KR102318084B1 - Organic EL display device, and method of forming a pixel dividing layer and a planarization layer - Google Patents

Abstract

An organic EL display device having excellent luminescence reliability by suppressing the occurrence of dark spots derived from development residues due to agglomerates of pigments. An organic EL display device comprising a first electrode, a pixel division layer, a light emitting pixel, a second electrode, a planarization layer, and a substrate, wherein the pixel division layer and/or the planarization layer have (a) a nitrogen-containing heterocyclic structure The black material, (b) dispersing agent, and (c) resin are contained, and this (b) dispersing agent contains the compound represented by the said General formula (1) and/or the compound represented by the said General formula (2) do.

Description

Organic EL display device, and method of forming a pixel dividing layer and a planarization layer

The present invention relates to an organic EL display device.

DESCRIPTION OF RELATED ART In display apparatuses with a thin display, such as a smart phone, a tablet PC, and a television, many products in which the organic electroluminescent (EL) display is mounted are developed. The organic EL display device is a self-luminous display device that emits light using energy generated by recombination of electrons injected from a cathode and holes injected from an anode. As the specific example, the organic electroluminescent display provided with the pixel division layer which has a function as an insulating film, and a planarization layer is disclosed (for example, patent document 1).

In recent years, attempts have been made to reduce reflection of external light such as sunlight by providing light-shielding properties to the pixel division layer and/or the planarization layer to improve the visibility and contrast of the organic EL display device. As the specific example, the organic electroluminescent display provided with the blackened pixel division layer is disclosed (for example, patent document 2).

Examples of the composition for forming the blackened pixel division layer include a photosensitive composition containing a plurality of types of organic pigments of different colors and pseudo-blackened by subtractive color mixing, and specific examples thereof include an organic red pigment and an organic blue color. The photosensitive composition containing a pigment is disclosed (for example, refer patent document 3).

However, when an organic pigment is to be dispersed in a resin solution, re-aggregation proceeds during or after the dispersion process, so that sufficient coloring power is not obtained, or color separation occurs in a dispersion system in which a plurality of types of pigments coexist. Problems like this often occur. In order to solve the above problem, the use of an organic dye derivative (synergist) as a dispersing agent for improving the resin adsorption property on the surface of the organic pigment and increasing the dispersion stability is well known. In the black matrix field of liquid crystal display devices where a function to reduce external light reflection is required, similar to the pixel division layer of organic EL display devices, it is a technology to replace carbon black, which has defects in electrical characteristics such as insufficient insulation and high dielectric constant. , the pseudo-blackened photosensitive composition attracts attention, and the technique which used the organic pigment and the organic dye derivative together is disclosed. As the specific example, the photosensitive composition which carried out the pseudo blackening containing a perylene-type organic pigment and the copper phthalocyanine derivative which has a sulfonic acid group is disclosed (for example, refer patent document 4).

International Publication No. 2016/047483 Japanese Patent Laid-Open No. 2013-30293 Japanese Patent Laid-Open No. 2013-207124 International Publication No. 2015/015962

However, when the pixel division layer and/or planarization layer of an organic electroluminescent display are formed using the photosensitive composition which carried out the pseudo blackening of patent documents 3 and 4, the dispersion stability in the photosensitive composition of an organic pigment is not enough. Moreover, since the dispersed state is easy to collapse|disintegrate during the developing process, the problem that the developing residue derived from a pigment aggregate generate|occur|produced on the ITO electrode of a pattern opening part generate|occur|produced, and the problem that a dark spot generate|occur|produced. In addition, when a pixel division layer and/or a planarization layer are formed using the photosensitive composition obtained with 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, luminescence reliability is impaired. , and there was a problem that suppression of dark spots and high luminescence reliability were not compatible.

From the above background, generation|occurrence|production of a dark spot is suppressed and the organic electroluminescent display which has high light emission reliability was desired.

The organic EL display device of the present invention is an organic EL display device including a first electrode, a pixel division layer, a light emitting pixel, a second electrode, a planarization layer, and a substrate, wherein the pixel division layer and/or the planarization layer ( a) a black material having a nitrogen-containing heterocyclic structure, (b) a dispersing agent, and (c) a resin, wherein the (b) dispersing agent is a compound represented by the following general formula (1) and/or the following general formula It is characterized by containing the compound represented by (2).

In the general formula (1), X ¹ is a substituent directly bonded to a perylene ring, and represents -SO ₃ H, -SO ₃ M, -SO ₂ NHR ¹ or -CONHR ¹ . M represents Na, K or NH ₄ . R ¹ represents an organic group having an N,N-dialkylamino group at the terminal thereof. Z ¹ represents an atom or a substituent directly bonded to the perylene ring, and represents a hydrogen atom, an alkyl group, or an alkoxy group. n and m are integers, n represents 1 or 2, and n+m=10 is satisfied.

In the general formula (2), R ² and R ³ are the same as each other and represent a hydrogen atom, an aryl group having a substituent or a methyl group, X ² is a substituent directly bonded to a perylene ring and/or a benzene ring, -SO ₃ H , -SO ₃ M, -SO ₂ NHR ⁴ or -CONHR ⁴ is represented. M represents Na, K or NH ₄ . R ⁴ represents an organic group having an N,N-dialkylamino group at the terminal thereof. Z ² represents an atom or a 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.

ADVANTAGE OF THE INVENTION According to the organic electroluminescent display of this invention, the dark spot originating in the image development residue by a pigment aggregate is suppressed, and it becomes possible to acquire the outstanding light emission reliability.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing of the TFT board|substrate of an organic electroluminescent display apparatus which shows embodiment of this invention.
Fig. 2 is a schematic diagram showing a method of manufacturing an organic EL display device including a pixel division layer according to an embodiment.
Fig. 3 is a schematic diagram showing a method of manufacturing an organic EL display device including a pixel dividing layer and a planarization layer according to an embodiment.

Hereinafter, the present invention will be described in detail. Incidentally, in this specification, the numerical range expressed using "to" means the range which includes the numerical value described before and after "to" as a lower limit and an upper limit. In this specification, the pixel dividing layer means a pixel dividing layer for organic EL display devices, and the flattening layer means a planarizing layer for organic EL display devices. The organic EL display device refers to both an organic EL display device of a rigid type that cannot be bent and an organic EL display device of a flexible type that can be bent.

In addition, light-shielding property shows the degree of shielding the light of wavelength 380-780 nm which is a visible light region, and shows that the transmittance|permeability of light is low, so that light-shielding property is high. "CI" used for the name of the colorant is an abbreviation of the Color Index Generic Name, and for the colorant registered in the color index based on the color index published by The Society of Dyers and Colorists, the Color Index Generic Name is a pigment or Indicates the chemical structure or crystalline form of the dye. The organic pigment derivative encompasses a pigment derivative obtained by derivatizing an organic pigment powder as a raw material, but may not necessarily be a compound obtained through the form of an organic pigment powder in the synthesis reaction formula.

In this specification, the description of an alkali developing solution refers to an organic type alkali aqueous solution, unless there is particular notice. A weight average molecular weight (Mw) is the value which analyzed by the gel permeation chromatography which uses tetrahydrofuran as a carrier, and converted using the analytical curve by standard polystyrene.

The present invention is an organic EL display device comprising a first electrode, a pixel division layer, a light emitting pixel, a second electrode, a planarization layer and a substrate, wherein the pixel division layer and/or the planarization layer comprises (a) a nitrogen-containing heterocyclic ring A black material having a structure, (b) a dispersant, and (c) a resin, wherein the (b) dispersant is a compound represented by the following general formula (1) and/or a compound represented by the following general formula (2) It is an organic electroluminescent display containing a compound. By taking the said structure, generation|occurrence|production of a dark spot was suppressed, and it discovered that it became possible to make the outstanding light emission reliability compatible, and this invention was completed. A dark spot here means a particulate-form local non-light-emitting site|part non-uniformly arrange|positioned in a pixel at the time of driving of an organic electroluminescent display apparatus. The long diameter of the dark spot derived from the developing residue enlarges to the same or larger size compared to the long diameter of the developing residue to inhibit light emission. value goes down The luminescence reliability as used herein means that when the organic EL display device is continuously turned on, the light emitting area of the light emitting element is reduced with the lapse of the lighting time based on the initial lighting period (pixel shrink). It refers to a difficult thing, and 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 a perylene ring, and represents -SO ₃ H, -SO ₃ M, -SO ₂ NHR ¹ or -CONHR ¹ . M represents Na, K or NH ₄ . R ¹ represents an organic group having an N,N-dialkylamino group at the terminal thereof. Z ¹ represents an atom or a substituent directly bonded to the perylene ring, and represents a hydrogen atom, an alkyl group, or an alkoxy group. n and m are integers, n represents 1 or 2, and n+m=10 is satisfied.

In the general formula (2), R ² and R ³ are the same as each other and represent a hydrogen atom, an aryl group having a substituent or a methyl group, X ² is a substituent directly bonded to a perylene ring and/or a benzene ring, -SO ₃ H , -SO ₃ M, -SO ₂ NHR ⁴ or -CONHR ⁴ is represented. M represents Na, K or NH ₄ . R ⁴ represents an organic group having an N,N-dialkylamino group at the terminal thereof. Z ² represents an atom or a 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 organic electroluminescence display of this invention is equipped with a 1st electrode, a pixel division layer, a light emitting pixel, a 2nd electrode, a planarization layer, and a base material. Fig. 1 is a cross-sectional view of a TFT substrate in an organic EL display device that can be given as a specific example of the embodiment of the present invention.

On the surface of the substrate 6, bottom-gate or top-gate TFTs 1 (thin film transistors) are provided in a matrix form, covering the TFT 1 and the wiring 2 connected to the TFT 1 . In this state, the TFT insulating layer 3 is formed. Further, a planarization 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 planarization layer 4 . The second electrode 5 is patterned on the surface of the planarization layer 4 and is connected to the wiring 2 . The pixel division layer 8 is formed so as to surround the periphery of the pattern of the second electrode 5 . An opening is provided in the pixel dividing layer 8 , and a light emitting pixel 9 containing an organic EL light emitting material is formed in the opening, and the first electrode 10 is formed between the pixel dividing layer 8 and the light emitting pixel 9 . ) is formed to cover the When a voltage is directly applied to the light-emitting pixel portion after the TFT substrate having the above-described laminated structure is sealed under vacuum, it is possible to emit light as an organic EL display device.

The light emitting pixel 9 is one in which different types of pixels having emission peak wavelengths of the three primary colors of light, red, blue, and green, respectively, are arranged, or a light emitting pixel emitting white light is produced on the entire surface, and separately What combined red, blue, and green color filters may be sufficient as a lamination|stacking member of this. Usually, the peak wavelength in the red region is 560 to 700 nm, the peak wavelength in the blue region is 420 to 500 nm, and the peak wavelength in 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, in addition to the light emitting layer, a material obtained by further combining a hole transport layer and/or an electron transport layer can be suitably used.

A mask vapor deposition method is mentioned as a method of pattern-forming a light emitting pixel. A mask vapor deposition method is a method of vapor-depositing and patterning an organic compound using a vapor deposition mask, Specifically, the method of vapor-depositing by arrange|positioning the vapor deposition mask which made the desired pattern an opening part on the board|substrate side is mentioned. In order to obtain a high-precision deposition pattern, it is important to attach a deposition mask with high flatness to the substrate. Generally, a technique for applying tension to the deposition mask or a magnet placed on the back of the substrate to bring the deposition mask into close contact with the substrate. technology can be used. Examples of the method for manufacturing the deposition mask include etching, mechanical polishing, sandblasting, sintering, laser processing, and use of a photosensitive resin. It is preferable to use the electroforming method.

As the second electrode 5, for example, a conductive metal oxide such as zinc oxide, tin oxide, indium oxide, indium tin oxide (ITO), or zinc indium oxide (IZO) can be used, and among them, transparency and conductivity From this excellent point, ITO can be used suitably. As a method of pattern-forming ITO, first, after forming ITO into a film by sputtering method, a positive resist material for etching is pattern-formed by photolithography method, and a resist pattern is obtained on the ITO film|membrane. Next, only the ITO film of the resist pattern non-formation portion is removed with an etching solution having a liquid temperature of 20 to 60° C., and then the resist pattern is removed with a resist stripping solution having a liquid temperature of 20 to 60° C. ways to do it can be found. ITO as used herein encompasses so-called amorphous ITO. As the positive resist material for etching, a positive photosensitive composition containing an alkali-soluble novolac-based 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, and commercially available products include, for example, ITO-101N (manufactured by Kanto Chemical Co., Ltd.), “Sclean” (registered trademark) IS-2, copper IS-3 (above, all are made by Sasaki Chemical Yakuhin Co., Ltd.). As the resist stripping solution, an organic amine-based aqueous solution can be used, and as a commercially available product, for example, “Unlast” (registered trademark) M6, M6B, TN-1-5, M71-2 (above, all are Mitsuwaka) Junyaku Genkyusho).

As the 1st electrode 10, although a silver alloy film can be used suitably, for example, as long as it is a layer which can function as an electrode, you may contain what kind of substance. As a specific example of the first electrode 10, when the organic EL display device of the present invention is a bottom-emission organic EL display device described later, a layer containing aluminum can be preferably used from the viewpoint of excellent light reflectivity. In the case of a top emission type organic EL display device, from the viewpoint of excellent light transmittance, a layer containing a silver alloy containing silver/magnesium can be preferably used. The first electrode can be obtained by forming a film on 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 toward the substrate side through the substrate 6, and the light emitted through the first electrode It may be a top emission type organic EL display device that takes out to the opposite side of the substrate 6, and is not particularly limited. In the case of a top emission type organic EL display device, between the planarization layer 4 and the second electrode 5 , in order to increase the light extraction efficiency in one direction, a pattern-shaped metal reflection layer may be further provided. As a metal reflection layer, the electrically conductive film containing the silver alloy containing dissimilar metal elements, such as copper, gallium, and magnesium, is mentioned, for example.

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

On the other hand, when a flexible base material is used for the base material 6, it can be set as the organic electroluminescent display of the flexible type which can bend. As the flexible substrate, a substrate containing a polyimide resin having high flexibility and excellent mechanical strength can be suitably used. After imidizing polyamic acid by heating then, and converting into polyimide resin, the method of peeling a support body with a laser etc. is mentioned. Polyamic acid can be synthesized by reacting tetracarboxylic dianhydride and a diamine compound in an amide solvent such as N-methyl-2-pyrrolidone, and among them, a small coefficient of thermal expansion and excellent dimensional stability. In this, polyamic acid having a residue of an aromatic tetracarboxylic dianhydride and a residue of an aromatic diamine compound is preferable. Specific examples include polyamic acid having a residue of 3,3',4,4'-biphenyltetracarboxylic dianhydride and a residue of p-phenylenediamine. The thickness is 10-40 micrometers normally, compared with the case where the said alkali free glass is used, and can make the base material 6 thin.

The pixel division layer and/or the planarization layer with which the organic electroluminescence display of this invention is equipped contains (a) the black material which has a nitrogen-containing heterocyclic structure. The black material having a nitrogen-containing heterocyclic structure as used herein refers to (a-1) an organic pigment having at least one nitrogen-containing heterocyclic structure selected from an organic yellow pigment, an organic red pigment, and an organic orange pigment; -2) a pigment mixture containing at least one organic pigment having a nitrogen-containing heterocyclic structure selected from an organic blue pigment and an organic purple pigment, or (a-3) an organic black pigment having a nitrogen-containing heterocyclic structure . (a) By containing the black material which has a nitrogen-containing heterocyclic structure, a pixel division layer and/or a planarization layer can be blackened and light-shielding property can be provided.

(a) The component belonging to the black material having a nitrogen-containing heterocyclic structure is finally contained in the photosensitive composition for pattern-forming the pixel division layer and/or the planarization layer included in the organic EL display device of the present invention. It can be filled in the film|membrane of the pixel division layer and/or planarization layer obtained.

The black material having a (a) nitrogen-containing heterocyclic structure contained in the pixel division layer and/or the planarization layer included in the organic EL display device of the present invention improves light emission reliability, and has high alkali resistance to organic alkali aqueous solution. And it is preferable that it is an organic pigment which has high heat resistance with respect to heating. Alkali resistance as used herein is specifically, 25°C conditions under atmospheric pressure with respect to a 2.38 wt% tetramethylammonium hydroxide aqueous solution normally used as a developer when patterning a pixel dividing layer and a planarization layer in a developing step to be described later. refers to resistance under When the organic pigment is brought into contact with the developer through the binder, the more suppressed the generation of dissolved and/or decomposed products of the pigment is better. Heat resistance as used herein refers to suppression of generation of thermal decomposition products and/or sublimates generated by heating at 250° C. under atmospheric pressure/in a nitrogen atmosphere when thermosetting the pixel division layer and the planarization layer in the curing step described later. say what you can do The heat resistance temperature as a permanent film required for the pixel division layer and the planarization layer of the organic EL display device is 250 ° C. or higher, and the less the amount of outgas generated from the pixel division layer and the planarization layer under high-temperature conditions, the more the light emission reliability is improved. can

(a) As a specific example of the nitrogen-containing heterocyclic structure that the organic pigment contained in the black material having a nitrogen-containing heterocyclic structure has in its molecule, in addition to being able to improve the heat resistance and alkali resistance of the organic pigment itself, the general formula Since interaction with the compound represented by (1) and/or the compound represented by the said General formula (2) is strong, and a higher inhibitory effect of a developing residue is acquired, an imide ring, a benzimidazolone ring, a benzimi A dazole ring is mentioned especially preferably. It is preferable to contain the organic pigment which has any 1 type of nitrogen-containing heterocyclic structure among these.

In improving the light-shielding property of the pixel division layer and/or the planarization layer in the entire visible light region, three colors of (a-1) an organic yellow pigment, an organic red pigment, and (a-2) an organic blue pigment are contained. It is preferable to set it as the combination containing three colors of (a-1) organic yellow pigment, (a-2) organic blue pigment, and organic purple pigment. (a-1) When setting it as a combination containing three colors of an organic yellow pigment, an organic red pigment, and (a-2) organic blue pigment, content of the organic pigment of three colors in the total pigment in the photosensitive composition is , each preferably 20% by weight or more. The content of the organic blue pigment is more preferably 30.0% by weight or more in the total pigment, and the exposure sensitivity in the exposure step to be described later, in sufficiently blocking light in the wavelength region of 550 to 780 nm to increase the optical density described later. From a viewpoint of 50.0 weight% or less is more preferable.

On the other hand, when a combination containing three colors of (a-1) an organic yellow pigment, (a-2) an organic blue pigment, and an organic purple pigment is used, the organic pigment of the three colors among the total pigments in the photosensitive composition As for content, 20.0 weight% or more is preferable, respectively. In order to sufficiently block light in the wavelength region of 450 to 650 nm to increase the optical density to be described later, the content of the organic purple pigment is more preferably 30.0 wt% or more, and more preferably 50.0 wt% or less, based on all the pigments.

As an organic yellow pigment which has a nitrogen-containing heterocyclic structure, CI pigment yellow 120, 138, 139, 151, 175, 180, 185, 181, 192, 194 is mentioned, for example, These are single or multiple types. It does not matter if it contains Especially, since it is excellent in alkali resistance and heat resistance, the organic yellow pigment which has a benzimidazolone ring structure and does not have a halogen atom is preferable, CI Pigment Yellow 120, 151, 175, 180, 181, 192, 194 is preferred. C.I. Pigment Yellow 194 and/or C.I. Pigment Yellow 192 represented by the following structural formula (3) are more preferable.

As an organic orange pigment which has a nitrogen-containing heterocyclic structure, C.I. pigment orange 13, 36, 43, 61, 64, 71, 72 is mentioned, for example, You may contain these individually or multiple types. Especially, since it is excellent in alkali resistance and heat resistance, the organic orange pigment which has a perinone structure is preferable, and C.I. pigment orange 43 represented by following structural formula (4) is more preferable. From the viewpoint of luminescence reliability, it is preferable to use a trans-chain CI pigment orange 43 isomerically separated, and the residual amount of cis-isomer (CI Pigment Red 194), which is a by-product at the time of synthesis, is CI Pigment Orange 43 It is preferable that it is 5.0 weight% or less with respect to it.

Examples of the organic red pigment having a nitrogen-containing heterocyclic structure include CI Pigment Red 122, 123, 149, 179, 180, 189, 190, 202, 209, 254, 255, 264. These are single or multiple types. It does not matter if it contains Especially, it is preferable to have a perylene ring structure and an imide ring structure, without having in a structure the halogen atom which has high alkali resistance and heat resistance, and exerts a bad influence on light emission reliability. CI Pigment Red 123 represented by the following structural formula (5), CI Pigment Red 149 represented by the following structural formula (6), CI Pigment Red 179 represented by the following structural formula (7), and represented by the following structural formula (8) CI Pigment Red 190 is preferable.

As the organic blue pigment having a nitrogen-containing heterocyclic structure, for example, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:6, 16, 60, 64, 75, 79, 80 These are mentioned, You may contain these individually or multiple types. Especially, it is preferable to have a phthalocyanine structure or an indanthrone structure, without having in a structure the halogen atom which has high alkali resistance and heat resistance and which exerts a bad influence on light emission reliability. CI Pigment Blue 15:3, which is a β-type stable crystal of copper phthalocyanine, and CI Pigment Blue 15:6, which is an ε-type stable crystal of copper phthalocyanine, represented by the following structural formula (9), represented by the following structural formula (10), CI Pigment Blue 60 which is indanthrone blue (indanthrene blue) which has an indanthrone structure is preferable.

Incidentally, the copper phthalocyanine-based organic blue pigments such as CI Pigment Blue 15:3 and 15:6 referred to herein are all unsubstituted phthalocyanine-based organic blue pigments having a stable crystal structure, and are patented as one type of organic dye derivative. It is excellent in heat resistance and alkali resistance compared with the copper phthalocyanine derivative which has a sulfonic acid group described in Document 4. Especially, it is preferable to use the thing of 500 ppm or less of free copper as an impurity from a viewpoint of luminescent reliability, and 100 ppm or less is more preferable.

As an organic purple pigment which has a nitrogen-containing heterocyclic structure, C.I. Pigment Violet 19, 23, 29, 32, 37 is mentioned, for example, You may contain these individually or multiple types. Especially, it is preferable to have a perylene ring structure and/or a dioxazine structure, without having in a structure the halogen atom which has high alkali resistance and heat resistance, which has a bad influence on light emission reliability. C.I. Pigment Violet 29 and 37 are preferable, and C.I. Pigment Violet 29 represented by the following Structural Formula (11) from the viewpoint of dispersibility is more preferable.

(a) When the black material having a nitrogen-containing heterocyclic structure contains a combination containing three colors of (a-1) an organic yellow pigment, an organic red pigment, and (a-2) an organic blue pigment, organic yellow A pigment contains a benzimidazolone type organic yellow pigment, an organic blue pigment contains a phthalocyanine type organic blue pigment and/or an indanthrone type organic blue pigment, An organic red pigment contains a perylene type organic red pigment. It is best to do By adsorbing the compound represented by the general formula (1) and/or the compound represented by the general formula (2), which will be described later, a plurality of types of pigments having these different chemical structures can be suitably dispersed and stabilized.

(a-3) Examples of the organic black pigment having a nitrogen-containing heterocyclic structure include a perylene-based organic black pigment, a benzodifuranone-based organic black pigment having a lactam ring structure, and an azomethine azo-based organic black pigment. have. Especially, since it is excellent in heat resistance and light-shielding property, and interaction with the compound represented by the said General formula (1) and/or the compound represented by the said General formula (2) is strong, and adsorption target is high, nitrogen-containing A perylene-based organic black pigment having two benzimidazole rings in the molecule as a heterocycle is preferable. 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 and/or a general formula represented by the general formula (1) described below. By adsorbing the compound represented by (2), a plurality of types of pigments having these 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 the 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 planarization layer with which the organic electroluminescence display of this invention is equipped are other than the organic pigment which belongs to said (a-1), (a-2), or (a-3) component for fine adjustment of an optical characteristic. The pigment of may be contained, for example, CI pigment green 7, 36, 58, 59, CI pigment brown 25, 26, 28 other than a titanium nitride, a titanium oxynitride, etc. are mentioned.

(a) In obtaining sufficient light-shielding property in a visible light region, as for content of the black material which has a nitrogen-containing heterocyclic structure, 5 weight% or more is preferable in the total solid of the photosensitive composition, and 10 weight% or more is more preferable. Moreover, in ensuring the dispersion stability of the photosensitive composition and obtaining sufficient sensitivity and developability with respect to exposure, 70 weight% or less is preferable and 50 weight% or less is more preferable. The total solid content here means the value which divided the sum of the weight of all components other than the solvent contained in the photosensitive composition by the weight of the photosensitive composition, and multiplied by 100.

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

The average primary particle diameter here means the number average value of the primary particle diameter computed by the particle size measurement method using the image analysis type particle size distribution analyzer. A transmission electron microscope (TEM) can be used for imaging|photography of an image, and an average primary particle diameter can be computed from the image in which 100 or more primary particles of an organic pigment were image|photographed under the conditions of 50000 times magnification. When an organic pigment is not spherical, let the average value of the long diameter and a short diameter be a primary particle diameter. Image analysis type particle size distribution software Mac-View manufactured by Muntech Corporation can be used for image analysis.

Before performing the wet media dispersion treatment described later, when it is necessary to reduce the average primary particle diameter of the organic pigment in advance or to pulverize the coarse powder, an average of 1 by wet grinding treatment such as a solvent salt milling method You may adjust a tea particle diameter to a desired range. The solvent salt milling method refers to 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 high-viscosity paste state. The water-soluble inorganic salt may be a particulate matter that functions as a grinding material, and among them, sodium chloride, potassium chloride or potassium sulfate can be preferably used. It is preferable that the average primary particle diameter of a water-soluble inorganic salt is about 0.5-50 micrometers. Examples of the water-soluble organic solvent include organic solvents such as glycol-based solvents, ether-based solvents, and alcohol-based solvents. Among them, a glycol-based solvent is preferable, and specific examples thereof include ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, and triethylene glycol monoethyl. Ether, dipropylene glycol, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether are mentioned. After kneading, it is preferable to remove the water-soluble inorganic salt and the water-soluble solvent by repeatedly washing with water.

As a wet grinder for kneading, for example, a kneader (manufactured by Inoue Seisakusho Co., Ltd.) can be used, and the speed at which the organic pigment is refined by mechanical energy and coarsening by crystal growth are increased. What is necessary is just to appropriately set kneading conditions, such as the pigment concentration at the time of kneading|mixing, grinding|polishing material density|concentration, kneading|mixing speed, temperature, and time, so that it may become a desired average primary particle diameter, adjusting the balance of the advancing speed|rate. (a) It is preferable to knead-process independently each of the various organic pigments which the black material which has a nitrogen-containing heterocyclic structure contains.

(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 NMR, infrared absorption spectrum, ICP mass spectrometry, flight time By combining mass spectrometry (TOF-MS) and powder X-ray diffraction by CuKα ray, the chemical structure and its crystalline form can be identified. 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), which will be described later, can be further analyzed by combining liquid chromatography.

The pixel division layer and/or the planarization layer with which the organic electroluminescence display of this invention is equipped contains (b) a dispersing agent. (b) As a component belonging to a dispersing agent, it can divide roughly into (b-1) a non-polymer type dispersing agent, and (b-2) a polymer type dispersing agent.

(b-1) As a non-polymer type dispersing agent, the rosin type dispersing agent other than the organic pigment derivative which introduce|transduced the acidic functional group and/or basic functional group into the molecule|numerator of organic pigments, such as an organic pigment and dye, is mentioned, for example. The acidic functional group as used herein encompasses a group in the form of a salt.

On the other hand, as a polymer type dispersing agent (b-2), the polymer which has an acidic adsorption group and/or a basic adsorption group in a molecule|numerator is mentioned.

(b) As a mechanism of action of the dispersant, acid-base interaction and π-π electron interaction, hydrogen bonding, Van-der-Waals force, etc. are complexly involved, and a pigment dispersion solution described later In the wet media dispersion treatment performed when producing The effect of stabilizing the dispersed state is exerted by promoting the deaggregation of

(b) The component belonging to the dispersing agent is contained in the photosensitive composition for pattern-forming the pixel division layer and/or planarization layer included in the organic EL display device of the present invention, thereby finally obtained pixel division layer and/or planarization It can be filled in the membrane of the layer.

The pixel division layer and/or planarization layer with which the organic electroluminescent display of this invention is equipped is (b-1) a non-polymer type dispersing agent, Comprising: The compound represented by the following general formula (1) and/or the following general formula (2) contains a compound represented by There is).

In the general formula (1), X ¹ is a substituent directly bonded to a perylene ring, and represents -SO ₃ H, -SO ₃ M, -SO ₂ NHR ¹ or -CONHR ¹ . M represents Na, K or NH ₄ . R ¹ represents an organic group having an N,N-dialkylamino group at the terminal thereof. Z ¹ represents an atom or a substituent directly bonded to the perylene ring, and represents a hydrogen atom, an alkyl group, or an alkoxy group. n and m are integers, n represents 1 or 2, and n+m=10 is satisfied.

In the general formula (2), R ² and R ³ are the same as each other and represent a hydrogen atom, an aryl group having a substituent or a methyl group, X ² is a substituent directly bonded to a perylene ring and/or a benzene ring, -SO ₃ H , -SO ₃ M, -SO ₂ NHR ⁴ or -CONHR ⁴ is represented. M represents Na, K or NH ₄ . R ⁴ represents an organic group having an N,N-dialkylamino group at the terminal thereof. Z ² represents an atom or a 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 characteristics of the perylene-based dye derivative of the specific structure will be described in turn.

As a result of investigation by the present inventors, a specific acidic functional group or a basic functional group is directly bonded to a carbon atom constituting a perylene ring and/or a carbon atom constituting a benzene ring having an aryl group by a specific number of substituents in one molecule peryl having a structure It has been found that the lene-based dye derivative exhibits the following three characteristics, and the use of the perylene-based dye derivative for the pixel division layer and/or the planarization layer of the organic EL display device is particularly effective in solving the problem. found out to do

First, the perylene-based dye derivative of the specific structure (a) interacts with and adsorbs the black material having a nitrogen-containing heterocyclic structure to increase the polarity of the pigment surface, and promote refinement in the wet media dispersion treatment described later And also has a function of improving the dispersion stability after refinement|miniaturization. As a result, even when the photosensitive composition is stored for a long time, the effect of suppressing generation of pigment aggregates and color separation is exhibited.

Second, since the perylene-based dye derivative of the specific structure has high alkali resistance, the molecular structure of the perylene-based dye derivative itself is not destroyed even when it comes into contact with a high-concentration organic alkali aqueous solution in the developing step described later. A dispersed state can be maintained favorably without losing the function as a dispersing agent during the developing process. As a result, the effect which suppresses generation|occurrence|production of the image development residue on the ITO electrode resulting from a pigment aggregate is exhibited.

"Storing the photosensitive composition for a long period of time here" means leaving the photosensitive composition still in a sealed state for 30 days under atmospheric pressure / under light-shielding/25 degreeC ± 1 degreeC constant temperature.

Third, the perylene-based dye derivative of the specific structure has a rigid perylene ring as a parent skeleton, does not contain heavy metals or halogen atoms in its structure, and can express high heat resistance, Thermal decomposition can be suppressed, and corrosion of an electrode by migration of a heavy metal can be avoided.

In addition, when a highly polar functional group such as an acidic functional group or a basic functional group is directly bonded to a carbon constituting the perylene ring or a carbon constituting the benzene ring of the aryl group having a substituent, detachment of the highly polar group can be suppressed. Moreover, since the number of substituents per molecule is 1 or 2, sublimation of organic dye derivative itself can be suppressed. As a specific example of the desorption referred to herein, for example, desulfonation in which a sulfonic acid group introduced into the molecular structure by a derivatization treatment described later is removed from a parent skeleton residue derived from an organic pigment by a high temperature treatment is exemplified.

Because of these excellent characteristics, it is possible to suppress the sublimation of the perylene-based dye derivative itself of a specific structure and the generation of thermal decomposition products in the curing step described later, and as a result, the above-described effect of suppressing the development residue is obtained, and high It becomes possible to make light emission reliability compatible.

The preferable structure of the functional group of the perylene-based dye derivative having the specific structure is preferably determined by the acid or basicity of the adsorbing group in the structure when the polymer-type dispersant (b-2) described later is included.

In the case of containing a polymeric dispersant having a basic adsorbing group, the structure of the perylene-based dye derivative of the specific structure is excellent in the effect of suppressing the development residue, and in the general formulas (1) and (2), It is preferable that X<^1> and X<^2> are an acidic functional group or its salt, ie, it is preferable that it is -SO ₃ H or -SO ₃ M, It is more preferable that it is _{-SO 3 H.} In the case of -SO ₃ M, among them, in order to improve luminescence reliability, M is preferably _{NH 4 .} You may contain these compounds individually or multiple types. In addition, _{the notation of -SO 3} H or -SO ₃ M in this specification is a hydrogen atom, a sodium ion, a potassium ion, or an ammonium ion in a sulfonic acid group in the photosensitive composition, and X ¹ and X ² are -SO ₃ ^It _{includes cases where -SO 3} ^- is in a bonded state with other constituents, such as the case of being in the state of an anion represented by - and forming an ionic bond with the polymer-type dispersing agent (b-2) described later. In the general formula (1), X ¹ may be directly bonded to any carbon among carbons at positions 1, 2, 5, 6, 7, 8, 9, 10, 11, and 12 constituting the perylene ring. indicates. In addition, in the said General formula (2), X<^2> is the carbon which comprises the 1, 2, 5, 6, 7, 8, 11, 12 position which comprises a perylene ring, and the carbon which comprises the benzene ring of the aryl group which has a substituent. It shows that it may couple|bond directly with any carbon among them. Among them, in order to obtain higher luminescence reliability, it is preferable that X ² is directly bonded to any carbon at positions 1, 2, 5, 6, 7, 8, 11, and 12 constituting the perylene ring. In addition, the notation method of each structural formula using [] in the general formulas (1) and (2) is based on the technical common knowledge of those skilled in the art, the number of introduction of each functional group per molecule of the organic dye derivative is the same, and each functional group is bonded It indicates that a mixture of a plurality of types of compounds having different positions of carbon to be used may be used. ^{For example, 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 in the general formula (1), perylene-3,4- It indicates that a mixture of perylene-3,4-dicarboxyimide-9-sulfonic acid, which is a monosulfonated product of dicarboxyimide, and perylene-3,4-dicarboxyimide-8-sulfonic acid may be used. In addition, taking the unsubstituted perylene-3,4-dicarboxyimide represented by the following structural formula (14), which is a part of the skeleton constituting the chemical structure of the perylene-based pigment derivative of the specific structure, as an example, each constituting the perylene ring Indicates the position number of the carbon.

In the general formula (2), R ² and R ³ are preferably an aryl group or a methyl group having a substituent from the viewpoint of improving the light emission reliability. As used herein, the aryl group or methyl group having a substituent is an aryl group having a substituent or a methyl group, or either group. The substituent here means a substituent other than ^{X 2 couple|} bonded with the carbon which comprises the benzene ring which an aryl group has. In addition, the aryl group here refers to the aryl group which has at least a benzene ring, and does not cover heteroaryl groups, such as a pyridyl group which has a nitrogen-containing heterocyclic structure. In addition, the aliphatic group couple|bonded with the aromatic ring which has a substituent, such as a 4-methoxyphenylmethyl group, is not covered. That is, for example, the organic dye derivative which has the molecular structure of CI pigment black 32 as a residue after a derivatization process is not contained in the element which comprises this 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, and as a more specific substitution form, from the viewpoint of improving luminescence reliability, 4 -Ethoxyphenyl group, 3,5-dimethylphenyl group, 4-methoxyphenyl group and 4-(phenylazo)phenyl group are preferable.

Moreover, in the said General formula (1) and the said General formula (2), when Z<^1> and Z<^2> improve the heat resistance of the perylene-type pigment derivative itself of a specific structure, it is preferable that both are hydrogen atoms.

When the polymer-type dispersing agent (b-2) described later contains a polymer-type dispersing agent having an acidic adsorption group as an adsorbing group, from the viewpoint of excellent effect of suppressing development residues, in the compound represented by the general formula (1), In the said General formula (1) ^{, it is preferable that X<1>} is a basic functional group. That is, -SO ₂ NHR ¹ or -CONHR ¹ is preferable. From the viewpoint of the light emission reliability, it is more preferable that -CONHR ^1.

On the other hand, in the compound represented by the said General formula (2) ^{, it is preferable that X<2>} is a basic functional group in General formula (2). That is, it is preferable that it is -SO ₂ NHR ⁴ or -CONHR ^{4 .} From the viewpoint of the light emission reliability, it is more preferable that -CONHR ^{4. As R 1} and R ⁴ which are organic groups having an N,N-dialkylamino group at the terminal, for example, 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, N,N-diethylaminobutyl group, N,N- Dipropylaminomethyl group, N,N-dipropylaminoethyl group, N,N-dipropylaminopropyl group, N,N-dipropylaminobutyl group, N,N-dibutylaminomethyl group, N,N-dibutylamino group an ethyl group, a N,N-dibutylaminopropyl group, and a N,N-dibutylaminobutyl group are mentioned.

Among them, an organic group or N,N-diethyl group having a terminal N,N-dimethylamino group or N,N-diethyl group from the viewpoint of a strong adsorption action with the polymer-type dispersant (b-2) described later and an excellent effect of suppressing development residues. An organic group having an amino group at the terminal is preferred. N,N-dimethylaminomethyl group, N,N-dimethylaminoethyl group, N,N-dimethylaminopropyl group, N,N-dimethylaminobutyl group, N,N-diethylaminomethyl group, N,N-diethylamino group An ethyl group, a N,N-diethylaminopropyl group, and a N,N-diethylaminobutyl group are preferable.

Specific examples of the compound in which X ¹ is a basic functional group include preferably compounds represented by the following structural formulas (15) and (16), and ^{examples of the compound in the case where X 2} is a basic functional group include, for example, , compounds represented by the following structural formulas (17) to (21) are preferably mentioned.

Even if the perylene-based dye derivative of the specific structure has an acidic functional group or a basic functional group, (a) the effect of suppressing the development residue derived from the black material having a nitrogen-containing heterocyclic structure can be obtained, but the ITO surface It is preferable that the perylene-type pigment derivative of a specific structure has an acidic functional group in making interaction smaller and improving the effect which suppresses a dark spot. Especially, it is more preferable to have a _{sulfonic acid group (-SO 3} H) as an acidic functional group from the point which is excellent in the effect of improving dispersion stability and suppressing image development residue. It is preferable to contain the compound represented by the following general formula (22) and/or the compound represented by the following general formula (23) as a perylene type pigment derivative of the specific structure which has a sulfonic acid group. It is more preferable to use together the compound represented by the following general formula (22) and the compound represented by the following general formula (23) at the point which is excellent in the effect of suppressing a dispersion stabilization effect and image development residue. In addition, in the following general formula (22), the sulfonic acid group (-SO ₃ H) is any carbon among the carbons at positions 1, 2, 5, 6, 7, 8, 9, 10, 11, and 12 constituting the perylene ring. may be directly combined with In the following general formula (23), the sulfonic acid group is at positions 1, 2, 5, 6, 7, 8, 11, 12 constituting the perylene ring, and among carbons constituting the benzene ring of the aryl group having a substituent, You may couple|bond directly with any carbon.

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

In the general formula (23), R ⁵ and R ⁶ are the same as each other and represent a hydrogen atom, an aryl group having a substituent, or a methyl group. X ⁴ _{represents -SO 3} H directly bonded to the perylene ring and/or the 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 the general formula (23), R ⁵ and R ⁶ are preferably an aryl group or a methyl group having a substituent from the viewpoint of heat resistance. As used herein, the aryl group or methyl group having a substituent is an aryl group having a substituent or a methyl group, or either group. As an aryl group which has a substituent, in the said general formula (2) ^{similarly to the illustration for R<2>} and R<^3> , for example, an ethoxyphenyl group, a dimethylphenyl group, a methoxyphenyl group, a phenylazophenyl group, a diisopropylphenyl group can be heard As a more specific substitution form, a 4-ethoxyphenyl group, 3, 5- dimethylphenyl group, 4-methoxyphenyl group, and 4-(phenylazo)phenyl group are preferable from a 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) is preferably exemplified. Moreover, as a compound represented by the said General formula (23), the compound represented by following structural formula (25) is mentioned preferably, for example. You may contain these individually or multiple types.

(b) The perylene-based dye derivative of a specific structure, which is a component belonging to a dispersing agent, is a compound in which the ^{number of substituents n of X 1} is 1 or 2 in the general formula (1), but even if it further contains a compound in which the number of substituents n is 3 or more Does not matter. However, in the case of containing a compound having 3 or more substituents n, in the general formula (1), the average number of substituents with the compound in which the number of substituents n of ^{X 1 is 1 or 2 is 1.0 to 2.0 in order to obtain high luminescence reliability.} It is preferable to be within the range of For example, when the compound whose number of substituents n is 1 and the compound whose number of substituents n is 3 are contained in equimolar amounts, the average number of substituents is set to 2.0. In the general formula (2) ^{, when the compound having the number of substituents p of X 2} is 1 or 2 and the compound having the number of substituents p of 3 or more are used in combination and contained, the average number of substituents is within the range of 1.0 to 2.0. It is preferable to do

As a method of synthesizing a perylene-based dye derivative having a specific structure contained in the pixel division layer and/or the planarization layer included in the organic EL display device of the present invention, for example, industrially available perylene-3,4- Dicarboxyimide, perylene-3,4-dicarboxyimide carboxylic acid, CI Pigment Red 123, CI Pigment Red 149, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 190, CI Pigment Ment Violet 29, N,N'-bis(2,6-diisopropylphenyl)-3,4,9,10-perylenetetracarboxylic acid diimide (hereinafter, may be referred to as "perylene orange") .) or a compound having a perylene ring structure as a starting material, and a method of performing various derivatization treatments described later so as to have a desired chemical structure.

In the general formula (1), as a method for synthesizing the compound having the above-described acidic functional group or a salt thereof, for example, 10 to 40% of perylene-3,4-dicarboxyimide, fuming sulfuric acid, 70 to 100% It is dissolved in concentrated sulfuric acid, chlorosulfonic acid, or a mixture thereof, and stirred for 1 to 6 hours while heating at 40 to 90°C. Thereafter, the red solid obtained by pouring in a large amount of water or ice water with a weight of 100 times or more with respect to the used perylene-3,4-dicarboxyimide and precipitating it is washed with water and filtered, washed with acetone, dried, and dried By performing a grinding|pulverization process, the ^{compound whose X<1>} is -SO ₃ H in the said General formula (1) can be obtained.

In addition, by neutralizing 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 into a sodium salt (-SO ₃ Na), a potassium salt (-SO ₃ K ) or an ammonium salt (-SO ₃ NH ₄ ), that is, a ^{compound in which X 1} is —SO ₃ M can be obtained. _{Moreover, the mixing ratio of -SO 3} H and -SO ₃ M can also be controlled by adjusting the quantity of an inorganic basic chemical|medical solution.

As a method for synthesizing the compound having the above-described basic functional group in the general formula (1), 10 to 40% fuming sulfuric acid, 70 to 100% concentrated sulfuric acid, chlorosulfonic acid, or a mixture thereof, perylene-3,4-dicarboxyimide dissolve in Subsequently, 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-dicarboxyimidesulfonyl chloride. Thereafter, in the presence of a catalyst, it is reacted with a predetermined amount of N,N-dialkylaminoalkylamine to obtain a sulfonamide, and a large amount of water or The dark red solid obtained by pouring into ice water and precipitating it is washed with water and filtered. Furthermore, by washing with acetone, drying after removing the catalyst, and performing dry grinding treatment, in the general formula (1), a compound in which ^{X 1} is —SO ₂ NHR ^{1 can be obtained.}

Further, perylene-3,4-dicarboxyimide carboxylic acid is dissolved in a methylene chloride solvent, thionyl chloride is added and stirred to obtain perylene-3,4-dicarboxyimide carbonyl chloride, followed by chloride The methylene solvent and unreacted thionyl chloride are removed under reduced pressure. Thereafter, the carboxamide is obtained by reacting with a predetermined amount of N,N-dialkylaminoalkylamines in the presence of a catalyst, and the obtained dark red solid is washed with water and filtered. Further, in the general formula (1), a compound in which ^{X 1} is -CONHR ¹ can be obtained by washing with acetone, drying after removing the catalyst, and performing dry grinding treatment. Examples of the catalyst for accelerating the reaction for obtaining the above-described sulfonamide or carboxamide include amine catalysts such as trimethylamine and triethylamine.

Examples of the N,N-dialkylaminoalkylamines include N,N-dimethylaminomethylamine, N,N-dimethylaminoethylamine, N,N-dimethylaminopropylamine, and 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, and N,N-dibutylaminobutylamine are mentioned. By using these individually or in mixture of multiple types, various perylene-type pigment derivatives which have a desired basic functional group can be synthesize|combined.

On the other hand, instead of the above perylene-3,4-dicarboxyimide or perylene-3,4-dicarboxyimide carboxylic acid, CI Pigment Red 123, CI Pigment Red 149, CI Pigment Red 178, CI Pig Ment Red 179, CI Pigment Red 190, CI Pigment Violet 29, Perylene Orange, or a compound having a perylene ring thereof as a starting material, the same as the synthesis method of the compound represented by the above-mentioned general formula (1) By performing a derivatization treatment according to the reaction scheme, compounds having various functional groups represented by the general formula (2) can be obtained.

For example, by derivatizing CI Pigment Red 123 represented by the structural formula (5) as a starting material, a ^{compound in which R 2} and R ^{3 in} the general formula (2) is a 4-ethoxyphenyl group can be obtained. have. By derivatizing CI pigment red 149 represented by the structural formula (6) as a starting material, in the general formula (2) ^{, a compound in which R 2} and R ³ is a 3,5-dimethylphenyl group can be obtained. ^{The compound in which R<2>} and R<^3> is a 4-(phenylazo) phenyl group in the said General formula (2) can be obtained by derivatizing using CI Pigment Red 178 as a starting material.

^{The compound in which R<2>} and R<^3> is a methyl group in the said general formula (2) can be obtained by derivatization-processing using CI pigment red 179 represented by the said structural formula (7) as a starting material. By derivatizing CI Pigment Red 190 represented by the structural formula (8) as a starting material, in the general formula (2) ^{, a compound in which R 2} and R ³ is a 4-methoxyphenyl group can be obtained. ^{The compound in which R<2>} and R<^3> is a hydrogen atom in the said general formula (2) can be obtained by derivatizing using CI pigment violet 29 represented by the said structural formula (11) as a starting material. By derivatizing perylene orange as a starting material, in the general formula (2) ^{, a compound in which R 2} and R ³ is a 2,6-diisopropylphenyl group can be obtained.

The perylene-based dye derivative having a specific structure obtained by the above method is preferably purified by itself to remove impurities in advance in order to obtain higher luminescence reliability. As the residual amount of ionic impurities derived from the chemical solution used for the derivatization treatment, each content of sulfate ion (SO ₄ ^2- ), sulfite ion (SO ₃ ⁻ ), and chlorine ion (Cl ⁻ ) is preferably 100 ppm or less, , more preferably 50 ppm or less. The residual amount of these ionic impurities can be measured by ion chromatography, and the removal rate may be increased by dispersing a powder of a perylene-based dye derivative having a specific structure in deionized water using a wet media disperser to form a slurry, or ion exchange resin The removal rate may be further improved by adding and stirring.

For the perylene-based dye derivative having a specific structure, in order to obtain a higher dispersion stabilization effect while avoiding residual coarse particles of their own in the pigment dispersion, it is preferable to use a dry powder that has been sufficiently dry pulverized. And it is preferable that the average primary particle diameter is 150 nm or less, and it is more preferable that it is 100 nm or less. The average primary particle diameter of the perylene-based dye derivative having a specific structure can be evaluated in the same manner as the black material having a nitrogen-containing heterocyclic structure (a) described above. In addition, in the case of containing impurities including sulfur-containing compounds derived from the chemical solution used for the derivatization treatment and salts of amine catalysts, from the viewpoint of luminescence reliability, it is preferable to dry powder after removing as much as possible by repeatedly washing with water. .

Although there is no restriction|limiting in particular about the method of making the perylene-type pigment derivative of the said specific structure contain in the photosensitive composition, Specific examples are illustrated below about a preferable method.

In the presence of a perylene-based pigment derivative of a specific structure, (a) among organic pigments belonging to a black material having a nitrogen-containing heterocyclic structure, at least one organic pigment is kneaded to adsorb/support it on the pigment surface in advance, followed by drying and ash By pulverization, a dry powdery organic dye derivative-treated secondary processed pigment is once prepared. Next, the method of manufacturing a photosensitive composition using the pigment dispersion liquid obtained by performing a wet media dispersion process collectively with other organic pigments is mentioned. Alternatively, in the presence of a perylene-based dye derivative having a specific structure, (a) a method for producing a photosensitive composition using a pigment dispersion obtained by collectively performing wet media dispersion treatment of a black material having a nitrogen-containing heterocyclic structure is mentioned. .

When content of the perylene-type pigment derivative of a specific structure improves dispersion stability and suppresses generation|occurrence|production of a pigment aggregate, 0.5 weight% or more is preferable with respect to the black material which has (a) nitrogen-containing heterocyclic structure. On the other hand, when suppressing the increase of interaction with the ITO electrode surface and suppressing generation|occurrence|production of the image development residue of the perylene-type pigment derivative itself of a specific structure, 10.0 weight% or less is preferable.

In addition, within the scope of not adversely affecting the luminescence reliability, an organic dye derivative other than the perylene-based dye derivative having the above specific structure or a compound having the same synergistic effect as it is used in combination to suppress dispersion stability and development residues. You can control the effect. 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, acid functional groups or basic The 1,3,5-triazine type compound which has a functional group is mentioned. (a) the black material having a nitrogen-containing heterocyclic structure comprises (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, (a- 2) In the case of a pigment mixture containing an organic blue pigment having a nitrogen-containing heterocyclic structure, it is preferable to use an anthraquinone-based pigment derivative in combination, for example, a compound represented by the following structural formula (56). can

(b-1) As a component belonging to a non-polymer type dispersing agent, you may contain a rosin type dispersing agent. The rosin-based dispersant exhibits the effect of improving the wettability of the pigment surface to the dispersion medium, and can be used as an auxiliary agent for further enhancing the dispersion stabilization effect of the perylene-based pigment derivative having a specific structure. Examples of the rosin-based dispersant include a rosin monomer, a rosin dimer (rosin dimer), a maleic acid-modified rosin, a fumaric acid-modified rosin, or a mixture thereof. Among them, a rosin-based dispersant containing a rosin monomer and a rosin dimer having at least one carboxyl group in the molecule and having a solid content acid value in the range of 100 to 300 (mgKOH/g) is preferable, and as a specific example of a commercial product, "Poly-Pale Partially" Dimerized Rosin" (registered trademark), "Dymerex Polymerized Rosin" (registered trademark) (above, all manufactured by EASTMAN CHEMICAL), Ardime R-95, Fine Crystal KR140 (above, all manufactured by Arakawa Chemical Industries, Ltd.) can be heard

It is preferable that the photosensitive composition for forming the pixel division layer and/or planarization layer with which the organic electroluminescence display of this invention is equipped further contains (b-2) a polymer type dispersing agent. (b-2) As a polymer type dispersing agent, the dispersing agent which has a polymer chain containing various resin systems as a main chain can be used. For example, an acrylic dispersing agent, a polyoxyalkylene type dispersing agent (polyether type dispersing agent), a polyurethane type dispersing agent, a polyester type dispersing agent, and a polyamine type dispersing agent are mentioned. Among them, in order to achieve both the solvent affinity related to dispersion stability and the moderate hydrophilicity related to developability, an acrylic dispersant and a polyoxyalkylene dispersant are preferable. In addition to the main chain, a polymeric dispersant having a basic adsorbing group and/or an acidic adsorbing group having high adsorption capacity to the perylene-based dye derivative of the specific structure is preferable.

(b-2) The weight average molecular weight (Mw) of the polymeric dispersant is preferably 1,000 or more, and more preferably 2,000 or more, in order to enhance the steric repulsion effect and sufficiently obtain the dispersion stabilization effect. Moreover, in order to suppress the raise of the thixotropic property of a photosensitive composition, 50,000 or less are preferable and 30,000 or less are more preferable.

(b-2) Examples of the basic adsorbing group of the polymeric dispersant include, for example, a tertiary amino group or a salt thereof, a quaternary ammonium base group, and an organic group having a heterocycle such as an isocyanurate ring at the molecular terminal thereof. . Especially, a tertiary amino group is more preferable at the point which is excellent in a dispersion stabilization effect and the effect which suppresses the image development residue on ITO is high.

Examples of the polymeric dispersant having a tertiary amino group include a copolymer of an ethylenically unsaturated monomer having a dialkylamino group and other ethylenically unsaturated monomers when the main chain is an acrylic polymer chain. As a specific example, the dispersing agent which has a structural unit represented by the following general formula (26) can be used preferably. Examples of the ethylenically unsaturated monomer having a dialkylamino group include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and diethylaminopropyl (meth)acrylate. and acrylates.

In the 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 an alkyl group having 1 to 4 carbon atoms.

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

(b-2) Examples of the acidic adsorption group of the polymeric dispersant include a phosphoric acid group, a sulfonic acid group, a carboxylic acid group, and a phenolic hydroxyl group. Among them, the dispersion stabilization effect is excellent, and the development residue on the ITO is removed. Since it is excellent in the inhibitory effect, a phosphoric acid group is preferable, and it is preferable to contain the polymer type dispersing agent which has a phosphoric acid group at least.

Specific examples of the polymeric dispersant having a phosphoric acid group include, for example, a copolymer of an ethylenically unsaturated monomer having a phosphoric acid group and other ethylenically unsaturated monomers when the main chain is an acrylic polymer chain. As a specific example, the dispersing agent which has a structural unit represented by the following general formula (27) can be used preferably.

In the 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 to 10.

Examples of the ethylenically unsaturated monomer having a phosphoric acid group include 2-methacryloyloxyethyl acid phosphate, acid phosphoxyethyl (meth)acrylate, acid phosphoxypropyl (meth)acrylate, acid phosphoxypolyoxypropylene Glycol (meth)acrylate is mentioned.

As other ethylenically unsaturated monomers for use in the copolymerization with the ethylenically unsaturated monomer having a dialkylamino group or an ethylenically unsaturated monomer having a phosphoric acid group, for example, benzyl (meth) acrylate, styrene, (meth) acrylic acid methyl, (meth)ethyl acrylate, (meth)propyl acrylate, (meth)acrylate n-butyl, (meth)acrylic acid polyethylene glycol, (meth)acrylic acid polypropylene glycol, and (meth)acrylic acid polyethylene/polypropylene glycol are mentioned. . It is preferable that the dispersant has a benzyl group in the side chain, and the use of benzyl (meth)acrylate is preferable from the viewpoint of high affinity with the perylene-based dye derivative of the specific structure, excellent dispersibility, and improved heat resistance. .

(b-2) A commercial item may be used as a polymer type dispersing agent, As a polymer type dispersing agent which has only an acidic adsorbent, For example, "DISPERBYK" (trademark)-102, 110, 111, 118, 2096, BYK-P104, P105, "Solsperse" (trademark) 3000, 21000, 36000, 36600 (above, all are made by Lubrizol), and Ajisper PA111 (made by Ajinomoto Fine Techno) are mentioned. These dispersants can be used individually or in mixture of multiple types.

As the polymer type dispersant having only basic adsorbent, for example, "DISPERBYK" (registered trademark) -161, 162, 2163, 164, 2164, 167, 168, 2000, 2050, 2150, 2155, 9075, 9077, BYK-LPN6919 , BYK-LPN21116, BYK-LPN21234 (above, all made by Bic Chemie), EFKA-4015, 4020, 4046, 4047, 4050, 4055, 4060, 4080, 4300, 4330, 4340, 4400, 4401, 4402, 4403, 4800 (above, all are made by BASF), "Solsperse" (trademark) 13240, 13940, 20000, 24000, 71000, 76500 (above, all are made by Lubrizol) are mentioned. These dispersants may be used alone or in combination.

As a polymer type dispersing agent which has an acidic adsorption group and a basic adsorption group, "DISPERBYK" (registered trademark)-142, 145, 2001, 2010, 2020, 2025 (above, all made by Big Chemi company), "SOLSPERSE" (registered trademark), for example ) 9000, 11200, 13650, 24000SC, 24000GR, 32000, 32500, 32550, 33000, 34750, 35100, 35200, 37500, 39000, 56000 (manufactured by Lubrizol), Azisper PB821, PB822, PB824, PB881, PB883 (or above) , all of which are manufactured by Ajinomoto Fine Techno Co., Ltd.).

The pixel division layer and/or the planarization layer with which the organic electroluminescence display of this invention is equipped contains (c) resin. The (c) resin as used herein is a so-called binder (binder) in the pixel division layer and/or the planarization layer, which immobilizes (a) the black material having a nitrogen-containing heterocyclic structure and (b) the dispersant; , refers to a component having a film-forming function under conditions under room temperature/atmospheric pressure.

(c) The component belonging to the resin is contained in the photosensitive composition for pattern-forming the pixel division layer and/or planarization layer included in the organic EL display device of the present invention, thereby finally obtaining the pixel division layer and/or planarization It can be filled in the membrane of the layer.

The photosensitive composition for forming the pixel division layer and/or the planarization layer reduces alkali solubility of the film of the exposed portion by pattern exposure through a negative exposure mask, and removes the film on the unexposed portion with an alkali developer to form a pattern , a negative photosensitive composition used for negative photolithography may be used. Alternatively, by pattern exposure through a positive type exposure mask, the alkali solubility of the film of the exposed portion is relatively high compared to the alkali solubility of the film of the unexposed portion, and the film of the exposed portion is removed with an alkali developer to form a pattern, a so-called positive type. The positive photosensitive composition used for the photolithography of may be sufficient. It is preferable that it is a negative photosensitive composition at the point from which high light-shielding property is acquired, maintaining favorable exposure sensitivity and pattern workability.

The pixel division layer and/or the planarization layer with which the organic electroluminescence display of this invention is equipped contains (c) resin. Moreover, in order to provide negative type or positive type photosensitivity to the photosensitive composition used in order to pattern-form the pixel division layer and/or planarization layer mentioned later, it is preferable to contain alkali-soluble resin. The alkali-soluble resin refers to a resin having a hydroxyl group, a carboxyl group and/or a sulfonic acid group as an alkali-soluble group, an acid value of 10 mgKOH/g or more, and a weight average molecular weight (Mw) of 1,000 or more and 150,000 or less. Incidentally, the cured product of the alkali-soluble resin contained in the photosensitive composition used for pattern-forming the pixel division layer and/or the planarization layer belongs to the resin (c) constituting the pixel division layer and/or the planarization layer finally obtained. become an ingredient

As alkali-soluble resin, For example, alkali-soluble cardo resin, alkali-soluble acrylic resin, alkali-soluble novolak resin, alkali-soluble polyimide resin, alkali-soluble polyimide precursor, alkali-soluble polybenzoxazole resin, alkali-soluble polybenzo An oxazole precursor, an alkali-soluble polyamide resin, and alkali-soluble siloxane resin are mentioned. Since these alkali-soluble resins eventually become one of the components constituting the resin (c), it is preferable that the amount of outgassing (gas generation) under high temperature can be reduced especially in improving the luminescence reliability.

When the photosensitive composition used in order to pattern-form a pixel dividing layer and/or planarization layer has negative photosensitivity, as alkali-soluble resin, from a viewpoint of making pattern processability and light emission reliability compatible, alkali-soluble cardo resin and/or It is preferable to contain alkali-soluble polyimide resin. Moreover, in improving light emission reliability, it is more preferable to contain alkali-soluble polyimide resin at least. When using alkali-soluble cardo resin and alkali-soluble polyimide resin together, it is preferable that content of alkali-soluble polyimide resin exceeds content of alkali-soluble cardo resin from a viewpoint of light emission reliability and dispersion stability.

On the other hand, when the photosensitive composition used to pattern-form the pixel division layer and/or the planarization layer has positive photosensitivity, from the viewpoint of achieving both pattern workability and luminescence reliability, alkali-soluble polyimide resin and alkali-soluble polyimide precursor It is preferable to contain at least 1 sort(s) of alkali-soluble resin chosen from alkali-soluble polybenzoxazole resin, alkali-soluble polybenzoxazole precursor, and alkali-soluble siloxane resin. Moreover, it is more preferable to contain alkali-soluble polyimide resin and/or alkali-soluble polyimide precursor from a viewpoint of improving the exposure sensitivity and light emission reliability in the exposure process mentioned later.

The alkali-soluble cardo resin refers to an alkali-soluble resin having a cardo skeleton, and the cardo skeleton refers to a skeleton in which two aromatic groups are connected by a single bond to a quaternary carbon atom that is a ring carbon atom constituting the cyclic structure.

Preferred specific examples of alkali-soluble cardo resin include alkali-soluble cardo resin having a fluorene skeleton and having a structural unit represented by the following general formula (28) and a radically polymerizable group, 1-phenyl-2,3-dihydro- An alkali-soluble cardo resin having a 1H-indene skeleton and a structural unit represented by the following general formula (29) and a radically polymerizable group, an N-phenylphenolphthalein skeleton having a structural unit represented by the following general formula (30); Alkali-soluble cardo resin which has a radically polymerizable group is mentioned.

In the general formulas (28), (29) and (30), Q ¹ to Q ⁸ each may be the same or different, and represent a substituent directly bonded to a benzene ring, and an alkyl group having 1 to 6 carbon atoms or 1 carbon number to 6 alkoxy group, a to h are integers, and 1 or 2.

In improving developability, 10 mgKOH/g or more is preferable, and, as for the acid value of alkali-soluble cardo resin, 50 mgKOH/g or more is more preferable. On the other hand, in suppressing peeling of the pattern edge of a pixel division layer and/or a planarization layer, 300 mgKOH/g or less is preferable, and 250 mgKOH/g or less is more preferable.

From a viewpoint of suppressing peeling of a pattern edge, 2,000 or more are preferable and, as for the weight average molecular weight of alkali-soluble cardo resin, 3,000 or more are more preferable. On the other hand, from a viewpoint of the gelation suppression at the time of superposition|polymerization of alkali-soluble cardo resin, 50,000 or less are preferable and 30,000 or less are more preferable.

In addition, as alkali-soluble cardo resin, a commercial item can also be used, For example, "ADEKA ARKLS" (trademark) WR-301 (made by ADEKA Corporation), "Ogsol" (trademark) CR-TR1, CR-TR2, CR-TR3, CR-TR4, CR-TR5, CR-TR6 (above, all are Osaka Gas Chemicals Co., Ltd. product) are mentioned.

As alkali-soluble polyimide resin, it is preferable to contain alkali-soluble polyimide resin which has a structural unit represented by following General formula (31).

In the general formula (31), R ²¹ represents a 4- to 10-valent organic group. R ²² represents a 2 to 8 valent organic group. R ²³ and R ²⁴ each independently represent a phenolic hydroxyl group, a sulfonic acid group, or a thiol group. i and j each independently represent the range of 0-6.

In the general formula (31), R ²¹ -(R ²³ ) _i represents a residue of an acid dianhydride. R ²¹ is preferably an organic group having an aromatic ring or a cyclic aliphatic group and having 5 to 40 carbon atoms.

As the acid dianhydride, for example, pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid Dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride tetracarboxylic dianhydride having an aromatic ring such as water, tetracarboxylic dianhydride having an aliphatic group such as butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride; tetracarboxylic dianhydride having a cyclic aliphatic group such as bicyclo[2.2.2]oct-7-ene-tetracarboxylic dianhydride and bicyclo[2.2.2]octanetetracarboxylic dianhydride; .

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

Examples of the diamine 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) C)phenyl]hexafluoropropane, bis[4-(3-aminophenoxy)phenyl]sulfone, 9,9-bis(4-aminophenyl)fluorene, diaminodiphenyl ether, diaminodiphenylsulfone, diamine having an aromatic ring, such as diaminodiphenylmethane, diaminodiphenylpropane, diaminodiphenylhexafluoropropane, diaminodiphenylthioether, benzidine, and 2,2'-bistrifluorobenzidine; and diamines having a cyclic aliphatic group such as 5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane.

It is preferable that alkali-soluble polyimide resin which has a structural unit represented by General formula (31) has a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and/or a thiol group in the main chain terminal. By sealing the terminal of the polyimide resin using a terminal blocker having a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group and/or a thiol group, these groups can be introduced into the main chain terminal. As a terminal blocker, a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound is mentioned, for example.

From a developable viewpoint, 10 mgKOH/g or more is preferable, and, as for the acid value of alkali-soluble polyimide resin, 50 mgKOH/g or more is more preferable. On the other hand, from a viewpoint of suppressing peeling of the pattern edge of a pixel division layer and/or a planarization layer, 300 mgKOH/g or less is more preferable as for an acid value.

From a viewpoint of the hardness of a pixel division layer and/or a planarization layer, 5,000 or more are preferable, and, as for the weight average molecular weight of alkali-soluble polyimide resin, 10,000 or more are more preferable. On the other hand, from a soluble viewpoint to an alkali developing solution, 100,000 or less are preferable and 70,000 or less are more preferable.

The perylene-based dye derivative of the above specific structure is an organic dye derivative having an aromatic ring and an imide ring in the molecule, has a high affinity for a resin having an aromatic ring and an imide ring in the molecule, By carrying out in coexistence with alkali-soluble polyimide resin which has an imide ring, the dispersibility of the perylene-type pigment derivative of the specific structure with respect to the black material which has (a) nitrogen-containing heterocyclic structure can be improved. 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, it is preferable to use an alkali-soluble polyimide resin in the production of the pigment dispersion to be described later. , a high dispersion stabilization effect can be obtained even with a small addition amount of the perylene-based dye derivative having a specific structure. In addition, the perylene-based dye derivative having a specific structure contains (c) a resin containing a cured product of an alkali-soluble polyimide resin having an aromatic ring and an imide ring in a molecule in the finally obtained pixel dividing layer and/or planarization layer film. Since it has a high affinity for and is charged in a uniformly dispersed state without localization, the luminescence reliability can be further improved.

The photosensitive composition used for pattern-forming the pixel division layer and/or planarization layer with which the organic electroluminescence display of this invention is equipped may contain a photosensitive agent in order to provide either negative type or positive type photosensitivity. .

When providing negative photosensitivity to a photosensitive composition, the compound and photoinitiator which have two or more radically polymerizable groups can be used as a 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, the film of the exposed portion is photocured to insolubilize, and only the unexposed portion is dissolved and removed with an alkali developer to remove the pattern. A pixel dividing layer and/or a planarization layer may be formed.

As a radically polymerizable group, a (meth)acryl group is preferable from a viewpoint of the sensitivity improvement at the time of exposure, and the hardness improvement of a cured film. As a compound which has two or more (meth)acryl groups, For example, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di( Meth) acrylate, trimethylol propane di (meth) acrylate, trimethylol propane tri (meth) acrylate, ethoxylated trimethylol propane di (meth) acrylate, ethoxylated trimethylol propane tri (meth) acrylate, di Trimethylolpropane tri(meth)acrylate, ditrimethylolpropanetetra(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, 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, ethoxy Sihwa 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 of dipentaerythritol (meth) acrylate, ethoxylated bisphenol A di (meth) ) acrylate, 2,2-bis [4- (3- (meth) acryloxy-2-hydroxypropoxy) phenyl] propane, 1,3,5-tris ((meth) acryloxyethyl) isocyanur 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 acid-modified products thereof, ethylene oxide-modified products or propylene oxide-modified products and the like. You may contain these individually or multiple types. Further, the cured product of the compound having two or more radically polymerizable groups is finally filled in the film of the pixel dividing layer and/or the planarization layer as an acrylic resin component contained in the (c) resin.

The photopolymerization initiator refers to a compound that generates radically active species by cleaving and/or reacting bonds with exposure, and photocuring a compound having two or more radically polymerizable groups with the radically active species to form a patterned pixel dividing layer and / or a planarization layer may be formed.

As a photoinitiator, For example, "Adeka Optomer" (registered trademark) N-1818, N-1919, "Adeca Cruz" (registered trademark) NCI-831 (above, all made by ADEKA Corporation), etc. Carbazole-based photopolymerization initiator, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (“Irgacure” (registered trademark) TPO manufactured by BASF), such as acylphosphine oxide-based photoinitiator, 1,2-octane Dione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime)] (BASF Corporation "Irgacure" (registered trademark) OXE01), ethanone, 1- [9-ethyl-6- ( 2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) ("Irgacure" (registered trademark) OXE02 manufactured by BASF), etc. oxime ester type photoinitiator, 2-methyl -1-(4-methylthiophenylphenyl)-2-morpholinopropan-1-one (“Irgacure” (registered trademark) 907 manufactured by BASF), 2-benzyl-2-dimethylamino-1-(4 -morpholinophenyl)-butanone-1 ("Irgacure" (registered trademark) 369 manufactured by BASF), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-( α-aminoalkylphenone-based photopolymerization initiators such as 4-morpholinyl)phenyl]-1-butanone (“Irgacure” (registered trademark) 379EG manufactured by BASF); and the like. Among them, the exposure sensitivity to mixed lines including j-line (wavelength 313 nm), i-line (365 nm), h-line (405 nm), and g-line (436 nm) is high, and deep sclerosis in the film depth direction is excellent. From an excellent point, a carbazole type photoinitiator and an oxime ester type photoinitiator are preferable.

When providing positive photosensitivity to the photosensitive composition, a photo-acid generator can be used as a photosensitive agent. By containing a photo-acid generator, the alkali solubility of an exposed part is relatively improved with respect to an unexposed part by exposure, and a patterned pixel division layer and/or a planarization layer can be formed by dissolving and removing an exposed part with an alkali developer.

As a photo-acid generator, a quinonediazide compound is preferable. As a quinonediazide compound, the reaction product which esterified the compound which has a phenolic hydroxyl group with quinonediazidesulfonyl acid chloride is more preferable.

Examples of the compound 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, methyleneris-p-CR, methylenetetra-p-CR, BisRS-26X, Bis-PFP-PC (all of Honshu Chemical Co., Ltd.) ), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (all are Asahi Yukizai High School Co., Ltd.) ) can be mentioned.

Examples of the quinone diazide sulfonyl acid chloride include 4-naphthoquinone diazide sulfonyl acid chloride and 5-naphthoquinone diazide sulfonyl acid chloride. Such a quinonediazide compound is exposed to a mixed line including j-line (wavelength 313 nm), i-line (365 nm), h-line (405 nm), and g-line (436 nm) in an exposure step to be described later. It is preferred because of its high sensitivity.

The photosensitive composition for forming the pixel division layer and/or planarization layer included in the organic EL display device of the present invention further enhances the heat resistance of the finally obtained pixel division layer and/or planarization layer. Does not matter. Examples of the thermal crosslinking agent include compounds having two or more alkoxymethyl groups and/or methylol groups, and compounds having two or more epoxy groups.

As the compound having two or more alkoxymethyl groups and/or methylol groups, for example, Nicalac (registered trademark) MW-100LM, MX-270, MX-280, MX-290 (manufactured by Sanwa Chemical Co., Ltd.), DML -PC (manufactured by Honshu Chemical High School Co., Ltd.)

As a compound having two or more epoxy groups, for example, "EPOLITE" (registered trademark) 40E, 100E, 200E, 400E, 70P, 200P, 400P, 4000, 3002(N) (above, all are Kyoesha Chemicals) Co., Ltd.), "jER" (registered trademark) 828, 1002, 1750, 1007, YX8100-BH30, E1256, E4250, E4275 (above, all manufactured by Mitsubishi Chemical Co., Ltd.), "TECHMORE" (registered trademark) VG-3101L (manufactured by PRINTEC Co., Ltd.; hereinafter "VG-3101L") and "TEPIC" (registered trademark) S, G, P, L (above, all manufactured by Nissan Chemical Industries, Ltd.) are mentioned. .

The photosensitive composition for forming the pixel division layer and/or planarization layer with which the organic electroluminescence display of this invention is equipped may contain a solvent. By containing a solvent, the viscosity of a photosensitive composition and applicability|paintability can be adjusted.

Examples of the solvent include ethers, acetates, esters, ketones, aromatic hydrocarbons, alcohols, and the like, and these may be used alone or in mixture. Especially, since it is excellent in dispersion stability and can improve film thickness uniformity, acetates and ethers are preferable. Especially, propylene glycol monomethyl ether acetate (henceforth "PGMEA"), 3-methoxybutyl acetate (henceforth "MBA"), and propylene glycol monomethyl ether are mentioned preferably.

As a method of preparing the photosensitive composition for forming the pixel division layer and/or planarization layer with which the organic electroluminescent display of this invention is equipped, For example, (a) a black material which has a nitrogen-containing heterocyclic structure, (b) -1) a non-polymer type dispersant, (b-2) a polymer type dispersant, and a solvent are mixed, and (a) a black material having a nitrogen-containing heterocyclic structure is refined by wet media dispersion treatment to prepare a pigment dispersion, Then, you may prepare a photosensitizer and other components by adding and stirring in the said pigment dispersion liquid, and filtering as needed.

In addition, the perylene-based dye derivative of the specific structure cannot obtain sufficient effects by only post-addition and stirring to the pigment dispersion obtained in the wet media dispersion treatment. However, the effect can be exhibited by providing sufficient mechanical energy in the coexistence of at least one organic pigment having a nitrogen-containing heterocyclic structure in a wet media dispersion treatment.

As a disperser for performing a wet media dispersion process, a horizontal or vertical type bead mill, a roll mill, etc. are mentioned. 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) (DuPont) priest) can be mentioned. Examples of the disperser media include zirconia beads, zircon beads, and alkali-free glass beads. In order to avoid a decrease in luminescence reliability due to contamination due to cracking or abrasion of the media itself, impurity sources such as metals and metal ions It is preferable to use the beads which do not contain this component. Moreover, as for the diameter of a bead, 0.03-5 mm is preferable, and it is so preferable that sphericity is high. As a specific example of a preferable commercial item, "Toray Ceram" (trademark) (made by Toray Co., Ltd.) is mentioned. What is necessary is just to set the operating conditions of a disperser suitably in consideration of bead hardness, handling property, productivity, etc. so that the average dispersed particle diameter and viscosity of the pigment mentioned later may become a desired range.

(a) It is preferable that the average dispersion particle diameter of all the pigments containing the black material which has a nitrogen-containing heterocyclic structure is 40 nm or more from the viewpoint of the applicability|paintability of a photosensitive composition and dispersion stability at the time of storage. On the other hand, in improving the pattern linearity of the pixel division layer and/or the planarization layer, it is preferably 200 nm or less. The average dispersed particle diameter of a pigment refers to the number average value of the secondary particle diameters of all the pigment particles which a pigment dispersion liquid contains here, and can be measured using a particle size distribution apparatus. As a particle size distribution analyzer, a dynamic light scattering method 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, the formation method of the pixel division layer and planarization layer with which the organic electroluminescent display of this invention is equipped is demonstrated.

The pixel division layer and the planarization layer can be obtained, for example, by a method including an application process, a prebaking process, an exposure process, a developing process, and a curing process in this order.

In an application|coating process, a photosensitive composition is apply|coated to a board|substrate, and a coating film is obtained. As a substrate, for example, when manufacturing a top emission type organic display device, as a coating device used for a coating process, for example, a slit coater, a spin coater, a gravure coater, a dip coater, a curtain flow coater, a roll coater , a spray coater, a screen printer, and an inkjet. Since the pixel division layer and the planarization layer are usually formed to have a thickness of about 0.5 to 3 μm in terms of member configuration, they are suitable for thin film coating and are unlikely to cause coating defects, and in terms of film thickness uniformity and productivity, use a slit coater or spin A coater is preferable, and a slit coater is more preferable from a viewpoint of reducing a liquid.

In a prebaking process, a prebaking film is obtained by volatilizing the solvent in a coating film by heating. As a heating apparatus, a hot-air oven, a hot plate, a far-infrared oven (IR oven) etc. are mentioned, for example. You may perform a pin-gap prebaking or a contact prebaking. As for the prebaking temperature, 50-150 degreeC is preferable, and, as for the prebaking time, 30 second - several hours are preferable. For example, after prebaking at 80 degreeC for 2 minute(s), you may prebaking in 2 steps or more multistep, such as prebaking at 120 degreeC for 2 minute(s). In order to improve film-thickness uniformity more, after volatilizing a part of the solvent which a coating film contains with a vacuum / reduced-pressure dryer after an application|coating process, you may perform the prebaking process by a heating.

In an exposure process, an active actinic ray is irradiated through a photomask from the film surface side of a prebaking film|membrane, and an exposure film is obtained. As an exposure apparatus used for an exposure process, a stepper, a mirror projection mask aligner (MPA), a parallel light mask aligner (PLA), etc. are mentioned. Examples of active actinic rays irradiated during exposure include ultraviolet rays, visible rays, electron beams, X-rays, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, 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 a mercury lamp is preferable, and a mixed line thereof is more preferable. The exposure dose is usually about 10 to 4000 mJ/cm 2 (i-line conversion value). As the mask, for example, a thin film having exposure light shielding properties containing a metal such as chromium or a black organic resin is formed in a pattern on one side surface of a substrate having light transmittance at an exposure wavelength such as glass, quartz, or a film. mask can be used. In the formation of the pixel division layer and the planarization layer using the photosensitive composition, any exposure mask of a negative type or a positive type can be used, and an exposure film is obtained by pattern exposing only the opening part by permeating active actinic rays. In addition, the mask in which the part to be made into a pixel division layer or a planarization layer is a pattern corresponding to the opening part in an exposure mask is called a negative exposure mask, and the mask which is a thin film which has exposure light shielding property is called a positive exposure mask.

In addition, when using as a pixel division layer which has both the spacer function in a panel member structure, you may have the site|part from which a pixel division layer differs in film thickness, ie, a step shape, in plane. As a method of obtaining a pixel division layer having a step difference with a different film thickness, in the exposure step, pattern exposure is performed through a negative or positive halftone exposure mask in which a plurality of types of openings having different light transmittances in the exposure light region are formed. method can be found.

In a developing process, when a photosensitive composition is a negative photosensitive composition, image development removes an unexposed part, and a pattern-shaped developing film is obtained. On the other hand, in the case of a positive photosensitive composition, an exposure part is removed by image development, and a pattern-shaped developing film is obtained. Here, the exposed portion refers to a portion to which exposure light is irradiated through the mask opening, while the unexposed portion refers to a portion to which exposure light is not irradiated. As a developing method, the method of immersing an exposure film for 10 second - 10 minutes by methods, such as a shower, dipping, and a paddle, is mentioned, for example in the aqueous alkali solution which is a developing solution.

When the photosensitive composition is a negative photosensitive composition, an unexposed part becomes a pattern opening part, when it is a positive type, an exposed part turns into a pattern opening part, and the ITO electrode which is a base is exposed in the site|part which became all opening parts. The photosensitive composition containing the perylene-type dye derivative of the said specific structure can exhibit the remarkable effect in suppressing the image development residue on an ITO electrode in this image development process. Moreover, the opening part finally becomes a light emitting pixel part in an organic electroluminescent display.

In the formation of the pixel division layer and/or the planarization layer of the organic EL display device, 1.0 to 3.0 wt% TMAH because it is easy to volatilize the developing solution remaining in the surface layer or inside of the developing film in the curing step after development. is preferred, and 2.38 wt% TMAH is usually used. As for 2.38 wt% TMAH, a commercially available product may be used, or a high-concentration product may be diluted and used, and a small amount of a nonionic surfactant may be added in a range that does not adversely affect the luminescence reliability and may be used for development. In addition, after image development, you may add the washing process by the shower of deionized water and/or the water removal process by air spraying.

In the curing step, the developing film is thermally cured by heating, and components such as moisture and permeated and remaining developer are volatilized to obtain a pixel division layer or a planarization layer. As a heating apparatus, a hot air oven, IR oven, etc. are mentioned, for example. 230-300 degreeC is preferable and, as for heating temperature, 250-300 degreeC is more preferable in obtaining high light emission reliability. The heating atmosphere is preferably air or nitrogen atmosphere, and the pressure at the time of heating is preferably atmospheric pressure.

The optical density per 1.0 µm thickness of the pixel dividing layer and the planarization layer of the organic EL display device of the present invention, which can be patterned through each of the above steps, is preferably 0.5 or more, more preferably 0.8 or more, , more preferably 1.0 or more. The optical density as used herein refers to the intensity of incident light and transmitted light by using an optical densitometer (manufactured by X-Rite; X-Rite 361T) for a pixel dividing layer or a planarization layer formed to have a film thickness of 1.0 µm on a translucent substrate. The intensity|strength is measured and the value computed from the following formula|equation is said. It shows that light-shielding property is so high that an optical density is high. As a translucent base material, "Tempax (manufactured by AGC Techno Glass Co., Ltd.)" which is a translucent glass base material can be used preferably.

Optical Concentration =log ₁₀ (I ₀ /I)

I ₀ : incident light intensity

I: transmitted light intensity

In order to stably drive a light emitting element, each of the dielectric constants in the pixel division layer and the planarization layer of an organic EL display device at a frequency of 1 kHz are preferably 7 or less, more preferably 5 or less, and still more preferably 4 or less. . The relative 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 display area can be made high-definition, the display quality of an image or video can be improved, and the value as a display device can be increased. As used herein, the aperture ratio refers to the area ratio of the opening of the pixel dividing layer to the area of the pixel dividing layer. Since the formation area of the pixel dividing layer in the display area becomes larger as the aperture ratio decreases, the performance related to the light emission reliability of the pixel dividing layer is greatly affected. That is, the effect of the present invention contributes more greatly to the organic EL display device having a low aperture ratio and a high-definition display area.

Example

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the aspect of the present invention is not limited thereto.

First, the evaluation method in each Example and a comparative example is demonstrated.

<Calculation method for minimum required exposure dose>

On the surface of a 100 mm x 100 mm alkali-free glass substrate, a 10 nm thick silver/copper alloy thin film (volume ratio 10:1) is formed over the entire surface by sputtering, and a patterned metal reflective layer is formed by etching. . Then, the entire surface of the 10 nm-thick ITO transparent conductive film was formed into a film by the sputtering method, and the board|substrate for minimum required exposure amount evaluation was obtained.

The photosensitive composition was applied on the surface of the obtained substrate for evaluation of the minimum required exposure dose by a spin coater while adjusting the rotation speed so that the thickness of the finally obtained cured film was 1.0 μm, to obtain a coating film, and hot plate (SCW-636; Dainippon Screen) Using Seijou Co., Ltd. product), the coating film was prebaked at 100 degreeC under atmospheric pressure for 120 second, and the prebaked film|membrane was obtained. Using a double-sided alignment single-sided exposure device (mask aligner PEM-6M; manufactured by Union Kogaku 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, it developed with 2.38 weight% TMAH aqueous solution using the small-size developing apparatus for photolithography (AD-2000; Takizawa Sangyo Co., Ltd. product), and the developing film was obtained. Next, using an FPD inspection microscope (MX-61L; manufactured by Olympus Co., Ltd.), the resolution pattern of the produced developing film is observed, and in the line-and-space pattern, the exposure amount formed by the pattern line width and the pitch width being one-to-one. (mJ/cm<2>: value of i-line illuminometer) was made into the minimum required exposure dose (sensitivity) of the photosensitive composition. As used herein, the pitch width refers to an interval between the same patterns. In addition, in a negative photosensitive composition and a positive photosensitive composition, since evaluation is performed with the same grayscale mask, arrangement|positioning of the pattern formed is inverted.

(1) Evaluation of dispersion stability of photosensitive composition

20.0 g of the photosensitive compositions obtained in Examples 1-22 and Comparative Examples 1-33 were capped in a glass bottle within 1 hour after preparation, and 24 in a constant temperature box under atmospheric pressure/under light blocking/room temperature of 25°C±1°C The time was set and stored. After storage, 1.0 g of the photosensitive composition was collected, dropped on a stage at room temperature of 25° C. of a type E viscometer (corn plate type viscometer), and a shear force was applied under the condition of a rotation speed of 50 rpm, and the viscosity indicated after 3 minutes was measured as the initial viscosity (mPa). ·s). Under the same storage environment, the photosensitive composition was continuously stored for 29 days at 25 ° C. ± 1 ° C. After confirming the presence or absence of sediment at the bottom of the glass bottle with a spatula, the composition was stirred on a shaker for 1 minute, and the viscosity was measured by the same method, and the viscosity (mPa·s) over time was used to determine the thickening rate (%) from the following formula. The smaller the absolute value of the thickening rate (%), the better the stability, the dispersion stability was evaluated based on the following criteria, and AA and A to C were passed, and D to F were rejected. However, when sedimentation occurred after storage, evaluation was set to E regardless of the thickening rate. In addition, when either the initial viscosity or the aging viscosity of the photosensitive composition exceeds 100 (mPa·s), comparative evaluation under the same viscosity measurement conditions is difficult, so regardless of the presence or absence of sediment or its thickening rate , the evaluation was made F.

Thickening rate (%) = (viscosity with time-initial viscosity)/initial viscosity x 100

In addition, when the thickening rate is a positive value, it shows high viscosity, and when it is a negative value, it shows low viscosity. In Examples 1-22 and Comparative Examples 1-33, for those evaluated as A to D, There was no indication of the value of

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: Since the viscosity is too high, evaluation under the same viscosity measurement conditions is impossible.

(2) Evaluation of light-shielding properties of cured films

With respect to the substrate for light-shielding evaluation having a cured film on the surface of the tempax obtained in Examples 1-22 and Comparative Examples 1-33, using an optical densitometer (manufactured by X-Rite; X-Rite 361T), from the film surface side The optical density (OD value) was measured in three places in a plane, the second decimal place of the average value was rounded off, and the numerical value to the first decimal place was calculated|required. By dividing the numerical value by the thickness (µm) of the cured film, the OD value (OD/µm) per 1.0 µm in thickness of the cured film was calculated, and the higher the OD value, the higher the evaluation was based on the criterion of a cured film excellent in light-shielding properties. . As a result of separately measuring the OD value intrinsic to the board|substrate of Tempax itself which does not form a cured film, since it was 0.00, the OD value of the board|substrate for light-shielding evaluation was regarded as the OD value of the cured film. Incidentally, 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 two decimal places, and the first decimal point is used. The number to the digit was obtained.

(3) Evaluation of development residues in the pixel division layer

10 openings located at the center of the pixel division layer forming substrates obtained in Examples 1-22 and Comparative Examples 1-33 were observed at a magnification of 50 times using an optical microscope, and the major diameter of each opening was 0.1 The number of developing residues of mu m or more and less than 3.0 mu m was counted. From the average number of the development residues observed per opening part, it evaluated based on the following criteria, AA and A-C were made into pass, and D-E was made into fail. However, when a residue exceeding 3.0 micrometers in long diameter was seen, it evaluated as E, irrespective of the average number of residues.

AA: No development residue is seen at all

A: Less than 5 development residues are seen

B: 5 or more and less than 10 development residues are seen

C: 10 or more and less than 15 development residues are seen

D: 15 or more development residues are seen

E: The development residue exceeding 3.0 micrometers in long diameter is seen.

(4) Emission reliability evaluation of an organic EL display device having a pixel dividing layer, (5) Emission reliability evaluation of an organic EL display device having a pixel dividing layer and a planarization layer

The organic EL display devices obtained in Examples 1 to 22 and Comparative Examples 1 to 33 were placed on a hot plate heated to 80°C with the light emitting surface facing up while emitting light by direct current driving at 10 mA/cm 2 , and the light emitting pixels were The area ratio of the light emitting part to the area (the pixel emission area ratio) was measured after 1 hour and after 500 hours. Based on the pixel emission area ratio after 1 hour, pixel shrinkage is unlikely to occur enough to maintain a high pixel emission area ratio, so that the emission reliability is excellent. , D to F were rejected. In other words, when there were too many dark spots in a pixel at the time immediately after a drive start and it was difficult to evaluate the pixel emission area ratio justly, evaluation was made into E. In addition, when there was one or more non-illuminated light emitting pixel parts at the time immediately after the start of driving, evaluation was made into 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: There are too many dark spots, it is difficult to make a fair evaluation

F: There is at least one light-emitting pixel portion that is completely non-illuminated (pixel emission area ratio of 0%) at the time immediately after driving, and a fair evaluation is difficult.

(6) Evaluation of dark spots (locally non-light-emitting regions) of organic EL display devices including pixel division layer and planarization layer

For the organic EL display devices having the pixel division layer and the planarization layer having a pixel opening ratio of 18% obtained in Examples 1-22 and Comparative Examples 1-33, the organic EL display device at a time point 2 hours after starting the driving In a pixel portion formed in an area of 16 mm in length / 16 mm in width by emitting light by driving the display device by direct current of 10 mA/cm 2 , 10 pixel portions located in the center are enlarged and displayed on the monitor at a magnification of 50 times. Observation was carried out, and the number of locally non-luminescent sites with a major diameter of 0.1 µm or more and less than 15.0 µm in each opening was counted. From the average number of locally non-luminescent sites observed per opening, it was evaluated based on the following criteria, AA and A to C were passed, and D to E were rejected. However, when dark spots exceeding 15.0 µm in long diameter were observed, it was evaluated as E regardless of the average number of dark spots.

AA: No dark spots visible at all

A: Less than 5 dark spots are visible

B: 5 or more but less than 10 dark spots are seen

C: 10 or more but less than 15 dark spots are seen

D: More than 15 dark spots are visible

E: A dark spot exceeding 15.0 µm in long diameter is seen

F: There is one or more light-emitting pixel portions that are completely non-illuminated (pixel emission area ratio of 0%), making a just evaluation difficult

(Synthesis Example 1: Synthesis of alkali-soluble polyimide resin solution A)

Under a stream of dry nitrogen, 150.15 g of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (0.41 mol), 6.20 g of 1,3-bis(3-aminopropyl)tetramethyldi Siloxane (0.02 mol) and 13.65 g of 3-aminophenol (0.13 mol) as a terminal blocker were dissolved in 500.00 g of N-methyl-2-pyrrolidone (hereinafter referred to as "NMP") as a solvent, followed by 155.10 g of bis(3,4-dicarboxyphenyl)ether dianhydride (0.50 mol) and 150.00 g of NMP were added, followed by stirring at 20° C. for 1 hour, and also stirring at 180° C. for 4 hours while removing water. After completion of the reaction, the reaction solution is poured into 10 L of water, the resulting precipitate is collected by filtration, washed with water 5 times, dried for 20 hours in a vacuum dryer at 80° C., and the structural unit represented by the above general formula (31) Alkali-soluble polyimide resin powder having an aromatic ring and an imide ring in the molecule, and having an aromatic ring and an imide ring in the molecule, is synthesized with an alkali-soluble polyimide resin powder having a weight average molecular weight (Mw) of 25,000, and this is dissolved in PGMEA so as to have a solid content of 30.00% by weight, and alkali-soluble polyimide resin solution A got

(Synthesis Example 2: Synthesis of polymer-type dispersant solution B)

12.91 g of methacrylic acid (0.15 mol), 55.07 g of methyl methacrylate (0.55 mol), and an ethylenically unsaturated monomer having a phosphoric acid group in 185.44 g of PGMEA maintained at a liquid temperature of 100° C. under a dry nitrogen stream. A mixture of 21.01 g of acid phosphoxyethyl methacrylate (0.10 mol), 26.43 g of benzyl methacrylate (0.15 mol), and 8.21 g of azobisisobutyronitrile is added dropwise over 30 minutes, and further After advancing the thermal polymerization reaction by stirring for 1 hour while maintaining the liquid temperature at 100 degreeC, it cooled and synthesize|combined the (meth)acrylic-type copolymer whose weight average molecular weight (Mw) is 9500. This was diluted with PGMEA so that it might become 30.00 weight% of solid content, and the polymer type dispersing agent solution B which is a polymer type dispersing agent which has a phosphoric acid group as an acidic adsorption group was obtained.

(Synthesis Example 3: Synthesis of quinonediazide compound a)

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

Chemical structures of the various organic pigment derivatives and organic pigments used in Examples and Comparative Examples are shown below.

"Perylene-based dye derivative 1": a compound represented by the following structural formula (33) (perylene-based dye derivative corresponding to the compound represented by the general formula (1))

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

“Perylene-based dye derivative 3”: a compound represented by the following structural formula (35) (a perylene-based dye derivative in which R ² and R ³ are aryl groups having a substituent, which is a compound represented by the aforementioned general formula (2))

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

“Perylene-based dye derivative 5”: a compound represented by the following structural formula (37) (a perylene-based dye derivative in which R ² and R ³ are aryl groups having a substituent, which is a compound represented by the aforementioned general formula (2))

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

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

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

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

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

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

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

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

"Copper phthalocyanine pigment derivative 4": a compound represented by the following structural formula (47) (C.I. Direct Blue 86)

"Copper phthalocyanine pigment derivative 5": a compound represented by the following structural formula (48) (C.I. Acid Blue 249)

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

"Diketopyrrolopyrrole pigment 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) (perylene-based dye derivative not corresponding to the compound represented by the aforementioned general formula (1) or (2))

"Perylene-based dye derivative 13": a compound represented by the following structural formula (53) (perylene-based dye derivative not corresponding to the compound represented by the aforementioned general formula (1) or (2))

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

“Perylene-based dye derivative 15”: a compound represented by the following structural formula (55) (perylene-based dye derivative not corresponding to the compound represented by the aforementioned general formula (1) or (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: Azo organic yellow pigment having no nitrogen-containing heterocyclic structure in its molecule

C.I. Pigment Violet 50: Azo organic purple pigment having no nitrogen-containing heterocyclic structure in its molecule

C.I. Pigment Red 224: Perylene-based organic red pigment having no nitrogen-containing heterocyclic structure in its molecule, represented by the following structural formula (59)

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

As the content of the glass ionic impurities contained in each of the above organic dye derivatives and organic pigments, each content of sulfate ion (SO ₄ ^2- ), sulfite ion (SO ₃ ⁻ ), and chlorine ion (Cl ⁻ ) is 50 ppm or less. It was confirmed by ion chromatography. Moreover, about the organic pigment derivative and organic pigment containing a copper atom, it confirmed that free copper was 100 ppm or less by ion chromatography.

(Preparation Example 1: Preparation of Pigment Dispersion Liquid 1)

89.06 g of alkali-soluble polyimide resin solution A and 28.13 g of SOLSPERSE20000 (a linear polyether dispersant having a polyethylene oxide/propylene oxide structure in the main chain and a tertiary amino group at the end of the main chain as a basic adsorbent; solid content 100.00 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) as a black material having a nitrogen-containing heterocyclic structure, 28.13 g of CI Pigment Yellow 192 (average primary particle diameter of 42 nm) and 28.13 g of CI Pigment Red 179 (average primary particle diameter of 48 nm) were obtained. ) and 37.50 g of CI Pigment Blue 60 (average primary particle diameter of 61 nm) were added, stirred for 30 minutes, and zirconia beads of 0.4 mmφ (manufactured by Toray Co., Ltd.; "Toray Ceram" (registered trademark)) were added Using the filled bead mill, the wet media dispersion treatment was carried out in circulation for 30 minutes. Next, in order to further promote refinement, using a bead mill filled with 0.05 mmφ zirconia beads (manufactured by Toray Co., Ltd.; "Toray Ceram" (registered trademark)), wet media dispersion treatment is performed in a circulating manner, After 30 minutes have elapsed, each time the dispersion treatment time has elapsed for 10 minutes, an appropriate amount of the sampled pigment dispersion liquid is drawn into a glass bottle and set in a dynamic light scattering method particle size distribution measuring device "SZ-100" to measure the average dispersed particle diameter, , The pigment dispersion liquid which became in the range of 150 nm±20 nm at the time of 30 minutes after sampling was made into the pigment dispersion liquid 1. Here, the solid content of the pigment dispersion liquid 1 was 15.00 weight%. Table 1 shows the compounding amount (g) of each raw material. Content of the organic dye derivative with respect to all the pigments is 1.50 weight%.

(Preparation Examples 2 to 7: Preparation of pigment dispersions 2 to 7)

In place of the perylene-based dye derivative 1, perylene-based dye derivatives 2 to 7 were used, respectively, and pigment dispersions 2 to 7 were prepared in the same manner as in Preparation Example 1. Table 1 shows the compounding amount (g) of each raw material.

(Preparation Example 8: Preparation of pigment dispersion 8)

A pigment dispersion 8 was prepared in the same manner as in Preparation Example 1 except that C.I. Pigment Red 123 (average primary particle diameter of 57 nm) was used instead of C.I. Pigment Red 179. Table 2 shows the compounding amount (g) of each raw material.

(Preparation Example 9: Preparation of pigment dispersion 9)

A pigment dispersion 9 was prepared in the same manner as in Preparation Example 8 except that the perylene-based dye derivative 4 was used instead of the perylene-based dye derivative 1. Table 2 shows the compounding amount (g) of each raw material.

(Preparation Example 10: Preparation of pigment dispersion 10)

A pigment dispersion 10 was prepared in the same manner as in Preparation Example 1, except that the perylene-based dye derivative 7 was used by increasing the content of the organic dye derivative to 5.00% by weight in place of the perylene-based dye derivative 1. Table 2 shows the compounding amount (g) of each raw material.

(Preparation Example 11: Preparation of pigment dispersion 11)

Preparation Example 1 except that instead of the perylene-based dye derivative 1, the content of the organic dye derivative with respect to all the pigments was increased to 5.00% by weight, and used in combination at a perylene-based dye derivative 1/perylene-based dye derivative 7 = 1/1 by weight Pigment dispersion 11 was prepared in the same procedure as described above. Table 2 shows the compounding amount (g) of each raw material.

(Preparation Example 12: Preparation of Pigment Dispersion 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-based dye derivative 7 were mixed and stirred for 10 minutes. Thereafter, (a) as a black material having a nitrogen-containing heterocyclic structure, 28.13 g of CI Pigment Yellow 194 (average primary particle diameter of 64 nm) and 28.13 g of CI Pigment Violet 29 (average primary particle diameter of 57 nm) ) and 37.50 g of CI Pigment Blue 60 (average primary particle diameter of 61 nm) were added and stirred for 30 minutes. The subsequent process performed the wet media dispersion process in the same procedure as Preparation Example 1, and prepared the pigment dispersion liquid 12. Table 2 shows the compounding amount (g) of each raw material.

(Preparation Example 13: Preparation of pigment dispersion 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-based dye derivative 7 were mixed and stirred for 10 minutes. Thereafter, (a) as a black material having a nitrogen-containing heterocyclic structure, 32.81 g of CI Pigment Yellow 192 (average primary particle diameter of 42 nm) and 46.88 g of Perylene Black A (average primary particle diameter of 55 nm) were obtained. And, 14.06 g of CI Pigment Blue 60 (average primary particle diameter of 61 nm) was added and stirred for 30 minutes. The subsequent process performed the wet media dispersion process in the same procedure as the preparation example 1, and prepared the pigment dispersion liquid 13. Table 2 shows the compounding amount (g) of each raw material.

(Preparation Example 14: Preparation of pigment dispersion 14)

A pigment dispersion 14 was prepared in the same manner as in Preparation Example 13 except that C.I. Pigment Blue 15:6 was used instead of C.I. Pigment Blue 60. Table 2 shows the compounding amount (g) of each raw material.

(Preparation Example 15: Preparation of pigment dispersion 15)

A rosin mixture containing 200.00 g of crude pigment A (CI Pigment Red 179; average primary particle diameter of 172 nm), 13.50 g of perylene-based pigment derivative 1, and a rosin dimer having at least one carboxyl group, 10.00 g 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 maintained at 100 to 110 ° C. got it Then, water is added to the red kneaded material, the water-soluble component is dissolved in 3 L of hot water maintained at 60 ° C., and water washing is repeated until the content of free chlorine in the red filtrate is less than 100 ppm, followed by filtration, It dried in an oven at 110 degreeC for 12 hours. Subsequently, it was sized by the dry grinding process using a jet mill, and the red surface treatment pigment A (average primary particle diameter of 44 nm) was obtained. The above process is the wet grinding process by the solvent salt milling method. In addition, in the above-mentioned filtration process, since the perylene type pigment derivative 1 partly lost|disappeared in the filtrate, the ratio of the structural component of the red surface treatment pigment A finally obtained is 100 weight part CI Pigment Red 179, and 5 weight part peryl It was the ene 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) as a black material having a nitrogen-containing heterocyclic structure, 28.13 g of CI Pigment Yellow 192, 30.94 g of Red Surface Treatment Pigment A, and 37.50 g of CI Pigment Blue 60 were added, and 30 minutes stirred. The subsequent process performed the wet media dispersion process in the same procedure as the preparation example 1, and prepared the pigment dispersion liquid 15. Table 2 shows the compounding amount (g) of each raw material.

(Preparation Example 16: Preparation of pigment dispersion 16)

89.06 g of alkali-soluble polyimide resin solution A, 93.75 g of polymer dispersant solution B, 722.03 g of PGMEA, and 1.41 g of perylene-based dye derivative 8 were mixed and stirred for 10 minutes. Then, 28.13 g of CI Pigment Yellow 192 (average primary particle diameter of 42 nm), 28.13 g of CI Pigment Red 179 (average primary particle diameter of 48 nm), and 37.50 g of CI Pigment Blue 60 (average of 1) A tea particle diameter of 61 nm) was added and stirred for 30 minutes. The subsequent process performed the wet media dispersion process in the procedure similar to Preparation Example 1, and prepared the pigment dispersion liquid 16. Content of the organic dye derivative with respect to all the pigments is 1.50 weight%.

Table 3 shows the compounding amount (g) of each raw material.

(Preparation Examples 17 to 19: Preparation of pigment dispersions 17 to 19)

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

(Preparation Example 20: Preparation of pigment dispersion 20)

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

(Preparation Example 21: Preparation of pigment dispersion 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-based dye derivative 1 were mixed and stirred for 10 minutes. Thereafter, 18.75 g of CI Pigment Yellow 83 (average primary particle diameter of 41 nm), which is an organic pigment having no nitrogen-containing heterocyclic structure, and 56.25 g of CI Pigment Violet 50 (average of nitrogen-containing heterocyclic structure) Primary particle size of 56 nm) and 18.75 g of CI Pigment Red 179 (average particle size of 48 nm) having a nitrogen-containing heterocyclic structure were added and stirred for 30 minutes. The subsequent process performed the wet media dispersion process in the same procedure as that of Preparation Example 1, and prepared the pigment dispersion liquid 21. Table 4 shows the compounding amount (g) of each raw material. Content of the organic dye derivative with respect to all the pigments is 1.50 weight%.

(Preparation Example 22: Preparation of pigment dispersion 22)

The compounding quantity of the perylene pigment derivative 1 was increased, and with the compounding quantity (g) shown in Table 4, the pigment dispersion 22 was prepared by the same procedure as Preparation Example 21. Content of the organic dye derivative with respect to all the pigments is 5.00 weight%.

(Preparation Example 23: Preparation of pigment dispersion 23)

Perylene-based dye derivative 4 was used instead of perylene-based dye derivative 1, and CI pigment red 224 (average primary particle diameter of 62 nm) having no nitrogen-containing heterocyclic structure was used instead of CI pigment red 179, With the compounding quantity (g) shown in Table 4, the pigment dispersion 23 was prepared by the same procedure as Preparation Example 21.

(Preparation Example 24: Preparation of Pigment Dispersion 24)

200.00 g of crude pigment B (CI Pigment Violet 29; average primary particle diameter of 163 nm), 2000.00 g of sodium chloride, and 400.00 g of diethylene glycol are mixed, and the liquid temperature is maintained at 90 to 100 ° C. It kneaded with time to obtain a purple kneaded product. Next, water is added to the purple kneaded material, the water-soluble component is dissolved in 2 L of hot water maintained at 60 ° C., and the water washing is repeated until the content of free chlorine in the purple filtrate is less than 100 ppm, followed by filtration. , and diluted again with water to obtain a purple pigment slurry having a solid content of 30% by weight. In the purple pigment slurry, an aqueous sodium hydroxide solution containing copper phthalocyanine pigment derivative 1 is added, and after stirring for 1 hour, hydrochloric acid is added until pH 7 to precipitate copper phthalocyanine pigment derivative 1 on the pigment surface, 110 It was dried in an oven at °C for 12 hours. Subsequently, it was sized by dry grinding treatment using a jet mill, and a purple surface-treated pigment A (average primary particle diameter of 25 nm) containing 100 parts by weight of CI Pigment Violet 29 and 5 parts by weight of copper phthalocyanine-based pigment derivative 1 was obtained. got it Next, 28.13 g of PB821 (manufactured by Ajinomoto Fine Techno; polyester polymer type dispersant having a basic adsorbing group and an acidic adsorbing group; solid content: 100.00 wt%) and 788.01 g of PGMEA were mixed and stirred for 10 minutes. Then, as an organic pigment, 27.33 g of CI Pigment Yellow 139 (average primary particle diameter of 65 nm), 32.43 g of purple surface treatment pigment A, and 35.55 g of CI Pigment Blue 15:6 (average primary particle diameter) 45 nm) and stirred for 30 minutes. In the subsequent steps, the wet media dispersion treatment was performed in the same manner as in Preparation Example 1. Next, it diluted by adding alkali-soluble polyimide resin solution A so that solid content of a pigment dispersion liquid might be 15.00 weight%, and the pigment dispersion liquid 24 was prepared. Moreover, content of solid content in alkali-soluble polyimide resin solution A with respect to all the organic pigments which pigment dispersion liquid 24 contains is 28.33 weight%, and content of organic dye derivative is 1.65 weight%. Table 4 shows the compounding amount (g) of each raw material.

(Preparation Example 25: Preparation of pigment dispersion 25)

A wet grinding treatment was performed in the same manner as in Preparation Example 24, except that the amount of the copper phthalocyanine-based dye derivative 1 was increased, and a purple surface treatment containing 100 parts by weight of CI Pigment Violet 29 and 12 parts by weight of the copper phthalocyanine-based dye derivative 1. Pigment B (average primary particle diameter of 25 nm) was obtained, and with the compounding quantity (g) shown in Table 4, the pigment dispersion 25 of 15.00 weight% of solid content was prepared in the same procedure as Preparation Example 24. Moreover, content of solid content in alkali-soluble polyimide resin solution A with respect to all the organic pigments contained in pigment dispersion 25 is 26.03 weight%, and content of organic dye derivative is 3.95 weight%. Table 4 shows the compounding amount (g) of each raw material.

(Preparation Example 26: Preparation of pigment dispersion 26)

A pigment dispersion 26 having a solid content of 15.00 wt% was prepared in the same manner as in Preparation Example 25 except that SOLSPERSE20000 was used instead of PB821. Table 4 shows the compounding amount (g) of each raw material.

(Preparation Example 27: Preparation of pigment dispersion 27)

A purple surface-treated pigment C (average primary particle diameter of 31 nm) was obtained by performing wet grinding treatment in the same manner as in Preparation Example 24 except that copper phthalocyanine-based dye derivative 2 was used instead of copper phthalocyanine-based dye derivative 1. In the subsequent steps, the wet media dispersion treatment was performed in the same manner as in Preparation Example 24. Next, it diluted by adding alkali-soluble polyimide resin solution A so that solid content of a pigment dispersion liquid might be 15.00 weight%, and the pigment dispersion liquid 27 was prepared. In addition, content of solid content in alkali-soluble polyimide resin solution A with respect to all the organic pigments contained in pigment dispersion liquid 27 is 28.33 weight%, and content of organic dye derivative is 1.65 weight%. Table 4 shows the compounding amount (g) of each raw material.

(Preparation Example 28: Preparation of pigment dispersion 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 pigment derivative 1 were mixed and stirred for 10 minutes. After that, (a) 27.33 g of CI Pigment Yellow 139 (average primary particle diameter of 65 nm) and 30.88 g of CI Pigment Violet 29 (average primary particle diameter of 57 nm) as a black material having a nitrogen-containing heterocyclic structure. And 35.55 g of CI Pigment Blue 15:6 (average primary particle diameter of 45 nm) was added and stirred for 30 minutes. The subsequent process performed the wet media dispersion process by the procedure similar to Preparation Example 1, and prepared the pigment dispersion liquid 28 of 15.00 weight% of solid content. In addition, content of the organic dye derivative with respect to all the organic pigments contained in the pigment dispersion liquid 28 is 10.00 weight%. Table 5 shows the compounding amount (g) of each raw material.

(Preparation Examples 29 to 33: Preparation of pigment dispersions 29 to 33)

Instead of the perylene-based dye derivative 1, except having used the copper phthalocyanine-based dye derivatives 1 to 5, respectively, in the same procedure as in Preparation Example 1, pigment dispersions 29 to 33 having a solid content of 15.00% by weight were prepared. In addition, content of the organic dye derivative with respect to all the organic pigments contained in the pigment dispersion liquids 29-33 is 1.50 weight%. Table 5 shows the compounding amount (g) of each raw material.

(Preparation Example 34: Preparation of pigment dispersion 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 copper phthalocyanine-based dye derivative 6 was used instead of the perylene-based dye derivative 8, respectively. In addition, content of the organic pigment derivative with respect to all the organic pigments contained in the pigment dispersion liquid 34 is 1.50 weight%. Table 6 shows the compounding amount (g) of each raw material.

(Preparation Example 35: Preparation of pigment dispersion 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 at the compounding amount (g) shown in Table 6 using the copper phthalocyanine dye derivative 6 instead of the perylene-based dye derivative 8. In addition, content of the organic dye derivative with respect to all the organic pigments contained in the pigment dispersion liquid 35 is 5.00 weight%. Table 6 shows the compounding amount (g) of each raw material.

(Preparation Examples 36 to 41: Preparation of pigment dispersions 36 to 41)

15.00 wt% of solid content in the same procedure as in Preparation Example 1, except that diketopyrrolopyrrole pigment derivative 1, isoindoline dye derivative 1, and perylene dye derivatives 12 to 15 were respectively used instead of perylene-based dye derivative 1 of pigment dispersions 36 to 41 were prepared. Table 6 shows the compounding amount (g) of each raw material.

(Preparation Example 42: Preparation of Pigment Dispersion Liquid 42)

The compounding quantity of the perylene pigment derivative 14 was increased, and with the compounding quantity (g) shown in Table 6, the pigment dispersion liquid 42 was prepared in the same procedure as in Preparation Example 1. In addition, content of the organic dye derivative with respect to all the pigments contained in the pigment dispersion liquid 42 is 5.00 weight%.

(Preparation Example 43: Preparation of Pigment Dispersion Liquid 43)

A pigment dispersion 43 having a solid content of 15.00 wt% was prepared in the same manner as in Preparation Example 1 by the compounding amount (g) shown in Table 7 without using the perylene-based dye derivative 1 .

(Preparation Example 44: Preparation of pigment dispersion 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) as a black material having a nitrogen-containing heterocyclic structure, 46.88 g of CI Pigment Red 254 (average primary particle size of 40 nm) and 46.88 g of CI Pigment Blue 15:6 (average primary particle size) of 45 nm) and stirred for 30 minutes. The subsequent process performed the wet media dispersion process by the procedure similar to Preparation Example 1, and prepared the pigment dispersion liquid 44 of 15.00 weight% of solid content. Table 7 shows the compounding amount (g) of each raw material.

(Preparation Example 45: Preparation of pigment dispersion 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 compounding 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 CI Pigment Yellow 139 (average primary particle diameter of 65 nm) and 30.88 g of CI Pigment Violet 23 (average primary particle diameter of 58 nm) as a black material having a nitrogen-containing heterocyclic structure. and 35.55 g of CI Pigment Blue 60 (average primary particle diameter of 61 nm) were added and stirred for 30 minutes. The subsequent process performed the wet media dispersion process by the procedure similar to Preparation Example 1, and prepared the pigment dispersion liquid 46 of 15.00 weight% of solid content. Table 7 shows the compounding amount (g) of each raw material. Here, content of the organic dye derivative with respect to all the organic pigments contained in the pigment dispersion liquid 46 is 3.00 weight%.

(Preparation Example 47: Preparation of pigment dispersion 47)

Except having increased the amount of the copper phthalocyanine pigment derivative 1, it was the same procedure as Preparation Example 46, and prepared the pigment dispersion 47 of 15.00 weight% of solid content with the compounding quantity of the raw material shown in Table 7. Here, content of the organic dye derivative with respect to all the organic pigments contained in the pigment dispersion liquid 47 is 10.00 weight%.

(Preparation Example 48: Preparation of Pigment Dispersion Liquid 48)

A pigment dispersion 48 having a solid content of 15.00% by weight was prepared in the same procedure as in Preparation Example 46 except that the dioxazine-based dye derivative 1 was used instead of the copper phthalocyanine-based dye derivative 1, and the blending amount of the raw materials shown in Table 7 was used.

(Preparation Example 49: Preparation of pigment dispersion 49)

Copper phthalocyanine-based dye derivative 1 and dioxazine-based dye derivative 1 were used in combination at a copper phthalocyanine-based dye derivative 1/dioxazine-based dye derivative 1 = weight ratio of 1/1. The pigment dispersion 49 of 15.00 weight% of solid content was prepared by the compounding quantity. Here, content of the organic dye derivative with respect to all the organic pigments contained in the pigment dispersion liquid 49 is 6.00 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 procedure as in Preparation Example 13 except that the perylene-based dye derivative 7 was not used, and in the amount of the raw materials shown in Table 8.

(Preparation Example 51: Preparation of Pigment Dispersion Liquid 51)

A pigment dispersion 51 having a solid content of 15.00% by weight was prepared in the same procedure as in Preparation Example 13 except that the copper phthalocyanine-based dye derivative 1 was used instead of the perylene-based dye derivative 7, and the blending amount of the raw materials shown in Table 8 was used. In addition, content of the organic dye derivative with respect to all the organic pigments contained in the pigment dispersion liquid 51 is 8.00 weight%.

(Preparation Example 52: Preparation of pigment dispersion 52)

A pigment dispersion 52 having a solid content of 15.00% by weight was prepared in the same procedure as in Preparation Example 13 except that the copper phthalocyanine-based dye derivative 1 was used instead of the perylene-based dye derivative 7, and the blending amount of the raw materials shown in Table 8 was used. In addition, content of the organic dye derivative with respect to all the organic pigments which the pigment dispersion liquid 52 contains is 4.00 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 addition acrylate of dipentaerythritol as a compound having two or more radically polymerizable groups (KAYARAD DPCA- 60; manufactured by Nippon Kayaku Co., Ltd.; in the table, "DPCA-60"), as a photoinitiator, 0.30 g of "Adeka Cruz" (registered trademark) NCI-831 (manufactured by ADEKA), and heat As a crosslinking agent, 0.30 g of VG-3101L, a compound having three epoxy groups in the molecule, and 7.85 g of PGMEA and 8.50 g of MBA as a solvent are mixed, capped and stirred on a shaker for 30 minutes, and the content of organic pigment The sum total was 33.00 weight% with respect to the total solid in a negative photosensitive composition, and prepared the negative photosensitive composition 1 whose solid content is 15.00 weight%. Then, dispersion stability was evaluated by the method described above. In addition, the pigment dispersion liquid used for preparation of the photosensitive composition was made to be used for preparation of a photosensitive composition within 2 hours after obtaining by a wet media dispersion process, without long-term storage alone as a pigment dispersion liquid. Table 9 shows the compounding quantity (g) of each raw material, and Table 14 shows the evaluation result of dispersion stability.

After preparing according to the above procedure, the negative photosensitive composition 1 after long-term storage under atmospheric pressure / under light blocking / in a constant temperature box at room temperature of 25 ° C. ± 1 ° C. for 30 days is stirred on a shaker for 1 minute, and Tempax (50 mm x 50 mm translucent glass substrate), the number of rotations was adjusted so that the thickness of the cured film finally obtained might be set to 1.0 micrometer, and it apply|coated with the spin coater, and obtained the coating film. Furthermore, the coating film was prebaked at 100 degreeC under atmospheric pressure for 120 second using the hotplate (SCW-636; Dainippon Screen Seijo Co., Ltd. product), and the prebaked film|membrane was obtained. Double-sided alignment j-line (wavelength 313 nm), i-line (wavelength 365 nm), h-line (wavelength 405 nm) of an ultra-high pressure mercury lamp using a single-sided exposure apparatus (mask aligner PEM-6M; manufactured by Union Kogaku Co., Ltd.) and a mixed line of g-line (wavelength 436 nm) was irradiated with exposure light to the entire surface of the prebaked film at the minimum required exposure amount obtained by the above-described method to obtain an exposure film. Then, using a small-sized developing device for photolithography (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.), it was developed with a 2.38 wt% TMAH aqueous solution for 60 seconds, rinsed with deionized water for 30 seconds to obtain a developing film, and a high-temperature inner Using a gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.), the developing film is heated at 250° C. for 60 minutes in a nitrogen atmosphere, and a cured film having a thickness of 1.0 μm is provided on the Tempax. A substrate for evaluation was obtained. Table 14 shows the results of evaluating the light-shielding properties of the cured film by the method described above.

Next, with the following method, the organic electroluminescent display for light emission reliability evaluation provided with the cured film containing the hardened|cured material of the negative photosensitive composition 1 as a pixel division layer was produced. 2 shows a manufacturing process of the organic EL display device including the forming process of the pixel division layer.

On the surface of the 38 mm x 46 mm alkali-free glass substrate 11, by sputtering, a thin film of silver/copper alloy with a thickness of 10 nm (volume ratio of 10:1) is formed over the entire surface and etched to form a patterned metal reflective layer. (12) was formed. Next, by sputtering, an ITO transparent conductive film with a thickness of 10 nm is formed on the entire surface, etched to form a second electrode 13 on the same pattern and an auxiliary electrode 14 as an outgoing electrode, followed by "Semicoclean" "(registered trademark) 56 (manufactured by Furuchi Chemical Co., Ltd.) was ultrasonically cleaned for 10 minutes, followed by washing 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 being stored for a long period of time under atmospheric pressure / under light blocking / in a constant temperature box at room temperature of 25 ° C ± 1 ° C for 30 days with a spin coater (MS-A100; Mikasa (MS-A100; Mikasa ( Note) was used, the rotation speed was adjusted so that the thickness of the pixel division layer finally obtained might be set to 1.0 micrometer, and it apply|coated to the surface of an electrode formation substrate, and obtained the coating film. Furthermore, the coating film was prebaked at 100 degreeC under atmospheric pressure for 120 second using the hotplate (SCW-636; Dainippon Screen Seijo Co., Ltd. product), and the prebaked film|membrane was obtained.

Using a double-sided alignment single-sided exposure apparatus (mask aligner PEM-6M; manufactured by Union Kogaku Co., Ltd.), j-line (wavelength 313 nm) and i-line (wavelength 365 nm) of an ultra-high pressure mercury lamp through a negative exposure mask , h-line (wavelength 405 nm), and g-line (wavelength 436 nm) mixed lines were pattern-irradiated with exposure light to the prebaked film at the minimum required exposure amount to obtain an exposure film. Then, using a small-sized developing device for photolithography (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.), it developed for 60 seconds with a 2.38 wt% TMAH aqueous solution, followed by rinsing with deionized water for 30 seconds to obtain a developing film. In addition, using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.), the developing film is heated at 250° C. for 60 minutes under a nitrogen atmosphere to form a cured film, and the vertical A pixel division layer forming substrate 1 having an aperture ratio of 25% was obtained, in which a pixel division layer 15 with a thickness of 1.0 μm was formed in an area of 16 mm/width 16 mm, with openings (70 μm wide/260 μm long) arranged. Table 14 shows the evaluation results of evaluating the development residue generated on the ITO electrode by the method described above. In addition, the opening part referred to here is a part which becomes the light emitting pixel part of an organic electroluminescent display finally after going through the process mentioned later.

Next, an organic EL display device was fabricated using the pixel division layer forming substrate 1 . In order to form the organic EL layer 16 including the light emitting layer by the vacuum deposition method, the pixel division layer forming substrate 1 is rotated with respect to the deposition source under the deposition condition of the ^{vacuum degree of 1×10 -3 Pa or less, and first, hole injection} As a layer, compound (HT-1) was formed to a thickness of 10 nm, and as a hole transport layer, compound (HT-2) was formed to a thickness of 50 nm. Next, on the light emitting layer, compound (GH-1) as a host material and compound (GD-1) as a dopant material were deposited to a thickness of 40 nm. Then, as an electron transport material, compound (ET-1) and compound (LiQ) were laminated in a volume ratio of 1:1 to a thickness of 40 nm.

Next, 2 nm of compound (LiQ) was vapor-deposited, and 10 nm of a silver/magnesium alloy (volume ratio 10:1) was vapor-deposited to form the first electrode 17 . Then, it sealed by adhering a cap-shaped glass plate using an epoxy resin adhesive in low humidity/nitrogen atmosphere, and the organic electroluminescent display 1 was obtained. In addition, the thickness mentioned here is a display value of 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 for formation of organic electroluminescent layer are shown below, respectively.

Next, separately, only the aperture ratio of the negative exposure mask was changed, and in the same procedure, an organic EL display device 2 having a pixel division layer having an aperture ratio of 18% was produced, and for the organic EL display devices 1 and 2, the method described above Table 14 shows the results of evaluating the luminescence reliability.

Moreover, the organic electroluminescent display for light emission reliability evaluation provided with the cured film containing the hardened|cured material of the negative photosensitive composition 1 as a pixel division layer and a planarization layer, respectively by the following method was produced.

Fig. 3 shows a manufacturing process of an organic EL display device including a process of forming a pixel dividing layer and a planarization layer.

On the surface of the 38 mm x 46 mm alkali-free glass substrate 18, using a spin coater, the number of rotations was adjusted so that the thickness of the planarization layer finally obtained was 1.5 mu m, the negative photosensitive composition 1 was applied, and the coating film was got it Using a hot plate, 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, j-line (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 through a negative exposure mask The mixed line was pattern-irradiated with exposure light to the prebaked film with the minimum required exposure amount, and the exposure film was obtained. Then, using a small-sized developing device for photolithography, it was developed for 60 seconds with a 2.38 wt% TMAH aqueous solution, followed by rinsing with deionized water for 30 seconds to obtain a developing film. Further, using a high-temperature inert gas oven, in a nitrogen atmosphere, the developing film is heated at 250° C. for 60 minutes to form a cured film, and a flattening layer 19 in the form of a solid film having no in-plane opening in the center of the alkali-free glass substrate ) was obtained.

Next, on the surface of the planarization layer 19, a thin film of a silver/copper alloy having a thickness of 10 nm (volume ratio of 10:1) and an ITO transparent conductive film having a thickness of 10 nm were sequentially formed on the entire surface by sputtering. A metal reflective layer/second electrode 20 and a metal reflective layer/auxiliary electrode 21 are patterned by collectively etching two layers of a silver/copper alloy thin film and ITO transparent conductive film, and then, "Semicoclean" 56 was ultrasonically cleaned for 10 minutes, and it wash|cleaned with ultrapure water, and obtained the electrode formation board|substrate. Here, 30 of the surface area of the planarization layer 19 is formed by forming a laminated pattern consisting of two layers of a 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%. % of the film surface was covered with the lamination pattern, and 70% of the film surface was exposed. For the subsequent steps, the pixel dividing layer 22 is formed using the negative photosensitive composition 1 in the same manner as when the above-described organic EL display device 2 was produced, and further, the light emitting pixel 23 and the first The electrodes 24 are sequentially formed and then sealed to produce an organic EL display device 3 comprising a pixel division layer having a film thickness of 1.0 µm/aperture ratio of 18% and a planarization layer having a film thickness of 1.5 µm/aperture ratio of 0%, In one method, luminescence reliability and dark spots were evaluated. The evaluation results are shown in Table 14.

(Examples 2 to 20, Comparative Examples 1 to 32)

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

Next, in the same procedure as in Example 1, except that negative photosensitive compositions 2 to 52 were respectively used instead of negative photosensitive composition 1, a light-shielding evaluation substrate, a pixel division layer evaluation substrate, and an organic EL display device were produced, The above-mentioned method evaluated light-shielding property, development residue, luminescence reliability, and a dark spot. The negative photosensitive compositions used and their evaluation results are summarized and shown in Tables 14 to 18. In addition, the pigment dispersion liquid used for preparation of the photosensitive composition was made to be used for preparation of a photosensitive composition within 2 hours after obtaining by the above-mentioned wet media dispersion process, without long-term storage alone as a pigment dispersion liquid. In addition, all the negative photosensitive compositions used were prepared in the same manner as in Example 1, and then stored for 30 days in a constant temperature box under atmospheric pressure / under light blocking / at room temperature of 25 ° C. ± 1 ° C. After long-term storage, stirred on a shaker for 1 minute. that was used

(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 photosensitizer, 0.30 g of VG-3101L as a thermal crosslinking agent, 15.15 g of PGMEA and 8.50 g of MBA was mixed, capped and stirred on a shaker for 30 minutes to prepare a positive photosensitive composition 1 having a solid content of 15.00 wt%, and dispersion stability was evaluated by the method described above. Here, the pigment dispersion used for preparation of the photosensitive composition was not stored for a long period of time by itself, but was used for preparation of the photosensitive composition within 2 hours after being obtained by the above-described wet media dispersion treatment. Table 19 shows the compounding quantity (g) of each raw material, and Table 20 shows the evaluation result of dispersion stability.

After preparation, using the positive photosensitive composition 1 stirred on a shaker for 1 minute after long-term storage under atmospheric pressure / under light shielding / in a constant temperature box at room temperature of 25 ° C ± 1 ° C for 30 days, exposure process and development process Table 20 shows the result of having obtained the board|substrate for light-shielding evaluation by the procedure similar to Example 1 except not carrying out, and evaluated the light-shielding property of a cured film by the above-mentioned method. Next, a pixel division layer evaluation substrate and an organic EL display device were manufactured in the same manner as in Example 1 except that the positive exposure mask in which the opening and the light-shielding portion of the negative exposure mask were inverted was used, and the development residue and light emission were produced in the same manner as described above. Reliability and dark spots were evaluated. The evaluation results are shown in Table 20.

(Example 22, Comparative Example 33)

Positive photosensitive compositions 2 to 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, respectively, and dispersion stability was evaluated by the method described above. Table 19 shows the compounding quantity (g) of each raw material, and Table 20 shows the evaluation result of dispersion stability.

After preparation, using the positive photosensitive compositions 2 to 3 stirred on a shaker for 1 minute after long-term storage for 30 days under atmospheric pressure / under light blocking / in a constant temperature box at room temperature 25 ° C ± 1 ° C, Example 21 and A substrate for light-shielding evaluation, a pixel division layer evaluation substrate, and an organic EL display device were produced in the same procedure, and the light-shielding property, development residue, luminescence reliability, and dark spot were evaluated by the method described above. The positive photosensitive composition used and its evaluation result are shown in Table 20.

In general, in the organic EL display devices of Comparative Examples 1 to 33, at least any one of dark spots and luminescence reliability are insufficient, but in the organic EL display devices of Examples 1-22, dark spots are suppressed and high It turns out that luminescence reliability is obtained and both characteristics are compatible.

From the above, it turns out that the organic electroluminescent display of this invention is useful.

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

1: TFT
2: wiring
3: TFT insulating film
4: planarization layer
5: Second electrode (ITO electrode)
6: Write
7: contact hole
8: pixel division layer
9: Emitting Pixels
10: first electrode
11: Alkali-free 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: alkali-free glass substrate
19: planarization layer
20: second electrode (ITO electrode)
21: auxiliary electrode (ITO electrode)
22: pixel division layer
23: light emitting pixel (organic EL layer)
24: first electrode

Claims (13)

An organic EL display device comprising a first electrode, a pixel division layer, a light emitting pixel, a second electrode, a planarization layer, and a base material, wherein the pixel division layer and/or the planarization layer have (a) a nitrogen-containing heterocyclic structure A black material, (b) a dispersing agent, and (c) resin are contained, and the (b) dispersing agent contains a compound represented by the following general formula (1) and/or a compound represented by the following general formula (2) which is an organic EL 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 is Na, K or NH ₄ R ¹ represents an organic group having an N,N-dialkylamino group at the terminal. Z ¹ represents an atom or a substituent directly bonded to a perylene ring, 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 general formula (2), R ² and R ³ are the same as each other, represent a hydrogen atom, an aryl group having a substituent, or a methyl group, X ² is a substituent directly bonded to a perylene ring and/or a benzene ring, -SO ₃ Represent H, -SO ₃ M, -SO ₂ NHR ⁴ or -CONHR ^4. M represents Na, K or NH ₄ R ⁴ represents an organic group having an N,N-dialkylamino group at the terminal Z ² represents an atom or a 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 to 8.) 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 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 n+m=10 is satisfied.)

(In the general formula (23), R ⁵ and R ⁶ are the same as each other and represent a hydrogen atom, an aryl group having a substituent, or a methyl group. X ⁴ represents _{-SO 3} H directly bonded to a perylene ring and/or a benzene ring; , 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 black material according to claim 1 or 2, wherein (a) the black material having a nitrogen-containing heterocyclic structure contains a perylene-based organic black pigment having two benzimidazole rings in a molecule as the nitrogen-containing heterocycle. EL display device. The black material having a nitrogen-containing heterocyclic structure (a) contains a mixture containing at least an organic yellow pigment, an organic red pigment, and an organic blue pigment, and the organic yellow pigment is benz An organic EL comprising an imidazolone-based organic yellow pigment, the organic blue pigment containing a phthalocyanine-based organic blue pigment and/or an indanthrone-based organic blue pigment, and the organic red pigment containing a perylene-based organic red pigment display device. The organic EL display device according to claim 1 or 2, wherein the resin (c) contains a polyimide resin. The organic EL display device according to claim 2, wherein the (b) dispersant contains the compound represented by the general formula (22) and the compound represented by the general formula (23). The organic EL display device according to any one of claims 1 to 6, wherein the (b) dispersing agent further contains a polymer type dispersing agent having a phosphoric acid group. The organic EL display device according to any one of claims 1 to 6, wherein the pixel dividing layer and/or the planarization layer contains a cured product of a negative photosensitive composition. The organic EL display device according to any one of claims 1 to 6, wherein the pixel dividing layer and/or the planarization layer contains a cured product of a positive photosensitive composition. The organic EL display device according to any one of claims 1 to 6, wherein the optical density per 1.0 µm of the pixel dividing layer and/or the flattening layer is 0.5 or more and 2.0 or less. The organic EL display device according to any one of claims 1 to 6, wherein the substrate is a flexible substrate containing a polyimide resin. The organic EL display device according to any one of claims 1 to 6, wherein an aperture ratio of the pixel dividing layer in a display area is 20% or less. A method of forming the pixel dividing layer and/or the planarization layer provided in the organic EL display device according to any one of claims 1 to 6, wherein 1.0 to 3.0 wt% of tetramethylammonium hydroxide is contained. A method of forming a pixel dividing layer and/or a planarization layer, comprising a developing step of obtaining a developing film using a developing solution.

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