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

Abstract

Provided is a positive photosensitive composition which is capable of suppressing the occurrence of foreign matter defects on the surface of an opening, has high thermal stability with respect to light shielding properties, and is capable of forming a high-resolution pixel division layer and / or planarization layer. The present invention is a positive photosensitive composition 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. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a positive photosensitive composition, a cured film, an organic EL display device and a pigment. Background Art

[0002] The further high functionality of a display device equipped with a flexible organic electroluminescent (EL) display is being studied. In the past, by setting a structure without a polarizing plate arranged in the front part of the display, the loss of brightness is eliminated, and it is expected to reduce power consumption. In order to replace the function of the polarizing plate, it is necessary to add a function of suppressing the reflection of external light such as sunlight, and the technology of giving light-shielding properties to the pixel segmentation layer and / or the planarization layer having the function of an insulating layer and forming a pattern using photolithography has attracted attention. As a pixel segmentation layer with light-shielding properties, for example, a black pixel segmentation layer, also called a black pixel definition film or a black embankment, can be cited. The black pixel segmentation layer is used to separate and configure the light-emitting pixels of each color such as red, green, and blue arranged in the opening. On the other hand, the planarization layer is configured as a base layer that enables the electrode and the black pixel segmentation layer to be smoothly formed, so as to cover the convex step difference caused by the TFT (Thin Film Transistor).

[0003] In recent years, in order to improve the display quality of organic EL displays, in small displays such as watch-type display devices, the light-emitting pixels are formed smaller and highly refined. In this regard, it is required to improve the resolution of the black pixel segmentation layer. In addition, in order to obtain high uniformity of light shielding properties in the surface even if there is a part that becomes high temperature locally in the oven during the curing process, it is required to improve the thermal stability of the light shielding properties of the black pixel segmentation layer. On the other hand, when the planarization layer is blackened, from the same point of view, it is also required to improve the resolution and improve the thermal stability of the light shielding properties.

[0004] As materials for forming a black pixel segmentation layer, a variety of photosensitive compositions containing non-carbon black color materials to replace carbon black, which has fatal defects in electrical properties such as low insulation and high dielectric constant, have been proposed. For example, Patent Documents 1, 2, and 3 disclose positive photosensitive compositions containing a black dye containing an azo chromium complex, namely CI Solvent Black 27, 29, or 34. Patent Document 4 discloses a positive photosensitive composition containing a salt-forming compound containing an acid dye and a basic dye. Patent Document 5 discloses a negative photosensitive composition containing a benzodifuranone-based black pigment. Patent Document 6 discloses a negative photosensitive composition containing a phthalocyanine compound having a basic functional group, an organic blue pigment, an organic violet pigment, and an organic yellow pigment.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: International Publication No. 2017 / 069172

[0008] Patent Document 2: International Publication No. 2021 / 246448

[0009] Patent Document 3: International Publication No. 2021 / 246444

[0010] Patent Document 4: International Publication No. 2022 / 039034

[0011] Patent Document 5: Japanese Patent Application Publication No. 2022-38599

[0012] Patent Document 6: Japanese Patent Application Publication No. 2019-207306 Summary of the invention

[0013] Problems to be solved by the invention

[0014] However, when using the positive photosensitive compositions disclosed in Patent Documents 1, 2, and 3, although it is easy to obtain a pixel segmentation layer and / or a planarization layer with high light-shielding thermal stability, on the other hand, it is generally known that black dyes containing azo chromium complexes such as CI Solvent Black 27, 29, or 34 may generate highly toxic hexavalent chromium due to high-temperature treatment. Therefore, there are problems from the perspectives of human safety and environmental protection. In addition, the positive photosensitive composition disclosed in Patent Document 4 has the problem of insufficient light-shielding thermal stability. The negative photosensitive composition disclosed in Patent Document 5 has the problem of insufficient resolution. The negative photosensitive composition disclosed in Patent Document 6 has the following problem: due to the high-temperature treatment usually performed when forming the pixel segmentation layer, protruding foreign matter defects will be generated on the surface of the opening.

[0015] Therefore, there is a strong demand for a photosensitive composition containing a color material having no chromium atom in the molecule, which can suppress the generation of protruding foreign matter defects on the surface of the opening, has high thermal stability of light-shielding properties, and can form a high-resolution pixel segmentation layer and / or planarization layer.

[0016] Means for solving problems

[0017] In order to solve the above problems, the positive photosensitive composition of the present invention has the following structure. That is,

[0018] (a) A positive photosensitive composition comprising 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.

[0019] [Chemical formula 1]

[0020]

[0021] In formula (1), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each independently represents a hydrogen atom, -SO3H, -SO3 - , an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, -CF3, -F, -Br or -CN. 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 In -SO3H and -SO3 - The total number is 1 to 4.

[0022] R 9 , R 10 , R 11 and R 12 Each independently represents a hydrogen atom, -OH, -F, -Br, -CN or an alkoxy group having 1 to 5 carbon atoms. 9 With R 10 , R 11 With R 12 Each independently optionally bonded to each other to form a linking group -X 1 -.-X 1 - represents -O- or -SO2-.

[0023] [Chemical formula 2]

[0024]

[0025] In formula (2), R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 Each independently represents a hydrogen atom, -SO3H, -SO3 - , an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, -CF3, -F, -Br or -CN. 13 , R 14 , R 15 , R 16 , R 17, R 18 , R 19 and R 20 In -SO3H and -SO3 - The total number is 1 to 4.

[0026] R 21 , R 22 , R 23 and R 24 Each independently represents a hydrogen atom, -OH, -F, -Br, -CN or an alkoxy group having 1 to 5 carbon atoms. 21 With R 22 , R 23 With R 24 Each independently optionally bonded to each other to form a linking group -X 2 -.-X 2 - represents -O- or -SO2-.

[0027] Effects of the Invention

[0028] According to the present invention, generation of foreign matter defects on the surface of the opening can be suppressed, the thermal stability of light-shielding properties is high, and a high-resolution pixel division layer and / or planarization layer can be formed. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] [ Figure 1 ] Figure 1 It is a cross-sectional view of a TFT substrate in an organic EL display device including a pixel dividing layer and a planarizing layer as a specific example of an embodiment of the present invention.

[0030] [ Figure 2 ] Figure 2 This is a scanning electron microscope (SEM) image of the protrusion-shaped foreign matter defect observed in Comparative Example 4.

[0031] [ Figure 3 ] Figure 3 This is a process for manufacturing an organic EL display device including a process for forming a pixel division layer in all the embodiments.

[0032] [ Figure 4 ] Figure 4 This is a graph comparing the transmittance (%) of the prebaked film obtained in Reference Example 1 (dashed line) and the prebaked film obtained in Reference Example 2 (solid line) in the wavelength range of 350 to 650 nm. DETAILED DESCRIPTION

[0033] The present invention is described in detail below. The numerical range represented by "~" refers to a range that includes the numerical values ​​recorded before and after "~" as the lower limit and upper limit. The pixel division layer refers to the pixel division layer possessed by the organic EL display device, and does not include the black matrix of the liquid crystal display device. Visible light refers to the light in the region with a wavelength of more than 380nm and less than 780nm, and near ultraviolet light refers to the light in the region of more than 200nm and less than 380nm. Near infrared light refers to the light in the region with a wavelength of more than 780nm and less than 1300nm.

[0034] The so-called light shielding refers to the function of reducing the intensity of transmitted light relative to the intensity of light incident on the cured film in the vertical direction, and the so-called light shielding property refers to the degree of shielding visible light. Transmittance refers to light transmittance. The so-called weight average molecular weight (Mw) refers to the value obtained by analyzing by gel permeation chromatography (GPC) using tetrahydrofuran as a carrier and converting it using a standard curve based on standard polystyrene.

[0035] "CI" used in the names of some coloring materials is the abbreviation of Colour Index Generic Name, which is based on the Dye Index published by The Society of Dyers and Colourists. For coloring materials registered in the Dye Index, Colour Index Generic Name indicates the chemical structure and crystal form of the pigment or dye. Solid content refers to the proportion (mass %) of the components other than organic solvent and water in the positive photosensitive composition.

[0036] The inventors of the present application have conducted intensive studies and found that a composition using a color material having a specific chemical structure as a component for imparting light-shielding properties and further combining a resin and a photoacid generator to impart positive photosensitivity has a particularly significant effect in solving the above-mentioned problems.

[0037] That is, the positive photosensitive composition of the present invention is a positive photosensitive composition 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.

[0038] [Chemical formula 3]

[0039]

[0040] In formula (1), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R8 Each independently represents a hydrogen atom, -SO3H, -SO3 - , an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, -CF3, -F, -Br or -CN. 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 In -SO3H and -SO3 - The total number is 1 to 4.

[0041] R 9 , R 10 , R 11 and R 12 Each independently represents a hydrogen atom, -OH, -F, -Br, -CN or an alkoxy group having 1 to 5 carbon atoms. 9 With R 10 , R 11 With R 12 Each independently optionally bonded to each other to form a linking group -X 1 -.-X 1 - represents -O- or -SO2-.

[0042] [Chemical formula 4]

[0043]

[0044] In formula (2), R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 Each independently represents a hydrogen atom, -SO3H, -SO3 - , an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, -CF3, -F, -Br or -CN. 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 In -SO3H and -SO3 - The total number is 1 to 4.

[0045] R 21 , R 22 , R23 and R 24 Each independently represents a hydrogen atom, -OH, -F, -Br, -CN or an alkoxy group having 1 to 5 carbon atoms. 21 With R 22 , R 23 With R 24 Each independently optionally bonded to each other to form a linking group -X 2 -.-X 2 - represents -O- or -SO2-.

[0046] The positive photosensitive composition of the present invention contains (a) a compound represented by the formula (1) and / or a compound represented by the formula (2) (hereinafter, sometimes referred to as component (a)).

[0047] Component (a) has the effect of providing light shielding properties to the pixel segmentation layer and / or planarization layer finally obtained. Component (a) is a polycyclic aromatic sulfonic acid having a skeleton of perylene-3,4,9,10-tetracarboxylic acid bisbenzimidazole (hereinafter sometimes referred to as PTCBI) and having 1 to 4 sulfonic groups substituted on the carbon atoms of the benzene rings in the two benzimidazole structures. The sulfonic group referred to here refers to -SO3H and -SO3 formed by proton dissociation. - The PTCBI skeleton refers to the meaning of the skeleton of the cis-isomer represented by formula (3) and the skeleton of the trans-isomer represented by formula (4), and exhibits high light-shielding properties by having two benzimidazole skeletons in the molecule. It should be noted that in order to facilitate understanding of the synthesis method for obtaining component (a) described later, the position numbers of some of the carbon atoms in the carbon atoms constituting the perylene ring are recorded in formula (3) and formula (4).

[0048] [Chemical formula 5]

[0049]

[0050] In the positive photosensitive composition, the presence form of the component (a) in the pixel segmentation layer and the planarization layer is not particularly limited, and it can be dispersed in the form of insoluble particles, or it can be dissolved. That is, the component (a) can be a pigment or a dye, and they can exist as a mixture. The presence form of the component (a) can usually be controlled by adjusting 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 to adjust the solubility in the organic solvent (d). In addition, it can be controlled by selecting the resin (b) and the organic solvent (d) according to the chemical structure of the component (a).

[0051] (a) component can be -SO3 -The salt is formed, and the solubility in the (d) organic solvent can be improved by forming a salt. As the form of the salt, for example, + , K + , Li + Salts formed by monovalent metal cations, Ca 2+ , Mn 2 + , Sr 2+ , Ba 2+ 、Zn 2+ 、Al 3+ The invention relates to salts formed with polyvalent metal cations such as chlorinated blue, chlorinated blue, etc., salts formed with the cationic site of cationic dyes such as CI basic blue 3 and 22, and salts formed with organic cations such as trialkylbenzylammonium cations and tetraalkylammonium cations. Among them, from the aspect of improving resolution, component (a) as an anionic compound preferably forms a salt with component (f) as a cationic compound described later. When a salt is formed, it is defined as a mixture of component (a) and other components.

[0052] However, when a high polarity functional group such as a sulfonic group or an amino group is introduced into the molecular structure of an organic pigment, the crystallinity is usually impaired. Compared with the organic pigment before the introduction of the high polarity functional group, it is not only easy to reduce the thermal stability and produce protruding foreign body defects caused by crystal growth, but also it will become a dark hue and reduce the near ultraviolet transmittance, which is widely known as the technical common sense of those skilled in the art. In contrast, with regard to component (a), regardless of which of the aforementioned forms of existence, even if a sulfonic group is introduced into the PTCBI skeleton, it is possible to suppress the generation of protruding foreign body defects such as protrusions under high temperature treatment (for example, 250 to 270°C) in the curing process described later, and obtain excellent light-shielding thermal stability. If protruding foreign body defects are generated on the surface of the opening of the pixel segmentation layer or the planarization layer, it is difficult to realize the lighting of the luminous pixel. Therefore, the more the generation of protruding foreign body defects is suppressed, the more ideal it is.

[0053] In addition, the sulfonic group of component (a) has a large steric volume, which has the effect of alleviating the strong intermolecular stacking from the PTCBI skeleton. Therefore, compared with PTCBI derivatives substituted with substituents other than the sulfonic group (hereinafter, sometimes referred to as PTCBI derivatives) and unsubstituted PTCBI, component (a) has both improved near-ultraviolet transmittance and equivalent light-shielding properties. Therefore, component (a) can better improve the reaction rate of the photoacid generator (c) in the exposure process described later, and increase the amount of acid generated in the film.

[0054] Furthermore, by providing the component (a) with a sulfonic group, self-dispersibility and / or high solubility in an alkaline developer can be suitably imparted in the development step described later, and generation of development residues can be suitably suppressed.

[0055] Based on the above principles, due to the characteristic chemical structure of component (a), the thermal stability of the light-shielding property is high, and a high-resolution pixel segmentation layer and / or planarization layer can be formed. The high thermal stability of the light-shielding property referred to here means that the change in the light-shielding property is small relative to the change in the heating temperature in the curing process. In addition, the change in the light-shielding property after the obtained pixel segmentation layer and / or planarization layer is heated again is small. On the other hand, the so-called high resolution refers to the narrow opening width of the opening. The size of the luminous pixel in the display area of ​​the organic EL display device is determined by the opening width of the opening of the pixel segmentation layer. The smaller the size of the luminous pixel, the more high-precision and high-quality display can be obtained. Therefore, the higher the resolution of the pixel segmentation layer, the better. In addition, in terms of panel composition, if the pixel segmentation layer has a high resolution, the planarization layer also needs a high resolution. Therefore, the higher the resolution of the planarization layer, the better.

[0056] Component (a) is a pigment having a maximum absorption wavelength in the region of 550 to 650 nm and being dark blue, and has different optical properties from PTCBI and PTCBI derivatives, which are pigments having a maximum absorption wavelength in the region of 480 to 540 nm and being dark purple. The pre-baked film of the positive photosensitive composition of the present invention containing component (a) has a higher maximum transmittance at 800 to 1,200 nm than the maximum transmittance in the region of 450 to 650 nm, which has high relative visibility and contributes greatly to light-shielding properties. Therefore, near-infrared alignment (which uses a near-infrared camera to automatically align the exposure mask with the electrode-forming substrate) can be used to obtain high positional accuracy and high productivity while having high light-shielding properties.

[0057] In the positive photosensitive composition of the present invention, the component (a) preferably contains a compound represented by formula (5) and / or a compound represented by formula (6) from the viewpoint of improving heat stability of light-shielding properties and resolution.

[0058] [Chemical formula 6]

[0059]

[0060] In formula (5), R 25 and R 26 Each independently represents -SO3H or -SO3 - .n 1 and n 2 is an integer, each independently representing 0 to 2. 1 and n 2 The total number is 1 to 4.

[0061] [Chemical formula 7]

[0062]

[0063] In formula (6), R 27 and R 28 Each independently represents -SO3H or -SO3 - .n 3 and n 4 is an integer, each independently representing 0 to 2. 3 and n 4 The total number is 1 to 4.

[0064] Specific examples of the component (a) contained in the positive photosensitive composition of the present invention include compounds represented by formula (7), compounds represented by formula (8), compounds represented by formula (9), compounds represented by formula (10), compounds represented by formula (11), compounds represented by formula (12), compounds represented by formula (13), compounds represented by formula (14), compounds represented by formula (15), compounds represented by formula (16), and a group of compounds corresponding to cis-isomers of these compounds.

[0065] [Chemical formula 8]

[0066]

[0067] [Chemical formula 9]

[0068]

[0069] [Chemical formula 10]

[0070]

[0071] [Chemical formula 11]

[0072]

[0073] Examples of the synthesis method for obtaining the component (a) include the first method and the second method described below.

[0074] As a first method, the following method can be cited: 1,2-diaminobenzene and / or a 1,2-diaminobenzene derivative in which the carbon atoms constituting the benzene ring are substituted with a substituent other than a sulfonic group is reacted with perylene-3,4,9,10-tetracarboxylic dianhydride (hereinafter, sometimes abbreviated as PTCDA) or a perylene-3,4,9,10-tetracarboxylic dianhydride derivative in which the carbon atoms constituting the perylene ring are substituted with a substituent other than a sulfonic group (hereinafter, sometimes abbreviated as a PTCDA derivative), and the obtained product is sulfonated to introduce a sulfonic group, thereby obtaining component (a).

[0075] Examples of the 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, and 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-pentyloxyperylene-3,4,9,10-tetracarboxylic dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride monosulfone, perylene-3,4,9,10-tetracarboxylic dianhydride disulfone. For example, commercially available products manufactured by Henan Tianfu Chemical Co., Ltd. can be used for these PTCDA derivatives. In addition, the method for obtaining the PTCDA derivative can refer to the synthesis method disclosed in, for example, International Publication No. 97 / 22607, Japanese Patent Application Publication No. 2018-165257, International Publication No. 2007 / 554787, and International Publication No. 2007 / 093643.

[0076] Examples of the 1,2-diaminobenzene derivative 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-phenylenediamine, 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, and 3,5-bis(trifluoromethyl)-1,2-phenylenediamine (all manufactured by Sigma-Aldrich Co.). One species or two or more species may be used in combination.

[0077] In addition, as a simpler method, the sulfonic group can be introduced by sulfonating the cis-isomer / trans-isomer mixture of PTCBI to obtain component (a). The cis-isomer / trans-isomer mixture of PTCBI can use commercial products. As commercial products, for example, "Spectrasense (registered trademark)" Black K0087 (manufactured by Color & Effect Co., Ltd.), perylene-3,4,9,10-tetracarboxylic acid bisbenzimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.), and PTCBI (manufactured by Luminescence Technology Corporation) can be cited.

[0078] The second method is to react a sulfo-substituted 1,2-diaminobenzene derivative with PTCDA (or a PTCDA derivative) to obtain component (a). Examples of the sulfo-substituted 1,2-diaminobenzene derivative include 1,2-diamino-4-sulfonic acid and 1,2-diamino-3-sulfonic acid.

[0079] The method for obtaining the component (a) will be described in more detail by taking the above-mentioned first method as an example.

[0080] Phenol melted at 70 to 100°C is used as a solvent, PTCDA (or a PTCDA derivative) and 1,2-diaminobenzene (or a 1,2-diaminobenzene derivative) as starting materials are added at a molar ratio of 1:2 to 1:2.5, and a basic catalyst such as piperazine is further added. The obtained mixture is stirred at a liquid temperature of 140 to 200°C for 6 to 10 hours to allow the reaction to proceed sufficiently, and then the generated water is distilled and separated in the form of an azeotropic mixture with phenol. Pyridine can be used instead of the solvent and the basic catalyst. Cool to 100°C, add ethanol, stir at 50 to 70°C for 1 to 3 hours, and then filter and separate. Furthermore, wash with ethanol and then with water until the filtrate becomes transparent, and dry at 40 to 80°C under reduced pressure for more than 24 hours to obtain PTCBI (or a PTCBI derivative). Generally, PTCBI (or a PTCBI derivative) can be obtained as a mixture containing 30 to 70% by mass of the trans isomer relative to 100% by mass of the total of the cis isomer and the trans isomer. If necessary, either the cis isomer or the trans isomer can be separated and obtained by chromatography.

[0081] Next, a sulfonation reaction is carried out. A mixture obtained by dissolving PTCBI (or a PTCBI derivative) in 10 to 70% by mass fuming sulfuric acid is heated, adjusted within the range of a liquid temperature of 40 to 150°C, and stirred for 3 to 15 hours. Next, it is put into water, preferably ice water, of a mass of 100 times or more relative to the aforementioned starting material to obtain a slurry containing a precipitate, which is filtered and separated. Next, until the residual amount of sulfate ions quantitatively determined by ion chromatography is less than 100 mass ppm, it is repeatedly washed with a mixed solution of ethanol and water, then washed with water, and then dried under reduced pressure at 60 to 80°C. Finally, the dry agglomeration is disintegrated by dry pulverization using a hammer mill or a jet mill to obtain a powdery component (a). The distribution of the number of sulfonic groups introduced per molecule of the target product can be controlled by the liquid temperature and reaction time corresponding to the concentration of fuming sulfuric acid, and the reaction can also be carried out in multiple stages as needed. After washing the obtained product, it can be purified by silica gel chromatography as needed to improve the purity of component (a) into which the number of sulfonic groups introduced is within a specific range. Liquid chromatography-mass spectrometry (LC-MS) can be used to conveniently monitor the molecular weight and purity corresponding to the chemical structure.

[0082] In addition, as a method for obtaining a salt of component (a) and a metal cation, for example, the following method can be cited: after adding component (a) to water, dissolving it under alkaline conditions while stirring, adding Na hydroxide or the like; + Source, potassium hydroxide, etc. + Source, aluminum chloride, etc. 3+ Source, barium chloride, etc. 2+ Source, or calcium chloride etc. Ca 2+ The source is heated at 30 to 60°C and stirred for 1 to 5 hours to form a salt, which is then separated, purified, dried and dry-pulverized.

[0083] On the other hand, as the method for obtaining the salt of (a) component and (f) component described later, for example, following method can be enumerated: after (a) component is added in water and organic solvent, stirring, adding secondary amine, tertiary amine, quaternary ammonium salt and / or phosphonium salt corresponding to the structure of target salt as the source of (f) component, stirring for 1 to 6 hours and forming salt at 30 to 90 ℃ of heating, separation, purification, drying and dry pulverization are processed. In addition, from the aspect of obtaining higher yield, it is also possible to replace (a) component and use the salt of (a) component and metal cation as raw material, by carrying out cation exchange with the source of (f) component and obtain. The operation of separation and purification of the salt comprising (a) component, for example, can be suitably applied to the common means such as decantation, decompression distillation, filter press and silica gel chromatography.

[0084] In the case where the positive photosensitive composition of the present invention contains at least a portion of the component (a) in the form of a pigment, from the perspective of improving resolution, the average primary particle size of the component (a) in the form of a pigment is preferably 10 nm or more, more preferably 30 nm or more. From the same point of view, it is preferably 300 nm or less, more preferably 150 nm or less. The average primary particle size referred to here refers to the number average of the primary particle size calculated by the particle size measurement method using an image analysis type particle size distribution measuring device. The image can be taken using a transmission electron microscope (TEM), and more than 100 primary particles of the component (a) can be photographed under a magnification of 50,000 times, and 50 primary particles randomly selected from the obtained image are analyzed to calculate the average primary particle size. In the case where the component (a) is not a perfect sphere, the average value of its major diameter and minor diameter is used as the primary particle size. In the image analysis, the image analysis type particle size distribution software Mac-View (Mountech; in accordance with JIS8827-1; particle size analysis-image analysis method) can be used.

[0085] As for the chemical structure of the component (a), the positive photosensitive composition of the present invention can be used as a sample, and a known method such as matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS), time of flight secondary ion mass spectrometry (TOF-SIMS), time of flight mass spectrometry (TOF-MS), liquid chromatography / electric field Fourier transform mass spectrometry (LC-FT-MS), nuclear magnetic resonance analysis (NMR), liquid chromatography mass spectrometry (LC-MS), infrared absorption spectroscopy and X-ray diffraction can be appropriately combined for analysis. In the case where the component (a) is present in the form of a pigment, its presence can be detected using a particle size distribution measuring device based on a dynamic light scattering method. A concentrate obtained by centrifuging the positive photosensitive composition, or a substance obtained by further dissolving it in an amide solvent described later, can be used as a sample to improve the accuracy of the analysis.

[0086] In order to obtain high light-shielding properties, the content of component (a) in 100% by mass of the solid content of the positive photosensitive composition is preferably 5% by mass or more, more preferably 10% by mass or more. In order to improve the resolution, it is preferably 40% by mass or less, more preferably 30% by mass or less.

[0087] From the perspective of obtaining high light-shielding properties and improving resolution, the positive photosensitive composition of the present invention preferably further contains a compound (f) represented by formula (70) (hereinafter, sometimes referred to as component (f)). In the positive photosensitive composition, the presence form of component (f) in the pixel segmentation layer and the planarization layer is not particularly limited, and it is preferred that at least a portion of component (f) forms a salt with component (a).

[0088] [Chemical formula 12]

[0089]

[0090] In formula (70), R 81 N + or P + . R 82 , R 83 , R 84 and R 85 Each independently represents an alkyl group having 1 to 20 carbon atoms, a phenyl group or a hydrogen atom which is optionally substituted with -OH or a phenyl group. 81 N + In the case of R 82 , R 83 , R 84 and R 85 The total number of hydrogen atoms is 0 to 2, R 81 P + In the case of R 82 , R 83 , R 84 and R 85 The total number of hydrogen atoms is 0.

[0091] R 81 N + In the case of + In the case of , it means that the component (f) has a phosphonium cation.

[0092] It should be noted that in formula (70), R 81 N + In the case of R 82 , R 83 , R 84 and R 85 In the formula, the total number of hydrogen atoms is 0 to 2, which means R 82 , R 83 , R 84 and R 85 One or two of the 81 The hydrogen atoms bonded to R 81 The hydrogen atom referred to herein as a bonded hydrogen atom does not refer to a hydrogen atom contained in an alkyl group having 1 to 20 carbon atoms which is optionally substituted with -OH or a phenyl group, or a phenyl group. 81 P + In the case of R 82 , R 83 , R 84 and R 85 In the above, the total number of hydrogen atoms is 0, which also means that R 82 , R83 , R 84 and R 85 Neither 81 Bonded hydrogen atoms.

[0093] In addition, in formula (70) and formula (71), the alkyl group having 1 to 20 carbon atoms which may be substituted with -OH or phenyl includes, for example, unsubstituted methyl (-CH3), methyl group substituted with one -OH (-CH2OH), methyl group substituted with one phenyl (i.e., benzyl), etc. In the case of substitution with -OH or phenyl, the number of substitutions in the alkyl group having 1 to 20 carbon atoms is preferably 1 from the viewpoint of resolution.

[0094] The component (f) preferably has an alkyl group having 1 to 15 carbon atoms which is optionally substituted with -OH or phenyl and has at least one unsubstituted alkyl group having 1 to 15 carbon atoms from the viewpoint of improving resolution.

[0095] That is, in the positive photosensitive composition of the present invention, it is more preferred that the component (f) contains a compound represented by the formula (71).

[0096] [Chemical formula 13]

[0097]

[0098] In formula (71), R 86 N + or P + . R 87 , R 88 , R 89 and R 90 Each independently represents an alkyl group having 1 to 15 carbon atoms which is optionally substituted with -OH or phenyl. 87 , R 88 , R 89 and R 90 At least one of R is an unsubstituted alkyl group having 1 to 15 carbon atoms. 86 N + In the case of (f), it means that the component has an ammonium cation, which is P + In the case of , it means that the component (f) has a phosphonium cation.

[0099] From the perspective of improving resolution, it is further preferred that R 86 N + , R 87 , R 88 , R 89 and R 90 It is an unsubstituted alkyl group having 1 to 15 carbon atoms.

[0100] Specific examples of the compound belonging to the component (f) and the preferred raw material compounds for obtaining the same are given below, but the examples are not limited thereto. Commercial products of the raw material compounds can be obtained from Tokyo Chemical Industry Co., Ltd. and Sigma-Aldrich Co., Ltd.

[0101] In formula (70), as R 81 N + , and R 82 , R 83 , R 84 and R 85 Middle and R 81 Specific examples of component (f) in which the total number of bonded hydrogen atoms is 1 or 2 include compounds represented by formula (72) derived from 2-(dodecylamino)ethanol, etc., compounds represented by formula (73) derived from bis(2-ethylhexyl)amine, etc., compounds represented by formula (74) derived from tri-n-octylamine, etc., compounds represented by formula (75) derived from stearyldiethanolamine, etc., and compounds represented by formula (76) derived from 2-diethylaminoethanol, etc.

[0102] [Chemical formula 14]

[0103]

[0104] In formula (70), as R 81 N + , and R 82 , R 83 , R 84 and R 85 Zhong and R 81 Specific examples of component (f) in which the total number of bonded hydrogen atoms is 0 include compounds represented by formula (77) derived from benzyldodecyldimethylammonium chloride, etc., compounds represented by formula (78) derived from tetraethylammonium bromide, etc., compounds represented by formula (79) derived from trimethylphenylammonium bromide, etc., compounds represented by formula (80) derived from tetrabutylammonium bromide, etc., and compounds represented by formula (81) derived from tri(dodecyl)methylammonium chloride, etc.

[0105] [Chemical formula 15]

[0106]

[0107] In formula (70), as R 81 P + Specific examples of the component (f) include compounds represented by formula (82) derived from tetrabutylphosphonium bromide, etc., compounds represented by formula (83) derived from tributylhexylphosphonium bromide, etc., and compounds represented by formula (84) derived from tetrakis(hydroxymethyl)phosphonium sulfate, etc.

[0108] [Chemical formula 16]

[0109]

[0110] These (f) components may be contained alone or in combination of two or more.

[0111] In the positive photosensitive composition, the -SO3H and -SO3 - When the total is set to 100 mol%, from the perspective of improving resolution, the content of component (f) is preferably 10 mol% or more, more preferably 20 mol% or more. From the perspective of improving the thermal stability of light-shielding properties, it is preferably 100 mol% or less, more preferably 80 mol% or less.

[0112] The positive photosensitive composition of the present invention contains (b) resin. The resin referred to herein refers to a compound having a polymer chain with a number of repeating units of 5 or more and a weight average molecular weight (Mw) of 1,000 or more. Component (b) is a component that provides positive photosensitivity together with component (c) described later, and has a function as a binder component for fixing component (a) in the pixel segmentation layer and / or planarization layer finally obtained.

[0113] The (b) resin is not particularly limited, but is preferably a (b-1) phenolic hydroxyl group-containing resin (hereinafter sometimes referred to as component (b-1)) from the viewpoint of improving resolution. That is, the positive photosensitive composition of the present invention preferably contains a (b-1) phenolic hydroxyl group-containing resin.

[0114] As (b-1) component, for example, polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, Novolac resin, resin and polysiloxane having repeating units of free radical polymerizable monofunctional monomers derived from phenolic hydroxyl groups can be cited. One or more of these resins can be contained. Among them, it is preferred to contain at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole precursor and their copolymers. The copolymer referred to herein can be a random copolymer or a block copolymer. Polyimide, polyimide precursor, polybenzoxazole precursor and their copolymers are not easy to thermally decompose, and the volume shrinkage of the film is small, so there is an effect of suppressing the light-shielding property of each 1.0 μm film thickness after high temperature treatment to change in a high direction. Therefore, the thermal stability of the light-shielding property of the pixel segmentation layer and / or the planarization layer can be further improved.

[0115] That is, with respect to the positive photosensitive composition of the present invention, preferably, the (b) resin contains (b-1) a phenolic hydroxyl-containing resin, and the (b-1) phenolic hydroxyl-containing resin is at least one resin selected from the group consisting of polyimide, a polyimide precursor, a polybenzoxazole precursor and their copolymers.

[0116] The weight average molecular weight (Mw) of the resin as the component (b-1) is preferably 5,000 to 50,000, and more preferably 10,000 to 30,000, from the viewpoint of achieving both light-shielding thermal stability and resolution.

[0117] Among them, from the perspective of improving resolution, a resin having a structural unit represented by formula (17) and / or a structural unit represented by formula (18) is more preferred. That is, in the positive photosensitive composition of the present invention, it is more preferred that the (b) resin contains (b-1) a phenolic hydroxyl group-containing resin, and the (b-1) component contains a resin having a structural unit represented by formula (17) and / or a resin having a structural unit represented by formula (18).

[0118] [Chemical formula 17]

[0119]

[0120] In formula (17), R 37 represents a 4- to 10-valent organic group. 38 represents a 2- to 8-valent organic group. 39 and R 40 Each independently represents a phenolic hydroxyl group or a carboxyl group, and each may be a single group or a mixture of different groups. 39 and R 40 At least one of them 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 bonding site.

[0121] [Chemical formula 18]

[0122]

[0123] In formula (18), R 41 and R 42 represents a 2- to 8-valent organic group. 43 and R 44 Each independently represents a phenolic hydroxyl group, a carboxyl group or -COOA, and each may be a single group or a mixture of different groups. 43 and R 44 At least one of them 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 bonding site.

[0124] From the perspective of improving resolution, the resin having a structural unit represented by formula (18) preferably has a group represented by -COOA. In formula (18), the monovalent hydrocarbon group A having 1 to 10 carbon atoms may be, for example, a methyl group, an ethyl group, a propyl group, a phenyl group or a benzyl group.

[0125] In formula (17), R 37 -(R 39 )p represents the residue of an acid dianhydride. 37 It is preferably an organic group having 5 to 40 carbon atoms and containing an aromatic ring or a cyclic aliphatic group. Examples of the acid dianhydride residue include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic 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)malonic dianhydride, 2,2-bis(2,3-dicarboxyphenyl)malonic dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethanedicarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethanedicarboxylic dianhydride, and bis(3,4-dicarboxyphenyl)ethanedicarboxylic dianhydride. Residues of aromatic tetracarboxylic dianhydrides such as (3,4-dicarboxyphenyl)formic anhydride, bis(2,3-dicarboxyphenyl)formic anhydride, 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, and the acid dianhydride having a structure represented by formula (19); residues of aliphatic tetracarboxylic dianhydrides such as butanetetracarboxylic dianhydride and the residue of 1,2,3,4-cyclopentanetetracarboxylic dianhydride; and the like.

[0126] [Chemical formula 19]

[0127]

[0128] In formula (19), R 45 Represents a single bond, -O-, -C(CF3)2-, -C(CH3)2- or -SO2-. 46 and R 47 Each independently represents a hydrogen atom or -OH.

[0129] In formula (18), R 41 -(R 43 )r represents an acid residue. 41 It is preferably an organic group having 5 to 40 carbon atoms and containing an aromatic ring or a cyclic aliphatic group.

[0130] Examples of the acid residue 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 trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, and biphenyl trimaric acid residues. Examples of the tetracarboxylic acid residue 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-dicarboxyphenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4-dicarboxyphenyl)ethane , residues of aromatic tetracarboxylic acids such as residues of 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-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, and 3,4,9,10-perylenetetracarboxylic acid, and residues of aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid.

[0131] R in formula (17) 38 -(R 40 )q and R in formula (18) 42 -(R 44 )s represents a diamine residue. 38 and R 42 It is preferably an organic group having 5 to 40 carbon atoms and containing an aromatic ring or a cyclic aliphatic group.

[0132] Examples of the diamine residue include residues of diamines such as 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 1,4-bis(4-aminophenoxy)benzene, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 1,6-naphthalenediamine, bis(4-aminophenoxy)biphenyl, 1,4-bis(4-aminophenoxy)benzene, 2-bis(3-amino-4-hydroxyphenyl)propane, 1,3-bis(4-aminophenoxy)benzene, and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane; residues of compounds represented by formula (20); and residues of compounds represented by formula (21).

[0133] [Chemical formula 20]

[0134]

[0135] In formula (20), R48 Represents a single bond, -O-, -C(CF3)2-, -C(CH3)2- or -SO2-. 49 and R 50 Each independently represents a hydrogen atom or -OH.

[0136] [Chemical formula 21]

[0137]

[0138] In formula (21), R 51 Represents a single bond, -O-, -C(CF3)2-, -C(CH3)2- or -SO2-. 52 and R 53 Each independently represents a hydrogen atom or -OH.

[0139] Furthermore, by capping the ends of these resins with monoamines, it is possible to easily adjust the weight average molecular weight (Mw) and improve the storage stability as the (b) resin.

[0140] Examples of the monoamine include 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-aminophenol, 3-aminophenol and 4-aminophenol.

[0141] In formula (18), the group represented by COOA is obtained by converting a carboxyl group using an esterifying agent. Examples of the esterifying agent include N,N-dimethylformamide dimethyl acetal and N,N-dimethylformamide diethyl acetal.

[0142] 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, it can be synthesized by the method disclosed in Japanese Patent No. 4341293, International Publication No. 2014 / 097992, and International Publication No. 2019 / 181782.

[0143] Novolac resin can be obtained by a known method, and can be synthesized by condensing an aldehyde compound such as formaldehyde or benzaldehyde with a compound having a phenol skeleton such as phenol, o-cresol, m-cresol, p-cresol, or xylenol in the presence of an acidic catalyst. Commercially available products of Novolac resin include, for example, TRR5030G, TRR5010G, TR4020G, TR4080G, TR4000B, TRM30B20G, and EP23F10G (all of which are manufactured by Asahi Organic Materials Co., Ltd.).

[0144] As the resin having repeating units derived from a radical polymerizable monofunctional monomer having a phenolic hydroxyl group, for example, there can be mentioned a resin obtained by polymerizing one or a combination of two or more radical polymerizable monofunctional monomers having a phenolic hydroxyl group, such as hydroxystyrene, hydroxyphenyl (meth)acrylate, and hydroxyphenyl (meth)acrylamide. Furthermore, a radical polymerizable monofunctional monomer having a thermal crosslinkable group, such as glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and allyl glycidyl (meth)acrylate, can be copolymerized.

[0145] In order to improve the resolution, the content of the (b) resin in 100% by mass of the solid content of the positive photosensitive composition is preferably 30% by mass or more, more preferably 50% by mass or more. In order to obtain high light-shielding properties, it is preferably 80% by mass or less, more preferably 60% by mass or less.

[0146] 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 is decomposed by irradiation with light including at least light with a wavelength of 200 to 450 nm and generates an acid. The acid generated is preferably a carboxylic acid and / or a sulfonic acid.

[0147] By containing component (c), the following effect is obtained: the solubility of the film of the exposed part in the alkaline developer is relatively increased by utilizing the acid generated, compared with the solubility of the film of the unexposed part in the alkaline developer. As a result, positive photolithography can be achieved, that is, the film of the exposed part that has been pattern-exposed through the exposure mask is removed to form a pattern. In addition, the amount of acid generated in the film can also be controlled by adjusting the exposure amount. By using an exposure mask having multiple openings and light shielding parts with different transmittances in the surface, that is, a halftone exposure mask, the solubility of the film of the exposed part exposed by a small exposure amount in the alkaline developer is relatively reduced compared with the solubility of the film of the exposed part exposed by a large exposure amount in the alkaline developer, thereby being able to form a pattern with a step difference by using a positive halftone process.

[0148] As component (c), a compound having absorption in the region of i-line (wavelength 365nm), h-line (wavelength 405nm) and g-line (wavelength 436nm) of a mercury lamp and generating acid is preferred, and examples thereof include quinonediazide compounds, oximesulfonate compounds, and naphthylimidesulfonate compounds. Among them, quinonediazide compounds are preferred from the viewpoints of being able to exhibit an excellent dissolution suppression effect on the unexposed portion of the film, further increasing the difference in dissolution rate between the exposed portion and the unexposed portion, and achieving excellent resolution.

[0149] From the viewpoint of improving resolution, the quinonediazide compound preferably contains (c-1) at least one compound selected from the group consisting of a compound having two or more groups represented by the formula (22) in the molecule and having a phenolic hydroxyl group, a compound having two or more groups represented by the formula (23) in the molecule and having a phenolic hydroxyl group, and a compound having a group represented by the formula (22) and a group represented by the formula (23) and having a phenolic hydroxyl group (hereinafter sometimes referred to as component (c-1)). From the viewpoint of improving resolution, it is more preferable to contain a compound having at least a group represented by the formula (22) in the molecule and having a phenolic hydroxyl group.

[0150] That is, in the positive photosensitive composition of the present invention, the (c) photoacid generator preferably contains (c-1) at least one compound selected from the group consisting of a compound having two or more groups represented by the formula (22) in the molecule and having a phenolic hydroxyl group, a compound having two or more groups represented by the formula (23) in the molecule and having a phenolic hydroxyl group, and a compound having a group represented by the formula (22) and a group represented by the formula (23) and having a phenolic hydroxyl group.

[0151] [Chemical formula 22]

[0152]

[0153] In formula (22), R 54 , R 55 , R 56 and R 57 Each independently represents 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.

[0154] [Chemical formula 23]

[0155]

[0156] In formula (23), R 58 , R 59 and R 60 Each independently represents 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.

[0157] In formula (22), from the perspective of improving resolution, R 54 , R 55 , R 56 and R 57 In formula (23), from the perspective of improving resolution, R 58 , R 59 and R 60 Preferred is a hydrogen atom.

[0158] A compound having two or more groups represented by formula (22) in the molecule and having a phenolic hydroxyl group can be synthesized, for example, by a partial esterification reaction between a compound having three or more phenolic hydroxyl groups in the molecule and 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride. A compound having two or more groups represented by formula (23) in the molecule and having a phenolic hydroxyl group can be synthesized, for example, by a partial esterification reaction between a compound having three or more phenolic hydroxyl groups in the molecule and 1,2-naphthoquinone-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 can be synthesized, for example, by a partial esterification reaction between a compound having three or more phenolic hydroxyl groups in the molecule and 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride and 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride.

[0159] Examples of the compound 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-PR, BisP-B, BisP-DE, BisP-DP, Bis P-DP, Bis RS-2P, Bis RS-3P, and Bis P-DEK (all manufactured by Honshu Chemical Industry Co., Ltd.).

[0160] Examples of the component (c-1) include a compound represented by formula (24), a compound represented by formula (25), a compound represented by formula (27), and a compound represented by formula (28).

[0161] [Chemical formula 24]

[0162]

[0163] In formula (24), Q 1 , Q 2 , Q 3 and Q 4 Each independently represents a hydrogen atom or a group represented by formula (26). 1 , Q 2 , Q 3 and Q 4 In the formula (26), the total number of the groups represented by the formula (26) is 2 or 3.

[0164] In formula (25), Q 5 , Q 6 and Q 7 Each independently represents a hydrogen atom or a group represented by formula (26). 5 , Q 6 and Q 7In the formula (26), the total number of the groups represented by the formula (26) is 2.

[0165] [Chemical formula 25]

[0166]

[0167] In formula (26), * represents a bonding site with an oxygen atom.

[0168] [Chemical formula 26]

[0169]

[0170] In formula (27), Q 8 , Q 9 and Q 10 Each independently represents a hydrogen atom or a group represented by formula (29). 8 , Q 9 and Q 10 In the formula (29), the total number of the groups represented by the formula (29) is 2.

[0171] In formula (28), Q 11 , Q 12 , Q 13 and Q 14 Each independently represents a hydrogen atom or a group represented by formula (29). 11 , Q 12 , Q 13 and Q 14 In the formula (29), the total number of the groups represented by the formula (29) is 2 or 3.

[0172] [Chemical formula 27]

[0173]

[0174] In formula (29), * represents a bonding site with an oxygen atom.

[0175] Commercially available products of the component (c) that is sensitive to i-rays and generates acid include PA-28 (manufactured by Daito Chemix Co., Ltd.) as a naphthoquinonediazide compound, PAG103 and PAG203 (all manufactured by BASF) as oximesulfonate compounds, and NP-TM2 and NP-SE10 (all manufactured by San-Apro Co., Ltd.) as naphthaleneimidesulfonate compounds. The components (c) above may be used alone or in combination of two or more. For example, in addition to the quinonediazide compound, a naphthaleneimidesulfonate compound having an -O-SO2-CF3 group bonded to a nitrogen atom constituting an imide bond may be contained.

[0176] From the viewpoint of generating a necessary and sufficient amount of acid in the film to improve the resolution, the content of the component (c) is preferably 3% by mass or more, more preferably 5% by mass or more, based on 100% by mass of the solid content of the positive photosensitive composition. From the viewpoint of suppressing excessive absorption of exposure light on the film surface to improve the resolution, it is preferably 30% by mass or less, more preferably 20% by mass or less.

[0177] The positive photosensitive composition of the present invention contains (d) an organic solvent (hereinafter, sometimes referred to as component (d)). The organic solvent (d) 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, thereby improving the smoothness of the pre-baked film described later.

[0178] As the component (d), an organic solvent (d-1) having a hydroxyl group (hereinafter, sometimes referred to as the component (d-1)) is preferred.

[0179] That is, the positive photosensitive composition of the present invention preferably contains (d-1) an organic solvent having a hydroxyl group. The component (d-1) has a high affinity with the component (a) and exhibits an effect of improving resolution.

[0180] Examples of the component (d-1) include 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.

[0181] 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) can be used to adjust the solubility of components other than component (a) and the viscosity of the positive photosensitive composition.

[0182] As the component (d-2), for example, there can be mentioned acetate solvents such as ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (hereinafter, referred to as "PGMEA"), 3-methoxybutyl acetate (hereinafter, referred to as "MBA"), lactone solvents such as γ-butyrolactone (hereinafter, referred to as "GBL"), γ-valerolactone, and amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone (hereinafter, referred to as "NMP"). When the component (a) is present in the form of a dye, for example, if the content of the lactone solvent is set to 30% by mass or more in 100% by mass of the component (d), there is a tendency to obtain high solubility.

[0183] From the perspective of improving storage stability, the content of component (d) is preferably 40% by mass or more, more preferably 60% by mass or more in 100% by mass of the positive photosensitive composition. From the perspective of improving the smoothness of the prebaked film, it is preferably 99% by mass or less, more preferably 95% by mass or less. In addition, from the perspective of improving resolution, the content of component (d-1) is preferably 50% by mass or more, more preferably 80% by mass or more in 100% by mass of component (d).

[0184] That is, in the positive photosensitive composition of the present invention, preferably, 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 in 100% by mass of component (d).

[0185] From the perspective of improving the thermal stability of light-shielding properties, the positive photosensitive composition of the present invention preferably further contains at least one compound selected from the group consisting of a compound represented by formula (e) (30), a compound represented by formula (31), and a compound having a triphenodioxazine skeleton (hereinafter sometimes referred to as component (e)). The triphenodioxazine skeleton referred to herein has the same meaning as the triphenodioxazine skeleton. It should be noted that the compound represented by formula (30) and the compound represented by formula (31) have the aforementioned PTCBI skeleton, but do not have a sulfonic group, and are compounds that do not belong to component (a).

[0186] [Chemical formula 28]

[0187]

[0188] 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 represents a hydrogen atom, -F, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms.

[0189] From the perspective of improving the thermal stability of light-shielding properties, R 61 , R 62 , R 63 , R 64 , R 65 , R 66 , R 67 and R 68 Preferred is a hydrogen atom.

[0190] Examples of the compound having a triphenodioxazine skeleton include a compound represented by formula (32), a compound represented by formula (33), CI Pigment Violet 23, CI Direct Violet 54, and CI Direct Blue 106, 107, 108, and 190.

[0191] [Chemical formula 29]

[0192]

[0193] In formula (32), R 69 , R 70 , R 71 and R 72 Each independently represents an alkyl group having 1 to 3 carbon atoms. 73 and R 74 Each independently represents -NH- or -O-.

[0194] [Chemical formula 30]

[0195]

[0196] In formula (33), R 75 and R 76 Each independently represents a hydrogen atom or a halogen atom. 77 , R 78 , R 79 and R 80 Each independently represents a hydrogen atom, a phenyl group or an alkyl group having 1 to 5 carbon atoms.

[0197] Among them, preferred are compounds represented by formula (30), compounds represented by formula (31), and compounds represented by formula (32).

[0198] The content of component (e) is preferably 10% by mass or more in 100% by mass of the total of components (a) and (e), from the perspective of improving thermal stability of light-shielding properties, and is preferably 60% by mass or less in terms of improving resolution.

[0199] The positive photosensitive composition of the present invention may contain a thermal crosslinking agent, a leveling agent, an adhesion improver to the substrate surface, and the like as other components as necessary.

[0200] As a method for preparing the positive photosensitive composition of the present invention, for example, the following method can be mentioned: when at least a part of the component (a) is present as an insoluble pigment, a pigment dispersion containing the component (a), the resin (b) and the component (d), and the component (e) added as required is prepared in advance by wet media dispersion treatment, and then the components (c) and (d), and other components added as required, are mixed and stirred with the pigment dispersion, and filtered by a filter as required. When the component (a) has a solubility distribution in the resin (b) and the component (d), and a trace amount of insoluble matter of the component (a) may be generated, it may be possible to obtain a completely dissolved dye by pulverizing it by wet media dispersion treatment. On the other hand, when the component (a) is present entirely as a dissolved dye, a step of dissolving the component (a) in the resin (b) and the component (d) under heating at 40 to 70° C. may be performed instead of the wet media dispersion treatment.

[0201] When component (f) is contained, the salt of component (a) and component (f) will be formed by simply mixing. However, from the perspective of further advancing the formation of the salt and improving the resolution, it is preferred to heat the source of the component (f) and the component (a) in the presence of a solvent to form a salt in advance, further purify and dry, and powder the obtained mixture before using it to prepare a positive photosensitive composition.

[0202] As a disperser for performing the wet media dispersion treatment, a bead mill filled with ceramic beads can be preferably used. Examples of the ceramic beads include "TORAYCERAM (registered trademark)" (manufactured by Toray Industries, Inc.).

[0203] The cured film of the present invention as the second embodiment of the present invention is a cured film containing a cured product of the positive photosensitive composition of the present invention. The cured product referred to herein is a substance obtained by a process of heating the 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 an excellent technical effect of high thermal stability of light-shielding properties, and can be preferably used, for example, for the pixel segmentation layer and TFT planarization layer of an organic EL display device.

[0204] Hereinafter, a preferred embodiment in which the cured film of the present invention is used as a pixel segmentation layer or a planarization layer of an organic EL display device will be described.

[0205] In terms of improving the value of a display device by suppressing external light reflection, the optical density per 1.00 μm film thickness of the pixel division layer and the planarization layer (Optical Density / μm, hereinafter sometimes referred to as OD / μm) is preferably 0.50 or more, more preferably 0.70 or more. In terms of improving the resolution, it is preferably 1.30 or less, more preferably 1.10 or less. In terms of improving the value of a display device by suppressing external light reflection, the film thickness of each of the pixel division layer and the planarization layer is preferably 1.00 μm or more. In terms of obtaining a high resolution, it is preferably 5.00 μm or less.

[0206] OD / μm refers to the following value: Using an X-Rite 361T (manufactured by X-Rite) densitometer, the incident light intensity and the transmitted light intensity are measured for the pixel division layer and / or the planarization layer formed on a transparent substrate so that the film thickness becomes 1.50 μm, and a numerical value is calculated according to the following formula, and the value obtained by dividing the numerical value by the film thickness value of 1.50. The higher the OD / μm, the higher the light shielding property. As the transparent substrate, a transparent glass substrate "Tempax" (manufactured by AGC Technoglass Co., Ltd.) with an OD / μm of 0.00 can be preferably used.

[0207] Optical density = log 10 (I0 / I)

[0208] In the above formula, I0: incident light intensity, I: transmitted light intensity.

[0209] In terms of suppressing the disconnection of the electrode and thus avoiding the generation of unlit pixels, the cross-sectional cone angle at the inclined portion at the end of the pixel division layer is preferably 50° or less, more preferably 40° or less. In terms of suppressing the reduction of the light shielding property at the end, it is preferably 15° or more, more preferably 20° or more.

[0210] As a method for forming the pixel division layer, a method preferably including the following steps in sequence is used: a coating step of coating a positive photosensitive composition to obtain a coating film; a pre-baking step of heating the coating film to obtain a pre-baked film; an exposure step of pattern-exposing actinic rays through a positive exposure mask to obtain an exposed film having exposed portions and unexposed portions in the plane; a developing step of developing using an alkaline developer to remove the exposed portions to obtain a developed film; and a curing step of thermally curing it to obtain the pixel division layer. On the other hand, the planarization layer can be formed by the same method as the method for forming the pixel division layer.

[0211] As a coating device used in the coating step, a spin coater or a slot coater can be preferably used in terms of excellent thin film coating properties.

[0212] The prebaking temperature in the prebaking step is preferably 50 to 150° C., and the prebaking time is preferably 30 seconds to 5 minutes. From the perspective of improving the uniformity of the film thickness, the film thickness of the prebaked film is preferably 3.0 to 6.0 μm.

[0213] As the exposure device used in the exposure process, for example, a stepper, a mirror projection mask aligner (MPA), and a parallel light mask aligner (PLA) can be cited. As the active chemical rays irradiated during exposure, the j line (wavelength 313nm), i line (wavelength 365nm), h line (wavelength 405nm) or g line (wavelength 436nm) of an ultra-high pressure mercury lamp can be cited. The exposed portion in the exposure film refers to the portion where the pattern is exposed through the transparent portion of the exposure mask, and the unexposed portion refers to the portion that is not exposed due to the shielding portion of the exposure mask. Considering the pixel segmentation layer and / or the flattening layer with high reproducibility of the design size of the opening width of the exposure mask, it is preferred to adjust the exposure amount to expose in a manner such that the value obtained by subtracting the opening width of the opening portion of the patterned opening from the opening width of the exposure mask, that is, the exposure mask deviation is within the range of ±0.2μm.

[0214] As the developing method in the developing process, for example, spraying, dipping, and immersion by spinning can be cited, and a method of immersing the exposure film for 10 seconds to 3 minutes can be cited. From the perspective of improving the in-plane uniformity of resolution, the immersion by spinning method is preferred. As an alkaline developer, a 0.4-2.5% by mass tetramethylammonium hydroxide aqueous solution (hereinafter referred to as "TMAH") is preferred, and as a commercially available product, for example, 2.38% by mass TMAH (manufactured by Tama Chemical Industry Co., Ltd.) can be cited. After the developing process, it is preferred to add a water washing process using deionized water, that is, a rinsing process, and then dry it to obtain a developed film. From the perspective of improving the in-plane uniformity of the film thickness of the developed film, the developing time is preferably set in a manner such that the value obtained by subtracting the film thickness of the developed film (unexposed portion) from the film thickness of the pre-baked film, that is, the film loss (μm) in the developing process becomes less than 1.00μm. From the perspective of improving the resolution, it is preferably set in a manner such that it becomes 0.50μm or more. In addition, the obtained developed film may be irradiated with exposure light again as a second exposure step to control the fluidity of the film in the curing step.

[0215] As a heating device used in the curing process, for example, a hot air oven, an IR oven, etc. can be cited, and the heating atmosphere can be nitrogen or air. The heating temperature is preferably 250 to 270° C. under atmospheric pressure, and the heating time can be 1 to 3 hours. The conditions of the curing process can be set so that at least a part of the (f) component disappears from the pixel segmentation layer or the planarization layer.

[0216] The organic EL display device of the present invention as a third embodiment of the present invention is an organic EL display device having a pixel division layer and a planarization layer, and the pixel division layer and / or the planarization layer contains the cured film of the present invention. The organic EL display device of the present invention exhibits a technical effect of ideal high visual recognition by making the pixel division layer and / or the planarization layer contain the cured film of the present invention having high light shielding properties and high uniformity in its surface and excellent resolution.

[0217] Figure 1 A cross-sectional view of a TFT substrate in an organic EL display device including a pixel dividing layer and a planarizing layer is shown as a specific example of an embodiment of the present invention.

[0218] On the surface of the substrate 6, bottom-gate or top-gate thin-film transistors 1 (hereinafter referred to as TFT1) are arranged in rows and columns, and a TFT insulating layer 3 is configured to cover the TFT1 and the wiring 2 connected to the TFT1. In addition, a pattern of a planarization layer 4 is formed on the surface of the TFT insulating layer 3, and the planarization layer 4 has a contact hole 7 as an opening for connecting the wiring 2 to the first electrode 5. On the surface of the planarization layer 4, a pattern of the first electrode 5 is formed and connected to the wiring 2. A pixel division layer 8 having a step difference and having a spacer function is formed in a manner surrounding the periphery of the pattern of the first electrode 5. The pixel division 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 is formed in a state of covering the pixel division layer 8 and the light-emitting pixel 9. If a voltage is applied to the light-emitting pixel portion after the TFT substrate containing the above stacked structure is sealed under vacuum, it can emit light as an organic EL display device.

[0219] The organic EL display device having the pixel segmentation layer and the planarization layer of the present invention can be a bottom emission type organic EL display device in which the emission light released from the light-emitting pixel 9 is taken out to the substrate side via the substrate 6, or can be a top emission type organic EL display device in which the emission light is taken out to the opposite side of the substrate 6 via the second electrode 10. The planarization layer 4 having light shielding properties can function as a light shielding layer for protecting the TFT 1. As TFT 1, for example, oxide semiconductors such as In-Ga-Zn-O (IGZO) and Ga-Zn-Sn, and TFTs obtained from low temperature polycrystalline silicon (LTPS) can be cited.

[0220] The shape of the openings of the pixel segmentation layer 8 and the planarization layer 4 is 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 opening width and shape of the opening of the pixel segmentation layer 8, and may be, for example, a circle with a diameter of 3 to 30 μm. The contact hole 7 as the opening of the planarization layer 4 may be, for example, a circle with a diameter of 3 to 7 μm. The higher the resolution of the pixel segmentation layer 8 and the planarization layer 4, the more useful the effect of the present invention, such as high thermal stability of light-shielding properties, becomes.

[0221] There is no particular restriction on the peak wavelength of the luminescent pixel 9. For example, different types of pixels having respective peak wavelengths of the three primary colors of light, i.e., blue, red, and green, can be cited as being arranged on the entire surface. The peak wavelength of the red region can be 560 to 700 nm, the peak wavelength of the blue region can be 420 to 480 nm, and the peak wavelength of the green region can be 500 to 550 nm. In addition, as another stacked component, a color filter substrate can be arranged in front of the display unit, and the color filter substrate is formed with blue, red, and green color filters and a black matrix separating them. As an organic EL light-emitting material constituting the luminescent pixel 9, a material that is combined with a hole transport layer and / or an electron transport layer in addition to the light-emitting layer can be appropriately used. The luminescent pixel 9 is formed, for example, by a mask evaporation method disclosed in Japanese Patent Gazette No. 2019-163543.

[0222] As the first electrode 5, for example, transparent conductive metal oxides such as indium tin oxide (ITO) and indium zinc oxide (IZO) can be used. As a method for forming a pattern of ITO, the following method can be cited: forming a film of ITO on the entire surface by sputtering, and then forming a positive resist material for etching into a pattern by photolithography, thereby obtaining a resist pattern on the ITO film, and removing only the ITO film in the portion where the resist pattern is not formed by an acidic etching solution; then, removing the resist pattern by a resist stripping solution. As a positive resist material for etching, a positive photosensitive composition containing an alkali-soluble Novolac resin can be used. In the case of a top-emitting organic EL display device, in order to improve the light extraction efficiency, the first electrode 5 can be a laminate of ITO / silver alloy / ITO.

[0223] The second electrode 10 may be formed of any material as long as it is a layer that functions as an electrode. In the case of a bottom-emitting organic EL display device, a layer obtained from aluminum may be preferably used from the perspective of excellent light reflectivity. In the case of a top-emitting organic EL display device, a silver alloy obtained from silver and magnesium may be preferably used from the perspective of excellent light transmittance. The second electrode 10 may be formed on the entire surface by sputtering.

[0224] In addition to using a glass substrate, the following flexible substrate can also be used as substrate 8: a polyamic acid solution is applied to the surface of a temporary support, followed by heat treatment at 250 to 400° C. to generate a polyimide-forming substrate, from which the temporary support is laser-detached to obtain a flexible substrate.

[0225] The dye of the present invention as a fourth embodiment of the present invention is a dye containing (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) (hereinafter, sometimes referred to as the dye of the present invention).

[0226] The pigment of the present invention can be preferably used as a coloring material for imparting light-shielding properties to a pixel segmentation layer and / or a planarization layer of an organic EL display device. In particular, by containing the pigment in a positive photosensitive composition, not only is the thermal stability of the light-shielding properties excellent, but also a particularly remarkable technical effect is achieved in that a cured film with high light-shielding properties and high resolution is obtained.

[0227] The compound represented by the formula (70) (f) contained in the pigment of the present invention preferably forms a salt with the compound represented by the formula (85) (a) and / or the compound represented by the formula (86). In addition to the content of the component (f), the salt may be increased by reacting with N + or P + The polarity is changed by the type of organic group to be bonded, and the compatibility with the resin and the solubility in the organic solvent are controlled.

[0228] [Chemical formula 31]

[0229]

[0230] In formula (70), R 81 N + or P + . R 82 , R 83 , R 84 and R 85 Each independently represents an alkyl group having 1 to 20 carbon atoms, a phenyl group or a hydrogen atom which is optionally substituted with -OH or a phenyl group. 81 N + In the case of R 82 , R 83 , R 84 and R 85 The total number of hydrogen atoms is 0 to 2, R 81 P + In the case of R 82 , R 83 , R 84 and R 85The total number of hydrogen atoms is 0.

[0231] In formula (85), R 91 , R 92 , R 93 , R 94 , R 95 , R 96 , R 97 and R 98 Each independently represents a hydrogen atom, -SO3H, -SO3 - , an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, -CF3, -F, -Br or -CN. 91 , R 92 , R 93 , R 94 , R 95 , R 96 , R 97 and R 98 In -SO3H and -SO3 - The total number of is 1 to 4, at least one of which is -SO3 - .

[0232] R 99 , R 100 , R 101 and R 102 Each independently represents a hydrogen atom, -OH, -F, -Br, -CN or an alkoxy group having 1 to 5 carbon atoms. 99 With R 100 , R 101 With R 102 Each independently optionally bonded to each other to form a linking group -X 3 -.-X 3 - represents -O- or -SO2-.

[0233] In formula (86), R 103 , R 104 , R 105 , R 106 , R 107 , R 108 , R 109 and R 110 Each independently represents a hydrogen atom, -SO3H, -SO3 - , an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, -CF3, -F, -Br or -CN. 103 , R 104 , R 105 , R 106 , R 107 , R 108 , R 109 and R110 In -SO3H and -SO3 - The total number of is 1 to 4, at least one of which is -SO3 - .

[0234] R 111 , R 112 , R 113 and R 114 Each independently represents a hydrogen atom, -OH, -F, -Br, -CN or an alkoxy group having 1 to 5 carbon atoms. 111 With R 112 , R 113 With R 114 Each independently optionally bonded to each other to form a linking group -X 4 -.-X 4 - represents -O- or -SO2-.

[0235] It should be noted that in formula (70), R 81 N + In the case of R 82 , R 83 , R 84 and R 85 In the formula, the total number of hydrogen atoms is 0 to 2, which means R 82 , R 83 , R 84 and R 85 One or two of them are 81 The hydrogen atoms bonded to R 81 The hydrogen atom referred to here does not refer to the hydrogen atom contained in the alkyl group having 1 to 20 carbon atoms which is optionally substituted with -OH or phenyl group, or the phenyl group. 81 P + In the case of R 82 , R 83 , R 84 and R 85 The statement that the total number of hydrogen atoms in R is 0 also refers to 82 , R 83 , R 84 and R 85 Neither 81 Bonded hydrogen atoms.

[0236] From the viewpoint of improving resolution, the dye of the present invention more preferably contains (f) a compound represented by formula (71).

[0237] [Chemical formula 32]

[0238]

[0239] In formula (71), R86 N + or P + . R 87 , R 88 , R 89 and R 90 Each independently represents an alkyl group having 1 to 15 carbon atoms which is optionally substituted with -OH or phenyl. 87 , R 88 , R 89 and R 90 At least one of them is an unsubstituted alkyl group having 1 to 15 carbon atoms. 86 N + In the case of + In the case of , it means that the component (f) has a phosphonium cation.

[0240] From the perspective of improving resolution, R 86 N + , and R 87 , R 88 , R 89 and R 90 It is an unsubstituted alkyl group having 1 to 15 carbon atoms.

[0241] Furthermore, from the viewpoint of improving the thermal stability and resolution of the light-shielding property, the dye of the present invention more preferably contains (a) a compound represented by formula (87) and / or a compound represented by formula (88).

[0242] [Chemical formula 33]

[0243]

[0244] In formula (87), R 115 and R 116 Each independently represents -SO3H or -SO3 - .n 5 and n 6 is an integer, each independently representing 0 to 2. 5 and n 6 The total number is 1 to 4, (R 115 ) 5 and (R 116 ) 6 At least one of them is -SO3 - .

[0245] In formula (88), R 117 and R 118 Each independently represents -SO3H or -SO3 - .n 7 and n 8is an integer, each independently representing 0 to 2. 7 and n 8 The total number is 1 to 4, (R 117 ) 7 and (R 118 ) 8 At least one of them is -SO3 - .

[0246] Examples of the dye of the present invention include, but are not limited to, a compound represented by formula (89), a compound represented by formula (90), and a compound represented by formula (91).

[0247] The compound represented by formula (89) contains as component (f) R 81 N + , and R 82 , R 83 , R 84 and R 85 A compound in which the total number of hydrogen atoms is 2.

[0248] The compound represented by formula (90) contains as component (f) R 81 N + , and R 82 , R 83 , R 84 and R 85 A compound in which the total number of hydrogen atoms is 0.

[0249] The compound represented by formula (91) contains as component (f) R 81 P + , and R 82 , R 83 , R 84 and R 85 A compound in which the total number of hydrogen atoms is 0.

[0250] [Chemical formula 34]

[0251]

[0252] The -SO3H and -SO3 - When the total is set to 100 mol%, the content of component (f) is preferably 10 mol% or more, more preferably 20 mol% or more, from the perspective of improving resolution. From the perspective of improving the thermal stability of light-shielding properties, it is preferably 100 mol% or less, more preferably 80 mol%.

[0253] As a method for obtaining the dye of the present invention, in addition to the above-mentioned method for obtaining the component (a), the above-mentioned method for obtaining the salt of the component (a) and the component (f) can also be preferably applied.

[0254] Example

[0255] Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these. First, the evaluation method in each Example and Comparative Example will be described.

[0256] <Determination of the optimal exposure>

[0257] A silver alloy (an alloy obtained from 99 mass % of silver and 1 mass % of copper) was formed on the entire surface of a 150 mm long / 150 mm wide alkali-free glass substrate by sputtering. Furthermore, an ITO film was formed 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.

[0258] The positive photosensitive compositions 1 to 15 obtained in Examples 1 to 13 and Comparative Examples 1 to 2 were applied to the ITO surface of the glass substrate having the silver alloy film / ITO film, respectively, using a spin coater and adjusting the rotation speed 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, to obtain coated films. Furthermore, the coated films were pre-baked at 110°C for 120 seconds under atmospheric pressure using a hot plate to obtain a pre-baked film, which was then exposed to light at 50 to 200 (mJ / cm2) using a double-sided alignment single-sided exposure device through a positive exposure mask (a hole pattern mask having 200 perfectly circular transparent portions with a diameter of 10.0 μm arranged). 2 The exposure amount is changed in stages every 10 mJ within the range of 10:i line conversion value), and the pre-baked film is pattern-exposed using the g, h, and i mixed lines of the ultra-high pressure mercury lamp to obtain an exposed film having an exposed portion and an unexposed portion in the surface. It should be noted that the pattern exposure is performed by contacting the positive exposure mask with the surface of the pre-baked film.

[0259] Next, as a development process, a small-sized developing device for lithography (AD-1200; manufactured by Ryusawa Industry Co., Ltd.) and a 2.38% by mass tetramethylammonium hydroxide aqueous solution as an alkaline developer are used to perform development by a rotary immersion method. The rotary immersion method referred to herein refers to the following method: after spraying an alkaline developer onto the surface of the exposure film for 10 seconds, the film is allowed to stand until a prescribed development time is reached, thereby performing development. Furthermore, after rinsing with deionized water by spraying for 30 seconds, the substrate is idly rotated at 200 rpm for 30 seconds to dry, thereby obtaining a developed film-forming substrate having a developed film. It should be noted that, with respect to the setting of the development time, within the range of 40 to 90 seconds, the value obtained by subtracting the film thickness of the developed film (unexposed portion) from the film thickness of the pre-baked film, that is, the time when the film loss (μm) in the development process becomes 0.80 μm, is set.

[0260] Next, as a curing step, the developed film was 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, Inc.) to obtain an optimal exposure evaluation substrate having a cured film with hole-like openings.

[0261] The center of the cured film was observed using an FPD inspection microscope (MX-61L; manufactured by Olympus Corporation), and the minimum exposure amount (mJ / cm) when the opening was opened so that the average opening width of 10 openings in the cured film in each exposure amount region was 10.0 μm was calculated. 2 : i-line conversion value) as the optimal exposure amount. When the shape of the opening is a perfect circle, its diameter is used as the opening width, and when it is an ellipse, its short axis is used as the opening width. It should be noted that for the film thickness in each process, a stylus-type film thickness measuring device (Tokyo Seimitsu Co., Ltd.; SURFCOM) is used to measure at three locations in the surface, and the third decimal place of the average value is rounded off to obtain a value accurate to the second decimal place.

[0262] On the other hand, for the negative photosensitive compositions 1 to 3 obtained in Comparative Examples 3 to 5, the optimal exposure amount was determined by the same method except that a negative exposure mask having an opposite mask design (a hole pattern mask having 200 perfectly circular shielding portions with a diameter of 10.0 μm arranged) was used instead of the aforementioned positive exposure mask, and the time until the film of the solid unexposed portion was dissolved and the substrate could be seen was multiplied by 1.5 as the development time.

[0263] (1) Evaluation of thermal stability of light-shielding properties of cured films

[0264] For the light-shielding evaluation substrates A and B obtained in Examples 1 to 13 and Comparative Examples 1 to 5, the total optical density (Total OD value) was measured at three locations in the film surface from the film surface side using a densitometer (manufactured by X-Rite; X-Rite361T), and the average value was calculated. The value was divided by the film thickness of the cured film, and the value obtained was taken 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 evaluation substrate B from the light-shielding property of the light-shielding evaluation substrate A, the better the thermal stability of the cured film with respect to the changes in the heating temperature and the heating time. The evaluation was performed according to the following criteria, and AA and A to C were qualified, and D was unqualified.

[0265] AA: ΔOD / μm is less than 0.03.

[0266] A: ΔOD / μm is 0.03 or more and less than 0.05.

[0267] B: ΔOD / μm is 0.05 or more and less than 0.10.

[0268] C: ΔOD / μm is 0.10 or more and less than 0.20.

[0269] D: ΔOD / μm is 0.20 or more.

[0270] (2) Evaluation of the resolution of cured films and protruding foreign matter defects

[0271] The resolution evaluation substrates formed with the cured films having a film thickness of 1.5 μm obtained in Examples 1 to 13 and Comparative Examples 1 to 5 were observed using an FPD inspection microscope. The value obtained by subtracting the average value of the opening widths of 10 openings of the corresponding cured film from the opening widths of the exposure mask (perfect circular transmission parts 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) (exposure mask deviation) was within the range of ±0.2 μm, and the minimum opening width in the openings that could form a pattern without generating development residues was taken as the resolution (μm). The smaller the minimum opening width, the higher and more excellent the resolution is. The evaluation was performed according to the following criteria, and AA, A to C were qualified, and D was unqualified. In particular, when a protruding foreign matter defect was observed on the surface of one or more openings, the evaluation was set to E and unqualified regardless of the resolution. In the case where there was no opening where generation of development residue was not observed and the resolution could not be evaluated, the evaluation was set to F and was deemed unacceptable. In addition, in the case where the evaluation was E and equivalent to F, the evaluation was set to F.

[0272] AA: Resolution 2.0±0.2μm.

[0273] A: The resolution is 3.0±0.2μm.

[0274] B: Resolution is 4.0±0.2μm or 5.0±0.2μm.

[0275] C: Resolution is 6.0±0.2μm or 7.0±0.2μm.

[0276] D: The resolution is 7.8 μm or more.

[0277] E: Generation of protruding foreign matter defects was observed on the surface of one or more openings.

[0278] F: There was no opening portion where generation of development residue was not observed, and the resolution could not be evaluated.

[0279] (3) Evaluation of Resolution of Organic EL Display Devices

[0280] The organic EL display devices obtained in Examples 14 to 26 were placed with the light emitting surface facing upward and subjected to a 10 mA / cm 2 The device is left to stand in a state where it emits light using a DC drive, and the light-emitting surface of the organic EL display device is observed using an FPD inspection microscope. The opening widths of 10 light-emitting pixel parts where normal light emission is confirmed are measured, and the average value is taken as the resolution (μm) of the organic EL display device. The higher the resolution, the better the display device is. The evaluation is performed according to the following criteria, with AA, A to C being qualified and D being unqualified. Among them, when more than one non-luminous pixel (unlit pixel) is observed on the light-emitting surface, the evaluation is set to E, which is unqualified. It should be noted that for photosensitive compositions that are evaluated as unqualified in at least any of the aforementioned (1) evaluation of the thermal stability of the light-shielding properties of the cured film and (2) the resolution of the cured film and the protruding foreign matter defects, the organic EL display device is not produced and is excluded from this evaluation.

[0281] AA: Resolution 2.0±0.2μm.

[0282] A: The resolution is 3.0±0.2μm.

[0283] B: Resolution is 4.0±0.2μm or 5.0±0.2μm.

[0284] C: Resolution is 6.0±0.2μm or 7.0±0.2μm.

[0285] D: The resolution is 7.8 μm or more.

[0286] E: One or more unlit pixels were observed.

[0287] (Synthesis Example 1: Synthesis of Hydroxyl-Containing Diamine Compound A)

[0288] 18.30 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 100 mL of acetone and 17.40 g (0.3 mol) of propylene oxide, and the mixture was cooled to -15°C. A solution obtained by dissolving 20.40 g (0.11 mol) of 3-nitrobenzoyl chloride in 100 mL of acetone was added dropwise thereto. After the addition was completed, the mixture was reacted at -15°C for 4 hours, and then returned to room temperature. The precipitated white solid was separated by filtration and vacuum dried 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 into the mixture using a balloon, and a reduction reaction was performed at room temperature. After about 2 hours, it was confirmed that the balloon was no longer deflated, and the reaction was completed. After the reaction was completed, the mixture was filtered to remove the palladium compound as a catalyst, and then concentrated using a rotary evaporator to obtain a phenolic hydroxyl group-containing diamine compound A represented by formula (34).

[0289] [Chemical formula 35]

[0290]

[0291] (Synthesis Example 2: Synthesis of polyimide precursor B)

[0292] Under a dry nitrogen stream, 31.00 g (0.10 mol) of 3,3',4,4'-diphenylether tetracarboxylic dianhydride was dissolved in 500.00 g of NMP. 45.35 g (0.075 mol) of the diamine compound A containing a phenolic hydroxyl group obtained in Synthesis Example 1 and 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane were added together with 50.00 g of NMP, and reacted at 20°C for 1 hour, and then at 50°C for 2 hours. 4.36 g (0.04 mol) of 3-aminophenol as a terminal blocking agent was added together with 5.00 g of NMP, and reacted at 50°C for 2 hours. Then, 28.60 g (0.24 mol) of N,N-dimethylformamide dimethyl acetal 50.00 g was added. After addition, stirring was performed at 50°C for 3 hours. After stirring, the solution was cooled to room temperature, and then the solution was added to 3L of water to obtain a white precipitate. The above operation was repeated 5 times, and the obtained white precipitate was collected in the form of a filter residue, washed with water 5 times, and dried in a vacuum dryer at 80°C for 24 hours to obtain a powdered polyimide precursor B. The polyimide precursor B is a resin belonging to the component (b-1), has a structural unit represented by formula (18), and has a weight average molecular weight (Mw) of 25,000.

[0293] (Synthesis Example 3: Synthesis of diimidazole compound C)

[0294] Under a dry nitrogen flow, 162.15 g (1.00 mol) of 1,1'-carbonyldiimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 1000.00 g of NMP and stirred at a liquid temperature of 10°C for 1 hour to dissolve it. Furthermore, the liquid temperature was maintained below 20°C, and 113.46 g (0.44 mol) of diphenyl ether 4,4'-dicarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred. Next, the liquid temperature was raised to 60°C and stirred, and after the generation of carbon dioxide was completed, it was cooled to 5°C. 1000.00 g of deionized water was maintained below 10°C and added dropwise, and the precipitate was filtered and separated. The precipitate was washed with deionized water and then washed with isopropyl alcohol. Drying was carried out at 50°C under reduced pressure for 6 hours to obtain a diimidazole compound C represented by formula (35).

[0295] [Chemical formula 36]

[0296]

[0297] (Synthesis Example 4: Synthesis of polybenzoxazole precursor D)

[0298] Under a dry nitrogen stream, 732.52 g (2.00 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added to 3662.60 g of NMP and stirred at a liquid temperature of 40°C for 1 hour. Furthermore, 573.38 g (1.60 mol) of diimidazole compound C prepared in Synthesis Example 3 was added together with 286.69 g of NMP, the 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 stirred at a liquid temperature of 80°C for 3 hours. After cooling to a liquid temperature of 20°C, 600.20 g of acetic acid was added and stirred for 30 minutes, and then 500.00 g of NMP was added and stirred for further 1 hour. The solution obtained by the above operation was put into 10 L of water to obtain a precipitate. The precipitate was separated by filtration, washed with deionized water 5 times, and dried under reduced pressure at 50°C for 3 days to obtain a powdered polybenzoxazole precursor D. The polybenzoxazole precursor D is a resin belonging to the component (b-1), has a structural unit represented by formula (18), and has a weight average molecular weight (Mw) of 26,000. It should be noted that the polybenzoxazole precursor D was analyzed by NMR and gas chromatography-mass spectrometry. As a result, no imidazole ring structure derived from the diimidazole compound C represented by formula (35) was detected, and it is believed that it has completely disappeared through the above-mentioned reaction operation.

[0299] (Synthesis Example 5: Synthesis of Quinonediazide Compound E)

[0300] Under a dry nitrogen stream, 127.36 g (0.30 mol) of the compound represented by formula (36) (manufactured by Honshu Chemical Industry Co., Ltd.), 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.) were added to 1910.43 g of 1,4-dioxane, and stirred at a liquid temperature of 20° C. for 1 hour. Furthermore, 303.57 g of an additive (triethylamine:1,4-dioxane=mass ratio 20:80) was added dropwise, and then stirred at a liquid temperature of 30° C. for 3 hours. The triethylamine salt was separated by filtration, the filtrate was put into water, the generated precipitate was recovered, washed with deionized water three times, separated by filtration, and dried under reduced pressure to obtain a quinonediazide compound E represented by formula (37) as a mixture containing at least a compound represented by formula (38). The compound represented by formula (38) is component (c-1), has a group represented by formula (22) and a group represented by formula (23), and is equivalent to a compound having a phenolic hydroxyl group. It should be noted that the compound represented by formula (38) was determined by LC-MS and MALDI-TOF MS.

[0301] [Chemical formula 37]

[0302]

[0303] In formula (37), * represents a bonding site with an oxygen atom.

[0304] [Chemical formula 38]

[0305]

[0306] (Synthesis Example 6: Synthesis of Quinonediazide Compound F)

[0307] Under a dry nitrogen stream, 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-diazide-5-sulfonyl chloride were added to 1910.43 g of 1,4-dioxane, and stirred at a liquid temperature of 20° C. for 1 hour. Furthermore, 303.57 g of an additive (triethylamine:1,4-dioxane=mass ratio 20:80) was added dropwise, and then stirred at a liquid temperature of 30° C. for 3 hours. The triethylamine salt was separated by filtration, and the filtrate was poured into water. The generated precipitate was recovered, washed three times with deionized water, separated by filtration, and dried under reduced pressure to obtain a quinonediazide compound F represented by formula (39) as a mixture containing at least the compound represented by formula (40). The compound represented by formula (40) is component (c-1), and corresponds to a compound having two groups represented by formula (23) in the molecule and having a phenolic hydroxyl group. The compound represented by formula (40) was identified by LC-MS and MALDI-TOF MS.

[0308] [Chemical formula 39]

[0309]

[0310] In formula (39), * represents a bonding site with an oxygen atom.

[0311] [Chemical formula 40]

[0312]

[0313] (Synthesis Example 7: Synthesis of Perylene Blue Pigment 1)

[0314] To 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 (manufactured by 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 the liquid temperature was raised to 170° C. while stirring the mixture. Then, stirring was performed at a liquid temperature of 170° C. for 8 hours to allow the reaction to proceed sufficiently, and then the generated water was distilled off in the form of an azeotropic mixture with phenol. Then, the mixture was cooled to 100° C., and 500 50 g of ethanol was added in stages, and then stirred at 60°C for 1 hour, washed with water, filtered and separated, and dried at 80°C for 24 hours under reduced pressure to obtain a reaction product. Next, 50.00 g of the reaction product was dissolved in 500.00 g of 30% by mass fuming sulfuric acid, and the liquid temperature was raised to 80°C while stirring. Stirring was performed at a liquid temperature of 80°C for 8 hours to allow the sulfonation reaction to proceed. Next, 7 kg of ice water was added to obtain a slurry containing a precipitate, which was filtered and separated. Next, the filter residue was washed with a mixed solution (ethanol: water = mass ratio 80:20), filtered and separated again, and dried at 80°C for 24 hours under reduced pressure. Furthermore, using Nano The product was dry-pulverized using a Jetmizer (manufactured by Aishin Nano Technologies Co., Ltd.), and coarse components were removed using a stainless steel mesh filter (opening diameter 20 μm) to obtain perylene blue pigment 1. Analysis using LC-MS and MALDI-TOF MS revealed that perylene blue pigment 1 was component (a), which was a mixture of compounds represented by formula (41), compounds represented by formula (42), compounds represented by formula (43), compounds represented by formula (44), compounds represented by formula (45), compounds represented by formula (46), compounds represented by formula (47), and compounds represented by formula (48). It should be noted that in 100% by mass of perylene blue pigment 1, the total content of compounds represented by formula (45), compounds represented by formula (46), compounds represented by formula (47), and compounds represented by formula (48) was 12% by mass.

[0315] [Chemical formula 41]

[0316]

[0317] [Chemical formula 42]

[0318]

[0319] (Synthesis Example 8: Synthesis of Perylene Blue Pigment 2)

[0320] 100.00 g of perylene-3,4,9,10-tetracarboxylic acid bisbenzimidazole (produced by Tokyo Chemical Industry Co., Ltd.; a mixture of cis-isomer and trans-isomer) was dissolved in 400.00 g of 20% fuming sulfuric acid, and the liquid temperature was raised to 70°C while stirring. The liquid was stirred at 70°C for 5 hours to allow the sulfonation reaction to proceed. Next, 9 kg of ice water was added to obtain a slurry containing a precipitate, which was filtered and separated. After washing the filter residue with a mixed solution (ethanol: water = mass ratio 80:20), it was filtered and separated again, and dried at 80°C under reduced pressure for 24 hours. Furthermore, a Nano Jetmizer was used for dry pulverization treatment, and a stainless steel mesh filter (opening diameter 20 μm) was used to remove coarse components to obtain perylene blue pigment 2. LC-MS and MALDI-TOF MS were used for analysis. As a result, perylene blue pigment 2 was component (a), which was a mixture of a compound represented by formula (49), a compound represented by formula (50), a compound represented by formula (51), and a compound represented by formula (52). It should be noted that in 100% by mass of perylene blue pigment 2, the total content of the compound represented by formula (51) and the compound represented by formula (52) was 74% by mass.

[0321] [Chemical formula 43]

[0322]

[0323] (Synthesis Example 9: Synthesis of Perylene Blue Pigment 3)

[0324] 40.00 g of perylene blue pigment 2 obtained in the above-mentioned synthesis example 8 was dissolved in 400.00 g of 10% by mass fuming sulfuric acid, and the liquid temperature was raised to 130°C while stirring. The solution was stirred at a liquid temperature of 130°C for 10 hours to allow the sulfonation reaction to proceed. Next, 7 kg of ice water was added to obtain a slurry containing a precipitate, which was filtered and separated. Next, the filter residue was washed with a mixed solution (ethanol: water = mass ratio 80:20), filtered and separated again, and dried at 80°C under reduced pressure for 24 hours. Furthermore, a Nano Jetmizer was used for dry pulverization treatment, and coarse components were removed using a stainless steel mesh filter (opening diameter 20 μm) to obtain perylene blue pigment 3. LC-MS and MALDI-TOF MS were used for analysis, and the results showed that perylene blue pigment 3 was component (a), which was a mixture of the compound represented by formula (53) and the compound represented by formula (54).

[0325] [Chemical formula 44]

[0326]

[0327] (Synthesis Example 10: Synthesis of Perylene Blue Pigment 4)

[0328] To 3,066.93 g of phenol melted at 70°C, 681.54 g (1.50 mol) of perylene-3,4,9,10-tetracarboxylic acid dianhydride monosulfone (manufactured by Sigma-Aldrich Co., Ltd.), 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. Then, stirring was performed at a liquid temperature of 170°C for 8 hours, and after the reaction was fully carried out, the generated water was distilled off as an azeotropic mixture with phenol. Then, the mixture was cooled to 100°C, 500 g of ethanol was added stepwise every 50 g, and after stirring at 60°C for 1 hour, the mixture was washed with water, separated by filtration, and dried at 80°C under reduced pressure for 24 hours to obtain a reaction product. Furthermore, dry pulverization was performed using a Nano Jetmizer, and coarse components were removed using a stainless steel mesh filter (opening diameter 20 μm) to obtain perylene blue pigment 4. Analysis using LC-MS and MALDI-TOF MS revealed that perylene blue pigment 4 was component (a), which was a mixture of the compound represented by formula (55) and the compound represented by formula (56).

[0329] [Chemical formula 45]

[0330]

[0331] (Synthesis Example 11: Synthesis of Perylene Blue Pigment 5)

[0332] To 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 (manufactured by Sigma-Aldrich Co., Ltd.), 366.51 g (3.00 mol) of 3-methylbenzene-1,2-diamine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 64.61 g of piperazine were added, and the liquid temperature was raised to 180°C while stirring the mixture. Then, stirring was performed at a liquid temperature of 180°C for 9 hours, and after the reaction was fully performed, the generated water was distilled off as an azeotropic mixture with phenol. Then, the mixture was cooled to 100°C, 500 g of ethanol was added stepwise every 50 g, and after further stirring at 60°C for 1 hour, the mixture was washed with water, separated by filtration, and dried at 80°C under reduced pressure for 24 hours to obtain a reaction product. Next, 50.00 g of the reaction product was dissolved in 500.00 g of 30% by mass fuming sulfuric acid, and the liquid temperature was raised to 80°C while stirring. The solution was stirred at a liquid temperature of 80°C for 8 hours to allow the sulfonation reaction to proceed. Next, 7 kg of ice water was added to obtain a slurry containing a precipitate, which was filtered and separated. Next, the filter residue was washed with a mixed solution (ethanol: water = mass ratio 80:20), filtered and separated again, and dried at 80°C under reduced pressure for 24 hours. Furthermore, dry pulverization was performed using a Nano Jetmizer, and coarse components were removed using a stainless steel mesh filter (opening diameter 20 μm) to obtain perylene blue pigment 5. LC-MS and MALDI-TOF MS were used for analysis, and the results showed that perylene blue pigment 5 was component (a), which was a mixture of a compound represented by formula (57), a compound represented by formula (58), a compound represented by formula (59), and a compound represented by formula (60).

[0333] [Chemical formula 46]

[0334]

[0335] (Synthesis Example 12: Synthesis of Perylene Blue Pigment 6)

[0336] 80.00 g of perylene blue pigment 2 obtained by the same method as the above-mentioned synthesis example 8 was dissolved in 800.00 g of 10% by mass fuming sulfuric acid, and the liquid temperature was raised to 130°C while stirring. Stirring at a liquid temperature of 130°C for 10 hours to allow the sulfonation reaction to proceed. Next, 14 kg of ice water was added to obtain a slurry, which was then filtered and separated while being washed with ethanol to obtain a wet cake in which the product was concentrated. Furthermore, an aqueous sodium hydroxide solution (10% by mass) was gradually added to the wet cake while stirring for neutralization until the pH reached 7.0. After stirring at a liquid temperature of 30°C for 3 hours, the mixture was filtered and separated while being washed with ethanol. Drying at 80°C under reduced pressure for 24 hours obtained sodium salt A, which is the sodium salt of perylene blue pigment. Analysis was performed using LC-MS and ICP-MS (inductively coupled plasma mass spectrometry). As a result, sodium salt A was composed of component (a) and Na + A mixture is a pigment containing a compound represented by formula (92) and a compound represented by formula (93).

[0337] [Chemical formula 47]

[0338]

[0339] Next, 20.00 g of sodium salt A was added to a flask having 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. Furthermore, 7.32 g of 2-(dodecylamino)ethanol hydrochloride (manufactured by Sigma-Aldrich) was added, and the mixture was stirred at a liquid temperature of 70°C for 3 hours, and then filtered and separated. The mixture was washed with deionized water, dried at 80°C under reduced pressure for 24 hours, and dry-pulverized using a Nano Jetmizer to obtain perylene blue pigment 6. The results of the analysis using LC-MS and MALDI-TOF MS showed that perylene blue pigment 6 was a mixture of a compound represented by formula (94) and a compound represented by formula (95) comprising components (a) and (f).

[0340] [Chemical formula 48]

[0341]

[0342] (Synthesis Example 13: Synthesis of Perylene Blue Pigment 7)

[0343] 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 pigment 7 was synthesized using sodium salt A as a starting material in the same manner as in Synthesis Example 12. Analysis using LC-MS and MALDI-TOF MS revealed that perylene blue pigment 7 was a mixture of a compound represented by formula (96) and a compound represented by formula (97) comprising components (a) and (f).

[0344] [Chemical formula 49]

[0345]

[0346] (Synthesis Example 14: Synthesis of Perylene Blue Pigment 8)

[0347] 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 pigment 8 was synthesized using sodium salt A as a starting material in the same manner as in Synthesis Example 12. Analysis using LC-MS and MALDI-TOF MS revealed that perylene blue pigment 8 was a mixture of a compound represented by formula (98) and a compound represented by formula (99) comprising components (a) and (f).

[0348] [Chemical formula 50]

[0349]

[0350] (Synthesis Example 15: Synthesis of Perylene Blue Pigment 9)

[0351] 100.00 g of "Spectrasense (registered trademark)" Black K0087 (manufactured by Color & Effect Co., Ltd.) was dissolved in 400.00 g of 20% fuming sulfuric acid, and the liquid temperature was raised to 70°C while stirring. Then, the mixture was stirred at a liquid temperature of 70°C for 10 hours to allow the sulfonation reaction to proceed. Next, 15 kg of ice water was added to obtain a slurry, which was then filtered and separated while being washed with ethanol to obtain a wet cake in which the product was concentrated. Furthermore, an aqueous sodium hydroxide solution (10% by mass) was gradually added to the wet cake, and the mixture was neutralized while stirring until the pH reached 7.0, and stirred at a liquid temperature of 30°C for 3 hours. The slurry obtained by neutralization was filtered and separated while being washed with ethanol. The solid separated by filtration was dried at 80°C under reduced pressure for 24 hours to obtain sodium salt B, which is the sodium salt of perylene blue pigment. Analysis using LC-MS and ICP-MS revealed that sodium salt B was a component (a) and Na + A mixture of is a pigment obtained from the compound represented by formula (106) and the compound represented by formula (107).

[0352] [Chemical formula 51]

[0353]

[0354] Next, 20.00 g of sodium salt B was added to a flask having 800.00 g of deionized water, and the mixture was stirred at a liquid temperature of 40°C for 10 minutes to dissolve the mixture. Furthermore, 15.14 g of hexyltrimethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at a liquid temperature of 50°C for 6 hours to confirm the generation of insoluble solid matter. Next, the generated solid matter was washed with deionized water and filtered and separated. The mixture was dried at 80°C for 24 hours under reduced pressure, and dry-pulverized using a Nano Jetmizer to obtain perylene blue pigment 9. The analysis was performed using LC-MS and MALDI-TOF MS, and the results showed that perylene blue pigment 9 was a mixture of a compound represented by formula (108) and a compound represented by formula (109) comprising components (a) and (f).

[0355] [Chemical formula 52]

[0356]

[0357] (Production Example 1: Production of Micronized Perylene Pigment A)

[0358] 1,000.00 g of "Spectrasense (registered trademark)" Black K0087 (manufactured by Color & Effect) was heated in an oven at 250°C for 1 hour under atmospheric pressure / air, and then brought to room temperature. The dried aggregate was disintegrated with a ball mill to obtain a dark purple pigment. 500.00 g of the dark purple pigment, 2.5 kg of ground material (sodium chloride particles), and 250.00 g of dipropylene glycol were mixed and added to a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), and kneaded at 90°C for 8 hours. The kneaded product was added to 5 L of hot water, stirred for 1 hour while maintaining at 70°C, and made into a slurry. Filtration and water washing were repeated until the chloride ions quantified by ion chromatography became less than 50 mass ppm, and the ground material and dipropylene glycol were removed. Furthermore, the mixture was dried in an oven at 100°C for 6 hours under atmospheric pressure and air, and then the dried aggregate was decomposed using a ball mill to obtain a micronized perylene pigment A obtained from a mixture of the compound represented by the formula (61) and the compound represented by the formula (62). The micronized perylene pigment A is the component (e), and corresponds to the compound represented by the formula (30) and the compound represented by the formula (31).

[0359] [Chemical formula 53]

[0360]

[0361] (Production Example 2: Production of Micronized Dioxazine Pigment B)

[0362] 1,000.00 g of "Cromophtal (registered trademark)" Violet D5700 (manufactured by BASF: CI Pigment Violet 37) was heated in an oven at 200°C for 1 hour under atmospheric pressure / air, then allowed to cool to room temperature and deagglomerated using a ball mill to obtain a purple pigment. 500.00 g of purple pigment, 2.5 kg of ground material (sodium chloride particles), and 250.00 g of dipropylene glycol were mixed and added to a stainless steel 1-gallon kneader and kneaded at 90°C for 5 hours. The kneaded product was added to 5 L of hot water and stirred for 1 hour while maintaining at 70°C to form a slurry. The filtration and water washing were repeated three times to remove the ground material and dipropylene glycol. Furthermore, it was dried in an oven at 100°C for 6 hours under atmospheric pressure / air, and then the dried agglomerates were deagglomerated using a ball mill to obtain a micronized dioxazine pigment B represented by formula (63). The micronized dioxazine pigment B is the component (e), and corresponds to the aforementioned compound having a triphenodioxazine skeleton.

[0363] [Chemical formula 54]

[0364]

[0365] (Production Example 3: Production of Salt-Forming Dye C)

[0366] 9.25 g of CI Basic Blue 7 and 200.00 g of deionized water were added to the flask as a basic dye, and stirred at a liquid temperature of 60° C. for 30 minutes. Next, a solution prepared by dissolving 11.50 g of CI Acid Red 52 in 120.00 g of deionized water was added as an acid dye, stirred at a liquid temperature of 60° C. for 1 hour, cooled to 25° C., and then filtered to obtain a purple solid product. The product was then dried at 60° C. for 8 hours to obtain a powdery salt-forming dye C.

[0367] (Synthesis Example 15: Synthesis of Methacrylic Resin Solution G)

[0368] A resin solution synthesized by the same method as that disclosed in Synthesis Example 14 (Resin (F-1) containing a tertiary amino group and an ethylenically unsaturated group) described in Patent Document 5 was used as methacrylic resin solution G.

[0369] 400.00 g of PGMEA was added to a pressure-resistant container equipped with a stirring device, a thermometer, a reflux condenser, and a pump for dropping. After the reaction container was filled 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 mixed solution of 2.0 g of azobisisobutyronitrile and 3.0 g of n-dodecyl mercaptan as a polymerization initiator were added dropwise over 3 hours to copolymerize. Next, the reaction container was replaced with air, and 10.00 g of glycidyl methacrylate was added dropwise over 1 hour to allow the addition reaction to proceed. The mixture was further stirred for 2 hours to obtain a resin solution containing a methacrylic resin having a weight average molecular weight (Mw) of 7000. Furthermore, a resin solution prepared using PGMEA so as to have a solid content of 20.00% by mass was referred to as methacrylic resin solution G.

[0370] (Synthesis Example 16: Synthesis of Methacrylic Resin Solution H)

[0371] A resin solution synthesized by the same method as the synthesis example of the acrylic resin 1 solution described in Patent Document 6 was used as methacrylic resin solution H.

[0372] 800.00 g of cyclohexanone was added to the reaction container, and the mixture was heated to 80° C. while nitrogen was injected into the container. Next, a mixed solution of 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 was added dropwise to the reaction container over 1 hour. After the addition, the mixture was further reacted at 100° C. for 3 hours, and then a solution in which 2.00 g of azobisisobutyronitrile was dissolved in 50.00 g of cyclohexanone was added dropwise, and the mixture was further reacted at 100° C. for 1 hour to obtain a solution containing a methacrylic acid resin having a mass average molecular weight of 40,000. The mixture was cooled to room temperature, and the mixture was diluted with cyclohexanone so that the solid content of the resin solution became 20.00% by mass to obtain a methacrylic acid resin solution H.

[0373] (Synthesis Example 17: Synthesis of Methacrylic Resin Solution I)

[0374] A resin solution synthesized by the same method as Synthesis Example 3: Alkali-soluble resin A-3 described in Patent Document 5 was used as methacrylic resin solution I.

[0375] 26.10 g of 4-hydroxyphenyl methacrylate (Showa Denko K.K. "PQMA") and 13.90 g of glycidyl methacrylate (Tokyo Chemical Industry Co., Ltd.) were added to 100.00 g of PGMEA and stirred for 30 minutes. Separately, a liquid prepared by dissolving 3.66 g of V-601 (Fujifilm Wako Pure Chemical Industries, Ltd.) as a thermal polymerization initiator in 15.00 g of PGMEA was added and stirred for 10 minutes. The two solutions obtained were added dropwise to 45.00 g of PGMEA maintained at a liquid temperature of 85° C. in a 300 mL three-necked flask under a nitrogen atmosphere over 2 hours. After the dropwise addition was completed, the mixture was stirred at a liquid temperature of 85°C for 3 hours and cooled to obtain a solution containing a copolymer having a weight average molecular weight (Mw) of 8600 and a molar ratio of 4-hydroxyphenyl methacrylate to glycidyl methacrylate of 60:40, which is component (b-1). The resin solution prepared using PGMEA so that the solid content was 20.00% by mass was referred to as methacrylic resin solution I.

[0376] (Preparation Example 1: Preparation of Pigment Dispersion Liquid 1)

[0377] To 900.00 g of a mixed solvent (PGME: ethyl lactate: GBL = mass ratio 50:30:20) as component (d), 25.00 g of a polyimide precursor B and 35.00 g of a polybenzoxazole precursor D as component (b-1) were added and stirred for 30 minutes to dissolve. Furthermore, 40.00 g of perylene blue pigment 1 as component (a) was added and stirred for 30 minutes to obtain a pre-mixed liquid. Next, the pre-mixed liquid was sent to a container filled with 75% by volume of the pre-mixed solvent. In a vertical bead mill "Ultra Apex Mill (registered trademark)" (manufactured by Toray Industries, Inc.) with zirconium oxide beads, the wet media dispersion treatment was carried out at a peripheral speed of 8 m / s for 1 hour, and then at a peripheral speed of 10 m / s for 3 hours. The pigment dispersion liquid 1 having a solid content of 10.00% by mass was obtained by filtering with a filter having an opening diameter of 0.5 μm. The blending mass of each raw material is shown in Table 1.

[0378]

[0379] (Preparation Examples 2 to 5: Preparation of Pigment Dispersions 2 to 5)

[0380] Except that perylene blue pigment 2 to 5 were used instead of perylene blue pigment 1 and the blending amounts of each raw material were set as shown in Table 1, wet media dispersion treatment and filtration were performed in the same manner as in Preparation Example 1 to obtain pigment dispersions 2 to 5. The blending mass of each raw material is shown in Table 1.

[0381] (Preparation Examples 6 to 7: Preparation of Pigment Dispersions 6 to 7)

[0382] Instead of perylene blue pigment 1, micronized perylene pigment A or micronized dioxazine pigment B, and perylene blue pigment 2 were used, and the proportions of the raw materials were set to those shown in Table 2. Except for this, wet media dispersion treatment and filtration were performed in the same manner as in Preparation Example 1 to obtain pigment dispersions 6 to 7.

[0383]

[0384] (Preparation Example 8: Preparation of Pigment Dispersion Liquid 8)

[0385] Instead of the mixed solvent (PGME: ethyl lactate: GBL = mass ratio 50: 30: 20), a mixed solvent (PGMEA: ethyl lactate: GBL = mass ratio 50: 30: 20) was used, and the blending amounts of the raw materials were set to those shown in Table 2. Except for this, wet media dispersion treatment and filtration were performed in the same manner as in Preparation Example 1 to obtain pigment dispersion 8. It should be noted that PGME and ethyl lactate are components (d-1), and PGMEA and GBL are components (d-2).

[0386] (Preparation Example 9: Preparation of Pigment Dispersion Liquid 9)

[0387] Instead of the polyimide precursor B and the polybenzoxazole precursor D, TR4020G (cresol Novolac type phenolic resin powder; manufactured by Asahi Organic Materials Co., Ltd.) was used as the (b-1) component, and the blending amounts of the raw materials were set to those shown in Table 2. Except for this, wet media dispersion treatment and filtration were carried out in the same manner as in Preparation Example 1 to obtain a pigment dispersion 9.

[0388] (Preparation Example 10: Preparation of Pigment Dispersion Liquid 10)

[0389] A pigment dispersion prepared according to the method disclosed in Production Example 1 (Production of Colored Pigment Dispersion (DB-1)) described in Patent Document 5 was used as pigment dispersion 10 .

[0390] To 1875.2 g of PGMEA, add 478.50 g of methacrylic resin solution G and 56.30 g of dispersant (dispersant with an amine value of 20 mgKOH / g described in Synthesis Example 2 of Japanese Patent Publication No. 2020-070352), and stir for 10 minutes. Furthermore, add 600.00 g of "Irgaphor Black (registered trademark)" S0100CF (manufactured by BASF; "S0100" in the table) as a lactam black pigment, stir for 20 minutes, and obtain a pre-stirred liquid. The pre-stirred liquid is sent to a container filled with a filling rate of 70% by volume as The pigment dispersion 10 having a solid content of 25.00% by mass and a pigment:resin mass ratio of 80:20 was obtained by performing a wet medium dispersion treatment for 3 hours at a peripheral speed of 10 m / s in a circulation manner in a vertical bead mill "TORAYCERAM (registered trademark)" (manufactured by Toray Industries, Ltd.; manufactured by HIROSHIMA MTEAL & MACHINERY Co., Ltd.) containing zirconium oxide beads. The pigment dispersion 10 having a solid content of 25.00% by mass and a pigment:resin mass ratio of 80:20 was obtained. The blending amount of each raw material is shown in Table 2.

[0391] (Preparation Example 11: Preparation of Pigment Dispersion Liquid 11)

[0392] A pigment dispersion 11 was obtained by performing wet media dispersion treatment and filtration in the same manner as in Preparation Example 1 except that micronized perylene pigment A was used instead of perylene blue pigment 1 and the blending amounts of the raw materials were as shown in Table 3.

[0393]

[0394] (Preparation Example 12: Preparation of Pigment Dispersion Liquid 12)

[0395] To 515.00 g of cyclohexanone, 5.00 g of Solsperse 24000 (manufactured by Lubrizol) as an amine resin and 20.00 g of MALKYD No. 32 (manufactured by Arakawa Chemical Co., Ltd.) as a rosin-modified maleic acid resin were added, and the mixture was 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) as a copper phthalocyanine compound having a basic functional group, 60.00 g of CI Pigment Blue 60 as an organic pigment, 100.00 g of CI Pigment Yellow 139, and 40.00 g of CI Pigment Violet 23 were added, and the mixture was stirred for 30 minutes to obtain a pre-stirred solution. Next, a 400 ml tumbler filled with The mixture was subjected to a wet media dispersion treatment using a sand mill with glass beads for 5 hours, and filtered using a filter having an opening diameter of 1 μm to obtain a pigment dispersion 12.

[0396] [Chemical formula 55]

[0397]

[0398] (Example 1)

[0399] Under a yellow light, 1.15 g of polyimide precursor B as component (b-1), 0.68 g of quinonediazide compound E as component (c), and 7.50 g of crosslinker solution X (manufactured by Honshu Chemical Industry Co., Ltd.; a solution prepared by dissolving the compound represented by formula (65) and the compound represented by formula (66) in a mixed solvent of PGME: ethyl lactate: GBL = 50:30:20 in a mass ratio) as component (d) were added, and stirred for 30 minutes to dissolve. 24.20 g of pigment dispersion 1 was further added, stirred for 1 hour, and filtered using a filter with an opening diameter of 0.5 μm to obtain a positive photosensitive composition 1 having a solid content of 10.00 mass%. The blending amount of each raw material is shown in Table 4. In addition, PGME and ethyl lactate are components (d-1).

[0400] [Chemical formula 56]

[0401]

[0402]

[0403] A coating step was performed to obtain a coating film. In the coating step, the rotation speed was adjusted so that the film thickness of the cured film after heating at 250° C. for 1 hour in a nitrogen atmosphere described later would be 1.50 μm, and the positive photosensitive composition 1 was applied to the surface of Tempax (AGC Technoglass Co., Ltd.) as a transparent glass substrate by a spin coater. A prebaking step of heating the coated film at 110° C. for 2 minutes under atmospheric pressure was performed using a hot plate to obtain a prebaked film. The exposure step was not performed, and the development step was performed by the same method as in the measurement of the above-mentioned optimal exposure amount to obtain a solid developed film. Next, the first curing step (under a nitrogen atmosphere, 250° C. for 1 hour) of heating the developed film using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.) was performed to obtain a substrate A for light-shielding property evaluation having a solid cured film with a film thickness of 1.50 μm, and the light-shielding property (OD / μm) was evaluated by the above-mentioned method.

[0404] On the other hand, a developing film was formed on Tempax by the same method, and the first curing step (under nitrogen atmosphere, 270°C for 1 hour) was performed. After being cooled to 30°C naturally, the film was placed in a high-temperature inert oven again, and the second curing step (under nitrogen atmosphere, 270°C for 1 hour) was further performed. The substrate thus obtained was used as a substrate B for light-shielding evaluation, and the light-shielding property (OD / μm) was evaluated. The thermal stability of the light-shielding property (ΔOD / μm) was evaluated by the aforementioned method. The results are shown in Table 5.

[0405]

[0406] Next, a positive exposure mask (a hole pattern mask having 200 perfectly circular transmission portions with a diameter of 10.0 μm arranged) was used instead of a positive exposure mask (a hole pattern mask having 50 perfectly circular transmission 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 arranged). Except for this, a coating step, a pre-baking step, an exposure step, a developing step and a curing step were performed by the same method as the above-mentioned determination of the optimal exposure amount, and a substrate for resolution evaluation having a cured film with a film thickness of 1.50 μm having hole-shaped openings on the ITO surface of a glass substrate having a silver alloy film / ITO film was obtained, and the resolution was evaluated by the above-mentioned method. The evaluation results are shown in Table 5.

[0407] (Examples 2 to 5)

[0408] Positive photosensitive compositions 2 to 5 were prepared in the amounts shown in Table 4. In addition to preparing substrates A and B for light-shielding evaluation, a substrate for resolution evaluation was also prepared using the same method as in Example 1. The thermal stability of light-shielding properties and resolution were evaluated using the aforementioned methods, and the results are shown in Table 5.

[0409] (Examples 6 to 10)

[0410] Positive photosensitive compositions 6 to 10 were prepared in the amounts shown in Table 6. In addition to preparing substrates A and B for light-shielding property evaluation, a substrate for resolution evaluation was prepared by the same method as in Example 1. The thermal stability of light-shielding property and resolution were evaluated by the aforementioned methods. The results are shown in Table 7. It should be noted that crosslinking agent solution Y (manufactured by Honshu Chemical Industry Co., Ltd.; a solution prepared by dissolving the compound represented by formula (65) and the compound represented by formula (66) in a mixed solvent of PGMEA:ethyl lactate:GBL at a mass ratio of 50:30:20) to give a solid content of 10.00 mass %) was used only in the preparation of positive photosensitive composition 8.

[0411]

[0412]

[0413] (Comparative Example 1)

[0414] Under a yellow light, 6.35 g of polyimide precursor B and 1.81 g of quinonediazide compound F were added to 26.50 g of a mixed solvent (ethyl lactate:GBL = mass ratio 50:50), and stirred for 30 minutes to dissolve. Next, 0.64 g of salt-forming dye C obtained in the above-mentioned Production Example 3, 1.63 g of CI Solvent Blue 45 as a dye, 10.89 g of the above-mentioned 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 of the compound represented by formula (69) were added, and stirred for 1 hour to dissolve, thereby obtaining a positive photosensitive composition 11. The blending mass of each raw material is shown in Table 8. Next, using the positive photosensitive composition 11, in addition to preparing substrates A and B for light-shielding evaluation, a substrate for resolution evaluation was also prepared by the same method as in Example 1, and the thermal stability of light-shielding property and resolution were evaluated by the above-mentioned method. The results are shown in Table 9.

[0415] [Chemical formula 57]

[0416]

[0417] [Table 8]

[0418]

[0419] [Table 9]

[0420]

[0421] (Comparative Example 2)

[0422] A positive photosensitive composition 12 was prepared with the amount shown in Table 8, and a substrate for evaluating resolution was prepared in addition to preparing substrates A and B for evaluating light-shielding properties in the same manner as in Example 1, and the thermal stability of light-shielding properties and resolution were evaluated by the aforementioned methods. The results are shown in Table 9.

[0423] (Comparative Example 3)

[0424] To 24.34 g of PGMEA, 14.22 g of methacrylic resin solution I, 2.12 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.; "DPHA" in the table) as a radical polymerizable compound, 0.27 g of "ADEKA ARKLS" (registered trademark) NCI-831 (manufactured by ADEKA Co., Ltd.; "NCI-831" in the table) as a photopolymerization initiator, and 0.01 g of BYK-333 (manufactured by BYK-Chemie) as a silicone surfactant were added and stirred for 30 minutes. Furthermore, 9.05 g of pigment dispersion 10 was added and stirred for 1 hour to prepare a negative photosensitive composition 1 having a solid content of 15.00% by mass. The blending mass of each raw material is shown in Table 10.

[0425] [Table 10]

[0426]

[0427] On the surface of Tempax, a coating process of applying a negative photosensitive composition 1 using a spin coater is carried out to obtain a coating film. In the coating process, the rotation speed is adjusted in such a way that the film thickness of the cured film after heating at 250°C for 1 hour in a nitrogen atmosphere described later becomes 1.50μm. Using a heating plate, a pre-baking process of heating the coating film at 110°C for 2 minutes under atmospheric pressure is carried out to obtain a pre-baked film. The exposure process is carried out with the optimal exposure amount measured by the aforementioned method, and the development process is carried out by the same method as when measuring the aforementioned optimal exposure amount to obtain a whole-surface developed film. Next, substrates A and B for light-shielding evaluation are obtained by the same method as in Example 1, and the thermal stability of light-shielding is evaluated by the aforementioned method. The evaluation results are shown in Table 11.

[0428] Next, except that a negative exposure mask (a hole pattern mask having 50 perfectly circular shielding portions of 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) was used, a coating step, a pre-baking step, an exposure step, a developing step and a curing step were performed by the same method as the above-mentioned determination of the optimal exposure amount, and a substrate for resolution evaluation having a cured film having a film thickness of 1.50 μm and hole-shaped openings on the ITO surface of the glass substrate having the silver alloy film / ITO film was obtained, and the resolution was evaluated by the above-mentioned method. The evaluation results are shown in Table 11.

[0429]

[0430] (Comparative Example 4)

[0431] To 20.64 g of cyclohexanone, add 1.85 g of methacrylic resin solution H, 2.00 g of dipentaerythritol hexaacrylate as a free radical polymerizable compound, and 0.50 g of "Irgacure" (registered trademark) 369 (manufactured by BASF; "Irgacure369" in the table) as a photopolymerization initiator, and stir for 30 minutes. Furthermore, add 25.01 g of pigment dispersion 12, stir for 1 hour, and prepare a negative photosensitive composition 2 with a solid content of 20.00% by mass. The blending mass of each raw material is shown in Table 10. Next, using the negative photosensitive composition 2, in addition to preparing substrates A and B for light-shielding evaluation, a substrate for resolution evaluation is also prepared using the same method as in Comparative Example 3, and the thermal stability and resolution of light-shielding are evaluated using the aforementioned method. The evaluation results are shown in Table 11.

[0432] (Comparative Example 5)

[0433] A negative photosensitive composition 3 was prepared with the proportions shown in Table 10. In addition to preparing substrates A and B for light-shielding evaluation, a substrate for resolution evaluation was also prepared using the same method as in Example 1. The thermal stability of light-shielding properties and resolution were evaluated using the aforementioned methods. The results are shown in Table 11.

[0434] (Preparation Example 13: Preparation of Pigment Dispersion Liquid 13)

[0435] To 360.00 g of a mixed solvent (PGME: ethyl lactate: GBL = mass ratio 50:30:20) as component (d), 10.00 g of a polyimide precursor B and 14.00 g of a polybenzoxazole precursor D as component (b-1) were added, and the mixture was stirred for 30 minutes to dissolve. Furthermore, 16.00 g of perylene blue pigment 6 as a salt of component (a) and component (f) was added, and the mixture was stirred for 30 minutes to dissolve, thereby obtaining a pre-mixed liquid. The pre-mixed liquid contained a small amount of insoluble components of perylene blue pigment 6, so the pre-mixed liquid was sent to a container filled with perylene blue pigment 6 at a filling rate of 75% by volume. The pigment dispersion 13 having a solid content of 10.00% by mass was obtained by filtering with a filter having an opening diameter of 0.5 μm. The blending mass of each raw material is shown in Table 12.

[0436]

[0437] (Preparation Examples 14 to 16: Preparation of Pigment Dispersions 14 to 16)

[0438] Pigment dispersions 14 to 16 were obtained in the same manner as in Preparation Example 13 except that perylene blue pigment 7, perylene blue pigment 8, and perylene blue pigment 9 were used instead of perylene blue pigment 6. Table 12 shows the blending mass of each raw material.

[0439] (Examples 11 to 13, and Example 27)

[0440] Positive photosensitive compositions 13 to 16 were prepared in the amounts shown in Table 13, and in addition to preparing substrates A and B for light-shielding evaluation, a substrate for resolution evaluation was prepared in the same manner as in Example 1, and the thermal stability of light-shielding properties and resolution were evaluated by the aforementioned methods. The results are shown in Table 14.

[0441]

[0442]

[0443] (Example 14)

[0444] A pixel dividing layer including a cured film of the positive photosensitive composition 1 and an organic EL display device including the pixel dividing layer were produced by the following method.

[0445] Figure 3 The following is a production process of an organic EL display device including a step of forming a pixel division layer.

[0446] On the surface of an alkali-free glass substrate 12 with a length of 70 mm and a width of 70 mm, a silver alloy (an alloy obtained from 99.00 wt% of silver and 1.00 wt% of copper) is formed on the entire surface by sputtering. Using an alkali-soluble Novolac-based positive resist, the substrate is immersed in a silver alloy etching solution with a liquid temperature of 30°C for etching to obtain a patterned silver alloy film 13 with a film thickness of 50 nm. Furthermore, an ITO film (indium-tin oxide) is formed on the entire surface by sputtering. Using an alkali-soluble Novolac-based positive resist, the substrate is immersed in a 5 wt% oxalic acid aqueous solution with a liquid temperature of 50°C for 5 minutes, and then rinsed with deionized water for 2 minutes. It is then dried by air blowing to obtain an ITO film 14 with the same pattern and a film thickness of 10 nm. Through the above steps, a first electrode forming substrate having a first electrode obtained from a stacked pattern of a silver alloy film / ITO film on the surface of an alkali-free glass substrate is obtained.

[0447] Using a spin coater, the rotation speed is adjusted in such a way that the film thickness of the pixel division layer finally obtained becomes 1.50μm, and the positive photosensitive composition 1 is applied to the surface of the first electrode forming substrate to obtain a coating film. Furthermore, using a hot plate, the coating film is pre-baked at 110°C for 120 seconds under atmospheric pressure to obtain a pre-baked film. The pre-baked film is pattern-exposed with the optimal exposure amount obtained by the above method through a positive exposure mask (a hole pattern mask with 200 perfectly circular transparent parts arranged) to obtain an exposure film. It should be noted that the opening width of the transparent part of the positive exposure mask is set to be the same as the opening width when the resolution of various positive photosensitive compositions is obtained in the evaluation of the resolution of the cured film and the protruding foreign matter defects mentioned above (2). That is, in the case of the positive photosensitive composition 1, a hole pattern mask with a diameter of 4.0μm of the perfectly circular transparent part is used. It should be noted that the pattern exposure is carried out by bringing the positive exposure mask into contact with the surface of the pre-baked 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 obtain a pixel division layer forming substrate having a pixel division layer 15 with 200 openings in a region of 30 mm in length and 30 mm in width in the central portion of the first electrode forming substrate.

[0448] Next, in order to form the organic EL layer 16 including the light emitting layer in the opening of the pixel division layer 15 by vacuum deposition, the vacuum degree was 1×10 -3 Under the vapor deposition conditions of less than 100 Pa, the pixel division layer forming substrate is rotated relative to the vapor deposition source. First, the compound (HT-1) represented by formula (100) is formed into a film with a thickness of 10 nm as a hole injection layer, and the compound (HT-2) represented by formula (101) is formed into a film with a thickness of 50 nm as a hole transport layer. Next, the compound (GH-1) represented by formula (102) as a host material and the compound (GD-1) represented by formula (103) as a dopant material are vapor deposited on the light-emitting layer with a thickness of 40 nm. Next, the compound (ET-1) represented by formula (104) as an electron transport material and the compound (LiQ) represented by formula (105) are stacked at a volume ratio of 1:1 and a thickness of 40 nm.

[0449] [Chemical formula 58]

[0450]

[0451] [Chemical formula 59]

[0452]

[0453] Next, after evaporating 2nm of the compound (LiQ), silver / magnesium alloy (volume ratio 10:1) was evaporated in a manner to a thickness of 150nm to form the second electrode 17. Next, an epoxy resin-based adhesive was used to bond a cap-shaped glass plate in a low humidity / nitrogen atmosphere, thereby sealing to obtain an organic EL display device arranged with green light-emitting pixels. It should be noted that the layers constituting the organic EL layer 16 are very thin compared to the aforementioned pixel division layer, and a high measurement accuracy cannot be obtained in a stylus-type film thickness measuring device. Therefore, a quartz oscillation film thickness monitor suitable for thin films less than 100nm was used for measurement, and the value obtained by rounding off the first decimal place of the average value of the three points in the plane was used as the thickness of the film. The resolution of the organic EL display device produced was evaluated using the aforementioned method, and the results are shown in Table 15.

[0454] [Table 15]

[0455]

[0456] (Examples 15 to 26, and Example 28)

[0457] Organic EL display devices were prepared by the same method as in Example 14 using positive photosensitive compositions 2 to 10 and 13 to 16 instead of positive photosensitive composition 1. The resolution of the organic EL display devices was evaluated by the above method. The results are shown in Table 15.

[0458] (Reference Example 1)

[0459] 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 22.50 g of pigment dispersion 11 was added and stirred to prepare reference composition 1. Reference composition 1 is a composition that does not contain component (c) and does not have any photosensitivity of negative type or positive type. The blending amount is shown in Table 16.

[0460] Next, the rotation speed is adjusted so that the transmittance of the prebaked film obtained after the prebaking step becomes 10% at a wavelength of 560nm, and a coating step of applying the reference composition 1 using a spin coater is performed to obtain a coated film on the surface of Tempax. Using a hot plate, a prebaking step of heating the coated film at 110°C for 2 minutes under atmospheric pressure is performed to obtain a prebaked film. The transmittance of the obtained prebaked film at a wavelength of 350 to 650nm is measured using a spectrophotometer U-4100 (manufactured by Hitachi, Ltd.). Figure 4In the graph, the measurement results are shown by a dotted line. In addition, the reference composition 1 was measured using a particle size distribution measuring device SZ-100 (manufactured by Horiba, Ltd.) based on a dynamic light scattering method, and the result outputted a particle size distribution. Therefore, it is considered that the micronized perylene pigment A exists in the reference composition 1 as a pigment.

[0461] (Reference Example 2)

[0462] Reference composition 2 was prepared by using pigment dispersion 16 instead of pigment dispersion 11 in the amount shown in Table 16. Reference composition 2 is a composition that does not contain component (c) and does not have any photosensitivity of negative type or positive type. Using reference composition 2, a prebaked film was obtained by the same method as reference example 1, and the transmittance at a wavelength of 350 to 650 nm was measured. Figure 4 In the graph, the measurement results are shown with a solid line. According to the comparison between Reference Example 1 and Reference Example 2, it is believed that perylene blue pigment 9 is relatively high in the near-ultraviolet region when the transmittance at a wavelength of 560nm is the same as that of micronized perylene pigment A, and is a color material suitable for obtaining high resolution. In addition, using the same method as Reference Example 1, SZ-100 was used to measure Reference Composition 2, and no particle components were detected, so it can be considered that perylene blue pigment 9 exists in the form of a dye in a completely dissolved state in Reference Composition 2.

[0463] [Table 16]

[0464]

[0465] From the above results, it can be seen that the positive photosensitive compositions in Examples 1 to 13 and Example 27 can form cured films having both high light-shielding properties, thermal stability and high resolution while suppressing the generation of protruding foreign matter defects, compared with the positive photosensitive compositions in Comparative Examples 1 to 2 and the negative photosensitive compositions in Comparative Examples 3 to 5. It is also known that the organic EL display device having a pixel segmentation layer containing the cured film of the present invention has excellent resolution.

[0466] Therefore, it was found that the positive photosensitive composition, cured film, organic EL display device, and dye of the present invention are useful.

[0467] Industrial Applicability

[0468] The positive photosensitive composition of the present invention is useful for applications requiring high light-shielding thermal stability and high resolution, and can be suitably used as a material for forming a planarization layer of a micro-LED display, a black matrix of a liquid crystal display, a black columnar spacer of a liquid crystal display, a near-infrared-transmissive visible light shielding film of a solid-state imaging element, etc., in addition to a pixel segmentation layer and a TFT planarization layer of an organic EL display device. Among them, it can be particularly suitably used as a material for forming a pixel segmentation layer and a TFT planarization layer of an organic EL display device.

[0469] Description of Reference Numerals

[0470] 1: TFT

[0471] 2: Wiring

[0472] 3: TFT insulation layer

[0473] 4: Flattening layer

[0474] 5: First electrode

[0475] 6: Substrate

[0476] 7: Contact hole

[0477] 8: Pixel segmentation layer

[0478] 9: Luminous Pixels

[0479] 10: Second electrode

[0480] 11: Protruding foreign body defect

[0481] 12: Alkali-free glass substrate

[0482] 13: Silver alloy film

[0483] 14: ITO film

[0484] 15: Pixel segmentation layer

[0485] 16: Organic EL layer

[0486] 17: Second electrode

Claims

1. A positive photosensitive composition comprising (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, [Chemical formula 1] In formula (1), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each independently represents a hydrogen atom, -SO3H, -SO3 - , an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, -CF3, -F, -Br or -CN; wherein, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 In -SO3H and -SO3 - The total number is 1 to 4; R 9 , R 10 , R 11 and R 12 Each independently represents a hydrogen atom, -OH, -F, -Br, -CN or an alkoxy group having 1 to 5 carbon atoms; wherein R 9 With R 10 , R 11 With R 12 Each independently optionally bonded to each other to form a linking group -X 1 -; -X 1 - represents -O- or -SO2-; In formula (2), R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 Each independently represents a hydrogen atom, -SO3H, -SO3 - , an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, -CF3, -F, -Br or -CN; wherein R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 In -SO3H and -SO3 - The total number is 1 to 4; R 21 , R 22 , R 23 and R 24 Each independently represents a hydrogen atom, -OH, -F, -Br, -CN or an alkoxy group having 1 to 5 carbon atoms; wherein R 21 With R 22 , R 23 With R 24 Each independently optionally bonded to each other to form a linking group -X 2 -; -X 2 - represents -O- or -SO2-.

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), [Chemical formula 2] In formula (5), R 25 and R 26 Each independently represents -SO3H or -SO3 - ;n 1 and n 2 is an integer, each independently representing 0 to 2; wherein, n 1 and n 2 The total number is 1 to 4; In formula (6), R 27 and R 28 Each independently represents -SO3H or -SO3 - ;n 3 and n 4 is an integer, each independently representing 0 to 2; wherein, n 3 and n 4 The total number is 1 to 4.

3. The positive photosensitive composition according to claim 1 or 2, further comprising (f) a compound represented by formula (70), [Chemical formula 3] In formula (70), R 81 N + or P + ; R 82 , R 83 , R 84 and R 85 Each independently represents an alkyl group having 1 to 20 carbon atoms, a phenyl group or a hydrogen atom which is optionally substituted with -OH or a phenyl group; wherein, R 81 N + In the case of R 82 , R 83 , R 84 and R 85 The total number of hydrogen atoms is 0 to 2, R 81 P + In the case of R 82 , R 83 , R 84 and R 85 The total number of hydrogen atoms is 0.

4. The positive photosensitive composition according to claim 1 or 2, wherein The resin (b) includes (b-1) a phenolic hydroxyl group-containing resin, and the (b-1) phenolic hydroxyl group-containing resin includes at least one resin selected from the group consisting of polyimide, a polyimide precursor, a polybenzoxazole precursor, and copolymers thereof.

5. The positive photosensitive composition according to claim 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 tribenzodioxazine skeleton, [Chemical formula 4] 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 represents a hydrogen atom, -F, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms.

6. The positive photosensitive composition according to claim 1 or 2, wherein The photoacid generator (c) contains (c-1) at least one compound selected from the group consisting of a compound having two or more groups represented by the formula (22) in the molecule and having a phenolic hydroxyl group, a compound having two or more groups represented by the formula (23) in the molecule and having a phenolic hydroxyl group, and a compound having a group represented by the formula (22) and a group represented by the formula (23) and having a phenolic hydroxyl group, [Chemical formula 5] In formula (22), R 54 , R 55 , R 56 and R 57 Each independently represents 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; In formula (23), R 58 , R 59 and R 60 Each independently represents 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.

7. The positive photosensitive composition according to claim 1 or 2, wherein: The component (d) contains (d-1) an organic solvent having a hydroxyl group, and the content of the component (d-1) is 50% by mass or more in 100% by mass of the component (d).

8. A cured film comprising a cured product of the positive photosensitive composition according to claim 1 or 2.

9. An organic EL display device comprising a pixel segmentation layer and a planarization layer, The pixel segmentation layer and / or the planarization layer contains the cured film according to claim 8.

10. A pigment comprising, in addition to (f) a compound represented by formula (70), (a) a compound represented by formula (85) and / or a compound represented by formula (86), [Chemical formula 6] In formula (70), R 81 N + or P + ; R 82 , R 83 , R 84 and R 85 Each independently represents an alkyl group having 1 to 20 carbon atoms, a phenyl group or a hydrogen atom which is optionally substituted with -OH or a phenyl group; wherein, R 81 N + In the case of R 82 , R 83 , R 84 and R 85 The total number of hydrogen atoms is 0 to 2, R 81 P + In the case of R 82 , R 83 , R 84 and R 85 In the equation, 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 represents a hydrogen atom, -SO3H, -SO3 - , an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, -CF3, -F, -Br or -CN; wherein R 91 , R 92 , R 93 , R 94 , R 95 , R 96 , R 97 and R 98 In -SO3H and -SO3 - The total number of is 1 to 4, at least one of which is -SO3 - ; R 99 , R 100 , R 101 and R 102 Each independently represents a hydrogen atom, -OH, -F, -Br, -CN or an alkoxy group having 1 to 5 carbon atoms; wherein R 99 With R 100 , R 101 With R 102 Each independently optionally bonded to each other to form a linking group -X 3 -; -X 3 - represents -O- or -SO2-; In formula (86), R 103 , R 104 , R 105 , R 106 , R 107 , R 108 , R 109 and R 110 Each independently represents a hydrogen atom, -SO3H, -SO3 - , an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, -CF3, -F, -Br or -CN; wherein R 103 , R 104 , R 105 , R 106 , R 107 , R 108 , R 109 and R 110 In -SO3H and -SO3 - The total number of is 1 to 4, at least one of which is -SO3 - ; R 111 , R 112 , R 113 and R 114 Each independently represents a hydrogen atom, -OH, -F, -Br, -CN or an alkoxy group having 1 to 5 carbon atoms; wherein R 111 With R 112 , R 113 With R 114 Each independently optionally bonded to each other to form a linking group -X 4 -; -X 4 - represents -O- or -SO2-.

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