TWI786189B - Organic EL display device, and method for forming pixel division layer and planarization layer - Google Patents

Abstract

The present invention provides an organic EL display device capable of suppressing black spots caused by development residues caused by pigment aggregates and having excellent luminescence reliability.

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

Description

Organic EL display device, and method for forming pixel division layer and planarization layer

The present invention relates to an organic EL display device.

Many products that incorporate organic electroluminescent (EL) displays in display devices with thin displays such as smartphones, tablet PCs, and TVs are currently being developed. The organic EL display device is a self-luminous display device that uses the energy released by the recombination of electrons injected from the cathode and holes injected from the anode to emit light. As a specific example thereof, an organic EL display device including a pixel dividing layer and a planarization layer having a function as an insulating film is disclosed (for example, Patent Document 1).

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

As a composition for forming a blackened pixel division layer, there may be mentioned a photosensitive composition containing organic pigments of various hues and performing blackening by subtractive color mixing. As a specific example, a composition containing organic A photosensitive composition of a red pigment and an organic blue pigment (for example, refer to Patent Document 3).

In addition, when an organic pigment is to be dispersed in a resin solution, due to re-agglomeration occurring during or after the dispersion step, sufficient coloring power may not be obtained in many cases, or in a dispersion system in which a plurality of pigments coexist. Cases where problems such as color separation occur. In order to solve the above-mentioned problems, it is known to use organic pigment derivatives (synergists) as dispersants to enhance resin adsorption on the surface of organic pigments and improve dispersion stability. Like the pixel division layer of organic EL display devices, in the field of black matrix of liquid crystal display devices that must have the function of reducing external light reflection, carbon black has the disadvantages of lack of insulation and high dielectric coefficient in terms of electrical characteristics. As a technique to replace the carbon black, a black-like photosensitive composition has attracted attention, and a technique of using an organic pigment and an organic pigment derivative in combination has been disclosed. As a specific example thereof, a photosensitive composition for imitating blackening containing a perylene-based organic pigment and a copper phthalocyanine derivative having a sulfonic acid group has been disclosed (for example, refer to Patent Document 4).

prior art literature patent documents

Patent Document 1 International Publication No. 2016/047483

Patent Document 2 Japanese Unexamined Patent Publication No. 2013-30293

Patent Document 3 Japanese Patent Laid-Open No. 2013-207124

Patent Document 4 International Publication No. 2015/015962

However, if the blackened photosensitive compositions described in Patent Documents 3 and 4 are used to form the pixel division layer and/or planarization layer of an organic EL display device, the dispersion stability of the organic pigment in the photosensitive composition is not stable. full. In addition, the dispersed state is easily destroyed in the development step, and development residues derived from pigment aggregates are generated on the ITO electrodes in the pattern openings, resulting in black spots. Also, Patent Document 4 describes a photosensitive composition that improves dispersion stability to some extent by increasing the content of copper phthalocyanine derivatives having sulfonic acid groups. However, if such a photosensitive composition is used If the pixel division layer and/or the planarization layer are not formed, there will be a problem that the reliability of light emission will be impaired, and there will be a problem that suppression of black spots and high reliability of light emission cannot be achieved at the same time.

Due to the above background, an organic EL display device that suppresses the occurrence of black spots and has high light emission reliability has been strongly desired.

The organic EL display device of the present invention is an organic EL display device provided with a first electrode, a pixel dividing layer, a light-emitting pixel, a second electrode, a planarization layer, and a substrate, and is characterized in that the pixel dividing layer and/or the planarization The layer includes: (a) a black material having a nitrogen-containing heterocyclic structure, (b) a dispersant, and (c) a resin; the (b) dispersant contains a compound represented by the following general formula (1) and/or is represented by the following general formula A compound represented by formula (2).

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

In the above general formula ( ² ), R2 and ^R3 are identical to each other, which represent a ^hydrogen atom, an aryl group or a methyl group with a substituent, and X2 is a substituent directly bonded to the perylene ring and/or benzene ring, which Represents -SO ₃ 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 a N,N-dialkylamino group at the end. Z ² represents an atom directly bonded to the perylene ring or a substituent, which represents a hydrogen atom, an alkyl group or an alkoxy group. p and q are integers, p means 1 or 2, and q means 6~8.

According to the organic EL display device of the present invention, black spots derived from development residue caused by pigment aggregates can be suppressed, and excellent light emission reliability can be obtained.

1‧‧‧TFT

2‧‧‧Wiring

3‧‧‧TFT insulating film

4‧‧‧planarization layer

5‧‧‧Second electrode (ITO electrode)

6‧‧‧Substrate

7‧‧‧Contact hole

8‧‧‧Pixel segmentation layer

9‧‧‧luminous 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 segmentation layer

16‧‧‧Light-emitting pixels (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 segmentation layer

23‧‧‧Light-emitting pixels (organic EL layer)

24‧‧‧First electrode

FIG. 1 is a cross-sectional view showing a TFT substrate of an organic EL display device according to an embodiment of the present invention.

FIG. 2 is a schematic diagram showing a method of manufacturing an organic EL display device provided with a pixel dividing layer in an example.

FIG. 3 is a schematic diagram showing a method of manufacturing an organic EL display device provided with a pixel dividing layer and a planarization layer in an embodiment.

form for carrying out the invention

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

In addition, the light-shielding property refers to the degree of shielding light with a wavelength of 380 to 780 nm in the visible light region, and the higher the light-shielding property, the lower the light transmittance. "C.I." used to refer to coloring materials is an abbreviation of Color Index Generic Name, which is based on the color index issued by The Society of Dyers and Colourists. Regarding the coloring materials registered in the color index, Color Index Generic Name means pigments Or the chemical structure or crystalline form of the dye. Organic pigment derivatives include pigment derivatives obtained by derivatization treatment using organic pigment powders as raw materials, but in the synthesis process, they do not necessarily have to be compounds obtained in the form of organic pigment powders.

In this specification, the description of an alkali developing solution means an organic alkali aqueous solution unless otherwise specified. The weight average molecular weight (Mw) was analyzed by gel permeation chromatography using tetrahydrofuran as a carrier, and a value converted from a standard polystyrene calibration curve was used.

The present invention is an organic EL display device, which is an organic EL display device provided with a first electrode, a pixel dividing layer, a light-emitting pixel, a second electrode, a planarization layer, and a substrate, wherein the pixel dividing layer and/or the planar The chemical layer comprises (a) a black material having a nitrogen-containing heterocyclic structure, (b) a dispersant and (c) a resin; the (b) dispersant contains a compound represented by the following general formula (1) and/or is represented by the following general formula A compound represented by formula (2). By adopting the above configuration, it was found that generation of black spots can be suppressed and excellent light emission reliability can be obtained, and the present invention has been completed. The black spots referred to here refer to the granular local non-luminous parts arranged unevenly in the pixel when the organic EL display device is driven. The long diameter of the black spots originating from the developing residue is the same as the long diameter of the developing residue or larger than the long diameter of the developing residue due to coarsening, which hinders light emission. Therefore, the more obvious the black spots, the lower the luminance, which in turn leads to display The value of the device decreases. The luminescence reliability referred to here means that when the organic EL display device is continuously turned on, the light-emitting area of the light-emitting element is not likely to shrink with the lapse of the lighting time (pixel Shrinkage), the higher the luminous reliability, the higher the value as a display device.

In the above general formula (1), X ¹ is a substituent directly bonded to the perylene ring, which 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. Z ¹ represents an atom directly bonded to the perylene ring or a substituent, which represents a hydrogen atom, an alkyl group or an alkoxy group. n and m are integers, n represents 1 or 2, and satisfies n+m=10.

In the above-mentioned general formula ( ² ), R2 and ^R3 are identical to each other, which represent a ^hydrogen atom, an aryl group or a methyl group with a substituent, and X2 is a substituent directly bonded to the perylene ring and/or benzene ring, which Represents -SO ₃ 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 a N,N-dialkylamino group at the end. Z ² represents an atom directly bonded to the perylene ring or a substituent, which represents a hydrogen atom, an alkyl group or an alkoxy group. p and q are integers, p means 1 or 2, and q means 6~8.

The organic EL display device of the present invention comprises a first electrode, a pixel dividing layer, a light emitting pixel, a second electrode, a planarization layer and a base material. FIG. 1 shows a cross-sectional view of a TFT substrate in an organic EL display device as a specific example of an embodiment of the present invention.

On the surface of the substrate 6 , lower-gate or upper-gate TFTs (thin film transistors) are provided in rows and rows, and the TFT insulating layer 3 is formed to cover the TFTs 1 and the wiring 2 connected to the TFTs 1 . Furthermore, 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 on the planarization layer 4 . The second electrode 5 is patterned on the surface of the planarization layer 4 and connected to the wiring 2 . The pixel dividing layer 8 is formed so as to surround the periphery of the pattern of the second electrode 5 . The pixel division layer 8 is provided with an opening, and the light-emitting pixel 9 including an organic EL light-emitting material is formed in the opening, and the first electrode 10 is formed to cover the pixel division layer 8 and the light-emitting pixel 9 . After sealing the TFT substrate including the above-mentioned multilayer structure under vacuum, if a voltage is directly applied to the light-emitting pixel portion, it can be made to emit light and become an organic EL display device.

The light-emitting pixels 9 are arranged by different types of pixels having light emission peak wavelengths in the three primary colors of light, that is, red, blue, and green regions, or light-emitting pixels that emit white light can also be fabricated on the entire surface. , and then combine red, blue, and green color filters as another laminated component. Usually, the peak wavelength of the displayed red region is 560-700nm, the peak wavelength of the blue region is 420-500nm, and the peak wavelength of the green region is 500-550nm, but in the organic EL display device of the present invention, the type of light-emitting pixels is not limited. Specifically defined, the emitted light may have any peak wavelength. As an organic EL light-emitting material constituting a light-emitting pixel, it is more preferable to use a material combining a hole transport layer and/or an electron transport layer in addition to the light-emitting layer.

As a method for patterning light-emitting pixels, a mask vapor deposition method is mentioned. The mask deposition method is a method in which an organic compound is vapor-deposited and patterned using a vapor-deposition mask. Specifically, a vapor-deposition mask having a desired pattern as an opening is placed on the substrate side and vapor-deposited. method. In order to obtain a high-precision vapor deposition pattern, it is important to make a high-planar vapor deposition mask and the substrate closely bonded. Generally, the technology of applying tension to the vapor deposition mask can be used, or the vapor deposition can be made by a magnet arranged on the back of the substrate. The technique of bonding the plating mask to the substrate, etc. As the method of manufacturing the vapor deposition mask, etching method or mechanical polishing, sand blasting method, sintering method, laser processing method, utilization of photosensitive resin, etc. can be mentioned, but in the case of forming a finer pattern, from using From the viewpoint of excellent machining accuracy, it is preferable to use an etching method or an electroforming method.

As the second electrode 5, for example, conductive metal oxides such as zinc oxide, tin oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), etc. can be used, among which, from the viewpoint of excellent transparency and conductivity In other words, ITO can be preferably used. As a method of patterning ITO, the following method can be mentioned: firstly, after forming the entire ITO film by the sputtering method, the positive photoresist material for etching is patterned by the lithography method, and the photoresist is obtained on the ITO film. pattern. Next, remove only the ITO film in the non-formed portion of the photoresist pattern with an etching solution at a temperature of 20-60°C, then remove the photoresist pattern with a photoresist stripping solution at a temperature of 20-60°C, and then perform heat treatment according to requirements to become expected crystallinity. The ITO referred to here includes so-called amorphous ITO. As a positive photoresist used for etching, a positive photosensitive composition containing an alkali-soluble novolac resin can be used. As the etchant, an aqueous solution containing nitric acid and hydrochloric acid or an aqueous solution of oxalic acid can be used. Examples of commercially available products include ITO-101N (manufactured by Kanto Chemical Co., Ltd.), "S-CLEAN" (registered trademark) IS- 2. IS-3 of the same series (the above are manufactured by Sasaki Chemical Co., Ltd.). As the photoresist stripping solution, an aqueous solution of an organic amine system can be used, and examples of commercially available products include "ANRASUTO" (registered trademark) M6, the same series of M6B, the same series of TN-1-5, the same series of M71- 2 (The above are Sanruo Pure Pharmaceutical Research Institute).

As the first electrode 10, for example, a silver alloy film is preferably used, but any substance may be contained as long as it has a layer functioning as an electrode. As a specific example of the first electrode 10 , when the organic EL display device of the present invention is a bottom emission type organic EL display device described later, a layer containing aluminum is preferably used from the viewpoint of excellent light reflectivity. In the case of a top emission type organic EL display device, it is preferable to use a layer containing a silver alloy having silver/magnesium from the viewpoint of excellent light transmission. The first electrode can be obtained by forming an entire film by a sputtering method.

The light extraction direction of the organic EL display device of the present invention can be a bottom emission type organic EL display device in which the emission light emitted by the light-emitting pixels is extracted to the substrate side through the substrate 6, or can be a bottom emission type organic EL display device through the first electrode. The top emission type organic EL display device in which the emitted light is extracted to the side opposite to the substrate 6 is not particularly limited. In the case of a top emission type organic EL display device, in order to improve light extraction efficiency in one direction, a patterned metal reflective layer or the like may be further provided between the planarization layer 4 and the second electrode 5 . Examples of the metal reflective layer include conductive films made of silver alloys containing different metal elements such as copper, gallium, and magnesium.

When a hard plate-like substrate represented by glass or the like is used as the substrate 6, a rigid organic EL display device that cannot be bent can be fabricated. As the glass, it is preferable to use an alkali-free glass containing less than 0.5% of an alkali metal element and containing silicon as a main component. Among them, those with a small coefficient of thermal expansion and excellent dimensional stability in high-temperature processes above 250°C are preferred, for example, OA-10G, OA-11 (the above are all manufactured by NEC Glass Co., Ltd.), AN- 100 (manufactured by Asahi Glass Co., Ltd.), and its thickness is usually 0.1 to 0.5 mm from the viewpoint of physical durability.

On the other hand, if a flexible base material is used as the base material 6, a bendable flexible organic EL display device can be produced. As a flexible base material, it is preferable to use a base material comprising polyimide resin with high flexibility and excellent mechanical strength. The surface of the support is followed by imidization of polyamic acid by heating to convert it into a polyimide resin, and then the temporary support is peeled off by laser or the like. Polyamic acid can be synthesized by reacting tetracarboxylic dianhydride and diamine compound in an amide-based solvent such as N-methyl-2-pyrrolidone. Among them, the coefficient of thermal expansion is small and the dimensional stability is excellent. From a viewpoint, polyamic acid which has the residue of an aromatic tetracarboxylic dianhydride and the 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. Its thickness is usually 10 to 40 μm, and the substrate 6 can be thinned compared to the case of using the above-mentioned alkali-free glass.

The pixel division layer and/or the planarization layer included in the organic EL display device of the present invention contains (a) a black material having a nitrogen-containing heterocyclic structure. The black material with nitrogen-containing heterocyclic structure referred to here refers to the pigment mixture containing the following (a-1) and (a-2) or refers to (a-3) organic black with nitrogen-containing heterocyclic structure Pigment; the (a-1) is selected from organic yellow pigments, organic red pigments and organic orange pigments with at least one organic pigment with a nitrogen-containing heterocyclic structure, and the (a-2) is selected from organic blue pigments and An organic pigment with nitrogen-containing heterocyclic ring structure of at least one color among organic purple pigments. By containing (a) a black material having a nitrogen-containing heterocyclic structure, the pixel dividing layer and/or the planarization layer can be blackened to impart light-shielding properties.

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

The (a) black material having a nitrogen-containing heterocyclic structure contained in the pixel division layer and/or planarization layer of the organic EL display device of the present invention is preferably compatible with an aqueous organic alkali solution in order to improve the reliability of light emission. An organic pigment with high alkali resistance and high heat resistance to heating. The alkali resistance referred to here specifically refers to the resistance to 2.38% by weight of tetramethylammonium hydroxide aqueous solution under the condition of atmospheric pressure and 25°C. The 2.38% by weight of tetramethylammonium hydroxide aqueous solution is developed later In the step of patterning the pixel dividing layer and the planarization layer, it is usually used as a developer. When the organic pigment is in contact with the developing solution through the binder, the more it can suppress the generation of dissolved and/or decomposed products of the pigment, the better. The heat resistance referred to here refers to the ability to suppress pyrolysis and/or sublimation generated by heating under atmospheric pressure/nitrogen atmosphere/250°C when the pixel division layer and planarization layer are thermally cured in the curing step described later. degree of things. The heat-resistant temperature of the permanent film required for the pixel division layer and the planarization layer of the organic EL display device is 250°C or higher. Luminous reliability.

As (a) a specific example of the nitrogen-containing heterocyclic structure in the molecule of the organic pigment contained in the black material having a nitrogen-containing heterocyclic structure, in addition to improving the heat resistance and alkali resistance of the organic pigment itself, from the following From the viewpoint that the compound represented by the above-mentioned general formula (1) and/or the compound represented by the above-mentioned general formula (2) have a strong interaction and can obtain a higher development residue suppression effect, particularly preferably, an imide ring , benzimidazolone ring, benzimidazole ring. It is preferable to make it contain the organic pigment which has any one of these nitrogen-containing heterocyclic structures.

In order to improve the light-shielding properties of the pixel division layer and/or planarization layer in the entire visible light region, it is preferable to contain three colors of (a-1) organic yellow pigment, organic red pigment, and (a-2) organic blue pigment. A combination or a combination of three colors including (a-1) an organic yellow pigment, (a-2) an organic blue pigment, and an organic violet pigment. In the case of a combination of (a-1) an organic yellow pigment, an organic red pigment, and (a-2) an organic blue pigment, the content of the organic pigments of the three colors in all pigment components in the photosensitive composition Preferably they are 20% by weight or more. In order to sufficiently shield light in the wavelength range of 550 to 780 nm and increase the optical density described later, the content of the organic blue pigment is more preferably 30.0% by weight or more in all pigments, and it is more preferable from the viewpoint of exposure sensitivity in the exposure step described later. 50.0% by weight or less.

On the other hand, in the case of a combination of three colors including (a-1) an organic yellow pigment, (a-2) an organic blue pigment, and an organic violet pigment, among all the pigment components in the photosensitive composition, the three colors The content of the organic pigments is preferably 20.0% by weight or more. In order to sufficiently shield light in a wavelength range of 450 to 650 nm and increase the optical density described later, the content of the organic violet pigment is more preferably 30.0% by weight or more, more preferably 50.0% by weight or less, in all the pigments.

Examples of organic yellow pigments having a nitrogen-containing heterocyclic structure include C.I. Pigment Yellow 120, 138, 139, 151, 175, 180, 185, 181, 192, and 194, including these pigments alone or in combination. It doesn't matter if you wait for the paint. Among them, from the standpoint of excellent alkali resistance and heat resistance, organic yellow pigments having a benzimidazolone ring structure and not containing halogen atoms are preferred, and C.I. Pigment Yellow 120, 151, 175, 180, and 181 are preferred. , 192, 194. More preferably, it is C.I. Pigment Yellow 194 and/or C.I. Pigment Yellow 192 represented by the following structural formula (3).

Examples of organic orange pigments having a nitrogen-containing heterocyclic structure include C.I. Pigment Orange 13, 36, 43, 61, 64, 71, and 72, and it does not matter if these pigments are contained alone or in combination. Among them, from the standpoint of excellent alkali resistance and heat resistance, organic orange pigments having a perinone structure are preferred, and C.I. Pigment Orange 43 represented by the following structural formula (4) is more preferred. As the trans isomer of C.I. Pigment Orange 43, from the viewpoint of luminescence reliability, it is ideal to use the one obtained by separating the isomers with high purity, and the cis isomer as a by-product during synthesis ( The residual amount of C.I. Pigment Red 194) is preferably 5.0% by weight or less relative to C.I. Pigment Orange 43.

Examples of organic red pigments having a nitrogen-containing heterocyclic structure include C.I. Pigment Red 122, 123, 149, 179, 180, 189, 190, 202, 209, 254, 255, and 264, including these pigments alone or including A plurality of such pigments is not harmful. Among them, those having high alkali resistance and heat resistance, containing no halogen atoms that adversely affect the reliability of light emission, and having a perylene ring structure and an imide ring structure are preferred. Preferred are C.I. Pigment Red 123 represented by the following structural formula (5), C.I. Pigment Red 149 represented by the following structural formula (6), C.I. Pigment Red 179 represented by the following structural formula (7), and C.I. Pigment Red 179 represented by the following structural formula ( 8) C.I. Pigment Red 190 represented.

Examples of organic blue pigments having a nitrogen-containing heterocyclic structure include C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:6, 16, 60, 64, 75, 79, 80 , these pigments may be contained alone or a plurality of such pigments may be contained. Among them, those with high alkali resistance and heat resistance, no halogen atoms in the structure that adversely affect the reliability of light emission, and those with a phthalocyanine structure or an indanthrene structure are preferred. It is preferably C.I. Pigment Blue 15:3 of the β-type stable crystal of copper phthalocyanine represented by the following structural formula (9) and C.I. Pigment Blue 15:6 of the ε-type stable crystal of copper phthalocyanine, with the following structural formula (10) C.I. Pigment Blue 60 represented by indanthrene blue (indanthrene blue) having an indanthrene structure.

In addition, the copper phthalocyanine organic blue pigments such as C.I. Pigment Blue 15:3, 15:6, etc. referred to here are all unsubstituted phthalocyanine organic blue pigments with stable crystal structure. Alkalinity is superior to copper phthalocyanine derivatives having a sulfonic acid group described in Patent Document 4, which is one of organic pigment derivatives. Among them, from the viewpoint of light emission reliability, it is preferable to use a free copper as an impurity with a content of 500 ppm or less, more preferably 100 ppm or less.

結構者。較佳為C.I.顏料紫29、37，從分散性之觀點而言，更佳為以下述結構式(11)表示之C.I.顏料紫29。 Examples of organic violet pigments having a nitrogen-containing heterocyclic structure include CI Pigment Violet 19, 23, 29, 32, and 37, and it does not matter if these pigments are contained alone or in plural. Among them, it is preferable to have high alkali resistance and heat resistance, no halogen atoms that have a bad influence on the reliability of luminescence in the structure, and a perylene ring structure and/or a bismuth ring structure.

Structurer. CI Pigment Violet 29 and 37 are preferable, and CI Pigment Violet 29 represented by the following structural formula (11) is more preferable from the viewpoint of dispersibility.

(a) When the black material having a nitrogen-containing heterocyclic structure includes a combination of three colors (a-1) organic yellow pigment, organic red pigment, and (a-2) organic blue pigment, the organic yellow pigment is the best It contains benzimidazolone-based organic yellow pigments, organic blue pigments preferably contain phthalocyanine-based organic blue pigments and/or indanthrene-based organic blue pigments, and organic red pigments preferably contain perylene-based organic pigments. red paint. By adsorbing the compound represented by the above-mentioned general formula (1) and/or the compound represented by the general formula (2) as described later, it is preferable to stably disperse the various pigments having different chemical structures.

Examples of (a-3) organic black pigments having a nitrogen-containing heterocyclic structure include perylene-based organic black pigments, benzodifuranone-based organic black pigments having a lactamide ring structure, azomethine azo (Azomethine-azo) is an organic black pigment. Among them, the compound represented by the above-mentioned general formula (1) and/or the compound represented by the above-mentioned general formula (2) are preferable in terms of excellent heat resistance and light-shielding property due to their strong interaction and high adsorption properties. It is a perylene-based organic black pigment having two benzimidazole rings in the molecule as nitrogen-containing heterocycles. As its specific example, a mixture of a compound represented by the following general formula (12) and a compound represented by the following general formula (13) can be mentioned, and the compound represented by the above general formula (1) and /or the compound represented by the general formula (2) can preferably stably disperse the various pigments with different chemical structures. The above-mentioned perylene-based organic black pigment having two benzimidazole rings in the molecule can be obtained as a cis-trans isomer mixture by reacting o-phenylenediamine or its derivatives with perylenetetracarboxylic dianhydride.

In the general formulas (12) and (13), R ⁷ to R ¹⁴ independently represent a hydrogen atom, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 6 carbons, or a hydroxyl group.

The pixel dividing layer and planarization layer included in the organic EL display device of the present invention may contain other than the organic pigments belonging to the above-mentioned (a-1), (a-2) or (a-3) components in order to fine-tune the optical characteristics. Pigments include, for example, titanium nitride, titanium oxynitride, and the like in addition to C.I. Pigment Green 7, 36, 58, 59, and C.I. Pigment Brown 25, 26, and 28.

(a) The content of the black material having a nitrogen-containing heterocyclic structure is preferably at least 5% by weight, more preferably 10% by weight, of the total solid content of the photosensitive composition in order to obtain sufficient light-shielding properties in the visible light region. %above. Moreover, in order to ensure the dispersion stability of the photosensitive composition and obtain sufficient sensitivity and developability to exposure, it is preferably at most 70% by weight, more preferably at most 50% by weight. The total solid content referred to here refers to the value obtained by dividing the weight sum of all components except the solvent contained in the photosensitive composition by the weight of the photosensitive composition and multiplying by 100.

(a) The average primary particle size of each of the various organic pigments contained in the black material having a nitrogen-containing heterocyclic structure, from the viewpoints of dispersion stability of the photosensitive composition, maintenance of dispersibility in the developing step, and luminescence reliability In terms of thickness, it is preferably at least 30 nm, more preferably at least 40 nm. On the other hand, it is preferably 150 nm or less, more preferably 100 nm or less, from the viewpoint of improving the linearity of the pattern of the pixel dividing layer and the planarization layer.

The average primary particle size referred to here refers to the number average value of the primary particle size calculated by the particle size measurement method using an image analysis type particle size distribution measuring device. The image can be taken using a transmission electron microscope (TEM), and the average primary particle size can be calculated from the image of more than 100 primary particles of organic pigments captured at a magnification of 50,000 times. When the organic pigment is non-spherical, the average value of the major axis and the minor axis is defined as the primary particle diameter. For image analysis, Mac-View, an image analysis type particle size distribution software manufactured by MOUNTECH, can be used.

When it is necessary to reduce the average primary particle size of the organic pigment or disintegrate the coarse part before carrying out the wet medium dispersion treatment described later, the average primary particle size is reduced by wet pulverization treatment such as solvent salt grinding method It doesn't hurt to adjust the diameter to the expected range. The solvent salt grinding method refers to the method of kneading and washing the mixture of organic pigments, water-soluble inorganic salts, and water-soluble organic solvents in a high-viscosity paste state. As the water-soluble inorganic salt, as long as it is a granular material that can be used as a grinding material, it is preferable to use sodium chloride, potassium chloride or potassium sulfate. The average primary particle size of the water-soluble inorganic salt is preferably about 0.5 to 50 μm. Examples of the water-soluble organic solvent include organic solvents such as glycol-based solvents, ether-based solvents, and alcohol-based solvents. Among them, glycol-based solvents are preferred, and specific examples include ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol, and triethylene glycol. Monomethyl ether, triethylene glycol monoethyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether. After kneading, it is preferable to repeatedly wash with water to remove water-soluble inorganic salts and water-soluble solvents.

The wet pulverizer used for kneading can use, for example, a kneader (manufactured by Inoue Manufacturing Co., Ltd.). On the one hand, the balance between the speed of micronization of organic pigments and the speed of coarsening due to crystal growth can be adjusted by mechanical power. On the one hand, kneading conditions such as pigment concentration, ground material concentration, kneading speed, temperature, and time during kneading may be appropriately set in order to obtain a desired average primary particle diameter. Preferably, each of the various organic pigments contained in the black material having a nitrogen-containing heterocyclic structure (a) is kneaded separately.

(a) The black material having a nitrogen-containing heterocyclic structure, the compound represented by the above-mentioned general formula (1) and/or the compound represented by the above-mentioned general formula (2), by combining NMR, infrared absorption spectrum, ICP mass analysis, Time-of-flight mass spectrometer (TOF-MS) and powder X-ray diffraction with CuKα line can identify its chemical structure and crystal form. In addition, the number of substituents n or p of the compound represented by the above-mentioned general formula (1) and/or the compound represented by the above-mentioned general formula (2) described later may be analyzed in combination with liquid chromatography.

The pixel dividing layer and/or planarization layer included in the organic EL display device of the present invention contains (b) a dispersant. Components belonging to the (b) dispersant are roughly classified into (b-1) non-polymer dispersants and (b-2) polymer dispersants.

Examples of (b-1) non-polymer dispersants include organic pigment derivatives, such as organic pigments and dyes, in which acidic functional groups and/or basic functional groups are introduced into molecules of organic pigments, and rosin Department of dispersants. The acidic functional groups referred to herein include groups in the form of salts.

On the other hand, examples of the (b-2) polymer-type dispersant include polymers having an acidic adsorption group and/or a basic adsorption group in the molecule.

(b) The action mechanism of the dispersant is not only acid-base interaction and π-π electron interaction, but also complexly related to hydrogen bond, Van-der-Waals force, etc., which will be described later in the production. In the wet medium dispersion treatment of the pigment dispersion, by improving the wettability of the organic pigment surface to the dispersion medium, and improving the steric repulsion effect and/or electrostatic repulsion effect of the organic pigments caused by the polymer chain, it can be Accelerates the de-agglomeration of secondary aggregates of organic pigments, and inhibits re-aggregation, thereby achieving the effect of stabilizing its dispersed state.

The photosensitive composition for patterning the pixel dividing layer and/or planarizing layer included in the organic EL display device of the present invention can be filled with the component belonging to (b) dispersant in advance. In the film of the resulting pixel division layer and/or planarization layer.

The pixel dividing layer and/or planarization layer of the organic EL display device of the present invention contains a compound represented by the following general formula (1) and/or a compound represented by the following general formula (2) (hereinafter sometimes referred to as The compound represented by the general formula (1) and/or the compound represented by the following general formula (2) are described as "perylene-based pigment derivatives with a specific structure") as (b-1) non-polymer dispersant.

In the above general formula (1), X ¹ is a substituent directly bonded to the perylene ring, which 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. Z ¹ represents an atom directly bonded to the perylene ring or a substituent, which represents a hydrogen atom, an alkyl group or an alkoxy group. n and m are integers, n represents 1 or 2, and satisfies n+m=10.

In the above-mentioned general formula ( ² ), R2 and ^R3 are identical to each other, which represent a ^hydrogen atom, an aryl group or a methyl group with a substituent, and X2 is a substituent directly bonded to the perylene ring and/or benzene ring, which Represents -SO ₃ 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 a N,N-dialkylamino group at the end. Z ² represents an atom directly bonded to the perylene ring or a substituent, which represents a hydrogen atom, an alkyl group or an alkoxy group. p and q are integers, p means 1 or 2, and q means 6~8.

The characteristics of the above-mentioned perylene-based dye derivatives with specific structures will be described in order.

As a result of research by the inventors of the present case, it has been found that "a specific acidic functional group or a basic functional group is directly bonded to the carbon atom constituting the perylene ring and/or constituting the aryl group with a specific number of substituents in one molecule." The structure of the carbon atom of the benzene ring" perylene-based pigment derivatives exhibits the following three characteristics; and it is found that the perylene-based pigment derivatives are used in the pixel division layer and/or planarization layer of an organic EL display device, It is particularly effective in solving problems.

First, the perylene-based pigment derivatives with the above-mentioned specific structure are adsorbed by interacting with (a) a black material having a nitrogen-containing heterocyclic structure, which has the ability to increase the polarity of the pigment surface and promote the dispersion process in wet media described later. Micronization, and the function of improving dispersion stability after miniaturization. As a result, even if the photosensitive composition is stored for a long period of time, the effect of suppressing the occurrence of pigment aggregates and color separation can be exhibited.

Second, because the perylene-based pigment derivatives of the above-mentioned specific structure have high alkali resistance, even if they are in contact with a high-concentration organic alkali aqueous solution in the developing step described later, the molecular structure of the perylene-based pigment derivatives will not be destroyed. A good dispersion state can be maintained without losing the function as a dispersant in the developing step. As a result, the effect of suppressing the development residue on the ITO electrode due to pigment aggregates can be exerted.

The long-term preservation of the photosensitive composition referred to here refers to leaving the photosensitive composition in an airtight state for 30 days under atmospheric pressure/under light shielding/at a constant temperature of 25°C±1°C.

Third, the perylene pigment derivatives with the above specific structure have a rigid perylene ring as the mother skeleton, and their structure does not contain heavy metals or halogen atoms, so they exhibit high heat resistance, so they can be suppressed in harsh environments above 250°C. Thermal decomposition, and can avoid electrode corrosion caused by migration of heavy metals.

In addition, a highly polar functional group such as an acidic functional group or a basic functional group is directly bonded to a carbon constituting a perylene ring or a carbon constituting a benzene ring of an aryl group having a substituent, thereby suppressing the formation of a highly polar group. break away. Also, since the number of substituents per molecule is 1 or 2, sublimation of the organic dye derivative itself can be suppressed. As a specific example of the desulphurization referred to here, for example, desulfonation can be mentioned, which means that the sulfonic acid gene introduced into the molecular structure by the derivatization treatment described later is detached from the parent skeleton residue derived from the organic pigment by high temperature treatment. .

With such excellent characteristics, it is possible to suppress the sublimation of the perylene-based pigment derivative itself and the generation of thermal decomposition products of a specific structure in the hardening step described later. As a result, the above-mentioned development residue suppression effect can be obtained while high luminescence can be obtained. reliability.

The preferred structure of the functional group of the perylene-based pigment derivative with the above-mentioned specific structure, in the case of including the polymer-type dispersant (b-2) described later, is preferably the acid of the adsorption group contained in the structure. or alkaline to decide.

In the case of containing a polymer-type dispersant having a basic adsorption group, the structure of the perylene-based pigment derivative with the above-mentioned specific structure is superior to the above-mentioned general formula (1) and the above-mentioned general formula from the viewpoint of excellent effect of suppressing development residue. In (2), X ¹ and X ² are preferably acidic functional groups or their salts, that is, they are preferably -SO ₃ H or -SO ₃ M, more preferably -SO ₃ H. In the case of -SO ₃ M, M is preferably NH ₄ in order to improve the reliability of light emission. It does not matter whether these compounds are contained alone or in plural. In addition, the description of -SO ₃ H or -SO ₃ M in this specification also includes in the photosensitive composition, the hydrogen atom, sodium ion, potassium ion or ammonium ion in the sulfonic acid group is detached, and X ¹ and When X ² is in the state of an anion represented by -SO ₃ ^- , and in a state where -SO ₃ ^- is bonded to other constituents by forming an ionic bond with the (b-2) polymer type dispersant described later. In the above general formula (1), X ¹ represents any one of carbons that can be directly bonded to the carbons at positions 1, 2, 5, 6, 7, 8, 9, 10, 11, and 12 of the perylene ring. Also, in the above-mentioned general formula ( ² ), X2 represents the carbon that can be directly bonded to the 1, 2, 5, 6, 7, 8, 11, and 12 positions constituting the perylene ring and the aryl group that constitutes the substituent. Any of the carbons of the benzene ring. Among them, in order to obtain higher luminescence reliability, X ² is preferably directly bonded to any one of the carbons at positions 1, 2, 5, 6, 7, 8, 11, and 12 of the perylene ring. In addition, the description method of each structural formula using [ ] in the general formulas (1) and (2) means that the number of each functional group introduced per molecule of the organic dye derivative may be the same according to the technical common sense of those skilled in the art. , and a mixture of various compounds in which the positions of the carbons to which each functional group is bonded are different. For example, in the case of a compound in which X ¹ is -SO ₃ H, n is 1, Z ¹ is a hydrogen atom, and m is 9 in the above general formula (1), it can be expressed as perylene-3,4-dicarboxyimide The monosulfonated compound of perylene-3,4-dicarboxyimide-9-sulfonic acid and perylene-3,4-dicarboxyimide-8-sulfonic acid. In addition, taking unsubstituted perylene-3,4-dicarboxyimide represented by the following structural formula (14), which constitutes a part of the skeleton of the chemical structure of the perylene-based dye derivative with the above-mentioned specific structure, as an example, Shows the position number of each carbon that makes up the perylene ring.

In the above-mentioned general formula ( ² ), R2 and ^R3 are preferably aryl groups or methyl groups having substituents from the viewpoint of improving the reliability of light emission. The aryl group or methyl group having a substituent referred to herein refers to an aryl group having a substituent or a methyl group, which means any one of them. The substituent referred to here refers to a substituent other than X ² bonded to the carbon constituting the benzene ring of the aryl group. In addition, the aryl group referred to here refers to an aryl group having at least a benzene ring, and does not include a heteroaryl group such as a pyridyl group having a nitrogen-containing heterocyclic structure. In addition, an aliphatic group bonded to an aromatic ring having a substituent, such as 4-methoxyphenylmethyl, is not included. That is, for example, an organic pigment derivative having the molecular structure of CI Pigment Black 32 as a residue after derivatization treatment is not included in the elements constituting the present invention.

The aryl group having a substituent includes, for example, ethoxyphenyl, dimethylphenyl, methoxyphenyl, phenylazophenyl, diisopropylphenyl, and more specific substituted Form, from the viewpoint of improving the reliability of luminescence, 4-ethoxyphenyl, 3,5-dimethylphenyl, 4-methoxyphenyl, 4-(phenylazo)benzene base.

In addition, in the above-mentioned general formula (1) and the above-mentioned general formula (2), in order to improve the heat resistance of the perylene-based pigment derivative itself with a specific structure, Z ¹ and Z ² are preferably both hydrogen atoms.

In the case where the (b-2) polymer-type dispersant described later includes a polymer-type dispersant having an acidic adsorption group as an adsorption group, from the viewpoint of excellent effect of suppressing development residue, the above formula (1) represents The compound, preferably in the above general formula (1), X ¹ is a basic functional group. That is -SO ₂ NHR ¹ or -CONHR ¹ . From the viewpoint of light emission reliability, -CONHR ¹ is more preferable.

On the other hand, the compound represented by the above-mentioned general formula (2) is preferably that X ² in the general formula (2) is a basic functional group. That is, it is preferably -SO ₂ NHR ⁴ or -CONHR ⁴ . From the viewpoint of light emission reliability, -CONHR ⁴ is more preferable. Examples of organic groups R ¹ and R ⁴ having N,N-dialkylamino groups at their terminals include N,N-dimethylaminomethyl, N,N-dimethylaminoethyl, N,N -Dimethylaminopropyl, N,N-dimethylaminobutyl, N,N-diethylaminomethyl, N,N-diethylaminoethyl, N,N-diethylaminopropyl N,N-diethylaminobutyl, N,N-dipropylaminomethyl, N,N-dipropylaminoethyl, N,N-dipropylaminopropyl, N,N-dipropylaminopropyl Butyl, N,N-dibutylaminomethyl, N,N-dibutylaminoethyl, N,N-dibutylaminopropyl, N,N-dibutylaminobutyl.

Among them, from the standpoint of strong adsorption with the polymer-type dispersant (b-2) described later and an excellent effect of suppressing development residue, it may be an organic group having an N,N-dimethylamino group at the end or an organic group having an N,N-dimethylamino group at the end. An organic group of N,N-diethylamino. Preferred are N,N-dimethylaminomethyl, N,N-dimethylaminoethyl, N,N-dimethylaminopropyl, N,N-dimethylaminobutyl, N,N - Diethylaminomethyl, N,N-diethylaminoethyl, N,N-diethylaminopropyl, N,N-diethylaminobutyl.

Specific examples of the compound in which X1 is ^a basic functional group include, for example, compounds represented by the following structural formulas (15) and (16), and specific examples of ^compounds in which X2 is a basic functional group. For example, preferably, compounds represented by the following structural formulas (17) to (21) are mentioned, for example.

The perylene-based pigment derivatives with the above-mentioned specific structure, regardless of having an acidic functional group or a basic functional group, can obtain the effect of suppressing the development residue derived from (a) a black material having a nitrogen-containing heterocyclic structure, but in order to make it more The interaction with the ITO surface is smaller and the effect of suppressing black spots is improved. The perylene pigment derivatives with specific structures preferably have acidic functional groups. Among them, it is more preferable to have a sulfonic acid group (—SO ₃ H) as the acidic functional group from the viewpoint of improving the dispersion stability and suppressing the development residue. As the perylene-based dye derivative having a specific structure of a sulfonic acid group, it is preferable to contain a compound represented by the following general formula (22) and/or a compound represented by the following general formula (23). It is more preferable to use a compound represented by the following general formula (22) and a compound represented by the following general formula (23) in combination from the viewpoint of excellent dispersion stabilization effect and development residue suppression effect. In addition, in the following general formula (22), the sulfonic acid group (-SO ₃ H) can also be directly bonded to No. 1, 2, 5, 6, 7, 8, 9, 10, 11, and 12 of the perylene ring. Any one of the carbons in the position. In the following general formula (23), the sulfonic acid group can also be directly bonded to the carbons at positions 1, 2, 5, 6, 7, 8, 11, and 12 of the perylene ring and the aryl groups with substituents. Any one of the carbons of the benzene ring.

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

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

In the above general formula (23), R ⁵ and R ⁶ are preferably substituted aryl or methyl groups from the viewpoint of heat resistance. The aryl group or methyl group having a substituent referred to herein refers to an aryl group having a substituent or a methyl group, which means any one of them. The aryl group having a substituent is the same as the examples of R2 and ^R3 in the above general formula ( ² ), for example, ethoxyphenyl, dimethylphenyl, methoxyphenyl, benzene Azophenyl, diisopropylphenyl. As a more specific form of substitution, 4-ethoxyphenyl, 3,5-dimethylphenyl, 4-methoxyphenyl, 4-(benzene azo)phenyl.

Preferable examples of the compound represented by the general formula (22) include compounds represented by the following structural formula (24). Moreover, as a compound represented by the said General formula (23), Preferably, the compound represented by the following structural formula (25) is mentioned, for example. These compounds may be contained alone or a plurality of such compounds may be contained.

A perylene-based pigment derivative of a specific structure as a component of the (b) dispersant is a compound in which the number of substituents n of X1 in the above general formula ( ¹ ) is 1 or 2, but may further include a number of substituents n is a compound of 3 or more. However, in the case of making it contain a compound having a substituent number n of 3 or more, in order to obtain high luminescence reliability, it is preferably the same as the average substituent number of a compound in which the substituent n of X1 in the general formula ( ¹ ) is 1 or 2 In the range of 1.0~2.0. For example, when a compound having a substituent n of 1 and a compound having a substituent n of 3 are contained in equimolar amounts, the average number of substituents is 2.0. It is also the same when the compound whose substituent p is 1 or ² and the compound whose substituent p is 3 or more in the general formula (2) is used to make it contained therein. ~2.0 range.

As a method for synthesizing a perylene-based dye derivative of a specific structure contained in the pixel dividing layer and/or planarization layer of the organic EL display device of the present invention, for example, industrially available perylene-3, 4-Dicarboxyimide, perylene-3,4-dicarboxyimide carboxylic acid, C.I. Pigment Red 123, C.I. Pigment Red 149, C.I. Pigment Red 178, C.I. Pigment Red 179, C.I. Pigment Red 190, C.I. Pigment Violet 29. N,N'-bis(2,6-diisopropylphenyl)-3,4,9,10-perylenetetracarboxylic acid diimide (hereinafter sometimes referred to as "perylene orange"), or Compounds having such perylene ring structures are used as starting materials, and subjected to various derivatization treatments described later to obtain desired chemical structures.

As a synthesis method of the compound having the above-mentioned acidic functional group or its salt in the above-mentioned general formula (1), for example, perylene-3,4-dicarboxyimide can be dissolved in 10~40% oleum, 70~100 % Concentrated sulfuric acid, chlorosulfonic acid or a mixture thereof, and stir for 1-6 hours while heating to 40-90°C. After that, a large amount of water or ice water whose weight is more than 100 times that of the perylene-3,4-dicarboxyimide used is added to precipitate to obtain a red solid, which is washed with water and filtered, and then After washing with acetone and drying, followed by dry pulverization, a compound in which X ¹ is -SO ₃ H in the above general formula (1) can be obtained.

Furthermore, at least one -SO ₃ H in the molecule can be made into a sodium salt (- SO ₃ Na), potassium salt (-SO ₃ K) or ammonium salt (-SO ₃ NH ₄ ), that is, the compound where X ¹ is -SO ₃ M can be obtained. Also, by adjusting the amount of the inorganic alkaline liquid, the mixing ratio of -SO ₃ H and -SO ₃ M can be controlled.

As a synthesis method of the compound having the above-mentioned basic functional group in the above-mentioned general formula (1), perylene-3,4-dicarboxyimide can be dissolved in 10~40% oleum, 70~100% concentrated sulfuric acid, Chlorosulfonic acid or mixtures thereof. Next, after stirring for 1 to 6 hours while heating to 40 to 90° C., thionyl chloride was added and stirred to obtain perylene-3,4-dicarboxyimidosulfonyl chloride. Afterwards, in the presence of a catalyst, it is reacted with a predetermined amount of N,N-dialkylaminoalkylamines, thereby serving as a sulfonamide, and then put into the weight relative to the used perylene-3,4-di Carboxylimide is precipitated in a large amount of water or ice water more than 100 times to obtain a dark red solid, which is washed with water and filtered. Then, it was washed with acetone to remove the catalyst, dried, and subjected to dry pulverization to obtain a compound in which X ¹ is -SO ₂ NHR ¹ in the above general formula (1).

Also, perylene-3,4-dicarboxyimide carboxylic acid was dissolved in a methylene chloride solvent, and thionyl chloride was added and stirred to prepare perylene-3,4-dicarboxyimide carbonyl chloride Finally, the methylene chloride solvent and unreacted thionyl chloride were removed under reduced pressure. Afterwards, in the presence of a catalyst, it was reacted with a predetermined amount of N,N-dialkylaminoalkylamines to form a carboxamide, and the obtained dark red solid was washed with water and filtered. Then wash with acetone, remove the catalyst, dry it, and perform dry pulverization treatment to obtain the compound in which X ¹ is -CONHR ¹ in the above general formula (1). Examples of the catalyst for promoting the reaction to obtain the above-mentioned aramide or carboxamide include amine-based catalysts such as trimethylamine and triethylamine.

Examples of N,N-dialkylaminoalkylamines include N,N-dimethylaminomethylamine, N,N-dimethylaminoethylamine, N,N-dimethylaminopropylamine, N,N-Dimethylaminobutylamine, N,N-Diethylaminomethylamine, N,N-Diethylaminoethylamine, N,N-Diethylaminopropylamine, N,N-Diethylamine butylamine, N,N-dipropylaminomethylamine, N,N-dipropylaminoethylamine, N,N-dipropylaminopropylamine, N,N-dipropylaminobutylamine, N,N-dibutylamine Methylamine, N,N-Dibutylaminoethylamine, N,N-Dibutylaminopropylamine, N,N-Dibutylaminobutylamine. Various perylene-based pigment derivatives having desired basic functional groups can be synthesized by using these compounds alone or in combination.

On the other hand, instead of the above-mentioned perylene-3,4-dicarboxyimide or perylene-3,4-dicarboxyimide carboxylic acid, C.I. Pigment Red 123, C.I. Pigment Red 149, C.I. Pigment Red 178, C.I. Pigment Red 179, C.I. Pigment Red 190, C.I. Pigment Violet 29, perylene orange or compounds having these perylene rings are used as starting materials, by the same synthesis method as the aforementioned compound represented by the above general formula (1) According to the reaction scheme of the derivatization treatment, compounds having various functional groups represented by the above general formula (2) can be obtained.

For example, by derivatizing CI Pigment Red 123 represented by the above structural formula (5) as a starting material, a compound in which R ² and R ³ are 4-ethoxyphenyl in the above general formula (2) can be obtained . By derivatizing CI Pigment Red 149 represented by the above structural formula (6) as a starting material, a compound in which R ² and R ³ are 3,5-dimethylphenyl in the above general formula (2) can be obtained . By derivatizing CI Pigment Red 178 as a starting material, a compound in which R ² and R ³ are 4-(phenylazo)phenyl in the above general formula (2) can be obtained.

By derivatizing CI Pigment Red 179 represented by the above structural formula (7) as a starting material, a compound in which R ² and R ³ are methyl groups in the above general formula (2) can be obtained. The compound in which R ² and R ³ are 4-methoxyphenyl in the above general formula (2) can be obtained by derivatizing CI Pigment Red 190 represented by the above structural formula (8) as a starting material. By derivatizing CI Pigment Violet 29 represented by the above structural formula (11) as a starting material, a compound in which R ² and R ³ are hydrogen atoms in the above general formula (2) can be obtained. A compound in which R ² and R ³ are 2,6-diisopropylphenyl in the above general formula (2) can be obtained by derivatizing perylene orange as a starting material.

In order to obtain high luminescence reliability, the perylene-based dye derivatives with a specific structure obtained by the above methods are preferably purified separately to remove impurities in advance. As the residual amount of ionic impurities derived from the chemical solution used for the above-mentioned derivatization treatment, sulfate ion (SO ₄ ^2- ), sulfite ion (SO ₃ ^- ), and chloride ion (Cl ^- ) are preferable. The contents are respectively 100 ppm or less, more preferably 50 ppm or less. The remaining amount of the ionic impurities can be measured by ion chromatography, and the powder of the perylene pigment derivative with a specific structure can be dispersed in deionized water to improve the removal rate by using a wet media disperser. Addition of ion exchange resin and agitation further enhances the removal rate.

Perylene-based pigment derivatives with a specific structure, on the one hand, in order to avoid their own coarse particles remaining in the pigment dispersion, and on the other hand, for a higher dispersion stabilization effect, it is ideal to use a dry powder that is fully dry pulverized Or, the average primary particle size thereof is preferably not more than 150 nm, more preferably not more than 100 nm. The average primary particle size of the perylene-based dye derivative with a specific structure can be evaluated by the same method as the above (a) black material having a nitrogen-containing heterocyclic structure. In addition, in the case of containing impurities derived from salts of sulfur-containing compounds and amine-based catalysts in the chemical solution used for the above-mentioned derivatization treatment, from the viewpoint of luminescence reliability, it is preferable to wash with water repeatedly. After removing it as much as possible, perform dry powdering.

The method of making the photosensitive composition contain the perylene-based dye derivative of the above-mentioned specific structure is not particularly limited, and specific examples are given below as preferred methods.

In the presence of a perylene-based pigment derivative of a specific structure, by kneading at least one color of organic pigments among the organic pigments belonging to (a) black materials having a nitrogen-containing heterocyclic structure, it is pre-adsorbed/supported on the pigment The surface is then dried and then pulverized, and a dry powdered organic pigment derivative-treated secondary processed pigment is produced first. Next, a method of performing a wet medium dispersion treatment with other organic pigments and using the obtained pigment dispersion to produce a photosensitive composition can be mentioned. Alternatively, the following method can be mentioned: in the presence of a perylene-based pigment derivative of a specific structure, (a) the black material having a nitrogen-containing heterocyclic structure is uniformly subjected to a wet medium dispersion treatment, and the resulting pigment dispersion is used to Manufacture of photosensitive composition.

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

系色素衍生物、紫環酮系色素衍生物以外，可列舉具有酸性官能基或鹼性官能基的1,3,5-三

系化合物。(a)具有含氮雜環結構 的黑色材為含有(a-1)選自有機黃色顏料、有機紅色顏料及有機橙色顏料之至少1色的具有含氮雜環結構的有機顏料與(a-2)具有含氮雜環結構之有機藍色顏料的顏料混合物的情況中，較佳為併用蒽醌系色素衍生物，可舉出例如以下述結構式(56)表示之化合物。 Also, within the range that does not adversely affect the light emission reliability, organic dye derivatives other than the perylene dye derivatives of the above-mentioned specific structure or compounds that can obtain the same effect as a synergist can also be used in combination. , to control the dispersion stability and the inhibitory effect of developing residue. For example, in addition to indanthrene-based pigment derivatives, metal-free phthalocyanine-based pigment derivatives, anthraquinone-based pigment derivatives, pyranthrone-based pigment derivatives, quinacridone-based pigment derivatives, di

In addition to pigment derivatives and perionone-based pigment derivatives, 1,3,5-tridiox having an acidic functional group or a basic functional group

Department of compounds. (a) The black material having a nitrogen-containing heterocyclic structure is an organic pigment having a nitrogen-containing heterocyclic structure containing (a-1) at least one color selected from organic yellow pigments, organic red pigments, and organic orange pigments and (a- 2) In the case of a pigment mixture of 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).

As the component belonging to the (b-1) non-polymer dispersant, it may contain a rosin-based dispersant. The rosin-based dispersant has the effect of improving the wettability of the dispersion medium on the surface of the pigment, and it can be used as an auxiliary agent to further enhance the dispersion stabilization effect of the perylene-based pigment derivative with a specific structure. Examples of rosin-based dispersants include rosin monomers, rosin dimers, maleic-acid-modified rosins, fumaric-acid-modified rosins, or mixtures thereof. Among them, a rosin-based dispersant containing a rosin monomer and a rosin dimer containing one or more carboxyl groups in the molecule and having an acid value in the solid content in the range of 100 to 300 (mgKOH/g) is preferred, as a commercially available Specific examples include "Poly-Pale Partially Dimerized Rosin" (registered trademark), "Dymerex Polymerized Rosin" (registered trademark) (all manufactured by EASTMAN CHEMICAL), ARDYME R-95, PINECRYSTAL KR140 (all manufactured by Arakawa Chemical Industry (stock) system).

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

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

(b-2) As the basic adsorption group possessed by the polymer type dispersant, for example, in addition to the tertiary amine group or its salt, and the quaternary ammonium salt group, there are also isocyanurate groups at the end of the molecule. An organic group of a heterocyclic ring such as a ring. Among them, a tertiary amino group is more preferable from the viewpoint of excellent dispersion stabilization effect and excellent effect of suppressing development residue on ITO.

As a polymer type dispersant having a tertiary amino group, for example, when the main chain is an acrylic polymer chain, ethylenically unsaturated monomers having a dialkylamino group and other ethylenically unsaturated monomers are mentioned. of copolymers. As a specific example, a dispersant having a structural unit represented by the following general formula (26) can be preferably used. Examples of ethylenically unsaturated monomers having a dialkylamino group include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethyl (meth)acrylate, Aminoethyl ester, diethylaminopropyl (meth)acrylate.

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 carbons, and R ¹⁷ and R ¹⁸ independently represent an alkyl group having 1 to 4 carbons.

On the other hand, when the main chain is a polyoxyalkylene-based polymer chain, as a specific example, it is preferable to use a dispersant having a tertiary amino group at a molecular end and an ethylene oxide/propylene oxide chain.

(b-2) The acidic adsorption group possessed by the polymer-type dispersant includes, for example, a phosphoric acid group, a sulfonic acid group, a carboxylic acid group, and a phenolic hydroxyl group. From the viewpoint of excellent effect of developing residues, phosphoric acid groups are preferred, and polymer-type dispersants containing at least phosphoric acid groups are preferred.

As a specific example of a polymer type dispersant having a phosphoric acid group, for example, in the case where the main chain is an acrylic polymer chain, a combination of an ethylenically unsaturated monomer having a phosphoric acid group and other ethylenically unsaturated monomers can be mentioned. copolymer. As a specific example, a dispersant having a structural unit represented by the following general formula (27) can be preferably used.

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 1-10.

Examples of ethylenically unsaturated monomers having a phosphoric acid group include 2-methacryloxyethyl acid phosphate, (meth)acrylic acid phosphonyloxyethyl, (meth)acrylic acid Acid phosphonyloxypropyl ester, acid phosphonyloxypolyoxypropylene glycol (meth)acrylate.

As other ethylenically unsaturated monomers for copolymerization with the above-mentioned ethylenically unsaturated monomer having a dialkylamino group or ethylenically unsaturated monomer having a phosphoric acid group, for example, benzyl (meth)acrylate ester, styrene, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, polyethylene glycol (meth)acrylate, (meth)acrylate Base) Acrylic Polypropylene Glycol, (Meth) Acrylic Polyethylene/Polypropylene Glycol. From the standpoint of high affinity with the perylene-based pigment derivatives of the above-mentioned specific structure, excellent dispersibility, and improved heat resistance, the dispersant preferably has a benzyl group on the side chain, and is preferably used (methyl ) benzyl acrylate.

Commercially available products can be used as (b-2) polymer-type dispersants, and examples of polymer-type dispersants having only acidic adsorption groups include "DISPERBYK" (registered trademark)-102, 110, 111, 118, 2096, BYK-P104, P105, "Solsperse" (registered trademark) 3000, 21000, 36000, 36600 (all manufactured by Lubrizol Corporation), AJISPER PA111 (manufactured by Ajinomoto Fine-Techno Corporation). These dispersants can be used alone or in combination.

Examples of polymer-type dispersants having only basic adsorption groups include "DISPERBYK" (registered trademark)-161, 162, 2163, 164, 2164, 167, 168, 2000, 2050, 2150, 2155, 9075 . . These dispersants can be used alone or in combination.

As a polymer type dispersant having an acidic adsorption group and a basic adsorption group, for example, "DISPERBYK" (registered trademark)-142, 145, 2001, 2010, 2020, 2025 (both are manufactured by BYK Corporation), "SOLSPERSE" (registered trademark) 9000, 11200, 13650, 24000SC, 24000GR, 32000, 32500, 32550, 33000, 34750, 35100, 35200, 37500, 39000, 56000 (manufactured by Lubrizol), AJISPER, B84, PB821, PB822 , PB883 (the above are all manufactured by Ajinomoto Fine-Techno).

The pixel dividing layer and/or the planarization layer included in the organic EL display device of the present invention contains (c) resin. The (c) so-called bonding material (adhesive) in the resin-based pixel division layer and/or planarization layer referred to here refers to the above-mentioned (a) black material having a nitrogen-containing heterocyclic structure and (b) The dispersant is immobilized and has a film-forming function under normal temperature/atmospheric pressure conditions.

The component belonging to (c) resin can be filled in the photosensitive composition for patterning the pixel dividing layer and/or planarizing layer included in the organic EL display device of the present invention by making it contained in the In the film of the resulting pixel division layer and/or planarization layer.

The photosensitive composition used to form the pixel dividing layer and/or the planarization layer may be a negative photosensitive composition used in negative photolithography by using a negative photolithography through a negative exposure mask. Pattern exposure reduces the alkali solubility of the film in the exposed area, and then removes the film in the unexposed area with an alkali developing solution to form a pattern. Alternatively, it may be a positive-type photosensitive composition used in so-called positive-type lithography, which is exposed through a pattern through a positive-type exposure mask, compared with the base of the film in the unexposed portion Solubility, relatively improve the alkali solubility of the film in the exposed part, and then remove the film in the exposed part with an alkaline developer to form a pattern. From the viewpoint of maintaining good exposure sensitivity and pattern processability while obtaining high light-shielding properties, a negative photosensitive composition is preferred.

The pixel dividing layer and/or the planarization layer included in the organic EL display device of the present invention contains (c) resin. Also, in order to impart either negative or positive photosensitivity to the photosensitive composition for patterning the pixel dividing layer and/or planarization layer described later, it is preferable to contain an alkali-soluble resin. Alkali-soluble resin refers to a resin having hydroxyl, carboxyl and/or sulfonic acid groups as alkali-soluble groups, an acid value of 10 mgKOH/g or more, and a weight average molecular weight (Mw) of 1,000 to 150,000. In addition, the cured product of the alkali-soluble resin contained in the photosensitive composition for patterning the pixel dividing layer and/or the planarizing layer belongs to (c ) composition of the resin.

唑樹脂、鹼可溶性聚苯并

唑前驅物、鹼可溶性聚醯胺樹脂、鹼可溶性矽氧烷樹脂。該等鹼可溶性樹脂，因為在最後成為構成上述(c)樹脂的成分之一，其中為了提高發光可靠度，較佳係可減少高溫下的排氣量(氣體產生量)者。 Examples of alkali-soluble resins include alkali-soluble cardo resins, alkali-soluble acrylic resins, alkali-soluble novolac resins, alkali-soluble polyimide resins, alkali-soluble polyimide precursors, alkali-soluble polyimide Benzo

Azole resin, alkali soluble polybenzo

Azole precursors, alkali-soluble polyamide resins, alkali-soluble silicone resins. These alkali-soluble resins become one of the components constituting the above (c) resin at the end, and among them, those that can reduce the outgassing amount (gas generation amount) at high temperature are preferable in order to improve the reliability of light emission.

In the case where the photosensitive composition for patterning the pixel dividing layer and/or the planarizing layer has negative photosensitivity, the alkali-soluble resin is preferable from the viewpoint of both pattern processability and light emission reliability. It contains alkali-soluble cardo resin and/or alkali-soluble polyimide resin. Furthermore, in order to improve the reliability of light emission, it is more preferable to contain at least an alkali-soluble polyimide resin. When alkali-soluble cardo resin and alkali-soluble polyimide resin are used together, the content of alkali-soluble polyimide resin is preferably higher than the content of alkali-soluble cardo resin from the viewpoint of luminescence reliability and dispersion stability .

唑樹脂、鹼可溶性聚苯并

唑前驅物、鹼可溶性矽氧烷樹脂中的至少1種的鹼可溶性樹脂。再者，從提升後述曝光步驟中的曝光感度與發光可靠度之觀點而言，更佳為含有鹼可溶性聚醯亞胺樹脂及/或鹼可溶性聚醯亞胺前驅物。 On the other hand, when the photosensitive composition for patterning the pixel dividing layer and/or the planarizing layer has positive photosensitivity, it is preferable to contain Alkali-soluble polyimide resin, alkali-soluble polyimide precursor, alkali-soluble polybenzo

Azole resin, alkali soluble polybenzo

An alkali-soluble resin of at least one of an azole precursor and an alkali-soluble silicone resin. Furthermore, from the viewpoint of improving exposure sensitivity and light emission reliability in the exposure step described later, it is more preferable to contain an alkali-soluble polyimide resin and/or an alkali-soluble polyimide precursor.

Alkali-soluble cardo resin refers to the alkali-soluble resin with a cardo skeleton, and the cardo skeleton refers to a skeleton with two aromatic groups connected by a single bond to the 4th carbon atom of the ring carbon atom constituting the ring structure.

As a preferred specific example of alkali-soluble cardo resin, alkali-soluble cardo resin having a fennel skeleton and having a structural unit represented by the following general formula (28) and a free radical polymerizable group, having a 1-phenyl- Alkali-soluble cardo resin having a 2,3-dihydro-1H-indene skeleton and a structural unit represented by the following general formula (29) and a radically polymerizable group, having an N-phenylphenolphthalein skeleton and having the following general formula An alkali-soluble cardo resin having a structural unit represented by (30) and a radically polymerizable group.

In the above general formulas (28), (29) and (30), Q ¹ ~ Q ⁸ can be the same or different respectively, which represent substituents directly bonded to the benzene ring, which are alkyl groups with 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, a to h is an integer, which is 1 or 2.

In order to improve developability, the acid value of the alkali-soluble cardo resin is preferably at least 10 mgKOH/g, more preferably at least 50 mgKOH/g. On the other hand, in order to suppress pattern edge peeling of the pixel dividing layer and/or the planarization layer, it is preferably 300 mgKOH/g or less, more preferably 250 mgKOH/g or less.

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

In addition, commercially available products can also be used as the alkali-soluble cardo resin, for example, "ADEKA ARKLS" (registered trademark) WR-301 (manufactured by ADEKA Co., Ltd.), "OGSOL" (registered trademark) CR-TR1 , CR-TR2, CR-TR3, CR-TR4, CR-TR5, CR-TR6 (the above are all manufactured by Osaka Gas Chemicals).

As the alkali-soluble polyimide resin, an alkali-soluble polyimide resin containing a structural unit represented by the following general formula (31) is preferable.

In the above general formula (31), R ²¹ represents a 4-10 valent organic group. R ²² represents a 2-8 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 are each independent, and 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 5 to 40 carbon atoms having an aromatic ring or a cycloaliphatic group.

Examples of the acid dianhydride include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetra Carboxylic acid dianhydride, bis(3,4-dicarboxyphenyl) anhydride, bis(3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis(3,4-dicarboxyphenyl) Tetracarboxylic dianhydrides having an aromatic ring such as hexafluoropropane dianhydride, tetracarboxylic dianhydrides having an aliphatic group such as butane tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetra Tetracarboxylic dianhydrides having cyclic aliphatic groups such as carboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-tetracarboxylic dianhydride, bicyclo[2.2.2]octanetetracarboxylic dianhydride, etc. .

In the general formula (31), R ²² -(R ²⁴ ) _j represents a diamine residue. ^R22 is preferably an organic group having 5 to 40 carbon atoms having an aromatic ring or a cycloaliphatic group.

Diamines include, for example, 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]pyridine, bis[4-(4-aminophenoxy)phenyl] Propane, bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, bis[4-(3-aminophenoxy)phenyl]pyridine, 9,9-bis(4-amino Phenyl) terpene, diaminodiphenyl ether, diaminodiphenylmethane, diaminodiphenylmethane, diaminodiphenylpropane, diaminodiphenylhexafluoropropane, diaminodiphenyl Diamines with aromatic rings such as sulfide, benzidine, 2,2-bistrifluorobenzidine, 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane, 2,6-bis Diamines having a cyclic aliphatic group such as (aminomethyl)bicyclo[2.2.1]heptane.

The alkali-soluble polyimide resin having a structural unit represented by the general formula (31) preferably has a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group and/or a thiol group at the end of the main chain. By blocking the end of the polyimide resin with an end-capping agent having a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and/or a thiol group, these groups can be introduced into the main chain end. Examples of the blocking agent include monoamines, acid anhydrides, monocarboxylic acids, monoacid chlorides, and monoactive esters.

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

The weight average molecular weight of the alkali-soluble polyimide resin is preferably 5,000 or more, more preferably 10,000 or more, from the viewpoint of the hardness of the pixel dividing layer and/or the planarization layer. On the other hand, it is preferably 100,000 or less, and more preferably 70,000 or less from the viewpoint of solubility with respect to an alkali developing solution.

The perylene pigment derivatives with the above-mentioned specific structure are organic pigment derivatives having an aromatic ring and an imide ring in the molecule, and have high affinity with resins having an aromatic ring and an imide ring in the molecule. Coexistence of an alkali-soluble polyimide resin having an aromatic ring and an imide ring in the molecule and carrying out the wet medium dispersion treatment described later can improve the perylene-based pigment derivative with a specific structure for (a) having a nitrogen-containing heterocyclic structure The dispersion energy of the black material. That is, more specifically, it is preferable to use an alkali-soluble polymer in which at least one of R ²¹ and R ²² in the above general formula (31) is a group having an aromatic ring in the manufacture of the pigment dispersion described later. The imide resin can obtain a high dispersion stabilization effect even if the added amount of the perylene-based dye derivative with a specific structure is small. In addition, the perylene-based pigment derivatives with a specific structure are mixed with an alkali-soluble polyimide resin having an aromatic ring and an imide ring in the molecule in the finally obtained film of the pixel division layer and/or planarization layer. The cured product (c) resin has high affinity and is filled therein in a uniformly dispersed state without shifting, so that the reliability of light emission can be further improved.

In the photosensitive composition for patterning the pixel dividing layer and/or planarizing layer included in the organic EL display device of the present invention, it is preferable to contain a photosensitizer in order to impart either negative or positive photosensitivity .

When imparting negative photosensitivity to a photosensitive composition, a compound having two or more radically polymerizable groups and a photopolymerization initiator can be used as a photosensitizer.

By containing a compound having two or more free radical polymerizable groups and a photopolymerization initiator described later, a radical polymerization reaction can be caused by exposure, and the film of the exposed part can be photohardened to insolubilize it, and then Alkaline developing solution only dissolves and removes the unexposed part, and can form a patterned pixel division layer and/or a planarization layer.

As the radical polymerizable group, a (meth)acrylic group is preferable from the viewpoint of improving the sensitivity at the time of exposure and improving the hardness of the cured film. As a compound having two or more (meth)acrylic acid groups, for example, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di( Meth)acrylate, Propylene Glycol Di(meth)acrylate, Trimethylolpropane Di(meth)acrylate, Trimethylolpropane Tri(meth)acrylate, Ethoxylated Trimethylolpropane Di(meth)acrylate, Ethoxylated trimethylolpropane tri(meth)acrylate, Ditrimethylolpropane tri(meth)acrylate, Ditrimethylolpropane tetra(meth)acrylate Acrylates, 1,3-Butanediol Di(meth)acrylate, Neopentyl Glycol Di(meth)acrylate, 1,4-Butanediol Di(meth)acrylate, 1,6-Hexane Diol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, dimethylol-tricyclodecane di (Meth)acrylates, Ethoxylated Glyceryl Tri(meth)acrylate, Neopentylthritol Tri(meth)acrylate, Neopentylthritol Tetra(meth)acrylate, Ethoxylated Neopentyl Tetrol Tri(meth)acrylate, Ethoxylated Neopentylthritol Tetra(meth)acrylate, Dineopenylthritol Penta(meth)acrylate, Dineopenylthritol Hexa(meth)acrylate Ester, Tri-Neopentylthritol Hepta(Meth)acrylate, Tri-Neopentylthritol Octa(Meth)acrylate, Tetra-Neopentylthritol Nona(Meth)acrylate, Tetra-Neopentylthritol Deca(Meth)acrylate ) acrylate, ε-caprolactone addition (meth)acrylate of diperythritol, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-(3- (Meth)acryloxy-2-hydroxypropoxy)phenyl]propane, 1,3,5-paraffin((meth)acryloxyethyl)isocyanuric acid, 1,3- Bis((meth)acryloyloxyethyl)isocyanuric acid, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl] fluorine, 9,9 - bis[4-(3-(meth)acryloxypropoxy)phenyl] fluorene, 9,9-bis(4-(meth)acryloxy phenyl) fluorine or their acids Modified body, ethylene oxide modified body or propylene oxide modified body, etc. These compounds may be contained alone or a plurality of such compounds may be contained. In addition, 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 planarizing layer as the acrylic resin component contained in the above-mentioned (c) resin.

The photopolymerization initiator refers to a compound that generates a free radical active species by breaking bonds and/or reacting with exposure, and photocures a compound having two or more free radical polymerizable groups through the free radical active species. Instead, a patterned pixel division layer and/or a planarization layer can be formed.

啉基丙烷-1-酮(BASF公司製「Irgacure」(註冊商標)907)、2-苄基-2-二甲胺基-1-(4-

啉基苯基)-丁酮-1(BASF公司製「Irgacure」(註冊商標)369)、2-(二甲胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-

啉基)苯基]-1-丁酮(BASF公司製「Irgacure」(註冊商標)379EG)等的α-胺基烷基苯酮系光聚合起始劑等。其中，從對於包含j線(波長313nm)、i線(365nm)、h線(405nm)、g線(436nm)之混合射線的曝光感度高、膜之深度方向上的深部硬化性優良之觀點而言，較佳為咔唑系光聚合起始劑、肟酯系光聚合起始劑。 Examples of photopolymerization initiators include "ADEKA OPTOMER" (registered trademark) N-1818, N-1919, "ADEKA CRUISE" (registered trademark) NCI-831 (all of which are manufactured by ADEKA Co., Ltd.), etc. Acylphosphine oxides such as carbazole-based photopolymerization initiators, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide ("Irgacure" (registered trademark) TPO manufactured by BASF Corporation) A photopolymerization initiator, 1,2-octanedione, 1-[4-(phenylthio)-,2-(o-phthalyl oxime)] ("Irgacure" (registered Trademark) OXE01), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(o-acetyloxime)( Oxime ester-based photopolymerization initiators such as "Irgacure" (registered trademark) OXE02) manufactured by BASF Corporation, 2-methyl-1-(4-methylphenylthiophenyl)-2-

Linylpropan-1-one ("Irgacure" (registered trademark) 907 manufactured by BASF Corporation), 2-benzyl-2-dimethylamino-1-(4-

Linylphenyl)-butanone-1 ("Irgacure" (registered trademark) 369 manufactured by BASF Corporation), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1- [4-(4-

α-aminoalkylphenone-based photopolymerization initiators such as phenyl)phenyl]-1-butanone (“Irgacure” (registered trademark) 379EG manufactured by BASF Corporation), and the like. Among them, from the viewpoint of high exposure sensitivity to mixed rays including j-line (wavelength 313nm), i-line (365nm), h-line (405nm), and g-line (436nm), and excellent deep curability in the depth direction of the film In other words, carbazole-based photopolymerization initiators and oxime ester-based photopolymerization initiators are preferred.

When imparting positive photosensitivity to the photosensitive composition, a photoacid generator can be used as a photosensitizer. By containing a photoacid generator, the alkali solubility of the exposed part relative to the unexposed part can be relatively increased by exposure, and then the exposed part can be dissolved and removed with an alkali developing solution, thereby forming a patterned pixel division layer and/or a planarization layer.

The photoacid generator is preferably a quinone diazide compound. The quinonediazide compound is more preferably a reactant obtained by esterifying a compound having a phenolic hydroxyl group with quinonediazidesulfonic acid chloride.

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

Examples of quinonediazidosulfonic acid chlorides include 4-naphthoquinonediazidosulfonic acid chlorides and 5-naphthoquinonediazidosulfonic acid chlorides. Such a quinonediazide compound has high exposure sensitivity to mixed rays including j-line (wavelength 313nm), i-line (365nm), h-line (405nm), and g-line (436nm) in the exposure step described later, and is therefore relatively good.

In the photosensitive composition used to form the pixel dividing layer and/or planarizing layer of the organic EL display device of the present invention, in order to further improve the heat resistance of the finally obtained pixel dividing layer and/or planarizing layer, it is also possible to Contains thermal crosslinkers. 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 a compound having two or more alkoxymethyl groups and/or hydroxymethyl groups, for example, NIKALAC (registered trademark) MW-100LM, MX-270, MX-280, MX-290 (Sanwa Chemical Co., Ltd. ) system), DML-PC (Honshu Chemical Industry Co., Ltd. system).

Examples of compounds having two or more epoxy groups include "EPOLIGHT" (registered trademark) 40E, 100E, 200E, 400E, 70P, 200P, 400P, 4000, 3002(N) Corporation Chemical Co., Ltd.), "jER" (registered trademark) 828, 1002, 1750, 1007, YX8100-BH30, E1256, E4250, E4275 (the above are all manufactured by Mitsubishi Chemical Co., Ltd.), "TECHMORE" (registered trademark ) VG-3101L (manufactured by Printeq Co., Ltd.; hereinafter referred to as "VG-3101L"), "TEPIC" (registered trademark) S, G, P, L (the above are all manufactured by Nissan Chemical Industry Co., Ltd.).

A solvent may be contained in the photosensitive composition for forming the pixel dividing layer and/or the planarization layer included in the organic EL display device of the present invention. By containing a solvent, the viscosity and applicability of a photosensitive composition 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 combination. Among these, acetates and ethers are preferable from the viewpoint of being excellent in dispersion stability and improving the uniformity of film thickness. Among them, propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA"), 3-methoxybutyl acetate (hereinafter referred to as "MBA"), and propylene glycol monomethyl ether are preferably mentioned.

As a method of preparing the photosensitive composition for forming the pixel division layer and/or planarization layer of the organic EL display device of the present invention, for example, by (a) a black material having a nitrogen-containing heterocyclic structure, (b-1) non-polymer dispersant, (b-2) polymer dispersant and solvent are mixed, and the (a) black material with nitrogen-containing heterocyclic structure is miniaturized by wet medium dispersion treatment to produce The pigment dispersion liquid is prepared by adding photosensitizer and other components into the pigment dispersion liquid, stirring, and filtering as required.

In addition, if only for the pigment dispersion obtained by the wet medium dispersion treatment, the perylene pigment derivatives with the above-mentioned specific structure are subsequently added and stirred, and sufficient effects cannot be obtained. By using the above-mentioned solvent salt grinding method The wet pulverization treatment or wet medium dispersion treatment performed by etc., in the coexistence of at least one color of organic pigment with a nitrogen-containing heterocyclic structure, fully imparts mechanical energy, thereby showing its effect.

Examples of the dispersing machine for carrying out the wet medium dispersion treatment include horizontal or vertical bead mills, roll mills, and the like. Examples include "DYNO-MILL" (registered trademark) (manufactured by Willy A. Bachofen), "SPIKE MILL" (registered trademark) (manufactured by Inoue Seisakusho Co., Ltd.), "sand mill" (registered trademark) ( DUPONT Corporation). As the medium for the disperser, zirconia beads, zircon beads or non-alkali glass beads can be mentioned. In order to avoid the medium itself being broken or worn to cause pollution and reduce the reliability of light emission, it is better to use metal-free or metal-free beads. Beads of components such as ions that become sources of impurities. Also, the diameter of the beads is preferably 0.03-5 mm, and the higher the sphericity, the better. Specific examples of preferable commercially available products include "TORAY CERAM" (registered trademark) (manufactured by TORAY Co., Ltd.). The operating conditions of the disperser may be appropriately set in consideration of bead hardness, operability, productivity, etc. so that the average dispersed particle diameter and viscosity of the pigments described later fall within the expected ranges.

The average dispersed particle size of all the pigments including (a) the black material having a nitrogen-containing heterocyclic structure is preferably 40 nm or more from the viewpoint of coating properties of the photosensitive composition and dispersion stability during storage. On the other hand, in order to improve the pattern linearity of the pixel dividing layer and/or the planarization layer, it is preferably 200nm or less. The average dispersed particle diameter of the pigment referred to here refers to the number average of the secondary particle diameters of all the pigment particles contained in the pigment dispersion liquid, which can be measured using a particle size distribution device. As a particle size distribution measuring device, a dynamic light scattering method particle size distribution measuring device "SZ-100 (manufactured by HORIBA)" or a laser diffraction and scattering method particle size distribution measuring device "MT-3000 (manufactured by Microtrac)" can be used.

Next, the method of forming the pixel dividing layer and the planarization layer included in the organic EL display device of the present invention will be described.

The pixel division layer and the planarization layer can be obtained, for example, by a method sequentially including a coating step, a prebaking step, an exposure step, a developing step, and a curing step.

In the coating step, the photosensitive composition is coated on the substrate to obtain a coating film. In the case where the substrate to be manufactured is, for example, a top-emission type organic display device, the coating device used in the coating step includes, for example, a slit coater, a spin coater, a gravure coater, a dip coater, and a curtain coater. machine, roll coater, spray coater, screen printing machine, inkjet. The pixel division layer and the planarization layer are generally formed with a thickness of about 0.5 to 3 μm in the component composition, and are preferably slits from the viewpoint of being suitable for thin film coating, less likely to cause coating defects, and excellent in film thickness uniformity and productivity. A coater or a spin coater is more preferably a slit coater from the viewpoint of saving liquid.

In the prebaking step, the solvent in the coating film is volatilized by heating to obtain a prebaked film. As a heating device, a hot-air oven, a hot plate, a far-infrared oven (IR oven), etc. are mentioned, for example. It does not hurt to perform a pin gap prebake or a contact prebake. The pre-baking temperature is preferably 50-150°C, and the pre-baking time is preferably 30 seconds to several hours. For example, after pre-baking at 80° C. for 2 minutes, then pre-baking at 120° C. for 2 minutes, etc., the pre-baking may be performed in two or more stages. In order to further improve the uniformity of the film thickness, after the coating step, a part of the solvent contained in the coating film can be volatilized by a vacuum/reduced pressure dryer, and then the pre-baking step can be performed by heating.

In the exposure step, active chemical rays are irradiated from the film surface side of the prebaked film through a photomask to obtain an exposed film. As an exposure apparatus used in an exposure process, a stepper, a mirror projection mask alignment exposure machine (MPA), a parallel light mask alignment exposure machine (PLA), etc. are mentioned. Examples of active chemical rays to be irradiated during exposure include ultraviolet rays, visible light, electron beams, X-rays, KrF (wavelength: 248 nm) lasers, ArF (wavelength: 193 nm) lasers, and the like. Among them, the j-line (wavelength: 313nm), i-line (wavelength: 365nm), h-line (wavelength: 405nm) or g-line (wavelength: 436nm) of the mercury lamp is preferred, and their mixed rays are more preferred. The exposure amount is usually about 10~4000mJ/cm ² (i-line conversion value). As a mask, for example, a mask in which a thin film is formed in a pattern on one surface of a base material such as glass, quartz, or film, which is light-transmitting in the exposure wavelength, the thin film is made of a metal such as chromium. Or black organic resin, and has exposure light shielding properties. In the process of forming the pixel division layer and the planarization layer using the photosensitive composition, any type of exposure mask, either negative or positive, can be used to allow the active chemical rays to only penetrate through the openings for pattern exposure, thereby obtaining exposure film. In addition, if the part where the pixel division layer or the planarization layer is to be formed corresponds to the pattern of the opening in the exposure mask, such a mask is called a negative exposure mask; film, such a mask is called a positive exposure mask.

In addition, when used as a pixel dividing layer that also functions as a spacer in the configuration of a panel member, the pixel dividing layer may have a portion having a different film thickness on a plane, that is, a step shape. As a method of obtaining a pixel division layer having a step difference in film thickness, in the exposure step, a method of performing pattern exposure through a negative or positive halftone exposure mask in which the There are various types of openings with different light transmittance in the area exposed to light.

In the image development step, when the photosensitive composition is a negative photosensitive composition, an unexposed portion is removed by image development to obtain a patterned developed film. On the other hand, in the case of a positive photosensitive composition, an exposed portion is removed by development to obtain a patterned developed film. Here, the exposed portion refers to a portion irradiated with exposure light through the opening of the mask, while the unexposed portion refers to a portion not irradiated with exposure light. As an image development method, the method of immersing an exposure film in the alkali aqueous solution which is a developing solution for 10 seconds - 10 minutes by methods, such as shower, dipping, and immersion (puddle), is mentioned, for example.

When the photosensitive composition is a negative photosensitive composition, the unexposed portion becomes the pattern opening, and in the case of the positive type, the exposed portion becomes the pattern opening, and in either case, the portion that becomes the opening is exposed to the base layer. The ITO electrode. The photosensitive composition containing the perylene dye derivative of the above-mentioned specific structure exhibits a remarkable effect in suppressing the development residue on the ITO electrode in the development step. In addition, the opening part finally becomes a light-emitting pixel part in the organic EL display device.

Since it is easy to volatilize the surface layer of the developing film or the developer remaining in the inside after penetration in the hardening step after development, it is preferable to use 1.0~ 3.0 wt% TMAH, usually 2.38 wt% TMAH is used. 2. 38% by weight of TMAH can also be used as a commercially available product, or a high-concentration product can be diluted for use, or a nonionic surfactant can be added in a small amount within the range that does not adversely affect the luminescence reliability and used for development. . In addition, after the development, there is no problem in adding washing treatment by rinsing with deionized water and/or drainage treatment by air jet.

In the curing step, the developing film is thermally cured by heating, and components such as moisture and permeated and remaining developing solution are volatilized to obtain a pixel dividing layer or a planarization layer. As a heating device, a hot air oven, an IR oven, etc. are mentioned, for example. The heating temperature is preferably 230~300°C, more preferably 250~300°C in order to obtain high light emission reliability. The heating environment is preferably air or nitrogen environment, and the pressure during heating is preferably atmospheric pressure.

The pixel dividing layer and the planarizing layer of the organic EL display device of the present invention that can be patterned through the above steps have an optical density of 0.5 or more, more preferably 0.8 or more, per film thickness of 1.0 μm, respectively, More preferably, it is 1.0 or more. The optical density referred to here is the intensity of incident light measured with an optical densitometer (manufactured by X-Rite Corporation; X-Rite 361T) with respect to a pixel division layer or a planarization layer with a film thickness of 1.0 μm formed on a light-transmitting substrate and the transmitted light intensity, and the value calculated by the following formula. A higher optical density indicates higher light-shielding properties. As the light-transmitting substrate, "TEMPAX (manufactured by AGC TECHNO GLASS Co., Ltd.)" using a light-transmitting glass substrate is preferable.

Optical density = log ₁₀ (I ₀ /I)

I ₀ : incident light intensity

I: penetrating light intensity

In order to stably drive the light-emitting element, the relative permittivity of the pixel division layer and the planarization layer of the organic EL display device at a frequency of 1 kHz is preferably 7 or less, more preferably 5 or less, and still more preferably 4 or less. The relative permittivity can be measured using a permittivity measuring device such as an LCR meter manufactured by Agilent Technologies.

The aperture ratio of the pixel dividing layer in the display area is preferably 20% or less from the viewpoint of making the display area more precise, improving the display quality of images or images, and increasing the value as a display device. The aperture ratio referred to here refers to the area ratio of the openings of the pixel dividing layer to the area of the pixel dividing layer. The lower the aperture ratio, the larger the area where the pixel dividing layer is formed in the display region, thus greatly affecting the performance related to the light emission reliability of the pixel dividing layer. That is, an organic EL display device having a lower aperture ratio and a high-definition display region contributes more to the effect of the present invention.

Example

The present invention will be described in detail below with examples and comparative examples, but the aspects of the present invention are not limited thereto.

First, the evaluation methods in the respective examples and comparative examples will be described.

<Calculation method of minimum necessary exposure>

A silver/copper alloy thin film (volume ratio 10:1) with a thickness of 10 nm was formed on the entire surface of an alkali-free glass substrate of 100 mm×100 mm by sputtering, and etched to form a patterned metal reflective layer. Next, an ITO transparent conductive film with a thickness of 10 nm was formed on the entire surface by a sputtering method to obtain a substrate with the minimum exposure dose required for evaluation.

With a spin coater, the number of rotations was adjusted so that the thickness of the finally obtained cured film was 1.0 μm, and the photosensitive composition was coated on the surface of the obtained substrate for evaluating the minimum exposure dose necessary to obtain a coating film. Furthermore, using a hot plate (SCW-636; manufactured by Dainippon Screen Mfg. Co., Ltd.), the coating film was prebaked at 100° C. for 120 seconds under atmospheric pressure to obtain a prebaked film. Using a double-side alignment single-side exposure device (mask alignment exposure machine PEM-6M; manufactured by UNION Optical Co., Ltd.), through a gray scale mask for sensitivity measurement (MDRM MODEL 4000-5-FS; Opto- Line InterNatioNal Co., Ltd.), pattern exposure was performed with mixed rays 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. Next, development was performed with a 2.38% by weight TMAH aqueous solution using a small-sized developing device for lithography (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.), to obtain a developed film. Next, observe the analytical pattern of the developed film produced using an FPD inspection microscope (MX-61L; manufactured by OLYMPUS Co., Ltd.), and form the line width and space width of the pattern in the line width/space pattern (line-and-space pattern) The exposure amount of 1:1 (mJ/cm ² : the value of the i-ray illuminance meter) was used as the minimum exposure amount (sensitivity) necessary for the photosensitive composition. The pitch width referred to here refers to the interval between identical patterns. In addition, since the negative photosensitive composition and the positive photosensitive composition were evaluated with the same gradation mask, the arrangement of the formed patterns was reversed.

(1) Evaluation of dispersion stability of photosensitive composition

Seal 20.0 g of the photosensitive composition obtained in Examples 1-22 and Comparative Examples 1-33 within 1 hour after preparation in a glass bottle, and place it in an incubator under atmospheric pressure/light shielding/actual temperature 25°C±1°C Let stand for 24 hours to preserve. Take 1.0 g of the preserved photosensitive composition, drop it on the stage of an E-type viscometer (cone-plate viscometer) at an actual temperature of 25° C., and apply a shearing force under the condition of a rotation speed of 50 rpm. The viscosity displayed after 3 minutes was taken as the initial viscosity (mPa‧s). Under the same storage environment, continue to store the photosensitive composition at 25°C±1°C for 29 days for long-term storage, use a spatula to confirm whether there is any sediment at the bottom of the glass bottle, and stir it on the shaker for 1 minute. Then measure the viscosity in the same way, and use it as the time-lapse viscosity (mPa‧s), and obtain the viscosity increase rate (%) from the following formula. The smaller the absolute value of the viscosity increase rate (%), the better the stability. The dispersion stability was evaluated according to the following criteria, and AA and A to C were regarded as acceptable, and D to F were regarded as unacceptable. However, in the case where a precipitate was generated after storage, it was evaluated as E regardless of the viscosity increase rate. In addition, when either the initial viscosity or the time-lapse viscosity of the photosensitive composition exceeds 100 (mPa‧s), it is difficult to make a comparative evaluation under the same viscosity measurement conditions. , all evaluated as F.

Viscosity increase rate (%)=(time-lapse viscosity-initial viscosity)/initial viscosity×100

In addition, when the viscosity increase ratio is positive, it indicates a high viscosity, and when it is negative, it indicates a low viscosity. However, in Examples 1 to 22 and Comparative Examples 1 to 33, for those evaluated as A to D, the viscosity increase rate None showed negative values.

AA: less than 5%

A: More than 5% and less than 10%

B: More than 10% and less than 25%

C: More than 25% and less than 50%

D: more than 50%

E: produce sediment

F: The viscosity is too high to be evaluated under the same viscosity measurement conditions.

(2) Evaluation of light-shielding property of cured film

For the light-shielding evaluation substrates having a cured film on the surface of TEMPAX obtained in Examples 1 to 22 and Comparative Examples 1 to 33, an optical densitometer (manufactured by X-Rite Corporation; X-Rite 361T) was used to measure from the film surface The optical density (OD value) was measured at 3 places on the side of the plane, and the second decimal place of the average value was rounded off to obtain the value up to the first decimal place. Divide this value by the thickness (μm) of the cured film to calculate the OD value (OD/μm) per 1.0 μm of the thickness of the cured film. The higher the OD value, the better the light-shielding cured film. Evaluation. In addition, the OD value of the substrate of TEMPAX itself without the formation of the cured film was measured, and the result was 0.00, so the OD value of the substrate for light-shielding property evaluation was regarded as the OD value of the cured film. In addition, the thickness of the cured film was measured at 3 places on a plane using a stylus-type film thickness measuring device (Tokyo Precision Co., Ltd.; SURFCOM), and the second decimal place of the average value was rounded to obtain the first decimal place. Numerical value up to one digit.

(3) Evaluation of development residue of pixel division layer

Using an optical microscope, with a magnification of 50 times, the openings located in the center of the pixel division layer forming substrates obtained in Examples 1 to 22 and Comparative Examples 1 to 33 were magnified at 10 places for observation, and the major diameter of each opening was calculated to be 0.1. The number of development residues of more than μm and less than 3.0 μm. The average number of development residues observed per opening was evaluated according to the following criteria, with AA and A to C as pass, and D to E as fail. However, when residues with a long diameter exceeding 3.0 μm were observed, the evaluation was E regardless of the average number of residues.

AA: Development residue is not observed at all

A: Less than 5 development residues are observed

B: 5 or more and less than 10 development residues observed

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

D: 15 or more development residues are observed

E: A development residue with a major diameter exceeding 3.0 μm is observed.

(4) Evaluation of light emission reliability of an organic EL display device including a pixel dividing layer, (5) Evaluation of light emission reliability of an organic EL display device including a pixel dividing layer and a planarization layer

Place the organic EL display devices obtained in Examples 1 to 22 and Comparative Examples 1 to 33 on a heating plate heated to 80°C with the light-emitting surface upward, and drive them to emit light with a direct current of 10 mA/cm ² . After standing still, the area ratio of the light-emitting portion to the area of the light-emitting pixel (pixel light-emitting area ratio) was measured after 1 hour and 500 hours. Taking the pixel luminous area ratio after 1 hour as a benchmark, the higher the pixel luminous area ratio can be maintained, the less prone to pixel shrinkage, and the better the luminous reliability. Evaluate according to the following criteria, and take A~C as pass , taking D~F as unqualified. Also, if there are too many black dots in the pixel and it is difficult to properly evaluate the light emitting area ratio of the pixel immediately after the driving is started, the evaluation is E. Also, when there is one or more unlit light-emitting pixel units immediately after the drive is started, the evaluation is F.

AA: more than 95%

A: More than 90% and less than 95%

B: More than 85% and less than 90%

C: More than 80% and less than 85%

D: less than 80%

E: There are too many black spots, it is difficult to make a proper evaluation

F: Immediately after driving, there is one or more light-emitting pixel portions that are not lit at all (the pixel light-emitting area ratio is 0%), and it is difficult to make a proper evaluation.

(6) Evaluation of black spots (partially non-luminous parts) of an organic EL display device equipped with a pixel division layer and a planarization layer

For the organic EL display device with a pixel dividing layer and a planarization layer having a pixel aperture ratio of 18% obtained in Examples 1 to 22 and Comparative Examples 1 to 33, drive it for 2 hours from the start with a DC drive of 10 mA/cm ² The organic EL display device at a later point in time emits light, and magnifies and displays 10 pixel parts located in the center among the pixel parts formed in the area of 16 mm in length and 16 mm in width at a magnification of 50 times for observation, and calculates the The number of partially non-luminous parts with a major axis of 0.1 μm or more and less than 15.0 μm in the opening. The average number of local non-luminous parts observed per opening is evaluated according to the following criteria, AA and A~C are regarded as pass, and D~E are regarded as fail. However, when black spots with a major diameter exceeding 15.0 μm were observed, the evaluation was E regardless of the average number of black spots.

AA: Black spots are not observed at all

A: Less than 5 black spots are observed

B: More than 5 and less than 10 black spots are observed

C: More than 10 and less than 15 black spots are observed

D: 15 or more black spots are observed

E: Black spots with a long diameter exceeding 15.0 μm are observed

F: There is one or more light-emitting pixel parts that are not lit at all (the pixel light-emitting area ratio is 0%), and it is difficult to evaluate properly

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

Under dry nitrogen flow, 150.15g of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (0.41mol), 6.20g of 1,3-bis(3-aminopropyl) Tetramethyldisiloxane (0.02mol), and 13.65g of 3-aminophenol (0.13mol) as a blocking agent were dissolved in 500.00g of N-methyl-2-pyrrolidone (hereinafter called "NMP"), and 155.10 g of bis(3,4-dicarboxyphenyl) ether dianhydride (0.50 mol) and 150.00 g of NMP were added thereto, stirred at 20°C for 1 hour, and water was removed While stirring at 180° C. for 4 hours. After the reaction, the reaction solution was dropped into 10 L of water, the resulting precipitate was filtered and collected, washed 5 times with water, and dried in a vacuum dryer at 80°C for 20 hours to synthesize a compound having the formula (31) above. Alkali-soluble polyimide resin powder having an aromatic ring and an imide ring in the molecule as a structural unit and having a weight average molecular weight (Mw) of 25,000 is dissolved in PGMEA so that the solid content becomes 30.00% by weight to obtain an alkali Soluble polyimide resin solution A.

(Synthesis Example 2: Synthesis of Polymer Type Dispersant Solution B)

Under a dry nitrogen stream, 12.91 g of methacrylic acid (0.15 mol) and 55.07 g of methyl methacrylate (0.55 mol) were added dropwise in 185.44 g of PGMEA at a liquid temperature of 100° C. over 30 minutes. 21.01 g of phosphonyloxyethyl methacrylate (0.10 mol), 26.43 g of benzyl methacrylate (0.15 mol), and 8.21 g of azobisiso The mixed solution of butyronitrile was stirred for 1 hour under the condition that the liquid temperature was maintained at 100° C. to allow the thermal polymerization to proceed and then cooled to synthesize a (meth)acrylic copolymer having a weight average molecular weight (Mw) of 9,500. This was diluted with PGMEA so that the solid content would be 30.00% by weight to obtain a polymer-type dispersant solution B which is a polymer-type dispersant having a phosphoric acid group as an acidic adsorption group.

(Synthesis example 3: Synthesis of quinonediazide compound a)

烷，並使其為室溫。此處，一邊使系統內維持在25~35℃，一邊滴下與50.00g的1,4-二

烷混合的12.65g(0.125mol)的三乙胺。滴下後，於30℃下攪拌2小時。接著，過濾三乙胺鹽，將濾液投入水，過濾所析出之沉澱物並且回收。以真空乾燥機使該沉澱物乾燥，藉此得到以下述結構式(32)表示之、固體成分100.00重量%的醌二疊氮化合物a。 Under a stream of dry nitrogen, a compound having a phenolic hydroxyl group, namely 21.23 g (0.05 mol) of TrisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.), 3.58 g (0.125 mol) of 5-naphthoquinonediazide sulfo Acid chloride dissolved in 450.00g of 1,4-bis

alkanes, and allow to come to room temperature. Here, 50.00 g of 1,4-bis

12.65 g (0.125 mol) of triethylamine mixed with alkanes. After dripping, it stirred at 30 degreeC for 2 hours. Next, the triethylamine salt was filtered, the filtrate was poured into water, and the separated precipitate was filtered and recovered. The precipitate was dried with a vacuum dryer to obtain a quinonediazide compound a represented by the following structural formula (32) and having a solid content of 100.00% by weight.

The chemical structures of various organic dye derivatives and organic pigments used in Examples and Comparative Examples are shown below.

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

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

"Perylene-based dye derivative 3": a compound represented by the following structural formula (35) (the compound represented by the above-mentioned general formula ( ² ), where R2 and ^R3 are perylene-based dye derivatives with aryl groups having substituents)

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

"Perylene-based dye derivative 5": a compound represented by the following structural formula (37) (the compound represented by the above-mentioned general formula ( ² ), where R2 and ^R3 are perylene-based dye derivatives with aryl groups having substituents)

"Perylene-based dye derivative 6": a compound represented by the following structural formula (38) (the compound represented by the above-mentioned general formula ( ² ), where R2 and ^R3 are perylene-based dye derivatives with aryl groups having substituents)

"Perylene-based dye derivative 7": a compound represented by the following structural formula (39) (the compound represented by the above-mentioned general formula (2), where R ² and R ³ are methyl perylene-based dye derivatives)

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

"Perylene-based pigment derivative 9": a compound represented by the following structural formula (41) (corresponding to the compound represented by the above-mentioned general formula (1), which is a perylene compound having an organic group having an N,N-dialkylamino group at the end. pigment derivatives)

"Perylene-based pigment derivative 10": a compound represented by the following structural formula (42) (corresponding to the compound represented by the above general formula (2), which contains an organic group having an N,N-dialkylamino group at the end perylene pigment derivatives)

"Perylene-based pigment derivative 11": a compound represented by the following structural formula (43) (corresponding to the compound represented by the above general formula (2), which contains an organic group with a N,N-dialkylamino group at the end perylene pigment derivatives)

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

"Copper phthalocyanine pigment derivative 2": a compound represented by the following structural formula (45) (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) (copper phthalocyanine derivative having two basic functional groups in the molecule)

"Diketopyrrolopyrrole-based 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) (a perylene-based dye derivative that does not correspond to the compound represented by the above-mentioned general formula (1) or the above-mentioned general formula (2))

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

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

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

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

"Perylene Black A": 3,4,9,10-perylenetetracarboxylic 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-based organic yellow pigment without nitrogen-containing heterocyclic structure in the molecule

C.I. Pigment Violet 50: Azo-based organic purple pigment without nitrogen-containing heterocyclic ring structure in the molecule

C.I. Pigment Red 224: a perylene-based organic red pigment that does not have a nitrogen-containing heterocyclic structure in the molecule represented by the following structural formula (59)

系色素衍生物1：具有C.I.顏料紫23殘基的以下述結構式(60)表示之單磺酸衍生物與以下述結構式(61)表示之二磺酸衍生物的混合物(重量比例3：7) two

Pigment derivative 1: 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 a residue of CI Pigment Violet 23 (weight ratio 3: 7)

As the content of free ionic impurities contained in the above organic pigment derivatives and organic pigments, sulfate ion (SO ₄ ^2- ), sulfite ion (SO ₃ ^- ), chloride ion were confirmed by ion chromatography. The content of each (Cl ⁻ ) is 50 ppm or less. Also, for organic pigment derivatives and organic pigments containing copper atoms, it was confirmed by ion chromatography that free copper was 100 ppm or less.

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

Alkali-soluble polyimide resin solution A of 89.06g, SOLSPERSE20000 of 28.13g (main chain has polyethylene oxide/propylene oxide structure and the end of the main chain has tertiary amine groups as basic adsorption group straight chain) A polyether-based dispersant; solid content 100.00% by weight), 787.66 g of PGMEA as an acetate-based solvent, and 1.41 g of perylene-based dye derivative 1 were mixed and stirred for 10 minutes. Then, as (a) a black material having a nitrogen-containing heterocyclic structure, 28.13 g of C.I. Pigment Yellow 192 (average primary particle size 42 nm), 28.13 g of C.I. Pigment Red 179 (average primary particle size 48 nm), and 37.50 g C.I. Pigment Blue 60 (average primary particle size: 61nm) was stirred for 30 minutes, using a bead mill filled with 0.4mmφ zirconia beads (manufactured by TORAY Co., Ltd.; "TORAYCERAM" (registered trademark)) in a circulating Wet media dispersion treatment was carried out for 30 minutes. Next, in order to further promote miniaturization, a bead mill filled with 0.05 mmφ zirconia beads (manufactured by TORAY Co., Ltd.; "TORAYCERAM" (registered trademark)) was used to perform wet medium dispersion treatment in a circulating manner. After 30 Minutes later, an appropriate amount of sample is taken into a glass bottle every 10 minutes of the dispersion treatment time, and the sampled pigment dispersion is set in a dynamic light scattering particle size distribution measuring device "SZ-100", and the average dispersed particle diameter is measured. At a time point 30 minutes after the sampling, the pigment dispersion within the range of 150nm±20nm was referred to as pigment dispersion 1. In addition, the solid content of the pigment dispersion liquid 1 was 15.00% by weight. The compounding quantity (g) of each raw material is shown in Table 1. The content of the organic pigment derivative was 1.50% by weight relative to all the pigments.

(Preparation Example 2~7: Preparation of Pigment Dispersion Liquid 2~7)

Pigment dispersions 2 to 7 were prepared in the same procedure as in Preparation Example 1, using perylene-based dye derivatives 2 to 7 instead of perylene-based dye derivative 1, respectively. Table 1 shows the compounding quantity (g) of each raw material.

(Preparation Example 8: Preparation of Pigment Dispersion Liquid 8)

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

(Preparation Example 9: Preparation of Pigment Dispersion Liquid 9)

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

(Preparation Example 10: Preparation of Pigment Dispersion Liquid 10)

Pigments were prepared in the same procedure as in Preparation Example 1, except that the perylene-based dye derivative 7 was used instead of the perylene-based dye derivative 1 so that the content of the organic dye derivative relative to all the pigments was increased to 5.00% by weight. Dispersion 10. Table 2 shows the compounding amount (g) of each raw material.

(Preparation Example 11: Preparation of Pigment Dispersion Liquid 11)

Increase the content of organic pigment derivatives relative to the pigment to 5.00% by weight, and use both in combination at a ratio of perylene-based pigment derivatives 1/perylene-based pigment derivatives 7 = weight ratio 1/1, thereby replacing perylene-based pigment derivatives. Pigment dispersion 11 was prepared in the same procedure as Preparation Example 1 except for Substance 1. Table 2 shows the compounding amount (g) of each raw material.

(Preparation Example 12: Preparation of Pigment Dispersion Liquid 12)

78.13 g of alkali-soluble polyimide resin solution A, 28.13 g of SOLSPERSE 20000, 795.31 g of PGMEA, and 4.69 g of perylene-based dye derivative 7 were mixed and stirred for 10 minutes. Then, as (a) a black material having a nitrogen-containing heterocyclic structure, 28.13 g of C.I. Pigment Yellow 194 (average primary particle size 64 nm), 28.13 g of C.I. C.I. Pigment Blue 60 (average primary particle size 61nm), stirred for 30 minutes. In the subsequent steps, the wet medium dispersion treatment was carried out in the same order as Preparation Example 1 to prepare the pigment dispersion liquid 12 . Table 2 shows the compounding amount (g) of each raw material.

(Preparation Example 13: Preparation of Pigment Dispersion Liquid 13)

68.75 g of alkali-soluble polyimide resin solution A, 28.13 g of SOLSPERSE 20000, 801.88 g of PGMEA, and 7.50 g of perylene-based dye derivative 7 were mixed and stirred for 10 minutes. Afterwards, as (a) a black material having a nitrogen-containing heterocyclic structure, 32.81 g of C.I. Pigment Yellow 192 (average primary particle diameter 42 nm), 46.88 g of perylene black A (average primary particle diameter 55 nm), and 14.06 g of C.I. Pigment Blue 60 (average primary particle size 61nm), stirred for 30 minutes. In the subsequent steps, the wet medium dispersion treatment was carried out in the same order as Preparation Example 1 to prepare the pigment dispersion liquid 13 . Table 2 shows the compounding amount (g) of each raw material.

(Preparation Example 14: Preparation of Pigment Dispersion Liquid 14)

Pigment dispersion 14 was prepared in the same procedure as 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 Liquid 15)

200.00 g of crude pigment A (C.I. Pigment Red 179; average primary particle size 172 nm), 13.50 g of perylene-based pigment derivative 1, and 10.00 g of Dymerex as a rosin mixture containing a rosin dimer having one or more carboxyl groups Mix Polymerized Rosin, 2000.00g of sodium chloride as a water-soluble inorganic salt, and 500.00g of diethylene glycol as a water-soluble solvent, keep the liquid temperature at 100~110°C, and knead with a kneader for 2 hours to obtain a red color Knead. Next, add water to the red kneading mixture, dissolve the water-soluble components in 3 L of warm water maintained at 60°C, wash repeatedly until the free chlorine content in the red filtrate is less than 100ppm, then filter, and use in an oven at 110°C It dries for 12 hours. Next, particle adjustment was performed by dry pulverization using a jet mill to obtain a red surface-treated pigment A (average primary particle diameter: 44 nm). The above steps are wet pulverization treatment by solvent salt milling method. In addition, since part of the perylene-based pigment derivative 1 disappeared in the filtrate in the above-mentioned filtration step, the ratio of the constituent components of the finally obtained red surface-treated pigment A was 100 parts by weight of C.I. Pigment Red 179, 5 Perylene pigment derivative 1 in parts by weight and Dymerex Polymerized Rosin in 5 parts by weight. Next, 84.38 g of alkali-soluble polyimide resin solution A, 28.13 g of SOLSPERSE 20000, and 790.94 g of PGMEA were mixed and stirred for 10 minutes. Then, as (a) a black material having a nitrogen-containing heterocyclic structure, 28.13 g of C.I. Pigment Yellow 192, 30.94 g of red surface-treated pigment A, and 37.50 g of C.I. Pigment Blue 60 were added, and stirred for 30 minutes. In the subsequent steps, the wet medium dispersion treatment was carried out in the same order as Preparation Example 1 to prepare the pigment dispersion liquid 15 . Table 2 shows the compounding amount (g) of each raw material.

(Preparation Example 16: Preparation of Pigment Dispersion Liquid 16)

89.06 g of alkali-soluble polyimide resin solution A, 93.75 g of polymer-type dispersant solution B, 722.03 g of PGMEA, and 1.41 g of perylene-based dye derivative 8 were mixed and stirred for 10 minutes. After that, put 28.13g of C.I. Pigment Yellow 192 (average primary particle size 42nm), 28.13g of C.I. Pigment Red 179 (average primary particle size 48nm), and 37.50g of C.I. Pigment Blue 60 (average primary particle size 61nm), and stir 30 minutes. In the subsequent steps, the wet medium dispersion treatment was carried out in the same order as Preparation Example 1 to prepare the pigment dispersion liquid 16 . The content of the organic pigment derivative was 1.50% by weight relative to all the pigments.

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

(Preparation Examples 17~19: Preparation of Pigment Dispersion Liquids 17~19)

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

(Preparation Example 20: Preparation of Pigment Dispersion Liquid 20)

Use perylene-based pigment derivative 11 instead of perylene-based pigment derivative 8, and use anthraquinone-based pigment derivative 1 in a ratio of perylene-based pigment derivative 11/anthraquinone-based pigment derivative 1=weight ratio 2/1, except Other than that, the pigment dispersion liquid 20 was prepared in the same procedure as in Preparation Example 17. Table 3 shows the compounding quantity (g) of each raw material.

(Preparation Example 21: Preparation of Pigment Dispersion Liquid 21)

89.06 g of alkali-soluble polyimide resin solution A, 28.13 g of SOLSPERSE 20000, 787.66 g of PGMEA, and 1.41 g of perylene-based dye derivative 1 were mixed and stirred for 10 minutes. Afterwards, 18.75 g of C.I. Pigment Yellow 83 (average primary particle diameter 41 nm) and 56.25 g of C.I. Pigment Violet 50 (average primary particle diameter 56 nm) not having nitrogen-containing heterocyclic structure were added into ), and 18.75 g of C.I. Pigment Red 179 (average particle diameter 48 nm) with a nitrogen-containing heterocyclic structure, stirred for 30 minutes. In the subsequent steps, the wet medium dispersion treatment was carried out in the same order as Preparation Example 1 to prepare the pigment dispersion liquid 21 . Table 4 shows the compounding quantity (g) of each raw material. The content of the organic pigment derivative was 1.50% by weight relative to all the pigments.

(Preparation Example 22: Preparation of Pigment Dispersion Liquid 22)

The blending amount of the perylene-based dye derivative 1 was increased, and the pigment dispersion liquid 22 was prepared in the same procedure as in Preparation Example 21 at the blending amount (g) shown in Table 4. The content of the organic pigment derivative was 5.00% by weight relative to all the pigments.

(Preparation Example 23: Preparation of Pigment Dispersion Liquid 23)

Use perylene-based pigment derivative 4 instead of perylene-based pigment derivative 1, and use C.I. Pigment Red 224 (average primary particle size 62nm) without nitrogen-containing heterocyclic structure instead of C.I. Pigment Red 179, with the blending amount shown in Table 4 (g) Pigment dispersion liquid 23 was prepared in the same procedure as Preparation Example 21.

(Preparation Example 24: Preparation of Pigment Dispersion Liquid 24)

Mix 200.00g of crude pigment B (C.I. Pigment Violet 29; average primary particle size 163nm), 2000.00g of sodium chloride, and 400.00g of diethylene glycol, keep the liquid temperature at 90~100°C, knead with a kneader for 7 hours, a purple kneader was obtained. Next, add water to the purple kneader, dissolve the water-soluble components in 2L of warm water maintained at 60°C, wash repeatedly until the free chlorine content in the purple filtrate is less than 100ppm, then filter and dilute with water again, A purple pigment slurry having a solid content of 30% by weight was obtained. Add an aqueous sodium hydroxide solution containing copper phthalocyanine pigment derivative 1 to the purple pigment slurry, stir for 1 hour, add hydrochloric acid until the pH is 7, and deposit copper phthalocyanine pigment derivative 1 on the surface of the pigment. Dry in an oven at 110°C for 12 hours. Next, particle adjustment was carried out by dry pulverization using a jet mill to obtain a purple surface-treated pigment A (average primary particle size 1) containing 100 parts by weight of C.I. Pigment Violet 29 and 5 parts by weight of copper phthalocyanine pigment derivative 1. Diameter 25nm). Next, 28.13 g of PB821 (manufactured by Ajinomoto Fine-Techno; polyester polymer type dispersant having basic adsorption groups and acidic adsorption groups; solid content 100.00% by weight) and 788.01 g of PGMEA were mixed and stirred for 10 minutes. Then, as organic pigments, 27.33g of C.I. Pigment Yellow 139 (average primary particle size 65nm), 32.43g of purple surface-treated pigment A, and 35.55g of C.I. Pigment Blue 15:6 (average primary particle size 45nm) were put in, and stirred 30 minutes. Subsequent steps were carried out in the same order as Preparation Example 1 for wet medium dispersion treatment. Next, the alkali-soluble polyimide resin solution A was added so that the solid content of the pigment dispersion liquid became 15.00% by weight, and diluted to prepare the pigment dispersion liquid 24 . In addition, the solid content in the alkali-soluble polyimide resin solution A was 28.33% by weight and the organic pigment derivative content was 1.65% by weight relative to the total organic pigment contained in the pigment dispersion liquid 24 . Table 4 shows the compounding quantity (g) of each raw material.

(Preparation Example 25: Preparation of Pigment Dispersion Liquid 25)

Except for increasing the amount of copper phthalocyanine pigment derivative 1, wet pulverization was performed in the same procedure as Preparation Example 24 to obtain 100 parts by weight of C.I. Pigment Violet 29 and 12 parts by weight of copper phthalocyanine For the purple surface-treated pigment B (average primary particle size: 25 nm) of cyan pigment derivative 1, a pigment with a solid content of 15.00% by weight was prepared in the same procedure as Preparation Example 24 at the blending amount (g) shown in Table 4. Dispersion 25. In addition, the solid content in the alkali-soluble polyimide resin solution A was 26.03% by weight and the organic pigment derivative content was 3.95% by weight relative to the total organic pigment contained in the pigment dispersion liquid 25. Table 4 shows the compounding quantity (g) of each raw material.

(Preparation Example 26: Preparation of Pigment Dispersion Liquid 26)

Pigment dispersion 26 having a solid content of 15.00% by weight was prepared in the same procedure as in Preparation Example 25 except that SOLSPERSE 20000 was used instead of PB821. Table 4 shows the compounding quantity (g) of each raw material.

(Preparation Example 27: Preparation of Pigment Dispersion Liquid 27)

Except that the copper phthalocyanine pigment derivative 2 was used instead of the copper phthalocyanine pigment derivative 1, the wet pulverization treatment was performed in the same procedure as Preparation Example 24 to obtain a purple surface-treated pigment C (average primary particle diameter: 31 nm). ). Subsequent steps were carried out in the same order as Preparation Example 24 for wet medium dispersion treatment. Next, the alkali-soluble polyimide resin solution A was added so that the solid content of the pigment dispersion liquid became 15.00% by weight, and diluted to prepare a pigment dispersion liquid 27 . In addition, the solid content in the alkali-soluble polyimide resin solution A was 28.33% by weight and the organic pigment derivative content was 1.65% by weight based on the total organic pigment contained in the pigment dispersion liquid 27 . Table 4 shows the compounding quantity (g) of each raw material.

(Preparation Example 28: Preparation of Pigment Dispersion Liquid 28)

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

(Preparation Example 29~33: Preparation of Pigment Dispersion Liquid 29~33)

Pigment dispersions 29 to 33 having a solid content of 15.00% by weight were prepared in the same procedure as in Preparation Example 1 except that copper phthalocyanine dye derivatives 1 to 5 were used instead of perylene dye derivative 1 . In addition, the content of the organic pigment derivative relative to all the organic pigments contained in the pigment dispersion liquids 29 to 33 was 1.50% by weight. Table 5 shows the compounding quantity (g) of each raw material.

(Preparation Example 34: Preparation of Pigment Dispersion Liquid 34)

Pigment dispersion 34 having a solid content of 15.00% by weight was prepared in the same procedure as in Preparation Example 16 except that copper phthalocyanine-based dye derivative 6 was used instead of perylene-based dye derivative 8 . In addition, the content of the organic pigment derivative relative to all the organic pigments contained in the pigment dispersion liquid 34 was 1.50% by weight. The compounding quantity (g) of each raw material is shown in Table 6.

(Preparation Example 35: Preparation of Pigment Dispersion Liquid 35)

Using the copper phthalocyanine dye derivative 6 instead of the perylene dye derivative 8, a pigment dispersion liquid 35 with a solid content of 15.00% by weight was prepared in the same procedure as Preparation Example 1 at the blending amount (g) shown in Table 6. . In addition, the content of the organic pigment derivative relative to all the organic pigments contained in the pigment dispersion liquid 35 was 5.00% by weight. The compounding quantity (g) of each raw material is shown in Table 6.

(Preparation Example 36~41: Preparation of Pigment Dispersion Liquid 36~41)

In place of the perylene-based pigment derivative 1, except that the diketopyrrolopyrrole-based pigment derivative 1, the isoindoline-based pigment derivative 1, and the perylene-based pigment derivatives 12 to 15 were used, the procedure was the same as in Preparation Example 1. Pigment dispersions 36 to 41 with a solid content of 15.00% by weight were prepared in the following order. The compounding quantity (g) of each raw material is shown in Table 6.

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

The blending amount of the perylene-based dye derivative 14 was increased, and the pigment dispersion liquid 42 was prepared in the same procedure as in Preparation Example 1 at the blending amount (g) shown in Table 6. In addition, the content of the organic pigment derivative relative to all the pigments contained in the pigment dispersion liquid 42 was 5.00% by weight.

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

Pigment dispersion 43 having a solid content of 15.00% by weight was prepared in the same procedure as in Preparation Example 1 without using the perylene-based dye derivative 1 at the blending amount (g) shown in Table 7.

(Preparation Example 44: Preparation of Pigment Dispersion Liquid 44)

93.75 g of alkali-soluble polyimide resin solution A, 28.13 g of SOLSPERSE 20000, and 784.38 g of PGMEA were mixed and stirred for 10 minutes. Afterwards, as (a) a black material having a nitrogen-containing heterocyclic structure, 46.88 g of C.I. Pigment Red 254 (average primary particle size 40 nm) and 46.88 g of C.I. Pigment Blue 15:6 (average primary particle size 45 nm) were added, Stir for 30 minutes. In the subsequent steps, wet medium dispersion treatment was performed in the same procedure as Preparation Example 1 to prepare a pigment dispersion 44 with a solid content of 15.00% by weight. The compounding quantity (g) of each raw material is shown in Table 7.

(Preparation Example 45: Preparation of Pigment Dispersion Liquid 45)

Pigment dispersion 45 having a solid content of 15.00% by weight was prepared in the same procedure as in Preparation Example 43 except that polymer-type dispersant solution B was used instead of SOLSPERSE 20000. The compounding quantity (g) of each raw material is shown in Table 7.

(Preparation Example 46: Preparation of Pigment Dispersion Liquid 46)

84.33 g of alkali-soluble polyimide resin solution A, 28.13 g of SOLSPERSE 20000, 790.97 g of PGMEA, and 2.81 g of copper phthalocyanine dye derivative 1 were mixed and stirred for 10 minutes. Then, as (a) a black material having a nitrogen-containing heterocyclic structure, 27.33 g of C.I. Pigment Yellow 139 (average primary particle size 65 nm), 30.88 g of C.I. Pigment Violet 23 (average primary particle size 58 nm), and 35.55 g C.I. Pigment Blue 60 (average primary particle size 61nm), stirred for 30 minutes. In the subsequent steps, the wet medium dispersion treatment was performed in the same procedure as in Preparation Example 1 to prepare a pigment dispersion 46 with a solid content of 15.00% by weight. The compounding quantity (g) of each raw material is shown in Table 7. In addition, the content of the organic pigment derivative relative to all the organic pigments contained in the pigment dispersion liquid 46 was 3.00% by weight.

(Preparation Example 47: Preparation of Pigment Dispersion Liquid 47)

Except for increasing the amount of the copper phthalocyanine dye derivative 1, a pigment dispersion 47 having a solid content of 15.00% by weight was prepared in the same procedure as in Preparation Example 46 with the blending amounts of the raw materials shown in Table 7. In addition, the content of the organic pigment derivative relative to all the organic pigments contained in the pigment dispersion liquid 47 was 10.00% by weight.

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

系色素衍生物1代替銅酞青系色素衍生物1，除此之外，以與調製例46相同的順序，以表7所示之原料的摻合量，調製固體成分15.00重量%的顏料分散液48。 use two

Pigment-based pigment derivative 1 instead of copper phthalocyanine-based pigment derivative 1, in the same procedure as in Preparation Example 46, a pigment dispersion with a solid content of 15.00% by weight was prepared with the blending amounts of raw materials shown in Table 7. Liquid 48.

(Preparation Example 49: Preparation of Pigment Dispersion Liquid 49)

系色素衍生物1=重量比1/1的比例併用銅酞青系色素衍生物1與二

系色素衍生物1，除此之外，以與調製例46相同的順序，以表7所示的原料的摻合量，調製固體成分15.00重量%的顏料分散液49。另外，有機色素衍生物相對於顏料分散液49所含有之所有有機顏料的含量為6.00重量%。 Copper Phthalocyanine Pigment Derivatives 1/2

Copper phthalocyanine pigment derivatives 1 = weight ratio 1/1 and copper phthalocyanine pigment derivatives 1 and 2

Pigment dispersion 49 having a solid content of 15.00% by weight was prepared in the same procedure as in Preparation Example 46 except for the pigment derivative 1, with the blending amounts of the raw materials shown in Table 7. In addition, the content of the organic pigment derivative relative to all the organic pigments contained in the pigment dispersion liquid 49 was 6.00% by weight.

(Preparation Example 50: Preparation of Pigment Dispersion Liquid 50)

Except that the perylene-based dye derivative 7 was not used, a pigment dispersion liquid 50 having a solid content of 15.00% by weight was prepared in the same procedure as in Preparation Example 13 with the blending amounts of the raw materials shown in Table 8.

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

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

(Preparation Example 52: Preparation of Pigment Dispersion Liquid 52)

In addition to using copper phthalocyanine-based dye derivative 1 instead of perylene-based dye derivative 7, in the same procedure as Preparation Example 13, a compound with a solid content of 15.00% by weight was prepared with the blending amount of the raw materials shown in Table 8. Pigment dispersion 52. In addition, the content of the organic pigment derivative relative to all the organic pigments contained in the pigment dispersion liquid 52 was 4.00% by weight.

(Example 1)

26.40 g of pigment dispersion 1, 5.30 g of alkali-soluble polyimide resin solution A, and 1.35 g of ε-caprolactone of dipenteoerythritol as a compound having two or more radically polymerizable groups Addition acrylate (KAYARAD DPCA-60; manufactured by Nippon Kayaku Co., Ltd.; "DPCA-60" in the table), 0.30 g of "ADEKA CRUISE" (registered trademark) NCI-831 ( ADEKA Co., Ltd.), 0.30 g of VG-3101L as a compound having 3 epoxy groups in the molecule as a thermal crosslinking agent, 7.85 g of PGMEA as a solvent, and 8.50 g of MBA were mixed and sealed, and placed in a shaker Stirring was carried out for 30 minutes to prepare a negative photosensitive composition 1 in which the total organic pigment content was 33.00% by weight and the solid content was 15.00% by weight based on the total solid content in the negative photosensitive composition. Next, the dispersion stability was evaluated by the method described above. In addition, the pigment dispersion used to prepare the photosensitive composition is not stored for a long time in the form of the pigment dispersion alone, but is used to prepare the photosensitive composition within 2 hours after being obtained by dispersion treatment in a wet medium. Table 9 shows the compounding amount (g) of each raw material, and Table 14 shows the evaluation results of dispersion stability.

After preparing in the above order, let it stand for 30 days in an incubator under atmospheric pressure/under shading/actual temperature 25°C±1°C, and stir the negative photosensitive composition 1 after long-term storage in this state on a shaker for 1 Minutes, with a spin coater, adjust the number of rotations so that the thickness of the finally obtained cured film becomes 1.0 μm, and apply it on the surface of TEMPAX (light-transmitting glass substrate of 50 mm×50 mm) to obtain a coating film. Furthermore, the coating film was prebaked at 100 degreeC for 120 second under atmospheric pressure using the hotplate (SCW-636; Dainippon Screen Mfg. Co., Ltd. product), and the prebaked film was obtained. Using a double-side alignment single-side exposure device (reticle alignment exposure machine PEM-6M; manufactured by UNION Optical Co., Ltd.), j-line (wavelength 313nm), i-line (wavelength 365nm), h-line (wavelength 365nm) and h-line ( The mixed radiation of wavelength 405nm) and g-line (wavelength 436nm), with the necessary minimum exposure dose obtained by the above method, irradiates the exposure light to the pre-baked film to obtain the exposure film. Next, using a small-sized developing device for lithography (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.), develop for 60 seconds with a 2.38% by weight TMAH aqueous solution, rinse with deionized water for 30 seconds to obtain a developed film, and use a high-temperature inert gas oven ( INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.), the developed film was heated at 250° C. for 60 minutes in a nitrogen atmosphere to obtain a substrate for light-shielding evaluation having a cured film with a thickness of 1.0 μm on TMEPAX. The light-shielding property of the cured film was evaluated by the aforementioned method, and the results are shown in Table 14.

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

On the entire surface of an alkali-free glass substrate 11 of 38 mm×46 mm, a silver/copper alloy thin film (volume ratio 10:1) with a thickness of 10 nm was formed by sputtering, and etched to form a patterned metal reflective layer 12 . Next, an ITO transparent conductive film with a thickness of 10nm was formed on the entire surface by sputtering, and after etching to form the second electrode 13 in the same pattern and the auxiliary electrode 14 as an extraction electrode, "SEMICO CLEAN" (registered trademark) 56 (manufactured by FURUUHCI CHEMICAL Co., Ltd.) was ultrasonically cleaned for 10 minutes, and washed with ultrapure water to obtain an electrode-forming substrate.

After preparation, let it stand for 30 days in an incubator under atmospheric pressure/shading/actual temperature of 25°C±1°C, and store it in this state for a long time, then stir it on a shaker for 1 minute, and the obtained negative photosensitive Composition 1 was coated on the surface of the electrode formation substrate using a spin coater (MS-A100; manufactured by MIKASA Co., Ltd.) by adjusting the number of rotations so that the thickness of the finally obtained pixel division layer became 1.0 μm, to obtain a coating film. Furthermore, the coating film was prebaked at 100 degreeC for 120 second under atmospheric pressure using the hotplate (SCW-636; Dainippon Screen Mfg. Co., Ltd. product), and the prebaked film was obtained.

Use a double-side alignment single-side exposure device (mask alignment exposure machine PEM-6M; manufactured by UNION Optical Co., Ltd.), and use the j-line (wavelength 313nm) and i-line of an ultra-high pressure mercury lamp through a negative exposure mask. (wavelength 365nm), h-line (wavelength 405nm) and g-line (wavelength 436nm) mixed rays, with the necessary minimum exposure dose, irradiate the exposure light to the pre-baked film to form a pattern to obtain an exposed film. Next, using a small-sized developing device for lithography (AD-2000; manufactured by Takizawa Sangyo Co., Ltd.), it was developed with a 2.38% by weight TMAH aqueous solution for 60 seconds, and rinsed with deionized water for 30 seconds to obtain a developed film. Furthermore, using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.), the developed film was heated at 250° C. for 60 minutes in a nitrogen atmosphere to form a cured film on the center of the electrode formation substrate. The pixel division layer 15 with an opening (70 μm in width/260 μm in width) and a thickness of 1.0 μm is arranged in a region of 16 mm in length/16 mm in width to obtain a substrate for forming a pixel division layer with an aperture ratio of 25%. The ITO electrode was evaluated by the above-mentioned method. Table 14 shows the evaluation results of the development residues generated above. In addition, the openings referred to here will eventually become part of the light-emitting pixel portion of the organic EL display device after undergoing the manufacturing process described later.

Next, an organic EL display device was fabricated using the pixel dividing layer forming substrate. In order to form the organic EL layer 16 including the light-emitting layer by the vacuum evaporation method, under the evaporation conditions of a vacuum degree of 1×10 ^-3 Pa or less, the substrate for forming the pixel dividing layer is rotated relative to the evaporation source. The compound (HT-1) was formed into a film to form a hole injection layer, and the compound (HT-2) was formed into a film with a thickness of 50 nm to form a hole transport layer. Next, compound (GH-1) was evaporated to a thickness of 40 nm as a host material, and compound (GD-1) was evaporated to a thickness of 40 nm as a dopant material on the light emitting layer. Thereafter, the compound (ET-1) and the compound (LiQ) were laminated at a volume ratio of 1:1 and a thickness of 40 nm to serve as an electron transport material.

Next, after vapor-depositing 2 nm of the compound (LiQ), 10 nm of silver/magnesium alloy (volume ratio 10:1) was vapor-deposited as the first electrode 17 . Thereafter, under a low-humidity/nitrogen atmosphere, the cap-shaped glass plate was bonded with an epoxy resin-based adhesive to seal it, thereby obtaining a first organic EL display device. In addition, the thickness referred to here is the display value of the quartz oscillator type film thickness monitor.

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

Next, only the aperture ratio of the negative exposure mask was changed, and a second organic EL display device with a pixel dividing layer having an aperture ratio of 18% was additionally produced in the same order. For the first and second organic EL display devices, the above-mentioned The method used to evaluate the reliability of luminescence, the results are shown in Table 14.

Furthermore, an organic EL display device for evaluating the reliability of light emission was produced by the following method, each including a cured film including a cured product of the negative photosensitive composition 1 as a pixel dividing layer and a planarization layer.

FIG. 3 shows the manufacturing steps of an organic EL display device including the steps of forming a pixel dividing layer and a planarization layer.

Using a spin coater, the number of rotations was adjusted so that the thickness of the finally obtained planarized layer became 1.5 μm, and the negative photosensitive composition 1 was coated on the surface of an alkali-free glass substrate 18 of 38 mm×46 mm, To obtain a coated film. Using a hot plate, the coating film was prebaked at 100° C. for 120 seconds under atmospheric pressure to obtain a prebaked film. Using a double-sided alignment single-sided exposure device, through a negative exposure mask, using the j-line (313nm), i-line (wavelength 365nm), h-line (wavelength 405nm) and g-line (wavelength 436nm) of the ultra-high pressure mercury lamp The rays are mixed, and the prebaked film is irradiated with exposure light at the minimum necessary exposure amount to form a pattern to obtain an exposed film. Next, using a small developing apparatus for lithography, it developed with 2.38 weight% TMAH aqueous solution for 60 seconds, rinsed with deionized water for 30 seconds, and obtained the developed film. Furthermore, using a high-temperature inert gas oven, under a nitrogen atmosphere, the developed film was heated at 250°C for 60 minutes to form a cured film, and a flat film-like planarization layer with no openings on the plane was obtained in the center of the alkali-free glass substrate. 19.

Next, a silver/copper alloy thin film (volume ratio 10:1) with a thickness of 10 nm and an ITO transparent conductive film with a thickness of 10 nm were sequentially formed on the entire surface of the planarization layer 19 by sputtering. After uniformly etching the silver/copper alloy film and the two layers of the ITO transparent conductive film to form the pattern of the metal reflection layer/second electrode 20 and the metal reflection layer/auxiliary electrode 21, perform ultrasonic cleaning with "SEMICO CLEAN" 56 After cleaning for 10 minutes, it was washed with ultrapure water to obtain an electrode-forming substrate. In addition, a two-layer laminated pattern including a metal reflective layer and a second electrode is formed so that the aperture ratio in the effective light-emitting region of the finally obtained organic EL display device becomes 70%, whereby the gap between the surface area of the planarizing layer 19 is reduced. In this case, 30% of the film surface was covered with the laminated pattern and 70% of the film surface was exposed. Subsequent steps are the same method as in the production of the above-mentioned second organic EL display device, using the negative photosensitive composition 1 to form the pixel dividing layer 22, and then forming the light-emitting pixel 23 and the first electrode 24 in sequence, and then sealing. Fabricate a third organic EL display device with a pixel division layer with a film thickness of 1.0 μm/aperture ratio of 18% and a planarization layer with a film thickness of 1.5 μm/aperture ratio of 0%, and evaluate the reliability of light emission and black spots by the above method . The evaluation results are shown in Table 14.

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

Except for using Pigment Dispersion Liquids 2 to 52 instead of Pigment Dispersion Liquid 1, Negative Photosensitive Compositions 2 to 52 with a solid content of 15% by weight were prepared in the same procedure as in Example 1, and evaluated by the above method dispersion stability. The compounding quantity (g) of each raw material is shown in Tables 9-13.

Next, except that negative photosensitive compositions 2 to 52 were used instead of negative photosensitive composition 1, a light-shielding evaluation substrate, a pixel dividing layer evaluation substrate, and an organic EL were produced in the same procedure as in Example 1. For the display device, the light-shielding properties, development residues, light emission reliability, and black spots were evaluated by the aforementioned methods. The negative photosensitive compositions used and their evaluation results are arranged and shown in Tables 14-18. In addition, the pigment dispersion used to prepare the photosensitive composition is not stored for a long time in the form of the pigment dispersion alone, but is used for the preparation of the photosensitive composition within 2 hours after being obtained by the above-mentioned wet medium dispersion treatment. . In addition, all the negative photosensitive compositions used were prepared in the same manner as in Example 1, and then left to stand for 30 days in an incubator with an actual temperature of 25° C.±1° C. Stir on a shaker for 1 minute before use.

(Example 21)

12.50 g of pigment dispersion 16, 11.75 g of alkali-soluble polyimide resin solution A, 1.80 g of quinonediazide compound a as a photosensitive agent, 0.30 g of VG-3101L as a thermal crosslinking agent, 15.15 g of PGMEA and 8.50 g of MBA were mixed and sealed, stirred on a shaker for 30 minutes to prepare a positive photosensitive composition 1 with a solid content of 15.00% by weight, and the dispersion stability was evaluated by the method described above. In addition, the pigment dispersion used to prepare the photosensitive composition is not stored for a long time in the form of the pigment dispersion alone, but is used to prepare the photosensitive composition within 2 hours after being obtained by the above-mentioned wet medium dispersion treatment. Table 19 shows the compounding amount (g) of each raw material, and Table 20 shows the evaluation results of dispersion stability.

After preparation, the positive-type photosensitive composition 1 was left to stand for 30 days in an incubator under atmospheric pressure/light-shielding/actual temperature 25°C±1°C for long-term storage, and then stirred on a shaker for 1 minute without performing the exposure step. And the developing process, except that, the substrate for light-shielding property evaluation was obtained by the procedure similar to Example 1, and the light-shielding property of the cured film was evaluated by the said method, and the result is shown in Table 20. Next, except for using a positive exposure mask in which the opening and the light shielding portion of the negative exposure mask are reversed, a pixel division layer evaluation substrate and an organic EL display device were produced in the same procedure as in Example 1, and the above-mentioned Evaluation of developing residue, luminescent reliability and black spots was carried out by the method. The evaluation results are shown in Table 20.

(Example 22, Comparative Example 33)

Except for using the pigment dispersion liquid 19 and 45 instead of the pigment dispersion liquid 16, positive photosensitive compositions 2 to 3 were prepared in the same procedure as in Example 21, and the dispersion stability was evaluated by the method described above. Table 19 shows the compounding amount (g) of each raw material, and Table 20 shows the evaluation results of dispersion stability.

After preparation, the positive photosensitive composition 2~3 was left to stand for 30 days in an incubator under atmospheric pressure/shading/actual temperature 25°C±1°C for long-term storage, and then stirred on a shaker for 1 minute to combine with In the same procedure as in Example 21, the light-shielding evaluation substrate, the pixel division layer evaluation substrate, and the organic EL display device were produced, and the light-shielding properties, development residues, light emission reliability, and black spots were evaluated by the aforementioned methods. Table 20 shows the positive photosensitive composition used and its evaluation results.

On the whole, it can be seen that the organic EL display devices of Comparative Examples 1 to 33 have at least one characteristic insufficient in black spots and luminous reliability, but the organic EL display devices of Examples 1 to 22, on the one hand, can suppress Black dots, on the one hand, can obtain high luminescence reliability, and can have both characteristics.

From the above, it can be seen that the organic EL display device of the present invention is useful.

Industrial availability

The organic EL display device of the present invention can be applied to applications that can suppress dark spots and require high light emission reliability, for example, electronic equipment such as smart phones, TVs, 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‧‧‧Substrate

7‧‧‧Contact hole

8‧‧‧Pixel segmentation layer

9‧‧‧luminous pixels

10‧‧‧First electrode

Claims (13)

An organic EL display device, which is an organic EL display device provided with a first electrode, a pixel dividing layer, a light-emitting pixel, a second electrode, a planarization layer, and a substrate, wherein the pixel dividing layer and/or the planarization layer contain (a) a black material having a nitrogen-containing heterocyclic structure, (b) a dispersant, and (c) a resin, and the (b) dispersant contains a compound represented by the following general formula (1) and/or a compound represented by the following general formula (2) The compound represented;

(In the above general formula (1), X ¹ is a substituent directly bonded to the perylene ring, which 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 with a N,N-dialkylamino group at the end; Z ¹ represents an atom directly bonded to the perylene ring or a substituent, which represents a hydrogen atom, an alkyl group or an alkoxy group ; n and m are integers, n represents 1 or 2, and satisfies n+m=10);

(In the above-mentioned general formula (2), R ² and R ³ are identical to each other and represent a hydrogen atom, an aryl group or a methyl group with a substituent; X ² is a substituent directly bonded to the perylene ring and/or benzene ring, which Represents -SO ₃ H, -SO ₃ M, -SO ₂ NHR ⁴ or -CONHR ⁴ ; M represents Na, K or NH ₄ ; R ⁴ represents an organic group with a N,N-dialkylamino group at the end; Z ² represents an atom directly bonded to the perylene ring or a substituent, which 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 EL display device according to claim 1, wherein the (b) dispersant contains a compound represented by the following general formula (22) and/or a compound represented by the following general formula (23):

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

(In the above general formula (23), R ⁵ and R ⁶ are the same as each other and represent a hydrogen atom, an aryl group or a methyl group with a substituent; X ⁴ represents -SO ₃ H directly bonded to the perylene ring and/or 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 6~8). The organic EL display device according to claim 1 or 2, wherein the (a) black material having a nitrogen-containing heterocyclic structure includes a perylene-based organic black pigment having two benzimidazole rings in the molecule as the nitrogen-containing heterocyclic ring. The organic EL display device according to claim 1 or 2, wherein the (a) black material having a nitrogen-containing heterocyclic structure comprises at least a mixture of organic yellow pigments, organic red pigments and organic blue pigments, and the organic yellow pigments contain benzene An imidazolone-based organic yellow pigment, the organic blue pigment includes a phthalocyanine-based organic blue pigment and/or an indanthrene-based organic blue pigment, and the organic red pigment includes a perylene-based organic red pigment. The organic EL display device according to claim 1 or 2, wherein the (c) resin contains 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 claim 1 or 2, wherein the (b) dispersant further contains a polymeric dispersant having a phosphoric acid group. The organic EL display device according to claim 1 or 2, wherein the pixel dividing layer and/or the planarization layer comprises a hardened negative photosensitive composition. The organic EL display device according to claim 1 or 2, wherein the pixel dividing layer and/or the planarization layer comprises a cured product of a positive photosensitive composition. The organic EL display device according to claim 1 or 2, wherein the optical density of the pixel dividing layer and/or the planarization layer per 1.0 μm of film thickness is not less than 0.5 and not more than 2.0. The organic EL display device according to claim 1 or 2, wherein the substrate is a flexible substrate comprising polyimide resin. The organic EL display device according to claim 1 or 2, wherein the aperture ratio in the display region of the pixel dividing layer is 20% or less. A method for forming a pixel dividing layer and/or a planarization layer, which is a method for forming the pixel dividing layer and/or the planarization layer provided by the organic EL display device according to any one of claims 1 to 12, wherein It includes a developing step of obtaining a developed film using a developing solution containing 1.0 to 3.0% by weight of tetramethylammonium hydroxide.

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