural units represented by the above formula (7), formula (10), formula (11), or formula (12). In this case, at least one selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and copolymers thereof preferably has at least 50 mol %, more preferably at least 70 mol %, of the total number of structural units represented by the above formula (7), formula (10), formula (11), or formula (12).

[0021] R in Equation (7) 68 -(R 70 ) p , and (R 77 ) r -R 75 -(R 78 ) s represents a residue of a tetracarboxylic acid or a residue of a derivative thereof. Examples of the residue of a tetracarboxylic acid derivative include residues of tetracarboxylic acid dianhydride, tetracarboxylic acid dichloride, and tetracarboxylic acid active diester.

[0022] Examples of the residue of a tetracarboxylic acid or a residue of a derivative thereof include pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 2,2',3,3'-benzophenonetetracarboxylic 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, Examples of the tetracarboxylic acid include aromatic tetracarboxylic acids having the structures shown below, such as butane tetracarboxylic acid and 1,2,3,4-cyclopentane tetracarboxylic acid, and residues of their tetracarboxylic acid dianhydrides, tetracarboxylic acid dichlorides, and tetracarboxylic acid active diesters. [ka] In the formula, R 88 represents an oxygen atom, C(CF3)2, or C(CH3)2. 89 and R 90 each independently represents a hydrogen atom or a hydroxyl group.

[0023] R in the above formula (11) 80 -(R 82 ) u , and R in formula (12) 84 -(R 86 ) xrepresents a residue of a dicarboxylic acid or a residue of a derivative thereof. Examples of the residue of a dicarboxylic acid derivative include residues of dicarboxylic acid anhydrides, dicarboxylic acid chlorides, dicarboxylic acid active esters, tricarboxylic acid anhydrides, tricarboxylic acid chlorides, tricarboxylic acid active esters, and diformyl compounds.

[0024] Examples of dicarboxylic acid residues or residues of derivatives thereof include residues of terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, triphenyl dicarboxylic acid, etc., or residues of their dicarboxylic acid anhydrides, dicarboxylic acid chlorides, dicarboxylic acid active esters, etc. Examples of tricarboxylic acid residues or residues of their derivatives include residues of trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, biphenyl tricarboxylic acid, etc., or residues of their tricarboxylic acid anhydrides, tricarboxylic acid chlorides, tricarboxylic acid active esters, etc.

[0025] R in Equation (7) 69 -(R 71 ) q and R in formula (10) 76 -(R 79 ) t represents a residue of a diamine or a residue of a derivative thereof.

[0026] In addition, R in formula (11) 81 -(R 83 ) v and (OH) in formula (12) w -R 85 -(R 87 ) y represents a residue of a bisaminophenol compound or a derivative thereof among diamines. Examples of the diamine and bisaminophenol derivative include a diisocyanate compound or a trimethylsilylated diamine.

[0027] Examples of residues of diamine and bisaminophenol compounds or residues of derivatives thereof include 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'-di(trifluoromethyl)-4,4'-diaminobiphenyl, 9,9-bis(4-aminophenyl)fluorene, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2'-bis(trifluoromethyl)-3,3'-dihydroxybenzidine, 2,2'-bis(trifluoromethyl)-5,5'-dihydroxybenzidine, or compounds in which at least a portion of the hydrogen atoms in these aromatic rings are substituted with an alkyl group, a hydroxyl group, or a halogen atom, or aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, and residues of diamines having the structures shown below. Two or more of these may be used. [ka] In the formula, R 88 represents an oxygen atom, C(CF3)2, or C(CH3)2. 89 ~R 92 each independently represents a hydrogen atom or a hydroxyl group.

[0028] In addition, by capping the ends of these alkali-soluble resins with a monoamine, acid anhydride, acid chloride, or monocarboxylic acid having an acidic group, an alkali-soluble resin having an acidic group at the end of the main chain can be obtained.

[0029] Preferred examples of such monoamines having an acidic group include 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these may be used.

[0030] Preferable examples of such acid anhydrides, acid chlorides, and monocarboxylic acids include acid anhydrides such as phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, and 3-hydroxyphthalic anhydride, monocarboxylic acids such as 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, and 4-carboxythiophenol, and monoacid chloride compounds in which the carboxyl groups of these are converted to acid chlorides, and active ester compounds obtained by reacting the monoacid chloride compounds with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide. Two or more of these may be used.

[0031] The (A) alkali-soluble resin used in the resin composition is synthesized by a known method. In the case of a polyimide precursor, such as a polyamic acid or a polyamic acid ester, the polyimide precursor can be synthesized by, for example, reacting a tetracarboxylic dianhydride with a diamine compound at low temperature, obtaining a diester from a tetracarboxylic dianhydride with an alcohol and then reacting it with an amine in the presence of a condensing agent, obtaining a diester from a tetracarboxylic dianhydride with an alcohol, then converting the remaining dicarboxylic acid into an acid chloride and reacting it with an amine, or the like.

[0032] In the case of polyimide, for example, it can be obtained by dehydrating and ring-closing the polyamic acid or polyamic acid ester obtained by the above-mentioned method through heating or chemical treatment with an acid or base.

[0033] In the case of a polybenzoxazole precursor, such as polyhydroxyamide, it can be produced by a condensation reaction between a bisaminophenol compound and a dicarboxylic acid. Specifically, there is a method of reacting a dehydration condensation agent such as dicyclohexylcarbodiimide (DCC) with an acid and adding a bisaminophenol compound thereto, or a method of dropping a solution of a dicarboxylic acid dichloride into a solution of a bisaminophenol compound to which a tertiary amine such as pyridine has been added.

[0034] Polybenzoxazole can be obtained, for example, by subjecting polyhydroxyamide obtained by the above-mentioned method to dehydration and ring closure by heating or chemical treatment with an acid or base.

[0035] <(B) 4-Naphthoquinone diazide sulfonyl ester compound> The photosensitive resin composition of the present invention contains (B) a 4-naphthoquinone diazide sulfonyl ester compound. By containing (B) a 4-naphthoquinone diazide sulfonyl ester compound, the resin composition becomes a photosensitive resin composition, which enables pattern processing by photolithography. In addition, by containing (B) a 4-naphthoquinone diazide sulfonyl ester compound, the compound represented by (C) formula (1) described below can be made to develop color upon thermal curing. The mechanism of color development is unclear, but it is thought to be due to the generation of a strongly acidic compound upon heating for thermal curing.

[0036] Examples of the 4-naphthoquinone diazide sulfonyl ester compound include a polyhydroxy compound to which the sulfonic acid of 4-naphthoquinone diazide is ester-bonded, a polyamino compound to which the sulfonic acid of 4-naphthoquinone diazide is sulfonamide-bonded, a polyhydroxypolyamino compound to which the sulfonic acid of 4-naphthoquinone diazide is ester-bonded and / or sulfonamide-bonded, etc. In the 4-naphthoquinone diazide sulfonyl ester compound, it is preferable that 50 mol % or more of the hydroxyl groups and amino groups of the polyhydroxy compound or polyamino compound are bonded to the sulfonic acid of 4-naphthoquinone diazide relative to the total of 100 mol %. By using a 4-naphthoquinone diazide compound substituted by 50 mol % or more, the affinity of the 4-naphthoquinone diazide sulfonyl ester compound to an alkaline aqueous solution is reduced, and the solubility of the resin composition in an alkaline aqueous solution of the unexposed part is greatly reduced. At the same time, the quinone diazide sulfonyl group is converted to an indene carboxylic acid by exposure, and a high dissolution rate of the resin composition in an alkaline aqueous solution of the exposed part can be obtained. As a result, the dissolution rate ratio of the exposed part and the unexposed part of the composition can be increased, and a pattern can be obtained with high resolution. By using such a 4-naphthoquinone diazide sulfonyl ester compound, a positive photosensitive resin composition that is sensitive to the i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a general mercury lamp can be obtained. Two or more 4-naphthoquinone diazide sulfonyl ester compounds may be used in combination.

[0037] From the viewpoint of sensitivity, the (B) 4-naphthoquinone diazide sulfonyl ester compound preferably contains a structure represented by formula (2), and further, in formula (2), R 21 , R 26 , R 31 It is more preferable that at least one of the above has a structure represented by formula (4). [ka] In formula (2), R 21 ~R 35R each independently represents a hydrogen atom, a hydroxyl group, a structure represented by formula (3), or a structure represented by formula (4). 36 R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 21 ~R 35 At least one of these contains or is a structure represented by formula (3). [ka] [ka] In formula (4), R 37 ~R 38 R each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 39 ~R 43 each independently represents a hydrogen atom, a hydroxyl group, or a structure represented by formula (3).

[0038] The molecular weight of the (B) 4-naphthoquinone diazide sulfonyl ester compound is preferably 300 or more, more preferably 350 or more, from the viewpoints of heat resistance, mechanical properties, and adhesion of the cured product obtained by heat treatment, and is preferably 3,000 or less, more preferably 1,500 or less.

[0039] The content of the (B) 4-naphthoquinone diazide sulfonyl ester compound is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and preferably 100 parts by mass or less, more preferably 80 parts by mass or less, based on 100 parts by mass of the (A) alkali-soluble resin. When the content is 1 to 100 parts by mass, photosensitivity can be imparted while maintaining the heat resistance, chemical resistance, and mechanical properties of the cured product after heat treatment.

[0040] <Other quinone diazide compounds> The photosensitive resin composition of the present invention may contain a photosensitive compound other than the 4-naphthoquinone diazide sulfonyl ester compound. Examples of such photosensitive compounds include 5-naphthoquinone diazide sulfonyl ester compounds. Compared with the 4-naphthoquinone diazide sulfonyl ester compound, the 5-naphthoquinone diazide sulfonyl ester compound has an absorption extended to the g-line region of a mercury lamp, and is suitable for g-line exposure and full-wavelength exposure.

[0041] <(C) Compound represented by formula (1)> The photosensitive resin composition of the present invention contains a compound represented by formula (1) (C). The compound represented by formula (1) (C) is a compound that has no maximum absorption wavelength in the region of 350 nm to 700 nm before heating, and when heated at 120° C. or higher, develops a maximum absorption wavelength somewhere in the region of 350 nm to 700 nm (sometimes called "thermal coloring"). The mechanism of coloring is unclear, but it is believed that the ester bond of the compound represented by formula (1) (C) is decomposed by a strong acidic compound generated from the 4-naphthoquinone diazide sulfonyl ester compound (B) by heat, and a quinoid structure is formed, thereby generating a color-developing body having a maximum absorption wavelength somewhere in the region of 350 nm to 700 nm. Since the decomposition reaction of the ester does not depend on the heating atmosphere during curing, coloring can be achieved without being restricted by the curing conditions. Furthermore, before heating, the compound represented by formula (1) (C) has no absorption in the range of 350 nm to 700 nm, and therefore does not block the exposure wavelength range (range of 350 nm to 450 nm) of a mercury lamp that is generally used as an exposure light source before curing, allowing pattern formation with high sensitivity. The compound represented by formula (1) (C) is preferably a compound that, when heated at 120° C. or higher, produces a maximum absorption wavelength in either the range of 350 nm to 500 nm in the range of 350 nm to 700 nm.

[0042] Examples of the compound represented by formula (1) include fluorescein diacetate, fluorescein dipropionate, fluorescein dibutyrate, fluorescein dipivalate, fluorescein dibenzoate, and fluorescein bis(t-butoxycarbonate).

[0043] Among these, from the viewpoint of the reliability of the display device, R 1 and R 2 is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms. 1 and R 2 It is more preferable that the structure is represented by formula (5). [ka] In formula (5), R 44 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 9 carbon atoms.

[0044] The content of the compound (C) represented by formula (1) used in the present invention is preferably 5 to 80 parts by mass, particularly preferably 10 to 60 parts by mass, relative to 100 parts by mass of the alkali-soluble resin (A). If the content of the compound (C) represented by formula (1) is 5 parts by mass or more, the transmittance of the cured product in the ultraviolet-visible light region can be reduced. If the content is 80 parts by mass or less, the heat resistance and strength of the cured product can be maintained, and the water absorption rate can be reduced.

[0045] <(D) A colorant having a maximum absorption wavelength in the range of more than 500 nm and not more than 700 nm in the region of 350 nm or more and not more than 700 nm> The photosensitive resin composition of the present invention preferably further contains (D) a colorant having a maximum absorption wavelength in the range of more than 500 nm to 700 nm in the region of 350 nm or more and 700 nm or less (hereinafter referred to as "(D) colorant"). By containing the (D) colorant, the transmittance can be reduced over a wide range of visible light, and the light-shielding properties can be improved. Examples of the (D) colorant include dyes, organic pigments, and inorganic pigments, and any of them can be used according to the purpose.

[0046] The (D) colorant preferably contains a compound represented by formula (6) from the viewpoint of compatibility with the compound represented by formula (1) and reliability of the display device. Examples of the compound represented by formula (6) include known xanthene acid dyes, compounds consisting of an ion pair of an anion portion of a xanthene acid dye and an ammonium cation, known xanthene basic dyes, and xanthene compounds described in International Publication No. 2023 / 013549. [ka] In formula (6), R 45 ~R 48 R each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. 49 ~R 54 R each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. 55 ~R 59 are each independently a hydrogen atom, a halogen atom, -SO3H, -SO3 - , -SO3NR 60 R 61 , -COOH, -COO - , -COOR 62 , -CONR 63 R 64 , -OR 65 , -NR 66 R 67 or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. 60 ~R 67 each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent; Z is a counter ion; R 45 ~R 67 Contains -SO3 - -COO - When the total number of is a (a is an integer greater than or equal to 0), if a=0, then m=-1, n=1; if a=1, then n=0; if a≧2, then m=1, n=a-1.

[0047] Here, examples of the substituent that may be possessed by the monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent or the monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent include a halogen atom, a hydroxyl group, an alkoxy group, a phenoxy group, a carboxyl group, a sulfo group, an acyl group, an amino group, an imino group, an amido group, an imido group, a nitro group, a cyano group, -SO3 - , -COO - Examples of known substituents include the following.

[0048] The photosensitive resin composition of the present invention may contain various known additives such as a thermal crosslinking agent, a compound having a phenolic hydroxyl group, an adhesion improver, and a surfactant as compounds other than (A) the alkali-soluble resin, (B) the 4-naphthoquinone diazide sulfonyl ester compound, (B) the other quinone diazide compound, (C) the compound represented by formula (1), and (D) the colorant.

[0049] <Solvent> The photosensitive resin composition of the present invention may contain a solvent. Examples of the solvent include polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone, N,N'-dimethylpropyleneurea, N,N-dimethylisobutyric acid amide, and methoxy-N,N-dimethylpropionamide, ethers such as tetrahydrofuran, dioxane, propylene glycol monomethyl ether, and propylene glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone, and diisobutyl ketone, esters such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate, and 3-methyl-3-methoxybutyl acetate, alcohols such as ethyl lactate, methyl lactate, diacetone alcohol, and 3-methyl-3-methoxybutanol, and aromatic hydrocarbons such as toluene and xylene. Two or more of these may be contained. The content of the solvent is preferably 100 parts by mass or more per 100 parts by mass of the (A) alkali-soluble resin in order to dissolve the composition.

[0050] The photosensitive resin composition of the present invention can be used for forming insulating films, protective films, planarizing films, etc. of semiconductor elements and display devices. In particular, since the photosensitive resin composition has excellent heat resistance and low outgassing properties for planarizing layers and pixel dividing layers, it is preferably used for forming planarizing layers and pixel dividing layers of organic EL display devices, and since the photosensitive resin composition can improve the contrast of organic EL display devices, it is particularly preferably used for forming pixel dividing layers of organic EL display devices.

[0051] <Method for producing photosensitive resin composition> Next, a method for producing the photosensitive resin composition of the present invention will be described. A resin composition can be obtained by mixing various known additives such as (A) an alkali-soluble resin, (B) a 4-naphthoquinone diazide sulfonyl ester compound, (C) a compound represented by formula (1), other quinone diazide compounds as necessary, (D) a colorant, a thermal crosslinking agent, a compound having a phenolic hydroxyl group, an adhesion improver, and a surfactant, which are components constituting the photosensitive resin composition of the present invention. The components of the resin composition to be used in the method for producing the photosensitive resin composition of the present invention preferably contain a solvent to dissolve each of the components. In such a case, methods for promoting dissolution include heating and stirring. When heating, the heating temperature is preferably set within a range that does not impair the performance of the resin composition, and is usually room temperature to 80°C. In this specification, room temperature is 25°C. In addition, the order in which each component is dissolved is not particularly limited, and examples thereof include a method in which a compound having low solubility in a solvent is dissolved in order. When stirring, the rotation speed is preferably set within a range that does not impair the performance of the resin composition, and is usually 200 rpm to 2000 rpm. When stirring, heating may be performed as necessary, and the temperature is usually from room temperature to 80° C. A surfactant or some adhesion improver may be added, and for components that tend to generate bubbles when dissolved by stirring, adding them last after dissolving the other components can prevent insufficient dissolution of the other components due to the generation of bubbles.

[0052] The obtained photosensitive resin composition is preferably filtered using a filter to remove dust and particles. The filter pore size is, for example, 0.5 μm, 0.2 μm, 0.1 μm, 0.05 μm, 0.02 μm, etc., but is not limited thereto. The material of the filter includes polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), etc., and polyethylene and nylon are preferable. In addition, when the resin composition contains an organic pigment, it is preferable to use a filter having a pore size larger than the particle size of the pigment.

[0053] <Cured product obtained by curing the photosensitive resin composition> The present invention also relates to a cured product obtained by curing the photosensitive resin composition. The cured product of the photosensitive resin composition is a cured product obtained by applying the above-mentioned resin composition to a substrate or the like and curing it by heat treatment. The heat treatment conditions are preferably 200° C. or higher, more preferably 250° C. or higher. The heat treatment conditions are preferably 400° C. or lower, more preferably 350° C. or lower.

[0054] <Method for producing a cured product using a photosensitive resin composition> A method for producing a cured product using the photosensitive resin composition of the present invention will now be described. The method for producing a cured product includes, in this order, the steps of: (1) applying the above-mentioned resin composition to a substrate to form a coating film; (2) exposing the coating film to active actinic rays to obtain an exposed coating film; (3) developing the exposed coating film with an alkaline solution to obtain a developed coating film; and (4) heating the developed coating film to obtain a cured product.

[0055] (1) In the step of forming a coating film of the resin composition, the photosensitive resin composition of the present invention is applied by a spin coating method, a slit coating method, a dip coating method, a spray coating method, a printing method, or the like to obtain a coating film of the resin composition. Prior to the application, the substrate to which the resin composition is applied may be pretreated with the adhesion improver described above. For example, a method of treating the substrate surface using a solution in which the adhesion improver is dissolved at 0.5 to 20 mass % in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, or diethyl adipate can be mentioned. Methods of treating the substrate surface include spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment. In the step of drying the coating film, the formed coating film is subjected to a reduced pressure drying treatment as necessary, and then heat treatment is performed at a range of 50°C to 180°C for 1 minute to several hours using a hot plate, an oven, infrared rays, or the like to obtain a coating film.

[0056] Next, the step (2) of exposing the coating film to light will be described. The coating film is irradiated with active actinic rays (hereinafter sometimes referred to as exposure). At this time, the exposure may be made through a photomask having a desired pattern, if necessary, or the coating film may be directly exposed with a laser or the like. The active actinic rays used for exposure include ultraviolet rays, visible light, electron beams, X-rays, etc., and in the present invention, it is preferable to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) from a mercury lamp.

[0057] Next, the step (3) of developing the exposed coating film with an alkaline solution to obtain a developed coating film will be described. The exposed coating film is developed using an alkaline solution to remove the exposed portion of the coating film. The developer is preferably an aqueous solution of an alkaline 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, or hexamethylenediamine. In some cases, polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, or dimethylacrylamide, alcohols such as methanol, ethanol, or isopropanol, esters such as ethyl lactate or propylene glycol monomethyl ether acetate, or ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, or methyl isobutyl ketone may be added to the aqueous alkaline solution. The development method may be spray, paddle, immersion, ultrasonic, or the like.

[0058] Next, the coating film (pattern) formed by development is preferably rinsed with distilled water. Here, too, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to the distilled water for rinsing.

[0059] Next, the step (4) of heat-treating the developed coating film (pattern) to obtain a cured product will be described. By subjecting the developed coating film to a heat treatment, residual solvents and components with low heat resistance can be removed, and the heat resistance and chemical resistance of the cured product can be improved. This heat treatment is carried out by selecting a certain temperature and gradually increasing the temperature, or by selecting a certain temperature range and continuously increasing the temperature for 5 minutes to 5 hours. For example, a method of heat treatment at 230°C for 60 minutes can be mentioned. The heat treatment conditions in the present invention are preferably 200°C or higher, more preferably 230°C or higher. The heat treatment conditions are preferably 400°C or lower, more preferably 350°C or lower.

[0060] <Display device> The display device of the present invention comprises a cured product obtained by curing the above-mentioned photosensitive resin composition. The cured product obtained by curing the resin composition is included in the planarization layer or pixel division layer of a display device having a substrate on which a TFT is formed, a planarization layer on a driving circuit, a pixel division layer and a display element on a first electrode, and a second electrode in this order. Examples of display devices having such a configuration include liquid crystal display devices and organic EL display devices. Among them, the cured product is particularly suitable for use in organic EL display devices, which require high heat resistance and low outgassing properties for the planarization layer or pixel division layer, and is particularly suitable for use in the pixel division layer because it can improve the contrast of the organic EL display device.

[0061] The cured product obtained by curing the photosensitive resin composition of the present invention may be used for either the planarization layer or the pixel division layer, or may be used for both. An active matrix display device has a TFT and wiring located on the side of the TFT and connected to the TFT on a substrate such as glass, a planarization layer is provided thereon so as to cover the unevenness, and a display element is further provided on the planarization layer. The display element and the wiring are connected via a contact hole formed in the planarization layer. EXAMPLES

[0062] The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0063] (1) Evaluation of transmittance A photosensitive resin composition was spin-coated onto a 5 cm square glass substrate so that the film thickness after heat treatment (curing) would be 1.5 μm, and the substrate was pre-baked at 120° C. for 120 seconds to produce a pre-baked film. The film thickness and the transmittance spectrum in the region of 300 nm to 800 nm of this pre-baked film were measured using a stylus profiler and an ultraviolet-visible spectrophotometer, respectively, and converted into the light transmittance when the pre-baked film had a film thickness of 1.5 μm.

[0064] Then, the film was cured at 250°C for 60 minutes under nitrogen or air using a high-temperature clean oven INH-9CD-S manufactured by Koyo Thermo Systems Co., Ltd. to produce a heat-resistant colored resin film (cured product). The film thickness and transmittance spectrum in the region of 300 nm to 800 nm were measured for this heat-resistant colored resin film (cured product) in the same manner as for the prebaked film, and converted into light transmittance when the film thickness of the cured film was 1.5 μm. The transmittance after curing was judged as follows, with C or higher (transmittance of 70% or less) being considered a pass. A: Transmittance is 50% or less B: Transmittance is more than 50% and less than 60% C: Transmittance is more than 60% and less than 70% D: Transmittance is over 70%

[0065] (2) Sensitivity assessment The resin compositions (hereinafter sometimes referred to as varnish) prepared in the examples and comparative examples were applied by spin coating onto an 8-inch silicon wafer so that the film thickness after heat treatment (curing) would be 3.0 μm, and the wafer was prebaked at 120°C for 2 minutes to produce a prebaked film. The resulting prebaked film was exposed to light at a dose of 10 to 250 mJ / cm through a mask having a 20 μm line and space pattern. 2 in the range of 5 mJ / cm 2 After exposure, the film was developed with a 2.38% by mass tetramethylammonium hydroxide aqueous solution for 60 seconds, then rinsed with pure water and spun dry to obtain a pattern. A coater / developer (ACT-8 manufactured by Tokyo Electron Limited) was used for coating, pre-baking, and development, and an i-line stepper (NSR-2005i9C manufactured by Nikon Corporation) was used for exposure.

[0066] The developed film pattern obtained by the above method was observed at a magnification of 100 times using an FPD microscope MX61 (Olympus Corporation). The exposure dose required to form a 20 μm line-and-space pattern with a 1:1 width (this is called the optimum exposure dose) was determined, and this was taken as the sensitivity. The sensitivity was evaluated as follows, and the optimum exposure dose was rated as C or higher (sensitivity of 50 mJ / cm 2 (see below) were deemed to have passed. A: Sensitivity is 30mJ / cm 2 below B: Sensitivity is 30mJ / cm 2 Super 40mJ / cm 2 below C: Sensitivity is 40mJ / cm 2 Super 50mJ / cm 2 below D: Sensitivity is 50mJ / cm 2 Super

[0067] (3) Evaluation of reliability The reliability was evaluated based on the light-emitting area ratio of an organic EL display device having, as a pixel dividing layer, the cured product made of the photosensitive resin composition prepared in each of the Examples and Comparative Examples. 1(a) to (d) show schematic diagrams of the substrates used. First, a 10 nm ITO transparent conductive film was formed on the entire surface of a 38×46 mm alkali-free glass substrate 1 by sputtering, and etched to form a first electrode 2. At the same time, an auxiliary electrode 3 was also formed to extract a second electrode (FIG. 1(a)). The obtained substrate was ultrasonically cleaned with "Semicoclean" (registered trademark) 56 (trade name, manufactured by Furuuchi Chemical Co., Ltd.) for 10 minutes, and then washed with ultrapure water. Next, the photosensitive resin composition prepared in each Example and Comparative Example was applied to the entire surface of the substrate by spin coating, and prebaked on a hot plate at 100° C. for 2 minutes. After exposing the film to UV light through a photomask, it was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution, and then rinsed with pure water to obtain a pattern. The obtained pattern was cured in an oven at 230° C. for 60 minutes under a nitrogen atmosphere. In this way, a pixel division layer 4 was formed in the effective area of ​​the substrate, with openings 70 μm wide and 260 μm long arranged at a pitch of 155 μm in the width direction and a pitch of 465 μm in the length direction, with each opening exposing the first electrode 2 (Figure 1(b)). These openings will ultimately become the light-emitting pixels. The effective area of ​​the substrate was 16 mm square, and the thickness of the pixel division layer was approximately 1.0 μm.

[0068] Next, an organic EL display device was fabricated using the substrate on which the first electrode 2, auxiliary electrode 3, and pixel division layer 4 were formed. After performing nitrogen plasma treatment as a pretreatment, an organic EL layer 5 including a light-emitting layer was formed by vacuum deposition (Figure 1(c)). Note that the degree of vacuum during deposition was 1×10 -3 The pressure was below 10 Pa, and the substrate was rotated relative to the deposition source during deposition. First, compound (HT-1) was deposited to a thickness of 10 nm as a hole injection layer, and compound (HT-2) was deposited to a thickness of 50 nm as a hole transport layer. Next, compound (GH-1) as a host material and compound (GD-1) as a dopant material were deposited to a thickness of 40 nm in the light-emitting layer so that the doping concentration was 10%. Next, compounds (ET-1) and (LiQ) were laminated to a thickness of 40 nm in a volume ratio of 1:1 as electron transport materials. The structures of the compounds used in the organic EL layer 5 are shown below. [ka]

[0069] Next, after depositing 2 nm of a compound (LiQ), 10 nm of MgAg was co-deposited with a volume ratio of Mg to Ag of 10:1 to form the second electrode 6 (Fig. 1(d)). Finally, a cap-shaped glass plate was attached using an epoxy resin adhesive in a low-humidity nitrogen atmosphere to seal the substrate, and four light-emitting devices measuring 5 mm square were fabricated on one substrate. The film thickness referred to here is the value displayed on a quartz crystal oscillator film thickness monitor.

[0070] The organic EL display device was tested at 10 mA / cm 2 The light-emitting area of ​​the light-emitting pixel (light-emitting area before UV light irradiation) was measured. Next, the device was placed on a hot plate heated to 80°C with the light-emitting surface facing up, and irradiated with a wavelength of 365 nm and an illuminance of 0.6 mW / cm. 2 After 1000 hours, the UV light was irradiated at 10 mA / cm 2 The light was emitted by direct current drive at 400 Hz, and the light-emitting area of ​​the light-emitting pixel (light-emitting area after UV light irradiation) was measured. From these measurements, the light-emitting area ratio was calculated using the following formula, and the reliability was judged from this value as follows, with C or higher (light-emitting area ratio of 80% or more) being considered a pass. Emitting area ratio [%] = (Emitting area after UV light irradiation) / (Emitting area before UV light irradiation) × 100 S: Light-emitting area ratio is 95% or more and 100% or less A: Light-emitting area ratio is 90% or more and less than 95% B: Light-emitting area ratio is 85% or more and less than 90% C: Light-emitting area ratio is 80% or more and less than 85% D: The light-emitting area ratio is less than 80%.

[0071] [Synthesis Example 1] In a three-neck flask, 18.31g (0.05mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as BAHF), 17.4g (0.3mol) of propylene oxide, and 100mL of acetone were weighed and dissolved. A solution of 20.41g (0.11mol) of 3-nitrobenzoyl chloride dissolved in 10mL of acetone was added dropwise to the flask. After the addition, the mixture was reacted at -15℃ for 4 hours, and then returned to room temperature. The precipitated white solid was collected by filtration and vacuum dried at 50℃. 30g of the obtained solid was placed in a 300mL stainless steel autoclave and dispersed in 250mL of 2-methoxyethanol, and 2g of 5% palladium-carbon was added. Hydrogen was introduced into the flask using a balloon, and the mixture was reacted at room temperature for 2 hours. After 2 hours, it was confirmed that the balloon did not deflate any more. After the reaction was completed, the catalyst palladium compound was removed by filtration, and the mixture was concentrated by distillation under reduced pressure to obtain a hydroxyl group-containing diamine compound (HA) having the following structure. [ka]

[0072] Under a dry nitrogen stream, 15.1g (0.025mol) of HA, 3.66g (0.01mol) of BAHF, and 0.62g (0.0025mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (hereinafter, SiDA) were dissolved in 200g of N-methylpyrrolidone (hereinafter, NMP). 22.2g (0.05mol) of 2,2-(3,4-dicarboxyphenyl)hexafluoropropane (hereinafter, 6FDA) was added together with 50g of NMP, and the mixture was stirred at 40°C for 1 hour. Then, 2.73g (0.025mol) of 3-aminophenol (hereinafter, MAP) was added, and the mixture was stirred at 40°C for 1 hour. Furthermore, a solution of 11.9g (0.1mol) of N,N-dimethylformamide dimethylacetal (hereinafter, DFA) diluted with 5g of NMP was added, and the mixture was stirred at 40°C for 2 hours. After stirring, the solution was poured into 2 L of water, and the polymer solid precipitate was collected by filtration. The polymer solid was washed three times with 2 L of water, and then dried in a vacuum dryer at 50°C for 72 hours to obtain polyimide precursor resin a-1 as an alkali-soluble resin (A).

[0073] [Synthesis Example 2] Under a dry nitrogen stream, 21.2 g (0.05 mol) of 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol (TrisP-PA) and 26.8 g (0.1 mol) of 4-naphthoquinone diazide sulfonic acid chloride were dissolved in 450 g of 1,4-dioxane and brought to room temperature. 12.7 g of triethylamine mixed with 50 g of 1,4-dioxane was added so that the temperature in the system did not exceed 35°C, and the mixture was stirred at 40°C for 2 hours. The triethylamine salt was filtered, and the filtrate was added to water. The precipitate was then collected by filtration and washed with 1 L of 1% hydrochloric acid. It was then washed twice with 2 L of water. The precipitate was dried in a vacuum dryer to obtain (B) 4-naphthoquinone diazide sulfonyl ester compound b-1.

[0074] [Synthesis Examples 3 to 5] In Synthesis Example 2, 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol (TrisP-PA) 21.2 g (0.05 mol) and 4-naphthoquinone diazide sulfonic acid chloride 26.8 g (0.1 mol) were replaced with compounds shown in Table 1, and the same procedure was repeated to obtain (B) 4-naphthoquinone diazide sulfonyl ester compounds b-2 to b-4.

[0075] [Table 1]

[0076] [Synthesis Example 6] A 5-naphthoquinone diazide sulfonyl ester compound z-1 was obtained in the same manner as in Synthesis Example 2, except that 26.8 g (0.1 mol) of 5-naphthoquinone diazide sulfonyl chloride was used instead of 26.8 g (0.1 mol) of 4-naphthoquinone diazide sulfonyl chloride.

[0077] [Synthesis Example 7] Under a dry nitrogen stream, 3.32 g (0.01 mol) of fluorescein, 2.45 g (0.024 mol) of acetic anhydride, and 2.93 g (0.024 mol) of N,N-dimethylaminopyridine (DMAP) were dissolved in 50 g of N-methylpyrrolidone and stirred at room temperature for 2 hours. The reaction solution was then poured into water, and the precipitate was collected by filtration and dried to obtain compound c-1 represented by formula (1) (C) shown in the structure column of Table 2.

[0078] [Synthesis Examples 8-10] Compounds c-2 to c-4 represented by formula (1) (C) shown in the structure column of Table 2 were obtained in the same manner as in Synthesis Example 7, except that the compound shown in Table 2 was used instead of 2.45 g (0.024 mol) of acetic anhydride.

[0079] [Table 2]

[0080] The compounds shown in each of the Examples and Comparative Examples are shown below. [ka]

[0081] [Example 1] Under yellow light, (A) the polyimide precursor resin a-1 obtained in Synthesis Example 1 as an alkali-soluble resin, (B) compound b-4 obtained in Synthesis Example 5 as a 4-naphthoquinone diazide sulfonyl ester compound, and (C) compound c-4 obtained in Synthesis Example 10 as a compound represented by formula (1) in the amounts shown in Table 3, as well as 5.0 g of γ-butyrolactone (GBL) and 5.0 g of ethyl lactate (EL) as solvents, were added and dissolved by stirring to prepare composition 1. Composition 1 was evaluated for sensitivity, transmittance, and reliability.

[0082] [Examples 2 to 10, Comparative Examples 1 to 3] Compositions 2 to 13 were prepared according to the compositions shown in Table 3 in the same manner as in Example 1. Compositions 2 to 13 were evaluated in the same manner as in Example 1. Note that, for compositions 11 to 13, the sensitivity or post-cure transmittance was unacceptable, so that reliability was not evaluated. Table 3 shows the components and evaluation results of the resin compositions of the respective Examples and Comparative Examples.

[0083] [Table 3] From the above results, it was confirmed that the photosensitive resin composition of the present invention has high sensitivity and can form a film having low transmittance after curing, regardless of the heating atmosphere during curing. [Explanation of symbols]

[0084] 1: Glass substrate 2:First electrode 3: Auxiliary electrode 4: Pixel division layer 5: Organic EL layer 6:Second electrode

Claims

1. A photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a 4-naphthoquinone diazide sulfonyl ester compound, and (C) a compound represented by formula (1). 【Chemistry 1】 (In formula (1), R １ and R ２ R each independently represents a monovalent hydrocarbon group or alkoxy group having 1 to 10 carbon atoms. ３ ~R ８ R each independently represents a hydrogen atom, a halogen atom, or a monovalent hydrocarbon group having 1 to 5 carbon atoms. ９ ~R １２ each independently represents a hydrogen atom, a halogen atom, or -SO ３ H, -SO ３ － (Z １ ) ＋ , -SO ３ N.R. １３ R １４ , -COOH, -COO － (Z １ ) ＋ , -COOR １５ , -CONR １６ R １７ , -OR １８ , -NR １９ R ２０ or a monovalent hydrocarbon group having 1 to 20 carbon atoms. １３ ~R ２０ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. １ ) ＋ represents an alkali metal cation or a quaternary ammonium cation having a monovalent hydrocarbon group having 1 to 20 carbon atoms. X represents -CO- or SO ２ - represents.)

2. The photosensitive resin composition according to claim 1, wherein the 4-naphthoquinone diazide sulfonyl ester compound (B) contains a structure represented by formula (2). 【Chemistry 2】 (In formula (2), R ２１ ~R ３５ R each independently represents a hydrogen atom, a hydroxyl group, a structure represented by formula (3), or a structure represented by formula (4). ３６ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ２１ ~R ３５ At least one of the above formulas contains or is a structure represented by formula (3). 【Chemistry 3】 【Chemistry 4】 (In formula (4), R ３７ ~R ３８ R each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. ３９ ~R ４３ each independently represents a hydrogen atom, a hydroxyl group, or a structure represented by formula (3).

3. In formula (2), R ２１ , R ２６ , and R ３１ The photosensitive resin composition according to claim 2 , wherein at least one of the above is a structure represented by formula (4).

4. In formula (1), R １ and R ２ The photosensitive resin composition according to any one of claims 1 to 3, wherein each of the is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms.

5. In formula (1), R １ and R ２ The photosensitive resin composition according to any one of claims 1 to 3, wherein each independently represents a structure represented by formula (5): 【Chemistry 5】 (In formula (5), R ４４ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 9 carbon atoms.

6. The photosensitive resin composition according to any one of claims 1 to 3, further comprising (D) a colorant having a maximum absorption wavelength in the range of more than 500 nm and not more than 700 nm in the region of 350 nm or more and not more than 700 nm (hereinafter referred to as "colorant (D)").

7. The photosensitive resin composition according to claim 6 , wherein the colorant (D) contains a compound represented by formula (6): 【Chemistry 6】 (In formula (6), R ４５ ~R ４８ R each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms which may have a substituent. ４９ ~R ５４ R each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. ５５ ~R ５９ each independently represents a hydrogen atom, a halogen atom, or -SO ３ H, -SO ３ － , -SO ３ N.R. ６０ R ６１ , -COOH, -COO － , -COOR ６２ , -CONR ６３ R ６４ , -OR ６５ , -NR ６６ R ６７ or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. ６０ ~R ６７ each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent; Z is a counter ion; R ４５ ~R ６７ -SO ３ － and-COO － If the total number of is a (a is an integer equal to or greater than 0), then if a=0, then m=-1, n=1; if a=1, then n=0; if a≧2, then m=1, n=a-1.)

8. The photosensitive resin composition according to any one of claims 1 to 3, wherein the alkali-soluble resin (A) contains one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, and copolymers thereof.

9. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 3.

10. A display device comprising the cured product according to claim 9.

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