JP7120022B2 - Organic EL display device and method for forming pixel division layer and planarization layer - Google Patents

Description

The present invention relates to an organic EL display device.

Many products equipped with organic electroluminescence (EL) displays have been developed for display devices having thin displays, such as smartphones, tablet PCs, and televisions. An organic EL display device is a self-luminous display device that emits light using energy resulting from recombination of electrons injected from a cathode and holes injected from an anode. As a specific example thereof, an organic EL display device having a pixel dividing layer and a planarization layer functioning as an insulating film is disclosed (eg, Patent Document 1).

Further, in recent years, attempts have been made to improve the visibility and contrast of organic EL display devices by imparting a light-shielding property to the pixel division layer and/or the planarization layer to reduce the reflection of external light such as sunlight. . As a specific example thereof, an organic EL display device having a blackened pixel division layer is disclosed (for example, Patent Document 2).

Examples of the composition for forming the blackened pixel dividing layer include a photosensitive composition containing a plurality of organic pigments of different hues and pseudo-blackened by subtractive color mixture. A photosensitive composition containing a pigment and an organic blue pigment has been disclosed (see, for example, Patent Document 3).

By the way, when trying to disperse an organic pigment in a resin solution, reaggregation progresses during or after the dispersion process, so that sufficient coloring power cannot be obtained, or in a dispersion system in which multiple types of pigments coexist. often causes problems such as color separation. In order to solve the above problems, it is well known to use an organic dye derivative (synergist) as a dispersant for improving the resin adsorptivity of the surface of the organic pigment and enhancing the dispersion stability. In the field of black matrices for liquid crystal display devices, which require a function to reduce external light reflection in the same way as pixel division layers for organic EL display devices, black matrices have the drawbacks of electrical characteristics such as poor insulation and high dielectric constant. As a technique for substituting carbon black, a pseudo-blackened photosensitive composition has attracted attention, and a technique using both an organic pigment and an organic dye derivative has been disclosed. As a specific example, a pseudo-blackened photosensitive composition containing a perylene-based organic pigment and a copper phthalocyanine derivative having a sulfonic acid group is disclosed (see, for example, Patent Document 4).

WO2016/047483 JP 2013-30293 A JP 2013-207124 A WO2015/015962

However, when a pixel division layer and/or a planarization layer of an organic EL display device are formed using the pseudo-blackened photosensitive composition described in Patent Documents 3 and 4, the organic pigment is dispersed stably in the photosensitive composition. not sexual enough. In addition, since the dispersed state is likely to collapse during the development process, there arises a problem that development residues originating from the pigment aggregates are generated on the ITO electrode in the pattern openings, resulting in the generation of dark spots. In addition, the pixel division layer and/or the planarization are performed using a photosensitive composition that has a certain improvement effect on dispersion stability by increasing the content of the copper phthalocyanine derivative having a sulfonic acid group described in Patent Document 4. When the layer is formed, there arises a problem that the reliability of light emission is impaired, and there is a problem that suppression of dark spots and high reliability of light emission cannot be achieved at the same time.
In view of the above background, an organic EL display device that suppresses the generation of dark spots and has high light emission reliability has been desired.

An organic EL display device of the present invention is an organic EL display device comprising a first electrode, a pixel dividing layer, a luminescent pixel, a second electrode, a planarizing layer and a substrate, wherein the pixel dividing layer and/or the planarizing layer The layer contains (a) a black material having a nitrogen-containing heterocyclic structure, (b) a dispersant, and (c) a resin, and the (b) dispersant is represented by the following general formula (1): and/or a compound represented by the following general formula (2).

In the general formula (1), X ¹ is a substituent directly bonded to the perylene ring and represents -SO ₃ H, -SO ₃ M, -SO ₂ NHR ¹ or -CONHR ¹ . M represents Na, K or _NH4 . R ¹ represents an organic group having a terminal N,N-dialkylamino group. Z ¹ represents an atom directly bonded to the perylene ring or a substituent, and represents a hydrogen atom, an alkyl group or an alkoxy group. n and m are integers, n represents 1 or 2, and satisfies n+m=10.

In the above general formula (2), R ² and R ³ are the same and represent a hydrogen atom, a substituted aryl group or a methyl group, and X ² is a substituent directly bonded to the perylene ring and/or benzene ring. and represents —SO ₃ H, —SO ₃ M, —SO ₂ NHR ⁴ or —CONHR ⁴ . M represents Na, K or _NH4 . R ⁴ represents an organic group having a terminal N,N-dialkylamino group. ^Z2 represents an atom or substituent directly bonded to the perylene ring, and represents a hydrogen atom, an alkyl group or an alkoxy group. p and q are integers, p represents 1 or 2, and q represents 6-8.

According to the organic EL display device of the present invention, dark spots caused by development residues caused by pigment aggregates are suppressed, and excellent light emission reliability can be obtained.

1 is a cross-sectional view of a TFT substrate of an organic EL display device, showing an embodiment of the present invention; FIG. FIG. 2 is a schematic diagram showing a method of manufacturing an organic EL display device having a pixel division layer in Examples. FIG. 2 is a schematic diagram showing a method of manufacturing an organic EL display device having a pixel division layer and a planarization layer in an example.

The present invention will be described in detail below. In this specification, the numerical range represented by "-" means a range including the numerical values before and after "-" as lower and upper limits. In this specification, the pixel division layer means a pixel division layer for an organic EL display device, and the planarization layer means a planarization layer for an organic EL display device. The organic EL display device refers to both a rigid type organic EL display device that cannot be bent and a flexible type organic EL display device that can be bent.

The light shielding property indicates the extent to which light with a wavelength of 380 to 780 nm in the visible light region is shielded, and the higher the light shielding property, the lower the light transmittance. "C.I." used in the name of the colorant is an abbreviation for Color Index Generic Name, and based on the color index published by The Society of Dyers and Colorists, Color Index A Generic Name represents the chemical structure or crystal form of a pigment or dye. The term "organic dye derivative" includes pigment derivatives obtained by subjecting organic pigment powder to derivatization treatment, but it does not necessarily have to be a compound obtained in the form of organic pigment powder in view of the synthesis scheme.

In the present specification, the term "alkali developer" refers to an organic alkaline aqueous solution unless otherwise specified. The weight average molecular weight (Mw) is a value analyzed by gel permeation chromatography using tetrahydrofuran as a carrier and converted using a standard polystyrene calibration curve.

The present invention provides an organic EL display device comprising a first electrode, a pixel division layer, a luminescent pixel, a second electrode, a planarizing layer and a substrate, wherein the pixel dividing layer and/or the planarizing layer comprises ( a) a black material having a nitrogen-containing heterocyclic structure, (b) a dispersant, and (c) a resin, wherein the (b) dispersant is a compound represented by the following general formula (1) and/or An organic EL display device containing a compound represented by the following general formula (2). The present invention has been completed based on the finding that by adopting the above configuration, it is possible to suppress the occurrence of dark spots and achieve excellent light emission reliability. The term "dark spot" as used herein refers to a granular local non-light-emitting portion that is unevenly arranged within a pixel when the organic EL display device is driven. The longer diameter of the dark spots originating from the development residue is enlarged to a size equal to or greater than the length of the development residue, which inhibits light emission. The value of the device will decrease. The light emission reliability here refers to the difficulty of occurrence of a phenomenon (pixel shrinkage) in which the light emitting area of the light emitting element shrinks with the passage of lighting time based on the initial lighting period when the organic EL display device is continuously lit. Good, the higher the light emission reliability, the higher the value as a display device.

In the general formula (1), X ¹ is a substituent directly bonded to the perylene ring and represents -SO ₃ H, -SO ₃ M, -SO ₂ NHR ¹ or -CONHR ¹ . M represents Na, K or _NH4 . R ¹ represents an organic group having a terminal N,N-dialkylamino group. Z ¹ represents an atom directly bonded to the perylene ring or a substituent, and represents a hydrogen atom, an alkyl group or an alkoxy group. n and m are integers, n represents 1 or 2, and satisfies n+m=10.

In the above general formula (2), R ² and R ³ are the same and represent a hydrogen atom, a substituted aryl group or a methyl group, and X ² is a substituent directly bonded to the perylene ring and/or benzene ring. and represents —SO ₃ H, —SO ₃ M, —SO ₂ NHR ⁴ or —CONHR ⁴ . M represents Na, K or _NH4 . R ⁴ represents an organic group having a terminal N,N-dialkylamino group. ^Z2 represents an atom or substituent directly bonded to the perylene ring, and represents a hydrogen atom, an alkyl group or an alkoxy group. p and q are integers, p represents 1 or 2, and q represents 6-8.

An organic EL display device of the present invention comprises a first electrode, a pixel dividing layer, a luminescent pixel, a second electrode, a planarizing layer and a substrate. FIG. 1 shows a cross-sectional view of a TFT substrate in an organic EL display device that is given as a specific example of an embodiment of the present invention.

Bottom-gate type or top-gate type TFTs 1 (thin film transistors) are provided in a matrix on the surface of the substrate 6, and a TFT insulating layer 3 is formed to cover the TFTs 1 and the wiring 2 connected to the TFTs 1. ing. Further, a flattening layer 4 is formed on the surface of the TFT insulating layer 3 , and a contact hole 7 for opening the wiring 2 is provided in the flattening layer 4 . A second electrode 5 is patterned on the surface of the planarizing layer 4 and connected to the wiring 2 . A pixel division layer 8 is formed so as to surround the pattern periphery of the second electrode 5 . The pixel division layer 8 is provided with an opening, and the opening is formed with a light emitting pixel 9 containing an organic EL light emitting material. A first electrode 10 separates the pixel dividing layer 8 and the light emitting pixel 9. A film is formed in a state of covering. By applying a voltage directly to the light-emitting pixel portion after sealing the TFT substrate having the above laminated structure under vacuum, it is possible to emit light as an organic EL display device.

The light-emitting pixels 9 are formed by arranging different types of pixels having light emission peak wavelengths in the three primary colors of red, blue, and green, respectively, or by forming light-emitting pixels emitting white light on the entire surface. A laminate member may be a combination of red, blue, and green color filters. The peak wavelength of the red region normally displayed 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. is not particularly limited, and the emitted light may have any peak wavelength. As the organic EL light-emitting material constituting the light-emitting pixel, a material obtained by combining a hole-transporting layer and/or an electron-transporting layer in addition to the light-emitting layer can be preferably used.

A method for patterning light-emitting pixels includes a mask vapor deposition method. The mask vapor deposition method is a method of vapor-depositing and patterning an organic compound using a vapor deposition mask. Specifically, vapor deposition is performed by arranging a vapor deposition mask having a desired pattern as an opening on the substrate side. mentioned. In order to obtain a highly precise deposition pattern, it is important to have a highly flat deposition mask in close contact with the substrate. can be used, for example, a technique of adhering the to the substrate. Etching methods, mechanical polishing, sandblasting, sintering, laser processing, and the use of photosensitive resin are examples of methods for manufacturing vapor deposition masks. It is preferable to use an etching method or an electroforming method because of their superiority.

As the second electrode 5, for example, conductive metal oxides such as zinc oxide, tin oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO) can be used. ITO can be preferably used because of its excellent properties. As a method for patterning the ITO, first, an ITO film is formed on the entire surface by a sputtering method, and then a positive resist material for etching is patterned by a photolithography method to obtain a resist pattern on the ITO film. Next, only the ITO film in the resist pattern non-formation portion is removed with an etchant at a liquid temperature of 20 to 60° C., then the resist pattern is removed with a resist stripper at a liquid temperature of 20 to 60° C., and if necessary. A method of performing a heat treatment to obtain a desired degree of crystallinity may be mentioned. The ITO referred to here includes so-called amorphous ITO. As a positive resist material for etching, a positive photosensitive composition containing an alkali-soluble novolac resin can be used. As the etchant, an aqueous solution containing nitric acid and hydrochloric acid or an aqueous oxalic acid solution can be used. 2. IS-3 (both of which are manufactured by Sasaki Chemicals Co., Ltd.). An organic amine-based aqueous solution can be used as the resist stripping solution, and commercially available products include, for example, "Anlast" (registered trademark) M6, Anlast M6B, TN-1-5, and M71-2 (both of which are Sanwaka Junyaku Research Institute).

As the first electrode 10, for example, a silver alloy film can be suitably used, but any material may be used as long as the layer can function as an electrode. As a specific example of the first electrode 10, when the organic EL display device of the present invention is a bottom emission type organic EL display device described later, a layer made of aluminum can be preferably used in terms of excellent light reflectivity. In the case of a top emission type organic EL display device, a layer made of a silver alloy made of silver/magnesium can be preferably used in terms of excellent light transmittance. The first electrode can be obtained by forming a film over the entire surface by sputtering.

The light extraction direction of the organic EL display device of the present invention may be a bottom emission type organic EL display device in which the emitted light emitted from the light emitting pixel is extracted to the base material side through the base material 6. It may be a top emission type organic EL display device in which emitted light is extracted to the opposite side of the substrate 6 via one electrode, and is not particularly limited. In the case of a top emission type organic EL display device, a patterned metal reflective layer may be further provided between the planarizing layer 4 and the second electrode 5 in order to increase the light extraction efficiency in one direction. good. Examples of the metal reflective layer include a conductive film made of a silver alloy containing dissimilar metal elements such as copper, gallium and magnesium.

If a rigid plate-like substrate such as glass is used as the substrate 6, a rigid type organic EL display device that cannot be bent can be obtained. As the glass, an alkali-free glass having an alkali metal element content of less than 0.5% and containing silicon as a main component can be suitably used. Among them, those having a small coefficient of thermal expansion and excellent dimensional stability in high-temperature processes at 250° C. or higher are preferred. 100 (manufactured by Asahi Glass Co., Ltd.), and its thickness is usually 0.1 to 0.5 mm from the viewpoint of physical durability.

On the other hand, if a flexible base material is used for the base material 6, a bendable flexible type organic EL display device can be obtained. As the flexible substrate, a substrate made of a polyimide resin having high flexibility and excellent mechanical strength can be suitably used. A method of applying and then heating to imidize the polyamic acid to convert it into a polyimide resin, and then peeling off the temporary support with a laser or the like can be used. Polyamic acid can be synthesized by reacting a tetracarboxylic dianhydride and a diamine compound in an amide solvent such as N-methyl-2-pyrrolidone. A polyamic acid having an aromatic tetracarboxylic dianhydride residue and an aromatic diamine compound residue is preferred because of its superiority. A specific example is a polyamic acid having a residue of 3,3′,4,4′-biphenyltetracarboxylic dianhydride and a residue of p-phenylenediamine. Its thickness is usually 10 to 40 μm, and the substrate 6 can be made thinner compared to the case of using the alkali-free glass.

The pixel dividing layer and/or planarizing layer included in the organic EL display device of the present invention contain (a) a black material having a nitrogen-containing heterocyclic structure. The black material having a nitrogen-containing heterocyclic structure here means (a-1) an organic pigment having at least one nitrogen-containing heterocyclic structure selected from organic yellow pigments, organic red pigments and organic orange pigments, and ( a-2) a pigment mixture containing at least one organic pigment having a nitrogen-containing heterocyclic structure selected from organic blue pigments and organic purple pigments, or (a-3) an organic pigment having a nitrogen-containing heterocyclic structure It refers to black pigment. (a) By including a black material having a nitrogen-containing heterocyclic structure, the pixel division layer and/or the flattening layer can be blackened to impart light-shielding properties.

(a) A component belonging to a black material having a nitrogen-containing heterocyclic structure is contained in a photosensitive composition for patterning a pixel dividing layer and/or a planarization layer included in the organic EL display device of the present invention. By keeping it, it can be filled in the finally obtained film of the pixel division layer and/or the flattening layer.

The (a) black material having a nitrogen-containing heterocyclic structure contained in the pixel dividing layer and/or the flattening layer included in the organic EL display device of the present invention is highly resistant to an organic alkaline aqueous solution in terms of improving light emission reliability. Organic pigments having both alkali resistance and high heat resistance to heating are preferred. The alkali resistance referred to here specifically means the resistance to a 2.38% by weight tetramethylammonium hydroxide aqueous solution, which is usually used as a developer when patterning the pixel dividing layer and the flattening layer in the development process described later. , refers to resistance under atmospheric pressure and 25°C conditions. When the organic pigment comes into contact with the developing solution via the binder, the more the pigment dissolves and/or decomposes, the better. The term "heat resistance" as used herein refers to a thermal decomposition product and/or a sublimate produced by heating at 250° C. under atmospheric pressure/in a nitrogen atmosphere when thermally curing the pixel division layer and the flattening layer in the curing step described later. It refers to the extent to which the occurrence can be suppressed. The heat-resistant temperature required for the pixel division layer and the planarization layer of the organic EL display device as a permanent film is 250° C. or more, and the smaller the amount of outgassing from the pixel division layer and the planarization layer under high temperature conditions, the higher the light emission reliability. can improve sexuality.
(a) Having a nitrogen-containing heterocyclic structure Specific examples of the nitrogen-containing heterocyclic structure in the molecule of the organic pigment contained in the black material include, in addition to improving the heat resistance and alkali resistance of the organic pigment itself, Since the interaction with the compound represented by the general formula (1) and/or the compound represented by the general formula (2) is strong and a higher effect of suppressing development residue can be obtained, imide ring, benzimidazo Ron ring and benzimidazole ring are particularly preferred. It is preferable to contain an organic pigment having a nitrogen-containing heterocyclic structure of any one of these.

In order to enhance the light-shielding properties of the pixel dividing layer and/or the planarizing layer in the entire visible light region, the three colors of (a-1) an organic yellow pigment, an organic red pigment, and (a-2) an organic blue pigment are contained. or a combination containing (a-1) an organic yellow pigment, (a-2) an organic blue pigment, and an organic purple pigment. (a-1) an organic yellow pigment, an organic red pigment, and (a-2) in the case of a combination containing three colors of an organic blue pigment, the three organic pigments out of all the pigments in the photosensitive composition is preferably 20% by weight or more. In order to sufficiently block light in the wavelength range of 550 to 780 nm and increase the optical density described later, the content of the organic blue pigment is more preferably 30.0% by weight or more in the total pigment, and the exposure in the exposure step described later. From the viewpoint of sensitivity, 50.0% by weight or less is more preferable.

On the other hand, in the case of a combination containing three colors of (a-1) an organic yellow pigment, (a-2) an organic blue pigment, and an organic purple pigment, three colors out of all pigments in the photosensitive composition The content of the organic pigment in each is preferably 20.0% by weight or more. In order to sufficiently block light in the wavelength region of 450 to 650 nm and increase the optical density described later, the content of the organic purple pigment is more preferably 30.0% by weight or more, and 50.0% by weight or less in the total pigment. is more preferred.

Examples of organic yellow pigments having a nitrogen-containing heterocyclic structure include C.I. I. Pigment Yellow 120, 138, 139, 151, 175, 180, 185, 181, 192, and 194, and these may be used alone or in combination. Among them, an organic yellow pigment having a benzimidazolone ring structure and not having a halogen atom is preferable because of its excellent alkali resistance and heat resistance. I. Pigment Yellow 120, 151, 175, 180, 181, 192, 194 are preferred. C. I. Pigment Yellow 194 and/or C.I. I. Pigment Yellow 192 is more preferred.

Examples of organic orange pigments having a nitrogen-containing heterocyclic structure include C.I. I. Pigment Orange 13, 36, 43, 61, 64, 71 and 72 can be mentioned, and these may be used singly or in combination. Among them, an organic orange pigment having a perinone structure is preferable from the viewpoint of excellent alkali resistance and heat resistance, and C.I. I. Pigment Orange 43 is more preferred. C., which is a trans form. I. Pigment Orange 43 is desirably isomer-separated with high purity from the viewpoint of emission reliability, and the residual amount of the cis-isomer (CI Pigment Red 194), which is a by-product during synthesis, is C . I. It is preferably 5.0% by weight or less based on Pigment Orange 43.

Examples of organic red pigments having a nitrogen-containing heterocyclic structure include C.I. I. Pigment Red 122, 123, 149, 179, 180, 189, 190, 202, 209, 254, 255, and 264, and these may be used singly or in combination. Among them, those having a perylene ring structure and an imide ring structure, which have high alkali resistance and heat resistance, do not have halogen atoms that adversely affect the light emission reliability in the structure, and have a perylene ring structure and an imide ring structure are preferable. C.I. represented by the following structural formula (5). I. Pigment Red 123, C.I. I. Pigment Red 149, C.I. I. Pigment Red 179, C.I. I. Pigment Red 190 is preferred.

Examples of organic blue pigments having a nitrogen-containing heterocyclic structure include C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:6, 16, 60, 64, 75, 79, and 80, and these may be used singly or in combination. do not have. Among them, those having a phthalocyanine structure or an indanthrone structure, which have high alkali resistance and heat resistance, do not have halogen atoms which adversely affect light emission reliability in the structure, are preferable. C.I., which is a β-type stable crystal of copper phthalocyanine, represented by the following structural formula (9). I. Pigment Blue 15:3 and C.I. I. pigment blue 15:6, C.I. I. Pigment Blue 60 is preferred.

Note that the C.I. I. Copper phthalocyanine-based organic blue pigments such as Pigment Blue 15:3 and 15:6 are all unsubstituted phthalocyanine-based organic blue pigments having a stable crystal structure, and are one type of organic dye derivatives. It has excellent heat resistance and alkali resistance as compared with the copper phthalocyanine derivative having a sulfonic acid group described in 4 above. Among them, from the viewpoint of light emission reliability, it is preferable to use an impurity containing free copper of 500 ppm or less, more preferably 100 ppm or less.

Examples of organic purple pigments having a nitrogen-containing heterocyclic structure include C.I. I. Pigment Violet 19, 23, 29, 32 and 37 can be mentioned, and these may be used singly or in combination. Among them, those having a perylene ring structure and/or a dioxazine structure, which have high alkali resistance and heat resistance, do not have halogen atoms that adversely affect the light emission reliability in the structure, are preferable. C. I. Pigment Violet 29 and 37 are preferred, and from the viewpoint of dispersibility, C.I. I. Pigment Violet 29 is more preferred.

(a) When the black material having a nitrogen-containing heterocyclic structure is a combination containing three colors: (a-1) an organic yellow pigment, an organic red pigment, and (a-2) an organic blue pigment, organic yellow The pigment contains a benzimidazolone organic yellow pigment, the organic blue pigment contains a phthalocyanine organic blue pigment and/or an indanthron organic blue pigment, and the organic red pigment contains a perylene organic red pigment. is most preferred. By adsorbing the compound represented by the general formula (1) and/or the compound represented by the general formula (2) described later, these plural types of pigments with different chemical structures are preferably dispersed and stabilized. can be done.

Examples of (a-3) organic black pigments having a nitrogen-containing heterocyclic structure include perylene organic black pigments, benzodifuranone organic black pigments having a lactam ring structure, and azomethine azo organic black pigments. Among them, it has excellent heat resistance and light-shielding properties, and has a strong interaction with the compound represented by the general formula (1) and / or the compound represented by the general formula (2), and has high absorbability. Perylene-based organic black pigments having two benzimidazole rings in the molecule as nitrogen-containing heterocycles are preferred. Specific examples thereof include a mixture of a compound represented by the following general formula (12) and a compound represented by the following general formula (13), and a compound represented by the general formula (1) described below and/or By adsorbing the compound represented by the general formula (2), these plural types of pigments having different chemical structures can be suitably dispersed and stabilized. The perylene-based organic black pigment having two benzimidazole rings in the molecule can be obtained as a cis-trans isomer mixture by reacting perylenetetracarboxylic dianhydride with o-phenylenediamine or a derivative thereof. .

In general formulas (12) and (13), R ⁷ to R ¹⁴ each independently represent 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.

The pixel division layer and the flattening layer included in the organic EL display device of the present invention contain an organic pigment belonging to the above component (a-1), (a-2) or (a-3) for fine adjustment of optical properties. pigments other than C.I. I. Pigment Green 7, 36, 58, 59, C.I. I. In addition to Pigment Brown 25, 26 and 28, titanium nitride, titanium oxynitride and the like can be used.

(a) The content of the black material having a nitrogen-containing heterocyclic structure is preferably 5% by weight or more, preferably 10% by weight or more, based on the total solid content of the photosensitive composition in order to obtain sufficient light shielding properties in the visible light region. is more preferred. In order to ensure the dispersion stability of the photosensitive composition and to obtain sufficient sensitivity and developability to exposure, it is preferably 70% by weight or less, more preferably 50% by weight or less. The term "total solid content" as used herein refers to a value obtained by dividing the sum of the weights of all components contained in the photosensitive composition other than the solvent by the weight of the photosensitive composition and multiplying by 100.

(a) The average primary particle size of each of the various organic pigments contained in the black material having a nitrogen-containing heterocyclic structure is, from the viewpoint of the dispersion stability of the photosensitive composition, maintenance of dispersibility during the development process, and light emission reliability, 30 nm or more is preferable, and 40 nm or more is more preferable. On the other hand, it is preferably 150 nm or less, more preferably 100 nm or less, from the viewpoint of improving the pattern linearity of the pixel dividing layer and the planarizing layer.

The average primary particle size as used herein refers to the number average value of the primary particle size calculated by a particle size measurement method using an image analysis type particle size distribution analyzer. A transmission electron microscope (TEM) can be used to take an image, and the average primary particle diameter can be calculated from an image of 100 or more primary particles of the organic pigment taken at a magnification of 50000 times. can. When the organic pigment is not spherical, the primary particle diameter is the average of the major and minor diameters. Image analysis type particle size distribution software Mac-View manufactured by Mountec can be used for image analysis.

If it is necessary to reduce the average primary particle size of the organic pigment in advance or crush coarse particles before performing the wet media dispersion treatment described later, the average primary particles are reduced by wet pulverization such as solvent salt milling. The diameter may be adjusted within the desired range. The solvent salt milling method is a method of kneading and washing a mixture of an organic pigment, a water-soluble inorganic salt and a water-soluble organic solvent in a highly viscous paste state. The water-soluble inorganic salt may be a particulate one that functions as a grinding agent, and sodium chloride, potassium chloride or potassium sulfate can be preferably used among them. The water-soluble inorganic salt preferably has an average primary particle size of about 0.5 to 50 μm. Examples of water-soluble organic solvents include organic solvents such as glycol-based solvents, ether-based solvents, and alcohol-based solvents. Among them, glycol-based solvents are preferable, and specific examples include ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, dipropylene glycol, and dipropylene. Glycol monomethyl ether, dipropylene glycol monoethyl ether can be mentioned. After kneading, the water-soluble inorganic salt and water-soluble solvent are preferably removed by repeatedly washing with water.

As a wet pulverizer for kneading, for example, a kneader (manufactured by Inoue Seisakusho Co., Ltd.) can be used. The kneading conditions such as pigment concentration, grinding agent concentration, kneading speed, temperature and time during kneading may be appropriately set so as to obtain a desired average primary particle size while adjusting the balance of the speed of mixing. (a) It is preferable to individually knead various organic pigments contained in the black material having a nitrogen-containing heterocyclic structure.

(a) the black material having a nitrogen-containing heterocyclic structure, the compound represented by the general formula (1) and/or the compound represented by the general formula (2) is measured by NMR, infrared absorption spectrum, ICP mass spectrometry , time-of-flight mass spectrometry (TOF-MS) and powder X-ray diffraction with CuKα radiation can be combined to identify the chemical structure and its crystalline form. The number of substituents n or p of the compound represented by the general formula (1) and/or the compound represented by the general formula (2) described later can be analyzed by further combining liquid phase chromatography.

The pixel dividing layer and/or planarizing layer included in the organic EL display device of the present invention contain (b) a dispersant. Components belonging to (b) dispersants can be broadly classified into (b-1) non-polymeric dispersants and (b-2) polymeric dispersants.

(b-1) Non-polymer type dispersants include, for example, organic pigments, dyes, and other organic dye derivatives in which an acidic functional group and/or a basic functional group are introduced into the molecule, and rosin-based dispersants. is mentioned. The term "acidic functional group" as used herein includes groups in the form of salts.
On the other hand, the (b-2) polymer-type dispersant includes a polymer having an acidic adsorptive group and/or a basic adsorptive group in its molecule.

(b) The action mechanism of the dispersant includes acid-base interaction, π-π electron interaction, hydrogen bonding, Van-der-Waals force, etc., and is involved in a complex manner to prepare a pigment dispersion described later. In the wet media dispersion treatment performed when the organic pigment By promoting the disaggregation of the secondary aggregates and suppressing the reaggregation, the effect of stabilizing the dispersed state is exhibited.

(b) A component belonging to the dispersant is included in the photosensitive composition for patterning the pixel dividing layer and/or the planarizing layer included in the organic EL display device of the present invention, so that the final can be filled in the film of the pixel division layer and/or the planarizing layer obtained in the first step.

The pixel dividing layer and/or planarizing layer included in the organic EL display device of the present invention comprises (b-1) a compound represented by the following general formula (1) as a non-polymer dispersant and/or (2) containing the compound represented by (hereinafter, the compound represented by the following general formula (1) and / or the compound represented by the following general formula (2) is referred to as a "perylene dye having a specific structure It may be described later in the notation of "derivative").

In the general formula (1), X ¹ is a substituent directly bonded to the perylene ring and represents -SO ₃ H, -SO ₃ M, -SO ₂ NHR ¹ or -CONHR ¹ . M represents Na, K or _NH4 . R ¹ represents an organic group having a terminal N,N-dialkylamino group. Z ¹ represents an atom directly bonded to the perylene ring or a substituent, and represents a hydrogen atom, an alkyl group or an alkoxy group. n and m are integers, n represents 1 or 2, and satisfies n+m=10.

In the above general formula (2), R ² and R ³ are the same and represent a hydrogen atom, a substituted aryl group or a methyl group, and X ² is a substituent directly bonded to the perylene ring and/or benzene ring. and represents —SO ₃ H, —SO ₃ M, —SO ₂ NHR ⁴ or —CONHR ⁴ . M represents Na, K or _NH4 . R ⁴ represents an organic group having a terminal N,N-dialkylamino group. ^Z2 represents an atom or substituent directly bonded to the perylene ring, and represents a hydrogen atom, an alkyl group or an alkoxy group. p and q are integers, p represents 1 or 2, and q represents 6-8.

The features of the perylene-based dye derivative having the above specific structure will be described in order.
As a result of studies by the present inventors, it has been found that a specific acidic functional group or basic functional group is attached to a carbon atom constituting a perylene ring and/or a carbon atom constituting a benzene ring possessed by an aryl group, and a specific To discover that a perylene-based dye derivative having a structure in which the number of substituents is directly bonded exhibits the following three characteristics, and to use the perylene-based dye derivative in a pixel dividing layer and/or a planarization layer of an organic EL display device. However, it has been found that there is a particularly remarkable effect in solving the problem.

First, the perylene-based dye derivative having the above-mentioned specific structure interacts with and adsorbs to (a) the black material having a nitrogen-containing heterocyclic ring structure, thereby increasing the polarity of the pigment surface, and fine particles in the wet media dispersion treatment described later. It has the function of promoting refinement and improving dispersion stability after refinement. As a result, even if the photosensitive composition is stored for a long period of time, the effect of suppressing the generation of pigment aggregates and color separation is exhibited.

Secondly, since the perylene dye derivative having the specific structure has high alkali resistance, the molecular structure of the perylene dye derivative itself is destroyed even when it comes into contact with a high-concentration organic alkaline aqueous solution in the development process described later. does not occur, it is possible to maintain a good dispersion state without losing its function as a dispersant during the development process. As a result, there is an effect of suppressing the generation of development residue on the ITO electrode caused by pigment aggregates.
Here, storing the photosensitive composition for a long period of time means that the photosensitive composition is allowed to stand in a sealed state under atmospheric pressure/under light shielding/at a constant temperature of 25° C.±1° C. for 30 days.

Thirdly, the perylene-based dye derivative having the specific structure has a rigid perylene ring as a base skeleton and can exhibit high heat resistance without containing heavy metals or halogen atoms in its structure. C. or more in a severe environment, and corrosion of electrodes due to migration of heavy metals can be avoided.

In addition, a highly polar functional group such as an acidic functional group or a basic functional group is directly bonded to a carbon constituting a perylene ring or a carbon constituting a benzene ring of an aryl group having a substituent, thereby forming a highly polar group. desorption can be suppressed. Further, since the number of substituents per molecule is 1 or 2, sublimation of the organic dye derivative itself can be suppressed. A specific example of elimination here is desulfonation, in which a sulfonic acid group introduced into the molecular structure by a derivatization treatment, which will be described later, is removed from the organic pigment-derived backbone residue by high-temperature treatment. transformation.
Due to such excellent characteristics, it is possible to suppress the sublimation of the perylene dye derivative itself and the generation of thermal decomposition products in the curing process described later, and as a result, the effect of suppressing the above-mentioned development residue can be obtained. However, it is possible to achieve both high light emission reliability.

The preferred structure of the functional group possessed by the perylene-based dye derivative having the above specific structure can be determined by the acidity or basicity of the adsorptive group possessed in the structure when the (b-2) polymer-type dispersant described later is included. preferable.

In the case of containing a polymer-type dispersant having a basic adsorptive group, the structure of the perylene-based dye derivative having the above-mentioned specific structure is excellent in the effect of suppressing development residue. ), X ¹ and X ² are preferably acidic functional groups or salts thereof, ie, —SO ₃ H or —SO ₃ M, more preferably —SO ₃ H. In the case of —SO ₃ M, M is preferably NH ₄ from the standpoint of improving light emission reliability. These compounds may be used singly or in combination. The notation of —SO ₃ H or —SO ₃ M in this specification means that the hydrogen atom, sodium ion, potassium ion or ammonium ion in the sulfonic acid group in the photosensitive composition is dissociated, X ¹ and When X ² is in the state of an anion represented by —SO ₃ ^— , or when —SO 3 — forms an ionic bond with a polymer-type dispersant (b-2) described later, or when —SO ₃ ^— forms an ionic bond with another component. It also includes the case of being in a combined state. In the above general formula (1), X ¹ is directly bonded to any carbon among the 1, 2, 5, 6, 7, 8, 9, 10, 11, and 12 carbon atoms constituting the perylene ring. indicates that it is permissible. In general formula (2) above, X ² constitutes a benzene ring of an aryl group having carbon atoms at positions 1, 2, 5, 6, 7, 8, 11, and 12 constituting a perylene ring and a substituent. It means that it may be directly bonded to any carbon among the carbons. Among them, in order to obtain higher emission reliability, it is preferable that X2 is directly bonded to any one of carbon atoms at positions 1, ² , 5, 6, 7, 8, 11, and 12 constituting the perylene ring. preferable. Note that the notation of each structural formula using [ ] in general formulas (1) and (2) is based on the technical common sense of those skilled in the art, and the number of each functional group introduced per molecule of the organic dye derivative is the same. and may be a mixture of a plurality of compounds having different carbon positions to which the functional groups are bonded. For example, in the above general formula (1), in the case of a compound in which X ¹ is —SO ₃ H, n is 1, Z ¹ is all hydrogen atoms, and m is 9, perylene-3,4 - It may be a mixture of perylene-3,4-dicarboximide-9-sulfonic acid and perylene-3,4-dicarboximide-8-sulfonic acid, which are monosulfonated products of dicarboximide. represents As an example, unsubstituted perylene-3,4-dicarboximide represented by the following structural formula (14), which is a part of the skeleton constituting the chemical structure of the perylene-based dye derivative having the above specific structure, The position number of each carbon constituting the perylene ring is shown.

In general formula (2) above, R ² and R ³ are preferably substituted aryl groups or methyl groups from the viewpoint of improving light emission reliability. The aryl group or methyl group having a substituent here means either an aryl group having a substituent or a methyl group. The term "substituent" as used herein refers to a substituent other than X ² bonded to the carbon constituting the benzene ring of the aryl group. The aryl group referred to here means an aryl group having at least a benzene ring, and does not include heteroaryl groups such as pyridyl groups having a nitrogen-containing heterocyclic ring structure. It does not include an aliphatic group bonded to an aromatic ring having a substituent, such as a 4-methoxyphenylmethyl group. For example, C.I. I. An organic dye derivative having the molecular structure of Pigment Black 32 as a residue after derivatization treatment is not included in the elements constituting the present invention.

Examples of the aryl group having a substituent include an ethoxyphenyl group, a dimethylphenyl group, a methoxyphenyl group, a phenylazophenyl group, and a diisopropylphenyl group. From the point of view, a 4-ethoxyphenyl group, a 3,5-dimethylphenyl group, a 4-methoxyphenyl group and a 4-(phenylazo)phenyl group are preferred.
Moreover, in general formulas (1) and (2) above, Z ¹ and Z ² are preferably all hydrogen atoms in order to increase the heat resistance of the perylene dye derivative having the specific structure.

When the polymer-type dispersant (b-2) described later contains a polymer-type dispersant having an acidic adsorptive group as an adsorptive group, it is represented by the above general formula (1) in that it is excellent in the effect of suppressing development residues. X ¹ in the above general formula (1) is preferably a basic functional group. That is, it is preferably —SO ₂ NHR ¹ or —CONHR ¹ . From the viewpoint of light emission reliability, -CONHR ¹ is more preferable.

On the other hand, in the compound represented by general formula (2) above, X ² is preferably a basic functional group. That is, -SO ₂ NHR ⁴ or -CONHR ⁴ is preferred. —CONHR ⁴ is more preferable from the viewpoint of emission reliability. Examples of R ¹ and R ⁴ , which are organic groups having N,N-dialkylamino groups at their ends, include N,N-dimethylaminomethyl, N,N-dimethylaminoethyl and N,N-dimethylaminopropyl. group, N,N-dimethylaminobutyl group, N,N-diethylaminomethyl group, N,N-diethylaminoethyl group, N,N-diethylaminopropyl group, N,N-diethylaminobutyl group, N,N-dipropylamino methyl group, N,N-dipropylaminoethyl group, N,N-dipropylaminopropyl group, N,N-dipropylaminobutyl group, N,N-dibutylaminomethyl group, N,N-dibutylaminoethyl group , N,N-dibutylaminopropyl group and N,N-dibutylaminobutyl group.

Among them, an organic group having an N,N-dimethylamino group at its end or an N,N-diethylamino An organic group having a group at its end is preferred. N,N-dimethylaminomethyl group, N,N-dimethylaminoethyl group, N,N-dimethylaminopropyl group, N,N-dimethylaminobutyl group, N,N-diethylaminomethyl group, N,N-diethylaminoethyl group, N,N-diethylaminopropyl group and N,N-diethylaminobutyl group are preferred.

Specific examples of compounds in which X ¹ is a basic functional group include, for example, compounds represented by the following structural formulas (15) and (16), and when X ² is a basic functional group: As specific examples of the compound, for example, compounds represented by the following structural formulas (17) to (21) can be preferably mentioned.

The perylene-based dye derivative having the above specific structure suppresses development residue derived from (a) a black material having a nitrogen-containing heterocyclic structure, regardless of whether it has an acidic functional group or a basic functional group. However, in order to reduce the interaction with the ITO surface and enhance the effect of suppressing dark spots, it is preferable that the perylene-based dye derivative having a specific structure have an acidic functional group. Among them, it is more preferable to have a sulfonic acid group (--SO ₃ H) as an acidic functional group in terms of improving dispersion stability and being excellent in the effect of suppressing development residue. The perylene dye derivative having a specific structure having a sulfonic acid group preferably contains a compound represented by the following general formula (22) and/or a compound represented by the following general formula (23). It is more preferable to use the compound represented by the following general formula (22) and the compound represented by the following general formula (23) in combination from the viewpoint of excellent dispersion stabilizing effect and development residue suppressing effect. In general formula (22) below, the sulfonic acid group (—SO ₃ H) is the , may be directly bonded to any carbon. In the following general formula (23), the sulfonic acid group constitutes carbon atoms at positions 1, 2, 5, 6, 7, 8, 11, and 12 constituting the perylene ring, and the benzene ring of the aryl group having a substituent. It may be directly bonded to any carbon among the carbons.

In general formula (22) above, X ³ represents —SO ₃ H directly bonded to the perylene ring. ^Z3 represents a hydrogen atom directly bonded to the perylene ring. n and m are integers, n represents 1 or 2, and satisfies n+m=10.

In general formula (23) above, R ⁵ and R ⁶ are the same and represent a hydrogen atom, a substituted aryl group or a methyl group. X ⁴ represents —SO ₃ H directly bonded to the perylene ring and/or benzene ring, and Z ⁴ represents a hydrogen atom directly bonded to the perylene ring. p and q are integers, p represents 1 or 2, and q represents 6-8.

In general formula (23) above, R ⁵ and R ⁶ are preferably substituted aryl groups or methyl groups from the viewpoint of heat resistance. The aryl group or methyl group having a substituent here means either an aryl group having a substituent or a methyl group. Examples of substituted aryl groups include ethoxyphenyl, dimethylphenyl, methoxyphenyl, phenylazophenyl, and diisopropylphenyl, as exemplified for R ² and R ³ in general formula (2) above. groups. As more specific substitution forms, a 4-ethoxyphenyl group, a 3,5-dimethylphenyl group, a 4-methoxyphenyl group, and a 4-(phenylazo)phenyl group are preferred from the viewpoint of improving light emission reliability.

As the compound represented by the general formula (22), for example, a compound represented by the following structural formula (24) can be preferably mentioned. Moreover, as the compound represented by the above general formula (23), for example, a compound represented by the following structural formula (25) can be preferably mentioned. These may be contained singly or in combination.

(b) The perylene-based dye derivative having a specific structure, which is a component belonging to the dispersant, is a compound in which the number of substituents n of X ¹ is 1 or 2 in the above general formula (1). A compound may be further contained. However, when a compound having a substituent number n of 3 or more is contained, in order to obtain high light emission reliability, in the general formula (1), the average number of substituents with a compound having a substituent number n of X ¹ of 1 or 2 is It is preferable to make it within the range of 1.0 to 2.0. For example, when a compound having a substituent number n of 1 and a compound having a substituent number n of 3 are contained in equimolar amounts, the average number of substituents is 2.0. In the general formula (2), when a compound in which the number p of substituents of X ² is 1 or 2 and a compound in which the number p of substituents is 3 or more are used in combination, the average number of substituents is 1 It is preferable to make it within the range of 0.0 to 2.0.

As a method for synthesizing a perylene-based dye derivative having a specific structure contained in the pixel dividing layer and/or the planarizing layer included in the organic EL display device of the present invention, for example, industrially available perylene-3,4- dicarboximide, perylene-3,4-dicarboximide carboxylic acid, C.I. I. Pigment Red 123, C.I. I. Pigment Red 149, C.I. I. Pigment Red 178, C.I. I. Pigment Red 179, C.I. I. Pigment Red 190, C.I. I. Pigment Violet 29, N,N'-bis(2,6-diisopropylphenyl)-3,4,9,10-perylenetetracarboxylic acid diimide (hereinafter sometimes referred to as "perylene orange"), or them Examples include a method in which a compound having a perylene ring structure or the like is used as a starting material and subjected to various derivatization treatments described later so as to have a desired chemical structure.

In the above general formula (1), a method for synthesizing the compound having the above-mentioned acidic functional group or a salt thereof includes, for example, perylene-3,4-dicarboximide, 10 to 40% fuming sulfuric acid, 70 to 100% concentrated Dissolve in sulfuric acid, chlorosulfonic acid or a mixture thereof, and stir for 1-6 hours while heating to 40-90°C. Then, the red solid obtained by pouring into a large amount of water or ice water having a weight of 100 times or more the weight of the perylene-3,4-dicarboximide used and precipitated is washed with water and filtered, and further treated with acetone. By drying after washing and performing dry pulverization, a compound in which X ¹ is —SO ₃ H in the general formula (1) can be obtained.

Furthermore, by neutralizing with a predetermined amount of an inorganic basic chemical solution such as an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, or an aqueous ammonia solution, at least one —SO ₃ H in the molecule is converted to a sodium salt (—SO ₃ Na ), the potassium salt (--SO ₃ K) or the ammonium salt (--SO ₃ NH ₄ ), ie compounds in which X ¹ is --SO ₃ M can be obtained. Also, the mixing ratio of —SO ₃ H and —SO ₃ M can be controlled by adjusting the amount of the inorganic basic chemical solution.

In the above general formula (1), the method for synthesizing the compound having the above basic functional group includes perylene-3,4-dicarboximide, 10 to 40% fuming sulfuric acid, 70 to 100% concentrated sulfuric acid, chlorosulfone. Dissolves in acids or mixtures thereof. Next, after stirring for 1 to 6 hours while heating to 40 to 90° C., thionyl chloride is further added and stirred to obtain perylene-3,4-dicarboximidesulfonyl chloride. Then, in the presence of a catalyst, it is reacted with a predetermined amount of N,N-dialkylaminoalkylamines to form a sulfonamide, and a large amount of the perylene-3,4-dicarboximide used is 100 times or more in weight. A dark red solid precipitated by pouring into water or ice water is washed with water and filtered. Further, the product is washed with acetone to remove the catalyst, dried, and subjected to dry pulverization to obtain a compound in which X ¹ is —SO ₂ NHR ¹ in the above general formula (1).

Also, perylene-3,4-dicarboximide carboxylic acid is dissolved in a methylene chloride solvent, thionyl chloride is added and stirred to obtain perylene-3,4-dicarboximide carbonyl chloride, and then a methylene chloride solvent and Unreacted thionyl chloride is removed under reduced pressure. It is then reacted with a predetermined amount of N,N-dialkylaminoalkylamines in the presence of a catalyst to form a carboxamide, and the resulting dark red solid is washed with water and filtered. Further, the product is washed with acetone to remove the catalyst, dried, and subjected to dry pulverization to obtain a compound in which X ¹ is —CONHR ¹ in the general formula (1). Examples of the catalyst for promoting the reaction to obtain the sulfonamide or carboxamide described above include amine-based catalysts such as trimethylamine and triethylamine.

Examples of N,N-dialkylaminoalkylamines include N,N-dimethylaminomethylamine, N,N-dimethylaminoethylamine, N,N-dimethylaminopropylamine, N,N-dimethylaminobutylamine, N, N-diethylaminomethylamine, N,N-diethylaminoethylamine, N,N-diethylaminopropylamine, N,N-diethylaminobutylamine, N,N-dipropylaminomethylamine, N,N-dipropylaminoethylamine, N,N -dipropylaminopropylamine, N,N-dipropylaminobutylamine, N,N-dibutylaminomethylamine, N,N-dibutylaminoethylamine, N,N-dibutylaminopropylamine, N,N-dibutylaminobutylamine mentioned. Various perylene dye derivatives having desired basic functional groups can be synthesized by using these alone or in combination.

On the other hand, C.I. I. Pigment Red 123, C.I. I. Pigment Red 149, C.I. I. Pigment Red 178, C.I. I. Pigment Red 179, C.I. I. Pigment Red 190, C.I. I. Pigment Violet 29, Perylene Orange, or a compound having a perylene ring thereof is used as a starting material, and derivatization treatment is performed according to a reaction scheme similar to the method for synthesizing the compound represented by the general formula (1) described above to obtain the above Various functional groups represented by general formula (2) and compounds having functional groups can be obtained.

For example, C.I. I. Pigment Red 123 as a starting material can be subjected to derivatization treatment to obtain a compound in which R ² and R ³ in the above general formula (2) are 4-ethoxyphenyl groups. The C.I. I. Pigment Red 149 as a starting material can be derivatized to give a compound represented by general formula (2) in which R ² and R ³ are 3,5-dimethylphenyl groups. C. I. Pigment Red 178 as a starting material can be subjected to derivatization treatment to obtain a compound in which R ² and R ³ in the general formula (2) are 4-(phenylazo)phenyl groups.

The C.I. I. Pigment Red 179 as a starting material can be derivatized to give a compound represented by the general formula (2) in which R ² and R ³ are methyl groups. C.I. represented by the above structural formula (8). I. Pigment Red 190 as a starting material can be derivatized to give a compound represented by general formula (2) in which R ² and R ³ are 4-methoxyphenyl groups. C.I. represented by the above structural formula (11). I. Pigment Violet 29 is used as a starting material and subjected to derivatization treatment to obtain a compound represented by general formula (2) in which R ² and R ³ are hydrogen atoms. A compound in which R ² and R ³ in the above general formula (2) are 2,6-diisopropylphenyl groups can be obtained by derivatization treatment using perylene orange as a starting material.

In order to obtain higher light emission reliability, it is desirable to use the perylene dye derivative having the specific structure obtained by the above method after purifying it alone and removing impurities in advance. As the residual amount of ionic impurities derived from the chemical solution used for the derivatization treatment, the content of each of sulfate ions (SO ₄ ²⁻ ), sulfite ions (SO ₃ ⁻ ), and chloride ions (Cl ⁻ ) is 100 ppm or less. It is preferably 50 ppm or less, more preferably 50 ppm or less. The remaining amount of these ionic impurities can be measured by ion chromatography, and the removal rate is increased by dispersing the powder of the perylene-based dye derivative with a specific structure in deionized water using a wet media dispersing machine to form a slurry. Alternatively, an ion exchange resin may be added and stirred to further improve the removal rate.

A perylene-based dye derivative with a specific structure is sufficiently dry pulverized to dry powder in order to obtain a higher dispersion stabilizing effect while avoiding the coarse particles of itself remaining in the pigment dispersion. It is desirable to use one having an average primary particle size of 150 nm or less, more preferably 100 nm or less. The average primary particle size of the perylene-based dye derivative having a specific structure can be evaluated by the same method as for the above-described (a) black material having a nitrogen-containing heterocyclic structure. In the case where the chemical solution used in the derivatization treatment contains an impurity consisting of a salt of a sulfur-containing compound and an amine-based catalyst, from the viewpoint of light emission reliability, it is removed as much as possible by repeated washing with water, and then dry powdered. It is desirable to

The method for incorporating the perylene dye derivative having the specific structure into the photosensitive composition is not particularly limited, but specific examples of preferred methods are given below.

In the presence of a perylene-based dye derivative having a specific structure, (a) at least one of the organic pigments belonging to the black material having a nitrogen-containing heterocyclic ring structure is kneaded to be previously adsorbed/supported on the surface of the pigment. After drying and re-pulverization, a dry powder-like organic dye derivative-treated type secondary processed pigment is produced. Next, there is a method of producing a photosensitive composition using a pigment dispersion liquid obtained by collectively performing a wet media dispersion treatment together with other organic pigments. Alternatively, in the presence of a perylene-based dye derivative having a specific structure, (a) a black material having a nitrogen-containing heterocyclic structure is collectively subjected to a wet media dispersion treatment to produce a photosensitive composition using a pigment dispersion. method.

The content of the perylene-based dye derivative having a specific structure is 0.5% by weight with respect to (a) the black material having a nitrogen-containing heterocyclic structure in order to improve the dispersion stability and suppress the generation of pigment aggregates. The above is preferable. On the other hand, it is preferably 10.0% by weight or less in order to suppress an increase in interaction with the ITO electrode surface and to suppress generation of development residue of the perylene dye derivative itself having a specific structure.

In addition, in the range that does not adversely affect the light emission reliability, further, an organic dye derivative other than the perylene dye derivative of the above specific structure or a compound that can obtain a synergistic effect similar to that is used in combination to improve dispersion stability and development. You may control the suppression effect of a residue. For example, indanthrone-based dye derivatives, metal-free phthalocyanine-based dye derivatives, anthraquinone-based dye derivatives, pyranthrone-based dye derivatives, quinacridone-based dye derivatives, dioxazine-based dye derivatives, perinone-based dye derivatives, acidic functional groups or basic functional groups 1,3,5-triazine compounds having (a) the black material having a nitrogen-containing heterocyclic structure is (a-1) an organic pigment having at least one nitrogen-containing heterocyclic structure selected from organic yellow pigments, organic red pigments and organic orange pigments; -2) In the case of a pigment mixture containing an organic blue pigment having a nitrogen-containing heterocyclic structure, among others, it is preferable to use an anthraquinone dye derivative in combination. For example, a compound represented by the following structural formula (56) mentioned.

(b-1) A component belonging to the non-polymer type dispersant may contain a rosin-based dispersant. The rosin-based dispersant has the effect of improving the wettability of the pigment surface with respect to the dispersion medium, and can be used as an auxiliary agent for further enhancing the dispersion-stabilizing effect of the perylene-based dye derivative having a specific structure. Examples of rosin-based dispersants include rosin monomers, rosin dimers (rosin dimers), maleic acid-modified rosins, fumaric acid-modified rosins, and mixtures thereof. Among them, a rosin-based dispersant containing a rosin monomer and a rosin dimer having one or more carboxyl groups in the molecule and having a solid content acid value in the range of 100 to 300 (mgKOH/g) is preferable. Specific examples of commercially available products include "Poly-Pale Partially Dimerized Rosin" (registered trademark), "Dymerex Polymerized Rosin" (registered trademark) (both of which are manufactured by EASTMAN CHEMICAL), Aradime R-95, and Pine Crystal KR140 (the above , both of which are manufactured by Arakawa Chemical Industries, Ltd.).

The photosensitive composition for forming the pixel dividing layer and/or the planarizing layer included in the organic EL display device of the present invention preferably further contains (b-2) a polymer-type dispersant. (b-2) As the polymer-type dispersant, a dispersant having a polymer chain composed of various resin systems as a main chain can be used. Examples thereof include acrylic dispersants, polyoxyalkylene dispersants (polyether dispersants), polyurethane dispersants, polyester dispersants, and polyamine dispersants. Among them, acrylic dispersants and polyoxyalkylene dispersants are preferable in order to achieve both solvent affinity related to dispersion stability and appropriate hydrophilicity related to developability. A polymer-type dispersant having, in addition to the main chain, a basic adsorptive group and/or an acidic adsorptive group having a high adsorption capacity for the perylene dye derivative having the specific structure is preferred.

(b-2) The weight average molecular weight (Mw) of the polymer-type dispersant is preferably 1,000 or more, more preferably 2,000 or more, in order to enhance the steric repulsion effect and sufficiently obtain the dispersion stabilizing effect. Moreover, in order to suppress an increase in the thixotropy of the photosensitive composition, it is preferably 50,000 or less, more preferably 30,000 or less.

(b-2) The basic adsorptive group possessed by the polymer-type dispersant includes, for example, a tertiary amino group or a salt thereof, a quaternary ammonium base, and an organic group having a heterocyclic ring such as an isocyanurate ring at the molecular end. mentioned. Among them, a tertiary amino group is more preferable because it has an excellent dispersion stabilizing effect and a high effect of suppressing development residue on ITO.

As the polymer-type dispersant having a tertiary amino group, for example, when the main chain is an acrylic polymer chain, an ethylenically unsaturated monomer having a dialkylamino group and a covalent ethylenically unsaturated monomer other than that polymers. As a specific example, a dispersant having a structural unit represented by the following general formula (26) can be preferably used. Ethylenically unsaturated monomers having a dialkylamino group include, for example, dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and diethylaminopropyl (meth)acrylate.

In general formula (26), R ¹⁵ represents a hydrogen atom or a methyl group, R ¹⁶ represents a divalent linking group having 1 to 4 carbon atoms, and R ¹⁷ and R ¹⁸ each independently represent 1 to 4 carbon atoms. represents an alkyl group of

On the other hand, when the main chain is a polyoxyalkylene polymer chain, as a specific example, a dispersant having a tertiary amino group at the molecular end and an ethylene oxide/propylene oxide chain can be preferably used.

(b-2) Examples of the acidic adsorption group possessed by the polymer-type dispersant include a phosphoric acid group, a sulfonic acid group, a carboxylic acid group, and a phenolic hydroxyl group. Phosphate groups are preferable because they are excellent in the effect of suppressing development residues, and it is preferable to contain a polymer-type dispersant having at least a phosphate group.

Specific examples of the polymer-type dispersant having a phosphoric acid group include, for example, when the main chain is an acrylic polymer chain, an ethylenically unsaturated monomer having a phosphoric acid group and another ethylenically unsaturated monomer A copolymer of As a specific example, a dispersant having a structural unit represented by the following general formula (27) can be preferably used.

In general formula (27), R ¹⁹ represents a hydrogen atom or a methyl group, R ²⁰ represents C ₂ H ₄ or C ₃ H ₆ and k represents an integer of 1-10.

Ethylenically unsaturated monomers having a phosphoric acid group include, for example, 2-methacryloyloxyethyl acid phosphate, acid phosphooxyethyl (meth)acrylate, acid phosphooxypropyl (meth)acrylate, acid phosphooxypolyoxypropylene glycol ( meth)acrylates.

Other ethylenically unsaturated monomers to be used for copolymerization with the ethylenically unsaturated monomer having a dialkylamino group or the ethylenically unsaturated monomer having a phosphoric acid group include, for example, benzyl (meth)acrylate, styrene, Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, (meth) acrylic acid polyethylene/polypropylene glycol. The dispersant preferably has a benzyl group in the side chain, and the use of benzyl (meth)acrylate is preferred, because it has a high affinity with the perylene-based dye derivative having the specific structure, is excellent in dispersibility, and can improve heat resistance.

As the (b-2) polymer-type dispersant, a commercially available product may be used. Examples of polymer-type dispersants having only acidic adsorption groups include "DISPERBYK" (registered trademark)-102, 110, 111, 118, 2096, BYK-P104, P105, "Solsperse" (registered trademark) 3000, 21000, 36000, 36600 (all of which are manufactured by Lubrizol) and Ajisper PA111 (manufactured by Ajinomoto Fine-Techno Co., Ltd.). These dispersants can be used singly or in combination.

Examples of polymeric dispersants having only basic adsorptive groups include "DISPERBYK" (registered trademark)-161, 162, 2163, 164, 2164, 167, 168, 2000, 2050, 2150, 2155, 9075, 9077, BYK-LPN6919, BYK-LPN21116, BYK-LPN21234 (all manufactured by BYK-Chemie), EFKA-4015, 4020, 4046, 4047, 4050, 4055, 4060, 4080, 4300, 4330, 4340, 4400, 4401, 4402 , 4403, 4800 (all of which are manufactured by BASF), and "Solsperse" (registered trademark) 13240, 13940, 20000, 24000, 71000, and 76500 (all of which are manufactured by Lubrizol). These dispersants can be contained singly or in combination.

Polymer-type dispersants having an acidic adsorptive group and a basic adsorptive group include, for example, "DISPERBYK" (registered trademark)-142, 145, 2001, 2010, 2020, 2025 (all manufactured by BYK-Chemie), " SOLSPERSE" (registered trademark) 9000, 11200, 13650, 24000SC, 24000GR, 32000, 32500, 32550, 33000, 34750, 35100, 35200, 37500, 39000, 56000 (manufactured by Lubrizol), Ajisper BPB821, PB822, PB822, , and PB883 (all manufactured by Ajinomoto Fine-Techno Co., Inc.).

The pixel dividing layer and/or planarizing layer included in the organic EL display device of the present invention contain (c) a resin. The (c) resin referred to here is a so-called binder in the pixel dividing layer and/or the flattening layer. A component that immobilizes a dispersant and has a film-forming function under normal temperature/atmospheric pressure conditions.

(c) The component belonging to the resin is included in the photosensitive composition for patterning the pixel dividing layer and/or the planarizing layer included in the organic EL display device of the present invention, and finally It can be filled in the resulting pixel dividing layer and/or planarizing layer film.

The photosensitive composition for forming the pixel dividing layer and/or the flattening layer reduces the alkali solubility of the exposed portion of the film by pattern exposure through a negative exposure mask, and the non-exposed portion by an alkaline developer. It may be a negative photosensitive composition used in negative photolithography, which removes a part of the film to form a pattern. Alternatively, by pattern exposure through a positive exposure mask, the alkali solubility of the exposed portion of the film is made relatively higher than that of the unexposed portion of the film, and the exposed portion of the film is removed with an alkaline developer. It may be a positive photosensitive composition used in so-called positive photolithography, which is removed to form a pattern. A negative photosensitive composition is preferable because high light shielding properties can be obtained while maintaining good exposure sensitivity and pattern processability.

The pixel dividing layer and/or planarizing layer included in the organic EL display device of the present invention contain (c) a resin. In order to impart either negative-type or positive-type photosensitivity to the photosensitive composition used for patterning the pixel dividing layer and/or the flattening layer described below, it is preferable to incorporate an alkali-soluble resin. An alkali-soluble resin has a hydroxyl group, a carboxyl group and/or a sulfonic acid group as an alkali-soluble group, has an acid value of 10 mgKOH/g or more, and has a weight average molecular weight (Mw) of 1,000 to 150,000. It refers to the resin of The cured alkali-soluble resin contained in the photosensitive composition used for patterning the pixel dividing layer and/or the planarizing layer constitutes the finally obtained pixel dividing layer and/or the planarizing layer. It becomes a component belonging to the (c) resin.

Alkali-soluble resins include, for example, alkali-soluble cardo resins, alkali-soluble acrylic resins, alkali-soluble novolak resins, alkali-soluble polyimide resins, alkali-soluble polyimide precursors, alkali-soluble polybenzoxazole resins, alkali-soluble polybenzoxazole precursors, alkali Examples include soluble polyamide resins and alkali-soluble siloxane resins. Since these alkali-soluble resins eventually become one of the components constituting the above resin (c), among others, the amount of outgassing (the amount of gas generated) at high temperatures can be reduced in order to improve the reliability of light emission. is good.

When the photosensitive composition used for patterning the pixel dividing layer and/or the planarizing layer has negative photosensitivity, the alkali-soluble resin is selected from the viewpoint of achieving both pattern workability and light emission reliability. It preferably contains a soluble cardo resin and/or an alkali-soluble polyimide resin. Further, it is more preferable to contain at least an alkali-soluble polyimide resin in order to improve light emission reliability. When an alkali-soluble cardo resin and an alkali-soluble polyimide resin are used together, the content of the alkali-soluble polyimide resin preferably exceeds the content of the alkali-soluble cardo resin from the viewpoint of light emission reliability and dispersion stability.

On the other hand, when the photosensitive composition used for patterning the pixel dividing layer and/or the planarizing layer has positive photosensitivity, from the viewpoint of achieving both pattern workability and light emission reliability, an alkali-soluble polyimide resin, It is preferable to contain at least one alkali-soluble resin selected from alkali-soluble polyimide precursors, alkali-soluble polybenzoxazole resins, alkali-soluble polybenzoxazole precursors, and alkali-soluble siloxane resins. Furthermore, from the viewpoint of improving the exposure sensitivity and light emission reliability in the exposure step described later, it is more preferable to contain an alkali-soluble polyimide resin and/or an alkali-soluble polyimide precursor.

Alkali-soluble cardo resin refers to an alkali-soluble resin having a cardo skeleton, and the cardo skeleton is a quaternary carbon atom that is a ring carbon atom that constitutes a cyclic structure, and two aromatic groups are connected by single bonds. It refers to the skeleton.

Preferred specific examples of the alkali-soluble cardo resin include an alkali-soluble cardo resin having a fluorene skeleton and a structural unit represented by the following general formula (28) and a radical polymerizable group, Having a dihydro-1H-indene skeleton, an alkali-soluble cardo resin having a structural unit represented by the following general formula (29) and a radically polymerizable group, an N-phenylphenolphthalein skeleton, having the following general formula ( 30) and an alkali-soluble cardo resin having a radically polymerizable group.

In the above general formulas (28), (29) and (30), Q ¹ to Q ⁸ , which may be the same or different, represent substituents directly bonded to a benzene ring, and have 1 to 1 carbon atoms. is an alkyl group of 6 or an alkoxy group having 1 to 6 carbon atoms, and a to h are integers of 1 or 2;

The acid value of the alkali-soluble cardo resin is preferably 10 mgKOH/g or more, and more preferably 50 mgKOH/g or more, in order to improve developability. On the other hand, it is preferably 300 mgKOH/g or less, more preferably 250 mgKOH/g or less, in order to suppress peeling of the pattern edges of the pixel division layer and/or the flattening layer.

The weight-average molecular weight of the alkali-soluble cardo resin is preferably 2,000 or more, more preferably 3,000 or more, from the viewpoint of suppressing peeling of pattern edges. On the other hand, it is preferably 50,000 or less, more preferably 30,000 or less, from the viewpoint of suppressing gelation during polymerization of the alkali-soluble cardo resin.

In addition, as the alkali-soluble cardo resin, a commercially available product can also be used. -TR2, CR-TR3, CR-TR4, CR-TR5 and CR-TR6 (all manufactured by Osaka Gas Chemicals Co., Ltd.).

The alkali-soluble polyimide resin preferably contains an alkali-soluble polyimide resin having a structural unit represented by the following general formula (31).

In general formula (31) above, R ²¹ represents a tetravalent to decavalent organic group. R ²² represents a divalent to octavalent organic group. ^R23 and ^R24 each independently represent a phenolic hydroxyl group, a sulfonic acid group or a thiol group. i and j each independently represent a range of 0 to 6;
In general formula (31), R ²¹ -(R ²³ ) _i represents a residue of an acid dianhydride. R ²¹ is preferably an organic group having 5 to 40 carbon atoms and having an aromatic ring or cycloaliphatic group.

Examples of acid dianhydrides include pyromellitic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, and 3,3′,4,4′-benzophenonetetracarboxylic dianhydride. bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane Tetracarboxylic dianhydrides having an aromatic ring such as anhydrides, tetracarboxylic dianhydrides having an aliphatic group such as butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, bicyclo[2.2.2]oct-7-ene-tetracarboxylic dianhydride, bicyclo[2.2.2]octanetetracarboxylic dianhydride and other tetracarboxylic acids having a cycloaliphatic group An acid dianhydride is mentioned.

In general formula (31), R ²² -(R ²⁴ ) _j represents a diamine residue. R ²² is preferably an organic group having 5 to 40 carbon atoms and having an aromatic ring or cycloaliphatic group.

Examples of diamines include 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]sulfone, bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, bis [4-(3-aminophenoxy)phenyl]sulfone, 9,9-bis(4-aminophenyl)fluorene, diaminodiphenyl ether, diaminodiphenylsulfone, diaminodiphenylmethane, diaminodiphenylpropane, diaminodiphenylhexafluoropropane, diaminodiphenylthioether, diamines having aromatic rings such as benzidine, 2,2'-bistrifluorobenzidine, 2,2'-bistrifluorobenzidine, 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane, 2,6 -diamines with cyclic aliphatic groups such as bis(aminomethyl)bicyclo[2.2.1]heptane.

The alkali-soluble polyimide resin having the structural unit represented by general formula (31) preferably has a carboxyl group, phenolic hydroxyl group, sulfonic acid group and/or thiol group at the main chain end. By blocking the ends of the polyimide resin with a terminal blocking agent having a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group and/or a thiol group, these groups can be introduced into the ends of the main chain. Terminal blocking agents include, for example, monoamines, acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and monoactive ester compounds.

From the viewpoint of developability, the acid value of the alkali-soluble polyimide resin is preferably 10 mgKOH/g or more, more preferably 50 mgKOH/g or more. On the other hand, the acid value is more preferably 300 mgKOH/g or less from the viewpoint of suppressing peeling of pattern edges of the pixel dividing layer and/or the planarizing layer.

The weight-average molecular weight of the alkali-soluble polyimide resin is preferably 5,000 or more, more preferably 10,000 or more, from the viewpoint of the hardness of the pixel dividing layer and/or the flattening layer. On the other hand, from the viewpoint of solubility in an alkaline developer, it is preferably 100,000 or less, more preferably 70,000 or less.

The perylene dye derivative having the above specific structure is an organic dye derivative having an aromatic ring and an imide ring in the molecule, and has a high affinity with a resin having an aromatic ring and an imide ring in the molecule. By performing the media dispersion treatment in the presence of an alkali-soluble polyimide resin having an aromatic ring and an imide ring in the molecule, (a) a perylene dye derivative having a specific structure for a black material having a nitrogen-containing heterocyclic structure can increase the dispersibility of That is, more specifically, in the general formula (31), at least one of R ²¹ and R ²² is a group having an aromatic ring. Used in the production of a pigment dispersion described later. A high dispersion stabilizing effect can be obtained even when the amount of the perylene-based dye derivative having a specific structure is small. In addition, the perylene-based dye derivative having a specific structure is a cured product of an alkali-soluble polyimide resin having an aromatic ring and an imide ring in the molecule in the film of the finally obtained pixel division layer and/or flattening layer. Since it has a high affinity with the resin (c) it contains and is uniformly dispersed without being unevenly distributed, the light emission reliability can be further improved.

The photosensitive composition used for patterning the pixel dividing layer and/or planarizing layer included in the organic EL display device of the present invention contains a photosensitive agent for imparting either negative-type or positive-type photosensitivity. is preferably contained.
When imparting negative photosensitivity to the photosensitive composition, a compound having two or more radically polymerizable groups and a photopolymerization initiator can be used as the photosensitive agent.

By containing a compound having two or more radically polymerizable groups and a photopolymerization initiator described later, a radical polymerization reaction is caused by exposure, and the film in the exposed area is photocured to be insolubilized, leaving only the unexposed area. can be dissolved and removed with an alkaline developer to form a patterned pixel dividing layer and/or a flattening layer.

As the radically polymerizable group, a (meth)acrylic group is preferable from the viewpoint of improving the sensitivity at the time of exposure and improving the hardness of the cured film. Examples of compounds having two or more (meth)acrylic groups include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane di(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditri Methylolpropane tetra(meth)acrylate, 1,3-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate ) acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, ethoxylated glycerin tri(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, tetrapentaerythritol deca (meth) acrylate, ε-caprolactone addition (meth) acrylate of dipentaerythritol, Ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-(3-(meth)acryloxy-2-hydroxypropoxy)phenyl]propane, 1,3,5-tris((meth)acryloxyethyl) isocyanuric acid, 1,3-bis((meth)acryloxyethyl)isocyanuric acid, 9,9-bis[4-(2-(meth)acryloxyethoxy)phenyl]fluorene, 9,9-bis[4-( 3-(meth)acryloxypropoxy)phenyl]fluorene, 9,9-bis(4-(meth)acryloxyphenyl)fluorene or These acid-modified products, ethylene oxide-modified products, propylene oxide-modified products, and the like can be mentioned. These may be contained singly or in combination. The cured product of the compound having two or more radically polymerizable groups is finally filled in the film of the pixel division layer and/or the flattening layer as the acrylic resin component contained in the resin (c).

The photopolymerization initiator refers to a compound that generates radical active species by bond cleavage and/or reaction by exposure to light. of pixel division layers and/or planarization layers can be formed.

Examples of photopolymerization initiators include "ADEKA OPTOMER" (registered trademark) N-1818, N-1919, "ADEKA CRUSE" (registered trademark) NCI-831 (both of which are manufactured by ADEKA Corporation). Carbazole-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (“Irgacure” (registered trademark) TPO manufactured by BASF), 1,2- Octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)] (manufactured by BASF "Irgacure" (registered trademark) OXE01), ethanone, 1-[9-ethyl-6-(2- Methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (BASF "Irgacure" (registered trademark) OXE02) and other oxime ester photopolymerization initiators, 2-methyl-1 -(4-methylthiophenylphenyl)-2-morpholinopropan-1-one (manufactured by BASF "Irgacure" (registered trademark) 907), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) -butanone-1 ("Irgacure" (registered trademark) 369 manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]- α-aminoalkylphenone-based photopolymerization initiators such as 1-butanone (“Irgacure” (registered trademark) 379EG manufactured by BASF) and the like. Among them, it has high exposure sensitivity to mixed rays consisting of j-line (wavelength 313 nm), i-line (365 nm), h-line (405 nm), and g-line (436 nm), and is excellent in deep part curability in the film depth direction. , carbazole-based photopolymerization initiators, and oxime ester-based photopolymerization initiators are preferred.

When imparting positive photosensitivity to the photosensitive composition, a photoacid generator can be used as the photosensitive agent. By containing a photoacid generator, the alkali solubility of the exposed area is relatively increased with respect to the unexposed area by exposure, and the exposed area is dissolved and removed with an alkaline developer to form patterned pixels. A dividing layer and/or a planarizing layer may be formed.

A quinonediazide compound is preferable as the photoacid generator. The quinonediazide compound is more preferably a reactant obtained by esterifying a compound having a phenolic hydroxyl group with quinonediazide sulfonyl chloride.

Compounds having a phenolic hydroxyl group include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-PHBA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP -IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-p-CR, methylenetetra-p-CR, BisRS-26X, Bis-PFP-PC (both Honshu Chemical Industry Co., Ltd. ), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (Asahi Organic Chemicals Industry (manufactured by Co., Ltd.).

The quinonediazide sulfonyl chloride includes 4-naphthoquinonediazide sulfonyl chloride and 5-naphthoquinonediazide sulfonyl chloride. Such a quinonediazide compound is preferable because it has high exposure sensitivity to a mixed ray consisting of j-line (wavelength 313 nm), i-line (365 nm), h-line (405 nm) and g-line (436 nm) in the exposure step described later.

The photosensitive composition for forming the pixel dividing layer and/or the planarizing layer included in the organic EL display device of the present invention further requires heat resistance of the finally obtained pixel dividing layer and/or planarizing layer. A thermal cross-linking agent may be contained in order to increase the strength. Examples of thermal cross-linking agents include compounds having two or more alkoxymethyl groups and/or methylol groups, and compounds having two or more epoxy groups.

Compounds having two or more alkoxymethyl groups and/or methylol groups include, for example, Nikalac (registered trademark) MW-100LM, MX-270, MX-280, MX-290 (manufactured by Sanwa Chemical Co., Ltd.), DML -PC (manufactured by Honshu Chemical Industry Co., Ltd.) Examples of compounds having two or more epoxy groups include "Epolite" (registered trademark) 40E, 100E, 200E, 400E, 70P, 200P, 400P, 4000, 3002 (N) (all manufactured by Kyoeisha Chemical Co., Ltd.), "jER" (registered trademark) 828, 1002, 1750, 1007, YX8100-BH30, E1256, E4250, E4275 (all manufactured by Mitsubishi Chemical Corporation ), “TECHMORE” (registered trademark) VG-3101L (manufactured by Printec Co., Ltd.; hereinafter “VG-3101L”), “TEPIC” (registered trademark) S, G, P, L (all of the above manufactured by Nissan Chemical Industries, Ltd.).

The photosensitive composition for forming the pixel division layer and/or the planarizing layer included in the organic EL display device of the present invention may contain a solvent. By containing a solvent, the viscosity and applicability of the photosensitive composition can be adjusted.

Examples of solvents include ethers, acetates, esters, ketones, aromatic hydrocarbons, and alcohols, and these may be used singly or in combination. Among them, acetates and ethers are preferable because they are excellent in dispersion stability and can improve film thickness uniformity. Among them, propylene glycol monomethyl ether acetate (hereinafter “PGMEA”), 3-methoxybutyl acetate (hereinafter “MBA”), and propylene glycol monomethyl ether are preferable.

Examples of the method for preparing a photosensitive composition for forming the pixel dividing layer and/or planarizing layer included in the organic EL display device of the present invention include (a) a black material having a nitrogen-containing heterocyclic structure; , (b-1) a non-polymeric dispersant, (b-2) a polymeric dispersant, and a solvent are mixed, and finely divided into (a) a black material having a nitrogen-containing heterocyclic structure by a wet media dispersion treatment. It may also be prepared by curing to prepare a pigment dispersion, then adding the photosensitizer and other components to the pigment dispersion, stirring, and optionally filtering.

It should be noted that the perylene-based dye derivative having the above specific structure cannot obtain a sufficient action and effect by simply post-adding and stirring the pigment dispersion liquid obtained by the wet media dispersion treatment. By applying sufficient mechanical energy in the coexistence of at least one organic pigment having a nitrogen-containing heterocyclic structure in a wet pulverization process such as salt milling or a wet media dispersion process, the effect is exhibited. be able to.

Horizontal or vertical bead mills, roll mills, and the like can be used as dispersers for wet media dispersion treatment. For example, "DYNO-MILL" (registered trademark) (manufactured by Willy A. Bachofen), "Spike Mill" (registered trademark) (manufactured by Inoue Seisakusho Co., Ltd.), "Sand Grinder" (registered trademark) (manufactured by DuPont) are mentioned. Media for the disperser include zirconia beads, zircon beads, and non-alkali glass beads. It is preferable to use beads that do not contain any component that can be an impurity source. Moreover, the diameter of the beads is preferably 0.03 to 5 mm, and the higher the sphericity, the better. A specific example of a preferred commercially available product is "Toreceram" (registered trademark) (manufactured by Toray Industries, Inc.). The operating conditions of the disperser may be appropriately set in consideration of the bead hardness, handleability, productivity, etc. so that the average dispersed particle size of the pigment described later and the viscosity are within desired ranges.

(a) The average dispersed particle size of all pigments including the black material having a nitrogen-containing heterocyclic structure is preferably 40 nm or more from the viewpoint of the applicability of the photosensitive composition and the dispersion stability during storage. On the other hand, the thickness is preferably 200 nm or less in order to improve the pattern linearity of the pixel dividing layer and/or the flattening layer. The average dispersed particle size of the pigment as used herein refers to the number average value of secondary particle sizes of all the pigment particles contained in the pigment dispersion, and can be measured using a particle size distribution apparatus. As the particle size distribution analyzer, a dynamic light scattering particle size distribution analyzer “SZ-100 (manufactured by HORIBA)” or a laser diffraction/scattering method particle size distribution analyzer “MT-3000 (manufactured by Microtrac)” can be used.

Next, a method for forming the pixel dividing layer and the planarizing layer provided in the organic EL display device of the present invention will be described.
The pixel dividing layer and the flattening layer can be obtained, for example, by a method including a coating step, a pre-baking step, an exposure step, a developing step, and a curing step in this order.
In the coating step, a coating film is obtained by coating the substrate with the photosensitive composition. As the substrate, for example, when manufacturing a top emission type organic display device, as the coating apparatus used in the coating process, for example, a slit coater, a spin coater, a gravure coater, a dip coater, a curtain flow coater, a roll coater, and a spray coater , screen printers, and inkjets. Since the pixel division layer and the flattening layer are usually formed with a thickness of about 0.5 to 3 μm due to the structure of the members, they are suitable for thin film coating, coating defects are unlikely to occur, and the thickness uniformity and productivity are excellent. Therefore, a slit coater or a spin coater is preferable, and a slit coater is more preferable from the viewpoint of liquid saving.

In the pre-baking process, a pre-baked film is obtained by volatilizing the solvent in the coating film by heating. Examples of heating devices include hot air ovens, hot plates, and far infrared ovens (IR ovens). Pin gap pre-baking or contact pre-baking may be performed. The prebaking temperature is preferably 50 to 150° C., and the prebaking time is preferably 30 seconds to several hours. For example, after pre-baking at 80° C. for 2 minutes, pre-baking may be performed in two or more stages such as pre-baking at 120° C. for 2 minutes. In order to further improve the film thickness uniformity, a pre-baking step by heating may be performed after part of the solvent contained in the coating film is volatilized by a vacuum/reduced pressure dryer after the coating step.

In the exposure step, an exposed film is obtained by irradiating actinic rays through a photomask from the film surface side of the prebaked film. Exposure apparatuses used in the exposure process include a stepper, a mirror projection mask aligner (MPA), a parallel light mask aligner (PLA), and the like. Actinic rays irradiated during exposure include, for example, ultraviolet rays, visible rays, electron beams, X-rays, KrF (wavelength: 248 nm) lasers, ArF (wavelength: 193 nm) lasers, and the like. Among them, j-line (wavelength: 313 nm), i-line (wavelength: 365 nm), h-line (wavelength: 405 nm) or g-line (wavelength: 436 nm) of mercury lamp is preferred, and a mixed line thereof is more preferred. The exposure dose is usually about 10 to 4000 mJ/cm ² (i-line conversion value). As a mask, for example, a thin film having an exposure light shielding property made of a metal such as chromium or a black organic resin is patterned on one surface of a base material such as glass, quartz, or film that is translucent at the exposure wavelength. A film-formed mask is mentioned. In the formation of the pixel dividing layer and the planarizing layer using the photosensitive composition, either a negative or positive exposure mask can be used, and pattern exposure is performed by transmitting actinic radiation only at the openings. to obtain an exposed film. A mask having a pattern corresponding to openings in the exposure mask for the pixel dividing layer or the flattening layer is called a negative exposure mask, and a mask made of a thin film that blocks exposure light is called a positive exposure mask.

Moreover, when it is used as a pixel division layer that also functions as a spacer in the structure of a panel member, the pixel division layer may have a portion with a different film thickness, that is, have a stepped shape in the plane. As a method for obtaining a pixel division layer having steps with different thicknesses, a negative or positive halftone exposure mask having a plurality of types of openings with different light transmittances in exposure light regions is used in the exposure process. and a method of patternwise exposing through.

In the developing step, when the photosensitive composition is a negative photosensitive composition, the unexposed portion is removed by development to obtain a patterned developed film. On the other hand, in the case of a positive photosensitive composition, the exposed portion is removed by development to obtain a patterned developed film. Here, the exposed portion refers to a portion irradiated with exposure light through the mask opening, while the unexposed portion refers to a portion not irradiated with exposure light. Examples of the developing method include a method in which the exposed film is immersed in an alkaline aqueous solution, which is a developer, for 10 seconds to 10 minutes by a method such as showering, dipping, or puddle.

When the photosensitive composition is a negative photosensitive composition, the unexposed area becomes the pattern opening, and when it is positive, the exposed area becomes the pattern opening. The underlying ITO electrode is exposed. The photosensitive composition containing the perylene-based dye derivative having the specific structure can exhibit a remarkable effect in suppressing development residue on the ITO electrode in the development process. Note that the opening eventually becomes a light-emitting pixel portion in the organic EL display device.

In the formation of the pixel dividing layer and/or the planarizing layer of the organic EL display device, the developing solution remaining after penetrating the surface layer or the inside of the developing film can be easily volatilized in the curing step after development. 1.0-3.0 wt% TMAH is preferred, and 2.38 wt% TMAH is commonly used. 2. 38% by weight TMAH may be a commercially available product, or may be used by diluting a high-concentration product. may Further, after development, washing treatment by showering with deionized water and/or draining treatment by blowing air may be added.

In the curing step, the developed film is thermally cured by heating, and at the same time, components such as moisture and permeated and remaining developing solution are volatilized to obtain a pixel dividing layer or a flattening layer. Heating devices include, for example, hot air ovens and IR ovens. The heating temperature is preferably 230-300° C., more preferably 250-300° C. in order to obtain high light emission reliability. The heating atmosphere is preferably air or nitrogen atmosphere, and the pressure during heating is preferably atmospheric pressure.

The optical density per 1.0 μm film thickness of the pixel division layer and the planarization layer included in the organic EL display device of the present invention, which can be patterned through each of the above steps, is 0.5 or more. is preferred, 0.8 or more is more preferred, and 1.0 or more is even more preferred. The optical density referred to here means that a pixel division layer or a flattening layer formed on a translucent substrate to have a film thickness of 1.0 μm is measured by an optical densitometer (manufactured by X-Rite; X-Rite 361T" is used to measure the incident light intensity and the transmitted light intensity, and the value is calculated from the following formula. The higher the optical density, the higher the light-shielding property. "Tempax (manufactured by AGC Techno Glass Co., Ltd.)", which is a translucent glass substrate, can be preferably used.
optical density = _log10 ( _I0 /I)
I ₀ : Incident light intensity I: Transmitted light intensity The dielectric constants of the pixel division layer and the planarization layer of the organic EL display device at a frequency of 1 kHz are preferably 7 or less, and 5 or less, respectively, in order to stably drive the light emitting element. is more preferred, and 4 or less is even more preferred. The dielectric constant can be measured using a dielectric constant measuring device such as an LCR meter manufactured by Agilent Technologies.

The aperture ratio of the pixel division layer in the display area is preferably 20% or less from the viewpoint that the definition of the display area can be increased, the display quality of images or videos can be improved, and the value of the display device can be increased. Here, the aperture ratio refers to the area ratio of the aperture of the pixel division layer to the area of the pixel division layer. The lower the aperture ratio, the larger the formation area of the pixel division layer in the display area. That is, the effect of the present invention contributes more greatly to an organic EL display device having a lower aperture ratio and a higher-definition display area.

EXAMPLES The present invention will be described in detail below with reference to Examples and Comparative Examples, but the aspects of the present invention are not limited to these.

First, the evaluation method in each example and comparative example will be described.
<Method for calculating the minimum required exposure>
A silver/copper alloy thin film (volume ratio: 10:1) with a thickness of 10 nm was deposited on the surface of a non-alkali glass substrate of 100 mm x 100 mm by sputtering, and etched to form a patterned metal reflective layer. do. Then, a 10 nm-thick ITO transparent conductive film was formed on the entire surface by a sputtering method to obtain a substrate for evaluation of the required minimum exposure amount.

A photosensitive composition was applied to the surface of the obtained substrate for evaluation of the minimum required amount of exposure with a spin coater while adjusting the number of rotations so that the thickness of the cured film finally obtained was 1.0 μm. A coated film was obtained and prebaked at 100° C. under atmospheric pressure for 120 seconds using a hot plate (SCW-636; manufactured by Dainippon Screen Mfg. Co., Ltd.) to obtain a prebaked film. Using a double-sided alignment single-sided exposure apparatus (mask aligner PEM-6M; manufactured by Union Optical Co., Ltd.), through a grayscale mask for sensitivity measurement (MDRM MODEL 4000-5-FS; manufactured by Opto-Line International), Patterning exposure is carried out with a mixed line of j-line (wavelength 313 nm), i-line (wavelength 365 nm), h-line (wavelength 405 nm) and g-line (wavelength 436 nm) of an ultra-high pressure mercury lamp. Then, using a compact developing device for photolithography (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.), the film was developed with a 2.38% by weight TMAH aqueous solution to obtain a developed film. Then, using an FPD inspection microscope (MX-61L; manufactured by Olympus Corporation), the resolution pattern of the prepared developed film was observed, and in the line and space pattern, the pattern line width and pitch width were 1:1. The amount of exposure (mJ/cm ² : i-line illuminance meter value) formed in the film was taken as the minimum necessary amount of exposure (sensitivity) of the photosensitive composition. Here, the pitch width means the interval between identical patterns. Since the same gray scale mask is used to evaluate the negative photosensitive composition and the positive photosensitive composition, the arrangement of the formed patterns is reversed.

(1) Evaluation of dispersion stability of photosensitive composition 20.0 g of the photosensitive compositions obtained in Examples 1 to 22 and Comparative Examples 1 to 33 were sealed in a glass bottle within 1 hour after preparation and It was stored for 24 hours in a constant temperature box under atmospheric pressure/under light shielding/at an actual temperature of 25°C ± 1°C. 1.0 g of the photosensitive composition after storage was sampled, dropped onto the stage of an E-type viscometer (cone plate type viscometer) at an actual temperature of 25° C., and a shear force was applied under the condition of a rotation speed of 50 rpm. The viscosity indicated after minutes was taken as the initial viscosity (mPa·s). Under the same storage environment, the photosensitive composition was subsequently stored for 29 days at 25° C.±1° C. for a long period of time. After stirring, the viscosity was measured in the same manner, and the viscosity over time (mPa·s) was used to obtain the viscosity increase rate (%) from the following formula. The smaller the absolute value of the viscosity increase rate (%), the better the stability, and the dispersion stability was evaluated based on the following criteria. However, when sedimentation occurred after storage, the evaluation was E regardless of the viscosity increase rate. In addition, if either the initial viscosity or the viscosity over time of the photosensitive composition exceeds 100 (mPa s), it is difficult to make a comparative evaluation under the same viscosity measurement conditions. Evaluation was set to F regardless of the viscosity increase rate.
Thickening rate (%) = (viscosity over time - initial viscosity) / initial viscosity x 100
In addition, when the viscosity increase rate is a positive value, the viscosity is increased, and when it is a negative value, the viscosity is decreased. None of the samples showed a negative value for the viscosity increase rate.
AA: Less than 5% A: 5% or more and less than 10% B: 10% or more and less than 25% C: 25% or more and less than 50% D: 50% or more E: Sedimentation occurs F: Viscosity is too high , impossible to evaluate under the same viscosity measurement conditions.

(2) Evaluation of light shielding property of cured film For light shielding evaluation substrates having a cured film on the surface of Tempax obtained in Examples 1 to 22 and Comparative Examples 1 to 33, an optical densitometer (X-Rite Measure the optical density (OD value) at three points in the plane from the film surface side using X-Rite 361T), round off the average value to the second decimal place, and calculate the value to the first decimal place. asked. By dividing the numerical value by the thickness (μm) of the cured film, the OD value (OD / μm) per 1.0 μm of the thickness of the cured film was calculated. The evaluation was performed according to the criteria that it is. As a result of separately measuring the OD value unique to the substrate of Tempax itself without forming a cured film, it was 0.00, so the OD value of the light shielding evaluation substrate was regarded as the OD value of the cured film. The thickness of the cured film is measured at three points in the plane using a stylus type film thickness measuring device (Tokyo Seimitsu Co., Ltd.; Surfcom), and the average value is rounded to the second decimal place. Figures were obtained to the first decimal place.

(3) Evaluation of Development Residue of Pixel Division Layer Ten openings located in the center of the pixel division layer forming substrates obtained in Examples 1 to 22 and Comparative Examples 1 to 33 were examined with an optical microscope at a magnification of 50. Observation was carried out at double magnification, and the number of development residues having a major diameter of 0.1 μm or more and less than 3.0 μm in each opening was counted. The average number of development residues observed per opening was evaluated according to the following criteria, AA and A to C were evaluated as acceptable, and D to E were evaluated as unacceptable. However, when residues exceeding 3.0 μm in major axis were observed, it was evaluated as E regardless of the average number of residues.
AA: no development residue is observed A: less than 5 development residues are observed B: 5 or more and less than 10 development residues are observed C: 10 or more and less than 15 development residues are observed D: 15 or more development residues are observed E: Development residues exceeding 3.0 µm in length are observed.

(4) Emission Reliability Evaluation of Organic EL Display Device Equipped with Pixel Division Layer, (5) Emission Reliability Evaluation of Organic EL Display Device Equipped with Pixel Division Layer and Flattening Layer Examples 1 to 22 and Comparison The organic EL display devices obtained in Examples 1 to 33 were placed on a hot plate heated to 80° C. with the light-emitting surface facing up, and allowed to emit light at 10 mA/cm ² by direct current driving. The area ratio of the light-emitting portion to the area (pixel light-emitting area ratio) was measured after 1 hour and 500 hours. Based on the pixel light emitting area ratio after 1 hour, it is assumed that the higher the pixel light emitting area ratio can be maintained, the less pixel shrinkage occurs and the light emission reliability is excellent. Passed, and D to F failed. If there were too many dark spots in the pixel immediately after the start of driving and it was difficult to properly evaluate the pixel emission area ratio, the evaluation was given as E. In addition, when there was one or more unlit light-emitting pixel portions immediately after the start of driving, the evaluation was made F.
AA: 95% or more A: 90% or more and less than 95% B: 85% or more and less than 90% C: 80% or more and less than 85% D: Less than 80% E: Too many dark spots, fair evaluation difficult F: Driving Immediately after this, there were one or more light-emitting pixel portions that were completely unlit (pixel light-emitting area ratio of 0%), making proper evaluation difficult.
(6) Evaluation of Dark Spots (Local Non-Light Emitting Sites) of Organic EL Display Devices Equipped with a Pixel Division Layer and a Flattening Layer Pixel aperture ratio of 18% obtained in Examples 1 to 22 and Comparative Examples 1 to 33 2 hours after the start of driving, the organic EL display device of the organic EL display device having the pixel dividing layer and the planarizing layer was caused to emit light by direct current driving at 10 mA/cm ² . Then, in the pixel portion formed in an area of 16 mm in length and 16 mm in width, 10 pixel portions located in the central portion were enlarged and displayed on a monitor at a magnification of 50 times and observed. The number of local non-light-emitting sites of more than 15.0 μm and less than 15.0 μm was counted. Based on the average number of local non-luminescent sites observed per opening, evaluation was made based on the following criteria, and AA and A to C were evaluated as acceptable, and D to E were evaluated as unacceptable. However, when dark spots exceeding 15.0 μm in major axis were observed, it was evaluated as E regardless of the average number of dark spots.
AA: No dark spots observed A: Less than 5 dark spots observed B: 5 or more but less than 10 dark spots observed C: 10 or more but less than 15 dark spots observed D: 15 or more dark spots observed E: Dark spots exceeding 15.0 μm in major diameter observed F: One or more completely non-illuminated (pixel emission area ratio 0%) light-emitting pixel part present, valid evaluation is difficult (Synthesis Example 1: Synthesis of alkali-soluble polyimide resin solution A)
150.15 g of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (0.41 mol), 6.20 g of 1,3-bis(3-aminopropyl) tetramethyl under dry nitrogen stream Disiloxane (0.02 mol), and 13.65 g of 3-aminophenol (0.13 mol) as a terminal blocking agent, 500.00 g of N-methyl-2-pyrrolidone (hereinafter, "NMP") as a solvent ), 155.10 g of bis(3,4-dicarboxyphenyl) ether dianhydride (0.50 mol) and 150.00 g of NMP were added thereto and stirred at 20 ° C. for 1 hour, and water was added. Stir at 180° C. for 4 hours while removing. After completion of the reaction, the reaction solution was poured into 10 L of water, and the resulting precipitate was collected by filtration, washed with water five times, dried in a vacuum dryer at 80°C for 20 hours, and treated with the above general formula (31). Synthesize an alkali-soluble polyimide resin powder having a weight average molecular weight (Mw) of 25,000, which has a structural unit represented by and has an aromatic ring and an imide ring in the molecule, and the solid content is 30.00 % by weight, to obtain an alkali-soluble polyimide resin solution A.

(Synthesis Example 2: Synthesis of polymer-type dispersant solution B)
Under a dry nitrogen stream, 12.91 g of methacrylic acid (0.15 mol), 55.07 g of methyl methacrylate (0.55 mol), and a phosphoric acid group were added to 185.44 g of PGMEA maintained at a liquid temperature of 100 ° C. 21.01 g acid phosphoxethyl methacrylate (0.10 mol), 26.43 g benzyl methacrylate (0.15 mol), and 8.21 g azobisisobutyronitrile, which are ethylenically unsaturated monomers The liquid is added dropwise over 30 minutes, further stirred for 1 hour while maintaining the liquid temperature at 100 ° C. to proceed with the thermal polymerization reaction, and then cooled, and the weight average molecular weight (Mw) is 9500 (meth) An acrylic copolymer was synthesized. This was diluted with PGMEA to a solids content of 30.00% by weight to obtain a polymer-type dispersant solution B, which is a polymer-type dispersant having a phosphoric acid group as an acidic adsorptive group.

(Synthesis Example 3: Synthesis of quinonediazide compound a)
Under a stream of dry nitrogen, 21.23 g (0.05 mol) of TrisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.), which is a compound having a phenolic hydroxyl group, and 33.58 g (0.125 mol) of 5-naphthoquinone diazidesulfonyl The acid chloride was dissolved in 450.00 g of 1,4-dioxane and brought to room temperature. 12.65 g (0.125 mol) of triethylamine mixed with 50.00 g of 1,4-dioxane was added dropwise while maintaining the temperature in the system at 25 to 35°C. After dropping, the mixture was stirred at 30°C for 2 hours. Then, the triethylamine salt was filtered, the filtrate was poured into water, and the deposited precipitate was collected by filtration. By drying this precipitate with a vacuum dryer, a quinonediazide compound a having a solid content of 100.00% by weight represented by the following structural formula (32) was obtained.

Chemical structures of various organic dye derivatives and organic pigments used in Examples and Comparative Examples are shown below.
"Perylene dye derivative 1": a compound represented by the following structural formula (33) (a perylene dye derivative corresponding to the compound represented by the above general formula (1))

"Perylene dye derivative 2": a compound represented by the following structural formula (34) (a perylene dye derivative corresponding to the compound represented by the above general formula (1))

“Perylene-based dye derivative 3”: a compound represented by the following structural formula (35) (a perylene-based compound represented by the above general formula (2), wherein R ² and R ³ are aryl groups having substituents dye derivative)

"Perylene-based dye derivative 4": a compound represented by the following structural formula (36) (a perylene-based dye derivative that is a compound represented by the above general formula (2) and in which R ² and R ³ are methyl groups)

“Perylene-based dye derivative 5”: a compound represented by the following structural formula (37) (a perylene-based compound represented by the above general formula (2), wherein R ² and R ³ are substituted aryl groups) dye derivative)

“Perylene-based dye derivative 6”: a compound represented by the following structural formula (38) (a perylene-based compound represented by the above general formula (2) in which R ² and R ³ are aryl groups having a substituent dye derivative)

"Perylene-based dye derivative 7": a compound represented by the following structural formula (39) (a perylene-based dye derivative that is a compound represented by the general formula (2) above and in which R ² and R ³ are methyl groups)

"Perylene dye derivative 8": a compound represented by the following structural formula (40) (corresponding to the compound represented by the above general formula (1), having an organic group having a terminal N,N-dialkylamino group perylene dye derivative)

“Perylene dye derivative 9”: a compound represented by the following structural formula (41) (corresponding to the compound represented by the above general formula (1), having an organic group having a terminal N,N-dialkylamino group perylene dye derivative)

"Perylene dye derivative 10": a compound represented by the following structural formula (42) (corresponding to the compound represented by the above general formula (2), having an organic group having a terminal N,N-dialkylamino group perylene dye derivative)

“Perylene dye derivative 11”: a compound represented by the following structural formula (43) (corresponding to the compound represented by the above general formula (2), having an organic group having a terminal N,N-dialkylamino group perylene dye derivative)

"Copper phthalocyanine dye derivative 1": a compound represented by the following structural formula (44) (copper phthalocyanine derivative having one sulfonic acid group in the molecule)

"Copper phthalocyanine dye derivative 2": a compound represented by the following structural formula (45) (copper phthalocyanine derivative having two sulfonic acid groups in the molecule)

"Copper phthalocyanine dye derivative 3": a compound represented by the following structural formula (46) (a barium salt of a copper phthalocyanine derivative having two sulfonic acid groups in the molecule)

"Copper phthalocyanine dye derivative 4": a compound represented by the following structural formula (47) (CI Direct Blue 86)

"Copper phthalocyanine dye derivative 5": a compound represented by the following structural formula (48) (CI Acid Blue 249)

"Copper phthalocyanine dye derivative 6": a compound represented by the following structural formula (49) (copper phthalocyanine derivative having two basic functional groups in the molecule)

"Diketopyrrolopyrrole dye derivative 1": a compound represented by the following structural formula (50)

"Isoindoline dye derivative 1": a compound represented by the following structural formula (51)

"Perylene-based dye derivative 12": a compound represented by the following structural formula (52) (a perylene-based dye derivative that does not correspond to the compound represented by the general formula (1) or the general formula (2))

"Perylene dye derivative 13": a compound represented by the following structural formula (53) (a perylene dye derivative that does not correspond to the compound represented by the general formula (1) or the general formula (2))

"Perylene-based dye derivative 14": a compound represented by the following structural formula (54) (a perylene-based dye derivative that does not correspond to the compound represented by the above general formula (1) or the above general formula (2))

"Perylene-based dye derivative 15": a compound represented by the following structural formula (55) (a perylene-based dye derivative that does not correspond to the compound represented by the general formula (1) or the general formula (2))

"Anthraquinone dye derivative 1": a compound represented by the following structural formula (56)

"Perylene Black A": 3,4,9,10-perylenetetracarboxylic acid bisbenzimidazole; a mixture of a compound represented by the following structural formula (57) and a compound represented by the following structural formula (58) (weight ratio : cis-isomer/trans-isomer = 30/70)

C. I. Pigment Yellow 83: an azo organic yellow pigment having no nitrogen-containing heterocyclic structure in its molecule C.I. I. Pigment Violet 50: an azo organic violet pigment having no nitrogen-containing heterocyclic structure in its molecule C.I. I. Pigment Red 224: A perylene-based organic red pigment having no nitrogen-containing heterocyclic structure in the molecule, represented by the following structural formula (59)

Dioxazine dye derivative 1: C.I. I. A mixture of a monosulfonic acid derivative represented by the following structural formula (60) having Pigment Violet 23 residues and a disulfonic acid derivative represented by the following structural formula (61) (weight ratio: 3:7)

As for the contents of free ionic impurities contained in the above organic dye derivatives and organic pigments, the contents of sulfate ions (SO4 ²⁻ ), sulfite ions (SO3 ⁻ ), and chloride ions (Cl ⁻ ) are 50 ppm or less. was confirmed by ion chromatography. In addition, it was confirmed by ion chromatography that free copper was 100 ppm or less in organic dye derivatives and organic pigments containing copper atoms.

(Preparation Example 1: Preparation of Pigment Dispersion Liquid 1)
89.06 g of alkali-soluble polyimide resin solution A and 28.13 g of SOLSPERSE 20000 (linear type having a polyethylene oxide/propylene oxide structure in the main chain and a tertiary amino group as a basic adsorption group at the end of the main chain Polyether-based dispersant; solid content: 100.00% by weight), 787.66 g of PGMEA as an acetate-based solvent, and 1.41 g of perylene-based dye derivative 1 were mixed and stirred for 10 minutes. Thereafter, (a) 28.13 g of C.I. I. Pigment Yellow 192 (average primary particle size 42 nm) and 28.13 g of C.I. I. Pigment Red 179 (average primary particle size 48 nm) and 37.50 g of C.I. I. Pigment Blue 60 (average primary particle diameter 61 nm) was added and stirred for 30 minutes, and then mixed with a bead mill filled with 0.4 mmφ zirconia beads (manufactured by Toray Industries, Inc.; "Toreceram" (registered trademark)) for 30 minutes. A wet media dispersion treatment was performed by a minute circulation system. Next, in order to further promote miniaturization, a bead mill filled with 0.05 mmφ zirconia beads (manufactured by Toray Industries, Inc.; "Toreceram" (registered trademark)) is used to perform wet media dispersion treatment in a circulation system, After 30 minutes, an appropriate amount of the pigment dispersion was sampled by extracting it into a glass bottle every 10 minutes of the dispersion treatment time. Pigment dispersion liquid 1 was defined as a pigment dispersion liquid in which the particle diameter was measured and within the range of 150 nm±20 nm 30 minutes after sampling. The solid content of Pigment Dispersion 1 was 15.00% by weight. Table 1 shows the blending amount (g) of each raw material. The content of organic dye derivatives for all pigments is 1.50% by weight.

(Preparation Examples 2-7: Preparation of Pigment Dispersions 2-7)
Pigment dispersions 2 to 7 were prepared in the same manner as in Preparation Example 1 by using perylene dye derivatives 2 to 7 instead of perylene dye derivative 1, respectively. Table 1 shows the blending amount (g) of each raw material.

(Preparation Example 8: Preparation of Pigment Dispersion Liquid 8)
C. I. Pigment Red 179, C.I. I. Pigment Red 123 (average primary particle size: 57 nm) was used to prepare Pigment Dispersion Liquid 8 in the same manner as in Preparation Example 1. Table 2 shows the blending amount (g) of each raw material.

(Preparation Example 9: Preparation of Pigment Dispersion Liquid 9)
A pigment dispersion 9 was prepared in the same manner as in Preparation Example 8, except that the perylene dye derivative 4 was used instead of the perylene dye derivative 1. Table 2 shows the blending amount (g) of each raw material.

(Preparation Example 10: Preparation of Pigment Dispersion Liquid 10)
In the same procedure as in Preparation Example 1, except that instead of the perylene dye derivative 1, the perylene dye derivative 7 was used in an amount increased so that the content of the organic dye derivative with respect to all the pigments was 5.00% by weight. A pigment dispersion 10 was prepared. Table 2 shows the blending amount (g) of each raw material.

(Preparation Example 11: Preparation of Pigment Dispersion Liquid 11)
Instead of the perylene dye derivative 1, the content of the organic dye derivative with respect to all the pigments was increased to 5.00% by weight, and the weight ratio of perylene dye derivative 1/perylene dye derivative 7 was 1/1. Pigment Dispersion Liquid 11 was prepared in the same manner as in Preparation Example 1, except that . Table 2 shows the blending amount (g) of each raw material.

(Preparation Example 12: Preparation of Pigment Dispersion Liquid 12)
78.13 g of alkali-soluble polyimide resin solution A, 28.13 g of SOLSPERSE20000, 795.31 g of PGMEA, and 4.69 g of perylene dye derivative 7 were mixed and stirred for 10 minutes. Thereafter, (a) 28.13 g of C.I. I. Pigment Yellow 194 (average primary particle size 64 nm) and 28.13 g of C.I. I. Pigment Violet 29 (average primary particle size 57 nm) and 37.50 g of C.I. I. Pigment Blue 60 (average primary particle size 61 nm) was added and stirred for 30 minutes. In the subsequent steps, wet media dispersion treatment was performed in the same procedure as in Preparation Example 1 to prepare Pigment Dispersion Liquid 12 . Table 2 shows the blending amount (g) of each raw material.

(Preparation Example 13: Preparation of Pigment Dispersion Liquid 13)
68.75 g of alkali-soluble polyimide resin solution A, 28.13 g of SOLSPERSE20000, 801.88 g of PGMEA, and 7.50 g of perylene dye derivative 7 were mixed and stirred for 10 minutes. Thereafter, (a) 32.81 g of C.I. I. Pigment Yellow 192 (average primary particle size 42 nm), 46.88 g of Perylene Black A (average primary particle size 55 nm), and 14.06 g of C.I. I. Pigment Blue 60 (average primary particle size 61 nm) was added and stirred for 30 minutes. In the subsequent steps, wet media dispersion treatment was performed in the same procedure as in Preparation Example 1 to prepare Pigment Dispersion Liquid 13 . Table 2 shows the blending amount (g) of each raw material.

(Preparation Example 14: Preparation of Pigment Dispersion Liquid 14)
C. I. Pigment Blue 60, C.I. I. Pigment Dispersion Liquid 14 was prepared in the same manner as in Preparation Example 13 except that Pigment Blue 15:6 was used. Table 2 shows the blending amount (g) of each raw material.

(Preparation Example 15: Preparation of Pigment Dispersion Liquid 15)
200.00 g of crude pigment A (CI Pigment Red 179; average primary particle size of 172 nm), 13.50 g of perylene dye derivative 1, and rosin containing rosin dimer having one or more carboxyl groups As a mixture, 10.00 g of Dymerex Polymerized Rosin, 2000.00 g of sodium chloride as a water-soluble inorganic salt, and 500.00 g of diethylene glycol as a water-soluble solvent are mixed, and the liquid temperature is adjusted to 100 to 110 ° C. The mixture was kneaded with a kneader for 2 hours to obtain a red kneaded product. Next, add water to the red kneaded product, dissolve the water-soluble components in 3 L of warm water maintained at 60 ° C., repeat washing with water until the content of free chlorine in the red filtered product is less than 100 ppm, and then filter. and dried in an oven at 110° C. for 12 hours. Then, the powder was granulated by dry pulverization using a jet mill to obtain a red surface-treated pigment A (average primary particle size: 44 nm). The above process is the wet pulverization treatment by the solvent salt milling method. In addition, since the perylene-based dye derivative 1 partially disappeared in the filtrate in the above filtration step, the ratio of the constituent components of the finally obtained red surface-treated pigment A was 100 parts by weight of C.I. I. Pigment Red 179, 5 parts by weight of perylene dye derivative 1, and 5 parts by weight of Dymerex Polymerized Rosin. Next, 84.38 g of alkali-soluble polyimide resin solution A, 28.13 g of SOLSPERSE20000, and 790.94 g of PGMEA were mixed and stirred for 10 minutes. Thereafter, (a) 28.13 g of C.I. I. Pigment Yellow 192, 30.94 g of Red Surface Treated Pigment A, and 37.50 g of C.I. I. Pigment Blue 60 was added and stirred for 30 minutes. In subsequent steps, wet media dispersion treatment was performed in the same procedure as in Preparation Example 1, and Pigment Dispersion Liquid 15 was prepared. Table 2 shows the blending amount (g) of each raw material.

(Preparation Example 16: Preparation of Pigment Dispersion Liquid 16)
89.06 g of alkali-soluble polyimide resin solution A, 93.75 g of polymer type dispersant solution B, 722.03 g of PGMEA, and 1.41 g of perylene dye derivative 8 were mixed and stirred for 10 minutes. Then 28.13 g of C.I. I. Pigment Yellow 192 (average primary particle size 42 nm) and 28.13 g of C.I. I. Pigment Red 179 (average primary particle size 48 nm) and 37.50 g of C.I. I. Pigment Blue 60 (average primary particle size 61 nm) was added and stirred for 30 minutes. In subsequent steps, wet media dispersion treatment was performed in the same procedure as in Preparation Example 1 to prepare Pigment Dispersion Liquid 16 . The content of organic dye derivatives for all pigments is 1.50% by weight.
Table 3 shows the blending amount (g) of each raw material.

(Preparation Examples 17-19: Preparation of Pigment Dispersions 17-19)
Pigment dispersions 17 to 19 were prepared in the same manner as in Preparation Example 16, except that perylene dye derivatives 9 to 11 were used instead of perylene dye derivative 8. Table 3 shows the blending amount (g) of each raw material.

(Preparation Example 20: Preparation of Pigment Dispersion Liquid 20)
Preparation Example 17 except that perylene dye derivative 11 was used instead of perylene dye derivative 8, and anthraquinone dye derivative 1 was used in combination at a weight ratio of perylene dye derivative 11/anthraquinone dye derivative 1=2/1. Pigment Dispersion Liquid 20 was prepared in the same procedure as . Table 3 shows the blending amount (g) of each raw material.

(Preparation Example 21: Preparation of Pigment Dispersion Liquid 21)
89.06 g of alkali-soluble polyimide resin solution A, 28.13 g of SOLSPERSE20000, 787.66 g of PGMEA, and 1.41 g of perylene dye derivative 1 were mixed and stirred for 10 minutes. After that, 18.75 g of C.I. I. Pigment Yellow 83 (average primary particle size 41 nm) and 56.25 g of C.I. I. Pigment Violet 50 (average primary particle size 56 nm) and 18.75 g of C.I. I. Pigment Red 179 (average particle size 48 nm) was added and stirred for 30 minutes. In subsequent steps, wet media dispersion treatment was performed in the same procedure as in Preparation Example 1 to prepare Pigment Dispersion Liquid 21 . Table 4 shows the blending amount (g) of each raw material. The content of organic dye derivatives for all pigments is 1.50% by weight.

(Preparation Example 22: Preparation of Pigment Dispersion Liquid 22)
Pigment Dispersion Liquid 22 was prepared in the same manner as in Preparation Example 21 by increasing the amount of Perylene Dye Derivative 1 and using the amount (g) shown in Table 4. The content of organic dye derivatives for all pigments is 5.00% by weight.

(Preparation Example 23: Preparation of Pigment Dispersion Liquid 23)
Using perylene dye derivative 4 instead of perylene dye derivative 1, C.I. I. Pigment Red 179, C.I. I. Pigment Red 224 (average primary particle size: 62 nm) was used, and the amount (g) shown in Table 4 was used to prepare Pigment Dispersion Liquid 23 in the same manner as in Preparation Example 21.

(Preparation Example 24: Preparation of Pigment Dispersion Liquid 24)
200.00 g of crude pigment B (C.I. Pigment Violet 29; average primary particle size 163 nm), 2000.00 g of sodium chloride, and 400.00 g of diethylene glycol are mixed, and the liquid temperature is 90 to 100 ° C. and kneaded with a kneader for 7 hours to obtain a purple kneaded product. Next, add water to the purple kneaded product, dissolve the water-soluble components in 2 L of warm water maintained at 60 ° C., repeat washing with water until the content of free chlorine in the purple filtered product is less than 100 ppm, and then filter. After that, it was diluted again with water to obtain a purple pigment slurry having a solid content of 30% by weight. An aqueous sodium hydroxide solution containing the copper phthalocyanine dye derivative 1 was added to the purple pigment slurry, and after stirring for 1 hour, hydrochloric acid was added until the pH reached 7, thereby precipitating the copper phthalocyanine dye derivative 1 on the surface of the pigment. After that, it was dried in an oven at 110° C. for 12 hours. Next, the particles were sieved by dry pulverization using a jet mill, and 100 parts by weight of C.I. I. Pigment Violet 29 and 5 parts by weight of copper phthalocyanine dye derivative 1 were used to obtain a purple surface-treated pigment A (average primary particle diameter: 25 nm). Next, 28.13 g of PB821 (manufactured by Ajinomoto Fine-Techno; polyester polymer dispersant having a basic adsorptive group and an acidic adsorptive group; solid content: 100.00% by weight) and 788.01 g of PGMEA were mixed. and stirred for 10 minutes. Thereafter, 27.33 g of C.I. I. Pigment Yellow 139 (average primary particle size 65 nm), 32.43 g of purple surface-treated pigment A, and 35.55 g of C.I. I. Pigment Blue 15:6 (average primary particle size 45 nm) was added and stirred for 30 minutes. In subsequent steps, wet media dispersion treatment was performed in the same manner as in Preparation Example 1. Next, the pigment dispersion was diluted by adding the alkali-soluble polyimide resin solution A so that the solid content of the pigment dispersion became 15.00% by weight, thereby preparing a pigment dispersion 24 . The content of solids in the alkali-soluble polyimide resin solution A for all organic pigments contained in the pigment dispersion 24 is 28.33% by weight, and the content of the organic dye derivative is 1.65% by weight. . Table 4 shows the blending amount (g) of each raw material.

(Preparation Example 25: Preparation of Pigment Dispersion Liquid 25)
A wet pulverization treatment was carried out in the same manner as in Preparation Example 24 except that the amount of copper phthalocyanine dye derivative 1 added was increased, and 100 parts by weight of C.I. I. Pigment Violet 29 and 12 parts by weight of copper phthalocyanine dye derivative 1 to obtain a purple surface-treated pigment B (average primary particle diameter 25 nm), and the amount (g) shown in Table 4 was used in the same manner as in Preparation Example 24. Pigment Dispersion 25 with a solids content of 15.00% by weight was prepared according to the procedure. The content of solids in the alkali-soluble polyimide resin solution A for all organic pigments contained in the pigment dispersion 25 is 26.03% by weight, and the content of the organic dye derivative is 3.95% by weight. . Table 4 shows the blending amount (g) of each raw material.

(Preparation Example 26: Preparation of Pigment Dispersion Liquid 26)
A pigment dispersion 26 having a solid content of 15.00% by weight was prepared in the same manner as in Preparation Example 25, except that SOLSPERSE20000 was used instead of PB821. Table 4 shows the blending amount (g) of each raw material.

(Preparation Example 27: Preparation of Pigment Dispersion Liquid 27)
A wet pulverization treatment was carried out in the same manner as in Preparation Example 24 except that copper phthalocyanine dye derivative 2 was used instead of copper phthalocyanine dye derivative 1 to obtain a purple surface-treated pigment C (average primary particle size: 31 nm). . In subsequent steps, wet media dispersion treatment was performed in the same manner as in Preparation Example 24. Then, the pigment dispersion was diluted by adding the alkali-soluble polyimide resin solution A so that the solid content of the pigment dispersion became 15.00% by weight, thereby preparing a pigment dispersion 27 . The content of solids in the alkali-soluble polyimide resin solution A for all organic pigments contained in the pigment dispersion 27 is 28.33% by weight, and the content of the organic dye derivative is 1.65% by weight. . Table 4 shows the blending amount (g) of each raw material.

(Preparation Example 28: Preparation of Pigment Dispersion Liquid 28)
62.45 g of alkali-soluble polyimide resin solution A, 28.13 g of PB821, 806.28 g of PGMEA, and 9.38 g of copper phthalocyanine dye derivative 1 were mixed and stirred for 10 minutes. After that, (a) 27.33 g of C.I. I. Pigment Yellow 139 (average primary particle size 65 nm) and 30.88 g of C.I. I. Pigment Violet 29 (average primary particle size 57 nm) and 35.55 g of C.I. I. Pigment Blue 15:6 (average primary particle size 45 nm) was added and stirred for 30 minutes. In subsequent steps, wet media dispersion treatment was performed in the same procedure as in Preparation Example 1 to prepare Pigment Dispersion Liquid 28 having a solid content of 15.00% by weight. Incidentally, the content of the organic dye derivative with respect to all the organic pigments contained in the pigment dispersion liquid 28 is 10.00% by weight. Table 5 shows the blending amount (g) of each raw material.

(Preparation Examples 29-33: Preparation of Pigment Dispersions 29-33)
Pigment dispersions 29 to 33 having a solid content of 15.00% by weight were prepared in the same manner as in Preparation Example 1, except that copper phthalocyanine dye derivatives 1 to 5 were used instead of perylene dye derivative 1. . The content of the organic dye derivative with respect to all the organic pigments contained in Pigment Dispersions 29 to 33 was 1.50% by weight. Table 5 shows the blending amount (g) of each raw material.

(Preparation Example 34: Preparation of Pigment Dispersion Liquid 34)
A pigment dispersion 34 having a solid content of 15.00% by weight was prepared in the same manner as in Preparation Example 16, except that the perylene dye derivative 8 was replaced with the copper phthalocyanine dye derivative 6. Incidentally, the content of the organic dye derivative with respect to all the organic pigments contained in the pigment dispersion liquid 34 is 1.50% by weight. Table 6 shows the blending amount (g) of each raw material.

(Preparation Example 35: Preparation of Pigment Dispersion Liquid 35)
A pigment dispersion 35 having a solid content of 15.00% by weight was prepared in the same manner as in Preparation Example 1 using the copper phthalocyanine dye derivative 6 instead of the perylene dye derivative 8 and the amount (g) shown in Table 6. was prepared. Incidentally, the content of the organic dye derivative with respect to all the organic pigments contained in the pigment dispersion liquid 35 is 5.00% by weight. Table 6 shows the blending amount (g) of each raw material.

(Preparation Examples 36-41: Preparation of Pigment Dispersions 36-41)
Instead of perylene dye derivative 1, diketopyrrolopyrrole pigment derivative 1, isoindoline dye derivative 1, and perylene dye derivatives 12 to 15 were used. 15.00 wt% pigment dispersions 36-41 were prepared. Table 6 shows the blending amount (g) of each raw material.

(Preparation Example 42: Preparation of Pigment Dispersion Liquid 42)
A pigment dispersion liquid 42 was prepared in the same manner as in Preparation Example 1, except that the amount of the perylene dye derivative 14 was increased and the amount (g) shown in Table 6 was used. Note that the content of the organic dye derivative with respect to all the pigments contained in the pigment dispersion liquid 42 is 5.00% by weight.

(Preparation Example 43: Preparation of Pigment Dispersion Liquid 43)
A pigment dispersion 43 having a solid content of 15.00% by weight was prepared in the same manner as in Preparation Example 1 using the amount (g) shown in Table 7 without using the perylene dye derivative 1.

(Preparation Example 44: Preparation of Pigment Dispersion Liquid 44)
93.75 g of alkali-soluble polyimide resin solution A, 28.13 g of SOLSPERSE20000, and 784.38 g of PGMEA were mixed and stirred for 10 minutes. Thereafter, (a) 46.88 g of C.I. I. Pigment Red 254 (average primary particle size 40 nm) and 46.88 g of C.I. I. Pigment Blue 15:6 (average primary particle size 45 nm) was added and stirred for 30 minutes. In subsequent steps, wet media dispersion treatment was performed in the same procedure as in Preparation Example 1 to prepare Pigment Dispersion Liquid 44 having a solid content of 15.00% by weight. Table 7 shows the blending amount (g) of each raw material.

(Preparation Example 45: Preparation of Pigment Dispersion Liquid 45)
A pigment dispersion 45 having a solid content of 15.00% by weight was prepared in the same manner as in Preparation Example 43, except that the polymer-type dispersant solution B was used instead of SOLSPERSE20000. Table 7 shows the blending amount (g) of each raw material.

(Preparation Example 46: Preparation of Pigment Dispersion Liquid 46)
84.33 g of alkali-soluble polyimide resin solution A, 28.13 g of SOLSPERSE20000, 790.97 g of PGMEA, and 2.81 g of copper phthalocyanine dye derivative 1 were mixed and stirred for 10 minutes. After that, (a) 27.33 g of C.I. I. Pigment Yellow 139 (average primary particle size 65 nm) and 30.88 g of C.I. I. Pigment Violet 23 (average primary particle size 58 nm) and 35.55 g of C.I. I. Pigment Blue 60 (average primary particle size 61 nm) was added and stirred for 30 minutes. In subsequent steps, wet media dispersion treatment was performed in the same procedure as in Preparation Example 1 to prepare a pigment dispersion 46 having a solid content of 15.00% by weight. Table 7 shows the blending amount (g) of each raw material. Incidentally, the content of the organic dye derivative with respect to all the organic pigments contained in the pigment dispersion liquid 46 is 3.00% by weight.

(Preparation Example 47: Preparation of Pigment Dispersion Liquid 47)
Pigment Dispersion 47 having a solid content of 15.00% by weight was prepared in the same manner as in Preparation Example 46 except that the amount of copper phthalocyanine dye derivative 1 was increased. Incidentally, the content of the organic dye derivative with respect to all the organic pigments contained in the pigment dispersion liquid 47 is 10.00% by weight.

(Preparation Example 48: Preparation of Pigment Dispersion Liquid 48)
Pigment Dispersion 48 having a solid content of 15.00% by weight with the ingredients shown in Table 7 was prepared in the same manner as in Preparation Example 46 except that Dioxazine Dye Derivative 1 was used instead of Copper Phthalocyanine Dye Derivative 1. was prepared.

(Preparation Example 49: Preparation of Pigment Dispersion Liquid 49)
Copper phthalocyanine dye derivative 1 and dioxazine dye derivative 1 were used in combination at a weight ratio of copper phthalocyanine dye derivative 1/dioxazine dye derivative 1 = 1/1. A pigment dispersion 49 having a solid content of 15.00% by weight was prepared with the blending amounts of the raw materials shown in . Incidentally, the content of the organic dye derivative with respect to all the organic pigments contained in the pigment dispersion liquid 49 is 6.00% by weight.

(Preparation Example 50: Preparation of Pigment Dispersion Liquid 50)
A pigment dispersion 50 having a solid content of 15.00% by weight was prepared in the same manner as in Preparation Example 13 except that the perylene-based dye derivative 7 was not used.

(Preparation Example 51: Preparation of Pigment Dispersion Liquid 51)
Pigment Dispersion 51 having a solid content of 15.00% by weight with the ingredients shown in Table 8 was prepared in the same manner as in Preparation Example 13, except that copper phthalocyanine dye derivative 1 was used instead of perylene dye derivative 7. was prepared. Incidentally, the content of the organic dye derivative with respect to all the organic pigments contained in the pigment dispersion liquid 51 is 8.00% by weight.

(Preparation Example 52: Preparation of Pigment Dispersion Liquid 52)
Pigment Dispersion 52 having a solid content of 15.00% by weight with the ingredients shown in Table 8 was prepared in the same manner as in Preparation Example 13, except that copper phthalocyanine dye derivative 1 was used instead of perylene dye derivative 7. was prepared. Incidentally, the content of the organic dye derivative with respect to all the organic pigments contained in the pigment dispersion liquid 52 is 4.00% by weight.

(Example 1)
26.40 g of pigment dispersion 1, 5.30 g of alkali-soluble polyimide resin solution A, and 1.35 g of ε-caprolactone-added acrylate of dipentaerythritol as a compound having two or more radically polymerizable groups (KAYARAD DPCA-60; Nippon Kayaku Co., Ltd.; “DPCA-60” in the table) and 0.30 g of “ADEKA CRUISE” (registered trademark) NCI-831 (manufactured by ADEKA Co., Ltd.) as a photopolymerization initiator ), 0.30 g of VG-3101L, which is a compound having three epoxy groups in the molecule as a thermal cross-linking agent, and 7.85 g of PGMEA and 8.50 g of MBA, which are solvents, were mixed and sealed. and stirred on a shaker for 30 minutes until the total content of the organic pigment is 33.00% by weight relative to the total solid content in the negative photosensitive composition, and the solid content is 15.00% by weight. A negative photosensitive composition 1 was prepared. Dispersion stability was then evaluated by the method described above. The pigment dispersion used for the preparation of the photosensitive composition was not stored alone for a long period of time, but was used for the preparation of the photosensitive composition within 2 hours after being obtained by the wet media dispersion treatment. Table 9 shows the blending amount (g) of each raw material, and Table 14 shows the evaluation results of dispersion stability.

After being prepared by the above procedure, the negative photosensitive composition 1 after long-term storage while standing for 30 days in a constant temperature box under atmospheric pressure/under light shielding/at an actual temperature of 25°C ± 1°C was shaken for 1 minute on a shaker. Stir and apply to the surface of Tempax (translucent glass substrate of 50 mm × 50 mm) with a spin coater while adjusting the rotation speed so that the thickness of the cured film finally obtained is 1.0 μm. to obtain a coating film. Furthermore, using a hot plate (SCW-636; manufactured by Dainippon Screen Mfg. Co., Ltd.), the coating film was prebaked at 100° C. under atmospheric pressure for 120 seconds to obtain a prebaked film. Using a double-sided alignment single-sided exposure apparatus (mask aligner PEM-6M; manufactured by Union Optical Co., Ltd.), j-line (wavelength 313 nm), i-line (wavelength 365 nm), h-line (wavelength 405 nm) and g-line (wavelength 405 nm) of an ultra-high pressure mercury lamp The entire surface of the pre-baked film was irradiated with a mixed beam having a wavelength of 436 nm at the minimum necessary exposure dose obtained by the above-described method to obtain an exposed film. Next, using a compact developing device for photolithography (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.), the film was developed with a 2.38% by weight TMAH aqueous solution for 60 seconds and rinsed with deionized water for 30 seconds to obtain a developed film. Then, using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.), the developed film was heated at 250° C. for 60 minutes in a nitrogen atmosphere to form a cured film having a thickness of 1.0 μm. A substrate for light shielding evaluation, which is provided on Pax, was obtained. Table 14 shows the results of evaluating the light shielding properties of the cured film by the method described above.

Next, an organic EL display device for evaluation of light emission reliability, which had a cured film made of a cured product of the negative photosensitive composition 1 as a pixel dividing layer, was produced by the following method. FIG. 2 shows a manufacturing process of an organic EL display including a process of forming a pixel division layer.

A silver/copper alloy thin film (volume ratio: 10:1) with a thickness of 10 nm was formed on the surface of an alkali-free glass substrate 11 of 38 mm x 46 mm over the entire surface by sputtering, and etched to form a patterned metal reflective layer 12 . formed. Next, a 10 nm-thick ITO transparent conductive film is formed on the entire surface by sputtering, and etched to form a second electrode 13 having the same pattern and an auxiliary electrode 14 as a lead-out electrode. 56 (manufactured by Furuuchi Chemical Co., Ltd.) for 10 minutes and then with ultrapure water to obtain an electrode-formed substrate.

After preparation, the negative photosensitive composition 1 was stirred on a shaker for 1 minute after long-term storage while standing still for 30 days in a constant temperature box under atmospheric pressure/under light shielding/actual temperature of 25°C ± 1°C. (MS-A100; manufactured by Mikasa Co., Ltd.), the number of revolutions is adjusted so that the thickness of the finally obtained pixel division layer is 1.0 μm, and the coating is applied to the surface of the electrode forming substrate, A coating film was obtained. Furthermore, using a hot plate (SCW-636; manufactured by Dainippon Screen Mfg. Co., Ltd.), the coating film was prebaked at 100° C. under atmospheric pressure for 120 seconds to obtain a prebaked film.

Using a double-sided alignment single-sided exposure apparatus (mask aligner PEM-6M; manufactured by Union Optical Co., Ltd.), through a negative exposure mask, the j-line (wavelength 313 nm), i-line (wavelength 365 nm), and h of an ultra-high pressure mercury lamp. The pre-baked film was pattern-irradiated with exposure light of a mixed line (wavelength: 405 nm) and g-line (wavelength: 436 nm) at the minimum necessary exposure dose to obtain an exposed film. Then, using a compact developing device for photolithography (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.), the developed film was developed with a 2.38% by weight TMAH aqueous solution for 60 seconds and rinsed with deionized water for 30 seconds. Obtained. Furthermore, using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.), the developed film was heated at 250° C. for 60 minutes in a nitrogen atmosphere to form a cured film. A pixel division layer forming substrate 1 having an aperture ratio of 25% is obtained, in which a pixel division layer 15 having a thickness of 1.0 μm and having openings (70 μm width/260 μm length) arranged in an area of 16 mm/16 mm width is obtained. Table 14 shows the results of evaluating the development residue generated on the ITO electrode by the method described above. The opening referred to here is a portion that will eventually become the light-emitting pixel portion of the organic EL display device after going through the processes described later.

Next, using the pixel division layer forming substrate 1, an organic EL display device was manufactured. In order to form the organic EL layer 16 including the light-emitting layer by a vacuum deposition method, the pixel division layer forming substrate 1 is rotated with respect to the deposition source under deposition conditions of a degree of vacuum of 1×10 ⁻³ Pa or less. A film of compound (HT-1) was formed to a thickness of 10 nm as a hole injection layer, and a film of compound (HT-2) was formed to a thickness of 50 nm as a hole transport layer. Next, the compound (GH-1) as a host material and the compound (GD-1) as a dopant material were vapor-deposited on the light-emitting layer to a thickness of 40 nm. After that, the compound (ET-1) and the compound (LiQ) were laminated as electron transport materials at a volume ratio of 1:1 to a thickness of 40 nm.

Next, after vapor-depositing a compound (LiQ) to a thickness of 2 nm, a silver/magnesium alloy (volume ratio: 10:1) was vapor-deposited to a thickness of 10 nm to form the first electrode 17 . After that, in a low humidity/nitrogen atmosphere, a cap-shaped glass plate was adhered and sealed using an epoxy resin adhesive to obtain an organic EL display device 1 . The thickness referred to here is a value displayed by a crystal oscillation type film thickness monitor.

The chemical structures of the compound groups (HT-1, HT-2, GH-1, GD-1, ET-1, LiQ) used to form the organic EL layer are shown below.

Next, an organic EL display device 2 having a pixel division layer with an aperture ratio of 18% was manufactured in the same manner except that only the aperture ratio of the negative exposure mask was changed. Table 14 shows the results of evaluating the light emission reliability by the method described above.

Further, an organic EL display device for evaluation of light emission reliability was produced by the following method, each having a cured film made of a cured product of the negative photosensitive composition 1 as a pixel dividing layer and a flattening layer.
FIG. 3 shows the manufacturing process of the organic EL display device including the process of forming the pixel dividing layer and the planarizing layer.

Using a spin coater, a negative photosensitive composition was applied to the surface of an alkali-free glass substrate 18 of 38 mm×46 mm by adjusting the number of rotations so that the thickness of the flattened layer finally obtained was 1.5 μm. 1 was applied to obtain a coating film. Using a hot plate, the coating film was prebaked at 100° C. under atmospheric pressure for 120 seconds to obtain a prebaked film. Mixed lines of j-line (313 nm), i-line (wavelength 365 nm), h-line (wavelength 405 nm) and g-line (wavelength 436 nm) of ultra-high pressure mercury lamp through a negative type exposure mask using a double-side alignment single-side exposure apparatus. was pattern-irradiated to the pre-baked film with exposure light at the required minimum exposure amount to obtain an exposed film. Next, using a compact developing device for photolithography, the film was developed with a 2.38% by weight TMAH aqueous solution for 60 seconds and rinsed with deionized water for 30 seconds to obtain a developed film. Furthermore, using a high-temperature inert gas oven, the developed film was heated at 250° C. for 60 minutes in a nitrogen atmosphere to form a cured film, and a solid film-like flat film having no in-plane openings was placed in the center of the alkali-free glass substrate. A modified layer 19 was obtained.

Then, a 10 nm-thick silver/copper alloy thin film (volume ratio: 10:1) and a 10 nm-thick ITO transparent conductive film were formed on the surface of the flattening layer 19 in sequence by sputtering. The two layers of the silver/copper alloy thin film and the ITO transparent conductive film are etched at once to pattern the metal reflective layer/second electrode 20 and the metal reflective layer/auxiliary electrode 21. Ultrasonic cleaning was performed for 10 minutes, followed by cleaning with ultrapure water to obtain an electrode-formed substrate. In addition, the flattening layer 19 is formed by forming the lamination pattern consisting of the two layers of the metal reflective layer/second electrode so that the aperture ratio in the effective light emitting area of the finally obtained organic EL display device is 70%. 30% of the surface area of the film was covered with the laminated pattern, and 70% of the film surface was exposed. In the subsequent steps, the negative photosensitive composition 1 is used to form the pixel division layer 22 in the same manner as the organic EL display device 2 described above, and furthermore, the light-emitting pixels 23 and the first electrodes 24 are formed. are sequentially formed and then sealed to form an organic EL display device 3 having a pixel division layer with a film thickness of 1.0 μm and an aperture ratio of 18% and a planarizing layer with a film thickness of 1.5 μm and an aperture ratio of 0%. It was fabricated and evaluated for emission reliability and dark spots by the methods described above. Table 14 shows the evaluation results.

(Examples 2 to 20, Comparative Examples 1 to 32)
Negative photosensitive compositions 2 to 52 having a solid content of 15% by weight were prepared in the same manner as in Example 1, except that the pigment dispersions 2 to 52 were used instead of the pigment dispersion 1. Dispersion stability was evaluated by the method described above. Tables 9 to 13 show the blending amount (g) of each raw material.

Then, in the same procedure as in Example 1, except that the negative photosensitive compositions 2 to 52 were used instead of the negative photosensitive composition 1, a light-shielding evaluation substrate, a pixel division layer evaluation substrate, and an organic An EL display device was produced and evaluated for light shielding properties, development residue, light emission reliability and dark spots by the methods described above. Tables 14 to 18 collectively show the negative photosensitive compositions used and the evaluation results thereof. The pigment dispersion used for the preparation of the photosensitive composition was not stored alone for a long period of time, but was used for the preparation of the photosensitive composition within 2 hours after being obtained by the wet media dispersion treatment described above. . In addition, after preparation in the same manner as in Example 1, all of the negative photosensitive compositions used were left to stand for 30 days in a constant temperature box under atmospheric pressure/under light shielding/actual temperature of 25°C ± 1°C for long-term storage. After that, the mixture was stirred on a shaker for 1 minute before use.

(Example 21)
12.50 g of pigment dispersion 16, 11.75 g of alkali-soluble polyimide resin solution A, 1.80 g of quinonediazide compound a as a photosensitive agent, and 0.30 g of VG-3101L as a thermal crosslinking agent, and 15 .15 g of PGMEA and 8.50 g of MBA were mixed, sealed and stirred on a shaker for 30 minutes to prepare positive photosensitive composition 1 having a solid content of 15.00% by weight, and dispersed by the method described above. Stability was evaluated. The pigment dispersion used for the preparation of the photosensitive composition was not stored alone for a long period of time, but was used for the preparation of the photosensitive composition within 2 hours after being obtained by the wet media dispersion treatment described above. . Table 19 shows the blending amount (g) of each raw material, and Table 20 shows the evaluation results of dispersion stability.

After preparation, the positive photosensitive composition 1 was stirred for 1 minute on a shaker after being stored for a long period of time while standing still for 30 days in a constant temperature box under atmospheric pressure/under light shielding/at an actual temperature of 25°C ± 1°C, and exposed. A light-shielding evaluation substrate was obtained in the same manner as in Example 1, except that the process and the developing process were not performed. Next, a pixel division layer evaluation substrate and an organic EL display device were produced in the same manner as in Example 1, except that a positive exposure mask in which the openings and light shielding portions of the negative exposure mask were reversed was used. were evaluated for development residue, emission reliability and dark spots. Table 20 shows the evaluation results.

(Example 22, Comparative Example 33)
Positive photosensitive compositions 2 and 3 were prepared in the same manner as in Example 21 except that pigment dispersions 19 and 45 were used instead of pigment dispersion 16, and the dispersion stability was evaluated by the method described above. evaluated. Table 19 shows the blending amount (g) of each raw material, and Table 20 shows the evaluation results of dispersion stability.

After preparation, the positive photosensitive compositions 2 and 3 were stirred on a shaker for 1 minute after being stored for a long period of time while standing still for 30 days in a constant temperature box under atmospheric pressure/under light shielding/actual temperature of 25°C ± 1°C. A light-shielding evaluation substrate, a pixel division layer evaluation substrate, and an organic EL display device were produced in the same manner as in Example 21, and light-shielding properties, development residues, light emission reliability, and dark spots were evaluated by the methods described above. . Table 20 shows the positive photosensitive compositions used and the evaluation results thereof.

In general, the organic EL display devices of Comparative Examples 1 to 33 are insufficient in at least one of dark spots and light emission reliability, but the organic EL display devices of Examples 1 to 22 have dark spots. Although it is suppressed, high light emission reliability is obtained, and it can be seen that both characteristics are compatible.
From the above, it can be seen that the organic EL display device of the present invention is useful.

The organic EL display device of the present invention is used in applications that require high light emission reliability while suppressing dark spots, for example, in electronic devices such as smartphones, televisions, and personal computers equipped with organic EL panels. be able to.

1: TFTs
2: Wiring 3: TFT insulating film 4: Flattening layer 5: Second electrode (ITO electrode)
6: Substrate 7: Contact hole 8: Pixel division layer 9: Light-emitting pixel 10: First electrode 11: Non-alkali glass substrate 12: Metal reflective layer 13: Second electrode (ITO electrode)
14: Auxiliary electrode (ITO electrode)
15: Pixel division layer 16: Light-emitting pixel (organic EL layer)
17: First electrode 18: Non-alkali glass substrate 19: Flattening layer 20: Second electrode (ITO electrode)
21: Auxiliary electrode (ITO electrode)
22: Pixel division layer 23: Light-emitting pixels (organic EL layer)
24: first electrode

Claims (13)

An organic EL display device comprising a first electrode, a pixel dividing layer, a luminescent pixel, a second electrode, a planarizing layer and a substrate, wherein the pixel dividing layer and/or the planarizing layer comprise (a) a nitrogen-containing It contains a black material having a heterocyclic structure, (b) a dispersant, and (c) a resin, and the (b) dispersant is a compound represented by the following general formula (1) and/or the following general formula ( 2) An organic EL display device containing the compound represented by .

(In general formula (1) above, X ¹ is a substituent directly bonded to the perylene ring and represents —SO ₃ H, —SO ₃ M, —SO ₂ NHR ¹ or —CONHR ^1. M is Na, K or NH _4. R ¹ represents an organic group having a terminal N,N-dialkylamino group, Z ¹ represents an atom or substituent directly bonded to the perylene ring, and is a hydrogen atom, an alkyl group or an alkoxy group. n and m are integers, n represents 1 or 2, and satisfies n+m=10.)

(In the above general formula (2), R ² and R ³ are the same and represent a hydrogen atom, an aryl group having a substituent or a methyl group, and X ² is a substituent directly bonded to the perylene ring and/or the benzene ring. and represents —SO ₃ H, —SO ₃ M, —SO ₂ NHR ⁴ or —CONHR ^4. M represents Na, K or NH _4. R ⁴ terminates an N,N-dialkylamino group. Z ² represents an atom directly bonded to the perylene ring or a substituent, and represents a hydrogen atom, an alkyl group or an alkoxy group, p and q are integers, p represents 1 or 2, and q represents 6 to 8.) 2. The organic EL display device according to claim 1, wherein the (b) dispersant contains a compound represented by the following general formula (22) and/or a compound represented by the following general formula (23).

(In the above general formula (22), X ³ represents —SO ₃ H directly bonded to the perylene ring, Z ³ represents a hydrogen atom directly bonded to the perylene ring, n and m are integers, and n is 1 or 2 and satisfies n+m=10.)

(In the above general formula (23), R ⁵ and R ⁶ are the same and represent a hydrogen atom, a substituted aryl group or a methyl group. X ⁴ is directly bonded to the perylene ring and/or the benzene ring- represents SO ₃ H, Z ⁴ represents a hydrogen atom directly bonded to the perylene ring, p and q are integers, p represents 1 or 2, and q represents 6 to 8.) The organic EL according to claim 1 or 2, wherein the (a) black material having a nitrogen-containing heterocyclic ring structure contains a perylene-based organic black pigment having two benzimidazole rings in the molecule as the nitrogen-containing heterocyclic ring. display device. The (a) black material having a nitrogen-containing heterocyclic structure comprises a mixture containing at least an organic yellow pigment, an organic red pigment, and an organic blue pigment, and the organic yellow pigment contains a benzimidazolone-based organic yellow pigment. 3. The organic EL according to claim 1 or 2, wherein the organic blue pigment contains a phthalocyanine organic blue pigment and/or an indanthron organic blue pigment, and the organic red pigment contains a perylene organic red pigment. display device. 5. The organic EL display device according to claim 1, wherein the resin (c) contains a polyimide resin. The organic EL according to any one of claims 1 to 5, wherein the (b) dispersant contains the compound represented by the general formula (22) and the compound represented by the general formula (23). display device. 7. The organic EL display device according to claim 1, wherein said (b) dispersant further contains a polymer-type dispersant having a phosphoric acid group. 8. The organic EL display device according to claim 1, wherein said pixel dividing layer and/or said planarizing layer is made of a cured product of a negative photosensitive composition. 8. The organic EL display device according to claim 1, wherein said pixel dividing layer and/or said planarizing layer are made of a cured product of a positive photosensitive composition. 10. The organic EL display device according to claim 1, wherein said pixel dividing layer and/or said planarizing layer have an optical density of 0.5 or more and 2.0 or less per 1.0 μm of film thickness. The organic EL display device according to any one of claims 1 to 10, wherein the base material is a flexible base material made of polyimide resin. 12. The organic EL display device according to claim 1, wherein the display area of said pixel division layer has an aperture ratio of 20% or less. 13. A method for forming the pixel division layer and/or the planarization layer included in the organic EL display device according to any one of claims 1 to 12, wherein 1.0 to 3.0 weight of tetramethylammonium hydroxide is used. A method of forming a pixel dividing layer and/or a planarizing layer, comprising a developing step of obtaining a developed film using a developing solution containing %.

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