Photosensitive composition, negative photosensitive composition, pixel division layer, and organic el display device

Abstract

Provided is a photosensitive composition that can suppress the generation of development residue on the surface of an electrode and corrosion of the electrode to form a black pixel partition layer, and can suppress the generation of non-lighting pixels in an organic EL display device provided with the pixel partition layer. The photosensitive composition contains: (a) a pigment; (b) a resin having two or more tertiary amino groups in the molecule; and (c) a photosensitizer, wherein the (b) component contains a resin having a structure represented by general formula (1).

Description

TECHNICAL FIELD

[0001] The present application relates to a photosensitive composition, a negative photosensitive composition, a pixel division layer, and an organic EL display device. BACKGROUND

[0002] In recent years, in technical fields of smartphones, televisions, monitors for vehicles, and the like, a large number of display devices equipped with organic electroluminescence (EL) displays have been developed, and various designs of products typified by flexible displays have been proposed. In general, in a light-emitting element included in an organic EL display device, a laminated film in which a transparent conductive film is laminated on the surface of a metal reflective layer is used as an electrode disposed on the side opposite to the light extraction direction. As the transparent conductive film, ITO (Indium Tin Oxide), ITZO (Indium Tin Zinc Oxide), IZO (Indium Zinc Oxide), or the like can be used. On the other hand, as the metal reflective layer, Ag / Cu or Ag / Pd / Cu or the like, which is a silver alloy, is particularly widely used from the viewpoint of the reflectance of visible light and the conductivity. For example, in Patent Document 1, a bottom emission type organic EL display device in which a display portion can be rolled up is disclosed, and as the metal reflective layer of the light-emitting element, a case where a silver alloy is used is exemplified. In Patent Document 2, a top emission type organic EL display device is disclosed, which includes a light-emitting element including an anode electrode formed of a patterned laminated film in which a transparent conductive film (film thickness: 10 nm) is formed on the surface of a silver alloy (film thickness: 100 nm). In Patent Document 3, it is disclosed that if an electrical short occurs in a light-emitting element, the light emission output of each of a plurality of pixels disposed decreases, or a part of the pixels is not lit, thereby degrading the quality of the display device.

[0003] However, as the organic EL display device of the self-emission type, there is a problem that the visual recognition easily decreases when external light such as sunlight is incident on the display portion. In recent years, in order to suppress the decrease in the visual recognition, a technology of blackening a pixel division layer formed for the purpose of dividing the pixels of each light-emitting element of red, blue, green, and the like, thereby imparting light shielding properties, has been attracting attention. The pixel division layer is required to have high insulation and low dielectric constant, and therefore, as a coloring material for imparting light shielding properties, a photosensitive composition containing an organic pigment exhibiting black color has been proposed, and various dispersants have been used in order to make the organic pigment fine and stable in dispersion. For example, in Patent Document 4, a negative photosensitive composition containing a polyether-based dispersant having one tertiary amino group in the molecule as a pigment adsorption group, and a negative photosensitive composition containing a urethane-based dispersant having a heterocycle are disclosed. Further, in Patent Document 5, a negative photosensitive composition containing an acrylic-based dispersant having a quaternary ammonium salt group and a tertiary amino group as pigment adsorption groups is disclosed.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: Japanese Patent Application Laid-Open (JP A) No. 2019-113847

[0007] Patent Document 2: Japanese Patent Application Laid-Open (JP A) No. 2008-108533

[0008] Patent Document 3: Japanese Patent Application Laid-Open (JP A) No. 2017-516271

[0009] Patent Document 4: International Publication No. 2017 / 057281

[0010] Patent Document 5: Japanese Patent Application Laid-Open (JP A) No. 2018-155878 SUMMARY

[0011] PROBLEMS TO BE SOLVED BY THE INVENTION

[0012] However, in the case where the first electrode is a layered film containing a silver alloy film, when the pixel partition layer is formed using the negative photosensitive composition disclosed in Patent Document 4 and Patent Document 5, respectively, there is a problem that a convex portion is generated on the surface of the electrode at the opening portion of the pixel partition layer due to generation of development residue. In addition, there is also a problem that a convex portion is generated due to generation of a bump by corrosion of the electrode. On the other hand, for the photosensitive composition for forming the pixel partition layer, in order to inactivate components such as a photosensitizer and a thermal curing agent, which have a tendency to deteriorate easily due to heat, the photosensitive composition is often stored for a long time at a constant temperature of -15°C or lower, and in such a frozen environment, the dispersion stabilization function that the dispersant should originally exhibit is easily impaired, and there is a problem that the convex portion on the electrode is more likely to be generated. Generation of the convex portion causes electrical short-circuiting when the organic EL display device is driven, and is one of the main causes of generation of pixels that do not light up, and thus there is an urgent need for a photosensitive composition or a negative photosensitive composition that can form a pixel partition layer while suppressing generation of development residue and corrosion of the electrode, and has excellent stability in frozen storage. Furthermore, there is an urgent need for an organic EL display device in which generation of pixels that do not light up is suppressed.

[0013] MEANS FOR SOLVING THE PROBLEMS

[0014] A first aspect of the present application is a photosensitive composition containing: (a) a pigment; (b) a resin having two or more tertiary amino groups in the molecule; and (c) a photosensitizer, wherein the (b) component contains a resin having a structure represented by General Formula (1).

[0015] Further, a second aspect of the present application is a negative photosensitive composition, which contains: (a-1) an organic black pigment or (a-2) a mixed-color organic black pigment; (b) a resin having two or more tertiary amino groups in a molecule; and (c) a photosensitizer, characterized in that the (b) component contains a resin having a structure represented by General Formula (1).

[0016] Further, a third aspect of the present application is an organic EL display device, which has a pixel partition layer containing a resin having two or more tertiary amino groups in a molecule and having a structure represented by General Formula (1).

[0017] Effects of the Invention

[0018] According to the photosensitive composition or the negative photosensitive composition of the present application, generation of development residue on the surface of an electrode formed of a laminated film of a transparent conductive film and a silver alloy film and corrosion of the electrode can be inhibited, thereby forming a pixel partition layer having light shielding properties, and the organic EL display device having the pixel partition layer can be stored under refrigeration, and generation of non-lighting pixels can be inhibited.

[0019] Further, according to the organic EL display device of the present application, generation of non-lighting pixels can be inhibited. BRIEF DESCRIPTION OF DRAWINGS

[0020] [ Figure 1 ] is a cross-sectional view of a TFT substrate of a top emission type organic EL display device having a pixel partition layer, which shows one example of an embodiment of the present application.

[0021] [ Figure 2 ] is a cross-sectional view of a measurement site of the maximum height difference Rmax in all of the examples and comparative examples. 2

[0022] [ Figure 3 ] is a three-dimensional measurement image obtained by an atomic force microscope, which shows the surface state of a silver alloy film after a curing step in Reference Example 1.

[0023] [ Figure 4 ] is a three-dimensional measurement image obtained by an atomic force microscope, which shows the surface state of a silver alloy film at an opening portion of a pixel partition layer in Example 5 (evaluation after refrigeration storage for 3 months).

[0024] [ Figure 5 ] is a three-dimensional measurement image obtained by an atomic force microscope, which shows the surface state of a silver alloy film at an opening portion of a pixel partition layer in Comparative Example 3 (evaluation after refrigeration storage for 3 months).

[0025] [ Figure 6 ​This refers to the manufacturing process of a top-emitting organic EL display device, including the pixel segmentation layer formation process, in all embodiments and comparative examples.

[0026] [ Figure 7 This is a cross-sectional view of a pixel segmentation layer forming substrate having thin film portions and thick film portions, fabricated in Example 15. Detailed Implementation

[0027] The present invention will now be described in detail. The numerical range indicated by “~” refers to the range of values ​​before and after “~” as a lower and upper limit. A pixel segmentation layer refers to the pixel segmentation layer provided in an organic EL display device. Visible light refers to light with wavelengths of 380 nm or more and below 780 nm; near-ultraviolet light refers to light with wavelengths of 200 nm or more and below 380 nm. Light blocking refers to the function of reducing the intensity of transmitted light compared to the intensity of light incident along a direction perpendicular to the cured film; light blocking property refers to the degree to which visible light is blocked.

[0028] Negative photosensitive compositions refer to those that are sensitive to near-ultraviolet light and are alkaline-developable, excluding compositions that are not sensitive to near-ultraviolet light and compositions that are organic solvent-developable. In this specification, resin refers to compounds with a high molecular weight chain and a weight-average molecular weight of 1000 or more, excluding low-molecular-weight compounds with a weight-average molecular weight below 1000. Weight-average molecular weight (Mw) refers to the value obtained by gel permeation chromatography using tetrahydrofuran as a carrier, converted using a standard curve based on standard polystyrene.

[0029] Unless otherwise specified, the term "developer" refers to an organic alkaline aqueous solution. The "CI" used in the designation of colorants stands for Colour Index Generic Name, based on the color index published by The Society of Dyers and Colourists. For colorants registered in the color index, the Colour Index Generic Name indicates the chemical structure and crystal form of the pigment or dye.

[0030] Regarding color classification, for example, the term "yellow pigment" includes pigments belonging to "CI Pigment Yellow," "blue pigment" includes pigments belonging to "CI Pigment Blue," "red pigment" includes pigments belonging to "CI Pigment Red," and "purple pigment" includes pigments belonging to "CI Pigment Violet." The same applies to the descriptions of orange, brown, green, and black pigments. It should be noted that for colorants not registered in the color index, their specific structures are shown.

[0031] Note that carbon black classified as C.I. Pigment Black 7 or the like is classified as an inorganic black pigment regardless of the crystallinity or the level of insulation. In addition, azine compounds typified by aniline black are classified as black dyes. Therefore, C.I. Pigment Black 1 and 21 belonging to the above range are not included in the organic black pigments in the present specification. In addition, the so-called azo-based black pigments do not include inorganic black pigments that have been surface-modified with an organic group having an azo group.

[0032] The first and second modes of the present application will be described.

[0033] The photosensitive composition (hereinafter, sometimes referred to as a photosensitive composition) of the first mode of the present application contains: (a) a pigment; (b) a resin having two or more tertiary amino groups in a molecule; and (c) a photosensitive agent, wherein the (b) component contains a resin having a structure represented by General Formula (1).

[0034] In addition, the negative photosensitive composition (hereinafter, sometimes referred to as a negative photosensitive composition) of the second mode of the present application contains: (a-1) an organic black pigment or (a-2) a mixed-color organic black pigment; (b) a resin having two or more tertiary amino groups in a molecule; and (c) a photosensitive agent, wherein the (b) component contains a resin having a structure represented by General Formula (1).

[0035] [Chemical Formula 1]

[0036]

[0037] In General Formula (1), * indicates a bonding site with a carbon atom or a nitrogen atom. 1 O, A 2 O, A 3 O and A 4 Each of O independently indicates an oxyalkylene group having 1 to 5 carbon atoms.a 1 and a 3 is an integer, each independently indicates 1 to 100.a 2 and a 4 is an integer, each independently indicates 0 to 100.X 1 and X 2 each independently indicates a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms.

[0038] The (b) resin having two or more tertiary amino groups in a molecule and the (c) photosensitive agent in the first and second modes of the present application are components common to the first and second modes.

[0039] The photosensitive composition in the first mode of the present application contains (a) a pigment. The pigment referred to herein is a pigment having a property of absorbing light of at least a part of wavelengths of visible light among the particle components contained in the photosensitive composition. Note that, based on the technical common sense of those skilled in the art, a metal filler such as silver or copper, regardless of the optical properties, does not belong to the category of (a) a pigment. By containing (a) a pigment, the pixel division layer obtained by curing the photosensitive composition of the present application can be imparted with light shielding properties. As (a) a pigment, known organic pigments or inorganic pigments can be cited, and from the aspect of excellent light shielding properties, a pigment in black is preferred.

[0040] As the organic pigment, for example, (a-1) an organic black pigment, (a-2) a mixed-color organic black pigment described later can be cited. The (a-2) a mixed-color organic black pigment referred to herein is a pigment mixture not containing (a-1) an organic black pigment, but containing a mixture of a pigment of at least one color selected from the group consisting of (a-2-1) an organic yellow pigment, an organic red pigment and an organic orange pigment, and (a-2-2) an organic blue pigment and / or an organic violet pigment, and the proportion of the (a-2-2) component is in the range of 20 to 90% by weight, relative to the total amount of the (a-2-1) component and the (a-2-2) component. By subtractive color mixing of the (a-2-1) component and the (a-2-2) component, a pixel division layer which is simulated to be black can be obtained. Note that, in the case of containing (a-1) an organic black pigment, even if an organic pigment belonging to the (a-2-1) component and / or the (a-2-2) component is contained, it is defined as a pigment belonging to the category of (a-1) an organic black pigment.

[0041] As the inorganic pigment, for example, carbon black, titanium nitride, titanium oxynitride, zirconium nitride, zirconium oxynitride can be cited. In terms of high insulation and low dielectric constant, it is preferred to contain at least an organic pigment to obtain the desired light shielding properties. The organic pigment preferably contains the (a-1) component or the (a-2) component.

[0042] As the content of (a) a pigment, in terms of light shielding properties and development properties of the pixel division layer, it is preferred to be 15 to 45% by weight, relative to the total solid content of the photosensitive composition. The solid content refers to the components contained in the photosensitive composition other than the solvent.

[0043] The organic pigment and the inorganic pigment can be used in a mixture, but from the aspect of improving the alignment accuracy of exposure using near-infrared light, i.e., the alignment accuracy of the exposure mask and the substrate described later, it is preferred that the (a) pigment contains 50% by weight or more of the organic pigment to obtain the desired light shielding properties.

[0044] The photosensitive composition of the present application has either of a negative photosensitivity or a positive photosensitivity. It can have a negative photosensitivity in which the film of the exposed portion is photocured by exposure through a pattern of an exposure mask described later, the alkali solubility is reduced, and the film of the unexposed portion is removed using an alkali developer to form a pattern. Alternatively, it can have a positive photosensitivity in which the alkali solubility of the film of the exposed portion is relatively increased compared with that of the film of the unexposed portion by exposure through a pattern of an exposure mask, whereby the film of the exposed portion is removed using an alkali developer to form a pattern. From the viewpoint that the minimum exposure amount required for obtaining a pixel division layer having a desired light shielding property can be reduced and the productivity can be improved, it is preferable to have a negative photosensitivity.

[0045] Further, the negative photosensitive composition in the second mode of the present application contains (a-1) an organic black pigment or (a-2) a mixed-color organic black pigment. The (a-1) organic black pigment and the (a-2) mixed-color organic black pigment are the same as described in the first mode above.

[0046] As the (a-1) organic black pigment, benzo difuranone-based black pigments, perylene-based black pigments, azo-based black pigments, and anthraquinone-based black pigments can be given. Among them, from the viewpoint of excellent heat resistance and dispersibility, benzo difuranone-based black pigments and perylene-based black pigments are preferable, and from the viewpoint of excellent light shielding property, benzo difuranone-based black pigments are more preferable.

[0047] The benzo difuranone-based black pigment refers to an organic black pigment having a polycyclic structure in which two difuranone rings are fused to one benzene ring in the molecule, and for example, bis-oxo bisindolylidene- benzo difuranone described in International Publication No. 2009 / 010521 can be given. Among them, from the viewpoint of heat resistance, benzo difuranone-based black pigments represented by General Formula (2) or General Formula (3) are preferable. The isomers include geometric isomers and tautomers. The isomers can be contained as a mixture, or a plurality of compounds in an isomeric relationship can form a mixed crystal to constitute one crystallite or primary particle.

[0048] [Chemical Formula 2]

[0049]

[0050] In General Formula (2) and General Formula (3), R 1 and R 2 each independently represent a hydrogen atom or a methyl group. R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R10 Each can be independently represented as an alkyl group having 1 to 12 hydrogen atoms or carbon atoms.

[0051] Among them, considering excellent heat resistance, those containing R are preferred. 1 ~R 10 The black pigment is a benzodifuranone-based pigment with hydrogen atoms and a lactam ring structure. Specifically, a benzodifuranone-based black pigment represented by structural formula (4) is preferred. Due to the excellent heat resistance of the pigment itself, it is preferable for use in pixel separation layers requiring high heat resistance (above 230°C) from the viewpoint of suppressing the generation of non-lit pixels. The benzodifuranone-based black pigment represented by general formula (2) or general formula (3) can be synthesized by reacting indigo or its derivatives with 2,5-dihydrobenzene-1,4-diacetic acid. From the viewpoint of suppressing corrosion of silver alloy films, it is preferable to purify the pigment beforehand so that the residual amount of indigo or its derivatives in the pigment is less than 100 ppm. The benzodifuranone-based black pigment represented by structural formula (4) can be a commercially available product, such as "Irgaphor" (registered trademark) Black S0100 (manufactured by BASF).

[0052] [Chemical Formula 3]

[0053]

[0054] Perylene-based black pigments refer to organic black pigments that have a perylene skeleton in their molecules. Examples include perylene-based black pigments represented by structural formulas (5) or (6) and CI pigments Black 31 and 32.

[0055] [Chemical Formula 4]

[0056]

[0057] R 11 ~R 18 Each can be independently represented by a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a hydroxyl group.

[0058] Among these, considering excellent light-blocking and heat resistance, a perylene-based black pigment comprising a mixture of isomers of a compound represented by structural formula (7) as a cis-body and a compound represented by structural formula (8) as a trans-body is more preferred. Considering high ultraviolet transmittance and excellent photocurability, a trans-body containing 30% by weight or more is further preferred, based on the total amount of the cis-body and trans-body.

[0059] [Chemical Formula 5]

[0060]

[0061] As for the isomer mixture of the compound represented by Structural Formula (5) as a cis body and the compound represented by Structural Formula (6) as a trans body, it can be synthesized by reacting o-phenylenediamine or a derivative thereof with perylene-3,4,9,10-tetracarboxylic dianhydride. In order to suppress corrosion of the silver alloy film, it is preferable to purify in advance in such a manner that the residual amount of o-phenylenediamine or a derivative thereof in the pigment becomes 100 ppm or less.

[0062] The so-called azo-based black pigment is an organic black pigment having an azo bond in the molecule, and examples thereof include azo-based black pigments described in Japanese Patent Application Publication No. 2010-116549 and Japanese Patent Application Publication No. 2017-193689. The azo-based black pigments can be synthesized by azo coupling reaction. From the aspect of suppressing corrosion of the silver alloy film, it is preferable to purify in advance in such a manner that the residual amount of free chlorine generated as a byproduct in the pigment becomes 100 ppm or less.

[0063] The so-called anthraquinone-based black pigment is a black pigment having an anthraquinone skeleton in the molecule, and examples thereof include anthraquinone-based black pigments described in Japanese Patent Application Publication No. 2018-145353, which have two lactam rings in the molecule. The quinone-based black pigments can be synthesized by reacting isatin or a derivative thereof with 1,5-diaminoanthraquinone. From the aspect of suppressing corrosion of the silver alloy film, it is preferable to purify in advance in such a manner that the residual amount of each of isatin or a derivative thereof and 1,5-diaminoanthraquinone in the pigment becomes 100 ppm or less.

[0064] Next, specific examples of the organic pigments constituting the (a-2) mixed-color organic black pigments will be described.

[0065] As the organic yellow pigments belonging to (a-2-1), for example, C.I. Pigment Yellow 120, 138, 139, 151, 175, 180, 185, 181, 192, 194 can be preferably mentioned, which can be used alone or in combination.

[0066] As the organic orange pigments belonging to (a-2-1), for example, C.I. Pigment Orange 13, 36, 43, 61, 64, 71, 72 can be mentioned, which can be used alone or in combination. From the aspect of excellent developability on a silver alloy film and heat resistance, a perinone-based orange pigment can be used, and among them, C.I. Pigment Orange 43 represented by Structural Formula (9) is preferable. C.I. Pigment Orange 43 can be synthesized by reacting naphthalene tetracarboxylic anhydride with o-phenylenediamine and removing the trans isomer generated as a byproduct. From the aspect of suppressing corrosion of the silver alloy film, it is preferable to purify in advance in such a manner that the residual amount of o-phenylenediamine in the pigment becomes 100 ppm or less.

[0067] [Chemical Formula 6]

[0068]

[0069] As the organic red pigment belonging to (a-2-1), for example, C.I. Pigment Red 122, 123, 149, 179, 180, 189, 190, 202, 209, 254, 255, 264 can be preferably selected, which can be used alone or also can be used by mixing a plurality of kinds. From the aspects of the development property on the silver alloy film and the excellent heat resistance, perylene-based red pigments can be used, among which C.I. Pigment Red 179 is preferable. C.I. Pigment Red 179 can be synthesized by the reaction of perylene-3,4,9,10-tetracarboxylic dianhydride and methylamine. From the aspect of suppressing the corrosion of the silver alloy film, purification in advance so that the residual amount of o-phenylenediamine in the pigment becomes 100 ppm or less is preferable.

[0070] [Chemical Formula 7]

[0071]

[0072] As the organic blue pigment belonging to (a-2-2), for example, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:6, 16, 25, 26, 56, 57, 60, 61, 64, 65, 66, 75, 79, 80 can be preferably selected, which can be used alone or also can be used by mixing a plurality of kinds. From the aspects of the development property on the silver alloy film and the excellent heat resistance, C.I. Pigment Blue 60 represented by Structural Formula (11) as an indathrene-based blue pigment and C.I. Pigment Blue 65 represented by Structural Formula (12) as a violanthrone-based blue pigment are preferable.

[0073] C.I. Pigment Blue 60 can be synthesized by dissolving 2-aminoanthraquinone base, and performing a condensation reaction. From the aspect of suppressing the corrosion of the silver alloy film, purification in advance so that the residual amount of 2-aminoanthraquinone in the pigment becomes 100 ppm or less is preferable. On the other hand, C.I. Pigment Blue 65 can be synthesized by a dimerization coupling reaction of benzanthrone. Also, from the aspect of improving the exposure sensitivity, C.I. Pigment Blue 25, 26 having excellent near-ultraviolet transmittance is preferably mixed with C.I. Pigment Blue 60, 65 and used.

[0074] [Chemical Formula 8]

[0075]

[0076] [Chemical Formula 9]

[0077]

[0078] As the organic purple pigment belonging to (a-2-2), for example, C.I. Pigment Violet 19, 23, 29, 32, 37 can be preferably selected, which can be used alone or also can be used by mixing a plurality of kinds. From the aspects of the development property on the silver alloy film and the excellent heat resistance, C.I. Pigment Violet 29 as a perylene-based purple pigment, or C.I. Pigment Violet 37 as a dioxazine-based purple pigment is preferred.

[0079] As for the chemical structure of the above (a-1) component and (a-2) component, the concentrate of the photosensitive composition or the negative photosensitive composition obtained by centrifugal separation or reduced pressure treatment is combined with time-of-flight secondary ion mass spectrometry (TOF-SIMS), time-of-flight mass spectrometry (TOF-MS), direct sample introduction-ion trap type mass spectrometry, NMR analysis, LC-MS, ICP mass spectrometry, infrared absorption spectroscopy, powder X-ray diffractometry using CuKa rays to identify. A solution dissolved in an amide-based organic solvent such as dimethylformamide, N-methylpyrrolidone, etc. can also be used as an analysis sample to improve the identification accuracy.

[0080] From the viewpoint of reducing the adsorptivity to the surface of the transparent conductive film and the silver alloy film and obtaining more excellent developability, the (a-1) component and the (a-2) component contained in the photosensitive composition or the negative photosensitive composition of the present application preferably have a coating layer containing at least one coating material selected from the group consisting of silicon dioxide, metal oxide, and metal hydroxide on the surface thereof, and the benzodifuranone-based black pigment represented by General Formula (2) or General Formula (3) more preferably has a coating layer containing at least one coating material selected from the group consisting of silicon dioxide, metal oxide, and metal hydroxide on the surface thereof. Among them, the coating layer more preferably contains silicon dioxide from the viewpoint of the non-activity of the silver alloy, the high insulating property, and the position of the isoelectric point on the negative side. From the viewpoint of obtaining a silicon dioxide layer having high alkali resistance in a developing solution, high Mohs hardness, and high density, a silicon dioxide obtained by the reaction of an organic acid or an inorganic acid with an alkali metal silicate is further preferred. As a specific example, a method in which a dilute aqueous solution of sulfuric acid and a dilute aqueous solution of an alkali metal silicate are added in parallel to each other in an aqueous medium maintained at pH 2 to 7, a silicon dioxide hydrate is precipitated on the surface of the pigment, and further dehydration and sintering thereof are performed by heating to form a silicon dioxide layer can be given. As the heating temperature, 200°C or higher is preferred in order to suppress the generation of moisture from the pixel division layer and prevent the deterioration of the light-emitting element, and 230°C or higher is more preferred from the viewpoint of obtaining high hardness for suppressing the damage of the coating layer in a wet medium dispersion treatment described later and high adhesion to the surface of the pigment for suppressing peeling. 300°C or lower is preferred in order to suppress the crystalline transition and thermal decomposition of the organic pigment, and 280°C or lower is more preferred from the viewpoint of suppressing the generation of sublimation foreign matter. As the heating time, 1 to 6 hours is preferred from the same viewpoint.

[0081] As the nucleated organic pigment, a pigment having high hydrophilicity, high acid resistance, and high heat resistance is preferred, and the benzodifuranone-based black pigment represented by General Formula (2) or General Formula (3) among the (a-1) component and the (a-2) component is most preferred. From the viewpoint of further improving the alkali resistance in a developing solution of the coating layer containing silicon dioxide, a part of the matrix structure containing a silicon atom and an oxygen atom can further contain a part of a zirconium atom, and thus a complex structure of -Si-O-Zr-O-Si- can be further introduced. By attaching a zirconium source to the coating layer containing silicon dioxide and then performing sintering, a zirconium atom can be introduced to a part of the coating layer. As the zirconium source, tetra-n-propoxy zirconium, tetra-isopropoxy zirconium, tetraethoxy zirconium, tetra-n-butoxy zirconium, and the like can be used.

[0082] As the (a-1) component or the (a-2) component contained in the photosensitive composition or the negative-type photosensitive composition of the present application, from the viewpoint of high light shielding property and excellent development property on a silver alloy film, an organic black pigment formed of a core containing a silicic acid-coated layer and a benzodifuranone-based black pigment represented by General Formula (2) or General Formula (3) or an isomer thereof is most preferable. By having a silicic acid-coated layer, the adsorptivity of the resin having a structure represented by General Formula (1) described later to the surface of the pigment can be improved, and the generation of development residue caused by the re-aggregation or re-attachment of the pigment due to contact with a developing solution in the development process can be reduced.

[0083] As the content of the (a-1) component, from the viewpoint of balancing the light shielding property and the development property of the pixel division layer, it is preferable to be 15 to 40% by weight in the entire solid component of the photosensitive composition or the negative-type photosensitive composition, and as the content of the (a-2) component, from the same viewpoint, it is preferable to be 25 to 45% by weight in the entire solid component. The entire solid component means a component other than a solvent contained in the photosensitive composition or the negative-type photosensitive composition.

[0084] From the viewpoint of improving the dispersion stabilization effect and the development residue suppression effect of the resin having a structure represented by General Formula (1), in order to avoid the mixed existence of coarse particles and suppress the generation of non-pointed pixels, the specific surface area of each of the organic pigments constituting the (a-1) component and the (a-2) component is preferably 10 m 2 / g or more. In the refinement to the desired average dispersed particle diameter, from the viewpoint of suppressing the increase in the viscosity of the pigment dispersion liquid, it is preferably 80 m 2 / g or less. The specific surface area can be measured by the BET method based on the nitrogen adsorption amount.

[0085] Further, as a component contributing to the optical properties of the pixel division layer, a dye can be contained within a range that does not adversely affect the effects of the present application, and the spectral reflectance of the pixel division layer, the light scattering property inside the film, and the like can be finely adjusted.

[0086] The photosensitive composition or the negative-type photosensitive composition of the present application contains a (b) resin having two or more tertiary amino groups in the molecule, and as this (b) component, a resin having a structure represented by General Formula (1) is contained. The tertiary amino group is not particularly limited in the bonding position in the molecule, and includes not only a tertiary amino group as a terminal group or a side chain but also a tertiary amine structure as a connecting group from the main chain of a polyamine.

[0087] As the first effect, since the resin having the structure represented by General Formula (1) has a high dispersion stabilizing effect on (a) pigments, particularly on the (a-1) component and the (a-2) component, the micronization can be sufficiently promoted at the time of manufacturing of a pigment dispersion liquid described later, and even if stored for a long period under freezing, the effect of stabilizing the above-described dispersion state is excellent, and thus the generation of an undesirable protrusion on an electrode caused by a developing residue containing a pigment aggregate can be suppressed. The so-called pigment aggregate includes not only a pigment aggregate that can be generated in a photosensitive composition or a negative photosensitive composition, but also a pigment aggregate that can be generated by contact with a developing solution in a developing step. As the second effect, crystallization or a concentration gradient does not occur even under freezing, and the generation of a developing residue caused by an insoluble component of the dispersant itself can be suppressed. Third, even if contact with the surface of a silver alloy film is made, corrosion is not promoted, and instead, a function of preventing corrosion is possessed, and an effect of suppressing the generation of a bump is exerted.

[0088] [Chemical Formula 10]

[0089]

[0090] In General Formula (1), * indicates a bonding site with a carbon atom or a nitrogen atom. 1 O, A 2 O, A 3 O and A 4 O each independently represents an oxyalkylene group having 1 to 5 carbon atoms.a 1 and a 3 are integers each independently representing 1 to 100.a 2 and a 4 are integers each independently representing 0 to 100.X 1 and X 2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms.

[0091] Note that in General Formula (1), the number of repeating units a 1 is 2 or more, the partial structure represented by [CO-A 1 O]a 1 may also be composed of repeating units including a plurality of alkylene groups different from each other in the number of carbon atoms. The partial structures represented by [CO-A 2 O]a 2 , [CO-A 3 O]a 3 , and [CO-A 4 O]a 4 are respectively the same.

[0092] A 1 O, A 2 O, A 3O and A 4 O, for example, methylene oxide, ethylene oxide (hereinafter sometimes written as "C2H4O"), propylene oxide (hereinafter sometimes written as "C3H6O"), butylene oxide (hereinafter sometimes written as "C4H8O"), amylene oxide. As A 1 O and A 3 O, from the viewpoint of giving consideration to both the excellent dispersibility of the organic pigment and the high developability on the silver alloy film, ethylene oxide and propylene oxide are preferred, and from the viewpoint of giving consideration to both the dispersibility and the developability, more preferably both ethylene oxide and propylene oxide are contained. As A 2 O and A 4 O, from the viewpoint of excellent dispersion stabilization effect and ease of synthesis, propylene oxide, butylene oxide, amylene oxide are preferred. As X 1 and X 2 , for example, a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, wherein, from the viewpoint of excellent developability, a hydrogen atom, a methyl group are preferred, and a hydrogen atom is more preferred.

[0093] a indicating the number of repeating units 1 and a 3 are integers, from the viewpoint of giving consideration to both the dispersion stabilization effect and the developability, each is preferably 5 to 60, and more preferably 10 to 40. From the same viewpoint as a 1 and a 3 , a 2 and a 4 are preferably 0 to 20, and more preferably 0 to 10.

[0094] [A 1 O]a 1 and [A 3 O]a 3The partial structure represented by (poly)oxyalkylene, for example, can be obtained by adding a cyclic ether such as ethylene oxide, propylene oxide, an alkylene glycol such as ethylene glycol, propylene glycol, a homopolymer of a polyalkylene glycol such as polyethylene glycol, polypropylene glycol, a block-type polyalkylene glycol of polyethylene glycol and polypropylene glycol, and converting the primary amino group (or primary and secondary amino groups) of the primary amino group-containing aliphatic amine described later. The block-type polyalkylene glycol is commercially available in various carbon atom numbers / repeating unit numbers, and examples include "Synperonic" (registered trademark) F108, Synperonic L35, Synperonic L64, Synperonic 121, "Poloxamer" (registered trademark) 237 (all manufactured by SIGMA-ALDRICH), "Pluronic" (registered trademark) P65, Pluronic P84, Pluronic P102, Pluronic 105, Pluronic F38, Pluronic F77, Pluronic F87 (all manufactured by BASF). On the other hand, the [CO-A 2 O]a 2 and [CO-A 4 O]a 4 The partial structure represented by (poly)oxyalkylene carbonyl, for example, can be obtained by adding a cyclic ester compound (or a condensate thereof) such as α-lactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone to the terminal hydroxyl group of (poly)oxyalkylene.

[0095] As the arrangement of the repeating units, from the aspect of being able to obtain a higher dispersion stabilizing effect, it is preferable that at least any one of [A 1 O]a 1 and [A 3 O]a 3 has a block-type polyoxyalkylene having a polyoxyethylene structure and a polyoxypropylene structure. By block-type, it is meant that, in a polyoxyalkylene chain formed of repeating units including a plurality of alkylene groups having different carbon atom numbers, the oxyalkylene group of a certain specific carbon atom number is bonded by being linked to 2 or more of the repeating units in 5 or more numbers.

[0096] From the aspect of improving the hydrophilicity to improve the developability, X 1 and X 2 are each preferably a hydrogen atom or a methyl group, and it is preferable that at least any one of them is a hydrogen atom.

[0097] As a specific example of the structure having a block type polyoxyalkylene formed of a polyoxyethylene structure and a polyoxypropylene, and the terminal of the polyoxyalkylene chain being a hydrogen atom, there are a structure represented by General Formula (13), a structure represented by General Formula (14), a structure represented by General Formula (15), among which, from the viewpoint of excellent development properties on a silver alloy film, the structure represented by General Formula (13) is more preferable. 5 The total of a 6 The total of a 1 The total of a 7 The total of a 8 The total of a 3 The total of a 9 The total of a 18 The same applies to a 5 , a 6 , a 7 , a 8 , and a 5 The total of a 6 The total of a 7 The total of a 8 The same applies to a 9 , a 10 , a 11 , a 12 , and a 9 The total of a 10 The total of a 11 The total of a 12 The same applies to a 13 , a 14 , a 15 , a 16 , a 17 , and a 18 The total of a 13 The total of a 14 The total of a 15

[0098] [Chemical Formula 11]

[0099]

[0100] In General Formula (13), a 5 , a 6 , a 7 , and a 8 are integers, the total of a 5 and a 6 is 1 to 100, and the total of a 7 and a 8 is 1 to 100.

[0101] In General Formula (14), a 9 , a 10 , a 11 , and a 12 are integers, the total of a 9 and a 10 is 1 to 100, and the total of a 11 and a 12 is 1 to 100.

[0102] In General Formula (15), a 13 , a 14 , a 15 , a 16 , a 17 , and a 18 are integers, the total of a 13 , a 14 , and a 15 is 1 to 100.16 , a 17 and a 18 The total of a and a is 1 to 100.

[0103] The resin having a structure represented by General Formula (1) preferably has a value obtained by dividing the total number of moles of the repeating unit containing an oxyalkylene group having a carbon number of 1 and 2 by the total number of moles of the repeating unit containing an oxyalkylene group having a carbon number of 3 to 5 is 0.76 to 4.00. That is, when the total of the repeating units containing an oxyalkylene group having a carbon number of 1 to 5 is assumed to be 100 mol%, the total of the repeating units containing an oxyalkylene group having a carbon number of 1 and 2 is preferably 43.20 to 80.00 mol%. If it is 0.76 or more, a significant effect that the developing time required for dissolving and removing the film of the unexposed portion in the vicinity of the surface of the silver alloy film becomes shorter compared to the developing time required for dissolving and removing the film of the unexposed portion in the vicinity of the surface of the transparent conductive film in the developing step described later can be obtained. Therefore, generally, when the developing is performed at an appropriate developing time optimized based on the necessary minimum developing time on the transparent conductive film as a result, the developing residue on the silver alloy film can be further reduced. More preferably, it is 1.00 or more. On the other hand, if it is 4.00 or less, the hydrophobicity can be moderately imparted, and the generation of the developing residue caused by the peeling of the film of the exposed portion in the developing step can be suppressed. More preferably, it is 3.00 or less.

[0104] Further, in terms of improving the dispersion stability, the weight average molecular weight is preferably 2000 or more, and in terms of improving the developing property, it is preferably 10000 or less. In terms of improving the dispersion stability, the amine value is preferably 5 (mgKOH / g) or more, and in terms of improving the developing property, it is preferably 100 (mgKOH / g) or less. The amine value can be measured by the potentiometric titration method based on "JIS K2501 (2003)". The content of the resin having a structure represented by General Formula (1) is preferably 5 to 60% by weight with respect to (a) the pigment. In the case where the (a-1) component or the (a-2) component is contained, in terms of improving the dispersion stability, it is preferably 5% by weight or more, and more preferably 15% by weight or more with respect to the total of the (a-1) component and the (a-2) component. In terms of improving the photocurability in the exposure step and improving the developing residue film rate described later, it is preferably 60% by weight or less, and more preferably 40% by weight or less.

[0105] As a preferable specific example of the resin having a structure represented by General Formula (1), a resin having a structure represented by General Formula (16), a resin having a structure represented by General Formula (17) can be given. In terms of the developing property on the silver alloy film, the resin having a structure represented by General Formula (16) is more preferable.

[0106] [Chemical Formula 12]

[0107]

[0108] In General Formula (16), * indicates a bonding site to a carbon atom. A 5 O, A 6 O, OA 7 and OA 8 each independently represents an oxyalkylene group having 1 to 5 carbon atoms. A 9 and A 10 each independently represents an alkylene group having 2 to 6 carbon atoms.

[0109] n 1 is an integer, and represents 0 to 7. X 3 to X 6 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. a 19 to a 22 is an integer, and each independently represents 1 to 100.

[0110] In General Formula (17), * indicates a bonding site to a carbon atom. A 11 O, A 12 O each independently represents an oxyalkylene group having 1 to 5 carbon atoms. A 13 and A 14 each independently represents an alkylene group having 2 to 6 carbon atoms.

[0111] n 2 is an integer, and represents 0 to 7. X 7 and X 8 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. X 9 and X 10 are the same as each other, and represent an alkyl group having 1 to 4 carbon atoms. a 23 to a 24 is an integer, and each independently represents 1 to 100.

[0112] The resin having a structure represented by General Formula (16) has a total number of tertiary amino groups in the molecule of 2 to 9, but from the viewpoint of excellent effects of improving adsorption to the surface of a pigment, and suppressing development residue on a silver alloy film from a pigment aggregate, n 1 is preferably 1 or more. From the viewpoint of excellent effects of suppressing cross-linking adsorption to the surface of a pigment and the surface of a silver alloy film, and suppressing development residue on a silver alloy film from a dispersant, n 1 is preferably 5 or less. That is, the total number of tertiary amino groups in the molecule is preferably in the range of 3 to 7. Furthermore, from the viewpoint of excellent dispersing and stabilizing effects, A 9 and A 10Each of the alkylene groups is preferably an alkylene group having 2 to 4 carbon atoms, and a straight-chain alkylene group is preferable. Specifically, ethylene, propylene, or butylene is preferable. The bonding site with the alkyl group having 1 to 5 carbon atoms is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably an alkylene group having 1 to 5 carbon atoms. The above-mentioned view is also applicable to the resin having a structure represented by General Formula (17).

[0113] As a method for synthesizing the above resin, a method in which an aliphatic amine having a primary amino group is used as a base material, and a polyoxyalkylene chain is added and polymerized by the above-mentioned method can be given. As the aliphatic amine having a primary amino group, for example, ethylenediamine (number of nitrogen atoms: 2), diethylenetriamine (number of nitrogen atoms: 3), triethylenetetramine (number of nitrogen atoms: 4), tetraethylenepentamine (number of nitrogen atoms: 5), pentaethylenehexamine (number of nitrogen atoms: 6), heptaethyleneoctamine (number of nitrogen atoms: 8), dipropylenetriamine (number of nitrogen atoms: 3), propylenediamine (number of nitrogen atoms: 2), hexamethylenediamine (number of nitrogen atoms: 2), N,N-bis(3-aminopropyl)methylamine (number of nitrogen atoms: 3), 3-diethylaminopropylamine (number of nitrogen atoms: 2), 3-dimethylaminopropylamine (number of nitrogen atoms: 2), 3-diethylaminoethylamine (number of nitrogen atoms: 2), 3-diethylaminoethylamine (number of nitrogen atoms: 2), spermine (number of nitrogen atoms: 4) can be given. Note that, from the viewpoint of improving dispersion stability and developability on a silver alloy film, it is possible to convert all of the primary amino groups (or primary amino groups and secondary amino groups) from the raw material into tertiary amino groups, and, in order to make the lengths of the polyoxyalkylene chains within the molecule uniform, it is preferable to perform the synthesis in the presence of a catalyst.

[0114] As the catalyst, an inorganic base catalyst such as sodium hydroxide or potassium hydroxide can be used. In order to avoid adverse effects on the light-emitting properties of the organic EL display device, it is preferable to use the inorganic base catalyst as a dispersant after removing the inorganic base catalyst with a catalyst scavenger after the reaction is completed. As the catalyst scavenger, a solid acid adsorbent such as synthetic aluminum silicate can be used. Note that, with respect to the presence of the aliphatic amine having a primary amino group, it is possible to determine the presence of the primary amino group by causing sodium nitrite to act under acidic conditions and using the release of nitrogen gas generated by diazotization decomposition. In addition, infrared absorption spectroscopy can be used to confirm the presence or absence of a secondary amino group based on the absorption peak at a wavelength of 1550 cm -1 On the other hand, it is possible to confirm the presence or absence of a primary amino group based on the absorption peak at a wavelength of 1600 cm -1 The structure of the resin having a structure represented by General Formula (1) can be analyzed by column separation on the basis of concentration of the photosensitive composition or the negative photosensitive composition by centrifugation or the like, and known methods such as NMR, IR, and mass spectrometry.

[0115] The tertiary polyamine main chain of the resin having the structure represented by General Formula (16) can be linear or branched, and is preferably linear from the viewpoint of excellent dispersion stabilization effect. When the tertiary polyamine main chain is linear, the structure represented by General Formula (1) is disposed only at both ends of the tertiary polyamine main chain. That is, the negative photosensitive composition of the present application preferably contains, as the component (b), a resin having the structure represented by General Formula (16) and having two structures represented by General Formula (1) in the molecule. As specific examples, the following linear tertiary polyamine resins represented by General Formula (18) and General Formula (19), and the branched tertiary polyamine resin represented by General Formula (20) are exemplified. In addition, as the resin having the structure represented by General Formula (17), for example, the resin represented by General Formula (21) can be given.

[0116] [Chemical Formula 13]

[0117]

[0118] [Chemical Formula 14]

[0119]

[0120] [Chemical Formula 15]

[0121]

[0122] In General Formula (18), General Formula (19), and General Formula (20), a 25 ~a 58 are integers, each independently represents an integer of 1 to 20.

[0123] [Chemical Formula 16]

[0124]

[0125] In General Formula (21), a 59 ~a 62 are integers, each independently represents an integer of 1 to 20.

[0126] In the case where the photosensitive composition of the present application has negative photosensitivity, or the negative photosensitive composition of the present application, it is preferable to further contain, as the component (b), a resin represented by General Formula (22). The resin represented by General Formula (22) stabilizes the dispersion state of the above-mentioned (a-1) component or (a-2) component, suppresses the effect of development residue from the unexposed portion, and in addition, promotes photocuring in the exposure step described later, and has the effect of suppressing the generation of development residue due to insufficient curing at the bottom of the pattern edge of the exposed portion.

[0127] [Chemical Formula 17]

[0128]

[0129] In general formula (22), A 15 O, A 16 O, OA 17 OA 18 and OA 19 Each can be used independently to represent an alkylene oxide with 1 to 5 carbon atoms.

[0130] A 20 and A 21 Each can be used independently to represent an alkylene group having 2 to 6 carbon atoms. 3 It is an integer, representing 0 to 9. X 11 ~X 15 Each can independently represent a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, an organic group represented by general formula (23), or an organic group represented by general formula (24). Wherein, X 11 and X 12 At least one of them and X 13 and X 14 At least one of them is an organic group represented by general formula (23) or an organic group represented by general formula (24). 63 ~a 67 Each integer represents 1 to 100 independently.

[0131] [Chemical Formula 18]

[0132]

[0133] In general formula (23), * indicates the bonding site with an oxygen atom. X 16 It represents a hydrogen atom or a methyl group.

[0134] In general formula (24), * indicates the bonding site with an oxygen atom. X 17 Represents a hydrogen atom or a methyl group. A 22 O represents an alkylene oxide with 1 to 5 carbon atoms. a 68 It is an integer, representing 1 to 5.

[0135] The resin represented by General Formula (22) can be synthesized by derivatizing a resin having a structure represented by General Formula (16). As specific examples of derivatization, there can be mentioned a method in which a radical polymerizable acyl halide compound such as acryloyl chloride and / or methacryloyl chloride is reacted in solution, the terminal hydrogen atoms of the polyoxyalkylene chain are converted into organic groups represented by General Formula (23), and then the chlorine ions are removed. Further, there can be mentioned a method in which a radical polymerizable isocyanate compound such as 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, and / or 2-(2-methacryloyloxyethyloxy)ethyl isocyanate is reacted in solution, the terminal hydrogen atoms of the polyoxyalkylene chain are converted into organic groups represented by General Formula (24). The number of introduction of the organic groups represented by General Formula (23) and / or the organic groups represented by General Formula (24) can be controlled by adjusting the ratio of hydrogen atoms at the terminal of the polyoxyalkylene chain possessed by the resin having a structure represented by General Formula (16) to hydrocarbon groups having a carbon atom number of 1 to 5.

[0136] For A 15 O, A 16 O, OA 17 , OA 18 , OA 19 , A 20 , A 21 and n 3 The preferred range of A is the same as that described above in the resin having a structure represented by General Formula (16). As specific examples of the resin represented by General Formula (22), there can be mentioned a resin represented by Structural Formula (25) and a resin represented by Structural Formula (26).

[0137] [Chemical Formula 19]

[0138]

[0139] [Chemical Formula 20]

[0140]

[0141] The photosensitive composition or the negative-type photosensitive composition of the present application can further be used in combination with a resin not having a structure represented by General Formula (1) as the (b) component. As the resin belonging to the (b) component and not having a structure represented by General Formula (1), there can be preferably mentioned a polyamide polyester-based resin, a block polymerization-type acrylic resin comprising an A block having a tertiary amino group and a B block not having a tertiary amino group, and a random polymerization-type acrylic resin in which a structural unit not having a tertiary amino group and a structural unit having a tertiary amino group are irregularly arranged in the side chain of the polymer.

[0142] The above resin can be used in admixture with a resin having a structure represented by General Formula (1), and the dissolution rate of the unexposed portion of the film in the developer, the exposure sensitivity can be adjusted in such a manner that the appropriate development time in the desired range is obtained, without impairing the effects of the present application. As the polyamide polyester-based resin, for example, "DISPERBYK" (registered trademark) -2200 (manufactured by BYK Chemie Co., Ltd.), "Solsperse" (registered trademark) 11200, Solsperse 28000, Solsperse 32000, 32500, 32600, 33500, M385 (all of which are manufactured by Lubrizol Co., Ltd.) can be given. As specific examples of the block polymerization type acrylic-based resin, for example, "DISPERBYK" (registered trademark) -2000, "BYK" (registered trademark) -6919 (both of which are manufactured by BYK Chemie Co., Ltd.), and the resins described in Japanese Patent Application Publication No. 2019-89954 can be given. As the random polymerization type acrylic-based resin, the resin in which a radical polymerization group is introduced described in Japanese Patent Application Publication No. 2013-245221 can be given.

[0143] As the form of the resin having a structure represented by General Formula (1) in the photosensitive composition or the negative-type photosensitive composition, at least a part of the tertiary amino group can form a salt with another component. As the salt-forming component, a phosphoric acid ester-based resin can be given, and for example, a straight-chain polyether (or polyether polyester) -based resin having a phosphoric acid group at one terminal, a straight-chain polyether (or polyether polyester) -based resin having phosphoric acid groups at both terminals, and more preferably, a straight-chain polyether-based resin having phosphoric acid groups at both terminals from the viewpoint of excellent development properties. As a specific example of the straight-chain polyether polyester-based resin having a phosphoric acid group at one terminal, a mono-phosphoric acid ester having a phosphoric acid group at one terminal of a straight-chain block copolymer of polyethylene glycol and polycaprolactone, that is, "DISPERBYK" (registered trademark) -111 (manufactured by BYK Chemie Co., Ltd.) can be given. As the straight-chain polyether-based resin having phosphoric acid groups at both terminals, a compound represented by General Formula (27) can be given, and from the viewpoint of balancing the effects of improving the development properties and the dispersion stability, the content thereof relative to the resin having a structure represented by General Formula (1) is preferably 0.5 to 20% by weight.

[0144] [Chemical Formula 21]

[0145]

[0146] In General Formula (27), A 23 O represents an oxyalkylene group having 1 to 5 carbon atoms.a 69 is an integer, and represents 20 to 100.

[0147] From the viewpoint of development properties, [A23 O]a 69 The partial structure represented by the formula (a) is preferably a polyoxyalkylene chain containing an ethylene oxide, a n-propylene oxide, and / or an isopropylene oxide, a is an integer of 1 to 20. 69 Preferably, a is 20 to 80.

[0148] The photosensitive composition or the negative type photosensitive composition of the present application contains (c) a photosensitizer. The photosensitizer in the case of the negative type photosensitive composition of the present application, or the photosensitizer in the negative type photosensitive composition of the present application refers to a compound having no tertiary amino group and having 2 or more radical polymerizable groups in the molecule, and a photopolymerization initiator, by containing both components, a function of being photosensitive to active chemical rays such as ultraviolet rays to cause radical polymerization reaction to perform photocuring can be imparted, and a negative type pattern in which the exposed portion is insolubilized in a developer is formed. As the radical polymerizable group, a vinyl group, a (meth)acrylic acid group can be mentioned, from the viewpoint of excellent photocurability, the (meth)acrylic acid group is preferred. The (meth)acrylic acid group refers to a methacrylic acid group or an acrylic acid group.

[0149] As the compound having no tertiary amino group and having 2 or more radical polymerizable groups in the molecule, for example, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, 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, DPHA-40H (10-functional monomer having a structure in which 2 molecules of dipentaerythritol pentaacrylate are connected by urethane bonds from hexamethylene diisocyanate (manufactured by Japan Epoxy Resin), ε-caprolactone-modified 6-functional (meth)acrylate, 2-functional (meth)acrylate having a bisphenol A skeleton.

[0150] From the viewpoint of taking into consideration both inhibition of development residue and pattern edge shape, it is preferred that the compound having 5 or more radical polymerizable groups in the molecule be used in combination with the compound having 4 or less radical polymerizable groups, and it is more preferred that the compound having 6 or more radical polymerizable groups be used in combination with the compound having 2 radical polymerizable groups.

[0151] Among them, considering excellent photocurability, ε-caprolactone-modified 6-functional acrylates represented by general formula (28) are preferred. As a specific example of a commercially available product, n in general formula (28) can be cited. 4 The "KAYARAD" (registered trademark) DPCA-20, n 4 KAYARAD DPCA-30 with a value of 3, n 4 KAYARAD DPCA-60 with a value of 6, n 4 KAYARAD DPCA-120 with a rating of 6 (all of the above are from Nippon Kayaku Corporation).

[0152] Furthermore, considering the potential to improve the adhesion of the pixel segmentation layer to the transparent conductive film, a difunctional (meth)acrylate having a bisphenol A backbone represented by general formula (29) is preferred. As a specific example of a commercially available product, one could cite a product where, in general formula (29), A... 24 O represents ethylene oxide, X represents... 18 and X 19 For hydrogen atoms, a 70 With a 71 The sum of 4 is BP-4EAL, A, "Light Acrylate" (registered trademark). 25 O represents isopropylidene oxide, X represents... 18 and X 19 For hydrogen atoms, a 70 With a 71 Light Acrylate BP-4PA (all manufactured by Kyoei Co., Ltd.) with a sum of 4. Furthermore, considering the need to moderately improve the hydrophobicity of the film to suppress peeling during development, and to set the pattern edges of the pixel segmentation layer to a low-tapered shape, it is preferable to use a difunctional acrylate with a fluorene structure. Specific examples include OGSOL EA-0250P, OGSOL EA-0200, and OGSOL EA-0300 (all manufactured by Osaka Gas Chemicals).

[0153] [Chemical Formula 22]

[0154]

[0155] In general formula (28), n 4 It is an integer, representing 1 to 6.

[0156] In general formula (29), a 70 and a 71 A is an integer, representing 1 to 4. 24 O and A 25 O represents an alkylene oxide with 1 to 3 carbon atoms. X 18and X 19 The same as each other indicates a hydrogen atom or a methyl group.

[0157] From the viewpoint of balancing the suppression of developing residue and the low-conical shape of the pattern edge, the content of compounds that do not have tertiary amines and have two or more free radical polymerizable groups in the solid components of the negative photosensitive composition is preferably 10 to 40 by weight.

[0158] As photopolymerization initiators, oxime ester-based photopolymerization initiators, alkyl phenyl ketone-based photopolymerization initiators, and acylphosphine oxide-based photopolymerization initiators are preferred examples.

[0159] Examples of oxime ester-based photopolymerization initiators include the compound represented by structural formula (30), namely "Adeka Arkls" (registered trademark) NCI-831E (manufactured by ADEKA Co., Ltd., hereinafter referred to as "NCI-831E"), the compound represented by structural formula (31), the compound described in Japanese Patent Application Publication No. 2008 / 100955, the compound described in International Patent Publication No. 2006 / 018405, and the compound represented by structural formula (32), namely "Irgacure" (registered trademark) OXE02 (hereinafter referred to as "OXE02"). It should be noted that NCI-831E has the same structure as NCI-831 described in Patent Document 4.

[0160] [Chemical Formula 23]

[0161]

[0162] [Chemical Formula 24]

[0163]

[0164] As the alkyl phenone-based photopolymerization initiator, "Omnirad" (registered trademark) 127 as 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropionyl)benzyl)phenyl)-2-methylpropane-1-one, "Omnirad" (registered trademark) 369 as 2-benzyl-2-(dimethylamino)-4-morpholinobutyrylbenzene, "Omnirad" (registered trademark) 379EG as 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (all of IGM Resins Co.), and the like can be given. As the acylphosphine oxide-based photopolymerization initiator, "Omnirad" (registered trademark) TPO H as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, "Omnirad" (registered trademark) 819 as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and the like can be given. The above photopolymerization initiators can be contained in combination with two or more kinds, and from the viewpoint of excellent bottom-up solubility of the film at the time of exposure and excellent inhibition of development residue, it is preferable that at least an oxime ester-based photopolymerization initiator be contained. From the viewpoint of giving consideration to both inhibition of development residue and taper shape of the pattern edge, the content of the photopolymerization initiator in the total solid content of the negative photosensitive composition is preferably 1 to 10% by weight.

[0165] On the other hand, in the case where the photosensitive composition of the present application is a positive photosensitive composition, the (c) photosensitive agent refers to a quinonediazide compound, imparts photosensitivity to active chemical rays such as ultraviolet rays, generates an indene carboxylic acid, and thereby improves the solubility in a developing solution, can relatively increase the solubility of the film at the exposed portion compared to the solubility of the film at the unexposed portion, and thereby form a positive pattern. As the quinonediazide compound, from the viewpoint of excellent exposure sensitivity, a naphthoquinone diazide compound is preferable.

[0166] The photosensitive composition or the negative photosensitive composition of the present application is further preferably contains a (d) alkali-soluble resin. The alkali-soluble resin refers to a resin having a carboxyl group and / or a hydroxyl group as an alkali-soluble group in its structure and not having an amino group and a phosphoric acid group, and does not belong to the above (b) component. By having a carboxyl group and / or a hydroxyl group, solubility in a developing solution is obtained, and in negative or positive lithography, the unexposed portion or the exposed portion is easily selectively removed, and the patterning property of the pixel partition layer becomes good.

[0167] As the alkali-soluble resin, for example, an alkali-soluble polyimide resin, an alkali-soluble polyimide precursor (alkali-soluble polyamic acid resin), an alkali-soluble epoxy acrylate resin, an alkali-soluble Cardo resin, an alkali-soluble acrylic resin, an alkali-soluble urethane (meth) acrylate resin, an alkali-soluble polybenzoxazole resin, an alkali-soluble polybenzoxazole precursor, an alkali-soluble polysiloxane resin, an alkali-soluble Novolac resin, and the like can be exemplified. The above-mentioned resins can be combined, containing two or more kinds.

[0168] Note that, in the present specification, the alkali-soluble Cardo resin means an alkali-soluble resin having a Cardo skeleton in the molecule and not having an imide skeleton. On the other hand, an alkali-soluble polyimide resin containing a structural unit having a Cardo skeleton is classified as an alkali-soluble polyimide resin. The Cardo skeleton means a skeleton having two aromatic groups bonded to a quaternary carbon atom as a ring carbon atom constituting a cyclic structure.

[0169] Among them, from the viewpoint of not hindering the dispersion stabilization effect by the resin having a structure represented by General Formula (1) under a freezing condition, an alkali-soluble polyimide resin, an alkali-soluble epoxy (meth) acrylate resin, and an alkali-soluble acrylic resin are preferred. From the viewpoint of improving the heat resistance of the pixel division layer, the component (d) is more preferably at least contains an alkali-soluble polyimide resin and / or an alkali-soluble epoxy (meth) acrylate resin.

[0170] As the alkali-soluble polyimide resin, a resin having a phenolic hydroxyl group is preferred, and an alkali-soluble polyimide resin having a structural unit represented by General Formula (33) can be exemplified.

[0171] [Chemical Formula 25]

[0172]

[0173] In General Formula (33), R 19 represents an organic group having a valence of 4 to 10. R 20 represents an organic group having a valence of 2 to 8. R 21 and R 22 represents a phenolic hydroxyl group. p and q are integers, and each independently represents 0 to 6.

[0174] In General Formula (33), R 19 -(R 21 )p represents a residue of a diacid anhydride. R 19 It is preferred to be an organic group having a carbon number of 5 to 50 having an aromatic ring or a cyclic aliphatic group.

[0175] As the dianhydride, for example, there can be mentioned pyromellitic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride, butane tetracarboxylic dianhydride, 4,4-oxydiphthalic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-tetracarboxylic dianhydride, bicyclo[2.2.2]octane tetracarboxylic dianhydride.

[0176] In General Formula (33), R 20 -(R 22 )q represents a residue of a diamine. R 20 Preferably, it is an organic group having an aromatic ring or a cyclic aliphatic group having 5 to 40 carbon atoms.

[0177] As the diamine, for example, there can be mentioned m-phenylenediamine, p-phenylenediamine, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)fluorene, diaminodiphenyl ether, diaminodiphenylmethane, diaminodiphenylpropane, diaminodiphenylhexafluoropropane, 2,2'-bistrifluorobenzidine, 2,2'-bistrifluorobenzidine, 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane, 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane.

[0178] From the viewpoint of improving the dispersion stabilizing effect of the resin having a structure represented by General Formula (1), the photosensitive composition or the negative photosensitive composition of the present application preferably contains an acetate-based solvent among the solvents described later. In order to improve the solubility in an acetate-based organic solvent, the base-soluble polyimide resin having a structural unit represented by General Formula (33) preferably has a fluorine atom in the molecule. As a specific example, there can be mentioned a resin having a structural unit from a dianhydride represented by Structural Formula (34) and / or (35), and a structural unit from a diamine represented by Structural Formula (36).

[0179] [Chemical Formula 26]

[0180]

[0181] From the viewpoint of inhibiting development residue, the acid value of the alkali-soluble polyimide resin is preferably 100 mgKOH / g or more. From the viewpoint of inhibiting pattern edge peeling in the development step, the acid value is preferably 400 mgKOH / g or less. The acid value can be measured by the potentiometric titration method based on "JIS K2501 (2003)" using a potentiometric titrator (AT-510; manufactured by Kyoto Electronic Industrial Co., Ltd.), using a 0.1 mol / L NaOH / ethanol solution as a titration reagent, using xylene / dimethylformamide = 1 / 1 (weight ratio) as a titration solvent.

[0182] In the present specification, the alkali-soluble epoxy (meth)acrylate resin refers to a resin which is obtained by introducing an epoxy group of a parent epoxy resin into an olefinic unsaturated group by ring-opening addition of a carboxyl group of an olefinic unsaturated monocarboxylic acid, and further introducing a carboxyl group by ring-opening of the epoxy group, among acid-modified epoxy resins having a radical-polymerizable group, and which does not have a Cardo skeleton in the molecule. The expression "(meth)acrylate resin" refers to a resin having a methacrylic acid group and / or an acrylic acid group.

[0183] As the epoxy resin serving as the parent, an epoxy resin having a biphenyl structure, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, and a cresol novolac type epoxy resin can be given. As the olefinic unsaturated monocarboxylic acid for modifying the epoxy resin, for example, acrylic acid and methacrylic acid can be given. As the polycarboxylic acid (or anhydride thereof), maleic anhydride, succinic anhydride, and tetrahydrophthalic anhydride can be given.

[0184] As a commercially available product of a PGMEA solution of an alkali-soluble epoxy (meth)acrylate resin, ZAR-1494H, ZAR-2001H, ZFR-1491H, ZCR-1569H, ZCR-1797H, ZCR-1798H, and ZCR-1761H (all manufactured by Japan Epoxy Resin Co., Ltd.) can be given.

[0185] As the alkali-soluble epoxy (meth)acrylate resin which can be preferably used in the photosensitive composition or the negative-type photosensitive composition of the present application, from the viewpoint of excellent development from a silver alloy film, an alkali-soluble epoxy (meth)acrylate resin having a structure represented by General Formula (37) having a hydroxyl group resulting from ring-opening of an epoxy group as a residue can be given.

[0186] [Chemical Formula 27]

[0187]

[0188] In General Formula (37), * indicates a bonding site with a carbon atom constituting an aromatic ring. R 23 represents a hydrogen atom or a methyl group. Among them, from the viewpoint of excellent developability on a silver alloy film, a substance having a biphenyl structure in addition to the structure represented by General Formula (37) is preferable, and as a specific example, a structure represented by General Formula (38) is preferable, and ZCR-1569H, ZCR-1797H, ZCR-1798H, ZCR-1761H among the above-mentioned commercially available products meet the requirement.

[0189] [Chemical Formula 28]

[0190]

[0191] From the viewpoint of suppressing development residue, the acid value of the alkali-soluble epoxy (meth)acrylate resin is preferably 30 mgKOH / g or more. From the viewpoint of suppressing pattern edge peeling in the development process, it is preferably 200 mgKOH / g or less.

[0192] As the alkali-soluble acrylic resin, a resin obtained by selecting two or more (meth)acrylate compounds having one ethylenic unsaturated double bond in the molecule and copolymerizing them can be given. As the (meth)acrylate compound, for example, benzyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, methyl (meth)acrylate, n-butyl (meth)acrylate, ethyl (meth)acrylate, polyethylene glycol (meth)acrylate, isobornyl acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, (meth)acrylic acid, glycidyl (meth)acrylate, oxazolidine (meth)acrylate, tricyclodecane (meth)acrylate, and the like can be given.

[0193] Among them, from the viewpoint of improving developability on a silver alloy film, the (d) component preferably contains an alkali-soluble acrylic resin having a structural unit represented by Structural Formula (39). In addition, from the viewpoint of being able to impart a moderate exposure sensitivity and a dissolution speed in a developer, it can be preferable in the case of forming a pixel division layer having a thick film site and a thin film site in the plane described later by halftone processing.

[0194] Among the above-mentioned (meth)acrylate-based compounds having one ethylenically unsaturated double bond in the molecule, the structural unit derived from (meth)acrylate ester of 2-hydroxyethyl, (meth)acrylate ester of 2-hydroxypropyl, (meth)acrylate ester of 2-hydroxybutyl, (meth)acrylate ester of 4-hydroxybutyl corresponds to the structural unit represented by Structural Formula (39). As specific examples, a methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer, an acrylic acid / 4-hydroxybutyl acrylate / 2-ethylhexyl methacrylate copolymer can be preferably mentioned.

[0195] [Chemical Formula 29]

[0196]

[0197] In General Formula (39), R 24 represents a hydrogen atom or a methyl group. R 25 is a divalent linking group, and represents a hydrocarbon group having 2 to 6 carbon atoms.

[0198] From the viewpoint of suppressing development residue, the acid value of the alkali-soluble acrylic resin is preferably 5 mgKOH / g or more. From the viewpoint of suppressing pattern edge peeling in the development process, it is preferably 200 mgKOH / g or less.

[0199] As the alkali-soluble resin, in addition to the above-mentioned alkali-soluble polyimide resin and / or alkali-soluble epoxy (meth)acrylate resin, an alkali-soluble acrylic resin having a structural unit represented by Structural Formula (39) is particularly preferable.

[0200] The photosensitive composition or negative-type photosensitive composition of the present application further preferably contains a solvent. By containing a solvent, the viscosity of the photosensitive composition can be adjusted according to the desired coating method, and the coatability can be improved.

[0201] As the solvent, for example, an ether-based solvent, an acetate-based solvent, an ester-based solvent, a ketone-based solvent, an alcohol-based solvent, and the like can be mentioned, and among them, from the viewpoint of being able to improve the dispersion stabilization effect of the resin having a structure represented by General Formula (1), an acetate-based solvent is preferable.

[0202] As the acetic acid ester-based organic solvent, for example, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, n-propyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 1,3-butanediol diacetate can be given. Among them, from the viewpoint of improving the dispersion stability, propylene glycol monomethyl ether acetate (hereinafter, "PGMEA"), 3-methoxybutyl acetate (hereinafter, "MBA") are preferable. In addition, in order to adjust the drying speed at the time of pre-baking, 3-methoxy-1-butanol (hereinafter, "MB"), propylene glycol monomethyl ether, or the like can be used in a small amount.

[0203] The photosensitive composition or the negative-type photosensitive composition of the present application can further contain water. By containing a small amount of water, sometimes (a) the dispersion stability of the pigment is improved. In the photosensitive composition, the content of water is preferably 1% by weight or less, more preferably 0.5% by weight or less. In the case of containing water, it is preferable that a part thereof exists in the form of adsorbed water on the surface of the pigment.

[0204] The photosensitive composition or the negative-type photosensitive composition of the present application can further contain an organic pigment derivative (a synergist) as a dispersion aid. The so-called organic pigment derivative is a compound in which a functional group selected from an acidic functional group, a basic functional group, and a neutral functional group is combined with an organic pigment skeleton, and the so-called organic pigment skeleton is a skeleton derived from a pigment such as a pigment or a dye. The organic pigment derivative can suppress the tendency of selective re-aggregation of a specific pigment and can suppress color separation during storage by reducing the difference in the adsorption of the dispersant on the surfaces of various pigments.

[0205] As the pigment to be the parent, perylene-based pigments, perinone-based pigments, cyanine-based pigments, phthalocyanine-based pigments, azo-based pigments, methine-based pigments, anthraquinone-based pigments, quinacridone-based pigments, dioxazine-based pigments, xanthene-based pigments, triarylmethane-based pigments, indigo-based pigments, thioindigo-based pigments, indigoid-based pigments, quinophthalone-based pigments can be given. As the acidic functional group, a sulfo group represented by Structural Formula (40), an aromatic group having a carboxyl group represented by Structural Formula (41) can be given. As the basic functional group, an organic group having one or more tertiary amino groups at the terminal through a linking group formed by a sulfonamide structure or a triazine ring can be given. As the neutral functional group, an organic group having a phthalimide structure represented by Structural Formula (42) can be given.

[0206] [Chemical Formula 30]

[0207]

[0208] In Structural Formula (40), Structural Formula (41), and Structural Formula (42), * indicates a bonding site with the pigment skeleton.

[0209] From the viewpoint of improving the dispersion stabilization effect on the (a-1) component, for example, a compound represented by Structural Formula (43) can be preferably used at times. From the viewpoint of improving the dispersion stabilization effect on the (a-2) component, for example, a compound represented by Structural Formula (44) can be preferably used at times.

[0210] [Chemical Formula 31]

[0211]

[0212] The photosensitive composition or the negative-type photosensitive composition of the present application can contain a thermal crosslinking agent. By containing a thermal crosslinking agent, the smoothness of the electrode surface after formation of the pixel division layer can be improved at times. As the thermal crosslinking agent, a polyfunctional epoxy compound can be used, and as a specific example of a commercially available product, TEPIC-L, TEPIC-S, TEPIC-PAS (all manufactured by Nissan Chemical Industries), NC-3000, XD-1000, XD-1000H (all manufactured by Japan Synthetic Rubber) can be mentioned.

[0213] The photosensitive composition or the negative-type photosensitive composition of the present application can further contain a surfactant, a leveling agent, an antioxidant, an ultraviolet absorber, and the like as other components.

[0214] As a method for producing the photosensitive composition or the negative-type photosensitive composition of the present application, for example, the (a) pigment and the (b) component, or the (a-1) component or the (a-2) component and the (b) component can be mixed with a solvent, and a pigment dispersion liquid can be produced by wet-type medium dispersion treatment, and then, the (c) photosensitive agent and other components can be added to the pigment dispersion liquid and stirred, and a filter can be filtered as necessary, whereby production can be performed.

[0215] As a dispersing machine for performing wet-type medium dispersion treatment, for example, a bead mill such as "Revo Mill" (registered trademark) (manufactured by Hatsuda Tekko), "Nano Getter" (registered trademark) (manufactured by Ashizawa Finetech), "DYNO-MILL" (registered trademark) (manufactured by Willy A. Bachofen), "SPIKE MILL" (registered trademark) (manufactured by Inoue Mfg.), "SandGrinder" (registered trademark) (manufactured by DuPont) can be mentioned. As a medium for the dispersing machine, zirconia beads, zircon beads, or alkali-free glass beads can be mentioned. Furthermore, the bead diameter is preferably 0.1 to 1 mm. The higher the sphericity, the more preferable. As a specific example of a commercially available product, "TORAY CERAM" (registered trademark) (manufactured by Toray Industries, Inc.) is given, and from the viewpoint of obtaining the desired average dispersed particle diameter described later, it is particularly preferable to use

[0216] The operating conditions of the wet-type disperser can be appropriately set so that the average dispersed particle diameter of the pigment described later is in the desired range. In terms of the average dispersed particle diameter of the entire particle component contained in the pigment dispersion liquid, or the photosensitive composition or negative-type photosensitive composition obtained by compounding the pigment dispersion liquid, from the viewpoint of avoiding short-circuiting at the time of application of voltage due to the generation of recrystallized foreign matter from the pigment in the forming process of the pixel division layer, it is preferable to be 30 nm or more, and more preferably 50 nm or more. From the viewpoint of avoiding short-circuiting at the time of application of voltage due to coarse particles, it is preferable to be 200 nm or less, and more preferably 150 nm or less. The average dispersed particle diameter refers to the secondary particle diameter D50 (cumulative 50% average diameter) of the pigment particles based on the light scattering intensity with respect to a light source (wavelength 532 nm / 10 mW, semiconductor excitation solid laser), and D50 can be calculated using a particle size distribution measuring device "SZ-100" (manufactured by Horiba Ltd.) as the cumulative average diameter with the fine particle diameter side as the base point (0%).

[0217] The photosensitive composition or negative-type photosensitive composition of the present application can be preferably used for the purpose of pixel division layer formation.

[0218] A method of forming a pixel division layer using the photosensitive composition or negative-type photosensitive composition of the present application will be described. The pixel division layer can be obtained, for example, by photolithography including a coating process, a pre-baking process, an exposure process, a development process, and a curing process in this order.

[0219] In the coating process, the photosensitive composition or negative-type photosensitive composition is coated on a substrate to obtain a coated film. As the substrate, for example, in the case of manufacturing an organic display device of a top emission type, as a coating device used in the coating process, for example, a slit coater, a spin coater, a gravure coater, a dip coater, a curtain coater, a roll coater, a spray coater, a screen printer, an inkjet machine can be given. For the pixel division layer, in terms of the panel configuration, in order to be formed into a film thickness of about 0.5 to 3 μm at the time after the curing process, from the viewpoint of being suitable for thin film coating, being less likely to cause coating defects, and being excellent in film thickness uniformity and productivity, a slit coater or a spin coater is preferable, and from the viewpoint of saving liquid, a slit coater is more preferable.

[0220] In the pre-baking step, the solvent in the coated film is volatilized by heating, thereby obtaining a pre-baked film. As the heating device, for example, a hot air oven, a hot plate, a far infrared oven (IR oven), or the like can be given. Pinhole pre-baking or contact pre-baking can also be performed. The pre-baking temperature is preferably 50 to 150°C, and the pre-baking time is preferably 30 seconds to 30 minutes. In order to further improve the film thickness uniformity, after the coating step, a portion of the solvent contained in the coated film can be volatilized using a vacuum / reduced pressure drier, and then the pre-baking step based on heating can be performed.

[0221] In the exposure step, active chemical rays are irradiated through an exposure mask from the film surface side of the pre-baked film, to obtain an exposed film. As the exposure device used in the exposure step, a step-and-exposure device, a mirror image projection mask aligner (MPA), a parallel light mask aligner (PLA), or the like can be given. As the active chemical rays irradiated at the time of exposure, a mixed ray of j line (wavelength 313 nm), i line (wavelength 365 nm), h line (wavelength 405 nm), g line (wavelength 436 nm), or the like, or i single line is generally used, and the exposure amount is generally 10 to 500 mJ / cm 2 (i line conversion value).

[0222] As the exposure mask, for example, a mask in which a thin film having light shielding properties formed of a metal such as chromium, a black organic resin, or the like is formed in a pattern on one side of the surface of a substrate such as glass, quartz, or a film having light transmittance at the exposure wavelength can be given. By performing pattern exposure so that active chemical rays are transmitted only through the opening portion, an exposed film having an exposed portion and an unexposed portion is obtained.

[0223] The exposed portion is a portion where exposure light is irradiated through the mask opening portion, and the unexposed portion is a portion where exposure light is not irradiated. In addition, in the case where the pixel division layer is used as a layer having a spacer function in the constitution of the panel member, the pixel division layer can have a thin film portion and a thick film portion in the plane. As a method of obtaining a pixel division layer having a thin film portion and a thick film portion, a method in which pattern exposure is performed through a half-tone exposure mask in which a plurality of opening portions having different light transmittances are formed in an exposure light region in the exposure step, that is, so-called half-tone processing, can be given.

[0224] In the developing step, in the case where the photosensitive composition of the present application is a negative photosensitive composition, only the unexposed portion is removed, and a patterned developed film is obtained. The unexposed portion becomes an opening portion of the pixel partition layer, and the electrode is exposed. In the case where it is a positive photosensitive composition, the exposed portion is removed, and a patterned developed film is obtained. The exposed portion becomes an opening portion of the pixel partition layer, and the electrode is exposed. The opening portion finally becomes a light-emitting pixel portion in the organic EL display device. As the developing method, for example, a method in which the exposed film is immersed in a developing solution which is an aqueous alkali solution for 10 seconds to 5 minutes by a spraying method, a dipping method, a spin-coating immersion method, or the like can be mentioned.

[0225] The so-called spin-coating immersion method is a method in which the unexposed portion is dissolved and removed by standing after the developing solution is just coated or sprayed. As the developing solution, an aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as "TMAH") at 0.3 to 3.0% by weight is preferred, and an aqueous solution of TMAH at 2.38% by weight is usually used. In addition, a cleaning treatment by spraying with deionized water and / or a dehydration treatment by air blowing can be added after development.

[0226] In the curing step, while the developed film is heat-cured by heating to improve heat resistance, moisture, components of the developing solution remaining by penetration, and the like are volatilized, and thus a pixel partition layer is obtained. As the heating device, for example, a hot-air oven, an IR oven, or the like can be mentioned. The heating temperature is preferably 230 to 300°C from the viewpoint of sufficiently heat-curing to obtain high light-emitting properties.

[0227] By the above steps, a pixel partition layer including a cured film of the photosensitive composition or the negative photosensitive composition of the present application can be obtained.

[0228] From the viewpoint of improving the value as a display device by suppressing reflection of external light, the optical density per 1.0 μm film thickness of the pixel partition layer is preferably 0.5 or more, and more preferably 1.0 or more. From the viewpoint of suppressing generation of developing residues and suppressing generation of non-lighting pixels, it is preferably 2.5 or less, and more preferably 2.0 or less. The so-called optical density is a value obtained by dividing, by the value of the film thickness, i.e., 1.5, a value calculated from the incident light intensity and the transmitted light intensity of the pixel partition layer formed on a transparent substrate in such a manner that the film thickness becomes 1.5 μm, and the higher the optical density, the higher the light-blocking property is indicated. As the transparent substrate, "TEMPAX" (manufactured by AGC TECHNO GLASS Co., Ltd.) as a transparent glass substrate can be preferably used.

[0229] Optical density = log 10 (I0 / I)

[0230] I0: incident light intensity

[0231] I: transmitted light intensity

[0232] Next, an organic EL display device having a pixel partition layer including a cured product of the photosensitive composition or the negative photosensitive composition of the present application will be described.

[0233] As the organic EL display device, for example, a configuration having a first electrode, a pixel partition layer, a light-emitting pixel, and a second electrode can be given. Figure 1 A cross-sectional view of a TFT substrate in an organic EL display device, which is preferably selected as a specific example of an embodiment of the present application, is shown.

[0234] On the surface of the substrate 6, a TFT 1 (thin film transistor) of a bottom gate type or a top gate type is provided in a matrix shape, and a TFT insulating layer 3 is formed so as to cover the TFT 1 and a wiring 2 connected to the TFT 1. Further, a planarization layer 4 is formed on the surface of the TFT insulating layer 3, and a contact hole 7 opening the wiring 2 is provided in the planarization layer 4. A first electrode 5 is patterned on the surface of the planarization layer 4 and connected to the wiring 2. A pixel partition layer 8 is formed so as to surround the pattern periphery of the first electrode 5. An opening portion is provided in the pixel partition layer 8, and a light-emitting pixel 9 including an organic EL light-emitting material is formed in the opening portion, and a second electrode 10 is formed so as to cover the pixel partition layer 8 and the light-emitting pixel 9. If the TFT substrate including the above-mentioned layers is sealed in vacuum, and then a voltage is directly applied to the light-emitting pixel portion, the light-emitting pixel 9 can emit light as an organic EL display device.

[0235] The light-emitting pixel 9 can be configured by arranging different kinds of pixels having light-emitting peak wavelengths of red, blue, and green regions each as a 3-primary color of light, or can be configured by forming a light-emitting pixel emitting white light over the entire surface and combining a color filter of red, blue, and green as another layer member. Generally, the peak wavelength of the red region of the display is 560 to 700 nm, the peak wavelength of the blue region is 420 to 500 nm, and the peak wavelength of the green region is 500 to 550 nm. As the organic EL light-emitting material configuring the light-emitting pixel, a material further combining a hole transport layer and an electron transport layer in addition to a light-emitting layer can be suitably used.

[0236] As a method of patterning the light-emitting pixels, a mask evaporation method can be given. The mask evaporation method is a method of patterning by evaporating an organic compound using an evaporation mask, and specifically, a method of evaporating while arranging the evaporation mask having a desired pattern as an opening portion on the substrate side. In order to obtain a high-precision evaporation pattern, it is important to adhere the evaporation mask having high flatness to the substrate, and generally, a technique of applying tension to the evaporation mask, a technique of adhering the evaporation mask to the substrate by a magnet arranged on the back side of the substrate, or the like can be used.

[0237] In the case of the top emission type organic EL display device, as the first electrode 5, a stacked pattern in which a transparent conductive film is stacked on the surface of a metal reflective layer can be given. The top emission type means a light emission mode in which light emitted from the light-emitting pixels is taken out in the opposite direction to the substrate 6 via the second electrode. As the metal reflective layer, a silver alloy film is generally used from the viewpoint of excellent reflectance of visible light and conductivity. The silver alloy means an alloy formed of silver and a metal other than silver, and an alloy in which the proportion of silver atoms is in the range of 60.0 to 99.9% by weight. From the viewpoint of improving the reflectance of visible light and conductivity, it is preferable to be 90.0% by weight or more, and from the viewpoint of improving chemical stability, it is preferable to be 99.5% by weight or less. As specific examples of the silver alloy, Ag / Cu (an alloy of silver and copper), Ag / Cu / Pd (an alloy of silver, copper, and palladium), and Ag / Cu / Nd (an alloy of silver, copper, and neodymium) can be given. As a commercially available product of a silver alloy target for sputtering that can be used for film formation of the first electrode or the second electrode of the organic EL light-emitting element described later, the "DIASILVER" (registered trademark) series (manufactured by Mitsubishi Materials Corporation) can be given.

[0238] As the transparent conductive film, a conductive metal oxide such as ITO (Indium Tin Oxide), ITZO (Indium Tin Zinc Oxide), or IZO (Indium Zinc Oxide) can be used. Among them, ITO is generally used from the viewpoint of excellent transparency and conductivity. Among them, amorphous ITO (hereinafter sometimes abbreviated as "a-ITO") or low-crystallinity ITO is preferable from the viewpoint of suppressing the deterioration of the silver alloy. In this specification, the low-crystallinity ITO means ITO obtained by heat-treating an amorphous ITO film obtained by a sputtering method or the like at a temperature in the range of 140 to 200°C. The amorphous ITO or the low-crystallinity ITO can be substantially subjected to high-temperature annealing treatment by heat in the curing process (for example, 230°C or higher) at the time of forming the pixel division layer, and is converted to a high-crystallinity ITO form in the finally obtained light-emitting element.

[0239] In order to improve the luminance of the light emitting pixel, the film thickness of the metal reflective layer is preferably 50 nm or more from the viewpoint of improving the reflectance, and the film thickness of the transparent conductive film is preferably 15 nm or less from the viewpoint of improving the transmittance.

[0240] As a method of forming the first electrode 5, a metal reflective layer is formed over the entire surface by a sputtering method, a positive resist for etching is then patterned by a photolithography method to obtain a resist film in a pattern, the metal reflective layer in a non-patterned portion of the resist is removed by an etching solution, the resist film is removed by a resist peeling solution, and a transparent conductive film in the same pattern is further layered by the same steps. The transparent conductive film can be formed so as to cover not only the upper portion of the metal reflective layer but also the side surface portion. In addition, in the case of layered constitution not covering the side surface portion, the metal reflective layer and the transparent conductive film can be formed together. In order to improve the adhesion of the metal reflective layer to the substrate, the layered constitution of the substrate / transparent conductive film / metal reflective layer / transparent conductive film can be used.

[0241] As the etching solution for the silver alloy film, for example, an inorganic etching solution such as a mixed acid of phosphoric acid and nitric acid can be used. As commercially available products, SEA-1, SEA-2, SEA-3, SEA-5 (all of which are manufactured by Kanto Chemical Co., Inc.) can be mentioned. As the etching solution for crystalline ITO, for example, an inorganic acid etching solution containing hydrochloric acid or the like can be used, and as commercially available products, ITO-02, ITO-301 (both of which are manufactured by Kanto Chemical Co., Inc.) can be mentioned. As the etching solution for amorphous ITO and IZO, for example, an organic acid etching solution containing oxalic acid or the like can be used, and as commercially available products, ITO-07N, ITO-101N (both of which are manufactured by Kanto Chemical Co., Inc.) can be mentioned. As the positive resist for etching, a positive photosensitive composition containing an alkali-soluble Novolac resin can be used. As the resist peeling solution, an organic amine aqueous solution can be used, and as commercially available products, for example, "Unlast" (registered trademark) M6, Unlast M6B, Unlast TN-1-5, Unlast M71-2 (all of which are manufactured by San-Apro Co., Ltd.) can be mentioned.

[0242] As the second electrode 10, a silver alloy film formed of Ag / Mg (an alloy of silver and magnesium) can be preferably used from the viewpoint of excellent transmittance of visible light, and can be formed by forming a film over the entire surface by a sputtering method. The film thickness of the second electrode is preferably 10 nm or more from the viewpoint of avoiding disconnection of the electrode. It is preferably 40 nm or less from the viewpoint of improving the transmittance and reducing the luminance loss of the light emitting pixel.

[0243] If the substrate 6 uses a hard plate-like substrate typified by glass, a rigid type organic EL display device that cannot be bent can be produced. As the glass, an alkali-free glass in which the content of alkali metal elements is less than 0.5% and silicon is the main component can be suitably used. Among them, a glass having a small coefficient of thermal expansion and excellent dimensional stability in a high-temperature process of 250°C or higher, such as OA-10G, OA-11 (both manufactured by Nippon Electric Glass Co., Ltd.), and AN-100 (manufactured by Asahi Glass Co., Ltd.), can be exemplified, and the thickness thereof is usually 0.1 to 0.5 mm from the viewpoint of physical durability.

[0244] On the other hand, if the substrate 6 uses a flexible substrate, a flexible type organic EL display device that can be bent can be produced. As the flexible substrate, a substrate formed of a polyimide resin having high flexibility and excellent mechanical strength can be suitably used, and as a method of producing the above substrate, a method in which a solution containing a polyamic acid is applied to the surface of a temporary support, and then the polyamic acid is imidized and converted into a polyimide resin by heat treatment at a high temperature of 300 to 500°C, and then the temporary support is peeled off by laser or the like can be exemplified. The polyamic acid can be synthesized by reacting a tetracarboxylic dianhydride and a diamine compound in an amide-based solvent such as N-methyl-2-pyrrolidone, and among them, a polyamic acid having a residue of an aromatic tetracarboxylic dianhydride and a residue of an aromatic diamine compound is preferable from the viewpoint of a small coefficient of thermal linear expansion and excellent dimensional stability. As a specific example, a polyamic acid having a residue of 3,3',4,4'-biphenyltetracarboxylic dianhydride and a residue of p-phenylenediamine can be exemplified. The thickness thereof is usually 10 to 40 μm, and the substrate 6 can be made thinner compared to the case where the above alkali-free glass is used.

[0245] Next, an organic EL display device as a third aspect of the present application will be described.

[0246] The organic EL display device as the third aspect of the present application has a pixel division layer containing a resin having two or more tertiary amino groups in a molecule and having a structure represented by General Formula (1).

[0247] By causing the pixel division layer to contain the resin having two or more tertiary amino groups in a molecule and having a structure represented by General Formula (1), generation of non-lighting pixels can be controlled.

[0248] From the viewpoint of controlling the generation of non-lighting pixels, the organic EL display device is preferably a top emission type.

[0249] The pixel partition layer of the organic EL display device of the present application preferably has a thin film portion having a film thickness of 0.5 μm or more and less than 2.0 μm, a thick film portion having a film thickness of 2.0 μm or more and 5.0 μm or less, and a portion where the difference between the film thickness of the thin film portion and the film thickness of the thick film portion is 1.0 μm or more. From the viewpoint of half-tone processability, the difference between the film thickness of the thin film portion and the film thickness of the thick film portion is more preferably 1.0 μm or more and 2.0 μm or less. The thin film portion and the thick film portion each refer to a portion having the thinnest film thickness and a portion having the thickest film thickness, respectively, in the pixel partition layer in the display region of the organic EL display device, except for the portion where the edge of the opening portion is inclined.

[0250] The thick film portion having a film thickness of 2.0 μm or more and 5.0 μm or less preferably functions as a spacer. On the other hand, the thin film portion having a film thickness of 0.5 μm or more and less than 2.0 μm is preferably provided for the opening portion for disposing a light-emitting pixel, and can be formed in a partition wall shape. Further, by having a portion where the difference between the film thickness of the thin film portion and the film thickness of the thick film portion is 1.0 μm or more, when the light-emitting pixel is patterned by the mask vapor deposition method described above, the thick film portion functions as a convex spacer, and damage to the thin film portion and the vapor deposition mask itself caused by contact with the vapor deposition mask can be prevented, and the yield of the organic EL display device at the time of production can be improved. For the pixel partition layer described above, although it can be formed in two layers by laminating a layer having a thick film portion on a surface of a layer having a thin film portion, from the viewpoint of reducing the number of processes, it is preferably formed at one time by the half-tone process described above.

[0251] Example

[0252] The present application will be described in detail below by citing examples and comparative examples thereof, but the present application is not limited to the following examples.

[0253] First, the evaluation method in each of the examples and comparative examples will be described.

[0254] <Calculation of the minimum necessary exposure amount>

[0255] On the surface of a 150 mm x 150 mm alkali-free glass substrate, an amorphous ITO film was formed by sputtering over the entire surface, and low-temperature annealing treatment was performed at 150°C for 30 minutes under a dry nitrogen atmosphere to obtain a substrate having a low-crystallinity ITO film with a film thickness of 10 nm. On the surface of the low-crystallinity ITO film, a negative photosensitive composition was coated with a spin coater so that the thickness of the cured film obtained finally would be 1.5 μm, using a spin coater, and a coating film was obtained. Using a hot plate (SCW-636; manufactured by Dainippon Screen Manufacturing Co., Ltd.), the coating film was subjected to prebaking at 100°C for 2 minutes under atmospheric pressure to obtain a prebaked film formation substrate, which was cut into two pieces. One of the prebaked film formation substrates was immersed in a tray containing a 2.38% by weight TMAH aqueous solution, and the prebaked film was dissolved, and the time at which a portion of the film was visually observed to have dissolved from the substrate was taken as the minimum necessary developing time. Further, using the other prebaked film formation substrate, an i-line transmission measurer that transmits only i-line light was installed in a single-side exposure device (mask aligner PEM-6M; manufactured by Union Optical Co., Ltd.) on both sides, and patterned exposure was performed with i-line light (wavelength: 365 nm) of an ultrahigh-pressure mercury lamp via a sensitivity-measuring gray mask (MDRM MODEL 4000-5-FS; manufactured by Opto-Line International, Inc.) to obtain an exposed film. Next, using a small-sized developing device for photolithography (AD-2000; manufactured by TAKIZAWA SANGYO K.K.), immersion-type developing was performed with a 2.38% by weight TMAH aqueous solution for a developing time of 1.5 times the minimum necessary developing time, and after rinsing with deionized water for 30 seconds, drying was performed by blowing air to obtain a developed film formation substrate having a patterned developed film. Next, using an FPD inspection microscope (MX-61L; manufactured by Olympus Corporation), the resolution pattern of the developed film thus produced was observed, and the minimum necessary exposure amount (sensitivity) of the negative photosensitive composition was determined with respect to the line-and-space pattern having an opening size of 40 μm width under the condition of mask deviation + 2 μm, at an exposure amount (mJ / cm 2 : value of the i-line illuminometer) of 42 μm (line width of the developed film).

[0256] <Half-tone processing>

[0257] On the surface of a substrate having a low-crystallinity ITO film obtained by the same method as described above, a coating film was obtained by adjusting the rotation speed so that the film thickness of the thick film portion formed by irradiation with the full-color-exposure amount to be described later in the finally obtained cured film was 3.0 μm, and then applying a negative photosensitive composition with a spin coater. The coating film was prebaked at 100°C for 2 minutes under atmospheric pressure using a hot plate to obtain a prebaked film formation substrate, and this was cut into two. One of the prebaked film formation substrates was immersed in a tray containing a 2.38% by weight aqueous TMAH solution, and the prebaked film was dissolved, and the time at which a portion in the plane was visually observed to reach the substrate was taken as the minimum necessary development time. Further, using the other prebaked film formation substrate, pattern exposure was performed with an i-line of an ultrahigh pressure mercury lamp through a sensitivity measurement gray scale mask to obtain an exposed film. Next, using an AD-2000, development was performed by spin immersion with a 2.38% by weight aqueous TMAH solution for a development time of 1.5 times the minimum necessary development time. After rinsing with deionized water for 30 seconds, drying was performed by blowing air to obtain a developed film formation substrate having a patterned developed film. Next, under air, a cured film formation substrate was obtained by heating at 230°C for 30 minutes. The exposure amount (mJ / cm2) at which the film thickness of the cured film was 1.5 μm was taken as the half-tone exposure amount of the negative photosensitive composition. In addition, the value of the half-tone exposure amount was multiplied by 100 and divided by 30 to obtain the full-color-exposure amount. That is, the half-tone exposure amount corresponds to 30% of the full-color-exposure amount. 2 : value of the i-line illuminance meter). In addition, the value of the half-tone exposure amount was multiplied by 100 and divided by 30 to obtain the full-color-exposure amount. That is, the half-tone exposure amount corresponds to 30% of the full-color-exposure amount.

[0258] (1) Evaluation of Optical Density (OD / μm) of Cured Film

[0259] The optical density of the substrate on which the cured film having a thickness of 1.5 μm was formed on the surface of "TEMPAX" (manufactured by AGC TECHNO GLASS Co., Ltd.) as a transparent glass substrate was measured using an optical densitometer (manufactured by X-Rite; X-Rite 361T) at three points in the plane from the film surface side, and the average value was calculated. The value obtained by dividing the value by 1.5 was rounded off at the second decimal place, and the value up to the first decimal place was obtained as the OD value per 1.0 μm thickness of the cured film (OD / μm). The higher the OD / μm, the more excellent the light-shielding property of the cured film was evaluated as a standard. The OD value of TEMPAX on which no cured film was formed was measured, and the result was 0.00, so the OD value of the substrate for optical density evaluation was regarded as the OD value of the cured film. The thickness of the cured film was measured at three points in the plane using a stylus-type film thickness measuring device (manufactured by Tokyo Precision (Co., Ltd.); Surfcom), and the average value was rounded off at the second decimal place, and the value up to the first decimal place was obtained.

[0260] (2) Evaluation of development residue on the transparent conductive film

[0261] The opening portions 10 in the central portion of the substrate for evaluation of development residue on the transparent conductive film obtained by Examples 1 to 16 and Comparative Examples 1 to 10 were observed using an optical microscope at a magnification of 100 times, and the number of development residues having a length diameter of 0.1 μm or more and less than 3.0 μm in each opening portion was counted. The average number of development residues observed per one opening portion was evaluated based on the following evaluation criteria, and AA and A to C were regarded as pass, and D to E were regarded as fail. In the case where residues having a length diameter exceeding 3.0 μm were observed, E was evaluated regardless of the average number of residues.

[0262] AA: No development residue was observed at all.

[0263] A: Less than 5 residues were observed.

[0264] B: More than 5 and less than 10 development residues were observed.

[0265] C: More than 10 and less than 20 development residues were observed.

[0266] D: More than 20 development residues were observed.

[0267] E: Development residues having a length diameter exceeding 3.0 μm were observed.

[0268] (3) Evaluation of change in surface roughness of silver alloy film

[0269] The substrate for surface roughness evaluation of the silver alloy film obtained by Examples 1 to 16 and Comparative Examples 1 to 10 was evaluated with respect to measurement items (i) and (ii), and the following measurement was performed using an atomic force microscope (AFM), the value output in μm was converted into nm, the second digit after the decimal point was rounded off, and the value up to the first digit after the decimal point was obtained. Note that, Figure 2 is a cross-sectional view showing the measurement site of the maximum height difference Rmax 2 .

[0270] Measurement Conditions

[0271] Atomic force microscope: Dimension Icon (manufactured by BRUKER Corporation)

[0272] Measurement area: 91.9 μm x 91.9 μm (in-plane 256-point measurement)

[0273] Sample temperature: 25°C

[0274] Output value: maximum height difference (Rmax)

[0275] Output unit: μm

[0276] Measurement Items

[0277] (i) Maximum height difference (Rmax 1 ) of the surface of the silver alloy film before coating

[0278] (ii) Maximum height difference (Rmax 2 ) of the surface of the silver alloy film after formation of the pixel division layer at the opening portion

[0279] The value obtained by subtracting Rmax 1 from Rmax 2 indicates the change after formation of the pixel division layer with the state before coating as the reference, and the smaller the value, the more excellent the surface roughness of the silver alloy film is maintained. Evaluation was performed based on the following evaluation criteria, and AA and A to C were set as acceptable, and D to E were set as unacceptable.

[0280] AA: The difference (Rmax 2 -Rmax 1 ) is less than 5.0 nm.

[0281] A: The difference (Rmax 2 -Rmax 1 ) is 5.0 nm or more and less than 10.0 nm.

[0282] B: The difference (Rmax 2 -Rmax 1) is 10.0 nm or more and less than 50.0 nm.

[0283] C: difference (Rmax 2 -Rmax 1 ) is 50.0 nm or more and less than 100.0 nm.

[0284] D: difference (Rmax 2 -Rmax 1 ) is 100.0 nm or more and less than 200.0 nm.

[0285] E: difference (Rmax 2 -Rmax 1 ) is 200.0 nm or more.

[0286] (4) Evaluation of generation rate (%) of non-lighting pixels

[0287] The top emission type organic EL display device obtained in each of Examples 1 to 16 and Comparative Examples 1 to 10 was caused to emit light for 500 hours by direct current driving at 10 mA / cm 2 , and each 1 part of the pixel parts 40 present in the plane was enlarged and displayed on a monitor at a magnification of 50 times. The number of non-lighting pixels contained in each of the top emission type organic EL display devices produced under the same conditions for every 10 parts was counted, and the generation rate (%) of non-lighting pixels was calculated by the following formula, and the value obtained by rounding off the first digit after the decimal point was calculated. Note that the total number of all the pixels serving as the evaluation object was 400. Evaluation was performed based on the following determination criteria, and A to C were set as pass, and D to E were set as fail.

[0288] Generation rate (%) of non-lighting pixels = total number of non-lighting pixels / total number of all the pixels x 100

[0289] A: generation rate of non-lighting pixels is less than 10%.

[0290] B: generation rate of non-lighting pixels is 10% or more and less than 15%.

[0291] C: generation rate of non-lighting pixels is 15% or more and less than 20%.

[0292] D: generation rate of non-lighting pixels is 20% or more and less than 30%.

[0293] E: generation rate of non-lighting pixels is 30% or more.

[0294] Hereinafter, information on chemical structures, solid content, and the like of various raw materials used in the examples and comparative examples will be shown.

[0295] "Dispersion 1": a compound represented by Structural Formula (45) (corresponding to a resin having a structure represented by General Formula (1). 100 wt% of the solid content).

[0296] [Chemical Formula 32]

[0297]

[0298] "Dispersion 2": a compound represented by Structural Formula (46) (corresponding to a resin having a structure represented by General Formula (1). 100 wt% of the solid content).

[0299] [Chemical Formula 33]

[0300]

[0301] "Dispersion 3": a compound represented by Structural Formula (47) (corresponding to a resin having a structure represented by General Formula (1). 100 wt% of the solid content).

[0302] [Chemical Formula 34]

[0303]

[0304] "Dispersion 4": a compound represented by Structural Formula (48) (corresponding to a resin having a structure represented by General Formula (1). 100 wt% of the solid content).

[0305] [Chemical Formula 35]

[0306]

[0307] "Dispersion 5": a compound represented by Structural Formula (49) (corresponding to a resin having a structure represented by General Formula (1). 100 wt% of the solid content).

[0308] [Chemical Formula 36]

[0309]

[0310] "Dispersion 6": a compound represented by Structural Formula (50) (corresponding to a resin having a structure represented by General Formula (1). 100 wt% of the solid content).

[0311] [Chemical Formula 37]

[0312]

[0313] "Dispersion 7": a compound represented by Structural Formula (51) (corresponding to a resin having a structure represented by General Formula (1). 100 wt% of the solid content).

[0314] [Chemical Formula 38]

[0315]

[0316] "Dispersion 8": a compound represented by Structural Formula (52) (corresponding to a resin having a structure represented by General Formula (1). Solid content 100% by weight).

[0317] [Chemical Formula 39]

[0318]

[0319] "Dispersion 9": a PGMEA solution of a compound represented by Structural Formula (53) (corresponding to a resin represented by General Formula (22). Solid content 20% by weight).

[0320] [Chemical Formula 40]

[0321]

[0322] "Dispersion 10": a compound represented by Structural Formula (54) (a resin not having a structure represented by General Formula (1). Solid content 100% by weight).

[0323] [Chemical Formula 41]

[0324]

[0325] "Dispersion 11": a compound represented by Structural Formula (55) (having one tertiary amino group in the molecule. Solid content 100% by weight).

[0326] [Chemical Formula 42]

[0327]

[0328] "Solsperse 24000 GR": a compound having a structural unit represented by Structural Formula (56) in the molecule (manufactured by Lubrizol Corporation: a resin not having a structure represented by General Formula (1), a polymer in which a plurality of side chains having an aliphatic chain are grafted to a main chain derived from polyethyleneimine. Solid content 100% by weight).

[0329] [Chemical Formula 43]

[0330]

[0331] In Structural Formula (56), * indicates a bonding site.

[0332] "DISPERBYK-LPN21116": an ethylene glycol monobutyl ether / 1-methoxy-2-propyl acetate solution of a compound having, within the molecule, a structural unit represented by Structural Formula (57), a structural unit represented by Structural Formula (58), and a structural unit represented by Structural Formula (59) (manufactured by BYK Chemie: resin not having a structure represented by General Formula (1), block-type acrylic copolymer having a quaternary ammonium salt group and a tertiary amino group. Solid content 40% by weight).

[0333] [Chemical Formula 44]

[0334]

[0335] "Solsperse 20000": a resin having one tertiary amino group at one end of a linear polyalkylene chain having an ethylene oxide structure and a propylene oxide structure (manufactured by Lubrizol: resin not having a structure represented by General Formula (1). Solid content 100% by weight).

[0336] "DISPERBYK-167": a solid content 52% by weight solution of a urethane resin having an isocyanurate ring and a polycaprolactone chain within the molecule (manufactured by BYK Chemie: resin not having a structure represented by General Formula (1)).

[0337] "DISPERBYK-111": a phosphoric acid monoester-based dispersant having a phosphoric acid group at one end of a linear block copolymer of polyethylene glycol and polycaprolactone (manufactured by BYK Chemie: resin not having a structure represented by General Formula (1). Solid content 100% by weight).

[0338] "Dispersion aid a": a compound represented by Structural Formula (44).

[0339] "Dispersant 12": a compound represented by Structural Formula (60) (low-molecular compound not belonging to the resins in this specification. Solid content 100% by weight).

[0340] [Chemical Formula 45]

[0341]

[0342] Information on the number of tertiary amino groups possessed within the molecule, the presence or absence of a structure represented by General Formula (1), and the like for Dispersants 1 to 12 is shown in Table 1.

[0343] [Table 1]

[0344]

[0345] "ZCR-1569H": PGMEA solution of an alkali-soluble epoxy (meth)acrylate resin having a structural unit represented by general formula (38) (manufactured by Japan Epoxy Resin Co., Ltd.: solid content acid value 98 mgKOH / g: weight average molecular weight 4500: solid content 70% by weight).

[0346] "ZCR-1797H": PGMEA solution of an alkali-soluble epoxy (meth)acrylate resin having a structural unit represented by general formula (38) (manufactured by Japan Epoxy Resin Co., Ltd.: solid content acid value 98 mgKOH / g: weight average molecular weight 6400: solid content 62% by weight).

[0347] "WR-301": PGMEA solution of an alkali-soluble Cardo resin (manufactured by ADEKA: solid content acid value 98 mgKOH / g: weight average molecular weight 5500: solid content 42% by weight).

[0348] "Benzodifuranone-based black pigment 1": benzodifuranone-based black pigment represented by structural formula (4) (specific surface area based on BET method 30 m 2

[0349] (Synthetic Example 1: Synthesis of alkali-soluble polyimide resin A)

[0350] Under a dry nitrogen stream, 150.15 g of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (0.41 mol), 6.20 g of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (0.02 mol), and 13.65 g of 3-aminophenol (0.13 mol) as an end-capping agent were dissolved in 500.00 g of N-methyl-2-pyrrolidone (hereinafter "NMP") as an organic solvent, 155.10 g of bis(3,4-dicarboxyphenyl)ether dianhydride (0.50 mol) and 150 g of NMP were added thereto, and stirring was performed at 20°C for 1 hour, and further, while water was removed, stirring was performed at 180°C for 4 hours. After the completion of the reaction, the reaction liquid was poured into 10 L of water, the resulting precipitate was collected by filtration, washed with water 5 times, and dried with a vacuum drier at 80°C for 20 hours, thereby synthesizing an alkali-soluble polyimide resin A in the form of a white powder having a weight average molecular weight (Mw) of 25000.

[0351] (Synthetic Example 2: Synthesis of alkali-soluble acrylic resin solution B)

[0352] ​Under a dry nitrogen stream, and with the liquid temperature maintained at 120°C and under stirring, a mixture of 72.10 g of 4-hydroxybutyl acrylate (0.50 mol), 92.15 g of 2-ethylhexyl acrylate (0.50 mol), 1.47 g of acrylic acid (0.02 mol), and 8.16 g of tert-butyl peroxide-2-ethylhexanoate as a polymerization initiator was added dropwise over 1 hour using a funnel until the weight-average molecular weight of the resulting copolymer reached 10,000. Copolymerization was carried out at 120°C with stirring to obtain a resin solution. This solution was cooled to 25°C and then diluted with PGMEA to a solid content of 30% by weight to obtain alkali-soluble acrylic resin solution B. Alkali-soluble acrylic resin solution B is a PGMEA solution containing a copolymer formed by a mol% ratio of 4-hydroxybutyl acrylate / 2-ethylhexyl acrylate / acrylic acid of 49 / 49 / 2.

[0353] (Synthesis Example 3: Synthesis of benzodifuranone-based black pigment 2 with a silica coating on its surface)

[0354] 500.00 g of the benzodifuranone-based black pigment represented by structural formula (4) was added to a glass container containing 4500.00 g of deionized water and stirred with a dissolver to obtain a pre-stirred solution of the aqueous pigment suspension. This solution was then pumped into a container filled with water at a filling rate of 75% by volume. The solution was fed into a bead mill containing zirconia beads (Toray Industries: TORAYCERAM (registered trademark)) and dispersed in two passes at a discharge rate of 300 mL / min. Next, the mixture was filled with zirconia beads at a 75% volume fraction. Zirconia beads (Toray Industries: TORAYCERAM (registered trademark)) were fed into a bead mill and dispersed for 6 hours at a discharge rate of 300 mL / min. The entire volume was then discharged back into the original glass container and stirred again in a dissolver. A 10 mL sample of the aqueous pigment suspension was taken and filtered through a 0.45 mm syringe filter, confirming that the entire volume could be passed through without clogging. A pH meter was set up in the glass container, with the electrode tip immersed 3–5 cm below the surface of the stirred aqueous pigment suspension. The pH of the resulting suspension was measured to be 4.5 (liquid temperature 25°C). Then, while stirring, the temperature of the aqueous pigment suspension was raised to 40°C. After 30 minutes, stirring was temporarily stopped. Two minutes later, after confirming no sediment buildup at the bottom of the glass container, stirring was resumed.

[0355] With respect to 100 parts by weight of the benzodifuranone-based black pigment represented by Structural Formula (4), in a manner that the coating amount of the silica is 10 parts by weight, sodium silicate (Na20-nSi02-mH20: 10% by weight in terms of sodium oxide, 30% by weight in terms of silica: basic) diluted 100 times with deionized water and a 0.001 mol / L aqueous solution of sulfuric acid are adjusted in their respective addition rates so as to maintain the pH of the aqueous pigment suspension in a range of 2 or more and less than 7, and are simultaneously and concurrently added, so as to precipitate silica hydrate and coat the surface of the benzodifuranone-based black pigment represented by Structural Formula (4). Next, filtration and water washing are repeatedly performed three times using a suction filter, a portion of the water-soluble impurities is removed, and purification is performed. In order to remove ionic impurities, 50 g each of a cation exchange resin and an anion exchange resin (both of which are manufactured by ORGANO: Amberlite) are added to the aqueous pigment suspension, stirring is performed for 12 hours, and filtration is performed to obtain a black filtrate. This is heated in a drying oven at an actual temperature of 90°C for 6 hours under dry air to remove moisture, is powdered, and is further heated in a drying oven at an actual temperature of 250°C for 1 hour under dry air to dehydrate and sinter, forming a coating layer formed of silica.

[0356] Finally, dry pulverization treatment is performed for 30 minutes using a jet mill to perform granulation, and 460.50 g of a benzodifuranone-based black pigment 2 is obtained. The elements on the surface and the cut surface of the benzodifuranone-based black pigment 2 are analyzed using SEM-EDX, and it is confirmed that the pigment surface is covered with silicon atoms and oxygen atoms. Furthermore, by firing using an electric furnace at an actual temperature of 800°C for 6 hours to remove the organic components by thermal decomposition, as a result of the weight of the residual components, it can be considered that the constituent components of the benzodifuranone-based black pigment 2 are 100 parts by weight of the benzodifuranone-based black pigment represented by Structural Formula (4) as the core, and 10 parts by weight of silica as the coating material. The specific surface area of the benzodifuranone-based black pigment 2 based on the BET method is 40 m 2 / g.

[0357] (Synthesis Example 4: Synthesis of Alkali-Soluble Acrylic Resin Solution C)

[0358] A mixed solution was prepared consisting of 65.07 g of 0.50 mol 2-hydroxyethyl methacrylate, 211.45 g of 1.20 mol benzyl methacrylate, 25.83 g of 0.30 mol methacrylic acid, 5.00 g of 2,2'-azobis(isobutyronitrile) as a polymerization initiator, and 200.00 g of PGMEA. Under a dry nitrogen stream, the mixture was added dropwise over 1 hour using a funnel to 261.02 g of PGMEA while maintaining a liquid temperature of 90°C and stirring. The solution was then heated to 120°C and maintained until the weight-average molecular weight of the resulting copolymer reached 8000, copolymerizing while stirring to obtain a resin solution. This solution was cooled to 25°C and then diluted with PGMEA to a solid content of 30% by weight to obtain an alkali-soluble acrylic resin solution C.

[0359] Alkali-soluble acrylic resin solution C is a PGMEA solution containing a copolymer formed by a molar ratio of 2-hydroxyethyl methacrylate / benzyl methacrylate / methacrylic acid of 25 / 60 / 15.

[0360] (Preparation Example 1: Preparation of Pigment Dispersion 1)

[0361] 37.50 g of dispersant 1 and 53.57 g of ZCR-1569H (70.00% by weight of solid content) were mixed with 783.93 g of PGMEA as an organic solvent and stirred for 10 minutes. Then, 125.00 g of benzodifuranone-based black pigment 2 was added and stirred for 30 minutes to obtain a pre-stirred solution. The pre-stirred solution was then transferred to a filling container... A bead mill containing zirconia beads (Toray Industries, Inc., "TORAYCERAM" (registered trademark)) was used for wet media dispersion treatment via a 30-minute circulation cycle. Then, the mixture was filled with... Zirconia beads (Toray Industries, Inc., "TORAYCERAM" (registered trademark)) were fed into a bead mill for wet dispersion using a circulating method. After 30 minutes, a sample was taken from a glass bottle every 15 minutes. The resulting pigment dispersion was then tested using a dynamic light scattering particle size distribution measuring device "SZ-100" to determine the average dispersed particle size. Among the pigment dispersions with an average dispersed particle size within the range of 100 ± 10 nm after 30 minutes of sampling, the dispersion with the shortest dispersion time was designated as "pigment dispersion 1". It should be noted that the solid component of pigment dispersion 1 is 20.00% by weight, and the solid component weight ratio is benzodifuranone-based black pigment 2 / dispersant 1 / ZCR-1569H = 100 / 30 / 30. The proportions (g) of each raw material and the average dispersed particle size are shown in Table 2.

[0362] [Table 2]

[0363]

[0364] (Preparation Example 2: Production of Pigment Dispersion Liquid 2)

[0365] Instead of the dispersant 1, the dispersants 2 to 8 were used respectively, and wet medium dispersion treatment was performed by the same procedure as in Preparation Example 1 to produce the pigment dispersion liquids 2 to 8. The blending amounts (g) of each raw material and the average dispersed particle diameter are shown in Table 2.

[0366] (Preparation Example 9: Production of Pigment Dispersion Liquid 9)

[0367] Instead of the dispersant 1, the dispersant 5 and the dispersant 9 were used in a dispersant 5: dispersant 9 = solid content weight ratio of 2: 1, and wet medium dispersion treatment was performed by the same procedure as in Preparation Example 1 to produce the pigment dispersion liquid 9. The blending amounts (g) of each raw material and the average dispersed particle diameter are shown in Table 3.

[0368] [Table 3]

[0369]

[0370] (Preparation Example 10: Production of Pigment Dispersion Liquid 10)

[0371] The dispersant 5 of 34.09 g and the ZCR-1569H of 74.68 g were mixed into the PGMEA of 777.60 g, stirred for 10 minutes, and then the benzodifuranone-based black pigment 1 of 113.64 g was put in and stirred for 30 minutes to obtain a pre-stirring liquid. The subsequent procedure was performed by the same procedure as in Preparation Example 1 to produce the pigment dispersion liquid 10. The solid content of the pigment dispersion liquid 10 was 20.00% by weight, and the solid content weight ratio was benzodifuranone-based black pigment 1 / dispersant 5 / ZCR-1569H = 100 / 30 / 46. The blending amounts (g) of each raw material and the average dispersed particle diameter are shown in Table 3.

[0372] (Preparation Example 11: Production of Pigment Dispersion Liquid 11)

[0373] The dispersant 5 of 37.50 g and the alkali-soluble polyimide resin A of 37.50 g were mixed into the PGMEA of 800.00 g, stirred for 10 minutes, and then the benzodifuranone-based black pigment 2 of 125.00 g was put in and stirred for 30 minutes to obtain a pre-stirring liquid. The subsequent procedure was performed by the same procedure as in Preparation Example 1 to produce the pigment dispersion liquid 11. The blending amounts (g) of each raw material and the average dispersed particle diameter are shown in Table 3.

[0374] (Preparation Example 12: Production of Pigment Dispersion Liquid 12)

[0375] A mixture of 37.50 g of dispersant 5, 48.21 g of ZCR-1569H and 3.75 g of dispersing aid a was mixed into 785.54 g of PGMEA, stirred for 10 minutes, and then 25.00 g of C.I. Pigment Orange 43 as an organic orange pigment, 31.25 g of C.I. Pigment Blue 60 as an organic blue pigment, 31.25 g of C.I. Pigment Blue 65 as an organic blue pigment, and 37.50 g of C.I. Pigment Red 179 as an organic red pigment were added, stirred for 30 minutes, to obtain a pre-stirring solution. The subsequent procedure was performed in the same manner as in Preparation Example 1 to perform wet medium dispersion treatment, and to prepare Pigment Dispersion Liquid 12. The solid content of Pigment Dispersion Liquid 12 was 20.00% by weight, and the solid content weight ratio was (a-2) component / dispersing aid a / dispersant 5 / ZCR-1569H = 100 / 3 / 30 / 27. The compounding amount (g) of each raw material and the average dispersed particle diameter are shown in Table 3.

[0376] (Preparation Example 13: Production of Pigment Dispersion Liquid 13)

[0377] A mixture of 15.00 g of Solsperse 20000 and 45.00 g of alkali-soluble polyimide resin A was mixed into 850.00 g of MBA as an organic solvent, stirred for 10 minutes, and then 90.00 g of benzodifuranone-based black pigment 1 was added and stirred for 30 minutes to obtain a pre-stirring solution. The subsequent procedure was performed in the same manner as in Preparation Example 1 to perform wet medium dispersion treatment, and to prepare Pigment Dispersion Liquid 13. The solid content of Pigment Dispersion Liquid 13 was 15.00% by weight, and the solid content weight ratio was benzodifuranone-based black pigment 1 / Solsperse 20000 / alkali-soluble polyimide resin A = 100 / 16.67 / 50. The compounding amount (g) of each raw material and the average dispersed particle diameter are shown in Table 4.

[0378] [Table 4]

[0379]

[0380] (Preparation Example 14: Production of Pigment Dispersion Liquid 14)

[0381] A mixture of 125.00 g of DISPERBYK-LPN21116 (solid content 40.00% by weight) and 71.43 g of ZCR-1569H was mixed into a mixed solvent (160.00 g of MB and 543.57 g of PGMEA), stirred for 10 minutes, and then 100.00 g of the benzodifuranone-based black pigment 1 was added and stirred for 30 minutes to obtain a pre-stirring solution. The subsequent procedure was performed in the same manner as in Preparation Example 1 to perform wet medium dispersion treatment, and a pigment dispersion liquid 14 was prepared. The solid content of the pigment dispersion liquid 14 was 20.00% by weight, and the solid content weight ratio was benzodifuranone-based black pigment 1 / DISPERBYK-LPN21116 / ZCR-1569H = 100 / 50 / 50. The compounding amount (g) of each raw material and the average dispersed particle diameter are shown in Table 4.

[0382] (Preparation Example 15: Production of Pigment Dispersion Liquid 15)

[0383] A mixture of 125.00 g of DISPERBYK-LPN21116, 6.00 g of DISPERBYK-111 and 62.86 g of ZCR-1569H was mixed into a mixed solvent (160.00 g of MB and 546.14 g of PGMEA), stirred for 10 minutes, and then 100.00 g of the benzodifuranone-based black pigment 1 was added and stirred for 30 minutes to obtain a pre-stirring solution. The subsequent procedure was performed in the same manner as in Preparation Example 1 to perform wet medium dispersion treatment, and a pigment dispersion liquid 15 was prepared. The solid content of the pigment dispersion liquid 15 was 20.00% by weight, and the solid content weight ratio was benzodifuranone-based black pigment 1 / DISPERBYK-LPN21116 / DISPERBYK-111 / ZCR-1569H = 100 / 50 / 6 / 44. The compounding amount (g) of each raw material and the average dispersed particle diameter are shown in Table 4.

[0384] (Preparation Example 16: Production of Pigment Dispersion Liquid 16)

[0385] A mixture of 93.75 g of DISPERBYK-LPN21116 and 53.57 g of ZCR-1569H was mixed into 727.68 g of PGMEA, stirred for 10 minutes, and then 125.00 g of the benzodifuranone-based black pigment 2 was added and stirred for 30 minutes to obtain a pre-stirring solution. The subsequent procedure was performed in the same manner as in Preparation Example 1 to perform wet medium dispersion treatment, and a pigment dispersion liquid 15 was prepared. The solid content of the pigment dispersion liquid 15 was 20.00% by weight, and the solid content weight ratio was benzodifuranone-based black pigment 2 / DISPERBYK-LPN21116 / ZCR-1569H = 100 / 30 / 30. The compounding amount (g) of each raw material and the average dispersed particle diameter are shown in Table 4.

[0386] (Preparation Example 17: Production of Pigment Dispersion Liquid 17)

[0387] Instead of dispersant 1, dispersant 10 was used, and wet medium dispersion treatment was performed by the same procedure as in Preparation Example 1 to produce Pigment Dispersion Liquid 18. The amounts (g) of the raw materials used are shown in Table 5, together with the average dispersion particle diameter.

[0388] (Preparation Examples 18 to 19: Production of Pigment Dispersion Liquids 18 to 19)

[0389] Instead of dispersant 1, dispersants 10 to 11 were used, respectively, and wet medium dispersion treatment was performed by the same procedure as in Preparation Example 1 to produce Pigment Dispersion Liquids 18 to 19. The amounts (g) of the raw materials used are shown in Table 5, together with the average dispersion particle diameter.

[0390] [Table 5]

[0391]

[0392] (Preparation Examples 20 to 21: Production of Pigment Dispersion Liquids 20 to 21)

[0393] Instead of dispersant 1, dispersants 12 and Solsperse 24000GR were used, respectively, and wet medium dispersion treatment was performed by the same procedure as in Preparation Example 1 to produce Pigment Dispersion Liquids 20 to 21. However, at a stage before the average dispersion particle diameter reached 100 ± 10 nm, significant re-agglomeration occurred. Since the viscosity of the pigment dispersion liquid increased sharply, the pressure in the pump increased, and it was difficult to feed the liquid into the container of the bead mill, so the wet medium dispersion treatment had to be terminated, and Pigment Dispersion Liquids 20 to 21 could not be obtained. The amounts (g) of the raw materials used are shown in Table 5.

[0394] (Preparation Example 22: Production of Pigment Dispersion Liquid 22)

[0395] A mixture of 72.12 g of DISPERBYK-167 (solid content 52.00% by weight) and 53.57 g of ZCR-1569H was mixed into 749.31 g of PGMEA, stirred for 10 minutes, and then 125.00 g of the benzodifuranone-based black pigment 2 was added and stirred for 30 minutes to obtain a pre-stirring solution. The subsequent procedure was performed in accordance with the same procedure as in Preparation Example 1 to perform wet medium dispersion treatment, and a pigment dispersion liquid 22 was prepared. The solid content of the pigment dispersion liquid 22 was 20.00% by weight, and the solid content weight ratio was benzodifuranone-based black pigment 1 / DISPERBYK-167 / ZCR-1569H = 100 / 30 / 30. The compounding amount (g) of each raw material and the average dispersed particle diameter are shown in Table 5.

[0396] (Preparation Example 23: Production of Pigment Dispersion Liquid 23)

[0397] A mixture of 93.75 g of DISPERBYK-LPN21116, 48.21 g of ZCR-1569H, and 3.75 g of a dispersing aid a was mixed into 729.29 g of PGMEA, stirred for 10 minutes, and then 25.00 g of C.I. Pigment Orange 43 as an organic orange pigment, 31.25 g of C.I. Pigment Blue 60 as an organic blue pigment, 31.25 g of C.I. Pigment Blue 65 as an organic blue pigment, and 37.50 g of C.I. Pigment Red 179 as an organic red pigment were added and stirred for 30 minutes to obtain a pre-stirring solution. The subsequent procedure was performed in accordance with the same procedure as in Preparation Example 1 to perform wet medium dispersion treatment, and a pigment dispersion liquid 23 was prepared. The solid content of the pigment dispersion liquid 23 was 20.00% by weight, and the solid content weight ratio was (a-2) component / dispersing aid a / DISPERBYK-LPN21116 / ZCR-1569H = 100 / 3 / 30 / 27. The compounding amount (g) of each raw material and the average dispersed particle diameter are shown in Table 5.

[0398] (Preparation Example 24: Production of Pigment Dispersion Liquid 24)

[0399] A mixture of 37.50 g of dispersant 5 and 89.29 g of WR-301 (solid content 42.00% by weight) as an alkali-soluble Cardo resin solution was mixed into 748.21 g of PGMEA, stirred for 10 minutes, and then 125.00 g of the benzodifuranone-based black pigment 2 was added and stirred for 30 minutes to obtain a pre-stirring solution. The subsequent procedure was performed in accordance with the same procedure as in Preparation Example 1 to perform wet medium dispersion treatment, and a pigment dispersion liquid 24 was prepared. The solid content of the pigment dispersion liquid 24 was 20.00% by weight, and the solid content weight ratio was benzodifuranone-based black pigment 2 / dispersant 5 / WR-301 = 100 / 30 / 30. The compounding amount (g) of each raw material and the average dispersed particle diameter are shown in Table 5.

[0400] (Example 1: Preparation and evaluation of negative photosensitive composition 1)

[0401] Under a yellow lamp, 0.18 g of NCI-831E as a photopolymerization initiator was added to a mixed solvent of 1.28 g of MBA and 12.66 g of PGMEA, and stirred for 3 minutes to dissolve it. To this, 1.29 g of ZCR-1569H and 0.60 g of alkali-soluble acrylic resin solution B were added, and 0.23 g of DPCA-20, 0.23 g of BP-4EAL, and 0.72 g of EA-0250P (PGMEA solution of 50% by weight of solid content) of a compound having no tertiary amino group and having 2 or more radical polymerizable groups in the molecule were added. Further, 0.90 g of a 5% by weight PGMEA solution of Emulgen A-60 (manufactured by Kawaken Corporation) as a nonionic surfactant was added, and stirring was performed for 10 minutes to obtain a mixture. This mixture was mixed with 11.93 g of pigment dispersion liquid 1 and stirred for 30 minutes to obtain negative photosensitive composition 1. The solid content of negative photosensitive composition 1 was 15.00% by weight, and the content of benzo dioxetone-based black pigment 2 in the solid content was 33.13% by weight (the content of the core was 30.11% by weight). The amounts (g) of the respective raw materials are shown in Table 6.

[0402] [Table 6]

[0403]

[0404] On the surface of "TEMPAX" (manufactured by AGC TECHNO GLASS Co., Ltd.) as a transparent glass substrate, negative photosensitive composition 1 was coated with a spin coater so as to have a thickness of 1.5 μm of the finally obtained cured film, and a prebaked film was obtained by prebaking the coated film at 100°C for 120 seconds under atmospheric pressure using a hot plate (SCW-636; manufactured by Dai Nippon Screen Manufacturing Co., Ltd.). Using a two-side alignment one-side exposure device, an i-line passing filter was set, and the prebaked film was exposed at an exposure amount of 80 mJ / cm2. After the exposure, the film was developed with PGMEA for 60 seconds, and a developed film was obtained. The developed film was baked at 200°C for 60 minutes using a hot plate (SCW-636; manufactured by Dai Nippon Screen Manufacturing Co., Ltd.) to obtain a cured film. The thickness of the cured film was 1.5 μm. 2(i line conversion value) The i line of an ultra-high pressure mercury lamp was irradiated to the entire surface of the pre-baked film to obtain an exposed film. Next, using a small-sized developing device for photolithography (AD-2000; manufactured by TAKIZAWA SANGYO K.K.), the exposed film was developed with a 2.38% by weight TMAH aqueous solution for a developing time of 1.5 times the minimum necessary developing time, rinsed with deionized water for 30 seconds to obtain a developed film, and the developed film was heated at 230°C for 30 minutes in an air atmosphere using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.) to obtain a substrate 1 having a cured film with a thickness of 1.5 μm, and the optical density (OD / μm) was evaluated by the above-described method, and the result was 1.4. Note that the thickness of the cured film refers to the average value of the thicknesses measured at three points in the plane of the cured film, rounded off to the second decimal place, and the value up to the first decimal place was obtained, and the result was 1.5 μm.

[0405] The minimum necessary exposure amount of the negative photosensitive composition 1 was calculated by the above-described method, and the substrate was used to evaluate the development residue on the transparent conductive film.

[0406] A silver alloy (an alloy formed of 99.00% by weight silver and 1.00% by weight copper) was formed into a film on the surface of a 150 mm x 150 mm alkali-free glass substrate by a sputtering method. In order to evaluate the surface state of the silver alloy film as a close external load history compared to when a low-crystallinity ITO film was further layered, the substrate was immersed in a 5% by weight oxalic acid aqueous solution maintained at a liquid temperature of 50°C for 5 minutes, rinsed with deionized water for 2 minutes, and then dried by blowing air. Note that the silver alloy film was insoluble in the 5% by weight oxalic acid aqueous solution. Further, the substrate was heated at 150°C for 30 minutes in a dry nitrogen atmosphere to obtain a substrate 1 having only a silver alloy film with a film thickness of 100 nm, and the maximum height difference (Rmax 1 ) of the surface of the silver alloy film before coating was measured by the above-described method, and the result was 60.0 nm.

[0407] On the surface of the silver alloy film of the substrate 1 having only the silver alloy film with a film thickness of 100 nm, the negative photosensitive composition 1 prepared after storage at 25°C for 24 hours was coated using a spin coater with the rotation speed adjusted so that the thickness of the finally obtained cured film would be 1.5 μm, and a prebaking of the coated film was performed at 100°C for 2 minutes under atmospheric pressure using a hot plate to obtain a prebaked film. A pattern exposure was performed using an i-line (wavelength: 365 nm) of an ultra-high pressure mercury lamp at the minimum necessary exposure amount using a two-side alignment one-side exposure device to obtain an exposed film. Next, a spin-coating immersion development was performed using a 2.38% by weight TMAH aqueous solution for a development time of 1.5 times the minimum necessary development time using a small-sized development device for photolithography, and after rinsing with deionized water for 30 seconds, drying was performed by blowing air to obtain a patterned developed film. A high-temperature inert gas oven was used as a curing step, and heating was performed at 230°C for 30 minutes under air to form a pixel division layer 1 on the surface of the silver alloy film. The maximum height difference (Rmax 2 ) of the surface of the silver alloy film at the opening portion after formation of the pixel division layer was measured by the above-described method, and the result was 75.2 nm, and the difference (Rmax 2 -Rmax 1 ) was 15.2 nm.

[0408] Separately, in order to investigate the evaluation results of the negative photosensitive composition 1, as Reference Example 1, the maximum height difference of the substrate 1 (Rmax 1 : 60.0 nm) having only the silver alloy film with a film thickness of 100 nm without using the negative photosensitive composition 1 was measured alone after the prebaking step, the exposure step, the development step, and the curing step under the same processing conditions as when the pixel division layer 1 was formed, and the result was 86.0 nm. That is, in the case where the negative photosensitive composition 1 was not involved at all, the difference caused by corrosion in the steps was 26.0 nm, and in contrast, the difference in the case where the pixel division layer 1 was formed was reduced to 15.2 nm, and furthermore, it was confirmed using an SEM that either difference was not caused by the local generation of a concave portion but a convex portion, and thus it was considered that the negative photosensitive composition 1 had an effect of suppressing the generation of a convex portion on the surface of the silver alloy film.

[0409] Next, after the negative photosensitive composition 1 was stored standing in a freezer maintained at -20°C for 3 months under atmospheric pressure, thawing was performed in a water bath at a liquid temperature of 25°C, and after stirring on a shaker, the same evaluation was performed to evaluate the freezing storage stability of the negative photosensitive composition 1.

[0410] The evaluation results with respect to the optical density, the developed residue on the transparent conductive film, the change in the maximum height difference of the surface of the silver alloy film, and the freezing storage stability described above are shown in Table 7.

[0411] [Table 7]

[0412]

[0413] Next, by the following method, a top emission type organic EL display device having a cured film formed of a cured product of the negative photosensitive composition 1 as a pixel partition layer was produced, and the generation rate (%) of non-lighting pixels was evaluated.

[0414] Figure 6 The production process of the top emission type organic EL display device including the formation process of the pixel partition layer is shown in FIG. 1.

[0415] On the surface of an alkali-free glass substrate 14 of 70 mm in length and 70 mm in width, a silver alloy (an alloy formed of 99.00% by weight of silver and 1.00% by weight of copper) was formed into a film by a sputtering method. Using an alkali-soluble Novolac-based positive resist, the silver alloy film was etched by immersion in a silver alloy etching liquid SEA-1 having a liquid temperature of 30°C to obtain a patterned silver alloy film 15 having a film thickness of 100 nm. Further, an amorphous ITO film as a metastable phase was formed into a film by a sputtering method. Using an alkali-soluble Novolac-based positive resist, the amorphous ITO film was etched by immersion in a 5% by weight oxalic acid aqueous solution having a liquid temperature of 50°C for 5 minutes, rinsed with water for 2 minutes using a water spray, and then dried by blowing air to obtain the same patterned amorphous ITO film having a film thickness of 10 nm. Under a dry nitrogen atmosphere, low-temperature annealing treatment was performed at 150°C for 30 minutes to form a low-crystallinity ITO film 16. By the above process, a first electrode formation substrate 1 having a first electrode formed of a laminated pattern of a silver alloy film / low-crystallinity ITO was obtained.

[0416] The negative photosensitive composition 1 was applied to the surface of the first electrode formation substrate 1 using a spin coater so that the film thickness of the finally obtained pixel partition layer would be 1.5 μm, and a coating film was obtained. Further, the coating film was subjected to pre-baking at 100°C for 120 seconds under atmospheric pressure using a hot plate to obtain a pre-baked film. Using a two-side alignment single-side exposure device provided with an i-line passing filter, the pre-baked film was subjected to pattern exposure with the necessary minimum exposure amount through a negative exposure mask to obtain an exposed film. Next, using a small-sized developing device for photolithography, the exposed film was subjected to spin-coating immersion development with a 2.38% by weight TMAH aqueous solution for a developing time of 1.5 times the necessary minimum developing time, and rinsed with deionized water for 30 seconds to obtain a patterned developed film. Using a high-temperature inert gas oven, the developed film was heated at 230°C for 30 minutes under air to obtain a pixel partition layer formation substrate 1 having a pixel partition layer 17 having a film thickness of 1.5 μm and having 55 opening portions (300 μm in length and 100 μm in width) arranged in a region of 30 mm in length and 30 mm in width in the central portion of the first electrode formation substrate.

[0417] Next, in order to form the organic EL layer 18 including the light-emitting layer by a vacuum evaporation method, the pixel-dividing layer-formed substrate 1 was rotated with respect to an evaporation source under evaporation conditions of a vacuum degree of 1 x 10 -3 The pixel-dividing layer-formed substrate 1 was rotated with respect to an evaporation source under evaporation conditions of a vacuum degree of 1 x 10

[0418] Next, the compound (LiQ) was evaporated by 2 nm, and then a pattern evaporation was performed with a silver / magnesium alloy (volume ratio 10:1) to form a second electrode 19 having a film thickness of 20 nm in a manner such that 40 of the 55 opening portions possessed by the pixel-dividing layer 1 function as light-emitting pixel portions. Then, under a low-humidity / nitrogen atmosphere, the sealing was performed by adhering a cover-like glass plate using an epoxy resin-based adhesive, to obtain a top-emission type organic EL display device 1. Note that the film thickness of each layer constituting the organic EL layer 18 and the second electrode was very thin as compared with the pixel-dividing layer described above, and was difficult to measure with high accuracy in a stylus-type film thickness measuring device, and thus a quartz oscillation-type film thickness monitor suitable for a thin film of less than 100 nm was used to measure each layer, and the value obtained by rounding off the first digit after the decimal point of the average value of three places in the plane was taken as the film thickness.

[0419] [Chemical Formula 46]

[0420]

[0421] [Chemical Formula 47]

[0422]

[0423] By the same method, nine identical devices were additionally produced using the negative photosensitive composition 1, and for a total of 10 top-emission type organic EL display devices 1, the generation rate of non-lighting pixels was evaluated by the above method, and the results are shown in Table 7.

[0424] (Examples 2 to 9: Production and Evaluation of Negative Photosensitive Compositions 2 to 9)

[0425] Instead of the pigment dispersion liquid 1, the pigment dispersion liquids 2 to 9 were used respectively, and negative-type photosensitive compositions 2 to 9 were prepared by the same procedure as in Example 1, and the optical density, the development residue on the transparent conductive film, the change in the maximum unevenness of the surface of the silver alloy film, the refrigerated storage stability, and the generation rate of non-lighted pixels were evaluated by the above-described methods. The solid content of each of the negative-type photosensitive compositions 2 to 9 was 15.00% by weight, and the content of the benzo difuranone-based black pigment 2 in the solid content was 33.13% by weight. The compounding amounts (g) of each of the raw materials are shown in Tables 6, 8, and 10, and the evaluation results are shown in Tables 7, 9, and 11.

[0426] [Table 8]

[0427]

[0428] [Table 9]

[0429]

[0430] [Table 10]

[0431]

[0432] [Table 11]

[0433]

[0434] (Example 10: Preparation and Evaluation of Negative-Type Photosensitive Composition 10)

[0435] Under a yellow lamp, 0.18 g of NCI-831E was added to a mixed solvent of 1.28 g of MBA and 11.81 g of PGMEA and stirred for 3 minutes to dissolve it. To this, 0.95 g of ZCR-1569H and 0.60 g of the alkali-soluble acrylic resin solution B were added, and 0.23 g of DPCA-20, 0.23 g of BP-4EAL, and 0.72 g of EA-0250P were added. Further, 0.90 g of a 5% by weight PGMEA solution of A-60 (manufactured by Showa Denko K.K.) was added and stirred for 10 minutes to obtain a compounded solution. This compounded solution and 13.12 g of the pigment dispersion liquid 10 were mixed and stirred for 30 minutes to prepare a negative-type photosensitive composition 10, and the optical density, the development residue on the transparent conductive film, the change in the maximum unevenness of the surface of the silver alloy film, the refrigerated storage stability, and the generation rate of non-lighted pixels were evaluated by the above-described methods. The solid content of the negative-type photosensitive composition 10 was 15.00% by weight, and the content of the benzo difuranone-based black pigment 1 in the solid content was 30.11% by weight. The compounding amounts (g) of each of the raw materials are shown in Table 10, and the evaluation results are shown in Table 11.

[0436] (Example 11: Preparation and Evaluation of Negative Photosensitive Composition 11)

[0437] Under a yellow lamp, 0.18 g of NCI-831E was added to a mixed solvent of 1.28 g of MBA and 13.01 g of PGMEA and stirred for 3 minutes to dissolve it. To this, 0.13 g of ZCR-1569H, 0.81 g of alkali-soluble polyimide resin A, and 0.60 g of alkali-soluble acrylic resin solution B were added, and 0.23 g of DPCA-20, 0.23 g of BP-4EAL, and 0.72 g of EA-0250P were added. Further, 0.90 g of a 5 wt% PGMEA solution of Emulgen A-60 was added and stirred for 10 minutes to obtain a mixture. This mixture and 11.93 g of pigment dispersion liquid 11 were mixed and stirred for 30 minutes to prepare negative photosensitive composition 11, and the optical density, development residue on the transparent conductive film, change in maximum unevenness of the surface of the silver alloy film, freeze storage stability, and generation rate of non-lighted pixels were evaluated by the above-described methods. The solid content of negative photosensitive composition 11 was 15.00 wt%, and the content of benzodifuranone-based black pigment 2 in the solid content was 33.13 wt%. The compounding amounts (g) of each raw material are shown in Table 10, and the evaluation results are shown in Table 11.

[0438] (Example 12: Preparation and Evaluation of Negative Photosensitive Composition 12)

[0439] Instead of pigment dispersion liquid 11, pigment dispersion liquid 12 was used, and negative photosensitive composition 12 was prepared by the same procedure as in Example 11, and the optical density, development residue on the transparent conductive film, change in maximum unevenness of the surface of the silver alloy film, freeze storage stability, and generation rate of non-lighted pixels were evaluated by the above-described methods. The solid content of negative photosensitive composition 12 was 15.00 wt%, and the content of the (a-2) component in the solid content was 30.11 wt%. The compounding amounts (g) of each raw material are shown in Table 10, and the evaluation results are shown in Table 11.

[0440] (Example 13: Preparation and Evaluation of Negative Photosensitive Composition 13)

[0441] A negative photosensitive composition 13 was prepared by the same procedure as in Example 5, except that the alkali-soluble acrylic resin solution B was not replaced with ZCR-1569H, PGMEA was changed to 13.01 g, and the optical density, development residue on a transparent conductive film, change in maximum unevenness of the surface of a silver alloy film, freeze storage stability, and generation rate of non-lighted pixels were evaluated by the above-described methods. The solid content of the negative photosensitive composition 13 was 15.00% by weight, and the content of the benzodifuranone-based black pigment 2 in the solid content was 33.13% by weight. The blending amount (g) of each raw material is shown in Table 12, and the evaluation results are shown in Table 13.

[0442] [Table 12]

[0443]

[0444] [Table 13]

[0445]

[0446] (Example 14: Preparation and Evaluation of Negative Photosensitive Composition 14)

[0447] Under a yellow lamp, 0.18 g of NCI-831E was added to a mixed solvent of 1.28 g of MBA and 11.98 g of PGMEA and stirred for 3 minutes to dissolve it. To this, 2.57 g of WR-301, 0.23 g of DPCA-20, 0.23 g of BP-4EAL, and 0.72 g of EA-0250P were added. Further, 0.90 g of a 5% by weight PGMEA solution of Emulgen A-60 was added and stirred for 10 minutes to obtain a mixture. This mixture and 11.93 g of the pigment dispersion liquid 24 were mixed and stirred for 30 minutes to prepare a negative photosensitive composition 14, and the optical density, development residue on a transparent conductive film, change in maximum unevenness of the surface of a silver alloy film, freeze storage stability, and generation rate of non-lighted pixels were evaluated by the above-described methods. The solid content of the negative photosensitive composition 14 was 15.00% by weight, and the content of the benzodifuranone-based black pigment 2 in the solid content was 33.13% by weight. The blending amount (g) of each raw material is shown in Table 12, and the evaluation results are shown in Table 13.

[0448] (Comparative Example 1: Preparation and Evaluation of Negative Photosensitive Composition 15)

[0449] Under a yellow lamp, 0.18 g of NCI-831E was added to 9.44 g of PGMEA and stirred for 3 minutes to dissolve. To this, 1.14 g of ZCR-1569H, 0.23 g of DPCA-20, 0.23 g of BP-4EAL, and 0.72 g of EA-0250P were added. Further, 0.90 g of a 5% by weight PGMEA solution of Emulgen A-60 was added and stirred for 10 minutes to obtain a dope. This dope and 16.56 g of the pigment dispersion liquid 13 were mixed and stirred for 30 minutes to prepare a negative photosensitive composition 16, and the optical density, development residue on a transparent conductive film, change in maximum unevenness of the surface of a silver alloy film, freeze storage stability, and generation rate of non-lighted pixels were evaluated by the above-described methods. The solid content of the negative photosensitive composition 16 was 15.00% by weight, and the content of the benzo difuranone-based black pigment 1 in the solid content was 30.11% by weight. The compounding amounts (g) of each raw material are shown in Table 14, and the evaluation results are shown in Table 15.

[0450] [Table 14]

[0451]

[0452] [Table 15]

[0453]

[0454] (Comparative Example 2: Preparation and Evaluation of Negative Photosensitive Composition 16)

[0455] Under a yellow lamp, 0.18 g of NCI-831E was added to 9.44 g of PGMEA and stirred for 3 minutes to dissolve. To this, 1.14 g of ZCR-1569H, 0.23 g of DPCA-20, 0.23 g of BP-4EAL, and 0.72 g of EA-0250P were added. Further, 0.90 g of a 5% by weight PGMEA solution of Emulgen A-60 was added and stirred for 10 minutes to obtain a dope. This dope and 16.56 g of the pigment dispersion liquid 13 were mixed and stirred for 30 minutes to prepare a negative photosensitive composition 16, and the optical density, development residue on a transparent conductive film, change in maximum unevenness of the surface of a silver alloy film, freeze storage stability, and generation rate of non-lighted pixels were evaluated by the above-described methods. The solid content of the negative photosensitive composition 16 was 15.00% by weight, and the content of the benzo difuranone-based black pigment 1 in the solid content was 30.11% by weight. The compounding amounts (g) of each raw material are shown in Table 14, and the evaluation results are shown in Table 15.

[0456] (Comparative Example 3: Preparation and Evaluation of Negative Photosensitive Composition 17)

[0457] Under a yellow lamp, 0.26 g of OXE02 as a photopolymerization initiator was added to a mixed solvent of 1.14 g of MBA and 3.03 g of PGMEA and stirred for 3 minutes to dissolve it. To this, 2.14 g of ZCR-1797H and 0.55 g of DPHA-40H were added. Further, 0.66 g of a 5% by weight PGMEA solution of KAYAMER PM-21 as a methacryloyl-containing phosphoric acid ester was added, and 0.10 g of a 5% by weight PGMEA solution of MEGAFAC F-559 (manufactured by DIC) as a surfactant was added, and stirring was performed for 10 minutes to obtain a letdown mixture. This letdown mixture and 23.76 g of Pigment Dispersion Liquid 14 were mixed and stirred for 30 minutes to prepare a negative photosensitive composition 17. Evaluation was performed on optical density, development residue on a transparent conductive film, change in maximum unevenness of the surface of a silver alloy film, refrigerated storage stability, and generation rate of non-lighted pixels by the above-described methods. The solid content of the negative photosensitive composition 17 was 22.00% by weight, and the content of the benzo[d]difuranone-based black pigment 1 in the solid content was 32.73% by weight. The compounding amounts (g) of each raw material are shown in Table 14, and the evaluation results are shown in Table 15.

[0458] (Comparative Example 4: Preparation and Evaluation of Negative Photosensitive Composition 18)

[0459] Under a yellow lamp, 0.26 g of NCI-831E as a photopolymerization initiator was added to a mixed solvent of 1.18 g of MBA and 3.97 g of PGMEA and stirred for 3 minutes to dissolve it. To this, 1.75 g of ZCR-1797H and 0.87 g of DPHA were added. Further, 0.10 g of a 5% by weight PGMEA solution of MEGAFAC F-559 (manufactured by DIC) as a nonionic surfactant was added, and stirring was performed for 10 minutes to obtain a letdown mixture. This letdown mixture and 21.86 g of Pigment Dispersion Liquid 15 were mixed and stirred for 30 minutes to prepare a negative photosensitive composition 18. Evaluation was performed on optical density, development residue on a transparent conductive film, change in maximum unevenness of the surface of a silver alloy film, refrigerated storage stability, and generation rate of non-lighted pixels by the above-described methods. The solid content of the negative photosensitive composition 18 was 22.00% by weight, and the content of the benzo[d]difuranone-based black pigment 1 in the solid content was 30.11% by weight. The compounding amounts (g) of each raw material are shown in Table 14, and the evaluation results are shown in Table 15.

[0460] (Comparative Example 5: Preparation and Evaluation of Negative Photosensitive Composition 19)

[0461] Instead of the pigment dispersion liquid 1, the pigment dispersion liquid 16 was used, and a negative photosensitive composition 19 was produced by the same procedure as in Example 1, and the optical density, the development residue on the transparent conductive film, the change in the maximum unevenness of the surface of the silver alloy film, the refrigerated storage stability, and the generation rate of non-lighted pixels were evaluated by the above-described methods. The solid content of the negative photosensitive composition 19 was 15.00% by weight, and the content of the benzo difuranone-based black pigment 2 in the solid content was 33.13% by weight. The blending amount (g) of each raw material is shown in Table 14, and the evaluation results are shown in Table 15.

[0462] (Comparative Examples 6 to 8: Production and Evaluation of Negative Photosensitive Compositions 20 to 22)

[0463] Instead of the pigment dispersion liquid 1, the pigment dispersion liquids 18, 19, and 22 were used, respectively, and negative photosensitive compositions 20 to 22 were produced by the same procedure as in Example 1, and the optical density, the development residue on the transparent conductive film, the change in the maximum unevenness of the surface of the silver alloy film, the refrigerated storage stability, and the generation rate of non-lighted pixels were evaluated by the above-described methods. The solid content of each of the negative photosensitive compositions 20 to 22 was 15.00% by weight, and the content of the benzo difuranone-based black pigment 2 in the solid content was 33.13% by weight. The blending amount (g) of each raw material is shown in Table 16, and the evaluation results are shown in Table 17.

[0464] [Table 16]

[0465]

[0466] [Table 17]

[0467]

[0468] (Comparative Example 9: Production and Evaluation of Negative Photosensitive Composition 23)

[0469] Instead of the pigment dispersion liquid 1, the pigment dispersion liquid 23 was used, and a negative photosensitive composition 23 was produced by the same procedure as in Example 1, and the optical density, the development residue on the transparent conductive film, the change in the maximum unevenness of the surface of the silver alloy film, the refrigerated storage stability, and the generation rate of non-lighted pixels were evaluated by the above-described methods. The solid content of the negative photosensitive composition 23 was 15.00% by weight, and the content of the (a-2) component in the solid content was 30.11% by weight. The blending amount (g) of each raw material is shown in Table 16, and the evaluation results are shown in Table 17.

[0470] (Example 15: Production and Evaluation of Negative Photosensitive Composition 24)

[0471] Under a yellow lamp, 0.18 g of a compound represented by Structural Formula (31) was added as a photopolymerization initiator to a mixed solvent of 2.55 g of MBA and 12.91 g of PGMEA, and stirred for 3 minutes to dissolve it. To this, 0.95 g of ZCR-1569H and 3.00 g of the alkali-soluble acrylic resin solution C were added, and 0.23 g of DPCA-60 and 1.17 g of EA-0250P (50% by weight of solid content in PGMEA) were added, and stirred for 10 minutes to obtain a let-down mixture. This let-down mixture and 8.84 g of the pigment dispersion liquid 5 were mixed and stirred for 30 minutes to obtain a negative photosensitive composition 24. The optical density, development residue on a transparent conductive film, change in maximum unevenness of the surface of a silver alloy film, and refrigerated storage stability were evaluated by the above-described methods. Furthermore, the negative photosensitive composition 24 was applied to the surface of a first electrode formation substrate at a revolution adjusted in such a manner that the film thickness of a thin film portion in the finally obtained pixel division layer became 1.5 μm and the film thickness of a thick film portion became 3.0 μm, a negative half-tone exposure mask having a half-transmissive portion having a i-line transmittance of 30% in the plane, a full-transmissive portion, and a full-shading portion was interposed, and pattern exposure was performed at a full-tone exposure amount in half-tone processing calculated by the above-described method, and otherwise, a pixel division layer formation substrate having a thin film portion with a film thickness of 1.5 μm and a thick film portion with a film thickness of 3.0 μm was obtained by the same method as in Example 1. Figure 7 ). The difference between the film thickness of the thin film portion and the film thickness of the thick film portion was 1.5 μm. Furthermore, an organic EL display device was produced by the same method as in Example 1, and the generation rate (%) of non-lighted pixels was evaluated. Note that the solid content of the negative photosensitive composition 24 was 15.00% by weight, and the content of the benzodifuranone-based black pigment 2 in the solid content was 24.56% by weight (the content of the core was 22.33% by weight). The compounding amounts (g) of each raw material are shown in Table 18, and the evaluation results are shown in Table 19.

[0472] [Table 18]

[0473]

[0474] [Table 19]

[0475]

[0476] (Example 16: Preparation and Evaluation of Negative Photosensitive Composition 25)

[0477] Instead of ZCR-1569H, an alkali-soluble polyimide resin A was used, and a negative photosensitive composition 25 was prepared by the same procedure as in Example 15. The optical density, the development residue on the transparent conductive film, the change in the maximum unevenness of the surface of the silver alloy film, and the freeze storage stability were evaluated by the above-described methods. In addition, by the same method as in Example 15, a pixel partition layer forming substrate having a thin film portion with a film thickness of 1.5 μm and a thick film portion with a film thickness of 3.0 μm was obtained, and the generation rate of non-lighting pixels was evaluated. Note that the solid content of the negative photosensitive composition 25 was 15.00% by weight, and the content of the benzo difuranone-based black pigment 2 in the solid content was 24.56% by weight (the content of the core was 22.33% by weight). The compounding amounts (g) of each raw material are shown in Table 18, and the evaluation results are shown in Table 19.

[0478] (Comparative Example 10: Preparation and Evaluation of Negative Photosensitive Composition 26)

[0479] Instead of the pigment dispersion liquid 5, the pigment dispersion liquid 14 was used, and a negative photosensitive composition 26 was prepared by the same procedure as in Example 15. The optical density, the development residue on the transparent conductive film, the change in the maximum unevenness of the surface of the silver alloy film, and the freeze storage stability were evaluated by the above-described methods. In addition, by the same method as in Example 15, a pixel partition layer forming substrate having a thin film portion with a film thickness of 1.5 μm and a thick film portion with a film thickness of 3.0 μm was obtained. An organic EL display device was produced by the same method as in Example 1, and the generation rate of non-lighting pixels was evaluated. Note that the solid content of the negative photosensitive composition 26 was 15.00% by weight, and the content of the benzo difuranone-based black pigment 1 in the solid content was 22.33% by weight. The compounding amounts (g) of each raw material are shown in Table 18, and the evaluation results are shown in Table 19.

[0480] (Comparative Example 11)

[0481] The above-described negative photosensitive composition 17 was prepared again with the same compounding amounts, and halftone processing was attempted, but the film was peeled off significantly, and an organic EL display device having a pixel partition layer having a thin film portion with a film thickness of 1.5 μm and a thick film portion with a film thickness of 3.0 μm could not be produced.

[0482] As can be seen, in Examples 1 to 16, not only the development on the transparent conductive film was excellent, but also the maximum unevenness of the surface of the silver alloy film (Rmax 2 ) could be reduced compared to Comparative Examples 1 to 10. In addition, it was found that the generation rate of non-lighting pixels in the organic EL display device could be suppressed to be low. Furthermore, the freeze storage stability was also excellent, and the performance as a photosensitive composition was maintained. From the above results, it was found that the photosensitive composition or the negative photosensitive composition of the present application is very useful.

[0483] Reference Signs List

[0484] 1: TFT

[0485] 2: Wiring

[0486] 3: TFT Insulating Layer

[0487] 4: Planarization Layer

[0488] 5: First Electrode

[0489] 6: Substrate

[0490] 7: Contact Hole

[0491] 8: Pixel Dividing Layer

[0492] 9: Light Emitting Pixel

[0493] 10: Second Electrode

[0494] 11: Pixel Dividing Layer

[0495] 12: Silver Alloy Film

[0496] 13: Alkali-Free Glass Substrate

[0497] 14: Alkali-Free Glass Substrate

[0498] 15: Silver Alloy Film

[0499] 16: Low Crystallinity ITO Film

[0500] 17: Pixel Dividing Layer

[0501] 18: Organic EL Layer

[0502] 19: Second Electrode

[0503] 20: Thin Film Portion of Pixel Dividing Layer

[0504] 21: Thick Film Portion of Pixel Dividing Layer

[0505] 22: First Electrode

[0506] 23: Alkali-Free Glass Substrate

Claims

1. A negative photosensitive composition comprising: (a-1) an organic black pigment or (a-2) a mixed-color organic black pigment; (b) a resin having two or more tertiary amino groups in a molecule; and (c) a photosensitizer, wherein the (b) component contains a resin having a structure represented by General Formula (1), In General Formula (1), represents a bonding site with a carbon atom or a nitrogen atom; A 1 O, A 2 O, A 3 O and A 4 O each independently represents an oxyalkylene group having 1 to 5 carbon atoms; a 1 and a 3 are integers each independently representing 5 to 60; a 2 and a 4 are integers each independently representing 0 to 100; X 1 and X 2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms.

2. The negative photosensitive composition according to claim 1, wherein the resin having a structure represented by General Formula (1) contains a resin represented by General Formula (16), in General Formula (16), represents a bonding site to a carbon atom; A 5 O, A 6 O, OA 7 and OA 8 each independently represents an oxyalkylene group having 1 to 5 carbon atoms; A 9 and A 10 each independently represents an alkylene group having 2 to 6 carbon atoms; n 1 is an integer representing 0 to 7; X 3 ~ X 6 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms; a 19 ~ a 22 is an integer, each independently represents 1 to 100.

3. The negative photosensitive composition according to claim 1, comprising the (a-1) organic black pigment, the organic black pigment comprising a benzodifuranone-based black pigment represented by General Formula (2) or General Formula (3), In General Formula (2) and General Formula (3), R 1 and R 2 each independently represent a hydrogen atom or a methyl group; R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

4. The negative photosensitive composition according to claim 3, wherein the benzodifuranone-based black pigment represented by General Formula (2) or General Formula (3) has a coating layer on its surface, the coating layer containing at least one coating material selected from the group consisting of silicon dioxide, a metal oxide, and a metal hydroxide.

5. The negative photosensitive composition according to claim 1, wherein the resin having a structure represented by General Formula (1) contains a resin in which the value obtained by dividing the total number of moles of repeating units containing an oxyalkylene group having a carbon number of 1 and 2 by the total number of moles of repeating units containing an oxyalkylene group having a carbon number of 3 to 5 is 0.76 to 4.

00.

6. The negative photosensitive composition according to claim 1, further comprising (d) an alkali-soluble resin, the (d) component containing an alkali-soluble polyimide resin and / or an alkali-soluble epoxy (meth)acrylate resin.

7. The negative photosensitive composition according to claim 1, wherein the (b) component further contains a resin having a structure represented by General Formula (22), In general formula (22), A 15 O, A 16 O, OA 17 OA 18 and OA 19 Each independently represents an alkylene oxide having 1 to 5 carbon atoms; A 20 and A 21 Each independently represents an alkylene group having 2 to 6 carbon atoms; n 3 X is an integer, representing 0 to 9; 11 ~X 15 Each can independently represent a hydrogen atom, a hydrocarbon group having 1 to 5 carbon atoms, a group represented by general formula (23), or a group represented by general formula (24); wherein, X 11 and X 12 At least one of them, and X 13 and X 14 At least one of them is an organic group represented by general formula (23) or an organic group represented by general formula (24); a 63 ~a 67 Each integer represents 1 to 100 independently. In General Formula (23), represents a bonding site to an oxygen atom; X 16 represents a hydrogen atom or a methyl group; in General Formula (24), represents a bonding site to an oxygen atom; X 17 represents a hydrogen atom or a methyl group; A 22 O represents an oxyalkylene group having 1 to 5 carbon atoms; a 68 is an integer, and represents 1 to 5.

8. The negative photosensitive composition according to claim 6, wherein the (d) component further contains an alkali-soluble acrylic resin having a structural unit represented by General Formula (39), In General Formula (39), R 24 represents a hydrogen atom or a methyl group; R 25 is a divalent linking group, and represents a hydrocarbon group having 2 to 6 carbon atoms.

9. The negative photosensitive composition according to any one of claims 1 to 8, used for forming a pixel division layer.

10. A pixel division layer comprising a cured product of the negative photosensitive composition according to claims 1 to 8.

11. An organic EL display device comprising the pixel partition layer according to claim 10, and a first electrode, a light-emitting pixel, and a second electrode. The first electrode comprises a silver alloy film.

12. An organic EL display device provided with a pixel division layer, the pixel division layer containing a resin having two or more tertiary amino groups in a molecule and having a structure represented by General Formula (1), In General Formula (1), represents a bonding site with a carbon atom or a nitrogen atom; A 1 O, A 2 O, A 3 O and A 4 O each independently represents an oxyalkylene group having 1 to 5 carbon atoms; a 1 and a 3 is an integer, each independently represents 5 to 60; a 2 and a 4 is an integer, each independently represents 0 to 100; X 1 and X 2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms.

13. The organic EL display device according to claim 12, wherein the organic EL display device is of a top emission type.

14. The organic EL display device according to claim 12, wherein the pixel division layer has a thin film site having a film thickness of 0.5 μm or more and less than 2.0 μm, and a thick film site having a film thickness of 2.0 μm or more and 5.0 μm or less, and has a site in which the difference between the film thickness of the thin film site and the film thickness of the thick film site is 1.0 μm or more.

Images