WO2022176831A1 - Photosensitve green resin composition, cured product, color filter, display device, and method for producing laminate of organic light-emitting element and external light antireflection film - Google Patents

Photosensitve green resin composition, cured product, color filter, display device, and method for producing laminate of organic light-emitting element and external light antireflection film Download PDF

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Publication number
WO2022176831A1
WO2022176831A1 PCT/JP2022/005835 JP2022005835W WO2022176831A1 WO 2022176831 A1 WO2022176831 A1 WO 2022176831A1 JP 2022005835 W JP2022005835 W JP 2022005835W WO 2022176831 A1 WO2022176831 A1 WO 2022176831A1
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group
mass
carbon atoms
resin composition
pigment
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PCT/JP2022/005835
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French (fr)
Japanese (ja)
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星児 石原
麻希 藤田
充史 小野
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株式会社Ｄｎｐファインケミカル
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Priority to KR1020237030228A priority Critical patent/KR20230146556A/en
Priority to JP2023500841A priority patent/JPWO2022176831A1/ja
Priority to CN202280013059.7A priority patent/CN116806327A/en
Publication of WO2022176831A1 publication Critical patent/WO2022176831A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B25/00—Quinophthalones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
    • C09B29/0074—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing nitrogen and sulfur as heteroatoms
    • C09B29/0077—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing nitrogen and sulfur as heteroatoms containing a five-membered heterocyclic ring with one nitrogen and one sulfur as heteroatoms
    • C09B29/0085—Thiazoles or condensed thiazoles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
    • C09B47/10—Obtaining compounds having halogen atoms directly bound to the phthalocyanine skeleton
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/04—Isoindoline dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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
    • 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
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • 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
    • 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
    • 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
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • 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
    • 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]
    • 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
    • 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
    • H10K59/10—OLED displays
    • 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
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/122—Pixel-defining structures or layers, e.g. banks
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/114—Initiator containing

Definitions

  • the present invention relates to a photosensitive green resin composition, a cured product, a color filter, a display device, and a method for producing a laminate of an organic light-emitting element and an external light antireflection film using the photosensitive green resin composition.
  • an organic light emitting element emitting white light or an inorganic light emitting element emitting white light may be used.
  • An organic light-emitting display device uses a color filter for color adjustment.
  • the color filter is generally formed on a substrate, a colored layer formed on the substrate and composed of colored patterns of the three primary colors of red, green, and blue, and formed on the substrate so as to partition each colored pattern. and a light shielding part.
  • a method for forming a colored layer in a color filter for example, a colored resin composition obtained by adding a binder resin, a photopolymerizable compound and a photoinitiator to a coloring material dispersion liquid in which a coloring material is dispersed using a dispersing agent or the like is prepared. After being coated on a substrate and dried, it is exposed to light using a photomask and developed to form a colored pattern, which is fixed by heating to form a colored layer.
  • a colored resin composition is applied to a substrate in a pattern by an inkjet method or the like, dried, and then cured to form a colored pattern, and the pattern is fixed by heating to form a colored layer. Formation These steps are repeated for each color to form a color filter.
  • C.I. I. Halogenated metal phthalocyanine pigments such as Pigment Green (PG) 7, 36, 58, and 59 are often used.
  • PG Pigment Green
  • a photosensitive green resin composition containing a large amount of a halogenated metal phthalocyanine pigment has a low transmittance of the i-line (spectral line of 365 nm), which is the main exposure wavelength, and is difficult to cure uniformly to the depth of the film. There is a problem that the bottom portion of the film is scraped during development and the pattern shape is deteriorated.
  • Patent Literature 1 discloses a green colorant composition for color filters comprising a blue pigment and a yellow pigment.
  • the colorant contains at least one selected from Color Index Pigment Blue 15:3 and Color Index Pigment Blue 15:4, and Color Index Pigment Yellow 150.
  • Color Index Pigment Blue 15:3 and Color Index Pigment Blue 15:4 are contained in a total of 35 to 55 parts by weight with respect to 100 parts by weight, and the coloring composition has an absorbance for light with a wavelength of 400 to 700 nm. Among them, when the absorbance for light with a wavelength of 450 nm is 1, the wavelength at which the absorbance is 0.14 is the range of 474 to 494 nm and the range of 530 to 570 nm.
  • a coloring composition that exists in each of the ranges and has an A 450 /A 620 ratio of the absorbance A 450 for light with a wavelength of 450 nm and the absorbance A 620 for light with a wavelength of 620 nm from 1.08 to 2.05 disclosed.
  • color filters have been formed on glass substrates, but in recent years there has been a demand for forming color filters directly on element substrates.
  • Elements such as organic light-emitting elements have low heat resistance, so the heat treatment in the manufacturing process for forming the color filter directly on the element substrate is preferably performed at, for example, 130° C. or less, and more preferably 100° C. or less. .
  • the colored layer is hardened by heat treatment at about 230°C on the glass substrate. hard to do. Therefore, in order to give the colored layer the solvent resistance required in the post-process, it is necessary to sufficiently cure the colored layer by exposure.
  • a photosensitive green resin composition containing a large amount of a halogenated metal phthalocyanine pigment has a low transmittance of the i-line (spectral line of 365 nm), which is the main exposure wavelength, and is difficult to cure uniformly to the depth of the film. There was a particular problem with the solvent resistance of the cured film when the treatment was performed.
  • Patent Document 1 is a technique aimed at providing a halogen-free, high-contrast-ratio, and high-adhesion color filter substrate. No mention is made of gender.
  • the cured film obtained by performing low-temperature heat treatment using the composition specifically described in Patent Document 1 still has a poor pattern shape and poor solvent resistance, as shown in Comparative Examples below. There is a problem of being sufficient.
  • Patent Document 2 is a technique aimed at obtaining a colored composition capable of forming a cured film having excellent light resistance and color separation from other colors, and pattern shape and low-temperature heat treatment. There is no description about the solvent resistance of the cured film in the case where the method is carried out.
  • the pattern shape deteriorated and the solvent resistance was poor, as shown in the comparative examples described later. There is a problem of being sufficient.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a photosensitive green resin composition capable of forming a colored layer having good solvent resistance and a good pattern shape even when subjected to low-temperature heat treatment. and The present invention also provides a color filter and a display device formed using the photosensitive green resin composition, and a laminate of an organic light emitting device and an external light antireflection film using the photosensitive green resin composition. The object is to provide a manufacturing method.
  • the photosensitive green resin composition according to the present invention contains a colorant, an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator,
  • the coloring material includes a blue pigment and a yellow pigment, and the yellow pigment is C.I. I. Pigment Yellow 139 with a halogenated metal phthalocyanine pigment of 10% or less,
  • the spectral transmittance at 360 nm to 370 nm is 0.7% or more.
  • the cured product according to the present invention is the cured product of the photosensitive green resin composition according to the present invention.
  • the color filter according to the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a cured photosensitive green resin composition according to the present invention. It is a thing.
  • a display device has the color filter according to the present invention. Further, the display device according to the present invention has a cured film of the photosensitive green resin composition according to the present invention on the organic light-emitting element.
  • the method for producing a laminate of an organic light-emitting element and an external light antireflection film according to the present invention includes: A step of forming a coating film by applying the photosensitive green resin composition according to the present invention on the organic light emitting device; a step of irradiating the coating film with light; A post-baking step of heating the film after the light irradiation, and By including the step of developing the film after the light irradiation, A step of forming a cured film of the photosensitive green resin composition according to the present invention on the organic light emitting device.
  • a photosensitive green resin composition capable of forming a colored layer having good solvent resistance and a good pattern shape even with low-temperature heat treatment. Further, according to the present invention, a color filter and a display device formed using the photosensitive green resin composition, and a laminate of an organic light emitting device and an external light antireflection film using the photosensitive green resin composition A method of manufacturing a body can be provided.
  • FIG. 1 is a schematic cross-sectional view showing an example of a color filter according to the invention.
  • FIG. 2 is a schematic cross-sectional view showing an example of a liquid crystal display device according to the present invention.
  • FIG. 3 is a schematic cross-sectional view showing an example of an organic light-emitting display device according to the present invention.
  • FIG. 4 is a schematic cross-sectional view showing another example of a display device having an organic light-emitting device according to the present invention.
  • FIG. 5 is a schematic cross-sectional view for explaining the taper angle ( ⁇ 1) of the cross-sectional shape of the colored layer of the fine line pattern.
  • light includes electromagnetic waves with wavelengths in the visible and non-visible regions, and radiation, and radiation includes, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves with a wavelength of 5 ⁇ m or less and electron beams.
  • (meth)acryloyl represents acryloyl and methacryloyl
  • (meth)acryl represents acrylic and methacrylic
  • (meth)acrylate represents acrylate and methacrylate.
  • the term "to" indicating a numerical range is used to include the numerical values before and after it as lower and upper limits.
  • the spectral transmittance of Z % or more in the wavelength range of X nm to Y nm means that the spectral transmittance is Z % or more in the entire wavelength range of X nm to Y nm.
  • the photosensitive green resin composition according to the present invention contains a colorant, an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator,
  • the coloring material includes a blue pigment and a yellow pigment, and the yellow pigment is C.I.
  • the colorant contains a blue pigment and a yellow pigment, and the yellow pigment is C.I. I. Pigment Yellow 139, the halogenated metal phthalocyanine pigment is 10% or less, and the predetermined spectral transmittance is satisfied in the predetermined wavelength range, so that even at low temperature heat treatment, solvent resistance is good and the pattern A colored layer having a good shape can be formed.
  • the coloring material includes a blue pigment and a yellow pigment, and the yellow pigment is C.I. I.
  • Pigment Yellow 139 is included and the halogenated metal phthalocyanine pigment is 10% or less, so when a cured film is formed with a film thickness of 3.0 ⁇ m, the spectral transmittance of 360 nm to 370 nm is easy to achieve 0.7% or more. .
  • C. I. Pigment Yellow 139 has high coloring power, so it is possible to reduce the concentration of coloring materials in the cured film, and because it is possible to relatively increase the concentration of curable components, it has good solvent resistance even at low temperature heat treatment. and a colored layer having a good pattern shape can be formed.
  • a cured film is formed with a film thickness of 3.0 ⁇ m, if the transmittance at 360 nm to 370 nm is 0.7% or more, the i-line ( 365 nm spectral line) is ensured, the film is easily cured evenly to the deep part, and it is possible to suppress deterioration of the pattern shape due to scraping of the bottom part of the film during development. In addition, since it becomes easy to cure uniformly to the deep part of the film, the solvent resistance becomes good even with low-temperature heat treatment.
  • the photosensitive green resin composition according to the present invention can form a colored layer having good solvent resistance and a good pattern shape even with low-temperature heat treatment, so the cured film formed on the organic light-emitting element It can be suitably used for That is, the photosensitive green resin composition according to the present invention can be suitably used for a cured film directly formed on a device substrate having an organic light-emitting device.
  • the photosensitive green resin composition according to the present invention is used for a cured film formed adjacent to or via at least one layer on an organic light emitting device, an external color formed on a substrate such as a glass substrate Compared to a display device in which a filter is attached to an organic light-emitting element, a display device that is thinner and more flexible can be manufactured.
  • the photosensitive green resin composition according to the present invention When the photosensitive green resin composition according to the present invention is used for a cured film formed adjacent to or via at least one layer on an organic light emitting device, a color filter as a substitute for a polarizing plate for suppressing external light reflection It can also be used as Furthermore, the cured film formed on the organic light-emitting element formed from the photosensitive green resin composition according to the present invention has a content of the halogenated metal phthalocyanine pigment of 10% by mass or less with respect to the total amount of the coloring material, and has a green color. Since it is realized, even if a weather resistance test is performed in a state where glass is bonded with a transparent adhesive, a decrease in transmittance is suppressed, and a display device with excellent weather resistance can be realized.
  • the photosensitive green resin composition according to the present invention contains at least a coloring material, an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator, in a range that does not impair the effects of the present invention, and further It may contain other components.
  • a coloring material an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator
  • a photoinitiator a photosensitive green resin composition according to the present invention.
  • the coloring material is not particularly limited as long as it can develop a desired color when the colored layer of the color filter is formed, and various organic pigments, inorganic pigments, dispersible dyes, and dyes Two or more kinds of salt-forming compounds can be mixed and used.
  • Pigment Yellow 139 containing 10% or less of a halogenated metal phthalocyanine pigment.
  • organic pigments are preferably used as coloring materials because they have high coloring properties and high heat resistance.
  • organic pigments include compounds classified as pigments in the Color Index (published by The Society of Dyers and Colorists). .) numbered ones can be mentioned.
  • blue pigment for example, C.I. I. Pigment Blue 1, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 61, 79, 80 and the like.
  • C. I. Pigment Blue 15:3, C.I. I. Pigment Blue 15:4, and C.I. I. Pigment Blue 16 has a slightly different rising wavelength of the transmission spectrum from the long wavelength side to the short wavelength side. It is preferable to select and use one kind alone or two or more kinds in combination. From the viewpoint of weather resistance, C.I. I. Pigment Blue 15:4 is preferred.
  • C.I. I. Contains Pigment Yellow 139 as an essential ingredient.
  • C. I. Pigment Yellow 139 has high coloring power, so it is possible to reduce the concentration of the coloring material in the cured film, and relatively increase the concentration of the curable component, so the cured film is subjected to low-temperature heat treatment. However, it is possible to form a colored layer having good solvent resistance and a good pattern shape.
  • C.I. I. When Pigment Yellow 139 is combined with a blue pigment, the wavelength at which the maximum transmittance of the transmission spectrum is exhibited tends to be within the range of 525 nm to 545 nm, and the half width of the peak of the transmission spectrum in the wavelength range of 525 nm to 545 nm. can be easily reduced, the effect of suppressing external light reflection can be easily improved when the cured film is used as an antireflection film.
  • C.I. I. Pigment Yellow 1 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 15, 16, 17, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 60, 61, 62, 62:1, 63, 65, 71, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 98, 100, 101, 104, 105, 106, 108, 109, 110, 111, 113, 114, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 142, 147, 148, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 173, 175,
  • the yellow pigment when combined with a blue pigment, it may contain at least one selected from the group consisting of Pigment Yellow 138, Pigment Yellow 150, and Pigment Yellow 185 from the viewpoint that it is easy to adjust the desired transmission spectrum. Well, it is more preferred to further include Pigment Yellow 150.
  • the blue pigment is C.I. I. Pigment Blue 15:3, C.I. I. Pigment Blue 15:4, and C.I. I. Pigment Blue 16, wherein the yellow pigment further contains C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 150, and C.I. I. Pigment Yellow 185 may contain at least one selected from the group consisting of Pigment Yellow 185.
  • coloring material other coloring materials may be used from the viewpoint of adjusting the color tone of the cured film and the effect of suppressing reflection of external light when used as an antireflection film.
  • Other coloring materials include, for example, green pigments, purple pigments, orange pigments, and the like.
  • green pigments include C.I. I. Pigment Green 7, 36, 58, 59, 62, 63 and the like.
  • the content of the halogenated metal phthalocyanine pigment is set to 10% by mass or less based on the total amount of the coloring material in order to improve the weather resistance.
  • purple pigment for example, C.I. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and the like.
  • orange pigments include C.I. I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73 and the like.
  • the blue pigment and yellow pigment used in the present invention formed a cured film with a film thickness of 3.0 ⁇ m with the photosensitive green resin composition. Sometimes it is adjusted so that the transmittance from 360 nm to 370 nm is 0.7% or more.
  • the transmittance at 360 nm to 370 nm is 0.7% or more, the exposure wavelength when curing the coating film of the composition
  • the transmittance of the main i-line (spectral line of 365 nm) is secured, the film is easily cured evenly to the deep part, and it is possible to suppress the deterioration of the pattern shape due to the bottom part of the film being scraped during development.
  • the solvent resistance becomes good even with low-temperature heat treatment.
  • the transmittance at 360 nm to 370 nm may be 0.8% or more, and may be 0.9% or more.
  • the spectral transmittance when a cured film having a thickness of 3.0 ⁇ m is formed can be specifically measured by the method described in Examples.
  • the content ratio of the blue pigment and yellow pigment used in the present invention, and other colorants that may be contained as necessary depends on the photosensitive green resin composition.
  • the spectral transmittance in the wavelength range of 380 nm to 480 nm is 20% or less
  • the spectral transmittance in the wavelength range of 580 nm to 700 nm is 25% or less
  • 510 nm to 550 nm. is preferably adjusted so that the spectral transmittance in the wavelength range is 40% or more and 80% or less.
  • the spectral transmittance at a wavelength of 380 nm to 480 nm is 20% or less, the deterioration of the color purity of green is suppressed, and the deterioration of the color purity from the light emitting element is also suppressed. It is easy to apply, and the anti-reflection performance is excellent.
  • the spectral transmittance at a wavelength of 380 nm to 480 nm may be 18% or less, and may be 13% or less.
  • the spectral transmittance at a wavelength of 510 nm to 550 nm is 40% or more and 80% or less, it is easy to suppress deterioration in brightness and poor visibility of the display device.
  • the spectral transmittance at a wavelength of 510 nm to 550 nm may be 45% or more, 75% or less, and further 70% or less.
  • the spectral transmittance at a wavelength of 580 nm to 700 nm may be 25% or less, 20% or less, or 18% or less.
  • the wavelength at which the maximum transmittance is exhibited in the wavelength range of 380 nm to 700 nm in the transmission spectrum is preferably in the range of 525 nm to 545 nm, more preferably in the range of 525 nm to 540 nm, and more preferably in the range of 526 nm to 540 nm. is more preferred and may be in the range of 527 nm to 535 nm.
  • the half width of the peak of the transmission spectrum at a wavelength in the range of 525 nm to 545 nm is 70 nm or less. is improved, color purity is improved, and the color reproduction range is widened.
  • the half width of the peak of the transmission spectrum in the wavelength range of 525 nm to 545 nm may be 65 nm or less, 63 nm or less, or 60 nm or less.
  • the content of the coloring material used in the present invention is not particularly limited as long as it is used so as to satisfy the predetermined spectral transmittance in the predetermined wavelength range.
  • the content of the blue pigment may be, for example, 1% by mass or more and 60% by mass or less, preferably 5% by mass or more, relative to the total amount of the colorant. It may be preferably 10% by mass or more, more preferably 15% by mass or more, preferably 50% by mass or less, and more preferably 40% by mass or less.
  • the content of the yellow pigment may be, for example, 20% by mass or more and 99% by mass or less, preferably 30% by mass or more, relative to the total amount of the colorant. It may be preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, preferably 90% by mass or less, more preferably It may be 85% by mass or less.
  • the content of Pigment Yellow 139 may be 1% by mass or more, more preferably 5% by mass or more, more preferably 10% by mass or more, and 80% by mass with respect to the total amount of yellow pigment or less, preferably 70% by mass or less.
  • the total content of Pigment Yellow 139 and Pigment Yellow 150 may be 40% by mass or more, more preferably 60% by mass, relative to the total amount of yellow pigment. or more, more preferably 80% by mass or more, 100% by mass or less, or 40% by mass or less.
  • the content of Pigment Yellow 139 may be 1% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, or 75% by mass with respect to the total amount of the coloring material. or less, preferably 70% by mass or less, more preferably 65% by mass or less.
  • the content ratio of the blue pigment to the total of the blue pigment and the yellow pigment is not particularly limited as long as it satisfies a predetermined spectral transmittance in the predetermined wavelength range, but is, for example, 1% by mass or more. It may be 60% by mass or less, preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, preferably 50% by mass or less. and more preferably 40% by mass or less.
  • the total content of the blue pigment and the yellow pigment is usually 80% by mass or more, preferably 90% by mass or more, relative to the total amount of the colorant. Preferably, it may be 95% by mass or more, and may be 100% by mass. However, when it contains other coloring material different from the halogenated metal phthalocyanine pigment, it may be 90% by mass or less.
  • the total content of the other coloring materials may be 0% by mass, may be 1% by mass or more, or may be 5% by mass or more with respect to the total amount of the coloring material. On the other hand, it is usually 20% by mass or less, preferably 10% by mass or less.
  • the total content is 10% by mass or less with respect to the total amount of the coloring material, and is usually 0.1% by mass or more and 10% by mass or less. It may be preferably 1% by mass or more, more preferably 3% by mass or more, and preferably 9.5% by mass or less.
  • the halogenated metal phthalocyanine pigment may be 0% by mass with respect to the total amount of the coloring material.
  • the average primary particle size of the colorant used in the present invention is such that when it is formed into a cured film, it can suppress external light reflection and transmit desired light from the light emitting element to suppress the decrease in luminance of the display device. It is not particularly limited as long as it is possible, and although it varies depending on the type of coloring material used, it is preferably in the range of 10 nm to 100 nm, more preferably 15 nm to 60 nm. When the average primary particle diameter of the colorant is in the above range, the display device provided with the cured film produced using the photosensitive green resin composition according to the present invention can suppress external light reflection and has high contrast. and can be of high quality.
  • the average dispersed particle size of the colorant in the photosensitive green resin composition varies depending on the type of colorant used, but is preferably in the range of 10 nm to 100 nm, and is in the range of 15 nm to 60 nm. is more preferred.
  • the average dispersed particle size of the colorant in the photosensitive green resin composition is the dispersed particle size of the colorant particles dispersed in the dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. It is a thing.
  • the solvent used in the photosensitive green resin composition is appropriately diluted to a concentration that can be measured by a laser light scattering particle size distribution meter. for example, 1000 times), and measured at 23° C. by a dynamic light scattering method using a laser light scattering particle size distribution analyzer (for example, Nanotrack particle size distribution analyzer UPA-EX150 manufactured by Nikkiso Co., Ltd.).
  • the average distribution particle size here is the volume average particle size.
  • the coloring material used in the present invention can be produced by known methods such as recrystallization and solvent salt milling. Alternatively, a commercially available coloring material may be used after undergoing fine processing.
  • the content of the coloring material in the photosensitive green resin composition according to the present invention is not particularly limited.
  • the content of the colorant from the viewpoint of dispersibility and dispersion stability, relative to the total solid content of the photosensitive green resin composition, for example preferably 3 wt% to 65 wt%, more preferably 4 wt% to 60 It is within the range of % by mass. If it is at least the above lower limit, the cured film when the photosensitive green resin composition is applied to a predetermined film thickness (usually 1.0 ⁇ m to 5.0 ⁇ m, for example, 3.0 ⁇ m) has sufficient color density. It's easy to do.
  • substrate can be obtained.
  • the content of the coloring material is, for example, preferably 3% by mass to 50% by mass, more preferably 4% by mass, relative to the total solid content of the photosensitive green resin composition. % to 40% by mass.
  • the solid content refers to all substances other than the solvent, which will be described later, and includes monomers and the like dissolved in the solvent.
  • the alkali-soluble resin used in the present invention has an acidic group, and can be appropriately selected and used from those that act as a binder resin and are soluble in an alkali developer used for pattern formation. can.
  • the alkali-soluble resin can be defined as having an acid value of 40 mgKOH/g or more.
  • alkali-soluble resin a conventionally known alkali-soluble resin can be appropriately selected and used.
  • an alkali-soluble resin described in International Publication No. 2016/104493 can be appropriately selected and used.
  • a preferable alkali-soluble resin in the present invention is a resin having an acidic group, usually a carboxy group. acrylic resins, epoxy (meth)acrylate resins having a carboxy group, and the like, and acrylic resins such as acrylic copolymers having a carboxy group and styrene-acrylic copolymers having a carboxy group are preferably used.
  • Two or more of these acrylic copolymers, acrylic resins such as styrene-acrylic copolymers, and epoxy acrylate resins may be used in combination.
  • the alkali-soluble resin used in the photosensitive green resin composition may be used singly or in combination of two or more.
  • the content of the alkali-soluble resin is not particularly limited, but is preferably 5% to 60% by mass, more preferably 10% to 40% by mass, based on the total solid content of the photosensitive green resin composition. Within range. When the content of the alkali-soluble resin is at least the above lower limit, sufficient alkali developability is obtained, and when the content of the alkali-soluble resin is at most the above upper limit, film roughness and pattern chipping during development are prevented. can be suppressed.
  • photopolymerizable compound used in the photosensitive green resin composition examples include compounds having a photopolymerizable group in the molecule.
  • the photopolymerizable group is not particularly limited as long as it can be polymerized by a photoinitiator, but includes ethylenically unsaturated double bonds, such as vinyl group, allyl group, acryloyl group or methacryloyl group. are mentioned.
  • an acryloyl group or a methacryloyl group is preferably used from the viewpoint of ultraviolet curability.
  • the photopolymerizable compound from the viewpoint of curability, it is preferable to contain a compound having two or more photopolymerizable groups in one molecule, and a compound having three or more photopolymerizable groups in one molecule is contained. is more preferable.
  • a compound having two or more ethylenically unsaturated double bonds is preferably used, and a polyfunctional (meth)acrylate having two or more acryloyl groups or methacryloyl groups is particularly preferable.
  • a polyfunctional (meth)acrylate it may be appropriately selected and used from conventionally known ones. Specific examples include those described in JP-A-2013-029832.
  • polyfunctional (meth)acrylates may be used singly or in combination of two or more. Further, when excellent photocurability (high sensitivity) is required for the photosensitive green resin composition of the present invention, the polyfunctional (meth) acrylate has three polymerizable double bonds (trifunctional) Those having the above are preferable, and poly (meth) acrylates of trihydric or higher polyhydric alcohols and dicarboxylic acid-modified products thereof are preferable.
  • trimethylolpropane tri (meth) acrylate, pentaerythritol tri (Meth)acrylate, succinic acid-modified pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol penta(meth) ) succinic acid-modified acrylate, dipentaerythritol hexa(meth)acrylate and the like are preferred.
  • the content of the photopolymerizable compound used in the photosensitive green resin composition is not particularly limited, relative to the total solid content of the photosensitive green resin composition, for example preferably 5 wt% to 60 wt%, More preferably, it is within the range of 10% by mass to 40% by mass. If the content of the photopolymerizable compound is at least the above lower limit, photocuring will proceed sufficiently, and the exposed portion will be able to suppress elution during development. Adequate alkali developability.
  • photoinitiator used in the photosensitive green resin composition of the present invention one or a combination of two or more of various conventionally known photoinitiators can be used.
  • photoinitiators include aromatic ketones, benzoin ethers, halomethyloxadiazole compounds, ⁇ -aminoketones, biimidazoles, N,N-dimethylaminobenzophenone, halomethyl-S-triazine compounds, and thioxanthone. , oxime esters, and the like.
  • a conventionally known photoinitiator can be used, and examples thereof include the photoinitiator described in WO 2018/062105.
  • Examples of the oxime ester photoinitiator used in the present invention include 1,2-octadione-1-[4-(phenylthio)phenyl]-,2-(o-benzoyloxime), ethanone, 1-[ 9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyloxime), JP-A-2000-80068, JP-A-2001-233842, special table 2010-527339, JP 2010-527338, JP 2013-041153, WO 2015/152153, JP 2010-256891, among the oxime ester photoinitiators described in It can be selected as appropriate.
  • the photoinitiator preferably contains at least one compound represented by the following general formula (A), because the solvent resistance of the cured film tends to be good even with low-temperature heat treatment.
  • R 1 and R 2 each independently represent R 11 , OR 11 , COR 11 , SR 11 , CONR 12 R 13 or CN;
  • R 11 , R 12 and R 13 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms or 2 to 20 carbon atoms.
  • R 21 , R 22 and R 23 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms or 2 to 20 carbon atoms.
  • R 21 , R 22 and R 23 represents a heterocyclic group of hydrogen atoms in the groups represented by R 21 , R 22 and R 23 may be further substituted with a hydroxyl group, a nitro group, CN, a halogen atom, or a carboxy group;
  • the alkylene portions of the groups represented by R 11 , R 12 , R 13 , R 21 , R 22 and R 23 are -O-, -S-, -COO-, -OCO-, -NR 24 -, -NR 24 CO-, -NR 24 COO-, -OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO- may contain 1 to 5 oxygen atoms not adjacent to each other,
  • R 24 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a
  • R 3 may be The hydrogen atoms of the group represented by R 3 may further be R 21 , OR 21 , COR 21 , SR 21 , NR 22 R 23 , CONR 22 R 23 , —NR 22 —OR 23 , —NCOR 22 —OCOR 23 , NR 22 COR 21 , OCOR 21 , COOR 21 , SCOR 21 , OCSR 21 , COSR 21 , CSOR 21 , a hydroxyl group, a nitro group, CN, or optionally substituted with a halogen atom
  • R 4 , R 5 , R 6 and R 7 are each independently R 11 , OR 11 , SR 11 , COR 14 , CONR 15 R 16 , NR 12 COR 11 , OCOR 11 , COOR 14 , SCOR 11 , OCSR 11 , COSR 14 , CSOR 11 , a hydroxyl group, CN or a halogen atom, R 4 and R 5 , R 6
  • R 8 is R 11 , OR 11 , SR 11 , COR 11 , CONR 12 R 13 , NR 12 COR 11 , OCOR 11 , COOR 11 , SCOR 11 , OCSR 11 , COSR 11 , CSOR 11 represents a hydroxyl group, CN or a halogen atom, k represents 0 or 1; )
  • the oxime ester compound represented by the general formula (A) includes geometric isomers due to the double bond of the oxime, but these are not distinguished. That is, in the present specification, the compound represented by the general formula (A), and the compound represented by the following general formula (A′), which is a preferred form of the compound described later, and the exemplary compounds thereof are a mixture of both or either It represents one or the other, and is not limited to the structure showing the isomer.
  • alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t- octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, cyclopentyl, cyclopentylmethyl, cyclopen
  • Examples of the aryl group having 6 to 30 carbon atoms represented by R 3 , R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 in the general formula (A) include phenyl , tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, phenyl substituted with one or more of the above alkyl groups, biphenylyl, naphthyl, anthryl, and the like.
  • Examples of arylalkyl groups having 7 to 30 carbon atoms represented by R 3 , R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 in general formula (A) include: benzyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, phenylethyl and the like.
  • heterocyclic groups having 2 to 20 carbon atoms represented by R 3 , R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 in the general formula (A) include , pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, piperazyl, morpholinyl, etc.
  • the rings that can be formed by R 4 and R 5 , R 5 and R 6 , R 6 and R 7 , R 3 and R 7 and R 3 and R 8 together include: Preferred examples include 5- to 7-membered rings such as cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, piperidine ring, morpholine ring, lactone ring and lactam ring.
  • Halogen atoms represented by R 4 , R 5 , R 6 , R 7 and R 8 in general formula (A), and R 3 , R 11 and R 12 in general formula (A) , R 13 , R 21 , R 22 and R 23 may be substituted with fluorine, chlorine, bromine and iodine.
  • the alkylene moieties of the groups represented by R 11 , R 12 , R 13 , R 21 , R 22 and R 23 in the above general formula (A) are -O-, -S-, -COO-, -OCO -, -NR 24 -, -NR 24 CO-, -NR 24 COO- , -OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO-, 1 to 1 under the condition that oxygen atoms are not adjacent to each other; It may contain 5 divalent groups, and the divalent groups contained at this time may be one or more groups, and in the case of groups that can be contained continuously, 2 or more may be contained continuously. .
  • alkyl (alkylene) moieties of the groups represented by R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 in the general formula (A) have branched side chains. may be a cyclic alkyl.
  • R 3 is an optionally condensed aromatic ring or compounds represented by the following general formula (A') have high sensitivity and can be manufactured is preferred because it is easy to
  • R 31 , R 32 , R 33 , R 34 and R 35 are each independently R 11 , OR 11 , SR 11 , COR 11 , CONR 15 R 16 , NR 12 COR 11 , OCOR 11 , COOR 14 , SCOR 11 , OCSR 11 , COSR 14 , CSOR 11 , hydroxyl group , a nitro group, CN or a halogen atom, and R 31 and R 32 , R 32 and R 33 , R 33 and R 34 and R 34 and R 35 may each form a ring together.
  • rings formed by R 31 and R 32 , R 32 and R 33 , R 33 and R 34 and R 34 and R 35 together include R 4 and R 5 , R 5 and R 6 and R 6 and R 7 and R 3 and R 7 and R 3 and R 8 together may be formed by the same rings as those mentioned above.
  • R 1 is an alkyl group having 1 to 12 carbon atoms or an arylalkyl group having 7 to 15 carbon atoms
  • R 11 is an aryl group having 6 to 12 carbon atoms
  • 1 carbon atom alkyl groups of 1 to 8 are preferred because they are highly soluble in solvents
  • R 2 is preferably a methyl group, ethyl group or phenyl group because of their high reactivity
  • R 4 to R 7 are hydrogen atoms or cyano A group, particularly a hydrogen atom, is preferred for ease of synthesis.
  • a hydrogen atom as R 8 is preferred for ease of synthesis.
  • k is preferably 1 for high sensitivity.
  • R 31 to R 35 is a nitro group, CN, a halogen atom, or COR 11
  • R 11 is an aryl group having 6 to 12 carbon atoms or an alkyl group having 1 to 8 carbon atoms.
  • R 31 to R 35 is a nitro group, CN or a halogen atom
  • R 33 is a nitro group, CN or a halogen atom.
  • Preferred specific examples of the compound represented by the general formula (A) include the following compounds.
  • the total content of the photoinitiator used in the photosensitive green resin composition of the present invention is not particularly limited as long as the effect of the present invention is not impaired, relative to the total solid content of the photosensitive green resin composition, It is preferably in the range of 0.1% by mass to 15.0% by mass, more preferably in the range of 1.0% by mass to 10.0% by mass. If the content is at least the above lower limit, photocuring will proceed sufficiently, and the solvent resistance and substrate adhesion will tend to be good. easy to form patterns.
  • the total content of at least one of the compounds represented by the general formula (A) is the total amount of the photoinitiator from the viewpoint that a cured film having good substrate adhesion and solvent resistance can be formed even in low-temperature heat treatment. is preferably 30.0% by mass or more, more preferably 50.0% by mass or more, still more preferably 70.0% by mass or more, and may be 100% by mass.
  • the photosensitive green resin composition of the present invention may contain a solvent.
  • the solvent used in the present invention is not particularly limited as long as it does not react with each component in the photosensitive green resin composition and is capable of dissolving or dispersing them.
  • a solvent can be used individually or in combination of 2 or more types.
  • solvents include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, i-propyl alcohol, methoxy alcohol and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ester solvents such as ethyl lactate and cyclohexanol acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and
  • glycol ether acetate-based solvents examples include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and one or more selected from the group consisting of 3-methoxybutyl acetate, from the viewpoint of solubility of other components and applicability.
  • BCA butyl carbitol acetate
  • 3-methoxy-3-methyl-1-butyl acetate ethyl ethoxypropionate
  • ethyl lactate examples include one or more selected from the group consisting of 3-methoxybutyl acetate, from the viewpoint of solubility of other components and applicability.
  • the content of the solvent may be appropriately set within a range in which the colored layer can be formed with high precision.
  • the content of the solvent is usually in the range of preferably 55% by mass to 95% by mass, more preferably 65% by mass to 88% by mass, based on the total amount of the photosensitive green resin composition containing the solvent. When the content of the solvent is within the above range, excellent applicability can be obtained.
  • a dispersant when the colorant is dispersed, a dispersant may be further included from the viewpoint of colorant dispersibility and colorant dispersion stability.
  • the dispersant can be appropriately selected and used from conventionally known dispersants.
  • the dispersant for example, cationic, anionic, nonionic, amphoteric, silicone, or fluorine surfactants can be used.
  • surfactants polymer dispersants are preferred because they can be uniformly and finely dispersed.
  • polymer dispersants include (meth)acrylate copolymer dispersants; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; amides obtained by reaction with free carboxyl group-containing polyesters and their bases); polyallylamine derivatives (polyallylamine and polyesters having free carboxyl groups, polyamides, or cocondensates of esters and amides (polyesteramides) (a reaction product obtained by reacting with one or more compounds selected from the compounds of ), and the like.
  • polymer dispersants include (meth)acrylate copolymer dispersants; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; amides obtained by reaction with free carboxyl group-containing polyesters and their bases); polyallylamine derivatives (polyallylamine and polyesters having free carboxyl groups, polyamides, or cocondensates of esters and
  • (Meth) acrylate copolymer-based dispersant has good compatibility with the photoinitiator containing the compound represented by the photopolymerizable compound and the general formula (A), so that the initiator is in the colored layer It is presumed that the colored layer is likely to exist uniformly, and the uniform curing of the colored layer reduces the amount of unreacted components and reduces the internal stress of the colored layer, so that the colored layer changes less when immersed in a solvent.
  • the (meth)acrylate copolymer-based dispersant refers to a dispersant that is a copolymer and contains at least a (meth)acrylate-derived structural unit.
  • the (meth)acrylate copolymer-based dispersant is preferably a copolymer containing a structural unit that functions as a coloring material adsorption site and a structural unit that functions as a solvent affinity site, and functions as a solvent affinity site. It is preferable that at least a (meth)acrylate-derived structural unit is included in the structural units to be used.
  • Examples of structural units that function as colorant adsorption sites include structural units derived from ethylenically unsaturated monomers copolymerizable with structural units derived from (meth)acrylate.
  • the coloring material adsorption site may be a structural unit derived from an ethylenically unsaturated monomer containing an acidic group, or a structural unit derived from an ethylenically unsaturated monomer containing a basic group.
  • a structural unit represented by the following general formula (I) is preferable from the viewpoint of excellent dispersibility.
  • R 71 is a hydrogen atom or a methyl group
  • a 1 is a divalent linking group
  • R 72 and R 73 are each independently a hydrogen atom, or a hydrocarbon which may contain a hetero atom. group, and R 72 and R 73 may combine with each other to form a ring structure.
  • a 1 is a divalent linking group.
  • the divalent linking group for example, a linear, branched or cyclic alkylene group, a linear, branched or cyclic alkylene group having a hydroxyl group, an arylene group, -CONH- group, -COO- group, -NHCOO- groups, ether groups (--O--groups), thioether groups (--S--groups), and combinations thereof.
  • the bonding direction of the divalent linking group is arbitrary.
  • a 1 in the general formula (I) is preferably a divalent linking group containing a -CONH- group or a -COO- group, and a -CONH- group or a -COO- group.
  • an alkylene group having 1 to 10 carbon atoms are more preferable.
  • Examples of the hydrocarbon group in the hydrocarbon group optionally containing a heteroatom for R 72 and R 73 include an alkyl group, an aralkyl group and an aryl group.
  • Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2-ethylhexyl group, cyclopentyl group, cyclohexyl group and the like, and the number of carbon atoms in the alkyl group is 1. to 18 are preferable, and among them, a methyl group or an ethyl group is more preferable.
  • the aralkyl group includes, for example, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like.
  • the number of carbon atoms in the aralkyl group is preferably 7-20, more preferably 7-14.
  • Aryl groups include phenyl, biphenyl, naphthyl, tolyl, and xylyl groups.
  • the number of carbon atoms in the aryl group is preferably 6-24, more preferably 6-12.
  • the number of carbon atoms of the substituent is not included in the preferable number of carbon atoms.
  • a hydrocarbon group containing a heteroatom has a structure in which a carbon atom in the hydrocarbon group is replaced with a heteroatom, or a structure in which a hydrogen atom in the hydrocarbon group is replaced by a substituent containing a heteroatom.
  • the heteroatom that the hydrocarbon group may contain include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom and the like.
  • hydrogen atoms in the hydrocarbon group may be substituted with halogen atoms such as fluorine, chlorine and bromine atoms.
  • R 72 and R 73 are bonded to each other to form a ring structure means that R 72 and R 73 form a ring structure via a nitrogen atom.
  • the ring structure formed by R72 and R73 may contain a heteroatom.
  • the ring structure is not particularly limited, examples thereof include pyrrolidine ring, piperidine ring, morpholine ring and the like.
  • R 72 and R 73 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, or R 72 and R 73 are bonded to form a pyrrolidine ring, piperidine It preferably forms a ring or a morpholine ring.
  • Examples of monomers that derive structural units represented by the general formula (I) include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, and the like.
  • Alkyl group-substituted amino group-containing (meth)acrylates, alkyl group-substituted amino group-containing (meth)acrylamides such as dimethylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, and the like can be mentioned.
  • dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylaminopropyl (meth)acrylamide can be preferably used in terms of improving dispersibility and dispersion stability.
  • the structural unit represented by formula (I) may consist of one type, or may contain two or more types of structural units.
  • the structural unit functioning as the coloring material adsorption site is selected from the group consisting of at least part of the nitrogen site possessed by the structural unit represented by the general formula (I), an organic acid compound, and a halogenated hydrocarbon. At least one of them may form a salt (hereinafter, such a copolymer may be referred to as a salt-type copolymer).
  • a compound represented by the following general formula (1) and a compound represented by the following general formula (3) are preferable.
  • at least one compound selected from the group consisting of the organic acid compound and the halogenated hydrocarbon is preferably one or more compounds selected from the group consisting of the following general formulas (1) to (3). can.
  • R a is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group which may have a substituent or a benzyl group, or -O- Represents R e
  • R e is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group which may have a substituent or a benzyl group, or a C 1 to 4 represents a (meth)acryloyl group via an alkylene group.
  • R b , R b′ , and R b′′ each independently represent a hydrogen atom, an acidic group or an ester group thereof, or a substituent.
  • a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms a vinyl group which may have a substituent, a phenyl group which may have a substituent or a benzyl group, or -O- R f represents an optionally substituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group optionally having a substituent, a substituted may be a phenyl group or a benzyl group, or a (meth)acryloyl group via an alkylene group having 1 to 4 carbon atoms, and X represents a chlorine atom, a bromine atom, or an iodine atom.
  • R c and R d are each independently a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl group or a benzyl group, Alternatively, —O—R e , where R e is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl group or a benzyl group, or a carbon number represents a (meth)acryloyl group via 1 to 4 alkylene groups, provided that at least one of R c and R d contains a carbon atom.
  • the organic acid compound is an acidic organic phosphorus compound such as phenylphosphonic acid or phenylphosphinic acid from the viewpoint of excellent dispersibility and dispersion stability of the coloring material.
  • the organic acid compound used in such a dispersant include, for example, the organic acid compounds described in JP-A-2012-236882 as suitable ones.
  • the halogenated hydrocarbon is preferably at least one selected from allyl halides such as allyl bromide and benzyl chloride, and aralkyl halides, from the viewpoint of excellent dispersibility and dispersion stability of the coloring material.
  • the content of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons forms a salt with the terminal nitrogen moiety of the structural unit represented by general formula (I). Therefore, the total of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons is 0 for the terminal nitrogen portion of the structural unit represented by general formula (I) It is preferably 0.01 mol or more, more preferably 0.05 mol or more, still more preferably 0.1 mol or more, and particularly preferably 0.2 mol or more. When it is at least the above lower limit, the effect of improving the dispersibility of the coloring material by salt formation is likely to be obtained.
  • At least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons may be used singly or in combination of two or more. When combining two or more, the total content is preferably within the above range.
  • the salt-type copolymer As a method for preparing the salt-type copolymer, at least one selected from the group consisting of the organic acid compound and the halogenated hydrocarbon is added to the solvent in which the copolymer before salt formation is dissolved or dispersed, and the mixture is stirred. and a method of heating if necessary.
  • the terminal nitrogen portion of the structural unit represented by the general formula (I) of the copolymer and at least one selected from the group consisting of the organic acid compound and the halogenated hydrocarbon form a salt. and the ratio thereof can be confirmed by a known method such as NMR.
  • the copolymer having the structural unit represented by the general formula (I) has the structural unit represented by the general formula (I), and the graft polymer chain ( A graft copolymer having a meth)acrylate-derived structural unit, and a block having an A block containing a structural unit represented by the general formula (I) and a B block containing a (meth)acrylate-derived structural unit is more preferably at least one of copolymers.
  • the graft copolymer and the block copolymer will be described in order.
  • a graft copolymer having a structural unit represented by the general formula (I) and having a (meth)acrylate-derived structural unit in the graft polymer chain the structural unit represented by the general formula (I) and A graft copolymer having a structural unit represented by the following general formula (II), and at least part of the nitrogen site of the structural unit represented by the general formula (I) of the graft copolymer and an organic At least one salt-type graft copolymer formed by forming a salt with at least one selected from the group consisting of acid compounds and halogenated hydrocarbons may be mentioned.
  • R 71′ is a hydrogen atom or a methyl group
  • a 2 is a direct bond or a divalent linking group
  • Polymer represents a polymer chain
  • the constituent units of the polymer chain include (meth)acrylate (Contains structural units derived from
  • A2 is a direct bond or a divalent linking group.
  • the divalent linking group for A2 is not particularly limited as long as it can link the carbon atom derived from the ethylenically unsaturated double bond and the polymer chain.
  • Examples of the divalent linking group for A 2 include those similar to the divalent linking group for A 1 .
  • a 2 in general formula (II) is preferably a divalent linking group containing a -CONH- group or a -COO- group, and a -CONH- group or a -COO- group. , and an alkylene group having 1 to 10 carbon atoms are more preferable.
  • Polymer represents a polymer chain, and structural units of the polymer chain include structural units derived from (meth)acrylate.
  • the graft copolymer has a structural unit represented by the general formula (II) having a specific polymer chain, so that the solvent affinity is improved, and the dispersibility and dispersion stability of the coloring material are improved. and compatibility with the photoinitiator described above is improved.
  • Examples of structural units of the polymer chain include structural units represented by the following general formula (III).
  • R 74′′ is a hydrogen atom or a methyl group
  • a 4 is a divalent linking group
  • R 80 is a hydrogen atom or a hydrocarbon group which may contain a hetero atom.
  • Examples of the divalent linking group for A 4 include those similar to the divalent linking group for A 1 .
  • a structural unit derived from (meth)acrylate a structural unit represented by general formula (III) in which A 4 in general formula (III) is a divalent linking group containing a —COO— group is , at least included.
  • a 4 in general formula (III) may contain a divalent linking group containing a -CONH- group.
  • hydrocarbon groups in the hydrocarbon group optionally containing a heteroatom in R 80 include alkyl groups, alkenyl groups, aryl groups, and combinations thereof such as aralkyl groups and alkyl-substituted aryl groups.
  • the hydrocarbon group in the hydrocarbon group optionally containing a heteroatom for R 80 includes, for example, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group, an aralkyl group, and an alkyl-substituted Combinations of these, such as aryl groups, are included.
  • the alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl and n- nonyl group, n-lauryl group, n-stearyl group, cyclopentyl group, cyclohexyl group, bornyl group, isobornyl group, dicyclopentanyl group, adamantyl group, lower alkyl group-substituted adamantyl group and the like.
  • the number of carbon atoms in the alkyl group is preferably 1-12, more preferably 1-6.
  • the alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. Examples of such alkenyl groups include vinyl groups, allyl groups, and propenyl groups. Although the position of the double bond of the alkenyl group is not limited, it is preferable that the alkenyl group has a double bond at the terminal from the viewpoint of the reactivity of the resulting polymer.
  • the alkenyl group preferably has 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms.
  • Aryl groups include phenyl, biphenyl, naphthyl, tolyl, and xylyl groups. The number of carbon atoms in the aryl group is preferably 6-24, more preferably 6-12.
  • the aralkyl group includes a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, and the like, and may further have a substituent.
  • the number of carbon atoms in the aralkyl group is preferably 7-20, more preferably 7-14.
  • a linear or branched alkyl group having 1 to 30 carbon atoms may be bonded as a substituent to the aromatic ring such as the aryl group or the aralkyl group.
  • hydrocarbon groups for R 80 from the viewpoint of dispersion stability, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 12 carbon atoms which may be substituted with an alkyl group, and an alkyl group.
  • aralkyl groups having 7 to 14 carbon atoms, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n It is preferably one or more selected from the group consisting of -nonyl group, n-lauryl group, n-stearyl group, phenyl group optionally substituted with an alkyl group, and benzyl group.
  • heteroatom examples include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom and the like.
  • the hydrocarbon group which may contain a heteroatom includes, for example, -CO-, -COO-, -OCO-, -O-, -S-, -CO-S-, - S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O- , —O—NH— and other connecting groups.
  • the hydrocarbon group may have a substituent as long as it does not interfere with the dispersion performance of the graft copolymer. Nitro group, cyano group, epoxy group, isocyanate group, thiol group and the like.
  • the hydrocarbon group optionally containing a heteroatom in R 80 may have a structure in which a polymerizable group such as an alkenyl group is added to the end of the hydrocarbon group via a linking group containing a heteroatom.
  • Examples of monomers that induce structural units represented by general formula (III) include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) Acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate , dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, (meth) acrylic acid, 2-methacryloyloxyethyl succinate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- Hydroxybut
  • the R 80 it is preferable to use one having excellent solubility in the organic solvent described later, and it may be appropriately selected according to the organic solvent used in the colorant dispersion.
  • the organic solvent is an ether-alcohol acetate-based, ether-based, ester-based, or alcohol-based organic solvent generally used as an organic solvent for a colorant dispersion
  • a structural unit represented by the following general formula (IV) and a structural unit represented by the following general formula (IV') are added to the structural unit of the polymer chain in the structural unit represented by the general formula (II).
  • the inclusion of at least one structural unit selected from the group consisting of structural units is further improved the solvent resistance of the cured product of the photosensitive green resin composition, and of the photosensitive green resin composition This is preferable from the viewpoint of shortening the development time.
  • the structural unit represented by the following general formula (IV) and the structural unit represented by the following general formula (IV') are structural units included in the structural unit represented by the general formula (III).
  • R 74 is a hydrogen atom or a methyl group
  • a 3 is a divalent linking group
  • R 75 is an ethylene group or a propylene group
  • R 76 is a hydrogen atom or a hydrocarbon group
  • m represents a number of 3 or more and 80 or less.
  • R 74' is a hydrogen atom or a methyl group
  • a 3' is a divalent linking group
  • R 77 is an alkylene group having 1 to 10 carbon atoms
  • R 78 has 3 to 7 carbon atoms.
  • the alkylene group of R 79 is a hydrogen atom or a hydrocarbon group
  • n represents a number of 1 or more and 40 or less.
  • Examples of the divalent linking group for A 3 include those similar to the divalent linking group for A 1 . Among them, from the viewpoint of solubility in organic solvents used for color filters, A 3 in general formula (IV) is preferably a divalent linking group containing a -CONH- group or a -COO- group. , -CONH- or -COO- group, and even more preferably -COO- group.
  • m represents the number of repeating units of an ethylene oxide chain or a propylene oxide chain, and represents a number of 3 or more. It is more preferable to have
  • the graft copolymer contains a main chain portion having a structural unit represented by general formula (I) and a structural unit represented by general formula (II),
  • the structural unit represented by the general formula (II) includes a structural unit represented by the general formula (IV) containing a polyethylene oxide chain or a polypropylene oxide chain having a specific repeating number in the polymer chain.
  • the constituent units of the polymer chain thus grafted include a constituent unit having a polyethylene oxide chain or polypropylene oxide chain having a specific repeating number,
  • the polymer chain itself has a branched structure. It is presumed that the multiple grafted polymer chains spread three-dimensionally in the film and the specific surface area increases, so that the penetration of the solvent into the coating film and the arrival of the coloring material can be further suppressed.
  • the upper limit of m is 80 or less, but preferably 50 or less from the viewpoint of solubility in organic solvents used for color filters.
  • the hydrocarbon group for R 76 may be the same as the hydrocarbon group for R 80 .
  • an alkyl group having 1 to 18 carbon atoms an aryl group having 6 to 12 carbon atoms which may be substituted with an alkyl group
  • the alkyl group is preferably one or more selected from the group consisting of optionally substituted aralkyl groups having 7 to 14 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl. It is preferably one or more selected from the group consisting of groups, n-nonyl groups, n-lauryl groups, n-stearyl groups, phenyl groups optionally substituted with alkyl groups, and benzyl groups.
  • examples of the divalent linking group for A3 ' include the same divalent linking groups as the divalent linking groups for A1.
  • a 3' in general formula (IV') is a divalent linking group containing a -CONH- or -COO- group. is preferred, a -CONH- group or a -COO- group is more preferred, and a -COO- group is even more preferred.
  • R 77 is an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 2 to 8 carbon atoms from the viewpoint of solvent resolubility.
  • R 78 is an alkylene group having 3 to 7 carbon atoms. Among them, an alkylene group having 3 to 5 carbon atoms, and more preferably an alkylene group having 5 carbon atoms are preferable from the standpoint of substrate adhesion.
  • R 79 is a hydrogen atom or a hydrocarbon group, and the hydrocarbon group for R 79 may be the same as the hydrocarbon group for R 76 above.
  • n in the general formula (IV′) represents the number of repeating units of the ester chain, and represents a number of 1 or more. There is preferably one, and more preferably 3 or more. On the other hand, the upper limit of n is 40 or less, but preferably 20 or less from the viewpoint of solubility in organic solvents used for color filters.
  • At least one structural unit selected from the group consisting of structural units represented by the general formula (IV) and structural units represented by the following general formula (IV′) may be used alone. Although it is good, 2 or more types may be mixed.
  • the inclusion of the structural unit represented by the general formula (IV) makes the action of the solvent affinity portion due to the oxygen atom more pronounced, and shortens the development time of the photosensitive green resin composition. , and solvent resistance is improved.
  • the structural unit of the polymer chain in the structural unit represented by the general formula (II) has m At least one selected from the group consisting of structural units represented by the general formula (IV) in which m is 19 or more and 80 or less, and a structural unit represented by the general formula (IV) in which m is 3 or more and 10 or less It is more preferable to contain in combination with at least one selected from the group consisting of at least one selected from the group consisting of structural units represented by the general formula (IV) in which m is 19 or more and 50 or less , m is 3 or more and m is 3 or more and 8 or less, and at least one selected from the group consisting of the structural units represented by the above general formula (IV) is further preferably combined.
  • the total proportion of the structural units represented by the general formula (IV) in which m is 19 or more and 80 or less is, when the total structural units of the polymer chain is 100% by mass, the effect of suppressing water staining Therefore, it is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 4% by mass or more, while solvent re-solubility and water stain suppression effect Therefore, it is preferably 75% by mass or less, more preferably 65% by mass or less, and even more preferably 50% by mass or less.
  • the total proportion of the constituent units represented by IV) is preferably 20% by mass or more when the total constituent units of the polymer chain are taken as 100% by mass.
  • the total proportion of the structural units represented by the general formula (IV) in which m is 3 or more and 10 or less is 100 mass of all the structural units of the polymer chain. %, it is preferably 80% by mass or less, more preferably 60% by mass or less. Further, in the polymer chain, a structural unit represented by the general formula (IV) in which m is 19 or more and 80 or less and a structural unit represented by the general formula (IV) in which m is 3 or more and 10 or less are mixed.
  • the ratio is represented by the structural unit represented by the general formula (IV) in which m is 19 or more and 80 or less and the general formula (IV) in which m is 3 or more and 10 or less from the viewpoint of improving the effect of suppressing development residue.
  • the total of the structural units is 100 parts by mass
  • the total of the structural units represented by the general formula (IV) in which m is 19 or more and 80 or less is preferably 3 parts by mass or more, and 6 parts by mass or more. more preferably 80 parts by mass or less, and more preferably 60 parts by mass or less.
  • the total structural units of the polymer chain is 100% by mass, it is represented by the general formula (IV). and at least one structural unit selected from the group consisting of structural units represented by the general formula (IV′) is preferably 1% by mass or more, and 2% by mass or more. It is more preferable that the content is 4% by mass or more.
  • the total proportion of at least one structural unit selected from the group consisting of the structural units represented by the general formula (IV) and the structural units represented by the general formula (IV') is the point of solvent re-solubility. Therefore, it is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less when the total constituent units of the polymer chain are 100% by mass.
  • the structural unit represented by the general formula (III) including the structural unit represented by the general formula (IV) and the structural unit represented by the general formula (IV') is one type. It may be used alone or in combination of two or more. From the viewpoint of the dispersibility and dispersion stability of the coloring material, the total proportion of the structural units represented by the general formula (III) is 70% by mass or more when the total structural units of the polymer chain are 100% by mass. It is preferably 90% by mass or more, more preferably 90% by mass or more. On the other hand, from the viewpoint of satisfying dispersion stability and excellent solvent resistance at the same time, the total proportion of the structural units represented by the general formula (III) in the polymer chain is 100 of the total structural units of the polymer chain.
  • the total proportion of (meth)acrylate-derived structural units is 60% by mass when the total structural units of the polymer chain is 100% by mass, from the viewpoint of dispersion stability, solvent resistance, and compatibility with the initiator. It is preferably 80% by mass or more, and more preferably 80% by mass or more.
  • the total proportion of structural units derived from (meth)acrylate in the polymer chain is 100% by mass of all structural units of the polymer chain. Sometimes it may be 100% by weight.
  • the structural units of the polymer chain in the structural units represented by the general formula (II) of the graft copolymer include other structural units in addition to the structural units represented by the general formula (III). You can stay Examples of other structural units include structural units derived from monomers having unsaturated double bonds copolymerizable with the monomers from which the structural units represented by general formula (III) are derived. Examples of monomers from which other structural units are derived include styrene, styrenes such as ⁇ -methylstyrene, vinyl ethers such as phenyl vinyl ether, and the like.
  • the total proportion of other structural units is 100% of the total structural units of the polymer chain, from the viewpoint of the effect of the present invention.
  • % by mass it is preferably 30% by mass or less, more preferably 10% by mass or less.
  • the weight average molecular weight Mw of the polymer chain in the polymer is preferably 2000 or more, more preferably 3000 or more, and even more preferably 4000 or more, from the viewpoint of the dispersibility and dispersion stability of the colorant. , 15000 or less, and even more preferably 12000 or less. Within the above range, a sufficient steric repulsion effect as a dispersant can be maintained, and the specific surface area of the solvent affinity part of the dispersant increases, allowing the solvent to penetrate the coating film and reach the coloring material. becomes easier to suppress.
  • the polymer chain in Polymer preferably has a solubility of 20 (g/100 g solvent) or more at 23° C. in the organic solvent used in combination.
  • the solubility of the polymer chain can be determined based on the solubility of the raw material into which the polymer chain is introduced when preparing the graft copolymer. For example, when using a polymerizable oligomer (macromonomer) containing a group having an ethylenically unsaturated double bond at the polymer chain and its terminal in order to introduce a polymer chain into the graft copolymer, the polymerizable oligomer is the above So long as it has solubility.
  • a copolymer is formed from a monomer containing a group having an ethylenically unsaturated double bond
  • a polymer chain containing a reactive group capable of reacting with the reactive group contained in the copolymer When a polymer chain is introduced, it is sufficient that the polymer chain containing the reactive group has the aforementioned solubility.
  • the structural unit represented by the general formula (I) is preferably contained in a proportion of 3% by mass to 60% by mass, more preferably 6% by mass to 45% by mass, 9% by mass to 30% by mass is more preferable. If the structural unit represented by the general formula (I) in the graft copolymer is within the above range, the ratio of the affinity portion with the coloring material in the graft copolymer will be appropriate, and the solubility in the organic solvent will be good. Since the deterioration of the properties can be suppressed, the adsorptivity to the coloring material is improved, and excellent dispersibility and dispersion stability can be easily obtained.
  • the structural unit represented by the general formula (II) is preferably contained in a proportion of 40% by mass to 97% by mass, more preferably 55% by mass to 94% by mass. Preferably, 70% by mass to 91% by mass is more preferable. If the structural unit represented by the general formula (II) in the graft copolymer is within the above range, the ratio of the solvent-affinity portion in the graft copolymer will be appropriate, resulting in sufficient stericity as a dispersant. Since the repulsion effect can be maintained and the specific surface area of the solvent affinity part of the dispersant is increased, it is easy to suppress penetration of the solvent into the coating film and arrival of the coloring material.
  • the graft copolymer used in the present invention other than the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II), within a range that does not impair the effects of the present invention.
  • it may have other structural units.
  • an ethylenically unsaturated double bond-containing monomer that can be copolymerized with the ethylenically unsaturated double bond-containing monomer from which the structural unit represented by the general formula (I) is derived is appropriately selected. can be copolymerized to introduce other structural units.
  • Other structural units copolymerized with the structural units represented by general formula (I) include, for example, structural units represented by general formula (III).
  • the content ratio of the structural unit is, at the time of production, the structural unit represented by the general formula (I), the structural unit represented by the general formula (II), and the structural unit represented by the general formula (II) when synthesizing the graft copolymer. It is calculated from the charged amount of the monomer that induces the structural unit represented by the general formula (III).
  • the weight average molecular weight Mw of the graft copolymer is preferably 4000 or more, more preferably 6000 or more, and even more preferably 8000 or more, from the viewpoint of dispersibility and dispersion stability. . On the other hand, it is preferably 50,000 or less, more preferably 30,000 or less, from the viewpoint of solvent resolubility.
  • the mass average molecular weight Mw in the present invention is a value measured by GPC (gel permeation chromatography).
  • the measurement was carried out using Tosoh's HLC-8120GPC, the elution solvent was N-methylpyrrolidone to which 0.01 mol/liter of lithium bromide was added, and the polystyrene standards for the calibration curve were Mw 377400, 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (Easi PS-2 series manufactured by Polymer Laboratories) and Mw 1090000 (manufactured by Tosoh), and the measurement column was TSK-GEL ALPHA-M ⁇ 2 (manufactured by Tosoh). is.
  • graft copolymer (Method for producing graft copolymer)
  • a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II) is produced. It is not particularly limited as long as it can be done.
  • a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II) for example, a monomer represented by the following general formula (Ia) and a polymerizable oligomer (macromonomer) comprising a group having an ethylenically unsaturated double bond at the end of the polymer chain as a copolymerization component, and copolymerizing to produce a graft copolymer. mentioned. If necessary, other monomers may also be used, and the graft copolymer can be produced using known polymerization means.
  • R 71 , A 1 , R 72 and R 73 are the same as in general formula (I).
  • the monomer represented by the general formula (Ia) and other monomers containing groups having ethylenically unsaturated double bonds are added to form a copolymer, after which the reactive groups contained in the copolymer and reactive groups that can react Polymer chains may be used to introduce polymer chains.
  • a functional group that reacts with the substituent is added.
  • a polymer chain may be introduced by reacting with a polymer chain contained therein.
  • a copolymer having a glycidyl group in the side chain is reacted with a polymer chain having a terminal carboxyl group, or a copolymer having an isocyanate group in the side chain is reacted with a polymer chain having a hydroxyl group at the terminal.
  • additives commonly used in polymerization such as polymerization initiators, dispersion stabilizers, and chain transfer agents, may be used.
  • each block in the block copolymer is not particularly limited, and examples thereof include AB block copolymers, ABA block copolymers, and BAB block copolymers. Among them, an AB block copolymer or an ABA block copolymer is preferable because of its excellent dispersibility.
  • the A block is a block that functions as a coloring material adsorption site and contains at least the structural unit represented by the general formula (I). At least part of the nitrogen sites of the structural units represented by the general formula (I) of the block copolymer and at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons form a salt. It may be a salt-type block copolymer.
  • the A block may have a structural unit other than the structural unit represented by general formula (I) within the scope of achieving the object of the present invention, and the structural unit represented by general formula (I) and Any structural unit that can be copolymerized can be contained. Specific examples thereof include structural units represented by the general formula (III).
  • the content ratio of the structural unit represented by general formula (I) in the A block in the block copolymer before salt formation is 50% by mass to 100% by mass with respect to the total mass of all structural units in the A block. preferably 80% by mass to 100% by mass, most preferably 100% by mass. This is because the higher the proportion of the structural unit represented by the general formula (I), the better the adsorptive power to the coloring material, and the better the dispersibility and dispersion stability of the block copolymer.
  • the content ratio of the structural unit is calculated from the charged mass when synthesizing the A block having the structural unit represented by the general formula (I).
  • the total content of all structural units of the A block including the structural unit represented by the general formula (I) is from the viewpoint of good dispersibility and dispersion stability. It is preferably 5% by mass to 60% by mass, more preferably 10% by mass to 50% by mass, based on the total mass of all structural units of the copolymer.
  • the content ratio of the structural unit represented by the general formula (I) in the block copolymer before salt formation is the total structural units of the block copolymer from the viewpoint of good dispersibility and dispersion stability. It is preferably 5% by mass to 60% by mass, more preferably 10% by mass to 50% by mass, based on the total mass of.
  • the content ratio of each structural unit in the block copolymer is calculated from the charged mass when synthesizing the block copolymer before salt formation.
  • the structural unit represented by the general formula (I) only needs to have an affinity with the colorant, and may consist of one type or may contain two or more types of structural units. good.
  • the B block is a block that functions as a solvent affinity site and contains at least a (meth)acrylate-derived structural unit.
  • (Meth)acrylate-derived structural units may be the same as those described above.
  • As the B block a monomer having an unsaturated double bond, which is copolymerizable with the monomer from which the structural unit represented by the general formula (I) is derived, is appropriately selected depending on the solvent so as to have solvent affinity. It is preferably used selectively. As a guideline, it is preferable to introduce the B block so that the solubility of the copolymer at 23° C. in the solvent used in combination is 20 (g/100 g solvent) or more.
  • the structural unit constituting the B block part may consist of one type, or may contain two or more types of structural units. Examples of structural units contained in the B block include structural units represented by the general formula (III).
  • the ratio of the unit number m of the structural unit represented by the general formula (I) to the unit number n of other structural units constituting the solvent-affinity block portion is m/ n is preferably in the range of 0.01 to 1, and more preferably in the range of 0.05 to 0.7 in terms of dispersibility and dispersion stability of the colorant.
  • the A block containing the structural unit represented by the general formula (I) and the B block containing the structural unit derived from the carboxy group-containing monomer and the (meth)acrylate-derived structural unit and from the group consisting of at least part of the nitrogen moiety of the structural unit represented by the general formula (I) of the block copolymer, an organic acid compound, and a halogenated hydrocarbon Contains at least one salt-type block copolymer formed with at least one selected salt, and the block copolymer and at least one of the salt-type block copolymers have an acid value of 1 mgKOH/g to 18 mgKOH.
  • the B block in this case contains a (meth)acrylate-derived structural unit as an essential component, and may be the same as the B block of WO 2016/104493.
  • the carboxy group-containing monomer a monomer that can be copolymerized with a monomer having a structural unit represented by general formula (I) and that contains an unsaturated double bond and a carboxy group can be used.
  • monomers include (meth)acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl esters, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimers.
  • addition reaction products of monomers having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and cyclic anhydrides such as maleic anhydride, phthalic anhydride and cyclohexanedicarboxylic anhydride, ⁇ -carboxy-polycaprolactone Mono (meth) acrylate and the like can also be used.
  • Acid anhydride group-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride may also be used as a precursor of the carboxy group.
  • (meth)acrylic acid is particularly preferable from the viewpoint of copolymerizability, cost, solubility, glass transition temperature, and the like.
  • the content of structural units derived from the carboxyl group-containing monomer may be appropriately set so that the acid value of the block copolymer is within the specific acid value range. Although not limited, it is preferably 0.05% by mass to 4.5% by mass, and 0.07% by mass to 3.7% by mass, based on the total mass of all structural units of the block copolymer. is more preferred.
  • the content of the structural unit derived from the carboxyl group-containing monomer is at least the lower limit value, the effect of suppressing development residue is exhibited, and when it is at most the upper limit value, development adhesion is deteriorated and solvent resolubility is reduced. It can prevent deterioration.
  • the structural unit derived from the carboxyl group-containing monomer may have the specific acid value, and may consist of one type or may contain two or more types of structural units.
  • the B block of the block copolymer contains a structural unit derived from a hydroxyl group-containing monomer from the viewpoint of improving development adhesion.
  • the B block contains a structural unit derived from a hydroxyl group-containing monomer, the development speed is further improved.
  • the hydroxyl group here refers to an alcoholic hydroxyl group bonded to an aliphatic hydrocarbon.
  • a monomer containing an unsaturated double bond and a hydroxyl group that is copolymerizable with the monomer that derives the structural unit represented by general formula (I) can be used.
  • Such monomers include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerin mono (meth) Acrylate, polyethylene glycol mono(meth)acrylate, ⁇ -caprolactone 1 mol adduct of 2-hydroxyethyl(meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate and the like.
  • one or more selected from the group consisting of 2-hydroxyethyl methacrylate and 2-hydroxy-3-phenoxypropyl (meth)acrylate is preferable from the viewpoint of improving development adhesion.
  • the content of structural units derived from hydroxyl group-containing monomers in the block copolymer before salt formation is preferably 1% by mass or more, preferably 2% by mass, based on the total mass of all structural units of the block copolymer. It is more preferably at least 3% by mass, even more preferably at least 3% by mass, and particularly preferably at least 4% by mass. When it is at least the above lower limit value, the development adhesion can be made preferable. Similarly, it is preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, and particularly preferably 40% by mass or less.
  • the content ratio of the structural unit is calculated from the charged mass when synthesizing the block copolymer before salt formation.
  • the lower limit of the acid value of at least one of the block copolymer and the salt-type block copolymer is preferably 1 mgKOH/g or more, more preferably 2 mgKOH/g or more, from the viewpoint of the effect of suppressing development residue. is more preferable.
  • the upper limit of the acid value of at least one of the block copolymer and the salt-type block copolymer is 18 mgKOH/g or less from the viewpoint of preventing deterioration of development adhesion and solvent re-solubility. preferably 16 mgKOH/g or less, and even more preferably 14 mgKOH/g or less.
  • the acid value of at least one of the block copolymer and the salt-type block copolymer can be determined by the method described in WO2016/104493.
  • the glass transition temperature of at least one of the block copolymer and the salt-type block copolymer is preferably 30° C. or higher, more preferably 32° C. or higher, more preferably 35° C. or higher, from the viewpoint of development adhesion. . On the other hand, the temperature is preferably 200° C. or less from the viewpoint of operability during use, such as facilitating accurate weighing.
  • the glass transition temperature of at least one of the block copolymer and the salt-type block copolymer is determined by differential scanning calorimetry (DSC) according to JIS K7121. When two or more peaks indicating the glass transition temperature are observed, the peak area, that is, the peak having the largest area of the portion projecting from the base line of the obtained chart is taken as the representative value of the glass transition temperature.
  • the mass-average molecular weight Mw of the block copolymer is not particularly limited, but is preferably from 1000 to 20000, more preferably from 2000 to 15000, from the viewpoint of improving colorant dispersibility and dispersion stability. It is more preferably 3,000 to 12,000.
  • the weight average molecular weight (Mw) can be measured in the same manner as described above.
  • the total proportion of structural units derived from (meth)acrylate is 100% by mass of all structural units in the B block in the block copolymer from the viewpoint of dispersion stability, solvent resistance, and compatibility with the photoinitiator.
  • the content is preferably 60% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.
  • the total proportion of structural units derived from (meth)acrylate is 100 mass% when all the structural units in the B block are 100 mass%. %.
  • the B block contains structural units derived from the carboxy group-containing monomer
  • the total proportion of the structural units derived from (meth)acrylate is different from the structural units derived from the carboxy group-containing monomer in the B block.
  • the unit is 100% by mass, it may be 100% by mass.
  • the total content of all structural units of the B block is, from the viewpoint of good dispersibility and dispersion stability, relative to the total mass of all structural units of the block copolymer. , preferably 5% to 60% by mass, more preferably 10% to 50% by mass.
  • the content ratio of the structural unit represented by the general formula (III) is the total mass of all structural units of the block copolymer from the viewpoint of improving the dispersibility of the coloring material. It is preferably 40% by mass to 95% by mass, more preferably 50% by mass to 90% by mass. The content ratio of the structural unit is calculated from the charged mass when synthesizing the block copolymer before salt formation.
  • the (meth)acrylate copolymer containing the structural unit represented by the general formula (I) is a copolymer having an amine value of 40 mgKOH/g to 120 mgKOH/g. It is preferable from the viewpoint of improving brightness and contrast without depositing foreign substances. When the amine value is within the above range, the viscosity stability over time and heat resistance are excellent, and alkali developability and solvent re-solubility are also excellent.
  • the (meth)acrylate copolymer containing the structural unit represented by the general formula (I) preferably has an amine value of 80 mgKOH/g or more, particularly 90 mgKOH/g or more. is more preferable.
  • the amine value of the (meth)acrylate copolymer containing the structural unit represented by the general formula (I) is preferably 110 mgKOH/g or less, and 105 mgKOH/g.
  • the following are more preferable.
  • the amine value refers to the number of mg of potassium hydroxide equivalent to perchloric acid required to neutralize the amine component contained in 1 g of the sample, and can be measured by the method defined in JIS-K7237. When measured by this method, even if the amino group forms a salt with the organic acid compound in the dispersant, the organic acid compound usually dissociates, so the block copolymer itself used as the dispersant can be measured.
  • the content ratio (mol%) of each structural unit in the copolymer in the dispersant can be obtained from the amount of raw materials charged at the time of production, and can be measured using an analyzer such as NMR. Also, the structure of the dispersant can be measured using NMR, various mass spectrometry, and the like. In addition, if necessary, the dispersant is decomposed by thermal decomposition or the like, and the obtained decomposition product is subjected to high performance liquid chromatography, gas chromatograph mass spectrometer, NMR, elemental analysis, XPS / ESCA, TOF-SIMS, etc. can ask.
  • the content of the dispersant is not particularly limited as long as it is selected so as to be excellent in the dispersibility and dispersion stability of the colorant, but in the photosensitive green resin composition
  • it is preferably in the range of 2% by mass to 30% by mass, more preferably 3% by mass to 25% by mass, based on the total solid content.
  • the dispersibility and dispersion stability of the coloring material are excellent, and the storage stability of the photosensitive green resin composition is excellent.
  • developability will become favorable.
  • the content of the dispersant is, for example, preferably 2% to 25% by mass, more preferably 2% by mass to 25% by mass, based on the total solid content of the photosensitive green resin composition. It is within the range of 3% by mass to 20% by mass.
  • the photosensitive green resin composition of the present invention preferably further contains a thiol compound from the viewpoint of improving solvent resistance after low-temperature heat treatment and substrate adhesion.
  • thiol compounds include monofunctional thiol compounds having one thiol group and polyfunctional thiol compounds having two or more thiol groups. From the viewpoint of suppressing line width shift and improving substrate adhesion, it is more preferable to use a monofunctional thiol compound having one thiol group.
  • Examples of monofunctional thiol compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3-mercapto propionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate and the like.
  • polyfunctional thiol compounds include 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2, 4,6(1H,3H,5H)-trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), di pentaerythritol hexakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate) and the like.
  • the thiol compound may be used alone or in combination of two or more. Among them, 2-mercaptobenzoxazole or 2-mercaptobenzothiazole improves solvent resistance and substrate adhesion after low-temperature heat treatment. It is preferable from the point of view.
  • the content of the thiol compound is usually in the range of 0.5% by mass to 10% by mass, preferably 1% by mass to 5% by mass, based on the total solid content of the photosensitive green resin composition. If it is at least the above lower limit, the solvent resistance after low-temperature heat treatment and substrate adhesion are excellent. On the other hand, when it is the above upper limit or less, the photosensitive green resin composition of the present invention tends to have good developability and suppressed line width shift.
  • the photosensitive green resin composition of the present invention may further contain various additives.
  • additives include antioxidants, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, antifoaming agents, silane coupling agents, ultraviolet absorbers, adhesion promoters, and the like.
  • specific examples of surfactants and plasticizers include those described in JP-A-2013-029832.
  • the photosensitive green resin composition of the present invention further contains an antioxidant from the viewpoint of suppressing the amount of line width shift of the cured film.
  • the photosensitive green resin composition of the present invention for example, by containing an antioxidant in combination with the compound represented by the general formula (A), excessive without impairing the curability when forming a cured film Since the radical chain reaction can be controlled, when forming a fine line pattern, the linearity is further improved, and the ability to form the fine line pattern according to the design of the mask line width is improved. In addition, the heat resistance can be improved, and the decrease in luminance after exposure and post-baking can be suppressed, so the luminance can be improved.
  • the antioxidant used in the present invention is not particularly limited, and may be appropriately selected from those conventionally known.
  • antioxidants include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, and the like. It is preferable to use a hindered phenol-based antioxidant from the viewpoint of improving the ability to form a fine line pattern according to the design of the line width and from the viewpoint of heat resistance. It may be a latent antioxidant as described in WO2014/021023.
  • Hindered phenol-based antioxidants include, for example, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: trade name: IRGANOX1010, manufactured by BASF), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4,6-tris(4-hydroxy-3 ,5-di-tert-butylbenzyl)mesitylene (trade name: Irganox 1330, manufactured by BASF), 2,2′-methylenebis(6-tert-butyl-4-methylphenol) (trade name: Sumilizer MDP-S, Sumitomo Chemical), 6,6′-thiobis(2-tert-butyl-4-methylphenol) (trade name: Irganox 1081, manufactured by BASF), 3,5-di-
  • pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX1010, manufactured by BASF) is preferable from the viewpoint of heat resistance and light resistance. .
  • the content of the antioxidant is usually 0.1% by mass to 10.0% by mass, preferably 0.5% by mass to 5.0% by mass, based on the total solid content of the photosensitive green resin composition. Within range. If it is at least the above lower limit, the ability to form a fine line pattern as designed with a mask line width is improved, and the heat resistance is excellent. On the other hand, if it is below the said upper limit, it will be easy to make the photosensitive green resin composition of this invention into a highly sensitive photosensitive green resin composition.
  • silane coupling agents examples include KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-903, KBE-903, KBM573, KBM-403, KBE-402, KBE-403 , KBM-303, KBM-802, KBM-803, KBE-9007, X-12-967C (manufactured by Shin-Etsu Silicone Co., Ltd.) and the like.
  • KBM-502, KBM-503, KBE-502, KBE-503 and KBM-5103 having a methacrylic group or an acrylic group are preferable from the viewpoint of adhesion to SiN substrates.
  • the content of the silane coupling agent is usually 0.05% by mass to 10.0% by mass, preferably 0.1% by mass to 5.0% by mass, relative to the total solid content in the photosensitive green resin composition. %. If it is more than the said lower limit and below the said upper limit, the board
  • Method for producing a photosensitive green resin composition of the present invention a colorant, a photopolymerizable compound, a photoinitiator, and optionally various additive components, by mixing using a known mixing means , can be prepared.
  • the photosensitive green resin composition of the present invention contains a colorant, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent, and various additive components optionally used
  • a method for preparing the resin composition for example, (1) first, a coloring material and a dispersing agent are added to a solvent to prepare a coloring material dispersion, and an alkali-soluble resin and an alkali-soluble resin are added to the dispersion; A method of mixing a photopolymerizable compound, a photoinitiator, and various additive components that are optionally used; A method of simultaneously adding and mixing an initiator and various additive components that are optionally used; (4) adding a coloring material, a dispersant, and an alkali-soluble resin to a solvent to prepare a coloring material dispersion; and a method of adding and mixing an alkali-soluble resin, a solvent, a photopolymerizable compound, a photoinitiator, and
  • the method for preparing the colorant dispersion can be appropriately selected from conventionally known dispersion methods. For example, (1) a dispersant is mixed with a solvent in advance and stirred to prepare a dispersant solution, and then an organic acid compound is mixed as necessary to form a salt between the amino group of the dispersant and the organic acid compound.
  • a method of mixing this with a coloring material and, if necessary, other components and dispersing using a known stirrer or disperser (2) mixing and stirring a dispersant in a solvent to prepare a dispersant solution; , a coloring material and, if necessary, an organic acid compound, and if necessary, other components are mixed and dispersed using a known stirrer or disperser; (3) a dispersant is mixed with a solvent and stirred; , Prepare a dispersant solution, then mix the coloring material and other components as necessary, make a dispersion using a known stirrer or disperser, and then add an organic acid compound as necessary. methods and the like.
  • dispersing machines for dispersing include roll mills such as two-roll and three-roll roll mills, ball mills such as ball mills and vibrating ball mills, bead mills such as paint conditioners, continuous disk-type bead mills, and continuous annular-type bead mills.
  • the diameter of the beads used is preferably 0.03 mm to 2.00 mm, more preferably 0.10 mm to 1.0 mm.
  • the photosensitive green resin composition according to the present invention has good solvent resistance even at low temperature heat treatment, and can form a colored layer with a good pattern shape, so it can be suitably used for color filters.
  • it can be suitably used for low-temperature heat treatment applications such as 130 ° C. or lower, further 100 ° C. or lower or 90 ° C. or lower, in which a color filter is formed directly on a substrate on which an element with low heat resistance such as an organic light-emitting device is formed. It can be suitably used for a cured film formed on an organic light emitting device.
  • the photosensitive green resin composition according to the present invention can be used for a cured film formed on an organic light emitting device, it is suitable for forming a colored cured film as a substitute for a circularly polarizing plate having an effect of suppressing reflection of external light. Used.
  • the cured film of the photosensitive green resin composition according to the present invention is used in place of a circularly polarizing plate, it can be a display device that does not contain a polarizing plate, so the photosensitive green resin composition according to the present invention is , is suitably used for display devices that do not contain a polarizing plate.
  • the photosensitive green resin composition according to the present invention is a photosensitive green resin composition used for a cured film formed on an organic light-emitting element, it can be It is suitable for use in organic light-emitting display devices with improved flexibility.
  • the cured product according to the present invention is a cured product of the photosensitive green resin composition according to the present invention.
  • the cured product according to the present invention is obtained, for example, by forming a coating film of the photosensitive green resin composition according to the present invention, drying the coating film, exposing, and developing as necessary, and heat treatment. be able to.
  • the methods of forming, exposing, developing, and heat-treating the coating film may be, for example, the same methods as those used in the formation of the colored layer provided in the color filter according to the present invention, which will be described later.
  • the cured product according to the present invention has good solvent resistance and good pattern shape even when the heat treatment is performed at a low temperature of 130° C. or lower, 100° C. or lower, or 90° C. or lower.
  • the cured product according to the present invention has good solvent resistance even when subjected to low-temperature heat treatment, and has a good pattern shape. Used.
  • the color filter according to the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is the photosensitive green resin composition according to the present invention. It is a hardened material.
  • FIG. 1 is a schematic cross-sectional view showing an example of the color filter of the present invention.
  • the color filter 10 of the present invention has a substrate 1, a light shielding portion 2 and a colored layer 3. As shown in FIG.
  • At least one of the colored layers used in the color filter of the present invention is a colored layer that is a cured product of the photosensitive green resin composition according to the present invention.
  • the colored layer is usually formed in the opening of the light shielding part on the substrate, which will be described later, and is usually composed of colored patterns of three or more colors.
  • the arrangement of the colored layers is not particularly limited, and may be a general arrangement such as a stripe type, mosaic type, triangle type, four-pixel arrangement type, or the like. Moreover, the width, area, etc. of the colored layer can be arbitrarily set.
  • the thickness of the colored layer can be appropriately controlled by adjusting the coating method, solid content concentration and viscosity of the photosensitive green resin composition, and is preferably in the range of 1 to 5 ⁇ m.
  • the colored layer can be formed, for example, by the following method.
  • a coating method such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, or a die coating method.
  • the spin coating method and the die coating method can be preferably used.
  • After drying the wet coating film using a hot plate or an oven it is exposed to light through a mask of a predetermined pattern, and the alkali-soluble resin and the polyfunctional monomer are photopolymerized and cured. It is used as a coating film.
  • Light sources used for exposure include, for example, ultraviolet light from low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and electron beams.
  • the amount of exposure is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
  • heat treatment may be performed.
  • the heating conditions are appropriately selected depending on the mixing ratio of each component in the photosensitive green resin composition to be used, the thickness of the coating film, and the like.
  • a coating film is formed in a desired pattern by developing with a developer to dissolve and remove the unexposed portions.
  • a developer a solution obtained by dissolving an alkali in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to this alkaline solution.
  • a general method can be adopted as the developing method. After development, the developer is usually washed and the cured coating film of the photosensitive green resin composition is dried to form a colored layer. In addition, you may heat-process in order to fully harden a coating film after development processing. The heating conditions are not particularly limited, and are appropriately selected according to the application of the coating film.
  • the heat treatment in the manufacturing process for forming the colored layer directly on the element substrate is preferably performed at 30° C. or higher and 100° C. or lower, more preferably 35° C. or higher and 95° C. or lower, and 40° C. or higher and 90° C. or lower. It is even more preferable to do so.
  • the colored layer is formed in a desired pattern by a conventionally known method for forming a patterned coating film such as an inkjet method. After the formation, the film is exposed to light and a photopolymerization reaction of a photopolymerizable compound or the like is performed to form a cured coating film. In the same manner as described above, heat treatment may be performed in order to promote the polymerization reaction after exposure.
  • the light-shielding portion in the color filter of the present invention is formed in a pattern on a substrate, which will be described later, and can be the same as those used as light-shielding portions in general color filters.
  • the pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape, a matrix shape, and the like.
  • the light shielding portion may be a metal thin film of chromium or the like formed by a sputtering method, a vacuum deposition method, or the like.
  • the light-shielding portion may be a resin layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, or organic pigments in a resin binder.
  • a method of patterning by development using a photosensitive resist a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring a photosensitive resist, and the like are available. be.
  • the film thickness of the light-shielding portion is set to about 0.2 to 0.4 ⁇ m in the case of a metal thin film, and is set to about 0.5 to 2 ⁇ m in the case of a black pigment dispersed or dissolved in a binder resin. be done.
  • a transparent substrate, a silicon substrate, and a transparent substrate or a silicon substrate on which an aluminum, silver, silver/copper/palladium alloy thin film or the like is formed are used.
  • Other color filter layers, resin layers, transistors such as TFTs, circuits, and the like may be formed on these substrates.
  • the substrate may be an element substrate such as an organic light emitting element which will be described later.
  • the transparent substrate in the color filter of the present invention is not particularly limited as long as it is transparent to visible light, and transparent substrates used in general color filters can be used. Specifically, transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible materials such as transparent resin films, optical resin plates, and flexible glass. material.
  • transparent resin films and optical resin plates examples include polyethylene terephthalate (PET) films, polyimide films, and polycarbonate films. It is preferably used.
  • PET polyethylene terephthalate
  • the thickness of the transparent substrate is not particularly limited, a thickness of about 100 ⁇ m to 1 mm, for example, can be used depending on the application of the color filter of the present invention.
  • the color filter of the present invention may be formed with, for example, an overcoat layer, a transparent electrode layer, an alignment film, columnar spacers, etc., in addition to the above substrate, light shielding portion and colored layer.
  • the color filter of the present invention can be used as a substitute for a circularly polarizing plate that prevents reflection of external light.
  • Display Device A display device according to the present invention includes the color filter according to the present invention.
  • the configuration of the display device is not particularly limited, and can be appropriately selected from conventionally known display devices, such as liquid crystal display devices and organic light-emitting display devices.
  • FIG. 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention.
  • a liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer formed between the color filter 10 and the counter substrate 20.
  • the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, and may have a known configuration as a liquid crystal display device generally using color filters.
  • the driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for liquid crystal display devices can be adopted. Examples of such driving methods include the TN method, the IPS method, the OCB method, and the MVA method. Any of these methods can be suitably used in the present invention. Also, the counter substrate can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention. Further, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used according to the driving method of the liquid crystal display device of the present invention.
  • a method for forming the liquid crystal layer a method generally used as a method for manufacturing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method. After the liquid crystal layer is formed by the above method, the liquid crystal cell is gradually cooled to room temperature, thereby aligning the enclosed liquid crystal.
  • FIG. 3 is a schematic diagram showing an example of the organic light-emitting display device of the present invention.
  • the organic light emitting diode display 100 of the present invention has an organic light emitting element 80 and a sealing layer 90 formed on a substrate 50, and a color filter 10 is formed thereon.
  • the substrate 50 may be a flexible substrate on which a TFT is formed.
  • the color filter 10 may be a color filter substituting for a circular polarizer.
  • a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light emitting layer 74, an electron injection layer 75, and a cathode 76 are sequentially formed on the substrate 50. and the like.
  • the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, the cathode 76, and other structures in the organic light emitting element 80 can be appropriately used known ones.
  • the sealing layer 90 can use a well-known thing suitably.
  • the organic light-emitting display device 100 manufactured in this way can be applied to, for example, a passive drive type organic EL display and an active drive type organic EL display.
  • the organic light-emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and may have a known configuration as an organic light-emitting display device generally using color filters.
  • the display device according to the present invention may have a cured film of the photosensitive green resin composition according to the present invention on the organic light-emitting element.
  • a display device according to the present invention since the cured film of the photosensitive green resin composition according to the present invention is formed on the organic light-emitting element, an external circularly polarizing plate, An external color filter substrate is unnecessary and may be absent.
  • Such a display device according to the present invention uses the photosensitive green resin composition according to the present invention to form a cured film on the organic light-emitting element. Since it does not have a substrate that is used as an attached color filter substrate, it has improved thinness and flexibility.
  • FIG. 4 is a schematic cross-sectional view showing another example of a display device having an organic light-emitting device according to the present invention.
  • a display device 200 according to the present invention includes an element substrate 130 having an organic light emitting element, and an external light reflection preventing film including colored cured films (109R, 109G, 109B) on the element substrate 130.
  • a membrane 120 is provided, and a sealing membrane 111 is provided thereon.
  • a device substrate 130 having the organic light emitting device includes a substrate 101 on which thin film transistors (TFTs) 102, which are driving devices, are arranged so as to correspond to respective sub-pixels, and a sealing film 103 is provided thereon.
  • An electrode 104 (anode) corresponding to each sub-pixel and partition walls 105 partitioning each sub-pixel are provided on 103, and organic light-emitting elements (106R, 106G , 106B) are arranged, and an electrode 107 (cathode) is further provided on the organic light-emitting elements (106R, 106G, 106B).
  • the element substrate 130 having the organic light emitting elements further includes a sealing layer 108 covering the organic light emitting elements from thereon.
  • a display device 200 according to the present invention in FIG. 4 further includes a cover material 113 on a sealing film 111 with a transparent adhesive layer 112 interposed therebetween.
  • the display device 200 according to the present invention has a known structure such as a touch sensor layer including an insulating film and a transparent electrode layer on the sealing film 111 and a hard coat layer on the touch sensor layer. may be further provided as appropriate.
  • the layers of the colored cured films (109R, 109G, 109B) and the light shielding part 110 provided on the element substrate 130 having the organic light emitting element are used as the external light antireflection film 120.
  • the external light antireflection film used in the present invention does not include a separate substrate such as an external circularly polarizing plate or an external color filter substrate, and can improve thinness and flexibility.
  • the colors (106R, 106G, 106B) of the sub-pixels of the organic light-emitting element and the colored cured films (109R, 109G, 109B) are preferably adjusted to be of the same kind.
  • the colored cured film provided on the organic light-emitting element blocks external light except for the color originally emitted by the organic light-emitting element, and does not block the light emitted by the organic light-emitting element, thereby improving the light utilization efficiency. It is possible to suppress the external light reflection without lowering it.
  • the cured film of the photosensitive green resin composition according to the present invention may be the green cured film (109G) among the three colored cured films (109R, 109G, 109B).
  • a substrate 101 used in a display device according to the present invention a thin film transistor (TFT) 102 as a driving element, a sealing film 103, an electrode 104 (anode), a partition wall 105 partitioning each sub-pixel, and an organic light-emitting element constituting a sub-pixel. (106R, 106G, 106B), the electrode 107 (cathode), etc. can be used by appropriately selecting known configurations.
  • the organic light-emitting device may have known structures such as a hole injection layer, a hole transport layer, an electron injection layer, etc., in addition to the light-emitting layer.
  • the sealing layer 108 on the organic EL element used in the display device according to the present invention is composed of an inorganic film, an organic film, and a multilayer film in which these are laminated. It is preferable to use a multilayer film because it has a high effect of suppressing penetration of moisture and oxygen. Specific examples thereof include a multilayer film in which an inorganic film such as a metal film, a metal oxide film, SiOx, SiNx, and an organic film are laminated.
  • At least one of the colored cured films used in the display device according to the present invention is a cured film of the photosensitive green resin composition according to the present invention.
  • the colored cured film is usually formed in an opening of a light shielding part, which will be described later, on the sealing layer 108 on the organic light emitting element, and is usually composed of colored patterns of three or more colors. These may be colored patterns similar to (106R, 106G, 106B) of the sub-pixels of the organic light emitting device.
  • the arrangement of the colored cured films (109R, 109G, 109B) may be, for example, a general arrangement such as a stripe type, mosaic type, triangle type, or 4-pixel arrangement type. Also, the width, area, etc.
  • the thickness of the colored cured film is appropriately controlled by adjusting the coating method, solid content concentration and viscosity of the photosensitive green resin composition, and is usually in the range of 1 ⁇ m to 5 ⁇ m.
  • the light shielding part 110 used in the display device according to the present invention is usually formed in a pattern on the sealing layer 108 on the organic light emitting element, and is used as a light shielding part in a general color filter.
  • the pattern shape of the light shielding portion may be appropriately selected according to the shape of the colored cured film, and examples thereof include a stripe shape and a matrix shape.
  • the light shielding portion may be a metal thin film of chromium or the like formed by a sputtering method, a vacuum deposition method, or the like.
  • the light-shielding portion may be a resin layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, or organic pigments in a resin binder.
  • a resin layer containing light-shielding particles a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring a photosensitive resist, and the like are available. be.
  • the film thickness of the light-shielding portion is set to about 0.2 ⁇ m to 0.4 ⁇ m in the case of a metal thin film, and is set to about 0.5 ⁇ m to 2 ⁇ m in the case of a black pigment dispersed or dissolved in a binder resin. be done.
  • known materials can be appropriately selected and used. Also, for the transparent adhesive layer 112 provided on the sealing film 111 and the cover material 113, known materials can be appropriately selected and used. In the present invention, even when glass is used as the cover material, glass can be used as the cover material because the green cured film has good weather resistance and the reduction in transmittance is suppressed.
  • the display device according to the present invention is not limited to the configuration shown in FIG. 4, and may further include the configuration of a display device having a known organic light-emitting element. .
  • Method for producing a laminate of an organic light-emitting element and an anti-reflection film for external light comprises: A step of forming a coating film by applying the photosensitive green resin composition according to the present invention on the organic light emitting device; a step of irradiating the coating film with light; A post-baking step of heating the film after the light irradiation, and By including the step of developing the film after the light irradiation, A step of forming a cured film of the photosensitive green resin composition according to the present invention on the organic light emitting device. Each step will be described below.
  • the photosensitive green resin composition according to the present invention on the organic light-emitting element, it is not necessary to apply the composition on the organic light-emitting element adjacent to the organic light-emitting element.
  • the electrodes 107 and the permeation of moisture and oxygen are usually further suppressed on the sub-pixels (106R, 106G, 106B) of the organic light emitting elements.
  • the sealing layer 108 is provided for the purpose, it may be applied onto the organic light-emitting element through these electrodes, the sealing layer, and the like.
  • the light shielding portion 110 is provided in advance on the sealing layer 108 by a known method as exemplified above, and the colored cured films (109R, 109G, 109B) are formed in the openings of the light shielding portion 110. It may be applied as follows.
  • a coating means such as a die coating method, the photosensitive green resin composition of the present invention described above, on the organic light emitting device to apply.
  • a spin coating method and a die coating method can be preferably used. Then, the wet coating film is dried using a hot plate, an oven, or the like to form a coating film.
  • the obtained coating film is irradiated with light (exposure) through a mask of a predetermined pattern, and the photopolymerizable compound and, if necessary, the alkali-soluble resin, etc. are photopolymerized.
  • Light sources used for exposure include, for example, ultraviolet light from low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, electron beams, and the like. The amount of exposure is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
  • a post-baking step of heating the film after the light irradiation may be performed.
  • the heating conditions may be appropriately selected according to the mixing ratio of each component in the photosensitive green resin composition to be used, the thickness of the coating film, and the like.
  • the post-baking process may be performed on the film after the light irradiation before the development process described later, after the development process, or before and after the development process.
  • the heating temperature in the post-baking step is preferably 130° C. or less because the colored cured film is directly formed on the element substrate having the organic light-emitting element.
  • the heating temperature is more preferably 100° C. or lower, still more preferably 90° C. or lower.
  • the heating temperature may be 30° C. or higher, 35° C. or higher, or 40° C. or higher.
  • the film after the light irradiation to be developed may be a film after post-baking.
  • a coating film is formed in a desired pattern by developing with a developer to dissolve and remove the unexposed portions.
  • a developer a solution obtained by dissolving an alkali in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to this alkaline solution.
  • a general method can be adopted as the developing method.
  • the heating temperature in this post-baking step is preferably 130° C. or less, more preferably 100° C. or less, and even more preferably 90° C. or less. . Also, the heating temperature may be 30° C. or higher, 35° C. or higher, or 40° C. or higher.
  • light irradiation may be additionally performed after development processing or in order to further harden the film after post-baking.
  • the mass average molecular weight (Mw) of the copolymer before salt formation was determined as a standard polystyrene equivalent value by GPC (gel permeation chromatography) according to the measurement method described in the specification of the present invention.
  • EEMA 1-ethoxyethyl methacrylate
  • TMSMA 2-(trimethylsilyloxy)ethyl methacrylate
  • EHMA 2-ethylhexyl methacrylate
  • BMA n-butyl methacrylate
  • BzMA benzyl methacrylate
  • MMA methyl methacrylate
  • DMMA dimethylaminoethyl methacrylate
  • block copolymer PGMEA solution was reprecipitated in hexane, filtered, and purified by vacuum drying to obtain block copolymer 1 (amine value: 95 mg KOH/ g, acid value 8 mgKOH/g, Tg 38°C).
  • the weight average molecular weight Mw was 7,730.
  • Example 1 Production of photosensitive green resin composition G-1)
  • Production of Colorant Dispersion B (1) In a 225 mL mayonnaise bottle, 64.9 parts by mass of PGMEA, 13.5 parts by mass of the alkali-soluble resin A solution of Preparation Example 1 (solid content: 40% by mass), Synthesis Example 1 9.2 parts by mass of a PGMEA solution (solid content: 35% by mass) of block copolymer 1 was added and stirred. 0.39 parts by mass of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Industries, Ltd.) was added thereto, and the mixture was stirred at room temperature for 30 minutes.
  • PPA phenylphosphonic acid
  • the block copolymer 1 is salt-formed with phenylphosphonic acid to form a salt-type block copolymer 1 .
  • Example 2 to 14 Production of photosensitive green resin compositions G-2 to G-14
  • Example 1 as shown in Table 1, by changing the type and / or mass ratio of the blue pigment, the yellow pigment and the green pigment, the alkali-soluble resin A solution, the polyfunctional monomer, and the formula (A-2)
  • photosensitive green resin compositions G-2 to G-14 were obtained.
  • C.I. I. Pigment Blue 15:6 B15:6)
  • C.I. I. Pigment Blue 15:3 B15:3
  • Comparative Examples 1 to 4 Production of Comparative Photosensitive Green Resin Compositions CG-1 to CG-4)
  • the green pigment halogenated phthalocyanine pigment
  • Comparative photosensitive green resin compositions CG-1 to CG-4 were obtained in the same manner as the photosensitive green resin compositions G-6, G-7, G-13 or G-14 except for the above.
  • Comparative Examples 5-6 Production of comparative photosensitive green resin compositions CG-5-CG-6)
  • Example 1 As shown in Table 1, in the same manner as in Examples 1 and 2 of Patent Document 2 (JP 2011-242568 A), the type and / or mass ratio of the blue pigment and the yellow pigment
  • the type of initiator Irgacure 907 (907, manufactured by BASF) and Kayacure DETX-S (DETX, manufactured by Nippon Kayaku) at a mass ratio of 2: 1
  • Comparative photosensitive green resin compositions CG-5 to CG-6 were obtained in the same manner as the photosensitive green resin composition G-1, except that the colorant concentration was changed.
  • Pigment Blue 16 (B16) colorant dispersion was prepared by C.I. I. Pigment Blue 15:4 (B15:4) was added to C.I. I. A colorant dispersion B(4) was obtained in the same manner as the colorant dispersion B(1), except that Pigment Blue 16 (B16) was used.
  • Comparative Examples 7 to 10 Production of comparative photosensitive green resin compositions CG-7 to CG-10)
  • Example 1 As shown in Table 1, the types of blue pigment and yellow pigment and / Or the mass ratio and the type of initiator (Irgacure OXE02 (OXE02, manufactured by BASF) were changed, and the amount of components other than the pigment was changed to the color material concentration shown in Table 1.
  • Photosensitive green resin Comparative photosensitive green resin compositions CG-7 to CG-10 were obtained in the same manner as composition G-1.
  • the photosensitive green resin composition obtained in each example and each comparative example is finally obtained on a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") using a spin coater. After coating so that the cured film had a thickness of 3.0 ⁇ m, it was dried at 80° C. for 3 minutes using a hot plate to form a coating film on the substrate. This coating film is exposed to ultraviolet rays of 50 mJ/cm 2 using an ultra-high pressure mercury lamp through a photomask (chromium mask) having a pattern with an opening size of 2 ⁇ m to 100 ⁇ m for forming independent fine lines. A postcoat was formed.
  • a photomask chromium mask
  • the transmission spectrum of 380 nm to 780 nm of the cured film is measured using a microscopic spectrometer (OSP-SP200, manufactured by Olympus), and the minimum transmittance of 360 nm to 370 nm and its wavelength, the maximum transmittance of 380 nm to 480 nm, and the maximum transmittance of 510 nm to 550 nm.
  • the maximum transmittance and minimum transmittance of , the maximum transmittance of 580 nm to 700 nm, and the difference between two wavelengths at which the peak showing the maximum transmittance in the wavelength range of 380 nm to 700 nm has half the maximum transmittance Calculation was performed to obtain the half width.
  • ⁇ Cross-sectional shape evaluation of fine line pattern colored layer The cross-sectional shape in the thickness direction of the resulting colored layer in the form of an independent fine line pattern was observed with a scanning electron microscope (manufactured by Shimadzu Corporation, super scan model 220, magnification of 10,000 times). The taper angle ( ⁇ 1) of the cross-sectional shape (see FIG. 5) was evaluated.
  • the taper angle ( ⁇ 1) is 15 degrees or more and less than 100 degrees
  • Comparative Examples 1 to 4 in which the green pigment (halogenated phthalocyanine pigment) was changed to be used in an amount exceeding 10% by mass in the total amount of the coloring material, when a cured film was formed with a film thickness of 3.0 ⁇ m, it was 360 nm to 370 nm. was less than 0.7%, and the solvent resistance and pattern shape of the cured film subjected to the low-temperature heat treatment were inferior.
  • Comparative Examples 5 and 6 which were the same blue pigment and yellow pigment types and / or mass ratios as in Examples 1 and 2 of Patent Document 2 (JP 2011-242568), respectively, cured at a film thickness of 3.0 ⁇ m.
  • Examples 1 to 14 which are the photosensitive green resin compositions according to the present invention, when a cured film is formed with a film thickness of 3.0 ⁇ m, the spectral transmittance at 360 nm to 370 nm is 0.7% or more. And, the colorant concentration is also low, and even if a cured film is formed by performing post-baking at a low temperature (90 ° C.) that is preferable when forming on an organic light emitting device, solvent resistance is good and the pattern shape is good. It was shown that a colored layer can be formed.

Abstract

A photosensitive green resin composition containing a coloring material, a photopolymerizable compound, and a photoinitiator, the coloring material including a blue pigment and a yellow pigment, the yellow pigment including C.I. Pigment Yellow 139, metal halide phthalocyanine pigments being 10% or less, and the 360-370 nm spectral transmittance being 0.7% or more when a cured film is formed at a film thickness of 3.0 μm.

Description

感光性緑色樹脂組成物、硬化物、カラーフィルタ、表示装置、及び有機発光素子と外光反射防止膜の積層体の製造方法Photosensitive green resin composition, cured product, color filter, display device, and method for producing laminate of organic light emitting element and external light antireflection film
　本発明は、感光性緑色樹脂組成物、硬化物、カラーフィルタ、表示装置、及び当該感光性緑色樹脂組成物を用いた有機発光素子と外光反射防止膜の積層体の製造方法に関する。 The present invention relates to a photosensitive green resin composition, a cured product, a color filter, a display device, and a method for producing a laminate of an organic light-emitting element and an external light antireflection film using the photosensitive green resin composition.
　近年、パーソナルコンピュータの発達、特に携帯用パーソナルコンピュータの発達に伴って、液晶ディスプレイの需要が増加している。モバイルディスプレイ（携帯電話、スマートフォン、タブレットＰＣ）の普及率も高まっており、益々液晶ディスプレイの市場は拡大する状況にある。自発光により視認性が高い有機ＥＬディスプレイのような有機発光表示装置も、次世代画像表示装置として注目されている。
　これらの液晶表示装置や有機発光表示装置には、カラーフィルタが用いられる。例えば液晶表示装置のカラー画像の形成は、カラーフィルタを通過した光がそのままカラーフィルタを構成する各画素の色に着色されて、それらの色の光が合成されてカラー画像を形成する。その際の光源としては、従来の冷陰極管のほか、白色発光の有機発光素子や白色発光の無機発光素子が利用される場合がある。有機発光表示装置では、色調整などのためにカラーフィルタを用いる。 In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays is increasing. The penetration rate of mobile displays (mobile phones, smart phones, tablet PCs) is also increasing, and the market for liquid crystal displays is expanding more and more. An organic light-emitting display device such as an organic EL display, which has high visibility due to self-luminescence, is also attracting attention as a next-generation image display device.
Color filters are used in these liquid crystal display devices and organic light emitting display devices. For example, when forming a color image in a liquid crystal display device, the light that has passed through the color filter is colored into the color of each pixel that constitutes the color filter, and the light of these colors is combined to form a color image. As a light source in that case, in addition to a conventional cold cathode tube, an organic light emitting element emitting white light or an inorganic light emitting element emitting white light may be used. An organic light-emitting display device uses a color filter for color adjustment.
　ここで、カラーフィルタは、一般的に、基板と、基板上に形成され、赤、緑、青の三原色の着色パターンからなる着色層と、各着色パターンを区画するように基板上に形成された遮光部とを有している。
　カラーフィルタにおける着色層の形成方法としては、例えば、分散剤等により色材を分散してなる色材分散液にバインダー樹脂、光重合性化合物及び光開始剤を添加してなる着色樹脂組成物を基板に塗布して乾燥後、フォトマスクを用いて露光し、現像を行うことによって着色パターンを形成し、加熱することによりパターンを固着して着色層を形成する。あるいは、着色樹脂組成物を基板にインクジェット法等でパターン状に塗布して乾燥後、硬化させることによって、着色パターンを形成し、加熱することによりパターンを固着して着色層を形成する。形成これらの工程を、各色ごとに繰り返してカラーフィルタを形成する。 Here, the color filter is generally formed on a substrate, a colored layer formed on the substrate and composed of colored patterns of the three primary colors of red, green, and blue, and formed on the substrate so as to partition each colored pattern. and a light shielding part.
As a method for forming a colored layer in a color filter, for example, a colored resin composition obtained by adding a binder resin, a photopolymerizable compound and a photoinitiator to a coloring material dispersion liquid in which a coloring material is dispersed using a dispersing agent or the like is prepared. After being coated on a substrate and dried, it is exposed to light using a photomask and developed to form a colored pattern, which is fixed by heating to form a colored layer. Alternatively, a colored resin composition is applied to a substrate in a pattern by an inkjet method or the like, dried, and then cured to form a colored pattern, and the pattern is fixed by heating to form a colored layer. Formation These steps are repeated for each color to form a color filter.
　近年、カラーフィルタの高輝度化等の要求が高まりを見せる中で、従来と比べカラーフィルタの着色層における色材濃度が高くなることで、相対的に硬化性成分が少なくなり、パターニングが難しくなってきている。さらにカラーフィルタの生産性を向上させるため、パターニングに必要な積算露光量を減少させることを求められており、パターニングに必要な硬化性をいかに確保するかが大きな課題となっている。 In recent years, as the demand for higher brightness of color filters has increased, the concentration of coloring materials in the colored layers of color filters has increased compared to conventional methods, resulting in relatively less curable components, making patterning more difficult. is coming. Furthermore, in order to improve the productivity of color filters, it is required to reduce the cumulative exposure dose required for patterning, and how to ensure the curability required for patterning has become a major issue.
　カラーフィルタ用の感光性緑色樹脂組成物には、従来、緑顔料として、Ｃ．Ｉ．ピグメントグリーン（ＰＧ）７、３６、５８、及び５９などのハロゲン化金属フタロシアニン顔料が多く使用されている。しかしながら、ハロゲン化金属フタロシアニン顔料が多く含まれる感光性緑色樹脂組成物は、露光波長としてメインとなるｉ線（３６５ｎｍのスペクトル線）の透過率が低く、膜の深部まで均一に硬化しにくいため、現像時に膜の底部が削られてパターン形状が悪化するという課題があった。 　Conventionally, C.I. I. Halogenated metal phthalocyanine pigments such as Pigment Green (PG) 7, 36, 58, and 59 are often used. However, a photosensitive green resin composition containing a large amount of a halogenated metal phthalocyanine pigment has a low transmittance of the i-line (spectral line of 365 nm), which is the main exposure wavelength, and is difficult to cure uniformly to the depth of the film. There is a problem that the bottom portion of the film is scraped during development and the pattern shape is deteriorated.
　一方で、特許文献１には、青色顔料と黄色顔料からなるカラーフィルター用緑色着色剤組成物が開示されている。
　また、特許文献２には、着色剤は、カラーインデックスピグメントブルー１５：３およびカラーインデックスピグメントブルー１５：４から選ばれる少なくとも１種と、カラーインデックスピグメントイエロー１５０とを含み、カラーインデックスピグメントイエロー１５０の１００質量部に対して、カラーインデックスピグメントブルー１５：３とカラーインデックスピグメントブルー１５：４とを合計で３５～５５質量部含有し、上記着色組成物は、波長４００～７００ｎｍの波長の光に対する吸光度のうち、波長４９５～５２５ｎｍの範囲に吸光度の最小値を有し、波長４５０ｎｍの光に対する吸光度を１としたとき、吸光度が０．１４となる波長が４７４～４９４ｎｍの範囲と、５３０～５７０ｎｍの範囲のそれぞれに存在し、波長４５０ｎｍの光に対する吸光度Ａ４５０と、波長６２０ｎｍの光に対する吸光度Ａ６２０との比であるＡ４５０／Ａ６２０が１．０８～２．０５である、着色組成物が開示されている。 On the other hand, Patent Literature 1 discloses a green colorant composition for color filters comprising a blue pigment and a yellow pigment.
Further, in Patent Document 2, the colorant contains at least one selected from Color Index Pigment Blue 15:3 and Color Index Pigment Blue 15:4, and Color Index Pigment Yellow 150. Color Index Pigment Blue 15:3 and Color Index Pigment Blue 15:4 are contained in a total of 35 to 55 parts by weight with respect to 100 parts by weight, and the coloring composition has an absorbance for light with a wavelength of 400 to 700 nm. Among them, when the absorbance for light with a wavelength of 450 nm is 1, the wavelength at which the absorbance is 0.14 is the range of 474 to 494 nm and the range of 530 to 570 nm. A coloring composition that exists in each of the ranges and has an A 450 /A 620 ratio of the absorbance A 450 for light with a wavelength of 450 nm and the absorbance A 620 for light with a wavelength of 620 nm from 1.08 to 2.05 disclosed.
特開２０１１－２４２５６８号公報JP 2011-242568 A 国際公開２０２０／１９６３９３号公報International publication 2020/196393
　従来、カラーフィルタはガラス基板上に形成されていたが、近年、素子基板上に直接カラーフィルタを形成することが求められてきている。
　有機発光素子等の素子は、耐熱性が低いため、素子基板上に直接カラーフィルタを形成する製造工程での加熱処理は、例えば１３０℃以下、更に１００℃以下で行うことが好ましいとされている。通常のカラーフィルタ製造工程ではガラス基板上で２３０℃程度の加熱処理を行って着色層を硬化させるのに対して、１３０℃以下や１００℃以下の加熱処理では、熱による着色層の硬化は進行しにくい。そのため、後工程で必要な耐溶剤性を着色層に持たせるためには、露光で十分に着色層を硬化させることが必要となる。ハロゲン化金属フタロシアニン顔料が多く含まれる感光性緑色樹脂組成物は、露光波長としてメインとなるｉ線（３６５ｎｍのスペクトル線）の透過率が低く、膜の深部まで均一に硬化しにくいため、低温加熱処理を行った場合の硬化膜の耐溶剤性に特に課題があった。 Conventionally, color filters have been formed on glass substrates, but in recent years there has been a demand for forming color filters directly on element substrates.
Elements such as organic light-emitting elements have low heat resistance, so the heat treatment in the manufacturing process for forming the color filter directly on the element substrate is preferably performed at, for example, 130° C. or less, and more preferably 100° C. or less. . In the normal color filter manufacturing process, the colored layer is hardened by heat treatment at about 230°C on the glass substrate. hard to do. Therefore, in order to give the colored layer the solvent resistance required in the post-process, it is necessary to sufficiently cure the colored layer by exposure. A photosensitive green resin composition containing a large amount of a halogenated metal phthalocyanine pigment has a low transmittance of the i-line (spectral line of 365 nm), which is the main exposure wavelength, and is difficult to cure uniformly to the depth of the film. There was a particular problem with the solvent resistance of the cured film when the treatment was performed.
　前記特許文献１は、ハロゲンフリー、高コントラスト比、かつ高密着力となるカラーフィルター基板を提供することを目的とする技術であり、パターン形状や、低温加熱処理を行った場合の硬化膜の耐溶剤性については一切記載されていない。特許文献１に具体的に記載されている組成物を用いて低温加熱処理を行った場合の硬化膜は、後述の比較例で示したように、未だパターン形状が悪化し、耐溶剤性が不十分であるという課題がある。
　また、特許文献２は、耐光性および他色との色分離性に優れた硬化膜を形成することができる着色組成物を得ることを目的とした技術であり、パターン形状や、低温加熱処理を行った場合の硬化膜の耐溶剤性については一切記載されていない。特許文献２に具体的に記載されている組成物を用いて低温加熱処理を行った場合の硬化膜についても、後述の比較例で示したように、パターン形状が悪化し、耐溶剤性が不十分であるという課題がある。 The above Patent Document 1 is a technique aimed at providing a halogen-free, high-contrast-ratio, and high-adhesion color filter substrate. No mention is made of gender. The cured film obtained by performing low-temperature heat treatment using the composition specifically described in Patent Document 1 still has a poor pattern shape and poor solvent resistance, as shown in Comparative Examples below. There is a problem of being sufficient.
In addition, Patent Document 2 is a technique aimed at obtaining a colored composition capable of forming a cured film having excellent light resistance and color separation from other colors, and pattern shape and low-temperature heat treatment. There is no description about the solvent resistance of the cured film in the case where the method is carried out. Regarding the cured film obtained by performing low-temperature heat treatment using the composition specifically described in Patent Document 2, the pattern shape deteriorated and the solvent resistance was poor, as shown in the comparative examples described later. There is a problem of being sufficient.
　本発明は、上記実情に鑑みてなされたものであり、低温加熱処理でも、耐溶剤性が良好で且つパターン形状が良好な着色層を形成可能な感光性緑色樹脂組成物を提供することを目的とする。また、本発明は、当該感光性緑色樹脂組成物を用いて形成されたカラーフィルタ及び表示装置、並びに、当該感光性緑色樹脂組成物を用いた有機発光素子と外光反射防止膜の積層体の製造方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a photosensitive green resin composition capable of forming a colored layer having good solvent resistance and a good pattern shape even when subjected to low-temperature heat treatment. and The present invention also provides a color filter and a display device formed using the photosensitive green resin composition, and a laminate of an organic light emitting device and an external light antireflection film using the photosensitive green resin composition. The object is to provide a manufacturing method.
　本発明に係る感光性緑色樹脂組成物は、色材と、アルカリ可溶性樹脂と、光重合性化合物と、光開始剤とを含有し、
　前記色材が、青色顔料と黄色顔料を含み、当該黄色顔料がＣ．Ｉ．ピグメントイエロー１３９を含み、ハロゲン化金属フタロシアニン顔料が１０％以下であり、
　膜厚３．０μｍで硬化膜を形成した時に、３６０ｎｍ～３７０ｎｍのスペクトル透過率が０．７％以上である。 The photosensitive green resin composition according to the present invention contains a colorant, an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator,
The coloring material includes a blue pigment and a yellow pigment, and the yellow pigment is C.I. I. Pigment Yellow 139 with a halogenated metal phthalocyanine pigment of 10% or less,
When a cured film with a film thickness of 3.0 μm is formed, the spectral transmittance at 360 nm to 370 nm is 0.7% or more.
　本発明に係る硬化物は、前記本発明に係る感光性緑色樹脂組成物の硬化物である。 The cured product according to the present invention is the cured product of the photosensitive green resin composition according to the present invention.
　本発明に係るカラーフィルタは、基板と、当該基板上に設けられた着色層とを少なくとも備えるカラーフィルタであって、当該着色層の少なくとも１つが前記本発明に係る感光性緑色樹脂組成物の硬化物である。 The color filter according to the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a cured photosensitive green resin composition according to the present invention. It is a thing.
　本発明に係る表示装置は、前記本発明に係るカラーフィルタを有する。
　また、本発明に係る表示装置は、有機発光素子上に、前記本発明に係る感光性緑色樹脂組成物の硬化膜を有する。 A display device according to the present invention has the color filter according to the present invention.
Further, the display device according to the present invention has a cured film of the photosensitive green resin composition according to the present invention on the organic light-emitting element.
　本発明に係る有機発光素子と外光反射防止膜の積層体の製造方法は、
有機発光素子上に、前記本発明に係る感光性緑色樹脂組成物を塗布することにより塗膜を形成する工程、
　前記塗膜に光照射する工程、
　前記光照射後の膜を、加熱するポストベイク工程、及び、
　前記光照射後の膜を、現像する工程を含有することにより、
有機発光素子上に前記本発明に係る感光性緑色樹脂組成物の硬化膜を形成する工程を有する。 The method for producing a laminate of an organic light-emitting element and an external light antireflection film according to the present invention includes:
A step of forming a coating film by applying the photosensitive green resin composition according to the present invention on the organic light emitting device;
a step of irradiating the coating film with light;
A post-baking step of heating the film after the light irradiation, and
By including the step of developing the film after the light irradiation,
A step of forming a cured film of the photosensitive green resin composition according to the present invention on the organic light emitting device.
　本発明によれば、低温加熱処理でも、耐溶剤性が良好で且つパターン形状が良好な着色層を形成可能な感光性緑色樹脂組成物を提供することができる。また、本発明によれば、当該感光性緑色樹脂組成物を用いて形成されたカラーフィルタ及び表示装置、並びに、当該感光性緑色樹脂組成物を用いた有機発光素子と外光反射防止膜の積層体の製造方法を提供することができる。 According to the present invention, it is possible to provide a photosensitive green resin composition capable of forming a colored layer having good solvent resistance and a good pattern shape even with low-temperature heat treatment. Further, according to the present invention, a color filter and a display device formed using the photosensitive green resin composition, and a laminate of an organic light emitting device and an external light antireflection film using the photosensitive green resin composition A method of manufacturing a body can be provided.
図１は、本発明に係るカラーフィルタの一例を示す概略断面図である。FIG. 1 is a schematic cross-sectional view showing an example of a color filter according to the invention. 図２は、本発明に係る液晶表示装置の一例を示す概略断面図である。FIG. 2 is a schematic cross-sectional view showing an example of a liquid crystal display device according to the present invention. 図３は、本発明に係る有機発光表示装置の一例を示す概略断面図である。FIG. 3 is a schematic cross-sectional view showing an example of an organic light-emitting display device according to the present invention. 図４は、本発明に係る有機発光素子を備えた表示装置の他の一例を示す概略断面図である。FIG. 4 is a schematic cross-sectional view showing another example of a display device having an organic light-emitting device according to the present invention. 図５は、細線パターンの着色層の断面形状のテーパー角（θ１）を説明する概略断面図である。FIG. 5 is a schematic cross-sectional view for explaining the taper angle (θ1) of the cross-sectional shape of the colored layer of the fine line pattern.
　以下、本発明の実施の形態や実施例などを、図面等を参照しながら説明する。但し、本発明は多くの異なる態様で実施することが可能であり、以下に例示する実施の形態や実施例等の記載内容に限定して解釈されるものではない。また、図面は説明をより明確にするため、実際の態様に比べ、各部の幅、厚さ、形状等について模式的に表される場合があるが、あくまで一例であって、本発明の解釈を限定するものではない。また、本明細書と各図において、既出の図に関して前述したものと同様の要素には、同一の符号を付して、詳細な説明を適宜省略することがある。また、説明の便宜上、上方又は下方という語句を用いて説明する場合があるが、上下方向が逆転してもよい。
　本明細書において、ある部材又はある領域等のある構成が、他の部材又は他の領域等の他の構成の「上に（又は下に）」あるとする場合、特段の限定がない限り、これは他の構成の直上（又は直下）にある場合のみでなく、他の構成の上方（又は下方）にある場合を含み、すなわち、他の構成の上方（又は下方）において間に別の構成要素が含まれている場合も含む。
　なお、本発明において光には、可視及び非可視領域の波長の電磁波、さらには放射線が含まれ、放射線には、例えばマイクロ波、電子線が含まれる。具体的には、波長５μｍ以下の電磁波、及び電子線のことをいう。
　本発明において（メタ）アクリロイルとは、アクリロイル及びメタクリロイルの各々を表し、（メタ）アクリルとは、アクリル及びメタクリルの各々を表し、（メタ）アクリレートとは、アクリレート及びメタクリレートの各々を表す。
　また、本明細書において数値範囲を示す「～」とは、その前後に記載された数値を下限値及び上限値として含む意味で使用される。
　また、本発明において、Ｘｎｍ～Ｙｎｍの範囲の波長におけるスペクトル透過率がＺ％以上とは、Ｘｎｍ～Ｙｎｍの範囲の波長域全体において、スペクトル透過率がＺ％以上であることを表す。
　以下、本発明に係る感光性緑色樹脂組成物、硬化物、カラーフィルタ、表示装置、及び有機発光素子と外光反射防止膜の積層体の製造方法について、順に詳細に説明する。 BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments and examples of the present invention will be described with reference to the drawings. However, the present invention can be implemented in many different aspects, and should not be construed as being limited to the descriptions of the embodiments, examples, and the like exemplified below. In addition, in order to make the description clearer, the drawings may schematically show the width, thickness, shape, etc. of each part compared to the actual embodiment, but this is only an example, and the interpretation of the present invention is not intended. It is not limited. In addition, in this specification and each figure, the same reference numerals may be given to the same elements as those described above with respect to the existing figures, and detailed description thereof may be omitted as appropriate. Also, for convenience of explanation, the terms "upper" and "lower" may be used, but the up-down direction may be reversed.
As used herein, when a feature, such as a member or region, is "above (or below)" another feature, such as another member or region, unless otherwise specified, This includes not only being directly above (or directly below) another structure, but also above (or below) another structure, i.e. above (or below) another structure and between another structure. Including when the element is included.
In the present invention, light includes electromagnetic waves with wavelengths in the visible and non-visible regions, and radiation, and radiation includes, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves with a wavelength of 5 μm or less and electron beams.
In the present invention, (meth)acryloyl represents acryloyl and methacryloyl, (meth)acryl represents acrylic and methacrylic, and (meth)acrylate represents acrylate and methacrylate.
Further, in this specification, the term "to" indicating a numerical range is used to include the numerical values before and after it as lower and upper limits.
Further, in the present invention, the spectral transmittance of Z % or more in the wavelength range of X nm to Y nm means that the spectral transmittance is Z % or more in the entire wavelength range of X nm to Y nm.
Hereinafter, the photosensitive green resin composition, the cured product, the color filter, the display device, and the method for producing the laminate of the organic light-emitting element and the external light antireflection film according to the present invention will be described in detail in order.
Ｉ．感光性緑色樹脂組成物 
　本発明に係る感光性緑色樹脂組成物は、色材と、アルカリ可溶性樹脂と、光重合性化合物と、光開始剤とを含有し、
　前記色材が、青色顔料と黄色顔料を含み、当該黄色顔料がＣ．Ｉ．ピグメントイエロー１３９を含み、ハロゲン化金属フタロシアニン顔料が１０％以下であり、
　膜厚３．０μｍで硬化膜を形成した時に、３６０ｎｍ～３７０ｎｍのスペクトル透過率が０．７％以上である。 I. Photosensitive green resin composition
The photosensitive green resin composition according to the present invention contains a colorant, an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator,
The coloring material includes a blue pigment and a yellow pigment, and the yellow pigment is C.I. I. Pigment Yellow 139 with a halogenated metal phthalocyanine pigment of 10% or less,
When a cured film with a film thickness of 3.0 μm is formed, the spectral transmittance at 360 nm to 370 nm is 0.7% or more.
　本発明に係る感光性緑色樹脂組成物は、前記色材が、青色顔料と黄色顔料を含み、当該黄色顔料がＣ．Ｉ．ピグメントイエロー１３９を含み、ハロゲン化金属フタロシアニン顔料が１０％以下であり、且つ、上記所定の波長域において所定のスペクトル透過率を満たすことにより、低温加熱処理でも、耐溶剤性が良好で、且つパターン形状が良好な着色層を形成可能である。
　前記色材が、青色顔料と黄色顔料を含み、当該黄色顔料がＣ．Ｉ．ピグメントイエロー１３９を含み、ハロゲン化金属フタロシアニン顔料が１０％以下であることから、膜厚３．０μｍで硬化膜を形成した時に、３６０ｎｍ～３７０ｎｍのスペクトル透過率が０．７％以上を達成しやすい。Ｃ．Ｉ．ピグメントイエロー１３９は、着色力が高いことから硬化膜中の色材濃度を下げることが可能であり、相対的に硬化性成分濃度を上げることができるため、低温加熱処理でも、耐溶剤性が良好で且つパターン形状が良好な着色層を形成可能になる。また、膜厚３．０μｍで硬化膜を形成した時に、３６０ｎｍ～３７０ｎｍの透過率が０．７％以上であれば、組成物の塗膜を硬化させる際に露光波長としてメインとなるｉ線（３６５ｎｍのスペクトル線）の透過率が確保され、膜の深部まで均一に硬化しやすくなり、現像時の膜の底部が削られてパターン形状が悪化することを抑制できる。また、膜の深部まで均一に硬化しやすくなることから、低温加熱処理でも耐溶剤性が良好になる。 In the photosensitive green resin composition according to the present invention, the colorant contains a blue pigment and a yellow pigment, and the yellow pigment is C.I. I. Pigment Yellow 139, the halogenated metal phthalocyanine pigment is 10% or less, and the predetermined spectral transmittance is satisfied in the predetermined wavelength range, so that even at low temperature heat treatment, solvent resistance is good and the pattern A colored layer having a good shape can be formed.
The coloring material includes a blue pigment and a yellow pigment, and the yellow pigment is C.I. I. Pigment Yellow 139 is included and the halogenated metal phthalocyanine pigment is 10% or less, so when a cured film is formed with a film thickness of 3.0 μm, the spectral transmittance of 360 nm to 370 nm is easy to achieve 0.7% or more. . C. I. Pigment Yellow 139 has high coloring power, so it is possible to reduce the concentration of coloring materials in the cured film, and because it is possible to relatively increase the concentration of curable components, it has good solvent resistance even at low temperature heat treatment. and a colored layer having a good pattern shape can be formed. Further, when a cured film is formed with a film thickness of 3.0 μm, if the transmittance at 360 nm to 370 nm is 0.7% or more, the i-line ( 365 nm spectral line) is ensured, the film is easily cured evenly to the deep part, and it is possible to suppress deterioration of the pattern shape due to scraping of the bottom part of the film during development. In addition, since it becomes easy to cure uniformly to the deep part of the film, the solvent resistance becomes good even with low-temperature heat treatment.
　また、本発明に係る感光性緑色樹脂組成物は、低温加熱処理でも、耐溶剤性が良好で且つパターン形状が良好な着色層を形成可能であることから、有機発光素子上に形成する硬化膜に好適に用いることができる。すなわち、本発明に係る感光性緑色樹脂組成物は、有機発光素子を備えた素子基板上に直接形成する硬化膜に好適に用いることができる。本発明に係る感光性緑色樹脂組成物を、有機発光素子上に隣接して又は少なくとも１層介して形成する硬化膜に用いる場合には、ガラス基板等の基板上に形成された外付けのカラーフィルタを有機発光素子に貼り合わせた表示装置に比べて、薄型化やフレキシブル化が向上した表示装置を製造可能である。本発明に係る感光性緑色樹脂組成物を、有機発光素子上に隣接して又は少なくとも１層介して形成する硬化膜に用いる場合には、外光反射を抑制するための偏光板代替のカラーフィルタとして用いることも可能である。
　さらに、本発明に係る感光性緑色樹脂組成物により形成された有機発光素子上に形成する硬化膜は、ハロゲン化金属フタロシアニン顔料の含有量が色材全量に対して１０質量％以下で、緑色を実現することから、ガラスを透明粘着剤で貼り合せた状態で耐候性試験を行っても透過率の低下が抑制されたものであり、耐候性に優れた表示装置を実現することができる。 In addition, the photosensitive green resin composition according to the present invention can form a colored layer having good solvent resistance and a good pattern shape even with low-temperature heat treatment, so the cured film formed on the organic light-emitting element It can be suitably used for That is, the photosensitive green resin composition according to the present invention can be suitably used for a cured film directly formed on a device substrate having an organic light-emitting device. When the photosensitive green resin composition according to the present invention is used for a cured film formed adjacent to or via at least one layer on an organic light emitting device, an external color formed on a substrate such as a glass substrate Compared to a display device in which a filter is attached to an organic light-emitting element, a display device that is thinner and more flexible can be manufactured. When the photosensitive green resin composition according to the present invention is used for a cured film formed adjacent to or via at least one layer on an organic light emitting device, a color filter as a substitute for a polarizing plate for suppressing external light reflection It can also be used as
Furthermore, the cured film formed on the organic light-emitting element formed from the photosensitive green resin composition according to the present invention has a content of the halogenated metal phthalocyanine pigment of 10% by mass or less with respect to the total amount of the coloring material, and has a green color. Since it is realized, even if a weather resistance test is performed in a state where glass is bonded with a transparent adhesive, a decrease in transmittance is suppressed, and a display device with excellent weather resistance can be realized.
　本発明に係る感光性緑色樹脂組成物は、少なくとも色材と、アルカリ可溶性樹脂と、光重合性化合物と、光開始剤とを含有するものであり、本発明の効果を損なわない範囲で、更に他の成分を含有してもよいものである。
　以下、このような本発明に係る感光性緑色樹脂組成物の各成分について、順に詳細に説明する。 The photosensitive green resin composition according to the present invention contains at least a coloring material, an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator, in a range that does not impair the effects of the present invention, and further It may contain other components.
Each component of the photosensitive green resin composition according to the present invention will be described in detail below.
＜色材＞
　本発明において、色材は、カラーフィルタの着色層を形成した際に所望の発色が可能なものであればよく、特に限定されず、種々の有機顔料、無機顔料、分散可能な染料、染料の造塩化合物等を、２種以上混合して用いることができるが、青色顔料と黄色顔料を含み、当該黄色顔料がＣ．Ｉ．ピグメントイエロー１３９を含み、ハロゲン化金属フタロシアニン顔料が１０％以下であることを特徴とする。 <Color material>
In the present invention, the coloring material is not particularly limited as long as it can develop a desired color when the colored layer of the color filter is formed, and various organic pigments, inorganic pigments, dispersible dyes, and dyes Two or more kinds of salt-forming compounds can be mixed and used. I. Pigment Yellow 139, containing 10% or less of a halogenated metal phthalocyanine pigment.
　色材としては、中でも有機顔料は、発色性が高く、耐熱性も高いので、好ましく用いられる。有機顔料としては、例えばカラーインデックス（Ｃ．Ｉ．；Ｔｈｅ　Ｓｏｃｉｅｔｙ　ｏｆ　Ｄｙｅｒｓ　ａｎｄ　Ｃｏｌｏｕｒｉｓｔｓ　社発行）においてピグメント（Ｐｉｇｍｅｎｔ）に分類されている化合物、具体的には、下記のようなカラーインデックス（Ｃ．Ｉ．）番号が付されているものを挙げることができる。 Among them, organic pigments are preferably used as coloring materials because they have high coloring properties and high heat resistance. Examples of organic pigments include compounds classified as pigments in the Color Index (published by The Society of Dyers and Colorists). .) numbered ones can be mentioned.
　青色顔料としては、例えば、Ｃ．Ｉ．ピグメントブルー１、１５、１５：１、１５：２、１５：３、１５：４、１５：６、１６、６０、６１、７９、８０等が挙げられる。 As a blue pigment, for example, C.I. I. Pigment Blue 1, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 61, 79, 80 and the like.
　青色顔料としては、所望の透過スペクトルを得やすく、外光反射の抑制効果を向上させやすい点から、Ｃ．Ｉ．ピグメントブルー１５：３、Ｃ．Ｉ．ピグメントブルー１５：４、ピグメントブルー１５：６及びＣ．Ｉ．ピグメントブルー１６からなる群から選択される少なくとも１種が好ましい。 As a blue pigment, C.I. I. Pigment Blue 15:3, C.I. I. Pigment Blue 15:4, Pigment Blue 15:6 and C.I. I. At least one selected from the group consisting of Pigment Blue 16 is preferred.
　Ｃ．Ｉ．ピグメントブルー１５：３、Ｃ．Ｉ．ピグメントブルー１５：４、及びＣ．Ｉ．ピグメントブルー１６は、それぞれ、透過スペクトルの立ち上がり波長が長波長側から短波長側に少しずつずれて異なることから、透過させる波長領域と透過率や、組み合わせる発光素子の発光スペクトルを考慮して、適宜選択して１種単独で又は２種以上組み合わせて用いることが好ましい。耐候性の点からは、中でもＣ．Ｉ．ピグメントブルー１５：４が好ましい。 　C. I. Pigment Blue 15:3, C.I. I. Pigment Blue 15:4, and C.I. I. Pigment Blue 16 has a slightly different rising wavelength of the transmission spectrum from the long wavelength side to the short wavelength side. It is preferable to select and use one kind alone or two or more kinds in combination. From the viewpoint of weather resistance, C.I. I. Pigment Blue 15:4 is preferred.
　黄色顔料には、Ｃ．Ｉ．ピグメントイエロー１３９を必須成分として含む。Ｃ．Ｉ．ピグメントイエロー１３９は、着色力が高いことから硬化膜中の色材濃度を下げることが可能であり、相対的に硬化性成分濃度を上げることができるため、硬化膜に対して低温加熱処理を行っても耐溶剤性が良好で、且つパターン形状が良好な着色層を形成可能になる。また、Ｃ．Ｉ．ピグメントイエロー１３９は、青色顔料と組み合わせた場合に、透過スペクトルの最大透過率を示す波長が５２５ｎｍ～５４５ｎｍの範囲内になりやすく、且つ、５２５ｎｍ～５４５ｎｍの範囲の波長における透過スペクトルのピークの半値幅を小さくしやすいことから、硬化膜を反射防止膜として用いる場合に外光反射の抑制効果を向上させやすい。 For the yellow pigment, C.I. I. Contains Pigment Yellow 139 as an essential ingredient. C. I. Pigment Yellow 139 has high coloring power, so it is possible to reduce the concentration of the coloring material in the cured film, and relatively increase the concentration of the curable component, so the cured film is subjected to low-temperature heat treatment. However, it is possible to form a colored layer having good solvent resistance and a good pattern shape. Also, C.I. I. When Pigment Yellow 139 is combined with a blue pigment, the wavelength at which the maximum transmittance of the transmission spectrum is exhibited tends to be within the range of 525 nm to 545 nm, and the half width of the peak of the transmission spectrum in the wavelength range of 525 nm to 545 nm. can be easily reduced, the effect of suppressing external light reflection can be easily improved when the cured film is used as an antireflection film.
　その他の黄色顔料としては、例えば、Ｃ．Ｉ．ピグメントイエロー１、１：１、２、３、４、５、６、９、１０、１２、１３、１４、１５、１６、１７、２０、２４、３１、３２、３４、３５、３５：１、３６、３６：１、３７、３７：１、４０、４１、４２、４３、４８、５３、５５、６０、６１、６２、６２：１、６３、６５、７１、７３、７４、７５、８１、８３、８７、９３、９４、９５、９７、９８、１００、１０１、１０４、１０５、１０６、１０８、１０９、１１０、１１１、１１３、１１４、１１６、１１７、１１９、１２０、１２６、１２７、１２７：１、１２８、１２９、１３３、１３４、１３６、１３８、１４２、１４７、１４８、１５０、１５１、１５２、１５３、１５４、１５５、１５６、１５７、１５８、１５９、１６０、１６１、１６２、１６３、１６４、１６５、１６６、１６７、１６８、１７３、１７５、１８５、１９４、２１１、２１４、２１５、２３１、及びＣ．Ｉ．ピグメントイエロー１５０の誘導体顔料等が挙げられる。 As other yellow pigments, for example, C.I. I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 15, 16, 17, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 60, 61, 62, 62:1, 63, 65, 71, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 98, 100, 101, 104, 105, 106, 108, 109, 110, 111, 113, 114, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 142, 147, 148, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 173, 175, 185, 194, 211, 214, 215, 231 and C.I. I. Examples thereof include pigment yellow 150 derivative pigments.
　黄色顔料としては、青色顔料と組み合わせた場合に、所望の透過スペクトルに調整しやすい点から、更にピグメントイエロー１３８、ピグメントイエロー１５０、及びピグメントイエロー１８５からなる群から選択される少なくとも１種を含んでもよく、更にピグメントイエロー１５０を含むことがより好ましい。 As the yellow pigment, when combined with a blue pigment, it may contain at least one selected from the group consisting of Pigment Yellow 138, Pigment Yellow 150, and Pigment Yellow 185 from the viewpoint that it is easy to adjust the desired transmission spectrum. Well, it is more preferred to further include Pigment Yellow 150.
　色材としては、前記青色顔料が、Ｃ．Ｉ．ピグメントブルー１５：３、Ｃ．Ｉ．ピグメントブルー１５：４、及びＣ．Ｉ．ピグメントブルー１６からなる群から選択される少なくとも１種を含み、黄色顔料が、更にＣ．Ｉ．ピグメントイエロー１３８、Ｃ．Ｉ．ピグメントイエロー１５０、及びＣ．Ｉ．ピグメントイエロー１８５からなる群から選択される少なくとも１種を含むものであってよい。 As the colorant, the blue pigment is C.I. I. Pigment Blue 15:3, C.I. I. Pigment Blue 15:4, and C.I. I. Pigment Blue 16, wherein the yellow pigment further contains C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 150, and C.I. I. Pigment Yellow 185 may contain at least one selected from the group consisting of Pigment Yellow 185.
　色材には、硬化膜の色調や、反射防止膜として用いる場合の外光反射の抑制効果を調整する点から、更にその他の色材を用いてもよい。その他の色材としては、例えば、緑色顔料、紫色顔料、オレンジ色顔料等が挙げられる。
　緑色顔料としては、例えば、Ｃ．Ｉ．ピグメントグリーン７、３６、５８、５９、６２、６３等が挙げられる。但し、緑色顔料を用いる場合であっても、耐候性を良好にする点から、ハロゲン化金属フタロシアニン顔料が色材全量に対して１０質量％以下とする。 As the coloring material, other coloring materials may be used from the viewpoint of adjusting the color tone of the cured film and the effect of suppressing reflection of external light when used as an antireflection film. Other coloring materials include, for example, green pigments, purple pigments, orange pigments, and the like.
Examples of green pigments include C.I. I. Pigment Green 7, 36, 58, 59, 62, 63 and the like. However, even when a green pigment is used, the content of the halogenated metal phthalocyanine pigment is set to 10% by mass or less based on the total amount of the coloring material in order to improve the weather resistance.
　また、紫色顔料としては、例えば、Ｃ．Ｉ．ピグメントバイオレット１、１９、２３、２９、３２、３６、３８等が挙げられる。
　オレンジ色顔料としては、例えば、Ｃ．Ｉ．ピグメントオレンジ１、５、１３、１４、１６、１７、２４、３４、３６、３８、４０、４３、４６、４９、５１、６１、６３、６４、７１、７３等が挙げられる。 Moreover, as a purple pigment, for example, C.I. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and the like.
Examples of orange pigments include C.I. I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73 and the like.
　本発明で用いられる青色顔料と黄色顔料、及び必要に応じて含まれていてもよい他の色材の含有割合は、当該感光性緑色樹脂組成物により膜厚３．０μｍで硬化膜を形成した時に、３６０ｎｍ～３７０ｎｍの透過率が０．７％以上となるように、調整される。
　当該感光性緑色樹脂組成物により膜厚３．０μｍで硬化膜を形成した時に、３６０ｎｍ～３７０ｎｍの透過率が０．７％以上であれば、組成物の塗膜を硬化させる際に露光波長としてメインとなるｉ線（３６５ｎｍのスペクトル線）の透過率が確保され、膜の深部まで均一に硬化しやすくなり、現像時の膜の底部が削られてパターン形状が悪化することを抑制できる。また、膜の深部まで均一に硬化しやすくなることから、低温加熱処理でも耐溶剤性が良好になる。膜厚３．０μｍで硬化膜を形成した時に、３６０ｎｍ～３７０ｎｍの透過率は、０．８％以上であってよく、０．９％以上であってよい。
　なお、本発明において、膜厚３．０μｍで硬化膜を形成した時のスペクトル透過率は、具体的には実施例に記載した方法により測定することができる。 The blue pigment and yellow pigment used in the present invention, and the content ratio of other colorants that may be contained as necessary, formed a cured film with a film thickness of 3.0 μm with the photosensitive green resin composition. Sometimes it is adjusted so that the transmittance from 360 nm to 370 nm is 0.7% or more.
When a cured film with a thickness of 3.0 μm is formed from the photosensitive green resin composition, if the transmittance at 360 nm to 370 nm is 0.7% or more, the exposure wavelength when curing the coating film of the composition The transmittance of the main i-line (spectral line of 365 nm) is secured, the film is easily cured evenly to the deep part, and it is possible to suppress the deterioration of the pattern shape due to the bottom part of the film being scraped during development. In addition, since it becomes easy to cure uniformly to the deep part of the film, the solvent resistance becomes good even with low-temperature heat treatment. When a cured film having a film thickness of 3.0 μm is formed, the transmittance at 360 nm to 370 nm may be 0.8% or more, and may be 0.9% or more.
In addition, in the present invention, the spectral transmittance when a cured film having a thickness of 3.0 μm is formed can be specifically measured by the method described in Examples.
　外光反射防止膜として用いる場合には、本発明で用いられる青色顔料と黄色顔料、及び必要に応じて含まれていてもよい他の色材の含有割合は、当該感光性緑色樹脂組成物により膜厚３．０μｍで硬化膜を形成した時に、３８０ｎｍ～４８０ｎｍの範囲の波長におけるスペクトル透過率が２０％以下、５８０ｎｍ～７００ｎｍの範囲の波長におけるスペクトル透過率が２５％以下、及び、５１０ｎｍ～５５０ｎｍの範囲の波長におけるスペクトル透過率が４０％以上８０％以下となるように、調整されることが好ましい。
　膜厚３．０μｍで硬化膜を形成した時に、３８０ｎｍ～４８０ｎｍの波長におけるスペクトル透過率が２０％以下であれば、緑色の色純度の低下が抑制され、発光素子からの色純度の低下も抑制しやすく、反射防止性能が優れやすい。膜厚３．０μｍで硬化膜を形成した時に、３８０ｎｍ～４８０ｎｍの波長におけるスペクトル透過率は、１８％以下であってよく、１３％以下であってよい。
　一方、膜厚３．０μｍで硬化膜を形成した時に、５１０ｎｍ～５５０ｎｍの波長におけるスペクトル透過率が４０％以上８０％以下であれば、表示装置の輝度低下や視認性の不良を抑制しやすい。膜厚３．０μｍで硬化膜を形成した時に、５１０ｎｍ～５５０ｎｍの波長におけるスペクトル透過率は、４５％以上であってよく、また、７５％以下、さらに７０％以下であってよい。
　また、膜厚３．０μｍで硬化膜を形成した時に、５８０ｎｍ～７００ｎｍの波長におけるスペクトル透過率が３０％以下であれば、反射防止性能が優れやすい。膜厚３．０μｍで硬化膜を形成した時に、５８０ｎｍ～７００ｎｍの波長におけるスペクトル透過率は、２５％以下であってよく、２０％以下であってよく、１８％以下であってよい。 When used as an external light antireflection film, the content ratio of the blue pigment and yellow pigment used in the present invention, and other colorants that may be contained as necessary, depends on the photosensitive green resin composition. When a cured film is formed with a thickness of 3.0 μm, the spectral transmittance in the wavelength range of 380 nm to 480 nm is 20% or less, the spectral transmittance in the wavelength range of 580 nm to 700 nm is 25% or less, and 510 nm to 550 nm. is preferably adjusted so that the spectral transmittance in the wavelength range is 40% or more and 80% or less.
When a cured film is formed with a thickness of 3.0 μm, if the spectral transmittance at a wavelength of 380 nm to 480 nm is 20% or less, the deterioration of the color purity of green is suppressed, and the deterioration of the color purity from the light emitting element is also suppressed. It is easy to apply, and the anti-reflection performance is excellent. When a cured film having a thickness of 3.0 μm is formed, the spectral transmittance at a wavelength of 380 nm to 480 nm may be 18% or less, and may be 13% or less.
On the other hand, when a cured film having a thickness of 3.0 μm is formed, if the spectral transmittance at a wavelength of 510 nm to 550 nm is 40% or more and 80% or less, it is easy to suppress deterioration in brightness and poor visibility of the display device. When a cured film having a thickness of 3.0 μm is formed, the spectral transmittance at a wavelength of 510 nm to 550 nm may be 45% or more, 75% or less, and further 70% or less.
Further, when a cured film having a thickness of 3.0 μm is formed, if the spectral transmittance at a wavelength of 580 nm to 700 nm is 30% or less, the antireflection performance tends to be excellent. When a cured film having a thickness of 3.0 μm is formed, the spectral transmittance at a wavelength of 580 nm to 700 nm may be 25% or less, 20% or less, or 18% or less.
　また、特定の有機発光素子と組み合わせた場合に輝度を向上し、外光反射防止膜として用いる場合の外光反射抑制効果を向上する点から、膜厚３．０μｍで硬化膜を形成した時に、透過スペクトルの３８０ｎｍ～７００ｎｍの範囲の波長において最大透過率を示す波長が５２５ｎｍ～５４５ｎｍの範囲内にあることが好ましく、５２５ｎｍ～５４０ｎｍの範囲にあることがより好ましく、５２６ｎｍ～５４０ｎｍの範囲にあることがさらに好ましく、５２７ｎｍ～５３５ｎｍの範囲にあってもよい。
　また、膜厚３．０μｍで硬化膜を形成した時に、５２５ｎｍ～５４５ｎｍの範囲の波長における透過スペクトルのピークの半値幅が７０ｎｍ以下となることが、外光反射防止膜として用いる場合の反射防止性能が向上する点、及び、色純度が向上し、色再現域が広がる点から好ましい。膜厚３．０μｍで硬化膜を形成した時に、５２５ｎｍ～５４５ｎｍの範囲の波長における透過スペクトルのピークの半値幅は６５ｎｍ以下であってよく、６３ｎｍ以下であってよく、６０ｎｍ以下であって良い。 In addition, from the viewpoint of improving the luminance when combined with a specific organic light emitting device and improving the effect of suppressing external light reflection when used as an external light antireflection film, when a cured film is formed with a thickness of 3.0 μm, The wavelength at which the maximum transmittance is exhibited in the wavelength range of 380 nm to 700 nm in the transmission spectrum is preferably in the range of 525 nm to 545 nm, more preferably in the range of 525 nm to 540 nm, and more preferably in the range of 526 nm to 540 nm. is more preferred and may be in the range of 527 nm to 535 nm.
In addition, when a cured film is formed with a thickness of 3.0 μm, the half width of the peak of the transmission spectrum at a wavelength in the range of 525 nm to 545 nm is 70 nm or less. is improved, color purity is improved, and the color reproduction range is widened. When a cured film having a thickness of 3.0 μm is formed, the half width of the peak of the transmission spectrum in the wavelength range of 525 nm to 545 nm may be 65 nm or less, 63 nm or less, or 60 nm or less.
　本発明に用いられる色材の含有量は、前記所定の波長域において所定のスペクトル透過率を満たすように用いられれば特に限定されるものではない。
　本発明に用いられる色材において、青色顔料の含有量は、色材全量に対して、例えば、１質量％以上６０質量％以下であってよく、好ましくは５質量％以上であってよく、より好ましくは１０質量％以上であってよく、さらに好ましくは１５質量％以上であってよく、好ましくは５０質量％以下であってよく、より好ましくは４０質量％以下であってよい。 The content of the coloring material used in the present invention is not particularly limited as long as it is used so as to satisfy the predetermined spectral transmittance in the predetermined wavelength range.
In the colorant used in the present invention, the content of the blue pigment may be, for example, 1% by mass or more and 60% by mass or less, preferably 5% by mass or more, relative to the total amount of the colorant. It may be preferably 10% by mass or more, more preferably 15% by mass or more, preferably 50% by mass or less, and more preferably 40% by mass or less.
　本発明に用いられる色材において、黄色顔料の含有量は、色材全量に対して、例えば、２０質量％以上９９質量％以下であってよく、好ましくは３０質量％以上であってよく、より好ましくは４０質量％以上であってよく、さらに好ましくは５０質量％以上であってよく、よりさらに好ましくは６０質量％以上であってよく、好ましくは９０質量％以下であってよく、より好ましくは８５質量％以下であってよい。 In the colorant used in the present invention, the content of the yellow pigment may be, for example, 20% by mass or more and 99% by mass or less, preferably 30% by mass or more, relative to the total amount of the colorant. It may be preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, preferably 90% by mass or less, more preferably It may be 85% by mass or less.
　ピグメントイエロー１３９の含有量は、黄色顔料全量に対して１質量％以上であってよく、より好ましくは５質量％以上であってよく、さらに好ましくは１０質量％以上であってよく、８０質量％以下であってよく、好ましくは７０質量％以下であってよい。
　黄色顔料として、ピグメントイエロー１３９とピグメントイエロー１５０とを含む場合、ピグメントイエロー１３９とピグメントイエロー１５０の合計含有量は、黄色顔料全量に対して４０質量％以上であってよく、より好ましくは６０質量％以上であってよく、さらに好ましくは８０質量％以上であってよく、１００質量％であってもよく、４０質量％以下であってよい。
　ピグメントイエロー１３９の含有量は、色材全量に対して１質量％以上であってよく、より好ましくは５質量％以上であってよく、さらに好ましくは８質量％以上であってよく、７５質量％以下であってよく、好ましくは７０質量％以下であってよく、より好ましくは６５質量％以下であってよい。 The content of Pigment Yellow 139 may be 1% by mass or more, more preferably 5% by mass or more, more preferably 10% by mass or more, and 80% by mass with respect to the total amount of yellow pigment or less, preferably 70% by mass or less.
When Pigment Yellow 139 and Pigment Yellow 150 are included as yellow pigments, the total content of Pigment Yellow 139 and Pigment Yellow 150 may be 40% by mass or more, more preferably 60% by mass, relative to the total amount of yellow pigment. or more, more preferably 80% by mass or more, 100% by mass or less, or 40% by mass or less.
The content of Pigment Yellow 139 may be 1% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, or 75% by mass with respect to the total amount of the coloring material. or less, preferably 70% by mass or less, more preferably 65% by mass or less.
　本発明に用いられる色材において、青色顔料と黄色顔料の合計に対する青色顔料の含有割合は、前記所定の波長域において所定のスペクトル透過率を満たせばよく特に限定されないが、例えば、１質量％以上６０質量％以下であってよく、好ましくは５質量％以上であってよく、より好ましくは１０質量％以上であってよく、さらに好ましくは１５質量％以上であってよく、好ましくは５０質量％以下であってよく、より好ましくは４０質量％以下であってよい。
　本発明に用いられる色材において、青色顔料と黄色顔料の合計含有量は、色材全量に対して、通常、８０質量％以上であってよく、好ましくは９０質量％以上であってよく、より好ましくは９５質量％以上であってよく、１００質量％であってよいが、ハロゲン化金属フタロシアニン顔料とは異なるその他色材を含有する場合には、９０質量％以下であってよい。 In the coloring material used in the present invention, the content ratio of the blue pigment to the total of the blue pigment and the yellow pigment is not particularly limited as long as it satisfies a predetermined spectral transmittance in the predetermined wavelength range, but is, for example, 1% by mass or more. It may be 60% by mass or less, preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, preferably 50% by mass or less. and more preferably 40% by mass or less.
In the colorant used in the present invention, the total content of the blue pigment and the yellow pigment is usually 80% by mass or more, preferably 90% by mass or more, relative to the total amount of the colorant. Preferably, it may be 95% by mass or more, and may be 100% by mass. However, when it contains other coloring material different from the halogenated metal phthalocyanine pigment, it may be 90% by mass or less.
　本発明に用いられる色材において、その他の色材の合計含有量は、色材全量に対して、０質量％であってよいが、１質量％以上であってよく、５質量％以上であってよく、一方で、通常、２０質量％以下であり、好ましくは１０質量％以下であってよい。
　但し、その他の色材としてハロゲン化金属フタロシアニン顔料が用いられる場合の合計含有量は、色材全量に対して１０質量％以下であり、通常、０．１質量％以上１０質量％以下であってよく、好ましくは１質量％以上であってよく、より好ましくは３質量％以上であってよく、好ましくは９．５質量％以下であってよい。ハロゲン化金属フタロシアニン顔料は色材全量に対して０質量％であってもよい。 In the coloring material used in the present invention, the total content of the other coloring materials may be 0% by mass, may be 1% by mass or more, or may be 5% by mass or more with respect to the total amount of the coloring material. On the other hand, it is usually 20% by mass or less, preferably 10% by mass or less.
However, when a halogenated metal phthalocyanine pigment is used as the other coloring material, the total content is 10% by mass or less with respect to the total amount of the coloring material, and is usually 0.1% by mass or more and 10% by mass or less. It may be preferably 1% by mass or more, more preferably 3% by mass or more, and preferably 9.5% by mass or less. The halogenated metal phthalocyanine pigment may be 0% by mass with respect to the total amount of the coloring material.
　本発明に用いられる色材の平均一次粒径としては、硬化膜とした場合に、外光反射を抑制可能で、且つ、発光素子からの所望の光を透過させて表示装置の輝度低下を抑制可能なものであればよく、特に限定されず、用いる色材の種類によっても異なるが、１０ｎｍ～１００ｎｍの範囲内であることが好ましく、１５ｎｍ～６０ｎｍであることがより好ましい。色材の平均一次粒径が上記範囲であることにより、本発明に係る感光性緑色樹脂組成物を用いて製造された硬化膜を備えた表示装置を、外光反射を抑制可能で、高コントラストで、かつ高品質なものとすることができる。 The average primary particle size of the colorant used in the present invention is such that when it is formed into a cured film, it can suppress external light reflection and transmit desired light from the light emitting element to suppress the decrease in luminance of the display device. It is not particularly limited as long as it is possible, and although it varies depending on the type of coloring material used, it is preferably in the range of 10 nm to 100 nm, more preferably 15 nm to 60 nm. When the average primary particle diameter of the colorant is in the above range, the display device provided with the cured film produced using the photosensitive green resin composition according to the present invention can suppress external light reflection and has high contrast. and can be of high quality.
　また、感光性緑色樹脂組成物中の色材の平均分散粒径は、用いる色材の種類によっても異なるが、１０ｎｍ～１００ｎｍの範囲内であることが好ましく、１５ｎｍ～６０ｎｍの範囲内であることがより好ましい。
　感光性緑色樹脂組成物中の色材の平均分散粒径は、少なくとも溶剤を含有する分散媒体中に分散している色材粒子の分散粒径であって、レーザー光散乱粒度分布計により測定されるものである。レーザー光散乱粒度分布計による粒径の測定としては、感光性緑色樹脂組成物に用いられている溶剤で、感光性緑色樹脂組成物をレーザー光散乱粒度分布計で測定可能な濃度に適宜希釈（例えば、１０００倍など）し、レーザー光散乱粒度分布計（例えば、日機装社製ナノトラック粒度分布測定装置ＵＰＡ－ＥＸ１５０）を用いて動的光散乱法により２３℃にて測定することができる。ここでの平均分布粒径は、体積平均粒径である。 Further, the average dispersed particle size of the colorant in the photosensitive green resin composition varies depending on the type of colorant used, but is preferably in the range of 10 nm to 100 nm, and is in the range of 15 nm to 60 nm. is more preferred.
The average dispersed particle size of the colorant in the photosensitive green resin composition is the dispersed particle size of the colorant particles dispersed in the dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. It is a thing. As the measurement of the particle size by a laser light scattering particle size distribution meter, the solvent used in the photosensitive green resin composition is appropriately diluted to a concentration that can be measured by a laser light scattering particle size distribution meter. for example, 1000 times), and measured at 23° C. by a dynamic light scattering method using a laser light scattering particle size distribution analyzer (for example, Nanotrack particle size distribution analyzer UPA-EX150 manufactured by Nikkiso Co., Ltd.). The average distribution particle size here is the volume average particle size.
　本発明に用いられる、色材は、再結晶法、ソルベントソルトミリング法等の公知の方法にて製造することができる。また、市販の色材を微細化処理して用いても良い。 The coloring material used in the present invention can be produced by known methods such as recrystallization and solvent salt milling. Alternatively, a commercially available coloring material may be used after undergoing fine processing.
　本発明に係る感光性緑色樹脂組成物において、色材の含有量は、特に限定されない。色材の含有量は、分散性及び分散安定性の点から、感光性緑色樹脂組成物の固形分全量に対して、例えば好ましくは３質量％～６５質量％、より好ましくは４質量％～６０質量％の範囲内である。上記下限値以上であれば、感光性緑色樹脂組成物を所定の膜厚（通常は１．０μｍ～５．０μｍ、例えば、３．０μｍ）に塗布した際の硬化膜が充分な色濃度を有しやすい。また、上記上限値以下であれば、保存安定性に優れると共に、充分な硬度や、基板との密着性を有する硬化膜を得ることができる。低温加熱処理を行う場合には、色材の含有量（色材濃度）は感光性緑色樹脂組成物の固形分全量に対して、例えば好ましくは３質量％～５０質量％、より好ましくは４質量％～４０質量％の範囲内である。
　尚、本発明において固形分は、後述する溶剤以外のもの全てであり、溶剤中に溶解しているモノマー等も含まれる。 The content of the coloring material in the photosensitive green resin composition according to the present invention is not particularly limited. The content of the colorant, from the viewpoint of dispersibility and dispersion stability, relative to the total solid content of the photosensitive green resin composition, for example preferably 3 wt% to 65 wt%, more preferably 4 wt% to 60 It is within the range of % by mass. If it is at least the above lower limit, the cured film when the photosensitive green resin composition is applied to a predetermined film thickness (usually 1.0 μm to 5.0 μm, for example, 3.0 μm) has sufficient color density. It's easy to do. Moreover, if it is below the said upper limit, while being excellent in storage stability, the cured film which has sufficient hardness and adhesiveness with a board|substrate can be obtained. When low-temperature heat treatment is performed, the content of the coloring material (coloring material concentration) is, for example, preferably 3% by mass to 50% by mass, more preferably 4% by mass, relative to the total solid content of the photosensitive green resin composition. % to 40% by mass.
In the present invention, the solid content refers to all substances other than the solvent, which will be described later, and includes monomers and the like dissolved in the solvent.
＜アルカリ可溶性樹脂＞
　本発明に用いられるアルカリ可溶性樹脂は酸性基を有するものであり、バインダー樹脂として作用し、かつパターン形成する際に用いられるアルカリ現像液に可溶性であるものの中から、適宜選択して使用することができる。
　本発明において、アルカリ可溶性樹脂とは、酸価が４０ｍｇＫＯＨ／ｇ以上であることを目安にすることができる。 <Alkali-soluble resin>
The alkali-soluble resin used in the present invention has an acidic group, and can be appropriately selected and used from those that act as a binder resin and are soluble in an alkali developer used for pattern formation. can.
In the present invention, the alkali-soluble resin can be defined as having an acid value of 40 mgKOH/g or more.
　アルカリ可溶性樹脂としては、従来公知のアルカリ可溶性樹脂を適宜選択して用いることができ、例えば、国際公開２０１６／１０４４９３号公報に記載のアルカリ可溶性樹脂を適宜選択して用いることができる。
　本発明における好ましいアルカリ可溶性樹脂は、酸性基、通常カルボキシ基を有する樹脂であり、具体的には、カルボキシ基を有するアクリル系共重合体及びカルボキシ基を有するスチレン－アクリル系共重合体等のアクリル系樹脂、カルボキシ基を有するエポキシ（メタ）アクリレート樹脂等が挙げられ、カルボキシ基を有するアクリル系共重合体及びカルボキシ基を有するスチレン－アクリル系共重合体等のアクリル系樹脂が好適に用いられる。これらの中で特に好ましいものは、側鎖にカルボキシ基を有するとともに、さらに側鎖にエチレン性不飽和基等の光重合性官能基を有するものである。光重合性官能基を含有することにより形成される硬化膜の膜強度が向上するからである。また、これらアクリル系共重合体及びスチレン－アクリル系共重合体等のアクリル系樹脂、並びにエポキシアクリレート樹脂は、２種以上混合して使用してもよい。 As the alkali-soluble resin, a conventionally known alkali-soluble resin can be appropriately selected and used. For example, an alkali-soluble resin described in International Publication No. 2016/104493 can be appropriately selected and used.
A preferable alkali-soluble resin in the present invention is a resin having an acidic group, usually a carboxy group. acrylic resins, epoxy (meth)acrylate resins having a carboxy group, and the like, and acrylic resins such as acrylic copolymers having a carboxy group and styrene-acrylic copolymers having a carboxy group are preferably used. Among these, particularly preferred are those having a carboxy group in the side chain and a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain. This is because the film strength of the cured film formed by containing the photopolymerizable functional group is improved. Two or more of these acrylic copolymers, acrylic resins such as styrene-acrylic copolymers, and epoxy acrylate resins may be used in combination.
　感光性緑色樹脂組成物において用いられるアルカリ可溶性樹脂は、１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。アルカリ可溶性樹脂の含有量としては特に制限はないが、感光性緑色樹脂組成物の固形分全量に対して、例えば好ましくは５質量％～６０質量％、さらに好ましくは１０質量％～４０質量％の範囲内である。アルカリ可溶性樹脂の含有量が上記下限値以上であると、充分なアルカリ現像性が得られ、また、アルカリ可溶性樹脂の含有量が上記上限値以下であると、現像時に膜荒れやパターンの欠けを抑制できる。 The alkali-soluble resin used in the photosensitive green resin composition may be used singly or in combination of two or more. The content of the alkali-soluble resin is not particularly limited, but is preferably 5% to 60% by mass, more preferably 10% to 40% by mass, based on the total solid content of the photosensitive green resin composition. Within range. When the content of the alkali-soluble resin is at least the above lower limit, sufficient alkali developability is obtained, and when the content of the alkali-soluble resin is at most the above upper limit, film roughness and pattern chipping during development are prevented. can be suppressed.
＜光重合性化合物＞
　感光性緑色樹脂組成物において用いられる光重合性化合物としては、光重合性基を分子中に有する化合物が挙げられる。光重合性基としては、光開始剤によって重合可能なものであればよく、特に限定されないが、エチレン性不飽和二重結合が挙げられ、例えば、ビニル基、アリル基、アクリロイル基又はメタクリロイル基等が挙げられる。光重合性基としては、中でも紫外線硬化性の点から、アクリロイル基又はメタクリロイル基が好適に用いられる。
　光重合性化合物としては、硬化性の点から、１分子中に光重合性基を２個以上有する化合物を含有することが好ましく、１分子中に光重合性基を３個以上有する化合物を含有することがより好ましい。 <Photopolymerizable compound>
Examples of the photopolymerizable compound used in the photosensitive green resin composition include compounds having a photopolymerizable group in the molecule. The photopolymerizable group is not particularly limited as long as it can be polymerized by a photoinitiator, but includes ethylenically unsaturated double bonds, such as vinyl group, allyl group, acryloyl group or methacryloyl group. are mentioned. As the photopolymerizable group, an acryloyl group or a methacryloyl group is preferably used from the viewpoint of ultraviolet curability.
As the photopolymerizable compound, from the viewpoint of curability, it is preferable to contain a compound having two or more photopolymerizable groups in one molecule, and a compound having three or more photopolymerizable groups in one molecule is contained. is more preferable.
　光重合性化合物としては、エチレン性不飽和二重結合を２つ以上有する化合物が好適に用いられ、特にアクリロイル基又はメタクリロイル基を２つ以上有する、多官能（メタ）アクリレートであることが好ましい。
　このような多官能（メタ）アクリレートとしては、従来公知のものの中から適宜選択して用いればよい。具体例としては、例えば、特開２０１３－０２９８３２号公報に記載のもの等が挙げられる。 As the photopolymerizable compound, a compound having two or more ethylenically unsaturated double bonds is preferably used, and a polyfunctional (meth)acrylate having two or more acryloyl groups or methacryloyl groups is particularly preferable.
As such a polyfunctional (meth)acrylate, it may be appropriately selected and used from conventionally known ones. Specific examples include those described in JP-A-2013-029832.
　これらの多官能（メタ）アクリレートは１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。また、本発明の感光性緑色樹脂組成物に優れた光硬化性（高感度）が要求される場合には、多官能（メタ）アクリレートが、重合可能な二重結合を３つ（三官能）以上有するものであるものが好ましく、３価以上の多価アルコールのポリ（メタ）アクリレート類やそれらのジカルボン酸変性物が好ましく、具体的には、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレートのコハク酸変性物、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレートのコハク酸変性物、ジペンタエリスリトールヘキサ（メタ）アクリレート等が好ましい。 These polyfunctional (meth)acrylates may be used singly or in combination of two or more. Further, when excellent photocurability (high sensitivity) is required for the photosensitive green resin composition of the present invention, the polyfunctional (meth) acrylate has three polymerizable double bonds (trifunctional) Those having the above are preferable, and poly (meth) acrylates of trihydric or higher polyhydric alcohols and dicarboxylic acid-modified products thereof are preferable. Specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (Meth)acrylate, succinic acid-modified pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol penta(meth) ) succinic acid-modified acrylate, dipentaerythritol hexa(meth)acrylate and the like are preferred.
　感光性緑色樹脂組成物において用いられる上記光重合性化合物の含有量は、特に制限はないが、感光性緑色樹脂組成物の固形分全量に対して、例えば好ましくは５質量％～６０質量％、さらに好ましくは１０質量％～４０質量％の範囲内である。光重合性化合物の含有量が上記下限値以上であると十分に光硬化が進み、露光部分が現像時の溶出を抑制でき、また、光重合性化合物の含有量が上記上限値以下であるとアルカリ現像性が十分である。 The content of the photopolymerizable compound used in the photosensitive green resin composition is not particularly limited, relative to the total solid content of the photosensitive green resin composition, for example preferably 5 wt% to 60 wt%, More preferably, it is within the range of 10% by mass to 40% by mass. If the content of the photopolymerizable compound is at least the above lower limit, photocuring will proceed sufficiently, and the exposed portion will be able to suppress elution during development. Adequate alkali developability.
＜光開始剤＞
　本発明の感光性緑色樹脂組成物において用いられる光開始剤としては、従来知られている各種光開始剤の中から、１種又は２種以上を組み合わせて用いることができる。
　光開始剤としては、例えば、芳香族ケトン類、ベンゾインエーテル類、ハロメチルオキサジアゾール化合物、α－アミノケトン類、ビイミダゾール類、Ｎ，Ｎ－ジメチルアミノベンゾフェノン、ハロメチル－Ｓ－トリアジン系化合物、チオキサントン、オキシムエステル類等を挙げることができる。このような光開始剤としては、従来公知の光開始剤を用いることができ、例えば、国際公開２０１８／０６２１０５号公報に記載されている光開始剤が挙げられる。 <Photoinitiator>
As the photoinitiator used in the photosensitive green resin composition of the present invention, one or a combination of two or more of various conventionally known photoinitiators can be used.
Examples of photoinitiators include aromatic ketones, benzoin ethers, halomethyloxadiazole compounds, α-aminoketones, biimidazoles, N,N-dimethylaminobenzophenone, halomethyl-S-triazine compounds, and thioxanthone. , oxime esters, and the like. As such a photoinitiator, a conventionally known photoinitiator can be used, and examples thereof include the photoinitiator described in WO 2018/062105.
　また、本発明に用いられるオキシムエステル系光開始剤としては、例えば、１，２－オクタジオン－１－［４－（フェニルチオ）フェニル］－，２－（ｏ－ベンゾイルオキシム）、エタノン，１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－，１－（ｏ－アセチルオキシム）、特開２０００－８００６８号公報、特開２００１－２３３８４２号公報、特表２０１０－５２７３３９号公報、特表２０１０－５２７３３８号公報、特開２０１３－０４１１５３号公報、国際公開２０１５／１５２１５３号公報、特開２０１０－２５６８９１号公報等に記載のオキシムエステル系光開始剤の中から適宜選択できる。 Examples of the oxime ester photoinitiator used in the present invention include 1,2-octadione-1-[4-(phenylthio)phenyl]-,2-(o-benzoyloxime), ethanone, 1-[ 9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyloxime), JP-A-2000-80068, JP-A-2001-233842, special table 2010-527339, JP 2010-527338, JP 2013-041153, WO 2015/152153, JP 2010-256891, among the oxime ester photoinitiators described in It can be selected as appropriate.
　低温加熱処理でも硬化膜の耐溶剤性が良好になりやすい点から、中でも、光開始剤が、下記一般式（Ａ）で表される化合物の少なくとも１種を含むことが好ましい。 The photoinitiator preferably contains at least one compound represented by the following general formula (A), because the solvent resistance of the cured film tends to be good even with low-temperature heat treatment.
Figure JPOXMLDOC01-appb-C000002
 （式中、Ｒ１及びＲ２は、それぞれ独立に、Ｒ１１、ＯＲ１１、ＣＯＲ１１、ＳＲ１１、ＣＯＮＲ１２Ｒ１３又はＣＮを表し、
　Ｒ１１、Ｒ１２及びＲ１３は、それぞれ独立に、水素原子、炭素数１～２０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアリールアルキル基又は炭素数２～２０の複素環基を表し、
　Ｒ１１、Ｒ１２及びＲ１３で表される基の水素原子は、更にＲ２１、ＯＲ２１、ＣＯＲ２１、ＳＲ２１、ＮＲ２２Ｒ２３、ＣＯＮＲ２２Ｒ２３、－ＮＲ２２－ＯＲ２３、－ＮＣＯＲ２２－ＯＣＯＲ２３、ＮＲ２２ＣＯＲ２１、ＯＣＯＲ２１、ＣＯＯＲ２１、ＳＣＯＲ２１、ＯＣＳＲ２１、ＣＯＳＲ２１、ＣＳＯＲ２１、水酸基、ニトロ基、ＣＮ、又はハロゲン原子で置換されていてもよく、
　Ｒ２１、Ｒ２２及びＲ２３は、それぞれ独立に、水素原子、炭素数１～２０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアリールアルキル基又は炭素数２～２０の複素環基を表し、
　Ｒ２１、Ｒ２２及びＲ２３で表される基の水素原子は、更に水酸基、ニトロ基、ＣＮ、ハロゲン原子、又はカルボキシ基で置換されていてもよく、
　Ｒ１１、Ｒ１２、Ｒ１３、Ｒ２１、Ｒ２２及びＲ２３で表される基のアルキレン部分は、－Ｏ－、－Ｓ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＲ２４－、－ＮＲ２４ＣＯ－、－ＮＲ２４ＣＯＯ－、－ＯＣＯＮＲ２４－、－ＳＣＯ－、－ＣＯＳ－、－ＯＣＳ－又は－ＣＳＯ－を酸素原子が隣り合わない条件で１～５個含んでいてもよく、
　Ｒ２４は、水素原子、炭素数１～２０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアリールアルキル基又は炭素数２～２０の複素環基を表し、
　Ｒ１１、Ｒ１２、Ｒ１３、Ｒ２１、Ｒ２２、Ｒ２３及びＲ２４で表される基のアルキル部分は、分岐側鎖があってもよく、環状アルキルであってもよく、
　Ｒ３は、水素原子、炭素数１～２０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアリールアルキル基又は炭素数２～２０の複素環基を表し、Ｒ３で表される基のアルキル部分は、分岐側鎖があってもよく、環状アルキルであってもよく、また、Ｒ３とＲ７、及びＲ３とＲ８はそれぞれ一緒になって環を形成していてもよく、
　Ｒ３で表される基の水素原子は、更にＲ２１、ＯＲ２１、ＣＯＲ２１、ＳＲ２１、ＮＲ２２Ｒ２３、ＣＯＮＲ２２Ｒ２３、－ＮＲ２２－ＯＲ２３、－ＮＣＯＲ２２－ＯＣＯＲ２３、ＮＲ２２ＣＯＲ２１、ＯＣＯＲ２１、ＣＯＯＲ２１、ＳＣＯＲ２１、ＯＣＳＲ２１、ＣＯＳＲ２１、ＣＳＯＲ２１、水酸基、ニトロ基、ＣＮ、又はハロゲン原子で置換されていてもよく、
　Ｒ４、Ｒ５、Ｒ６及びＲ７は、それぞれ独立に、Ｒ１１、ＯＲ１１、ＳＲ１１、ＣＯＲ１４、ＣＯＮＲ１５Ｒ１６、ＮＲ１２ＣＯＲ１１、ＯＣＯＲ１１、ＣＯＯＲ１４、ＳＣＯＲ１１、ＯＣＳＲ１１、ＣＯＳＲ１４、ＣＳＯＲ１１、水酸基、ＣＮ又はハロゲン原子を表し、Ｒ４とＲ５、Ｒ５とＲ６、及びＲ６とＲ７はそれぞれ一緒になって環を形成していてもよく、
　Ｒ１４、Ｒ１５及びＲ１６は、水素原子又は炭素数１～２０のアルキル基を表し、Ｒ１４、Ｒ１５及びＲ１６で表される基のアルキル部分は、分岐側鎖があってもよく、環状アルキルであってもよく、Ｒ８は、Ｒ１１、ＯＲ１１、ＳＲ１１、ＣＯＲ１１、ＣＯＮＲ１２Ｒ１３、ＮＲ１２ＣＯＲ１１、ＯＣＯＲ１１、ＣＯＯＲ１１、ＳＣＯＲ１１、ＯＣＳＲ１１、ＣＯＳＲ１１、ＣＳＯＲ１１、水酸基、ＣＮ又はハロゲン原子を表し、
　ｋは、０又は１を表す。）
Figure JPOXMLDOC01-appb-C000002
 (wherein R 1 and R 2 each independently represent R 11 , OR 11 , COR 11 , SR 11 , CONR 12 R 13 or CN;
R 11 , R 12 and R 13 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms or 2 to 20 carbon atoms. represents a heterocyclic group of
The hydrogen atoms of the groups represented by R 11 , R 12 and R 13 are further represented by R 21 , OR 21 , COR 21 , SR 21 , NR 22 R 23 , CONR 22 R 23 , —NR 22 —OR 23 , —NCOR 22 —OCOR 23 , NR 22 COR 21 , OCOR 21 , COOR 21 , SCOR 21 , OCSR 21 , COSR 21 , CSOR 21 , optionally substituted with a hydroxyl group, a nitro group, CN, or a halogen atom,
R 21 , R 22 and R 23 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms or 2 to 20 carbon atoms. represents a heterocyclic group of
hydrogen atoms in the groups represented by R 21 , R 22 and R 23 may be further substituted with a hydroxyl group, a nitro group, CN, a halogen atom, or a carboxy group;
The alkylene portions of the groups represented by R 11 , R 12 , R 13 , R 21 , R 22 and R 23 are -O-, -S-, -COO-, -OCO-, -NR 24 -, -NR 24 CO-, -NR 24 COO-, -OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO- may contain 1 to 5 oxygen atoms not adjacent to each other,
R 24 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms;
The alkyl portion of the groups represented by R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 may have a branched side chain or may be a cyclic alkyl,
R 3 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms; The alkyl portion of the represented groups may have branched side chains or may be cyclic alkyl, and R 3 and R 7 and R 3 and R 8 each together form a ring. may be
The hydrogen atoms of the group represented by R 3 may further be R 21 , OR 21 , COR 21 , SR 21 , NR 22 R 23 , CONR 22 R 23 , —NR 22 —OR 23 , —NCOR 22 —OCOR 23 , NR 22 COR 21 , OCOR 21 , COOR 21 , SCOR 21 , OCSR 21 , COSR 21 , CSOR 21 , a hydroxyl group, a nitro group, CN, or optionally substituted with a halogen atom,
R 4 , R 5 , R 6 and R 7 are each independently R 11 , OR 11 , SR 11 , COR 14 , CONR 15 R 16 , NR 12 COR 11 , OCOR 11 , COOR 14 , SCOR 11 , OCSR 11 , COSR 14 , CSOR 11 , a hydroxyl group, CN or a halogen atom, R 4 and R 5 , R 5 and R 6 , and R 6 and R 7 may together form a ring,
R 14 , R 15 and R 16 represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl portion of the groups represented by R 14 , R 15 and R 16 may have a branched side chain. , which may be cyclic alkyl, and R 8 is R 11 , OR 11 , SR 11 , COR 11 , CONR 12 R 13 , NR 12 COR 11 , OCOR 11 , COOR 11 , SCOR 11 , OCSR 11 , COSR 11 , CSOR 11 represents a hydroxyl group, CN or a halogen atom,
k represents 0 or 1; )
　前記一般式（Ａ）で表されるオキシムエステル化合物には、オキシムの二重結合による幾何異性体が存在するが、これらを区別するものではない。即ち、本明細書において、前記一般式（Ａ）で表わされる化合物、並びに後述する該化合物の好ましい形態である下記一般式（Ａ’）で表わされる化合物及びその例示化合物は、両方の混合物又はどちらか一方を表すものであり、異性体を示した構造に限定するものではない。 The oxime ester compound represented by the general formula (A) includes geometric isomers due to the double bond of the oxime, but these are not distinguished. That is, in the present specification, the compound represented by the general formula (A), and the compound represented by the following general formula (A′), which is a preferred form of the compound described later, and the exemplary compounds thereof are a mixture of both or either It represents one or the other, and is not limited to the structure showing the isomer.
　上記一般式（Ａ）中の、Ｒ３、Ｒ１１、Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５、Ｒ１６、Ｒ２１、Ｒ２２、Ｒ２３及びＲ２４で表される炭素数１～２０のアルキル基としては、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｓ－ブチル、ｔ－ブチル、アミル、イソアミル、ｔ－アミル、ヘキシル、ヘプチル、オクチル、イソオクチル、２－エチルヘキシル、ｔ－オクチル、ノニル、イソノニル、デシル、イソデシル、ウンデシル、ドデシル、テトラデシル、ヘキサデシル、オクタデシル、イコシル、シクロペンチル、シクロペンチルメチル、シクロペンチルエチル、シクロヘキシル、シクロヘキシルメチル、シクロヘキシルエチル等が挙げられる。 1 to 20 carbon atoms represented by R 3 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 21 , R 22 , R 23 and R 24 in the above general formula (A) Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t- octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl and the like.
　上記一般式（Ａ）中の、Ｒ３、Ｒ１１、Ｒ１２、Ｒ１３、Ｒ２１、Ｒ２２、Ｒ２３及びＲ２４で表される炭素数６～３０のアリール基としては、例えば、フェニル、トリル、キシリル、エチルフェニル、ナフチル、アンスリル、フェナンスレニル、上記アルキル基で１つ以上置換されたフェニル、ビフェニリル、ナフチル、アンスリル等が挙げられる。 Examples of the aryl group having 6 to 30 carbon atoms represented by R 3 , R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 in the general formula (A) include phenyl , tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl, phenyl substituted with one or more of the above alkyl groups, biphenylyl, naphthyl, anthryl, and the like.
　上記一般式（Ａ）中の、Ｒ３、Ｒ１１、Ｒ１２、Ｒ１３、Ｒ２１、Ｒ２２、Ｒ２３及びＲ２４で表される炭素数７～３０のアリールアルキル基としては、例えば、ベンジル、α－メチルベンジル、α、α－ジメチルベンジル、フェニルエチル等が挙げられる。 Examples of arylalkyl groups having 7 to 30 carbon atoms represented by R 3 , R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 in general formula (A) include: benzyl, α-methylbenzyl, α,α-dimethylbenzyl, phenylethyl and the like.
　上記一般式（Ａ）中の、Ｒ３、Ｒ１１、Ｒ１２、Ｒ１３、Ｒ２１、Ｒ２２、Ｒ２３、及びＲ２４で表される炭素数２～２０の複素環基としては、例えば、ピリジル、ピリミジル、フリル、チエニル、テトラヒドロフリル、ジオキソラニル、ベンゾオキサゾール－２－イル、テトラヒドロピラニル、ピロリジル、イミダゾリジル、ピラゾリジル、チアゾリジル、イソチアゾリジル、オキサゾリジル、イソオキサゾリジル、ピペリジル、ピペラジル、モルホリニル等の５～７員複素環が挙げられる。
上記一般式（Ａ）中の、Ｒ４とＲ５、Ｒ５とＲ６及びＲ６とＲ７並びにＲ３とＲ７及びＲ３とＲ８が一緒になって形成し得る環としては、例えば、シクロペンタン環、シクロヘキサン環、シクロペンテン環、ベンゼン環、ピペリジン環、モルホリン環、ラクトン環、ラクタム環等の５～７員環が好ましく挙げられる。 Examples of heterocyclic groups having 2 to 20 carbon atoms represented by R 3 , R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 in the general formula (A) include , pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, piperazyl, morpholinyl, etc. ~7-membered heterocycles.
In the above general formula (A), the rings that can be formed by R 4 and R 5 , R 5 and R 6 , R 6 and R 7 , R 3 and R 7 and R 3 and R 8 together include: Preferred examples include 5- to 7-membered rings such as cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, piperidine ring, morpholine ring, lactone ring and lactam ring.
　また、上記一般式（Ａ）中の、Ｒ４、Ｒ５、Ｒ６、Ｒ７及びＲ８で表されるハロゲン原子、並びに上記一般式（Ａ）中の、Ｒ３、Ｒ１１、Ｒ１２、Ｒ１３、Ｒ２１、Ｒ２２及びＲ２３を置換してもよいハロゲン原子としては、フッ素、塩素、臭素、ヨウ素が挙げられる。 Halogen atoms represented by R 4 , R 5 , R 6 , R 7 and R 8 in general formula (A), and R 3 , R 11 and R 12 in general formula (A) , R 13 , R 21 , R 22 and R 23 may be substituted with fluorine, chlorine, bromine and iodine.
　上記一般式（Ａ）中の、Ｒ１１、Ｒ１２、Ｒ１３、Ｒ２１、Ｒ２２及びＲ２３で表される基のアルキレン部分は、－Ｏ－、－Ｓ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＲ２４－、－ＮＲ２４ＣＯ－、－ＮＲ２４ＣＯＯ－、－ＯＣＯＮＲ２４－、－ＳＣＯ－、－ＣＯＳ－、－ＯＣＳ－又は－ＣＳＯ－により酸素原子が隣合わない条件で１～５個含んでいてもよく、この時含まれる２価の基は１種又は２種以上の基でもよく、連続して含まれ得る基の場合は２個以上連続して含まれていてもよい。 The alkylene moieties of the groups represented by R 11 , R 12 , R 13 , R 21 , R 22 and R 23 in the above general formula (A) are -O-, -S-, -COO-, -OCO -, -NR 24 -, -NR 24 CO-, -NR 24 COO- , -OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO-, 1 to 1 under the condition that oxygen atoms are not adjacent to each other; It may contain 5 divalent groups, and the divalent groups contained at this time may be one or more groups, and in the case of groups that can be contained continuously, 2 or more may be contained continuously. .
　また、上記一般式（Ａ）中の、Ｒ１１、Ｒ１２、Ｒ１３、Ｒ２１、Ｒ２２、Ｒ２３及びＲ２４で表される基のアルキル（アルキレン）部分は、分岐側鎖があってもよく、環状アルキルであってもよい。
　上記一般式（Ａ）で表される化合物の中でも、Ｒ３が縮合していてもよい芳香族環であるもの、あるいは下記一般式（Ａ’）で表される化合物は、感度が高く、製造が容易であるため好ましい。 In addition, the alkyl (alkylene) moieties of the groups represented by R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 in the general formula (A) have branched side chains. may be a cyclic alkyl.
Among the compounds represented by the above general formula (A), those in which R 3 is an optionally condensed aromatic ring or compounds represented by the following general formula (A') have high sensitivity and can be manufactured is preferred because it is easy to
Figure JPOXMLDOC01-appb-C000003
 （式中、Ｒ１、Ｒ２、Ｒ４、Ｒ５、Ｒ６、Ｒ７、Ｒ８及びｋは、上記一般式（Ａ）と同じであり、Ｒ３１、Ｒ３２、Ｒ３３、Ｒ３４及びＲ３５は、それぞれ独立に、Ｒ１１、ＯＲ１１、ＳＲ１１、ＣＯＲ１１、ＣＯＮＲ１５Ｒ１６、ＮＲ１２ＣＯＲ１１、ＯＣＯＲ１１、ＣＯＯＲ１４、ＳＣＯＲ１１、ＯＣＳＲ１１、ＣＯＳＲ１４、ＣＳＯＲ１１、水酸基、ニトロ基、ＣＮ又はハロゲン原子を表し、Ｒ３１とＲ３２、Ｒ３２とＲ３３、Ｒ３３とＲ３４及びＲ３４とＲ３５はそれぞれ一緒になって環を形成していてもよい。）
Figure JPOXMLDOC01-appb-C000003
 (Wherein, R 1 , R 2 , R 4 , R 5 , R 6 , R 7 , R 8 and k are the same as in general formula (A) above, R 31 , R 32 , R 33 , R 34 and R 35 are each independently R 11 , OR 11 , SR 11 , COR 11 , CONR 15 R 16 , NR 12 COR 11 , OCOR 11 , COOR 14 , SCOR 11 , OCSR 11 , COSR 14 , CSOR 11 , hydroxyl group , a nitro group, CN or a halogen atom, and R 31 and R 32 , R 32 and R 33 , R 33 and R 34 and R 34 and R 35 may each form a ring together.)
　Ｒ３１とＲ３２、Ｒ３２とＲ３３、Ｒ３３とＲ３４及びＲ３４とＲ３５が一緒になって形成する環の例としては、Ｒ４とＲ５、Ｒ５とＲ６及びＲ６とＲ７並びにＲ３とＲ７及びＲ３とＲ８が一緒になって形成し得る環の例として上記で挙げたものと同様の環が挙げられる。 Examples of rings formed by R 31 and R 32 , R 32 and R 33 , R 33 and R 34 and R 34 and R 35 together include R 4 and R 5 , R 5 and R 6 and R 6 and R 7 and R 3 and R 7 and R 3 and R 8 together may be formed by the same rings as those mentioned above.
　上記一般式（Ａ）及び（Ａ’）において、Ｒ１として炭素数１～１２のアルキル基又は炭素数７～１５のアリールアルキル基、Ｒ１１が炭素数６～１２のアリール基、炭素数１～８のアルキル基であるものが、溶媒溶解性が高いので好ましく、Ｒ２としてメチル基、エチル基又はフェニル基であるものが反応性が高いので好ましく、Ｒ４～Ｒ７として水素原子又はシアノ基、特に水素原子であるものが合成が容易なので好ましく、Ｒ８として水素原子であるものが合成が容易なので好ましく、ｋは１であるのが、感度が高いので好ましく、上記一般式（Ａ’）において、Ｒ３１～Ｒ３５のうち少なくとも１つがニトロ基、ＣＮ、ハロゲン原子、ＣＯＲ１１であり、Ｒ１１が炭素数６～１２のアリール基、炭素数１～８のアルキル基であるものが感度が高いので好ましく、Ｒ３１～Ｒ３５のうち少なくとも１つがニトロ基、ＣＮ又はハロゲン原子であるものがより好ましく、Ｒ３３がニトロ基、ＣＮ又はハロゲン原子であるものが特に好ましい。 In the above general formulas (A) and (A′), R 1 is an alkyl group having 1 to 12 carbon atoms or an arylalkyl group having 7 to 15 carbon atoms, R 11 is an aryl group having 6 to 12 carbon atoms, and 1 carbon atom. Alkyl groups of 1 to 8 are preferred because they are highly soluble in solvents, R 2 is preferably a methyl group, ethyl group or phenyl group because of their high reactivity, and R 4 to R 7 are hydrogen atoms or cyano A group, particularly a hydrogen atom, is preferred for ease of synthesis. A hydrogen atom as R 8 is preferred for ease of synthesis. k is preferably 1 for high sensitivity. ), wherein at least one of R 31 to R 35 is a nitro group, CN, a halogen atom, or COR 11 , and R 11 is an aryl group having 6 to 12 carbon atoms or an alkyl group having 1 to 8 carbon atoms. Preferred because of their high sensitivity, more preferred are those in which at least one of R 31 to R 35 is a nitro group, CN or a halogen atom, and particularly preferred are those in which R 33 is a nitro group, CN or a halogen atom.
　上記一般式（Ａ）で表される化合物の好ましい具体例としては、例えば、以下の化合物が挙げられる。また、国際公開２０１５／１５２１５３号公報に記載されている、化合物Ｎｏ．１～Ｎｏ．２１２が挙げられる。 Preferred specific examples of the compound represented by the general formula (A) include the following compounds. In addition, Compound No. described in International Publication No. 2015/152153. 1 to No. 212.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　上記一般式（Ａ）で表される化合物は、例えば、国際公開２０１５／１５２１５３号公報を参照し、使用する材料に応じて溶剤、反応温度、反応時間、精製方法等を適宜選択することにより、合成できる。また、市販品を適宜入手して用いても良い。 For the compound represented by the general formula (A), for example, referring to International Publication 2015/152153, by appropriately selecting a solvent, reaction temperature, reaction time, purification method, etc. according to the material to be used, Can be synthesized. Moreover, you may obtain and use a commercial item suitably.
　本発明の感光性緑色樹脂組成物において用いられる光開始剤の合計含有量は、本発明の効果が損なわれない限り特に制限はないが、感光性緑色樹脂組成物の固形分全量に対して、好ましくは０．１質量％～１５．０質量％、さらに好ましくは１．０質量％～１０．０質量％の範囲内である。この含有量が上記下限値以上であると十分に光硬化が進みやすく、耐溶剤性や基板密着性が良好になりやすく、一方上記上限値以下であると、線幅シフトが抑制され、高精細なパターンを形成しやすい。 The total content of the photoinitiator used in the photosensitive green resin composition of the present invention is not particularly limited as long as the effect of the present invention is not impaired, relative to the total solid content of the photosensitive green resin composition, It is preferably in the range of 0.1% by mass to 15.0% by mass, more preferably in the range of 1.0% by mass to 10.0% by mass. If the content is at least the above lower limit, photocuring will proceed sufficiently, and the solvent resistance and substrate adhesion will tend to be good. easy to form patterns.
　前記一般式（Ａ）で表される化合物の少なくとも１種の合計含有量は、低温加熱処理でも基板密着性、及び耐溶剤性が良好な硬化膜を形成可能な点から、光開始剤の全量に対して、好ましくは３０．０質量％以上、より好ましくは５０．０質量％以上、更に好ましくは７０．０質量％以上であり、１００質量％であってよい。 The total content of at least one of the compounds represented by the general formula (A) is the total amount of the photoinitiator from the viewpoint that a cured film having good substrate adhesion and solvent resistance can be formed even in low-temperature heat treatment. is preferably 30.0% by mass or more, more preferably 50.0% by mass or more, still more preferably 70.0% by mass or more, and may be 100% by mass.
＜溶剤＞
　本発明の感光性緑色樹脂組成物は、溶剤を含んでもよい。本発明に用いられる溶剤としては、感光性緑色樹脂組成物中の各成分とは反応せず、これらを溶解もしくは分散可能な有機溶剤であればよく、特に限定されない。溶剤は単独もしくは２種以上組み合わせて使用することができる。
　溶剤の具体例としては、例えば、メチルアルコール、エチルアルコール、Ｎ－プロピルアルコール、ｉ－プロピルアルコール、メトキシアルコール、エトキシアルコールなどのアルコール系溶剤；メトキシエトキシエタノール、エトキシエトキシエタノールなどのカルビトール系溶剤；酢酸エチル、酢酸ブチル、メトキシプロピオン酸メチル、メトキシプロピオン酸エチル、エトキシプロピオン酸エチル、乳酸エチル、ヒドロキシプロピオン酸メチル、ヒドロキシプロピオン酸エチル、ｎ－ブチルアセテート、イソブチルアセテート、酪酸イソブチル、酪酸ｎ－ブチル、乳酸エチル、シクロヘキサノールアセテートなどのエステル系溶剤；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、２－ヘプタノンなどのケトン系溶剤；メトキシエチルアセテート、プロピレングリコールモノメチルエーテルアセテート、３－メトキシ－３－メチル－１－ブチルアセテート、３－メトキシブチルアセテート、エトキシエチルアセテートなどのグリコールエーテルアセテート系溶剤；メトキシエトキシエチルアセテート、エトキシエトキシエチルアセテート、ブチルカルビトールアセテート（ＢＣＡ）などのカルビトールアセテート系溶剤；プロピ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等のジアセテート類；エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、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メチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテル、ジプロピレングリコールジメチルエーテルなどのグリコールエーテル系溶剤；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリドンなどの非プロトン性アミド溶剤；γ－ブチロラクトンなどのラクトン系溶剤；テトラヒドロフランなどの環状エーテル系溶剤；ベンゼン、トルエン、キシレン、ナフタレンなどの不飽和炭化水素系溶剤；Ｎ－ヘプタン、Ｎ－ヘキサン、Ｎ－オクタンなどの飽和炭化水素系溶剤；トルエン、キシレン等の芳香族炭化水素類などの有機溶剤が挙げられる。これらの溶剤の中ではグリコールエーテルアセテート系溶剤、カルビトールアセテート系溶剤、グリコールエーテル系溶剤、エステル系溶剤が他の成分の溶解性の点で好適に用いられる。中でも、本発明に用いる溶剤としては、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、ブチルカルビトールアセテート（ＢＣＡ）、３－メトキシ－３－メチル－１－ブチルアセテート、エトキシプロピオン酸エチル、乳酸エチル、及び、３－メトキシブチルアセテートよりなる群から選択される１種以上であることが、他の成分の溶解性や塗布適性の点から好ましい。 <Solvent>
The photosensitive green resin composition of the present invention may contain a solvent. The solvent used in the present invention is not particularly limited as long as it does not react with each component in the photosensitive green resin composition and is capable of dissolving or dispersing them. A solvent can be used individually or in combination of 2 or more types.
Specific examples of solvents include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, i-propyl alcohol, methoxy alcohol and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ester solvents such as ethyl lactate and cyclohexanol acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and 2-heptanone; methoxyethyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-3-methyl-1 -glycol ether acetate solvents such as butyl acetate, 3-methoxybutyl acetate and ethoxyethyl acetate; carbitol acetate solvents such as methoxyethoxyethyl acetate, ethoxyethoxyethyl acetate and butyl carbitol acetate (BCA); propylene glycol diacetate , 1,3-butylene glycol diacetate and other diacetates; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, dipropylene glycol Glycol ether solvents such as dimethyl ether; Aprotic amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone; Lactone solvents such as γ-butyrolactone; Cyclic ether solvents such as tetrahydrofuran unsaturated hydrocarbon solvents such as benzene, toluene, xylene and naphthalene; saturated hydrocarbon solvents such as N-heptane, N-hexane and N-octane; organic solvents such as aromatic hydrocarbons such as toluene and xylene are mentioned. Among these solvents, glycol ether acetate-based solvents, carbitol acetate-based solvents, glycol ether-based solvents, and ester-based solvents are preferably used in terms of solubility of other components. Among them, the solvent used in the present invention includes propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and one or more selected from the group consisting of 3-methoxybutyl acetate, from the viewpoint of solubility of other components and applicability.
　本発明に係る感光性緑色樹脂組成物において、溶剤の含有量は、着色層を精度良く形成することができる範囲で適宜設定すればよい。溶剤の含有量は、該溶剤を含む感光性緑色樹脂組成物の全量に対して、通常、好ましくは５５質量％～９５質量％、より好ましくは６５質量％～８８質量％の範囲内である。上記溶剤の含有量が、上記範囲内であることにより、塗布性に優れたものとすることができる。 In the photosensitive green resin composition according to the present invention, the content of the solvent may be appropriately set within a range in which the colored layer can be formed with high precision. The content of the solvent is usually in the range of preferably 55% by mass to 95% by mass, more preferably 65% by mass to 88% by mass, based on the total amount of the photosensitive green resin composition containing the solvent. When the content of the solvent is within the above range, excellent applicability can be obtained.
＜分散剤＞
　本発明の感光性緑色樹脂組成物において、色材を分散させる場合には、色材分散性と色材分散安定性の点から、分散剤を更に含んでいても良い。
　本発明において分散剤は、従来公知の分散剤の中から適宜選択して用いることができる。分散剤としては、例えば、カチオン系、アニオン系、ノニオン系、両性、シリコーン系、フッ素系等の界面活性剤を使用できる。界面活性剤の中でも、均一に、微細に分散し得る点から、高分子分散剤が好ましい。 <Dispersant>
In the photosensitive green resin composition of the present invention, when the colorant is dispersed, a dispersant may be further included from the viewpoint of colorant dispersibility and colorant dispersion stability.
In the present invention, the dispersant can be appropriately selected and used from conventionally known dispersants. As the dispersant, for example, cationic, anionic, nonionic, amphoteric, silicone, or fluorine surfactants can be used. Among surfactants, polymer dispersants are preferred because they can be uniformly and finely dispersed.
　高分子分散剤としては、例えば、（メタ）アクリレート共重合体系分散剤；ポリウレタン類；不飽和ポリアミド類；ポリシロキサン類；長鎖ポリアミノアミドリン酸塩類；ポリエチレンイミン誘導体（ポリ（低級アルキレンイミン）と遊離カルボキシ基含有ポリエステルとの反応により得られるアミドやそれらの塩基）；ポリアリルアミン誘導体（ポリアリルアミンと、遊離のカルボキシ基を有するポリエステル、ポリアミド又はエステルとアミドの共縮合物（ポリエステルアミド）の３種の化合物の中から選ばれる１種以上の化合物とを反応させて得られる反応生成物）等が挙げられる。 Examples of polymer dispersants include (meth)acrylate copolymer dispersants; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; amides obtained by reaction with free carboxyl group-containing polyesters and their bases); polyallylamine derivatives (polyallylamine and polyesters having free carboxyl groups, polyamides, or cocondensates of esters and amides (polyesteramides) (a reaction product obtained by reacting with one or more compounds selected from the compounds of ), and the like.
　本発明においては、分散剤として、（メタ）アクリレート共重合体系分散剤を用いることが低温加熱処理でも耐溶剤性が良好になりやすい点から好ましい。（メタ）アクリレート共重合体系分散剤は、前記光重合性化合物と前記一般式（Ａ）で表される化合物を含む光開始剤との相溶性が良好になるため、開始剤が着色層中に均一に存在し易くなり、着色層が均一に硬化することで未反応成分が減少し、着色層の内部応力も小さくなるため、溶剤に浸漬した時の着色層の変化が小さくなると推定される。 In the present invention, it is preferable to use a (meth)acrylate copolymer-based dispersant as the dispersant, since solvent resistance tends to be improved even with low-temperature heat treatment. (Meth) acrylate copolymer-based dispersant has good compatibility with the photoinitiator containing the compound represented by the photopolymerizable compound and the general formula (A), so that the initiator is in the colored layer It is presumed that the colored layer is likely to exist uniformly, and the uniform curing of the colored layer reduces the amount of unreacted components and reduces the internal stress of the colored layer, so that the colored layer changes less when immersed in a solvent.
　本発明において、（メタ）アクリレート共重合体系分散剤とは、共重合体であって、少なくとも（メタ）アクリレート由来の構成単位を含む分散剤をいう。
　（メタ）アクリレート共重合体系分散剤は、色材吸着部位として機能する構成単位と、溶剤親和性部位として機能する構成単位とを含有する共重合体であることが好ましく、溶剤親和性部位として機能する構成単位に少なくとも（メタ）アクリレート由来の構成単位を含むことが好ましい。 In the present invention, the (meth)acrylate copolymer-based dispersant refers to a dispersant that is a copolymer and contains at least a (meth)acrylate-derived structural unit.
The (meth)acrylate copolymer-based dispersant is preferably a copolymer containing a structural unit that functions as a coloring material adsorption site and a structural unit that functions as a solvent affinity site, and functions as a solvent affinity site. It is preferable that at least a (meth)acrylate-derived structural unit is included in the structural units to be used.
　色材吸着部位として機能する構成単位は、（メタ）アクリレート由来の構成単位と共重合可能なエチレン性不飽和モノマー由来の構成単位を挙げることができる。色材吸着部位としては、酸性基含有エチレン性不飽和モノマー由来の構成単位であってもよいし、塩基性基含有エチレン性不飽和モノマー由来の構成単位であってもよい。
　塩基性基含有エチレン性不飽和モノマー由来の構成単位としては、下記一般式（Ｉ）で表される構成単位が、分散性に優れている点から好ましい。 Examples of structural units that function as colorant adsorption sites include structural units derived from ethylenically unsaturated monomers copolymerizable with structural units derived from (meth)acrylate. The coloring material adsorption site may be a structural unit derived from an ethylenically unsaturated monomer containing an acidic group, or a structural unit derived from an ethylenically unsaturated monomer containing a basic group.
As the structural unit derived from the basic group-containing ethylenically unsaturated monomer, a structural unit represented by the following general formula (I) is preferable from the viewpoint of excellent dispersibility.
Figure JPOXMLDOC01-appb-C000005
 （一般式（Ｉ）中、Ｒ７１は水素原子又はメチル基、Ａ１は２価の連結基、Ｒ７２及びＲ７３は、それぞれ独立して、水素原子、又はヘテロ原子を含んでもよい炭化水素基を表し、Ｒ７２及びＲ７３が互いに結合して環構造を形成してもよい。）
Figure JPOXMLDOC01-appb-C000005
 (In general formula (I), R 71 is a hydrogen atom or a methyl group, A 1 is a divalent linking group, R 72 and R 73 are each independently a hydrogen atom, or a hydrocarbon which may contain a hetero atom. group, and R 72 and R 73 may combine with each other to form a ring structure.)
　一般式（Ｉ）において、Ａ１は、２価の連結基である。２価の連結基としては、例えば、直鎖、分岐又は環状のアルキレン基、水酸基を有する、直鎖、分岐又は環状のアルキレン基、アリーレン基、－ＣＯＮＨ－基、－ＣＯＯ－基、－ＮＨＣＯＯ－基、エーテル基（－Ｏ－基）、チオエーテル基（－Ｓ－基）、及びこれらの組み合わせ等が挙げられる。なお、本発明において、２価の連結基の結合の向きは任意である。すなわち、２価の連結基に－ＣＯＮＨ－が含まれる場合、－ＣＯが主鎖の炭素原子側で－ＮＨが側鎖の窒素原子側であっても良いし、反対に、－ＮＨが主鎖の炭素原子側で－ＣＯが側鎖の窒素原子側であっても良い。
　中でも、分散性の点から、一般式（Ｉ）におけるＡ１は、－ＣＯＮＨ－基又は－ＣＯＯ－基を含む２価の連結基であることが好ましく、－ＣＯＮＨ－基又は－ＣＯＯ－基と、炭素数１～１０のアルキレン基とを含む２価の連結基であることがより好ましい。 In general formula (I), A 1 is a divalent linking group. As the divalent linking group, for example, a linear, branched or cyclic alkylene group, a linear, branched or cyclic alkylene group having a hydroxyl group, an arylene group, -CONH- group, -COO- group, -NHCOO- groups, ether groups (--O--groups), thioether groups (--S--groups), and combinations thereof. In the present invention, the bonding direction of the divalent linking group is arbitrary. That is, when -CONH- is included in the divalent linking group, -CO may be on the carbon atom side of the main chain and -NH may be on the nitrogen atom side of the side chain, on the contrary, -NH is the main chain --CO may be on the nitrogen atom side of the side chain.
Among them, from the viewpoint of dispersibility, A 1 in the general formula (I) is preferably a divalent linking group containing a -CONH- group or a -COO- group, and a -CONH- group or a -COO- group. , and an alkylene group having 1 to 10 carbon atoms are more preferable.
　Ｒ７２及びＲ７３における、ヘテロ原子を含んでもよい炭化水素基における炭化水素基は、例えば、アルキル基、アラルキル基、アリール基などが挙げられる。
　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、イソプロピル基、ｔｅｒｔ－ブチル基、２－エチルヘキシル基、シクロペンチル基、シクロヘキシル基等が挙げられ、アルキル基の炭素数は、１～１８が好ましく、中でも、メチル基又はエチル基であることがより好ましい。
　アラルキル基としては、例えば、ベンジル基、フェネチル基、ナフチルメチル基、ビフェニルメチル基等が挙げられる。アラルキル基の炭素数は、７～２０が好ましく、更に７～１４が好ましい。
　また、アリール基としては、フェニル基、ビフェニル基、ナフチル基、トリル基、キシリル基等が挙げられる。アリール基の炭素数は、６～２４が好ましく、更に６～１２が好ましい。なお、上記好ましい炭素数には、置換基の炭素数は含まれない。
　ヘテロ原子を含む炭化水素基とは、上記炭化水素基中の炭素原子がヘテロ原子で置き換えられた構造を有するか、上記炭化水素基中の水素原子がヘテロ原子を含む置換基で置き換えられた構造を有する。炭化水素基が含んでいてもよいヘテロ原子としては、例えば、酸素原子、窒素原子、硫黄原子、ケイ素原子等が挙げられる。
　また、炭化水素基中の水素原子は、フッ素原子、塩素原子、臭素原子等のハロゲン原子により置換されていてもよい。 Examples of the hydrocarbon group in the hydrocarbon group optionally containing a heteroatom for R 72 and R 73 include an alkyl group, an aralkyl group and an aryl group.
Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2-ethylhexyl group, cyclopentyl group, cyclohexyl group and the like, and the number of carbon atoms in the alkyl group is 1. to 18 are preferable, and among them, a methyl group or an ethyl group is more preferable.
The aralkyl group includes, for example, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like. The number of carbon atoms in the aralkyl group is preferably 7-20, more preferably 7-14.
Aryl groups include phenyl, biphenyl, naphthyl, tolyl, and xylyl groups. The number of carbon atoms in the aryl group is preferably 6-24, more preferably 6-12. In addition, the number of carbon atoms of the substituent is not included in the preferable number of carbon atoms.
A hydrocarbon group containing a heteroatom has a structure in which a carbon atom in the hydrocarbon group is replaced with a heteroatom, or a structure in which a hydrogen atom in the hydrocarbon group is replaced by a substituent containing a heteroatom. have Examples of the heteroatom that the hydrocarbon group may contain include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom and the like.
Further, hydrogen atoms in the hydrocarbon group may be substituted with halogen atoms such as fluorine, chlorine and bromine atoms.
　Ｒ７２及びＲ７３が互いに結合して環構造を形成しているとは、Ｒ７２及びＲ７３が窒素原子を介して環構造を形成していることをいう。Ｒ７２及びＲ７３が形成する環構造にヘテロ原子が含まれていても良い。環構造は特に限定されないが、例えば、ピロリジン環、ピペリジン環、モルフォリン環等が挙げられる。 The expression that R 72 and R 73 are bonded to each other to form a ring structure means that R 72 and R 73 form a ring structure via a nitrogen atom. The ring structure formed by R72 and R73 may contain a heteroatom. Although the ring structure is not particularly limited, examples thereof include pyrrolidine ring, piperidine ring, morpholine ring and the like.
　本発明においては、中でも、Ｒ７２及びＲ７３が各々独立に、水素原子、炭素数１～５のアルキル基、フェニル基であるか、又は、Ｒ７２及びＲ７３が結合してピロリジン環、ピペリジン環、モルフォリン環を形成していることが好ましい。 In the present invention, among others, R 72 and R 73 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, or R 72 and R 73 are bonded to form a pyrrolidine ring, piperidine It preferably forms a ring or a morpholine ring.
　上記一般式（Ｉ）で表される構成単位を誘導するモノマーとしては、ジメチルアミノエチル（メタ）アクリレート、ジメチルアミノプロピル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、ジエチルアミノプロピル（メタ）アクリレート等のアルキル基置換アミノ基含有（メタ）アクリレート等、ジメチルアミノエチル（メタ）アクリルアミド、ジメチルアミノプロピル（メタ）アクリルアミドなどのアルキル基置換アミノ基含有（メタ）アクリルアミド等が挙げられる。中でも分散性、及び分散安定性が向上する点でジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、ジメチルアミノプロピル（メタ）アクリルアミドを好ましく用いることができる。
　重合体において、一般式（Ｉ）で表される構成単位は、１種類からなるものであってもよく、２種以上の構成単位を含むものであってもよい。 Examples of monomers that derive structural units represented by the general formula (I) include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, and the like. Alkyl group-substituted amino group-containing (meth)acrylates, alkyl group-substituted amino group-containing (meth)acrylamides such as dimethylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, and the like can be mentioned. Among them, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylaminopropyl (meth)acrylamide can be preferably used in terms of improving dispersibility and dispersion stability.
In the polymer, the structural unit represented by formula (I) may consist of one type, or may contain two or more types of structural units.
　また、色材吸着部位として機能する構成単位としては、前記一般式（Ｉ）で表される構成単位が有する窒素部位の少なくとも一部と、有機酸化合物及びハロゲン化炭化水素からなる群から選ばれる少なくとも１種とが塩を形成してもよい（以下、このような共重合体を、塩型共重合体と称することがある）。
　　前記有機酸化合物としては、中でも、下記一般式（１）で表される化合物及び下記一般式（３）で表される化合物が好ましく、前記ハロゲン化炭化水素としては、中でも、下記一般式（２）で表される化合物が好ましい。すなわち、前記有機酸化合物及びハロゲン化炭化水素からなる群から選ばれる少なくとも１種としては、下記一般式（１）～（３）よりなる群から選択される１種以上の化合物を好ましく用いることができる。 Further, the structural unit functioning as the coloring material adsorption site is selected from the group consisting of at least part of the nitrogen site possessed by the structural unit represented by the general formula (I), an organic acid compound, and a halogenated hydrocarbon. At least one of them may form a salt (hereinafter, such a copolymer may be referred to as a salt-type copolymer).
As the organic acid compound, among others, a compound represented by the following general formula (1) and a compound represented by the following general formula (3) are preferable. ) are preferred. That is, at least one compound selected from the group consisting of the organic acid compound and the halogenated hydrocarbon is preferably one or more compounds selected from the group consisting of the following general formulas (1) to (3). can.
Figure JPOXMLDOC01-appb-C000006
 （一般式（１）において、Ｒａは、炭素数１～２０の直鎖、分岐鎖又は環状のアルキル基、ビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは－Ｏ－Ｒｅを表し、Ｒｅは、炭素数１～２０の直鎖、分岐鎖又は環状のアルキル基、ビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは炭素数１～４のアルキレン基を介した（メタ）アクリロイル基を表す。一般式（２）において、Ｒｂ、Ｒｂ’、及びＲｂ”はそれぞれ独立に、水素原子、酸性基又はそのエステル基、置換基を有してもよい炭素数１～２０の直鎖、分岐鎖又は環状のアルキル基、置換基を有してもよいビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは－Ｏ－Ｒｆを表し、Ｒｆは、置換基を有してもよい炭素数１～２０の直鎖、分岐鎖又は環状のアルキル基、置換基を有してもよいビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは炭素数１～４のアルキレン基を介した（メタ）アクリロイル基を表し、Ｘは、塩素原子、臭素原子、又はヨウ素原子を表す。一般式（３）において、Ｒｃ及びＲｄはそれぞれ独立に、水素原子、水酸基、炭素数１～２０の直鎖、分岐鎖又は環状のアルキル基、ビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは－Ｏ－Ｒｅを表し、Ｒｅは、炭素数１～２０の直鎖、分岐鎖又は環状のアルキル基、ビニル基、置換基を有してもよいフェニル基又はベンジル基、或いは炭素数１～４のアルキレン基を介した（メタ）アクリロイル基を表す。但し、Ｒｃ及びＲｄの少なくとも一つは炭素原子を含む。）
Figure JPOXMLDOC01-appb-C000006
 (In the general formula (1), R a is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group which may have a substituent or a benzyl group, or -O- Represents R e , R e is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group which may have a substituent or a benzyl group, or a C 1 to 4 represents a (meth)acryloyl group via an alkylene group.In general formula (2), R b , R b′ , and R b″ each independently represent a hydrogen atom, an acidic group or an ester group thereof, or a substituent. a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group which may have a substituent, a phenyl group which may have a substituent or a benzyl group, or -O- R f represents an optionally substituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group optionally having a substituent, a substituted may be a phenyl group or a benzyl group, or a (meth)acryloyl group via an alkylene group having 1 to 4 carbon atoms, and X represents a chlorine atom, a bromine atom, or an iodine atom. , R c and R d are each independently a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl group or a benzyl group, Alternatively, —O—R e , where R e is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl group or a benzyl group, or a carbon number represents a (meth)acryloyl group via 1 to 4 alkylene groups, provided that at least one of R c and R d contains a carbon atom.)
　前記一般式（１）～（３）の各符号については、国際公開第２０１６／１０４４９３号の記載と同様であってよい。
　前記有機酸化合物がフェニルホスホン酸やフェニルホスフィン酸等の酸性有機リン化合物であることが、色材の分散性及び分散安定性に優れる点から好ましい。このような分散剤に用いられる有機酸化合物の具体例としては、例えば、特開２０１２－２３６８８２号公報等に記載の有機酸化合物が好適なものとして挙げられる。
　また、前記ハロゲン化炭化水素としては、臭化アリル、塩化ベンジル等のハロゲン化アリル及びハロゲン化アラルキルの少なくとも１種であることが、色材の分散性及び分散安定性に優れる点から好ましい。 Each symbol of the general formulas (1) to (3) may be the same as described in WO 2016/104493.
It is preferable that the organic acid compound is an acidic organic phosphorus compound such as phenylphosphonic acid or phenylphosphinic acid from the viewpoint of excellent dispersibility and dispersion stability of the coloring material. Specific examples of the organic acid compound used in such a dispersant include, for example, the organic acid compounds described in JP-A-2012-236882 as suitable ones.
Further, the halogenated hydrocarbon is preferably at least one selected from allyl halides such as allyl bromide and benzyl chloride, and aralkyl halides, from the viewpoint of excellent dispersibility and dispersion stability of the coloring material.
　塩型共重合体において、有機酸化合物及びハロゲン化炭化水素からなる群から選ばれる少なくとも１種の含有量は、一般式（Ｉ）で表される構成単位が有する末端の窒素部位と塩形成しているものであることから、一般式（Ｉ）で表される構成単位が有する末端の窒素部位に対して、有機酸化合物及びハロゲン化炭化水素からなる群から選ばれる少なくとも１種の合計を０．０１モル以上とすることが好ましく、０．０５モル以上とすることがより好ましく、０．１モル以上とすることがさらに好ましく、０．２モル以上とすることが特に好ましい。上記下限値以上であると、塩形成による色材分散性向上の効果が得られやすい。同様に、１モル以下とすることが好ましく、０．８モル以下とすることがより好ましく、０．７モル以下とすることがさらに好ましく、０．６モル以下とすることが特に好ましい。上記上限値以下であると現像密着性や溶剤再溶解性に優れたものとすることができる。
　なお、有機酸化合物及びハロゲン化炭化水素からなる群から選ばれる少なくとも１種は、１種単独で用いてもよく、２種以上を組み合わせてもよい。２種以上を組み合わせる場合は、その合計の含有量が上記範囲内であることが好ましい。 In the salt-type copolymer, the content of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons forms a salt with the terminal nitrogen moiety of the structural unit represented by general formula (I). Therefore, the total of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons is 0 for the terminal nitrogen portion of the structural unit represented by general formula (I) It is preferably 0.01 mol or more, more preferably 0.05 mol or more, still more preferably 0.1 mol or more, and particularly preferably 0.2 mol or more. When it is at least the above lower limit, the effect of improving the dispersibility of the coloring material by salt formation is likely to be obtained. Similarly, it is preferably 1 mol or less, more preferably 0.8 mol or less, even more preferably 0.7 mol or less, and particularly preferably 0.6 mol or less. When it is not more than the above upper limit, it can be excellent in development adhesion and solvent re-solubility.
At least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons may be used singly or in combination of two or more. When combining two or more, the total content is preferably within the above range.
　塩型共重合体の調製方法としては、塩形成前の共重合体を溶解乃至分散した溶剤中に、前記有機酸化合物及びハロゲン化炭化水素からなる群から選ばれる少なくとも１種を添加し、攪拌、更に必要により加熱する方法などが挙げられる。
　なお、共重合体の当該一般式（Ｉ）で表される構成単位が有する末端の窒素部位と、前記有機酸化合物及びハロゲン化炭化水素からなる群から選ばれる少なくとも１種とが塩を形成していること、及びその割合は、例えばＮＭＲ等、公知の手法により確認することができる。 As a method for preparing the salt-type copolymer, at least one selected from the group consisting of the organic acid compound and the halogenated hydrocarbon is added to the solvent in which the copolymer before salt formation is dissolved or dispersed, and the mixture is stirred. and a method of heating if necessary.
The terminal nitrogen portion of the structural unit represented by the general formula (I) of the copolymer and at least one selected from the group consisting of the organic acid compound and the halogenated hydrocarbon form a salt. and the ratio thereof can be confirmed by a known method such as NMR.
　前記一般式（Ｉ）で表される構成単位を有する共重合体は、分散性及び分散安定性の点から、前記一般式（Ｉ）で表される構成単位を有し、グラフトポリマー鎖に（メタ）アクリレート由来の構成単位を有するグラフト共重合体、及び、前記一般式（Ｉ）で表される構成単位を含むＡブロックと、（メタ）アクリレート由来の構成単位を含むＢブロックとを有するブロック共重合体、の少なくとも１種であることがより好ましい。
　以下、前記グラフト共重合体、及び、前記ブロック共重合体について、順に説明する。 From the viewpoint of dispersibility and dispersion stability, the copolymer having the structural unit represented by the general formula (I) has the structural unit represented by the general formula (I), and the graft polymer chain ( A graft copolymer having a meth)acrylate-derived structural unit, and a block having an A block containing a structural unit represented by the general formula (I) and a B block containing a (meth)acrylate-derived structural unit is more preferably at least one of copolymers.
Hereinafter, the graft copolymer and the block copolymer will be described in order.
　前記一般式（Ｉ）で表される構成単位を有し、グラフトポリマー鎖に（メタ）アクリレート由来の構成単位を有するグラフト共重合体としては、前記一般式（Ｉ）で表される構成単位と下記一般式（ＩＩ）で表される構成単位とを有するグラフト共重合体、並びに、当該グラフト共重合体の当該一般式（Ｉ）で表される構成単位が有する窒素部位の少なくとも一部と有機酸化合物及びハロゲン化炭化水素からなる群から選ばれる少なくとも１種とが塩を形成した塩型グラフト共重合体の少なくとも１種が挙げられる。 As a graft copolymer having a structural unit represented by the general formula (I) and having a (meth)acrylate-derived structural unit in the graft polymer chain, the structural unit represented by the general formula (I) and A graft copolymer having a structural unit represented by the following general formula (II), and at least part of the nitrogen site of the structural unit represented by the general formula (I) of the graft copolymer and an organic At least one salt-type graft copolymer formed by forming a salt with at least one selected from the group consisting of acid compounds and halogenated hydrocarbons may be mentioned.
Figure JPOXMLDOC01-appb-C000007
 （一般式（ＩＩ）中、Ｒ７１’は水素原子又はメチル基、Ａ２は直接結合又は２価の連結基、Ｐｏｌｙｍｅｒはポリマー鎖を表し、当該ポリマー鎖の構成単位には、（メタ）アクリレート由来の構成単位が含まれる。）
Figure JPOXMLDOC01-appb-C000007
 (In general formula (II), R 71′ is a hydrogen atom or a methyl group, A 2 is a direct bond or a divalent linking group, Polymer represents a polymer chain, and the constituent units of the polymer chain include (meth)acrylate (Contains structural units derived from
　前記一般式（ＩＩ）において、Ａ２は、直接結合又は２価の連結基である。Ａ２における２価の連結基としては、エチレン性不飽和二重結合由来の炭素原子とポリマー鎖を連結可能であれば、特に制限はない。Ａ２における２価の連結基としては、例えば、前記Ａ１における２価の連結基と同様のものが挙げられる。
　中でも、分散性の点から、一般式（ＩＩ）におけるＡ２は、－ＣＯＮＨ－基又は－ＣＯＯ－基を含む２価の連結基であることが好ましく、－ＣＯＮＨ－基又は－ＣＯＯ－基と、炭素数１～１０のアルキレン基とを含む２価の連結基であることがより好ましい。 In the general formula (II), A2 is a direct bond or a divalent linking group. The divalent linking group for A2 is not particularly limited as long as it can link the carbon atom derived from the ethylenically unsaturated double bond and the polymer chain. Examples of the divalent linking group for A 2 include those similar to the divalent linking group for A 1 .
Among them, from the viewpoint of dispersibility, A 2 in general formula (II) is preferably a divalent linking group containing a -CONH- group or a -COO- group, and a -CONH- group or a -COO- group. , and an alkylene group having 1 to 10 carbon atoms are more preferable.
　前記一般式（ＩＩ）において、Ｐｏｌｙｍｅｒは、ポリマー鎖を表し、当該ポリマー鎖の構成単位には、（メタ）アクリレート由来の構成単位が含まれる。グラフト共重合体は、特定のポリマー鎖を有する前記一般式（ＩＩ）で表される構成単位を有することにより、溶剤親和性が良好になり、色材の分散性及び分散安定性が良好なものとなり、且つ、前述の光開始剤との相溶性も良好になる。
　当該ポリマー鎖の構成単位としては、下記一般式（ＩＩＩ）で表される構成単位が挙げられる。 In the general formula (II), Polymer represents a polymer chain, and structural units of the polymer chain include structural units derived from (meth)acrylate. The graft copolymer has a structural unit represented by the general formula (II) having a specific polymer chain, so that the solvent affinity is improved, and the dispersibility and dispersion stability of the coloring material are improved. and compatibility with the photoinitiator described above is improved.
Examples of structural units of the polymer chain include structural units represented by the following general formula (III).
Figure JPOXMLDOC01-appb-C000008
 （一般式（ＩＩＩ）中、Ｒ７４”は水素原子又はメチル基、Ａ４は２価の連結基、Ｒ８０は、水素原子、又はヘテロ原子を含んでもよい炭化水素基である。）
Figure JPOXMLDOC01-appb-C000008
 (In general formula (III), R 74″ is a hydrogen atom or a methyl group, A 4 is a divalent linking group, and R 80 is a hydrogen atom or a hydrocarbon group which may contain a hetero atom.)
　Ａ４の２価の連結基としては、例えば、前記Ａ１における２価の連結基と同様のものが挙げられる。本発明においては、（メタ）アクリレート由来の構成単位として、一般式（ＩＩＩ）中のＡ４が－ＣＯＯ－基を含む２価の連結基である一般式（ＩＩＩ）で表される構成単位が、少なくとも含まれる。カラーフィルタ用途に使用される有機溶剤への溶解性の点から、一般式（ＩＩＩ）におけるＡ４は、－ＣＯＮＨ－基を含む２価の連結基を含んでいてもよい。 Examples of the divalent linking group for A 4 include those similar to the divalent linking group for A 1 . In the present invention, as a structural unit derived from (meth)acrylate, a structural unit represented by general formula (III) in which A 4 in general formula (III) is a divalent linking group containing a —COO— group is , at least included. From the viewpoint of solubility in organic solvents used for color filters, A 4 in general formula (III) may contain a divalent linking group containing a -CONH- group.
　Ｒ８０における、ヘテロ原子を含んでもよい炭化水素基における炭化水素基は、例えば、アルキル基、アルケニル基、アリール基、及びアラルキル基やアルキル置換アリール基等のこれらの組み合わせが挙げられる。Ｒ８０における、ヘテロ原子を含んでもよい炭化水素基における炭化水素基としては、例えば、炭素数１～１８のアルキル基、炭素数２～１８のアルケニル基、アリール基、及び、アラルキル基やアルキル置換アリール基等のこれらの組み合わせが挙げられる。
　前記炭素数１～１８のアルキル基は、直鎖状、分岐状、環状のいずれであってもよく、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、ｎ－ノニル基、ｎ－ラウリル基、ｎ－ステアリル基、シクロペンチル基、シクロヘキシル基、ボルニル基、イソボルニル基、ジシクロペンタニル基、アダマンチル基、低級アルキル基置換アダマンチル基などを挙げることができる。アルキル基の炭素数は、１～１２が好ましく、更に１～６が好ましい。
　前記炭素数２～１８のアルケニル基は、直鎖状、分岐状、環状のいずれであってもよい。このようなアルケニル基としては、例えばビニル基、アリル基、プロペニル基などを挙げることができる。アルケニル基の二重結合の位置には限定はないが、得られたポリマーの反応性の点からは、アルケニル基の末端に二重結合があることが好ましい。アルケニル基の炭素数は、２～１２が好ましく、更に２～８が好ましい。
　アリール基としては、フェニル基、ビフェニル基、ナフチル基、トリル基、キシリル基等が挙げられる。アリール基の炭素数は、６～２４が好ましく、更に６～１２が好ましい。
　また、アラルキル基としては、ベンジル基、フェネチル基、ナフチルメチル基、ビフェニルメチル基等が挙げられ、更に置換基を有していてもよい。アラルキル基の炭素数は、７～２０が好ましく、更に７～１４が好ましい。
　また、前記アリール基やアラルキル基等の芳香環には、置換基として炭素数１～３０の直鎖状、分岐状のアルキル基が結合していても良い。 Examples of hydrocarbon groups in the hydrocarbon group optionally containing a heteroatom in R 80 include alkyl groups, alkenyl groups, aryl groups, and combinations thereof such as aralkyl groups and alkyl-substituted aryl groups. The hydrocarbon group in the hydrocarbon group optionally containing a heteroatom for R 80 includes, for example, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group, an aralkyl group, and an alkyl-substituted Combinations of these, such as aryl groups, are included.
The alkyl group having 1 to 18 carbon atoms may be linear, branched or cyclic, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl and n- nonyl group, n-lauryl group, n-stearyl group, cyclopentyl group, cyclohexyl group, bornyl group, isobornyl group, dicyclopentanyl group, adamantyl group, lower alkyl group-substituted adamantyl group and the like. The number of carbon atoms in the alkyl group is preferably 1-12, more preferably 1-6.
The alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. Examples of such alkenyl groups include vinyl groups, allyl groups, and propenyl groups. Although the position of the double bond of the alkenyl group is not limited, it is preferable that the alkenyl group has a double bond at the terminal from the viewpoint of the reactivity of the resulting polymer. The alkenyl group preferably has 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms.
Aryl groups include phenyl, biphenyl, naphthyl, tolyl, and xylyl groups. The number of carbon atoms in the aryl group is preferably 6-24, more preferably 6-12.
Moreover, the aralkyl group includes a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group, and the like, and may further have a substituent. The number of carbon atoms in the aralkyl group is preferably 7-20, more preferably 7-14.
Further, a linear or branched alkyl group having 1 to 30 carbon atoms may be bonded as a substituent to the aromatic ring such as the aryl group or the aralkyl group.
　Ｒ８０における炭化水素基としては、中でも、分散安定性の点から、炭素数１～１８のアルキル基、アルキル基が置換されていても良い炭素数６～１２のアリール基、及び、アルキル基が置換されていても良い炭素数７～１４のアラルキル基からなる群から選択される１種以上であることが好ましく、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、ｎ－ノニル基、ｎ－ラウリル基、ｎ－ステアリル基、アルキル基が置換されていても良いフェニル基及びベンジル基からなる群から選択される１種以上であることが好ましい。 Among the hydrocarbon groups for R 80 , from the viewpoint of dispersion stability, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 12 carbon atoms which may be substituted with an alkyl group, and an alkyl group. It is preferably one or more selected from the group consisting of optionally substituted aralkyl groups having 7 to 14 carbon atoms, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n It is preferably one or more selected from the group consisting of -nonyl group, n-lauryl group, n-stearyl group, phenyl group optionally substituted with an alkyl group, and benzyl group.
　炭化水素基が含んでいてもよいヘテロ原子としては、例えば、酸素原子、窒素原子、硫黄原子、ケイ素原子等が挙げられる。ヘテロ原子を含んでもよい炭化水素基としては、例えば、炭化水素基の炭素鎖中に、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－Ｏ－、－Ｓ－、－ＣＯ－Ｓ－、－Ｓ－ＣＯ－、－Ｏ－ＣＯ－Ｏ－、－ＣＯ－ＮＨ－、－ＮＨ－ＣＯ－、－ＯＣＯ－ＮＨ－、－ＮＨ－ＣＯＯ－、－ＮＨ－ＣＯ－ＮＨ－、－ＮＨ－Ｏ－、－Ｏ－ＮＨ－等の連結基が含まれる構造が挙げられる。
　また、当該炭化水素基は、前記グラフト共重合体の分散性能等を妨げない範囲で、置換基を有しても良く、置換基としては、例えば、ハロゲン原子、水酸基、カルボキシ基、アルコキシ基、ニトロ基、シアノ基、エポキシ基、イソシアネート基、チオール基等が挙げられる。 Examples of the heteroatom that the hydrocarbon group may contain include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom and the like. The hydrocarbon group which may contain a heteroatom includes, for example, -CO-, -COO-, -OCO-, -O-, -S-, -CO-S-, - S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O- , —O—NH— and other connecting groups.
Further, the hydrocarbon group may have a substituent as long as it does not interfere with the dispersion performance of the graft copolymer. Nitro group, cyano group, epoxy group, isocyanate group, thiol group and the like.
　また、Ｒ８０におけるヘテロ原子を含んでもよい炭化水素基としては、炭化水素基においてヘテロ原子を含む連結基を介して末端にアルケニル基等の重合性基が付加された構造であっても良い。例えば、一般式（ＩＩＩ）で表される構成単位が（メタ）アクリル酸由来の構成単位にグリシジル（メタ）アクリレートを反応させたような構造であっても良い。すなわち、一般式（ＩＩＩ）における－Ａ４－Ｒ８０の構造が、－ＣＯＯ－ＣＨ２ＣＨ（ＯＨ）ＣＨ２－ＯＣＯ－ＣＲ＝ＣＨ２（ここで、Ｒは水素原子又はメチル基）で示される構造であっても良い。また、一般式（ＩＩＩ）で表される構成単位がヒドロキシアルキル（メタ）アクリレート由来の構成単位に２－イソシアナトアルキル（メタ）アクリレートを反応させたような構造であっても良い。すなわち、一般式（ＩＩＩ）におけるＲ８０が、－Ｒ’－ＯＣＯＮＨ－Ｒ”－ＯＣＯ－ＣＲ＝ＣＨ２（ここで、Ｒ’及びＲ”はそれぞれ独立にアルキレン基、Ｒは水素原子又はメチル基）で示される構造であっても良い。 The hydrocarbon group optionally containing a heteroatom in R 80 may have a structure in which a polymerizable group such as an alkenyl group is added to the end of the hydrocarbon group via a linking group containing a heteroatom. For example, the structural unit represented by general formula (III) may have a structure obtained by reacting a structural unit derived from (meth)acrylic acid with glycidyl (meth)acrylate. That is, the structure of -A 4 -R 80 in general formula (III) is -COO-CH 2 CH(OH)CH 2 -OCO-CR=CH 2 (where R is a hydrogen atom or a methyl group). It may be a structure that can be Further, the structural unit represented by general formula (III) may have a structure obtained by reacting a structural unit derived from hydroxyalkyl(meth)acrylate with 2-isocyanatoalkyl(meth)acrylate. That is, R 80 in general formula (III) is -R'-OCONH-R"-OCO-CR=CH 2 (wherein R' and R" are each independently an alkylene group, R is a hydrogen atom or a methyl group ) may be the structure shown.
　一般式（ＩＩＩ）で表される構成単位を誘導するモノマーとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、２－エトキシエチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、アダマンチル（メタ）アクリレート、（メタ）アクリル酸、２－メタクリロイルオキシエチルサクシネート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート及びポリエチレングリコール（メタ）アクリレート、フェノキシエチレングリコール（メタ）アクリレート等由来の構成単位を有するものが好ましい。しかしながら、これらに限定されるものではない。 Examples of monomers that induce structural units represented by general formula (III) include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) Acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate , dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, (meth) acrylic acid, 2-methacryloyloxyethyl succinate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- Hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, phenoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate and polyethylene glycol (meth)acrylate , phenoxyethylene glycol (meth)acrylate and the like are preferred. However, it is not limited to these.
　本発明において、前記Ｒ８０としては、中でも、後述する有機溶剤との溶解性に優れたものを用いることが好ましく、色材分散液に使用する有機溶剤に合わせて適宜選択されれば良い。具体的には、例えば前記有機溶剤が、色材分散液の有機溶剤として一般的に使用されているエーテルアルコールアセテート系、エーテル系、エステル系、アルコール系などの有機溶剤を用いる場合には、メチル基、エチル基、イソブチル基、ｎ－ブチル基、２－エチルヘキシル基、ベンジル基、シクロヘキシル基、ジシクロペンタニル基、ヒドロキシエチル基、フェノキシエチル基、アダマンチル基、メトキシポリエチレングリコール基、メトキシポリプロピレングリコール基、ポリエチレングリコール基等が好ましい。 In the present invention, as the R 80 , it is preferable to use one having excellent solubility in the organic solvent described later, and it may be appropriately selected according to the organic solvent used in the colorant dispersion. Specifically, for example, when the organic solvent is an ether-alcohol acetate-based, ether-based, ester-based, or alcohol-based organic solvent generally used as an organic solvent for a colorant dispersion, methyl group, ethyl group, isobutyl group, n-butyl group, 2-ethylhexyl group, benzyl group, cyclohexyl group, dicyclopentanyl group, hydroxyethyl group, phenoxyethyl group, adamantyl group, methoxypolyethylene glycol group, methoxypolypropylene glycol group , polyethylene glycol group and the like are preferred.
　前記グラフト共重合体は、前記一般式（ＩＩ）で表される構成単位中のポリマー鎖の構成単位に、下記一般式（ＩＶ）で表される構成単位及び下記一般式（ＩＶ’）で表される構成単位からなる群から選択される少なくとも１種の構成単位が含まれることが、感光性緑色樹脂組成物の硬化物の耐溶剤性が更に良好になり、且つ感光性緑色樹脂組成物の現像時間の短縮化の点から好ましい。
　下記一般式（ＩＶ）で表される構成単位及び下記一般式（ＩＶ’）で表される構成単位は、前記一般式（ＩＩＩ）で表される構成単位に包含される構成単位である。 In the graft copolymer, a structural unit represented by the following general formula (IV) and a structural unit represented by the following general formula (IV') are added to the structural unit of the polymer chain in the structural unit represented by the general formula (II). The inclusion of at least one structural unit selected from the group consisting of structural units is further improved the solvent resistance of the cured product of the photosensitive green resin composition, and of the photosensitive green resin composition This is preferable from the viewpoint of shortening the development time.
The structural unit represented by the following general formula (IV) and the structural unit represented by the following general formula (IV') are structural units included in the structural unit represented by the general formula (III).
Figure JPOXMLDOC01-appb-C000009
 （一般式（ＩＶ）中、Ｒ７４は水素原子又はメチル基、Ａ３は２価の連結基、Ｒ７５はエチレン基又はプロピレン基、Ｒ７６は、水素原子、又は炭化水素基であり、ｍは３以上８０以下の数を表す。
一般式（ＩＶ’）中、Ｒ７４’は水素原子又はメチル基、Ａ３’は２価の連結基、Ｒ７７は炭素数が１～１０のアルキレン基、Ｒ７８は炭素数が３～７のアルキレン基、Ｒ７９は、水素原子、又は炭化水素基であり、ｎは１以上４０以下の数を表す。）
Figure JPOXMLDOC01-appb-C000009
 (In general formula (IV), R 74 is a hydrogen atom or a methyl group, A 3 is a divalent linking group, R 75 is an ethylene group or a propylene group, R 76 is a hydrogen atom or a hydrocarbon group, m represents a number of 3 or more and 80 or less.
In general formula (IV'), R 74' is a hydrogen atom or a methyl group, A 3' is a divalent linking group, R 77 is an alkylene group having 1 to 10 carbon atoms, and R 78 has 3 to 7 carbon atoms. The alkylene group of R 79 is a hydrogen atom or a hydrocarbon group, and n represents a number of 1 or more and 40 or less. )
　Ａ３の２価の連結基としては、例えば、前記Ａ１における２価の連結基と同様のものが挙げられる。中でも、カラーフィルタ用途に使用される有機溶剤への溶解性の点から、一般式（ＩＶ）におけるＡ３は、－ＣＯＮＨ－基又は－ＣＯＯ－基を含む２価の連結基であることが好ましく、－ＣＯＮＨ－基又は－ＣＯＯ－基であることがより好ましく、－ＣＯＯ－基であることがより更に好ましい。 Examples of the divalent linking group for A 3 include those similar to the divalent linking group for A 1 . Among them, from the viewpoint of solubility in organic solvents used for color filters, A 3 in general formula (IV) is preferably a divalent linking group containing a -CONH- group or a -COO- group. , -CONH- or -COO- group, and even more preferably -COO- group.
　前記ｍは、エチレンオキシド鎖又はプロピレンオキシド鎖の繰り返し単位数を表し、３以上の数を表すが、中でも水染み発生抑制、及び耐溶剤性の点から、１９以上であることが好ましく、２１以上であることがより好ましい。
　前記ｍが１９以上の場合には、前記グラフト共重合体は、一般式（Ｉ）で表される構成単位と一般式（ＩＩ）で表される構成単位とを有する主鎖部分を含有し、前記一般式（ＩＩ）で表される構成単位はポリマー鎖において、特定の繰り返し数を有するポリエチレンオキシド鎖又はポリプロピレンオキシド鎖を含む一般式（ＩＶ）で表される構成単位が含まれる。本発明に用いられる特定のグラフト共重合体においては、このようにグラフトしているポリマー鎖の構成単位に、特定の繰り返し数を有するポリエチレンオキシド鎖又はポリプロピレンオキシド鎖を有する構成単位が含まれ、グラフトしているポリマー鎖自体が枝分かれ構造を有する。グラフトしている複数のポリマー鎖が膜中で立体的に広がり、比表面積が大きくなることから、溶剤の塗膜への侵入や色材への到達をより抑制することができると推定される。
　一方、ｍの上限値は８０以下であるが、カラーフィルタ用途に使用される有機溶剤への溶解性の点から、５０以下であることが好ましい。 The above m represents the number of repeating units of an ethylene oxide chain or a propylene oxide chain, and represents a number of 3 or more. It is more preferable to have
When m is 19 or more, the graft copolymer contains a main chain portion having a structural unit represented by general formula (I) and a structural unit represented by general formula (II), The structural unit represented by the general formula (II) includes a structural unit represented by the general formula (IV) containing a polyethylene oxide chain or a polypropylene oxide chain having a specific repeating number in the polymer chain. In the specific graft copolymer used in the present invention, the constituent units of the polymer chain thus grafted include a constituent unit having a polyethylene oxide chain or polypropylene oxide chain having a specific repeating number, The polymer chain itself has a branched structure. It is presumed that the multiple grafted polymer chains spread three-dimensionally in the film and the specific surface area increases, so that the penetration of the solvent into the coating film and the arrival of the coloring material can be further suppressed.
On the other hand, the upper limit of m is 80 or less, but preferably 50 or less from the viewpoint of solubility in organic solvents used for color filters.
　Ｒ７６における炭化水素基としては、前記Ｒ８０における炭化水素基と同様であって良い。
　Ｒ７６における炭化水素基としては、中でも、分散安定性や相溶性の点から、炭素数１～１８のアルキル基、アルキル基が置換されていても良い炭素数６～１２のアリール基、及び、アルキル基が置換されていても良い炭素数７～１４のアラルキル基からなる群から選択される１種以上であることが好ましく、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、ｎ－ノニル基、ｎ－ラウリル基、ｎ－ステアリル基、アルキル基が置換されていても良いフェニル基及びベンジル基からなる群から選択される１種以上であることが好ましい。 The hydrocarbon group for R 76 may be the same as the hydrocarbon group for R 80 .
As the hydrocarbon group for R 76 , from the viewpoint of dispersion stability and compatibility, among others, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 12 carbon atoms which may be substituted with an alkyl group, and The alkyl group is preferably one or more selected from the group consisting of optionally substituted aralkyl groups having 7 to 14 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl. It is preferably one or more selected from the group consisting of groups, n-nonyl groups, n-lauryl groups, n-stearyl groups, phenyl groups optionally substituted with alkyl groups, and benzyl groups.
　また、前記一般式（ＩＶ’）中、Ａ３’の２価の連結基としては、例えば、前記Ａ１における２価の連結基と同様のものが挙げられる。中でも、カラーフィルタ用途に使用される有機溶剤への溶解性の点から、一般式（ＩＶ’）におけるＡ３’は、－ＣＯＮＨ－基又は－ＣＯＯ－基を含む２価の連結基であることが好ましく、－ＣＯＮＨ－基又は－ＣＯＯ－基であることがより好ましく、－ＣＯＯ－基であることがより更に好ましい。
　前記一般式（ＩＶ’）において、Ｒ７７は炭素数が１～１０のアルキレン基であるが、中でも炭素数が２～８のアルキレン基であることが、溶剤再溶解性の点から好ましい。
　Ｒ７８は炭素数が３～７のアルキレン基であるが、中でも炭素数が３～５のアルキレン基、更に炭素数が５のアルキレン基であることが基材密着性の点から好ましい。
　Ｒ７９は、水素原子、又は炭化水素基であり、前記Ｒ７９における炭化水素基としては、前記Ｒ７６における炭化水素基と同様であって良い。 Further, in the general formula (IV'), examples of the divalent linking group for A3 ' include the same divalent linking groups as the divalent linking groups for A1. Among them, from the viewpoint of solubility in organic solvents used for color filters, A 3' in general formula (IV') is a divalent linking group containing a -CONH- or -COO- group. is preferred, a -CONH- group or a -COO- group is more preferred, and a -COO- group is even more preferred.
In the general formula (IV′), R 77 is an alkylene group having 1 to 10 carbon atoms, preferably an alkylene group having 2 to 8 carbon atoms from the viewpoint of solvent resolubility.
R 78 is an alkylene group having 3 to 7 carbon atoms. Among them, an alkylene group having 3 to 5 carbon atoms, and more preferably an alkylene group having 5 carbon atoms are preferable from the standpoint of substrate adhesion.
R 79 is a hydrogen atom or a hydrocarbon group, and the hydrocarbon group for R 79 may be the same as the hydrocarbon group for R 76 above.
　前記一般式（ＩＶ’）における前記ｎはエステル鎖の繰り返し単位数を表し、１以上の数を表すが、中でも現像時間の短縮化、及び優れた耐溶剤性を同時に満たす点から、２以上であることが好ましく、更に３以上であることが好ましい。
　一方、ｎの上限値は４０以下であるが、カラーフィルタ用途に使用される有機溶剤への溶解性の点から、２０以下であることが好ましい。 The n in the general formula (IV′) represents the number of repeating units of the ester chain, and represents a number of 1 or more. There is preferably one, and more preferably 3 or more.
On the other hand, the upper limit of n is 40 or less, but preferably 20 or less from the viewpoint of solubility in organic solvents used for color filters.
　前記ポリマー鎖において、前記一般式（ＩＶ）で表される構成単位及び下記一般式（ＩＶ’）で表される構成単位からなる群から選択される少なくとも１種の構成単位は、１種単独でも良いが、２種以上混合されていても良い。
　前記ポリマー鎖において、前記一般式（ＩＶ）で表される構成単位が含まれることが、酸素原子による溶剤親和性部の作用がより顕著になり、感光性緑色樹脂組成物の現像時間の短縮化、及び耐溶剤性が向上する点から好ましい。 In the polymer chain, at least one structural unit selected from the group consisting of structural units represented by the general formula (IV) and structural units represented by the following general formula (IV′) may be used alone. Although it is good, 2 or more types may be mixed.
In the polymer chain, the inclusion of the structural unit represented by the general formula (IV) makes the action of the solvent affinity portion due to the oxygen atom more pronounced, and shortens the development time of the photosensitive green resin composition. , and solvent resistance is improved.
　中でも、耐溶剤性が向上し、水染み抑制効果が向上し、且つ現像残渣抑制効果が向上する点から、前記一般式（ＩＩ）で表される構成単位中のポリマー鎖の構成単位に、ｍが１９以上８０以下の前記一般式（ＩＶ）で表される構成単位からなる群から選択される少なくとも１種と、ｍが３以上１０以下の前記一般式（ＩＶ）で表される構成単位からなる群から選択される少なくとも１種とを組み合わせて含有することがより好ましく、ｍが１９以上５０以下の前記一般式（ＩＶ）で表される構成単位からなる群から選択される少なくとも１種と、ｍが３以上８以下の前記一般式（ＩＶ）で表される構成単位からなる群から選択される少なくとも１種とを組み合わせて含有することがよりさらに好ましい。 Among them, from the viewpoint of improving solvent resistance, improving the effect of suppressing water staining, and improving the effect of suppressing development residue, the structural unit of the polymer chain in the structural unit represented by the general formula (II) has m At least one selected from the group consisting of structural units represented by the general formula (IV) in which m is 19 or more and 80 or less, and a structural unit represented by the general formula (IV) in which m is 3 or more and 10 or less It is more preferable to contain in combination with at least one selected from the group consisting of at least one selected from the group consisting of structural units represented by the general formula (IV) in which m is 19 or more and 50 or less , m is 3 or more and m is 3 or more and 8 or less, and at least one selected from the group consisting of the structural units represented by the above general formula (IV) is further preferably combined.
　前記一般式（ＩＩ）で表される構成単位中のポリマー鎖の構成単位に、ｍが１９以上８０以下の前記一般式（ＩＶ）で表される構成単位からなる群から選択される少なくとも１種を含有する場合、ｍが１９以上８０以下の前記一般式（ＩＶ）で表される構成単位の合計割合は、前記ポリマー鎖の全構成単位を１００質量％とした時に、水染み抑制効果の点から、１質量％以上であることが好ましく、２質量％以上であることがより好ましく、４質量％以上であることがより更に好ましく、一方で、溶剤再溶解性、及び水染み抑制効果の点から、７５質量％以下であることが好ましく、６５質量％以下であることがより好ましく、５０質量％以下であることがより更に好ましい。 At least one selected from the group consisting of structural units represented by the general formula (IV) in which m is 19 or more and 80 or less, in the structural unit of the polymer chain in the structural unit represented by the general formula (II) When containing, the total proportion of the structural units represented by the general formula (IV) in which m is 19 or more and 80 or less is, when the total structural units of the polymer chain is 100% by mass, the effect of suppressing water staining Therefore, it is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 4% by mass or more, while solvent re-solubility and water stain suppression effect Therefore, it is preferably 75% by mass or less, more preferably 65% by mass or less, and even more preferably 50% by mass or less.
　前記一般式（ＩＩ）で表される構成単位中のポリマー鎖の構成単位に、ｍが１９以上８０以下の前記一般式（ＩＶ）で表される構成単位からなる群から選択される少なくとも１種と、ｍが３以上１０以下の前記一般式（ＩＶ）で表される構成単位からなる群から選択される少なくとも１種とを組み合わせて含有する場合、ｍが３以上１０以下の前記一般式（ＩＶ）で表される構成単位の合計割合は、前記ポリマー鎖の全構成単位を１００質量％とした時に、２０質量％以上であることが好ましい。一方で、溶剤再溶解性の点から、前記ポリマー鎖において、ｍが３以上１０以下の前記一般式（ＩＶ）で表される構成単位の合計割合は、当該ポリマー鎖の全構成単位を１００質量％とした時に、８０質量％以下であることが好ましく、６０質量％以下であることがより好ましい。
　また、前記ポリマー鎖において、ｍが１９以上８０以下の前記一般式（ＩＶ）で表される構成単位と、ｍが３以上１０以下の前記一般式（ＩＶ）で表される構成単位との混合割合は、現像残渣抑制効果向上の点から、ｍが１９以上８０以下の前記一般式（ＩＶ）で表される構成単位と、ｍが３以上１０以下の前記一般式（ＩＶ）で表される構成単位との合計を１００質量部とした時に、ｍが１９以上８０以下の前記一般式（ＩＶ）で表される構成単位の合計が３質量部以上であることが好ましく、６質量部以上であることがより好ましく、８０質量部以下であることが好ましく、６０質量部以下であることがより好ましい。 At least one selected from the group consisting of structural units represented by the general formula (IV) in which m is 19 or more and 80 or less, in the structural unit of the polymer chain in the structural unit represented by the general formula (II) and at least one selected from the group consisting of structural units represented by the general formula (IV) in which m is 3 or more and 10 or less, when m is 3 or more and 10 or less in the general formula ( The total proportion of the constituent units represented by IV) is preferably 20% by mass or more when the total constituent units of the polymer chain are taken as 100% by mass. On the other hand, from the viewpoint of solvent resolubility, in the polymer chain, the total proportion of the structural units represented by the general formula (IV) in which m is 3 or more and 10 or less is 100 mass of all the structural units of the polymer chain. %, it is preferably 80% by mass or less, more preferably 60% by mass or less.
Further, in the polymer chain, a structural unit represented by the general formula (IV) in which m is 19 or more and 80 or less and a structural unit represented by the general formula (IV) in which m is 3 or more and 10 or less are mixed. The ratio is represented by the structural unit represented by the general formula (IV) in which m is 19 or more and 80 or less and the general formula (IV) in which m is 3 or more and 10 or less from the viewpoint of improving the effect of suppressing development residue. When the total of the structural units is 100 parts by mass, the total of the structural units represented by the general formula (IV) in which m is 19 or more and 80 or less is preferably 3 parts by mass or more, and 6 parts by mass or more. more preferably 80 parts by mass or less, and more preferably 60 parts by mass or less.
　分散安定性、高コントラスト化、現像時間の短縮化、及び優れた耐溶剤性を同時に満たす点から、前記ポリマー鎖の全構成単位を１００質量％とした時に、前記一般式（ＩＶ）で表される構成単位及び前記一般式（ＩＶ’）で表される構成単位からなる群から選択される少なくとも１種の構成単位の合計割合は、１質量％以上であることが好ましく、２質量％以上であることがより好ましく、４質量％以上であることがより更に好ましい。前記一般式（ＩＶ）で表される構成単位及び前記一般式（ＩＶ’）で表される構成単位からなる群から選択される少なくとも１種の構成単位の合計割合は、溶剤再溶解性の点から、前記ポリマー鎖の全構成単位を１００質量％とした時に、８０質量％以下であることが好ましく、７０質量％以下であることがより好ましく、６０質量％以下であることがより更に好ましい。 From the viewpoint of satisfying dispersion stability, high contrast, shortening of development time, and excellent solvent resistance at the same time, when the total structural units of the polymer chain is 100% by mass, it is represented by the general formula (IV). and at least one structural unit selected from the group consisting of structural units represented by the general formula (IV′) is preferably 1% by mass or more, and 2% by mass or more. It is more preferable that the content is 4% by mass or more. The total proportion of at least one structural unit selected from the group consisting of the structural units represented by the general formula (IV) and the structural units represented by the general formula (IV') is the point of solvent re-solubility. Therefore, it is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less when the total constituent units of the polymer chain are 100% by mass.
　前記ポリマー鎖において、前記一般式（ＩＶ）で表される構成単位及び前記一般式（ＩＶ’）で表される構成単位を包含する前記一般式（ＩＩＩ）で表される構成単位は、１種単独でも良いが、２種以上混合されていても良い。
　色材の分散性及び分散安定性の点から、前記一般式（ＩＩＩ）で表される構成単位の合計割合は、当該ポリマー鎖の全構成単位を１００質量％とした時に、７０質量％以上であることが好ましく、９０質量％以上であることがより好ましい。一方で、分散安定性、及び優れた耐溶剤性を同時に満たす点から、前記ポリマー鎖において、前記一般式（ＩＩＩ）で表される構成単位の合計割合は、当該ポリマー鎖の全構成単位を１００質量％とした時に、１００質量％であってもよい。
　中でも（メタ）アクリレート由来の構成単位の合計割合は、分散安定性及び耐溶剤性、開始剤との相溶性の点から、当該ポリマー鎖の全構成単位を１００質量％とした時に、６０質量％以上であることが好ましく、８０質量％以上であることがより好ましい。一方で、分散安定性、及び優れた耐溶剤性を同時に満たす点から、前記ポリマー鎖において、（メタ）アクリレート由来の構成単位の合計割合は、当該ポリマー鎖の全構成単位を１００質量％とした時に、１００質量％であってもよい。 In the polymer chain, the structural unit represented by the general formula (III) including the structural unit represented by the general formula (IV) and the structural unit represented by the general formula (IV') is one type. It may be used alone or in combination of two or more.
From the viewpoint of the dispersibility and dispersion stability of the coloring material, the total proportion of the structural units represented by the general formula (III) is 70% by mass or more when the total structural units of the polymer chain are 100% by mass. It is preferably 90% by mass or more, more preferably 90% by mass or more. On the other hand, from the viewpoint of satisfying dispersion stability and excellent solvent resistance at the same time, the total proportion of the structural units represented by the general formula (III) in the polymer chain is 100 of the total structural units of the polymer chain. When expressed as % by mass, it may be 100% by mass.
Among them, the total proportion of (meth)acrylate-derived structural units is 60% by mass when the total structural units of the polymer chain is 100% by mass, from the viewpoint of dispersion stability, solvent resistance, and compatibility with the initiator. It is preferably 80% by mass or more, and more preferably 80% by mass or more. On the other hand, from the viewpoint of satisfying dispersion stability and excellent solvent resistance at the same time, the total proportion of structural units derived from (meth)acrylate in the polymer chain is 100% by mass of all structural units of the polymer chain. Sometimes it may be 100% by weight.
　前記グラフト共重合体の前記一般式（ＩＩ）で表される構成単位中のポリマー鎖の構成単位には、前記一般式（ＩＩＩ）で表される構成単位の他に、その他の構成単位を含んでいても良い。
　その他の構成単位としては、前記一般式（ＩＩＩ）で表される構成単位を誘導するモノマーと共重合可能な不飽和二重結合を有する単量体由来の構成単位を挙げることができる。
　その他の構成単位を誘導するモノマーとしては、例えば、スチレン、α－メチルスチレン等のスチレン類、フェニルビニルエーテル等のビニルエーテル類等が挙げられる。 The structural units of the polymer chain in the structural units represented by the general formula (II) of the graft copolymer include other structural units in addition to the structural units represented by the general formula (III). You can stay
Examples of other structural units include structural units derived from monomers having unsaturated double bonds copolymerizable with the monomers from which the structural units represented by general formula (III) are derived.
Examples of monomers from which other structural units are derived include styrene, styrenes such as α-methylstyrene, vinyl ethers such as phenyl vinyl ether, and the like.
　前記グラフト共重合体の前記一般式（ＩＩ）で表される構成単位中のポリマー鎖において、その他の構成単位の合計割合は、本発明の効果の点から、当該ポリマー鎖の全構成単位を１００質量％とした時に、３０質量％以下であることが好ましく、１０質量％以下であることがより好ましい。 In the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer, the total proportion of other structural units is 100% of the total structural units of the polymer chain, from the viewpoint of the effect of the present invention. When expressed as % by mass, it is preferably 30% by mass or less, more preferably 10% by mass or less.
　Ｐｏｌｙｍｅｒにおけるポリマー鎖の質量平均分子量Ｍｗは、色材の分散性及び分散安定性の点から、２０００以上であることが好ましく、３０００以上であることがより好ましく、４０００以上であることがより更に好ましく、１５０００以下であることがより好ましく、１２０００以下であることがより更に好ましい。
　前記範囲であることにより、分散剤としての十分な立体反発効果を保持できるとともに、分散剤の溶剤親和性部の比表面積が大きくなることにより、溶剤の塗膜への侵入や色材への到達を抑制しやすくなる。 The weight average molecular weight Mw of the polymer chain in the polymer is preferably 2000 or more, more preferably 3000 or more, and even more preferably 4000 or more, from the viewpoint of the dispersibility and dispersion stability of the colorant. , 15000 or less, and even more preferably 12000 or less.
Within the above range, a sufficient steric repulsion effect as a dispersant can be maintained, and the specific surface area of the solvent affinity part of the dispersant increases, allowing the solvent to penetrate the coating film and reach the coloring material. becomes easier to suppress.
　また、Ｐｏｌｙｍｅｒにおけるポリマー鎖は、目安として、組み合わせて用いられる有機溶剤に対して、２３℃における溶解度が２０（ｇ／１００ｇ溶剤）以上であることが好ましい。
　当該ポリマー鎖の溶解性は、グラフト共重合体を調製する際のポリマー鎖を導入する原料が前記溶解度を有することを目安にすることができる。例えば、グラフト共重合体にポリマー鎖を導入するために、ポリマー鎖及びその末端にエチレン性不飽和二重結合を有する基を含む重合性オリゴマー（マクロモノマー）を用いる場合、当該重合性オリゴマーが前記溶解度を有すれば良い。また、エチレン性不飽和二重結合を有する基を含むモノマーにより共重合体が形成された後に、共重合体中に含まれる反応性基と反応可能な反応性基を含むポリマー鎖を用いて、ポリマー鎖を導入する場合、当該反応性基を含むポリマー鎖が前記溶解度を有すれば良い。 In addition, as a guideline, the polymer chain in Polymer preferably has a solubility of 20 (g/100 g solvent) or more at 23° C. in the organic solvent used in combination.
The solubility of the polymer chain can be determined based on the solubility of the raw material into which the polymer chain is introduced when preparing the graft copolymer. For example, when using a polymerizable oligomer (macromonomer) containing a group having an ethylenically unsaturated double bond at the polymer chain and its terminal in order to introduce a polymer chain into the graft copolymer, the polymerizable oligomer is the above So long as it has solubility. Further, after a copolymer is formed from a monomer containing a group having an ethylenically unsaturated double bond, using a polymer chain containing a reactive group capable of reacting with the reactive group contained in the copolymer, When a polymer chain is introduced, it is sufficient that the polymer chain containing the reactive group has the aforementioned solubility.
　前記グラフト共重合体において、前記一般式（Ｉ）で表される構成単位は、３質量％～６０質量％の割合で含まれていることが好ましく、６質量％～４５質量％がより好ましく、９質量％～３０質量％がさらに好ましい。グラフト共重合体中の一般式（Ｉ）で表される構成単位が前記範囲内にあれば、グラフト共重合体中の色材との親和性部の割合が適切になり、かつ有機溶剤に対する溶解性の低下を抑制できるので、色材に対する吸着性が良好となり、優れた分散性、及び分散安定性が得られやすい。
　一方、前記グラフト共重合体において、前記一般式（ＩＩ）で表される構成単位は、４０質量％～９７質量％の割合で含まれていることが好ましく、５５質量％～９４質量％がより好ましく、７０質量％～９１質量％がさらに好ましい。グラフト共重合体中の一般式（ＩＩ）で表される構成単位が前記範囲内にあれば、グラフト共重合体中の溶剤親和性部の割合が適切になって、分散剤としての十分な立体反発効果を保持できるとともに、分散剤の溶剤親和性部の比表面積が大きくなることにより、溶剤の塗膜への侵入や色材への到達を抑制しやすい。 In the graft copolymer, the structural unit represented by the general formula (I) is preferably contained in a proportion of 3% by mass to 60% by mass, more preferably 6% by mass to 45% by mass, 9% by mass to 30% by mass is more preferable. If the structural unit represented by the general formula (I) in the graft copolymer is within the above range, the ratio of the affinity portion with the coloring material in the graft copolymer will be appropriate, and the solubility in the organic solvent will be good. Since the deterioration of the properties can be suppressed, the adsorptivity to the coloring material is improved, and excellent dispersibility and dispersion stability can be easily obtained.
On the other hand, in the graft copolymer, the structural unit represented by the general formula (II) is preferably contained in a proportion of 40% by mass to 97% by mass, more preferably 55% by mass to 94% by mass. Preferably, 70% by mass to 91% by mass is more preferable. If the structural unit represented by the general formula (II) in the graft copolymer is within the above range, the ratio of the solvent-affinity portion in the graft copolymer will be appropriate, resulting in sufficient stericity as a dispersant. Since the repulsion effect can be maintained and the specific surface area of the solvent affinity part of the dispersant is increased, it is easy to suppress penetration of the solvent into the coating film and arrival of the coloring material.
　本発明に用いられる前記グラフト共重合体は、本発明の効果が損なわれない範囲内で、前記一般式（Ｉ）で表される構成単位及び前記一般式（ＩＩ）で表される構成単位以外に、更に他の構成単位を有していても良い。他の構成単位としては、前記一般式（Ｉ）で表される構成単位を誘導するエチレン性不飽和二重結合含有モノマー等と共重合可能な、エチレン性不飽和二重結合含有モノマーを適宜選択して共重合し、他の構成単位を導入することができる。
　前記一般式（Ｉ）で表される構成単位と共重合されている他の構成単位としては、例えば、前記一般式（ＩＩＩ）で表される構成単位等が挙げられる。
　なお、前記構成単位の含有割合は、製造時には、グラフト共重合体を合成する際の、前記一般式（Ｉ）で表される構成単位、前記一般式（ＩＩ）で表される構成単位、及び前記一般式（ＩＩＩ）で表される構成単位等を誘導するモノマーの仕込み量から算出される。 The graft copolymer used in the present invention, other than the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II), within a range that does not impair the effects of the present invention. In addition, it may have other structural units. As the other structural unit, an ethylenically unsaturated double bond-containing monomer that can be copolymerized with the ethylenically unsaturated double bond-containing monomer from which the structural unit represented by the general formula (I) is derived is appropriately selected. can be copolymerized to introduce other structural units.
Other structural units copolymerized with the structural units represented by general formula (I) include, for example, structural units represented by general formula (III).
It should be noted that the content ratio of the structural unit is, at the time of production, the structural unit represented by the general formula (I), the structural unit represented by the general formula (II), and the structural unit represented by the general formula (II) when synthesizing the graft copolymer. It is calculated from the charged amount of the monomer that induces the structural unit represented by the general formula (III).
　また、前記グラフト共重合体の質量平均分子量Ｍｗは、分散性及び分散安定性の点から、４０００以上であることが好ましく、６０００以上であることがより好ましく、８０００以上であることがより更に好ましい。一方、溶剤再溶解性の点から、５００００以下であることが好ましく、３００００以下であることがより好ましい。
　なお、本発明において質量平均分子量Ｍｗは、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）により測定された値である。測定は、東ソー製のＨＬＣ－８１２０ＧＰＣを用い、溶出溶剤を０．０１モル／リットルの臭化リチウムを添加したＮ－メチルピロリドンとし、校正曲線用ポリスチレンスタンダードをＭｗ３７７４００、２１０５００、９６０００、５０４００、２０６５０、１０８５０、５４６０、２９３０、１３００、５８０（以上、Ｐｏｌｙｍｅｒ　Ｌａｂｏｒａｔｏｒｉｅｓ製　Ｅａｓｉ　ＰＳ－２シリーズ）及びＭｗ１０９００００（東ソー製）とし、測定カラムをＴＳＫ－ＧＥＬ　ＡＬＰＨＡ－Ｍ×２本（東ソー製）として行われたものである。 Further, the weight average molecular weight Mw of the graft copolymer is preferably 4000 or more, more preferably 6000 or more, and even more preferably 8000 or more, from the viewpoint of dispersibility and dispersion stability. . On the other hand, it is preferably 50,000 or less, more preferably 30,000 or less, from the viewpoint of solvent resolubility.
In addition, the mass average molecular weight Mw in the present invention is a value measured by GPC (gel permeation chromatography). The measurement was carried out using Tosoh's HLC-8120GPC, the elution solvent was N-methylpyrrolidone to which 0.01 mol/liter of lithium bromide was added, and the polystyrene standards for the calibration curve were Mw 377400, 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (Easi PS-2 series manufactured by Polymer Laboratories) and Mw 1090000 (manufactured by Tosoh), and the measurement column was TSK-GEL ALPHA-M × 2 (manufactured by Tosoh). is.
（グラフト共重合体の製造方法）
　本発明において、前記グラフト共重合体の製造方法としては、前記一般式（Ｉ）で表される構成単位と、前記一般式（ＩＩ）で表される構成単位とを有するグラフト共重合体を製造することができる方法であればよく、特に限定されない。前記一般式（Ｉ）で表される構成単位と前記一般式（ＩＩ）で表される構成単位とを有するグラフト共重合体を製造する場合、例えば、下記一般式（Ｉａ）で表されるモノマーと、前記ポリマー鎖及びその末端にエチレン性不飽和二重結合を有する基からなる重合性オリゴマー（マクロモノマー）とを共重合成分として含有して共重合し、グラフト共重合体を製造する方法が挙げられる。
　必要に応じて更にその他のモノマーも用い、公知の重合手段を用いてグラフト共重合体を製造することができる。 (Method for producing graft copolymer)
In the present invention, as the method for producing the graft copolymer, a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II) is produced. It is not particularly limited as long as it can be done. When producing a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II), for example, a monomer represented by the following general formula (Ia) and a polymerizable oligomer (macromonomer) comprising a group having an ethylenically unsaturated double bond at the end of the polymer chain as a copolymerization component, and copolymerizing to produce a graft copolymer. mentioned.
If necessary, other monomers may also be used, and the graft copolymer can be produced using known polymerization means.
Figure JPOXMLDOC01-appb-C000010
 （一般式（Ｉａ）中、Ｒ７１、Ａ１、Ｒ７２及びＲ７３は、一般式（Ｉ）と同様である。）
Figure JPOXMLDOC01-appb-C000010
 (In general formula (Ia), R 71 , A 1 , R 72 and R 73 are the same as in general formula (I).)
　また、前記一般式（Ｉ）で表される構成単位と前記一般式（ＩＩ）で表される構成単位とを有するグラフト共重合体を製造する場合、前記一般式（Ｉａ）で表されるモノマーとその他のエチレン性不飽和二重結合を有する基を含むモノマーとを付加重合して共重合体が形成された後に、共重合体中に含まれる反応性基と反応可能な反応性基を含むポリマー鎖を用いて、ポリマー鎖を導入しても良い。具体的には例えば、アルコキシ基、水酸基、カルボキシル基、アミノ基、エポキシ基、イソシアネート基、水素結合形成基等の置換基を有する共重合体を合成した後に、当該置換基と反応する官能基を含むポリマー鎖とを反応させて、ポリマー鎖を導入したものであっても良い。
　例えば、側鎖にグリシジル基を有する共重合体に、末端にカルボキシル基を有するポリマー鎖を反応させたり、側鎖にイソシアネート基を有する共重合体に、末端にヒドロキシ基を有するポリマー鎖を反応させたりして、ポリマー鎖を導入することができる。
　なお、前記重合においては、重合に一般的に用いられる添加剤、例えば重合開始剤、分散安定剤、連鎖移動剤などを用いてもよい。 Further, when producing a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II), the monomer represented by the general formula (Ia) and other monomers containing groups having ethylenically unsaturated double bonds are added to form a copolymer, after which the reactive groups contained in the copolymer and reactive groups that can react Polymer chains may be used to introduce polymer chains. Specifically, for example, after synthesizing a copolymer having a substituent such as an alkoxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, an isocyanate group, or a hydrogen bond forming group, a functional group that reacts with the substituent is added. A polymer chain may be introduced by reacting with a polymer chain contained therein.
For example, a copolymer having a glycidyl group in the side chain is reacted with a polymer chain having a terminal carboxyl group, or a copolymer having an isocyanate group in the side chain is reacted with a polymer chain having a hydroxyl group at the terminal. can introduce polymer chains.
In addition, in the polymerization, additives commonly used in polymerization, such as polymerization initiators, dispersion stabilizers, and chain transfer agents, may be used.
　次に、前記一般式（Ｉ）で表される構成単位を含むＡブロックと、（メタ）アクリレート由来の構成単位を含むＢブロックとを有するブロック共重合体を説明する。
　本発明においてブロック共重合体の各ブロックの配置は特に限定されず、例えば、ＡＢブロック共重合体、ＡＢＡブロック共重合体、ＢＡＢブロック共重合体等とすることができる。中でも、分散性に優れる点で、ＡＢブロック共重合体、又はＡＢＡブロック共重合体が好ましい。 Next, a block copolymer having an A block containing a structural unit represented by the general formula (I) and a B block containing a (meth)acrylate-derived structural unit will be described.
In the present invention, the arrangement of each block in the block copolymer is not particularly limited, and examples thereof include AB block copolymers, ABA block copolymers, and BAB block copolymers. Among them, an AB block copolymer or an ABA block copolymer is preferable because of its excellent dispersibility.
　Ａブロックは色材吸着部位として機能するブロックであり、少なくとも前記一般式（Ｉ）で表される構成単位を含む。当該ブロック共重合体の当該一般式（Ｉ）で表される構成単位が有する窒素部位の少なくとも一部と有機酸化合物及びハロゲン化炭化水素からなる群から選ばれる少なくとも１種とが塩を形成した塩型ブロック共重合体であってもよい。
　Ａブロックは、本発明の目的を達成する範囲で、一般式（Ｉ）で表される構成単位以外の構成単位を有するものであってもよく、一般式（Ｉ）で表される構成単位と共重合可能な構成単位であれば含有することができる。具体的には例えば、前記一般式（ＩＩＩ）で表される構成単位等が挙げられる。
　塩形成前のブロック共重合体におけるＡブロック中、一般式（Ｉ）で表される構成単位の含有割合は、Ａブロックの全構成単位の合計質量に対して、５０質量％～１００質量％であることが好ましく、８０質量％～１００質量％であることがより好ましく、１００質量％であることが最も好ましい。一般式（Ｉ）で表される構成単位の割合が高いほど、色材への吸着力が向上し、ブロック共重合体の分散性、及び分散安定性が良好となるからである。なお、上記構成単位の含有割合は、一般式（Ｉ）で表される構成単位を有するＡブロックを合成する際の仕込み質量から算出される。 The A block is a block that functions as a coloring material adsorption site and contains at least the structural unit represented by the general formula (I). At least part of the nitrogen sites of the structural units represented by the general formula (I) of the block copolymer and at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons form a salt. It may be a salt-type block copolymer.
The A block may have a structural unit other than the structural unit represented by general formula (I) within the scope of achieving the object of the present invention, and the structural unit represented by general formula (I) and Any structural unit that can be copolymerized can be contained. Specific examples thereof include structural units represented by the general formula (III).
The content ratio of the structural unit represented by general formula (I) in the A block in the block copolymer before salt formation is 50% by mass to 100% by mass with respect to the total mass of all structural units in the A block. preferably 80% by mass to 100% by mass, most preferably 100% by mass. This is because the higher the proportion of the structural unit represented by the general formula (I), the better the adsorptive power to the coloring material, and the better the dispersibility and dispersion stability of the block copolymer. In addition, the content ratio of the structural unit is calculated from the charged mass when synthesizing the A block having the structural unit represented by the general formula (I).
　塩形成前のブロック共重合体中、一般式（Ｉ）で表される構成単位を含むＡブロックの全構成単位の合計含有割合は、分散性、及び分散安定性が良好となる点から、ブロック共重合体の全構成単位の合計質量に対して、５質量％～６０質量％であることが好ましく、１０質量％～５０質量％であることがより好ましい。
　また、塩形成前のブロック共重合体中、一般式（Ｉ）で表される構成単位の含有割合は、分散性、及び分散安定性が良好となる点から、ブロック共重合体の全構成単位の合計質量に対して、５質量％～６０質量％であることが好ましく、１０質量％～５０質量％であることがより好ましい。なお、上記ブロック共重合体における各構成単位の含有割合は、塩形成前のブロック共重合体を合成する際の仕込み質量から算出される。
　なお、一般式（Ｉ）で表される構成単位は、色材との親和性を有すればよく、１種からなるものであっても良いし、２種以上の構成単位を含んでいてもよい。 In the block copolymer before salt formation, the total content of all structural units of the A block including the structural unit represented by the general formula (I) is from the viewpoint of good dispersibility and dispersion stability. It is preferably 5% by mass to 60% by mass, more preferably 10% by mass to 50% by mass, based on the total mass of all structural units of the copolymer.
In addition, the content ratio of the structural unit represented by the general formula (I) in the block copolymer before salt formation is the total structural units of the block copolymer from the viewpoint of good dispersibility and dispersion stability. It is preferably 5% by mass to 60% by mass, more preferably 10% by mass to 50% by mass, based on the total mass of. The content ratio of each structural unit in the block copolymer is calculated from the charged mass when synthesizing the block copolymer before salt formation.
In addition, the structural unit represented by the general formula (I) only needs to have an affinity with the colorant, and may consist of one type or may contain two or more types of structural units. good.
　Ｂブロックは溶剤親和性部位として機能するブロックであり、少なくとも（メタ）アクリレート由来の構成単位を含む。
　（メタ）アクリレート由来の構成単位としては、前記と同様であってよい。
　Ｂブロックとしては、一般式（Ｉ）で表される構成単位を誘導するモノマーと共重合可能な、不飽和二重結合を有するモノマーの中から、溶剤親和性を有するように溶剤に応じて適宜選択して用いられることが好ましい。目安として、組み合わせて用いられる溶剤に対して、共重合体の２３℃における溶解度が２０（ｇ／１００ｇ溶剤）以上となるように、Ｂブロックを導入することが好ましい。Ｂブロック部を構成する構成単位は１種からなるものであっても良いし、２種以上の構成単位を含んでいてもよい。
　Ｂブロックに含まれる構成単位としては、例えば、前記一般式（ＩＩＩ）で表される構成単位等が挙げられる。 The B block is a block that functions as a solvent affinity site and contains at least a (meth)acrylate-derived structural unit.
(Meth)acrylate-derived structural units may be the same as those described above.
As the B block, a monomer having an unsaturated double bond, which is copolymerizable with the monomer from which the structural unit represented by the general formula (I) is derived, is appropriately selected depending on the solvent so as to have solvent affinity. It is preferably used selectively. As a guideline, it is preferable to introduce the B block so that the solubility of the copolymer at 23° C. in the solvent used in combination is 20 (g/100 g solvent) or more. The structural unit constituting the B block part may consist of one type, or may contain two or more types of structural units.
Examples of structural units contained in the B block include structural units represented by the general formula (III).
　分散剤として用いられるブロック共重合体において、前記一般式（Ｉ）で表される構成単位のユニット数ｍと、溶剤親和性のブロック部を構成する他の構成単位のユニット数ｎの比率ｍ／ｎとしては、０．０１以上１以下の範囲内であることが好ましく、０．０５以上０．７以下の範囲内であることが、色材の分散性、分散安定性の点からより好ましい。 In the block copolymer used as a dispersant, the ratio of the unit number m of the structural unit represented by the general formula (I) to the unit number n of other structural units constituting the solvent-affinity block portion is m/ n is preferably in the range of 0.01 to 1, and more preferably in the range of 0.05 to 0.7 in terms of dispersibility and dispersion stability of the colorant.
　分散剤として用いられるブロック共重合体の中でも、前記一般式（Ｉ）で表される構成単位を含むＡブロックとカルボキシ基含有モノマー由来の構成単位及び（メタ）アクリレート由来の構成単位を含むＢブロックとを含有するブロック共重合体、並びに、当該ブロック共重合体の前記一般式（Ｉ）で表される構成単位が有する窒素部位の少なくとも一部と有機酸化合物及びハロゲン化炭化水素からなる群から選ばれる少なくとも１種とが塩を形成した塩型ブロック共重合体の少なくとも１種を含有し、前記ブロック共重合体並びに塩型ブロック共重合体の少なくとも１種の酸価が１ｍｇＫＯＨ／ｇ～１８ｍｇＫＯＨ／ｇで、ガラス転移温度が３０℃以上であることが、低温加熱処理でも硬化膜の基板密着性及び耐溶剤性が良好になる点、及び現像残渣の発生が抑制される点から好ましい。また当該特定の分散剤は、前記一般式（Ａ）で表される化合物を含む光開始剤と組み合わせると、耐溶剤性がより向上する点から好ましい。
　この場合のＢブロックは、（メタ）アクリレート由来の構成単位を必須成分として含むが、国際公開第２０１６／１０４４９３号のＢブロックと同様であってよい。 Among the block copolymers used as dispersants, the A block containing the structural unit represented by the general formula (I) and the B block containing the structural unit derived from the carboxy group-containing monomer and the (meth)acrylate-derived structural unit and from the group consisting of at least part of the nitrogen moiety of the structural unit represented by the general formula (I) of the block copolymer, an organic acid compound, and a halogenated hydrocarbon Contains at least one salt-type block copolymer formed with at least one selected salt, and the block copolymer and at least one of the salt-type block copolymers have an acid value of 1 mgKOH/g to 18 mgKOH. /g and a glass transition temperature of 30°C or higher is preferable from the viewpoint that the substrate adhesion and solvent resistance of the cured film are improved even in low-temperature heat treatment, and the generation of development residue is suppressed. Moreover, the specific dispersant is preferable from the viewpoint of further improving solvent resistance when combined with a photoinitiator containing the compound represented by the general formula (A).
The B block in this case contains a (meth)acrylate-derived structural unit as an essential component, and may be the same as the B block of WO 2016/104493.
　前記カルボキシ基含有モノマーとしては、一般式（Ｉ）で表される構成単位を有するモノマーと共重合可能で、不飽和二重結合とカルボキシ基を含有するモノマーを用いることができる。このようなモノマーとしては、例えば、（メタ）アクリル酸、ビニル安息香酸、マレイン酸、マレイン酸モノアルキルエステル、フマル酸、イタコン酸、クロトン酸、桂皮酸、アクリル酸ダイマーなどが挙げられる。また、２－ヒドロキシエチル（メタ）アクリレートなどの水酸基を有する単量体と無水マレイン酸や無水フタル酸、シクロヘキサンジカルボン酸無水物のような環状無水物との付加反応物、ω－カルボキシ－ポリカプロラクトンモノ（メタ）アクリレートなども利用できる。また、カルボキシ基の前駆体として無水マレイン酸、無水イタコン酸、無水シトラコン酸などの酸無水物基含有モノマーを用いてもよい。中でも、共重合性やコスト、溶解性、ガラス転移温度などの点から（メタ）アクリル酸が特に好ましい。 As the carboxy group-containing monomer, a monomer that can be copolymerized with a monomer having a structural unit represented by general formula (I) and that contains an unsaturated double bond and a carboxy group can be used. Examples of such monomers include (meth)acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl esters, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimers. Also, addition reaction products of monomers having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and cyclic anhydrides such as maleic anhydride, phthalic anhydride and cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylate and the like can also be used. Acid anhydride group-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride may also be used as a precursor of the carboxy group. Among them, (meth)acrylic acid is particularly preferable from the viewpoint of copolymerizability, cost, solubility, glass transition temperature, and the like.
　塩形成前のブロック共重合体中、カルボキシ基含有モノマー由来の構成単位の含有割合は、ブロック共重合体の酸価が前記特定の酸価の範囲内になるように適宜設定すればよく、特に限定されないが、ブロック共重合体の全構成単位の合計質量に対して、０．０５質量％～４．５質量％であることが好ましく、０．０７質量％～３．７質量％であることがより好ましい。
　カルボキシ基含有モノマー由来の構成単位の含有割合が、前記下限値以上であることより、現像残渣の抑制効果が発現され、前記上限値以下であることより現像密着性の悪化や溶剤再溶解性の悪化を防止できる。
　なお、カルボキシ基含有モノマー由来の構成単位は、上記特定の酸価となればよく、１種からなるものであっても良いし、２種以上の構成単位を含んでいてもよい。 In the block copolymer before salt formation, the content of structural units derived from the carboxyl group-containing monomer may be appropriately set so that the acid value of the block copolymer is within the specific acid value range. Although not limited, it is preferably 0.05% by mass to 4.5% by mass, and 0.07% by mass to 3.7% by mass, based on the total mass of all structural units of the block copolymer. is more preferred.
When the content of the structural unit derived from the carboxyl group-containing monomer is at least the lower limit value, the effect of suppressing development residue is exhibited, and when it is at most the upper limit value, development adhesion is deteriorated and solvent resolubility is reduced. It can prevent deterioration.
The structural unit derived from the carboxyl group-containing monomer may have the specific acid value, and may consist of one type or may contain two or more types of structural units.
　また、ブロック共重合体のＢブロック中に、水酸基含有モノマー由来の構成単位が含まれることが、現像密着性を向上する点から好ましい。Ｂブロック中に、水酸基含有モノマー由来の構成単位が含まれる場合には、更に現像速度も向上する。なお、ここでの水酸基は、脂肪族炭化水素に結合したアルコール性水酸基をいう。 In addition, it is preferable that the B block of the block copolymer contains a structural unit derived from a hydroxyl group-containing monomer from the viewpoint of improving development adhesion. When the B block contains a structural unit derived from a hydroxyl group-containing monomer, the development speed is further improved. In addition, the hydroxyl group here refers to an alcoholic hydroxyl group bonded to an aliphatic hydrocarbon.
　水酸基含有モノマー由来の構成単位としては、一般式（Ｉ）で表される構成単位を誘導するモノマーと共重合可能な不飽和二重結合と水酸基を含有するモノマーを用いることができる。このようなモノマーとしては、例えば、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、グリセリンモノ（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレートのε－カプロラクトン１モル付加物、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート等が挙げられる。
　現像密着性が向上する点から、中でも、２－ヒドロキシエチルメタクリレート、及び２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレートよりなる群から選択される１種以上であることが好ましい。 As the structural unit derived from the hydroxyl group-containing monomer, a monomer containing an unsaturated double bond and a hydroxyl group that is copolymerizable with the monomer that derives the structural unit represented by general formula (I) can be used. Such monomers include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerin mono (meth) Acrylate, polyethylene glycol mono(meth)acrylate, ε-caprolactone 1 mol adduct of 2-hydroxyethyl(meth)acrylate, 2-hydroxy-3-phenoxypropyl(meth)acrylate and the like.
Among them, one or more selected from the group consisting of 2-hydroxyethyl methacrylate and 2-hydroxy-3-phenoxypropyl (meth)acrylate is preferable from the viewpoint of improving development adhesion.
　塩形成前のブロック共重合体中、水酸基含有モノマー由来の構成単位の含有割合は、ブロック共重合体の全構成単位の合計質量に対して、１質量％以上であることが好ましく、２質量％以上であることがより好ましく、３質量％以上であることがより更に好ましく、４質量％以上であることが特に好ましい。上記下限値以上であると現像密着性が好ましいものとすることができる。同様に、７０質量％以下であることが好ましく、６０質量％以下であることがより好ましく、５０質量％以下であることがより更に好ましく、４０質量％以下であることが特に好ましい。上記上限値以下であると他の有用なモノマーの導入比率を上げられる点から好ましいものとすることができる。なお、上記構成単位の含有割合は、塩形成前のブロック共重合体を合成する際の仕込み質量から算出される。 The content of structural units derived from hydroxyl group-containing monomers in the block copolymer before salt formation is preferably 1% by mass or more, preferably 2% by mass, based on the total mass of all structural units of the block copolymer. It is more preferably at least 3% by mass, even more preferably at least 3% by mass, and particularly preferably at least 4% by mass. When it is at least the above lower limit value, the development adhesion can be made preferable. Similarly, it is preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, and particularly preferably 40% by mass or less. If it is equal to or less than the above upper limit, it can be preferable from the point that the introduction ratio of other useful monomers can be increased. In addition, the content ratio of the structural unit is calculated from the charged mass when synthesizing the block copolymer before salt formation.
　前記ブロック共重合体並びに塩型ブロック共重合体の少なくとも１種の酸価は、現像残渣の抑制効果の点から、下限としては、１ｍｇＫＯＨ／ｇ以上であることが好ましく、２ｍｇＫＯＨ／ｇ以上であることがより好ましい。また、前記ブロック共重合体並びに塩型ブロック共重合体の少なくとも１種の酸価は、現像密着性の悪化や溶剤再溶解性の悪化を防止できる点から、上限としては、１８ｍｇＫＯＨ／ｇ以下であることが好ましく、１６ｍｇＫＯＨ／ｇ以下であることがより好ましく、１４ｍｇＫＯＨ／ｇ以下であることがさらにより好ましい。
　前記ブロック共重合体並びに塩型ブロック共重合体の少なくとも１種の酸価は、国際公開第２０１６／１０４４９３号に記載の方法で求めることができる。 The lower limit of the acid value of at least one of the block copolymer and the salt-type block copolymer is preferably 1 mgKOH/g or more, more preferably 2 mgKOH/g or more, from the viewpoint of the effect of suppressing development residue. is more preferable. The upper limit of the acid value of at least one of the block copolymer and the salt-type block copolymer is 18 mgKOH/g or less from the viewpoint of preventing deterioration of development adhesion and solvent re-solubility. preferably 16 mgKOH/g or less, and even more preferably 14 mgKOH/g or less.
The acid value of at least one of the block copolymer and the salt-type block copolymer can be determined by the method described in WO2016/104493.
　前記ブロック共重合体並びに塩型ブロック共重合体の少なくとも１種のガラス転移温度は、現像密着性の点から３０℃以上であることが好ましく、中でも３２℃以上が好ましく、３５℃以上がより好ましい。一方、精秤が容易など、使用時の操作性の観点から、２００℃以下であることが好ましい。
　前記ブロック共重合体並びに塩型ブロック共重合体の少なくとも１種のガラス転移温度は、ＪＩＳ　Ｋ７１２１に準拠し、示差走査熱量測定（ＤＳＣ）により測定することにより求める。ガラス転移温度を示すピークが２つ以上見られる場合には、ピーク面積、すなわち、得られたチャートのベースラインから突出した部分の面積が最も大きいピークをガラス転移温度の代表値とする。 The glass transition temperature of at least one of the block copolymer and the salt-type block copolymer is preferably 30° C. or higher, more preferably 32° C. or higher, more preferably 35° C. or higher, from the viewpoint of development adhesion. . On the other hand, the temperature is preferably 200° C. or less from the viewpoint of operability during use, such as facilitating accurate weighing.
The glass transition temperature of at least one of the block copolymer and the salt-type block copolymer is determined by differential scanning calorimetry (DSC) according to JIS K7121. When two or more peaks indicating the glass transition temperature are observed, the peak area, that is, the peak having the largest area of the portion projecting from the base line of the obtained chart is taken as the representative value of the glass transition temperature.
　前記ブロック共重合体の質量平均分子量Ｍｗは、特に限定されないが、色材分散性及び分散安定性を良好なものとする点から、１０００～２００００であることが好ましく、２０００～１５０００であることがより好ましく、更に３０００～１２０００であることがより好ましい。
　ここで、質量平均分子量は（Ｍｗ）、前記と同様に測定することができる。 The mass-average molecular weight Mw of the block copolymer is not particularly limited, but is preferably from 1000 to 20000, more preferably from 2000 to 15000, from the viewpoint of improving colorant dispersibility and dispersion stability. It is more preferably 3,000 to 12,000.
Here, the weight average molecular weight (Mw) can be measured in the same manner as described above.
　また、（メタ）アクリレート由来の構成単位の合計割合は、分散安定性及び耐溶剤性、光開始剤との相溶性の点から、ブロック共重合体におけるＢブロック中の全構成単位を１００質量％とした時に、６０質量％以上であることが好ましく、８０質量％以上であることがより好ましく、９０質量％以上であることが更に好ましい。一方で、分散安定性、及び優れた耐溶剤性を同時に満たす点から、（メタ）アクリレート由来の構成単位の合計割合は、当該Ｂブロック中の全構成単位を１００質量％とした時に、１００質量％であってもよい。Ｂブロック中に前記カルボキシ基含有モノマー由来の構成単位を含む場合には、（メタ）アクリレート由来の構成単位の合計割合は、Ｂブロック中の前記カルボキシ基含有モノマー由来の構成単位とは異なる全構成単位を１００質量％とした時に、１００質量％であってもよい。 In addition, the total proportion of structural units derived from (meth)acrylate is 100% by mass of all structural units in the B block in the block copolymer from the viewpoint of dispersion stability, solvent resistance, and compatibility with the photoinitiator. , the content is preferably 60% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more. On the other hand, from the point of satisfying dispersion stability and excellent solvent resistance at the same time, the total proportion of structural units derived from (meth)acrylate is 100 mass% when all the structural units in the B block are 100 mass%. %. When the B block contains structural units derived from the carboxy group-containing monomer, the total proportion of the structural units derived from (meth)acrylate is different from the structural units derived from the carboxy group-containing monomer in the B block. When the unit is 100% by mass, it may be 100% by mass.
　塩形成前のブロック共重合体中、Ｂブロックの全構成単位の合計含有割合は、分散性、及び分散安定性が良好となる点から、ブロック共重合体の全構成単位の合計質量に対して、５質量％～６０質量％であることが好ましく、１０質量％～５０質量％であることがより好ましい。
　また、塩形成前のブロック共重合体中、上記一般式（ＩＩＩ）で表される構成単位の含有割合は、色材分散性を向上する点から、ブロック共重合体の全構成単位の合計質量に対して、４０質量％～９５質量％であることが好ましく、５０質量％～９０質量％であることがより好ましい。なお、上記構成単位の含有割合は、塩形成前のブロック共重合体を合成する際の仕込み質量から算出される。　 In the block copolymer before salt formation, the total content of all structural units of the B block is, from the viewpoint of good dispersibility and dispersion stability, relative to the total mass of all structural units of the block copolymer. , preferably 5% to 60% by mass, more preferably 10% to 50% by mass.
Further, in the block copolymer before salt formation, the content ratio of the structural unit represented by the general formula (III) is the total mass of all structural units of the block copolymer from the viewpoint of improving the dispersibility of the coloring material. It is preferably 40% by mass to 95% by mass, more preferably 50% by mass to 90% by mass. The content ratio of the structural unit is calculated from the charged mass when synthesizing the block copolymer before salt formation.
　前記一般式（Ｉ）で表される構成単位を含む（メタ）アクリレート系共重合体は、アミン価が４０ｍｇＫＯＨ／ｇ～１２０ｍｇＫＯＨ／ｇである共重合体が、分散性が良好で塗膜形成時に異物を析出せず、輝度及びコントラストを向上する点から好ましい。
　アミン価が上記範囲内であることにより、粘度の経時安定性や耐熱性に優れると共に、アルカリ現像性や、溶剤再溶解性にも優れている。本発明において、前記一般式（Ｉ）で表される構成単位を含む（メタ）アクリレート系共重合体のアミン価は、中でも、アミン価が８０ｍｇＫＯＨ／ｇ以上であることが好ましく、９０ｍｇＫＯＨ／ｇ以上であることがより好ましい。一方、溶剤再溶解性の点から、前記一般式（Ｉ）で表される構成単位を含む（メタ）アクリレート系共重合体のアミン価は、１１０ｍｇＫＯＨ／ｇ以下であることが好ましく、１０５ｍｇＫＯＨ／ｇ以下であることがより好ましい。
　アミン価は、試料１ｇ中に含まれるアミン成分を中和するのに要する過塩素酸と当量の水酸化カリウムのｍｇ数をいい、ＪＩＳ－Ｋ７２３７に定義された方法により測定することができる。当該方法により測定した場合には、分散剤中の有機酸化合物と塩形成しているアミノ基であっても、通常、当該有機酸化合物が解離するため、分散剤として用いられるブロック共重合体そのもののアミン価を測定することができる。 The (meth)acrylate copolymer containing the structural unit represented by the general formula (I) is a copolymer having an amine value of 40 mgKOH/g to 120 mgKOH/g. It is preferable from the viewpoint of improving brightness and contrast without depositing foreign substances.
When the amine value is within the above range, the viscosity stability over time and heat resistance are excellent, and alkali developability and solvent re-solubility are also excellent. In the present invention, the (meth)acrylate copolymer containing the structural unit represented by the general formula (I) preferably has an amine value of 80 mgKOH/g or more, particularly 90 mgKOH/g or more. is more preferable. On the other hand, from the viewpoint of solvent resolubility, the amine value of the (meth)acrylate copolymer containing the structural unit represented by the general formula (I) is preferably 110 mgKOH/g or less, and 105 mgKOH/g. The following are more preferable.
The amine value refers to the number of mg of potassium hydroxide equivalent to perchloric acid required to neutralize the amine component contained in 1 g of the sample, and can be measured by the method defined in JIS-K7237. When measured by this method, even if the amino group forms a salt with the organic acid compound in the dispersant, the organic acid compound usually dissociates, so the block copolymer itself used as the dispersant can be measured.
　分散剤における共重合体中の各構成単位の含有割合（モル％）は、製造時には原料の仕込み量から求めることができ、また、ＮＭＲ等の分析装置を用いて測定することができる。また、分散剤の構造は、ＮＭＲ、各種質量分析等を用いて測定することができる。また、分散剤を必要に応じて熱分解等により分解し、得られた分解物について、高速液体クロマトグラフィー、ガスクロマトグラフ質量分析計、ＮＭＲ、元素分析、ＸＰＳ／ＥＳＣＡ及びＴＯＦ－ＳＩＭＳ等を用いて求めることができる。 The content ratio (mol%) of each structural unit in the copolymer in the dispersant can be obtained from the amount of raw materials charged at the time of production, and can be measured using an analyzer such as NMR. Also, the structure of the dispersant can be measured using NMR, various mass spectrometry, and the like. In addition, if necessary, the dispersant is decomposed by thermal decomposition or the like, and the obtained decomposition product is subjected to high performance liquid chromatography, gas chromatograph mass spectrometer, NMR, elemental analysis, XPS / ESCA, TOF-SIMS, etc. can ask.
　本発明に係る感光性緑色樹脂組成物において、分散剤の含有量は、色材の分散性及び分散安定性に優れるように選択されればよく、特に限定されないが、感光性緑色樹脂組成物中の固形分全量に対して、例えば好ましくは２質量％～３０質量％、より好ましくは３質量％～２５質量％の範囲内である。上記下限値以上であれば、色材の分散性及び分散安定性に優れ、感光性緑色樹脂組成物の保存安定性により優れている。また、上記上限値以下であれば、現像性が良好なものとなる。特に色材濃度が高い硬化膜を形成する場合には、分散剤の含有量は、感光性緑色樹脂組成物の固形分全量に対して、例えば好ましくは２質量％～２５質量％、より好ましくは３質量％～２０質量％の範囲内である。 In the photosensitive green resin composition according to the present invention, the content of the dispersant is not particularly limited as long as it is selected so as to be excellent in the dispersibility and dispersion stability of the colorant, but in the photosensitive green resin composition For example, it is preferably in the range of 2% by mass to 30% by mass, more preferably 3% by mass to 25% by mass, based on the total solid content. When it is at least the above lower limit, the dispersibility and dispersion stability of the coloring material are excellent, and the storage stability of the photosensitive green resin composition is excellent. Moreover, if it is below the said upper limit, developability will become favorable. Especially when forming a cured film having a high colorant concentration, the content of the dispersant is, for example, preferably 2% to 25% by mass, more preferably 2% by mass to 25% by mass, based on the total solid content of the photosensitive green resin composition. It is within the range of 3% by mass to 20% by mass.
＜チオール化合物＞
　本発明の感光性緑色樹脂組成物は、低温加熱処理後の耐溶剤性、及び基板密着性を向上する点から、更に、チオール化合物を含有することが好ましい。
　チオール化合物としては、チオール基が１つの単官能チオール化合物、チオール基が２つ以上の多官能チオール化合物が挙げられる。線幅シフトの抑制と基板密着性の向上の点からは、チオール基が１つの単官能チオール化合物を用いることがより好ましい。
　単官能チオール化合物としては、例えば、２－メルカプトベンゾチアゾール、２－メルカプトベンゾオキサゾール、２－メルカプトベンゾイミダゾール、２－メルカプト－５－メトキシベンゾチアゾール、２－メルカプト－５－メトキシベンゾイミダゾール、３－メルカプトプロピオン酸、３－メルカプトプロピオン酸メチル、３－メルカプトプロピオン酸エチル、３－メルカプトプロピオン酸オクチル等が挙げられる。
　多官能チオール化合物としては、例えば、１，４－ビス（３－メルカプトブチリルオキシ）ブタン、１，３，５－トリス（３－メルカプトブチルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン、トリメチロールプロパントリス（３－メルカプトプロピオネート）、ペンタエリスリトールテトラキス（３－メルカプトブチレート）、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、ジペンタエリスリトールヘキサキス（３－メルカプトプロピオネート）、およびテトラエチレングリコールビス（３－メルカプトプロピオネート）等が挙げられる。
　チオール化合物としては、単独で又は２種以上組み合わせて用いても良く、中でも、２－メルカプトベンゾオキサゾール、又は２－メルカプトベンゾチアゾールが、低温加熱処理後の耐溶剤性、及び基板密着性を向上する点から好ましい。
　チオール化合物の含有量としては、感光性緑色樹脂組成物の固形分全量に対して、通常０．５質量％～１０質量％、好ましくは１質量％～５質量％の範囲内である。上記下限値以上であれば、　低温加熱処理後の耐溶剤性、及び基板密着性に優れている。一方、上記上限値以下であれば、本発明の感光性緑色樹脂組成物を　現像性が良好で線幅シフトが抑制されたものとしやすい。 <thiol compound>
The photosensitive green resin composition of the present invention preferably further contains a thiol compound from the viewpoint of improving solvent resistance after low-temperature heat treatment and substrate adhesion.
Examples of thiol compounds include monofunctional thiol compounds having one thiol group and polyfunctional thiol compounds having two or more thiol groups. From the viewpoint of suppressing line width shift and improving substrate adhesion, it is more preferable to use a monofunctional thiol compound having one thiol group.
Examples of monofunctional thiol compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3-mercapto propionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate and the like.
Examples of polyfunctional thiol compounds include 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2, 4,6(1H,3H,5H)-trione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopropionate), di pentaerythritol hexakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate) and the like.
The thiol compound may be used alone or in combination of two or more. Among them, 2-mercaptobenzoxazole or 2-mercaptobenzothiazole improves solvent resistance and substrate adhesion after low-temperature heat treatment. It is preferable from the point of view.
The content of the thiol compound is usually in the range of 0.5% by mass to 10% by mass, preferably 1% by mass to 5% by mass, based on the total solid content of the photosensitive green resin composition. If it is at least the above lower limit, the solvent resistance after low-temperature heat treatment and substrate adhesion are excellent. On the other hand, when it is the above upper limit or less, the photosensitive green resin composition of the present invention tends to have good developability and suppressed line width shift.
＜その他の成分＞
　本発明の感光性緑色樹脂組成物には、必要に応じて、更に各種添加剤を含むものであってもよい。添加剤としては、例えば、酸化防止剤、重合停止剤、連鎖移動剤、レベリング剤、可塑剤、界面活性剤、消泡剤、シランカップリング剤、紫外線吸収剤、密着促進剤等などが挙げられる。
　界面活性剤及び可塑剤の具体例としては、例えば、特開２０１３－０２９８３２号公報に記載のものが挙げられる。 <Other ingredients>
If necessary, the photosensitive green resin composition of the present invention may further contain various additives. Examples of additives include antioxidants, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, antifoaming agents, silane coupling agents, ultraviolet absorbers, adhesion promoters, and the like. .
Specific examples of surfactants and plasticizers include those described in JP-A-2013-029832.
　本発明の感光性緑色樹脂組成物は、更に酸化防止剤を含むものであることが、硬化膜の線幅シフト量の抑制の点から好ましい。本発明の感光性緑色樹脂組成物は、例えば、前記一般式（Ａ）で表される化合物と組み合わせて酸化防止剤を含むことにより、硬化膜を形成する際に硬化性を損なうことなく過度なラジカル連鎖反応を制御できるため、細線パターンを形成する際に、直線性がより向上したり、マスク線幅の設計通りに細線パターンを形成する能力が向上する。また、耐熱性を向上することができ、露光及びポストベイク後の輝度低下を抑制できるため輝度を向上することができる。
　本発明に用いられる酸化防止剤としては、特に限定されず、従来公知のものの中から適宜選択すればよい。酸化防止剤の具体例としては、例えば、ヒンダードフェノール系酸化防止剤、アミン系酸化防止剤、リン系酸化防止剤、硫黄系酸化防止剤、ヒドラジン系酸化防止剤等が挙げられ、線幅マスク線幅の設計通りに細線パターンを形成する能力が向上する点、及び耐熱性の点から、ヒンダードフェノール系酸化防止剤を用いることが好ましい。国際公開第２０１４／０２１０２３号に記載されているような潜在性酸化防止剤であっても良い。 It is preferable that the photosensitive green resin composition of the present invention further contains an antioxidant from the viewpoint of suppressing the amount of line width shift of the cured film. The photosensitive green resin composition of the present invention, for example, by containing an antioxidant in combination with the compound represented by the general formula (A), excessive without impairing the curability when forming a cured film Since the radical chain reaction can be controlled, when forming a fine line pattern, the linearity is further improved, and the ability to form the fine line pattern according to the design of the mask line width is improved. In addition, the heat resistance can be improved, and the decrease in luminance after exposure and post-baking can be suppressed, so the luminance can be improved.
The antioxidant used in the present invention is not particularly limited, and may be appropriately selected from those conventionally known. Specific examples of antioxidants include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, and the like. It is preferable to use a hindered phenol-based antioxidant from the viewpoint of improving the ability to form a fine line pattern according to the design of the line width and from the viewpoint of heat resistance. It may be a latent antioxidant as described in WO2014/021023.
　ヒンダードフェノール系酸化防止剤としては、例えば、ペンタエリトリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオナート］（商品名：商品名：ＩＲＧＡＮＯＸ１０１０、ＢＡＳＦ社製）、１，３，５－トリス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）イソシアヌレート（商品名：イルガノックス３１１４、ＢＡＳＦ製）、２，４，６－トリス（４－ヒドロキシ－３，５－ジ－ｔｅｒｔ－ブチルベンジル）メシチレン（商品名：イルガノックス１３３０、ＢＡＳＦ製）、２，２’－メチレンビス（６－ｔｅｒｔ－ブチル－４－メチルフェノール）（商品名：スミライザーＭＤＰ－Ｓ、住友化学製）、６，６’－チオビス（２－ｔｅｒｔ－ブチル－４－メチルフェノール）（商品名：イルガノックス１０８１、ＢＡＳＦ製）、３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジルホスホン酸ジエチル（商品名：イルガモド１９５、ＢＡＳＦ製）等が挙げられる。中でも、耐熱性及び耐光性の点から、ペンタエリトリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオナート］（商品名：商品名：ＩＲＧＡＮＯＸ１０１０、ＢＡＳＦ社製）が好ましい。 Hindered phenol-based antioxidants include, for example, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: trade name: IRGANOX1010, manufactured by BASF), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4,6-tris(4-hydroxy-3 ,5-di-tert-butylbenzyl)mesitylene (trade name: Irganox 1330, manufactured by BASF), 2,2′-methylenebis(6-tert-butyl-4-methylphenol) (trade name: Sumilizer MDP-S, Sumitomo Chemical), 6,6′-thiobis(2-tert-butyl-4-methylphenol) (trade name: Irganox 1081, manufactured by BASF), 3,5-di-tert-butyl-4-hydroxybenzylphosphone and diethyl acid (trade name: Irgamod 195, manufactured by BASF). Among them, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX1010, manufactured by BASF) is preferable from the viewpoint of heat resistance and light resistance. .
　酸化防止剤の含有量としては、感光性緑色樹脂組成物の固形分全量に対して、通常０．１質量％～１０．０質量％、好ましくは０．５質量％～５．０質量％の範囲内である。上記下限値以上であれば、マスク線幅の設計通りに細線パターンを形成する能力が向上する点、及び耐熱性に優れている。一方、上記上限値以下であれば、本発明の感光性緑色樹脂組成物を高感度の感光性緑色樹脂組成物としやすい。 The content of the antioxidant is usually 0.1% by mass to 10.0% by mass, preferably 0.5% by mass to 5.0% by mass, based on the total solid content of the photosensitive green resin composition. Within range. If it is at least the above lower limit, the ability to form a fine line pattern as designed with a mask line width is improved, and the heat resistance is excellent. On the other hand, if it is below the said upper limit, it will be easy to make the photosensitive green resin composition of this invention into a highly sensitive photosensitive green resin composition.
　またシランカップリング剤としては、例えばＫＢＭ－５０２、ＫＢＭ－５０３、ＫＢＥ－５０２、ＫＢＥ－５０３、ＫＢＭ－５１０３、ＫＢＭ－９０３、ＫＢＥ－９０３、ＫＢＭ５７３、ＫＢＭ－４０３、ＫＢＥ－４０２、ＫＢＥ－４０３、ＫＢＭ－３０３、ＫＢＭ－８０２、ＫＢＭ－８０３、ＫＢＥ－９００７、Ｘ－１２－９６７Ｃ(信越シリコーン社製)などが挙げられる。中でもＳｉＮ基板の密着性の点からメタクリル基、アクリル基を有するＫＢＭ－５０２、ＫＢＭ－５０３、ＫＢＥ－５０２、ＫＢＥ－５０３、ＫＢＭ－５１０３が好ましい。 Examples of silane coupling agents include KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-903, KBE-903, KBM573, KBM-403, KBE-402, KBE-403 , KBM-303, KBM-802, KBM-803, KBE-9007, X-12-967C (manufactured by Shin-Etsu Silicone Co., Ltd.) and the like. Among them, KBM-502, KBM-503, KBE-502, KBE-503 and KBM-5103 having a methacrylic group or an acrylic group are preferable from the viewpoint of adhesion to SiN substrates.
　シランカップリング剤の含有量としては、感光性緑色樹脂組成物中の固形分全量に対して、通常０．０５質量％～１０．０質量％、好ましくは０．１質量％～５．０質量％の範囲内である。上記下限値以上、上記上限値以下であれば、基板密着性向上効果が良好になりやすい。 The content of the silane coupling agent is usually 0.05% by mass to 10.0% by mass, preferably 0.1% by mass to 5.0% by mass, relative to the total solid content in the photosensitive green resin composition. %. If it is more than the said lower limit and below the said upper limit, the board|substrate adhesiveness improvement effect will become favorable easily.
＜感光性緑色樹脂組成物の製造方法＞
　本発明の感光性緑色樹脂組成物の製造方法は、色材と、光重合性化合物と、光開始剤と、所望により用いられる各種添加成分とを、公知の混合手段を用いて混合することにより、調製することができる。
　本発明の感光性緑色樹脂組成物が、色材と、分散剤と、アルカリ可溶性樹脂と、光重合性化合物と、光開始剤と、溶剤と、所望により用いられる各種添加成分とを含有する場合、当該樹脂組成物の調製方法としては、例えば、（１）まず溶剤中に、色材と、分散剤とを添加して色材分散液を調製し、当該分散液に、アルカリ可溶性樹脂と、光重合性化合物と、光開始剤と、所望により用いられる各種添加成分を混合する方法；（２）溶剤中に、色材と、分散剤と、アルカリ可溶性樹脂と、光重合性化合物と、光開始剤と、所望により用いられる各種添加成分とを同時に投入し混合する方法；（３）溶剤中に、分散剤と、アルカリ可溶性樹脂と、光重合性化合物と、光開始剤と、所望により用いられる各種添加成分とを添加し、混合したのち、色材を加えて分散する方法；（４）溶剤中に、色材と、分散剤と、アルカリ可溶性樹脂とを添加して色材分散液を調製し、当該分散液に、更にアルカリ可溶性樹脂と、溶剤と、光重合性化合物と、光開始剤と、所望により用いられる各種添加成分を添加し、混合する方法；などを挙げることができる。
　これらの方法の中で、上記（１）及び（４）の方法が、色材の凝集を効果的に防ぎ、均一に分散させ得る点から好ましい。 <Method for producing photosensitive green resin composition>
Method for producing a photosensitive green resin composition of the present invention, a colorant, a photopolymerizable compound, a photoinitiator, and optionally various additive components, by mixing using a known mixing means , can be prepared.
When the photosensitive green resin composition of the present invention contains a colorant, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent, and various additive components optionally used As a method for preparing the resin composition, for example, (1) first, a coloring material and a dispersing agent are added to a solvent to prepare a coloring material dispersion, and an alkali-soluble resin and an alkali-soluble resin are added to the dispersion; A method of mixing a photopolymerizable compound, a photoinitiator, and various additive components that are optionally used; A method of simultaneously adding and mixing an initiator and various additive components that are optionally used; (4) adding a coloring material, a dispersant, and an alkali-soluble resin to a solvent to prepare a coloring material dispersion; and a method of adding and mixing an alkali-soluble resin, a solvent, a photopolymerizable compound, a photoinitiator, and optionally various additive components to the dispersion; and the like.
Among these methods, the above methods (1) and (4) are preferable because they can effectively prevent the aggregation of the colorant and uniformly disperse the colorant.
　色材分散液を調製する方法は、従来公知の分散方法の中から適宜選択して用いることができる。例えば、（１）予め、分散剤を溶剤に混合、撹拌し、分散剤溶液を調製し、次いで必要に応じて有機酸化合物を混合して分散剤が有するアミノ基と有機酸化合物との塩形成させる。これを色材と必要に応じてその他の成分を混合し、公知の攪拌機または分散機を用いて分散させる方法；（２）分散剤を溶剤に混合、撹拌し、分散剤溶液を調製し、次いで、色材及び必要に応じて有機酸化合物と、更に必要に応じてその他の成分を混合し、公知の攪拌機または分散機を用いて分散させる方法；（３）分散剤を溶剤に混合、攪拌し、分散剤溶液を調整し、次いで、色材及び必要に応じてその他の成分を混合し、公知の攪拌機または分散機を用いて分散液としたのちに、必要に応じて有機酸化合物を添加する方法などが挙げられる。 The method for preparing the colorant dispersion can be appropriately selected from conventionally known dispersion methods. For example, (1) a dispersant is mixed with a solvent in advance and stirred to prepare a dispersant solution, and then an organic acid compound is mixed as necessary to form a salt between the amino group of the dispersant and the organic acid compound. Let A method of mixing this with a coloring material and, if necessary, other components and dispersing using a known stirrer or disperser; (2) mixing and stirring a dispersant in a solvent to prepare a dispersant solution; , a coloring material and, if necessary, an organic acid compound, and if necessary, other components are mixed and dispersed using a known stirrer or disperser; (3) a dispersant is mixed with a solvent and stirred; , Prepare a dispersant solution, then mix the coloring material and other components as necessary, make a dispersion using a known stirrer or disperser, and then add an organic acid compound as necessary. methods and the like.
　分散処理を行うための分散機としては、２本ロール、３本ロール等のロールミル、ボールミル、振動ボールミル等のボールミル、ペイントコンディショナー、連続ディスク型ビーズミル、連続アニュラー型ビーズミル等のビーズミルが挙げられる。ビーズミルの好ましい分散条件として、使用するビーズ径は０．０３ｍｍ～２．００ｍｍが好ましく、より好ましくは０．１０ｍｍ～１．０ｍｍである。 Examples of dispersing machines for dispersing include roll mills such as two-roll and three-roll roll mills, ball mills such as ball mills and vibrating ball mills, bead mills such as paint conditioners, continuous disk-type bead mills, and continuous annular-type bead mills. As preferable dispersing conditions for the bead mill, the diameter of the beads used is preferably 0.03 mm to 2.00 mm, more preferably 0.10 mm to 1.0 mm.
＜用途＞
　本発明に係る感光性緑色樹脂組成物は、低温加熱処理でも耐溶剤性が良好で、且つパターン形状が良好な着色層を形成可能であることから、カラーフィルタ用途に好適に用いることができ、中でも有機発光素子等、耐熱性が低い素子が形成された基板上に直接カラーフィルタを形成する１３０℃以下、更に１００℃以下や９０℃以下の低温加熱処理用途等に好適に用いることができ、有機発光素子上に形成する硬化膜に好適に用いることができる。
　また、本発明に係る感光性緑色樹脂組成物は、有機発光素子上に形成する硬化膜に用いることができることから、外光反射抑制効果を有する円偏光板代替の着色硬化膜の形成に好適に用いられる。本発明に係る感光性緑色樹脂組成物の硬化膜を円偏光板の代替に用いる場合には、偏光板を含まない表示装置とすることができるため、本発明に係る感光性緑色樹脂組成物は、偏光板を含まない表示装置用途に好適に用いられる。
　また、本発明に係る感光性緑色樹脂組成物は、有機発光素子上に形成する硬化膜に用いる感光性緑色樹脂組成物であることから、外付けのカラーフィルタ基板を含まない表示装置用途、薄膜でフレキシブル性が向上した有機発光表示装置用途に好適に用いられる。 <Application>
The photosensitive green resin composition according to the present invention has good solvent resistance even at low temperature heat treatment, and can form a colored layer with a good pattern shape, so it can be suitably used for color filters. Among them, it can be suitably used for low-temperature heat treatment applications such as 130 ° C. or lower, further 100 ° C. or lower or 90 ° C. or lower, in which a color filter is formed directly on a substrate on which an element with low heat resistance such as an organic light-emitting device is formed. It can be suitably used for a cured film formed on an organic light emitting device.
In addition, since the photosensitive green resin composition according to the present invention can be used for a cured film formed on an organic light emitting device, it is suitable for forming a colored cured film as a substitute for a circularly polarizing plate having an effect of suppressing reflection of external light. Used. When the cured film of the photosensitive green resin composition according to the present invention is used in place of a circularly polarizing plate, it can be a display device that does not contain a polarizing plate, so the photosensitive green resin composition according to the present invention is , is suitably used for display devices that do not contain a polarizing plate.
Further, since the photosensitive green resin composition according to the present invention is a photosensitive green resin composition used for a cured film formed on an organic light-emitting element, it can be It is suitable for use in organic light-emitting display devices with improved flexibility.
ＩＩ．硬化物
　本発明に係る硬化物は、前記本発明に係る感光性緑色樹脂組成物の硬化物である。
　本発明に係る硬化物は、例えば、前記本発明に係る感光性緑色樹脂組成物の塗膜を形成し、該塗膜を乾燥させたのち、露光、及び必要に応じて現像、加熱処理により得ることができる。塗膜の形成、露光、現像、及び加熱処理の方法としては、例えば、後述する本発明に係るカラーフィルタが備える着色層の形成において用いられる方法と同様の方法とすることができる。
　本発明に係る硬化物は、加熱処理が１３０℃以下、更に１００℃以下や９０℃以下という低温の加熱処理であっても、耐溶剤性が良好であり、且つパターン形状が良好である。
　本発明に係る硬化物は、低温加熱処理でも耐溶剤性が良好で、且つパターン形状が良好であり、カラーフィルタの着色層として好適に用いられ、有機発光素子上に形成する硬化膜に好適に用いられる。 II. Cured Product The cured product according to the present invention is a cured product of the photosensitive green resin composition according to the present invention.
The cured product according to the present invention is obtained, for example, by forming a coating film of the photosensitive green resin composition according to the present invention, drying the coating film, exposing, and developing as necessary, and heat treatment. be able to. The methods of forming, exposing, developing, and heat-treating the coating film may be, for example, the same methods as those used in the formation of the colored layer provided in the color filter according to the present invention, which will be described later.
The cured product according to the present invention has good solvent resistance and good pattern shape even when the heat treatment is performed at a low temperature of 130° C. or lower, 100° C. or lower, or 90° C. or lower.
The cured product according to the present invention has good solvent resistance even when subjected to low-temperature heat treatment, and has a good pattern shape. Used.
ＩＩＩ．カラーフィルタ
　本発明に係るカラーフィルタは、基板と、当該基板上に設けられた着色層とを少なくとも備えるカラーフィルタであって、当該着色層の少なくとも１つが、前記本発明に係る感光性緑色樹脂組成物の硬化物である。 III. Color filter The color filter according to the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is the photosensitive green resin composition according to the present invention. It is a hardened material.
　このような本発明に係るカラーフィルタについて、図を参照しながら説明する。図１は、本発明のカラーフィルタの一例を示す概略断面図である。図１によれば、本発明のカラーフィルタ１０は、基板１と、遮光部２と、着色層３とを有している。 Such a color filter according to the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of the color filter of the present invention. According to FIG. 1, the color filter 10 of the present invention has a substrate 1, a light shielding portion 2 and a colored layer 3. As shown in FIG.
＜着色層＞
　本発明のカラーフィルタに用いられる着色層は、少なくとも１つが、前記本発明に係る感光性緑色樹脂組成物の硬化物である着色層である。
　着色層は、通常、後述する基板上の遮光部の開口部に形成され、通常３色以上の着色パターンから構成される。
　また、当該着色層の配列としては、特に限定されず、例えば、ストライプ型、モザイク型、トライアングル型、４画素配置型等の一般的な配列とすることができる。また、着色層の幅、面積等は任意に設定することができる。
　当該着色層の厚みは、塗布方法、感光性緑色樹脂組成物の固形分濃度や粘度等を調整することにより、適宜制御されるが、通常、１～５μｍの範囲であることが好ましい。 <Colored layer>
At least one of the colored layers used in the color filter of the present invention is a colored layer that is a cured product of the photosensitive green resin composition according to the present invention.
The colored layer is usually formed in the opening of the light shielding part on the substrate, which will be described later, and is usually composed of colored patterns of three or more colors.
The arrangement of the colored layers is not particularly limited, and may be a general arrangement such as a stripe type, mosaic type, triangle type, four-pixel arrangement type, or the like. Moreover, the width, area, etc. of the colored layer can be arbitrarily set.
The thickness of the colored layer can be appropriately controlled by adjusting the coating method, solid content concentration and viscosity of the photosensitive green resin composition, and is preferably in the range of 1 to 5 μm.
　当該着色層は、例えば、下記の方法により形成することができる。
　まず、前述した本発明の感光性緑色樹脂組成物を、スプレーコート法、ディップコート法、バーコート法、ロールコート法、スピンコート法、ダイコート法などの塗布手段を用いて後述する基板上に塗布して、ウェット塗膜を形成させる。なかでもスピンコート法、ダイコート法を好ましく用いることができる。
　次いで、ホットプレートやオーブンなどを用いて、該ウェット塗膜を乾燥させたのち、これに、所定のパターンのマスクを介して露光し、アルカリ可溶性樹脂及び多官能モノマー等を光重合反応させて硬化塗膜とする。露光に使用される光源としては、例えば低圧水銀灯、高圧水銀灯、メタルハライドランプなどの紫外線、電子線等が挙げられる。露光量は、使用する光源や塗膜の厚みなどによって適宜調整される。
　また、露光後に重合反応を促進させるために、加熱処理を行ってもよい。加熱条件は、使用する感光性緑色樹脂組成物中の各成分の配合割合や、塗膜の厚み等によって適宜選択される。 The colored layer can be formed, for example, by the following method.
First, the photosensitive green resin composition of the present invention described above is applied onto a substrate described later using a coating method such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, or a die coating method. to form a wet coating. Among them, the spin coating method and the die coating method can be preferably used.
Next, after drying the wet coating film using a hot plate or an oven, it is exposed to light through a mask of a predetermined pattern, and the alkali-soluble resin and the polyfunctional monomer are photopolymerized and cured. It is used as a coating film. Light sources used for exposure include, for example, ultraviolet light from low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and electron beams. The amount of exposure is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
Moreover, in order to accelerate the polymerization reaction after exposure, heat treatment may be performed. The heating conditions are appropriately selected depending on the mixing ratio of each component in the photosensitive green resin composition to be used, the thickness of the coating film, and the like.
　次に、現像液を用いて現像処理し、未露光部分を溶解、除去することにより、所望のパターンで塗膜が形成される。現像液としては、通常、水や水溶性溶剤にアルカリを溶解させた溶液が用いられる。このアルカリ溶液には、界面活性剤などを適量添加してもよい。また、現像方法は一般的な方法を採用することができる。
　現像処理後は、通常、現像液の洗浄、感光性緑色樹脂組成物の硬化塗膜の乾燥が行われ、着色層が形成される。なお、現像処理後に、塗膜を十分に硬化させるために加熱処理を行ってもよい。加熱条件としては特に限定はなく、塗膜の用途に応じて適宜選択される。
　素子基板上に直接着色層を形成する製造工程での加熱処理は、３０℃以上１００℃以下で行うことが好ましく、３５℃以上９５℃以下で行うことがより好ましく、４０℃以上９０℃以下で行うことが更に好ましい。 Next, a coating film is formed in a desired pattern by developing with a developer to dissolve and remove the unexposed portions. As the developer, a solution obtained by dissolving an alkali in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to this alkaline solution. Moreover, a general method can be adopted as the developing method.
After development, the developer is usually washed and the cured coating film of the photosensitive green resin composition is dried to form a colored layer. In addition, you may heat-process in order to fully harden a coating film after development processing. The heating conditions are not particularly limited, and are appropriately selected according to the application of the coating film.
The heat treatment in the manufacturing process for forming the colored layer directly on the element substrate is preferably performed at 30° C. or higher and 100° C. or lower, more preferably 35° C. or higher and 95° C. or lower, and 40° C. or higher and 90° C. or lower. It is even more preferable to do so.
　前記本発明に係る感光性緑色樹脂組成物にアルカリ現像性を有しない場合には、着色層は、例えば、インクジェット法等の従来公知のパターン状塗膜の形成方法により所望のパターンで塗膜を形成後、露光し、光重合性化合物等を光重合反応させて硬化塗膜とする。前記と同様、露光後に重合反応を促進させるために、加熱処理を行ってもよい。 When the photosensitive green resin composition according to the present invention does not have alkali developability, the colored layer is formed in a desired pattern by a conventionally known method for forming a patterned coating film such as an inkjet method. After the formation, the film is exposed to light and a photopolymerization reaction of a photopolymerizable compound or the like is performed to form a cured coating film. In the same manner as described above, heat treatment may be performed in order to promote the polymerization reaction after exposure.
＜遮光部＞
　本発明のカラーフィルタにおける遮光部は、後述する基板上にパターン状に形成されるものであって、一般的なカラーフィルタに遮光部として用いられるものと同様とすることができる。
　当該遮光部のパターン形状としては、特に限定されず、例えば、ストライプ状、マトリクス状等の形状が挙げられる。遮光部は、スパッタリング法、真空蒸着法等によるクロム等の金属薄膜であっても良い。或いは、遮光部は、樹脂バインダー中にカーボン微粒子、金属酸化物、無機顔料、有機顔料等の遮光性粒子を含有させた樹脂層であってもよい。遮光性粒子を含有させた樹脂層の場合には、感光性レジストを用いて現像によりパターニングする方法、遮光性粒子を含有するインクジェットインクを用いてパターニングする方法、感光性レジストを熱転写する方法等がある。 <Light shielding part>
The light-shielding portion in the color filter of the present invention is formed in a pattern on a substrate, which will be described later, and can be the same as those used as light-shielding portions in general color filters.
The pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape, a matrix shape, and the like. The light shielding portion may be a metal thin film of chromium or the like formed by a sputtering method, a vacuum deposition method, or the like. Alternatively, the light-shielding portion may be a resin layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, or organic pigments in a resin binder. In the case of a resin layer containing light-shielding particles, a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring a photosensitive resist, and the like are available. be.
　遮光部の膜厚としては、金属薄膜の場合は０．２～０．４μｍ程度で設定され、黒色顔料をバインダー樹脂中に分散又は溶解させたものである場合は０．５～２μｍ程度で設定される。 The film thickness of the light-shielding portion is set to about 0.2 to 0.4 μm in the case of a metal thin film, and is set to about 0.5 to 2 μm in the case of a black pigment dispersed or dissolved in a binder resin. be done.
＜基板＞
　基板としては、後述する透明基板、シリコン基板、及び、透明基板又はシリコン基板上にアルミニウム、銀、銀／銅／パラジウム合金薄膜などを形成したものが用いられる。これらの基板上には、別のカラーフィルタ層、樹脂層、ＴＦＴ等のトランジスタ、回路等が形成されていてもよい。基板としては、後述する有機発光素子のような素子基板であってもよい。
　本発明のカラーフィルタにおける透明基板としては、可視光に対して透明な基材であればよく、特に限定されず、一般的なカラーフィルタに用いられる透明基板を使用することができる。具体的には、石英ガラス、無アルカリガラス、合成石英板等の可撓性のない透明なリジッド材、あるいは、透明樹脂フィルム、光学用樹脂板、フレキシブルガラス等の可撓性を有する透明なフレキシブル材が挙げられる。透明樹脂フィルム、光学用樹脂板としては、例えば、ポリエチレンテレフタレート（ＰＥＴ）フィルム、ポリイミドフィルム、ポリカーボネートフィルム等が挙げられるが、中でも酸素原子、窒素原子等のヘテロ原子を含むＰＥＴフィルム、ポリイミドフィルム等が好適に用いられる。
　当該透明基板の厚みは、特に限定されるものではないが、本発明のカラーフィルタの用途に応じて、例えば１００μｍ～１ｍｍ程度のものを使用することができる。
　なお、本発明のカラーフィルタは、上記基板、遮光部及び着色層以外にも、例えば、オーバーコート層や透明電極層、さらには配向膜や柱状スペーサ等が形成されたものであってもよい。
　また、本発明のカラーフィルタは、外光反射を防止する円偏光板代替としても利用できる。 <Substrate>
As the substrate, a transparent substrate, a silicon substrate, and a transparent substrate or a silicon substrate on which an aluminum, silver, silver/copper/palladium alloy thin film or the like is formed are used. Other color filter layers, resin layers, transistors such as TFTs, circuits, and the like may be formed on these substrates. The substrate may be an element substrate such as an organic light emitting element which will be described later.
The transparent substrate in the color filter of the present invention is not particularly limited as long as it is transparent to visible light, and transparent substrates used in general color filters can be used. Specifically, transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible materials such as transparent resin films, optical resin plates, and flexible glass. material. Examples of transparent resin films and optical resin plates include polyethylene terephthalate (PET) films, polyimide films, and polycarbonate films. It is preferably used.
Although the thickness of the transparent substrate is not particularly limited, a thickness of about 100 μm to 1 mm, for example, can be used depending on the application of the color filter of the present invention.
The color filter of the present invention may be formed with, for example, an overcoat layer, a transparent electrode layer, an alignment film, columnar spacers, etc., in addition to the above substrate, light shielding portion and colored layer.
Moreover, the color filter of the present invention can be used as a substitute for a circularly polarizing plate that prevents reflection of external light.
ＩＶ．表示装置
　本発明に係る表示装置は、前記本発明に係るカラーフィルタを有することを特徴とする。本発明において表示装置の構成は特に限定されず、従来公知の表示装置の中から適宜選択することができ、例えば、液晶表示装置や、有機発光表示装置などが挙げられる。 IV. Display Device A display device according to the present invention includes the color filter according to the present invention. In the present invention, the configuration of the display device is not particularly limited, and can be appropriately selected from conventionally known display devices, such as liquid crystal display devices and organic light-emitting display devices.
［液晶表示装置］
　本発明の液晶表示装置としては、例えば、前述した本発明に係るカラーフィルタと、対向基板と、前記カラーフィルタと前記対向基板との間に形成された液晶層とを有する液晶表示装置が挙げられる。
　このような本発明の液晶表示装置について、図を参照しながら説明する。図２は、本発明の液晶表示装置の一例を示す概略図である。図２に例示するように本発明の液晶表示装置４０は、カラーフィルタ１０と、ＴＦＴアレイ基板等を有する対向基板２０と、上記カラーフィルタ１０と上記対向基板２０との間に形成された液晶層３０とを有している。
　なお、本発明の液晶表示装置は、この図２に示される構成に限定されるものではなく、一般的にカラーフィルタが用いられた液晶表示装置として公知の構成とすることができる。 [Liquid crystal display device]
Examples of the liquid crystal display device of the present invention include a liquid crystal display device having the above-described color filter according to the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate. .
Such a liquid crystal display device of the present invention will be described with reference to the drawings. FIG. 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention. As illustrated in FIG. 2, a liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer formed between the color filter 10 and the counter substrate 20. 30.
The liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, and may have a known configuration as a liquid crystal display device generally using color filters.
　本発明の液晶表示装置の駆動方式としては、特に限定はなく一般的に液晶表示装置に用いられている駆動方式を採用することができる。このような駆動方式としては、例えば、ＴＮ方式、ＩＰＳ方式、ＯＣＢ方式、及びＭＶＡ方式等を挙げることができる。本発明においてはこれらのいずれの方式であっても好適に用いることができる。
　また、対向基板としては、本発明の液晶表示装置の駆動方式等に応じて適宜選択して用いることができる。
　さらに、液晶層を構成する液晶としては、本発明の液晶表示装置の駆動方式等に応じて、誘電異方性の異なる各種液晶、及びこれらの混合物を用いることができる。 The driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for liquid crystal display devices can be adopted. Examples of such driving methods include the TN method, the IPS method, the OCB method, and the MVA method. Any of these methods can be suitably used in the present invention.
Also, the counter substrate can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention.
Further, as the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used according to the driving method of the liquid crystal display device of the present invention.
　液晶層の形成方法としては、一般に液晶セルの作製方法として用いられる方法を使用することができ、例えば、真空注入方式や液晶滴下方式等が挙げられる。前記方法によって液晶層を形成後、液晶セルを常温まで徐冷することにより、封入された液晶を配向させることができる。 As a method for forming the liquid crystal layer, a method generally used as a method for manufacturing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method. After the liquid crystal layer is formed by the above method, the liquid crystal cell is gradually cooled to room temperature, thereby aligning the enclosed liquid crystal.
［有機発光表示装置］
　本発明の有機発光表示装置としては、例えば、前述した本発明に係るカラーフィルタと、有機発光素子とを有する有機発光表示装置が挙げられる。
　このような本発明の有機発光表示装置について、図を参照しながら説明する。図３は、本発明の有機発光表示装置の一例を示す概略図である。図３に例示するように本発明の有機発光表示装置１００は、基板５０上に有機発光素子８０と封止層９０が形成され、その上にカラーフィルタ１０が形成されている。基板５０としては、フレキシブル基板上にＴＦＴが形成されている基板であってよい。図３の有機発光表示装置において、カラーフィルタ１０は、円偏光板代替カラーフィルタであって良い。 [Organic Light Emitting Display Device]
Examples of the organic light-emitting display device of the present invention include an organic light-emitting display device having the above-described color filter according to the present invention and an organic light-emitting element.
The organic light-emitting display device of the present invention will be described with reference to the drawings. FIG. 3 is a schematic diagram showing an example of the organic light-emitting display device of the present invention. As illustrated in FIG. 3, the organic light emitting diode display 100 of the present invention has an organic light emitting element 80 and a sealing layer 90 formed on a substrate 50, and a color filter 10 is formed thereon. The substrate 50 may be a flexible substrate on which a TFT is formed. In the organic light emitting diode display of FIG. 3, the color filter 10 may be a color filter substituting for a circular polarizer.
　有機発光素子８０の積層方法としては、例えば、基材５０上に、透明陽極７１、正孔注入層７２、正孔輸送層７３、発光層７４、電子注入層７５、および陰極７６を逐次形成していく方法などが挙げられる。有機発光素子８０における、透明陽極７１、正孔注入層７２、正孔輸送層７３、発光層７４、電子注入層７５、および陰極７６、その他の構成は、公知のものを適宜用いることができる。また、封止層９０は、公知のものを適宜用いることができる。このようにして作製された有機発光表示装置１００は、例えば、パッシブ駆動方式の有機ＥＬディスプレイにもアクティブ駆動方式の有機ＥＬディスプレイにも適用可能である。
　なお、本発明の有機発光表示装置は、この図３に示される構成に限定されるものではなく、一般的にカラーフィルタが用いられた有機発光表示装置として公知の構成とすることができる。 As a lamination method of the organic light emitting element 80, for example, a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light emitting layer 74, an electron injection layer 75, and a cathode 76 are sequentially formed on the substrate 50. and the like. The transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, the cathode 76, and other structures in the organic light emitting element 80 can be appropriately used known ones. Moreover, the sealing layer 90 can use a well-known thing suitably. The organic light-emitting display device 100 manufactured in this way can be applied to, for example, a passive drive type organic EL display and an active drive type organic EL display.
The organic light-emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and may have a known configuration as an organic light-emitting display device generally using color filters.
　また、本発明に係る表示装置は、有機発光素子上に、前記本発明に係る感光性緑色樹脂組成物の硬化膜を有するものであってよい。
　このような本発明に係る表示装置は、前記本発明に係る感光性緑色樹脂組成物の硬化膜が、有機発光素子上に形成されているものであることから、外付けの円偏光板や、外付けのカラーフィルタ基板が不要であり、これらを有しないものであってよい。
　このような本発明に係る表示装置は、前記本発明に係る感光性緑色樹脂組成物を用いて、有機発光素子上に硬化膜が形成されることから、有機発光素子と硬化膜の間に外付けのカラーフィルタ基板に用いられるような基板を有しないため、薄膜化とフレキシブル性が向上したものである。 Moreover, the display device according to the present invention may have a cured film of the photosensitive green resin composition according to the present invention on the organic light-emitting element.
In such a display device according to the present invention, since the cured film of the photosensitive green resin composition according to the present invention is formed on the organic light-emitting element, an external circularly polarizing plate, An external color filter substrate is unnecessary and may be absent.
Such a display device according to the present invention uses the photosensitive green resin composition according to the present invention to form a cured film on the organic light-emitting element. Since it does not have a substrate that is used as an attached color filter substrate, it has improved thinness and flexibility.
　このような本発明に係る有機発光素子を含む有機発光表示装置について、図を参照しながら説明する。図４は、本発明に係る有機発光素子を備えた表示装置の他の一例を示す概略断面図である。図４に例示するように本発明に係る表示装置２００は、有機発光素子を備えた素子基板１３０と、当該素子基板１３０上に、着色硬化膜（１０９Ｒ、１０９Ｇ、１０９Ｂ）を含む外光反射防止膜１２０を備え、更にその上に封止膜１１１を備える。
　前記有機発光素子を備えた素子基板１３０は、基板１０１上に駆動素子である薄膜トランジスタ（ＴＦＴ）１０２が各サブピクセルに対応するよう配置され、その上に封止膜１０３を備え、さらに封止膜１０３上には各サブピクセルに対応する電極１０４（陽極）、各サブピクセルを区画する隔壁１０５を備え、その区画内にＲ、Ｇ，Ｂ３色のサブピクセルを構成する有機発光素子（１０６Ｒ、１０６Ｇ、１０６Ｂ）が配置され、当該有機発光素子（１０６Ｒ、１０６Ｇ、１０６Ｂ）上に、更に電極１０７（陰極）を備えている。前記有機発光素子を備えた素子基板１３０は、さらにその上から有機発光素子を覆う封止層１０８を備える。
　素子基板１３０における有機ＥＬ素子（１０６Ｒ、１０６Ｇ、１０６Ｂ）上の封止層１０８上に、光硬化性着色樹脂組成物を用いて形成される各有機ＥＬ素子に対応した３色の着色硬化膜（１０９Ｒ、１０９Ｇ、１０９Ｂ）及び遮光部１１０を含む外光反射防止膜１２０を備え、更にその上に封止膜１１１を備える。
　図４の本発明に係る表示装置２００は、封止膜１１１の上に、更に、透明粘着剤層１１２を介してカバー材１１３を備えている。
　本発明に係る表示装置２００は、図示しないが、例えば、さらに封止膜１１１上に絶縁膜および透明電極層からなるタッチセンサー層を備え、さらにタッチセンサー層上にハードコート層等、公知の構成をさらに適宜備えていてよいものである。
　上記のように、前記有機発光素子を備えた素子基板１３０上に設けられた、着色硬化膜（１０９Ｒ、１０９Ｇ、１０９Ｂ）及び遮光部１１０の層が、外光反射防止膜１２０として用いられることから、本発明に用いられる外光反射防止膜は、外付けの円偏光板や外付けのカラーフィルタ基板のように別途基板が含まれず、薄膜化及びフレキシブル性を向上できる。 An organic light-emitting display device including the organic light-emitting device according to the present invention will be described with reference to the drawings. FIG. 4 is a schematic cross-sectional view showing another example of a display device having an organic light-emitting device according to the present invention. As illustrated in FIG. 4, a display device 200 according to the present invention includes an element substrate 130 having an organic light emitting element, and an external light reflection preventing film including colored cured films (109R, 109G, 109B) on the element substrate 130. A membrane 120 is provided, and a sealing membrane 111 is provided thereon.
A device substrate 130 having the organic light emitting device includes a substrate 101 on which thin film transistors (TFTs) 102, which are driving devices, are arranged so as to correspond to respective sub-pixels, and a sealing film 103 is provided thereon. An electrode 104 (anode) corresponding to each sub-pixel and partition walls 105 partitioning each sub-pixel are provided on 103, and organic light-emitting elements (106R, 106G , 106B) are arranged, and an electrode 107 (cathode) is further provided on the organic light-emitting elements (106R, 106G, 106B). The element substrate 130 having the organic light emitting elements further includes a sealing layer 108 covering the organic light emitting elements from thereon.
Three colored cured films ( 109R, 109G, 109B) and a light blocking portion 110, and a sealing film 111 is further provided thereon.
A display device 200 according to the present invention in FIG. 4 further includes a cover material 113 on a sealing film 111 with a transparent adhesive layer 112 interposed therebetween.
Although not shown, the display device 200 according to the present invention has a known structure such as a touch sensor layer including an insulating film and a transparent electrode layer on the sealing film 111 and a hard coat layer on the touch sensor layer. may be further provided as appropriate.
As described above, the layers of the colored cured films (109R, 109G, 109B) and the light shielding part 110 provided on the element substrate 130 having the organic light emitting element are used as the external light antireflection film 120. The external light antireflection film used in the present invention does not include a separate substrate such as an external circularly polarizing plate or an external color filter substrate, and can improve thinness and flexibility.
　本発明に係る表示装置においては、有機発光素子のサブピクセルの（１０６Ｒ、１０６Ｇ、１０６Ｂ）の色と、例えば封止層１０８等の少なくとも１層を介して直上の着色硬化膜（１０９Ｒ、１０９Ｇ、１０９Ｂ）の色が同種の色であるように調整することが好ましい。この有機発光素子上に設けられた着色硬化膜により、外光は、本来有機発光素子が発光する色を除いて遮蔽されるとともに、有機発光素子が発光する光はカットされないため、光利用効率を低下させることなく、外光反射を抑制することが可能となる。
　前記本発明に係る感光性緑色樹脂組成物の硬化膜は、前記３色の着色硬化膜（１０９Ｒ、１０９Ｇ、１０９Ｂ）のうち、緑色硬化膜（１０９Ｇ）であってよい。 In the display device according to the present invention, the colors (106R, 106G, 106B) of the sub-pixels of the organic light-emitting element and the colored cured films (109R, 109G, 109B) are preferably adjusted to be of the same kind. The colored cured film provided on the organic light-emitting element blocks external light except for the color originally emitted by the organic light-emitting element, and does not block the light emitted by the organic light-emitting element, thereby improving the light utilization efficiency. It is possible to suppress the external light reflection without lowering it.
The cured film of the photosensitive green resin composition according to the present invention may be the green cured film (109G) among the three colored cured films (109R, 109G, 109B).
　本発明に係る表示装置に用いられる基板１０１、駆動素子である薄膜トランジスタ（ＴＦＴ）１０２、封止膜１０３、電極１０４（陽極）、各サブピクセルを区画する隔壁１０５、サブピクセルを構成する有機発光素子（１０６Ｒ、１０６Ｇ、１０６Ｂ）、電極１０７（陰極）等は、公知の構成を適宜選択して用いることができる。
　有機発光素子には、発光層の他に、正孔注入層、正孔輸送層、電子注入層等、公知の構成を備えていてもよい。 A substrate 101 used in a display device according to the present invention, a thin film transistor (TFT) 102 as a driving element, a sealing film 103, an electrode 104 (anode), a partition wall 105 partitioning each sub-pixel, and an organic light-emitting element constituting a sub-pixel. (106R, 106G, 106B), the electrode 107 (cathode), etc. can be used by appropriately selecting known configurations.
The organic light-emitting device may have known structures such as a hole injection layer, a hole transport layer, an electron injection layer, etc., in addition to the light-emitting layer.
　本発明に係る表示装置に用いられる有機ＥＬ素子上の封止層１０８としては、無機膜、または有機膜、及びそれらを積層した多層膜からなる。水分や酸素の浸入を抑制する効果が高い点から、多層膜を用いることが好ましい。
　具体的には例えば、金属膜、金属酸化物膜、ＳｉＯｘ、ＳｉＮｘ等の無機膜と有機膜を積層した多層膜等が挙げられる。 The sealing layer 108 on the organic EL element used in the display device according to the present invention is composed of an inorganic film, an organic film, and a multilayer film in which these are laminated. It is preferable to use a multilayer film because it has a high effect of suppressing penetration of moisture and oxygen.
Specific examples thereof include a multilayer film in which an inorganic film such as a metal film, a metal oxide film, SiOx, SiNx, and an organic film are laminated.
　本発明に係る表示装置に用いられる着色硬化膜は、少なくとも１つが、前記本発明に係る感光性緑色樹脂組成物の硬化膜である。
　着色硬化膜は、通常、有機発光素子上の封止層１０８上の後述する遮光部の開口部に形成され、通常３色以上の着色パターンから構成される。これらは有機発光素子のサブピクセルの（１０６Ｒ、１０６Ｇ、１０６Ｂ）と同様の着色パターンであってよい。
　着色硬化膜（１０９Ｒ、１０９Ｇ、１０９Ｂ）の配列としては、例えば、ストライプ型、モザイク型、トライアングル型、４画素配置型等の一般的な配列とすることができる。また、着色層の幅、面積等は有機発光素子のサブピクセルの（１０６Ｒ、１０６Ｇ、１０６Ｂ）に適合するように適宜設定することができる。
　当該着色硬化膜の厚みは、塗布方法、感光性緑色樹脂組成物の固形分濃度や粘度等を調整することにより、適宜制御されるが、通常、１μｍ～５μｍの範囲である。 At least one of the colored cured films used in the display device according to the present invention is a cured film of the photosensitive green resin composition according to the present invention.
The colored cured film is usually formed in an opening of a light shielding part, which will be described later, on the sealing layer 108 on the organic light emitting element, and is usually composed of colored patterns of three or more colors. These may be colored patterns similar to (106R, 106G, 106B) of the sub-pixels of the organic light emitting device.
The arrangement of the colored cured films (109R, 109G, 109B) may be, for example, a general arrangement such as a stripe type, mosaic type, triangle type, or 4-pixel arrangement type. Also, the width, area, etc. of the colored layer can be appropriately set so as to match the sub-pixels (106R, 106G, 106B) of the organic light-emitting element.
The thickness of the colored cured film is appropriately controlled by adjusting the coating method, solid content concentration and viscosity of the photosensitive green resin composition, and is usually in the range of 1 μm to 5 μm.
　本発明に係る表示装置に用いられる遮光部１１０は、通常、有機発光素子上の封止層１０８上にパターン状に形成されるものであって、一般的なカラーフィルタに遮光部として用いられるものと同様とすることができる。
　当該遮光部のパターン形状としては、前記着色硬化膜の形状に合わせて適宜選択されればよく、例えば、ストライプ状、マトリクス状等の形状が挙げられる。遮光部は、スパッタリング法、真空蒸着法等によるクロム等の金属薄膜であっても良い。或いは、遮光部は、樹脂バインダー中にカーボン微粒子、金属酸化物、無機顔料、有機顔料等の遮光性粒子を含有させた樹脂層であってもよい。遮光性粒子を含有させた樹脂層の場合には、感光性レジストを用いて現像によりパターニングする方法、遮光性粒子を含有するインクジェットインクを用いてパターニングする方法、感光性レジストを熱転写する方法等がある。 The light shielding part 110 used in the display device according to the present invention is usually formed in a pattern on the sealing layer 108 on the organic light emitting element, and is used as a light shielding part in a general color filter. can be the same as
The pattern shape of the light shielding portion may be appropriately selected according to the shape of the colored cured film, and examples thereof include a stripe shape and a matrix shape. The light shielding portion may be a metal thin film of chromium or the like formed by a sputtering method, a vacuum deposition method, or the like. Alternatively, the light-shielding portion may be a resin layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, or organic pigments in a resin binder. In the case of a resin layer containing light-shielding particles, a method of patterning by development using a photosensitive resist, a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring a photosensitive resist, and the like are available. be.
　遮光部の膜厚としては、金属薄膜の場合は０．２μｍ～０．４μｍ程度で設定され、黒色顔料をバインダー樹脂中に分散又は溶解させたものである場合は０．５μｍ～２μｍ程度で設定される。 The film thickness of the light-shielding portion is set to about 0.2 μm to 0.4 μm in the case of a metal thin film, and is set to about 0.5 μm to 2 μm in the case of a black pigment dispersed or dissolved in a binder resin. be done.
　着色硬化膜（１０９Ｒ、１０９Ｇ、１０９Ｂ）及び遮光部１１０の上に設けられる封止膜１１１としては、公知の材料を適宜選択して用いることができる。
　また、封止膜１１１上に設けられる透明粘着剤層１１２や、カバー材１１３としても、公知の材料を適宜選択して用いることができる。本発明においてはカバー材にガラスを用いた場合であっても、緑色硬化膜の耐候性が良好で、透過率の低下が抑制される点から、カバー材としてガラスを用いることができる。 As the colored cured films (109R, 109G, 109B) and the sealing film 111 provided on the light shielding portion 110, known materials can be appropriately selected and used.
Also, for the transparent adhesive layer 112 provided on the sealing film 111 and the cover material 113, known materials can be appropriately selected and used. In the present invention, even when glass is used as the cover material, glass can be used as the cover material because the green cured film has good weather resistance and the reduction in transmittance is suppressed.
　なお、本発明に係る表示装置は、前記図４に示される構成に限定されるものではなく、その他にも、公知の有機発光素子を備えた表示装置の構成をさらに備えていて良いものである。 In addition, the display device according to the present invention is not limited to the configuration shown in FIG. 4, and may further include the configuration of a display device having a known organic light-emitting element. .
Ｖ．有機発光素子と外光反射防止膜の積層体の製造方法
　本発明に係る有機発光素子と外光反射防止膜の積層体の製造方法は、
有機発光素子上に、前記本発明に係る感光性緑色樹脂組成物を塗布することにより塗膜を形成する工程、
　前記塗膜に光照射する工程、
　前記光照射後の膜を、加熱するポストベイク工程、及び、
　前記光照射後の膜を、現像する工程を含有することにより、
有機発光素子上に前記本発明に係る感光性緑色樹脂組成物の硬化膜を形成する工程を有する。
　以下各工程について、説明する。 V. Method for producing a laminate of an organic light-emitting element and an anti-reflection film for external light The method for producing a laminate of an organic light-emitting element and an anti-reflection film for external light according to the present invention comprises:
A step of forming a coating film by applying the photosensitive green resin composition according to the present invention on the organic light emitting device;
a step of irradiating the coating film with light;
A post-baking step of heating the film after the light irradiation, and
By including the step of developing the film after the light irradiation,
A step of forming a cured film of the photosensitive green resin composition according to the present invention on the organic light emitting device.
Each step will be described below.
　有機発光素子上に、前記本発明に係る感光性緑色樹脂組成物を塗布する工程において、有機発光素子上とは、有機発光素子に隣接して塗布しなくてもよく、少なくとも１層介して塗布してよい。図４のように、有機発光素子を備える素子基板１３０においては、有機発光素子のサブピクセルの（１０６Ｒ、１０６Ｇ、１０６Ｂ）の上に、通常、更に電極１０７や、水分や酸素の浸入を抑制するための封止層１０８が設けられることから、これらの電極及び封止層等を介して、有機発光素子上に塗布してよい。 In the step of applying the photosensitive green resin composition according to the present invention on the organic light-emitting element, it is not necessary to apply the composition on the organic light-emitting element adjacent to the organic light-emitting element. You can As shown in FIG. 4, in the element substrate 130 including the organic light emitting elements, the electrodes 107 and the permeation of moisture and oxygen are usually further suppressed on the sub-pixels (106R, 106G, 106B) of the organic light emitting elements. Since the sealing layer 108 is provided for the purpose, it may be applied onto the organic light-emitting element through these electrodes, the sealing layer, and the like.
　例えば、封止層１０８上に、前述に例示したような公知の方法によって、遮光部１１０を予め設け、当該遮光部１１０の開口部に、着色硬化膜（１０９Ｒ、１０９Ｇ、１０９Ｂ）が形成されるように塗布してよい。 For example, the light shielding portion 110 is provided in advance on the sealing layer 108 by a known method as exemplified above, and the colored cured films (109R, 109G, 109B) are formed in the openings of the light shielding portion 110. It may be applied as follows.
　例えば、スプレーコート法、ディップコート法、バーコート法、ロールコート法、スピンコート法、ダイコート法などの塗布手段を用いて、前述した本発明の感光性緑色樹脂組成物を、前記有機発光素子上に、塗布する。塗布手段としては、なかでもスピンコート法、ダイコート法を好ましく用いることができる。
　次いで、ホットプレートやオーブンなどを用いて、該ウェット塗膜を乾燥させ、塗膜を形成する。 For example, a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, using a coating means such as a die coating method, the photosensitive green resin composition of the present invention described above, on the organic light emitting device to apply. As the coating means, a spin coating method and a die coating method can be preferably used.
Then, the wet coating film is dried using a hot plate, an oven, or the like to form a coating film.
　得られた塗膜に、所定のパターンのマスクを介して光照射（露光）し、光重合性化合物、及び必要に応じてアルカリ可溶性樹脂等を光重合反応させる。露光に使用される光源としては、例えば低圧水銀灯、高圧水銀灯、メタルハライドランプなどの紫外線、電子線等が挙げられる。露光量は、使用する光源や塗膜の厚みなどによって適宜調整される。 The obtained coating film is irradiated with light (exposure) through a mask of a predetermined pattern, and the photopolymerizable compound and, if necessary, the alkali-soluble resin, etc. are photopolymerized. Light sources used for exposure include, for example, ultraviolet light from low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, electron beams, and the like. The amount of exposure is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
　次いで、露光後に重合反応を促進させるために、前記光照射後の膜を、加熱するポストベイク工程を行ってもよい。加熱条件は、使用する感光性緑色樹脂組成物中の各成分の配合割合や、塗膜の厚み等によって適宜選択されればよい。
　ポストベイク工程は、前記光照射後の膜に対して、後述する現像工程前に行ってもよいし、現像工程後に行ってもよいし、現像工程前後に行ってもよい。 Then, in order to promote the polymerization reaction after exposure, a post-baking step of heating the film after the light irradiation may be performed. The heating conditions may be appropriately selected according to the mixing ratio of each component in the photosensitive green resin composition to be used, the thickness of the coating film, and the like.
The post-baking process may be performed on the film after the light irradiation before the development process described later, after the development process, or before and after the development process.
　本発明においては、有機発光素子を備えた素子基板上に直接着色硬化膜を形成することから、前記ポストベイク工程における加熱温度が、１３０℃以下であることが好ましい。加熱温度は、１００℃以下がより好ましく、９０℃以下が更に好ましい。また、加熱温度は、３０℃以上であってよく、３５℃以上であってよく、４０℃以上であってよい。 In the present invention, the heating temperature in the post-baking step is preferably 130° C. or less because the colored cured film is directly formed on the element substrate having the organic light-emitting element. The heating temperature is more preferably 100° C. or lower, still more preferably 90° C. or lower. Also, the heating temperature may be 30° C. or higher, 35° C. or higher, or 40° C. or higher.
　次に、前記光照射後の膜を、現像する。現像する前記光照射後の膜は、ポストベイク後の膜であってもよい。
　現像工程においては、現像液を用いて現像処理し、未露光部分を溶解、除去することにより、所望のパターンで塗膜が形成される。現像液としては、通常、水や水溶性溶剤にアルカリを溶解させた溶液が用いられる。このアルカリ溶液には、界面活性剤などを適量添加してもよい。また、現像方法は一般的な方法を採用することができる。 Next, the film after the light irradiation is developed. The film after light irradiation to be developed may be a film after post-baking.
In the developing step, a coating film is formed in a desired pattern by developing with a developer to dissolve and remove the unexposed portions. As the developer, a solution obtained by dissolving an alkali in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to this alkaline solution. Moreover, a general method can be adopted as the developing method.
　現像処理後は、通常、現像液の洗浄、感光性緑色樹脂組成物の硬化膜の乾燥が行われ、着色硬化膜が形成される。なお、現像処理後に、塗膜を十分に硬化させるために加熱処理を行ってもよい。
　本発明では有機発光素子を備えた素子基板上に直接着色硬化膜を形成することから、このポストベイク工程における加熱温度も、１３０℃以下が好ましく、１００℃以下がより好ましく、９０℃以下が更に好ましい。また、加熱温度は、３０℃以上であってよく、３５℃以上であってよく、４０℃以上であってよい。 After the development treatment, the developer is usually washed and the cured film of the photosensitive green resin composition is dried to form a colored cured film. In addition, you may heat-process in order to fully harden a coating film after development processing.
In the present invention, since a colored cured film is directly formed on an element substrate provided with an organic light-emitting element, the heating temperature in this post-baking step is preferably 130° C. or less, more preferably 100° C. or less, and even more preferably 90° C. or less. . Also, the heating temperature may be 30° C. or higher, 35° C. or higher, or 40° C. or higher.
　また、現像処理後や、ポストベイク後の膜を更に硬化するために、追加で光照射（露光）してもよい。 In addition, light irradiation (exposure) may be additionally performed after development processing or in order to further harden the film after post-baking.
　以下、本発明について実施例を示して具体的に説明する。これらの記載により本発明を制限するものではない。
　塩形成前の共重合体の質量平均分子量（Ｍｗ）は、前述の本発明の明細書に記載した測定方法に従って、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）により標準ポリスチレン換算値として求めた。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to Examples. These descriptions do not limit the invention.
The mass average molecular weight (Mw) of the copolymer before salt formation was determined as a standard polystyrene equivalent value by GPC (gel permeation chromatography) according to the measurement method described in the specification of the present invention.
（合成例１：ブロック共重合体１の合成）
　冷却管、添加用ロート、窒素用インレット、機械的攪拌機、デジタル温度計を備えた５００ｍＬ丸底４口セパラブルフラスコにＴＨＦ２５０質量部、塩化リチウム０．６質量部を加え、充分に窒素置換を行った。反応フラスコを－６０℃まで冷却した後、ブチルリチウム４．９質量部（１５質量％ヘキサン溶液）、ジイソプロピルアミン１．１質量部、イソ酪酸メチル１．０質量部をシリンジを用いて注入した。Ｂブロック用モノマーのメタクリル酸１－エトキシエチル（ＥＥＭＡ）２．２質量部、メタクリル酸２－（トリメチルシリルオキシ）エチル（ＴＭＳＭＡ）　２９．１質量部、メタクリル酸２－エチルヘキシル（ＥＨＭＡ）１２．８質量部、メタクリル酸ｎ－ブチル（ＢＭＡ）１３．７質量部、メタクリル酸ベンジル（ＢｚＭＡ）９．５質量部、メタクリル酸メチル（ＭＭＡ）１７．５質量部を、添加用ロートを用いて６０分かけて滴下した。３０分後、Ａブロック用モノマーであるメタクリル酸ジメチルアミノエチル（ＤＭＭＡ）２６．７質量部を２０分かけて滴下した。３０分間反応させた後、メタノール１．５質量部を加えて反応を停止させた。得られた前駆体ブロック共重合体ＴＨＦ溶液はヘキサン中で再沈殿させ、濾過、真空乾燥により精製を行い、ＰＧＭＥＡで希釈し固形分３０質量％溶液とした。水を３２．５質量部加え、１００℃に昇温し７時間反応させ、ＥＥＭＡ由来の構成単位を脱保護しメタクリル酸（ＭＡＡ）由来の構成単位とし、ＴＭＳＭＡ由来の構成単位を脱保護してメタクリル酸２－ヒドロキシエチル（ＨＥＭＡ）由来の構成単位とした。得られたブロック共重合体ＰＧＭＥＡ溶液はヘキサン中で再沈殿させ、濾過、真空乾燥により精製を行い、前記一般式（Ｉ）で表される構成単位を含むブロック共重合体１（アミン価　９５ｍｇＫＯＨ／ｇ、酸価　８ｍｇＫＯＨ／ｇ、Ｔｇ３８℃）を得た。重量平均分子量Ｍｗは７７３０であった。 (Synthesis Example 1: Synthesis of Block Copolymer 1)
250 parts by mass of THF and 0.6 parts by mass of lithium chloride were added to a 500 mL round-bottomed 4-necked separable flask equipped with a cooling tube, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, and the mixture was sufficiently purged with nitrogen. rice field. After cooling the reaction flask to −60° C., 4.9 parts by mass of butyllithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 parts by mass of methyl isobutyrate were injected using a syringe. B-block monomers 1-ethoxyethyl methacrylate (EEMA) 2.2 parts by mass, 2-(trimethylsilyloxy)ethyl methacrylate (TMSMA) 29.1 parts by mass, and 2-ethylhexyl methacrylate (EHMA) 12.8 parts by mass Part, n-butyl methacrylate (BMA) 13.7 parts by mass, benzyl methacrylate (BzMA) 9.5 parts by mass, methyl methacrylate (MMA) 17.5 parts by mass, using an addition funnel for 60 minutes dripped. After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA), which is a monomer for A block, was added dropwise over 20 minutes. After reacting for 30 minutes, 1.5 parts by mass of methanol was added to terminate the reaction. The obtained precursor block copolymer THF solution was reprecipitated in hexane, filtered, purified by vacuum drying, and diluted with PGMEA to obtain a solid content 30% by mass solution. Add 32.5 parts by mass of water, raise the temperature to 100 ° C. and react for 7 hours, deprotect the structural unit derived from EEMA to make it a structural unit derived from methacrylic acid (MAA), and deprotect the structural unit derived from TMSMA. A structural unit derived from 2-hydroxyethyl methacrylate (HEMA) was used. The resulting block copolymer PGMEA solution was reprecipitated in hexane, filtered, and purified by vacuum drying to obtain block copolymer 1 (amine value: 95 mg KOH/ g, acid value 8 mgKOH/g, Tg 38°C). The weight average molecular weight Mw was 7,730.
（合成例２：式（Ａ－２）で表されるオキシムエステル系光開始剤の合成）
　国際公開２０１５／１５２１５３号公報の段落０１１４～０１１７の化合物Ｎｏ．７３の製造と同様にして、前記式（Ａ－２）で表されるオキシムエステル系光開始剤を合成した。 (Synthesis Example 2: Synthesis of oxime ester photoinitiator represented by formula (A-2))
Compound No. of paragraphs 0114 to 0117 of WO 2015/152153. An oxime ester photoinitiator represented by the above formula (A-2) was synthesized in the same manner as in the production of No. 73.
（調製例１：アルカリ可溶性樹脂Ａの調製）
　重合槽に、ＰＧＭＥＡを３００質量部仕込み、窒素雰囲気下で１００℃に昇温した後、メタクリル酸２－フェノキシエチル（ＰｈＥＭＡ）９０質量部、ＭＭＡ５４質量部、メタクリル酸（ＭＡＡ）３６質量部及びパーブチルＯ（日油株式会社製）６質量部、連鎖移動剤（ｎ－ドデシルメルカプタン）２質量部を１．５時間かけて連続的に滴下した。その後、１００℃を保持して反応を続け、上記主鎖形成用混合物の滴下終了から２時間後に重合禁止剤として、ｐ－メトキシフェノール０．１質量部を添加して重合を停止した。
　次に、空気を吹き込みながら、エポキシ基含有化合物としてメタクリル酸グリシジル（ＧＭＡ）２０質量部を添加して、１１０℃に昇温した後、トリエチルアミン０．８質量部を添加して１１０℃で１５時間付加反応させ、アルカリ可溶性樹脂Ａ溶液（重量平均分子量（Ｍｗ）８５００、酸価７５ｍｇＫＯＨ／ｇ、固形分４０質量％）を得た。
　なお、上記重量平均分子量の測定方法は、ポリスチレンを標準物質とし、ＴＨＦを溶離液としてショウデックスＧＰＣシステム－２１Ｈ（Ｓｈｏｄｅｘ　ＧＰＣ　Ｓｙｓｔｅｍ－２１Ｈ）により重量平均分子量を測定した。また酸価の測定方法は、ＪＩＳ　Ｋ　００７０に基づいて測定した。 (Preparation Example 1: Preparation of alkali-soluble resin A)
A polymerization tank was charged with 300 parts by mass of PGMEA, heated to 100° C. under a nitrogen atmosphere, and then 90 parts by mass of 2-phenoxyethyl methacrylate (PhEMA), 54 parts by mass of MMA, 36 parts by mass of methacrylic acid (MAA) and perbutyl. 6 parts by mass of O (manufactured by NOF Corporation) and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. Thereafter, the reaction was continued while maintaining the temperature at 100° C., and 0.1 part by mass of p-methoxyphenol was added as a polymerization inhibitor to terminate the polymerization two hours after the completion of dropping the mixture for forming the main chain.
Next, while blowing in air, 20 parts by mass of glycidyl methacrylate (GMA) as an epoxy group-containing compound was added, and the temperature was raised to 110°C. Then, 0.8 parts by mass of triethylamine was added and the temperature was maintained at 110°C for 15 hours. Addition reaction was carried out to obtain an alkali-soluble resin A solution (weight average molecular weight (Mw) 8500, acid value 75 mgKOH/g, solid content 40% by mass).
The weight average molecular weight was measured by Shodex GPC System-21H using polystyrene as a standard substance and THF as an eluent. Moreover, the method for measuring the acid value was based on JIS K 0070.
（実施例１：感光性緑色樹脂組成物Ｇ－１の製造）
（１）色材分散液Ｂ（１）の製造
　２２５ｍＬマヨネーズ瓶中に、ＰＧＭＥＡ６４．９質量部、調製例１のアルカリ可溶性樹脂Ａ溶液（固形分４０質量％）１３．５質量部、合成例１のブロック共重合体１のＰＧＭＥＡ溶液（固形分３５質量％）９．２質量部を入れ攪拌した。そこへフェニルホスホン酸（商品名：ＰＰＡ、日産化学社製）０．３９質量部を加え、室温で３０分攪拌した。
　そこへ、青色顔料としてＣ．Ｉ．ピグメントブルー１５：４（Ｂ１５：４）を１２．０質量部、粒径２．０ｍｍジルコニアビーズ１００質量部を入れ、予備解砕としてペイントシェーカー（浅田鉄工社製）で１時間振とうし、次いで粒径０．１ｍｍのジルコニアビーズ２００部に変更し本解砕としてペイントシェーカーで４時間分散を行い、色材分散液Ｂ（１）を得た。なお、ブロック共重合体１は、フェニルホスホン酸によって塩形成され、塩型ブロック共重合体１となっている。 (Example 1: Production of photosensitive green resin composition G-1)
(1) Production of Colorant Dispersion B (1) In a 225 mL mayonnaise bottle, 64.9 parts by mass of PGMEA, 13.5 parts by mass of the alkali-soluble resin A solution of Preparation Example 1 (solid content: 40% by mass), Synthesis Example 1 9.2 parts by mass of a PGMEA solution (solid content: 35% by mass) of block copolymer 1 was added and stirred. 0.39 parts by mass of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Industries, Ltd.) was added thereto, and the mixture was stirred at room temperature for 30 minutes.
C.I. I. 12.0 parts by mass of Pigment Blue 15:4 (B15:4) and 100 parts by mass of zirconia beads with a particle size of 2.0 mm were added, and the mixture was shaken for 1 hour with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for preliminary crushing, and then 200 parts of zirconia beads having a particle diameter of 0.1 mm were used, and dispersion was carried out for 4 hours using a paint shaker as main pulverization to obtain a coloring material dispersion liquid B(1). The block copolymer 1 is salt-formed with phenylphosphonic acid to form a salt-type block copolymer 1 .
（２）色材分散液Ｙ（１）の製造
　色材分散液Ｂ（１）の製造において、Ｃ．Ｉ．ピグメントブルー１５：４（Ｂ１５：４）を、Ｃ．Ｉ．ピグメントイエロー１３９（Ｙ１３９）に変更した以外は色材分散液Ｂ（１）の製造と同様にして、色材分散液Ｙ（１）を得た。 (2) Production of colorant dispersion liquid Y(1) In the production of colorant dispersion liquid B(1), C.I. I. Pigment Blue 15:4 (B15:4) was added to C.I. I. Pigment Yellow 139 (Y139) was used to obtain a colorant dispersion liquid Y(1) in the same manner as the colorant dispersion liquid B(1).
（３）色材分散液Ｙ（２）の製造
　色材分散液Ｂ（１）の製造において、Ｃ．Ｉ．ピグメントブルー１５：４（Ｂ１５：４）を、Ｃ．Ｉ．ピグメントイエロー１５０（Ｙ１５０）に変更した以外は色材分散液Ｂ（１）の製造と同様にして、色材分散液Ｙ（２）を得た。 (3) Production of colorant dispersion liquid Y(2) In the production of colorant dispersion liquid B(1), C.I. I. Pigment Blue 15:4 (B15:4) was added to C.I. I. Pigment Yellow 150 (Y150) was used to obtain a colorant dispersion liquid Y(2) in the same manner as the colorant dispersion liquid B(1).
（４）色材分散液Ｙ（３）の製造
　色材分散液Ｂ（１）の製造において、Ｃ．Ｉ．ピグメントブルー１５：４（Ｂ１５：４）を、Ｃ．Ｉ．ピグメントイエロー１３８（Ｙ１３８）に変更した以外は色材分散液Ｂ（１）の製造と同様にして、色材分散液Ｙ（３）を得た。 (4) Production of colorant dispersion liquid Y(3) In the production of colorant dispersion liquid B(1), C.I. I. Pigment Blue 15:4 (B15:4) was added to C.I. I. A colorant dispersion Y(3) was obtained in the same manner as the colorant dispersion B(1), except that Pigment Yellow 138 (Y138) was used.
（５）感光性緑色樹脂組成物Ｇ－１の製造
　上記で得られた色材分散液Ｂ（１）を６．４質量部、色材分散液Ｙ（１）を５．２質量部、色材分散液Ｙ（２）を９．０質量部、色材分散液Ｙ（３）を１５．０質量部、調製例１で得られたアルカリ可溶性樹脂Ａ溶液を３．５質量部、多官能モノマー（商品名アロニックスＭ－３０５、東亞合成（株）社製）を５．６質量部、前記式（Ａ－２）で表されるオキシムエステル系光開始剤を０．５質量部、フッ素系界面活性剤（商品名メガファックＲ－０８ＭＨ、ＤＩＣ（株）製）を０．０３質量部、ＰＧＭＥＡを５４．６質量部加え、感光性緑色樹脂組成物Ｇ－１を得た。 (5) Production of photosensitive green resin composition G-1 6.4 parts by mass of the colorant dispersion B (1) obtained above, 5.2 parts by mass of the colorant dispersion Y (1), color 9.0 parts by mass of material dispersion Y (2), 15.0 parts by mass of colorant dispersion Y (3), 3.5 parts by mass of alkali-soluble resin A solution obtained in Preparation Example 1, polyfunctional 5.6 parts by mass of a monomer (trade name Aronix M-305, manufactured by Toagosei Co., Ltd.), 0.5 parts by mass of the oxime ester photoinitiator represented by the formula (A-2), fluorine-based 0.03 parts by mass of a surfactant (trade name Megafac R-08MH, manufactured by DIC Corporation) and 54.6 parts by mass of PGMEA were added to obtain a photosensitive green resin composition G-1.
（実施例２～１４：感光性緑色樹脂組成物Ｇ－２～Ｇ－１４の製造）
　実施例１において、表１に示したように、青色顔料と黄色顔料と緑色顔料の種類及び／又は質量比を変更し、アルカリ可溶性樹脂Ａ溶液、多官能モノマー、及び前記式（Ａ－２）で表されるオキシムエステル系光開始剤の比率は実施例１と同じまま、色材濃度が表１に示した値になるように変更した以外は、感光性緑色樹脂組成物Ｇ－１と同様にして、感光性緑色樹脂組成物Ｇ－２～Ｇ－１４を得た。
　なお、Ｃ．Ｉ．ピグメントブルー１５：６（Ｂ１５：６）、Ｃ．Ｉ．ピグメントブルー１５：３（Ｂ１５：３）、Ｃ．Ｉ．ピグメントグリーン５９（Ｇ５９）又はＣ．Ｉ．ピグメントグリーン７（Ｇ７）の色材分散液はそれぞれ、色材分散液Ｂ（１）の製造において、Ｃ．Ｉ．ピグメントブルー１５：４（Ｂ１５：４）を、Ｃ．Ｉ．ピグメントブルー１５：６（Ｂ１５：６）、Ｃ．Ｉ．ピグメントブルー１５：３（Ｂ１５：３）、Ｃ．Ｉ．ピグメントグリーン５９（Ｇ５９）又はＣ．Ｉ．ピグメントグリーン７（Ｇ７）に変更した以外は色材分散液Ｂ（１）の製造と同様にして、色材分散液Ｂ（２）、色材分散液Ｂ（３）、色材分散液Ｇ（１）、又は色材分散液Ｇ（２）として得た。 (Examples 2 to 14: Production of photosensitive green resin compositions G-2 to G-14)
In Example 1, as shown in Table 1, by changing the type and / or mass ratio of the blue pigment, the yellow pigment and the green pigment, the alkali-soluble resin A solution, the polyfunctional monomer, and the formula (A-2) The same as the photosensitive green resin composition G-1 except that the ratio of the oxime ester photoinitiator represented by is the same as in Example 1 and the colorant concentration is changed to the value shown in Table 1. Then, photosensitive green resin compositions G-2 to G-14 were obtained.
In addition, C.I. I. Pigment Blue 15:6 (B15:6), C.I. I. Pigment Blue 15:3 (B15:3), C.I. I. Pigment Green 59 (G59) or C.I. I. Pigment Green 7 (G7) colorant dispersion, respectively, in the production of colorant dispersion B(1), C.I. I. Pigment Blue 15:4 (B15:4) was added to C.I. I. Pigment Blue 15:6 (B15:6), C.I. I. Pigment Blue 15:3 (B15:3), C.I. I. Pigment Green 59 (G59) or C.I. I. Colorant dispersion B(2), colorant dispersion B(3), colorant dispersion G( 1), or obtained as colorant dispersion liquid G(2).
（比較例１～４：比較感光性緑色樹脂組成物ＣＧ－１～ＣＧ－４の製造）
　実施例６、７、１３、及び１４において、それぞれ表１に示したように、緑色顔料（ハロゲン化フタロシアニン顔料）を色材全量中に１０質量％を超える量で用いるように顔料割合を変更した以外は、感光性緑色樹脂組成物Ｇ－６、Ｇ－７、Ｇ－１３又はＧ－１４と同様にして、比較感光性緑色樹脂組成物ＣＧ－１～ＣＧ－４を得た。 (Comparative Examples 1 to 4: Production of Comparative Photosensitive Green Resin Compositions CG-1 to CG-4)
In Examples 6, 7, 13, and 14, as shown in Table 1, the green pigment (halogenated phthalocyanine pigment) was used in an amount exceeding 10% by mass in the total amount of the coloring material, so that the pigment ratio was changed. Comparative photosensitive green resin compositions CG-1 to CG-4 were obtained in the same manner as the photosensitive green resin compositions G-6, G-7, G-13 or G-14 except for the above.
（比較例５～６：比較感光性緑色樹脂組成物ＣＧ－５～ＣＧ－６の製造）
　実施例１において、表１に示したように、特許文献２（特開２０１１－２４２５６８号公報）の実施例１及び２と同様になるように、青色顔料と黄色顔料の種類及び／又は質量比と、開始剤の種類（イルガキュア９０７（９０７、ＢＡＳＦ製）及びカヤキュアＤＥＴＸ－Ｓ（ＤＥＴＸ、日本化薬製）を質量比２：１）を変更し、顔料以外の成分量を表１に示した色材濃度になるよう変更した以外は、感光性緑色樹脂組成物Ｇ－１と同様にして、比較感光性緑色樹脂組成物ＣＧ－５～ＣＧ－６を得た。
　なお、Ｃ．Ｉ．ピグメントブルー１６（Ｂ１６）の色材分散液は、色材分散液Ｂ（１）の製造において、Ｃ．Ｉ．ピグメントブルー１５：４（Ｂ１５：４）を、Ｃ．Ｉ．ピグメントブルー１６（Ｂ１６）に変更した以外は色材分散液Ｂ（１）の製造と同様にして、色材分散液Ｂ（４）として得た。 (Comparative Examples 5-6: Production of comparative photosensitive green resin compositions CG-5-CG-6)
In Example 1, as shown in Table 1, in the same manner as in Examples 1 and 2 of Patent Document 2 (JP 2011-242568 A), the type and / or mass ratio of the blue pigment and the yellow pigment And, by changing the type of initiator (Irgacure 907 (907, manufactured by BASF) and Kayacure DETX-S (DETX, manufactured by Nippon Kayaku) at a mass ratio of 2: 1), the amounts of components other than pigments are shown in Table 1. Comparative photosensitive green resin compositions CG-5 to CG-6 were obtained in the same manner as the photosensitive green resin composition G-1, except that the colorant concentration was changed.
In addition, C.I. I. Pigment Blue 16 (B16) colorant dispersion was prepared by C.I. I. Pigment Blue 15:4 (B15:4) was added to C.I. I. A colorant dispersion B(4) was obtained in the same manner as the colorant dispersion B(1), except that Pigment Blue 16 (B16) was used.
（比較例７～１０：比較感光性緑色樹脂組成物ＣＧ－７～ＣＧ－１０の製造）
　実施例１において、表１に示したように、特許文献３（国際公開２０２０／１９６３９３号公報）の実施例２、５、７及び１０と同様になるように、青色顔料と黄色顔料の種類及び／又は質量比と、開始剤の種類（イルガキュアＯＸＥ０２（ＯＸＥ０２、ＢＡＳＦ社製）を変更し、顔料以外の成分量を表１に示した色材濃度になるよう変更した以外は、感光性緑色樹脂組成物Ｇ－１と同様にして、比較感光性緑色樹脂組成ＣＧ－７～ＣＧ－１０を得た。 (Comparative Examples 7 to 10: Production of comparative photosensitive green resin compositions CG-7 to CG-10)
In Example 1, as shown in Table 1, the types of blue pigment and yellow pigment and / Or the mass ratio and the type of initiator (Irgacure OXE02 (OXE02, manufactured by BASF) were changed, and the amount of components other than the pigment was changed to the color material concentration shown in Table 1. Photosensitive green resin Comparative photosensitive green resin compositions CG-7 to CG-10 were obtained in the same manner as composition G-1.
［評価方法］
　各実施例及び各比較例で得られた感光性緑色樹脂組成物を、ガラス基板（ＮＨテクノグラス（株）社製、「ＮＡ３５」）上にそれぞれ、スピンコーターを用いて、最終的に得られる硬化膜が厚さ３．０μｍとなるように塗布した後、ホットプレートを用いて８０℃で３分間乾燥し基板上に塗膜を形成した。この塗膜に、独立細線を形成するための開口寸法２μｍから１００μｍのパターンを有するフォトマスク（クロムマスク）を介して、超高圧水銀灯を用いて５０ｍＪ／ｃｍ２の紫外線で露光することにより、露光後塗膜を形成した。次いで、０．０５ｗｔ％水酸化カリウム水溶液を現像液としてスピン現像し、現像液に６０秒間接液させた後に純水で洗浄することで現像処理し、独立細線パターン状の塗膜を得た。その後、９０℃のクリーンオーブンで３０分間ポストベイクすることにより、独立細線パターン状の硬化膜を形成した。得られた硬化膜について、透過率と、断面形状と、耐溶剤性の評価を行った。 [Evaluation method]
The photosensitive green resin composition obtained in each example and each comparative example is finally obtained on a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") using a spin coater. After coating so that the cured film had a thickness of 3.0 μm, it was dried at 80° C. for 3 minutes using a hot plate to form a coating film on the substrate. This coating film is exposed to ultraviolet rays of 50 mJ/cm 2 using an ultra-high pressure mercury lamp through a photomask (chromium mask) having a pattern with an opening size of 2 μm to 100 μm for forming independent fine lines. A postcoat was formed. Next, spin development was performed using a 0.05 wt % potassium hydroxide aqueous solution as a developer, and the film was developed by immersing it in the developer for 60 seconds and then washing with pure water to obtain a coating film having an independent fine line pattern. Thereafter, post-baking was performed in a clean oven at 90° C. for 30 minutes to form a cured film having an independent fine line pattern. The obtained cured film was evaluated for transmittance, cross-sectional shape, and solvent resistance.
＜透過率＞
　顕微分光測定装置（オリンパス製、ＯＳＰ－ＳＰ２００）を用いて硬化膜の３８０ｎｍ～７８０ｎｍの透過スペクトルを測定し、３６０ｎｍ～３７０ｎｍの最小透過率とその波長、３８０ｎｍ～４８０ｎｍの最大透過率、５１０ｎｍ～５５０ｎｍの最大透過率と最小透過率、５８０ｎｍ～７００ｎｍの最大透過率、及び３８０ｎｍ～７００ｎｍの範囲の波長において最大透過率を示すピークにおいて最大透過率の半分の透過率となる２点の波長の差を計算して半値幅を求めた。 <Transmittance>
The transmission spectrum of 380 nm to 780 nm of the cured film is measured using a microscopic spectrometer (OSP-SP200, manufactured by Olympus), and the minimum transmittance of 360 nm to 370 nm and its wavelength, the maximum transmittance of 380 nm to 480 nm, and the maximum transmittance of 510 nm to 550 nm. The maximum transmittance and minimum transmittance of , the maximum transmittance of 580 nm to 700 nm, and the difference between two wavelengths at which the peak showing the maximum transmittance in the wavelength range of 380 nm to 700 nm has half the maximum transmittance Calculation was performed to obtain the half width.
＜細線パターン状の着色層の断面形状評価＞
　得られた独立細線パターン状の着色層の厚み方向断面形状を、走査型電子顕微鏡（（株）島津製作所製、ｓｕｐｅｒ　ｓｃａｎ　ｍｏｄｅｌ　２２０、倍率１００００倍）により観察し、下記評価基準により、着色層の断面形状のテーパー角（θ１）（図５参照）について評価した。
（パターン状着色層の断面形状の評価基準）
Ａ：テーパー角（θ１）が１５度以上１００度未満
Ｂ：テーパー角（θ１）が１００度以上１１０度未満
Ｃ：テーパー角（θ１）が１１０度以上１２０度未満
Ｄ：テーパー角（θ１）が１２０度以上
　評価結果がＢであれば着色層の断面形状は良好であり、評価結果がＡであれば着色層の断面形状に優れている。 <Cross-sectional shape evaluation of fine line pattern colored layer>
The cross-sectional shape in the thickness direction of the resulting colored layer in the form of an independent fine line pattern was observed with a scanning electron microscope (manufactured by Shimadzu Corporation, super scan model 220, magnification of 10,000 times). The taper angle (θ1) of the cross-sectional shape (see FIG. 5) was evaluated.
(Evaluation criteria for cross-sectional shape of patterned colored layer)
A: The taper angle (θ1) is 15 degrees or more and less than 100 degrees B: The taper angle (θ1) is 100 degrees or more and less than 110 degrees C: The taper angle (θ1) is 110 degrees or more and less than 120 degrees D: The taper angle (θ1) is 120 degrees or more If the evaluation result is B, the cross-sectional shape of the colored layer is good, and if the evaluation result is A, the cross-sectional shape of the colored layer is excellent.
＜耐溶剤性（耐ＰＧＭＥ）評価＞
　得られた着色層の膜厚を測定した後、プロピレングリコールモノメチルエーテル（ＰＧＭＥ）に１０分間浸漬した後、風乾し、再び膜厚を測定した。なお、膜厚測定には、触針式段差膜厚計「Ｐ－１５Ｔｅｎｃｏｒ」（Ｉｎｓｔｒｕｍｅｎｔｓ製）を用いた。溶剤浸漬後膜厚／溶剤浸漬前膜厚を×１００を、残膜率として算出した。
（耐溶剤性評価基準）
Ａ：溶剤浸漬後の残膜率が９８％以上
Ｂ：溶剤浸漬後の残膜率が９６％以上９８％未満
Ｃ：溶剤浸漬後の残膜率が９４％以上９６％未満
Ｄ：溶剤浸漬後の残膜率が９４％未満
　評価結果がＢであれば耐溶剤性は良好であり、評価結果がＡであれば耐溶剤性に優れている。 <Solvent resistance (PGME resistance) evaluation>
After measuring the film thickness of the obtained colored layer, it was immersed in propylene glycol monomethyl ether (PGME) for 10 minutes, air-dried, and the film thickness was measured again. For the film thickness measurement, a stylus type step film thickness meter "P-15 Tencor" (manufactured by Instruments) was used. Film thickness after solvent immersion/film thickness before solvent immersion×100 was calculated as the residual film ratio.
(Solvent resistance evaluation criteria)
A: Remaining film rate after solvent immersion is 98% or more B: Remaining film rate after solvent immersion is 96% or more and less than 98% C: Remaining film rate after solvent immersion is 94% or more and less than 96% D: After solvent immersion is less than 94%. If the evaluation result is B, the solvent resistance is good, and if the evaluation result is A, the solvent resistance is excellent.
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
［結果のまとめ］
　緑色顔料（ハロゲン化フタロシアニン顔料）を色材全量中に１０質量％を超える量で用いるように変更した比較例１～４においては、膜厚３．０μｍで硬化膜を形成した時に、３６０ｎｍ～３７０ｎｍのスペクトル透過率が０．７％未満であり、低温加熱処理を行った硬化膜の耐溶剤性及びパターン形状が劣っていた。
　特許文献２（特開２０１１－２４２５６８号公報）の実施例１及び２と同様の青色顔料と黄色顔料の種類及び／又は質量比とした比較例５及び６はそれぞれ、膜厚３．０μｍで硬化膜を形成した時に、３６０ｎｍ～３７０ｎｍのスペクトル透過率が０．７％以上であったものの、低温加熱処理を行った硬化膜の耐溶剤性及びパターン形状が劣ることが示された。
　また、特許文献３（国際公開２０２０／１９６３９３号公報）の実施例２、５、７及び１０と同様の青色顔料と黄色顔料の種類及び／又は質量比とした比較例７～１０もそれぞれ、膜厚３．０μｍで硬化膜を形成した時に、３６０ｎｍ～３７０ｎｍのスペクトル透過率が０．７％以上であったものの、色材濃度が高くなり、低温加熱処理を行った硬化膜の耐溶剤性及びパターン形状が劣ることが示された。
　それに対して、本発明に係る感光性緑色樹脂組成物である実施例１～１４では、膜厚３．０μｍで硬化膜を形成した時に、３６０ｎｍ～３７０ｎｍのスペクトル透過率が０．７％以上となり、且つ、色材濃度も低く、有機発光素子上に形成する際に好ましい低温（９０℃）でポストベイクを行って硬化膜が形成されても、耐溶剤性が良好で、且つパターン形状が良好な着色層を形成可能であることが示された。 [Summary of results]
In Comparative Examples 1 to 4 in which the green pigment (halogenated phthalocyanine pigment) was changed to be used in an amount exceeding 10% by mass in the total amount of the coloring material, when a cured film was formed with a film thickness of 3.0 μm, it was 360 nm to 370 nm. was less than 0.7%, and the solvent resistance and pattern shape of the cured film subjected to the low-temperature heat treatment were inferior.
Comparative Examples 5 and 6, which were the same blue pigment and yellow pigment types and / or mass ratios as in Examples 1 and 2 of Patent Document 2 (JP 2011-242568), respectively, cured at a film thickness of 3.0 μm. When the film was formed, the spectral transmittance at 360 nm to 370 nm was 0.7% or more, but it was shown that the solvent resistance and pattern shape of the cured film subjected to low-temperature heat treatment were inferior.
In addition, Comparative Examples 7 to 10 in which the same blue pigment and yellow pigment types and / or mass ratios as in Examples 2, 5, 7 and 10 of Patent Document 3 (International Publication No. 2020/196393) are used, respectively, When a cured film was formed with a thickness of 3.0 μm, the spectral transmittance of 360 nm to 370 nm was 0.7% or more, but the concentration of the coloring material increased, and the solvent resistance and solvent resistance of the cured film subjected to low-temperature heat treatment. Poor pattern shape was shown.
On the other hand, in Examples 1 to 14, which are the photosensitive green resin compositions according to the present invention, when a cured film is formed with a film thickness of 3.0 μm, the spectral transmittance at 360 nm to 370 nm is 0.7% or more. And, the colorant concentration is also low, and even if a cured film is formed by performing post-baking at a low temperature (90 ° C.) that is preferable when forming on an organic light emitting device, solvent resistance is good and the pattern shape is good. It was shown that a colored layer can be formed.
　１　基板
　２　遮光部
　３　着色層（着色硬化膜）
　１０　カラーフィルタ
　２０　対向基板
　３０　液晶層
　４０　液晶表示装置
　５０　基板
　７１　透明陽極
　７２　正孔注入層
　７３　正孔輸送層
　７４　発光層
　７５　電子注入層
　７６　陰極
　８０　有機発光素子
　９０　封止層
１００　有機発光表示装置
　１０１　基板
　１０２　薄膜トランジスタ（ＴＦＴ）
　１０３　封止膜
　１０４　電極
　１０５　隔壁
　１０６Ｒ、１０６Ｇ、１０６Ｂ　有機発光素子
　１０７　電極
　１０８　封止層
　１０９Ｒ、１０９Ｇ、１０９Ｂ　着色硬化膜
　１１０　遮光部
　１１１　封止膜
　１１２　透明粘着剤層
　１１３　カバー材
　１２０　外光反射防止膜
　１３０　有機発光素子を備えた素子基板
　２００　表示装置 REFERENCE SIGNS LIST 1 substrate 2 light shielding part 3 colored layer (colored cured film)
REFERENCE SIGNS LIST 10 color filter 20 counter substrate 30 liquid crystal layer 40 liquid crystal display device 50 substrate 71 transparent anode 72 hole injection layer 73 hole transport layer 74 light emitting layer 75 electron injection layer 76 cathode 80 organic light emitting element 90 sealing layer 100 organic light emitting display device 101 substrate 102 thin film transistor (TFT)
103 sealing film 104 electrode 105 partition wall 106R, 106G, 106B organic light-emitting element 107 electrode 108 sealing layer 109R, 109G, 109B colored cured film 110 light shielding part 111 sealing film 112 transparent adhesive layer 113 cover material 120 external light reflection prevention Film 130 Device substrate provided with organic light emitting device 200 Display device

Claims (11)

  1. 　色材と、アルカリ可溶性樹脂と、光重合性化合物と、光開始剤とを含有し、
    　前記色材が、青色顔料と黄色顔料を含み、当該黄色顔料がＣ．Ｉ．ピグメントイエロー１３９を含み、ハロゲン化金属フタロシアニン顔料が１０％以下であり、
    　膜厚３．０μｍで硬化膜を形成した時に、３６０ｎｍ～３７０ｎｍのスペクトル透過率が０．７％以上である、感光性緑色樹脂組成物。     Containing a coloring material, an alkali-soluble resin, a photopolymerizable compound, and a photoinitiator,
    The coloring material includes a blue pigment and a yellow pigment, and the yellow pigment is C.I. I. Pigment Yellow 139 with a halogenated metal phthalocyanine pigment of 10% or less,
    A photosensitive green resin composition having a spectral transmittance of 0.7% or more at 360 nm to 370 nm when a cured film having a thickness of 3.0 μm is formed.
  2. 　前記青色顔料が、Ｃ．Ｉ．ピグメントブルー１５：３、Ｃ．Ｉ．ピグメントブルー１５：４、及びＣ．Ｉ．ピグメントブルー１６からなる群から選択される少なくとも１種を含み、黄色顔料が、更にＣ．Ｉ．ピグメントイエロー１３８、Ｃ．Ｉ．ピグメントイエロー１５０、及びＣ．Ｉ．ピグメントイエロー１８５からなる群から選択される少なくとも１種を含んでもよい、請求項１に記載の感光性緑色樹脂組成物。 The blue pigment is C.I. I. Pigment Blue 15:3, C.I. I. Pigment Blue 15:4, and C.I. I. Pigment Blue 16, wherein the yellow pigment further contains C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 150, and C.I. I. Pigment Yellow 185. The photosensitive green resin composition according to claim 1, which may contain at least one selected from the group consisting of Pigment Yellow 185.
  3. 　前記光開始剤が、下記一般式（Ａ）で表される化合物の少なくとも１種を含む、請求項１又は２に記載の感光性緑色樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ１及びＲ２は、それぞれ独立に、Ｒ１１、ＯＲ１１、ＣＯＲ１１、ＳＲ１１、ＣＯＮＲ１２Ｒ１３又はＣＮを表し、
    　Ｒ１１、Ｒ１２及びＲ１３は、それぞれ独立に、水素原子、炭素数１～２０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアリールアルキル基又は炭素数２～２０の複素環基を表し、
    　Ｒ１１、Ｒ１２及びＲ１３で表される基の水素原子は、更にＲ２１、ＯＲ２１、ＣＯＲ２１、ＳＲ２１、ＮＲ２２Ｒ２３、ＣＯＮＲ２２Ｒ２３、－ＮＲ２２－ＯＲ２３、－ＮＣＯＲ２２－ＯＣＯＲ２３、ＮＲ２２ＣＯＲ２１、ＯＣＯＲ２１、ＣＯＯＲ２１、ＳＣＯＲ２１、ＯＣＳＲ２１、ＣＯＳＲ２１、ＣＳＯＲ２１、水酸基、ニトロ基、ＣＮ、又はハロゲン原子で置換されていてもよく、
    　Ｒ２１、Ｒ２２及びＲ２３は、それぞれ独立に、水素原子、炭素数１～２０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアリールアルキル基又は炭素数２～２０の複素環基を表し、
    　Ｒ２１、Ｒ２２及びＲ２３で表される基の水素原子は、更に水酸基、ニトロ基、ＣＮ、ハロゲン原子、又はカルボキシ基で置換されていてもよく、
    　Ｒ１１、Ｒ１２、Ｒ１３、Ｒ２１、Ｒ２２及びＲ２３で表される基のアルキレン部分は、－Ｏ－、－Ｓ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＲ２４－、－ＮＲ２４ＣＯ－、－ＮＲ２４ＣＯＯ－、－ＯＣＯＮＲ２４－、－ＳＣＯ－、－ＣＯＳ－、－ＯＣＳ－又は－ＣＳＯ－を酸素原子が隣り合わない条件で１～５個含んでいてもよく、
    　Ｒ２４は、水素原子、炭素数１～２０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアリールアルキル基又は炭素数２～２０の複素環基を表し、
    　Ｒ１１、Ｒ１２、Ｒ１３、Ｒ２１、Ｒ２２、Ｒ２３及びＲ２４で表される基のアルキル部分は、分岐側鎖があってもよく、環状アルキルであってもよく、
    　Ｒ３は、水素原子、炭素数１～２０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアリールアルキル基又は炭素数２～２０の複素環基を表し、Ｒ３で表される基のアルキル部分は、分岐側鎖があってもよく、環状アルキルであってもよく、また、Ｒ３とＲ７、及びＲ３とＲ８はそれぞれ一緒になって環を形成していてもよく、
    　Ｒ３で表される基の水素原子は、更にＲ２１、ＯＲ２１、ＣＯＲ２１、ＳＲ２１、ＮＲ２２Ｒ２３、ＣＯＮＲ２２Ｒ２３、－ＮＲ２２－ＯＲ２３、－ＮＣＯＲ２２－ＯＣＯＲ２３、ＮＲ２２ＣＯＲ２１、ＯＣＯＲ２１、ＣＯＯＲ２１、ＳＣＯＲ２１、ＯＣＳＲ２１、ＣＯＳＲ２１、ＣＳＯＲ２１、水酸基、ニトロ基、ＣＮ、又はハロゲン原子で置換されていてもよく、
    　Ｒ４、Ｒ５、Ｒ６及びＲ７は、それぞれ独立に、Ｒ１１、ＯＲ１１、ＳＲ１１、ＣＯＲ１４、ＣＯＮＲ１５Ｒ１６、ＮＲ１２ＣＯＲ１１、ＯＣＯＲ１１、ＣＯＯＲ１４、ＳＣＯＲ１１、ＯＣＳＲ１１、ＣＯＳＲ１４、ＣＳＯＲ１１、水酸基、ＣＮ又はハロゲン原子を表し、Ｒ４とＲ５、Ｒ５とＲ６、及びＲ６とＲ７はそれぞれ一緒になって環を形成していてもよく、
    　Ｒ１４、Ｒ１５及びＲ１６は、水素原子又は炭素数１～２０のアルキル基を表し、Ｒ１４、Ｒ１５及びＲ１６で表される基のアルキル部分は、分岐側鎖があってもよく、環状アルキルであってもよく、Ｒ８は、Ｒ１１、ＯＲ１１、ＳＲ１１、ＣＯＲ１１、ＣＯＮＲ１２Ｒ１３、ＮＲ１２ＣＯＲ１１、ＯＣＯＲ１１、ＣＯＯＲ１１、ＳＣＯＲ１１、ＯＣＳＲ１１、ＣＯＳＲ１１、ＣＳＯＲ１１、水酸基、ＣＮ又はハロゲン原子を表し、
    　ｋは、０又は１を表す。）     The photosensitive green resin composition according to claim 1 or 2, wherein the photoinitiator contains at least one compound represented by the following general formula (A).
    Figure JPOXMLDOC01-appb-C000001
     (wherein R 1 and R 2 each independently represent R 11 , OR 11 , COR 11 , SR 11 , CONR 12 R 13 or CN;
    R 11 , R 12 and R 13 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms or 2 to 20 carbon atoms. represents a heterocyclic group of
    The hydrogen atoms of the groups represented by R 11 , R 12 and R 13 are further represented by R 21 , OR 21 , COR 21 , SR 21 , NR 22 R 23 , CONR 22 R 23 , —NR 22 —OR 23 , —NCOR 22 —OCOR 23 , NR 22 COR 21 , OCOR 21 , COOR 21 , SCOR 21 , OCSR 21 , COSR 21 , CSOR 21 , optionally substituted with a hydroxyl group, a nitro group, CN, or a halogen atom,
    R 21 , R 22 and R 23 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms or 2 to 20 carbon atoms. represents a heterocyclic group of
    hydrogen atoms in the groups represented by R 21 , R 22 and R 23 may be further substituted with a hydroxyl group, a nitro group, CN, a halogen atom, or a carboxy group;
    The alkylene portions of the groups represented by R 11 , R 12 , R 13 , R 21 , R 22 and R 23 are -O-, -S-, -COO-, -OCO-, -NR 24 -, -NR 24 CO-, -NR 24 COO-, -OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO- may contain 1 to 5 oxygen atoms not adjacent to each other,
    R 24 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms;
    The alkyl portion of the groups represented by R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 may have a branched side chain or may be a cyclic alkyl,
    R 3 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms; The alkyl portion of the represented groups may have branched side chains or may be cyclic alkyl, and R 3 and R 7 and R 3 and R 8 each together form a ring. may be
    The hydrogen atoms of the group represented by R 3 may further be R 21 , OR 21 , COR 21 , SR 21 , NR 22 R 23 , CONR 22 R 23 , —NR 22 —OR 23 , —NCOR 22 —OCOR 23 , NR 22 COR 21 , OCOR 21 , COOR 21 , SCOR 21 , OCSR 21 , COSR 21 , CSOR 21 , a hydroxyl group, a nitro group, CN, or optionally substituted with a halogen atom,
    R 4 , R 5 , R 6 and R 7 are each independently R 11 , OR 11 , SR 11 , COR 14 , CONR 15 R 16 , NR 12 COR 11 , OCOR 11 , COOR 14 , SCOR 11 , OCSR 11 , COSR 14 , CSOR 11 , a hydroxyl group, CN or a halogen atom, R 4 and R 5 , R 5 and R 6 , and R 6 and R 7 may together form a ring,
    R 14 , R 15 and R 16 represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl portion of the groups represented by R 14 , R 15 and R 16 may have a branched side chain. , which may be cyclic alkyl, and R 8 is R 11 , OR 11 , SR 11 , COR 11 , CONR 12 R 13 , NR 12 COR 11 , OCOR 11 , COOR 11 , SCOR 11 , OCSR 11 , COSR 11 , CSOR 11 represents a hydroxyl group, CN or a halogen atom,
    k represents 0 or 1; )
  4. 　膜厚３．０μｍで硬化膜を形成した時に、透過スペクトルの３８０ｎｍ～７００ｎｍの範囲の波長において最大透過率を示す波長が５２５ｎｍ～５４５ｎｍの範囲内にある、請求項１～３のいずれか１項に記載の感光性緑色樹脂組成物。 4. Any one of claims 1 to 3, wherein when a cured film having a thickness of 3.0 μm is formed, the wavelength at which the maximum transmittance is exhibited in the wavelength range of 380 nm to 700 nm in the transmission spectrum is in the range of 525 nm to 545 nm. The photosensitive green resin composition according to .
  5. 　有機発光素子上に形成する硬化膜に用いる、請求項１～４のいずれか１項に記載の感光性緑色樹脂組成物。 The photosensitive green resin composition according to any one of claims 1 to 4, which is used for a cured film formed on an organic light emitting device.
  6. 　請求項１～４のいずれか１項に記載の感光性緑色樹脂組成物の硬化物。 A cured product of the photosensitive green resin composition according to any one of claims 1 to 4.
  7. 　基板と、当該基板上に設けられた着色層とを少なくとも備えるカラーフィルタであって、当該着色層の少なくとも１つが請求項６に記載の感光性緑色樹脂組成物の硬化物である、カラーフィルタ。 A color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a cured product of the photosensitive green resin composition according to claim 6.
  8. 　前記請求項７に記載のカラーフィルタを有する、表示装置。 A display device having the color filter according to claim 7.
  9. 　有機発光素子上に、請求項１～４のいずれか１項に記載の感光性緑色樹脂組成物の硬化膜を有する、表示装置。 A display device comprising a cured film of the photosensitive green resin composition according to any one of claims 1 to 4 on an organic light-emitting element.
  10. 　有機発光素子上に、請求項１～４のいずれか１項に記載の感光性緑色樹脂組成物を塗布することにより塗膜を形成する工程、
    前記塗膜に光照射する工程、
    前記光照射後の膜を、加熱するポストベイク工程、及び、
    前記光照射後の膜を、現像する工程を含有することにより、
    有機発光素子上に請求項１～４のいずれか１項に記載の感光性緑色樹脂組成物の硬化膜を形成する工程を有する、有機発光素子と外光反射防止膜の積層体の製造方法。     A step of forming a coating film by applying the photosensitive green resin composition according to any one of claims 1 to 4 on the organic light emitting device;
    a step of irradiating the coating film with light;
    A post-baking step of heating the film after the light irradiation, and
    By including the step of developing the film after the light irradiation,
    A method for producing a laminate of an organic light emitting device and an external light antireflection film, comprising the step of forming a cured film of the photosensitive green resin composition according to any one of claims 1 to 4 on the organic light emitting device.
  11. 　前記ポストベイク工程における加熱温度が、１３０℃以下である、請求項１０に記載の有機発光素子と外光反射防止膜の積層体の製造方法。 11. The method for producing a laminate of an organic light-emitting element and an external light antireflection film according to claim 10, wherein the heating temperature in the post-baking step is 130° C. or less.
PCT/JP2022/005835 2021-02-19 2022-02-15 Photosensitve green resin composition, cured product, color filter, display device, and method for producing laminate of organic light-emitting element and external light antireflection film WO2022176831A1 (en)

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JP2023500841A JPWO2022176831A1 (en) 2021-02-19 2022-02-15
CN202280013059.7A CN116806327A (en) 2021-02-19 2022-02-15 Photosensitive green resin composition, cured product, color filter, display device, and method for producing laminate of organic light-emitting element and anti-external light reflection film

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