WO2024038810A1

WO2024038810A1 - Positive-type photosensitive composition, cured film, organic el display device, and colorant

Info

Publication number: WO2024038810A1
Application number: PCT/JP2023/029066
Authority: WO
Inventors: 暁宏石川; 充杉原
Original assignee: 東レ株式会社
Priority date: 2022-08-19
Filing date: 2023-08-09
Publication date: 2024-02-22

Abstract

The present invention provides a positive-type photosensitive composition capable of suppressing generation of foreign matter defects on a surface of an opening part and forming a pixel division layer and/or planarized layer with high thermal stability of light blocking effect and with high resolution.　The present invention is a positive-type photosensitive composition containing: (a) a compound represented by formula (1) and/or a compound represented by formula (2); (b) a resin; (c) a photo-acid generator; and (d) an organic solvent.

Description

Positive photosensitive composition, cured film, organic EL display device, and dye

The present invention relates to a positive photosensitive composition, a cured film, an organic EL display device, and a dye.

Further enhancement of the functionality of display devices equipped with flexible type organic electroluminescence (EL) displays is being considered. By eliminating the polarizing plate that was conventionally placed on the front of the display, it is expected that loss of brightness will be eliminated and power consumption will be reduced. In order to replace the function of a polarizing plate, it is necessary to add a function to suppress the reflection of external light such as sunlight, and it is necessary to add a function to suppress the reflection of external light such as sunlight. A technique for forming a pattern using a photolithography method is attracting attention. An example of the pixel dividing layer imparted with light-shielding properties is a black pixel dividing layer, which is also called a black pixel defining film or black bank. The black pixel dividing layer is arranged to separate the light emitting pixels of each color, such as red, green, and blue, arranged in the opening. On the other hand, the flattening layer serves as a base layer that allows the electrodes and the black pixel dividing layer to be formed smoothly, and is arranged so as to cover the convex steps formed by TFTs (Thin Film Transistors).

In recent years, with the aim of improving the display quality of organic EL displays, there has been a need to improve the resolution of black pixel dividing layers in order to make light-emitting pixels smaller and higher definition in small displays such as wristwatch-type display devices. In addition, in order to obtain a highly uniform light-shielding property even if there are parts of the oven that experience high temperatures locally during the curing process, we have also improved the thermal stability of the light-shielding property of the black pixel dividing layer. Improvement is required. On the other hand, in the case of blackening the planarization layer, improvement in resolution and improvement in thermal stability of light-shielding properties are required from the same viewpoint.

As a material for forming the black pixel dividing layer, instead of carbon black, which has a fatal defect in electrical properties such as low insulation and high dielectric constant, various materials containing non-carbon black coloring materials are used. Photosensitive compositions have been proposed. For example, C.I., a black dye consisting of an azo chromium complex, I. Positive-working photosensitive compositions containing Solvent Black 27, 29 or 34 are disclosed in Patent Documents 1, 2 and 3. A positive photosensitive composition containing a salt-forming compound consisting of an acidic dye and a basic dye is disclosed in Patent Document 4. A negative photosensitive composition containing a benzodifuranone black pigment is disclosed in Patent Document 5. Patent Document 6 discloses a negative photosensitive composition containing a phthalocyanine compound having a basic functional group, an organic blue pigment, an organic purple pigment, and an organic yellow pigment.

International Publication No. 2017/069172 International Publication No. 2021/246448 International Publication No. 2021/246444 International Publication No. 2022/039034 JP 2022-38599 Publication JP2019-207306A

However, when using the positive photosensitive compositions disclosed in Patent Documents 1, 2, and 3, it is easy to obtain a pixel dividing layer and/or a flattening layer that has light-shielding properties and high thermal stability. ．． I. It is generally known that black dyes made of azo chromium complexes, such as Solvent Black 27, 29, or 34, are likely to generate highly toxic hexavalent chromium when subjected to high-temperature treatment. Therefore, there were problems from the viewpoints of human safety and environmental conservation. Further, the positive photosensitive composition disclosed in Patent Document 4 has a problem in that the thermal stability of light-shielding properties is insufficient. The negative photosensitive composition disclosed in Patent Document 5 had a problem of insufficient resolution. The negative photosensitive composition disclosed in Patent Document 6 has a problem in that protruding foreign matter defects are generated on the surface of the opening due to the high temperature treatment normally performed when forming the pixel division layer.

From the above, the pixel dividing layer contains a coloring material that does not have chromium atoms in its molecules, suppresses the occurrence of protruding foreign matter defects on the surface of the opening, has high light-shielding thermal stability, and has high resolution. A photosensitive composition capable of forming a flattening layer and/or a flattening layer has been desired.

In order to solve the above problems, the positive photosensitive composition of the present invention has the following configuration. That is,
A positive material containing (a) a compound represented by formula (1) and/or a compound represented by formula (2), (b) a resin, (c) a photoacid generator, and (d) an organic solvent. It is a type photosensitive composition.

In formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, -SO ₃ H, -SO ₃ ^- , carbon number Represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, -CF ₃ , -F, -Br or -CN. However, the total number of -SO ₃ H and -SO ₃ ^- in R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ is 1 to 4.
R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each independently represent a hydrogen atom, -OH, -F, -Br, -CN or an alkoxy group having 1 to 5 carbon atoms. However, R ⁹ and R ¹⁰ and R ¹¹ and R ¹² may each independently be bonded to each other to form a linking group -X ¹ -. -X ¹ - represents -O- or -SO ₂ -.

In formula (2), R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, -SO ₃ H, -SO ₃ ^- , carbon number Represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, -CF ₃ , -F, -Br or -CN. However, the total number of -SO ₃ H and -SO ₃ ^- in R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ is 1 to 4.
R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom, -OH, -F, -Br, -CN or an alkoxy group having 1 to 5 carbon atoms. However, R ²¹ and R ²² and R ²³ and R ²⁴ may each independently be bonded to each other to form a linking group -X ² -. -X ² - represents -O- or -SO ₂ -.

According to the present invention, it is possible to suppress the occurrence of foreign matter defects on the surface of the opening, and form a pixel division layer and/or a planarization layer with high light-shielding properties, high thermal stability, and high resolution.

FIG. 1 is a cross-sectional view of a TFT substrate in an organic EL display device including a pixel dividing layer and a planarization layer as a specific example of an embodiment of the present invention. FIG. 2 is a scanning electron microscope (SEM) image of a protruding foreign particle defect observed in Comparative Example 4. FIG. 3 shows a manufacturing process of an organic EL display device including a process of forming a pixel dividing layer in all Examples. FIG. 4 is a graph comparing the transmittance (%) of the prebaked film obtained in Reference Example 1 (broken line) and the prebaked film obtained in Reference Example 2 (solid line) at a wavelength of 350 to 650 nm.

Hereinafter, the present invention will be explained in detail. A numerical range expressed using "~" means a range that includes the numerical values written before and after "~" as lower and upper limits. The pixel dividing layer means a pixel dividing layer included in an organic EL display device, and does not include the black matrix of a liquid crystal display device. Visible light means light with a wavelength of 380 nm or more and less than 780 nm, and near ultraviolet rays means light with a wavelength of 200 nm or more and less than 380 nm. Near-infrared rays mean light in a wavelength range of 780 nm or more and 1300 nm or less.

Light-shielding refers to the function of reducing the intensity of transmitted light relative to the intensity of light incident perpendicularly to the cured film, and light-shielding property refers to the extent to which visible light is blocked. Transmittance means light transmittance. The weight average molecular weight (Mw) is a value analyzed by gel permeation chromatography (GPC) using tetrahydrofuran as a carrier and converted using a standard polystyrene calibration curve.

"C.I." used in the name of some coloring materials is an abbreviation for Color Index Generic Name, and is based on the color index published by The Society of Dyers and Colorists, and is based on the coloring materials registered in the color index. Color Index Generic Name represents the chemical structure and crystal form of the pigment or dye. Solid content means the proportion (mass %) of components excluding organic solvent and water in a positive photosensitive composition.

As a result of intensive studies by the present inventors, we adopted a coloring material with a specific chemical structure as a component for imparting light-shielding properties, and furthermore, a composition that imparts positive photosensitivity by combining a resin and a photoacid generator. We have discovered that this product has a particularly remarkable effect in solving the above-mentioned problems.

That is, the positive photosensitive composition of the present invention comprises (a) a compound represented by formula (1) and/or a compound represented by formula (2), (b) a resin, and (c) a photoacid. It is a positive photosensitive composition containing a generator and (d) an organic solvent.

The positive photosensitive composition of the present invention contains (a) a compound represented by formula (1) and/or a compound represented by formula (2) (hereinafter sometimes referred to as component (a)). do.

Component (a) has the effect of imparting light-shielding properties to the finally obtained pixel division layer and/or planarization layer. Component (a) has a perylene-3,4,9,10-tetracarboxylic acid bisbenzimidazole (hereinafter sometimes referred to as PTCBI) skeleton, and the carbon atoms constituting the benzene ring in the two benzimidazole structures. It is a condensed polycyclic aromatic sulfonic acid in which an atom is substituted with one to four sulfo groups. The sulfo group herein includes -SO ₃ H and -SO ₃ ^- in which protons have been dissociated (ie, sulfonate group). The PTCBI skeleton includes the cis skeleton represented by the formula (3) and the trans skeleton represented by the formula (4), and has two benzimidazole skeletons in the molecule. Light-shielding properties are developed. In order to help understand the synthesis method for obtaining component (a) described later, the position numbers of some of the carbon atoms constituting the perylene ring are shown in formula (3) and formula (4). Also listed in

The form of component (a) present in the positive photosensitive composition, pixel dividing layer, and flattening layer is not particularly limited, and may be dispersed as insoluble particles or dissolved. good. That is, component (a) may be a pigment or a dye, or a mixture of them may be used. (a) The existing form of the component is generally adjusted by the number of carbon atoms of the alkyl group having 1 to 5 carbon atoms and/or the alkoxy group having 1 to 5 carbon atoms and the number of substituents in the molecule (d) solubility in organic solvents. It can be controlled by Moreover, it can be controlled by selecting (b) resin and (d) organic solvent depending on the chemical structure of component (a).

Component (a) may form a salt derived from -SO ₃ ^- , and by forming a salt, the solubility in the organic solvent (d) may be improved. Examples of the salt form include salts with monovalent metal cations such as Na ⁺ , K ⁺ , and Li ^{+ ,} and polyvalent salts such as Ca ²⁺ , Mn ²⁺ , Sr ²⁺ , Ba ²⁺ , Zn ²⁺ , and Al ³⁺ . Salts with metal cations, C. I. Examples include salts with cation moieties of cationic dyes such as Basic Blue 3 and 22, and salts with organic cations such as trialkylbenzylammonium cations and tetraalkylammonium cations. Among these, in order to improve resolution, it is preferable that component (a), which is an anionic compound, forms a salt with component (f), which is a cationic compound, which will be described later. When a salt is formed, it is defined as a mixture of component (a) and other components.

By the way, when a highly polar functional group such as a sulfo group or an amino group is introduced into the molecular structure of an organic pigment, the crystallinity is generally impaired and the thermal stability becomes lower than that of the organic pigment before the highly polar functional group is introduced. It is well known as common general knowledge among those skilled in the art that not only is it likely to cause defects such as protrusion-like foreign matter defects due to crystal growth, but also a dark hue and a decrease in near-ultraviolet transmittance. On the other hand, component (a) has a sulfo group introduced into the PTCBI skeleton, irrespective of the above-mentioned existence form, but becomes protrusive under high temperature treatment (for example, 250 to 270°C) in the curing process described below. It is possible to suppress the occurrence of foreign matter defects such as, and obtain excellent light-shielding thermal stability. When a protruding foreign particle defect occurs on the surface of the opening of the pixel dividing layer or the planarizing layer, it becomes difficult to light up the light emitting pixel. Therefore, it is desirable to suppress the occurrence of protruding foreign matter defects.

Furthermore, the sulfo group possessed by component (a) is sterically bulky and has the effect of alleviating the strong stacking property between molecules derived from the PTCBI skeleton. Therefore, compared to PTCBI derivatives substituted with substituents other than sulfo groups (hereinafter sometimes referred to as PTCBI derivatives) and unsubstituted PTCBI, component (a) has rather increased near-ultraviolet transmittance, equivalent to It also has light blocking properties. Therefore, the component (a) can preferably improve the reaction rate of the photoacid generator (c) in the exposure step described below, thereby increasing the amount of acid generated in the film.

Furthermore, since the component (a) has a sulfo group, it is preferably provided with self-dispersibility and/or high solubility in an alkaline developer in the development step described below, and the generation of development residues can be preferably suppressed.

Based on the above principle, it is possible to form a pixel dividing layer and/or a flattening layer that has high light-shielding properties, high thermal stability, and high resolution due to the characteristic chemical structure of component (a). High thermal stability of the light-shielding property means that the light-shielding property changes little with respect to changes in heating temperature in the curing process, and that the resulting pixel dividing layer and/or planarization layer is heated again. This means that the change in light shielding properties is small. On the other hand, high resolution means that the aperture width of the aperture is narrow. The size of a light-emitting pixel in the display area of an organic EL display device is determined by the aperture width of the aperture of the pixel dividing layer, and the smaller the light-emitting pixel size, the higher the resolution and display quality can be obtained, so the resolution of the pixel dividing layer is higher. The more desirable. Further, due to the panel configuration, if the pixel division layer has a high resolution, the flattening layer also needs to have a high resolution. Therefore, it is desirable that the resolution of the planarization layer is also higher.

Component (a) is a pigment that has a maximum absorption wavelength in the wavelength range of 550 to 650 nm and exhibits a dark blue color, and PTCBI and PTCBI derivatives that have a maximum absorption wavelength in the wavelength range of 480 to 540 nm and are pigments that exhibit a dark purple color. It has different optical properties. The pre-baked film of the positive photosensitive composition of the present invention containing component (a) has a maximum transmittance of 800 to 1 , the maximum transmittance at 200 nm is high. Therefore, it is possible to use near-infrared alignment, which automatically aligns the exposure mask to the electrode-forming substrate using a near-infrared camera, and it is possible to obtain high positional accuracy and high productivity while having high light-shielding properties. Can be done.

In the positive photosensitive composition of the present invention, the component (a) is a compound represented by the formula (5) and/or a compound represented by the formula (6) in improving the thermal stability and resolution of the light-shielding property. It is preferable to contain a compound.

In formula (5), R ²⁵ and R ²⁶ each independently represent -SO ₃ H or -SO ₃ ^- . n ¹ and n ² are integers and each independently represents 0 to 2. However, the total number of n ¹ and n ² is 1 to 4.

In formula (6), R ²⁷ and R ²⁸ each independently represent -SO ₃ H or -SO ₃ ^- . n ³ and n ⁴ are integers and each independently represents 0 to 2. However, the total number of n ³ and n ⁴ is 1 to 4.

Specific examples of the component (a) contained in the positive photosensitive composition of the present invention include a compound represented by formula (7), a compound represented by formula (8), and a compound represented by formula (9). Compound, compound represented by formula (10), compound represented by formula (11), compound represented by formula (12), compound represented by formula (13), compound represented by formula (14) Examples include a group of compounds represented by formula (15), compounds represented by formula (16), and cis-compounds corresponding to isomers of these compounds.

Examples of the synthesis method for obtaining component (a) include the first method and the second method described below.

The first method is perylene-3,4,9,10-tetracarboxylic dianhydride (hereinafter sometimes abbreviated as PTCDA) or a carbon atom in which a substituent other than a sulfo group constitutes a perylene ring. perylene-3,4,9,10-tetracarboxylic dianhydride derivative (hereinafter sometimes abbreviated as PTCDA derivative) substituted with 1,2-diaminobenzene and/or a substituent other than the sulfo group. A method for obtaining component (a) is to sulfonate a product obtained by reacting a 1,2-diaminobenzene derivative in which is substituted with a carbon atom constituting a benzene ring to introduce a sulfo group.

Examples of PTCDA derivatives include 1,12-dihydroxyperylene-3,4,9,10-tetracarboxylic dianhydride, 1,7-dihydroxyperylene-3,4,9,10-tetracarboxylic dianhydride , 1-bromoperylene-3,4,9,10-tetracarboxylic dianhydride, 1,7-dibromoperylene-3,4,9,10-tetracarboxylic dianhydride, 1,7-difluoroperylene- 3,4,9,10-tetracarboxylic dianhydride, 1,6-difluoroperylene-3,4,9,10-tetracarboxylic dianhydride, 1,6,7,12-tetrafluoroperylene-3 , 4,9,10-tetracarboxylic dianhydride, 1,6,7,12-tetracyanoperylene-3,4,9,10-tetracarboxylic dianhydride, 1,12-methoxyperylene-3, 4,9,10-tetracarboxylic dianhydride, 1,12-ethoxyperylene-3,4,9,10-tetracarboxylic dianhydride, 1,12-propoxyperylene-3,4,9,10- Tetracarboxylic dianhydride, 1,12-isopropoxyperylene-3,4,9,10-tetracarboxylic dianhydride, 1,12-butoxyperylene-3,4,9,10-tetracarboxylic dianhydride 1,12-pentoxyperylene-3,4,9,10-tetracarboxylic dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride monosulfone, perylene-3,4, Examples include 9,10-tetracarboxylic dianhydride disulfone. These PTCDA derivatives may be commercially available from Henan Tianfu Chemical Co., Ltd., for example. Further, for the method of obtaining the PTCDA derivative, refer to the synthesis methods disclosed in, for example, WO 97/22607, JP 2018-165257, WO 2007/554787, and WO 2007/093643. can.

Examples of 1,2-diaminobenzene derivatives include 4,5-dimethyl-1,2-phenylenediamine, 2,3-diaminotoluene, 4,5-diethyl-1,2-phenylenediamine, 4,5-dipropyl -1,2-phenylenediamine, 1,2-diamino-4-fluorobenzene, 1,2-diamino-4-bromobenzene, 4-methoxy-1,2-phenylenediamine, 4-ethoxy-1,2-phenylene Diamine, 4-propoxy-1,2-phenylenediamine, 4-butoxy-1,2-phenylenediamine, 1,2-diamino-4,5-methoxybenzene, 1,2-diamino-4,5-ethoxybenzene, 1,2-diamino-4,5-propoxybenzene, 1,2-diamino-4,5-butoxybenzene, 3,5-bis(trifluoromethyl)-1,2-phenylenediamine (all of the above are Sigma- (manufactured by Aldrich), and may be used alone or in combination of two or more.

In addition, as a simpler method, component (a) may be obtained by sulfonating a cis/trans mixture of PTCBI and introducing a sulfo group. A commercially available product may be used as the cis/trans isomer mixture of PTCBI. Commercially available products include, for example, “Spectrasense (registered trademark)” Black K0087 (manufactured by Color & Effect), perylene-3,4,9,10-tetracarboxylic acid bisbenzimidazole (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and PTCBI (manufactured by Tokyo Chemical Industry Co., Ltd.). (manufactured by Luminescence Technology Corporation).

The second method includes a method in which component (a) is obtained by reacting PTCDA (or a PTCDA derivative) with a 1,2-diaminobenzene derivative substituted with a sulfo group. Examples of the 1,2-diaminobenzene derivatives substituted with a sulfo group include 1,2-diamino-4-sulfonic acid and 1,2-diamino-3-sulfonic acid.

The method for obtaining component (a) will be explained in more detail by taking the above-mentioned first method as an example.
Using phenol melted at 70 to 100°C as a solvent, the starting material PTCDA (or PTCDA derivative) and 1,2-diaminobenzene (or 1,2-diaminobenzene derivative) were mixed in a ratio of 1:2 to 1:1, respectively. 2.5 and a basic catalyst such as piperazine was stirred for 6 to 10 hours at a liquid temperature of 140 to 200°C to allow the reaction to proceed sufficiently, and then The resulting water is separated by distillation as an azeotrope with phenol. Pyridine may be used in place of the solvent and basic catalyst. Cool to 100°C, add ethanol, stir at 50-70°C for 1-3 hours, and then filter. Further, the filtrate is washed with ethanol and water until it becomes clear, and dried under reduced pressure at 40 to 80° C. for 24 hours or more to obtain PTCBI (or PTCBI derivative). Usually, PTCBI (or PTCBI derivative) is obtained as a mixture containing 30 to 70% by mass of the trans isomer based on the total of 100% by mass of the cis and trans isomers. If necessary, either the cis form or the trans form may be isolated by chromatography.

Next, a sulfonation reaction is performed. A mixture of PTCBI (or PTCBI derivative) dissolved in 10 to 70% by mass of oleum is heated, the liquid temperature is adjusted to a range of 40 to 150°C, and the mixture is stirred for 3 to 15 hours. Next, the starting material is poured into water of 100 times or more mass, preferably ice water, to obtain a slurry containing precipitates, which is filtered. Next, it is washed repeatedly with a mixture of ethanol and water until the residual amount of sulfate ions determined by ion chromatography is less than 100 mass ppm, then washed with water, and further dried at 60 to 80° C. under reduced pressure. Finally, the dry agglomerates are loosened by dry pulverization using a hammer mill or jet mill to obtain powdered component (a). The distribution of the number of sulfo groups introduced per molecule of the target product can be controlled by the liquid temperature and reaction time depending on the concentration of fuming sulfuric acid, and the reaction may be carried out in multiple stages if necessary. Furthermore, after washing the obtained product, it may be purified by silica gel chromatography if necessary to increase the purity of component (a) into which a specific range of numbers of sulfo groups have been introduced. The molecular weight corresponding to the chemical structure and its purity can be conveniently monitored by liquid chromatography mass spectrometry (LC-MS).

Furthermore, as a method for obtaining a salt of component (a) and a metal cation, for example, after adding component (a) to water, it is dissolved under alkaline conditions while stirring, and a Na ⁺ source such as sodium hydroxide, Add a K ⁺ source such as potassium hydroxide, an Al ³⁺ source such as aluminum chloride, a Ba ²⁺ source such as barium chloride, or a Ca ²⁺ source such as calcium chloride, and stir at 30 to 60°C for 1 to 5 hours. Examples include a method in which salt formation is performed, followed by separation, purification, drying, and dry pulverization.

On the other hand, as a method for obtaining a salt of component (a) and component (f) (described later), for example, after adding component (a) to water and an organic solvent, while stirring, the salt is A secondary amine, a tertiary amine, a quaternary ammonium salt and/or a phosphonium salt corresponding to the structure of the salt is added and stirred at 30 to 90°C for 1 to 6 hours to form a salt, and then separated. , purification, drying and dry pulverization. Furthermore, in order to obtain a higher yield, a salt of component (a) and a metal cation may be used as a raw material instead of component (a), and the salt may be obtained by cation exchange with the source of component (f). For the separation and purification of the salt containing component (a), common means such as decantation, distillation under reduced pressure, filter press, and silica gel chromatography can be preferably applied.

When the positive photosensitive composition of the present invention contains at least a part of the component (a) in the form of a pigment, the average primary particle diameter of the component (a) in the form of a pigment is determined to improve resolution. It is preferably 10 nm or more, more preferably 30 nm or more. From the same point of view, the thickness is preferably 300 nm or less, more preferably 150 nm or less. The average primary particle diameter herein refers to the number average value of primary particle diameters calculated by a particle size measurement method using an image analysis type particle size distribution measuring device. A transmission electron microscope (TEM) can be used to take the image, and 50 primary particles of component (a) are randomly selected from images taken of 100 or more primary particles at a magnification of 50,000 times. The average primary particle diameter can be calculated by analyzing the primary particles. When component (a) is not perfectly spherical, the average value of its major axis and minor axis is taken as the primary particle diameter. Image analysis type particle size distribution software Mac-View (manufactured by Mountec, compliant with JIS 8827-1; particle size analysis - image analysis method) can be used for image analysis.

The chemical structure of component (a) was determined using matrix-assisted laser desorption ionization-time-of-flight mass spectrometry (MALDI-TOF MS) and time-of-flight secondary ion mass spectrometry using the positive photosensitive composition of the present invention as a sample. method (TOF-SIMS), time-of-flight mass spectrometry (TOF-MS), liquid chromatography/electric field Fourier transform mass spectrometry (LC-FT-MS), nuclear magnetic resonance spectrometry (NMR), liquid chromatography mass spectrometry The analysis can be performed by appropriately combining known techniques such as analytical methods (LC-MS), infrared absorption spectroscopy, and X-ray diffraction. When component (a) is present in the form of a pigment, its presence can be detected with a particle size distribution measuring device based on dynamic light scattering. The accuracy of analysis may be improved by using as a sample a concentrate obtained by centrifuging a positive photosensitive composition, or a sample dissolved in an amide solvent described below.

In order to obtain high light-shielding properties, the content of component (a) is preferably 5% by mass or more, more preferably 10% by mass or more based on 100% by mass of the solid content of the positive photosensitive composition. In order to improve resolution, the content is preferably 40% by mass or less, more preferably 30% by mass or less.

The positive photosensitive composition of the present invention improves resolution while obtaining high light-shielding properties, and further includes (f) a compound represented by formula (70) (hereinafter sometimes referred to as component (f)). ) is preferably contained. The form of the component (f) present in the positive photosensitive composition, the pixel dividing layer and the flattening layer is not particularly limited, but at least a part of the component (f) is a salt of the component (a). It is preferable that the

In formula (70), R ⁸¹ represents N ⁺ or P ⁺ . R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ each independently represent an alkyl group having 1 to 20 carbon atoms, a phenyl group, or a hydrogen atom which may be substituted with -OH or a phenyl group. However, when R ⁸¹ is N ⁺ , the total number of hydrogen atoms in R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ is 0 to 2, and when R ⁸¹ is P ⁺ , R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ , the total number of hydrogen atoms is 0.
When R ⁸¹ is N ⁺ , it means that the (f) component has an ammonium cation, and when it is P ⁺ , it means that the (f) component has a phosphonium cation.

In addition, in formula (70), when R ⁸¹ is N ⁺ , the total number of hydrogen atoms in R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ is 0 to 2 means that R ⁸² , R ⁸³ , This means that one or two of R ⁸⁴ and R ⁸⁵ are hydrogen atoms bonded to R ⁸¹ , or not all are hydrogen atoms bonded to R ⁸¹ , and the hydrogen atom here does not mean an alkyl group having 1 to 20 carbon atoms which may be substituted with --OH or a phenyl group, or a hydrogen atom contained in a phenyl group. When R ⁸¹ is P ⁺ , the expression that the total number of hydrogen atoms in R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ is 0 also applies to R ⁸² , R ⁸³ , R ⁸⁴ and R This means that none of ⁸⁵ is a hydrogen atom bonded to R ⁸¹ .
Furthermore, in formula (70) and formula (71), the alkyl group having 1 to 20 carbon atoms which may be substituted with -OH or a phenyl group includes, for example, an unsubstituted methyl group (-CH ₃ ), - Included are a methyl group substituted with one OH (-CH ₂ OH), a methyl group substituted with one phenyl group (ie, benzyl group), and the like. When substituted with -OH or a phenyl group, from the viewpoint of resolution, the number of substitutions in the alkyl group having 1 to 20 carbon atoms is preferably one.

In order to improve the resolution, the component (f) has an alkyl group having 1 to 15 carbon atoms which may be substituted with -OH or a phenyl group, and an unsubstituted alkyl group having 1 to 15 carbon atoms. It is preferable to have at least one.
That is, in the positive photosensitive composition of the present invention, the component (f) more preferably contains a compound represented by formula (71).

In formula (71), R ⁸⁶ represents N ⁺ or P ⁺ . R ⁸⁷ , R ⁸⁸ , R ⁸⁹ and R ⁹⁰ each independently represent an alkyl group having 1 to 15 carbon atoms which may be substituted with -OH or a phenyl group. However, at least one of R ⁸⁷ , R ⁸⁸ , R ⁸⁹ and R ⁹⁰ is an unsubstituted alkyl group having 1 to 15 carbon atoms. When R ⁸⁶ is N ⁺ , it means that the (f) component has an ammonium cation, and when it is P ⁺ , it means that the (f) component has a phosphonium cation.

In order to improve resolution, it is more preferable that R ⁸⁶ is N ⁺ and R ⁸⁷ , R ⁸⁸ , R ⁸⁹ and R ⁹⁰ are unsubstituted alkyl groups having 1 to 15 carbon atoms.

Specific examples of compounds belonging to component (f) and raw material compounds preferably used to obtain them will be given below, but the invention is not limited thereto. Note that commercially available raw material compounds are available from Tokyo Kasei Kogyo Co., Ltd. and Sigma-Aldrich.
In formula (70), R ⁸¹ is N ⁺ and the total number of hydrogen atoms bonded to R ⁸¹ in R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ is 1 or 2. Examples include the compound represented by formula (72) derived from 2-(dodecylamino)ethanol etc., the compound represented by formula (73) derived from bis(2-ethylhexyl)amine etc., tri-n- A compound represented by formula (74) derived from octylamine etc., a compound represented by formula (75) derived from stearyldiethanolamine etc., a compound represented by formula (76) derived from 2-diethylaminoethanol etc. Can be mentioned.

As a specific example of component (f) in formula (70), R ⁸¹ is N ⁺ and the total number of hydrogen atoms bonded to R ⁸¹ in R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ is 0. is a compound represented by formula (77) derived from benzyldodecyldimethylammonium chloride etc., a compound represented by formula (78) derived from tetraethylammonium bromide etc., a compound represented by formula (79) derived from trimethylphenylammonium bromide etc. Examples include a compound represented by the formula (80) derived from tetrabutylammonium bromide and the like, and a compound represented by the formula (81) derived from tridodecylmethylammonium chloride and the like.

Specific examples of component (f) in which R ⁸¹ is P ⁺ in formula (70) include compounds represented by formula (82) derived from tetrabutylphosphonium bromide and the like, and formulas derived from tributylhexylphosphonium bromide and the like. Examples include a compound represented by formula (83) and a compound represented by formula (84) derived from tetrakis(hydroxymethyl)phosphonium sulfate.

These (f) components may be contained alone or in combination.
The content of component (f) should be 10 mol% or more in order to improve resolution, when the total of -SO ₃ H and -SO ₃ ^- contained in component (a) is 100 mol% in the positive photosensitive composition. It is preferably present, and more preferably 20 mol% or more. In order to improve the thermal stability of light-shielding properties, the content is preferably 100 mol% or less, more preferably 80 mol% or less.

The positive photosensitive composition of the present invention contains (b) a resin. The resin here means a compound having a polymer chain having 5 or more repeating units and a weight average molecular weight (Mw) of 1,000 or more. Component (b), along with component (c) described below, is a component that provides positive photosensitivity, and also serves to fix component (a) in the finally obtained pixel dividing layer and/or flattening layer. It has a function as a binder component.

(b) Resin is not particularly limited, but (b-1) phenolic hydroxyl group-containing resin (hereinafter sometimes referred to as component (b-1)) is preferred in order to improve resolution. That is, the positive photosensitive composition of the present invention preferably contains (b-1) a phenolic hydroxyl group-containing resin.

Component (b-1) includes, for example, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, novolak resin, resin having a repeating unit derived from a radically polymerizable monofunctional monomer having a phenolic hydroxyl group, and polyamide. Examples include siloxane. One or more types of these resins may be contained. Among these, it is preferable to contain at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole precursor, and copolymers thereof. The copolymer referred to herein may be a random copolymer or a block copolymer. Polyimide, polyimide precursors, polybenzoxazole precursors, and their copolymers are all difficult to thermally decompose, and the volumetric shrinkage of the film is small, so after high-temperature treatment, the one with higher light-shielding property per 1.0 μm film thickness It has the effect of suppressing changes in Therefore, the thermal stability of the light-shielding property of the pixel division layer and/or the planarization layer can be further improved.

That is, in the positive photosensitive composition of the present invention, the (b) resin contains (b-1) a phenolic hydroxyl group-containing resin, and the (b-1) phenolic hydroxyl group-containing resin is a polyimide or a polyimide precursor. It is preferable to contain at least one resin selected from the group consisting of polybenzoxazole precursors, polybenzoxazole precursors, and copolymers thereof.

The weight average molecular weight (Mw) of the resin belonging to component (b-1) is preferably 5,000 to 50,000 in order to achieve both thermal stability of light-shielding property and resolution. More preferably 10,000 to 30,000.

Among these, resins having a structural unit represented by formula (17) and/or a structural unit represented by formula (18) are more preferable in terms of improving resolution. That is, in the positive photosensitive composition of the present invention, the (b) resin contains (b-1) a phenolic hydroxyl group-containing resin, and the (b-1) component is represented by formula (17). It is more preferable to contain a resin having a structural unit and/or a resin having a structural unit represented by formula (18).

In formula (17), R ³⁷ represents a 4- to 10-valent organic group. R ³⁸ represents a divalent to octavalent organic group. R ³⁹ and R ⁴⁰ each independently represent a phenolic hydroxyl group or a carboxyl group, and each may be a single group or a mixture of different groups. However, at least one of R ³⁹ and R ⁴⁰ contains a phenolic hydroxyl group. p and q are integers and each independently represents 0 to 6. However, p+q>0 is satisfied. * represents a binding site.

In formula (18), R ⁴¹ and R ⁴² represent a divalent to octavalent organic group. R ⁴³ and R ⁴⁴ each independently represent a phenolic hydroxyl group, a carboxyl group, or -COOA, and each may be a single group or different groups may be mixed. However, at least one of R ⁴³ and R ⁴⁴ contains a phenolic hydroxyl group. A represents a monovalent hydrocarbon group having 1 to 10 carbon atoms. r and s are integers and each independently represents 0 to 6. However, r+s>0 is satisfied. * represents a binding site.

The resin having a structural unit represented by formula (18) preferably has a group represented by -COOA in order to improve resolution, and in formula (18), a monovalent carbonized group having 1 to 10 carbon atoms Examples of the hydrogen group A include a methyl group, an ethyl group, a propyl group, a phenyl group, and a benzyl group.

In formula (17), R ³⁷ -(R ³⁹ )p represents a residue of an acid dianhydride. R ³⁷ is preferably an organic group containing an aromatic ring or a cycloaliphatic group and having 5 to 40 carbon atoms. Examples of the acid dianhydride residue include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 2,3,3',4'-biphenyltetracarboxylic dianhydride. Acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3' -benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1 -Bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyne)methane dianhydride , bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3 , 6,7-naphthalenetetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis{4-(3,4-dicarboxyphenoxy) phenyl}fluorene dianhydride, aromatic tetracarboxylic dianhydride residues such as residues of acid dianhydride having the structure represented by formula (19), butanetetracarboxylic dianhydride, 1, Examples include residues of aliphatic tetracarboxylic dianhydrides such as residues of 2,3,4-cyclopentanetetracarboxylic dianhydrides.

In formula (19), R ⁴⁵ represents a single bond, -O-, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ - or -SO ₂ -. R ⁴⁶ and R ⁴⁷ each independently represent a hydrogen atom or -OH.

In formula (18), R ⁴¹ -(R ⁴³ )r represents an acid residue. R ⁴¹ is preferably an organic group containing an aromatic ring or a cycloaliphatic group and having 5 to 40 carbon atoms.

Examples of acid residues include dicarboxylic acid residues, tricarboxylic acid residues, and tetracarboxylic acid residues. Examples of dicarboxylic acids include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyl dicarboxylic acid. Examples of tricarboxylic acids include residues of trimellitic acid, trimesic acid, diphenyl ethertricarboxylic acid, and biphenyltricarboxylic acid. Examples of tetracarboxylic acid residues include pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3, 3'-biphenyltetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 2,2',3,3'-benzophenonetetracarboxylic acid, 2,2-bis(3,4-dicarboxylic acid) phenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3- dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)ether, 1,2,5,6- Aromatic compounds such as residues of naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, and 3,4,9,10-perylenetetracarboxylic acid Examples thereof include tetracarboxylic acid residues and aliphatic tetracarboxylic acid residues such as butanetetracarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid.

R ³⁸ -(R ⁴⁰ )q in formula (17) and R ⁴² -(R ⁴⁴ )s in formula (18) represent a diamine residue. R ³⁸ and R ⁴² are preferably organic groups containing an aromatic ring or a cycloaliphatic group and having 5 to 40 carbon atoms.

Examples of diamine residues include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, and 1,4-bis(4-aminodiphenylmethane). phenoxy)benzene, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 1,6-naphthalenediamine, bis(4-aminophenoxy)biphenyl, 1,4-bis(4-aminophenoxy)benzene, of diamines such as 2-bis(3-amino-4-hydroxyphenyl)propane, 1,3-bis(4-aminophenoxy)benzene, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane. Examples thereof include a residue, a residue of a compound represented by formula (20), and a residue of a compound represented by formula (21).

In formula (20), R ⁴⁸ represents a single bond, -O-, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ - or -SO ₂ -. R ⁴⁹ and R ⁵⁰ each independently represent a hydrogen atom or -OH.

In formula (21), R ⁵¹ represents a single bond, -O-, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ - or -SO ₂ -. R ⁵² and R ⁵³ each independently represent a hydrogen atom or -OH.

Furthermore, by capping the ends of these resins with monoamine, it becomes easier to adjust the weight average molecular weight (Mw), and (b) the storage stability as a resin can be improved.

Examples of monoamines include 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, and 1-carboxy-7-aminonaphthalene. , 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-aminophenol, 3-aminophenol, 4-amino Examples include phenol.

In formula (18), the group represented by COOA can be obtained by converting a carboxyl group with an esterifying agent. Examples of the esterifying agent include N,N-dimethylformamide dimethyl acetal and N,N-dimethylformamide diethyl acetal.

A resin having a structural unit represented by formula (17) and/or a structural unit represented by formula (18) can be obtained by a known method, for example, Japanese Patent No. 4341293, International Publication No. 2014/ It can be synthesized by the method disclosed in No. 097992 and International Publication No. 2019/181782.

Novolak resin can be obtained by a known method, in which an aldehyde compound such as formaldehyde or benzaldehyde is added to a compound having a phenol skeleton such as phenol, o-cresol, m-cresol, p-cresol, or xyresol in the coexistence of an acidic catalyst. It can be synthesized by condensation with Commercially available novolak resins include, for example, TRR5030G, TRR5010G, TR4020G, TR4080G, TR4000B, TRM30B20G, and EP23F10G (all manufactured by Asahi Yokuzai Co., Ltd.).

Examples of resins having repeating units derived from radically polymerizable monofunctional monomers having a phenolic hydroxyl group include radically polymerizable monomers having a phenolic hydroxyl group such as hydroxystyrene, hydroxyphenyl (meth)acrylate, and hydroxyphenyl (meth)acrylamide. Examples include resins obtained by polymerizing one type or a combination of two or more functional monomers. Furthermore, a radically polymerizable monofunctional monomer having a thermally crosslinkable group such as glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, or allylglycidyl (meth)acrylate may be copolymerized.

(b) The content of the resin is preferably 30% by mass or more, more preferably 50% by mass or more based on 100% by mass of the solid content of the positive photosensitive composition, in order to improve resolution. In order to obtain high light-shielding properties, the content is preferably 80% by mass or less, more preferably 60% by mass or less.

The positive photosensitive composition of the present invention contains (c) a photoacid generator (hereinafter sometimes referred to as component (c)). Component (c) is not particularly limited as long as it is a compound that decomposes and generates acid when irradiated with light containing at least a wavelength of 200 to 450 nm. The generated acid is preferably a carboxylic acid and/or a sulfonic acid.

By containing component (c), the generated acid has the effect of making the solubility of the film in the exposed area relatively higher in the alkaline developer compared to the solubility of the film in the unexposed area in the alkaline developer. . As a result, it becomes possible to perform positive photolithography in which a pattern is formed by removing a film in an exposed area that has been pattern-exposed through an exposure mask. In addition, it is also possible to control the amount of acid generated in the film by adjusting the exposure amount. The solubility of the film in the exposed area in an alkaline developer that has been exposed with a small amount of light through an exposure mask that has multiple types of openings and light shielding areas with different transmittances in its plane, that is, a halftone exposure mask, is determined by By making the solubility in an alkaline developer relatively low compared to the solubility of the film in the exposed area exposed to a large amount of light, it is possible to form a pattern with steps through positive halftone processing.

Component (c) is preferably a compound that has absorption in the i-line (wavelength 365 nm), h-line (wavelength 405 nm) and g-line (wavelength 436 nm) regions of a mercury lamp and generates an acid, such as a quinonediazide compound, Examples include oxime sulfonate compounds and naphthalimide sulfonate compounds. Among these, quinonediazide compounds are preferred because they exhibit an excellent dissolution inhibiting effect on the unexposed area of the film, can increase the difference in dissolution rate between the exposed area and the unexposed area, and have excellent resolution.

In order to improve resolution, quinonediazide compounds include (c-1) a compound having two or more groups represented by formula (22) in the molecule and a phenolic hydroxyl group, and a compound represented by formula (23). A compound having two or more groups in the molecule and a phenolic hydroxyl group, and a compound having a group represented by formula (22) and a group represented by formula (23) and a phenolic hydroxyl group. It is preferable to contain at least one compound selected from the group consisting of compounds (hereinafter sometimes referred to as component (c-1)). In order to improve the resolution, it is more preferable to contain a compound having at least a group represented by formula (22) in the molecule and a phenolic hydroxyl group.

That is, in the positive photosensitive composition of the present invention, (c) the photoacid generator has two or more groups represented by formula (22) (c-1) in the molecule, and a phenolic hydroxyl group. A compound having two or more groups represented by formula (23) in the molecule and having a phenolic hydroxyl group, and a group represented by formula (22) and a compound represented by formula (23) It is preferable to contain at least one compound selected from the group consisting of a compound having a phenolic hydroxyl group and a phenolic hydroxyl group.

In formula (22), R ⁵⁴ , R ⁵⁵ , R ⁵⁶ and R ⁵⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. * represents a binding site.

In formula (23), R ⁵⁸ , R ⁵⁹ and R ⁶⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. * represents a binding site.
In formula (22), R ⁵⁴ , R ⁵⁵ , R ⁵⁶ and R ⁵⁷ are preferably hydrogen atoms in order to improve resolution. In formula (23), R ⁵⁸ , R ⁵⁹ and R ⁶⁰ are preferably hydrogen atoms in order to improve resolution.

Compounds having two or more groups represented by formula (22) in the molecule and phenolic hydroxyl groups include, for example, compounds having three or more phenolic hydroxyl groups in the molecule, and 1,2-naphthoquinone- It can be synthesized by a partial esterification reaction of 2-diazide-4-sulfonyl chloride. Compounds having two or more groups represented by formula (23) in the molecule and phenolic hydroxyl groups include, for example, compounds having three or more phenolic hydroxyl groups in the molecule, and 1,2-naphthoquinone- It can be synthesized by a partial esterification reaction of 2-diazide-5-sulfonyl chloride. A compound having a group represented by formula (22) and a group represented by formula (23) and having a phenolic hydroxyl group is, for example, a compound having three or more phenolic hydroxyl groups in the molecule, 1, It can be synthesized by a partial esterification reaction of 2-naphthoquinone-2-diazido-4-sulfonyl chloride and 1,2-naphthoquinone-2-diazido-5-sulfonyl chloride.

Examples of compounds having three or more phenolic hydroxyl groups in the molecule include TrisP-HAP, TrisP-PA, TekP-4HBPA, TrisP-SA, TrisOCR-PA, Bis P-AP, Bis P-NO, Bis P- Examples include PR, BisP-B, BisP-DE, BisP-DP, Bis P-DP, Bis RS-2P, Bis RS-3P, and Bis P-DEK (all manufactured by Honshu Kagaku Kogyo Co., Ltd.).

As the component (c-1), for example, a compound represented by formula (24), a compound represented by formula (25), a compound represented by formula (27), a compound represented by formula (28) can be mentioned.

In formula (24), Q ¹ , Q ² , Q ³ and Q ⁴ each independently represent a hydrogen atom or a group represented by formula (26). However, among Q ¹ , Q ² , Q ³ and Q ⁴ , the total number of groups represented by formula (26) is 2 or 3.
In formula (25), Q ⁵ , Q ⁶ and Q ⁷ each independently represent a hydrogen atom or a group represented by formula (26). However, the total number of groups represented by formula (26) in Q ⁵ , Q ⁶ and Q ⁷ is 2.

In formula (26), * represents a bonding site with an oxygen atom.

In formula (27), Q ⁸ , Q ⁹ and Q ¹⁰ each independently represent a hydrogen atom or a group represented by formula (29). However, among Q ⁸ , Q ⁹ and Q ¹⁰ , the total number of groups represented by formula (29) is 2.
In formula (28), Q ¹¹ , Q ¹² , Q ¹³ and Q ¹⁴ each independently represent a hydrogen atom or a group represented by formula (29). However, among Q ¹¹ , Q ¹² , Q ¹³ and Q ¹⁴ , the total number of groups represented by formula (29) is 2 or 3.

In formula (29), * represents a bonding site with an oxygen atom.

Commercial products of component (c), which generates acid upon exposure to i-rays, include PA-28 (manufactured by Daito Chemix Co., Ltd.), which is a naphthoquinone diazide compound, and PAG103 and PAG203, which are oxime sulfonate compounds (both manufactured by BASF). (manufactured by San-Apro Co., Ltd.), and naphthalimide sulfonate compounds NP-TM2 and NP-SE10 (both manufactured by San-Apro Co., Ltd.). The above component (c) may be used alone or in combination. For example, in addition to a quinone diazide compound, a compound in which -O-SO ₂ -CF ₃ groups are bonded to the nitrogen atom constituting the imide bond is used. A phthalimide sulfonate compound may also be included.

The content of component (c) is preferably 3% by mass or more based on 100% by mass of the solid content of the positive photosensitive composition, in order to generate a necessary and sufficient amount of acid in the film and improve resolution. More preferably, the content is 5% by mass or more. In order to suppress excessive absorption of exposure light on the film surface and improve resolution, the content is preferably 30% by mass or less, more preferably 20% by mass or less.

The positive photosensitive composition of the present invention contains (d) an organic solvent (hereinafter sometimes referred to as component (d)). (d) The organic solvent functions as a dispersion medium or solvent for component (a), and not only improves the storage stability of the positive photosensitive composition but also improves the coating properties of the positive photosensitive composition. This has the effect of increasing the smoothness of the pre-baked film, which will be described later.

As component (d), (d-1) an organic solvent having a hydroxyl group (hereinafter sometimes referred to as component (d-1)) is preferred.
That is, the positive photosensitive composition of the present invention preferably contains (d-1) an organic solvent having a hydroxyl group. Component (d-1) has a high affinity with component (a) and has the effect of improving resolution.

Component (d-1) includes, for example, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (hereinafter referred to as "PGME") ), propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methyl lactate, ethyl lactate, ethanol, isopropyl alcohol, and butanol.

The positive photosensitive composition of the present invention may contain (d-2) an organic solvent having no hydroxyl group (hereinafter sometimes referred to as component (d-2)). Component (d-2) may be used to adjust the solubility of components other than component (a) and the viscosity of the positive photosensitive composition.

Component (d-2) includes, for example, acetate solvents such as ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA"), and 3-methoxybutyl acetate (hereinafter referred to as "MBA"); - Lactone solvents such as butyrolactone (hereinafter referred to as "GBL") and γ-valerolactone, amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone (hereinafter referred to as "NMP") can be mentioned. When component (a) is present as a dye, high solubility tends to be obtained, for example, if the content of the lactone solvent is 30% by mass or more based on 100% by mass of component (d).

In terms of improving storage stability, the content of component (d) is preferably 40% by mass or more, more preferably 60% by mass or more, based on 100% by mass of the positive photosensitive composition. In order to improve the smoothness of the prebaked film, the content is preferably 99% by mass or less, more preferably 95% by mass or less. Further, the content of component (d-1) is preferably 50% by mass or more, more preferably 80% by mass or more, based on 100% by mass of component (d), in order to improve resolution.

That is, in the positive photosensitive composition of the present invention, component (d) contains (d-1) an organic solvent having a hydroxyl group, and the content of component (d-1) is 100% by mass of component (d). Among them, it is preferably 50% by mass or more.

The positive photosensitive composition of the present invention improves the thermal stability of light-shielding properties, and further includes (e) a compound represented by the formula (30), a compound represented by the formula (31), and a triphendi It is preferable to contain at least one compound selected from the group consisting of compounds having an oxazine skeleton (hereinafter sometimes referred to as component (e)). The triphendioxazine skeleton herein is synonymous with the triphenodioxazine skeleton. Note that the compound represented by formula (30) and the compound represented by formula (31) have the aforementioned PTCBI skeleton, but do not have a sulfo group and do not belong to component (a).

In formula (30) and formula (31), R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ and R ⁶⁸ are each independently a hydrogen atom, -F, or a carbon number of 1 to 3 alkyl group or an alkoxy group having 1 to 3 carbon atoms.
R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ , R ⁶⁷ and R ⁶⁸ are preferably hydrogen atoms in order to improve the thermal stability of light-shielding properties.

Examples of the compound having a triphendioxazine skeleton include a compound represented by formula (32), a compound represented by formula (33), a C.I. I. Pigment Violet 23, C. I. Direct Violet 54, C. I. Examples include Direct Blue 106, 107, 108, and 190.

In formula (32), R ⁶⁹ , R ⁷⁰ , R ⁷¹ and R ⁷² each independently represent an alkyl group having 1 to 3 carbon atoms. R ⁷³ and R ⁷⁴ each independently represent -NH- or -O-.

In formula (33), R ⁷⁵ and R ⁷⁶ each independently represent a hydrogen atom or a halogen atom. R ⁷⁷ , R ⁷⁸ , R ⁷⁹ and R ⁸⁰ each independently represent a hydrogen atom, a phenyl group or an alkyl group having 1 to 5 carbon atoms.
Among these, the compound represented by formula (30), the compound represented by formula (31), and the compound represented by formula (32) are preferred.

The content of component (e) is preferably 10% by mass or more based on the total 100% by mass of components (a) and (e) in order to improve the thermal stability of light-shielding properties. In order to improve resolution, it is preferably 60% by mass or less.

The positive photosensitive composition of the present invention may contain other components such as a thermal crosslinking agent, a leveling agent, and an adhesion improver to the substrate surface, if necessary.

As a method for preparing the positive photosensitive composition of the present invention, for example, when at least a part of the component (a) is present as an insoluble pigment, the component (a) and the resin (b) are treated by wet media dispersion treatment. A pigment dispersion containing component (d) and, if necessary, component (e) is prepared in advance, and then components (c) and (d), and other components as necessary, are mixed with the pigment dispersion. , stirring, and filtering if necessary. If component (a) has a solubility distribution with respect to resin (b) and component (d), and a small amount of component (a) remains undissolved, pulverization using a wet media dispersion process will completely dissolve the component. In some cases, it can be used as a dye. On the other hand, when all of component (a) is present as a dye in dissolved form, instead of wet media dispersion treatment, component (a) is dissolved in component (b) and component (d) under heating at 40 to 70°C. All you have to do is perform the process of
When component (f) is included, a salt is formed between component (a) and component (f) simply by mixing, but in order to promote salt formation and improve resolution, it is necessary to A positive photosensitive composition is prepared using the source of the component (a) and the mixture obtained by forming a salt in advance by heating the component (a) in the presence of a solvent, and further refining and drying the resulting mixture into a powder. It is preferable to do so.

A bead mill filled with ceramic beads can be preferably used as a dispersing machine for performing wet media dispersion treatment. Examples of ceramic beads include "Treceram (registered trademark)" (manufactured by Toray Industries, Inc.).

The cured film of the present invention, which is the second aspect of the present invention, is a cured film containing a cured product of the positive photosensitive composition of the present invention. The term "cured product" as used herein means a product obtained through a step of heating a positive photosensitive composition at a temperature of 200° C. to 400° C. for 10 minutes or more under atmospheric pressure. The cured film of the present invention has excellent technical effects such as high light-shielding and thermal stability, and can be preferably used, for example, as a pixel dividing layer or a TFT flattening layer of an organic EL display device.

Preferred embodiments of the case where the cured film of the present invention is used as a pixel dividing layer or a flattening layer of an organic EL display device will be described below.

The optical density/μm (hereinafter sometimes referred to as OD/μm) per 1.00 μm thickness of the pixel dividing layer and the planarization layer is important for suppressing reflection of external light and increasing the value of the display device. and is preferably 0.50 or more, more preferably 0.70 or more. In order to improve resolution, it is preferably 1.30 or less, more preferably 1.10 or less. The thickness of each of the pixel division layer and the planarization layer is preferably 1.00 μm or more in order to suppress reflection of external light and increase the value of the display device. In order to obtain high resolution, it is preferably 5.00 μm or less.

OD/μm is measured using an optical densitometer X-Rite 361T (manufactured by X-Rite) by measuring a pixel dividing layer and/or flattening layer formed to a thickness of 1.50 μm on a transparent substrate with incident light. It means the value obtained by measuring the intensity and transmitted light intensity and dividing the value calculated from the following formula by 1.50, which is the value of the film thickness. The higher the OD/μm, the higher the light shielding property. As the transparent base material, a transparent glass substrate "Tempax (manufactured by AGC Techno Glass Co., Ltd.)" having an OD/μm of 0.00 can be preferably used.
Optical density = log ₁₀ (I ₀ /I)
In the above formula, _I0 : incident light intensity, I: transmitted light intensity.

The cross-sectional taper angle of the inclined portion located at the end of the pixel dividing layer is preferably 50° or less, more preferably 40° or less, in order to suppress electrode disconnection and avoid the occurrence of non-lighted pixels. The angle is preferably 15° or more, more preferably 20° or more in order to suppress a decrease in light shielding properties at the end portions.

The methods for forming the pixel division layer include a coating process in which a positive-working photosensitive composition is applied to obtain a coating film, a pre-bake process in which the coating film is heated to obtain a pre-baked film, and an activation process is performed through a positive-working exposure mask. An exposure step to obtain an exposed film having exposed and unexposed regions in the plane by pattern exposure to actinic radiation, a development step to obtain a developed film by developing with an alkaline developer and removing the exposed regions, and heating. A method including, in order, a curing step of thermally curing to obtain a pixel dividing layer is preferred. On the other hand, the planarization layer can be formed by the same method as the pixel division layer.

As the coating device used in the coating step, a spin coater or a slit coater can be preferably used since they have excellent thin film coating properties.
The prebake temperature in the prebake step is preferably 50 to 150°C, and the prebake time is preferably 30 seconds to 5 minutes. In order to improve film thickness uniformity, the thickness of the prebaked film is preferably 3.0 to 6.0 μm.

Examples of the exposure apparatus used in the exposure process include a stepper, a mirror projection mask aligner (MPA), and a parallel light mask aligner (PLA). The actinic rays irradiated during exposure include J-line (wavelength 313 nm), i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) from an ultra-high pressure mercury lamp. The exposed portion of the exposure film refers to a portion that is pattern-exposed through the transparent portion of the exposure mask, and the unexposed portion refers to a portion that is not exposed to light due to the shielding portion of the exposure mask. In order to obtain a pixel dividing layer and/or a flattening layer with high reproducibility of the design dimension of the opening width of the exposure mask, the value obtained by subtracting the opening width of the patterned opening from the opening width of the exposure mask, that is, the exposure It is preferable to perform exposure by adjusting the exposure amount so that the mask bias is within the range of ±0.2 μm.

Examples of the development method in the development step include shower, dipping, and paddle methods, including a method in which the exposed film is immersed for 10 seconds to 3 minutes. The paddle method is preferable in terms of improving in-plane uniformity of resolution. As the alkaline developer, a 0.4 to 2.5 mass % tetramethylammonium hydroxide aqueous solution (hereinafter referred to as "TMAH") is preferable, and as a commercial product, for example, 2.38 mass % TMAH (Tama Chemical Industry Co., Ltd. ) manufactured by ). After the development step, it is preferable to wash with deionized water, that is, add a rinsing step, and then dry the film to obtain a developed film. The development time is determined by subtracting the thickness of the developed film (unexposed area) from the thickness of the pre-baked film, that is, the film reduction (μm) during the development process, in order to improve the in-plane uniformity of the thickness of the developed film. , is preferably set to 1.00 μm or less. In order to improve resolution, it is preferable to set the thickness to 0.50 μm or more. Furthermore, the obtained developed film may be irradiated with exposure light again in a second exposure step to control the fluidity of the film in the curing step.

Examples of the heating device used in the curing step include a hot air oven and an IR oven, and the heating atmosphere includes nitrogen or air. The heating temperature is preferably 250 to 270° C. under atmospheric pressure, and the heating time may be 1 to 3 hours. The conditions of the curing step may be set so that at least a part of the (f) component disappears from the pixel division layer or the planarization layer.

The organic EL display device of the present invention, which is a third aspect of the present invention, is an organic EL display device comprising a pixel dividing layer and a flattening layer, wherein the pixel dividing layer and/or the flattening layer are cured according to the present invention. It is an organic EL display device containing a film. Since the pixel dividing layer and/or the flattening layer contain the cured film of the present invention which has high light-shielding properties, high in-plane uniformity, and excellent resolution, the organic EL display device of the present invention has a desirable high visibility. This has the technical effect of

FIG. 1 shows a cross-sectional view of a TFT substrate in an organic EL display device including a pixel dividing layer and a planarization layer as a specific example of an embodiment of the present invention.

Bottom-gate or top-gate thin film transistors 1 (hereinafter abbreviated as TFT1) are provided in a matrix on the surface of the substrate 6, and the TFTs cover the TFT1 and the wiring 2 connected to the TFT1. An insulating layer 3 is arranged. Further, a planarization layer 4 is patterned on the surface of the TFT insulating layer 3, and the planarization layer 4 has a contact hole 7, which is an opening for connecting the wiring 2 and the first electrode 5. A first electrode 5 is patterned on the surface of the planarization layer 4 and connected to the wiring 2 . A pixel dividing layer 8 having a step and may have a spacer function is formed so as to surround the pattern periphery of the first electrode 5. The pixel dividing layer 8 has an opening, and a light emitting pixel 9 containing an organic EL light emitting material is formed in the opening, and the second electrode 10 covers the pixel dividing layer 8 and the light emitting pixel 9. A film has been formed. If a voltage is applied to the light emitting pixel portion after the TFT substrate having the above laminated structure is sealed under vacuum, it can be made to emit light as an organic EL display device.

The organic EL display device including the pixel dividing layer and the planarization layer of the present invention is a bottom emission type organic EL display device that extracts light emitted from the light emitting pixels 9 to the substrate side via the substrate 6. Alternatively, it may be a top emission type organic EL display device in which emitted light is extracted to the opposite side of the substrate 6 via the second electrode 10. The planarization layer 4 having a light blocking property may function as a light blocking layer for protecting the TFT 1. Examples of the TFT 1 include TFTs made of oxide semiconductors such as In-Ga-Zn-O (IGZO) and Ga-Zn-Sn, and low-temperature polysilicon (LTPS).

The shapes of the openings in the pixel dividing layer 8 and the flattening layer 4 are not particularly limited, and may be square, rectangular, circular, or elliptical. The size and shape of the light emitting pixel 9 are determined by the width and shape of the opening in the pixel dividing layer 8, and may be circular with a diameter of 3 to 30 μm, for example. The contact hole 7, which is an opening in the planarization layer 4, may have a circular shape with a diameter of 3 to 7 μm, for example. The higher the resolution of the pixel dividing layer 8 and the flattening layer 4, the more useful the effect of the present invention is that the thermal stability of the light shielding property is higher.

Although the light emission peak wavelength of the light emitting pixel 9 is not particularly limited, for example, a structure in which different types of pixels having emission peak wavelengths for each of the three primary colors of light, blue, red, and green, are arranged is formed on the entire surface. can be mentioned. The peak wavelength of the red region may be 560 to 700 nm, the peak wavelength of the blue region may be 420 to 480 nm, and the peak wavelength of the green region may be 500 to 550 nm. Furthermore, a color filter substrate on which blue, red, and green color filters and a black matrix separating them may be arranged as a separate laminated member in front of the display section. As the organic EL light-emitting material constituting the light-emitting pixel 9, a material in which a hole transport layer and/or an electron transport layer are further combined in addition to a light emitting layer can be suitably used. The light-emitting pixel 9 is formed, for example, by a mask vapor deposition method disclosed in Japanese Patent Application Publication No. 2019-163543.

As the first electrode 5, for example, a transparent conductive metal oxide such as indium tin oxide (ITO) or indium zinc oxide (IZO) can be used. The method for patterning ITO is to form a film of ITO on the entire surface by sputtering, then pattern a positive resist material for etching by photolithography to obtain a resist pattern on the ITO film, and then remove the resist pattern. Only the ITO film in the formed portion is removed using an acidic etching solution. Next, there is a method of removing the resist pattern using a resist stripping solution. As a positive resist material for etching, a positive photosensitive composition containing an alkali-soluble novolak resin can be used. In the case of a top emission type organic EL display device, the first electrode 5 may be a laminate of ITO/silver alloy/ITO in order to improve light extraction efficiency.

The second electrode 10 may be made of any material as long as it is a layer that functions as an electrode. In the case of a bottom emission type organic EL display device, a layer made of aluminum can be preferably used because it has excellent light reflectivity. In the case of a top emission type organic EL display device, a silver alloy consisting of silver and magnesium can be preferably used because it has excellent light transmittance. The second electrode 10 can be formed over the entire surface by sputtering.

In addition to the glass substrate, the substrate 8 is a flexible substrate obtained by coating the surface of a temporary support with a polyamic acid solution and then laser-peeling the temporary support from a polyimide-formed substrate produced after heat treatment at 250 to 400°C. Can be used.

The dye of the present invention, which is the fourth aspect of the present invention, includes (a) a compound represented by formula (85) and/or a compound represented by formula (86) in addition to (f) a compound represented by formula (70). A dye containing a compound represented by (hereinafter sometimes referred to as the dye of the present invention).

The dye of the present invention can be preferably used as a coloring material for imparting light-shielding properties to a pixel dividing layer and/or a flattening layer included in an organic EL display device, and can particularly be incorporated into a positive photosensitive composition. Not only does it have excellent light-shielding properties and thermal stability, but it also has a particularly remarkable technical effect in that a cured film with high resolution can be obtained while having high light-shielding properties.

(f) The compound represented by formula (70) contained in the dye of the present invention and (a) the compound represented by formula (85) and/or the compound represented by formula (86) do not form a salt. In addition to the content of component (f), the polarity can be changed depending on the type of organic group bonded to N ⁺ or P ⁺ to control compatibility with the resin and solubility in organic solvents. Can be done.

In formula (70), R ⁸¹ represents N ⁺ or P ⁺ . R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ each independently represent an alkyl group having 1 to 20 carbon atoms, a phenyl group, or a hydrogen atom which may be substituted with -OH or a phenyl group. However, when R ⁸¹ is N ⁺ , the total number of hydrogen atoms in R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ is 0 to 2, and when R ⁸¹ is P ⁺ , R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ , the total number of hydrogen atoms is 0.
In formula (85), R ⁹¹ , R ⁹² , R ⁹³ , R ⁹⁴ , R ⁹⁵ , R ⁹⁶ , R ⁹⁷ and R ⁹⁸ each independently represent a hydrogen atom, -SO ₃ H, -SO ₃ ^- , carbon number Represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, -CF ₃ , -F, -Br or -CN. However, in R ⁹¹ , R ⁹² , R ⁹³ , R ⁹⁴ , R ⁹⁵ , R ⁹⁶ , R ⁹⁷ and R ⁹⁸ , the total number of -SO ₃ H and -SO ₃ ^- is 1 to 4, and at least one -SO ₃ ^- .
R ⁹⁹ , R ¹⁰⁰ , R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom, -OH, -F, -Br, -CN or an alkoxy group having 1 to 5 carbon atoms. However, R ⁹⁹ and R ¹⁰⁰ and R ¹⁰¹ and R ¹⁰² may each independently be bonded to each other to form a linking group -X ³ -. -X ³ - represents -O- or -SO ₂ -.
In formula (86), R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ^{107 , R 108} ^, R ¹⁰⁹ and R ¹¹⁰ each independently represent a hydrogen atom, -SO ₃ H, -SO ₃ ^- , carbon number Represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, -CF ₃ , -F, -Br or -CN. However, in R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ , R ¹⁰⁸ , R ¹⁰⁹ and R ¹¹⁰ , the total number of -SO ₃ H and -SO ₃ ^- is 1 to 4, and at least one -SO ₃ ^- .
R ¹¹¹ , R ¹¹² , R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom, -OH, -F, -Br, -CN or an alkoxy group having 1 to 5 carbon atoms. However, R ¹¹¹ and R ¹¹² and R ¹¹³ and R ¹¹⁴ may each independently be bonded to each other to form a linking group -X ⁴ -. -X ⁴ - represents -O- or -SO ₂ -.

In addition, in formula (70), when R ⁸¹ is N ⁺ , the total number of hydrogen atoms in R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ is 0 to 2 means that R ⁸² , R ⁸³ , This means that one or two of R ⁸⁴ and R ⁸⁵ are hydrogen atoms bonded to R ⁸¹ or none of them are hydrogen atoms bonded to R ⁸¹ . The hydrogen atom here does not mean an alkyl group having 1 to 20 carbon atoms which may be substituted with -OH or a phenyl group, or a hydrogen atom contained in a phenyl group. When R ⁸¹ is P ⁺ , the expression that the total number of hydrogen atoms in R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ is 0 also applies to R ⁸² , R ⁸³ , R ⁸⁴ and R This means that none of ⁸⁵ is a hydrogen atom bonded to R ⁸¹ .

The dye of the present invention more preferably contains (f) a compound represented by formula (71) in order to improve resolution.

Further, the dye of the present invention may contain (a) a compound represented by formula (87) and/or a compound represented by formula (88) in order to improve the thermal stability of light-shielding property and resolution. More preferred.

In formula (87), R ¹¹⁵ and R ¹¹⁶ each independently represent -SO ₃ H or -SO ₃ ^- . n ⁵ and n ⁶ are integers and each independently represents 0 to 2. However, the total number of n ⁵ and n ⁶ is 1 to 4, and at least one of (R ¹¹⁵ ) n ⁵ and (R ¹¹⁶ ) n ⁶ is -SO ₃ ^- .
In formula (88), R ¹¹⁷ and R ¹¹⁸ each independently represent -SO ₃ H or -SO ₃ ^- . n ⁷ and n ⁸ are integers and each independently represents 0 to 2. However, the total number of n ⁷ and n ⁸ is 1 to 4, and at least one of (R ¹¹⁷ ) n ⁷ and (R ¹¹⁸ ) n ⁸ is -SO ₃ ^- .

Examples of the dye of the present invention include, but are not limited to, the compound represented by formula (89), the compound represented by formula (90), and the compound represented by formula (91). isn't it.
In the compound represented by formula (89), in formula (70), R ⁸¹ is N ⁺ and the total number of hydrogen atoms in R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ is Contains a compound that is 2.
In the compound represented by formula (90), R ⁸¹ is N ⁺ in formula (70) as the component (f), and the total number of hydrogen atoms in R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ is Contains compounds that are 0.
In the compound represented by formula (91), R ⁸¹ is P ⁺ in formula (70) as the component (f), and the total number of hydrogen atoms in R ⁸² , R ⁸³ , R ⁸⁴ and R ⁸⁵ is Contains compounds that are 0.

The content of component (f) should be 10 mol% or more in order to improve resolution, when the sum of -SO ₃ H and -SO ₃ ^- contained in component (a) contained in the dye of the present invention is 100 mol%. is preferable, and 20 mol% or more is more preferable. In order to improve the thermal stability of light-shielding properties, the content is preferably 100 mol% or less, and more preferably 80 mol%.

As a method for obtaining the dye of the present invention, in addition to the method for obtaining the above-mentioned component (a), the method for obtaining the salts of the above-mentioned components (a) and (f) is preferably applied.

The present invention will be described in detail below with reference to Examples and Comparative Examples, but the embodiments of the present invention are not limited thereto. First, evaluation methods in each example and comparative example will be explained.

<Measurement of optimal exposure amount>
A silver alloy (an alloy consisting of 99% by mass of silver and 1% by mass of copper) was deposited on the entire surface of an alkali-free glass substrate measuring 150 mm in length and 150 mm in width by sputtering. Furthermore, an ITO film was deposited on the entire surface by sputtering to obtain a glass substrate having a silver alloy film/ITO film on the entire surface of the alkali-free glass substrate.

Film thickness of cured film after heating positive photosensitive compositions 1 to 15 obtained in Examples 1 to 13 and Comparative Examples 1 to 2 at 250 ° C. for 1 hour in a nitrogen atmosphere described below using a spin coater The rotational speed was adjusted so that the distance was 1.50 μm, and the ITO surfaces of the glass substrates each having a silver alloy film/ITO film were coated to obtain coated films. Furthermore, the coated film was prebaked for 120 seconds at 110°C under atmospheric pressure using a hot plate to obtain a prebaked film, and a positive exposure mask (200 perfectly circular transparent parts with a diameter of 10.0 μm was arranged) Using a double-sided alignment single-sided exposure device, the exposure amount was changed stepwise in steps of 10 mJ within the range of 50 to 200 (mJ/cm ² : i-line equivalent value) using an ultra-high pressure mercury lamp. The prebaked film was pattern-exposed to the mixed lines g, h, and i of , to obtain an exposed film having an exposed portion and an unexposed portion within the plane. Note that pattern exposure was performed by bringing a positive exposure mask into contact with the surface of the prebaked film.

Next, as a development step, development was carried out using a paddle method using a small-sized developing device for photolithography (AD-1200; manufactured by Takizawa Sangyo Co., Ltd.) and a 2.38 mass % tetramethylammonium hydroxide aqueous solution, which is an alkaline developer. did. The paddle method here refers to a method in which an alkaline developer is shower coated on the surface of the exposed film for 10 seconds and then left to stand until a predetermined development time is reached for development. Furthermore, after rinsing with deionized water in a shower for 30 seconds, the substrate was dried by drying at 200 rpm for 30 seconds to obtain a developed film-forming substrate having a developed film. The development time is set within the range of 40 to 90 seconds, and the value obtained by subtracting the film thickness of the developed film (unexposed area) from the film thickness of the pre-baked film, that is, the film reduction (μm) in the development process is 0.80 μm. It was set as the time.

Next, as a curing process, the developed film is heated at 250°C for 1 hour in a nitrogen atmosphere using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.) to form a cured film with hole-shaped openings. A substrate for evaluating the optimum exposure amount provided with a film was obtained.

The central part of the cured film was observed using an FPD inspection microscope (MX-61L; manufactured by Olympus Corporation), and the average opening width of 10 openings in the cured film in each exposure area was 10.0 μm. The minimum exposure amount (mJ/cm ² : i-line equivalent value) when the aperture was opened such that the following was defined as the optimum exposure amount. When the shape of the opening was a perfect circle, its diameter was taken as the opening width, and when it was an ellipse, its short axis was taken as the opening width. The film thickness in each process is measured at three locations within the surface using a stylus-type film thickness measuring device (Tokyo Seimitsu Co., Ltd.; Surfcom), and the average value is rounded to the second decimal place. The numbers up to second place were calculated.

On the other hand, for negative photosensitive compositions 1 to 3 obtained in Comparative Examples 3 to 5, a negative exposure mask with an inverted mask design (a perfect circle with a diameter of 10.0 μm) was used instead of the above-mentioned positive exposure mask. A hole pattern mask (with 200 shaped shielding parts arranged) was used, and the development time was the time required for the film in the unexposed area of the solid area to dissolve and the substrate to be visually observed, multiplied by 1.5. The optimum exposure amount was measured in the same manner except for the following.

(1) Evaluation of thermal stability of light-shielding properties of cured films The light-shielding properties evaluation substrate A and the light-shielding properties evaluation substrate B obtained in Examples 1 to 13 and Comparative Examples 1 to 5 were evaluated using an optical densitometer (X- Rite (manufactured by Rite; The value divided by was defined as the light-shielding property (OD/μm) of the cured film. The smaller the absolute value (ΔOD/μm) of the value obtained by subtracting the light shielding property of the light shielding property evaluation board B from the light shielding property of the light blocking property evaluation board A, the better the thermal stability against changes in heating temperature and heating time. The cured film was excellent and was evaluated using the following criteria, with AA and A to C being passed and D being failing.
AA: ΔOD/μm is less than 0.03.
A: ΔOD/μm is 0.03 or more and less than 0.05.
B: ΔOD/μm is 0.05 or more and less than 0.10.
C: ΔOD/μm is 0.10 or more and less than 0.20.
D: ΔOD/μm is 0.20 or more.

(2) Evaluation of resolution of cured film and protrusion-like foreign matter defects Using an FPD inspection microscope for resolution evaluation substrates on which cured films with a film thickness of 1.5 μm obtained in Examples 1 to 13 and Comparative Examples 1 to 5 were formed. I observed it. Opening width of exposure mask (perfect circular transparent part with diameters of 10.0 μm, 9.0 μm, 8.0 μm, 7.0 μm, 6.0 μm, 5.0 μm, 4.0 μm, 3.0 μm, and 2.0 μm) The value obtained by subtracting the average opening width of 10 corresponding openings of the cured film (exposure mask bias) is within the range of ±0.2 μm, and pattern formation is possible without generating development residue. Among the openings, the smallest opening width was defined as the resolution (μm). The smaller the minimum aperture width, the higher the resolution and the better. Evaluation was made using the following criteria, and AA, A to C were judged as passing, and D was judged as failing. However, if a protruding foreign particle defect was observed on the surface of one or more openings, the evaluation was rated E and the test was rejected, regardless of the resolution. In addition, if there were no openings where no development residue was observed and it was impossible to evaluate the resolution, the evaluation was given as F and the film was judged as a failure. In addition, when it is E and corresponds to F, the evaluation was set as F.
AA: Resolution is 2.0±0.2 μm.
A: Resolution is 3.0±0.2 μm.
B: Resolution is 4.0±0.2 μm or 5.0±0.2 μm.
C: Resolution is 6.0±0.2 μm or 7.0±0.2 μm.
D: Resolution is 7.8 μm or more.
E: Protrusion-like foreign particle defects are observed on the surface of one or more openings.
F: There are no openings where no development residue is observed, making it impossible to evaluate the resolution.

(3) Evaluation of resolution of organic EL display devices The organic EL display devices obtained in Examples 14 to 26 were left standing with their light-emitting surfaces facing up and emitted by direct current driving at 10 mA/cm ² , and the FPD The light emitting surface of the organic EL display device was observed using an inspection microscope, and the aperture widths of 10 light emitting pixel parts where normal light emission was observed were measured, and the average value was taken as the resolution (μm) of the organic EL display device. . The higher the resolution, the better the display device, and evaluation was made using the following criteria, with AA and A to C being passed and D being failing. However, if one or more pixels that did not emit light (non-lighted pixels) were observed within the light emitting surface, the evaluation was given as E and the test was rejected. Regarding the photosensitive compositions that failed in at least one of the above-mentioned (1) evaluation of the thermal stability of light-shielding properties of the cured film and (2) resolution and protruding foreign object defects of the cured film. did not produce an organic EL display device and was excluded from this evaluation.
AA: Resolution is 2.0±0.2 μm.
A: Resolution is 3.0±0.2 μm.
B: Resolution is 4.0±0.2 μm or 5.0±0.2 μm.
C: Resolution is 6.0±0.2 μm or 7.0±0.2 μm.
D: Resolution is 7.8 μm or more.
E: One or more non-lit pixels are observed.

(Synthesis Example 1: Synthesis of hydroxyl group-containing diamine compound A)
18.30 g (0.05 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was dissolved in 100 mL of acetone, 17.40 g (0.3 mol) of propylene oxide, and - Cooled to 15°C. A solution of 20.40 g (0.11 mol) of 3-nitrobenzoyl chloride dissolved in 100 mL of acetone was added dropwise thereto. After the dropwise addition was completed, the mixture was allowed to react at -15°C for 4 hours, and then the temperature was returned to room temperature. The precipitated white solid was filtered off and dried under vacuum at 50°C. 30.00 g of the solid was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, and 2.00 g of 5% palladium-carbon was added. Hydrogen was introduced here using a balloon, and the reduction reaction was carried out at room temperature. After about 2 hours, it was confirmed that the balloon did not deflate any further, and the reaction was terminated. After the reaction was completed, the catalyst was filtered to remove the palladium compound, and the mixture was concentrated using a rotary evaporator to obtain a phenolic hydroxyl group-containing diamine compound A represented by formula (34).

(Synthesis Example 2: Synthesis of polyimide precursor B)
Under a stream of dry nitrogen, 31.00 g (0.10 mol) of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride was dissolved in 500.00 g of NMP. Here, 45.35 g (0.075 mol) of phenolic hydroxyl group-containing diamine compound A obtained in Synthesis Example 1 and 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyl diamine were added. The siloxane was added along with 50.00 g of NMP and reacted for 1 hour at 20°C and then for 2 hours at 50°C. As an end-capping agent, 4.36 g (0.04 mol) of 3-aminophenol was added together with 5.00 g of NMP, and the mixture was reacted at 50° C. for 2 hours. Thereafter, 50.00 g of 28.60 g (0.24 mol) of N,N-dimethylformamide dimethyl acetal was added. After the addition, the mixture was stirred at 50°C for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and then poured into 3 L of water to obtain a white precipitate. The white precipitate obtained by repeating the above operation five times was collected as a filter material, washed five times with water, and then dried in a vacuum dryer at 80° C. for 24 hours to obtain a powdery polyimide precursor B. Polyimide precursor B was a resin belonging to component (b-1), had a structural unit represented by formula (18), and had a weight average molecular weight (Mw) of 25,000.

(Synthesis Example 3: Synthesis of diimidazolide compound C)
Under a stream of dry nitrogen, 162.15 g (1.00 mol) of 1,1'-carbonyldiimidazole (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added to 1000.00 g of NMP, and the mixture was stirred for 1 hour at a liquid temperature of 10°C. and dissolved. Further, 113.46 g (0.44 mol) of diphenyl ether 4,4'-dicarboxylic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added and stirred while maintaining the liquid temperature at 20° C. or lower. Next, the liquid temperature was raised to 60°C and stirred, and after the generation of carbon dioxide gas was completed, the mixture was cooled to 5°C. 1000.00g of deionized water was added dropwise while maintaining the temperature below 10°C, and the precipitate was filtered off. The precipitate was washed with deionized water and then with isopropanol. It was dried under reduced pressure at 50° C. for 6 hours to obtain a diimidazolide compound C represented by formula (35).

(Synthesis Example 4: Synthesis of polybenzoxazole precursor D)
Under a stream of dry nitrogen, 732.52 g (2.00 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added to 3662.60 g of NMP, and the mixture was heated at 40°C for 1 hour. Stirred. Furthermore, 573.38 g (1.60 mol) of diimidazolide compound C produced in Synthesis Example 3 was added together with 286.69 g of NMP, the liquid temperature was raised to 80° C., and the mixture was stirred for 5 hours. Next, 131.33 g (0.80 mol) of 5-norbornene-2,3-dicarboxylic anhydride was added, and the mixture was stirred at a liquid temperature of 80° C. for 3 hours. The liquid temperature was cooled to 20° C., 600.20 g of acetic acid was added, and the mixture was stirred for 30 minutes, followed by the addition of 500.00 g of NMP, and further stirred for 1 hour. The solution obtained by the above operation was poured into 10 L of water to obtain a precipitate. This precipitate was filtered, washed five times with deionized water, and then dried under reduced pressure at 50° C. for 3 days to obtain polybenzoxazole precursor D in powder form. Polybenzoxazole precursor D was a resin belonging to component (b-1), had a structural unit represented by formula (18), and had a weight average molecular weight (Mw) of 26,000. When polybenzoxazole precursor D was analyzed by NMR and gas chromatography-mass spectrometry, no imidazole ring structure derived from diimidazolide compound C represented by formula (35) was detected. It was thought that it had completely disappeared.

(Synthesis Example 5: Synthesis of quinonediazide compound E)
Under a stream of dry nitrogen, 127.36 g (0.30 mol) of the compound represented by formula (36) (manufactured by Honshu Chemical Industry Co., Ltd.) and 80.60 g (0.30 mol) of 1,2-naphthoquinone-2 -Diazide-4-sulfonyl chloride (manufactured by Toyo Gosei Co., Ltd.) and 80.60 g (0.30 mol) of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride (manufactured by Toyo Gosei Co., Ltd.), The mixture was added to 1,910.43 g of 1,4-dioxane and stirred for 1 hour at a liquid temperature of 20°C. Further, 303.57 g of additive (triethylamine:1,4-dioxane = mass ratio 20:80) was added dropwise, and the mixture was stirred for 3 hours at a liquid temperature of 30°C. The triethylamine salt is separated by filtration, the filtrate is poured into water, the generated precipitate is collected, washed three times with deionized water, filtered and dried under reduced pressure to obtain a mixture containing at least the compound represented by formula (38). A quinonediazide compound E represented by formula (37) was obtained. The compound represented by formula (38) is the component (c-1), and has a group represented by formula (22) and a group represented by formula (23), and has a phenolic hydroxyl group. Equivalent to. The compound represented by formula (38) was identified by LC-MS and MALDI-TOF MS.

In formula (37), * represents a bonding site with an oxygen atom.

(Synthesis Example 6: Synthesis of quinonediazide compound F)
Under a stream of dry nitrogen, 127.36 g (0.30 mol) of the compound represented by formula (36) and 161.20 g (0.60 mol) of 1,2-naphthoquinone-2-diazido-5-sulfonyl chloride, The mixture was added to 1,910.43 g of 1,4-dioxane and stirred for 1 hour at a liquid temperature of 20°C. Further, 303.57 g of additive (triethylamine:1,4-dioxane = mass ratio 20:80) was added dropwise, and the mixture was stirred for 3 hours at a liquid temperature of 30°C. The triethylamine salt is separated by filtration, the filtrate is poured into water, the generated precipitate is collected, washed three times with deionized water, filtered and dried under reduced pressure to obtain a mixture containing at least the compound represented by formula (40). A quinonediazide compound F represented by formula (39) was obtained. The compound represented by formula (40) is the component (c-1) and corresponds to a compound having two groups represented by formula (23) in the molecule and a phenolic hydroxyl group. The compound represented by formula (40) was identified by LC-MS and MALDI-TOF MS.

In formula (39), * represents a bonding site with an oxygen atom.

(Synthesis Example 7: Synthesis of perylene blue dye 1)
In 2,545.92 g of phenol melted at 70°C, 636.48 g (1.50 mol) of 1,12-dihydroxyperylene-3,4,9,10-tetracarboxylic dianhydride (Sigma-Aldrich 378.39 g (3.00 mol) of 1,2-diamino-3-fluorobenzene (manufactured by Sigma-Aldrich), and 64.61 g of piperazine were added, and while stirring the mixture, the liquid temperature The temperature was raised to 170°C.Next, stirring was performed for 8 hours at a liquid temperature of 170°C to allow the reaction to proceed sufficiently, and the produced water was separated by distillation as an azeotrope with phenol.Then, the temperature was raised to 100°C. After cooling, 500 g of ethanol was added stepwise in 50 g increments, and the mixture was further stirred at 60°C for 1 hour, washed with water, filtered, and dried under reduced pressure at 80°C for 24 hours to obtain a reaction product. .00g of the reaction product was dissolved in 500.00g of 30% by mass oleum and the solution temperature was raised to 80°C while stirring.The solution was stirred at 80°C for 8 hours to allow the sulfonation reaction to proceed. Then, it was poured into 7 kg of ice water to obtain a slurry containing precipitates, which was filtered.Then, the filtrate was washed with a mixed solution (ethanol:water = mass ratio of 80:20), and then filtered again. It was dried at 80°C under reduced pressure for 24 hours.Furthermore, it was dry-pulverized using a Nano Jet Mizer (manufactured by Aisin Nano Technologies Co., Ltd.), and coarse particles were removed by passing it through a stainless steel sieve filter (opening diameter 20 μm). was removed to obtain perylene blue dye 1. As a result of analysis using LC-MS and MALDI-TOF MS, perylene blue dye 1 was component (a), and was a compound represented by formula (41), formula ( 42), a compound represented by formula (43), a compound represented by formula (44), a compound represented by formula (45), a compound represented by formula (46), a compound represented by formula ( It was a mixture of the compound represented by formula (47) and the compound represented by formula (48).The compound represented by formula (45), the compound represented by formula (46), and the compound represented by formula (47) were The total content of the compound represented by the above formula and the compound represented by formula (48) was 12% by mass in 100% by mass of perylene blue dye 1.

(Synthesis example 8: Synthesis of perylene blue dye 2)
100.00 g of perylene-3,4,9,10-tetracarboxylic acid bisbenzimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.; mixture of cis and trans forms) was dissolved in 400.00 g of 20% by mass oleum. The liquid temperature was raised to 70°C while stirring. The mixture was stirred at a liquid temperature of 70° C. for 5 hours to allow the sulfonation reaction to proceed. Next, it was poured into 9 kg of ice water to obtain a slurry containing precipitates, which was filtered. The filtrate was washed with a mixed solution (ethanol:water = mass ratio 80:20), filtered again, and dried under reduced pressure at 80°C for 24 hours. Furthermore, dry pulverization was performed using a nanojet miser, and coarse components were removed by passing through a stainless steel sieve filter (opening diameter 20 μm) to obtain perylene blue dye 2. As a result of analysis using LC-MS and MALDI-TOF MS, perylene blue dye 2 was the component (a), and was found to be a compound represented by formula (49), a compound represented by formula (50), and a compound represented by formula (51). ) and the compound represented by formula (52). The total content of the compound represented by formula (51) and the compound represented by formula (52) was 74% by mass in 100% by mass of perylene blue dye 2.

(Synthesis Example 9: Synthesis of perylene blue dye 3)
40.00 g of perylene blue dye 2 obtained in Synthesis Example 8 above was dissolved in 400.00 g of 10% by mass oleum, and the temperature of the solution was raised to 130° C. with stirring. The mixture was stirred at a liquid temperature of 130° C. for 10 hours to allow the sulfonation reaction to proceed. Next, it was poured into 7 kg of ice water to obtain a slurry containing precipitates, which was filtered. Next, the filtrate was washed with a mixed solution (ethanol:water = mass ratio 80:20), filtered again, and dried under reduced pressure at 80°C for 24 hours. Furthermore, dry pulverization was performed using a nanojet miser, and coarse components were removed by passing through a stainless steel sieve filter (opening diameter 20 μm) to obtain perylene blue dye 3. As a result of analysis using LC-MS and MALDI-TOF MS, perylene blue dye 3 was component (a), and was a mixture of the compound represented by formula (53) and the compound represented by formula (54). Ta.

(Synthesis Example 10: Synthesis of perylene blue dye 4)
In 3,066.93 g of phenol melted at 70° C., 681.54 g (1.50 mol) of perylene-3,4,9,10-tetracarboxylic dianhydride monosulfone (manufactured by Sigma-Aldrich) was added. , 564.60 g (3.00 mol) of 3,4-diaminobenzenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 64.61 g of piperazine were added, and the liquid temperature was raised to 170°C while stirring the mixture. The temperature rose. Next, the mixture was stirred at a liquid temperature of 170° C. for 8 hours to allow the reaction to proceed sufficiently, and then the produced water was separated by distillation as an azeotrope with phenol. Next, the mixture was cooled to 100°C, 500g of ethanol was added stepwise in 50g increments, and the mixture was further stirred at 60°C for 1 hour, washed with water, filtered, and dried under reduced pressure at 80°C for 24 hours to obtain a reaction product. Ta. Furthermore, dry pulverization was performed using a nanojet miser, and coarse components were removed by passing through a stainless steel sieve filter (opening diameter 20 μm) to obtain perylene blue dye 4. As a result of analysis using LC-MS and MALDI-TOF MS, perylene blue dye 4 was component (a), and was a mixture of the compound represented by formula (55) and the compound represented by formula (56). Ta.

(Synthesis Example 11: Synthesis of perylene blue dye 5)
In 2,569.80 g of phenol melted at 70°C, 642.45 g (1.50 mol) of 1,7-difluoroperylene-3,4,9,10-tetracarboxylic dianhydride (Sigma-Aldrich 366.51 g (3.00 mol) of 3-methylbenzene-1,2-diamine (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and 64.61 g of piperazine were added, and the mixture was stirred. The temperature was raised to 180°C. Next, the mixture was stirred at a liquid temperature of 180° C. for 9 hours to allow the reaction to proceed sufficiently, and then the produced water was separated by distillation as an azeotrope with phenol. Next, the mixture was cooled to 100°C, 500g of ethanol was added stepwise in 50g increments, and the mixture was further stirred at 60°C for 1 hour, washed with water, filtered, and dried under reduced pressure at 80°C for 24 hours to obtain a reaction product. Ta. Next, 50.00 g of the reaction product was dissolved in 500.00 g of 30% by mass oleum, and the solution temperature was raised to 80° C. with stirring. The mixture was stirred at a liquid temperature of 80° C. for 8 hours to advance the sulfonation reaction. Next, it was poured into 7 kg of ice water to obtain a slurry containing precipitates, which was filtered. Next, the filtrate was washed with a mixed solution (ethanol:water = mass ratio 80:20), filtered again, and dried at 80° C. under reduced pressure for 24 hours. Furthermore, dry pulverization was performed using a nanojet miser, and coarse components were removed by passing through a stainless steel sieve filter (opening diameter 20 μm) to obtain perylene blue dye 5. As a result of analysis using LC-MS and MALDI-TOF MS, perylene blue dye 5 was the component (a), and was found to be a compound represented by formula (57), a compound represented by formula (58), and a compound represented by formula (59). ) and the compound represented by formula (60).

(Synthesis Example 12: Synthesis of perylene blue dye 6)
80.00 g of perylene blue dye 2 obtained in the same manner as in Synthesis Example 8 above was dissolved in 800.00 g of 10% by mass oleum, and the temperature of the solution was raised to 130° C. with stirring. The mixture was stirred at a liquid temperature of 130° C. for 10 hours to allow the sulfonation reaction to proceed. Next, the slurry was poured into 14 kg of ice water to obtain a slurry, which was then filtered while washing with ethanol to obtain a wet cake in which the product was concentrated. Furthermore, a sodium hydroxide aqueous solution (10% by mass) was gradually added to the wet cake while stirring until the pH reached 7.0 to neutralize it, and after stirring for 3 hours at a liquid temperature of 30°C, it was filtered while washing with ethanol. did. It was dried at 80° C. under reduced pressure for 24 hours to obtain sodium salt A, which is a sodium salt of perylene blue dye. As a result of analysis using LC-MS and ICP-MS (inductively coupled plasma mass spectrometry), sodium salt A is a mixture of component (a) and Na ⁺ , and is a compound represented by formula (92) and formula ( It was a dye consisting of a compound represented by 93).

Next, 20.00 g of sodium salt A was added to a flask containing 700.00 g of deionized water and 50.00 g of PGME, and the mixture was stirred at a liquid temperature of 70° C. for 10 minutes. Further, 7.32 g of 2-(dodecylamino)ethanol hydrochloride (manufactured by Sigma-Aldrich) was added, and the mixture was stirred at a temperature of 70° C. for 3 hours, and then filtered. It was washed with deionized water, dried under reduced pressure at 80° C. for 24 hours, and dry-pulverized using a nanojet miser to obtain perylene blue dye 6. As a result of analysis using LC-MS and MALDI-TOF MS, perylene blue dye 6 is a compound represented by formula (94) and formula (95) containing component (a) and (f). It was a mixture of compounds.

(Synthesis Example 13: Synthesis of perylene blue dye 7)
Sodium salt A was used as the starting material in the same manner as in Synthesis Example 12, except that 9.36 g of benzyldodecyldimethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 2-(dodecylamino)ethanol hydrochloride. Perylene blue dye 7 was synthesized as follows. As a result of analysis using LC-MS and MALDI-TOF MS, perylene blue dye 7 is a compound represented by formula (96) and formula (97) containing component (a) and component (f). It was a mixture of compounds.

(Synthesis Example 14: Synthesis of perylene blue dye 8)
Sodium salt A was used as the starting material in the same manner as in Synthesis Example 12, except that 9.34 g of tetrabutylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 2-(dodecylamino)ethanol hydrochloride. , perylene blue dye 8 was synthesized. As a result of analysis using LC-MS and MALDI-TOF MS, perylene blue dye 8 is a compound represented by formula (98) and formula (99) containing component (a) and (f). It was a mixture of compounds.

(Synthesis Example 15: Synthesis of perylene blue dye 9)
100.00 g of "Spectrasense (registered trademark)" Black K0087 (manufactured by Color & Effect) was dissolved in 400.00 g of 20% by mass oleum, and the temperature of the solution was raised to 70° C. while stirring. Subsequently, the mixture was stirred at a liquid temperature of 70° C. for 10 hours to advance the sulfonation reaction. Next, the slurry was poured into 15 kg of ice water to obtain a slurry, which was then filtered while washing with ethanol to obtain a wet cake in which the product was concentrated. Further, an aqueous sodium hydroxide solution (10% by mass) was gradually added to the wet cake to neutralize it with stirring until the pH reached 7.0, and the mixture was stirred at a liquid temperature of 30° C. for 3 hours. The slurry obtained by neutralization was filtered while washing with ethanol. The filtered solid was dried at 80° C. under reduced pressure for 24 hours to obtain sodium salt B, which is a sodium salt of perylene blue dye. As a result of analysis using LC-MS and ICP-MS, sodium salt B is a mixture of component (a) and Na ⁺ , and is a mixture of the compound represented by formula (106) and the compound represented by formula (107). It was a pigment consisting of

Next, 20.00 g of sodium salt B was added to a flask containing 800.00 g of deionized water, and dissolved by stirring for 10 minutes at a liquid temperature of 40°C. Furthermore, 15.14 g of hexyltrimethylammonium bromide (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added and stirred at a liquid temperature of 50° C. for 6 hours, and the formation of insoluble solids was confirmed. The resulting solid was then washed with deionized water and filtered. It was dried at 80° C. under reduced pressure for 24 hours and dry-pulverized using a nano jet miser to obtain perylene blue dye 9. As a result of analysis using LC-MS and MALDI-TOF MS, perylene blue dye 9 is a compound represented by formula (108) and formula (109) containing component (a) and (f). It was a mixture of compounds.

(Production Example 1: Production of finely divided perylene pigment A)
1,000.00 g of "Spectrasense (registered trademark)" Black K0087 (manufactured by Color & Effect) was heated in an oven at 250°C under atmospheric pressure/air for 1 hour, then brought to room temperature, and the dried agglomerations were loosened using a ball mill to form a dark purple pigment. I got it. 500.00 g of dark purple pigment, 2.5 kg of grinding material (sodium chloride particles), and 250.00 g of dipropylene glycol were mixed, charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), and heated at 90°C. The mixture was kneaded for 8 hours. This kneaded material was poured into 5 L of warm water, stirred for 1 hour while maintaining the temperature at 70°C to form a slurry, and filtered and washed with water repeatedly until the chlorine ions determined by ion chromatography became 50 mass ppm or less. The crushed wood and dipropylene glycol were removed. Furthermore, after drying in an oven at 100°C under atmospheric pressure/in air for 6 hours, the dried agglomerates were loosened using a ball mill, and fine particles consisting of a mixture of the compound represented by formula (61) and the compound represented by formula (62) were prepared. Perylene pigment A was obtained. The finely divided perylene pigment A is the component (e) and corresponds to the compound represented by the above-mentioned formula (30) and the compound represented by the formula (31).

(Production Example 2: Production of finely divided dioxazine pigment B)
1,000.00 g of "Cromophtal (registered trademark)" Violet D5700 (manufactured by BASF: C.I. Pigment Violet 37) was heated in an oven at 200°C under atmospheric pressure/air for 1 hour, brought to room temperature, and then heated in a ball mill. The dried agglomerates were loosened to obtain a purple pigment. 500.00 g of purple pigment, 2.5 kg of grinding material (sodium chloride particles), and 250.00 g of dipropylene glycol were mixed, charged into a 1-gallon stainless steel kneader, and kneaded at 90° C. for 5 hours. This kneaded material was poured into 5 L of warm water and stirred for 1 hour while maintaining the temperature at 70° C. to form a slurry. Filtration and water washing were repeated three times to remove the grinding material and dipropylene glycol. Furthermore, after drying in an oven at 100° C. under atmospheric pressure/in air for 6 hours, the dried agglomerates were loosened in a ball mill to obtain a finely divided dioxazine pigment B represented by formula (63). Finely divided dioxazine pigment B is component (e) and corresponds to the above-mentioned compound having the triphendioxazine skeleton.

(Production Example 3: Production of salt-forming dye C)
A flask was charged with 9.25 g of C.I., a basic dye. I. Basic Blue 7 and 200.00 g of deionized water were added, and the mixture was stirred at a liquid temperature of 60° C. for 30 minutes. Next, 11.50 g of C.I., which is an acid dye, is added. I. A solution of Acid Red 52 dissolved in 120.00 g of deionized water was added, stirred at a liquid temperature of 60° C. for 1 hour, cooled to 25° C., and filtered to obtain a purple solid product. It was further dried at 60° C. for 8 hours to obtain powdered salt-forming dye C.

(Synthesis Example 15: Synthesis of methacrylic resin solution G)
A resin solution synthesized by the same method as that disclosed in Synthesis Example 14 (tertiary amino group and ethylenically unsaturated group-containing resin (F-1)) described in Patent Document 5 was used as methacrylic resin solution G.

400.00 g of PGMEA was charged into a pressure vessel equipped with a stirrer, a thermometer, a reflux condenser, and a dripping pump, and after filling the reaction vessel with nitrogen, the temperature was raised to 90°C. 2.00 g of 2-dimethylaminoethyl methacrylate, 31.00 g of methyl methacrylate, 20.00 g of 2-ethylhexyl methacrylate, 30.00 g of styrene, 17.0 g of methacrylic acid, and a polymerization initiator. A mixed solution of 2.0 g of azobisisobutyronitrile and 3.0 g of n-dodecyl mercaptan was added dropwise over 3 hours to cause copolymerization. Next, the inside of the reaction vessel was purged with air, and 10.00 g of glycidyl methacrylate was added dropwise over 1 hour to advance the addition reaction, and the mixture was further stirred for 2 hours to form a methacrylic resin with a weight average molecular weight (Mw) of 7000. A containing resin solution was obtained. Furthermore, a resin solution prepared using PGMEA to have a solid content of 20.00% by mass was designated as methacrylic resin solution G.

(Synthesis Example 16: Synthesis of methacrylic resin solution H)
A resin solution synthesized by the same method as the synthesis example of acrylic resin 1 solution described in Patent Document 6 was designated as methacrylic resin solution H.

800.00 g of cyclohexanone was placed in a reaction vessel and heated to 80°C while nitrogen gas was injected into the vessel. Then, 60.00 g of styrene, 60.00 g of methacrylic acid, 65.00 g of methyl methacrylate, 65.00 g of butyl methacrylate, and 10.00 g of azobisisobutyronitrile as a polymerization initiator were mixed. The solution was added dropwise into the reaction vessel over 1 hour. After the dropwise addition, the reaction was further carried out at 100°C for 3 hours, and then a solution of 2.00g of azobisisobutyronitrile dissolved in 50.00% of cyclohexanone was added dropwise, and the reaction was further carried out at 100°C for 1 hour to reduce the mass. A solution containing a methacrylic resin having an average molecular weight of 40,000 was obtained. It was cooled to room temperature and diluted with cyclohexanone so that the solid content of the resin solution was 20.00% by mass to obtain a methacrylic resin solution H.

(Synthesis Example 17: Synthesis of methacrylic resin solution I)
Synthesis Example 3 described in Patent Document 5: A resin solution synthesized in the same manner as alkali-soluble resin A-3 was designated as methacrylic resin solution I.

26.10 g of 4-hydroxyphenyl methacrylate (PQMA, manufactured by Showa Denko K.K.) and 13.90 g of glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 100.00 g of PGMEA for 30 minutes. Stirred. Separately, a solution of 3.66 g of V-601 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), a thermal polymerization initiator, dissolved in 15.00 g of PGMEA was added and stirred for 10 minutes. The two obtained solutions were simultaneously added dropwise over 2 hours to 45.00 g of PGMEA maintained at a liquid temperature of 85° C. under a nitrogen atmosphere in a 300 mL three-necked flask. After completion of the dropwise addition, the liquid was stirred for 3 hours at a temperature of 85°C and cooled to obtain a solution having a weight average molecular weight (Mw) of 8600 and belonging to component (b-1), 4-hydroxyphenyl methacrylate:glycidyl methacrylate = mol ratio of 60:40. A solution containing the copolymer was obtained. A resin solution obtained by preparing this with PGMEA to have a solid content of 20.00% by mass was designated as methacrylic resin solution I.

(Preparation example 1: Preparation of dye dispersion 1)
In 900.00 g of a mixed solvent (PGME: ethyl lactate: GBL = mass ratio 50:30:20), which is component (d), 25.00 g of polyimide precursor B, which is component (b-1), and 35. 00g of Polybenzoxazole Precursor D was added and stirred for 30 minutes to dissolve. Furthermore, 40.00 g of perylene blue dye 1, which is component (a), was added and stirred for 30 minutes to obtain a pre-stirred liquid. Next, a vertical bead mill “Ultra Apex Mill Advance (registered trademark)” was used, in which the vessel was filled with “Treceram (registered trademark)” (manufactured by Toray Industries, Inc.), which is a 0.05 mmφ zirconia bead, at a filling rate of 75% by volume. ; manufactured by Hiroshima Metal & Machinery Co., Ltd.), and wet media dispersion treatment was carried out using a circulation method at a circumferential speed of 8 m/s for 1 hour and then at a circumferential speed of 10 m/s for 3 hours. Filtration was performed using a filter with an opening diameter of 0.5 μm to obtain a dye dispersion liquid 1 with a solid content of 10.00% by mass. Table 1 shows the blended mass of each raw material.

(Preparation Examples 2 to 5: Preparation of dye dispersions 2 to 5)
Wet media dispersion treatment and filtration were performed in the same manner as in Preparation Example 1, except that perylene blue dyes 2 to 5 were used in place of perylene blue dye 1, and the amounts of each raw material were as shown in Table 1, to obtain a dye dispersion. I got 2-5. Table 1 shows the blended mass of each raw material.

(Preparation Examples 6-7: Preparation of dye dispersions 6-7)
In place of perylene blue pigment 1, finely divided perylene pigment A or finely divided dioxazine pigment B, and perylene blue pigment 2 were used, and the wet method was carried out in the same manner as in Preparation Example 1, except that the amounts of each raw material were as shown in Table 2. Media dispersion treatment and filtration were performed to obtain dye dispersions 6 to 7.

(Preparation example 8: Preparation of dye dispersion liquid 8)
Using a mixed solvent (PGMEA: ethyl lactate: GBL = mass ratio 50:30:20) instead of the mixed solvent (PGME: ethyl lactate: GBL = mass ratio 50:30:20), the formulation of each raw material shown in Table 2 A wet media dispersion treatment and filtration were performed in the same manner as in Preparation Example 1, except that the amount was determined, and dye dispersion liquid 8 was obtained. Note that PGME and ethyl lactate are components (d-1), and PGMEA and GBL are components (d-2).

(Preparation Example 9: Preparation of dye dispersion 9)
In place of polyimide precursor B and polybenzoxazole precursor D, component (b-1) TR4020G (powder of cresol novolac type phenolic resin; manufactured by Asahi Yokuzai Co., Ltd.) was used, and each raw material shown in Table 2 was used. A wet media dispersion treatment and filtration were carried out in the same manner as in Preparation Example 1, except that the amount was changed to obtain a pigment dispersion 9.

(Preparation Example 10: Preparation of dye dispersion 10)
A pigment dispersion prepared based on the method disclosed in Production Example 1 (production of colored pigment dispersion (DB-1)) described in Patent Document 5 was designated as pigment dispersion 10.

To 1875.2 g of PGMEA, 478.50 g of methacrylic resin solution G and 56.30 g of dispersant (dispersant with an amine value of 20 mg KOH / g described in Synthesis Example 2 of JP 2020-070352 A) were added. The mixture was stirred for 10 minutes. Furthermore, 600.00 g of "Irgaphor Black (registered trademark)" S0100CF (manufactured by BASF Corporation; "S0100" in the table), which is a lactam black pigment, was added and stirred for 20 minutes to obtain a pre-stirred liquid. Vertical bead mill "Ultra Apex Mill (registered trademark)" whose vessel is filled with 0.10 mm diameter zirconia beads "Treceram (registered trademark)" (manufactured by Toray Industries, Inc.) at a filling rate of 70% by volume; The pre-stirred liquid was sent to a tank (manufactured by Hiroshima Metal & Machinery) and subjected to wet media dispersion treatment for 3 hours at a circumferential speed of 10 m/s using a circulation method.The solid content was 25.00% by mass, and pigment: resin = mass. A dye dispersion 10 with a ratio of 80:20 was obtained. Table 2 shows the blending amount of each raw material.

(Preparation Example 11: Preparation of dye dispersion liquid 11)
A wet media dispersion treatment and filtration were carried out in the same manner as in Preparation Example 1, except that finely divided perylene pigment A was used in place of perylene blue dye 1, and the amounts of each raw material were as shown in Table 3. Obtained.

(Preparation example 12: Preparation of dye dispersion liquid 12)
To 515.00 g of cyclohexanone, 5.00 g of Solsperse 24000 (manufactured by Lubrizol), which is an amine resin, and 20.00 g of Marquid No. 2, which is a rosin-modified maleic acid resin, were added. 32 (manufactured by Arakawa Chemical Co., Ltd.) was added and stirred for 1 hour to dissolve. Furthermore, 250.00 g of methacrylic resin solution H, 10.00 g of a compound represented by formula (64) which is a copper phthalocyanine compound having a basic functional group, and 60.00 g of C.I. I. Pigment Blue 60 and 100.00g of C.I. I. Pigment Yellow 139 and 40.00g of C.I. I. Pigment Violet 23 was added and stirred for 30 minutes to obtain a pre-stirred liquid. Next, a wet media dispersion treatment was performed for 5 hours using a sand mill filled with glass beads of 1.0 mmφ, and the mixture was filtered through a filter with an opening diameter of 1 μm to obtain a dye dispersion 12.

(Example 1)
Under yellow light, 1.15 g of polyimide precursor, which is component (b-1), was added to 16.47 g of a mixed solvent (PGME: ethyl lactate: GBL = mass ratio 50:30:20), which is component (d). B, 0.68 g of quinonediazide compound E, which is component (c), and 7.50 g of crosslinking agent solution X (manufactured by Honshu Chemical Industry Co., Ltd.; a compound represented by formula (65) and A solution in which the represented compound was dissolved using a mixed solvent of PGME:ethyl lactate:GBL=mass ratio of 50:30:20 so that the solid content was 10.00% by mass was added, and the mixture was stirred for 30 minutes. and dissolved. Further, 24.20 g of dye dispersion 1 was added, stirred for 1 hour, and then filtered using a filtration filter with an opening diameter of 0.5 μm to obtain positive photosensitive composition 1 with a solid content of 10.00% by mass. Obtained. Table 4 shows the blending amount of each raw material. Note that PGME and ethyl lactate are components (d-1).

The thickness of the cured film after heating the positive photosensitive composition 1 at 250 ° C. for 1 hour in a nitrogen atmosphere described below on the surface of Tempax (manufactured by AGC Techno Glass Co., Ltd.), which is a transparent glass substrate, is as follows. A coating film was obtained by performing a coating process using a spin coater while adjusting the rotation speed so that the coating thickness was 1.50 μm. A prebaking process was performed in which the coated film was heated at 110° C. for 2 minutes under atmospheric pressure using a hot plate to obtain a prebaked film. A development process was performed in the same manner as in the measurement of the optimum exposure amount described above without performing an exposure process, to obtain a solid developed film. Next, a first curing process (under nitrogen atmosphere, 250°C for 1 hour) was performed in which the developed film was heated using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.), and the film thickness was 1 hour. A substrate A for evaluating light-shielding properties having a solid cured film of 50 μm was obtained, and its light-shielding properties (OD/μm) were evaluated by the method described above.

On the other hand, a developed film was formed on Tempax using the same method, a first curing process was performed (under nitrogen atmosphere, 270°C for 1 hour), and after being naturally cooled to 30°C, it was placed in a high-temperature inert oven again, and then The substrate subjected to the second curing process (270°C for 1 hour in a nitrogen atmosphere) was used as substrate B for evaluating light shielding properties, and the light shielding properties (OD/μm) were evaluated, and the thermal stability of the light shielding properties (ΔOD /μm) was evaluated. The results are shown in Table 5.

Next, instead of using a positive exposure mask (a hole pattern mask in which 200 perfectly circular transparent parts with a diameter of 10.0 μm are arranged), a positive exposure mask (diameters of 10.0 μm, 9.0 μm, 8.0 μm, 7 The optimum exposure amount described above was used, except that a hole pattern mask (hole pattern mask in which 50 perfectly circular transparent parts of 0 μm, 6.0 μm, 5.0 μm, 4.0 μm, 3.0 μm, and 2.0 μm were arranged) was used. The coating process, pre-baking process, exposure process, development process, and curing process were performed in the same manner as in the measurement of 1 to 100 ml, and the ITO surface of the glass substrate having the silver alloy film/ITO film was coated with a film thickness of 1. A substrate for resolution evaluation having a cured film of .50 μm was obtained, and the resolution was evaluated by the method described above. The evaluation results are shown in Table 5.

(Examples 2 to 5)
Positive photosensitive compositions 2 to 5 were prepared in the amounts shown in Table 4, and in addition to the light-shielding evaluation substrates A and B, a resolution evaluation substrate was prepared in the same manner as in Example 1. Table 5 shows the results of evaluating the thermal stability and resolution of light shielding properties using the method.

(Examples 6 to 10)
Positive photosensitive compositions 6 to 10 were each prepared in the amounts shown in Table 6, and in addition to substrates A and B for light-shielding evaluation were prepared in the same manner as in Example 1, a substrate for resolution evaluation was prepared, and the same method was used as described above. Table 7 shows the results of evaluating the thermal stability and resolution of light shielding properties. In addition, only in the preparation of positive photosensitive composition 8, crosslinking agent solution Y (manufactured by Honshu Chemical Industry Co., Ltd.; the compound represented by formula (65) and the compound represented by formula (66) were mixed with PGMEA: A solution prepared by dissolving ethyl lactate:GBL using a mixed solvent with a mass ratio of 50:30:20 to give a solid content of 10.00% by mass was used.

(Comparative example 1)
Under yellow light, 6.35 g of polyimide precursor B and 1.81 g of quinonediazide compound F were added to 26.50 g of mixed solvent (ethyl lactate: GBL = mass ratio 50:50) and dissolved by stirring for 30 minutes. I let it happen. Next, 0.64 g of salt-forming dye C obtained in Production Example 3 and 1.63 g of C. dye were added. I. Solvent Blue 45, the aforementioned 10.89 g of crosslinking agent solution X, 1.27 g of the compound represented by formula (67), 0.73 g of the compound represented by formula (68), and 0.18 g A compound represented by formula (69) was added and dissolved by stirring for 1 hour to prepare positive photosensitive composition 11. Table 8 shows the blended mass of each raw material. Next, using the positive photosensitive composition 11, a resolution evaluation substrate was prepared in addition to the light-shielding evaluation substrates A and B in the same manner as in Example 1, and the thermal stability of the light-shielding property and the The resolution was evaluated. The results are shown in Table 9.

(Comparative example 2)
A positive photosensitive composition 12 was prepared with the amount shown in Table 8, and in addition to the light-shielding evaluation substrates A and B in the same manner as in Example 1, a resolution evaluation substrate was prepared. The thermal stability and resolution were evaluated. The results are shown in Table 9.

(Comparative example 3)
In 24.34 g of PGMEA, 14.22 g of methacrylic resin solution I and 2.12 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.; "DPHA" in the table), which is a radically polymerizable compound, 0.27 g of "ADEKA Arkles" (registered trademark) NCI-831 (manufactured by ADEKA Corporation; "NCI-831" in the table), which is a photopolymerization initiator, and 0.01 g, which is a silicone surfactant. BYK-333 (manufactured by BYK Chemie) was added and stirred for 30 minutes. Further, 9.05 g of dye dispersion 10 was added and stirred for 1 hour to prepare negative photosensitive composition 1 with a solid content of 15.00% by mass. Table 10 shows the blended mass of each raw material.

Negative photosensitive composition 1 was applied to the surface of Tempax using a spin coater with the rotation speed adjusted so that the thickness of the cured film after heating at 250° C. for 1 hour in a nitrogen atmosphere (described later) would be 1.50 μm. A coating film was obtained by performing a coating process. A prebaking process was performed in which the coated film was heated at 110° C. for 2 minutes under atmospheric pressure using a hot plate to obtain a prebaked film. An exposure step was carried out using the optimum exposure amount measured by the method described above, and a developing step was carried out in the same manner as in the measurement of the optimum exposure amount described above, to obtain a solid developed film. Next, substrates A and B for evaluating light-shielding properties were obtained in the same manner as in Example 1, and the thermal stability of the light-shielding properties was evaluated by the method described above. The evaluation results are shown in Table 11.

Next, a negative exposure mask (complete circular shielding portions with diameters of 10.0 μm, 9.0 μm, 8.0 μm, 7.0 μm, 6.0 μm, 5.0 μm, 4.0 μm, 3.0 μm, and 2.0 μm) The coating process, pre-bake process, exposure process, development process and curing process were carried out in the same manner as in the measurement of the optimum exposure dose described above, except that a hole pattern mask (with 50 hole pattern masks arranged each) was used, and the silver alloy film/ITO A resolution evaluation substrate having a cured film having a thickness of 1.50 μm and having hole-shaped openings on the ITO surface of a glass substrate having the film was obtained, and the resolution was evaluated using the method described above. The evaluation results are shown in Table 11.

(Comparative example 4)
In 20.64 g of cyclohexanone, 1.85 g of methacrylic resin solution H, 2.00 g of dipentaerythritol hexaacrylate which is a radical polymerizable compound, and 0.50 g of "Irgacure" (registered) which is a photopolymerization initiator. Trademark) 369 (manufactured by BASF; "Irgacure 369" in the table) was added and stirred for 30 minutes. Further, 25.01 g of dye dispersion 12 was added and stirred for 1 hour to prepare negative photosensitive composition 2 with a solid content of 20.00% by mass. Table 10 shows the blended mass of each raw material. Next, using the negative photosensitive composition 2, a resolution evaluation substrate was prepared in addition to the light-shielding evaluation substrates A and B in the same manner as in Comparative Example 3, and the thermal stability of the light-shielding property and the The resolution was evaluated. The evaluation results are shown in Table 11.

(Comparative example 5)
Negative photosensitive composition 3 was prepared with the amount shown in Table 10, and in addition to the light-shielding evaluation substrates A and B in the same manner as in Example 1, a resolution evaluation substrate was prepared. Table 11 shows the results of evaluating the thermal stability and resolution of .

(Preparation Example 13: Preparation of dye dispersion liquid 13)
In 360.00 g of a mixed solvent (PGME: ethyl lactate: GBL = mass ratio 50:30:20), which is component (d), 10.00 g of polyimide precursor B, which is component (b-1), and 14. 00g of Polybenzoxazole Precursor D was added and stirred for 30 minutes to dissolve. Furthermore, 16.00 g of perylene blue dye 6, which is a salt of components (a) and (f), was added and stirred for 30 minutes to dissolve it, thereby obtaining a pre-stirred liquid. Because the pre-stirred liquid contained a small amount of insoluble perylene blue dye 6, 0.05 mm diameter zirconia beads "Treceram (registered trademark)" (manufactured by Toray Industries, Inc.) were added to the vessel at a filling rate of 75% by volume. The pre-stirred liquid was sent to the vertical bead mill “Ultra Apex Mill (registered trademark)” (manufactured by Hiroshima Metal & Machinery Co., Ltd.) filled in the interior, and wet-processed for 30 minutes at a circumferential speed of 8 m/s using a circulation method. Performed media distribution processing. Filtration was performed using a filter with an opening diameter of 0.5 μm to obtain a dye dispersion liquid 13 with a solid content of 10.00% by mass. Table 12 shows the blended mass of each raw material.

(Preparation Examples 14 to 16: Preparation of dye dispersions 14 to 16)
Dye dispersions 14 to 16 were obtained in the same manner as in Preparation Example 13, except that Perylene Blue Dye 7, Perylene Blue Dye 8, and Perylene Blue Dye 9 were used in place of Perylene Blue Dye 6. Table 12 shows the blended mass of each raw material.

(Examples 11 to 13 and Example 27)
Positive photosensitive compositions 13 to 16 were prepared in the amounts shown in Table 13, and in addition to the light-shielding evaluation substrates A and B, a resolution evaluation substrate was prepared in the same manner as in Example 1. The thermal stability and resolution of light shielding properties were evaluated using the method. The results are shown in Table 14.

(Example 14)
A pixel dividing layer containing a cured film of positive photosensitive composition 1 and an organic EL display device including the pixel dividing layer were manufactured by the following method.
FIG. 3 shows a manufacturing process of an organic EL display device including a process of forming a pixel division layer.
A silver alloy (an alloy consisting of 99.00% by weight of silver and 1.00% by weight of copper) was deposited on the entire surface of an alkali-free glass substrate 12 measuring 70 mm in length and 70 mm in width by sputtering. Using an alkali-soluble novolak positive type resist, etching was performed by immersing it in a silver alloy etching solution at a liquid temperature of 30° C. to obtain a patterned silver alloy film 13 with a thickness of 50 nm. Furthermore, an ITO film (indium-tin oxide) was formed on the entire surface by sputtering. Using an alkali-soluble novolak positive resist, it was immersed in a 5% by weight oxalic acid aqueous solution at a temperature of 50°C for 5 minutes, washed with deionized water for 2 minutes, and then dried with air blow to form the same pattern with a film thickness of 10 nm. An ITO film 14 was obtained. Through the above steps, a first electrode-forming substrate having a first electrode formed of a laminated pattern of a silver alloy film/ITO film on the surface of an alkali-free glass substrate was obtained.

Positive photosensitive composition 1 is coated on the surface of the first electrode forming substrate using a spin coater, adjusting the rotation speed so that the thickness of the final pixel dividing layer is 1.50 μm. A coating film was obtained. Furthermore, the coated film was prebaked for 120 seconds at 110° C. under atmospheric pressure using a hot plate to obtain a prebaked film. The prebaked film was pattern-exposed to light through a positive exposure mask (a hole pattern mask having 200 perfectly circular transparent portions arranged) at the optimum exposure amount determined by the method described above to obtain an exposed film. Note that the opening width of the transparent part of the positive exposure mask is the same as the opening width when the resolution of various positive photosensitive compositions is obtained in the above-mentioned (2) resolution of cured film and evaluation of protruding foreign matter defects. I made sure that they were the same. That is, in the case of positive photosensitive composition 1, a hole pattern mask having a perfectly circular transparent portion having a diameter of 4.0 μm was used. Note that pattern exposure was performed by bringing a positive exposure mask into contact with the surface of the prebaked film. Next, development, rinsing and drying were performed in the same manner as in the evaluation of the optimum exposure amount to obtain a patterned developed film. The developed film was heated at 270° C. for 2 hours in a nitrogen atmosphere using a high-temperature inert gas oven to form a pixel dividing layer 15 having 200 openings in an area of 30 mm long/30 mm wide at the center of the first electrode forming substrate. A pixel division layer forming substrate was obtained.

Next, in order to form the organic EL layer 16 including the light-emitting layer in the opening of the pixel dividing layer ¹⁵ by vacuum evaporation, the pixel is The split layer forming substrate was rotated, and first, as a hole injection layer, a compound (HT-1) represented by formula (100) was added to a thickness of 10 nm, and as a hole transport layer, a compound (HT-1) represented by formula (101) was added to a thickness of 10 nm. -2) was formed into a film with a thickness of 50 nm. Next, a compound (GH-1) represented by formula (102) as a host material and a compound (GD-1) represented by formula (103) as a dopant material are placed on the light emitting layer to a thickness of 40 nm. Deposited. Next, a compound (ET-1) represented by formula (104) and a compound (LiQ) represented by formula (105) were laminated as electron transport materials at a volume ratio of 1:1 to a thickness of 40 nm.

Next, a compound (LiQ) was deposited to a thickness of 2 nm, and then a silver/magnesium alloy (volume ratio 10:1) was deposited to a thickness of 150 nm to form the second electrode 17. Next, a cap-shaped glass plate was adhered and sealed using an epoxy resin adhesive under a low humidity/nitrogen atmosphere to obtain an organic EL display device in which green light-emitting pixels were arranged. Note that each layer constituting the organic EL layer 16 is extremely thin compared to the pixel dividing layer described above, and a stylus-type film thickness measuring device cannot obtain high measurement accuracy. Each was measured using a type film thickness monitor, and the value obtained by rounding off the average value at three points within the plane to the first decimal place was taken as the film thickness. Table 15 shows the results of evaluating the resolution of the manufactured organic EL display device using the method described above.

(Examples 15 to 26 and Example 28)
An organic EL display device was produced in the same manner as in Example 14 using positive photosensitive compositions 2 to 10 and 13 to 16 instead of positive photosensitive composition 1, and the resolution of the organic EL display device was Table 15 shows the results evaluated by the method described above.

(Reference example 1)
2.75 g of polyimide precursor B was dissolved in 24.75 g of a mixed solvent (PGME: ethyl lactate: GBL = mass ratio 50:30:20), and further 22.50 g of pigment dispersion 11 was added. The mixture was stirred to prepare Reference Composition 1. Reference composition 1 is a composition that does not contain component (c) and does not have either negative or positive photosensitivity. Table 16 shows the blending amounts.

Next, a coating process was performed in which Reference Composition 1 was coated on the surface of Tempax by adjusting the rotation speed so that the prebaked film obtained after the prebaking process had a transmittance of 10% at a wavelength of 560 nm using a spin coater. A membrane was obtained. A prebaking process was performed in which the coated film was heated at 110° C. for 2 minutes under atmospheric pressure using a hot plate to obtain a prebaked film. The transmittance of the obtained prebaked film at a wavelength of 350 to 650 nm was measured using a spectrophotometer U-4100 (manufactured by Hitachi, Ltd.). The measurement results are shown by broken lines in the graph of FIG. In addition, when Reference Composition 1 was measured using a particle size distribution analyzer SZ-100 (manufactured by Horiba, Ltd.) based on the dynamic light scattering method, the particle size distribution was output. It was thought that it existed as a pigment in substance 1.

(Reference example 2)
Reference Composition 2 was prepared using Dye Dispersion 16 in place of Dye Dispersion 11 in the amounts shown in Table 16. Reference composition 2 is a composition that does not contain component (c) and does not have either negative or positive photosensitivity. A prebaked film was obtained using Reference Composition 2 in the same manner as in Reference Example 1, and the transmittance at a wavelength of 350 to 650 nm was measured. The measurement results are shown as a solid line in the graph of FIG. Comparison of Reference Example 1 and Reference Example 2 shows that Perylene Blue Pigment 9 has a relatively higher transmittance in the near ultraviolet region than Fine Perylene Pigment A when the transmittance at a wavelength of 560 nm is the same. It was considered to be a suitable coloring material for obtaining resolution. Furthermore, when Reference Composition 2 was measured using SZ-100 in the same manner as Reference Example 1, no particle components were detected, indicating that perylene blue dye 9 was completely dissolved in Reference Composition 2. It was thought to exist as a dye.

From the above results, the positive photosensitive compositions in Examples 1 to 13 and Example 27 are the same as the positive photosensitive compositions in Comparative Examples 1 to 2 and the negative photosensitive compositions in Comparative Examples 3 to 5. It can be seen that it is possible to form a cured film that has both high light-shielding thermal stability and high resolution while suppressing the occurrence of protruding foreign particle defects. Furthermore, it can be seen that the organic EL display device including the pixel dividing layer containing the cured film of the present invention has excellent resolution.

Therefore, it can be seen that the positive photosensitive composition, cured film, organic EL display device, and dye of the present invention are useful.

The positive photosensitive composition of the present invention is useful for applications requiring high light-shielding thermal stability and high resolution, and is useful in applications such as pixel dividing layers and TFT flattening layers of organic EL display devices, as well as micro LED displays. It can be preferably used as a material for forming a flattening layer for liquid crystal display devices, a black matrix for liquid crystal display devices, a black column spacer for liquid crystal display devices, a near-infrared transparent visible light shielding film for solid-state imaging devices, and the like. Among these, it can be particularly preferably used as a material for forming a pixel dividing layer and a TFT flattening layer included in an organic EL display device.

1: TFT
2: Wiring 3: TFT insulating layer 4: Flattening layer 5: First electrode 6: Substrate 7: Contact hole 8: Pixel division layer 9: Light-emitting pixel 10: Second electrode 11: Protruding foreign matter defect 12: Alkali-free glass Substrate 13: Silver alloy film 14: ITO film 15: Pixel division layer 16: Organic EL layer 17: Second electrode

Claims

A positive material containing (a) a compound represented by formula (1) and/or a compound represented by formula (2), (b) a resin, (c) a photoacid generator, and (d) an organic solvent. type photosensitive composition.

(In formula (1), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently represent a hydrogen atom, -SO 3 H, -SO 3 - , carbon Represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, -CF 3 , -F, -Br or -CN.However, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 , the total number of -SO 3 H and -SO 3 - is 1 to 4.
R 9 , R 10 , R 11 and R 12 each independently represent a hydrogen atom, -OH, -F, -Br, -CN or an alkoxy group having 1 to 5 carbon atoms. However, R 9 and R 10 and R 11 and R 12 may each independently be bonded to each other to form a linking group -X 1 -. -X 1 - represents -O- or -SO 2 -.
In formula (2), R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 each independently represent a hydrogen atom, -SO 3 H, -SO 3 - , carbon number Represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, -CF 3 , -F, -Br or -CN. However, the total number of -SO 3 H and -SO 3 - in R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 is 1 to 4.
R 21 , R 22 , R 23 and R 24 each independently represent a hydrogen atom, -OH, -F, -Br, -CN or an alkoxy group having 1 to 5 carbon atoms. However, R 21 and R 22 and R 23 and R 24 may each independently be bonded to each other to form a linking group -X 2 -. -X 2 - represents -O- or -SO 2 -. )
The positive photosensitive composition according to claim 1, wherein the component (a) contains a compound represented by formula (5) and/or a compound represented by formula (6).

(In formula (5), R 25 and R 26 each independently represent -SO 3 H or -SO 3 - . n 1 and n 2 are integers and each independently represent 0 to 2. However, the total number of n 1 and n 2 is 1 to 4.
In formula (6), R 27 and R 28 each independently represent -SO 3 H or -SO 3 - . n 3 and n 4 are integers and each independently represents 0 to 2. However, the total number of n 3 and n 4 is 1 to 4. )
The positive photosensitive composition according to claim 1 or 2, further comprising (f) a compound represented by formula (70).

(In formula (70), R 81 represents N + or P + . R 82 , R 83 , R 84 and R 85 each independently have a carbon number of 1 which may be substituted with -OH or a phenyl group. ~20 alkyl group, phenyl group, or hydrogen atom.However, when R 81 is N + , the total number of hydrogen atoms in R 82 , R 83 , R 84 and R 85 is 0 to 2, When R 81 is P + , the total number of hydrogen atoms in R 82 , R 83 , R 84 and R 85 is 0.)
The (b) resin contains (b-1) a phenolic hydroxyl group-containing resin, and the (b-1) phenolic hydroxyl group-containing resin contains a polyimide, a polyimide precursor, a polybenzoxazole precursor, and a copolymer thereof. The positive photosensitive composition according to claim 1 or 2, which contains at least one resin selected from the group consisting of:
1 or 2, further comprising (e) at least one compound selected from the group consisting of a compound represented by formula (30), a compound represented by formula (31), and a compound having a triphendioxazine skeleton. 2. The positive photosensitive composition according to 2.

(In formula (30) and formula (31), R 61 , R 62 , R 63 , R 64 , R 65 , R 66 , R 67 and R 68 each independently represent a hydrogen atom, -F, or a carbon number of 1 ~3 alkyl group or an alkoxy group having 1 to 3 carbon atoms.)
The (c) photoacid generator is (c-1) a compound having two or more groups represented by formula (22) in the molecule and a phenolic hydroxyl group, and a compound represented by formula (23). Compounds having two or more groups in the molecule and having a phenolic hydroxyl group, and compounds having a group represented by formula (22) and a group represented by formula (23) and having a phenolic hydroxyl group 3. The positive photosensitive composition according to claim 1, comprising at least one compound selected from the group consisting of.

(In formula (22), R 54 , R 55 , R 56 and R 57 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. * is a bond (Represents the part.)
(In formula (23), R 58 , R 59 and R 60 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. * represents a bonding site. .)
Component (d) contains (d-1) an organic solvent having a hydroxyl group, and the content of component (d-1) is 50% by mass or more based on 100% by mass of component (d). 3. The positive photosensitive composition according to 1 or 2.
A cured film containing a cured product of the positive photosensitive composition according to claim 1 or 2.
An organic EL display device comprising a pixel dividing layer and a planarization layer,
An organic EL display device, wherein the pixel dividing layer and/or the planarization layer contain the cured film according to claim 8.
(f) A dye containing, in addition to the compound represented by formula (70), (a) a compound represented by formula (85) and/or a compound represented by formula (86).

(In formula (70), R 81 represents N + or P + . R 82 , R 83 , R 84 and R 85 each independently have a carbon number of 1 which may be substituted with -OH or a phenyl group. ~20 alkyl group, phenyl group, or hydrogen atom.However, when R 81 is N + , the total number of hydrogen atoms in R 82 , R 83 , R 84 and R 85 is 0 to 2, When R 81 is P + , the total number of hydrogen atoms in R 82 , R 83 , R 84 and R 85 is 0.
In formula (85), R 91 , R 92 , R 93 , R 94 , R 95 , R 96 , R 97 and R 98 each independently represent a hydrogen atom, -SO 3 H, -SO 3 - , carbon number Represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, -CF 3 , -F, -Br or -CN. However, in R 91 , R 92 , R 93 , R 94 , R 95 , R 96 , R 97 and R 98 , the total number of -SO 3 H and -SO 3 - is 1 to 4, and at least one -SO 3 - .
R 99 , R 100 , R 101 and R 102 each independently represent a hydrogen atom, -OH, -F, -Br, -CN or an alkoxy group having 1 to 5 carbon atoms. However, R 99 and R 100 and R 101 and R 102 may each independently be bonded to each other to form a linking group -X 3 -. -X 3 - represents -O- or -SO 2 -.
In formula (86), R 103 , R 104 , R 105 , R 106 , R 107 , R 108 , R 109 and R 110 each independently represent a hydrogen atom, -SO 3 H, -SO 3 - , carbon number Represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, -CF 3 , -F, -Br or -CN. However, in R 103 , R 104 , R 105 , R 106 , R 107 , R 108 , R 109 and R 110 , the total number of -SO 3 H and -SO 3 - is 1 to 4, and at least one -SO 3 - .
R 111 , R 112 , R 113 and R 114 each independently represent a hydrogen atom, -OH, -F, -Br, -CN or an alkoxy group having 1 to 5 carbon atoms. However, R 111 and R 112 and R 113 and R 114 may each independently be bonded to each other to form a linking group -X 4 -. -X 4 - represents -O- or -SO 2 -. )