WO2022270182A1 - ポジ型感光性顔料組成物、およびその硬化物を含有する硬化膜、ならびに、有機el表示装置 - Google Patents
ポジ型感光性顔料組成物、およびその硬化物を含有する硬化膜、ならびに、有機el表示装置 Download PDFInfo
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- WO2022270182A1 WO2022270182A1 PCT/JP2022/020484 JP2022020484W WO2022270182A1 WO 2022270182 A1 WO2022270182 A1 WO 2022270182A1 JP 2022020484 W JP2022020484 W JP 2022020484W WO 2022270182 A1 WO2022270182 A1 WO 2022270182A1
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- C09B62/4403—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system the heterocyclic system being a triazine ring
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-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/22—Exposing sequentially with the same light pattern different positions of the same surface
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
Definitions
- the present invention relates to a positive photosensitive pigment composition, a cured film containing a cured product thereof, and an organic EL display device.
- a pixel division layer having a stepped shape is collectively formed by a photolithography method including an exposure step of irradiating exposure light containing at least near-ultraviolet rays through a halftone exposure mask having an in-plane portion and a shielding portion.
- a technique halftoning is known.
- Halftone processing is useful because it can greatly reduce manufacturing process costs compared to two-layer processing in which a thick film portion is formed by laminating a thin film portion after forming a thin film portion.
- Patent Document 1 discloses a negative photosensitive pigment composition containing Pigment Black 31 and a polymeric dispersant having an N,N-dialkylaminoalkyl group.
- a positive photosensitive pigment composition for forming a black pixel division layer for example, C.I. I. Pigment Yellow 192 and C.I. I. Pigment Red 179 and C.I. I.
- Patent Document 3 discloses a positive photosensitive pigment composition containing zirconium nitride particles.
- the pre-baked film of the positive photosensitive pigment composition disclosed in Patent Document 3 has extremely low near-infrared transmittance due to the optical properties of zirconium nitride particles, and alignment of an exposure mask using a near-infrared camera is difficult.
- the positive photosensitive pigment composition of the present invention has the following constitution. i.e. (a) a pigment containing a compound having two structures represented by formula (1) in the molecule and having one perylene skeleton in the molecule (hereinafter sometimes referred to as “component (a)”); , (b) a compound having a structure represented by formula (2) and having no N,N-dialkylaminoalkyl group or a metal salt thereof (hereinafter sometimes referred to as “(b) component”), (c) resin (hereinafter sometimes referred to as “(c) component"), (d) photoacid generator (hereinafter sometimes referred to as "(d) component”) and (e) organic solvent (hereinafter sometimes referred to as "(d) component”) , sometimes referred to as "(e) component”).
- component (a) a pigment containing a compound having two structures represented by formula (1) in the molecule and having one perylene skeleton in the molecule
- component (b) component) a compound having
- R 1 represents an optionally substituted phenylene group or an optionally substituted naphthylene group.
- * represents a bonding site with a carbon atom constituting the perylene skeleton.
- R 2 to R 5 each independently represent a hydrogen atom, a fluorine atom, or a bromine atom.
- R6 represents 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 bonding site with a carbon atom.
- the cured film of the present invention has the following constitution. i.e. A cured film containing a cured product of the positive photosensitive pigment composition.
- the organic EL display device of the present invention has the following configuration. i.e. An organic EL display device comprising the cured film.
- component (b) is a compound having a structure represented by (b-1) formula (14) or a metal salt thereof (hereinafter referred to as "component (b-1) ) is preferably contained.
- R 73 to R 76 each independently represent a hydrogen atom, a fluorine atom, a bromine atom, or a hydroxyl group.
- R 77 represents an alkylene group having 1 to 6 carbon atoms.
- R78 represents a sulfo group or a carboxyl group.
- n 1 is an integer and represents 1 or 2; When n 1 is 2, two R 78 may be the same substituent or different substituents.
- R 79 represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.
- n2 is an integer and represents 0-2. When n 2 is 2, two R 79 may be the same substituent or different substituents.
- * represents a bonding site with a carbon atom.
- component (b) is a compound having a structure represented by (b-2) formula (15) or a metal salt thereof (hereinafter referred to as "component (b-2) ) is preferably contained.
- R 80 to R 83 each independently represent a hydrogen atom, a fluorine atom, a bromine atom or a hydroxyl group.
- R 84 represents a single bond or an alkylene group having 1 to 6 carbon atoms.
- R85 represents a single bond or NH.
- R 86 is 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 or an alkoxy group having 1 to 6 carbon atoms. represents one group selected from the group consisting of substituted naphthylene groups and unsubstituted naphthylene groups.
- R87 represents a sulfo group or a carboxyl group.
- n3 is an integer and represents 1 or 2; When n 3 is 2, two R 87 may be the same substituent or different substituents.
- R 88 represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.
- n4 is an integer and represents 0-2. When n 4 is 2, two R 88 may be the same substituent or different substituents.
- * represents a bonding site with a carbon atom.
- the average aspect ratio of the primary particles of component (a) is preferably 1.0 to 1.8.
- the amine value of the resin (c) is preferably 5.0 mgKOH/g or less.
- the component (a) preferably contains a compound represented by formula (3) and/or a compound represented by formula (4).
- R 7 to R 14 each independently represent a hydrogen atom, a fluorine atom, a bromine atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
- R 15 to R 22 each independently represent a hydrogen atom, a fluorine atom or a bromine atom.
- the (c) resin preferably contains a resin having a structural unit represented by formula (39).
- R 101 and R 102 represent divalent to octavalent organic groups.
- R 103 and R 104 each independently represent a phenolic hydroxyl group, a carboxyl group or COOA, each of which may be a single group or a mixture of different groups.
- A represents a monovalent hydrocarbon group having 1 to 10 carbon atoms.
- r and s are integers and each independently represent 0-6. However, r+s>0 is satisfied.
- * represents a binding site.
- the content of the component (b) is 5 to 50 parts by weight with respect to the total 100 parts by weight of the pigments contained in the positive photosensitive pigment composition. is preferred.
- the positive photosensitive pigment composition of the present invention includes (f) a compound that is converted by heating into a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm in the wavelength range of 350 to 780 nm (hereinafter referred to as "(f ) component”.) is preferably contained.
- 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 "component (h)").
- the content of the component (h) is 1 to 50 parts by weight with respect to a total of 100 parts by weight of the components (a) and (h). preferable.
- the positive photosensitive pigment composition of the present invention preferably contains a pigment containing a compound represented by formula (12) as the component (h).
- R 131 , R 132 , R 133 and R 134 each independently represent an alkyl group having 1 to 5 carbon atoms.
- R 135 and R 136 each independently represent NH or an oxygen atom.
- the positive photosensitive pigment composition of the present invention preferably further contains (i) aminobenzenesulfonic acid.
- the organic EL display device of the present invention is an organic EL display device comprising a substrate, a first electrode, a pixel division layer, light emitting pixels and a second electrode, wherein the pixel division layer is ( a) a pigment containing a compound having two structures represented by formula (1) in the molecule and having one perylene skeleton in the molecule; and (b) a structure represented by formula (2). , an organic EL display device containing a compound having no N,N-dialkylaminoalkyl group or a metal salt thereof.
- R 1 represents an optionally substituted phenylene group or an optionally substituted naphthylene group.
- * represents a bonding site with a carbon atom constituting the perylene skeleton.
- R 2 to R 5 each independently represent a hydrogen atom, a fluorine atom, a bromine atom or a hydroxyl group.
- R6 represents 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 bonding site with a carbon atom.
- the pixel division layer has a thick film portion with a thickness of 2.5 to 4.0 ⁇ m and a thin film portion with a thickness of 1.0 to 2.5 ⁇ m, and the thick film It is preferable to have a portion where the difference in film thickness between the portion and the thin film portion is 1.0 ⁇ m or more.
- a pixel division layer having a level difference which has a light shielding property, a high in-plane uniformity of the opening width in the opening, and a stable high exposure sensitivity by halftone processing.
- FIG. 10 is an image obtained by observing a cross section of the substrate for exposure sensitivity evaluation provided with a pixel dividing layer having steps obtained in Example 16 with a scanning electron microscope (SEM).
- 1 is a cross-sectional view of a TFT substrate in an organic EL display device given as a specific example of an embodiment of the present invention;
- FIG. It is a manufacturing process of an organic EL display device including a process of forming a pixel division layer in all examples and comparative examples.
- FIG . 4 is a schematic diagram showing an example of the maximum aperture width W1 and the minimum aperture width W2 of the apertures of the pixel division layer forming substrate in all the examples and comparative examples.
- a numerical range represented using “to” means a range including the numerical values described before and after “to” as lower and upper limits.
- a pixel division layer means a pixel division layer provided in an organic EL display device, and does not include a black matrix of a liquid crystal display device. Visible light means light with a wavelength of 380 nm or more and less than 780 nm, and near-ultraviolet means light with a wavelength of 200 nm or more and less than 380 nm. Near-infrared light means light with a wavelength of 780 nm or more and 1300 nm or less.
- the term “light shielding” refers to the function of reducing the intensity of light transmitted through the cured film relative to the intensity of light incident on the cured film in the vertical direction, and the term “light shielding property” refers to the extent to which visible light is shielded.
- Transmittance means light transmittance.
- the weight average molecular weight (Mw) is a value analyzed by gel permeation chromatography using tetrahydrofuran as a carrier and converted using a standard polystyrene calibration curve.
- Color Index Generic Name used in the names of some coloring materials is an abbreviation for Color Index Generic Name, and based on the Color Index published by The Society of Dyers and Colorists, regarding coloring materials registered in the Color Index , Color Index Generic Name represents the chemical structure and crystal form of a pigment or dye.
- C.I. I. Carbon black classified as Pigment Black 7 is classified as an inorganic black pigment.
- the solid content means the ratio (% by weight) of components excluding the organic solvent and water in the positive photosensitive pigment composition.
- a pigment having a specific chemical structure and a dye having a specific chemical structure are combined, and a pigment imparted with positive photosensitivity by a resin and a photoacid generator. It has been found that the composition has a particularly remarkable effect in solving the aforementioned problems.
- the positive photosensitive pigment composition of the present invention includes (a) a pigment containing a compound having two structures represented by formula (1) in the molecule and having one perylene skeleton in the molecule; (b) a compound having a structure represented by formula (2) and having no N,N-dialkylaminoalkyl group or a metal salt thereof, (c) a resin, (d) a photoacid generator, and (e) It is a positive photosensitive pigment composition containing an organic solvent.
- R 1 represents an optionally substituted phenylene group or an optionally substituted naphthylene group.
- * represents a bonding site with a carbon atom constituting the perylene skeleton.
- R 2 to R 5 each independently represent a hydrogen atom, a fluorine atom, a bromine atom or a hydroxyl group.
- R6 represents 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 bonding site with a carbon atom.
- the positive photosensitive pigment composition of the present invention comprises (a) a pigment containing a compound having two structures represented by formula (1) in the molecule and having one perylene skeleton in the molecule. Contained as a component.
- the component (a) has the effect of imparting light-shielding properties to the finally obtained pixel division layer.
- the maximum transmittance in the wavelength range of 300 to 450 nm can be made higher than the minimum transmittance of the component (a) in the wavelength range of 500 to 600 nm. While excellent in optical density, exposure light containing at least light in the wavelength region of 300 to 450 nm can easily reach deep into the film, and high exposure sensitivity can be obtained.
- exposure sensitivity means the minimum exposure dose required to form a pixel dividing layer having openings with a desired film thickness and a desired opening width in the exposure step described later. It means that the minimum exposure dose is small.
- component (a) has a higher maximum transmittance at 800 to 1,200 nm than the maximum transmittance in the wavelength range of 300 to 450 nm. can be performed automatically, exposure with high positional accuracy is possible by near-infrared alignment, and higher productivity and yield can be obtained.
- the component (a) has two structures represented by the formula (1) in the molecule. I.
- Pigment Black 31 and pseudo black pigments It has higher heat resistance than Pigment Black 31 and pseudo black pigments, and can maintain high light-shielding properties without causing discoloration or fading even after high-temperature treatment at 250° C. or higher in the curing step described later, regardless of the oxygen concentration. Therefore, the pigment content in the film can be reduced in order to obtain desired light-shielding properties, and desirably high exposure sensitivity can be exhibited.
- R 1 represents an optionally substituted phenylene group or an optionally substituted naphthylene group.
- * represents a bonding site with a carbon atom constituting the perylene skeleton.
- Examples of the compound having two structures represented by formula (1) in the molecule and having one perylene skeleton in the molecule include, for example, a compound represented by formula (3) in cis form, and a compound in trans form.
- R 7 to R 14 each independently represent a hydrogen atom, a fluorine atom, a bromine atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
- R 15 to R 22 each independently represent a hydrogen atom, a fluorine atom or a bromine atom.
- R 23 to R 34 each independently represent a hydrogen atom, a fluorine atom, a bromine atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
- R 35 to R 42 each independently represent a hydrogen atom, a fluorine atom or a bromine atom.
- R 43 to R 54 each independently represent a hydrogen atom, a fluorine atom, a bromine atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
- R 55 to R 62 each independently represent a hydrogen atom, a fluorine atom or a bromine atom.
- the positive photosensitive pigment composition of the present invention contains a compound represented by the formula (3) and/or a compound represented by the formula (4) as the component (a). It is preferable to contain. It is more preferable to contain the compound represented by the formula (9) which is the cis form and/or the compound represented by the formula (10) which is the trans form.
- the compound (a) having two structures represented by formula (1) in the molecule and having one perylene skeleton in the molecule may contain one or a plurality of kinds, and the exposure sensitivity is improved. For improvement, it is more preferable to contain 40 to 100% by weight of the trans isomer with respect to 100% by weight of the total of the cis and trans isomers.
- Component (a) is 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.
- perylene-3,4,9,10-tetracarboxylic dianhydride and 1,2-diaminobenzene which are starting materials, were added to phenol melted at 70° C. at a ratio of 1:2, respectively. mol ratio, and a basic catalyst such as piperazine is added, and the mixture is stirred at a liquid temperature of 120 to 190 ° C. for 6 to 10 hours to allow the reaction to proceed sufficiently.
- a pigment crude corresponding to a compound having one skeleton in the molecule is obtained.
- the pigment crude is obtained as a mixture containing 30 to 70 parts by weight of the trans form per 100 parts by weight of the total of the cis form and the trans form.
- pigment crude is meant a pigment precursor prior to the pigmentation step.
- chemical refining treatment and / or physical refining treatment described later are performed, and (a) consisting of a compound represented by formula (3) and a compound represented by formula (4) get the ingredients.
- 1,8-diaminonaphthalene or a derivative thereof is used instead of the above-mentioned 1,2-diaminobenzene or a derivative thereof to synthesize and pigmentize a compound represented by formula (5), and the component (a) containing the compound represented by the formula (6) can be obtained. Also, by synthesizing and pigmenting using 1,2-diaminonaphthalene or a derivative thereof, obtaining the component (a) consisting of the compound represented by the formula (7) and the compound represented by the formula (8) can be done.
- Derivatives of perylene-3,4,9,10-tetracarboxylic dianhydride as a starting material include, for example, 1,7-dibromo obtained by the selective synthesis method disclosed in WO 97/22607.
- Examples include perylene-3,4,9,10-tetracarboxylic dianhydride and monobromoperylene-3,4,9,10-tetracarboxylic dianhydride disclosed in JP-A-2018-165257.
- As these perylene-3,4,9,10-tetracarboxylic dianhydride derivatives for example, commercial products manufactured by Henan Tianfu Chemical may be used.
- 1,2-diaminobenzene examples include, for example, 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- Examples include diamino-4,5-propoxybenzene and 1,2-diamino-4,5-butoxybenzene, which may be used singly or in combination of two or more.
- Pigments composed of the compound represented by the formula (9) and the compound represented by the formula (10) may be commercially available products, for example, "Spectrasense (registered trademark)" Black K0087 (manufactured by BASF). .
- the content of the compound represented by the formula (9) is very small, and the high-purity product of the trans isomer containing 80% by weight or more of the compound represented by the formula (10) is PTCBI (manufactured by Luminescence Technology Corporation). is mentioned.
- the average primary particle size of component (a) is preferably 10 nm or more, more preferably 20 nm or more, in order to improve halftone workability. It is preferably 120 nm or less, more preferably 80 nm or less, to improve exposure sensitivity.
- the average primary particle size here refers to the number average value of primary particle sizes calculated by a particle size measurement method using an image analysis type particle size distribution measuring device.
- a transmission electron microscope (TEM) can be used for taking an image, and 50 particles are randomly selected from an image of 100 or more primary particles of component (a) taken at a magnification of 50,000 times.
- the average primary particle size can be calculated by analyzing the primary particles.
- the primary particle size is the average value of its major axis and minor axis.
- image analysis type particle size distribution software Mac-View manufactured by Mountech; compliant with JIS8827-1; particle size analysis-image analysis method
- 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 order to improve exposure sensitivity and halftone processability.
- the average aspect ratio of the primary particles of component (a) is preferably 1.0 to 1.8.
- the aspect ratio of the primary particles means the value obtained by dividing the major axis value of the primary particles by the minor axis value and rounding off to the second decimal place.
- the average aspect ratio of the primary particles is the aspect ratio of 50 primary particles randomly selected from images of 100 or more primary particles of the component (a) taken at a magnification of 50,000 using a TEM. mean the number average value of
- the maximum primary particle size of component (a) is preferably 40 nm or more, more preferably 80 nm or more, in order to improve storage stability. It is preferably 200 nm or less, more preferably 150 nm or less, to improve exposure sensitivity.
- the maximum primary particle size means the maximum value among the 50 primary particle sizes used when calculating the aforementioned average primary particle size.
- Methods for controlling the average primary particle size, the average aspect ratio of primary particles and the maximum primary particle size of component (a) include a chemical refinement process such as an acid paste method and/or a physical refinement process such as a solvent salt milling method.
- a hardening treatment can be preferably applied.
- the acid paste method is particularly effective for refining high-hardness organic pigments
- the solvent salt milling method is particularly effective for reducing coarse primary particles. can do.
- a liquid in which an organic pigment crude or an organic pigment is dissolved in a strong acid such as a 50 to 98% by weight aqueous sulfuric acid solution is poured into a large amount of water to precipitate, granulated, filtered, and further strong acid. is removed by washing with water, dried, and pulverized to obtain a finely divided organic pigment.
- a strong acid such as a 50 to 98% by weight aqueous sulfuric acid solution
- the solvent salt milling method involves wet-kneading a paste in which an organic pigment, a grinding agent, and a water-soluble organic solvent are mixed at 20 to 80 ° C., then adding a large amount of water and stirring. It refers to a method of obtaining a finely divided organic pigment by drying and pulverizing the filtrate after removing the water-soluble organic solvent by washing with water.
- a kneader for example, a kneader (manufactured by Inoue Seisakusho Co., Ltd.) can be used.
- fine particulate water-soluble inorganic salts having an average primary particle size of 0.1 to 50 ⁇ m can be used, examples of which include sodium chloride, potassium chloride and potassium sulfate. It is desirable to reduce the water content to 0.5% by weight or less in advance by heat-treating at 200° C. or higher to increase the hardness.
- a glycol-based solvent is preferable. Examples of glycol-based solvents include ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol.
- Chemical refining treatment and/or physical refining treatment is performed in the presence of component (a) and component (b), and at least part of component (a) is subjected to surface treatment with component (b). Higher exposure sensitivity may be obtained by using a pigment with
- the total amount of residual ionic impurities derived from the strong acid in the acid paste method, the grinding agent in the solvent salt milling method, and these is preferably 500 ppm by weight or less, more preferably 100 ppm by weight or less, in component (a).
- a step of washing component (a) with a solution in which 0.1 to 1.0% by weight of nonionic surfactant is mixed with warm water may be added.
- Component (a) may be a pigment consisting of only a compound having two structures represented by formula (1) in the molecule and having one perylene skeleton in the molecule, and further with other dye compounds. may be a pigment composed of a mixed crystal of
- the mixed crystal pigment referred to herein is, for example, a compound having two structures represented by formula (1) in the molecule and having one perylene skeleton in the molecule, and an organic dye compound as another dye compound.
- a pigment composed of a mixed crystal of a compound having two structures represented by formula (1) in the molecule and having one perylene skeleton in the molecule and a compound having a dioxazine skeleton Defined as a mixture of components (a) and (h). The mixing ratio is determined based on the weight ratio converted from the mol ratio of both compounds.
- primary particles of component (a) and secondary particles composed of aggregates of primary particles of component (h), pigments obtained by treating the surface of component (a) with component (h), and component (a) is also defined as a mixture of component (a) and component (h).
- the content of the compound having two structures represented by formula (1) in the molecule and having one perylene skeleton in the molecule contained in the component (a) increases the light-shielding property of the pixel division layer.
- the content 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. 30% by weight or less is preferable, and 20% by weight or less is more preferable for improving exposure sensitivity.
- 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 here means a triphendioxazine skeleton.
- Component (h) has the effect of imparting a light-shielding property to the finally obtained pixel division layer in the same manner as component (a) described above. It is easy to reach deep parts, and high exposure sensitivity can be obtained. Moreover, from the same point of view, it is possible to suppress a decrease in exposure sensitivity particularly when forming a pixel division layer having a high light shielding property (OD/ ⁇ m) exceeding 0.8.
- the content of component (h) is preferably 1 part by weight or more, more preferably 10 parts by weight or more, with respect to a total of 100 parts by weight of components (a) and (h) in order to improve exposure sensitivity.
- it is preferably 50 parts by weight or less, more preferably 40 parts by weight or less.
- the content of component (h) is preferably 1 to 50 parts by weight with respect to a total of 100 parts by weight of components (a) and (h). .
- Component (h) includes, for example, a pigment containing a compound represented by formula (11) and a pigment containing a compound represented by formula (12).
- the compound represented by Formula (11) and the compound represented by Formula (12) have two oxazine rings in the molecule. That is, it is a compound having one dioxazine skeleton in the molecule.
- a specific example of the compound represented by formula (11) is, in formula (11), R 63 and R 64 are chlorine atoms, R 65 and R 68 are hydrogen atoms, R 66 and R 67 are ethyl A C.I. I. Pigment Blue 80 can be mentioned.
- a specific example of the compound represented by formula (12) is that in formula (12), R 131 and R 132 are ethyl groups, R 133 and R 134 are methyl groups, R 135 and R 136 are NH C.I. I. Pigment Violet 37 can be mentioned.
- R63 and R64 each independently represent a hydrogen atom or a halogen atom.
- R 65 to R 68 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group.
- R 131 , R 132 , R 133 and R 134 each independently represent an alkyl group having 1 to 5 carbon atoms.
- R 135 and R 136 each independently represent NH or an oxygen atom.
- a pigment containing a compound represented by formula (12) is preferable for obtaining high exposure sensitivity.
- the positive photosensitive pigment composition of the present invention more preferably contains a pigment containing a compound represented by formula (12) as component (h).
- R 131 and R 132 are the same and are preferably alkyl groups having 1 to 3 carbon atoms, R 133 and R 134 are preferably methyl groups, R 135 and R 136 are NH preferable.
- the positive photosensitive pigment composition of the present invention most preferably contains a pigment containing a compound represented by formula (13) as component (h).
- R 69 and R 70 are the same and represent an alkyl group having 1 to 3 carbon atoms.
- the positive-working photosensitive pigment composition of the present invention comprises (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 component contains as
- the metal salt referred to herein means a metal salt of sulfonic acid and a metal salt of carboxylic acid. have a group.
- the positive photosensitive pigment composition of the present invention preferably contains an organic dye compound or a metal salt thereof as the component (b) in order to improve halftone processability, exposure sensitivity and storage stability.
- organic dye compound as used herein means organic dyes and organic pigments.
- the component (b) has the effect of improving halftone workability, exposure sensitivity and storage stability. Improving the halftone workability means improving the in-plane uniformity of the opening width in the opening of the pixel division layer having steps. By improving the in-plane uniformity of the opening width, it is possible to suppress variations in the size of the light-emitting pixels formed in the openings of the pixel dividing layer, and to suppress luminance unevenness.
- the storage stability refers to the rate of change in exposure sensitivity of the positive photosensitive pigment composition after storage for 30 days based on the exposure sensitivity of the positive photosensitive pigment composition after storage for 1 day after preparation. means. High storage stability means that the rate of change in exposure sensitivity is desirably small.
- Storage means leaving the hermetically sealed positive photosensitive pigment composition in a cool and dark place under atmospheric pressure, shielded from light, and maintained at -20 ⁇ 1° C. in a hermetically sealed state. It is common general technical knowledge for those skilled in the art to store the positive photosensitive pigment composition containing a photoacid generator that is highly active against heat and light under the above-mentioned environment in order to reduce deterioration over time. By improving the exposure sensitivity, the productivity of the panel can be improved, and by improving the storage stability, the pixel division layer having steps can be formed with stable exposure sensitivity.
- the compound belonging to component (b) does not have an N,N-dialkylaminoalkyl group, high A ⁇ - ⁇ stacking effect and a high charge imparting effect derived from 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 can be exhibited. Effects of improving tone processability, exposure sensitivity and storage stability can be obtained. Further, when the positive photosensitive pigment composition contains the component (h), the component (b) can exert the same effect not only on the component (a) but also on the component (h). Effects of improving tone processability, exposure sensitivity and storage stability can be obtained.
- the N,N-dialkylaminoalkyl group referred to here includes, for example, N,N-dimethylaminoethyl group, N,N-dimethylaminopropyl group, N,N-diethylaminopropyl group, N,N-dipropylaminopropyl group, but does not include the imide ring that the component (b) has in the molecule.
- it is a compound having two structures represented by formula (1) in the molecule and having one perylene skeleton in the molecule, and having a structure represented by formula (2), N, N A compound or metal salt thereof that does not have a -dialkylaminoalkyl group is defined as a compound belonging to component (b).
- R 2 to R 5 each independently represent a hydrogen atom, a fluorine atom, a bromine atom or a hydroxyl group.
- R6 represents 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 bonding site with a carbon atom.
- the sulfo group here means not only —SO 3 H, but also encompasses —SO 3 — in which protons are dissociated as a form of existence in the positive photosensitive pigment composition.
- the carboxyl group not only means -COOH, but also includes -COO- , which is a proton-dissociated form.
- R 2 to R 5 are preferably hydrogen atoms for improving exposure sensitivity.
- R6 is a monovalent group having one or two sulfo groups bonded to carbon atoms constituting an aromatic ring.
- * is a bonding site with a carbon atom constituting the naphthalene skeleton.
- Examples of groups 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 possessed by R 6 which is a monovalent group, include, for example, a sulfophenyl group, disulfophenyl group, carboxyphenyl group, dicarboxyphenyl group, carboxy-sulfophenyl group, methyl-sulfophenyl group, methoxy-sulfophenyl group, sulfonaphthyl group, disulfonaphthyl group, carboxynaphthyl group, dicarboxynaphthyl group, A carboxy-sulfonaphthyl group, a methyl-sulfonaphthyl group and a methoxy-sulfonaphthyl group can be mentioned. Among them, a group in which
- Examples of the metal salt of the compound having the structure represented by formula (2) include salts with monovalent metal cations such as Na + , K + , Li + , Ca 2+ , Mn 2+ , Sr 2+ , Salts with polyvalent metal cations such as Ba 2+ , Zn 2+ and Al 3+ are included.
- Component (b) is 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, in order to improve exposure sensitivity and storage stability. is bonded to the nitrogen atom of the imide ring via a divalent linking group containing an alkylene group having 1 to 6 carbon atoms and/or an azo bond.
- (b-1) a compound having a structure represented by formula (14) or a metal salt thereof, or (b-2) a compound having a structure represented by formula (15) or a metal salt thereof preferable.
- component (b) preferably contains (b-1) a compound having a structure represented by formula (14) or a metal salt thereof.
- component (b-1) It is more preferable that the compound having the structure represented by formula (14) or a metal salt thereof contains an organic dye compound or a metal salt thereof.
- component (b) preferably contains (b-2) a compound having a structure represented by formula (15) or a metal salt thereof.
- component (b-2) More preferably, the compound having the structure represented by formula (15) or a metal salt thereof contains an organic dye compound or a metal salt thereof.
- a compound having both a structure represented by formula (14) and a structure represented by formula (15) in the molecule has an azo bond, so (b-2) Defined as a compound belonging to a component.
- R 73 to R 76 each independently represent a hydrogen atom, a fluorine atom, a bromine atom or a hydroxyl group.
- R 77 represents an alkylene group having 1 to 6 carbon atoms.
- R78 represents a sulfo group or a carboxyl group.
- n 1 is an integer and represents 1 or 2; When n 1 is 2, two R 78 may be the same substituent or different substituents.
- R 79 represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.
- n2 is an integer and represents 0-2. When n 2 is 2, two R 79 may be the same substituent or different substituents.
- * represents a bonding site with a carbon atom.
- R 80 to R 83 each independently represent a hydrogen atom, a fluorine atom, a bromine atom or a hydroxyl group.
- R 84 represents a single bond or an alkylene group having 1 to 6 carbon atoms.
- R85 represents a single bond or NH.
- R 86 is 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 or an alkoxy group having 1 to 6 carbon atoms. represents one group selected from the group consisting of substituted naphthylene groups and unsubstituted naphthylene groups.
- R87 represents a sulfo group or a carboxyl group.
- n3 is an integer and represents 1 or 2; When n 3 is 2, two R 87 may be the same substituent or different substituents.
- R 88 represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.
- n4 is an integer and represents 0-2. When n 4 is 2, two R 88 may be the same substituent or different substituents.
- * represents a bonding site with a carbon atom.
- component (b-1) more preferably contains a compound represented by formula (16).
- the compound represented by formula (16) corresponds to an organic dye compound.
- the component (b-2) more preferably contains a compound represented by formula (17).
- the compound represented by formula (17) corresponds to an organic dye compound.
- R 89 and R 90 each independently represent an alkylene group having 1 to 6 carbon atoms.
- n5 is an integer and represents 0-2.
- R91 and R92 represent a sulfo group or a carboxyl group.
- n6 is an integer and represents 1 or 2;
- n7 is an integer and represents 0 or 1. When n6 is 2, two R91 may be the same substituent or different substituents.
- R 93 and R 94 are each independently 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, or a phenylene group having 1 to 6 carbon atoms.
- n8 is an integer and represents 0-2.
- R95 and R96 represent a sulfo group or a carboxyl group.
- n9 is an integer and represents 1 or 2.
- n10 is an integer and represents 0 or 1. When n 9 is 2, the two R 95 may be the same substituent or different substituents.
- the compound represented by formula (16) has a naphthalene skeleton when n5 is 0, a perylene skeleton when n5 is 1 , and a terylene skeleton when n5 is 2 .
- the compound represented by formula (17) has a naphthalene skeleton when n8 is 0, a perylene skeleton when n8 is 1 , and a terylene skeleton when n8 is 2 .
- Specific examples of the compound belonging to 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). compounds represented are mentioned, and these compounds correspond to organic dye compounds.
- Specific examples of the compound belonging to component (b-2) include the compound represented by formula (18), the compound represented by formula (19), the compound represented by formula (24), and the compound represented by formula (25).
- Examples of methods for obtaining compounds belonging to the component (b) include sulfonation reactions and imidization reactions. If necessary, both reactions may be combined to form a two-step synthesis route.
- a method for obtaining the component (b-2) by a sulfonation reaction is as follows.
- I. Pigment Red 178 is dissolved in 10 to 50% by weight of fuming sulfuric acid or 50 to 100% by weight of concentrated sulfuric acid. Adjust the temperature in the range of 90° C. and stir for 3 to 10 hours.
- the liquid temperature By setting the liquid temperature to 40°C or higher, the remaining unreacted portion of the starting material can be suppressed, and by setting the liquid temperature to 90°C or lower, the decomposition reaction of the starting material can be suppressed, and the purity of the product can be increased.
- the mixture is poured into water, preferably ice water, which is 100 times or more the weight of the starting material described above to obtain a slurry containing red precipitates, which is then filtered. Then, after washing with methanol or ethanol, it is preferably washed with water repeatedly until the residual amount of sulfate ions is less than 50 ppm by weight, and dried at 60 to 80° C. under reduced pressure. Finally, a dry pulverization process using a hammer mill or a jet mill is used to disentangle dry aggregates and powderize.
- the compound represented by the monosulfo formula (24), the disulfo formula (25), and/or the trisulfo formula ( 26) (or their metal salts) can be obtained.
- the number of sulfo groups introduced per molecule of the target product and its distribution can be controlled by the liquid temperature and reaction time depending on the concentration of fuming sulfuric acid or concentrated sulfuric acid.
- the end point of the reaction can be determined by performing Purification using silica gel chromatography can also increase the purity of a compound into which a specific range of sulfo groups has been introduced.
- the component (b-1) can also be obtained by a similar sulfonation reaction.
- I. Pigment Red 178, C.I. represented by the formula (34) was used as a starting material.
- I. Pigment Black 31 can be used to synthesize the compound represented by the above formula (21).
- C. I. Commercially available products of Pigment Black 31 include "Spectrasense (registered trademark)" Black S0084 (manufactured by BASF).
- the method of obtaining the component (b) by imidization reaction is as follows.
- Perylene-3,4,9,10-tetracarboxylic dianhydride represented by the formula (35) or a derivative thereof as a starting material, and 3-(aminomethyl)benzoic acid represented by the formula (36), etc. and an amino acid having a primary amino group are preferably added and mixed in a basic synthetic solvent such as molten imidazole.
- a catalyst such as zinc acetate may be added as necessary.
- the mixture is stirred for 3 to 10 hours while maintaining a heating temperature of 80 to 160°C under a nitrogen atmosphere to allow the imidization reaction to proceed.
- a heating temperature of 80 to 160°C under a nitrogen atmosphere to allow the imidization reaction to proceed.
- 10 to 50% by weight of hydrochloric acid is added as necessary, and a large amount of water having a weight of 100 times or more based on the starting material used, preferably ice water.
- a slurry containing a red precipitate is obtained and filtered.
- it is preferably washed with water repeatedly until the residual amount of amino acid is less than 50 ppm by weight, and dried at 60 to 80° C. under reduced pressure.
- Component (b-2) can also be obtained by a similar imidization reaction. compounds can be synthesized.
- the compound represented by the above formula (19) can be obtained.
- terylene-3,4,11,12-tetracarboxylic dianhydride or naphthalene-1,4,5,8-tetracarboxylic dianhydride and 3-[(4-aminophenyl)azo]benzenesulfonic acid The imidization reaction of can synthesize the compound represented by the formula (30) and the compound represented by the formula (31).
- a compound having a structure represented by the formula (2) and having no N,N-dialkylaminoalkyl group is dispersed in water to prepare a slurry, followed by Under the conditions, an Al 3+ source such as aluminum chloride, a Ba 2+ source such as barium chloride, or a Ca 2+ source such as calcium chloride is added and stirred under heating at 30 to 60° C. to form salt, followed by purification.
- an Al 3+ source such as aluminum chloride, a Ba 2+ source such as barium chloride, or a Ca 2+ source such as calcium chloride is added and stirred under heating at 30 to 60° C. to form salt, followed by purification.
- a method of pulverizing by drying and dry pulverization can be mentioned.
- the existence form of the component (b) in the positive photosensitive pigment composition and in the pixel division layer is not particularly limited, and at least a portion thereof may be insoluble particles or may be dissolved. In order to improve the storage stability, it is preferable that 90% by weight or more of the component (b) exists as insoluble particles, and the form of existence can be preferably controlled by the resin (c) and the organic solvent (e) described later. More preferably, at least part of the component (b) is adsorbed on the surface of the component (a) by coexisting when preparing the pigment dispersion described later. Also when the component (h) is contained, it is preferred that at least part of the component (b) is adsorbed on the surface of the component (h).
- Component (b) may form a solid solution with at least one of component (a) and component (h).
- component (b) contains insoluble particles
- the same viewpoints as those for the component (a) described above are preferably applied to the average primary particle diameter and the average aspect ratio thereof.
- the content of the component (b) is preferably 5 parts by weight or more relative to the total 100 parts by weight of the pigments contained in the positive photosensitive pigment composition, and 12 parts by weight or more, in order to improve storage stability. more preferred. 50 parts by weight or less is preferable, and 40 parts by weight or less is more preferable for improving exposure sensitivity.
- the content of the component (b) is 5 to 50 parts by weight with respect to the total 100 parts by weight of the pigments contained in the positive photosensitive pigment composition. is more preferred.
- the pigment contained in the positive photosensitive pigment composition as used herein refers to the above-described group of pigments exemplified as other pigments in addition to the components (a) and (h), and the component (b). does not include the component (b), regardless of whether it is dissolved and/or insoluble particles in the positive photosensitive pigment composition.
- the content of the component (b) can be obtained by converting each to weight.
- the chemical structures of the compounds constituting components (a), (h) and (b) were determined by using a concentrate obtained by centrifuging the positive photosensitive pigment composition of the present invention as a sample.
- Desorption ionization-time-of-flight mass spectrometry MALDI-TOF MS
- time-of-flight secondary ion mass spectrometry TOF-SIMS
- time-of-flight mass spectrometry TOF-MS
- nuclear magnetic resonance (NMR) nuclear magnetic resonance
- LC-MS liquid chromatography-mass spectrometry
- infrared absorption spectrum and X-ray diffraction.
- the positive photosensitive pigment composition of the present invention contains (c) a resin as an essential component.
- resin used herein means a compound having a polymer chain with 5 or more repeating units and a weight average molecular weight (Mw) of 1,000 or more.
- Component (c), together with component (d) described later, is a component that imparts positive photosensitivity. It has a function as a binder component for fixing to.
- Component (c) is not particularly limited, but contains (c-1) a resin having an alkali-soluble group (hereinafter sometimes referred to as "(c-1) component") in order to improve halftone processability.
- the alkali-soluble group here means a hydroxyl group, a carboxyl group, a phosphoric acid group and a sulfo group.
- a hydroxyl group is preferred as the alkali-soluble group, and a phenolic hydroxyl group is more preferred.
- component (c-1) examples include polyimides, polyimide precursors, polybenzoxazole precursors, phenol resins, resins having repeating units derived from radically polymerizable monofunctional monomers having alkali-soluble groups, and polysiloxanes. . These resins may be resins having multiple types of alkali-soluble groups in the molecule, and may contain two or more types of resins.
- polyimides, polyimide precursors, polybenzoxazole precursors, or copolymers thereof are preferable because they can improve halftone processability.
- the method for producing the copolymer referred to here is not particularly limited, and it may be a random copolymer or a block copolymer.
- the block copolymer as used herein means a copolymer having repeating units of different resin types in the molecule and having a polymer chain in which 10 or more repeating units having the same structure are linked.
- R 97 represents a 4- to 10-valent organic group.
- R 98 represents a divalent to octavalent organic group.
- R 99 and R 100 each independently represent a hydroxyl group or a carboxyl group, each of which may be a single group or a mixture of different groups.
- p and q are integers and each independently represents 0-6. However, p+q>0 is satisfied. * represents a binding site.
- R 101 and R 102 represent divalent to octavalent organic groups.
- R 103 and R 104 each independently represent a phenolic hydroxyl group, a carboxyl group or COOA, each of which may be a single group or a mixture of different groups.
- A represents a monovalent hydrocarbon group having 1 to 10 carbon atoms.
- r and s are integers and each independently represent 0-6. However, r+s>0 is satisfied.
- * represents a binding site.
- the resin having the structural unit represented by formula (39) preferably has a group represented by COOA in order to improve the halftone workability.
- Valent hydrocarbon groups A include, for example, methyl, ethyl, propyl, phenyl or benzyl groups.
- the component (c-1) preferably has a structural unit having an amide bond that has a high interaction with the component (b) in order to improve storage stability, and is represented by the formula (39) It is more preferable to contain a resin having a structural unit.
- (c) resin more preferably contains a resin having a structural unit represented by formula (39).
- the weight average molecular weight (Mw) of the resin having the structural unit represented by formula (39) is preferably 10,000 or more and 50,000 or less in order to improve storage stability.
- R 97 -(R 99 )p represents an acid dianhydride residue.
- R 97 is preferably an organic group having 5 to 40 carbon atoms containing an aromatic ring or cycloaliphatic group.
- Acid dianhydride residues include, for example, pyromellitic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic acid acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3' -benzophenonetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1
- R105 represents a single bond, an oxygen atom, C ( CF3 ) 2 , C( CH3 ) 2 or SO2.
- R 106 and R 107 each independently represent a hydrogen atom or a hydroxyl group.
- R 101 -(R 103 )r represents an acid residue.
- R 101 is preferably an organic group having 5 to 40 carbon atoms containing an aromatic ring or a cycloaliphatic group.
- Examples of acid residues include dicarboxylic acid residues, tricarboxylic acid residues, and tetracarboxylic acid residues.
- Dicarboxylic acids include terephthalic acid, isophthalic acid, diphenyletherdicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyldicarboxylic acid, benzophenonedicarboxylic acid, and triphenyldicarboxylic acid.
- Examples of tricarboxylic acids include residues of trimellitic acid, trimesic acid, diphenylethertricarboxylic acid, and biphenyltricarboxylic acid.
- Tetracarboxylic acid residues include pyromellitic acid, 3,3′,4,4′-biphenyltetracarboxylic acid, 2,3,3′,4′-biphenyltetracarboxylic acid, 2,2′,3, 3′-biphenyltetracarboxylic acid, 3,3′,4,4′-benzophenonetetracarboxylic acid, 2,2′,3,3′-benzophenonetetracarboxylic acid, 2,2-bis(3,4-dicarboxy phenyl)hexafluoropropane, 2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3- dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane, bis(3,
- R 98 -(R 100 )q in formula (38) and R 102 -(R 104 )s in formula (39) represent diamine residues.
- R 98 and R 102 are preferably C 5-40 organic groups containing an aromatic ring or a cycloaliphatic group.
- Diamine residues include, for example, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 1,4-bis(4-amino phenoxy)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, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-diethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl -4,4'-diaminobiphenyl, 3,3'-
- R 108 represents a single bond, an oxygen atom, C(CF 3 ) 2 , C(CH 3 ) 2 or SO 2 .
- R 109 and R 110 each independently represent a hydrogen atom or a hydroxyl group.
- R 111 represents a single bond, an oxygen atom, C(CF 3 ) 2 , C(CH 3 ) 2 or SO 2 .
- R 112 and R 113 each independently represent a hydrogen atom or a hydroxyl group.
- R 114 , R 115 , R 116 and R 117 each independently represent a hydrogen atom or a hydroxyl group.
- R 118 and R 119 each independently represent a hydrogen atom or a hydroxyl group.
- the weight average molecular weight (Mw) can be easily adjusted, and (c) the storage stability of the resin can be improved.
- Examples of monoamines include 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene and 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-amino Phenol is mentioned.
- esterifying agents include, for example, N,N-dimethylformamide dimethylacetal and N,N-dimethylformamide diethylacetal.
- a resin having a structural unit represented by formula (38) and/or a structural unit represented by formula (39) can be obtained by a known method. 097992 and WO 2019/181782.
- Phenolic resins include, for example, novolac-type phenolic resins and resol-type phenolic resins having structural units represented by formula (45) and/or structural units represented by formula (46).
- a phenol resin may be used in combination for the purpose of adjusting the dissolution rate in an alkaline developer and the thermal fluidity of the developed film.
- the weight average molecular weight (Mw) of the phenol resin is preferably 1,500 or more and 15,000 or less from the viewpoint of developability.
- R 120 and R 121 each independently represent a methylene group or a CH-Ar group.
- Ar represents a phenyl group substituted with an alkyl group having 1 to 3 carbon atoms or an unsubstituted phenyl group. * represents a binding site.
- a phenol resin can be obtained by a known method, and a compound having a phenol skeleton such as phenol, o-cresol, m-cresol, p-cresol and xyresol is added with an aldehyde compound such as formaldehyde and benzaldehyde in the presence of an acidic catalyst. It can be synthesized by condensing with Examples of commercially available phenolic resins include TRR5030G, TRR5010G, TR4020G, TR4080G, TR4000B, TRM30B20G, and EP23F10G (all of which are manufactured by Asahi Organic Chemicals Co., Ltd.).
- resins having repeating units derived from radically polymerizable monofunctional monomers having alkali-soluble groups include hydroxyl groups such as hydroxystyrene, hydroxyphenyl (meth)acrylate, hydroxyphenyl (meth)acrylamide, and N-hydroxyphenyl-substituted maleimide.
- a radically polymerizable monofunctional monomer having a thermally crosslinkable group such as glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and allylglycidyl (meth)acrylate may be copolymerized.
- (Meth)acrylate here means methacrylate or acrylate.
- a resin having a structure represented by formula (47) and a resin having a structure represented by formula (48) are preferable.
- the weight-average molecular weight (Mw) of the resin having repeating units derived from a radically polymerizable monofunctional monomer having an alkali-soluble group is preferably 3,000 or more and 30,000 or less from the viewpoint of developability.
- R 122 and R 124 each independently represent a hydrogen atom or a methyl group.
- R 123 represents a single bond, COO or CONH.
- R 125 represents a monovalent organic group having an epoxy group. * represents a binding site.
- (c-2) a resin having no alkali-soluble group (hereinafter sometimes referred to as "(c-2) component”) may be included.
- the component (c-2) include (meth)acrylic resins having no alkali-soluble group, and at least part of the surface of the component (a) and/or the pigment other than the component (a). It can be preferably used as a surface treatment material for coating.
- a (meth)acrylic resin When 5 to 20 parts by weight of a (meth)acrylic resin is coexisted with 100 parts by weight of the pigment and the physical refining treatment described above is performed, active surfaces are generated and crystal growth and aggregation tend to proceed. However, there are cases where miniaturization is likely to proceed.
- the component (c-2) is contained as a pigment surface treatment material, it is preferably a water-insoluble resin in order to avoid elution when the grinding material is removed by washing with water and fix it on the pigment surface.
- (Meth)acrylic resins having no alkali-soluble group include, for example, glycidyl (meth)acrylate, allylglycidyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate , iso-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, benzyl ( Examples thereof include resins obtained by radically polymerizing one or a combination of two or more radically polymerizable monofunctional monomers having no alkali-soluble group, such as meth)acrylate and nonylphenoxypolyethylene glycol (meth)acrylate.
- the content of the resin (c) 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 order to improve the storage stability. From the viewpoint of improving exposure sensitivity, it is preferably 90% by weight or less, more preferably 60% by weight or less.
- the content of the resin having a structural unit represented by formula (39) is preferably 50% by weight or more, more preferably 80% by weight or more, in the resin (c) in terms of improving exposure sensitivity and storage stability. more preferred.
- the amine value of the resin is preferably 5.0 mgKOH/g or less, more preferably 3.0 mgKOH/g or less, in order to improve storage stability.
- the weighted average value according to the content ratio can be regarded as the amine value of the (c) resin.
- the (c) resin preferably has an amine value of 5.0 mgKOH/g or less.
- the method for measuring the amine value referred to here will be described below.
- the sample was dissolved by adding 60 mL of the solvent ( ⁇ -butyrolactone) to a 100 mL Erlenmeyer flask, and the titrant ( Titration is performed with 0.1 mol/L hydrochloric acid), and the obtained inflection point is taken as the end point.
- blank titration is performed in the same manner without containing the sample, and the amine value is calculated from the following formula.
- Amine value (mgKOH/g) (V 1 -V 0 ) x f x 0.1 x 56.11/S
- S mass (g) of sample ((c) resin)
- V 0 amount of titrant required for blank titration (mL)
- V 1 amount of titrant required for titration of sample (mL)
- f titrant factor (1.006).
- any means may be used.
- the resin may be diluted with ⁇ -butyrolactone and centrifuged several times to separate the pigment from the bottom liquid.
- the concentrate may be filtered as an insoluble particulate component, and if necessary, may be subjected to separation treatment by column purification or drying treatment under reduced pressure.
- the amine value of the resin solution may be converted into the amine value of the (c) resin according to the solid content.
- the positive photosensitive pigment composition of the present invention contains (d) a photoacid generator as an essential component.
- the photoacid generator is not particularly limited as long as it is a compound that is decomposed by light irradiation to generate an acid.
- the generated acid has the effect of increasing the solubility of the exposed portion of the film in an alkaline developer relative to the solubility of the unexposed portion of the film in an alkaline developer.
- positive photolithography is possible in which a pattern is formed by removing the exposed portion of the film that has been pattern-exposed through an exposure mask.
- the amount of acid generated in the film can be controlled by adjusting the amount of exposure, and the solubility of the exposed portion of the film in an alkaline developer exposed through the halftone exposure mask with a small amount of exposure can be increased by adjusting the amount of exposure. It has the effect of lowering the solubility of the exposed portion of the film exposed in a sufficient amount to an alkaline developer, making it possible to form a pattern having steps by positive halftone processing.
- (d) components include quinonediazide compounds, oxime sulfonate compounds, and imidosulfonate compounds.
- a quinone diazide compound is preferred because it exerts an excellent dissolution inhibiting effect on the film in the unexposed area, can increase the dissolution rate difference between the exposed area and the unexposed area, and has excellent exposure sensitivity.
- the quinonediazide compound is an esterification reaction of a compound having a phenolic hydroxyl group and 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride (hereinafter sometimes referred to as "4-naphthoquinonediazide sulfonyl chloride").
- a 4-naphthoquinonediazide sulfonyl ester compound or a compound having a phenolic hydroxyl group, which is the resulting compound, and 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride (hereinafter referred to as "5-naphthoquinonediazide sulfonyl chloride")
- a 5-naphthoquinone diazide sulfonyl ester compound which is a compound obtained by an esterification reaction of (1), is preferred.
- a compound having two or more phenolic hydroxyl groups in the molecule is preferable for improving the exposure sensitivity.
- compounds having two or more phenolic hydroxyl groups in the molecule include TrisP-HAP represented by formula (49), TrisP-PA represented by formula (50), and TekP represented by formula (51).
- TrisP-HAP represented by formula (49)
- TrisP-PA represented by formula (50)
- TekP represented by formula (51).
- -4HBPA, TrisP-SA, TrisOCR-PA, Bis P-AP, Bis P-NO, Bis P-PR, Bis P-B, Bis P-DE, Bis P-DP, Bis P-DP, Bis RS-2P, Bis RS -3P and Bis P-DEK both of which are manufactured by Honshu Chemical Industry Co., Ltd.).
- a quinonediazide compound having a 4-naphthoquinonediazidesulfonyl group and a 5-naphthoquinonediazidesulfonyl group in the molecule may also be contained.
- the transmittance of the film containing the components (a) and (b) in the wavelength region of 365 to 436 nm is generally maximum in the wavelength region of 410 to 440 nm.
- a compound having a 5-naphthoquinonediazidosulfonyl group When the compound having the structure represented by formula (52) is contained, carboxylic acid is generated in the exposed portion of the film.
- R 126 to R 130 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. * represents a binding site.
- component (d) may contain a compound having an alkoxyalkyl group or an epoxy group as a thermally crosslinkable group and a naphthoquinonediazidosulfonyl group as a photosensitive group in the molecule.
- a compound having an alkoxyalkyl group or an epoxy group as a thermally crosslinkable group and a naphthoquinonediazidosulfonyl group as a photosensitive group in the molecule include quinonediazide compounds having an alkoxymethyl group disclosed in JP-A-2018/158263. In this specification, these compounds are defined as compounds belonging to component (d) rather than thermal cross-linking agents (g) (hereinafter sometimes referred to as "component (g)").
- component (d) Commercially available products for component (d) include PA-28 (manufactured by Daito Chemix Co., Ltd.), a naphthoquinone diazide compound that generates an acid when exposed to i-rays, and an oxime sulfonate compound that generates an acid when exposed to i-rays.
- PA-28 manufactured by Daito Chemix Co., Ltd.
- a naphthoquinone diazide compound that generates an acid when exposed to i-rays and an oxime sulfonate compound that generates an acid when exposed to i-rays.
- PAG103 and PAG203 all of which are manufactured by BASF
- NIT, NIN, and ILP-110 all of which are manufactured by Heraeus
- the content of component (d) is 1% by weight or more based on 100% by weight of the solid content of the positive photosensitive pigment composition in order to generate a necessary and sufficient amount of acid in the film to improve the exposure sensitivity.
- 5% by weight or more is more preferable. It is preferably 30% by weight or less, more preferably 20% by weight or less, in order to suppress excessive absorption of exposure light on the film surface and improve exposure sensitivity.
- the positive photosensitive pigment composition of the present invention contains (e) an organic solvent as an essential component.
- the organic solvent not only contributes to improving the storage stability as a dispersion medium for the component (a), but also improves the applicability of the positive photosensitive pigment composition and enhances the smoothness of the pre-baked film described later. , has the effect of improving the halftone workability.
- (e) component includes, for example, ether-based solvents, glycol-based solvents, acetate-based solvents, ketone-based solvents, lactone-based solvents, aromatic carbon-based solvents, and amide-based solvents.
- Ether solvents include ethylene glycol monomethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- butyl ether, propylene glycol monomethyl ether (hereinafter "PGME”), propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether.
- PGME propylene glycol monomethyl ether
- Glycol-based solvents include ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol.
- Acetate solvents include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA”), propylene glycol monoethyl ether acetate, Examples include methyl lactate, ethyl lactate, and 3-methoxybutyl acetate (hereinafter “MBA”).
- Ketone solvents include methyl ethyl ketone, diisobutyl ketone, cyclohexanone, 2-heptanone and 3-heptanone.
- lactone solvents include ⁇ -butyrolactone and ⁇ -valerolactone.
- Aromatic carbon solvents include toluene, xylene, and benzene.
- amide-based solvents include N-methylpyrrolidone (hereinafter referred to as "NMP"), N,N-dimethylformamide, and N,N-dimethylacetamide. Above all, it preferably contains an ether solvent and/or an acetate solvent, and more preferably contains a lactone solvent, in order to improve storage stability.
- the content of 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 order to improve storage stability. It is preferably 99% by weight or less, more preferably 95% by weight or less, in order to improve the smoothness of the prebaked film.
- the content of the aromatic hydrocarbon-based solvent and the amide-based solvent is preferably 0.5% by weight or less in 100% by weight of the positive photosensitive pigment composition in order to improve storage stability. Moreover, the storage stability may be further improved by containing 0.01 to 0.5% by weight of water in 100% by weight of the positive photosensitive pigment composition.
- the positive photosensitive pigment composition of the present invention further contains (f) a compound that is converted by heating into a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm in the wavelength range of 350 to 780 nm. is preferred.
- the component (f) referred to here is a compound that does not belong to any of the components (a) to (i), and the principle of thermal coloring is not particularly limited.
- the components (a) and (h) have a higher transmittance in the wavelength range of 410 to 440 nm than the transmittance in the range of 500 to 650 nm.
- the resulting pixel dividing layer can preferably have a low maximum transmittance in the wavelength range of 410 to 440 nm.
- the component (f) after thermal color development is By exhibiting yellow, orange, or brown color, it is possible to obtain a black pixel division layer that is also excellent in the function of suppressing external light reflection in the blue region.
- the minimum temperature at which color development starts is preferably 150° C. or higher in order to avoid deterioration of exposure sensitivity, and is preferably 230° C. or lower in order to sufficiently obtain the effect of reducing transmittance.
- Component (f) includes, for example, thermochromic compounds described in JP-A-2004-326094.
- the component (f) contains a hydroxyl group-containing compound in order to improve the halftone workability.
- hydroxyl group-containing compounds include 4,4′,4′′,4′′′-(1,4-phenylenedimethylidene)tetrakisphenol (maximum absorption wavelength after heat treatment: 440 nm) represented by formula (53). 4,4′,4′′-trihydroxytriphenylmethane (maximum absorption wavelength after heat treatment: 460 nm), 4-[bis(4-hydroxyphenyl)methyl)]2-methoxyphenol (maximum absorption wavelength after heat treatment: 470 nm).
- the positive photosensitive pigment composition of the present invention may further contain component (g).
- component (g) compounds having two or more alkoxymethyl groups or epoxy groups in the molecule are preferred.
- Alkoxymethyl groups include methoxymethyl, ethoxymethyl, propoxymethyl and butoxymethyl groups.
- the heat resistance and flexibility of the pixel dividing layer can be improved by the crosslinked structure formed by the reaction between the component (g) and the resin (c) and the reaction between the components (g).
- the cured film containing the cured product of the positive photosensitive pigment composition of the present invention can be used as a TFT (Thin -film transistors)
- TFT Thin -film transistors
- Compounds having two or more alkoxymethyl groups in the molecule include, for example, HMOM-TPHAP, DML-PC, DML-PEP, DML-OC, and DML-POP (all manufactured by Honshu Chemical Industry Co., Ltd.). , "NIKALAC (registered trademark)" MX-390, MX-290, MX-280, MX-270, MW-100LM, and MX-750LM (both of which are manufactured by Sanwa Chemical Co., Ltd.) mentioned.
- NIKALAC registered trademark
- Examples of compounds having two or more epoxy groups in the molecule include TEPIC-S, TEPIC-PAS, TEPIC-VL, TEPIC-UC (all of which are manufactured by Nissan Chemical Industries, Ltd.), XD-1000, and XD. -1000-H, XD-1000-2L, NC-3000 (all manufactured by Nippon Kayaku Co., Ltd.), TECHMORE VG3101L (manufactured by Printec Co., Ltd.), TR-FR-201 (manufactured by Tronly) mentioned.
- the positive photosensitive pigment composition of the present invention preferably further contains (i) aminobenzenesulfonic acid (hereinafter sometimes referred to as "component (i)") in order to improve exposure sensitivity.
- component (i) includes, for example, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, and 4-aminobenzenesulfonic acid (all of which are manufactured by Tokyo Chemical Industry Co., Ltd.).
- the content of the component (i) is preferably 0.01% or more in the solid content of the positive photosensitive pigment composition in order to improve the exposure sensitivity. 0.5% by weight or less is preferable for maintaining storage stability.
- the positive photosensitive pigment composition of the present invention may contain a leveling agent and an adhesion improver to the substrate surface as other components.
- a surfactant containing a fluorine atom in the molecule may be added to impart liquid repellency to the surface of the pixel dividing layer.
- a pigment dispersion containing components (a), (b), (c) resin and (e) is prepared in advance by wet dispersion treatment, and then ( Components d) and (e), and if necessary, components (f), (g), (i) and other components are mixed with a pigment dispersion, stirred, and optionally filtered through a filter. method.
- the component (h) is contained, the components (a), (b), (c) resin, (e) and (h) are used to improve the storage stability of the positive photosensitive pigment composition. It is desirable to prepare in advance a pigment dispersion containing
- a wet media dispersing machine or a wet medialess dispersing machine may be used.
- preferred to use By the wet media dispersion treatment, secondary aggregates of pigment components such as the component (a) are deaggregated, and preferably the secondary particle size can be controlled in a finer direction to a region close to the primary particle size.
- wet media dispersers examples include “Revomill (registered trademark)” (manufactured by Asada Iron Works Co., Ltd.), “Nano Getter (registered trademark)” (manufactured by Ashizawa Finetech Co., Ltd.), and “DYNO-MILL ( Registered trademark)” (manufactured by Willy A.
- the primary particles can be prevented from being destroyed, and secondary aggregates in which a large number of primary particles are aggregated can be disentangled while maintaining the average primary particle size, the average aspect ratio of the primary particles, and the maximum primary particle size. Ultra Apex Mill Advance is preferred.
- Ceramic beads such as zirconia are preferable for the material of the media, and the diameter thereof is preferably 0.03 to 0.5 mm ⁇ .
- Commercially available products include “Torayceram (registered trademark)” (manufactured by Toray Industries, Inc.).
- D50 (cumulative 50% secondary particle diameter) in the particle size distribution of the particle component in the positive photosensitive pigment composition on a volume basis, measured by a dynamic light scattering method, is important for improving storage stability. , 30 nm or more. 70 nm or less is preferable for improving the exposure sensitivity.
- D90 (cumulative 90% secondary particle diameter) is preferably 80 nm or more for improving storage stability. 150 nm or less is preferable for improving the exposure sensitivity.
- D50 and D90 refer to values obtained by measuring a particle size distribution measurement sample.
- the diluting solvent a solvent having the same composition as the (e) organic solvent contained in the positive photosensitive pigment composition is used.
- the particle size distribution referred to here can be measured by a dynamic light scattering particle size distribution analyzer SZ-100 (manufactured by HORIBA, Ltd.), and refers to the particle size distribution based on the volume with respect to the light source.
- D50 and D90 mean particle diameters (nm) corresponding to 50% and 90%, respectively, accumulated from the smaller particle size side to the larger particle size side in the cumulative particle size distribution curve (0%). do.
- 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.
- cured product as used herein means a product obtained through a step of heating a positive photosensitive pigment composition at a temperature of 200° C. or higher and 400° C. or lower under atmospheric pressure for 10 minutes or longer.
- the organic EL display device of the present invention preferably comprises a cured film containing a cured product of 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, it may be, for example, a pixel dividing layer or a TFT flattening layer.
- the organic EL display device of the present invention is excellent in the function of suppressing external light reflection and is provided with a polarizing plate. It has a technical effect of being excellent in visibility.
- 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, for example, moisture mixed during the formation process of the cured film, the underlying substrate or Examples thereof include metal ions such as Na + and Ag + that are mixed in the cured film originating from electrodes and the like.
- 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.
- the optical density per 1.0 ⁇ m film thickness of the pixel dividing layer is preferably 0.5 or more, more preferably 0.7 or more, in order to suppress external light reflection and increase the value of the display device. . From the viewpoint of exposure sensitivity, it is preferably 1.3 or less, more preferably 1.1 or less.
- the optical density is obtained by comparing the pixel division layer formed on the transparent substrate to a film thickness of 1.5 ⁇ m with the incident light intensity using an optical densitometer X-Rite 361T (manufactured by X-Rite). It means a value obtained by measuring the intensity of transmitted light and dividing the value calculated from the following formula by 1.5, which is the value of the film thickness.
- a transparent glass substrate “Tempax (manufactured by AGC Techno Glass Co., Ltd.)" can be preferably used as the transparent substrate.
- optical density log10 ( I0 /I) In the above formula, I 0 : incident light intensity, I: transmitted light intensity.
- the thickness of the thick film portion of the pixel dividing layer having steps is set to 2.5. It is preferably 5 to 4.0 ⁇ m, and the thickness of the thin film portion is preferably 1.0 to 2.5 ⁇ m.
- the film thickness of the thick film portion and the film thickness of the thin film portion referred to here mean the film thickness of the flat portion, excluding the film thickness of the inclined portion located at the edge of the film.
- the difference in film thickness between the thick film portion and the thin film portion is preferably 1.0 to 1.5 ⁇ m.
- An opening may be formed only in the thin film portion, and the thick film portion may be locally arranged in the form of a spacer.
- the cross-sectional taper angle of the inclined portion located at the end of the thin film portion of the pixel dividing layer having a step is preferably 50° or less, and preferably 40° or less, in order to suppress disconnection of the electrode and avoid occurrence of unlit pixels. more preferred.
- the angle is preferably 15° or more, more preferably 20° or more, in order to suppress deterioration of the light-shielding properties at the edge of the thin film portion.
- the method for forming a pixel dividing layer having steps includes a coating step of applying a positive photosensitive pigment composition to obtain a coating film, a prebaking step of heating the coating film to obtain a prebaked film, and a positive halftone.
- a method including a developing step of removing part of the semi-exposed area and the unexposed area to obtain a developed film, and a curing step of obtaining a cured film by thermally curing by heating is preferred.
- a spin coater or a slit coater can be preferably used as a coating device used in the coating process because of its excellent thin film coating properties. After application, pin gap pre-baking or contact pre-baking may be performed.
- the prebaking temperature in the prebaking step is preferably 50 to 150°C, and the prebaking time is preferably 30 seconds to 5 minutes.
- the film thickness of the pre-baked film is preferably 3.5 to 6.0 ⁇ m.
- the maximum transmittance at a wavelength of 800 to 1,300 nm of the prebaked film of the positive photosensitive pigment composition is preferably 20% or more, and 30%, in order to increase the positional accuracy. The above is more preferable.
- Examples of exposure apparatuses used in the exposure process include steppers, mirror projection mask aligners (MPA), and parallel light mask aligners (PLA).
- the actinic radiation irradiated during exposure includes j-line (wavelength 313 nm), i-line (wavelength 365 nm), h-line (wavelength 405 nm) or g-line (wavelength 436 nm) of an extra-high pressure mercury lamp.
- Mixed lines containing at least h-lines are preferred, and mixed lines containing g-lines, h-lines and i-lines are more preferred.
- a positive halftone exposure mask has a total transmission portion, a semi-transmission portion, and a shielding portion within the substrate surface. It is preferable to use a mask designed so that the amount of exposure in some areas is 10 to 50%.
- the exposed portion in the exposed film means a portion pattern-exposed through the full-transmissive portion of the exposure mask
- the semi-exposed portion means a portion pattern-exposed through the semi-transmissive portion of the exposure mask, which is not exposed.
- a portion means a portion that is not exposed by the shielding portion of the exposure mask.
- Examples of the developing method in the developing process include methods such as showering, dipping, and puddle, and include a method of immersing the exposed film for 10 seconds to 3 minutes.
- the paddle method is preferable for improving the halftone workability.
- As the alkaline developer a 0.4 to 2.5% by weight tetramethylammonium hydroxide aqueous solution (hereinafter referred to as "TMAH") is preferable. ) made).
- TMAH tetramethylammonium hydroxide aqueous solution
- the development time is the value obtained by subtracting the thickness of the thick film portion (unexposed portion) of the developed film having a step from the film thickness of the prebaked film. It is preferable to set the film reduction ( ⁇ m) in the development process to 1.0 ⁇ m or less. It is preferable to set the thickness to 0.5 ⁇ m or more in order to improve the exposure sensitivity. Further, the obtained developed film may be irradiated again with exposure light as a second exposure step to control the fluidity of the film in the curing step.
- the developed film is thermally cured by heating, and the developer and moisture remaining in the film are volatilized to obtain a cured film.
- the heating apparatus include a hot air oven and an IR oven, and the heating atmosphere includes nitrogen or air.
- the heating temperature is preferably 200 to 350°C, more preferably 220 to 280°C under atmospheric pressure.
- the organic EL display device of the present invention is an organic EL display device comprising a substrate, a first electrode, a pixel division layer, a light-emitting pixel and a second electrode, wherein the pixel division layer is represented by (a) formula (1) and (b) a pigment containing a compound having one perylene skeleton in the molecule, and (b) a structure represented by formula (2), wherein the N,N-dialkylaminoalkyl An organic EL display device containing a compound having no group or a metal salt thereof.
- R 1 represents an optionally substituted phenylene group or an optionally substituted naphthylene group.
- * represents a bonding site with a carbon atom constituting the perylene skeleton.
- R 2 to R 5 each independently represent a hydrogen atom, a fluorine atom, a bromine atom or a hydroxyl group.
- R6 represents 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 bonding site with a carbon atom.
- the organic EL display device of the present invention it is possible to obtain the advantageous technical effect of reducing variations in luminance in the plane of the panel display portion, that is, less unevenness in luminance.
- FIG. 2 shows a cross-sectional view of a TFT substrate in an organic EL display device that is given as a specific example of an embodiment of the present invention.
- TFTs 3 Bottom-gate type or top-gate type thin film transistors 3 (hereinafter abbreviated as TFTs 3) are provided in a matrix on the surface of the substrate 8, and the TFTs cover the TFTs 3 and the wiring 4 connected to the TFTs 3.
- An insulating layer 5 is formed. Further, a flattening layer 6 is formed on the surface of the TFT insulating layer 5 , and a contact hole 9 is provided in the flattening layer 6 to connect the first electrode 7 to the wiring 4 .
- a first electrode 7 is patterned on the surface of the planarizing layer 6 and connected to the wiring 4 .
- a pixel division layer 10 is formed so as to surround the pattern periphery of the first electrode 7 .
- the pixel division layer 10 is provided with an opening, the opening is formed with a light emitting pixel 11 containing an organic EL light emitting material, and the second electrode 12 separates the pixel dividing layer 10 and the light emitting pixel 11. A film is formed in a state of covering.
- the shape of the opening of the pixel division 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 light-emitting pixel 11, which will be described later.
- the minor axis may be 10 to 50 ⁇ m. The smaller the minor axis of the opening width of the opening, the more useful the effect of suppressing the luminance unevenness exhibited by the organic EL display device of the present invention.
- the pixel dividing layer has a thick film portion with a thickness of 2.5 to 4.0 ⁇ m and a thin film portion with a thickness of 1.0 to 2.5 ⁇ m, and the thick film portion It is preferable to have a portion where the difference in film thickness between the thin film portion and the thin film portion is 1.0 ⁇ m or more.
- the thick film portion has a spacer effect, reduces the contact area with the vapor deposition mask when forming the light-emitting pixels 11, improves the production yield, prevents defects in the organic EL elements, and suppresses the occurrence of non-lighting pixels. can.
- the emission peak wavelength of the emission pixels 11 is not particularly limited, for example, a configuration in which different types of pixels having emission peak wavelengths in the three primary colors of light, blue, red, and green, are arrayed on the entire surface. is mentioned.
- the peak wavelength in the red region may be 560-700 nm
- the peak wavelength in the blue region may be 420-480 nm
- the peak wavelength in the green region may be 500-550 nm.
- blue, red, and green color filters and a black matrix separating them may be combined and arranged on the front surface of the display section.
- the organic EL light-emitting material constituting the light-emitting pixel 11 a material obtained by combining a hole-transporting layer and/or an electron-transporting layer in addition to the light-emitting layer can be preferably used.
- a mask vapor deposition method can be used as a method for patterning the light-emitting pixels 11.
- the mask vapor deposition method is a method of vapor-depositing and patterning an organic compound using a vapor deposition mask. Specifically, vapor deposition is performed by arranging a vapor deposition mask having a desired pattern as an opening on the substrate side. mentioned.
- a vapor deposition mask used for forming high-definition light-emitting pixels for example, a vapor deposition mask disclosed in Japanese Patent Application Laid-Open No. 2019-163543 can be mentioned.
- conductive metal oxides such as indium tin oxide (ITO) and indium zinc oxide (IZO) can be used.
- ITO is preferable because of its excellent transparency and conductivity.
- a positive resist material for etching is patterned by photolithography to obtain a resist pattern on the ITO film. Only the ITO film in the formation portion is removed with an etchant. Next, the resist pattern is removed with a resist stripping solution, and if necessary, a heat treatment is performed so as to achieve a desired degree of crystallinity.
- a positive photosensitive pigment composition containing an alkali-soluble novolac resin can be used as a positive photosensitive pigment composition containing an alkali-soluble novolac resin.
- an aqueous solution containing nitric acid and hydrochloric acid or an aqueous oxalic acid solution can be used. 2. IS-3 (both of which are manufactured by Sasaki Chemicals Co., Ltd.). An organic amine-based aqueous solution can be used as the resist stripping solution. Sanwaka Junyaku Research Institute).
- the organic EL display device of the present invention is a top emission type organic EL display device, the first electrode 7 has a lamination structure of ITO/silver alloy/ITO in order to improve light reflectivity and adhesion to the substrate. may
- the second electrode 12 may be made of any material as long as it is a layer that functions as an electrode.
- the second electrode 12 for example, when the organic EL display device of the present invention is a bottom emission type organic EL display device, a layer made of aluminum can be preferably used from the viewpoint of excellent light reflectivity.
- a silver alloy such as silver/magnesium can be preferably used because of its excellent light transmittance.
- the second electrode 12 can be obtained by forming a film on the entire surface by sputtering.
- the light extraction direction of the organic EL display device of the present invention is not particularly limited. It may be a top emission type organic EL display device in which emitted light is extracted to the opposite side of the substrate 8 via the second electrode 12 .
- a substrate made of glass that does not have flexibility or a substrate made of polyimide resin that has flexibility can be used.
- glass examples include OA-10G and OA-11 (all of which are manufactured by Nippon Electric Glass Co., Ltd.) and AN-100 (manufactured by Asahi Glass Co., Ltd.).
- a substrate made of polyimide resin a solution containing polyamic acid is applied to the surface of the temporary support, and then the polyamic acid is imidized by heat treatment at 250 to 400 ° C. to convert it into a polyimide resin. can be obtained by peeling off with a laser or the like.
- the polyamic acid used in this case can be synthesized by reacting a tetracarboxylic dianhydride and a diamine compound in an amide solvent such as N-methyl-2-pyrrolidone.
- a polyamic acid having a residue of an aromatic tetracarboxylic dianhydride and a residue of an aromatic diamine compound is preferred because it is small and has excellent dimensional stability.
- a specific example is a polyamic acid having a residue of 3,3′,4,4′-biphenyltetracarboxylic dianhydride and a residue of p-phenylenediamine.
- 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 applied to the finally obtained stepped pixel division layer using a spin coater.
- the rotation speed was adjusted so that the film thickness of the thick film portion was 3.0 ⁇ 0.2 ⁇ m and the film thickness of the thin film portion was 1.5 ⁇ m, and the ITO surface of the glass substrate provided with the silver alloy film/ITO film was coated with Each was applied to obtain a coating film. Furthermore, using a hot plate, the coating film is pre-baked at 110 ° C.
- a near-infrared camera (light source wavelength: 800 nm) is used to use a positive halftone exposure mask (longitudinal: 220 square fully-transmissive portions of 30.0 ⁇ m and 30.0 ⁇ m in width are arranged. A mask designed to be 15%) was aligned.
- the exposure amount is changed in steps of 10 mJ within the range of 40 to 300 (mJ/cm 2 : i-line conversion value).
- the pre-baked film was pattern-exposed to g, h and i mixed lines of a high-pressure mercury lamp to obtain an exposed film having an exposed portion, a semi-exposed portion and an unexposed portion in its plane.
- the pattern exposure was performed by bringing a positive halftone exposure mask into contact with the surface of the prebaked film.
- development is performed by a paddle method using a compact developing device for photolithography (AD-1200; manufactured by Takizawa Sangyo Co., Ltd.) and a 2.38% by weight aqueous solution of tetramethylammonium hydroxide, which is an alkaline developer. did.
- the puddle method used herein refers to a method in which the surface of the exposed film is shower-coated with an alkaline developer for 10 seconds and then allowed to stand until a predetermined development time is reached for development.
- the development time is within the range of 40 to 90 seconds, and the thickness of the thick film portion of the pixel division layer having a step obtained after the curing process described later is 3.0 ⁇ 0.2 ⁇ m, and the thickness of the thin film portion is 1.0 ⁇ m. 0.5 ⁇ m. Further, after rinsing with deionized water by a shower method for 30 seconds, the substrate was idled at 200 rpm for 30 seconds and dried to obtain a developed film-formed substrate having a developed film having steps.
- FIG. 1 shows an image obtained by observing a cross section of the exposure sensitivity evaluation substrate provided with a pixel dividing layer having steps obtained in Example 16 with a scanning electron microscope (SEM).
- SEM scanning electron microscope
- the thin film portion of the pixel division layer was observed using an FPD inspection microscope (MX-61L; manufactured by Olympus Corporation).
- the required minimum exposure dose (mJ/cm 2 : i-line conversion value) when the opening was within the range of 1 ⁇ m was taken as the exposure sensitivity, and the smaller the value, the better. Evaluation was made based on the following criteria, and A to C were accepted, and D to E were rejected. However, if the film thickness of the thick film portion is 3.0 ⁇ 0.2 ⁇ m and the film thickness of the thin film portion is not 1.5 ⁇ m in the range of the above conditions, the evaluation will be F and fail.
- the value obtained by subtracting the thickness of the thick film portion (unexposed portion) of the developed film having a step from the film thickness of the prebaked film, that is, the film reduction ( ⁇ m) in the development process was also evaluated. If it exceeds 0 ⁇ m, it is excluded from the exposure sensitivity evaluation. In addition, when the silver alloy film could not be visually recognized by the near-infrared camera, the near-infrared alignment was impossible and was excluded from the exposure sensitivity evaluation.
- a negative halftone exposure mask (length: 30.0 ⁇ m, width: 30.0 ⁇ m) was used. 220 square shielding parts are arranged, and when the exposure amount of the full transmission part is 100% and the exposure amount of the shielding part is 0%, the exposure amount of the semi-transmission part is 30%.
- the exposure sensitivity was determined in the same manner except that a mask was used.
- B The exposure sensitivity is 100 mJ/cm 2 or more and less than 150 mJ/cm 2 .
- Exposure sensitivity is 150 mJ/cm 2 or more and less than 200 mJ/cm 2 .
- D Exposure sensitivity is 200 mJ/cm 2 or more and less than 250 mJ/cm 2 .
- Exposure sensitivity is 250 mJ/cm 2 or more and 300 mJ/cm 2 or less.
- F Halftone processing is difficult and fair evaluation is impossible.
- the evaluation was performed on the basis that the larger the value of OD/ ⁇ m, the higher the light-shielding properties of the cured film. As a result of separately measuring the OD value of Tempax on which no cured film was formed, it was 0.00, so the OD value of the substrate for optical property evaluation was regarded as the OD value of the cured film.
- the film thickness of the cured film is measured at three points in the plane using a stylus type film thickness measuring device (Tokyo Seimitsu Co., Ltd.; Surfcom), and the average value is rounded to the first decimal place. I found the numerical value up to the digit.
- the film thickness of the thick film portion is 3.0 ⁇ 0.2 ⁇ m, and the film thickness of the thin film portion is collectively formed to 1.5 ⁇ m.
- the evaluation was set to F, and it was set as failure.
- the exposure sensitivity was 200 mJ/cm 2 or more in the evaluation at least after one day of storage or after 30 days of storage, the evaluation was given as G and failed. When it corresponded to F and G, the evaluation was made into F and it was set as failure.
- B The rate of change in exposure sensitivity is 5% or more and less than 15%.
- C Change rate of exposure sensitivity is 15% or more and less than 30%.
- D The rate of change in exposure sensitivity is 30% or more and less than 40%.
- E Change rate of exposure sensitivity is 40% or more.
- F Halftone processing is difficult and fair evaluation is impossible.
- G The exposure sensitivity is 200 mJ/cm 2 or more in evaluation at least at any point after storage for 1 day or storage for 30 days.
- W3 is 1.2 ⁇ m or more and less than 1.5 ⁇ m.
- D W3 is 1.5 ⁇ m or more and less than 2.0 ⁇ m.
- E W3 is 2.0 ⁇ m or more.
- F Halftone processing is difficult and fair evaluation is impossible.
- polyimide precursor B As a terminal blocking agent, 4.36 g (0.04 mol) of 4-aminophenol was added together with 5 g of NMP and reacted at 50° C. for 2 hours. After that, 50 g of 28.6 g (0.24 mol) of N,N-dimethylformamide dimethylacetal were added. After charging, the mixture was stirred at 50°C for 3 hours. After the stirring was completed, the solution was cooled to room temperature and then poured into 3 L of water to obtain a white precipitate. A white precipitate obtained by repeating the above operation five times was collected as a filtered product, washed with water five times, and then dried in a vacuum dryer at 80° C. for 24 hours to obtain a polyimide precursor B. Polyimide precursor B was component (c-1), had a weight average molecular weight (Mw) of 25,000 and an amine value of 1.0 mgKOH/g.
- polyimide resin C having a structural unit represented by the formula (39) and having no structural unit represented by the formula (39) was obtained.
- Polyimide resin C was component (c-1), had a weight average molecular weight (Mw) of 25,000 and an amine value of 1.0 mgKOH/g.
- the methacrylic resin d was component (c-1) and had a weight average molecular weight (Mw) of 9,500.
- a methacrylic resin solution D was obtained by diluting this with PGMEA so that the solid content was 30% by weight.
- Polyimide resin E having no structural units was obtained.
- Polyimide resin E was component (c-1), had a number average molecular weight (Mw) of 8,200 and an amine value of 1.0 mgKOH/g.
- the triethylamine salt was filtered and the filtrate was poured into water. Filtration was then performed, and the deposited precipitate was collected. This precipitate was dried in a vacuum dryer to obtain the quinonediazide compound a represented by the formula (55) as the component (d).
- the quinonediazide compound a is the component (d).
- * represents a bonding site with an oxygen atom.
- Synthesis Example 7 Synthesis of quinonediazide compound b
- Synthesis was carried out in the same manner as in Synthesis Example 3, except that 36.27 g (0.135 mol) of 5-naphthoquinonediazide sulfonyl chloride was replaced with 36.27 g (0.135 mol) of 4-naphthoquinone diazidesulfonyl chloride. to obtain a quinonediazide compound b represented by the formula (56).
- the quinonediazide compound b is the component (d).
- black pigment 1 500.00 g of black pigment 1, 2.5 kg of grinding material (sodium chloride particles with an average primary particle size of 0.5 ⁇ m that have been heat-treated at 230° C. for 1 hour to make the water content 0.1% by weight in advance), The mixture was mixed with 250.00 g of dipropylene glycol, charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), and kneaded at 90° C. for 8 hours. This kneaded product is put into 5 L of hot water and stirred for 1 hour while maintaining the temperature at 70 ° C.
- grinding material sodium chloride particles with an average primary particle size of 0.5 ⁇ m that have been heat-treated at 230° C. for 1 hour to make the water content 0.1% by weight in advance
- the finely divided perylene black pigment 1 is component (a) and has an average primary particle size of 25 nm, a maximum primary particle size of 98 nm, and an average aspect ratio of 1.1.
- the chemical structure of finely divided perylene black pigment 1 was analyzed using MALDI-TOF MS.
- Pigment Crude 2 500.00 g of Pigment Crude 2 and 2.5 kg of grinding material (sodium chloride particles having an average primary particle size of 0.5 ⁇ m and having a water content of 0.1% by weight in advance by heat treatment at 230° C. for 1 hour), The mixture was mixed with 250.00 g of dipropylene glycol, charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), and kneaded at 90° C. for 10 hours. This kneaded product is put into 5 L of hot water and stirred for 1 hour while maintaining the temperature at 70 ° C.
- grinding material sodium chloride particles having an average primary particle size of 0.5 ⁇ m and having a water content of 0.1% by weight in advance by heat treatment at 230° C. for 1 hour
- the finely divided perylene black pigment 2 is component (a) and has an average primary particle size of 26 nm, a maximum primary particle size of 110 nm, and an average aspect ratio of 1.1.
- the chemical structure of finely divided perylene black pigment 2 was analyzed using MALDI-TOF MS.
- Pigment Crude 3 Thereafter, physical refining treatment by solvent salt milling is performed in the same manner as in Production Example 2, and a finely divided perylene black comprising an isomer mixture of the compound represented by the formula (59) and the compound represented by the formula (60) is obtained. Pigment 3 is obtained.
- the finely divided perylene black pigment 3 is component (a), and has an average primary particle size of 45 nm, an average aspect ratio of 1.3, and a maximum primary particle size of 119 nm.
- the chemical structure of finely divided perylene black pigment 3 was analyzed using MALDI-TOF MS.
- the finely divided perylene black pigment 4 is component (a), and has an average primary particle size of 85 nm, an average aspect ratio of 1.6, and a maximum primary particle size of 125 nm.
- the chemical structure of finely divided perylene black pigment 4 was analyzed using MALDI-TOF MS.
- the micronized dioxazine pigment 1 is component (h) and has an average primary particle size of 34 nm, a maximum primary particle size of 140 nm, and an average aspect ratio of 1.2.
- the chemical structure of micronized dioxazine pigment 1 was analyzed using MALDI-TOF MS.
- the micronized dioxazine pigment 2 is component (h) and has an average primary particle size of 30 nm, a maximum primary particle size of 110 nm, and an average aspect ratio of 1.0.
- the chemical structure of micronized dioxazine pigment 2 was analyzed using MALDI-TOF MS.
- Dye A is component (b-2), and is composed of a compound represented by formula (24), a compound represented by formula (25) and a compound represented by formula (26) at a weight ratio of 42:55:3. A mixture.
- the chemical structure of Dye A was analyzed using MALDI-TOF MS, and the weight ratio of the compounds constituting Dye A was analyzed using LC-MS.
- Dye B is component (b-2), and is composed of a compound represented by formula (24), a compound represented by formula (25) and a compound represented by formula (26) at a weight ratio of 25:65:10. A mixture.
- the chemical structure of Dye B was analyzed using MALDI-TOF MS, and the weight ratio of the compounds constituting Dye B was analyzed using LC-MS.
- Dye D is component (b-1) and is a compound represented by formula (23). The chemical structure of Dye D was analyzed using MALDI-TOF MS.
- Dye E is component (b-2) and is a compound represented by formula (64).
- the chemical structure of Dye E was analyzed using MALDI-TOF MS.
- Dye F is a compound that does not correspond to component (b) and is a compound represented by formula (65).
- the chemical structure of Dye F was analyzed using MALDI-TOF MS.
- Dye G is a compound that does not correspond to component (b) and is a compound represented by formula (66) having an N,N-dialkylaminoalkyl group.
- the chemical structure of Dye G was analyzed using MALDI-TOF MS.
- Dye H Perylene-based dye derivative 8 disclosed in Patent Document 2.
- red precipitate A was a monosulfonate of N,N'-diphenyl-3,4,9,10-perylenedicarboximide.
- the filtrate containing Red Precipitate A was then added to 3 kg of deionized water and stirred to reslurry. Further, a 20% by weight aqueous solution of sodium hydroxide was added stepwise with stirring until the pH of the slurry reached 11.0. Then, a 5% by weight aqueous solution of calcium chloride (manufactured by Sigma-Aldrich) was added stepwise with stirring until the pH of the slurry reached 3.5 to form a red precipitate B, which was filtered off and repeatedly washed with water.
- Dye I is the component (b) and is a compound represented by formula (75).
- Dye J A compound represented by formula (76) synthesized according to Example 7 of European Patent Application Publication No. 0486531 and purified by silica gel chromatography. The chemical structure of Dye J was analyzed using MALDI-TOF MS.
- Dye K Perylene-3-sulfonic acid represented by formula (77) (manufactured by Sigma-Aldrich)
- Table 2 summarizes the number of structures represented by formula (2) in the molecules of the above dyes A to K and the number of functional groups in the molecules.
- the notation of "0" means not having.
- a vertical bead mill “Ultra Apex Mill Advance (registered trademark)” in which 0.05 mm ⁇ zirconia beads “Toreceram (registered trademark)” (manufactured by Toray Industries, Inc.) are filled in the vessel at a filling rate of 75% by volume. (manufactured by Hiroshima Metal & Machinery Co., Ltd.), and subjected to wet media dispersion treatment for 5 hours at a peripheral speed of 10 m / s in a circulation system to obtain a pigment dispersion with a solid content of 10.00% by weight. Obtained. A first filtration was performed with a 0.8 ⁇ m aperture filter, and a second filtration was performed with a 0.2 ⁇ m aperture filter.
- Preparation Examples 2-5 Preparation of Pigment Dispersions 2-5) Wet media dispersion treatment and filtration were performed in the same manner as in Preparation Example 1, except that instead of "Spectrasense (registered trademark)" Black K0087, finely divided perylene black pigments 1 to 4 were used, respectively. Got 5. Table 3 shows the blending weight of each raw material.
- Preparation Examples 6-9 Preparation of Pigment Dispersions 6-9)
- Wet media dispersion treatment and filtration were carried out in the same manner as in Preparation Example 1 except that dyes B to E were used instead of dye A, to obtain pigment dispersions 6 to 9.
- Table 4 shows the blending weight of each raw material.
- Preparation Example 10 Preparation of Pigment Dispersion Liquid 10.
- a wet media dispersion treatment and filtration were performed in the same manner as in Preparation Example 1, except that the polyimide resin C was used instead of the polyimide precursor B, and a pigment dispersion liquid 10 was obtained.
- Table 4 shows the blending weight of each raw material.
- Preparation Examples 11-12 Preparation of Pigment Dispersions 11-12
- Preparation Example 6 wet media dispersion treatment and filtration were carried out in the same manner as in Preparation Example 1, except that the blending ratio of each raw material was changed, to obtain Pigment Dispersions 11 and 12.
- Table 4 shows the blending weight of each raw material.
- Preparation Examples 13-14 Preparation of Pigment Dispersions 13-14
- Wet media dispersion treatment and filtration were carried out in the same manner as in Preparation Example 1, except that dyes F to G were used instead of dye A, to obtain pigment dispersions 13 and 14.
- Table 5 shows the blending weight of each raw material.
- a horizontal bead mill (“DYNO-MILL (registered trademark)” manufactured by Willy A. Bachofen) filled with “Toreceram (registered trademark)” (manufactured by Toray Industries, Inc.), which is zirconia beads of 0.4 mm ⁇ , 30 A wet media dispersion treatment was performed by a minute circulation system.
- a vertical bead mill (“Ultra Apex Mill (registered trademark)” in which 0.05 mm ⁇ zirconia beads “Toreceram (registered trademark)” (manufactured by Toray Industries, Inc.) are filled in the vessel at a filling rate of 75% by volume.
- the average dispersed particle size as used herein means the number average value of the secondary particle sizes of all the pigment particles contained in the pigment dispersion.
- Preparation Example 17 Preparation of Pigment Dispersion Liquid 17
- 30.00 g of "SOLSPERSE (registered trademark)" 20000 manufactured by Lubrizol; solid content 100% by weight; amine value 32 mg KOH/g; polyether resin having N,N-dialkylaminoalkyl groups) and 850.00 g of MBA and stirred for 30 minutes.
- Black S0084 (manufactured by BASF; hereinafter referred to as "Black S0084") is mixed and a high-speed stirrer (Homo Disper 2.5 type; manufactured by Primix Co., Ltd.) is used. Then, a vertical bead mill (“Ultra Apex Mill (registered trademark) "manufactured by Hiroshima Metal & Machinery Co., Ltd.) is fed with the preliminary dispersion liquid and treated at a peripheral speed of 7.0 m / s for 3 hours to disperse the pigment with a solid content of 15.00% by weight. A liquid 17 was obtained.
- Example 1 Under yellow light, 0.83 g of polyimide as component (c-1) was added to 8.03 g of mixed solvent (PGME, ethyl lactate and ⁇ -butyrolactone; weight ratio 50:40:10) as component (e).
- PGME mixed solvent
- e ethyl lactate and ⁇ -butyrolactone
- Precursor B 1.27 g of quinonediazide compound a, 0.15 g of quinonediazide compound b, 0.68 g of 4,4′,4′′-trihydroxytriphenylmethane as component (f), and (g ) component 0.75 g of HMOM-TPHAP (manufactured by Honshu Chemical Industry Co., Ltd.; compound represented by formula (68)) and 0.05 g of BYK-333 (BYK Chemie Japan Co., Ltd.) as a leveling agent PGME solution with a solid content of 5% by weight was added and stirred for 30 minutes to dissolve.Furthermore, 38.25 g of pigment dispersion liquid 1 was added and stirred for 30 minutes to obtain a positive solid content of 15.00% by weight. Thus, a type photosensitive pigment composition 1 was obtained.Table 6 shows the blending weight of each raw material.
- each of the positive photosensitive pigment composition 1 was added to two 50 mL light-shielding glass bottles, sealed and stored (under atmospheric pressure/under light shielding/closed in a cool dark place maintained at -20 ⁇ 1 ° C. left undisturbed). After storage for 1 day, one side was taken out of the cold and dark place and brought to room temperature (23° C.), and the exposure sensitivity was evaluated by the method described above.
- the positive photosensitive pigment composition 1 is applied to the surface of a transparent glass substrate "Tempax (manufactured by AGC Techno Glass Co., Ltd.), and the resulting cured film has a thickness of 1.5 ⁇ m.
- a coating film was obtained by coating with a spin coater while adjusting the number of rotations as follows: A coating film was formed at 110° C. under atmospheric pressure for 120 seconds using a hot plate (SCW-636; manufactured by Dainippon Screen Mfg. Co., Ltd.).
- a pre-baked film was obtained.
- g, h, i mixed lines of an extra-high pressure mercury lamp correspond to 15% of the exposure sensitivity (required minimum exposure amount) determined by the above method.
- the entire surface of the pre-baked film was irradiated with the exposure amount to obtain an exposed film.
- Development, rinsing and drying were performed in the same manner as in the evaluation of the exposure sensitivity to obtain a solid developed film.
- High-temperature inert gas oven (INH- Using 9CD-S; manufactured by Koyo Thermo Systems Co., Ltd.), the developed film was heated at 250° C.
- the optical density (OD/ ⁇ m) and the maximum transmittance at a wavelength of 410 to 440 nm were evaluated by the method described above.
- a pixel division layer made of a cured film of the positive photosensitive pigment composition 1 and an organic EL display device having a pixel division layer were produced by the following method.
- FIG. 3 shows the manufacturing process of the organic EL display device including the process of forming the pixel division layer.
- a silver alloy (99.00% by weight silver and 1.00% by weight copper alloy) was deposited on the entire surface of the non-alkali glass substrate 13 with a length of 70 mm and a width of 70 mm by sputtering.
- etching was performed by immersing in a silver alloy etching solution SEA-1 at a liquid temperature of 30° C. to obtain a patterned silver alloy film 14 with a film thickness of 50 nm.
- an ITO film indium-tin oxide
- the positive photosensitive pigment composition 1 was applied using a spin coater so that the thickness of the thick film portion of the finally obtained pixel division layer having steps was 3.0 ⁇ 0.2 ⁇ m, and the thickness of the thin film portion was 1.0 ⁇ m. The number of revolutions was adjusted so that the thickness would be 0.5 ⁇ m, and the coating was applied to the surface of the first electrode forming substrate to obtain a coating film. Furthermore, using a hot plate, the coating film is pre-baked at 110 ° C.
- a near-infrared camera (light source wavelength: 800 nm) is used to use a positive halftone exposure mask (longitudinal: 220 square fully-transmissive portions of 30.0 ⁇ m and 30.0 ⁇ m in width are arranged. A mask designed to be 15%) was aligned.
- An exposed film was obtained by subjecting the pre-baked film to pattern exposure through a positive halftone exposure mask with the required minimum exposure amount (exposure sensitivity) determined by the method described above. The pattern exposure was performed by bringing a positive halftone exposure mask into contact with the surface of the prebaked film.
- the pixels are exposed to the deposition source under deposition conditions with a degree of vacuum of 1 ⁇ 10 ⁇ 3 Pa or less.
- the split layer forming substrate is rotated, and first, the compound (HT-1) represented by the formula (69) is deposited to 10 nm as the hole injection layer, and the compound (HT-1) represented by the formula (70) is deposited as the hole transport layer. -2) was deposited to a thickness of 50 nm.
- the compound (GH-1) represented by the formula (71) as a host material and the compound (GD-1) represented by the formula (72) as a dopant material were applied to a thickness of 40 nm on the light-emitting layer. evaporated.
- the compound (ET-1) represented by the formula (73) and the compound (LiQ) represented by the formula (74) as electron transport materials were laminated at a volume ratio of 1:1 to a thickness of 40 nm.
- a silver/magnesium alloy (volume ratio: 10:1) was vapor-deposited to a thickness of 150 nm to form the second electrode 18 .
- a cap-shaped glass plate was adhered and sealed using an epoxy resin adhesive to obtain an organic EL display device in which green light emitting pixels were arranged.
- Each layer constituting the organic EL layer 17 is much thinner than the pixel division layer described above, and a stylus-type film thickness measuring device cannot obtain high measurement accuracy.
- Table 7 shows the results of evaluation of luminance unevenness of the manufactured organic EL display device by the method described above.
- Examples 2-6 Using the pigment dispersions 2 to 5 instead of the pigment dispersion 1, positive photosensitive pigment compositions 2 to 10 were prepared in the amounts shown in Table 6, respectively, and exposure sensitivity and curing were performed in the same manner as in Example 1.
- Example 7-10 Using pigment dispersions 6 to 9 instead of pigment dispersion 1, positive photosensitive pigment compositions 7 to 10 were prepared in the amounts shown in Table 8, respectively, and exposure sensitivity and curing were performed in the same manner as in Example 1.
- Pigment Dispersion 10 was used instead of Pigment Dispersion 1
- Polyimide Resin C was used instead of Polyimide Precursor B
- positive photosensitive pigment composition 11 was prepared in the amounts shown in Table 10.
- the exposure sensitivity, the light shielding property of the cured film, the maximum transmittance at a wavelength of 410 to 440 nm, the storage stability, the halftone workability, and the luminance unevenness of the organic EL display device were evaluated by the same methods as described above. Table 11 shows the evaluation results.
- Example 12 Pigment Dispersion 6 was used instead of Pigment Dispersion 1, Polyimide Resin C was used instead of Polyimide Precursor B, and positive photosensitive pigment composition 12 was prepared in the amounts shown in Table 10.
- the exposure sensitivity, the light shielding property of the cured film, the maximum transmittance at a wavelength of 410 to 440 nm, the storage stability, the halftone workability, and the luminance unevenness of the organic EL display device were evaluated by the same methods as described above. Table 11 shows the evaluation results.
- Example 13-14 Pigment dispersions 11 and 12 were used instead of pigment dispersion 1, and positive photosensitive pigment composition 12 was prepared at the blending amounts shown in Table 10, and exposure sensitivity and light shielding properties of the cured film were measured in the same manner as in Example 1. Also, maximum transmittance at a wavelength of 410 to 440 nm, storage stability, halftone workability, and luminance unevenness of the organic EL display device were evaluated. Table 11 shows the evaluation results.
- Example 15 shows the evaluation results.
- Preparation Example 18 Preparation of Pigment Dispersion Liquid 18
- polyimide precursor B as component (c-1) was added to 900.00 g of mixed solvent (PGME, ethyl lactate and ⁇ -butyrolactone; weight ratio 50:40:10) as component (e). added and stirred for 30 minutes to dissolve.
- PGME mixed solvent
- dye B as component (b-2)
- stirring for 30 minutes 18.92 g of finely divided perylene black pigment 1 as component (a) and 8.11 g of finely divided Dioxazine pigment 1 was added and stirred for 30 minutes to obtain a pre-stirred liquid.
- a vertical bead mill “Ultra Apex Mill Advance (registered trademark)” in which 0.4 mm ⁇ zirconia beads “Toreceram (registered trademark)” (manufactured by Toray Industries, Inc.) are filled in the vessel at a filling rate of 75% by volume. (manufactured by Hiroshima Metal & Machinery Co., Ltd.), and subjected to wet media dispersion treatment for 1 hour at a peripheral speed of 10 m/s in a circulation system.
- the liquid was sent to a vertical bead mill filled with 0.1 mm ⁇ zirconia beads “Toreceram (registered trademark)” (manufactured by Toray Industries, Inc.) at a filling rate of 75% by volume in the vessel, and the peripheral speed was A wet media dispersion treatment was performed at 8 m/s for 4 hours to obtain a pigment dispersion having a solid content of 10.00% by weight.
- a first filtration was performed with a 0.8 ⁇ m aperture filter, and a second filtration was performed with a 0.2 ⁇ m aperture filter.
- Preparation Example 19 Preparation of Pigment Dispersion Liquid 19
- Wet media 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.
- Component: (c) resin weight ratio 70:30:17:253, pigment dispersion 19 having a solid content of 10.00% by weight was obtained.
- Table 16 shows the blending weight of each raw material.
- Preparation Example 20 Preparation of Pigment Dispersion Liquid 20
- Wet media 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.
- Component: (c) resin weight ratio 55:45:17:253, pigment dispersion 20 having a solid content of 10.00% by weight was obtained.
- Table 16 shows the blending weight of each raw material.
- Example 15-17 Using pigment dispersions 18 to 20 instead of pigment dispersion 1, positive photosensitive pigment compositions 20 to 22 were prepared in the amounts shown in Table 17, respectively, and exposure sensitivity and curing were performed in the same manner as in Example 1.
- Table 18 shows the evaluation results.
- Preparation Examples 21-23 Wet media dispersion was carried out in the same manner as in Preparation Example 1, except that Micronized Perylene Black Pigment 1 was used in place of "Spectrasense (registered trademark)" Black K0087, and Colorants I, J and K were used in place of Colorant A. Work-up and filtration provided Pigment Dispersions 21-23. Table 19 shows the blending weight of each raw material.
- Example 18 Pigment Dispersion Liquid 21 was used in place of Pigment Dispersion Liquid 1 to prepare positive photosensitive pigment composition 23 at the blending amounts shown in Table 20, and the exposure sensitivity and light shielding properties of the cured film were measured in the same manner as in Example 1. Also, maximum transmittance at a wavelength of 410 to 440 nm, storage stability, halftone workability, and luminance unevenness of the organic EL display device were evaluated. Table 21 shows the evaluation results.
- Pigment dispersion 22 was used in place of pigment dispersion 1 to prepare positive photosensitive pigment composition 24 at the blending amounts shown in Table 20, and the exposure sensitivity and light shielding properties of the cured film were measured in the same manner as in Example 1. Also, maximum transmittance at a wavelength of 410 to 440 nm, storage stability, halftone workability, and luminance unevenness of the organic EL display device were evaluated. Table 21 shows the evaluation results.
- Pigment Dispersion Liquid 23 was used in place of Pigment Dispersion Liquid 1 to prepare Positive Type Photosensitive Pigment Composition 25 at the blending amounts shown in Table 20.
- the viscosity of the positive photosensitive pigment composition 25 increased markedly. The coatability was poor, and the preparation of the pre-baked film and the halftone process were difficult.
- Example 19 Using Pigment Dispersion 19 instead of Pigment Dispersion 1, and using 4-aminobenzenesulfonic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as component (I), a positive type was prepared in the amount shown in Table 20.
- a photosensitive pigment composition 26 was prepared, and the exposure sensitivity, the light shielding property of the cured film, the maximum transmittance at a wavelength of 410 to 440 nm, the storage stability, the halftone processability and the brightness of the organic EL display device were measured in the same manner as in Example 1. Evaluated unevenness. Table 21 shows the evaluation results.
- Example 9 Using the positive photosensitive resin composition (PB-1) disclosed in Example 1 of WO 2021/182499, an attempt was made to evaluate the exposure sensitivity in the same manner as in Example 1, but the near-infrared camera It was difficult to align the positive halftone exposure mask using , and was excluded from the evaluation. Also, pre-baked films were formed on the first electrode forming substrate so as to have thicknesses of 2.0, 3.0 and 4.0 ⁇ m, respectively, but in all cases it was difficult to align the positive halftone exposure mask. , it was impossible to fabricate an organic EL display device by the same method as in Example 1.
- the positive photosensitive pigment composition of the present invention the cured film containing the cured product of the positive photosensitive pigment composition, and the organic EL display device having the same are useful.
- the positive photosensitive pigment composition of the present invention is used for applications where it is required to stably form a cured film with high exposure sensitivity and high definition, such as a pixel division layer of an organic EL display device and a TFT of an organic EL display device.
- Flattening layer, partition wall of quantum dot organic EL display device (QD-OLED), flattening layer of micro LED display, black matrix of liquid crystal display device, black column spacer of liquid crystal display device, near-infrared transmissive visible of solid-state imaging device It can be preferably used as a material for forming light shielding films, black bezels of display devices, and the like. Among others, it can be particularly preferably used as a material for forming a pixel dividing layer provided in an organic EL display device equipped with a bendable flexible display.
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Abstract
Description
以上から、近赤外線を用いた露光マスクのアライメントが可能であり、ハーフトーン加工性に優れ、高い露光感度と高い保存安定性とを兼ね備えた感光性組成物が切望されていた。また、画素分割層の開口部の開口幅が小さい場合であっても輝度ムラが抑制された有機EL表示装置が切望されていた。
(a)式(1)で表される構造を分子内に2つ有し、ペリレン骨格を分子内に1つ有する化合物を含有する顔料(以下、「(a)成分」という場合がある。)、(b)式(2)で表される構造を有し、N,N-ジアルキルアミノアルキル基を有さない化合物またはその金属塩(以下、「(b)成分」という場合がある。)、(c)樹脂(以下、「(c)成分」という場合がある。)、(d)光酸発生剤(以下、「(d)成分」という場合がある。)および(e)有機溶剤(以下、「(e)成分」という場合がある。)を含有するポジ型感光性顔料組成物、である。
前記ポジ型感光性顔料組成物の硬化物を含有する硬化膜、である。
前記硬化膜を具備する有機EL表示装置、である。
中でも、高い露光感度を得る上で、式(12)で表される化合物を含有する顔料が好ましい。
ここでいう有機色素化合物とは、有機染料および有機顔料を意味する。
また、式(39)で表される構造単位を有する樹脂の含有量は、露光感度と保存安定性を向上する上で、(c)樹脂中、50重量%以上が好ましく、80重量%以上がより好ましい。
試料を100mLの三角フラスコに溶媒(γ-ブチロラクトン)60mLを加えて溶解させ、電位差滴定装置AT-710およびガラス電極C-173(いずれも京都電子工業(株)製)を用いて、滴定液(0.1mol/L塩酸)で滴定を行い、得られた変曲点を終点とする。別途、同様の方法で試料を含有させずブランク滴定を行い、下記式からアミン価を算出する。
上式中、S:試料((c)樹脂)の質量(g)、V0:ブランク滴定で要した滴定液の量(mL)、V1:試料の滴定で要した滴定液の量(mL)、f:滴定液のファクター(1.006)である。
上式中、I0:入射光強度、I:透過光強度である。
縦150mm/横150mmの無アルカリガラス基板の表面に、スパッタ法により銀合金(99.00重量%の銀と、1.00重量%の銅からなる合金)を全面成膜した。さらに、スパッタ法によりITO膜を全面成膜し、無アルカリガラス基板の表面の全面に銀合金膜/ITO膜を具備するガラス基板を得た。
A:露光感度が、40mJ/cm2以上、100mJ/cm2未満である。
B:露光感度が、100mJ/cm2以上、150mJ/cm2未満である。
C:露光感度が、150mJ/cm2以上、200mJ/cm2未満である。
D:露光感度が、200mJ/cm2以上、250mJ/cm2未満である。
E:露光感度が、250mJ/cm2以上、300mJ/cm2以下である。
F:ハーフトーン加工が困難であり正当な評価が不可能。
実施例1~19、比較例1~7で得られた膜厚1.5μmの硬化膜を形成した光学特性評価用基板について、光学濃度計(X-Rite社製;X-Rite 361T)を用いて膜面側から面内3箇所において全光学濃度(Total OD値)を測定して平均値を算出し、その数値を1.5で除した値を、小数点第二位を四捨五入した小数点第一位までの数値を、硬化膜の厚さ1.0μmあたりのOD値(OD/μm)とした。OD/μmの値が大きいほど遮光性が高く優れた硬化膜であるとの基準で評価を行った。硬化膜を形成していないテンパックスのOD値を別途測定した結果、0.00であったため、光学特性評価用基板のOD値を、硬化膜のOD値とみなした。硬化膜の膜厚は、触針式膜厚測定装置(東京精密(株);サーフコム)を用いて面内3箇所において測定し、その平均値の小数点第二位を四捨五入して、小数点第一位までの数値を求めた。
実施例1~19、比較例1~5および比較例7で得られたポジ型感光性顔料組成物1~24、26、比較例6で得られたネガ型感光性顔料組成物1を用いて得られた膜厚1.5μmの硬化膜を形成した光学特性評価用基板について、紫外可視分光光度計「UV-260(島津製作所(株)製)」を用いて、波長380~780nmの範囲における透過率を波長1nmごとに測定した。波長410~440nmにおける最大透過率(%)を面内3箇所において測定した値の平均値を算出し、その値が小さいほど優れた硬化膜であるとの基準で評価を行った。
実施例1~19、比較例1~5および比較例7で得られたポジ型感光性顔料組成物1~24、26、および比較例6で得られたネガ型感光性顔料組成物1について、調製してから30日間貯蔵後の露光感度の値から、1日間貯蔵後の露光感度の値を差し引いた値を、1日間貯蔵後の露光感度の値で除して、さらに100を乗じた値の小数点第一位を四捨五入した値を、露光感度の変化率(%)とした。露光感度の変化率が小さいほど保存安定性が高く優れているとし、以下の判定基準に基づいて評価し、A~Cを合格、D~Eを不合格とした。ただし、調製してから1日間貯蔵後または30日間貯蔵後の少なくともいずれかの場合において、厚膜部の膜厚が3.0±0.2μm、薄膜部の膜厚が1.5μmに一括形成できなかった場合は、その評価をFとし、不合格とした。また、1日間貯蔵後または30日間貯蔵後、少なくともいずれかの時点での評価において露光感度が200mJ/cm2以上であった場合は、その評価をGとし、不合格とした。FかつGに相当する場合、その評価をFとし、不合格とした。
A:露光感度の変化率が、5%未満である。
B:露光感度の変化率が、5%以上、15%未満である。
C:露光感度の変化率が、15%以上、30%未満である。
D:露光感度の変化率が、30%以上、40%未満である。
E:露光感度の変化率が、40%以上である。
F:ハーフトーン加工が困難であり正当な評価が不可能。
G:1日間貯蔵後または30日間貯蔵後、少なくともいずれかの時点での評価において露光感度が200mJ/cm2以上である。
実施例1~19、比較例1~3、および比較例6~7で得られた画素分割層形成基板について、FPD検査顕微鏡を用いて観察し、面内10箇所の開口部の開口幅を測長した。最大開口幅W1(μm)から最小開口幅W2(μm)を差し引いた値W3(μm)が小さいほど優れているとし、以下の判定基準に基づいて評価し、A~Cを合格、D~Eを不合格とした。ただし、厚膜部の膜厚が3.0±0.2μm、薄膜部の膜厚が1.5μmに一括形成できなかった場合は、その評価をFとし、不合格とした。
A:W3が、1.0μm未満である。
B:W3が、1.0μm以上、1.2μm未満である。
C:W3が、1.2μm以上、1.5μm未満である。
D:W3が、1.5μm以上、2.0μm未満である。
E:W3が、2.0μm以上である。
F:ハーフトーン加工が困難であり正当な評価が不可能。
実施例1~19、比較例1~3、および比較例6~7で得られた有機EL表示装置を、10mA/cm2の直流駆動により発光させて、縦30mm/横30mmのエリア内に形成した画素部において中央部に位置する画素部30箇所を、倍率50倍でモニター上に拡大表示させて観察し、面内の輝度のムラを以下の判定基準に基づいて評価し、A~Cを合格、D~Eを不合格とした。ただし、非点灯画素が1箇所以上観られた場合は、その評価をEとし、不合格とした。
A:輝度ムラが観られない。
B:輝度ムラが僅かに観られる。
C:輝度ムラが観られる。
D:輝度ムラが顕著に観られる。
E:非点灯画素が1箇所以上観られる。
18.3g(0.05 mol)の2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパンを、100mLのアセトン、17.4g(0.3mol)のプロピレンオキシドに溶解させ、-15℃に冷却した。ここに0.11mol(20.4g)の3-ニトロベンゾイルクロリドを、100mLのアセトンに溶解させた溶液を滴下した。滴下終了後、-15℃で4時間反応させて、その後室温に戻した。析出した白色固体を濾別し、50℃で真空乾燥した。固体30gを300mLのステンレスオートクレーブに入れ、メチルセロソルブ250mLに分散させ、5%パラジウム-炭素を2g加えた。ここに水素を風船で導入して、還元反応を室温で行なった。約2時間後、風船がこれ以上しぼまないことを確認して反応を終了させた。反応終了後、濾過して触媒であるパラジウム化合物を除き、ロータリーエバポレーターで濃縮し、式(54)で表されるヒドロキシル基含有ジアミン化合物Aを得た。
乾燥窒素気流下、31.0g(0.10mol)の3,3’,4,4’-ジフェニルエーテルテトラカルボン酸二無水物を、500gのNMPに溶解させた。ここに合成例1で得られた45.35g(0.075mol)のヒドロキシル基含有ジアミン化合物Aと、1.24g(0.005mol)の1,3-ビス(3-アミノプロピル)テトラメチルジシロキサンを、50gのNMPとともに加えて、20℃で1時間反応させ、次いで50℃で2時間反応させた。末端封止剤として、4.36g(0.04mol)の4-アミノフェノールを、5gのNMPとともに加え、50℃で2時間反応させた。その後、28.6g(0.24mol)のN,N-ジメチルホルムアミドジメチルアセタールを50g投入した。投入後、50℃で3時間撹拌した。撹拌終了後、溶液を室温まで冷却した後、溶液を3Lの水に投入して白色沈殿を得た。以上の操作を5回繰り返して得られた白色沈殿を濾物として集め、水で5回洗浄した後、80℃の真空乾燥機で24時間乾燥させ、ポリイミド前駆体Bを得た。ポリイミド前駆体Bは(c-1)成分であり、重量平均分子量(Mw)は25,000であり、アミン価は1.0mgKOH/gであった。
乾燥窒素気流下、150.15g(0.41mol)の2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン、6.20g(0.02mol)の1,3-ビス(3-アミノプロピル)テトラメチルジシロキサン、および末端封止剤である13.65g(0.13mol)の3-アミノフェノールを、500.00gのNMPに溶解し、そこに155.10g(0.50mol)のビス(3,4-ジカルボキシフェニル)エーテル二無水物、および150.00gのNMPを加えて20℃で1時間撹拌し、さらに水を除去しながら180℃で4時間撹拌した。反応終了後、反応液を10Lの水に投入し、生成した沈殿物を濾過して集め、水で5回洗浄し、80℃ の真空乾燥機で20時間乾燥して、式(38)で表される構造単位を有し、式(39)で表される構造単位を有さないポリイミド樹脂Cを得た。ポリイミド樹脂Cは(c-1)成分であり、重量平均分子量(Mw)は25,000であり、アミン価は1.0mgKOH/gであった。
特許文献2の合成例2を参照し、以下の方法でメタクリル系樹脂溶液Dを得た。
乾燥窒素気流下、58.60g(0.16mol)の2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン、末端封止剤として8.73g(0.08mol)の3-アミノフェノールを、300.00gのNMPに溶解した。ここに、62.04g(0.20mol)の3,3’,4,4’-ジフェニルエーテルテトラカルボン酸二無水物を、100.00gのNMPとともに添加し、20℃で1時間攪拌し、次いで50℃で4時間攪拌した。その後、キシレンを15g添加し、水をキシレンとともに共沸しながら、150℃で5時間撹拌した。撹拌終了後、溶液を水5Lに投入して白色沈殿を集めた。この沈殿を濾過で集めて、水で3回洗浄した後、80℃の真空乾燥機で24時間乾燥し、式(38)で表される構造単位を有し、式(39)で表される構造単位を有さないポリイミド樹脂Eを得た。ポリイミド樹脂Eは(c-1)成分であり、数平均分子量(Mw)は8,200であり、アミン価は1.0mgKOH/gであった。
乾燥窒素気流下、21.22g(0.05mol)のTrisP-PA(本州化学工業(株)製) と、36.27g(0.135mol)の5-ナフトキノンジアジドスルホニル酸クロリドを、450gの1,4-ジオキサンに溶解させ、室温にした。ここに、15.18gのトリエチルアミンを、50gの1,4 -ジオキサンに溶解させた液を、系内が35℃以下となるように滴下した。滴下後30℃で2時間攪拌した。トリエチルアミン塩を濾過し、濾液を水に投入した。その後濾過を行い、析出した沈殿物を集めた。この沈殿物を真空乾燥機で乾燥させ、(d)成分である式(55)で表されるキノンジアジド化合物aを得た。キノンジアジド化合物aは(d)成分である。
36.27g(0.135mol)の5-ナフトキノンジアジドスルホニル酸クロリドに替えて、36.27g(0.135mol)の4-ナフトキノンジアジドスルホニル酸クロリドを用いた以外は合成例3と同じ方法で合成を行い、式(56)で表されるキノンジアジド化合物bを得た。キノンジアジド化合物bは(d)成分である。
1,000.00gの“Spectrasense(登録商標)”Black K0087(BASF社製)を、大気圧下/空気下250℃のオーブンで1時間加熱し、室温となるまで冷却した後にボールミルで乾燥凝集を解きほぐし、紫味がかった黒色顔料1を得た。次いで、以下の手順でソルベントソルトミリングによる物理的微細化処理を行った。
70℃で融解させた2,648.16gのフェノール中に、588.48g(1.50mol)のペリレン-3,4,9,10-テトラカルボン酸二無水物と、408.60g(3.00mol)の4,5-ジメチル-1,2-フェニレンジアミンと、64.61gのピペラジンとを添加した混合物を、攪拌を維持しながら液温を170℃に昇温した。次いで、170℃の加熱条件で8時間撹拌を行い、反応を十分に進行させた後、生成した水をフェノールとの共沸混合物として蒸留分離した。次いで、130℃に冷却し、エタノール500gを50gずつ段階的に添加し、60℃で1時間撹拌した後に反応生成物を濾別した。濾液が透明になるまでエタノールで洗浄した後に水洗し、減圧下80℃で24時間乾燥させて、顔料クルード2を得た。次いで、以下の手順でソルベントソルトミリングによる物理的微細化処理を行った。
70℃で融解させた2,648.16gのフェノール中に、588.48g(1.50mol)のペリレン-3,4,9,10-テトラカルボン酸二無水物と、378.30g(3.00mol)の4-フルオロ-1,2-フェニレンジアミンと、64.61gのピペラジンとを添加した混合物を、攪拌を維持しながら液温を170℃に昇温した。次いで、170℃の加熱条件で8時間撹拌を行い、反応を十分に進行させた後、生成した水をフェノールとの共沸混合物として蒸留分離した。次いで、130℃に冷却し、エタノール500gを50gずつ段階的に添加し、60℃で1時間撹拌した後に反応生成物を濾別した。濾液が透明になるまでエタノールで洗浄した後に水洗し、減圧下80℃で24時間乾燥させて、顔料クルード3を得た。以降は製造例2と同じ方法でソルベントソルトミリングによる物理的微細化処理を行い、式(59)で表される化合物および式(60)で表される化合物の異性体混合物からなる微細化ペリレンブラック顔料3を得た。
70℃で融解させた2,648.16gのフェノール中に、588.48g(1.50mol)のペリレン-3,4,9,10-テトラカルボン酸二無水物と、474.60g(3.00mol)の1,8-ジアミノナフタレンと、64.61gのピペラジンとを添加した混合物を、攪拌を維持しながら液温を170℃に昇温した。次いで、170℃の加熱条件で8時間撹拌を行い、反応を十分に進行させた後、生成した水をフェノールとの共沸混合物として蒸留分離した。次いで、130℃に冷却し、エタノール500gを50gずつ段階的に添加し、60℃で1時間撹拌した後に反応生成物を濾別した。濾液が透明になるまでエタノールで洗浄した後に水洗し、減圧下80℃で24時間乾燥させて、顔料クルード4を得た。以降は製造例2と同じ方法でソルベントソルトミリングによる物理的微細化処理を行い、式(61)で表される化合物および式(62)で表される化合物の異性体混合物からなる微細化ペリレンブラック顔料4を得た。
1,000.00gのC.I.ピグメントブルー80(クラリアント社製)を、大気圧下/空気下200℃のオーブンで1時間加熱した後に、室温となるまで冷却した後にボールミルで乾燥凝集を解きほぐし、紫味がかった青色のジオキサジン顔料である青色顔料1を得た。次いで、以下の手順でソルベントソルトミリングによる物理的微細化処理を行った。
1,000.00gの“Cromophtal(登録商標)”Violet D5700(BASF社製:C.I.ピグメントバイオレット37)を、大気圧下/空気下200℃のオーブンで1時間加熱した後に、室温となるまで冷却した後にボールミルで乾燥凝集を解きほぐし、紫色のジオキサジン顔料である紫色顔料1を得た。次いで、以下の手順でソルベントソルトミリングによる物理的微細化処理を行った。
なお、微細化ジオキサジン顔料2は(h)成分であり、平均一次粒子径30nm、最大一次粒子径110nm、平均アスペクト比1.0である。なお、微細化ジオキサジン顔料2の化学構造はMALDI-TOF MSを用いて分析した。
顆粒状の色素であるDaiwa Red 178(ダイワ化成(株)製)を乳鉢で磨り潰し、ステンレス製ふるい濾過器(開口径38μm)にかけて粗大分を除去して得られた50.00gのパウダーを、950.00gのPGME:水=重量比1:1混合溶液に添加して30分間撹拌して予備攪拌液を得た。1.0mmφのジルコニアビーズ(“トレセラム(登録商標)”東レ(株)製)が充填率75体積%でベッセル内に充填された横型ビーズミル(“DYNO-MILL(登録商標)”Willy A.Bachofen社製)に予備攪拌液を送液し、循環方式で湿式メディア分散処理を周速10m/sで2時間行った後、濾過フィルタに通液させた薄い赤色の濾液を廃棄し、イオンクロマトグラフィで定量される硫酸イオンが50ppmを下回るまで水洗を行い、濾物を集めた。濾物を減圧下80℃で24時間乾燥させて、固形分100%のパウダー状の色素Aを得た。色素Aは(b-2)成分であり、式(24)で表される化合物、式(25)で表される化合物および式(26)で表される化合物の重量比率42:55:3の混合物である。なお、色素Aの化学構造はMALDI-TOF MSを用いて分析し、色素Aを構成する化合物の重量比率はLC-MSを用いて分析した。
50.00gのC.I.ピグメントレッド178を、500.00gの80重量%濃硫酸に溶解させて加熱し、液温70℃で6時間攪拌を行い、スルホン化反応を進行させた。次いで、5kgの氷水の中に投入して析出物を含むスラリーを得て濾過を行った。次いで、濾物をエタノールで洗浄した後に、硫酸イオンの残存量が50重量ppmを下回るまで繰り返し水洗を行い、減圧下80℃で24時間乾燥させた。さらに、ナノジェットマイザー((株)アイシンナノテクノロジーズ製)を用いて乾式粉砕処理を行い、ステンレス製ふるい濾過器(開口径50μm)にかけて粗大分を除去し、パウダー状の色素Bを得た。色素Bは(b-2)成分であり、式(24)で表される化合物、式(25)で表される化合物および式(26)で表される化合物の重量比率25:65:10の混合物である。なお、色素Bの化学構造はMALDI-TOF MSを用いて分析し、色素Bを構成する化合物の重量比率はLC-MSを用いて分析した。
50.00gのC.I.ピグメントブラック31を、500.00gの80重量%濃硫酸に溶解させて加熱し、液温60℃で4時間攪拌を行い、スルホン化反応を進行させた。以降の工程は合成例6と同様の方法で行い、パウダー状の色素Cを得た。色素Cは(b-1)成分であり、式(21)で表される化合物および式(63)で表される化合物の重量比率33:67の混合物である。なお、色素Cの化学構造はMALDI-TOF MSを用いて分析し、色素Cを構成する化合物の重量比率はLC-MSを用いて分析した。
196.16g(0.50mol)のペリレン-3,4,9,10-テトラカルボン酸二無水物と、151.16g(1.00mol)の3-(アミノメチル)安息香酸とを、100℃で融解させた1,961.60gのイミダゾール中に添加し、窒素雰囲気下で130℃の加熱温度で6時間攪拌してイミド化反応を進行させた。得られた反応生成物を10℃に冷却した後、5kgの氷水の中に投入して析出物を含むスラリーを得て濾過を行った。次いで、濾物をエタノールで洗浄した後に水洗を行い、減圧下80℃で24時間乾燥させた。さらに、ナノジェットマイザーを用いて乾式粉砕処理を行い、ステンレス製ふるい濾過器(開口径50μm)にかけて粗大分を除去し、パウダー状の色素Dを得た。色素Dは(b-1)成分であり、式(23)で表される化合物である。なお、色素Dの化学構造はMALDI-TOF MSを用いて分析した。
134.09g(0.50mol)のナフタレン-1,4,5,8-テトラカルボン酸二無水物と、291.33g(1.00mol)の3-[(4-アミノ-3-メチルフェニル)アゾ]ベンゼンスルホン酸とを、100℃で融解させた1340.90gのイミダゾール中に添加して加熱し、窒素雰囲気下、液温150℃で6時間攪拌してイミド化反応を進行させた。得られた反応生成物を10℃に冷却した後、5kgの氷水の中に投入して析出物を含むスラリーを得て濾過を行った。次いで、濾物をエタノールで洗浄した後に水洗を行い、減圧下80℃で24時間乾燥させた。さらに、ナノジェットマイザーを用いて乾式粉砕処理を行い、ステンレス製ふるい濾過器(開口径50μm)にかけて粗大分を除去し、パウダー状の色素Eを得た。色素Eは(b-2)成分であり、式(64)で表される化合物である。なお、色素Eの化学構造はMALDI-TOF MSを用いて分析した。
50.00gのC.I.ピグメントイエロー138を、250.00gの11重量%の発煙硫酸に溶解させて加熱し、液温90℃で6時間攪拌を行い、スルホン化反応を進行させた。25℃まで冷却した後に500gの水の中に投入して析出物を含むスラリーを得て濾過を行った。次いで、濾物を硫酸イオンの残存量が50重量ppmを下回るまで繰り返し水洗を行い、減圧下90℃で24時間乾燥させた。さらに、ナノジェットマイザーを用いて乾式粉砕処理を行い、ステンレス製ふるい濾過器(開口径50μm)にかけて粗大分を除去し、パウダー状の色素Fを得た。色素Fは(b)成分に相当しない化合物であり、式(65)で表される化合物である。なお、色素Fの化学構造はMALDI-TOF MSを用いて分析した。
78.46g(0.20mol)のペリレン-3,4,9,10-テトラカルボン酸二無水物と、34.73g(0.27mol)の3-ジエチルアミノプロピルアミンとを、1307.73gのo-ジクロロベンゼンに添加し、液温120℃で3時間攪拌を行い、イミド化反応を進行させた。減圧蒸留によりo-ジクロロベンゼンを除去し、アセトンで洗浄した後に、水洗および濾過を行い、減圧下90℃で24時間乾燥させた。さらに、ナノジェットマイザーを用いて乾式粉砕処理を行い、ステンレス製ふるい濾過器(開口径50μm)にかけて粗大分を除去し、パウダー状の色素Gを得た。色素Gは(b)成分に相当しない化合物であり、N,N-ジアルキルアミノアルキル基を有する、式(66)で表される化合物である。なお、色素Gの化学構造はMALDI-TOF MSを用いて分析した。
50.00gのN,N’-ジフェニル-3,4,9,10-ペリレンジカルボキシミド(Sigma-Aldrich社製)を、500.00gの70重量%濃硫酸に溶解させて加熱し、液温70℃で3時間攪拌を行い、スルホン化反応を進行させた。液温40℃に冷却した後に5kgの氷水の中に投入して赤色析出物を含むスラリーを得て濾過を行った。エタノールおよび脱イオン水で洗浄して濾過を行い、赤色析出物Aを濾物として得た。MALDI-TOF MSを用いて分析したところ、赤色析出物AはN,N’-ジフェニル-3,4,9,10-ペリレンジカルボキシミドのモノスルホン化物であった。次いで、赤色析出物Aを含む濾物を3kgの脱イオン水に添加、攪拌して再度スラリー化した。さらに、スラリーのpHが11.0になるまで、水酸化ナトリウムの20重量%水溶液を攪拌しながら段階的に添加した後に液温60℃に昇温し、3時間攪拌を行った。次いで、スラリーのpHが3.5を示すまで塩化カルシウム(Sigma-Aldrich社製)の5重量%水溶液を攪拌しながら段階的に添加して赤色析出物Bを生成させ、これを濾別して繰り返し水洗を行い、減圧下80℃で24時間乾燥させた。さらに、ナノジェットマイザー((株)アイシンナノテクノロジーズ製)を用いて乾式粉砕処理を行い、ステンレス製ふるい濾過器(開口径50μm)にかけて粗大分を除去し、パウダー状の色素Iを得て、蛍光X線分析によりカルシウム塩であることを確認した。色素Iは(b)成分であり、式(75)で表される化合物である。
(e)成分である900.00gの混合溶剤(PGME、乳酸エチルおよびγ-ブチロラクトン;重量比率50:40:10)中に、(c-1)成分である68.38gのポリイミド前駆体Bを添加し、30分間攪拌して溶解させた。さらに、(b-2)成分である4.59gの色素Aを添加し、30分間攪拌した後に、(a)成分である27.03gの“Spectrasense(登録商標)”Black K0087(表3中、「Spectrasense Black K0087」)を添加して30分間攪拌し、予備攪拌液を得た。次いで、0.05mmφのジルコニアビーズである“トレセラム(登録商標)”(東レ(株)製)が充填率75体積%でベッセル内に充填された縦型ビーズミル“ウルトラアペックスミル アドバンス(登録商標)”;(株)広島メタル&マシナリー製)に予備攪拌液を送液し、循環方式で周速10m/sで5時間の湿式メディア分散処理を行い、固形分10.00重量%の顔料分散液を得た。口径0.8μmの濾過フィルタで第一の濾過を行い、さらに口径0.2μmの濾過フィルタで第二の濾過を行った。濾過前後で小数点第二位までの固形分の値としては変動が観られず、(a)成分:(b)成分:(c)樹脂=重量比率100:17:253であり、固形分10.00重量%の顔料分散液1を得た。各原料の配合重量を表3に示す。
“Spectrasense(登録商標)”Black K0087に替えて、微細化ペリレンブラック顔料1~4をそれぞれ用いたこと以外は調製例1と同様の方法で湿式メディア分散処理および濾過を行い、顔料分散液2~5を得た。各原料の配合重量を表3に示す。
色素Aに替えて、色素B~Eをそれぞれ用いたこと以外は調製例1と同様の方法で湿式メディア分散処理および濾過を行い、顔料分散液6~9を得た。各原料の配合重量を表4に示す。
ポリイミド前駆体Bに替えて、ポリイミド樹脂Cを用いたこと以外は調製例1と同様の方法で湿式メディア分散処理および濾過を行い、顔料分散液10を得た。各原料の配合重量を表4に示す。
調製例6を基準に、各原料の配合量の比率を変えたこと以外は調製例1と同様の方法で湿式メディア分散処理および濾過を行い、顔料分散液11~12を得た。各原料の配合重量を表4に示す。
色素Aに替えて、色素F~Gをそれぞれ用いたこと以外は調製例1と同様の方法で湿式メディア分散処理および濾過を行い、顔料分散液13~14を得た。各原料の配合重量を表5に示す。
26.72gのポリイミド樹脂Cと、93.75gのメタクリル系樹脂溶液D(固形分30重量%)と、784.38gのPGMEAと、1.41gの色素Hとを混合して30分間撹拌して予備攪拌液を得た。次いで、28.13gのC.I.ピグメントイエロー192(平均一次粒子径42nm)と、28.13gのC.I.ピグメントレッド179(平均一次粒子径48nm)と、37.50gのC.I.ピグメントブルー60(平均一次粒子径61nm)を投入して30分間撹拌した。0.4mmφのジルコニアビーズである“トレセラム(登録商標)”(東レ(株)製)が充填された横型ビーズミル(“DYNO-MILL(登録商標)”Willy A.Bachofen社製)を用いて、30分間循環式で湿式メディア分散処理を行った。次いで、0.05mmφのジルコニアビーズである“トレセラム(登録商標)”(東レ(株)製)が充填率75体積%でベッセル内に充填された縦型ビーズミル(“ウルトラアペックスミル(登録商標)”(株)広島メタル&マシナリー製)を用いて、循環式で湿式メディア分散処理を行い、30分間を経過して以降、分散処理時間が10分間経過するごとにガラス瓶へ適量抜き出してサンプリングした顔料分散液を、動的光散乱法粒度分布測定装置SZ-100にセットして平均分散粒子径を測定して、サンプリング後30分間後の時点で150nm±20nmの範囲内となった顔料分散液を顔料分散液13とした。ここでいう平均分散粒子径とは、顔料分散液が含有する全ての顔料粒子の二次粒子径の数平均値を意味する。
891.71gのPGMEA中に、60.00gのTRR5010G(旭有機材(株)製;固形分100重量%;(c-1)成分であるPGMEA可溶性フェノール樹脂)を添加し、30分間攪拌して溶解させた。次いで、(c-2)成分である21.27gのBYK-LPN6919(ビックケミージャパン(株)製;固形分61重量%のPGMEA溶液。溶剤を除いた樹脂分のアミン価118mgKOH/g;N,N-ジアルキルアミノアルキル基を有するブロック重合型メタクリル系樹脂)を添加して5分間攪拌した後に、(a)成分である27.03gの“Spectrasense(登録商標)”Black K0087を添加して30分間攪拌し、予備攪拌液を得た。以降は調製例1と同様の方法で湿式メディア分散処理および濾過を行い、固形分10.00重量%の顔料分散液16を得た。各原料の配合重量を表5に示す。
30.00gのポリイミド樹脂Eと、(c-1)成分である。30.00gの“SOLSPERSE(登録商標)”20000(ルーブリゾール社製;固形分100重量%;アミン価32mgKOH/g;N,N-ジアルキルアミノアルキル基を有するポリエーテル系樹脂)と、850.00gのMBAとを混合して30分間撹拌した。次いで、90.00gの“IRGAPHOR(登録商標)”Black S0084(BASF社製;(以下、「Black S0084」)を混合し、高速攪拌機(ホモディスパー2.5型;プライミクス(株)製)を用いて20分間攪拌し、予備攪拌液を得た。次いで、0.30mmφのジルコニア粉砕ボール(YTZ;東ソー(株)製)が充填率75体積%でベッセル内に充填された縦型ビーズミル(“ウルトラアペックスミル(登録商標)”(株)広島メタル&マシナリー製)に、予備分散液を送液し、周速7.0m/sで3時間処理して、固形分15.00重量%の顔料分散液17を得た。
黄色灯下、(e)成分である8.03gの混合溶剤(PGME、乳酸エチルおよびγ-ブチロラクトン;重量比率50:40:10)中に、(c-1)成分である0.83gのポリイミド前駆体Bと、1.27gのキノンジアジド化合物aと、0.15gのキノンジアジド化合物bと、(f)成分である0.68gの4,4’,4”-トリヒドロキシトリフェニルメタンと、(g)成分である0.75gのHMOM-TPHAP(本州化学工業(株)製;式(68)で表される化合物)と、レベリング剤である0.05gのBYK-333(ビックケミージャパン(株)製)の固形分5重量%PGME溶液を添加し、30分間攪拌し溶解させた。さらに、38.25gの顔料分散液1を添加し、30分間攪拌して固形分15.00重量%のポジ型感光性顔料組成物1を得た。各原料の配合重量を表6に示す。
顔料分散液1に替えて顔料分散液2~5を用いて、表6に示す配合量でポジ型感光性顔料組成物2~10をそれぞれ調製し、実施例1と同じ方法で露光感度、硬化膜の遮光性および波長410~440nmにおける最大透過率、保存安定性、ハーフトーン加工性および有機EL表示装置の輝度ムラを評価した。評価結果を表7に示す。
顔料分散液1に替えて顔料分散液6~9を用いて、表8に示す配合量でポジ型感光性顔料組成物7~10をそれぞれ調製し、実施例1と同じ方法で露光感度、硬化膜の遮光性および波長410~440nmにおける最大透過率、保存安定性、ハーフトーン加工性および有機EL表示装置の輝度ムラを評価した。評価結果を表9に示す。
顔料分散液1に替えて顔料分散液10を用い、ポリイミド前駆体Bに替えてポリイミド樹脂Cを用いて、表10に示す配合量でポジ型感光性顔料組成物11を調製し、実施例1と同じ方法で露光感度、硬化膜の遮光性および波長410~440nmにおける最大透過率、保存安定性、ハーフトーン加工性および有機EL表示装置の輝度ムラを評価した。評価結果を表11に示す。
顔料分散液1に替えて顔料分散液6を用い、ポリイミド前駆体Bに替えてポリイミド樹脂Cを用いて、表10に示す配合量でポジ型感光性顔料組成物12を調製し、実施例1と同じ方法で露光感度、硬化膜の遮光性および波長410~440nmにおける最大透過率、保存安定性、ハーフトーン加工性および有機EL表示装置の輝度ムラを評価した。評価結果を表11に示す。
顔料分散液1に替えて顔料分散液11~12を用い、表10に示す配合量でポジ型感光性顔料組成物12を調製し、実施例1と同じ方法で露光感度、硬化膜の遮光性および波長410~440nmにおける最大透過率、保存安定性、ハーフトーン加工性および有機EL表示装置の輝度ムラを評価した。評価結果を表11に示す。
顔料分散液1に替えて顔料分散液13~15を用い、表12に示す配合量でポジ型感光性顔料組成物15~17を調製し、実施例1と同じ方法で露光感度、硬化膜の遮光性および波長410~440nmにおける最大透過率、保存安定性、ハーフトーン加工性および有機EL表示装置の輝度ムラを評価した。評価結果を表13に示す。
顔料分散液1に替えて顔料分散液16~17を用い、表14に示す配合量でポジ型感光性顔料組成物16~17を調製し、実施例1と同じ方法で露光感度、硬化膜の遮光性および波長410~440nmにおける最大透過率を評価した。評価結果を表15に示す。なお、30日間貯蔵後はハーフトーン加工が困難となったため正当に評価することができなかった。
黄色灯下、21.95gのMBA中に、オキシムエステル系光重合開始剤である0.41gの“ アデカアークルズ(登録商標)”NCI-831((株)ADEKA製)と、7.27gのポリイミド樹脂Eを添加し、10分間攪拌して溶解させた。さらに、(g)成分である0.55gのMW-100LM(本州化学(株)製)と、光硬化性モノマーである0.82gのライトエステルDCP-M(共栄社(株)製)と、0.82gの“ KAYARAD(登録商標)”DPCA-60(日本化薬(株)製)と、18.18gの顔料分散液17を添加し、30分間攪拌して、ネガ型感光性顔料組成物1を調製した。各原料の配合重量を表14に示す。実施例1と同じ方法で露光感度、硬化膜の遮光性および波長410~440nmにおける最大透過率、保存安定性、ハーフトーン加工性および有機EL表示装置の輝度ムラを評価した。評価結果を表15に示す。
(e)成分である900.00gの混合溶剤(PGME、乳酸エチルおよびγ-ブチロラクトン;重量比率50:40:10)中に、(c-1)成分である68.38gのポリイミド前駆体Bを添加し、30分間攪拌して溶解させた。さらに、(b-2)成分である4.59gの色素Bを添加し、30分間攪拌した後に、(a)成分である18.92gの微細化ペリレンブラック顔料1と、8.11gの微細化ジオキサジン顔料1を添加して30分間攪拌し、予備攪拌液を得た。次いで、0.4mmφのジルコニアビーズである“トレセラム(登録商標)”(東レ(株)製)が充填率75体積%でベッセル内に充填された縦型ビーズミル“ウルトラアペックスミル アドバンス(登録商標)”;(株)広島メタル&マシナリー製)に予備攪拌液を送液し、循環方式で周速10m/sで1時間の湿式メディア分散処理を行った。次いで、0.1mmφのジルコニアビーズである“トレセラム(登録商標)”(東レ(株)製)が充填率75体積%でベッセル内に充填された縦型ビーズミルに送液し、循環方式で周速8m/sで4時間の湿式メディア分散処理を行い、固形分10.00重量%の顔料分散液を得た。口径0.8μmの濾過フィルタで第一の濾過を行い、さらに口径0.2μmの濾過フィルタで第二の濾過を行った。濾過前後で小数点第二位までの固形分の値としては変動が観られず、(a)成分:(h)成分:(b)成分:(c)樹脂=重量比率70:30:17:253であり、固形分10.00重量%の顔料分散液18を得た。各原料の配合重量を表16に示す。
微細化ジオキサジン顔料1に替えて、微細化ジオキサジン顔料2を用いたこと以外は調製例18と同様の方法で湿式メディア分散処理および濾過を行い、(a)成分:(h)成分:(b)成分:(c)樹脂=重量比率70:30:17:253であり、固形分10.00重量%の顔料分散液19を得た。各原料の配合重量を表16に示す。
微細化ジオキサジン顔料1に替えて、微細化ジオキサジン顔料2を用いたこと以外は調製例18と同様の方法で湿式メディア分散処理および濾過を行い、(a)成分:(h)成分:(b)成分:(c)樹脂=重量比率55:45:17:253であり、固形分10.00重量%の顔料分散液20を得た。各原料の配合重量を表16に示す。
顔料分散液1に替えて顔料分散液18~20を用いて、表17に示す配合量でポジ型感光性顔料組成物20~22をそれぞれ調製し、実施例1と同じ方法で露光感度、硬化膜の遮光性および波長410~440nmにおける最大透過率、保存安定性、ハーフトーン加工性および有機EL表示装置の輝度ムラを評価した。評価結果を表18に示す。
“Spectrasense(登録商標)”Black K0087に替えて微細化ペリレンブラック顔料1を用い、色素Aに替えて色素I、JおよびKをそれぞれ用いたこと以外は調製例1と同様の方法で湿式メディア分散処理および濾過を行い、顔料分散液21~23を得た。各原料の配合重量を表19に示す。
顔料分散液1に替えて、顔料分散液21を用いて、表20に示す配合量でポジ型感光性顔料組成物23を調製し、実施例1と同じ方法で露光感度、硬化膜の遮光性および波長410~440nmにおける最大透過率、保存安定性、ハーフトーン加工性および有機EL表示装置の輝度ムラを評価した。評価結果を表21に示す。
顔料分散液1に替えて、顔料分散液22を用いて、表20に示す配合量でポジ型感光性顔料組成物24を調製し、実施例1と同じ方法で露光感度、硬化膜の遮光性および波長410~440nmにおける最大透過率、保存安定性、ハーフトーン加工性および有機EL表示装置の輝度ムラを評価した。評価結果を表21に示す。
顔料分散液1に替えて、顔料分散液23を用いて、表20に示す配合量でポジ型感光性顔料組成物25を調製したが、1日間貯蔵後の時点で著しい高粘度化が生じて塗布性に劣り、プリベーク膜の作製およびハーフトーン加工が困難であった。
顔料分散液1に替えて顔料分散液19を用いて、また、(I)成分として4-アミノベンゼンスルホン酸(東京化成工業(株)製)を用いて、表20に示す配合量でポジ型感光性顔料組成物26を調製し、実施例1と同じ方法で露光感度、硬化膜の遮光性および波長410~440nmにおける最大透過率、保存安定性、ハーフトーン加工性および有機EL表示装置の輝度ムラを評価した。評価結果を表21に示す。
国際公開第2021/182499号の実施例1に開示されたポジ型感光性樹脂組成物(PB-1)を用いて、実施例1と同じ方法で露光感度の評価を試みたが、近赤外線カメラを用いたポジ型ハーフトーン露光マスクの位置合わせが困難であり、評価対象から除外した。また、第一電極形成基板上に2.0、3.0および4.0μmの膜厚となるようにそれぞれプリベーク膜を形成したが、いずれもポジ型ハーフトーン露光マスクの位置合わせが困難であり、実施例1と同じ方法で有機EL表示装置を作製することは不可能であった。
また、実施例1~19における有機EL表示装置は、比較例2~3および比較例6における有機EL表示装置と比べて輝度ムラが少ない点で優れている。
2:薄膜部
3:TFT
4:配線
5:TFT絶縁層
6:平坦化層
7:第一電極
8:基板
9:コンタクトホール
10:画素分割層
11:発光画素
12:第二電極
13:無アルカリガラス基板
14:銀合金膜
15:ITO膜
16:画素分割層
17:有機EL層
18:第二電極
Claims (17)
- (a)式(1)で表される構造を分子内に2つ有し、ペリレン骨格を分子内に1つ有する化合物を含有する顔料、(b)式(2)で表される構造を有し、N,N-ジアルキルアミノアルキル基を有さない化合物またはその金属塩、(c)樹脂、(d)光酸発生剤および(e)有機溶剤を含有するポジ型感光性顔料組成物。
- 前記(b)成分が、(b-1)式(14)で表される構造を有する化合物またはその金属塩を含有する請求項1に記載のポジ型感光性顔料組成物。
- 前記(b)成分が、(b-2)式(15)で表される構造を有する化合物またはその金属塩を含有する請求項1または2に記載のポジ型感光性顔料組成物。
- 前記(a)成分の一次粒子の平均アスペクト比が1.0~1.8である請求項1~3のいずれかに記載のポジ型感光性顔料組成物。
- 前記(c)樹脂のアミン価が5.0mgKOH/g以下である請求項1~4のいずれかに記載のポジ型感光性顔料組成物。
- 前記(b)成分の含有量が、ポジ型感光性顔料組成物中に含有する顔料の合計100重量部に対して5~50重量部である請求項1~7のいずれかに記載のポジ型感光性顔料組成物。
- さらに、(f)加熱により、波長350~780nmの領域において、波長350~500nmの領域に極大吸収波長を有する化合物に変換される化合物を含有する請求項1~8のいずれかに記載のポジ型感光性顔料組成物。
- さらに、(h)ジオキサジン骨格を有する化合物を含有する顔料を含有する請求項1~9のいずれかに記載のポジ型感光性顔料組成物。
- 前記(a)成分と前記(h)成分の合計100重量部に対して、前記(h)成分の含有量が1~50重量部である請求項10に記載のポジ型感光性顔料組成物。
- さらに、(i)アミノベンゼンスルホン酸を含有する請求項1~12のいずれかに記載のポジ型感光性顔料組成物。
- 請求項1~13のいずれかに記載のポジ型感光性顔料組成物の硬化物を含有する硬化膜。
- 請求項14に記載の硬化膜を具備する有機EL表示装置。
- 基板、第一電極、画素分割層、発光画素および第二電極を具備する有機EL表示装置であって、該画素分割層が(a)式(1)で表される構造を分子内に2つ有し、ペリレン骨格を分子内に1つ有する化合物を含有する顔料および(b)式(2)で表される構造を有し、N,N-ジアルキルアミノアルキル基を有さない化合物またはその金属塩を含有する有機EL表示装置。
- 前記画素分割層が、膜厚2.5~4.0μmの厚膜部と、膜厚1.0~2.5μmの薄膜部を有し、かつ該厚膜部と該薄膜部との膜厚の差が1.0μm以上の部位を有する請求項16に記載の有機EL表示装置。
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