Negative photosensitive resin composition, cured film, organic el display, and method for producing cured film

Abstract

The present invention aims to obtain a negative photosensitive resin composition with high sensitivity, excellent halftone properties, capable of forming a low-cone pattern after development, and able to suppress residue adhesion at the opening of the pattern after thermosetting. A negative photosensitive resin composition comprising (A) an alkali-soluble resin and two or more (C1-1) oxime ester-based photopolymerization initiators as (C1) photopolymerization initiators, wherein the (C1-1) oxime ester-based photopolymerization initiators comprise at least (C1-1a) a photopolymerization initiator containing a fused polycyclic skeleton and (C1-1b) a photopolymerization initiator containing a fused polycyclic heterocyclic skeleton, wherein the (C1-1a) photopolymerization initiator containing the fused polycyclic skeleton comprises a specific structure, and the (C1-1a) photopolymerization initiator containing the fused polycyclic skeleton has a structure in which an oxime ester structure or an oxime ester carbonyl structure is bonded to the fused polycyclic heterocyclic skeleton, and the (C1-1b) photopolymerization initiator containing the fused polycyclic heterocyclic skeleton has a structure in which an oxime ester structure or an oxime ester carbonyl structure is bonded to the fused polycyclic heterocyclic skeleton.

Description

Technical Field

[0001] This invention relates to a negative photosensitive resin composition, a cured film, an organic EL display, and a method for manufacturing the cured film. Background Technology

[0002] In recent years, a large number of products using organic electroluminescent (hereinafter, "EL") displays have been developed in display devices with thin displays such as smartphones, tablet PCs, and televisions.

[0003] To improve the reliability of organic EL displays, high heat resistance / high sensitivity photosensitive resin compositions are used in the pixel segmentation layer, thin-film transistor (hereinafter, "TFT") planarization layer, TFT protective layer, or interlayer insulating layer or gate insulating layer in the formation of the TFT array. In particular, for the pixel segmentation layer, in order to minimize the contact area between the evaporation mask in the light-emitting layer film formation and the pixel segmentation layer, a stepped shape is required. It is also required that the stepped shape of the pixel segmentation layer be formed by using a halftone photomask for simultaneous exposure (hereinafter, "halftone characteristic").

[0004] Examples of photosensitive resin compositions include negative photosensitive resin compositions comprising an oxime ester photopolymerization initiator containing a fluorene skeleton and an oxime ester photopolymerization initiator containing a diphenyl sulfide skeleton (see Patent Document 1), and negative photosensitive resin compositions comprising an oxime ester photopolymerization initiator containing a fluorene skeleton and an oxime ester photopolymerization initiator containing a diphenyl sulfide skeleton with a specific structure (see Patent Document 2).

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2016-141770

[0008] Patent Document 2: International Publication No. 2018 / 052024 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] To improve the reliability of organic EL displays and simplify their manufacturing, the photosensitive resin composition requires high sensitivity, excellent halftone properties, the ability to form low-cone patterns after development, and the ability to suppress residue adhesion at the pattern openings after thermal curing. However, the photosensitive resin compositions described in the aforementioned documents, when used in organic EL displays, do not possess any of the aforementioned characteristics sufficiently.

[0011] Methods for solving problems

[0012] To address the aforementioned issues, the negative photosensitive resin composition of the present invention is a negative photosensitive resin composition comprising (A) an alkali-soluble resin and two or more (C1-1) oxime ester-based photopolymerization initiators as (C1) photopolymerization initiators. The (C1-1) oxime ester-based photopolymerization initiators comprise at least (C1-1a) a photopolymerization initiator containing a fused polycyclic skeleton and (C1-1b) a photopolymerization initiator containing a fused polycyclic heterocyclic skeleton. Photopolymerization initiators with fused polycyclic skeletons have a fused polycyclic skeleton containing an aromatic skeleton, and the fused polycyclic skeleton is composed only of carbon atoms and hydrogen atoms. The photopolymerization initiator (C1-1a) containing a fused polycyclic skeleton has a structure incorporating an oxime ester structure or an oxime ester carbonyl structure on the fused polycyclic skeleton, and the photopolymerization initiator (C1-1b) containing a fused polycyclic heterocyclic skeleton has a structure incorporating an oxime ester structure or an oxime ester carbonyl structure on the fused polycyclic heterocyclic skeleton.

[0013] The effects of the invention

[0014] The negative photosensitive resin composition according to the present invention has high sensitivity, excellent halftone properties, and can form a low-cone pattern after development, which can suppress the adhesion of residue at the opening of the pattern after thermosetting. Attached Figure Description

[0015] Figure 1 This is a process diagram illustrating, in schematic cross-section, the manufacturing process of steps 1 to 7 in an organic EL display using a cured film of the negative photosensitive resin composition of the present invention.

[0016] Figure 2 A cross-sectional view showing an example of a cured pattern with a stepped shape.

[0017] Figure 3 Here is a schematic diagram showing the configuration and dimensions of the light-transmitting, light-blocking, and semi-transparent parts in a halftone mask used for halftone characteristic evaluation.

[0018] Figure 4 This is a schematic diagram illustrating the manufacturing process of steps 1 to 4 in the substrate of an organic EL display used for evaluating light emission characteristics, presented in plan view.

[0019] Figure 5 Here is a schematic cross-section of an organic EL display without a polarizing layer. Detailed Implementation

[0020] The negative photosensitive resin composition of the present invention is a negative photosensitive resin composition comprising (A) an alkali-soluble resin and two or more (C1-1) oxime ester-based photopolymerization initiators as (C1) photopolymerization initiators. The (C1-1) oxime ester-based photopolymerization initiators comprise 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 the fused polycyclic skeleton has a fused polycyclic skeleton containing an aromatic skeleton. The (C1-1a) photopolymerization initiator containing the fused polycyclic skeleton has a structure incorporating an oxime ester structure or an oxime ester carbonyl structure on the fused polycyclic skeleton, and the (C1-1b) photopolymerization initiator containing the fused polycyclic heterocyclic skeleton has a structure incorporating an oxime ester structure or an oxime ester carbonyl structure on the fused polycyclic heterocyclic skeleton.

[0021] The materials contained in the negative photosensitive resin composition of the present invention are described below.

[0022] <<(A) Alkali-soluble resin>>

[0023] <(A1) First Resin>

[0024] The negative photosensitive resin composition of the present invention contains (A) an alkali-soluble resin. As (A) the alkali-soluble resin, it preferably contains at least (A1) a first resin. As (A1) the first resin, it preferably contains a resin selected from (A1-1) polyimide, (A1-2) a polyimide precursor, and (A1-3) polybenzo[a] azole, and (A1-4) polybenzo[ One or more of the azole precursors. In this invention, (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzo[a] azole, and (A1-4) polybenzo[ The azole precursor can be a single resin or a copolymer thereof.

[0025] As the (A) alkali-soluble resin, from the viewpoints of improving the formation of a low-cone pattern after development, enhancing halftone characteristics, improving the heat resistance of the cured film, and improving the reliability of the light-emitting element, the (A1) first resin preferably contains a mixture selected from (A1-1) polyimide, (A1-2) polyimide precursor, and (A1-3) polybenzo[a]pyrene. azole, and (A1-4) polybenzo[ One or more of the azole precursors, more preferably containing (A1-1) polyimide and / or (A1-3) polybenzo[a] The azole is further preferably containing (A1-1) polyimide.

[0026] (A1-1) polyimide and (A1-2) polyimide precursors have imide and / or amide bonds as polar bonds. Furthermore, (A1-3) polybenzo[…] azole and (A1-4) polybenzo[ azole precursor has Azolium bonds and / or amide bonds are polar bonds. Therefore, as the (D) colorant described later, especially in the case of (D1) pigment, these polar bonds interact strongly with the (D1) pigment, thus improving the dispersion stability of the (D1) pigment.

[0027] <(A1-1)polyimide and (A1-2)polyimide precursor>

[0028] Examples of (A1-2) polyimide precursors include diisocyanate compounds obtained by reacting tetracarboxylic acid, the corresponding tetracarboxylic dianhydride, tetracarboxylic acid dichloride, or tetracarboxylic acid reactive diester with diamine, diamine, and phosgene, or substances obtained by reacting with trimethylsilyldiamine, having tetracarboxylic acid residues and / or tetracarboxylic acid derivative residues, as well as diamine residues and / or diamine derivative residues. Examples of (A1-2) polyimide precursors include polyamic acid, polyamic acid ester, polyamic acid amide, or polyisoimide.

[0029] Examples of (A1-1) polyimides include substances obtained by dehydrating and clotting the above-mentioned polyamic acid, polyamic acid ester, polyamic acid amide, or polyisoimide through heating or a reaction using an acid or base.

[0030] From the viewpoints of pattern formation of a low cone shape after development, improved halftone characteristics, improved heat resistance of the cured film, and improved reliability of the light-emitting element, the (A1-1) polyimide used in this invention preferably contains the structural unit shown in the following general formula (1).

[0031]

[0032] In general formula (1), R 1 R represents a 4- to 10-valent organic group. 2 Represents a divalent to decavalent organic group. R 3 and R 4 Each group 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 from 0 to 6, and q represents an integer from 0 to 8. Wherein, in R... 3 or R 4 When representing a phenolic hydroxyl group, R is bound to the phenolic hydroxyl group. 1 or R 2 This indicates an aromatic structure.

[0033] R in general formula (1) 1 R represents tetracarboxylic acid residues and / or tetracarboxylic acid derivative residues. 2 This refers to diamine residues and / or diamine derivative residues. Examples of tetracarboxylic acid derivatives include tetracarboxylic dianhydrides, tetracarboxylic acid dichlorides, or tetracarboxylic acid active diesters. Examples of diamine derivatives include diisocyanate compounds or trimethylsilyldiamine.

[0034] In general formula (1), R 1 Preferably, it has one or more 4- to 10-valent organogroups selected from aliphatic structures with 2 to 20 carbon atoms, alicyclic structures with 4 to 20 carbon atoms, and aromatic structures with 6 to 30 carbon atoms. Furthermore, R 2 Preferably, it has one or more 2- to 10-valent organogroups selected from aliphatic structures with 2 to 20 carbon atoms, alicyclic structures with 4 to 20 carbon atoms, and aromatic structures with 6 to 30 carbon atoms. q is preferably 1 to 8. The aforementioned aliphatic, alicyclic, and aromatic structures may have heteroatoms and may be either unsubstituted or substituted.

[0035]

[0036] In general formulas (5) and (6), R 19 ~R 21 Each of these groups independently represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, an acyl group with 2 to 6 carbon atoms, or an aryl group with 6 to 15 carbon atoms. In general formulas (5) and (6), R 19 ~R 21 Each of the following is 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 alkyl, acyl, and aryl groups mentioned above can be any of the unsubstituted or substituted forms.

[0037] As a (A1-1) polyimide, it is preferable to contain structural units represented by general formula (1). The content ratio of the structural units represented by general formula (1) in all structural units of the (A1-1) polyimide is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and even more preferably 70 to 100 mol%. If the content ratio is 50 to 100 mol%, the formation of low-cone pattern after development, halftone characteristics, heat resistance of the cured film, and reliability of the light-emitting element can be improved.

[0038] As the (A1-2) polyimide precursor used in this invention, from the viewpoint of improving the sensitivity during exposure, improving the heat resistance of the cured film, and improving the reliability of the light-emitting element, it is preferable to contain the structural unit shown in the following general formula (3).

[0039]

[0040] In general formula (3), R 9 R represents a 4- to 10-valent organic group. 10 Represents a divalent to decavalent organic group. R 11 R represents the substituent shown in general formula (5) or general formula (6) above. 12 R indicates a phenolic hydroxyl group, sulfonic acid group, or mercapto group. 13 This represents a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or a substituent represented by the above general formula (5) or general formula (6). t represents an integer from 2 to 8, u represents an integer from 0 to 6, v represents an integer from 0 to 8, and 2 ≤ t + u ≤ 8. Wherein, in R... 12 or R 13 When representing a phenolic hydroxyl group, R is bound to the phenolic hydroxyl group. 9 or R 10 This indicates an aromatic structure.

[0041] R in general formula (3) 9 R represents tetracarboxylic acid residues and / or tetracarboxylic acid derivative residues. 10 This refers to diamine residues and / or diamine derivative residues. Examples of tetracarboxylic acid derivatives include tetracarboxylic dianhydrides, tetracarboxylic acid dichlorides, or tetracarboxylic acid active diesters. Examples of diamine derivatives include diisocyanate compounds or trimethylsilyldiamine.

[0042] In general formula (3), R 9 Preferably, it has one or more 4- to 10-valent organogroups selected from aliphatic structures with 2 to 20 carbon atoms, alicyclic structures with 4 to 20 carbon atoms, and aromatic structures with 6 to 30 carbon atoms. Furthermore, R 10 Preferably, it has one or more 2- to 10-valent organogroups selected from aliphatic structures with 2 to 20 carbon atoms, alicyclic structures with 4 to 20 carbon atoms, and aromatic structures with 6 to 30 carbon atoms. v is preferably 1 to 8. The aforementioned aliphatic, alicyclic, and aromatic structures may have heteroatoms and may be either unsubstituted or substituted.

[0043] As a (A1-2) polyimide precursor, it preferably contains structural units represented by general formula (3). The content ratio of the structural units represented by general formula (3) in all structural units in the (A1-2) polyimide precursor is preferably 50-100 mol%, more preferably 60-100 mol%, and even more preferably 70-100 mol%. If the content ratio is 50-100 mol%, the sensitivity during exposure, the heat resistance of the cured film, and the reliability of the light-emitting element can be improved.

[0044] As a (A1-2) polyimide precursor, R in the structural unit shown in general formula (3)11 In the case of substituents represented by general formula (5), R 19 The structural unit containing a hydrogen atom is called an ammonium acid structural unit. The ammonium acid structural unit in the (A1-2) polyimide precursor has a carboxyl group as a tetracarboxylic acid residue and / or a tetracarboxylic acid derivative residue. As the (A1-2) polyimide precursor, the R in the structural unit shown in general formula (3) is... 11 In the case of substituents represented by general formula (5), R 19 Structural units consisting of alkyl groups with 1 to 10 carbon atoms, acyl groups with 2 to 6 carbon atoms, or aryl groups with 6 to 15 carbon atoms are called amide ester structural units. As a (A1-2) polyimide precursor, the R in the structural unit shown in general formula (3) is... 11 The structural unit with substituents as shown in general formula (6) is called an amide acid amide structural unit.

[0045] From the viewpoint of improved resolution after development and formation of a low-conical pattern after development, (A1-2) polyimide precursors preferably contain the aforementioned ammonium acid structural unit, as well as the aforementioned ammonium ester structural unit and / or the aforementioned ammonium acid amide structural unit. (A1-2) polyimide precursors containing ammonium acid structural units, as well as ammonium ester structural units and / or ammonium acid amide structural units, can be synthesized by esterifying and / or amidating a portion of the carboxyl group that is an ammonium acid structural unit and is a tetracarboxylic acid residue and / or a tetracarboxylic acid derivative residue.

[0046] <(A1-3) Polybenzo[ azole, and (A1-4) polybenzo[ Azole precursor>

[0047] As (A1-4) polybenzo[ The azole precursor, for example, is a substance obtained by reacting a dicarboxylic acid, a dicarboxylic acid dichloride obtained by reacting a dicarboxylic acid with a thionyl chloride, or an active diester of a dicarboxylic acid with a diaminophenol compound as a diamine, having dicarboxylic acid residues and / or dicarboxylic acid derivative residues, and diaminophenol compound residues and / or diaminophenol compound derivative residues. As (A1-4) polybenzo[…] Azole precursors, for example, are polyhydroxyamides.

[0048] As (A1-3) polybenzo[ Examples of azoles include substances obtained by dehydrating and cyclizing a dicarboxylic acid with a diaminophenol compound as a diamine through a reaction with polyphosphoric acid, and substances obtained by dehydrating and cyclizing the aforementioned polyhydroxyamide through heating or by a reaction with a phosphoric anhydride, a base, or a carbodiimide compound, having dicarboxylic acid residues and / or dicarboxylic acid derivative residues, as well as diaminophenol compound residues and / or diaminophenol compound derivative residues.

[0049] As used in this invention, (A1-3) polybenzo[…] From the viewpoints of pattern formation of a low cone shape after development, improved halftone characteristics, improved heat resistance of the cured film, and improved reliability of the light-emitting element, it is preferable to contain the structural unit shown in general formula (2).

[0050]

[0051] In general formula (2), R 5 R represents a divalent to a decavalent organic group. 6 Represents 4- to 10-valent organic groups with aromatic structures. R 7 R represents a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or a substituent represented by the above general formula (5) or general formula (6). 8 The r represents a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or a substituent represented by the above general formula (5) or general formula (6). r represents an integer from 0 to 8, and s represents an integer from 0 to 6. Wherein, in R... 7 When representing a phenolic hydroxyl group, R is bound to the phenolic hydroxyl group. 5 This indicates an aromatic structure.

[0052] R in general formula (2) 5 R represents dicarboxylic acid residues and / or dicarboxylic acid derivative residues. 6 This refers to residues of bisaminophenol compounds and / or residues of bisaminophenol compound derivatives. Examples of dicarboxylic acid derivatives include dicarboxylic anhydrides, dicarboxylic acid chlorides, dicarboxylic acid reactive esters, tricarboxylic anhydrides, tricarboxylic acid chlorides, tricarboxylic acid reactive esters, and diformyl compounds.

[0053] In general formula (2), R 5 Preferably, it has one or more 2- to 10-valent organic groups selected from aliphatic structures with 2 to 20 carbon atoms, alicyclic structures with 4 to 20 carbon atoms, and aromatic structures with 6 to 30 carbon atoms. Furthermore, R 6 Preferably, it is a 4-10 valent organogroup with an aromatic structure having 6-30 carbon atoms. s is preferably 1-6. The above-mentioned aliphatic, alicyclic, and aromatic structures may have heteroatoms and may be either unsubstituted or substituted.

[0054] As (A1-3) polybenzo[ azole, preferably containing the structural unit shown in general formula (2), wherein the structural unit shown in general formula (2) is in (A1-3) polybenzo[] The content of all structural units in the azole is preferably 50-100 mol%, more preferably 60-100 mol%, and even more preferably 70-100 mol%. If the content is 50-100 mol%, the formation of low-cone pattern after development, halftone characteristics, heat resistance of the cured film, and reliability of the light-emitting element can be improved.

[0055] As used in this invention, (A1-4) polybenzo[…] From the viewpoint of improving the sensitivity during exposure, improving the heat resistance of the cured film, and improving the reliability of the light-emitting element, the azole precursor preferably contains the structural unit shown in general formula (4).

[0056]

[0057] In general formula (4), R 14 R represents a divalent to a decavalent organic group. 15 Represents 4- to 10-valent organic groups with aromatic structures. R 16 R represents a phenolic hydroxyl group, a sulfonic acid group, a mercapto group, or a substituent represented by the above general formula (5) or general formula (6). 17 R represents a phenolic hydroxyl group. 18 The group represents a sulfonic acid group, a mercapto group, or a substituent represented by the above general formula (5) or general formula (6). w represents an integer from 0 to 8, x represents an integer from 2 to 8, y represents an integer from 0 to 6, and 2 ≤ x + y ≤ 8. Wherein, in R... 16 When representing a phenolic hydroxyl group, R is bound to the phenolic hydroxyl group. 14 This indicates an aromatic structure.

[0058] R in general formula (4) 14 R represents dicarboxylic acid residues and / or dicarboxylic acid derivative residues. 15 This refers to residues of bisaminophenol compounds and / or residues of bisaminophenol compound derivatives. Examples of dicarboxylic acid derivatives include dicarboxylic anhydrides, dicarboxylic acid chlorides, dicarboxylic acid reactive esters, tricarboxylic anhydrides, tricarboxylic acid chlorides, tricarboxylic acid reactive esters, and diformyl compounds.

[0059] In general formula (4), R 14 Preferably, it has one or more 2- to 10-valent organic groups selected from aliphatic structures with 2 to 20 carbon atoms, alicyclic structures with 4 to 20 carbon atoms, and aromatic structures with 6 to 30 carbon atoms. Furthermore, R 15 Preferably, it is a 4-10 valent organic group with an aromatic structure having 6-30 carbon atoms. The above-mentioned aliphatic, alicyclic, and aromatic structures may have heteroatoms and may be either unsubstituted or substituted.

[0060] As (A1-4) polybenzo[ The azole precursor preferably contains the structural unit shown in general formula (4), wherein the structural unit shown in general formula (4) is in (A1-4) polybenzo[] The content of all structural units in the azole precursor is preferably 50-100 mol%, more preferably 60-100 mol%, and even more preferably 70-100 mol%. If the content is 50-100 mol%, the sensitivity during exposure, the heat resistance of the cured film, and the reliability of the light-emitting element can be improved.

[0061] Examples of tetracarboxylic acids, dicarboxylic acids, and carboxylic acid derivatives, as well as diamines and diamine derivatives, used in the synthesis of the first resin in (A1) above include, for example, the compounds described in International Publication No. 2017 / 057281.

[0062] <Structural units containing fluorine atoms>

[0063] Selected from (A1-1) polyimide, (A1-2) polyimide precursor, and (A1-3) polybenzo[] azole, and (A1-4) polybenzo[ One or more of the azole precursors preferably contain structural units having fluorine atoms in 10-100 mol% of all structural units. This is achieved by selecting from (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzo[a]pyrene. azole, and (A1-4) polybenzo[ One or more structural units containing fluorine atoms in the azole precursor improve transparency, thereby increasing exposure sensitivity and enabling the formation of low-cone patterns after development. Furthermore, halftone properties are improved. This is presumably because the increased film transparency allows for deeper free radical curing of the film. Additionally, in the case of (C1-1) oxime ester photopolymerization initiators having halogen-substituted groups, it is believed that the compatibility between the alkali-soluble resin and the photopolymerization initiator is improved, and UV curing during deep film exposure is also efficient. Furthermore, it is believed that the fluorine atoms impart water-repellent properties to the film surface, inhibiting the penetration of the developer into the film surface during alkaline development and suppressing lateral etching caused by the developer. Here, "exposure" refers to irradiation by reactive chemical rays (radiation), such as visible light, ultraviolet light, electron beams, or X-rays. From the viewpoint of a light source for general use, for example, an ultra-high pressure mercury lamp light source capable of irradiation with visible light or ultraviolet light is preferred, and irradiation with gamma rays (wavelength 313 nm), i rays (wavelength 365 nm), h rays (wavelength 405 nm), or gamma rays (wavelength 436 nm) is more preferred. Hereinafter, "exposure" refers to irradiation with reactive chemical rays (radiation).

[0064] Structural units containing fluorine atoms as precursors of (A1-1) polyimide and / or (A1-2) polyimide include structural units derived from tetracarboxylic acids containing fluorine atoms, structural units derived from tetracarboxylic acid derivatives containing fluorine atoms, structural units derived from diamines containing fluorine atoms, or structural units derived from diamine derivatives containing fluorine atoms.

[0065] As (A1-3) polybenzo[ azoles and / or (A1-4) polybenzoxazoles The azole precursor contains structural units with fluorine atoms, which may be derived from structural units of dicarboxylic acids with fluorine atoms, structural units of dicarboxylic acid derivatives with fluorine atoms, structural units of bisaminophenol compounds with fluorine atoms, or structural units of bisaminophenol compound derivatives with fluorine atoms.

[0066] Selected from (A1-1) polyimide, (A1-2) polyimide precursor, and (A1-3) polybenzo[] azole, and (A1-4) polybenzo[ The percentage of fluorine-containing structural units in one or more resins of the azole precursor is preferably 30-100 mol%. More preferably, the percentage of fluorine-containing structural units is 50 mol% or more, and even more preferably 70 mol% or more. A percentage of 30-100 mol% can improve the sensitivity during exposure.

[0067] Selected from (A1-1) polyimide, (A1-2) polyimide precursor, and (A1-3) polybenzo[] azole, and (A1-4) polybenzo[ The content of one or more structural units selected from tetracarboxylic acids having fluorine atoms, tetracarboxylic acid derivatives having fluorine atoms, dicarboxylic acids having fluorine atoms, and dicarboxylic acid derivatives having fluorine atoms in the resin of the azole precursor is preferably 30 to 100 mol% of the total number of structural units derived from all carboxylic acids and structural units derived from all 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 the sensitivity during exposure.

[0068] Selected from (A1-1) polyimide, (A1-2) polyimide precursor, and (A1-3) polybenzo[] azole, and (A1-4) polybenzo[ The content of one or more structural units selected from diamines having fluorine atoms, diamine derivatives having fluorine atoms, bisaminophenol compounds having fluorine atoms, and bisaminophenol compound derivatives having fluorine atoms in the resin of the azole precursor is preferably 30 to 100 mol% of the total number of structural units derived from all amines and structural units derived from all amine 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 the sensitivity during exposure.

[0069] <Structural units containing fused multi-ring framework>

[0070] Selected from (A1-1) polyimide, (A1-2) polyimide precursor, and (A1-3) polybenzo[] azole, and (A1-4) polybenzo[ One or more of the azole precursors preferably contain structural units comprising a fused polycyclic backbone. By containing structural units comprising a fused polycyclic backbone, the sensitivity during exposure can be improved, and a low-cone pattern can be formed after development. In addition, halftone properties can be improved. As structural units comprising a fused polycyclic backbone, it is preferable to contain one or more structural units selected from those having a fluorene backbone and those having an indene backbone. This is because the above structural units interact significantly with the photopolymerization initiator containing a fused polycyclic backbone (C1-1a) and the photopolymerization initiator containing a fused polycyclic heterocyclic backbone (C1-1b) described later, thereby improving the compatibility between the alkali-soluble resin and the photopolymerization initiator, and allowing for efficient UV curing during exposure to deeper layers of the film. Selected from (A1-1) polyimide, (A1-2) polyimide precursor, (A1-3) polybenzo[…] azole, and (A1-4) polybenzo[ The percentage of structural units comprising a fused polycyclic skeleton in one or more resins of the azole precursor is preferably 10 to 50 mol%, more preferably 20 to 50 mol% or more, and even more preferably 30 to 50 mol% or more.

[0071] Structural units comprising a fused polycyclic backbone, which are present in (A1-1) polyimide and / or (A1-2) polyimide precursors, can be exemplified by structural units derived from tetracarboxylic acids containing a fused polycyclic backbone, structural units derived from tetracarboxylic acid derivatives containing a fused polycyclic backbone, structural units derived from diamines containing a fused polycyclic backbone, or structural units derived from diamine derivatives containing a fused polycyclic backbone.

[0072] As (A1-3) polybenzo[ azoles and / or (A1-4) polybenzoxazoles The structural units of the azole precursor that contain a fused polycyclic skeleton can be derived from structural units of dicarboxylic acids containing a fused polycyclic skeleton, structural units of dicarboxylic acid derivatives containing a fused polycyclic skeleton, structural units of bisaminophenol compounds containing a fused polycyclic skeleton, or structural units of bisaminophenol compound derivatives containing a fused polycyclic skeleton.

[0073] <Other Structural Units>

[0074] From the perspective of improving the heat resistance and halftone properties of the cured film due to the heat resistance of aromatic groups, the following are selected: (A1-1) polyimide, (A1-2) polyimide precursor, and (A1-3) polybenzo[…]. azole, and (A1-4) polybenzo[ One or more of the azole precursors preferably contain structural units derived from aromatic carboxylic acids and / or structural units derived from aromatic carboxylic acid derivatives. Similarly, structural units derived from aromatic amines and / or structural units derived from aromatic amine derivatives are also preferred. Furthermore, from the viewpoint of improving the adhesion between the cured film and the substrate, structural units derived from diamines having silyl or siloxane bonds and / or structural units derived from diamine derivatives having silyl or siloxane bonds are also preferred. It should be noted that, from the viewpoint of improving the formation of a low-cone shape pattern after thermosetting and the mechanical properties of the cured film, structural units derived from amines having an oxide structure and / or structural units derived from amine derivatives having an oxide structure are also preferred.

[0075] <End-capping agent>

[0076] From the viewpoint of improving the storage stability of the resin composition coating and the pattern processing properties using alkaline developing solution, the following are selected: (A1-1) polyimide, (A1-2) polyimide precursor, and (A1-3) polybenzo[…]. azole, and (A1-4) polybenzo[ The ends of one or more preferred resins in the azole precursor are sealed with end-capping agents such as monoamines, dicarboxylic anhydrides, monocarboxylic acids, monocarboxylic acid chlorides, or monocarboxylic acid reactive esters.

[0077] <Introduction of olefinic unsaturated double bonds>

[0078] Selected from (A1-1) polyimide, (A1-2) polyimide precursor, and (A1-3) polybenzo[] azole, and (A1-4) polybenzo[ One or more of the azole precursors preferably have olefinically unsaturated double bonds. It is also preferred to introduce olefinically unsaturated double bonds into the side chains of these resins through a reaction that introduces the olefinically unsaturated double bonds. Having olefinically unsaturated double bonds improves sensitivity during exposure and allows for the formation of low-cone patterns after development.

[0079] Selected from (A1-1) polyimide, (A1-2) polyimide precursor, and (A1-3) polybenzo[] azole, and (A1-4) polybenzo[ One or more of the azole precursors are preferably obtained by reacting some of their phenolic hydroxyl and / or carboxyl groups with a compound having an olefinic unsaturated double bond. Through the above reaction, an olefinic unsaturated double bond can be introduced into the side chain of the resin.

[0080] From a reactivity point of view, electrophilic compounds having olefinic unsaturated double bonds are preferred as compounds having olefinic unsaturated double bonds. From the viewpoints of reactivity and compound usability, isocyanate compounds, epoxide compounds, alcohol compounds, aldehyde compounds, ketone compounds, or carboxylic anhydrides are preferred as electrophilic compounds, and isocyanate compounds or epoxide compounds are more preferred.

[0081] <(A1-1)polyimide, (A1-2)polyimide precursor, (A1-3)polybenzo[] azole, and (A1-4) polybenzo[ The physical properties of the azole precursor >

[0082] As a selection from (A1-1) polyimide, (A1-2) polyimide precursor, and (A1-3) polybenzo[…] azole, and (A1-4) polybenzo[ The weight-average molecular weight (hereinafter "Mw") of one or more of the azole precursors, from the viewpoint of improving image resolution after development and improving the reliability of the light-emitting element, is preferably 1,000 or more, more preferably 3,000 or more, and even more preferably 5,000 or more, calculated as polystyrene by gel permeation chromatography (hereinafter "GPC"). On the other hand, as Mw, from the viewpoint of improving the formation of low-cone-shaped patterns after thermosetting and improving the pattern processability with alkaline developer, it is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 30,000 or less, and particularly preferably 20,000 or less. (A1-1) Polyimide, (A1-2) Polyimide precursor, (A1-3) Polybenzo[…] azole, and (A1-4) polybenzo[ The azole precursor can be synthesized using known methods.

[0083] <(A2) Second Resin>

[0084] The negative photosensitive resin composition of the present invention preferably further contains a second resin (A2) as the alkali-soluble resin (A). As the second resin (A2), from the viewpoint of improved sensitivity during exposure and reduced taper due to control of the pattern shape after development, it is preferable to contain one or more selected from (A2-1) polysiloxane, (A2-2) a resin containing polycyclic side chains, (A2-3) an acid-modified epoxy resin, and (A2-4) an acrylic resin. In the present invention, (A2-1) polysiloxane, (A2-2) a resin containing polycyclic side chains, (A2-3) an acid-modified epoxy resin, and (A2-4) an acrylic resin can be any single resin or a copolymer thereof.

[0085] As the alkali-soluble resin (A), from the viewpoints of improved halftone characteristics, increased sensitivity during exposure, and reduced taper due to control over the pattern shape after development, the second resin (A2) preferably contains one or more selected from (A2-1) polysiloxane, (A2-2) a resin containing polycyclic side chains, and (A2-3) acid-modified epoxy resin; more preferably, it contains (A2-1) polysiloxane and / or (A2-2) a resin containing polycyclic side chains; and even more preferably, it contains (A2-1) polysiloxane. Furthermore, by containing (A2-1) polysiloxane, a pattern with a low taper shape can be formed after thermosetting. On the other hand, from the viewpoints of improved sensitivity during exposure and suppression of residue adhesion at the opening of the pattern after thermosetting, the second resin (A2) preferably contains (A2-2) a resin containing polycyclic side chains and / or (A2-3) acid-modified epoxy resin; and more preferably, it contains (A2-2) a resin containing polycyclic side chains.

[0086] In the negative photosensitive resin composition of the present invention, from the viewpoint that the effects of improved sensitivity during exposure, low-cone pattern formation after development, and improved halftone properties become significant, the (A) alkali-soluble resin contains polyimide selected from (A1-1) polyimide, (A1-2) polyimide precursor, and (A1-3) polybenzo[a]pyrene. azole, and (A1-4) polybenzo[ When one or more of the azole precursors are used as the (A1) first resin, the (A) alkali-soluble resin preferably further contains (A2-1) polysiloxane as the (A2) second resin.

[0087] In the negative photosensitive resin composition of the present invention, from the viewpoint that the effects of improved sensitivity during exposure, low-cone pattern formation after development, and improved halftone properties become significant, the (A) alkali-soluble resin contains polyimide selected from (A1-1) polyimide, (A1-2) polyimide precursor, and (A1-3) polybenzo[a]pyrene. azole, and (A1-4) polybenzo[ When one or more of the azole precursors are used as the first resin (A1), it is preferable that the alkali-soluble resin (A) further contains a resin (A2-2) containing polycyclic side chains and / or an acid-modified epoxy resin (A2-3) as the second resin (A2), and the resin (A2-2) containing polycyclic side chains and the acid-modified epoxy resin (A2-3) contain structural units having a fused polycyclic backbone.

[0088] <(A2-1) Polysiloxane>

[0089] In this invention, the (A2-1) polysiloxane can be, for example, obtained by hydrolyzing one or more of a trifunctional organosilane, a tetrafunctional organosilane, a difunctional organosilane, and a monofunctional organosilane to induce dehydration condensation.

[0090] From the viewpoint of improving the heat resistance of the cured film and the resolution after development, the (A2-1) polysiloxane used in this invention preferably contains trifunctional organosilane units and / or tetrafunctional organosilane units.

[0091] <Trifunctional organosilane units and tetrafunctional organosilane units>

[0092] As the polysiloxane (A2-1) used in this invention, from the viewpoint of improving the heat resistance of the cured film and improving the resolution after development, it is preferable to contain trifunctional organosilane units and / or tetrafunctional organosilane units. As a trifunctional organosilane, the organosilane unit shown in general formula (7) is preferred. As a tetrafunctional organosilane unit, the organosilane unit shown in general formula (8) is preferred. Furthermore, from the viewpoint of reducing the tapering of the pattern shape and improving the mechanical properties of the cured film, it may contain difunctional organosilane units. Furthermore, from the viewpoint of improving the storage stability of the resin composition coating, it may contain a monofunctional organosilane unit.

[0093]

[0094] In general formulas (7) and (8), R 22 Represents a hydrogen atom, alkyl, cycloalkyl, alkenyl, or aryl group. In general formulas (7) and (8), R 22 Preferably, the alkyl group has hydrogen atoms, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, or an aryl group with 6 to 15 carbon atoms. The aforementioned alkyl, cycloalkyl, alkenyl, and aryl groups may have heteroatoms and may be either unsubstituted or substituted. Examples of the aforementioned organosilanes include, for instance, the compound described in International Publication No. 2017 / 057281.

[0095] The percentage of the organosilane unit represented by general formula (7) in the (A2-1) polysiloxane is preferably 50-100 mol%, more preferably 60-100 mol%, and even more preferably 70-100 mol%, based on the molar ratio of Si atoms. A percentage of 50-100 mol% can improve the heat resistance of the cured film. The organosilane unit represented by general formula (7) is preferably an organosilane unit with an epoxy group. By including an epoxy-based organosilane unit in the (A2-1) polysiloxane, improved pattern processing during alkaline development and increased sensitivity during exposure can be achieved.

[0096] The percentage of the organosilane unit represented by general formula (8) in the (A2-1) polysiloxane is preferably 0 to 40 mol% based on the Si atomic molar ratio, more preferably 0 to 30 mol%, and even more preferably 0 to 20 mol%. If the percentage is 0 to 40 mol%, improved pattern processability during alkaline development, improved sensitivity during exposure, and improved heat resistance of the cured film can be achieved. Furthermore, a low-conical pattern can be formed after development, suppressing changes in the pattern opening width before and after thermal curing.

[0097] In (A2-1) polysiloxane, the aforementioned organosilane units can be either regularly arranged or irregularly arranged. Examples of regularly arranged arrangements include alternating copolymerization, periodic copolymerization, block copolymerization, or graft copolymerization. Examples of irregular arrangements include random copolymerization. Furthermore, the aforementioned organosilane units can be either two-dimensional or three-dimensional arranged. Examples of two-dimensional arrangements include, for example, linear chains. Examples of three-dimensional arrangements include, for example, ladder-like, cage-like, or mesh-like structures.

[0098] As the (A2-1) polysiloxane used in this invention, from the viewpoint of improving the heat resistance of the cured film due to the heat resistance of the aromatic groups and improving the halftone characteristics, it is preferable to contain organosilane units having aromatic groups. As the Mw of the (A2-1) polysiloxane, from the viewpoint of improving the resolution after development and improving the reliability of the light-emitting element, it is preferably 500 or more based on polystyrene conversion measured by GPC. On the other hand, as the Mw, from the viewpoint of improving the formation of low-cone pattern after thermosetting and improving the pattern processability with alkaline developer, it is preferably 50,000 or less. The (A2-1) polysiloxane can be synthesized by known methods.

[0099] <(A2-2) Resins containing polycyclic side chains>

[0100] Examples of resins containing polycyclic side chains that can be used in this invention (A2-2) include, for example, the following (I) to (IV) resins containing polycyclic side chains.

[0101] (I) A resin containing polycyclic side chains obtained by reacting an epoxy compound with a compound obtained by reacting a polyfunctional phenolic compound with a polyfunctional carboxylic acid dianhydride.

[0102] (II) A resin containing polycyclic side chains obtained by reacting a polyfunctional carboxylic acid dianhydride with a compound obtained by reacting a polyfunctional phenol compound with an epoxy compound.

[0103] (III) A resin containing polycyclic side chains obtained by reacting an epoxy compound with a compound obtained by reacting a polyfunctional epoxy compound with a polyfunctional carboxylic acid compound.

[0104] (IV) A resin containing polycyclic side chains obtained by reacting a polyfunctional carboxylic acid dianhydride with a compound obtained by reacting a polyfunctional epoxy compound with a carboxylic acid compound.

[0105] Examples of phenolic compounds, epoxy compounds, carboxylic anhydrides, and carboxylic acid compounds include, for example, the compounds described in International Publication No. 2017 / 057281.

[0106] (A2-2) The resin containing polycyclic side chains is a thermosetting resin and has a structure in which the main chain and bulky side chains are linked by a single atom. The bulky side chains have cyclic structures such as fluorene rings, which exhibit high heat resistance. Therefore, by including the (A2-2) polycyclic side chain resin with a cyclic structure such as fluorene rings, which exhibits high heat resistance, in the negative photosensitive resin composition, the heat resistance of the resulting cured film can be improved. Therefore, it is suitable for applications requiring heat resistance, such as using the cured film. The (A2-2) polycyclic side chain resin used in this invention preferably has olefinically unsaturated double bonds. By including the (A2-2) polycyclic side chain resin with olefinically unsaturated double bonds in the negative photosensitive resin composition, the sensitivity during exposure can be improved, and a low-cone pattern can be formed after development.

[0107] As the (A2-2) resin containing polycyclic side chains used in this invention, from the viewpoint of improving the heat resistance of the cured film, it is preferable to contain one or more structural units selected from the structural units shown in general formula (47), general formula (48), general formula (49), and general formula (50). Furthermore, as the (A2-2) resin containing polycyclic side chains used in this invention, from the viewpoint of improving sensitivity during exposure and forming a low-conical-shape pattern after development, it is preferable to contain olefinically unsaturated double bonds at any of the main chain, side chains, and ends.

[0108]

[0109] In general formulas (47) to (50), X 69 X 70 X 72 X 73 X 75 X 76 X 78 and X 79 Each can be used independently to represent a monocyclic or fused polycyclic hydrocarbon ring. 71 X 74 X 77 and X 80 Each independently represents a divalent to a decavalent organogroup of a carboxylic acid residue and / or a carboxylic acid derivative residue. W 1 ~W 4 Each can be used independently to represent an organic group having two or more aromatic groups. R 160 ~R 167 Each independently represents an alkyl group having 1 to 6 hydrogen atoms or carbon atoms, R 170 ~R 175 R 177 and R 178 Each can independently represent a hydrogen atom or an organic group having an alkene unsaturated double bond. R 176 It represents an alkyl group with 1 to 10 hydrogen or carbon atoms. a, b, c, d, e, f, g, and h each independently represent an integer from 0 to 10, and α, β, γ, and δ each independently represent 0 or 1.

[0110] In general formulas (47) to (50), X 69 X 70 X 72 X 73 X 75 X 76 X 78 and X 79 Each is preferably a monocyclic or fused polycyclic hydrocarbon ring with 6 to 15 carbon atoms and 2 to 10 valences. Furthermore, X 71 X 74 X 77 and X 80 Each component is preferably composed of one or more 2- to 10-valent organic groups selected from aliphatic structures with 2 to 20 carbon atoms, alicyclic structures with 4 to 20 carbon atoms, and aromatic structures with 6 to 30 carbon atoms. Furthermore, from the viewpoints of improved halftone characteristics, improved heat resistance of the cured film, and improved reliability of the light-emitting element, W... 1 ~W 4 Each substituent is preferably represented by any one of the general formulas (51) to (56). Furthermore, R 170 ~R 175 R 177 and R178 Each substituent is preferably represented by the general formula (57). The alkyl, aliphatic, alicyclic, aromatic, monocyclic, or fused polycyclic aromatic hydrocarbon rings and the organogroups having olefinic unsaturated double bonds may have heteroatoms and may be either unsubstituted or substituted.

[0111]

[0112] In general formulas (51) to (56), R 179 ~R 182 R 185 and R 188 Each can independently represent an alkyl group having 1 to 10 carbon atoms. R 183 R 184 R 186 R 187 R 189 R 191 and R 193 ~R 196 Each can independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, or an aryl group with 6 to 15 carbon atoms. R 190 and R 192 Each can independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, or an aryl group with 6 to 15 carbon atoms, and can be represented by R. 190 and R 192 Forming a ring. This is achieved using R... 190 and R 192 The formed ring can be, for example, a benzene ring or a cyclohexane ring. R 183 and R 184 At least one of the atoms is an aryl group having 6 to 15 carbon atoms. R 186 and R 187 At least one of the atoms is an aryl group having 6 to 15 carbon atoms. R 189 and R 190 At least one of them is an aryl group having 6 to 15 carbon atoms, R 191 and R 192 At least one of the aryl groups has 6 to 15 carbon atoms, which can be utilized by R 190 and R 192 Forming a ring. R 193 and R 194 At least one of them is an aryl group having 6 to 15 carbon atoms, R 195 and R 196 At least one of them is an aryl group with 6 to 15 carbon atoms. i, j, k, l, m, and n each independently represent integers from 0 to 4. In general formulas (51) to (56), R 190 and R 192Each is 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, as the component utilizing R. 190 and R 192 The formed ring is preferably a benzene ring. The alkyl, cycloalkyl, and aryl groups can be any of the unsubstituted or substituted forms.

[0113]

[0114] In general formula (57), X 81 X represents a directly bonded alkylene chain with 1 to 10 carbon atoms, a cycloalkylene chain with 4 to 10 carbon atoms, or an arylene chain with 6 to 15 carbon atoms. 82 Represents a directly bonded or aryl chain with 6 to 15 carbon atoms. R 197 This indicates vinyl, aryl, or (meth)acryloyl. In general formula (57), X 81 Preferably, it is a directly bonded alkylene chain with 1 to 6 carbon atoms, a cycloalkylene chain with 4 to 7 carbon atoms, or an arylene chain with 6 to 10 carbon atoms. Furthermore, X 82 Preferably, it is a directly bonded or arylene chain with 6 to 10 carbon atoms. The alkylene chain, cycloalkylene chain, arylene chain, vinyl group, aryl group, and (meth)acryloyl group can be any of the unsubstituted or substituted forms.

[0115] As for the resin containing polycyclic side chains (A2-2) that can be used in this invention, from the viewpoint of improving sensitivity during exposure and forming a low-cone pattern after development, it is preferable to include structural units having a fused polycyclic backbone. As structural units having a fused polycyclic backbone, it is preferable to include one or more structural units selected from those having a fluorene backbone and those having an indane backbone. By including one or more structural units selected from those having a fluorene backbone and those having an indane backbone in the resin containing polycyclic side chains (A2-2), the sensitivity during exposure can be improved, and a low-cone pattern can be formed after development. In addition, halftone characteristics can be improved. This is because the above-mentioned structural units interact significantly with the photopolymerization initiator containing a fused polycyclic backbone (C1-1a) and the photopolymerization initiator containing a fused polycyclic heterocyclic backbone (C1-1b) described later, thereby improving the compatibility between the alkali-soluble resin and the photopolymerization initiator, and allowing UV curing to proceed efficiently even during exposure to deep layers of the film. In the above general formulas (47) to (50), if W 1 ~W 4 If the resin is of general formula (51) or general formula (53), then (A2-2) containing polycyclic side chains comprises one or more structural units selected from structural units having a fluorene backbone and structural units having an indene backbone.

[0116] <Acidic groups derived from carboxylic acids and acidic groups derived from carboxylic acid derivatives>

[0117] As a resin containing polycyclic side chains (A2-2), from the viewpoint of improving pattern processing properties with alkaline developing solution and improving resolution after development, it is preferable to contain structural units derived from carboxylic acids and / or structural units derived from carboxylic acid derivatives. The resin containing polycyclic side chains (A2-2) has acidic groups. Examples of acidic groups include carboxyl groups, carboxylic anhydride groups, sulfonic acid groups, phenolic hydroxyl groups, or hydroxyimide groups. From the viewpoint of improving pattern processing properties with alkaline developing solution and improving resolution after development, carboxyl groups, carboxylic anhydride groups, or phenolic hydroxyl groups are preferred, and carboxyl groups or carboxylic anhydride groups are more preferred.

[0118] <End-capping agent>

[0119] As a resin containing polycyclic side chains (A2-2), from the viewpoint of improving the preservation stability of the resin composition coating and improving the pattern processing properties with alkaline developer, it is preferable that the ends of the resin are sealed with end-capping agents such as tricarboxylic anhydride, dicarboxylic anhydride, or monocarboxylic acid.

[0120] As for the (A2-2) resin containing polycyclic side chains, from the viewpoint of improving the heat resistance of the cured film due to the heat resistance of the aromatic groups and improving the halftone characteristics, it is preferable to contain structural units derived from aromatic carboxylic acids and / or structural units derived from aromatic carboxylic acid derivatives. As for the (A2-2) resin containing polycyclic side chains, the Mw (weight-average weight) is preferably 500 or more, calculated as polystyrene by GPC, from the viewpoint of improving the resolution after development and improving the reliability of the light-emitting element. On the other hand, as for the Mw, it is preferably 50,000 or less, from the viewpoint of improving the formation of low-cone pattern after thermosetting and improving the pattern processability with alkaline developer. The (A2-2) resin containing polycyclic side chains can be synthesized by known methods.

[0121] <(A2-2) Specific examples of resins containing polycyclic side chains>

[0122] Examples of resins containing polycyclic side chains (A2-2) include, for example, “ADEKA ARKLS” (registered trademark) WR-101 or “ADEKA ARKLS” WR-301 (all manufactured by ADEKA), OGSOL (registered trademark) CR-1030, OGSOL CR-TR1, OGSOL CR-TR2, OGSOL CR-TR3, OGSOL CR-TR4, OGSOL CR-TR5, OGSOL CR-TR6, OGSOL CR-TR7, OGSOL CR-TR8, OGSOL CR-TR9, or OGSOL CR-TR10 (all manufactured by Osaka Gaskemikar), or TR-B201 or TR-B202 (all manufactured by TRONLY).

[0123] <(A2-3) Acid-Modified Epoxy Resin>

[0124] Examples of acid-modified epoxy resins (A2-3) that can be used in the present invention include, for example, the acid-modified epoxy resins (I) to (VI) below.

[0125] (I) An acid-modified epoxy resin obtained by reacting an epoxy compound with a compound obtained by reacting a polyfunctional phenolic compound with a polyfunctional carboxylic acid dianhydride.

[0126] (II) An acid-modified epoxy resin obtained by reacting a polyfunctional carboxylic acid dianhydride with a compound obtained by reacting a polyfunctional phenolic compound with an epoxy compound.

[0127] (III) An acid-modified epoxy resin obtained by reacting an epoxy compound with a compound obtained by reacting a polyfunctional alcohol compound with a polyfunctional carboxylic acid dianhydride.

[0128] (IV) An acid-modified epoxy resin obtained by reacting a polyfunctional carboxylic acid dianhydride with a compound obtained by reacting a polyfunctional alcohol compound with an epoxy compound.

[0129] (V) An acid-modified epoxy resin obtained by reacting an epoxy compound with a compound obtained by reacting a polyfunctional epoxy compound with a polyfunctional carboxylic acid compound.

[0130] (VI) An acid-modified epoxy resin obtained by reacting a polyfunctional carboxylic acid dianhydride with a compound obtained by reacting a polyfunctional epoxy compound with a carboxylic acid compound.

[0131] Examples of phenolic compounds, alcoholic compounds, epoxide compounds, carboxylic anhydrides, and carboxylic acid compounds include, for example, the compounds described in International Publication No. 2017 / 057281.

[0132] As an (A2-3) acid-modified epoxy resin, it is preferable to have olefinically unsaturated double bonds. By containing an (A2-3) acid-modified epoxy resin with olefinically unsaturated double bonds in the resin composition, the sensitivity during exposure can be improved, and a low-cone pattern can be formed after development.

[0133] As an (A2-3) acid-modified epoxy resin, from the viewpoints of improved halftone characteristics, improved heat resistance of the cured film, and improved reliability of the light-emitting element, it is preferable to contain one or more structural units selected from the structural units shown in general formula (35), general formula (36), general formula (37), general formula (38), general formula (41), general formula (42), and general formula (43). Furthermore, from the viewpoints of improved sensitivity during exposure and formation of a low-cone pattern after development, the (A2-3) acid-modified epoxy resin used in this invention preferably has olefinically unsaturated double bonds at any of the main chain, side chains, and ends.

[0134]

[0135] In general formulas (35) to (38), X 51 ~X 54 Each can independently represent an aliphatic structure with 1 to 6 carbon atoms. Z 53 R represents aromatic structures with 10–25 carbon atoms and valences of 3–16. 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 R represents an alkyl group having 1 to 10 carbon atoms. 78 ~R 82 Each can independently represent a halogen, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, or an aryl group with 6 to 15 carbon atoms, R 83 ~R 88 Each of the substituents represented by the general formula (39) is independent. a, b, c, d, and e each represent an integer from 0 to 10, f represents an integer from 0 to 14, h, i, j, and k each represent an integer from 0 to 3, and l represents an integer from 0 to 4. The alkyl, cycloalkyl, aryl, aliphatic, and aromatic structures mentioned above may have heteroatoms and may be either unsubstituted or substituted.

[0136] Z as general formula (38) 53 The aromatic structure contains one or more skeletons selected from terphenyl, naphthalene, anthracene, and fluorene. Furthermore, Z, as a general formula (38) 53Other aromatic structures include, for example, 1,2,3,4-tetrahydronaphthalene skeleton, 2,2-diphenylpropane skeleton, diphenyl ether skeleton, diphenyl ketone skeleton, or diphenyl sulfone skeleton.

[0137]

[0138] In general formula (39), X 55 R represents an alkylene chain with 1 to 6 carbon atoms or a cycloalkylene chain with 4 to 10 carbon atoms. 89 ~R 91 Each can independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. R 92 Represents a hydrogen atom or a substituent as shown in general formula (40). In general formula (39), R 89 and R 90 Each is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom. R 91 Preferably, it is an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group. In general formula (40), X 56 This refers to an alkylene chain with 1 to 6 carbon atoms, an alkenylene chain with 1 to 6 carbon atoms, a cycloalkylene chain with 4 to 10 carbon atoms, or a cycloalkylene chain with 4 to 10 carbon atoms. In general formula (40), X 56 Preferably, the alkylene chain has 1 to 4 carbon atoms, the alkenylene chain has 1 to 4 carbon atoms, the cycloalkylene chain has 4 to 7 carbon atoms, or the cycloalkylene chain has 4 to 7 carbon atoms. The aforementioned alkylene chain, cycloalkylene chain, alkyl group, and aryl group can be any of the unsubstituted or substituted forms.

[0139]

[0140] In general formulas (41) to (43), X 57 ~X 61 Each independently represents an aliphatic structure with 1 to 6 carbon atoms, X 62 and X 63 Each can independently represent an alkylene chain with 1 to 6 carbon atoms or a cycloalkylene chain with 4 to 10 carbon atoms. R 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 can independently represent a halogen, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, or an aryl group with 6 to 15 carbon atoms, R 105 R represents an alkyl group having 1 to 6 hydrogen atoms or carbon atoms. 106 and R 107Each of the substituents represented independently by the general formula (39), R 108 The numbers represent hydrogen atoms, substituents represented by general formula (39), or substituents represented by general formula (40). m, n, o, p, and q each independently represent integers from 0 to 10, r and s each independently represent integers from 0 to 3, and t, u, v, w, and x each independently represent integers from 0 to 4. The aforementioned alkylene chains, cycloalkylene chains, alkyl groups, cycloalkyl groups, aryl groups, and aliphatic structures may have heteroatoms and may be either unsubstituted or substituted.

[0141] The (A2-3) acid-modified epoxy resin that can be used in the present invention, as an (A2-3) acid-modified epoxy resin having the structural unit shown in general formula (43), preferably having a substituent shown in general formula (44) and / or a substituent shown in general formula (45) at the end.

[0142]

[0143] In general formula (44), R 109 The substituents shown in general formula (39) are represented. In general formula (45), X 64 Represents aliphatic structures with 1 to 6 carbon atoms. R 110 R 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. 111 and R 112 Each can independently represent a halogen, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, or an aryl group with 6 to 15 carbon atoms. R 113 The substituents shown in general formula (39) are represented. α represents an integer from 0 to 10. β and γ represent integers from 0 to 4. In general formula (45), X 64 Preferably, it has an aliphatic structure with 1 to 4 carbon atoms. 110 Preferably, it is 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, R 111 and R 112 Each of the following is 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.

[0144] As for the acid-modified epoxy resin (A2-3) that can be used in this invention, from the viewpoint of improved sensitivity during exposure and formation of a low-cone pattern after development, it is preferable to include structural units having a fused polycyclic skeleton. As a structural unit having a fused polycyclic skeleton, it is preferable to include units selected from those having three rings [5.2.1.0]. 2,6The structural unit comprises one or more of the following: a decane skeleton, a naphthalene skeleton, an anthracene skeleton, and a fluorene skeleton. By incorporating these structural units into the (A2-3) acid-modified epoxy resin, the sensitivity during exposure can be improved, and a low-cone pattern can be formed after development. Furthermore, halftone properties can be improved. This can be attributed to the significant interaction between the aforementioned structural units and the photopolymerization initiators (C1-1a) and (C1-1b) containing fused polycyclic heterocyclic skeletons, thereby improving the compatibility between the alkali-soluble resin and the photopolymerization initiator, and enabling efficient UV curing even during deep exposure of the film. In the case of containing the structural unit shown in the above general formula (37), or in the case of the above general formula (38) in Z... 53 When the epoxy resin contains one or more of a terphenyl skeleton, naphthalene skeleton, anthracene skeleton, and fluorene skeleton, (A2-3) acid-modified epoxy resin comprises a compound selected from those having a tricyclic [5.2.1.0] structure. 2,6 [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.]

[0145] <Acidic groups derived from carboxylic acids and acidic groups derived from carboxylic acid derivatives>

[0146] (A2-3) The acid-modified epoxy resin contains structural units derived from carboxylic acids and / or carboxylic acid derivatives in its backbone. As functional groups providing alkali solubility to the resin, it has carboxyl groups and / or carboxylic anhydride groups. By having carboxyl groups and / or carboxylic anhydride groups, the patterning processability with alkaline developer can be improved, and the resolution after development can be improved. Furthermore, other acidic groups can be present. Examples of acidic groups include sulfonic acid groups, phenolic hydroxyl groups, or hydroxyimide groups. From the viewpoint of improved patterning processability with alkaline developer and improved resolution after development, phenolic hydroxyl groups are preferred.

[0147] <End-capping agent>

[0148] From the viewpoint of improving the preservation stability of the coating solution of the resin composition and improving the pattern processing properties with alkaline developer, (A2-3) acid-modified epoxy resin preferably has its ends sealed with end-capping agents such as tricarboxylic anhydride, dicarboxylic anhydride, or monocarboxylic acid.

[0149] From the viewpoint of improved heat resistance of the cured film due to the heat resistance of aromatic groups and improved halftone properties, the (A2-3) acid-modified epoxy resin preferably contains structural units derived from aromatic carboxylic acids and / or structural units derived from aromatic carboxylic acid derivatives in its backbone. As the Mw of the (A2-3) acid-modified epoxy resin, from the viewpoint of improved resolution after development and improved reliability of the light-emitting element, it is preferably 500 or more, calculated as polystyrene by GPC. On the other hand, as the Mw, from the viewpoint of improved low-cone pattern formation after thermosetting and improved pattern processability with alkaline developer, it is preferably 50,000 or less. The (A2-3) acid-modified epoxy resin can be synthesized by known methods.

[0150] <(A2-3) Specific Examples of Acid-Modified Epoxy Resins>

[0151] Examples of acid-modified epoxy resins (A2-3) include, for example, "KAYARAD" (registered trademark) PCR-1222H, "KAYARAD" CCR-1171H, "KAYARAD" TCR-1348H, "KAYARAD" ZAR-1494H, "KAYARAD" ZFR-1401H, "KAYARAD" ZCR-1798H, "KAYARAD" ZXR-1807H, "KAYARAD" ZCR-6002H, or "KAYARAD" ZCR-8001H (all of which are manufactured by Nippon Kayaku Co., Ltd.), or "NK OLIGO" (registered trademark) EA-6340, "NK OLIGO" EA-7140, or "NKOLIGO" EA-7340 (all of which are manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0152] <(A2-4) Acrylic Resins>

[0153] As an acrylic resin (A2-4) that can be used in the present invention, examples include acrylic resins obtained by free radical copolymerization of one or more copolymers selected from those having an acidic group, copolymers derived from (meth)acrylates, and other copolymers.

[0154] Examples of copolymers containing acidic groups, copolymers derived from (meth)acrylates, and other copolymers include, for example, the compound described in International Publication No. 2017 / 057281.

[0155] As for the (A2-4) acrylic resin, from the viewpoint of improving the sensitivity during exposure and improving the mechanical properties of the cured film, it is preferable to contain the structural unit shown in general formula (61) and / or the structural unit shown in general formula (62).

[0156]

[0157] In general formulas (61) and (62), Rd 1 and Rd 2 Each of these groups 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. R 200 ~R 205 Each can independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, or an aryl group with 6 to 15 carbon atoms. X 90 and X 91 Each can be used independently to represent a directly bonded alkylene chain with 1 to 10 carbon atoms, a cycloalkylene chain with 4 to 10 carbon atoms, or an arylene chain with 6 to 15 carbon atoms.

[0158] In general formulas (61) and (62), Rd 1 and Rd 2 Each is preferably an alkyl group having an olefinic unsaturated double bond and 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. Furthermore, R 200 ~R 205 Each is 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. Furthermore, X 90 and X 91 Each of the following is preferably a directly bonded alkylene chain with 1 to 6 carbon atoms, a cycloalkylene chain with 4 to 7 carbon atoms, or an arylene chain with 6 to 10 carbon atoms. The aforementioned alkyl, cycloalkyl, aryl, alkylene, cycloalkylene, and arylene chains may have heteroatoms and may be any of the unsubstituted or substituted forms.

[0159] <Structural units derived from copolymer components with acidic groups>

[0160] From the viewpoint of improving pattern processing properties with alkaline developing solution and improving resolution after development, it is preferable that the (A2-4) acrylic resin contains structural units derived from copolymer components having acidic groups. Examples of acidic groups include carboxyl groups, carboxylic anhydride groups, sulfonic acid groups, phenolic hydroxyl groups, or hydroxyimide groups. From the viewpoint of improving pattern processing properties with alkaline developing solution and improving resolution after development, carboxyl groups, carboxylic anhydride groups, or phenolic hydroxyl groups are preferred, and carboxyl groups or carboxylic anhydride groups are more preferred.

[0161] <Introduction of olefinic unsaturated double bonds>

[0162] As the (A2-4) acrylic resin that can be used in this invention, it is preferable to have olefinically unsaturated double bonds. By including the (A2-4) acrylic resin with olefinically unsaturated double bonds in the negative photosensitive resin composition, the sensitivity during exposure can be improved, and a low-cone pattern can be formed after development. Preferably, the resin is obtained by performing a ring-opening addition reaction between an unsaturated compound having olefinically unsaturated double bonds and epoxy groups and the acidic groups of the (A2-4) acrylic resin. By reacting the epoxy groups with the acidic groups, an (A2-4) acrylic resin that incorporates olefinically unsaturated double bonds while lacking epoxy groups can be obtained.

[0163] As for the (A2-4) acrylic resin, from the viewpoint of improving pattern processing properties with alkaline developing solution and improving the storage stability of the coating solution, if the (A2-4) acrylic resin has carboxyl groups, it is preferable to have an (A2-4) acrylic resin without epoxy groups. Furthermore, from the viewpoint of improving the heat resistance of the cured film due to the heat resistance of aromatic groups and improving halftone characteristics, it is preferable to contain structural units derived from copolymer components having aromatic groups. It should be noted that, as for the (A2-4) acrylic resin, from the viewpoint of improving the heat resistance of the cured film due to the heat resistance and transparency of alicyclic groups and improving the sensitivity during exposure, it is also preferable to contain structural units derived from copolymer components having alicyclic groups. As for the Mw of the (A2-4) acrylic resin, from the viewpoint of improving resolution after development and improving the reliability of the light-emitting element, it is preferably 1,000 or more, calculated as polystyrene by GPC. On the other hand, as for Mw, from the viewpoint of pattern formation with a low cone shape after thermosetting and improved pattern processability with alkaline developer, it is preferably 50,000 or less. (A2-4) Acrylic resins can be synthesized by known methods.

[0164] <Other Alkali-Soluble Resins>

[0165] The negative photosensitive resin composition of the present invention may further contain other alkali-soluble resins as (A) alkali-soluble resins. From the viewpoint of improving low-cone pattern formation and halftone properties after development, it is preferable that the other alkali-soluble resins contain one or more selected from phenolic varnish resins, methyl phenolic resins, and polyhydroxystyrene, and more preferably phenolic varnish resins. In the present invention, phenolic varnish resins, methyl phenolic resins, and polyhydroxystyrene can be any single resin or copolymers thereof.

[0166] From the viewpoint of improving halftone properties, phenolic hydroxyl groups are preferred as alkali-soluble groups among the phenolic varnish resins, methyl phenolic resins, and polyhydroxystyrene that can be used in the present invention.

[0167] The phenolic varnish resin, methyl phenolic resin, and polyhydroxystyrene used in this invention may also have acidic groups other than phenolic hydroxyl groups. Examples of acidic groups include carboxyl groups, carboxylic anhydride groups, sulfonic acid groups, or hydroxyimide groups. From the viewpoint of improving pattern processability with alkaline developing solution and improving resolution after development, carboxyl groups and carboxylic anhydride groups are preferred. Furthermore, the phenolic varnish resin, methyl phenolic resin, and polyhydroxystyrene used in this invention preferably have olefinic unsaturated double bonds. By having olefinic unsaturated double bonds, the sensitivity during exposure can be improved, and a low-cone pattern can be formed after development.

[0168] <Ratio of (A1) first resin, (A2) second resin, and other alkali-soluble resins>

[0169] In the negative photosensitive resin composition of the present invention, the content ratio of (A1) first resin in a total of 100% by mass of (A1) first resin and (A2) second resin is preferably 25% by mass or more, more preferably 50% by mass or more, further preferably 60% by mass or more, further more preferably 70% by mass or more, and particularly preferably 80% by mass or more. If the content ratio is 25% by mass or more, the heat resistance of the cured film and the reliability of the light-emitting element can be improved. In addition, halftone characteristics can be improved. On the other hand, the content ratio of (A1) first resin is preferably 99% by mass or less, more preferably 98% by mass or less, further preferably 97% by mass or less, further more preferably 95% by mass or less, and particularly preferably 90% by mass or less. If the content ratio is 99% by mass or less, the sensitivity during exposure can be improved, and a low-cone pattern can be formed after development. In addition, halftone characteristics can be improved.

[0170] In the negative photosensitive resin composition of the present invention, from the viewpoint of improving the formation of a low-cone pattern after development and enhancing halftone characteristics, the content ratio of other alkali-soluble resins in the total 100% by mass of (A1) first resin, (A2) second resin, and other alkali-soluble resins is preferably 1% by mass or more, more preferably 5% by mass or more. On the other hand, from the viewpoint of improving sensitivity during exposure and enhancing the reliability of the light-emitting element, the content ratio of other alkali-soluble resins is preferably 30% by mass or less, more preferably 15% by mass or less.

[0171] <<(B) Free Radical Polymers>>

[0172] In the negative photosensitive resin composition of the present invention, it is preferable to further contain a (B) radical polymerizable compound. A (B) radical polymerizable compound refers to a compound having multiple olefinic unsaturated double bonds in its molecule. During exposure, the (B) radical polymerizable compound undergoes free radical polymerization via free radicals generated by the (C1) photopolymerization initiator (described later). The exposed portion of the resin composition film becomes insoluble in the alkaline developer, thereby enabling the formation of a negative pattern.

[0173] By incorporating a (B) radical polymerizable compound, UV curing during exposure is promoted, thereby increasing the sensitivity during exposure. Furthermore, the increased crosslinking density after thermal curing improves the hardness of the cured film. As the (B) radical polymerizable compound, a compound having (meth)acryloyl groups that facilitates free radical polymerization is preferred. From the viewpoint of improved sensitivity during exposure and improved hardness of the cured film, a compound having two or more (meth)acryloyl groups in the molecule is more preferred. As for the double bond equivalent of the (B) radical polymerizable compound, from the viewpoint of improved sensitivity during exposure and formation of low-cone pattern, 80 to 800 g / mol is preferred.

[0174] From the viewpoint of improved sensitivity during exposure and formation of a low-cone pattern after development, the content of the free radical polymerizable compound (B) 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, when the total amount of the alkali-soluble resin (A) and the free radical polymerizable compound (B) is set to 100 parts by mass. On the other hand, from the viewpoint of improved heat resistance of the cured film and improved reliability of the light-emitting element, the content of the free radical polymerizable compound (B) is preferably 65 parts by mass or less, more preferably 55 parts by mass or less.

[0175] <(B1) Radical polymers containing a fluorene skeleton and (B2) Radical polymers containing an indane skeleton>

[0176] The negative photosensitive resin composition of the present invention preferably further contains one or more of the following as (B) radical polymerizable compounds: (B1) a free radical polymerizable compound containing a fluorene skeleton and (B2) a free radical polymerizable compound containing an indane skeleton. The (B1) free radical polymerizable compound containing a fluorene skeleton refers to a compound having multiple olefinic unsaturated double bonds and a fluorene skeleton in its molecule. The (B2) free radical polymerizable compound containing an indane skeleton refers to a compound having multiple olefinic unsaturated double bonds and an indane skeleton in its molecule. From the viewpoint of improving sensitivity during exposure and suppressing residue after development, compounds having two or more (meth)acryloyl groups in their molecule are preferred as the (B1) free radical polymerizable compound containing a fluorene skeleton and the (B2) free radical polymerizable compound containing an indane skeleton.

[0177] By containing one or more of a free radical polymerizable compound selected from (B1) containing a fluorene skeleton and (B2) containing an indane skeleton, the sensitivity during exposure and the ability to form low-cone patterns after development can be improved, as well as the ability to form low-cone patterns after heat curing. In addition, halftone properties can be improved. Furthermore, in the case of the black agent described later (Da), particularly in the case of a benzofuranone-based black pigment containing (D1a-1a), development residues originating from the pigment sometimes occur due to insufficient alkali resistance of the pigment. In such cases, by containing one or more of the aliphatic free radical polymerizable compound containing a soft chain (B3) and a free radical polymerizable compound selected from (B1) containing a fluorene skeleton and (B2) containing an indane skeleton, the generation of development residues originating from the pigment can be suppressed.

[0178] This can be attributed to the fact that the fluorene and indane skeletons significantly interact with the fused polycyclic skeletons of the photopolymerization initiators (C1-1a) and (C1-1b) containing fused polycyclic heterocyclic skeletons, thereby improving the compatibility between the free radical polymerizable compound and the photopolymerization initiator, and enabling efficient UV curing even when exposed to deep layers of the film.

[0179] Examples of free radical polymerizable compounds containing a fluorene skeleton in (B1) include, for example, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene, 9,9-bis[4-(3-(meth)acryloyloxypropoxy)phenyl]fluorene, 9,9-bis(4-(meth)acryloyloxyphenyl)fluorene, 9,9-bis[4-(2-hydroxy-3-(meth)acryloyloxypropoxy)phenyl]fluorene, or 9,9-bis[3,4-bis(2-(meth)acryloyloxyethoxy)phenyl]fluorene.

[0180] Examples of free radical polymerizable compounds containing an indaminozide skeleton (B2) include, for example, 1,1-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]indaminozide, 1,1-bis(4-(meth)acryloyloxyphenyl)indaminozide, 1,1-bis[4-(2-hydroxy-3-(meth)acryloyloxypropoxy)phenyl]indaminozide, 1,1-bis[3,4-bis(2-(meth)acryloyloxyethoxy)phenyl]indaminozide, 2,2-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]indaminozide, or 2,2-bis(4-(meth)acryloyloxyphenyl)indaminozide.

[0181] From the viewpoint of improving the formation of a low-cone pattern after development and enhancing halftone properties, the total content of (B1) the free radical polymerizable compound containing a fluorene framework and (B2) the free radical polymerizable compound containing an indane framework in the negative photosensitive resin composition of the present invention is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, when the total content of (A) the alkali-soluble resin and (B) the free radical polymerizable compound is set to 100 parts by mass. On the other hand, from the viewpoint of suppressing residue after development, the total content of (B1) the free radical polymerizable compound containing a fluorene framework and (B2) the free radical polymerizable compound containing an indane framework is preferably 25 parts by mass or less, more preferably 20 parts by mass or less.

[0182] <(B3) Aliphatic free radical polymerizable compounds containing soft chains>

[0183] The negative photosensitive resin composition of the present invention preferably further contains (B3) an aliphatic free radical polymerizable compound with a flexible chain as the (B) free radical polymerizable compound. The (B3) aliphatic free radical polymerizable compound with a flexible chain refers to a compound having multiple olefinic unsaturated double bonds and a flexible backbone such as an aliphatic chain or an oxidized olefinic chain in its molecule. Preferably, the (B3) aliphatic free radical polymerizable compound has (I) a structure derived from a compound having at least two hydroxyl groups in its molecule, (II) at least two olefinic unsaturated double bonds, and (III) at least one aliphatic chain.

[0184] By using an aliphatic radical polymerizable compound containing (B3) with a soft chain, UV curing during exposure is carried out efficiently, improving exposure sensitivity and halftone properties. Furthermore, when used as a colorant (D) in the subsequent description, particularly containing a (D1) pigment, the (D1) pigment is immobilized in the cured portion through cross-linking during UV curing of the aliphatic radical polymerizable compound containing (B3) with a soft chain, thereby suppressing the generation of residues from the (D1) pigment after development. Moreover, even when used as a black agent (Da) in the subsequent description, particularly containing a (D1a-1a) benzofuranone-based black pigment, the generation of development residues from the pigment due to insufficient alkali resistance of the subsequent pigment can be suppressed.

[0185] As (B3) an aliphatic free radical polymerizable compound containing a soft chain, it is preferably a compound having a group represented by general formula (24) as at least one aliphatic chain in (III) above, and having three or more groups represented by general formula (25) as at least two olefinic unsaturated double bonds in (II) above.

[0186]

[0187] In general formula (24), R 125 Represents an alkyl group having 1 to 10 hydrogen or carbon atoms. Z 17 Represents the group shown in general formula (29) or general formula (30). a represents an integer from 1 to 10, b represents an integer from 1 to 4, c represents 0 or 1, d represents an integer from 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 can independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. In general formula (30), R 129 This refers to an alkyl group having 1 to 10 hydrogen or carbon atoms. From the viewpoint of improving sensitivity during exposure and suppressing residue after development, in general formula (24), c is preferably 1 and e is preferably 1. In general formula (25), R... 126 Preferably, it is an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group. 127 and R 128 Each is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom. In general formula (30), R 129 Preferably, it is an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom or a methyl group.

[0188] As an aliphatic radical polymerizable compound containing a soft chain (B3), from the viewpoints of improved sensitivity during exposure, improved halftone properties, and suppression of residue after development, it is preferable that at least one aliphatic chain (III) above has at least one lactone modified chain and / or at least one lactam modified chain. In the above general formula (24), if c is 1 and e is 1, then the aliphatic radical polymerizable compound containing a soft chain (B3) has at least one lactone modified chain and / or at least one lactam modified chain.

[0189] From the viewpoint of improving sensitivity during exposure, the (B3) aliphatic radical polymerizable compound containing a soft chain preferably has 2 or more olefinic unsaturated double bonds in its molecule, more preferably 3 or more, and even more preferably 4 or more. On the other hand, from the viewpoint of forming a low-conical pattern after thermosetting, the (B3) aliphatic radical polymerizable compound containing a soft chain preferably has 12 or less olefinic unsaturated double bonds in its molecule, more preferably 10 or less, and even more preferably 8 or less.

[0190] Examples of (B3) aliphatic free radical polymerizable compounds containing a soft chain, and compounds having three or more olefinic unsaturated double bonds in their molecules, include, for example, ethoxylated pentaerythritol hexa(meth)acrylate, propoxylated pentaerythritol hexa(meth)acrylate, ε-caprolactone-modified pentaerythritol hexa(meth)acrylate, δ-valerolactone-modified pentaerythritol hexa(meth)acrylate, γ-butyrolactone-modified pentaerythritol hexa(meth)acrylate, β-propiolactone-modified pentaerythritol hexa(meth)acrylate, ε... -Caprolactam-modified dipentaerythritol hexa(meth)acrylate, ε-caprolactone-modified dipentaerythritol penta(meth)acrylate, ε-caprolactone-modified trimethylolpropane tri(meth)acrylate, ε-caprolactone-modified bis(trimethylolpropane tetra(meth)acrylate, ε-caprolactone-modified glycerol tri(meth)acrylate, ε-caprolactone-modified pentaerythritol tri(meth)acrylate, ε-caprolactone-modified pentaerythritol tetra(meth)acrylate, or ε-caprolactone-modified 1,3,5-tris((meth)acryloyloxyethyl)isocyanuric acid.

[0191] Examples of compounds having two olefinic unsaturated double bonds in their molecules include, for example, ε-caprolactone-modified neopentyl glycol di(meth)acrylate, ε-caprolactone-modified trimethylolpropane di(meth)acrylate, ε-caprolactone-modified bis(trimethylolpropane)acrylate, ε-caprolactone-modified glycerol di(meth)acrylate, ε-caprolactone-modified pentaerythritol di(meth)acrylate, ε-caprolactone-modified dimethylol-tricyclodecane di(meth)acrylate, or ε-caprolactone-modified 1,3-bis((meth)acryloyloxyethyl)isocyanuric acid.

[0192] From the viewpoints of improved sensitivity during exposure, suppression of residue after development, and improved halftone properties, the content of the aliphatic free radical polymerizable compound (B3) containing a soft chain in the negative photosensitive resin composition of the present invention is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, when the total amount of (A) alkali-soluble resin and (B) free radical polymerizable compound is set to 100 parts by mass. On the other hand, from the viewpoint of forming a low-cone pattern after thermosetting, the content of the aliphatic free radical polymerizable compound (B3) containing a soft chain is preferably 40 parts by mass or less, more preferably 35 parts by mass or less.

[0193] <(B4) Radical polymerizable compounds containing alicyclic groups>

[0194] The negative photosensitive resin composition of the present invention preferably further contains a (B4) radical polymerizable compound containing an alicyclic group as the (B) radical polymerizable compound. The (B4) radical polymerizable compound containing an alicyclic group refers to a compound having multiple olefinic unsaturated double bonds and alicyclic groups in its molecule. From the viewpoint of improving sensitivity during exposure and suppressing residue after development, compounds having two or more (meth)acryloyl groups in their molecule are preferred as the (B4) radical polymerizable compound containing an alicyclic group.

[0195] As the alicyclic group in the molecule of the radical polymerizable compound (B4) containing an alicyclic group, a fused polycyclic alicyclic backbone is preferred. Having a fused polycyclic alicyclic backbone improves the sensitivity during exposure and allows for the formation of a low-cone pattern after development. Furthermore, halftone properties are improved. This is because the fused polycyclic alicyclic backbone significantly interacts with the fused polycyclic backbone of the photopolymerization initiator (C1-1a) and the fused polycyclic heterocyclic backbone of the photopolymerization initiator (C1-1b), thereby improving the compatibility between the radical polymerizable compound and the photopolymerization initiator, and enabling efficient UV curing even during exposure to deep layers of the film.

[0196] Examples of fused polycyclic alicyclic skeletons possessed by (B4) radical polymerizable compounds containing alicyclic groups include, for example, bicyclic [4.3.0]nonane skeleton, bicyclic [5.4.0]undecane skeleton, bicyclic [2.2.2]octane skeleton, and tricyclic [5.2.1.0]octane skeleton. 2,6 Decane skeleton, pentacyclic pentadecane skeleton, adamantane skeleton or hydroxyadamantane skeleton.

[0197] Examples of free radical polymerizable compounds containing alicyclic groups (B4) with a fused polycyclic alicyclic skeleton include, for example, dihydroxymethyl-bicyclo[4.3.0]nonane di(meth)acrylate, dihydroxymethyl-bicyclo[5.4.0]undecane di(meth)acrylate, dihydroxymethyl-bicyclo[2.2.2]octane di(meth)acrylate, and dihydroxymethyl-tricyclo[5.2.1.0]undecane di(meth)acrylate. 2,6 Decane di(meth)acrylate, dihydroxymethyl-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.

[0198] From the viewpoint of improving the formation of a low-cone pattern after development and enhancing halftone properties, the content of the alicyclic free radical polymerizable compound (B4) in the negative photosensitive resin composition of the present invention is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, when the total amount of (A) alkali-soluble resin and (B) free radical polymerizable compound is set to 100 parts by mass. On the other hand, from the viewpoint of suppressing residue after development, the content of the alicyclic free radical polymerizable compound (B4) is preferably 30 parts by mass or less, more preferably 25 parts by mass or less.

[0199] <<(C) Photosensitive Agent>>

[0200] <(C1) Photopolymerization Initiator>

[0201] The negative photosensitive resin composition of the present invention contains a (C1) photopolymerization initiator as a (C) photosensitizer. The (C1) photopolymerization initiator refers to a compound that generates free radicals through bond breaking and / or reaction upon exposure. By containing the (C1) photopolymerization initiator, free radical polymerization of the aforementioned (B) free radical polymerizable compound occurs, and the exposed portion of the resin composition film is insoluble in alkaline developing solutions, thus enabling the formation of negative patterns. Furthermore, since UV curing during exposure is promoted, the sensitivity during exposure can be improved.

[0202] As the (C1) photopolymerization initiator, preferably, for example, a benzoyl ketal photopolymerization initiator, an α-hydroxy ketone photopolymerization initiator, an α-amino ketone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, a biimidazole photopolymerization initiator, an oxime ester photopolymerization initiator, an acridine photopolymerization initiator, a titanium cephalodecene photopolymerization initiator, a benzophenone photopolymerization initiator, an acetophenone photopolymerization initiator, an aromatic ketone ester photopolymerization initiator, or a benzoic acid ester photopolymerization initiator, from the viewpoint of improving the sensitivity during exposure, preferably an α-hydroxy ketone photopolymerization initiator, an α-amino ketone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, a biimidazole photopolymerization initiator, or an oxime ester photopolymerization initiator, and even more preferably an oxime ester photopolymerization initiator.

[0203] From the viewpoint of improving sensitivity during exposure, the content of the (C1) photopolymerization initiator in the negative photosensitive resin composition of the present invention is preferably 0.5 parts by mass or more, more preferably 5 parts by mass or more, when the total amount of (A) alkali-soluble resin and (B) free radical polymerizable compound is set to 100 parts by mass. On the other hand, from the viewpoint of improving resolution after development and forming a low-cone pattern after development, the content of the (C1) photopolymerization initiator is preferably 30 parts by mass or less, more preferably 20 parts by mass or less.

[0204] <(C1-1)oxime ester photopolymerization initiator>

[0205] The negative photosensitive resin composition of the present invention contains two or more (C1-1) oxime ester photopolymerization initiators with different structures as (C1) photopolymerization initiators. A (C1-1) oxime ester photopolymerization initiator refers to a compound having an oxime ester skeleton in its molecule as the skeleton for generating free radicals through bond breaking and / or reaction upon exposure. By containing two or more (C1-1) oxime ester photopolymerization initiators, the sensitivity during exposure can be improved. This is presumably because, compared to the case containing a single (C1-1) oxime ester photopolymerization initiator, the energy of the UV light during exposure can be more efficiently utilized for free radical curing.

[0206] (C1-1a) Photopolymerization initiators containing fused polycyclic frameworks and (C1-1b) photopolymerization initiators containing fused polycyclic heterocyclic frameworks

[0207] The negative photosensitive resin composition of the present invention 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 having a fused polycyclic skeleton in its molecule, which generates free radicals through bond cleavage and / or reaction upon exposure. The (C1-1b) photopolymerization initiator containing a fused polycyclic heterocyclic skeleton refers to a compound having a fused polycyclic heterocyclic skeleton in its molecule, which generates free radicals through bond cleavage and / or reaction upon exposure. A fused polycyclic skeleton refers to a cyclic skeleton formed by two or more rings bonding one or more atoms of each ring in a manner shared by two or more rings. The fused polycyclic skeleton has two or more bridgehead atoms among the atoms constituting the rings. Examples of fused polycyclic frameworks include bicyclic, tricyclic, tetracyclic, pentacyclic, and spirocyclic frameworks. A fused polycyclic heterocyclic framework refers to a cyclic framework in which the atoms constituting the rings include heteroatoms other than carbon and hydrogen atoms. Examples of heteroatoms other than carbon and hydrogen atoms in fused polycyclic heterocyclic frameworks include oxygen, nitrogen, sulfur, fluorine, silicon, phosphorus, boron, chlorine, bromine, or iodine atoms.

[0208] By using (C1-1) oxime ester-based photopolymerization initiators containing at least (C1-1a) a photopolymerization initiator with a fused polycyclic skeleton and (C1-1b) a photopolymerization initiator with a fused polycyclic heterocyclic skeleton, the sensitivity during exposure can be improved, and residue adhesion at the openings of the pattern after thermosetting can be suppressed. This is presumably because UV curing is carried out efficiently using two or more (C1-1) oxime ester-based photopolymerization initiators, reducing the amount of unreacted (B) radical polymerizable compounds. Furthermore, it can be believed that the heat resistance of the fused polycyclic and heterocyclic skeletons suppresses degassing caused by the thermal decomposition of the photopolymerization initiator.

[0209] As photopolymerization initiators containing a fused polycyclic framework (C1-1a) and a fused polycyclic heterocyclic framework (C1-1b), respectively, these initiators possess structures in which at least one oxime ester structure or at least one oxime ester carbonyl structure is bonded to each of the fused polycyclic and heterocyclic frameworks. By having structures in which at least one oxime ester structure or at least one oxime ester carbonyl structure is bonded to each of the fused polycyclic and heterocyclic frameworks, the sensitivity during exposure can be improved, and a low-conical pattern can be formed after development. This is because the energy of the UV light absorbed by the fused polycyclic and heterocyclic frameworks during exposure is efficiently transferred, and the generation of free radicals caused by bond breaking and / or reactions of the oxime ester or oxime ester carbonyl structures proceeds efficiently. Furthermore, from the viewpoint of improved sensitivity during exposure and formation of a low-conical pattern after development, a structure having at least one oxime ester structure bonded to one or more of the fused polycyclic framework and the fused polycyclic heterocyclic framework is preferred. Furthermore, from the viewpoint of improved sensitivity during exposure, a structure having two or more oxime ester structures bonded to the fused polycyclic framework and the fused polycyclic heterocyclic framework, or a structure having two or more oxime ester carbonyl structures bonded to it, is also preferred. It should be noted that a substance having an oxime ester structure bonded to a fused polycyclic framework or a fused polycyclic heterocyclic framework is called an α-oxime. Furthermore, a substance having an oxime ester carbonyl structure bonded to a fused polycyclic framework or a fused polycyclic heterocyclic framework (i.e., a substance having an oxime ester structure bonded via a carbonyl structure) is called a β-oxime.

[0210] As photopolymerization initiators containing a fused polycyclic framework (C1-1a) and a fused polycyclic heterocyclic framework (C1-1b) as described above, from the viewpoints of improved sensitivity during exposure and formation of a low-conical-shape pattern after development, it is preferable to 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 framework or the fused polycyclic heterocyclic framework. The group represented by general formula (11) is a group having an oxime ester structure, and is a group having a structure that generates free radicals by bond breaking and / or reaction under UV light during exposure.

[0211]

[0212] In general formula (11), X 7 Indicates a directly bonded alkylene group with 1 to 10 carbon atoms, a cycloalkylene group with 4 to 10 carbon atoms, or an arylene group with 6 to 15 carbon atoms. R 29Represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an aryl group with 6 to 15 carbon atoms, an alkenyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, a haloalkoxy group with 1 to 10 carbon atoms, a heterocyclic group with 4 to 10 carbon atoms, a heterocyclic group with 4 to 10 carbon atoms, an acyl group with 2 to 10 carbon atoms, or a nitro group. R 30 It represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, or an aryl group with 6 to 15 carbon atoms. 'a' represents 0 or 1, and 'b' represents an integer from 1 to 10.

[0213] In general formula (11), considering the improvement in solubility in the solvent, X 7 Preferably, it is an alkylene group having 1 to 10 carbon atoms, or, from the viewpoint of improving sensitivity during exposure, preferably an aryl group having 6 to 15 carbon atoms. From the viewpoint of improving solubility in solvents, R... 29 Preferably, it is a cycloalkyl group with 4 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, or a haloalkoxy group with 1 to 10 carbon atoms. Furthermore, from the viewpoint of improved sensitivity during exposure and the formation of a low-cone pattern after development, R... 29 Preferably, it is an alkenyl group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, a haloalkoxy group with 1 to 10 carbon atoms, a heterocyclic group with 4 to 10 carbon atoms, a heterocyclic group with 4 to 10 carbon atoms, an acyl group with 2 to 10 carbon atoms, or a nitro group. From the viewpoint of improving sensitivity during exposure, R... 30 Preferably, it is an alkyl group having 1 to 10 hydrogen atoms or carbon atoms, more preferably an alkyl group having 1 to 4 hydrogen atoms or carbon atoms, and even more preferably a methyl group. From the viewpoint of improving sensitivity during exposure, a is preferably 0.

[0214] From the viewpoint of improving sensitivity during exposure, one or more photopolymerization initiators selected from (C1-1a) containing a fused polycyclic skeleton and (C1-1b) containing a fused polycyclic heterocyclic skeleton preferably have substituents comprising non-shared electron pairs that can be conjugated with the fused polycyclic skeleton or the fused polycyclic heterocyclic skeleton. Similarly, from the viewpoint of improving sensitivity during exposure, it is preferable to have substituents comprising π bonds that can be conjugated with the fused polycyclic skeleton or the fused polycyclic heterocyclic skeleton. Examples of substituents comprising non-shared electron pairs include halogen, amino, hydroxyl, alkoxy, or mercapto. Examples of substituents comprising π bonds include aryl, nitro, cyano, carboxyl, formyl, alkylcarbonyl, alkyloxycarbonyl, or sulfonyl. In addition, as substituents containing π bonds, examples include carbon atoms on fused polycyclic skeletons or carbon atoms on fused polycyclic heterocyclic skeletons that form unsaturated double bonds containing π bonds with nitrogen, oxygen, or sulfur atoms (dialkyl carbonyl, or dialkyl thiocarbonyl, etc.).

[0215] As a photopolymerization initiator containing a fused polycyclic framework (C1-1a), it has a fused polycyclic framework comprising an aromatic backbone, which is composed only of carbon and hydrogen atoms. Because the aforementioned photopolymerization initiator containing a fused polycyclic framework (C1-1a) has a fused polycyclic framework comprising an aromatic backbone, a low-cone pattern can be formed after development, and halftone properties can be improved. This is presumably because the photopolymerization initiator containing a fused polycyclic framework (C1-1a) is compatible with the entire film due to the aromatic backbone, allowing UV curing to proceed to the depths of the film during exposure. Furthermore, it can be considered that because the fused polycyclic framework is composed only of carbon and hydrogen atoms, it has low polarity and improved hydrophobicity, thus suppressing side etching during alkaline development.

[0216] As a photopolymerization initiator containing a fused polycyclic framework (C1-1a), the fused polycyclic framework preferably comprises one or more selected from fluorene, benzo[a]fluorene, dibenzo[a]fluorene, indene, indane, benzo[a]indene, benzo[a]indene, dihydroanthracene, dihydrobenzanthracene, dihydrophenanthrene, dihydrobenzanthracene, dihydronaphthalene, dihydrobenzonaphthalene, tetrahydronaphthalene, and tetrahydrobenzonaphthalene frameworks. More preferably, it comprises one or more selected from fluorene, benzo[a]fluorene, dibenzo[a]fluorene, indene, indane, benzo[a]indene, and benzo[a]indene frameworks. By having the above structure, a low-cone pattern can be formed after development, and halftone characteristics can be improved. Furthermore, residue adhesion at the openings of the pattern after thermosetting can be suppressed.

[0217] As a photopolymerization initiator (C1-1a) containing a fused polycyclic backbone, from the viewpoint of photobleaching properties, it is further preferred to have one or more backbones selected from fluorene, benzo[a]fluorene, and dibenzo[a]fluorene. Photobleaching properties refer to the reduction of absorbance in the ultraviolet-visible region due to bond breaking and / or reactions caused by UV light during exposure. By possessing photobleaching properties, the sensitivity during exposure can be improved, and a low-cone pattern can be formed after development. Furthermore, halftone characteristics can be improved. Furthermore, residue adhesion at the openings of the pattern after thermal curing can be suppressed. This is presumably because the absorbance of UV light decreases while free radicals are generated during exposure, thus allowing UV curing to proceed to the depth of the film.

[0218] In the negative photosensitive resin composition of the present invention, the content ratio of the photoinitiator containing a fused polycyclic skeleton (C1-1a) in the (C1) photoinitiator is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, further more preferably 17% by mass or more, and particularly preferably 20% by mass or more. If the content ratio is 5% by mass or more, the sensitivity during exposure can be improved, and a low-cone pattern can be formed after development. In addition, halftone characteristics can be improved. Furthermore, residue adhesion at the opening of the pattern after thermosetting can be suppressed. On the other hand, the content ratio of the photoinitiator containing a fused polycyclic skeleton (C1-1a) is preferably 45% by mass or less, more preferably 43% by mass or less, further preferably 40% by mass or less, further more preferably 38% by mass or less, and particularly preferably 35% by mass or less. If the content ratio is 45% by mass or less, the sensitivity during exposure can be improved, and a low-cone pattern can be formed after development. In addition, halftone characteristics can be improved. This can further suppress the adhesion of residue to the openings of the pattern after thermosetting.

[0219] As a photopolymerization initiator (C1-1b) containing a fused polycyclic heterocyclic framework, it is preferable to have a fused polycyclic heterocyclic framework comprising an aromatic framework, which contains at least carbon and hydrogen atoms, and further comprises one or more heteroatoms selected from oxygen, nitrogen, sulfur, fluorine, silicon, and phosphorus atoms. Because the photopolymerization initiator (C1-1b) containing a fused polycyclic heterocyclic framework has a fused polycyclic framework comprising an aromatic framework, a low-cone pattern can be formed after development, and halftone characteristics can be improved. This is presumably because the photopolymerization initiator (C1-1b) containing a fused polycyclic heterocyclic framework is compatible with the entire film through the aromatic framework, and UV curing occurs during exposure until the depth of the film. Furthermore, it can be argued that the fused polycyclic heterocyclic framework contains at least carbon and hydrogen atoms, and further includes one or more heteroatoms selected from oxygen, nitrogen, sulfur, fluorine, silicon, and phosphorus atoms, thereby improving compatibility with free radical polymerizable compounds and enabling efficient UV curing even when exposed to deep layers of the film.

[0220] As a photopolymerization initiator (C1-1b) containing a fused polycyclic heterocyclic skeleton, the fused polycyclic heterocyclic skeleton preferably has a skeleton selected from carbazole, dibenzofuran, dibenzothiophene, benzocarbazole, naphthobenzofuran, naphthobenzothiophene, indole, benzofuran, benzothiophene, dihydroindole, benzodihydrofuran, benzodihydrothiophene, benzoindole, naphthofuran, naphthothiophene, benzodihydroindole, naphthodihydrofuran, naphthodihydrothiophene, acridine, xanthon, thiophene, and benzoacridine skeletons. The structure comprises one or more of the following: benzo[a]xanthanene skeleton, benzo[a]thioxanthanene skeleton, quinoline skeleton, benzo[a]pyran skeleton, benzo[a]thioxan skeleton, benzo[a]quinoline skeleton, naph[a]pyran skeleton, naph[a]thioxan skeleton, dihydroquinoline skeleton, benzo[a]dihydropyran skeleton, benzo[a]dihydrothioxan skeleton, benzo[a]dihydroquinoline skeleton, naph[a]dihydropyran skeleton, and naph[a]dihydrothioxan skeleton. More preferably, it comprises one or more of the following: carbazole skeleton, benzo[a]carbazole skeleton, indole skeleton, dihydroindole skeleton, benzo[a]indole skeleton, and benzo[a]dihydroindole skeleton. Even more preferably, it comprises one or more of the following: benzo[a]carbazole skeleton, benzo[a]indole skeleton, and benzo[a]dihydroindole skeleton. By having the above structure, a low-cone pattern can be formed after development, and halftone characteristics can be improved. Furthermore, residue adhesion at the opening of the pattern after thermosetting can be suppressed.

[0221] In the negative photosensitive resin composition of the present invention, the content ratio of the photopolymerization initiator (C1-1b) containing a fused polycyclic heterocyclic backbone in the (C1) photopolymerization initiator is preferably 55% by mass or more, more preferably 57% by mass or more, further preferably 60% by mass or more, further more preferably 62% by mass or more, and particularly preferably 65% ​​by mass or more. If the content ratio is 55% by mass or more, the sensitivity during exposure can be improved, and a low-cone pattern can be formed after development. In addition, halftone characteristics can be improved. Furthermore, residue adhesion at the opening of the pattern after thermosetting can be suppressed. On the other hand, the content ratio of the photopolymerization initiator (C1-1b) containing a fused polycyclic heterocyclic backbone is preferably 95% by mass or less, more preferably 90% by mass or less, further preferably 85% by mass or less, further more preferably 83% by mass or less, and particularly preferably 80% by mass or less. If the content ratio is 95% by mass or less, the sensitivity during exposure can be improved, and a low-cone pattern can be formed after development. In addition, halftone characteristics can be improved. This can further suppress the adhesion of residue to the openings of the pattern after thermosetting.

[0222] The photopolymerization initiator selected from (C1-1a) containing a fused polycyclic skeleton and the photopolymerization initiator selected from (C1-1b) containing a fused polycyclic heterocyclic skeleton preferably has one or more structures selected from nitro, naphthyl carbonyl, trimethylbenzoyl, thiophene carbonyl, and furanyl carbonyl. By having one or more structures selected from nitro, naphthyl carbonyl, trimethylbenzoyl, thiophene carbonyl, and furanyl carbonyl, the sensitivity during exposure can be improved, and a low-cone pattern can be formed after development. In addition, halftone properties can be improved. This is presumably because the conjugated structure introduced by the above structure allows for efficient absorption of UV light during exposure, and UV curing proceeds to the depth of the film. In particular, when the colorant (D) described later contains a black pigment (D1a), sometimes the UV light during exposure is blocked, resulting in insufficient curing; therefore, the above structure is particularly preferred to promote UV curing. Furthermore, from the viewpoints of improved sensitivity during exposure, formation of a low-cone pattern after development, and improved halftone properties, one or more of the photopolymerization initiators selected from (C1-1a) containing a fused polycyclic skeleton and (C1-1b) containing a fused polycyclic heterocyclic skeleton preferably have one or more structures selected from nitro, naphthyl carbonyl, trimethylbenzoyl, thiophene carbonyl, and furanyl carbonyl structures bonded to the fused polycyclic skeleton and the fused polycyclic heterocyclic skeleton.

[0223] From the viewpoints of improved sensitivity during exposure, formation of a low-cone pattern after development, and improved halftone properties, one or more photopolymerization initiators selected from (C1-1a) containing a fused polycyclic skeleton and (C1-1b) containing a fused polycyclic heterocyclic skeleton preferably have halogen-substituted groups. Furthermore, solubility in solvents can be improved. Fluorine is preferred as the halogen. This is because, by having halogen-substituted groups, the photopolymerization initiator becomes compatible with the entire film, allowing UV curing to proceed to the depths of the film during exposure. Furthermore, this is because the first resin selected from (A1-1) polyimide, (A1-2) polyimide precursor, and (A1-3) polybenzo[a]pyrene, as described above, is preferred. azole, and (A1-4) polybenzo[ When one or more structural units containing fluorine atoms are present in the azole precursor, the compatibility between the alkali-soluble resin and the photopolymerization initiator can be further improved, and UV curing can be carried out efficiently even when exposed to deep layers of the film. Examples of halogen-substituted groups include, for example, fluoromethyl, fluoroethyl, chloroethyl, bromoethyl, iodoethyl, trifluoromethyl, trifluoropropyl, trichloropropyl, tetrafluoropropyl, trifluoropentyl, tetrafluoropentyl, pentafluoropentyl, heptafluoropentyl, heptafluorodecyl, fluorocyclopentyl, tetrafluorocyclopentyl, fluorophenyl, pentafluorophenyl, trifluoromethoxy, trifluoropropoxy, tetrafluoropropoxy, trifluoropentyloxy, pentafluoropentyloxy, tetrafluorocyclopentyloxy, or pentafluorophenoxy.

[0224] From the viewpoints of improved sensitivity during exposure, formation of a low-cone pattern after development, and improved halftone properties, one or more of the photopolymerization initiators selected from (C1-1a) containing a fused polycyclic skeleton and (C1-1b) containing a fused polycyclic heterocyclic skeleton preferably have an alkenyl group, and more preferably, the photopolymerization initiator (C1-1a) containing a fused polycyclic skeleton has an alkenyl group. This can be considered because by having an alkenyl group, the compatibility of alkali-soluble resins and / or free radical polymerizable compounds with the photopolymerization initiator can be further improved, and UV curing can be carried out efficiently even when exposed to deep layers of the film. In particular, when the colorant (D) described later contains a black pigment (D1a), sometimes the UV light during exposure is blocked, resulting in insufficient curing; therefore, the structure described above is particularly preferred to promote UV curing. Furthermore, from the viewpoints of improved sensitivity during exposure, formation of a low-cone pattern after development, and improved halftone properties, one or more of the photopolymerization initiators selected from (C1-1a) containing a fused polycyclic framework and (C1-1b) containing a fused polycyclic heterocyclic framework preferably have a structure in which at least one alkenyl group having 1 to 5 carbon atoms is bonded to the fused polycyclic framework and the fused polycyclic heterocyclic framework. More preferably, the photopolymerization initiator in (C1-1a) containing a fused polycyclic framework has a structure in which at least one alkenyl group having 1 to 5 carbon atoms is bonded to the fused polycyclic framework.

[0225] Examples of alkenyl groups include, for example, vinyl, 1-methylvinyl, 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, acryloyl, or methacryloyl. Examples of alkenyl groups having 1 to 5 carbon atoms include, for example, vinyl, 1-methylvinyl, 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, acryloyl, or methacryloyl.

[0226] From the viewpoints of improved sensitivity during exposure, formation of a low-cone pattern after development, improved halftone characteristics, and suppression of residue adhesion after thermosetting, one or more of the photopolymerization initiators selected from (C1-1a) containing a fused polycyclic framework and (C1-1b) containing a fused polycyclic heterocyclic framework preferably contain one or more of the compounds shown in general formula (12) and general formula (13), and more preferably contain the compound shown in general formula (13). It should be noted that, as the photopolymerization initiator containing a fused polycyclic framework in (C1-1a), in general formulas (12) and (13), Y... 1 and Y 2 It is carbon. Furthermore, as the above-mentioned (C1-1b) photopolymerization initiator containing a fused polycyclic heterocyclic framework, in general formulas (12) and (13), Y 1 and Y 2 Each can be used independently to represent nitrogen, oxygen, or sulfur.

[0227]

[0228] In general formulas (12) and (13), X 1 X 2 X 4 and X 5 Each can be independently represented as a directly bonded alkylene group with 1 to 10 carbon atoms, a cycloalkylene group with 4 to 10 carbon atoms, or an arylene group with 6 to 15 carbon atoms. 1 and Y 2 Each can be independently represented as a carbon atom, nitrogen atom, oxygen atom, or sulfur atom. R 31 ~R 34 Each of these can be independently represented as 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. R 37 and R 38 Each group independently represents the group represented by general formula (15), general formula (16), general formula (17), general formula (18), or nitro group. 40 ~R 43 Each of the following groups 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. R 46 and R 47Each of the following can independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an aryl group with 6 to 15 carbon atoms, an alkenyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, a haloalkoxy group with 1 to 10 carbon atoms, or an acyl group with 2 to 15 carbon atoms. 49 and R 50 Each of the following can independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an aryl group with 6 to 15 carbon atoms, an alkenyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, a haloalkoxy group with 1 to 10 carbon atoms, a heterocyclic group with 4 to 10 carbon atoms, a heterocyclic group with 4 to 10 carbon atoms, an acyl group with 2 to 10 carbon atoms, or a nitro group. R 52 and R 53 Each can independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, or an aryl group with 6 to 15 carbon atoms. 'a' represents an integer from 0 to 3, 'b' represents 0 or 1, 'c' represents an integer from 0 to 5, and 'd' represents 0 or 1. In Y 1 and Y 2 If each is an independent carbon atom, then g and h are each independently 2. In Y... 1 and Y 2 When each is an independent nitrogen atom, g and h are each independently 1. In Y... 1 and Y 2 When each is an oxygen atom or a sulfur atom, g and h are each independently 0. j and k each independently represent 0 or 1, m and n each independently represent integers from 1 to 10. p and q each independently represent integers from 1 to 4, and x and y each independently represent integers from 1 to 4.

[0229] From the viewpoint of improved solubility in solvents, in general formulas (12) and (13), X 1 X 2 X 4 and X 5 Each is preferably an alkylene group having 1 to 10 carbon atoms. Furthermore, from the viewpoint of improving sensitivity during exposure, X... 1 X 2 X 4 and X 5 Each is preferably an aryl group with 6 to 15 carbon atoms. From the viewpoint of improving sensitivity during exposure, Y... 1 and Y 2 Each atom is preferably either a carbon atom or a nitrogen atom. As in R 40 ~R 43The rings formed in the form of carbon atoms, having 4 to 10 carbon atoms, can be exemplified by, for example, benzene rings or cyclohexane rings. From the viewpoint of improved solubility in solvents, R... 46 and R 47 Each of the following is 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. Furthermore, from the viewpoints of improved sensitivity during exposure, formation of a low-cone pattern after development, and improved halftone characteristics, R... 46 and R 47 Each of the following 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, or an acyl group having 2 to 10 carbon atoms. From the viewpoint of improved solubility in solvents, R... 49 and R 50 Each of the following 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. Furthermore, from the viewpoints of improved sensitivity during exposure, formation of a low-cone pattern after development, and improved halftone characteristics, R... 49 and R 50 Each group is preferably an alkenyl group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, a haloalkoxy group with 1 to 10 carbon atoms, a heterocyclic group with 4 to 10 carbon atoms, a heterocyclic group with 4 to 10 carbon atoms, an acyl group with 2 to 10 carbon atoms, or a nitro group. From the viewpoint of improving sensitivity during exposure, R... 52 and R 53 Each of the components is preferably an alkyl group having 1 to 10 hydrogen atoms or carbon atoms, more preferably an alkyl group having 1 to 4 hydrogen atoms or carbon atoms, and even more preferably a methyl group. From the viewpoint of improving sensitivity during exposure, j and k are each preferably 0.

[0230]

[0231] In general formulas (15) to (18), R 55 ~R 58 Each of these groups 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. As a group consisting of multiple R groups... 55 ~R 58 The formed ring can be, for example, a benzene ring, a naphthalene ring, anthracene ring, a cyclopentane ring, or a cyclohexane ring. a is an integer from 0 to 7, b is an integer from 0 to 2, and c and d are each independently an integer from 0 to 3. As a group of multiple R... 55 ~R 58 The formed ring is preferably a benzene ring or a naphthalene ring.

[0232] Examples of photopolymerization initiators containing a fused polycyclic framework (C1-1a) include compounds with the structures shown below.

[0233]

[0234]

[0235] Examples of photopolymerization initiators containing a fused polycyclic heterocyclic skeleton (C1-1b) include compounds with the structures shown below.

[0236]

[0237]

[0238]

[0239]

[0240] Photopolymerization initiators containing a fused polycyclic skeleton (C1-1a) and a fused polycyclic heterocyclic skeleton (C1-1b) can be synthesized by known methods. Examples of such synthesis methods include those described in Japanese Patent Application Publication No. 2013-190459, Japanese Patent Application Publication No. 2016-191905, and International Patent Publication No. 2014 / 500852.

[0241] The maximum absorption wavelength, selected from one or more photopolymerization initiators containing a fused polycyclic framework (C1-1a) and a fused polycyclic heterocyclic framework (C1-1b), is preferably 330 nm or more, more preferably 340 nm or more, and even more preferably 350 nm or more. If the maximum absorption wavelength is 330 nm or more, the sensitivity during exposure can be improved, and a low-cone pattern can be formed after development. In addition, halftone characteristics can be improved. On the other hand, the maximum absorption wavelength of the specific oxime ester photopolymerization initiator (C1-1) is preferably 410 nm or less, more preferably 400 nm or less, even more preferably 390 nm or less, and particularly preferably 380 nm or less. If the maximum absorption wavelength is 410 nm or less, the sensitivity during exposure can be improved, and a low-cone pattern can be formed after development. In addition, halftone characteristics can be improved. It should be noted that the maximum absorption wavelength refers to the wavelength in the absorption spectrum exhibiting maximum absorption in the wavelength range of 300 to 800 nm.

[0242] The absorbance at 360 nm in a 0.01 g / L propylene glycol monomethyl ether acetate solution, selected from one or more photopolymerization initiators selected from (C1-1a) containing a fused polycyclic framework and (C1-1b) containing a fused polycyclic heterocyclic framework, is preferably 0.20 or more, more preferably 0.25 or more, further preferably 0.30 or more, more preferably 0.35 or more, particularly preferably 0.40 or more, and most preferably 0.45 or more. If the absorbance is 0.20 or more, the sensitivity during exposure can be improved, and a low-conical pattern can be formed after development. In addition, the change in the pattern opening size width before and after thermosetting can be suppressed, and the halftone characteristics can be improved. On the other hand, the absorbance at 360 nm in a 0.01 g / L propylene glycol monomethyl ether acetate solution, of the specific (C1-1) oxime ester photopolymerization initiator, is preferably 1.00 or less. If the absorbance is below 1.00, the formation of residue after development can be suppressed, and the resolution after development can be improved.

[0243] The total content of the photoinitiator containing a fused polycyclic skeleton (C1-1a) and the photoinitiator containing a fused polycyclic heterocyclic skeleton (C1-1b) in the negative photosensitive resin composition of the present invention, when the total amount of (A) alkali-soluble resin and (B) free radical polymerizable compound is set to 100 parts by mass, is preferably 0.5 parts by mass or more, more preferably 3 parts by mass or more, further preferably 5 parts by mass or more, further more preferably 7 parts by mass or more, and particularly preferably 10 parts by mass or more. If the total content is 0.5 parts by mass or more, the sensitivity during exposure can be improved, and a low-cone pattern can be formed after development. In addition, halftone characteristics can be improved. Furthermore, residue adhesion at the opening of the pattern after thermosetting can be suppressed. On the other hand, the total content of the photopolymerization initiator containing a fused polycyclic framework (C1-1a) and the photopolymerization initiator containing a fused polycyclic heterocyclic framework (C1-1b) 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. If the content is 30 parts by mass or less, the resolution after development can be improved, and a low-cone pattern can be formed after development. In addition, halftone characteristics can be improved.

[0244] <(C1-1c) Oxime ester photopolymerization initiators containing a diphenyl sulfide skeleton, (C1-2) α-amino ketone photopolymerization initiators, (C1-3) α-hydroxy ketone photopolymerization initiators, (C1-4) phosphine oxide photopolymerization initiators, and (C1-5) biimidazole photopolymerization initiators>

[0245] The negative photosensitive resin composition of the present invention preferably further contains one or more of the following as a (C1) photopolymerization initiator: (C1-1c) oxime ester photopolymerization initiator containing a diphenyl sulfide skeleton, (C1-2) α-amino ketone photopolymerization initiator, (C1-3) α-hydroxy ketone photopolymerization initiator, (C1-4) phosphine oxide photopolymerization initiator, and (C1-5) biimidazole photopolymerization initiator. An (C1-1c) oxime ester photopolymerization initiator containing a diphenyl sulfide skeleton refers to a compound having a diphenyl sulfide skeleton in its molecule, and having an oxime ester skeleton as the skeleton for generating free radicals through bond cleavage and / or reaction upon exposure. An (C1-2) α-amino ketone photopolymerization initiator refers to a compound having an α-amino ketone skeleton in its molecule, and generating free radicals through bond cleavage and / or reaction upon exposure. The term "(C1-3) α-hydroxyketone photopolymerization initiator" refers to a compound whose molecule contains an α-hydroxyketone skeleton and generates free radicals through bond cleavage and / or reaction upon exposure. Similarly, "(C1-4) phosphine oxide photopolymerization initiator" refers to a compound whose molecule contains a phosphine oxide skeleton and generates free radicals through bond cleavage and / or reaction upon exposure. Finally, "(C1-5) biimidazole photopolymerization initiator" refers to a compound whose molecule contains a biimidazole skeleton and generates free radicals through bond cleavage and / or reaction upon exposure.

[0246] By using one or more photoinitiators selected from (C1-1c) oxime esters containing a diphenyl sulfide skeleton, (C1-2) α-aminoketones, (C1-3) α-hydroxyketones, (C1-4) phosphine oxides, and (C1-5) biimidazoles, the sensitivity during exposure can be improved, resulting in a low-cone pattern after development. The presumed reason is that these photoinitiators have different main skeleton structures or maximum absorption wavelengths compared to the photoinitiators (C1-1a) and (C1-1b) containing fused polycyclic heterocyclic skeletons, thus supplementing the absorption of UV light during exposure, thereby enabling more efficient free radical curing.

[0247] From the viewpoints of improved sensitivity during exposure, formation of low-cone pattern after development, and improved halftone properties, (C1-1c) oxime ester photopolymerization initiators containing a diphenyl sulfide skeleton preferably contain compounds represented by general formula (14).

[0248]

[0249] In general formula (14), X 6Indicates a directly bonded alkylene group with 1 to 10 carbon atoms, a cycloalkylene group with 4 to 10 carbon atoms, or an arylene group with 6 to 15 carbon atoms. R 35 and R 36 Each of these can be independently represented as 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. R 39 Represents the group shown in general formula (15), the group shown in general formula (16), the group shown in general formula (17), the group shown in general formula (18), or a nitro group. 44 R 45 R 59 and R 60 Each of the following groups 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. R 51 Represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an aryl group with 6 to 15 carbon atoms, an alkenyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, a haloalkoxy group with 1 to 10 carbon atoms, a heterocyclic group with 4 to 10 carbon atoms, a heterocyclic group with 4 to 10 carbon atoms, an acyl group with 2 to 10 carbon atoms, or a nitro group. R 54 This represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, or an aryl group with 6 to 15 carbon atoms. e represents an integer from 0 to 4, f represents an integer from 0 to 2. l represents 0 or 1, o represents an integer from 1 to 10. r represents an integer from 1 to 4, z represents an integer from 1 to 4.

[0250] In general formula (14), considering the improvement in solubility in the solvent, X 6 Preferably, it is an alkylene group having 1 to 10 carbon atoms. Furthermore, from the viewpoint of improving sensitivity during exposure, X... 6 Preferably, it is an arylene group having 6 to 15 carbon atoms. As in R 44 R 45 R 59 and R 60 The rings formed in the form of carbon atoms, having 4 to 10 carbon atoms, can be exemplified by, for example, benzene rings or cyclohexane rings. From the viewpoint of improved solubility in solvents, R... 51 Preferably, it is a cycloalkyl group with 4 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, or a haloalkoxy group with 1 to 10 carbon atoms. Furthermore, from the viewpoints of improved sensitivity during exposure, formation of a low-cone pattern after development, and improved halftone characteristics, R... 51Each group is preferably an alkenyl group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, a haloalkoxy group with 1 to 10 carbon atoms, a heterocyclic group with 4 to 10 carbon atoms, a heterocyclic group with 4 to 10 carbon atoms, an acyl group with 2 to 10 carbon atoms, or a nitro group. From the viewpoint of improving sensitivity during exposure, R... 54 Preferably, it is an alkyl group having 1 to 10 hydrogen atoms or carbon atoms, more preferably an alkyl group having 1 to 4 hydrogen atoms or carbon atoms, and even more preferably a methyl group. From the viewpoint of improving sensitivity during exposure, l is preferably 0.

[0251] Examples of (C1-1c) oxime ester photopolymerization initiators containing a diphenyl sulfide skeleton include compounds with the structures shown below.

[0252]

[0253] Examples of (C1-2)α-aminoketone photopolymerization initiators include, for example, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)-butane-1-one, or 3,6-bis(2-methyl-2-morpholinopropionyl)-9-octyl-9H-carbazole.

[0254] Examples of (C1-3)α-hydroxyketone photopolymerization initiators include, for example, 2-hydroxy-1-[4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl]-2-methylpropane-1-one, 2-hydroxy-1-[4-[4-(2-hydroxy-2-methylpropionyl)phenoxy]phenyl]-2-methylpropane-1-one, 2-hydroxy-1-[4-[5-(2-hydroxy-2-methylpropionyl)-1,3,3-trimethyl-2,3-dihydro-indene-1-yl]phenyl]-2-methylpropane-1-one, or oligomeric [2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1-one].

[0255] Examples of (C1-4)phosphine oxide photopolymerization initiators include, for example, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, or bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide.

[0256] Examples of (C1-5) biimidazole-based photopolymerization initiators include, for example, 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, or 2,2'-bis(2-methoxyphenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.

[0257] In the negative photosensitive resin composition of the present invention, the total content of (C1-1c) an oxime ester photoinitiator containing a diphenyl sulfide skeleton, (C1-2) an α-aminoketone photoinitiator, (C1-3) an α-hydroxyketone photoinitiator, (C1-4) a phosphine oxide photoinitiator, and (C1-5) a biimidazole photoinitiator in the (C1) photoinitiator is preferably 5% by mass or more, more preferably 7% by mass or more, further preferably 10% by mass or more, further more preferably 12% by mass or more, and particularly preferably 15% by mass or more. If the content is 5% by mass or more, the sensitivity during exposure can be improved, and a low-cone pattern can be formed after development. On the other hand, the total content of (C1-1c) an oxime ester photoinitiator containing a diphenyl sulfide skeleton, (C1-2) an α-amino ketone photoinitiator, (C1-3) an α-hydroxy ketone photoinitiator, (C1-4) a phosphine oxide photoinitiator, and (C1-5) a biimidazole photoinitiator 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. If the content is 35% by mass or less, the sensitivity during exposure can be improved, and a low-cone pattern can be formed after development.

[0258] <(C2) Photoacid Generator>

[0259] The negative photosensitive resin composition of the present invention preferably further contains a (C2) photoacid generator as a (C) photosensitizer. By containing the (C2) photoacid generator, UV curing during exposure is promoted, thus improving the sensitivity during exposure. Furthermore, the increased crosslinking density after thermosetting improves chemical resistance. As an ionic compound, the (C2) photoacid generator is preferably a triorganosulfonium salt compound. Examples of nonionic (C2) photoacid generators include, for example, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate compounds, carboxylic acid ester compounds, sulfonylimide compounds, phosphate ester compounds, or sulfonebenzotriazole compounds. The content of the (C2) photoacid generator in the negative photosensitive resin composition of the present invention is preferably 0.1 parts by mass or more, provided that the total amount of (A) alkali-soluble resin and (B) free radical polymerizable compound is 100 parts by mass. On the other hand, the content of the (C2) photoacid generator is preferably 25 parts by mass or less.

[0260] In the negative photosensitive resin composition of the present invention, from the viewpoint that the effects of improved sensitivity during exposure, low-cone pattern formation after development, improved halftone characteristics, and suppression of residue adhesion at the pattern openings after thermosetting become significant, when the photopolymerization initiator containing a fused polycyclic skeleton in (C1-1a) and the photopolymerization initiator containing a fused polycyclic heterocyclic skeleton in (C1-1b) have one or more structures selected from nitro, naphthyl carbonyl, trimethylbenzoyl, thiophene carbonyl, and furanyl carbonyl, the content ratio of the photopolymerization initiator containing a fused polycyclic skeleton in (C1) is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, further more preferably 17% by mass or more, and particularly preferably 20% by mass or more.

[0261] On the other hand, in the negative photosensitive resin composition of the present invention, from the viewpoints of improved sensitivity during exposure, formation of a low-cone pattern after development, improved halftone characteristics, and suppression of residue adhesion at the pattern openings after thermosetting, when the photopolymerization initiator containing a fused polycyclic skeleton in (C1-1a) and the photopolymerization initiator containing a fused polycyclic heterocyclic skeleton in (C1-1b) have one or more structures selected from nitro, naphthyl carbonyl, trimethylbenzoyl, thiophene carbonyl, and furanyl carbonyl, the content ratio of the photopolymerization initiator containing a fused polycyclic skeleton in (C1) is preferably 45% by mass or less, more preferably 43% by mass or less, further preferably 40% by mass or less, further more preferably 38% by mass or less, and particularly preferably 35% by mass or less.

[0262] Furthermore, in the negative photosensitive resin composition of the present invention, from the viewpoint that the effects of improved sensitivity during exposure, low-cone pattern formation after development, improved halftone characteristics, and suppression of residue adhesion at the pattern openings after thermosetting become significant, when the photopolymerization initiator containing a fused polycyclic skeleton in (C1-1a) and the photopolymerization initiator containing a fused polycyclic heterocyclic skeleton in (C1-1b) have one or more structures selected from nitro, naphthyl carbonyl, trimethylbenzoyl, thiophene carbonyl, and furanyl carbonyl, and in the photopolymerization initiator containing a fused polycyclic heterocyclic skeleton in (C1-1b), as the fused polycyclic heterocyclic skeleton, it is more preferable to have one or more structures selected from carbazole skeleton, benzo[carbazole] skeleton, indole skeleton, dihydroindole skeleton, benzo[indole] skeleton, and benzo[dihydroindole] skeleton, and even more preferably to have one or more structures selected from benzo[carbazole] skeleton, benzo[indole] skeleton, and benzo[dihydroindole] skeleton.

[0263] Similarly, in the negative photosensitive resin composition of the present invention, from the viewpoint that the effects of improved sensitivity during exposure, low-cone pattern formation after development, improved halftone characteristics, and suppression of residue adhesion at the pattern openings after thermosetting become significant, in the case where the photopolymerization initiator containing a fused polycyclic skeleton in (C1-1a) has one or more selected from fluorene skeleton, benzo[a]fluorene skeleton, dibenzo[a]fluorene skeleton, indene skeleton, indane skeleton, benzo[a]indene skeleton, and benzo[a]indane skeleton as the fused polycyclic skeleton, in the case where the photopolymerization initiator containing a fused polycyclic heterocyclic skeleton in (C1-1b) has one or more selected from carbazole skeleton, benzo[a]carbazole skeleton, indole skeleton, dihydroindole skeleton, benzo[a]indole skeleton, and benzo[a]dihydroindole skeleton as the fused polycyclic heterocyclic skeleton, more preferably has one or more selected from carbazole skeleton, benzo[a]indole skeleton, and benzo[a]dihydroindole skeleton, and even more preferably has one or more selected from benzo[a]carbazole skeleton, benzo[a]indole skeleton, and benzo[a]dihydroindole skeleton.

[0264] <<(D) colorant, (Da) black agent, and (Db) colorant other than black>>

[0265] As the negative photosensitive resin composition of the present invention, it is preferable to further contain a (D) colorant. A (D) colorant is a compound that absorbs light of a specific wavelength, particularly a compound that colors light by absorbing wavelengths of visible light (380–780 nm). By containing a (D) colorant, light transmitted through the film of the resin composition, or light reflected from the 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. In addition, a (Da) black agent is always present, and furthermore, a (Db) colorant other than black may be contained.

[0266] As a (D) colorant, (D1) pigments and (D2) dyes can be used, especially when light-shielding properties are required for visible light. As the negative photosensitive resin composition of the present invention, it is preferable to contain a (Da) black agent. A (Da) black agent refers to a compound that colors itself black by absorbing light of the wavelength of visible light. By containing a (Da) black agent, the film of the resin composition is blackened, thereby improving the light-shielding properties of the resin composition film and enhancing the reliability of the light-emitting element. Therefore, it is suitable for applications such as pixel dividing layers, electrode insulating layers, wiring insulating layers, TFT planarization layers, electrode planarization layers, wiring planarization layers, TFT protective layers, electrode protective layers, wiring protective layers, interlayer insulating layers, gate insulating layers, color filters, black matrices, or black columnar spacers. It is particularly suitable for applications requiring high contrast through suppression of external light reflection, and is preferred as a light-shielding pixel dividing layer, TFT planarization layer, TFT protective layer, interlayer insulating layer, or gate insulating layer for organic EL displays.

[0267] (D) The term "black" in colorant refers to a color containing "BLACK" in the Colour Index Generic Name (hereinafter, "CI number"). When a color without a CI number is present, it refers to a color that is black when the film is cured. "Black" in the context of a cured film means that, in the transmission spectrum of the cured film of the resin composition containing (D) colorant, when the transmittance per 1.0 μm film thickness at 550 nm is converted using the Lambert-Beer formula, with the transmittance at 550 nm being 10%, and the film thickness is within the range of 0.1–1.5 μm, the transmittance at wavelengths of 450–650 nm is 25% or less.

[0268] 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 such that the (D) colorant accounts for 35% by mass of the total solid components of the resin composition. After coating the resin composition onto a Tenpace glass substrate (manufactured by AGC Technograss Co., Ltd.), a pre-baked film is obtained by pre-baking at 110°C for 2 minutes. Next, a cured film with a thickness of 1.0 μm containing the (D) colorant is prepared by heat curing at 250°C for 60 minutes under a nitrogen atmosphere using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Service System Co., Ltd.). Furthermore, a resin composition containing the aforementioned adhesive resin but without (D) colorant was prepared, and a cured film (hereinafter, "blank cured film") with a film thickness of 1.0 μm was produced by coating, pre-baking, and thermal curing on a tampax glass substrate using the same method as described above. Using a UV-Vis spectrophotometer (MultiSpec-1500; manufactured by Shimadzu Corporation), the UV-Vis absorption spectrum of the tampax glass substrate with the blank cured film formed at a thickness of 1.0 μm was first measured, and this UV-Vis absorption spectrum was set as the blank. Next, the tampax glass substrate with the prepared colorant-containing cured film was measured using a single beam, and the transmittance per 1.0 μm film thickness at wavelengths of 450–650 nm was determined. The transmittance of the colorant-containing cured film was calculated from the difference between the transmittance and the blank.

[0269] From the viewpoints of improved sensitivity during exposure, formation of a low-cone pattern after development, and improved halftone characteristics, the maximum transmission wavelength of the (Da) black agent is preferably 330 nm or more, and more preferably 340 nm or more. On the other hand, from the viewpoints of improved sensitivity during exposure, formation of a low-cone pattern after development, and improved halftone characteristics, the maximum transmission wavelength of the (Da) black agent is preferably 410 nm or less, and more preferably 390 nm or less. Furthermore, as described above, when the maximum transmission wavelength of the (Da) black agent is 330–410 nm, the maximum absorption wavelength of the aforementioned (C1-1) specific oxime ester photopolymerization initiator is preferably 330–410 nm. It should be noted that the maximum transmission wavelength refers to the wavelength in the transmission spectrum that exhibits maximum transmission within the wavelength range of 300–800 nm. (D) The maximum transmission wavelength in the colorant can be determined by measuring the transmittance of the cured film at wavelengths of 300 to 800 nm per 1.0 μm film thickness, in the same way as the method for measuring the transmittance of the cured film described above.

[0270] From the viewpoints of improved light-shielding properties and increased reliability of the light-emitting element, the content of colorant (D) in all solid components 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. On the other hand, from the viewpoints of improved sensitivity during exposure, formation of a low-cone pattern after development, and increased reliability of the light-emitting element, the content of colorant (D) is preferably 70% by mass or less, more preferably 55% by mass or less.

[0271] In the negative photosensitive resin composition of the present invention, the preferred content ratio of the (Da) black agent is as described above for the preferred content ratio of the (D) colorant. If the content ratio of the (Da) black agent is within the above range, the reliability of the light-emitting element can be particularly improved.

[0272] <(D1) Pigment, and (D2) Dye>

[0273] As the negative photosensitive resin composition of the present invention, the aforementioned (D) colorant preferably contains a (D1) pigment. In the embodiment where the aforementioned (D) colorant contains a (D1) pigment, it must contain the aforementioned (Da) black agent, and optionally may contain a (Db) colorant other than black. The term (D1) pigment refers to a compound that colors an object by physically adsorbing onto the surface of the object or interacting with the surface of the object, and is generally insoluble in solvents. By containing a (D1) pigment, a color with excellent opacity can be achieved, and the opacity and weather resistance of the resin composition film can be improved. Examples of (D1) pigments include, for example, organic or inorganic pigments.

[0274] From the viewpoint of suppressing residue after development and improving the storage stability of the coating solution, the number-average particle size of the (D1) pigment is preferably 10 nm or more, and more preferably 30 nm or more. On the other hand, from the viewpoint of improving sensitivity during exposure and forming a low-conical pattern after development, the number-average particle size of the (D1) pigment is preferably 500 nm or less, and more preferably 300 nm or less. Here, the number-average particle size of the (D1) pigment can be determined by measuring the laser scattering (dynamic light scattering method) of the (D1) pigment in the solution caused by Brownian motion using a submicron particle size distribution measuring device (N4-PLUS; manufactured by Beckman Coulter) or a zeta potential / particle size / molecular weight measuring device (Zeta Siasana No ZS; manufactured by Sismex Co.). Furthermore, the number-average particle size of the (D1) pigment in the cured film obtained from the resin composition can be determined using a scanning electron microscope (hereinafter, "SEM") and a transmission electron microscope (hereinafter, "TEM"). The number-average particle size of the (D1) pigment is directly measured at a magnification of 50,000 to 200,000. If the (D1) pigment is spherical, the diameter of the sphere is measured and set as the number-average particle size. If the (D1) pigment is not spherical, the longest diameter (hereinafter, "major axis diameter") and the longest diameter in the direction orthogonal to the major axis diameter (hereinafter, "minor axis diameter") are measured, and the biaxial average diameter obtained by averaging the major axis diameter and the minor axis diameter is set as the number-average particle size.

[0275] The preferred content ratio of the pigment (D1) in all solid components of the negative photosensitive resin composition of the present invention, excluding the solvent, is as described in the preferred content ratio of the colorant (D) above. If the content ratio of the pigment (D1) is within the above range, then, in particular, a low-cone pattern can be formed after development.

[0276] (D2) dyes refer to compounds that color an object through chemical adsorption onto its surface structure, and are generally soluble in solvents. Furthermore, (D2) dyes exhibit high tinting strength and high color development efficiency because each molecule adsorbs onto the object individually. Examples of (D2) dyes include anthraquinone dyes, azo dyes, azine dyes, phthalocyanine dyes, and methylene dyes. Azide dyes, quinoline dyes, indigo dyes, indigo-based dyes, carbon dyes Dyes of various types, including terpenoid dyes, vat dyes, violet ketone dyes, perylene dyes, triarylmethane dyes, or thallium dyes.

[0277] <(D1a) Black pigment, and (D1b) pigments other than black>

[0278] As the negative photosensitive resin composition of the present invention, the (D1) pigment preferably contains a (D1a) black pigment, or a (D1a) black pigment and a (D1b) pigment other than black. The (D1a) black pigment refers to a pigment that colors itself black by absorbing light of visible wavelengths. By containing a (D1a) black pigment, the light-shielding properties of the resin composition film can be improved, and the reliability of the light-emitting element can be enhanced. As the negative photosensitive resin composition of the present invention, the (Da) black agent is preferably a (D1a) black pigment, and the (D1a) black pigment is selected from one or more of the following: (D1a-1) black organic pigment, (D1a-2) black inorganic pigment, and (D1a-3) mixtures of two or more colored pigments.

[0279] As the negative photosensitive resin composition of the present invention, when the (D1a) black pigment is selected from one or more of the (D1a-1) black organic pigment and (D1a-2) black inorganic pigment described later, it may further contain a pigment other than black (D1b). The pigment other than black (D1b) refers to a pigment that colors by absorbing light of a wavelength visible to the naked eye. By containing a pigment other than black (D1b), the film of the resin composition can be imparted with tinting properties. By combining two or more pigments, tinting can be performed to adjust the film of the resin composition to a desired color coordinate. As the negative photosensitive resin composition of the present invention, the pigment other than black (D1b) is preferably selected from one or more of the blue, red, yellow, purple, orange, and green pigments described later.

[0280] In the negative photosensitive resin composition of the present invention, the preferred content ratio of the (D1a) black pigment is as described above for the preferred content ratio of the (D) colorant. If the content ratio of the (D1a) black pigment is within the above-described range, the reliability of the light-emitting element can be improved, in particular.

[0281] <(D1a-1) Black organic pigment, (D1a-2) Black inorganic pigment, and (D1a-3) Mixture of two or more coloring pigments>

[0282] As the negative photosensitive resin composition of the present invention, the aforementioned (D1a) black pigment is preferably selected from one or more of (D1a-1) black organic pigment, (D1a-2) black inorganic pigment, and (D1a-3) two or more colored pigment mixtures. From the viewpoint of improving the reliability of the light-emitting element, (D1a-1) black organic pigment and / or (D1a-3) two or more colored pigment mixtures are more preferred. From the viewpoint of improving the sensitivity during exposure, (D1a-1) black organic pigment is even more preferred. The (D1a-1) black organic pigment refers to an organic pigment that is colored black by absorbing light of visible wavelengths. By containing the (D1a) black pigment, the light-shielding property of the resin composition film can be improved, and the reliability of the light-emitting element can be improved. Compared with general inorganic pigments, the (D1a-1) black organic pigment has excellent insulation and low dielectric properties, thus improving the resistivity of the film. It is particularly suitable for light-shielding pixel partitioning layers, TFT planarization layers, TFT protective layers, interlayer insulating layers, or gate insulating layers in organic EL displays, which can improve the reliability of light-emitting elements.

[0283] Examples of (D1a-1) black organic pigments include, for example, anthraquinone-based black pigments, benzofuranone-based black pigments, perylene-based black pigments, aniline-based black pigments, azo-based black pigments, azomethyl alkali-based black pigments, or carbon black. Examples of carbon black include, for example, channel black, furnace black, thermal cracking black, acetylene black, or lampblack.

[0284] So-called (D1a-2) black inorganic pigments refer to inorganic pigments that color black by absorbing wavelengths of visible light. Compared with general organic pigments, (D1a-2) black inorganic pigments have superior heat resistance and weather resistance, thus improving the opacity of resin composition films and enhancing their heat resistance and weather resistance. Examples of (D1a-2) black inorganic pigments include, for example, graphite or silver-tin alloys, or metals such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, or silver, as well as particulate matter, oxides, complex oxides, sulfides, sulfates, nitrates, carbonates, nitrides, carbides, or oxynitrides.

[0285] The term "(D1a-3) two- or more color pigment mixture" refers to a color pigment mixture that simulates black by combining two or more pigments selected from red, orange, yellow, green, blue, or purple. Because it mixes two or more pigments, it is possible to adjust the transmission or absorption spectrum of the resin composition film, and to adjust the film of the resin composition towards the desired color coordinates. As the negative photosensitive resin composition of the present invention, the aforementioned "(D1a-3) two- or more color pigment mixture" is preferably (D1a-3a) a color pigment mixture containing blue, red, and yellow pigments; (D1a-3b) a color pigment mixture containing purple and yellow pigments; (D1a-3c) a color pigment mixture containing blue, red, and orange pigments; or (D1a-3d) a color pigment mixture containing blue, purple, and orange pigments. If the "(D1a-3) two or more color pigment mixture" has the above-described configuration, the sensitivity during exposure can be improved, and a low-cone pattern can be formed after development.

[0286] Examples of pigments that color blue include, for example, Pigment Blue 15, 15:3, 15:4, 15:6, 22, 60, or 64 (all values ​​are CI codes). Examples of pigments that color red include, for example, 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, or 250 (all values ​​are CI codes). Examples of pigments that color yellow include, for example, 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, or 194 (all values ​​are CI codes). Examples of pigments that color purple include, for example, Pigment Violet 19, 23, 29, 30, 32, 37, 40, or 50 (all values ​​are CI codes). Examples of pigments that color orange include, for example, Pigment Orange 12, 36, 38, 43, 51, 55, 59, 61, 64, 65, 71, or 72 (all values ​​are CI codes). Examples of pigments that color green include, for example, Pigment Green 7, 10, 36, or 58 (these are all CI numbers).

[0287] As the negative photosensitive resin composition of the present invention, in the above-mentioned (D1a-3) two or more coloring pigment mixtures, the blue pigment is preferably selected from one or more of CI pigment blue 15:4, CI pigment blue 15:6, and CI pigment blue 60; the red pigment is preferably selected from one or more of CI pigment red 123, CI pigment red 149, CI pigment red 177, CI pigment red 179, and CI pigment red 190; the yellow pigment is preferably selected from one or more of CI pigment yellow 120, CI pigment yellow 151, CI pigment yellow 175, CI pigment yellow 180, CI pigment yellow 181, CI pigment yellow 192, and CI pigment yellow 194; the purple pigment is preferably selected from one or more of CI pigment purple 19, CI pigment purple 29, and CI pigment purple 37; and the orange pigment is preferably selected from one or more of CI pigment orange 43, CI pigment orange 64, and CI pigment orange 72. If the mixture of two or more coloring pigments (D1a-3) has the above-described configuration, the sensitivity during exposure can be improved, and a low-cone pattern can be formed after development. Furthermore, these pigments exhibit excellent heat resistance and can reduce the halogen content derived from the pigments in the resin composition. They also possess excellent insulation and low dielectric properties, thus improving the reliability of the light-emitting element.

[0288] In the negative photosensitive resin composition of the present invention, the preferred content ratio of one or more selected from (D1a-1) black organic pigment, (D1a-2) black inorganic pigment, and (D1a-3) a mixture of two or more coloring pigments is as described in the preferred content ratio of the colorant (D) above. If the content ratio is within the above range, in particular, the reliability of the light-emitting element can be improved.

[0289] <(D1a-1a) Benzofuranone black pigment, (D1a-1b) Perylene black pigment, and (D1a-1c) Azo black pigment>

[0290] As the negative photosensitive resin composition of the present invention, from the viewpoints of improved sensitivity during exposure, reduced taper due to pattern shape control after development, and improved halftone properties, the aforementioned (D1a-1) black organic pigment is preferably selected from one or more of (D1a-1a) benzofuranone-based black pigment, (D1a-1b) perylene-based black pigment, and (D1a-1c) azo-based black pigment, more preferably (D1a-1a) benzofuranone-based black pigment. Compared with general organic pigments, (D1a-1a) benzofuranone-based black pigment, (D1a-1b) perylene-based black pigment, and (D1a-1c) azo-based black pigment have superior opacity per unit content ratio of pigment in the resin composition, thus achieving equivalent opacity with a lower content ratio. Therefore, the opacity of the film can be improved, and the sensitivity during exposure can be increased. Furthermore, compared with general organic and inorganic pigments, they exhibit superior insulation and low dielectric properties, thus improving the resistivity of the film. It is particularly suitable for light-shielding pixel partitioning layers, TFT planarization layers, TFT protective layers, interlayer insulating layers, or gate insulating layers in organic EL displays, which can improve the reliability of light-emitting elements.

[0291] In particular, (D1a-1a) benzofuranone-based black pigments absorb visible light wavelengths, while having high transmittance in the ultraviolet region (e.g., below 400 nm), thus improving exposure sensitivity and enabling the formation of low-cone patterns after development. However, in the case of (D1a-1a) benzofuranone-based black pigments, development residues originating from the pigment sometimes occur due to insufficient alkali resistance. That is, during development, because the surface of the (D1a-1a) benzofuranone-based black pigment is exposed to alkaline developing solution, a portion of the surface may decompose or dissolve, remaining on the substrate as the aforementioned development residues from the pigment. In such cases, as described above, by containing one or more of the following: (B3) an aliphatic free radical polymerizable compound containing a soft chain; (B1) a free radical polymerizable compound containing a fluorene skeleton; and (B2) a free radical polymerizable compound containing an indane skeleton, the generation of the aforementioned development residues from the pigment can be suppressed.

[0292] As a (D1a-1a) benzofuranone black pigment, the molecule has a benzofuran-2(3H)-one structure or a benzofuran-3(2H)-one structure, preferably a benzofuranone compound, its geometric isomer, its salt, or a salt of its geometric isomer represented by general formula (63) or general formula (64).

[0293]

[0294] In general formulas (63) and (64), R 206 R207 R 214 and R 215 Each of the following can be independently represented as a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 20 fluorine atoms having 1 to 10 carbon atoms. R 208 R 209 R 216 and R 217 Each independently represents a hydrogen atom, a halogen atom, and 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 NR 212 R 213 , NHCOR 212 NR 212 COR 213 N=CH2, N=CHR 212 N = CR 212 R 213 SH, SR 212 SOR 212 SO2R 212 SO3R 212 SO3H, SO3 - SO2NH2, SO2NHR 212 or SO2NR 212 R 213 R 212 and R 213 Each can independently represent an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, a cycloalkenyl group with 4 to 10 carbon atoms, or an alkynyl group with 2 to 10 carbon atoms. Multiple R groups can be used. 208 R 209 R 216 、or R 217 Through direct bonding, or oxygen atom bridging, sulfur atom bridging, NH bridging, or NR... 212 A ring is formed by bridging. R 210 R 211 R 218 and R 219Each of these groups 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 from 0 to 4. The aforementioned alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, and aryl groups may have heteroatoms and may be either unsubstituted or substituted.

[0295] Examples of (D1a-1a) benzofuranone black pigments include, for example, the black pigment described in "IRGAPHOR" (registered trademark) BLACKS0100CF (manufactured by BASF), International Publication No. 2010 / 081624, or International Publication No. 2010 / 081756.

[0296] The so-called (D1a-1b) perylene black pigment has a perylene structure in its molecule, and is preferably a perylene compound represented by the general formula (69).

[0297]

[0298] In general formula (69), X 92 and X 93 Each can be used independently to represent a directly bonded or alkylene chain with 1 to 10 carbon atoms. 92 and Y 93 Each can be used independently to represent a directly bonded or aryl chain with 6 to 15 carbon atoms. R 224 and R 225 Each can independently represent a hydrogen atom, a hydroxyl group, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, or an acyl group with 2 to 6 carbon atoms. R 226 This represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 20 fluorine atoms and 1 to 10 carbon atoms. a and b each independently represent integers from 0 to 5. c represents integers from 0 to 8. In X 92 and X 93 For direct bonding, and Y 92 and Y 93 In the case of direct bonding, R 224 and R 225 Each is preferably an alkyl group having 1 to 10 carbon atoms, and a and b are both 1. In X 92 and X 93 It is an alkylene chain with 1 to 10 carbon atoms, and Y 92 and Y 93 In the case of direct bonding, R 224 and R 225 Preferably, hydroxyl groups are present, and a and b are both 1. In X 92 and X 93 It is an alkylene chain with 1 to 10 carbon atoms, and Y 92 and Y93 In the case of an arylene chain with 6 to 15 carbon atoms, R 224 and R 225 Each is preferably a hydroxyl group, an alkoxy group with 1 to 6 carbon atoms, or an acyl group with 2 to 6 carbon atoms. a and b each independently represent an integer from 0 to 5. The alkylene chain, arylene chain, alkoxy group, acyl group, and alkyl group may have heteroatoms and may be either unsubstituted or substituted.

[0299] Examples of (D1a-1b) perylene black pigments include Pigment Black 31 or 32 (both numbers are CI codes). Other examples include "PALIOGEN" (registered trademark) BLACK S0084, "PALIOGEN" K0084, "PALIOGEN" L0086, "PALIOGEN" K0086, "PALIOGEN" EH0788, or "PALIOGEN" FK4281 (all manufactured by BASF).

[0300] The so-called (D1a-1c) azo black pigment has an azo group in its molecule, preferably an azo compound represented by the general formula (72).

[0301]

[0302] In general formula (72), X 96 Y represents an aryl chain with 6 to 15 carbon atoms. 96 R represents an aryl chain with 6 to 15 carbon atoms. 275 R 276 and R 277 Each can independently represent a halogen or an alkyl group having 1 to 10 carbon atoms. R 278 R represents halogen, alkyl group with 1 to 10 carbon atoms, alkoxy group with 1 to 6 carbon atoms, or nitro group. 279 R represents halogen, alkyl group with 1 to 10 carbon atoms, alkoxy group with 1 to 6 carbon atoms, acylamino group with 2 to 10 carbon atoms, or nitro group. 280 R 281 R 282 and R 283 Each of the following independently represents an alkyl group having 1 to 10 hydrogen atoms or carbon atoms. 'a' represents an integer from 0 to 4, 'b' represents an integer from 0 to 2, 'c' represents an integer from 0 to 4, 'd' and 'e' each independently represent an integer from 0 to 8, and 'n' represents an integer from 1 to 4. The aforementioned arylene chains, alkyl groups, alkoxy groups, and acylamino groups may have heteroatoms and may be either unsubstituted or substituted.

[0303] Examples of (D1a-1c) azo black pigments include, for example, "CHROMOFINE" (registered trademark) BLACKA1103 (manufactured by Dainippon Seika Co., Ltd.), the black pigment described in Japanese Patent Application Publication No. 01-170601, or the black pigment described in Japanese Patent Application Publication No. 02-034664.

[0304] From the viewpoints of improved light-shielding properties and enhanced reliability of the light-emitting element, the content of one or more selected from (D1a-1a) benzofuranone-based black pigments, (D1a-1b) perylene-based black pigments, and (D1a-1c) azo-based black pigments in the total solid components of the negative photosensitive resin composition of the present invention, excluding the solvent, is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and particularly preferably 30% by mass or more. On the other hand, from the viewpoints of improved sensitivity during exposure, formation of a low-cone pattern after development, and enhanced reliability of the light-emitting element, the content of one or more selected from (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.

[0305] In the negative photosensitive resin composition of the present invention, from the viewpoint that the effects of improved sensitivity during exposure, low-cone pattern formation after development, improved halftone properties, and suppression of residue adhesion at the pattern openings after thermosetting become significant, the photopolymerization initiator (C1-1a) containing a fused polycyclic skeleton and the photopolymerization initiator (C1-1b) containing a fused polycyclic heterocyclic skeleton have one selected from nitro, naphthyl carbonyl, trimethylbenzoyl, thiophenyl carbonyl, and furanyl carbonyl structures. In the above cases, it is preferable to use a mixture of (D1a-1) black organic pigment and / or (D1a-3) two or more coloring pigments as (D) colorant. The (D1a-1) black organic pigment contains one or more selected from (D1a-1a) benzofuranone black pigment, (D1a-1b) perylene black pigment, and (D1a-1c) azo black pigment. The (D1a-3) two or more coloring pigment mixture contains two or more pigments selected from red, orange, yellow, green, blue, and purple pigments.

[0306] <(DC) Cover>

[0307] As the negative photosensitive resin composition of the present invention, the aforementioned (D1a-1) black organic pigment preferably further contains a (DC) coating layer. The (DC) coating layer refers to a layer that coats the surface of the pigment, formed, for example, through 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 containing the (DC) coating layer, the surface state of the particles of the aforementioned (D1a-1) black organic pigment can be modified by acidification, alkaliification, hydrophilicity, or hydrophobicity, thereby improving acid resistance, alkali resistance, solvent resistance, dispersion stability, or heat resistance. This suppresses the generation of development residues originating from the pigment. Furthermore, side etching during development is suppressed, and a low-cone pattern can be formed after development. In addition, halftone characteristics can be improved. Moreover, by forming an insulating coating layer on the particle surface, the leakage current is reduced due to the increased insulation of the cured film, thereby improving the reliability of the light-emitting element. In the case of the above-mentioned (D1a-1) black organic pigment, especially the (D1a-1a) benzofuranone-based black pigment, by making the (D1a-1a) benzofuranone-based black pigment contain a (DC) coating layer, the alkali resistance of the pigment can be improved and the generation of the above-mentioned pigment-derived development residue can be suppressed.

[0308] The average coverage of the (DC) coating layer relative to the aforementioned (D1a-1) black organic pigment is preferably 50% or more, preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If 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 (DC) coating layer relative to the aforementioned (D1a-1) black organic pigment is observed using a transmission electron microscope (H9500; manufactured by Hitachi Hightech Noroge Co., Ltd.) 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 rate M (%) of each black pigment is calculated using the following formula, and the mean value is calculated, thereby the average coverage rate N (%) can be obtained.

[0309] Coverage rate M (%) = {L1 / (L1+L2)} × 100

[0310] L1: The total length (nm) of the portion of the particle's periphery covered by the coating layer.

[0311] L2: The total length (nm) of the portion of the particle's periphery not covered by the coating layer (the portion where the interface is directly in contact with the embedded resin).

[0312] L1+L2: The outer perimeter length of the particle (nm).

[0313] <(DC-1) Silica coating, (DC-2) Metal oxide coating, and (DC-3) Metal hydroxide coating>

[0314] As the (DC) coating layer, it is preferable to contain one selected from (DC-1) silica coating layer, (DC-2) metal oxide coating layer, and (DC-3) metal hydroxide coating layer. Silica, metal oxide, and metal hydroxide impart alkali resistance to the pigment, thereby suppressing the generation of development residues from the pigment. Examples of silica include silica or its aqueous form. Examples of metal oxides include metal oxides or their hydrates. Examples of metal oxides include aluminum oxide, for example, aluminum oxide (Al2O3) or aluminum oxide hydrate (Al2O3·nH2O). Examples of metal hydroxides include, for example, aluminum hydroxide (Al(OH)3). Since silica has a low dielectric constant, it can suppress the increase in dielectric constant when the content of the (DC) coating layer containing (D1a-1) black organic pigment is increased, thus improving the reliability of the light-emitting element.

[0315] <<(E) Dispersant>>

[0316] As the negative photosensitive resin composition of the present invention, it is preferable to further contain an (E) dispersant. The (E) dispersant refers to a compound having a surface affinity group that interacts with the surface of the aforementioned (D1) pigment, etc., and a dispersion stabilizing structure that improves the dispersion stability of the (D1) pigment, etc. Examples of dispersion stabilizing structures for the (E) dispersant include polymer chains that contribute to dispersion stabilization due to steric hindrance, or ionic or polar substituents that contribute to dispersion stabilization due to 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 more likely the particles will aggregate due to the increased surface area, sometimes becoming a cause of residue after development. In particular, when the negative photosensitive resin composition contains (D1) pigment as a (D) colorant, the presence of an (E) dispersant can improve the dispersion stability of the negative photosensitive resin composition containing (D1) pigment, thereby improving the pattern processing properties with alkaline developer, the resolution after development, and the storage stability of the coating solution.

[0317] Examples of dispersants (E) include, for example, dispersants having only a basic group, dispersants having both a basic group and an acidic group, dispersants having only an acidic group, dispersants having a structure in which a basic group forms a salt with an acid, dispersants having a structure in which an acidic group forms a salt with a base, or dispersants having neither a basic group nor an acidic group. From the viewpoints of improved dispersion stability, improved pattern processing properties with alkaline developer, and improved resolution after development, dispersants having only a basic group, dispersants having both a basic group and an acidic group, dispersants having a structure in which a basic group forms a salt with an acid, or dispersants having a structure in which an acidic group forms a salt with a base are preferred, and dispersants having only a basic group or dispersants having both a basic group and an acidic group are more preferred.

[0318] Examples of dispersants that function as (E) include those with a basic group or a structure in which the basic group forms a salt with an acid, such as tertiary amino or quaternary ammonium salt structures, or pyrrolidine skeletons, pyrrole skeletons, imidazole skeletons, pyrazole skeletons, triazole skeletons, tetraazole skeletons, and imidazoleline skeletons. azole skeleton, isoazole azole skeleton, Azoline skeleton, iso Nitrogen-containing ring skeletons, such as azoline, thiazole, isothiazole, thiazoline, isothiazolinite, thiazide, piperidine, piperazine, morpholine, pyridine, pyridazine, pyrimidine, triazine, isocyanuric acid, imidazolidinone, propylidene urea, butylidene urea, hydantoin, barbituric acid, alloxan, or glycourea skeletons, or structures formed by these nitrogen-containing skeletons, can be used as counter anions in structures where a basic group and an acid form a salt.

[0319] The amine value of the (E) dispersant is preferably 5 mg KOH / g or more, more preferably 8 mg KOH / g or more, and even more preferably 10 mg KOH / g or more. If the amine value is 5 mg KOH / g or more, the dispersion stability of the (D1) pigment can be improved. On the other hand, the amine value is preferably 150 mg KOH / g or less, more preferably 120 mg KOH / g or less, and even more preferably 100 mg KOH / g or less. If the amine value is 150 mg KOH / g or less, the storage stability of the resin composition can be improved. Here, the amine value refers to the weight of potassium hydroxide equivalent to the amount of acid reacting with each 1 g of (E) dispersant, expressed in mg KOH / g. It can be determined by neutralizing 1 g of the (E) dispersant with acid and then titrating it with an aqueous solution of potassium hydroxide. From the amine value, the amine equivalent (in g / mol) of the resin weight per 1 mol of amino or other basic groups can be calculated, and the number of amino or other basic groups in the (E) dispersant can be determined.

[0320] The acid value of the (E) dispersant is preferably 5 mg KOH / g or more, more preferably 8 mg KOH / g or more, and even more preferably 10 mg KOH / g or more. An acid value of 5 mg KOH / g or more improves the dispersion stability of the (D1) pigment. Conversely, the acid value is preferably 200 mg KOH / g or less, more preferably 170 mg KOH / g or less, and even more preferably 150 mg KOH / g or less. An acid value of 200 mg KOH / g or less improves the storage stability of the resin composition. Here, the acid value refers to the weight of potassium hydroxide reacting with 1 g of (E) dispersant, expressed in mg KOH / g. It can be determined by titrating 1 g of (E) dispersant with an aqueous potassium hydroxide solution. The acid equivalent (in g / mol) of the resin weight per 1 mol of acidic groups can be calculated from the acid value, and the number of acidic groups in the (E) dispersant can be determined.

[0321] Examples of dispersants with polymer chains (E) include acrylic resin-based dispersants, polyoxyethylene ether-based dispersants, polyester-based dispersants, polyurethane-based dispersants, polyol-based dispersants, polyethyleneimine-based dispersants, and polyallylamine-based dispersants. From the viewpoint of pattern processing properties with alkaline developing solutions, acrylic resin-based dispersants, polyoxyethylene ether-based dispersants, polyester-based dispersants, polyurethane-based dispersants, and polyol-based dispersants are preferred.

[0322] When the negative photosensitive resin composition of the present invention contains (D1) pigment, from the viewpoint of improving dispersion stability and pattern processing properties with alkaline developer, the content ratio of (E) dispersant in the negative photosensitive resin composition of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, when the total of (D1) pigment and (E) dispersant is set to 100% by mass. On the other hand, from the viewpoint of improving the formation of low-cone pattern after development and the reliability of light-emitting element, the content ratio of (E) dispersant is preferably 60% by mass or less, more preferably 50% by mass or less.

[0323] <<(F) Crosslinking Agent>>

[0324] As the negative photosensitive resin composition of the present invention, it is preferable to further contain a (F) crosslinking agent. The (F) crosslinking agent refers to a compound having crosslinking groups capable of binding with the resin. By containing the (F) crosslinking agent, chemical resistance can be improved, and a low-cone pattern can be formed after thermosetting. This is presumably because the (F) crosslinking agent introduces a new crosslinking structure into the cured film of the resin composition, increasing the crosslinking density. Furthermore, by introducing the new crosslinking structure, the dense orientation of the polymer chains is hindered, and the steric hindrance of aromatic rings and the like contained in the resin is alleviated, thereby improving reflowability during thermosetting. As the (F) crosslinking agent, in addition to the epoxy crosslinking agent (F1) containing a fluorene backbone and the epoxy crosslinking agent (F2) containing an indane backbone described later, alkoxymethyl crosslinking agents, hydroxymethyl crosslinking agents, isocyanuric acid-based epoxy crosslinking agents, or oxetane-butyl crosslinking agents are also preferred. Furthermore, as a (F) crosslinking agent, it is preferable to be a compound having two or more thermally crosslinking groups selected from alkoxymethyl, hydroxymethyl, epoxy, and oxetane.

[0325] <(F1) Epoxy crosslinking agent containing a fluorene backbone and (F2) Epoxy crosslinking agent containing an indene backbone>

[0326] The negative photosensitive resin composition of the present invention preferably further contains an epoxy crosslinking agent as a (F) crosslinking agent. Epoxy groups have high thermal reactivity. Since the thermal crosslinking reaction occurs even at lower temperatures, the presence of an epoxy crosslinking agent allows for the formation of a low-cone pattern after thermosetting. The negative photosensitive resin composition of the present invention preferably further contains an epoxy crosslinking agent having a fused polycyclic backbone as a (F) crosslinking agent. The (F) crosslinking agent has a fused polycyclic backbone, allowing for the formation of a low-cone pattern after development and improving halftone properties. Furthermore, residue adhesion to the openings of the pattern after thermosetting can be suppressed. This can be attributed to the significant interaction between the fused polycyclic backbone and the fused polycyclic backbone of the photopolymerization initiator (C1-1a) described later, resulting in the hydrophobic fused polycyclic backbone of the crosslinking agent being biased around the photopolymerization initiator, suppressing lateral etching during development.

[0327] The fused polycyclic skeleton of the (F) crosslinking agent preferably has one or more selected from fluorene skeleton, benzo[a]fluorene skeleton, dibenzo[a]fluorene skeleton, indene skeleton, indane skeleton, benzo[a]indene skeleton, benzo[a]indane skeleton, dihydroanthracene skeleton, dihydrobenzanthracene skeleton, dihydrophenanthrene skeleton, dihydrobenzanthracene skeleton, dihydronaphthalene skeleton, dihydrobenzanthracene skeleton, tetrahydronaphthalene skeleton, and tetrahydrobenzanthracene skeleton.

[0328] The negative photosensitive resin composition of the present invention preferably contains one or more epoxy crosslinking agents selected from (F1) epoxy crosslinking agents containing a fluorene backbone and (F2) epoxy crosslinking agents containing an indane backbone as epoxy crosslinking agents having a fused polycyclic backbone. The epoxy crosslinking agent containing a fluorene backbone (F1) refers to a compound having an epoxy group as a thermal crosslinking group and a fluorene backbone in its molecule. The epoxy crosslinking agent containing an indane backbone (F2) refers to a compound having an epoxy group as a thermal crosslinking group and an indane backbone in its molecule. By containing one or more epoxy crosslinking agents selected from (F1) epoxy crosslinking agents containing a fluorene backbone and (F2) epoxy crosslinking agents containing an indane backbone, a low-cone pattern can be formed after development, and halftone characteristics can be improved. This can be attributed to the fact that the fluorene and indane skeletons interact significantly with the fused polycyclic skeletons of the photopolymerization initiator (C1-1a) described later, thereby biasing the hydrophobic fluorene or indane skeleton crosslinker around the photopolymerization initiator and suppressing lateral etching during development.

[0329] Examples of epoxy crosslinking agents containing a fluorene backbone (F1) include, for example, 9,9-bis[4-(2-epoxypropoxyethoxy)phenyl]fluorene, 9,9-bis(4-epoxypropoxyphenyl)fluorene, 9,9-bis[4-(2-epoxypropoxyethoxy)-1-naphthyl]fluorene, or 9,9-bis[3,4-bis(2-epoxypropoxyethoxy)phenyl]fluorene.

[0330] Examples of epoxy crosslinking agents containing an indaminozide skeleton (F2) include, for example, 1,1-bis[4-(2-epoxypropoxyethoxy)phenyl]indaminozide, 1,1-bis(4-epoxypropoxyphenyl)indaminozide, 1,1-bis[4-(2-epoxypropoxyethoxy)phenyl]-3-phenylindaminozide, 1,1-bis[4-(2-epoxypropoxyethoxy)-1-naphthyl]indaminozide, 1,1-bis[3,4-bis(2-epoxypropoxyethoxy)phenyl]indaminozide, 2,2-bis[4-(2-epoxypropoxyethoxy)phenyl]indaminozide, or 2,2-bis[3,4-bis(2-epoxypropoxyethoxy)phenyl]indaminozide.

[0331] (F1) Epoxy crosslinking agents containing a fluorene backbone and (F2) epoxy crosslinking agents containing an indane backbone can be synthesized by known methods.

[0332] From the viewpoint of improving the low-cone pattern formation after development and heat curing, and enhancing halftone properties, the total content of the epoxy crosslinking agent containing the fluorene skeleton (F1) and the epoxy crosslinking agent containing the indane skeleton in the negative photosensitive resin composition of the present invention is preferably 1 part by mass or more, more preferably 5 parts by mass or more, when the total amount of the alkali-soluble resin (A) and the free radical polymerizable compound (B) is set to 100 parts by mass. On the other hand, from the viewpoint of suppressing residue generation after development, the total content of the epoxy crosslinking agent containing the fluorene skeleton (F1) and the epoxy crosslinking agent containing the indane skeleton (F2) is preferably 50 parts by mass or less, more preferably 30 parts by mass or less.

[0333] <<(G) Sensitizer>>

[0334] As the negative photosensitive resin composition of the present invention, it is preferable to further contain a (G) sensitizer. A (G) sensitizer is a compound that absorbs the energy of UV light during exposure, generates excited triplet electrons through internal conversion and intersystem crossing, and can transfer energy to the aforementioned (C1) photopolymerization initiator, etc., thus exhibiting sensitizing activity. By containing a (G) sensitizer, the sensitivity during exposure can be improved. This is presumably because, for example, by absorbing long-wavelength light that is not absorbed by the (C1) photopolymerization initiator, etc., the (G) sensitizer transfers its energy from the (G) sensitizer to the (C1) photopolymerization initiator, etc., thereby improving the photoreaction efficiency. As a (G) sensitizer, in addition to the (G1) sensitizer containing a fluorene skeleton and the (G2) sensitizer containing an indane skeleton described later, thioxanone-based sensitizers are also preferred. Examples of thioxanthone-based sensitizers include, for example, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, or 2,4-dichlorothioxanthone.

[0335] <(G1) Sensitizers containing a fluorene framework and (G2) sensitizers containing an indane framework>

[0336] The negative photosensitive resin composition of the present invention preferably further contains a (G) sensitizer having a fused polycyclic framework as the (G) sensitizer. The (G) sensitizer having a fused polycyclic framework improves the sensitivity during exposure and allows for the formation of a low-cone pattern after development. Furthermore, halftone properties are improved. This is because the fused polycyclic framework interacts significantly with the fused polycyclic framework of the photopolymerization initiator (C1-1a) described later, thereby improving the compatibility between the sensitizer and the photopolymerization initiator, and enabling efficient energy transfer of UV light during exposure.

[0337] The fused polycyclic skeleton of the (G) sensitizer preferably has one or more selected from fluorene skeleton, benzo[a]fluorene skeleton, dibenzo[a]fluorene skeleton, indene skeleton, indane skeleton, benzo[a]indene skeleton, benzo[a]indane skeleton, dihydroanthracene skeleton, dihydrobenzanthracene skeleton, dihydrophenanthrene skeleton, dihydrobenzanthracene skeleton, dihydronaphthalene skeleton, dihydrobenzonaphthalene skeleton, tetrahydronaphthalene skeleton, and tetrahydrobenzonaphthalene skeleton.

[0338] Furthermore, sensitization can be achieved by having substituents containing non-shared electron pairs that can conjugate with the fused polycyclic skeleton, and / or substituents containing π bonds that can conjugate with the fused polycyclic skeleton. Examples of substituents containing non-shared electron pairs include halogens, amino groups, hydroxyl groups, alkoxy groups, or mercapto groups. Examples of substituents containing π bonds include aryl, nitro, cyano, carboxyl, formyl, alkyl carbonyl, alkyloxy carbonyl, or sulfonyl groups. Additionally, examples of substituents containing π bonds include structures where the carbon atom on the fused polycyclic skeleton forms an unsaturated double bond containing a π bond with a nitrogen atom, oxygen atom, or sulfur atom (dialkyl oxime, dialkyl carbonyl, or dialkyl thiocarbonyl, etc.).

[0339] The negative photosensitive resin composition of the present invention preferably contains one or more of a sensitizer selected from (G1) a sensitizer containing a fluorene skeleton and (G2) a sensitizer containing an indane skeleton as a (G) sensitizer having a fused polycyclic skeleton. The (G1) sensitizer containing a fluorene skeleton refers to a compound whose molecule contains a fluorene skeleton and has sensitizing activity. The (G2) sensitizer containing an indane skeleton refers to a compound whose molecule contains an indane skeleton and has sensitizing activity. By containing one or more of a sensitizer selected from (G1) a sensitizer containing a fluorene skeleton and (G2) a sensitizer containing an indane skeleton, the sensitivity during exposure can be improved, and a low-cone pattern can be formed after development. In addition, halftone characteristics can be improved. Furthermore, residue adhesion at the opening of the pattern after thermosetting can be suppressed. This can be attributed to the fact that the fluorene and indane skeletons significantly interact with the fused polycyclic skeletons of the photopolymerization initiator (C1-1a) and the fused polycyclic heterocyclic skeletons of the photopolymerization initiator (C1-1b), thereby improving the compatibility between the sensitizer and the photopolymerization initiator and enabling efficient energy transfer of UV light during exposure.

[0340] Examples of sensitizers containing a fluorene skeleton (G1) include, for example, 2-bromofluorene, 2-phenylfluorene, 2-nitrofluorene, 2,7-dinitrofluorene, 2-cyanofluorene, benzo[a]fluorene, 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, or 2-carboxy-9-fluorenone.

[0341] Examples of sensitizers containing an indane skeleton (G2) include, for example, 6-bromoindane, 6-phenylindane, 6-nitroindane, 6-cyanoindane, 6-bromoindane, 6-nitroindane, benzo[a]indane, indane-1-one, benzo[a]indane-1-one, benzo[a]indane, indane-1-one, benzo[a]indane-1-one, 6-chloroindane-1-one, 6-bromoindane-1-one, 6-iodoindane-1-one, 6-phenylindane-1-one, 6-nitroindane-1-one, 6-cyanoindane-1-one, or 6-carboxyindane-1-one, 6-bromoindane-1-one, or 6-nitroindane-1-one.

[0342] (G1) Sensitizers containing a fluorene skeleton and (G2) sensitizers containing an indane skeleton can be synthesized by known methods.

[0343] From the viewpoints of improved sensitivity during exposure, formation of a low-cone pattern after development, and improved halftone properties, the total content of the sensitizer (G1) containing a fluorene skeleton and the sensitizer (G2) containing an indane skeleton in the negative photosensitive resin composition of the present invention is preferably 0.1 parts by mass or more, more preferably 3 parts by mass or more, when the total amount of (A) alkali-soluble resin and (B) free radical polymerizable compound is set to 100 parts by mass. On the other hand, from the viewpoints of improved sensitivity during exposure and suppression of residue formation after development, the total content of the sensitizer (G1) containing a fluorene skeleton and the sensitizer (G2) containing an indane skeleton is preferably 20 parts by mass or less, more preferably 10 parts by mass or less.

[0344] <Chain transfer agent>

[0345] The negative photosensitive resin composition of the present invention preferably further contains a chain transfer agent. By containing an appropriate amount of chain transfer agent, the sensitivity during exposure can be improved, and a low-cone pattern can be formed after development. A thiol compound is preferred as the chain transfer agent. The content of the chain transfer agent in the negative photosensitive resin composition of the present invention is preferably 0.01 parts by mass or more, provided that the total amount of (A) alkali-soluble resin and (B) free radical polymerizable compound is 100 parts by mass. On the other hand, the content of the chain transfer agent is preferably 15 parts by mass or less.

[0346] <Polymerization inhibitor>

[0347] The negative photosensitive resin composition of the present invention preferably further contains a polymerization inhibitor. By containing an appropriate amount of polymerization inhibitor, the generation of residue after development can be suppressed, and the resolution after development can be improved. As a polymerization inhibitor, a hindered phenolic compound, a hindered amine compound, or a benzimidazole compound is preferred. The content of the polymerization inhibitor in the negative photosensitive resin composition of the present invention is preferably 0.01 parts by mass or more when the total amount of (A) alkali-soluble resin and (B) free radical polymerizable compound is set to 100 parts by mass. On the other hand, the content of the polymerization inhibitor is preferably 10 parts by mass or less.

[0348] <Silane Coupling Agent>

[0349] The negative photosensitive resin composition of the present invention preferably further contains a silane coupling agent. By including an appropriate amount of the silane coupling agent, the adhesion between the cured film and the substrate can be improved. As the silane coupling agent, trifunctional organosilanes, tetrafunctional organosilanes, or silicate compounds are preferred. The content of the silane coupling agent in the negative photosensitive resin composition of the present invention is preferably 0.01 parts by mass or more, provided that the total amount of (A) alkali-soluble resin and (B) free radical polymerizable compound is 100 parts by mass. On the other hand, the content of the silane coupling agent is preferably 15 parts by mass or less.

[0350] <surfactants>

[0351] The negative photosensitive resin composition of the present invention preferably further contains a surfactant. By including an appropriate amount of surfactant, the surface tension of the resin composition can be adjusted arbitrarily, thereby improving the leveling during coating and the uniformity of the coating thickness. Fluoropolymer surfactants, silicone surfactants, polyoxyethylene ether surfactants, or acrylic resin surfactants are preferred as surfactants. The surfactant content 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 surfactant content is preferably 1% by mass or less.

[0352] <Solvent>

[0353] As the negative photosensitive resin composition of the present invention, it is preferable to further contain a solvent. By containing a solvent, the resin composition can be formed on a substrate with a desired film thickness. In addition, leveling during coating and film thickness uniformity can be improved. As a solvent, from the viewpoint of the solubility of various resins and additives, compounds having alcoholic hydroxyl groups, compounds having carbonyl groups, or compounds having three or more ether bonds are preferred. As a solvent, from the viewpoint of improving film thickness uniformity by suppressing coating unevenness, compounds with a boiling point of 110°C or higher at atmospheric pressure are more preferred. On the other hand, from the viewpoint of improving flatness and film thickness uniformity by suppressing film shrinkage during heat curing, compounds with a boiling point of 250°C or lower at atmospheric pressure are more preferred. The content ratio of the solvent in the negative photosensitive resin composition of the present invention can be appropriately adjusted according to the coating method, etc. For example, in the case of forming a film by spin coating, it is generally 50 to 95% by mass of the entire negative photosensitive resin composition.

[0354] As the negative photosensitive resin composition of the present invention, when containing (D1) pigment as (D) colorant, a solvent having a carbonyl group or ester bond is preferred as the solvent. By containing a solvent having a carbonyl group or ester bond, the dispersion stability of the negative photosensitive resin composition containing (D1) pigment, etc., can be improved, the generation of residue in the developing solution can be suppressed, and the storage stability of the coating solution can be improved. From the viewpoint of improving dispersion stability and suppressing residue after development, as the carbonyl group, alkyl carbonyl, dialkyl carbonyl, formyl, carboxyl, amide, imide, urea bond, or urethane bond is preferred, alkyl carbonyl, dialkyl carbonyl, or formyl is more preferred, and alkyl carbonyl or dialkyl carbonyl is even more preferred. As the ester bond, carboxylic acid ester bond, carbonate bond, or formate bond is preferred, and carboxylic acid ester bond is even more preferred. Among the carboxylic acid ester bonds, acetate bond, propionate bond, or butyrate bond is more preferred, and acetate bond is even more preferred.

[0355] Examples of solvents containing acetate bonds include, for example, 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, or 1,4-butanediol diacetate.

[0356] In the negative photosensitive resin composition of the present invention, the solvent having carbonyl or ester bonds is preferably present in a concentration of 30 to 100% by mass, more preferably 50 to 100% by mass, and even more preferably 70 to 100% by mass. If the concentration is 30 to 100% by mass, the dispersion stability of the (D1) pigment can be improved, the formation of residues in the developer can be suppressed, and the storage stability of the coating solution can be improved.

[0357] <<Method for manufacturing the negative photosensitive resin composition of the present invention>>

[0358] A representative method for manufacturing the negative photosensitive resin composition of the present invention will now be described. In the case of a pigment (D1) containing a blackening agent (Da) as a colorant (D), a dispersant (E) is added to a solution of an alkali-soluble resin (A), and the pigment (D1) is dispersed in the mixed solution using a disperser to prepare a pigment dispersion. Next, an alkali-soluble resin (A), a free radical polymerizable compound (B), a photopolymerization initiator (C1), other additives, and any solvent are added to the pigment dispersion, and the mixture is stirred for 20 minutes to 3 hours to prepare a homogeneous solution. After stirring, the resulting solution is filtered to obtain the negative photosensitive resin composition of the present invention. From the viewpoint of maximizing dispersion efficiency and achieving microdispersion, a bead mill is preferred as the disperser. Examples of beads used in the bead mill include titanium dioxide beads, zirconium oxide beads, or 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.

[0359] <Curing pattern with a low cone shape>

[0360] A cured film can be manufactured by curing the negative photosensitive resin composition of the present invention. This allows for the acquisition of a cured film containing a pattern with a low taper shape. From the viewpoint of improving the resolution of the display device, the taper angle of the inclined edge in the cross-section of the cured pattern contained in the cured film obtained from the negative photosensitive resin composition of the present invention is preferably 10° or more, more preferably 15° or more. On the other hand, from the viewpoint of preventing electrode breakage, suppressing electric field concentration, and suppressing the deterioration of the light-emitting element, the taper angle of the inclined edge in the cross-section of the cured pattern contained in the cured film is preferably 60° or less, more preferably 45° or less.

[0361] <Optical density of the cured film>

[0362] As for the cured film obtained by curing the negative photosensitive resin composition of the present invention, from the viewpoint of reducing external light reflection due to improved light-shielding properties and improving the contrast of the display device, the optical density in the visible light region per 1 μm film thickness is preferably 0.3 or more, more preferably 1.0 or more, and even more preferably 1.5 or more. The wavelength of the visible light region is about 400 to 700 nm. It is particularly suitable for applications requiring high contrast and is preferred as a light-shielding pixel dividing layer, TFT planarization layer, TFT protective layer, interlayer insulating layer, or gate insulating layer for organic EL displays. On the other hand, from the viewpoint of improving sensitivity during exposure and forming low-cone pattern, the optical density per 1 μm film thickness is preferably 5.0 or less, more preferably 3.0 or less. The optical density per 1 μm film thickness of the cured film can be adjusted by the composition and content ratio of the colorant described in (D).

[0363] <Curing pattern with step shape>

[0364] The negative photosensitive resin composition of the present invention can form a stepped pattern with a sufficient thickness difference between the thick film portion and the thin film portion while maintaining high sensitivity. Furthermore, it enables low taper due to pattern shape control after development. Therefore, it is suitable for applications where a stepped shape is formed simultaneously in pixel dividing layers, electrode insulating layers, wiring insulating layers, TFT planarization layers, electrode planarization layers, wiring planarization layers, TFT protective layers, electrode protective layers, wiring protective layers, interlayer insulating layers, gate insulating layers, color filters, black matrices, or black columnar spacers. It is preferred as a pixel dividing layer, TFT planarization layer, TFT protective layer, interlayer insulating layer, or gate insulating layer, and more preferably as a pixel dividing layer, TFT planarization layer, or TFT protective layer. The negative photosensitive resin composition of the present invention is particularly suitable for applications requiring a pixel dividing layer in organic EL displays that combine high sensitivity, halftone characteristics, and low taper, where a stepped shape is formed simultaneously.

[0365] 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 In the stepped shape, the thick film portion 34 corresponds to the curing portion during exposure, having the maximum film thickness of the cured pattern. The thin film portions 35a, 35b, and 35c in the stepped shape correspond to the halftone exposure portion during exposure, having a film thickness less than that of the thick film portion 34. The respective cone angle θ of the inclined sides 36a, 36b, 36c, 36d, and 36e in the cross-section of the cured pattern with the stepped shape. a θ b θ c θ d θ eIdeally, all should be low-conical. The cone angle θ referred to here... a θ b θ c θ d θ e ,like Figure 2 As shown, this refers to the angle inside the cross-section of the stepped-shaped cured pattern formed by the horizontal edge 37 of the substrate of the substrate forming the cured pattern, or the horizontal edge of the film portions 35a, 35b, 35c, and the inclined edges 36a, 36b, 36c, 36d, 36e of the cross-section of the stepped-shaped cured pattern intersecting with the horizontal edges of the film portions 35a, 35b, 35c. Here, "upright cone" refers to a cone angle in the range of greater than 0° and less than 90°, and "inverted cone" refers to a cone angle in the range of greater than 90° and less than 180°. Furthermore, "rectangular" refers to a cone angle of 90°, and "low cone" refers to a cone angle in the range of greater than 0° and 60°.

[0366] The cone 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 like the preferred cone angle of the cured pattern with a low cone shape described above.

[0367] In the thickness between the plane of the lower surface and the plane of the upper surface of the cured pattern having a stepped shape obtained from the negative photosensitive resin composition of the present invention, the region having the largest thickness is designated as the thick film portion 34, and the region having a thickness less than that of the thick film portion 34 is designated as the thin film portion 35. The film thickness of the thick film portion 34 is set as (T... FT )μm, the film thickness of the thin film portions 35a, 35b, 35c disposed in the thick film portion 34 via at least one step shape is set as (T)μm. HT In the case of )μm, (T FT ) and (T HT ) film thickness difference (ΔT FT-HT The thickness difference (ΔT) is preferably 0.5 μm or more, more preferably 1.0 μm or more, further 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 vapor deposition mask during the formation of the light-emitting layer can be reduced, which can suppress the decrease in panel yield and improve the reliability of the light-emitting element. Furthermore, since a sufficient film thickness difference can be achieved in a single layer using a curing pattern with a stepped shape, the process time can be shortened. On the other hand, the film thickness difference (ΔT) FT-HTThe thickness difference 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. If the film thickness difference is 10.0 μm or less, the exposure amount during the formation of the stepped curing pattern can be reduced, and the takt time can be shortened.

[0368] The film thickness (T) of the thick film portion 34 FT The film thickness (T) of the thin film portions 35a, 35b, and 35c is 0.05 μm. HT The μm preferably satisfies the relationship shown in the general formula (α)~(γ).

[0369] 2.0≤(T FT )≤10.0(α)

[0370] 0.20≤(T HT )≤7.5(β)

[0371] 0.10×(T FT )≤(T HT )≤0.75×(T FT )(γ)

[0372] The film thickness (T) of the thick film portion 34 FT The film thickness (T) of the thin film portions 35a, 35b, and 35c is 0.05 μm. HT The μm is preferably further satisfied with the relationship shown in the general formula (δ)~(ζ).

[0373] 2.0≤(T FT )≤10.0(δ)

[0374] 0.30≤(T HT )≤7.0(ε)

[0375] 0.15×(T FT )≤(T HT )≤0.70×(T FT (ζ)

[0376] If the film thickness of the thick film portion 34 (T) FT The film thickness (T) of the thin film portions 35a, 35b, and 35c is 0.05 μm. HT If the micrometer is within the above range, the reliability of the light-emitting element can be improved and the process time can be shortened.

[0377] <An organic EL display equipped with a cured film obtained by curing the negative photosensitive resin composition of the present invention>

[0378] The negative photosensitive resin composition of the present invention can obtain a cured film with excellent heat resistance, capable of forming patterns with a low taper shape. Furthermore, it can improve the reliability of light-emitting elements, and is therefore particularly suitable for applications where element defects or performance degradation are assumed due to degassing caused by thermal decomposition, or for electrode wiring breakage due to high taper pattern shapes. Therefore, it is suitable for applications such as pixel dividing layers, TFT planarization layers, TFT protective layers, interlayer insulating layers, or gate insulating layers in organic EL displays.

[0379] In addition, the presence of the aforementioned (D) colorant enables the prevention of visible electrode wiring or the reduction of external light reflection, thereby improving the contrast ratio of the organic EL display. Therefore, with the increased contrast ratio, a polarizer and a quarter-wave plate are not required on the light extraction side of the light-emitting element, thus improving the flexibility of the organic EL display and enabling the manufacture of a highly flexible organic EL display. Furthermore, the organic EL display of the present invention preferably has a curved display section. From the viewpoint of suppressing display defects in a display section formed by a curved surface, the radius of curvature of this curved surface is preferably 0.1 mm or more, more preferably 0.3 mm or more. Furthermore, from the viewpoint of miniaturization and high resolution of the organic EL display, 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.

[0380] <Schematic cross-sectional view of the manufacturing process of organic EL displays>

[0381] As an example of a process using the negative photosensitive resin composition of the present invention, taking the process of using a cured film of this composition as a light-shielding pixel segmentation layer for an organic EL display as an example, in... Figure 1The following is a schematic cross-sectional view for illustration. First, (step 1) a thin-film transistor (hereinafter, "TFT") 2 is formed on a glass substrate 1. A photosensitive material for TFT planarization is deposited, patterned by photolithography, and then thermally cured to form a cured film 3 for TFT planarization. Next, (step 2) a silver-palladium-copper alloy (hereinafter, "APC") is deposited by sputtering, and a pattern is formed by etching using a photoresist to form an APC layer. Further, an indium tin oxide (hereinafter, "ITO") film is deposited on top of the APC layer by sputtering, and a pattern is formed by etching using a photoresist to form a reflective electrode 4 as the first electrode. Then, (step 3) the negative photosensitive resin composition of the present invention is coated and pre-baked to form a pre-baked film 5a. Next, (step 4) an active chemical ray 7 is irradiated through a mask 6 having the desired pattern. Next, in step 5, after developing and patterning, bleaching exposure and intermediate baking are performed as needed to thermally cure the material, thereby forming a cured pattern 5b with the desired pattern as a light-shielding pixel segmentation layer. Then, in step 6, an EL light-emitting material is deposited through a mask to form an EL light-emitting layer 8, a magnesium-silver alloy (hereinafter, "MgAg") is deposited through a mask to form a film, and a transparent electrode 9 is formed as a second electrode by etching using a photoresist. Next, in step 7, a photosensitive material for planarization is deposited, patterned by photolithography, and thermally cured to form a cured film 10 for planarization. Then, a cover glass 11 is bonded to obtain an organic EL display having a negative photosensitive resin composition of the present invention as a light-shielding pixel segmentation layer.

[0382] <Method for manufacturing cured film>

[0383] The manufacturing method of 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).

[0384] (1) The step of forming a coating film of the negative photosensitive resin composition of the present invention on a substrate.

[0385] (2) The step of irradiating the coating of the negative photosensitive resin composition with active chemical rays through a photomask.

[0386] (3) The step of developing the negative photosensitive resin composition using an alkaline solution, and,

[0387] (4) The process of heating the pattern to obtain a cured pattern of the negative photosensitive resin composition.

[0388] <The process of forming a coating>

[0389] The method for manufacturing a display device using the negative photosensitive resin composition of the present invention includes a step of (1) forming a coating film of the negative photosensitive resin composition on a substrate. Examples of methods for forming a film of the negative photosensitive resin composition include, for example, coating the resin composition on a substrate or patterning the resin composition on a substrate.

[0390] As a substrate, for example, a substrate on which one or more oxides, metals (molybdenum, silver, copper, aluminum, chromium, or titanium, etc.) selected from indium, tin, zinc, aluminum, and gallium are formed as electrodes or wirings can be used. Examples of substrates containing one or more oxides selected from indium, tin, zinc, aluminum, and gallium include indium tin oxide (ITO).

[0391] <Method for coating a negative photosensitive resin composition onto a substrate>

[0392] Examples of methods for coating a negative photosensitive resin composition onto a substrate include spin coating, curtain coating, jet coating, or slot coating. The coating thickness varies depending on the coating method, the concentration of solid components in the resin composition, viscosity, etc., but is generally coated such that the film thickness after coating and pre-baking is 0.1 to 30 μm.

[0393] Preferably, the film is formed by pre-baking after coating a negative photosensitive resin composition onto a substrate. Pre-baking can be performed using an oven, hot plate, infrared radiation, rapid annealing device, or laser annealing device. The preferred pre-baking temperature is 50–150°C. The preferred pre-baking time is 30 seconds to several hours. Pre-baking can be performed in two or more stages, such as pre-baking at 80°C for 2 minutes followed by pre-baking at 120°C for 2 minutes.

[0394]

[0395] Examples of methods for patterning a coating film of a negative photosensitive resin composition formed on a substrate include direct patterning by photolithography and patterning by etching. From the viewpoint of increased productivity and shorter processing time due to a reduction in the number of steps, direct patterning by photolithography is preferred.

[0396] <Process of irradiating active chemical rays through a light mask>

[0397] The method for manufacturing a display device using the negative photosensitive resin composition of the present invention includes a step of irradiating an active chemical ray onto a coating of the negative photosensitive resin composition through a photomask. Examples of methods for irradiating an active chemical ray onto a coating of the negative photosensitive resin composition through a photomask include, for example, a pattern forming exposure method using an exposure machine such as a stepper, a scanner, a mirror projection mask exposure machine (MPA), or a parallel light mask exposure machine (PLA).

[0398] The exposure wavelength for active chemical 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 for active chemical rays is preferably 450 nm or less, more preferably 420 nm or less, and even more preferably 380 nm or less. Furthermore, mercury lamp gamma rays (wavelength 313 nm), i-rays (wavelength 365 nm), h-rays (wavelength 405 nm), or gamma rays (wavelength 436 nm), or a mixture of i-rays, h-rays, and gamma rays, are particularly preferred. Examples of active chemical rays include, for example, ultraviolet light, visible light, electron beams, X-rays, XeF (wavelength 351 nm) lasers, XeCl (wavelength 308 nm) lasers, KrF (wavelength 248 nm) lasers, or ArF (wavelength 193 nm) lasers. The exposure dose for active chemical rays, measured in i-ray illuminance, is preferably 100 J / m². 2 (10mJ / cm 2 ~30,000 J / m 2 (3,000mJ / cm 2 )the following.

[0399] As a photomask, a photomask having a pattern including a light-transmitting portion and a light-shielding portion is preferably used, and a halftone photomask having a semi-transparent portion with a transmittance lower than that of the light-transmitting portion and a transmittance higher than that of the light-shielding portion between the light-transmitting portion and the light-shielding portion. By exposing using a halftone photomask, a pattern with a stepped shape can be formed after development. It should be noted that in the pattern with a stepped shape, the position formed by the exposed portion obtained by irradiating the light-transmitting portion with active chemical rays corresponds to a thick film portion, and the position formed by the halftone exposed portion obtained by irradiating the semi-transparent portion with active chemical rays corresponds to a thin film portion. The halftone photomask has the aforementioned positions where the light-transmitting portion and the aforementioned semi-transparent portion are adjacent. By having the aforementioned positions where the light-transmitting portion and the semi-transparent portion are adjacent, a pattern having the aforementioned thick film portion corresponding to the light-transmitting portion on the photomask after development, and the aforementioned thin film portion corresponding to the semi-transparent portion on the photomask, can be formed. Furthermore, as a halftone photomask, the aforementioned positions where the light-shielding portion and the aforementioned semi-transparent portion are adjacent are used. A pattern can be formed having an opening corresponding to the light-blocking portion on the photomask after development, and a thin film portion corresponding to the semi-transparent portion on the photomask. By having the aforementioned positions on the halftone photomask, a stepped pattern comprising the thick film portion, the thin film portion, and the opening portion can be formed after development.

[0400] Let the transmittance of the light-transmitting portion in the above halftone mask be set to (%T). FT When )%, the transmittance of the above semi-transparent portion (%T) HT )% is preferably (%T) FT The transmittance of the semi-transparent portion is 10% or more, more preferably 15% or more, further preferably 20% or more, and particularly preferably 25% or more. HT If the transmittance (%T) of the semi-transparent portion is within the above range, the exposure during the formation of stepped patterns can be reduced, thereby shortening the cycle time. On the other hand, the transmittance (%T) of the semi-transparent portion... HT )% is preferably (%T) FT The transmittance of the semi-transparent portion is 60% or less, more preferably 55% or less, further preferably 50% or less, and particularly preferably 45% or less. HT If the thickness difference is within the range described above, the thickness difference between the thick film portion and the thin film portion, and the thickness difference between adjacent thin film portions on both sides of any step, can be sufficiently large, thereby suppressing the degradation of the light-emitting element. Furthermore, since a sufficient thickness difference can be achieved with just one layer of a pattern having a step shape, the processing time can be shortened.

[0401] In a stepped pattern obtained by irradiating active chemical rays through a halftone mask, the transmittance (%T) of the semi-transparent portion will be... HT )% is (%T) FTIn the case of 30% of the film, the film thickness of the thin film portion is set to (T). HT30 μm, and the transmittance of the semi-transparent portion (%T) HT )% is (%T) FT In the case of 20% of the film thickness, the film thickness of the thin film portion is set to (T). HT20 In the case of )μm, (T HT30 ) and (T HT20 ) film thickness difference (ΔT HT30-HT20 The thickness difference (ΔT) 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. If 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 adjacent thin film portions on both sides of any step, can be sufficiently large, thereby suppressing the degradation of the light-emitting element. Furthermore, since a sufficient film thickness difference is achieved with just one layer of the pattern having a step shape, the processing time can be shortened. On the other hand, the film thickness difference (ΔT) HT30-HT20 The thickness difference 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. If the film thickness difference is within the above range, the film thickness deviation caused by slight variations in exposure due to the device, etc., can be reduced, thereby improving film thickness uniformity and yield in the manufacture of organic EL displays.

[0402] After exposure, post-exposure baking can be performed. By performing post-exposure baking, effects such as improved resolution after development or increased allowable range of development conditions can be expected.

[0403] <The process of forming a pattern by developing with an alkaline solution>

[0404] The method for manufacturing a display device using the negative photosensitive resin composition of the present invention includes a step of (3) developing the negative photosensitive resin composition using an alkaline solution to form a pattern. As a method of developing the negative photosensitive resin composition using an alkaline solution after irradiation with an active chemical ray through a photomask, an example is an automatic developing machine. Because the negative photosensitive resin composition has negative photosensitivity, after development, the unexposed areas are removed by the developing solution, and an embossed pattern can be formed. Furthermore, by using an alkaline solution for development, the generation of developing residue in the openings can be suppressed, and the light emission reliability of the display device can be improved.

[0405] As the developer, an alkaline solution is preferred. As the alkaline solution, an organic alkaline solution or an aqueous solution of a compound exhibiting alkalinity is preferred; examples include diethanolamine, sodium hydroxide, potassium hydroxide, sodium carbonate, or potassium carbonate. On the other hand, from the viewpoint of reducing metallic impurities and improving the reliability of the display device, the alkaline solution preferably contains one or more selected from tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine, and triethylamine, and more preferably contains one or more selected from tetramethylammonium hydroxide and tetraethylammonium hydroxide. Organic solvents can also be used as the developer. A mixed solution containing both an organic solvent and a solvent that is unsuitable for the negative photosensitive resin composition can also be used as the developer.

[0406] 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. If the alkali concentration is within the above range, the generation of residue after development can be suppressed, and the cycle time during development can be shortened.

[0407] Examples of development methods include paddle development, jet development, and immersion development. From the viewpoint of suppressing equipment contamination during development and reducing process costs due to reduced developer usage, paddle development is preferred. By suppressing equipment contamination during development, substrate contamination during development can be suppressed, thereby improving the reliability of the display device. On the other hand, from the viewpoint of suppressing residue generation after development, jet development is preferred. Furthermore, from the viewpoint of reducing developer usage and reducing process costs due to developer reuse, immersion development is preferred.

[0408] The development time is preferably 5 seconds or more, more preferably 10 seconds or more, further preferably 30 seconds or more, and particularly preferably 1 minute or more. If 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 development cycle time, the development time is preferably 30 minutes or less, more preferably 15 minutes or less, further preferably 10 minutes or less, and particularly preferably 5 minutes or less. It is preferable to wash the resulting embossed pattern with a rinsing solution after development. As the rinsing solution, water is preferred when using an alkaline aqueous solution as the developer. As the rinsing solution, aqueous solutions of alcohols, aqueous solutions of esters, aqueous solutions of acidic compounds, or organic solvents can be used.

[0409] <Process for curing the pattern>

[0410] The method for manufacturing a display device using the negative photosensitive resin composition of the present invention preferably includes, after the step of developing the negative photosensitive resin composition with an alkaline solution as described in (3) above, a step of photocuring the pattern. As the step of photocuring the pattern, it is preferable to irradiate the pattern of the negative photosensitive resin composition with active chemical rays. The method and the active chemical rays used for irradiating are the same as the step of irradiating the coating of the negative photosensitive resin composition with active chemical rays through a photomask as described in (2) above.

[0411] By performing a photocuring process on the pattern, the crosslinking density of the pattern is increased, and the amount of low-molecular-weight components that cause degassing is reduced, thereby improving the reliability of the display device with the pattern of the negative photosensitive resin composition. Furthermore, when the pattern of the negative photosensitive resin composition is a stepped pattern, pattern backflow during thermal curing can be suppressed, and even after thermal curing, a stepped pattern with a sufficient film thickness difference between the thick and thin film portions can be formed. In addition, by maintaining the backflow properties of the film surface during thermal curing, flatness is improved, and panel yield reduction can be suppressed. Furthermore, in the manufacture of an organic EL display with a pattern of the negative photosensitive resin composition, the contact area with the vapor deposition mask during the formation of the organic EL layer can be minimized, thereby suppressing panel yield reduction and improving the reliability of the light-emitting elements.

[0412] In the case where the photomask used in the above-mentioned step (2) of irradiating the coating of the negative photosensitive resin composition with reactive chemical rays through a photomask is a halftone photomask, the exposure amount of the reactive chemical rays in the step of photocuring the above-mentioned pattern is set to (E BLEACH )mJ / cm 2 In the process of irradiating active chemical rays through a photomask as described above (2), the exposure amount in the transmission part of the photomask is set as (E). EXPO )mJ / cm 2 At that time, the exposure ratio (E) BLEACH ) / (E EXPO The exposure ratio is preferably 0.1 or higher, more preferably 0.3 or higher, even more preferably 0.5 or higher, even more preferably 0.7 or higher, and particularly preferably 1 or higher. If the exposure ratio is within the above range, pattern reflow during the thermal curing of the pattern in the negative photosensitive resin composition can be suppressed. Furthermore, it can suppress the decrease in panel yield. From the viewpoint of improving step film thickness, the exposure ratio is preferably 0.5 or higher, more preferably 0.7 or higher, and even more preferably 1 or higher. Furthermore, from the viewpoint of improving yield, the exposure ratio is preferably less than 4, more preferably less than 3.5, and even more preferably less than 3.

[0413] After obtaining the pattern of the negative photosensitive resin composition, intermediate baking can be performed. By performing intermediate baking, the resolution after thermosetting is improved, and the shape of the pattern after thermosetting can be arbitrarily controlled.

[0414] <The process of heating a pattern to obtain a cured pattern>

[0415] A method for manufacturing a display device using the negative photosensitive resin composition of the present invention includes a step of (4) heating a pattern of the negative photosensitive resin composition 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, for example, using an oven, a hot plate, infrared radiation, a rapid annealing apparatus, or a laser annealing apparatus. By heating the pattern of the negative photosensitive resin composition to thermally cure it, the heat resistance of the cured film can be improved, and a low-cone pattern can be formed.

[0416] From the viewpoint of improving the heat resistance of the cured film and forming a low-conical pattern after heat curing, the heat curing temperature is preferably 150°C or higher, more preferably 200°C or higher, and even more preferably 250°C or higher. On the other hand, from the viewpoint of shortening the cycle 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. From the viewpoint of forming a low-conical pattern after heat curing, the heat curing time is preferably 1 minute or more, more preferably 5 minutes or more, even more preferably 10 minutes or more, and particularly preferably 30 minutes or more. On the other hand, from the viewpoint of shortening the cycle time, the heat curing time is preferably 300 minutes or lower, more preferably 250 minutes or lower, even more preferably 200 minutes or lower, and particularly preferably 150 minutes or lower. Furthermore, heat curing can be achieved in two or more stages, such as heat curing at 150°C for 30 minutes followed by heat curing at 250°C for 30 minutes.

[0417] Examples of suitable atmospheres for thermosetting include air, oxygen, nitrogen, helium, neon, argon, krypton, or xenon, 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 cycle time during thermosetting, air is preferred. Furthermore, from the viewpoint of improving the reliability of the light-emitting element, a gas atmosphere containing 1 to 10,000 ppm (0.0001 to 1% by mass) of oxygen, or a vacuum, is preferred. As for 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 of oxygen is even more preferred.

[0418] Example

[0419] The present invention is further illustrated by the following examples and comparative examples, but the invention is not limited to these scopes. It should be noted that substances using abbreviations in the compounds used are listed below by name.

[0420] 6FDA: 2,2-(3,4-dicarboxyphenyl)hexafluoropropane dianhydride; 4,4'-hexafluoropropane-2,2-diyl-bis(1,2-phthalic anhydride)

[0421] A-BPEF: "NK ESTER" (registered trademark) A-BPEF (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.; 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene)

[0422] A-DCP: "NK ESTER" (registered trademark) A-DCP (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.; dimethyloltricyclodecane diacrylate)

[0423] APC: Argentum-Palladium-Cupper (silver-palladium-copper alloy)

[0424] BAHF: 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane

[0425] BAPF: 9,9-bis(3-amino-4-hydroxyphenyl)fluorene

[0426] BFE: 1,2-bis(4-formylphenyl)ethane

[0427] BGPF: 9,9-bis(4-epoxypropoxyphenyl)fluorene

[0428] Bk-A1103: "CHROMOFINE" (registered trademark) BLACK A1103 (manufactured by Dainippon Seika Kogyo Co., Ltd.; azo black pigment with a primary particle size of 50-100 nm)

[0429] Bk-CBF1: Surface coated with benzofuranone-based black pigment

[0430] Bk-S0084: "PALIOGEN" (registered trademark) BLACK S0084 (manufactured by BASF; perylene-based black pigment with a primary particle size of 50-100 nm)

[0431] Bk-S0100CF: "IRGAPHOR" (registered trademark) BLACK S0100CF (manufactured by BASF; benzofuranone-based black pigment with a primary particle size of 40-80nm)

[0432] cyEpoTMS: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane

[0433] D.BYK-167: "DISPERBYK" (registered trademark)-167 (manufactured by Big Kemmy Japan Co., Ltd.; a polyurethane dispersant with tertiary amines, amine value of 13 mg KOH / g (solid content concentration: 52% by mass)).

[0434] DNFLN: 2,7-dinitro-9-fluorenone

[0435] DPCA-60: "KAYARAD" (registered trademark) DPCA-60 (manufactured by Nippon Kayaku Co., Ltd.; ε-caprolactone-modified dipentaerythritol hexaacrylate with a 6-oxypentylcarbonyl structure in the molecule)

[0436] DPHA: "KAYARAD" (registered trademark) DPHA (manufactured by Nippon Kayaku Co., Ltd.; dipentaerythritol hexaacrylate)

[0437] GMA: Glycidyl methacrylate

[0438] HA: N,N'-bis[5,5'-hexafluoropropane-2,2-diyl-bis(2-hydroxyphenyl)]bis(3-aminobenzoic acid amide)

[0439] IDN-1: 1,1-Bis[4-(2-Acryloyloxyethoxy)phenyl]indane

[0440] IGZO: Indium gallium zinc oxide

[0441] ITO: Indium Tin Oxide

[0442] MAA: Methacrylic acid

[0443] MAP: 3-Aminophenol; m-Aminophenol

[0444] MBA: 3-Methoxy-n-Butyl Acetate

[0445] MeTMS: Methyltrimethoxysilane

[0446] MgAg: Magnesium-Argentum (Magnesium-Silver Alloy)

[0447] NA: 5-norbornene-2,3-dicarboxylic anhydride; Nadic anhydride

[0448] NC-7300L: An epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) containing a naphthalene backbone, a benzene backbone, and two epoxy groups.

[0449] NMP: N-methyl-2-pyrrolidone

[0450] ODB-HBT: A mixture of dicarboxylic acid derivatives obtained by reacting bis(4-carboxyphenyl) ether with 1-hydroxy-1,2,3-benzotriazole.

[0451] ODPA: Bis(3,4-dicarboxyphenyl) ether dianhydride; Oxybis(phthalic acid) dianhydride

[0452] PB60: CI Pigment Blue 60

[0453] PR179: CI Pigment Red 179

[0454] PY139: CI Pigment Yellow 139

[0455] PY192: CI Pigment Yellow 192

[0456] PGMEA: Propylene glycol monomethyl ether acetate

[0457] PHA: Phthalic anhydride

[0458] PhTMS: Phenylacetyltrimethoxysilane

[0459] S-20000: "SOLSPERSE" (registered trademark) 20000 (manufactured by Lubrizol; a polyoxyethylene ether dispersant with a tertiary amine content of 32 mg KOH / g (solid content concentration: 100% by mass)).

[0460] SiDA: 1,3-bis(3-aminopropyl)tetramethyldisiloxane

[0461] STR: Styrene

[0462] TCDM: Tricyclic methacrylate [5.2.1.0] 2,6 Decane-8-yl ester; Dihydroxymethyl-tricyclodecane dimethacrylate

[0463] THPHA: 1,2,3,6-Tetrahydrophthalic anhydride

[0464] TMAH: Tetramethylammonium hydroxide

[0465] TMOS: Tetramethoxysilane

[0466] TPK-1227: Carbon black with a surface treatment incorporating sulfonic acid groups (manufactured by CABOT).

[0467] TR-FR-201: 9,9-bis(4-epoxypropoxyphenyl)fluorene (Tronly)

[0468] WR-301: “ADEKA ARKLS” (registered trademark) WR-301 (manufactured by ADEKA; a resin containing polycyclic side chains obtained by reacting a carboxylic anhydride with an aromatic compound having an epoxy group and an unsaturated carboxylic acid through a ring-opening addition reaction; acid equivalent: 560, double bond equivalent: 450)

[0469] ZXR-1816H: An acid-modified epoxy resin obtained by reacting a carboxylic anhydride with an epoxy resin having structural units including a tricyclic decane skeleton, a benzene skeleton, and an epoxy group with an unsaturated carboxylic acid through a ring-opening addition reaction. Acid equivalent: 570, double bond equivalent: 520 g / mol (manufactured by Nippon Kayaku Co., Ltd.)

[0470] It should be noted that the hydroxyl-containing diamine compound (HA) used in Synthesis Example 4 was synthesized by a known method.

[0471]

[0472] As (A) alkali-soluble resins, the compositions of the resins obtained in Synthetic Examples 1 to 10 are summarized in Table 1. It should be noted that Synthetic Examples 1 to 5, 7, 8, and 10 are based on the method described in International Publication No. 2017 / 057281, Synthetic Example 6 is based on the method described in International Publication No. 2017 / 057143, and Synthetic Example 9 is based on the method described in International Publication No. 2017 / 159876. Each resin is synthesized using a known method. In Synthetic Example 10, GMA having epoxy groups reacts with the carboxyl groups in a resin derived from MAA, causing all epoxy groups of the GMA to undergo ring-opening addition.

[0473] [Table 1]

[0474] Table 1

[0475]

[0476] Example 1: Synthesis of benzofuranone-based black pigment (Bk-CBF1) for surface coating

[0477] As a black pigment, 150g of Bk-S0100CF (untreated) as a benzofuranone-based black pigment was added to a glass container containing 2,850g of deionized water and stirred to obtain an aqueous pigment suspension. This suspension was then dispersed in a horizontal bead mill filled with 0.4mm φ zirconia beads, and the entire volume was discharged back into the original glass container. While stirring again, the liquid temperature of the aqueous pigment suspension was raised to 60°C and stirred for 30 minutes.

[0478] Compared to an aqueous pigment suspension, a liquid obtained by diluting an aqueous sodium silicate solution (Na2O·nSiO2·mH2O; 30% by mass of sodium oxide and 10% by mass of silica) with deionized water was added, with the amount of silica coating being 10.0 parts by mass relative to 100 parts by mass of black pigment (SiO2 conversion value), and 0.001 mol / L sulfuric acid, so that silica precipitates on the surface of the black pigment particles and is coated. Next, relative to the aqueous pigment suspension, with the alumina coating amount being 2.0 parts by mass relative to 100 parts by mass of black pigment (calculated as Al2O3), a liquid obtained by diluting sodium aluminate aqueous solution (Na2O·nAl2O3·mH2O; 40% by mass of sodium oxide and 50% by mass of alumina) 100 times with deionized water and 0.001 mol / L sulfuric acid were added to precipitate alumina onto the surface of the silica coating layer. The filtration and washing process was then repeated three times, followed by dispersion treatment in a horizontal bead mill filled with 0.4 mm φ zirconia beads, and filtration yielded a black filter. After drying in a drying oven, it was granulated by dry grinding to obtain a surface-coated benzofuranone-based black pigment (Bk-CBF1).

[0479] The results of analysis by time-of-flight secondary ion mass spectrometry and X-ray diffraction showed that the coating amounts of silica and alumina of the obtained surface-coated benzofuranone-based black pigment (Bk-CBF1) were 10.0 parts by mass (SiO2 equivalent) and 2.0 parts by mass (Al2O3 equivalent) per 100 parts by mass of the black pigment, respectively, with an average coating rate of 97.5% relative to the pigment coating layer.

[0480] Preparation of Pigment Dispersion (Bk-1) Example 1

[0481] 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 for diffusion. Then, 103.5 g of Bk-S0100CF as a colorant was weighed and mixed, and stirred for 30 minutes. Wet dispersion was performed using a horizontal bead mill filled with 0.40 mm φ zirconia beads to achieve a number-average particle size of 100 nm, resulting in a pigment dispersion (Bk-1) with a solid content of 15% by mass and a colorant / dispersant ratio of 75 / 25 (mass ratio). The number-average particle size of the pigment in the resulting pigment dispersion was 100 nm.

[0482] Preparation of Pigment Dispersion (Bk-2) in Example 2

[0483] 92.0 g of a 30% by mass MBA solution of polyimide (PI-1) obtained in Synthesis Example 1 as resin, 27.6 g of S-20000 as dispersant, and 717.6 g of MBA as solvent were weighed and mixed. After diffusion by stirring for 10 minutes, 82.8 g of Bk-S0100CF as colorant was weighed and mixed and stirred for 30 minutes. Wet media dispersion was performed using a horizontal bead mill filled with 0.40 mm φ zirconia beads to achieve a number average particle size of 100 nm, resulting in a pigment dispersion (Bk-2) with a solid content concentration of 15% by mass and a colorant / resin / dispersant ratio of 60 / 20 / 20 (mass ratio). The number average particle size of the pigment in the obtained pigment dispersion was 100 nm.

[0484] Preparation of pigment dispersions (Bk-3) to (Bk-8) in Examples 3-8

[0485] Based on the types and ratios of (D) colorant, (A1) first resin and (E) dispersant as recorded in Table 2-1, pigment dispersions were prepared in the same manner as in Preparation Example 2, and pigment dispersions (Bk-3) to (Bk-8) were obtained.

[0486] The composition of modulation examples 1 to 8 is summarized in Table 2-1.

[0487] [Table 2-1]

[0488] Table 2-1

[0489]

[0490] It should be noted that the following shows the maximum transmission wavelengths of the colorant Bk-S0100CF contained in pigment dispersions (Bk-1) to (Bk-3) as (Da) black agents, Bk-S0084 contained in pigment dispersion (Bk-4), and the colorant (a mixture of PR179, PY192 and PB60) contained in pigment dispersion (Bk-9).

[0491] Bk-S0100CF: 340nm

[0492] Bk-S0084: 350nm

[0493] A mixture of PR179, PY192 and PB60: 390nm

[0494] A summary of the (C1-1) oxime ester photopolymerization initiators used in each example and comparative example is shown in Table 2-2.

[0495] [Table 2-2]

[0496] Table 2-2

[0497]

[0498] Furthermore, the following shows the respective 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 the various embodiments and comparative examples.

[0499]

[0500]

[0501] Furthermore, the following shows the structural units of the acid-modified epoxy resin (ZXR-1816H) and the acid-modified epoxy resin (AE-1) obtained in Synthesis Example 8. The acid-modified epoxy resin (ZXR-1816H) has the structural units shown in general formula (37a). The acid-modified epoxy resin (AE-1) has the structural units shown in general formula (38a).

[0502]

[0503] The following shows the evaluation methods in each embodiment and comparative example.

[0504] (1) Weight-average molecular weight of resin

[0505] Using a GPC analytical apparatus (HLC-8220; manufactured by Higashi Soy Co., Ltd.), with tetrahydrofuran or NMP as the mobile phase, the weight-average molecular weight of polystyrene was determined by measuring the molecular weight at near room temperature according to "JIS K7252-3 (2008)".

[0506] (2) Acid value, acid equivalent

[0507] Using an automatic potentiometric titration apparatus (AT-510; manufactured by Kyoto Electron Kogyo Co., Ltd.), a 0.1 mol / L sodium hydroxide / ethanol solution was used as the titrant, and xylene / N,N-dimethylformamide was used as the titrant solvent in a 1:1 mass ratio. The acid value (unit: mgKOH / g) was determined by potentiometric titration according to JIS K2501 (2003). The acid equivalent (unit: g / mol) was then calculated from the measured acid value.

[0508] (3) Double bond equivalent

[0509] An automatic potentiometric titration apparatus (AT-510; manufactured by Kyoto Electron Kogyo Co., Ltd.) was used, employing an iodine monochloride solution (a mixed solution of iodine trichloride = 7.9 g, iodine = 8.9 g, and acetic acid = 1,000 mL) as the iodine supply source, a 100 g / L potassium iodide aqueous solution as a trapping solution for unreacted iodine, and a 0.1 mol / L sodium thiosulfate aqueous solution as the titrant, based on JIS standards. The method described in Section 6, "Iodine Value," of K0070:1992, "Test Methods for Acid Value, Saponification Value, Ester Value, Iodine Value, Hydroxyl Value, and Unsaponifiable Matter of Chemical Products," was used to determine the iodine value of resins via the Wigges method. The double bond equivalent (in g / mol) was calculated from the determined iodine value (in gI / 100g).

[0510] (4) Number-average particle size of pigment

[0511] Using a zeta potential / particle size / molecular weight measuring device (Zeta Saizerana ZS; manufactured by Sismex Co.), and with PGMEA as the diluent, the pigment dispersion was diluted to 1.0 × 10⁻⁶. -5 The number-average particle size of the pigment in the pigment dispersion was measured by irradiating it with a laser with a wavelength of 633 nm at a concentration of ~40% by volume, setting the refractive index of the diluent to that of PGMEA, setting the refractive index of the test object to 1.6, and using a laser with a wavelength of ~40% by volume.

[0512] (5) Pretreatment of substrate

[0513] A glass substrate (manufactured by Geomatic Co., Ltd.; hereinafter, "ITO substrate") on which ITO is sputtered to form a 100nm film is used, and then subjected to a 100-second UV-O3 cleaning process using a benchtop surface treatment apparatus (PL16-110; manufactured by Sen Special Light Source Co., Ltd.). A Si wafer (manufactured by Electro-Xex Engineering Co., Ltd.) is used, and then subjected to a dehydration baking process by heating at 130°C for 2 minutes using a hot plate (HP-1SA; manufactured by Azwan Co., Ltd.).

[0514] (6) Film thickness measurement

[0515] Using a surface roughness / profile shape measuring machine (SURFCOM1400D; manufactured by Tokyo Seijinsha), with a measurement magnification of 10,000x, a measurement length of 1.0 mm, and a measurement speed of 0.30 mm / s, the film thickness was measured after development and after heat curing after pre-baking.

[0516] (7) Sensitivity

[0517] Hereinafter, using the method described in Example 1, a pattern-forming exposure apparatus (PEM-6M lithography machine; manufactured by Union Optics) was used, with a grayscale mask for sensitivity measurement (MDRM MODEL 4000-5-FS; manufactured by Opto-Line International), and pattern-forming exposure was performed using i-rays (wavelength 365nm), h-rays (wavelength 405nm), and g-rays (wavelength 436nm) from an ultra-high pressure mercury lamp. Development was then performed using a small lithography developing apparatus (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.) to produce a post-developed film of a negative photosensitive resin composition. The image pattern of the developed film was observed using an FPD / LSI inspection microscope (OPTIPHOT-300; manufactured by Nicon Co., Ltd.), and the sensitivity was set as the exposure amount (value of an i-ray illuminometer) with a 20μm line-to-gap pattern width of 1:1. The sensitivity was determined as follows, and a value of 90 mJ / cm² was set. 2 The following values, A+, A, B, and C, are set as qualified, and the sensitivity is set to 60 mJ / cm. 2 The following values, A+, A, and B, are set as having good sensitivity, with a sensitivity of 45 mJ / cm. 2 The following values, A+ and A, are set to excellent sensitivity.

[0518] A+: Sensitivity is 30mJ / cm 2 the following

[0519] A: Sensitivity exceeds 30mJ / cm 2 And it is 45mJ / cm 2 the following

[0520] B: Sensitivity exceeds 45mJ / cm 2 And it is 60mJ / cm 2 the following

[0521] C: Sensitivity exceeds 60mJ / cm 2 And it is 90mJ / cm 2 the following

[0522] D: Sensitivity exceeds 90mJ / cm 2 And it is 150mJ / cm 2 the following

[0523] E: Sensitivity exceeds 150 mJ / cm 2 And it is 500mJ / cm 2 the following.

[0524] (8) Cross-sectional shape of the pattern after development

[0525] Hereinafter, using the method described in Example 1, a double-sided alignment single-sided exposure apparatus (PEM-6M lithography machine; manufactured by Union Optics) was used. Pattern formation exposure was performed using i-rays (wavelength 365nm), h-rays (wavelength 405nm), and g-rays (wavelength 436nm) from an ultra-high pressure mercury lamp, separated by a grayscale mask for sensitivity measurement (MDRM MODEL 4000-5-FS; manufactured by Opto-Line International). Development was then performed using a small lithography developing apparatus (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.) to produce a post-developed film of a negative photosensitive resin composition. Using a field emission scanning electron microscope (S-4800; manufactured by Hitachi High Tech Noroze), the cross-section of the image pattern of the developed film with a gap width of 20μm and the gap pattern was observed, and the cone angle of the cross-section was measured. As follows, sections with a cone angle of 60° or less, A+, A, and B are considered acceptable; sections with a cone angle of 45° or less, A+ and A are considered to have good pattern shape; and sections with a cone angle of 30° or less, A+ is considered to have excellent pattern shape.

[0526] A+: The cone angle of the cross section is less than 30°.

[0527] A: The cone angle of the cross section exceeds 30° but is less than 45°.

[0528] B: The cone angle of the cross section exceeds 45° but is less than 60°.

[0529] C: The cone angle of the cross section exceeds 60° but is less than 70°.

[0530] D: The cone angle of the cross section exceeds 70° but is less than 80°.

[0531] E: The cone angle of the cross section exceeds 80° but is less than 180°.

[0532] (9) Halftone characteristics

[0533] Hereinafter, using the method described in Example 1, a pre-baked film of a negative photosensitive resin composition was formed on an ITO substrate with a film thickness of 5 μm. Using a double-sided alignment single-sided exposure apparatus (PEM-6M lithography machine; manufactured by Union Optics), and with a halftone photomask for halftone characteristic evaluation in between, the exposure amount of the light-transmitting portion was adjusted to the sensitivity given that the pre-baked film thickness was 5 μm. Pattern formation exposure was performed using i-rays (wavelength 365 nm), h-rays (wavelength 405 nm), and g-rays (wavelength 436 nm) from an ultra-high pressure mercury lamp. After development using a small photolithography developing apparatus (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.), a cured film of the negative photosensitive resin composition was produced using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Service System Co., Ltd.).

[0534] As a halftone mask, a photomask having a light-transmitting portion, a light-blocking portion, and a semi-transparent portion between the light-transmitting portion and the light-blocking portion was used. The transmittance (%T) of the semi-transparent portion is... HT )% represents the transmittance of the light-transmitting portion (%T) mentioned above. FT Positions where the light-transmitting portion is 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% of the light-transmitting portion. The light-transmitting portion is adjacent to the semi-transmitting portion, and the semi-transmitting portion is adjacent to the light-shielding portion. Positions where the pattern shapes of the light-transmitting portion, the semi-transmitting portion, and the light-shielding portion are all linear. Positions where the light-transmitting portion and the light-shielding portion are both quadrilateral. Positions where the pattern size of the light-transmitting portion is 2μm, 5μm, 10μm, 15μm, 20μm, 30μm, 40μm, 50μm, or 100μm. Furthermore, the pattern size of the light-shielding portion is 10μm. On the other hand, the patterns having the aforementioned semi-transparent portions are positioned at sizes of 2μm, 5μm, 10μm, 15μm, 20μm, 25μm, 30μm, 35μm, 40μm, 45μm, 50μm, or 100μm. As an example of a halftone mask, an example of the arrangement and size of the light-transmitting portion, the light-blocking portion, and the semi-transparent portion is shown below. Figure 3 middle.

[0535] Using a surface roughness / profile shape measuring machine (SURFCOM1400D; manufactured by Tokyo Seijinsha), with a measurement magnification of 10,000x, a measurement length of 1.0 mm, and a measurement speed of 0.30 mm / s, the film thickness after development of the transparent portion and the film thickness after thermosetting were measured (T). FT ) μm. Regarding the semi-transparent portion, the film thickness after development and the film thickness after thermosetting were measured at locations with different transmittance (T). HT ) μm, calculate the minimum film thickness (T) after thermal curing in the semi-transparent portion of the residual film after development. HT / min) μm. The maximum step film thickness is calculated using the following formula as an indicator of halftone characteristics.

[0536] Maximum step film thickness = (T) FT )-(T HT / min ).

[0537] As determined below, A+, A, B, and C with a maximum step film thickness of 1.0 μm or more are considered acceptable; A+, A, and B with a maximum step film thickness of 1.5 μm or more are considered to have good halftone characteristics; and A+ and A with a maximum step film thickness of 2.0 μm or more are considered to have excellent halftone characteristics.

[0538] A+: Maximum step film thickness is 2.5 μm or more.

[0539] A: The maximum step thickness is greater than 2.0 μm and less than 2.5 μm.

[0540] B: The maximum step thickness is greater than 1.5 μm and less than 2.0 μm.

[0541] C: The maximum step thickness is greater than 1.0 μm and less than 1.5 μm.

[0542] D: The maximum step film thickness is greater than 0.5 μm and less than 1.0 μm.

[0543] E: The maximum step thickness is greater than 0.1 μm and less than 0.5 μm.

[0544] F: The maximum step film thickness is less than 0.1 μm or there is no film residue after development, making it impossible to determine.

[0545] (10) Residue at the opening

[0546] Hereinafter, using the method described in Example 1, a pattern-forming exposure was performed using a double-sided alignment single-sided exposure apparatus (PEM-6M lithography machine; manufactured by Union Optics Co., Ltd.) with i-rays (wavelength 365nm), h-rays (wavelength 405nm), and g-rays (wavelength 436nm) from an ultra-high pressure mercury lamp, through a gray-level mask for sensitivity measurement (MDRM MODEL 4000-5-FS; manufactured by Opto-Line International Co., Ltd.). After development using a small lithography developing apparatus (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.), a cured film of a negative photosensitive resin composition was produced using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Service System Co., Ltd.). The image pattern of the cured film was observed using an FPD / LSI inspection microscope (OPTIPHOT-300; manufactured by Niconico). The presence or absence of residue in the openings of the 20μm line and gap pattern was also observed. The following criteria were used to determine the residue levels: A+, A, and B were considered acceptable if the area of ​​residue presence in the openings was 10% or less; A+ and A were considered good if the area of ​​residue presence in the openings was 5% or less; and A+ was considered excellent if there was no residue presence in the openings.

[0547] A+: No residue in the opening, or the area of ​​residue in the opening is less than 1%.

[0548] A: The area of ​​residue present in the opening exceeds 1% but is less than 5%.

[0549] B: The area of ​​residue present in the opening exceeds 5% but is less than 10%.

[0550] C: The area of ​​residue present in the opening exceeds 10% but is less than 30%.

[0551] D: The area of ​​residue present in the opening exceeds 30% but is less than 50%.

[0552] E: The area of ​​residue present in the opening exceeds 50% but is less than 100%.

[0553] (11) Light blocking property (optical density value (hereinafter, "OD value"))

[0554] Hereinafter, using the method described in Example 1, a pattern-forming exposure was performed using a double-sided alignment single-sided exposure apparatus (PEM-6M lithography machine; manufactured by Union Optics), with a grayscale mask for sensitivity measurement (MDRM MODEL 4000-5-FS; manufactured by Opto-Line International), and using i-rays (wavelength 365nm), h-rays (wavelength 405nm), and g-rays (wavelength 436nm) from an ultra-high pressure mercury lamp. After development using a small lithography developing apparatus (AD-2000; manufactured by Takizawa Sangyo), a cured film of a negative photosensitive resin composition was produced using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Service System). The incident light intensity (I0) and transmitted light intensity (I) of the cured film were measured using a transmission density meter (X-Rite361T(V); manufactured by X-Rite). As an indicator of light-blocking properties, the OD value is calculated using the following formula.

[0555] OD value = log 10 (I0 / I).

[0556] (12) Insulation properties (surface resistivity)

[0557] Hereinafter, using the method described in Example 1, a pattern-forming exposure was performed using a double-sided alignment single-sided exposure apparatus (PEM-6M lithography machine; manufactured by Union Optics), with a grayscale mask for sensitivity measurement (MDRM MODEL 4000-5-FS; manufactured by Opto-Line International), and using i-rays (wavelength 365nm), h-rays (wavelength 405nm), and g-rays (wavelength 436nm) from an ultra-high pressure mercury lamp. After development using a small lithography developing apparatus (AD-2000; manufactured by Takizawa Sangyo), a cured film of a negative photosensitive resin composition was produced using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Service System). The surface resistivity (Ω / □) of the cured film was measured using a high-resistivity meter (“High Resistivity” UP; manufactured by Mitsubishi Chemical Co., Ltd.).

[0558] (13) Light emission characteristics of organic EL displays

[0559] (Method for manufacturing organic EL displays)

[0560] exist Figure 4 The diagram shows a schematic of the substrate used. First, a 10nm ITO transparent conductive film is formed on the entire surface of a 38×46mm alkali-free glass substrate 47 by sputtering, serving as the first electrode 48, and then etched to form a transparent electrode. Furthermore, an auxiliary electrode 49 is simultaneously formed to facilitate the removal of the second electrode. Figure 4(Step 1) The obtained substrate was ultrasonically cleaned for 10 minutes using "Semicoclean" (registered trademark) 56 (manufactured by Fullwitch Chemical Co., Ltd.), and then washed with ultrapure water. Next, a negative photosensitive resin composition was coated and pre-baked on the substrate using the method described in Example 1. After pattern formation exposure through a photomask with a predetermined pattern, and after development and rinsing, it was thermally cured by heating. Using the above method, an insulating layer 50 was formed in the effective area of ​​the substrate, with openings 70 μm wide and 260 μm long arranged at a spacing of 155 μm along the width direction and 465 μm along the length direction, and each opening exposing the first electrode. Figure 4 (Step 2) It should be noted that this opening ultimately becomes the light-emitting pixel of the organic EL display. In addition, the effective area of ​​the substrate is 16 mm square, and the thickness of the insulating layer 50 is formed at approximately 1.0 μm.

[0561] Next, an organic EL display was fabricated using a substrate on which the first electrode 48, auxiliary electrode 49, and insulating layer 50 were formed. As a pretreatment, nitrogen plasma treatment was performed, and then an organic EL layer 51 containing the light-emitting layer was formed by vacuum evaporation. Figure 4 (Step 3) It should be noted that the vacuum degree during vapor deposition is 1×10⁻⁶. -3 Below Pa, the substrate is rotated relative to the evaporation source during evaporation. First, compound (HT-1) is deposited for 10 nm as a hole injection layer, and compound (HT-2) is deposited for 50 nm as a hole transport layer. Next, in the light-emitting layer, compound (GH-1) as the host material and compound (GD-1) as the dopant material are deposited at a doping concentration of 10% to a thickness of 40 nm. Then, compound (ET-1) and compound (LiQ) are stacked at a volume ratio of 1:1 to a thickness of 40 nm as the electron transport material. It should be noted that the compound used in the organic EL layer is the same compound as the one described in International Publication No. 2017 / 057281.

[0562] Next, after depositing 2 nm of compound (LiQ), MgAg (magnesium / silver = 10 / 1 (volume ratio)) was deposited for 100 nm to form the second electrode 52, thus forming the reflective electrode. Figure 4 (Step 4) Then, under a low-humidity nitrogen atmosphere, an epoxy resin adhesive was used to bond the cover glass plate to seal it, thus fabricating four 5mm square bottom-emitting organic EL displays on a single substrate. It should be noted that the film thickness referred to here is the value displayed by a crystal vibrating film thickness monitor.

[0563] (Evaluation of luminescent properties)

[0564] Let the organic EL display fabricated by the above method emit light with a current density of 10 mA / cm² 2 using DC driving, and observe whether there are any defective emissions such as non-emitting areas or brightness unevenness. The fabricated organic EL display was maintained at 80 °C for 500 hours as a durability test. After the durability test, with a current density of 10 mA / cm² 2 let the organic EL display emit light using DC driving, and observe any changes in emission characteristics such as emission areas or brightness unevenness. As judged below, when the emission area before the durability test is set as 100%, those with an emission area after the durability test of 80% or more, namely A+, A, and B, are considered qualified; those with an emission area of 90% or more, namely A+ and A, are considered to have good emission characteristics; and those with an emission area of 95% or more, namely A+, are considered to have excellent emission characteristics.

[0565] A+: The emission area after the durability test is 95% or more

[0566] A: The emission area after the durability test is 90% or more and less than 95%

[0567] B: The emission area after the durability test is 80% or more and less than 90%

[0568] C: The emission area after the durability test is 70% or more and less than 80%

[0569] D: The emission area after the durability test is 50% or more and less than 70%

[0570] E: The emission area after the durability test is less than 50%.

[0571] [Example 1]

[0572] Under a yellow light, weigh 0.087 g of OXL-73 and 0.202 g of OXL-21, add 6.426 g of MBA and 5.100 g of PGMEA, and stir to dissolve. Next, add 5.165 g of a 30 mass% MBA solution of the polyimide (PI-1) obtained in Synthesis Example 1, 0.578 g of a 50 mass% MBA solution of b-1, and 1.446 g of a 50 mass% MBA solution of b-3, and stir to obtain a blend solution in a homogeneous form. Next, weigh 9.163 g of the pigment dispersion (Bk-1) obtained in Formulation Example 1, add 15.837 g of the blend solution obtained by the above method thereto, and stir to form a homogeneous solution. Then, filter the resulting solution through a filter with a pore size of 0.45 μmφ to prepare Composition 1.

[0573] The prepared composition 1 was coated on an ITO substrate using a spin coater (MS-A100; manufactured by Mikasa Co., Ltd.) at an arbitrary rotation speed. Then, a pre-baked film with a thickness of about 1.8 μm was produced by pre-baking at 110°C for 120 seconds using a buzzer hot plate (HPD-3000BZN; manufactured by Azuwan Co., Ltd.).

[0574] The pre-baked film was developed using a small photolithography developing apparatus (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.) with 2.38% by mass TMAH aqueous solution by jet development, and the time for complete dissolution of the pre-baked film (unexposed portion) was measured (Breaking Point; hereinafter, "BP").

[0575] The pre-baked film was prepared in the same manner as described above. Using a double-sided alignment, single-sided exposure apparatus (PEM-6M lithography machine; manufactured by Union Optics), and with a grayscale mask for sensitivity measurement (MDRM MODEL 4000-5-FS; manufactured by Opto-Line International), the pre-baked film was exposed for pattern formation using i-rays (wavelength 365nm), h-rays (wavelength 405nm), and g-rays (wavelength 436nm) from an ultra-high pressure mercury lamp. After exposure, it was developed using a small lithography developing apparatus (AD-2000; manufactured by Takizawa Sangyo) with a 2.38% (w / w) TMAH aqueous solution, followed by rinsing with water for 30 seconds. The development time was set to 1.5 times the BP.

[0576] After development, the film was heat-cured at 250°C using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Service Co., Ltd.) to produce a cured film with a thickness of approximately 1.2 μm. The heat curing conditions were: heat curing at 250°C for 60 minutes under a nitrogen atmosphere.

[0577] [Examples 2-66 and Comparative Examples 1-7]

[0578] Similar to Example 1, compositions 2 to 73 were prepared using the compositions described in Tables 3 to 7. Using each of the obtained compositions, films were formed on a substrate, similar to Example 1, and the photosensitivity, properties of the cured film, and luminescence properties were evaluated. These evaluation results are summarized in Tables 3 to 7. It should be noted that, for ease of comparison, the composition and evaluation results of Example 1 are listed in each of Tables 4 to 7.

[0579] It should be noted that the following shows the names corresponding to the abbreviations in Tables 3 to 7.

[0580] b-1: A-BPEF (“NK ESTER” (registered trademark) A-BPEF (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.; 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene))

[0581] b-2: IDN-1 (1,1-bis[4-(2-acryloyloxyethoxy)phenyl]indane)

[0582] b-3: DPHA (“KAYARAD” (registered trademark) DPHA (manufactured by Nippon Kayaku Co., Ltd.; dipentaerythritol hexaacrylate))

[0583] b-4: DPCA-60 (“KAYARAD” (registered trademark) DPCA-60 (manufactured by Nippon Kayaku Co., Ltd.; ε-caprolactone-modified dipentaerythritol hexaacrylate with a 6-oxypentylcarbonyl structure in the molecule)

[0584] b-5: A-DCP (“NK ESTER” (registered trademark) A-DCP (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.; dihydroxymethyl-tricyclodecane diacrylate))

[0585] d-1: Bk-S0100CF (“IRGAPHOR” (registered trademark) BLACK S0100CF (manufactured by BASF; benzofuranone-based black pigment with a primary particle size of 40-80 nm))

[0586] d-2: Bk-S0084 (“PALIOGEN” (registered trademark) BLACK S0084 (manufactured by BASF; perylene-based black pigment with a primary particle size of 50-100 nm))

[0587] d-3: Bk-A1103 (“CHROMOFINE” (registered trademark) BLACK A1103 (manufactured by Dainippon Seika Kogyo Co., Ltd.; azo black pigment with a primary particle size of 50-100 nm))

[0588] d-4: A mixture of PR179 / PY192 / PB60 (a mixture of CI Pigment Red 179 / CI Pigment Yellow 192 / CI Pigment Blue 60).

[0589] d-5: A mixture of PR179 / PY139 / PB60 (a mixture of CI Pigment Red 179 / CI Pigment Yellow 139 / CI Pigment Blue 60).

[0590] d-6: Bk-CBF1 (a black pigment coated with benzofuranone)

[0591] d-7: TPK-1227 (Carbon black with sulfonic acid group incorporation surface treatment (manufactured by CABOT))

[0592] e-1: S-20000 (“SOLSPERSE” (registered trademark) 20000 (manufactured by Lubrizol; a polyoxyethylene ether dispersant with a tertiary amine content of 32 mg KOH / g (solid content concentration: 100% by mass))

[0593] e-2: D.BYK-167 (“DISPERBYK” (registered trademark)-167 (manufactured by Big Kemmy Japan Co., Ltd.; a polyurethane dispersant with tertiary amines, amine value of 13 mg KOH / g (solid content concentration: 52% by mass))

[0594] f-1: TR-FR-201 (9,9-bis(4-epoxypropoxyphenyl)fluorene (Tronly))

[0595] g-1: DNFLN (2,7-dinitro-9-fluorenone)

[0596] [Table 3]

[0597] Table 3

[0598]

[0599] [Table 4]

[0600] Table 4

[0601]

[0602] [Table 5]

[0603] Table 5

[0604]

[0605] [Table 6]

[0606] Table 6

[0607]

[0608] [Table 7]

[0609]

[0610] [Example 67]

[0611] (Manufacturing method of organic EL display without polarizing layer)

[0612] An outline of the organic EL display being fabricated is shown below. Figure 5First, a chromium and gold laminate is formed on a 38×46mm alkali-free glass substrate 53 by electron beam evaporation, and the source electrode 54 and drain electrode 55 are formed by etching. Next, an APC (silver / palladium / copper = 98.07 / 0.87 / 1.06 (mass ratio)) film is sputtered to a thickness of 100nm, and patterned by etching to form an APC layer. Further, an ITO film is sputtered to a thickness of 10nm on top of the APC layer, and a reflective electrode 56 is formed as the first electrode by etching. After washing the electrode surface with oxygen plasma, an amorphous IGZO film is formed by sputtering, and an oxide semiconductor layer 57 is formed between the source and drain electrodes by etching. Next, a positive photosensitive polysiloxane material (SP-P2301; manufactured by Higashi Rei Co., Ltd.) film is formed by spin coating, and the vias 58 and pixel regions 59 are opened by photolithography, and then thermally cured to form a gate insulating layer 60. Then, gold is deposited into a film by electron beam evaporation and the gate electrode 61 is formed by etching, thereby fabricating an oxide TFT array.

[0613] Using the method described in Example 1 above, composition 1 is coated and pre-baked on an oxide TFT array to form a film. After pattern formation exposure through a photomask with a predetermined pattern, followed by development and washing to open the pixel area, it is thermally cured to form a light-shielding TFT protective layer / pixel segmentation layer 62. Using the above method, a pixel segmentation layer is formed in the effective area of ​​the substrate, with openings 70 μm wide and 260 μm long arranged at a spacing of 155 μm along the width direction and 465 μm along the length direction, each opening exposing a reflective electrode. It should be noted that these openings ultimately become the light-emitting pixels of the organic EL display. Furthermore, the effective area of ​​the substrate is 16 mm square, and the thickness of the pixel segmentation layer is approximately 1.0 μm.

[0614] Next, using the method described in (13) above, compound (HT-1) was used as a hole injection layer, compound (HT-2) as a hole transport layer, compound (GH-1) as a host material, compound (GD-1) as a dopant material, compound (ET-1) as an electron transport material, and compound (LiQ) to form an organic EL light-emitting layer 63. Then, MgAg (magnesium / silver = 10 / 1 (volume ratio)) was deposited to a film of 10 nm 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 sealing material (Stract Bond (registered trademark) XMF-T; manufactured by Mitsui Chemicals) under a low-humidity nitrogen atmosphere. Furthermore, an alkali-free glass substrate 66 was bonded to the sealing film, and four 5 mm square top-emitting organic EL displays without polarizing layers were fabricated on one substrate. It should be noted that the film thickness referred to here is the value displayed by a crystal vibrating film thickness monitor.

[0615] (Evaluation of luminescent properties)

[0616] At 10mA / cm 2 An organic EL display fabricated using the above method was driven to emit light using a DC drive. The brightness (Y') when external light irradiates the pixel segmentation layer and the brightness (Y0) when no external light irradiates it were measured. The contrast ratio was calculated using the following formula as an indicator of the reduction in external light reflection.

[0617] Contrast ratio = Y0 / Y'.

[0618] As determined below, a contrast ratio of 0.80 or higher (A+, A, and B) is considered acceptable; a contrast ratio of 0.90 or higher (A+ and A) is considered good at reducing external light reflection; and a contrast ratio of 0.95 or higher (A+) is considered excellent at reducing external light reflection. It has been confirmed that the organic EL display produced using the above method has a contrast ratio of 0.90 and can achieve reduced external light reflection.

[0619] A+: Contrast ratio of 0.95 or higher

[0620] A: Contrast ratio above 0.90 and below 0.95

[0621] B: Contrast ratio above 0.80 and below 0.90

[0622] C: Contrast ratio above 0.70 and below 0.80

[0623] D: Contrast ratio above 0.50 and below 0.70

[0624] E: Contrast ratio less than 0.50.

[0625] Explanation of symbols

[0626] 1. Glass substrate

[0627] 2 TFT

[0628] 3. Cured film for TFT planarization

[0629] 4, 56 Reflective Electrodes

[0630] 5a Pre-baked film

[0631] 5b Cured Pattern

[0632] 6. Mask

[0633] 7. Active chemical rays

[0634] 8 EL light-emitting layer

[0635] 9.64 Transparent Electrode

[0636] 10 Cured film for planarization

[0637] 11 Covered Glass

[0638] 34 Thick film department

[0639] 35a, 35b, 35c Thin Film Section

[0640] Inclined edges in the cross-sections of the cured patterns 36a, 36b, 36c, 36d, and 36e

[0641] 37. Horizontal edge of the substrate.

[0642] 47, 53, 66 Alkali-free glass substrates

[0643] 48 First electrode

[0644] 49 Auxiliary Electrode

[0645] 50 Insulation Layer

[0646] 51 Organic EL layer

[0647] 52 Second electrode

[0648] 54 Source Electrode

[0649] 55 Drain electrode

[0650] 57 Oxide semiconductor layer

[0651] 58 Through Hole

[0652] 59 pixel area

[0653] 60 Gate insulating layer

[0654] 61 Gate electrode

[0655] 62 TFT protective layer / pixel segmentation layer

[0656] 63 Organic EL light-emitting layer

[0657] 65. Sealing film.

Claims

1. A negative photosensitive resin composition comprising (A) an alkali-soluble resin and two or more (C1-1) oxime ester-based photopolymerization initiators as (C1) photopolymerization initiators. The (C1-1) oxime ester photopolymerization initiator comprises 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 framework has a fused polycyclic framework comprising an aromatic backbone, and this fused polycyclic framework consists only of carbon and hydrogen atoms. The photopolymerization initiator (C1-1a) containing a fused polycyclic framework has a structure incorporating at least one oxime ester structure or at least one oxime ester carbonyl structure on the fused polycyclic framework, and the photopolymerization initiator (C1-1b) containing a fused polycyclic heterocyclic framework has a structure incorporating at least one oxime ester structure or at least one oxime ester carbonyl structure on the fused polycyclic heterocyclic framework. The (C1-1b) photopolymerization initiator containing a fused polycyclic heterocyclic skeleton contains one or more compounds selected from those shown in general formula (12) and general formula (13). The negative photosensitive resin composition further contains one or more of the following: (B1) a free radical polymerizable compound containing a fluorene backbone, and (B2) a free radical polymerizable compound containing an indane backbone. In general formulas (12) and (13), X 1 X 2 X 4 and X 5 Each independently represents a directly bonded alkylene group with 1 to 10 carbon atoms, a cycloalkylene group with 4 to 10 carbon atoms, or an arylene group with 6 to 15 carbon atoms; Y 1 and Y 2 Each can independently represent a nitrogen atom, an oxygen atom, or a sulfur atom; R 31 ~R 34 Each of these can independently represent 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; R 37 and R 38 Each of the following groups independently represents the group represented by general formula (15), general formula (16), general formula (17), general formula (18), or nitro; R 40 ~R 43 Each of these groups independently represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an aryl group with 6 to 15 carbon atoms, or a group forming a ring with 4 to 10 carbon atoms; R 46 and R 47 Each of the following can independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an aryl group with 6 to 15 carbon atoms, an alkenyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, a haloalkoxy group with 1 to 10 carbon atoms, or an acyl group with 2 to 15 carbon atoms; R 49 and R 50 Each of the following can independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an aryl group with 6 to 15 carbon atoms, an alkenyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, a haloalkoxy group with 1 to 10 carbon atoms, a heterocyclic group with 4 to 10 carbon atoms, a heterocyclic group with 4 to 10 carbon atoms, an acyl group with 2 to 10 carbon atoms, or a nitro group; R 52 and R 53 Each of these elements independently represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, or an aryl group with 6 to 15 carbon atoms; a represents an integer from 0 to 3, b represents 0 or 1, c represents an integer from 0 to 5, and d represents 0 or 1; in Y 1 and Y 2 When each is an independent nitrogen atom, g and h are each independently 1; in Y 1 and Y 2 When each is an oxygen atom or a sulfur atom, g and h are each independently 0; j and k each independently represent 0 or 1; m and n each independently represent integers from 1 to 10; p and q each independently represent integers from 1 to 4; and x and y each independently represent integers from 1 to 4. In general formulas (15) to (18), R 55 ~R 58 Each of the following groups independently represents an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an aryl group with 6 to 15 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a hydroxyalkyl group with 1 to 10 carbon atoms, or a group that forms a ring; a is an integer from 0 to 7, b is an integer from 0 to 2, and c and d are each an integer from 0 to 3.

2. The negative photosensitive resin composition according to claim 1, wherein the photopolymerization initiator containing a fused polycyclic skeleton in (C1-1a) and the photopolymerization initiator containing a fused polycyclic heterocyclic skeleton in (C1-1b) have one or more selected from nitro, naphthyl carbonyl, trimethylbenzoyl, thiophenyl carbonyl, and furanyl carbonyl structures.

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

4. The negative photosensitive resin composition according to claim 2 or 3, further comprising (D1a-1) a black organic pigment and / or a mixture of two or more (D1a-3) coloring pigments as (D) colorant. The (D1a-1) black organic pigment contains one or more of the following: (D1a-1a) benzofuranone black pigment, (D1a-1b) perylene black pigment, and (D1a-1c) azo black pigment. The (D1a-3) two-color or higher coloring pigment mixture contains two or more pigments selected from red, orange, yellow, green, blue, and purple.

5. The photosensitive resin composition according to claim 4, wherein the (D1a-1) black organic pigment comprises a (D1a-1a) benzofuranone-based black pigment.

6. The negative photosensitive resin composition according to any one of claims 1 to 3, wherein the (C1-1a) photopolymerization initiator containing a fused polycyclic skeleton has an alkenyl group.

7. The negative photosensitive resin composition according to claim 2 or 3, wherein the (C1-1b) photopolymerization initiator containing a fused polycyclic heterocyclic skeleton has a benzocarbazole skeleton as the fused polycyclic heterocyclic skeleton.

8. The negative photosensitive resin composition according to any one of claims 1 to 3, wherein the (A) alkali-soluble resin contains a material selected from (A1-1) polyimide, (A1-2) polyimide precursor, and (A1-3) polybenzo[a]pyrene. azole, and (A1-4) polybenzo[ One or more of the azole precursors are used as (A1) first resin.

9. The negative photosensitive resin composition according to claim 8, wherein the (A) alkali-soluble resin further comprises (A2-2) a resin containing polycyclic side chains and / or (A2-3) an acid-modified epoxy resin as the (A2) second resin. The (A2-2) resin containing polycyclic side chains and the (A2-3) acid-modified epoxy resin contain structural units with a fused polycyclic backbone.

10. The negative photosensitive resin composition according to any one of claims 1 to 3, further comprising (B4) a free radical polymerizable compound containing an alicyclic group. The (B4) radical polymerizable compound containing alicyclic groups has a fused polycyclic alicyclic skeleton.

11. A negative photosensitive resin composition comprising (A) an alkali-soluble resin and two or more (C1-1) oxime ester-based photopolymerization initiators as (C1) photopolymerization initiators. The (C1-1) oxime ester photopolymerization initiator comprises 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 framework has a fused polycyclic framework comprising an aromatic backbone, and this fused polycyclic framework consists only of carbon and hydrogen atoms. The photopolymerization initiator (C1-1a) containing a fused polycyclic framework has a structure incorporating at least one oxime ester structure or at least one oxime ester carbonyl structure on the fused polycyclic framework, and the photopolymerization initiator (C1-1b) containing a fused polycyclic heterocyclic framework has a structure incorporating at least one oxime ester structure or at least one oxime ester carbonyl structure on the fused polycyclic heterocyclic framework. The (C1-1b) photopolymerization initiator containing a fused polycyclic heterocyclic skeleton contains one or more compounds selected from those shown in general formula (12) and general formula (13). The negative photosensitive resin composition further contains (B3) an aliphatic free radical polymerizable compound containing a soft chain. The (B3) aliphatic free radical polymerizable compound containing a soft chain has a structure derived from compounds having at least two hydroxyl groups in the molecule, at least two olefinic unsaturated double bonds, and at least one aliphatic chain. The at least one aliphatic chain has at least one lactone-modified chain and / or at least one lactam-modified chain. In general formulas (12) and (13), X 1 X 2 X 4 and X 5 Each independently represents a directly bonded alkylene group with 1 to 10 carbon atoms, a cycloalkylene group with 4 to 10 carbon atoms, or an arylene group with 6 to 15 carbon atoms; Y 1 and Y 2 Each can independently represent a nitrogen atom, an oxygen atom, or a sulfur atom; R 31 ~R 34 Each of these can independently represent 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; R 37 and R 38 Each of the following groups independently represents the group represented by general formula (15), general formula (16), general formula (17), general formula (18), or nitro; R 40 ~R 43 Each of these groups independently represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an aryl group with 6 to 15 carbon atoms, or a group forming a ring with 4 to 10 carbon atoms; R 46 and R 47 Each of the following can independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an aryl group with 6 to 15 carbon atoms, an alkenyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, a haloalkoxy group with 1 to 10 carbon atoms, or an acyl group with 2 to 15 carbon atoms; R 49 and R 50 Each of the following can independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an aryl group with 6 to 15 carbon atoms, an alkenyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, a haloalkoxy group with 1 to 10 carbon atoms, a heterocyclic group with 4 to 10 carbon atoms, a heterocyclic group with 4 to 10 carbon atoms, an acyl group with 2 to 10 carbon atoms, or a nitro group; R 52 and R 53 Each of these elements independently represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, or an aryl group with 6 to 15 carbon atoms; a represents an integer from 0 to 3, b represents 0 or 1, c represents an integer from 0 to 5, and d represents 0 or 1; in Y 1 and Y 2 When each is an independent nitrogen atom, g and h are each independently 1; in Y 1 and Y 2 When each is an oxygen atom or a sulfur atom, g and h are each independently 0; j and k each independently represent 0 or 1; m and n each independently represent integers from 1 to 10; p and q each independently represent integers from 1 to 4; and x and y each independently represent integers from 1 to 4. In general formulas (15) to (18), R 55 ~R 58 Each of the following groups independently represents an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an aryl group with 6 to 15 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a hydroxyalkyl group with 1 to 10 carbon atoms, or a group that forms a ring; a is an integer from 0 to 7, b is an integer from 0 to 2, and c and d are each an integer from 0 to 3.

12. A negative photosensitive resin composition comprising (A) an alkali-soluble resin and two or more (C1-1) oxime ester-based photopolymerization initiators as (C1) photopolymerization initiators. The (C1-1) oxime ester photopolymerization initiator comprises 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 framework has a fused polycyclic framework comprising an aromatic backbone, and this fused polycyclic framework consists only of carbon and hydrogen atoms. The photopolymerization initiator (C1-1a) containing a fused polycyclic framework has a structure incorporating at least one oxime ester structure or at least one oxime ester carbonyl structure on the fused polycyclic framework, and the photopolymerization initiator (C1-1b) containing a fused polycyclic heterocyclic framework has a structure incorporating at least one oxime ester structure or at least one oxime ester carbonyl structure on the fused polycyclic heterocyclic framework. The (C1-1b) photopolymerization initiator containing a fused polycyclic heterocyclic skeleton contains one or more compounds selected from those shown in general formula (12) and general formula (13). The negative photosensitive resin composition further contains (E) dispersant. The (E) dispersant is a dispersant 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. In general formulas (12) and (13), X 1 X 2 X 4 and X 5 Each independently represents a directly bonded alkylene group with 1 to 10 carbon atoms, a cycloalkylene group with 4 to 10 carbon atoms, or an arylene group with 6 to 15 carbon atoms; Y 1 and Y 2 Each can independently represent a nitrogen atom, an oxygen atom, or a sulfur atom; R 31 ~R 34 Each of these can independently represent 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; R 37 and R 38 Each of the following groups independently represents the group represented by general formula (15), general formula (16), general formula (17), general formula (18), or nitro; R 40 ~R 43 Each of these groups independently represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an aryl group with 6 to 15 carbon atoms, or a group forming a ring with 4 to 10 carbon atoms; R 46 and R 47 Each of the following can independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an aryl group with 6 to 15 carbon atoms, an alkenyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, a haloalkoxy group with 1 to 10 carbon atoms, or an acyl group with 2 to 15 carbon atoms; R 49 and R 50 Each of the following can independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an aryl group with 6 to 15 carbon atoms, an alkenyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, a haloalkoxy group with 1 to 10 carbon atoms, a heterocyclic group with 4 to 10 carbon atoms, a heterocyclic group with 4 to 10 carbon atoms, an acyl group with 2 to 10 carbon atoms, or a nitro group; R 52 and R 53 Each of these elements independently represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, or an aryl group with 6 to 15 carbon atoms; a represents an integer from 0 to 3, b represents 0 or 1, c represents an integer from 0 to 5, and d represents 0 or 1; in Y 1 and Y 2 When each is an independent nitrogen atom, g and h are each independently 1; in Y 1 and Y 2 When each is an oxygen atom or a sulfur atom, g and h are each independently 0; j and k each independently represent 0 or 1; m and n each independently represent integers from 1 to 10; p and q each independently represent integers from 1 to 4; and x and y each independently represent integers from 1 to 4. In general formulas (15) to (18), R 55 ~R 58 Each of the following groups independently represents an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an aryl group with 6 to 15 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a hydroxyalkyl group with 1 to 10 carbon atoms, or a group that forms a ring; a is an integer from 0 to 7, b is an integer from 0 to 2, and c and d are each an integer from 0 to 3.

13. A negative photosensitive resin composition comprising (A) an alkali-soluble resin and two or more (C1-1) oxime ester-based photopolymerization initiators as (C1) photopolymerization initiators. The (C1-1) oxime ester photopolymerization initiator comprises 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 framework has a fused polycyclic framework comprising an aromatic backbone, and this fused polycyclic framework consists only of carbon and hydrogen atoms. The photopolymerization initiator (C1-1a) containing a fused polycyclic framework has a structure incorporating at least one oxime ester structure or at least one oxime ester carbonyl structure on the fused polycyclic framework, and the photopolymerization initiator (C1-1b) containing a fused polycyclic heterocyclic framework has a structure incorporating at least one oxime ester structure or at least one oxime ester carbonyl structure on the fused polycyclic heterocyclic framework. The photopolymerization initiator (C1-1a) containing a fused polycyclic framework and the photopolymerization initiator (C1-1b) containing a fused polycyclic heterocyclic framework have one or more structures selected from nitro, naphthyl carbonyl, trimethylbenzoyl, thiophenyl carbonyl, and furanyl carbonyl. The (C1-1b) photopolymerization initiator containing a fused polycyclic heterocyclic skeleton contains one or more compounds selected from those shown in general formula (12) and general formula (13). In general formulas (12) and (13), X 1 X 2 X 4 and X 5 Each independently represents a directly bonded alkylene group with 1 to 10 carbon atoms, a cycloalkylene group with 4 to 10 carbon atoms, or an arylene group with 6 to 15 carbon atoms; Y 1 and Y 2 Each can independently represent a nitrogen atom, an oxygen atom, or a sulfur atom; R 31 ~R 34 Each of these can independently represent 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; R 37 and R 38 Each of the following groups independently represents the group represented by general formula (15), general formula (16), general formula (17), general formula (18), or nitro; R 40 ~R 43 Each of these groups independently represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an aryl group with 6 to 15 carbon atoms, or a group forming a ring with 4 to 10 carbon atoms; R 46 and R 47 Each of the following can independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an aryl group with 6 to 15 carbon atoms, an alkenyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, a haloalkoxy group with 1 to 10 carbon atoms, or an acyl group with 2 to 15 carbon atoms; R 49 and R 50 Each of the following can independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an aryl group with 6 to 15 carbon atoms, an alkenyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, a haloalkoxy group with 1 to 10 carbon atoms, a heterocyclic group with 4 to 10 carbon atoms, a heterocyclic group with 4 to 10 carbon atoms, an acyl group with 2 to 10 carbon atoms, or a nitro group; R 52 and R 53 Each of these elements independently represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, or an aryl group with 6 to 15 carbon atoms; a represents an integer from 0 to 3, b represents 0 or 1, c represents an integer from 0 to 5, and d represents 0 or 1; in Y 1 and Y 2 When each is an independent nitrogen atom, g and h are each independently 1; in Y 1 and Y 2 When each is an oxygen atom or a sulfur atom, g and h are each independently 0; j and k each independently represent 0 or 1; m and n each independently represent integers from 1 to 10; p and q each independently represent integers from 1 to 4; and x and y each independently represent integers from 1 to 4. In general formulas (15) to (18), R 55 ~R 58 Each of the following groups independently represents an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an aryl group with 6 to 15 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a hydroxyalkyl group with 1 to 10 carbon atoms, or a group that forms a ring; a is an integer from 0 to 7, b is an integer from 0 to 2, and c and d are each an integer from 0 to 3.

14. A negative photosensitive resin composition comprising (A) an alkali-soluble resin and two or more (C1-1) oxime ester-based photopolymerization initiators as (C1) photopolymerization initiators. The (C1-1) oxime ester photopolymerization initiator comprises 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 framework has a fused polycyclic framework comprising an aromatic backbone, and this fused polycyclic framework consists only of carbon and hydrogen atoms. The photopolymerization initiator (C1-1a) containing a fused polycyclic framework has a structure incorporating at least one oxime ester structure or at least one oxime ester carbonyl structure on the fused polycyclic framework, and the photopolymerization initiator (C1-1b) containing a fused polycyclic heterocyclic framework has a structure incorporating at least one oxime ester structure or at least one oxime ester carbonyl structure on the fused polycyclic heterocyclic framework. The photopolymerization initiator (C1-1a) containing a fused polycyclic framework and the photopolymerization initiator (C1-1b) containing a fused polycyclic heterocyclic framework have a maximum absorption wavelength of 340 nm or higher and 380 nm or lower. The photopolymerization initiator (C1-1a) containing a fused polycyclic framework and the photopolymerization initiator (C1-1b) containing a fused polycyclic heterocyclic framework both have an absorbance of ≥0.20 at a wavelength of 360 nm in a 0.01 g / L propylene glycol monomethyl ether acetate solution. The (C1-1b) photopolymerization initiator containing a fused polycyclic heterocyclic skeleton contains one or more compounds selected from those shown in general formula (12) and general formula (13). The negative photosensitive resin composition further contains a (Da) black agent as a (D) colorant. The maximum transmission wavelength of this (Da) black agent is above 330 nm and below 410 nm. In general formulas (12) and (13), X 1 X 2 X 4 and X 5 Each independently represents a directly bonded alkylene group with 1 to 10 carbon atoms, a cycloalkylene group with 4 to 10 carbon atoms, or an arylene group with 6 to 15 carbon atoms; Y 1 and Y 2 Each can independently represent a nitrogen atom, an oxygen atom, or a sulfur atom; R 31 ~R 34 Each of these can independently represent 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; R 37 and R 38 Each of the following groups independently represents the group represented by general formula (15), general formula (16), general formula (17), general formula (18), or nitro; R 40 ~R 43 Each of these groups independently represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an aryl group with 6 to 15 carbon atoms, or a group forming a ring with 4 to 10 carbon atoms; R 46 and R 47 Each of the following can independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an aryl group with 6 to 15 carbon atoms, an alkenyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, a haloalkoxy group with 1 to 10 carbon atoms, or an acyl group with 2 to 15 carbon atoms; R 49 and R 50 Each of the following can independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an aryl group with 6 to 15 carbon atoms, an alkenyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, a haloalkoxy group with 1 to 10 carbon atoms, a heterocyclic group with 4 to 10 carbon atoms, a heterocyclic group with 4 to 10 carbon atoms, an acyl group with 2 to 10 carbon atoms, or a nitro group; R 52 and R 53 Each of these elements independently represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, or an aryl group with 6 to 15 carbon atoms; a represents an integer from 0 to 3, b represents 0 or 1, c represents an integer from 0 to 5, and d represents 0 or 1; in Y 1 and Y 2 When each is an independent nitrogen atom, g and h are each independently 1; in Y 1 and Y 2 When each is an oxygen atom or a sulfur atom, g and h are each independently 0; j and k each independently represent 0 or 1; m and n each independently represent integers from 1 to 10; p and q each independently represent integers from 1 to 4; and x and y each independently represent integers from 1 to 4. In general formulas (15) to (18), R 55 ~R 58 Each of the following groups independently represents an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an aryl group with 6 to 15 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a hydroxyalkyl group with 1 to 10 carbon atoms, or a group that forms a ring; a is an integer from 0 to 7, b is an integer from 0 to 2, and c and d are each an integer from 0 to 3.

15. A negative photosensitive resin composition comprising (A) an alkali-soluble resin and two or more (C1-1) oxime ester-based photopolymerization initiators as (C1) photopolymerization initiators. The (C1-1) oxime ester photopolymerization initiator comprises 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 framework has a fused polycyclic framework comprising an aromatic backbone, and this fused polycyclic framework consists only of carbon and hydrogen atoms. The photopolymerization initiator (C1-1a) containing a fused polycyclic framework and the photopolymerization initiator (C1-1b) containing a fused polycyclic heterocyclic framework have structures that incorporate two or more oxime ester structures or structures that incorporate two or more oxime ester carbonyl structures on the fused polycyclic and heterocyclic frameworks. The (C1-1b) photopolymerization initiator containing a fused polycyclic heterocyclic skeleton contains one or more compounds selected from those shown in general formula (12) and general formula (13). In general formulas (12) and (13), X 1 X 2 X 4 and X 5 Each independently represents a directly bonded alkylene group with 1 to 10 carbon atoms, a cycloalkylene group with 4 to 10 carbon atoms, or an arylene group with 6 to 15 carbon atoms; Y 1 and Y 2 Each can independently represent a nitrogen atom, an oxygen atom, or a sulfur atom; R 31 ~R 34 Each of these can independently represent 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; R 37 and R 38 Each of the following groups independently represents the group represented by general formula (15), general formula (16), general formula (17), general formula (18), or nitro; R 40 ~R 43 Each of these groups independently represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an aryl group with 6 to 15 carbon atoms, or a group forming a ring with 4 to 10 carbon atoms; R 46 and R 47 Each of the following can independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an aryl group with 6 to 15 carbon atoms, an alkenyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, a haloalkoxy group with 1 to 10 carbon atoms, or an acyl group with 2 to 15 carbon atoms; R 49 and R 50 Each of the following can independently represent a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an aryl group with 6 to 15 carbon atoms, an alkenyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a haloalkyl group with 1 to 10 carbon atoms, a haloalkoxy group with 1 to 10 carbon atoms, a heterocyclic group with 4 to 10 carbon atoms, a heterocyclic group with 4 to 10 carbon atoms, an acyl group with 2 to 10 carbon atoms, or a nitro group; R 52 and R 53 Each of these elements independently represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, or an aryl group with 6 to 15 carbon atoms; a represents an integer from 0 to 3, b represents 0 or 1, c represents an integer from 0 to 5, and d represents 0 or 1; in Y 1 and Y 2 When each is an independent nitrogen atom, g and h are each independently 1; in Y 1 and Y 2 When each is an oxygen atom or a sulfur atom, g and h are each independently 0; j and k each independently represent 0 or 1; m and n each independently represent integers from 1 to 10; p and q each independently represent integers from 1 to 4; x and y each independently represent integers from 1 to 4, where x and y are not integers of 1. In general formulas (15) to (18), R 55 ~R 58 Each of the following groups independently represents an alkyl group with 1 to 10 carbon atoms, a cycloalkyl group with 4 to 10 carbon atoms, an aryl group with 6 to 15 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a hydroxyalkyl group with 1 to 10 carbon atoms, or a group that forms a ring; a is an integer from 0 to 7, b is an integer from 0 to 2, and c and d are each an integer from 0 to 3.

16. A cured film obtained by curing the negative photosensitive resin composition according to any one of claims 1 to 15.

17. An organic EL display comprising the cured film of claim 16 as selected from one or more of a pixel dividing layer, a TFT planarization layer, a TFT protective layer, an interlayer insulating layer, and a gate insulating layer.

18. A method for manufacturing a cured film, comprising the following steps: (1) The step of forming a coating film of the negative photosensitive resin composition according to any one of claims 1 to 15 on a substrate. (2) The step of irradiating the coating of the negative photosensitive resin composition with active chemical rays through a photomask. (3) The step of developing the negative photosensitive resin composition using an alkaline solution, and, (4) The process of heating the pattern to obtain a cured pattern of the negative photosensitive resin composition.

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