WO2024034637A1 - 感光性着色樹脂組成物、顔料分散液、硬化物、隔壁、有機電界発光素子、カラーフィルター及び画像表示装置 - Google Patents
感光性着色樹脂組成物、顔料分散液、硬化物、隔壁、有機電界発光素子、カラーフィルター及び画像表示装置 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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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
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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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 [2D] 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 [2D] radiating surfaces
- H05B33/22—Light sources with substantially two-dimensional [2D] 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
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
Definitions
- the present invention relates to a photosensitive colored resin composition, a pigment dispersion, a cured product, a partition wall, an organic electroluminescent device, a color filter, and an image display device.
- Liquid crystal displays utilize the property that the arrangement of liquid crystal molecules is switched by turning on and off a voltage to the liquid crystal.
- many of the members constituting the cell of an LCD are formed by a method using a photosensitive composition, typified by a photolithography method.
- the range of application of this photosensitive composition is expanding further because it is easy to form a fine structure and it is easy to process substrates for large screens.
- Image display devices that include organic electroluminescent elements (also referred to as organic electroluminescence, organic EL) have excellent visibility and responsiveness such as contrast and viewing angle, and are designed to reduce power consumption, be thinner and lighter, and display the display itself. Because it can be made flexible, it is attracting attention as a next-generation flat panel display (FPD).
- An organic electroluminescent device has a structure in which a light emitting layer or an organic layer including various functional layers is sandwiched between a pair of electrodes, at least one of which is translucent.
- An image display device displays an image by driving a panel in which an organic electroluminescent element is arranged for each pixel.
- organic electroluminescent devices Conventionally, such organic electroluminescent devices have been manufactured by forming barrier ribs (banks) on a substrate and then stacking a light-emitting layer or various functional layers within a region surrounded by the barrier ribs.
- a vapor deposition method is mainly used in which a material is sublimated in a vacuum and deposited on a substrate to form a film.
- wet process methods such as casting, spin coating, and inkjet printing have attracted attention.
- the inkjet printing method can reduce unevenness in film thickness when printing on large areas, and can also improve the resolution of displays, reduce the amount of materials used, and improve yields by separating the coatings during coating. Therefore, it is suitable as a method for forming an organic layer in a large panel.
- a method of easily forming partition walls a method of forming them by photolithography using a photosensitive composition is known. Furthermore, as a method of imparting light-shielding properties to partition walls and suppressing light leakage between pixels, a method of incorporating a coloring agent into a photosensitive composition is known.
- Patent Document 1 describes a photosensitive colored resin composition that has high light-shielding properties and a low dielectric constant by using a specific organic black pigment and a dispersant.
- Patent Document 2 describes a photosensitive colored resin composition used for partition walls of organic electroluminescent devices that is effective in suppressing outgas generation by using a specific organic black pigment and an alkali-soluble resin. ing.
- a known method for preparing a photosensitive colored resin composition used for light-shielding partition wall applications is to add a pigment as a coloring agent and mix a pigment dispersion, which is dispersed using a dispersant, with other components. ing.
- a pigment dispersion which is dispersed using a dispersant, with other components. ing.
- sufficient dispersibility and storage stability may not be ensured depending on the type of pigment, dispersant, and dispersion resin.
- the remaining film rate of the photosensitive colored resin composition is low in the developing process and baking process during the production of partition walls, the developer resistance and heat resistance during baking will be poor, resulting in decomposition products and by-products in the composition. uncured substances may remain or re-deposit on the anode.
- the inventors have investigated that when a partition wall is used in an organic electroluminescent device, it may not be possible to obtain sufficient brightness due to residues and re-deposition on the anode if the device current density with respect to the applied voltage is low. It has also been found that the photosensitive colored resin compositions described in Patent Documents 1 and 2 have insufficient film remaining ratio and device current density.
- the first object of the present invention is to provide a photosensitive colored resin composition having a high residual film rate.
- Another object of the present invention is to provide a photosensitive colored resin composition that has a high residual film rate and has a high device current density when used for a partition wall for an organic electroluminescent device.
- a second object of the present invention is to provide a pigment dispersion with excellent dispersibility. Furthermore, it is an object of the present invention to provide a photosensitive colored resin composition, an organic electroluminescent device, and an image display device.
- a photosensitive colored resin composition containing (A) a colorant, (B) a dispersant, (C) an alkali-soluble resin, and (D) a photoinitiator,
- the colorant (A) contains an organic pigment (A-1)
- R 1 represents a hydrogen atom or a methyl group.
- Each R 2 independently represents an alkyl group having 1 to 4 carbon atoms.
- L represents an alkylene group having 2 to 6 carbon atoms, and has at least a hydroxyl group or an ester group of a hydroxyl group and a polybasic acid as a substituent.
- Each * represents a bond.
- [2] The photosensitive colored resin composition of [1], wherein the resin (C1) has a structural unit represented by the following general formula (2).
- A represents a hydrogen atom or a polybasic acid residue.
- R 1 represents a hydrogen atom or a methyl group.
- Each R 2 independently represents an alkyl group having 1 to 4 carbon atoms.
- Each * represents a bond.
- the organic black pigment includes a benzodifuranone-based organic black pigment.
- the organic black pigment contains an organic black pigment that is a compound represented by the following general formula (A-1-1), a geometric isomer thereof, a salt thereof, or a salt of the geometric isomer.
- Photosensitive colored resin composition is a compound represented by the following general formula (A-1-1), a geometric isomer thereof, a salt thereof, or a salt of the geometric isomer.
- R 611 and R 616 each independently represent a hydrogen atom, CH 3 , CF 3 , fluorine atom or chlorine atom;
- a pigment dispersion containing (A) a colorant, (B) a dispersant, and (C) an alkali-soluble resin contains an organic pigment (A-1), A pigment dispersion, wherein the alkali-soluble resin (C) contains a resin (C1) having a structural unit represented by the following general formula (1).
- R 1 represents a hydrogen atom or a methyl group.
- Each R 2 independently represents an alkyl group having 1 to 4 carbon atoms.
- L represents an alkylene group having 2 to 6 carbon atoms, and has at least a hydroxyl group or an ester group of a hydroxyl group and a polybasic acid as a substituent.
- Each * represents a bond.
- A represents a hydrogen atom or a polybasic acid residue.
- R 1 represents a hydrogen atom or a methyl group.
- Each R 2 independently represents an alkyl group having 1 to 4 carbon atoms.
- Each * represents a bond.
- the organic black pigment contains an organic black pigment that is a compound represented by the following general formula (A-1-1), a geometric isomer thereof, a salt thereof, or a salt of the geometric isomer. ] Pigment dispersion.
- R 611 and R 616 each independently represent a hydrogen atom, CH 3 , CF 3 , fluorine atom or chlorine atom;
- An organic electroluminescent device comprising the partition wall of [18].
- a color filter comprising luminescent nanocrystal particles and having the partition wall of [19].
- An image display device comprising the partition wall of [19].
- R 1 represents a hydrogen atom or a methyl group.
- Each R 2 independently represents an alkyl group having 1 to 4 carbon atoms.
- L represents an alkylene group having 2 to 6 carbon atoms, and has at least a hydroxyl group or an ester group of a hydroxyl group and a polybasic acid as a substituent.
- Each * represents a bond.
- a photosensitive colored resin composition with a high residual film rate can be provided.
- a pigment dispersion liquid having excellent dispersibility can be provided.
- an organic electroluminescent device and an image display device can be provided.
- FIG. 1 is a schematic cross-sectional view of an example of a color filter including the partition walls of the present invention.
- (meth)acrylic means “acrylic and/or methacrylic", and the same applies to "(meth)acrylate” and "(meth)acryloyl”.
- Acrylic resin means a (co)polymer containing (meth)acrylic acid and a (co)polymer containing (meth)acrylic acid ester having a carboxy group.
- Total solid content means all components other than the solvent contained in the photosensitive colored resin composition or pigment dispersion, and even if the components other than the solvent are liquid at room temperature, the components are Not included in solvent, included in total solids.
- (Co)polymer means to include both a single polymer (homopolymer) and a copolymer (copolymer), and “acid (anhydride)” and “(anhydride)...acid” , is meant to include both acids and their anhydrides.
- the term “monomer” refers to a so-called high-molecular substance (polymer), and includes dimers, trimers, and oligomers in addition to monomers in the narrow sense.
- Weight average molecular weight means a weight average molecular weight (Mw) in terms of polystyrene measured by GPC (gel permeation chromatography).
- amine value refers to the amine value in terms of effective solid content, and is a value expressed by the mass of KOH equivalent to the amount of base per gram of solid content of the dispersant. The measurement method will be described later.
- Acid value refers to the acid value in terms of effective solid content, unless otherwise specified, and is calculated by neutralization titration.
- C.I means Color Index. In this specification, percentages and parts expressed by “mass” are synonymous with percentages and parts expressed by “weight.”
- the photosensitive colored resin composition according to the first aspect of the present invention contains (A) a colorant, (B) a dispersant, (C) an alkali-soluble resin, and (D) a photoinitiator, and (A)
- the colorant contains an organic pigment (A-1), and the alkali-soluble resin (C) contains a resin (C1) represented by formula (1).
- the pigment dispersion according to the second aspect of the present invention contains (A) a colorant, (B) a dispersant, and (C) an alkali-soluble resin, and the (A) colorant contains an organic pigment (A-1).
- (C) alkali-soluble resin contains resin (C1) represented by formula (1).
- (A) colorant, (B) dispersant, (C) alkali-soluble resin, and (D) photoinitiator are the photosensitive colored resin composition according to the first aspect, and the constituent requirements of both the pigment dispersion liquid according to the second aspect.
- the photosensitive colored resin composition of the present invention is Contains (A) a colorant, (B) a dispersant, (C) an alkali-soluble resin, and (D) a photopolymerization initiator.
- the photosensitive colored resin composition of the present invention contains (A) a coloring agent.
- a coloring agent By containing the colorant (A), it is possible to obtain appropriate light absorbing properties, particularly appropriate light blocking properties when used for forming light blocking members such as partition walls.
- the colorant (A) of the present invention contains an organic pigment (A-1). Containing the organic pigment (A-1) tends to improve insulation properties.
- the number of pigments contained in the coloring agent may be one type alone, or two or more types may be used. From the viewpoint of achieving both uniform light shielding in the visible region and OD per unit film thickness, it is preferable to use two or more types.
- Organic pigments that can be used as the colorant are not particularly limited, and examples include organic coloring pigments and organic black pigments.
- the organic colored pigment means an organic pigment exhibiting a color other than black, and includes, for example, a red pigment, an orange pigment, a blue pigment, a violet pigment, a green pigment, and a yellow pigment.
- organic pigments it is preferable to use organic coloring pigments from the viewpoint of suppressing absorption of ultraviolet rays, having high curability, and making it easier to control the shape of the cured product.
- organic black pigment it is preferable to use an organic black pigment from the viewpoint of having high light-shielding properties and being able to lower the pigment concentration relative to the solid content.
- organic black pigments examples include perylene black pigments, aniline black pigments, and benzodifuranone black pigments.
- perylene-based black pigments examples include Lumogen Black (registered trademark) FK4281, K0087, and Paliogen Black (registered trademark) EH0788 (all manufactured by BASF).
- aniline black pigment examples include Paliotol Black (registered trademark) L0080, D0080, and K0080 (all manufactured by BASF).
- benzodifuranone black pigments are preferred from the viewpoints of light-shielding properties, dispersibility, developability, and luminescent properties.
- benzodifuranone black pigments from the viewpoint of light-shielding properties, dispersibility, developability, and luminescent properties, compounds represented by the following general formula (A-1-1) (hereinafter referred to as "compounds (A-1-1)”) ), geometric isomers of compound (A-1-1), salts of compound (A-1-1), and salts of geometric isomers of compound (A-1-1). It is preferable to use an organic black pigment (hereinafter sometimes referred to as "organic black pigment represented by general formula (A-1-1)”) containing at least one member selected from the group.
- R 611 and R 616 each independently represent a hydrogen atom, CH 3 , CF 3 , a fluorine atom or a chlorine atom;
- compound (A-1-1) When compound (A-1-1) is anionic, its charge can be reduced to any known suitable cation, such as a metal, organic, inorganic or metal-organic cation, in particular an alkali metal, alkaline earth metal, transition Salts compensated with metals, primary ammonium, secondary ammonium, tertiary ammonium such as trialkylammonium, quaternary ammonium such as tetraalkylammonium, or organometallic complexes are preferred. Furthermore, when the geometric isomer of compound (A-1-1) is anionic, a similar salt is preferable.
- a metal, organic, inorganic or metal-organic cation in particular an alkali metal, alkaline earth metal, transition Salts compensated with metals, primary ammonium, secondary ammonium, tertiary ammonium such as trialkylammonium, quaternary ammonium such as tetraalkylammonium, or organometallic complexe
- R 612 , R 614 , R 615 , R 617 , R 619 and R 620 are each independently preferably a hydrogen atom, a fluorine atom or a chlorine atom, more preferably a hydrogen atom.
- R 613 and R 618 each independently preferably represent a hydrogen atom, NO 2 , OCH 3 , OC 2 H 5 , bromine atom, chlorine atom, CH 3 , C 2 H 5 , N(CH 3 ) 2 , N(CH 3 ) (C 2 H 5 ), N(C 2 H 5 ) 2 , ⁇ -naphthyl, ⁇ -naphthyl, SO 3 H or SO 3 - , more preferably a hydrogen atom or SO 3 H, particularly preferably is a hydrogen atom.
- R 611 and R 616 are each independently preferably a hydrogen atom, CH 3 or CF 3 , more preferably a hydrogen atom.
- at least one combination selected from the group consisting of R 611 and R 616 , R 612 and R 617 , R 613 and R 618 , R 614 and R 619 , and R 615 and R 620 is the same, and more preferably R 611 is the same as R 616 , R 612 is the same as R 617 , R 613 is the same as R 618 , R 614 is the same as R 619 , and R 615 is the same as R 620 . are the same.
- alkyl group having 1 to 12 carbon atoms examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, 2-methylbutyl group, n -pentyl group, 2-pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, n-heptyl group, n-octyl group, 1,1,3,3-tetramethylbutyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group or dodecyl group.
- Examples of the cycloalkyl group having 3 to 12 carbon atoms include a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl group, a trimethylcyclohexyl group, a tuzyl group, a norbornyl group, a bornyl group, and a norcalyl group. , calyl group, menthyl group, norpinyl group, pinyl group, adamantan-1-yl group or adamantan-2-yl group.
- alkenyl groups having 2 to 12 carbon atoms include vinyl group, allyl group, 2-propen-2-yl group, 2-buten-1-yl group, 3-buten-1-yl group, and 1,3-butadiene group.
- Examples of the cycloalkenyl group having 3 to 12 carbon atoms include 2-cyclobuten-1-yl group, 2-cyclopenten-1-yl group, 2-cyclohexen-1-yl group, 3-cyclohexen-1-yl group, 2-cyclohexen-1-yl group, , 4-cyclohexadien-1-yl group, 1-p-menthen-8-yl group, 4(10)-thujen-10-yl group, 2-norbornen-1-yl group, 2,5-norbornadien-1 -yl group, 7,7-dimethyl-2,4-norcaladien-3-yl group, or camphenyl group.
- alkynyl group having 2 to 12 carbon atoms examples include 1-propyn-3-yl group, 1-butyn-4-yl group, 1-pentyn-5-yl group, and 2-methyl-3-butyn-2-yl group. group, 1,4-pentadiyn-3-yl group, 1,3-pentadiyn-5-yl group, 1-hexyn-6-yl group, cis-3-methyl-2-penten-4-yn-1-yl group, trans-3-methyl-2-penten-4-yn-1-yl group, 1,3-hexadiyn-5-yl group, 1-octyn-8-yl group, 1-nonyn-9-yl group, It is a 1-decyn-10-yl group or a 1-dodecyn-12-yl group.
- the halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
- the organic black pigment represented by formula (A-1-1) is preferably a compound represented by the following general formula (A-1-2) (hereinafter also referred to as "compound (A-1-2)"). ), and geometric isomers of compound (A-1-2).
- Examples of the compound (A-1-2) include the trade name Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF).
- This organic black pigment is preferably used after being dispersed using a dispersant, solvent, and method described below.
- the sulfonic acid derivative of compound (A-1-1), especially the sulfonic acid derivative of compound (A-1-2) is present during dispersion, dispersibility and storage stability may be improved.
- the black pigment contains these sulfonic acid derivatives.
- the chemical structure of the organic coloring pigment is not particularly limited, but examples include azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. Specific examples of pigments that can be used are shown below using pigment numbers. "C.I.” in “C.I. Pigment Red 2" and the like listed below means a color index.
- red pigments examples include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200
- C. I. It is preferable to use Pigment Red 177, 254, and 272.
- a red pigment with low ultraviolet absorbance When curing the photosensitive colored resin composition with ultraviolet rays, it is preferable to use a red pigment with low ultraviolet absorbance, and from this point of view, C.I. I. It is more preferable to use Pigment Red 254 and 272.
- orange pigments examples include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. From the viewpoint of dispersibility and light blocking properties, C. I. It is preferable to use Pigment Orange 13, 43, 64, and 72. When curing the photosensitive colored resin composition with ultraviolet rays, it is preferable to use an orange pigment with a low ultraviolet absorbance, and from this point of view, C.I. I. It is more preferable to use Pigment Orange 64 and 72.
- blue pigments examples include C.I. I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. From the viewpoint of light-shielding properties, C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 60, more preferably C.I. I. Pigment Blue 15:6 may be mentioned. In addition, in terms of dispersibility and light blocking properties, C. I. Pigment Blue 15:6, 16, 60 is preferably used. When curing the photosensitive colored resin composition with ultraviolet rays, it is preferable to use a blue pigment with low ultraviolet absorbance, and from this point of view, C.I. I. It is more preferable to use Pigment Blue 60.
- the purple pigment for example, C.I. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50.
- C.I. I. Pigment Violet 19 23, 29, more preferably C.I. I. Pigment Violet 23 may be mentioned.
- C. I. It is preferable to use Pigment Violet 23, 29.
- When curing the photosensitive colored resin composition with ultraviolet rays it is preferable to use a purple pigment with a low ultraviolet absorbance, and from this point of view, C.I. I. It is more preferable to use Pigment Violet 29.
- green pigments examples include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59. .
- C. I. Pigment Green 7 and 36 can be mentioned.
- yellow pigments examples include C.I. I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184
- Red pigment C. I. Pigment Red 177, 254, 272
- Orange pigment C. I. Pigment orange 43, 64, 72
- Blue pigment C. I. Pigment Blue 15:6,60 Purple pigment: C. I. pigment violet 23, 29
- the combination of organic coloring pigments when two or more types of organic coloring pigments are used together is not particularly limited, but from the viewpoint of light shielding, at least one type selected from the group consisting of red pigments and orange pigments, and blue pigments and purple pigments. It is preferable to contain at least one member selected from the group consisting of:
- the combination of colors is not particularly limited, but from the viewpoint of light-shielding properties, examples include a combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment, and a combination of a blue pigment, an orange pigment, and a violet pigment.
- colorants other than the organic pigment (A-1) may be used in combination.
- the colorant that can be used in combination is not particularly limited, and pigments or dyes may be used.
- the other coloring agents used in combination with the organic pigment one type may be used alone, or two or more types may be used in combination. From the viewpoint of durability, it is preferable to use pigments. Examples include inorganic pigments.
- inorganic black pigment it is preferable to use an inorganic black pigment from the viewpoint of higher light-shielding properties.
- inorganic black pigments include carbon black, acetylene black, lamp black, bone black, graphite, iron black, cyanine black, and titanium black.
- Carbon black can be preferably used from the viewpoint of light-shielding properties and image characteristics.
- Examples of carbon black include the following carbon blacks. Made by Mitsubishi Chemical: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, #5, #10, #20, #25, #30, #32, #33, #40 , #44, #45, #47, #50, #52, #55, #650, #750, #850, #900, #950, #960, #970, #980, #990, #1000, # 2200, #2300, #2350, #2400, #2600, #2650, #3030, #3050, #3150, #3250, #3400, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B , OIL11B, OIL30B, OIL31B.
- Printex registered trademark, same hereinafter
- Printex3OP Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex8 5, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBla ck4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170.
- Monarch registered trademark, same hereinafter
- Monarch280 Monarch280
- Monarch460 Monarch460
- Monarch800 Monarch880
- Monarch900 Monarch1000, Monarch1100, Monarch1300, Monarch1 400, Monarch4630
- REGAL registered trademark, same hereinafter
- REGAL registered trademark, same hereinafter
- REGAL99R REGAL415
- REGAL415R REGAL250
- REGAL250R REGAL330
- REGAL400R REGAL550R
- REGAL660R BLACK PEARLS480, PEARLS130
- VULCAN registered trademark, the same applies hereinafter
- XC72R ELFTEX (registered trademark) Trademark)-8.
- RAVEN registered trademark, same hereinafter
- RAVEN14 RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, R AVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U , RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000 .
- Carbon black whose surface has been acid-treated may be used.
- carbon black described in Japanese Patent No. 3,674,086 can be suitably used.
- carbon black coated with a resin may be used.
- Use of resin-coated carbon black has the effect of improving adhesion to glass substrates and volume resistivity.
- the resin-coated carbon black for example, the carbon black described in Japanese Patent Application Laid-Open No. 09-71733 can be suitably used.
- Resin-coated carbon black is preferably used in terms of volume resistivity and dielectric constant.
- the average particle diameter of the pigment is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and still more preferably 0.25 ⁇ m or less.
- the standard for the average particle diameter is the number of pigment particles.
- the average particle diameter of the pigment is a value determined from the pigment particle diameter measured by dynamic light scattering (DLS). Particle size measurement is performed using a sufficiently diluted photosensitive colored resin composition (usually diluted to a pigment concentration of about 0.005 to 0.2% by mass. However, if the concentration is recommended by the measuring device) , according to its concentration) and measured at 25°C.
- dyes may also be used.
- dyes that can be used as colorants include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
- azo dyes examples include C.I. I. Acid Yellow 11, C. I. Acid Orange 7, C. I. Acid Red 37, C. I. Acid Red 180, C. I. Acid Blue 29, C. I. Direct Red 28, C. I. Direct Red 83, C. I. Direct Yellow 12, C. I. Direct Orange 26, C. I. Direct Green 28, C. I. Direct Green 59, C. I. Reactive Yellow 2, C. I. Reactive Red 17, C. I. Reactive Red 120, C. I. Reactive Black 5, C. I. Disperse Orange 5, C. I. Dispersed Red 58, C. I. Disperse Blue 165, C. I. Basic Blue 41, C. I. Basic Red 18, C. I. Mordant Red 7, C. I. Mordant Yellow 5, C. I. Mordant Black 7 is mentioned.
- anthraquinone dyes examples include C.I. I. Bat Blue 4, C. I. Acid Blue 40, C. I. Acid Green 25, C. I. Reactive Blue 19, C. I. Reactive Blue 49, C. I. Dispersed Red 60, C. I. Disperse Blue 56, C. I. An example is Disperse Blue 60.
- phthalocyanine dyes examples include C.I. I. Bat Blue 5 is an example.
- quinoneimine dyes include C.I. I. Basic Blue 3, C. I. Basic Blue 9 is an example.
- quinoline dyes examples include C.I. I. Solvent Yellow 33, C. I. Acid Yellow 3, C. I. Disperse Yellow 64 is mentioned.
- nitro dyes examples include C.I. I. Acid Yellow 1, C. I. Acid Orange 3, C. I. An example is Disperse Yellow 42.
- the photosensitive colored resin composition of the present invention contains (B) a dispersant in order to finely disperse the colorant (A) and stabilize the dispersion state.
- a dispersant a polymer dispersant having a functional group is preferable, and from the viewpoint of dispersion stability, a carboxy group; a phosphoric acid group; a sulfonic acid group; or a base thereof; a primary, secondary or tertiary Polymer dispersants having functional groups such as an amino group; a quaternary ammonium group; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, and pyrazine are preferred.
- polymer dispersants having basic functional groups such as primary, secondary or tertiary amino groups; quaternary ammonium groups; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine are used in small amounts as dispersants. It is particularly preferred from the viewpoint of being able to disperse pigments.
- polymeric dispersants include urethane-based dispersants, acrylic-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants consisting of monomers and macromonomers having amino groups, and polyoxyethylene alkyl ether-based dispersants.
- examples include dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.
- dispersants examples include, for example, the trade names EFKA (registered trademark, manufactured by BASF Corporation), DISPERBYK (registered trademark, manufactured by BYK-Chemie Corporation), DISPARBYK (registered trademark, manufactured by Kusumoto Kasei Co., Ltd.), and SOLSPERSE (registered trademark, manufactured by Kusumoto Kasei Co., Ltd.). (registered trademark, manufactured by Lubrizol Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and Ajisper (registered trademark, manufactured by Ajinomoto Co., Ltd.).
- One type of polymer dispersant may be used alone, or two or more types may be used in combination.
- the dispersant (B) preferably contains one or both of a urethane polymer dispersant having a functional group and an acrylic polymer dispersant, and an acrylic polymer dispersant. It is particularly preferable to include. From the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and one or both of a polyester bond and a polyether bond is preferred.
- urethane-based and acrylic-based polymer dispersants examples include DISPERBYK-160 to 167, 182 series (all urethane-based), DISPERBYK-2000, 2001, BYK-LPN21116 (all acrylic) (all manufactured by BYK Chemie). ).
- the amine value of the polymer dispersant having a basic functional group is not particularly limited, but is preferably 1 mgKOH/g or more, more preferably 10 mgKOH/g or more, even more preferably 20 mgKOH/g or more, even more preferably 40 mgKOH/g or more. , 50 mgKOH/g or more is particularly preferred. Further, it is preferably 140 mgKOH/g or less, more preferably 120 mgKOH/g or less, even more preferably 100 mgKOH/g or less, even more preferably 90 mgKOH/g or less, and particularly preferably 80 mgKOH/g or less. The above upper and lower limits can be arbitrarily combined.
- it is preferably 1 to 140 mgKOH/g, more preferably 10 to 120 mgKOH/g, even more preferably 20 to 100 mgKOH/g, even more preferably 40 to 90 mgKOH/g, and particularly preferably 50 to 80 mgKOH/g.
- the content is equal to or more than the lower limit, the dispersibility tends to be improved.
- the content is below the upper limit, the compatibility with the alkali-soluble resin (C) tends to improve.
- the acrylic dispersant is preferably an AB or BAB block copolymer composed of an A block having the above functional group and a B block not having the above functional group.
- the A block in addition to the partial structure derived from the unsaturated group-containing monomer containing the above-mentioned functional group, contains a partial structure derived from the unsaturated group-containing monomer that does not contain the above-mentioned functional group. These may be contained in the A block in either random copolymerization or block copolymerization.
- the content of the partial structure not containing a functional group in the A block is preferably 80% by mass or less, more preferably 50% by mass or less, even more preferably 30% by mass or less, even more preferably 10% by mass or less, Particularly preferably, it is 0% by mass.
- the B block is preferably composed only of partial structures derived from unsaturated group-containing monomers that do not contain the above-mentioned functional groups, and two or more types of monomers are contained in one B block. may contain a partial structure derived from a body, and these may be contained in the B block in either random copolymerization or block copolymerization mode.
- the AB or BAB block copolymer is prepared, for example, by the living polymerization method shown below. Living polymerization methods include anionic living polymerization methods, cationic living polymerization methods, and radical living polymerization methods. Among these, in the anionic living polymerization method, the polymerization active species is an anion, and is represented by the following scheme, for example.
- Ar 1 is a monovalent organic group
- Ar 2 is a monovalent organic group different from Ar 1
- M is a metal atom
- s and t are each an integer of 1 or more.
- the polymerization active species is a radical, and is shown, for example, in the scheme below.
- Ar 1 is a monovalent organic group
- Ar 2 is a monovalent organic group different from Ar 1
- j and k are each an integer of 1 or more
- R a is a hydrogen atom or 1 It is a valent organic group
- R b is a hydrogen atom or a monovalent organic group different from R a .
- the acrylic dispersant that can be used in the present invention may be an AB block copolymer or a BAB block copolymer, and the A block/B block copolymer constituting the copolymer may be
- the block ratio is also not particularly limited, and is preferably 1/99 to 80/20 (mass ratio), more preferably 5/95 to 60/40 (mass ratio). By keeping it within this range, it tends to be easier to ensure a balance between dispersibility and storage stability.
- the amount of quaternary ammonium groups in 1 g of the AB block copolymer and BAB block copolymer that can be used in the present invention is preferably 0.1 to 10 mmol. By keeping it within this range, it tends to be easy to ensure good dispersibility.
- Such an acrylic dispersant may contain an amino group.
- the amine value of the acrylic dispersant is preferably 1 mgKOH/g or more, more preferably 10 mgKOH/g or more, even more preferably 20 mgKOH/g or more, even more preferably 40 mgKOH/g or more, particularly preferably 50 mgKOH/g or more. Further, it is preferably 140 mgKOH/g or less, more preferably 120 mgKOH/g or less, even more preferably 100 mgKOH/g or less, even more preferably 90 mgKOH/g or less, and particularly preferably 80 mgKOH/g or less.
- the above upper and lower limits can be arbitrarily combined.
- the content is preferably 1 to 140 mgKOH/g, more preferably 10 to 120 mgKOH/g, even more preferably 20 to 100 mgKOH/g, even more preferably 40 to 90 mgKOH/g, and particularly preferably 50 to 80 mgKOH/g.
- the content is equal to or more than the lower limit, the dispersibility tends to be improved.
- the content is below the upper limit, the compatibility with the alkali-soluble resin (C) tends to improve.
- the amine value of the acrylic dispersant is expressed by the mass of KOH equivalent to the amount of base per gram of solid content excluding the solvent in the dispersant sample, and is measured by the following method.
- Amine value [mgKOH/g] (561 ⁇ V)/(W ⁇ S) [However, W: weighed amount of dispersant sample [g], V: titration amount at titration end point [mL], S: solid content concentration of dispersant sample [mass %]. ]
- the weight average molecular weight (Mw) of the acrylic dispersant is not particularly limited, but is preferably 1,000 or more, more preferably 3,000 or more, even more preferably 4,000 or more, and particularly preferably 5,000 or more. Further, it is preferably 50,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less.
- the above upper and lower limits can be arbitrarily combined. For example, it is preferably 1,000 to 50,000, more preferably 3,000 to 50,000, even more preferably 4,000 to 20,000, and particularly preferably 5,000 to 15,000.
- the acrylic dispersant preferably has a tertiary amino group and/or a quaternary ammonium group.
- the acrylic dispersant has a quaternary ammonium group as a functional group
- the chemical structure of the repeating unit containing the quaternary ammonium group is not particularly limited. From the viewpoint of dispersibility, it is preferable that the acrylic dispersant has a repeating unit represented by the following general formula (V) (hereinafter sometimes referred to as "repeat unit (V)").
- R 31 to R 33 each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. and two or more of R 31 to R 33 may be bonded to each other to form a cyclic structure.
- R 34 is a hydrogen atom or a methyl group.
- X is a divalent linking group, and Y - is a counter anion.
- the alkyl group which may have a substituent in R 31 to R 33 of formula (V) may be linear or branched. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
- the number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 or more, preferably 10 or less, more preferably 6 or less, even more preferably 4 or less, and particularly preferably 2 or less.
- the number is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 4, and particularly preferably 1 to 2.
- alkyl group examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, and octyl group;
- a group is preferable, a methyl group, an ethyl group, a propyl group, and a butyl group are more preferable, and a methyl group and an ethyl group are even more preferable.
- the number of carbon atoms in the optionally substituted aryl group in R 31 to R 33 of formula (V) is not particularly limited, but is preferably 6 or more, preferably 16 or less, and more preferably 12 or less.
- 6 to 16 is preferable, and 6 to 12 is more preferable.
- aryl group examples include phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, diethylphenyl group, naphthyl group, and anthracenyl group; phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, A diethylphenyl group is preferable, and a phenyl group, a methylphenyl group, and an ethylphenyl group are more preferable.
- the number of carbon atoms in the optionally substituted aralkyl group in R 31 to R 33 of formula (V) is not particularly limited, but is preferably 7 or more, preferably 16 or less, more preferably 12 or less, It is more preferably 10 or less, particularly preferably 8 or less.
- the number is preferably 7 to 16, more preferably 7 to 12, even more preferably 7 to 10, and particularly preferably 7 to 8.
- Examples of the aralkyl group include phenylmethyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, and phenylisopropyl group, with phenylmethyl group, phenylethyl group, phenylpropyl group, and phenylbutyl group being preferred, and phenylmethyl and phenylethyl group are more preferred.
- R 31 to R 33 are each independently an alkyl group or an aralkyl group, and it is preferable that R 31 to R 33 are each independently a methyl group or a phenylmethyl group.
- Y ⁇ in formula (V) include Cl ⁇ , Br ⁇ , I ⁇ , ClO 4 ⁇ , BF 4 ⁇ , CH 3 COO ⁇ , and PF ⁇ .
- Sulfate anions and alkylsulfonate anions can also be suitably used.
- Cl - is preferable as Y - .
- alkylsulfonate anions are preferred.
- repeating unit (VI) When a polymeric dispersant has a tertiary amine as a functional group, from the viewpoint of dispersibility and luminescent properties, the repeating unit represented by the following general formula (VI) (hereinafter referred to as “repeating unit (VI)”) ) is preferable.
- R 35 and R 36 each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent.
- R 35 and R 36 may be bonded to each other to form a cyclic structure.
- R 37 is a hydrogen atom or a methyl group.
- Z is a divalent linking group.
- alkyl group which may have a substituent in R 35 and R 36 of formula (VI) those exemplified as R 31 to R 33 of formula (V) can be preferably employed.
- aryl group which may have a substituent in R 35 and R 36 of formula (VI) those exemplified as R 31 to R 33 of formula (V) can be preferably employed.
- aralkyl group which may have a substituent in R 35 and R 36 of formula (VI) those exemplified as R 31 to R 33 of formula (V) can be preferably employed.
- R 35 and R 36 are each independently an alkyl group which may have a substituent, and more preferably a methyl group or an ethyl group.
- Examples of the substituent that the alkyl group, aralkyl group, or aryl group in R 31 to R 33 of formula (V) and R 35 and R 36 of formula (VI) may have include a halogen atom, an alkoxy group, Examples include benzoyl group and hydroxyl group.
- X in formula (V) and Z in formula (VI) are, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CONH-R 43 - group, -COOR 44 -, respectively.
- the content ratio of the repeating unit (V) in all repeating units of the dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 1 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more. , 8 mol% or more is particularly preferred. Further, it is preferably 50 mol% or less, more preferably 30 mol% or less, even more preferably 20 mol% or less, and particularly preferably 15 mol% or less.
- the content of the repeating unit (VI) in all repeating units of the dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more. , 20 mol% or more is particularly preferred. Moreover, it is preferably 60 mol% or less, more preferably 40 mol% or less, even more preferably 30 mol% or less, and particularly preferably 25 mol% or less.
- acrylic dispersants are used as repeating units represented by the following general formula (VII) (hereinafter referred to as “repeating units (VII)”). )”) is preferable.
- R 40 is an ethylene group or a propylene group
- R 41 is an alkyl group which may have a substituent
- R 42 is a hydrogen atom or a methyl group.
- n is an integer from 1 to 20.
- the alkyl group which may have a substituent in R 41 of formula (VII) may be either linear or branched. It may also contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
- the number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 or more, more preferably 2 or more. Further, it is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less.
- alkyl group examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, and octyl group;
- a group is preferable, and a methyl group, an ethyl group, a propyl group, and a butyl group are more preferable.
- n is preferably 1 or more, and more preferably 2 or more, from the viewpoint of compatibility and dispersibility with an alkali-soluble resin component such as a solvent. Moreover, 10 or less is preferable, and 5 or less is more preferable. The above upper and lower limits can be arbitrarily combined. For example, 1 to 10 is preferable, and 2 to 5 is more preferable.
- the content of the repeating unit (VII) in all repeating units of the dispersant is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, and even more preferably 4 mol% or more. Moreover, it is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less.
- the above upper and lower limits can be arbitrarily combined. For example, it is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and even more preferably 4 to 10 mol%. When it is within the above range, it tends to be easy to achieve both compatibility with an alkali-soluble resin component such as a solvent and dispersion stability.
- the acrylic dispersant is a repeating unit represented by the following general formula (VIII) (hereinafter referred to as a "repeat unit ( VIII).
- R 38 is an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.
- R 39 is a hydrogen atom or a methyl group.
- the alkyl group which may have a substituent in R 38 of formula (VIII) may be either linear or branched. It may also contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
- the number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and even more preferably 4 or more. Moreover, 10 or less is preferable, and 8 or less is more preferable.
- alkyl group examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, and 2-ethylhexyl group; , pentyl group, hexyl group, and 2-ethylhexyl group are preferable, and methyl group, ethyl group, propyl group, butyl group, and 2-ethylhexyl group are more preferable.
- the number of carbon atoms in the aryl group which may have a substituent in R 38 of formula (VIII) is not particularly limited, but is preferably 6 or more. Moreover, it is preferably 16 or less, more preferably 12 or less, and even more preferably 8 or less. For example, the number is preferably 6 to 16, more preferably 6 to 12, and even more preferably 6 to 8.
- aryl group examples include phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, diethylphenyl group, naphthyl group, and anthracenyl group; phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, A diethylphenyl group is preferable, and a phenyl group, a methylphenyl group, and an ethylphenyl group are more preferable.
- the number of carbon atoms in the optionally substituted aralkyl group in R 38 of formula (VIII) is not particularly limited, but is preferably 7 or more, preferably 16 or less, more preferably 12 or less, and 10 or less. More preferred. For example, the number is preferably 7 to 16, more preferably 7 to 12, and even more preferably 7 to 10.
- the aralkyl group include phenylmethyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, and phenylisopropyl group, and phenylmethyl group, phenylethyl group, phenylpropyl group, or phenylbutyl group is mentioned.
- a phenylmethyl group or a phenylethyl group is more preferable.
- R 38 is preferably an alkyl group or an aralkyl group, and more preferably a methyl group, ethyl group, butyl group, 2-ethylhexyl group or phenylmethyl group.
- substituents that the alkyl group in R 38 may have include a halogen atom and an alkoxy group.
- substituents that the aryl group or aralkyl group may have include a chain alkyl group, a halogen atom, and an alkoxy group.
- the chain alkyl group represented by R 38 includes both straight chain and branched chain alkyl groups.
- the content of the repeating unit (VIII) in all repeating units of the dispersant is preferably 30 mol% or more, more preferably 40 mol% or more, and even more preferably 50 mol% or more. Further, it is preferably 80 mol% or less, more preferably 70 mol% or less.
- the above upper and lower limits can be arbitrarily combined. For example, it is preferably 30 to 80 mol%, more preferably 40 to 80 mol%, even more preferably 50 to 70 mol%.
- the acrylic dispersant may have repeating units other than repeating units (V), repeating units (VI), repeating units (VII), and repeating units (VIII).
- repeating units include styrene monomers such as styrene and ⁇ -methylstyrene; (meth)acrylate monomers such as (meth)acrylic acid chloride; (meth)acrylamide, N- Examples include (meth)acrylamide monomers such as methylol acrylamide; repeating units derived from monomers such as vinyl acetate, acrylonitrile, allyl glycidyl ether, crotonic acid glycidyl ether, and N-methacryloylmorpholine.
- the acrylic dispersant consists of an A block having a repeating unit (V) and a repeating unit (VI), and a B block not having a repeating unit (V) and a repeating unit (VI). It is preferable that it is a block copolymer having the following.
- the block copolymer is preferably an AB block copolymer or a BAB block copolymer.
- the B block has a repeating unit (VII), and more preferably a repeating unit (VIII).
- the repeating unit (V) and the repeating unit (VI) may be contained in either random copolymerization or block copolymerization.
- two or more types of repeating units (V) and repeating units (VI) may be contained in one A block, and in that case, each repeating unit may be randomly copolymerized or block It may be contained in any form of copolymerization.
- Repeating units other than the repeating unit (V) and the repeating unit (VI) may be contained in the A block, and examples of such repeating units include the above-mentioned (meth)acrylic acid ester monomers. Examples include repeating units derived from The content of repeating units other than repeating units (V) and repeating units (VI) in A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, but such repeating units are It is particularly preferred that it is not contained in the block.
- Repeating units other than the repeating unit (VII) and the repeating unit (VIII) may be contained in the B block, and examples of such repeating units include styrene monomers such as styrene and ⁇ -methylstyrene.
- (meth)acrylate monomers such as (meth)acrylic acid chloride;
- (meth)acrylamide monomers such as (meth)acrylamide and N-methylol acrylamide; vinyl acetate, acrylonitrile, allyl glycidyl ether, croton
- Examples include repeating units derived from monomers such as acid glycidyl ether and N-methacryloylmorpholine.
- the content ratio of repeating units other than the repeating unit (VII) and the repeating unit (VIII) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, but such repeating units are It is particularly preferred that it is not contained in the block.
- These acrylic dispersants may be used alone or in combination of two or more.
- the photosensitive colored resin composition of the present invention contains (C) an alkali-soluble resin.
- the alkali-soluble resin contains a resin (C1) having a structural unit represented by the following general formula (1).
- R 1 represents a hydrogen atom or a methyl group.
- Each R 2 independently represents an alkyl group having 1 to 4 carbon atoms.
- L represents an alkylene group having 2 to 6 carbon atoms, and has at least a hydroxyl group or an ester group of a hydroxyl group and a polybasic acid as a substituent.
- Each * represents a bond.
- the resin (C1) has a high affinity with pigments, contains a methylene group in its main chain, and has flexibility that can follow the pigment, so it tends to exhibit high pigment dispersibility.
- the resin (C1) contains many aromatic rings in the main chain, it has high developer resistance during development in photosensitive colored resin compositions, and high heat resistance during baking, resulting in a high residual film rate.
- a high residual film rate tends to prevent decomposed products, by-products, uncured products, etc. in the composition from remaining on the electrode (anode) or re-adhering.
- an organic electroluminescent device is formed using a barrier rib obtained by curing a photosensitive colored resin composition, the amount of residue and re-deposition on the anode is reduced, which reduces the amount of deposits on the pixel area. This tends to increase the current density when a voltage is applied to the organic electroluminescent device and improve the brightness of the light emitting device.
- Each R 2 in formula (1) independently represents an alkyl group having 1 to 4 carbon atoms. From the viewpoint of solvent solubility, the number of carbon atoms in the alkyl group in R 2 is preferably 1 or more, preferably 3 or less, and more preferably 2 or less.
- the alkyl group may be straight chain or branched. Examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, and tert-butyl group. A methyl group is preferred from the viewpoint of dispersibility.
- (L) L represents an alkylene group having 2 to 6 carbon atoms, and has at least a hydroxyl group or an ester group of a hydroxyl group and a polybasic acid as a substituent.
- L preferably has 3 or more carbon atoms, more preferably 4 carbon atoms. Moreover, 5 or less is preferable. For example, it may be 3-6, it may be 3-5, it may be 4-6, it may be 4-5.
- L has at least a hydroxyl group or an ester group of a hydroxyl group and a polybasic acid as a substituent, and may be further substituted with a methoxy group or an ethoxy group.
- the polybasic acid means a polybasic acid listed in the polybasic acid residues described below.
- the ester group of a hydroxyl group and a polybasic acid means a group in which a hydroxyl group bonded to L forms an ester with a polybasic acid.
- the structural units of formula (1) it is preferable to have a structural unit described by the following general formula (2).
- A represents a hydrogen atom or a polybasic acid residue.
- R 1 represents a hydrogen atom or a methyl group.
- Each R 2 independently represents an alkyl group having 1 to 4 carbon atoms.
- Each * represents a bond.
- a in formula (1) represents a hydrogen atom or a polybasic acid residue.
- the polybasic acid residue means a monovalent or divalent group obtained by removing one or two OH groups from a polybasic acid.
- the polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endo.
- Examples include methylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
- maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and more Preferred are phthalic acid, succinic acid, trimellitic acid, and pyromellitic acid.
- trimellitic acid is preferred because the number of hydroxyl groups with high solvent affinity increases relative to the other basic acid residues.
- R 1 ) R 1 in formula (1) represents a hydrogen atom or a methyl group. Hydrogen atoms are preferred from the viewpoint of curability.
- Each R 2 in formula (1) independently represents an alkyl group having 1 to 4 carbon atoms. From the viewpoint of solvent solubility, the number of carbon atoms in the alkyl group in R 2 is preferably 1 or more, preferably 3 or less, and more preferably 2 or less.
- the alkyl group may be straight chain or branched. Examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, and tert-butyl group. A methyl group is preferred from the viewpoint of dispersibility.
- the partial structure represented by formula (1) contained in the resin (C1) may be one type or two or more types, for example, one where A is a hydrogen atom and one where A is a polybasic acid residue. They may be mixed.
- Examples of the resin (C1) include structures represented by the following general formulas (C1-1) to (C1-8).
- the resin (C1) preferably has a structure represented by formula (C1-1), formula (C1-3), formula (C1-7), or formula (C1-8).
- the acid value of the resin (C1) is not particularly limited, but is preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, even more preferably 40 mgKOH/g or more, and even more preferably 50 mgKOH/g or more. Further, it is preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less, even more preferably 100 mgKOH/g or less, and particularly preferably 80 mgKOH/g or less.
- the above upper and lower limits can be arbitrarily combined. For example, it is preferably 10 to 200 mgKOH/g, more preferably 30 to 150 mgKOH/g, even more preferably 40 to 100 mgKOH/g, and even more preferably 50 to 80 mgKOH/g.
- the amount is at least the lower limit, development solubility tends to improve and resolution tends to improve. There is a tendency for the residual film rate to become good by setting it below the upper limit value.
- the method for producing the resin (C1) is not particularly limited, but for example, (meth)acrylic acid is added to an epoxy resin represented by the following general formula (1-2), and then reacted with a polybasic acid and/or its anhydride. It can be obtained by letting
- R 2 and * in formula (1-2) have the same meanings as in formula (1).
- Examples of the epoxy resin represented by formula (1-2) include the following epoxy resins.
- m represents an integer from 2 to 8.
- an epoxy resin and (meth)acrylic acid can be reacted at a temperature of 50 to 150° C. in the presence of an esterification catalyst.
- an esterification catalyst for example, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride can be used.
- tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine
- quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride can be used.
- polybasic acid and/or its anhydride the above-mentioned polybasic acid or its anhydride can be mentioned.
- the addition reaction of a polybasic acid and/or its anhydride can be performed using a known method.
- the photosensitive colored resin composition used in the present invention may contain (C) an alkali-soluble resin other than the resin (C1).
- an alkali-soluble resin other than the resin (C1) there is no particular limitation as long as the resin exhibits alkali solubility, and examples thereof include resins containing carboxyl groups or hydroxyl groups. More specifically, examples include epoxy (meth)acrylate resins, acrylic resins, and carboxyl group-containing epoxy resins. Examples include resins, carboxyl group-containing urethane resins, novolac resins, polyvinylphenol resins, and isocyanuric skeleton-containing resins.
- the alkali-soluble resin (C) other than resin (C1) is (C2) Epoxy (meth)acrylate resin (C3) Isocyanuric skeleton-containing resin (C4)
- Acrylic copolymer resin is preferably used from the viewpoint of excellent plate-making properties. These can be used alone or in combination of two or more.
- the (C2) epoxy (meth)acrylate resin in the present invention is an alkali-soluble resin (C) other than the resin (C1), and is composed of an epoxy compound (epoxy resin) and an ⁇ , ⁇ -unsaturated monocarboxylic acid and/or ester.
- a compound that has two or more substituents that can further react with a hydroxyl group such as a polybasic acid and/or its anhydride, in addition to the hydroxyl group produced by the reaction with an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group in its moiety.
- the isocyanuric skeleton-containing resin (C3) described below is not included. Before reacting the polybasic acid and/or its anhydride with a hydroxyl group, a compound having two or more substituents that can react with a hydroxyl group is reacted, and then the polybasic acid and/or its anhydride is reacted. The resin obtained by this is also included in the (C2) epoxy (meth)acrylate resin.
- Epoxy (meth)acrylate resin has a chemical structure that substantially does not have an epoxy group, and is not limited to "(meth)acrylate,” but it uses an epoxy compound (epoxy resin) as a raw material, and , "(meth)acrylate” is a typical example, so it is named this way according to common usage.
- epoxy (meth)acrylate resin used in the present invention the following epoxy (meth)acrylate resin (C2-1) and/or epoxy (meth)acrylate resin (C2-2) (hereinafter referred to as "carboxylic (sometimes referred to as “group-containing epoxy (meth)acrylate resin”) is preferably used from the viewpoint of developability and reliability.
- carboxylic sometimes referred to as "group-containing epoxy (meth)acrylate resin”
- epoxy (meth)acrylate resin one having an aromatic ring in the main chain can be more preferably used from the viewpoint of outgassing.
- the epoxy resin includes a raw material compound before forming a resin by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins. Further, as the epoxy resin, a compound obtained by reacting a phenolic compound and epihalohydrin can be used.
- the phenolic compound is preferably a compound having a divalent or more than divalent phenolic hydroxyl group, and may be a monomer or a polymer. Examples of the types of epoxy resins used as raw materials include cresol novolak epoxy resin, phenol novolac epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, trisphenolmethane epoxy resin, biphenyl novolac epoxy resin, and naphthalene.
- Novolak-type epoxy resins epoxy resins that are reaction products of polyaddition products of dicyclopentadiene and phenol or cresol, and epihalohydrin, adamantyl group-containing epoxy resins, and fluorene-type epoxy resins can be suitably used. Those having an aromatic ring can be more preferably used.
- epoxy resins examples include bisphenol A type epoxy resins (for example, "jER (registered trademark, the same applies hereinafter) 828", “jER1001", “jER1002", “jER1004", etc. manufactured by Mitsubishi Chemical Corporation), bisphenol A type epoxy resins, etc. Epoxy resins obtained by the reaction of alcoholic hydroxyl groups of epoxy resins with epichlorohydrin (for example, "NER-1302” manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent: 323, softening point 76°C)), bisphenol F type resins (for example, manufactured by Mitsubishi Chemical Co., Ltd.) "JER807", “EP-4001”, “EP-4002", “EP-4004", etc.
- bisphenol A type epoxy resins for example, "jER (registered trademark, the same applies hereinafter) 828", “jER1001", “jER1002", “jER1004", etc. manufactured by Mitsubishi Chemical Corporation
- a is an average value and represents a number from 0 to 10
- each R 111 is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. group, phenyl group, naphthyl group, or biphenyl group. Note that a plurality of R 111s present in one molecule may be the same or different.
- b1 and b2 are average values, and each independently represents a number from 0 to 10, and R 121 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or 3 carbon atoms. ⁇ 10 cycloalkyl, phenyl, naphthyl, or biphenyl groups. Note that the plurality of R 121s present in one molecule may be the same or different.
- X represents a linking group represented by the following general formula (C2 ⁇ -1) or (C2 ⁇ -2).
- the molecular structure contains one or more adamantane structures.
- c represents 2 or 3.
- R 131 to R 134 and R 135 to R 137 each independently represent an adamantyl group which may have a substituent, a hydrogen atom, or a substituent. represents an optionally substituted alkyl group having 1 to 12 carbon atoms, or a phenyl group optionally having a substituent, and * represents a bond.
- R 141 and R 142 each independently represent an alkyl group having 1 to 4 carbon atoms or a halogen atom
- R 143 and R 144 are Each independently represents an alkylene group having 1 to 4 carbon atoms
- x and y each independently represents an integer of 0 or more.
- epoxy resin it is preferable to use an epoxy resin represented by any of the formulas (C2 ⁇ ) to (C2 ⁇ ).
- Examples of the ⁇ , ⁇ -unsaturated monocarboxylic acid or the ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group include (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, Monocarboxylic acids such as ⁇ -position haloalkyl, alkoxyl, halogen, nitro, and cyano substituted products of (meth)acrylic acid; 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethyladipic acid, 2 -(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethylmaleic acid, 2-(meth)acryloyloxypropyl succinic acid, 2 -(meth)acryloyl
- a method for adding an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin a known method can be used. For example, it is possible to react an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group with an epoxy resin at a temperature of 50 to 150°C in the presence of an esterification catalyst. can.
- esterification catalyst used here for example, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, and quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride can be used.
- tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine
- quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride
- Each component of the epoxy resin, ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group, and esterification catalyst may be selected one by one and used. , two or more types may be used in combination.
- the amount of ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group is preferably 0.5 to 1.2 equivalents per equivalent of epoxy group in the epoxy resin, and Preferably it is 0.7 to 1.1 equivalent.
- polybasic acids and/or anhydrides examples include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, and methylhexahydrophthalic acid.
- examples include hydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.
- maleic acid succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, and anhydrides thereof.
- Particularly preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.
- the addition reaction of a polybasic acid and/or its anhydride can be carried out using a known method.
- the desired product can be obtained by continuing the reaction under the same conditions as the addition reaction of carboxylic acid esters.
- the amount of polybasic acid and/or its anhydride component added is preferably such that the acid value of the resulting carboxyl group-containing epoxy (meth)acrylate resin is 10 to 150 mgKOH/g, and more preferably 20 to 150 mgKOH/g. It is preferable that the amount added be ⁇ 140 mgKOH/g.
- the amount is equal to or more than the lower limit, the alkali developability tends to be improved. There is a tendency for curing performance to be improved by setting the amount to be less than or equal to the upper limit value.
- polyfunctional alcohols such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, 1,2,3-propanetriol, etc.
- polyfunctional alcohols such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, 1,2,3-propanetriol, etc.
- any hydroxyl group present in the mixture of the epoxy resin and the reaction product of ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxyl group and polyfunctional alcohol is removed.
- a polybasic acid and/or its anhydride undergoes an addition reaction.
- carboxyl group-containing epoxy (meth)acrylate resin in addition to the above-mentioned ones, examples include those described in Korean Patent Publication No. 10-2013-0022955.
- the weight average molecular weight (Mw) of the carboxyl group-containing epoxy (meth)acrylate resin in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 1000 or more, more preferably 1500 or more, even more preferably 2000 or more, It is even more preferably 3,000 or more, particularly preferably 4,000 or more, particularly preferably 5,000 or more. Further, it is preferably 30,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 1,000 to 30,000, more preferably 1,500 to 20,000, even more preferably 1,500 to 15,000, and even more preferably 2,000 to 15,000.
- the amount By setting the amount to be at least the lower limit, it tends to be possible to prevent the solubility in the developer from becoming too high. By setting it below the above-mentioned upper limit, there is a tendency that the solubility in the developer tends to be good.
- the acid value of the carboxyl group-containing epoxy (meth)acrylate resin is not particularly limited, but is preferably 20 mgKOH/g or more, more preferably 40 mgKOH/g or more, even more preferably 60 mgKOH/g or more, even more preferably 80 mgKOH/g or more. , 100 mgKOH/g or more is particularly preferred. Moreover, 200 mgKOH/g or less is preferable, 150 mgKOH/g or less is more preferable, 130 mgKOH/g or less is still more preferable, and 120 mgKOH/g or less is particularly preferable. The above upper and lower limits can be arbitrarily combined.
- it is preferably 20 to 200 mgKOH/g, more preferably 60 to 150 mgKOH/g, even more preferably 80 to 130 mgKOH/g, and even more preferably 100 to 130 mgKOH/g.
- amount is at least the lower limit, development solubility tends to improve and resolution tends to improve.
- the residual film rate of the photosensitive colored resin composition tends to be good.
- the chemical structure of the epoxy (meth)acrylate resin is not particularly limited, but from the viewpoint of developability and reliability, an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (C2-I) Resin (hereinafter sometimes abbreviated as "(C2-I) epoxy (meth)acrylate resin”) and/or epoxy (meth)acrylate having a partial structure represented by the following general formula (C2-II) It is preferable to contain a resin (hereinafter sometimes abbreviated as "(C2-II) epoxy (meth)acrylate resin").
- R 11 represents a hydrogen atom or a methyl group
- R 12 represents a divalent hydrocarbon group that may have a substituent
- k represents 1 or 2
- the benzene ring in formula (C2-I) may be further substituted with any substituent.
- R 13 each independently represents a hydrogen atom or a methyl group
- R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain
- R 15 and R 16 each independently represents a divalent aliphatic group which may have a substituent
- m and n each independently represent an integer of 0 to 2
- * represents a bond.
- R 11 represents a hydrogen atom or a methyl group
- R 12 represents a divalent hydrocarbon group that may have a substituent
- k represents 1 or 2
- the benzene ring in formula (C2-I) may be further substituted with any substituent.
- R 12 represents a divalent hydrocarbon group which may have a substituent.
- divalent hydrocarbon groups include divalent aliphatic groups, divalent aromatic ring groups, and groups in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are connected. Can be mentioned.
- Examples of divalent aliphatic groups include linear, branched, and cyclic aliphatic groups. From the viewpoint of development solubility, linear aliphatic groups are preferred. On the other hand, a cyclic aliphatic group is preferable from the viewpoint of reducing permeation of the developer into the exposed area.
- the number of carbon atoms is preferably 1 or more, more preferably 3 or more, and even more preferably 6 or more. Further, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The above upper and lower limits can be arbitrarily combined. For example, the number is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10.
- the amount is at least the lower limit, a strong film is easily obtained, the surface roughness that occurs during development is less likely to occur, and the adhesion to the substrate tends to be good.
- the upper limit By setting it below the upper limit, deterioration of sensitivity can be suppressed, the residual film rate after development tends to be high, and resolution tends to improve.
- divalent linear aliphatic group examples include methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, and n-heptylene group. From the viewpoint of the rigidity of the skeleton, a methylene group is preferred.
- the divalent branched aliphatic group includes, for example, a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group as a side chain in addition to the above-mentioned divalent linear aliphatic group.
- Examples include structures having a group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
- the number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is preferably 1 or more, and more preferably 2 or more. Moreover, 12 or less is preferable, and 10 or less is more preferable.
- the above upper and lower limits can be arbitrarily combined. For example, the number is preferably 1 to 12, more preferably 1 to 10, and even more preferably 2 to 10. When the amount is equal to or more than the lower limit, the film tends to be strong and have good adhesion to the substrate.
- divalent cyclic aliphatic groups include hydrogen atoms removed from rings such as cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, dicyclopentadiene, and dicyclopentane.
- groups divided by two From the viewpoint of rigidity of the skeleton, a group obtained by removing two hydrogen atoms from a dicyclopentadiene ring, a dicyclopentane ring, or an adamantane ring is preferable.
- Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group. From the viewpoint of ease of synthesis, it is preferable that it is unsubstituted.
- divalent aromatic ring group examples include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
- the number of carbon atoms is not particularly limited, but is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more. Further, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
- the above upper and lower limits can be arbitrarily combined. For example, the number is preferably 4 to 20, more preferably 5 to 15, and even more preferably 6 to 10.
- the amount is at least the lower limit, a strong film is easily obtained, the surface roughness that occurs during development is less likely to occur, and the adhesion to the substrate tends to be good. By setting it below the upper limit, deterioration of sensitivity can be suppressed, the residual film rate after development tends to be high, and resolution tends to improve.
- the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a fused ring.
- Examples of the divalent aromatic hydrocarbon ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, Examples include triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.
- the aromatic heterocycle in the divalent aromatic heterocyclic group may be a single ring or a condensed ring.
- divalent aromatic heterocyclic group examples include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, and indole ring having two free valences.
- benzene ring or a naphthalene ring having two free valence examples include pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring.
- a benzene ring or a naphthalene ring having two free valence examples include pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring.
- Examples of the substituents that the divalent aromatic ring group may have include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. From the viewpoint of development solubility, non-substitution is preferred.
- the group linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups includes one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic ring group.
- Examples include groups in which one or more are linked.
- the number of divalent aliphatic groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, also preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
- the above upper and lower limits can be arbitrarily combined. For example, the number is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 2 to 3.
- the number of divalent aromatic ring groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
- the above upper and lower limits can be arbitrarily combined. For example, the number is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 2 to 3.
- the amount is at least the lower limit, a strong film is easily obtained, the surface roughness that occurs during development is less likely to occur, and the adhesion to the substrate tends to be good.
- the upper limit By setting it below the upper limit, deterioration of sensitivity can be suppressed, the residual film rate after development tends to be high, and resolution tends to improve.
- Examples of groups connecting one or more divalent aliphatic groups and one or more divalent aromatic ring groups include those represented by the following formulas (C2-I-A) to (C2-IF). Examples include groups such as In the following formulas (C2-IA) to (C2-IF), * represents a bond. From the viewpoint of rigidity of the skeleton and hydrophobicization of the membrane, a group represented by the following formula (C2-IA) is preferable.
- k represents 1 or 2. From the viewpoint of adhesion and plate-making properties, k is preferably 1. From the viewpoint of sensitivity, k is preferably 2. Furthermore, both a partial structure in which k is 1 and a partial structure in which k is 2 may be contained in the (C2-I) epoxy (meth)acrylate.
- the benzene ring in formula (C2-I) may be further substituted with any substituent.
- substituents include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
- the number of substituents is not particularly limited either, and may be one or two or more. From the viewpoint of plate-making properties, it is preferable that no substitution be made.
- the partial structure represented by formula (C2-I) is preferably a partial structure represented by the following general formula (C2-I-1) from the viewpoint of ease of synthesis.
- R 11 , R 12 and k have the same meanings as in formula (C2-I), R x represents a hydrogen atom or a polybasic acid residue, and * represents a bond. .
- the benzene ring in formula (C2-I-1) may be further substituted with any substituent.
- the polybasic acid residue means a monovalent or divalent group obtained by removing one or two OH groups from a polybasic acid.
- polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylene.
- examples include tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
- maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid are preferable, and tetrahydrophthalic acid is more preferable.
- phthalic acid, biphenyltetracarboxylic acid, and biphenyltetracarboxylic acid are preferable, and tetrahydrophthalic acid.
- the benzene ring in formula (C2-I-1) may be further substituted with any substituent.
- substituent those listed for the benzene ring in formula (C2-I) can be preferably employed.
- the partial structure represented by formula (C2-I-1) contained in one molecule of epoxy (meth)acrylate resin may be one type or two or more types, for example, R x is hydrogen. There may be a mixture of atoms and those in which R x is a polybasic acid residue.
- the number of partial structures represented by formula (C2-I) contained in one molecule of the epoxy (meth)acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 3 or more. Moreover, 20 or less is preferable, and 15 or less is more preferable.
- the above upper and lower limits can be arbitrarily combined. The number is preferably 1 to 20, more preferably 1 to 15, and even more preferably 3 to 15.
- the amount is equal to or more than the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting it below the upper limit, deterioration of sensitivity can be suppressed, the residual film rate after development tends to be high, and resolution tends to improve.
- the weight average molecular weight (Mw) of the epoxy (meth)acrylate resin in terms of polystyrene measured by gel permeation chromatography (GPC) is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more. , more preferably 2,000 or more, even more preferably 3,000 or more, particularly preferably 4,000 or more, most preferably 5,000 or more, and preferably 30,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less.
- the above upper and lower limits can be arbitrarily combined. For example, it is preferably 1,000 to 30,000, more preferably 1,500 to 2,000, even more preferably 1,500 to 15,000, even more preferably 2,000 to 1,500.
- the amount is equal to or more than the lower limit, the remaining film rate of the photosensitive colored resin composition tends to be good.
- the solubility in the developer tends to be improved.
- the acid value of the epoxy (meth)acrylate resin is not particularly limited, but is preferably 20 mgKOH/g or more, more preferably 40 mgKOH/g or more, even more preferably 60 mgKOH/g or more, and 80 mgKOH/g or more. It is even more preferable, and particularly preferably 100 mgKOH/g or more. Moreover, 200 mgKOH/g or less is preferable, 150 mgKOH/g or less is more preferable, 130 mgKOH/g or less is even more preferable, and 120 mgKOH/g or less is particularly preferable. The above upper and lower limits can be arbitrarily combined.
- it is preferably 20 to 200 mgKOH/g, more preferably 60 to 150 mgKOH/g, even more preferably 80 to 130 mgKOH/g, and even more preferably 100 to 130 mgKOH/g.
- amount is at least the lower limit, development solubility tends to improve and resolution tends to improve.
- the residual film rate of the photosensitive colored resin composition tends to be good.
- R 13 each independently represents a hydrogen atom or a methyl group
- R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain
- R 15 and R 16 each independently represents a divalent aliphatic group which may have a substituent
- m and n each independently represent an integer of 0 to 2
- * represents a bond.
- R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
- the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
- the number of rings that the aliphatic cyclic group has is not particularly limited, but is preferably 1 or more, and more preferably 2 or more. Further, it is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
- the above upper and lower limits can be arbitrarily combined.
- the number is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 2 to 3.
- the amount is equal to or more than the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur.
- the amount is equal to or more than the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur.
- deterioration of sensitivity can be suppressed, the residual film rate after development tends to be high, and resolution tends to improve.
- the number of carbon atoms in the aliphatic cyclic group is not particularly limited, but is preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more. Further, it is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less.
- the above upper and lower limits can be arbitrarily combined.
- the number is preferably 4 to 40, more preferably 4 to 30, even more preferably 6 to 20, and particularly preferably 8 to 15. When the amount is equal to or more than the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur.
- the aliphatic ring in the aliphatic cyclic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. From the viewpoint of the residual film rate and resolution of the photosensitive colored resin composition, an adamantane ring is preferred.
- the number of rings that the aromatic ring group has is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. Further, it is preferably 10 or less, more preferably 5 or less, and even more preferably 4 or less.
- the above upper and lower limits can be arbitrarily combined.
- the number is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 4, even more preferably 2 to 4, and particularly preferably 3 to 4.
- the amount is equal to or more than the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur.
- the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
- the number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, even more preferably 10 or more, and particularly preferably 12 or more. Further, it is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less.
- the above upper and lower limits can be arbitrarily combined.
- the number is preferably 4 to 40, more preferably 6 to 40, even more preferably 8 to 30, even more preferably 10 to 20, and particularly preferably 12 to 15.
- the amount is equal to or more than the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur.
- patterning characteristics tend to be improved.
- Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
- Examples include rings. From the viewpoint of patterning properties, a fluorene ring is preferred.
- the divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, but includes, for example, a divalent aliphatic group, a divalent aromatic ring group, and one or more divalent hydrocarbon groups. Examples include groups in which a valent aliphatic group and one or more divalent aromatic ring groups are connected.
- Examples of divalent aliphatic groups include linear, branched, and cyclic aliphatic groups.
- a linear aliphatic group is preferred from the viewpoint of development solubility, while a cyclic aliphatic group is preferred from the viewpoint of reducing permeation of the developer into the exposed area.
- the number of carbon atoms is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and even more preferably 6 or more. Further, it is preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less. The above upper and lower limits can be arbitrarily combined. For example, the number is preferably 1 to 25, more preferably 3 to 20, and even more preferably 6 to 15.
- the amount is at least the lower limit, a strong film is easily obtained, the surface roughness that occurs during development is less likely to occur, and the adhesion to the substrate tends to be good.
- the upper limit By setting it below the upper limit, deterioration of sensitivity can be suppressed, the residual film rate after development tends to be high, and resolution tends to improve.
- Examples of the divalent linear aliphatic group include methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, and n-heptylene group. From the viewpoint of the rigidity of the skeleton, a methylene group is preferred.
- Examples of the divalent branched aliphatic group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group as a side chain in addition to the above-mentioned divalent linear aliphatic group. , an isobutyl group, a sec-butyl group, and a tert-butyl group.
- the number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is preferably 1 or more, and more preferably 2 or more. Further, it is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
- the above upper and lower limits can be arbitrarily combined.
- the number is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 2 to 3.
- the content is equal to or more than the lower limit, the film tends to be strong and have good adhesion to the substrate.
- the upper limit deterioration of sensitivity can be suppressed, the residual film rate after development tends to be high, and resolution tends to improve.
- Examples of the divalent cyclic aliphatic group include groups obtained by removing two hydrogen atoms from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. From the viewpoint of skeleton rigidity, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable.
- Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group. From the viewpoint of ease of synthesis, it is preferable that it is unsubstituted.
- divalent aromatic ring group examples include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
- the number of carbon atoms is not particularly limited, but is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more. Further, it is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less.
- the above upper and lower limits can be arbitrarily combined. For example, the number is preferably 4 to 30, more preferably 5 to 20, and even more preferably 6 to 15.
- the amount is at least the lower limit, a strong film is easily obtained, the surface roughness that occurs during development is less likely to occur, and the adhesion to the substrate tends to be good. By setting it below the upper limit, deterioration of sensitivity can be suppressed, the residual film rate after development tends to be high, and resolution tends to improve.
- the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a fused ring.
- Examples of the divalent aromatic hydrocarbon ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, Examples include triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.
- the aromatic heterocycle in the divalent aromatic heterocyclic group may be a single ring or a condensed ring.
- divalent aromatic heterocyclic group examples include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, and indole ring having two free valences.
- benzene ring or a naphthalene ring having two free valence examples include pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring.
- a benzene ring or a naphthalene ring having two free valence examples include pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring.
- Examples of the substituents that the divalent aromatic ring group may have include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. From the viewpoint of development solubility, non-substitution is preferred.
- the group linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups includes one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic ring group.
- Examples include groups in which one or more are linked.
- the number of divalent aliphatic groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
- the above upper and lower limits can be arbitrarily combined. For example, the number is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 2 to 3.
- the number of divalent aromatic ring groups is not particularly limited, but is preferably 1 or more, more preferably 2 or more, 10 or less, more preferably 5 or less, and even more preferably 3 or less.
- the above upper and lower limits can be arbitrarily combined.
- the number is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 2 to 3.
- the amount is at least the lower limit, a strong film is easily obtained, the surface roughness that occurs during development is less likely to occur, and the adhesion to the substrate tends to be good.
- the upper limit By setting it below the upper limit, deterioration of sensitivity can be suppressed, the residual film rate after development tends to be high, and resolution tends to improve.
- Examples of groups linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups include those represented by the above-mentioned formulas (C2-I-A) to (C2-IF). The following groups are mentioned. From the viewpoint of skeleton rigidity and membrane hydrophobization, a group represented by formula (C2-IC) is preferred.
- the bonding mode of the cyclic hydrocarbon group as a side chain to these divalent hydrocarbon groups is not particularly limited, but for example, if one hydrogen atom of an aliphatic group or an aromatic ring group is Examples include an embodiment in which the aliphatic group is substituted with a hydrocarbon group, and an embodiment in which a cyclic hydrocarbon group that is a side chain includes one of the carbon atoms of the aliphatic group.
- R 15 and R 16 each independently represent a divalent aliphatic group which may have a substituent.
- Examples of divalent aliphatic groups include linear, branched, and cyclic aliphatic groups.
- a linear aliphatic group is preferred from the viewpoint of development solubility, while a cyclic aliphatic group is preferred from the viewpoint of reducing permeation of the developer into the exposed area.
- the number of carbon atoms is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and even more preferably 6 or more. Further, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The above upper and lower limits can be arbitrarily combined. For example, the number is preferably 1 to 20, more preferably 3 to 15, and even more preferably 6 to 10.
- the amount is at least the lower limit, a strong film is easily obtained, the surface roughness that occurs during development is less likely to occur, and the adhesion to the substrate tends to be good.
- the upper limit By setting it below the upper limit, deterioration of sensitivity can be suppressed, the residual film rate after development tends to be high, and resolution tends to improve.
- divalent linear aliphatic group examples include methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, and n-heptylene group. From the viewpoint of the rigidity of the skeleton, a methylene group is preferred.
- the divalent branched aliphatic group includes, for example, a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group as a side chain in addition to the above-mentioned divalent linear aliphatic group.
- Examples include structures having a group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
- the number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is preferably 1 or more, and more preferably 2 or more. Moreover, 12 or less is preferable, and 10 or less is more preferable.
- the above upper and lower limits can be arbitrarily combined. For example, 1 to 12 is preferable, and 2 to 10 is more preferable. When the amount is equal to or more than the lower limit, the film tends to be strong and have good adhesion to the substrate.
- divalent cyclic aliphatic groups include groups obtained by removing two hydrogen atoms from a cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, and dicyclopentadiene ring. Can be mentioned. From the viewpoint of skeleton rigidity, a group obtained by removing two hydrogen atoms from a dicyclopentadiene ring or an adamantane ring is preferable.
- Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group. From the viewpoint of ease of synthesis, it is preferable that it is unsubstituted.
- m and n each independently represent an integer of 0 to 2.
- the amount is at least the lower limit, patterning becomes more appropriate and surface roughness that occurs during development tends to be less likely to occur, and when the amount is at most the upper limit, the developability tends to be good.
- m and n are preferably 0.
- m and n are preferably 1 or more.
- the partial structure represented by the formula (C2-II) is preferably a partial structure represented by the following general formula (C2-II-1) from the viewpoint of adhesion to the substrate.
- R 13 , R 15 , R 16 , m and n have the same meanings as in formula (C2-II), and R ⁇ is a monovalent group which may have a substituent. represents a cyclic hydrocarbon group, p represents an integer of 1 or more, and * represents a bond.
- the benzene ring in formula (C2-II-1) may be further substituted with any substituent.
- R ⁇ represents a monovalent cyclic hydrocarbon group which may have a substituent.
- the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
- the number of rings that the aliphatic cyclic group has is not particularly limited, but is preferably one or more, and more preferably two or more. Further, it is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.
- the above upper and lower limits can be arbitrarily combined. For example, 1 to 6 are preferred, 1 to 4 are more preferred, 1 to 3 are even more preferred, and 2 to 3 are particularly preferred.
- the amount is equal to or more than the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting it below the above-mentioned upper limit, patterning characteristics tend to be improved.
- the number of carbon atoms in the aliphatic cyclic group is not particularly limited, but is preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more. Further, it is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less.
- the above upper and lower limits can be arbitrarily combined.
- the number is preferably 4 to 40, more preferably 4 to 30, even more preferably 6 to 20, and particularly preferably 8 to 15.
- the amount is equal to or more than the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting it below the above-mentioned upper limit, patterning characteristics tend to be improved.
- Examples of the aliphatic ring in the aliphatic cyclic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. From the viewpoint of strong film properties, an adamantane ring is preferred.
- the number of rings that the aromatic ring group has is not particularly limited, but is preferably 1 or more, preferably 2 or more, and more preferably 3 or more. Moreover, 10 or less is preferable, and 5 or less is more preferable.
- the above upper and lower limits can be arbitrarily combined. For example, the number is preferably 1 to 10, more preferably 1 to 5, even more preferably 2 to 5, and particularly preferably 3 to 5.
- the amount is at least the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting it below the above-mentioned upper limit, patterning characteristics tend to be improved.
- the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
- the number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more. Further, it is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less.
- the above upper and lower limits can be arbitrarily combined. For example, the number is preferably 4 to 30, more preferably 5 to 20, and even more preferably 6 to 15.
- the amount is at least the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting it below the above-mentioned upper limit, patterning characteristics tend to be improved.
- Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. From the viewpoint of development solubility, a fluorene ring is preferred.
- substituents that the cyclic hydrocarbon group may have include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, amyl group, Examples include alkyl groups having 1 to 5 carbon atoms such as isoamyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; and carboxy group. From the viewpoint of ease of synthesis, no substitution is preferred.
- p represents an integer of 1 or more, preferably 2 or more. Moreover, 3 or less is preferable. For example, 1 to 3 are preferable, and 2 to 3 are more preferable.
- the amount is equal to or more than the lower limit, the degree of film curing and the remaining film rate tend to be good.
- the amount is below the upper limit, developability tends to be improved.
- R ⁇ is preferably a monovalent aliphatic cyclic group, and more preferably an adamantyl group.
- the benzene ring in formula (C2-II-1) may be further substituted with any substituent.
- substituents include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
- the number of substituents is not particularly limited either, and may be one or two or more. From the viewpoint of patterning properties, it is preferable that no substitution be made.
- the partial structure represented by the formula (C2-II) is preferably a partial structure represented by the following general formula (C2-II-2) from the viewpoint of skeleton rigidity and membrane hydrophobization.
- R 13 , R 15 , R 16 , m and n have the same meanings as in formula (C2-II), and R ⁇ is a divalent group which may have a substituent. represents a cyclic hydrocarbon group, and * represents a bond.
- the benzene ring in formula (C2-II-2) may be further substituted with any substituent.
- R ⁇ represents a divalent cyclic hydrocarbon group which may have a substituent.
- examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
- the number of rings that the aliphatic cyclic group has is not particularly limited, but is preferably one or more, and more preferably two or more. Moreover, 10 or less is preferable, and 5 or less is more preferable.
- the above upper and lower limits can be arbitrarily combined. For example, 1 to 10 is preferable, and 2 to 5 is more preferable.
- the amount is equal to or more than the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur. By setting it below the upper limit, deterioration of sensitivity can be suppressed, the residual film rate after development tends to be high, and resolution tends to improve.
- the number of carbon atoms in the aliphatic cyclic group is preferably 4 or more, more preferably 6 or more, and even more preferably 8 or more. Further, it is preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less.
- the above upper and lower limits can be arbitrarily combined. For example, the number is preferably 4 to 40, more preferably 6 to 35, and even more preferably 8 to 30.
- Examples of the aliphatic ring in the aliphatic cyclic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. From the viewpoint of the residual film rate after development and the resolution, an adamantane ring is preferable.
- the number of rings that the aromatic ring group has is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more. Moreover, 10 or less is preferable, and 5 or less is more preferable.
- the above upper and lower limits can be arbitrarily combined.
- the number is preferably 1 to 10, more preferably 1 to 5, even more preferably 2 to 5, and particularly preferably 3 to 5.
- the amount is equal to or more than the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur.
- deterioration of sensitivity and film thinning can be easily suppressed, and resolution tends to improve.
- the aromatic ring group examples include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
- the number of carbon atoms in the aromatic ring group is preferably 4 or more, more preferably 6 or more, even more preferably 8 or more, and even more preferably 10 or more. Further, it is preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less.
- the above upper and lower limits can be arbitrarily combined.
- the number is preferably 4 to 40, more preferably 6 to 30, even more preferably 8 to 20, and particularly preferably 10 to 15. When the amount is equal to or more than the lower limit, a strong film can be easily obtained, and surface roughness that occurs during development tends to be less likely to occur.
- the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring.
- fluorene rings are preferred. Since the plane forming the fluorene ring is perpendicular to the bond connecting the two benzene rings, it becomes bulkier and has a more rigid skeleton, making it difficult for developer solution to penetrate and shrinkage during baking.As a result, there is no residual film. It is estimated that the rate will increase.
- substituents that the cyclic hydrocarbon group may have include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, amyl group, Examples include alkyl groups having 1 to 5 carbon atoms such as isoamyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; and carboxy group. From the viewpoint of ease of synthesis, no substitution is preferred.
- R ⁇ is preferably a divalent aliphatic cyclic group, and more preferably a divalent adamantane cyclic group.
- R ⁇ is preferably a divalent aromatic ring group, and more preferably a divalent fluorene ring group.
- the benzene ring in formula (C2-II-2) may be further substituted with any substituent.
- substituents include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
- the number of substituents is not particularly limited either, and may be one or two or more.
- two benzene rings may be connected via a substituent.
- Examples of the substituent in this case include divalent groups such as -O-, -S-, -NH-, and -CH 2 -. From the viewpoint of patterning properties, it is preferable that no substitution be made. Furthermore, from the viewpoint of making film thinning less likely to occur, methyl group substitution is preferable.
- the partial structure represented by the formula (C2-II) is preferably a partial structure represented by the following general formula (C2-II-3) from the viewpoint of coating film residual rate and patterning characteristics.
- R 13 , R 14 , R 15 , R 16 , m and n have the same meanings as in formula (C2-II), and R Z represents a hydrogen atom or a polybasic acid residue. represent.
- the polybasic acid residue means a monovalent or divalent group obtained by removing one or two OH groups from a polybasic acid. Note that one more OH group may be removed and shared with R Z in another molecule represented by formula (C2-II-3). That is, a plurality of formulas (C2-II-3) may be connected via R Z.
- polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylene.
- Examples include tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
- maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid are preferable, and tetrahydrophthalic acid is more preferable.
- They are phthalic acid, biphenyltetracarboxylic acid, and biphenyltetracarboxylic acid.
- the partial structure represented by formula (C2-II-3) contained in one molecule of epoxy (meth)acrylate resin may be one type or two or more types, for example, R Z is hydrogen. There may be a mixture of atoms and those in which R Z is a polybasic acid residue.
- the number of partial structures represented by the formula (C2-II) contained in one molecule of the epoxy (meth)acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 3 or more. Further, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
- the above upper and lower limits can be arbitrarily combined.
- the number is preferably 1 to 20, more preferably 1 to 15, and even more preferably 3 to 10.
- the weight average molecular weight (Mw) of the epoxy (meth)acrylate resin measured by gel permeation chromatography (GPC) in terms of polystyrene is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more. , more preferably 2000 or more, even more preferably 3000 or more, even more preferably 4000 or more, particularly preferably 5000 or more. Further, it is preferably 10,000 or less, more preferably 8,000 or less, and even more preferably 7,000 or less. The above upper and lower limits can be arbitrarily combined.
- it is preferably 1,000 to 10,000, more preferably 1,500 to 10,000, even more preferably 1,500 to 8,000, even more preferably 2,000 to 8,000, and particularly preferably 2,000 to 7,000.
- the amount is equal to or more than the lower limit, the remaining film rate of the photosensitive colored resin composition tends to be good.
- the content is below the upper limit, the solubility in the developer tends to be improved.
- the acid value of the epoxy (meth)acrylate resin is not particularly limited, but is preferably 20 mgKOH/g or more, more preferably 40 mgKOH/g or more, even more preferably 60 mgKOH/g or more, and even more preferably 80 mgKOH/g or more. More preferably, 100 mgKOH/g or more is particularly preferable. Moreover, 200 mgKOH/g or less is preferable, 150 mgKOH/g or less is more preferable, 130 mgKOH/g or less is even more preferable, and 120 mgKOH/g or less is particularly preferable. The above upper and lower limits can be arbitrarily combined.
- it is preferably 20 to 200 mgKOH/g, more preferably 60 to 150 mgKOH/g, even more preferably 80 to 130 mgKOH/g, and even more preferably 100 to 130 mgKOH/g.
- amount is at least the lower limit, development solubility tends to improve and resolution tends to improve.
- the residual film rate of the photosensitive colored resin composition tends to be good.
- the epoxy (meth)acrylate resin may be used alone or in combination of two or more.
- an isocyanuric skeleton-containing resin having an ethylenic double bond and a carboxyl group may be used as the alkali-soluble resin (C) other than the resin (C1).
- C3 isocyanuric skeleton-containing resin Having an isocyanuric skeleton, an ethylenic double bond, and a carboxy group improves chemical resistance and heat resistance, and reduces the amount of decomposed products during development and baking, making it easier to apply voltage in organic electric field devices. There is a tendency for the current density to become high.
- Isocyanuric skeleton-containing resin is an alkali-soluble resin (C) other than resin (C1), and is not particularly limited as long as it has an ethylenic double bond, a carboxyl group, and an isocyanuric skeleton, but for example, the following ( Examples include resins C3-1) and (C3-2).
- Examples of the epoxy group-containing compound having an isocyanuric skeleton include a compound represented by the following general formula (C3-1-1).
- R 4 to R 6 each independently represent an alkylene group, and the alkylene group may be interrupted by an etheric oxygen atom.
- the alkylene group preferably has 1 or more carbon atoms. Further, the number of carbon atoms is preferably 6 or less, more preferably 4 or less, and even more preferably 2 or less.
- the above upper and lower limits can be arbitrarily combined. For example, 1 to 6 are preferred, 1 to 4 are more preferred, and 1 to 2 are even more preferred.
- the alkylene group may be linear or branched. When the amount is below the upper limit, developability tends to be good and gas barrier properties tend to improve. Examples of the alkylene group include methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, n-pentylene group, and n-hexylene group.
- an alkylene group that is split by an etheric oxygen atom in the middle 1 to 10 carbon atoms of the alkylene chain, which may be a straight chain or branched with 4 to 30 carbon atoms, are replaced with oxygen atoms.
- a group containing 2 to 9 ethoxy groups linked together and a group containing 2 to 7 propoxy groups linked together can be mentioned.
- methylene groups, ethylene groups, and n-propylene groups are preferred, and methylene groups are more preferred.
- Examples of the ⁇ , ⁇ -unsaturated monocarboxylic acid and/or ester compound include monocarboxylic acids such as (meth)acrylic acid, ⁇ -haloalkyl, alkoxyl, halogen, nitro, and cyano substituted products of (meth)acrylic acid; 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethyladipate, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxypropyl succinic acid, 2-(meth)acryloyloxypropyl adipate, 2-(meth)acryloyloxypropyltetrahydrophthalic acid, 2 -(meth)acryloyloxypropyl phthalic acid, 2-
- polybasic acids and/or anhydrides examples include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, and methylhexahydrophthalic acid.
- examples include hydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.
- the same method as for (C2) epoxy (meth)acrylate resin can be used.
- the ⁇ , ⁇ -unsaturated monocarboxylic acid and/or ester compound include the same compounds as those described in the section of (C2) epoxy (meth)acrylate resin.
- examples of the polybasic acid and/or its anhydride include the same compounds as those described in the section of resin (C1).
- (C3-2) A resin obtained by reacting an epoxy group-containing (meth)acrylate compound with a compound obtained by reacting a polyisocyanate compound having an isocyanuric skeleton with an acid or an acid anhydride.
- the resin (C3-2) include the resin described in Japanese Patent Application Publication No. 2020-75994, and intermediates thereof.
- the weight average molecular weight (Mw) of the isocyanuric skeleton-containing resin is not particularly limited, but is preferably 1,000 or more, more preferably 1,500 or more, even more preferably 2,000 or more, even more preferably 3,000 or more, and even more preferably 4,000 or more. , 5000 or more is particularly preferred. Further, it is preferably 10,000 or less, more preferably 8,000 or less, and even more preferably 7,000 or less. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 1,000 to 10,000, more preferably 1,500 to 10,000, even more preferably 1,500 to 8,000, even more preferably 2,000 to 8,000, and particularly preferably 2,000 to 7,000.
- the amount By setting the amount to be at least the lower limit, it tends to be possible to prevent the solubility in the developer from becoming too high. By setting it below the above-mentioned upper limit, there is a tendency that the solubility in the developer tends to be good.
- the acid value of the isocyanuric skeleton-containing resin is not particularly limited, but is preferably at least 20 mgKOH/g, more preferably at least 40 mgKOH/g, even more preferably at least 60 mgKOH/g, even more preferably at least 80 mgKOH/g, and even more preferably at least 100 mgKOH/g. g or more is particularly preferable. Moreover, 200 mgKOH/g or less is preferable, and 150 mgKOH/g or less is more preferable. The above upper and lower limits can be arbitrarily combined. For example, 20 to 200 mgKOH/g is preferable, and 60 to 150 mgKOH/g is more preferable. When the amount is at least the lower limit, development solubility tends to improve and resolution tends to improve. By setting it below the upper limit, the residual film rate of the photosensitive colored resin composition tends to be good.
- Acrylic copolymer resin may be used as the alkali-soluble resin (C4) in addition to resin (C1) from the viewpoint of compatibility with pigments, dispersants, etc.
- acrylic copolymer resin for example, those described in Japanese Patent Application Publication No. 2014-137466 can be preferably used.
- the acrylic copolymer resin includes, for example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "unsaturated monomer (C4-1)”) and other copolymer resins. Examples include copolymers with possible ethylenically unsaturated monomers (hereinafter referred to as “unsaturated monomers (C4-2)"). Examples of the unsaturated monomer (C4-1) include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, ⁇ -chloroacrylic acid, and cinnamic acid; maleic acid, maleic anhydride, and fumaric acid.
- unsaturated monomer (C4-1) include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, ⁇ -chloroacrylic acid, and cinnamic acid; maleic acid, maleic anhydride, and fumaric acid.
- Examples of the unsaturated monomer (C4-2) include N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; Aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, p-hydroxystyrene, p-hydroxy- ⁇ -methylstyrene, p-vinylbenzyl glycidyl ether, acenaphthylene;
- Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.0 2,6 ]decane-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3-(vinyloxymethyl)-3-ethyloxetane, etc. ;
- Examples include macromonomers having a mono(meth)acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane.
- These unsaturated monomers (C4-2) can be used alone or in combination of two or more.
- the copolymerization ratio of unsaturated monomer (C4-1) is preferably 5 to 50% by mass. , more preferably 10 to 40% by mass.
- copolymers of unsaturated monomers (C4-1) and unsaturated monomers (C4-2) include Japanese Patent Application Publication No. 7-140654, Japanese Patent Application Publication No. 8-259876, Japanese Unexamined Patent Publication No. 10-31308, Japanese Unexamined Patent Publication No. 10-300922, Unexamined Japanese Patent Application No. 11-174224, Unexamined Japanese Patent Application No. 11-258415, Unexamined Japanese Patent Application No. 2000-56118, Copolymers disclosed in Japanese Patent Application Publication No. 2004-101728 can be mentioned.
- the copolymer of unsaturated monomer (C4-1) and unsaturated monomer (C4-2) can be produced by a known method, but for example, Japanese Patent Application Publication No. 2003-222717,
- the structure, Mw, and Mw/Mn (Mn is the number average molecular weight) can also be controlled by the methods disclosed in Japanese Patent Application Publication No. 2006-259680 and International Publication No. 2007/029871.
- the photosensitive colored resin composition of the present invention contains (D) a photopolymerization initiator.
- the photopolymerization initiator is a component that has the function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating polymerization-active radicals.
- Additives such as a polymerization accelerator (chain transfer agent) and a sensitizing dye may be added as necessary.
- photopolymerization initiators for example, metallocene compounds including titanocene compounds described in Japanese Patent Application Laid-Open No. 59-152396 and Japanese Patent Application Publication No.
- metallocene compounds include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, and dicyclopentadienyl titanium bis(2,3,4,5,6-pentafluorophenyl-1-yl).
- hexaarylbiimidazole derivatives examples include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl) ) imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazole dimer, (4'- methoxyphenyl)-4,5-diphenylimidazole dimer.
- halomethylated oxadiazole derivatives examples include 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[ ⁇ -(2'- benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[ ⁇ -(2'-(6''-benzofuryl)vinyl)]-1,3,4-oxadiazole, Examples include 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.
- halomethyl-s-triazine derivatives examples include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis( trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl) -s-triazine is mentioned.
- Examples of ⁇ -aminoalkylphenone derivatives include 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4- morpholinophenyl)-butanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-( Examples include 4-morpholinophenyl)butan-1-one and 3,6-bis(2-methyl-2-morpholinopropionyl)-9-octylcarbazole.
- oxime ester compounds are particularly effective in terms of sensitivity and plate-making properties.
- an oxime ester compound is particularly effective in such sensitivity.
- Oxime ester compounds are useful. Oxime ester compounds have a structure that absorbs ultraviolet light, a structure that transmits light energy, and a structure that generates radicals, so they are highly sensitive even in small amounts and are stable against thermal reactions. Therefore, it is possible to obtain a highly sensitive photosensitive colored resin composition in a small amount.
- oxime ester compounds include compounds represented by the following general formula (IV).
- R 21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
- R 21b represents an arbitrary substituent containing an aromatic ring.
- R 22a represents an alkanoyl group which may have a substituent or an aroyl group which may have a substituent.
- n represents an integer of 0 or 1.
- the number of carbon atoms in the alkyl group in R21a is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is preferably 1 or more, more preferably 2 or more, and preferably 20 or less, more preferably 15 or less, 10 The following are more preferred.
- examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a cyclopentylethyl group.
- alkyl group may have include aromatic ring groups, hydroxyl groups, carboxy groups, halogen atoms, amino groups, amide groups, 4-(2-methoxy-1-methyl)ethoxy-2- Examples include methylphenyl group and N-acetyl-N-acetoxyamino group. From the viewpoint of ease of synthesis, it is preferable that it is unsubstituted.
- Examples of the aromatic ring group for R 21a include aromatic hydrocarbon ring groups and aromatic heterocyclic groups.
- the number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the photosensitive colored resin composition. Further, from the viewpoint of developability, the number is preferably 30 or less, more preferably 20 or less, and even more preferably 12 or less. For example, the number is preferably 5 to 30, more preferably 5 to 20, and even more preferably 5 to 12.
- Examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, and a furyl group. From the viewpoint of developability, a phenyl group or a naphthyl group is preferred, and a phenyl group is more preferred.
- Examples of the substituent that the aromatic ring group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, and a group in which these substituents are linked.
- R 21a is preferably an aromatic ring group which may have a substituent, and more preferably an aromatic ring group having a linked alkoxy group as a substituent.
- R 21b is an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, an optionally substituted diphenyl sulfide group, an optionally substituted fluorenyl group, or an optionally substituted indolyl group can be mentioned. From the viewpoint of sensitivity, an optionally substituted carbazolyl group is preferred. From the viewpoint of electrical reliability, an optionally substituted diphenyl sulfide group is preferred.
- the number of carbon atoms in the alkanoyl group in R22a is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is preferably 2 or more, preferably 20 or less, more preferably 15 or less, even more preferably 10 or less, 5 The following are particularly preferred.
- examples of the alkanoyl group include an acetyl group, a propanoyl group, and a butanoyl group.
- substituents that the alkanoyl group may have include aromatic ring groups, hydroxyl groups, carboxy groups, halogen atoms, amino groups, and amide groups. From the viewpoint of ease of synthesis, it is preferable that it is unsubstituted.
- the number of carbon atoms in the aroyl group in R22a is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is preferably 7 or more, more preferably 8 or more, and preferably 20 or less, more preferably 15 or less, 10 The following are more preferred.
- Examples of the aroyl group include a benzoyl group and a naphthoyl group.
- substituents that the aroyl group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, and an alkyl group. From the viewpoint of ease of synthesis, it is preferable that it is unsubstituted.
- R 22a is preferably an alkanoyl group that may have a substituent, more preferably an unsubstituted alkanoyl group, and even more preferably an acetyl group.
- the initiator described in Japanese Patent Application Publication No. 2016-133574 can also be suitably used in terms of reducing staining caused by colorants.
- the photopolymerization initiator may contain a sensitizing dye and a polymerization accelerator depending on the wavelength of the image exposure light source, if necessary, for the purpose of increasing the sensitivity.
- the sensitizing dye include xanthene dyes described in Japanese Patent Application Laid-Open No. 4-221958 and Japanese Patent Application Publication No. 4-219756, Japanese Patent Application Publication No. 3-239703, and Japanese Patent Application Publication No. 5-289335.
- a sensitizing dye containing an amino group is preferable, and a compound having an amino group and a phenyl group in the same molecule is more preferable.
- a sensitizing dye a sensitizing dye containing an amino group is preferable, and a compound having an amino group and a phenyl group in the same molecule is more preferable.
- Benzophenone compounds such as benzophenone; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benz
- polymerization accelerator for example, aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate, aliphatic amines such as n-butylamine and N-methyldiethanolamine, and mercapto compounds described below are used. .
- aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate
- aliphatic amines such as n-butylamine and N-methyldiethanolamine
- mercapto compounds described below are used.
- the polymerization accelerators may be used alone or in combination of two or more.
- the photosensitive colored resin composition of the present invention may also contain (E) an ethylenically unsaturated compound.
- (E) Containing an ethylenically unsaturated compound tends to improve sensitivity.
- the ethylenically unsaturated compound (E) used in the present invention is a compound having at least one ethylenically unsaturated group in the molecule. Specific examples include (meth)acrylic acid, (meth)acrylic acid alkyl ester, acrylonitrile, styrene, carboxylic acid having one ethylenically unsaturated bond, and monoester of polyhydric or monohydric alcohol.
- a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule is particularly preferable to use.
- the number of ethylenically unsaturated groups that the polyfunctional ethylenic monomer has is not particularly limited, but is preferably 2 or more, more preferably 4 or more, even more preferably 5 or more, and preferably 8 or less, More preferably, the number is 7 or less.
- the above upper and lower limits can be arbitrarily combined.
- the number is preferably 2 to 8, more preferably 2 to 7, even more preferably 4 to 7, and particularly preferably 5 to 7.
- the value is equal to or higher than the lower limit value, there is a tendency for high sensitivity to be obtained.
- polyfunctional ethylenic monomers include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatic polyhydroxy Examples include esters obtained by an esterification reaction between a polyhydric hydroxy compound such as a compound, and an unsaturated carboxylic acid and a polybasic carboxylic acid.
- esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate.
- pentaerythritol tetraacrylate dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, and other aliphatic polyhydroxy compound acrylic esters; methacrylic esters in which these acrylates are replaced with methacrylate; Examples include itaconate esters in which acrylate is replaced with itaconate; crotonic esters in which these acrylates are replaced with cronates; and maleate esters in which these acrylates are replaced with maleates.
- esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic esters and methacrylates of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.
- esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic esters and methacrylates of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.
- acid esters include acid esters.
- the ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid with a polyhydric hydroxy compound is not necessarily a single substance, but for example, a condensate of acrylic acid, phthalic acid, and ethylene glycol, Examples include condensates of acrylic acid, maleic acid, and diethylene glycol, condensates of methacrylic acid, terephthalic acid, and pentaerythritol, and condensates of acrylic acid, adipic acid, butanediol, and glycerin.
- the polyfunctional ethylenic monomer used in the present invention includes, for example, a polyisocyanate compound and a hydroxyl group-containing (meth)acrylic ester, or a polyisocyanate compound, a polyol, and a hydroxyl group-containing (meth)acrylic ester.
- Urethane (meth)acrylates such as those obtained; Epoxy acrylates such as addition reaction products of polyvalent epoxy compounds and hydroxy (meth)acrylate or (meth)acrylic acid; Acrylamides such as ethylene bisacrylamide; Diallyl phthalate and vinyl group-containing compounds such as divinyl phthalate.
- urethane (meth)acrylates examples include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U- 10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B, UV- Examples include 7600B, UV-7605B, UV-7630B, and UV7640B (manufactured by Mitsubishi Chemical Corporation).
- (E) ethylenically unsaturated compounds include (meth)acrylic acid alkyl esters, polyisocyanate compounds and hydroxyl group-containing (meth)acrylic esters, or polyisocyanate compounds and polyols and hydroxyl group-containing (meth)acrylic esters. It is preferable to use urethane (meth)acrylates such as those obtained by reacting the following, and it is more preferable to use a polyisocyanate compound and a hydroxyl group-containing (meth)acrylic acid ester. These may be used alone or in combination of two or more.
- the photosensitive colored resin composition of the present invention includes adhesion improvers such as silane coupling agents, surfactants, pigment derivatives, photoacid generators, crosslinking agents, mercapto compounds, polymerization inhibitors, etc. Additives may be appropriately blended.
- the photosensitive colored resin composition of the present invention may contain an adhesion improver in order to improve the adhesion with the substrate.
- an adhesion improver silane coupling agents and phosphoric acid group-containing compounds are preferred.
- silane coupling agent various types such as epoxy type, (meth)acrylic type, and amino type may be used alone or in combination of two or more types.
- silane coupling agent examples include (meth)acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, epoxysilanes such as 3-glycidoxypropyltriethoxysilane, ureidosilanes such as 3-ureidopropyltriethoxysilane, Examples include isocyanate silanes such as 3-isocyanatepropyltriethoxysilane.
- Silane coupling agents such as epoxysilanes are particularly preferred.
- (meth)acryloyl group-containing phosphates are preferred, and those represented by the following general formula (g1), (g2) or (g3) are preferred.
- R 51 represents a hydrogen atom or a methyl group
- l and l' are integers of 1 to 10
- m is 1, 2 or 3.
- These phosphoric acid group-containing compounds may be used alone or in combination of two or more.
- the photosensitive colored resin composition of the present invention may contain a surfactant to improve coating properties.
- surfactant various types of surfactants can be used, such as anionic, cationic, nonionic, and amphoteric surfactants. It is preferable to use nonionic surfactants because they are less likely to adversely affect various properties, and fluorine-based or silicone-based surfactants are more preferable from the viewpoint of coating properties. Examples of such surfactants include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by BYK Chemie), and KP340.
- surfactant manufactured by Shin-Etsu Silicone
- F-470, F-475, F-478, F-554, F-559 manufactured by DIC
- SH7PA manufactured by Toray Dow Corning
- DS-401 manufactured by Daikin
- L-77 manufactured by Nippon Unicar
- FC4430 manufactured by 3M.
- One type of surfactant may be used, or two or more types may be used in combination.
- Pigment derivative The photosensitive colored resin composition of the present invention may contain a pigment derivative as a dispersion aid in order to improve dispersibility and storage stability.
- pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, and diketopyrrolopyrrole. and dioxazine derivatives, with phthalocyanine derivatives and quinophthalone derivatives being preferred.
- substituents on pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxy groups, and amide groups directly on the pigment skeleton, or, for example, alkyl Examples include those bonded via a group, an aryl group, or a heterocyclic group, and preferably a sulfonic acid group.
- a single pigment skeleton may be substituted with a plurality of substituents, or may be substituted with a plurality of types of substituents.
- pigment derivatives include sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, sulfonic acid derivatives of diketopyrrolopyrrole, and sulfonic acid derivatives of dioxazine. These may be used alone or in combination of two or more.
- the photosensitive colored resin composition of the present invention may contain a mercapto compound as a polymerization accelerator and to improve adhesion to the substrate.
- Examples of mercapto compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bis Thioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate nate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, ethylene glycol bis(3-mercaptobutyrate), butanediol
- the photosensitive colored resin composition of the present invention may contain a polymerization inhibitor from the viewpoint of controlling the shape of the cured product. Since the inclusion of a polymerization inhibitor inhibits the radical polymerization of the lower layer of the coating film, it is thought that the taper angle (the angle between the support and the cured product in the cross section of the cured product) can be controlled.
- the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT). From the viewpoint of shape control, 2,6-di-tert-butyl-4-cresol is preferred.
- Hydroquinone monomethyl ether and methylhydroquinone are preferred from the viewpoint of particularly excellent safety to the human body.
- the polymerization inhibitors may be used alone or in combination of two or more.
- a polymerization inhibitor may be contained in the resin, and it may be used as the polymerization inhibitor of the present invention, or in addition to the polymerization inhibitor in the resin, The same or different polymerization inhibitor may be added during production of the photosensitive colored resin composition.
- the photosensitive colored resin composition contains a polymerization inhibitor
- its content is not particularly limited, but is preferably 0.0005% by mass or more, more preferably 0.0005% by mass or more, based on the total solid content of the photosensitive colored resin composition. .001% by mass or more, more preferably 0.01% by mass or more, and preferably 0.3% by mass or less, more preferably 0.2% by mass or less, even more preferably 0.1% by mass or less. .
- the above upper and lower limits can be arbitrarily combined. For example, it is preferably 0.0005% to 0.3% by weight, more preferably 0.001% to 0.2% by weight, and even more preferably 0.01% to 0.1% by weight.
- the shape of the cured product can be controlled by setting it above the lower limit value.
- necessary sensitivity can be maintained by setting it below the upper limit value.
- the photosensitive colored resin composition of the present invention preferably contains a solvent. By including a solvent, the colorant can be dispersed or dissolved in the solvent, and application becomes easier.
- the photosensitive colored resin composition of the present invention includes, for example, (A) a colorant, (B) a dispersant, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and various other materials used as necessary. The materials are used dissolved or dispersed in a solvent. Organic solvents are preferred from the viewpoint of dispersibility and coating properties.
- an organic solvent with a boiling point of 100 to 300°C, more preferably 120 to 280°C.
- the boiling point here means the boiling point at a pressure of 1013.25 hPa, and the same applies to all boiling points below.
- organic solvents examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol mono-n-butyl ether.
- propylene glycol-t-butyl ether diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl - Glycol monoalkyl ethers such as 3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether; Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;
- Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionate linear or cyclic esters such as butyl, ⁇ -butyrolactone; Alkoxycarboxylic acids such as 3-methoxyprop
- organic solvents include, for example, Mineral Spirit, Valsol #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No. 1 and no. 2.
- Solvesso #150 Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve (“Cellosolve” is a registered trademark. The same applies hereinafter), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all may also be used (trade name).
- These organic solvents may be used alone or in combination of two or more.
- an organic solvent with a boiling point of 100 to 240°C, more preferably 120 to 200°C, even more preferably 120 to 170°C. .
- glycol alkyl ether acetates are preferred from the standpoint of good balance in coating properties, surface tension, etc., and relatively high solubility of the constituent components in the composition.
- One type of glycol alkyl ether acetate may be used alone, or two or more types may be used in combination.
- glycol alkyl ether acetates may be used alone, other organic solvents may also be used in combination.
- As the organic solvent used in combination glycol monoalkyl ethers are preferred. Propylene glycol monomethyl ether is preferred from the viewpoint of solubility of the components in the composition.
- Glycol monoalkyl ethers have high polarity, and if the amount added is too large, the pigment tends to aggregate, which tends to reduce the storage stability such as increasing the viscosity of the photosensitive colored resin composition obtained later.
- the proportion of glycol monoalkyl ethers in the solvent is preferably 5 to 30% by mass, more preferably 5 to 20% by mass.
- the photosensitive colored resin composition will be difficult to dry, but the pigment will not be uniformly dispersed in the composition.
- a high boiling point solvent may be used in combination, since this has the effect of preventing the state from being destroyed by rapid drying. For example, it has the effect of preventing the occurrence of foreign matter defects due to precipitation and solidification of colorants and the like at the tip of the slit nozzle.
- diethylene glycol mono-n-butyl ether diethylene glycol mono-n-butyl ether acetate
- diethylene glycol monoethyl ether acetate diethylene glycol monoethyl ether acetate
- the content of the high boiling point solvent in the organic solvent is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 5 to 30% by mass.
- the amount By setting the amount to be equal to or more than the lower limit, it tends to be possible to suppress the precipitation and solidification of the coloring agent and the like at the tip of the slit nozzle, thereby causing foreign matter defects.
- it By setting it below the above upper limit, it is possible to suppress an increase in the drying time of the composition and tend to suppress problems such as tact failure in the vacuum drying process and pin marks during prebaking.
- the high boiling point solvent may be a glycol alkyl ether acetate or a glycol alkyl ether. In this case, there is no need to separately contain a high boiling point solvent.
- Preferred high-boiling solvents include, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate, and triacetin. .
- the content ratio of the colorant (A) in the photosensitive colored resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more based on the total solid content of the photosensitive colored resin composition. It is preferably 15% by mass or more, and more preferably 15% by mass or more. Further, it is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 20% by mass or less. The above upper and lower limits can be arbitrarily combined.
- it is preferably 5 to 40% by weight, more preferably 10 to 30% by weight, even more preferably 15 to 30% by weight, even more preferably 15 to 25% by weight, and particularly preferably 15 to 20% by weight.
- light-shielding properties can be ensured by setting the amount to be equal to or more than the lower limit value. By setting it below the above upper limit, the amount of dispersant can be reduced and surface roughness tends to be suppressed.
- the content of the organic pigment (A-1) in the photosensitive colored resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, and 10% by mass based on the total solid content of the photosensitive colored resin composition.
- the content is more preferably 15% by mass or more, and even more preferably 15% by mass or more.
- it is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 20% by mass or less.
- the above upper and lower limits can be arbitrarily combined. For example, it is preferably 5 to 40% by weight, more preferably 10 to 30% by weight, even more preferably 15 to 30% by weight, even more preferably 15 to 25% by weight, and particularly preferably 15 to 20% by weight.
- There is a tendency that light-shielding properties can be ensured by setting the amount to be equal to or more than the lower limit value. By setting it below the upper limit value, the residual film rate tends to increase.
- the content ratio of the organic black pigment in the photosensitive colored resin composition is not particularly limited, but is based on the total solid content of the photosensitive colored resin composition.
- the content is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. Further, it is preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and particularly preferably 20% by mass or less.
- the above upper and lower limits can be arbitrarily combined. For example, it is preferably 5 to 40% by weight, more preferably 10 to 30% by weight, even more preferably 15 to 30% by weight, even more preferably 15 to 25% by weight, and particularly preferably 15 to 20% by weight.
- There is a tendency that light-shielding properties can be ensured by setting the amount to be equal to or more than the lower limit value. By setting it below the upper limit value, the residual film rate tends to increase.
- the content thereof is not particularly limited, but is 1% by mass in the total solid content of the photosensitive colored resin composition.
- the content is preferably at least 5% by mass, more preferably at least 10% by mass. Further, it is preferably 30% by mass or less, more preferably 20% by mass or less.
- the above upper and lower limits can be arbitrarily combined. For example, it is preferably 1 to 30% by weight, more preferably 5 to 20% by weight, and even more preferably 10 to 20% by weight.
- the amount is equal to or more than the lower limit, the light blocking property tends to be enhanced while suppressing the loss of ultraviolet light necessary for curing. By setting it below the upper limit value, the residual film rate tends to increase.
- the content ratio of the dispersant is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, based on the total solid content of the photosensitive colored resin composition.
- the content is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, even more preferably 7% by mass or less.
- the above upper and lower limits can be arbitrarily combined. For example, it is preferably 1 to 20% by weight, more preferably 2 to 15% by weight, even more preferably 3 to 10% by weight, and particularly preferably 3 to 7% by weight.
- sufficient dispersibility can be easily obtained by setting the amount to be equal to or more than the lower limit value.
- outgassing can be reduced by setting it below the upper limit value.
- the content ratio of the dispersant (B) to 100 parts by mass of the colorant (A) is not particularly limited, but is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, and 50 parts by mass or more.
- the amount is preferably at most 30 parts by mass, more preferably at most 30 parts by mass.
- the above upper and lower limits can be arbitrarily combined. For example, it is preferably 5 to 50 parts by weight, more preferably 10 to 50 parts by weight, and even more preferably 15 to 30 parts by weight. There is a tendency that sufficient dispersibility can be easily obtained by setting the amount to be equal to or more than the lower limit value. By setting it below the upper limit value, the residual film rate tends to increase.
- the content ratio of the alkali-soluble resin (C) is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more based on the total solid content of the photosensitive colored resin composition. , even more preferably 30% by mass or more, particularly preferably 40% by mass or more, and preferably 85% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less, even more preferably 60% by mass or less. It is not more than 55% by mass, particularly preferably not more than 55% by mass.
- the above upper and lower limits can be arbitrarily combined.
- the amount is preferably 5 to 80% by weight, more preferably 10 to 70% by weight, even more preferably 20 to 60% by weight, even more preferably 30 to 60% by weight, even more preferably 30 to 55% by weight, and even more preferably 40 to 55% by weight. % by weight is particularly preferred.
- the amount By setting the amount to be equal to or higher than the lower limit, it tends to be possible to suppress a decrease in the solubility of an unexposed area in a developer and to suppress development defects.
- the upper limit value By setting it below the upper limit value, appropriate sensitivity can be maintained, dissolution of the exposed area by the developer can be suppressed, and the taper angle tends to be low.
- the content ratio of the resin (C1) is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, based on the total solid content of the photosensitive colored resin composition.
- the content is preferably 20% by mass or less, more preferably 17% by mass or less, still more preferably 15% by mass or less, even more preferably 10% by mass or less.
- the above upper and lower limits can be arbitrarily combined. For example, it is preferably 1 to 20% by weight, more preferably 3 to 17% by weight, even more preferably 3 to 15% by weight, and particularly preferably 5 to 10% by weight.
- dispersion stability can be improved by setting the above lower limit value or more. When the amount is below the upper limit, the solubility in the developer tends to be good.
- the content ratio of the resin (C1) is not particularly limited, but in the alkali-soluble resin (C), it is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more. Further, it is preferably 100% by mass or less, more preferably 80% by mass or less, even more preferably 60% by mass or less, even more preferably 40% by mass or less, particularly preferably 20% by mass or less.
- the above upper and lower limits can be arbitrarily combined. For example, it is preferably 1 to 100% by weight, more preferably 5 to 80% by weight, even more preferably 10 to 60% by weight, even more preferably 10 to 40% by weight, and particularly preferably 10 to 20% by weight.
- the amount By setting the amount to be equal to or higher than the lower limit, it tends to be possible to suppress a decrease in the solubility of an unexposed area in a developer and to suppress development defects.
- it By setting it below the above-mentioned upper limit, it is possible to maintain appropriate sensitivity, suppress dissolution of the exposed area by the developer, and tend to suppress deterioration of sharpness and adhesion of the pattern.
- the content ratio of (C2) epoxy (meth)acrylate resin is not particularly limited, but the photosensitive colored resin of the present invention Preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, especially It is preferably 40% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, particularly preferably 55% by mass or less.
- the above upper and lower limits can be arbitrarily combined.
- it is preferably 5 to 80% by weight, more preferably 10 to 70% by weight, even more preferably 15 to 60% by weight, even more preferably 20 to 60% by weight, even more preferably 30 to 55% by weight, and even more preferably 40 to 60% by weight. Particularly preferred is 55% by weight.
- the content ratio of the (C2) epoxy (meth)acrylate resin contained in the alkali-soluble resin (C) is not particularly limited, but Preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and preferably 100% by mass or less, more preferably 90% by mass or less, still more preferably 80% by mass or less. be.
- the above upper and lower limits can be arbitrarily combined. For example, it is preferably 20 to 100% by weight, more preferably 30 to 90% by weight, even more preferably 40 to 80% by weight.
- the content ratio of the (C3) isocyanuric skeleton-containing resin contained in the (C) alkali-soluble resin is not particularly limited, but is preferably 20% by mass or more. , more preferably 30% by mass or more, still more preferably 40% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less.
- the above upper and lower limits can be arbitrarily combined. For example, it is preferably 20 to 90% by weight, more preferably 30 to 80% by weight, even more preferably 40 to 70% by weight.
- the amount is equal to or more than the lower limit, the light emitting characteristics tend to be improved. There is a tendency for developability to be improved by setting it below the upper limit value.
- the content ratio of the photopolymerization initiator is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass based on the total solid content of the photosensitive colored resin composition of the present invention. Above, more preferably 1% by mass or more, even more preferably 2% by mass or more, particularly preferably 3% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass or less. It is less than 6% by mass, particularly preferably less than 6% by mass. The above upper and lower limits can be arbitrarily combined.
- it is preferably 0.1 to 15% by mass, more preferably 0.5 to 15% by mass, even more preferably 1 to 10% by mass, even more preferably 2 to 8% by mass, and particularly preferably 3 to 6% by mass.
- a decrease in sensitivity can be suppressed by setting the value to be equal to or more than the lower limit value. By setting it below the upper limit, it is possible to suppress a decrease in the solubility of an unexposed area in a developer, and tend to suppress development defects.
- the content of the polymerization accelerator is not particularly limited, but is preferably 0.05% by mass based on the total solid content of the photosensitive colored resin composition of the present invention. or more, and preferably 10% by mass or less, more preferably 5% by mass or less. For example, it is preferably 0.05 to 10% by weight, more preferably 0.05 to 5% by weight.
- the polymerization accelerator is preferably used in a proportion of 0.1 to 50 parts by mass, more preferably 0.1 to 20 parts by mass, per 100 parts by mass of the photopolymerization initiator (D).
- the content of the sensitizing dye is not particularly limited, but from the viewpoint of sensitivity, it is preferably 20% by mass based on the total solid content in the photosensitive colored resin composition. % or less, more preferably 15% by mass or less, still more preferably 10% by mass or less.
- the content of (E) the ethylenically unsaturated compound is not particularly limited, but the total content of the photosensitive colored resin composition of the present invention is Based on the solid content, it is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, particularly preferably 15% by mass or more, and preferably 30% by mass or less, more preferably is 25% by mass or less, more preferably 20% by mass or less.
- the above upper and lower limits can be arbitrarily combined.
- it is preferably 1 to 30% by weight, more preferably 5 to 25% by weight, even more preferably 10 to 25% by weight, and particularly preferably 15 to 20% by weight.
- the above lower limit or more it is possible to maintain appropriate sensitivity, suppress dissolution of the exposed area by the developer, and tend to suppress deterioration of sharpness and adhesion of the pattern.
- the upper limit value there is a tendency that the permeability of the developer into the exposed area is suppressed from increasing and it becomes easy to obtain a good image.
- the content ratio of (C) alkali-soluble resin to 100 parts by mass of (E) ethylenically unsaturated compound is not particularly limited, but may be 100 parts by mass. It is preferably at least 200 parts by mass, more preferably at least 250 parts by mass, even more preferably at least 300 parts by mass, and particularly preferably at least 350 parts by mass. Moreover, it is preferably 700 parts by mass or less, more preferably 500 parts by mass or less, even more preferably 450 parts by mass or less, and particularly preferably 400 parts by mass or less. The above upper and lower limits can be arbitrarily combined.
- it is preferably 100 to 700 parts by weight, more preferably 200 to 700 parts by weight, even more preferably 250 to 500 parts by weight, even more preferably 300 to 450 parts by weight, and particularly preferably 350 to 400 parts by weight.
- it is preferably 100 to 700 parts by weight, more preferably 200 to 700 parts by weight, even more preferably 250 to 500 parts by weight, even more preferably 300 to 450 parts by weight, and particularly preferably 350 to 400 parts by weight.
- an adhesion improver When using an adhesion improver, its content is not particularly limited, but it is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass based on the total solid content of the photosensitive colored resin composition. , more preferably 0.4 to 2% by mass. There is a tendency that the effect of improving adhesion can be sufficiently obtained by setting the amount to be equal to or more than the lower limit value. By setting it below the upper limit, it tends to be possible to suppress decreases in sensitivity and defects caused by residue remaining after development.
- the content is not particularly limited, but it is preferably 0.001 to 10% by mass, more preferably 0.005 to 1% by mass, based on the total solid content of the photosensitive colored resin composition. , more preferably 0.01 to 0.5% by weight, particularly preferably 0.03 to 0.3% by weight.
- the amount is equal to or more than the lower limit, the coating film tends to exhibit smoothness and uniformity. By setting it below the above-mentioned upper limit, smoothness and uniformity of the coating film are likely to be exhibited, and deterioration of other properties tends to be suppressed.
- the photosensitive colored resin composition of the present invention has a total solid content of preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and , preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less.
- the above upper and lower limits can be arbitrarily combined.
- the content is preferably 5 to 50% by weight, more preferably 10 to 30% by weight, and even more preferably 15 to 25% by weight.
- the optical density (OD) of the photosensitive colored resin composition of the present invention per 1 ⁇ m of coating film thickness is not particularly limited, but is preferably 0.2 or more, more preferably 0.5 or more, and 0.7 or more. is more preferably 0.9 or more, further preferably 4.0 or less, more preferably 3.0 or less, even more preferably 2.0 or less, and particularly preferably 1.5 or less.
- the above upper and lower limits can be arbitrarily combined. For example, it is preferably 0.2 to 4.0, more preferably 0.5 to 4.0, even more preferably 0.5 to 3.0, even more preferably 0.5 to 2.0, and even more preferably 0.7 to 4.0. 2.0 is particularly preferred, and 0.9 to 1.5 is particularly preferred.
- the optical density (OD) per 1 ⁇ m of the film thickness of the coating film may be measured using a coating film cured from the photosensitive colored resin composition of the present invention, and is 0.5 to 0.00000 ⁇ m after curing by heating at 230°C for 20 minutes. It can be measured using a coating film of about 1.5 ⁇ m.
- the optical density refers to the transmission optical density where the spectral sensitivity characteristic of the light receiving section is indicated by ISO Visual density in the ISO 5-3 standard.
- an A light source defined by CIE (Commission Internationale de l'Eclairage) is used.
- CIE Commission Internationale de l'Eclairage
- An example of a measuring instrument that can be used to measure transmission optical density is X-Rite 361T (V) manufactured by Sakata Inx Engineering Co., Ltd.
- the components constituting the pigment dispersion of the present invention and their composition will be explained.
- the pigment dispersion of the present invention contains (A) a colorant, (B) a dispersant, and (C) an alkali-soluble resin, and in particular, the colorant (A) contains an organic pigment (A-1). , (C) alkali-soluble resin contains resin (C1). Moreover, it is preferable that a solvent is included.
- the constituent components of the pigment dispersion of the present invention those listed as the same items in the photosensitive colored resin composition of the present invention can be preferably employed.
- the resin (C1) Since the resin (C1) has a high affinity with pigments and also contains a methylene group in its main chain and has flexibility that can follow the pigment, the pigment dispersion of the present invention tends to exhibit high pigment dispersibility. be. Furthermore, the photosensitive colored resin composition using the pigment dispersion of the present invention tends to have a high residual film rate. This is because, as described above, the resin (C1) contains many aromatic rings in its main chain, so it tends to have high developer resistance during development and high heat resistance during baking. Furthermore, when an organic electroluminescent device is formed using partition walls obtained from a photosensitive colored resin composition, the current density when voltage is applied tends to be high, as described above.
- the content of the colorant (A) is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass based on the total solid content in the pigment dispersion. More preferably, the content is 40% by weight or more, particularly preferably 50% by weight or more, particularly preferably 55% by weight or more. Further, it is usually 100% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 65% by mass or less.
- a photosensitive colored resin composition can be produced with an appropriate solid content concentration, and by setting it to below the above upper limit, the dispersibility tends to improve.
- the combination of upper and lower limits is preferably 10 to 80% by mass, more preferably 20 to 80% by mass, even more preferably 30 to 70% by mass, even more preferably 40 to 70% by mass, and even more preferably 50 to 65% by mass. Particularly preferred, and most preferably 55 to 65% by weight.
- the content of the organic pigment (A-1) is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more based on the total solid content in the pigment dispersion. It is at least 40% by weight, even more preferably at least 40% by weight, even more preferably at least 50% by weight, particularly preferably at least 55% by weight. Further, it is usually 100% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 65% by mass or less.
- the combination of upper and lower limits is preferably 10 to 80% by mass, more preferably 20 to 80% by mass, even more preferably 30 to 70% by mass, even more preferably 40 to 70% by mass, and even more preferably 50 to 65% by mass. Particularly preferred, and most preferably 55 to 65% by weight.
- the content of the organic black pigment is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, based on the total solid content in the pigment dispersion. It is even more preferably 40% by weight or more, particularly preferably 50% by weight or more, particularly preferably 55% by weight or more. Further, it is usually 100% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 65% by mass or less.
- the combination of upper and lower limits is preferably 10 to 80% by mass, more preferably 20 to 80% by mass, even more preferably 30 to 70% by mass, even more preferably 40 to 70% by mass, and even more preferably 50 to 65% by mass. Particularly preferred, and most preferably 55 to 65% by weight.
- the content of the dispersant (B) is preferably 2% by mass or more, more preferably 5% by mass or more, and even more preferably 8% by mass based on the total solid content in the pigment dispersion. That's all. Further, it is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 15% by mass or less. Setting the value above the lower limit tends to improve dispersibility, and setting the value below the upper limit prevents excess dispersant from being reduced, improving the developability of the resulting photosensitive colored resin composition. tends to be good.
- the combination of upper and lower limits is preferably 2 to 50% by mass, more preferably 5 to 40% by mass, even more preferably 5 to 30% by mass, even more preferably 5 to 20% by mass, and even more preferably 8 to 15% by mass. Particularly preferred.
- the content of the acrylic dispersant is preferably 2% by mass or more, more preferably 2% by mass or more based on the total solid content in the pigment dispersion. Preferably it is 5% by mass or more, more preferably 8% by mass or more. Further, it is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, even more preferably 20% by mass or less, and particularly preferably 15% by mass or less.
- the value is at least the above lower limit, the dispersibility tends to be good and the pattern adhesion during development of the cured product tends to be good. Developability tends to be good.
- the combination of upper and lower limits is preferably 2 to 50% by mass, more preferably 5 to 40% by mass, even more preferably 5 to 30% by mass, even more preferably 5 to 20% by mass, and even more preferably 10 to 15% by mass. Particularly preferred.
- the content of the alkali-soluble resin (C) is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass based on the total solid content in the pigment dispersion. % or more, even more preferably 20% by mass or more, particularly preferably 25% by mass or more. Further, it is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less. Setting the value above the lower limit tends to improve dispersibility, and setting the value below the upper limit allows the amount of colorant in the resulting photosensitive colored resin composition to be optimized, resulting in sufficient light-shielding properties. tends to be secured.
- the combination of upper and lower limits is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, even more preferably 15 to 35% by mass, even more preferably 20 to 35% by mass, and even more preferably 25 to 35% by mass. Particularly preferred.
- the content of the resin (C1) is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, based on the total solid content in the pigment dispersion. It is even more preferably 20% by mass or more, particularly preferably 25% by mass or more. Further, it is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less.
- the combination of upper and lower limits is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, even more preferably 15 to 35% by mass, even more preferably 20 to 35% by mass, and even more preferably 25 to 35% by mass. Particularly preferred.
- the pigment dispersion of the present invention is prepared using the above-mentioned organic solvent so that its solid content concentration is preferably 5 to 50% by mass, more preferably 10 to 30% by mass.
- the viscosity of the pigment dispersion is preferably 1 MPa ⁇ s or more, more preferably 3 MPa ⁇ s or more, and even more preferably 5 MPa ⁇ s or more. Further, the pressure is preferably 15 MPa ⁇ s or less, and more preferably 10 MPa ⁇ s or less. The viscosity can be measured using, for example, a rotational viscometer.
- the pigment dispersion of the present invention is produced according to a conventional method.
- the colorant is preferably dispersed in advance using a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, or the like. Since the colorant (A) is made into fine particles by the dispersion treatment, the coating properties of the photosensitive colored resin composition tend to improve and the surface roughness tends to decrease.
- the dispersion treatment is performed using a system that uses part or all of (A) a colorant, (B) a dispersant, and a solvent, and (C) an alkali-soluble resin, or a system that uses (A) a colorant, (B) a dispersant, It is preferable to use a system in which a part or all of the alkali-soluble resin (C), a solvent, and (C) are used in combination. In particular, it is preferable to use a polymer dispersant as the dispersant (B) because it suppresses thickening of the obtained pigment dispersion and photosensitive colored resin composition over time, that is, it has excellent dispersion stability.
- the (A) colorant, (B) dispersant, and solvent that can be used in the pigment dispersion those described as those that can be used in the photosensitive colored resin composition can be preferably employed.
- a dispersion treatment When a dispersion treatment is performed on a liquid containing all components to be blended into a photosensitive colored resin composition, highly reactive components may be denatured due to the heat generated during the dispersion treatment. Therefore, it is preferable to carry out the dispersion treatment in a system containing a polymeric dispersant.
- a polymeric dispersant When dispersing the colorant (A) with a sand grinder, glass beads or zirconia beads having a particle size of about 0.1 to 8 mm are preferably used.
- the temperature is preferably from 0°C to 100°C, more preferably from room temperature to 80°C.
- the appropriate dispersion time varies depending on the composition of the liquid, the size of the dispersion processing apparatus, etc., and is therefore adjusted as appropriate.
- a guideline for dispersion is to control the gloss of the pigment dispersion so that the 20 degree specular gloss (JIS Z8741) of the photosensitive colored resin composition is in the range of 50 to 300.
- the dispersion treatment is often insufficient and rough pigment (colorant) particles remain, which may affect developability, adhesion, resolution, surface roughness, etc. may be insufficient.
- the dispersion treatment is performed until the gloss value exceeds the above range, the pigment will be crushed and a large number of ultrafine particles will be produced, which tends to impair the dispersion stability.
- the dispersed particle diameter of the pigment dispersed in the pigment dispersion is preferably 0.03 to 0.3 ⁇ m, and can be measured by a dynamic light scattering method.
- the pigment dispersion obtained by the above dispersion treatment and other components contained in the photosensitive colored resin composition are mixed to form a uniform solution or dispersion.
- fine dust may be mixed into the liquid, so it is desirable to filter the obtained photosensitive colored resin composition using a filter or the like.
- the cured product of the present invention can be obtained by curing the photosensitive colored resin composition of the present invention.
- the cured product obtained by curing the photosensitive colored resin composition of the present invention can be suitably used as a black matrix, an insulating film, and a partition wall, and can be more suitably used as a partition wall.
- the film thickness of the cured product is preferably 0.5 ⁇ m or more, more preferably 0.7 ⁇ m or more, and even more preferably 0.9 ⁇ m or more. Moreover, it is preferably 15 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less.
- the thickness is preferably 0.5 to 15 ⁇ m, more preferably 0.7 to 10 ⁇ m, and even more preferably 0.9 to 5 ⁇ m.
- the optical density (OD) per 1 ⁇ m of the cured product of the present invention is preferably 0.2 or more, more preferably 0.5 or more, even more preferably 0.7 or more, and 0.9 or more from the viewpoint of light shielding properties. Particularly preferred. Further, it is preferably 4.0 or less, more preferably 3.0 or less, even more preferably 2.0 or less, and particularly preferably 1.5 or less.
- optical density (OD) is a value measured by a method described later.
- the material of the support for forming the cured product is not particularly limited as long as it has appropriate strength.
- Substrates are mainly used, and materials include, for example, polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, and epoxy resins. , thermosetting resin sheets such as unsaturated polyester resins, poly(meth)acrylic resins, and various glasses. From the viewpoint of heat resistance, glass and heat-resistant resin are preferred. Further, a transparent electrode such as ITO or IZO, or a metal electrode such as silver, gold, platinum, aluminum, or magnesium may be formed on the surface of the substrate. In addition to the above-mentioned substrates, it is also possible to form on a TFT array.
- the support may be subjected to, for example, corona discharge treatment, ozone treatment, or thin film formation treatment of various resins such as silane coupling agents and urethane resins, as necessary, in order to improve surface properties such as adhesion.
- the thickness of the support is preferably in the range of 0.05 to 10 mm, more preferably 0.1 to 7 mm. Further, when performing a thin film formation treatment of various resins, the film thickness is preferably in the range of 0.01 to 10 ⁇ m, more preferably 0.05 to 5 ⁇ m.
- a photosensitive colored resin composition is supplied in the form of a film or pattern by a method such as coating onto the support on which the cured product is to be provided, and the solvent is dried. Subsequently, pattern formation is performed by a method such as photolithography that involves exposure and development. Thereafter, a cured product is formed on the substrate by performing additional exposure or heat curing treatment if necessary.
- the photosensitive colored resin composition of the present invention is preferably supplied onto a support in a state in which it is dissolved or dispersed in a solvent.
- a method for supplying it conventionally known methods such as a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, and a spray coating method can be used.
- it may be supplied in a pattern by, for example, an inkjet method or a printing method.
- the die coating method the amount of coating liquid used is significantly reduced, there is no influence of mist etc. that adheres when using the spin coating method, and the generation of foreign matter is suppressed, from a comprehensive perspective. preferable.
- the amount of coating varies depending on the application, it is applied so that the dry film thickness is preferably 0.5 to 10 ⁇ m, more preferably 1 to 9 ⁇ m, particularly preferably 1 to 7 ⁇ m. It is important that the dry film thickness or the height of the finally formed cured product be uniform over the entire support. By reducing the variation, the light-shielding property within the support becomes uniform, and when used as a partition wall, the light-emitting layer can be made uniform, and display defects during light emission can be suppressed.
- the photosensitive colored resin composition of the present invention When the photosensitive colored resin composition of the present invention is used to collectively form cured products with different heights by photolithography, the heights of the finally formed cured products will be different.
- Drying method The drying after supplying the photosensitive colored resin composition onto the support is preferably carried out by a drying method using a hot plate, an IR oven, or a convection oven.
- a reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature may be combined.
- Drying conditions can be selected as appropriate depending on the type of solvent component, the performance of the dryer used, etc.
- the drying time is preferably selected in the range of 15 seconds to 5 minutes at a temperature of 40 to 130°C, more preferably at a temperature of 50 to 110°C, depending on the type of solvent component, the performance of the dryer used, etc.
- the duration is selected from 30 seconds to 3 minutes.
- Exposure is performed by overlaying a negative mask pattern on the coating film of the photosensitive colored resin composition and irradiating it with an ultraviolet or visible light source through this mask pattern.
- the exposure mask may be placed close to the coating film of the photosensitive colored resin composition, or the exposure mask may be placed at a position away from the coating film of the photosensitive colored resin composition.
- a method of projecting exposure light through an exposure mask may also be used.
- a scanning exposure method using laser light without using a mask pattern may also be used.
- exposure may be carried out in an oxygen-free atmosphere or after forming an oxygen barrier layer such as a polyvinyl alcohol layer on the photopolymerizable layer. Good too.
- a light-shielding area (light transmittance 0%) and an opening with the highest average light transmittance (completely transparent opening) are formed as multiple openings. ) is used.
- An exposure mask having an opening (intermediate transmission opening) with a small average light transmittance is used.
- the difference in film remaining ratio is caused by the difference in average light transmittance between the intermediate transmission aperture and the complete transmission aperture, that is, the difference in exposure amount.
- a method is known in which the intermediate transmission opening is fabricated using a matrix-like light-shielding pattern having minute polygonal light-shielding units.
- a method is known in which the absorber is manufactured by controlling the light transmittance using a film of a chromium-based, molybdenum-based, tungsten-based, or silicone-based material, for example.
- the light source used for exposure is not particularly limited.
- Examples of light sources include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, fluorescent lamps, argon ion lasers, YAG lasers, Laser light sources include excimer lasers, nitrogen lasers, helium cadmium lasers, blue-violet semiconductor lasers, and near-infrared semiconductor lasers. When using irradiation with light of a specific wavelength, an optical filter can also be used.
- the optical filter may be, for example, a thin film type that can control the light transmittance at the exposure wavelength, and the material in this case may be, for example, a Cr compound (Cr oxide, nitride, oxynitride, fluoride, etc.). , MoSi, Si, W, and Al.
- a Cr compound Cr oxide, nitride, oxynitride, fluoride, etc.
- MoSi Si, W, and Al.
- the exposure amount is not particularly limited, but is preferably 1 mJ/cm 2 or more, more preferably 5 mJ/cm 2 or more, even more preferably 10 mJ/cm 2 or more, and preferably 300 mJ/cm 2 or less, more preferably is 200 mJ/cm 2 or less, more preferably 150 mJ/cm 2 or less.
- an image pattern can be formed on the support by development using an aqueous solution of an alkaline compound or an organic solvent.
- the aqueous solution of the alkaline compound may further contain, for example, a surfactant, an organic solvent, a buffer, a complexing agent, a dye, or a pigment.
- alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, and phosphorus.
- Inorganic alkaline compounds such as acid potassium, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-, di- or triethanolamine, mono-, di- or Organics such as trimethylamine, mono-, di- or triethylamine, mono- or di-isopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc.
- Examples include alkaline compounds. These alkaline compounds may be used alone or in combination of two or more.
- surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; alkylbenzene sulfonic acids
- alkylbenzene sulfonic acids examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinic acid ester salts; amphoteric surfactants such as alkyl betaines and amino acids.
- organic solvent examples include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. Two or more of these organic solvents may be used in combination. Further, the organic solvent may be used alone or in combination with water or an aqueous solution of an alkaline compound.
- the conditions for the development treatment are not particularly limited, and the development temperature is preferably 10 to 50°C, more preferably 15 to 45°C, and still more preferably 20 to 40°C.
- the development method can be, for example, an immersion development method, a spray development method, a brush development method, or an ultrasonic development method.
- thermosetting treatment also referred to as baking
- the heat curing treatment conditions are such that the temperature is preferably 100 to 280°C, more preferably 150 to 250°C, and the time is 5 to 60 minutes.
- the photosensitive colored resin composition of the present invention can be suitably used to form partition walls, particularly partition walls for partitioning organic layers of an organic electroluminescent device.
- the organic layer used in the organic electroluminescent device include a hole injection layer, a hole transport layer, or a hole transport layer on the hole injection layer, as described in Japanese Patent Application Publication No. 2016-165396. Examples include the organic layer used.
- the size, shape, etc. are appropriately adjusted depending on the specifications of the organic electroluminescent device to which it is applied, but the film thickness of the partition formed from the photosensitive colored resin composition of the present invention is , the optical density (OD) per ⁇ m is similar to that of the cured film.
- the organic electroluminescent device of the present invention includes a cured product formed from the photosensitive colored resin composition of the present invention, for example, a partition wall.
- various organic electroluminescent devices are manufactured using a substrate provided with a barrier rib pattern manufactured by the method described above.
- the method for forming an organic electroluminescent device is not particularly limited, but preferably, after forming a barrier rib pattern on a substrate by the method described above, the functional material is sublimated in a vacuum to form an area surrounded by the barrier ribs on the substrate.
- An organic electroluminescent device is manufactured by forming an organic layer such as a pixel by a wet process such as a vapor deposition method, a casting method, a spin coating method, or an inkjet printing method.
- Types of organic electroluminescent devices include bottom emission type and top emission type.
- a partition wall is formed on a glass substrate laminated with a transparent electrode, and a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode layer are stacked in the opening surrounded by the partition wall. Ru.
- a partition is formed on a glass substrate with a metal electrode layer laminated as a reflective layer, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are formed in the opening surrounded by the partition. It is made by laminating layers.
- the anode is mounted on a support, but is not limited thereto.
- Examples of the light-emitting layer include organic electroluminescent layers as described in Japanese Patent Application Publication No. 2009-146691 and Japanese Patent No. 5734681.
- quantum dots such as those described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may be used.
- each layer of the hole transport layer and the electron transport layer may have a laminated structure consisting of two or more layers from the viewpoint of luminous efficiency.
- the thickness of each layer is not particularly limited, but from the viewpoint of luminous efficiency and brightness, it is preferably 1 to 500 nm.
- the organic electroluminescent element may be formed with RGB colors separated for each opening, or two or more colors may be stacked in one opening.
- the organic electroluminescent device may include a sealing layer from the viewpoint of improving reliability.
- the sealing layer has a function of preventing moisture in the air from adsorbing to the organic electroluminescent element and reducing luminous efficiency.
- the organic electroluminescent device may include a low-reflection film at the interface with air from the viewpoint of improving light extraction efficiency. By arranging a low-reflection film at the interface between air and the element, it is expected that the gap in refractive index will be reduced and reflection at the interface will be suppressed. For example, a moth-eye structure or a super multilayer film technique can be applied to such a low reflection film.
- an organic electroluminescent device When using an organic electroluminescent device as a pixel in an image display device, it is necessary to prevent light from the light emitting layer of one pixel from leaking to other pixels, and in addition, if the electrodes are made of metal, it is necessary to prevent the light from the light emitting layer of one pixel from leaking to other pixels. Since it is necessary to prevent image quality from deteriorating due to reflection of light, it is preferable to impart light-shielding properties to the partition walls constituting the organic electroluminescent device. In an organic electroluminescent device, it is necessary to provide electrodes on the upper and lower surfaces of the partition walls, so from the viewpoint of insulation, the partition walls preferably have high resistance and low dielectric constant. Therefore, when using a coloring agent to impart light-shielding properties to the partition walls, it is preferable to use the organic pigment that has high resistance and low dielectric constant.
- the color filter containing the luminescent nanocrystal particles according to the present invention is not particularly limited as long as it is provided with the barrier ribs of the present invention, and examples thereof include those in which pixels are formed in regions partitioned by the barrier ribs.
- FIG. 1 is a schematic cross-sectional view of an example of a color filter including partition walls of the present invention.
- the color filter 100 includes a substrate 10, a partition wall 20 provided on the substrate, a red pixel 30, a green pixel 40, and a blue pixel 50.
- the red pixel 30, the green pixel 40, and the blue pixel 50 are arranged in a grid pattern so as to be repeated in this order.
- the partition wall 20 is provided between these adjacent pixels. In other words, these adjacent pixels are separated by the partition wall 20.
- the red pixel 30 contains red light-emitting nanocrystal particles 2
- the green pixel 40 contains green light-emitting nanocrystal particles 1.
- the blue pixel 50 is a pixel that transmits blue light from a light source.
- nanocrystal particles are nano-sized crystals that absorb excitation light and emit fluorescence or phosphorescence, and have a maximum particle diameter of 100 nm or less as measured by, for example, a transmission electron microscope or a scanning electron microscope. It is a crystalline substance.
- Luminescent nanocrystal particles are particles that can emit light (fluorescence or phosphorescence) at a wavelength different from the absorbed wavelength by absorbing light at a predetermined wavelength; for example, red luminescent nanocrystal particles 2 emits light (red light) having an emission peak wavelength in the range of 605 to 665 nm, and green-emitting nanocrystal particles 1 emit light (green light) having an emission peak wavelength in the range of 500 to 560 nm. ).
- the wavelength of light emitted by a luminescent nanocrystal particle depends on the size of the luminescent nanocrystal particle (for example, particle diameter). It also depends on the energy gap that the crystal grains have. Therefore, the color of the emitted light can be selected by changing the constituent material and size of the luminescent nanocrystal particles used. Examples of the luminescent nanocrystal particles include quantum dots and the like.
- the method for producing a color filter containing luminescent nanocrystal particles is not particularly limited, but it may be necessary to prepare a substrate having partition walls formed from the cured product of the present invention, and to contain luminescent nanocrystal particles in regions partitioned by the partition walls.
- Examples include a method of forming a layer.
- the method for forming a layer containing luminescent nanocrystal particles is not particularly limited, but for example, an ink composition containing luminescent nanocrystal particles is selectively deposited by an inkjet method, and the ink composition is formed by irradiation with active energy rays or heating. It can be manufactured by a method of curing an object.
- Examples of the image display device of the present invention include an organic EL display device having partition walls and organic electroluminescent elements containing the cured product of the present invention.
- the organic EL display device includes the above-mentioned organic electroluminescent device, there are no particular restrictions on the type or structure of the image display device, and for example, the organic EL display device can be assembled according to a conventional method using an active drive type organic electroluminescent device. can. For example, it can be formed by the method described in "Organic EL Display” (Ohmsha, published August 20, 2004, written by Seiji Tokito, Chinaya Adachi, and Hideyuki Murata). For example, an image may be displayed by combining an organic electroluminescent device that emits white light and a color filter, or an image may be displayed by combining organic electroluminescent devices that emit light of different colors, such as RGB.
- the alkali-soluble resin-I thus obtained has a weight average molecular weight Mw of 2456 and an acid value of 64 mgKOH/g as measured by GPC, and corresponds to resin (C1) and has a structure represented by formula (C1-1). Applicable.
- EPICLON HP7200HH manufactured by DIC Corporation polyglycidyl ether of dicyclopentadiene/phenol polymer, weight average molecular weight 1000, epoxy equivalent weight 270
- EPICLON HP7200HH manufactured by DIC Corporation polyglycidyl ether of dicyclopentadiene/phenol polymer, weight average molecular weight 1000, epoxy equivalent weight 270
- 155 parts by mass 41 parts by mass of acrylic acid, 0.1 part by mass of p-methoxyphenol, triphenylphosphine 2.5 parts by mass and 270 parts by mass of propylene glycol monomethyl ether acetate were charged into a reaction vessel, and heated and stirred at 100°C until the acid value became 3.0 mgKOH/g or less. It took 9 hours for the acid value to reach the target (acid value 2.9 mgKOH/g).
- alkali-soluble resin-II has a weight average molecular weight Mw of 3500 and an acid value of 60 mgKOH/g, and does not correspond to resin (C1).
- TMP trimethylolpropane
- BPDA biphenyltetracarboxylic dianhydride
- THPA tetrahydrophthalic anhydride
- Alkali-soluble resin-VI > "KBR-201" manufactured by KISCO.
- Alkali-soluble resin-VI corresponds to (C2) epoxy (meth)acrylate resin.
- Alkali-soluble resin-VII was obtained having a weight average molecular weight (Mw) of 2800 in terms of polystyrene and a weight average molecular weight (Mw) of 145 mgKOH/g measured by GPC.
- Alkali-soluble resin-VII corresponds to (C3) isocyanuric skeleton-containing resin.
- alkali-soluble resin-I has a weight average molecular weight Mw of 1668 and an acid value of 96.3 mgKOH/g as measured by GPC, and corresponds to resin (C1) and is represented by formula (C1-1). Applies to structure.
- ⁇ Dispersant-I> A block copolymer consisting of an A block containing a repeating unit having a solvent-philic group and a B block containing a repeating unit having a tertiary amino group.
- ⁇ Dispersant-II> A block copolymer consisting of an A block containing a repeating unit having a solvent-philic group and a B block containing a repeating unit having a tertiary amino group and a quaternary ammonium group.
- Viscosity evaluation> Immediately after preparing the pigment dispersion using a RE-85L viscometer manufactured by Toki Sangyo Co., Ltd. (measurement conditions: 23°C, 20rpm), after preparing the pigment dispersion, leave it at room temperature (24°C) for one day. , and after standing for 3 days, the viscosity of the pigment dispersion was measured and determined as follows. From the viewpoint of applicability and stability over time of the photosensitive colored resin composition, it is preferable that the viscosity of the pigment dispersion is low. A: Viscosity is 10 mPa ⁇ s or less B: Viscosity is greater than 10 mPa ⁇ s C: Solidifies without being able to disperse
- a spinner was used on a substrate on which an indium tin oxide (ITO) film was formed on the surface of a glass substrate with a film thickness of 0.7 mm, and each example A photosensitive colored resin composition of a comparative example was applied. Thereafter, a drying process was performed for 60 seconds using a vacuum dryer. Subsequently, it was heated and dried for 100 seconds on a hot plate heated to 100° C. to obtain a coated film substrate. The film thickness of the heat-dried coating film was measured by the method described below, and the film thickness T1 ( ⁇ m) was determined. The obtained coated substrate was exposed to light using a photomask.
- ITO indium tin oxide
- a mirror projection type exposure machine (MPA-600FA) manufactured by Canon Inc.
- exposure was performed for 20 seconds so that the exposure amount was 80 mJ/cm 2 .
- the illuminance was 500 mW/cm 2 and the slit width was 1.6 mm.
- a mask having a grid-like opening (having a 50 ⁇ m square-shaped underside and having a plurality of the above-mentioned covering portions through an exposed portion of 50 ⁇ m) was used.
- the water pressure was 0 at 24°C.
- the developing solution was flushed with pure water to stop the development, and the film was washed with water washing spray for 10 seconds.
- the shower development time was set to be 1.6 times the time for dissolving and removing the unexposed areas of the coating film.
- the photosensitive colored resin composition is washed away in the portion corresponding to the square light-shielding portion, so that the ITO substrate is exposed and a hole portion is formed. This substrate was heated and cured (baked) at 230° C. for 30 minutes in an oven to obtain a patterned substrate for patternability measurement. At this time, the film thickness T2 ( ⁇ m) was measured.
- the film thickness of the coating film at each step (after drying, after baking) on the patterned substrate was measured using a non-contact surface/layer cross-sectional shape measuring system VertScan (R) 2.0 manufactured by Ryoka System Co., Ltd.
- VertScan the ratio of the film thickness after firing (T2) to the film thickness after drying (T1) was calculated as the residual film ratio.
- Remaining film rate (%) (T2/T1) x 100 (%)
- the calculated residual film rate was determined as follows. A has the highest residual film rate and is good, and if the residual film rate is 75% or more, there is a tendency that there is no problem in practical use.
- Remaining film rate 80% or more B: Remaining film rate less than 80% but 75% or more
- C Remaining film rate less than 75% Note that the residual film rate depends on the exposure sensitivity of the resist, its solubility in the developer, and the time of baking. Thermal decomposability is involved, and the higher the residual film rate, the better.
- optical density per unit film thickness (unit OD value)> The optical density per unit film thickness was measured according to the following procedure.
- the photosensitive colored resin compositions of each example and comparative example were applied onto a glass substrate using a spinner so that the thickness would be 1.5 ⁇ m after heat curing (baking). Thereafter, a drying process was performed for 60 seconds using a vacuum dryer. Subsequently, it was heated and dried for 100 seconds on a hot plate heated to 100°C. The obtained coating film was exposed to light without using an exposure mask.
- a mirror projection type exposure machine (MPA-600FA) manufactured by Canon Inc. was used as the irradiation light source, and exposure was performed for 20 seconds so that the exposure amount was 80 mJ/cm 2 .
- the illuminance was 500 mW/ cm2 .
- the resist-coated substrate 1 was obtained by heating and curing in an oven at 230° C. for 30 minutes.
- the optical density (OD value) of the obtained resist-coated substrate 1 was measured using an X-Rite 361T(V) transmission densitometer (color temperature of illumination light source: approximately 2850K (equivalent to CIE standard light source A), spectral sensitivity of light receiving part).
- the film thickness was measured using VertScan (R) 2.0, a non-contact surface/layer cross-sectional shape measurement system manufactured by Ryoka System Co., Ltd., and the optical density ( The optical density (unit OD value) per unit film thickness (1 ⁇ m) was calculated from the OD value) and the film thickness.
- the OD value is a numerical value indicating the light-shielding ability, and the larger the value, the higher the light-shielding ability.
- ⁇ Preparation of patterned substrate for organic electroluminescent device> Each example was prepared using a spinner on a substrate on which an anode was formed by depositing an indium tin oxide (ITO) transparent conductive film to a thickness of 70 nm on glass using ordinary photolithography technology and hydrochloric acid etching. - A photosensitive colored resin composition of a comparative example was applied. Thereafter, a drying process was performed for 60 seconds using a vacuum dryer. Subsequently, it was heated and dried for 100 seconds on a hot plate heated to 100°C. The obtained coated substrate was exposed to light using a photomask.
- ITO indium tin oxide
- the photomask is a mask having a grid-like opening (having a rectangular covering part of 40 ⁇ m in length x 80 ⁇ m in width, and having a plurality of said covering parts through an exposed part of 20 ⁇ m in the long axis and short axis directions). It was used.
- the water pressure was 0 at 24°C.
- the developing solution was flushed with pure water to stop the development, and the film was washed with water washing spray for 10 seconds.
- the shower development time was set to be 1.6 times the time for dissolving and removing the unexposed areas of the coating film.
- An organic electroluminescent device was fabricated by sequentially stacking 8-hydroxyquinolinolato-lithium as an electron injection layer to a thickness of 1 nm and aluminum as a cathode to a thickness of 80 nm using a vacuum evaporation method. Next, a desiccant was applied to the recessed part of the sealing glass having a recessed part in the center, and a UV curing resin was applied to the frame portion around the recessed part. The concave portion of the sealing glass is arranged so as to cover all the organic electroluminescent elements on the electrode substrate, the sealing glass is attached to the electrode substrate, and the UV curing resin is cured by irradiating UV to seal the hollow structure. By doing this, a device for evaluating organic electroluminescent elements was fabricated.
- Examples 1 to 4 using alkali-soluble resin-I were observed to have low viscosity and excellent dispersibility.
- Comparative Examples 1, 3, and 4 could not be dispersed and solidified, and Comparative Example 2 was dispersible but had a high viscosity and poor dispersibility.
- the viscosity of Examples 3 to 5 remains stable even 3 days after the preparation of the pigment dispersion, but the viscosity of Comparative Example 5 gradually increases immediately after the preparation of the pigment dispersion. was observed.
- resin (C1) has a high affinity with pigments because it contains many aromatic rings in its main chain, and also has a flexibility that can follow the surface shape of pigments because it also contains methylene groups in its main chain. It is considered to have a high effect on pigment dispersibility.
- Alkali-soluble resin-I and alkali-soluble resin-VIII correspond to resin (C1) and are considered to have high pigment dispersibility. Furthermore, it is thought that the pigment dispersibility and viscosity stability were improved because the alkali-soluble resin-VIII had more hydroxyl groups with higher solvent affinity than the alkali-soluble resin-I.
- alkali-soluble resin-II has a low content of aromatic rings in its main chain, it has a bulky dicyclopentane skeleton, so it is considered to have a low pigment dispersibility effect.
- alkali-soluble resins III and IV contain many aromatic rings in their main chains, their main chains are rigid and have poor flexibility, and are disadvantageous in that they follow the surface shape of pigments, so they have poor pigment dispersibility effects. considered to be low.
- Table 5 shows the evaluation results of organic electroluminescent devices produced using the adjusted photosensitive colored resin compositions of Examples 6, 8, and 10 and Comparative Examples 6 and 7.
- Examples 6, 8, and 10 in Table 5 tend to have high current densities during light emission. This is because Alkali Soluble Resin-I and Alkali Soluble Resin-VIII contain many aromatic rings in their main chains, which improves developer resistance during development. It is assumed that this is because the accumulation of decomposed products is reduced. In addition, the alkali-soluble resin-VII has an isocyanuric skeleton with high heat resistance, and it is thought that the accumulation of thermal decomposition products in the pixels during firing is reduced, resulting in a higher current density value. On the other hand, in Comparative Examples 6 and 7, the current density tends to be low. It is presumed that this is because the number of aromatic rings contained in the main chain is small and developer resistance is reduced, which increases the amount of decomposed products deposited in the pixel portion of the organic electroluminescent device during development.
- Green-emitting nanocrystal particles 1 Green-emitting nanocrystal particles 2 Red-emitting nanocrystal particles 10 Substrate 20 Partition wall 30 Red pixel 40 Green pixel 50 Blue pixel 100 Color filter
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Abstract
Description
本願は、2022年8月9日に日本に出願された特願2022-127367号に基づき優先権を主張し、その内容をここに援用する。
この感光性組成物は、微細な構造を形成し易く、大画面用の基板に対しての処理もし易いといった理由から、さらにその適用範囲は広がっている。
有機電界発光素子は、少なくとも一方が透光性を有する一対の電極間に、発光層あるいは種々の機能層を含む有機層が狭持された構造を有するものである。画像表示装置は画素毎に有機電界発光素子が配置されたパネルを駆動させることにより、画像表示を行うものである。
従来からこのような有機電界発光素子は、基板上に、隔壁(バンク)を形成した後に、隔壁に囲まれた領域内に、発光層あるいは種々の機能層を積層して製造されている。
近年では、キャスト法、スピンコート法、インクジェット印刷法といったウェットプロセスにて成膜する方法が注目されている。特に、インクジェット印刷法は、大面積にした場合の膜厚ムラを低減することができるとともに、塗布時の塗り分けによるディスプレイの高精細化、材料の使用量の削減、歩留まりの向上を図ることが可能となるため、大型パネルにおける有機層の成膜方法として好適である。
また、隔壁の製造時の現像工程や焼成工程において、感光性着色樹脂組成物の残膜率が低い場合、現像液耐性や焼成時の熱耐性に劣るため、組成物中の分解物、副生成物、未硬化物などが、陽極上に残留、あるいは再付着することがある。
[1](A)着色剤、(B)分散剤、(C)アルカリ可溶性樹脂及び(D)光重合開始剤を含有する感光性着色樹脂組成物であって、
前記(A)着色剤が有機顔料(A-1)を含み、
前記(C)アルカリ可溶性樹脂が、下記一般式(1)で表される構造単位を有する樹脂(C1)を含有することを特徴とする、感光性着色樹脂組成物。
R2は各々独立に、炭素数1~4のアルキル基を表す。
Lは炭素数2~6のアルキレン基を表し、置換基として、少なくとも水酸基、又は水酸基と多塩基酸とのエステル基を有する。
*は各々結合手を表す。)
[2]前記樹脂(C1)が、下記一般式(2)で表される構造単位を有する[1]の感光性着色樹脂組成物。
R1は水素原子又はメチル基を表す。
R2は各々独立に、炭素数1~4のアルキル基を表す。
*は各々結合手を表す。)
[3]前記有機顔料(A-1)が有機黒色顔料を含む、[1]又は[2]の感光性着色樹脂組成物。
[4]前記有機黒色顔料が、ベンゾジフラノン系有機黒色顔料を含む、[3]の感光性着色樹脂組成物。
[5]前記有機黒色顔料が、下記一般式(A-1-1)で表される化合物、その幾何異性体、その塩、又はその幾何異性体の塩である有機黒色顔料を含む、[4]の感光性着色樹脂組成物。
R612、R613、R614、R615、R617、R618、R619及びR620は各々独立に、水素原子、ハロゲン原子、R621、COOH、COOR621、COO-、CONH2、CONHR611、CONR621R622、CN、OH、OR621、COCR621、OOCNH2、OOCNHR621、OOCNR621R622、NO2、NH2、NHR621、NR621R622、NHCOR622、NR621COR622、N=CH2、N=CHR621、N=CR621R622、SH、SR621、SOR621、SO2R621、SO3R621、SO3H、SO3 -、SO2NH2、SO2NHR621又はSO2NR621R622を表し;
R612とR613、R613とR614、R614とR615、R617とR618、R618とR619、及びR619とR620からなる群から選ばれる少なくとも1つの組み合わせは、互いに直接結合してもよく、又は酸素原子、硫黄原子、NH若しくはNR621ブリッジによって互いに結合してもよく;
R621及びR622は各々独立に、炭素数1~12のアルキル基、炭素数3~12のシクロアルキル基、炭素数2~12のアルケニル基、炭素数3~12のシクロアルケニル基又は炭素数2~12のアルキニル基を表す。)
[6]前記(B)分散剤が、3級アミノ基及び/又は4級アンモニウム基を有するアクリル系分散剤を含む、[1]又は[2]の感光性着色樹脂組成物。
[7]前記(C)アルカリ可溶性樹脂が、(C2)エポキシ(メタ)アクリレート樹脂を含有する、[1]又は[2]の感光性着色樹脂組成物。
[8]前記(C)アルカリ可溶性樹脂が、(C3)イソシアヌル骨格含有樹脂を含有する、[1]又は[2]の感光性着色樹脂組成物。
[9]前記(C)アルカリ可溶性樹脂における、前記樹脂(C1)の含有割合が4~80質量%の範囲である、[1]又は[2]の感光性着色樹脂組成物。
前記(A)着色剤が有機顔料(A-1)を含み、
前記(C)アルカリ可溶性樹脂が、下記一般式(1)で表される構造単位を有する樹脂(C1)を含有することを特徴とする顔料分散液。
R2は各々独立に、炭素数1~4のアルキル基を表す。
Lは炭素数2~6のアルキレン基を表し、置換基として、少なくとも水酸基、又は水酸基と多塩基酸とのエステル基を有する。
*は各々結合手を表す。)
[11]前記樹脂(C1)が、下記一般式(2)で表される構造単位を有する[10]の顔料分散液。
R1は水素原子又はメチル基を表す。
R2は各々独立に、炭素数1~4のアルキル基を表す。
*は各々結合手を表す。)
[12]前記有機顔料(A-1)が有機黒色顔料を含む、[10]又は[11]の顔料分散液。
[13]前記有機黒色顔料が、ベンゾジフラノン系有機黒色顔料を含む、[12]の顔料分散液。
[14]前記有機黒色顔料が、下記一般式(A-1-1)で表される化合物、その幾何異性体、その塩、又はその幾何異性体の塩である有機黒色顔料を含む、[13]の顔料分散液。
R612、R613、R614、R615、R617、R618、R619及びR620は各々独立に、水素原子、ハロゲン原子、R621、COOH、COOR621、COO-、CONH2、CONHR621、CONR621R622、CN、OH、OR621、COCR621、OOCNH2、OOCNHR621、OOCNR621R622、NO2、NH2、NHR621、NR621R622、NHCOR622、NR621COR622、N=CH2、N=CHR621、N=CR621R622、SH、SR621、SOR621、SO2R621、SO3R621、SO3H、SO3 -、SO2NH2、SO2NHR621又はSO2NR621R622を表し;
R612とR613、R613とR614、R614とR615、R617とR618、R618とR619、及びR619とR620からなる群から選ばれる少なくとも1つの組み合わせは、互いに直接結合してもよく、又は酸素原子、硫黄原子、NH若しくはNR621ブリッジによって互いに結合してもよく;
R621及びR622は各々独立に、炭素数1~12のアルキル基、炭素数3~12のシクロアルキル基、炭素数2~12のアルケニル基、炭素数3~12のシクロアルケニル基又は炭素数2~12のアルキニル基を表す。)
[15]前記(B)分散剤が、3級アミノ基及び/又は4級アンモニウム基を有するアクリル系分散剤を含む、[10]又は[11]の顔料分散液。
[17][1]~[9]及び[16]のいずれかの感光性着色樹脂組成物を硬化させた硬化物。
[18][17]の硬化物から形成される、隔壁。
[19][18]の隔壁を備える、有機電界発光素子。
[20][19]の隔壁を備える、発光性ナノ結晶粒子を含むカラーフィルター。
[21][19]の隔壁を備える、画像表示装置。
R2は各々独立に、炭素数1~4のアルキル基を表す。
Lは炭素数2~6のアルキレン基を表し、置換基として、少なくとも水酸基、又は水酸基と多塩基酸とのエステル基を有する。
*は各々結合手を表す。)
本発明において、「(メタ)アクリル」とは、「アクリル及び/又はメタクリル」を意味し、「(メタ)アクリレート」、「(メタ)アクリロイル」についても同様である。
「アクリル系樹脂」とは、(メタ)アクリル酸を含む(共)重合体、カルボキシ基を有する(メタ)アクリル酸エステルを含む(共)重合体を意味する。
「全固形分」とは、感光性着色樹脂組成物中、又は顔料分散液中に含まれる、溶剤以外の全成分を意味し、溶剤以外の成分が常温で液体であっても、その成分は溶剤には含めず、全固形分に含める。
「(共)重合体」とは、単一重合体(ホモポリマー)と共重合体(コポリマー)の双方を含むことを意味し、「酸(無水物)」、「(無水)…酸」とは、酸とその無水物の双方を含むことを意味する。
「モノマー」とは、いわゆる高分子物質(ポリマー)に相対する用語であり、狭義の単量体(モノマー)の他に、二量体、三量体、オリゴマーも含む意味である。
「重量平均分子量」とは、GPC(ゲルパーミエーションクロマトグラフィー)によるポリスチレン換算の重量平均分子量(Mw)を意味する。
「アミン価」とは、特に断りのない限り、有効固形分換算のアミン価を表し、分散剤の固形分1gあたりの塩基量と当量のKOHの質量で表される値である。測定方法については後述する。
「酸価」とは、特に断りのない限り、有効固形分換算の酸価を表し、中和滴定により算出される。
顔料に関し、「C.I.」とはカラーインデックスを意味する。
本明細書において、「質量」で表される百分率や部は「重量」で表される百分率や部と同義である。
本発明の感光性着色樹脂組成物は、
(A)着色剤
(B)分散剤
(C)アルカリ可溶性樹脂
(D)光重合開始剤
を含有する。
本発明の感光性着色樹脂組成物は、(A)着色剤を含有する。(A)着色剤を含有することで、適度な光吸収性、特に隔壁等の遮光部材を形成する用途に用いる場合には適度な遮光性を得ることができる。
本発明の(A)着色剤は有機顔料(A-1)を含有する。有機顔料(A-1)を含有することで絶縁性が良好となる傾向がある。
(A)着色剤として用いることができる有機顔料は特に限定されないが、例えば、有機着色顔料や有機黒色顔料が挙げられる。ここで、有機着色顔料とは、黒色以外の色を呈する有機顔料のことを意味し、例えば、赤色顔料、橙色顔料、青色顔料、紫色顔料、緑色顔料、黄色顔料が挙げられる。
ペリレン系黒色顔料としては、例えば、Lumogen Black(登録商標)FK4281、K0087、Paliogen Black(登録商標)EH0788(いずれもBASF社製)が挙げられる。
アニリン系黒色顔料としては、例えば、Paliotol Black(登録商標)L0080、D0080、K0080(いずれもBASF社製)が挙げられる。
ベンゾジフラノン系黒色顔料のうち、遮光性、分散性、現像性、発光特性の観点からは、下記一般式(A-1-1)で表される化合物(以下、「化合物(A-1-1)」と称する場合がある。)、化合物(A-1-1)の幾何異性体、化合物(A-1-1)の塩、及び化合物(A-1-1)の幾何異性体の塩からなる群から選ばれる少なくとも1種を含む有機黒色顔料(以下、「一般式(A-1-1)で表される有機黒色顔料」と称する場合がある。)を用いることが好ましい。
R612、R613、R614、R615、R617、R618、R619及びR620は各々独立に、水素原子、ハロゲン原子、R621、COOH、COOR621、COO-、CONH2、CONHR621、CONR621R622、CN、OH、OR621、COCR621、OOCNH2、OOCNHR621、OOCNR621R622、NO2、NH2、NHR621、NR621R622、NHCOR622、NR621COR622、N=CH2、N=CHR621、N=CR621R622、SH、SR621、SOR621、SO2R621、SO3R621、SO3H、SO3 -、SO2NH2、SO2NHR621又はSO2NR621R622を表し;
R612とR613、R613とR614、R614とR615、R617とR618、R618とR619、及びR619とR620からなる群から選ばれる少なくとも1つの組み合わせは、互いに直接結合してもよく、又は酸素原子、硫黄原子、NH若しくはNR621ブリッジによって互いに結合してもよく;
R621及びR622は各々独立に、炭素数1~12のアルキル基、炭素数3~12のシクロアルキル基、炭素数2~12のアルケニル基、炭素数3~12のシクロアルケニル基又は炭素数2~12のアルキニル基を表す。
R612、R614、R615、R617、R619及びR620は各々独立に、好ましくは水素原子、フッ素原子、又は塩素原子であり、さらに好ましくは水素原子である。
R613及びR618は各々独立に、好ましくは水素原子、NO2、OCH3、OC2H5、臭素原子、塩素原子、CH3、C2H5、N(CH3)2、N(CH3)(C2H5)、N(C2H5)2、α-ナフチル、β-ナフチル、SO3H又はSO3 -であり、さらに好ましくは水素原子又はSO3Hであり、特に好ましくは水素原子である。
好ましくは、R611とR616、R612とR617、R613とR618、R614とR619、及びR615とR620からなる群から選ばれる少なくとも1つの組み合わせが同一であり、より好ましくは、R611はR616と同一であり、R612はR617と同一であり、R613はR618と同一であり、R614はR619と同一であり、かつ、R615はR620と同一である。
この有機黒色顔料は、好ましくは後述される分散剤、溶剤、方法によって分散して使用される。また、分散の際に化合物(A-1-1)のスルホン酸誘導体、特に化合物(A-1-2)のスルホン酸誘導体が存在すると、分散性や保存性が向上する場合があるため、有機黒色顔料がこれらのスルホン酸誘導体を含むことが好ましい。
赤色顔料:C.I.ピグメントレッド177、254、272
橙色顔料:C.I.ピグメントオレンジ43、64、72
青色顔料:C.I.ピグメントブルー15:6、60
紫色顔料:C.I.ピグメントバイオレット23、29
色の組み合わせについては特に限定されないが、遮光性の観点からは、例えば、赤色顔料と青色顔料の組み合わせ、青色顔料と橙色顔料の組み合わせ、青色顔料と橙色顔料と紫色顔料の組み合わせが挙げられる。
耐久性の観点から、顔料を用いることが好ましい。例えば、無機顔料が挙げられる。
無機黒色顔料としては、例えば、カーボンブラック、アセチレンブラック、ランプブラック、ボーンブラック、黒鉛、鉄黒、シアニンブラック、チタンブラックが挙げられる。
遮光性、画像特性の観点からカーボンブラックを好ましく用いることができる。
三菱ケミカル社製:MA7、MA8、MA11、MA77、MA100、MA100R、MA100S、MA220、MA230、MA600、MCF88、#5、#10、#20、#25、#30、#32、#33、#40、#44、#45、#47、#50、#52、#55、#650、#750、#850、#900、#950、#960、#970、#980、#990、#1000、#2200、#2300、#2350、#2400、#2600、#2650、#3030、#3050、#3150、#3250、#3400、#3600、#3750、#3950、#4000、#4010、OIL7B、OIL9B、OIL11B、OIL30B、OIL31B。
デグサ社製:Printex(登録商標、以下同じ。)3、Printex3OP、Printex30、Printex30OP、Printex40、Printex45、Printex55、Printex60、Printex75、Printex80、Printex85、Printex90、Printex A、Printex L、Printex G、Printex P、Printex U、Printex V、PrintexG、SpecialBlack550、SpecialBlack350、SpecialBlack250、SpecialBlack100、SpecialBlack6、SpecialBlack5、SpecialBlack4、Color Black FW1、Color Black FW2、Color Black FW2V、Color Black FW18、Color Black FW200、Color Black S160、Color Black S170。
キャボット社製:Monarch(登録商標、以下同じ。)120、Monarch280、Monarch460、Monarch800、Monarch880、Monarch900、Monarch1000、Monarch1100、Monarch1300、Monarch1400、Monarch4630、REGAL(登録商標、以下同じ。)99、REGAL99R、REGAL415、REGAL415R、REGAL250、REGAL250R、REGAL330、REGAL400R、REGAL550R、REGAL660R、BLACK PEARLS480、PEARLS130、VULCAN(登録商標、以下同じ。) XC72R、ELFTEX(登録商標)-8。
ビルラー社製:RAVEN(登録商標、以下同じ。)11、RAVEN14、RAVEN15、RAVEN16、RAVEN22、RAVEN30、RAVEN35、RAVEN40、RAVEN410、RAVEN420、RAVEN450、RAVEN500、RAVEN780、RAVEN850、RAVEN890H、RAVEN1000、RAVEN1020、RAVEN1040、RAVEN1060U、RAVEN1080U、RAVEN1170、RAVEN1190U、RAVEN1250、RAVEN1500、RAVEN2000、RAVEN2500U、RAVEN3500、RAVEN5000、RAVEN5250、RAVEN5750、RAVEN7000。
本発明の感光性着色樹脂組成物において、顔料の平均粒子径は、動的光散乱(DLS)により測定された顔料粒子径から求めた値である。粒子径測定は、十分に希釈された感光性着色樹脂組成物(通常は希釈して、顔料濃度0.005~0.2質量%程度に調製する。但し測定機器により推奨された濃度があれば、その濃度に従う。)に対して行い、25℃にて測定する。
キノンイミン系染料として、例えば、C.I.ベーシックブルー3、C.I.ベーシックブルー9が挙げられる。
キノリン系染料として、例えば、C.I.ソルベントイエロー33、C.I.アシッドイエロー3、C.I.ディスパースイエロー64が挙げられる。
ニトロ系染料として、例えば、C.I.アシッドイエロー1、C.I.アシッドオレンジ3、C.I.ディスパースイエロー42が挙げられる。
品質の安定性を確保する目的で、(A)着色剤を微細に分散させ、且つその分散状態を安定化させるため、本発明の感光性着色樹脂組成物は(B)分散剤を含む。
(B)分散剤としては、官能基を有する高分子分散剤が好ましく、さらに、分散安定性の面からカルボキシ基;リン酸基;スルホン酸基;又はこれらの塩基;一級、二級又は三級アミノ基;四級アンモニウム基;ピリジン、ピリミジン、ピラジン等の含窒素ヘテロ環由来の基、等の官能基を有する高分子分散剤が好ましい。特に、一級、二級又は三級アミノ基;四級アンモニウム基;ピリジン、ピリミジン、ピラジン等の含窒素ヘテロ環由来の基、等の塩基性官能基を有する高分子分散剤が少量の分散剤で顔料を分散することができるとの観点から特に好ましい。
高分子分散剤は、1種を単独で用いてもよく、2種以上を併用してもよい。
分散性、保存性の観点からは、塩基性官能基を有し、ポリエステル結合及びポリエーテル結合のいずれか一方又は両方を有する高分子分散剤が好ましい。
A-B又はB-A-Bブロック共重合体は、例えば、以下に示すリビング重合法にて調製される。
リビング重合法には、アニオンリビング重合法、カチオンリビング重合法、ラジカルリビング重合法があり、このうち、アニオンリビング重合法は、重合活性種がアニオンであり、例えば下記スキームで表される。
本発明で用いることができるA-Bブロック共重合体、B-A-Bブロック共重合体1g中の4級アンモニウム基の量は、0.1~10mmolであることが好ましい。この範囲内にすることで良好な分散性を確保しやすい傾向がある。
ここで、アクリル系分散剤のアミン価は、分散剤試料中の溶剤を除いた固形分1gあたりの塩基量と当量のKOHの質量で表し、次の方法により測定する。
100mLのビーカーに分散剤試料の0.5~1.5gを精秤し、50mLの酢酸で溶解する。pH電極を備えた自動滴定装置を使って、この溶液を0.1mol/LのHClO4酢酸溶液にて中和滴定する。滴定pH曲線の変曲点を滴定終点とし次式によりアミン価を求める。
〔但し、W:分散剤試料秤取量[g]、V:滴定終点での滴定量[mL]、S:分散剤試料の固形分濃度[質量%]を表す。〕
アルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基が挙げられ、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基が好ましく、メチル基、エチル基、プロピル基、ブチル基がより好ましく、メチル基、エチル基がさらに好ましい。
式(V)における、Y-としては、例えば、Cl-、Br-、I-、ClO4 -、BF4 -、CH3COO-、PF-が挙げられる。
また、国際公開第2018/079659号に記載された芳香族ジカルボン酸イミドアニオン、芳香族スルホン酸アニオン、芳香族ホスホン酸アニオン、芳香族カルボン酸アニオン;国際公開第2019/107020号に記載されたアルキル硫酸アニオン、アルキルスルホン酸アニオン;も好適に用いうる。
Y-としては、現像形態の観点からはCl-が好ましい。発光特性の観点からは、アルキルスルホン酸アニオンが好ましい。
式(VI)のR35及びR36における、置換基を有していてもよいアリール基としては、式(V)のR31~R33として例示したものを好ましく採用することができる。
式(VI)のR35及びR36における、置換基を有していてもよいアラルキル基としては、式(V)のR31~R33として例示したものを好ましく採用することができる。
分散性の観点から、繰り返し単位(V)を有することが好ましく、さらに発光特性の観点から、繰り返し単位(V)及び繰り返し単位(VI)を有することが好ましい。
R38における、アルキル基が有していてもよい置換基としては、例えば、ハロゲン原子、アルコキシ基が挙げられる。アリール基又はアラルキル基が有していてもよい置換基としては、例えば、鎖状のアルキル基、ハロゲン原子、アルコキシ基が挙げられる。R38で示される鎖状のアルキル基には、直鎖状及び分岐鎖状のいずれも含まれる。
これらのアクリル系分散剤は1種を単独で使用してもよく、又は2種以上を併用してもよい。
本発明の感光性着色樹脂組成物は、(C)アルカリ可溶し樹脂を含有する。(C)アルカリ可溶性樹脂は、下記一般式(1)で表される構造単位を有する樹脂(C1)を含有する。
R2は各々独立に、炭素数1~4のアルキル基を表す。
Lは炭素数2~6のアルキレン基を表し、置換基として、少なくとも水酸基、又は水酸基と多塩基酸とのエステル基を有する。
*は各々結合手を表す。
さらには、感光性着色樹脂組成物を硬化して得られる隔壁を用いて有機電界発光素子を形成した場合、陽極上への残留物、再付着物が減少することで、画素部への堆積が少なくなり、有機電界発光素子において電圧を印加した際の電流密度が高くなり、発光素子の輝度が向上する傾向がある。
式(1)におけるR2は各々独立に、炭素数1~4のアルキル基を表す。
R2におけるアルキル基の炭素数は、溶媒溶解性の観点から、1以上が好ましく、また、3以下が好ましく、2以下がより好ましい。
アルキル基は直鎖、又は分岐していてもよい。例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基が挙げられる。分散性の観点からメチル基が好ましい。
Lは炭素数2~6のアルキレン基を表し、置換基として、少なくとも水酸基、又は水酸基と多塩基酸とのエステル基を有する。
Lは炭素数3以上が好ましく、炭素数4がより好ましい。また5以下が好ましい。例えば、3~6であってよく、3~5であってよく、4~6であってよく、4~5であってよい。
Lは置換基として、少なくとも水酸基、又は水酸基と多塩基酸とのエステル基を有し、さらにメトキシ基、エトキシ基により置換されていてもよい。
ここで多塩基酸とは、後述する多塩基酸残基に挙げられている多塩基酸を意味する。また、水酸基と多塩基酸とのエステル基とは、Lに結合した水酸基が多塩基酸とエステルを形成した基を意味する。
式(1)の構造単位のうち、下記一般式(2)で記載される構造単位を有することが好ましい。
R1は水素原子又はメチル基を表す。
R2は各々独立に、炭素数1~4のアルキル基を表す。
*は各々結合手を表す。)
式(1)におけるAは水素原子又は多塩基酸残基を表す。
多塩基酸残基とは、多塩基酸からOH基を1又は2つ除した、1又は2価の基を意味する。前記多塩基酸としては、例えば、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ベンゾフェノンテトラカルボン酸、メチルヘキサヒドロフタル酸、エンドメチレンテトラヒドロフタル酸、クロレンド酸、メチルテトラヒドロフタル酸、ビフェニルテトラカルボン酸が挙げられる。
これらの中でも分散安定性の観点から、好ましくは、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ビフェニルテトラカルボン酸であり、より好ましくは、フタル酸、コハク酸、トリメリット酸、ピロメリット酸である。
特に酸価を同一にした場合、溶媒親和性の高い水酸基が前記他塩基酸残基より相対的に増加するためトリメリット酸が好ましい。
式(1)におけるR1は水素原子又はメチル基を表す。硬化性の観点から水素原子が好ましい。
式(1)におけるR2は各々独立に、炭素数1~4のアルキル基を表す。
R2におけるアルキル基の炭素数は、溶媒溶解性の観点から、1以上が好ましく、また、3以下が好ましく、2以下がより好ましい。
アルキル基は直鎖、又は分岐していてもよい。例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基が挙げられる。分散性の観点からメチル基が好ましい。
樹脂(C1)中に含まれる、式(1)で表される部分構造は、1種でも2種以上でもよく、例えば、Aが水素原子のものと、Aが多塩基酸残基のものが混在していてもよい。
(C2)エポキシ(メタ)アクリレート系樹脂
(C3)イソシアヌル骨格含有樹脂
(C4)アクリル共重合樹脂
が優れた製版性の観点から好適に用いられる。これらは1種を単独で、あるいは2種以上を併用することができる。
本発明における(C2)エポキシ(メタ)アクリレート系樹脂は、樹脂(C1)以外の(C)アルカリ可溶性樹脂であり、エポキシ化合物(エポキシ樹脂)とα,β-不飽和モノカルボン酸及び/又はエステル部分にカルボキシ基を有するα,β-不飽和モノカルボン酸エステルとの反応により生成した水酸基を、さらに多塩基酸及び/又はその無水物等の水酸基と反応し得る置換基を2個以上有する化合物と反応させて得られる樹脂である。ただし後述の(C3)イソシアヌル骨格含有樹脂は含めないものとする。
上記、多塩基酸及び/又はその無水物を水酸基と反応させる前に、水酸基と反応し得る置換基を2個以上有する化合物を反応させた後、多塩基酸及び/又はその無水物を反応させて得られる樹脂も、(C2)エポキシ(メタ)アクリレート系樹脂に含まれる。
エポキシ(メタ)アクリレート系樹脂は化学構造上、実質的にエポキシ基を有さず、かつ「(メタ)アクリレート」に限定されるものではないが、エポキシ化合物(エポキシ樹脂)が原料であり、かつ、「(メタ)アクリレート」が代表例であるので慣用に従いこのように命名されている。
(C2)エポキシ(メタ)アクリレート系樹脂としては、アウトガスの観点から、主鎖に芳香族環を有するものをより好適に用いることができる。
エポキシ樹脂にα,β-不飽和モノカルボン酸又はカルボキシ基を有するα,β-不飽和モノカルボン酸エステルを付加させ、さらに、多塩基酸及び/又はその無水物を反応させることによって得られたアルカリ可溶性樹脂。
<エポキシ(メタ)アクリレート系樹脂(C2-2)>
エポキシ樹脂にα,β-不飽和モノカルボン酸又はカルボキシ基を有するα,β-不飽和モノカルボン酸エステルを付加させ、さらに、多価アルコール、及び多塩基酸及び/又はその無水物と反応させることによって得られたアルカリ可溶性樹脂。
原料となるエポキシ樹脂の種類としては、例えば、クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、トリスフェノールメタン型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂、ナフタレンノボラック型エポキシ樹脂、ジシクロペンタジエンとフェノール又はクレゾールとの重付加反応物とエピハロヒドリンとの反応生成物であるエポキシ樹脂、アダマンチル基含有エポキシ樹脂、フルオレン型エポキシ樹脂を好適に用いることができ、主鎖に芳香族環を有するものをより好適に用いることができる。
α,β-不飽和モノカルボン酸又はカルボキシ基を有するα,β-不飽和モノカルボン酸エステルの使用量は、エポキシ樹脂のエポキシ基1当量に対し0.5~1.2当量が好ましく、さらに好ましくは0.7~1.1当量である。α,β-不飽和モノカルボン酸又はカルボキシ基を有するα,β-不飽和モノカルボン酸エステルの使用量を前記下限値以上とすることで不飽和基の導入量の不足が抑制でき、引き続く多塩基酸及び/又はその無水物との反応も十分なものとしやすい傾向がある。前記上限値以下とすることでα,β-不飽和モノカルボン酸又はカルボキシ基を有するα,β-不飽和モノカルボン酸エステルの未反応物の残存を抑制でき、硬化特性を良好なものとしやすい傾向が認められる。
式(C2-I)中のベンゼン環は、さらに任意の置換基により置換されていてもよい。
式(C2-I)中のベンゼン環は、さらに任意の置換基により置換されていてもよい。
式(C2-I)において、R12は置換基を有していてもよい2価の炭化水素基を表す。
2価の炭化水素基としては、2価の脂肪族基、2価の芳香族環基、1以上の2価の脂肪族基と1以上の2価の芳香族環基とを連結した基が挙げられる。
2価の分岐鎖状の脂肪族基としては、前述の2価の直鎖状の脂肪族基に、側鎖として、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基を有する構造が挙げられる。
2価の環状の脂肪族基が有する環の数は特に限定されないが、1以上が好ましく、2以上がより好ましい。また、12以下が好ましく、10以下がより好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、1~12が好ましく、1~10がより好ましく、2~10がさらに好ましい。前記下限値以上とすることで強固な膜となり、基板密着性が良好となる傾向がある。前記上限値以下とすることで感度の悪化を抑制でき、現像後の残膜率が高く、解像性が向上する傾向がある。
2価の環状の脂肪族基としては、例えば、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、ジシクロペンタジエン、ジシクロペンタン等の環から水素原子を2つ除した基が挙げられる。骨格の剛直性の観点から、ジシクロペンタジエン環、ジシクロペンタン環、アダマンタン環から水素原子を2つ除した基が好ましい。
2価の芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよい。2価の芳香族複素環基としては、例えば、2個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環が挙げられる。
パターニング特性の観点から、2個の遊離原子価を有するベンゼン環又はナフタレン環が好ましく、2個の遊離原子価を有するベンゼン環がより好ましい。
2価の脂肪族基の数は特に限定されないが、1以上が好ましく、2以上がより好ましく、また、10以下が好ましく、5以下がより好ましく、3以下がさらに好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、1~10が好ましく、1~5がより好ましく、1~3がさらに好ましく、2~3が特に好ましい。前記下限値以上とすることで強固な膜が得られやすく、現像時に生じる表面荒れが生じにくく、基板への密着性が良好となる傾向がある。前記上限値以下とすることで感度の悪化を抑制でき、現像後の残膜率が高く、解像性が向上する傾向がある。
2価の芳香族環基の数は特に限定されないが、1以上が好ましく、2以上がより好ましく、また、10以下が好ましく、5以下がより好ましく、3以下がさらに好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、1~10が好ましく、1~5がより好ましく、1~3がさらに好ましく、2~3が特に好ましい。前記下限値以上とすることで強固な膜が得られやすく、現像時に生じる表面荒れが生じにくく、基板への密着性が良好となる傾向がある。前記上限値以下とすることで感度の悪化を抑制でき、現像後の残膜率が高く、解像性が向上する傾向がある。
置換基としては、例えば、ヒドロキシ基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基が挙げられる。置換基の数も特に限定されず、1つでもよいし、2つ以上でもよい。
製版性の観点から、無置換であることが好ましい。
式(C2-I-1)中のベンゼン環は、さらに任意の置換基により置換されていてもよい。
パターニング特性の観点から、好ましくは、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ビフェニルテトラカルボン酸であり、より好ましくは、テトラヒドロフタル酸、ビフェニルテトラカルボン酸、ビフェニルテトラカルボン酸である。
式(C2-II)において、R14は、環状炭化水素基を側鎖として有する2価の炭化水素基を表す。
環状炭化水素基としては、脂肪族環基又は芳香族環基が挙げられる。
脂肪族環基における脂肪族環としては、例えば、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環が挙げられる。感光性着色樹脂組成物の残膜率と解像性の観点から、アダマンタン環が好ましい。
芳香族環基としては、芳香族炭化水素環基、芳香族複素環基が挙げられる。芳香族環基の炭素数は特に限定されないが、4以上が好ましく、6以上がより好ましく、8以上がさらに好ましく、10以上がよりさらに好ましく、12以上が特に好ましい。また、40以下が好ましく、30以下がより好ましく、20以下がさらに好ましく、15以下が特に好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、4~40が好ましく、6~40がより好ましく、8~30がさらに好ましく、10~20がよりさらに好ましく、12~15が特に好ましい。前記下限値以上とすることで強固な膜が得られやすく、現像時に生じる表面荒れが生じにくくなる傾向がある。前記上限値以下とすることでパターニング特性が良好となる傾向がある。
芳香族環基における芳香族環としては、例えば、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環が挙げられる。パターニング特性の観点から、フルオレン環が好ましい。
2価の分岐鎖状の脂肪族基としては、例えば、前述の2価の直鎖状の脂肪族基に、側鎖としてメチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基を有する構造が挙げられる。
2価の環状の脂肪族基が有する環の数は特に限定されないが、1以上が好ましく、2以上がより好ましい。また、10以下が好ましく、5以下がより好ましく、3以下がさらに好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、1~10が好ましく、1~5がより好ましく、1~3がさらに好ましく、2~3が特に好ましい。前記下限値以上とすることで強固な膜となり、基板密着性と良好となる傾向がある。また、前記上限値以下とすることで感度の悪化を抑制でき、現像後の残膜率が高く、解像性が向上する傾向がある。
2価の環状の脂肪族基としては、例えば、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環の環から水素原子を2つ除した基が挙げられる。骨格の剛直性の観点から、アダマンタン環から水素原子を2つ除した基が好ましい。
2価の芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよい。2価の芳香族複素環基としては、例えば、2個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環が挙げられる。パターニング特性の観点から、2個の遊離原子価を有するベンゼン環又はナフタレン環が好ましく、2個の遊離原子価を有するベンゼン環がより好ましい。
2価の脂肪族基の数は特に限定されないが、1以上が好ましく、2以上がより好ましく、10以下が好ましく、5以下がより好ましく、3以下がさらに好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、1~10が好ましく、1~5がより好ましく、1~3がさらに好ましく、2~3が特に好ましい。前記下限値以上とすることで強固な膜が得られやすく、現像時に生じる表面荒れが生じにくく、基板への密着性が良好となる傾向がある。前記上限値以下とすることで感度の悪化を抑制でき、現像後の残膜率が高く、解像性が向上する傾向がある。
2価の芳香族環基の数は特に限定されないが、1以上が好ましく、2以上がより好ましく、10以下が好ましく、5以下がより好ましく、3以下がさらに好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、1~10が好ましく、1~5がより好ましく、1~3がさらに好ましく、2~3が特に好ましい。前記下限値以上とすることで強固な膜が得られやすく、現像時に生じる表面荒れが生じにくく、基板への密着性が良好となる傾向がある。前記上限値以下とすることで感度の悪化を抑制でき、現像後の残膜率が高く、解像性が向上する傾向がある。
式(C2-II)において、R15及びR16は各々独立に、置換基を有していてもよい2価の脂肪族基を表す。
2価の分岐鎖状の脂肪族基としては、前述の2価の直鎖状の脂肪族基に、側鎖として、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基を有する構造が挙げられる。
2価の環状の脂肪族基が有する環の数は特に限定されないが、1以上が好ましく、2以上がより好ましい。また、12以下が好ましく、10以下がより好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、1~12が好ましく、2~10がより好ましい。前記下限値以上とすることで強固な膜となり、基板密着性が良好となる傾向がある。前記上限値以下とすることで感度の悪化を抑制でき、現像後の残膜率が高く、解像性が向上する傾向がある。
2価の環状の脂肪族基としては、例えば、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、ジシクロペンタジエン環から水素原子を2つ除した基が挙げられる。骨格の剛直性の観点から、ジシクロペンタジエン環、アダマンタン環から水素原子を2つ除した基が好ましい。
式(C2-II)において、m及びnは各々独立に0~2の整数を表す。前記下限値以上とすることでパターニング適正が良好となり、現像時に生じる表面荒れが生じにくくなる傾向があり、また、前記上限値以下とすることで現像性が良好となる傾向がある。現像性の観点からm及びnが0であることが好ましい。パターニング適正、現像時に生じる表面荒れを抑制する観点からm及びnが1以上であることが好ましい。
式(C2-II-1)において、Rαは、置換基を有していてもよい1価の環状炭化水素基を表す。
環状炭化水素基としては、脂肪族環基又は芳香族環基が挙げられる。
脂肪族環基の炭素数は特に限定されないが、4以上が好ましく、6以上がより好ましく、8以上がさらに好ましい。また、40以下が好ましく、30以下がより好ましく、20以下がさらに好ましく、15以下が特に好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、4~40が好ましく、4~30がより好ましく、6~20がさらに好ましく、8~15が特に好ましい。前記下限値以上とすることで強固な膜が得られやすく、現像時に生じる表面荒れが生じにくくなる傾向がある。前記上限値以下とすることでパターニング特性が良好となる傾向がある。
脂肪族環基における脂肪族環としては、例えば、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環が挙げられる。強固な膜特性の観点から、アダマンタン環が好ましい。
芳香族環基としては、芳香族炭化水素環基、芳香族複素環基が挙げられる。また、芳香族環基の炭素数は特に限定されないが、4以上が好ましく、5以上がより好ましく、6以上がさらに好ましい。また、30以下が好ましく、20以下がより好ましく、15以下がさらに好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、4~30が好ましく、5~20がより好ましく、6~15がさらに好ましい。前記下限値以上とすることで強固な膜が得られやすく、現像時に生じる表面荒れが生じにくくなる傾向がある。前記上限値以下とすることでパターニング特性が良好となる傾向がある。
芳香族環基における芳香族環としては、例えば、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、フルオレン環が挙げられる。現像溶解性の観点から、フルオレン環が好ましい。
パターニング特性の観点から、無置換であることが好ましい。
下記例中、*は結合手を表す。
式(C2-II-2)中のベンゼン環は、さらに任意の置換基により置換されていてもよい。
式(C2-II-2)において、Rβは、置換基を有していてもよい2価の環状炭化水素基を表す。
環状炭化水素基としては、脂肪族環基又は芳香族環基が挙げられる。
脂肪族環基の炭素数は4以上が好ましく、6以上がより好ましく、8以上がさらに好ましい。また、40以下が好ましく、35以下がより好ましく、30以下がさらに好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、4~40が好ましく、6~35がより好ましく、8~30がさらに好ましい。前記下限値以上とすることで現像時の膜表面の荒れを抑制する傾向がある。前記上限値以下とすることで感度の悪化を抑制でき、現像後の残膜率が高く、解像性が向上する傾向がある。
脂肪族環基における脂肪族環としては、例えば、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環が挙げられる。現像後の残膜率、解像性の観点から、アダマンタン環が好ましい。
芳香族環基としては、芳香族炭化水素環基、芳香族複素環基が挙げられる。
芳香族環基の炭素数は4以上が好ましく、6以上がより好ましく、8以上がさらに好ましく、10以上がよりさらに好ましい。また、40以下が好ましく、30以下がより好ましく、20以下がさらに好ましく、15以下が特に好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、4~40が好ましく、6~30がより好ましく、8~20がさらに好ましく、10~15が特に好ましい。前記下限値以上とすることで強固な膜が得られやすく、現像時に生じる表面荒れが生じにくくなる傾向がある。前記上限値以下とすることで感度の悪化や膜減りを抑制しやすく、解像性が向上する傾向がある。
芳香族環基における芳香族環としては、例えば、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、フルオレン環が挙げられる。残膜率の観点から、フルオレン環が好ましい。2つのベンゼン環につながる結合に対し、フルオレン環を形成する平面が直行するため、嵩高くなることでより剛直な骨格となり、現像液の浸透、焼成時の収縮が生じにくく、その結果、残膜率が高くなると推定される。
また、置換基を介して2つのベンゼン環が連結していてもよい。この場合の置換基としては、-O-、-S-、-NH-、-CH2-等の2価の基が挙げられる。 パターニング特性の観点から、無置換であることが好ましい。また、膜減り等を生じにくくする観点から、メチル基置換であることが好ましい。
多塩基酸としては、例えば、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ベンゾフェノンテトラカルボン酸、メチルヘキサヒドロフタル酸、エンドメチレンテトラヒドロフタル酸、クロレンド酸、メチルテトラヒドロフタル酸、ビフェニルテトラカルボン酸が挙げられる。
パターニング特性の観点から、好ましくは、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ビフェニルテトラカルボン酸であり、より好ましくは、テトラヒドロフタル酸、ビフェニルテトラカルボン酸、ビフェニルテトラカルボン酸である。
本発明の感光性着色樹脂組成物は、樹脂(C1)以外の(C)アルカリ可溶性樹脂として、エチレン性二重結合及びカルボキシ基を有するイソシアヌル骨格含有樹脂を用いてもよい。(以降、単に(C3)イソシアヌル骨格含有樹脂と記載する場合がある。)
イソシアヌル骨格、エチレン性二重結合、及びカルボキシ基を有することで、耐薬品性、耐熱性が向上し、現像、焼成時の分解物の量を低下することで、有機電界素子において電圧を印加した際の電流密度が高くなる傾向がある。
(C3)イソシアヌル骨格含有樹脂は、樹脂(C1)以外の(C)アルカリ可溶性樹脂であり、エチレン性二重結合、カルボキシ基及びイソシアヌル骨格を有していれば特に限定されないが、例えば、以下(C3-1)、(C3-2)の樹脂が挙げられる。
アルキレン基としては、例えば、メチレン基、エチレン基、n-プロピレン基、イソプロピレン基、n-ブチレン基、イソブチレン基、n-ペンチレン基、n-ヘキシレン基が挙げられる。また、途中で、エーテル性酸素原子で分断されているアルキレン基としては、炭素数4~30の直鎖若しくは分岐を有してもよいアルキレン鎖の1~10個の炭素原子が酸素原子に置き換えられた基が挙げられ、例えば、2~9個のエトキシ基が連結した基、2~7個のプロポキシ基が連結した基を含む基が挙げられる。
これらのうち、ガスバリア性の観点から、好ましくは、メチレン基、エチレン基、n-プロピレン基であり、より好ましくはメチレン基である。
α,β-不飽和モノカルボン酸及び/又はエステル化合物としては、(C2)エポキシ(メタ)アクリレート系樹脂の項記載の化合物と同様の化合物が挙げられる。
さらに多塩基酸及び/又はその無水物としては、樹脂(C1)の項記載の化合物と同様の化合物が挙げられる。
(C3-2)の樹脂としては、例えば、日本国特開2020-75994号公報に記載の樹脂、及びその中間体が挙げられる。
(C)アルカリ可溶性樹脂として、顔料や分散剤等との相溶性の観点から、樹脂(C1)以外に(C4)アクリル共重合樹脂を用いてもよい。(C4)アクリル共重合樹脂としては、例えば、日本国特開2014-137466号公報に記載のものを好ましく用いることができる。
不飽和単量体(C4-1)としては、例えば、(メタ)アクリル酸、クロトン酸、α-クロルアクリル酸、けい皮酸等の不飽和モノカルボン酸;マレイン酸、無水マレイン酸、フマル酸、シトラコン酸、無水シトラコン酸、メサコン酸等の不飽和ジカルボン酸又はその無水物;こはく酸モノ〔2-(メタ)アクリロイロキシエチル〕、フタル酸モノ〔2-(メタ)アクリロイロキシエチル〕等の2価以上の多価カルボン酸のモノ〔(メタ)アクリロイロキシアルキル〕エステル;ω-カルボキシポリカプロラクトンモノ(メタ)アクリレート等の両末端にカルボキシ基と水酸基とを有するポリマーのモノ(メタ)アクリレート;p-ビニル安息香酸を挙げることができる。
これらの不飽和単量体(C4-1)は、単独で又は2種以上を併用することができる。
スチレン、α-メチルスチレン、p-ヒドロキシスチレン、p-ヒドロキシ-α-メチルスチレン、p-ビニルベンジルグリシジルエーテル、アセナフチレン等の芳香族ビニル化合物;
ポリスチレン、ポリメチル(メタ)アクリレート、ポリ-n-ブチル(メタ)アクリレート、ポリシロキサン等の重合体分子鎖の末端にモノ(メタ)アクリロイル基を有するマクロモノマー;を挙げることができる。
これらの不飽和単量体(C4-2)は、単独で又は2種以上を併用することができる。
不飽和単量体(C4-1)と不飽和単量体(C4-2)の共重合体は、公知の方法により製造することができるが、例えば、日本国特開2003-222717号公報、日本国特開2006-259680号公報、国際公開第2007/029871号に開示されている方法により、その構造やMw、Mw/Mn(Mnは数平均分子量である。)を制御することもできる。
本発明の感光性着色樹脂組成物は、(D)光重合開始剤を含有する。(D)光重合開始剤は、光を直接吸収し、分解反応又は水素引き抜き反応を起こし、重合活性ラジカルを発生する機能を有する成分である。必要に応じて重合促進剤(連鎖移動剤)、増感色素等の付加剤を添加して使用してもよい。
光重合開始剤としては、例えば、日本国特開昭59-152396号公報、日本国特開昭61-151197号公報に記載のチタノセン化合物を含むメタロセン化合物;日本国特開2000-56118号公報に記載のヘキサアリールビイミダゾール誘導体類;日本国特開平10-39503号公報に記載のハロメチル化オキサジアゾール誘導体類、ハロメチル-s-トリアジン誘導体類;α-アミノアルキルフェノン誘導体類;日本国特開2000-80068号公報、日本国特開2006-36750号公報等に記載されているオキシムエステル系化合物が挙げられる。
R21bは芳香環を含む任意の置換基を示す。
R22aは、置換基を有していてもよいアルカノイル基、又は、置換基を有していてもよいアロイル基を示す。
nは0又は1の整数を示す。
アルキル基が有していてもよい置換基としては、例えば、芳香族環基、水酸基、カルボキシ基、ハロゲン原子、アミノ基、アミド基、4-(2-メトキシ-1-メチル)エトキシ-2-メチルフェニル基、N-アセチル-N-アセトキシアミノ基が挙げられる。合成容易性の観点からは、無置換であることが好ましい。
芳香族環基が有していてもよい置換基としては、例えば、水酸基、カルボキシ基、ハロゲン原子、アミノ基、アミド基、アルキル基、アルコキシ基、これらの置換基が連結した基が挙げられる。現像性の観点からアルキル基、アルコキシ基、これらを連結した基が好ましく、連結したアルコキシ基がより好ましい。
現像性の観点から、R21aが置換基を有していてもよい芳香族環基であることが好ましく、連結したアルコキシ基を置換基に有する芳香族環基であることがさらに好ましい。
アルカノイル基が有していてもよい置換基としては、例えば、芳香族環基、水酸基、カルボキシ基、ハロゲン原子、アミノ基、アミド基が挙げられる。合成容易性の観点からは、無置換であることが好ましい。
アロイル基が有していてもよい置換基としては、例えば、水酸基、カルボキシ基、ハロゲン原子、アミノ基、アミド基、アルキル基が挙げられる。合成容易性の観点からは、無置換であることが好ましい。
感度の観点から、R22aが置換基を有していてもよいアルカノイル基であることが好ましく、無置換のアルカノイル基であることがより好ましく、アセチル基であることがさらに好ましい。
光重合開始剤には、必要に応じて、感応感度を高める目的で、画像露光光源の波長に応じた増感色素、重合促進剤を配合させることができる。増感色素としては、例えば、日本国特開平4-221958号公報、日本国特開平4-219756号公報に記載のキサンテン色素、日本国特開平3-239703号公報、日本国特開平5-289335号公報に記載の複素環を有するクマリン色素、日本国特開平3-239703号公報、日本国特開平5-289335号公報に記載の3-ケトクマリン化合物、日本国特開平6-19240号公報に記載のピロメテン色素、日本国特開昭47-2528号公報、日本国特開昭54-155292号公報、日本国特公昭45-37377号公報、日本国特開昭48-84183号公報、日本国特開昭52-112681号公報、日本国特開昭58-15503号公報、日本国特開昭60-88005号公報、日本国特開昭59-56403号公報、日本国特開平2-69号公報、日本国特開昭57-168088号公報、日本国特開平5-107761号公報、日本国特開平5-210240号公報、日本国特開平4-288818号公報に記載のジアルキルアミノベンゼン骨格を有する色素を挙げることができる。
増感色素は、1種を単独で用いてもよく、2種以上を併用してもよい。
本発明の感光性着色樹脂組成物は、(E)エチレン性不飽和化合物を含んでもよい。(E)エチレン性不飽和化合物を含むことで、感度が向上する傾向がある。
本発明に用いられる(E)エチレン性不飽和化合物は、分子内にエチレン性不飽和基を少なくとも1個有する化合物である。具体的には、例えば、(メタ)アクリル酸、(メタ)アクリル酸アルキルエステル、アクリロニトリル、スチレン、エチレン性不飽和結合を1個有するカルボン酸、多価又は1価アルコールのモノエステルが挙げられる。
多官能エチレン性単量体としては、例えば、脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル;芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル;脂肪族ポリヒドロキシ化合物、芳香族ポリヒドロキシ化合物等の多価ヒドロキシ化合物と、不飽和カルボン酸及び多塩基性カルボン酸とのエステル化反応により得られるエステル;が挙げられる。
これらは1種を単独で用いてもよく、2種以上を併用してもよい。
本発明の感光性着色樹脂組成物には、上述の成分の他、シランカップリング剤等の密着向上剤、界面活性剤、顔料誘導体、光酸発生剤、架橋剤、メルカプト化合物、重合禁止剤等の添加剤を適宜配合することができる。
本発明の感光性着色樹脂組成物は、基板との密着性を改善するため、密着向上剤を含有してもよい。密着向上剤としては、シランカップリング剤、燐酸基含有化合物が好ましい。
シランカップリング剤としては、例えば、エポキシ系、(メタ)アクリル系、アミノ系等種々のものを1種単独で用いても、2種以上を併用してもよい。
燐酸基含有化合物としては、(メタ)アクリロイル基含有ホスフェート類が好ましく、下記一般式(g1)、(g2)又は(g3)で表されるものが好ましい。
これらの燐酸基含有化合物は、1種単独で用いても、2種以上を併用してもよい。
本発明の感光性着色樹脂組成物は、塗布性向上ため、界面活性剤を含有してもよい。
このような界面活性剤としては、例えば、TSF4460(モメンティブ・パフォーマンス・マテリアルズ社製)、DFX-18(ネオス社製)、BYK-300、BYK-325、BYK-330(ビックケミー社製)、KP340(信越シリコーン社製)、F-470、F-475、F-478、F-554、F-559(DIC社製)、SH7PA(東レ・ダウコーニング社製)、DS-401(ダイキン社製)、L-77(日本ユニカー社製)、FC4430(3M社製)が挙げられる。
界面活性剤は、1種を用いてもよく、2種以上を併用してもよい。
本発明の感光性着色樹脂組成物は、分散性、保存性向上のため、分散助剤として顔料誘導体を含有してもよい。
顔料誘導体としては、例えば、アゾ系、フタロシアニン系、キナクリドン系、ベンズイミダゾロン系、キノフタロン系、イソインドリノン系、ジオキサジン系、アントラキノン系、インダンスレン系、ペリレン系、ペリノン系、ジケトピロロピロール系、ジオキサジン系の誘導体が挙げられ、フタロシアニン系、キノフタロン系が好ましい。
顔料誘導体の置換基としては、例えば、スルホン酸基、スルホンアミド基及びその4級塩、フタルイミドメチル基、ジアルキルアミノアルキル基、水酸基、カルボキシ基、アミド基が顔料骨格に直接、又は、例えば、アルキル基、アリール基、複素環基を介して結合したものが挙げられ、好ましくはスルホン酸基である。置換基は一つの顔料骨格に複数置換していてもよく、複数種の置換基が置換していてもよい。
本発明の感光性着色樹脂組成物は、重合促進剤として、また、基板への密着性の向上のため、メルカプト化合物を含有してもよい。
本発明の感光性着色樹脂組成物は、硬化物の形状制御の観点から、重合禁止剤を含有してもよい。重合禁止剤を含有することでそれが塗布膜下層のラジカル重合を阻害することから、テーパー角(硬化物断面において支持体と硬化物のなす角度)を制御できると考えられる。
重合禁止剤としては、例えば、ハイドロキノン、ハイドロキノンモノメチルエーテル、メチルヒドロキノン、メトキシフェノール、2,6-ジ-tert-ブチル-4-クレゾール(BHT)が挙げられる。形状制御の観点から、2,6-ジ-tert-ブチル-4-クレゾールが好ましい。人体への安全性が特に優れるとの観点から、ハイドロキノンモノメチルエーテル、メチルヒドロキノンが好ましい。
重合禁止剤は、1種単独で用いてもよく、2種以上を併用してもよい。
(C)アルカリ可溶性樹脂を製造する際に、樹脂中に重合禁止剤が含まれることがあり、それを本発明の重合禁止剤として用いてもよいし、樹脂中に重合禁止剤の他に、それと同一、又は異なる重合禁止剤を感光性着色樹脂組成物製造時に添加してもよい。
本発明の感光性着色樹脂組成物は、溶剤を含むことが好ましい。溶剤を含むことで、着色剤を溶剤中に分散又は溶解でき、また、塗布が容易となる。
本発明の感光性着色樹脂組成物は、例えば、(A)着色剤、(B)分散剤、(C)アルカリ可溶性樹脂、(D)光重合開始剤及び必要に応じて使用されるその他の各種材料が、溶剤に溶解又は分散した状態で使用される。分散性や塗布性の観点から有機溶剤が好ましい。
エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジプロピルエーテル、ジエチレングリコールジブチルエーテル、ジプロピレングリコールジメチルエーテルのようなグリコールジアルキルエーテル類;
エチレングリコールジアセテート、1,3-ブチレングリコールジアセテート、1,6-ヘキシレングリコールジアセテート等のグリコールジアセテート類;
シクロヘキサノールアセテート等のアルキルアセテート類;
アミルエーテル、ジエチルエーテル、ジプロピルエーテル、ジイソプロピルエーテル、ジブチルエーテル、ジアミルエーテル、エチルイソブチルエーテル、ジヘキシルエーテルのようなエーテル類;
エタノール、プロパノール、ブタノール、ヘキサノール、シクロヘキサノール、エチレングリコール、プロピレングリコール、ブタンジオール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、メトキシメチルペンタノール、グリセリン、ベンジルアルコールのような1価又は多価アルコール類;
n-ペンタン、n-オクタン、ジイソブチレン、n-ヘキサン、ヘキセン、イソプレン、ジペンテン、ドデカンのような脂肪族炭化水素類;
シクロヘキサン、メチルシクロヘキサン、メチルシクロヘキセン、ビシクロヘキシルのような脂環式炭化水素類;
アミルホルメート、エチルホルメート、酢酸エチル、酢酸ブチル、酢酸プロピル、酢酸アミル、メチルイソブチレート、エチレングリコールアセテート、エチルプロピオネート、プロピルプロピオネート、酪酸ブチル、酪酸イソブチル、イソ酪酸メチル、エチルカプリレート、ブチルステアレート、エチルベンゾエート、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、3-メトキシプロピオン酸メチル、3-メトキシプロピオン酸エチル、3-メトキシプロピオン酸プロピル、3-メトキシプロピオン酸ブチル、γ-ブチロラクトンのような鎖状又は環状エステル類;
3-メトキシプロピオン酸、3-エトキシプロピオン酸のようなアルコキシカルボン酸類;
ブチルクロリド、アミルクロリドのようなハロゲン化炭化水素類;
メトキシメチルペンタノンのようなエーテルケトン類;
アセトニトリル、ベンゾニトリルのようなニトリル類;が挙げられる。
これらの有機溶剤は、単独で用いてもよく、2種以上を併用してもよい。
グリコールアルキルエーテルアセテート類は、1種を単独で用いてもよく、2種以上を併用してもよい。
グリコールアルキルエーテルアセテート類のみで使用してもよいが、他の有機溶剤を併用してもよい。併用する有機溶剤としては、グリコールモノアルキルエーテル類が好ましい。組成物中の構成成分の溶解性から、プロピレングリコールモノメチルエーテルが好ましい。
グリコールモノアルキルエーテル類は極性が高く、添加量が多すぎると顔料が凝集しやすく、後に得られる感光性着色樹脂組成物の粘度が上がっていく等の保存安定性が低下する傾向があるので、溶剤中のグリコールモノアルキルエーテル類の割合は5~30質量%が好ましく、5~20質量%がより好ましい。
好ましい高沸点溶剤として、例えば、ジエチレングリコールモノ-n-ブチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジプロピレングリコールメチルエーテルアセテート、1,3-ブチレングリコールジアセテート、1,6-ヘキサノールジアセテート、トリアセチンが挙げられる。
本発明の感光性着色樹脂組成物における(A)着色剤の含有割合は特に限定されないが、感光性着色樹脂組成物の全固形分に対して5質量%以上が好ましく、10質量%以上がより好ましく、15質量%以上がさらに好ましい。また、40質量%以下が好ましく、30質量%以下がより好ましく、25質量%以下がさらに好ましく、20質量%以下が特に好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、5~40質量%が好ましく、10~30質量%がより好ましく、15~30質量%がさらに好ましく、15~25質量%がよりさらに好ましく、15~20質量%が特に好ましい。前記下限値以上とすることで遮光性を確保出来る傾向がある。前記上限値以下とすることで分散剤量を減らすことができ、表面荒れを抑止できる傾向がある。
本発明の感光性着色樹脂組成物は、その塗膜の膜厚1μm当たりの光学濃度(OD)は特に限定されないが、0.2以上が好ましく、0.5以上がより好ましく、0.7以上がさらに好ましく、0.9以上がさらに好ましく、また、4.0以下が好ましく、3.0以下がより好ましく、2.0以下がさらに好ましく、1.5以下が特に好ましい。上記の上限及び下限は任意に組み合わせることができる。例えば、0.2~4.0が好ましく、0.5~4.0がより好ましく、0.5~3.0がさらに好ましく、0.5~2.0がよりさらに好ましく、0.7~2.0がことさらに好ましく、0.9~1.5が特に好ましい。前記下限値以上とすることで、十分な遮光性が得られる傾向がある。前記上限値以下とすることで電極の表面荒れが抑制され、残膜率が高くなる傾向がある。
塗膜の膜厚1μm当たりの光学濃度(OD)は、本発明の感光性着色樹脂組成物を硬化した塗膜を用いて測定すればよく、230℃で20分間加熱硬化させた0.5~1.5μmほどの塗膜を用いて測定することができる。
光学濃度とは、受光部の分光感度特性がISO 5-3規格におけるISO Visual densityで示される透過光学濃度をいう。通常、光源としては、CIE(国際照明委員会)が規定するA光源が用いられる。透過光学濃度の測定に用いることができる測定器としては、例えば、サカタインクスエンジニアリング社のX-Rite 361T(V)を挙げることができる。
本発明の顔料分散液を構成する成分及びその組成について説明する。
本発明の顔料分散液は、(A)着色剤、(B)分散剤、及び(C)アルカリ可溶性樹脂を含有し、特に、前記(A)着色剤が有機顔料(A-1)を含有し、(C)アルカリ可溶性樹脂が、樹脂(C1)を含有する。また溶剤を含むことが好ましい。
本発明の顔料分散液における構成成分は、本発明の感光性着色樹脂組成物における同項目として挙げたものを好ましく採用することができる。
また、本発明の顔料分散液を用いた感光性着色樹脂組成物は、残膜率が高くなる傾向がある。これは前述のとおり、樹脂(C1)が主鎖に芳香環を多く含有するため、現像時の現像液耐性が高く、また焼成時の熱耐性が高い傾向がある。
また、感光性着色樹脂組成物から得られる隔壁を用いて有機電界発光素子を形成した場合、前述のとおり、電圧を印加した際の電流密度が高くなる傾向がある。
本発明の顔料分散液において、(A)着色剤の含有割合は、顔料分散液中の全固形分に対して好ましくは10質量%以上、より好ましくは20質量%以上、さらに好ましくは30質量%以上、よりさらに好ましくは40質量%以上、ことさらに好ましくは50質量%以上、特に好ましくは55質量%以上である。また、通常100質量%以下、好ましくは80質量%以下、より好ましくは70質量%以下、さらに好ましくは65質量%以下である。前記下限値以上とすることで感光性着色樹脂組成物を適切な固形分濃度にて製造することができ、また、前記上限値以下とすることで分散性が良好となる傾向がある。上限と下限の組み合わせとしては、10~80質量%が好ましく、20~80質量%がより好ましく、30~70質量%がさらに好ましく、40~70質量%がよりさらに好ましく、50~65質量%が特に好ましく、55~65質量%が最も好ましい。
本発明の顔料分散液において樹脂(C1)の含有割合は、顔料分散液中の全固形分に対して好ましくは5質量%以上、より好ましくは10質量%以上、さらに好ましくは15質量%以上、よりさらに好ましくは20質量%以上、特に好ましくは25質量%以上である。また、好ましくは50質量%以下、より好ましくは40質量%以下、さらに好ましくは35質量%以下である。前記下限値以上とすることで分散性が良好となる傾向があり、また、前記上限値以下とすることで得られる感光性着色樹脂組成物中の着色剤量を適正化でき、十分な遮光性が確保できる傾向がある。上限と下限の組み合わせとしては、5~50質量%が好ましく、10~40質量%がより好ましく、15~35質量%がさらに好ましく、20~35質量%がよりさらに好ましく、25~35質量%が特に好ましい。
顔料分散液の粘度は、1MPa・s以上が好ましく、3MPa・s以上がより好ましく、5MPa・s以上がさらに好ましい。また15MPa・s以下が好ましく、10MPa・s以下がさらに好ましい。粘度は、例えば回転式粘度計等で測定することができる。
本発明の顔料分散液は、常法に従って製造される。
(A)着色剤は、予めペイントコンディショナー、サンドグラインダー、ボールミル、ロールミル、ストーンミル、ジェットミル、ホモジナイザー等を用いて分散処理されるのが好ましい。分散処理により(A)着色剤が微粒子化されるため、感光性着色樹脂組成物の塗布特性が向上し、表面粗度が低くなる傾向がある。
顔料分散液に用いることができる(A)着色剤、(B)分散剤、及び溶剤としては、それぞれ感光性着色樹脂組成物に用いることができるものとして記載したものを好ましく採用することができる。
サンドグラインダーで(A)着色剤を分散させる場合には、0.1~8mm程度の粒子径のガラスビーズ又はジルコニアビーズが好ましく用いられる。分散処理条件は、温度は0℃から100℃が好ましく、室温から80℃がより好ましい。分散時間は液の組成及び分散処理装置のサイズ等により適正時間が異なるため適宜調節する。感光性着色樹脂組成物の20度鏡面光沢度(JIS Z8741)が50~300の範囲となるように、顔料分散液の光沢を制御するのが分散の目安である。感光性着色樹脂組成物の光沢度が低い場合には、分散処理が十分でなく荒い顔料(着色剤)粒子が残っていることが多く、現像性、密着性、解像性、表面粗度等が不十分となる可能性がある。光沢値が上記範囲を超えるまで分散処理を行うと、顔料が破砕して超微粒子が多数生じるため、却って分散安定性が損なわれる傾向がある。
顔料分散液中に分散した顔料の分散粒径は0.03~0.3μmが好ましく、動的光散乱法により測定されうる。
次に、上記分散処理により得られた顔料分散液と、感光性着色樹脂組成物中に含まれる他の成分を混合し、均一な溶液若しくは分散液とする。感光性着色樹脂組成物の製造工程においては、微細なゴミが液中に混じることがあるため、得られた感光性着色樹脂組成物はフィルター等により濾過処理するのが望ましい。
本発明の感光性着色樹脂組成物を硬化させることで、本発明の硬化物を得ることができる。本発明の感光性着色樹脂組成物を硬化してなる硬化物は、ブラックマトリックス、絶縁膜、隔壁として好適に用いることができ、隔壁として、より好適に用いることができる。
硬化物の膜厚は、0.5μm以上が好ましく、0.7μm以上がより好ましく、0.9μm以上がさらに好ましい。また15μm以下であることが好ましく、10μm以下であることがより好ましく、5μm以下であることがさらに好ましい。例えば、0.5~15μmが好ましく、0.7~10μmがより好ましく、0.9~5μmがさらに好ましい。
本発明の硬化物の1μm当たりの光学濃度(OD)は、遮光性の観点から、0.2以上が好ましく、0.5以上がより好ましく、0.7以上がさらに好ましく、0.9以上が特に好ましい。また4.0以下であることが好ましく、3.0以下であることがより好ましく、2.0以下がさらに好ましく、1.5以下が特に好ましい。例えば、0.2~4.0が好ましく、0.5~4.0がより好ましく、0.5~3.0がさらに好ましく、0.5~2.0がよりさらに好ましく、0.7~2.0がことさらに好ましく、0.9~1.5が特に好ましい。ここで光学濃度(OD)は後述する方法にて測定した値である。
硬化物を形成するための支持体としては、適度の強度があれば、その材質は特に限定されるものではない。主に基板が使用されるが、材質としては、例えば、ポリエチレンテレフタレート等のポリエステル系樹脂、ポリプロピレン、ポリエチレン等のポリオレフィン系樹脂、ポリカーボネート、ポリメチルメタクリレート、ポリスルフォン等の熱可塑性樹脂製シート、エポキシ樹脂、不飽和ポリエステル樹脂、ポリ(メタ)アクリル系樹脂等の熱硬化性樹脂シート、各種ガラスが挙げられる。耐熱性の観点からガラス、耐熱性樹脂が好ましい。また、基板の表面にITO、IZO等の透明電極、あるいは銀、金、白金、アルミニウム、マグネシウムのような金属電極が成膜されている場合もある。上述の基板以外では、TFTアレイ上に形成することも可能である。
支持体の厚さは、好ましくは0.05~10mm、より好ましくは0.1~7mmの範囲とされる。また各種樹脂の薄膜形成処理を行う場合、その膜厚は、好ましくは0.01~10μm、より好ましくは0.05~5μmの範囲である。
本発明の感光性着色樹脂組成物は、溶剤に溶解あるいは分散された状態で、支持体上へ供給されることが好ましい。その供給方法としては、従来公知の方法、例えば、スピナー法、ワイヤーバー法、フローコート法、ダイコート法、ロールコート法、スプレーコート法によって行うことができる。また、例えば、インクジェット法や印刷法により、パターン状に供給されてもよい。ダイコート法によれば、塗布液の使用量が大幅に削減され、かつ、スピンコート法によった際に付着するミスト等の影響が全くない、異物発生が抑制される等、総合的な観点から好ましい。
支持体上に感光性着色樹脂組成物を供給した後の乾燥は、ホットプレート、IRオーブン、コンベクションオーブンを使用した乾燥方法によるのが好ましい。温度を高めず、減圧チャンバー内で乾燥を行う、減圧乾燥法を組み合わせてもよい。
露光は、感光性着色樹脂組成物の塗布膜上に、ネガのマスクパターンを重ね、このマスクパターンを介し、紫外線又は可視光線の光源を照射して行う。露光マスクを用いて露光を行う場合には、露光マスクを感光性着色樹脂組成物の塗布膜に近接させる方法や、露光マスクを感光性着色樹脂組成物の塗布膜から離れた位置に配置し、露光マスクを介した露光光を投影する方法によってもよい。マスクパターンを用いないレーザー光による走査露光方式によってもよい。必要に応じ、酸素による光重合性層の感度の低下を防ぐため、脱酸素雰囲気下で行ったり、光重合性層上にポリビニルアルコール層等の酸素遮断層を形成した後に露光を行ったりしてもよい。
中間透過開口部は、例えば、微小な多角形の遮光ユニットを有するマトリックス状遮光パターンによって作製する方法が知られている。吸収体として、例えば、クロム系、モリブデン系、タングステン系、シリコーン系材料の膜によって、光透過率を制御し作製する方法が知られている。
上記の露光を行った後、アルカリ性化合物の水溶液、又は有機溶剤を用いる現像によって、支持体上に画像パターンを形成することができる。アルカリ性化合物の水溶液は、さらに、例えば、界面活性剤、有機溶剤、緩衝剤、錯化剤、染料又は顔料が含まれていてもよい。
現像の後の基板には、必要により上記の露光方法と同様な方法により追露光を行ってもよい。現像後、又は追露光後、熱硬化処理(焼成ともいう)を行ってもよい。熱硬化処理条件は、温度が好ましくは100~280℃、より好ましくは150~250℃であり、時間が5~60分間である。
本発明の感光性着色樹脂組成物は隔壁、特に有機電界発光素子の有機層を区画するための隔壁を形成するために好適に用いることができる。有機電界発光素子に用いる有機層としては、例えば日本国特開2016-165396号公報に記載されているような、正孔注入層、正孔輸送層あるいは正孔注入層上の正孔輸送層に用いる有機層が挙げられる。
本発明の有機電界発光素子は、本発明の感光性着色樹脂組成物で形成される硬化物、例えば隔壁を備える。
例えば、上述した方法により製造された隔壁パターンを備える基板を用いて、種々の有機電界発光素子が製造される。有機電界発光素子を形成する方法は特に限定されないが、好ましくは、上述した方法により基板上に隔壁のパターンを形成した後に、機能材料を真空状態で昇華させ、基板上の隔壁により囲まれた領域内に付着させて成膜する蒸着法や、キャスト法、スピンコート法、インクジェット印刷法といったウェットプロセスにて画素等の有機層を形成することによって、有機電界発光素子が製造される。
ボトムエミッション型では、例えば、透明電極を積層したガラス基板上に隔壁を形成し、隔壁で囲まれた開口部に正孔輸送層、発光層、電子輸送層、金属電極層を積層して作製される。一方でトップエミッション型では、例えば、反射層として金属電極層を積層したガラス基板上に隔壁を形成し、隔壁で囲まれた開口部に電子輸送層、発光層、正孔輸送層、透明電極層を積層して作製される。多くの場合、支持体上に陽極を設置されるが、これに限定されない。
発光層としては、日本国特開2009-146691号公報や日本国特許第5734681号公報に記載されているような有機電界発光層が挙げられる。また、日本国特許第5653387号公報や日本国特許第5653101号公報に記載されているような量子ドットを用いてもよい。
有機電界発光素子においては、隔壁の上面及び下面に電極を付与することが必要であるため、絶縁性の観点から、隔壁は高抵抗、低誘電率であることが好ましい。そのため、隔壁に遮光性を付与するために着色剤を使用する場合には、高抵抗かつ低誘電率である前記有機顔料を用いることが好ましい。
本発明に係る発光性ナノ結晶粒子を含むカラーフィルターは、本発明の隔壁を備えていれば特に限定されず、隔壁で区画された領域に画素を形成したものが挙げられる。
本発明の画像表示装置としては、本発明の硬化物を含む隔壁や有機電界発光素子を有する有機EL表示装置を挙げることができる。
有機EL表示装置は、上述の有機電界発光素子を含むものであれば画像表示装置の型式や構造については特に制限はなく、例えば、アクティブ駆動型有機電界発光素子を用いて常法に従って組み立てることができる。例えば、「有機ELディスプレイ」(オーム社、平成16年8月20日発行、時任静士、安達千波矢、村田英幸著)に記載されているような方法で形成することができる。例えば、白色光を発光する有機電界発光素子とカラーフィルターとを組み合わせて画像表示させてもよいし、RGB等の発光色の異なる有機電界発光素子を組み合わせて画像表示させてもよい。
以下の実施例及び比較例で用いた感光性着色樹脂組成物の構成成分、並びにそれらの評価方法は次のとおりである。
DIC社製EPICLON HP7200HH(ジシクロペンタジエン・フェノール重合物のポリグリシジルエーテル、重量平均分子量1000、エポキシ当量270)155質量部、アクリル酸41質量部、p-メトキシフェノール0.1質量部、トリフェニルホスフィン2.5質量部、プロピレングリコールモノメチルエーテルアセテート270質量部を反応容器に仕込み、100℃で酸価が3.0mgKOH/g以下になるまで加熱撹拌をした。酸価が目標に達するまで9時間を要した(酸価2.9mgKOH/g)。次いでさらにテトラヒドロ無水フタル酸74gを添加し、120℃で4時間反応させた。こうして得られたアルカリ可溶性樹脂-IIは、重量平均分子量Mwは3500、酸価は60mgKOH/gであり、樹脂(C1)には該当しない。
日本化薬社製「ZCR-1664H」(重量平均分子量Mw=5200、酸価=60mgKOH/g)。下記式で表される部分構造を有し、下記式において*は結合手を表す。
アルカリ可溶性樹脂-IIIは樹脂(C1)には該当しない。
日本化薬社製「CCR-1342H」(重量平均分子量Mw=6500、酸価=60mgKOH/g)。下記式で表される部分構造を有し、下記式において*は結合手を表す。
アルカリ可溶性樹脂-IVは樹脂(C1)には該当しない。
次いで、上記反応により得られた反応液にトリメチロールプロパン(TMP)9.2質量部、ビフェニルテトラカルボン酸2無水物(BPDA)115.6質量部、テトラヒドロフタル酸無水物(THPA)25.1質量部を、温度計、攪拌機、冷却管を取り付けたフラスコに入れ、攪拌しながら105℃までゆっくり昇温し反応させ、固形分酸価104mgKOH/g、GPCで測定したポリスチレン換算の重量平均分子量(Mw)2660であるアルカリ可溶性樹脂-Vを得た。アルカリ可溶性樹脂-Vは(C2)エポキシ(メタ)アクリレート樹脂に該当する。
KISCO社製「KBR-201」。フルオレンビスフェノール骨格を有する樹脂。重量平均分子量5107、酸価113mgKOH/g。アルカリ可溶性樹脂-VIは(C2)エポキシ(メタ)アクリレート樹脂に該当する。
BASF社製、Irgaphor(登録商標) Black S 0100 CF(下記式(A-1-2)で表される化学構造を有する)。
親溶媒基を有する繰り返し単位を含むAブロックと、3級アミノ基を有する繰り返し単位を含むBブロックからなるブロック共重合体。
<分散剤-II>
親溶媒基を有する繰り返し単位を含むAブロックと、3級アミノ基と4級アンモニウム基を有する繰り返し単位を含むBブロックからなるブロック共重合体。
PGMEA:プロピレングリコールモノメチルエーテルアセテート。
<溶剤-II>
MB:3-メトキシ-1-ブタノール。
<溶剤-III>
MBA:3-メトキシ-ブチルアセテート。
以下の化学構造を有するオキシムエステル系光重合開始剤。
DPHA:日本化薬社製 ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートの混合物。
DIC社製 メガファック F-559。
東機産業社製 RE-85L型粘度計(測定条件:23℃、20rpm)を用い、顔料分散液の調製直後、顔料分散液を調製してから室温(24℃)にて1日静置後、及び3日静置後に顔料分散液の粘度を測定し、以下のように判定した。
感光性着色樹脂組成物の塗布性、経時安定性の点から、顔料分散液の粘度は低い方が好ましい。
A:粘度が10mPa・s以下
B:粘度が10mPa・sより大きい
C:分散できずに固化する
膜厚0.7mmのガラス基板表面にインジウム・スズ酸化物(ITO)膜を形成した基板上にスピナーを用いて、加熱硬化(焼成)後に1.5μmの厚みになるように、各実施例・比較例の感光性着色樹脂組成物を塗布した。その後真空乾燥機で60秒間乾燥処理を施した。続けて、100℃に昇温したホットプレート上で100秒間加熱乾燥し、塗膜基板を得た。
加熱乾燥した塗膜の膜厚を後述の方法で測定し、膜厚T1(μm)を求めた。
得られた塗膜基板に、フォトマスクを用いて露光を行った。キヤノン社製ミラープロジェクション型の露光機(MPA-600FA)を使用し、露光量が80mJ/cm2となるよう、20秒の露光を行った。照度は500mW/cm2、スリット幅は1.6mmであった。フォトマスクは格子状の開口部を有するマスク(50μmの正方形状の被腹部を有し、50μmの露光部を介して前記被覆部を複数有する)を使用した。
続いて、0.05質量%の水酸化カリウムと0.08質量%のノニオン性界面活性剤(花王社製「A-60」)を含有する水溶液からなる現像液を用い、24℃において水圧0.05MPaのシャワー現像を施した後、純水で現像液を流して現像を停止し、水洗スプレーにて10秒間洗浄した。シャワー現像時間は塗膜の未露光部が溶解除去される時間の1.6倍とした。正方形遮光部に対応する部分は現像後で感光性着色樹脂組成物が流されるためITO基板が露出され、ホール部分が形成される。
この基板をオーブン中230℃で30分間加熱硬化(焼成)させ、パターニング性測定用パターン基板が得られた。この時の膜厚T2(μm)を測定した。
前記パターン基板における各工程時(乾燥後、焼成後)の塗膜の膜厚を菱化システム社製非接触表面・層断面形状計測システムVertScan(R)2.0を用いて測定した。測定膜厚のうち、乾燥後の膜厚(T1)に対する焼成後の膜厚(T2)の比率を残膜率として算出した。
残膜率(%)=(T2/T1)×100(%)
算出した残膜率について、以下のように判定した。Aがもっとも残膜率が高く、良好であることを示し、残膜率が75%以上であれば実用上問題ない傾向がある。
A:残膜率 80%以上
B:残膜率 80%より小さく、75%以上
C:残膜率 75%未満
なお、残膜率はレジストの露光感度と現像液への溶解性、焼成時の熱分解性が関与しており、残膜率は高いほど好ましい。
単位膜厚当たりの光学濃度は以下の手順にて測定した。
ガラス基板上にスピナーを用いて、加熱硬化(焼成)後に1.5μmの厚みになるように、各実施例・比較例の感光性着色樹脂組成物を塗布した。その後真空乾燥機で60秒間乾燥処理を施した。続けて、100℃に昇温したホットプレート上で100秒間加熱乾燥した。
得られた塗膜に対し、露光マスクを用いず、露光を行った。照射光源としてはキヤノン社製ミラープロジェクション型の露光機(MPA-600FA)を使用し、露光量が80mJ/cm2となるよう、20秒の露光を行った。照度は500mW/cm2であった。続いてオーブン230℃で30分間加熱硬化する事で、レジスト塗工基板1を得た。
得られたレジスト塗工基板1の光学濃度(OD値)をX-Rite社製361T(V)透過濃度計(照明光源の色温度:約2850K(CIE標準光源A相当)、受光部の分光感度特性:ISO 5-3規格でのISO Visual density)を用いて測定し、膜厚を菱化システム社製非接触表面・層断面形状計測システム VertScan(R)2.0により測定し、光学濃度(OD値)及び膜厚から、単位膜厚(1μm)当たりの光学濃度(単位OD値)を算出した。なお、OD値は遮光能力を示す数値であり、数値が大きいほど高遮光性であることを示す。
ガラス上にインジウム・スズ酸化物(ITO)透明導電膜を70nmの厚さに堆積したものを通常のフォトリソグラフィー技術と塩酸エッチングを用いて陽極を形成した基板上にスピナーを用いて、各実施例・比較例の感光性着色樹脂組成物を塗布した。その後真空乾燥機で60秒間乾燥処理を施した。続けて、100℃に昇温したホットプレート上で100秒間加熱乾燥した。
得られた塗膜基板に、フォトマスクを用いて露光を行った。キヤノン社製ミラープロジェクション型の露光機(MPA-600FA)を使用し、露光量が80mJ/cm2となるよう、20秒の露光を行った。照度は500mW/cm2、スリット幅は1.6mmであった。フォトマスクは格子状の開口部を有するマスク(縦40μm×横80μmの長方形状の被覆部を有し、それを長軸、短軸方向に20μmの露光部を介して前記被覆部を複数有する)を使用した。
続いて、0.05質量%の水酸化カリウムと0.08質量%のノニオン性界面活性剤(花王社製「A-60」)を含有する水溶液からなる現像液を用い、24℃において水圧0.05MPaのシャワー現像を施した後、純水で現像液を流して現像を停止し、水洗スプレーにて10秒間洗浄した。シャワー現像時間は塗膜の未露光部が溶解除去される時間の1.6倍とした。
これらの操作により開口部分を現像除去し、隔壁がパターニングされた電極基板を得た。当該パターンの形成された電極基板をオーブン中、230℃で30分間加熱硬化(焼成)して、有機電界発光素子用パターン基板が得られた。
作製した有機電界発光素子用パターン基板上全面に、正孔注入層として酸化モリブデンを膜厚10nm、正孔輸送層としてN-([1,1’-ビフェニル]-4-イル)-9,9-ジメチル-N-[4-(9-フェニル-9H-カルバゾール-3-イル)フェニル]-9H-フルオレン-2-アミンを膜厚60nm、発光層としてトリス(8-ヒドロキシキノリナート)アルミニウムを膜厚60nm、電子注入層として8-ヒドロキシキノリノラト-リチウムを膜厚1nm、陰極としてアルミニウムを膜厚80nmとなるように真空蒸着法によって順に積層して有機電界発光素子を作製した。
次に、中央に凹部を有する封止ガラスの該凹部に乾燥剤を貼り付けて、凹部の周囲の枠部分にUV硬化樹脂を塗布した。封止ガラスの凹部が前記電極基板上の有機電界発光素子をすべて覆うように配置し、封止ガラスを前記電極基板に貼り付け、UV硬化樹脂にUVを照射し硬化させ、中空構造の封止をすることで有機電界発光素子評価用デバイスを作製した。
作製した有機電界発光素子評価用デバイスに直流電流を通電し、駆動電圧が4V時の電流密度を測定した。
測定した電流密度について、以下のように判定した。電流密度は高いほうが好ましく、電流密度 0.6mA/cm2以上であれば実用上問題ない傾向がある。
A:電流密度 0.8mA/cm2以上
B:電流密度 0.6mA/cm2以上0.8mA/cm2未満
C:電流密度 0.6/cm2未満
表1、表2に記載の顔料、分散剤、アルカリ可溶性樹脂、及び溶剤を、表1に記載の質量比となるように混合した。この混合液をペイントシェーカーにより25~45℃の範囲で3時間分散処理を行った。ビーズとしては、0.5mmφのジルコニアビーズを用い、分散液の2.5倍の質量を加えた。分散終了後、フィルターによりビーズと分散液を分離した。顔料分散液1~9を調製した。
なお、表1、表2中の溶剤の量は、分散剤及びアルカリ可溶性樹脂由来の溶剤の量も含まれる。
また、表2に示すとおり、実施例3~5は顔料分散液の調製から3日後も粘度が安定しているが、比較例5は顔料分散液の調製直後から徐々に増粘していることが観察された。
上記現象について、樹脂(C1)は主鎖に芳香環を多く含有するため、顔料との親和性が高く、また、主鎖にメチレン基も含むために顔料の表面形状に追従可能な柔軟性を有しており、顔料分散性に高い効果があると考えられる。アルカリ可溶性樹脂-I、アルカリ可溶性樹脂-VIIIは樹脂(C1)に該当し、高い顔料分散性を示したと考えられる。さらにアルカリ可溶性樹脂-VIIIはアルカリ可溶性樹脂-Iより溶媒親和性の高い水酸基が増加するため、顔料分散性、粘度安定性が良好になったと考えられる。
アルカリ可溶性樹脂-IIは主鎖に含まれる芳香環の含有率も低い一方で、かさ高いジシクロペンタン骨格を有するため、顔料分散性の効果が低いと考えられる。
また、アルカリ可溶性樹脂-III、IVは主鎖に芳香環を多く含むものの、主鎖が剛直であり柔軟性が乏しく、顔料の表面形状に追従する点において不利なため、顔料分散性の効果が低いと考えられる。
実施例5~9、比較例6、7は顔料分散液7~9に全固形分中に占める各成分の固形分の含有割合が表2に記載の値になるように各成分を加え、さらにPGMEA/MB/MBA=72/20/8、全固形分の含有割合が17質量%となるように溶剤を加え、攪拌、溶解させて、実施例5~10及び比較例6、7の感光性着色樹脂組成物を調製した。
単位OD値、残膜率の評価結果を表3、表4に示す。
実施例8~10、12の比較から、アルカリ可溶性樹脂-VIを使用した場合、残膜率はより向上することが分かった。これはアルカリ可溶性樹脂-VIの構造にアルカリ可溶性樹脂-V、-VIIより多くの芳香環が含まれるからであると考えられる。
またアルカリ可溶性樹脂-VIIは、耐熱性の高いイソシアヌル骨格を有しており、焼成時に画素内へ熱分解物の堆積が少なくなることで、さらに電流密度が高い値を示したと考えられる。
一方、比較例6、7では電流密度が低い傾向にある。主鎖に含まれる芳香環が少なく現像液耐性が低下することで、有機電界発光素子の画素部への現像時の分解物の堆積が多くなるため、と推定される。
2 赤色発光性のナノ結晶粒子
10 基板
20 隔壁
30 赤色画素
40 緑色画素
50 青色画素
100 カラーフィルター
Claims (21)
- 前記有機顔料(A-1)が有機黒色顔料を含む、請求項1又は2に記載の感光性着色樹脂組成物。
- 前記有機黒色顔料が、ベンゾジフラノン系有機黒色顔料を含む、請求項3に記載の感光性着色樹脂組成物。
- 前記有機黒色顔料が、下記一般式(A-1-1)で表される化合物、その幾何異性体、その塩、又はその幾何異性体の塩である有機黒色顔料を含む、請求項4に記載の感光性着色樹脂組成物。
(式(A-1-1)中、R611及びR616は各々独立に、水素原子、CH3、CF3、フッ素原子又は塩素原子を表し;
R612、R613、R614、R615、R617、R618、R619及びR620は各々独立に、水素原子、ハロゲン原子、R621、COOH、COOR621、COO-、CONH2、CONHR611、CONR621R622、CN、OH、OR621、COCR621、OOCNH2、OOCNHR621、OOCNR621R622、NO2、NH2、NHR621、NR621R622、NHCOR622、NR621COR622、N=CH2、N=CHR621、N=CR621R622、SH、SR621、SOR621、SO2R621、SO3R621、SO3H、SO3 -、SO2NH2、SO2NHR621又はSO2NR621R622を表し;
R612とR613、R613とR614、R614とR615、R617とR618、R618とR619、及びR619とR620からなる群から選ばれる少なくとも1つの組み合わせは、互いに直接結合してもよく、又は酸素原子、硫黄原子、NH若しくはNR621ブリッジによって互いに結合してもよく;
R621及びR622は各々独立に、炭素数1~12のアルキル基、炭素数3~12のシクロアルキル基、炭素数2~12のアルケニル基、炭素数3~12のシクロアルケニル基又は炭素数2~12のアルキニル基を表す。) - 前記(B)分散剤が、3級アミノ基及び/又は4級アンモニウム基を有するアクリル系分散剤を含む、請求項1又は2に記載の感光性着色樹脂組成物。
- 前記(C)アルカリ可溶性樹脂が、(C2)エポキシ(メタ)アクリレート樹脂を含有する、請求項1又は2に記載の感光性着色樹脂組成物。
- 前記(C)アルカリ可溶性樹脂が、(C3)イソシアヌル骨格含有樹脂を含有する、請求項1又は2に記載の感光性着色樹脂組成物。
- 前記(C)アルカリ可溶性樹脂における、前記樹脂(C1)の含有割合が4~80質量%の範囲である、請求項1又は2に記載の感光性着色樹脂組成物。
- 前記有機顔料(A-1)が有機黒色顔料を含む、請求項10又は11に記載の顔料分散液。
- 前記有機黒色顔料が、ベンゾジフラノン系有機黒色顔料を含む、請求項12に記載の顔料分散液。
- 前記有機黒色顔料が、下記一般式(A-1-1)で表される化合物、その幾何異性体、その塩、又はその幾何異性体の塩である有機黒色顔料を含む、請求項13に記載の顔料分散液。
(式(A-1-1)中、R611及びR616は各々独立に、水素原子、CH3、CF3、フッ素原子又は塩素原子を表し;
R612、R613、R614、R615、R617、R618、R619及びR620は各々独立に、水素原子、ハロゲン原子、R621、COOH、COOR621、COO-、CONH2、CONHR621、CONR621R622、CN、OH、OR621、COCR621、OOCNH2、OOCNHR621、OOCNR621R622、NO2、NH2、NHR621、NR621R622、NHCOR622、NR621COR622、N=CH2、N=CHR621、N=CR621R622、SH、SR621、SOR621、SO2R621、SO3R621、SO3H、SO3 -、SO2NH2、SO2NHR621又はSO2NR621R622を表し;
R612とR613、R613とR614、R614とR615、R617とR618、R618とR619、及びR619とR620からなる群から選ばれる少なくとも1つの組み合わせは、互いに直接結合してもよく、又は酸素原子、硫黄原子、NH若しくはNR621ブリッジによって互いに結合してもよく;
R621及びR622は各々独立に、炭素数1~12のアルキル基、炭素数3~12のシクロアルキル基、炭素数2~12のアルケニル基、炭素数3~12のシクロアルケニル基又は炭素数2~12のアルキニル基を表す。) - 前記(B)分散剤が、3級アミノ基及び/又は4級アンモニウム基を有するアクリル系分散剤を含む、請求項10又は11に記載の顔料分散液。
- 請求項1~9のいずれか1項に記載の感光性着色樹脂組成物を硬化させた硬化物。
- 請求項16に記載の硬化物から形成される、隔壁。
- 請求項17に記載の隔壁を備える、有機電界発光素子。
- 請求項18に記載の隔壁を備える、発光性ナノ結晶粒子を含むカラーフィルター。
- 請求項18に記載の隔壁を備える、画像表示装置。
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| CN202511485428.4A CN121254561A (zh) | 2022-08-09 | 2023-08-09 | 感光性着色树脂组合物、颜料分散液、固化物、分隔壁、有机电致发光元件、滤色器和图像显示装置 |
| CN202380047921.0A CN119384640B (zh) | 2022-08-09 | 2023-08-09 | 感光性着色树脂组合物、颜料分散液、固化物、分隔壁、有机电致发光元件、滤色器和图像显示装置 |
| JP2024540508A JPWO2024034637A1 (ja) | 2022-08-09 | 2023-08-09 | |
| KR1020257033666A KR20250152686A (ko) | 2022-08-09 | 2023-08-09 | 감광성 착색 수지 조성물, 안료 분산액, 경화물, 격벽, 유기 전계 발광 소자, 컬러 필터 및 화상 표시 장치 |
| KR1020247039376A KR102874587B1 (ko) | 2022-08-09 | 2023-08-09 | 감광성 착색 수지 조성물, 안료 분산액, 경화물, 격벽, 유기 전계 발광 소자, 컬러 필터 및 화상 표시 장치 |
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| JP2001247648A (ja) * | 2000-03-03 | 2001-09-11 | Mitsubishi Gas Chem Co Inc | 高耐熱性感光性樹脂 |
| JP2004296675A (ja) * | 2003-03-26 | 2004-10-21 | Mitsubishi Gas Chem Co Inc | 表面平滑性に優れたレジスト組成物永久保護皮膜の形成方法 |
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| JP7263031B2 (ja) * | 2019-02-01 | 2023-04-24 | 株式会社Dnpファインケミカル | 色材分散液、分散補助樹脂、感光性着色樹脂組成物及びその硬化物、カラーフィルタ、表示装置 |
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| CN114450630A (zh) * | 2019-11-06 | 2022-05-06 | 三菱化学株式会社 | 感光性树脂组合物、固化物、间隔壁、有机场致发光元件、滤色器及图像显示装置 |
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| JP2004296675A (ja) * | 2003-03-26 | 2004-10-21 | Mitsubishi Gas Chem Co Inc | 表面平滑性に優れたレジスト組成物永久保護皮膜の形成方法 |
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