Positive-type photosensitive pigment composition and a cured film containing the cured product thereof, and organic EL display device

Abstract

The purpose of the present invention is to provide a positive photosensitive pigment composition having high long-term storage stability with respect to halftone processability, with which an organic EL display device having excellent light resistance reliability can be obtained and light-shielding pixel division layers and spacer layers can be collectively formed. The present invention is a positive photosensitive pigment composition containing (a) a triphendioxazine pigment having a carboxylic acid amide bond and / or a carboxylic acid ester bond, (b) a resin having a structure represented by formula (1) and / or a structure represented by formula (2), (c) a photoacid generator, and (d) an organic solvent.

Description

[Technical Field]

[0001] The present invention relates to a positive-type photosensitive pigment composition and a cured film containing the same, as well as to an organic EL display device. [Background technology]

[0002] In recent years, products incorporating flexible organic electroluminescent (EL) display devices have been developed. By eliminating the use of thick polarizing plates that were conventionally placed on the front of the panel, not only is the flexibility of the panel improved, but brightness loss is eliminated, and an extension of the lifespan of the light-emitting pixels is expected. The light-emitting elements of organic EL display devices have patterns that function as insulating layers called pixel division layers or pixel definition layers to separate each light-emitting pixel. To replace the function of the polarizing plate, it is necessary to add a function that suppresses the reflection of external light such as sunlight, and technology to give light-shielding properties to the pixel division layer is attracting attention. In addition to increasing the resolution by narrowing the aperture width of the pixel division layer and reducing the size of the light-emitting pixels, further improvement in light resistance reliability is also required to extend the product lifespan of the display device.

[0003] Incidentally, in order to significantly improve the yield during panel production, a technique is known in which a convex spacer layer is formed on a part of the surface of the pixel division layer when pattern-depositing the light-emitting layer at the openings of the pixel division layer. This reduces the contact area between the deposition mask and the pixel division layer, thereby suppressing the occurrence of defects. As a method for forming the pixel division layer and the spacer layer, a technique is known in which the pixel division layer and the spacer layer are formed together by a photolithography method that includes an exposure step of irradiating exposure light including at least near ultraviolet light through a halftone exposure mask having fully transparent, semi-transparent, and shielding areas in its plane (halftone processing). Halftone processing is economically advantageous because it can significantly reduce manufacturing process costs compared to two-layer processing, in which the spacer layer is further laminated after the pixel division layer is formed.

[0004] Technical document 1 discloses a negative-type photosensitive pigment composition containing CI pigment violet 37, which is a triphendioxazine pigment, and a polymer-type dispersant having an N,N-dialkylaminoalkyl group, as a material for simultaneously forming a light-shielding pixel division layer and a spacer layer.

[0005] On the other hand, Patent Document 2 discloses a positive-type photosensitive pigment composition as a material for forming a light-shielding pixel division layer, which contains an organic pigment that has been pseudo-blackened by mixing CI Pigment Yellow 192, CI Pigment Red 179, and CI Pigment Blue 60, a perylene-based dye derivative type dispersant having an N,N-dialkylaminoalkyl group, and a polymer-type dispersant having a phosphate group. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] International Publication No. 2019 / 087985 [Patent Document 2] International Publication No. 2019 / 065359 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] However, when the pixel splitting layer and spacer layer are formed collectively using the negative-type photosensitive pigment composition disclosed in Patent Document 1 and the positive-type photosensitive pigment composition disclosed in Patent Document 2, the long-term storage stability of the photosensitive pigment composition in terms of halftone processing is insufficient, resulting in a problem of a low pixel emission area ratio in organic EL display devices equipped with the pixel splitting layer and spacer layer. Furthermore, the light resistance reliability of the organic EL display device is insufficient, which further reduces the pixel emission area ratio. Therefore, there has been a strong desire for a photosensitive composition that allows for the simultaneous formation of a light-shielding pixel division layer and a spacer layer, resulting in an organic EL display device with high long-term storage stability in halftone processing and excellent light resistance. [Means for solving the problem]

[0008] To solve the above problems, the present invention has the following configuration. [1](a) A triphendioxazine pigment having a carboxylic acid amide bond and / or a carboxylic acid ester bond, (b) A resin having a structure represented by formula (1) and / or formula (2), (c) Photoacid generator and, (d) A positive-type photosensitive pigment composition containing an organic solvent.

[0009] [ka]

[0010] In formula (1), n 1 is an integer, representing either 1 or 2. n 1 If R is 1, 1 n represents a divalent organic group with 2 to 30 carbon atoms that does not contain a carboxylic acid amide bond or a carboxyl group. 1 If R is 2, 1 * represents a trivalent organic group with 5 to 30 carbon atoms that does not contain carboxylic acid amide bonds or carboxyl groups. * represents a bonding site with a carbon atom.

[0011] [ka]

[0012] In formula (2), R 2 * represents a trivalent organic group with 5 to 30 carbon atoms that does not contain carboxylic acid amide bonds or carboxyl groups. * represents a bonding site with a carbon atom. [2] The positive-type photosensitive pigment composition according to [1], wherein the component (a) comprises a triphendioxazine pigment represented by formula (4) and / or a triphendioxazine pigment represented by formula (5) described later. [3] The positive-type photosensitive pigment composition according to [1] or [2], wherein the component (a) contains a triphendioxazine pigment represented by formula (6) described later. [4] A positive-type photosensitive pigment composition according to any one of [1] to [3], wherein the component (a) contains a triphendioxazine pigment represented by formula (7) described later. [5] Furthermore, the positive-type photosensitive pigment composition according to any one of [1] to [4], comprising (e) an organic dye having a sulfo group bonded to a carbon atom constituting an aromatic ring and / or a carboxyl group bonded to a carbon atom constituting an aromatic ring, and having no chlorine atoms in the molecule. [6] The positive-type photosensitive pigment composition according to [5], wherein the component (e) is selected from the group consisting of triphendioxazine dyes, perylenebisimide dyes, and anthraquinone dyes. [7] The positive-type photosensitive pigment composition according to [5] or [6], wherein the component (e) contains a compound represented by formula (62) and / or a compound represented by formula (63) described later. [8] A positive-type photosensitive pigment composition according to any one of [1] to [7], wherein the component (b) comprises a repeating unit represented by formula (36) described later and a resin having a structure represented by formula (47) described later. [9] A positive-type photosensitive pigment composition according to any one of [1] to [8], further comprising (g) a perylene-based black pigment having a benzimidazole skeleton. A cured film comprising a cured product of a positive-type photosensitive pigment composition as described in any of

[10] [1] to [9]. An organic EL display device comprising the cured film described in

[11]

[10] .

[0013] Furthermore, the organic EL display device of the present invention is

[12] An organic EL display device comprising a pixel splitting layer containing a triphendioxazine pigment represented by formula (7).

[0014] [ka]

[0015] In formula (7), R 43 , R 44 , R 45 and R 46 each independently represents an alkyl group having 1 to 4 carbon atoms.

[13] The organic EL display device according to

[12] , wherein the pixel division layer further contains a triphendioxazine-based dye having a sulfo group bonded to a carbon atom constituting an aromatic ring and / or a carboxyl group bonded to a carbon atom constituting an aromatic ring and having no chlorine atom in the molecule.

Advantages of the Invention

[0016] According to the positive photosensitive pigment composition of the present invention, an organic EL display device having high long-term storage stability in halftone processing properties and excellent light resistance reliability can be obtained, and a light-shielding pixel division layer and a spacer layer can be formed together.

Brief Description of the Drawings

[0017] [Figure 1] It is an image obtained by observing a cross section of a substrate for evaluating the required minimum exposure amount obtained in Example 1 with a scanning electron microscope (SEM). [Figure 2] It is a schematic diagram of a light-emitting pixel portion having a light-emitting portion and no non-light-emitting portion. [Figure 3] It is a schematic diagram of a light-emitting pixel portion having a light-emitting portion and a non-light-emitting portion. [Figure 4] It is a manufacturing process of an organic EL display device including a process of forming a pixel division layer in all Examples and Comparative Examples.

Modes for Carrying Out the Invention

[0018] The present invention will be described in detail below. A numerical range expressed using "~" means a range that includes the values ​​written before and after "~" as the lower and upper limits. The pixel division layer refers to the pixel division layer provided by an organic EL display device and does not include the black matrix of a liquid crystal display device. Visible light refers to light in the region of wavelengths from 380 nm to less than 780 nm, and near ultraviolet refers to light in the region of wavelengths from 200 nm to less than 380 nm. Light shielding refers to the function of reducing the intensity of transmitted light relative to the intensity of light incident perpendicular to the cured film, and light shielding property refers to the degree to which visible light is shielded. Transmittance refers to light transmittance. Weight-average molecular weight (Mw) is a value obtained by analysis using gel permeation chromatography (GPC) with tetrahydrofuran as the carrier and converted using a calibration curve with standard polystyrene.

[0019] The abbreviation "CI" used in the names of some colorants stands for Colour Index Generic Name. Based on the Color Index published by The Society of Dyers and Colourists, for colorants registered in the Color Index, the Colour Index Generic Name represents the chemical structure or crystalline form of the pigment or dye. Carbon black, such as CI Pigment Black 7, is classified as an inorganic black pigment. Solids content refers to the proportion (by weight) of components in a positive-type photosensitive pigment composition, excluding organic solvents and water.

[0020] As a result of diligent research, the inventors have found that a pigment composition obtained by dispersing a pigment having a specific structure in an organic solvent in combination with a resin having a specific structure, and further imparting positive-type photosensitivity with a photoacid generator, exhibits a particularly remarkable effect in solving the aforementioned problems.

[0021] In other words, the positive-type photosensitive pigment composition of the present invention is (a) A triphendioxazine pigment having a carboxylic acid amide bond and / or a carboxylic acid ester bond, (b) A resin having a structure represented by formula (1) and / or formula (2), (c) Photoacid generator and, (d) A positive-type photosensitive pigment composition containing an organic solvent.

[0022] [ka]

[0023] In formula (1), n 1 is an integer, representing either 1 or 2. n 1 If R is 1, 1 n represents a divalent organic group with 2 to 30 carbon atoms that does not contain a carboxylic acid amide bond or a carboxyl group. 1 If R is 2, 1 * represents a trivalent organic group with 5 to 30 carbon atoms that does not contain carboxylic acid amide bonds or carboxyl groups. * represents a bonding site with a carbon atom.

[0024] [ka]

[0025] In formula (2), R 2 * represents a trivalent organic group with 5 to 30 carbon atoms that does not contain carboxylic acid amide bonds or carboxyl groups. * represents a bonding site with a carbon atom.

[0026] The positive-type photosensitive pigment composition of the present invention contains (a) a triphendioxazine pigment having a carboxylic acid amide bond and / or a carboxylic acid ester bond (hereinafter sometimes referred to as "component (a)"). Having a carboxylic acid amide bond means having a group represented by -CONH-. Therefore, sulfonamide bonds and phosphate amide bonds are not included. Having a carboxylic acid ester bond means having a group represented by -COO-. Therefore, sulfonyl ester bonds and phosphate ester bonds are not included. A triphendioxazine pigment means an organic pigment containing a compound having a triphendioxazine skeleton in its molecule. A triphendioxazine skeleton means a skeleton represented by formula (3). The triphendioxazine skeleton is also called a triphenodioxazine skeleton. Therefore, in this specification, triphendioxazine pigment is defined as synonymous with triphenodioxazine pigment. Generally, organic pigments composed of triphendioxazine compounds exhibit a reddish or bluish dark purple hue.

[0027] [ka]

[0028] Component (a) provides light-shielding properties to the pixel division layer and, through a synergistic effect with components (b) and (c) described later, provides excellent halftone processing capabilities and enhances the light resistance reliability of organic EL display devices equipped with a pixel division layer and a spacer layer.

[0029] In this context, "excellent halftone processing capability" means that a pixel division layer having an aperture of a desired aperture width and a spacer layer can be formed simultaneously to the desired film thickness, and that the area ratio of the parts where normal light emission is observed during the initial operation of the organic EL display device is high, when the area of ​​the light-emitting pixel is set to 100%. In this context, "high light resistance reliability" means that when the organic EL display device is continuously operated and continuously irradiated with light including at least near-ultraviolet and visible light, the aforementioned pixel light emission area ratio remains high. Generally, when light is irradiated while the organic EL display device is continuously operated, the degradation of the organic EL elements progresses more easily and the pixel light emission area ratio tends to decrease compared to when light is irradiated while the device is not operated. Since the brightness per unit area of ​​the panel display area can be increased, it is desirable to maintain a high pixel light emission area ratio. The pixel light emission area ratio is more susceptible to influence and tends to be lower the smaller the area of ​​each aperture in the pixel division layer. In other words, the smaller the pixel size and the higher the display quality of the high-definition panel, the more advantageous the technical effects of the present invention become. As mentioned above, the light resistance reliability of the organic EL display device as used herein is a completely different characteristic from the light resistance of a coating film, which is generally well known, such as the degree of change in hue or transmittance.

[0030] Furthermore, component (a) is a pigment that combines high light-shielding properties in the visible light region with high transmittance in the near-infrared region, allowing for easy exposure alignment using a near-infrared camera and improving production yield by increasing the positional accuracy of the exposure mask relative to the substrate.

[0031] (a) As a component, a triphendioxazine pigment containing a triphendioxazine compound having a carboxylic acid amide bond and / or a carboxylic acid ester bond and not containing a chlorine atom in the molecule is preferred in order to improve lightfastness reliability. As a triphendioxazine pigment containing a triphendioxazine compound having a carboxylic acid amide bond and / or a carboxylic acid ester bond and not containing a chlorine atom in the molecule, the triphendioxazine pigment represented by formula (4) and / or the triphendioxazine pigment represented by formula (5) are preferred. In other words, it is preferable that the positive-type photosensitive pigment composition of the present invention contains a triphendioxazine pigment represented by formula (4) and / or a triphendioxazine pigment represented by formula (5) as component (a).

[0032] [ka]

[0033] In formula (4), R 3 and R 4 Each of these independently represents an alkyl group having 1 to 8 carbon atoms. 5 and R 6 Each of these independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group substituted with an alkyl group having 1 to 8 carbon atoms, or an unsubstituted phenyl group. 7 and R 8 Each of these independently represents either a -NH- or an oxygen atom. 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 Each of these independently represents a hydrogen atom, a C1-C4 alkyl group, or a C1-C4 alkoxy group. 19 and R 20 This represents -CONH-. In formula (4), the carbon atom of the carbonyl group of the -CONH- group may be bonded to a carbon atom constituting the triphendioxazine skeleton, or it may be bonded to a carbon atom constituting a phenyl group which may have a substituent.

[0034] [ka]

[0035] In formula (5), R 21 and R 22 Each of these independently represents a hydrogen atom and an alkyl group having 1 to 8 carbon atoms. 23 and R 24 Each of these independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group substituted with an alkyl group having 1 to 8 carbon atoms, or an unsubstituted phenyl group. 25 and R 26 Each of these independently represents either an -NH- or an oxygen atom.

[0036] (a) As for the component, a triphendioxazine pigment represented by formula (6), which is a compound belonging to the triphendioxazine pigment represented by formula (4), is more preferred in order to improve lightfastness reliability. In other words, the positive-type photosensitive pigment composition of the present invention more preferably contains a triphendioxazine pigment represented by formula (6) as component (a).

[0037] [ka]

[0038] In formula (6), R 27 , R 28 , R 29 and R 30 Each of these independently represents an alkyl group having 1 to 4 carbon atoms. R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R38 , R 39 and R 40 Each of these independently represents a hydrogen atom, a C1-C4 alkyl group, or a C1-C4 alkoxy group. R 41 and R 42 This represents -CONH-. In formula (6), the carbon atom of the carbonyl group of the -CONH- group may be bonded to a carbon atom constituting the triphendioxazine skeleton, or it may be bonded to a carbon atom constituting a phenyl group which may have a substituent.

[0039] (a) As for the component, a triphendioxazine pigment represented by formula (7), which is a compound belonging to the triphendioxazine pigment represented by formula (5), is more preferred in order to improve lightfastness reliability. In other words, the positive-type photosensitive pigment composition of the present invention more preferably contains a triphendioxazine pigment represented by formula (7) as component (a).

[0040] [ka]

[0041] In formula (7), R 43 , R 44 , R 45 and R 46 Each of these independently represents an alkyl group having 1 to 4 carbon atoms.

[0042] (a)Specific examples of component include the triphendioxazine pigment represented by formula (8), the triphendioxazine pigment represented by formula (9), the triphendioxazine pigment represented by formula (10), the triphendioxazine pigment represented by formula (11), the triphendioxazine pigment represented by formula (12), the triphendioxazine pigment represented by formula (13), the triphendioxazine pigment represented by formula (14), the triphendioxazine pigment represented by formula (15), the triphendioxazine pigment represented by formula (16), the triphendioxazine pigment represented by formula (17), the triphendioxazine pigment represented by formula (18), and the triphendioxazine pigment represented by formula (19). Component (a) may be a single triphendioxazine pigment, or a mixture of two or more or a mixed crystal.

[0043] [ka]

[0044] [ka]

[0045] [ka]

[0046] [ka]

[0047] Of the above components (a), it is most preferable to include a triphendioxazine pigment represented by formula (7) in order to improve lightfastness reliability.

[0048] The method for synthesizing component (a) is not particularly limited, but for example, the method described in French Patent Application Publication No. 1269107 can be referenced. Furthermore, the method for synthesizing the triphendioxazine pigment represented by formula (8) is given as a specific example, and the preferred method for synthesizing component (a) in the present invention will be described below.

[0049] In the first step, ammonium hydroxide is preferably added to 1 mole of chloranil in a solvent and stirred. Preferably, the mixture is reacted at a liquid temperature of 30 to 100°C for 1 to 6 hours to obtain a product, namely 2,5-diamino-3,6-dichloro-1,4-benzoquinone, in which two of the four chlorine atoms in chloranil are converted to primary amino groups, and this product is filtered off. As solvents, for example, 2-methoxy-1-methylethyl acetate, 2-methoxyethyl acetate, and 3-methoxybutyl acetate can be used.

[0050] In the second step, the aforementioned product is added to acetic anhydride and reacted with stirring at a liquid temperature of preferably 10 to 60°C for 1 to 24 hours to obtain acetanilide, and the intermediate represented by formula (20) is filtered off. Organic acids such as benzenesulfonic acid and p-toluenesulfonic acid may be added to increase the reaction rate. The product obtained in the first step or the intermediate obtained in the second step may be a commercially available product from Tokyo Chemical Industry Co., Ltd.

[0051] [ka]

[0052] In the third step, 2 to 3 moles of the compound represented by formula (21) as an aromatic primary amine are preferably added to 1 mole of the intermediate represented by formula (20) in a solvent and stirred. Preferably, the reaction is carried out by stirring at a liquid temperature of 70 to 130°C for 5 to 10 hours to obtain a triphendioxazine precursor represented by formula (22). To increase the reaction rate, tertiary amines such as triethylamine, tripropylamine, and tributylamine may be used. Examples of solvents include dichlorobenzene, trichlorobenzene, 3-methoxytoluene, 4-methoxytoluene, methylphenyl ether, ethylphenyl ether, nonane, decane, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, and 1,3-dipropyl-2-imidazolidinone.

[0053] [ka]

[0054] [ka]

[0055] In the fourth step, an oxidizing agent is added as a ring-closing aid, and the mixture is preferably stirred at a liquid temperature of 140-200°C for 5-10 hours to cyclize the triphendioxazine precursor represented by formula (22), thereby forming an oxazine ring. The triphendioxazine compound represented by formula (8) is obtained as a pigment crude. If necessary, recrystallization may be performed to control the shape of the primary particles. Examples of oxidizing agents include benzenesulfonyl chloride, p-toluenesulfonyl chloride, m-nitrobenzenesulfonyl chloride, p-nitrobenzenesulfonyl chloride, p-chlorobenzenesulfonyl chloride, and p-toluenesulfonic acid.

[0056] As a fifth step, after cooling to below 100°C, the mixture may be washed with water and filtered repeatedly, and if necessary, purified using a solvent such as ethanol, butanol, or acetone to increase the purity of component (a). Then, after heating or drying under reduced pressure, it is pulverized to produce a powder, which is a dark purple organic pigment called triphendioxazine pigment represented by formula (8).

[0057] Based on the above synthesis method, various triphendioxazine pigments with different chemical structures belonging to component (a) can be synthesized. For example, by using 3-amino-9-ethylcarbazole as the aromatic primary amine in the third step, a triphendioxazine pigment represented by formula (11) can be obtained. Alternatively, by using sodium hydroxide instead of ammonium hydroxide in the first step to produce a compound having a carboxylic acid ester bond, namely 2,5-dichloro-3,6-dihydroxy-p-benzoquinone, and then cyclizing it using 3-amino-9-hexylcarbazole as the aromatic primary amine in the third step, a triphendioxazine pigment represented by formula (13) can be obtained.

[0058] Furthermore, a specific example of how a triphendioxazine pigment represented by formula (14) can be obtained by changing the third and subsequent steps in the aforementioned synthesis method is explained below.

[0059] In the third step, 2 to 3 moles of 2-ethoxy-4-aminobenzoic acid are preferably added to 1 mole of the intermediate represented by formula (20) in a solvent, and the mixture is preferably stirred at a liquid temperature of 70 to 130°C for 5 to 10 hours to react and obtain a triphendioxazine precursor represented by formula (23). Examples of solvents include dichlorobenzene, trichlorobenzene, 3-methoxytoluene, 4-methoxytoluene, methylphenyl ether, ethylphenyl ether, nonane, decane, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, and 1,3-dipropyl-2-imidazolidinone.

[0060] [ka]

[0061] In the fourth step, an oxidizing agent is added, and the mixture is preferably stirred at a liquid temperature of 140-200°C for 5-10 hours to cyclize the triphendioxazine precursor represented by formula (23) to form an oxazine ring and obtain the compound represented by formula (24). As the oxidizing agent, the same group of compounds as those described above can be used.

[0062] [ka]

[0063] Next, as the fifth step, 1 mole of the compound represented by formula (24), which is a dicarboxylic acid, is added to 10 to 15 moles of thionyl chloride, and the mixture is stirred for 5 to 10 hours, preferably at a liquid temperature of 40 to 70°C, to obtain the acid chloride represented by formula (25). Furthermore, 2 to 3 moles of aminobenzene as an aromatic primary amine are added and the mixture is stirred for 5 to 10 hours to obtain the aforementioned triphendioxazine compound represented by formula (14) in the form of a pigment crude.

[0064] [ka]

[0065] After cooling to below 100°C, the mixture is washed with water, filtered, dried, and pulverized to form a powder. If necessary, the purity of component (a) may be increased by purifying it with a solvent such as ethanol, butanol, or acetone. Next, the mixture is heated or dried under reduced pressure and then pulverized to form a powder, yielding a dark purple organic pigment, the triphendioxazine pigment represented by formula (14). For pulverization, known dry pulverization methods using a ball mill, hammer mill, or jet mill can be applied.

[0066] Based on the above synthesis method, various triphendioxazine pigments with different chemical structures belonging to component (a) can be synthesized. For example, if 4-ethylaniline is used as the aromatic primary amine in the fifth step, a triphendioxazine pigment represented by formula (15) can be obtained.

[0067] Other components of component (a) besides the compound having the triphendioxazine skeleton include, for example, residues such as raw materials and by-products used to synthesize the compound having the triphendioxazine skeleton. The content of these residues is preferably less than 2.0 parts by weight, and more preferably less than 0.5 parts by weight, per 100 parts by weight of component (a) in order to improve lightfastness reliability. In other words, the content of the compound having the triphendioxazine skeleton per 100 parts by weight of component (a) is preferably 98.0 parts by weight or more, and more preferably 99.5 parts by weight or more, in order to improve lightfastness reliability.

[0068] (a) The average primary particle diameter of component (a) is preferably 10 nm or more, and more preferably 20 nm or more, in order to improve halftone processability. From the same viewpoint, it is preferably 100 nm or less, and more preferably 80 nm or less. The average primary particle diameter referred to here is the numerical average of the primary particle diameters calculated by a particle size measurement method using an image analysis type particle size distribution analyzer. A transmission electron microscope (TEM) can be used to capture images, and the average primary particle diameter can be calculated by analyzing 50 primary particles randomly selected from an image in which 100 or more primary particles of component (a) have been captured under a magnification of 50,000x. If component (a) is not perfectly spherical, the primary particle diameter (nm) is taken by rounding the average of its major axis to the first decimal place. Furthermore, the maximum primary particle diameter is taken from the 50 primary particles selected from the TEM image used to calculate the average primary particle diameter. The maximum primary particle diameter of component (a) is preferably 200 nm or less, and more preferably 150 nm or less, in order to improve halftone processability. For image analysis, the image analysis particle size distribution software Mac-View (manufactured by Mountec Co., Ltd.; compliant with JIS8827-1; particle size analysis - image analysis method) can be used.

[0069] (a) The average aspect ratio of component is preferably 1.0 or higher, and more preferably 1.3 or higher, in order to improve halftone processability and long-term storage stability. From the same viewpoint, it is preferably 3.0 or lower, and more preferably 2.5 or lower. The average aspect ratio referred to here means the value obtained by measuring the major and minor diameters of the primary particles observed in the TEM image for each of the 50 primary particles randomly selected to calculate the average primary particle diameter, calculating the average value of the major diameter divided by the minor diameter, and rounding to the second decimal place.

[0070] (a) As a method for controlling the average primary particle diameter, maximum primary particle diameter, and average aspect ratio of the component to be small, the solvent salt milling method can be preferably applied. The solvent salt milling method is a method in which an organic pigment, grinding agent, and water-soluble organic solvent are mixed into a paste, which is wet-kneaded at 20 to 80°C, then added to a large amount of water and stirred, the grinding agent and water-soluble organic solvent are removed by washing with water, and the resulting filtrate is dried and pulverized to obtain a finely milled organic pigment. As a kneader, for example, a kneader (manufactured by Inoue Seisakusho Co., Ltd.) can be used. As the grinding agent, finely granular water-soluble inorganic salts with an average primary particle diameter of 0.1 to 50 μm are preferred, such as sodium chloride, potassium chloride, or potassium sulfate. As the water-soluble organic solvent, glycol-based solvents are preferred. Examples of glycol-based solvents include ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol.

[0071] (a) The content of component (a) is preferably 5% by weight or more, and more preferably 10% by weight or more, of 100% by weight of the solids content of the positive-type photosensitive pigment composition, in order to improve lightfastness reliability. In order to improve halftone processing properties, it is preferably 50% by weight or less, and more preferably 40% by weight or less.

[0072] The positive-type photosensitive pigment composition of the present invention contains (b) a resin having a structure represented by formula (1) and / or formula (2) (hereinafter sometimes referred to as "component (b)"). In this specification, "resin" means a compound having a weight-average molecular weight (Mw) of 1000 or more, having repeating units containing organic groups, and having three or more repeating units in the molecule.

[0073] Component (b), through a synergistic effect with component (a) described above and component (c) described later, provides excellent halftone processing capabilities and enhances the light resistance reliability of an organic EL display device that has a pixel division layer and a spacer layer formed collectively by halftone processing. Furthermore, component (b) has the effect of maintaining excellent halftone processing properties after long-term storage, based on the positive-type photosensitive pigment composition of the present invention one day after preparation, i.e., it enhances long-term storage stability. Long-term storage here means leaving the tightly sealed positive-type photosensitive pigment composition undisturbed for 180 days in a cool, dark place maintained at atmospheric pressure, shielded from light, and at -20±1℃. Storing the composition under the above conditions to suppress changes over time in the composition containing the (c) photoacid generator, which is highly active against heat and light, is common practice in the art. Maintaining excellent halftone processing properties even after long-term storage allows for a consistently high pixel emission area ratio.

[0074] [ka]

[0075] In formula (1), n 1 is an integer, representing either 1 or 2. n 1 If R is 1, 1 n represents a divalent organic group with 2 to 30 carbon atoms that does not contain a carboxylic acid amide bond or a carboxyl group. 1 If R is 2, 1 * represents a trivalent organic group with 5 to 30 carbon atoms that does not contain carboxylic acid amide bonds or carboxyl groups. * represents a bonding site with a carbon atom.

[0076] [ka]

[0077] In formula (2), R 2 * represents a trivalent organic group with 5 to 30 carbon atoms that does not contain a carboxyl group. * represents a bonding site with a carbon atom.

[0078] In formula (1), "not containing a carboxylic acid amide bond" means not containing a group represented by -CONH-. The structure represented by formula (1) is preferably the structure of a residue after a reaction between a dicarboxylic acid anhydride or tricarboxylic acid anhydride and a compound having a primary amino group, and more preferably the structure of a residue after a reaction between a dicarboxylic acid anhydride or tricarboxylic acid anhydride and a diamine compound having two primary amino groups (-NH2) in the molecule. On the other hand, the structure represented by formula (2) is preferably the structure of a residue after a reaction between a tricarboxylic acid anhydride and a compound having a primary amino group, and more preferably the structure of a residue after a reaction between a tricarboxylic acid anhydride and a diamine compound having two primary amino groups in the molecule. The structures represented by formula (1) and formula (2) can be introduced as terminal structures of component (b) from dicarboxylic acid anhydrides, tricarboxylic acid anhydrides, or monoamines described below that are readily available industrially.

[0079] Examples of dicarboxylic acid anhydrides include maleic anhydride (R after reaction). 1 Number of carbon atoms: 2), 2,3-Pyridinedicarboxylic acid anhydride (R after reaction) 1 Number of carbon atoms: 5), phthalic anhydride (R after reaction) 1 Number of carbon atoms: 6), 1,2,3,6-tetrahydrophthalic anhydride (R after reaction) 1 Number of carbon atoms: 6), acid anhydride represented by formula (26) (R after reaction) 1 Number of carbon atoms: 6), acid anhydride represented by formula (27) (R after reaction) 1Number of carbon atoms: 6), tetrahydro-4-methylphthalic anhydride (R after reaction) 1 Number of carbon atoms: 7), 5-norbornene-2,3-dicarboxylic anhydride (R after reaction) 1 Number of carbon atoms: 7), 1,3-isochromandionic anhydride (R after reaction) 1 Number of carbon atoms: 7), methyl-5-norbornene-2,3-dicarboxylic anhydride (R after reaction) 1 Number of carbon atoms: 8), 1,2-naphthalenedicarboxylic anhydride (R after reaction) 1 Number of carbon atoms: 10), 2,3-naphthalenedicarboxylic anhydride (R after reaction) 1 Number of carbon atoms: 10), 1,8-naphthalenedicarboxylic anhydride (R after reaction) 1 Number of carbon atoms: 10), the acid anhydride represented by formula (28) (R after reaction) 1 Number of carbon atoms: 10), the acid anhydride represented by formula (29) (R after reaction) 1 Number of carbon atoms: 10), 3,4-dihydro-1,2-naphthalenedicarboxylic anhydride (R after reaction) 1 Number of carbon atoms: 10), 1,2,3,4-tetrahydro-1,4-methanonaphthalene-2,3-dicarboxylic anhydride (R after reaction) 1 Number of carbon atoms: 11), the acid anhydride represented by formula (31) (R after reaction) 1 Number of carbon atoms: 12), the acid anhydride represented by formula (30) (R after reaction) 1 Number of carbon atoms: 14), 2,3-anthracenedicarboxylic anhydride (R after reaction) 1 Number of carbon atoms: 14), 4-phenylethynylphthalic anhydride (R after reaction) 1 Examples thereof include those having a carbon number of 14).

[0080]

Chemical formula

[0081] Examples of the tricarboxylic anhydride include, for example, pyridine-2,3,4-tricarboxylic acid-3,4-anhydride (R after reaction) 1 Number of carbon atoms: 5, R after reaction 2 Number of carbon atoms: 5), trimellitic anhydride (R after reaction) 1 Number of carbon atoms: 6, R after reaction2 Number of carbon atoms: 6), cyclohexane-1,2,4-tricarboxylic acid 1,2-anhydride (R after reaction 1 Number of carbon atoms: 6, R after reaction 2 Number of carbon atoms: 6), 1,2,5-naphthalenetricarboxylic acid 1,2-anhydride (R after reaction 1 Number of carbon atoms: 10, R after reaction 2 Number of carbon atoms: 10) can be mentioned.

[0082] (b) As the structure represented by formula (1) possessed by the resin belonging to the component, in order to improve the long-term storage stability, in formula (1), when n 1 is 1, R 1 is preferably a divalent organic group having 2 to 15 carbon atoms and not containing a carboxylic acid amide bond and a carboxyl group. When n 1 is 2, R 1 is preferably a trivalent organic group having 5 to 15 carbon atoms and not containing a carboxylic acid amide bond and a carboxyl group.

[0083] (b) As the structure represented by formula (2) possessed by the resin belonging to the component, in order to improve the long-term storage stability, in formula (2), R 2 is preferably a trivalent organic group having 5 to 15 carbon atoms and not containing a carboxyl group. Specific examples of the structure represented by formula (1) and the structure represented by formula (2) include the structure represented by formula (32) which is the residue of 5-norbornene-2,3-dicarboxylic anhydride, the structure represented by formula (33) which is the residue of 1,2-naphthalenedicarboxylic anhydride, the structure represented by formula (34) which is the residue of trimellitic anhydride, and the structure represented by formula (35).

[0084]

Chemical formula

[0085] In formulas (32) to (35), * represents the bonding site with a carbon atom.

[0086] For structural parts other than the structure represented by formula (1) and / or the structure represented by formula (2), component (b) preferably has repeating units having carboxylic acid amide bonds and / or imide bonds. In other words, the positive-type photosensitive pigment composition of the present invention preferably contains a resin having repeating units having carboxylic acid amide bonds and / or imide bonds as component (b). The structures represented by formula (1) and formula (2) described above are not included in the repeating units as referred to herein. Component (b) may contain a copolymer of a resin having repeating units having carboxylic acid amide bonds and a resin having repeating units having imide bonds.

[0087] Examples of resins having repeating units with carboxylic acid amide bonds include hydroxyl group-containing polyamide resins having repeating units represented by formula (36). Examples of resins having repeating units with imide bonds include hydroxyl group-containing polyimide resins having repeating units represented by formula (37). Examples of resins having repeating units with both carboxylic acid amide bonds and imide bonds include hydroxyl group-containing polyamideimide resins having repeating units represented by formula (38). Among these, it is preferable to have at least the repeating units represented by formula (36) in terms of excellent long-term storage stability. In other words, the positive-type photosensitive pigment composition of the present invention preferably contains a resin having repeating units represented by formula (36) as component (b).

[0088] [ka]

[0089] In formula (36), R 47 R represents a divalent organic group with 5 to 30 carbon atoms that does not contain a carboxylic acid amide bond or a carboxyl group. 48 This represents a hydroxyl group that does not contain a hydroxyl group and has 6 to 40 carbon atoms with a valency of 3 to 6. 2 * is an integer, representing 1 to 4. 1 * represents the bonding site with the nitrogen atom. 2This represents the bonding site with a carbon atom.

[0090] [ka]

[0091] In formula (37), R 49 R represents a tetravalent organic group. 50 This represents a 3- to 6-valent organic group. n 3 is an integer, representing 1 to 4. * represents a connection point.

[0092] [ka]

[0093] In formula (38), R 51 R represents a divalent organic group. 52 This represents a 3- to 6-valent organic group. n 4 is an integer, representing 1 to 4. * represents a connection point.

[0094] The repeating unit represented by formula (36) is preferably the structure of a residue obtained after a reaction between a dicarboxylic acid derivative and a diamine compound having two primary amino groups in the molecule, due to its ease of synthesis. As the dicarboxylic acid derivative, a diimidazolide compound or an acid chloride can be used. Examples of diimidazolide compounds include the compound represented by formula (39), the compound represented by formula (40), and the compound represented by formula (42). Examples of acid chlorides include the compound represented by formula (41) and the compound represented by formula (43).

[0095] [ka]

[0096] Examples of diamine compounds having two primary amino groups in the molecule include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 4,4'-diaminodiphenyl ether, 2,2'-bis(trifluoromethyl)benzidine, 9,9-bis(4-aminophenyl)fluorene, Examples include bis(3-aminophenyl)sulfone, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, 1,1,3,3-tetramethyl-1,3-bis(3-aminopropyl)disiloxane, compounds represented by formula (44), compounds represented by formula (45), and compounds represented by formula (46).

[0097] [ka]

[0098] The repeating units represented by formula (37) and formula (38) are preferably the structures of residues obtained after a reaction between an acid dianhydride and a diamine compound having two primary amino groups in its molecule, because they are easy to synthesize.

[0099] Examples of acid dianhydrides include 4,4'-oxydiphthalic acid dianhydride, 3,4'-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic acid dianhydride, diphenyl-2,3,3',4'-tetracarboxylic acid dianhydride, and 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride. As diamine compounds having two primary amino groups in the molecule, the same group of compounds as described above can be used.

[0100] (b) Preferably, the component contains a resin having a structure represented by formula (47) in addition to the repeating unit represented by formula (36) in order to improve halftone processability, long-term storage stability and lightfastness reliability. In other words, the positive-type photosensitive pigment composition of the present invention more preferably contains a resin having a repeating unit represented by formula (36) and a structure represented by formula (47) as component (b).

[0101] [ka]

[0102] In formula (47), R 113 R represents a divalent organic group with 5 to 30 carbon atoms that does not contain a carboxylic acid amide bond or a carboxyl group. 114 This represents a hydroxyl group that does not contain a hydroxyl group and has 6 to 40 carbon atoms with a valency of 3 to 6. 32 * is an integer, representing 1 to 4. 3 This represents the bonding site with the nitrogen atom.

[0103] Examples of structures represented by formula (47) include, for example, the structure represented by formula (48), the structure represented by formula (49), and the structure represented by formula (50).

[0104] [ka]

[0105] In formulas (48), (49), and (50), * represents a bond site with a nitrogen atom.

[0106] (b) The weight-average molecular weight (Mw) of component is preferably 10,000 to 150,000 in order to improve halftone processability and long-term storage stability. (b) Component can be synthesized by known polymerization methods, for example, by referring to the methods disclosed in Japanese Patent No. 4341293, International Publication No. 2014 / 097992, and International Publication No. 2019 / 181782. Examples of methods for synthesizing resins having the structure represented by formula (1) and the structure represented by formula (47) include the following:

[0107] As raw materials, 100 mol% of a diamine compound having two primary amino groups in its molecule and a total of 70-110 mol% of a diimidazolide compound and dicarboxylic acid anhydride are dissolved in an organic solvent and reacted under mild conditions, preferably at a liquid temperature of 50-100°C. If the total amount of diimidazolide compound and dicarboxylic acid anhydride is 100 mol% or more, the reaction is stopped by cooling before the primary amino groups derived from the diamine compound disappear. Then, by removing unreacted raw materials by reprecipitation treatment, component (b) can be obtained, in which a primary amino group preferably remains at one end.

[0108] (b) The content of component (b) is preferably 10% by weight or more, and more preferably 30% by weight or more, of 100% by weight of the solids content of the positive-type photosensitive pigment composition, in order to improve lightfastness reliability. In order to improve halftone processing properties, it is preferably 70% by weight or less, and more preferably 50% by weight or less.

[0109] The positive-type photosensitive pigment composition of the present invention contains (c) a photoacid generator (hereinafter sometimes referred to as "component (c)"). The photoacid generator is not particularly limited as long as it is a compound that decomposes upon light irradiation and generates acid. As the generated acid, carboxylic acids and sulfonic acids are preferred in order to improve halftone processing properties.

[0110] (c) The inclusion of component (c) has the effect of making the solubility of the film in the exposed area relative to the alkaline developer relatively higher due to the acid generated, compared to the solubility of the film in the unexposed area, enabling positive-type photolithography in which the film in the exposed area, which has been pattern-exposed via an exposure mask, is removed to form a pattern. In addition, by controlling the amount of acid generated in the film by adjusting the exposure amount, the solubility of the film in the exposed area, which has been exposed with a small exposure amount via a halftone exposure mask, is relatively lower compared to the solubility of the film in the exposed area, which has been exposed with a large exposure amount, enabling the simultaneous formation of the pixel division layer and spacer layer by positive-type halftone processing.

[0111] Examples of component (c) include quinone diazide compounds, oxime sulfonate compounds, and imido sulfonate compounds. Among these, quinone diazide compounds are preferred because they exhibit an excellent dissolution inhibitory effect on the unexposed film, can increase the difference in dissolution rates between the exposed and unexposed areas, and have excellent exposure sensitivity. Compounds obtained by reacting a compound having two or more phenolic hydroxyl groups in its molecule with 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride (hereinafter sometimes referred to as "4-naphthoquinone diazide sulfonyl ester compounds") and compounds obtained by reacting a compound having two or more phenolic hydroxyl groups in its molecule with 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride (hereinafter sometimes referred to as "5-naphthoquinone diazide sulfonyl ester compounds") are more preferred. In other words, it is preferable that the positive-type photosensitive pigment composition of the present invention contains a quinone diazide compound as component (c).

[0112] Examples of 4-naphthoquinone diazidosulfonyl ester compounds and 5-naphthoquinone diazidosulfonyl ester compounds include the compound represented by formula (51), the compound represented by formula (52), the compound represented by formula (53), the compound represented by formula (54), the compound represented by formula (55), the compound represented by formula (56), the compound represented by formula (57), the resin having a repeating unit represented by formula (58), and the resin having a repeating unit represented by formula (59). These compounds may be included individually or in combination. Resins that decompose upon light irradiation and generate acid are defined as belonging to component (c), other than component (b) described later, and not to the aforementioned component (b). Therefore, for example, a resin having the structure represented by formula (1) and / or the structure represented by formula (2), and corresponding to a quinone diazide compound, is component (c).

[0113] [ka]

[0114] [ka]

[0115] In formulas (51) to (59), Q represents a hydrogen atom, a structure represented by formula (60), or a structure represented by formula (61). However, in each compound, at least one Q is a structure represented by formula (60) or a structure represented by formula (61). * represents a binding site. In formula (58), R 55 and R 56 n represents an alkyl group with 1 to 3 carbon atoms. 5 and n 6 This is an integer, representing either 0 or 1. In formula (59), R 57 and R 58 n represents a hydrogen atom or a methyl group. 7 and n 8 This is an integer, representing 1 to 3.

[0116] [ka]

[0117] In formulas (60) and (61), * represents a bonding site with an oxygen atom.

[0118] The product may contain a 4-naphthoquinone diazidosulfonyl ester compound that absorbs in the i-line (wavelength 365 nm) region of mercury lamps, and a 5-naphthoquinone diazidosulfonyl ester compound that absorbs broadly from the i-line to the h-line (wavelength 405 nm) and g-line (wavelength 436 nm) regions. It may also contain a quinone diazide compound having a 4-naphthoquinone diazidosulfonyl group and a 5-naphthoquinone diazidosulfonyl group in its molecule.

[0119] (c) The content of component (c) is preferably 1 part by weight or more, and more preferably 10 parts by weight or more, per 100 parts by weight of all resins contained in the positive-type photosensitive pigment composition, in order to improve halftone processability and lightfastness reliability. From the same viewpoint, it is preferably 50 parts by weight or less, and more preferably 30 parts by weight or less. All resins as used herein include component (b) but do not include resins belonging to component (c).

[0120] (c) Naphthoquinone diazidosulfonyl ester compounds that can be preferably used as component (c) can be synthesized, for example, by an esterification reaction of a compound having two or more phenolic hydroxyl groups in its molecule with naphthoquinone diazidosulfonyl chloride under a basic catalyst such as triethylamine.

[0121] (c) Commercially available products of component (c) include PA-28 (manufactured by Daito Chemix Co., Ltd.), a naphthoquinone diazide compound that generates acid upon exposure to i-rays; PAG103 and PAG203 (both manufactured by BASF), oximesulfonate compounds that generate acid upon exposure to i-rays; and NIT, NIN, and ILP-110 (all manufactured by Heraeus), imidosulfonate compounds that generate acid upon exposure to i-rays.

[0122] The positive-type photosensitive pigment composition of the present invention contains (d) an organic solvent (hereinafter sometimes referred to as "component (d)").

[0123] (d) Examples of components include ether-based solvents, glycol-based solvents, acetate-based solvents, ketone-based solvents, lactone-based solvents, aromatic hydrocarbon-based solvents, and amide-based solvents.

[0124] Examples of ether-based solvents include ethylene glycol monomethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether (hereinafter referred to as "PGME"), propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether. Examples of glycol-based solvents include ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol. Examples of acetate solvents include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA"), propylene glycol monoethyl ether acetate, methyl lactate, ethyl lactate, and 3-methoxybutyl acetate (hereinafter referred to as "MBA"). Examples of ketone solvents include methyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone. Examples of lactone solvents include γ-butyrolactone (hereinafter referred to as "GBL") and γ-valerolactone. Examples of aromatic hydrocarbon solvents include toluene, xylene, and benzene. Examples of amide solvents include N-methylpyrrolidone (hereinafter referred to as "NMP"), N,N-dimethylformamide, and N,N-dimethylacetamide. In particular, to improve long-term storage stability, it is preferable to include an ether-based solvent, and more preferably to include a lactone-based solvent.To achieve both good applicability and a suitable drying speed while improving film thickness uniformity, it is desirable to use ether-based solvents and lactone-based solvents in combination.

[0125] (d) The content of component (d) is more preferably 60% by weight or more per 100% by weight of the positive-type photosensitive pigment composition in order to improve storage stability. More preferably 95% by weight or less in order to improve coatability and the smoothness of the pre-baked film. The content of aromatic hydrocarbon solvents and amide solvents is more preferably 0.5% by weight or less per 100% by weight of the positive-type photosensitive pigment composition in order to improve long-term storage stability. In addition, long-term storage stability may be further improved by including 0.01 to 0.5% by weight of water per 100% by weight of the positive-type photosensitive pigment composition.

[0126] The positive-type photosensitive pigment composition of the present invention preferably further contains an organic dye (hereinafter sometimes referred to as "component (e)") having a sulfo group bonded to a carbon atom constituting an aromatic ring and / or a carboxyl group bonded to a carbon atom constituting an aromatic ring, and not having a chlorine atom in the molecule, in order to improve halftone workability, long-term storage stability and lightfastness reliability. The sulfo group referred to here means not only -SO3H, but may also have a proton dissociated in the positive-type photosensitive pigment composition, -SO3 - This includes. The carboxyl group referred to here means not only -COOH, but also -COO, in which the proton may be dissociated in the positive-type photosensitive pigment composition. - This includes the following. In this specification, the terms carboxyl group and carboxyl group are defined as synonymous.

[0127] The term "organic dye" as used herein refers to organic dyes and organic pigments that have absorption in at least the visible light region. The form in which component (e) exists as an organic dye in the positive-type photosensitive pigment composition is not particularly limited; it may be included in a dissolved form, i.e., as an organic dye, but it is preferable to include it dispersed as insoluble fine particles, i.e., as an organic pigment. The form in which component (e) exists can be controlled by adjusting component (d) with respect to the total number of sulfo groups and / or carboxyl groups that the organic dye belonging to component (e) has in its molecule. Furthermore, component (e) may be included as a surface treatment agent for component (a), and components (a) and (e) may form a mixed crystal. When it is a surface treatment agent or a mixed crystal, it is defined as a mixture of components (a) and (e). In addition, an organic dye that has a carboxylic acid amide bond and / or carboxylic acid ester bond, as well as a triphendioxazine skeleton, and has sulfo groups and / or carboxyl groups bonded to carbon atoms constituting an aromatic ring, and does not have a chlorine atom in its molecule, is defined as component (e).

[0128] (e) The method for producing component is not particularly limited and may be a pigment derivative obtained by derivatizing so-called organic pigments, or it may be an organic dye synthesized using an intermediate compound as a raw material that has a sulfo group bonded to a carbon atom constituting an aromatic ring and / or a carboxyl group bonded to a carbon atom constituting an aromatic ring, and does not contain a chlorine atom in the molecule, without going through the form of an organic pigment.

[0129] (e) Examples of components include triphendioxazine dyes, perylenebisimide dyes, anthraquinone dyes, perinone dyes, phthalocyanine dyes, quinacridone dyes, benzofuranone dyes, and flavantron dyes. Among these, triphendioxazine dyes, perylenebisimide dyes, and anthraquinone dyes are more preferred for improving halftone processing properties and long-term storage stability.

[0130] In other words, the positive-type photosensitive pigment composition of the present invention more preferably contains at least one component (e) selected from the group consisting of triphendioxazine-based dyes, perylenebisimide-based dyes, and anthraquinone-based dyes. Here, triphendioxazine-based dyes mean organic dyes having a triphendioxazine skeleton in their molecule. Perylenebisimide-based dyes mean organic dyes having a perylenebisimide skeleton in their molecule. Anthraquinone-based dyes mean organic dyes having an anthraquinone skeleton in their molecule.

[0131] (e) Examples of sulfo groups and / or carboxyl groups bonded to carbon atoms constituting the aromatic ring of component include sulfophenyl group, disulfophenyl group, carboxyphenyl group, dicarboxyphenyl group, carboxy-sulfophenyl group, methyl-sulfophenyl group, methoxy-sulfophenyl group, sulfonaphthyl group, disulfonaphthyl group, carboxynaphthyl group, dicarboxynaphthyl group, carboxy-sulfonaphthyl group, methyl-sulfonaphthyl group, and methoxy-sulfonaphthyl group.

[0132] Examples of triphendioxazine dyes belonging to component (e) include the compound represented by formula (62) and the compound represented by formula (63).

[0133] [ka]

[0134] In formula (62), R 57 and R 58 Each of these independently represents either an -NH- or an oxygen atom. R 59 and R 60 Each of these independently represents an alkyl group having 1 to 4 carbon atoms. 61 and R 62 These represent -NH- or -CONH- independently. 63 , R 64 , R 67 and R68 These are -SO3H and -SO3, respectively, independently. - -COOH or -COO - Represents R 65 and R 66 Each of these independently represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. 9 and n 10 n is an integer, each independently representing either 0 or 1. 11 , n 12 , n 13 and n 14 n are integers, each independently representing 0 to 2. 15 n is an integer, representing either 0 or 1. 9 , n 11 and n 15 The sum of n is 2 or less, 10 , n 12 and n 15 The sum is 2 or less. 15 If n is 0, 11 and n 12 The sum is between 1 and 3. 15 If n is 1, 11 , n 12 , n 13 and n 14 The total is between 1 and 3.

[0135] [ka]

[0136] In formula (63), R 69 and R 70 Each of these independently represents either an -NH- or an oxygen atom. R 71 and R 72 Each of these independently represents an alkyl group having 1 to 4 carbon atoms. 73 , R 74 , R 75 and R 76 These are -SO3H and -SO3, respectively, independently. - -COOH or -COO - Represents R 77 and R78 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n 16 , n 17 , n 18 and n 19 are integers and each independently represents 0 or 1. n 16 , n 17 , n 18 and n 19 The sum of and n is 1 to 3.

[0137] (e) The triphendioxazine-based dye belonging to the component can be synthesized, for example, by the following method. Based on the synthesis method of the aforementioned (a) component, for 1 mol of the intermediate represented by the formula (20) obtained in the second step, as the third step, 2 to 3 mol of the compound represented by the formula (64), the compound represented by the formula (65) or the compound represented by the formula (66) is added and reacted, and then the ring closure reaction is allowed to proceed to obtain a slurry containing a blue-violet precipitate. Further, repeated washing with water is performed, followed by filtration, drying and pulverization. By the above operations, a triphendioxazine-based dye belonging to the (e) component, having a sulfo group bonded to a carbon atom constituting an aromatic ring and having no chlorine atom in the molecule can be obtained. Specific examples include the compound represented by the formula (67) and the compound represented by the formula (68).

[0138]

Chemical formula

[0139]

Chemical formula

[0140] On the other hand, in the third step, by using an aromatic carboxylic acid having an amino group, a triphendioxazine-based dye belonging to the (e) component, having a carboxyl group bonded to a carbon atom constituting an aromatic ring and having no chlorine atom in the molecule can be obtained by the same procedure as described above.

[0141] Examples of perylenebisimide dyes belonging to component (e) include the compound represented by formula (69) and the compound represented by formula (70).

[0142] [ka]

[0143] In formula (69), R 79 and R 80 Each of these independently represents a phenylene group substituted with an alkyl group having 1 to 6 carbon atoms, a phenylene group substituted with an alkoxy group having 1 to 6 carbon atoms, an unsubstituted phenylene group, a naphthylene group substituted with an alkyl group having 1 to 6 carbon atoms, a naphthylene group substituted with an alkoxy group having 1 to 6 carbon atoms, or an unsubstituted naphthylene group. 81 and R 82 These are -SO3H and -SO3, respectively, independently. - -COOH or -COO - Represents n 20 and n 21 n is an integer, representing 0 to 2. 20 and n 21 The total is between 1 and 3.

[0144] [ka]

[0145] In formula (70), R 83 and R 84 Each of these independently represents an alkyl group having 1 to 6 carbon atoms. R 85 and R 86 These are -SO3H and -SO3, respectively, independently. - -COOH or -COO - Represents n 22 and n 23 n is an integer, representing 0 to 2. 22 and n 23 The total is between 1 and 3.

[0146] Perylenebisimide dyes belonging to component (e) can be synthesized, for example, by the following method.

[0147] As a starting material, a mixture of CI Pigment Red 178 or CI Pigment Black 31 dissolved in 10-50% by weight fuming sulfuric acid or 50-100% by weight concentrated sulfuric acid is heated, and the mixture is stirred for 3-10 hours while the liquid temperature is adjusted to 40-90°C to selectively introduce sulfo groups to terminal phenyl groups, thereby allowing the sulfonation reaction to proceed. By raising the liquid temperature above 40°C, the residue of unreacted starting materials can be suppressed, and by lowering the temperature below 90°C, the decomposition reaction of the starting materials can be suppressed, thereby increasing the purity of the product. Next, the mixture is added to water at least 100 times the weight of the starting materials, preferably ice water, to obtain a slurry containing a red precipitate, which is then filtered. After washing with methanol or ethanol, the mixture is preferably washed repeatedly with water until the residual amount of sulfate ions is less than 50 ppm by weight, and then dried under reduced pressure at 60-80°C. Finally, the dried aggregates are broken down and the mixture is powdered by dry grinding using a hammer mill or jet mill. The number of sulfo groups introduced per molecule of the target product and their distribution can be controlled by adjusting the liquid temperature and reaction time according to the concentration of fuming sulfuric acid or concentrated sulfuric acid, and the reaction endpoint can be determined by structural analysis using nuclear magnetic resonance (NMR) or liquid chromatography-mass spectrometry (LC-MS). Furthermore, the purity of compounds with a specific range of sulfo groups introduced can be increased by purification using silica gel chromatography. Through these operations, a perylenebisimide dye belonging to component (e), which has a carboxyl group bonded to a carbon atom constituting an aromatic ring and does not contain a chlorine atom in the molecule, is obtained. Specific examples include the compound represented by formula (71), the compound represented by formula (72), the compound represented by formula (73), and the compound represented by formula (74).

[0148] [ka]

[0149] On the one hand, by reacting a perylene tetracarboxylic dianhydride with an aromatic carboxylic acid having a primary amino group, a perylene bisimide-based dye belonging to the (e) component, which has a carboxyl group bonded to a carbon atom constituting an aromatic ring and does not have a chlorine atom in the molecule, can be obtained. Specific examples include the compound represented by formula (75).

[0150]

Chemical formula

[0151] Examples of the anthraquinone-based dye belonging to the (e) component include, for example, the compound represented by formula (76) and the compound represented by formula (77).

[0152]

Chemical formula

[0153] In formula (76), R 87 and R 88 represent an alkyl group having 1 to 3 carbon atoms. n 24 and n 25 are integers and represent 0 to 3. R 89 and R 90 each independently represent -SO3H or -SO3 - 26 n 27 and n 26 are integers and represent 0 to 2. n 27 and n 91 The sum of is 1 to 3.

[0154]

Chemical formula

[0155] In formula (77), R 91 and R 92 represent an alkyl group having 1 to 3 carbon atoms. n 28 and n 29 are integers and represent 0 to 3. R 93 and R 94These are, independently, -COOH or -COO - Represents R 95 and R 96 n represents an alkyl group with 1 to 3 carbon atoms. 30 and n 31 This is an integer, representing either 0 or 1.

[0156] Anthraquinone dyes belonging to component (e) can be synthesized, for example, by the following method: Using CI Solvent Blue 104 or CI Solvent Green 3 as a starting material, the sulfonation reaction is carried out in the same manner as described above, preferably by repeatedly washing with water and filtering until the amount of residual sulfate ions is less than 50 ppm by weight, and then by dry grinding, a compound represented by formula (76) is obtained, which has a sulfo group bonded to the carbon atoms constituting the aromatic ring and does not contain a chlorine atom in the molecule. If necessary, purification treatment using silica gel chromatography may be performed. Specific examples include the compound represented by formula (78) and the compound represented by formula (79).

[0157] [ka]

[0158] On the other hand, sulfonic acid chloride or thionyl chloride is added to CI Solvent Blue 104 or CI Solvent Green 3 and stirred at a liquid temperature of 10°C or below for 3 to 10 hours. The mixture is then added to water at least 100 times the weight of the starting material, preferably ice water, to obtain a slurry containing a blue precipitate, which is then filtered off. Preferably, the mixture is repeatedly washed with water until the remaining amount of chloride ions is less than 50 ppm by weight, and then dried under reduced pressure at 60 to 80°C to obtain anthraquinone-based sulfonyl chloride. Next, 2 to 3 moles of 3-aminobenzoic acid or 3-amino-4-methylbenzoic acid are added to 1 mole of anthraquinone-based sulfonyl chloride in the solvent and stirred at a liquid temperature of 30 to 60°C for 3 to 10 hours. After repeated washing and filtration, the mixture is filtered off. If necessary, purification treatment using silica gel chromatography may be performed. Finally, the mixture is dry-ground to produce a powder. Through the above operations, a compound represented by formula (77) is obtained, which has a carboxyl group bonded to a carbon atom constituting an aromatic ring and does not contain a chlorine atom in the molecule. Specific examples include the compound represented by formula (80) and the compound represented by formula (81).

[0159] [ka]

[0160] Among the compounds belonging to component (e) described above, the compounds represented by formula (62) and formula (63) are more preferred in terms of improving halftone processability and long-term storage stability. In other words, the positive-type photosensitive pigment composition of the present invention more preferably contains a compound represented by formula (62) and / or a compound represented by formula (63) as component (e).

[0161] In a positive-type photosensitive pigment composition, if component (e) exists in the form of insoluble pigment particles, the average primary particle diameter of component (e) is preferably 10 nm or more, and more preferably 20 nm or more, in order to improve halftone processability. From the same viewpoint, it is preferably 100 nm or less, and more preferably 80 nm or less. The average aspect ratio of component (e) is preferably 1.0 or more, and more preferably 1.3 or more, in order to improve halftone processability and long-term storage stability. From the same viewpoint, it is preferably 3.0 or less, and more preferably 2.5 or less.

[0162] If the positive-type photosensitive pigment composition of the present invention contains component (e), the content of component (e) is preferably 1 to 40 parts by weight, and more preferably 5 to 30 parts by weight, per 100 parts by weight of component (a), in order to achieve both halftone processing properties and long-term storage stability.

[0163] The positive-type photosensitive pigment composition of the present invention preferably further contains a compound (hereinafter sometimes referred to as "component (f)") that, before heating, does not have a maximum absorption wavelength in the 350-500 nm wavelength region in the wavelength region of 350-780 nm, but is converted upon heating to a compound having a maximum absorption wavelength in the 350-500 nm wavelength region. The component (f) referred to here is a compound that does not belong to any of components (a) to (g), and the principle of thermal color development is not particularly limited. As mentioned above, component (a) is dark purple and has optical properties in which the maximum transmittance at wavelengths of 400-440 nm is higher than the maximum transmittance at wavelengths of 500-600 nm. By including component (f), the maximum transmittance in the wavelength range of 410-440 nm of the pixel division layer obtained after heat treatment in the curing process described later can be preferably controlled to be low, that is, a pixel division layer exhibiting black color can be obtained. The heating temperature for converting component (f) into a compound having a maximum absorption wavelength in the wavelength range of 350-500 nm is preferably 150°C or higher in order to improve halftone processability, and preferably 230°C or lower in order to control the maximum transmittance in the wavelength range of 410-440 nm to be low. Examples of component (f) include the thermochromic compound described in Japanese Patent Application Publication No. 2004-326094. In particular, it is preferable that component (f) contains a hydroxyl group-containing compound in order to improve halftone processability. Examples of hydroxyl group-containing compounds include 4,4',4”,4'''-(1,4-phenylenedimethylidene)tetrakisphenol (maximum absorption wavelength after heat treatment: 440 nm), 4,4',4”-trihydroxytriphenylmethane (maximum absorption wavelength after heat treatment: 460 nm), and 4-[bis(4-hydroxyphenyl)methyl)]2-methoxyphenol (maximum absorption wavelength after heat treatment: 470 nm).

[0164] The positive-type photosensitive pigment composition of the present invention may further contain other pigments other than component (a) for the purpose of fine-tuning the optical properties of the pixel splitting layer. Examples of other pigments include organic yellow pigments such as CI Pigment Yellow 24, 120, 138, 139, 150, 151, 175, 180, 185, 181, 192, 193, 194; organic orange pigments such as CI Pigment Orange 13, 36, 43, 60, 61, 62, 64, 71, 72; and CI Pigment Red 122, 123, 149, 178, 177, 179, 180, 189, 1 Examples of organic pigments include red pigments such as 90, 202, 209, 254, 255, and 264; blue pigments such as CI Pigment Blue 16, 25, 56, 57, 60, 61, 64, 65, 66, 75, 79, and 80; purple pigments such as CI Pigment Violet 19, 29, and 32; and black pigments such as perylene black. In addition, inorganic black pigments such as titanium nitride, zirconium nitride, and carbon black are also used. Among these, perylene-based black pigments having a benzimidazole skeleton (hereinafter sometimes referred to as "component (g)") are preferred for improving long-term storage stability. In other words, it is preferable that the positive-type photosensitive pigment composition of the present invention further contains a perylene-based black pigment having a (g) benzimidazole skeleton.

[0165] Examples of perylene-based black pigments having a benzimidazole skeleton include, for example, the compound represented by formula (82) and / or the compound represented by formula (83).

[0166] [ka]

[0167] In equations (82) and (83), R 97 ~R 104 Each of these independently represents a hydrogen atom, a fluorine atom, a bromine atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. R 105 ~R 112Each of these independently represents a hydrogen atom, a fluorine atom, a bromine atom, or a hydroxyl group.

[0168] A commercially available perylene-based black pigment containing a benzimidazole skeleton is "Spectrasense" (registered trademark) Black K0087 (manufactured by BASF), which is a mixture of the cis and trans isomers of 3,4,9,10-perylenetetracarboxylic acid bis-benzimidazole.

[0169] (g) The average primary particle size of component (g) is preferably 10 nm or more, and more preferably 20 nm or more, in order to improve halftone processability. From the same viewpoint, it is preferably 100 nm or less, and more preferably 80 nm or less. (e) The average aspect ratio of component (e) is preferably 1.0 or more, and more preferably 1.3 or more, in order to improve halftone processability and long-term storage stability. From the same viewpoint, it is preferably 3.0 or less, and more preferably 2.5 or less.

[0170] The positive-type photosensitive pigment composition of the present invention may contain other resins besides component (b). By combining the other resins with component (b), the exposure sensitivity in the exposure process described later and the optimal development time in the development process described later may be adjusted to a desired range. Examples of other resins include alkali-soluble polyimide precursors, alkali-soluble polyimide resins, alkali-soluble polysiloxane resins, alkali-soluble acrylic resins, alkali-soluble novolac resins, alkali-soluble polyether resins, alkali-soluble epoxy acrylate resins, and alkali-soluble maleimide resins. Among these, alkali-soluble polyimide precursors are preferred in terms of their excellent exposure sensitivity. The alkali-soluble polyimide precursor referred to here is an alkali-soluble resin that can be converted into a polyimide resin by heat treatment in the curing process described later, and specifically includes alkali-soluble polyamic acid or alkali-soluble polyamic acid esters. Here, "alkali-soluble resin" refers to a resin having a hydroxyl group, carboxyl group, phosphate group, and / or sulfo group as alkali-soluble groups within its molecule. Hydroxyl groups are preferred as alkali-soluble groups, and phenolic hydroxyl groups are more preferred. The content of other resins in the positive-type photosensitive pigment composition should be appropriately determined considering the type and concentration of the alkaline developer used in the development process, the development method, etc.

[0171] The positive-type photosensitive pigment composition of the present invention may further contain (h) a thermal crosslinking agent (hereinafter sometimes referred to as "component (h)"). Including component (h) makes it easier to adjust the optimal development time in the development process described later to an appropriate range, and may also improve the film strength of the pixel division layer and the spacer layer. As component (h), a compound having two or more alkoxymethyl groups or epoxy groups in its molecule is preferred. Examples of alkoxymethyl groups include methoxymethyl group, ethoxymethyl group, propoxymethyl group, and butoxymethyl group.

[0172] Examples of compounds having two or more alkoxymethyl groups in their molecule include HMOM-TPHAP, DML-PC, DML-PEP, DML-OC, DML-POP (all manufactured by Honshu Chemical Industry Co., Ltd.), NIKALAC® MX-390, MX-290, MX-280, MX-270, MW-100LM, and MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.).

[0173] Examples of compounds having two or more epoxy groups in their molecule include TEPIC-S, TEPIC-PAS, TEPIC-VL, TEPIC-UC (all manufactured by Nissan Chemical Corporation), XD-1000, XD-1000-H, XD-1000-2L, NC-3000 (all manufactured by Nippon Kayaku Co., Ltd.), TECHMORE VG3101L (manufactured by Printec Co., Ltd.), TR-FR-201 (manufactured by Tronly), KR-470, X-40-2678, X-40-2669 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0174] The positive-type photosensitive pigment composition of the present invention may optionally contain a nonionic surfactant as a leveling agent and a silane coupling agent as an adhesion improver to the substrate surface.

[0175] The chemical structures of the compounds belonging to the aforementioned components (a), (b), (c), (d), (e), (f), (g), and (h) can be analyzed using the positive-type photosensitive pigment composition of the present invention as a sample, by combining known analytical techniques such as time-of-flight secondary ion mass spectrometry (TOF-SIMS), time-of-flight mass spectrometry (TOF-MS), nuclear magnetic resonance (NMR), liquid chromatography-mass spectrometry (LC-MS), gas chromatography-mass spectrometry (GC-MS), ICP mass spectrometry, infrared absorption spectrometry, and X-ray diffraction. In particular, for components (a), (e), and (g), the positive-type photosensitive pigment composition may be centrifuged, and the concentrated obtained as a filtrate may be analyzed as a sample to improve identification accuracy. On the other hand, for components (b), (c), and (h), the filtrate obtained by filtering the supernatant after centrifugation may be analyzed as a sample to improve identification accuracy.

[0176] The method for preparing the positive-type photosensitive pigment composition is not particularly limited, but for example, a pigment dispersion containing component (a), component (b), component (d), and optionally component (e) and component (g) is prepared in advance by wet dispersion treatment, and then component (c), component (d), and optionally component (f), component (h), and other components are mixed and stirred with the pigment dispersion, and filtered as necessary. In particular, it is desirable to use component (b) in the production of the pigment dispersion because it interacts with component (a) to easily achieve higher long-term storage stability.

[0177] For wet dispersion processing, either a wet media disperser or a wet medialess disperser may be used, but the use of a wet media disperser is preferable due to its superior dispersion processing speed and economic advantages. Examples of wet media dispersers include bead mills such as "RevoMill" (registered trademark) (manufactured by Asada Iron Works Co., Ltd.), "Nano-Getter" (registered trademark) (manufactured by Ashizawa Finetech Co., Ltd.), "DYNO-MILL" (registered trademark) (manufactured by Willy A. Bachofen), "SpikeMill" (registered trademark) (manufactured by Inoue Seisakusho Co., Ltd.), "SandGrinder" (registered trademark) (manufactured by DuPont), "UltraApexMill" (registered trademark) (manufactured by Hiroshima Metal & Machinery Co., Ltd.), and "NEO-AlphaMill" (registered trademark) (manufactured by AIMEX Co., Ltd.). The media material is preferably ceramic beads such as zirconia, and the diameter is preferably 0.03 to 0.5 mmφ. A commercially available product is "Treceram" (registered trademark) (manufactured by Toray Industries, Inc.).

[0178] The D90 (cumulative 90% secondary particle diameter) of the particle size distribution of the particulate components in a positive-type photosensitive pigment composition, measured by dynamic light scattering, is preferably 150 nm or higher to improve long-term storage stability. On the other hand, it is preferably 300 nm or lower to improve halftone processability. D90 refers to the value measured on a particle size distribution measurement sample. A particle size distribution measurement sample is a sample obtained by mixing the positive-type photosensitive pigment composition with an equal amount of diluent solvent in three separate steps so that the ratio of positive-type photosensitive pigment composition to diluent solvent is 1:99 (by weight), and then stirring it on a shaker for 10 minutes. As the diluent solvent, an organic solvent with the same composition as component (d) contained in the positive-type photosensitive pigment composition is used. The particle size distribution referred to here can be measured using the SZ-100 dynamic light scattering particle size distribution analyzer (manufactured by Horiba, Ltd.), and D90 represents the particle size (nm) that corresponds to 90% of the cumulative particle size distribution curve, with the smaller particle size side as the base point (0%) and accumulating towards the larger particle size side.

[0179] A cured film according to a second aspect of the present invention is a cured film comprising a cured product of the positive-type photosensitive pigment composition of the present invention. The cured product referred to herein means a product obtained by heating the positive-type photosensitive pigment composition at a temperature of 200°C to 400°C under atmospheric pressure for 10 minutes or more.

[0180] A third aspect of the present invention is an organic EL display device comprising the cured film of the present invention.

[0181] When the cured film of the present invention is used as a pixel splitting layer in an organic EL display device, the optical density per 1.0 μm of film thickness of the pixel splitting layer is preferably 0.5 or higher, and more preferably 0.7 or higher, in order to suppress external light reflection and enhance the value as a display device. From the viewpoint of halftone processability, it is preferably 1.5 or lower, and more preferably 1.3 or lower.

[0182] Optical density refers to the value obtained by measuring the incident and transmitted light intensity of a pixel division layer formed on a transparent substrate to a thickness of 1.5 μm using an X-Rite 361T optical densitometer (manufactured by X-Rite Corporation), and dividing the value calculated from the following formula by the film thickness value of 1.5. A higher optical density indicates higher light shielding performance. As the transparent substrate, "Tempax" (manufactured by AGC Techno Glass Co., Ltd.), a transparent glass substrate, can be preferably used.

[0183] Optical density = log 10 (I0 / I) In the above equation, I0 is the incident light intensity and I is the transmitted light intensity.

[0184] To improve yield by reducing the contact area with the deposition mask when pattern deposition of the light-emitting layer, and to achieve both this and halftone processability, the film thickness of the pixel division layer is preferably 1.0 to 2.0 μm, and the film thickness of the spacer layer, which is placed on a part of the surface of the pixel division layer, is preferably 1.0 to 2.0 μm. Therefore, the film thickness of the area where the pixel division layer and the spacer layer are stacked is preferably 2.0 to 4.0 μm.

[0185] The cross-sectional taper angle at the edge of the pixel division layer is preferably 50° or less, and more preferably 40° or less, in order to suppress electrode disconnection and avoid the occurrence of unlit pixels. It is preferably 15° or more, and more preferably 20° or more, in order to suppress the decrease in light shielding performance at the edge of the pixel division layer.

[0186] It is preferable to form the pixel splitting layer and spacer layer together using a single positive-type photosensitive pigment composition, as this has the advantage of significantly reducing manufacturing process costs. A preferred method for forming the pixel splitting layer and spacer layer together includes a coating step of applying a positive-type photosensitive pigment composition to obtain a coated film, a pre-baking step of heating the coated film to obtain a pre-baked film, an exposure step of pattern-exposing activation lines through a positive-type halftone exposure mask to obtain an exposure film having exposed areas, semi-exposed areas, and unexposed areas in the plane, a developing step of developing with an alkaline developer to remove a portion of the exposed and semi-exposed areas to obtain a developed film, and a curing step of heat-curing to obtain a cured film.

[0187] As the coating apparatus used in the coating process, a spin coater or a slit coater can be preferably used due to its excellent thin-film coating properties. After coating, pin gap pre-baking or contact pre-baking may be performed.

[0188] In the pre-bake process, the pre-bake temperature is preferably 50 to 150°C, and the pre-bake time is preferably 30 seconds to 5 minutes. The thickness of the pre-bake film is preferably 3.5 to 6.0 μm. When near-infrared alignment is performed in the exposure process described later, the maximum transmittance of the pre-bake film of the positive-type photosensitive pigment composition at wavelengths of 800 to 1,300 nm is preferably 20% or more, and more preferably 30% or more, in order to improve positional accuracy.

[0189] Examples of exposure equipment used in the exposure process include steppers, mirror projection mask aligners (MPAs), and parallel light mask aligners (PLAs). Examples of activation rays used for exposure include the j-line (wavelength 313 nm), i-line (wavelength 365 nm), h-line (wavelength 405 nm), or g-line (wavelength 436 nm) of a high-pressure mercury lamp. A mixed line including at least the h-line is preferred, and a mixed line including the g-line, h-line, and i-line is more preferred. It is preferable to use a positive-type halftone exposure mask that has a fully transparent area, a semi-transparent area, and a shielding area within the substrate surface, and is designed so that when the exposure amount in the fully transparent area is 100% and the exposure amount in the shielding area is 0%, the exposure amount in the semi-transparent area is 10 to 50%.

[0190] In an exposure film, the exposed area refers to the area pattern-exposed through the fully transparent portion of the exposure mask, the partially exposed area refers to the area pattern-exposed through the semi-transparent portion of the exposure mask, and the unexposed area refers to the area not exposed by the shielding portion of the exposure mask. The difference in dissolution rate per unit time of the exposed, partially exposed, and unexposed areas in the alkaline developer, due to the difference in exposure amount within the same plane, enables the simultaneous formation of the pixel division layer and spacer layer by halftone processing.

[0191] Examples of development methods in the development process include shower, dipping, and paddle methods, and a method of immersing the exposed film for 10 seconds to 3 minutes is also possible. The paddle method is preferred for improving halftone processing. A 0.4 to 2.5 wt% aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as "TMAH") is preferred as the alkaline developer, and a commercially available product is, for example, 2.38 wt% TMAH (manufactured by Tama Chemical Industry Co., Ltd.). After the development process, a washing treatment by showering with deionized water and / or a dewatering treatment by air spraying may be added. 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.

[0192] In the curing process, the developing film is heat-cured by heating, and any remaining developer or moisture in the film is volatilized to obtain a cured film. Examples of heating devices include hot air ovens and IR ovens, and the heating atmosphere can be nitrogen or air. The heating temperature is preferably 200 to 350°C under atmospheric pressure, and more preferably 220 to 280°C.

[0193] A fourth aspect of the present invention is an organic EL display device comprising a pixel splitting layer containing a triphendioxazine pigment represented by formula (7). The pixel splitting layer contains a triphendioxazine pigment represented by formula (7), which provides the advantageous effects of high pixel emission area ratio and high lightfastness reliability. To further improve the pixel emission area ratio and lightfastness reliability, it is more preferable that the pixel splitting layer further contains a triphendioxazine dye having (e) a sulfo group bonded to a carbon atom constituting an aromatic ring and / or a carboxyl group bonded to a carbon atom constituting an aromatic ring, and not having a chlorine atom in the molecule. The same considerations as those applied to the triphendioxazine dyes belonging to component (e) mentioned above can be applied to component (e) here, and specific examples include the compounds represented by formula (67) and formula (68) mentioned above. [Examples]

[0194] The present invention will be described in detail below with reference to examples and comparative examples thereof, but the embodiments of the present invention are not limited thereto. First, we will explain the evaluation methods used in each example and comparative example.

[0195] <Evaluation of the minimum required exposure (exposure sensitivity)> A silver alloy (an alloy consisting of 99.00 wt% silver and 1.00 wt% copper) was deposited over the entire surface of an alkali-free glass substrate measuring 150 mm in length and 150 mm in width by sputtering. Furthermore, an ITO (indium-tin oxide) film was deposited over the entire surface by sputtering, resulting in a glass substrate with both a silver alloy film and an ITO film covering the entire surface of the alkali-free glass substrate.

[0196] Positive-type photosensitive pigment compositions 1-28 obtained in Examples 1-21, Comparative Examples 1-6 and 9, and negative-type photosensitive pigment compositions 1-2 obtained in Comparative Examples 7-8 were applied to the ITO surface of a glass substrate equipped with a silver alloy film / ITO film using a spin coater, adjusting the rotation speed so that the final pixel division layer thickness was 1.5 μm and the spacer layer thickness was 1.5 ± 0.1 μm (i.e., the thickness of the area where the pixel division layer and spacer layer are stacked was 3.0 ± 0.1 μm), respectively, to obtain coated films. Furthermore, the coated films were pre-baked for 120 seconds at 110°C under atmospheric pressure using a hot plate to obtain pre-baked films. Next, using a double-sided alignment single-sided exposure apparatus, exposure is performed through a positive halftone exposure mask (a mask designed so that when the exposure amount in the fully transparent areas is 100% and the exposure amount in the shielded areas is 0%, the exposure amount in the semi-transparent areas is 15%) at 50-200 mJ / cm². 2 Within the range of (h line reference), the exposure amount was gradually changed in increments of 10 mJ within the plane of the pre-baked film, and the g, h, and i mixed lines of an ultra-high pressure mercury lamp were pattern-exposed onto the pre-baked film to obtain an exposed film having exposed areas, partially exposed areas, and unexposed areas within its plane. The pattern exposure was performed by bringing a positive-type halftone exposure mask into contact with the surface of the pre-baked film.

[0197] Next, as a development step, development was performed using a paddle method with a small photolithography developing device (AD-1200; manufactured by Takizawa Sangyo Co., Ltd.) and an alkaline developer solution, a 2.38 wt% aqueous solution of tetramethylammonium hydroxide. The paddle method refers to a method in which the alkaline developer solution is showered onto the surface of the exposure film for 10 seconds, and then left to stand for a predetermined development time. The development time was set to the time at which the film thickness was within the range of 0.5 to 1.0 μm. Film thickness here refers to the value obtained by subtracting the film thickness in the unexposed areas of the developed film from the film thickness of the pre-baked film. Furthermore, after rinsing with deionized water using the shower method for 30 seconds, the substrate was dried by running it empty at 200 rpm for 30 seconds to obtain a developed film-forming substrate with a developed film.

[0198] Next, as a curing step, the developing film was heated at 250°C under air for 1 hour using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.) to obtain a substrate for evaluating the minimum required exposure with a patterned cured film. For reference, Figure 1 shows an image of the cross-section of the substrate for evaluating the minimum required exposure obtained in Example 1, observed with a scanning electron microscope (SEM). In Figure 1, 1 is the pixel division layer and 2 is the spacer layer.

[0199] Using an FPD inspection microscope (MX-61L; manufactured by Olympus Corporation), the patterned cured film was observed, and the average value of the aperture widths of 10 apertures in each exposure range was within the range of 30.0 ± 0.1 μm, and the minimum required exposure (mJ / cm²) when the film was formed in one piece such that the thickness of the pixel division layer was 1.5 μm and the thickness of the spacer layer was 1.5 ± 0.1 μm. 2 (The value was calculated using the h-line equivalent). If the opening was not square, the major axis was used as the opening width.

[0200] On the other hand, for negative-type photosensitive pigment compositions 1 and 2, the minimum required exposure was determined using the same method as described above, except that a negative-type halftone exposure mask (a reverse mask with 220 square shielding areas measuring 30.0 μm vertically and 30.0 μm horizontally arranged, designed so that when the exposure amount in the fully transparent areas is 100% and the exposure amount in the shielding areas is 0%, the exposure amount in the semi-transparent areas is 30%) was used instead of the positive-type halftone exposure mask described above, and the development time was set to 1.5 times the time it takes for the film in the unexposed areas to dissolve and be removed.

[0201] Furthermore, if it was difficult to form the 10 apertures in a single stage so that the average aperture width was within the range of 30.0 ± 0.1 μm, and the pixel division layer thickness was 1.5 μm and the spacer layer thickness was 1.5 ± 0.1 μm, the product was excluded from evaluation.

[0202] (1) Evaluation of the light-shielding properties (OD / μm) of the cured film For the light-shielding evaluation substrates on which cured films with a thickness of 1.5 μm were formed using the methods obtained in Examples 1-21 and Comparative Examples 1-9, the total optical density (Total OD value) was measured at three in-plane locations from the film surface side using an optical densitometer (X-Rite 361T). The average value of these measurements was calculated, and the result was divided by 1.5 and rounded to the second decimal place. This value was taken as the OD value per 1.0 μm of film thickness, i.e., the light-shielding performance (OD / μm). The evaluation was based on the criterion that a higher light-shielding performance indicates a better cured film. The OD value of Tempax without a cured film was measured separately and found to be 0.00, so the OD value of the optical density evaluation substrate was considered to be the OD value of the cured film. The thickness of the cured film was calculated by averaging the values ​​measured at three in-plane locations using a stylus-type film thickness measuring device (Tokyo Seimitsu Co., Ltd.; Surfcom) and rounding to the second decimal place.

[0203] (2) Evaluation of halftone workability and (3) storage stability The organic EL display devices obtained in Examples 1-21 and Comparative Examples 1-9 were placed on a hot plate with the light-emitting surface facing upwards and maintained at a surface temperature of 85°C, and driven by DC current (10 mA / cm²). 2 The pixel emission area ratio (area ratio of the light-emitting portion to 100% of the area of ​​the light-emitting pixel) of the organic EL display device was evaluated one hour after starting illumination. The pixel emission area ratio of the organic EL display device was calculated by measuring the pixel emission area ratio (%) for each of the 20 light-emitting pixels located in the center of the display unit, magnified on a monitor at 100x magnification, and rounding the average value of these measurements to the first decimal place. A higher pixel emission area ratio with fewer non-light-emitting areas (pixel shrinkage) in the pixel unit was considered superior. The evaluation was based on the following criteria, with AA and A-C being passable and D-G being failing. The evaluation results obtained for the first organic EL display device in each example and comparative example were designated as (2) Halftone processability (evaluation before long-term storage), and the evaluation results obtained for the second organic EL display device were designated as (3) Storage stability (evaluation after long-term storage). AA: The pixel luminescence area ratio of the organic EL display device is 95% or higher. A: The pixel emission area ratio of the organic EL display device is 90% or more but less than 95%. B: The pixel luminescence area ratio of the organic EL display device is 85% or more but less than 90%. C: The pixel luminescence area ratio of the organic EL display device is 80% or more but less than 85%. D: The pixel emission area ratio of the organic EL display device is 50% or more but less than 80%. E: The pixel emission area ratio of the organic EL display device is less than 50%. F: One or more pixels that are completely unlit (pixel light emission area ratio of 0%) are observed. G: Due to poor halftone processing capabilities, it is difficult to measure the minimum required exposure amount, making a proper evaluation impossible.

[0204] (4) Evaluation of light resistance reliability of organic EL display devices The organic EL display device (second organic EL display device) used in the aforementioned (3) evaluation of storage stability was placed on a hot plate with the light-emitting surface facing upwards and maintained at a surface temperature of 85°C, and driven by DC current (10mA / cm²). 2 The process was started and then restarted. The display unit of the organic EL display device was kept lit, and a xenon lamp was used as the light source to simulate sunlight containing near-ultraviolet light, with an illuminance of 3.0 W / cm² at a wavelength of 420 nm. 2 The OLED display was continuously irradiated with light. The pixel emission area ratio of the OLED display was evaluated 100 hours and 500 hours after the start of irradiation. The pixel emission area ratio of the OLED display was calculated by measuring the pixel emission area ratio (%) for each of the 20 light-emitting pixels located in the center of the display unit, magnified on a monitor at 100x magnification, and rounding the average value to the first decimal place. A higher pixel emission area ratio with fewer non-emitting areas in the pixel unit was considered superior. The following criteria were used for evaluation, with AA and A-C being passable and D-G being failing. For reference, Figure 2 shows a schematic diagram of a light-emitting pixel unit that has 3 light-emitting areas and no non-light-emitting areas. Also, as an example of a case where non-light-emitting areas occur, Figure 3 shows a schematic diagram of a light-emitting pixel unit that has 4 light-emitting areas and 5 non-light-emitting areas. AA: The pixel luminescence area ratio of the organic EL display device is 95% or higher. A: The pixel emission area ratio of the organic EL display device is 90% or more but less than 95%. B: The pixel luminescence area ratio of the organic EL display device is 85% or more but less than 90%. C: The pixel luminescence area ratio of the organic EL display device is 80% or more but less than 85%. D: The pixel emission area ratio of the organic EL display device is 50% or more but less than 80%. E: The pixel emission area ratio of the organic EL display device is less than 50%. F: One or more pixels that are completely unlit (pixel light emission area ratio of 0%) are observed. G: Due to poor halftone processing capabilities, it is difficult to measure the minimum required exposure amount, making a proper evaluation impossible.

[0205] (Manufacturing Example 1: Production of Micronized Triphendioxazine Pigment A) 1000.00 g of "Cromophtal" (registered trademark) Violet D5700 (BASF: CI Pigment Violet 37) was heated in an oven at 200°C under atmospheric pressure / air for 1 hour, then cooled to room temperature. The dried aggregates were then broken up using a ball mill to obtain triphendioxazine pigment 1. Next, the pigment was refined by solvent salt milling according to the following procedure.

[0206] 500.00 g of triphendioxazine pigment 1, 2.5 kg of grinding material (sodium chloride particles with an average primary particle size of 0.5 μm, pre-treated at 230°C for 1 hour to remove 0.1% by weight of moisture), and 250.00 g of dipropylene glycol were mixed and placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), and kneaded at 90°C for 5 hours to obtain a dark purple mixture. This mixture was added to 5 L of warm water and stirred for 1 hour while maintaining the temperature at 70°C to form a slurry. Washing with deionized water and filtration were repeated three times to remove the grinding material and dipropylene glycol. Furthermore, after drying in an oven at 200°C under atmospheric pressure / air for 6 hours, the dried aggregates were broken down by grinding with a ball mill to obtain finely ground triphendioxazine pigment A consisting of the compound represented by formula (84). The finely milled triphendioxazine pigment A was component (a), with an average primary particle diameter of 30 nm, a maximum primary particle diameter of 110 nm, and an average aspect ratio of 1.5. The composition and classification of finely milled triphendioxazine pigment A are shown in Table 1.

[0207] [ka]

[0208] [Table 1]

[0209] (Manufacturing Example 2: Manufacturing of Micronized Triphendioxazine Pigment B) 1500.00 g of acetic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a flask, and 500.00 g (2.42 mol) of 2,5-diamino-3,6-dichloro-1,4-benzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 20.00 g of benzenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. The mixture was stirred at a temperature of 30°C for 10 hours to react and obtain the intermediate represented by formula (85), which was then filtered off.

[0210] [ka]

[0211] Next, 5365.05 g of 1,3-dimethyl-2-imidazolidinone (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a flask, and 684.04 g (2.35 mol) of the intermediate represented by formula (85) was added. 1037.73 g (4.94 mol) of 3-amino-9-ethylcarbazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and the mixture was stirred at 30°C for 30 minutes. Further, 5.00 g of triethylamine was added and the mixture was stirred at 40°C for 7 hours to generate a triphendioxazine precursor. Then, 190.22 g (1.00 mol) of p-toluenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as an oxidizing agent, and the mixture was heated to 180°C and stirred for 6 hours to cyclize the triphendioxazine precursor, obtaining a slurry containing the pigment crude. This slurry was cooled to 50°C and filtered. The filtrate was washed once with 1,3-dimethyl-2-imidazolidinone and twice with ethanol. Afterward, the mixture was repeatedly washed with water and filtered until the p-toluenesulfonic acid content, as quantified by LC-MS, was 50 ppm by weight or less in the pigment. Triphendioxazine pigment 2 was obtained by drying in an oven at 120°C under atmospheric pressure / air for 6 hours. 500.00 g of triphendioxazine pigment 2, 2.5 kg of grinding material (same as in Production Example 1), and 250.00 g of dipropylene glycol were mixed and placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), and kneaded at 90°C for 8 hours to obtain a dark purple mixture. This mixture was added to 5 L of warm water and stirred for 1 hour while maintaining the temperature at 70°C to form a slurry. Washing with deionized water and filtration were repeated three times to remove the grinding material and dipropylene glycol. Furthermore, after drying in an oven at 200°C under atmospheric pressure / air for 6 hours, dry grinding was performed using a nanojetmizer (manufactured by Aisin Nanotechnologies Corporation) to obtain finely ground triphendioxazine pigment B consisting of the compound represented by formula (86). The finely milled triphendioxazine pigment B was component (a), with an average primary particle diameter of 35 nm, a maximum primary particle diameter of 115 nm, and an average aspect ratio of 1.7. The composition and classification of the finely milled triphendioxazine pigment B are shown in Table 1.

[0212] [ka]

[0213] (Manufacturing Example 3: Production of Micronized Triphendioxazine Pigment C) 1500.00 g of pentanoic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a flask, and 505.73 g (2.42 mol) of 2,5-dichloro-3,6-dihydroxy-p-benzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 20.00 g of benzenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. The mixture was stirred at a temperature of 30°C for 10 hours to react and obtain the intermediate represented by formula (87), which was then filtered off.

[0214] [ka]

[0215] Next, 5365.05 g of 1,3-dimethyl-2-imidazolidinone was placed in a flask, and 886.44 g (2.35 mol) of the intermediate represented by formula (87) and 1037.73 g (4.94 mol) of 3-amino-9-ethylcarbazole were added, and the mixture was stirred at 30°C for 30 minutes. Furthermore, 5.00 g of triethylamine was added, and the mixture was stirred at 40°C for 7 hours to produce a triphendioxazine precursor. Then, 190.22 g (1.00 mol) of p-toluenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as an oxidizing agent, and the mixture was heated to 180°C and stirred for 6 hours to cyclize the triphendioxazine precursor, obtaining a slurry containing the pigment crude. This slurry was then cooled to 50°C and filtered off. The filtrate was washed once with 1,3-dimethyl-2-imidazolidinone and twice with ethanol. Then, repeated washing with deionized water and filtration were performed until the amount of p-toluenesulfonic acid quantified by LC-MS was 50 ppm by weight or less in the pigment. The mixture was dried in an oven at 120°C under atmospheric pressure / air for 6 hours to obtain triphendioxazine pigment 3.

[0216] 500.00 g of triphendioxazine pigment 3, 2.5 kg of grinding material (same as in Production Example 1), and 250.00 g of dipropylene glycol were mixed and charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho). The mixture was kneaded at 90°C for 8 hours to obtain a dark purple paste. This paste was added to 5 L of warm water and stirred for 1 hour while maintaining the temperature at 70°C to form a slurry. Washing with deionized water and filtration were repeated three times to remove the grinding material and dipropylene glycol. Furthermore, after drying in an oven at 200°C under atmospheric pressure / air for 6 hours, dry grinding was performed using a nanojet miller to obtain finely milled triphendioxazine pigment C consisting of the compound represented by formula (88). Finely milled triphendioxazine pigment C is component (a), with an average primary particle diameter of 40 nm, a maximum primary particle diameter of 115 nm, and an average aspect ratio of 1.8. Table 1 shows the composition and classification of the micronized triphendioxazine pigment C.

[0217] [ka]

[0218] (Manufacturing Example 4: Production of Micronized Triphendioxazine Pigment D) The intermediate represented by formula (85) above was obtained using the same procedure as in Production Example 2. 5365.05 g of 1,3-dimethyl-2-imidazolidinone was placed in a flask, and 684.04 g (2.35 mol) of the intermediate represented by formula (85) and 1064.49 g (5.88 mol) of 2-ethoxy-4-aminobenzoic acid were added. The mixture was stirred at a liquid temperature of 80°C for 6 hours to react and produce a triphendioxazine precursor. Furthermore, 190.22 g (1.00 mol) of p-toluenesulfonic acid monohydrate was added as an oxidizing agent, and the liquid temperature was raised to 180°C. Stirring was maintained for 6 hours to cyclize the triphendioxazine precursor, and the product was filtered off. After washing once with ethanol, the mixture was washed with water and filtered three times. The mixture was dried in an oven at 100°C under atmospheric pressure / air for 6 hours to obtain a dicarboxylic acid having a triphendioxazine skeleton.

[0219] 1153.64 g (2.00 mol) of a dicarboxylic acid having a triphendioxazine skeleton was added to 2617.34 g of thionyl chloride, and the reaction was carried out by stirring at a liquid temperature of 70°C for 6 hours. The filtrate was washed twice with ethanol, and then washed with water and filtered repeatedly until the chloride ion content, as quantified by ion chromatography, was 50 ppm by weight or less in the acid chloride having a triphendioxazine skeleton described later. The mixture was dried in an oven at 100°C under atmospheric pressure / air for 6 hours to obtain the acid chloride having a triphendioxazine skeleton.

[0220] Next, 920.10 g (1.50 mol) of an acid chloride having a triphendioxazine skeleton was added to 5136.75 g of 1,3-dimethyl-2-imidazolidinone to form a slurry. While stirring the slurry, 349.24 g (3.75 mol) of aminobenzene was added and the mixture was stirred at a liquid temperature of 70°C for 6 hours to react and obtain a slurry containing the pigment crude. This slurry was cooled to 50°C and filtered. The filtrate was washed once with 1,3-dimethyl-2-imidazolidinone, twice with ethanol, and then washed three times with deionized water and filtered. The filtrate was dried in an oven at 120°C under atmospheric pressure / air for 6 hours to obtain triphendioxazine pigment 4. Next, in addition to fine milling by solvent salt milling in the same manner as in Production Example 3, drying and grinding were performed to obtain finely milled triphendioxazine pigment D consisting of the compound represented by formula (89). The finely milled triphendioxazine pigment D was component (a), with an average primary particle diameter of 39 nm, a maximum primary particle diameter of 97 nm, and an average aspect ratio of 1.9. The composition and classification of the finely milled triphendioxazine pigment D are shown in Table 1.

[0221] [ka]

[0222] (Manufacturing Example 5: Manufacturing of Micronized Triphendioxazine Pigment E) A finely milled triphendioxazine pigment E, consisting of the compound represented by formula (90), was prepared using the same method as in Production Example 4, except that 454.43 g (3.75 mol) of 4-ethylaniline was used instead of 349.24 g (3.75 mol) of aminobenzene. The finely milled triphendioxazine pigment E was component (a), with an average primary particle diameter of 40 nm, a maximum primary particle diameter of 104 nm, and an average aspect ratio of 1.8. The composition and classification of the finely milled triphendioxazine pigment E are shown in Table 1.

[0223] [ka]

[0224] (Manufacturing Example 6: Production of triphendioxazine-based dye F) The intermediate represented by formula (85) above was obtained using the same procedure as in Production Example 2. 1361.50 g of 1,3-dimethyl-2-imidazolidinone was placed in a flask, and 145.54 g (0.50 mol) of the intermediate represented by formula (85) and 330.38 g (1.25 mol) of 5-amino-2-phenylaminobenzenesulfonic acid (Sigma-Aldrich) were added. The mixture was stirred at a liquid temperature of 80°C for 10 hours to react and produce a triphendioxazine precursor containing a sulfo group. Furthermore, 47.555 g (0.25 mol) of p-toluenesulfonic acid monohydrate was added as an oxidizing agent, and the liquid temperature was raised to 180°C. Stirring was maintained for 6 hours to cyclize the triphendioxazine precursor containing a sulfo group, and the product was filtered off. After washing the filtrate with ethanol, the mixture was repeatedly washed with deionized water and filtered until the residual amount of p-toluenesulfonic acid, as quantified by LC-MS, was less than 50 ppm by weight. It was then dried under reduced pressure at 80°C for 24 hours to obtain a powder. Furthermore, it was subjected to dry grinding using a nanojet mill, and the mixture was passed through a stainless steel sieve filter (aperture diameter 50 μm) to remove coarse dried aggregates, yielding component (e), the triphendioxazine-based dye F, represented by formula (91). The composition and classification of triphendioxazine-based dye F are shown in Table 2.

[0225] [ka]

[0226] [Table 2]

[0227] (Manufacturing Example 7: Production of triphendioxazine-based dye G) The triphendioxazine-based dye G, which is component (e) and represented by formula (92), was prepared using the same method as in Production Example 6, except that 3-amino-9-ethyl-9H-carbazole-2-sulfonic acid (manufactured by Innopharmchem) was used instead of 330.38 g (1.25 mol) of 5-amino-2-phenylaminobenzenesulfonic acid. The composition and classification of triphendioxazine-based dye G are shown in Table 2.

[0228] [ka]

[0229] (Manufacturing Example 8: Production of Perylenebisimide Dye H) 50.00 g of CI Pigment Red 178 was dissolved in 500.00 g of 80 wt% concentrated sulfuric acid and heated, and stirred at a liquid temperature of 70°C for 6 hours to allow the sulfonation reaction to proceed. Next, the mixture was placed in 5 kg of ice water to obtain a slurry containing precipitate, which was then filtered. The filtrate was then washed with ethanol, and then washed with deionized water and filtered repeatedly until the residual sulfate ion content was less than 50 wt ppm. It was then dried under reduced pressure at 80°C for 24 hours to obtain a powder. Furthermore, it was subjected to dry grinding using a nanojetmizer, and the coarse dried aggregates were removed by passing it through a stainless steel sieve filter to obtain component (e), a perylene bisimide-based dye H. LC-MS and proton nuclear magnetic resonance spectroscopy (hereinafter, 1Analysis by 1H-NMR revealed that the perylenebisimide dye H was a mixture of compounds represented by formula (93), formula (94), and formula (95) in a weight ratio of 25:65:10. The composition and classification of the perylenebisimide dye H are shown in Table 2.

[0230] [ka]

[0231] (Manufacturing Example 9: Manufacturing of Anthraquinone Dye I) 50.00 g of CI Solvent Green 3 was dissolved in 500.00 g of 40 wt% concentrated sulfuric acid and heated. The mixture was stirred at 40°C for 4 hours to allow the sulfonation reaction to proceed. Next, the mixture was placed in 5 kg of ice water to obtain a slurry containing precipitate, which was then filtered. The filtrate was then repeatedly washed with deionized water and filtered until the residual sulfate ion content was less than 50 wt ppm. It was then dried under reduced pressure at 80°C for 24 hours to obtain a powder. Furthermore, it was subjected to dry grinding using a nanojet pulverizer and filtered through a stainless steel sieve filter to remove coarse dried aggregates, yielding anthraquinone-based dye I. LC-MS and 1 Analysis by 1H-NMR revealed that the anthraquinone-based dye I was component (e), which is the compound represented by formula (96).

[0232] [ka]

[0233] (Manufacturing Example 9: Manufacturing of Anthraquinone Dye J) 100.00 g of CI Solvent Blue 104 was added to 1400.00 g of thionyl chloride and stirred at 5°C for 1 hour, then stirred at 20°C for 3 hours. The mixture was placed in 2 kg of ice water to obtain a slurry containing a blue precipitate, which was filtered off. The slurry was repeatedly washed with water and filtered until the remaining chloride ion content was less than 50 ppm by weight, and dried under reduced pressure at 80°C to obtain an anthraquinone-based dye, sulfonyl chloride. Next, 74.60 g (0.50 mol) of methyl 3-amino-4-methylbenzoate was added to a flask containing 456.60 g of 1,3-dimethyl-2-imidazolidinone and stirred at 10°C for 30 minutes. Furthermore, 134.32 g (0.20 mol) of the aforementioned anthraquinone-based dye sulfonyl chloride was added, and the mixture was stirred at 20°C for 4 hours. After filtration, the mixture was washed with water and filtered five times to obtain the anthraquinone-based dye carboxylic acid ester. 134.56 g (0.15 mol) of the aforementioned anthraquinone-based dye carboxylic acid ester was added to a flask containing 342.45 g of 1,3-dimethyl-2-imidazolidinone and 264.00 g of 5 wt% aqueous sodium hydroxide solution. The mixture was stirred at 40°C for 3 hours to induce hydrolysis. The mixture was cooled to 20°C, and 240.62 g of 5 wt% aqueous hydrochloric acid solution was added and stirred. After filtration, the mixture was washed with water and filtered repeatedly until the remaining sodium ions and chloride ions in the filtrate were each less than 50 wt ppm. The mixture was then purified using silica gel chromatography and dried under reduced pressure at 80°C for 24 hours. Furthermore, dry grinding was performed using a nanojet pulverizer, and coarse dried aggregates were removed by filtering through a stainless steel sieve to obtain anthraquinone-based dye J. LC-MS and 1 Analysis by 1H-NMR revealed that the anthraquinone-based dye J was component (e), and was a compound represented by formula (97).

[0234] [ka]

[0235] (Manufacturing Example 10: Manufacturing of Micronized Perylene Black Pigment K) 1,000.00 g of "Spectrasense" (registered trademark) Black K0087 (manufactured by BASF) was heated in an oven at 250°C under atmospheric pressure / air for 1 hour, then cooled to room temperature, and the dried aggregates were broken up in a ball mill to obtain black pigment 1. Next, the pigment was refined by solvent salt milling according to the following procedure.

[0236] 500.00 g of black pigment 1, 2.5 kg of grinding material (sodium chloride particles with an average primary particle size of 0.5 μm, pre-treated at 230°C for 1 hour to remove 0.1% by weight of moisture), and 250.00 g of dipropylene glycol were mixed and placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), and kneaded at 90°C for 8 hours. This mixture was added to 5 L of warm water and stirred for 1 hour while maintaining the temperature at 70°C to form a slurry. Washing with deionized water and filtration were repeated until the sodium ions and chloride ions quantified by ion chromatography were each 50 ppm by weight or less, thereby removing the grinding material and dipropylene glycol. Furthermore, after drying in an oven at 100°C under atmospheric pressure / air for 6 hours, the dried aggregates were broken up with a ball mill to obtain finely milled perylene black pigment K consisting of a compound represented by formula (98) and a mixture of isomers of the compound represented by formula (99). The finely milled perylene black pigment K is component (g), with an average primary particle diameter of 25 nm, a maximum primary particle diameter of 98 nm, and an average aspect ratio of 1.9. The composition and classification of the finely milled perylene black pigment K are shown in Table 1.

[0237] [ka]

[0238] (Manufacturing Example 11: Manufacturing of Micronized Triphendioxazine Pigment L) A refined triphendioxazine pigment L consisting of the compound represented by formula (100) was obtained using the same method as in Production Example 1, except that CI pigment violet 23 represented by formula (100) was used instead of "Cromophtal" (registered trademark) Violet D5700. The refined triphendioxazine pigment L is a pigment that does not belong to component (a), and had an average primary particle diameter of 32 nm, a maximum primary particle diameter of 118 nm, and an average aspect ratio of 1.8. The composition and classification of the refined triphendioxazine pigment L are shown in Table 1.

[0239] [ka]

[0240] (Manufacturing Example 12: Manufacturing of Quinone Diazide Compound M) Under a dry nitrogen atmosphere, 127.36 g (0.30 mol) of the compound represented by formula (101) (manufactured by Honshu Chemical Industry Co., Ltd.), 80.60 g (0.30 mol) of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride, and 80.60 g (0.30 mol) of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride were added to 1910.43 g of 1,4-dioxane, and the mixture was stirred at a liquid temperature of 20°C for 1 hour. Furthermore, 303.57 g of an additive (triethylamine:1,4-dioxane = weight ratio 20:80) was added dropwise, and the mixture was stirred at a liquid temperature of 30°C for 3 hours. The triethylamine salt was filtered off, the filtrate was added to water, and the resulting precipitate was collected. After washing it three times with deionized water, it was filtered off and dried under reduced pressure to obtain component (c), a quinone diazide compound M represented by formula (102).

[0241] [ka]

[0242] In equation (102), * represents the bonding site with the oxygen atom. 1:1:1 represents the molar ratio.

[0243] (Manufacturing Example 13: Manufacturing of quinone diazide compound N) Under a stream of dry nitrogen, 316.45 g (0.50 mol) of the compound represented by formula (103) (manufactured by Honshu Chemical Industry Co., Ltd.) and 335.84 g (1.25 mol) of 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride were added to 4746.68 g of 1,4-dioxane, and the mixture was stirred at a liquid temperature of 20°C for 1 hour. Furthermore, 632.44 g of additive (triethylamine:1,4-dioxane = weight ratio 20:80) was added dropwise, and the mixture was stirred at a liquid temperature of 30°C for 3 hours. The triethylamine salt was filtered off, and the precipitate formed by adding the filtrate to water was collected. After washing three times with deionized water, the precipitate was filtered off and dried under reduced pressure to obtain component (c), the quinone diazide compound N represented by formula (104).

[0244] [ka]

[0245] In equation (104), * represents a bonding site with an oxygen atom. 1:2.5 represents the molar ratio. (Manufacturing Example 14: Production of Polyimide Precursor O) 18.31 g (0.05 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was dissolved in 100 mL of acetone and 17.4 g of propylene oxide, and cooled to -15°C. A solution of 20.41 g (0.11 mol) of 3-nitrobenzoyl chloride dissolved in 100 mL of acetone was added dropwise. After the addition was complete, the mixture was reacted at -15°C for 4 hours, and then allowed to return to room temperature. The precipitated white solid was filtered off and vacuum-dried at 50°C. 30 g of the solid was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon was added. Hydrogen was introduced using a balloon, and the reduction reaction was carried out at room temperature. After approximately 2 hours, the reaction was terminated when it was confirmed that the balloon no longer deflated. After the reaction was complete, the palladium catalyst was removed by filtration, and the mixture was concentrated using a rotary evaporator to obtain hydroxyl group-containing diamine compound a.

[0246] Next, under a stream of dry nitrogen, 31.02 g (0.10 mol) of 4,4'-oxydiphthalic acid dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 500.00 g of NMP. To this, 45.34 g (0.075 mol) of hydroxyl group-containing diamine compound a and 1.24 g (0.005 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane (manufactured by Tokyo Chemical Industry Co., Ltd.) were added along with 50.00 g of NMP, and the mixture was reacted at 20°C for 1 hour, followed by a reaction at a liquid temperature of 50°C for 2 hours. As a terminal encapsulant, 4.36 g (0.04 mol) of 4-aminophenol was added along with 5.00 g of NMP, and the mixture was reacted at 50°C for 2 hours. Subsequently, 28.60 g (0.24 mol) of N,N-dimethylformamide dimethylacetal was added, and the mixture was stirred at 50°C for 3 hours. After stirring, the solution was cooled to room temperature, and then added to 3 L of water to obtain a white precipitate, which was then filtered. The purified white precipitate was collected as a filtrate after being washed with water and filtered four more times, washed five times with deionized water, and then dried in a vacuum dryer at 80°C for 24 hours to obtain polyimide precursor O with a weight-average molecular weight (Mw) of 25,000. Polyimide precursor O is a resin that does not belong to component (b), and does not have the structure represented by formula (1), formula (2), and formula (47) mentioned above, but has the structure represented by formula (105). 1 This was confirmed by 1H-NMR analysis.

[0247] [ka]

[0248] In equation (105), * represents a bonding site.

[0249] (Manufacturing Example 15: Manufacturing of Diimidazolide Compound P) Under a stream of dry nitrogen, 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. Then, maintaining the liquid temperature below 20°C, 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. After the generation of carbon dioxide gas was complete, it was cooled to 5°C. 1000.00 g of deionized water was added dropwise while maintaining the temperature below 10°C, and the precipitate was filtered off. The precipitate was washed with deionized water and then with isopropanol. The precipitate was dried under reduced pressure at 50°C for 6 hours to obtain the diimidazolide compound P represented by formula (106).

[0250] [ka]

[0251] (Manufacturing Example 16: Manufacturing of diimidazolide compound Q) Diimidazolide compound Q, represented by formula (107), was obtained by the same method as in Production Example 15, except that 106.43 g (0.44 mol) of 4,4'-biphenyldicarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of diphenyl ether 4,4'-dicarboxylic acid.

[0252] [ka]

[0253] (Manufacturing Example 17: Manufacturing of hydroxyl group-containing polyamide resin R) Under a stream of dry nitrogen, 732.52 g (2.00 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added to 3662.60 g of NMP and stirred at 40°C for 1 hour. Then, 573.38 g (1.60 mol) of diimidazolide compound P, prepared in Preparation Example 15, was added along 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 acid anhydride was added and the mixture was stirred at 80°C for 3 hours. The mixture was cooled to 20°C, 600.20 g of acetic acid was added and stirred for 30 minutes, then 500.00 g of NMP was added and the mixture was stirred for another hour. The solution obtained from the above operations was added to 10 L of water to obtain a precipitate. The precipitate was filtered, washed five times with deionized water, and then dried under reduced pressure at 50°C for three days to obtain a hydroxyl group-containing polyamide resin R with a weight-average molecular weight (Mw) of 26,000. The hydroxyl group-containing polyamide resin R is a resin belonging to component (b) and has a structure represented by formula (32), a structure represented by formula (47), and repeating units represented by formula (36). 1 This was confirmed by 1H-NMR and infrared absorption spectroscopy. The structure of the hydroxyl group-containing polyamide resin R is shown in Table 3.

[0254] [Table 3]

[0255] (Manufacturing Example 18: Production of hydroxyl group-containing polyamide resin S) Instead of diimidazolide compound P, 547.78 g (1.60 mol) of diimidazolide compound Q prepared in Preparation Example 16 was used to obtain hydroxyl group-containing polyamide resin S in the same manner as in Preparation Example 17. Hydroxyl group-containing polyamide resin S is a resin belonging to component (b), and has a structure represented by formula (32), a structure represented by formula (47), and a repeating unit represented by formula (36). 1 This was confirmed by 1H-NMR and infrared absorption spectroscopy. The structure of the hydroxyl group-containing polyamide resin S is shown in Table 3.

[0256] (Manufacturing Example 19: Manufacturing of hydroxyl group-containing polyamide resin T) Hydroxyl group-containing polyamide resin T was obtained by the same method as in Production Example 17, except that 158.54 g (0.80 mol) of 1,2-naphthalenedicarboxylic acid anhydride was used instead of 5-norbornene-2,3-dicarboxylic acid anhydride. Hydroxyl group-containing polyamide resin T is a resin belonging to component (b), and has a structure represented by formula (33), a structure represented by formula (47), and a repeating unit represented by formula (36). 1 This was confirmed by 1H-NMR and infrared absorption spectroscopy. The structure of hydroxyl group-containing polyamide resin T is shown in Table 3.

[0257] (Manufacturing Example 20: Manufacturing of hydroxyl group-containing polyamide resin U) Hydroxyl group-containing polyamide resin U was obtained by the same method as in Production Example 17, except that 153.70 g (0.80 mol) of trimellitic anhydride was used instead of 5-norbornene-2,3-dicarboxylic acid anhydride. Hydroxyl group-containing polyamide resin U is a resin belonging to component (b), and has a structure represented by formula (34), a structure represented by formula (47), and a repeating unit represented by formula (36). 1 This was confirmed by 1H-NMR and infrared absorption spectroscopy. The structure of hydroxyl group-containing polyamide resin U is shown in Table 3.

[0258] (Manufacturing Example 21: Manufacturing of hydroxyl group-containing polyamide resin V) Hydroxyl group-containing polyamide resin U was obtained by the same method as in Production Example 17, except that 198.59 g (0.80 mol) of 2,3-anthracenedicarboxylic acid anhydride was used instead of 5-norbornene-2,3-dicarboxylic acid anhydride. Hydroxyl group-containing polyamide resin U is a resin belonging to component (b), and has a structure represented by formula (1), a structure represented by formula (47), and a repeating unit represented by formula (36). 1 This was confirmed by 1H-NMR and infrared absorption spectroscopy. The structure of hydroxyl group-containing polyamide resin V is shown in Table 3.

[0259] (Manufacturing Example 22: Manufacturing of hydroxyl group-containing polyamide resin W) A hydroxyl group-containing polyamide resin W was obtained by the same method as in Production Example 17, except that 78.45 g (0.80 mol) of maleic anhydride was used instead of 5-norbornene-2,3-dicarboxylic acid anhydride. The hydroxyl group-containing polyamide resin W is a resin belonging to component (b), and has a structure represented by formula (1), a structure represented by formula (47), and a repeating unit represented by formula (36). 1 This was confirmed by 1H-NMR and infrared absorption spectroscopy. The structure of the hydroxyl group-containing polyamide resin W is shown in Table 3.

[0260] (Manufacturing Example 23: Manufacturing of hydroxyl group-containing polyimide resin X) Under a stream of dry nitrogen, 366.26 g (1.00 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added to 2563.82 g of NMP, and the mixture was stirred at 40°C for 1 hour. Then, 248.18 g (0.80 mol) of 4,4-oxydiphthalic acid dianhydride, 79.27 g (0.40 mol) of cyclohexane-1,2,4-tricarboxylic acid 1,2-anhydride, and 300.00 g of NMP were added, and the mixture was stirred at 40°C for 1 hour. After that, the temperature was raised to 180°C, and the mixture was maintained at 180°C for 5 hours while removing the generated water. After the reaction was complete, the mixture was cooled to 40°C and added to 10 L of water. The resulting precipitate was filtered and collected, washed five times with deionized water, and dried under reduced pressure at 80°C for 24 hours to obtain a hydroxyl group-containing polyimide resin X with a weight-average molecular weight (Mw) of 28,000. The hydroxyl group-containing polyimide resin X is a resin belonging to component (b), and does not have the structure represented by formula (47), but has the structure represented by formula (2) and the repeating units represented by formula (37). 1 This was confirmed by 1H-NMR and infrared absorption spectroscopy. The structure of the hydroxyl group-containing polyamide resin X is shown in Table 3.

[0261] (Manufacturing Example 24: Manufacturing of hydroxyl polyimide resin Y) A hydroxyl group-containing polyimide resin Y with a weight-average molecular weight (Mw) of 31,000 was obtained by the same method as in Production Example 23, except that 96.87 g (0.40 mol) of 1,2,5-naphthalentricarboxylic acid 1,2-anhydride was used instead of cyclohexane-1,2,4-tricarboxylic acid 1,2-anhydride. The hydroxyl group-containing polyimide resin Y is a resin belonging to component (b), and does not have the structure represented by formula (47), but has the structure represented by formula (2) and the repeating unit represented by formula (37). 1 This was confirmed by 1H-NMR and infrared absorption spectroscopy. The structure of hydroxyl group-containing polyamide resin Y is shown in Table 3.

[0262] (Manufacturing Example 25: Manufacturing of hydroxyl group-containing polyimide resin Z) Under a stream of dry nitrogen, 256.38 g (0.70 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added to 2563.82 g of NMP, and the mixture was stirred at 40°C for 1 hour. Further, 444.24 g (1.00 mol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 82.28 g (0.60 mol) of 3-aminobenzoic acid, and 300.00 g of NMP were added, and the mixture was stirred at 40°C for 1 hour. The temperature was then raised to 180°C, and the mixture was maintained at 180°C for 5 hours while removing the generated water. After the reaction was complete, the mixture was cooled to 40°C and added to 10 L of water. The resulting precipitate was filtered and collected, washed 5 times with deionized water, and dried under reduced pressure at 80°C for 24 hours to obtain hydroxyl group-containing polyimide resin Z. The hydroxyl group-containing polyimide resin Z is a resin belonging to component (b), and does not have the structure represented by formula (47), but has the structure represented by formula (108) which corresponds to the structure represented by formula (2), and repeating units represented by formula (37). 1 This was confirmed by 1H-NMR and infrared absorption spectroscopy. The structure of the hydroxyl group-containing polyamide resin Z is shown in Table 3.

[0263] [ka]

[0264] In equation (108), * represents a bonding site.

[0265] (Manufacturing Example 26: Manufacturing of Polyimide Resin 1) Polyimide resin 1 was synthesized based on the method described in Synthesis Example 1 of International Publication No. 2019 / 065359. Under a stream of dry nitrogen, 150.15 g (0.41 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 6.20 g (0.02 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 13.65 g (0.13 mol) of 3-aminophenol were dissolved in 500.00 g of NMP. To this, 155.10 g (0.50 mol) of bis(3,4-dicarboxyphenyl) ether dianhydride and 150.00 g of NMP were added and the mixture was stirred at 20°C for 1 hour, and then stirred at 180°C for 4 hours while removing water. After the reaction was complete, the reaction mixture was added to 10 L of water, and the resulting precipitate was collected by filtration and washed five times with deionized water. Polyimide resin 1 with a weight-average molecular weight (Mw) of 25,000 was obtained by drying in a vacuum dryer at 80°C for 20 hours. Polyimide resin 1 is a resin that does not belong to component (b), and does not have the structure represented by formula (1), the structure represented by formula (2), and the structure represented by formula (47), but has the structure represented by formula (109). 1 This was confirmed by 1H-NMR and infrared absorption spectroscopy. The structure of polyimide resin 1 is shown in Table 3.

[0266] [ka]

[0267] In equation (109), * represents a bonding site.

[0268] (Manufacturing Example 27: Manufacturing of Polyimide Resin 2) Polyimide resin 2 was synthesized based on the method described in Synthesis Example 1 of International Publication No. 2019 / 087985. Under a stream of dry nitrogen, 31.13 g (0.085 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1.24 g (0.0050 mol) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, and 2.18 g (0.020 mol) of 3-aminophenol were dissolved in 150.00 g of NMP. Furthermore, a solution of 31.02 g (0.10 mol) of 4,4'-oxydiphthalic acid dianhydride dissolved in 50.00 g of NMP was added, and the mixture was stirred at 20°C for 1 hour, followed by stirring at 50°C for 4 hours. Subsequently, 15.00 g of xylene was added, and the mixture was stirred at 150°C for 5 hours while azeotropically stirring with water. After the reaction was complete, the reaction solution was added to 3 L of water, and the precipitated solid was filtered off. The obtained solid precipitate was washed three times with deionized water. It was dried in a vacuum dryer at 80°C for 24 hours to obtain polyimide resin 2 with a weight-average molecular weight (Mw) of 27,000. Polyimide resin 2 is a resin that does not belong to component (b), and like polyimide resin 1 described above, it does not have the structure represented by formula (1), the structure represented by formula (2), and the structure represented by formula (47), but has the structure represented by formula (109). 1 This was confirmed by 1H-NMR and infrared absorption spectroscopy. The structure of polyimide resin 2 is shown in Table 3. Furthermore, powdered polyimide resin 2 was dissolved in MBA to a solid content of 30% by weight, and this was prepared as polyimide resin solution 2.

[0269] (Manufacturing Example 28: Synthesis of Methacrylic Resin Solution 3) Based on the method described in Synthesis Example 2 of International Publication No. 2019 / 065359, a methacrylic resin solution 3 was obtained by the following method. To 185.44 g of PGMEA, maintained at a liquid temperature of 100°C under a stream of dry nitrogen, a mixture of 12.91 g (0.15 mol) of methacrylic acid, 55.07 g (0.55 mol) of methyl methacrylate, 21.01 g (0.10 mol) of acid phosphooxyethyl methacrylate (an ethylenically unsaturated monomer having a phosphate group), 26.43 g (0.15 mol) of benzyl methacrylate, and 8.21 g of azobisisobutyronitrile was added dropwise over 30 minutes. The mixture was then stirred for 1 hour while maintaining the liquid temperature at 100°C to allow the thermal polymerization reaction to proceed, after which it was cooled to synthesize a methacrylic resin 3 having a phosphate group. The methacrylic resin 3 is a resin that does not belong to component (b) and does not have the structure represented by formula (1), the structure represented by formula (2), and the structure represented by formula (47). 1 This was confirmed by 1H-NMR and infrared absorption spectroscopy. The weight-average molecular weight (Mw) was 9500. This was diluted with PGMEA to a solid content of 30% by weight to obtain methacrylic resin solution 3.

[0270] (Manufacturing Example 29: Manufacturing of Triphendioxazine Dye 1) 50.00 g of CI Pigment Violet 23 was dissolved in 500.00 g of 60 wt% concentrated sulfuric acid and heated. The mixture was stirred at 50°C for 5 hours to allow the sulfonation reaction to proceed. Next, the mixture was placed in 5 kg of ice water to obtain a slurry containing precipitate, which was then filtered. The filtrate was then repeatedly washed with deionized water and filtered until the residual sulfate ion content was less than 50 wt ppm. It was then dried under reduced pressure at 80°C for 24 hours to obtain a powder. Furthermore, it was subjected to dry grinding using a nanojet pulverizer and filtered through a stainless steel sieve to remove coarse dried aggregates, yielding triphendioxazine-based dye 1. LC-MS and 1Analysis by 1H-NMR revealed that triphendioxazine dye 1 is a mixture of the compound represented by formula (110) and the compound represented by formula (111) in a weight ratio of 14:86, containing two chlorine atoms in its molecule, and is an organic dye that does not belong to component (e). The composition of triphendioxazine dye 1 is shown in Table 2.

[0271] [ka]

[0272] (Manufacturing Example 30: Production of Triphendioxazine Dye 2) 50.00 g of CI Pigment Violet 23 was added to 500.00 g of chlorosulfonic acid and stirred for 1 hour. Next, 50.00 g of thionyl chloride was added and stirred at 60°C for 5 hours. The mixture was then placed in 5 kg of ice water to obtain a slurry containing precipitate, which was filtered. After repeating washing and filtration with deionized water three times, the slurry was added to 500.00 g of deionized water, and 70.00 g of 3-diethylaminopropylamine was added while stirring. After stirring at 80°C for 2 hours, washing and filtration with deionized water were repeated three times, and the mixture was dried under reduced pressure at 80°C for 24 hours to obtain a powder. Furthermore, dry grinding was performed using a nanojet pulverizer, and coarse dried aggregates were removed by passing the mixture through a stainless steel sieve filter to obtain triphendioxazine-based dye 2. LC-MS and 1 Analysis by 1H-NMR revealed that triphendioxazine dye 2 is a mixture of the compound represented by formula (112) and the compound represented by formula (113) in a weight ratio of 8:92, containing two chlorine atoms in its molecule, and is an organic dye that does not belong to component (e). The composition of triphendioxazine dye 2 is shown in Table 2.

[0273] [ka]

[0274] (Manufacturing example 31) Under a stream of dry nitrogen, 21.22 g (0.05 mol) of TrisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) and 36.27 g (0.135 mol) of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride were dissolved in 450.00 g of 1,4-dioxane and allowed to rise to room temperature. A solution of 15.18 g of triethylamine dissolved in 50.00 g of 1,4-dioxane was added dropwise, ensuring the system temperature did not exceed 35°C, and the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was added to water. The precipitated material was then collected by filtration. This precipitate was dried in a vacuum dryer to obtain quinone diazide compound b.

[0275] (Manufacturing Example 32: Manufacturing of hydroxyl group-containing polyamide resin R2) Under a stream of dry nitrogen, 732.52 g (2.00 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added to 3662.60 g of NMP and stirred at a liquid temperature of 40°C for 1 hour. Furthermore, 573.38 g (1.60 mol) of diimidazolide compound P, prepared in Preparation Example 15, was added together with 286.69 g of NMP, and the liquid temperature was raised to 80°C and stirred for 5 hours. Next, 196.99 g (1.20 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride was added, and the liquid temperature was raised to 110°C and stirred for 5 hours. The liquid temperature was cooled to 20°C, 900.30 g of acetic acid was added and stirred for 30 minutes, then 1 kg of NMP was added and stirred for a further 1 hour. The solution obtained by the above operations was added to 10 L of water to obtain a precipitate. This precipitate was filtered off, washed five times with deionized water, and then dried under reduced pressure at 50°C for three days to obtain a hydroxyl group-containing polyamide resin R2 with a weight-average molecular weight (Mw) of 28,000. The hydroxyl group-containing polyamide resin R2 is a resin belonging to component (b), and does not have the structure represented by formula (47), but has the structure represented by formula (32) and the repeating units represented by formula (36). 1 This was confirmed by 1H-NMR and infrared absorption spectroscopy. The structure of the hydroxyl group-containing polyamide resin R2 is shown in Table 3.

[0276] (Manufacturing Example 33: Manufacturing of hydroxyl group-containing polyamide resin R3) Under a stream of dry nitrogen, 293.01 g (0.80 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 309.98 g (1.20 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane were added to 3014.96 g of NMP and stirred at 40°C for 1 hour. Next, 573.38 g (1.60 mol) of diimidazolide compound P was added along with 286.69 g of NMP, the temperature was raised to 80°C, and the mixture was stirred for 5 hours. Then, 131.33 g (0.80 mol) of 5-norbornene-2,3-dicarboxylic acid anhydride was added and the mixture was stirred at 80°C for 3 hours. The solution was cooled to 20°C, 600.20 g of acetic acid was added and stirred for 30 minutes, then 500.00 g of NMP was added and stirred for another hour. The solution obtained by the above procedure was added to 10 L of water to obtain a precipitate. This precipitate was filtered off, washed 5 times with deionized water, and then dried under reduced pressure at 50°C for 3 days to obtain a hydroxyl group-containing polyamide resin R3 with a weight-average molecular weight (Mw) of 28000. The hydroxyl group-containing polyamide resin R3 is a resin belonging to component (b) and has a structure represented by formula (32), a structure represented by formula (47), and repeating units represented by formula (36). 1 This was confirmed by 1H-NMR and infrared absorption spectroscopy. The structure of the hydroxyl group-containing polyamide resin R3 is shown in Table 3.

[0277] (Preparation Example 1: Preparation of Pigment Dispersion 1) (d) 31.25 g of polyimide precursor O and 31.25 g of hydroxyl group-containing polyamide resin R were added to 900.00 g of a mixed solvent (PGME:ethyl lactate:GBL = weight ratio 75:20:5), and the mixture was stirred for 1 hour to dissolve. Then, 6.25 g of perylenebisimide dye H, which is component (e), was added and stirred for 30 minutes, after which 31.25 g of finely milled triphendioxazine pigment A, which is component (a), was added and stirred for 30 minutes to obtain a preliminary stirring solution. Next, a wet media dispersion treatment was performed using the following method. A pre-mixed liquid was supplied to a vertical bead mill "Ultra Apex Mill Advance" (registered trademark, manufactured by Hiroshima Metal & Machinery Co., Ltd.) in which 0.4 mmφ zirconia beads, "Treceram" (registered trademark, manufactured by Toray Industries, Inc.), were packed into the vessel at a packing rate of 75 vol%. A wet media dispersion treatment was performed for 1 hour at a peripheral speed of 10 m / s using a circulating system. Then, the liquid was supplied to another vertical bead mill in which 0.1 mmφ zirconia beads, "Treceram" (registered trademark, manufactured by Toray Industries, Inc.), were packed into the vessel at a packing rate of 75 vol%. A wet media dispersion treatment was performed for 3 hours at a peripheral speed of 8 m / s using a circulating system. The mixture was filtered through a 0.5 μm diameter filter to obtain pigment dispersion 1 with a solid content of 10.00 wt%. No change was observed in the solid content value to two decimal places before and after filtration. The blending weights of each raw material are shown in Table 4.

[0278] [Table 4]

[0279] (Preparation Examples 2-5: Preparation of Pigment Dispersions 2-5) Pigment dispersions 2 to 5 were prepared in the same manner as in Preparation Example 1, except that micronized triphendioxazine pigment B, micronized triphendioxazine pigment C, micronized triphendioxazine pigment D, or micronized triphendioxazine pigment E were used instead of micronized triphendioxazine pigment A, with the formulation weights shown in Table 4.

[0280] (Preparation Examples 6-10: Preparation of Pigment Dispersions 6-10) Pigment dispersions 6 to 10 were prepared in the same manner as in Preparation Example 1, except that hydroxyl group-containing polyamide resin S, hydroxyl group-containing polyamide resin T, hydroxyl group-containing polyamide resin U, hydroxyl group-containing polyamide resin V, or hydroxyl group-containing polyamide resin W were used instead of hydroxyl group-containing polyamide resin R, with the blending weights shown in Table 5.

[0281] [Table 5]

[0282] (Preparation Examples 11-13: Preparation of Pigment Dispersions 11-13) Pigment dispersions 11 to 13 were prepared in the same manner as in Preparation Example 1, except that hydroxyl group-containing polyimide resin X, hydroxyl group-containing polyimide resin Y, or hydroxyl group-containing polyimide resin Z were used instead of hydroxyl group-containing polyamide resin R, with the blending weights shown in Table 6.

[0283] [Table 6]

[0284] (Preparation Examples 14-17: Preparation of Pigment Dispersions 14-17) Pigment dispersions 14 to 17 were prepared in the same manner as in Preparation Example 1, except that perylenebisimide dye H was replaced with triphendioxazine dye F, triphendioxazine dye G, anthraquinone dye I, or anthraquinone dye J, in the formulation weights shown in Table 7. Only in pigment dispersion 15, micronized triphendioxazine pigment B was used as component (a) instead of micronized triphendioxazine pigment A.

[0285] [Table 7]

[0286] (Preparation Example 18: Preparation of Pigment Dispersion 18) Pigment dispersion 18 was prepared in the same manner as in Preparation Example 1, except that it was prepared by mixing finely milled triphendioxazine pigment A with finely milled perylene black pigment K, which is component (g), in the weights shown in Table 7.

[0287] (Preparation Example 19: Preparation of Pigment Dispersion 19) Pigment dispersion 19 was prepared in the same manner as in Preparation Example 1, except that component (e) was not used, in the proportions shown in Table 7.

[0288] (Preparation Example 20: Preparation of Pigment Dispersion 20) Pigment dispersions 20 were prepared in the same manner as in Preparation Example 1, except that a hydroxyl group-containing polyamide resin R and a perylene bisimide dye H were not used, in the formulation weights shown in Table 8.

[0289] [Table 8]

[0290] (Preparation Example 21: Preparation of Pigment Dispersion 21) Except for using finely milled triphendioxazine pigment C instead of finely milled triphendioxazine pigment A, and not using hydroxyl group-containing polyamide resin R and perylene bisimide dye H, pigment dispersions 21 were prepared in the same manner as in Preparation Example 1, with the formulation weights shown in Table 8.

[0291] (Preparation Example 22: Preparation of Pigment Dispersion 22) Pigment dispersion 22 was prepared in the same manner as in Preparation Example 1, except that micronized triphendioxazine pigment L was used instead of micronized triphendioxazine pigment A, and hydroxyl group-containing polyamide resin R and perylene bisimide dye H were not used, in the proportions shown in Table 8.

[0292] (Preparation Example 23: Preparation of Pigment Dispersion 23) Pigment dispersion 23 was prepared in the same manner as in Preparation Example 1, with the following differences: micronized triphendioxazine pigment L was used instead of micronized triphendioxazine pigment A; hydroxyl group-containing polyamide resin R was not used; and triphendioxazine-based dye 1 was used instead of perylenebisimide-based dye H, in the proportions shown in Table 8.

[0293] (Preparation Example 24: Preparation of Pigment Dispersion 24) Pigment dispersion 24 was prepared in the same manner as in Preparation Example 1, with the following differences: micronized triphendioxazine pigment L was used instead of micronized triphendioxazine pigment A; hydroxyl group-containing polyamide resin R was not used; and triphendioxazine-based dye 2 was used instead of perylenebisimide-based dye H, in the proportions shown in Table 8.

[0294] (Preparation Example 25: Preparation of Pigment Dispersion 25) Based on the method described in Preparation Example 16 of International Publication No. 2019 / 065359, pigment dispersion 25 was prepared by the following method: 26.72 g of polyimide resin 1 and 93.75 g of methacrylic resin solution 3 (solids content 30% by weight) were added to 784.38 g of PGMEA and stirred for 30 minutes. Then, 1.41 g of perylene-based dye derivative 8 (perylene-based dye derivative 8 disclosed in International Publication No. 2019 / 065359) was added and stirred for 30 minutes to obtain a pre-mixed solution. Next, 28.13 g of CI pigment yellow 192 (average primary particle size 42 nm), 28.13 g of CI pigment red 179 (average primary particle size 48 nm), and 37.50 g of CI pigment blue 60 (average primary particle size 61 nm) were added and stirred for 30 minutes. A horizontal bead mill ("DYNO-MILL" (registered trademark), manufactured by Willy A. Bachofen) filled with 0.4 mmφ zirconia beads, "Treceram" (registered trademark), was used to perform a wet media dispersion treatment in a circulating manner for 30 minutes. Next, a vertical bead mill ("Ultra Apex Mill" (registered trademark), manufactured by Hiroshima Metal & Machinery Co., Ltd.) filled with 0.05 mmφ zirconia beads, "Treceram" (registered trademark), manufactured by Toray Industries, Inc., at a filling rate of 75 volume%, was used to perform a wet media dispersion treatment in a circulating manner. After 30 minutes, an appropriate amount of the pigment dispersion was extracted into a glass bottle every 10 minutes of dispersion time and sampled. This sample was then placed in a dynamic light scattering particle size distribution analyzer SZ-100 to measure the average dispersed particle size. The pigment dispersion that measured within the range of 150 nm ± 20 nm 30 minutes after sampling was designated as pigment dispersion 25. The solid content of pigment dispersion 25 was 15.00% by weight. Here, the average dispersed particle diameter refers to the numerical average of the secondary particle diameters of all pigment particles contained in the pigment dispersion. The blending weights are shown in Table 9.

[0295] [Table 9]

[0296] (Preparation Example 26: Preparation of Pigment Dispersion 26) Based on the method described in Preparation Example 10 of International Publication No. 2019 / 087985, pigment dispersion 26 was prepared by the following method: 100.00 g of polyimide resin solution 2 and 57.69 g of DISPERBYK®-167 (manufactured by BIC Chemie Japan: amine value 13 mg KOH / g, solids content 52 wt% solution), a urethane-based dispersant solution, were added to 752.31 g of MBA and stirred for 10 minutes. Next, 58.50 g of "Cromophtal" (registered trademark) Violet D5700 (BASF: CI Pigment Violet 37), which is component (a), and 31.50 g of CIPigment Yellow 192 (Clariant) were added and stirred for 30 minutes. Then, using a horizontal bead mill filled with 0.40 mmφ zirconia beads, a wet media dispersion treatment was performed to obtain a pigment dispersion 26 with a solid content of 15.00 wt%. The blending weights are shown in Table 9.

[0297] (Preparation Example 27: Preparation of Pigment Dispersion 27) 57.21 g of “KAYARAD” (registered trademark) 1569H (manufactured by Nippon Kayaku Co., Ltd., 69 wt% solids PGMEA solution), an epoxy acrylate resin solution, and 77.02 g of BYK-LPN21116 (manufactured by BIC Chemie Japan, 41 wt% solids solution), an acrylic dispersant solution, were added to 786.82 g of PGMEA and stirred for 10 minutes. Next, 78.95 g of “Irgaphor Black” (registered trademark) S0100CF (manufactured by BASF), a lactam-based organic black pigment, was added and stirred for 30 minutes. Wet media dispersion treatment was performed using a horizontal bead mill filled with 0.40 mmφ zirconia beads to obtain a pigment dispersion 27 with a solids content of 15.00 wt%. The blending weights are shown in Table 9.

[0298] (Preparation Example 28: Preparation of Pigment Dispersion 28) 40.00 g of polyimide precursor O was dissolved in 800.00 g of GBL, and 160.00 g of ZrN-1 (manufactured by Nisshin Engineering Co., Ltd.), which is zirconium nitride particles produced by the thermal plasma method, was added. The mixture was stirred in a homomixer for 20 minutes to obtain a preliminary dispersion. The preliminary dispersion was fed into an Ultraapex Mill (manufactured by Hiroshima Metal & Machinery Co., Ltd.) packed with 75 vol% of 0.05 mmφ zirconia beads, and wet media dispersion treatment was performed at a peripheral speed of 10 m / s for 3 hours to obtain a pigment dispersion 28 with a solid content of 20.00 wt%. The pigment dispersion 28 was coated onto a glass substrate, and after pre-baking on a hot plate at 120°C for 2 minutes, a pre-baked film with a thickness of 3.0 μm was created. The X-ray diffraction spectrum was measured by wide-angle X-ray diffraction using a RU-200R (manufactured by Rigaku Corporation), and the crystallite size of the zirconium nitride particles was found to be 15 nm. (Example 1) Under a yellow light, 1.74 g of polyimide precursor O, 0.40 g of quinone diazide compound M, 0.30 g of quinone diazide compound N, 0.70 g of 4,4',4”-trihydroxytriphenylmethane (manufactured by Tokyo Chemical Industry Co., Ltd.), which is component (f), and 0.80 g of HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.), which is component (h), were mixed in 34.45 g of a mixed solvent (PGME:ethyl lactate:GBL = weight ratio 75:20:5), and stirred for 30 minutes to dissolve. Furthermore, 2.00 g of a nonionic surfactant was added as a leveling agent. A 5% by weight PGME solution of Emulgen A-60 (manufactured by Kao Corporation) and a 5% by weight PGME solution of BYK-333 (manufactured by BYChemie Japan Co., Ltd.), a silicone-based surfactant, were added and stirred for 30 minutes to dissolve. Next, 59.55 g of pigment dispersion 1 was added and stirred for 30 minutes, after which the mixture was filtered through a 0.5 μm diameter filter to obtain a positive-type photosensitive pigment composition 1 with a solid content of 10.00% by weight. No change was observed in the solid content value to two decimal places before and after filtration. The blending weights of each raw material are shown in Table 10.

[0299] [Table 10]

[0300] After preparation, 48 g of positive-type photosensitive pigment composition 1 was added to each of two 100 mL light-shielding glass bottles and stored (at atmospheric pressure / light-shielding / in a cool, dark place maintained at -20±1°C, sealed and undisturbed). After 1 day of storage, one of the bottles was removed from the cool, dark place, the liquid temperature was allowed to rise to 23°C, and the minimum required exposure was evaluated using the method described above.

[0301] Next, the positive-type photosensitive pigment composition 1 was applied to the surface of a transparent glass substrate, "Tempax" (manufactured by AGC Technoglass Co., Ltd.), using a spin coater with the rotation speed adjusted so that the final cured film thickness would be 1.5 μm, thereby obtaining a coated film. The coated film was pre-baked at 110°C for 120 seconds under atmospheric pressure using a hot plate (SCW-636; manufactured by Dainippon Screen Mfg. Co., Ltd.) to obtain a pre-baked film. Using a double-sided alignment single-sided exposure apparatus, the g, h, i mixed lines of an ultra-high pressure mercury lamp were exposed using the method described above. An exposed film was obtained by irradiating the entire surface of the pre-baked film with an exposure dose equivalent to 15% of the required minimum exposure dose. Development, rinsing, and drying were performed in the same manner as when evaluating the required minimum exposure dose to obtain a solid developed film. The developed film was cured by heating it at 250°C under air for 1 hour using a high-temperature inert gas oven (INH-9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.) to obtain a substrate for light-shielding evaluation with a solid cured film of 1.5 μm thickness. The results of evaluating the light-shielding properties (OD / μm) using the above method are shown in Table 11.

[0302] [Table 11]

[0303] Furthermore, a pixel-splitting layer, a spacer layer, and a first organic EL display device comprising them were fabricated using the following method. Figure 4 shows the fabrication process of the organic EL display device, including the steps for forming the pixel-splitting layer and the spacer layer.

[0304] A silver alloy (an alloy consisting of 99.00 wt% silver and 1.00 wt% copper) was deposited over the entire surface of an alkali-free glass substrate measuring 70 mm in length and 70 mm in width (6 in Figure 4) by sputtering. Using an alkali-soluble novolac-based positive resist, the substrate was etched by immersion in a silver alloy etching solution SEA-1 at a liquid temperature of 30°C to obtain a patterned silver alloy film with a thickness of 50 nm (7 in Figure 4). Furthermore, an ITO film was deposited over the entire surface by sputtering. Using an alkali-soluble novolac-based positive resist, the substrate was immersed in a 5 wt% oxalic acid aqueous solution at a liquid temperature of 50°C for 5 minutes, shower-washed with deionized water for 2 minutes, and then dried with an air blower to obtain a patterned ITO film with a thickness of 10 nm (8 in Figure 4). Through these steps, a first electrode-forming substrate was obtained on the surface of the alkali-free glass substrate, comprising a first electrode consisting of a layered pattern of silver alloy film / ITO film.

[0305] Positive-type photosensitive pigment composition 1 was applied to the surface of the first electrode formation substrate using a spin coater, adjusting the rotation speed so that the thickness of the pixel division layer obtained after the curing process was 1.5 μm and the thickness of the spacer layer was 1.5 ± 0.1 μm (i.e., the thickness of the area where the pixel division layer and the spacer layer are stacked is 3.0 ± 0.1 μm), thereby obtaining a coated film. Furthermore, the coated film was pre-baked for 120 seconds at 110°C under atmospheric pressure using a hot plate to obtain a pre-baked film. Using a double-sided alignment single-sided exposure apparatus, the pre-baked film was pattern-exposed to the pre-baked film with the minimum required exposure amount determined by the method described above, via a positive-type halftone exposure mask (a mask designed so that when the exposure amount in the fully transparent areas is 100% and the exposure amount in the shielded areas is 0%, the exposure amount in the semi-transparent areas is 15%), thereby obtaining an exposed film. Pattern exposure was performed by bringing a positive-type halftone exposure mask into contact with the surface of the pre-baked film. Next, development, rinsing, and drying were performed in the same manner as when evaluating the minimum required exposure to obtain a patterned developed film. The developed film was heated in a high-temperature inert gas oven at 250°C under air for 1 hour to obtain a pixel-splitting layer / spacer layer forming substrate having 220 openings and comprising a pixel-splitting layer with a thickness of 1.5 μm and a spacer layer (9 in Figure 4) with a thickness of 1.5 μm within a 30 mm vertical / 30 mm horizontal area in the center of the first electrode forming substrate.

[0306] Next, an organic EL layer (10 in Figure 4) containing the light-emitting layer is formed at the opening of the pixel division layer by vacuum deposition, using a vacuum degree of 1 × 10⁻¹⁰. -3 Under deposition conditions below Pa, the pixel-splitting layer-forming substrate was rotated relative to the deposition source. First, a 10 nm thick layer of compound (HT-1) represented by formula (114) was deposited as a hole injection layer, and a 50 nm thick layer of compound (HT-2) represented by formula (115) was deposited as a hole transport layer. Next, a 40 nm thick layer of compound (GH-1) represented by formula (116) was deposited as a host material, and a 40 nm thick layer of compound (GD-1) represented by formula (117) was deposited as a dopant material. Subsequently, a 40 nm thick layer of compound (ET-1) represented by formula (118) and a 40 nm thick layer of compound (LiQ) represented by formula (119) was deposited as electron transport materials in a volume ratio of 1:1.

[0307] [ka]

[0308] Next, after depositing a compound (LiQ) at a thickness of 2 nm, a silver / magnesium alloy (volume ratio 10:1) was deposited to a thickness of 150 nm to form a second electrode (11 in Figure 4). Then, under a low humidity / nitrogen atmosphere, a cap-shaped glass plate was sealed by bonding it using an epoxy resin adhesive to obtain a first organic EL display device with an array of green light-emitting pixels. Note that each layer constituting the organic EL layer (10 in Figure 4) is very thin compared to the aforementioned pixel division layer and spacer layer, and high measurement accuracy cannot be obtained with a stylus-type film thickness measuring device. Therefore, each layer was measured using a quartz oscillator type film thickness monitor suitable for thin films of less than 100 nm, and the film thickness was taken by rounding the average value of three in-plane points to the first decimal place. The results of evaluating the halftone processability (2) using the first organic EL display device fabricated by the method described above are shown in Table 11. Next, after long-term storage (at atmospheric pressure / shielded / held in a cool, dark place at -20±1℃, in a sealed state), that is, after 180 days had elapsed since storage, the other positive-type photosensitive pigment composition 1 was removed from the cool, dark place, its liquid temperature was set to 23℃, and the minimum required exposure amount was evaluated using the method described above. A pixel-splitting layer / spacer layer forming substrate comprising a pixel-splitting layer with a thickness of 1.5 μm and a spacer layer with a thickness of 1.5 μm was then fabricated. Next, a second organic EL display device was fabricated using the same method as the first organic EL display device described above, and (3) storage stability and (4) light resistance reliability were evaluated using the method described above. The results are shown in Table 11.

[0309] (Examples 2-5) Positive-type photosensitive pigment compositions 2 to 5 were prepared using pigment dispersions 2 to 5 in the amounts shown in Table 10, instead of pigment dispersion 1. The following properties were evaluated in the same manner as in Example 1: (1) light shielding properties of the cured film, (2) halftone processability, (3) storage stability, and (4) lightfastness reliability. The evaluation results are shown in Table 11.

[0310] (Examples 6-10) Positive-type photosensitive pigment compositions 6 to 10 were prepared using pigment dispersions 6 to 10 in the amounts shown in Table 12, instead of pigment dispersion 1. The following were evaluated using the same method as in Example 1: (1) light shielding properties of the cured film, (2) halftone processability, (3) storage stability, and (4) lightfastness reliability. The evaluation results are shown in Table 13.

[0311] [Table 12]

[0312] [Table 13]

[0313] (Examples 11-13) Using pigment dispersions 11 to 13 instead of pigment dispersion 1, positive-type photosensitive pigment compositions 11 to 13 were prepared in the proportions shown in Table 14, and (1) the light-shielding properties of the cured film, (2) halftone processability, (3) storage stability, and (4) lightfastness reliability were evaluated using the same method as in Example 1. The evaluation results are shown in Table 15.

[0314] [Table 14]

[0315] [Table 15]

[0316] (Examples 14-19) Using pigment dispersions 14-19 instead of pigment dispersion 1, positive-type photosensitive pigment compositions 14-19 were prepared in the amounts shown in Table 16, and (1) the light-shielding properties of the cured film, (2) halftone processability, (3) storage stability, and (4) lightfastness reliability were evaluated using the same method as in Example 1. The evaluation results are shown in Table 17.

[0317] [Table 16]

[0318] [Table 17]

[0319] (Comparative Examples 1-5) Positive-type photosensitive pigment compositions 20-24 were prepared using pigment dispersions 20-24 instead of pigment dispersion 1, in the proportions shown in Table 18. The following were evaluated using the same method as in Example 1: (1) light shielding properties of the cured film, (2) halftone processability, (3) storage stability, and (4) lightfastness reliability. The evaluation results are shown in Table 19.

[0320] [Table 18]

[0321] [Table 19]

[0322] (Comparative Example 6) Based on the method described in Synthesis Example 3 of International Publication No. 2019 / 065359, quinone diazide compound a was synthesized by the following method. Under a stream of dry nitrogen, 21.23 g (0.05 mol) of TrisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.), a compound having a phenolic hydroxyl group, and 33.58 g (0.125 mol) of 5-naphthoquinone diazide sulfonylate chloride were dissolved in 450.00 g of 1,4-dioxane and brought to room temperature. To this, 12.65 g (0.125 mol) of triethylamine mixed with 50.00 g of 1,4-dioxane was added dropwise while maintaining the system temperature at 25-35°C. After addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was then filtered, the filtrate was added to water, and the precipitated precipitate was filtered and collected. By drying this precipitate in a vacuum dryer, a quinone diazide compound a with a solid content of 100.00% by weight was obtained.

[0323] Next, under a yellow light, 7.05 g of polyimide precursor 1, 3.60 g of quinone diazide compound a, and 0.60 g of VG-3101L (manufactured by Printec Co., Ltd.), which is component (h), were mixed in 63.75 g of a mixed solvent (PGMEA:MBA = weight ratio 80:20) and stirred for 30 minutes to dissolve. Furthermore, 25.00 g of pigment dispersion 25 was added and stirred for 30 minutes to prepare a positive-type photosensitive pigment composition 25 with a solid content of 15.00 wt%. The blending weights of each raw material are shown in Table 20. Using the positive-type photosensitive pigment composition 25, the following evaluations were performed in the same manner as in Example 1: (1) light shielding properties of the cured film, (2) halftone processability, (3) storage stability, and (4) lightfastness reliability. The evaluation results are shown in Table 21.

[0324] [Table 20]

[0325] [Table 21]

[0326] (Comparative Example 7) Based on the method described in Example 57 of International Publication No. 2019 / 087985, negative-type photosensitive pigment composition 1 was prepared by the following method. Under a yellow light, 0.41 g of OXL-21, a photopolymerization initiator, was dissolved in 11.13 g of PGMEA and 17.00 g of MBA. Then, 12.42 g of polyimide resin solution 2 (30% solids by weight), 1.64 g of a 50% by weight MBA solution of "KAYARAD" (registered trademark) DPHA (manufactured by Nippon Kayaku Co., Ltd., referred to as "DPHA" in the table), 4.10 g of a 50% by weight MBA solution of "KAYARAD" (registered trademark) DPCA-60 (manufactured by Nippon Kayaku Co., Ltd., referred to as "DPCA-60" in the table), and 53.30 g of pigment dispersion 26 were mixed and stirred for 30 minutes. Furthermore, the mixture was filtered through a filter (aperture diameter 0.45 μm) to prepare a negative-type photosensitive pigment composition 1 with a solid content of 15.00% by weight.

[0327] Using the negative-type photosensitive pigment composition 1, the following evaluations were conducted in the same manner as in Example 1, except that a negative-type halftone exposure mask (a reverse mask designed so that when the exposure amount in the fully transparent area is 100% and the exposure amount in the shielded area is 0%, the exposure amount in the semi-transparent area is 30%) was used instead of the positive-type halftone exposure mask described above, and the development time was set to 1.5 times the time it takes for the unexposed film to dissolve and be removed. The evaluations were conducted using the same method as in Example 1, except that (1) the light-shielding properties of the cured film, (2) halftone processability, (3) storage stability, and (4) lightfastness reliability were evaluated. The formulation amounts are shown in Table 20, and the evaluation results are shown in Table 21.

[0328] (Comparative Example 8) Under a yellow light, 0.41 g of "Irgacure" (registered trademark) OXE-04 (manufactured by BASF, referred to as "OXE-04" in the table), a photopolymerization initiator, and 0.75 g of VG-3101L were dissolved in 44.76 g of PGMEA. Next, 8.28 g of ZCR-1569H, 2.10 g of a 50 wt% MBA solution of "KAYARAD" (registered trademark) DPHA (manufactured by Nippon Kayaku Co., Ltd., referred to as "DPHA" in the table), 1.50 g of a 50 wt% MBA solution of "KAYARAD" (registered trademark) DPCA-60 (manufactured by Nippon Kayaku Co., Ltd., referred to as "DPCA-60" in the table), and 42.20 g of pigment dispersion 27 were mixed and stirred for 30 minutes. Furthermore, the mixture was filtered through a filter (aperture diameter 0.45 μm) to prepare negative-type photosensitive pigment composition 2 with a solid content of 15.00 wt%. Using negative-type photosensitive pigment composition 2, the following evaluations were performed in the same manner as in Comparative Example 7: (1) light shielding properties of the cured film, (2) halftone processability, (3) storage stability, and (4) lightfastness reliability. The formulation amounts are shown in Table 20, and the evaluation results are shown in Table 21.

[0329] (Comparative Example 9) To a mixed solvent (72.00 g of PGME and 10.48 g of GBL), 5.06 g of polyimide precursor O, 1.70 g of quinone diazide compound b, 1.36 g of bisphenol-AF (manufactured by Tokyo Chemical Industry Co., Ltd.), and a 5 wt% PGME solution of BYK-333 were added, and the mixture was stirred for 30 minutes. Then, 9.38 g of pigment dispersion 28 was added, and the mixture was stirred for 1 hour to prepare a positive-type photosensitive pigment composition 26. Using the positive-type photosensitive pigment composition 26, the following evaluations were performed in the same manner as in Example 1: (1) light shielding properties of the cured film, (2) halftone processability, (3) storage stability, and (4) lightfastness reliability. The amounts used are shown in Table 20, and the evaluation results are shown in Table 21.

[0330] (Preparation Example 29: Preparation of Pigment Dispersion 29) Pigment dispersion 29 was prepared in the same manner as in Preparation Example 1, except that hydroxyl group-containing polyamide resin R2 was used instead of hydroxyl group-containing polyamide resin R, in the blending weights shown in Table 22.

[0331] [Table 22]

[0332] (Example 20) Using pigment dispersion 29 instead of pigment dispersion 1, a positive-type photosensitive pigment composition 27 was prepared in the proportions shown in Table 23, and (1) the light-shielding properties of the cured film, (2) halftone workability, (3) storage stability, and (4) lightfastness reliability were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 24.

[0333] [Table 23]

[0334] [Table 24]

[0335] (Preparation Example 30: Preparation of Pigment Dispersion 30) Pigment dispersion 30 was prepared in the same manner as in Preparation Example 1, except that hydroxyl group-containing polyamide resin R3 was used instead of hydroxyl group-containing polyamide resin R, in the blending weights shown in Table 22.

[0336] (Example 21) Using pigment dispersion 30 instead of pigment dispersion 1, a positive-type photosensitive pigment composition 28 was prepared in the proportions shown in Table 23, and (1) the light-shielding properties of the cured film, (2) halftone processability, (3) storage stability, and (4) lightfastness reliability were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 24.

[0337] From the above results, it can be seen that the positive-type photosensitive pigment compositions 1-19 and 27-28 in Examples 1-21 are superior to the positive-type photosensitive pigment compositions 20-26 in Comparative Examples 1-6 and 9, and the negative-type photosensitive pigment compositions 1-2 in Comparative Examples 7-8, resulting in an organic EL display device with excellent halftone processing ability, long-term storage stability, and lightfastness reliability. Therefore, it can be seen that the positive-type photosensitive pigment composition, the cured film containing the cured product of the positive-type photosensitive pigment composition, and the organic EL display device equipped therewith are useful. [Industrial applicability]

[0338] The positive-type photosensitive pigment composition of the present invention can be preferably used as a material for forming the pixel splitting layer and spacer layer of an organic EL display device, the TFT planarization layer of an organic EL display device, the partition wall of a quantum dot organic EL display device (QD-OLED), the planarization layer of a micro-LED display, the black matrix of a liquid crystal display device, the black column spacer of a liquid crystal display device, the near-infrared transparent visible light shielding film of a solid-state image sensor, and the black bezel of a display device. In particular, it can be preferably used as a material for forming the pixel splitting layer and spacer layer of an organic EL display device, which may be used outdoors and requires high light resistance reliability. [Explanation of Symbols]

[0339] 1: Pixel division layer 2: Spacer layer 3: Luminous part 4: Luminous part 5: Non-luminescent areas 6: Alkali-free glass substrate 7: Silver alloy film 8: ITO film 9: Pixel splitting layer and spacer layer 10: Organic EL layer 11:Second electrode

Claims

1. (a) A triphendioxazine pigment having a carboxylic acid amide bond and / or a carboxylic acid ester bond, (b) A resin having the structure represented by formula (1) and / or the structure represented by formula (2), (c) Photoacid generator and (d) A positive-type photosensitive pigment composition containing an organic solvent. 【Chemistry 1】 (In formula (1), n １ This is an integer, representing either 1 or 2. n １ If R is 1, １ n represents a divalent organic group with 2 to 30 carbon atoms that does not contain a carboxylic acid amide bond or a carboxyl group. １ If R is 2, １ (* represents a trivalent organic group with 5 to 30 carbon atoms that does not contain carboxylic acid amide bonds or carboxyl groups.) 【Chemistry 2】 (In formula (2), R ２ (* represents a trivalent organic group with 5 to 30 carbon atoms that does not contain carboxylic acid amide bonds or carboxyl groups.)

2. The positive-type photosensitive pigment composition according to claim 1, wherein component (a) contains a triphendioxazine pigment represented by formula (4) and / or a triphendioxazine pigment represented by formula (5). 【Transformation 3】 (In formula (4), R ３ and R ４ each independently represent an alkyl group having 1 to 8 carbon atoms. R ５ and R ６ each independently represent an alkyl group having 1 to 8 carbon atoms, a phenyl group substituted with an alkyl group having 1 to 8 carbon atoms, or an unsubstituted phenyl group. R ７ and R ８ each independently represent -NH- or an oxygen atom. R ９ , R １０ , R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ and R １８ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. R １９ and R ２０ represent -CONH-. ) 【Chemistry 4】 (In formula (5), R ２１ and R ２２ Each of these independently represents a hydrogen atom and an alkyl group having 1 to 8 carbon atoms. ２３ and R ２４ Each of these independently represents an alkyl group having 1 to 8 carbon atoms, a phenyl group substituted with an alkyl group having 1 to 8 carbon atoms, or an unsubstituted phenyl group. ２５ and R ２６ Each of these independently represents either -NH- or an oxygen atom.

3. The positive-type photosensitive pigment composition according to claim 1, wherein the component (a) contains a triphendioxazine pigment represented by formula (6). 【Transformation 5】 (In formula (6), R ２７ , R ２８ , R ２９ and R ３０ Each of these independently represents an alkyl group having 1 to 4 carbon atoms. R ３１ , R ３２ , R ３３ , R ３４ , R ３５ , R ３６ , R ３７ , R ３８ , R ３９ and R ４０ Each of these independently represents a hydrogen atom, a C1-C4 alkyl group, or a C1-C4 alkoxy group. R ４１ and R ４２ (This represents -CONH-.)

4. The positive-type photosensitive pigment composition according to claim 1, wherein the component (a) contains a triphendioxazine pigment represented by formula (7). 【Transformation 6】 (In formula (7), R ４３ , R ４４ , R ４５ and R ４６ Each of these independently represents an alkyl group having 1 to 4 carbon atoms.

5. Furthermore, the positive-type photosensitive pigment composition according to claim 1, further comprising (e) an organic dye having a sulfo group bonded to a carbon atom constituting an aromatic ring and / or a carboxyl group bonded to a carbon atom constituting an aromatic ring, and having no chlorine atoms in the molecule.

6. The positive-type photosensitive pigment composition according to claim 5, wherein the (e) component contains at least one selected from the group consisting of triphendioxazine-based dyes, perylenebisimide-based dyes, and anthraquinone-based dyes.

7. The positive-type photosensitive pigment composition according to claim 5, wherein the (e) component contains a compound represented by formula (62) and / or a compound represented by formula (63). 【Transformation 7】 (In formula (62), R ５７ and R ５８ Each of these independently represents either -NH- or an oxygen atom. R ５９ and R ６０ Each of these independently represents an alkyl group having 1 to 4 carbon atoms. ６１ and R ６２ These represent -NH- or -CONH- independently. ６３ , R ６４ , R ６７ and R ６８ Each of these is independently, -SO ３ H, -SO ３ － -COOH or -COO － Represents R ６５ and R ６６ Each of these independently represents an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. ９ and n １０ n is an integer, each independently representing either 0 or 1. １１ , n １２ , n １３ and n １４ n is an integer, each independently representing 0 to 2. １５ n is an integer, representing either 0 or 1. ９ , n １１ and n １５ The sum of n is 2 or less, １０ , n １２ and n １５ The sum is 2 or less. １５ If n is 0, １１ and n １２ The sum is between 1 and 3. １５ If n is 1, １１ , n １２ , n １３ and n １４ The sum is between 1 and 3. 【Transformation 8】 (In formula (63), R ６９ and R ７０ Each of these independently represents either -NH- or an oxygen atom. R ７１ and R ７２ each independently represents an alkyl group having 1 to 4 carbon atoms. R ７３ R ７４ R ７５ and R ７６ each independently represents -SO ３ H, -SO ３ － -COOH or -COO － represents. R ７７ and R ７８ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n １６ n １７ n １８ and n １９ are integers and each independently represents 0 or 1. n １６ n １７ n １８ and n １９ The sum of is 1 to 3.)

8. The positive-type photosensitive pigment composition according to claim 1, wherein the component (b) contains a resin having a repeating unit represented by formula (36) and a structure represented by formula (47). 【Chemistry 9】 (In formula (36), R ４７ R represents a divalent organic group with 5 to 30 carbon atoms that does not contain a carboxylic acid amide bond or a carboxyl group. ４８ This represents a hydroxyl group that does not contain a hydroxyl group and has 6 to 40 carbon atoms with a valency of 3 to 6. ２ * is an integer, representing 1 to 4. １ * represents the bonding site with the nitrogen atom. ２ (This represents the bonding site with a carbon atom.) 【Chemistry 10】 (In formula (47), R １１３ R represents a divalent organic group with 5 to 30 carbon atoms that does not contain a carboxylic acid amide bond or a carboxyl group. １１４ This represents a hydroxyl group that does not contain a hydroxyl group and has 6 to 40 carbon atoms with a valency of 3 to 6. ３２ * is an integer, representing 1 to 4. ３ (This represents the bonding site with the nitrogen atom.)

9. Furthermore, the positive-type photosensitive pigment composition according to claim 1, further comprising (g) a perylene-based black pigment having a benzimidazole skeleton.

10. A cured film comprising a cured product of a positive-type photosensitive pigment composition according to any one of claims 1 to 9.

11. An organic EL display device comprising the cured film described in claim 10.

12. An organic EL display device comprising a pixel splitting layer containing a triphendioxazine pigment represented by formula (7). 【Chemistry 11】 (In formula (7), R ４３ , R ４４ , R ４５ and R ４６ Each of these independently represents an alkyl group having 1 to 4 carbon atoms.

13. The organic EL display device according to claim 12, wherein the pixel splitting layer further contains (e) a triphendioxazine dye having a sulfo group bonded to a carbon atom constituting an aromatic ring and / or a carboxyl group bonded to a carbon atom constituting an aromatic ring, and having no chlorine atoms in the molecule.

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