WO2022270358A1 - 感光性着色樹脂組成物、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
感光性着色樹脂組成物、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 PDFInfo
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- WO2022270358A1 WO2022270358A1 PCT/JP2022/023797 JP2022023797W WO2022270358A1 WO 2022270358 A1 WO2022270358 A1 WO 2022270358A1 JP 2022023797 W JP2022023797 W JP 2022023797W WO 2022270358 A1 WO2022270358 A1 WO 2022270358A1
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
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- 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
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- G—PHYSICS
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
-
- 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
Definitions
- the present invention relates to a photosensitive colored 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 colored 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.
- the cross-sectional shape of the resulting pattern tends to be an undercut shape (also called a reverse tapered shape), that is, a shape in which the top surface of the pattern is the widest and the bottom surface is the narrowest.
- Undercut shapes cause various problems, such as pattern peeling and chipping, gaps at the edges of pixels, and uneven coating when applied to the top in the next process. become
- Patent Document 1 a non-reactive alkali-soluble resin and a photopolymerization initiator (A ), the photopolymerization initiator (A) contains a photopolymerization initiator (a1) containing two oxime groups in one molecule, and the glass transition temperature (Tg) of the non-reactive alkali-soluble resin is , and a temperature of 0° C. or lower.
- the colored photosensitive resin composition of Patent Document 1 contains a resin having a low glass transition temperature, so that post-baking belonging to high heat treatment such as 220 ° C. in the color filter manufacturing process is performed to melt and flow the colored layer. It is a technique that enables formation of a forward tapered pattern after the baking process.
- the present invention has been made in view of the above circumstances, and provides a photosensitive colored resin composition capable of suppressing the generation of development residues even in low-temperature heat treatment and forming a colored layer with a good pattern shape. With the goal.
- the present invention also provides a color filter and a display device formed using the photosensitive colored resin composition, and a laminate of an organic light-emitting element and an external light antireflection film using the photosensitive colored resin composition.
- the object is to provide a manufacturing method.
- the photosensitive colored resin composition according to the present invention contains a coloring material, an alkali-soluble resin, a non-reactive resin, a photopolymerizable compound, a photoinitiator, and a solvent,
- the alkali-soluble resin has an acid value of more than 50 mgKOH/g
- the non-reactive resin has an acid value of 7 mgKOH/g to 50 mgKOH/g, a content of structural units derived from methyl methacrylate in all structural units of 50% to 99% by mass, and a weight average molecular weight of 5000 to 50000.
- the cured product according to the present invention is the cured product of the photosensitive colored 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 colored 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 colored resin composition according to the present invention on the organic light-emitting element.
- a method for manufacturing 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 colored 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 colored resin composition according to the present invention on the organic light-emitting element.
- a photosensitive colored resin composition capable of suppressing the generation of development residues and forming a colored layer with a good pattern shape even when subjected to low-temperature heat treatment.
- a color filter and a display device formed using the photosensitive colored resin composition, and a laminate of an organic light emitting device and an external light antireflection film using the photosensitive colored 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.
- 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 photosensitive colored resin composition, the cured product, the color filter, the display device, and the method for producing the laminate of the organic light-emitting element and the external light antireflection film according to the present invention will be described in detail in order.
- the photosensitive colored resin composition according to the present invention contains a colorant, an alkali-soluble resin, a non-reactive resin, a photopolymerizable compound, a photoinitiator, and a solvent,
- the alkali-soluble resin has an acid value of more than 50 mgKOH/g
- the non-reactive resin has an acid value of 7 mgKOH/g to 50 mgKOH/g, a content of structural units derived from methyl methacrylate in all structural units of 50% to 99% by mass, and a weight average molecular weight of 5000 to 50000.
- the photosensitive colored resin composition according to the present invention contains an alkali-soluble resin having an acid value exceeding 50 mgKOH/g and a non-reactive resin having an acid value of 7 mgKOH/g to 50 mgKOH/g.
- the content of the structural unit derived from methyl methacrylate is 50% by mass to 99% by mass in all the structural units, and the weight average molecular weight is 5000 to 50000, so that generation of development residue is suppressed even in low-temperature heat treatment. , and a colored layer having a good pattern shape can be formed.
- the action of the combination ensures the developability of the unexposed areas.
- the lower portion of the resin composition layer in the exposed area is less likely to flow during development, and undercutting of the cross section after development can be suppressed.
- the specific non-reactive resin used in the present invention is selected so as to have the specific acid value, structural unit and weight average molecular weight. Therefore, when combined with an alkali-soluble resin having a specific acid value or higher, development residue can be suppressed.
- the photosensitive colored resin composition according to the present invention can suppress the generation of development residues even in low-temperature heat treatment, and can form a colored layer with a good pattern shape. It can be suitably used for a cured film. That is, the photosensitive colored 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 colored 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 element, 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.
- a color filter as an alternative to a polarizing plate for suppressing external light reflection It can also be used as
- the photosensitive colored resin composition according to the present invention contains at least a colorant, an alkali-soluble resin, a non-reactive resin, a photopolymerizable compound, a photoinitiator, and a solvent, and the present invention It may contain other components as long as the effects of the above are not impaired.
- a colorant an alkali-soluble resin, a non-reactive resin, a photopolymerizable compound, a photoinitiator, and a solvent
- the present invention It may contain other components as long as the effects of the above are not impaired.
- Each component of the photosensitive colored resin composition according to the present invention will be described in detail below.
- 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 Salt-forming compounds and the like can be used alone or in combination of two or more.
- organic pigments are preferably used because of their high color developability and high heat resistance. Examples of organic pigments include compounds classified as pigments in the Color Index (C.I.; published by The Society of Dyers and Colorists). .) numbered ones can be mentioned.
- the inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, Prussian blue, oxide Chromium green, cobalt green, amber, titanium black, synthetic iron black, carbon black and the like can be mentioned.
- a black pigment having high light-shielding properties is blended in the ink.
- a black pigment with high light shielding properties for example, an inorganic pigment such as carbon black or triiron tetroxide, or an organic pigment such as cyanine black can be used.
- the dispersible dyes include dyes that are made dispersible by adding various substituents to the dye or by using the dye in combination with a solvent having low solubility.
- the salt-forming compound of the dye refers to a compound in which the dye forms a salt with a counterion. Examples thereof include a salt-forming compound of a basic dye and an acid, and a salt-forming compound of an acid dye and a base, which are soluble in solvents. It also includes a lake pigment obtained by insolubilizing the dye in a solvent using a known lake formation (chlorination) technique.
- a coloring material containing at least one selected from dyes and salt-forming compounds of dyes is used in combination with the dispersant of the present invention to improve the dispersibility and dispersion stability of the coloring material. can be done.
- the dye can be appropriately selected from conventionally known dyes.
- examples of such dyes include azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, and phthalocyanine dyes.
- azo dyes metal complex salt azo dyes
- anthraquinone dyes triphenylmethane dyes
- xanthene dyes cyanine dyes
- naphthoquinone dyes naphthoquinone dyes
- quinoneimine dyes methine dyes
- phthalocyanine dyes a guideline
- the coloring material is at least one selected from the group consisting of diketopyrrolopyrrole pigments, quinophthalone pigments, copper phthalocyanine pigments, zinc phthalocyanine pigments, quinophthalone dyes, coumarin dyes, cyanine dyes, and salt-forming compounds of these dyes.
- the effect of suppressing the sublimation or precipitation of the colorant due to the use of the dispersant is high, and it is preferable in that a colored layer with high brightness can be formed.
- the coloring material contains at least one selected from the group consisting of diketopyrrolopyrrole pigments, quinophthalone pigments, copper phthalocyanine pigments, zinc phthalocyanine pigments, and quinophthalone dyes.
- diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, 255, 264, 272, 291, and diketopyrrolopyrrole pigments represented by the following general formula (i), among which C.I. I. Pigment Red 254, 272, 291, and at least one selected from diketopyrrolopyrrole pigments in which R 21 and R 22 in the following general formula (i) are each a 4-bromophenyl group are preferred.
- R 51 and R 52 are each independently a 4-chlorophenyl group or a 4-bromophenyl group.
- Examples of quinophthalone pigments include C.I. I. Pigment Yellow 138 and the like.
- Examples of copper phthalocyanine pigments include C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, C.I. I. Pigment Green 7, 36 and the like, among which C.I. I. Pigment Blue 15:6 is preferred.
- Examples of zinc phthalocyanine pigments include C.I. I. Pigment Green 58, 59 and the like.
- Examples of quinophthalone dyes include C.I. I. Disperse Yellow 54, 64, 67, 134, 149, 160, C.I. I. Solvent Yellow 114, 157 and the like, among which C.I. I. Disperse Yellow 54 is preferred.
- 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 size of the colorant is in the above range, the display device provided with the cured film produced using the photosensitive colored resin composition according to the present invention can suppress reflection of external light and has high contrast. and can be of high quality.
- the average dispersed particle size of the colorant in the photosensitive colored resin composition varies depending on the type of colorant used, but is preferably in the range of 10 nm to 100 nm, and preferably in the range of 15 nm to 60 nm. is more preferred.
- the average dispersed particle size of the colorant in the photosensitive colored 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 colored resin composition is diluted appropriately 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 (eg, 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 colored resin composition according to the present invention is not particularly limited.
- the content of the coloring material from the viewpoint of dispersibility and dispersion stability, relative to the total solid content of the photosensitive colored 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 colored 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 colored 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 acid value of more than 50 mgKOH/g, is a resin having an acidic group, acts as a binder resin, and is soluble in an alkaline developer used for pattern formation. It can be appropriately selected and used from among them.
- Preferred alkali-soluble resins in the present invention are, specifically, (meth)acrylic resins such as (meth)acrylic copolymers having a carboxy group and styrene-(meth)acrylic copolymers having a carboxy group, Epoxy (meth)acrylate resins having a carboxyl group and the like are included.
- (meth)acrylic resins such as (meth)acrylic copolymers having a carboxy group and styrene-(meth)acrylic copolymers having a carboxy group
- Epoxy (meth)acrylate resins having a carboxyl group and the like are included.
- particularly preferred are reactive alkali-soluble resins having a carboxy group in the side chain and a reactive group in the side chain. This is because the film strength of the cured film formed by containing the reactive group is improved.
- the reactive group includes at least one selected from the group consisting of ethylenically unsaturated bond-containing groups, epoxy
- (Meth)acrylic copolymers having a structural unit having a carboxyl group, and (meth)acrylic resins such as styrene-(meth)acrylic copolymers having a carboxyl group are, for example, carboxyl group-containing ethylenic It is a (co)polymer obtained by (co)polymerizing a saturated monomer and optionally other copolymerizable monomers by a known method.
- Carboxy group-containing ethylenically unsaturated monomers include, for example, (meth)acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. be done. Also, addition reaction products of monomers having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate and cyclic anhydrides such as maleic anhydride, phthalic anhydride and cyclohexanedicarboxylic anhydride, ⁇ -carboxy-polycaprolactone Mono (meth) acrylate and the like can also be used.
- Anhydride-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride may also be used as precursors of the carboxy group.
- (meth)acrylic acid is particularly preferable from the viewpoint of copolymerizability, cost, solubility, glass transition temperature, and the like.
- the alkali-soluble resin preferably further has a hydrocarbon ring from the viewpoint of excellent adhesion of the colored layer.
- the present inventors have found that the presence of a hydrocarbon ring, which is a bulky group, in the alkali-soluble resin suppresses the solvent resistance of the resulting colored layer, particularly swelling of the colored layer. Although the action is not clear, the presence of bulky hydrocarbon rings in the colored layer suppresses the movement of molecules in the colored layer, which increases the strength of the coating film and suppresses swelling due to solvents.
- hydrocarbon rings include cyclic aliphatic hydrocarbon rings which may have substituents, aromatic rings which may have substituents, and combinations thereof, and hydrocarbon rings may have a substituent such as a carbonyl group, a carboxy group, an oxycarbonyl group or an amide group.
- hydrocarbon rings may have a substituent such as a carbonyl group, a carboxy group, an oxycarbonyl group or an amide group.
- hydrocarbon rings include aliphatic hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, tricyclo[5.2.1.0(2,6)]decane (dicyclopentane), and adamantane.
- Aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, and fluorene; chain polycyclic rings such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, and stilbene; cardo structures represented by the following chemical formula (ii); be done.
- the alkali-soluble resin preferably has a maleimide structure represented by the following general formula (iii).
- RM is an optionally substituted hydrocarbon ring.
- the alkali-soluble resin has a maleimide structure represented by the general formula (iii), it has a nitrogen atom in the hydrocarbon ring, so that it has very good compatibility with the dispersant of the present invention, and the effect of suppressing development residue is excellent. improves.
- Specific examples of the optionally substituted hydrocarbon ring in RM of the general formula (iii) are the same as the specific examples of the hydrocarbon ring described above.
- the heat resistance and adhesiveness of the colored layer are improved, and the brightness of the obtained colored layer is also preferably improved.
- the curability of the colored layer is improved, and the solvent resistance (NMP swelling suppression) is improved, which is particularly preferable.
- the alkali-soluble resin used in the present invention using a (meth)acrylic copolymer having a structural unit having a hydrocarbon ring separately from a structural unit having a carboxy group can adjust the amount of each structural unit. It is preferable from the viewpoint that it is easy to increase the amount of the structural unit having the hydrocarbon ring and the function of the structural unit can be easily improved.
- the (meth)acrylic copolymer having a structural unit having a carboxyl group and the above hydrocarbon ring may use an ethylenically unsaturated monomer having a hydrocarbon ring as the above-mentioned "other copolymerizable monomer".
- ethylenically unsaturated monomers having a hydrocarbon ring examples include cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, phenoxy Ethyl (meth) acrylate, styrene, etc., and from the point that the cross-sectional shape of the colored layer after development is maintained even in heat treatment, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (Meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate and styrene are preferred.
- a method for introducing an ethylenically unsaturated bond-containing group into an alkali-soluble resin may be appropriately selected from conventionally known methods. For example, a method in which a compound having both an epoxy group and an ethylenically unsaturated bond in the molecule, such as glycidyl (meth)acrylate, is added to the carboxyl group of the alkali-soluble resin to introduce an ethylenically unsaturated bond into the side chain.
- a structural unit having a hydroxyl group is introduced into a copolymer, a compound having an isocyanate group and an ethylenically unsaturated bond is added to the molecule, and an ethylenically unsaturated bond is introduced into the side chain. etc.
- the alkali-soluble resin used in the present invention may further contain other structural units such as a structural unit having an ester group such as methyl (meth)acrylate and ethyl (meth)acrylate.
- a structural unit having an ester group functions not only as a component that suppresses the alkali solubility of the photosensitive colored resin composition, but also as a component that improves the solubility in a solvent and the solvent re-solubility.
- the alkali-soluble resin used in the present invention is a (meth)acrylic copolymer and a styrene-(meth)acrylic copolymer having a structural unit having a carboxy group and a structural unit having a hydrocarbon ring ( It is preferably a meth)acrylic resin, and a (meth)acrylic copolymer and styrene having a structural unit having a carboxy group, a structural unit having a hydrocarbon ring, and a structural unit having an ethylenically unsaturated bond - (Meth)acrylic resins such as (meth)acrylic copolymers are more preferred.
- the alkali-soluble resin can be made into an alkali-soluble resin with desired performance by appropriately adjusting the charging amount of each structural unit.
- the amount of the carboxyl group-containing ethylenically unsaturated monomer to be charged is preferably 5% by mass or more, more preferably 10% by mass or more, based on the total amount of the monomers in order to obtain a good pattern.
- the amount of the carboxyl group-containing ethylenically unsaturated monomer charged is preferably 50% by mass or less, and 40% by mass or less relative to the total amount of the monomer.
- the resulting coating film has sufficient solubility in an alkaline developer, and the proportion of the carboxy group containing ethylenically unsaturated monomer is at the above upper limit. If it is below, the formed pattern tends not to come off from the substrate and the film roughening on the pattern surface tends not to occur during development with an alkaline developer.
- (meth)acrylic copolymers and styrene-(meth)acrylic copolymers having structural units having ethylenically unsaturated bonds in side chains which are more preferably used as alkali-soluble resins
- the compound having both an epoxy group and an ethylenically unsaturated bond is preferably 10% by mass to 95% by mass with respect to the charged amount of the carboxyl group-containing ethylenically unsaturated monomer, and 15% by mass to 90% by mass. % by mass is more preferred.
- the weight average molecular weight (Mw) of the alkali-soluble resin such as the carboxy group-containing copolymer is preferably 3,000 or more, more preferably 5,000 or more, from the viewpoint of the binder function after curing. It is preferably 30,000 or less, more preferably 20,000 or less, from the viewpoint of pattern formability during development.
- the weight average molecular weight (Mw) in the present invention can be measured by Shodex GPC System-21H using polystyrene as a standard substance and THF as an eluent.
- the epoxy (meth)acrylate resin having a carboxy group is not particularly limited, but epoxy (meth) obtained by reacting a reaction product of an epoxy compound and an unsaturated group-containing monocarboxylic acid with an acid anhydride.
- Acrylate compounds are suitable.
- Epoxy compounds, unsaturated group-containing monocarboxylic acids, and acid anhydrides can be appropriately selected from known ones and used. For example, the description in paragraphs 0226 to 0240 of Japanese Patent No. 6911365 can be referred to and used as appropriate.
- epoxy (meth)acrylate resins having a carboxy group examples include polymers of epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate, or epoxy group-containing (meth)acrylates and other ethylenically unsaturated monomers.
- Epoxy (meth)acrylate resins having a carboxy group may be used alone or in combination of two or more.
- an alkali-soluble resin having an acid value of more than 50 mgKOH/g is selected and used.
- the alkali-soluble resin preferably has an acid value of 60 mgKOH/g or more and 300 mgKOH/g or less, especially 70 mgKOH/g or more, in terms of developability with an alkaline aqueous solution used in the developer and adhesion to the substrate. It is preferably 200 mgKOH/g or less.
- the upper limit of the acid value may be 150 mgKOH/g or less, 120 mgKOH/g or less, or 100 mgKOH/g or less.
- the acid value in the present invention can be measured according to JIS K 0070:1992.
- the ethylenically unsaturated bond equivalent when the side chain of the alkali-soluble resin has an ethylenically unsaturated bond improves the film strength of the cured film, improves solvent resistance and development resistance, and has excellent adhesion to the substrate. From the viewpoint of obtaining such effects, it is preferably in the range of 100 to 2000, and particularly preferably in the range of 140 to 1500. If the ethylenically unsaturated bond equivalent is 2000 or less, the solvent resistance, development resistance and adhesion are excellent. Also, if it is 100 or more, the ratio of other structural units such as structural units having a carboxy group and structural units having a hydrocarbon ring can be relatively increased, so that excellent developability and heat resistance can be obtained.
- the ethylenically unsaturated bond equivalent is the weight average molecular weight per mole of the ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following formula (1).
- Ethylenically unsaturated bond equivalent (g / mol) W (g) / M (mol) (In formula (1), W represents the mass (g) of the alkali-soluble resin, and M represents the number of moles (mol) of ethylenically unsaturated bonds contained in the alkali-soluble resin W (g).)
- the ethylenically unsaturated bond equivalent is obtained, for example, by measuring the number of ethylenically unsaturated bonds contained per 1 g of the alkali-soluble resin in accordance with the iodine value test method described in JIS K 0070: 1992. can be calculated.
- the alkali-soluble resins used in the photosensitive colored 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 colored 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.
- the non-reactive resin used in the present invention has an acid value of 7 mgKOH/g to 50 mgKOH/g, and the content of structural units derived from methyl methacrylate is 50% to 99% by mass of all structural units, It has a weight average molecular weight of 5,000 to 50,000.
- the non-reactive resin used in the present invention is basically a resin that does not have at least one reactive group selected from the group consisting of an ethylenically unsaturated bond-containing group, an epoxy group, an oxetane group, and a blocked isocyanate group. is.
- the non-reactive resin used in the present invention has an acid value of 7 mgKOH/g or more, preferably 20 mgKOH/g or more, more preferably 30 mgKOH/g or more, from the viewpoint of suppressing development residues.
- the non-reactive resin used in the present invention has an acid value of 50 mgKOH/g or less, may be 47 mgKOH/g or less, preferably 45 mgKOH/g or less, more preferably 45 mgKOH/g or less, from the viewpoint of improving the undercut shape. is 40 mgKOH/g or less.
- the non-reactive resin used in the present invention may be a copolymer containing structural units derived from methyl methacrylate.
- the content of structural units derived from methyl methacrylate in all structural units is 50% by mass or more, preferably 90% by mass or more, from the viewpoint of improving the undercut shape. Yes, more preferably 92% by mass or more.
- the content of structural units derived from methyl methacrylate is 99% by mass or less, preferably 98% by mass or less, and more preferably 97% by mass or less, based on all structural units, from the viewpoint of suppressing development residues.
- the non-reactive resin used in the present invention may be a (meth)acrylic copolymer containing a structural unit derived from an ethylenically unsaturated monomer copolymerizable with a structural unit derived from methyl methacrylate. It may be a (meth)acrylic copolymer having a structural unit derived from methyl and a structural unit having an acidic group, and a (meth)acrylic copolymer containing a structural unit derived from methyl methacrylate and a structural unit having a carboxy group. It may be a system copolymer. Examples of structural units having a carboxy group include structural units derived from carboxy group-containing ethylenically unsaturated monomers.
- the carboxy group-containing ethylenically unsaturated monomer may be the same as the carboxy group-containing ethylenically unsaturated monomers listed in the alkali-soluble resin.
- Acrylic acid is particularly preferred.
- the content of the structural unit having a carboxy group may be appropriately adjusted according to the acid value, and is selected from the range of 1% by mass to 10% by mass, preferably 2% by mass or more, more preferably 2% by mass or more, of all the structural units. is 3% by mass or more, preferably 9% by mass or less, and more preferably 8% by mass or less.
- the non-reactive resin used in the present invention is a structural unit derived from methyl methacrylate and a structural unit having an acidic group, as well as a structural unit derived from methyl methacrylate, as long as the effects of the present invention are not impaired. It may have other constitutional units derived from polymerizable ethylenically unsaturated monomers. Other copolymerizable ethylenically unsaturated monomers may be the same as the ethylenically unsaturated monomers exemplified for the alkali-soluble resin. Among other copolymerizable ethylenically unsaturated monomers, those having no alkali-soluble substituents are preferable from the viewpoint of suppressing undercut shapes.
- copolymerizable ethylenically unsaturated monomers include, for example, ethyl methacrylate, butyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate, isobornyl methacrylate, tetrahydrofurfuryl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, dimethylaminomethyl methacrylate, diethylaminoethyl methacrylate, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane ethoxysilane, 3-methacryloxypropyltriethoxysilane, and the like.
- Other structural units may be used in combination of two or more.
- the total content of structural units derived from methyl methacrylate and structural units having an acidic group may be 100% by mass of all structural units, and the structural units derived from methyl methacrylate and The total content of structural units having a carboxy group may be 100% by mass in all structural units.
- the weight average molecular weight (Mw) of the non-reactive resin used in the present invention is 5,000 or more, preferably 7,000 or more, more preferably 9,000 or more from the viewpoint of improving the undercut shape.
- the weight average molecular weight (Mw) is 50,000 or less, preferably 30,000 or less, more preferably 20,000 or less, from the viewpoint of suppressing development residue.
- the non-reactive resin used in the present invention can be prepared in the same manner as the alkali-soluble resin.
- the non-reactive resin used in the present invention may have a glass transition temperature (Tg) exceeding 0°C, 20°C or higher, or 50°C or higher.
- the glass transition temperature (Tg) of the alkali-soluble resin is measured using differential scanning calorimetry (DSC) (for example, EXSTAR DSC 7020 manufactured by SII Nanotechnology) according to the method described in JIS K7121. be able to.
- DSC differential scanning calorimetry
- EXSTAR DSC 7020 manufactured by SII Nanotechnology the method described in JIS K7121.
- 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 glass transition temperature (Tg) of the copolymer can be calculated by the following formula and used as a guideline.
- Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer.
- Tgi homopolymer glass transition temperature value of each monomer, the value in Polymer Handbook (3rd Edition) (J. Brandrup, EHImmergut (Wiley-Interscience, 1989)) can be adopted.
- the non-reactive resin used in the photosensitive colored resin composition may be used singly or in combination of two or more.
- the content of the non-reactive resin may be appropriately selected and used, but from the viewpoint of improving the undercut shape, it is preferably 1% by mass or more relative to the total solid content of the photosensitive colored resin composition. It is preferably 2% by mass or more, more preferably 4% by mass or more.
- the content of the non-reactive resin is preferably 20% by mass or less, more preferably 15% by mass or less, more preferably 15% by mass or less, based on the total solid content of the photosensitive colored resin composition. It is 12% by mass or less.
- the content of the non-reactive resin used in the photosensitive colored resin composition is preferably It is 1% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more.
- the content of the non-reactive resin is preferably 80% by mass or less, more preferably 70% by mass, based on the total content of the reactive alkali-soluble resin and the non-reactive resin. % or less, more preferably 60 mass % or less.
- photopolymerizable compound used in the photosensitive colored 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, and includes ethylenically unsaturated bond-containing groups such as vinyl, allyl, acryloyl and methacryloyl groups. 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 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 may be appropriately selected from among conventionally known ones and used. 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 colored resin composition of the present invention, the polyfunctional (meth)acrylate has three polymerizable ethylenically unsaturated bonds (three Functionality) or more is preferable, and poly(meth)acrylates of trihydric or higher polyhydric alcohols and their dicarboxylic acid-modified products are preferable.
- trimethylolpropane tri(meth)acrylate penta Erythritol 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)acrylate modified with succinic acid, dipentaerythritol hexa(meth)acrylate and the like are preferred.
- the content of the photopolymerizable compound used in the photosensitive colored resin composition is not particularly limited, but relative to the total solid content of the photosensitive colored resin composition, for example preferably 5% by mass to 60% by mass, 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 colored resin composition of the present invention one or a combination of two or more of conventionally known various 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 photoinitiator 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 oxime ester photoinitiator is a compound represented by the following general formula (A) and the following general formula ( It preferably contains at least one compound represented by B).
- 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; )
- X 1 , X 3 and X 6 each independently represent R 41 , OR 41 , COR 41 , SR 41 , CONR 42 R 43 or CN;
- X 2 has 1 to represents an alkyl group having 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms, and
- X 4 and X 5 each independently represent R 41 , OR 41 , SR 41 , COR 41 , CONR 42 R 43 , NR 42 COR 41 , OCOR 41 , COOR 41 , SCOR 41 , COSR 41 , COSR 41 , CSOR 41 , CN, halogen atom or hydroxyl group;
- R 41 , R 42 and R 43 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 arylal
- R 51 , R 52 and R 53 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 54 represents a heterocyclic group of hydrogen atoms of the groups represented by R 51 , R 52 and R 53 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 41 , R 42 , R 43 , X 2 , R 51 , R 52 and R 53 are -O-, -S-, -COO-, -OCO-, -NR 54 - , -NR 54 CO-, -NR 54 COO-, -OCONR 54 -, -SCO-, -COS-, -OCS- or -CSO-, even if 1 to 5 oxygen atoms are not adjacent Often, R 54 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 heterocycl
- 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 to be 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 group 1 to 20 carbon atoms represented by R 3 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 21 , R 22 , R 23 and R 24 in the above general formula (A)
- alkyl group examples 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, cyclopenty
- 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 is preferable because of its high solvent solubility
- an alkyl group of R 2 is preferably a methyl group, an ethyl group or a phenyl group because of its high reactivity
- R 4 to R 7 is a hydrogen atom or a 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.
- High sensitivity is preferred, and at least one of R 31 to R 35 is more preferably a nitro group, CN, a halogen atom, or COPh (where Ph is a phenyl group), and R 33 is a nitro group, CN, or a halogen atom. Atoms, or COPh, are particularly preferred.
- Preferred specific examples of the compound represented by the general formula (A) include the following compounds.
- the oxime ester compound represented by the general formula (B) also has 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 (B) and its exemplified compounds represent a mixture of both or either one, and are not limited to structures showing isomers.
- the alkyl group having 1 to 20 carbon atoms represented by X 2 , R 41 , R 42 , R 43 , R 51 , R 52 , R 53 and R 54 may be The same as the alkyl group having 1 to 20 carbon atoms in (A) can be mentioned.
- the aryl group having 6 to 30 carbon atoms represented by X 2 , R 41 , R 42 , R 43 , R 51 , R 52 , R 53 and R 54 in the general formula (B) is Examples thereof include the same aryl groups having 6 to 30 carbon atoms in (A).
- the arylalkyl group having 7 to 30 carbon atoms represented by X 2 , R 41 , R 42 , R 43 , R 51 , R 52 , R 53 and R 54 in the general formula (B) includes Examples thereof include the same arylalkyl groups having 7 to 30 carbon atoms in formula (A).
- the heterocyclic group having 2 to 20 carbon atoms represented by X 2 , R 41 , R 42 , R 43 , R 51 , R 52 , R 53 and R 54 in the general formula (B) includes Examples thereof include the same heterocyclic groups having 2 to 20 carbon atoms in formula (A).
- examples of the halogen atom in the general formula (B) include the same halogen atoms as the halogen atoms in the general formula (A).
- alkylene moieties of the groups represented by R 41 , R 42 , R 43 , X 2 , R 51 , R 52 and R 53 in the above general formula (B) are -O-, -S-, -COO- , -OCO-, -NR 54 -, -NR 54 CO-, -NR 54 COO- , -OCONR 54 -, -SCO-, -COS-, -OCS- or -CSO- under conditions where oxygen atoms are not adjacent to each other may contain 1 to 5, 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, two or more are contained continuously. may
- X 1 is more preferably a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, from the viewpoint of sensitivity, solubility and compatibility.
- Alkyl groups having 1 to 10 carbon atoms such as t-butyl, n-amyl, isoamyl, t-amyl, n-hexyl and 2-ethylhexyl groups, and 5 carbon atoms such as cyclopentyl and cyclohexyl groups cyclic alkyl groups which may have up to 10 side chains, or groups such as methoxymethyl, ethoxymethyl, ethoxyethyl, 2-(1-methoxypropyl) and 2-(1-ethoxypropyl) groups It is an alkyl group having 2 to 10 carbon atoms and having one ether bond in a methylene chain, more preferably an alkyl group having 1 to 10 carbon atoms such as methyl, ethyl and 2-ethylhexyl.
- X 2 , X 3 and X 6 are each independently from the viewpoint of sensitivity, solubility and compatibility, and particularly preferably methyl group, ethyl group, n-propyl group and isopropyl alkyl groups having 1 to 6 carbon atoms such as groups, n-butyl groups, isobutyl groups, t-butyl groups, n-amyl groups, isoamyl groups, t-amyl groups and n-hexyl groups, cyclopentyl groups and cyclohexyl groups
- a cyclic alkyl group having 5 to 6 carbon atoms such as, or a carbon number such as methoxymethyl group, ethoxymethyl group, ethoxyethyl group, 2-(1-methoxypropyl) group and 2-(1-ethoxypropyl) group is an alkyl group having 2 to 6 carbon atoms and one ether bond in the methylene chain, more preferably an
- X 3 and X 6 are each independently preferably an alkyl group having 1 to 6 carbon atoms in terms of sensitivity, solubility and compatibility. From the viewpoint of sensitivity, solubility and compatibility, X2 is more preferably an alkyl group having 2 to 6 carbon atoms and having one ether bond in the methylene chain.
- X 4 and X 5 are each independently from the viewpoint of sensitivity, solubility and compatibility, and particularly preferably hydrogen, or a methyl group, an ethyl group, an n-propyl group, C1-C6 alkyl groups such as isopropyl, n-butyl, isobutyl, t-butyl, n-amyl, isoamyl, t-amyl and n-hexyl groups.
- a and b are each independently an integer of 0 to 3, may be an integer of 0 to 1, or may be 0;
- Preferred specific examples of the compound represented by the general formula (B) include the following compounds.
- the total content of the photoinitiator used in the photosensitive colored 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 colored 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 compound represented by the general formula (A) and the compound represented by the general formula (B) is a cured film having good substrate adhesion and solvent resistance even in low-temperature heat treatment.
- the total amount of the photoinitiator 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 100% by mass can be
- the solvent used in the present invention is not particularly limited as long as it does not react with each component in the photosensitive colored resin composition and is capable of dissolving or dispersing them.
- a solvent can be used individually or in combination of 2 or more types.
- Specific examples of solvents include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, i-propyl alcohol, methoxy alcohol and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ester solvents such
- 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 colored 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 dispersing agent for example, a cationic, anionic, nonionic, amphoteric, silicone or fluorine surfactant 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 it is preferable to use a (meth)acrylate copolymer-based dispersant as the dispersant, since solvent resistance tends to be improved even with low-temperature heat treatment.
- (Meth) acrylate copolymer-based dispersant has good compatibility with the alkali-soluble resin, the non-reactive resin, the photopolymerizable compound and the photoinitiator, so that the initiator can be uniformly dispersed in the colored layer. As the colored layer hardens uniformly, the amount of unreacted components decreases and the internal stress of the colored layer decreases, so it is presumed 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 formed.
- 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, organic acid compounds described in JP-A-2012-236882 and the like 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, even 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 a 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.
- a graft polymer chain having a structural unit derived from (meth)acrylate a conventionally known structure can be appropriately selected and used.
- graft copolymer and the salt-type graft copolymer described in WO2021/006077 may be used.
- block copolymer as the B block containing a structural unit derived from (meth)acrylate, a conventionally known structure can be appropriately selected and used.
- block copolymers and salt-type block copolymers described in WO2016/104493 may be used.
- 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 (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 resulting 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 coloring material, but in the photosensitive colored 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 colored resin composition is excellent.
- developability will become favorable.
- the content of the dispersant is, for example, preferably 2% by mass to 25% by mass, more preferably 2% by mass to 25% by mass, based on the total solid content of the photosensitive colored resin composition. It is within the range of 3% by mass to 20% by mass.
- the photosensitive colored resin composition of the present invention preferably further contains at least one of a polyfunctional epoxy compound and a polyfunctional blocked isocyanate compound from the viewpoint of improving solvent resistance after low-temperature heat treatment.
- a polyfunctional epoxy compound is a compound having two or more epoxy groups in one molecule.
- An epoxy group means a group containing a three-membered cyclic ether structure, and includes an alicyclic epoxy group.
- Epoxy groups include an oxiranyl group and a 3,4-epoxycyclohexyl group. Some or all of the hydrogen atoms in these epoxy groups may be substituted with substituents such as alkyl groups.
- polyfunctional epoxy compounds include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, and hydrogenated bisphenol AD diglycidyl ether.
- Polyfunctional epoxy compounds may be used alone or in combination of two or more. Among them, 1,2-epoxy-4-(2-oxiranyl)cyclohexane of 2,2-bis(hydroxymethyl)-1-butanol An adduct is preferred because it tends to improve solvent resistance after low-temperature heat treatment.
- a polyfunctional blocked isocyanate compound is a compound having two or more blocked isocyanate groups in one molecule.
- a blocked isocyanate group is a group obtained by blocking an isocyanate group with a blocking agent.
- the polyfunctional blocked isocyanate compound remains stable at around room temperature, and the blocking agent is dissociated by heat treatment to regenerate the active isocyanate group. Obtained by reacting a compound with a blocking agent.
- polyfunctional isocyanate compounds include 2,4- and/or 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, 3, aromatic diisocyanates such as 3′-dimethyldiphenyl-4,4′-diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, trans-1,4-cyclohexyl diisocyanate and norbornane diisocyanate; diethylene Diisocyanate, tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4 and/or (2,4,4)-trimethylhexamethylene diisocyanate, lysine diisocyanate, cyclohex
- heterocyclic diisocyanates, etc., and diisocyanates such as carbodiimide-modified, isocyanurate-modified, and biuret-modified products of these diisocyanate compounds.
- triphenylmethane triisocyanate 1-methylbenzol-2,4,6-triisocyanate, dimethyltriphenylmethane tetraisocyanate, N,N′,N′′-tri(1-isocyanatohexyl)isocyanuric acid, lysine triisocyanate , tris(phenylisocyanate) thiophosphate, 4,4′,4′′-triisocyanate-2,5-dimethoxyphenylamine, 1,3,5-triisocyanatocyclohexane, 1,3,5-tris(isocyanatomethyl ) cyclohexane, etc.
- Trifunctional or higher isocyanate compounds such as carbodiimide-modified, isocyanurate-modified and biuret-modified products of these isocyanate compounds can be mentioned. These can be used singly or in combination of two or more. Among these isocyanate compounds, alicyclic diisocyanates and aliphatic diisocyanates are more preferable from the viewpoint of transparency.
- the blocking agent known blocking agents can be appropriately selected and used. Active methylene compounds such as acetylacetone and acetoacetate esters (methyl acetoacetate, ethyl acetoacetate, etc.), 3,5-dimethylpyrazole and the like are preferably used.
- the content of at least one of the polyfunctional epoxy compound and the polyfunctional blocked isocyanate compound is usually 3% to 30% by mass, preferably 5% to 20% by mass, based on the total solid content of the photosensitive colored resin composition. It is within the range of % by mass. If it is at least the above lower limit, it is easy to improve the solvent resistance and substrate adhesion after low-temperature heat treatment. On the other hand, if it is the above upper limit or less, the photosensitive colored resin composition of the present invention tends to have good developability.
- the photosensitive colored 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 in one molecule and polyfunctional thiol compounds having two or more thiol groups in one molecule. 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 colored 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, if it is at most the above upper limit, the photosensitive colored resin composition of the present invention tends to have good developability and suppressed line width shift.
- the photosensitive colored 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 colored resin composition of the present invention preferably further contains an antioxidant from the viewpoint of suppressing the line width shift amount of the cured film.
- the photosensitive colored 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 also be a latent antioxidant as described in WO 2014/021023.
- 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 colored 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 colored resin composition of this invention into a highly sensitive photosensitive colored 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, based on the total solid content in the photosensitive colored resin composition. %. If it is more than the said lower limit and below the said upper limit, the board
- the method for producing a photosensitive colored resin composition of the present invention comprises a coloring material, an alkali-soluble resin, a non-reactive resin, a photopolymerizable compound, a photoinitiator, a solvent, and various additive components optionally used. can be prepared by mixing with using a known mixing means.
- the photosensitive colored resin composition of the present invention is, for example, a colorant, an alkali-soluble resin, a non-reactive resin, a photopolymerizable compound, a photoinitiator, a dispersant, a solvent, and various kinds of materials used as desired.
- the method for preparing the resin composition includes, for example, (1) First, a coloring material and a dispersant are added to a solvent to prepare a coloring material dispersion, and the dispersion is (2) a method of mixing an alkali-soluble resin, a non-reactive resin, a photopolymerizable compound, a photoinitiator, and various additive components optionally used; (2) a coloring material and a dispersing agent in a solvent; , a method of simultaneously adding and mixing an alkali-soluble resin, a non-reactive resin, a photopolymerizable compound, a photoinitiator, and optionally various additive components; (3) a dispersant in a solvent; A method of adding and mixing an alkali-soluble resin, a non-reactive resin, a photopolymerizable compound, a photoinitiator, and various additive components that are optionally used, and then adding and dispersing a coloring material; (4) A coloring material, a
- the above methods (1) and (4) are preferable because they can effectively prevent the aggregation of the colorant and uniformly disperse the colorant.
- the dispersant may be removed and prepared by the above method (2), (3) or (4).
- 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 colored resin composition according to the present invention can suppress the generation of development residues even in 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 less, further 100° C. or less or 90° C. or less in which a color filter is directly formed on a substrate on which an element having low heat resistance such as an organic light-emitting element is formed. It can be suitably used for a cured film formed on an organic light-emitting device.
- the photosensitive colored 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 external light reflection suppressing effect. Used.
- the cured film of the photosensitive colored resin composition according to the present invention is used in place of the circularly polarizing plate, it can be a display device that does not contain a polarizing plate, so the photosensitive colored resin composition according to the present invention is , is suitably used for display devices that do not contain a polarizing plate.
- the photosensitive colored resin composition according to the present invention is a photosensitive colored 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 colored resin composition according to the present invention.
- the cured product according to the present invention forms a coating film of the photosensitive colored resin composition according to the present invention, and after drying the coating film, exposure, and if necessary development, obtained by 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 colored 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 colored 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 colored 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, oven, etc. it is exposed through a mask of a predetermined pattern to photopolymerize the alkali-soluble resin and the polyfunctional monomer, etc. to cure. 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, 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.
- heat treatment may be performed.
- the heating conditions are appropriately selected according to the mixing ratio of each component in the photosensitive colored 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 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 developing solution is usually washed and the cured coating film of the photosensitive colored resin composition is dried to form a colored layer.
- 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 also 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 device 80 known structures can be appropriately used.
- 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 colored 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 colored 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 colored 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 colored resin composition according to the present invention may be any one of the three colored cured films (109R, 109G, 109B), or may be all of them. .
- 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, SiON, and 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 colored 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 colored 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 in accordance with 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 can be used. 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 colored 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 colored resin composition according to the present invention on the organic light-emitting element. Each step will be described below.
- the above-mentioned organic light-emitting element may not be applied adjacent to the organic light-emitting element, and may be applied through at least one layer.
- 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 above-described photosensitive colored resin composition of the present invention, on the organic light-emitting element to apply.
- spin coating and die coating are 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 colored 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. .
- 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.
- Synthesis Example 2 Synthesis of non-reactive resin 2
- Synthesis Example 1 was carried out in the same manner as in Synthesis Example 1, except that methyl methacrylate was changed from 95% by mass to 93% by mass in all monomers, and methacrylic acid was changed from 5% by mass to 7% by mass in all monomers.
- a non-reactive resin 2 was synthesized by Table 2 shows the weight average molecular weight and acid value of the obtained non-reactive resin 2.
- Synthesis Example 3 Synthesis of non-reactive resin 3
- Synthesis Example 1 was carried out in the same manner as in Synthesis Example 1, except that methyl methacrylate was changed from 95% by mass to 99% by mass in all monomers, and methacrylic acid was changed from 5% by mass to 1% by mass in all monomers.
- a non-reactive resin 3 was synthesized by Table 2 shows the weight average molecular weight and acid value of the obtained non-reactive resin 3.
- Synthesis Example 10 Synthesis of non-reactive resin 10. Same as Synthesis Example 1 except that in Synthesis Example 1, methyl methacrylate was changed from 95% by mass in all monomers to 70% by mass in all monomers and ethyl methacrylate was changed to 25% by mass in all monomers. Then, a non-reactive resin 10 was synthesized. Table 2 shows the weight average molecular weight and acid value of the obtained non-reactive resin 10.
- Synthesis Example 11 Synthesis of non-reactive resin 11
- Synthesis Example 11 Synthesis of non-reactive resin 11
- methyl methacrylate was changed from 95% by mass in all monomers to 50% by mass in all monomers and ethyl methacrylate was changed to 45% by mass in all monomers.
- a non-reactive resin 11 was synthesized.
- Table 2 shows the weight average molecular weight and acid value of the obtained non-reactive resin 11.
- Comparative non-reactive resin c1 was synthesized in the same manner as in Synthesis Example 1, except that 95% by mass of methyl methacrylate monomer was changed to 95% by mass of butyl methacrylate monomer.
- Table 5 shows the weight average molecular weight and acid value of the obtained comparative non-reactive resin c1.
- Comparative Synthesis Example 2 Synthesis of comparative non-reactive resin c2
- a comparative non-reactive resin c2 was synthesized in the same manner as in Synthesis Example 1, except that the amount of the chain transfer agent (n-dodecylmercaptan) added was changed to 0 parts by mass.
- Table 5 shows the weight average molecular weight and acid value of the obtained comparative non-reactive resin c2.
- Comparative Synthesis Example 3 Synthesis of comparative non-reactive resin c3
- a comparative non-reactive resin c3 was synthesized in the same manner as in Synthesis Example 1, except that the amount of the chain transfer agent (n-dodecylmercaptan) added was changed to 10 parts by mass.
- Table 5 shows the weight average molecular weight and acid value of the obtained comparative non-reactive resin c3.
- Comparative Synthesis Example 4 Synthesis of comparative non-reactive resin c4
- a comparative non-reactive resin c4 was synthesized in the same manner as in Synthesis Example 1, except that the methyl methacrylate monomer was changed from 95% by mass to 100% by mass.
- Table 5 shows the weight average molecular weight and acid value of the obtained comparative non-reactive resin c4.
- 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 colored resin composition R-1)
- Production of Colorant Dispersion R (1) In a 225 mL mayonnaise bottle, 72.1 parts by mass of PGMEA, 15.0 parts by mass of the alkali-soluble resin A solution of Preparation Example 1 (solid content: 40% by mass), Preparation Example 12 10.2 parts by mass of a PGMEA solution (solid content: 35% by mass) of block copolymer 1 was added and stirred. 0.4 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 .
- Examples 2 to 11 Production of photosensitive colored resin compositions R-2 to R-11
- the type and / or mass ratio of the non-reactive resin was changed, and the formula (A-2) represented Photosensitive colored resin composition R-1 except that the ratio of the oxime ester photoinitiator was the same as in Example 1 and the mass ratio of the polyfunctional monomer was changed so that the pigment concentration was the same as in Example 1.
- photosensitive colored resin compositions R-2 to R-11 were obtained.
- Example 12 to 21 Production of photosensitive colored resin compositions R-12 to R-21
- (1) Production of Colorant Dispersion Liquids R(2) to (11) A colorant dispersion was prepared in the same manner as the colorant dispersion liquid R (1), except that the type of resin was changed to alkali-soluble resin B, C, D, E, F, G, H, I, J, or K. Liquids R (2) to (11) were obtained.
- Example 22 Production of photosensitive colored resin composition R-22
- oxime ester photoinitiator represented by the formula (A-2), a fluorine-based surfactant (trade name Megafac R-08MH, DIC Corporation )), 0.1 parts by mass of a polyfunctional epoxy compound (1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, trade name EHPE3150, 10 parts by mass of Daicel Co., Ltd.) and 170.5 parts by mass of PGMEA were added to obtain a photosensitive colored resin composition R-22.
- A-2 the oxime ester photoinitiator represented by the formula (A-2), a fluorine-based surfactant (trade name Megafac R-08MH, DIC Corporation )), 0.1 parts by mass of a polyfunctional epoxy compound (1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, trade name EHPE31
- Example 23 Production of photosensitive colored resin composition R-23)
- the polyfunctional epoxy compound was changed to a polyfunctional blocked isocyanate compound (trade name Duranate MF-K60B, manufactured by Asahi Kasei Corporation) in the same manner as the photosensitive colored resin composition R-22.
- a colored resin composition R-23 was obtained.
- Example 24 Production of photosensitive colored resin composition G-1)
- Production of Colorant Dispersion G (1) In a 225 mL mayonnaise bottle, 72.1 parts by mass of PGMEA, 15 parts by mass of the alkali-soluble resin A solution (solid content: 40% by mass) of Preparation Example 1, and the block of Preparation Example 12 are mixed. 10.2 parts by mass of a PGMEA solution of copolymer 1 (solid content: 35% by mass) was added and stirred. 0.4 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
- Pigment Green 59 in 8.0 parts by mass and C.I. I. 5.3 parts by mass of Pigment Yellow 150 (Y150) and 100 parts by mass of zirconia beads with a particle size of 2.0 mm are added and shaken for 1 hour with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for pre-disintegration. 200 parts of zirconia beads of 1 mm were used, and dispersion was carried out for 4 hours with a paint shaker as main pulverization to obtain a coloring material dispersion liquid G(1).
- the block copolymer 1 is salt-formed with phenylphosphonic acid to form a salt-type block copolymer 1 .
- Examples 25 to 34 Production of photosensitive colored resin compositions G-2 to G-11
- the type and / or mass ratio of the non-reactive resin was changed, and the formula (A-2) represented Photosensitive colored resin composition G-1 except that the ratio of the oxime ester photoinitiator was the same as in Example 24, and the mass ratio of the polyfunctional monomer was changed so that the pigment concentration was the same as in Example 24.
- photosensitive colored resin compositions G-2 to G-11 were obtained.
- Example 45 Production of photosensitive colored resin composition G-22
- 111 parts by mass of the colorant dispersion G (1) obtained above 10 parts by mass of the non-reactive resin 1 obtained in Synthesis Example 1, a polyfunctional monomer (trade name Aronix M-305, Toagosei Co., Ltd.
- Example 46 Production of photosensitive colored resin composition G-23)
- the polyfunctional epoxy compound was changed to a polyfunctional blocked isocyanate compound (trade name Duranate MF-K60B, manufactured by Asahi Kasei Corporation)
- photosensitive coloring was performed in the same manner as for the photosensitive colored resin composition G-22.
- a resin composition G-23 was obtained.
- Example 47 Production of photosensitive colored resin composition B-1) (1) Production of Colorant Dispersion B (1) In a 225 mL mayonnaise bottle, 48.1 parts by mass of PGMEA, 10 parts by mass of the alkali-soluble resin A solution of Preparation Example 1 (solid content: 40% by mass), and the block of Preparation Example 12 6.8 parts by mass of a PGMEA solution of copolymer 1 (solid content: 35% by mass) was added and stirred. 0.3 parts by mass of phenylphosphonic acid (trade name: PPA, manufactured by Nissan Chemical Industries, Ltd.) was added thereto, and the mixture was stirred at room temperature for 30 minutes. C.I. I.
- Pigment Blue 15:6 (B15:6) was added at 7.1 parts by mass, and C.I. I. 1.8 parts by mass of Pigment Violet 23 (V23) and 100 parts by mass of zirconia beads with a particle size of 2.0 mm were added, and the mixture was shaken for 1 hour with a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for preliminary crushing. 200 parts of zirconia beads of 1 mm were used, and dispersion was carried out for 4 hours with a paint shaker as main pulverization to obtain a coloring material dispersion liquid B(1).
- the block copolymer 1 is salt-formed with phenylphosphonic acid to form a salt-type block copolymer 1 .
- Example 48 to 57 Production of photosensitive colored resin compositions B-2 to B-11
- the type and / or mass ratio of the non-reactive resin was changed, and represented by the formula (A-2)
- the ratio of the oxime ester photoinitiator remains the same as in Example 47, except that the mass ratio of the polyfunctional monomer is changed so that the pigment concentration is the same as in Example 47.
- Photosensitive colored resin composition B-1 In the same manner as above, photosensitive colored resin compositions B-2 to B-11 were obtained.
- Example 68 Production of photosensitive colored resin composition B-22
- a polyfunctional monomer trade name Aronix M-305, Toagosei Co., Ltd.
- Example 69 Production of photosensitive colored resin composition B-273
- the polyfunctional epoxy compound was changed to a polyfunctional blocked isocyanate compound (trade name Duranate MF-K60B, manufactured by Asahi Kasei Corporation).
- a colorant resin composition B-23 was obtained.
- Comparative Examples 1 to 6 Production of Comparative Photosensitive Colored Resin Compositions CR-1 to CR-6)
- Example 1 As shown in Table 5, except that no non-reactive resin was used or any of the comparative non-reactive resins c1 to c5 was used instead of non-reactive resin 1
- Comparative photosensitive colored resin compositions CR-1 to CR-6 were obtained in the same manner as the colored resin composition R-1.
- the photosensitive colored resin composition obtained in each example and each comparative example was coated on a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") using a spin coater to form a cured coating film having a thickness. After coating to 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
- ⁇ 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.
- Examples 1 to 69 which are photosensitive colored resin compositions according to the present invention
- the alkali-soluble resin was combined with a specific non-reactive resin, so that the generation of development residue was suppressed even in low-temperature heat treatment, and It was shown that a colored layer with a good pattern shape can be formed.
- the non-reactive resin the use of a non-reactive resin in which the content of structural units derived from methyl methacrylate is 90% by mass to 99% by mass in all structural units is shown to improve the cross-sectional shape. was done.
- the addition of a polyfunctional epoxy resin or a polyfunctional isocyanate compound among others improves the solvent resistance.
- Comparative Example 2 in which a non-reactive resin having an acid value and a weight average molecular weight in the same range as the non-reactive resin of the present invention but using a butyl methacrylate monomer instead of a methyl methacrylate monomer was combined with an alkali-soluble resin.
- the photosensitive colored resin compositions Nos. 8 and 14 the cross-sectional shape of the colored layer was shown to be an undercut shape.
- Comparative Examples 3, 9 and 15 a non-reactive resin having a structural unit and an acid value in the same range as the non-reactive resin of the present invention but having a weight-average molecular weight larger than the specific value of the present invention was combined with an alkali-soluble resin. It has been shown that the photosensitive colored resin composition leaves a development residue in the colored layer formation area. Further, in Comparative Examples 4, 10 and 16, a non-reactive resin having a constitutional unit and an acid value in the same range as the non-reactive resin of the present invention but having a weight average molecular weight lower than the specific value of the present invention was combined with an alkali-soluble resin.
- the cross-sectional shape of the colored layer of the photosensitive colored resin composition becomes an undercut shape.
- the weight average molecular weight is in the same range as the non-reactive resin of the present invention, but the content of structural units derived from methyl methacrylate is 100 mol% of all structural units, and the acid value is 0 mgKOH/g.
- the photosensitive colored resin compositions of Comparative Examples 5, 11 and 17 in which the was combined with an alkali-soluble resin were shown to produce development residues in the colored layer formation portion.
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Abstract
Description
これらの液晶表示装置や有機発光表示装置には、カラーフィルタが用いられる。例えば液晶表示装置のカラー画像の形成は、カラーフィルタを通過した光がそのままカラーフィルタを構成する各画素の色に着色されて、それらの色の光が合成されてカラー画像を形成する。その際の光源としては、従来の冷陰極管のほか、白色発光の有機発光素子や白色発光の無機発光素子が利用される場合がある。有機発光表示装置では、色調整などのためにカラーフィルタを用いる。
カラーフィルタにおける着色層の形成方法としては、例えば、分散剤等により色材を分散してなる色材分散液にバインダー樹脂、光重合性化合物及び光開始剤を添加してなる着色樹脂組成物を基板に塗布して乾燥後、フォトマスクを用いて露光し、現像を行うことによって着色パターンを形成し、加熱することによりパターンを固着して着色層を形成する。あるいは、着色樹脂組成物を基板にインクジェット法等でパターン状に塗布して乾燥後、硬化させることによって、着色パターンを形成し、加熱することによりパターンを固着して着色層を形成する。形成これらの工程を、各色ごとに繰り返してカラーフィルタを形成する。
例えば、着色パターンを形成する際、着色樹脂組成物を露光すると層の上方から露光が行われるので、露光量は、層の上部ほど多く、層の下部に行くほど少なくなる。そのため、露光後に現像を行うと、現像時の層の下部が削られてパターン形状が悪化しやすい。すなわち、得られるパターンの断面形状は、パターンの上面が一番幅広く下面が一番狭い形状、すなわち、アンダーカット形状(逆テーパー形状ともいわれる)になりやすい。アンダーカット形状になると、パターンの剥がれれや欠けが発生しやすくなったり、画素端部に空隙が発生したり、次工程で上に塗布する場合に均一に塗工できない等、様々な問題が顕在化する。
有機発光素子等の素子は、耐熱性が低いため、素子基板上に直接カラーフィルタを形成する製造工程での加熱処理は、例えば130℃以下、更に100℃以下で行うことが好ましいとされている。通常のカラーフィルタ製造工程ではガラス基板上で230℃程度の加熱処理を行って着色層を硬化させるのに対して、130℃以下や100℃以下の加熱処理では、熱によるメルトフローが起こらず、加熱処理後もアンダーカット形状のままになりやすいという課題がある。
一方で、酸価を有しない成分を使用して、アンダーカットを抑制する場合には、現像残渣が発生しやすいという課題がある。そのため、現像残渣の抑制と良好なパターン形状の両立は困難であった。
前記アルカリ可溶性樹脂は、酸価が50mgKOH/g超過であり、
前記非反応性樹脂は、酸価が7mgKOH/g~50mgKOH/gであり、メタクリル酸メチルに由来する構成単位の含有量が全構成単位中50質量%~99質量%であり、重量平均分子量が5000~50000である。
また、本発明に係る表示装置は、有機発光素子上に、前記本発明に係る感光性着色樹脂組成物の硬化膜を有する。
有機発光素子上に、前記本発明に係る感光性着色樹脂組成物を塗布することにより塗膜を形成する工程、
前記塗膜に光照射する工程、
前記光照射後の膜を、加熱するポストベイク工程、及び、
前記光照射後の膜を、現像する工程を含有することにより、
有機発光素子上に前記本発明に係る感光性着色樹脂組成物の硬化膜を形成する工程を有する。
本明細書において、ある部材又はある領域等のある構成が、他の部材又は他の領域等の他の構成の「上に(又は下に)」あるとする場合、特段の限定がない限り、これは他の構成の直上(又は直下)にある場合のみでなく、他の構成の上方(又は下方)にある場合を含み、すなわち、他の構成の上方(又は下方)において間に別の構成要素が含まれている場合も含む。
なお、本発明において光には、可視及び非可視領域の波長の電磁波、さらには放射線が含まれ、放射線には、例えばマイクロ波、電子線が含まれる。具体的には、波長5μm以下の電磁波、及び電子線のことをいう。
本発明において(メタ)アクリロイルとは、アクリロイル及びメタクリロイルの各々を表し、(メタ)アクリルとは、アクリル及びメタクリルの各々を表し、(メタ)アクリレートとは、アクリレート及びメタクリレートの各々を表す。
また、本明細書において数値範囲を示す「~」とは、その前後に記載された数値を下限値及び上限値として含む意味で使用される。
以下、本発明に係る感光性着色樹脂組成物、硬化物、カラーフィルタ、表示装置、及び有機発光素子と外光反射防止膜の積層体の製造方法について、順に詳細に説明する。
本発明に係る感光性着色樹脂組成物は、色材と、アルカリ可溶性樹脂と、非反応性樹脂と、光重合性化合物と、光開始剤と、溶剤とを含有を含有し、
前記アルカリ可溶性樹脂は、酸価が50mgKOH/g超過であり、
前記非反応性樹脂は、酸価が7mgKOH/g~50mgKOH/gであり、メタクリル酸メチルに由来する構成単位の含有量が全構成単位中50質量%~99質量%であり、重量平均分子量が5000~50000である。
酸価が特定以上のアルカリ可溶性樹脂に、前記特定の酸価、構成単位及び重量平均分子量を有する非反応性樹脂を組み合わせて含むことから、組み合わせの作用によって、未露光部の現像性が確保されるとともに、露光部の樹脂組成物層の下部が現像で流れにくくなり、現像後の断面のアンダーカットを抑制することができる。
組み合わせる非反応性樹脂の種類によっては、現像残渣が発生しやすくなるが、本発明で用いられる特定の非反応性樹脂は前記特定の酸価、構成単位及び重量平均分子量を有するように選択されていることから、酸価が特定以上のアルカリ可溶性樹脂と組み合わせた場合に、現像残渣を抑制することができる。
以下、このような本発明に係る感光性着色樹脂組成物の各成分について、順に詳細に説明する。
本発明において、色材は、カラーフィルタの着色層を形成した際に所望の発色が可能なものであればよく、特に限定されず、種々の有機顔料、無機顔料、分散可能な染料、染料の造塩化合物等を、単独で又は2種以上混合して用いることができる。中でも有機顔料は、発色性が高く、耐熱性も高いので、好ましく用いられる。有機顔料としては、例えばカラーインデックス(C.I.;The Society of Dyers and Colourists 社発行)においてピグメント(Pigment)に分類されている化合物、具体的には、下記のようなカラーインデックス(C.I.)番号が付されているものを挙げることができる。
C.I.ピグメントオレンジ1、5、13、14、16、17、24、34、36、38、40、43、46、49、51、61、63、64、71、73;
C.I.ピグメントバイオレット1、19、23、29、32、36、38;
C.I.ピグメントレッド1、2、3、4、5、6、7、8、9、10、11、12、14、15、16、17、18、19、21、22、23、30、31、32、37、38、40、41、42、48:1、48:2、48:3、48:4、49:1、49:2、50:1、52:1、53:1、57、57:1、57:2、58:2、58:4、60:1、63:1、63:2、64:1、81:1、83、88、90:1、97、101、102、104、105、106、108、112、113、114、122、123、144、146、149、150、151、166、168、170、171、172、174、175、176、177、178、179、180、185、187、188、190、193、194、202、206、207、208、209、215、216、220、224、226、242、243、245、254、255、264、265、269、272、291;
C.I.ピグメントブルー15、15:3、15:4、15:6、60;
C.I.ピグメントグリーン7、36、58、59、62、63;
C.I.ピグメントブラウン23、25;
C.I.ピグメントブラック1、7。
染料の造塩化合物としては、染料がカウンターイオンと塩を形成した化合物をいい、例えば、塩基性染料と酸との造塩化合物、酸性染料と塩基との造塩化合物が挙げられ、溶剤に可溶性の染料を公知のレーキ化(造塩化)手法を用いて、溶剤に不溶化したレーキ顔料も包含する。
本発明においては、染料及び染料の造塩化合物から選ばれる少なくとも一種を含む色材と、前記本発明の分散剤とを組み合わせて用いることにより当該色材の分散性や分散安定性を向上することができる。
なお、目安として、10gの溶剤(又は混合溶剤)に対して染料の溶解量が10mg以下であれば、当該溶剤(又は混合溶剤)において、当該染料が分散可能であると判定することができる。
銅フタロシアニン顔料としては、例えば、C.I.ピグメントブルー15、15:1、15:2、15:3、15:4、15:5、15:6、C.I.ピグメントグリーン7、36等が挙げられ、中でも、C.I.ピグメントブルー15:6が好ましい。
亜鉛フタロシアニン顔料としては、例えば、C.I.ピグメントグリーン58、59等が挙げられる。
キノフタロン染料としては、例えば、C.I.ディスパースイエロー54、64、67、134、149、160、C.I.ソルベントイエロー114、157等が挙げられ、中でも、C.I.ディスパースイエロー54が好ましい。
感光性着色樹脂組成物中の色材の平均分散粒径は、少なくとも溶剤を含有する分散媒体中に分散している色材粒子の分散粒径であって、レーザー光散乱粒度分布計により測定されるものである。レーザー光散乱粒度分布計による粒径の測定としては、感光性着色樹脂組成物に用いられている溶剤で、感光性着色樹脂組成物をレーザー光散乱粒度分布計で測定可能な濃度に適宜希釈(例えば、1000倍など)し、レーザー光散乱粒度分布計(例えば、日機装社製ナノトラック粒度分布測定装置UPA-EX150)を用いて動的光散乱法により23℃にて測定することができる。ここでの平均分布粒径は、体積平均粒径である。
尚、本発明において固形分は、後述する溶剤以外のもの全てであり、溶剤中に溶解しているモノマー等も含まれる。
本発明に用いられるアルカリ可溶性樹脂は酸価が50mgKOH/g超過であって、酸性基を有する樹脂であり、バインダー樹脂として作用し、かつパターン形成する際に用いられるアルカリ現像液に可溶性であるものの中から、適宜選択して使用することができる。
カルボキシ基含有エチレン性不飽和モノマーとしては、例えば、(メタ)アクリル酸、ビニル安息香酸、マレイン酸、マレイン酸モノアルキルエステル、フマル酸、イタコン酸、クロトン酸、桂皮酸、アクリル酸ダイマーなどが挙げられる。また、2-ヒドロキシエチル(メタ)アクリレートなどの水酸基を有する単量体と無水マレイン酸や無水フタル酸、シクロヘキサンジカルボン酸無水物のような環状無水物との付加反応物、ω-カルボキシ-ポリカプロラクトンモノ(メタ)アクリレートなども利用できる。また、カルボキシ基の前駆体として無水マレイン酸、無水イタコン酸、無水シトラコン酸などの無水物含有モノマーを用いてもよい。中でも、共重合性やコスト、溶解性、ガラス転移温度などの点から(メタ)アクリル酸が特に好ましい。
このような炭化水素環としては、置換基を有していてもよい環状の脂肪族炭化水素環、置換基を有していてもよい芳香族環、及びこれらの組み合わせが挙げられ、炭化水素環がカルボニル基、カルボキシ基、オキシカルボニル基、アミド基等の置換基を有していてもよい。中でも、脂肪族環を含む場合には、着色層の耐熱性や密着性が向上すると共に、得られた着色層の輝度が向上する。
炭化水素環の具体例としては、シクロプロパン、シクロブタン、シクロペンタン、シクロヘキサン、ノルボルナン、トリシクロ[5.2.1.0(2,6)]デカン(ジシクロペンタン)、アダマンタン等の脂肪族炭化水素環;ベンゼン、ナフタレン、アントラセン、フェナントレン、フルオレン等の芳香族環;ビフェニル、ターフェニル、ジフェニルメタン、トリフェニルメタン、スチルベン等の鎖状多環や、下記化学式(ii)に示されるカルド構造等が挙げられる。
前記一般式(iii)のRMにおける、置換されていてもよい炭化水素環の具体例としては、前記炭化水素環の具体例と同様のものが挙げられる。
また、前記化学式(ii)に示されるカルド構造を含む場合には、着色層の硬化性が向上し、耐溶剤性(NMP膨潤抑制)が向上する点から特に好ましい。
カルボキシ基を有する構成単位と、上記炭化水素環とを有する(メタ)アクリル系共重合体は、前述の“共重合可能なその他のモノマー”として炭化水素環を有するエチレン性不飽和モノマーを用いることにより調製することができる。
前記炭化水素環を有するエチレン性不飽和モノマーとしては、例えば、シクロヘキシル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、アダマンチル(メタ)アクリレート、イソボルニル(メタ)アクリレート、ベンジル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、スチレンなどが挙げられ、現像後の着色層の断面形状が加熱処理においても維持される効果が大きい点から、シクロヘキシル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、アダマンチル(メタ)アクリレート、ベンジル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、スチレンが好ましい。
アルカリ可溶性樹脂中に、エチレン性不飽和結合含有基を導入する方法は、従来公知の方法から適宜選択すればよい。例えば、アルカリ可溶性樹脂が有するカルボキシ基に、分子内にエポキシ基とエチレン性不飽和結合とを併せ持つ化合物、例えばグリシジル(メタ)アクリレート等を付加させ、側鎖にエチレン性不飽和結合を導入する方法や、水酸基を有する構成単位を共重合体に導入しておいて、分子内にイソシアネート基とエチレン性不飽和結合とを備えた化合物を付加させ、側鎖にエチレン性不飽和結合を導入する方法などが挙げられる。
カルボキシ基含有エチレン性不飽和モノマーの割合が上記下限値以上であると得られる塗膜のアルカリ現像液に対する溶解性が十分であり、また、カルボキシ基含有エチレン性不飽和モノマーの割合が上記上限値以下であると、アルカリ現像液による現像時に、形成されたパターンの基板からの脱落やパターン表面の膜荒れが起こり難い傾向がある。
なお、本発明における重量平均分子量(Mw)は、ポリスチレンを標準物質とし、THFを溶離液としてショウデックスGPCシステム-21H(Shodex GPC System-21H)により測定することができる。
エポキシ化合物、不飽和基含有モノカルボン酸、及び酸無水物は、公知のものの中から適宜選択して用いることができる。例えば、特許第6911365号公報の段落0226~0240の記載を参照して適宜用いることができる。カルボキシ基を有するエポキシ(メタ)アクリレート樹脂としては、例えば、グリシジル(メタ)アクリレート等のエポキシ基含有(メタ)アクリレートの重合体またはエポキシ基含有(メタ)アクリレートと他のエチレン性不飽和モノマーとの共重合体のエポキシ基の少なくとも一部に、不飽和基含有モノカルボン酸を付加させ、該付加反応により生じた水酸基の少なくとも一部に酸無水物を付加させて得られるアルカリ可溶性樹脂であってよい。
カルボキシ基を有するエポキシ(メタ)アクリレート樹脂は、それぞれ1種単独で使用してもよいし、二種以上を併用してもよい。
なお、本発明における酸価はJIS K 0070:1992に従って測定することができる。
ここで、エチレン性不飽和結合当量とは、上記アルカリ可溶性樹脂におけるエチレン性不飽和結合1モル当りの重量平均分子量のことであり、下記数式(1)で表される。
(数式(1)中、Wは、アルカリ可溶性樹脂の質量(g)を表し、Mはアルカリ可溶性樹脂W(g)中に含まれるエチレン性不飽和結合のモル数(mol)を表す。)
本発明に用いられる非反応性樹脂は、酸価が7mgKOH/g~50mgKOH/gであり、メタクリル酸メチルに由来する構成単位の含有量が全構成単位中50質量%~99質量%であり、重量平均分子量が5000~50000である。
本発明に用いられる非反応性樹脂は、基本的にエチレン性不飽和結合含有基、エポキシ基、オキセタン基、及びブロックイソシアネート基からなる群から選択される少なくとも1種の反応性基を有しない樹脂である。
カルボキシ基を有する構成単位としては、カルボキシ基含有エチレン性不飽和モノマー由来の構成単位が挙げられる。カルボキシ基含有エチレン性不飽和モノマーとしては、前記アルカリ可溶性樹脂で挙げたカルボキシ基含有エチレン性不飽和モノマーと同様であって良く、中でも、共重合性やコスト、溶解性などの点から(メタ)アクリル酸が特に好ましい。
カルボキシ基を有する構成単位の含有量は、酸価に合わせて適宜調整されればよいが、全構成単位中1質量%~10質量%の範囲から選択され、好ましくは2質量%以上、より好ましくは3質量%以上であり、好ましくは9質量%以下、より好ましくは8質量%以下である。
他の共重合可能なエチレン性不飽和モノマーとしては、中でも、アンダーカット形状抑制の点から、アルカリ可溶性の置換基を有しないものが良い。他の共重合可能なエチレン性不飽和モノマーとしては、例えば、メタクリル酸エチル、メタクリル酸ブチル、ベンジルメタクリレート、フェノキシエチルメタクリレート、シクロヘキシルメタクリレート、ジシクロペンタニルメタクリレート、イソボルニルメタクリレート、テトラヒドロフルフリルメタクリレート、メタクリル酸2-メトキシエチル、メタクリル酸2-エトキシエチル、メタクリル酸ジメチルアミノメチル、メタクリル酸ジエチルアミノエチル、3-メタクリロキシプロピルトリメトキシシラン、3-メタクリロキシプロピルメチルジメトキシシラン、3-メタクリロキシプロピルメチルジエトキシシラン、3-メタクリロキシプロピルトリエトキシシラン等が挙げられる。その他の構成単位は、2種以上混合して用いられてもよい。
当該その他の構成単位は、好ましくは49質量%以下、より好ましくは9質量%以下であり、5質量%以下であってよく、0質量%であってよい。
現像残渣抑制の点から重量平均分子量(Mw)は50000以下であり、好ましくは30000以下、より好ましくは20000以下である。
本発明に用いられる非反応性樹脂は、前記アルカリ可溶性樹脂と同様に調製することができる。
なお、アルカリ可溶性樹脂のガラス転移温度(Tg)は、JIS K7121に記載の方法に準ずる方法により、示差走査熱量測定(DSC)(例えば、SIIナノテクノロジー社製、EXSTAR DSC 7020)を用いて測定することができる。ガラス転移温度を示すピークが2つ以上見られる場合には、ピーク面積、すなわち、得られたチャートのベースラインから突出した部分の面積が最も大きいピークをガラス転移温度の代表値とする。
また、共重合体のガラス転移温度(Tg)は下記式で計算して目安とすることができる。
1/Tg=Σ(Xi/Tgi)
ここでは、共重合体はi=1からnまでのn個のモノマー成分が共重合しているとする。Xiはi番目のモノマーの重量分率(ΣXi=1)、Tgiはi番目のモノマーの単独重合体のガラス転移温度(絶対温度)である。ただしΣはi=1からnまでの和をとる。なお、各モノマーの単独重合体ガラス転移温度の値(Tgi)は、Polymer Handbook (3rd Edition) (J.Brandrup, E.H.Immergut著 (Wiley-Interscience、1989))の値を採用することができる。
感光性着色樹脂組成物において用いられる光重合性化合物としては、光重合性基を分子中に有する化合物が挙げられる。光重合性基としては、光開始剤によって重合可能なものであればよく、特に限定されないが、エチレン性不飽和結合含有基が挙げられ、例えば、ビニル基、アリル基、アクリロイル基又はメタクリロイル基等が挙げられる。光重合性基としては、中でも紫外線硬化性の点から、アクリロイル基又はメタクリロイル基が好適に用いられる。
光重合性化合物としては、硬化性の点から、1分子中に光重合性基を2個以上有する化合物を含有することが好ましく、1分子中に光重合性基を3個以上有する化合物を含有することがより好ましい。
このような多官能(メタ)アクリレートとしては、従来公知のものの中から適宜選択して用いればよい。具体例としては、例えば、特開2013-029832号公報に記載のもの等が挙げられる。
本発明の感光性着色樹脂組成物において用いられる光開始剤としては、従来知られている各種光開始剤の中から、1種又は2種以上を組み合わせて用いることができる。
光開始剤としては、例えば、芳香族ケトン類、ベンゾインエーテル類、ハロメチルオキサジアゾール化合物、α-アミノケトン類、ビイミダゾール類、N,N-ジメチルアミノベンゾフェノン、ハロメチル-S-トリアジン系化合物、チオキサントン、オキシムエステル類等を挙げることができる。このような光開始剤としては、従来公知の光開始剤を用いることができ、例えば、国際公開2018/062105号公報に記載されている光開始剤が挙げられる。
R11、R12及びR13は、それぞれ独立に、水素原子、炭素数1~20のアルキル基、炭素数6~30のアリール基、炭素数7~30のアリールアルキル基又は炭素数2~20の複素環基を表し、
R11、R12及びR13で表される基の水素原子は、更にR21、OR21、COR21、SR21、NR22R23、CONR22R23、-NR22-OR23、-NCOR22-OCOR23、NR22COR21、OCOR21、COOR21、SCOR21、OCSR21、COSR21、CSOR21、水酸基、ニトロ基、CN、又はハロゲン原子で置換されていてもよく、
R21、R22及びR23は、それぞれ独立に、水素原子、炭素数1~20のアルキル基、炭素数6~30のアリール基、炭素数7~30のアリールアルキル基又は炭素数2~20の複素環基を表し、
R21、R22及びR23で表される基の水素原子は、更に水酸基、ニトロ基、CN、ハロゲン原子、又はカルボキシ基で置換されていてもよく、
R11、R12、R13、R21、R22及びR23で表される基のアルキレン部分は、-O-、-S-、-COO-、-OCO-、-NR24-、-NR24CO-、-NR24COO-、-OCONR24-、-SCO-、-COS-、-OCS-又は-CSO-を酸素原子が隣り合わない条件で1~5個含んでいてもよく、
R24は、水素原子、炭素数1~20のアルキル基、炭素数6~30のアリール基、炭素数7~30のアリールアルキル基又は炭素数2~20の複素環基を表し、
R11、R12、R13、R21、R22、R23及びR24で表される基のアルキル部分は、分岐側鎖があってもよく、環状アルキルであってもよく、
R3は、水素原子、炭素数1~20のアルキル基、炭素数6~30のアリール基、炭素数7~30のアリールアルキル基又は炭素数2~20の複素環基を表し、R3で表される基のアルキル部分は、分岐側鎖があってもよく、環状アルキルであってもよく、また、R3とR7、及びR3とR8はそれぞれ一緒になって環を形成していてもよく、
R3で表される基の水素原子は、更にR21、OR21、COR21、SR21、NR22R23、CONR22R23、-NR22-OR23、-NCOR22-OCOR23、NR22COR21、OCOR21、COOR21、SCOR21、OCSR21、COSR21、CSOR21、水酸基、ニトロ基、CN、又はハロゲン原子で置換されていてもよく、
R4、R5、R6及びR7は、それぞれ独立に、R11、OR11、SR11、COR14、CONR15R16、NR12COR11、OCOR11、COOR14、SCOR11、OCSR11、COSR14、CSOR11、水酸基、CN又はハロゲン原子を表し、R4とR5、R5とR6、及びR6とR7はそれぞれ一緒になって環を形成していてもよく、
R14、R15及びR16は、水素原子又は炭素数1~20のアルキル基を表し、R14、R15及びR16で表される基のアルキル部分は、分岐側鎖があってもよく、環状アルキルであってもよく、R8は、R11、OR11、SR11、COR11、CONR12R13、NR12COR11、OCOR11、COOR11、SCOR11、OCSR11、COSR11、CSOR11、水酸基、CN又はハロゲン原子を表し、
kは、0又は1を表す。)
R41、R42及びR43は、それぞれ独立に、水素原子、炭素数1~20のアルキル基、炭素数6~30のアリール基、炭素数7~30のアリールアルキル基又は炭素数2~20の複素環基を表し、
R41、R42及びR43、並びにX2で表される基の水素原子は、更にR51、OR51、COR51、SR51、NR52R53、CONR52R53、-NR52-OR53、-NCOR52-OCOR53、NR52COR51、OCOR51、COOR51、SCOR51、OCSR51、COSR51、CSOR51、水酸基、ニトロ基、CN、又はハロゲン原子で置換されていてもよく、
R51、R52及びR53は、それぞれ独立に、水素原子、炭素数1~20のアルキル基、炭素数6~30のアリール基、炭素数7~30のアリールアルキル基又は炭素数2~20の複素環基を表し、
R51、R52及びR53で表される基の水素原子は、更に水酸基、ニトロ基、CN、ハロゲン原子、又はカルボキシ基で置換されていてもよく、
R41、R42、R43、X2、R51、R52及びR53で表される基のアルキレン部分は、-O-、-S-、-COO-、-OCO-、-NR54-、-NR54CO-、-NR54COO-、-OCONR54-、-SCO-、-COS-、-OCS-又は-CSO-を酸素原子が隣り合わない条件で1~5個含んでいてもよく、
R54は、水素原子、炭素数1~20のアルキル基、炭素数6~30のアリール基、炭素数7~30のアリールアルキル基又は炭素数2~20の複素環基を表し、
R41、R42、R43、R51、R52、R53及びR54で表される基のアルキル部分は、分岐側鎖があってもよく、環状アルキルであってもよい。
a及びbは、それぞれ独立に、0~3の整数である。)
前記一般式(A)で表されるオキシムエステル化合物には、オキシムの二重結合による幾何異性体が存在するが、これらを区別するものではない。即ち、本明細書において、前記一般式(A)で表わされる化合物、並びに後述する該化合物の好ましい形態である下記一般式(A’)で表わされる化合物及びその例示化合物は、両方の混合物又はどちらか一方を表すものであり、異性体を示した構造に限定するものではない。
上記一般式(A)中の、R4とR5、R5とR6及びR6とR7並びにR3とR7及びR3とR8が一緒になって形成し得る環としては、例えば、シクロペンタン環、シクロヘキサン環、シクロペンテン環、ベンゼン環、ピペリジン環、モルホリン環、ラクトン環、ラクタム環等の5~7員環が好ましく挙げられる。
上記一般式(A)で表される化合物の中でも、R3が縮合していてもよい芳香族環であるもの、あるいは下記一般式(A’)で表される化合物は、感度が高く、製造が容易であるため好ましい。
前記一般式(B)で表されるオキシムエステル化合物にも、オキシムの二重結合による幾何異性体が存在するが、これらを区別するものではない。即ち、本明細書において、前記一般式(B)で表わされる化合物及びその例示化合物は、両方の混合物又はどちらか一方を表すものであり、異性体を示した構造に限定するものではない。
上記一般式(B)中の、X2、R41、R42、R43、R51、R52、R53及びR54で表される炭素数6~30のアリール基としては、前記一般式(A)における炭素数6~30のアリール基と同様のものが挙げられる。
上記一般式(B)中の、X2、R41、R42、R43、R51、R52、R53及びR54で表される炭素数7~30のアリールアルキル基としては、前記一般式(A)における炭素数7~30のアリールアルキル基と同様のものが挙げられる。
上記一般式(B)中の、X2、R41、R42、R43、R51、R52、R53及びR54で表される炭素数2~20の複素環基としては、前記一般式(A)における炭素数2~20の複素環基と同様のものが挙げられる。
また、上記一般式(B)中のハロゲン原子としては、前記一般式(A)におけるハロゲン原子と同様のものが挙げられる。
X3、及びX6は、それぞれ独立に、感度、溶解性、相溶性の点から、さらに好ましくは炭素数が1~6のアルキル基である。
X2は感度、溶解性、相溶性の点から、さらに好ましくは炭素数が2~6のメチレン鎖中に1つのエーテル結合を有するアルキル基である。
a及びbは、それぞれ独立に、0~3の整数であるが、0~1の整数であってよく、0であってよい。
本発明に用いられる溶剤としては、感光性着色樹脂組成物中の各成分とは反応せず、これらを溶解もしくは分散可能な有機溶剤であればよく、特に限定されない。溶剤は単独もしくは2種以上組み合わせて使用することができる。
溶剤の具体例としては、例えば、メチルアルコール、エチルアルコール、N-プロピルアルコール、i-プロピルアルコール、メトキシアルコール、エトキシアルコールなどのアルコール系溶剤;メトキシエトキシエタノール、エトキシエトキシエタノールなどのカルビトール系溶剤;酢酸エチル、酢酸ブチル、メトキシプロピオン酸メチル、メトキシプロピオン酸エチル、エトキシプロピオン酸エチル、乳酸エチル、ヒドロキシプロピオン酸メチル、ヒドロキシプロピオン酸エチル、n-ブチルアセテート、イソブチルアセテート、酪酸イソブチル、酪酸n-ブチル、乳酸エチル、シクロヘキサノールアセテートなどのエステル系溶剤;アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、2-ヘプタノンなどのケトン系溶剤;メトキシエチルアセテート、プロピレングリコールモノメチルエーテルアセテート、3-メトキシ-3-メチル-1-ブチルアセテート、3-メトキシブチルアセテート、エトキシエチルアセテートなどのグリコールエーテルアセテート系溶剤;メトキシエトキシエチルアセテート、エトキシエトキシエチルアセテート、ブチルカルビトールアセテート(BCA)などのカルビトールアセテート系溶剤;プロピレングリコールジアセテート、1,3-ブチレングリコールジアセテート等のジアセテート類;エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテル、ジプロピレングリコールジメチルエーテルなどのグリコールエーテル系溶剤;N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチルピロリドンなどの非プロトン性アミド溶剤;γ-ブチロラクトンなどのラクトン系溶剤;テトラヒドロフランなどの環状エーテル系溶剤;ベンゼン、トルエン、キシレン、ナフタレンなどの不飽和炭化水素系溶剤;N-ヘプタン、N-ヘキサン、N-オクタンなどの飽和炭化水素系溶剤;トルエン、キシレン等の芳香族炭化水素類などの有機溶剤が挙げられる。これらの溶剤の中ではグリコールエーテルアセテート系溶剤、カルビトールアセテート系溶剤、グリコールエーテル系溶剤、エステル系溶剤が他の成分の溶解性の点で好適に用いられる。中でも、本発明に用いる溶剤としては、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、ブチルカルビトールアセテート(BCA)、3-メトキシ-3-メチル-1-ブチルアセテート、エトキシプロピオン酸エチル、乳酸エチル、及び、3-メトキシブチルアセテートよりなる群から選択される1種以上であることが、他の成分の溶解性や塗布適性の点から好ましい。
本発明の感光性着色樹脂組成物において、色材を分散させる場合には、色材分散性と色材分散安定性の点から、分散剤を更に含んでいても良い。
本発明において分散剤は、従来公知の分散剤の中から適宜選択して用いることができる。分散剤としては、例えば、カチオン系、アニオン系、ノニオン系、両性、シリコーン系、フッ素系等の界面活性剤を使用できる。界面活性剤の中でも、均一に、微細に分散し得る点から、高分子分散剤が好ましい。
(メタ)アクリレート共重合体系分散剤は、色材吸着部位として機能する構成単位と、溶剤親和性部位として機能する構成単位とを含有する共重合体であることが好ましく、溶剤親和性部位として機能する構成単位に少なくとも(メタ)アクリレート由来の構成単位を含むことが好ましい。
塩基性基含有エチレン性不飽和モノマー由来の構成単位としては、下記一般式(I)で表される構成単位が、分散性に優れている点から好ましい。
中でも、分散性の点から、一般式(I)におけるA1は、-CONH-基又は-COO-基を含む2価の連結基であることが好ましく、-CONH-基又は-COO-基と、炭素数1~10のアルキレン基とを含む2価の連結基であることがより好ましい。
アルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、イソプロピル基、tert-ブチル基、2-エチルヘキシル基、シクロペンチル基、シクロヘキシル基等が挙げられ、アルキル基の炭素数は、1~18が好ましく、中でも、メチル基又はエチル基であることがより好ましい。
アラルキル基としては、例えば、ベンジル基、フェネチル基、ナフチルメチル基、ビフェニルメチル基等が挙げられる。アラルキル基の炭素数は、7~20が好ましく、更に7~14が好ましい。
また、アリール基としては、フェニル基、ビフェニル基、ナフチル基、トリル基、キシリル基等が挙げられる。アリール基の炭素数は、6~24が好ましく、更に6~12が好ましい。なお、上記好ましい炭素数には、置換基の炭素数は含まれない。
ヘテロ原子を含む炭化水素基とは、上記炭化水素基中の炭素原子がヘテロ原子で置き換えられた構造を有するか、上記炭化水素基中の水素原子がヘテロ原子を含む置換基で置き換えられた構造を有する。炭化水素基が含んでいてもよいヘテロ原子としては、例えば、酸素原子、窒素原子、硫黄原子、ケイ素原子等が挙げられる。
また、炭化水素基中の水素原子は、フッ素原子、塩素原子、臭素原子等のハロゲン原子により置換されていてもよい。
重合体において、一般式(I)で表される構成単位は、1種類からなるものであってもよく、2種以上の構成単位を含むものであってもよい。
前記有機酸化合物としては、中でも、下記一般式(1)で表される化合物及び下記一般式(3)で表される化合物が好ましく、前記ハロゲン化炭化水素としては、中でも、下記一般式(2)で表される化合物が好ましい。すなわち、前記有機酸化合物及びハロゲン化炭化水素からなる群から選ばれる少なくとも1種としては、下記一般式(1)~(3)よりなる群から選択される1種以上の化合物を好ましく用いることができる。
前記有機酸化合物がフェニルホスホン酸やフェニルホスフィン酸等の酸性有機リン化合物であることが、色材の分散性及び分散安定性に優れる点から好ましい。このような分散剤に用いられる有機酸化合物の具体例としては、例えば、特開2012-236882号公報等に記載の有機酸化合物が好適なものとして挙げられる。
また、前記ハロゲン化炭化水素としては、臭化アリル、塩化ベンジル等のハロゲン化アリル及びハロゲン化アラルキルの少なくとも1種であることが、色材の分散性及び分散安定性に優れる点から好ましい。
なお、有機酸化合物及びハロゲン化炭化水素からなる群から選ばれる少なくとも1種は、1種単独で用いてもよく、2種以上を組み合わせてもよい。2種以上を組み合わせる場合は、その合計の含有量が上記範囲内であることが好ましい。
なお、共重合体の当該一般式(I)で表される構成単位が有する末端の窒素部位と、前記有機酸化合物及びハロゲン化炭化水素からなる群から選ばれる少なくとも1種とが塩を形成していること、及びその割合は、例えばNMR等、公知の手法により確認することができる。
前記グラフト共重合体において、(メタ)アクリレート由来の構成単位を有するグラフトポリマー鎖としては、従来公知の構造を適宜選択して用いることができる。例えば、国際公開第2021/006077号公報に記載されているグラフト共重合体及び塩型グラフト共重合体の少なくとも1種を用いてもよい。
また、前記ブロック共重合体において、(メタ)アクリレート由来の構成単位を含むBブロックとしては、従来公知の構造を適宜選択して用いることができる。例えば、国際公開第2016/104493号に記載されているブロック共重合体及び塩型ブロック共重合体の少なくとも1種を用いてもよい。
この場合のBブロックは、(メタ)アクリレート由来の構成単位を必須成分として含むが、国際公開第2016/104493号のBブロックと同様であってよい。
アミン価が上記範囲内であることにより、粘度の経時安定性や耐熱性に優れると共に、アルカリ現像性や、溶剤再溶解性にも優れている。本発明において、前記一般式(I)で表される構成単位を含む(メタ)アクリレート系共重合体のアミン価は、中でも、アミン価が80mgKOH/g以上であることが好ましく、90mgKOH/g以上であることがより好ましい。一方、溶剤再溶解性の点から、前記一般式(I)で表される構成単位を含む(メタ)アクリレート系共重合体のアミン価は、110mgKOH/g以下であることが好ましく、105mgKOH/g以下であることがより好ましい。
アミン価は、試料1g中に含まれるアミン成分を中和するのに要する過塩素酸と当量の水酸化カリウムのmg数をいい、JIS-K7237に定義された方法により測定することができる。当該方法により測定した場合には、分散剤中の有機酸化合物と塩形成しているアミノ基であっても、通常、当該有機酸化合物が解離するため、分散剤として用いられるブロック共重合体そのもののアミン価を測定することができる。
本発明の感光性着色樹脂組成物は、低温加熱処理後の耐溶剤性を向上する点から、更に、多官能エポキシ化合物及び多官能ブロックイソシアネート化合物の少なくとも1種を含有することが好ましい。
多官能エポキシ化合物は、1分子中に2つ以上のエポキシ基を有する化合物である。
エポキシ基とは、3員環の環状エーテル構造を含む基を意味し、脂環式エポキシ基も含む。エポキシ基としては、オキシラニル基、3,4-エポキシシクロヘキシル基等が挙げられる。これらのエポキシ基は、水素原子の一部又は全部がアルキル基等の置換基で置換されたものであってもよい。
ブロックイソシアネート基は、イソシアネート基をブロック化剤でブロックした基である。多官能ブロックイソシアネート化合物は、室温付近では安定を保ち、熱処理することによってブロック化剤が乖離し、活性イソシアネート基が再生されるものであり、イソシアネート基が1分子中に2つ以上の多官能イソシアネート化合物とブロック化剤を反応させることにより得られる。
これらのイソシアネート化合物の中では、透明性の点から、脂環式ジイソシアネート、脂肪族ジイソシアネートがより好ましい。
一方、ブロック化剤としては、公知のブロック化剤を適宜選択して用いることができ、中でもマロン酸ジメチル、マロン酸ジエチル、マロン酸ジベンジル、マロン酸ジエチルメチル等のカルボン酸エステル類;マロン酸、アセチルアセトン、アセト酢酸エステル(アセト酢酸メチル、アセト酢酸エチル等)等の活性メチレン化合物、3,5-ジメチルピラゾール等が好適に用いられる。
本発明の感光性着色樹脂組成物は、低温加熱処理後の耐溶剤性、及び基板密着性を向上する点から、更に、チオール化合物を含有することが好ましい。
チオール化合物としては、1分子中に1つのチオール基を有する単官能チオール化合物、1分子中に2つ以上のチオール基を有する多官能チオール化合物が挙げられる。線幅シフトの抑制と基板密着性の向上の点からは、チオール基が1つの単官能チオール化合物を用いることがより好ましい。
単官能チオール化合物としては、例えば、2-メルカプトベンゾチアゾール、2-メルカプトベンゾオキサゾール、2-メルカプトベンゾイミダゾール、2-メルカプト-5-メトキシベンゾチアゾール、2-メルカプト-5-メトキシベンゾイミダゾール、3-メルカプトプロピオン酸、3-メルカプトプロピオン酸メチル、3-メルカプトプロピオン酸エチル、3-メルカプトプロピオン酸オクチル等が挙げられる。
多官能チオール化合物としては、例えば、1,4-ビス(3-メルカプトブチリルオキシ)ブタン、1,3,5-トリス(3-メルカプトブチルオキシエチル)-1,3,5-トリアジン-2,4,6(1H,3H,5H)-トリオン、トリメチロールプロパントリス(3-メルカプトプロピオネート)、ペンタエリスリトールテトラキス(3-メルカプトブチレート)、ペンタエリスリトールテトラキス(3-メルカプトプロピオネート)、ジペンタエリスリトールヘキサキス(3-メルカプトプロピオネート)、およびテトラエチレングリコールビス(3-メルカプトプロピオネート)等が挙げられる。
チオール化合物としては、単独で又は2種以上組み合わせて用いても良く、中でも、2-メルカプトベンゾオキサゾール、又は2-メルカプトベンゾチアゾールが、低温加熱処理後の耐溶剤性、及び基板密着性を向上する点から好ましい。
チオール化合物の含有量としては、感光性着色樹脂組成物の固形分全量に対して、通常0.5質量%~10質量%、好ましくは1質量%~5質量%の範囲内である。上記下限値以上であれば、低温加熱処理後の耐溶剤性、及び基板密着性に優れている。一方、上記上限値以下であれば、本発明の感光性着色樹脂組成物を 現像性が良好で線幅シフトが抑制されたものとしやすい。
本発明の感光性着色樹脂組成物には、必要に応じて、更に各種添加剤を含むものであってもよい。添加剤としては、例えば、酸化防止剤、重合停止剤、連鎖移動剤、レベリング剤、可塑剤、界面活性剤、消泡剤、シランカップリング剤、紫外線吸収剤、密着促進剤等などが挙げられる。
界面活性剤及び可塑剤の具体例としては、例えば、特開2013-029832号公報に記載のものが挙げられる。
本発明に用いられる酸化防止剤としては、特に限定されず、従来公知のものの中から適宜選択すればよい。酸化防止剤の具体例としては、例えば、ヒンダードフェノール系酸化防止剤、アミン系酸化防止剤、リン系酸化防止剤、硫黄系酸化防止剤、ヒドラジン系酸化防止剤等が挙げられ、線幅マスク線幅の設計通りに細線パターンを形成する能力が向上する点、及び耐熱性の点から、ヒンダードフェノール系酸化防止剤を用いることが好ましい。国際公開第2014/021023号に記載されているような潜在性酸化防止剤であっても良い。
本発明の感光性着色樹脂組成物の製造方法は、色材と、アルカリ可溶性樹脂と、非反応性樹脂と、光重合性化合物と、光開始剤と、溶剤と、所望により用いられる各種添加成分とを、公知の混合手段を用いて混合することにより、調製することができる。
本発明の感光性着色樹脂組成物が、例えば色材と、アルカリ可溶性樹脂と、非反応性樹脂と、光重合性化合物と、光開始剤と、分散剤と、溶剤と、所望により用いられる各種添加成分とを含有する場合、当該樹脂組成物の調製方法としては、例えば、(1)まず溶剤中に、色材と、分散剤とを添加して色材分散液を調製し、当該分散液に、アルカリ可溶性樹脂と、非反応性樹脂と、光重合性化合物と、光開始剤と、所望により用いられる各種添加成分を混合する方法;(2)溶剤中に、色材と、分散剤と、アルカリ可溶性樹脂と、非反応性樹脂と、光重合性化合物と、光開始剤と、所望により用いられる各種添加成分とを同時に投入し混合する方法;(3)溶剤中に、分散剤と、アルカリ可溶性樹脂と、非反応性樹脂と、光重合性化合物と、光開始剤と、所望により用いられる各種添加成分とを添加し、混合したのち、色材を加えて分散する方法;(4)溶剤中に、色材と、分散剤と、アルカリ可溶性樹脂とを添加して色材分散液を調製し、当該分散液に、更にアルカリ可溶性樹脂と、非反応性樹脂と、溶剤と、光重合性化合物と、光開始剤と、所望により用いられる各種添加成分を添加し、混合する方法;などを挙げることができる。
これらの方法の中で、上記(1)及び(4)の方法が、色材の凝集を効果的に防ぎ、均一に分散させ得る点から好ましい。
分散剤を用いない場合には、分散剤を除き、上記(2)、(3)、又は(4)の方法において調製すればよい。
本発明に係る感光性着色樹脂組成物は、低温加熱処理でも、現像残渣の発生を抑制し、且つパターン形状が良好な着色層を形成可能であることから、カラーフィルタ用途に好適に用いることができ、中でも有機発光素子等、耐熱性が低い素子が形成された基板上に直接カラーフィルタを形成する130℃以下、更に100℃以下や90℃以下の低温加熱処理用途等に好適に用いることができ、有機発光素子上に形成する硬化膜に好適に用いることができる。
また、本発明に係る感光性着色樹脂組成物は、有機発光素子上に形成する硬化膜に用いることができることから、外光反射抑制効果を有する円偏光板代替の着色硬化膜の形成に好適に用いられる。本発明に係る感光性着色樹脂組成物の硬化膜を円偏光板の代替に用いる場合には、偏光板を含まない表示装置とすることができるため、本発明に係る感光性着色樹脂組成物は、偏光板を含まない表示装置用途に好適に用いられる。
また、本発明に係る感光性着色樹脂組成物は、有機発光素子上に形成する硬化膜に用いる感光性着色樹脂組成物であることから、外付けのカラーフィルタ基板を含まない表示装置用途、薄膜でフレキシブル性が向上した有機発光表示装置用途に好適に用いられる。
本発明に係る硬化物は、前記本発明に係る感光性着色樹脂組成物の硬化物である。
本発明に係る硬化物は、例えば、前記本発明に係る感光性着色樹脂組成物の塗膜を形成し、該塗膜を乾燥させたのち、露光、及び必要に応じて現像、加熱処理により得ることができる。塗膜の形成、露光、現像、及び加熱処理の方法としては、例えば、後述する本発明に係るカラーフィルタが備える着色層の形成において用いられる方法と同様の方法とすることができる。
本発明に係る硬化物は、加熱処理が130℃以下、更に100℃以下や90℃以下という低温の加熱処理であっても、耐溶剤性が良好であり、且つパターン形状が良好である。
本発明に係る硬化物は、低温加熱処理でも耐溶剤性が良好で、且つパターン形状が良好であり、カラーフィルタの着色層として好適に用いられ、有機発光素子上に形成する硬化膜に好適に用いられる。
本発明に係るカラーフィルタは、基板と、当該基板上に設けられた着色層とを少なくとも備えるカラーフィルタであって、当該着色層の少なくとも1つが、前記本発明に係る感光性着色樹脂組成物の硬化物である。
本発明のカラーフィルタに用いられる着色層は、少なくとも1つが、前記本発明に係る感光性着色樹脂組成物の硬化物である着色層である。
着色層は、通常、後述する基板上の遮光部の開口部に形成され、通常3色以上の着色パターンから構成される。
また、当該着色層の配列としては、特に限定されず、例えば、ストライプ型、モザイク型、トライアングル型、4画素配置型等の一般的な配列とすることができる。また、着色層の幅、面積等は任意に設定することができる。
当該着色層の厚みは、塗布方法、感光性着色樹脂組成物の固形分濃度や粘度等を調整することにより、適宜制御されるが、通常、1~5μmの範囲であることが好ましい。
まず、前述した本発明の感光性着色樹脂組成物を、スプレーコート法、ディップコート法、バーコート法、ロールコート法、スピンコート法、ダイコート法などの塗布手段を用いて後述する基板上に塗布して、ウェット塗膜を形成させる。なかでもスピンコート法、ダイコート法を好ましく用いることができる。
次いで、ホットプレートやオーブンなどを用いて、該ウェット塗膜を乾燥させたのち、これに、所定のパターンのマスクを介して露光し、アルカリ可溶性樹脂及び多官能モノマー等を光重合反応させて硬化塗膜とする。露光に使用される光源としては、例えば低圧水銀灯、高圧水銀灯、メタルハライドランプなどの紫外線、電子線等が挙げられる。露光量は、使用する光源や塗膜の厚みなどによって適宜調整される。
また、露光後に重合反応を促進させるために、加熱処理を行ってもよい。加熱条件は、使用する感光性着色樹脂組成物中の各成分の配合割合や、塗膜の厚み等によって適宜選択される。
現像処理後は、通常、現像液の洗浄、感光性着色樹脂組成物の硬化塗膜の乾燥が行われ、着色層が形成される。なお、現像処理後に、塗膜を十分に硬化させるために加熱処理を行ってもよい。加熱条件としては特に限定はなく、塗膜の用途に応じて適宜選択される。
素子基板上に直接着色層を形成する製造工程での加熱処理は、30℃以上100℃以下で行うことが好ましく、35℃以上95℃以下で行うことがより好ましく、40℃以上90℃以下で行うことが更に好ましい。
本発明のカラーフィルタにおける遮光部は、後述する基板上にパターン状に形成されるものであって、一般的なカラーフィルタに遮光部として用いられるものと同様とすることができる。
当該遮光部のパターン形状としては、特に限定されず、例えば、ストライプ状、マトリクス状等の形状が挙げられる。遮光部は、スパッタリング法、真空蒸着法等によるクロム等の金属薄膜であっても良い。或いは、遮光部は、樹脂バインダー中にカーボン微粒子、金属酸化物、無機顔料、有機顔料等の遮光性粒子を含有させた樹脂層であってもよい。遮光性粒子を含有させた樹脂層の場合には、感光性レジストを用いて現像によりパターニングする方法、遮光性粒子を含有するインクジェットインクを用いてパターニングする方法、感光性レジストを熱転写する方法等がある。
基板としては、後述する透明基板、シリコン基板、及び、透明基板又はシリコン基板上にアルミニウム、銀、銀/銅/パラジウム合金薄膜などを形成したものが用いられる。これらの基板上には、別のカラーフィルタ層、樹脂層、TFT等のトランジスタ、回路等が形成されていてもよい。基板としては、後述する有機発光素子のような素子基板であってもよい。
本発明のカラーフィルタにおける透明基板としては、可視光に対して透明な基材であればよく、特に限定されず、一般的なカラーフィルタに用いられる透明基板を使用することができる。具体的には、石英ガラス、無アルカリガラス、合成石英板等の可撓性のない透明なリジッド材、あるいは、透明樹脂フィルム、光学用樹脂板、フレキシブルガラス等の可撓性を有する透明なフレキシブル材が挙げられる。透明樹脂フィルム、光学用樹脂板としては、例えば、ポリエチレンテレフタレート(PET)フィルム、ポリイミドフィルム、ポリカーボネートフィルム等が挙げられるが、中でも酸素原子、窒素原子等のヘテロ原子を含むPETフィルム、ポリイミドフィルム等が好適に用いられる。
当該透明基板の厚みは、特に限定されるものではないが、本発明のカラーフィルタの用途に応じて、例えば100μm~1mm程度のものを使用することができる。
なお、本発明のカラーフィルタは、上記基板、遮光部及び着色層以外にも、例えば、オーバーコート層や透明電極層、さらには配向膜や柱状スペーサ等が形成されたものであってもよい。
また、本発明のカラーフィルタは、外光反射を防止する円偏光板代替としても利用できる。
本発明に係る表示装置は、前記本発明に係るカラーフィルタを有することを特徴とする。本発明において表示装置の構成は特に限定されず、従来公知の表示装置の中から適宜選択することができ、例えば、液晶表示装置や、有機発光表示装置などが挙げられる。
本発明の液晶表示装置としては、例えば、前述した本発明に係るカラーフィルタと、対向基板と、前記カラーフィルタと前記対向基板との間に形成された液晶層とを有する液晶表示装置が挙げられる。
このような本発明の液晶表示装置について、図を参照しながら説明する。図2は、本発明の液晶表示装置の一例を示す概略図である。図2に例示するように本発明の液晶表示装置40は、カラーフィルタ10と、TFTアレイ基板等を有する対向基板20と、上記カラーフィルタ10と上記対向基板20との間に形成された液晶層30とを有している。
なお、本発明の液晶表示装置は、この図2に示される構成に限定されるものではなく、一般的にカラーフィルタが用いられた液晶表示装置として公知の構成とすることができる。
また、対向基板としては、本発明の液晶表示装置の駆動方式等に応じて適宜選択して用いることができる。
さらに、液晶層を構成する液晶としては、本発明の液晶表示装置の駆動方式等に応じて、誘電異方性の異なる各種液晶、及びこれらの混合物を用いることができる。
本発明の有機発光表示装置としては、例えば、前述した本発明に係るカラーフィルタと、有機発光素子とを有する有機発光表示装置が挙げられる。
このような本発明の有機発光表示装置について、図を参照しながら説明する。図3は、本発明の有機発光表示装置の一例を示す概略図である。図3に例示するように本発明の有機発光表示装置100は、基板50上に有機発光素子80と封止層90が形成され、その上にカラーフィルタ10が形成されている。基板50としては、フレキシブル基板上にTFTが形成されている基板であってよい。図3の有機発光表示装置において、カラーフィルタ10は、円偏光板代替カラーフィルタであって良い。
なお、本発明の有機発光表示装置は、この図3に示される構成に限定されるものではなく、一般的にカラーフィルタが用いられた有機発光表示装置として公知の構成とすることができる。
このような本発明に係る表示装置は、前記本発明に係る感光性着色樹脂組成物の硬化膜が、有機発光素子上に形成されているものであることから、外付けの円偏光板や、外付けのカラーフィルタ基板が不要であり、これらを有しないものであってよい。
このような本発明に係る表示装置は、前記本発明に係る感光性着色樹脂組成物を用いて、有機発光素子上に硬化膜が形成されることから、有機発光素子と硬化膜の間に外付けのカラーフィルタ基板に用いられるような基板を有しないため、薄膜化とフレキシブル性が向上したものである。
前記有機発光素子を備えた素子基板130は、基板101上に駆動素子である薄膜トランジスタ(TFT)102が各サブピクセルに対応するよう配置され、その上に封止膜103を備え、さらに封止膜103上には各サブピクセルに対応する電極104(陽極)、各サブピクセルを区画する隔壁105を備え、その区画内にR、G,B3色のサブピクセルを構成する有機発光素子(106R、106G、106B)が配置され、当該有機発光素子(106R、106G、106B)上に、更に電極107(陰極)を備えている。前記有機発光素子を備えた素子基板130は、さらにその上から有機発光素子を覆う封止層108を備える。
素子基板130における有機EL素子(106R、106G、106B)上の封止層108上に、光硬化性着色樹脂組成物を用いて形成される各有機EL素子に対応した3色の着色硬化膜(109R、109G、109B)及び遮光部110を含む外光反射防止膜120を備え、更にその上に封止膜111を備える。
図4の本発明に係る表示装置200は、封止膜111の上に、更に、透明粘着剤層112を介してカバー材113を備えている。
本発明に係る表示装置200は、図示しないが、例えば、さらに封止膜111上に絶縁膜および透明電極層からなるタッチセンサー層を備え、さらにタッチセンサー層上にハードコート層等、公知の構成をさらに適宜備えていてよいものである。
上記のように、前記有機発光素子を備えた素子基板130上に設けられた、着色硬化膜(109R、109G、109B)及び遮光部110の層が、外光反射防止膜120として用いられることから、本発明に用いられる外光反射防止膜は、外付けの円偏光板や外付けのカラーフィルタ基板のように別途基板が含まれず、薄膜化及びフレキシブル性を向上できる。
前記本発明に係る感光性着色樹脂組成物の硬化膜は、前記3色の着色硬化膜(109R、109G、109B)のうち、いずれか1つであってもよいが、全てであってもよい。
有機発光素子には、発光層の他に、正孔注入層、正孔輸送層、電子注入層等、公知の構成を備えていてもよい。
具体的には例えば、金属膜、金属酸化物膜、SiOx、SiON、SiNx等の無機膜と有機膜を積層した多層膜等が挙げられる。
着色硬化膜は、通常、有機発光素子上の封止層108上の後述する遮光部の開口部に形成され、通常3色以上の着色パターンから構成される。これらは有機発光素子のサブピクセルの(106R、106G、106B)と同様の着色パターンであってよい。
着色硬化膜(109R、109G、109B)の配列としては、例えば、ストライプ型、モザイク型、トライアングル型、4画素配置型等の一般的な配列とすることができる。また、着色層の幅、面積等は有機発光素子のサブピクセルの(106R、106G、106B)に適合するように適宜設定することができる。
当該着色硬化膜の厚みは、塗布方法、感光性着色樹脂組成物の固形分濃度や粘度等を調整することにより、適宜制御されるが、通常、1μm~5μmの範囲である。
当該遮光部のパターン形状としては、前記着色硬化膜の形状に合わせて適宜選択されればよく、例えば、ストライプ状、マトリクス状等の形状が挙げられる。遮光部は、スパッタリング法、真空蒸着法等によるクロム等の金属薄膜であっても良い。或いは、遮光部は、樹脂バインダー中にカーボン微粒子、金属酸化物、無機顔料、有機顔料等の遮光性粒子を含有させた樹脂層であってもよい。遮光性粒子を含有させた樹脂層の場合には、感光性レジストを用いて現像によりパターニングする方法、遮光性粒子を含有するインクジェットインクを用いてパターニングする方法、感光性レジストを熱転写する方法等がある。
また、封止膜111上に設けられる透明粘着剤層112や、カバー材113としても、公知の材料を適宜選択して用いることができる。本発明においてはカバー材にガラスを用いた場合であっても、緑色硬化膜の耐候性が良好で、透過率の低下が抑制される点から、カバー材としてガラスを用いることができる。
本発明に係る有機発光素子と外光反射防止膜の積層体の製造方法は、
有機発光素子上に、前記本発明に係る感光性着色樹脂組成物を塗布することにより塗膜を形成する工程、
前記塗膜に光照射する工程、
前記光照射後の膜を、加熱するポストベイク工程、及び、
前記光照射後の膜を、現像する工程を含有することにより、
有機発光素子上に前記本発明に係る感光性着色樹脂組成物の硬化膜を形成する工程を有する。
以下各工程について、説明する。
次いで、ホットプレートやオーブンなどを用いて、該ウェット塗膜を乾燥させ、塗膜を形成する。
ポストベイク工程は、前記光照射後の膜に対して、後述する現像工程前に行ってもよいし、現像工程後に行ってもよいし、現像工程前後に行ってもよい。
現像工程においては、現像液を用いて現像処理し、未露光部分を溶解、除去することにより、所望のパターンで塗膜が形成される。現像液としては、通常、水や水溶性溶剤にアルカリを溶解させた溶液が用いられる。このアルカリ溶液には、界面活性剤などを適量添加してもよい。また、現像方法は一般的な方法を採用することができる。
本発明では有機発光素子を備えた素子基板上に直接着色硬化膜を形成することから、このポストベイク工程における加熱温度も、130℃以下が好ましく、100℃以下がより好ましく、90℃以下が更に好ましい。また、加熱温度は、30℃以上であってよく、35℃以上であってよく、40℃以上であってよい。
重合槽に、PGMEAを300質量部仕込み、窒素雰囲気下で100℃に昇温した後、メタクリル酸メチル(MMA)190質量部(全モノマー中95質量%)、メタクリル酸(MAA)10質量部(全モノマー中5質量%)及びパーブチルO(日油株式会社製)3質量部、連鎖移動剤(n-ドデシルメルカプタン)2質量部を1.5時間かけて連続的に滴下した。その後、100℃を保持して反応を続け、上記主鎖形成用混合物の滴下終了から2時間後に重合禁止剤として、p-メトキシフェノール0.1質量部を添加して重合を停止し、非反応性樹脂1溶液(固形分40質量%)を得た。
得られた非反応性樹脂1の重量平均分子量と酸価を表2に示す。
合成例1において、メタクリル酸メチルを全モノマー中95質量%から93質量%に変更し、且つ、メタクリル酸を全モノマー中5質量%から7質量%に変更した以外は、合成例1と同様にして非反応性樹脂2を合成した。得られた非反応性樹脂2の重量平均分子量と酸価を表2に示す。
合成例1において、メタクリル酸メチルを全モノマー中95質量%から99質量%に変更し、且つ、メタクリル酸を全モノマー中5質量%から1質量%に変更した以外は、合成例1と同様にして非反応性樹脂3を合成した。得られた非反応性樹脂3の重量平均分子量と酸価を表2に示す。
合成例3において、連鎖移動剤(n-ドデシルメルカプタン)の添加量を0.5質量部に変更した以外は、合成例3と同様にして非反応性樹脂4を合成した。得られた非反応性樹脂4の重量平均分子量と酸価を表2に示す。
合成例1において、連鎖移動剤(n-ドデシルメルカプタン)の添加量を0.5質量部に変更した以外は、合成例1と同様にして非反応性樹脂5を合成した。得られた非反応性樹脂5の重量平均分子量と酸価を表2に示す。
合成例1において、連鎖移動剤(n-ドデシルメルカプタン)の添加量を6質量部に変更した以外は、合成例1と同様にして非反応性樹脂6を合成した。得られた非反応性樹脂6の重量平均分子量と酸価を表2に示す。
合成例2において、連鎖移動剤(n-ドデシルメルカプタン)の添加量を6質量部に変更した以外は、合成例2と同様にして非反応性樹脂7を合成した。得られた非反応性樹脂7の重量平均分子量と酸価を表2に示す。
合成例1において、メタクリル酸を全モノマー中5質量%からアクリル酸を全モノマー中5質量%に変更した以外は、合成例1と同様にして非反応性樹脂8を合成した。得られた非反応性樹脂8の重量平均分子量と酸価を表2に示す。
合成例1において、メタクリル酸メチルを全モノマー中95質量%から、メタクリル酸メチルを全モノマー中90質量%と、メタクリル酸エチルを全モノマー中5質量%に変更した以外は、合成例1と同様にして非反応性樹脂9を合成した。得られた非反応性樹脂9の重量平均分子量と酸価を表2に示す。
合成例1において、メタクリル酸メチルを全モノマー中95質量%から、メタクリル酸メチルを全モノマー中70質量%と、メタクリル酸エチルを全モノマー中25質量%に変更した以外は、合成例1と同様にして非反応性樹脂10を合成した。得られた非反応性樹脂10の重量平均分子量と酸価を表2に示す。
合成例1において、メタクリル酸メチルを全モノマー中95質量%から、メタクリル酸メチルを全モノマー中50質量%と、メタクリル酸エチルを全モノマー中45質量%に変更した以外は、合成例1と同様にして非反応性樹脂11を合成した。得られた非反応性樹脂11の重量平均分子量と酸価を表2に示す。
合成例1において、メタクリル酸メチルモノマーを95質量%からメタクリル酸ブチルモノマー95質量%に変更した以外は、合成例1と同様にして比較非反応性樹脂c1を合成した。得られた比較非反応性樹脂c1の重量平均分子量と酸価を表5に示す。
合成例1において、連鎖移動剤(n-ドデシルメルカプタン)の添加量を0質量部に変更した以外は、合成例1と同様にして比較非反応性樹脂c2を合成した。得られた比較非反応性樹脂c2の重量平均分子量と酸価を表5に示す。
合成例1において、連鎖移動剤(n-ドデシルメルカプタン)の添加量を10質量部に変更したに変更した以外は、合成例1と同様にして比較非反応性樹脂c3を合成した。得られた比較非反応性樹脂c3の重量平均分子量と酸価を表5に示す。
合成例1において、メタクリル酸メチルモノマーを95質量%から100質量%に変更した以外は、合成例1と同様にして比較非反応性樹脂c4を合成した。得られた比較非反応性樹脂c4の重量平均分子量と酸価を表5に示す。
合成例1において、メタクリル酸メチルモノマーを95質量%から90質量%に変更し、且つ、メタクリル酸モノマーを5質量%から10質量%に変更した以外は、合成例1と同様にして比較非反応性樹脂c5を合成した。得られた比較非反応性樹脂c5の重量平均分子量と酸価を表5に示す。
重合槽に、PGMEAを300質量部仕込み、窒素雰囲気下で100℃に昇温した後、メタクリル酸2-フェノキシエチル(PhEMA)90質量部、MMA54質量部、メタクリル酸(MAA)36質量部及びパーブチルO(日油株式会社製)6質量部、連鎖移動剤(n-ドデシルメルカプタン)2質量部を1.5時間かけて連続的に滴下した。その後、100℃を保持して反応を続け、上記主鎖形成用混合物の滴下終了から2時間後に重合禁止剤として、p-メトキシフェノール0.1質量部を添加して重合を停止した。
次に、空気を吹き込みながら、エポキシ基含有化合物としてメタクリル酸グリシジル(GMA)20質量部を添加して、110℃に昇温した後、トリエチルアミン0.8質量部を添加して110℃で15時間付加反応させ、アルカリ可溶性樹脂A溶液(固形分40質量%)を得た。得られたアルカリ可溶性樹脂Aの重量平均分子量と酸価を表1に示す。
なお、上記重量平均分子量の測定方法は、ポリスチレンを標準物質とし、THFを溶離液としてショウデックスGPCシステム-21H(Shodex GPC System-21H)により重量平均分子量を測定した。また酸価の測定方法は、JIS K 0070に基づいて測定した。
重合槽に、PGMEAを300質量部仕込み、窒素雰囲気下で100℃に昇温した後、メタクリル酸2-フェノキシエチル(PhEMA)90質量部、MMA48質量部、メタクリル酸(MAA)42質量部及びパーブチルO(日油株式会社製)6質量部、連鎖移動剤(n-ドデシルメルカプタン)2質量部を1.5時間かけて連続的に滴下した。その後、100℃を保持して反応を続け、上記主鎖形成用混合物の滴下終了から2時間後に重合禁止剤として、p-メトキシフェノール0.1質量部を添加して重合を停止した。
次に、空気を吹き込みながら、エポキシ基含有化合物としてメタクリル酸グリシジル(GMA)20質量部を添加して、110℃に昇温した後、トリエチルアミン0.8質量部を添加して110℃で15時間付加反応させ、アルカリ可溶性樹脂B溶液(固形分40質量%)を得た。得られたアルカリ可溶性樹脂Bの重量平均分子量と酸価を表1に示す。
重合槽に、PGMEAを300質量部仕込み、窒素雰囲気下で100℃に昇温した後、メタクリル酸2-フェノキシエチル(PhEMA)90質量部、MMA60質量部、メタクリル酸(MAA)30質量部及びパーブチルO(日油株式会社製)6質量部、連鎖移動剤(n-ドデシルメルカプタン)2質量部を1.5時間かけて連続的に滴下した。その後、100℃を保持して反応を続け、上記主鎖形成用混合物の滴下終了から2時間後に重合禁止剤として、p-メトキシフェノール0.1質量部を添加して重合を停止した。
次に、空気を吹き込みながら、エポキシ基含有化合物としてメタクリル酸グリシジル(GMA)20質量部を添加して、110℃に昇温した後、トリエチルアミン0.8質量部を添加して110℃で15時間付加反応させ、アルカリ可溶性樹脂C溶液(固形分40質量%)を得た。得られたアルカリ可溶性樹脂Cの重量平均分子量と酸価を表1に示す。
重合槽に、PGMEAを300質量部仕込み、窒素雰囲気下で100℃に昇温した後、メタクリル酸2-フェノキシエチル(PhEMA)90質量部、MMA32質量部、メタクリル酸(MAA)58質量部及びパーブチルO(日油株式会社製)6質量部、連鎖移動剤(n-ドデシルメルカプタン)2質量部を1.5時間かけて連続的に滴下した。その後、100℃を保持して反応を続け、上記主鎖形成用混合物の滴下終了から2時間後に重合禁止剤として、p-メトキシフェノール0.1質量部を添加して重合を停止した。
次に、空気を吹き込みながら、エポキシ基含有化合物としてメタクリル酸グリシジル(GMA)20質量部を添加して、110℃に昇温した後、トリエチルアミン0.8質量部を添加して110℃で15時間付加反応させ、アルカリ可溶性樹脂D溶液(固形分40質量%)を得た。得られたアルカリ可溶性樹脂Dの重量平均分子量と酸価を表1に示す。
重合槽に、PGMEAを300質量部仕込み、窒素雰囲気下で100℃に昇温した後、メタクリル酸2-フェノキシエチル(PhEMA)90質量部、MMA54質量部、メタクリル酸(MAA)36質量部及びパーブチルO(日油株式会社製)6質量部、連鎖移動剤(n-ドデシルメルカプタン)6質量部を1.5時間かけて連続的に滴下した。その後、100℃を保持して反応を続け、上記主鎖形成用混合物の滴下終了から2時間後に重合禁止剤として、p-メトキシフェノール0.1質量部を添加して重合を停止した。
次に、空気を吹き込みながら、エポキシ基含有化合物としてメタクリル酸グリシジル(GMA)20質量部を添加して、110℃に昇温した後、トリエチルアミン0.8質量部を添加して110℃で15時間付加反応させ、アルカリ可溶性樹脂E溶液(固形分40質量%)を得た。得られたアルカリ可溶性樹脂Eの重量平均分子量と酸価を表1に示す。
重合槽に、PGMEAを300質量部仕込み、窒素雰囲気下で100℃に昇温した後、メタクリル酸2-フェノキシエチル(PhEMA)90質量部、MMA54質量部、メタクリル酸(MAA)36質量部及びパーブチルO(日油株式会社製)6質量部、連鎖移動剤(n-ドデシルメルカプタン)4質量部を1.5時間かけて連続的に滴下した。その後、100℃を保持して反応を続け、上記主鎖形成用混合物の滴下終了から2時間後に重合禁止剤として、p-メトキシフェノール0.1質量部を添加して重合を停止した。
次に、空気を吹き込みながら、エポキシ基含有化合物としてメタクリル酸グリシジル(GMA)20質量部を添加して、110℃に昇温した後、トリエチルアミン0.8質量部を添加して110℃で15時間付加反応させ、アルカリ可溶性樹脂F溶液(固形分40質量%)を得た。得られたアルカリ可溶性樹脂Fの重量平均分子量と酸価を表1に示す。
重合槽に、PGMEAを300質量部仕込み、窒素雰囲気下で100℃に昇温した後、メタクリル酸2-フェノキシエチル(PhEMA)90質量部、MMA54質量部、メタクリル酸(MAA)36質量部及びパーブチルO(日油株式会社製)6質量部、連鎖移動剤(n-ドデシルメルカプタン)1.5質量部を1.5時間かけて連続的に滴下した。その後、100℃を保持して反応を続け、上記主鎖形成用混合物の滴下終了から2時間後に重合禁止剤として、p-メトキシフェノール0.1質量部を添加して重合を停止した。
次に、空気を吹き込みながら、エポキシ基含有化合物としてメタクリル酸グリシジル(GMA)20質量部を添加して、110℃に昇温した後、トリエチルアミン0.8質量部を添加して110℃で15時間付加反応させ、アルカリ可溶性樹脂G溶液(固形分40質量%)を得た。得られたアルカリ可溶性樹脂Gの重量平均分子量と酸価を表1に示す。
重合槽に、PGMEAを300質量部仕込み、窒素雰囲気下で100℃に昇温した後、メタクリル酸2-フェノキシエチル(PhEMA)90質量部、MMA54質量部、メタクリル酸(MAA)36質量部及びパーブチルO(日油株式会社製)6質量部、連鎖移動剤(n-ドデシルメルカプタン)0.5質量部を1.5時間かけて連続的に滴下した。その後、100℃を保持して反応を続け、上記主鎖形成用混合物の滴下終了から2時間後に重合禁止剤として、p-メトキシフェノール0.1質量部を添加して重合を停止した。
次に、空気を吹き込みながら、エポキシ基含有化合物としてメタクリル酸グリシジル(GMA)20質量部を添加して、110℃に昇温した後、トリエチルアミン0.8質量部を添加して110℃で15時間付加反応させ、アルカリ可溶性樹脂H溶液(固形分40質量%)を得た。得られたアルカリ可溶性樹脂Hの重量平均分子量と酸価を表1に示す。
調製例1において、メタクリル酸2-フェノキシエチル(PhEMA)をベンジルメタクリレート(BzMA)に変更した以外は、調製例1と同様にしてアルカリ可溶性樹脂Iを合成した。得られたアルカリ可溶性樹脂I(固形分40質量%)の重量平均分子量と酸価を表1に示す。
調製例1において、メタクリル酸2-フェノキシエチル(PhEMA)をシクロヘキシルメタクリレート(CHMA)に変更した以外は、調製例1と同様にしてアルカリ可溶性樹脂Jを合成した。得られたアルカリ可溶性樹脂J(固形分40質量%)の重量平均分子量と酸価を表1に示す。
重合槽に、PGMEAを300質量部仕込み、窒素雰囲気下で100℃に昇温した後、メタクリル酸グリシジル(GMA)116質量部及びパーブチルO(日油株式会社製)6質量部、連鎖移動剤(n-ドデシルメルカプタン)2質量部を1.5時間かけて連続的に滴下した。その後、100℃を保持して反応を続け、上記主鎖形成用混合物の滴下終了から2時間後に重合禁止剤として、p-メトキシフェノール0.1質量部を添加して重合を停止した。
次に、空気を吹き込みながら、アクリル酸(AA)56質量部を添加して、110℃に昇温した後、トリエチルアミン0.8質量部を添加して110℃で8時間付加反応させた。さらに、無水コハク酸28質量部を添加し、110℃で8時間付加反応させた。アルカリ可溶性樹脂K溶液(固形分40質量%)を得た。得られたアルカリ可溶性樹脂Kの重量平均分子量と酸価を表1に示す。
冷却管、添加用ロート、窒素用インレット、機械的攪拌機、デジタル温度計を備えた500mL丸底4口セパラブルフラスコにTHF250質量部、塩化リチウム0.6質量部を加え、充分に窒素置換を行った。反応フラスコを-60℃まで冷却した後、ブチルリチウム4.9質量部(15質量%ヘキサン溶液)、ジイソプロピルアミン1.1質量部、イソ酪酸メチル1.0質量部をシリンジを用いて注入した。Bブロック用モノマーのメタクリル酸1-エトキシエチル(EEMA)2.2質量部、メタクリル酸2-(トリメチルシリルオキシ)エチル(TMSMA) 29.1質量部、メタクリル酸2-エチルヘキシル(EHMA)12.8質量部、メタクリル酸n-ブチル(BMA)13.7質量部、メタクリル酸ベンジル(BzMA)9.5質量部、メタクリル酸メチル(MMA)17.5質量部を、添加用ロートを用いて60分かけて滴下した。30分後、Aブロック用モノマーであるメタクリル酸ジメチルアミノエチル(DMMA)26.7質量部を20分かけて滴下した。30分間反応させた後、メタノール1.5質量部を加えて反応を停止させた。得られた前駆体ブロック共重合体THF溶液はヘキサン中で再沈殿させ、濾過、真空乾燥により精製を行い、PGMEAで希釈し固形分30質量%溶液とした。水を32.5質量部加え、100℃に昇温し7時間反応させ、EEMA由来の構成単位を脱保護しメタクリル酸(MAA)由来の構成単位とし、TMSMA由来の構成単位を脱保護してメタクリル酸2-ヒドロキシエチル(HEMA)由来の構成単位とした。得られたブロック共重合体PGMEA溶液はヘキサン中で再沈殿させ、濾過、真空乾燥により精製を行い、前記一般式(I)で表される構成単位を含むブロック共重合体1(アミン価 95mgKOH/g、酸価 8mgKOH/g、Tg38℃)を得た。重量平均分子量Mwは7730であった。
国際公開2015/152153号公報の段落0114~0117の化合物No.73の製造と同様にして、前記式(A-2)で表されるオキシムエステル系光開始剤を合成した。
(1)色材分散液R(1)の製造
225mLマヨネーズ瓶中に、PGMEA72.1質量部、調製例1のアルカリ可溶性樹脂A溶液(固形分40質量%)15.0質量部、調製例12のブロック共重合体1のPGMEA溶液(固形分35質量%)10.2質量部を入れ攪拌した。そこへフェニルホスホン酸(商品名:PPA、日産化学社製)0.4質量部を加え、室温で30分攪拌した。
そこへ、赤色顔料としてC.I.ピグメントレッド177(R177)を13.3質量部、粒径2.0mmジルコニアビーズ100質量部を入れ、予備解砕としてペイントシェーカー(浅田鉄工社製)で1時間振とうし、次いで粒径0.1mmのジルコニアビーズ200部に変更し本解砕としてペイントシェーカーで4時間分散を行い、色材分散液R(1)を得た。なお、ブロック共重合体1は、フェニルホスホン酸によって塩形成され、塩型ブロック共重合体1となっている。
上記で得られた色材分散液R(1)を111質量部、合成例1で得られた非反応性樹脂1溶液(固形分40質量%)を10質量部、多官能モノマー(商品名アロニックスM-305、東亞合成(株)社製)を17.2質量部、前記式(A-2)で表されるオキシムエステル系光開始剤を2質量部、フッ素系界面活性剤(商品名メガファックR-08MH、DIC(株)製)を0.1質量部、PGMEAを170.5質量部加え、感光性着色樹脂組成物R-1を得た。
実施例1の感光性着色樹脂組成物R-1の製造において、表2に示したように、非反応性樹脂の種類及び/又は質量比を変更し、前記式(A-2)で表されるオキシムエステル系光開始剤の比率は実施例1と同じまま、顔料濃度が実施例1と同じになるように多官能モノマーの質量比を変更した以外は、感光性着色樹脂組成物R-1と同様にして、感光性着色樹脂組成物R-2~R-11を得た。
(1)色材分散液R(2)~(11)の製造
実施例1の色材分散液R(1)の製造において、アルカリ可溶性樹脂Aの代わりに、表2に示したようにアルカリ可溶性樹脂の種類をアルカリ可溶性樹脂B、C、D、E、F、G、H、I、J、又はKにそれぞれ変更した以外は、色材分散液R(1)と同様にして、色材分散液R(2)~(11)を得た。
(2)感光性着色樹脂組成物R-12~R-21の製造
実施例1の感光性着色樹脂組成物R-1の製造において、表2に示したように、色材分散液R(1)の代わりに、アルカリ可溶性樹脂の種類が異なる色材分散液R(2)~(11)に変更し、非反応性樹脂の質量比を変更し、前記式(A-2)で表されるオキシムエステル系光開始剤の比率は実施例1と同じまま、顔料濃度が実施例1と同じになるように多官能モノマーの質量比を変更した以外は、感光性着色樹脂組成物R-1と同様にして、感光性着色樹脂組成物R-12~R-21を得た。
上記で得られた色材分散液R(1)を111質量部、合成例1で得られた非反応性樹脂1を10質量部、多官能モノマー(商品名アロニックスM-305、東亞合成(株)社製)を7.2質量部、前記式(A-2)で表されるオキシムエステル系光開始剤を2質量部、フッ素系界面活性剤(商品名メガファックR-08MH、DIC(株)製)を0.1質量部、多官能エポキシ化合物(2,2-ビス(ヒドロキシメチル)-1-ブタノールの1,2-エポキシ-4-(2-オキシラニル)シクロヘキサン付加物、商品名EHPE3150、ダイセル社製)を10質量部、PGMEAを170.5質量部加え、感光性着色樹脂組成物R-22を得た。
実施例22において、多官能エポキシ化合物を、多官能ブロックイソシアネート化合物(商品名デュラネートMF-K60B、旭化成社製)に変更した以外は、感光性着色樹脂組成物R-22と同様にして、感光性着色樹脂組成物R-23を得た。
(1)色材分散液G(1)の製造
225mLマヨネーズ瓶中に、PGMEA72.1質量部、調製例1のアルカリ可溶性樹脂A溶液(固形分40質量%)15質量部、調製例12のブロック共重合体1のPGMEA溶液(固形分35質量%)10.2質量部を入れ攪拌した。そこへフェニルホスホン酸(商品名:PPA、日産化学社製)0.4質量部を加え、室温で30分攪拌した。
そこへ、緑色顔料としてC.I.ピグメントグリーン59(G59)を8.0質量部、黄色顔料としてC.I.ピグメントイエロー150(Y150)を5.3質量部、粒径2.0mmジルコニアビーズ100質量部を入れ、予備解砕としてペイントシェーカー(浅田鉄工社製)で1時間振とうし、次いで粒径0.1mmのジルコニアビーズ200部に変更し本解砕としてペイントシェーカーで4時間分散を行い、色材分散液G(1)を得た。なお、ブロック共重合体1は、フェニルホスホン酸によって塩形成され、塩型ブロック共重合体1となっている。
上記で得られた色材分散液G(1)を111質量部、合成例1で得られた非反応性樹脂1を10質量部、多官能モノマー(商品名アロニックスM-305、東亞合成(株)社製)を17.2質量部、前記式(A-2)で表されるオキシムエステル系光開始剤を2質量部、フッ素系界面活性剤(商品名メガファックR-08MH、DIC(株)製)を0.1質量部、PGMEAを170.5質量部加え、感光性着色樹脂組成物G-1を得た。
実施例24の感光性着色樹脂組成物G-1の製造において、表3に示したように、非反応性樹脂の種類及び/又は質量比を変更し、前記式(A-2)で表されるオキシムエステル系光開始剤の比率は実施例24と同じまま、顔料濃度が実施例24と同じになるように多官能モノマーの質量比を変更した以外は、感光性着色樹脂組成物G-1と同様にして、感光性着色樹脂組成物G-2~G-11を得た。
(1)色材分散液G(2)~(11)の製造
実施例24の色材分散液G(1)の製造において、アルカリ可溶性樹脂Aの代わりに、表3に示したようにアルカリ可溶性樹脂の種類をアルカリ可溶性樹脂B、C、D、E、F、G、H、I、J、又はKにそれぞれ変更した以外は、色材分散液G(1)と同様にして、色材分散液G(2)~(11)を得た。
(2)感光性着色樹脂組成物G-12~G-21の製造
実施例24の感光性着色樹脂組成物G-1の製造において、表3に示したように、色材分散液G(1)の代わりに、アルカリ可溶性樹脂の種類が異なる色材分散液G(2)~(11)に変更し、非反応性樹脂の質量比を変更し、前記式(A-2)で表されるオキシムエステル系光開始剤の比率は実施例24と同じまま、顔料濃度が実施例24と同じになるように多官能モノマーの質量比を変更した以外は、感光性着色樹脂組成物G-1と同様にして、感光性着色樹脂組成物G-12~G-21を得た。
上記で得られた色材分散液G(1)を111質量部、合成例1で得られた非反応性樹脂1を10質量部、多官能モノマー(商品名アロニックスM-305、東亞合成(株)社製)を7.2質量部、前記式(A-2)で表されるオキシムエステル系光開始剤を2質量部、フッ素系界面活性剤(商品名メガファックR-08MH、DIC(株)製)を0.1質量部、多官能エポキシ樹脂(2,2-ビス(ヒドロキシメチル)-1-ブタノールの1,2-エポキシ-4-(2-オキシラニル)シクロヘキサン付加物、商品名EHPE3150、ダイセル社製)を10質量部PGMEAを170.5質量部加え、感光性着色樹脂組成物G-22を得た。
実施例45において、多官能エポキシ化合物を多官能ブロックイソシアネート化合物(商品名デュラネートMF-K60B、旭化成社製)に変更した以外は、感光性着色樹脂組成物G-22と同様にして、感光性着色樹脂組成物G-23を得た。
(1)色材分散液B(1)の製造
225mLマヨネーズ瓶中に、PGMEA48.1質量部、調製例1のアルカリ可溶性樹脂A溶液(固形分40質量%)10質量部、調製例12のブロック共重合体1のPGMEA溶液(固形分35質量%)6.8質量部を入れ攪拌した。そこへフェニルホスホン酸(商品名:PPA、日産化学社製)0.3質量部を加え、室温で30分攪拌した。
そこへ、青色顔料としてC.I.ピグメントブルー15:6(B15:6)を7.1質量部、紫色顔料としてC.I.ピグメントバイオレット23(V23)を1.8質量部、粒径2.0mmジルコニアビーズ100質量部を入れ、予備解砕としてペイントシェーカー(浅田鉄工社製)で1時間振とうし、次いで粒径0.1mmのジルコニアビーズ200部に変更し本解砕としてペイントシェーカーで4時間分散を行い、色材分散液B(1)を得た。なお、ブロック共重合体1は、フェニルホスホン酸によって塩形成され、塩型ブロック共重合体1となっている。
上記で得られた色材分散液B(1)を74.1質量部、合成例1で得られた非反応性樹脂1を5質量部、多官能モノマー(商品名アロニックスM-305、東亞合成(株)社製)を16質量部、前記式(A-2)で表されるオキシムエステル系光開始剤を2質量部、フッ素系界面活性剤(商品名メガファックR-08MH、DIC(株)製)を0.1質量部、PGMEAを140.6質量部加え、感光性着色樹脂組成物B-1を得た。
実施例47の感光性着色樹脂組成物B-1の製造において、表4に示したように、非反応性樹脂の種類及び/又は質量比を変更し、前記式(A-2)で表されるオキシムエステル系光開始剤の比率は実施例47と同じまま、顔料濃度が実施例47と同じになるように多官能モノマーの質量比を変更した以外は、感光性着色樹脂組成物B-1と同様にして、感光性着色樹脂組成物B-2~B-11を得た。
(1)色材分散液B(2)~(11)の製造
実施例47の色材分散液B(1)の製造において、アルカリ可溶性樹脂Aの代わりに、表4に示したようにアルカリ可溶性樹脂の種類をアルカリ可溶性樹脂B、C、D、E、F、G、H、I、J、又はKにそれぞれ変更した以外は、色材分散液B(1)と同様にして、色材分散液B(2)~(11)を得た。
(2)感光性着色樹脂組成物B-12~B-21の製造
実施例47の感光性着色樹脂組成物B-1の製造において、表4に示したように、色材分散液B(1)の代わりに、アルカリ可溶性樹脂の種類が異なる色材分散液B(2)~(11)に変更し、非反応性樹脂の質量比を変更し、前記式(A-2)で表されるオキシムエステル系光開始剤の比率は実施例47と同じまま、顔料濃度が実施例47と同じになるように多官能モノマーの質量比を変更した以外は、感光性着色樹脂組成物B-1と同様にして、感光性着色樹脂組成物B-12~B-21を得た。
上記で得られた色材分散液B(1)を74.1質量部、合成例1で得られた非反応性樹脂1を5質量部、多官能モノマー(商品名アロニックスM-305、東亞合成(株)社製)を6質量部、前記式(A-2)で表されるオキシムエステル系光開始剤を2質量部、フッ素系界面活性剤(商品名メガファックR-08MH、DIC(株)製)を0.1質量部、多官能エポキシ化合物(2,2-ビス(ヒドロキシメチル)-1-ブタノールの1,2-エポキシ-4-(2-オキシラニル)シクロヘキサン付加物、商品名EHPE3150、ダイセル社製)を10質量部PGMEAを140.6質量部加え、感光性着色樹脂組成物B-22を得た。
実施例68において、前記多官能エポキシ化合物を、多官能ブロックイソシアネート化合物(商品名デュラネートMF-K60B、旭化成社製)に変更した以外は、感光性着色樹脂組成物B-22と同様にして、感光性着色樹脂組成物B-23を得た。
実施例1において、それぞれ表5に示したように、非反応性樹脂を用いなかったか、非反応性樹脂1の代わりに比較非反応性樹脂c1~c5のいずれかを用いた以外は、感光性着色樹脂組成物R-1と同様にして、比較感光性着色樹脂組成物CR-1~CR-6を得た。
実施例24において、それぞれ表5に示したように、非反応性樹脂を用いなかったか、非反応性樹脂1の代わりに比較非反応性樹脂c1~c5のいずれかを用いた以外は、感光性着色樹脂組成物G-1と同様にして、比較感光性着色樹脂組成物CG-1~CG-6を得た。
実施例47において、それぞれ表5に示したように、非反応性樹脂を用いなかったか、非反応性樹脂1の代わりに比較非反応性樹脂c1~c5のいずれかを用いた以外は、感光性着色樹脂組成物B-1と同様にして、比較感光性着色樹脂組成物CB-1~CB-6を得た。
各実施例及び各比較例で得られた感光性着色樹脂組成物を、ガラス基板(NHテクノグラス(株)社製、「NA35」)上にそれぞれ、スピンコーターを用いて硬化塗膜が厚さ3.0μmとなるように塗布した後、ホットプレートを用いて80℃で3分間乾燥し基板上に塗膜を形成した。この塗膜に、独立細線を形成するための開口寸法2μmから100μmのパターンを有するフォトマスク(クロムマスク)を介して、超高圧水銀灯を用いて50mJ/cm2の紫外線で露光することにより、露光後塗膜を形成した。次いで、0.05wt%水酸化カリウム水溶液を現像液としてスピン現像し、現像液に60秒間接液させた後に純水で洗浄することで現像処理し、独立細線パターン状の塗膜を得た。その後、90℃のクリーンオーブンで30分間ポストベイクすることにより、独立細線パターン状の硬化膜を形成した。得られた硬化膜について、透過率と、断面形状と、耐溶剤性の評価を行った。
実施例及び比較例で得られた感光性着色樹脂組成物を、それぞれガラス基板(NHテクノグラス(株)社製、「NA35」)上に、スピンコーターを用いて塗布後に厚さ3.0μmの着色層を形成する膜厚で塗布した後、ホットプレートを用いて80℃で3分間乾燥し、ガラス基板上に着色層を形成した。上記着色層が形成されたガラス板を、アルカリ現像液として0.05質量%水酸化カリウム水溶液を用いて60秒間シャワー現像させた後に純水で洗浄することで現像処理した。現像後の上記着色層の形成部を、目視により観察した後、エタノールを含ませたレンズクリーナー(東レ社製、商品名トレシーMKクリーンクロス)で十分に拭き取り、そのレンズクリーナーの着色度合いを目視で観察した。
(現像残渣評価基準)
◎:目視により現像残渣が確認されず、レンズクリーナーが全く着色しなかった
○:目視により現像残渣が確認されず、レンズクリーナーの着色がわずかに確認された
×:目視により現像残渣が確認され、レンズクリーナーの着色が確認された
評価結果が〇であれば、実用上使用できるが、判定結果が◎であればより効果が優れている。
得られた独立細線パターン状の着色層の厚み方向断面形状を、走査型電子顕微鏡((株)島津製作所製、super scan model 220、倍率10000倍)により観察し、下記評価基準により、着色層の断面形状のテーパー角(θ1)(図5参照)について評価した。
(パターン状着色層の断面形状の評価基準)
◎:テーパー角(θ1)が15度以上100度未満
○:テーパー角(θ1)が100度以上110度未満
△:テーパー角(θ1)が110度以上120度未満
×:テーパー角(θ1)が120度以上
評価結果が△であれば実用上使用できるが、評価結果が○であれば着色層の断面形状は良好である。評価結果が◎であれば着色層の断面形状に優れている。
得られた着色層の膜厚を測定した後、プロピレングリコールモノメチルエーテル(PGME)に10分間浸漬した後、風乾し、再び膜厚を測定した。なお、膜厚測定には、触針式段差膜厚計「P-15Tencor」(Instruments製)を用いた。溶剤浸漬後膜厚/溶剤浸漬前膜厚を×100を、残膜率として算出した。
(耐溶剤性評価基準)
◎:溶剤浸漬後の残膜率が98%以上
○:溶剤浸漬後の残膜率が96%以上98%未満
△:溶剤浸漬後の残膜率が94%以上96%未満
×:溶剤浸漬後の残膜率が94%未満
評価結果が△であれば実用上使用できるが、評価結果が○であれば耐溶剤性は良好であり、評価結果が◎であれば耐溶剤性に優れている。
本発明に係る感光性着色樹脂組成物である実施例1~69では、アルカリ可溶性樹脂に、特定の非反応性樹脂を組み合わせたことから、低温加熱処理でも、現像残渣の発生を抑制し、且つパターン形状が良好な着色層を形成可能であることが示された。中でも前記非反応性樹脂として、メタクリル酸メチルに由来する構成単位の含有量が全構成単位中90質量%~99質量%である非反応性樹脂を用いると断面形状がより良好になることが示された。また、中でも多官能エポキシ樹脂や多官能イソシアネート化合物を添加すると、耐溶剤性が向上することが示された。
それに対して、特定の非反応性樹脂を用いなかった比較例1、7及び13の感光性着色樹脂組成物は、着色層の断面形状がアンダーカット形状になってしまうことが示された。
また、酸価と重量平均分子量は本発明の非反応性樹脂と同じ範囲だがメタクリル酸メチルモノマーの代わりにメタクリル酸ブチルモノマーを用いた非反応性樹脂を、アルカリ可溶性樹脂に組み合わせた比較例2、8及び14の感光性着色樹脂組成物は、着色層の断面形状がアンダーカット形状になってしまうことが示された。
また、構成単位と酸価は本発明の非反応性樹脂と同じ範囲だが重量平均分子量が本発明の特定よりも大きい非反応性樹脂を、アルカリ可溶性樹脂に組み合わせた比較例3、9及び15の感光性着色樹脂組成物は、着色層の形成部に現像残渣が生じることが示された。
また、構成単位と酸価は本発明の非反応性樹脂と同じ範囲だが重量平均分子量が本発明の特定よりも小さい非反応性樹脂を、アルカリ可溶性樹脂に組み合わせた比較例4、10及び16の感光性着色樹脂組成物は、着色層の断面形状がアンダーカット形状になってしまうことが示された。
また、重量平均分子量は本発明の非反応性樹脂と同じ範囲だが、メタクリル酸メチルに由来する構成単位の含有量が全構成単位中100モル%で酸価が0mgKOH/gである非反応性樹脂を、アルカリ可溶性樹脂に組み合わせた比較例5、11及び17の感光性着色樹脂組成物は、着色層の形成部に現像残渣が生じることが示された。
また、構成単位と重量平均分子量は本発明の非反応性樹脂と同じ範囲だが酸価が本発明の特定よりも大きい非反応性樹脂を、アルカリ可溶性樹脂に組み合わせた比較例6、12及び18の感光性着色樹脂組成物は、着色層の断面形状がアンダーカット形状になってしまうことが示された。
2 遮光部
3 着色層(着色硬化膜)
10 カラーフィルタ
20 対向基板
30 液晶層
40 液晶表示装置
50 基板
71 透明陽極
72 正孔注入層
73 正孔輸送層
74 発光層
75 電子注入層
76 陰極
80 有機発光素子
90 封止層
100 有機発光表示装置
101 基板
102 薄膜トランジスタ(TFT)
103 封止膜
104 電極
105 隔壁
106R、106G、106B 有機発光素子
107 電極
108 封止層
109R、109G、109B 着色硬化膜
110 遮光部
111 封止膜
112 透明粘着剤層
113 カバー材
120 外光反射防止膜
130 有機発光素子を備えた素子基板
200 表示装置
Claims (14)
- 色材と、アルカリ可溶性樹脂と、非反応性樹脂と、光重合性化合物と、光開始剤と、溶剤とを含有を含有し、
前記アルカリ可溶性樹脂は、酸価が50mgKOH/g超過であり、
前記非反応性樹脂は、酸価が7mgKOH/g~50mgKOH/gであり、メタクリル酸メチルに由来する構成単位の含有量が全構成単位中50質量%~99質量%であり、重量平均分子量が5000~50000である、感光性着色樹脂組成物。 - 前記非反応性樹脂の含有量は、感光性着色樹脂組成物の固形分全量に対して、1質量%~20質量%である、請求項1に記載の感光性着色樹脂組成物。
- 前記アルカリ可溶性樹脂の重量平均分子量が3000~30000である、請求項1又は2に記載の感光性着色樹脂組成物。
- 前記非反応性樹脂の含有量は、前記アルカリ可溶性樹脂と前記非反応性樹脂の合計含有量に対して、1質量%~80質量%である、請求項1~3のいずれか1項に記載の感光性着色樹脂組成物。
- 前記非反応性樹脂は、メタクリル酸メチルに由来する構成単位の含有量が全構成単位中90質量%~99質量%である、請求項1~4のいずれか1項に記載の感光性着色樹脂組成物。
- 前記光開始剤が、下記一般式(A)で表される化合物及び下記一般式(B)で表される化合物の少なくとも1種を含む、請求項1~5のいずれか1項に記載の感光性着色樹脂組成物。
R11、R12及びR13は、それぞれ独立に、水素原子、炭素数1~20のアルキル基、炭素数6~30のアリール基、炭素数7~30のアリールアルキル基又は炭素数2~20の複素環基を表し、
R11、R12及びR13で表される基の水素原子は、更にR21、OR21、COR21、SR21、NR22R23、CONR22R23、-NR22-OR23、-NCOR22-OCOR23、NR22COR21、OCOR21、COOR21、SCOR21、OCSR21、COSR21、CSOR21、水酸基、ニトロ基、CN、又はハロゲン原子で置換されていてもよく、
R21、R22及びR23は、それぞれ独立に、水素原子、炭素数1~20のアルキル基、炭素数6~30のアリール基、炭素数7~30のアリールアルキル基又は炭素数2~20の複素環基を表し、
R21、R22及びR23で表される基の水素原子は、更に水酸基、ニトロ基、CN、ハロゲン原子、又はカルボキシ基で置換されていてもよく、
R11、R12、R13、R21、R22及びR23で表される基のアルキレン部分は、-O-、-S-、-COO-、-OCO-、-NR24-、-NR24CO-、-NR24COO-、-OCONR24-、-SCO-、-COS-、-OCS-又は-CSO-を酸素原子が隣り合わない条件で1~5個含んでいてもよく、
R24は、水素原子、炭素数1~20のアルキル基、炭素数6~30のアリール基、炭素数7~30のアリールアルキル基又は炭素数2~20の複素環基を表し、
R11、R12、R13、R21、R22、R23及びR24で表される基のアルキル部分は、分岐側鎖があってもよく、環状アルキルであってもよく、
R3は、水素原子、炭素数1~20のアルキル基、炭素数6~30のアリール基、炭素数7~30のアリールアルキル基又は炭素数2~20の複素環基を表し、R3で表される基のアルキル部分は、分岐側鎖があってもよく、環状アルキルであってもよく、また、R3とR7、及びR3とR8はそれぞれ一緒になって環を形成していてもよく、
R3で表される基の水素原子は、更にR21、OR21、COR21、SR21、NR22R23、CONR22R23、-NR22-OR23、-NCOR22-OCOR23、NR22COR21、OCOR21、COOR21、SCOR21、OCSR21、COSR21、CSOR21、水酸基、ニトロ基、CN、又はハロゲン原子で置換されていてもよく、
R4、R5、R6及びR7は、それぞれ独立に、R11、OR11、SR11、COR14、CONR15R16、NR12COR11、OCOR11、COOR14、SCOR11、OCSR11、COSR14、CSOR11、水酸基、CN又はハロゲン原子を表し、R4とR5、R5とR6、及びR6とR7はそれぞれ一緒になって環を形成していてもよく、
R14、R15及びR16は、水素原子又は炭素数1~20のアルキル基を表し、R14、R15及びR16で表される基のアルキル部分は、分岐側鎖があってもよく、環状アルキルであってもよく、R8は、R11、OR11、SR11、COR11、CONR12R13、NR12COR11、OCOR11、COOR11、SCOR11、OCSR11、COSR11、CSOR11、水酸基、CN又はハロゲン原子を表し、
kは、0又は1を表す。)
R41、R42及びR43は、それぞれ独立に、水素原子、炭素数1~20のアルキル基、炭素数6~30のアリール基、炭素数7~30のアリールアルキル基又は炭素数2~20の複素環基を表し、
R41、R42及びR43、並びにX2で表される基の水素原子は、更にR51、OR51、COR51、SR51、NR52R53、CONR52R53、-NR52-OR53、-NCOR52-OCOR53、NR52COR51、OCOR51、COOR51、SCOR51、OCSR51、COSR51、CSOR51、水酸基、ニトロ基、CN、又はハロゲン原子で置換されていてもよく、
R51、R52及びR53は、それぞれ独立に、水素原子、炭素数1~20のアルキル基、炭素数6~30のアリール基、炭素数7~30のアリールアルキル基又は炭素数2~20の複素環基を表し、
R51、R52及びR53で表される基の水素原子は、更に水酸基、ニトロ基、CN、ハロゲン原子、又はカルボキシ基で置換されていてもよく、
R41、R42、R43、X2、R51、R52及びR53で表される基のアルキレン部分は、-O-、-S-、-COO-、-OCO-、-NR54-、-NR54CO-、-NR54COO-、-OCONR54-、-SCO-、-COS-、-OCS-又は-CSO-を酸素原子が隣り合わない条件で1~5個含んでいてもよく、
R54は、水素原子、炭素数1~20のアルキル基、炭素数6~30のアリール基、炭素数7~30のアリールアルキル基又は炭素数2~20の複素環基を表し、
R41、R42、R43、R51、R52、R53及びR54で表される基のアルキル部分は、分岐側鎖があってもよく、環状アルキルであってもよい。
a及びbは、それぞれ独立に、0~3の整数である。) - さらに多官能エポキシ化合物及び多官能ブロックイソシアネート化合物の少なくとも1種を、感光性着色樹脂組成物の固形分全量に対して、5質量%~20質量%含有する、請求項1~6のいずれか1項に記載の感光性着色樹脂組成物。
- 有機発光素子上に形成する硬化膜に用いる、請求項1~7のいずれか1項に記載の感光性着色樹脂組成物。
- 請求項1~8のいずれか1項に記載の感光性着色樹脂組成物の硬化物。
- 基板と、当該基板上に設けられた着色層とを少なくとも備えるカラーフィルタであって、当該着色層の少なくとも1つが請求項9に記載の感光性着色樹脂組成物の硬化物である、カラーフィルタ。
- 前記請求項10に記載のカラーフィルタを有する、表示装置。
- 有機発光素子上に、請求項1~7のいずれか1項に記載の感光性着色樹脂組成物の硬化膜を有する、表示装置。
- 有機発光素子上に、請求項1~7のいずれか1項に記載の感光性着色樹脂組成物を塗布することにより塗膜を形成する工程、
前記塗膜に光照射する工程、
前記光照射後の膜を、加熱するポストベイク工程、及び、
前記光照射後の膜を、現像する工程を含有することにより、
有機発光素子上に請求項1~7のいずれか1項に記載の感光性着色樹脂組成物の硬化膜を形成する工程を有する、有機発光素子と外光反射防止膜の積層体の製造方法。 - 前記ポストベイク工程における加熱温度が、130℃以下である、請求項13に記載の有機発光素子と外光反射防止膜の積層体の製造方法。
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WO2017030005A1 (ja) * | 2015-08-17 | 2017-02-23 | 株式会社Adeka | 組成物 |
JP2019038985A (ja) * | 2017-08-25 | 2019-03-14 | 東洋インキScホールディングス株式会社 | アゾ顔料、カラーフィルタ用着色剤、着組成物およびカラーフィルタ |
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JP2010015025A (ja) * | 2008-07-04 | 2010-01-21 | Adeka Corp | 特定の光重合開始剤を含有する感光性組成物 |
WO2017030005A1 (ja) * | 2015-08-17 | 2017-02-23 | 株式会社Adeka | 組成物 |
JP2019038985A (ja) * | 2017-08-25 | 2019-03-14 | 東洋インキScホールディングス株式会社 | アゾ顔料、カラーフィルタ用着色剤、着組成物およびカラーフィルタ |
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JP7407330B1 (ja) * | 2023-03-06 | 2023-12-28 | 東洋インキScホールディングス株式会社 | 感光性組成物、膜、光学フィルタ、固体撮像素子、画像表示装置、及び赤外線センサ |
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CN117480452A (zh) | 2024-01-30 |
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