Negative-type photosensitive resin composition, cured film, organic EL display, and method for producing the cured film

Abstract

The purpose of the present invention is to provide a negative photosensitive resin composition which has high sensitivity and excellent half-tone characteristics, while being capable of forming a pattern having a low tapered shape after development, and which is able to be suppressed in residue adhesion to an opening part of the pattern after thermal curing. A negative photosensitive resin composition which contains (A) an alkali-soluble resin and two or more kinds of (C1-1) oxime ester-based photopolymerization initiators serving as (C1) a photopolymerization initiator; the oxime ester-based photopolymerization initiators (C1-1) contain at least (C1-1a) a fused polycyclic skeleton-containing photopolymerization initiator and (C1-1b) a fused polycyclic heterocyclic skeleton-containing photopolymerization initiator; the fused polycyclic skeleton-containing photopolymerization initiator (C1-1a) comprises a specific structure; and an oxime ester structure or an oxime ester carbonyl structure is bonded to each of the fused polycyclic skeleton and the fused polycyclic heterocyclic skeleton.

Description

[Technical Field]

[0001] The present invention relates to a negative photosensitive resin composition, a cured film, an organic EL display, and a method for producing the cured film. [Background technology]

[0002] BACKGROUND ART In recent years, many products using organic electroluminescence (hereinafter, "EL") displays have been developed in the field of display devices having thin displays, such as smartphones, tablet PCs, and televisions.

[0003] To improve the reliability of organic electroluminescent (EL) displays, highly heat-resistant and highly sensitive photosensitive resin compositions are used for the pixel division layer, thin film transistor (hereinafter "TFT") planarization layer, or TFT protective layer of the organic electroluminescent display, as well as the interlayer insulating layer or gate insulating layer in forming the TFT array. The pixel division layer, in particular, requires a stepped shape to reduce the contact area between the deposition mask and the pixel division layer during light-emitting layer deposition, and the ability to form the stepped shape of the pixel division layer in one go by one-shot exposure using a half-tone photomask (hereinafter "half-tone characteristics") is also required.

[0004] Examples of the photosensitive resin composition include a negative-type photosensitive resin composition containing a fluorene skeleton-containing oxime ester-based photopolymerization initiator and a diphenyl sulfide skeleton-containing oxime ester-based photopolymerization initiator (see Patent Document 1), and a negative-type photosensitive resin composition containing a fluorene skeleton-containing oxime ester-based photopolymerization initiator and a diphenyl sulfide skeleton-containing oxime ester-based photopolymerization initiator of a specific structure (see Patent Document 2). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-141770 [Patent Document 2] International Publication No. 2018 / 052024 Summary of the Invention [Problem to be solved by the invention]

[0006] In order to improve the reliability of organic EL displays and simplify their production, photosensitive resin compositions are required to have high sensitivity, excellent halftone characteristics, the ability to form patterns with low taper shapes after development, and the ability to suppress the adhesion of residues at pattern openings after thermal curing. However, all of the photosensitive resin compositions described in the above documents were insufficient in any of the above properties as materials for use in organic EL displays. [Means for solving the problem]

[0007] In order to achieve the above-described object, the negative-tone photosensitive resin composition of the present invention comprises (A) an alkali-soluble resin and (C1) two or more (C1-1) oxime ester photopolymerization initiators as photopolymerization initiators, wherein the (C1-1) oxime ester photopolymerization initiators comprise at least a (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator and a (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiator, and the (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator has a fused polycyclic skeleton containing an aromatic skeleton, the fused polycyclic skeleton being composed only of carbon atoms and hydrogen atoms, and the fused polycyclic skeleton and the fused polycyclic heterocyclic skeleton each having an oxime ester structure or an oxime ester carbonyl structure bonded to them. [Effects of the Invention]

[0008] The negative photosensitive resin composition of the present invention has high sensitivity, excellent halftone characteristics, can form a pattern with a low taper shape after development, and can suppress the adhesion of residues at pattern openings after thermal curing. [Brief explanation of the drawings]

[0009] [Figure 1]FIG. 1 is a process diagram illustrating, in schematic cross section, steps 1 to 7 of the manufacturing process for an organic EL display using a cured film of the negative photosensitive resin composition of the present invention. [Figure 2] FIG. 2 is a cross-sectional view showing an example of a cross section of a cured pattern having a stepped shape. [Figure 3] FIG. 3 is a schematic diagram illustrating the arrangement and dimensions of light-transmitting portions, light-shielding portions, and semi-light-transmitting portions in a half-tone photomask used for evaluating half-tone characteristics. [Figure 4] FIG. 4 is a schematic plan view illustrating the manufacturing process of steps 1 to 4 for the substrate of the organic EL display used in the evaluation of the light-emitting characteristics. [Figure 5] FIG. 5 is a schematic diagram illustrating a schematic cross section of an organic EL display that does not have a polarizing layer. DETAILED DESCRIPTION OF THE INVENTION

[0010] The negative-tone photosensitive resin composition of the present invention comprises (A) an alkali-soluble resin and (C1) two or more (C1-1) oxime ester photopolymerization initiators as photopolymerization initiators, the (C1-1) oxime ester photopolymerization initiators comprising at least a (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator and a (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiator, the (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator having a fused polycyclic skeleton containing an aromatic skeleton, the fused polycyclic skeleton being composed only of carbon atoms and hydrogen atoms, and the fused polycyclic skeleton and the fused polycyclic heterocyclic skeleton each having an oxime ester structure or an oxime ester carbonyl structure bonded to them.

[0011] The materials contained in the negative photosensitive resin composition of the present invention will be described below.

[0012] <<(A) Alkali-soluble resin>> <(A1) First Resin> The negative-type photosensitive resin composition of the present invention contains (A) an alkali-soluble resin. The alkali-soluble resin (A) preferably contains at least (A1) a first resin. The (A1) first resin preferably contains one or more resins selected from the group consisting of (A1-1) a polyimide, (A1-2) a polyimide precursor, (A1-3) a polybenzoxazole, and (A1-4) a polybenzoxazole precursor. In the present invention, the (A1-1) polyimide, (A1-2) a polyimide precursor, (A1-3) a polybenzoxazole, and (A1-4) a polybenzoxazole precursor may be a single resin or a copolymer thereof.

[0013] From the viewpoints of forming a pattern with a low taper shape after development, improving halftone characteristics, improving the heat resistance of the cured film, and improving the reliability of the light-emitting device, the alkali-soluble resin (A) preferably contains one or more resins selected from the group consisting of (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor as the first resin (A1), more preferably contains (A1-1) polyimide and / or (A1-3) polybenzoxazole, and even more preferably contains (A1-1) polyimide.

[0014] The polyimide (A1-1) and the polyimide precursor (A1-2) have imide and / or amide bonds as polar bonds. The polybenzoxazole (A1-3) and the polybenzoxazole precursor (A1-4) have oxazole and / or amide bonds as polar bonds. Therefore, when the pigment (D1) is incorporated as the colorant (D) described below, these polar bonds strongly interact with the pigment (D1), thereby improving the dispersion stability of the pigment (D1).

[0015] <(A1-1) Polyimide and (A1-2) Polyimide Precursor> Examples of the polyimide precursor (A1-2) include those obtained by reacting a tetracarboxylic acid, a corresponding tetracarboxylic dianhydride, a tetracarboxylic dichloride, or an activated tetracarboxylic diester with a diamine, a diisocyanate compound obtained by reacting a diamine with phosgene, or a trimethylsilylated diamine, and contain tetracarboxylic acid residues and / or tetracarboxylic acid derivative residues and diamine residues and / or diamine derivative residues. Examples of the polyimide precursor (A1-2) include polyamic acid, polyamic acid ester, polyamic acid amide, and polyisoimide.

[0016] Examples of the (A1-1) polyimide include those obtained by dehydrating and ring-closing the above-mentioned polyamic acid, polyamic acid ester, polyamic acid amide, or polyisoimide by heating or by a reaction using an acid or a base.

[0017] The polyimide (A1-1) used in the present invention preferably contains a structural unit represented by the following general formula (1), from the viewpoints of forming a pattern with a low taper shape after development, improving halftone characteristics, improving the heat resistance of the cured film, and improving the reliability of the light-emitting device:

[0018] [ka]

[0019] In general formula (1), R 1 represents a tetravalent to decavalent organic group, and R 2 represents a divalent to decavalent organic group. 3 and R 4 each independently represents a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or a substituent represented by general formula (5) or general formula (6), p represents an integer of 0 to 6, and q represents an integer of 0 to 8, provided that R 3 or R 4 When represents a phenolic hydroxyl group, R bonded to the phenolic hydroxyl group 1 or R2 represents an aromatic structure.

[0020] R in general formula (1) 1 represents a tetracarboxylic acid residue and / or a tetracarboxylic acid derivative residue, R 2 represents a diamine residue and / or a diamine derivative residue. Examples of the tetracarboxylic acid derivative include tetracarboxylic acid dianhydrides, tetracarboxylic acid dichlorides, and tetracarboxylic acid activated diesters. Examples of the diamine derivative include diisocyanate compounds and trimethylsilylated diamines.

[0021] In general formula (1), R 1 is preferably a tetravalent to decavalent organic group having one or more selected from the group consisting of an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 30 carbon atoms. 2 is preferably a divalent to decavalent organic group having one or more selected from the group consisting of an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 30 carbon atoms. q is preferably an integer of 1 to 8. The above-mentioned aliphatic structure, alicyclic structure, and aromatic structure may have a heteroatom, and may be either unsubstituted or substituted.

[0022] [ka]

[0023] In general formulas (5) and (6), R 19 ~R 21 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. 19 ~R 21 are each independently preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms. The above alkyl groups, acyl groups, and aryl groups may be unsubstituted or substituted.

[0024] The polyimide (A1-1) preferably contains a structural unit represented by general formula (1), and the content of the structural unit represented by general formula (1) relative to all structural units in the polyimide (A1-1) is preferably 50 to 100 mol %, more preferably 60 to 100 mol %, and even more preferably 70 to 100 mol %. A content of 50 to 100 mol % can improve the formation of a low-taper pattern after development, halftone characteristics, heat resistance of the cured film, and reliability of the light-emitting device.

[0025] The polyimide precursor (A1-2) used in the present invention preferably contains a structural unit represented by the following general formula (3), from the viewpoints of improving sensitivity during exposure, improving the heat resistance of the cured film, and improving the reliability of the light-emitting device:

[0026] [ka]

[0027] In general formula (3), R 9 represents a tetravalent to decavalent organic group, and R 10 represents a divalent to decavalent organic group. 11 represents a substituent represented by the above general formula (5) or general formula (6), and R 12 represents a phenolic hydroxyl group, a sulfonic acid group, or a mercapto group, and R 13 represents a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or a substituent represented by the above-mentioned general formula (5) or general formula (6). t represents an integer of 2 to 8, u represents an integer of 0 to 6, and v represents an integer of 0 to 8, and 2≦t+u≦8. However, R 12 or R 13 When represents a phenolic hydroxyl group, R bonded to the phenolic hydroxyl group 9 or R 10 represents an aromatic structure.

[0028] R in general formula (3) 9 represents a tetracarboxylic acid residue and / or a tetracarboxylic acid derivative residue, R 10represents a diamine residue and / or a diamine derivative residue. Examples of the tetracarboxylic acid derivative include tetracarboxylic acid dianhydrides, tetracarboxylic acid dichlorides, and tetracarboxylic acid activated diesters. Examples of the diamine derivative include diisocyanate compounds and trimethylsilylated diamines.

[0029] In general formula (3), R 9 is preferably a tetravalent to decavalent organic group having one or more selected from the group consisting of an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 30 carbon atoms. 10 is preferably a divalent to decavalent organic group having one or more selected from the group consisting of an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 30 carbon atoms. v is preferably an integer of 1 to 8. The above-mentioned aliphatic structure, alicyclic structure, and aromatic structure may have a heteroatom, and may be either unsubstituted or substituted.

[0030] The polyimide precursor (A1-2) preferably contains a structural unit represented by general formula (3), and the content of the structural unit represented by general formula (3) relative to all structural units in the polyimide precursor (A1-2) is preferably 50 to 100 mol %, more preferably 60 to 100 mol %, and even more preferably 70 to 100 mol %. A content of 50 to 100 mol % can improve sensitivity during exposure, heat resistance of the cured film, and reliability of the light-emitting device.

[0031] (A1-2) The polyimide precursor may be a polyimide precursor having a structural unit represented by general formula (3) R 11 is a substituent represented by general formula (5), R 19 A structural unit in which R is a hydrogen atom is called an amic acid structural unit. The amic acid structural unit in the (A1-2) polyimide precursor has a carboxy group as a tetracarboxylic acid residue and / or a tetracarboxylic acid derivative residue. The (A1-2) polyimide precursor includes a structural unit represented by general formula (3) in which R 11 is a substituent represented by general formula (5), R19 is 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, is called an amic acid ester structural unit. 11 is a substituent represented by general formula (6), the structural unit is called an amic acid amide structural unit.

[0032] From the viewpoints of improving resolution after development and forming a pattern with a low taper shape after development, the polyimide precursor (A1-2) preferably contains the amic acid structural unit, as well as the amic acid ester structural unit and / or the amic acid amide structural unit. The polyimide precursor (A1-2) containing the amic acid structural unit, as well as the amic acid ester structural unit and / or the amic acid amide structural unit can be synthesized by esterifying and / or amidating a portion of the carboxy groups of the tetracarboxylic acid residues and / or tetracarboxylic acid derivative residues of the amic acid structural units.

[0033] <(A1-3) Polybenzoxazole and (A1-4) Polybenzoxazole Precursor> Examples of the polybenzoxazole precursor (A1-4) include those obtained by reacting a dicarboxylic acid, a dicarboxylic acid dichloride obtained by reacting a dicarboxylic acid with thionyl chloride, or a dicarboxylic acid activated diester with a diamine such as a bisaminophenol compound, and contain dicarboxylic acid residues and / or dicarboxylic acid derivative residues and bisaminophenol compound residues and / or bisaminophenol compound derivative residues. Examples of the polybenzoxazole precursor (A1-4) include polyhydroxyamides.

[0034] Examples of (A1-3) polybenzoxazoles include those obtained by dehydrating and cyclizing a dicarboxylic acid and a bisaminophenol compound as a diamine using polyphosphoric acid, and those obtained by dehydrating and cyclizing the above-mentioned polyhydroxyamides using heating or a reaction using phosphoric anhydride, a base, a carbodiimide compound, or the like, and have dicarboxylic acid residues and / or dicarboxylic acid derivative residues and bisaminophenol compound residues and / or bisaminophenol compound derivative residues.

[0035] The polybenzoxazole (A1-3) used in the present invention preferably contains a structural unit represented by general formula (2), from the viewpoints of forming a pattern with a low taper shape after development, improving halftone characteristics, improving the heat resistance of the cured film, and improving the reliability of the light-emitting device.

[0036] [ka]

[0037] In general formula (2), R 5 represents a divalent to decavalent organic group, and R 6 R represents a tetravalent to decavalent organic group having an aromatic structure. 7 R represents a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or a substituent represented by the above-mentioned general formula (5) or general formula (6). 8 represents a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or a substituent represented by the above-mentioned general formula (5) or general formula (6). r represents an integer of 0 to 8, and s represents an integer of 0 to 6. However, R 7 When represents a phenolic hydroxyl group, R bonded to the phenolic hydroxyl group 5 represents an aromatic structure.

[0038] R in general formula (2) 5 represents a dicarboxylic acid residue and / or a dicarboxylic acid derivative residue, R 6represents a residue of a bisaminophenol compound and / or a residue of a bisaminophenol compound derivative. Examples of the dicarboxylic acid derivative include dicarboxylic acid anhydrides, dicarboxylic acid chlorides, dicarboxylic acid activated esters, tricarboxylic acid anhydrides, tricarboxylic acid chlorides, tricarboxylic acid activated esters, and diformyl compounds.

[0039] In general formula (2), R 5 is preferably a divalent to decavalent organic group having one or more selected from the group consisting of an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 30 carbon atoms. 6 is preferably a tetravalent to decavalent organic group having an aromatic structure with 6 to 30 carbon atoms. s is preferably an integer of 1 to 6. The aliphatic structure, alicyclic structure, and aromatic structure described above may have a heteroatom, and may be either unsubstituted or substituted.

[0040] The polybenzoxazole (A1-3) preferably contains a structural unit represented by general formula (2), and the content of the structural unit represented by general formula (2) relative to all structural units in the polybenzoxazole (A1-3) is preferably 50 to 100 mol %, more preferably 60 to 100 mol %, and even more preferably 70 to 100 mol %. A content of 50 to 100 mol % can improve the formation of a low-taper pattern after development, halftone characteristics, heat resistance of the cured film, and reliability of the light-emitting device.

[0041] The polybenzoxazole precursor (A1-4) used in the present invention preferably contains a structural unit represented by general formula (4), from the viewpoints of improving sensitivity during exposure, improving the heat resistance of the cured film, and improving the reliability of the light-emitting device.

[0042] [ka]

[0043] In general formula (4), R 14 represents a divalent to decavalent organic group, and R 15R represents a tetravalent to decavalent organic group having an aromatic structure. 16 represents a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or a substituent represented by the above-mentioned general formula (5) or general formula (6), and R 17 represents a phenolic hydroxyl group, and R 18 represents a sulfonic acid group, a mercapto group, or a substituent represented by the above-mentioned general formula (5) or general formula (6). w represents an integer of 0 to 8, x represents an integer of 2 to 8, and y represents an integer of 0 to 6, and 2≦x+y≦8. However, R 16 When represents a phenolic hydroxyl group, R bonded to the phenolic hydroxyl group 14 represents an aromatic structure.

[0044] R in general formula (4) 14 represents a dicarboxylic acid residue and / or a dicarboxylic acid derivative residue, R 15 represents a residue of a bisaminophenol compound and / or a residue of a bisaminophenol compound derivative. Examples of the dicarboxylic acid derivative include dicarboxylic acid anhydrides, dicarboxylic acid chlorides, dicarboxylic acid activated esters, tricarboxylic acid anhydrides, tricarboxylic acid chlorides, tricarboxylic acid activated esters, and diformyl compounds.

[0045] In general formula (4), R 14 is preferably a divalent to decavalent organic group having one or more selected from the group consisting of an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 30 carbon atoms. 15 is preferably a tetravalent to decavalent organic group having an aromatic structure with 6 to 30 carbon atoms. The aliphatic structure, alicyclic structure, and aromatic structure described above may have a heteroatom, and may be either unsubstituted or substituted.

[0046] The polybenzoxazole precursor (A1-4) preferably contains a structural unit represented by general formula (4), and the content of the structural unit represented by general formula (4) relative to all structural units in the polybenzoxazole precursor (A1-4) is preferably 50 to 100 mol %, more preferably 60 to 100 mol %, and even more preferably 70 to 100 mol %. A content of 50 to 100 mol % can improve sensitivity during exposure, heat resistance of the cured film, and reliability of the light-emitting device.

[0047] Examples of the tetracarboxylic acids, dicarboxylic acids, and carboxylic acid derivatives, as well as the diamines and diamine derivatives used in the synthesis of the first resin (A1) above include the compounds described in WO 2017 / 057281.

[0048] <Structural unit containing a fluorine atom> At least one selected from the group consisting of (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor preferably contains fluorine-containing structural units in an amount of 10 to 100 mol% of all structural units. When at least one selected from the group consisting of (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor contains fluorine-containing structural units, transparency is improved, sensitivity during exposure is improved, and a pattern with a low taper shape can be formed after development. In addition, halftone characteristics are improved. This is presumably due to the improved film transparency, which enables radical curing deep within the film. Furthermore, when the (C1-1) oxime ester photopolymerization initiator described below has a halogen-substituted group, it is believed that the compatibility between the alkali-soluble resin and the photopolymerization initiator can be improved, allowing UV curing during exposure to proceed efficiently even deep within the film. In addition, fluorine atoms can impart water repellency to the film surface, preventing penetration of the developer into the film surface during alkaline development and suppressing side etching by the developer. Herein, exposure refers to irradiation with activated actinic rays (radiation), such as visible light, ultraviolet light, electron beams, or X-rays. From the perspective of commonly used light sources, for example, ultra-high-pressure mercury lamps capable of irradiating visible light or ultraviolet light are preferred, with j-rays (wavelength 313 nm), i-rays (wavelength 365 nm), h-rays (wavelength 405 nm), or g-rays (wavelength 436 nm) being more preferred. Hereinafter, exposure refers to irradiation with activated actinic rays (radiation).

[0049] Examples of the structural unit having a fluorine atom contained in the polyimide (A1-1) and / or the polyimide precursor (A1-2) include a structural unit derived from a tetracarboxylic acid having a fluorine atom, a structural unit derived from a tetracarboxylic acid derivative having a fluorine atom, a structural unit derived from a diamine having a fluorine atom, and a structural unit derived from a diamine derivative having a fluorine atom.

[0050] Examples of the structural unit having a fluorine atom contained in the polybenzoxazole (A1-3) and / or polybenzoxazole precursor (A1-4) include a structural unit derived from a dicarboxylic acid having a fluorine atom, a structural unit derived from a dicarboxylic acid derivative having a fluorine atom, a structural unit derived from a bisaminophenol compound having a fluorine atom, and a structural unit derived from a bisaminophenol compound derivative having a fluorine atom.

[0051] In one or more resins selected from the group consisting of (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor, the content of structural units having fluorine atoms relative to all structural units is preferably 30 to 100 mol %. The content of structural units having fluorine atoms is more preferably 50 mol % or more, and even more preferably 70 mol % or more. A content of 30 to 100 mol % can improve sensitivity during exposure.

[0052] In one or more resins selected from the group consisting of (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor, the content of one or more selected from the group consisting of structural units derived from tetracarboxylic acid having fluorine atoms, structural units derived from tetracarboxylic acid derivatives having fluorine atoms, structural units derived from dicarboxylic acid having fluorine atoms, and structural units derived from dicarboxylic acid derivatives having fluorine atoms is preferably 30 to 100 mol % relative to the total of all structural units derived from carboxylic acids and all structural units derived from carboxylic acid derivatives. The content of structural units having fluorine atoms is more preferably 50 mol % or more, and even more preferably 70 mol % or more. A content of 30 to 100 mol % can improve sensitivity during exposure.

[0053] In one or more resins selected from the group consisting of (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor, the content of one or more selected from the group consisting of structural units derived from fluorine-containing diamines, structural units derived from fluorine-containing diamine derivatives, structural units derived from fluorine-containing bisaminophenol compounds, and structural units derived from fluorine-containing bisaminophenol compound derivatives is preferably 30 to 100 mol % relative to the total of all structural units derived from amines and all structural units derived from amine derivatives. The content of fluorine-containing structural units is more preferably 50 mol % or more, and even more preferably 70 mol % or more. A content of 30 to 100 mol % can improve sensitivity during exposure.

[0054] <Structural unit containing a fused polycyclic skeleton> At least one selected from the group consisting of (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor preferably contains a structural unit containing a fused polycyclic skeleton. The inclusion of a structural unit containing a fused polycyclic skeleton improves sensitivity during exposure and enables the formation of a pattern with a low taper shape after development. In addition, it improves halftone characteristics. The structural unit containing a fused polycyclic skeleton preferably contains at least one selected from the group consisting of structural units having a fluorene skeleton and structural units having an indane skeleton. This is thought to be because the structural unit exhibits significant interaction with the (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator and the (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiator described below, thereby enhancing compatibility with the alkali-soluble resin at the initiation of photopolymerization, and thereby allowing efficient UV curing during exposure even deep within the film. In one or more resins selected from the group consisting of (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor, the content of structural units containing a fused polycyclic skeleton relative to all structural units is preferably 10 to 50 mol %, more preferably 20 to 50 mol % or more, and even more preferably 30 to 50 mol % or more.

[0055] Examples of the structural unit containing a fused polycyclic skeleton contained in the polyimide (A1-1) and / or the polyimide precursor (A1-2) include a structural unit derived from a tetracarboxylic acid containing a fused polycyclic skeleton, a structural unit derived from a tetracarboxylic acid derivative containing a fused polycyclic skeleton, a structural unit derived from a diamine containing a fused polycyclic skeleton, and a structural unit derived from a diamine derivative containing a fused polycyclic skeleton.

[0056] Examples of structural units containing a fused polycyclic skeleton contained in the polybenzoxazole (A1-3) and / or polybenzoxazole precursor (A1-4) include structural units derived from dicarboxylic acids containing a fused polycyclic skeleton, structural units derived from dicarboxylic acid derivatives containing a fused polycyclic skeleton, structural units derived from bisaminophenol compounds containing a fused polycyclic skeleton, and structural units derived from bisaminophenol compound derivatives containing a fused polycyclic skeleton.

[0057] <Other structural units> From the viewpoints of improving the heat resistance of the cured film due to the heat resistance of the aromatic group and improving halftone properties, one or more selected from the group consisting of (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor preferably contain structural units derived from aromatic carboxylic acids and / or structural units derived from aromatic carboxylic acid derivatives. Similarly, it is also preferable to contain structural units derived from aromatic amines and / or structural units derived from aromatic amine derivatives. Furthermore, from the viewpoint of improving adhesion between the cured film and the underlying substrate, it is also preferable to contain structural units derived from diamines having silyl groups or siloxane bonds and / or structural units derived from diamine derivatives having silyl groups or siloxane bonds. Furthermore, from the viewpoints of forming a pattern with a low taper shape after thermal curing and improving the mechanical properties of the cured film, it is also preferable to contain structural units derived from amines having an oxyalkylene structure and / or structural units derived from amine derivatives having an oxyalkylene structure.

[0058] <End-capping agent> From the viewpoints of improving the storage stability of a coating solution of the resin composition and improving pattern processability in an alkaline developer, it is preferable that one or more selected from the group consisting of (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor have their resin ends capped with an end-capping agent such as a monoamine, a dicarboxylic acid anhydride, a monocarboxylic acid, a monocarboxylic acid chloride, or a monocarboxylic acid active ester.

[0059] <Introduction of an ethylenically unsaturated double bond group> At least one selected from the group consisting of (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor preferably has an ethylenically unsaturated double bond group. Also preferred are resins in which an ethylenically unsaturated double bond group has been introduced into the side chain of these resins by a reaction to introduce an ethylenically unsaturated double bond group. The presence of an ethylenically unsaturated double bond group can improve sensitivity during exposure and enable the formation of a pattern with a low taper shape after development.

[0060] One or more selected from the group consisting of (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor are preferably obtained by reacting some of their phenolic hydroxyl groups and / or carboxyl groups with a compound having an ethylenically unsaturated double bond group. The above-mentioned reaction makes it possible to introduce an ethylenically unsaturated double bond group into the side chain of the resin.

[0061] As the compound having an ethylenically unsaturated double bond group, from the viewpoint of reactivity, an electrophilic compound having an ethylenically unsaturated double bond group is preferred. As the electrophilic compound, from the viewpoint of reactivity and compound availability, an isocyanate compound, an epoxy compound, an alcohol compound, an aldehyde compound, a ketone compound, or a carboxylic acid anhydride is preferred, and an isocyanate compound or an epoxy compound is more preferred.

[0062] <Physical Properties of (A1-1) Polyimide, (A1-2) Polyimide Precursor, (A1-3) Polybenzoxazole, and (A1-4) Polybenzoxazole Precursor> The weight-average molecular weight (hereinafter "Mw") of one or more selected from the group consisting of (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor is preferably 1,000 or more, more preferably 3,000 or more, and even more preferably 5,000 or more, in terms of polystyrene, as measured by gel permeation chromatography (hereinafter "GPC"), from the viewpoints of improving resolution after development and reliability of light-emitting devices. On the other hand, from the viewpoints of forming a pattern with a low taper shape after thermal curing and improving pattern processability in an alkaline developer, Mw is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 30,000 or less, and especially preferably 20,000 or less. (A1-1) Polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor can be synthesized by known methods.

[0063] <(A2) Second Resin> The negative-type photosensitive resin composition of the present invention preferably further contains a second resin (A2) as the alkali-soluble resin (A). From the viewpoints of improving sensitivity during exposure and reducing taper by controlling the pattern shape after development, the second resin (A2) preferably contains one or more resins selected from the group consisting of polysiloxane (A2-1), polycyclic side chain-containing resin (A2-2), acid-modified epoxy resin (A2-3), and acrylic resin (A2-4). In the present invention, the polysiloxane (A2-1), polycyclic side chain-containing resin (A2-2), acid-modified epoxy resin (A2-3), and acrylic resin (A2-4) may be a single resin or a copolymer thereof.

[0064] From the viewpoints of improving halftone characteristics, improving sensitivity during exposure, and reducing taper by controlling pattern shape after development, the alkali-soluble resin (A) preferably contains one or more resins selected from the group consisting of (A2-1) polysiloxane, (A2-2) polycyclic side chain-containing resin, and (A2-3) acid-modified epoxy resin as the second resin (A2). It is more preferable to contain (A2-1) polysiloxane and / or (A2-2) polycyclic side chain-containing resin, and even more preferable to contain (A2-1) polysiloxane. Furthermore, by including (A2-1) polysiloxane, a pattern with a low taper shape can be formed after thermal curing. On the other hand, from the viewpoints of improving sensitivity during exposure and suppressing residue adhesion at pattern openings after thermal curing, it is preferable to contain (A2-2) polycyclic side chain-containing resin and / or (A2-3) acid-modified epoxy resin as the second resin (A2). It is more preferable to contain (A2-2) polycyclic side chain-containing resin.

[0065] In the negative-tone photosensitive resin composition of the present invention, from the viewpoint of significantly improving sensitivity during exposure, forming a pattern with a low taper shape after development, and improving halftone characteristics, when the alkali-soluble resin (A) contains, as the first resin (A1), one or more selected from the group consisting of (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor, it is preferred that the alkali-soluble resin (A) further contains, as the second resin (A2), polysiloxane (A2-1).

[0066] In the negative-tone photosensitive resin composition of the present invention, from the viewpoint of significantly improving sensitivity during exposure, forming a pattern with a low taper shape after development, and improving halftone characteristics, when the alkali-soluble resin (A) contains, as the first resin (A1), one or more selected from the group consisting of (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor, it is preferred that the alkali-soluble resin (A) further contains, as the second resin (A2), a polycyclic side chain-containing resin (A2-2) and / or an acid-modified epoxy resin (A2-3), and that the polycyclic side chain-containing resin (A2-2) and the acid-modified epoxy resin (A2-3) contain structural units having a fused polycyclic skeleton.

[0067] <(A2-1) Polysiloxane> In the present invention, examples of the polysiloxane (A2-1) include polysiloxanes obtained by hydrolyzing and dehydrating condensation of one or more organosilanes selected from the group consisting of trifunctional organosilanes, tetrafunctional organosilanes, difunctional organosilanes, and monofunctional organosilanes.

[0068] The polysiloxane (A2-1) used in the present invention preferably contains a trifunctional organosilane unit and / or a tetrafunctional organosilane unit, from the viewpoint of improving the heat resistance of the cured film and improving the resolution after development.

[0069] <Trifunctional organosilane unit and tetrafunctional organosilane unit> The polysiloxane (A2-1) used in the present invention preferably contains a trifunctional organosilane unit and / or a tetrafunctional organosilane unit from the viewpoints of improving the heat resistance of the cured film and improving the resolution after development. The trifunctional organosilane is preferably an organosilane unit represented by general formula (7). The tetrafunctional organosilane unit is preferably an organosilane unit represented by general formula (8). Furthermore, from the viewpoints of reducing the taper of the pattern shape and improving the mechanical properties of the cured film, the polysiloxane may contain a bifunctional organosilane unit. Furthermore, from the viewpoint of improving the storage stability of the resin composition coating liquid, the polysiloxane may contain a monofunctional organosilane unit.

[0070] [ka]

[0071] In general formulas (7) and (8), R 22 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. 22 is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. The alkyl group, cycloalkyl group, alkenyl group, and aryl group may have a heteroatom and may be unsubstituted or substituted. Examples of the above organosilanes include the compounds described in WO 2017 / 057281.

[0072] The content of the organosilane unit represented by general formula (7) in the polysiloxane (A2-1) is preferably 50 to 100 mol %, more preferably 60 to 100 mol %, and even more preferably 70 to 100 mol %, in terms of the molar ratio of Si atoms. A content of 50 to 100 mol % can improve the heat resistance of the cured film. The organosilane unit represented by general formula (7) is preferably an organosilane unit having an epoxy group. When the polysiloxane (A2-1) contains an organosilane unit having an epoxy group, it is possible to improve pattern processability during alkaline development and sensitivity during exposure.

[0073] The content of organosilane units represented by general formula (8) in polysiloxane (A2-1) is preferably 0 to 40 mol %, more preferably 0 to 30 mol %, and even more preferably 0 to 20 mol %, in terms of the molar ratio of Si atoms. A content of 0 to 40 mol % improves pattern processability during alkaline development, sensitivity during exposure, and heat resistance of the cured film. In addition, it is possible to form a pattern with a low taper shape after development, and to suppress changes in the dimensional width of pattern openings before and after thermal curing.

[0074] In the polysiloxane (A2-1), the organosilane units may be arranged in either a regular or irregular arrangement. Examples of regular arrangements include alternating copolymerization, periodic copolymerization, block copolymerization, and graft copolymerization. Examples of irregular arrangements include random copolymerization. The organosilane units may be arranged in either a two-dimensional or three-dimensional arrangement. Examples of two-dimensional arrangements include linear arrangements. Examples of three-dimensional arrangements include ladder, cage, and network arrangements.

[0075] The polysiloxane (A2-1) used in the present invention preferably contains an organosilane unit having an aromatic group, from the viewpoints of improving the heat resistance of the cured film due to the heat resistance of the aromatic group and improving halftone characteristics. The Mw of the polysiloxane (A2-1), measured by GPC in terms of polystyrene, is preferably 500 or more, from the viewpoints of improving the resolution after development and the reliability of the light-emitting device. On the other hand, the Mw is preferably 50,000 or less, from the viewpoints of forming a pattern with a low taper shape after thermal curing and improving pattern processability in an alkaline developer. The polysiloxane (A2-1) can be synthesized by a known method.

[0076] <(A2-2) Polycyclic side chain containing resin> Examples of the polycyclic side chain-containing resin (A2-2) that can be used in the present invention include the following polycyclic side chain-containing resins (I) to (IV). (I) A polycyclic side chain-containing resin obtained by reacting a compound obtained by reacting a polyfunctional phenol compound with a polyfunctional carboxylic acid dianhydride, with an epoxy compound. (II) A polycyclic side chain-containing resin obtained by reacting a compound obtained by reacting a polyfunctional phenol compound with an epoxy compound with a polyfunctional carboxylic acid dianhydride. (III) A polycyclic side chain-containing resin obtained by reacting a compound obtained by reacting a polyfunctional epoxy compound with a polyfunctional carboxylic acid compound, with an epoxy compound. (IV) A polycyclic side chain-containing resin obtained by reacting a compound obtained by reacting a polyfunctional epoxy compound with a carboxylic acid compound, with a polyfunctional carboxylic acid dianhydride.

[0077] Examples of the phenol compound, epoxy compound, carboxylic acid anhydride, and carboxylic acid compound include the compounds described in WO 2017 / 057281.

[0078] The (A2-2) polycyclic side chain-containing resin is a thermosetting resin having a structure in which the main chain and bulky side chains are connected by a single atom, and the bulky side chain has a highly heat-resistant and rigid cyclic structure such as a fluorene ring. Therefore, by incorporating a (A2-2) polycyclic side chain-containing resin having a highly heat-resistant and rigid cyclic structure such as a fluorene ring into a negative-tone photosensitive resin composition, the heat resistance of the resulting cured film can be improved. This makes the cured film suitable for applications requiring heat resistance. The (A2-2) polycyclic side chain-containing resin used in the present invention preferably has an ethylenically unsaturated double bond group. By incorporating a (A2-2) polycyclic side chain-containing resin having an ethylenically unsaturated double bond group into a negative-tone photosensitive resin composition, sensitivity during exposure can be improved and a pattern with a low taper shape can be formed after development.

[0079] From the viewpoint of improving the heat resistance of the cured film, the polycyclic side chain-containing resin (A2-2) used in the present invention preferably contains one or more structural units selected from the group consisting of structural units represented by general formula (47), structural units represented by general formula (48), structural units represented by general formula (49), and structural units represented by general formula (50). Furthermore, from the viewpoint of improving sensitivity during exposure and forming a pattern with a low taper shape after development, the polycyclic side chain-containing resin (A2-2) used in the present invention preferably contains an ethylenically unsaturated double bond group at one or more of the main chain, side chain, and terminal.

[0080] [ka]

[0081] In the general formulas (47) to (50), X 69 , X 70 , X 72 , X 73 , X 75 , X 76 , X 78 , and X 79 Each of X independently represents a monocyclic or fused polycyclic hydrocarbon ring. 71 , X 74 , X 77 , and X80 W each independently represents a divalent to decavalent organic group of a carboxylic acid residue and / or a carboxylic acid derivative residue. 1 ~W 4 R each independently represents an organic group having two or more aromatic groups. 160 ~R 167 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R 170 ~R 175 , R 177 , and R 178 R each independently represents a hydrogen atom or an organic group having an ethylenically unsaturated double bond group. 176 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. a, b, c, d, e, f, g, and h each independently represent an integer of 0 to 10, and α, β, γ, and δ each independently represent 0 or 1.

[0082] In the general formulas (47) to (50), X 69 , X 70 , X 72 , X 73 , X 75 , X 76 , X 78 , and X 79 are each preferably a monocyclic or fused polycyclic hydrocarbon ring having 6 to 15 carbon atoms and a valence of 2 to 10. 71 , X 74 , X 77 , and X 80 are preferably each independently a divalent to decavalent organic group having at least one selected from the group consisting of an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, and an aromatic structure having 6 to 30 carbon atoms. From the viewpoints of improving halftone characteristics, improving the heat resistance of the cured film, and improving the reliability of the light-emitting device, W 1 ~W 4 are each preferably independently a substituent represented by any one of general formulas (51) to (56). 170 ~R 175 , R 177 , and R 178are each independently preferably a substituent represented by general formula (57). The above-mentioned alkyl group, aliphatic structure, alicyclic structure, aromatic structure, monocyclic or fused polycyclic aromatic hydrocarbon ring, and organic group having an ethylenically unsaturated double bond group may have a hetero atom, and may be either unsubstituted or substituted.

[0083] [ka]

[0084] In the general formulas (51) to (56), R 179 ~R 182 , R 185 , and R 188 R each independently represents an alkyl group having 1 to 10 carbon atoms. 183 , R 184 , R 186 , R 187 , R 189 , R 191 , and R 193 ~R 196 R each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. 190 and R 192 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms; R 190 and R 192 It is also acceptable to form a ring with R 190 and R 192 Examples of the ring formed by R include a benzene ring and a cyclohexane ring. 183 and R 184 At least one of R is an aryl group having 6 to 15 carbon atoms. 186 and R 187 At least one of R is an aryl group having 6 to 15 carbon atoms. 189 and R 190 at least one of R is an aryl group having 6 to 15 carbon atoms; 191 and R 192at least one of R is an aryl group having 6 to 15 carbon atoms; 190 and R 192 It is also acceptable to form a ring with R 193 and R 194 at least one of R is an aryl group having 6 to 15 carbon atoms; 195 and R 196 At least one of R is an aryl group having 6 to 15 carbon atoms. i, j, k, l, m, and n each independently represent an integer of 0 to 4. In general formulas (51) to (56), R 190 and R 192 are each independently preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and R 190 and R 192 A benzene ring is preferred as the ring formed by the formula: The alkyl group, cycloalkyl group, and aryl group may be unsubstituted or substituted.

[0085] [ka]

[0086] In general formula (57), X 81 represents a direct bond, an alkylene chain having 1 to 10 carbon atoms, a cycloalkylene chain having 4 to 10 carbon atoms, or an arylene chain having 6 to 15 carbon atoms; X 82 represents a direct bond or an arylene chain having 6 to 15 carbon atoms. 197 represents a vinyl group, an aryl group, or a (meth)acrylic group. 81 is preferably a direct bond, an alkylene chain having 1 to 6 carbon atoms, a cycloalkylene chain having 4 to 7 carbon atoms, or an arylene chain having 6 to 10 carbon atoms. 82 is preferably a direct bond or an arylene chain having 6 to 10 carbon atoms. The alkylene chain, cycloalkylene chain, arylene chain, vinyl group, aryl group, and (meth)acrylic group may be unsubstituted or substituted.

[0087] The polycyclic side chain-containing resin (A2-2) that can be used in the present invention preferably contains a structural unit having a fused polycyclic skeleton, from the viewpoints of improving sensitivity during exposure and forming a pattern with a low taper shape after development. The structural unit having a fused polycyclic skeleton preferably contains one or more structural units selected from the group consisting of structural units having a fluorene skeleton and structural units having an indane skeleton. By including one or more structural units selected from the group consisting of structural units having a fluorene skeleton and structural units having an indane skeleton in the polycyclic side chain-containing resin (A2-2), sensitivity during exposure can be improved and a pattern with a low taper shape can be formed after development. In addition, halftone characteristics can be improved. This is thought to be due to the significant interaction between the structural unit and the fused polycyclic skeleton-containing photopolymerization initiator (C1-1a) and the fused polycyclic heterocyclic skeleton-containing photopolymerization initiator (C1-1b), which will be described later, thereby increasing the compatibility of the alkali-soluble resin with the photopolymerization initiator at the initiation of photopolymerization, and thereby allowing efficient UV curing during exposure even deep within the film. In the above general formulas (47) to (50), W 1 ~W 4 is general formula (51) or general formula (53), the polycyclic side chain-containing resin (A2-2) contains one or more structural units selected from the group consisting of structural units having a fluorene skeleton and structural units having an indane skeleton.

[0088] <Acidic groups derived from carboxylic acids and acidic groups derived from carboxylic acid derivatives> From the viewpoints of improving pattern processability in an alkaline developer and improving resolution after development, the polycyclic side chain-containing resin (A2-2) preferably contains a structural unit derived from a carboxylic acid and / or a structural unit derived from a carboxylic acid derivative, and the polycyclic side chain-containing resin (A2-2) preferably has an acidic group. Examples of the acidic group include a carboxy group, a carboxylic acid anhydride group, a sulfonic acid group, a phenolic hydroxyl group, and a hydroxyimide group. From the viewpoints of improving pattern processability in an alkaline developer and improving resolution after development, a carboxy group, a carboxylic acid anhydride group, or a phenolic hydroxyl group is preferred, and a carboxy group or a carboxylic acid anhydride group is more preferred.

[0089] <End-capping agent> As the (A2-2) polycyclic side chain-containing resin, from the viewpoints of improving the storage stability of a coating liquid of the resin composition and improving pattern processability in an alkaline developer, it is preferred that the resin terminals be capped with a terminal capping agent such as a tricarboxylic acid anhydride, a dicarboxylic acid anhydride, or a monocarboxylic acid.

[0090] The polycyclic side chain-containing resin (A2-2) preferably contains a structural unit derived from an aromatic carboxylic acid and / or a structural unit derived from an aromatic carboxylic acid derivative, from the viewpoints of improving the heat resistance of the cured film due to the heat resistance of the aromatic group and improving halftone characteristics. The polycyclic side chain-containing resin (A2-2) preferably has a weight average molecular weight (Mw) of 500 or more, calculated as polystyrene equivalent as measured by GPC, from the viewpoints of improving the resolution after development and the reliability of the light-emitting device. On the other hand, the Mw is preferably 50,000 or less, from the viewpoints of forming a pattern with a low taper shape after thermal curing and improving pattern processability in an alkaline developer. The polycyclic side chain-containing resin (A2-2) can be synthesized by a known method.

[0091] <(A2-2) Specific Examples of Polycyclic Side Chain-Containing Resins> (A2-2) Examples of polycyclic side chain-containing resins include "ADEKA ARKLS" (registered trademark) WR-101 or WR-301 (both manufactured by ADEKA Corporation), OGSOL (registered trademark) CR-1030, CR-TR1, CR-TR2, CR-TR3, CR-TR4, CR-TR5, CR-TR6, CR-TR7, CR-TR8, CR-TR9, and CR-TR10 (all manufactured by Osaka Gas Chemicals Co., Ltd.), and TR-B201 or TR-B202 (all manufactured by TRONLY).

[0092] <(A2-3) Acid-modified epoxy resin> Examples of the acid-modified epoxy resin (A2-3) that can be used in the present invention include the following acid-modified epoxy resins (I) to (VI). (I) An acid-modified epoxy resin obtained by reacting a compound obtained by reacting a polyfunctional phenol compound with a polyfunctional carboxylic acid dianhydride, with an epoxy compound. (II) An acid-modified epoxy resin obtained by reacting a compound obtained by reacting a polyfunctional phenol compound with an epoxy compound with a polyfunctional carboxylic acid dianhydride. (III) An acid-modified epoxy resin obtained by reacting a compound obtained by reacting a polyfunctional alcohol compound with a polyfunctional carboxylic acid dianhydride, with an epoxy compound. (IV) An acid-modified epoxy resin obtained by reacting a compound obtained by reacting a polyfunctional alcohol compound with an epoxy compound, with a polyfunctional carboxylic acid dianhydride. (V) An acid-modified epoxy resin obtained by reacting a compound obtained by reacting a polyfunctional epoxy compound with a polyfunctional carboxylic acid compound, and then reacting the resulting compound with an epoxy compound. (VI) An acid-modified epoxy resin obtained by reacting a compound obtained by reacting a polyfunctional epoxy compound with a carboxylic acid compound, with a polyfunctional carboxylic acid dianhydride.

[0093] Examples of the phenol compound, alcohol compound, epoxy compound, carboxylic acid anhydride, and carboxylic acid compound include the compounds described in WO 2017 / 057281.

[0094] The acid-modified epoxy resin (A2-3) preferably has an ethylenically unsaturated double bond group. By incorporating the acid-modified epoxy resin (A2-3) having an ethylenically unsaturated double bond group into the resin composition, sensitivity during exposure can be improved and a pattern with a small taper shape can be formed after development.

[0095] From the viewpoints of improving halftone properties, improving the heat resistance of the cured film, and improving the reliability of the light-emitting device, the acid-modified epoxy resin (A2-3) preferably contains one or more structural units selected from the group consisting of structural units represented by general formula (35), structural units represented by general formula (36), structural units represented by general formula (37), structural units represented by general formula (38), structural units represented by general formula (41), structural units represented by general formula (42), and structural units represented by general formula (43). Furthermore, from the viewpoints of improving sensitivity during exposure and forming a pattern with a low taper shape after development, the acid-modified epoxy resin (A2-3) used in the present invention preferably has an ethylenically unsaturated double bond group at one or more of the main chain, side chain, and terminal.

[0096] [ka]

[0097] In the general formulas (35) to (38), X 51 ~X 54 each independently represents an aliphatic structure having 1 to 6 carbon atoms. 53 R represents an aromatic structure having 10 to 25 carbon atoms and a valence of 3 to 16. 71 ~R 75 each independently represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms; R 76 represents an alkyl group having 1 to 10 carbon atoms, and R 78 ~R 82 each independently represents a halogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms; R 83 ~R 88each independently represents a substituent represented by general formula (39). a, b, c, d, and e each independently represent an integer of 0 to 10, f represents an integer of 0 to 14, h, i, j, and k each independently represent an integer of 0 to 3, and l represents an integer of 0 to 4. The above-mentioned alkyl groups, cycloalkyl groups, aryl groups, aliphatic structures, and aromatic structures may have heteroatoms and may be either unsubstituted or substituted.

[0098] Z in general formula (38) 53 The aromatic structure of the formula (38) contains one or more selected from the group consisting of a terphenyl skeleton, a naphthalene skeleton, an anthracene skeleton, and a fluorene skeleton. 53 Examples of other aromatic structures include a 1,2,3,4-tetrahydronaphthalene skeleton, a 2,2-diphenylpropane skeleton, a diphenyl ether skeleton, a diphenyl ketone skeleton, and a diphenyl sulfone skeleton.

[0099] [ka]

[0100] In the general formula (39), X 55 represents an alkylene chain having 1 to 6 carbon atoms or a cycloalkylene chain having 4 to 10 carbon atoms. 89 ~R 91 R each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. 92 represents a hydrogen atom or a substituent represented by general formula (40). 89 and R 90 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom. 91 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group. 56represents an alkylene chain having 1 to 6 carbon atoms, an alkenylene chain having 1 to 6 carbon atoms, a cycloalkylene chain having 4 to 10 carbon atoms, or a cycloalkenylene chain having 4 to 10 carbon atoms. 56 is preferably an alkylene chain having 1 to 4 carbon atoms, an alkenylene chain having 1 to 4 carbon atoms, a cycloalkylene chain having 4 to 7 carbon atoms, or a cycloalkenylene chain having 4 to 7 carbon atoms. The alkylene chain, cycloalkylene chain, alkyl group, and aryl group may be unsubstituted or substituted.

[0101] [ka]

[0102] In the general formulas (41) to (43), X 57 ~X 61 each independently represents an aliphatic structure having 1 to 6 carbon atoms, and X 62 and X 63 R each independently represents an alkylene chain having 1 to 6 carbon atoms or a cycloalkylene chain having 4 to 10 carbon atoms. 93 ~R 97 each independently represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms; R 98 ~R 104 each independently represents a halogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms; R 105 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 106 and R 107 each independently represents a substituent represented by general formula (39), R 108represents a hydrogen atom, a substituent represented by general formula (39), or a substituent represented by general formula (40). m, n, o, p, and q each independently represent an integer of 0 to 10, r and s each independently represent an integer of 0 to 3, and t, u, v, w, and x each independently represent an integer of 0 to 4. The above-mentioned alkylene chains, cycloalkylene chains, alkyl groups, cycloalkyl groups, aryl groups, and aliphatic structures may have heteroatoms and may be either unsubstituted or substituted.

[0103] Of the acid-modified epoxy resins (A2-3) that can be used in the present invention, the acid-modified epoxy resin (A2-3) having a structural unit represented by general formula (43) preferably has a terminal substituent represented by general formula (44) and / or a terminal substituent represented by general formula (45).

[0104] [ka]

[0105] In general formula (44), R 109 represents a substituent represented by general formula (39). In general formula (45), X 64 represents an aliphatic structure having 1 to 6 carbon atoms. 110 represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms; R 111 and R 112 R each independently represents a halogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. 113 represents a substituent represented by general formula (39). α represents an integer of 0 to 10. β and γ represent integers of 0 to 4. In general formula (45), X 64 R is preferably an aliphatic structure having 1 to 4 carbon atoms. 110 is preferably an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and R 111 and R 112are each independently preferably a halogen, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

[0106] The acid-modified epoxy resin (A2-3) that can be used in the present invention preferably contains a structural unit having a fused polycyclic skeleton, from the viewpoints of improving sensitivity during exposure and forming a pattern with a low taper shape after development. Examples of the structural unit having a fused polycyclic skeleton include tricyclo[5.2.1.0] 2,6 ] It is preferable that the resin contains one or more structural units selected from the group consisting of structural units having a decane skeleton, structural units having a naphthalene skeleton, structural units having an anthracene skeleton, and structural units having a fluorene skeleton. When the acid-modified epoxy resin (A2-3) contains these structural units, it is possible to improve sensitivity during exposure and form a pattern with a low taper shape after development. In addition, it is possible to improve halftone characteristics. This is thought to be because the structural units described above significantly interact with the fused polycyclic skeleton-containing photopolymerization initiator (C1-1a) and the fused polycyclic heterocyclic skeleton-containing photopolymerization initiator (C1-1b) described below, thereby improving the compatibility between the alkali-soluble resin and the resin at the start of photopolymerization, and UV curing during exposure proceeds efficiently even deep in the film. When the resin contains a structural unit represented by the above general formula (37), or when Z in the above general formula (38) is contained, 53 contains one or more skeletons selected from the group consisting of a terphenyl skeleton, a naphthalene skeleton, an anthracene skeleton, and a fluorene skeleton, the acid-modified epoxy resin (A2-3) is 2,6 ] The compound contains at least one selected from the group consisting of a structural unit having a decane skeleton, a structural unit having a naphthalene skeleton, a structural unit having an anthracene skeleton, and a structural unit having a fluorene skeleton.

[0107] <Acidic groups derived from carboxylic acids and acidic groups derived from carboxylic acid derivatives> The acid-modified epoxy resin (A2-3) contains structural units derived from carboxylic acid and / or structural units derived from carboxylic acid derivatives in its skeleton, and has a carboxy group and / or a carboxylic acid anhydride group as a functional group that imparts alkali solubility to the resin. The presence of a carboxy group and / or a carboxylic acid anhydride group can improve pattern processability in an alkaline developer and can also improve resolution after development. Other acidic groups may also be present. Examples of acidic groups include sulfonic acid groups, phenolic hydroxyl groups, and hydroxyimide groups. From the viewpoints of improving pattern processability in an alkaline developer and improving resolution after development, phenolic hydroxyl groups are preferred.

[0108] <End-capping agent> In the acid-modified epoxy resin (A2-3), from the viewpoints of improving the storage stability of a coating liquid of the resin composition and improving pattern processability in an alkaline developer, it is preferable that the resin terminals be capped with a terminal capping agent such as a tricarboxylic acid anhydride, a dicarboxylic acid anhydride, or a monocarboxylic acid.

[0109] The acid-modified epoxy resin (A2-3) preferably contains in its skeleton a structural unit derived from an aromatic carboxylic acid and / or a structural unit derived from an aromatic carboxylic acid derivative, from the viewpoints of improving the heat resistance of the cured film due to the heat resistance of the aromatic group and improving halftone characteristics. The Mw of the acid-modified epoxy resin (A2-3), as measured by GPC in terms of polystyrene, is preferably 500 or more, from the viewpoints of improving the resolution after development and the reliability of the light-emitting device. On the other hand, the Mw is preferably 50,000 or less, from the viewpoints of forming a pattern with a low taper shape after thermal curing and improving the pattern processability in an alkaline developer. The acid-modified epoxy resin (A2-3) can be synthesized by a known method.

[0110] <(A2-3) Specific Examples of Acid-Modified Epoxy Resins> (A2-3) Examples of acid-modified epoxy resins include "KAYARAD" (registered trademark) PCR-1222H, CCR-1171H, TCR-1348H, ZAR-1494H, ZFR-1401H, ZCR-1798H, ZXR-1807H, ZCR-6002H, and ZCR-8001H (all manufactured by Nippon Kayaku Co., Ltd.), and "NK OLIGO" (registered trademark) EA-6340, EA-7140, and EA-7340 (all manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0111] <(A2-4) Acrylic resin> Examples of the acrylic resin (A2-4) that can be used in the present invention include acrylic resins obtained by radical copolymerization of one or more copolymerization components selected from the group consisting of copolymerization components having an acidic group, copolymerization components derived from a (meth)acrylic acid ester, and other copolymerization components.

[0112] Examples of the copolymerization component having an acidic group, the copolymerization component derived from a (meth)acrylic acid ester, and other copolymerization components include the compounds described in WO 2017 / 057281.

[0113] The acrylic resin (A2-4) preferably contains a structural unit represented by general formula (61) and / or a structural unit represented by general formula (62), from the viewpoints of improving sensitivity during exposure and improving the mechanical properties of the cured film.

[0114] [ka]

[0115] In the general formulas (61) and (62), Rd 1 and Rd 2 R each independently represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 15 carbon atoms, or an aryl group having 6 to 15 carbon atoms, each having an ethylenically unsaturated double bond group. 200 ~R 205X each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. 90 and X 91 each independently represents a direct bond, an alkylene chain having 1 to 10 carbon atoms, a cycloalkylene chain having 4 to 10 carbon atoms, or an arylene chain having 6 to 15 carbon atoms.

[0116] In the general formulas (61) and (62), Rd 1 and Rd 2 are each independently preferably an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, each having an ethylenically unsaturated double bond group. 200 ~R 205 are each independently preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, or an aryl group having 6 to 10 carbon atoms. 90 and X 91 are each independently preferably a direct bond, an alkylene chain having 1 to 6 carbon atoms, a cycloalkylene chain having 4 to 7 carbon atoms, or an arylene chain having 6 to 10 carbon atoms. The above-mentioned alkyl groups, cycloalkyl groups, aryl groups, alkylene chains, cycloalkylene chains, and arylene chains may have a heteroatom, and may be either unsubstituted or substituted.

[0117] <Structural Units Derived from Copolymerization Components Having Acidic Groups> From the viewpoints of improving pattern processability in an alkaline developer and improving resolution after development, the acrylic resin (A2-4) preferably contains a structural unit derived from a copolymer component having an acidic group, and the acrylic resin (A2-4) preferably has an acidic group. Examples of the acidic group include a carboxy group, a carboxylic acid anhydride group, a sulfonic acid group, a phenolic hydroxyl group, and a hydroxyimide group. From the viewpoints of improving pattern processability in an alkaline developer and improving resolution after development, a carboxy group, a carboxylic acid anhydride group, or a phenolic hydroxyl group is preferred, and a carboxy group or a carboxylic acid anhydride group is more preferred.

[0118] <Introduction of an ethylenically unsaturated double bond group> The acrylic resin (A2-4) that can be used in the present invention preferably has an ethylenically unsaturated double bond group. By incorporating an acrylic resin (A2-4) having an ethylenically unsaturated double bond group into a negative-tone photosensitive resin composition, sensitivity during exposure can be improved and a pattern with a low taper shape can be formed after development. Resins obtained by subjecting an acidic group in the acrylic resin (A2-4) to a ring-opening addition reaction with an unsaturated compound having an ethylenically unsaturated double bond group and an epoxy group are preferred. By reacting an epoxy group with the acidic group, an acrylic resin (A2-4) without an epoxy group can be obtained while incorporating an ethylenically unsaturated double bond group.

[0119] When the (A2-4) acrylic resin contains a carboxy group, it is preferably an (A2-4) acrylic resin without an epoxy group, from the viewpoints of improving pattern processability in an alkaline developer and improving the storage stability of the coating liquid. Furthermore, from the viewpoints of improving the heat resistance of the cured film due to the heat resistance of the aromatic group and improving halftone characteristics, it is preferable for the (A2-4) acrylic resin to contain a structural unit derived from a copolymerization component having an aromatic group. Furthermore, from the viewpoints of improving the heat resistance of the cured film due to the heat resistance and transparency of the alicyclic group and improving sensitivity during exposure, it is also preferable for the (A2-4) acrylic resin to contain a structural unit derived from a copolymerization component having an alicyclic group. From the viewpoints of improving resolution after development and improving the reliability of light-emitting devices, the Mw of the (A2-4) acrylic resin is preferably 1,000 or more in terms of polystyrene equivalent as measured by GPC. On the other hand, from the viewpoints of forming a pattern with a low taper shape after thermal curing and improving pattern processability in an alkaline developer, the Mw is preferably 50,000 or less. The (A2-4) acrylic resin can be synthesized by a known method.

[0120] <Other alkali-soluble resins> The negative-type photosensitive resin composition of the present invention may further contain other alkali-soluble resins as the alkali-soluble resin (A). From the viewpoints of forming a pattern with a low taper shape after development and improving halftone characteristics, the other alkali-soluble resins preferably contain one or more resins selected from the group consisting of novolac resins, resole resins, and polyhydroxystyrenes, and more preferably contain novolac resins. In the present invention, the novolac resins, resole resins, and polyhydroxystyrenes may be single resins or copolymers thereof.

[0121] The novolak resin, resol resin, and polyhydroxystyrene that can be used in the present invention preferably have a phenolic hydroxyl group as the alkali-soluble group, from the viewpoint of improving halftone characteristics.

[0122] The novolac resin, resole resin, and polyhydroxystyrene used in the present invention may have an acidic group other than a phenolic hydroxyl group. Examples of the acidic group include a carboxy group, a carboxylic acid anhydride group, a sulfonic acid group, and a hydroxyimide group. From the viewpoint of improving pattern processability in an alkaline developer and improving resolution after development, a carboxy group or a carboxylic acid anhydride group is preferred. Furthermore, the novolac resin, resole resin, and polyhydroxystyrene used in the present invention preferably have an ethylenically unsaturated double bond group. The presence of an ethylenically unsaturated double bond group can improve sensitivity during exposure and form a pattern with a low taper shape after development.

[0123] <Content ratio of (A1) first resin, (A2) second resin, and other alkali-soluble resins> In the negative-type photosensitive resin composition of the present invention, the content of the first resin (A1) relative to the total 100% by mass of the first resin (A1) and the second resin (A2) is preferably 25% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, even more preferably 70% by mass or more, and particularly preferably 80% by mass or more. A content of 25% by mass or more can improve the heat resistance of the cured film and the reliability of the light-emitting device. In addition, halftone characteristics can be improved. On the other hand, the content of the first resin (A1) is preferably 99% by mass or less, more preferably 98% by mass or less, even more preferably 97% by mass or less, even more preferably 95% by mass or less, and particularly preferably 90% by mass or less. A content of 99% by mass or less can improve sensitivity during exposure and form a pattern with a low taper shape after development. In addition, halftone characteristics can be improved.

[0124] In the negative-type photosensitive resin composition of the present invention, the content of the other alkali-soluble resins relative to the total 100% by mass of the first resin (A1), the second resin (A2), and the other alkali-soluble resins is preferably 1% by mass or more, more preferably 5% by mass or more, from the viewpoints of forming a pattern with a low taper shape after development and improving halftone characteristics. On the other hand, the content of the other alkali-soluble resins is preferably 30% by mass or less, more preferably 15% by mass or less, from the viewpoints of improving sensitivity during exposure and improving the reliability of the light-emitting device.

[0125] <<(B) Radical polymerizable compound>> The negative-tone photosensitive resin composition of the present invention preferably further contains (B) a radically polymerizable compound. The (B) radically polymerizable compound refers to a compound having multiple ethylenically unsaturated double bond groups in the molecule. During exposure, radicals generated from the (C1) photopolymerization initiator described below cause radical polymerization of the (B) radically polymerizable compound, and the exposed areas of the resin composition film become insoluble in an alkaline developer, thereby forming a negative-tone pattern.

[0126] By including a (B) radically polymerizable compound, UV curing during exposure is accelerated, thereby improving sensitivity during exposure. In addition, the crosslinking density after thermal curing is improved, thereby improving the hardness of the cured film. As the (B) radically polymerizable compound, a compound having a (meth)acrylic group, which facilitates radical polymerization, is preferred. From the viewpoints of improving sensitivity during exposure and improving the hardness of the cured film, a compound having two or more (meth)acrylic groups in the molecule is more preferred. From the viewpoints of improving sensitivity during exposure and improving the hardness of the cured film, the double bond equivalent of the (B) radically polymerizable compound is preferably 80 to 800 g / mol.

[0127] The content of the (B) radical polymerizable compound in the negative photosensitive resin composition of the present invention is preferably 15 parts by mass or more, more preferably 25 parts by mass or more, from the viewpoints of improving sensitivity during exposure and forming a pattern with a low taper shape after development, where the total of the (A) alkali-soluble resin and the (B) radical polymerizable compound is taken as 100 parts by mass. On the other hand, the content of the (B) radical polymerizable compound is preferably 65 parts by mass or less, more preferably 55 parts by mass or less, from the viewpoints of improving the heat resistance of the cured film and the reliability of the light-emitting device.

[0128] <(B1) Fluorene Skeleton-Containing Radical Polymerizable Compound and (B2) Indane Skeleton-Containing Radical Polymerizable Compound> The negative-type photosensitive resin composition of the present invention preferably further contains, as the radical polymerizable compound (B), one or more compounds selected from the group consisting of (B1) a fluorene skeleton-containing radical polymerizable compound and (B2) an indane skeleton-containing radical polymerizable compound. The (B1) fluorene skeleton-containing radical polymerizable compound refers to a compound having multiple ethylenically unsaturated double bond groups and a fluorene skeleton in the molecule. The (B2) indane skeleton-containing radical polymerizable compound refers to a compound having multiple ethylenically unsaturated double bond groups and an indane skeleton in the molecule. From the viewpoints of improving sensitivity during exposure and suppressing residues after development, the (B1) fluorene skeleton-containing radical polymerizable compound and the (B2) indane skeleton-containing radical polymerizable compound are preferably compounds having two or more compounds having (meth)acrylic groups in the molecule.

[0129] Incorporation of one or more compounds selected from the group consisting of (B1) a fluorene skeleton-containing radical polymerizable compound and (B2) an indane skeleton-containing radical polymerizable compound improves sensitivity during exposure and enables the formation of a pattern with a low taper shape after development, as well as the formation of a pattern with a low taper shape after thermal curing. In addition, halftone characteristics can be improved. Furthermore, when a benzofuranone-based black pigment (D1a-1a) is incorporated as the black agent (Da) described below, pigment-derived development residues may be generated due to the pigment's insufficient alkali resistance. In such cases, incorporation of one or more compounds selected from the group consisting of (B3) a flexible chain-containing aliphatic radical polymerizable compound and (B1) a fluorene skeleton-containing radical polymerizable compound and (B2) an indane skeleton-containing radical polymerizable compound can suppress the generation of pigment-derived development residues.

[0130] This is thought to be because the fluorene skeleton and indane skeleton interact significantly with the fused polycyclic skeleton of the (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator and the fused polycyclic heterocyclic skeleton of the (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiator, which will be described later, thereby increasing the compatibility between the radical polymerizable compound and the photopolymerization initiator, and allowing UV curing during exposure to proceed efficiently even deep within the film.

[0131] Examples of the (B1) fluorene skeleton-containing radical polymerizable compound include 9,9-bis[4-(2-(meth)acryloxyethoxy)phenyl]fluorene, 9,9-bis[4-(3-(meth)acryloxypropoxy)phenyl]fluorene, 9,9-bis(4-(meth)acryloxyphenyl)fluorene, 9,9-bis[4-(2-hydroxy-3-(meth)acryloxypropoxy)phenyl]fluorene, and 9,9-bis[3,4-bis(2-(meth)acryloxyethoxy)phenyl]fluorene.

[0132] Examples of the (B2) indane skeleton-containing radical polymerizable compound include 1,1-bis[4-(2-(meth)acryloxyethoxy)phenyl]indan, 1,1-bis(4-(meth)acryloxyphenyl)indan, 1,1-bis[4-(2-hydroxy-3-(meth)acryloxypropoxy)phenyl]indan, 1,1-bis[3,4-bis(2-(meth)acryloxyethoxy)phenyl]indan, 2,2-bis[4-(2-(meth)acryloxyethoxy)phenyl]indan, and 2,2-bis(4-(meth)acryloxyphenyl)indan.

[0133] The total content of the (B1) fluorene skeleton-containing radical polymerizable compound and the (B2) indane skeleton-containing radical polymerizable compound in the negative-type photosensitive resin composition of the present invention is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, per 100 parts by mass of the (A) alkali-soluble resin and the (B) radical polymerizable compound, from the viewpoints of forming a pattern with a low taper shape after development and improving halftone characteristics. On the other hand, the total content of the (B1) fluorene skeleton-containing radical polymerizable compound and the (B2) indane skeleton-containing radical polymerizable compound is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, from the viewpoint of suppressing residues after development.

[0134] <(B3) Flexible Chain-Containing Aliphatic Radically Polymerizable Compound> The negative-type photosensitive resin composition of the present invention preferably further contains (B3) a flexible-chain-containing aliphatic radical-polymerizable compound as the (B) radical-polymerizable compound. The (B3) flexible-chain-containing aliphatic radical-polymerizable compound refers to a compound having multiple ethylenically unsaturated double bond groups in the molecule and a flexible skeleton such as an aliphatic chain or an oxyalkylene chain. The (B3) flexible-chain-containing aliphatic radical-polymerizable compound is preferably a compound having (I) a structure derived from a compound having at least two hydroxy groups in the molecule, (II) at least two ethylenically unsaturated double bond groups, and (III) at least one aliphatic chain.

[0135] By incorporating the (B3) flexible-chain-containing aliphatic radical-polymerizable compound, UV curing during exposure proceeds efficiently, improving sensitivity during exposure and halftone characteristics. Additionally, when the (D1) pigment is incorporated as the (D) colorant (described below), the (D1) pigment is fixed in the cured portion by crosslinking during UV curing of the (B3) flexible-chain-containing aliphatic radical-polymerizable compound, thereby suppressing the generation of residues after development originating from the (D1) pigment. Furthermore, when the (Da) black agent (described below) is incorporated as the (D1a-1a) benzofuranone-based black pigment, the generation of residues after development originating from the pigment, due to the pigment's insufficient alkali resistance, can also be suppressed.

[0136] As the (B3) flexible chain-containing aliphatic radical polymerizable compound, a compound having in the molecule (III) a group represented by general formula (24) as at least one aliphatic chain and (II) three or more groups represented by general formula (25) as at least two ethylenically unsaturated double bond groups is preferred.

[0137] [ka]

[0138] In general formula (24), R 125 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. 17 represents a group represented by general formula (29) or a group represented by general formula (30). a represents an integer of 1 to 10, b represents an integer of 1 to 4, c represents 0 or 1, d represents an integer of 1 to 4, and e represents 0 or 1. When c is 0, d is 1. In general formula (25), R 126 ~R 128 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. 129 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. In terms of improving sensitivity during exposure and suppressing residues after development, in general formula (24), c is preferably 1 and e is preferably 1. In general formula (25), R 126 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group. 127 and R 128 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom. 129 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group.

[0139] From the viewpoints of improving sensitivity during exposure, improving halftone characteristics, and suppressing residues after development, the (B3) flexible chain-containing aliphatic radical polymerizable compound preferably has at least one lactone-modified chain and / or at least one lactam-modified chain as the (III) at least one aliphatic chain. When c is 1 and e is 1 in the above general formula (24), the (B3) flexible chain-containing aliphatic radical polymerizable compound has at least one lactone-modified chain and / or at least one lactam-modified chain.

[0140] From the viewpoint of improving sensitivity during exposure, the number of ethylenically unsaturated double bond groups contained in the molecule of (B3) flexible chain-containing aliphatic radical polymerizable compound is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. On the other hand, from the viewpoint of forming a pattern with a low taper shape after thermal curing, the number of ethylenically unsaturated double bond groups contained in the molecule of (B3) flexible chain-containing aliphatic radical polymerizable compound is preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less.

[0141] (B3) Flexible chain-containing aliphatic radical polymerizable compounds include compounds having three or more ethylenically unsaturated double bond groups in the molecule, such as ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, ε-caprolactone-modified dipentaerythritol hexa(meth)acrylate, δ-valerolactone-modified dipentaerythritol hexa(meth)acrylate, γ-butyrolactone-modified dipentaerythritol hexa(meth)acrylate, β-propiolactone-modified dipentaerythritol hexa(meth)acrylate, ε-caprolactone-modified dipentaerythritol hexa(meth)acrylate, Examples of the copolymer include dipentaerythritol hexa(meth)acrylate, ε-caprolactone-modified dipentaerythritol penta(meth)acrylate, ε-caprolactone-modified trimethylolpropane tri(meth)acrylate, ε-caprolactone-modified ditrimethylolpropane tetra(meth)acrylate, ε-caprolactone-modified glycerin tri(meth)acrylate, ε-caprolactone-modified pentaerythritol tri(meth)acrylate, ε-caprolactone-modified pentaerythritol tetra(meth)acrylate, and ε-caprolactone-modified 1,3,5-tris((meth)acryloxyethyl)isocyanuric acid.

[0142] Examples of compounds having two ethylenically unsaturated double bond groups in the molecule include ε-caprolactone-modified hydroxypivalic acid neopentyl glycol di(meth)acrylate, ε-caprolactone-modified trimethylolpropane di(meth)acrylate, ε-caprolactone-modified ditrimethylolpropane di(meth)acrylate, ε-caprolactone-modified glycerin di(meth)acrylate, ε-caprolactone-modified pentaerythritol di(meth)acrylate, ε-caprolactone-modified dimethylol-tricyclodecane di(meth)acrylate, and ε-caprolactone-modified 1,3-bis((meth)acryloxyethyl)isocyanuric acid.

[0143] The content of the (B3) flexible chain-containing aliphatic radical polymerizable compound in the negative-type photosensitive resin composition of the present invention is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, per 100 parts by mass of the total of the (A) alkali-soluble resin and the (B) radical polymerizable compound, from the viewpoints of improving sensitivity during exposure, suppressing residue after development, and improving halftone characteristics. On the other hand, the content of the (B3) flexible chain-containing aliphatic radical polymerizable compound is preferably 40 parts by mass or less, more preferably 35 parts by mass or less, from the viewpoint of forming a pattern with a low taper shape after thermal curing.

[0144] <(B4) Alicyclic Group-Containing Radically Polymerizable Compound> The negative-type photosensitive resin composition of the present invention preferably further contains (B4) an alicyclic group-containing radical polymerizable compound as the (B) radical polymerizable compound. The (B4) alicyclic group-containing radical polymerizable compound refers to a compound having multiple ethylenically unsaturated double bond groups and an alicyclic group in the molecule. From the viewpoints of improving sensitivity during exposure and suppressing residues after development, the (B4) alicyclic group-containing radical polymerizable compound is preferably a compound having two or more compounds having (meth)acrylic groups in the molecule.

[0145] The alicyclic group contained in the molecule of the (B4) alicyclic group-containing radical polymerizable compound is preferably a fused polycyclic alicyclic skeleton. The presence of a fused polycyclic alicyclic skeleton improves sensitivity during exposure and enables the formation of a pattern with a low taper shape after development. In addition, halftone characteristics can be improved. This is thought to be due to the significant interaction between the fused polycyclic alicyclic skeleton and the fused polycyclic skeleton of the (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator and the fused polycyclic heterocyclic skeleton of the (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiator, which will be described later. This enhances the compatibility between the radical polymerizable compound and the photopolymerization initiator, allowing efficient UV curing during exposure even deep within the film.

[0146] Examples of the condensed polycyclic alicyclic skeleton of the (B4) alicyclic group-containing radical polymerizable compound include a bicyclo[4.3.0]nonane skeleton, a bicyclo[5.4.0]undecane skeleton, a bicyclo[2.2.2]octane skeleton, a tricyclo[5.2.1.0] 2,6 ]decane skeleton, pentacyclopentadecane skeleton, adamantane skeleton, or hydroxyadamantane skeleton.

[0147] Examples of the alicyclic group-containing radical polymerizable compound (B4) having a condensed polycyclic alicyclic skeleton include dimethylol-bicyclo[4.3.0]nonane di(meth)acrylate, dimethylol-bicyclo[5.4.0]undecane di(meth)acrylate, dimethylol-bicyclo[2.2.2]octane di(meth)acrylate, dimethylol-tricyclo[5.2.1.0 2,6 ]decane di(meth)acrylate, dimethylol-pentacyclopentadecane di(meth)acrylate, 1,3-adamantane di(meth)acrylate, 1,3,5-adamantane tri(meth)acrylate, or 5-hydroxy-1,3-adamantane di(meth)acrylate.

[0148] The content of the alicyclic group-containing radical polymerizable compound (B4) in the negative-type photosensitive resin composition of the present invention is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, per 100 parts by mass of the total of the alkali-soluble resin (A) and the radical polymerizable compound (B), from the viewpoints of forming a pattern with a low taper shape after development and improving halftone characteristics. On the other hand, the content of the alicyclic group-containing radical polymerizable compound (B4) is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, from the viewpoint of suppressing residue after development. <<(C) Photosensitizer>> <(C1) Photopolymerization initiator> The negative-tone photosensitive resin composition of the present invention contains (C1) a photopolymerization initiator as (C) a photosensitizer. The (C1) photopolymerization initiator refers to a compound that generates radicals through bond cleavage and / or reaction upon exposure. By including the (C1) photopolymerization initiator, radical polymerization of the above-mentioned (B) radically polymerizable compound proceeds, and exposed areas of the resin composition film become insoluble in alkaline developer, thereby forming a negative-tone pattern. Furthermore, UV curing during exposure is promoted, thereby improving sensitivity during exposure.

[0149] The (C1) photopolymerization initiator is preferably, for example, a benzyl ketal-based photopolymerization initiator, an α-hydroxyketone-based photopolymerization initiator, an α-aminoketone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, a biimidazole-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 ketoester-based photopolymerization initiator, or a benzoate ester-based photopolymerization initiator. From the viewpoint of improving sensitivity during exposure, an α-hydroxyketone-based photopolymerization initiator, an α-aminoketone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, a biimidazole-based photopolymerization initiator, or an oxime ester-based photopolymerization initiator is more preferred, and an oxime ester-based photopolymerization initiator is even more preferred.

[0150] The content of the (C1) photopolymerization initiator in the negative-type photosensitive resin composition of the present invention is preferably 0.5 parts by mass or more, more preferably 5 parts by mass or more, based on 100 parts by mass of the total of the (A) alkali-soluble resin and the (B) radical-polymerizable compound, from the viewpoint of improving sensitivity during exposure. On the other hand, the content of the (C1) photopolymerization initiator is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, from the viewpoint of improving resolution after development and forming a pattern with a low taper shape after development.

[0151] <(C1-1) Oxime ester photopolymerization initiators> The negative-type photosensitive resin composition of the present invention contains, as the (C1) photopolymerization initiator, two or more (C1-1) oxime ester photopolymerization initiators with different structures. The (C1-1) oxime ester photopolymerization initiator refers to a compound having an oxime ester skeleton in the molecule, which undergoes bond cleavage and / or reaction upon exposure to generate radicals. The inclusion of two or more (C1-1) oxime ester photopolymerization initiators can improve sensitivity during exposure. This is presumably because the energy of UV light during exposure can be more efficiently utilized for radical curing than when a single (C1-1) oxime ester photopolymerization initiator is contained. (C1-1a) Photopolymerization initiators containing a fused polycyclic skeleton, and (C1-1b) Photopolymerization initiators containing a fused polycyclic heterocyclic skeleton In the negative-type photosensitive resin composition of the present invention, the (C1-1) oxime ester photopolymerization initiator contains at least (C1-1a) a photopolymerization initiator containing a fused polycyclic skeleton and (C1-1b) a photopolymerization initiator containing a fused polycyclic heterocyclic skeleton. The (C1-1a) photopolymerization initiator containing a fused polycyclic skeleton refers to a compound that has a fused polycyclic skeleton in its molecule and generates radicals upon exposure to bond cleavage and / or reaction. The (C1-1b) photopolymerization initiator containing a fused polycyclic heterocyclic skeleton refers to a compound that has a fused polycyclic heterocyclic skeleton in its molecule and generates radicals upon exposure to bond cleavage and / or reaction. The fused polycyclic skeleton refers to a cyclic skeleton formed by bonding two or more rings together, with one or more atoms constituting each ring shared by the two or more rings. The fused polycyclic skeleton has two or more bridgehead atoms among the atoms constituting the ring. Examples of the fused polycyclic skeleton include a bicyclo skeleton, a tricyclo skeleton, a tetracyclo skeleton, a pentacyclo skeleton, and a spiro skeleton. A fused polycyclic heterocyclic skeleton refers to a cyclic skeleton in which the atoms constituting the ring contain heteroatoms other than carbon atoms and hydrogen atoms, among the fused polycyclic skeletons. In the fused polycyclic heterocyclic skeleton, examples of the heteroatoms other than carbon atoms and hydrogen atoms include oxygen atoms, nitrogen atoms, sulfur atoms, fluorine atoms, silicon atoms, phosphorus atoms, boron atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0152] By including at least a (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator and a (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiator in the (C1-1) oxime ester photopolymerization initiator, sensitivity during exposure can be improved and residue deposition at pattern openings after thermal curing can be suppressed. This is presumably because the two or more (C1-1) oxime ester photopolymerization initiators allow efficient UV curing, reducing unreacted (B) radically polymerizable compound. Furthermore, the heat resistance of the fused polycyclic skeleton and fused polycyclic heterocyclic skeleton is thought to suppress degassing and other problems caused by thermal decomposition of the photopolymerization initiator.

[0153] The (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator and the (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiator each have a structure in which at least one oxime ester structure or at least one oxime ester carbonyl structure is bonded to the fused polycyclic skeleton and the fused polycyclic heterocyclic skeleton. Having a structure in which at least one oxime ester structure or at least one oxime ester carbonyl structure is bonded to the fused polycyclic skeleton and the fused polycyclic heterocyclic skeleton can improve sensitivity during exposure and form a pattern with a low taper shape after development. This is thought to be because the energy of UV light absorbed by the fused polycyclic skeleton and the fused polycyclic heterocyclic skeleton during exposure is efficiently transferred, allowing efficient radical generation by bond cleavage and / or reaction of the oxime ester structure or the oxime ester carbonyl structure. From the viewpoints of improving sensitivity during exposure and forming a pattern with a low taper shape after development, it is preferable that the compound has a structure in which at least one oxime ester structure is bonded to one or more selected from the group consisting of the fused polycyclic skeleton and the fused polycyclic heterocyclic skeleton. From the viewpoint of improving sensitivity during exposure, it is also preferable that the compound has a structure in which two or more oxime ester structures or two or more oxime ester carbonyl structures are bonded to the fused polycyclic skeleton and the fused polycyclic heterocyclic skeleton. Note that a compound in which an oxime ester structure is bonded to a fused polycyclic skeleton or a fused polycyclic heterocyclic skeleton is referred to as an α-oxime compound. A compound in which an oxime ester carbonyl structure is bonded to a fused polycyclic skeleton or a fused polycyclic heterocyclic skeleton (i.e., a compound in which an oxime ester structure is bonded via a carbonyl structure) is referred to as a β-oxime compound.

[0154] From the viewpoints of improving sensitivity during exposure and forming a pattern with a low taper shape after development, the (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator and the (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiator preferably have a structure in which at least one oxime ester structure or at least one oxime ester carbonyl structure is bonded to the fused polycyclic skeleton or the fused polycyclic heterocyclic skeleton, and at least one group represented by general formula (11) is bonded to the fused polycyclic skeleton or the fused polycyclic heterocyclic skeleton. The group represented by general formula (11) is a group having an oxime ester structure, and has a structure that undergoes bond cleavage and / or reaction by UV light during exposure to generate radicals.

[0155] [ka]

[0156] In general formula (11), X 7 represents a direct bond, an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 10 carbon atoms, or an arylene group having 6 to 15 carbon atoms. 29 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a haloalkoxy group having 1 to 10 carbon atoms, a heterocyclic group having 4 to 10 carbon atoms, a heterocyclic oxy group having 4 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or a nitro group. 30 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. a represents 0 or 1, and b represents an integer of 1 to 10.

[0157] In general formula (11), X 7 R is preferably an alkylene group having 1 to 10 carbon atoms from the viewpoint of improving solubility in a solvent, or is preferably an arylene group having 6 to 15 carbon atoms from the viewpoint of improving sensitivity during exposure. 29From the viewpoint of improving solubility in a solvent, R is preferably a cycloalkyl group having 4 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or a haloalkoxy group having 1 to 10 carbon atoms. 29 From the viewpoints of improving sensitivity during exposure and forming a pattern with a low taper shape after development, R is preferably an alkenyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a haloalkoxy group having 1 to 10 carbon atoms, a heterocyclic group having 4 to 10 carbon atoms, a heterocyclic oxy group having 4 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or a nitro group. 30 From the viewpoint of improving sensitivity during exposure, a is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group. From the viewpoint of improving sensitivity during exposure, a is preferably 0.

[0158] From the viewpoint of improving sensitivity during exposure, one or more selected from the group consisting of (C1-1a) fused polycyclic skeleton-containing photopolymerization initiators and (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiators preferably have a substituent containing an unshared electron pair capable of conjugating with the fused polycyclic skeleton or the fused polycyclic heterocyclic skeleton. Similarly, from the viewpoint of improving sensitivity during exposure, they preferably have a substituent containing a π bond capable of conjugating with the fused polycyclic skeleton or the fused polycyclic heterocyclic skeleton. Examples of the substituent containing an unshared electron pair include halogen, amino, hydroxy, alkoxy, and mercapto. Examples of the substituent containing a π bond include an aryl group, nitro, cyano, carboxy, formyl, alkylcarbonyl, alkyloxycarbonyl, and sulfo groups. Further, examples of the substituent containing a π bond include a structure in which a carbon atom on a fused polycyclic skeleton or a carbon atom on a fused polycyclic heterocyclic skeleton forms an unsaturated double bond containing a π bond with a nitrogen atom, an oxygen atom, or a sulfur atom (e.g., a dialkylcarbonyl group or a dialkylthiocarbonyl group).

[0159] The (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator has a fused polycyclic skeleton containing an aromatic skeleton, and the fused polycyclic skeleton is composed only of carbon and hydrogen atoms. The (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator has a fused polycyclic skeleton containing an aromatic skeleton, which allows for the formation of a pattern with a low taper shape after development and improves halftone characteristics. This is presumably because the aromatic skeleton allows the (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator to be compatible with the entire film, allowing UV curing to proceed deep into the film upon exposure. Furthermore, the fused polycyclic skeleton composed only of carbon and hydrogen atoms is thought to reduce polarity and improve hydrophobicity, thereby suppressing side etching during alkaline development.

[0160] The (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator preferably has one or more fused polycyclic skeletons selected from the group consisting of a fluorene skeleton, a benzofluorene skeleton, a dibenzofluorene skeleton, an indene skeleton, an indane skeleton, a benzoindene skeleton, a benzoindene skeleton, a dihydroanthracene skeleton, a dihydrobenzanthracene skeleton, a dihydrophenanthrene skeleton, a dihydrobenzophenanthrene skeleton, a dihydronaphthalene skeleton, a dihydrobenzonaphthalene skeleton, a tetrahydronaphthalene skeleton, and a tetrahydrobenzonaphthalene skeleton, and more preferably has one or more fused polycyclic skeletons selected from the group consisting of a fluorene skeleton, a benzofluorene skeleton, a dibenzofluorene skeleton, an indene skeleton, an indane skeleton, a benzoindene skeleton, and a benzoindene skeleton. Having the above-described structure enables the formation of a pattern with a low taper shape after development and improves halftone characteristics. Furthermore, the adhesion of residues at pattern openings after thermal curing can be suppressed.

[0161] The (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator preferably has one or more skeletons selected from the group consisting of a fluorene skeleton, a benzofluorene skeleton, and a dibenzofluorene skeleton, from the viewpoint of photobleachability. Photobleachability refers to a decrease in absorbance in the ultraviolet-visible region due to bond cleavage and / or reaction caused by UV light during exposure. Having photobleachability can improve sensitivity during exposure and form a pattern with a low taper shape after development. In addition, halftone characteristics can be improved. Furthermore, residue adhesion at pattern openings after thermal curing can be suppressed. This is presumably because radicals are generated during exposure, simultaneously decreasing the absorbance of UV light, allowing UV curing to proceed deep into the film.

[0162] In the negative-type photosensitive resin composition of the present invention, the content of the fused polycyclic skeleton-containing photopolymerization initiator (C1-1a) in the photopolymerization initiator (C1) is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, even more preferably 17% by mass or more, and particularly preferably 20% by mass or more. A content of 5% by mass or more can improve sensitivity during exposure and form a pattern with a low taper shape after development. In addition, halftone characteristics can be improved. Furthermore, adhesion of residues at pattern openings after thermal curing can be suppressed. Meanwhile, the content of the fused polycyclic skeleton-containing photopolymerization initiator (C1-1a) is preferably 45% by mass or less, more preferably 43% by mass or less, even more preferably 40% by mass or less, even more preferably 38% by mass or less, and particularly preferably 35% by mass or less. A content of 45% by mass or less can improve sensitivity during exposure and form a pattern with a low taper shape after development. In addition, halftone characteristics can be improved, and adhesion of residues to pattern openings after thermal curing can be suppressed.

[0163] The (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiator preferably has a fused polycyclic heterocyclic skeleton containing an aromatic skeleton, and the fused polycyclic heterocyclic skeleton contains at least carbon and hydrogen atoms, and further contains one or more heteroatoms selected from the group consisting of oxygen, nitrogen, sulfur, fluorine, silicon, and phosphorus. The (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiator has a fused polycyclic skeleton containing an aromatic skeleton, which enables the formation of a pattern with a low taper shape after development and improves halftone characteristics. This is presumably because the aromatic skeleton allows the (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiator to be compatible with the entire film, allowing UV curing to proceed deep into the film upon exposure. Furthermore, it is believed that the fused polycyclic heterocyclic skeleton contains at least carbon atoms and hydrogen atoms, and further contains one or more heteroatoms selected from the group consisting of oxygen atoms, nitrogen atoms, sulfur atoms, fluorine atoms, silicon atoms, and phosphorus atoms, thereby improving compatibility with radical polymerizable compounds and allowing UV curing during exposure to proceed efficiently even in deep parts of the film.

[0164] Examples of the (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiator include, as the fused polycyclic heterocyclic skeleton, a carbazole skeleton, a dibenzofuran skeleton, a dibenzothiophene skeleton, a benzocarbazole skeleton, a naphthobenzofuran skeleton, a naphthobenzothiophene skeleton, an indole skeleton, a benzofuran skeleton, a benzothiophene skeleton, an indoline skeleton, a benzodihydrofuran skeleton, a benzodihydrothiophene skeleton, a benzoindole skeleton, a naphthofuran skeleton, a naphthothiophene skeleton, a benzoindoline skeleton, a naphthodihydrofuran skeleton, a naphthodihydrothiophene skeleton, an acridine skeleton, a xanthene skeleton, a thioxanthene skeleton, a benzoacridine skeleton, a benzoxanthene skeleton, a benzothioxanthene skeleton, and a quinoline skeleton. Preferably, the compound has one or more skeletons selected from the group consisting of a benzopyran skeleton, a benzothiopyran skeleton, a benzoquinoline skeleton, a naphthopyran skeleton, a naphthothiopyran skeleton, a dihydroquinoline skeleton, a benzodihydropyran skeleton, a benzodihydrothiopyran skeleton, a benzodihydroquinoline skeleton, a naphthodihydropyran skeleton, and a naphthodihydrothiopyran skeleton; more preferably, the compound has one or more skeletons selected from the group consisting of a carbazole skeleton, a benzocarbazole skeleton, an indole skeleton, an indoline skeleton, a benzoindole skeleton, and a benzoindoline skeleton; and even more preferably, the compound has one or more skeletons selected from the group consisting of a benzocarbazole skeleton, a benzoindole skeleton, and a benzoindoline skeleton. Having the above-described structure allows for the formation of a pattern with a low taper shape after development and improves halftone characteristics. Furthermore, the compound can suppress the adhesion of residues at pattern openings after thermal curing.

[0165] In the negative-type photosensitive resin composition of the present invention, the content of the (C1-1b) photopolymerization initiator having a fused polycyclic heterocyclic skeleton in the (C1) photopolymerization initiator is preferably 55% by mass or more, more preferably 57% by mass or more, even more preferably 60% by mass or more, even more preferably 62% by mass or more, and particularly preferably 65% by mass or more. A content of 55% by mass or more can improve sensitivity during exposure and form a pattern with a low taper shape after development. In addition, halftone characteristics can be improved. Furthermore, adhesion of residues at pattern openings after thermal curing can be suppressed. Meanwhile, the content of the (C1-1b) photopolymerization initiator having a fused polycyclic heterocyclic skeleton is preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 85% by mass or less, even more preferably 83% by mass or less, and particularly preferably 80% by mass or less. When the content is 95% by mass or less, the sensitivity during exposure can be improved, a pattern with a low taper shape can be formed after development, halftone characteristics can be improved, and adhesion of residues at pattern openings after thermal curing can be suppressed.

[0166] The (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator and the (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiator preferably have one or more selected from the group consisting of a nitro group, a naphthylcarbonyl structure, a trimethylbenzoyl structure, a thiophenylcarbonyl structure, and a furylcarbonyl structure. Having one or more selected from the group consisting of a nitro group, a naphthylcarbonyl structure, a trimethylbenzoyl structure, a thiophenylcarbonyl structure, and a furylcarbonyl structure can improve sensitivity during exposure and form a pattern with a low taper shape after development. In addition, halftone characteristics can be improved. This is presumably because the conjugated structure introduced by the above-mentioned structure efficiently absorbs UV light during exposure, allowing UV curing to proceed deep into the film. In particular, when a black pigment (D1a) is contained as the colorant (D) described below, UV light may be blocked during exposure, resulting in insufficient curing, and therefore it is particularly preferable to promote UV curing using the above-mentioned structure. Furthermore, from the viewpoints of improving sensitivity during exposure, forming a pattern with a low taper shape after development, and improving halftone characteristics, it is preferable that one or more members selected from the group consisting of the fused polycyclic skeleton-containing photopolymerization initiator (C1-1a) and the fused polycyclic heterocyclic skeleton-containing photopolymerization initiator (C1-1b) have a structure in which one or more members selected from the group consisting of a nitro group, a naphthylcarbonyl structure, a trimethylbenzoyl structure, a thiophenylcarbonyl structure, and a furylcarbonyl structure are bonded to the fused polycyclic skeleton and the fused polycyclic heterocyclic skeleton.

[0167] At least one selected from the group consisting of (C1-1a) fused polycyclic skeleton-containing photopolymerization initiators and (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiators preferably contains a halogen-substituted group, from the viewpoints of improving sensitivity during exposure, forming a pattern with a low taper profile after development, and improving halftone characteristics. Furthermore, solubility in solvents can be improved. Fluorine is preferred as the halogen. This is presumably because the halogen-substituted group allows the photopolymerization initiator to be compatible with the entire film, allowing UV curing to proceed deep into the film upon exposure. Furthermore, when at least one selected from the group consisting of (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzoxazole, and (A1-4) polybenzoxazole precursor as the first resin (A1), contains a structural unit containing a fluorine atom, the compatibility between the alkali-soluble resin and the photopolymerization initiator can be further improved, and UV curing to proceed efficiently even deep into the film upon exposure. Examples of the halogen-substituted group include a fluoromethyl group, a fluoroethyl group, a chloroethyl group, a bromoethyl group, an iodoethyl group, a trifluoromethyl group, a trifluoropropyl group, a trichloropropyl group, a tetrafluoropropyl group, a trifluoropentyl group, a tetrafluoropentyl group, a pentafluoropentyl group, a heptafluoropentyl group, a heptafluorodecyl group, a fluorocyclopentyl group, a tetrafluorocyclopentyl group, a fluorophenyl group, a pentafluorophenyl group, a trifluoromethoxy group, a trifluoropropoxy group, a tetrafluoropropoxy group, a trifluoropentyloxy group, a pentafluoropentyloxy group, a tetrafluorocyclopentyloxy group, and a pentafluorophenoxy group.

[0168] At least one member selected from the group consisting of the (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator and the (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiator preferably contains an alkenyl group, from the viewpoints of improving sensitivity during exposure, forming a pattern with a low taper profile after development, and improving halftone characteristics. It is more preferable for the (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator to contain an alkenyl group. This is believed to be because the presence of an alkenyl group enhances the compatibility of the photopolymerization initiator with the alkali-soluble resin and / or radically polymerizable compound, thereby allowing efficient UV curing during exposure even deep within the film. In particular, when a (D1a) black pigment is added as the (D) colorant (described below), UV light may be blocked during exposure, resulting in insufficient curing. Therefore, the above-described structure is particularly preferred to promote UV curing. From the viewpoints of improving sensitivity during exposure, forming a pattern with a low taper shape after development, and improving halftone characteristics, one or more selected from the group consisting of the (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator and the (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiator preferably have a structure in which at least one alkenyl group having 1 to 5 carbon atoms is bonded to the fused polycyclic skeleton and the fused polycyclic heterocyclic skeleton.More preferably, the (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator has a structure in which at least one alkenyl group having 1 to 5 carbon atoms is bonded to the fused polycyclic skeleton.

[0169] Examples of alkenyl groups include vinyl, 1-methylethenyl, allyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 2,3-dimethyl-2-butenyl, 3-butenyl, cinnamyl, acrylic, and methacrylic groups. Examples of alkenyl groups having 1 to 5 carbon atoms include vinyl, 1-methylethenyl, allyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 3-butenyl, acrylic, and methacrylic groups.

[0170] From the viewpoints of improving sensitivity during exposure, forming a pattern with a low taper shape after development, improving halftone characteristics, and suppressing residue adhesion after thermal curing, the one or more types selected from the group consisting of the (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator and the (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiator preferably contain one or more types selected from the group consisting of a compound represented by general formula (12) and a compound represented by general formula (13), and more preferably a compound represented by general formula (13). The (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator is preferably a compound represented by general formula (12) or general formula (13) in which Y 1 and Y 2 In addition, the (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiator may be a compound represented by the general formula (12) or (13), wherein Y 1 and Y 2 each independently represents nitrogen, oxygen, or sulfur.

[0171] [ka]

[0172] In the general formula (12) and the general formula (13), X 1 , X2 , X 4 , and X 5 each independently represents a direct bond, an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 10 carbon atoms, or an arylene group having 6 to 15 carbon atoms. Y 1 and Y 2 R each independently represents a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom. 31 ~R 34 R each independently represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyalkyl group having 1 to 10 carbon atoms. 37 and R 38 R each independently represents a group represented by general formula (15), a group represented by general formula (16), a group represented by general formula (17), a group represented by general formula (18), or a nitro group. 40 ~R 43 R each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or a group forming a ring having 4 to 10 carbon atoms. 46 and R 47 R each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a haloalkoxy group having 1 to 10 carbon atoms, or an acyl group having 2 to 15 carbon atoms. 49 and R 50 R each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a haloalkoxy group having 1 to 10 carbon atoms, a heterocyclic group having 4 to 10 carbon atoms, a heterocyclic oxy group having 4 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or a nitro group. 52 and R 53each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. a represents an integer of 0 to 3, b represents 0 or 1, c represents an integer of 0 to 5, and d represents 0 or 1. Y 1 and Y 2 are each independently a carbon atom, then g and h are each independently 2. 1 and Y 2 are each independently a nitrogen atom, then g and h are each independently 1. 1 and Y 2 are each independently an oxygen atom or a sulfur atom, then g and h are each independently 0. j and k are each independently 0 or 1, and m and n are each independently an integer of 1 to 10. p and q are each independently an integer of 1 to 4, and x and y are each independently an integer of 1 to 4.

[0173] In the general formula (12) and the general formula (13), X 1 , X 2 , X 4 , and X 5 are each independently preferably an alkylene group having 1 to 10 carbon atoms from the viewpoint of improving solubility in a solvent. 1 , X 2 , X 4 , and X 5 and Y are each independently preferably an arylene group having 6 to 15 carbon atoms from the viewpoint of improving sensitivity during exposure. 1 and Y 2 R is preferably a carbon atom or a nitrogen atom from the viewpoint of improving sensitivity during exposure. 40 ~R 43 Examples of the ring having 4 to 10 carbon atoms formed in R include a benzene ring and a cyclohexane ring. 46 and R 47 are each independently preferably an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or a haloalkoxy group having 1 to 10 carbon atoms, from the viewpoint of improving solubility in a solvent. 46and R 47 R are each independently preferably an alkenyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a haloalkoxy group having 1 to 10 carbon atoms, or an acyl group having 2 to 10 carbon atoms, from the viewpoints of improving sensitivity during exposure, forming a pattern with a low taper shape after development, and improving halftone characteristics. 49 and R 50 are each independently preferably a cycloalkyl group having 4 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or a haloalkoxy group having 1 to 10 carbon atoms, from the viewpoint of improving solubility in a solvent. 49 and R 50 From the viewpoints of improving sensitivity during exposure, forming a pattern with a low taper shape after development, and improving halftone characteristics, R is preferably each independently an alkenyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a haloalkoxy group having 1 to 10 carbon atoms, a heterocyclic group having 4 to 10 carbon atoms, a heterocyclic oxy group having 4 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or a nitro group. 52 and R 53 are each independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group, from the viewpoint of improving sensitivity during exposure. j and k are each independently preferably 0, from the viewpoint of improving sensitivity during exposure.

[0174] [ka]

[0175] In the general formulas (15) to (18), R 55 ~R 58 each independently represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, or a group that forms a ring. 55 ~R 58Examples of the ring formed by R include a benzene ring, a naphthalene ring, an anthracene ring, a cyclopentane ring, and a cyclohexane ring. a is an integer of 0 to 7, b is an integer of 0 to 2, and c and d are each independently an integer of 0 to 3. 55 ~R 58 The ring formed by is preferably a benzene ring or a naphthalene ring.

[0176] Examples of the fused polycyclic skeleton-containing photopolymerization initiator (C1-1a) include compounds having the structure shown below.

[0177] [ka]

[0178] [ka]

[0179] [ka]

[0180] (C1-1b) Examples of the photopolymerization initiator containing a fused polycyclic heterocyclic skeleton include compounds having the structure shown below.

[0181] [ka]

[0182] [ka]

[0183] [ka]

[0184] [ka]

[0185] The (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator and the (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiator can be synthesized by known methods, such as those described in JP 2013-190459 A, JP 2016-191905 A, and WO 2014 / 500852 A.

[0186] The maximum absorption wavelength of one or more selected from the group consisting of (C1-1a) fused polycyclic skeleton-containing photopolymerization initiators and (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiators is preferably 330 nm or longer, more preferably 340 nm or longer, and even more preferably 350 nm or longer. A maximum absorption wavelength of 330 nm or longer can improve sensitivity during exposure and enable the formation of a pattern with a low taper shape after development. In addition, halftone characteristics can be improved. On the other hand, the maximum absorption wavelength of (C1-1) specific oxime ester photopolymerization initiator is preferably 410 nm or shorter, more preferably 400 nm or shorter, even more preferably 390 nm or shorter, and particularly preferably 380 nm or shorter. A maximum absorption wavelength of 410 nm or shorter can improve sensitivity during exposure and enable the formation of a pattern with a low taper shape after development. In addition, halftone characteristics can be improved. The maximum absorption wavelength refers to a wavelength within the wavelength range of 300 to 800 nm that exhibits maximum absorption in the absorption spectrum.

[0187] The absorbance at 360 nm of one or more selected from the group consisting of (C1-1a) fused polycyclic skeleton-containing photopolymerization initiators and (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiators in a 0.01 g / L propylene glycol monomethyl ether acetate solution is preferably 0.20 or higher, more preferably 0.25 or higher, even more preferably 0.30 or higher, even more preferably 0.35 or higher, particularly preferably 0.40 or higher, and most preferably 0.45 or higher. An absorbance of 0.20 or higher can improve sensitivity during exposure and enable the formation of a pattern with a low taper shape after development. Additionally, changes in pattern opening dimensional width before and after thermal curing can be suppressed, and halftone characteristics can be improved. Meanwhile, the absorbance at 360 nm of (C1-1) a specific oxime ester-based photopolymerization initiator in a 0.01 g / L propylene glycol monomethyl ether acetate solution is preferably 1.00 or lower. When the absorbance is 1.00 or less, the generation of residues after development can be suppressed and the resolution after development can be improved.

[0188] The total content of the (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator and the (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiator in the negative-type photosensitive resin composition of the present invention is preferably 0.5 parts by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, even more preferably 7 parts by mass or more, and particularly preferably 10 parts by mass or more, based on 100 parts by mass of the total of the (A) alkali-soluble resin and the (B) radically polymerizable compound. When the total content is 0.5 parts by mass or more, sensitivity during exposure can be improved, and a pattern with a low taper shape can be formed after development. In addition, halftone characteristics can be improved. Furthermore, adhesion of residues at pattern openings after thermal curing can be suppressed. On the other hand, the total content of the (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator and the (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiator is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, even more preferably 22 parts by mass or less, and particularly preferably 20 parts by mass or less. When the content is 30 parts by mass or less, the resolution after development can be improved, and a pattern with a low taper shape can be formed after development. In addition, halftone characteristics can be improved.

[0189] <(C1-1c) Diphenyl sulfide skeleton-containing oxime ester photoinitiators, (C1-2) α-aminoketone photoinitiators, (C1-3) α-hydroxyketone photoinitiators, (C1-4) phosphine oxide photoinitiators, and (C1-5) biimidazole photoinitiators> The negative-type photosensitive resin composition of the present invention preferably further contains, as the (C1) photopolymerization initiator, one or more selected from the group consisting of (C1-1c) diphenyl sulfide skeleton-containing oxime ester photopolymerization initiators, (C1-2) α-aminoketone photopolymerization initiators, (C1-3) α-hydroxyketone photopolymerization initiators, (C1-4) phosphine oxide photopolymerization initiators, and (C1-5) biimidazole photopolymerization initiators. The (C1-1c) diphenyl sulfide skeleton-containing oxime ester photopolymerization initiator refers to a compound having a diphenyl sulfide skeleton in its molecule and an oxime ester skeleton as a skeleton that generates radicals upon bond cleavage and / or reaction upon exposure. The (C1-2) α-aminoketone photopolymerization initiator refers to a compound having an α-aminoketone skeleton in its molecule and that generates radicals upon bond cleavage and / or reaction upon exposure. (C1-3) α-hydroxyketone-based photopolymerization initiators are compounds that have an α-hydroxyketone skeleton in their molecules and generate radicals through bond cleavage and / or reaction upon exposure. (C1-4) phosphine oxide-based photopolymerization initiators are compounds that have a phosphine oxide skeleton in their molecules and generate radicals through bond cleavage and / or reaction upon exposure. (C1-5) biimidazole-based photopolymerization initiators are compounds that have a biimidazole skeleton in their molecules and generate radicals through bond cleavage and / or reaction upon exposure.

[0190] The inclusion of one or more photopolymerization initiators selected from the group consisting of (C1-1c) diphenyl sulfide skeleton-containing oxime ester photopolymerization initiators, (C1-2) α-aminoketone photopolymerization initiators, (C1-3) α-hydroxyketone photopolymerization initiators, (C1-4) phosphine oxide photopolymerization initiators, and (C1-5) biimidazole photopolymerization initiators improves sensitivity during exposure and enables the formation of a pattern with a low taper shape after development. These photopolymerization initiators have different main skeleton structures or maximum absorption wavelengths from the above-mentioned (C1-1a) fused polycyclic skeleton-containing photopolymerization initiators and (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiators, and are therefore thought to compensate for the absorption of UV light during exposure, thereby allowing radical curing to proceed more efficiently.

[0191] The diphenyl sulfide skeleton-containing oxime ester photopolymerization initiator (C1-1c) preferably contains a compound represented by general formula (14), from the viewpoints of improving sensitivity during exposure, forming a pattern with a low taper shape after development, and improving halftone characteristics.

[0192] [ka]

[0193] In general formula (14), X 6 represents a direct bond, an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 4 to 10 carbon atoms, or an arylene group having 6 to 15 carbon atoms. 35 and R 36 R each independently represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyalkyl group having 1 to 10 carbon atoms. 39 R represents a group represented by the above general formula (15), a group represented by the above general formula (16), a group represented by the general formula (17), a group represented by the general formula (18), or a nitro group. 44 , R 45 , R 59 and R 60R each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or a group forming a ring having 4 to 10 carbon atoms. 51 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a haloalkoxy group having 1 to 10 carbon atoms, a heterocyclic group having 4 to 10 carbon atoms, a heterocyclic oxy group having 4 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or a nitro group. 54 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. e represents an integer of 0 to 4, and f represents an integer of 0 to 2. l represents 0 or 1, and o represents an integer of 1 to 10. r represents an integer of 1 to 4, and z represents an integer of 1 to 4.

[0194] In general formula (14), X 6 From the viewpoint of improving solubility in a solvent, X is preferably an alkylene group having 1 to 10 carbon atoms. 6 From the viewpoint of improving sensitivity during exposure, R is preferably an arylene group having 6 to 15 carbon atoms. 44 , R 45 , R 59 and R 60 Examples of the ring having 4 to 10 carbon atoms formed in R include a benzene ring and a cyclohexane ring. 51 From the viewpoint of improving solubility in a solvent, R is preferably a cycloalkyl group having 4 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, or a haloalkoxy group having 1 to 10 carbon atoms. 51 From the viewpoints of improving sensitivity during exposure, forming a pattern with a low taper shape after development, and improving halftone characteristics, R are each independently preferably an alkenyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a haloalkoxy group having 1 to 10 carbon atoms, a heterocyclic group having 4 to 10 carbon atoms, a heterocyclic oxy group having 4 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or a nitro group. 54From the viewpoint of improving sensitivity during exposure, is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group. From the viewpoint of improving sensitivity during exposure, 1 is preferably 0.

[0195] (C1-1c) Examples of the diphenyl sulfide skeleton-containing oxime ester photopolymerization initiator include compounds having the structure shown below.

[0196] [ka]

[0197] Examples of the (C1-2) α-aminoketone photopolymerization initiator include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-butan-1-one, and 3,6-bis(2-methyl-2-morpholinopropionyl)-9-octyl-9H-carbazole.

[0198] Examples of the (C1-3) α-hydroxyketone photopolymerization initiator include 2-hydroxy-1-[4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl]-2-methylpropan-1-one, 2-hydroxy-1-[4-[4-(2-hydroxy-2-methylpropionyl)phenoxy]phenyl]-2-methylpropan-1-one, 2-hydroxy-1-[4-[5-(2-hydroxy-2-methylpropionyl)-1,3,3-trimethyl-2,3-dihydro-inden-1-yl]phenyl]-2-methylpropan-1-one, and oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one].

[0199] Examples of the (C1-4) phosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide.

[0200] Examples of the (C1-5) biimidazole photopolymerization initiator include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2',5-tris(2-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,2'-biimidazole, 2,2',5-tris(2-fluorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,2'-biimidazole, and 2,2'-bis(2-methoxyphenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.

[0201] In the negative-tone photosensitive resin composition of the present invention, the total content of the (C1-1c) diphenyl sulfide skeleton-containing oxime ester photoinitiator, (C1-2) α-aminoketone photoinitiator, (C1-3) α-hydroxyketone photoinitiator, (C1-4) phosphine oxide photoinitiator, and (C1-5) biimidazole photoinitiator in the (C1) photoinitiator is preferably 5% by mass or more, more preferably 7% by mass or more, even more preferably 10% by mass or more, even more preferably 12% by mass or more, and particularly preferably 15% by mass or more. A content of 5% by mass or more can improve sensitivity during exposure and enable the formation of a pattern with a low taper shape after development. On the other hand, the total content of the (C1-1c) diphenyl sulfide skeleton-containing oxime ester photopolymerization initiator, (C1-2) α-aminoketone photopolymerization initiator, (C1-3) α-hydroxyketone photopolymerization initiator, (C1-4) phosphine oxide photopolymerization initiator, and (C1-5) biimidazole photopolymerization initiator is preferably 35% by mass or less, more preferably 33% by mass or less, even more preferably 30% by mass or less, even more preferably 28% by mass or less, and particularly preferably 25% by mass or less. A content of 35% by mass or less can improve sensitivity during exposure and enable the formation of a pattern with a low taper shape after development.

[0202] <(C2) Photoacid generator> The negative-type photosensitive resin composition of the present invention preferably further contains a (C2) photoacid generator as the (C) photosensitizer. The inclusion of the (C2) photoacid generator accelerates UV curing during exposure, thereby improving sensitivity during exposure. Furthermore, the crosslink density after thermal curing is improved, thereby improving chemical resistance. As the ionic (C2) photoacid generator, a triorganosulfonium salt compound is preferred. As the nonionic (C2) photoacid generator, for example, a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonate ester compound, a carboxylic acid ester compound, a sulfonimide compound, a phosphate ester compound, or a sulfonebenzotriazole compound may be mentioned. The content of the (C2) photoacid generator in the negative-type photosensitive resin composition of the present invention is preferably 0.1 parts by mass or more, based on 100 parts by mass of the total of the (A) alkali-soluble resin and the (B) radically polymerizable compound. On the other hand, the content of the (C2) photoacid generator is preferably 25 parts by mass or less.

[0203] In the negative-tone photosensitive resin composition of the present invention, from the viewpoints of significantly improving sensitivity during exposure, forming a pattern with a low taper shape after development, improving halftone characteristics, and suppressing the adhesion of residues at pattern openings after thermal curing, when the (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator and the (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiator each have one or more selected from the group consisting of a nitro group, a naphthylcarbonyl structure, a trimethylbenzoyl structure, a thiophenylcarbonyl structure, and a furylcarbonyl structure, the content of the (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator in the (C1) photopolymerization initiator is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, even more preferably 17% by mass or more, and particularly preferably 20% by mass or more.

[0204] On the other hand, in the negative-tone photosensitive resin composition of the present invention, from the viewpoints of improving sensitivity during exposure, forming a pattern with a low taper shape after development, improving halftone characteristics, and suppressing the adhesion of residues at pattern openings after thermal curing, when the (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator and the (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiator each have one or more selected from the group consisting of a nitro group, a naphthylcarbonyl structure, a trimethylbenzoyl structure, a thiophenylcarbonyl structure, and a furylcarbonyl structure, the content of the (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator in the (C1) photopolymerization initiator is preferably 45% by mass or less, more preferably 43% by mass or less, even more preferably 40% by mass or less, even more preferably 38% by mass or less, and particularly preferably 35% by mass or less.

[0205] Furthermore, in the negative-tone photosensitive resin composition of the present invention, from the viewpoints of significantly improving sensitivity during exposure, forming a pattern with a low taper shape after development, improving halftone characteristics, and suppressing the adhesion of residues at pattern openings after thermal curing, when the (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator and the (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiator each have one or more structures selected from the group consisting of a nitro group, a naphthylcarbonyl structure, a trimethylbenzoyl structure, a thiophenylcarbonyl structure, and a furylcarbonyl structure, it is more preferable that the (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiator have, as the fused polycyclic heterocyclic skeleton, one or more structures selected from the group consisting of a carbazole skeleton, a benzocarbazole skeleton, an indole skeleton, an indoline skeleton, a benzoindole skeleton, and a benzoindoline skeleton, and even more preferably one or more structures selected from the group consisting of a benzocarbazole skeleton, a benzoindole skeleton, and a benzoindoline skeleton.

[0206] Similarly, in the negative-tone photosensitive resin composition of the present invention, from the viewpoint of significantly improving sensitivity during exposure, forming a pattern with a low taper shape after development, improving halftone characteristics, and suppressing the adhesion of residues at pattern openings after thermal curing, when the (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator has, as the fused polycyclic skeleton, one or more skeletons selected from the group consisting of a fluorene skeleton, a benzofluorene skeleton, a dibenzofluorene skeleton, an indene skeleton, an indane skeleton, a benzoindene skeleton, and a benzoindane skeleton, it is more preferable that the (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiator has, as the fused polycyclic heterocyclic skeleton, one or more skeletons selected from the group consisting of a carbazole skeleton, a benzocarbazole skeleton, an indole skeleton, an indoline skeleton, a benzoindole skeleton, and a benzoindoline skeleton, and even more preferably one or more skeletons selected from the group consisting of a benzocarbazole skeleton, a benzoindole skeleton, and a benzoindoline skeleton.

[0207] <<(D) Coloring agents, (Da) black agents, and (Db) coloring agents other than black>> The negative photosensitive resin composition of the present invention preferably further contains a (D) colorant. The (D) colorant is a compound that absorbs light of a specific wavelength, and in particular, a compound that is colored by absorbing light of a visible light wavelength (380 to 780 nm). By including a (D) colorant, light transmitted through or reflected from a film of the resin composition can be colored to a desired color. Furthermore, light-blocking properties can be imparted to the film of the resin composition. Furthermore, the (Da) black agent is always included, and a (Db) colorant other than black may also be included.

[0208] Examples of the (D) colorant include (D1) pigments and (D2) dyes. When light-blocking properties against visible light are particularly required, the negative-type photosensitive resin composition of the present invention preferably contains a (Da) blackening agent. The (Da) blackening agent refers to a compound that absorbs light in the visible wavelength range and thereby produces a black color. The inclusion of the (Da) blackening agent blackens the resin composition film, thereby improving the light-blocking properties of the resin composition film and the reliability of the light-emitting device. Therefore, the composition is suitable for applications such as pixel dividing layers, electrode insulating layers, wiring insulating layers, TFT planarizing layers, electrode planarizing layers, wiring planarizing layers, TFT protective layers, electrode protective layers, wiring protective layers, interlayer insulating layers, gate insulating layers, color filters, black matrices, and black column spacers. The composition is particularly suitable for applications requiring high contrast by suppressing external light reflection, and is preferred as a light-blocking pixel dividing layer, TFT planarizing layer, TFT protective layer, interlayer insulating layer, or gate insulating layer for organic electroluminescence (EL) displays.

[0209] The term "black" in the case of (D) colorants refers to those whose Color Index Generic Name (hereinafter referred to as "CI number") includes "BLACK." When a colorant without a CI number is contained, the term refers to a black film when cured. The term "black" in the case of a cured film refers to a film in which, in the transmission spectrum of a cured film of a resin composition containing (D) colorant, the transmittance per 1.0 μm of film thickness at a wavelength of 550 nm is converted to a film thickness of 0.1 to 1.5 μm based on the Beer-Lambert equation so that the transmittance at a wavelength of 550 nm is 10%, and the converted transmission spectrum has a transmittance of 25% or less at wavelengths of 450 to 650 nm.

[0210] The transmission spectrum of the cured film can be determined by the following method. A resin composition containing at least any binder resin and (D) colorant is prepared so that the content of (D) colorant in the total solid content of the resin composition is 35 mass%. A film of the resin composition is applied to a Tempax glass substrate (manufactured by AGC Technoglass Co., Ltd.) and then prebaked at 110°C for 2 minutes to form a prebaked film. Next, the resin composition is thermally cured in a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.) at 250°C for 60 minutes under a nitrogen atmosphere to produce a 1.0 μm thick cured film of the resin composition containing (D) colorant (hereinafter referred to as a "colorant-containing cured film"). A resin composition containing the binder resin but not containing (D) a colorant was prepared, and the composition was coated, prebaked, and thermally cured on a Tempax glass substrate in the same manner as above to produce a 1.0 μm thick cured film of the resin composition not containing (D) a colorant (hereinafter referred to as a "blank cured film"). First, a Tempax glass substrate on which a blank cured film was formed with a thickness of 1.0 μm was measured using a UV-visible spectrophotometer (MultiSpec-1500; manufactured by Shimadzu Corporation), and the UV-visible absorption spectrum was used as the blank. Next, the Tempax glass substrate on which the colorant-containing cured film was formed was measured with a single beam to determine the transmittance per 1.0 μm thick film at wavelengths of 450 to 650 nm. The transmittance of the colorant-containing cured film was calculated from the difference with the blank.

[0211] The maximum transmission wavelength of the black agent (Da) is preferably 330 nm or more, more preferably 340 nm or more, from the viewpoints of improving sensitivity during exposure, forming a pattern with a low taper shape after development, and improving halftone characteristics. On the other hand, the maximum transmission wavelength of the black agent (Da) is preferably 410 nm or less, more preferably 390 nm or less, from the viewpoints of improving sensitivity during exposure, forming a pattern with a low taper shape after development, and improving halftone characteristics. Furthermore, as described above, when the maximum transmission wavelength of the black agent (Da) is 330 to 410 nm, the maximum absorption wavelength of the specific oxime ester photopolymerization initiator (C1-1) described above is preferably 330 to 410 nm. The maximum transmission wavelength refers to the wavelength showing maximum transmission in the transmission spectrum within a wavelength range of 300 to 800 nm. The maximum transmission wavelength of the (D) colorant can be calculated by measuring the transmittance per 1.0 μm of film thickness at wavelengths of 300 to 800 nm, in the same manner as in the method for measuring the transmission spectrum of the cured film described above, and determining the wavelength showing the maximum transmission in the transmission spectrum within the wavelength range of 300 to 800 nm.

[0212] The content of the (D) colorant in the total solid content of the negative photosensitive resin composition of the present invention, excluding the solvent, is preferably 5% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, from the viewpoints of improving the light-shielding property and improving the reliability of the light-emitting device. On the other hand, the content of the (D) colorant is preferably 70% by mass or less, more preferably 55% by mass or less, from the viewpoints of improving the sensitivity during exposure, forming a pattern with a low taper shape after development, and improving the reliability of the light-emitting device.

[0213] In the negative-type photosensitive resin composition of the present invention, the preferred content ratio of the black agent (Da) is the same as the preferred content ratio of the colorant (D) described above. When the content ratio of the black agent (Da) is within the above range, the reliability of the light-emitting device can be particularly improved.

[0214] <(D1) Pigment and (D2) Dye> In the negative-type photosensitive resin composition of the present invention, the aforementioned (D) colorant preferably contains a (D1) pigment. In an embodiment in which the aforementioned (D) colorant contains a (D1) pigment, the aforementioned (Da) black agent is always contained, and a non-black colorant (Db) may optionally be contained. The (D1) pigment refers to a compound that colors an object by physically adsorbing to the surface of the object or by interacting with the surface of the object, and is generally insoluble in solvents, etc. The inclusion of the (D1) pigment allows for coloring with a color having excellent hiding power, thereby improving the light-blocking properties and weather resistance of the resin composition film. Examples of the (D1) pigment include organic pigments and inorganic pigments.

[0215] The number-average particle size of the (D1) pigment is preferably 10 nm or more, more preferably 30 nm or more, from the viewpoints of suppressing residue after development and improving the storage stability of the coating liquid. On the other hand, the number-average particle size of the (D1) pigment is preferably 500 nm or less, more preferably 300 nm or less, from the viewpoints of improving sensitivity during exposure and forming a pattern with a low taper shape after development. Here, the number-average particle size of the (D1) pigment can be determined by measuring laser scattering due to Brownian motion of the (D1) pigment in solution (dynamic light scattering method) using a submicron particle size distribution analyzer (N4-PLUS; manufactured by Beckman Coulter) or a zeta potential / particle size / molecular weight analyzer (Zetasizer Nano ZS; manufactured by Sysmex Corporation). The number-average particle size of the (D1) pigment in a cured film obtained from the resin composition can be determined by measurement using a scanning electron microscope (hereinafter referred to as "SEM") and a transmission electron microscope (hereinafter referred to as "TEM"). (D1) The number average particle size of the pigment is directly measured at a magnification of 50,000 to 200,000 times. (D1) If the pigment is a perfect sphere, the diameter of the sphere is measured and used as the number average particle size. (D1) If the pigment is not a perfect sphere, the longest diameter (hereinafter referred to as the "major axis diameter") and the longest diameter in the direction perpendicular to the major axis diameter (hereinafter referred to as the "minor axis diameter") are measured, and the biaxial average diameter obtained by averaging the major axis diameter and the minor axis diameter is used as the number average particle size.

[0216] The preferred content ratio of the pigment (D1) in the total solid content of the negative photosensitive resin composition of the present invention, excluding the solvent, is the same as the preferred content ratio of the colorant (D) described above. When the content ratio of the pigment (D1) is within the above range, a pattern with a small taper shape can be formed particularly after development.

[0217] (D2) dyes are compounds that color an object by chemically adsorbing to the surface structure of the object, and are generally soluble in solvents. Furthermore, coloring with (D2) dyes is achieved by adsorbing each molecule to the object, resulting in high coloring power and high color-developing efficiency. Examples of (D2) dyes include anthraquinone dyes, azo dyes, azine dyes, phthalocyanine dyes, methine dyes, oxazine dyes, quinoline dyes, indigo dyes, indigoid dyes, carbonium dyes, threne dyes, perinone dyes, perylene dyes, triarylmethane dyes, and xanthene dyes.

[0218] <(D1a) Black pigment and (D1b) non-black pigment> In the negative-type photosensitive resin composition of the present invention, the above-mentioned (D1) pigment preferably contains a (D1a) black pigment, or a (D1a) black pigment and a (D1b) non-black pigment. The (D1a) black pigment refers to a pigment that absorbs light of visible light wavelengths and thereby colors the resin composition black. The inclusion of the (D1a) black pigment can improve the light-blocking properties of the resin composition film and can also improve the reliability of the light-emitting device. In the negative-type photosensitive resin composition of the present invention, the above-mentioned (Da) black agent is preferably a (D1a) black pigment, and this (D1a) black pigment is preferably one or more selected from the group consisting of a (D1a-1) black organic pigment, a (D1a-2) black inorganic pigment, and a (D1a-3) mixture of two or more colored pigments, which will be described later.

[0219] The negative-type photosensitive resin composition of the present invention may further contain (D1b) a non-black pigment when the (D1a) black pigment is at least one selected from the group consisting of (D1a-1) black organic pigments and (D1a-2) black inorganic pigments described below. The (D1b) non-black pigment refers to a pigment that is colored by absorbing light of visible light wavelengths. By including (D1b) a non-black pigment, it is possible to impart color-tuning properties to the resin composition film. By combining two or more pigments, it is possible to adjust the color of the resin composition film to the desired color coordinates. In the negative-type photosensitive resin composition of the present invention, the (D1b) non-black pigment is preferably at least one selected from the group consisting of blue pigments, red pigments, yellow pigments, purple pigments, orange pigments, and green pigments described below.

[0220] In the negative-type photosensitive resin composition of the present invention, the preferred content ratio of the black pigment (D1a) is the same as the preferred content ratio of the colorant (D) described above. When the content ratio of the black pigment (D1a) is within the above range, the reliability of the light-emitting device can be particularly improved.

[0221] <(D1a-1) Black organic pigment, (D1a-2) Black inorganic pigment, and (D1a-3) Mixture of two or more colored pigments> In the negative-type photosensitive resin composition of the present invention, the black pigment (D1a) is preferably one or more selected from the group consisting of (D1a-1) black organic pigment, (D1a-2) black inorganic pigment, and (D1a-3) a mixture of two or more colored pigments. From the viewpoint of improving the reliability of light-emitting devices, the black organic pigment (D1a-1) and / or (D1a-3) a mixture of two or more colored pigments is more preferable. From the viewpoint of improving sensitivity during exposure, the black organic pigment (D1a-1) is even more preferable. The black organic pigment (D1a-1) refers to an organic pigment that is colored black by absorbing light in the visible light wavelength range. The inclusion of the black pigment (D1a) can improve the light-blocking properties of a resin composition film and can also improve the reliability of light-emitting devices. The black organic pigment (D1a-1) has superior insulating properties and low dielectric constant compared to general inorganic pigments, and therefore can improve the resistance value of the film. In particular, it is suitable for a pixel dividing layer, a TFT planarizing layer, a TFT protective layer, an interlayer insulating layer, or a gate insulating layer having light-shielding properties in an organic EL display, and can improve the reliability of the light-emitting device.

[0222] (D1a-1) Examples of black organic pigments include anthraquinone-based black pigments, benzofuranone-based black pigments, perylene-based black pigments, aniline-based black pigments, azo-based black pigments, azomethine-based black pigments, and carbon black, such as channel black, furnace black, thermal black, acetylene black, and lamp black.

[0223] The (D1a-2) black inorganic pigment refers to an inorganic pigment that absorbs light in the visible light wavelength range and thereby colors the film black. The (D1a-2) black inorganic pigment has superior heat resistance and weather resistance compared to general organic pigments, and therefore can improve the light-blocking properties of a resin composition film as well as the heat resistance and weather resistance of the film. Examples of the (D1a-2) black inorganic pigment include fine particles, oxides, composite oxides, sulfides, sulfates, nitrates, carbonates, nitrides, carbides, or oxynitrides of graphite or silver-tin alloys, or metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, or silver.

[0224] The (D1a-3) two or more color pigment mixture refers to a color pigment mixture that is colored pseudo-black by combining two or more pigments selected from the group consisting of red, orange, yellow, green, blue, and purple pigments. Mixing two or more pigments enables adjustment of the transmission spectrum or absorption spectrum of the resin composition film, and color matching to adjust the resin composition film to desired color coordinates. For the negative-type photosensitive resin composition of the present invention, the (D1a-3) two or more color pigment mixture described above is preferably (D1a-3a) a color pigment mixture containing a blue pigment, a red pigment, and a yellow pigment; (D1a-3b) a color pigment mixture containing a purple pigment and a yellow pigment; (D1a-3c) a color pigment mixture containing a blue pigment, a red pigment, and an orange pigment; or (D1a-3d) a color pigment mixture containing a blue pigment, a purple pigment, and an orange pigment. (D1a-3) When the mixture of two or more color pigments has the above-mentioned structure, it is possible to improve the sensitivity during exposure and to form a pattern with a low taper shape after development.

[0225] Examples of pigments that impart blue color include Pigment Blue 15, 15:3, 15:4, 15:6, 22, 60, and 64 (all numbers are CI numbers). Examples of pigments that impart red color include Pigment Red 9, 48, 97, 122, 123, 144, 149, 166, 168, 177, 179, 180, 190, 192, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, and 250 (all numbers are CI numbers). Examples of pigments that impart yellow color include Pigment Yellow 12, 13, 17, 20, 24, 83, 86, 93, 95, 109, 110, 117, 120, 125, 129, 137, 138, 139, 147, 148, 150, 151, 153, 154, 166, 168, 175, 180, 181, 185, 192, and 194 (all numbers are CI numbers). Examples of pigments that impart purple color include Pigment Violet 19, 23, 29, 30, 32, 37, 40, and 50 (all numbers are CI numbers). Examples of pigments that impart orange color include Pigment Orange 12, 36, 38, 43, 51, 55, 59, 61, 64, 65, 71, and 72 (all numbers are CI numbers). Examples of pigments that impart green color include Pigment Green 7, 10, 36, and 58 (all numbers are CI numbers).

[0226] In the negative photosensitive resin composition of the present invention, in the above-mentioned (D1a-3) mixture of two or more color pigments, the above-mentioned blue pigment is preferably one or more selected from the group consisting of CI Pigment Blue 15:4, CI Pigment Blue 15:6, and CI Pigment Blue 60, the above-mentioned red pigment is preferably one or more selected from the group consisting of CI Pigment Red 123, CI Pigment Red 149, CI Pigment Red 177, CI Pigment Red 179, and CI Pigment Red 190, and the above-mentioned yellow pigment is preferably one or more selected from the group consisting of CI Pigment Yellow 120, CI Pigment Yellow Preferably, the purple pigment is one or more selected from the group consisting of CI Pigment Violet 151, CI Pigment Yellow 175, CI Pigment Yellow 180, CI Pigment Yellow 181, CI Pigment Yellow 192, and CI Pigment Yellow 194. Preferably, the purple pigment is one or more selected from the group consisting of CI Pigment Violet 19, CI Pigment Violet 29, and CI Pigment Violet 37. Preferably, the orange pigment is one or more selected from the group consisting of CI Pigment Orange 43, CI Pigment Orange 64, and CI Pigment Orange 72. (D1a-3) When the two or more color pigment mixture has the above-described configuration, sensitivity during exposure can be improved and a pattern with a low taper shape can be formed after development. Furthermore, these pigments have excellent heat resistance, can reduce the pigment-derived halogen content in the resin composition, and have excellent insulating properties and low dielectric constant, thereby improving the reliability of light-emitting devices.

[0227] In the negative-tone photosensitive resin composition of the present invention, the preferred content ratio of one or more selected from the group consisting of (D1a-1) black organic pigment, (D1a-2) black inorganic pigment, and (D1a-3) a mixture of two or more colored pigments is the same as the preferred content ratio of the colorant (D) described above. When the content ratio is within the above range, the reliability of the light-emitting device can be particularly improved.

[0228] <(D1a-1a) Benzofuranone-based black pigment, (D1a-1b) Perylene-based black pigment, and (D1a-1c) Azo-based black pigment> In the negative-tone photosensitive resin composition of the present invention, from the viewpoints of improving sensitivity during exposure, reducing taper by controlling pattern shape after development, and improving halftone characteristics, the above-mentioned (D1a-1) black organic pigment is preferably one or more selected from the group consisting of (D1a-1a) benzofuranone-based black pigments, (D1a-1b) perylene-based black pigments, and (D1a-1c) azo-based black pigments, and (D1a-1a) benzofuranone-based black pigments are more preferred. (D1a-1a) Benzofuranone-based black pigments, (D1a-1b) perylene-based black pigments, and (D1a-1c) azo-based black pigments have superior light-blocking properties per unit pigment content in the resin composition compared to general organic pigments, and therefore can impart equivalent light-blocking properties at lower content ratios. This improves the light-blocking properties of the film and also improves sensitivity during exposure. Furthermore, due to their superior insulating properties and low dielectric constant compared to general organic pigments and inorganic pigments, the film's resistance value can be improved. In particular, it is suitable for a pixel dividing layer, a TFT planarizing layer, a TFT protective layer, an interlayer insulating layer, or a gate insulating layer having light-shielding properties in an organic EL display, and can improve the reliability of the light-emitting device.

[0229] In particular, the benzofuranone-based black pigment (D1a-1a) absorbs light in the visible light wavelength range while exhibiting high transmittance in the ultraviolet wavelength range (e.g., 400 nm or less), thereby improving sensitivity during exposure and enabling the formation of a pattern with a low taper shape after development. On the other hand, when the benzofuranone-based black pigment (D1a-1a) is incorporated, pigment-derived development residues may be generated due to the pigment's insufficient alkali resistance. Specifically, when the surface of the benzofuranone-based black pigment (D1a-1a) is exposed to an alkaline developer during development, a portion of the surface may decompose or dissolve, leaving behind the pigment-derived development residue on the substrate. In such cases, as described above, the incorporation of one or more compounds selected from the group consisting of the flexible-chain-containing aliphatic radical polymerizable compound (B3) and the fluorene skeleton-containing radical polymerizable compound (B1) and the indane skeleton-containing radical polymerizable compound (B2) can suppress the generation of the pigment-derived development residues.

[0230] (D1a-1a) The benzofuranone black pigment is preferably a benzofuranone compound having a benzofuran-2(3H)-one structure or a benzofuran-3(2H)-one structure in the molecule and represented by general formula (63) or general formula (64), a geometric isomer thereof, a salt thereof, or a salt of the geometric isomer.

[0231] [ka]

[0232] In the general formula (63) and the general formula (64), R 206 , R 207 , R 214 , and R 215 R each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms and 1 to 20 fluorine atoms. 208 , R 209 , R 216 , and R 217 are each independently a hydrogen atom, a halogen atom, or R 212 , COOH, COOR 212 , COO- , CONH2, CONHR 212 ,CONR 212 R 213 , CN, OH, OR 212 ,OCOR 212 , OCONH2, OCONHR 212 , OCONR 212 R 213 , NO2, NH2, NHR 212 , N.R. 212 R 213 , NHCOR 212 , N.R. 212 COR 213 , N=CH2, N=CHR 212 , N=CR 212 R 213 , S.H., S.R. 212 , SOR 212 , SO2R 212 , SO3R 212 , SO3H, SO3 - , SO2NH2, SO2NHR 212 , or SO2NR 212 R 213 represents R 212 and R 213 each independently represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkenyl group having 4 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms. 208 , R 209 , R 216 , or R 217 and a direct bond, or an oxygen atom bridge, a sulfur atom bridge, an N-H bridge, or an N-R 212 A bridge may form a ring. 210 , R 211 , R 218 , and R 219 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. a, b, c, and d each independently represent an integer of 0 to 4. The above-mentioned alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, and aryl groups may have a heteroatom, and may be either unsubstituted or substituted.

[0233] (D1a-1a) Examples of benzofuranone-based black pigments include "IRGAPHOR" (registered trademark) BLACK S0100CF (manufactured by BASF), black pigments described in WO 2010 / 081624, and black pigments described in WO 2010 / 081756.

[0234] The perylene-based black pigment (D1a-1b) is preferably a perylene compound having a perylene structure in the molecule and represented by general formula (69).

[0235] [ka]

[0236] In the general formula (69), X 92 , and X 93 each independently represents a direct bond or an alkylene chain having 1 to 10 carbon atoms. 92 , and Y 93 R each independently represents a direct bond or an arylene chain having 6 to 15 carbon atoms. 224 and R 225 R each independently represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an acyl group having 2 to 6 carbon atoms. 226 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms and 1 to 20 fluorine atoms. a and b each independently represent an integer of 0 to 5. c represents an integer of 0 to 8. X 92 , and X 93 is a direct bond, and Y 92 , and Y 93 In the case of a direct bond, R 224 and R 225 are each preferably independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and a and b are each 1. 92 , and X 93 is an alkylene chain having 1 to 10 carbon atoms, and Y 92 , and Y 93 is a direct bond, R224 and R 225 is preferably a hydroxy group, and a and b are 1. 92 , and X 93 is an alkylene chain having 1 to 10 carbon atoms, and Y 92 , and Y 93 In the case of an arylene chain having 6 to 15 carbon atoms, R 224 and R 225 are each independently preferably a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or an acyl group having 2 to 6 carbon atoms. a and b are each independently an integer of 0 to 5. The above-mentioned alkylene chains, arylene chains, alkoxy groups, acyl groups, and alkyl groups may have a heteroatom, and may be either unsubstituted or substituted.

[0237] (D1a-1b) Examples of perylene-based black pigments include Pigment Black 31 and 32 (all numbers are CI numbers). In addition to the above, examples of the perylene-based black pigments include "PALIOGEN" (registered trademark) BLACK S0084, K0084, L0086, K0086, EH0788, and FK4281 (all manufactured by BASF).

[0238] The azo black pigment (D1a-1c) is preferably an azo compound having an azo group in the molecule and represented by the general formula (72).

[0239] [ka]

[0240] In general formula (72), X 96 represents an arylene chain having 6 to 15 carbon atoms. 96 represents an arylene chain having 6 to 15 carbon atoms. 275 , R 276 , and R 277 R each independently represents a halogen or an alkyl group having 1 to 10 carbon atoms. 278 represents a halogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a nitro group. 279represents a halogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acylamino group having 2 to 10 carbon atoms, or a nitro group. 280 , R 281 , R 282 , and R 283 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. a represents an integer of 0 to 4, b represents an integer of 0 to 2, c represents an integer of 0 to 4, d and e each independently represent an integer of 0 to 8, and n represents an integer of 1 to 4. The above-mentioned arylene chain, alkyl group, alkoxy group, and acylamino group may have a heteroatom, and may be either unsubstituted or substituted.

[0241] (D1a-1c) Examples of azo black pigments include "CHROMOFINE" (registered trademark) BLACK A1103 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.), the black pigments described in JP-A-01-170601, and the black pigments described in JP-A-02-034664.

[0242] The content of one or more selected from the group consisting of (D1a-1a) benzofuranone-based black pigments, (D1a-1b) perylene-based black pigments, and (D1a-1c) azo-based black pigments in the total solids content of the negative-type photosensitive resin composition of the present invention, excluding the solvent, is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, and particularly preferably 30% by mass or more, from the viewpoints of improving light-blocking properties and improving the reliability of light-emitting devices. On the other hand, the content of one or more selected from the group consisting of (D1a-1a) benzofuranone-based black pigments, (D1a-1b) perylene-based black pigments, and (D1a-1c) azo-based black pigments is preferably 70% by mass or less, more preferably 55% by mass or less, from the viewpoints of improving sensitivity during exposure, forming a pattern with a low taper shape after development, and improving the reliability of light-emitting devices.

[0243] In the negative photosensitive resin composition of the present invention, from the viewpoint of significantly improving sensitivity during exposure, forming a pattern with a low taper shape after development, improving halftone characteristics, and suppressing adhesion of residues at pattern openings after thermal curing, the (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator and the (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiator each have one or more structures selected from the group consisting of a nitro group, a naphthylcarbonyl structure, a trimethylbenzoyl structure, a thiophenylcarbonyl structure, and a furylcarbonyl structure. When the composition has at least one type of pigment, it is preferred that the (D) colorant comprises (D1a-1) a black organic pigment and / or (D1a-3) a mixture of two or more colored pigments, the (D1a-1) black organic pigment contains one or more pigments selected from the group consisting of (D1a-1a) benzofuranone-based black pigments, (D1a-1b) perylene-based black pigments, and (D1a-1c) azo-based black pigments, and the (D1a-3) mixture of two or more colored pigments contains two or more pigments selected from the group consisting of red, orange, yellow, green, blue, and purple pigments.

[0244] <(DC) coating layer> In the negative-tone photosensitive resin composition of the present invention, the black organic pigment (D1a-1) preferably further contains a (DC) coating layer. The (DC) coating layer refers to a layer that coats the pigment surface, formed by, for example, surface treatment with a silane coupling agent, surface treatment with a silicate, surface treatment with a metal alkoxide, or coating treatment with a resin. By incorporating a (DC) coating layer, the particle surface of the black organic pigment (D1a-1) can be acidified, basified, hydrophilized, or hydrophobized, thereby modifying the particle surface condition and improving properties such as acid resistance, alkali resistance, solvent resistance, dispersion stability, and heat resistance. This can suppress the generation of pigment-derived development residues. Furthermore, side etching during development is suppressed, enabling the formation of a pattern with a low taper shape after development. In addition, halftone characteristics can be improved. Furthermore, forming an insulating coating layer on the particle surface can improve the insulation properties of the cured film, thereby reducing leakage current and improving the reliability of light-emitting devices. In particular, when a benzofuranone-based black pigment (D1a-1a) is contained as the black organic pigment (D1a-1), by containing a coating layer (DC) on the benzofuranone-based black pigment (D1a-1a), the alkali resistance of the pigment can be improved and the generation of development residues derived from the pigment can be suppressed.

[0245] The average coverage of the (D1a-1) black organic pigment by the (DC) coating layer is preferably 50% or more, more preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. When the average coverage of the (DC) coating layer is 80% or more, the generation of residue after development can be suppressed. The average coverage of the (D1a-1) black organic pigment by the (DC) coating layer can be determined by observing a cross section of the black organic pigment using a transmission electron microscope (H9500; manufactured by Hitachi High-Technologies Corporation) at an accelerating voltage of 300 kV and a magnification of 50,000 to 200,000 times. For 100 randomly selected black pigment particles, the coverage of each black pigment, M (%), is calculated using the following formula, and the number average value is calculated to determine the average coverage, N (%). Coverage rate M(%)={L1 / (L1+L2)}×100 L1: Total length of the particle periphery covered by the coating layer (nm) L2: Total length (nm) of the outer periphery of the particle that is not covered by the coating layer (the area where the interface and the embedding resin are in direct contact) L1+L2: Particle perimeter (nm).

[0246] <(DC-1) Silica Coating Layer, (DC-2) Metal Oxide Coating Layer, and (DC-3) Metal Hydroxide Coating Layer> The (DC) coating layer preferably contains one selected from the group consisting of (DC-1) a silica coating layer, (DC-2) a metal oxide coating layer, and (DC-3) a metal hydroxide coating layer. Silica, metal oxides, and metal hydroxides impart alkali resistance to the pigment, thereby suppressing the generation of pigment-derived development residues. Examples of silica include silicon dioxide and its hydrates. Examples of metal oxides include metal oxides and their hydrates. Examples of metal oxides include alumina, such as alumina (Al2O3) or alumina hydrate (Al2O3·nH2O). Examples of metal hydroxides include aluminum hydroxide (Al(OH)3). Because silica has a low dielectric constant, it can suppress an increase in dielectric constant when the content of the (DC) coating layer of the (D1a-1) black organic pigment is increased, thereby improving the reliability of the light-emitting device.

[0247] <<(E) Dispersant>> The negative-tone photosensitive resin composition of the present invention preferably further contains a (E) dispersant. The (E) dispersant refers to a compound having a surface-affinity group that interacts with the surface of the (D1) pigment or the like and a dispersion-stabilizing structure that improves the dispersion stability of the (D1) pigment or the like. Examples of the dispersion-stabilizing structure of the (E) dispersant include a polymer chain that contributes to dispersion stabilization through steric hindrance, or an ionic or polar substituent that contributes to dispersion stabilization through electrostatic repulsion. When the number-average particle size of the (D1) pigment is 500 nm or less, the smaller the number-average particle size, the greater the increase in surface area, which can lead to particle aggregation and the generation of residue after development. In particular, when the (D1) pigment is contained as the (D) colorant, the inclusion of the (E) dispersant can improve the dispersion stability of the negative-tone photosensitive resin composition containing the (D1) pigment or the like, thereby improving pattern processability in an alkaline developer, resolution after development, and storage stability of the coating solution.

[0248] Examples of the (E) dispersant include a dispersant having only a basic group, a dispersant having both a basic group and an acidic group, a dispersant having only an acidic group, a dispersant having a structure in which a basic group forms a salt with an acid, a dispersant having a structure in which an acidic group forms a salt with a base, and a dispersant having neither a basic group nor an acidic group. From the viewpoints of improving dispersion stability, improving pattern processability in an alkaline developer, and improving resolution after development, dispersants having only a basic group, a dispersant having both a basic group and an acidic group, a dispersant having a structure in which a basic group forms a salt with an acid, or a dispersant having a structure in which an acidic group forms a salt with a base are preferred, and dispersants having only a basic group or a dispersant having both a basic group and an acidic group are more preferred.

[0249] Examples of the basic group contained in the (E) dispersant, or a structure in which a basic group forms a salt with an acid, include a tertiary amino group or a quaternary ammonium salt structure, or a nitrogen-containing ring skeleton such as a pyrrolidine skeleton, a pyrrole skeleton, an imidazole skeleton, a pyrazole skeleton, a triazole skeleton, a tetrazole skeleton, an imidazoline skeleton, an oxazole skeleton, an isoxazole skeleton, an oxazoline skeleton, an isoxazoline skeleton, a thiazole skeleton, an isothiazole skeleton, a thiazoline skeleton, an isothiazol skeleton, a thiazine skeleton, a piperidine skeleton, a piperazine skeleton, a morpholine skeleton, a pyridine skeleton, a pyridazine skeleton, a pyrimidine skeleton, a pyrazine skeleton, a triazine skeleton, an isocyanuric acid skeleton, an imidazolidinone skeleton, a propylene urea skeleton, a butylene urea skeleton, a hydantoin skeleton, a barbituric acid skeleton, an alloxane skeleton, or a glycoluril skeleton, or a structure in which such a nitrogen-containing skeleton forms a salt. In the structure in which a basic group forms a salt with an acid, examples of the counter anion include a halogen ion, a sulfate ion, a sulfonate ion, a nitrate ion, a carboxylate ion, and a phenoxy ion.

[0250] The amine value of the (E) dispersant is preferably 5 mgKOH / g or more, more preferably 8 mgKOH / g or more, and even more preferably 10 mgKOH / g or more. An amine value of 5 mgKOH / g or more can improve the dispersion stability of the (D1) pigment. On the other hand, the amine value is preferably 150 mgKOH / g or less, more preferably 120 mgKOH / g or less, and even more preferably 100 mgKOH / g or less. An amine value of 150 mgKOH / g or less can improve the storage stability of the resin composition. The amine value here refers to the weight of potassium hydroxide equivalent to the acid that reacts with 1 g of the (E) dispersant, expressed in mgKOH / g. It can be determined by neutralizing 1 g of the (E) dispersant with acid and then titrating with an aqueous potassium hydroxide solution. From the amine value, the amine equivalent (unit: g / mol), which is the weight of resin per 1 mol of basic groups such as amino groups, can be calculated, and the number of basic groups such as amino groups in the (E) dispersant can be determined.

[0251] The acid value of the (E) dispersant is preferably 5 mgKOH / g or more, more preferably 8 mgKOH / g or more, and even more preferably 10 mgKOH / g or more. An acid value of 5 mgKOH / g or more can improve the dispersion stability of the (D1) pigment. On the other hand, the acid value is preferably 200 mgKOH / g or less, more preferably 170 mgKOH / g or less, and even more preferably 150 mgKOH / g or less. An acid value of 200 mgKOH / g or less can improve the storage stability of the resin composition. The acid value here refers to the weight of potassium hydroxide that reacts with 1 g of the (E) dispersant, and is expressed in mgKOH / g. It can be determined by titrating 1 g of the (E) dispersant with an aqueous potassium hydroxide solution. From the acid value, the acid equivalent (unit: g / mol), which is the weight of resin per 1 mole of acidic groups, can be calculated, and the number of acidic groups in the (E) dispersant can be determined.

[0252] Examples of the (E) dispersant having a polymer chain include an acrylic resin-based dispersant, a polyoxyalkylene ether-based dispersant, a polyester-based dispersant, a polyurethane-based dispersant, a polyol-based dispersant, a polyethyleneimine-based dispersant, and a polyallylamine-based dispersant. From the viewpoint of pattern processability in an alkaline developer, an acrylic resin-based dispersant, a polyoxyalkylene ether-based dispersant, a polyester-based dispersant, a polyurethane-based dispersant, and a polyol-based dispersant are preferred.

[0253] When the negative-tone photosensitive resin composition of the present invention contains the pigment (D1), the content of the dispersant (E) in the negative-tone photosensitive resin composition of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, based on 100% by mass of the total of the pigment (D1) and the dispersant (E), from the viewpoints of improving dispersion stability and improving pattern processability in an alkaline developer. On the other hand, the content of the dispersant (E) is preferably 60% by mass or less, more preferably 50% by mass or less, from the viewpoints of forming a pattern with a low taper shape after development and improving the reliability of the light-emitting device.

[0254] <<(F) Crosslinking agent>> The negative-tone photosensitive resin composition of the present invention preferably further contains a (F) crosslinking agent. The (F) crosslinking agent refers to a compound having a crosslinkable group capable of bonding with a resin. The inclusion of the (F) crosslinking agent can improve chemical resistance and form a pattern with a low taper shape after thermal curing. This is presumably because the (F) crosslinking agent introduces a new crosslinking structure into the cured film of the resin composition, thereby increasing the crosslinking density. The introduction of the new crosslinking structure also inhibits the dense alignment of polymer chains, alleviating steric hindrance from aromatic rings and other components contained in the resin, thereby improving reflowability during thermal curing. As the (F) crosslinking agent, in addition to the epoxy crosslinking agents (F1) fluorene skeleton-containing epoxy crosslinking agent and (F2) indane skeleton-containing epoxy crosslinking agent described below, alkoxymethyl crosslinking agents, methylol crosslinking agents, isocyanuric acid-based epoxy crosslinking agents, and oxetanyl crosslinking agents are also preferred. The crosslinking agent (F) is preferably a compound having, in the molecule, two or more types of thermally crosslinkable groups selected from the group consisting of an alkoxymethyl group, a methylol group, an epoxy group, and an oxetanyl group.

[0255] <(F1) Fluorene skeleton-containing epoxy crosslinker, and (F2) Indane skeleton-containing epoxy crosslinker> The negative-tone photosensitive resin composition of the present invention preferably further contains an epoxy crosslinking agent as the crosslinking agent (F). Epoxy groups have high thermal reactivity. Because the thermal crosslinking reaction proceeds even at relatively low temperatures, the inclusion of an epoxy crosslinking agent enables the formation of a pattern with a low taper shape after thermal curing. The negative-tone photosensitive resin composition of the present invention preferably further contains an epoxy crosslinking agent having a fused polycyclic skeleton as the crosslinking agent (F). The presence of a fused polycyclic skeleton in the (F) crosslinking agent enables the formation of a pattern with a low taper shape after development and improves halftone characteristics. Furthermore, the adhesion of residues at the openings of the pattern after thermal curing can be suppressed. This is thought to be due to the significant interaction between the fused polycyclic skeleton and the fused polycyclic skeleton of the (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator described below, resulting in the uneven distribution of the hydrophobic crosslinking agent having the fused polycyclic skeleton around the photopolymerization initiator, thereby suppressing side etching during development.

[0256] The fused polycyclic skeleton of the (F) crosslinking agent preferably has one or more skeletons selected from the group consisting of a fluorene skeleton, a benzofluorene skeleton, a dibenzofluorene skeleton, an indene skeleton, an indane skeleton, a benzoindene skeleton, a benzoindane skeleton, a dihydroanthracene skeleton, a dihydrobenzanthracene skeleton, a dihydrophenanthrene skeleton, a dihydrobenzophenanthrene skeleton, a dihydronaphthalene skeleton, a dihydrobenzonaphthalene skeleton, a tetrahydronaphthalene skeleton, and a tetrahydrobenzonaphthalene skeleton.

[0257] The negative photosensitive resin composition of the present invention preferably contains, as the epoxy crosslinking agent having a fused polycyclic skeleton, one or more selected from the group consisting of (F1) a fluorene skeleton-containing epoxy crosslinking agent and (F2) an indane skeleton-containing epoxy crosslinking agent. The (F1) fluorene skeleton-containing epoxy crosslinking agent refers to a compound having an epoxy group, which is a thermally crosslinkable group, in the molecule and a fluorene skeleton. The (F2) indane skeleton-containing epoxy crosslinking agent refers to a compound having an indane skeleton, which is a thermally crosslinkable group, in the molecule. By containing one or more selected from the group consisting of (F1) a fluorene skeleton-containing epoxy crosslinking agent and (F2) an indane skeleton-containing epoxy crosslinking agent, a pattern with a low taper shape can be formed after development, and halftone characteristics can be improved. This is thought to be because the fluorene skeleton and indane skeleton interact significantly with the fused polycyclic skeleton of the fused polycyclic skeleton-containing photopolymerization initiator (C1-1a) described below, causing the crosslinker having the hydrophobic fluorene skeleton or indane skeleton to be unevenly distributed around the photopolymerization initiator, thereby suppressing side etching during development.

[0258] Examples of the fluorene skeleton-containing epoxy crosslinking agent (F1) include 9,9-bis[4-(2-glycidoxyethoxy)phenyl]fluorene, 9,9-bis(4-glycidoxyphenyl)fluorene, 9,9-bis[4-(2-glycidoxyethoxy)-1-naphthyl]fluorene, and 9,9-bis[3,4-bis(2-glycidoxyethoxy)phenyl]fluorene.

[0259] Examples of (F2) indane skeleton-containing epoxy crosslinking agents include 1,1-bis[4-(2-glycidoxyethoxy)phenyl]indan, 1,1-bis(4-glycidoxyphenyl)indan, 1,1-bis[4-(2-glycidoxyethoxy)phenyl]-3-phenylindan, 1,1-bis[4-(2-glycidoxyethoxy)-1-naphthyl]indan, 1,1-bis[3,4-bis(2-glycidoxyethoxy)phenyl]indan, 2,2-bis[4-(2-glycidoxyethoxy)phenyl]indan, and 2,2-bis[3,4-bis(2-glycidoxyethoxy)phenyl]indan.

[0260] The fluorene skeleton-containing epoxy crosslinking agent (F1) and the indane skeleton-containing epoxy crosslinking agent (F2) can be synthesized by a known method.

[0261] The total content of the (F1) fluorene skeleton-containing epoxy crosslinker and the (F2) indane skeleton-containing epoxy crosslinker in the negative-tone photosensitive resin composition of the present invention is preferably 1 part by mass or more, more preferably 5 parts by mass or more, per 100 parts by mass of the (A) alkali-soluble resin and the (B) radical-polymerizable compound, from the viewpoints of forming a pattern with a low taper shape after development and thermal curing and improving halftone characteristics. On the other hand, the total content of the (F1) fluorene skeleton-containing epoxy crosslinker and the (F2) indane skeleton-containing epoxy crosslinker is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, from the viewpoint of suppressing the generation of residues after development.

[0262] <<(G) Sensitizer>> The negative-tone photosensitive resin composition of the present invention preferably further contains a (G) sensitizer. The (G) sensitizer is a compound that absorbs UV light energy during exposure, generates excited triplet electrons through internal conversion and intersystem crossing, and transfers the energy to the (C1) photopolymerization initiator or the like. The inclusion of the (G) sensitizer can improve sensitivity during exposure. This is presumably because the (G) sensitizer absorbs long-wavelength light that is not absorbed by the (C1) photopolymerization initiator or the like, and transfers the energy from the (G) sensitizer to the (C1) photopolymerization initiator or the like, thereby improving the photoreaction efficiency. In addition to the (G1) fluorene skeleton-containing sensitizer and the (G2) indane skeleton-containing sensitizer described below, thioxanthone-based sensitizers are also preferred as (G) sensitizers. Examples of thioxanthone sensitizers include thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone.

[0263] <(G1) Fluorene skeleton-containing sensitizers and (G2) Indane skeleton-containing sensitizers> The negative-tone photosensitive resin composition of the present invention preferably further contains a (G) sensitizer having a fused polycyclic skeleton. The (G) sensitizer having a fused polycyclic skeleton can improve sensitivity during exposure and form a pattern with a low taper shape after development. In addition, halftone characteristics can be improved. This is thought to be because the fused polycyclic skeleton significantly interacts with the fused polycyclic skeleton of the (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator described below, thereby increasing the compatibility between the sensitizer and the photopolymerization initiator and allowing efficient energy transfer of UV light during exposure.

[0264] The fused polycyclic skeleton of the (G) sensitizer is preferably one or more selected from the group consisting of a fluorene skeleton, a benzofluorene skeleton, a dibenzofluorene skeleton, an indene skeleton, an indane skeleton, a benzoindene skeleton, a benzoindane skeleton, a dihydroanthracene skeleton, a dihydrobenzanthracene skeleton, a dihydrophenanthrene skeleton, a dihydrobenzophenanthrene skeleton, a dihydronaphthalene skeleton, a dihydrobenzonaphthalene skeleton, a tetrahydronaphthalene skeleton, and a tetrahydrobenzonaphthalene skeleton.

[0265] Furthermore, the compound exhibits a sensitizing effect by having a substituent containing an unshared electron pair capable of conjugating with the fused polycyclic skeleton and / or a substituent containing a π bond capable of conjugating with the fused polycyclic skeleton. Examples of the substituent containing an unshared electron pair include halogen, an amino group, a hydroxy group, an alkoxy group, and a mercapto group. Examples of the substituent containing a π bond include an aryl group, a nitro group, a cyano group, a carboxy group, a formyl group, an alkylcarbonyl group, an alkyloxycarbonyl group, and a sulfo group. Examples of the substituent containing a π bond also include a structure in which a carbon atom on the fused polycyclic skeleton forms an unsaturated double bond containing a π bond with a nitrogen atom, an oxygen atom, or a sulfur atom (e.g., a dialkyloxime group, a dialkylcarbonyl group, or a dialkylthiocarbonyl group).

[0266] The negative-tone photosensitive resin composition of the present invention preferably contains, as the (G) sensitizer having a fused polycyclic skeleton, one or more selected from the group consisting of (G1) fluorene skeleton-containing sensitizers and (G2) indane skeleton-containing sensitizers. The (G1) fluorene skeleton-containing sensitizer refers to a compound containing a fluorene skeleton in its molecule and having a sensitizing effect. The (G2) indane skeleton-containing sensitizer refers to a compound containing an indane skeleton in its molecule and having a sensitizing effect. By containing one or more selected from the group consisting of the (G1) fluorene skeleton-containing sensitizer and the (G2) indane skeleton-containing sensitizer, sensitivity during exposure can be improved and a pattern with a low taper shape can be formed after development. In addition, halftone characteristics can be improved. Furthermore, adhesion of residues at pattern openings after thermal curing can be suppressed. This is thought to be because the fluorene skeleton and indane skeleton interact significantly with the fused polycyclic skeleton of the (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator and the fused polycyclic heterocyclic skeleton of the (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiator, which will be described later, thereby increasing the compatibility between the sensitizer and the photopolymerization initiator and allowing efficient energy transfer of UV light during exposure.

[0267] Examples of the fluorene skeleton-containing sensitizer (G1) include 2-bromofluorene, 2-phenylfluorene, 2-nitrofluorene, 2,7-dinitrofluorene, 2-cyanofluorene, benzofluorene, 9-fluorenone, 9-thiofluorenone, benzo-9-fluorenone, dibenzo-9-fluorenone, 2-chloro-9-fluorenone, 2-bromo-9-fluorenone, 2-iodo-9-fluorenone, 2-phenyl-9-fluorenone, 2-nitro-9-fluorenone, 2,7-dinitro-9-fluorenone, 2-cyano-9-fluorenone, and 2-carboxy-9-fluorenone.

[0268] Examples of the (G2) indan skeleton-containing sensitizer include 6-bromoindan, 6-phenylindan, 6-nitroindan, 6-cyanoindan, 6-bromoindene, 6-nitroindene, benzoindan, indan-1-one, benzoindan-1-one, benzoindene, inden-1-one, benzoinden-1-one, 6-chloroindan-1-one, 6-bromoindan-1-one, 6-iodoindan-1-one, 6-phenylindan-1-one, 6-nitroindan-1-one, 6-cyanoindan-1-one, 6-carboxyindan-1-one, 6-bromoinden-1-one, and 6-nitroinden-1-one.

[0269] The fluorene skeleton-containing sensitizer (G1) and the indane skeleton-containing sensitizer (G2) can be synthesized by known methods.

[0270] The total content of the fluorene skeleton-containing sensitizer (G1) and the indane skeleton-containing sensitizer (G2) in the negative-tone photosensitive resin composition of the present invention is preferably 0.1 parts by mass or more, more preferably 3 parts by mass or more, per 100 parts by mass of the alkali-soluble resin (A) and the radical-polymerizable compound (B), from the viewpoints of improving sensitivity during exposure, forming a pattern with a low taper shape after development, and improving halftone characteristics. On the other hand, the total content of the fluorene skeleton-containing sensitizer (G1) and the indane skeleton-containing sensitizer (G2) is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, from the viewpoints of improving sensitivity during exposure and suppressing the generation of residues after development.

[0271] <Chain transfer agent> The negative-type photosensitive resin composition of the present invention preferably further contains a chain transfer agent. By incorporating an appropriate amount of chain transfer agent, sensitivity during exposure can be improved and a pattern with a low taper shape can be formed after development. The chain transfer agent is preferably a thiol compound. The content of the chain transfer agent in the negative-type photosensitive resin composition of the present invention is preferably 0.01 parts by mass or more, relative to 100 parts by mass of the total of (A) the alkali-soluble resin and (B) the radically polymerizable compound. On the other hand, the content of the chain transfer agent is preferably 15 parts by mass or less.

[0272] <Polymerization inhibitor> The negative-type photosensitive resin composition of the present invention preferably further contains a polymerization inhibitor. By incorporating an appropriate amount of polymerization inhibitor, it is possible to suppress the generation of residues after development and improve the resolution after development. The polymerization inhibitor is preferably a hindered phenol compound, a hindered amine compound, or a benzimidazole compound. The content of the polymerization inhibitor in the negative-type photosensitive resin composition of the present invention is preferably 0.01 parts by mass or more, relative to 100 parts by mass of the total of (A) the alkali-soluble resin and (B) the radically polymerizable compound. On the other hand, the content of the polymerization inhibitor is preferably 10 parts by mass or less.

[0273] <Silane coupling agent> The negative-type photosensitive resin composition of the present invention preferably further contains a silane coupling agent. By incorporating an appropriate amount of the silane coupling agent, the adhesion between the cured film and the underlying substrate can be improved. The silane coupling agent is preferably a trifunctional organosilane, a tetrafunctional organosilane, or a silicate compound. The content of the silane coupling agent in the negative-type photosensitive resin composition of the present invention is preferably 0.01 parts by mass or more, based on 100 parts by mass of the total of (A) the alkali-soluble resin and (B) the radically polymerizable compound. Meanwhile, the content of the silane coupling agent is preferably 15 parts by mass or less.

[0274] <Surfactant> The negative photosensitive resin composition of the present invention preferably further contains a surfactant. By incorporating an appropriate amount of surfactant, the surface tension of the resin composition can be adjusted as desired, thereby improving the leveling properties during application and the uniformity of the coating film thickness. The surfactant is preferably a fluororesin-based surfactant, a silicone-based surfactant, a polyoxyalkylene ether-based surfactant, or an acrylic resin-based surfactant. The content of the surfactant in the negative photosensitive resin composition of the present invention is preferably 0.001% by mass or more of the total negative photosensitive resin composition. On the other hand, the content of the surfactant is preferably 1% by mass or less.

[0275] <Solvent> The negative-type photosensitive resin composition of the present invention preferably further contains a solvent. By incorporating a solvent, the resin composition can be formed into a film of the desired thickness on a substrate. Additionally, the leveling properties during application and the thickness uniformity of the coating film can be improved. From the viewpoint of solubility of various resins and additives, the solvent is preferably a compound having an alcoholic hydroxyl group, a compound having a carbonyl group, or a compound having three or more ether bonds. From the viewpoint of improving thickness uniformity by suppressing coating unevenness, a compound having a boiling point of 110°C or higher at atmospheric pressure is more preferred. On the other hand, from the viewpoint of improving flatness and thickness uniformity by suppressing film shrinkage during thermal curing, a compound having a boiling point of 250°C or lower at atmospheric pressure is more preferred. The content of the solvent in the negative-type photosensitive resin composition of the present invention can be appropriately adjusted depending on the application method, etc. For example, when forming a coating film by spin coating, the solvent typically accounts for 50 to 95% by mass of the entire negative-type photosensitive resin composition.

[0276] When the negative-tone photosensitive resin composition of the present invention contains a pigment (D1) as the colorant (D), the solvent is preferably a solvent having a carbonyl group or an ester bond. By including a solvent having a carbonyl group or an ester bond, the dispersion stability of the negative-tone photosensitive resin composition containing a pigment (D1) or the like can be improved, the generation of developer residue can be suppressed, and the storage stability of the coating liquid can be improved. From the viewpoint of improving dispersion stability and suppressing residue after development, the carbonyl group is preferably an alkylcarbonyl group, a dialkylcarbonyl group, a formyl group, a carboxyl group, an amide group, an imide group, a urea bond, or a urethane bond, more preferably an alkylcarbonyl group, a dialkylcarbonyl group, or a formyl group, and even more preferably an alkylcarbonyl group or a dialkylcarbonyl group. The ester bond is preferably a carboxylic acid ester bond, a carbonate ester bond, or a formic acid ester bond, and more preferably a carboxylic acid ester bond. Among the carboxylic acid ester bonds, acetate bonds, propionate bonds, and butyrate bonds are more preferred, and acetate bonds are even more preferred.

[0277] Examples of solvents having an acetate bond include 3-methoxy-n-butyl acetate, 3-methyl-3-methoxy-n-butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, cyclohexanol acetate, propylene glycol diacetate, and 1,4-butanediol diacetate.

[0278] In the negative-type photosensitive resin composition of the present invention, the content of the solvent having a carbonyl group or an ester bond in the solvent is preferably 30 to 100 mass%, more preferably 50 to 100 mass%, and even more preferably 70 to 100 mass%. When the content is 30 to 100 mass%, the dispersion stability of the pigment (D1) can be improved, the generation of residues in the developer can be suppressed, and the storage stability of the coating liquid can be improved.

[0279] <<Method for producing the negative-type photosensitive resin composition of the present invention>> A typical method for producing the negative-tone photosensitive resin composition of the present invention will now be described. When the composition contains a (D1) pigment containing a (Da) black agent as the (D) colorant, a (E) dispersant is added to a solution of an (A) alkali-soluble resin, and the (D1) pigment is dispersed in this mixed solution using a disperser to prepare a pigment dispersion. Next, the (A) alkali-soluble resin, (B) radical-polymerizable compound, (C1) photopolymerization initiator, other additives, and an optional solvent are added to this pigment dispersion, and the mixture is stirred for 20 minutes to 3 hours to obtain a homogeneous solution. After stirring, the resulting solution is filtered to obtain the negative-tone photosensitive resin composition of the present invention. From the viewpoints of dispersion efficiency and fine dispersion, a bead mill is preferred as the disperser. Examples of beads for the bead mill include titania beads, zirconia beads, and zircon beads. The bead diameter of the bead mill is preferably 0.01 to 6 mm, more preferably 0.015 to 5 mm, and even more preferably 0.03 to 3 mm.

[0280] <Low taper curing pattern> A cured film can be produced by curing the negative photosensitive resin composition of the present invention. It is possible to obtain a cured film containing a pattern with a small taper shape. The taper angle of the inclined sides in the cross section of the cured pattern contained in the cured film from the negative photosensitive resin composition of the present invention is preferably 10° or more, more preferably 15° or more, from the viewpoint of improving the resolution of the display device. On the other hand, the taper angle of the inclined sides in the cross section of the cured pattern contained in the cured film is preferably 60° or less, more preferably 45° or less, from the viewpoint of preventing electrode disconnection, suppressing electric field concentration, and suppressing degradation of the light-emitting device.

[0281] <Optical density of cured film> The optical density per μm of film thickness in the visible light region of the cured film obtained by curing the negative-type photosensitive resin composition of the present invention is preferably 0.3 or more, more preferably 1.0 or more, and even more preferably 1.5 or more, from the viewpoints of reducing external light reflection due to improved light-shielding properties and improving the contrast of display devices. The visible light region has wavelengths of approximately 400 to 700 nm. This film is particularly suitable for applications requiring high contrast, and is preferred as a light-shielding pixel dividing layer, TFT planarizing layer, TFT protective layer, interlayer insulating layer, or gate insulating layer for organic electroluminescence displays. On the other hand, the optical density per μm of film thickness is preferably 5.0 or less, more preferably 3.0 or less, from the viewpoints of improving sensitivity during exposure and forming patterns with a low taper shape. The optical density per μm of film thickness of the cured film can be adjusted by the composition and content ratio of the colorant (D) described above.

[0282] <Curing pattern with step shape> The negative-type photosensitive resin composition of the present invention can form a pattern having a stepped shape with a sufficient difference in film thickness between thick and thin film portions while maintaining high sensitivity. In addition, it is possible to reduce the taper by controlling the pattern shape after development. Therefore, the composition is suitable for applications involving the simultaneous formation of stepped shapes, such as pixel dividing layers, electrode insulating layers, wiring insulating layers, TFT planarizing layers, electrode planarizing layers, wiring planarizing layers, TFT protective layers, electrode protective layers, wiring protective layers, interlayer insulating layers, gate insulating layers, color filters, black matrices, and black column spacers. The composition is preferred as a pixel dividing layer, TFT planarizing layer, TFT protective layer, interlayer insulating layer, or gate insulating layer, and more preferred as a pixel dividing layer, TFT planarizing layer, or TFT protective layer. In particular, the negative-type photosensitive resin composition of the present invention is particularly suitable for the simultaneous formation of stepped shapes in pixel dividing layers in organic electroluminescent (EL) displays, which require a combination of high sensitivity, halftone characteristics, and a low taper shape.

[0283] An example of a cross section of a cured pattern having a stepped shape obtained from the negative photosensitive resin composition of the present invention is shown in Figure 2. The thick film portion 34 in the stepped shape corresponds to the cured portion during exposure and has the maximum film thickness of the cured pattern. The thin film portions 35a, 35b, and 35c in the stepped shape correspond to the half-tone exposed portion during exposure and have a film thickness smaller than that of the thick film portion 34. The taper angles θ of the inclined sides 36a, 36b, 36c, 36d, and 36e in the cross section of the cured pattern having a stepped shape are a ,θ b ,θ c ,θ d ,θ e It is preferable that each of the taper angles is small. a ,θ b ,θ c ,θ d ,θ e As shown in Figure 2, the term "rectangular" refers to the angle within the cross section of the cured pattern having a stepped shape, formed by the horizontal side 37 of the underlying substrate on which the cured pattern is formed, or the horizontal side of the thin film portions 35a, 35b, and 35c, and the inclined sides 36a, 36b, 36c, 36d, and 36e in the cross section of the cured pattern having a stepped shape that intersects with the horizontal sides of the thin film portions 35a, 35b, and 35c. Here, "forward taper" refers to a taper angle that is greater than 0° and less than 90°, and "reverse taper" refers to a taper angle that is greater than 90° and less than 180°. Furthermore, "rectangular" refers to a taper angle of 90°, and "low taper" refers to a taper angle that is greater than 0° and less than 60°.

[0284] The taper angle of the inclined side in the cross section of the cured pattern having a stepped shape obtained from the negative photosensitive resin composition of the present invention is the same as the preferred taper angle of the cured pattern having a low taper shape described above.

[0285] The area having the largest thickness between the plane of the lower surface and the plane of the upper surface of the cured pattern having a step shape obtained from the negative photosensitive resin composition of the present invention is called the thick film portion 34, and the area having a thickness smaller than that of the thick film portion 34 is called the thin film portion 35. The thickness of the thick film portion 34 is (T FT) μm, and the thickness of the thin film portions 35a, 35b, and 35c arranged on the thick film portion 34 via at least one step shape is (T HT )μm, (T FT ) and (T HT ) and the film thickness difference (ΔT FT-HT ) μm is preferably 0.5 μm or more, more preferably 1.0 μm or more, even more preferably 1.5 μm or more, even more preferably 2.0 μm or more, particularly preferably 2.5 μm or more, and most preferably 3.0 μm or more. If the film thickness difference is 1.5 μm or more, the contact area with the deposition mask when forming the light-emitting layer can be reduced, which can suppress a decrease in panel yield and improve the reliability of the light-emitting element. In addition, since a single layer of the cured pattern having a stepped shape has a sufficient film thickness difference, it is possible to shorten the process time. On the other hand, the film thickness difference (ΔT FT-HT ) μm is preferably 10.0 μm or less, more preferably 9.5 μm or less, even more preferably 9.0 μm or less, even more preferably 8.5 μm or less, and particularly preferably 8.0 μm or less. When the film thickness difference is 10.0 μm or less, the exposure dose during formation of a cured pattern having a stepped shape can be reduced, enabling a reduction in takt time.

[0286] The thickness of the thick film portion 34 (T FT ) μm and the film thickness of the thin film portions 35a, 35b, and 35c (T HT ) μm preferably satisfy the relationships expressed by the general formulas (α) to (γ).

[0287] 2.0≦(T FT )≦10.0 (α) 0.20≦(T HT )≦7.5 (β) 0.10×(T FT )≦(T HT )≦0.75×(T FT ) (γ) The thickness of the thick film portion 34 (T FT ) μm and the film thickness of the thin film portions 35a, 35b, and 35c (T HT ) μm preferably further satisfies the relationship expressed by the general formulas (δ) to (ζ).

[0288] 2.0≦(TFT )≦10.0 (δ) 0.30≦(T HT )≦7.0 (ε) 0.15×(T FT )≦(T HT )≦0.70×(T FT ) (ζ) The thickness of the thick film portion 34 (T FT ) μm and the film thickness of the thin film portions 35a, 35b, and 35c (T HT When the thickness is within the above range, the reliability of the light-emitting device can be improved and the process time can be shortened.

[0289] <Organic EL display having a cured film obtained by curing the negative-type photosensitive resin composition of the present invention> The negative-type photosensitive resin composition of the present invention can form a pattern with a low taper shape and can also produce a cured film with excellent heat resistance. Furthermore, since it can improve the reliability of light-emitting devices, it is particularly suitable for applications where device failure or performance degradation due to degassing caused by thermal decomposition, or breakage of electrode wiring due to a highly tapered pattern shape, are anticipated. Therefore, it is suitable for applications such as pixel dividing layers, TFT planarizing layers, TFT protective layers, interlayer insulating layers, and gate insulating layers in organic EL displays.

[0290] In addition, when the organic EL display contains the colorant (D), it is possible to prevent the electrode wiring from becoming visible or reduce external light reflection, thereby improving the contrast of the organic EL display. Therefore, as the contrast improves, it is not necessary to form a polarizing plate or a quarter-wave plate on the light extraction side of the light-emitting element, which improves the bendability of the organic EL display and enables the production of an organic EL display with excellent flexibility. The organic EL display of the present invention preferably has a curved display unit. The radius of curvature of this curved surface is preferably 0.1 mm or more, more preferably 0.3 mm or more, from the viewpoint of suppressing display defects in the curved display unit. The radius of curvature of the curved surface is preferably 10 mm or less, more preferably 7 mm or less, and even more preferably 5 mm or less, from the viewpoint of miniaturization and high resolution of the organic EL display.

[0291] <Schematic cross-sectional view of the manufacturing process for an OLED display> As an example of a process using the negative-tone photosensitive resin composition of the present invention, a process in which a cured film of the composition is used as a light-shielding pixel dividing layer in an organic electroluminescence display will be described with reference to the schematic cross-sectional view shown in FIG. 1. First, (Step 1) a thin-film transistor (hereinafter, "TFT") 2 is formed on a glass substrate 1, and a photosensitive material for a TFT planarization film is deposited and patterned by photolithography, followed by thermal curing to form a cured TFT planarization film 3. Next, (Step 2) a silver-palladium-copper alloy (hereinafter, "APC") is deposited by sputtering and patterned by etching using a photoresist to form an APC layer. Furthermore, a film of indium tin oxide (hereinafter, "ITO") is deposited on top of the APC layer by sputtering and patterned by etching using a photoresist to form a reflective electrode 4 as a first electrode. Then, (Step 3) a negative-tone photosensitive resin composition of the present invention is applied and prebaked to form a prebaked film 5a. Next, (Step 4) the film is irradiated with actinic rays 7 through a mask 6 having a desired pattern. Next, (Step 5) development and patterning are performed, followed by bleaching exposure and middle baking as necessary, and thermal curing to form a cured pattern 5b having the desired pattern as a light-shielding pixel division layer. Thereafter, (Step 6) an EL-emitting material is deposited by vapor deposition through a mask to form an EL-emitting layer 8, a magnesium-silver alloy (hereinafter referred to as "MgAg") is deposited by vapor deposition, and patterned by etching using a photoresist to form a transparent electrode 9 as a second electrode. Next, (Step 7) a photosensitive material for a planarization film is deposited, patterned by photolithography, and thermally cured to form a planarization cured film 10. A cover glass 11 is then bonded to the film to obtain an organic EL display having the negative-type photosensitive resin composition of the present invention as a light-shielding pixel division layer.

[0292] <Method of manufacturing the cured film> The method for producing a display device such as an organic EL display using the negative photosensitive resin composition of the present invention includes the following steps (1) to (4). (1) forming a coating film of the negative photosensitive resin composition of the present invention on a substrate; (2) a step of irradiating the coating film of the negative photosensitive resin composition with actinic rays through a photomask; (3) developing the pattern using an alkaline solution to form a pattern of the negative photosensitive resin composition; and (4) A step of heating the pattern to obtain a cured pattern of the negative photosensitive resin composition.

[0293] <Process for forming coating film> The method for manufacturing a display device using the negative photosensitive resin composition of the present invention includes the step of (1) forming a coating film of the negative photosensitive resin composition on a substrate. Examples of the method for forming a film of the negative photosensitive resin composition include a method of applying the above-described resin composition on a substrate, or a method of applying the above-described resin composition in a pattern on a substrate.

[0294] The substrate may be, for example, a glass substrate having, as an electrode or wiring, an oxide containing one or more elements selected from indium, tin, zinc, aluminum, and gallium, a metal (molybdenum, silver, copper, aluminum, chromium, titanium, etc.), or CNTs (Carbon Nano Tubes). An example of an oxide containing one or more elements selected from indium, tin, zinc, aluminum, and gallium is indium tin oxide (ITO).

[0295] <Method of applying a negative photosensitive resin composition onto a substrate> Examples of methods for applying the negative photosensitive resin composition onto a substrate include spin coating, curtain flow coating, spray coating, and slit coating. The coating thickness varies depending on the coating method, the solid content and viscosity of the resin composition, etc., but the composition is usually applied so that the film thickness after coating and pre-baking is 0.1 to 30 μm.

[0296] It is preferable to form a film by applying a negative photosensitive resin composition onto a substrate and then prebaking it. Prebaking can be performed using an oven, a hot plate, infrared radiation, a flash annealing device, a laser annealing device, or the like. The prebaking temperature is preferably 50 to 150°C. The prebaking time is preferably 30 seconds to several hours. Prebaking may be performed in two or more stages, such as prebaking at 80°C for 2 minutes and then prebaking at 120°C for 2 minutes.

[0297] <Method for patterning a coating film formed on a substrate> Methods for patterning a coating film of a negative photosensitive resin composition formed on a substrate include, for example, a method of directly patterning by photolithography and a method of patterning by etching. From the viewpoints of improving productivity by reducing the number of steps and shortening the process time, the method of directly patterning by photolithography is preferred.

[0298] <Step of irradiating activated actinic rays through a photomask> The method for producing a display device using the negative photosensitive resin composition of the present invention includes the step of (2) irradiating a coating film of the negative photosensitive resin composition with actinic rays through a photomask. Examples of the method for irradiating a coating film of the negative photosensitive resin composition with actinic rays through a photomask include patterning exposure using an exposure machine such as a stepper, a scanner, a mirror projection mask aligner (MPA), or a parallel light mask aligner (PLA).

[0299] The exposure wavelength of the actinic rays is preferably 10 nm or more, more preferably 100 nm or more, and even more preferably 200 nm or more. On the other hand, the exposure wavelength of the actinic rays is preferably 450 nm or less, more preferably 420 nm or less, and even more preferably 380 nm or less. Furthermore, the j-line (wavelength 313 nm), i-line (wavelength 365 nm), h-line (wavelength 405 nm), or g-line (wavelength 436 nm) of a mercury lamp, or a mixture of the i-line, h-line, and g-line, is particularly preferred. Examples of actinic rays include ultraviolet light, visible light, electron beams, X-rays, XeF (wavelength 351 nm) lasers, XeCl (wavelength 308 nm) lasers, KrF (wavelength 248 nm) lasers, and ArF (wavelength 193 nm) lasers. The exposure dose of the actinic rays is 100 J / m in terms of i-line illuminance. 2 (10mJ / cm 2 )~30,000J / m 2 (3,000mJ / cm 2 ) or less is preferred.

[0300] The photomask preferably has a pattern including a light-transmitting portion and a light-shielding portion, and a half-tone photomask having a semi-transmitting portion between the light-transmitting portion and the light-shielding portion, the semi-transmitting portion having a transmittance lower than that of the light-transmitting portion and higher than that of the light-shielding portion. By exposing using a half-tone photomask, a pattern having a stepped shape can be formed after development. In the pattern having a stepped shape, the portion formed from the exposed portion irradiated with activated actinic rays through the light-transmitting portion corresponds to a thick film portion, and the portion formed from the half-tone exposed portion irradiated with activated actinic rays through the semi-transmitting portion corresponds to a thin film portion. The half-tone photomask has a portion where the light-transmitting portion and the semi-transmitting portion are adjacent. By having a portion where the light-transmitting portion and the semi-transmitting portion are adjacent, a pattern having the thick film portion corresponding to the light-transmitting portion on the photomask and the thin film portion corresponding to the semi-transmitting portion on the photomask can be formed after development. Furthermore, the half-tone photomask has a portion where the light-shielding portion and the semi-transmitting portion are adjacent. After development, a pattern can be formed having openings corresponding to the light-shielding portions on the photomask and the thin film portions corresponding to the semi-transparent portions on the photomask. By having the above-mentioned portions in the halftone photomask, a pattern having a stepped shape including the thick film portions, the thin film portions, and the openings can be formed after development.

[0301] The transmittance of the light-transmitting portion of the halftone photomask is (%T FT )%, the transmittance (%T HT )% is (%T FT The transmittance (%T) of the semi-transparent portion is preferably 10% or more, more preferably 15% or more, even more preferably 20% or more, and particularly preferably 25% or more. HT When the transmittance (%T HT )% is (%T FT The transmittance (%T) of the semi-transparent portion is preferably 60% or less, more preferably 55% or less, even more preferably 50% or less, and particularly preferably 45% or less. HTWhen the % is within the above range, the difference in film thickness between the thick film portion and the thin film portion, and the difference in film thickness between the adjacent thin film portions on both sides of any step can be made sufficiently large, thereby suppressing deterioration of the light-emitting element. In addition, since there is a sufficient difference in film thickness in one layer of a pattern having a step shape, the process time can be shortened.

[0302] In a pattern having a stepped shape obtained by irradiating activated actinic rays through a halftone photomask, the transmittance (%T HT )% is, (%T FT )%, the film thickness of the thin film part when it is 30% of (T HT30 ) μm, and the transmittance of the semi-transparent part (%T HT )% is, (%T FT ) is 20% of the film thickness of the thin film part (T HT20 )μm, (T HT30 ) and (T HT20 ) and the film thickness difference (ΔT HT30-HT20 ) μm is preferably 0.3 μm or more, more preferably 0.5 μm or more, even more preferably 0.7 μm or more, and particularly preferably 0.8 μm or more. When the film thickness difference is within the above range, the film thickness difference between the thick film portion and the thin film portion, and the film thickness difference between the adjacent thin film portions on both sides of any step can be made sufficiently large, thereby suppressing deterioration of the light-emitting element. In addition, since there is a sufficient film thickness difference in one layer of a pattern having a step shape, it is possible to shorten the process time. On the other hand, the film thickness difference (ΔT HT30-HT20 ) μm is preferably 1.5 μm or less, more preferably 1.4 μm or less, even more preferably 1.3 μm or less, and particularly preferably 1.2 μm or less. When the film thickness difference is within the above range, it is possible to reduce the occurrence of film thickness variations due to slight fluctuations in the exposure amount caused by the device, etc., thereby improving film thickness uniformity and the yield in the production of organic EL displays.

[0303] After exposure, post-exposure baking may be performed, which is expected to have the effect of improving the resolution after development or increasing the tolerance range of development conditions.

[0304] <Step of forming a pattern by developing using an alkaline solution> The method for manufacturing a display device using the negative-tone photosensitive resin composition of the present invention includes the step of (3) developing with an alkaline solution to form a pattern of the negative-tone photosensitive resin composition. Examples of the method for developing with an alkaline solution after irradiating with actinic rays through a photomask include a method using an automatic developer. Because the negative-tone photosensitive resin composition has negative photosensitivity, after development, the unexposed areas are removed with the developer, forming a relief pattern. Furthermore, developing with an alkaline solution can suppress the generation of development residues in the openings and improve the light-emitting reliability of the display device.

[0305] The developer is preferably an alkaline solution. The alkaline solution is preferably an organic alkaline solution or an aqueous solution of an alkaline compound, such as diethanolamine, sodium hydroxide, potassium hydroxide, sodium carbonate, or potassium carbonate. From the viewpoint of reducing metal impurities and improving the reliability of the display device, the alkaline solution preferably contains one or more compounds selected from tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine, and triethylamine, and more preferably contains one or more compounds selected from the group consisting of tetramethylammonium hydroxide and tetraethylammonium hydroxide. An organic solvent may be used as the developer. A mixed solution containing both an organic solvent and a poor solvent for the negative photosensitive resin composition may be used as the developer.

[0306] The alkali concentration of the alkaline solution is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 1% by mass or more, and particularly preferably 2% by mass or more. On the other hand, the alkali concentration is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less. When the alkali concentration is within the above range, the generation of residue after development can be suppressed and the takt time during development can be shortened.

[0307] Examples of the development method include paddle development, spray development, and dip development. From the viewpoint of suppressing contamination of the device during development and reducing process costs by reducing the amount of developer used, paddle development is preferred as the development method. By suppressing contamination of the device during development, substrate contamination during development can be suppressed, and the reliability of the display device can be improved. On the other hand, from the viewpoint of suppressing the generation of residues after development, spray development is preferred as the development method. Furthermore, from the viewpoint of reducing the amount of developer used by reusing the developer and reducing process costs, dip development is preferred as the development method.

[0308] The development time is preferably 5 seconds or more, more preferably 10 seconds or more, even more preferably 30 seconds or more, and particularly preferably 1 minute or more. When the development time is within the above range, the generation of residue after development can be suppressed. On the other hand, from the viewpoint of shortening the takt time during development, the development time is preferably 30 minutes or less, more preferably 15 minutes or less, even more preferably 10 minutes or less, and particularly preferably 5 minutes or less. After development, it is preferable to wash the obtained relief pattern with a rinse solution. When an alkaline aqueous solution is used as the developer, water is preferred as the rinse solution. As the rinse solution, an aqueous solution of alcohols, an aqueous solution of esters, an aqueous solution of an acidic compound, or an organic solvent may also be used.

[0309] <Process for photo-curing the pattern> The method for manufacturing a display device using the negative photosensitive resin composition of the present invention preferably further comprises a step of photocuring the pattern after the step (3) of developing with an alkaline solution to form a pattern of the negative photosensitive resin composition. The step of photocuring the pattern preferably involves irradiating the pattern of the negative photosensitive resin composition with activated actinic rays. The method of irradiating activated actinic rays and the activated actinic rays are the same as those in the step (2) of irradiating a coating film of the negative photosensitive resin composition with activated actinic rays through a photomask.

[0310] The process of photocuring the pattern improves the crosslink density of the pattern and reduces the amount of low-molecular-weight components that cause degassing, thereby improving the reliability of display devices equipped with a pattern of the negative photosensitive resin composition. Furthermore, when the pattern of the negative photosensitive resin composition has a stepped shape, pattern reflow during thermal curing of the pattern can be suppressed, and a stepped pattern with a sufficient film thickness difference between the thick and thin film portions can be formed even after thermal curing. Additionally, maintaining the reflowability of the film surface during thermal curing improves flatness, thereby suppressing a decrease in panel yield. Furthermore, in the production of organic EL displays equipped with a pattern of the negative photosensitive resin composition, the contact area with the vapor deposition mask during formation of the organic EL layer can be reduced, thereby suppressing a decrease in panel yield and improving the reliability of the light-emitting element.

[0311] When the photomask in the step (2) of irradiating the coating film of the negative photosensitive resin composition with actinic rays through a photomask is a halftone photomask, the exposure dose of actinic rays in the step of photocuring the pattern is set to (E BLEACH )mJ / cm 2 and the exposure dose in the transparent portion of the photomask in the step (2) of irradiating the active actinic ray through the photomask is (E EXPO )mJ / cm 2 When the exposure ratio (E BLEACH ) / (E EXPO ) is preferably 0.1 or more, more preferably 0.3 or more, even more preferably 0.5 or more, even more preferably 0.7 or more, and particularly preferably 1 or more. When the exposure dose ratio is within the above range, pattern reflow during thermal curing of the pattern of the negative photosensitive resin composition can be suppressed. In addition, a decrease in panel yield can be suppressed. Furthermore, from the viewpoint of improving the step film thickness, the exposure dose ratio is preferably 0.5 or more, more preferably 0.7 or more, and even more preferably 1 or more. Furthermore, from the viewpoint of improving the yield, the exposure dose ratio is preferably less than 4, more preferably less than 3.5, and even more preferably less than 3.

[0312] After obtaining a pattern of the negative photosensitive resin composition, middle baking may be performed. By performing middle baking, the resolution after thermal curing is improved and the pattern shape after thermal curing can be controlled as desired.

[0313] <Step of heating the pattern to obtain a hardened pattern> The method for manufacturing a display device using the negative photosensitive resin composition of the present invention includes (4) a step of heating the pattern of the negative photosensitive resin composition described above to obtain a cured pattern of the negative photosensitive resin composition. Examples of methods for heating the pattern of the negative photosensitive resin composition include methods using an oven, a hot plate, infrared radiation, a flash annealing device, or a laser annealing device. Heating the pattern of the negative photosensitive resin composition to thermally cure it improves the heat resistance of the cured film and also enables the formation of a pattern with a low taper shape.

[0314] The heat curing temperature is preferably 150°C or higher, more preferably 200°C or higher, and even more preferably 250°C or higher, from the viewpoint of improving the heat resistance of the cured film and forming a pattern with a low taper shape after heat curing. On the other hand, from the viewpoint of shortening the takt time, the heat curing temperature is preferably 500°C or lower, more preferably 450°C or lower, and even more preferably 400°C or lower. The heat curing time is preferably 1 minute or longer, more preferably 5 minutes or longer, even more preferably 10 minutes or longer, and particularly preferably 30 minutes or longer, from the viewpoint of forming a pattern with a low taper shape after heat curing. On the other hand, from the viewpoint of shortening the takt time, the heat curing time is preferably 300 minutes or shorter, more preferably 250 minutes or shorter, even more preferably 200 minutes or shorter, and particularly preferably 150 minutes or shorter. Heat curing may also be performed in two or more stages, such as heat curing at 150°C for 30 minutes and then heat curing at 250°C for 30 minutes.

[0315] Examples of the treatment atmosphere for thermal curing include air, oxygen, nitrogen, helium, neon, argon, krypton, or xenon atmosphere, a gas atmosphere containing 1 to 10,000 ppm (0.0001 to 1% by mass) of oxygen, or a vacuum. From the viewpoint of shortening the takt time during thermal curing, air is preferred. Furthermore, from the viewpoint of improving the reliability of the light-emitting device, nitrogen, helium, neon, argon, krypton, or xenon atmosphere, a gas atmosphere containing 1 to 10,000 ppm (0.0001 to 1% by mass) of oxygen, or a vacuum is preferred. As the oxygen-containing gas, a gas containing 1,000 ppm or less of oxygen is more preferred, and a gas containing 100 ppm or less is even more preferred. [Example]

[0316] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. The names of the compounds used, for which abbreviations are used, are shown below. 6FDA: 2,2-(3,4-dicarboxyphenyl)hexafluoropropane dianhydride; 4,4'-hexafluoropropane-2,2-diyl-bis(1,2-phthalic anhydride) A-BPEF: "NK ESTER" (registered trademark) A-BPEF (manufactured by Shin-Nakamura Chemical Co., Ltd.; 9,9-bis[4-(2-acryloxyethoxy)phenyl]fluorene) A-DCP: "NK ESTER" (registered trademark) A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.; dimethylol-tricyclodecane diacrylate) APC: Argentum-Palladium-Copper (silver-palladium-copper alloy) BAHF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane BAPF: 9,9-bis(3-amino-4-hydroxyphenyl)fluorene BFE: 1,2-bis(4-formylphenyl)ethane BGPF: 9,9-bis(4-glycidoxyphenyl)fluorene Bk-A1103: "CHROMOFINE" (registered trademark) BLACK A1103 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.; azo-based black pigment with a primary particle size of 50 to 100 nm) Bk-CBF1: Surface-coated benzofuranone-based black pigment Bk-S0084: "PALIOGEN" (registered trademark) BLACK S0084 (manufactured by BASF; perylene-based black pigment with a primary particle size of 50 to 100 nm) Bk-S0100CF: "IRGAPHOR" (registered trademark) BLACK S0100CF (manufactured by BASF; benzofuranone-based black pigment with a primary particle size of 40 to 80 nm) cyEpoTMS: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane D. BYK-167: "DISPERBYK" (registered trademark)-167 (manufactured by BYK Japan; polyurethane-based dispersant having a tertiary amino group and an amine value of 13 mg KOH / g (solid content: 52% by mass)) DNFLN: 2,7-dinitro-9-fluorenone DPCA-60: "KAYARAD" (registered trademark) DPCA-60 (manufactured by Nippon Kayaku Co., Ltd.; ε-caprolactone-modified dipentaerythritol hexaacrylate having six oxypentylenecarbonyl structures in the molecule) DPHA: "KAYARAD" (registered trademark) DPHA (manufactured by Nippon Kayaku Co., Ltd.; dipentaerythritol hexaacrylate) GMA: Glycidyl methacrylate HA: N,N'-bis[5,5'-hexafluoropropane-2,2-diyl-bis(2-hydroxyphenyl)]bis(3-aminobenzoic acid amide) IDN-1: 1,1-bis[4-(2-acryloxyethoxy)phenyl]indan IGZO: Indium Gallium Zinc Oxide ITO: Indium tin oxide MAA: methacrylic acid MAP: 3-aminophenol; meta-aminophenol MBA: 3-methoxy-n-butyl acetate MeTMS: methyltrimethoxysilane MgAg: Magnesium-Argentum (Magnesium-Silver Alloy) NA: 5-norbornene-2,3-dicarboxylic anhydride; Nadic anhydride NC-7300L: Epoxy resin with a structural unit containing a naphthalene skeleton, a benzene skeleton, and two epoxy groups (manufactured by Nippon Kayaku Co., Ltd.) NMP: N-methyl-2-pyrrolidone ODB-HBT: A mixture of dicarboxylic acid derivatives obtained by reacting bis(4-carboxyphenyl) ether with 1-hydroxy-1,2,3-benzotriazole. ODPA: Bis(3,4-dicarboxyphenyl) ether dianhydride; Oxydiphthalic dianhydride PB60: CI Pigment Blue 60 PR179: CI Pigment Red 179 PY139: CI Pigment Yellow 139 PY192: CI Pigment Yellow 192 PGMEA: Propylene glycol monomethyl ether acetate PHA: Phthalic anhydride PhTMS: phenyltrimethoxysilane S-20000: "SOLSPERSE" (registered trademark) 20000 (manufactured by Lubrizol; a polyoxyalkylene ether dispersant having a tertiary amino group and an amine value of 32 mg KOH / g (solids concentration: 100% by mass) SiDA: 1,3-bis(3-aminopropyl)tetramethyldisiloxane STR: Styrene TCDM: Tricyclo[5.2.1.0 methacrylate 2,6 ]Decan-8-yl;Dimethylol-tricyclodecane dimethacrylate THPHA: 1,2,3,6-tetrahydrophthalic anhydride TMAH: Tetramethylammonium hydroxide TMOS: Tetramethoxysilane TPK-1227: Carbon black with a surface treatment that introduces sulfonic acid groups (manufactured by CABOT) TR-FR-201: 9,9-bis(4-glycidoxyphenyl)fluorene (T Ronly) WR-301: "ADEKA ARKLS" (registered trademark) WR-301 (manufactured by ADEKA Corporation; a polycyclic side chain-containing resin obtained by reacting a resin obtained by ring-opening addition reaction of an aromatic compound having an epoxy group and an unsaturated carboxylic acid with a carboxylic acid anhydride; acid equivalent: 560, double bond equivalent: 450) ZXR-1816H: An acid-modified epoxy resin obtained by reacting a resin obtained by ring-opening addition reaction of an epoxy resin having structural units containing a tricyclodecane skeleton, a benzene skeleton, and an epoxy group with an unsaturated carboxylic acid, with a carboxylic acid anhydride. Acid equivalent: 570, double bond equivalent: 520 g / mol (manufactured by Nippon Kayaku Co., Ltd.) The hydroxyl group-containing diamine compound (HA) having the following structure used in Synthesis Example 4 was synthesized by a known method.

[0317] [ka]

[0318] The compositions of the (A) alkali-soluble resins obtained in Synthesis Examples 1 to 10 are summarized in Table 1. Synthesis Examples 1 to 5, 7, 8, and 10 are based on the method described in WO 2017 / 057281, Synthesis Example 6 is based on the method described in WO 2017 / 057143, and Synthesis Example 9 is based on the method described in WO 2017 / 159876, and each resin was synthesized by a known method. In Synthesis Example 10, GMA having an epoxy group was reacted with a carboxy group in the resin derived from MAA, and all of the epoxy groups of GMA were subjected to ring-opening addition.

[0319] [Table 1]

[0320] Coating Example 1: Synthesis of surface-coated benzofuranone-based black pigment (Bk-CBF1) 150 g of the benzofuranone black pigment Bk-S0100CF (surface untreated) was added to a glass vessel containing 2,850 g of deionized water and stirred to obtain an aqueous pigment suspension. This was then transferred to a horizontal bead mill filled with 0.4 mm diameter zirconia beads for dispersion treatment, after which the entire amount was discharged back into the original glass vessel, and the temperature of the aqueous pigment suspension was raised to 60°C while stirring again, and the mixture was stirred for 30 minutes.

[0321] To the aqueous pigment suspension, a sodium silicate solution (Na2O·nSiO2·mH2O; 30% sodium oxide, 10% silicon dioxide) diluted 100 times with deionized water and 0.001 mol / L sulfuric acid were added to deposit silica onto the black pigment particle surface, resulting in a silica coating of 10.0 parts SiO2 per 100 parts black pigment. Next, a sodium aluminate solution (Na2O·nAl2O3·mH2O; 40% sodium oxide, 50% alumina) diluted 100 times with deionized water and 0.001 mol / L sulfuric acid were added to deposit alumina onto the silica coating layer, resulting in a silica coating of 2.0 parts Al2O3 per 100 parts black pigment. Subsequently, the filtration and water washing operations were repeated three times, and the mixture was dispersed in a horizontal bead mill filled with 0.4 mmφ zirconia beads and filtered to obtain a black residue, which was then dried in a drying oven and sized by dry grinding to obtain a surface-coated benzofuranone-based black pigment (Bk-CBF1).

[0322] Analysis by time-of-flight secondary ion mass spectrometry and X-ray diffraction revealed that the coating amounts of silica and alumina on the obtained surface-coated benzofuranone-based black pigment (Bk-CBF1) were 10.0 parts by mass in terms of SiO2 and 2.0 parts by mass in terms of Al2O3, per 100 parts by mass of the black pigment, and the average coverage rate of the coating layer on the pigment was 97.5%.

[0323] Preparation Example 1 Preparation of pigment dispersion (Bk-1) 34.5 g of S-20000 as a dispersant and 782.0 g of MBA as a solvent were weighed and mixed, and stirred for 10 minutes to disperse the pigment. After that, 103.5 g of Bk-S0100CF as a colorant was weighed and mixed, and stirred for 30 minutes. Using a horizontal bead mill filled with 0.40 mmφ zirconia beads, a wet media dispersion process was performed to obtain a number average particle size of 100 nm, resulting in a pigment dispersion (Bk-1) with a solids concentration of 15% by mass and a colorant / dispersant ratio of 75 / 25 (by mass). The number average particle size of the pigment in the resulting pigment dispersion was 100 nm.

[0324] Preparation Example 2: Preparation of pigment dispersion (Bk-2) 92.0 g of a 30% by weight MBA solution of polyimide (PI-1) obtained in Synthesis Example 1 was weighed and mixed as the resin, 27.6 g of S-20000 as the dispersant, and 717.6 g of MBA as the solvent. The mixture was stirred for 10 minutes to disperse the resin, and then 82.8 g of Bk-S0100CF as the colorant was weighed and mixed. The mixture was stirred for 30 minutes, and then subjected to wet media dispersion treatment using a horizontal bead mill filled with 0.40 mmφ zirconia beads to obtain a pigment dispersion (Bk-2) with a solids concentration of 15% by weight and a colorant / resin / dispersant ratio of 60 / 20 / 20 (by weight). The number average particle size of the pigment in the resulting pigment dispersion was 100 nm.

[0325] Preparation Examples 3 to 8: Preparation of pigment dispersions (Bk-3) to (Bk-8) Pigment dispersions (Bk-3) to (Bk-8) were obtained by dispersing pigments in the same manner as in Preparation Example 2 using the types and ratios of (D) colorant, (A1) first resin, and (E) dispersant listed in Table 2-1.

[0326] The compositions of Preparation Examples 1 to 8 are shown in Table 2-1.

[0327] [Table 2-1]

[0328] As the (Da) black agent, the maximum transmission wavelengths of the colorant Bk-S0100CF contained in the pigment dispersions (Bk-1) to (Bk-3), the colorant Bk-S0084 contained in the pigment dispersion (Bk-4), and the colorant (a mixture of PR179, PY192, and PB60) contained in the pigment dispersion (Bk-9) are shown below. Bk-S0100CF:340nm Bk-S0084:350nm Mixture of PR179, PY192 and PB60: 390 nm A list of the (C1-1) oxime ester photopolymerization initiators used in each of the examples and comparative examples and their physical properties are shown in Table 2-2.

[0329] [Table 2-2]

[0330] The structural formulas of the (C1-1) oxime ester photopolymerization initiator and other photopolymerization initiators (IC-379EG, IC-127, IC-819, and HABI-102) used in each example and comparative example are shown below.

[0331] [ka]

[0332] [ka]

[0333] The structural units of the acid-modified epoxy resin (ZXR-1816H) and the acid-modified epoxy resin (AE-1) obtained in Synthesis Example 8 are shown below. The acid-modified epoxy resin (ZXR-1816H) has a structural unit represented by general formula (37a). The acid-modified epoxy resin (AE-1) has a structural unit represented by general formula (38a).

[0334] [ka]

[0335] The evaluation methods used in each of the examples and comparative examples are shown below.

[0336] (1) Weight-average molecular weight of resin The weight average molecular weight in terms of polystyrene was measured and determined using a GPC analyzer (HLC-8220; manufactured by Tosoh Corporation) and tetrahydrofuran or NMP as a fluidized bed according to JIS K7252-3 (2008) at around room temperature.

[0337] (2) Acid value, acid equivalent Using an automatic potentiometric titrator (AT-510; Kyoto Electronics Manufacturing Co., Ltd.), the acid value (unit: mgKOH / g) was measured by potentiometric titration according to JIS K2501 (2003) using a 0.1 mol / L sodium hydroxide / ethanol solution as the titration reagent and a xylene / N,N-dimethylformamide = 1 / 1 (mass ratio) as the titration solvent. The acid equivalent (unit: g / mol) was calculated from the measured acid value.

[0338] (3) Double bond equivalent The iodine value of the resin was measured by the Wiess method using an automatic potentiometric titrator (AT-510; Kyoto Electronics Manufacturing Co., Ltd.) with iodine monochloride solution (7.9 g iodine trichloride, 8.9 g iodine, 1,000 mL acetic acid) as the iodine source, 100 g / L potassium iodide solution as a trapping solution for unreacted iodine, and 0.1 mol / L sodium thiosulfate solution as the titration reagent, according to Section 6, "Iodine Value," of JIS K0070:1992, "Testing Methods for Acid Value, Saponification Value, Ester Value, Iodine Value, Hydroxyl Value, and Unsaponifiable Matter of Chemical Products." The double bond equivalent (g / mol) was calculated from the measured iodine value (gI / 100 g).

[0339] (4) Number average particle size of pigment Using a zeta potential, particle size, and molecular weight analyzer (Zetasizer Nano ZS; Sysmex Corporation), the pigment dispersion was measured at 1.0 × 10 -5 The pigment dispersion was diluted to a concentration of about 40% by volume, and the refractive index of the dilution solvent was set to that of PGMEA, and the refractive index of the object to be measured was set to 1.6. The number average particle size of the pigment in the pigment dispersion was measured by irradiating it with laser light having a wavelength of 633 nm.

[0340] (5) Pretreatment of the substrate Glass substrates (Geomatec Co., Ltd.; hereafter referred to as "ITO substrates") with a 100-nm ITO film formed by sputtering were subjected to a UV-O3 cleaning treatment for 100 seconds using a tabletop optical surface treatment device (PL16-110; Sen Special Light Sources Co., Ltd.). Si wafers (Electronics and Materials Corporation) were subjected to a dehydration bake treatment by heating at 130°C for 2 minutes using a hot plate (HP-1SA; AS ONE Corporation).

[0341] (6) Film thickness measurement Using a surface roughness and contour measuring instrument (SURFCOM1400D; manufactured by Tokyo Seimitsu Co., Ltd.), the film thickness was measured after pre-baking, development, and thermal curing at a measurement magnification of 10,000x, a measurement length of 1.0 mm, and a measurement speed of 0.30 mm / s.

[0342] (7) Sensitivity Using the method described in Example 1 below, a double-sided alignment single-sided exposure system (Mask Aligner PEM-6M; manufactured by Union Optical Co., Ltd.) was used to pattern the film using the i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) from an ultra-high pressure mercury lamp through a grayscale mask for sensitivity measurement (MDRM MODEL 4000-5-FS; manufactured by Opto-Line International). The film was then developed using a compact photolithography developing system (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.) to produce a developed film of a negative-tone photosensitive resin composition. The resolved pattern of the developed film was observed using an FPD / LSI inspection microscope (OPTIPHOT-300; manufactured by Nikon Corporation). The exposure dose (value measured by an i-line illuminometer) required to form a 20 μm line-and-space pattern with a 1:1 width was taken as the sensitivity. The sensitivity was determined as follows: 90 mJ / cm . 2 A+, A, B, and C are considered pass marks, and the sensitivity is 60mJ / cm 2 The following are considered to be good sensitivities: A+, A, and B, and the sensitivity is 45 mJ / cm 2 The following A+ and A were rated as excellent sensitivity. A+: Sensitivity is 30mJ / cm 2 below A: Sensitivity is 30mJ / cm 2 and more than 45 mJ / cm 2 below B: Sensitivity is 45mJ / cm 2 and more than 60 mJ / cm 2 below C: Sensitivity is 60mJ / cm 2 and more than 90mJ / cm 2 below D: Sensitivity is 90mJ / cm 2 and more than 150 mJ / cm 2 below E: Sensitivity is 150mJ / cm 2 and more than 500mJ / cm 2 below.

[0343] (8) Cross-sectional shape of pattern after development As described in Example 1 below, a developed film of a negative-tone photosensitive resin composition was prepared by patterning exposure using an ultra-high-pressure mercury lamp's i-line (365 nm wavelength), h-line (405 nm wavelength), and g-line (436 nm wavelength) through a sensitivity measurement grayscale mask (MDRM MODEL 4000-5-FS; Opto-Line International) using a double-sided alignment single-sided exposure system (Mask Aligner PEM-6M; Union Optical Co., Ltd.). The film was then developed using a compact photolithography developing system (AD-2000; Takizawa Sangyo Co., Ltd.). A field-emission scanning electron microscope (S-4800; Hitachi High-Technologies Corporation) was used to observe the cross section of a 20 μm line-and-space pattern in the developed film, and the taper angle of the cross section was measured. The evaluation was made as follows, with A+, A, and B, which indicate a cross-sectional taper angle of 60° or less, being considered pass, A+ and A, which indicate a cross-sectional taper angle of 45° or less, being considered good pattern shape, and A+, which indicates a cross-sectional taper angle of 30° or less, being considered excellent pattern shape. A+: Cross-sectional taper angle is 30° or less A: The cross-sectional taper angle is greater than 30° and less than 45° B: The cross-sectional taper angle is greater than 45° and less than 60° C: The cross-sectional taper angle is greater than 60° and less than 70° D: The cross-sectional taper angle is greater than 70° and less than 80° E: The cross-sectional taper angle is greater than 80° and less than 180°.

[0344] (9) Halftone characteristics Using the method described in Example 1 below, a prebaked film of a negative photosensitive resin composition was formed on an ITO substrate to a thickness of 5 μm. Using a double-sided alignment single-sided exposure system (Mask Aligner PEM-6M; manufactured by Union Optical Co., Ltd.), the film was patterned using i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) from an ultra-high pressure mercury lamp through a halftone photomask for evaluating halftone characteristics, so that the exposure amount in the light-transmitting area was the exposure amount for the sensitivity when the film thickness after prebaking was 5 μm. The film was then developed using a small photolithography developing system (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.), and a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.) to produce a cured film of the negative photosensitive resin composition.

[0345] The half-tone photomask used had a light-transmitting portion, a light-shielding portion, and a semi-transmitting portion between the light-transmitting portion and the light-shielding portion. HT )% are the transmittance (%T FT ) is 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% of the original area. The transparent portion and the semi-transparent portion are adjacent to each other, and the semi-transparent portion and the light-shielding portion are adjacent to each other. The transparent portion, the semi-transparent portion, and the light-shielding portion all have a line-shaped pattern. The transparent portion and the light-shielding portion all have a quadrangular pattern. The transparent portion has a pattern dimension of 2 μm, 5 μm, 10 μm, 15 μm, 20 μm, 30 μm, 40 μm, 50 μm, or 100 μm, respectively. The light-shielding portion has a pattern dimension of 10 μm. On the other hand, the pattern dimensions of the semi-transmitting portions are 2 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, or 100 μm. As an example of a half-tone photomask, an example of the arrangement and dimensions of the light-transmitting portions, light-shielding portions, and semi-transmitting portions is shown in FIG.

[0346] Using a surface roughness and contour measuring instrument (SURFCOM1400D; manufactured by Tokyo Seimitsu Co., Ltd.), the measurement magnification was 10,000 times, the measurement length was 1.0 mm, and the measurement speed was 0.30 mm / s. The film thickness after development of the light-transmitting area and the film thickness after heat curing (T FT The film thickness after development and the film thickness after thermal curing (T HT ) μm, and the minimum film thickness (T HT / min As an index of halftone characteristics, the maximum step thickness was calculated using the following formula. Maximum step film thickness = (T FT )-(T HT / min ).

[0347] The evaluation was made as follows, with A+, A, B and C being acceptable, where the maximum step thickness was 1.0 μm or more; A+, A and B being acceptable, where the maximum step thickness was 1.5 μm or more; and A+ and A being excellent, where the maximum step thickness was 2.0 μm or more. A+: Maximum step thickness is 2.5 μm or more A: Maximum step thickness is 2.0 μm or more and less than 2.5 μm B: Maximum step thickness is 1.5 μm or more and less than 2.0 μm C: Maximum step thickness is 1.0 μm or more and less than 1.5 μm D: Maximum step thickness is 0.5 μm or more and less than 1.0 μm E: Maximum step thickness is 0.1 μm or more and less than 0.5 μm F: The maximum step thickness is less than 0.1 μm or no film remains after development, making it impossible to measure.

[0348] (10) Opening residue Using the method described in Example 1 below, a double-sided alignment single-sided exposure system (Mask Aligner PEM-6M; Union Optical Co., Ltd.) was used to pattern the photoresist using an ultra-high pressure mercury lamp's i-line (365 nm wavelength), h-line (405 nm wavelength), and g-line (436 nm wavelength) through a sensitivity measurement grayscale mask (MDRM MODEL 4000-5-FS; Opto-Line International). The photoresist was then developed using a compact photolithography developer (AD-2000; Takizawa Sangyo Co., Ltd.) and then cured using a high-temperature inert gas oven (INH-9CD-S; Koyo Thermo Systems Co., Ltd.) to produce a negative-tone photosensitive resin composition cured film. The resolution pattern of the cured film was observed using an FPD / LSI inspection microscope (OPTIPHOT-300; Nikon Corporation) to check for the presence or absence of residues in the openings of the 20 μm line-and-space pattern. The evaluation was made as follows: A+, A, and B, which indicate that the area of residue in the opening was 10% or less, were considered pass; A+ and A, which indicate that the area of residue in the opening was 5% or less, were considered good in terms of residue; and A+, which indicates that there was no area of residue in the opening, was considered excellent in terms of residue. A+: No residue at the opening, or the area of residue at the opening is 1% or less A: The area of residue in the opening is more than 1% and less than 5% B: The area of residue in the opening is more than 5% and less than 10% C: The area of residue in the opening is more than 10% and less than 30% D: The area of residue in the opening is more than 30% and less than 50% E: The area of the opening where residue exists is more than 50% and not more than 100%.

[0349] (11) Light-blocking property (optical density value (hereinafter referred to as "OD value")) Using the method described in Example 1 below, a double-sided alignment single-sided exposure device (Mask Aligner PEM-6M; manufactured by Union Optical Co., Ltd.) was used to pattern the sample using a sensitivity measurement grayscale mask (MDRM MODEL 4000-5-FS; manufactured by Opto-Line International) with the i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) from an ultra-high pressure mercury lamp. The sample was then developed using a compact photolithography developing device (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.). A cured film of the negative photosensitive resin composition was then prepared using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.). The incident light intensity (I0) and transmitted light intensity (I) of the prepared cured film were measured using a transmission densitometer (X-Rite 361T(V); manufactured by X-Rite). The OD value was calculated as an index of light-blocking ability using the following formula: OD value = log 10 (I0 / I).

[0350] (12) Insulation (surface resistivity) Using the method described in Example 1 below, a double-sided alignment single-sided exposure device (Mask Aligner PEM-6M; manufactured by Union Optical Co., Ltd.) was used to pattern the i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) from an ultra-high pressure mercury lamp through a grayscale mask for sensitivity measurement (MDRM MODEL 4000-5-FS; manufactured by Opto-Line International). After patterning, the film was developed using a compact photolithography developing device (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.). A cured film of the negative photosensitive resin composition was then prepared using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.). The surface resistivity (Ω / □) of the prepared cured film was measured using a high-resistance resistivity meter ("Hiresta" UP; manufactured by Mitsubishi Chemical Corporation).

[0351] (13) Emission characteristics of organic EL displays (Method for manufacturing organic EL displays) Figure 4 shows a schematic diagram of the substrate used. First, a 10 nm ITO transparent conductive film was formed over the entire surface of a 38 x 46 mm alkali-free glass substrate 47 by sputtering, and then etched to form a first electrode 48, forming a transparent electrode. An auxiliary electrode 49 was also formed at the same time to connect the second electrode (Figure 4 (Step 1)). The resulting substrate was ultrasonically cleaned for 10 minutes using "Semicoclean" (registered trademark) 56 (Furuuchi Chemical Co., Ltd.) and then washed with ultrapure water. Next, a negative photosensitive resin composition was applied to this substrate and prebaked using the method described in Example 1. It was then patterned, exposed through a photomask with a predetermined pattern, developed, rinsed, and then heated for thermal curing. Using the above method, an insulating layer 50 was formed in the effective substrate area, 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, each opening exposing the first electrode (FIG. 4 (Step 2)). These openings will ultimately become the light-emitting pixels of the organic EL display. The effective substrate area was 16 mm square, and the insulating layer 50 was formed to a thickness of approximately 1.0 μm.

[0352] Next, an organic EL display was fabricated using the substrate on which the first electrode 48, auxiliary electrode 49, and insulating layer 50 were formed. After nitrogen plasma treatment as a pretreatment, an organic EL layer 51 including a light-emitting layer was formed by vacuum deposition (FIG. 4 (step 3)). The degree of vacuum during deposition was 1×10 -3 The pressure was below 1 Pa, and the substrate was rotated relative to the evaporation source during evaporation. First, 10 nm of compound (HT-1) was evaporated as a hole injection layer, and 50 nm of compound (HT-2) was evaporated as a hole transport layer. Next, compound (GH-1) was evaporated as a host material and compound (GD-1) was evaporated as a dopant material to a thickness of 40 nm so that the doping concentration was 10%. Then, compound (ET-1) and compound (LiQ) were laminated as electron transport materials in a volume ratio of 1:1 to a thickness of 40 nm. The compounds used in the organic EL layer were the same as those described in WO 2017 / 057281.

[0353] Next, a compound (LiQ) was vapor-deposited to a thickness of 2 nm, followed by vapor deposition of 100 nm of MgAg (magnesium / silver = 10 / 1 (volume ratio)) to form a second electrode 52 and a reflective electrode (Figure 4 (step 4)). After that, in a low-humidity nitrogen atmosphere, a cap-shaped glass plate was attached using an epoxy resin adhesive to seal the surface, and four 5 mm square bottom-emission organic EL displays were fabricated on one substrate. Note that the film thickness here is the value displayed on a quartz crystal oscillator film thickness monitor.

[0354] (Evaluation of light-emitting properties) The organic EL display fabricated by the above method was subjected to a current of 10 mA / cm 2 The organic EL display was driven by a direct current of 10 mA / cm and observed for any light emission defects such as non-light emitting areas or uneven brightness. The organic EL display was then held at 80°C for 500 hours as a durability test. After the durability test, the organic EL display was driven by a direct current of 10 mA / cm. 2 The test pieces were driven with a direct current and made to emit light, and observed for any changes in light-emitting characteristics such as the light-emitting area and brightness unevenness. The test pieces were judged as follows: if the light-emitting area before the durability test was 100%, then A+, A, and B, which indicate that the light-emitting area after the durability test was 80% or more, were deemed to be pass; A+ and A, which indicate that the light-emitting area was 90% or more, were deemed to have good light-emitting characteristics; and A+, which indicates that the light-emitting area was 95% or more, were deemed to have excellent light-emitting characteristics. A+: The light-emitting area after the durability test is 95% or more A: The light-emitting area after the durability test is 90% or more and less than 95% B: The light-emitting area after the durability test is 80% or more and less than 90% C: The light-emitting area after the durability test is 70% or more and less than 80% D: The light-emitting area after the durability test is 50% or more and less than 70% E: The luminous area after the durability test is less than 50%.

[0355] [Example 1] Under yellow light, 0.087 g of OXL-73 and 0.202 g of OXL-21 were weighed out, and 6.426 g of MBA and 5.100 g of PGMEA were added and stirred to dissolve. Next, 5.165 g of a 30% by weight MBA solution of polyimide (PI-1) obtained in Synthesis Example 1, 0.578 g of a 50% by weight MBA solution of b-1, and 1.446 g of a 50% by weight MBA solution of b-3 were added and stirred to obtain a homogeneous solution. Next, 9.163 g of the pigment dispersion (Bk-1) obtained in Preparation Example 1 was weighed out, and 15.837 g of the prepared solution obtained by the above-mentioned method was added and stirred to obtain a homogeneous solution. The resulting solution was then filtered through a 0.45 μmφ filter to prepare Composition 1.

[0356] The prepared composition 1 was applied to an ITO substrate by spin coating at an arbitrary rotation speed using a spin coater (MS-A100; manufactured by Mikasa Corporation), and then prebaked at 110°C for 120 seconds using a buzzer hotplate (HPD-3000BZN; manufactured by AS ONE Corporation) to produce a prebaked film with a thickness of approximately 1.8 μm.

[0357] The prepared prebaked film was spray-developed with a 2.38% by mass TMAH aqueous solution using a small photolithography developing device (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.), and the time it took for the prebaked film (unexposed area) to completely dissolve (Breaking Point; hereinafter, "BP") was measured.

[0358] A prebaked film was prepared in the same manner as described above. The resulting prebaked film was patterned using a double-sided alignment single-sided exposure system (Mask Aligner PEM-6M; Union Optical Co., Ltd.) with an ultra-high pressure mercury lamp's i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) through a grayscale mask for sensitivity measurement (MDRM MODEL 4000-5-FS; Opto-Line International). After exposure, the film was developed in a 2.38 wt% TMAH aqueous solution using a compact photolithography developing system (AD-2000; Takizawa Sangyo Co., Ltd.) and rinsed with water for 30 seconds. The development time was 1.5 times that of the BP.

[0359] After development, the film was thermally cured at 250°C in a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.) to produce a cured film with a thickness of approximately 1.2 μm. The thermal curing conditions were a nitrogen atmosphere at 250°C for 60 minutes.

[0360] [Examples 2 to 66 and Comparative Examples 1 to 7] As in Example 1, compositions 2 to 73 were prepared according to the formulations shown in Tables 3 to 7. Using each of the resulting compositions, a film was formed on a substrate as in Example 1, and the photosensitive properties, properties of the cured film, and luminescent properties were evaluated. The results of these evaluations are summarized in Tables 3 to 7. For ease of comparison, the compositions and evaluation results of Example 1 are also listed in Tables 4 to 7, respectively.

[0361] In Tables 3 to 7, the names corresponding to the abbreviations are shown below. b-1: A-BPEF ("NK ESTER" (registered trademark) A-BPEF (manufactured by Shin-Nakamura Chemical Co., Ltd.; 9,9-bis[4-(2-acryloxyethoxy)phenyl]fluorene) b-2: IDN-1 (1,1-bis[4-(2-acryloxyethoxy)phenyl]indan) b-3: DPHA ("KAYARAD" (registered trademark) DPHA (manufactured by Nippon Kayaku Co., Ltd.; dipentaerythritol hexaacrylate)) b-4: DPCA-60 ("KAYARAD" (registered trademark) DPCA-60 (manufactured by Nippon Kayaku Co., Ltd.; ε-caprolactone-modified dipentaerythritol hexaacrylate having six oxypentylenecarbonyl structures in the molecule)) b-5: A-DCP ("NK ESTER" (registered trademark) A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.; dimethylol-tricyclodecane diacrylate)) d-1: Bk-S0100CF ("IRGAPHOR" (registered trademark) BLACK S0100CF (manufactured by BASF; a benzofuranone-based black pigment with a primary particle size of 40 to 80 nm) d-2: Bk-S0084 ("PALIOGEN" (registered trademark) BLACK S0084 (manufactured by BASF; perylene-based black pigment with a primary particle size of 50 to 100 nm)) d-3: Bk-A1103 ("CHROMOFINE" (registered trademark) BLACK A1103 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.; azo-based black pigment with a primary particle size of 50 to 100 nm) d-4: PR179 / PY192 / PB60 mixture (CI Pigment Red 179 / CI Pigment Yellow 192 / CI Pigment Blue 60 mixture) d-5: PR179 / PY139 / PB60 mixture (CI Pigment Red 179 / CI Pigment Yellow 139 / CI Pigment Blue 60 mixture) d-6: Bk-CBF1 (surface-coated benzofuranone-based black pigment) d-7: TPK-1227 (carbon black with a surface treatment that introduces sulfonic acid groups (manufactured by CABOT)) e-1: S-20000 ("SOLSPERSE" (registered trademark) 20000 (manufactured by Lubrizol; a polyoxyalkylene ether dispersant having a tertiary amino group and an amine value of 32 mg KOH / g (solids concentration: 100% by mass)) e-2: D.BYK-167 ("DISPERBYK" (registered trademark)-167 (manufactured by BYK Japan; polyurethane-based dispersant having a tertiary amino group and an amine value of 13 mg KOH / g (solids concentration: 52% by mass)) f-1: TR-FR-201 (9,9-bis(4-glycidoxyphenyl)fluorene (Tronly)) g-1: DNFLN (2,7-dinitro-9-fluorenone)

[0362] [Table 3]

[0363] [Table 4]

[0364] [Table 5]

[0365] [Table 6]

[0366] [Table 7]

[0367] [Example 67] (Method of manufacturing an organic EL display without a polarizing layer) Figure 5 shows a schematic diagram of the fabricated OLED display. First, a chromium and gold layer was deposited by electron beam evaporation on a 38 × 46 mm alkali-free glass substrate 53, followed by etching to form source and drain electrodes 54 and 55. Next, a 100 nm thick film of APC (silver / palladium / copper = 98.07 / 0.87 / 1.06 (mass ratio)) was sputtered and patterned by etching to form an APC layer. A 10 nm thick film of ITO was then sputtered on top of the APC layer, followed by etching to form a reflective electrode 56 as the first electrode. After cleaning the electrode surface with oxygen plasma, an amorphous IGZO film was sputtered and then etched to form an oxide semiconductor layer 57 between the source and drain electrodes. Next, a film of a positive photosensitive polysiloxane material (SP-P2301; manufactured by Toray Industries, Inc.) was formed by spin coating, and via holes 58 and pixel regions 59 were opened by photolithography, followed by thermal curing to form a gate insulating layer 60. After that, a gold film was formed by electron beam evaporation, and a gate electrode 61 was formed by etching, completing an oxide TFT array.

[0368] Using the method described in Example 1 above, Composition 1 was applied to an oxide TFT array and pre-baked to form a film. The film was then patterned and exposed through a photomask with a predetermined pattern, developed, and rinsed to create openings in the pixel areas. The resulting film was then thermally cured to form a light-blocking TFT protective layer / pixel division layer 62. Using the above method, a pixel division layer was formed in the effective substrate area, with openings measuring 70 μm wide and 260 μm long, arranged at a widthwise pitch of 155 μm and a lengthwise pitch of 465 μm, each exposing a reflective electrode. These openings ultimately became the light-emitting pixels of the organic EL display. The effective substrate area was 16 mm square, and the pixel division layer was formed to a thickness of approximately 1.0 μm.

[0369] Next, an organic EL light-emitting layer 63 was formed using the method described in (13) above, using compound (HT-1) as the hole injection layer, compound (HT-2) as the hole transport layer, compound (GH-1) as the host material, compound (GD-1) as the dopant material, and compound (ET-1) and compound (LiQ) as the electron transport materials. Subsequently, a 10-nm MgAg film (magnesium / silver = 10 / 1 (volume ratio)) was deposited by vapor deposition, and a transparent electrode 64 was formed as the second electrode by etching. Next, a sealing film 65 was formed using an organic EL sealant (Structbond® XMF-T; manufactured by Mitsui Chemicals, Inc.) in a low-humidity nitrogen atmosphere. Furthermore, an alkali-free glass substrate 66 was bonded to the sealing film, and four 5-mm square top-emission organic EL displays without a polarizing layer were fabricated on one substrate. The film thicknesses referred to here are values displayed on a quartz crystal oscillator film thickness monitor.

[0370] (Evaluation of light-emitting properties) The organic EL display fabricated by the above method was subjected to a current of 10 mA / cm 2 The brightness (Y') when external light was irradiated onto the pixel division layer and the brightness (Y0) when external light was not irradiated were measured. The contrast was calculated using the following formula as an index of reduction in external light reflection. Contrast = Y0 / Y'.

[0371] The evaluation was made as follows: A+, A, and B, which indicate a contrast of 0.80 or more, were considered pass, A+ and A, which indicate a contrast of 0.90 or more, were considered good in reducing external light reflection, and A+, which indicates a contrast of 0.95 or more, was considered excellent in reducing external light reflection. The organic EL display fabricated by the above-mentioned method had a contrast of 0.90, confirming that it was possible to reduce external light reflection. A+: Contrast is 0.95 or higher A: Contrast is 0.90 or more and less than 0.95 B: Contrast is 0.80 or more and less than 0.90 C: Contrast is 0.70 or more and less than 0.80 D: Contrast is 0.50 or more and less than 0.70 E: Contrast less than 0.50. [Explanation of symbols]

[0372] 1. Glass substrate 2. TFT 3 Cured film for TFT planarization 4,56 reflective electrode 5a Pre-baked film 5b Hardening pattern 6. Mask 7 Actinic radiation 8 EL light-emitting layer 9,64 Transparent electrode 10 Cured film for flattening 11 Coverslip 34 Thick film section 35a,35b,35c Thin film part 36a, 36b, 36c, 36d, 36e Inclined edges in cross sections of hardening patterns 37 Horizontal edge of the base board 47,53,66 Alkali-free glass substrate 48 1st electrode 49 Auxiliary electrode 50 insulating layer 51 Organic EL layer 52 2nd electrode 54 Source electrode 55 Drain electrode 57 Oxide semiconductor layer 58 Beer Hall 59 pixel area 60 Gate insulating layer 61 gate electrode 62 TFT protection layer / pixel division layer 63 Organic EL light-emitting layer 65 Sealing film

Claims

1. (A) an alkali-soluble resin; and (C1) two or more kinds of (C1-1) oxime ester photopolymerization initiators as photopolymerization initiators, the oxime ester photopolymerization initiator (C1-1) contains at least a fused polycyclic skeleton-containing photopolymerization initiator (C1-1a) and a fused polycyclic heterocyclic skeleton-containing photopolymerization initiator (C1-1b); the fused polycyclic skeleton-containing photopolymerization initiator (C1-1a) has a fused polycyclic skeleton containing an aromatic skeleton, and the fused polycyclic skeleton is composed only of carbon atoms and hydrogen atoms; a structure in which at least one oxime ester structure is bonded to each of the fused polycyclic skeleton and the fused polycyclic heterocyclic skeleton, or a structure in which at least one oxime ester carbonyl structure is bonded to each of the fused polycyclic skeleton and the fused polycyclic heterocyclic skeleton; Further, (B3) a flexible chain-containing aliphatic radical polymerizable compound is contained, the flexible chain-containing aliphatic radical polymerizable compound (B3) has a structure derived from a compound having at least two hydroxy groups in the molecule, at least two ethylenically unsaturated double bond groups, and at least one aliphatic chain; A negative-type photosensitive resin composition, wherein the at least one fatty chain has at least one lactone-modified chain and / or at least one lactam-modified chain.

2. 2. The negative photosensitive resin composition according to claim 1, wherein the (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator and the (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiator each have one or more structures selected from the group consisting of a nitro group, a naphthylcarbonyl structure, a trimethylbenzoyl structure, a thiophenylcarbonyl structure, and a furylcarbonyl structure.

3. 3. The negative photosensitive resin composition according to claim 2, wherein a content ratio of the fused polycyclic skeleton-containing photopolymerization initiator (C1-1a) in the photopolymerization initiator (C1) is 5 to 45 mass%.

4. The photopolymerization initiator (C1-1b) having a fused polycyclic heterocyclic skeleton may contain, as the fused polycyclic heterocyclic skeleton, a dibenzofuran skeleton, a dibenzothiophene skeleton, a benzocarbazole skeleton, a naphthobenzofuran skeleton, a naphthobenzothiophene skeleton, an indole skeleton, a benzofuran skeleton, a benzothiophene skeleton, an indoline skeleton, a benzodihydrofuran skeleton, a benzodihydrothiophene skeleton, a benzoindole skeleton, a naphthofuran skeleton, a naphthothiophene skeleton, a benzoindoline skeleton, a naphthodihydrofuran skeleton, a naphthodihydrothiophene skeleton, an acrididine skeleton, 4. The negative photosensitive resin composition according to claim 1, further comprising one or more skeletons selected from the group consisting of a benzoquinone skeleton, a xanthene skeleton, a thioxanthene skeleton, a benzacridine skeleton, a benzoxanthene skeleton, a benzothioxanthene skeleton, a quinoline skeleton, a benzopyran skeleton, a benzothiopyran skeleton, a benzoquinoline skeleton, a naphthopyran skeleton, a naphthothiopyran skeleton, a dihydroquinoline skeleton, a benzodihydropyran skeleton, a benzodihydrothiopyran skeleton, a benzodihydroquinoline skeleton, a naphthodihydropyran skeleton, and a naphthodihydrothiopyran skeleton.

5. 5. The negative photosensitive resin composition according to claim 4, wherein the fused polycyclic heterocyclic skeleton has one or more skeletons selected from the group consisting of a benzocarbazole skeleton, an indole skeleton, an indoline skeleton, a benzoindole skeleton, and a benzoindoline skeleton.

6. The negative photosensitive resin composition according to any one of claims 1 to 5, wherein one or more selected from the group consisting of the (C1-1a) fused polycyclic skeleton-containing photopolymerization initiator and the (C1-1b) fused polycyclic heterocyclic skeleton-containing photopolymerization initiator have a group substituted with a halogen, and the group substituted with a halogen is a group substituted with a fluorine.

7. at least one selected from the group consisting of (C1-1a) the fused polycyclic skeleton-containing photopolymerization initiator and (C1-1b) the fused polycyclic heterocyclic skeleton-containing photopolymerization initiator, The negative photosensitive resin composition according to any one of claims 1 to 6, which has a structure in which two or more oxime ester structures are bonded to the fused polycyclic skeleton or the fused polycyclic heterocyclic skeleton, or a structure in which two or more oxime ester carbonyl structures are bonded to the fused polycyclic skeleton or the fused polycyclic heterocyclic skeleton.

8. The negative photosensitive resin composition according to any one of claims 1 to 7, wherein at least one selected from the group consisting of the fused polycyclic skeleton-containing photopolymerization initiator (C1-1a) and the fused polycyclic heterocyclic skeleton-containing photopolymerization initiator (C1-1b) has an alkenyl group.

9. Further, (D) the colorant contains (D1a-1) a black organic pigment and / or (D1a-3) a mixture of two or more color pigments, the black organic pigment (D1a-1) contains one or more pigments selected from the group consisting of benzofuranone-based black pigments (D1a-1a), perylene-based black pigments (D1a-1b), and azo-based black pigments (D1a-1c); The negative photosensitive resin composition according to any one of claims 2 to 8, wherein the mixture of two or more color pigments (D1a-3) contains two or more color pigments selected from the group consisting of red, orange, yellow, green, blue, and purple pigments.

10. 10. The negative photosensitive resin composition according to claim 9, wherein the black organic pigment (D1a-1) comprises a benzofuranone-based black pigment (D1a-1a).

11. the maximum absorption wavelength of each of the fused polycyclic skeleton-containing photopolymerization initiator (C1-1a) and the fused polycyclic heterocyclic skeleton-containing photopolymerization initiator (C1-1b) is 340 nm or more and 380 nm or less; the absorbance at a wavelength of 360 nm of each of the fused polycyclic skeleton-containing photopolymerization initiator (C1-1a) and the fused polycyclic heterocyclic skeleton-containing photopolymerization initiator (C1-1b) in a 0.01 g / L propylene glycol monomethyl ether acetate solution is 0.20 or more; Further, (Da) a black agent is contained as a colorant (D), The negative photosensitive resin composition according to any one of claims 1 to 10, wherein the black agent (Da) has a maximum transmission wavelength of 330 nm or more and 410 nm or less.

12. A cured film obtained by curing the negative photosensitive resin composition according to any one of claims 1 to 11.

13. An organic EL display comprising the cured film according to claim 12 as one or more layers selected from the group consisting of a pixel dividing layer, a TFT planarizing layer, a TFT protective layer, an interlayer insulating layer, and a gate insulating layer.

14. A method for producing a cured film, comprising: (1) forming a coating film of the negative photosensitive resin composition according to any one of claims 1 to 11 on a substrate; (2) a step of irradiating the coating film of the negative photosensitive resin composition with actinic rays through a photomask; (3) developing the resist using an alkaline solution to form a pattern of the negative photosensitive resin composition; and (4) a step of heating the pattern to obtain a cured pattern of the negative-type photosensitive resin composition; A method for producing a cured film comprising the steps of:

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