Positive photosensitive pigment composition, cured film containing cured product thereof, organic el display device, electronic apparatus, and block copolymer

Abstract

According to the present invention, there is provided a positive photosensitive pigment composition which, after being stored in a sealed container under atmospheric pressure / room temperature, suppresses the generation of semi-dry film-like foreign matter including pigment aggregates, and which enables a black pixel division layer and a spacer layer to be stably formed all at once with high exposure sensitivity by positive halftone processing.　The present invention is a positive photosensitive pigment composition containing (a) a resin, (b) an organic pigment, (c) a photoacid generator, and (d) an organic solvent, wherein the (a) resin contains (a-1) a resin having a repeating unit a and a repeating unit b, the repeating unit a is one or more selected from the group consisting of repeating units having a specific structure, and the repeating unit b is a repeating unit having a specific structure.

Description

Positive photosensitive pigment composition, cured film containing the cured product thereof, organic EL display device, electronic device, and block copolymer

[0001] The present invention relates to a positive-type photosensitive pigment composition, a cured film containing the cured product thereof, an organic EL display device, an electronic device, and a block copolymer.

[0002] It is well known that utilizing an adsorption mechanism based on acid-base interactions is extremely effective in finely dispersing pigments in organic solvents, suppressing reagglomeration, and achieving high dispersion stability. Organic pigments are generally less polar than inorganic pigments, making them more difficult to disperse. Resins containing tertiary amino groups bonded to aliphatic hydrocarbon groups (hereinafter sometimes referred to as aliphatic tertiary amino groups), such as N,N-dialkylaminoalkyl groups, are used as pigment dispersants in a wide range of technical fields because of their excellent adsorption properties to the acidic adsorption sites on the organic pigment surface.

[0003] For example, in the technical field of negative-tone photosensitive pigment compositions containing organic pigments, there has often been a demand for pigment dispersants that can exhibit high pigment dispersion performance and that do not impair patterning properties or film properties in photolithography. That is, pigment dispersants must be designed or selected with due consideration given to achieving both pigment dispersion performance and other properties that are important for the application, and because this significantly affects the value of the final product, numerous technical proposals have been made to date.

[0004] Against this background, (meth)acrylic dispersants having an aliphatic tertiary amino group are commonly used in the technical field of negative-tone photosensitive pigment compositions, such as materials for forming color filters, black matrices, and black column spacers in liquid crystal displays. Patent Document 1 discloses a technique for achieving not only good average particle size and contrast but also solvent resolubility of a dried film of a negative-tone photosensitive pigment composition, which may occur during standby for discharge from a coating device, by using a methacrylic dispersant in which a portion of the aliphatic tertiary amino group is converted to a quaternary ammonium salt (e.g., dispersant solutions a, b, and c in the examples). Patent Document 2 discloses a negative-tone photosensitive pigment composition that achieves low viscosity, contrast, and development speed by using a pigment dispersant with an amine value derived from an aliphatic tertiary amino group within a specific range (e.g., dispersants B, C, and D in the examples).

[0005] Furthermore, attempts have been made to apply pigment dispersants having aliphatic tertiary amino groups to materials for forming black pixel division layers in organic EL display devices. As coloring materials, the use of organic pigments has been primarily proposed due to their excellent insulating properties, heat resistance, and near-infrared transmittance. In addition to functioning as an insulating layer separating each emitting pixel, the black pixel division layer also functions to suppress external light reflection, thereby providing benefits such as improved visibility and reduced power consumption.

[0006] Patent Document 3 discloses a negative-tone photosensitive pigment composition containing a methacrylic dispersant in which aliphatic tertiary amino groups or a portion thereof have been converted to a quaternary ammonium salt (for example, Dispersants I and II in the Examples). Meanwhile, Patent Document 4 discloses a negative-tone photosensitive pigment composition containing an aliphatic tertiary polyamine dispersant in which multiple graft chains of polyether structure have been introduced into an aliphatic polyamine (for example, Dispersant 4 in the Examples).

[0007] Recently, from the viewpoint of reducing the manufacturing process costs of organic EL display devices, attempts have been made to develop a technique for simultaneously forming a black pixel division layer and a spacer layer disposed on a part of its surface using a halftone exposure mask. Compared to negative halftone processing, a black pixel division layer can be obtained with extremely high in-plane uniformity of the opening width of the opening, and the in-plane variation in the size of the light-emitting pixels determined by the opening width can be stably suppressed. Therefore, materials that enable positive halftone processing have attracted attention.

[0008] Patent Document 5 discloses a positive photosensitive pigment composition that does not contain a pigment dispersant having an aliphatic tertiary amino group. According to Patent Document 5, the composition has the technical features of enabling excellent positive halftone processing with high exposure sensitivity, and suppressing a decrease in exposure sensitivity before and after storage in a cool, dark place (atmospheric pressure / shielded, −20°C±1°C).

[0009] On the other hand, Patent Document 6 discloses a positive-type photosensitive dye composition containing an amine salt of C.I. Solvent Black 27 or 34, which is an azo-based chromium complex, or C.I. Solvent Black 29, as a black dye having high heat resistance comparable to that of organic pigments and high solubility in organic solvents.

[0010] JP 2011-75847 A JP 2012-212054 A International Publication No. 2022 / 065490 International Publication No. 2021 / 111860 International Publication No. 2022 / 270182 International Publication No. 2017 / 069172

[0011] However, when the positive photosensitive pigment composition disclosed in Patent Document 5 is removed from a cool, dark place and stored in a sealed container under atmospheric pressure / room temperature (for example, a liquid temperature of 25±1°C), there is a problem in that semi-dry film-like foreign matter containing pigment aggregates that are difficult to redisperse in an organic solvent forms and adheres to the surface of the inner wall of the container. Furthermore, this problem causes foreign matter defects in the black pixel dividing layer, which causes unlit pixels when an organic EL display device is driven, thereby impairing the display characteristics.

[0012] On the other hand, when the pigment dispersants disclosed in Patent Documents 1 to 4 are applied to the positive photosensitive pigment composition disclosed in Patent Document 5, a certain improvement effect on the above-mentioned problems may be obtained depending on the amount added, but there are fatal drawbacks such as a deterioration in productivity due to a significant decrease in exposure sensitivity and difficulty in positive halftone processing.

[0013] It is generally known that azo-based chromium complexes such as C.I. Solvent Black 27, 29, or 34 may generate highly toxic hexavalent chromium when treated at high temperatures, and the positive-type photosensitive dye composition and its developer wastewater disclosed in Patent Document 6 have problems in terms of safety for the human body and environmental conservation when put into industrial practical use.

[0014] For these reasons, there has been a strong demand for a positive photosensitive pigment composition that suppresses the generation of semi-dry film-like foreign matter and that allows black pixel division layers and spacer layers to be formed stably and simultaneously with high exposure sensitivity by positive halftone processing.

[0015] The present invention is as follows. [1] A positive photosensitive pigment composition containing (a) a resin, (b) an organic pigment, (c) a photoacid generator, and (d) an organic solvent, wherein the (a) resin contains (a-1) a resin having a repeating unit a and a repeating unit b, the repeating unit a being at least one selected from the group consisting of a repeating unit represented by formula (1), a repeating unit represented by formula (2), a repeating unit represented by formula (3), a repeating unit represented by formula (4), and a repeating unit represented by formula (5), as described below, and the repeating unit b being a repeating unit represented by formula (6), as described below. [2] The positive photosensitive pigment composition according to [1], wherein the repeating unit represented by formula (6) contains a repeating unit containing a monovalent organic group having 6 to 30 carbon atoms and containing one or two phenolic hydroxyl groups. [3] The positive photosensitive pigment composition according to [2], wherein the repeating unit represented by formula (6) includes a repeating unit represented by formula (33) and / or a repeating unit represented by formula (34), which will be described later. [4] The positive photosensitive pigment composition according to any one of [1] to [3], wherein the resin (a-1) having repeating unit a and repeating unit b is a block copolymer having a block chain consisting only of repeating unit a, and repeating unit b. [5] The positive photosensitive pigment composition according to any one of [1] to [4], wherein the resin (a-1) having repeating unit a and repeating unit b further includes repeating unit c, and the repeating unit c is a repeating unit represented by formula (54), which will be described later. [6] The positive photosensitive pigment composition according to any one of [1] to [5], wherein the (b) organic pigment contains (b-2) an organic pigment having a sulfo group. [7] The positive photosensitive pigment composition according to [6], wherein the component (b-2) contains one or more compounds selected from the group consisting of compounds represented by formula (98), compounds represented by formula (99), compounds represented by formula (100), and compounds represented by formula (101), which will be described later. [8] A cured film containing a cured product of the positive photosensitive pigment composition according to any one of [1] to [7]. [9] An organic EL display device comprising the cured film according to [8].

[10] An electronic device comprising the organic EL display device according to [9].

[11] A block copolymer having a block chain consisting only of repeating units a and repeating units b, wherein the repeating units a are at least one selected from the group consisting of repeating units represented by formula (1), repeating units represented by formula (2), repeating units represented by formula (3), repeating units represented by formula (4), and repeating units represented by formula (5), which will be described later, and the repeating units b are repeating units represented by formula (33) and / or repeating units represented by formula (34), which will be described later.

[0016] According to the present invention, there is provided a positive photosensitive pigment composition that, after storage in a sealed container under atmospheric pressure / room temperature, is inhibited from generating semi-dry film-like foreign matter including pigment aggregates, and that can stably form black pixel dividing layers and spacer layers in one go with positive halftone processing at high exposure sensitivity.

[0017] 1 is a cross-sectional view of a TFT substrate in an organic EL display device that is a specific example of an embodiment of the present invention. It is a schematic diagram of the appearance of a glass vial after a positive photosensitive pigment composition is dropped into the glass vial and sealed in the glass vial in Examples and Comparative Examples. It is a schematic diagram of the appearance of a glass vial when a semi-dried film-like foreign substance is formed on the inner wall surface of the glass vial in Examples and Comparative Examples. In all Examples and Comparative Examples, the maximum opening width W of the opening of the substrate for measuring exposure sensitivity is １ and the minimum opening width W ２ 1 is a schematic diagram showing an example of a manufacturing process of an organic EL display device, which includes a step of forming a pixel dividing layer and a spacer layer in all examples and comparative examples.

[0018] The present invention will be described in detail below. A numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. The pixel division layer refers to a pixel division layer provided in an organic EL display device, and does not include a black matrix provided in an organic EL display device or a liquid crystal display device. Visible light refers to light in the wavelength range of 380 nm or more and less than 780 nm, and near ultraviolet refers to light in the wavelength range of 200 nm or more and less than 380 nm. Near infrared refers to light in the wavelength range of 780 nm or more and less than 1300 nm. Light-shielding refers to the function of reducing the intensity of transmitted light relative to the intensity of light incident perpendicularly to the cured film, and light-shielding properties refer to the degree of blocking visible light. Transmittance refers to light transmittance. The weight-average molecular weight (hereinafter sometimes referred to as Mw) and number-average molecular weight (hereinafter sometimes referred to as Mn) are values ​​obtained by analysis using gel permeation chromatography (hereinafter sometimes referred to as GPC) and conversion using a calibration curve based on standard polystyrene.

[0019] The "C.I." used in the names of some colorants is an abbreviation for Color Index Generic Name, which is based on the Color Index published by the Society of Dyers and Colourists. For colorants registered in the Color Index, the Color Index Generic Name represents the chemical structure and crystalline form of the pigment or dye. Carbon blacks classified as C.I. Pigment Black 7, for example, are classified as inorganic black pigments. The solid content refers to the proportion (mass%) of components in a positive-type photosensitive pigment composition excluding organic solvents and water.

[0020] The inventors have conducted verification and found that while the positive photosensitive pigment composition (solid content: 5 to 30% by mass) disclosed in Patent Document 5 has excellent pigment dispersion stability, the pigment dispersion stability in a semi-dried film (solid content: 60 to 90% by mass) is insufficient.

[0021] Furthermore, the above-mentioned problem was thought to arise on a different principle from the insufficient resolubility in organic solvents of a dried film in a non-closed environment disclosed in Patent Document 1. That is, the above-mentioned problem was thought to be caused by irreversible pigment aggregation that occurs when the pigment concentration increases and becomes concentrated due to the evaporation of a certain amount of organic solvent on the surface of the inner wall of a closed container, and when the state in which movable pigments in the film are kept in close proximity to each other is maintained for a long period of time.

[0022] Furthermore, it has been found that while the pigment dispersants disclosed in Patent Documents 1 to 4 have no adverse effect on the photopolymerization initiator, which is a photosensitizer that imparts negative photosensitivity, they promote the undesired decomposition of the photoacid generator, which is a photosensitizer that imparts positive photosensitivity, causing rapid deterioration. Furthermore, it has been found that they trap at least a portion of the acid that is desirably generated in the film in the exposed area during the exposure process, thereby inhibiting the normal function of the photoacid generator. In addition, the inventors have also found that there is a region in which a certain correlation is observed between the amount of semi-dry film-like foreign matter generated and the incidence of non-illuminated pixels in organic EL display devices.

[0023] No pigment dispersant has been known to date that is effective in dispersing organic pigments and is suitable for positive-working photosensitive systems, regardless of whether or not it suppresses the generation of semi-dry film-like foreign matter including pigment aggregates.

[0024] In view of the above, the present inventors have conducted extensive research focusing on the coexistence of a pigment dispersion mechanism based on acid-base interaction without inhibiting the positive photosensitive mechanism based on acid generation, and have found that a positive photosensitive pigment composition containing a pigment dispersant with a specific structure is particularly effective in solving the above-mentioned problems.

[0025] That is, the positive photosensitive pigment composition according to a first embodiment of the present invention is a positive photosensitive pigment composition comprising (a) a resin, (b) an organic pigment, (c) a photoacid generator, and (d) an organic solvent, wherein the resin (a) comprises (a-1) a resin having a repeating unit a and a repeating unit b, the repeating unit a being one or more selected from the group consisting of a repeating unit represented by formula (1), a repeating unit represented by formula (2), a repeating unit represented by formula (3), a repeating unit represented by formula (4), and a repeating unit represented by formula (5), and the repeating unit b is a repeating unit represented by formula (6).

[0026]

[0027] In formula (1), formula (2), formula (3), formula (4), formula (5), and formula (6), * represents a binding site, R １ , R ４ , R ７ , R １１ , R １５ and R ２０ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R ２ , R ５ , R ８ , R １２ , and R １６ each independently represents a single bond or a divalent linking group having 1 to 8 carbon atoms and not containing a nitrogen atom, ３ , R ６ , R ９ , R １４ , and R １９ each independently represents an alkyl group having 1 to 3 carbon atoms; １ , n ２ , n ３ , n ４ , and n ５ are integers, each independently representing 0 to 2; １０ and R １３ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R １７ and R １８ each independently represents an alkyl group having 1 to 5 carbon atoms; R ２１represents a monovalent group containing a hydroxyl group and having 1 to 30 carbon atoms. ２１ does not contain any nitrogen atom other than the nitrogen atom contained in —CONH—.

[0028] The positive photosensitive pigment composition of the present invention has positive photosensitivity. Possessing positive photosensitivity allows a pixel dividing layer having extremely high in-plane uniformity in the aperture width of the apertures to be formed by positive halftone processing, thereby stably suppressing in-plane variations in the size of the light-emitting pixels determined by the aperture width, and enabling the production of an organic EL display device with reduced brightness unevenness. This effect is the same as that of the positive photosensitive pigment composition disclosed in Patent Document 5.

[0029] Positive photosensitivity means a property in which, by irradiating a prebaked film of a photosensitive composition with light including near ultraviolet light and exposing it, the solubility of the film in an alkaline developer in the exposed portion, which will be described later, becomes higher than the solubility of the film in an alkaline developer in the unexposed portion, which will be described later.

[0030] On the other hand, a composition having the property that the solubility of the exposed portion of the film in an alkaline developer is lower than the solubility of the unexposed portion of the film in an alkaline developer, i.e., a negative photosensitivity, is not included in the positive photosensitive pigment composition of this specification, even if it contains (a) a resin, (b) an organic pigment, (c) a photoacid generator, and (d) an organic solvent. The alkaline developer referred to here is not particularly limited in type or concentration, as long as it contains at least water and has a pH of 1.0 or more and less than 7.0 as measured with a pH meter.

[0031] The positive photosensitive pigment composition of the present invention contains a resin (a), and the resin (a) contains (a-1) a resin having a repeating unit a and a repeating unit b, wherein the repeating unit a is at least one selected from the group consisting of a repeating unit represented by formula (1), a repeating unit represented by formula (2), a repeating unit represented by formula (3), a repeating unit represented by formula (4), and a repeating unit represented by formula (5), and the repeating unit b is a repeating unit represented by formula (6).

[0032]

[0033] In formula (1), formula (2), formula (3), formula (4), formula (5), and formula (6), * represents a binding site, R １ , R ４ , R ７ , R １１ , R １５ and R ２０ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R ２ , R ５ , R ８ , R １２ , and R １６ each independently represents a single bond or a divalent linking group having 1 to 8 carbon atoms and not containing a nitrogen atom, ３ , R ６ , R ９ , R １４ , and R １９ each independently represents an alkyl group having 1 to 3 carbon atoms; １ , n ２ , n ３ , n ４ , and n ５ are integers, each independently representing 0 to 2; １０ and R １３ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R １７ and R １８ each independently represents an alkyl group having 1 to 5 carbon atoms; R ２１ represents a monovalent group containing a hydroxyl group and having 1 to 30 carbon atoms. ２１ does not contain any nitrogen atom other than the nitrogen atom contained in —CONH—.

[0034] The term "resin (a)" used herein refers to a compound having a polymer chain in which five or more repeating units each having three or more carbon atoms are linked together, and having a molecular weight (Mw) of 1,000 or more.

[0035] The positive photosensitive pigment composition of the present invention contains (a) a resin (a-1) having repeating units a and b (hereinafter, sometimes referred to as component (a-1)). Four advantageous features of component (a-1) are described below.

[0036] The first advantageous feature is that it has the effect of promoting fine dispersion of the (b) organic pigment described below and improving its dispersion stability in the positive-tone photosensitive pigment composition. The improved dispersion stability in a liquid form broadens the particle size distribution of the pigment and suppresses an increase in the viscosity of the positive-tone photosensitive pigment composition, resulting in improved film thickness uniformity of the pixel division layer and spacer layer obtained as a result.

[0037] A second advantageous feature is that when a positive photosensitive pigment composition is stored in a sealed container (for example, at a liquid temperature of 25±1°C) under atmospheric pressure / room temperature, the composition has the effect of suppressing the formation of semi-dry film-like foreign matter (hereinafter, sometimes simply referred to as "semi-dry film-like foreign matter") containing pigment aggregates that are difficult to redisperse in an organic solvent on the surface of the inner wall of the container.

[0038] The organic solvent referred to here is not particularly limited, but examples thereof include organic solvents having the same structure as or a similar structure to the (d) organic solvent contained in the positive photosensitive pigment composition. Therefore, when the positive photosensitive pigment composition is replenished, the adhesions are easily removed by redispersing the pigment, and the inside of the container can be easily cleaned with the organic solvent.

[0039] This effect prevents the problem that, when semi-dry film-like foreign matter comes into contact with a cleaning solvent or a positive-tone photosensitive pigment composition, at least a portion of the foreign matter peels off from the inner wall of the container in the form of a film, contaminating the positive-tone photosensitive pigment composition and becoming insoluble foreign matter. Furthermore, it is possible to form pixel division layers and spacer layers with excellent smoothness and free of convex foreign matter defects, thereby enabling the manufacture of organic EL display devices in which the occurrence of non-lighting pixels is suppressed. Here, non-lighting pixels refer to defective light-emitting pixels that do not light up even when voltage is applied when the organic EL display device is driven, and thus are unable to emit light. The fewer non-lighting pixels there are, the more valuable the display device and the more desirable it is. Furthermore, non-lighting pixels caused by semi-dry film-like foreign matter tend to occur more easily when the second electrode, described below, is formed with a thinner film. In other words, the second advantageous feature is particularly useful when the organic EL display device of the present invention, described below, is a top-emission organic EL display device.

[0040] The change in particle size distribution of the insoluble components in the positive photosensitive pigment composition caused by at least a portion of the semi-dry film-like foreign matter peeling off in a film form from the inner wall of the container and being mixed in can be measured by the maximum particle diameter (μm) measured with a laser diffraction particle size distribution analyzer "MT3000II (manufactured by MICROTRAC)" or by image analysis with a laser microscope. On the other hand, the major axis of the insoluble foreign matter is generally 1 μm or more and has poor Brownian motion, so measurement with a dynamic light scattering particle size distribution analyzer is theoretically difficult.

[0041] A third advantageous feature is that it does not impair the positive-tone photosensitive function. This suppresses degradation of the (c) photoacid generator (described below), allowing for the generation of a large amount of acid during the exposure process, and also prevents the generated acid from being trapped in the film in the exposed areas, resulting in high exposure sensitivity. High exposure sensitivity here means a smaller minimum exposure dose required to simultaneously form pixel division layers with openings of the desired aperture widths and spacer layers through positive-tone halftone processing. In other words, higher exposure sensitivity enables shorter exposure times, thereby improving the productivity of organic EL display devices. Generally, the more light-blocking a prebaked film is, the less light reaches the bottom of the exposed film in the exposure process, which tends to result in lower exposure sensitivity for the same formed film thickness. Therefore, the higher the light-blocking property of the pixel division layer to be formed, the greater the effect.

[0042] A fourth advantageous feature is that the component (a-1) has excellent developability in an alkaline developer, making it possible to suppress the generation of development residues.

[0043] In addition, when component (a-1) consists only of repeating units a and b, component (a-1) is solid at atmospheric pressure and 25° C. and has the film-forming ability of a binder resin.

[0044] The repeating unit a in component (a-1) has a pigment-adsorbing group with a nitrogen-containing structure that has an appropriately low basicity, and the pigment-adsorbing group adsorbs to the surface of the organic pigment (b) and exhibits an effect as a pigment dispersant. By adjusting the presence or absence of an alkyl group substituted on the aromatic ring in the repeating unit a or the number of carbon atoms in the alkyl group, it is possible to control the affinity according to the polarity of the organic pigment (b).

[0045] The repeating unit a contained in the component (a-1) is, in order to suppress the generation of semi-dry film-like foreign matter, R ２ , R ５ , R ８ , R １２ , and R １６ is preferably a repeating unit in which the repeating unit represents a single bond, —COO—, an alkylene group having 1 to 8 carbon atoms, or —COO-alkylene group having 1 to 7 carbon atoms. Here, the —COO-alkylene group having 1 to 7 carbon atoms means a group in which a carboxylic acid ester bond (—COO—) and an alkylene group having 1 to 7 carbon atoms are bonded.

[0046] Among these, in order to suppress the generation of semi-dry film-like foreign matter and to obtain high exposure sensitivity, it is more preferable to use one or more repeating units selected from the group consisting of repeating units represented by formula (7), repeating units represented by formula (8), and repeating units represented by formula (9). In terms of a high effect of suppressing the generation of unlit pixels, it is most preferable to use a repeating unit represented by formula (9). That is, it is more preferable that the positive photosensitive pigment composition of the present invention contains an (a) resin, wherein the (a) resin contains (a-1) a resin having repeating units a and repeating units b, wherein the repeating unit a is one or more selected from the group consisting of repeating units represented by formula (7), repeating units represented by formula (8), and repeating units represented by formula (9), and the repeating unit b is a repeating unit represented by formula (6).

[0047]

[0048] In formulas (7), (8), and (9), * represents a binding site, and R ２２ , R ２５ , and R ２８each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R ２３ , R ２６ , and R ２９ each independently represents a single bond, —COO—, an alkylene group having 1 to 8 carbon atoms, or —COO- an alkylene group having 1 to 7 carbon atoms; R ２４ , R ２７ , and R ３０ each independently represents an alkyl group having 1 to 3 carbon atoms; ６ , n ７ , and n ８ are integers, each independently representing 0 to 2.

[0049] Specific examples of repeating units belonging to repeating unit a include repeating units represented by formulas (10) to (32). One or more of these may be present.

[0050]

[0051]

[0052]

[0053] In formulas (10) to (32), * represents a binding site.

[0054] The repeating unit b in the component (a-1) exhibits the effect of further suppressing deterioration of the photoacid generator (c) described below through intramolecular and / or intermolecular interactions with the repeating unit a that is not adsorbed to the pigment surface, and of improving exposure sensitivity by suppressing the capture of acid generated in the film. In addition, the repeating unit b has a steric repulsion effect, and due to a synergistic effect with the effect of the repeating unit a, the positive photosensitive pigment composition is concentrated on the surface of the inner wall of a container under atmospheric pressure / sealed conditions, and even if the pigments are maintained in close proximity to each other, the generation of semi-dry film-like foreign matter can be suppressed.

[0055] The repeating unit b is a repeating unit represented by the above formula (6), and R ２１is a monovalent group having 1 to 30 carbon atoms and containing a hydroxyl group. Examples of the hydroxyl group or a group containing a hydroxyl group include an alcoholic hydroxyl group, a phenolic hydroxyl group, a carboxyl group, a phosphate group, and a sulfo group. The carboxyl group here has the same meaning as a carboxy group.

[0056] However, in formula (6), R ２１ The hydroxyl group contained in does not include a structure in which a hydrogen atom is bonded to an oxygen atom located at the terminal of a polyalkylene oxide structure. The polyalkylene oxide structure refers to a divalent group in which two or more alkylene oxides are bonded in series, i.e., a group represented by -(AO)x-. A represents an alkylene group, and the number of repeating units, x, is an integer of 2 or more. Therefore, in the structure represented by -(AO)x-H, the oxygen atom bonded to the terminal hydrogen atom is considered to be part of the atoms constituting the polyalkylene oxide structure, rather than part of the atoms constituting the hydroxyl group referred to here.

[0057] In order to improve exposure sensitivity, the repeating unit represented by formula (6) preferably contains a repeating unit which is a monovalent organic group having 6 to 30 carbon atoms and containing one or two phenolic hydroxyl groups. That is, in the positive photosensitive pigment composition of the present invention, the repeating unit represented by formula (6) preferably contains a repeating unit which contains a monovalent organic group having 6 to 30 carbon atoms and containing one or two phenolic hydroxyl groups.

[0058] The repeating unit containing a monovalent organic group having 6 to 30 carbon atoms and one or two phenolic hydroxyl groups more preferably contains a repeating unit represented by formula (33) and / or a repeating unit represented by formula (34), in order to improve exposure sensitivity and suppress non-lighting pixels. That is, in the positive photosensitive pigment composition of the present invention, the repeating unit represented by formula (6) more preferably contains a repeating unit represented by formula (33) and / or a repeating unit represented by formula (34).

[0059]

[0060] In formula (33) and formula (34), * represents a binding site, R ３１ and R ３４represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R ３２ and R ３５ each independently represents a single bond or a divalent linking group having 1 to 8 carbon atoms; R ３３ , R ３６ , and R ３７ each independently represents an alkyl group having 1 to 3 carbon atoms; ９ is an integer representing 1 or 2; １０ , n １１ , n １２ , n １３ , n １４ are integers, each independently representing 0 to 2. ３２ and R ３５ does not contain any nitrogen atom other than the nitrogen atom contained in —CONH—, and n １１ and １２ The sum of n is 0 to 3, １２ and １４ The sum is 1 or 2.

[0061] The repeating unit b contained in the component (a-1) is, in order to improve exposure sensitivity, R ３２ , and R ３５ are each independently a single bond, —COO—, or —CONH—. Depending on the presence or absence of an alkyl group substituted on the aromatic ring in the repeating unit b, or the number of carbon atoms in the alkyl group, it is possible to control the affinity according to the polarity of (d) the organic solvent.

[0062] Specific examples of the repeating unit b include repeating units represented by formulas (35) to (53).

[0063]

[0064]

[0065]

[0066] In formulas (35) to (53), * represents a binding site.

[0067] In order to suppress the formation of semi-dry film-like foreign matter, it is preferable that component (a-1) further contains a repeating unit c represented by formula (54). Repeating unit c further enhances the affinity of component (a-1) with organic solvent (d), improves molecular mobility, and enhances the steric repulsion effect of component (a-1). In other words, in the positive photosensitive pigment composition of the present invention, it is preferable that resin (a-1) having repeating unit a and repeating unit b further contains repeating unit c, and that repeating unit c is a repeating unit represented by formula (54).

[0068]

[0069] In formula (54), * represents a binding site, R ３８ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R ３９ represents -COO- or -O-, R ４０ represents an alkylene group having 1 to 3 carbon atoms; n １５ is an integer from 2 to 30, R ４１ represents a phenyl group substituted with an alkyl group having 1 to 10 carbon atoms, an unsubstituted phenyl group, or an alkyl group having 1 to 10 carbon atoms. ４０ -O)n １５ The partial structure represented by - is a group consisting of multiple R ４０ may have the same or different carbon atoms. ２ H ４ O) ５ -(C ３ H ６ O) ５ - includes a partial structure represented by R ４１ In order to suppress the formation of semi-dry film-like foreign matter, a phenyl group substituted with an alkyl group having 1 to 10 carbon atoms or an unsubstituted phenyl group is preferred.

[0070] Specific examples of the repeating unit c include repeating units represented by formulae (55) to (57).

[0071]

[0072] In formulas (55) to (57), * represents a binding site.

[0073] The content of the (a) resin is preferably 20 parts by mass or more per 100 parts by mass of the solid content of the positive photosensitive pigment composition in order to minimize the change in the amount of film loss (described below) with respect to the change in development time. The content of the (a) resin is preferably 70 parts by mass or less in order to ensure a sufficient content of components other than the (a) resin and to achieve both high light-blocking properties and high exposure sensitivity. The component belonging to the (a) resin category may be only the component (a-1).

[0074] In order to suppress semi-dry film-like foreign matter, the content of component (a-1) is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more, per 100 parts by mass of component (b) described below.

[0075] Methods for synthesizing component (a-1) include copolymerizing a monomer that serves as a source for introducing repeating unit a, a monomer that serves as a source for introducing repeating unit b, and, if necessary, a monomer that serves as a source for introducing repeating unit c, and monomers that serve as sources for introducing other repeating units. The term "monomer" as used herein refers to a compound having one structure represented by formula (58) in the molecule. The term "other repeating units" as used herein refers to repeating units that do not belong to repeating unit a, repeating unit b, or repeating unit c.

[0076]

[0077] In formula (58), * represents a binding site, R ４２ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0078] Examples of monomers that can be used as a source for introducing the repeating unit a include 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-vinyl-6-methylpyridine, 2-propyl-5-vinylpyridine, 5-propyl-2-vinylpyridine, 4-(4-vinylphenyl)pyridine, 4-(1-methylethenyl)pyridine, 2-(allyldimethylsilyl)pyridine, 4-ethenyl-3,5-dimethylpyridine, 2-(1-ethenylpentyl)pyridine, 1-vinylimidazole, 4-(1-imidazolyl)styrene, 2-(1H-imidazole Examples of suitable monomers include 1-(4-penten-1-yl)ethyl methacrylate, 4-(1H-imidazol-1-yl)butyl (meth)acrylate, 1-(6-hepten-1-yl)1H-imidazole, 2-methyl-1-vinylimidazole, 1-vinyl-1H-benzimidazole, 1-(4-penten-1-yl)1H-benzimidazole, 2-methyl-1-(4-penten-1-yl)1H-benzimidazole, 4-(dimethylamino)styrene, 4-(diethylamino)styrene, 4-(dipropylamino)styrene, and 4-(dibutylamino)styrene. One or more of these may be used in combination. The term "(meth)acrylate" as used herein refers to methacrylate and acrylate. These monomers are readily available commercially as raw materials for pharmaceutical manufacturing intermediates and the like.

[0079] Examples of monomers that can be used as a source for introducing repeating unit b include 4-vinylphenol, 4-isopropenylphenol, 3-propyl-4-vinylphenol, 3-methyl-4-vinylphenol, 4-(1-methylenepropyl)phenol, 4-vinylcatechol, 4-hydroxyphenyl(meth)acrylate, N-(4-hydroxyphenyl)(meth)acrylamide, 5-allyl-1,3-benzenediol, 1-vinyl-2-naphthol, 2-naphthalenol-6-ethenyl, 1-naphthalenol-4-ethenyl, 4-hydroxy-1-naphthyl(meth)acrylate, 2-((6-hydroxynaphthalene-2-yl)-2-isopropyl)-2-isopropyl Examples of the repeating unit b include 2-hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate-phthalic anhydride adduct, 2-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate-phthalic anhydride adduct, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxy-1-methacryloyloxyadamantane, (meth)acrylic acid, mono(2-hydroxyethyl methacrylate)phosphate, 2-sulfoethyl methacrylate, and 2-acrylamido-2-methylpropanesulfonic acid. Furthermore, repeating unit b may be obtained by copolymerizing a monomer in which the hydroxyl group is protected with a protecting group, followed by a step of deprotecting the hydroxyl group to restore it to the original hydroxyl group. Examples of monomers in which the hydroxyl group is protected with a protecting group include 4-acetoxystyrene, 4-methoxystyrene, 4-tert-butoxystyrene, p-(tert-butyldimethylsiloxy)styrene, p-(1-ethoxyethoxy)styrene, 2-tert-butoxy-6-vinylnaphthalene, 4-vinyl-1,3-benzodioxole, and 5-vinyl-1,3-benzodioxole (all manufactured by Tokyo Chemical Industry Co., Ltd.). One of these may be used alone, or two or more may be used in combination. The term "(meth)acrylate" as used herein refers to methacrylate and acrylate. These monomers are readily available as commercial products industrially as raw materials for KrF photoresists used in semiconductor manufacturing.

[0080] Examples of monomers that can be used as a source for introducing repeating unit c include triethylene glycol methyl vinyl ether, triethylene glycol ethyl vinyl ether, tetraethylene glycol methyl vinyl ether, tetraethylene glycol ethyl vinyl ether, 2-ethylhexyl diglycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, butoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, ethylphenoxypolyethylene glycol (meth)acrylate, butylphenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, phenoxypolypropylene glycol (meth)acrylate, ethylphenoxypolypropylene glycol (meth)acrylate, butylphenoxypolypropylene glycol (meth)acrylate, and nonylphenoxypolypropylene glycol (meth)acrylate. One or more of these may be used in combination. The term "(meth)acrylate" as used herein refers to methacrylate and acrylate. These monomers are readily available commercially as raw materials for paints, color filter forming materials, and the like.

[0081] Examples of monomers that can be used as sources for introducing other repeating units include styrene, 3-methylstyrene, α-methylstyrene, cyclohexyl (meth)acrylate, methyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and allyl glycidyl (meth)acrylate (all manufactured by Tokyo Chemical Industry Co., Ltd.). Furthermore, examples of sources for introducing repeating units having the structure represented by -(AO)x-H include tripropylene glycol (meth)acrylate and tetraethylene glycol (meth)acrylate. These may be used alone or in combination of two or more. The term "(meth)acrylate" as used herein refers to both methacrylate and acrylate.

[0082] Another example of a synthesis method is to introduce the repeating unit represented by formula (1) into component (a-1) by reacting a carboxyl group of 4-pyridinecarboxylic acid or 2-pyridinecarboxylic acid with an epoxy group of a copolymer of a monomer that serves as a source for introducing the repeating unit b and glycidyl methacrylate.

[0083] In order to achieve both suppression of semi-dry film-like foreign matter and high exposure sensitivity, the content of repeating unit a in component (a-1) is preferably 5 to 40 mol %, and the content of repeating unit b is preferably 15 to 90 mol %, relative to 100 mol % of the total content of repeating units derived from compounds having one structure represented by formula (58) in the molecule.

[0084] The component (a-1) may be a resin consisting of only the repeating unit a and the repeating unit b, but when it further contains the repeating unit c, the content of the repeating unit c is preferably 1 to 15 mol %.

[0085] The positive photosensitive pigment composition of the present invention may contain a component (a) containing a repeating unit represented by formula (59) and / or a repeating unit represented by formula (60), as long as the effects of the present invention are not impaired. The total content of the repeating unit represented by formula (59) and the repeating unit represented by formula (60) is preferably 0.05 parts by mass or less, more preferably 0.01 parts by mass or less, and most preferably zero, per 100.00 parts by mass of the solids content of the positive photosensitive pigment composition, in order to suppress a decrease in exposure sensitivity. Examples of components containing the repeating unit represented by formula (59) and / or the repeating unit represented by formula (60) include, among the (a-2) other resins described below, at least "DISPERBYK" (registered trademark) 2000, 2001, 2013, "BYK-LPN" (registered trademark) 6919, 21116, and Efka-4300.

[0086]

[0087] In formula (59) and formula (60), * represents a binding site, R ４３ , and R ４７each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R ４４ , and R ４８ represents an alkylene group having 1 to 8 carbon atoms, R ４５ , R ４６ , R ４９ , and R ５０ represents an alkyl group having 1 to 5 carbon atoms, and R ５１ represents a benzyl group or an alkyl group having 1 to 5 carbon atoms; X － represents a monovalent counter anion.

[0088] The Mw of component (a-1) is preferably 2,000 or more, more preferably 5,000 or more, in order to suppress the formation of semi-dry film-like foreign matter. In order to suppress the generation of development residues, it is preferably 30,000 or less, more preferably 20,000 or less. In order to suppress the formation of semi-dry film-like foreign matter, the value obtained by dividing Mw by Mn, i.e., the molecular weight distribution (Mw / Mn), is preferably 1.0 to 3.0, more preferably 1.0 to 2.0. To obtain a molecular weight distribution (Mw / Mn) of 1.0 to 2.0, for example, the organotellurium-mediated radical polymerization method or living anionic polymerization method described below can be preferably employed. Suitable GPC columns for measuring the molecular weight distribution of component (a-1) include, for example, Shodex (registered trademark) LF-804 (manufactured by Resonac Co., Ltd.), TSKgel Super AW2500, TSKgel Super AW3000, TSKgel Super AW4000, TSKgel Super AW5000, and TSKgel guard column Super AW-L and TSKgel Super AW-H (all manufactured by Tosoh Corporation). Suitable eluents for measuring the molecular weight distribution include tetrahydrofuran and N,N'-dimethylacetamide.

[0089] The component (a-1) may be a random copolymer or a block copolymer, but in order to suppress the generation of semi-dry film-like foreign matter, it is preferably a block copolymer having a block chain consisting only of repeating unit a. Here, the block chain consisting only of repeating unit a refers to a structure in which 10 or more repeating units belonging to repeating unit a are linked in series and have a molecular weight of 1,000 or more. The arrangement of the repeating units in the block copolymer other than the block chain consisting only of repeating unit a is not particularly limited. That is, in the positive photosensitive pigment composition of the present invention, the resin (a-1) having repeating unit a and repeating unit b is preferably a block copolymer having a block chain consisting only of repeating unit a and repeating unit b.

[0090] If a block chain consisting only of repeating unit a is referred to as polymer chain A and a polymer chain containing repeating unit b is referred to as polymer chain B, examples of the arrangement of polymer chains in a block copolymer having a block chain consisting only of repeating unit a and a repeating unit b include an A-B type (diblock), an A-B-A type (triblock), a B-A-B type (triblock), an A-B-A-B type (tetrablock), and a B-A-B-A-B type (pentablock).

[0091] When the polymer chain B further contains a repeating unit other than the repeating unit b, the polymer chain B may have a portion where the repeating units b are randomly arranged, or may contain a block chain consisting of only the repeating unit b.

[0092] In this specification, the term "block copolymer" also includes, as long as it has a block chain consisting of only the repeating unit a and the repeating unit b, a so-called graft copolymer formed by adding a macromonomer having a block chain consisting of only the repeating unit a, and a so-called gradient copolymer having a linear polymer structure in which the hydrophilicity gradually changes from one molecular end to the other molecular end.

[0093] The Mw of the block chain consisting of only the repeating unit a is preferably 1,500 to 5,000 in order to suppress the formation of semi-dry film-like foreign matter.

[0094] As a method for synthesizing the component (a-1) by copolymerizing the above-mentioned monomers, known methods such as free radical polymerization, living radical polymerization, and living anionic polymerization can be applied. Examples of living radical polymerization methods include atom transfer radical polymerization, reversible addition-fragmentation chain transfer polymerization, iodine transfer polymerization, nitroxide-mediated radical polymerization, and organotellurium-mediated radical polymerization.

[0095] Among these, free radical polymerization, nitroxide-mediated radical polymerization, and living anionic polymerization are preferred because they can suppress semi-dry film-like foreign matter while achieving high exposure sensitivity, and can also avoid residual heavy metal atoms to obtain high insulating properties.

[0096] The method for synthesizing component (a-1) will be specifically explained below, taking as an example a block copolymer having a block chain consisting of only repeating unit a and repeating unit b.

[0097] Examples of free radical polymerization methods include dissolving a monomer serving as a source for introducing repeating unit a in an organic solvent and stirring the solution in the presence of a thermal radical polymerization initiator at a nitrogen atmosphere and a temperature of 50 to 120°C for 2 to 30 hours to obtain a polymer consisting only of repeating unit a. Next, a monomer serving as a source for introducing repeating unit b, a monomer serving as a source for introducing other repeating units, and optionally a molecular weight distribution modifier are added, followed by stirring at 50 to 120°C for 2 to 30 hours. If a large amount of unreacted monomer remains after obtaining a polymer consisting only of repeating unit a, a purification / removal step may be added. The heating temperature can be appropriately set taking into account the 10-hour half-life temperature of the thermal radical polymerization initiator and the monomer reactivity. The heating time required to obtain the desired Mw under a given heating temperature condition varies depending on the solids concentration and stirring speed of the reaction system. Therefore, it is desirable to, for example, sample the solution during the reaction at regular intervals and obtain a prior understanding of the Mw increase curve using GPC. The reaction endpoint can be appropriately set by measuring the desired Mw and the amount of remaining unreacted monomer. Examples of the thermal radical polymerization initiator that can be used include azo-based thermal radical polymerization initiators such as azobisisobutyronitrile (hereinafter referred to as AIBN), AIBN-HP, V-65HP, V-601, VR-110, and V-40 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). The amount of the thermal radical polymerization initiator added is preferably 0.5 to 1.5 parts by mass per 100 parts by mass of the monomer. Examples of the organic solvent that can be used include isopropyl alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and ethyl lactate. Examples of the molecular weight distribution modifier that can be used include alkyl mercaptans such as hexyl mercaptan, dodecyl mercaptan, and n-octyl mercaptan.

[0098] Examples of nitroxide-mediated radical polymerization methods include dissolving a monomer that serves as a source for introducing repeating unit b and a monomer that serves as a source for introducing other repeating units in an organic solvent, stirring the resulting mixture for 3 to 30 hours in a nitrogen atmosphere at a liquid temperature of 50 to 150°C in the presence of a nitroxide-based reaction inhibitor to obtain a random polymer of repeating unit b and other repeating units, and then adding a monomer that serves as a source for introducing repeating unit a, followed by stirring the resulting mixture for 3 to 30 hours at a liquid temperature of 50 to 150°C. Commercially available nitroxide-based reaction inhibitors include Bloc Builder (registered trademark) MA and Bloc Builder RC-50 (both manufactured by ARKEMA). Examples of organic solvents that can be used include isopropyl alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and ethyl lactate.

[0099] Examples of living anionic polymerization methods include dissolving a monomer serving as a source for introducing repeating unit b and a monomer serving as a source for introducing other repeating units in an organic solvent, stirring the resulting mixture in the presence of an anionic polymerization initiator under a nitrogen atmosphere at a liquid temperature of -80 to 0°C for 10 minutes to 5 hours to obtain a random copolymer of repeating unit b and other repeating units, and then adding a monomer serving as a source for introducing repeating unit a, followed by stirring the resulting mixture at a liquid temperature of -80 to 0°C for 10 minutes to 5 hours. If a large amount of unreacted monomer remains after obtaining the random copolymer, a purification / removal step may be added. From a safety perspective, it is desirable to maintain the liquid temperature at 0°C or below after the start of the reaction and the water content in the reaction system at 1,000 ppm by mass or below. The reaction endpoint may be appropriately determined by measuring the desired Mw and the amount of remaining unreacted monomer using GPC. Examples of anionic polymerization initiators that can be used include the reaction product of a lithium compound such as ethyllithium, sec-butyllithium, n-butyllithium, tert-butyllithium, or lithium chloride with diphenylethylene (or a substituted derivative thereof). Examples of the organic solvent that can be used include tetrahydrofuran, ethylene glycol dimethyl ether, and diethyl ether. A lower alcohol such as methanol or ethanol can be used as a reaction terminator. When the aforementioned monomer in which the hydroxyl group is protected with a protecting group is used as the monomer from which the repeating unit b is introduced, a step of deprotecting the monomer using a strong acid such as hydrochloric acid may be added after obtaining the copolymer.

[0100] Specific examples of a block copolymer having a block chain consisting only of repeating unit a and repeating unit b include a block copolymer having a structure represented by formula (61) synthesized by nitroxide-mediated radical polymerization, and a block copolymer having a structure represented by formula (62) synthesized by living anionic polymerization.

[0101]

[0102] In formula (61) and formula (62), the integer represents the number of repeating units.

[0103] In the positive photosensitive pigment composition, the component belonging to the (a) resin may be only the component (a-1). However, in order to adjust the appropriate development time in the development step described below to fall within the desired range depending on the film thickness of the intended pixel division layer and spacer layer to be formed and the type / concentration of the developer, the positive photosensitive pigment composition of the present invention may contain another resin (a-2) (hereinafter, sometimes referred to as the (a-2) component). The component (a-2) here refers to a compound that does not belong to the component (a-1) among the components belonging to the (a) resin. The mixing ratio of the component (a-1) and the component (a-2) may be set as desired depending on the dissolution rate (nm / min) of each component in the developer, the ease with which the developer penetrates into the film surface, the desired process takt time, and the like.

[0104] Preferred examples of the component (a-2) include polyimide resins, polyimide precursors, polybenzoxazole precursors, novolak resins, and (meth)acrylic resins. These may be used alone or in combination of two or more. Among these, hydroxyl-containing novolak resins and hydroxyl-containing (meth)acrylic resins are preferred because they have excellent compatibility with the component (a-1), and because they facilitate controlling the alkali dissolution rate (nm / min) of the unexposed portion of the exposed film to a lower value through interaction with the component (c), which will be described later, and therefore have excellent exposure sensitivity. Hydroxyl-containing (meth)acrylic resins are more preferred in terms of suppressing semi-dry film-like foreign matter.

[0105] The hydroxyl group-containing novolak resin means a hydroxyl group-containing resin having a structural unit obtained by a polycondensation reaction between a compound having one phenol skeleton and an aldehyde.

[0106] Examples of compounds having one phenol skeleton include phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol, catechol, and 1,3-dihydroxy-5-methylbenzene.

[0107] Examples of aldehydes include formaldehyde, paraformaldehyde, benzaldehyde, and hydroxybenzaldehyde.

[0108] In order to suppress development residues in positive halftone processing, the Mw of the hydroxyl group-containing novolak resin is preferably 1500 to 15000. Commercially available products include, for example, TRR5030G, TRR5010G, TR4020G, TR4080G, TR4000B, TRM30B20G, and EP23F10G (all manufactured by Asahi Organic Chemicals Co., Ltd.).

[0109] The hydroxyl group-containing (meth)acrylic resin referred to here means a hydroxyl group-containing resin in which the content of repeating units derived from a compound having one methacryloyl group in the molecule and / or repeating units derived from a compound having one acryloyl group in the molecule is 40 to 100 mass %.

[0110] Examples of compounds having one methacryloyl group in the molecule and compounds having one acryloyl group in the molecule include (meth)acrylic acid, 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxyphenyl (meth)acrylate, 4-hydroxy-1-naphthyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, isodecyl methacrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate.

[0111] Furthermore, it may have a repeating unit derived from a compound that does not have a methacryloyl group or an acryloyl group in the molecule, such as a repeating unit derived from a styrene-based monomer or a repeating unit derived from a maleimide-based monomer.

[0112] Examples of styrene-based monomers include styrene, α-methylstyrene, 4-isopropenylphenol, 2-vinylphenol, 3-vinylphenol, and 4-vinylphenol. Examples of maleimide-based monomers include maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. Among these, in terms of improving halftone processability, a hydroxyl group-containing (meth)acrylic resin derived from repeating units derived from one or more phenolic hydroxyl group-containing compounds selected from the group consisting of 4-hydroxyphenyl(meth)acrylate, 4-hydroxy-1-naphthyl(meth)acrylate, and 4-isopropenylphenol, and also derived from repeating units derived from (meth)acrylic acid, is preferred.

[0113] The Mw of the (meth)acrylic resin is preferably 10,000 to 30,000 in order to suppress development residues in positive halftone processing.

[0114] The positive-type photosensitive pigment composition of the present invention may further contain a commercially available polymer dispersant belonging to component (a-2) as long as the effects of the present invention are not impaired. Examples of commercially available polymer dispersants belonging to component (a-2) include "DISPERBYK" (registered trademark) -102, P104, P105, 110, 111, 118, 142, 145, 161, 162, 164, 167, 168, 2000, 2001, 2010, 2013, 2020, 2025, 2050, 2096, 2150, 2155, 2163, 2164, 9075, 90 76, 9077, "BYK-LPN" (registered trademark) 6919, 21116, 21234, 24074, 22906 (all manufactured by BYK-Chemie), Efka-4015, 4020, 4046, 4047, 4050, 4055, 4060, 4080, 4300, 4310, 4320, 4330, 4340, 4400, 4401, 4402, 4403, 4800, Dispex Ultra PX4575 (all manufactured by BASF), "Solsperse" (registered trademark) 3000, 9000, 11200, 13240, 13650, 13940, 20000, 21000, 24000SC, 24000GR, 32000, 32500, 32550, 32600, 33000, 33500, 34750, 35100, 352 00, 36000, 36600, 37500, 39000, 40000, 41000, 56000, 71000, 76500 (all manufactured by Lubrizol Corporation), and "Ajisper" (registered trademark) PA111, PB821, PB822, PB824, PB881, PB883 (all manufactured by Ajinomoto Fine-Techno Co., Ltd.). Among these, phosphate ester-based polyether dispersants such as DISPERBYK-110, 111, Solsperse 40000, and 41000 may facilitate the suppression of minute development residues. These commercially available polymer-type dispersants belonging to component (a-2) can be used alone or in combination.

[0115] The positive photosensitive pigment composition of the present invention contains (b) an organic pigment (hereinafter, sometimes referred to as component (b)). The organic pigment here refers to a compound that absorbs light in the visible light region and exists in the positive photosensitive pigment composition in the form of insoluble particles. Component (b) has the effect of imparting light-blocking properties to the pixel dividing layer. Additionally, component (b) suppresses excessive thermal flow of the film after the development step in the curing step described below, thereby preventing pattern burying of openings in positive halftone processing and improving the in-plane uniformity of the opening width.

[0116] From the viewpoint of optical properties, examples of component (b) include organic blue pigments, organic purple pigments, organic red pigments, organic orange pigments, organic yellow pigments, organic brown pigments, and organic black pigments. To achieve both high light-blocking properties and high exposure sensitivity, organic blue pigments and / or organic purple pigments are preferred, and it is more preferable to use an organic blue pigment and an organic purple pigment in combination. Furthermore, by combining with component (e) described below, a pixel dividing layer that ultimately exhibits black can be obtained. That is, in the positive photosensitive pigment composition of the present invention, it is preferable that the organic pigment (b) contains an organic blue pigment and / or an organic purple pigment.

[0117] On the other hand, from the viewpoint of molecular structure, examples of the component (b) include (b-1) an organic pigment that does not have a sulfo group (hereinafter, sometimes referred to as component (b-1)), and (b-2) an organic pigment that has a sulfo group (hereinafter, sometimes referred to as component (b-2)). An organic pigment in which at least a portion of the surface of component (b-1) has been surface-treated with component (b-2) may also be used. Note that a pigment derivative in which a sulfo group has been introduced into an organic pigment that does not have a sulfo group, and particles that are insoluble in a positive photosensitive pigment composition, are defined as compounds belonging to component (b-2). The sulfo group referred to here is -SO ３ In addition to H, -SO ３ － (i.e., sulfonate group). ３ － is, for example, -SO ３ Na that makes up Na ＋ may be a group generated by dissociation of the above in the positive photosensitive pigment composition.

[0118] It is known in the technical common sense of a person skilled in the art that the component (b-2) is used as an auxiliary additive for the purpose of improving the dispersibility of the component (b-1) in the presence of the component (d) described below. However, in the positive photosensitive pigment composition of the present invention, the component (b-2) can be used as a component that exerts the effect of imparting light-blocking properties to the pixel division layer.

[0119] When the positive photosensitive pigment composition of the present invention contains component (b-1) and component (b-2), the organic pigment skeleton of component (b-2) strongly adsorbs to the surface of component (b-1), and the sulfo group of component (b-2) strongly adsorbs to the pigment adsorption group of repeating unit a of component (a-1). Alternatively, the positive photosensitive pigment composition of the present invention may contain only component (b-2) without component (b-1), and the sulfo group of component (b-2) strongly adsorbs to the pigment adsorption group of repeating unit a of component (a-1). Based on this mechanism, component (b-2) not only further suppresses the formation of semi-dry film-like foreign matter, but also neutralizes a larger number of pigment adsorption groups, thereby suppressing deterioration of the photoacid generator and trapping of acid generated in the film in exposed areas, thereby further improving exposure sensitivity. Therefore, in the positive photosensitive pigment composition of the present invention, the (b) organic pigment preferably contains (b-2) an organic pigment having a sulfo group.

[0120] Examples of the component (b-1) include organic blue pigments such as C.I. Pigment Blue 15, 60, 64, 80, and C.I. Disperse Blue 14, 79:1, 134, and 281; compounds represented by formula (63); organic purple pigments such as C.I. Pigment Violet 19 and 29, perylene-3,4,9,10-tetracarboxylic acid bisbenzimidazole (hereinafter sometimes referred to as "PTCBI"); C.I. Disperse Violet 27; and C.I. Vat Violet 13; perylene black consisting of a mixed crystal of PTCBI and C.I. Pigment Black 31; and a mixture of PTCBI and C.I. Examples of organic black pigments include perylene black, which is a mixed crystal of C.I. Pigment Black 32, and lactam black disclosed in WO 2009 / 010521. Among these, the compound represented by formula (63) is preferred in that it has high near-ultraviolet transmittance, can increase the amount of acid derived from the component (c) described below, and can improve exposure sensitivity.

[0121]

[0122] In formula (63), R ５２ , R ５３ , R ５４ , R ５５ , R ５６ , R ５７ , R ５８ , R ５９ , R ６０ , and R ６１ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; R ６２ , R ６３ , R ６４ , and R ６５ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ６６ , and R ６７ represents —CONH—.

[0123] Although the compound represented by formula (63) does not contain chlorine atoms in its molecular structure, the pigment powder may contain chlorine atoms due to trace amounts of residual chlorine-containing synthetic solvent. To improve the light-emitting properties of organic EL display devices, it is preferable to purify a pigment powder containing 70% by mass or more of the compound represented by formula (63) so that the chlorine atom content, as determined by combustion ion chromatography, is 1,000 ppm by mass or less. 500 ppm by mass or less is more preferable. Furthermore, excessive purification may change the pigment surface properties, making it more likely to produce semi-dry film-like foreign matter. To avoid this, a chlorine atom content of 10 ppm by mass or more is preferable, and 50 ppm by mass or more is more preferable. Purification methods include, for example, washing with water and / or an organic solvent, as well as heating at atmospheric pressure at 180 to 250°C for 30 to 120 minutes.

[0124] Examples of the component (b-2) include a compound represented by formula (64), a compound represented by formula (65), a mono / disulfonic acid derivative of C.I. Pigment Blue 60, a mono / disulfonic acid derivative of C.I. Pigment Blue 15, a mono / disulfonic acid derivative of C.I. Pigment Red 178, a mono / disulfonic acid derivative of C.I. Pigment Red 255, and a mono / disulfonic acid derivative of bis-oxodihydroindolylene-benzodifuranone described in WO 2009 / 010521. Among these, the compound represented by formula (64), the compound represented by formula (65), the compound represented by formula (98), the compound represented by formula (99), the compound represented by formula (100), and / or the compound represented by formula (101) are preferred in terms of high near-ultraviolet transmittance, the ability to increase the amount of acid generated from the component (c) described below, the ability to improve exposure sensitivity, and excellent light-blocking properties. In addition to the effect of suppressing semi-dry film-like foreign matter, the compound represented by formula (98), the compound represented by formula (99), the compound represented by formula (100), and the compound represented by formula (101) are more preferred in terms of their high effect of suppressing non-illuminated pixels.

[0125] That is, it is more preferable that the positive photosensitive pigment composition of the present invention contains, as component (b-2), one or more compounds selected from the group consisting of compounds represented by formula (98), compounds represented by formula (99), compounds represented by formula (100), and compounds represented by formula (101).

[0126]

[0127] In formula (64) and formula (65), R ６８ , R ６９ , R ７０ , R ７１ , R ７２ , R ７３ , R ７４ , and R ７５ are each independently a hydrogen atom, —SO ３ H, -SO ３ － , an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, -F, -Br, or -CN. ６８ , R ６９ , R ７０ , R ７１ , R ７２ , R ７３ , R ７４ , and R ７５ Middle, -SO ３ H, and -SO ３ － The total number of R is 1 or 2. ７６ , R ７７ , R ７８ , and R ７９ each independently represents a hydrogen atom, —OH, —F, —Br, —CN, or an alkoxy group having 1 to 5 carbon atoms. ７６ and R ７７ , R ７８ and R ７９ are each independently bonded to each other to form a linking group -X ２ - may be -X ２ - is -O- or -SO ２ Represents -.

[0128]

[0129] In formula (98), formula (99), formula (100), and formula (101), R８７ , R ９２ , R ９７ , and R １００ are each independently -SO ３ H, or -SO ３ － represents R ８８ , R ８９ , R ９０ , R ９１ , R ９３ , R ９４ , R ９５ , and R ９６ each independently represents a phenyl group, a benzyl group, or an alkyl group having 1 to 20 carbon atoms; R ９８ , and R １０１ each independently represents an alkyl group having 1 to 20 carbon atoms; R ９９ , and R １０２ each independently represents an alkyl group having 1 to 3 carbon atoms; n １６ , and n １７ are integers, each independently representing 0 to 2. ８８ , R ８９ , R ９０ , and R ９１ one or two groups are a phenyl group, a benzyl group, or an alkyl group having 8 to 20 carbon atoms, and R ９３ , R ９４ , R ９５ , and R ９６ Among these, one or two groups are a phenyl group, a benzyl group, or an alkyl group having 8 to 20 carbon atoms.

[0130] Examples of methods for synthesizing the compound represented by formula (64) and the compound represented by formula (65) include a method in which a mixed powder of cis / trans isomers of PTCBI or a derivative thereof is heated in concentrated sulfuric acid or fuming sulfuric acid, preferably at 50 to 90°C, until it becomes a mono- or disulfonic acid, and then poured into an excess amount of ice water and stirred, followed by filtration, purification, drying, and pulverization. The purification process may include a solvent treatment, filtration, and isolation by silica gel chromatography. If necessary, a step of converting at least a portion of the sulfo groups into alkali metal salts by adding an aqueous solution of an inorganic alkali such as sodium hydroxide may be added to increase the solubility in water and improve productivity. Subsequently, a salt formation operation is performed using an ammonium salt of a specific structure, followed by purification, drying, and pulverization, thereby synthesizing the compound represented by formula (98) and the compound represented by formula (99). Furthermore, by using a pyridinium salt of a specific structure instead of the ammonium salt of a specific structure, the compound represented by formula (100) and the compound represented by formula (101) can be synthesized.

[0131] Examples of the ammonium salt having a specific structure include benzyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium bromide, dimethyldioctylammonium bromide, and benzyldimethylphenylammonium chloride.

[0132] Examples of pyridinium salts having a specific structure include 1-ethyl-4-methylpyridinium bromide, 1-ethyl-4-propylpyridinium chloride, 1-ethyl-2-methylpyridinium bromide, 1-dodecylpyridinium bromide, 1-butylpyridinium chloride, 1-butyl-3-methylpyridinium chloride, hexadecylpyridinium chloride, and hexadecylpyridinium bromide.

[0133] Specific examples of the component (b-2) obtained by the above-described method preferably include a compound represented by formula (102) and a compound represented by formula (103). Note that at least a portion of the counter cation moiety derived from the ammonium salt of a specific structure or the pyridinium salt of a specific structure may be volatilized and removed in the curing step when forming the pixel dividing layer and the spacer layer.

[0134]

[0135] The sulfo group in component (b-2) and the pigment-adsorptive group in repeating unit a may form a salt. An ionic bond can be considered one form of adsorption as a pigment dispersant, and the salt here is defined as a mixture of component (b-2) and a resin having repeating units a and b. A preferred example of the salt structure is a structure represented by formula (66).

[0136]

[0137] In formula (66), * represents a binding site.

[0138] The primary particle size distribution of component (b) is preferably 5 to 150 nm, more preferably 20 to 100 nm, in order to achieve high light-shielding properties and avoid development residues in positive halftone processing. The primary particle size distribution can be measured using a transmission electron microscope (TEM).

[0139] In order to obtain high light-blocking properties, the content of component (b) is preferably 15 parts by mass or more per 100 parts by mass of the solid content of the positive photosensitive pigment composition. Furthermore, by making the content 15 parts by mass or more, even if the glass transition temperature (Tg) of the (a) resin is lower than the heating temperature of the curing process, excessive thermal flow of the film can be avoided, making it possible to obtain a pixel division layer with high resolution. In order to suppress development residues in positive halftone processing, the content of component (b-1) or less is preferably 40 parts by mass or less. When the positive photosensitive pigment composition of the present invention contains component (b-1) and component (b-2), in order to suppress the formation of semi-dry film-like foreign matter, the content of component (b-2) is preferably 10 parts by mass or more per 100 parts by mass of component (b-1).

[0140] The positive photosensitive pigment composition of the present invention may contain a small amount of a pigment other than component (b), i.e., an inorganic pigment, such as carbon black, titanium oxynitride, or zirconium oxynitride, for the purpose of adjusting reflected chromaticity, as long as the effects of the present invention are not impaired and the alignment of the electrode-forming substrate and the exposure mask by near-infrared alignment in the exposure step disclosed in Patent Document 5 is not impaired, and insulation is not impaired.

[0141] The positive photosensitive pigment composition of the present invention contains (c) a photoacid generator (hereinafter, sometimes referred to as component (c)). Component (c) is not particularly limited as long as it is a compound that generates an acid upon irradiation with light containing at least light with a wavelength of 200 to 450 nm. The principle of acid generation may be conversion of component (c) into a chemical structure having an acid, or dissociation of the acid by photolysis, and the acid generated is preferably a carboxylic acid and / or a sulfonic acid.

[0142] Component (c) is an essential component that generates acid to increase the solubility of the exposed portions of the film in alkaline developer relative to the solubility of the unexposed portions, thereby imparting positive photosensitivity. Based on this principle, pattern formability, i.e., positive photosensitivity, is achieved by removing the exposed portions of the film pattern-exposed through a positive exposure mask. In addition, the amount of acid generated in the film can be controlled by adjusting the exposure dose. By performing pattern exposure through an exposure mask having multiple types of openings with different transmittances and light-shielding portions within the surface, i.e., a positive halftone exposure mask, the solubility in alkaline developer of the exposed portions of the film exposed with a low exposure dose can be reduced relative to the solubility in alkaline developer of the exposed portions of the film exposed with a high exposure dose, allowing patterns of different film thicknesses to be formed on the same surface. Based on this principle, a pixel division layer and a spacer layer can be formed simultaneously. As component (c), a compound that absorbs in the i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (wavelength 436 nm) regions of a mercury lamp and generates an acid is preferred, such as a quinone diazide compound, an imide sulfonate compound, an oxime sulfonate compound, a sulfonium salt compound, or an iodonium salt compound. Among these, non-salt-type photoacid generators are desirable because they exhibit weak interaction with the pigment dispersion and provide excellent application properties for the positive photosensitive pigment composition, with quinone diazide compounds, imide sulfonate compounds, and oxime sulfonate compounds being preferred. Furthermore, quinone diazide compounds are more preferred because they exhibit a high dissolution-inhibiting effect on the unexposed film, thereby increasing the difference in dissolution rate between the exposed and unexposed film regions, resulting in excellent thick-film processability suitable for positive halftone processing, and high exposure sensitivity. That is, in the positive photosensitive pigment composition of the present invention, it is more preferred that the photoacid generator (c) contains a quinone diazide compound.

[0143] The quinone diazide compound is preferably a quinone diazide compound having a group represented by formula (67) and / or a group represented by formula (68), in order to achieve both high exposure sensitivity and high developability. It is more preferable to contain at least one compound selected from the group consisting of quinone diazide compounds having two or more groups represented by formula (67) in one molecule and having a phenolic hydroxyl group, quinone diazide compounds having two or more groups represented by formula (68) in one molecule and having a phenolic hydroxyl group, and quinone diazide compounds having a group represented by formula (67) and a group represented by formula (68), and having a phenolic hydroxyl group.

[0144]

[0145] In formula (67) and formula (68), * represents a binding site, R ８０ , R ８１ , R ８２ , R ８３ , R ８４ , R ８５ , and R ８６ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. ８０ , R ８１ , R ８２ , R ８３ , R ８４ , R ８５ , and R ８６ is preferably a hydrogen atom in order to improve resolution.

[0146] Specific examples of the quinone diazide compound include compounds represented by formulae (69) to (74). These compounds are photoacid generators that generate carboxylic acids and / or sulfonic acids upon exposure to light.

[0147]

[0148] In formulas (69) to (74), Q １ , Q ２ , Q ３ , Q ４ , Q ５ , Q ６ , Q ７ , Q ８ , Q９ , Q １０ , Q １１ , Q １２ , Q １３ , Q １４ , Q １５ , Q １６ , Q １７ , and Q １８ each independently represents a hydrogen atom, a structure represented by formula (75), or a structure represented by formula (76), １ , Q ２ , Q ３ , and Q ４ One or two of Q are hydrogen atoms, ５ , Q ６ , and Q ７ One or two of Q are hydrogen atoms, １３ , and Q １４ One of them is a hydrogen atom, and Q １５ , Q １６ , Q １７ , and Q １８ Among these, one or two are hydrogen atoms.

[0149]

[0150] In formulas (75) and (76), * represents a binding site.

[0151] Specific examples of the imide sulfonate compound include compounds represented by formulas (77) to (79). These compounds are photoacid generators that generate sulfonic acid upon exposure to light.

[0152]

[0153] Specific examples of the oxime sulfonate compound include compounds represented by formulas (80) to (82). These compounds are photoacid generators that generate sulfonic acid upon exposure to light.

[0154]

[0155] Commercially available products of the component (c) that are sensitive to i-rays include quinone diazide compounds such as DTEP4G-300 and DTEPG-350 (both manufactured by Daito ChemiX Co., Ltd.), CNB-250 and TEKOC (4)-200 (manufactured by Toyo Gosei Co., Ltd.), imidosulfonate compounds such as NIT, NIN and ILP-110 (all manufactured by Heraeus), NP-TM2 and NP-SE10 (all manufactured by San-Apro Co., Ltd.), and oxime sulfonate compounds such as PAG103 and PAG203 (both manufactured by BASF).

[0156] The content of component (c) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, per 100 parts by mass of the solid content of the positive photosensitive pigment composition, in order to generate a necessary and sufficient amount of acid in the film and improve exposure sensitivity, and is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, in order to suppress excessive absorption of exposure light on the film surface and improve exposure sensitivity.

[0157] The positive photosensitive pigment composition of the present invention contains (d) an organic solvent (hereinafter, sometimes referred to as component (d)). Component (d) is a dispersion medium for component (b), and provides fluidity to the positive photosensitive pigment composition, improving its coatability and the smoothness of the prebaked film, which will be described later.

[0158] Examples of the component (d) 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 Examples of the propylene glycol monomethyl ether include tripropylene glycol monoethyl ether, methyl lactate, ethyl lactate, 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, 3-methoxybutyl acetate, 3-methoxybutanol, γ-butyrolactone (hereinafter referred to as GBL), γ-valerolactone, N-methylpyrrolidone (hereinafter referred to as "NMP"), N,N-dimethylformamide, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropanamide, and 3-butoxy-N,N-dimethylpropanamide. Among these, from the viewpoints of the coatability of the positive photosensitive pigment composition, the leveling properties after application, and the appropriate drying properties, it is preferable to contain a combination of two or more species selected from the group consisting of PGME, methyl lactate, ethyl lactate, PGMEA, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, 3-methoxybutanol, and GBL.

[0159] The content of component (d) is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, per 100 parts by mass of the positive photosensitive pigment composition in order to improve coatability, and is preferably 99 parts by mass or less, more preferably 95 parts by mass or less in order to improve the smoothness of the prebaked film.

[0160] The positive photosensitive pigment composition of the present invention preferably further contains (e) a compound that, upon heating, is converted into a compound having an absorption maximum in the wavelength range of 350 to 500 nm within the wavelength range of 350 to 780 nm. Note that component (e) here refers to a compound that does not belong to any of components (a), (b), (c), (d), or (f). The mechanism of thermal color development is not particularly limited. The minimum temperature at which color development begins is preferably 150°C or higher to avoid a decrease in exposure sensitivity, and preferably 230°C or lower to fully achieve the effect of reducing transmittance in the wavelength range of 350 to 500 nm. Examples of component (e) include the thermochromic compounds described in JP-A-2004-326094. These compounds are converted into compounds having an absorption maximum in the wavelength range of 350 to 500 nm, and after heat treatment at, for example, 250°C, component (e) exhibits a yellow, orange, or brown hue in the film. Among these, in order to improve positive halftone processability, it is preferable that component (e) contains a hydroxyl group-containing compound. 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). Furthermore, when the curing process is performed under a low oxygen concentration, polyhydric phenol compounds such as trihydroxybenzene, phenol compounds having a specific structure disclosed in WO 2024 / 135186, and phenol compounds having a specific structure disclosed in WO 2024 / 135186 are preferred because of their excellent effect of reducing transmittance in the wavelength range of 350 to 500 nm.

[0161] The positive photosensitive pigment composition of the present invention may further contain (f) a thermal crosslinking agent (hereinafter, sometimes referred to as component (f)). By containing component (f), the chemical resistance and mechanical strength of the pixel dividing layer and the spacer layer can be improved.

[0162] As the component (f), a compound having two or more alkoxymethyl groups or epoxy groups in the molecule is preferred.

[0163] Examples of compounds having two or more alkoxymethyl groups in the molecule include HMOM-TPHAP, DML-PC, DML-PEP, DML-OC, and DML-POP (all manufactured by Honshu Chemical Industry Co., Ltd.), and NIKALAC (registered trademark) MX-390, MX-290, MX-280, MX-270, MW-100LM, and MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.).

[0164] Examples of compounds having two or more epoxy groups in the molecule include TEPIC-S, TEPIC-PAS, TEPIC-VL, and TEPIC-UC (all manufactured by Nissan Chemical Industries, Ltd.), XD-1000, XD-1000-H, XD-1000-2L, and NC-3000 (all manufactured by Nippon Kayaku Co., Ltd.), TECHMORE VG3101L (manufactured by Printec Co., Ltd.), and TR-FR-201 (manufactured by Tronly).

[0165] The positive photosensitive pigment composition of the present invention may further contain, as necessary, other components such as a silicone or acrylic leveling agent, or an agent for improving adhesion to the substrate surface, such as a silane coupling agent.

[0166] The chemical structures of the (a) resin, (b) component, (c) component, (d) component, (e) component, and (f) component were determined by pyrolysis gas chromatography mass spectrometry (pyrolysis GC-MS), liquid chromatography mass spectrometry (LC-MS), matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF MS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), proton nuclear magnetic resonance spectrometry ( １The analysis can be carried out by appropriately combining known techniques such as H-NMR, microscopic infrared absorption spectroscopy, etc. Alternatively, a positive photosensitive pigment composition can be used as an analytical sample, and pre-treated with a centrifugal separator to separate and remove the component (b) to obtain a concentrated solution, which can then be analyzed by carbon nuclear magnetic resonance analysis ( １３ By analyzing the sequence of the repeating units by C-NMR, it is possible to detect block chains consisting only of repeating units a in the component (a-1). The accuracy of the analysis may be further improved by adding hydrochloric acid and an alcoholic solvent to the analysis sample to extract soluble components containing the (a) resin, or by using GPC to increase the purity of the (a) resin in the concentrated solution.

[0167] A method for preparing the positive photosensitive pigment composition includes a method in which a pigment dispersion containing the (a) resin, the (b) component, and the (d) component is prepared in advance by wet dispersion treatment, and then the (c) component and the (d) component, and optionally the (e) component, the (f) component, and other components are mixed and stirred with the pigment dispersion, and optionally filtered.

[0168] The disperser used for the wet dispersion treatment may be a wet media disperser or a wet medialess disperser, but it is preferable to use a wet media disperser because it has excellent dispersion treatment speed and is economically advantageous. The wet media dispersion treatment deagglomerates the secondary aggregates of component (b), thereby obtaining a fine and sharp particle size distribution. Examples of wet media dispersers include bead mills such as "Levomill (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), "Spike Mill (registered trademark)" (manufactured by Inoue Manufacturing Co., Ltd.), "Sand Grinder (registered trademark)" (manufactured by DuPont), "Ultra Apex Mill Advance (registered trademark)" (manufactured by Hiroshima Metal & Machinery Co., Ltd.), and "NEO-Alpha Mill (registered trademark)" (manufactured by AIMEX Co., Ltd.). The media is preferably made of ceramic beads such as zirconia, with a diameter of 0.03 to 0.5 mm. Commercially available products include "Toraceram (registered trademark)" (manufactured by Toray Industries, Inc.).

[0169] The cured film of the present invention, which is a second aspect of the present invention, is a cured film containing a cured product of the positive photosensitive pigment composition of the present invention. The cured product here refers to a film obtained by a process of heating the positive photosensitive pigment composition at a temperature of 200°C or higher and 400°C or lower under atmospheric pressure for 10 minutes or longer.

[0170] The cured film of the present invention has the advantageous technical feature of suppressing the occurrence of defective portions due to semi-dry film-like foreign matter and suppressing the occurrence of non-illuminated pixels, and therefore can be suitably used as a pixel dividing layer and / or a spacer layer of an organic EL display device. Components other than the cured product of the positive photosensitive pigment composition include, for example, moisture mixed in during the cured film formation process and Na mixed into the cured film from the underlying substrate or electrodes. ＋ , Ag ＋ Examples of metal ions include:

[0171] A preferred embodiment in which the cured film of the present invention is used as a pixel dividing layer and a spacer layer in an organic EL display device will be described below.

[0172] The optical density per 1.0 μm of the film thickness of the pixel division layer, which is an index of the light-blocking property of the pixel division layer, is preferably 0.5 or more, more preferably 0.7 or more, in order to suppress reflection of external light and enhance the value of the display device. From the viewpoint of the exposure sensitivity of the positive photosensitive pigment composition, it is preferably 1.5 or less, more preferably 1.3 or less.

[0173] The optical density referred to here means the value obtained by measuring the incident light intensity and transmitted light intensity of a pixel division layer formed on a transparent substrate to a thickness of 1.5 μm using an optical densitometer X-Rite 361T (manufactured by X-Rite Corporation), calculating the value using the following formula, and dividing the calculated value by 1.5, which is the film thickness value, and the higher the optical density, the higher the light-blocking property. As the transparent substrate, a transparent glass substrate "Tempax (manufactured by AGC Technoglass Co., Ltd.)" can be preferably used. Optical density = log １０ (I ０ / I) In the above formula, I ０ : incident light intensity, I: transmitted light intensity.

[0174] To improve yield by reducing the contact area with the deposition mask when pattern-depositing the light-emitting layer, and to also achieve exposure sensitivity, the thickness of the pixel division layer is preferably 1.0 to 2.5 μm. The thickness of the spacer layer is preferably 1.0 to 2.0 μm. From the viewpoint of exposure sensitivity, the thickness of the portion where the pixel division layer and the spacer layer are stacked is preferably 2.0 to 4.0 μm.

[0175] A method for forming a cured film that can be used as a pixel dividing layer and a spacer layer preferably includes a coating step of applying a positive photosensitive pigment composition to obtain a coating film, a pre-baking step of heating the coating film to obtain a pre-baked film, an exposure step of pattern-exposing the pre-baked film to actinic rays through a positive half-tone exposure mask to obtain an exposed film having exposed areas, semi-exposed areas, and unexposed areas within its surface, a development step of developing the exposed film with an alkaline developer to obtain a developed film by removing part of the semi-exposed and unexposed areas in addition to the exposed areas, and a curing step of thermally curing the film by heating to obtain a cured film.

[0176] As the coating device used in the coating step, a spin coater or a slit coater can be preferably used because of its excellent thin film coating ability.

[0177] The pre-baking temperature in the pre-baking step is preferably 50 to 150°C, and the pre-baking time is preferably 30 seconds to 5 minutes. When the pixel dividing layer and the spacer layer are formed simultaneously, the thickness of the pre-baked film is preferably 3.5 to 6.0 μm. To improve the film thickness uniformity, a reduced pressure drying step may be provided between the coating step and the pre-baking step.

[0178] Examples of exposure devices used in the exposure step include a stepper, a mirror projection mask aligner (MPA), and a parallel light mask aligner (PLA). Examples of active actinic rays irradiated during exposure include the j-line (wavelength 313 nm), i-line (wavelength 365 nm), h-line (wavelength 405 nm), or g-line (wavelength 436 nm) from an ultra-high pressure mercury lamp. Mixed rays containing at least the h-line are preferred, and mixed rays containing the g-line, h-line, and i-line are more preferred. A positive halftone exposure mask preferably has a fully transparent portion, a semi-transparent portion, and a shielding portion within the substrate plane, and is designed so that when the exposure amount in the fully transparent portion is 100% and the exposure amount in the shielding portion is 0%, the exposure amount in the semi-transparent portion is 10 to 50%.

[0179] The exposed portion of the exposed film means a portion that has been pattern-exposed through the fully transparent portion of the exposure mask, the partially exposed portion means a portion that has been pattern-exposed through the semi-transparent portion of the exposure mask, and the unexposed portion means a portion that has not been exposed due to the shielding portion of the exposure mask.

[0180] Examples of development methods used in the development process include showering, dipping, and puddling, and include a method in which the exposed film is immersed for 10 seconds to 3 minutes. The puddling method is preferred to improve the uniformity of the opening width of the pixel division layer. The alkaline developer is preferably a 0.4 to 2.5 wt% aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as "TMAH"), and a commercially available example is 2.38 wt% TMAH (manufactured by Tama Chemicals Co., Ltd.). After the development process, a cleaning process using a shower of deionized water and / or a water-removing process using air spray may be performed. To improve the in-plane uniformity of the developed film thickness, it is preferable to set the development time so that the film loss (μm) during the development process, calculated by subtracting the film thickness of the unexposed developed film from the film thickness of the prebaked film, is 1.0 μm or less. To improve exposure sensitivity, it is preferable to set the development time so that the film loss (μm) is 0.5 μm or more.

[0181] In the curing step, the developed film is thermally cured by heating, and the developer and moisture remaining in the film are evaporated to obtain a cured film. Examples of heating devices include a hot air oven and an IR oven, and the heating atmosphere can be nitrogen or air. The heating temperature is preferably 220 to 280°C.

[0182] The organic EL display device of the present invention, which is a third aspect of the present invention, is an organic EL display device comprising the cured film of the present invention. The organic EL display device of the present invention has the advantageous technical effect of suppressing the occurrence of unlit pixels. Furthermore, by providing a pixel division layer and a spacer layer formed simultaneously by positive halftone processing, the pixel division layer has high in-plane uniformity in the aperture width, and is characterized by advantageous manufacturing costs compared to when the pixel division layer and the spacer layer are formed separately and laminated. As a specific example of an embodiment of an organic EL display device of the present invention comprising the cured film of the present invention as the pixel division layer and the spacer layer, a cross-sectional view of a TFT substrate in the organic EL display device is shown in Figure 1.

[0183] Bottom-gate or top-gate thin film transistors 1 (hereinafter abbreviated as TFT1) are arranged in a matrix on the surface of a substrate 6, and a TFT insulating layer 3 is formed to cover the TFT1 and the wiring 2 connected to the TFT1. Furthermore, a planarization layer 4 is formed on the surface of the TFT insulating layer 3, and contact holes 7 are formed in the planarization layer 4 to connect first electrodes 5 to the wiring 2. First electrodes 5 are patterned on the surface of the planarization layer 4 and connected to the wiring 2. A pixel division layer 8 is arranged to surround the periphery of the pattern of the first electrodes 5. The pixel division layer 8 has openings, and light-emitting pixels 10 containing an organic EL light-emitting material are arranged in the openings. A convex spacer layer 9 is arranged on a portion of the surface of the pixel division layer 8. A second electrode 11 is arranged to cover the pixel division layer 8, the spacer layer 9, and the light-emitting pixels 10.

[0184] If a TFT substrate having the above-described laminated structure is sealed under vacuum and then a voltage is applied to the light-emitting pixel portion, the organic EL display device can emit light. The shape of the openings in the pixel dividing layer 8 is not particularly limited and may be square, rectangular, or elliptical. The opening width of the openings may be determined appropriately depending on the size of the light-emitting pixels 10, and may have a minor axis of 10 to 50 μm, for example. The spacer layer 9 reduces the contact area with the vapor deposition mask when forming the light-emitting pixels 10, thereby preventing defects in the organic EL elements and improving production yield.

[0185] The emission peak wavelength of the light-emitting pixel 10 is not particularly limited, but a specific example of the configuration includes an array of different types of pixels having emission peak wavelengths in the blue, red, and green regions, which are the three primary colors of light. The peak wavelength in the red region may be 560 to 700 nm, the peak wavelength in the blue region may be 420 to 480 nm, and the peak wavelength in the green region may be 500 to 550 nm. In addition to the TFT substrate shown in FIG. 1, to improve the color reproducibility of the emitted light, a color adjustment layer consisting of blue, red, and green color filters and a black matrix separating them may be provided on the light extraction side. Examples of color filters include the color filters with high color reproducibility disclosed in JP 2022-164709 A.

[0186] As the organic EL light-emitting material constituting the light-emitting pixel 10, a material that further combines a hole transport layer and / or an electron transport layer in addition to the light-emitting layer can be suitably used. A mask vapor deposition method can be used as a method for forming a pattern of the light-emitting pixel 10. The mask vapor deposition method is a method of vapor-depositing an organic compound using a vapor deposition mask to form a pattern. Specifically, a method of vapor deposition can be used in which a vapor deposition mask with openings in a desired pattern is placed on the substrate side. An example of a vapor deposition mask used to form high-definition light-emitting pixels is the vapor deposition mask disclosed in JP 2019-163543 A.

[0187] The first electrode 5 can be made of conductive metal oxides such as indium tin oxide (ITO) and indium zinc oxide (IZO). Among these, ITO is preferred due to its excellent transparency and conductivity. A method for patterning ITO involves forming an ITO film over the entire surface by sputtering, then patterning a positive etching resist material by photolithography to obtain a resist pattern on the ITO film, and then removing only the ITO film in the areas where the resist pattern is not formed with an etching solution. The resist pattern is then removed with a resist stripper, and if necessary, heat treatment is performed to achieve the desired crystallinity. A positive photosensitive composition containing an alkali-soluble novolac resin can be used as the positive etching resist material. As the etching solution, an aqueous solution containing nitric acid and hydrochloric acid or an aqueous solution of oxalic acid can be used, and commercially available products include, for example, ITO-101N (manufactured by Kanto Chemical Co., Ltd.), "Sclean (registered trademark)" IS-2, and "Sclean (registered trademark)" IS-3 (all manufactured by Sasaki Chemical Co., Ltd.). As the resist stripping solution, an organic amine-based aqueous solution can be used, and commercially available products include, for example, "Anlast (registered trademark)" M6, M6B, TN-1-5, and M71-2 (all manufactured by Miwa Pure Chemical Research Institute). When the organic EL display device of the present invention is a top-emission organic EL display device, the first electrode 5 may have a laminated structure of ITO / silver alloy / ITO in order to improve light reflectivity and adhesion to the substrate.

[0188] The second electrode 11 may be made of any material as long as it functions as an electrode. For example, when the organic EL display device of the present invention is a bottom-emission organic EL display device, a layer made of aluminum is preferably used as the second electrode 11 because of its excellent light reflectivity. When the organic EL display device is a top-emission organic EL display device, a silver alloy such as silver / magnesium is preferably used because of its excellent light transmittance. The second electrode 11 can be obtained by forming a film over the entire surface by sputtering.

[0189] The light extraction direction of the organic EL display device of the present invention is not particularly limited, and the organic EL display device may be a bottom-emission type organic EL display device in which emitted light from the light-emitting pixels 10 is extracted to the substrate side through the substrate 6, or a top-emission type organic EL display device in which emitted light is extracted to the opposite side of the substrate 6 through the second electrode 11. In the case of a bottom-emission type, the film thickness of the second electrode 11 is preferably 70 nm or more in order to improve light reflectivity. In the case of a top-emission type, the film thickness of the second electrode 11 is preferably 40 nm or less in order to improve light transmittance.

[0190] The substrate 6 may be a substrate made of rigid glass or a substrate made of flexible polyimide resin. Examples of glass include OA-10G and OA-11 (both manufactured by Nippon Electric Glass Co., Ltd.) and AN-100 (manufactured by Asahi Glass Co., Ltd.). Examples of substrates made of polyimide resin include substrates obtained by applying a solution containing polyamic acid to the surface of a temporary support, followed by heat treatment at 250 to 400°C to imidize the polyamic acid and convert it into a polyimide resin, and then peeling off the temporary support using a laser or the like. A specific example is polyamic acid having a residue of 3,3',4,4'-biphenyltetracarboxylic dianhydride and a residue of p-phenylenediamine.

[0191] The electronic device of the present invention, a fourth aspect, is an electronic device equipped with the organic EL display device of the present invention. As described above, the electronic device of the present invention has the technical effects of high in-plane uniformity of luminescent pixel size and suppressed occurrence of non-illuminated pixels. Furthermore, by incorporating an organic EL display device having a collectively formed pixel division layer and spacer layer, the electronic device of the present invention has the advantageous characteristics of suppressing brightness unevenness, excellent visibility, and low cost. Here, an electronic device equipped with an organic EL display device refers to a device that includes at least an organic EL display device, a driving circuit, and a power supply, and is capable of independently displaying text information, images, and / or video. Specific examples of embodiments of the electronic device of the present invention include personal computers, foldable smartphones, non-foldable rigid smartphones, wristwatches, table clocks, eyeglasses, in-vehicle monitors, car navigation systems, gaming monitors, portable game consoles, televisions, and head-mounted displays.

[0192] The block copolymer of the present invention, which is a fifth aspect of the present invention, is a block copolymer having a block chain consisting only of repeating units a and repeating units b, wherein the repeating units a are at least one selected from the group consisting of repeating units represented by formula (1), repeating units represented by formula (2), repeating units represented by formula (3), repeating units represented by formula (4), and repeating units represented by formula (5), and the repeating units b are repeating units represented by formula (33) and / or repeating units represented by formula (34).

[0193]

[0194] In formulas (1), (2), (3), (4), and (5), * represents a binding site, and R １ , R ４ , R ７ , R １１ , and R １５ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R ２ , R ５ , R ８ , R １２ , and R１６ each independently represents a single bond or a divalent linking group having 1 to 8 carbon atoms and not containing a nitrogen atom, ３ , R ６ , R ９ , R １４ , and R １９ each independently represents an alkyl group having 1 to 3 carbon atoms; １ , n ２ , n ３ , n ４ , and n ５ are integers, each independently representing 0 to 2; １０ and R １３ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R １７ and R １８ each independently represents an alkyl group having 1 to 5 carbon atoms.

[0195]

[0196] In formula (33) and formula (34), * represents a binding site, R ３１ and R ３４ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R ３２ and R ３５ each independently represents a single bond or a divalent linking group having 1 to 8 carbon atoms; R ３３ , R ３６ , and R ３７ each independently represents an alkyl group having 1 to 3 carbon atoms; ９ is an integer representing 1 or 2; １０ , n １１ , n １２ , n １３ , n １４ are integers, each independently representing 0 to 2. ３２ and R ３５ does not contain any nitrogen atom other than the nitrogen atom contained in —CONH—, and n １１ and １２ The sum of n is 0 to 3, １２ and １４ The sum is 1 or 2.

[0197] The block copolymer of the present invention is a compound belonging to the component (a-1) in the first aspect of the present invention, and is useful as a pigment dispersant having the above-mentioned four advantageous characteristics.

[0198] The block chain consisting only of repeating unit a herein means a structure in which 10 or more repeating units belonging to repeating unit a are linked together and have a molecular weight of 1000 or more. The arrangement of repeating units other than the block chain consisting only of repeating unit a in the block copolymer herein is not particularly limited.

[0199] When used in the production of a positive-type photosensitive pigment composition, the preferred chemical structure of the block copolymer of the present invention is based on the same viewpoints as those for the preferred chemical structure of the aforementioned component (a-1).

[0200] In order to suppress the generation of semi-dry film-like foreign matter and to obtain high exposure sensitivity, it is more preferable that the repeating unit a be one or more selected from the group consisting of the repeating unit represented by the above-mentioned formula (7), the repeating unit represented by the formula (8), and the repeating unit represented by the formula (9). In terms of the high effect of suppressing the generation of non-illuminated pixels, it is most preferable to have the repeating unit represented by the formula (9).

[0201] The block copolymer of the present invention can be suitably used for producing a pigment dispersion, and for producing a positive-type photosensitive pigment composition for forming a pixel dividing layer and a spacer layer provided in an organic EL display device.

[0202] The block copolymer of the present invention can be synthesized by the same method as that for synthesizing the component (a-1) described above.

[0203] The present invention will be described in detail below with reference to examples and comparative examples, but the aspects of the present invention are not limited to these. First, the evaluation methods used in each example and comparative example will be described.

[0204] (1) Evaluation of the amount of semi-dry film-like foreign matter generated The positive photosensitive pigment compositions were stored in a freezer (atmospheric pressure / shielded from light, -20°C±1°C) for 30 days and then removed from the freezer. 10.00 g of each positive photosensitive pigment composition was dropped into 50 mL transparent glass vials (manufactured by AS ONE Corporation / Labolan (registered trademark) screw cap bottle No. 7; hereinafter sometimes referred to as "vials") serving as storage containers, and the vials were then tightly sealed. A schematic diagram of the appearance of the positive photosensitive pigment compositions after being dropped into the glass vials and tightly sealed is shown in Figure 2.

[0205] This was stirred for 1 minute, so that the entire inner wall surface of the vial was brought into contact with and wetted by the positive photosensitive pigment composition. After standing for 7 days in a thermostatic chamber maintained at atmospheric pressure and a liquid temperature of 25±1° C., the vial was opened, and the vial was turned upside down and held for 1 minute, and the liquid that fell out was transferred to another container and discarded.

[0206] Next, 35.00 g of PGME was poured as a cleaning solvent into the vial containing the components derived from the positive photosensitive pigment composition, and the vial was sealed and stirred for 1 minute. The vial was opened and held upside down for 5 minutes, and the liquid that fell out was transferred to another container and discarded. Figure 3 shows a schematic diagram of the appearance of a glass vial with semi-dry film-like foreign matter on its inner wall surface. The vial was left open and dried in an oven maintained at 100°C for 3 hours, after which the mass of the vial was measured and the mass (g) of the deposit remaining on the inner wall surface of the vial was calculated by subtracting the mass of the vial alone, which had been measured before use. The mass of the deposit remaining on the inner wall surface of the vial was considered to be the amount (g) of semi-dry film-like foreign matter generated, and the smaller the amount generated, the better the result.

[0207] Evaluation was based on the following criteria, with AA and A to C being pass, and D to E being fail. The above evaluations were performed under yellow light, which does not expose component (c). AA: The amount of semi-dry film-like foreign matter generated is less than 0.05g. A: The amount of semi-dry film-like foreign matter generated is 0.05g or more but less than 0.10g. B: The amount of semi-dry film-like foreign matter generated is 0.10g or more but less than 0.15g. C: The amount of semi-dry film-like foreign matter generated is 0.15g or more but less than 0.20g. D: The amount of semi-dry film-like foreign matter generated is 0.20g or more but less than 0.40g. E: The amount of semi-dry film-like foreign matter generated is 0.40g or more.

[0208] (2) Evaluation of Exposure Sensitivity (Minimum Required Exposure Amount) The positive photosensitive pigment compositions were stored in a freezer (atmospheric pressure / shielded from light, -20°C±1°C) for 30 days, then removed from the freezer and cooled to 25°C. The first exposure sensitivity was evaluated as a reference index based on the method for evaluating exposure sensitivity (minimum required exposure amount) described below. Next, 10.00 g of each positive photosensitive pigment composition was dropped into the same 50 mL transparent glass vials described above, which were then sealed and stirred for 1 minute to bring the entire inner wall surface of the vial into contact with and wet the positive photosensitive pigment composition. After allowing the vials to stand for 7 days in a thermostatic chamber maintained at atmospheric pressure / a liquid temperature of 25±1°C, the vials were opened, and the second exposure sensitivity was evaluated. The above evaluations were performed under yellow light, which does not expose component (c) to light.

[0209] The higher the second exposure sensitivity, that is, the smaller the minimum exposure dose required after standing for 7 days in a constant temperature room, the better the film is. Evaluation was performed based on the following criteria, with AA and A to C being considered as pass, and D to E being considered as fail. However, if the film could not be formed with the specified film thickness or if the maximum exposure dose condition (300 mJ / cm) was exceeded, the film was considered to be unsatisfactory. ２ ) but it was difficult to evaluate the exposure sensitivity (required minimum exposure dose) due to problems such as not being able to form an opening due to lack of resolution, the sample was rated as F and was rejected. ２ , or 50 mJ / cm ２ A: The minimum required exposure amount is 60 mJ / cm ２ , or 70 mJ / cm ２ B: The minimum required exposure dose is 80 to 100 mJ / cm２ C: The minimum required exposure amount is 110 to 150 mJ / cm ２ D: The minimum required exposure amount is 160 to 250 mJ / cm ２ E: The minimum required exposure amount is 260 to 300 mJ / cm ２ F: It is difficult to evaluate the exposure sensitivity.

[0210] <Method for evaluating exposure sensitivity (minimum required exposure dose)> A silver alloy film (an alloy consisting of 99.00 mass % silver and 1.00 mass % copper) was formed on the entire surface of an alkali-free glass substrate measuring 150 mm long and 150 mm wide by a sputtering method. An ITO film was then formed on the entire surface by a sputtering method, thereby obtaining a glass substrate having a silver alloy film / ITO film on the entire surface of the alkali-free glass substrate.

[0211] The positive photosensitive pigment composition was applied to the ITO surface of a glass substrate having a silver alloy film / ITO film using a spin coater, adjusting the rotation speed so that the final pixel division layer had a film thickness of 1.5 μm and the spacer layer disposed on the surface of the pixel division layer had a film thickness of 1.5±0.1 μm, to obtain a coating film. The coating film was then pre-baked using a hot plate at 110°C under atmospheric pressure for 120 seconds to obtain a pre-baked film, and a positive halftone exposure mask (a mask with an arrangement of 220 fully transparent square portions, each 30.0 μm long and 30.0 μm wide, designed so that the exposure amount in the semi-transparent portions is 15% when the exposure amount in the fully transparent portions is 100% and the exposure amount in the shielding portions is 0%) was aligned using a near-infrared camera (light source wavelength: 800 nm). Using a double-sided alignment single-sided exposure device, the positive halftone exposure mask was exposed to 40 to 300 (mJ / cm ２ The prebaked film was pattern-exposed to a mixture of g, h, and i rays from an ultra-high pressure mercury lamp, with the exposure dose varied in steps of 10 mJ within the range of 10 mJ / 100 mJ (i-ray equivalent value), to obtain an exposed film having exposed, semi-exposed, and unexposed areas within its surface. The pattern exposure was carried out by contacting a positive half-tone exposure mask with the surface of the prebaked film.

[0212] Next, in the development step, development was carried out using a small photolithography developing device (AD-1200; manufactured by Takizawa Sangyo Co., Ltd.) and a 2.38% by weight aqueous solution of tetramethylammonium hydroxide as an alkaline developer, using a paddle method. The paddle method referred to here refers to a method in which the alkaline developer is shower-applied to the surface of the exposed film for 10 seconds, and then allowed to stand until a predetermined development time is reached, followed by development. The development time was within the range of 30 to 100 seconds, and was determined as the value obtained by subtracting the film thickness of the unexposed portion of the developed film formed on the developed film-formed substrate described below from the film thickness of the pre-baked film, i.e., the time until the film loss (μm) in the development step reached 0.8 μm. Furthermore, after rinsing with deionized water for 30 seconds using a shower method, the substrate was dried by idling at 200 rpm for 30 seconds, and a developed film-formed substrate having a developed film was obtained.

[0213] Next, as a curing step, the developed film was heated in air at 250°C 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 measuring exposure sensitivity having a pixel dividing layer and a spacer layer.

[0214] The openings in the pixel division layer were observed using an FPD inspection microscope (MX-61L; manufactured by Olympus Corporation), and the minimum required exposure dose (mJ / cm) was calculated when the openings were opened so that the average opening width of 10 openings in each exposure dose region was within the range of 30.0±0.1 μm. ２ The exposure sensitivity was determined by the measured aperture width for the square apertures resulting from the exposure mask and the circular apertures resulting from the thermal flow in the curing process, and apertures in which foreign matter defects were observed were excluded from the measurement.

[0215] (3) Evaluation of in-plane uniformity of aperture width of pixel division layer The substrate for measuring exposure sensitivity used in the second evaluation of exposure sensitivity described above was observed using an FPD inspection microscope, and the aperture widths of 10 apertures were measured. １ (μm) to the minimum opening width W ２ (μm) minus the value W ３ The smaller the value (μm), the better the result. Evaluation was performed based on the following criteria, with A to C being considered acceptable and D to E being unacceptable.１ and minimum opening width W ２ An example of this is shown in Figure 4. However, this evaluation was not carried out for the positive photosensitive pigment composition for which it was difficult to evaluate the second exposure sensitivity. The aperture width measurement was also carried out for apertures where foreign matter defects were observed. A:W ３ is less than 1.0 μm. ３ is 1.0 μm or more and less than 1.2 μm. ３ is 1.2 μm or more and less than 1.5 μm. ３ is 1.5 μm or more and less than 2.0 μm. ３ However, the thickness is 2.0 μm or more.

[0216] (4) Evaluation of Light-Shielding Property (OD / μm) of Cured Film The positive photosensitive pigment compositions were stored in a freezer (atmospheric pressure / shielded from light, −20° C.±1° C.) for 30 days, then removed from the freezer and the liquid temperature was adjusted to 25° C. 10 g of each positive photosensitive pigment composition was dropped into the same 50 mL transparent glass vials as above, which were then sealed and stirred for 1 minute to bring the entire inner wall surface of the vial into contact with and wet the positive photosensitive pigment composition. The container was left to stand for 7 days in a thermostatic chamber maintained at atmospheric pressure and a liquid temperature of 25±1°C, and then opened. The positive photosensitive pigment composition was applied to the surface of a transparent glass substrate "Tempax (manufactured by AGC Technoglass Co., Ltd.)" using a spin coater, adjusting the rotation speed so that the final cured film would have a thickness of 1.5 μm, to obtain a coating film. The coating film was prebaked at 110°C under atmospheric pressure for 120 seconds using a hot plate (SCW-636; manufactured by Dainippon Screen Mfg. Co., Ltd.), to obtain a prebaked film. A double-sided alignment single-sided exposure device was used to irradiate the entire surface of the prebaked film with mixed rays of g, h, and i from an ultra-high pressure mercury lamp at an exposure dose equivalent to 15% of the second exposure sensitivity (required minimum exposure dose) determined by the above-mentioned method, thereby obtaining an exposed film. Development, rinsing, and drying were carried out in the same manner as in the evaluation of the second exposure sensitivity, thereby obtaining a solid developed film. Using a high-temperature inert gas oven, the developed film was heated in air at 250°C for 1 hour to obtain a substrate for light-blocking evaluation having a solid cured film with a film thickness of 1.5 μm.

[0217] For the substrate for evaluating light-shielding properties, the total optical density (Total OD value) was measured at three locations on the film surface using an optical densitometer (X-Rite Corporation; X-Rite 361T), and the average value was calculated. This value was divided by 1.5, and the value was rounded to one decimal place to obtain the light-shielding property per 1.0 μm of cured film thickness (OD / μm). The higher the OD / μm value, the higher the light-shielding property and the better the cured film. The OD value of Tempax without a cured film was separately measured and found to be 0.00, so the total optical density of the substrate for evaluating light-shielding properties was considered to be the total optical density of the cured film. The thickness of the cured film was measured at three locations on the surface using a stylus film thickness measuring device (Tokyo Seimitsu Co., Ltd.; Surfcom), and the average value was calculated by rounding to one decimal place. For the positive photosensitive pigment compositions for which it was difficult to evaluate the second exposure sensitivity, the light-shielding properties of the cured films were not evaluated.

[0218] (5) Evaluation of the incidence of non-illuminated pixels in organic EL display devices A top-emission organic EL display device was subjected to a 10 mA / cm ２ Each display was driven by a direct current (DC) and 50 light-emitting pixel regions per display were magnified and observed on a monitor at 50x magnification. The total number of unlit pixels observed in five top-emission organic EL display devices fabricated using the same method was divided by the total number of all light-emitting pixels (250), multiplied by 100, and rounded to one decimal place to obtain the unlit pixel incidence (%). When one or more unlit pixels occurred, the incidence was 0.4 to 100.0%. Evaluation was performed based on the following criteria, with AA and A to C being considered acceptable, and D to E being considered unacceptable. For positive-tone photosensitive pigment compositions for which it was difficult to evaluate the second exposure sensitivity, the incidence of unlit pixels was not evaluated. AA: The incidence of unlit pixels was 0.0%. (i.e., no unlit pixels were observed.) A: The incidence of unlit pixels was 0.4% or more but less than 2.0%. B: The incidence rate of non-lighting pixels is 2.0% or more and less than 4.0%. C: The incidence rate of non-lighting pixels is 4.0% or more and less than 6.0%. D: The incidence rate of non-lighting pixels is 6.0% or more and less than 10.0%. E: The incidence rate of non-lighting pixels is 10.0% or more.

[0219] In the synthesis of pigment dispersant solutions 1 to 25 and the synthesis of hydroxyl group-containing acrylic resin solution X described below, the weight average molecular weight (Mw) was determined under the following measurement conditions. GPC apparatus: HLC-8420GPC manufactured by Tosoh Corporation Column: TSKgel SuperAW4000 Guard column: TSK guard column SuperAW-L Eluent: a solution prepared by dissolving 8.67 g of lithium bromide in 10 L of N,N'-dimethylacetamide Analysis sample: a solution prepared by dissolving a resin solution (1 part by mass as resin) in 180 parts by mass of the eluent (Synthesis Example 1: Synthesis of pigment dispersant solution 1) In the first polymerization step, 21.03 g (0.20 mol) of 4-vinylpyridine (manufactured by Tokyo Chemical Industry Co., Ltd.), a monomer serving as a source for introducing repeating unit a, and 0.21 g of AIBN (manufactured by Tokyo Chemical Industry Co., Ltd.), a thermal polymerization initiator, were dissolved in 178.76 g of PGME, an organic solvent, and the mixture was stirred under a nitrogen atmosphere at a liquid temperature of 70°C until a molecular weight of 2,000 was reached. The required heating time was 3 hours. Next, in the second polymerization step, a solution containing 142.55 g (0.80 mol) of 4-hydroxyphenyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.43 g of AIBN dissolved in 706.02 g of PGME was added dropwise. The mixture was stirred at a liquid temperature of 70°C until a molecular weight of 10,000 was reached, and then cooled to terminate the reaction. The required heating time was 6.5 hours. The obtained resin solution was diluted with PGME to obtain a pigment dispersant solution 1 having a solid content of 10.00% by mass.

[0220] １３ C-NMR confirmed that pigment dispersant solution 1 contained a block copolymer having a block chain composed of a repeating unit represented by formula (12) and a repeating unit represented by formula (40). The amounts of each raw material added are shown in Table 1.

[0221]

[0222] Synthesis Example 2: Synthesis of pigment dispersant solution 2 Pigment dispersant solution 2 having a solids content of 10.00 mass % was synthesized in the same manner as in Synthesis Example 1, except that 2-vinylpyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 4-vinylpyridine, in the blending amounts shown in Table 1. １３ ​It was confirmed by C-NMR that pigment dispersant solution 2 contained a block chain composed of a repeating unit represented by formula (10) and a block copolymer having a repeating unit represented by formula (40).

[0223] Synthesis Example 3 Synthesis of Pigment Dispersant Solution 3 Pigment dispersant solution 3 having a solids content of 10.00 mass % was synthesized in the same manner as in Synthesis Example 1, except that 3-vinylpyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 4-vinylpyridine, in the blending amounts shown in Table 1.

[0224] １３ It was confirmed by C-NMR that pigment dispersant solution 3 contained a block copolymer having a block chain composed of a repeating unit represented by formula (11) and a repeating unit represented by formula (40).

[0225] Synthesis Example 4 Synthesis of Pigment Dispersant Solution 4 Pigment dispersant solution 4 having a solids content of 10.00 mass % was synthesized in the same manner as in Synthesis Example 1, except that 5-propyl-2-vinylpyridine (manufactured by Sigma-Aldrich) was used instead of 4-vinylpyridine and the blending amounts shown in Table 1 were used.

[0226] １３ It was confirmed by C-NMR that pigment dispersant solution 4 contained a block copolymer having a block chain composed of a repeating unit represented by formula (15) and a repeating unit represented by formula (40).

[0227] Synthesis Example 5 Synthesis of Pigment Dispersant Solution 5 Pigment dispersant solution 5 having a solids content of 10.00 mass % was synthesized in the same manner as in Synthesis Example 1, except that 2-methyl-1-vinylimidazole (manufactured by Sigma-Aldrich) was used instead of 4-vinylpyridine and the blending amounts shown in Table 2 were used.

[0228] １３ It was confirmed by C-NMR that pigment dispersant solution 5 contained a block copolymer having a block chain composed of a repeating unit represented by formula (26) and a repeating unit represented by formula (40).

[0229]

[0230] ​​​Synthesis Example 6 Synthesis of Pigment Dispersant Solution 6 Pigment dispersant solution 6 having a solids content of 10.00 mass % was synthesized in the same manner as in Synthesis Example 1, except that 4-(1H-imidazol-1-yl)butyl methacrylate (manufactured by Sigma-Aldrich) was used instead of 4-vinylpyridine and in the blending amounts shown in Table 2.

[0231] １３ It was confirmed by C-NMR that pigment dispersant solution 6 contained a block copolymer having a block chain composed of a repeating unit represented by formula (24) and a repeating unit represented by formula (40).

[0232] Synthesis Example 7 Synthesis of Pigment Dispersant Solution 7 Pigment dispersant solution 7 having a solids content of 10.00 mass % was synthesized in the same manner as in Synthesis Example 1, except that 4-(1-imidazolyl)styrene (manufactured by Sigma-Aldrich) was used instead of 4-vinylpyridine and in the blending amounts shown in Table 2.

[0233] １３ It was confirmed by C-NMR that pigment dispersant solution 7 contained a block copolymer having a block chain composed of a repeating unit represented by formula (22) and a repeating unit represented by formula (40).

[0234] Synthesis Example 8 Synthesis of Pigment Dispersant Solution 8 Pigment dispersant solution 8 having a solids content of 10.00 mass % was synthesized in the same manner as in Synthesis Example 1, except that a compound represented by formula (83) (manufactured by Sigma-Aldrich) was used in place of 4-vinylpyridine and in the blending amounts shown in Table 2.

[0235] １３ It was confirmed by C-NMR that pigment dispersant solution 8 contained a block copolymer having a block chain composed of a repeating unit represented by formula (27) and a repeating unit represented by formula (40).

[0236]

[0237] ​​​Synthesis Example 9 Synthesis of Pigment Dispersant Solution 9 Pigment dispersant solution 9 having a solids content of 10.00 mass % was synthesized in the same manner as in Synthesis Example 1, except that a compound represented by formula (84) (manufactured by Aurora Fine Chemicals) was used instead of 4-vinylpyridine and in the blending amounts shown in Table 3.

[0238] １３ It was confirmed by C-NMR that pigment dispersant solution 9 contained a block copolymer having a block chain composed of a repeating unit represented by formula (31) and a repeating unit represented by formula (40).

[0239]

[0240]

[0241] Synthesis Example 10 Synthesis of Pigment Dispersant Solution 10 A pigment dispersant solution 10 having a solids content of 10.00 mass % was synthesized in the same manner as in Synthesis Example 1, except that N,N-dimethyl-4-vinylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 4-vinylpyridine, and 115.82 g (0.65 mol) of 4-hydroxyphenyl methacrylate and 20.42 g (0.15 mol) of 4-allyl-1,2-dihydroxybenzene (manufactured by Tokyo Chemical Industry Co., Ltd.) were used in the blending amounts shown in Table 3.

[0242] １３ C-NMR confirmed that pigment dispersant solution 10 contained a block copolymer having a block chain composed of a repeating unit represented by formula (32), a repeating unit represented by formula (40), and a repeating unit represented by formula (39). (Synthesis Example 11: Synthesis of pigment dispersant solution 11) Pigment dispersant solution 11 having a solids content of 10.00 mass% was synthesized in the same manner as in Synthesis Example 1, except that 21.03 g (0.20 mol) of 2-vinylpyridine was used instead of 4-vinylpyridine, 70.88 g (0.40 mol) of N-(4-hydroxyphenyl)methacrylamide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 91.30 g (0.40 mol) of the compound represented by formula (85) (manufactured by Aurora Fine Chemicals) were used instead of 4-hydroxyphenyl methacrylate, and the blending amounts were as shown in Table 3. ​​

[0243] １３ It was confirmed by C-NMR that pigment dispersant solution 11 contained a block copolymer having a block chain composed of a repeating unit represented by formula (10), a repeating unit represented by formula (41), and a repeating unit represented by formula (46).

[0244]

[0245] Synthesis Example 12 Synthesis of Pigment Dispersant Solution 12 A pigment dispersant solution 12 having a solids content of 10.00 mass % was synthesized in the same manner as in Synthesis Example 1, except that 91.10 g (0.70 mol) of 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 8.61 g (0.10 mol) of methacrylic acid were used instead of 4-hydroxyphenyl methacrylate, and the blending amounts were as shown in Table 3.

[0246] １３ It was confirmed by C-NMR that pigment dispersant solution 12 contained a block copolymer having a block chain composed of a repeating unit represented by formula (12), a repeating unit represented by formula (50), and a repeating unit represented by formula (51).

[0247] Synthesis Example 13 Synthesis of Pigment Dispersant Solution 13 A pigment dispersant solution 13 having a solids content of 10.00 mass % was synthesized in the same manner as in Synthesis Example 1, except that 21.03 g (0.20 mol) of 2-vinylpyridine was used instead of 4-vinylpyridine, and 28.24 g (0.05 mol) of the compound represented by formula (86) (manufactured by NOF Corporation) was used in addition to 133.64 g (0.75 mol) of 4-hydroxyphenyl methacrylate, in the blending amounts shown in Table 4.

[0248] １３ It was confirmed by C-NMR that pigment dispersant solution 13 contained a block copolymer having a block chain composed of a repeating unit represented by formula (10), a repeating unit represented by formula (40), and a repeating unit represented by formula (57).

[0249]

[0250]

[0251] ​​​Synthesis Example 14 Synthesis of Pigment Dispersant Solution 14 A pigment dispersant solution 14 having a solids content of 10.00 mass % was synthesized in the same manner as in Synthesis Example 1, except that 21.03 g (0.20 mol) of 2-vinylpyridine was used instead of 4-vinylpyridine, 26.84 g (0.20 mol) of 4-isopropenylphenol (Mirex (registered trademark) PM, manufactured by Mitsui Chemicals, Inc.) was used instead of 4-hydroxyphenyl methacrylate, and further 24.83 g (0.05 mol) of the compound represented by formula (87) (PME, manufactured by NOF Corporation) and 78.21 g (0.55 mol) of n-butyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) were used in the blending amounts shown in Table 5.

[0252] １３ It was confirmed by C-NMR that pigment dispersant solution 14 contained a block copolymer having a block chain composed of a repeating unit represented by formula (10), a repeating unit represented by formula (37), a repeating unit represented by formula (55), and a repeating unit represented by formula (88).

[0253]

[0254] In formula (88), * represents a binding site.

[0255]

[0256] Synthesis Example 15 Synthesis of Pigment Dispersant Solution 15 A pigment dispersant solution 15 having a solids content of 10.00 mass % was synthesized in the same manner as in Synthesis Example 1, except that 21.03 g (0.20 mol) of 2-vinylpyridine was used instead of 4-vinylpyridine, 34.04 g (0.20 mol) of the compound represented by formula (89) (manufactured by Hefei Home Sunshine Pharma) was used instead of 4-hydroxyphenyl methacrylate, and further 24.83 g (0.05 mol) of the compound represented by formula (87) and 78.21 g (0.55 mol) of n-butyl methacrylate were used in the blending amounts shown in Table 5.

[0257] １３ ​​It was confirmed by C-NMR that pigment dispersant solution 15 contained a block copolymer having a block chain composed of a repeating unit represented by formula (10), a repeating unit represented by formula (44), a repeating unit represented by formula (55), and a repeating unit represented by formula (88).

[0258]

[0259] (Synthesis Example 16: Synthesis of Pigment Dispersant Solution 16) In the first polymerization step, 21.03 g (0.20 mol) of 4-vinylpyridine, 142.55 g (0.80 mol) of 4-hydroxyphenyl methacrylate, and 1.64 g of AIBN were dissolved in 884.78 g of PGME, an organic solvent, and the solution was stirred under a nitrogen atmosphere while maintaining a liquid temperature of 70°C until the Mw reached 10,000. The solution was then cooled to terminate the reaction. The required heating time was 8 hours. PGME was added to the resulting resin solution to dilute it, yielding a pigment dispersant solution 16 with a solids content of 10.00 mass%. Note that the second polymerization step was not performed.

[0260] １３ It was confirmed by C-NMR that pigment dispersant solution 16 did not contain a block copolymer having a block chain composed of repeating unit a, but contained a random copolymer having a repeating unit represented by formula (12) and a repeating unit represented by formula (40). The amounts of each raw material blended are shown in Table 6.

[0261]

[0262] Synthesis Example 17 Synthesis of Pigment Dispersant Solution 17 A pigment dispersant solution 17 having a solids content of 10.00 mass % was synthesized in the same manner as in Synthesis Example 1, except that 4-hydroxyphenyl methacrylate was not used and 24.83 g (0.05 mol) of the compound represented by formula (87) and 106.65 g (0.75 mol) of n-butyl methacrylate were used in the blending amounts shown in Table 7.

[0263] １３ ​​C-NMR confirmed that pigment dispersant solution 17 contained a block copolymer having a block chain consisting of a repeating unit represented by formula (12), a repeating unit represented by formula (55), and a repeating unit represented by formula (88). It was also confirmed that pigment dispersant solution 17 did not contain repeating unit b.

[0264]

[0265] Synthesis Example 18 Synthesis of Pigment Dispersant Solution 18 Pigment dispersant solution 18 having a solids content of 10.00 mass % was synthesized in the same manner as in Synthesis Example 1, except that 2-vinylpyrazine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 4-vinylpyridine, in the blending amounts shown in Table 8.

[0266] １３ C-NMR confirmed that pigment dispersant solution 18 contained a block copolymer having a block chain composed of a repeating unit represented by formula (90) and a repeating unit represented by formula (40). It was also confirmed that pigment dispersant solution 18 did not contain repeating unit a.

[0267]

[0268] In formula (90), * represents a binding site.

[0269]

[0270] Synthesis Example 19 Synthesis of Pigment Dispersant Solution 19 Pigment dispersant solution 19 having a solids content of 10.00 mass % was synthesized in the same manner as in Synthesis Example 1, except that 4-vinylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 4-vinylpyridine, in the blending amounts shown in Table 8.

[0271] １３ C-NMR confirmed that pigment dispersant solution 19 contained a block copolymer having a block chain composed of a repeating unit represented by formula (91) and a repeating unit represented by formula (40). It was also confirmed that pigment dispersant solution 19 did not contain repeating unit a.

[0272]

[0273] In formula (91), * represents a binding site.​​

[0274] The (a) resins contained in the pigment dispersant solutions 1 to 19 obtained in the above synthesis examples and in the pigment dispersant solutions 23 to 25 described below are classified as components (a-1) and (a-2), and information about their respective structures is summarized and shown in Table 9.

[0275]

[0276] Synthesis Example 20: Synthesis of quinone diazide compound a Under a dry nitrogen stream, 21.22 g (0.05 mol) of TrisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) and 36.27 g (0.135 mol) of 5-naphthoquinone diazide sulfonyl chloride were dissolved in 450 g of 1,4-dioxane and the solution was allowed to reach room temperature. To this solution, a solution prepared by dissolving 15.18 g of triethylamine in 50 g of 1,4-dioxane was added dropwise so that the temperature in the system was 35°C or less. After the dropwise addition, the mixture was stirred at 30°C for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. Thereafter, filtration was carried out, and the precipitate that formed was collected. This precipitate was dried in a vacuum dryer to obtain quinone diazide compound a represented by formula (92), which is component (c).

[0277]

[0278] In formula (92), * represents the bonding site with the oxygen atom.

[0279] Synthesis Example 21 Synthesis of quinone diazide compound b A quinone diazide compound b represented by formula (93), which is component (c), was obtained by performing synthesis in the same manner as in Synthesis Example 20, except that 36.27 g (0.135 mol) of 4-naphthoquinone diazide sulfonyl chloride was used instead of 36.27 g (0.135 mol) of 5-naphthoquinone diazide sulfonyl chloride.

[0280]

[0281] In formula (93), * represents a bonding site with an oxygen atom.

[0282] (Production Example 1: Production of Micronized Perylene Black Pigment 1) Micronized perylene black pigment 1, which is a mixed crystal of a compound represented by formula (104) and a compound represented by formula (105), was produced by the same method as the production method of micronized perylene black pigment 1 disclosed in Production Example 1 of Patent Document 5. Micronized perylene black pigment 1 is component (b-1). The content of chlorine atoms contained in micronized perylene black pigment 1 was quantified by ion chromatography, and was found to be less than 2 ppm by mass, which is the lower limit of quantitation.

[0283]

[0284] (Production Example 2: Production of Micronized Dioxazine Pigment 2) Micronized dioxazine pigment 2 was produced by the same method as the production method of micronized dioxazine pigment 2 disclosed in Production Example 6 of Patent Document 5. Micronized dioxazine pigment 2 is a compound represented by the formula (63), ５２ ~R ６１ are all hydrogen atoms, and R ６２ and R ６３ is an ethyl group, and R ６４ and R ６５ is a methyl group, and R ６６ and R ６７ The content of chlorine atoms contained in the finely divided dioxazine pigment 2 was determined by ion chromatography and was found to be 320 ppm by mass.

[0285] (Synthesis Example 21: Synthesis of Polyimide Precursor B) Polyimide precursor B was synthesized by the same method as the synthesis method of polyimide precursor B disclosed in Synthesis Examples 1 and 2 of Patent Document 5. Polyimide precursor B is component (a-2).

[0286] Synthesis Example 22: Synthesis of Pigment Dispersant Solution 20 Dispersant solution b was synthesized using BYK-LPN6919 (manufactured by BYK-Chemie) as a starting material using the same method as the synthesis method for dispersant solution b disclosed in Production Example 2 of Patent Document 1. Dispersant solution b is a PGMEA solution with a solids content of 30.00 mass % of a methacrylic resin having a repeating unit represented by formula (59) and a repeating unit represented by formula (60). Furthermore, dispersant solution b was diluted with PGME to a solids content of 10.00 mass %, and this was used to prepare pigment dispersant solution 20. The solution was transparent with no precipitation or cloudiness observed, and had good solubility in PGME.

[0287] (Synthesis Example 23: Synthesis of Dye B) Dye B was synthesized using C.I. Pigment Red 178 as a starting material by the same method as the synthesis method of dye B disclosed in Synthesis Example 9 of Patent Document 5. Dye B is a compound belonging to the component (b-2).

[0288] Synthesis Example 24: Synthesis of Perylene Blue Pigment 3 100.00 g of PTCBI (Tokyo Chemical Industry Co., Ltd.; a mixture of cis and trans isomers) was dissolved in 400.00 g of 20% by mass fuming sulfuric acid, and the liquid temperature was raised to 70°C while stirring. The liquid was stirred at 70°C for 5 hours to allow the sulfonation reaction to proceed. The mixture was then poured into 9 kg of ice water to obtain a slurry containing a precipitate, which was then filtered off. The precipitate was washed with a mixed liquid (ethanol:water = 80:20 mass ratio), filtered again, and dried under reduced pressure at 80°C for 24 hours. The mixture was then subjected to a dry pulverization treatment using a nanojetmizer, and passed through a stainless steel sieve filter (opening diameter 20 μm) to remove coarse components, yielding Perylene Blue Pigment 3. Analysis using LC-MS and MALDI-TOF MS revealed that Perylene Blue Pigment 3 was a mixture of the compound represented by formula (94), the compound represented by formula (95), the compound represented by formula (96), and the compound represented by formula (97). The total content of the compound represented by formula (96) and the compound represented by formula (97) was 74 parts by mass in 100 parts by mass of Perylene Blue Pigment 3. Perylene Blue Pigment 3 was component (b-2), and the cumulative 90% secondary particle diameter in the volume-based particle size distribution measured with an MT3000II (manufactured by MICROTRAC Corporation) was 5 μm.

[0289]

[0290] Synthesis Example 25: Synthesis of Perylene Blue Solution 100.00 g of PTCBI was dissolved in 400.00 g of 20% by mass fuming sulfuric acid, and the liquid temperature was raised to 80°C while stirring. The solution was stirred at 80°C for 8 hours to allow the sulfonation reaction to proceed. The solution was then poured into 15 kg of ice water, stirred, and filtered to obtain a wet cake. The wet cake was washed with a mixed solution (ethanol:water = 80:20 mass ratio) until the sulfate ion concentration was below 50 ppm by mass, and then filtered. Deionized water was then added to obtain a perylene blue solution with a solids content of 1% by mass. LC-MS and MALDI-TOF MS were used to confirm that the perylene blue solution was an aqueous solution of a disulfonic acid derivative of PTCBI.

[0291] Synthesis Example 26: Synthesis of Perylene Blue Pigment 4 3,000.00 g of the perylene blue solution (solid content 1% by mass) synthesized in Synthesis Example 25 was placed in a flask, and 533.60 g of a 5% by mass aqueous solution of hexadecyltrimethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added with stirring. The mixture was stirred at a liquid temperature of 50°C for 12 hours and then allowed to stand for 7 days. The precipitate was then washed with a mixed solution (PGME:PGMEA = 50:50 by mass ratio), the dissolved filtrate was discarded, and the residue was washed with deionized water and filtered again. The mixture was dried under reduced pressure at 80°C for 24 hours, subjected to a dry pulverization treatment using a nanojetmizer, and passed through a stainless steel sieve filter (opening diameter 20 μm) to remove coarse components, thereby obtaining perylene blue pigment 4, which is a mixture of the compound represented by formula (106) and the compound represented by formula (107). Perylene blue pigment 4 was component (b-2), and the cumulative 90% secondary particle diameter in the volume-based particle size distribution measured with an MT3000II was 5 μm. The suspension slurry (perylene blue pigment 4:deionized water = mass ratio 1:99) showed a pH of 3.9, and perylene blue pigment 4 was considered to be insoluble particles having an acidic surface.

[0292]

[0293] Synthesis Example 27: Synthesis of Perylene Blue Pigment 5 3,000.00 g of the perylene blue solution (solid content 1% by mass) synthesized in Synthesis Example 25 was placed in a flask, and 562.88 g of a 5% by mass aqueous solution of hexadecylpyridinium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added with stirring. The mixture was stirred at a liquid temperature of 50°C for 12 hours and then allowed to stand for 7 days. The precipitate was then washed with a mixed solution (PGME:PGMEA = 50:50 by mass ratio), the dissolved filtrate was discarded, and the residue was washed with deionized water and filtered again. The mixture was dried under reduced pressure at 80°C for 24 hours, subjected to a dry pulverization treatment using a nanojetmizer, and passed through a stainless steel sieve filter (opening diameter 20 μm) to remove coarse components, thereby obtaining perylene blue pigment 5, which is a mixture of the compound represented by formula (108) and the compound represented by formula (109). Perylene blue pigment 5 was component (b-2), and the cumulative 90% secondary particle diameter in the volume-based particle size distribution measured with an MT3000II was 5 μm. The suspension slurry (perylene blue pigment 5:deionized water = mass ratio 1:99) showed a pH of 4.1, and perylene blue pigment 5 was considered to be insoluble particles having an acidic surface.

[0294]

[0295] Synthesis Example 28: Synthesis of Perylene Blue Pigment 6 Perylene Blue Pigment 6 was obtained in the same manner as in Synthesis Example 26, except that 562.88 g of a 5% by mass aqueous solution of benzyldodecyldimethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of the 5% by mass aqueous solution of hexadecyltrimethylammonium bromide. Perylene Blue Pigment 6 is component (b-2), and in formula (98), R ８８ , and R ８９ is a methyl group, and R ９０ is a benzyl group, and R ９１ is an alkyl group having 12 carbon atoms, and a compound represented by the formula (99), ９３ , and R ９４ is a methyl group, and R ９５ is a benzyl group, and R ９６is an alkyl group having 12 carbon atoms. The cumulative 90% secondary particle diameter in the volume-based particle size distribution measured with an MT3000II was 5 μm. The suspension slurry (Perylene Blue Pigment 6:deionized water = mass ratio 1:99) showed a pH of 3.8, and Perylene Blue Pigment 6 was considered to be insoluble particles with an acidic surface.

[0296] Synthesis Example 29 Synthesis of Hydroxyl Group-Containing Acrylic Resin Solution X A flask equipped with a condenser and a stirrer was charged with 750.00 g of PGME, and 38.57 g of dimethyl 2,2-azobis(isobutyrate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added and dissolved. Next, 128.17 g (1.00 mol) of n-butyl acrylate (Tokyo Chemical Industry Co., Ltd.), 77.11 g (0.50 mol) of cyclohexyl acrylate (Tokyo Chemical Industry Co., Ltd.), 68.76 g (0.33 mol) of dicyclopentanyl acrylate (Tokyo Chemical Industry Co., Ltd.), 30.37 g (0.17 mol) of 3,4-epoxycyclohexylmethyl acrylate (Tokyo Chemical Industry Co., Ltd.), 36.03 g (0.50 mol) of acrylic acid (Tokyo Chemical Industry Co., Ltd.), 111.82 g (0.83 mol) of 4-isopropenylphenol, and 29.87 g (0.17 mol) of N-cyclohexylmaleimide (Nippon Shokubai Co., Ltd.) were added and the mixture was placed under a nitrogen atmosphere. The temperature was raised to 80°C and heated for 5 hours, then cooled to a liquid temperature of 23°C, and diluted with PGME to prepare a solution of component (a-2) with a solid content of 30.00 mass%, which was designated as hydroxyl group-containing acrylic resin solution X. The Mw was 23,000.

[0297] Preparation Example 1: Preparation of Pigment Dispersion Liquid 1 To 720.00 g of a mixed solvent (PGME:ethyl lactate:GBL = mass ratio 50:40:10), 40.00 g of TR4020G (manufactured by Asahi Organic Chemicals Co., Ltd.; hydroxyl group-containing novolak resin having a structure derived from m-cresol and a structure derived from p-cresol) was added and stirred for 30 minutes to dissolve. Further, 200.00 g of Pigment Dispersant Solution 1 and 12.00 g of Perylene Blue Pigment 3 were added and stirred for 5 minutes, after which 28.00 g of Micronized Dioxazine Pigment 2 was added and stirred for 30 minutes to obtain a pre-mixed liquid. The pre-mixed liquid was then sent to a vertical bead mill (Ultra Apex Mill Advance (registered trademark) manufactured by Hiroshima Metal & Machinery Co., Ltd.) whose vessel was filled with 0.05 mm diameter zirconia beads (Toray Industries, Inc.) at a filling rate of 75% by volume. A wet media dispersion treatment was performed using a circulation system at a peripheral speed of 10 m / s for 5 hours, yielding Pigment Dispersion Liquid 1 with a solids content of 10.00% by mass. A first filtration was performed using a 0.8 μm diameter filter, followed by a second filtration using a 0.2 μm diameter filter. It was confirmed that there was no change in the solids content measured to two decimal places before and after filtration. The mass ratio of the solids content of Pigment Dispersion Liquid 1 was 70:30:50:100 for component (b-1):component (b-2):component (a-1):component (a-2). The blending amounts of each raw material are shown in Table 10.

[0298]

[0299] (Preparation Examples 2 to 19: Preparation of Pigment Dispersions 2 to 19) Pigment Dispersions 2 to 19 were prepared in the same manner as in Preparation Example 1, except that Pigment Dispersant Solutions 2 to 19 were used, respectively, instead of Pigment Dispersant Solution 1. The blending amounts of each raw material are shown in Tables 10 to 14.

[0300]

[0301]

[0302]

[0303]

[0304] (Preparation Example 20: Preparation of pigment dispersion 20) Pigment dispersion 20 was prepared in the same manner as in Preparation Example 1, except that pigment dispersant solution 1 was not used and the blending amounts of each raw material shown in Table 14 were used.

[0305] Preparation Example 21: Preparation of Pigment Dispersion Liquid 21 52.57 g of Polyimide Precursor B was added to 757.70 g of a mixed solvent (PGME:ethyl lactate:GBL = mass ratio 50:40:10) and dissolved by stirring for 30 minutes. Further, 158.11 g of Pigment Dispersant Solution 1 and 4.59 g of Dye B were added and stirred for 5 minutes, after which 18.92 g of Micronized Perylene Black Pigment 1 and 8.11 g of Micronized Dioxazine Pigment 2 were added and stirred for 30 minutes to obtain a preliminary stirred solution. The pre-mixed liquid was then sent to a vertical bead mill (Ultra Apex Mill Advance®; manufactured by Hiroshima Metal & Machinery Co., Ltd.) whose vessel was filled with 0.05 mm diameter zirconia beads (Toray Industries, Inc.) at a filling rate of 75% by volume. A wet media dispersion process was performed using a circulation system at a peripheral speed of 10 m / s for 5 hours, yielding Pigment Dispersion Liquid 21 with a solids content of 10.00% by mass. The first filtration was performed using a 0.8 μm diameter filter, followed by a second filtration using a 0.2 μm diameter filter. It was confirmed that there was no change in the solids content measured to two decimal places before and after filtration. The mass ratio of the solids content of Pigment Dispersion Liquid 21 was 100:17:59:195 (component (b-1): component (b-2): component (a-1): component (a-2). The blending amounts of each raw material are shown in Table 15.

[0306]

[0307] (Preparation Example 22: Preparation of Pigment Dispersion 22) Pigment dispersion 22 was prepared in the same manner as in Preparation Example 21, except that pigment dispersant solution 2 was used instead of pigment dispersant solution 1. The blending amounts of each raw material are shown in Table 15.

[0308] (Preparation Example 23: Preparation of Pigment Dispersion 23) Pigment Dispersion 23 was prepared in the same manner as in Preparation Example 21, except that pigment dispersant solution 1 was not used and the blending amounts shown in Table 16 were used. Pigment Dispersion 23 is the same as Pigment Dispersion 19 disclosed in Patent Document 5.

[0309]

[0310] (Preparation Examples 24 to 27: Preparation of Pigment Dispersions 24 to 27) BYK-LPN6919 was diluted with PGME to a solid content of 10.00% by mass, and the resulting solution was used as pigment dispersant solution 21. １ Analysis by H-NMR and measurement of the amine value (mg KOH / g) confirmed that BYK-LPN6919 is completely identical in repeating unit structure, molar ratio, and amine value to "Dispersant-I" disclosed in the examples of Patent Document 3.

[0311] Meanwhile, "Dispersant 4" (solid content 100% by mass) disclosed in an example of Patent Document 4 was dissolved in PGME to give a solution with a solid content of 10.00% by mass, which was designated as pigment dispersant solution 22. All of the dispersants were transparent without any precipitation or cloudiness upon dilution, and had good solubility in PGME.

[0312] Pigment Dispersions 24 to 27 were prepared in the same manner as in Preparation Example 21, except that Pigment Dispersant Solutions 20 to 22 were used instead of Pigment Dispersant Solution 1 in the amounts shown in Table 16.

[0313] Example 1 Under yellow light, 2.64 g of TR4020G, 0.96 g of quinone diazide compound a, 0.60 g of quinone diazide compound b, 1.20 g of 4,4′,4″-trihydroxytriphenylmethane (manufactured by Tokyo Chemical Industry Co., Ltd.) as component (e), and 1.3 g of component (f) were added to 40.41 g of a mixed solvent (PGME:ethyl lactate:GBL=mass ratio 50:40:10). 2 g of HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.) and 0.07 g of a leveling agent, BYK-333 (manufactured by BYK-Chemie), in a PGME solution with a solids content of 5% by mass were added and stirred for 30 minutes to dissolve. 52.80 g of Pigment Dispersion 1 was then added and stirred for 30 minutes to obtain a positive-type photosensitive pigment composition 1 with a solids content of 12.00% by mass. The blending amounts of each raw material are shown in Table 17.

[0314]

[0315] Using the methods described above, the amount of semi-dry film-like foreign matter generated, the first exposure sensitivity, the second exposure sensitivity, the in-plane uniformity of the opening width, and the light-shielding properties of the cured film were evaluated. The evaluation results are shown in Tables 18 and 19.

[0316]

[0317]

[0318] Next, a top-emission organic EL display device was fabricated using the following method, which included a cured film containing a cured product of positive-type photosensitive pigment composition 1 as a pixel dividing layer and a spacer layer, and the incidence (%) of unlit pixels was evaluated. The fabrication process is shown in Figure 5.

[0319] A silver alloy film (99.00% by mass of silver and 1.00% by mass of copper) was formed on the entire surface of an alkali-free glass substrate 17 measuring 70 mm in length and 70 mm in width by sputtering. Using an alkali-soluble novolac-based positive resist, the substrate was immersed in a silver alloy etching solution at a solution temperature of 30°C and etched to obtain a patterned silver alloy film 18 with a thickness of 100 nm. Furthermore, a metastable amorphous ITO (indium-tin oxide) film was formed on the entire surface by sputtering. The alkali-soluble novolac-based positive resist was immersed in a 5% by mass oxalic acid solution at a solution temperature of 50°C for 5 minutes, shower-washed with deionized water for 2 minutes, and then dried with an air blower to form a 10 nm-thick, patterned amorphous ITO film. This was then subjected to low-temperature annealing at 150°C for 30 minutes in a dry nitrogen atmosphere to obtain a low-crystalline ITO film 19. Through the above steps, a first electrode-forming substrate was obtained, which was provided with a first electrode consisting of a laminated pattern of silver alloy film / low-crystalline ITO.

[0320] Positive photosensitive pigment composition 1 was stored in a freezer (atmospheric pressure / shielded from light, -20°C±1°C) for 30 days, then removed from the freezer and the liquid temperature was adjusted to 25°C. Five 50 mL transparent glass vials were prepared by dripping 10.00 g of positive photosensitive pigment composition 1 into each vial and sealing them, and the vials were stirred for one minute to wet the entire inner wall surface with positive photosensitive pigment composition 1. After standing for seven days in a thermostatic chamber maintained at atmospheric pressure / liquid temperature of 25±1°C, the five vials were stirred for 10 minutes, then opened, inverted, and held for one minute. The dropped liquid was poured into a 100 mL container, and the mixed liquid was applied to the surface of first electrode-forming substrate 1 using a spin coater, adjusting the rotation speed so that the final pixel division layer had a film thickness of 1.5 μm and the spacer layer disposed on the surface of the pixel division layer had a film thickness of 1.5±0.1 μm, to obtain a coating film.

[0321] The coating film was then prebaked at 110°C for 120 seconds under atmospheric pressure using a hot plate to obtain a prebaked film. Using a positive halftone exposure mask (a mask with 220 fully transparent squares, each 30.0µm long and 30.0µm wide, arranged such that the exposure in the semi-transparent areas is 15% when the exposure in the fully transparent areas is 100% and the exposure in the opaque areas is 0%), the prebaked film was pattern-exposed to mixed rays of g, h, and i from an ultra-high pressure mercury lamp using a double-sided alignment single-sided exposure device at the minimum required exposure dose (i.e., the second exposure sensitivity), to obtain an exposed film having exposed, semi-exposed, and unexposed areas within its surface. The pattern exposure was performed by contacting the positive halftone exposure mask with the surface of the prebaked film.

[0322] Next, a developing step and a curing step were carried out in the same manner as in the second exposure sensitivity measurement method, thereby obtaining a pixel division layer / spacer layer-formed substrate 1 having a pixel division layer / spacer layer 20. The film thickness of the pixel division layer was 1.5 μm, and the film thickness of the portion where the pixel division layer and the spacer layer were stacked was 3.0 μm.

[0323] Next, in order to form the organic EL layer 21 including the light-emitting layer by vacuum deposition, a vacuum of 1×10 －３Under evaporation conditions of 0.1 Pa or less, the pixel dividing layer / spacer layer-forming substrate 1 was rotated relative to the evaporation source, and first, a compound (HT-1) represented by structural formula (110) was deposited to a thickness of 10 nm as a hole injection layer, and a compound (HT-2) represented by structural formula (111) was deposited to a thickness of 50 nm as a hole transport layer. Next, on the light-emitting layer, a compound (GH-1) represented by structural formula (112) was deposited to a thickness of 40 nm as a host material, and a compound (GD-1) represented by structural formula (113) was deposited to a thickness of 40 nm. Next, a compound (ET-1) represented by structural formula (115) and a compound (LiQ) represented by structural formula (114) were deposited to a thickness of 40 nm as electron transport materials in a volume ratio of 1:1.

[0324] Next, a 2-nm thick compound (LiQ) was vapor-deposited, followed by pattern-deposition of a silver / magnesium alloy (volume ratio 10:1) to form a 30-nm-thick second electrode 22, thereby forming 50 of the 220 openings in the pixel division layer as light-emitting pixel areas. The resulting structure was then sealed by bonding a cap-shaped glass plate using an epoxy resin adhesive under a low-humidity / nitrogen atmosphere, resulting in a top-emission organic EL display device 1. The thicknesses of the layers constituting the organic EL layer 21 and the second electrode were very thin compared to the pixel division layer described above, making them difficult to measure with high accuracy using a stylus-type film thickness measurement device. Therefore, the thicknesses were measured using a quartz crystal oscillator film thickness monitor, which is suitable for thin films less than 100 nm, and the average value of three in-plane measurements, rounded to the nearest tenth, was used as the film thickness.

[0325]

[0326] Four additional units of the same organic EL display device 1 as described above were produced using the same method, and a total of five units of the top-emission type organic EL display device 1 were evaluated for the rate of occurrence (%) of non-lighted pixels using the method described above. The results are shown in Table 19.

[0327] (Examples 2 to 16) Positive photosensitive pigment compositions 2 to 16 were prepared in the same manner as in Example 1, except that pigment dispersions 2 to 16 were used instead of pigment dispersion 1. Using the methods described above, the amount of semi-dry film-like foreign matter generated, the first exposure sensitivity, the second exposure sensitivity, the light-blocking ability of the cured film, and the incidence of unlit pixels were evaluated. The evaluation results are shown in Tables 18 and 19. The blending amounts of each raw material are shown in Tables 17 and 20 to 22.

[0328]

[0329]

[0330]

[0331] Comparative Examples 1 to 4 Positive photosensitive pigment compositions 17 to 20 were prepared in the same manner as in Example 1, except that pigment dispersions 17 to 20 were used instead of pigment dispersion 1. Positive photosensitive pigment compositions 17 to 20 do not contain component (a-1). The blending amounts of each raw material are shown in Table 23. Using the methods described above, the amount of semi-dry film-like foreign matter generated, the first exposure sensitivity, the second exposure sensitivity, the light-blocking ability of the cured film, and the incidence of unlit pixels were evaluated. The evaluation results are shown in Tables 24 and 25.

[0332]

[0333]

[0334]

[0335] Examples 17 and 18 Positive photosensitive pigment compositions 21 and 22 were prepared in the same manner as in Example 1, except that pigment dispersion 1 was replaced with pigment dispersion 21 and 22, respectively, polyimide precursor B was used instead of TR4020G, and the blending amounts of each raw material were as shown in Table 26. Using the methods described above, the amount of semi-dry film-like foreign matter generated, the first exposure sensitivity, the second exposure sensitivity, the light-blocking ability of the cured film, and the incidence of unlit pixels were evaluated. The evaluation results are shown in Tables 24 and 25.

[0336]

[0337] Comparative Examples 5 to 9 Positive-type photosensitive pigment compositions 23 to 27 were prepared in the same manner as in Example 1, except that pigment dispersions 24 to 27 were used instead of pigment dispersion 1, polyimide precursor B was used instead of TR4020G, and the amounts of each raw material were as shown in Table 27. Positive-type photosensitive pigment compositions 23 to 27 did not contain component (a-1). Using the methods described above, the amount of semi-dry film-like foreign matter generated, the first exposure sensitivity, the second exposure sensitivity, the light-blocking properties of the cured film, and the incidence of unlit pixels were evaluated. The evaluation results are shown in Tables 24 and 25. Note that positive-type photosensitive composition 23 in this specification has the same composition as positive-type photosensitive composition 21 (Example 16) disclosed in Patent Document 5.

[0338]

[0339] Synthesis Example 30 Synthesis of Pigment Dispersant Solution 23 A pigment dispersant solution 23 having a solids content of 10.00% by mass was synthesized in the same manner as in Synthesis Example 1, except that 1-vinylimidazole (manufactured by Sigma-Aldrich) was used instead of 4-vinylpyridine, and further methoxytetraethylene glycol methacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.), 2-ethylhexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), and methacrylic acid were used, and a mixed solvent (ethyl lactate:PGMEA=mass ratio of 50:50) was used instead of PGME, and the blending amounts shown in Table 28 were used.

[0340] １３ It was confirmed by C-NMR that pigment dispersant solution 23 contained a block copolymer having a block chain consisting only of the repeating unit represented by formula (21), a repeating unit represented by formula (40), a repeating unit represented by formula (51), a repeating unit represented by formula (116), and a repeating unit represented by formula (117).

[0341]

[0342] In formulas (116) and (117), * represents a binding site.

[0343]

[0344] ​Synthesis Example 31 Synthesis of Pigment Dispersant Solution 24 In the first polymerization step, 14.12 g (0.15 mol) of 1-vinylimidazole, 62.37 g (0.35 mol) of 4-hydroxyphenyl methacrylate, 3.44 g (0.04 mol) of methacrylic acid, 44.21 g (0.16 mol) of methoxytetraethylene glycol methacrylate, 55.28 g (0.30 mol) of 2-ethylhexyl acrylate, and 5.67 g of AIBN were dissolved in 709.12 g of a mixed solvent (ethyl lactate:PGMEA = mass ratio 50:50). The solution was stirred under a nitrogen atmosphere while maintaining a liquid temperature of 70°C until the Mw reached 10,000, and then cooled to terminate the reaction. The required heating time was 5 hours. The obtained resin solution was diluted with a mixed solvent (ethyl lactate:PGMEA=mass ratio 50:50) to obtain a pigment dispersant solution 24 with a solid content of 10.00 mass %. The second polymerization step was not carried out.

[0345] １３ C-NMR confirmed that pigment dispersant solution 24 did not contain a block copolymer having a block chain composed of repeating unit a, but contained a random copolymer having repeating units represented by formula (21), (40), (51), (116), and (117). The amounts of each raw material added are shown in Table 29.

[0346]

[0347] Synthesis Example 32 Synthesis of Pigment Dispersant Solution 25 Pigment dispersant solution 25 having a solids content of 10.00 mass % was synthesized in the same manner as in Synthesis Example 1, except that methoxytetraethylene glycol methacrylate, 2-ethylhexyl acrylate, and methacrylic acid were further used, a mixed solvent (ethyl lactate:PGMEA = mass ratio of 50:50) was used instead of PGME, and the blending amounts were as shown in Table 30.

[0348] １３ ​​It was confirmed by C-NMR that pigment dispersant solution 25 contained a block copolymer having a block chain consisting only of the repeating unit represented by formula (12), a repeating unit represented by formula (40), a repeating unit represented by formula (51), a repeating unit represented by formula (116), and a repeating unit represented by formula (117).

[0349]

[0350] Preparation Example 28: Preparation of pigment dispersion 28 To 676.00 g of a mixed solvent (ethyl lactate:PGMEA = mass ratio 50:50), 212.00 g of hydroxyl group-containing acrylic resin solution X and 84.00 g of pigment dispersant solution 23 were added and stirred for 5 minutes, and then 28.00 g of perylene blue pigment 3 was added and stirred for 30 minutes to obtain a preliminary stirred liquid. Next, the pre-stirred liquid was sent to a vertical bead mill "Ultra Apex Mill Advance (registered trademark)" (manufactured by Hiroshima Metal & Machinery Co., Ltd.) whose vessel was filled with 0.4 mmφ zirconia beads "TORECERAM (registered trademark)" (manufactured by Toray Industries, Inc.) at a filling rate of 75 volume%, and a wet media dispersion treatment was performed for 3 hours using a circulation system at a peripheral speed of 10 m / s. Further, the bead was changed to 0.05 mmφ zirconia beads with the same filling rate of 75 volume%, and a wet media dispersion treatment was performed for 3 hours using a circulation system at a peripheral speed of 8 m / s, yielding pigment dispersion liquid 28 with a solids content of 10.00 mass%. A first filtration was performed using a 0.8 μm diameter filter, and a second filtration was performed using a 0.2 μm diameter filter. It was confirmed that there was no change in the solids content value up to two decimal places before and after filtration. The mass ratio of the solid content of the pigment dispersion 28 was (b-2) component:(a-1) component:(a-2) component=28:8.4:63.6. The blending amounts of each raw material are shown in Table 31.

[0351]

[0352] (Preparation Examples 29 to 31: Preparation of Pigment Dispersions 29 to 31) Pigment dispersions 29 to 31 were prepared in the same manner as in Preparation Example 28, except that perylene blue pigments 4 to 6 were used, respectively, instead of perylene blue pigment 3. The light-blocking properties per mass of perylene blue pigments 4 to 6 were lower than the light-blocking property per mass of perylene blue pigment 3. In order to demonstrate the effect of a composition that can produce a cured film having the same light-blocking properties as in Example 19 in Examples 20 to 22 described below, the mass ratio of the solid content of pigment dispersions 29 to 31 was adjusted to be component (b-2):component (a-1):component (a-2)=34.15:7.68:58.17.

[0353] (Preparation Example 32: Preparation of Pigment Dispersion 32) Pigment dispersion 32 was prepared in the same manner as in Preparation Example 28, except that Perylene Blue Pigment 4 was used instead of Perylene Blue Pigment 3, and Pigment Dispersant Solution 23 was not used, and the blending amounts shown in Table 31 were used. The mass ratio of the solid contents of pigment dispersion 32 was component (b-2):component (a-2) = 34.15:65.85. Pigment dispersion 32 does not contain component (a-1).

[0354] (Preparation Examples 33 to 34: Preparation of Pigment Dispersions 33 to 34) Pigment dispersions 33 to 34 were prepared in the same manner as in Preparation Example 28, except that Perylene Blue Pigment 4 was used instead of Perylene Blue Pigment 3, and Pigment Dispersant Solutions 24 and 25 were used instead of Pigment Dispersant Solution 23, in the amounts shown in Table 32.

[0355]

[0356] Example 19 Under yellow light, 2.39 g of hydroxyl group-containing acrylic resin solution X, 0.96 g of quinone diazide compound a, 0.48 g of quinone diazide compound b, 0.72 g of 1,2,4-trihydroxybenzene (component (e)), 0.07 g of MW-100LM (component (f)), and 0.07 g of BYK-333 (leveling agent) in a 5% by weight solids PGME solution were added to 12.82 g of a mixed solvent (ethyl lactate:PGMEA = 50:50 by mass ratio), and the mixture was stirred for 30 minutes to dissolve. Furthermore, 81.60 g of pigment dispersion 28 was added, and the mixture was stirred for 30 minutes to obtain a positive photosensitive pigment composition 28 with a solids content of 12.00% by mass. The blending amounts of each raw material are shown in Table 33.

[0357]

[0358] Using the methods described above, the amount of semi-dry film-like foreign matter generated, the first exposure sensitivity, the second exposure sensitivity, the in-plane uniformity of the aperture width, the light-shielding ability of the cured film, and the rate of non-illuminated pixels were evaluated. The evaluation results are shown in Tables 34 and 35.

[0359]

[0360]

[0361] (Examples 20 to 22) Positive photosensitive pigment compositions 29 to 31 were prepared in the same manner as in Example 19, except that pigment dispersions 29 to 31 were used instead of pigment dispersion 28, in the amounts shown in Table 33. Using the methods described above, the amount of semi-dry film-like foreign matter generated, the first exposure sensitivity, the second exposure sensitivity, the light-shielding ability of the cured film, and the incidence of unlit pixels were evaluated. The evaluation results are shown in Tables 34 and 35.

[0362] (Comparative Example 10) A positive photosensitive pigment composition 32 was prepared in the same manner as in Example 19, using Pigment Dispersion 32 instead of Pigment Dispersion 28, in the amounts shown in Table 30. Using the methods described above, the amount of semi-dry film-like foreign matter generated, the first exposure sensitivity, the second exposure sensitivity, the light-shielding ability of the cured film, and the incidence of unlit pixels were evaluated. The evaluation results are shown in Tables 34 and 35.

[0363] (Examples 23-24) Positive photosensitive pigment compositions 33-34 were prepared in the same manner as in Example 19, except that pigment dispersions 33-34 were used instead of pigment dispersion 28, in the amounts shown in Table 36. Using the methods described above, the amount of semi-dry film-like foreign matter generated, the first exposure sensitivity, the second exposure sensitivity, the light-shielding ability of the cured film, and the incidence of unlit pixels were evaluated. The evaluation results are shown in Tables 34-35.

[0364]

[0365] Reference Example: When the Safety Data Sheet (revised on July 11, 2016) for VALIFAST (registered trademark) BLACK 3804 (an onium salt of C.I. Solvent Black 34 and an amine; manufactured by Orient Chemical Industry Co., Ltd.), which is a black dye, was referenced, it states that "there is a concern that hexavalent chromium may be generated depending on the oxidation conditions" and "depending on the conditions, incineration, etc., may result in hexavalent Cr." Therefore, from the viewpoints of safety for the human body and environmental conservation, it was not possible to evaluate the positive-tone photosensitive dye composition disclosed in Patent Document 6, which contains the black dye.

[0366] The above examples and comparative examples demonstrate the usefulness of the positive photosensitive pigment composition of the present invention, the cured film containing the cured product thereof, the organic EL display device, the electronic device, and the block copolymer.

[0367] Example 1, which employed a component (a-1) having a block chain consisting only of repeating unit a, obtained superior results compared to Example 16, which employed a component (a-1) not having a block chain consisting only of repeating unit a. Furthermore, Example 29, which employed a component (a-1) having a block chain consisting only of repeating unit a, obtained superior results compared to Example 33, which employed a component (a-1) not having a block chain consisting only of repeating unit a. In other words, it can be seen that a block copolymer having a block chain consisting only of repeating unit a and a repeating unit b is preferred.

[0368] Furthermore, it can be seen that in Examples 20 to 22, which employed as the component (a-1) a block copolymer having a block chain consisting only of a repeating unit represented by formula (9), a repeating unit represented by formula (33), and a repeating unit represented by formula (54), and which employed as the component (b-2) one or more compounds selected from the group consisting of a compound represented by formula (98), a compound represented by formula (99), a compound represented by formula (100), and a compound represented by formula (101), the best results were obtained in each of the evaluations (1) to (5) above.

[0369] The positive photosensitive pigment composition of the present invention can be preferably used as a material for forming pixel dividing layers and spacer layers in organic EL display devices, TFT planarizing layers in organic EL display devices, partition walls in quantum dot organic EL display devices (QD-OLEDs), planarizing layers in micro LED displays, black matrices in liquid crystal display devices, black column spacers in liquid crystal display devices, near-infrared-transmitting visible light-shielding films in solid-state imaging devices, etc. In particular, the composition can be particularly preferably used as a material for simultaneously forming pixel dividing layers and spacer layers in bendable, flexible, top-emission organic EL display devices.

[0370] 1: TFT 2: Wiring 3: TFT insulating layer 4: Planarization layer 5: First electrode 6: Substrate 7: Contact hole 8: Pixel dividing layer 9: Spacer layer 10: Light-emitting pixel 11: Second electrode 12: Vial lid 13: Vial 14: Positive photosensitive pigment composition 15: Vial 16: Semi-dry film-like foreign matter 17: Alkali-free glass substrate 18: Silver alloy film 19: Low-crystalline ITO film 20: Pixel dividing layer / spacer layer 21: Organic EL layer 22: Second electrode

Claims

1. A positive photosensitive pigment composition comprising (a) a resin, (b) an organic pigment, (c) a photoacid generator, and (d) an organic solvent, wherein the resin (a) comprises (a-1) a resin having a repeating unit a and a repeating unit b, the repeating unit a being one or more selected from the group consisting of a repeating unit represented by formula (1), a repeating unit represented by formula (2), a repeating unit represented by formula (3), a repeating unit represented by formula (4), and a repeating unit represented by formula (5), and the repeating unit b is a repeating unit represented by formula (6). In the formulas (1), (2), (3), (4), (5), and (6), * represents a binding site, R １ , R ４ , R ７ , R １１ , R １５ and R ２０ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R ２ , R ５ , R ８ , R １２ , and R １６ each independently represents a single bond or a divalent linking group having 1 to 8 carbon atoms and not containing a nitrogen atom, ３ , R ６ , R ９ , R １４ , and R １９ each independently represents an alkyl group having 1 to 3 carbon atoms; １ , n ２ , n ３ , n ４ , and n ５ are integers each independently representing 0 to 2; R １０ and R １３ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R １７ and R １８ each independently represents an alkyl group having 1 to 5 carbon atoms; R ２１ represents a monovalent group having 1 to 30 carbon atoms and containing a hydroxyl group. ２１ does not contain any nitrogen atom other than the nitrogen atom contained in -CONH-.) 2. The positive photosensitive pigment composition according to claim 1, wherein the repeating unit represented by formula (6) comprises a repeating unit containing a monovalent organic group having 6 to 30 carbon atoms and containing one or two phenolic hydroxyl groups.

3. The positive photosensitive pigment composition according to claim 2, wherein the repeating unit represented by formula (6) includes a repeating unit represented by formula (33) and / or a repeating unit represented by formula (34). In formula (33) and formula (34), * represents a binding site, R ３１ and R ３４ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R ３２ and R ３５ each independently represents a single bond or a divalent linking group having 1 to 8 carbon atoms; R ３３ , R ３６ , and R ３７ each independently represents an alkyl group having 1 to 3 carbon atoms; ９ is an integer number representing 1 or 2; １０ , n １１ , n １２ , n １３ , n １４ are integers, each independently representing 0 to 2. ３２ and R ３５ does not contain any nitrogen atom other than the nitrogen atom contained in -CONH-, １１ and １２ The sum of n is 0 to 3, １２ and １４ The sum of is 1 or 2.) 4. The positive photosensitive pigment composition according to claim 1, wherein the resin (a-1) having the repeating unit a and the repeating unit b is a block copolymer having a block chain consisting of only the repeating unit a and the repeating unit b.

5. The positive photosensitive pigment composition according to claim 1, wherein the resin (a-1) having the repeating unit a and the repeating unit b further has a repeating unit c, which is a repeating unit represented by formula (54). (In formula (54), * represents a binding site, R ３８ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R ３９ represents -COO- or -O-; R ４０ represents an alkylene group having 1 to 3 carbon atoms; １５ is an integer ranging from 2 to 30; R ４１ represents a phenyl group substituted with an alkyl group having 1 to 10 carbon atoms, an unsubstituted phenyl group, or an alkyl group having 1 to 10 carbon atoms.

6. The positive photosensitive pigment composition according to claim 1, wherein the (b) organic pigment contains (b-2) an organic pigment having a sulfo group.

7. The positive photosensitive pigment composition according to claim 6, wherein the component (b-2) contains at least one compound selected from the group consisting of a compound represented by formula (98), a compound represented by formula (99), a compound represented by formula (100), and a compound represented by formula (101). (In formula (98), formula (99), formula (100), and formula (101), R ８７ , R ９２ , R ９７ , and R １００ Each independently represents -SO ３ H, or -SO ３ － represents R ８８ , R ８９ , R ９０ , R ９１ , R ９３ , R ９４ , R ９５ , and R ９６ each independently represents a phenyl group, a benzyl group, or an alkyl group having 1 to 20 carbon atoms; R ９８ , and R １０１ each independently represents an alkyl group having 1 to 20 carbon atoms; R ９９ , and R １０２ each independently represents an alkyl group having 1 to 3 carbon atoms; １６ , and n １７ are integers, each independently representing 0 to 2. ８８ , R ８９ , R ９０ , and R ９１ one or two of the groups are a phenyl group, a benzyl group, or an alkyl group having 8 to 20 carbon atoms; R ９３ , R ９４ , R ９５ , and R ９６ Among these, one or two groups are a phenyl group, a benzyl group, or an alkyl group having 8 to 20 carbon atoms.

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

9. An organic EL display device comprising the cured film according to claim 8.

10. An electronic device comprising the organic EL display device according to claim 9.

11. A block copolymer having a block chain consisting only of repeating unit a and repeating unit b, wherein the repeating unit a is one or more selected from the group consisting of repeating units represented by formula (1), repeating units represented by formula (2), repeating units represented by formula (3), repeating units represented by formula (4), and repeating units represented by formula (5), and the repeating unit b is a repeating unit represented by formula (33) and / or a repeating unit represented by formula (34). In the formulas (1), (2), (3), (4), and (5), * represents a binding site, R １ , R ４ , R ７ , R １１ , and R １５ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R ２ , R ５ , R ８ , R １２ , and R １６ each independently represents a single bond or a divalent linking group having 1 to 8 carbon atoms and not containing a nitrogen atom, ３ , R ６ , R ９ , R １４ , and R １９ each independently represents an alkyl group having 1 to 3 carbon atoms; １ , n ２ , n ３ , n ４ , and n ５ are integers each independently representing 0 to 2; R １０ and R １３ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R １７ and R １８ each independently represents an alkyl group having 1 to 5 carbon atoms. In formula (33) and formula (34), * represents a binding site, R ３１ and R ３４ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R ３２ and R ３５ each independently represents a single bond or a divalent linking group having 1 to 8 carbon atoms; R ３３ , R ３６ , and R ３７ each independently represents an alkyl group having 1 to 3 carbon atoms; ９ is an integer number representing 1 or 2; １０ , n １１ , n １２ , n １３ , n １４ are integers, each independently representing 0 to 2. ３２ and R ３５ does not contain any nitrogen atom other than the nitrogen atom contained in -CONH-, １１ and １２ The sum of n is 0 to 3, １２ and １４ The sum of is 1 or 2.)

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