WO2025047654A1 - Positive photosensitive pigment composition, cured film containing cured product thereof, organic el display device, electronic apparatus, and block copolymer - Google Patents

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

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

　It is well known that the use of an adsorption mechanism based on acid-base interactions is extremely effective in finely dispersing pigments in organic solvents, inhibiting re-agglomeration, and achieving high dispersion stability. In general, organic pigments are less polar than inorganic pigments, making them more difficult to disperse. Resins that have 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 to the acidic adsorption sites on the organic pigment surface.

For example, in the technical field of negative-type photosensitive pigment compositions containing organic pigments, there has been a frequent demand for pigment dispersants that can exhibit high pigment dispersion performance and that do not impair patterning properties or film properties in photolithography. In other words, pigment dispersants must be designed or selected with due consideration given to the compatibility between pigment dispersion performance and other properties that are important for the application, and since this greatly affects the value of the final product, numerous technical proposals have been made to date.

In light of this background, (meth)acrylic dispersants having an aliphatic tertiary amino group are commonly used in the technical field of negative photosensitive pigment compositions, such as materials for forming color filters of liquid crystal displays, materials for forming black matrices, and materials for forming black column spacers. Patent Document 1 discloses a technology that uses a methacrylic dispersant in which a portion of an aliphatic tertiary amino group is converted to a quaternary ammonium salt (e.g., dispersant solutions a, b, and c in the examples) to achieve good average particle size and contrast, as well as solvent resolubility of the dried film of the negative photosensitive pigment composition that may occur during standby for discharge from a coating device. Patent Document 2 discloses a negative photosensitive pigment composition that achieves low viscosity, contrast, and development speed by using a pigment dispersant with a specific range of amine value derived from an aliphatic tertiary amino group (e.g., dispersants B, C, and D in the examples).

Also, attempts are being made to use pigment dispersants with aliphatic tertiary amino groups as materials for forming black pixel division layers in organic EL display devices. As coloring materials, the use of organic pigments has been proposed mainly due to their excellent insulation 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 has the function of suppressing external light reflection, providing value such as improved visibility and reduced power consumption.

Patent Document 3 discloses a negative-type photosensitive pigment composition containing a methacrylic dispersant in which an aliphatic tertiary amino group or a portion of the group has been converted to a quaternary ammonium salt (e.g., Dispersant-I and -II in the Examples). On the other hand, Patent Document 4 discloses a negative-type photosensitive pigment composition containing an aliphatic tertiary polyamine dispersant in which multiple graft chains of a polyether structure have been introduced into an aliphatic polyamine (e.g., Dispersant 4 in the Examples).

In recent years, from the viewpoint of reducing the manufacturing process costs of organic EL display devices, attempts have been made to develop a technology that uses a halftone exposure mask to simultaneously form a black pixel division layer and a spacer layer that is placed on part of its surface. Compared to negative halftone processing, a black pixel division layer with extremely high in-plane uniformity in the aperture width of the opening can be obtained, and the in-plane variation in the light-emitting pixel size determined by the aperture width can be stably suppressed. Therefore, materials that enable positive halftone processing have attracted attention.

Patent Document 5 discloses a positive-type 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 feature of enabling excellent positive-type halftone processing with high exposure sensitivity, and suppressing the decrease in exposure sensitivity before and after storage in a cool, dark place (atmospheric pressure/shielded from light, -20°C±1°C).

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 organic pigments and high solubility in organic solvents.

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

However, when the positive photosensitive pigment composition disclosed in Patent Document 5 is taken out of a cool, dark place and stored in a sealed container under atmospheric pressure/room temperature (for example, liquid temperature 25±1°C), there is an issue 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. In addition, this issue causes foreign matter defects in the black pixel division layer, and when an organic EL display device is driven, non-lit pixels occur, impairing the display characteristics.

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 degree of improvement in 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 the difficulty of positive halftone processing.

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 human safety and environmental conservation when put into industrial use.

For these reasons, there has been a strong demand for a positive-type photosensitive pigment composition that suppresses the generation of semi-dry film-like foreign matter and that allows the black pixel division layer and spacer layer to be formed in one go with a positive-type halftone process, with stable and high exposure sensitivity.

The present invention is as follows.
[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), which will be described later, and the repeating unit b is a repeating unit represented by formula (6), which will be described later.
[2] The positive photosensitive pigment composition according to [1], wherein the repeating unit represented by formula (6) includes 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) contains a repeating unit represented by formula (33) and/or a repeating unit represented by formula (34) described below.
[4] The positive photosensitive pigment composition according to any one of [1] to [3], wherein the (a-1) resin having the repeating unit a and the repeating unit b is a block copolymer having a block chain consisting only of the repeating unit a and the repeating unit b.
[5] The positive photosensitive pigment composition according to any one of [1] to [4], wherein the (a-1) resin having the repeating unit a and the repeating unit b further has a repeating unit c, and the repeating unit c is a repeating unit represented by formula (54) 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 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), which will be described later.
[8] A cured film comprising a cured product of the positive photosensitive pigment composition according to any one of [1] to [7].
[9] An organic electroluminescence 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 of only 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), which will be described later;
The repeating unit b is a repeating unit represented by formula (33) and/or a repeating unit represented by formula (34) described below.

The present invention provides a positive photosensitive pigment composition that suppresses the generation of semi-dry film-like foreign matter containing pigment aggregates after storage in a sealed container under atmospheric pressure/room temperature, and that can stably form black pixel division layers and spacer layers in one go with positive halftone processing with high exposure sensitivity.

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. FIG. 2 is a schematic diagram of the appearance of a positive photosensitive pigment composition in an example and a comparative example after it is dropped into a glass vial and sealed. FIG. 2 is a schematic diagram of the appearance of semi-dry film-like foreign matter formed on the inner wall surface of a glass vial in the examples and comparative examples. FIG. 2 is a schematic diagram showing an example of the maximum opening width _W1 and the minimum opening width _W2 of the opening of the exposure sensitivity measurement substrate in all the examples and comparative examples. In all of the examples and comparative examples, the process for producing an organic EL display device includes the steps of forming a pixel dividing layer and a spacer layer.

The present invention will be described in detail below. A numerical range expressed using "~" means a range including the numerical values written before and after "~" as the lower and upper limits. The pixel division layer means 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 means light in the wavelength range of 380 nm or more and less than 780 nm, and near ultraviolet light means light in the range of 200 nm or more and less than 380 nm. Near infrared light means light in the wavelength range of 780 nm or more and less than 1300 nm. Light shielding means a function of reducing the intensity of transmitted light relative to the intensity of light incident perpendicularly to the cured film, and light shielding property means the degree of shielding of visible light. Transmittance means 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 analyzed by gel permeation chromatography (hereinafter sometimes referred to as GPC) and converted using a calibration curve based on standard polystyrene.

The "C.I." used to name some colorants is an abbreviation for Colour Index Generic Name, which is based on the Colour Index issued by the Society of Dyers and Colourists, and for colorants that are registered in the Colour Index, the Colour Index Generic Name indicates the chemical structure or crystal form of the pigment or dye. Carbon blacks classified as C.I. Pigment Black 7 are classified as inorganic black pigments. The solid content refers to the proportion (mass%) of the components in the positive photosensitive pigment composition excluding organic solvents and water.

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

Furthermore, it was thought that the principle behind the above-mentioned problem was different from the lack of resolubility in organic solvents of dried films in non-closed environments as disclosed in Patent Document 1. In other words, 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 pigments that are movable in the film are kept in close proximity to each other for a long period of time.

Furthermore, it was 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 undesirable decomposition of the photoacid generator, which is a photosensitizer that imparts positive photosensitivity, causing rapid deterioration. Furthermore, it was found that they capture at least a portion of the acid that is desirably generated in the film in the exposed area during the exposure process, 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 an organic EL display device.

　Until now, no pigment dispersant has been known that is effective in dispersing organic pigments and is suitable for positive-tone photosensitive systems, regardless of whether or not it suppresses the generation of semi-dry film-like foreign matter containing pigment aggregates.

In light of the above, the inventors have conducted extensive research with a focus on allowing the pigment dispersion mechanism based on acid-base interactions to coexist without inhibiting the positive photosensitive mechanism based on acid generation. As a result, they have discovered that a positive photosensitive pigment composition containing a pigment dispersant with a specific structure is particularly effective in solving the problems described above.

That is, the positive photosensitive pigment composition according to the first embodiment of the present invention comprises:
A positive-type photosensitive pigment composition comprising: (a) a resin; (b) an organic pigment; (c) a photoacid generator; and (d) an organic solvent,
The (a) resin contains (a-1) a resin having a repeating unit a and a repeating unit b,
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),
The repeating unit b is a repeating unit represented by formula (6) in the positive photosensitive pigment composition.

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 represent 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 represent a single bond or a divalent linking group having 1 to 8 carbon atoms and not containing a nitrogen atom;
R ³ , R ⁶ , R ⁹ , R ¹⁴ , and R ¹⁹ each independently represent an alkyl group having 1 to 3 carbon atoms;
n 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 represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
R ¹⁷ and R ¹⁸ each independently represent 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.
However, R ²¹ does not contain any nitrogen atom other than the nitrogen atom contained in —CONH—.

The positive photosensitive pigment composition of the present invention has positive photosensitivity. Possessing positive photosensitivity, it is possible to form a pixel division layer with extremely high in-plane uniformity of the aperture width of the opening by positive halftone processing, and it is possible to stably suppress in-plane variation in the light-emitting pixel size determined by the aperture width, thereby manufacturing an organic EL display device with suppressed unevenness in brightness. This effect is the same as that of the positive photosensitive pigment composition disclosed in Patent Document 5.

Positive photosensitivity refers to the property that, when a prebaked film of a photosensitive composition is irradiated with light including near ultraviolet light and exposed, the solubility of the exposed portion of the film in an alkaline developer, which will be described later, becomes higher than the solubility of the unexposed portion of the film in an alkaline developer, which will be described later.

On the other hand, compositions that have 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., have negative photosensitivity, are not included in the positive photosensitive pigment composition of this specification, even if they contain (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, so long as it contains at least water and has a pH of 1.0 or more and less than 7.0 as measured using a pH meter.

The positive photosensitive pigment composition of the present invention contains (a) a resin,
The (a) resin contains (a-1) a resin having a repeating unit a and a repeating unit b,
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),
The repeating unit b is a repeating unit represented by formula (6).

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 represent 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 represent a single bond or a divalent linking group having 1 to 8 carbon atoms and not containing a nitrogen atom;
R ³ , R ⁶ , R ⁹ , R ¹⁴ , and R ¹⁹ each independently represent an alkyl group having 1 to 3 carbon atoms;
n 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 represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
R ¹⁷ and R ¹⁸ each independently represent 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.
However, R ²¹ does not contain any nitrogen atom other than the nitrogen atom contained in —CONH—.

The term (a) resin here refers to a compound that has a polymer chain in which five or more repeating units each having three or more carbon atoms are linked together, and has a Mw of 1,000 or more.

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

The first advantageous feature is that it has the effect of promoting fine dispersion of the organic pigment (b) described below and improving the dispersion stability in the positive photosensitive pigment composition. The improvement in dispersion stability in liquid form broadens the particle size distribution of the pigment and suppresses an increase in the viscosity of the positive photosensitive pigment composition, leading to improved film thickness uniformity of the pixel division layer and spacer layer that are finally obtained.

The second advantageous feature is that when the positive photosensitive pigment composition is stored in a sealed container (e.g., liquid temperature 25±1°C) under atmospheric pressure/room temperature, it has the effect of suppressing the phenomenon in which 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 organic solvents appears on the surface of the inner wall of the container.

The organic solvent referred to here is not particularly limited, but examples include organic solvents that are the same as or have a similar structure to the (d) organic solvent contained in the positive photosensitive pigment composition. Therefore, refilling the positive photosensitive pigment composition makes it easy to remove adhesions due to redispersion of the pigment, and to clean the inside of the container with the organic solvent.

This effect makes it possible to avoid the problem that when the semi-dry film-like foreign matter comes into contact with the cleaning solvent or the positive photosensitive pigment composition, at least a part of it peels off from the inner wall of the container in the form of a film, and gets mixed into the positive photosensitive pigment composition to become an insoluble foreign matter. Furthermore, it is possible to form a pixel division layer and a spacer layer that are excellent in smoothness and free of convex foreign matter defects, and it is possible to manufacture an organic EL display device in which the occurrence of non-lighting pixels is suppressed. The non-lighting pixels referred to here mean light-emitting pixels that are defective parts that do not light up even when a voltage is applied when the organic EL display device is driven and cannot emit light. The fewer the non-lighting pixels, the higher the value of the display device and the more desirable it is. In addition, non-lighting pixels caused by semi-dry film-like foreign matter tend to occur more easily when the film thickness of the second electrode described later is formed. In other words, the second advantageous feature is more useful when the organic EL display device of the present invention described later is a top-emission type organic EL display device.

Changes in the particle size distribution of insoluble components in a positive photosensitive pigment composition caused by at least a portion of the semi-dry film-like foreign matter peeling off in a film-like manner from the inner wall of the container and becoming mixed in can be measured from the maximum particle size (μm) measured using a laser diffraction particle size distribution analyzer "MT3000II (MICROTRAC)" or from image analysis using a laser microscope. On the other hand, the long diameter of insoluble foreign matter is generally 1 μm or more and has poor Brownian motion, making it difficult in principle to measure it using a dynamic light scattering particle size distribution analyzer.

The third advantageous feature is that the positive-tone photosensitive function is not impaired, and since the deterioration of the photoacid generator (c) described below is suppressed, a large amount of acid can be generated in the exposure step, and the phenomenon in which the generated acid is trapped in the film in the exposed area can be suppressed, thereby obtaining high exposure sensitivity.
The high exposure sensitivity here means that the minimum exposure dose required to simultaneously form the pixel division layer having the opening of the desired opening width and the spacer layer by positive halftone processing is small. In other words, the higher the exposure sensitivity, the shorter the exposure time becomes, and the better the productivity of the organic EL display device can be improved. In general, the higher the light-shielding property of the pre-baked film, the less light reaches the bottom of the exposed part of the film in the exposure process, so that the exposure sensitivity tends to be low for the same formed film thickness. Therefore, the third advantageous feature is that the higher the light-shielding property of the pixel division layer to be formed, the greater the effect can be obtained.

The fourth advantageous feature is that component (a-1) has excellent developability in an alkaline developer, which can suppress the generation of development residues.

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

The repeating unit a in component (a-1) has a pigment adsorption group with a nitrogen-containing structure that has a moderately low basicity, and the pigment adsorption group adsorbs to the surface of the organic pigment (b) and exerts an effect as a pigment dispersant. By adjusting the presence or absence of an alkyl group substituted on the aromatic ring in 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).

As the repeating unit a in component (a-1), in order to suppress the generation of semi-dry film-like foreign matter, repeating units in which R ² , R 5 , R ⁸ , R ¹² and R ¹⁶ in formulas (1), (2), (3), ( ⁴ ) and (5) are a single bond, -COO-, an alkylene group having 1 to 8 carbon atoms, or -COO-alkylene group having 1 to 7 carbon atoms are preferred. Here, -COO-alkylene group having 1 to 7 carbon atoms means a group in which a carboxylate bond (-COO-) is bonded to an alkylene group having 1 to 7 carbon atoms.

Among them, 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). It is most preferable to have a repeating unit represented by formula (9) in terms of its high effect of suppressing the generation of non-illuminated pixels.
That is, the positive photosensitive pigment composition of the present invention contains (a) a resin,
The (a) resin contains (a-1) a resin having a repeating unit a and a repeating unit b,
The repeating unit a is at least one selected from the group consisting of a repeating unit represented by formula (7), a repeating unit represented by formula (8), and a repeating unit represented by formula (9),
The repeating unit b is more preferably a repeating unit represented by formula (6).

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

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.

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

The repeating unit b in the (a-1) component has intramolecular and/or intermolecular interactions with the repeating unit a that is not adsorbed to the pigment surface, which further suppresses the deterioration of the photoacid generator (c) described below and suppresses the capture of acid generated in the film, thereby improving exposure sensitivity. 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 the 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.

The repeating unit b is a repeating unit represented by the above formula (6), and ^R21 in formula (6) is a monovalent group containing a hydroxyl group and having 1 to 30 carbon atoms. 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.

However, in formula (6), the hydroxyl group contained in R ²¹ does not include a structure in which a hydrogen atom is bonded to an oxygen atom located at the end of a polyalkylene oxide structure. The polyalkylene oxide structure means a divalent group in which two or more alkylene oxides are bonded in a row, that is, a group represented by -(AO)x-. A represents an alkylene group, and the number of repeating units x represents 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 regarded as a part of the atoms constituting the polyalkylene oxide structure, not as a part of the atoms constituting the hydroxyl group as used herein.

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

As the repeating unit containing a monovalent organic group having 6 to 30 carbon atoms and containing one or two phenolic hydroxyl groups, it is more preferable to include 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).

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

As the repeating unit b in component (a-1), in terms of improving exposure sensitivity, a repeating unit in which R ³² and R ³⁵ in formula (33) and formula (34) are each independently a single bond, -COO-, or -CONH- is more preferable. Depending on the presence or absence of an alkyl group substituted on the aromatic ring in repeating unit b, or the number of carbon atoms in the alkyl group, it is possible to control the affinity in accordance with the polarity of the (d) organic solvent.

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

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

In order to suppress the formation of semi-dry film-like foreign matter, it is preferable that the component (a-1) further contains a repeating unit represented by formula (54) as the repeating unit c. The repeating unit c further increases the affinity of the component (a-1) with the organic solvent (d), improves molecular mobility, and enhances the steric repulsion effect of the component (a-1).
That is, in the positive photosensitive pigment composition of the present invention, it is preferred that the (a-1) resin having the repeating unit a and the repeating unit b further contains a repeating unit c, and that the repeating unit c 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;
n ¹⁵ is an integer of 2 to 30, and 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.
The partial structure represented by -(R ⁴⁰ -O)n ¹⁵ - herein means that the number of carbon atoms in the multiple R ⁴⁰ may be the same or different, and therefore includes, for example, a partial structure represented by -(C ₂ H ₄ O) ₅ -(C ₃ H ₆ O) ₅ -.
R ⁴¹ is preferably a phenyl group substituted with an alkyl group having 1 to 10 carbon atoms, or an unsubstituted phenyl group, in order to suppress the formation of semi-dry film-like foreign matter.

Specific examples of repeating unit c include repeating units represented by formulas (55) to (57).

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

The content of (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 reduce the change in the amount of film loss (described later) with respect to the change in development time. In order to ensure a sufficient content of components other than (a) resin and to achieve both high light blocking properties and high exposure sensitivity, the content is preferably 70 parts by mass or less. The component belonging to (a) resin may be only component (a-1).

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, in order to suppress semi-dry film-like foreign matter.

The method of synthesizing component (a-1) includes copolymerizing a monomer that is the source of repeating unit a, a monomer that is the source of repeating unit b, and, if necessary, a monomer that is the source of repeating unit c, and monomers that are the source of other repeating units. The monomer here means a compound that has one structure represented by formula (58) in the molecule. The other repeating units here mean repeating units that do not belong to repeating unit a, repeating unit b, or repeating unit c.

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

Examples of monomers that can be used as the source of 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 such monomers include 1-(6-hepten-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. These monomers may be used alone or in combination of two or more. The term (meth)acrylate here refers to methacrylate and acrylate. These monomers are commercially available and are easily available as raw materials for pharmaceutical manufacturing intermediates.

Examples of monomers that can be used as the source of 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- Examples of the repeating unit b include mono(2-hydroxyethyl)oxy)ethyl (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. In addition, the 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 monomer to return it to the 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 or more of these may be used in combination. The term (meth)acrylate here refers to methacrylate and acrylate. These monomers are commercially available and are readily available industrially as raw materials for KrF photoresists for semiconductor manufacturing.

Examples of monomers that can be used as the source of introduction of 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 here refers to methacrylate and acrylate. These monomers are readily available commercially as raw materials for paints and color filter forming materials.

Other monomers that can be used as the source of repeating units include, for example, 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.). In addition, 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 used here means methacrylate and acrylate.

Another 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 is the source of introduction of the repeating unit b and glycidyl methacrylate.

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

Component (a-1) may be a resin consisting of only repeating units a and b, but if it further contains repeating unit c, the content of repeating unit c is preferably 1 to 15 mol%.

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) within a range that does not impair the effects of the present invention. In order to suppress a decrease in exposure sensitivity, 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 none at all, per 100.00 parts by mass of the solid content of the positive photosensitive pigment composition. Examples of components containing the repeating unit represented by formula (59) and/or the repeating unit represented by formula (60) include at least "DISPERBYK" (registered trademark)-2000, 2001, 2013, "BYK-LPN" (registered trademark)-6919, 21116, and Efka-4300, among the (a-2) other resins described below.

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

The Mw of component (a-1) is preferably 2000 or more, more preferably 5000 or more, in order to suppress 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. 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, in order to suppress semi-dry film-like foreign matter. 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 adopted. As a GPC column for measuring the molecular weight distribution of component (a-1), for example, Shodex (registered trademark) LF-804 (manufactured by Resonac Co., Ltd.), TSKgel Super AW2500, AW3000, AW4000, AW5000, TSKgel guardcolumn Super AW-L, AW-H (all manufactured by Tosoh Corporation) can be suitably used. As an eluent for measuring the molecular weight distribution, tetrahydrofuran, N,N'-dimethylacetamide, etc. can be suitably used.

The component (a-1) may be a random copolymer or a block copolymer, but is preferably a block copolymer having a block chain consisting of only repeating unit a in order to suppress the generation of semi-dry film-like foreign matter. The block chain consisting of only repeating unit a here means a structure having a molecular weight of 1000 or more in which 10 or more repeating units belonging to repeating unit a are linked together. The arrangement of the repeating units other than the block chain consisting of only repeating unit a in the block copolymer here is not particularly limited.
That is, in the positive photosensitive pigment composition of the present invention, (a-1) the resin having the repeating unit a and the repeating unit b is preferably a block copolymer having a block chain consisting of only the repeating unit a and the repeating unit b.

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

When polymer chain B further contains a repeating unit other than repeating unit b, polymer chain B may have a portion in which repeating units b are randomly arranged, or may contain a block chain consisting of only repeating units b.

In this specification, the term "block copolymer" includes, for example, a so-called graft copolymer formed by adding a macromonomer having a block chain consisting of only repeating unit a, and a so-called gradient copolymer having a linear polymer structure that gradually transitions from hydrophilic to hydrophobic from one molecular end to the other molecular end, as long as the block chain consists of only repeating unit a and repeating unit b.

The Mw of the block chain consisting only of repeating unit a is preferably 1500 to 5000 in order to suppress semi-dry film-like foreign matter.

As a method for copolymerizing the aforementioned monomers to synthesize component (a-1), 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.

Among these, the free radical polymerization method, the nitroxide-mediated radical polymerization method, and the living anionic polymerization method are preferred because they can achieve both suppression of semi-dry film-like foreign matter and high exposure sensitivity, and can also avoid residual heavy metal atoms to obtain high insulation properties.

The method for synthesizing component (a-1) is specifically explained below using as examples a block chain consisting of only repeating unit a and a block copolymer having repeating unit b.

The free radical polymerization method may, for example, be a method in which a monomer that is the source of introduction of repeating unit a is dissolved in an organic solvent, and stirred in the presence of a thermal radical polymerization initiator at a nitrogen atmosphere/liquid temperature of 50 to 120°C for 2 to 30 hours to obtain a polymer consisting of only repeating unit a, and then a monomer that is the source of introduction of repeating unit b, a monomer that is the source of introduction of other repeating units, and optionally a molecular weight distribution regulator are added, and the mixture is stirred at 50 to 120°C for 2 to 30 hours. If there is a large amount of unreacted monomer after obtaining a polymer consisting of only repeating unit a, a purification/removal step may be added. The heating temperature may be appropriately set in consideration of the 10-hour half-life temperature of the thermal radical polymerization initiator and the monomer reactivity, and the heating time required to obtain the desired Mw under a specified heating temperature condition varies depending on the solid concentration and stirring speed of the reaction system, so it is desirable to, for example, sample the liquid during the reaction at certain intervals and use GPC to grasp the Mw increase curve in advance. The reaction end point may be appropriately set by measuring the desired Mw and the amount of remaining unreacted monomer. As the thermal radical polymerization initiator, for example, azo-based thermal radical polymerization initiators such as azobisisobutyronitrile (hereinafter, AIBN), AIBN-HP, V-65HP, V-601, VR-110, and V-40 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) can be used. 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 monomer. As the organic solvent, for example, isopropyl alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and ethyl lactate can be used. As the molecular weight distribution regulator, for example, alkyl mercaptans such as hexyl mercaptan, dodecyl mercaptan, and n-octyl mercaptan can be used.

As an example of the nitroxide-mediated radical polymerization method, a monomer that is the source of introduction of repeating unit b and a monomer that is the source of introduction of other repeating units are dissolved in an organic solvent, and stirred in the presence of a nitroxide-based reaction inhibitor under a nitrogen atmosphere at a liquid temperature of 50 to 150°C for 3 to 30 hours to obtain a random polymer of repeating unit b and other repeating units, and then a monomer that is the source of introduction of repeating unit a is added and stirred at a liquid temperature of 50 to 150°C for 3 to 30 hours. Examples of commercially available nitroxide-based reaction inhibitors include Bloc Builder (registered trademark) MA and 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.

The living anionic polymerization method may, for example, be a method in which a monomer that is the source of introduction of repeating unit b and a monomer that is the source of introduction of other repeating units are dissolved in an organic solvent, and stirred 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 a monomer that is the source of introduction of repeating unit a is added and stirred at a liquid temperature of -80 to 0°C for 10 minutes to 5 hours. If there is a large amount of unreacted monomer after obtaining the random copolymer, a purification/removal step may be further added. From the viewpoint of safety, it is desirable to maintain the liquid temperature after the start of the reaction at 0°C or less and the water content in the reaction system at 1000 mass ppm or less. The reaction end point may be appropriately set by measuring the desired Mw and the amount of remaining unreacted monomer using GPC. As the anionic polymerization initiator, for example, a reaction product of a lithium compound such as ethyl lithium, sec-butyl lithium, n-butyl lithium, tert-butyl lithium, or lithium chloride with diphenylethylene (or a substituted derivative thereof) can be used. As the organic solvent, for example, tetrahydrofuran, ethylene glycol dimethyl ether, and diethyl ether can be used. As the reaction terminator, a lower alcohol such as methanol or ethanol can be used. When the above-mentioned 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 can be added after obtaining the copolymer.

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

In formula (61) and formula (62), the integers represent the number of repeating units.

In the positive photosensitive pigment composition, the component belonging to the (a) resin may be only the component (a-1), but in order to adjust the appropriate development time in the development step described below to a desired range depending on the intended film thickness of the pixel division layer and spacer layer and the type/concentration of the developer, the positive photosensitive pigment composition of the present invention may contain other resins (a-2) (hereinafter, sometimes referred to as the (a-2) component). The (a-2) component here means a compound that does not belong to the (a-1) component among the components belonging to the (a) resin. The mixing ratio of the (a-1) component and the (a-2) component may be set arbitrarily depending on the dissolution rate (nm/min) of each component in the developer, the ease of penetration of the developer into the film surface, and the required process takt time.

Preferred examples of the (a-2) component include polyimide resins, polyimide precursors, polybenzoxazole precursors, novolac resins, and (meth)acrylic resins. These may be used alone or in combination of two or more. Among these, hydroxyl-containing novolac resins and hydroxyl-containing (meth)acrylic resins are preferred because they have excellent compatibility with the (a-1) component, and because they have excellent exposure sensitivity and can easily control the alkali dissolution rate (nm/min) of the unexposed parts of the exposed film to a smaller value due to their interaction with the (c) component described below. Hydroxyl-containing (meth)acrylic resins are more preferred in terms of suppressing semi-dry film-like foreign matter.

Hydroxyl-containing novolac resin refers to a hydroxyl-containing resin that has structural units obtained by a polycondensation reaction between a compound having one phenol skeleton and aldehydes.

Examples of compounds with 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.

Examples of aldehydes include formaldehyde, paraformaldehyde, benzaldehyde, and hydroxybenzaldehyde.

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

Here, hydroxyl group-containing (meth)acrylic resin refers to 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% by mass.

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.

Furthermore, it may have repeating units derived from compounds that do not have a methacryloyl group or an acryloyl group in the molecule, such as repeating units derived from styrene monomers and repeating units derived from maleimide monomers.

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 order to improve halftone processability, a hydroxyl-containing (meth)acrylic resin derived from a repeating unit derived from (meth)acrylic acid in addition to a repeating unit derived from one or more phenolic hydroxyl-containing compounds selected from the group consisting of 4-hydroxyphenyl(meth)acrylate, 4-hydroxy-1-naphthyl(meth)acrylate, and 4-isopropenylphenol is preferred.

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

The positive photosensitive pigment composition of the present invention may further contain a commercially available polymer dispersant belonging to component (a-2) as long as it does not impair the effects of the present invention. 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, 9076, 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, 44 03, 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, 35200, 36000, 36600, 37500, 39000, 40000, 41000, 56000, 71000, 76500 (all manufactured by Lubrizol Corporation), "Ajisper" (registered trademark) PA111, PB821, PB822, PB824, PB881, PB883 (all manufactured by Ajinomoto Fine-Techno Co., Ltd.). Among them, phosphate ester polyether dispersants such as DISPERBYK-110, 111, Solsperse 40000, 41000 may be used to suppress minute development residues. These commercially available polymer dispersants belonging to the (a-2) component can be used alone or in combination.

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 means a compound that has absorption 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-shielding properties to the pixel division layer. In addition, component (b) suppresses excessive thermal flow of the film after the development process in the curing process described below, thereby preventing the pattern filling of the openings in positive halftone processing and improving the in-plane uniformity of the opening width.

From the viewpoint of optical properties, the (b) component may be an organic blue pigment, an organic purple pigment, an organic red pigment, an organic orange pigment, an organic yellow pigment, an organic brown pigment, or an organic black pigment. In order to achieve both high light blocking properties and high exposure sensitivity, an organic blue pigment and/or an organic purple pigment are preferred, and it is more preferred to use an organic blue pigment and an organic purple pigment in combination. Furthermore, by combining with the (e) component described later, a pixel division layer that finally exhibits black color can be obtained.
That is, in the positive photosensitive pigment composition of the present invention, the organic pigment (b) preferably contains an organic blue pigment and/or an organic violet pigment.

On the other hand, from the viewpoint of molecular structure, the component (b) may be (b-1) an organic pigment having no sulfo group (hereinafter, sometimes referred to as the component (b-1)) and (b-2) an organic pigment having a sulfo group (hereinafter, sometimes referred to as the component (b-2)). An organic pigment in which at least a part of the surface of the component (b-1) has been surface-treated with the component (b-2) may be used. Note that a pigment derivative in which a sulfo group has been introduced into an organic pigment having no sulfo group and which is insoluble in the positive photosensitive pigment composition is defined as a compound belonging to the component (b-2). The sulfo group here includes -SO ₃ H as well as -SO ₃ ^- (i.e., a sulfonate group). -SO ₃ ^- may be, for example, a group generated by dissociation of Na ⁺ constituting -SO ₃ Na in the positive photosensitive pigment composition.

It is known in the technical common knowledge of those skilled in the art that component (b-2) is used as an auxiliary additive in the presence of component (d) described below for the purpose of improving the dispersibility of component (b-1), but in the positive-type photosensitive pigment composition of the present invention, it can be used as a component that has the effect of imparting light-shielding properties to the pixel division layer.

When the positive photosensitive pigment composition of the present invention contains the component (b-1) and the component (b-2), the mother skeleton of the organic pigment contained in the component (b-2) is strongly adsorbed to the surface of the component (b-1), and the sulfo group contained in the component (b-2) is strongly adsorbed to the pigment adsorption group contained in the repeating unit a of the component (a-1). The positive photosensitive pigment composition of the present invention may contain only the component (b-2) without containing the component (b-1), and the sulfo group contained in the component (b-2) is strongly adsorbed to the pigment adsorption group contained in the repeating unit a of the component (a-1). Based on this mechanism, the component (b-2) not only exerts the effect of further suppressing the semi-dry film-like foreign matter, but also neutralizes a larger number of pigment adsorption groups, thereby suppressing the deterioration of the photoacid generator and the capture of the acid generated in the film in the exposed area, leading to a further improvement in 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.

Examples of the (b-1) component include organic blue pigments such as C.I. Pigment Blue 15, 60, 64, 80, C.I. Disperse Blue 14, 79:1, 134, 281, and the like; compounds represented by formula (63), organic purple pigments such as C.I. Pigment Violet 19, 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; Examples of organic black pigments include perylene black, which is a mixed crystal of C.I. Pigment Black 32, and lactam black, which is disclosed in International Publication No. 2009/010521. Among these, the compound represented by formula (63) is preferred because it has a high near-ultraviolet transmittance, can increase the amount of acid derived from the component (c) described below, and can improve exposure sensitivity.

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 represent 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 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; and R ⁶⁶ and R ⁶⁷ represent -CONH-.

The compound represented by formula (63) does not contain chlorine atoms in its molecular structure, but may contain chlorine atoms in the pigment powder due to trace amounts of residual chlorine-containing synthetic solvents. In order to improve the light-emitting properties of an organic EL display device, it is preferable to purify the pigment powder containing 70% by mass or more of the compound represented by formula (63) so that the content of chlorine atoms, as determined by combustion ion chromatography, is 1000 ppm by mass or less. 500 ppm by mass or less is more preferable. In addition, excessive purification may cause changes in the pigment surface properties, which may lead to the formation of semi-dry film-like foreign matter. In order to avoid this, 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.

Examples of the (b-2) component include the compound represented by formula (64), the compound represented by formula (65), mono/disulfonic acid derivatives of C.I. Pigment Blue 60, mono/disulfonic acid derivatives of C.I. Pigment Blue 15, mono/disulfonic acid derivatives of C.I. Pigment Red 178, mono/disulfonic acid derivatives of C.I. Pigment Red 255, and mono/disulfonic acid derivatives of bis-oxodihydroindolylene-benzodifuranone described in WO 2009/010521. Among them, 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, ability to increase the amount of acid generated originating from the component (c) described below, ability to improve exposure sensitivity, and excellent light-shielding 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.

In other words, 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 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).

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

In formula (98), formula (99), formula (100), and formula (101), R ⁸⁷ , R ⁹² , R ⁹⁷ , and R ¹⁰⁰ each independently represent -SO ₃ H or -SO ₃ ^- , R ⁸⁸ , R ⁸⁹ , R ⁹⁰ , R ⁹¹ , R ⁹³ , R ⁹⁴ , R ⁹⁵ , and R ⁹⁶ each independently represent a phenyl group, a benzyl group, or an alkyl group having 1 to 20 carbon atoms, R ⁹⁸ and R ¹⁰¹ each independently represent an alkyl group having 1 to 20 carbon atoms, R ⁹⁹ and R ¹⁰² each independently represent an alkyl group having 1 to 3 carbon atoms, and n ¹⁶ and n ¹⁷ are integers each independently represent 0 to 2. However, one or two of R ⁸⁸ , R ⁸⁹ , R ⁹⁰ , and R ⁹¹ are a phenyl group, a benzyl group, or an alkyl group having 8 to 20 carbon atoms, and one or two of R ⁹³ , R ⁹⁴ , R ⁹⁵ , and R ⁹⁶ are a phenyl group, a benzyl group, or an alkyl group having 8 to 20 carbon atoms.

The method for synthesizing the compound represented by formula (64) and the compound represented by formula (65) includes, for example, 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/disulfonic acid, and then poured into an excess amount of ice water and stirred, filtered, purified, dried, and pulverized. The purification process may include a solvent treatment and filtration process, and an isolation process by silica gel chromatography. If necessary, a process may be added in which an aqueous solution of an inorganic alkali such as sodium hydroxide is added to convert at least a part of the sulfo group into an alkali metal salt in order to increase the solubility in water and improve productivity. Next, a salt formation operation is performed using an ammonium salt of a specific structure, and the resultant is purified, dried, and pulverized, thereby synthesizing the compound represented by formula (98) and the compound represented by formula (99). In addition, a compound represented by formula (100) and a compound represented by formula (101) can be synthesized by using a pyridinium salt of a specific structure instead of an ammonium salt of a specific structure.

Examples of ammonium salts with specific structures include benzyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium bromide, dimethyldioctylammonium bromide, and benzyldimethylphenylammonium chloride.

Pyridinium salts of specific structures 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.

Specific examples of the component (b-2) obtained by the above-mentioned method preferably include a compound represented by formula (102) and a compound represented by formula (103). 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.

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

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

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 blocking properties and to avoid development residues in positive halftone processing. The primary particle size distribution can be measured using a transmission electron microscope (TEM).

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

The positive photosensitive pigment composition of the present invention may contain trace amounts of inorganic black pigments such as carbon black, titanium oxynitride, and zirconium oxynitride as inorganic pigments other than component (b), that is, pigments other than component (b) for the purpose of adjusting the reflected chromaticity, as long as the effects of the present invention are not impaired and there is no problem with the alignment of the electrode formation substrate and the exposure mask by near-infrared alignment in the exposure step disclosed in Patent Document 5, and with insulation.

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 when irradiated with light containing at least light with a wavelength of 200 to 450 nm. The principle of acid generation may be the conversion of component (c) to 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.

The component (c) is an essential component that exerts the effect of relatively increasing the solubility of the exposed portion of the film in an alkaline developer by the acid generated, compared to the solubility of the unexposed portion of the film in an alkaline developer, and imparts positive photosensitivity. Based on this principle, the pattern formability, i.e., positive photosensitivity, is expressed by removing the exposed portion of the film that has been pattern-exposed through a positive exposure mask. In addition, it is also possible to control the amount of acid generated in the film by adjusting the exposure dose. By performing pattern exposure through an exposure mask having multiple types of openings with different transmittances and a light shielding portion in the plane, i.e., a positive halftone exposure mask, the solubility of the exposed portion of the film exposed with a small amount of exposure in an alkaline developer can be relatively lowered compared to the solubility of the exposed portion of the film exposed with a large amount of exposure in an alkaline developer, and patterns of different film thicknesses can be formed in the same plane. Based on this principle, a pixel division layer and a spacer layer can be formed in one go. As the component (c), a compound that has absorption in the region of i-line (wavelength 365 nm), h-line (wavelength 405 nm) and g-line (wavelength 436 nm) of a mercury lamp and generates an acid is preferred, for example, quinone diazide compounds, imide sulfonate compounds, oxime sulfonate compounds, sulfonium salt compounds, and iodonium salt compounds. Among them, a non-salt type photoacid generator is preferred in terms of weak interaction with the pigment dispersion system and excellent application properties of the positive photosensitive pigment composition, and quinone diazide compounds, imide sulfonate compounds, and oxime sulfonate compounds are preferred. In addition, quinone diazide compounds are more preferred in terms of being able to exert a high dissolution suppression effect on the film in the unexposed area, making the difference in dissolution rate between the film in the exposed area and the unexposed area larger, being excellent in thick film processability suitable for positive halftone processing, and being able to obtain high exposure sensitivity.
That is, in the positive photosensitive pigment composition of the present invention, the photoacid generator (c) more preferably contains a quinonediazide compound.

As the quinone diazide compound, in order to achieve both high exposure sensitivity and high developability, a quinone diazide compound having a group represented by formula (67) and/or a group represented by formula (68) is preferred. It is more preferred 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.

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 represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.
In formula (67) and formula (68), R ⁸⁰ , R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ and R ⁸⁶ are preferably hydrogen atoms in order to improve the resolution.

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

In formulas (69) to (74), Q ¹ , Q ² , Q ³ , Q ⁴ , Q ⁵ , Q ⁶ , Q ⁷ , Q ⁸ , Q ⁹ , Q ¹⁰ , Q ¹¹ , Q ¹² , Q ¹³ , Q ¹⁴ , Q ¹⁵ , Q ¹⁶ , Q ¹⁷ , and Q ¹⁸ each independently represent a hydrogen atom, a structure represented by formula (75), or a structure represented by formula (76);
one or two of Q ¹ , Q ² , Q ³ , and Q ⁴ are a hydrogen atom;
one or two of Q ⁵ , Q ⁶ and Q ⁷ are hydrogen atoms;
one of Q ¹³ and Q ¹⁴ is a hydrogen atom;
One or two of Q ¹⁵ , Q ¹⁶ , Q ¹⁷ and Q ¹⁸ are a hydrogen atom.

In formula (75) and formula (76), * represents a binding site.

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

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

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

The content of component (c) is preferably 1 part by mass or more, and 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 the exposure sensitivity. In order to suppress excessive absorption of the exposure light on the film surface and improve the exposure sensitivity, the content is preferably 30 parts by mass or less, and more preferably 20 parts by mass or less.

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 described below.

Examples of 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 Cholesteric acid monomethyl ether, 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, "PGMEA"), propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, 3-methoxybutanol, γ-butyrolactone (hereinafter, "GBL"), γ-valerolactone, N-methylpyrrolidone (hereinafter, "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 coating, and appropriate drying properties, it is preferable to incorporate a combination of multiple types selected from the group consisting of PGME, methyl lactate, ethyl lactate, PGMEA, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, 3-methoxybutanol, and GBL.

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

The positive photosensitive pigment composition of the present invention preferably further contains (e) a compound that is converted by heating in the wavelength range of 350 to 780 nm into a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm. The component (e) here is a compound that does not belong to any of the components (a), (b), (c), (d), and (f). The principle of thermal coloring is not particularly limited. The minimum temperature at which coloring begins is preferably 150°C or higher in order to avoid a decrease in exposure sensitivity, and preferably 230°C or lower in order to fully obtain the effect of reducing the transmittance in the wavelength range of 350 to 500 nm. Examples of the component (e) include the thermal coloring compounds described in JP-A-2004-326094, which are converted into compounds having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, and after heat treatment at, for example, 250°C, the component (e) exhibits a yellow, orange, or brown hue in the film. Among these, in order to improve the positive halftone processability, it is preferable that the 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). In addition, 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 preferable because of their excellent effect of reducing transmittance in the wavelength range of 350 to 500 nm.

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 division layer and spacer layer can be improved.

The (f) component is preferably a compound having two or more alkoxymethyl groups or epoxy groups in the molecule.

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.).

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

The positive photosensitive pigment composition of the present invention may further contain other components, such as silicone or acrylic leveling agents and adhesion improvers for the substrate surface, such as silane coupling agents, as necessary.

The chemical structures of the (a) resin, the (b), the (c), the (d), the (e), and the (f) components can be analyzed by an appropriate combination of known techniques such as 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 ( ¹ H-NMR), and microscopic infrared absorption spectrometry. In addition, a positive photosensitive pigment composition is used as an analysis sample, and pretreatment is performed using a centrifuge to obtain a concentrated liquid from which the (b) component is separated and removed. The sequence of the repeating units is analyzed by carbon nuclear magnetic resonance spectrometry ( ¹³ C-NMR), whereby a block chain consisting only of the repeating unit a in the (a-1) component can be detected. The accuracy of the analysis may be further improved by adding a step of adding hydrochloric acid and an alcohol-based solvent to the analysis sample to extract the soluble matter including the (a) resin, or by using GPC to increase the purity of the (a) resin in the concentrated solution.

A method for preparing a positive photosensitive pigment composition includes preparing a pigment dispersion liquid containing the (a) resin, the (b) component, and the (d) component by wet dispersion processing, and then mixing and stirring the (c) component and the (d) component, and optionally the (e) component, the (f) component, and other components with the pigment dispersion liquid, and filtering the mixture through a filter as necessary.

The dispersing machine for carrying out the wet dispersion process may be either a wet media dispersing machine or a wet media-less dispersing machine, but it is preferable to use a wet media dispersing machine because of its excellent dispersion processing speed and economical advantages. The wet media dispersing process can deagglomerate the secondary aggregates of component (b) to obtain a fine and sharp particle size distribution. Examples of wet media dispersing machines 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 Co., Ltd.), "Spike Mill (registered trademark)" (manufactured by Inoue Seisakusho Co., Ltd.), "Sand Grinder (registered trademark)" (manufactured by DuPont Co., Ltd.), "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 material is preferably ceramic beads such as zirconia, with a diameter of 0.03 to 0.5 mm. Commercially available products include "TORECERAM (registered trademark)" (manufactured by Toray Industries, Inc.).

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 means a product obtained through a process of heating the positive photosensitive pigment composition at a temperature of 200°C or more and 400°C or less under atmospheric pressure for 10 minutes or more.

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

The following describes preferred embodiments of the cured film of the present invention when used as a pixel dividing layer and a spacer layer in an organic EL display device.

The optical density per 1.0 μm of 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, and more preferably 0.7 or more, in order to suppress external light reflection and increase 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, and more preferably 1.3 or less.

The optical density here means a value obtained by measuring the incident light intensity and the 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) and dividing the value calculated from the following formula by the film thickness value of 1.5, 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 is the incident light intensity, and I is the transmitted light intensity.

In order to improve yield by reducing the contact area with the deposition mask when pattern-depositing the light-emitting layer, while also achieving good 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 standpoint of exposure sensitivity, the thickness of the portion where the pixel division layer and the spacer layer are laminated is preferably 2.0 to 4.0 μm.

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 in which a positive photosensitive pigment composition is applied to obtain a coating film, a pre-baking step in which the coating film is heated to obtain a pre-baked film, an exposure step in which the pre-baked film is pattern-exposed to activated actinic rays through a positive half-tone exposure mask to obtain an exposed film having exposed, semi-exposed and unexposed parts within its surface, a development step in which the exposed film is developed with an alkaline developer to obtain a developed film by removing a part of the semi-exposed and unexposed parts in addition to the exposed parts, and a curing step in which the film is thermally cured by heating to obtain a cured film.

As the coating device used in the coating process, a spin coater or slit coater is preferably used because of its excellent thin film coating properties.

The pre-bake temperature in the pre-bake process is preferably 50 to 150°C, and the pre-bake time is preferably 30 seconds to 5 minutes. When forming the pixel division layer and the spacer layer at the same time, the thickness of the pre-bake film is preferably 3.5 to 6.0 μm. To improve the film thickness uniformity, a reduced pressure drying process may be provided between the coating process and the pre-bake process.

Examples of exposure devices used in the exposure process include steppers, mirror projection mask aligners (MPAs), and parallel light mask aligners (PLAs). Activated 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) of an ultra-high pressure mercury lamp. Mixed rays containing at least the h-line are preferred, and mixed rays containing g-line, h-line, and i-line are more preferred. It is preferable to use a positive halftone exposure mask that has a fully transparent portion, a semi-transparent portion, and a shielding portion within the substrate surface, 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 10-50%.

The exposed area of the exposed film refers to the area that is pattern-exposed through the fully transparent area of the exposure mask, the semi-exposed area refers to the area that is pattern-exposed through the semi-transparent area of the exposure mask, and the unexposed area refers to the area that is not exposed due to the shielding area of the exposure mask.

The developing method in the developing step includes, for example, shower, dipping, paddle, etc., and includes a method in which the exposed film is immersed for 10 seconds to 3 minutes. The paddle method is preferred to improve the uniformity of the opening width of the opening of the pixel division layer. The alkaline developer is preferably a 0.4 to 2.5 mass% aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as "TMAH"), and an example of a commercially available product is 2.38 mass% TMAH (manufactured by Tama Chemicals Co., Ltd.). After the developing step, a cleaning process using a shower of deionized water and/or a water draining process using air injection may be added. In order to improve the in-plane uniformity of the developed film thickness, it is preferable to set the development time so that the value obtained by subtracting the film thickness of the developed film in the unexposed part from the film thickness of the pre-baked film, that is, the film loss (μm) in the developing step, is 1.0 μm or less. In order to improve the exposure sensitivity, it is preferable to set it to 0.5 μm or more.

In the curing process, 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 hot air ovens and IR ovens, and the heating atmosphere can be nitrogen or air. The heating temperature is preferably 220 to 280°C.

The organic EL display device of the present invention, which is a third aspect of the present invention, is an organic EL display device that includes the cured film of the present invention. The organic EL display device of the present invention has an advantageous technical effect of suppressing the occurrence of non-illuminated pixels. In addition, by including a pixel division layer and a spacer layer that are formed collectively by positive halftone processing, the pixel division layer has high in-plane uniformity in the aperture width, and is characterized by being more cost-effective than a case in which 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 that includes the cured film of the present invention as a pixel division layer and a spacer layer, a cross-sectional view of a TFT substrate in an organic EL display device is shown in Figure 1.

On the surface of the substrate 6, bottom-gate or top-gate thin-film transistors 1 (hereinafter abbreviated as TFT1) are arranged in a matrix, 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 a contact hole 7 is provided in the planarization layer 4 to connect the first electrode 5 to the wiring 2. A first electrode 5 is patterned on the surface of the planarization layer 4 and connected to the wiring 2. A pixel division layer 8 is arranged so as to surround the periphery of the pattern of the first electrode 5. The pixel division layer 8 has an opening, and a light-emitting pixel 10 containing an organic EL light-emitting material is arranged in the opening. A convex spacer layer 9 is arranged on a part 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 pixel 10.

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

The emission peak wavelength of the light-emitting pixel 10 is not particularly limited, but a specific example of the configuration is an arrangement of different types of pixels having emission peak wavelengths in the regions of blue, red, and green, 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, in order 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. As the color filter, for example, a color filter having high color reproducibility disclosed in JP 2022-164709 A may be mentioned.

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

The first electrode 5 may be made of conductive metal oxides such as indium tin oxide (ITO) and indium zinc oxide (IZO), among which ITO is preferred due to its excellent transparency and conductivity. The method of patterning ITO involves forming an ITO film over the entire surface by sputtering, then patterning a positive resist material for etching by photolithography to obtain a resist pattern on the ITO film, and removing only the ITO film in the areas where the resist pattern is not formed by an etching solution. Next, the resist pattern is removed by a resist stripper, and heat treatment is performed as necessary to obtain the desired crystallinity. The positive resist material for etching may be a positive photosensitive composition containing an alkali-soluble novolac resin. The etching solution may be an aqueous solution containing nitric acid and hydrochloric acid or an aqueous solution of oxalic acid. Commercially available products include, for example, ITO-101N (Kanto Chemical Co., Ltd.), "Sclean (registered trademark)" IS-2 and IS-3 (all of which are manufactured by Sasaki Chemical Co., Ltd.). The resist stripping solution may be an aqueous solution of an organic amine system. Commercially available products include, for example, "Anlast (registered trademark)" M6, M6B, TN-1-5, and M71-2 (all of which are manufactured by Miwako Pure Chemical Research Institute). When the organic EL display device of the present invention is a top-emission type 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.

The second electrode 11 may be made of any material as long as it is a layer that functions as an electrode. For example, when the organic EL display device of the present invention is a bottom-emission type 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 type 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 using a sputtering method.

The light extraction direction of the organic EL display device of the present invention is not particularly limited, and may be a bottom-emission type organic EL display device in which the light emitted from the light-emitting pixels 10 is extracted to the substrate side via the substrate 6, or a top-emission type organic EL display device in which the light emitted is extracted to the opposite side of the substrate 6 via 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.

The substrate 6 may be a substrate made of glass that does not have flexibility, or a substrate made of polyimide resin that has flexibility. 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.). An example of a substrate made of polyimide resin is a substrate obtained by applying a solution containing polyamic acid to the surface of a temporary support, then heating the polyamic acid at 250 to 400°C to imidize it and convert it into polyimide resin, and then peeling off the temporary support with a laser or the like. A specific example is polyamic acid having residues of 3,3',4,4'-biphenyltetracarboxylic dianhydride and residues of p-phenylenediamine.

The electronic device of the present invention, which is a fourth aspect of the present invention, is an electronic device equipped with the organic EL display device of the present invention. As described above, by providing an organic EL display device having a pixel division layer and a spacer layer, which have the technical effects of high in-plane uniformity of the light-emitting pixel size and suppressing the occurrence of non-illuminated pixels, and which is formed collectively, the electronic device of the present invention has advantageous features of suppressing uneven brightness, excellent visibility, and low cost. An electronic device equipped with an organic EL display device here means an apparatus that has at least an organic EL display device, a driving circuit, and a power source, and is capable of displaying text information, images, and/or videos by itself. Specific examples of embodiments of the electronic device of the present invention include a personal computer, a foldable smartphone, a non-foldable rigid smartphone, a wristwatch, a table clock, glasses, an in-vehicle monitor, a car navigation system, a gaming monitor, a portable game console, a television, and a head-mounted display.

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 of only repeating units a and repeating units b,
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),
The repeating unit b is a block copolymer which is a repeating unit represented by formula (33) and/or a repeating unit represented by formula (34).

In formula (1), formula (2), formula (3), formula (4), and formula (5), * represents a binding site.
R ¹ , R ⁴ , R ⁷ , R ¹¹ , and R ¹⁵ each independently represent 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 represent a single bond or a divalent linking group having 1 to 8 carbon atoms and not containing a nitrogen atom;
R ³ , R ⁶ , R ⁹ , R ¹⁴ , and R ¹⁹ each independently represent an alkyl group having 1 to 3 carbon atoms;
n 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 represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
R ¹⁷ and R ¹⁸ each independently represent an alkyl group having 1 to 5 carbon atoms.

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

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

The block chain consisting only of repeating unit a here means a structure in which 10 or more repeating units belonging to repeating unit a are linked together, with 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 here is not particularly limited.

When used to manufacture a positive-type photosensitive pigment composition, the preferred chemical structure of the block copolymer of the present invention is based on the same principles as the preferred chemical structure of component (a-1) described above.

In order to suppress the generation of semi-dry film-like foreign matter and obtain high exposure sensitivity, it is more preferable that the repeating unit a is 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 its high effect of suppressing the generation of non-illuminated pixels, it is most preferable to have a repeating unit represented by the formula (9).

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

The method for synthesizing the block copolymer of the present invention can be the same as the method for synthesizing component (a-1) described above.

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.

(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 a 50 mL transparent glass vial (manufactured by AS ONE Corporation/Labolan (registered trademark) screw tube bottle No. 7; hereinafter sometimes referred to as "vial") serving as a storage container, and the vial was then tightly sealed. A schematic diagram of the appearance of the positive photosensitive pigment composition after being dropped into the glass vial and tightly sealed is shown in Figure 2.

This was stirred for one minute, bringing all of the inner wall surfaces of the vial into contact with the positive photosensitive pigment composition and causing it to become wet. After leaving it to stand for seven days in a temperature-controlled room maintained at atmospheric pressure and a liquid temperature of 25±1°C, the vial was opened and held upside down for one minute, and the liquid that had fallen out was transferred to another container and discarded.

Next, 35.00 g of PGME was poured as a cleaning solvent into the aforementioned vial to which the components derived from the positive photosensitive pigment composition had adhered, 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 had fallen out was transferred to another container and discarded. A schematic diagram of the appearance of a semi-dry film-like foreign matter formed on the inner wall surface of a glass vial is shown in Figure 3. 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 regarded as the amount (g) of semi-dry film-like foreign matter formed, and the smaller the amount of formation, the better.

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

(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 evaluation method for 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 vial as described above, sealed, and stirred for 1 minute to bring the entire inner wall surface of the vial into contact with the positive photosensitive pigment composition and wet it. After leaving the vial to stand for 7 days in a thermostatic chamber maintained at atmospheric pressure/liquid temperature of 25±1°C, the vial was opened and the second exposure sensitivity was evaluated.
The above evaluations were carried out under yellow light, which does not expose the component (c).

The higher the second exposure sensitivity, i.e., the smaller the required minimum exposure dose after standing for 7 days in a constant temperature room, the better the film was evaluated, and evaluation was performed based on the following criteria, with AA and A to C being passed and D to E being failed. However, when it was difficult to evaluate the exposure sensitivity (required minimum exposure dose) due to problems such as failure to form a film with a predetermined thickness or failure to form an opening even under the maximum exposure dose condition (300 mJ/cm ² ), it was evaluated as F and failed.
AA: The minimum required exposure dose is 40 mJ/cm ² or 50 mJ/cm ² .
A: The required minimum exposure amount is 60 mJ/cm ² or 70 mJ/cm ² .
B: The minimum required exposure amount is 80 to 100 mJ/ ^cm2 .
C: The minimum required exposure amount is 110 to 150 mJ/ ^cm2 .
D: The minimum required exposure dose is 160 to 250 mJ/ ^cm2 .
E: The required minimum exposure amount is 260 to 300 mJ/ ^cm2 .
F: It is difficult to evaluate the exposure sensitivity.

<Evaluation method of exposure sensitivity (minimum required exposure amount)>
A silver alloy (an alloy of 99.00 mass % silver and 1.00 mass % copper) was formed on the entire surface of an alkali-free glass substrate having a length of 150 mm and a width of 150 mm by a sputtering method. An ITO film was then formed on the entire surface by a sputtering method to obtain a glass substrate having a silver alloy film/ITO film on the entire surface of the alkali-free glass substrate.

The positive photosensitive pigment composition was applied to the ITO surface of the glass substrate having a silver alloy film/ITO film by adjusting the rotation speed using a spin coater so that the film thickness of the pixel division layer finally obtained was 1.5 μm, and the film thickness of the spacer layer arranged on the surface of the pixel division layer was 1.5±0.1 μm, respectively, to obtain a coating film.Furthermore, the coating film was pre-baked at 110° C. under atmospheric pressure for 120 seconds using a hot plate to obtain a pre-baked film, and the positioning of a positive halftone exposure mask (a mask designed so that 220 square transmission parts of length: 30.0 μm, width: 30.0 μm are arranged, and the exposure amount of the semi-transmission part is 15% when the exposure amount of the total transmission part is 100% and the exposure amount of the shielding part is 0%) was performed using a near-infrared camera (light source wavelength: 800 nm). Using a double-sided alignment single-sided exposure device, the prebaked film was pattern-exposed to a mixture of g, h, and i rays from an ultra-high pressure mercury lamp by changing the exposure amount stepwise in increments of 10 mJ within the range of 40 to 300 (mJ/ ^cm2 : i-line equivalent value) through a positive half-tone exposure mask, to obtain an exposed film having exposed, semi-exposed, and unexposed areas within its surface. The pattern exposure was performed by contacting the positive half-tone exposure mask with the surface of the prebaked film.

Next, in the development process, development was performed by the paddle method using a small photolithography developing device (AD-1200; manufactured by Takizawa Sangyo Co., Ltd.) and an alkaline developer of 2.38% by mass tetramethylammonium hydroxide aqueous solution. The paddle method here refers to a method in which the alkaline developer is shower-coated on the surface of the exposed film for 10 seconds, and then left to stand until a predetermined development time is reached for development. The development time was in the range of 30 to 100 seconds, and was set to the value obtained by subtracting the film thickness of the unexposed part of the developed film formed on the developed film-formed substrate described below from the film thickness of the pre-baked film, that is, the time at which the film loss (μm) in the development process becomes 0.8 μm. Furthermore, after rinsing with deionized water for 30 seconds by the shower method, the substrate was rotated at 200 rpm for 30 seconds to dry, and a developed film-formed substrate provided with a developed film was obtained.

Then, 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 that includes a pixel division layer and a spacer layer.

The openings of the pixel division layer were observed using an FPD inspection microscope (MX-61L; manufactured by Olympus Corporation), and the minimum required exposure dose (mJ/ ^cm2 : i-line equivalent value) when the average opening width of 10 openings in each exposure dose region was within the range of 30.0±0.1 μm was defined as the exposure sensitivity. Note that the opening width was measured only for openings that were square due to the exposure mask and openings that were circular due to thermal flow in the curing process, and openings in which foreign matter defects were observed were excluded from the measurement.

(3) Evaluation of in-plane uniformity of aperture width of pixel division layer The substrate for measuring the exposure sensitivity used in the evaluation of the second exposure sensitivity described above was observed using an FPD inspection microscope, and the aperture widths of 10 apertures were measured. The smaller the value W ₃ (μm) obtained by subtracting the minimum aperture width W ₂ (μm) from the maximum aperture width W ₁ (μm), the better the result was. Evaluation was performed based on the following criteria, with A to C being passed and D to E being failed. An example of the maximum aperture width W ₁ and the minimum aperture width W ₂ is shown in FIG. 4. However, this evaluation was not performed for the positive photosensitive pigment composition for which it was difficult to evaluate the second exposure sensitivity described above. The aperture width measurement was performed including the apertures in which foreign matter defects were observed.
A: _W3 is less than 1.0 μm.
B: _W3 is 1.0 μm or more and less than 1.2 μm.
C: _W3 is 1.2 μm or more and less than 1.5 μm.
D: _W3 is 1.5 μm or more and less than 2.0 μm.
E: _W3 is 2.0 μm or more.

(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, and 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 described above, which were then sealed and stirred for 1 minute to bring the entire inner wall surface of the vial into contact with the positive photosensitive pigment composition and wet it. 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 the stopper was opened. The positive photosensitive pigment composition was applied to the surface of a transparent glass substrate "Tempax (manufactured by AGC Technoglass Co., Ltd.) by a spin coater, adjusting the rotation speed so that the final cured film had 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 g, h, and i mixed rays of an ultra-high pressure mercury lamp at an exposure amount equivalent to 15% of the second exposure sensitivity (required minimum exposure amount) obtained by the above-mentioned method, to obtain an exposed film. Development, rinsing, and drying were performed in the same manner as in the evaluation of the second exposure sensitivity, to obtain a solid developed film. The developed film was heated at 250° C. for 1 hour under air using a high-temperature inert gas oven, to obtain a light-shielding evaluation substrate having a solid cured film with a film thickness of 1.5 μm.

For the substrates used for light-shielding evaluation, the total optical density (Total OD value) was measured at three points on the film side using an optical densitometer (X-Rite Corporation; X-Rite 361T) to calculate the average value, which was then divided by 1.5 and rounded to the nearest tenth to obtain the light-shielding property per 1.0 μm of cured film thickness (OD/μm). The higher the OD/μm value, the better the cured film. The OD value of Tempax, which does not have a cured film formed, was measured separately and found to be 0.00, so the total optical density of the substrates used for light-shielding evaluation was regarded as the total optical density of the cured film. The thickness of the cured film was measured at three points on the surface using a stylus film thickness measuring device (Tokyo Seimitsu Co., Ltd.; Surfcom), and the average value was rounded to the nearest tenth to obtain the light-shielding property per 1.0 μm of cured film thickness. In addition, for positive-type photosensitive pigment compositions for which it was difficult to evaluate the second exposure sensitivity, the light-blocking properties of the cured film were not evaluated.

(5) Evaluation of the incidence of non-lighting pixels in organic EL display devices A top-emission organic EL display device was driven to emit light by direct current at 10 mA/ ^cm2 , and 50 light-emitting pixel portions per unit were enlarged and displayed on a monitor at a magnification of 50 times and observed. The total number of non-lighting pixels observed in 5 top-emission organic EL display devices manufactured by the same method was divided by the total number of all light-emitting pixels, 250, and multiplied by 100 to calculate the incidence of non-lighting pixels (%). When one or more non-lighting 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 as pass, and D to E being considered as fail. In addition, the incidence of non-lighting pixels was not evaluated for the positive photosensitive pigment composition for which it was difficult to evaluate the second exposure sensitivity.
AA: The incidence of non-lighted pixels is 0.0% (i.e., no non-lighted pixels are observed).
A: The incidence rate of non-lighted pixels is 0.4% or more and less than 2.0%.
B: The incidence rate of non-lighted pixels is 2.0% or more and less than 4.0%.
C: The incidence rate of non-lighted pixels is 4.0% or more and less than 6.0%.
D: The incidence rate of non-lit pixels is 6.0% or more and less than 10.0%.
E: The incidence rate of non-lighted pixels is 10.0% or more.

In the synthesis of pigment dispersant solutions 1 to 25 and the synthesis of hydroxyl-containing acrylic resin solution X described below, the weight average molecular weight (Mw) was determined under the following measurement conditions.
GPC device: Tosoh Corporation HLC-8420GPC
Column: TSKgel SuperAW4000
Guard column: TSK guard column Super AW-L
Eluent: a solution in which 8.67 g of lithium bromide was dissolved in 10 L of N,N'-dimethylacetamide. Analysis sample: a solution in which a resin solution (1 part by mass as resin) was dissolved 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.), which is a monomer serving as a source of introduction of the repeating unit a, and 0.21 g of AIBN (manufactured by Tokyo Chemical Industry Co., Ltd.), which is a thermal polymerization initiator, were dissolved in 178.76 g of PGME, which is an organic solvent, and stirred under a nitrogen atmosphere/liquid temperature of 70° C. until Mw2000 was reached. The required heating time was 3 hours. Next, in the second polymerization step, a solution in which 142.55 g (0.80 mol) of 4-hydroxyphenyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.43 g of AIBN were dissolved in 706.02 g of PGME was additionally dropped, and the solution was stirred while maintaining a liquid temperature of 70° C. until Mw10000 was reached, and then cooled to stop 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.

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

(Synthesis Example 2: Synthesis of Pigment Dispersant Solution 2)
Pigment dispersant solution 2 having a solid 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. It was confirmed by ¹³ 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).

(Synthesis Example 3: Synthesis of Pigment Dispersant Solution 3)
Pigment dispersant solution 3 having a solid content of 10.00% by 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, and in the blending amounts shown in Table 1.

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

(Synthesis Example 4: Synthesis of Pigment Dispersant Solution 4)
A pigment dispersant solution 4 having a solid content of 10.00% by 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 were as shown in Table 1.

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

(Synthesis Example 5: Synthesis of Pigment Dispersant Solution 5)
A pigment dispersant solution 5 having a solid content of 10.00% by 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.

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

(Synthesis Example 6: Synthesis of Pigment Dispersant Solution 6)
A pigment dispersant solution 6 having a solid content of 10.00% by 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 the blending amounts shown in Table 2 were used.

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

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

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

(Synthesis Example 8: Synthesis of Pigment Dispersant Solution 8)
A pigment dispersant solution 8 having a solid 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.

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

(Synthesis Example 9: Synthesis of Pigment Dispersant Solution 9)
A pigment dispersant solution 9 having a solid 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 in place of 4-vinylpyridine and in the blending amounts shown in Table 3.

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

(Synthesis Example 10: Synthesis of Pigment Dispersant Solution 10)
A pigment dispersant solution 10 having a solid 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, 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.

It was confirmed by ^13C -NMR that pigment dispersant solution 10 contains 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)
A pigment dispersant solution 11 having a solid 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.

It was confirmed by ^13C -NMR that pigment dispersant solution 11 contains 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).

(Synthesis Example 12: Synthesis of Pigment Dispersant Solution 12)
A pigment dispersant solution 12 having a solid 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.

It was confirmed by ^13C -NMR that pigment dispersant solution 12 contains 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).

(Synthesis Example 13: Synthesis of Pigment Dispersant Solution 13)
A pigment dispersant solution 13 having a solid 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 amounts shown in Table 4.

It was confirmed by ^13C -NMR that pigment dispersant solution 13 contains 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).

(Synthesis Example 14: Synthesis of Pigment Dispersant Solution 14)
A pigment dispersant solution 14 having a solid 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 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.

It was confirmed by ^13C -NMR that pigment dispersant solution 14 contains 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).

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

(Synthesis Example 15: Synthesis of Pigment Dispersant Solution 15)
A pigment dispersant solution 15 having a solid 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 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.

It was confirmed by ^13C -NMR that pigment dispersant solution 15 contains 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).

(Synthesis Example 16: Synthesis of Pigment Dispersant Solution 16)
As 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, which is an organic solvent, and the solution was stirred under a nitrogen atmosphere/liquid temperature of 70° C. until Mw reached 10,000, and then cooled to stop the reaction. The required heating time was 8 hours. PGME was added to the obtained resin solution to dilute it, and a pigment dispersant solution 16 with a solid content of 10.00% by mass was obtained. The second polymerization step was not performed.

It was confirmed by ^13C -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 used are shown in Table 6.

(Synthesis Example 17: Synthesis of Pigment Dispersant Solution 17)
A pigment dispersant solution 17 having a solid 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.

It was confirmed by ^13C -NMR that pigment dispersant solution 17 contains a block copolymer having a block chain composed 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 does not contain the repeating unit b.

(Synthesis Example 18: Synthesis of Pigment Dispersant Solution 18)
Pigment dispersant solution 18 having a solid 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, and in the blending amounts shown in Table 8.

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

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

(Synthesis Example 19: Synthesis of Pigment Dispersant Solution 19)
Pigment dispersant solution 19 having a solid 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, and in the blending amounts shown in Table 8.

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

In formula (91), * represents a binding site.

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 regarding their structures is summarized and shown in Table 9.

(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. A solution of 15.18 g of triethylamine dissolved in 50 g of 1,4-dioxane was added dropwise to the system so that the temperature in the system was 35°C or lower. 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. Then, filtration was performed, and the precipitate that had precipitated was collected. The precipitate was dried in a vacuum dryer to obtain quinone diazide compound a represented by formula (92), which is component (c).

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

(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.

In formula (93), * represents the bonding site with the oxygen atom.

(Production Example 1: Production of Fine Perylene Black Pigment 1)
Fine 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 method for producing fine perylene black pigment 1 disclosed in Production Example 1 of Patent Document 5. Fine perylene black pigment 1 is component (b-1). The content of chlorine atoms contained in fine 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 quantification.

(Production Example 2: Production of Micronized Dioxazine Pigment 2)
Fine dioxazine pigment 2 was produced by the same method as that for producing fine dioxazine pigment 2 disclosed in Production Example 6 of Patent Document 5. Fine dioxazine pigment 2 is a compound in which, in formula (63), R ⁵² to R ⁶¹ are all hydrogen atoms, R ⁶² and R ⁶³ are ethyl groups, R ⁶⁴ and R ⁶⁵ are methyl groups, and R ⁶⁶ and R ⁶⁷ are -CONH-, and is component (b-1). The content of chlorine atoms contained in fine dioxazine pigment 2 was quantified by ion chromatography and found to be 320 ppm by mass.

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

(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 in the same manner as the synthesis method of dispersant solution b disclosed in Production Example 2 of Patent Document 1. Dispersant solution b is a PGMEA solution with a solid 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 solid content of 10.00 mass%, to obtain pigment dispersant solution 20. The solution was transparent with no precipitation or cloudiness observed, and had good solubility in PGME.

(Synthesis Example 23: Synthesis of Dye B)
Dye B was synthesized using CI Pigment Red 178 as a starting material in the same manner 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).

(Synthesis Example 24: Synthesis of Perylene Blue Pigment 3)
100.00 g of PTCBI (Tokyo Chemical Industry Co., Ltd.; cis and trans isomer mixture) 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. The filtered product was washed with a mixed liquid (ethanol:water = mass ratio 80:20) and then filtered again, and dried under reduced pressure at 80° C. for 24 hours. Further, a dry grinding process was performed using a nanojet mister, and coarse components were removed through a stainless steel sieve filter (opening diameter 20 μm), to obtain 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 MT3000II (manufactured by MICROTRAC Corporation) was 5 μm.

(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 liquid was stirred at 80° C. for 8 hours to allow the sulfonation reaction to proceed. Next, the liquid was poured into 15 kg of ice water, stirred, and then filtered to obtain a wet cake. The wet cake was washed with a mixed solution (ethanol:water = mass ratio 80:20) until the sulfate ion was below 50 ppm by mass, and then filtered, and deionized water was added to obtain a solid content of 1% by mass to prepare a perylene blue solution. Using LC-MS and MALDI-TOF MS, it was confirmed that the perylene blue solution was an aqueous solution of a disulfonic acid derivative of PTCBI.

(Synthesis Example 26: Synthesis of Perylene Blue Pigment 4)
3000.00 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 while stirring, and 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 = mass ratio 50:50), the dissolved filtrate was discarded, and the filtrate was washed with deionized water and filtered again. The mixture was dried under reduced pressure at 80 ° C. for 24 hours, subjected to dry grinding treatment using a nanojet mister, and passed through a stainless steel sieve filter (opening diameter 20 μm) to remove coarse particles, and perylene blue pigment 4, which is a mixture of the compound represented by formula (106) and the compound represented by formula (107), was obtained. Perylene blue pigment 4 is component (b-2), and the cumulative 90% secondary particle diameter in the volume-based particle size distribution measured with 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.

(Synthesis Example 27: Synthesis of Perylene Blue Pigment 5)
3000.00 g of the perylene blue solution (solid content 1% by mass) synthesized in Synthesis Example 25 was charged into 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 while stirring, and the mixture was stirred at a liquid temperature of 50 ° C. for 12 hours, and then allowed to stand for 7 days. Next, the precipitate was washed with a mixed solution (PGME:PGMEA = mass ratio 50:50), the dissolved filtrate was discarded, and the filtrate was washed with deionized water and filtered again. The mixture was dried under reduced pressure at 80 ° C. for 24 hours, subjected to dry grinding treatment using a nanojet mister, and passed through a stainless steel sieve filter (opening diameter 20 μm) to remove coarse components, and perylene blue pigment 5, which is a mixture of the compound represented by formula (108) and the compound represented by formula (109), was obtained. Perylene Blue Pigment 5 is 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 an insoluble particle having an acidic surface.

(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 mass% aqueous solution of benzyldodecyldimethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of the 5 mass% aqueous solution of hexadecyltrimethylammonium bromide. Perylene Blue Pigment 6 is component (b-2), and is a mixture of a compound in which, in formula (98), R ⁸⁸ and R ⁸⁹ are methyl groups, R ⁹⁰ is a benzyl group, and R ⁹¹ is an alkyl group having 12 carbon atoms, and a compound in which, in formula (99), R ⁹³ and R ⁹⁴ are methyl groups, R ⁹⁵ is a benzyl group, and R ⁹⁶ is 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) had a pH of 3.8, and perylene blue pigment 6 was considered to be insoluble particles having an acidic surface.

(Synthesis Example 29: Synthesis of Hydroxyl-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 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 the solution of component (a-2) was diluted with PGME to a solid content of 30.00% by mass, to give a hydroxyl group-containing acrylic resin solution X. The Mw was 23,000.

(Preparation Example 1: Preparation of Pigment Dispersion 1)
40.00 g of TR4020G (manufactured by Asahi Organic Chemicals Co., Ltd.; a hydroxyl group-containing novolak resin having a structure derived from m-cresol and a structure derived from p-cresol) was added to 720.00 g of a mixed solvent (PGME:ethyl lactate:GBL = mass ratio 50:40:10) and dissolved by stirring for 30 minutes. 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 finely divided dioxazine pigment 2 was added and stirred for 30 minutes to obtain a preliminary stirred liquid. Next, the preliminary stirring liquid was sent to a vertical bead mill "Ultra Apex Mill Advance (registered trademark)" (manufactured by Hiroshima Metal & Machinery Co., Ltd.) in which 0.05 mmφ zirconia beads "TORECERAM (registered trademark)" (manufactured by Toray Industries, Inc.) were filled in a vessel at a filling rate of 75 volume %, and a wet media dispersion treatment was performed for 5 hours at a peripheral speed of 10 m/s using a circulation method, thereby obtaining a pigment dispersion liquid 1 having a solid content of 10.00 mass %. A first filtration was performed using a filter having an aperture of 0.8 μm, and a second filtration was performed using a filter having an aperture of 0.2 μm. It was confirmed that there was no change in the value of the solid content up to the second decimal place before and after filtration. The mass ratio of the solid content of the pigment dispersion liquid 1 was (b-1) component:(b-2) component:(a-1) component:(a-2) component=70:30:50:100. The blending amounts of each raw material are shown in Table 10.

(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 amounts of each raw material used are shown in Tables 10 to 14.

(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 amounts of each raw material shown in Table 14 were used.

(Preparation Example 21: Preparation of Pigment Dispersion 21)
52.57 g of polyimide precursor B was added to 757.70 g of 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, and then 18.92 g of finely divided perylene black pigment 1 and 8.11 g of finely divided dioxazine pigment 2 were added and stirred for 30 minutes to obtain a preliminary stirring liquid. Next, the preliminary stirring liquid was sent to a vertical bead mill "Ultra Apex Mill Advance (registered trademark)" (manufactured by Hiroshima Metal & Machinery Co., Ltd.) in which 0.05 mmφ zirconia beads "TORECERAM (registered trademark)" (manufactured by Toray Industries, Inc.) were filled in a vessel at a filling rate of 75 volume %, and a wet media dispersion treatment was performed for 5 hours at a peripheral speed of 10 m/s using a circulation method, to obtain a pigment dispersion liquid 21 having a solid content of 10.00 mass %. A first filtration was performed using a filter having an aperture of 0.8 μm, and a second filtration was performed using a filter having an aperture of 0.2 μm. It was confirmed that there was no change in the value of the solid content up to the second decimal place before and after filtration. The mass ratio of the solid content of the pigment dispersion liquid 21 was (b-1) component:(b-2) component:(a-1) component:(a-2) component=100:17:59:195. The blending amounts of each raw material are shown in Table 15.

(Preparation Example 22: Preparation of Pigment Dispersion 22)
Pigment Dispersion Liquid 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 amounts of each raw material used are shown in Table 15.

(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.

(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, which was used as pigment dispersant solution 21. It was confirmed from pyrolysis GC-MS and ¹ H-NMR analyses, and from measurement of the amine value (mgKOH/g), that BYK-LPN6919 has the same repeating unit structure, molar ratio, and amine value as “Dispersant-I” disclosed in the examples of Patent Document 3.

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

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.

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 quinone diazide compound b (manufactured by Tokyo Chemical Industry Co., Ltd.) as 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 PGME solution containing 5% by mass of solids as a leveling agent, BYK-333 (manufactured by BYK-Chemie), were added and dissolved by stirring for 30 minutes. Furthermore, 52.80 g of Pigment Dispersion 1 was added and stirred for 30 minutes to obtain a positive photosensitive pigment composition 1 with a solids content of 12.00% by mass. The amounts of each raw material used are shown in Table 17.

Using the method 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 to 19.

Next, a top-emission organic EL display device was fabricated using the following method, which had a cured film containing the cured product of positive-type photosensitive pigment composition 1 as a pixel dividing layer and a spacer layer, and the occurrence rate (%) of non-illuminated pixels was evaluated. Figure 5 shows the fabrication process.

A silver alloy (an alloy consisting of 99.00% by mass silver and 1.00% by mass 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. An alkali-soluble novolac-based positive resist was used, and the substrate was immersed in a silver alloy etching solution at a liquid temperature of 30°C for etching, to obtain a patterned silver alloy film 18 with a thickness of 100 nm. Furthermore, an amorphous ITO (indium-tin oxide) film, which is a metastable phase, was formed on the entire surface by sputtering. An alkali-soluble novolac-based positive resist was used, and the substrate was immersed in a 5% by mass oxalic acid solution at a liquid temperature of 50°C for 5 minutes, washed with deionized water for 2 minutes, and then dried with an air blower to form an amorphous ITO film with a thickness of 10 nm in the same pattern. The substrate was then subjected to low-temperature annealing treatment 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 that had a first electrode consisting of a laminated pattern of silver alloy film/low-crystalline ITO.

The positive photosensitive pigment composition 1 was stored in a freezer (atmospheric pressure/light-shielded, -20°C±1°C) for 30 days, then removed from the freezer and cooled to 25°C. Five 50-mL transparent glass vials were prepared by dripping 10.00 g of the positive photosensitive pigment composition 1 into them and sealing them, and the entire inner wall surface of the vial was wetted with the positive photosensitive pigment composition 1 by stirring for one minute. After leaving the vials 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, turned upside down and held for one minute, and the dropped liquid was poured into a 100-mL container and mixed. The mixture was applied to the surface of the first electrode-forming substrate 1 using a spin coater, adjusting the rotation speed so that the final pixel division layer had a thickness of 1.5 μm and the spacer layer disposed on the surface of the pixel division layer had a thickness of 1.5±0.1 μm, to obtain a coating film.

Furthermore, the coating film was prebaked at atmospheric pressure at 110°C for 120 seconds using a hot plate to obtain a prebaked film. The prebaked film was pattern-exposed to g, h, and i mixed rays of an ultra-high pressure mercury lamp at the minimum required exposure amount (i.e., second exposure sensitivity) using a double-sided alignment single-sided exposure device through a positive halftone exposure mask (a mask with 220 square total transmission parts of 30.0 μm length and 30.0 μm width, designed so that the exposure amount in the semi-transmission parts is 15% when the exposure amount in the total transmission parts is 100% and the exposure amount in the shielding parts is 0%) to obtain an exposed film having exposed parts, semi-exposed parts, and unexposed parts in its surface. The pattern exposure was performed by contacting the positive halftone exposure mask with the surface of the prebaked film.

Then, a development process and a curing process were carried out in the same manner as in the second exposure sensitivity measurement method, and a pixel division layer/spacer layer-forming substrate 1 having a pixel division layer/spacer layer 20 was obtained. The thickness of the pixel division layer was 1.5 μm, and the thickness of the portion where the pixel division layer and the spacer layer were laminated was 3.0 μm.

Next, in order to form an organic EL layer 21 including a light-emitting layer by a vacuum deposition method, the pixel division layer/spacer layer forming substrate 1 was rotated with respect to the deposition source under deposition conditions with a vacuum degree of 1×10 ⁻³ Pa or less, and first, a compound (HT-1) represented by structural formula (110) was formed as a hole injection layer with a thickness of 10 nm, and a compound (HT-2) represented by structural formula (111) was formed as a hole transport layer with a thickness of 50 nm. Next, on the light-emitting layer, a compound (GH-1) represented by structural formula (112) was deposited as a host material, and a compound (GD-1) represented by structural formula (113) was deposited as a dopant material with 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 as an electron transport material with a volume ratio of 1:1 to a thickness of 40 nm.

　Next, after depositing a compound (LiQ) to a thickness of 2 nm, a silver/magnesium alloy (volume ratio 10:1) was pattern-deposited to form a second electrode 22 with a thickness of 30 nm, and 50 of the 220 openings in the pixel division layer were made into light-emitting pixel sections. After that, in a low humidity/nitrogen atmosphere, a cap-shaped glass plate was attached and sealed using an epoxy resin adhesive to obtain a top-emission type organic EL display device 1. Note that the thicknesses of the layers constituting the organic EL layer 21 and the second electrode are very thin compared to the pixel division layer described above, and are difficult to measure with high accuracy using a stylus-type film thickness measurement device. Therefore, each was measured using a quartz crystal oscillation-type film thickness monitor, which is suitable for thin films of less than 100 nm, and the value obtained by rounding off the first decimal place of the average value of three points in the plane was taken as the film thickness.

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 top-emission type organic EL display device 1 were evaluated for the rate of non-illuminated pixels (%) using the method described above. The results are shown in Table 19.

(Examples 2 to 16)
Positive photosensitive pigment compositions 2 to 16 were prepared in the same manner as in Example 1, using pigment dispersions 2 to 16, respectively, 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-shielding property of the cured film, and the rate of generation of non-lighted 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.

(Comparative Examples 1 to 4)
Positive photosensitive pigment compositions 17 to 20 were prepared in the same manner as in Example 1, using pigment dispersions 17 to 20, respectively, 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-shielding property of the cured film, and the rate of generation of non-lit pixels were evaluated. The evaluation results are shown in Tables 24 and 25.

(Examples 17 to 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 or 22, polyimide precursor B was used instead of TR4020G, and the 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-shielding property of the cured film, and the rate of non-illuminated pixels were evaluated. The evaluation results are shown in Tables 24 and 25.

(Comparative Examples 5 to 9)
Positive photosensitive pigment compositions 23 to 27 were prepared in the same manner as in Example 1, except that pigment dispersion 1 was replaced with pigment dispersion 24 to 27, polyimide precursor B was used instead of TR4020G, and the amounts of each raw material were as shown in Table 27. Positive photosensitive pigment compositions 23 to 27 do not contain component (a-1). Using the above-mentioned method, the amount of semi-dried film-like foreign matter generated, the first exposure sensitivity, the second exposure sensitivity, the light-shielding property of the cured film, and the rate of non-illuminated pixels were evaluated. The evaluation results are shown in Tables 24 to 25. Note that the positive photosensitive composition 23 in this specification has the same composition as the positive photosensitive composition 21 (Example 16) disclosed in Patent Document 5.

(Synthesis Example 30: Synthesis of pigment dispersant solution 23)
Pigment dispersant solution 23 having a solid 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 50:50) was used instead of PGME, and the blending amounts shown in Table 28 were used.

It was confirmed by ¹³ C-NMR that pigment dispersant solution 23 contains a block copolymer having a block chain consisting only of the repeating unit represented by formula (21), and 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).

In formula (116) and formula (117), * represents a binding site.

(Synthesis Example 31: Synthesis of Pigment Dispersant Solution 24)
As 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), and the solution was stirred under a nitrogen atmosphere / liquid temperature was maintained at 70 ° C. until Mw reached 10000, and then cooled to stop 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 having a solid content of 10.00 mass %. The second polymerization step was not carried out.

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

(Synthesis Example 32: Synthesis of Pigment Dispersant Solution 25)
A pigment dispersant solution 25 having a solid 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.

It was confirmed by ¹³ C-NMR that pigment dispersant solution 25 contains 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).

(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 the hydroxyl group-containing acrylic resin solution X and 84.00 g of the pigment dispersant solution 23 were added and stirred for 5 minutes, and then 28.00 g of the perylene blue pigment 3 was added and stirred for 30 minutes to obtain a preliminary stirred liquid. Next, the preliminary stirring liquid was sent to a vertical bead mill "Ultra Apex Mill Advance (registered trademark)" (manufactured by Hiroshima Metal & Machinery Co., Ltd.) in which 0.4 mmφ zirconia beads "TORECERAM (registered trademark)" (manufactured by Toray Industries, Inc.) were filled in a vessel at a filling rate of 75 volume %, and a wet media dispersion treatment was performed for 3 hours by a circulation method at a peripheral speed of 10 m/s. Furthermore, the same filling rate of 75 volume % was changed to 0.05 mmφ zirconia beads, and a wet media dispersion treatment was performed for 3 hours by a circulation method at a peripheral speed of 8 m/s to obtain a pigment dispersion liquid 28 with a solid content of 10.00 mass %. A first filtration was performed with a filter having a diameter of 0.8 μm, and a second filtration was performed with a filter having a diameter of 0.2 μm. It was confirmed that no change was observed in the value of the solid content up to the second decimal place 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 amount of each raw material is shown in Table 31.

(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, in the amounts shown in Table 31. Note that the light-shielding properties per mass of Perylene Blue Pigment 4 to 6 were lower than the light-shielding property per mass of Perylene Blue Pigment 3, and in order to demonstrate the effect of a composition that gives a cured film having the same light-shielding properties as in Example 19 in Examples 20 to 22 described below, the mass ratio in the solid content of Pigment Dispersions 29 to 31 was adjusted to component (b-2):component (a-1):component (a-2)=34.15:7.68:58.17.

(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, in the amounts shown in Table 31. The mass ratio of the solid content in pigment dispersion 32 was component (b-2):component (a-2)=34.15:65.85. Pigment dispersion 32 does not contain component (a-1).

(Preparation Examples 33 to 34: Preparation of Pigment Dispersions 33 to 34)
Pigment dispersions 33 and 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.

(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 as component (e), 0.07 g of MW-100LM as component (f), and 0.07 g of BYK-333 as a leveling agent in a 5% solids by mass PGME solution were added to 12.82 g of mixed solvent (ethyl lactate: PGMEA = mass ratio 50:50), 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.

Using the method 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 properties of the cured film, and the rate of non-illuminated pixels were evaluated. The evaluation results are shown in Tables 34 to 35.

(Examples 20 to 22)
Positive photosensitive pigment compositions 29 to 31 were prepared in the same manner as in Example 19 using pigment dispersions 29 to 31 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 property of the cured film, and the rate of generation of non-lit pixels were evaluated. The evaluation results are shown in Tables 34 to 35.

(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-dried film-like foreign matter generated, the first exposure sensitivity, the second exposure sensitivity, the light-shielding property of the cured film, and the rate of non-illuminated pixels were evaluated. The evaluation results are shown in Tables 34 and 35.

(Examples 23 to 24)
Positive photosensitive pigment compositions 33 and 34 were prepared in the same manner as in Example 19 using Pigment Dispersions 33 and 34 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 property of the cured film, and the rate of non-illuminated pixels were evaluated. The evaluation results are shown in Tables 34 and 35.

(Reference example)
When the Safety Data Sheet (revised on July 11, 2016) for VALIFAST (registered trademark) BLACK 3804 (onium salt of C.I. Solvent Black 34 and an amine; manufactured by Orient Chemical Industry Co., Ltd.), which is a black dye, is referred to, 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 turn into hexavalent Cr." From the viewpoints of safety for the human body and environmental conservation, it was not possible to evaluate the positive-type photosensitive dye composition disclosed in Patent Document 6, which contains the black dye.

The above examples and comparative examples demonstrate the usefulness of the positive-type 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.

Example 1, which employs an (a-1) component having a block chain consisting of only repeating unit a, has better results than Example 16, which employs an (a-1) component having no block chain consisting of only repeating unit a. Also, Example 29, which employs an (a-1) component having a block chain consisting of only repeating unit a, has better results than Example 33, which employs an (a-1) component having no block chain consisting of only repeating unit a. In other words, it can be seen that a block copolymer having a block chain consisting of only repeating unit a and a repeating unit b is preferable.

Furthermore, in Examples 20 to 22, which use as the component (a-1) a block copolymer having a block chain consisting only of repeating units represented by formula (9), repeating units represented by formula (33), and repeating units represented by formula (54), and which use as the 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), the best results were obtained in each of the evaluations (1) to (5) above.

The positive photosensitive pigment composition of the present invention can be preferably used as a material for forming pixel division layers and spacer layers in organic EL display devices, TFT planarization layers in organic EL display devices, partition walls in quantum dot organic EL display devices (QD-OLEDs), planarization 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, and other applications requiring the formation of highly precise cured films with high light-shielding properties and high exposure sensitivity. In particular, it can be preferably used as a material for collectively forming pixel division layers and spacer layers in flexible, bendable top-emission organic EL display devices.

1: TFT
2: Wiring 3: TFT insulating layer 4: Planarization layer 5: First electrode 6: Substrate 7: Contact hole 8: Pixel division 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: Non-alkali glass substrate 18: Silver alloy film 19: Low-crystalline ITO film 20: Pixel division layer/spacer layer 21: Organic EL layer 22: Second electrode

Claims (11)

A positive-type photosensitive pigment composition comprising: (a) a resin; (b) an organic pigment; (c) a photoacid generator; and (d) an organic solvent,
The (a) resin contains (a-1) a resin having a repeating unit a and a repeating unit b,
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),
The repeating unit b is a repeating unit represented by formula (6).

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 represent 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 represent a single bond or a divalent linking group having 1 to 8 carbon atoms and not containing a nitrogen atom;
R ³ , R ⁶ , R ⁹ , R ¹⁴ , and R ¹⁹ each independently represent an alkyl group having 1 to 3 carbon atoms;
n 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 represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
R ¹⁷ and R ¹⁸ each independently represent 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.
However, R ²¹ does not contain any nitrogen atom other than the nitrogen atom contained in -CONH-.) The positive photosensitive pigment composition according to claim 1, wherein the repeating unit represented by formula (6) includes 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 each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
R ³² and R ³⁵ each independently represent a single bond or a divalent linking group having 1 to 8 carbon atoms;
R ³³ , R ³⁶ , and R ³⁷ each independently represent an alkyl group having 1 to 3 carbon atoms;
n ⁹ is an integer number which is 1 or 2;
n ¹⁰ , n ¹¹ , n ¹² , n ¹³ and n ¹⁴ are integers, each independently representing 0 to 2.
However, R ³² and R ³⁵ do not contain any nitrogen atom other than the nitrogen atom contained in -CONH-.
The sum of ⁿ¹¹ and ⁿ¹² is 0 to 3, and the sum of ⁿ¹² and ⁿ¹⁴ is 1 or 2. The positive photosensitive pigment composition according to claim 1, wherein the (a-1) resin having repeating units a and b is a block copolymer having a block chain consisting of only repeating units a and repeating units b. 2. 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, and the repeating unit c 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;
ⁿ¹⁵ is an integer of 2 to 30, and ^R41 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. The positive photosensitive pigment composition according to claim 1, wherein the (b) organic pigment contains (b-2) an organic pigment having a sulfo group. The positive photosensitive pigment composition according to claim 6, wherein the component (b-2) contains 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).

(In formula (98), formula (99), formula (100), and formula (101), R ⁸⁷ , R ⁹² , R ⁹⁷ , and R ¹⁰⁰ each independently represent -SO ₃ H or -SO ₃ ^- ; R ⁸⁸ , R ⁸⁹ , R ⁹⁰ , R ⁹¹ , R ⁹³ , R ⁹⁴ , R ⁹⁵ , and R ⁹⁶ each independently represent a phenyl group, a benzyl group, or an alkyl group having 1 to 20 carbon atoms; R ⁹⁸ and R ¹⁰¹ each independently represent an alkyl group having 1 to 20 carbon atoms ^; R ⁹⁹ and R ¹⁰² each independently represent an alkyl group having ¹ to 3 carbon atoms; and n ¹⁶ and n ¹⁷ are integers each independently represent 0 to 2. Among ^{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 among R ⁹³ , R ⁹⁴ , R ⁹⁵ , and R ⁹⁶ , one or two groups are a phenyl group, a benzyl group, or an alkyl group having 8 to 20 carbon atoms. A cured film containing a cured product of the positive photosensitive pigment composition according to claim 1. An organic EL display device comprising the cured film according to claim 8. An electronic device equipped with the organic EL display device according to claim 9. A block copolymer having a block chain consisting of only repeating units a and repeating units b,
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),
The repeating unit b is a repeating unit represented by formula (33) and/or a repeating unit represented by formula (34).

In formula (1), formula (2), formula (3), formula (4), and formula (5), * represents a binding site,
R ¹ , R ⁴ , R ⁷ , R ¹¹ , and R ¹⁵ each independently represent 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 represent a single bond or a divalent linking group having 1 to 8 carbon atoms and not containing a nitrogen atom;
R ³ , R ⁶ , R ⁹ , R ¹⁴ , and R ¹⁹ each independently represent an alkyl group having 1 to 3 carbon atoms;
n 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 represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
R ¹⁷ and R ¹⁸ each independently represent an alkyl group having 1 to 5 carbon atoms.

In formula (33) and formula (34), * represents a binding site.
R ³¹ and R ³⁴ each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms;
R ³² and R ³⁵ each independently represent a single bond or a divalent linking group having 1 to 8 carbon atoms;
R ³³ , R ³⁶ , and R ³⁷ each independently represent an alkyl group having 1 to 3 carbon atoms;
n ⁹ is an integer number which is 1 or 2;
n ¹⁰ , n ¹¹ , n ¹² , n ¹³ and n ¹⁴ are integers, each independently representing 0 to 2.
However, R ³² and R ³⁵ do not contain any nitrogen atom other than the nitrogen atom contained in -CONH-.
The sum of ⁿ¹¹ and ⁿ¹² is 0 to 3, and the sum of ⁿ¹² and ⁿ¹⁴ is 1 or 2.

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