CN117043676A

CN117043676A - Positive photosensitive pigment composition, cured film containing cured product thereof, and organic EL display device

Info

Publication number: CN117043676A
Application number: CN202280022641.XA
Authority: CN
Inventors: 石川暁宏; 杉原充; 山本洋平
Original assignee: Toray Industries Inc
Current assignee: Toray Industries Inc
Priority date: 2021-06-22
Filing date: 2022-05-17
Publication date: 2023-11-10

Abstract

The invention provides a positive photosensitive pigment composition which can align an exposure mask by using near infrared rays, has excellent halftone processing property and has high exposure sensitivity and high storage stability. A positive photosensitive pigment composition comprising: (a) a pigment containing a compound having two structures represented by the formula (1) in the molecule and one perylene skeleton in the molecule, (b) a compound having a structure represented by the formula (2) and having no N, N-dialkylaminoalkyl group or a metal salt thereof, (c) a resin, (d) a photoacid generator, and (e) an organic solvent.(in the formula (1), R ¹ Represents phenylene which may have a substituent or naphthylene which may have a substituent. * Represents a bond site with a carbon atom constituting the perylene skeleton. ) (in the formula (2), R ² ～R ⁵ Each independently represents a hydrogen atom, a fluorine atom, a bromine atom or a hydroxyl group. R is R ⁶ A monovalent group having a sulfo group bonded to a carbon atom constituting an aromatic ring and/or a carboxyl group bonded to a carbon atom constituting an aromatic ring. * Represents a bond site with a carbon atom. )

Description

Positive photosensitive pigment composition, cured film containing cured product thereof, and organic EL display device

Technical Field

The present invention relates to a positive photosensitive pigment composition, a cured film containing the same, and an organic Electroluminescent (EL) display device.

Background

In recent years, products having a flexible organic Electroluminescent (EL) display device mounted thereon have been developed. By not using a thick polarizing plate that has been previously disposed on the front surface of the panel, it is desired to improve the flexibility of the panel, and to eliminate the loss of brightness, thereby improving the lifetime of the light-emitting element. In order to replace the function of the polarizing plate, a technique of imparting a light shielding property by blackening a pixel dividing layer by further imparting a function of suppressing reflection of external light such as sunlight to the patterned pixel dividing layer having the function of an insulating layer has been attracting attention.

In order to improve the yield in the production of the panel, the following technique (halftone processing) is known: when forming a light-emitting layer in an opening of a pixel division layer by pattern vapor deposition, the pixel division layer having a step shape is formed together by a photolithography method including an exposure step of irradiating exposure light including at least near ultraviolet rays through a halftone exposure mask having a full-transparent portion, a half-transparent portion, and a shielding portion in a plane, for the purpose of reducing a contact area between a vapor deposition mask and the pixel division layer. The halftone processing is useful because it can greatly reduce the manufacturing process cost compared with the two-layer processing in which thick film portions are laminated after thin film portions are formed.

As a material for forming a black pixel-divided layer having a step shape by halftone processing together, patent document 1 discloses a negative photosensitive pigment composition containing c.i. pigment black 31 as a perylene black pigment and a polymer type dispersant having an N, N-dialkylaminoalkyl group.

On the other hand, as a positive photosensitive pigment composition for forming a black pixel-dividing layer, for example, patent document 2 discloses a positive photosensitive pigment composition containing a pseudo black pigment obtained by mixing c.i. pigment yellow 192 with c.i. pigment red 179 and c.i. pigment blue 60, a perylene pigment derivative type dispersant having an N, N-dialkylaminoalkyl group, and a polymer type dispersant having a phosphate group. Patent document 3 discloses a positive photosensitive pigment composition containing zirconium nitride particles.

Prior art literature

Patent literature

Patent document 1: international publication No. 2018/180592

Patent document 2: international publication No. 2019/065359

Patent document 3: international publication No. 2021/182499

Disclosure of Invention

Problems to be solved by the invention

However, when the black pixel-divided layer having a step is formed together using the negative photosensitive pigment composition disclosed in patent document 1, the halftone processing property is insufficient, and therefore, particularly in a high-definition panel designed to have a small opening width of the opening, there is a problem that the in-plane uniformity of the opening width is low, and uneven brightness occurs in the organic EL display device. On the other hand, when the positive photosensitive pigment composition disclosed in patent document 2 is used, the required exposure amount of the finally obtained pixel division layer increases, and the required exposure amount increases due to an increase in the time course after long-term storage because of insufficient storage stability, so that the panel productivity is low, and there are problems in addition to the above-mentioned problems: the in-plane uniformity of the opening width is low, and uneven brightness occurs in the organic EL display device. In addition, the pre-baked film of the positive photosensitive pigment composition disclosed in patent document 3 has the following problems: because of the optical characteristics of the zirconium nitride particles, the near infrared transmittance is extremely low, and alignment of the exposure mask using a near infrared camera is not possible, making it difficult to perform halftone processing.

Under the above circumstances, a photosensitive composition which can align an exposure mask using near infrared rays, has excellent halftone processability, and has both high exposure sensitivity and high storage stability has been desired. In addition, an organic EL display device that suppresses luminance unevenness even when the opening width of the opening of the pixel dividing layer is small is desired.

Technical means for solving the problems

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

a positive photosensitive pigment composition comprising: (a) a pigment containing a compound having two structures represented by the formula (1) in the molecule and one perylene skeleton in the molecule (hereinafter, sometimes referred to as "component (a)"), (b) a compound having a structure represented by the formula (2) and having no N, N-dialkylaminoalkyl group or a metal salt thereof (hereinafter, sometimes referred to as "component (b)"), (c) a resin (hereinafter, sometimes referred to as "component (c)"), (d) a photoacid generator (hereinafter, sometimes referred to as "component (d)"), and (e) an organic solvent (hereinafter, sometimes referred to as "component (e)").

[ chemical 1]

In the formula (1), R ¹ Represents phenylene which may have a substituent or naphthylene which may have a substituent. * Represents a bond site with a carbon atom constituting the perylene skeleton.

[ chemical 2]

In the formula (2), R ² ～R ⁵ Each independently represents a hydrogen atom, a fluorine atom, or a bromine atom. R is R ⁶ A monovalent group having a sulfo group bonded to a carbon atom constituting an aromatic ring and/or a carboxyl group bonded to a carbon atom constituting an aromatic ring. * Represents a bond site with a carbon atom.

The cured film of the present invention has the following structure. That is to say,

a cured film comprising a cured product of the positive photosensitive pigment composition.

The organic EL display device of the present invention has the following structure. That is to say,

an organic EL display device includes the cured film.

The positive photosensitive pigment composition of the present invention preferably contains a compound having a structure represented by formula (14) or a metal salt thereof (hereinafter, sometimes referred to as "(b-1) component") in component (b-1).

[ chemical 3]

In the formula (14), R ⁷³ ～R ⁷⁶ Each independently represents a hydrogen atom, a fluorine atom, a bromine atom, or a hydroxyl group. R is R ⁷⁷ Represents an alkylene group having 1 to 6 carbon atoms. R is R ⁷⁸ Represents sulfo or carboxyl. n is n ¹ Is an integer, and represents 1 or 2. At n ¹ In the case of 2, two R ⁷⁸ The substituents may be the same or different from each other. R is R ⁷⁹ Represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. n is n ² Is an integer of 0 to 2. At n ² In the case of 2, two R ⁷⁹ The substituents may be the same or different from each other. * Represents a bond site with a carbon atom.

The positive photosensitive pigment composition of the present invention preferably contains a compound having a structure represented by formula (15) or a metal salt thereof (hereinafter, sometimes referred to as "(b-2 component") in component (b-2)).

[ chemical 4]

In the formula (15), R ⁸⁰ ～R ⁸³ Each independently represents a hydrogen atom, a fluorine atom, a bromine atom or a hydroxyl group. R is R ⁸⁴ Represents a single bond or an alkylene group having 1 to 6 carbon atoms. R is R ⁸⁵ Represents a single bond or NH. R is R ⁸⁶ Represents one group selected from the group consisting of a phenylene group substituted with an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, an unsubstituted phenylene group, a naphthylene group substituted with an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and an unsubstituted naphthylene group. R is R ⁸⁷ Represents sulfo or carboxyl. n is n ³ Is an integer, and represents 1 or 2. At n ³ In the case of 2, two R ⁸⁷ The substituents may be the same or different from each other. R is R ⁸⁸ Represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. n is n ⁴ Is an integer of 0 to 2. At n ⁴ In the case of 2, two R ⁸⁸ The substituents may be the same or different from each other. * Represents a bond site with a carbon atom.

The positive photosensitive pigment composition of the present invention preferably has an average aspect ratio of the primary particles of the component (a) of 1.0 to 1.8.

In the positive photosensitive pigment composition of the present invention, the amine value of the resin (c) is preferably 5.0mgKOH/g or less.

The positive photosensitive pigment composition of the present invention preferably contains the compound represented by the formula (3) and/or the compound represented by the formula (4) as the component (a).

[ chemical 5]

In the formula (3) and the formula (4), R ⁷ ～R ¹⁴ Each independently represents a hydrogen atom, a fluorine atom, a bromine atom, a C1-6 alkyl group or a C1-6 alkoxy group. R is R ¹⁵ ～R ²² Each independently represents a hydrogen atom, a fluorine atom or a bromine atom.

The positive photosensitive pigment composition of the present invention is preferably one wherein the resin (c) contains a structural unit represented by the formula (39).

[ chemical 6]

In the formula (39), R ¹⁰¹ R is R ¹⁰² Represents a divalent to octavalent organic group. R is R ¹⁰³ R is R ¹⁰⁴ Each independently represents a phenolic hydroxyl group, a carboxyl group or COOA, and may be a single group, or may be a mixture of groups. A represents a monovalent hydrocarbon group having 1 to 10 carbon atoms. r and s are integers and each independently represents 0 to 6. Wherein r+s > 0 is satisfied. * Indicating the bonding site.

The positive photosensitive pigment composition of the present invention preferably contains the component (b) in an amount of 5 to 50 parts by weight based on 100 parts by weight of the total pigment contained in the positive photosensitive pigment composition.

The positive photosensitive pigment composition of the present invention preferably contains (f) a compound (hereinafter, sometimes referred to as "component (f)") which is converted by heating into a compound having a wavelength of maximum absorption in a region of 350nm to 500nm in a region of 350nm to 780 nm.

The positive photosensitive pigment composition of the present invention preferably contains (h) a pigment containing a compound having a dioxazine skeleton (hereinafter, sometimes referred to as "(h) component").

The positive photosensitive pigment composition of the present invention preferably contains 1 to 50 parts by weight of the (h) component based on 100 parts by weight of the total of the (a) component and the (h) component.

The positive photosensitive pigment composition of the present invention preferably contains a pigment having a compound represented by the formula (12) as the component (h).

[ chemical 7]

In the formula (12), R ¹³¹ 、R ¹³² 、R ¹³³ R is R ¹³⁴ Each independently represents an alkyl group having 1 to 5 carbon atoms. R is R ¹³⁵ R is R ¹³⁶ Each independently represents NH or an oxygen atom.

The positive photosensitive pigment composition of the present invention preferably further contains (i) aminobenzenesulfonic acid.

In order to solve the above problems, an organic EL display device according to the present invention is an organic EL display device including a substrate, a first electrode, a pixel-dividing layer, a light-emitting pixel, and a second electrode, wherein the pixel-dividing layer includes (a) a pigment containing a compound having a structure represented by formula (1) in a molecule and having one perylene skeleton in a molecule, and (b) a compound having a structure represented by formula (2) and having no N, N-dialkylaminoalkyl group, or a metal salt thereof.

[ chemical 8]

[ chemical 9]

In the formula (2), R ² ～R ⁵ Each independently represents a hydrogen atom, a fluorine atom, a bromine atom or a hydroxyl group. R is R ⁶ A monovalent group having a sulfo group bonded to a carbon atom constituting an aromatic ring and/or a carboxyl group bonded to a carbon atom constituting an aromatic ring. * Represents a bond site with a carbon atom.

In the organic EL display device of the present invention, the pixel dividing layer preferably has a thick film portion having a film thickness of 2.5 μm to 4.0 μm and a thin film portion having a film thickness of 1.0 μm to 2.5 μm, and the difference between the film thicknesses of the thick film portion and the thin film portion is 1.0 μm or more.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a pixel dividing layer having a light shielding property, a high in-plane uniformity of an opening width in an opening portion, and a step can be formed at the same time with a stable high exposure sensitivity by halftone processing.

Drawings

Fig. 1 is a captured image obtained in example 16 and including a cross section of a substrate for exposure sensitivity evaluation having a step difference, which was observed by a scanning electron microscope (scanning electron microscope, SEM).

Fig. 2 is a cross-sectional view of a thin-film transistor (TFT) substrate in an organic EL display device as an example of an embodiment of the present invention.

Fig. 3 shows a process for manufacturing an organic EL display device including a process for forming a pixel division layer in all of examples and comparative examples.

[ FIG. 4 ]]The maximum opening width W of the opening of the pixel dividing layer forming substrate in all examples and comparative examples is shown ₁ And minimum opening width W ₂ Is a schematic diagram of one example of (a).

Detailed Description

The present invention will be described in detail below. The numerical range indicated by the term "to" means a range including the numerical values described before and after the term "to" as a lower limit value and an upper limit value. The pixel division layer is a pixel division layer included in the organic EL display device, and does not include a black matrix of the liquid crystal display device. The visible light rays refer to light having a wavelength of 380nm or more and less than 780nm, and the near ultraviolet rays refer to light having a wavelength of 200nm or more and less than 380 nm. Near infrared refers to light having a wavelength of 780nm or more and 1300nm or less. The light shielding means a function of reducing the intensity of light transmitted through the cured film with respect to the intensity of light incident in the vertical direction, and the light shielding means a degree of shielding visible light. The transmittance refers to light transmittance. The weight average molecular weight (Mw) is a value obtained by analysis by gel permeation chromatography using tetrahydrofuran as a carrier and conversion using a calibration curve based on standard polystyrene.

The term "c.i." used in the designation of a part of coloring materials is an abbreviation of a common name (Colour Index Generic Name) of color index, and the common name (Colour Index Generic Name) of color index indicates a chemical structure or crystal form of a pigment or dye with respect to coloring materials registered in the color index based on the color index issued by the society of dyes and colorists (The Society of Dyers and Colourists). Carbon black classified as c.i. pigment black 7 and the like is classified as an inorganic black pigment. The solid component refers to the proportion (wt%) of the components excluding the organic solvent and water in the positive photosensitive pigment composition.

The present inventors have made an intensive study and as a result, have found that a pigment composition obtained by combining a pigment having a specific chemical structure with a pigment having a specific chemical structure and further imparting positive photosensitivity with a resin and a photoacid generator has a particularly remarkable effect in solving the above problems.

Specifically, the positive photosensitive pigment composition of the present invention is a positive photosensitive pigment composition containing (a) a pigment containing a compound having a structure represented by the formula (1) and having one perylene skeleton in the molecule, (b) a compound having a structure represented by the formula (2) and having no N, N-dialkylaminoalkyl group or a metal salt thereof, (c) a resin, (d) a photoacid generator, and (e) an organic solvent.

[ chemical 10]

[ chemical 11]

The positive photosensitive pigment composition of the present invention contains (a) a pigment containing a compound having two structures represented by formula (1) in a molecule and one perylene skeleton in a molecule as an essential structural element. (a) The component has an effect of imparting light shielding property to the pixel division layer finally obtained. When the component (b) is present together, the maximum transmittance in the region of 300nm to 450nm can be further improved with respect to the minimum transmittance in the region of 500nm to 600nm of the component (a), while the exposure light including at least the light of the region of 300nm to 450nm can easily reach the deep portion of the film, thereby obtaining high exposure sensitivity. The exposure sensitivity referred to herein means the minimum exposure amount required for forming the pixel division layer having the opening portion having the desired film thickness and the desired opening width in the exposure step described later, and the high exposure sensitivity means the minimum exposure amount is small. In addition, the maximum transmittance in the range of 800nm to 1,200nm is higher in the component (a) than in the range of 300nm to 450nm, and the exposure mask is automatically aligned with respect to the electrode forming substrate by using the near infrared camera, so that exposure can be performed with high positional accuracy by near infrared alignment, and higher productivity and high yield can be obtained. Further, since the component (a) has not only a perylene skeleton but also two structures represented by the formula (1) in the molecule, the component (a) has higher heat resistance than the c.i. pigment black 31 or the pseudo-black pigment, which are the perylene black pigment, and does not depend on the oxygen concentration in the curing step described later, and does not undergo discoloration or discoloration even after the high-temperature treatment at 250 ℃. Accordingly, the pigment component in the film can be reduced in addition to the desired light-shielding property, and thus a desirably high exposure sensitivity can be exhibited.

[ chemical 12]

Examples of the compound having two structures represented by the formula (1) in the molecule and one perylene skeleton in the molecule include: a compound represented by formula (3) as a cis-form, a compound represented by formula (4) as a trans-form, a compound represented by formula (5) as a cis-form, a compound represented by formula (6) as a trans-form, a compound represented by formula (7) as a cis-form, and a compound represented by formula (8) as a trans-form.

[ chemical 13]

[ chemical 14]

In the formula (5) and the formula (6), R ²³ ～R ³⁴ Each independently represents a hydrogen atom, a fluorine atom, a bromine atom, a C1-6 alkyl group or a C1-6 alkoxy group. R is R ³⁵ ～R ⁴² Each independently represents a hydrogen atom, a fluorine atom or a bromine atom.

[ 15]

In the formula (7) and the formula (8), R ⁴³ ～R ⁵⁴ Each independently represents a hydrogen atom, a fluorine atom, a bromine atom, a C1-6 alkyl group or a C1-6 alkoxy group. R is R ⁵⁵ ～R ⁶² Each independently represents a hydrogen atom, a fluorine atom or a bromine atom.

Among them, in terms of improving the exposure sensitivity, the positive photosensitive pigment composition of the present invention preferably contains the compound represented by the formula (3) and/or the compound represented by the formula (4) as the component (a). More preferably, the compound represented by the formula (9) is a cis-form compound and/or the compound represented by the formula (10) is a trans-form compound.

The compound (a) having two structures represented by the formula (1) in the molecule and one perylene skeleton in the molecule may be contained singly or in a plurality of types, and is more preferably contained in an amount of 40 to 100% by weight based on 100% by weight of the sum of cis-form and trans-form, in order to improve the exposure sensitivity.

[ 16]

(a) The component (A) can be obtained, for example, by pigmenting a reaction product of perylene-3, 4,9, 10-tetracarboxylic dianhydride or a derivative thereof and 1, 2-diaminobenzene or a derivative thereof. Specifically, perylene-3, 4,9, 10-tetracarboxylic dianhydride and 1, 2-diaminobenzene as starting materials are added to phenol melted at 70 ℃ in a molar (mol) ratio of 1:2, and the mixture to which an alkaline catalyst such as piperazine is added is stirred at a liquid temperature of 120 to 190 ℃ for 6 to 10 hours, whereby the reaction is sufficiently performed, and then the produced water is distilled off as an azeotropic mixture with phenol. Then, the mixture is cooled to 130 ℃, methanol or ethanol is added, and the mixture is stirred for 1 hour at 50-70 ℃ and then filtered and separated. Further, the resultant is washed with methanol or ethanol until the filtrate is transparent, and then washed with water, and dried at 40 to 80 ℃ under reduced pressure for 24 hours or more, whereby a pigment crude product corresponding to a compound having two structures represented by formula (1) in the molecule and one perylene skeleton in the molecule is obtained. The pigment crude product is obtained as a mixture containing 30 to 70 parts by weight of a trans-form relative to 100 parts by weight of the total of the cis-form and the trans-form. The pigment crude refers to a pigment precursor before the pigment forming step. Further, as the pigment formation step, chemical and/or physical fine treatments described later are performed to obtain a component (a) containing the compound represented by the formula (3) and the compound represented by the formula (4).

The component (a) comprising the compound represented by the formula (5) and the compound represented by the formula (6) can be obtained by synthesis and pigmenting using 1, 8-diaminonaphthalene or a derivative thereof instead of the 1, 2-diaminobenzene or a derivative thereof by the same method. Further, the component (a) comprising the compound represented by the formula (7) and the compound represented by the formula (8) can be obtained by synthesis and pigmentation using 1, 2-diaminonaphthalene or a derivative thereof.

As the derivative of perylene-3, 4,9, 10-tetracarboxylic dianhydride as a starting material, for example, 1, 7-dibromoperylene-3, 4,9, 10-tetracarboxylic dianhydride obtained by a selective synthesis method disclosed in international publication No. 97/22607, or monobromoperylene-3, 4,9, 10-tetracarboxylic dianhydride disclosed in japanese patent laid-open publication No. 2018-165257 can be cited. For example, commercially available perylene-3, 4,9, 10-tetracarboxylic dianhydride derivatives manufactured by Henan Tianfu chemical (Henan Tianfu Chemical) are used.

Examples of the derivative of 1, 2-diaminobenzene include: 4, 5-dimethyl-1, 2-phenylenediamine, 4, 5-diethyl-1, 2-phenylenediamine, 4, 5-dipropyl-1, 2-phenylenediamine, 1, 2-diamino-4-fluorobenzene, 1, 2-diamino-4-bromobenzene, 4-methoxy-1, 2-phenylenediamine, 4-ethoxy-1, 2-phenylenediamine, 4-propoxy-1, 2-phenylenediamine, 4-butoxy-1, 2-phenylenediamine, 1, 2-diamino-4, 5-methoxybenzene, 1, 2-diamino-4, 5-ethoxybenzene, 1, 2-diamino-4, 5-propoxybenzene, 1, 2-diamino-4, 5-butoxybenzene may be used singly or in combination.

Examples of pigments that include the compound represented by the formula (9) and the compound represented by the formula (10) include commercially available pigments such as "spettrasse (registered trademark)" Black K0087 (manufactured by BASF). The high-purity product in which the content of the compound represented by the formula (9) is a trace amount and the compound represented by the formula (10) contains 80 wt% or more of a trans-form is manufactured by PTCBI (manufactured by the institute of technology and electronics) (Luminescence Technology Corporation).

In terms of improving the halftone processing property, the average primary particle diameter of the component (a) is preferably 10nm or more, more preferably 20nm or more. In terms of improving the exposure sensitivity, it is preferably 120nm or less, more preferably 80nm or less.

The average primary particle diameter as used herein refers to a number average value of primary particle diameters calculated by a particle size measurement method using an image analysis type particle size distribution measuring apparatus. For image capturing, a transmission electron microscope (transmission electron microscope, TEM) may be used, and 50 primary particles randomly selected from images of 100 or more primary particles of component (a) captured at a magnification of 50,000 times may be analyzed to calculate an average primary particle diameter. When the component (a) is not spherical, the average value of the major axis and the minor axis is defined as the primary particle diameter. Image analysis type particle size distribution software Mac-View (manufactured by Mount technology) Inc., according to JIS8827-1, particle size analysis-image analysis method can be used in image analysis.

The average aspect ratio of the primary particles of component (a) is preferably 1.0 to 1.8, more preferably 1.0 to 1.4, in terms of improving the exposure sensitivity and halftone processing properties.

That is, the positive photosensitive pigment composition of the present invention preferably has an average aspect ratio of the primary particles of component (a) of 1.0 to 1.8.

The aspect ratio of the primary particles is a value obtained by rounding the second decimal point of the value obtained by dividing the value of the long diameter by the value of the short diameter of the primary particles. The average aspect ratio of the primary particles is a number average value of aspect ratios of 50 primary particles randomly selected from images of 100 or more primary particles of component (a) captured by TEM at a magnification of 50,000 times.

In terms of improving the storage stability, the maximum primary particle diameter of the component (a) is preferably 40nm or more, more preferably 80nm or more. In terms of improving the exposure sensitivity, it is preferably 200nm or less, more preferably 150nm or less. The maximum primary particle diameter is the maximum value of 50 primary particle diameters used in calculating the average primary particle diameter.

As a method for controlling the average primary particle diameter, the average aspect ratio of primary particles, and the maximum primary particle diameter of the component (a), a chemical micronization treatment such as an acid paste method and/or a physical micronization treatment such as a solvent salt mill method can be preferably applied. The acid paste method is particularly effective for the fine-sizing of high-hardness organic pigments, and the solvent salt milling method is particularly effective for the reduction of coarse primary particles, and all the methods can be preferably applied to the fine-sizing treatment of the component (a).

The acid paste method is a method comprising the steps of: a crude organic pigment or a liquid of an organic pigment is dissolved in a strong acid such as 50 to 98 wt% sulfuric acid aqueous solution, and the obtained solution is poured into a large amount of water to precipitate and granulate the solution, and then the solution is filtered and separated, and further the strong acid is removed by washing with water, and dried and pulverized to obtain a fine organic pigment.

On the other hand, the solvent salt milling method is a method comprising: the paste in which the organic pigment, the milled material and the water-soluble organic solvent are mixed is wet-kneaded at 20 to 80 ℃, and then put into a large amount of water to be stirred, and the filtrate from which the milled material and the water-soluble organic solvent are removed by washing with water is dried and pulverized to obtain the fine organic pigment. As the kneader, for example, a kneader (manufactured by well manufacturing stations (strands)) can be used. As the grinding material, water-soluble inorganic salts in the form of fine particles having an average primary particle diameter of 0.1 μm to 50 μm are used, and examples thereof include sodium chloride, potassium chloride and potassium sulfate. It is desirable to perform a heat treatment at 200 ℃ or higher to reduce the moisture content to 0.5 wt% or less in advance, thereby improving the hardness. The water-soluble organic solvent is preferably a glycol solvent. Examples of the glycol-based solvent include: ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol. By allowing the component (a) and the component (b) to coexist and performing chemical and/or physical micronization treatment, a pigment in which at least a part of the component (a) is subjected to surface treatment with the component (b) may be produced, and thus higher exposure sensitivity may be obtained.

The total amount of the strong acid in the acid paste method, the ground material in the solvent salt grinding method, and the residual amount of the ionic impurities as a source is preferably 500 ppm by weight or less, more preferably 100 ppm by weight or less in the component (a) in terms of improving the insulation property of the pixel dividing layer and avoiding short-circuiting at the time of voltage application. For the purpose of improving the removal rate, the following steps may be added: the component (a) is washed with a solution in which 0.1 to 1.0 wt% of a nonionic surfactant is mixed in warm water.

(a) The form of the compound having two structures represented by the formula (1) in the molecule and one perylene skeleton in the molecule is not particularly limited. (a) The component (c) may be a pigment containing only a compound having two structures represented by formula (1) in the molecule and one perylene skeleton in the molecule, or may be a pigment further containing mixed crystals with other pigment compounds. The pigment comprising mixed crystals described herein can be produced, for example, by: the chemical refining treatment such as the acid pasting method is performed by allowing a compound having two structures represented by the formula (1) in a molecule and one perylene skeleton in a molecule to coexist with an organic dye compound and/or an organometallic complex dye compound as another dye compound. In the present specification, a pigment containing a mixed crystal of a compound having two structures represented by the formula (1) in a molecule and one perylene skeleton in a molecule and a compound having a dioxazine skeleton is defined as a mixture of the component (a) and the component (h). The mixing ratio was obtained based on the weight ratio calculated from the ratio of the mol numbers of the two compounds. Similarly, secondary particles including an agglomerate of primary particles of the component (a) and primary particles of the component (h), pigments obtained by treating the component (h) on the surface of the component (a), pigments obtained by treating the component (a) on the surface of the component (h), and the like are also defined as a mixture of the component (a) and the component (h).

In terms of improving the light-shielding property of the pixel-dividing layer, the content of the compound having two structures represented by the formula (1) in the molecule and one perylene skeleton in the molecule contained in the component (a) is preferably 1% by weight or more, more preferably 5% by weight or more, based on 100% by weight of the solid content of the positive photosensitive pigment composition. In terms of improving the exposure sensitivity, it is preferably 30% by weight or less, more preferably 20% by weight or less.

The positive photosensitive pigment composition of the present invention preferably further contains (h) a pigment containing a compound having a dioxazine skeleton. The dioxazine skeleton as used herein refers to a trimellitic dioxazine skeleton. (h) The component (a) has an effect of imparting light shielding properties to the pixel division layer to be finally obtained, and is easy to allow exposure light including at least light having a wavelength of 300nm to 450nm to reach the deep portion of the film, so that high exposure sensitivity can be obtained. In addition, from the viewpoint described above, particularly in the case of forming a pixel dividing layer having a high light-shielding property (OD/μm) exceeding 0.8, a decrease in exposure sensitivity can be suppressed.

In terms of improving the exposure sensitivity, the content of the component (h) is preferably 1 part by weight or more, more preferably 10 parts by weight or more, relative to 100 parts by weight of the total of the component (a) and the component (h). On the other hand, in terms of improving the storage stability, it is preferably 50 parts by weight or less, more preferably 40 parts by weight or less.

That is, the positive photosensitive pigment composition of the present invention preferably contains 1 to 50 parts by weight of the component (h) based on 100 parts by weight of the total of the component (a) and the component (h).

Examples of the component (h) include a pigment containing a compound represented by the formula (11) and a pigment containing a compound represented by the formula (12). The compound represented by the formula (11) and the compound represented by the formula (12) have two oxazine rings in the molecule. Namely, the compound has a dioxazine skeleton in the molecule. Specific examples of the compound represented by the formula (11) include compounds represented by the formula (11), wherein R ⁶³ R is R ⁶⁴ Is a chlorine atom, R ⁶⁵ R is R ⁶⁸ Is a hydrogen atom, R ⁶⁶ R is R ⁶⁷ Pigment which is a compound of ethyl, i.e. c.i. pigment blue 80. Specific examples of the compound represented by the formula (12) include compounds represented by the formula (12), wherein R ¹³¹ R is R ¹³² Is ethyl, R ¹³³ R is R ¹³⁴ Is methyl, R ¹³⁵ R is R ¹³⁶ The pigment of the compound being NH is c.i. pigment violet 37.

[ chemical 17]

In the formula (11), R ⁶³ R is R ⁶⁴ Each independently represents a hydrogen atom or a halogen atom. R is R ⁶⁵ ～R ⁶⁸ Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.

[ chemical 18]

Among them, a pigment containing a compound represented by formula (12) is preferable in terms of obtaining high exposure sensitivity.

That is, the positive photosensitive pigment composition of the present invention more preferably contains a pigment having a compound represented by the formula (12) as the component (h).

In the formula (12), R ¹³¹ R is R ¹³² Mutually identical, preferably C1-3 alkyl radicals, R ¹³³ R is R ¹³⁴ Preferably methyl, R ¹³⁵ R is R ¹³⁶ Preferably NH.

That is, the positive photosensitive pigment composition of the present invention most preferably contains a pigment having a compound represented by the formula (13) as the component (h).

[ chemical 19]

In the formula (13), R ⁶⁹ R is R ⁷⁰ The same as each other, represents an alkyl group having 1 to 3 carbon atoms.

As other pigments, there may be mentioned: organic yellow pigments such as c.i. pigment yellow 24, 120, 138, 139, 150, 151, 175, 180, 185, 181, 192, 193, 194, organic orange pigments such as c.i. pigment orange 13, 36, 43, 60, 61, 62, 64, 71, 72, organic red pigments such as c.i. pigment red 122, 123, 149, 178, 177, 179, 180, 189, 190, 202, 209, 254, 255, 264, c.i. pigment blue 15, 15: 1. 15: 2. 15: 3. 15: 6. 16, 25, 56, 57, 60, 61, 64, 65, 66, 75, 79, 80, etc., and c.i. pigment violet 19, 29, 32, etc.

The positive photosensitive pigment composition of the present invention contains (b) a compound having a structure represented by formula (2) and having no N, N-dialkylaminoalkyl group or a metal salt thereof as an essential structural element. The metal salt as referred to herein means a metal salt of a sulfonic acid and a metal salt of a carboxylic acid, that is, a group of a metal salt having a sulfo group and/or a group of a metal salt of a carboxyl group, which are metal salts of the component (b).

In order to improve halftone processing properties, exposure sensitivity and storage stability, the positive photosensitive pigment composition of the present invention preferably contains an organic pigment compound or a metal salt thereof as the component (b).

The organic pigment compound as described herein means an organic dye or an organic pigment.

(b) The composition has effects of improving halftone processing property, exposure sensitivity and storage stability. The improvement of halftone processing means improvement of in-plane uniformity of opening width of an opening of a pixel division layer having a step. By improving the in-plane uniformity of the opening width, variation in the size of the light-emitting pixels formed in the opening of the pixel dividing layer can be suppressed, and uneven brightness can be suppressed. The storage stability is the rate of change in the exposure sensitivity of the positive-type photosensitive pigment composition after 30 days of storage, based on the exposure sensitivity of the positive-type photosensitive pigment composition after 1 day of storage after preparation. The high storage stability means that the rate of change in exposure sensitivity is desirably small. The term "storage" means that the positive photosensitive pigment composition is left in a closed state under an atmospheric pressure in a dark place maintained at-20.+ -. 1 ℃ under light shielding. In general, the general knowledge of those skilled in the art is stored in such an environment in order to reduce the time-dependent change of a positive photosensitive pigment composition containing a photoacid generator having high activity against heat or light. By improving the exposure sensitivity, the panel productivity can be improved, and by improving the storage stability, the pixel division layer having a step difference can be formed with stable exposure sensitivity.

By the compound belonging to the component (b) having no N, N-dialkylaminoalkyl group, the following effects can be exhibited without impairing the storage stability: the effect of improving halftone processability, exposure sensitivity, and storage stability can be obtained by providing a high pi-pi stacking effect of the component (a) having the structure represented by the formula (2) as a source, and a high charge imparting effect of the sulfo group bonded to a carbon atom constituting an aromatic ring and/or the carboxyl group bonded to a carbon atom constituting an aromatic ring as a source. In addition, when the positive photosensitive pigment composition contains the component (h), the component (b) can exhibit the above-described action effect not only on the component (a) but also on the component (h), and thus an effect of improving halftone processability, exposure sensitivity and storage stability can be obtained. As the N, N-dialkylaminoalkyl group described herein, for example, there may be mentioned: n, N-dimethylaminoethyl group, N-dimethylaminopropyl group, N-diethylaminopropyl group, and N, N-dipropylaminopropyl group, but does not contain an imide ring contained in the molecule of the component (b). The compound having a structure represented by the formula (1) and one perylene skeleton in the molecule, the compound having a structure represented by the formula (2) and not having an N, N-dialkylaminoalkyl group, or a metal salt thereof, is defined as a compound belonging to the component (b).

[ chemical 20]

The sulfo groups described herein are not only-SO ₃ H is present in the positive photosensitive pigment composition in a form of being dissociated from protons, namely-SO ₃ ^- . The carboxyl group is also referred to as-COO, which is a form of proton dissociation, in addition to-COOH ^- 。

In the formula (2), R is preferable in terms of improving the exposure sensitivity ² ～R ⁵ All hydrogen atoms. Preferably R ⁶ Is a monovalent group having one or two sulfo groups bonded to carbon atoms constituting an aromatic ring. Preferably, the bond is to a carbon atom constituting the naphthalene skeleton. Regarding R as a monovalent group ⁶ Examples of the group having a sulfo group bonded to a carbon atom constituting an aromatic ring and/or a carboxyl group bonded to a carbon atom constituting an aromatic ring include: sulfophenyl, disulfophenyl, carboxyphenyl, dicarboxyphenyl, carboxy-sulfophenyl, methyl-sulfophenyl, methoxy-sulfophenyl, sulfonaphthyl, disulfonaphthyl, carboxynaphthyl, dicarboxynaphthyl, carboxy-sulfonaphthyl, methyl-sulfonaphthyl, methoxy-sulfonaphthyl. Wherein the storage stability is improved In terms of the surface, a group in which one or two sulfo groups are substituted with phenyl groups is preferable.

Examples of the metal salt of the compound having the structure represented by the formula (2) include: with Na and Na ⁺ 、K ⁺ 、Li ⁺ Salts of monovalent metal cations, or with Ca ²⁺ 、Mn ²⁺ 、Sr ²⁺ 、Ba ²⁺ 、Zn ²⁺ 、Al ³⁺ Salts of alike polyvalent metal cations.

As the component (b), an aromatic ring having a sulfo group bonded to a carbon atom constituting an aromatic ring and/or a carboxyl group bonded to a carbon atom constituting an aromatic ring is preferably a compound having a structure bonded to a nitrogen atom of an imide ring via an alkylene group having 1 to 6 carbon atoms and/or a divalent linking group containing an azo bond in terms of improving exposure sensitivity and storage stability. Specifically, it is preferable that (b-1) the compound having the structure represented by the formula (14) or a metal salt thereof, or (b-2) the compound having the structure represented by the formula (15) or a metal salt thereof.

That is, the positive photosensitive pigment composition of the present invention preferably contains a compound having a structure represented by the formula (14) as the component (b) or a metal salt thereof. More preferably, (b-1) the compound having the structure represented by the formula (14) or a metal salt thereof contains an organic dye compound or a metal salt thereof.

The positive photosensitive pigment composition of the present invention preferably contains a compound having a structure represented by formula (15) as component (b-2) or a metal salt thereof. More preferably, (b-2) the compound having the structure represented by the formula (15) or a metal salt thereof contains an organic dye compound or a metal salt thereof.

In the present specification, a compound having both the structure represented by the formula (14) and the structure represented by the formula (15) in the molecule is defined as a compound belonging to the component (b-2).

[ chemical 21]

In the formula (14), R ⁷³ ～R ⁷⁶ Each independently represents a hydrogen atom, a fluorine atom, a bromine atom or a hydroxyl group. R is R ⁷⁷ Represents an alkylene group having 1 to 6 carbon atoms. R is R ⁷⁸ Represents sulfo or carboxyl. n is n ¹ Is an integer, and represents 1 or 2. At n ¹ In the case of 2, two R ⁷⁸ The substituents may be the same or different from each other. R is R ⁷⁹ Represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. n is n ² Is an integer of 0 to 2. At n ² In the case of 2, two R ⁷⁹ The substituents may be the same or different from each other. * Represents a bond site with a carbon atom.

As the form of the metal salt of the compound having the structure represented by the formula (14), the same viewpoints as those of the form of the metal salt of the compound having the structure represented by the formula (2) can be applied.

[ chemical 22]

As the form of the metal salt of the compound having the structure represented by formula (15), the same viewpoints as those of the form of the metal salt of the compound having the structure represented by formula (2) can be applied.

The positive photosensitive pigment composition of the present invention more preferably contains the compound represented by the formula (16) as the component (b-1). The compound represented by the formula (16) corresponds to an organic dye compound.

The positive photosensitive pigment composition of the present invention more preferably contains the compound represented by the formula (17) as the component (b-2). The compound represented by the formula (17) corresponds to an organic dye compound.

[ chemical 23]

In the formula (16), R ⁸⁹ R is R ⁹⁰ Each independently represents an alkylene group having 1 to 6 carbon atoms. n is n ⁵ Is an integer of 0 to 2.R is R ⁹¹ R is R ⁹² Represents sulfo or carboxyl. n is n ⁶ Is an integer, and represents 1 or 2.n is n ⁷ Is an integer, and represents 0 or 1. At n ⁶ In the case of 2, two R ⁹¹ The substituents may be the same or different from each other.

[ chemical 24]

In the formula (17), R ⁹³ R is R ⁹⁴ Each independently represents one group selected from the group consisting of a phenylene group substituted with an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, an unsubstituted phenylene group, an alkyl group having 1 to 6 carbon atoms, a naphthylene group substituted with an alkoxy group having 1 to 6 carbon atoms, and an unsubstituted naphthylene group. n is n ⁸ Is an integer of 0 to 2.R is R ⁹⁵ R is R ⁹⁶ Represents sulfo or carboxyl. n is n ⁹ Is an integer, and represents 1 or 2.n is n ¹⁰ Is an integer, and represents 0 or 1. At n ⁹ In the case of 2, two R ⁹⁵ Can be the same substituentMay be different substituents.

Further, the compound represented by the formula (16) is represented by n ⁵ Having a naphthalene skeleton in the case of 0, and n ⁵ 1, has a perylene skeleton in the case of 1, and n ⁵ In the case of 2, there is a tribenzo [ de, kl, rst ]]A valerfene (terylene) backbone. The compound represented by the formula (17) is represented by n ⁸ Having a naphthalene skeleton in the case of 0, and n ⁸ 1, has a perylene skeleton in the case of 1, and n ⁸ In the case of 2, there is a tribenzo [ de, kl, rst ]]A valerfene backbone.

Specific examples of the compound belonging to the component (b-1) include: the compound represented by formula (20), the compound represented by formula (21), the compound represented by formula (22), and the compound represented by formula (23) correspond to organic dye compounds. Specific examples of the compound belonging to the component (b-2) include: the compound represented by formula (18), the compound represented by formula (19), the compound represented by formula (24), the compound represented by formula (25), the compound represented by formula (26), the compound represented by formula (27), the compound represented by formula (28), the compound represented by formula (29), the compound represented by formula (30), the compound represented by formula (31), and the compound represented by formula (32) correspond to organic dye compounds.

[ chemical 25]

[ chemical 26]

[ chemical 27]

[ chemical 28]

Examples of the method for obtaining the compound belonging to the component (b) include sulfonation and imidization. If necessary, the two reactions may be combined to form a two-stage synthesis route.

When the method of obtaining the component (b-2) by sulfonation is exemplified, the following will be described. The c.i. pigment red 178 represented by the formula (33) as a starting material is dissolved in 10 to 50 wt% fuming sulfuric acid or 50 to 100 wt% concentrated sulfuric acid, and the mixture is heated, and the liquid temperature is adjusted in the range of 40 to 90 ℃ and stirred for 3 to 10 hours so that a sulfo group is selectively introduced into the terminal phenyl group. The liquid temperature is set to 40 ℃ or higher, whereby the residual unreacted components of the starting material can be suppressed, and the liquid temperature is set to 90 ℃ or lower, whereby the decomposition reaction of the starting material can be suppressed, and the purity of the product can be improved.

[ chemical 29]

Then, the mixture is poured into water, preferably ice water, in an amount of 100 times or more the weight of the starting materials, to obtain a slurry containing red precipitates, and the slurry is filtered. After washing with methanol or ethanol, the washing with water is preferably repeated until the residual amount of sulfate ions is less than 50 ppm by weight, and the mixture is dried under reduced pressure at 60 to 80 ℃. Finally, the powder is formed by dry pulverization using a hammer mill or jet mill to remove the dry agglomeration. By the above-described operations, a compound represented by the formula (24) of the monosulfo matrix, a compound represented by the formula (25) of the disulfo matrix, and/or a compound represented by the formula (26) of the trisulfo matrix (or metal salts thereof) corresponding to the component (b-2) can be obtained. The number of introduction of sulfo groups per molecule of the target product and the distribution thereof can be controlled by the liquid temperature and the reaction time corresponding to the concentration of fuming sulfuric acid or concentrated sulfuric acid, and the reaction end point can be determined by structural analysis by liquid chromatography-mass spectrometry (liquid chromatography-mass spectrometry, LC-MS) and nuclear magnetic resonance (nuclear magnetic resonance, NMR) as described above. Further, by performing purification treatment using silica gel chromatography, the purity of the compound having a specific number of sulfo groups introduced therein can be improved.

The component (b-1) can also be obtained by the same sulfonation reaction, and for example, if the c.i. pigment black 31 represented by the formula (34) is used as a starting material instead of the c.i. pigment red 178, the compound represented by the formula (21) can be synthesized. Examples of the commercial product of c.i. pigment Black 31 include "spettrasse (registered trademark)" Black S0084 (manufactured by BASF).

[ chemical 30]

On the other hand, when a method of obtaining the component (b) by imidization is exemplified, the following will be described. The perylene-3, 4,9, 10-tetracarboxylic dianhydride represented by the formula (35) or a derivative thereof, which is a starting material, and an amino acid having a primary amino group such as 3- (aminomethyl) benzoic acid represented by the formula (36) are preferably added to and mixed with an alkaline synthetic solvent such as molten imidazole. Optionally, a catalyst such as zinc acetate may be added.

[ 31]

Then, the imidization reaction is performed by maintaining a heating temperature of 80 to 160 ℃ under a nitrogen atmosphere and stirring for 3 to 10 hours. After the obtained mixture is cooled to 20 ℃ or lower, 10 to 50 wt% hydrochloric acid is added as needed, and the mixture is poured into a large amount of water, preferably ice water, which is 100 times or more by weight relative to the starting material used, to obtain a slurry containing red precipitate, and the slurry is filtered. After washing with methanol or ethanol, the washing with water is preferably repeated until the residual amount of the amino acid is less than 50 ppm by weight, and the resultant mixture is dried under reduced pressure at 60 to 80 ℃. Finally, the powder is formed by dry pulverization using a hammer mill or jet mill to remove the dry agglomeration. By the above-described operation, the compound represented by the formula (23) corresponding to the component (b-1) can be obtained.

The component (b-2) can also be obtained by the same imidization reaction, and for example, if the compound represented by the formula (37) is used instead of the amino acid, the compound represented by the formula (27) can be synthesized.

[ chemical 32]

In addition, if N- (1-naphthyl) ethylenediamine is used instead of the amino acid, the compound represented by the formula (19) can be obtained. The compound represented by the above formula (30) and the compound represented by the above formula (31) can be synthesized by imidization reaction of perylene-3, 4,11, 12-tetracarboxylic dianhydride or naphthalene-1, 4,5, 8-tetracarboxylic dianhydride with 3- [ (4-aminophenyl) azo ] benzenesulfonic acid, respectively.

Examples of the method for obtaining the component (b) include the following methods: after preparing a slurry in which a compound having a structure represented by formula (2) and having no N, N-dialkylaminoalkyl group is dispersed in water, al such as aluminum chloride is added under alkaline conditions ³⁺ Source, barium chloride and the like Ba ²⁺ Source, or Ca such as calcium chloride ²⁺ The raw materials are heated to 30-60 ℃ and stirred to form salt, and then refined, dried and dried to be crushed into powder.

The form of the component (b) in the positive photosensitive pigment composition and in the pixel-dividing layer is not particularly limited, and at least a part of the component (b) may be insoluble particles or may be soluble. In terms of improving the storage stability, it is preferable that 90% by weight or more of the component (b) is present as insoluble particles, and the presence form can be preferably controlled by the component (c) and the organic solvent (e) described later. More preferably, the pigment dispersion liquid to be described later is prepared in such a manner that at least a part of the component (b) is adsorbed on the surface of the component (a) in the coexistence. In the case of containing the component (h), it is preferable that at least a part of the component (b) is adsorbed on the surface of the component (h). (b) The component (c) may form a solid solution with at least any one of the component (a) and the component (h). When the component (b) contains insoluble particles, the average primary particle diameter and the average aspect ratio thereof can be preferably the same as those of the component (a).

The content of the component (b) is preferably 5 parts by weight or more, more preferably 12 parts by weight or more, based on 100 parts by weight of the total pigment contained in the positive photosensitive pigment composition, in terms of improving the storage stability. In terms of improving the exposure sensitivity, it is preferably 50 parts by weight or less, more preferably 40 parts by weight or less.

That is, the positive photosensitive pigment composition of the present invention more preferably contains 5 to 50 parts by weight of the component (b) based on 100 parts by weight of the total pigment contained in the positive photosensitive pigment composition. The pigment contained in the positive photosensitive pigment composition described herein means a group of the component (a) and the component (h) and the pigment exemplified as other pigments, and the component (b) is not contained regardless of whether the component (b) exists in the positive photosensitive pigment composition in the form of dissolved and/or insoluble particles. When the component (b) forms a solid solution with at least one of the component (a) and the component (h), the content of the component (b) can be obtained by converting the mol number of the compound constituting the component (b) and the mol number of the compound constituting the pigment into weight.

The chemical structure of the compound constituting the component (a), the component (h) and the component (b) can be analyzed by: the concentrate obtained by subjecting the positive photosensitive pigment composition of the present invention to centrifugal separation is used as a sample, and known analysis methods such as matrix-assisted laser desorption ionization-time-of-flight mass spectrometry (matrix assisted laser desorption ionization-time-of-flight mass spectrometry, MALDI-TOF MS), time-of-flight secondary ion mass spectrometry (time-of-flight secondary ion mass spectrometry, TOF-SIMS), time-of-flight mass spectrometry (time-of-flight mass spectrometry, TOF-MS), nuclear Magnetic Resonance (NMR), liquid chromatography mass spectrometry (LC-MS), infrared absorption spectrometry, X-ray diffraction, and the like are combined.

The positive photosensitive pigment composition of the present invention contains (c) a resin as an essential constituent. The resin as used herein refers to a compound having a polymer chain with a number of repeating units of 5 or more and a weight average molecular weight (Mw) of 1,000 or more. (c) The component (c) is a component that imparts positive photosensitivity together with the component (d) described later, and has a function as an adhesive component for dispersing the component (a) and the component (b) in the finally obtained pixel-divided layer and fixing to the substrate.

(c) The component (c-1) is preferably a resin having an alkali-soluble group (hereinafter, may be referred to as "component (c-1)") in terms of improving halftone processing properties. The alkali-soluble group as used herein means a hydroxyl group, a carboxyl group, a phosphate group, a sulfo group. The alkali-soluble group is preferably a hydroxyl group, and among these, a phenolic hydroxyl group is more preferred.

Examples of the component (c-1) include: polyimide, polyimide precursor, polybenzoxazole precursor, phenol resin, resin having a repeating unit derived from a radically polymerizable monofunctional monomer having an alkali-soluble group, polysiloxane. These resins may be resins having various alkali-soluble groups in the molecule, or may contain two or more kinds of resins.

Among them, polyimide, a polyimide precursor, a polybenzoxazole precursor or a copolymer of these are preferable in terms of improving halftone processability. The method for producing the copolymer described herein is not particularly limited, and may be a random copolymer or a block copolymer. The block copolymer as described herein refers to a copolymer having repeating units of different resin types in the molecule and having a polymer chain in which ten or more repeating units having the same structure are linked.

Specifically, a resin having a structural unit represented by formula (38) and/or a structural unit represented by formula (39) can be exemplified.

[ 33]

In the formula (38), R ⁹⁷ Represents a tetravalent to decavalent organic group. R is R ⁹⁸ Represents a divalent to octavalent organic group. R is R ⁹⁹ R is R ¹⁰⁰ Each independently represents a hydroxyl group or a carboxyl group, and may be a single group, or may be a mixture of groups. p and q are integers and each independently represents 0 to 6. Wherein p+q > 0 is satisfied. * Indicating the bonding site.

[ chemical 34]

In terms of improving halftone processing properties, the resin having a structural unit represented by the formula (39) is preferably a resin having a group represented by COOA, and examples of the monovalent hydrocarbon group a having 1 to 10 carbon atoms in the formula (39) include: methyl, ethyl, propyl, phenyl or benzyl.

Among them, the component (c-1) preferably has a structural unit containing an amide bond having a high interaction with the component (b), and more preferably contains a resin having a structural unit represented by the formula (39) in terms of improving storage stability.

That is, the positive photosensitive pigment composition of the present invention is more preferably a resin (c) containing a resin having a structural unit represented by the formula (39). In terms of improving the storage stability, the weight average molecular weight (Mw) of the resin having the structural unit represented by formula (39) is preferably 10,000 to 50,000.

In the formula (38), R ⁹⁷ -(R ⁹⁹ ) p represents the residue of an acid dianhydride. R is R ⁹⁷ Preferably an organic group having 5 to 40 carbon atoms which contains an aromatic ring or a cyclic aliphatic group. Examples of the acid dianhydride residue include: pyromellitic dianhydride, 3',4' -biphenyl tetracarboxylic dianhydride, 2, 3',4' -biphenyl tetracarboxylic dianhydride, 2',3,3' -biphenyltetracarboxylic dianhydride, 3',4' -benzophenone tetracarboxylic dianhydride, 2',3,3' -benzophenone tetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, bis (3, 4-dicarboxyphenyl) methane dianhydride, bis (2, 3-dicarboxyphenyl) methane dianhydride, bis (3, 4-dicarboxyphenyl) ether dianhydride, 1,2,5, 6-naphthalene tetracarboxylic dianhydride and aromatic tetracarboxylic acid dianhydride residues such as 2,3,6, 7-naphthalene tetracarboxylic acid dianhydride, 9-bis (3, 4-dicarboxyphenyl) fluorenoic acid dianhydride, and 9, 9-bis {4- (3, 4-dicarboxyphenoxy) phenyl } fluorenoic acid dianhydride, acid dianhydride residues having the structure represented by the formula (40), and aliphatic tetracarboxylic acid dianhydride residues such as butane tetracarboxylic acid dianhydride and 1,2,3, 4-cyclopentane tetracarboxylic acid dianhydride residues.

[ 35]

In the formula (40), R ¹⁰⁵ Represents a single bond, an oxygen atom, C (CF) ₃ ) ₂ 、C(CH ₃ ) ₂ Or SO ₂ 。R ¹⁰⁶ R is R ¹⁰⁷ Each independently represents a hydrogen atom or a hydroxyl group.

In the formula (39), R ¹⁰¹ -(R ¹⁰³ ) r represents the residue of an acid. R is R ¹⁰¹ Preferably an organic group having 5 to 40 carbon atoms which contains an aromatic ring or a cyclic aliphatic group.

Examples of the acid residue include: residues of dicarboxylic acids, residues of tricarboxylic acids, residues of tetracarboxylic acids, and the like. Examples of the dicarboxylic acid include: terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyldicarboxylic acid. As the tricarboxylic acid, there may be mentioned: residues of trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, biphenyl tricarboxylic acid, and the like. The residue of the tetracarboxylic acid may be: pyromellitic acid, 3',4' -biphenyltetracarboxylic acid, 2, 3',4' -biphenyltetracarboxylic acid, 2',3,3' -biphenyltetracarboxylic acid, 3',4' -benzophenone tetracarboxylic acid, 2', aliphatic tetracarboxylic acid residues such as residues of 3,3' -benzophenone tetracarboxylic acid, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane, 2-bis (2, 3-dicarboxyphenyl) hexafluoropropane, 1-bis (3, 4-dicarboxyphenyl) ethane, 1-bis (2, 3-dicarboxyphenyl) ethane, bis (3, 4-dicarboxyphenyl) methane, bis (2, 3-dicarboxyphenyl) methane, bis (3, 4-dicarboxyphenyl) ether, 1,2,5, 6-naphthalene tetracarboxylic acid, 2,3,6, 7-naphthalene tetracarboxylic acid, 2,3,5, 6-pyridine tetracarboxylic acid, 3,4,9, 10-perylene tetracarboxylic acid, or butane tetracarboxylic acid, 1,2,3, 4-cyclopentane tetracarboxylic acid.

R in formula (38) ⁹⁸ -(R ¹⁰⁰ ) q and R in formula (39) ¹⁰² -(R ¹⁰⁴ ) s represents the residue of a diamine. R is R ⁹⁸ R is R ¹⁰² Preferably an organic group having 5 to 40 carbon atoms which contains an aromatic ring or a cyclic aliphatic group.

Examples of the residue of the diamine include: 3,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl ether, 3,4 '-diaminodiphenyl methane, 4' -diaminodiphenyl methane, 1, 4-bis (4-aminophenoxy) benzene, m-phenylenediamine, p-phenylenediamine, 1, 5-naphthalenediamine, 2, 6-naphthalenediamine, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl } ether, 1, 4-bis (4-aminophenoxy) benzene, 2 '-dimethyl-4, 4' -diaminobiphenyl, 2 '-diethyl-4, 4' -diaminobiphenyl 3,3 '-dimethyl-4, 4' -diaminobiphenyl, 3 '-diethyl-4, 4' -diaminobiphenyl, a residue of 9-bis (4-aminophenyl) fluorene or a residue of a compound in which at least a part of hydrogen atoms of these aromatic rings are substituted with an alkyl group or a halogen atom, a compound represented by formula (41), a compound represented by formula (42), a compound represented by formula (43), a compound represented by formula (44), and a residue of a compound represented by formula (45).

[ 36]

In the formula (41), R ¹⁰⁸ Represents a single bond, an oxygen atom, C (CF) ₃ ) ₂ 、C(CH ₃ ) ₂ Or SO ₂ 。R ¹⁰⁹ R is R ¹¹⁰ Each independently represents a hydrogen atom or a hydroxyl group.

[ 37]

In the formula (42), R ¹¹¹ Represents a single bond, an oxygen atom, C (CF) ₃ ) ₂ 、C(CH ₃ ) ₂ Or SO ₂ 。R ¹¹² R is R ¹¹³ Each independently represents a hydrogen atom or a hydroxyl group.

[ 38]

In the formula (43), R ¹¹⁴ 、R ¹¹⁵ 、R ¹¹⁶ R is R ¹¹⁷ Each independently represents a hydrogen atom or a hydroxyl group.

[ 39]

In the formula (44), R ¹¹⁸ R is R ¹¹⁹ Each independently represents a hydrogen atom or a hydroxyl group.

In addition, by sealing the ends of these resins with monoamines, the weight average molecular weight (Mw) can be easily adjusted, and the storage stability as (c) resin can be improved.

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

In the formula (39), the group represented by COOA can be obtained by converting a carboxyl group with an esterifying agent. Examples of the esterifying agent include N, N-dimethylformamide dimethyl acetal and N, N-dimethylformamide diethyl acetal.

The resin having the structural unit represented by the formula (38) and/or the structural unit represented by the formula (39) can be obtained by a known method, and can be synthesized, for example, by a method disclosed in Japanese patent No. 4341293, international publication No. 2014/097992, and International publication No. 2019/181782.

Examples of the phenol resin include novolac-type phenol resins or resol-type phenol resins having a structural unit represented by the formula (45) and/or a structural unit represented by the formula (46). The phenol resin may be used in combination for the purpose of adjusting the dissolution rate with respect to the alkaline developer or the thermal fluidity of the developed film. From the viewpoint of developability, the weight average molecular weight (Mw) of the phenol resin is preferably 1,500 or more and 15,000 or less.

[ 40]

In the formula (45) and the formula (46), R ¹²⁰ R is R ¹²¹ Each independently represents a methylene group or a CH-Ar group. Ar represents a phenyl group in which an alkyl group having 1 to 3 carbon atoms is substituted or an unsubstituted phenyl group. * Indicating the bonding site.

The phenol resin can be obtained by a known method, and can be synthesized by condensing an aldehyde compound such as formaldehyde or benzaldehyde with a compound having a phenol skeleton such as phenol, o-cresol, m-cresol, p-cresol, or xylenol in the presence of an acidic catalyst. Examples of the commercial products of the phenol resin include: TRR5030G, TRR5010G, TR4020G, TR4080G, TR4000B, TRM B20G, EP F10G (all of the above were manufactured from Asahi organic materials (stock)).

Examples of the resin having a repeating unit derived from a radically polymerizable monofunctional monomer having an alkali-soluble group include resins obtained by radical polymerization of a combination of one or two or more radically polymerizable monofunctional monomers having a hydroxyl group, such as hydroxystyrene, hydroxyphenyl (meth) acrylate, hydroxyphenyl (meth) acrylamide, and N-hydroxyphenyl-substituted maleimide. Further, a radically polymerizable monofunctional monomer having a thermally crosslinkable group such as glycidyl (meth) acrylate, 3, 4-epoxycyclohexyl (meth) acrylate, or allyl glycidyl (meth) acrylate may be copolymerized. The (meth) acrylate mentioned herein is a methacrylate or acrylate. Specifically, a resin having a structure represented by formula (47) or a resin having a structure represented by formula (48) is preferable. From the viewpoint of developability, the weight average molecular weight (Mw) of the resin having a repeating unit derived from a radically polymerizable monofunctional monomer having an alkali-soluble group is preferably 3,000 or more and 30,000 or less.

[ chemical 41]

In the formula (47) and the formula (48), R ¹²² R is R ¹²⁴ Each independently represents a hydrogen atom or a methyl group. R is R ¹²³ Represents a single bond, COO or CONH. R is R ¹²⁵ Represents a monovalent organic group having an epoxy group. * Indicating the bonding site.

The resin (c) may contain (c-2) a resin having no alkali-soluble group (hereinafter, may be referred to as "(c-2 component"). Examples of the component (c-2) include (meth) acrylic resins having no alkali-soluble group, and the (meth) acrylic resins are preferably used as a surface treatment material for coating at least a part of the surface of the component (a) and/or a pigment other than the component (a). When the physical refinement treatment is performed by allowing 5 to 20 parts by weight of the (meth) acrylic resin to coexist with respect to 100 parts by weight of the pigment, even an organic pigment in which the active surface is generated and crystal growth or aggregation is easily performed may be easily refined. In the case of a surface treatment material containing the component (c-2) as a pigment, a water-insoluble resin is desirable in terms of avoiding elution when the milled material is removed by washing with water and fixing it to the pigment surface.

Examples of the alkali-insoluble (meth) acrylic resin include resins obtained by radical polymerization of one or more kinds of alkali-insoluble radical-polymerizable monofunctional monomers such as glycidyl (meth) acrylate, allyl glycidyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, and the like.

In terms of improving the storage stability, the content of the (c) resin is preferably 10% by weight or more, more preferably 30% by weight or more, based on 100% by weight of the solid content of the positive photosensitive pigment composition. In terms of improving the exposure sensitivity, it is preferably 90% by weight or less, more preferably 60% by weight or less.

In addition, in terms of improving the exposure sensitivity and the storage stability, the content of the resin having the structural unit represented by the formula (39) is preferably 50% by weight or more, more preferably 80% by weight or more, in the resin (c).

In terms of improving the storage stability, the amine value of the resin (c) is preferably 5.0mgKOH/g or less, more preferably 3.0mgKOH/g or less. In the case of containing a plurality of resins having different amine values, (c) the resin may be regarded as the amine value of (c) the weighted average value corresponding to the content ratio.

That is, the positive photosensitive pigment composition of the present invention preferably has (c) a resin having an amine value of 5.0mgKOH/g or less. The method for measuring the amine value described herein will be described below.

60mL of a solvent (. Gamma. -butyrolactone) was added to a 100mL Erlenmeyer flask to dissolve the sample, and titration was performed with a titration solution (0.1 mol/L hydrochloric acid) using a potential difference titration apparatus AT-710 and a glass electrode C-173 (both manufactured by Kyoto electronics industries, ltd.) and the obtained inflection point was used as an end point. In addition, blank titration was performed by the same method without containing a sample, and the amine value was calculated from the following formula.

Amine value (mgKOH/g) = (V) ¹ -V ⁰ )×f×0.1×56.11/S

In the above formula, S: mass (g), V of sample ((c) resin) ⁰ : quantity of titration solution (mL), V required for blank titration ¹ : amount of titration solution (mL) required for sample titration, f: factor of titration solution (1.006).

As a method for separating the resin (c) from the positive photosensitive pigment composition, any method can be used, for example, dilution with γ -butyrolactone can be performed, and the pigment concentrate of the base liquid is separated as insoluble particle components by filtration in a centrifugal separator several times, and further, if necessary, separation treatment by column purification or drying under reduced pressure is performed. When the resin solution is used as the sample, the amine value of the resin solution may be converted to (c) the amine value of the resin according to the solid content thereof.

The positive photosensitive pigment composition of the present invention contains (d) a photoacid generator as an essential constituent. The photoacid generator is not particularly limited as long as it is a compound that generates an acid by decomposition by light irradiation.

By containing the component (d), the effect of making the solubility of the film of the exposed portion with respect to the alkaline developer relatively higher than the solubility of the film of the unexposed portion with respect to the alkaline developer is obtained, and thus positive-type lithography in which the film of the exposed portion after pattern exposure through the exposure mask is removed to form a pattern can be realized. Further, the amount of acid generated in the film can be controlled by adjusting the exposure amount, and the effect of making the solubility of the film of the exposed portion after exposure with a small exposure amount through the halftone exposure mask relatively lower than the solubility of the film of the exposed portion after exposure with a large exposure amount with respect to the alkaline developer is achieved, and a pattern having a step can be formed by positive halftone processing.

The component (d) may be: quinone diazide compounds, oxime sulfonate compounds, imide sulfonate compounds. Among them, the quinone diazide compound is preferable in terms of showing an excellent dissolution inhibiting effect on the film of the unexposed portion, further increasing the difference in dissolution rate between the exposed portion and the unexposed portion, and excellent exposure sensitivity. As the quinone diazide compound, a 4-naphthoquinone diazide sulfonyl ester compound which is a compound obtained by an esterification reaction of a compound having a phenolic hydroxyl group with 1, 2-naphthoquinone-2-diazide-4-sulfonyl chloride (hereinafter, sometimes referred to as "4-naphthoquinone diazide sulfonyl chloride"), or a 5-naphthoquinone diazide sulfonyl ester compound which is a compound obtained by an esterification reaction of a compound having a phenolic hydroxyl group with 1, 2-naphthoquinone-2-diazide-5-sulfonyl chloride (hereinafter, sometimes referred to as "5-naphthoquinone diazide sulfonyl chloride") may be preferably cited.

As the compound having a phenolic hydroxyl group, a compound having two or more phenolic hydroxyl groups in the molecule is preferable in terms of improving the exposure sensitivity. Examples of the compound having two or more phenolic hydroxyl groups in the molecule include: trisP-HAP represented by formula (49), trisP-PA represented by formula (50), tekP-4HBPA represented by formula (51), trisP-SA, trisOCR-PA, bis P-AP, bis P-NO, bis P-PR, bis P-B, bisP-DE, bis P-DP, bis RS-2P, bis RS-3P, bis P-DEK (all manufactured by the present state chemical industry (stock) above).

[ chemical 42]

The composition may contain a 4-naphthoquinone diazide sulfonyl ester compound having an absorption in the i-ray (wavelength 365 nm) region and a 5-naphthoquinone diazide sulfonyl ester compound having a broad absorption in the i-ray to h-ray (wavelength 405 nm) and g-ray (wavelength 436 nm) regions of a mercury lamp. In addition, a quinone diazide compound having a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the molecule may be contained. Among them, the film containing the component (a) and the component (b) in the region of 365nm to 436nm has a transmittance substantially at the region of 410nm to 440nm, and thus a compound containing a 5-naphthoquinone diazide sulfonyl group represented by the formula (52) is more preferable in terms of improving the exposure sensitivity. Further, when the compound having the structure represented by formula (52) is contained, carboxylic acid is generated in the film of the exposed portion.

[ chemical 43]

In the formula (52), R ¹²⁶ ～R ¹³⁰ Each independently represents a hydrogen atom, a C1-6 alkyl group or a C1-6 alkoxy group. * Indicating the bonding site.

The component (d) may contain a compound having an alkoxyalkyl group or an epoxy group as a thermally crosslinkable group and a naphthoquinone diazide sulfonyl group as a photosensitive group in the molecule. Specific examples thereof include quinone diazide compounds having an alkoxymethyl group disclosed in Japanese patent application laid-open No. 2018/158263. In the present specification, these compounds are defined as compounds belonging to the component (d) rather than the thermal crosslinking agent (g) (hereinafter, sometimes referred to as the "component (g)").

Examples of the commercial product of the component (d) include: PA-28 (manufactured by Daito Chemix) which is a naphthoquinone diazide compound that generates an acid upon exposure to i-rays, PAG103 and PAG203 (manufactured by BASF) which are oxime sulfonate compounds that generate an acid upon exposure to i-rays, and NIT, NIN, ILP-110 (manufactured by Heraeus) which are imide sulfonate compounds that generate an acid upon exposure to i-rays (manufactured by He Lishi).

The content of the component (d) is preferably 1% by weight or more, more preferably 5% by weight or more, based on 100% by weight of the solid content of the positive photosensitive pigment composition, in terms of producing a necessary and sufficient amount of acid in the film to improve the exposure sensitivity. In terms of suppressing excessive absorption of exposure light on the film surface and improving exposure sensitivity, it is preferably 30% by weight or less, more preferably 20% by weight or less.

The positive photosensitive pigment composition of the present invention contains (e) an organic solvent as an essential constituent. (e) The organic solvent as a dispersion medium of the component (a) not only contributes to improvement of storage stability but also has the following effects: the coating property of the positive photosensitive pigment composition is improved, the smoothness of a pre-baked film to be described later is improved, and the halftone processing property is improved.

Examples of the component (e) include: ether solvents, glycol solvents, acetate solvents, ketone solvents, lactone solvents, aromatic carbon solvents, and amide solvents.

Examples of the ether solvent 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 monomethyl ether (hereinafter, "PGME (propyleneglycol monomethyl ether)"), propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether. The glycol-based solvents include: ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol. Examples of the acetate solvent include: ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (hereinafter, "PGMEA (propyleneglycol monomethyl ether acetate)"), propylene glycol monoethyl ether acetate, methyl lactate, ethyl lactate, 3-methoxybutyl acetate (hereinafter, "MBA (3-methoxybutyl acetate)"). Examples of the ketone solvent include: methyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone, 3-heptanone. Examples of the lactone-based solvent include gamma-butyrolactone and gamma-valerolactone. Examples of the aromatic carbon-based solvent include toluene, xylene, and benzene. The amide-based solvents include: n-methylpyrrolidone (hereinafter referred to as "NMP (N-methyl pyrrolidone)"), N-dimethylformamide, and N, N-dimethylacetamide. Among them, the ether-based solvent and/or the acetate-based solvent are preferably contained, and the lactone-based solvent is more preferably contained, in terms of improving the storage stability.

In terms of improving the storage stability, the content of the component (e) is preferably 30% by weight or more, more preferably 50% by weight or more, based on 100% by weight of the positive photosensitive pigment composition. In terms of improving the smoothness of the pre-baked film, it is preferably 99% by weight or less, more preferably 95% by weight or less.

In terms of improving the storage stability, the content of the aromatic hydrocarbon solvent and the amide solvent is preferably 0.5% by weight or less, respectively, based on 100% by weight of the positive photosensitive pigment composition. Further, the storage stability may be further improved by adding 0.01 to 0.5% by weight of water to 100% by weight of the positive photosensitive pigment composition.

The positive photosensitive pigment composition of the present invention preferably further contains (f) a compound which is converted by heating into a compound having a maximum absorption wavelength in a region of 350nm to 500nm in a region of 350nm to 780nm in wavelength. The component (f) is a compound not belonging to any of the components (a) to (i), and the principle of thermal color development is not particularly limited. As described above, since the transmittance of the component (a) and the component (h) is higher in the region of the wavelength of 410nm to 440nm than in the region of 500nm to 650nm, the maximum transmittance of the pixel dividing layer obtained after the heat treatment in the region of the wavelength of 410nm to 440nm can be preferably reduced by containing the component (f). Therefore, for example, a black pixel-dividing layer having excellent external light reflection suppressing function in a blue region can be obtained by adding a pigment containing the compound represented by the formula (9) and the compound represented by the formula (10) which are dark purple as the component (a) and the component (f) after the thermal color development is yellow, orange or brown. The minimum temperature at which color development is started is preferably 150 ℃ or higher in order to avoid a decrease in exposure sensitivity, and is preferably 230 ℃ or lower in order to sufficiently obtain a decrease effect in transmittance. Examples of the component (f) include a thermally color-developing compound described in Japanese patent application laid-open No. 2004-326094. Among them, the component (f) preferably contains a hydroxyl group-containing compound in terms of improving halftone processing properties. Examples of the hydroxyl group-containing compound include 4,4',4",4 '" - (1, 4-phenylene-dimethylene) tetraphenol (maximum absorption wavelength after heat treatment: 440 nm), 4' -trihydroxy triphenylmethane represented by formula (53) (maximum absorption wavelength after heat treatment: 460 nm), 4- [ bis (4-hydroxyphenyl) methyl ] 2-methoxyphenol (maximum absorption wavelength after heat treatment: 470 nm).

[ 44]

The positive photosensitive pigment composition of the present invention may further contain a component (g). The component (g) is preferably a compound having two or more alkoxymethyl groups or epoxy groups in the molecule. Examples of the alkoxymethyl group include: methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl. The heat resistance and flexibility of the pixel dividing layer can be improved by a crosslinked structure formed by the reaction of the component (g) and the resin (c) and the reaction of the components (g) with each other. In addition, the resistance to a strongly acidic etching solution or a strongly alkaline resist stripping solution, that is, the chemical resistance can be improved, and when a cured film containing a cured product of the positive photosensitive pigment composition of the present invention is used as a TFT (Thin film transistors) planarization layer, partial dissolution of the cured film or a decrease in light-shielding property can be suppressed.

Examples of the compound having two or more alkoxymethyl groups in the molecule include: HMOM-TPHAP, DML-PC, DML-PEP, DML-OC, DML-POP (all manufactured by the present state chemical industry (stock) supra), "Nikaraoke (NIKALAC) (registered trademark)" MX-390, nikaraoke (NIKALAC) MX-290, nikaraoke (NIKALAC) MX-280, nikaraoke (NIKALAC) MX-270, nikaraoke (NIKALAC) MW-100LM, nikaraoke (NIKALAC) MX-750LM (all manufactured by Sanhe Chemie (stock) supra).

Examples of the compound having two or more epoxy groups in the molecule include: terpicae (TEPIC) -S, terpicae (TEPIC) -PAS, terpicae (TEPIC) -VL, terpicae (TEPIC) -UC (all manufactured by the company of geneva chemistry, above), XD-1000-H, XD-1000-2L, NC-3000 (all manufactured by the company of japan chemicals, above), terkomo (techme) VG3101L (manufactured by Printec), TR-FR-201 (manufactured by the company of strongback).

In order to improve the exposure sensitivity, the positive photosensitive pigment composition of the present invention preferably further contains (i) aminobenzenesulfonic acid (hereinafter, sometimes referred to as "(i) component"). Examples of the component (i) include 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, and 4-aminobenzenesulfonic acid (all of which are manufactured by tokyo chemical industry (co.)). In terms of improving the exposure sensitivity, the content of the component (i) in the solid component of the positive photosensitive pigment composition is preferably 0.01% or more. In terms of maintaining the storage stability, it is preferably 0.5% by weight or less.

The positive photosensitive pigment composition of the present invention may contain a leveling agent or an adhesion improver to the surface of a substrate as other components, as required. In addition, a surfactant containing a fluorine atom in a molecule may be contained to impart liquid repellency to the surface of the pixel dividing layer.

As a method for producing the positive photosensitive pigment composition, the following methods are listed: a pigment dispersion liquid containing the component (a), the component (b), the resin (c) and the component (e) is prepared in advance by wet dispersion treatment, and then the component (d), the component (e), optionally the component (f), the component (g), the component (i) and the other components are mixed with the pigment dispersion liquid and stirred, and optionally filtered. When the component (h) is contained, it is desirable to prepare a pigment dispersion liquid containing the component (a), the component (b), the resin (c), the component (e) and the component (h) in advance in order to improve the storage stability of the positive photosensitive pigment composition.

As a disperser for performing the wet dispersion treatment, a wet medium disperser may be used, or a wet medium-free disperser may be used, and it is desirable to use a wet medium disperser in view of excellent dispersion treatment speed and economical advantage. The secondary aggregates of the pigment component such as component (a) can be deagglomerated by the wet medium dispersion treatment, and the secondary particle diameter is preferably controlled to a region close to the primary particle diameter in the fine direction. Examples of the wet medium dispenser include: bead MILLs such as "Revomill (registered trademark)" (shallow Tian Tiegong (manufactured by thigh)), "Nanocover tower (Nanogetter) (registered trademark)" (manufactured by Luze fine technology (Ashizawa Finetech) (manufactured by thigh)), "Dyno-MILL (DYNO-MILL) (registered trademark)" (manufactured by Willi A. Bachofen, inc.), "spike MILL (registered trademark)" (manufactured by well manufacturing company (manufactured by thigh)), "Sand MILL (Sand Grinder)" (registered trademark) "(manufactured by Dupont), super advanced Bessel MILL (ultra apex MILL advance) (registered trademark)" (manufactured by Guangshi Metal & Machinery (manufactured by Hiroshimetal), NEO-alpha MILL (NEO-alpha MILL) (registered trademark) "(manufactured by AIX (manufactured by thigh)"). Among them, the super advanced attire mill is preferable in terms of avoiding breakage of primary particles and capable of deagglomerating secondary agglomerates of a plurality of primary particles while maintaining an average primary particle diameter, an average aspect ratio of primary particles, and a maximum primary particle diameter. The material of the medium is preferably ceramic beads such as zirconia, and the diameter thereof is preferably 0.03mm phi-0.5 mm phi. The commercial product includes "torayfera (registered trademark)" (manufactured by torayfera corporation).

In terms of improving the storage stability, the D50 (cumulative 50% secondary particle diameter) in the particle size distribution of the particle components in the positive photosensitive pigment composition based on volume measured by the dynamic light scattering method is preferably 30nm or more. In terms of improving the exposure sensitivity, it is preferably 70nm or less. On the other hand, in terms of improving the storage stability, D90 (cumulative 90% secondary particle diameter) is preferably 80nm or more. In terms of improving the exposure sensitivity, 150nm or less is preferable. D50 and D90 refer to values obtained by measuring a particle size distribution measurement sample. The particle size distribution measurement sample is a positive photosensitive pigment composition prepared by the method of diluting solvent=1: 99 (weight ratio) the diluted solvent was mixed in three portions with the positive photosensitive pigment composition, and the mixture was stirred on a shaker for 10 minutes to obtain a measurement object. As the diluting solvent, a solvent having the same composition as the organic solvent (e) contained in the positive photosensitive pigment composition is used. The particle size distribution as referred to herein is a particle size distribution based on the volume of the light source, which can be measured by a particle size distribution measuring apparatus SZ-100 (manufactured by horiba corporation) using a dynamic light scattering method. D50 and D90 refer to particle diameters (nm) corresponding to 50% and 90% respectively, which are integrated on the larger particle diameter side with the smaller particle diameter side as the base point (0%) in the integrated particle size distribution curve.

The cured film of the present invention is preferably a cured film containing a cured product of the positive photosensitive pigment composition of the present invention. The cured product as described herein is a cured product obtained by a step of heating the positive photosensitive pigment composition at a temperature of 200 ℃ or higher and 400 ℃ or lower for 10 minutes or more under atmospheric pressure.

The organic EL display device of the present invention is preferably a cured film comprising a cured product containing the positive photosensitive pigment composition of the present invention. The form of the cured film in the organic EL display device is not particularly limited, and examples thereof include a pixel dividing layer and a TFT planarizing layer. In the case of including the pixel dividing layer and/or the TFT planarizing layer containing the cured product of the positive photosensitive pigment composition, the organic EL display device of the present invention has the following technical effects: the external light reflection suppressing function is excellent, and the visibility is excellent without including a polarizing plate. Examples of the components other than the cured product of the positive photosensitive pigment composition contained in the cured film included in the organic EL display device of the present invention include: moisture mixed in the step of forming the cured film, or Na mixed in the cured film by using the base substrate, the electrode, or the like as a source ⁺ 、Ag ⁺ And (3) plasma metal ions. The content of the cured product of the positive photosensitive pigment composition in the cured film included in the organic EL display device of the present invention is preferably 90% by weight or more, more preferably 95% by weight or more.

A preferred mode when the cured film of the present invention is used as a pixel dividing layer of an organic EL display device will be described below.

In order to suppress reflection of external light and to improve the value as a display device, the Optical Density (Optical Density) of the pixel dividing layer per 1.0 μm film thickness is preferably 0.5 or more, more preferably 0.7 or more. From the viewpoint of exposure sensitivity, it is preferably 1.3 or less, more preferably 1.1 or less.

The optical density means the following value: the light-shielding property is higher as the optical density of the pixel-divided layer formed on the transparent substrate so as to have a film thickness of 1.5 μm is higher, by measuring the incident light intensity and the transmitted light intensity using an optical density meter alic (X-Rite) 361T (manufactured by alic (X-Rite)) and dividing the value calculated by the following equation by the film thickness value, that is, a value of 1.5. As the transparent substrate, a transparent glass substrate, that is, "tenpap (Tempax) (manufactured by AGC technology glass)", can be preferably used.

Optical concentration = log ₁₀ (I ₀ /I)

In the above, I ₀ : intensity of incident light, I: the transmitted light intensity.

In terms of reducing the contact area with the vapor deposition mask when pattern vapor deposition is performed on the light-emitting layer, improving the yield and achieving both the exposure sensitivity and the resolution, the thick film portion of the pixel dividing layer having a step is preferably 2.5 μm to 4.0 μm, and the thin film portion is preferably 1.0 μm to 2.5 μm. The thickness of the thick film portion and the thickness of the thin film portion described herein refer to the thickness of the flat portion other than the thickness of the inclined portion located at the end portion of the film. The difference in film thickness between the thick film portion and the thin film portion is preferably 1.0 μm to 1.5 μm. The opening may be formed only in the thin film portion, and the thick film portion may be partially arranged in a spacer shape. In terms of suppressing disconnection of the electrode and avoiding occurrence of non-lit pixels, the cross-sectional taper angle of the inclined portion at the end of the thin film portion of the pixel dividing layer having a step is preferably 50 ° or less, more preferably 40 ° or less. In order to suppress a decrease in light-shielding property at the end of the thin film portion, it is preferably 15 ° or more, more preferably 20 ° or more.

As a method of forming the pixel dividing layer having a step, a method including: a coating step of coating a positive photosensitive pigment composition to obtain a coating film; a pre-baking step of heating the coating film to obtain a pre-baked film; an exposure step of performing pattern exposure on the active chemical rays through a positive halftone exposure mask to obtain an exposure film having an exposure portion, a half-exposure portion, and an unexposed portion in a plane; a developing step of performing development using an alkaline developer to remove not only the exposed portion but also a part of the half-exposed portion and the unexposed portion to obtain a developed film; and a curing step of thermally curing the cured film by heating to obtain a cured film.

As the coating device used in the coating step, a spin coater or a slit coater is preferably used in terms of excellent film coatability. Needle gap pre-baking or contact pre-baking may also be performed after coating.

The pre-baking temperature in the pre-baking step is preferably 50 to 150 ℃, and the pre-baking time is preferably 30 seconds to 5 minutes. In the case of forming the pixel dividing layers having the step at the same time, the film thickness of the pre-baked film is preferably 3.5 μm to 6.0 μm. When near infrared ray alignment is performed in the exposure step described later, the maximum transmittance of the pre-baked film of the positive photosensitive pigment composition at a wavelength of 800nm to 1,300nm is preferably 20% or more, more preferably 30% or more, in terms of improving positional accuracy.

Examples of the exposure device used in the exposure step include a stepper, a mirror projection mask aligner (mirror projection mask aligner, MPA), and a parallel photomask aligner (parallel light mask aligner, PLA). Examples of the active chemical rays to be irradiated during exposure include j rays (wavelength 313 nm), i rays (wavelength 365 nm), h rays (wavelength 405 nm), and g rays (wavelength 436 nm) of an ultra-high pressure mercury lamp. Preferably, the mixed ray includes at least an h-ray, and more preferably, the mixed ray includes a g-ray, an h-ray, and an i-ray. The positive type halftone exposure mask is preferably a mask designed to have a full-transmissive portion, a half-transmissive portion, and a shielding portion in the substrate surface, and the exposure amount of the half-transmissive portion is preferably 10% to 50% when the exposure amount of the full-transmissive portion is 100% and the exposure amount of the shielding portion is 0%.

The exposure portion in the exposure film refers to a portion that is subjected to pattern exposure through the full-transmission portion of the exposure mask, the half-exposure portion refers to a portion that is subjected to pattern exposure through the half-transmission portion of the exposure mask, and the non-exposure portion refers to a portion that is not subjected to exposure through the shielding portion of the exposure mask. The pixel division layer having the step obtained after the curing step is an opening, a thin film, and a thick film, respectively.

Examples of the development method in the development step include spraying, dipping, and liquid coating, and examples thereof include a method of dipping an exposed film for 10 seconds to 3 minutes. In terms of improving halftone processing, a liquid-coating method is preferable. The alkali developer is preferably a tetramethyl ammonium hydroxide aqueous solution (hereinafter, referred to as "TMAH (tetramethylammonium hydroxide)") in an amount of 0.4 to 2.5 wt%, and examples of the commercial product include 2.38 wt% TMAH (manufactured by polymorphous chemical industry (ltd)). After the developing process, a cleaning process using a shower of deionized water and/or a moisture removal process using air spraying may also be applied. In terms of improving the in-plane uniformity of the film thickness of the developed film, the development time is preferably set to a value obtained by subtracting the film thickness of the thick film portion (unexposed portion) of the developed film having a step from the film thickness of the pre-baked film, that is, the film reduction amount (μm) in the development step is 1.0 μm or less. In order to improve the exposure sensitivity, the thickness is preferably set to 0.5 μm or more. Further, the fluidity of the film in the curing step may be controlled by re-irradiating the obtained developed film with exposure light as the second exposure step.

In the curing step, the developed film is thermally cured by heating, and the developer, moisture, and the like remaining in the film are volatilized to obtain a cured film. Examples of the heating device include a hot air oven and an Infrared (IR) oven, and examples of the heating environment include nitrogen and air. The heating temperature is preferably 200 to 350℃under atmospheric pressure, more preferably 220 to 280 ℃.

An organic EL display device according to the present invention is an organic EL display device including a substrate, a first electrode, a pixel-dividing layer, a light-emitting pixel, and a second electrode, wherein the pixel-dividing layer contains (a) a pigment containing a compound having a structure represented by formula (1) in a molecule and having one perylene skeleton in a molecule, and (b) a compound having a structure represented by formula (2) and having no N, N-dialkylaminoalkyl group, or a metal salt thereof.

[ 45]

[ chemical 46]

The organic EL display device according to the present invention has an advantageous technical effect that variation in luminance in the plane of the panel display section, that is, luminance unevenness is small.

Fig. 2 is a cross-sectional view of a TFT substrate in an organic EL display device according to an embodiment of the present invention.

A thin film transistor 3 of a bottom gate type or a top gate type (hereinafter, simply referred to as TFT 3) is provided in a matrix on the surface of the substrate 8, and a TFT insulating layer 5 is formed so as to cover the TFT 3 and the wiring 4 connected to the TFT 3. Further, a planarization layer 6 is formed on the surface of the TFT insulating layer 5, and a contact hole 9 is provided in the planarization layer 6 to be opened for connecting the first electrode 7 to the wiring 4. On the surface of the planarization layer 6, a first electrode 7 is patterned and connected to the wiring 4. The pixel dividing layer 10 is formed so as to surround the pattern peripheral edge of the first electrode 7. An opening is provided in the pixel dividing layer 10, a light emitting pixel 11 containing an organic EL light emitting material is formed in the opening, and a second electrode 12 is formed in a state of covering the pixel dividing layer 10 and the light emitting pixel 11. When a voltage is applied to the light-emitting pixel portion after sealing the TFT substrate including the above laminated structure under vacuum, light can be emitted as an organic EL display device. The shape of the opening of the pixel dividing layer 10 is not particularly limited, and may be square, rectangular, or elliptical. The opening width of the opening may be appropriately determined according to the size of the pixel 11 described later, and may be, for example, 10 μm to 50 μm in minor diameter. The smaller the short diameter of the opening width of the opening portion, the more useful the effect of suppressing luminance unevenness that the organic EL display device of the present invention plays.

The organic EL display device of the present invention preferably has a pixel dividing layer having a thick film portion with a film thickness of 2.5 μm to 4.0 μm and a thin film portion with a film thickness of 1.0 μm to 2.5 μm, and has a portion where a difference in film thickness between the thick film portion and the thin film portion is 1.0 μm or more. The thick film portion has a spacer effect, and can reduce the contact area with the vapor deposition mask when forming the light emitting pixels 11, thereby improving the yield, preventing defects of the organic EL element, and suppressing the occurrence of non-lit pixels.

The emission peak wavelength of the light-emitting pixel 11 is not particularly limited, and examples thereof include a structure in which pixels of different types having emission peak wavelengths in respective blue, red, and green regions of three primary colors of light are arranged so as to form a film on the entire surface. The peak wavelength of the red region may be 560nm to 700nm, the peak wavelength of the blue region may be 420nm to 480nm, and the peak wavelength of the green region may be 500nm to 550nm. The other laminated member may be a laminated member in which blue, red, and green color filters and black matrices are combined and arranged on the front surface of the display unit. As the organic EL light-emitting material constituting the light-emitting pixel 11, a material which is further combined with a hole transport layer and/or an electron transport layer in addition to the light-emitting layer can be preferably used. As a method for patterning the light emitting pixels 11, a mask vapor deposition method is exemplified. The mask vapor deposition method is a method of patterning an organic compound by vapor deposition using a vapor deposition mask, and specifically, a method of vapor deposition by disposing a vapor deposition mask having a desired pattern as an opening on the substrate side is exemplified. Examples of the vapor deposition mask used for forming high-definition light emitting pixels include those disclosed in japanese patent application laid-open No. 2019-163543.

As the first electrode 7, for example, a conductive metal oxide such as Indium Tin Oxide (ITO) or indium zinc oxide (indium zinc oxide, IZO) can be used, and among them, ITO is preferably used in terms of excellent transparency and conductivity. As a method of patterning ITO, a film is formed over the entire surface of ITO by a sputtering method, and then a positive resist material for etching is patterned by a photolithography method, a resist pattern is obtained on the ITO film, and only the ITO film in the non-formation portion of the resist pattern is removed by an etching solution. Then, the following methods can be listed: the resist pattern is removed by a resist stripping liquid, and heat treatment is further performed as needed to obtain a desired degree of crystallization. As the positive resist material for etching, a positive photosensitive pigment composition containing an alkali-soluble novolak-based resin can be used. As the etching solution, an aqueous solution containing nitric acid and hydrochloric acid or an aqueous oxalic acid solution IS used, and as commercial products, for example, ITO-101N (manufactured by kanto chemical (strands)), IS-2, IS-3 (manufactured by zozuki chemical (strands) in the name of "askulin (S-clean) (registered trademark)", and IS-3 (manufactured by zozuki chemical (strands) in the name of "askulin (S-clean) (registered trademark)") are cited. As the resist stripping liquid, an aqueous solution of an organic amine is used, and as a commercial product, for example, "An Lasi dtex (registered trademark)" M6, "anglast (registered trademark)" M6B, "anglast (registered trademark)" TN-1-5, "anglast (registered trademark)" M71-2 (all of them are "sanzhu" institute of pure chemicals ") may be cited. In the case where the organic EL display device of the present invention is a top emission type organic EL display device, the first electrode 7 may have a laminated structure of ITO/silver alloy/ITO in order to improve light reflectivity and adhesion to a substrate.

The second electrode 12 may include any substance as long as it is a layer functioning as an electrode. As the second electrode 12, for example, in the case where the organic EL display device of the present invention is a bottom emission type organic EL display device, a layer containing aluminum may be preferably used in terms of excellent light reflectivity. In the case of the top emission type organic EL display device, a silver alloy such as silver/magnesium is preferably used in terms of excellent light transmittance. The second electrode 12 can be obtained by forming a film over the entire surface by sputtering.

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 light emitted from the light-emitting pixels 11 is extracted to the substrate side via the substrate 8, or a top emission type organic EL display device in which light emitted to the opposite side of the substrate 8 is extracted via the second electrode 12.

As the substrate 8, a substrate including glass having no flexibility, or a substrate including polyimide resin having flexibility can be used. Examples of the glass include OA-10G, OA-11 (manufactured by Nitro Kogyo Co., ltd., japan) and AN-100 (manufactured by Asahi Kara Co., ltd.). As a substrate containing a polyimide resin, a substrate obtained by: the temporary support is peeled off by a laser or the like after the solution containing the polyamic acid is applied to the surface of the temporary support and then heat-treated at 250 to 400 ℃ to imidize the polyamic acid to convert it into a polyimide resin. The polyamic acid used in this case can be synthesized by reacting a tetracarboxylic dianhydride with a diamine compound in an amide solvent such as N-methyl-2-pyrrolidone, and among these, a polyamic acid having a residue of an aromatic tetracarboxylic dianhydride and a residue of an aromatic diamine compound is preferable in terms of small coefficient of thermal expansion and excellent dimensional stability. Specific examples thereof include polyamic acids having a residue of 3,3', 4' -biphenyltetracarboxylic dianhydride and a residue of p-phenylenediamine.

Examples

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the form of the present invention is not limited to these. First, evaluation methods in each of examples and comparative examples will be described.

(1) Evaluation of exposure sensitivity (minimum required exposure)

On the surface of the alkali-free glass substrate having a vertical dimension of 150 mm/a horizontal dimension of 150mm, a silver alloy (an alloy containing 99.00 wt% silver and 1.00 wt% copper) was formed into a film on the entire surface by sputtering. Further, an entire surface of the ITO film was formed by sputtering, and a glass substrate including a silver alloy film/an ITO film over the entire surface of the alkali-free glass substrate was obtained.

The positive photosensitive pigment compositions 1 to 24 and 26 obtained in examples 1 to 19, comparative examples 1 to 5 and comparative example 7 were each coated on the ITO surface of a glass substrate including a silver alloy film/ITO film by adjusting the rotation speed so that the thickness of the thick film portion of the pixel division layer having the step difference was 3.0 μm±0.2 μm and the thickness of the thin film portion was 1.5 μm, respectively, using a spin coater. Further, the coated film was prebaked at 110℃for 120 seconds using a hot plate under atmospheric pressure to obtain a prebaked film, and alignment of a positive halftone exposure mask (a mask in which 220 square full-permeation portions having a vertical dimension of 30.0 μm and a horizontal dimension of 30.0 μm were arranged, and the exposure amount in the full-permeation portion was 100%, and the exposure amount in the half-permeation portion was 15% when the exposure amount in the shielding portion was 0%) was performed using a near infrared camera (light source wavelength: 800 nm). A double-sided alignment single-sided exposure apparatus is used to form a positive half-tone exposure mask at a temperature of 40 to 300 (mJ/cm) ² : i-ray converted value), and exposing the pre-baked film pattern to g, h, i mixed rays of the ultra-high pressure mercury lamp in a stepwise manner in a unit of 10 mJ/unit, thereby obtaining an exposed film having an exposed portion, an unexposed portion, and an unexposed portion in a plane. The pattern exposure is performed by bringing the positive type halftone exposure mask into contact with the surface of the pre-bake film.

Then, as the development step, development was carried out in a liquid-covered manner using a small-sized developing device for lithography (AD-1200; manufactured by the greenish industry (stock)) and a 2.38 wt% aqueous tetramethylammonium hydroxide solution as an alkaline developer. The liquid-coating method described here is a method in which an alkaline developer is applied by spraying for 10 seconds to the surface of an exposed film, and then the film is subjected to static development until a predetermined development time is reached. The development time is set to be in the range of 40 seconds to 90 seconds, and the thickness of the thick film portion of the pixel dividing layer having the step obtained after the curing step described later is 3.0 μm.+ -. 0.2 μm, and the thickness of the thin film portion is 1.5. Mu.m. Further, after rinsing with deionized water for 30 seconds in a shower system, the substrate was dried by idling at 200rpm under a condition of 30 seconds, and a developed film-forming substrate including a developed film having a step was obtained.

Then, as a curing step, a high-temperature inert gas oven (INH-9 CD-S; photo-thermal system (Koyo Thermo System) (stock) was used, and the developed film was heated at 250 ℃ for 1 hour under air, thereby obtaining a substrate for exposure sensitivity evaluation including a pixel division layer having a step. For reference, a captured image obtained in example 16 and including a cross section of the substrate for exposure sensitivity evaluation having a step difference was observed by a Scanning Electron Microscope (SEM) is shown in fig. 1. In fig. 1, 1 is a thick film portion of the pixel dividing layer, and 2 is a thin film portion of the pixel dividing layer.

A required minimum exposure amount (mJ/cm) when a film portion of a pixel dividing layer is observed by a flame photometry detector (flame photometric detector, FPD) inspection microscope (MX-61L; olympus (manufactured by Olympus)), and the average value of the opening widths of ten portions of the opening portion in each exposure amount region is opened so as to be in the range of 30.0 [ mu ] m.+ -. 0.1 [ mu ] m ² : i-ray converted value) is set as the exposure sensitivity, and the smaller the value, the more excellent. The evaluation was performed based on the following criteria, and a to C were regarded as acceptable, and D to E were regarded as unacceptable. When the film thickness of the thick film portion cannot be formed at the same time to 3.0 μm.+ -. 0.2 μm and the film thickness of the thin film portion cannot be formed at the same time to 1.5 μm in the range of the above conditions, the evaluation was set to F and the evaluation was set to be failed. Further, the film thickness of the thick film portion (unexposed portion) of the developed film having the step was subtracted from the film thickness of the pre-baked film, that is, the film reduction amount (μm) in the development step was evaluated, and when the film reduction amount exceeded 1.0 μm, it was assumed to be excluded from the evaluation target of the exposure sensitivity. In addition, when the silver alloy film is not visually recognized by the near infrared camera, near infrared alignment is not performed and is excluded from the evaluation target of the exposure sensitivity.

The exposure sensitivity was obtained by the same method as that of the negative-type photosensitive pigment composition 1 obtained in comparative example 6 except that a negative-type halftone exposure mask (a reverse mask in which 220 square shielding portions having a vertical dimension of 30.0 μm and a horizontal dimension of 30.0 μm were arranged and the exposure amount in the full-permeation portion was 100% and the exposure amount in the semi-permeation portion was 30% was 0%) was used instead of the positive-type halftone exposure mask.

A: the exposure sensitivity was 40mJ/cm ² Above and less than 100mJ/cm ² 。

B: the exposure sensitivity was 100mJ/cm ² Above and less than 150mJ/cm ² 。

C: the exposure sensitivity was 150mJ/cm ² Above and less than 200mJ/cm ² 。

D: the exposure sensitivity was 200mJ/cm ² Above and less than 250mJ/cm ² 。

E: the exposure sensitivity was 250mJ/cm ² Above and 300mJ/cm ² The following is given.

F: halftone processing is difficult and cannot be evaluated effectively.

(2) Evaluation of light-blocking Property (OD/. Mu.m) of cured film

For the substrates for evaluating optical characteristics of the cured films having film thickness of 1.5 μm obtained in examples 1 to 19 and comparative examples 1 to 7, the Total optical concentration (Total OD value) was measured at three points in the plane from the film surface side using an optical concentration meter (manufactured by alic (X-Rite)) 361T, the average value was calculated, the decimal second digit of the value obtained by dividing the value by 1.5 was rounded, and the value obtained up to the decimal first digit was set as OD value (OD/μm) of each 1.0 μm thickness of the cured film. The evaluation was made on the basis of a cured film excellent in light-shielding property as the OD/μm value was larger. Since the OD of the cured film was measured separately and was 0.00, the OD of the substrate for evaluating optical properties was regarded as the OD of the cured film. The film thickness of the cured film was measured at three points in the plane using a stylus film thickness measuring device (Tokyo precision (Co.; surfcom)), and the second decimal point of the average value was rounded off to obtain a value up to the first decimal point.

(3) Evaluation of maximum transmittance of cured film at wavelength of 410nm to 440nm

The transmittance in the wavelength range of 380nm to 780nm was measured in units of 1nm using an ultraviolet-visible spectrophotometer "UV-260 (manufactured by Shimadzu corporation)" for the optical property evaluation substrate having a cured film having a film thickness of 1.5 μm obtained using the positive type photosensitive pigment compositions 1 to 24, 26 and 1 obtained in examples 1 to 19, 1 to 5 and 7. The average value of the values obtained by measuring the maximum transmittance (%) at the wavelengths of 410nm to 440nm at three points in the plane was calculated, and the smaller the value, the more excellent the cured film was, the evaluation was made.

(4) Evaluation of storage stability (rate of change in sensitivity to exposure)

The positive photosensitive pigment compositions 1 to 24, the positive photosensitive pigment composition 26, and the negative photosensitive pigment composition 1 obtained in comparative example 6 obtained in examples 1 to 19, comparative examples 1 to 5, and comparative example 7 were obtained by dividing the value obtained by subtracting the value of the exposure sensitivity after storage for 1 day from the value of the exposure sensitivity after storage for 30 days after production by the value of the exposure sensitivity after storage for 1 day and multiplying by 100, and the value obtained by rounding the first decimal point of the value was set as the change rate (%) of the exposure sensitivity. The smaller the rate of change in exposure sensitivity, the higher and more excellent the storage stability, and the evaluation was made based on the following criterion, with A to C being acceptable and D to E being unacceptable. In at least one of the cases after 1 day or 30 days of storage after the preparation, the evaluation was set to F and failed when the film thickness of the thick film portion could not be formed at the same time to 3.0 μm±0.2 μm and the film thickness of the thin film portion could not be formed at the same time to 1.5 μm. In addition, the exposure sensitivity in the evaluation at least at any one time was 200mJ/cm after 1 day of storage or 30 days of storage ² In the above cases, the evaluation was set to G, and was set to be failed. When the evaluation is F and G, the evaluation is F, and the evaluation is setAnd is disqualified.

A: the rate of change of exposure sensitivity was less than 5%.

B: the rate of change in exposure sensitivity is 5% or more and less than 15%.

C: the rate of change in exposure sensitivity is 15% or more and less than 30%.

D: the rate of change of the exposure sensitivity is 30% or more and less than 40%.

E: the rate of change of the exposure sensitivity was 40% or more.

F: halftone processing is difficult and cannot be evaluated effectively.

G: after 1 day of storage or 30 days of storage, the exposure sensitivity in the evaluation at least at any one time was 200mJ/cm ² The above.

(5) Evaluation of halftone processability

The pixel division layer forming substrates obtained in examples 1 to 19, comparative examples 1 to 3, and comparative examples 6 to 7 were observed with an FPD inspection microscope, and the opening widths of the openings at ten positions in the plane were measured. From the maximum opening width W ₁ (μm) minus the minimum opening width W ₂ Value W (μm) ₃ The smaller the (μm), the better, the evaluation was made based on the following criterion, and a to C were judged as acceptable, and D to E were judged as unacceptable. However, if the film thickness of the thick film portion cannot be formed to be 3.0 μm±0.2 μm at one time and the film thickness of the thin film portion cannot be formed to be 1.5 μm at one time, the evaluation was set to F and the evaluation was set to be failed.

A：W ₃ Less than 1.0 μm.

B：W ₃ Is 1.0 μm or more and less than 1.2 μm.

C：W ₃ Is 1.2 μm or more and less than 1.5 μm.

D：W ₃ Is 1.5 μm or more and less than 2.0 μm.

E：W ₃ Is more than 2.0 mu m.

F: halftone processing is difficult and cannot be evaluated effectively.

(6) Evaluation of organic EL display device

By 10mA/cm ² The organic EL display devices obtained in examples 1 to 19, comparative examples 1 to 3, and comparative examples 6 to 7 were made to emit light, and among the pixel portions formed in the region of 30mm in the vertical direction and 30mm in the horizontal direction, 30 portions of the pixel portion located in the central portion were enlarged by a magnification of 50 times and displayed on a monitor for observation, and a to C were made to be acceptable and D to E were made to be unacceptable based on the following determination criterion evaluation of the unevenness in luminance in the plane. When one or more non-lit pixels are seen, the evaluation is set to E and the non-lit pixels are not qualified.

A: no brightness unevenness was observed.

B: the brightness unevenness was slightly seen.

C: uneven brightness is seen.

D: uneven brightness is clearly seen.

E: more than one non-illuminated pixel is seen.

Information about the various raw materials used in examples and comparative examples is shown below.

Synthesis example 1 Synthesis of hydroxyl group-containing diamine Compound A

18.3g (0.05 mol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane were dissolved in 100mL of acetone, 17.4g (0.3 mol) of propylene oxide, and cooled to-15 ℃. A solution of 0.11mol (20.4 g) of 3-nitrobenzoyl chloride dissolved in 100mL of acetone was added dropwise thereto. After the completion of the dropwise addition, the reaction was carried out at-15℃for 4 hours, and then the reaction was allowed to return to room temperature. The white solid precipitated was isolated by filtration and dried under vacuum at 50 ℃. 30g of the solid was placed in a 300mL stainless steel autoclave, dispersed in 250mL of methyl cellosolve, and 2g of 5% palladium-carbon was added. Hydrogen was introduced into the reactor by means of a balloon, and the reduction reaction was carried out at room temperature. After about 2 hours, it was confirmed that the balloon did not collapse and the reaction ended. After the completion of the reaction, the palladium compound as a catalyst was filtered and removed, and the mixture was concentrated by a rotary evaporator to obtain a hydroxyl group-containing diamine compound a represented by the formula (54).

[ 47]

Synthesis example 2 Synthesis of polyimide precursor B

31.0g (0.10 mol) of 3,3', 4' -diphenyl ether tetracarboxylic dianhydride was dissolved in 500g of NMP under a stream of dry nitrogen. 45.35g (0.075 mol) of the hydroxyl group-containing diamine compound A obtained in Synthesis example 1, 1.24g (0.005 mol) of 1, 3-bis (3-aminopropyl) tetramethyldisiloxane, and 50g of NMP were added together, and reacted at 20℃for 1 hour, followed by 50℃for 2 hours. As a terminal sealer, 4.36g (0.04 mol) of 4-aminophenol was added together with 5g of NMP and reacted at 50℃for 2 hours. Then, 28.6g (0.24 mol) of N, N-dimethylformamide dimethyl acetal (50 g) was charged. After the addition, the mixture was stirred at 50℃for 3 hours. After completion of stirring, the solution was cooled to room temperature, and then the solution was poured into 3L of water to obtain a white precipitate. The white precipitate obtained by repeating the above operation five times was collected as a filtrate, washed five times with water, and dried for 24 hours by a vacuum dryer at 80 ℃. The polyimide precursor B was the component (c-1), the weight average molecular weight (Mw) was 25,000, and the amine value was 1.0mgKOH/g.

Synthesis example 3 Synthesis of polyimide resin C

150.15g (0.41 mol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 6.20g (0.02 mol) of 1, 3-bis (3-aminopropyl) tetramethyldisiloxane, and 13.65g (0.13 mol) of 3-aminophenol as an end sealer were dissolved in 500.00g of NMP under a dry nitrogen stream, 155.10g (0.50 mol) of bis (3, 4-dicarboxyphenyl) ether dianhydride, and 150.00g of NMP were added thereto and stirred at 20℃for 1 hour, and further stirred at 180℃for 4 hours while removing water. After the completion of the reaction, the reaction solution was poured into 10L of water, and the resulting precipitate was filtered and collected, washed five times with water, and dried for 20 hours with a vacuum dryer at 80 ℃ to obtain a polyimide resin C having the structural unit represented by formula (38) and having no structural unit represented by formula (39). The polyimide resin C was the component (C-1), the weight average molecular weight (Mw) was 25,000, and the amine value was 1.0mgKOH/g.

Synthesis example 4 Synthesis of methacrylic resin solution D

The methacrylic resin solution D was obtained by the following method with reference to synthesis example 2 of patent document 2.

A mixed solution of 12.91g (0.15 mol) of methacrylic acid, 55.07g (0.55 mol) of methyl methacrylate, 21.01g (0.10 mol) of acidic phospho ethyl methacrylate which is an ethylenically unsaturated monomer having a phosphate group, 26.43g (0.15 mol) of benzyl methacrylate, and 8.21g of azobisisobutyronitrile was added dropwise to 185.44g of PGMEA maintained at a liquid temperature of 100℃over 30 minutes, and stirred for 1 hour while maintaining the liquid temperature, whereby a thermal polymerization reaction was performed and then cooled to synthesize a methacrylic resin d having a phosphate group. The methacrylic resin d was the component (c-1), and the weight average molecular weight (Mw) was 9,500. The resultant was diluted with PGMEA so that the solid content became 30 wt%, thereby obtaining a methacrylic resin solution D.

Synthesis example 5 Synthesis of polyimide resin E

58.60g (0.16 mol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 8.73g (0.08 mol) of 3-aminophenol as a terminal sealer were dissolved in 300.00g of NMP under a stream of dry nitrogen. 62.04g (0.20 mol) of 3,3', 4' -diphenyl ether tetracarboxylic dianhydride was added thereto together with 100.00g of NMP, and stirred at 20℃for 1 hour, followed by 50℃for 4 hours. Then, 15g of xylene was added thereto, and the mixture was stirred at 150℃for 5 hours while azeotroping water with xylene. After the stirring was completed, the solution was poured into water 5L and a white precipitate was collected. The precipitate was collected by filtration and washed three times with water, and then dried for 24 hours by a vacuum dryer at 80 ℃ to obtain a polyimide resin E having the structural unit represented by formula (38) and having no structural unit represented by formula (39). The polyimide resin E was the component (c-1), the number average molecular weight (Mw) was 8,200, and the amine value was 1.0mgKOH/g.

Synthesis example 6 Synthesis of quinone diazide compound a

21.22g (0.05 mol) of TrisP-PA (manufactured by the chemical industry, benstate) and 36.27g (0.135 mol) of 5-naphthoquinone diazide sulfonyl chloride were dissolved in 450g of 1, 4-dioxane under a dry nitrogen stream, and the mixture was set at room temperature. To this solution, a solution of 15.18g of triethylamine dissolved in 50g of 1, 4-dioxane was added dropwise at a temperature of 35℃or lower in the system. After the dropwise addition, the mixture was stirred at 30℃for 2 hours. The triethylamine salt was filtered, and the filtrate was poured into water. Filtration is then carried out to collect the precipitated precipitate. The precipitate was dried by a vacuum dryer to obtain a quinone diazide compound a represented by formula (55) as component (d). The quinone diazide compound a is the component (d).

[ 48]

In formula (55), the bond site to the oxygen atom is represented.

Synthesis example 7 Synthesis of quinone diazide compound b

Synthesis was performed in the same manner as in Synthesis example 3 except for using 36.27g (0.135 mol) of 4-naphthoquinone diazide sulfonyl chloride instead of 36.27g (0.135 mol) of 5-naphthoquinone diazide sulfonyl chloride, thereby obtaining quinone diazide compound b represented by formula (56). The quinone diazide compound b is the component (d).

[ 49]

In formula (56), the bond site to the oxygen atom is represented.

PREPARATION EXAMPLE 1 preparation of micronized perylene black pigment 1

1,000.00g of "Speranson (registered trademark)" Black K0087 (manufactured by Basf) was heated by an oven at 250℃under atmospheric pressure/air for 1 hour, cooled to room temperature, and then dried and coagulated by a ball mill to obtain a purple Black pigment 1. Then, physical refinement treatment was performed by solvent salt milling according to the following procedure.

500.00g of black pigment 1 was mixed with 2.5kg of a ground material (sodium chloride particles having an average primary particle diameter of 0.5 μm, which had been heat-treated at 230℃for 1 hour and had been set to have a water content of 0.1% by weight in advance), 250.00g of dipropylene glycol, and the mixture was put into a stainless steel 1-gallon kneader (manufactured by well manufacturing) and kneaded at 90℃for 8 hours. The kneaded material was put into 5L of warm water and stirred for 1 hour while maintaining the temperature at 70 ℃ to prepare a slurry, and filtration and washing were repeated until the amount of chloride ions quantified by ion chromatography became 50 ppm by weight or less, and the ground material and dipropylene glycol were removed. Further, after drying at 100℃for 6 hours under atmospheric pressure/air in an oven, the drying and aggregation were released by a ball mill, whereby a micronized perylene black pigment 1 comprising a mixture of isomers of the compound represented by formula (9) and the compound represented by formula (10) was obtained. Further, the micronized perylene black pigment 1 was component (a), the average primary particle diameter was 25nm, the maximum primary particle diameter was 98nm, and the average aspect ratio was 1.1. Further, the chemical structure of the micronized perylene black pigment 1 was analyzed by MALDI-TOF MS.

PREPARATION EXAMPLE 2 preparation of micronized perylene black pigment 2

To a mixture of 2,648.16g of phenol melted at 70℃was added 588.48g (1.50 mol) of perylene-3, 4,9, 10-tetracarboxylic dianhydride, 408.60g (3.00 mol) of 4, 5-dimethyl-1, 2-phenylenediamine, and 64.61g of piperazine, and the temperature of the liquid was raised to 170℃while maintaining stirring. Then, the mixture was stirred under heating at 170℃for 8 hours to allow the reaction to proceed sufficiently, and then the water produced was distilled off as an azeotropic mixture with phenol. Then, the mixture was cooled to 130℃and 500g of ethanol was added in stages in 50g units, and the reaction product was separated by filtration after stirring at 60℃for 1 hour. After washing with ethanol until the filtrate became transparent, washing with water and drying at 80℃under reduced pressure for 24 hours, pigment crude 2 was obtained. Then, physical refinement treatment was performed by solvent salt milling according to the following procedure.

500.00g of pigment crude 2 was mixed with 2.5kg of ground material (sodium chloride particles having an average primary particle diameter of 0.5 μm, which were heat-treated at 230℃for 1 hour and had a water content of 0.1% by weight in advance), 250.00g of dipropylene glycol, and the mixture was charged into a stainless steel 1-gallon kneader (manufactured by well manufacturing) and kneaded at 90℃for 10 hours. The kneaded material was put into 5L of warm water and stirred for 1 hour while maintaining the temperature at 70 ℃ to prepare a slurry, and filtration and washing were repeated until the amount of chloride ions quantified by ion chromatography became 50 ppm by weight or less, and the ground material and dipropylene glycol were removed. Further, after drying in an oven at 100℃for 6 hours under atmospheric pressure/air, the drying and aggregation were released by a ball mill, whereby a micronized perylene black pigment 2 comprising a mixture of isomers of the compound represented by formula (57) and the compound represented by formula (58) was obtained.

Further, the micronized perylene black pigment 2 was component (a), the average primary particle diameter was 26nm, the maximum primary particle diameter was 110nm, and the average aspect ratio was 1.1. Further, the chemical structure of the micronized perylene black pigment 2 was analyzed by MALDI-TOF MS.

[ 50]

PREPARATION EXAMPLE 3 preparation of micronized perylene black pigment 3

To a mixture of 2,648.16g of phenol melted at 70℃was added 588.48g (1.50 mol) of perylene-3, 4,9, 10-tetracarboxylic dianhydride, 378.30g (3.00 mol) of 4-fluoro-1, 2-phenylenediamine, and 64.61g of piperazine, and the liquid temperature was raised to 170℃while maintaining stirring. Then, the mixture was stirred under heating at 170℃for 8 hours to allow the reaction to proceed sufficiently, and then the water produced was distilled off as an azeotropic mixture with phenol. Then, the mixture was cooled to 130℃and 500g of ethanol was added in stages in 50g units, and the reaction product was separated by filtration after stirring at 60℃for 1 hour. After washing with ethanol until the filtrate became transparent, washing with water and drying at 80℃under reduced pressure for 24 hours, pigment crude 3 was obtained. Thereafter, by performing physical refinement treatment by solvent salt milling in the same manner as in production example 2, a micronized perylene black pigment 3 including an isomer mixture of the compound represented by formula (59) and the compound represented by formula (60) was obtained.

Further, the micronized perylene black pigment 3 was component (a), the average primary particle diameter was 45nm, the average aspect ratio was 1.3, and the maximum primary particle diameter was 119nm. Further, the chemical structure of the micronized perylene black pigment 3 was analyzed by MALDI-TOF MS.

[ 51]

PREPARATION EXAMPLE 4 preparation of micronized perylene black pigment 4

To a mixture of 2,648.16g of phenol melted at 70℃was added 588.48g (1.50 mol) of perylene-3, 4,9, 10-tetracarboxylic dianhydride, 474.60g (3.00 mol) of 1, 8-diaminonaphthalene, and 64.61g of piperazine, and the liquid temperature was raised to 170℃while maintaining stirring. Then, the mixture was stirred under heating at 170℃for 8 hours to allow the reaction to proceed sufficiently, and then the water produced was distilled off as an azeotropic mixture with phenol. Then, the mixture was cooled to 130℃and 500g of ethanol was added in stages in 50g units, and the reaction product was separated by filtration after stirring at 60℃for 1 hour. After washing with ethanol until the filtrate became transparent, washing with water and drying at 80℃under reduced pressure for 24 hours, thereby obtaining a pigment crude 4. Thereafter, by performing physical refinement treatment by solvent salt milling in the same manner as in production example 2, a micronized perylene black pigment 4 including a compound represented by formula (61) and an isomer mixture of a compound represented by formula (62) was obtained.

Further, the micronized perylene black pigment 4 was component (a), the average primary particle diameter was 85nm, the average aspect ratio was 1.6, and the maximum primary particle diameter was 125nm. Further, the chemical structure of the perylene black pigment 4 was refined and analyzed by MALDI-TOF MS.

[ 52]

PREPARATION EXAMPLE 5 preparation of micronized dioxazine pigment 1

1,000.00g of C.I. pigment blue 80 (manufactured by Clariant) was heated by an oven at 200℃under atmospheric pressure/air for 1 hour, cooled to room temperature, and then dried and coagulated by a ball mill to obtain a violet-colored blue dioxazine pigment, namely, blue pigment 1. Then, physical refinement treatment was performed by solvent salt milling according to the following procedure.

500.00g of blue pigment 1 was mixed with 2.5kg of a milled material (the same milled material as used in production example 2) and 250.00g of dipropylene glycol, and the mixture was charged into a stainless steel 1 gallon kneader (manufactured by well manufacturing) and kneaded at 90℃for 5 hours. The kneaded material was put into 5L of warm water, stirred for 1 hour while maintaining at 70 ℃ to prepare a slurry, and the filtration and water washing were repeated three times to remove the ground material and dipropylene glycol. Further, after drying at 100℃for 6 hours under atmospheric pressure/air in an oven, the drying and aggregation were removed by a ball mill to obtain a composition containing R in the formula (11) ⁶³ R is R ⁶⁴ Is a chlorine atom, R ⁶⁵ R is R ⁶⁸ Is a hydrogen atom, R ⁶⁶ R is R ⁶⁷ Micronization of ethyl Compound dioxazine pigment 1. Further, the micronized dioxazine pigment 1 was the component (h), the average primary particle diameter was 34nm, the maximum primary particle diameter was 140nm, and the average aspect ratio was 1.2. Further, the chemical structure of the micronized dioxazine pigment 1 was analyzed by MALDI-TOF MS.

Production example 6 production of micronized dioxazine pigment 2

1,000.00g of "kulao Mo Fuda (Cromophtal) (registered trademark)" Violet D5700 (manufactured by BASF) was heated by an oven at 200℃under atmospheric pressure/air for 1 hour, cooled to room temperature, and then dried and coagulated by a ball mill to obtain a Violet dioxazine pigment, namely Violet pigment 1. Then, physical refinement treatment was performed by solvent salt milling according to the following procedure.

500.00g of violet pigment 1 was mixed with 2.5kg of a milled material (the same milled material as used in production example 2) and 250.00g of dipropylene glycol, and the mixture was charged into a stainless steel 1 gallon kneader (manufactured by well manufacturing) and kneaded at 90℃for 5 hours. The kneaded material was put into 5L of warm water, stirred for 1 hour while maintaining at 70 ℃ to prepare a slurry, and the filtration and water washing were repeated three times to remove the ground material and dipropylene glycol. Further, after drying at 100℃for 6 hours under atmospheric pressure/air in an oven, the drying and aggregation were removed by a ball mill to obtain a composition containing R in the formula (12) ¹³¹ R is R ¹³² Is ethyl, R ¹³³ R is R ¹³⁴ Is methyl, R ¹³⁵ R is R ¹³⁶ Micronization of NH Compound dioxazine pigment 2.

Further, the micronized dioxazine pigment 2 was the component (h), the average primary particle diameter was 30nm, the maximum primary particle diameter was 110nm, and the average aspect ratio was 1.0. Further, the chemical structure of the micronized dioxazine pigment 2 was analyzed by MALDI-TOF MS.

The average primary particle diameters, average aspect ratios, and maximum primary particle diameters of the micronized perylene Black pigments 1 to 4, the micronized dioxazine pigments 1 to 2, and the micronized perylene Black pigments 1 to 4, and the micronized perylene pigment 2, respectively, are shown in table 1.

TABLE 1

Synthesis example 8 Synthesis of pigment A

Particulate pigment, namely, daiwa Red 178 (manufactured by Daiwa Red) was ground with a mortar, and 50.00g of powder obtained by removing coarse components with a stainless steel screen filter (opening diameter 38 μm) was added to 950.00g of PGME: water=weight ratio 1:1 mixed solution, and stirred for 30 minutes to obtain a pre-stirred solution. The pre-stirred solution was fed to a horizontal bead MILL ("Dyno-MILL (registered trademark)"; (manufactured by Tory (stock)) having a filling rate of 75% by volume and filled with zirconia beads of 1.0mm phi in a vessel (vessel); (Toray Corp.); (registered trademark) "; (manufactured by Wily A. Bachofen, inc.), the pale red filtrate introduced into the filter was discarded after being subjected to wet medium dispersion treatment at a peripheral speed of 10m/s in a cyclic manner for 2 hours, and the filtrate was collected by washing with water until sulfate ions quantified by ion chromatography were less than 50ppm, the filtrate was dried at 80℃under reduced pressure for 24 hours to obtain a powdery pigment A having a solid content of 100% as a component (b-2) and a mixture of a compound represented by the formula (24), a compound represented by the formula (25) and a compound represented by the formula (26) in a weight ratio of 42:55, and the dye A was analyzed by chemical analysis was performed by using MALDI-LC.

Synthesis example 9 Synthesis of pigment B

50.00g of C.I. pigment Red 178 was dissolved in 500.00g of 80 wt% concentrated sulfuric acid, heated, and stirred at 70℃for 6 hours to carry out sulfonation. Then, the slurry was poured into 5kg of ice water to obtain a precipitate-containing slurry, and the slurry was filtered. Then, after washing the filtrate with ethanol, the washing was repeated until the residual amount of sulfate ions was less than 50 ppm by weight, and the filtrate was dried at 80℃under reduced pressure for 24 hours. Then, dry pulverization was performed using a nanojet atomizer (manufactured by attorney docket (Aisin nanotechnology) (strand)), and coarse components were removed by using a stainless steel screen filter (opening diameter: 50 μm), whereby powdery pigment B was obtained. Pigment B is a component (B-2), and is a compound represented by formula (24), a compound represented by formula (25), and a compound represented by formula (26) in a weight ratio of 25:65: 10. The chemical structure of pigment B was analyzed by MALDI-TOF MS, and the weight ratio of the compound constituting pigment B was analyzed by LC-MS.

Synthesis example 10 Synthesis of pigment C

50.00g of C.I. pigment black 31 was dissolved in 500.00g of 80 wt% concentrated sulfuric acid, heated, and stirred at 60℃for 4 hours to carry out sulfonation. The subsequent steps were carried out in the same manner as in Synthesis example 6 to obtain powdery pigment C. Pigment C is a component (b-1), and the weight ratio of the compound represented by formula (21) to the compound represented by formula (63) is 33: 67. The chemical structure of pigment C was analyzed by MALDI-TOF MS, and the weight ratio of the compound constituting pigment C was analyzed by LC-MS.

[ 53]

Synthesis example 11 Synthesis of pigment D

196.16g (0.50 mol) of perylene-3, 4,9, 10-tetracarboxylic dianhydride and 151.16g (1.00 mol) of 3- (aminomethyl) benzoic acid were added to 1,961.60g of imidazole melted at 100℃and stirred under nitrogen at a heating temperature of 130℃for 6 hours to effect imidization. The obtained reaction product was cooled to 10 ℃, and then, the reaction product was poured into 5kg of ice water to obtain a slurry containing a precipitate, and the slurry was filtered. The filtrate was washed with ethanol, washed with water, and dried at 80℃under reduced pressure for 24 hours. Further, dry pulverization was performed using a nano jet atomizer, and coarse components were removed by a stainless steel screen filter (opening diameter: 50 μm), whereby powdery pigment D was obtained. Pigment D is a component (b-1) and is a compound represented by formula (23). Furthermore, the chemical structure of pigment D was analyzed by MALDI-TOF MS.

Synthesis example 12 Synthesis of pigment E

134.09g (0.50 mol) of naphthalene-1, 4,5, 8-tetracarboxylic dianhydride and 291.33g (1.00 mol) of 3- [ (4-amino-3-methylphenyl) azo ] benzenesulfonic acid were added to 1340.90g of imidazole melted at 100℃and heated, and stirred under nitrogen at 150℃for 6 hours to effect imidization. The obtained reaction product was cooled to 10 ℃, and then, the reaction product was poured into 5kg of ice water to obtain a slurry containing a precipitate, and the slurry was filtered. The filtrate was washed with ethanol, washed with water, and dried at 80℃under reduced pressure for 24 hours. Then, dry pulverization was performed using a nano jet atomizer, and coarse components were removed by a stainless steel screen filter (opening diameter: 50 μm), whereby powdery pigment E was obtained. Pigment E is a component (b-2) and is a compound represented by formula (64). Furthermore, the chemical structure of pigment E was analyzed by MALDI-TOF MS.

[ 54]

Synthesis example 13 Synthesis of pigment F

50.00g of C.I. pigment yellow 138 was dissolved in 250.00g of 11 wt% fuming sulfuric acid, heated, and stirred at a liquid temperature of 90℃for 6 hours to carry out sulfonation. After cooling to 25 ℃, the mixture was poured into 500g of water to obtain a slurry containing a precipitate, and the slurry was filtered. The filtrate was then repeatedly washed with water until the residual sulfate ion content was less than 50 ppm by weight, and dried at 90℃under reduced pressure for 24 hours. Further, dry pulverization was performed using a nano jet atomizer, and coarse components were removed by a stainless steel screen filter (opening diameter: 50 μm), whereby powdery pigment F was obtained. The dye F is a compound not corresponding to the component (b), and is a compound represented by the formula (65). Furthermore, the chemical structure of pigment F was analyzed by MALDI-TOF MS.

[ 55]

Synthesis example 14 Synthesis of pigment G

78.46g (0.20 mol) of perylene-3, 4,9, 10-tetracarboxylic dianhydride and 34.73g (0.27 mol) of 3-diethylaminopropyl amine were added to 1307.73g of o-dichlorobenzene, and the mixture was stirred at 120℃for 3 hours to effect imidization. O-dichlorobenzene was removed by distillation under reduced pressure, washed with acetone, then water-washed and filtered, and dried at 90℃under reduced pressure for 24 hours. Then, dry pulverization was performed using a nano jet atomizer, and coarse components were removed by a stainless steel screen filter (opening diameter: 50 μm), whereby powdery pigment G was obtained. The dye G is a compound which does not correspond to the component (b) and is a compound represented by the formula (66) having an N, N-dialkylaminoalkyl group. Furthermore, the chemical structure of pigment G was analyzed by MALDI-TOF MS.

[ 56]

Pigment H: perylene dye derivative 8 disclosed in patent document 2. Is a compound which does not correspond to the component (b) and is a compound represented by the formula (67) having an N, N-dialkylaminoalkyl group.

[ 57]

Synthesis example 15 Synthesis of pigment I

50.00g of N, N' -diphenyl-3, 4,9, 10-perylene dicarboximide (manufactured by Sigma-Aldrich) was dissolved in 500.00g of 70% by weight concentrated sulfuric acid, heated, and stirred at 70℃for 3 hours to carry out sulfonation. After cooling to a liquid temperature of 40 ℃, the mixture was poured into 5kg of ice water to obtain a slurry containing red precipitate, and the slurry was filtered. The mixture was washed with ethanol and deionized water and filtered to obtain a red precipitate a as a filtrate. Analysis using MALDI-TOF MS gave red precipitate A as a monosulfonate of N, N' -diphenyl-3, 4,9, 10-perylene dicarboximide. Subsequently, the filtrate containing the red precipitate a was added to 3kg of deionized water, stirred and slurried again. Further, while stirring a 20 wt% aqueous solution of sodium hydroxide, the slurry was added stepwise until the pH of the slurry became 11.0, and then the temperature was raised to 60℃and stirring was performed for 3 hours. Then, while stirring a 5 wt% aqueous solution of calcium chloride (manufactured by Sigma Aldrich) until the pH of the slurry became 3.5, a red precipitate B was formed, which was separated by filtration, repeatedly washed with water, and dried at 80 ℃ under reduced pressure for 24 hours. Further, dry pulverization was performed using a nanojet atomizer (manufactured by Aishi nanotechnology (Aisin nanotechnology) (strand)), coarse components were removed by a stainless steel screen filter (opening diameter: 50 μm), and pigment I was obtained in the form of powder, and it was confirmed that it was a calcium salt by fluorescent X-ray analysis. The dye I is a component (b) and is a compound represented by the formula (75).

[ 58]

Pigment J: the compound represented by the formula (76) was synthesized based on example 7 of European patent application publication No. 0486531 and purified by silica gel chromatography. The chemical structure of pigment J was analyzed using MALDI-TOF MS.

[ 59]

Pigment K: perylene-3-sulfonic acid (manufactured by Sigma Aldrich) represented by formula (77)

[ chemical 60]

Table 2 summarizes the number of structures represented by the formula (2) and the number of functional groups contained in the molecule of the above pigments A to K. In table 2, the expression "0" means not having.

TABLE 2

Preparation example 1 preparation of pigment Dispersion 1

To 900.00g of the mixed solvent (PGME, ethyl lactate and gamma-butyrolactone; weight ratio 50:40:10) as the component (e), 68.38g of the polyimide precursor B as the component (c-1) was added, and the mixture was stirred for 30 minutes to dissolve the polyimide precursor B. Further, 4.59g of pigment A as the component (b-2) was added, and after stirring for 30 minutes, 27.03g of "Speranson (registered trademark)" Black K0087 (in Table 3, "Speranson (Spectrase)) as the component (a) was added, and stirred for 30 minutes, to thereby obtain a pre-stirred solution. Then, the pre-stirred solution was fed to a horizontal bead mill ("super advanced ai bas mill (ultra apex mill advance) (registered trademark)"; manufactured by Hiroshima Metal & Machinery) in which a vessel was filled with zirconia beads of 0.05mm Φ, namely, "Torayceram (registered trademark)" (manufactured by eastern strand), at a filling rate of 75% by volume, and a wet medium dispersion treatment was performed at a peripheral speed of 10m/s for 5 hours by a circulation system, whereby a pigment dispersion liquid having a solid content of 10.00% by weight was obtained. The first filtration was performed by a filter having a diameter of 0.8. Mu.m, and the second filtration was performed by a filter having a diameter of 0.2. Mu.m. As the value of the solid content up to the second decimal point before and after filtration, the component (a) was obtained without any fluctuation: component (b): (c) resin = weight ratio 100:17:253 and a solid content of 10.00% by weight. The blending weights of the respective raw materials are shown in Table 3.

TABLE 3

( Preparation examples 2 to 5: preparation of pigment Dispersion 2 to pigment Dispersion 5 )

Pigment dispersions 2 to 5 were obtained by performing wet medium dispersion treatment and filtration in the same manner as in preparation example 1, except that the micronized perylene Black pigments 1 to 4 were used instead of "spettrassen (registered trademark)" Black K0087, respectively. The blending weights of the respective raw materials are shown in Table 3.

( Preparation examples 6 to 9: preparation of pigment Dispersion 6 to pigment Dispersion 9 )

Pigment B to pigment E were used instead of pigment a, respectively, and a wet medium dispersion treatment and filtration were performed in the same manner as in preparation example 1, to obtain pigment dispersions 6 to 9. The blending weights of the respective raw materials are shown in Table 4.

TABLE 4

Preparation example 10 preparation of pigment Dispersion 10

A pigment dispersion liquid 10 was obtained by performing wet medium dispersion treatment and filtration in the same manner as in production example 1 except that the polyimide resin C was used instead of the polyimide precursor B. The blending weights of the respective raw materials are shown in Table 4.

( Preparation examples 11 to 12: preparation of pigment Dispersion 11 to pigment Dispersion 12 )

Pigment dispersion 11 to pigment dispersion 12 were obtained by performing wet medium dispersion treatment and filtration in the same manner as in preparation example 1 except that the ratio of the blending amounts of the respective raw materials was changed based on preparation example 6. The blending weights of the respective raw materials are shown in Table 4.

( Preparation examples 13 to 14: preparation of pigment Dispersion 13 to pigment Dispersion 14 )

Pigment F to pigment G were used instead of pigment a, respectively, and wet medium dispersion treatment and filtration were performed in the same manner as in preparation example 1, to obtain pigment dispersions 13 to 14. The blending weights of the respective raw materials are shown in Table 5.

TABLE 5

Preparation example 15 preparation of pigment Dispersion 15

26.72g of a polyimide resin C, 93.75g of a methacrylic resin solution D (solid content: 30% by weight), 784.38g of PGMEA, and 1.41g of a pigment H were mixed and stirred for 30 minutes, thereby obtaining a pre-stirred solution. Then, 28.13g of c.i. pigment yellow 192 (average primary particle diameter: 42 nm), 28.13g of c.i. pigment red 179 (average primary particle diameter: 48 nm), and 37.50g of c.i. pigment blue 60 (average primary particle diameter: 61 nm) were charged and stirred for 30 minutes. A horizontal bead MILL ("DYNO-MILL (registered trademark)"; manufactured by wili a. bahofen (Willy a.bachofen)) filled with 0.4mm Φ zirconia beads, "toraug (registered trademark)" (manufactured by eastern strand) was used, and wet medium dispersion treatment was performed for 30 minutes by a circulation method. Then, a horizontal bead mill ("super advanced ebeck mill (ultra apex mill advance) (registered trademark)"; manufactured by Hiroshima Metal & Machinery) in which a vessel was filled with zirconia beads having a filling rate of 75% by volume, namely, "torayfera (registered trademark)" (manufactured by toray), was used, a wet medium dispersion treatment was performed by a circulation method, after 30 minutes, a pigment dispersion in which a proper amount was extracted into a glass bottle every 10 minutes for a dispersion treatment time was sampled was set in a dynamic light scattering particle size distribution measuring device SZ-100, the average dispersion particle diameter was measured, and a pigment dispersion in which the time after 30 minutes was sampled was within a range of 150nm±20nm was set as a pigment dispersion 13. The average dispersion particle diameter as used herein refers to the number average of the secondary particle diameters of all pigment particles contained in the pigment dispersion liquid.

PREPARATION EXAMPLE 16 preparation of pigment Dispersion 16

To 891.71G of PGMEA, 60.00G of TRR5010G (manufactured by Asahi organic materials (stock); 100% by weight of solid matter; PGMEA-soluble phenol resin as component (c-1)) was added, and the mixture was stirred for 30 minutes to dissolve the same. Then, 21.27g of Pick (BYK) -LPN6919 (manufactured by Pick chemical (BYK-Chemie Japan) (strand; 61 wt% of PGMEA solution as a solid component) as a component (c-2) was added thereto, and the mixture was stirred for 5 minutes, followed by adding 27.03g of "Speranson (registered trademark)" Black K0087 as a component (a) and stirring for 30 minutes, thereby obtaining a pre-stirred solution. Thereafter, a wet medium dispersion treatment and filtration were carried out in the same manner as in production example 1 to obtain a pigment dispersion 16 having a solid content of 10.00% by weight. The blending weights of the respective raw materials are shown in Table 5.

Preparation example 17 preparation of pigment Dispersion 17

30.00g of polyimide resin E, 30.00g of "SOLSPERSE (registered trademark)" 20000 (Lu Borun (Lubrizol)) as the component (c-1), 100% by weight of a solid content, 32mgKOH/g of an amine value, a polyether resin having an N, N-dialkylaminoalkyl group, and 850.00g of MBA were mixed and stirred for 30 minutes. Then, 90.00g of "Yi Jiafo mol (IRGAPHOR) (registered trademark)" Black S0084 (manufactured by BASF corporation; hereinafter "Black S0084") was mixed, and stirred for 20 minutes using a high-speed stirrer (type 2.5 of a homomixer; manufactured by spectral lemi (Primix)), to obtain a pre-stirred liquid. Then, the pre-stirred solution was fed to a horizontal bead mill ("ultra apex mill (registered trademark)"; manufactured by Hiroshima Metal & Machinery) which was filled with zirconia crushed balls (YTZ; manufactured by Tosoh) having a filling rate of 75% by volume and a filling rate of 0.30mm phi in a container, and the mixture was treated at a peripheral speed of 7.0m/s for 3 hours, whereby a pigment dispersion 17 having a solid content of 15.00% by weight was obtained.

Example 1

To 8.03g of a mixed solvent (PGME, ethyl lactate and gamma-butyrolactone; weight ratio 50:40:10) as component (e) were added 0.83g of polyimide precursor B as component (c-1), 1.27g of quinone diazide compound a, 0.15g of quinone diazide compound B, 0.68g of 4,4' -trihydroxy triphenylmethane as component (f), 0.75g of HMOM-TPHAP (manufactured by Benzhou chemical industry (strand)), as component (g), a compound represented by formula (68), and a solid 5 wt% PGME solution of 0.05g of Pick (BYK) -333 (manufactured by Japanese Pick chemistry (strand)) as a leveling agent under a yellow lamp, and stirred for 30 minutes to dissolve the mixture. Further, 38.25g of the pigment dispersion liquid 1 was added and stirred for 30 minutes to obtain a positive photosensitive pigment composition 1 having a solid content of 15.00 wt%. The blending weights of the respective raw materials are shown in Table 6.

[ chemical 61]

TABLE 6

After the preparation, 24g of each positive photosensitive pigment composition 1 was added to two 50mL light-shielding glass bottles, which were covered tightly and stored (at atmospheric pressure/under light shielding/kept at-20.+ -. 1 ℃ C., left standing in a closed state). After 1 day of storage, one of them was taken out from the dark place and set to room temperature (23 ℃ C.), and the exposure sensitivity was evaluated by the method described above.

Then, the rotation speed was adjusted so that the thickness of the finally obtained cured film became 1.5 μm, and the positive photosensitive pigment composition 1 was coated on the surface of "tenbacus (Tempax)" (manufactured by AGC technical glass (strands)) as a transparent glass substrate by a spin coater, thereby obtaining a coated film. The coated film was prebaked at 110℃for 120 seconds under atmospheric pressure using a hot plate (SCW-636; manufactured by Dakai Screen Co., ltd.) to obtain a prebaked film. The entire surface of the pre-baked film was irradiated with mixed radiation of g, h, and i of an ultra-high pressure mercury lamp using a double-sided alignment single-sided exposure apparatus at an exposure amount corresponding to 15% of the exposure sensitivity (required minimum exposure amount) obtained by the above-described method, to obtain an exposed film. Development, rinsing and drying were performed by the same method as in evaluating the exposure sensitivity, thereby obtaining an integral developed film. The developed film was heated at 250℃for 1 hour in an inert gas oven (INH-9 CD-S; photo ocean thermal System (Koyo Thermo System) (stock)) at a high temperature to obtain a substrate for evaluating optical characteristics, which comprises a cured film having a film thickness of 1.5 μm in a monolithic form, and the optical density (OD/. Mu.m) and the maximum transmittance at a wavelength of 410nm to 440nm were evaluated by the above-mentioned method.

On the other hand, after 30 days of storage after preparation, the other positive photosensitive pigment composition 1 was taken out from the dark place and set to room temperature (23 ℃), the exposure sensitivity was measured again by the above method, and the storage stability was evaluated, and the obtained results are shown in table 7.

TABLE 7

Further, a pixel-divided layer including a cured film of the positive photosensitive pigment composition 1 and an organic EL display device including the pixel-divided layer were manufactured by the following method.

Fig. 3 shows a process for manufacturing an organic EL display device including a process for forming a pixel division layer.

On the surface of the alkali-free glass substrate 13 having a vertical dimension of 70 mm/a horizontal dimension of 70mm, a silver alloy (an alloy containing 99.00 wt% silver and 1.00 wt% copper) was formed into a film on the entire surface by sputtering. An alkali-soluble novolak type positive resist was immersed in a silver alloy etching solution SEA-1 having a liquid temperature of 30 ℃ and etched to obtain a patterned silver alloy film 14 having a film thickness of 50 nm. Further, an ITO film (indium-tin oxide) was formed over the entire surface by a sputtering method. An alkali-soluble novolak type positive resist was immersed in a 5 wt% oxalic acid aqueous solution at a liquid temperature of 50 ℃ for 5 minutes, washed with deionized water for 2 minutes, and then dried by air blowing, whereby the patterned ITO film 15 having a film thickness of 10nm was obtained. Through the above steps, a first electrode-forming substrate including a first electrode including a stacked pattern of a silver alloy film/an ITO film on the surface of the alkali-free glass substrate was obtained.

The rotation speed was adjusted using a spin coater so that the thickness of the thick film portion of the finally obtained pixel-divided layer having a step became 3.0 μm.+ -. 0.2 μm and the thickness of the thin film portion became 1.5 μm, and the positive photosensitive pigment composition 1 was applied to the surface of the first electrode-forming substrate, thereby obtaining a coating film. Further, the coated film was prebaked at 110℃for 120 seconds using a hot plate under atmospheric pressure to obtain a prebaked film, and alignment of a positive halftone exposure mask (a mask in which 220 square full-permeation portions having a vertical dimension of 30.0 μm and a horizontal dimension of 30.0 μm were arranged, and exposure in the full-permeation portion was set to 100% and exposure in the half-permeation portion was set to 15% when exposure in the shielding portion was set to 0%) was performed using a near infrared camera (light source wavelength: 800 nm). The pre-baked film is pattern-exposed with the required minimum exposure amount (exposure sensitivity) obtained by the above method interposed between the positive type halftone exposure masks, thereby obtaining an exposed film. The pattern exposure is performed by bringing the positive type halftone exposure mask into contact with the surface of the pre-bake film. Then, development, rinsing and drying were performed by the same method as in the evaluation of the minimum exposure amount required to obtain a patterned developed film. The developed film was heated at 250 ℃ for 1 hour under air using a high temperature inert gas oven to obtain a pixel-divided layer-forming substrate including a pixel-divided layer 16 having a step, the pixel-divided layer 16 having 220 openings in a region of 30mm in the longitudinal/30 mm in the lateral direction of the central portion of the first electrode-forming substrate. The opening width was measured by the above method and the halftone processing property was evaluated, and the obtained results are shown in table 7.

Next, in order to form the organic EL layer 17 including the light-emitting layer at the opening of the pixel dividing layer 16 by the vacuum deposition method, the vacuum degree was 1×10 ^-3 Under vapor deposition conditions of Pa or less, the pixel-divided layer-forming substrate is rotated relative to the vapor deposition source, and first, the compound (HT-1) represented by formula (69) is formed into a film at a thickness of 10nm as a hole injection layer, and the compound (HT-2) represented by formula (70) is formed into a film at a thickness of 50nm as a hole transport layer. Next, a compound (GH-1) represented by the formula (71) as a host material and a compound (GD-1) represented by the formula (72) as a dopant material were vapor deposited on the light-emitting layer at a thickness of 40 nm. Then, according to the volume ratio of 1:1 a 40nm thick laminate of an electron transporting material represented by the formula (73)And (LiQ) represented by the formula (74).

[ 62]

[ 63]

Next, a compound (LiQ) of 2nm was vapor-deposited, and then, a silver/magnesium alloy (volume ratio: 10:1) was vapor-deposited so that the thickness became 150nm, thereby forming a second electrode 18. Then, the cover glass plate was bonded using an epoxy resin adhesive under a low humidity/nitrogen atmosphere, and sealed, thereby obtaining an organic EL display device in which green light emitting pixels were arranged. Further, since each layer constituting the organic EL layer 17 is extremely thin compared to the pixel-divided layer, and high measurement accuracy cannot be obtained by the stylus type film thickness measuring apparatus, measurement is performed using a crystal oscillation type film thickness monitor suitable for a thin film of less than 100nm, and a value obtained by rounding the first decimal point of the average value of 3 points in a plane is set as the film thickness. The luminance unevenness of the produced organic EL display device was evaluated by the above method, and the obtained results are shown in table 7.

Examples 2 to 6

Positive photosensitive pigment compositions 2 to 10 were prepared in the amounts shown in table 6 by using the pigment dispersions 2 to 5 instead of the pigment dispersion 1, and the exposure sensitivity, the light-shielding property of the cured film, and the maximum transmittance at a wavelength of 410nm to 440nm, the storage stability, the halftone processability, and the luminance unevenness of the organic EL display were evaluated in the same manner as in example 1. The evaluation results are shown in table 7.

Example 7 to example 10

Positive photosensitive pigment compositions 7 to 10 were prepared in the amounts shown in table 8 by using the pigment dispersions 6 to 9 instead of the pigment dispersion 1, and the exposure sensitivity, the light-shielding property of the cured film, and the maximum transmittance at a wavelength of 410nm to 440nm, the storage stability, the halftone processability, and the luminance unevenness of the organic EL display were evaluated in the same manner as in example 1. The evaluation results are shown in table 9.

TABLE 8

Example 11

A positive photosensitive pigment composition 11 was prepared in the same amount as shown in table 10 by using the pigment dispersion 10 instead of the pigment dispersion 1 and using the polyimide resin C instead of the polyimide precursor B, and the exposure sensitivity, the light-shielding property of the cured film, and the maximum transmittance at a wavelength of 410nm to 440nm, the storage stability, the halftone processability, and the luminance unevenness of the organic EL display device were evaluated in the same manner as in example 1. The evaluation results are shown in table 11.

TABLE 10

Example 12

A positive photosensitive pigment composition 12 was prepared in the same amount as shown in table 10 by using the pigment dispersion 6 instead of the pigment dispersion 1 and using the polyimide resin C instead of the polyimide precursor B, and the exposure sensitivity, the light-shielding property of the cured film, and the maximum transmittance at a wavelength of 410nm to 440nm, the storage stability, the halftone processability, and the luminance unevenness of the organic EL display device were evaluated in the same manner as in example 1. The evaluation results are shown in table 11.

Examples 13 to 14

The positive photosensitive pigment composition 12 was prepared in the amounts shown in table 10 by using the pigment dispersions 11 to 12 instead of the pigment dispersion 1, and the exposure sensitivity, the light-shielding property of the cured film, and the maximum transmittance at a wavelength of 410nm to 440nm, the storage stability, the halftone processability, and the luminance unevenness of the organic EL display device were evaluated in the same manner as in example 1. The evaluation results are shown in table 11.

Comparative examples 1 to 3

The positive photosensitive pigment compositions 15 to 17 were prepared in the amounts shown in table 12 by using the pigment dispersions 13 to 15 instead of the pigment dispersion 1, and the exposure sensitivity, the light-shielding property of the cured film, and the maximum transmittance at a wavelength of 410nm to 440nm, the storage stability, the halftone processability, and the luminance unevenness of the organic EL display were evaluated in the same manner as in example 1. The evaluation results are shown in table 13.

TABLE 12

Comparative examples 4 to 5

The positive photosensitive pigment compositions 16 to 17 were prepared in the amounts shown in table 14 by using the pigment dispersions 16 to 17 instead of the pigment dispersion 1, and the exposure sensitivity, the light-shielding property of the cured film, and the maximum transmittance at a wavelength of 410nm to 440nm were evaluated in the same manner as in example 1. The evaluation results are shown in table 15. Further, since halftone processing becomes difficult after 30 days of storage, efficient evaluation cannot be performed.

TABLE 14

Comparative example 6

Under a yellow lamp, 0.41g of "Ai Dike Arklys (registered trademark)" NCI-831 (Ai Dike (manufactured by ADEKA) (Co.)) as an oxime ester photopolymerization initiator and 7.27g of polyimide resin E were added to 21.95g of MBA, and stirred for 10 minutes to dissolve the mixture. Further, 0.55g of MW-100LM (manufactured by Benzhou chemical Co., ltd.), 0.82g of "Light ester" DCP-M (manufactured by Kayanad Co., ltd.), 0.82g of "Kayarad (registered trademark)" DPCA-60 (manufactured by Japanese chemical Co., ltd.), and 18.18g of pigment dispersion 17 were added as the component (g), and stirred for 30 minutes to prepare a negative photosensitive pigment composition 1. The blending weights of the respective raw materials are shown in Table 14. The exposure sensitivity, the light-shielding property of the cured film, and the maximum transmittance at a wavelength of 410nm to 440nm, the storage stability, the halftone processability, and the luminance unevenness of the organic EL display device were evaluated in the same manner as in example 1. The evaluation results are shown in table 15.

PREPARATION EXAMPLE 18 preparation of pigment Dispersion 18

To 900.00g of the mixed solvent (PGME, ethyl lactate and gamma-butyrolactone; weight ratio 50:40:10) as the component (e), 68.38g of the polyimide precursor B as the component (c-1) was added, and the mixture was stirred for 30 minutes to dissolve the polyimide precursor B. Further, 4.59g of pigment B as the component (B-2) was added, and after stirring for 30 minutes, 18.92g of the micronized perylene black pigment 1 and 8.11g of the micronized dioxazine pigment 1 as the component (a) were added, and stirring was carried out for 30 minutes, thereby obtaining a pre-stirred solution. Then, the pre-stirred solution was fed to a horizontal bead mill "super advanced ai bas mill (ultra apex mill advance) (registered trademark)" which was a horizontal bead mill "Torayceram (registered trademark)", which was filled with zirconia beads of 0.4mm Φ at a filling rate of 75 vol%; the wet medium dispersion treatment was performed at a peripheral speed of 10m/s for 1 hour by a circulation method, manufactured by Hiroshima Metal & Machinery (stock). Then, the liquid was fed to a horizontal bead mill of "torayfera (registered trademark)" (manufactured by toray (r) which was filled with zirconia beads of 0.1mm Φ at a filling rate of 75% by volume in a container, and wet medium dispersion treatment was performed at a peripheral speed of 8m/s for 4 hours by a circulation system, whereby a pigment dispersion liquid having a solid content of 10.00% by weight was obtained. The first filtration was performed by a filter having a diameter of 0.8. Mu.m, and the second filtration was performed by a filter having a diameter of 0.2. Mu.m. As the value of the solid content up to the second decimal point before and after filtration, the component (a) was obtained without any fluctuation: and (h) component (a): component (b): (c) resin = weight ratio 70:30:17:253 and a pigment dispersion 18 having a solid content of 10.00% by weight. The blending weights of the respective raw materials are shown in Table 16.

TABLE 16

PREPARATION EXAMPLE 19 preparation of pigment Dispersion 19

A wet medium dispersion treatment and filtration were carried out in the same manner as in preparation example 18 except that the micronized dioxazine pigment 2 was used instead of the micronized dioxazine pigment 1, to obtain a component (a): and (h) component (a): component (b): (c) resin = weight ratio 70:30:17:253 and a pigment dispersion 19 having a solid content of 10.00% by weight. The blending weights of the respective raw materials are shown in Table 16.

Preparation example 20 preparation of pigment Dispersion 20

A wet medium dispersion treatment and filtration were carried out in the same manner as in preparation example 18 except that the micronized dioxazine pigment 2 was used instead of the micronized dioxazine pigment 1, to obtain a component (a): and (h) component (a): component (b): (c) resin=weight ratio 55:45:17:253 and a pigment dispersion 20 having a solid content of 10.00% by weight. The blending weights of the respective raw materials are shown in Table 16.

(example 15-example 17)

The positive photosensitive pigment compositions 20 to 22 were prepared in the amounts shown in table 17 by using the pigment dispersions 18 to 20 instead of the pigment dispersion 1, and the exposure sensitivity, the light-shielding property of the cured film, and the maximum transmittance at a wavelength of 410nm to 440nm, the storage stability, the halftone processability, and the luminance unevenness of the organic EL display were evaluated in the same manner as in example 1. The evaluation results are shown in table 18.

TABLE 17

Preparation examples 21 to 23

Pigment dispersion 21 to pigment dispersion 23 were obtained by performing wet medium dispersion treatment and filtration in the same manner as in preparation example 1 except that the micronized perylene Black pigment 1 was used instead of "spesterasense (registered trademark)" Black K0087, and pigment I, pigment J, and pigment K were used instead of pigment a, respectively. The blending weights of the respective raw materials are shown in Table 19.

TABLE 19

Example 18

A positive photosensitive pigment composition 23 was prepared in the amount shown in table 20 by using the pigment dispersion 21 instead of the pigment dispersion 1, and the exposure sensitivity, the light-shielding property of the cured film, and the maximum transmittance at a wavelength of 410nm to 440nm, the storage stability, the halftone processability, and the luminance unevenness of the organic EL display device were evaluated in the same manner as in example 1. The evaluation results are shown in table 21.

TABLE 20

Comparative example 7

The positive photosensitive pigment composition 24 was prepared in the amounts shown in table 20 by using the pigment dispersion 22 instead of the pigment dispersion 1, and the exposure sensitivity, the light-shielding property of the cured film, and the maximum transmittance at a wavelength of 410nm to 440nm, the storage stability, the halftone processability, and the luminance unevenness of the organic EL display device were evaluated in the same manner as in example 1. The evaluation results are shown in table 21.

Comparative example 8

The positive photosensitive pigment composition 25 was prepared in the blending amount shown in table 20 by using the pigment dispersion 23 instead of the pigment dispersion 1, but the viscosity was significantly increased at the time after 1 day of storage, the coatability was poor, and it was difficult to prepare a pre-baked film and perform halftone processing.

Example 19

Using pigment dispersion 19 as a component (I) instead of pigment dispersion 1 and using 4-aminobenzenesulfonic acid (manufactured by tokyo chemical industry (co.)), positive photosensitive pigment compositions 26 were prepared in the amounts shown in table 20, and the exposure sensitivity, light-shielding properties of the cured film, and maximum transmittance at a wavelength of 410nm to 440nm, storage stability, halftone processability, and brightness unevenness of the organic EL display device were evaluated by the same methods as in example 1. The evaluation results are shown in table 21.

Comparative example 9

Using the positive photosensitive resin composition (PB-1) disclosed in example 1 of international publication No. 2021/182499, an attempt was made to evaluate exposure sensitivity in the same manner as in example 1, except that alignment of the positive halftone exposure mask was difficult using a near infrared camera, except for the evaluation object. Further, although the pre-bake films were formed on the first electrode forming substrate so as to have film thicknesses of 2.0 μm, 3.0 μm and 4.0 μm, alignment of the positive halftone exposure mask was difficult, and an organic EL display device could not be fabricated by the same method as in example 1.

From the above results, it is clear that the positive-type photosensitive pigment compositions of examples 1 to 19 can align an exposure mask using near infrared rays, are excellent in halftone processability, and have both high exposure sensitivity and high storage stability, as compared with the positive-type photosensitive pigment compositions of comparative examples 1 to 5 and 7 to 9 and the negative-type photosensitive pigment composition of comparative example 6. In the case of forming a pixel dividing layer having high light-shielding properties with OD/μm=1.0, excellent exposure sensitivity was obtained in examples 15 to 17 containing the component (h) compared with example 12, and further, more excellent exposure sensitivity was obtained in example 19 containing the component (i).

The organic EL display devices in examples 1 to 19 are superior to those in comparative examples 2 to 3 and 6 in that the organic EL display devices have less luminance unevenness.

Accordingly, it is found that the positive photosensitive pigment composition, the cured film containing the cured product of the positive photosensitive pigment composition, and the organic EL display device including the cured film of the present invention are useful.

Industrial applicability

The positive photosensitive pigment composition of the present invention is preferably used as a material for forming a cured film required to be stably formed with high exposure sensitivity, for example, a pixel dividing layer of an organic EL display device, a TFT planarizing layer of an organic EL display device, a partition wall of a quantum dot organic EL display device (QD-OLED), a planarizing layer of a micro LED display, a black matrix of a liquid crystal display device, a black column spacer of a liquid crystal display device, a near infrared ray transmissive visible light shielding film of a solid image pickup element, a black frame of a display device, or the like. Among them, it is particularly preferable to use a material for forming a pixel dividing layer included in an organic EL display device on which a flexible display that can be bent is mounted.

Description of symbols

1: thick film part

2: film portion

3：TFT

4: wiring harness

5: TFT insulating layer

6: planarization layer

7: first electrode

8: substrate board

9: contact hole

10: pixel dividing layer

11: light-emitting pixel

12: second electrode

13: alkali-free glass substrate

14: silver alloy film

15: ITO film

16: pixel dividing layer

17: organic EL layer

18: second electrode

Claims

1. A positive photosensitive pigment composition comprising: (a) a pigment containing a compound having two structures represented by the formula (1) in the molecule and one perylene skeleton in the molecule, (b) a compound having a structure represented by the formula (2) and not having an N, N-dialkylaminoalkyl group or a metal salt thereof, (c) a resin, (d) a photoacid generator, and (e) an organic solvent,

[ chemical 1]

(in the formula (1), R ¹ Represents a phenylene group which may have a substituent or a naphthylene group which may have a substituent; * Represents the bond site with the carbon atom constituting the perylene skeleton)

[ chemical 2]

(in the formula (2), R ² ～R ⁵ Each independently represents a hydrogen atom, a fluorine atom, a bromine atom or a hydroxyl group; r is R ⁶ A monovalent group having a sulfo group bonded to a carbon atom constituting an aromatic ring and/or a carboxyl group bonded to a carbon atom constituting an aromatic ring; * Representing the bond site to a carbon atom).

2. The positive-type photosensitive pigment composition according to claim 1, wherein the component (b) contains (b-1) a compound having a structure represented by formula (14) or a metal salt thereof,

[ chemical 3]

(in the formula (14), R ⁷³ ～R ⁷⁶ Each independently represents a hydrogen atom, a fluorine atom, a bromine atom or a hydroxyl group; r is R ⁷⁷ Represents a single bond or an alkylene group having 1 to 6 carbon atoms; r is R ⁷⁸ Represents sulfo or carboxyl; n is n ¹ Is an integer, representing 1 or 2; at n ¹ In the case of 2, two R ⁷⁸ Can be the same substituent or can be mutually different substituents; r is R ⁷⁹ Represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms; n is n ² Is an integer of 0 to 2; at n ² In the case of 2, two R ⁷⁹ Can be the same substituent or can be mutually different substituents; * Representing the bond site to a carbon atom).

3. The positive-type photosensitive pigment composition according to claim 1 or 2, wherein the component (b) contains (b-2) a compound having a structure represented by formula (15) or a metal salt thereof,

[ chemical 4]

(in the formula (15), R ⁸⁰ ～R ⁸³ Each independently represents a hydrogen atom, a fluorine atom, a bromine atom or a hydroxyl group; r is R ⁸⁴ Represents a single bond or an alkylene group having 1 to 6 carbon atoms; r is R ⁸⁵ Represents a single bond or NH; r is R ⁸⁶ Represents one group selected from the group consisting of a phenylene group substituted with an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, an unsubstituted phenylene group, a naphthylene group substituted with an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and an unsubstituted naphthylene group; r is R ⁸⁷ Represents sulfo or carboxyl; n is n ³ Is an integer, representing 1 or 2; at n ³ In the case of 2, two R ⁸⁷ Can be the same substituent or can be mutually different substituents; r is R ⁸⁸ Represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms; n is n ⁴ Is an integer of 0 to 2; at n ⁴ In the case of 2, two R ⁸⁸ Can be the same substituent or can be mutually different substituents; * Representing the bond site to a carbon atom).

4. The positive-type photosensitive pigment composition according to any one of claims 1 to 3, wherein the average aspect ratio of the primary particles of the component (a) is 1.0 to 1.8.

5. The positive-type photosensitive pigment composition according to any one of claims 1 to 4, wherein the amine value of the (c) resin is 5.0mgKOH/g or less.

6. The positive-type photosensitive pigment composition according to any one of claims 1 to 5, wherein the component (a) contains a compound represented by the formula (3) and/or a compound represented by the formula (4),

[ chemical 5]

(in the formula (3) and the formula (4), R ⁷ ～R ¹⁴ Respectively and independently represent hydrogen atom, fluorine atom, bromine atom, and carbonAlkyl groups having 1 to 6 carbon atoms or alkoxy groups having 1 to 6 carbon atoms; r is R ¹⁵ ～R ²² Each independently represents a hydrogen atom, a fluorine atom or a bromine atom).

7. The positive-type photosensitive pigment composition according to any one of claims 1 to 6, wherein the (c) resin contains a resin having a structural unit represented by formula (39),

[ chemical 6]

(in the formula (39), R ¹⁰¹ R is R ¹⁰² An organic group having a valence of two to eight; r is R ¹⁰³ R is R ¹⁰⁴ Each independently represents a hydroxyl group, a carboxyl group or COOA, and may be a single group, or may be mixed with each other; a represents a monovalent hydrocarbon group having 1 to 10 carbon atoms; r and s are integers and each independently represents 0 to 6; wherein r+s > 0 is satisfied; * Indicating the bonding site).

8. The positive photosensitive pigment composition according to any one of claims 1 to 7, wherein the content of the component (b) is 5 to 50 parts by weight relative to 100 parts by weight of the total pigments contained in the positive photosensitive pigment composition.

9. The positive-type photosensitive pigment composition according to any one of claims 1 to 8, further comprising (f) a compound which is converted by heating into a compound having a maximum absorption wavelength in a region of 350nm to 500nm in a region of 350nm to 780nm in wavelength.

10. The positive-type photosensitive pigment composition according to any one of claims 1 to 9, further comprising (h) a pigment containing a compound having a dioxazine skeleton.

11. The positive-type photosensitive pigment composition according to claim 10, wherein the content of the component (h) is 1 to 50 parts by weight based on 100 parts by weight of the total of the component (a) and the component (h).

12. The positive-type photosensitive pigment composition according to claim 10 or 11, wherein the component (h) contains a pigment having a compound represented by formula (12),

[ chemical 7]

(in the formula (12), R ¹³¹ 、R ¹³² 、R ¹³³ R is R ¹³⁴ Each independently represents an alkyl group having 1 to 5 carbon atoms; r is R ¹³⁵ R is R ¹³⁶ Each independently represents NH or an oxygen atom).

13. The positive-type photosensitive pigment composition according to any one of claims 1 to 12, further comprising (i) aminobenzenesulfonic acid.

14. A cured film comprising the cured product of the positive-type photosensitive pigment composition according to any one of claims 1 to 13.

15. An organic electroluminescent display device comprising the cured film according to claim 14.

16. An organic electroluminescent display device comprising a substrate, a first electrode, a pixel-dividing layer, a light-emitting pixel, and a second electrode, wherein the pixel-dividing layer comprises (a) a pigment comprising a compound having two structures represented by formula (1) in a molecule and one perylene skeleton in a molecule and (b) a compound having a structure represented by formula (2) and having no N, N-dialkylaminoalkyl group or a metal salt thereof,

[ chemical 8]

(in the formula (1), R ¹ Represents a phenylene group which may have a substituent or a naphthylene group which may have a substituent; * Represents a bond site with a carbon atom constituting a perylene skeleton);

[ chemical 9]

17. The organic electroluminescent display device according to claim 16, wherein the pixel dividing layer has a thick film portion having a film thickness of 2.5 μm to 4.0 μm and a thin film portion having a film thickness of 1.0 μm to 2.5 μm, and has a portion where a difference in film thickness between the thick film portion and the thin film portion is 1.0 μm or more.