WO2022176831A1 - 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 - Google Patents

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 Download PDF

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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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English (en)
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 JP2023500841A priority Critical patent/JPWO2022176831A1/ja
Priority to CN202280013059.7A priority patent/CN116806327A/zh
Priority to KR1020237030228A priority patent/KR20230146556A/ko
Publication of WO2022176831A1 publication Critical patent/WO2022176831A1/ja

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8791—Arrangements for improving contrast, e.g. preventing reflection of ambient light
    • 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
    • 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
    • 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.

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PCT/JP2022/005835 2021-02-19 2022-02-15 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 WO2022176831A1 (ja)

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