WO2022210497A1 - Colored photosensitve resin composition, cured product, partition wall, color filter, and image display device - Google Patents

Colored photosensitve resin composition, cured product, partition wall, color filter, and image display device Download PDF

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WO2022210497A1
WO2022210497A1 PCT/JP2022/014893 JP2022014893W WO2022210497A1 WO 2022210497 A1 WO2022210497 A1 WO 2022210497A1 JP 2022014893 W JP2022014893 W JP 2022014893W WO 2022210497 A1 WO2022210497 A1 WO 2022210497A1
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PCT/JP2022/014893
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French (fr)
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恵理子 利光
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三菱ケミカル株式会社
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Priority to JP2023511236A priority Critical patent/JPWO2022210497A1/ja
Priority to KR1020237032528A priority patent/KR20230166082A/en
Priority to CN202280025486.7A priority patent/CN117136333A/en
Publication of WO2022210497A1 publication Critical patent/WO2022210497A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00

Definitions

  • the present invention relates to a colored photosensitive resin composition, a cured product, partition walls, a color filter and an image display device.
  • This application claims priority based on Japanese Patent Application No. 2021-061055 filed in Japan on March 31, 2021 and Japanese Patent Application No. 2021-090323 filed in Japan on May 28, 2021, and the content thereof is incorporated herein.
  • pixels and color filters using luminescent nanoparticles such as quantum dots
  • Methods for manufacturing pixels and color filters include a photolithography method and an inkjet method, and the latter method is known to reduce the loss of ink materials (see, for example, Patent Document 1).
  • pixels or color filters containing luminescent nanoparticles are manufactured by an ink jet method, pixels are formed by ejecting ink containing luminescent nanoparticles into regions (pixel portions) surrounded by prefabricated partition walls.
  • Organic electroluminescence elements used in organic electric field displays and the like are manufactured by forming partitions (banks) on a substrate and laminating various functional layers in regions surrounded by the partitions.
  • An inkjet method is known as a method for laminating a functional layer in the partition walls.
  • the barrier ribs for color filters containing luminescent nanoparticles and the barrier ribs for organic electroluminescent elements must prevent mixing of ink between adjacent pixel portions when ink is ejected by inkjet. Inkability is required.
  • Patent Document 2 discloses a colored photosensitive resin composition having high ink repellency and good linearity by using two types of specific alkali-soluble resins together. It is stated that a product is obtained.
  • Patent Document 3 describes a method for avoiding color unevenness over time by using titanium oxide particles or the like as a white film for an optical sensor together with a resin containing fluorine or siloxane.
  • Patent Document 4 describes a display device using liquid-repellent partition walls for quantum dots containing a white pigment.
  • the composition described in Patent Document 3 has a problem that it is difficult to form a pattern because the content of metal oxide particles is high.
  • the liquid-repellent barrier ribs for quantum dots described in Patent Document 4 do not describe a specific content of the composition, and it is unclear whether or not a barrier rib pattern can be formed.
  • An object of the present invention is to provide a colored photosensitive resin composition capable of forming partition walls with excellent patterning properties.
  • Another aspect of the present invention aims to provide a cured product obtained by curing the colored photosensitive resin composition, partition walls composed of the cured product, a color filter and an image display device comprising the partition walls.
  • the gist of the present invention is as follows.
  • a colored photosensitive resin composition containing (a) a coloring agent, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) a photopolymerizable compound and (e) a liquid repellent agent,
  • the content of the (a) colorant is 20% by mass or less with respect to the total solid content of the colored photosensitive resin composition
  • the (a) colorant contains (a1) titanium oxide particles,
  • the double bond equivalent of the (b) alkali-soluble resin is 1000 g/mol or less
  • the (c) photopolymerization initiator contains an oxime ester photopolymerization initiator (c1) having a maximum absorption wavelength ( ⁇ max) at a wavelength of 300 to 350 nm
  • the colored photosensitive resin composition, wherein the (e) liquid-repellent agent contains a compound (e1) having a cross-linking group and having a fluorine atom and/or a siloxane chain.
  • a colored photosensitive resin composition [6] The colored photosensitive resin composition of any one of [1] to [5], wherein the alkali-soluble resin (b) has a double bond equivalent of greater than 400 g/mol. [7] The colored photosensitive resin composition of any one of [1] to [6] containing a solvent. [8] The colored photosensitive resin composition according to any one of [1] to [7] for forming partition walls.
  • An image display device comprising the partition of [10].
  • FIG. 1 is a schematic cross-sectional view of an example of a color filter having partition walls of the present invention.
  • FIG. 2 is a schematic cross-sectional view of the partition wall of the present invention.
  • 3 is a schematic cross-sectional view of partition walls formed in Comparative Examples 3 and 4.
  • FIG. 4 shows measurement results of the total reflectance of the substrate for reflectance measurement at a wavelength of 250 to 800 nm.
  • total solid content means the amount of all components other than the solvent in the colored photosensitive resin composition. Even if a component other than the solvent is liquid at room temperature, that component is not included in the solvent but is included in the total solid content.
  • a numerical range represented by "-" means a range including the numerical values described before and after "-" as lower and upper limits.
  • (co)polymer means including both a single polymer (homopolymer) and a copolymer (copolymer), and includes “(acid) anhydride", “(anhydrous) ... "Acid” is meant to include both acids and their anhydrides.
  • “perfluoro or polyfluoro” means "one or both of perfluoro and polyfluoro.”
  • a partition wall material means a bank material, a wall material, and a wall material, and similarly, a partition wall means a bank, a wall, and a wall.
  • the weight average molecular weight means the weight average molecular weight (Mw) in terms of polystyrene by GPC (gel permeation chromatography).
  • the acid value means an acid value in terms of effective solid content, unless otherwise specified, and is calculated by neutralization titration.
  • the partition wall can be used, for example, for partitioning a functional layer such as a color filter or a light emitting element containing quantum dot nanoparticles as luminescent nanoparticles, and the partitioned region (pixel region)
  • a functional layer such as a color filter or a light emitting element containing quantum dot nanoparticles as luminescent nanoparticles
  • the partitioned region pixel region
  • ink which is a material for forming the functional layer, and drying or curing as necessary, it can be used to form pixels and the like including the functional layer and partition walls.
  • the colored photosensitive resin composition of the present invention includes (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) a photopolymerizable compound and ( e) contains a liquid-repellent agent as an essential component, and if necessary, may contain other components, for example, (f) a dispersant.
  • the colored photosensitive resin composition of the present invention contains (a) a colorant, and (a) the colorant contains (a1) titanium oxide particles.
  • the reflectance of the barrier ribs formed from the colored photosensitive resin composition tends to be increased, and the brightness of the image display device can be improved.
  • the crystal system of titanium oxide particles includes, for example, anatase type and rutile type, and is not particularly limited. From the viewpoint of stability, the rutile type with low catalytic activity is preferred.
  • Colorant may contain other metal oxide particles in addition to (a1) titanium oxide particles.
  • Other metal oxide particles include, for example, zirconium oxide, hafnium oxide, aluminum oxide, iron oxide, copper oxide, zinc oxide, yttrium oxide, niobium oxide, molybdenum oxide, indium oxide, tin oxide, tantalum oxide, tungsten oxide, Examples include particles of lead oxide, bismuth oxide, cerium oxide, antimony oxide, germanium oxide and barium titanate, and zirconium oxide and hafnium oxide are particularly preferred.
  • Composite oxide particles composed of two or more metal elements can also be used.
  • the average particle size of the primary particles of the (a1) titanium oxide particles is not particularly limited. It is preferably 500 nm or less, more preferably 400 nm or less, still more preferably 300 nm or less, and particularly preferably 250 nm or less. Moreover, it is preferably 10 nm or more, more preferably 50 nm or more, still more preferably 100 nm or more, and particularly preferably 150 nm or more.
  • the average particle size of the primary particles is equal to or less than the upper limit, the dispersion tends to be stable. If it is at least the above lower limit, there is a tendency that efficient scattering can be achieved and the light shielding property will be good.
  • the above upper and lower limits can be combined arbitrarily. For example, 10 to 500 nm is preferred, 50 to 400 nm is more preferred, 100 to 300 nm is even more preferred, and 150 to 250 nm is particularly preferred.
  • the average particle size of the primary particles of the titanium oxide particles is obtained by directly measuring the size of the primary particles from the electron micrograph using a transmission electron microscope (TEM) or a scanning electron microscope (SEM). method. Specifically, the primary particle diameter of each particle is calculated as the equivalent circle diameter. Measurements are performed on all particles within the imaging area of 100-500 nm square. Imaging different areas several times, measuring the particle size of a total of 200 to 1000 primary particles, and taking the number average, the average particle size is obtained. The measurement of the primary particle size can also be carried out on, for example, a dispersion of titanium oxide particles and a cured film of a colored photosensitive resin composition. When preparing a measurement sample, the (a1) titanium oxide particles must be uniformly present in the sample.
  • TEM transmission electron microscope
  • SEM scanning electron microscope
  • a dispersion liquid the dispersion liquid immediately after dispersion is used, and the measurement is performed after the solvent is volatilized.
  • a cured film a cured film is prepared using a colored photosensitive resin composition in which particles are uniformly dispersed, cut in the thickness direction of the film, and the cross section is observed to carry out the measurement. .
  • the average particle size of dispersed titanium oxide particles (a1) is not particularly limited, but is preferably 50 nm or more, more preferably 100 nm or more, still more preferably 120 nm or more, and particularly preferably 140 nm or more. Also, it is preferably 400 nm or less, more preferably 350 nm or less, even more preferably 300 nm or less, and particularly preferably 250 nm or less.
  • the average particle size of the dispersed particles is equal to or less than the above upper limit, there is a tendency that the dispersion is likely to be maintained. Further, when the content is at least the above lower limit, there is a tendency that the light scattering property and the light shielding property as a function of the partition wall become good.
  • the above upper and lower limits can be combined arbitrarily. For example, 50 to 400 nm is preferred, 100 to 350 nm is more preferred, 120 to 300 nm is even more preferred, and 140 to 250 nm is particularly preferred.
  • the average particle size of the dispersed particles can be measured using a dynamic light scattering method, a laser diffraction method, or a method of forming a coating film of the dispersion, drying it, and measuring the particle size with an SEM.
  • the shape of the titanium oxide particles is not particularly limited, but may be, for example, spherical, hollow, porous, rod-like, plate-like, fibrous, or irregular, preferably spherical.
  • the hollow shape has the advantage that it does not easily sink even if the particle size is large, and is effective when the particle size is larger than 200 nm, for example.
  • the coloring agent may contain coloring agents other than (a1) titanium oxide particles and other metal oxide particles (hereinafter sometimes referred to as “other coloring agents”).
  • other coloring agents The combined use of titanium oxide particles and other colorants tends to achieve both light-scattering properties and light-shielding properties.
  • the type is not particularly limited, and pigments or dyes may be used. Among these, pigments are preferably used from the viewpoint of durability.
  • One or two or more pigments may be contained in the other colorant.
  • the types of pigments that can be used as other colorants are not particularly limited, and examples thereof include organic pigments and inorganic pigments. Among these, it is preferable to use an organic pigment from the viewpoint of controlling the transmission wavelength of the colored photosensitive resin composition for efficient curing.
  • Organic pigments include organic coloring pigments and organic black pigments.
  • the organic coloring pigment means an organic pigment exhibiting a color other than black, and examples thereof include red pigment, orange pigment, blue pigment, purple pigment, green pigment, and yellow pigment.
  • organic pigments it is preferable to use an organic coloring pigment from the viewpoint of ultraviolet absorption, and it is preferable to use an organic black pigment from the viewpoint of light shielding properties and insulating properties.
  • An organic coloring pigment may be used individually by 1 type, and may use 2 or more types together.
  • organic pigments are not particularly limited, but examples include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, and perylene-based pigments. Specific examples of pigments that can be used are shown below by pigment numbers. In the following, terms such as "C.I. Pigment Red 2" refer to the Color Index (C.I.).
  • C.I. I. Pigment Red 48 1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment Red 177, 209, 224, 254 may be mentioned.
  • C.I. I. Pigment Red 177, 254, and 272 are preferable, and when the colored photosensitive resin composition is cured with ultraviolet rays, red pigments having a low ultraviolet absorption rate are preferable. I. Pigment Red 254, 272 are more preferred.
  • C.I. I. Pigment Orange 1 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 can be mentioned.
  • C.I. I. Pigment Orange 13, 43, 64, and 72 are preferable, and when the colored photosensitive resin composition is cured with ultraviolet rays, the orange pigment having a low ultraviolet absorption rate is preferable.
  • I. Pigment Orange 64, 72 are more preferred.
  • C.I. I. Pigment Blue 1 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 can be mentioned.
  • C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 60 more preferably C.I. I. Pigment Blue 15:6 may be mentioned.
  • C.I. I. Pigment Blue 15:6, 16, 60 is preferable, and when the colored photosensitive resin composition is cured with ultraviolet rays, a blue pigment having a low ultraviolet absorption rate is preferable. I. Pigment Blue 60 is more preferred.
  • C.I. I. Pigment Violet 1 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 can be mentioned.
  • C.I. I. Pigment Violet 19 23, more preferably C.I. I. Pigment Violet 23 may be mentioned.
  • C.I. I. Pigment Violet 23, 29 is preferably used, and when the colored photosensitive resin composition is cured with ultraviolet rays, the purple pigment preferably has a low ultraviolet absorption rate. I. Pigment Violet 29 is more preferred.
  • C.I. I. Pigment Green 1 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 can be mentioned.
  • C.I. I. Pigment Green 7, 36 can be mentioned.
  • C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, 180 can be mentioned.
  • At least one pigment selected from the group consisting of red pigments, orange pigments, blue pigments and violet pigments.
  • Red pigment C.I. I. Pigment Red 177, 254, 272
  • Orange pigment C.I. I. Pigment Orange 43, 64, 72
  • Blue pigment C.I. I. pigment blue 15:6,60 Purple pigment: C.I. I. Pigment Violet 23, 29
  • the combination of the organic coloring pigments is not particularly limited, but from the viewpoint of light-shielding properties, the other coloring agent is selected from the group consisting of red pigments and orange pigments. It is preferable to contain at least one kind and at least one kind selected from the group consisting of blue pigments and violet pigments.
  • the combination of colors is not particularly limited. From the viewpoint of light-shielding properties, for example, a combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment, and a combination of a blue pigment, an orange pigment and a violet pigment can be mentioned.
  • the absorption wavelength of the purple pigment is preferable in order to prevent the emission of the green quantum dot nanoparticles from causing the adjacent red quantum dot nanoparticles to emit light.
  • a wavelength pigment can be selected.
  • organic black pigments examples include perylene black, aniline black, fast black HB, and lactam compounds. From the viewpoint of plate-making properties, lactam compounds are preferred, and compounds represented by the following general formula (A) (hereinafter also referred to as "compound (A)”), geometric isomers of compound (A), compound (A ) and at least one selected from the group consisting of salts of geometric isomers of compound (A) (hereinafter sometimes referred to as “organic black pigment represented by formula (A)”) There is.) is more preferably used.
  • organic black pigment is Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF).
  • This organic black pigment is preferably used by dispersing it with a dispersant, solvent, and method, which will be described later. If a sulfonic acid derivative of compound (A) is present during dispersion, the dispersibility and storage stability may be improved, so the organic black pigment preferably contains these sulfonic acid derivatives.
  • inorganic pigments include inorganic black pigments such as carbon black, acetylene black, lamp black, bone black, graphite, iron black, and titanium black.
  • the content of (a) the colorant is 20% by mass or less with respect to the total solid content of the colored photosensitive resin composition. 15% by mass or less is preferable, 13% by mass or less is more preferable, 12% by mass or less is even more preferable, and 10% by mass or less is particularly preferable. Moreover, it is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 4% by mass or more, and particularly preferably 5% by mass or more. The above upper and lower limits can be combined arbitrarily.
  • 3 to 20% by mass is preferable, 4 to 20% by mass is more preferable, 5 to 15% by mass is more preferable, 5 to 13% by mass is even more preferable, 5 to 12% by mass is particularly preferable, and 5 to 10% by weight is particularly preferred.
  • the light-shielding property can be ensured.
  • the above upper limit there is a tendency to easily ensure dispersion stability and patterning properties.
  • the content of (a1) titanium oxide particles is 20% by mass or less with respect to the total solid content of the colored photosensitive resin composition. 15% by mass or less is preferable, 13% by mass or less is more preferable, 12% by mass or less is even more preferable, and 10% by mass or less is particularly preferable. Moreover, it is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 4% by mass or more, and particularly preferably 5% by mass or more. The above upper and lower limits can be combined arbitrarily.
  • 3 to 20% by mass is preferable, 4 to 20% by mass is more preferable, 5 to 15% by mass is more preferable, 5 to 13% by mass is even more preferable, 5 to 12% by mass is particularly preferable, and 5 to 10% by mass is more preferable.
  • % by weight is particularly preferred.
  • the content of (a1) titanium oxide particles in (a) the colorant is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and particularly preferably 80% by mass or more. , and 100% by mass or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 50 to 100% by mass is preferable, 60 to 100% by mass is more preferable, 70 to 100% by mass is even more preferable, and 80 to 100% by mass is particularly preferable. By making it more than the said lower limit, there exists a tendency which is easy to ensure light-scattering property.
  • the colored photosensitive resin composition of the present invention contains (b) an alkali-soluble resin.
  • the alkali-soluble resin is not particularly limited as long as it can be developed with an alkali developer.
  • Alkali-soluble resins include various resins having a carboxy group or a hydroxyl group, and those having a carboxy group are preferable from the viewpoint of excellent developability. From the viewpoint of improving ink repellency, an alkali-soluble resin having an ethylenically unsaturated group is preferable.
  • the (b) alkali-soluble resin of the colored photosensitive resin composition of the present invention is, from the viewpoint of ink repellency, an acrylic copolymer resin (b11) having an ethylenically unsaturated group in a side chain (hereinafter referred to as "acrylic copolymer resin (b11)" may be abbreviated.) is preferably included. From the viewpoint of the linearity of the pattern, it is preferable that the epoxy (meth)acrylate resin (b12) is included.
  • the (b) alkali-soluble resin includes both an acrylic copolymer resin (b11) and an epoxy (meth)acrylate resin (b12).
  • the acrylic copolymer resin (b11) has ethylenically unsaturated groups in side chains. By having an ethylenically unsaturated group, it is believed that photocuring by exposure occurs to form a stronger film, the liquid repellent agent is less likely to flow out during development, and ink repellency is likely to be exhibited.
  • the partial structure containing a side chain having an ethylenically unsaturated group, which the acrylic copolymer resin (b11) has, is not particularly limited. From the viewpoint of easiness of radical divergence associated with flexibility of the film, it is preferable to have, for example, a partial structure represented by the following general formula (I).
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group. * represents a bond.
  • partial structures represented by formula (I) partial structures represented by the following general formula (I') are preferable from the viewpoint of sensitivity and alkali developability.
  • R 1 and R 2 each independently represent a hydrogen atom or a methyl group.
  • R X represents a hydrogen atom or a polybasic acid residue.
  • a polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride.
  • polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylene.
  • One or more selected from tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid can be used.
  • maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and tetrahydrophthalic acid is more preferred.
  • phthalic acid and biphenyltetracarboxylic acid are preferred.
  • the acrylic copolymer resin (b11) contains the partial structure represented by formula (I), the content is not particularly limited. It is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, still more preferably 40 mol% or more, and 50 99 mol% or less is particularly preferable, 95 mol% or less is more preferable, 90 mol% or less is even more preferable, 80 mol% or less is even more preferable, and 70 mol% or less is particularly preferable.
  • the above upper and lower limits can be combined arbitrarily.
  • the ink repellency tends to be improved by making it equal to or higher than the lower limit.
  • the content is equal to or less than the above upper limit, there is a tendency that high-definition partition walls with a narrow line width can be formed.
  • the content is not particularly limited. It is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, still more preferably 40 mol% or more, and 50 99 mol% or less is particularly preferable, 95 mol% or less is more preferable, 90 mol% or less is even more preferable, 80 mol% or less is even more preferable, and 70 mol% or less is particularly preferable.
  • the above upper and lower limits can be combined arbitrarily.
  • the ink repellency tends to be improved by making it equal to or higher than the lower limit.
  • the content is equal to or less than the above upper limit, there is a tendency that high-definition partition walls with a narrow line width can be formed.
  • R3 represents a hydrogen atom or a methyl group
  • R4 represents an optionally substituted alkyl group, an optionally substituted aromatic ring group, or a substituent. represents an alkenyl group which may be present.
  • R 4 represents an optionally substituted alkyl group, an optionally substituted aromatic ring group, or an optionally substituted alkenyl group.
  • Alkyl groups for R 4 include linear, branched and cyclic alkyl groups.
  • the number of carbon atoms is preferably 1 or more, more preferably 3 or more, more preferably 5 or more, particularly preferably 8 or more, and preferably 20 or less, more preferably 18 or less, further preferably 16 or less, and 14 or less. Even more preferably, 12 or less is particularly preferable.
  • the above upper and lower limits can be combined arbitrarily.
  • 1 to 20 are preferred, 1 to 18 are more preferred, 3 to 16 are even more preferred, 5 to 14 are even more preferred, and 8 to 12 are particularly preferred.
  • the content is at least the above lower limit, the film strength tends to increase and the development adhesion tends to improve. A residue tends to be reduced by making it below the said upper limit.
  • alkyl groups include methyl, ethyl, cyclohexyl, dicyclopentanyl, and dodecanyl groups. From the viewpoint of developability, a dicyclopentanyl group or a dodecanyl group is preferable, and a dicyclopentanyl group is more preferable.
  • Substituents that the alkyl group may have include, for example, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group and carboxy group. , an acryloyl group, and a methacryloyl group, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
  • the aromatic ring group for R 4 includes monovalent aromatic hydrocarbon ring groups and monovalent aromatic heterocyclic groups.
  • the number of carbon atoms is preferably 6 or more, preferably 24 or less, more preferably 22 or less, still more preferably 20 or less, and particularly preferably 18 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 6-24, preferably 6-22, more preferably 6-20, and even more preferably 6-18. When the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. A residue tends to be reduced by making it below the said upper limit.
  • the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring.
  • Examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.
  • the aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring, such as furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring and imidazole ring.
  • oxadiazole ring indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring. From the viewpoint of developability, the aromatic ring group for
  • Substituents which the aromatic ring group may have include, for example, methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group and epoxy group. , an oligoethylene glycol group, a phenyl group, and a carboxy group, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
  • Alkenyl groups for R 4 include linear, branched and cyclic alkenyl groups.
  • the number of carbon atoms is 2 or more, preferably 22 or less, more preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 2-22, preferably 2-20, more preferably 2-18, even more preferably 2-16, even more preferably 2-14.
  • the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. A residue tends to be reduced by making it below the said upper limit.
  • alkenyl group may have include, for example, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxy group. , and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
  • R 4 is preferably an alkyl group or an alkenyl group, more preferably an alkyl group, from the viewpoint of developability and film strength.
  • the content ratio is not particularly limited, but 1 mol% with respect to the total number of moles of the structural units of the acrylic copolymer resin (b11). 2 mol% or more is more preferable, 5 mol% or more is more preferable, 10 mol% or more is particularly preferable, 20 mol% or more is particularly preferable, and 70 mol% or less is preferable, and 60 mol% or less is preferable. More preferably, 50 mol % or less is even more preferable, and 40 mol % or less is particularly preferable. The above upper and lower limits can be combined arbitrarily.
  • Adhesion tends to be improved by making it more than the said lower limit.
  • a residue tends to be reduced by making it below the said upper limit.
  • R 5 represents a hydrogen atom or a methyl group
  • R 6 represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted represents an optionally substituted alkynyl group, a hydroxy group, a carboxy group, a halogen atom, an optionally substituted alkoxy group, a thiol group, or an optionally substituted alkylsulfide group.
  • t represents an integer of 0 to 5;
  • R 6 is an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a hydroxy group, a carboxy group, represents a halogen atom, an optionally substituted alkoxy group, a thiol group, or an optionally substituted alkylsulfide group.
  • Alkyl groups for R 6 include linear, branched and cyclic alkyl groups.
  • the number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, even more preferably 14 or less, and 12 or less. is particularly preferred.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 20, preferably 1 to 18, more preferably 3 to 16, even more preferably 5 to 14. When the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. A residue tends to be reduced by making it below the said upper limit.
  • alkyl groups examples include methyl, ethyl, cyclohexyl, dicyclopentanyl, and dodecanyl groups. From the viewpoint of developability and film strength, a dicyclopentanyl group and a dodecanyl group are preferred, and a dicyclopentanyl group is more preferred.
  • Substituents that the alkyl group may have include, for example, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group and carboxy group. , an acryloyl group, and a methacryloyl group, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
  • Alkenyl groups for R 6 include linear, branched and cyclic alkenyl groups.
  • the number of carbon atoms is 2 or more, preferably 22 or less, more preferably 20 or less, still more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 2-22, preferably 2-20, more preferably 2-18, even more preferably 2-16, even more preferably 2-14.
  • the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. A residue tends to be reduced by making it below the said upper limit.
  • alkenyl group may have include, for example, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxy group. , and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
  • Alkynyl groups for R 6 include linear, branched and cyclic alkynyl groups.
  • the number of carbon atoms is 2 or more, preferably 22 or less, more preferably 20 or less, still more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 2-22, preferably 2-20, more preferably 2-18, even more preferably 2-16, even more preferably 2-14.
  • the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. A residue tends to be reduced by making it below the said upper limit.
  • Substituents that the alkynyl group may have include, for example, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group and carboxy group. , and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
  • the halogen atom for R 6 includes, for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferred from the viewpoint of ink repellency.
  • Alkoxy groups for R 6 include linear, branched and cyclic alkoxy groups.
  • the number of carbon atoms is 1 or more, preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 1-20, preferably 1-18, more preferably 1-16, even more preferably 1-14, even more preferably 1-12.
  • the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. A residue tends to be reduced by making it below the said upper limit.
  • Substituents that the alkoxy group may have include, for example, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxy group.
  • an acryloyl group, and a methacryloyl group, and from the viewpoint of developability a hydroxy group and an oligoethylene glycol group are preferred.
  • the alkylsulfide group for R 6 includes linear, branched and cyclic alkylsulfide groups.
  • the number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 1-20, preferably 1-18, more preferably 1-16, even more preferably 1-14, even more preferably 1-12.
  • the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. A residue tends to be reduced by making it below the said upper limit.
  • substituents that the alkyl group in the alkylsulfide group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl group, carboxyl group, acryloyl group, and methacryloyl group, and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferred.
  • R 6 is preferably a hydroxy group or a carboxy group, more preferably a carboxy group, from the viewpoint of developability.
  • t represents an integer of 0 to 5, and t is preferably 0 from the viewpoint of ease of production.
  • the content is not particularly limited. It is preferably 0.5 mol % or more, more preferably 1 mol % or more, still more preferably 2 mol % or more, and particularly preferably 4 mol % or more, relative to the total number of moles of the structural units of the acrylic copolymer resin (b11). Also, it is preferably 50 mol % or less, more preferably 30 mol % or less, even more preferably 20 mol % or less, even more preferably 10 mol % or less, and particularly preferably 6 mol % or less. The above upper and lower limits can be combined arbitrarily.
  • it is 0.5 to 50 mol %, preferably 1 to 30 mol %, more preferably 1 to 20 mol %, even more preferably 2 to 10 mol %, still more preferably 4 to 6 mol %.
  • content is equal to or higher than the lower limit, there is a tendency that the uniformity of the film is improved. A residue tends to be reduced by making it below the said upper limit.
  • R7 represents a hydrogen atom or a methyl group.
  • the acrylic copolymer resin (b11) contains the partial structure represented by formula (IV), the content is not particularly limited. It is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, and preferably 80 mol% or less, based on the total number of moles of the structural units of the acrylic copolymer resin (b11). mol % or less is more preferable, and 60 mol % or less is even more preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 5 to 80 mol %, preferably 10 to 70 mol %, more preferably 20 to 60 mol %. Residue tends to be reduced by making it equal to or higher than the lower limit. The ink repellency tends to be improved by making it equal to or less than the above upper limit.
  • the acid value of the acrylic copolymer resin (b11) is not particularly limited. Preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, still more preferably 30 mgKOH/g or more, even more preferably 50 mgKOH/g or more, particularly preferably 60 mgKOH/g or more, and preferably 150 mgKOH/g or less, 140 mgKOH /g or less, more preferably 130 mgKOH/g or less, and even more preferably 120 mgKOH/g or less.
  • the above upper and lower limits can be combined arbitrarily.
  • 10 to 150 mgKOH/g preferably 20 to 140 mgKOH/g, more preferably 30 to 130 mgKOH/g, still more preferably 50 to 120 mgKOH/g, even more preferably 60 to 120 mgKOH/g.
  • Developability tends to be improved by setting the content to be at least the above lower limit. When the amount is set to the above upper limit or less, there is a tendency that development adhesion is improved.
  • the weight average molecular weight (Mw) of the acrylic copolymer resin (b11) is not particularly limited. 1000 or more is preferable, 2000 or more is more preferable, 4000 or more is more preferable, 6000 or more is even more preferable, 7000 or more is particularly preferable, 8000 or more is particularly preferable, 30000 or less is preferable, and 20000 or less is more preferable, 15,000 or less is more preferable, and 10,000 or less is particularly preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 1,000 to 30,000 is preferred, 2,000 to 20,000 is more preferred, 4,000 to 20,000 is even more preferred, 6,000 to 15,000 is even more preferred, 7,000 to 15,000 is even more preferred, and 8,000 to 10,000 is particularly preferred.
  • the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. A residue tends to be reduced by making it below the said upper limit.
  • the content of the acrylic copolymer resin (b11) contained in the alkali-soluble resin is not particularly limited.
  • (b) is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, even more preferably 50% by mass or more, and particularly 55% by mass or more, relative to the total mass of the alkali-soluble resin 90% by mass or less is preferable, 80% by mass or less is more preferable, 70% by mass or less is even more preferable, and 65% by mass or less is particularly preferable.
  • the above upper and lower limits can be combined arbitrarily.
  • the ink repellency tends to be improved by making it equal to or higher than the lower limit.
  • the content is equal to or less than the above upper limit, there is a tendency that high-definition partition walls with a narrow line width can be formed.
  • the content of the acrylic copolymer resin (b11) is It is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and even more preferably 50% by mass or more, relative to the total content of the epoxy (meth)acrylate resin (b12). , 55% by mass or more is particularly preferable, 90% by mass or less is preferable, 80% by mass or less is more preferable, 70% by mass or less is even more preferable, and 65% by mass or less is particularly preferable. The above upper and lower limits can be combined arbitrarily.
  • the ink repellency tends to be improved by making it equal to or higher than the lower limit. By making it equal to or less than the above upper limit, there is a tendency that the verticality of the cross section of the partition wall is improved.
  • acrylic copolymer resin (b11) examples include resins described in Japanese Patent Application Laid-Open Nos. 8-297366 and 2001-89533.
  • Epoxy (meth)acrylate resin (b12) Epoxy (meth)acrylate resin (b12) is obtained by adding an ethylenically unsaturated monocarboxylic acid or an ester compound to an epoxy resin, optionally reacting with an isocyanate group-containing compound, and then further reacting with a polybasic acid or its anhydride.
  • Epoxy (meth)acrylate resin has substantially no epoxy group in terms of chemical structure, and is not limited to "(meth)acrylate", but epoxy compound (epoxy resin) is a raw material, and Since "(meth)acrylate” is a representative example, the name is used in this way according to common practice.
  • epoxy (b12) epoxy (meth)acrylate resin those having an aromatic ring in the main chain can be more preferably used from the viewpoint of pattern linearity.
  • the epoxy resin includes a raw material compound before forming a resin by thermosetting, and the epoxy resin can be appropriately selected and used from known epoxy resins.
  • the epoxy resin a compound obtained by reacting a phenolic compound and epihalohydrin can be used.
  • the phenolic compound is preferably a compound having a divalent or more divalent phenolic hydroxyl group, and may be a monomer or a polymer.
  • Epoxy resin dihydroxylfluorene-type epoxy resin, dihydroxylalkyleneoxylfluorene-type epoxy resin, 9,9-bis(4′-hydroxyphenyl)diglycidyl ether of fluorene, 1,1-bis(4′-hydroxy phenyl)adamantane, and those having an aromatic ring in the main chain can be preferably used.
  • bisphenol A epoxy resin bisphenol A epoxy resin
  • phenol novolak epoxy resin cresol novolak epoxy resin
  • polymerized epoxy resin of phenol and dicyclopentadiene diglycidyl of 9,9-bis(4′-hydroxyphenyl)fluorene.
  • Etherates are preferred, and bisphenol A epoxy resins are particularly preferred.
  • epoxy resins include bisphenol A type epoxy resins (e.g., "jER (registered trademark, hereinafter the same) 828", “jER1001", “jER1002", “jER1004" manufactured by Mitsubishi Chemical Corporation, manufactured by Nippon Kayaku Co., Ltd.).
  • NER-1302 epoxy equivalent 323, softening point 76 ° C.
  • bisphenol F type resin for example, Mitsubishi Chemical "jER807”, “jER4004P”, “jER4005P”, “jER4007P”, Nippon Kayaku "NER-7406” (epoxy equivalent 350, softening point 66 ° C.), etc.
  • EOCN triglycidyl isocyanate Nurate
  • TEPIC trisphenolmethane type epoxy resin
  • EPPN-501 e.g., "EPPN-502”, "EPPN-503” manufactured by Nippon Kayaku Co., Ltd.
  • alicyclic epoxy resins e.g., "Celoxide (registered trademark) 2021P” and “Celoxide EHPE” manufactured by Daicel Corporation
  • epoxy resins obtained by glycidylating phenol resins by reaction of dicyclopentadiene and phenol for example, "EXA-7200” manufactured by DIC Corporation, "NC-7300” manufactured by Nippon Kayaku Co., Ltd.
  • epoxy resins represented by the following general formulas (i-11) to (i-14) can be suitably used.
  • epoxy resin represented by the following general formula (i-11) As an epoxy resin represented by the following general formula (i-11), "XD-1000” manufactured by Nippon Kayaku Co., Ltd., and as an epoxy resin represented by the following general formula (i-12), Japan “NC-3000” manufactured by Kayaku Co., Ltd., and "ESF-300” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. as an epoxy resin represented by the following general formula (i-14).
  • n is an average value and represents a number from 0 to 10.
  • Each R 111 independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. Plural R 111 in one molecule may be the same or different.
  • n is an average value and represents a number from 0 to 10.
  • Each R 121 independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. Plural R 121 in one molecule may be the same or different.
  • X represents a linking group represented by general formula (i-13-1) or (i-13-2) below. However, it contains one or more adamantane structures in its molecular structure.
  • c represents 2 or 3;
  • R 131 to R 134 and R 135 to R 137 each independently represent an optionally substituted adamantyl group, a hydrogen atom, It represents an optionally substituted alkyl group having 1 to 12 carbon atoms, or an optionally substituted phenyl group. * represents a bond.
  • p and q each independently represent an integer of 0 to 4
  • R 141 and R 142 each independently represent an alkyl group having 1 to 4 carbon atoms or a halogen atom
  • R 143 and R 144 each independently represent an alkylene group having 1 to 4 carbon atoms
  • x and y each independently represent an integer of 0 or more.
  • Examples of ethylenically unsaturated monocarboxylic acids include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, pentaerythritol tri(meth)acrylate succinic anhydride adduct, penta Erythritol tri(meth)acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta(meth)acrylate succinic anhydride adduct, dipentaerythritol penta(meth)acrylate phthalic anhydride adduct, dipentaerythritol penta(meth)acrylate tetrahydro Examples include phthalic anhydride adducts and reaction products of (meth)acrylic acid and ⁇ -caprolactone. From the viewpoint of sensitivity, (meth)acrylic acid is preferred.
  • polybasic acids examples include succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4 - ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid , benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, and their anhydrides.
  • succinic anhydride succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are preferable, and succinic anhydride and tetrahydrophthalic anhydride are more preferable.
  • the use of a polyhydric alcohol tends to increase the molecular weight of the epoxy (meth)acrylate resin (b12), introduce branches into the molecule, and balance the molecular weight and viscosity. In addition, the rate of introduction of acid groups into the molecule can be increased, and there is a tendency to easily balance sensitivity, adhesion, and the like.
  • the polyhydric alcohol is, for example, one or more polyhydric alcohols selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. Preferably.
  • epoxy (meth)acrylate resins examples include resins described in Korean Patent Publication No. 10-2013-0022955 in addition to the resins described above.
  • the acid value of the epoxy (meth)acrylate resin (b12) is not particularly limited. 10 mgKOH/g or more is preferable, 30 mgKOH/g or more is more preferable, 50 mgKOH/g or more is still more preferable, 70 mgKOH/g or more is even more preferable, 80 mgKOH/g or more is particularly preferable, and 200 mgKOH/g or less is preferable, and 180 mgKOH/g is preferable. /g or less, more preferably 150 mgKOH/g or less, even more preferably 120 mgKOH/g or less, and particularly preferably 110 mgKOH/g or less.
  • the above upper and lower limits can be combined arbitrarily.
  • 10 to 200 mgKOH/g is preferred, 30 to 180 mgKOH/g is more preferred, 50 to 150 mgKOH/g is even more preferred, 70 to 120 mgKOH/g is even more preferred, and 80 to 110 mgKOH/g is particularly preferred.
  • Developability tends to be improved by setting the content to be at least the above lower limit. When the content is equal to or less than the above upper limit, there is a tendency that the film strength is improved.
  • the weight average molecular weight (Mw) of the epoxy (meth)acrylate resin (b12) is not particularly limited. 1000 or more is preferable, 2000 or more is more preferable, 3000 or more is more preferable, 4000 or more is particularly preferable, 5000 or more is particularly preferable, 30000 or less is preferable, 20000 or less is more preferable, 15000 or less is more preferable, 10000 The following is particularly preferable, and 8000 or less is particularly preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 1,000 to 30,000 is preferred, 2,000 to 20,000 is more preferred, 3,000 to 15,000 is even more preferred, 4,000 to 10,000 is particularly preferred, and 5,000 to 8,000 is particularly preferred.
  • the content is equal to or higher than the lower limit, there is a tendency that the film strength is improved. A residue tends to be reduced by making it below the said upper limit.
  • the alkali-soluble resin contains the epoxy (meth)acrylate resin (b12), the content is not particularly limited.
  • (b) is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, even more preferably 35% by mass or more, and particularly 40% by mass or more, relative to the total mass of the alkali-soluble resin 50% by mass or more is most preferable, 90% by mass or less is preferable, 70% by mass or less is more preferable, and 60% by mass or less is even more preferable.
  • the above upper and lower limits can be combined arbitrarily.
  • 10 to 90% by mass preferably 20 to 90% by mass, more preferably 30 to 70% by mass, still more preferably 35 to 70% by mass, even more preferably 40 to 60% by mass, particularly preferably 50 to 60% by mass. % by mass.
  • the linearity tends to be improved by making it equal to or higher than the lower limit.
  • the content is equal to or less than the above upper limit, there is a tendency that high-definition partition walls with a narrow line width can be formed.
  • the epoxy (meth)acrylate resin (b12) can be synthesized by a conventionally known method. Specifically, the epoxy resin is dissolved in an organic solvent, and in the presence of a catalyst and a thermal polymerization inhibitor, the acid or ester compound having the ethylenically unsaturated bond is added for addition reaction, and further polybasic acid or its A method of continuing the reaction by adding anhydride can be used. For example, the methods described in Japanese Patent No. 3938375 and Japanese Patent No. 5169422 can be mentioned.
  • Examples of the organic solvent used for the reaction include one or more organic solvents such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate.
  • Examples of catalysts include tertiary amines such as triethylamine, benzyldimethylamine and tribenzylamine; One or more of ammonium salts, phosphorus compounds such as triphenylphosphine, stibines such as triphenylstibine, and the like can be used.
  • Examples of thermal polymerization inhibitors include one or more of hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, and the like.
  • the amount of the acid or ester compound having an ethylenically unsaturated bond is preferably 0.7 to 1.3 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents, per one chemical equivalent of the epoxy group of the epoxy resin. more preferred.
  • the temperature during the addition reaction is preferably 60 to 150°C, more preferably 80 to 120°C.
  • the amount of polybasic acid (anhydride) to be used is preferably 0.1 to 1.2 chemical equivalents, more preferably 0.2 to 1.1 chemical equivalents, with respect to 1 chemical equivalent of hydroxyl groups generated in the addition reaction. .
  • epoxy (meth)acrylate resins (b12) from the viewpoint of film strength and linearity, epoxy (meth)acrylate resins having a partial structure represented by the following general formula (i) and epoxy (meth)acrylate resins represented by the following general formula (ii) It is preferable that at least one selected from the group consisting of epoxy (meth)acrylate resins having a partial structure is included.
  • R a represents a hydrogen atom or a methyl group
  • R b represents a divalent hydrocarbon group which may have a substituent.
  • the benzene ring in formula (i) may be further substituted with any substituent. * represents a bond.
  • each R c independently represents a hydrogen atom or a methyl group.
  • R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. * represents a bond.
  • epoxy (meth)acrylate resin having a partial structure represented by formula (i) (hereinafter sometimes referred to as "epoxy (meth)acrylate resin (b12-1)") will be described in detail.
  • R a represents a hydrogen atom or a methyl group
  • R b represents a divalent hydrocarbon group which may have a substituent.
  • the benzene ring in formula (i) may be further substituted with any substituent. * represents a bond.
  • R b represents a divalent hydrocarbon group which may have a substituent.
  • the divalent hydrocarbon group includes a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked. mentioned.
  • the divalent aliphatic group includes linear, branched and cyclic aliphatic groups.
  • a linear aliphatic group is preferred from the viewpoint of development solubility.
  • a cyclic aliphatic group is preferred from the viewpoint of reducing permeation of the developer into the exposed area.
  • the number of carbon atoms in the divalent aliphatic group is preferably 1 or more, more preferably 3 or more, still more preferably 6 or more, and is preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 20 are preferred, 3 to 15 are more preferred, and 6 to 10 are even more preferred.
  • the ink repellency tends to be improved by making it equal to or less than the above upper limit.
  • divalent linear aliphatic groups examples include methylene group, ethylene group, n-propylene group, n-butylene group, n-hexylene group and n-heptylene group.
  • a methylene group is preferable from the viewpoint of ink repellency and manufacturing cost.
  • the divalent branched aliphatic group includes a divalent linear aliphatic group, and side chains such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group. , a sec-butyl group, and a structure having a tert-butyl group.
  • the number of rings that the divalent cyclic aliphatic group has is not particularly limited. 1 or more is preferable, 2 or more is more preferable, 10 or less is preferable, and 5 or less is more preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 10 are preferred, and 2 to 5 are more preferred.
  • the content is equal to or higher than the lower limit, there is a tendency that the film strength is improved.
  • the developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
  • the divalent cyclic aliphatic group for example, two hydrogen atoms are removed from a ring such as cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, and cyclododecane ring. groups. From the viewpoint of film strength and developability, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable.
  • substituents that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.
  • the divalent aromatic ring group includes a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
  • the number of carbon atoms is preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 4 to 20 are preferred, 5 to 15 are more preferred, and 6 to 10 are even more preferred.
  • the developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
  • the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring.
  • the divalent aromatic hydrocarbon ring group includes, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.
  • the aromatic heterocyclic ring in the aromatic heterocyclic group may be monocyclic or condensed.
  • divalent aromatic heterocyclic groups include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, and indole ring having two free valences.
  • the divalent aromatic ring group is preferably a benzene ring or naphthalene ring having two free val
  • substituents that the divalent aromatic ring group may have include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. From the viewpoint of curability, non-substitution is preferred.
  • one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic ring groups is linked to one or more.
  • the number of divalent aliphatic groups is not particularly limited, it is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 10 are preferred, 1 to 5 are more preferred, and 2 to 3 are even more preferred. Developability tends to be improved by setting the content to be at least the above lower limit.
  • the content is equal to or less than the above upper limit, there is a tendency that the film strength is improved.
  • the number of divalent aromatic ring groups is not particularly limited, it is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 10 are preferred, 1 to 5 are more preferred, and 2 to 3 are even more preferred.
  • the content is equal to or higher than the lower limit, there is a tendency that the film strength is improved.
  • the developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
  • Examples of groups in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups represented by the following formulas (iA) to (iF). be done.
  • a group represented by the following formula (iA) is preferable from the viewpoint of rigidity of the skeleton and hydrophobicity of the membrane.
  • Examples of acceptable substituents for the benzene ring in formula (i) include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
  • the number of substituents is also not particularly limited, and may be one or two or more. From the viewpoint of curability, it is preferably unsubstituted.
  • the partial structure represented by formula (i) is preferably a partial structure represented by formula (i-1) below from the viewpoint of development solubility.
  • R a and R b have the same definitions as in formula (i).
  • RY represents a hydrogen atom or a polybasic acid residue. * represents a bond.
  • the benzene ring in formula (i-1) may be further substituted with any substituent.
  • a polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride.
  • polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylene.
  • tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid can be mentioned.
  • maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and tetrahydrophthalic acid is more preferred.
  • phthalic acid and biphenyltetracarboxylic acid are preferred.
  • the repeating unit structure represented by the formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin (b12-1) may be one or two or more.
  • the number of partial structures represented by formula (i) contained in one molecule of the epoxy (meth)acrylate resin (b12-1) is not particularly limited. 1 or more is preferable, 2 or more is more preferable, 3 or more is more preferable, 10 or less is preferable, and 8 or less is more preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 10 are preferred, 2 to 10 are more preferred, and 3 to 8 are even more preferred.
  • Developability tends to be improved by setting the content to be at least the above lower limit. When the content is equal to or less than the above upper limit, there is a tendency that the film strength is improved.
  • the number of partial structures represented by formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin (b12-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and 3. Above is more preferable, 10 or less is preferable, and 8 or less is more preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 10 are preferred, 2 to 10 are more preferred, and 3 to 8 are even more preferred.
  • Developability tends to be improved by setting the content to be at least the above lower limit. When the content is equal to or less than the above upper limit, there is a tendency that the film strength is improved.
  • epoxy (meth)acrylate resin (b12-1) Specific examples of the epoxy (meth)acrylate resin (b12-1) are given below.
  • epoxy (meth)acrylate resin having the partial structure represented by formula (ii) (hereinafter sometimes referred to as "epoxy (meth)acrylate resin (b12-2)") will be described in detail.
  • each R c independently represents a hydrogen atom or a methyl group.
  • R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. * represents a bond.
  • R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
  • the cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.
  • the number of rings that the aliphatic ring group has is not particularly limited. 1 or more is preferable, 2 or more are preferable, 10 or less are preferable, 5 or less are more preferable, and 3 or less are more preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 10 are preferred, 1 to 5 are more preferred, and 2 to 3 are even more preferred.
  • the number of carbon atoms in the aliphatic ring group is preferably 4 or more, more preferably 6 or more, still more preferably 8 or more, preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 4 to 40 are preferred, 4 to 30 are more preferred, 6 to 20 are even more preferred, and 8 to 15 are particularly preferred.
  • Examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, and cyclododecane ring.
  • An adamantane ring is preferred from the viewpoint of film strength and developability.
  • the number of rings that the aromatic ring group has is not particularly limited. It is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, preferably 10 or less, more preferably 5 or less, and even more preferably 4 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 10 are preferred, 2 to 5 are more preferred, and 3 to 4 are even more preferred.
  • the content is equal to or higher than the lower limit, there is a tendency that the film strength is improved. The developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
  • Aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups.
  • the number of carbon atoms in the aromatic ring group is preferably 4 or more, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, particularly preferably 12 or more, preferably 40 or less, and more preferably 30 or less. , is more preferably 20 or less, and particularly preferably 15 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 4 to 40 are preferred, 6 to 40 are more preferred, 8 to 30 are even more preferred, 10 to 20 are even more preferred, and 12 to 15 are particularly preferred.
  • When the content is equal to or higher than the lower limit, there is a tendency that the film strength is improved. The developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
  • the aromatic ring in the aromatic ring group includes, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring.
  • a fluorene ring is preferred from the viewpoint of patterning properties.
  • the divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited. Examples thereof include divalent aliphatic groups, divalent aromatic ring groups, and groups in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked.
  • the divalent aliphatic group includes linear, branched and cyclic aliphatic groups.
  • a linear aliphatic group is preferred from the viewpoint of improving developability, and a cyclic aliphatic group is preferred from the viewpoint of film strength.
  • the number of carbon atoms in the divalent aliphatic group is preferably 1 or more, more preferably 3 or more, still more preferably 6 or more, and is preferably 25 or less, more preferably 20 or less, and still more preferably 15 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 25 are preferred, 3 to 20 are more preferred, and 6 to 15 are even more preferred.
  • the developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
  • divalent linear aliphatic groups examples include methylene group, ethylene group, n-propylene group, n-butylene group, n-hexylene group and n-heptylene group.
  • a methylene group is preferable from the viewpoint of ink repellency.
  • the divalent branched aliphatic group includes the divalent linear aliphatic group described above, and side chains such as methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl. structures having a group, a sec-butyl group, and a tert-butyl group.
  • the number of rings that the divalent cyclic aliphatic group has is not particularly limited. 1 or more is preferable, 2 or more is more preferable, 10 or less is preferable, 5 or less is more preferable, and 3 or less is more preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 10 are preferred, 1 to 5 are more preferred, and 2 to 3 are even more preferred.
  • the divalent cyclic aliphatic group includes, for example, a group obtained by removing two hydrogen atoms from a cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, or cyclododecane ring. is mentioned. From the viewpoint of film strength, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable.
  • substituents that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.
  • the divalent aromatic ring group includes a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
  • the number of carbon atoms in the divalent aromatic ring group is preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 4 to 30 are preferred, 5 to 20 are more preferred, and 6 to 15 are even more preferred.
  • the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring.
  • the divalent aromatic hydrocarbon ring group includes, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.
  • the aromatic heterocycle in the divalent aromatic heterocyclic group may be a monocyclic ring or a condensed ring.
  • divalent aromatic heterocyclic groups include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, and indole ring having two free valences.
  • the divalent aromatic ring group is preferably a benzene ring or naphthalene ring having two free val
  • substituents that the divalent aromatic ring group may have include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. From the viewpoint of curability, non-substitution is preferred.
  • one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic ring groups is linked to one or more.
  • the number of divalent aliphatic groups is not particularly limited. 1 or more is preferable, 2 or more is more preferable, 10 or less is preferable, 5 or less is more preferable, and 3 or less is more preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 10 are preferred, 1 to 5 are more preferred, and 2 to 3 are even more preferred. Developability tends to be improved by setting the content to be at least the above lower limit.
  • the number of divalent aromatic ring groups is not particularly limited. 1 or more is preferable, 2 or more is more preferable, 10 or less is preferable, 5 or less is more preferable, and 3 or less is more preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 10 are preferred, 1 to 5 are more preferred, and 2 to 3 are even more preferred.
  • the developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
  • Examples of groups in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups represented by formulas (iA) to (iF) described above. mentioned. From the viewpoint of achieving both film strength and ink repellency, the group represented by formula (iC) is preferred.
  • the bonding mode of the side chain cyclic hydrocarbon group is not particularly limited to these divalent hydrocarbon groups.
  • an aspect in which one hydrogen atom of an aliphatic group or an aromatic ring group is substituted with a cyclic hydrocarbon group that is a side chain, or a cyclic hydrocarbon group that is a side chain including one of the carbon atoms of the aliphatic group The aspect which constituted is mentioned.
  • the partial structure represented by formula (ii) is preferably a partial structure represented by general formula (ii-1) below.
  • R c has the same meaning as in formula (ii).
  • R ⁇ represents a monovalent cyclic hydrocarbon group which may have a substituent.
  • n is an integer of 1 or more. * represents a bond.
  • the benzene ring in formula (ii-1) may be further substituted with any substituent.
  • R ⁇ represents a monovalent cyclic hydrocarbon group which may have a substituent.
  • the cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.
  • the number of rings that the aliphatic ring group has is not particularly limited. 1 or more is preferable, 2 or more is more preferable, 6 or less is preferable, 4 or less is more preferable, and 3 or less is more preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 6 are preferred, 1 to 4 are more preferred, and 2 to 3 are even more preferred.
  • the number of carbon atoms in the aliphatic ring group is preferably 4 or more, more preferably 6 or more, still more preferably 8 or more, preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 4 to 40 are preferred, 4 to 30 are more preferred, 6 to 20 are even more preferred, and 8 to 15 are particularly preferred.
  • Examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, and cyclododecane ring.
  • An adamantane ring is preferable from the viewpoint of compatibility between film strength and developability.
  • the number of rings possessed by the aromatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and preferably 10 or less, more preferably 5 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 10 are preferred, 2 to 10 are more preferred, and 3 to 5 are even more preferred.
  • Aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups.
  • the number of carbon atoms in the aromatic ring group is preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 4 to 30 are preferred, 5 to 20 are more preferred, and 6 to 15 are even more preferred.
  • aromatic ring in the aromatic ring group examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, and fluorene ring.
  • a fluorene ring is preferable from the viewpoint of achieving both film strength and developability.
  • Substituents that the cyclic hydrocarbon group may have include, for example, hydroxy group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, Alkyl groups having 1 to 5 carbon atoms such as amyl group and isoamyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; nitro group; cyano group; and carboxy group. Unsubstituted is preferred from the viewpoint of ease of synthesis.
  • n represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 3 are preferred, and 2 to 3 are more preferred.
  • Developability tends to be improved by setting the content to be at least the above lower limit. When the content is equal to or less than the above upper limit, there is a tendency that the film strength is improved.
  • R ⁇ is preferably a monovalent aliphatic cyclic group, more preferably an adamantyl group.
  • Examples of acceptable substituents on the benzene ring in formula (ii-1) include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
  • the number of substituents is also not particularly limited, and may be one or two or more. From the viewpoint of curability, it is preferably unsubstituted.
  • the partial structure represented by formula (ii) is preferably a partial structure represented by the following general formula (ii-2) from the viewpoint of development adhesion.
  • R c has the same definition as in formula (ii) above.
  • R ⁇ represents a divalent cyclic hydrocarbon group which may have a substituent. * represents a bond.
  • the benzene ring in formula (ii-2) may be further substituted with any substituent.
  • R ⁇ represents an optionally substituted divalent cyclic hydrocarbon group.
  • the cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.
  • the number of rings that the aliphatic ring group has is not particularly limited. 1 or more is preferable, 2 or more is more preferable, 10 or less is preferable, and 5 or less is more preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 10 are preferred, and 2 to 5 are more preferred.
  • the developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
  • the number of carbon atoms in the aliphatic ring group is preferably 4 or more, more preferably 6 or more, still more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and still more preferably 30 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 4 to 40 are preferred, 6 to 35 are more preferred, and 8 to 30 are even more preferred.
  • the developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
  • the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring and cyclododecane ring.
  • An adamantane ring is preferable from the viewpoint of compatibility between film strength and developability.
  • the number of rings that the aromatic ring group has is not particularly limited. It is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, preferably 10 or less, and more preferably 5 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 10 are preferred, 2 to 10 are more preferred, and 3 to 5 are even more preferred.
  • Aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups.
  • the number of carbon atoms in the aromatic ring group is preferably 4 or more, more preferably 6 or more, more preferably 8 or more, particularly preferably 10 or more, preferably 40 or less, more preferably 30 or less, and further preferably 20 or less, 15 or less is particularly preferred.
  • the above upper and lower limits can be combined arbitrarily. For example, 4 to 40 are preferred, 6 to 30 are more preferred, 8 to 20 are even more preferred, and 10 to 15 are particularly preferred.
  • aromatic ring in the aromatic ring group examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, and fluorene ring.
  • a fluorene ring is preferred from the viewpoint of film strength and developability.
  • Substituents that the cyclic hydrocarbon group may have include, for example, hydroxy group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, Alkyl groups having 1 to 5 carbon atoms such as amyl group and isoamyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; nitro group; cyano group; and carboxy group. Unsubstituted is preferred from the viewpoint of ease of synthesis.
  • R ⁇ is preferably a divalent aliphatic cyclic group, more preferably a divalent adamantane cyclic group. From the viewpoint of achieving both film strength and developability, R ⁇ is preferably a divalent aromatic ring group, more preferably a divalent fluorene ring group.
  • Examples of acceptable substituents for the benzene ring in formula (ii-2) include hydroxy, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy groups.
  • the number of substituents is also not particularly limited, and may be one or two or more. From the viewpoint of curability, it is preferably unsubstituted.
  • the partial structure represented by formula (ii) is preferably a partial structure represented by general formula (ii-3) below.
  • R c and R d have the same definitions as in formula (ii).
  • R Z represents a hydrogen atom or a polybasic acid residue.
  • a polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride.
  • polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylene.
  • tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid can be mentioned.
  • maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and tetrahydrophthalic acid is more preferred.
  • phthalic acid and biphenyltetracarboxylic acid are preferred.
  • the partial structure represented by the formula (ii-3) contained in one molecule of the epoxy (meth)acrylate resin (b12-2) may be one type or two or more types.
  • the number of partial structures represented by formula (ii) contained in one molecule of the epoxy (meth)acrylate resin (b12-2) is not particularly limited. 1 or more is preferable, 3 or more is more preferable, 20 or less is preferable, 15 or less is more preferable, and 10 or less is more preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 20 are preferred, 1 to 15 are more preferred, and 3 to 10 are even more preferred.
  • the ink repellency tends to be improved by making it equal to or higher than the lower limit.
  • the developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
  • the number of partial structures represented by formula (ii-1) contained in one molecule of the epoxy (meth)acrylate resin (b12-2) is not particularly limited. 1 or more is preferable, 3 or more is more preferable, 20 or less is preferable, 15 or less is more preferable, and 10 or less is more preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 20 are preferred, 1 to 15 are more preferred, and 3 to 10 are even more preferred.
  • the ink repellency tends to be improved by making it equal to or higher than the lower limit.
  • the developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
  • the number of partial structures represented by formula (ii-2) contained in one molecule of the epoxy (meth)acrylate resin (b12-2) is not particularly limited. 1 or more is preferable, 3 or more is more preferable, 20 or less is preferable, 15 or less is more preferable, and 10 or less is more preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 20 are preferred, 1 to 15 are more preferred, and 3 to 10 are even more preferred.
  • the ink repellency tends to be improved by making it equal to or higher than the lower limit.
  • the developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
  • the number of partial structures represented by formula (ii-3) contained in one molecule of the epoxy (meth)acrylate resin (b12-2) is not particularly limited. 1 or more is preferable, 3 or more is more preferable, 20 or less is preferable, 15 or less is more preferable, and 10 or less is more preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 20 are preferred, 1 to 15 are more preferred, and 3 to 10 are even more preferred.
  • the ink repellency tends to be improved by making it equal to or higher than the lower limit.
  • the developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
  • the (b) alkali-soluble resin in the present invention may contain an alkali-soluble resin other than the acrylic copolymer resin (b11) and the epoxy (meth)acrylate resin (b12).
  • the acid value of the alkali-soluble resin is not particularly limited. 10 mgKOH/g or more is preferable, 20 mgKOH/g or more is more preferable, 25 mgKOH/g or more is still more preferable, 200 mgKOH/g or less is preferable, 150 mgKOH/g or less is more preferable, and 100 mgKOH/g or less is more preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 15 to 150 mgKOH/g is preferred, 20 to 120 mgKOH/g is more preferred, and 25 to 100 mgKOH/g is even more preferred. Developability tends to be improved by setting the content to be at least the above lower limit.
  • the acid value means a weighted average value according to the content ratio.
  • the double bond equivalent of the alkali-soluble resin is 1000 g/mol or less, preferably 800 g/mol or less, more preferably 700 g/mol or less, and particularly preferably 600 g/mol or less. Also, it is preferably 300 g/mol or more, more preferably greater than 390 g/mol, even more preferably greater than 400 g/mol, and particularly preferably 450 g/mol or more.
  • the above upper and lower limits can be combined arbitrarily. For example, it is preferably from 300 to 1000 g/mol, more preferably from 390 g/mol to 1000 g/mol, even more preferably from 400 g/mol to 1000 g/mol, and particularly preferably from 450 to 800 g/mol. .
  • the alkali-soluble resin is a mixture of two or more kinds
  • the double bond equivalent of the (b) alkali-soluble resin is the weight average molecular weight of the whole alkali-soluble resin
  • the ethylenicity of the whole alkali-soluble resin It can be calculated by dividing by the average number of unsaturated double bonds. Alternatively, it can be calculated from the harmonic average value of each double bond equivalent.
  • the content of (b) the alkali-soluble resin in the colored photosensitive resin composition of the present invention is not particularly limited.
  • the total solid content of the colored photosensitive resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, even more preferably 30% by mass or more, and 40% by mass or more. 50% by mass or more is even more preferable, 60% by mass or more is particularly preferable, 90% by mass or less is preferable, 80% by mass or less is more preferable, and 70% by mass or less is even more preferable.
  • the above upper and lower limits can be combined arbitrarily.
  • Residue tends to be reduced by making it equal to or higher than the lower limit.
  • the ink repellency tends to be improved by making it equal to or less than the above upper limit.
  • the total content of (d) the photopolymerizable compound and (b) the alkali-soluble resin relative to the total solid content of the colored photosensitive resin composition is not particularly limited. 10% by mass or more is preferable, 30% by mass or more is more preferable, 60% by mass or more is more preferable, 80% by mass or more is particularly preferable, and 95% by mass or less is preferable, and 92% by mass or less is more preferable, and 90% by mass. % or less is more preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 10 to 95% by mass is preferable, 30 to 95% by mass is more preferable, 60 to 92% by mass is even more preferable, and 80 to 90% by mass is particularly preferable.
  • the colored photosensitive resin composition of the present invention contains (c) a photopolymerization initiator, and (c) the photopolymerization initiator has a maximum wavelength of 300 to 350 nm. It contains an oxime ester photopolymerization initiator (c1) having an absorption wavelength ( ⁇ max) (hereinafter sometimes abbreviated as “oxime ester photopolymerization initiator (c1)”).
  • the colored photosensitive resin composition of the present invention contains an oxime ester photopolymerization initiator (c1) having a maximum absorption wavelength ( ⁇ max) at a wavelength of 300 to 350 nm, so that it is affected by scattered light due to titanium oxide particles. Since sufficient curability can be ensured without the need for curing, it is possible to achieve a favorable patterning shape, line width, and adhesion at the same time.
  • the oxime ester photopolymerization initiator (c1) has a maximum absorption wavelength ( ⁇ max) at a wavelength of 300-350 nm.
  • the maximum absorption wavelength of the oxime ester photopolymerization initiator (c1) is 300 nm or longer, preferably 310 nm or longer, and more preferably 320 nm or longer. Moreover, it is 350 nm or less, preferably 345 nm or less, and more preferably 340 nm or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 310-345 nm is preferable, and 320-340 nm is more preferable. By making it more than the said lower limit, there exists a tendency which can ensure adhesiveness enough. When the thickness is equal to or less than the above upper limit, there is a tendency that a shape with less skirting can be secured.
  • the maximum absorption wavelength of the oxime ester photopolymerization initiator (c1) can be measured, for example, by the following method. First, a 0.01% by mass propylene glycol monomethyl ether acetate (PGMEA) solution of the oxime ester photopolymerization initiator (c1) was prepared, placed in a 1 cm square quartz cell, and irradiated with light having a wavelength of 250 to 400 nm with a spectrophotometer. It can be obtained by irradiating and measuring every 1 nm. Examples of spectrophotometers include UV-3000 series, UV-3000 series (manufactured by Shimadzu Corporation), and V-700 series (manufactured by JASCO Corporation), but are not limited to these.
  • PMEA propylene glycol monomethyl ether acetate
  • the oxime ester photopolymerization initiator (c1) preferably has a maximum absorbance of 2 or less, particularly preferably 1.5 or less, at 360 to 400 nm in a 0.01% by mass propylene glycol monomethyl ether acetate solution. .
  • the thickness equal to or less than the above upper limit, there is a tendency that a shape with a small skirting can be secured.
  • the oxime ester photopolymerization initiator (c1) is not particularly limited as long as it has a maximum absorption wavelength ( ⁇ max) at a wavelength of 300 to 350 nm. mentioned.
  • a compound having a carbazole skeleton is preferable in terms of adhesion.
  • a compound having a diphenyl sulfide skeleton is preferred because the maximum absorption wavelength ( ⁇ max) can be easily controlled to an appropriate wavelength.
  • the chemical structure of the oxime ester-based photopolymerization initiator (c1) is not particularly limited, it may be a compound having a chemical structure represented by the following general formula (c1-1) or the following general formula (c1-2). preferable.
  • R 3 represents an optionally substituted alkyl group or an optionally substituted aromatic ring group.
  • R 4 represents an optionally substituted alkyl group or an optionally substituted aromatic ring group.
  • R5 represents any monovalent substituent.
  • q represents an integer of 0 to 3;
  • R6 represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aromatic ring group.
  • optionally substituted alkyl groups for R 3 in formula (c1-1) include alkyl groups having 1 to 6 carbon atoms and cycloalkyl groups having 4 to 20 carbon atoms.
  • Examples of the optionally substituted aromatic ring group for R 3 in formula (c1-1) include a phenyl group and a naphthyl group.
  • R 3 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group.
  • the optionally substituted alkyl group includes, for example, an alkyl group having 2 to 12 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 20 carbon atoms.
  • Examples include alkyl groups and cycloalkylalkyl groups having 3 to 20 carbon atoms.
  • the aromatic ring group optionally having a substituent includes a phenyl group and a naphthyl group.
  • r is an integer from 0 to 3;
  • R 4 is an unsubstituted linear alkyl group such as a methyl group, an ethyl group, a propyl group, a cycloalkylalkyl group, or a propyl group substituted with an N-acetyl-N-acetoxyamino group. is preferred, and a propyl group substituted with an N-acetyl-N-acetoxyamino group is more preferred.
  • Examples of monovalent substituents for R 5 include alkyl groups having 1 to 10 carbon atoms such as methyl group and ethyl group; alkoxy groups having 1 to 10 carbon atoms such as methoxy group and ethoxy group; F, Cl and Br.
  • acyl groups having 1 to 10 carbon atoms alkyl ester groups having 1 to 10 carbon atoms; alkoxycarbonyl groups having 1 to 10 carbon atoms; halogenated alkyl groups having 1 to 10 carbon atoms; ⁇ 10 aromatic ring group; amino group; aminoalkyl group having 1 to 10 carbon atoms; hydroxyl group; CN group; optionally substituted benzoyl group; optionally substituted naphthoyl group; A thenoyl group which may have a substituent is exemplified. From the viewpoint of liquid repellency, an unsubstituted benzoyl group and an unsubstituted naphthoyl group are preferable, and an unsubstituted naphthoyl group is more preferable.
  • the optionally substituted alkyl group for R 6 includes an alkyl group having 2 to 12 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, an alkenyl group having 3 to 25 carbon atoms, and an alkenyl group having 3 to 25 carbon atoms.
  • An alkyl group is mentioned.
  • a phenyl group and a naphthyl group are mentioned as an aromatic ring group which may have a substituent in R6 .
  • R6 is preferably an unsubstituted methyl group or ethyl group.
  • q represents an integer of 0-3. From the viewpoint of radical generation efficiency, q is preferably 0 or 1, more preferably 1.
  • R 13A represents an optionally substituted alkyl group or an optionally substituted aromatic ring group.
  • R 14A represents an alkyl group or an aromatic ring group.
  • R 15A represents a monovalent substituent.
  • n represents 0 or 1;
  • h represents an integer of 0 to 2;
  • the alkyl group for R 13A in formula (c1-2) may be linear, branched, cyclic, or a combination thereof.
  • the number of carbon atoms in the alkyl group is not particularly limited. It is preferably 1 or more, more preferably 2 or more, still more preferably 4 or more, preferably 20 or less, more preferably 10 or less, even more preferably 8 or less, even more preferably 7 or less, and particularly preferably 4 or less.
  • the solubility in a solvent tends to be improved by adjusting the content to the above upper limit or less.
  • the above upper and lower limits can be combined arbitrarily.
  • the number of carbon atoms in the alkyl group is preferably 1-20, more preferably 1-10, still more preferably 1-8, even more preferably 1-7, and particularly preferably 1-4.
  • alkyl groups include methyl, ethyl, propyl, butyl, pentyl, isopentyl, hexyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, and cyclohexylethyl groups. From the viewpoint of developability, preferred are a methyl group, a hexyl group, an isopentyl group, a hexyl group, a cyclopentylmethyl group and a cyclohexylmethyl group, and more preferred are a hexyl group and a cyclopentylmethyl group.
  • substituents that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, and an alkoxycarbonyl group.
  • a methyl group is preferred from the standpoint of developability. From the viewpoint of solubility, an alkoxycarbonyl group is preferred. From the viewpoint of ease of synthesis, it is preferably unsubstituted.
  • the aromatic ring group for R 13A in formula (c1-2) includes an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 4 or more, more preferably 5 or more, preferably 30 or less, more preferably 20 or less, and still more preferably 12 or less.
  • the aromatic ring group preferably has 4 to 30 carbon atoms, more preferably 4 to 20 carbon atoms, still more preferably 4 to 12 carbon atoms, and particularly preferably 5 to 12 carbon atoms.
  • Examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, and a furyl group. Among these, from the viewpoint of developability, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.
  • R 13A is preferably an optionally substituted alkyl group, more preferably a methyl group, a hexyl group or a methoxycarbonylethyl group, and even more preferably a methoxycarbonyl group.
  • the alkyl group for R 14A in formula (c1-2) may be linear, branched, cyclic, or a combination thereof.
  • the number of carbon atoms in the alkyl group is not particularly limited. 1 or more is preferable, 5 or less is preferable, and 3 or less is more preferable.
  • the sensitivity tends to be good when the content is equal to or less than the above upper limit.
  • the above upper and lower limits can be combined arbitrarily.
  • the number of carbon atoms in the alkyl group is preferably 1-5, more preferably 1-3.
  • alkyl group examples include methyl group, ethyl group, propyl group, and pentyl group, and among these, the methyl group is preferable from the viewpoint of sensitivity.
  • the aromatic ring group for R 14A in formula (c1-2) includes an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the number of carbon atoms in the aromatic ring group is not particularly limited. 4 or more is preferable, 5 or more is more preferable, 30 or less is preferable, 20 or less is more preferable, and 12 or less is more preferable.
  • the aromatic ring group preferably has 4 to 30 carbon atoms, more preferably 4 to 20 carbon atoms, still more preferably 4 to 12 carbon atoms, and particularly preferably 5 to 12 carbon atoms.
  • aromatic ring groups examples include phenyl groups, naphthyl groups, pyridyl groups, and furyl groups. From the viewpoint of patterning properties, a phenyl group and a naphthyl group are preferred, and a phenyl group is more preferred.
  • R 14A in formula (c1-2) is preferably an aromatic ring group, more preferably a phenyl group or a naphthyl group, and still more preferably a phenyl group. From the viewpoint of liquid repellency, a methyl group is preferred.
  • R 16A includes an optionally substituted alkyl group and an optionally substituted aromatic ring group.
  • the alkyl group for R 16A may be linear, branched, cyclic, or a combination thereof.
  • the number of carbon atoms in the alkyl group is not particularly limited. 1 or more is preferable, 2 or more is more preferable, 3 or more is still more preferable, 8 or less is preferable, and 5 or less is more preferable.
  • the lower limit value or more tends to improve the developability, and the upper limit value or less tends to improve the patterning property.
  • the above upper and lower limits can be combined arbitrarily.
  • the number of carbon atoms in the alkyl group is preferably 1-8, more preferably 2-5.
  • alkyl groups include methyl, ethyl, propyl, and pentyl groups. From the viewpoint of solubility, a methyl group and an ethyl group are preferred, and an ethyl group is more preferred.
  • substituent that the alkyl group may have include a hydroxyl group and a carboxy group, and a hydroxyl group is preferable from the viewpoint of developability.
  • the aromatic ring group for R 16A includes aromatic hydrocarbon ring groups and aromatic heterocyclic groups.
  • the number of carbon atoms in the aromatic ring group is not particularly limited. 4 or more is preferable, 5 or more is more preferable, 30 or less is preferable, 20 or less is more preferable, and 12 or less is more preferable.
  • the developability tends to be improved by making it equal to or higher than the above lower limit.
  • the patterning property tends to be good by making it equal to or less than the above upper limit.
  • the above upper and lower limits can be combined arbitrarily.
  • the aromatic ring group preferably has 4 to 30 carbon atoms, more preferably 4 to 20 carbon atoms, still more preferably 4 to 12 carbon atoms, and particularly preferably 5 to 12 carbon atoms.
  • aromatic ring groups examples include phenyl, naphthyl, thienyl, furyl, benzothienyl, and benzofuryl groups. From the viewpoint of patterning properties, a benzothienyl group and a benzofuryl group are preferable, and a benzofuryl group is more preferable.
  • substituent that the aromatic ring group may have include an alkyl group, a hydroxyl group, and a carboxy group, and unsubstituted is preferred from the viewpoint of synthesis.
  • n is preferably 1 from the viewpoint of patterning properties, and preferably 0 from the viewpoint of sensitivity.
  • h is preferably 0 or 1, more preferably 0, from the viewpoint of patterning properties.
  • the substitution position of R 15A is not particularly limited, but from the viewpoint of synthesis, the o-position or p-position is preferable, and the p-position is more preferable.
  • Examples of the oxime ester-based photopolymerization initiator (c1) include the following compounds.
  • the oxime ester photopolymerization initiator (c1) may be used alone or in combination of two or more.
  • the (c) photopolymerization initiator in the colored photosensitive resin composition of the present invention is optionally a photopolymerization initiator other than the oxime ester photopolymerization initiator (c1) (hereinafter referred to as “other photopolymerization initiators ) may be included.
  • Other photopolymerization initiators may be oxime ester compounds, or may be compounds other than oxime ester compounds.
  • photopolymerization initiators those commonly used in this field can be used.
  • metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197; hexaarylbiimidazole derivatives described in JP-A-2000-56118 halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, N-aryl- ⁇ -amino acids such as N-phenylglycine, N-aryl- ⁇ - Examples include radical activators such as amino acid salts, N-aryl- ⁇ -amino acid esters, and ⁇ -aminoalkylphenone derivatives.
  • the metallocene compounds include, for example, dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis(2,3,4,5,6-pentafluorophenyl ), dicyclopentadienyl titanium bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyl titanium bis(2,4,6-trifluorophenyl), dicyclopentadienyl titanium di( 2,6-difluorophenyl), dicyclopentadienyl titanium di(2,4-difluorophenyl), di(methylcyclopentadienyl) titanium bis(2,3,4,5,6-pentafluorophenyl), Di(methylcyclopentadienyl) titanium bis(2,6-difluorophenyl), dicyclopentadienyl titanium [2,6-di-fluoro-3-(pyrrol-1
  • Biimidazole derivatives include, for example, 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole dimer, 2-(2′-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2′-methoxyphenyl)-4,5-diphenylimidazole dimer, (4′-methoxyphenyl )-4,5-diphenylimidazole dimer.
  • halomethylated oxadiazole derivatives examples include 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[ ⁇ -(2'- benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[ ⁇ -(2′-(6′′-benzofuryl)vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.
  • halomethyl-s-triazine derivatives examples include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis( trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl) -s-triazines.
  • ⁇ -aminoalkylphenone derivatives include 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Morpholinophenyl)butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4 -dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, 4-(diethylamino)chalcone.
  • an oxime ester photopolymerization initiator other than the oxime ester photopolymerization initiator (c1) may be used.
  • Another photoinitiator may be used individually by 1 type, or may be used in combination of 2 or more types.
  • the photopolymerization initiator can be blended with a sensitizing dye and a polymerization accelerator according to the wavelength of the image exposure light source, if necessary, for the purpose of increasing sensitivity.
  • sensitizing dyes include the xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, JP-A-3-239703 and JP-A-5-289335. JP-A-3-239703, 3-ketocoumarin compounds described in JP-A-5-289335, and JP-A-6-19240.
  • an amino group-containing sensitizing dye is preferable, and a compound having an amino group and a phenyl group in the same molecule is more preferable.
  • 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 3,4-diamino Benzophenone compounds such as benzophenone; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2- (p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)-1
  • polymerization accelerators examples include aromatic amines such as ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone, and 4-dimethylaminopropiophenone, and n-butylamine. , N-methyldiethanolamine, and 2-dimethylaminoethyl benzoate can be used.
  • the polymerization accelerator may be used alone or in combination of two or more.
  • the content of (c) the photopolymerization initiator in the colored photosensitive resin composition of the present invention is not particularly limited. Preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 1% by mass or more, and even more preferably 1.5% by mass, relative to the total solid content of the colored photosensitive resin composition Above, particularly preferably 2% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, even more preferably 10% by mass or less, particularly preferably 8 % by mass or less, most preferably 6% by mass or less.
  • the above upper and lower limits can be combined arbitrarily.
  • ink repellency tends to be improved by making it equal to or higher than the lower limit.
  • a residue tends to be reduced by making it below the said upper limit.
  • the content of the oxime ester photopolymerization initiator (c1) in the colored photosensitive resin composition of the present invention is not particularly limited.
  • 0.01% by mass or more Preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 1% by mass or more, and even more preferably 1.5% by mass, relative to the total solid content of the colored photosensitive resin composition
  • particularly preferably 2% by mass or more preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, even more preferably 10% by mass or less, particularly preferably 8 % by mass or less, most preferably 6% by mass or less.
  • the above upper and lower limits can be combined arbitrarily.
  • ink repellency tends to be improved by making it equal to or higher than the lower limit.
  • a residue tends to be reduced by making it below the said upper limit.
  • the content of the oxime ester photopolymerization initiator (c1) in the photopolymerization initiator (c) in the colored photosensitive resin composition of the present invention is not particularly limited.
  • (c) is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass or more, and particularly preferably 90% by mass or more, relative to the total mass of the photopolymerization initiator.
  • 100 mass % or less is preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 30 to 100% by mass is preferable, 50 to 100% by mass is more preferable, 70 to 100% by mass is even more preferable, and 90 to 100% by mass is particularly preferable. By making it more than the said lower limit, there exists a tendency for sufficient ink repellency to arise.
  • the patterning property tends to be good by making it equal to or less than the above upper limit.
  • the mixing ratio of (c) photopolymerization initiator to (d) photopolymerizable compound in the colored photosensitive resin composition is preferably 1 part by weight or more with respect to 100 parts by weight of (d) photopolymerizable compound, More preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, preferably 200 parts by mass or less, more preferably 100 parts by mass or less, 50 parts by mass or less is more preferable, and 30 parts by mass or less is particularly preferable.
  • the above upper and lower limits can be combined arbitrarily.
  • the ink repellency tends to be improved by making it equal to or higher than the lower limit.
  • a residue tends to be reduced by making it below the said upper limit.
  • the mixing ratio of the oxime ester photopolymerization initiator (c1) to the (d) photopolymerizable compound in the colored photosensitive resin composition is 1 part by mass or more with respect to 100 parts by mass of the (d) photopolymerizable compound. is preferable, 5 parts by mass or more is more preferable, 10 parts by mass or more is more preferable, 15 parts by mass or more is even more preferable, 20 parts by mass or more is particularly preferable, and 200 parts by mass or less is preferable, and 100 parts by mass or less is It is more preferably 50 parts by mass or less, and particularly preferably 30 parts by mass or less.
  • the above upper and lower limits can be combined arbitrarily.
  • the ink repellency tends to be improved by making it equal to or higher than the lower limit.
  • a residue tends to be reduced by making it below the said upper limit.
  • a chain transfer agent may be used in combination with the photopolymerization initiator.
  • chain transfer agents include mercapto group-containing compounds and carbon tetrachloride. It is more preferable to use a mercapto group-containing compound because it tends to have a high chain transfer effect. This is probably because bond cleavage is likely to occur due to the small SH bond energy, and hydrogen abstraction reaction and chain transfer reaction are likely to occur.
  • the use of a chain transfer agent is effective in improving sensitivity and surface curability, and is therefore advantageous in developing liquid repellency.
  • the mercapto group-containing compound may have a plurality of mercapto groups in the molecule.
  • - Mercapto group-containing compounds having an aromatic ring such as triazole, 2-mercapto-4(3H)-quinazoline, ⁇ -mercaptonaphthalene, 1,4-dimethylmercaptobenzene; Hexanedithiol, decanedithiol, butanediol bis(3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol bis(3-mercaptopropionate), ethylene glycol bisthioglycolate, trimethylolpropane tris ( 3-mercaptopropionate), trimethylolpropane tristhioglycolate, trishydroxyethyl tristhiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptoprop
  • 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred, and among aliphatic mercapto group-containing compounds, trimethylolpropane tris (3-mercaptopropionate) , pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol Tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione are preferred.
  • aliphatic mercapto group-containing compounds are preferred, and specifically, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris.
  • a chain transfer agent may be used individually by 1 type, and may use 2 or more types together.
  • 2-mercaptobenzothiazole 2-mercaptobenzimidazole
  • 2-mercaptobenzoxazole 2-mercaptobenzoxazole
  • 2-mercaptobenzothiazole 2-mercaptobenzimidazole
  • 2-mercaptobenzothiazole and 2-mercaptobenzimidazole may be used in combination.
  • one or more selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoxazole, and pentaerythritol tetrakis (3-mercaptopropionate) It is preferable to use one or more selected from the group consisting of pentaerythritol tetrakis(3-mercaptobutyrate) in combination with a photopolymerization initiator.
  • the content of the chain transfer agent is not particularly limited, but is preferably 0.01% by mass based on the total solid content of the colored photosensitive resin composition. Above, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, still more preferably 0.8% by mass or more, and preferably 5% by mass or less, more preferably 4% by mass Below, more preferably 3 mass % or less, still more preferably 2 mass % or less. The above upper and lower limits can be combined arbitrarily.
  • the ink repellency tends to be improved by making it equal to or higher than the lower limit.
  • the content is equal to or less than the above upper limit, there is a tendency that high-definition partition walls with a narrow line width can be formed.
  • the content ratio of the chain transfer agent to the (c) photopolymerization initiator is 5 parts by weight with respect to 100 parts by weight of the (c) photopolymerization initiator.
  • parts by mass or more more preferably 10 parts by mass or more, more preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, and preferably 500 parts by mass or less, more preferably 300 parts by mass or less, and 100 parts by mass or less. is more preferable, and 50 parts by mass or less is particularly preferable.
  • the above upper and lower limits can be combined arbitrarily.
  • the ink repellency tends to be improved by making it equal to or higher than the lower limit.
  • the content is equal to or less than the above upper limit, there is a tendency that high-definition partition walls with a narrow line width can be formed.
  • Photopolymerizable compound The colored photosensitive resin composition of the present invention contains (d) a photopolymerizable compound. (d) It is believed that the inclusion of the photopolymerizable compound increases the curability of the coating film and improves the ink repellency. (d) Photopolymerizable compounds include compounds having one or more ethylenically unsaturated bonds in the molecule (hereinafter also referred to as ethylenically unsaturated compounds).
  • a compound having two or more ethylenically unsaturated bonds in the molecule is preferable from the viewpoint of being able to expand the difference in developer solubility between the exposed area and the non-exposed area due to polymerizability, crosslinkability, and the like.
  • the unsaturated bond is more preferably derived from a (meth)acryloyloxy group, that is, a (meth)acrylate compound.
  • polyfunctional ethylenic monomers having two or more ethylenically unsaturated bonds in one molecule.
  • the number of ethylenically unsaturated groups possessed by the polyfunctional ethylenic monomer is not particularly limited, but is preferably 2 or more, more preferably 3 or more, still more preferably 5 or more, and preferably 15. Below, more preferably 10 or less, still more preferably 8 or less, particularly preferably 7 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 2 to 15 are preferred, 2 to 10 are more preferred, 3 to 8 are even more preferred, and 5 to 7 are particularly preferred.
  • Ethylenically unsaturated compounds include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds, etc. and esters obtained by an esterification reaction of polyhydric hydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids.
  • esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol ethane triacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate.
  • pentaerythritol tetraacrylate dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate
  • acrylic acid esters of aliphatic polyhydroxy compounds such as glycerol acrylate
  • methacrylics obtained by replacing the acrylates of these exemplary compounds with methacrylates acid esters
  • crotonate esters obtained by replacing the acrylates of these exemplary compounds with crotonates
  • maleate esters obtained by replacing the acrylates of these exemplary compounds with maleates obtained by replacing the acrylates of these exemplary compounds with maleates.
  • Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters and methacryl esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. acid esters. Esters obtained by the esterification reaction of polyhydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids are not necessarily single substances, but are representative.
  • condensates of acrylic acid, phthalic acid and ethylene glycol condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, and adipine.
  • Condensates of acids, butanediol and glycerin may be mentioned.
  • polyfunctional ethylenic monomer used in the present invention for example, a polyisocyanate compound and a hydroxyl group-containing (meth)acrylic acid ester or a polyisocyanate compound, a polyol and a hydroxyl group-containing (meth)acrylic acid ester are reacted.
  • Urethane (meth)acrylates such as those obtained; epoxy acrylates such as addition reaction products of polyepoxy compounds and hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylenebisacrylamide; diallyl phthalate and vinyl group-containing compounds such as divinyl phthalate.
  • Urethane (meth)acrylates include, for example, DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U- 10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B, Examples include UV-7600B, UV-7605B, UV-7630B, and UV7640B (manufactured by Mitsubishi Chemical Corporation).
  • the photopolymerizable compound is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid or a urethane (meth)acrylate, and dipentaerythritol hexa (Meth)acrylates, dipentaerythritol penta(meth)acrylate, 2,2,2-tris(meth)acryloyloxymethylethyl phthalate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipenta A dibasic acid anhydride adduct of erythritol penta(meth)acrylate and a dibasic acid anhydride adduct of pentaerythritol tri(meth)acrylate are more preferred.
  • Photopolymerizable compounds may be used singly or
  • the molecular weight of (d) the photopolymerizable compound is not particularly limited. From the viewpoint of ink repellency and the formation of high-definition partition walls with a narrow line width, the is 500 or more, preferably 1000 or less, more preferably 700 or less.
  • the above upper and lower limits can be arbitrarily crossed. For example, 100 to 1000 is preferred, 150 to 1000 is more preferred, 200 to 1000 is even more preferred, 300 to 700 is even more preferred, 400 to 700 is even more preferred, and 500 to 700 is particularly preferred.
  • the number of carbon atoms in the photopolymerizable compound is not particularly limited. From the viewpoint of ink repellency and residue suppression, it is preferably 7 or more, more preferably 10 or more, still more preferably 15 or more, even more preferably 20 or more, particularly preferably 25 or more, and preferably 50 or less, more preferably It is 40 or less, more preferably 35 or less, and particularly preferably 30 or less.
  • the above upper and lower limits can be arbitrarily crossed. For example, 7 to 50 are preferred, 10 to 50 are more preferred, 15 to 40 are even more preferred, 20 to 35 are even more preferred, and 25 to 30 are particularly preferred.
  • Photopolymerizable compounds include ester (meth)acrylates, epoxy (meth)acrylates, and urethane (meth)acrylates from the viewpoint of ink repellency and formation of high-definition partition walls with a narrow line width.
  • trifunctional or higher ester (meth)acrylates such as pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and dipentaerythritol penta(meth)acrylate, 2,2, 2-tris(meth)acryloyloxymethylethyl phthalic acid, acid anhydride adducts to tri- or higher functional ester (meth)acrylates such as dibasic acid anhydride adducts of dipentaerythritol penta(meth)acrylate is more preferable in terms of ink repellency and formation of fine partition walls with a narrow line width.
  • the content of (d) the photopolymerizable compound in the colored photosensitive resin composition of the present invention is not particularly limited. With respect to the total solid content of the colored photosensitive resin composition, preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, even more preferably 15% by mass or more, particularly preferably 20% by mass or more % by mass or more, preferably 80% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, and even more preferably 45% by mass or less.
  • the above upper and lower limits can be combined arbitrarily.
  • the ink repellency tends to be improved by making it equal to or higher than the lower limit.
  • the content is equal to or less than the above upper limit, there is a tendency that high-definition partition walls with a narrow line width can be formed.
  • the content of (d) the photopolymerizable compound relative to 100 parts by mass of the alkali-soluble resin (b) is not particularly limited. Preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, still more preferably 20 parts by mass or more, even more preferably 25 parts by mass or more, even more preferably 30 parts by mass or more , Most preferably 40 parts by mass or more, preferably 150 parts by mass or less, more preferably 100 parts by mass or less, still more preferably 90 parts by mass or less, even more preferably 80 parts by mass or less, particularly preferably 70 parts by mass It is below the department.
  • the above upper and lower limits can be combined arbitrarily.
  • the ink repellency tends to be improved by making it equal to or higher than the lower limit.
  • the content is equal to or less than the above upper limit, there is a tendency that high-definition partition walls with a narrow line width can be formed.
  • liquid repellent agent The colored photosensitive resin composition of the present invention contains (e) a liquid repellent agent, and (e) the liquid repellent agent has a cross-linking group and a fluorine atom and/or It contains a compound (e1) having a siloxane chain. (e) By containing a liquid-repellent agent, ink repellency can be imparted to the surface of the obtained partition wall, so that the obtained partition wall can prevent color mixture for each pixel.
  • Compound (e1) has a cross-linking group, a fluorine atom and/or a siloxane chain.
  • the cross-linking group of the compound (e1) include an epoxy group, an ethylenically unsaturated group, and an active group that generates a radical upon irradiation with an active energy ray. Ethylenically unsaturated groups are preferred. It is believed that when a liquid repellent agent having a cross-linking group is used, the liquid repellent agent itself participates in the cross-linking reaction, making it difficult for the liquid repellent agent to flow out during development, and as a result, the partition walls obtained exhibit high ink repellency.
  • the liquid repellent agent tends to be oriented on the surface of the partition wall and work to prevent ink bleeding and color mixing. More specifically, the fluorine atom-containing groups and/or siloxane chains tend to repel ink and prevent ink bleeding and color mixing due to ink crossing the partition into adjacent areas.
  • a liquid repellent agent having a cross-linking group, a fluorine atom and a siloxane chain in one molecule a liquid repellent agent having a cross-linking group and a fluorine atom, and a liquid repellent agent having a cross-linking group and a siloxane chain are used singly. may be used, or two or more may be used in combination.
  • compound (e1) When compound (e1) has a fluorine atom, compound (e1) preferably has at least one of the group consisting of a fluoroalkyl group, a fluoroalkylene group, a fluoroalkylene ether chain and a fluoroaromatic group. Having a perfluoroalkyl group, a perfluoroalkylene group, a perfluoroalkylene ether chain, or a perfluoroaromatic group is more preferable from the viewpoint of liquid repellency.
  • Having at least one selected from the group consisting of a fluoroalkyl group, a fluoroalkylene group, a fluoroalkylene ether chain, and a fluoroaromatic group makes it easier for the compound (e1) to be oriented on the partition wall surface, resulting in higher ink repellency. and tend to further prevent ink bleeding and color mixing.
  • fluoroalkyl groups Specific examples of fluoroalkyl groups, fluoroalkylene groups, fluoroalkylene ether chains and fluoroaromatic groups are shown below. and "polyfluoro" with some hydrogen atoms remaining.
  • fluoroalkyl groups include fluoromethyl, fluoroethyl, fluoropropyl, fluorobutyl, and fluorohexyl groups.
  • Fluoroalkylene chains include, for example, fluoromethylene chains, fluoroethylene chains, fluoropropylene chains, fluorobutylene groups, and fluorohexylene chains.
  • fluoroalkylene ether chains examples include -CF 2 -O-, -(CF 2 ) 2 -O-, -(CF 2 ) 3 -O-, -CF 2 -C(CF 3 )O-, -C Examples thereof include (CF 3 )--CF 2 --O-- and divalent groups having repeating units thereof, and those in which a portion of the fluorine atoms in the above fluoroalkylene ether chain are hydrogen atoms.
  • Fluoroaromatic groups include, for example, fluorophenyl groups, fluoronaphthyl groups, and fluoroanthracyl groups.
  • Liquid repellent agents having a cross-linking group and a fluorine atom include, for example, an acrylic copolymer resin having an epoxy group and a fluoroalkyl group, an acrylic copolymer resin having an epoxy group and a fluoroalkylene ether chain, an ethylenically unsaturated group and a fluoroalkyl group.
  • an acrylic copolymer resin having an ethylenically unsaturated group and a fluoroalkylene ether chain an epoxy (meth)acrylate resin having an epoxy group and a fluoroalkyl group, an epoxy having an epoxy group and a fluoroalkylene ether chain
  • examples include meth)acrylate resins, epoxy (meth)acrylate resins having an ethylenically unsaturated group and a fluoroalkyl group, and epoxy (meth)acrylate resins having an ethylenically unsaturated group and a fluoroalkylene ether chain.
  • an acrylic copolymer resin having an ethylenically unsaturated group and a fluoroalkyl group an acrylic copolymer resin having an ethylenically unsaturated group and a fluoroalkylene ether chain are preferable, and an ethylenically unsaturated group and a fluoroalkylene ether chain are preferable.
  • An acrylic copolymer resin having an ether chain is more preferred.
  • liquid repellent agents having a cross-linking group and a fluorine atom include, for example, DIC's "Megafac (registered trademark, hereinafter the same.) F116", “Megafac F120", “Megafac F142D”, and “Megafac F144D”.
  • “Megaface RS-72-K”, “Megaface RS-78” and “Megaface RS-90” can be preferably used as acrylic copolymer resins having an ethylenically unsaturated group and a fluoroalkylene ether chain. can.
  • the fluorine atom content in compound (e1) is not particularly limited. It is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and even more preferably 20% by mass or more, relative to the total mass of compound (e1). Moreover, 50 mass % or less is preferable and 35 mass % or less is more preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 5 to 50% by mass is preferable, 10 to 50% by mass is more preferable, 15 to 35% by mass is even more preferable, and 20 to 35% by mass is particularly preferable. By making it more than the said lower limit, there exists a tendency which shows a high contact angle. When the content is equal to or less than the upper limit value, there is a tendency that the outflow to the pixel portion can be suppressed.
  • the siloxane chain possessed by the compound (e1) is preferably polysiloxane represented by the following structural formula (E).
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently represent a monovalent organic group or a hydrogen atom.
  • the monovalent organic group is preferably a hydrocarbon group having 1 to 10 carbon atoms, such as an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group; a vinyl group.
  • n is an integer of 0 or more, preferably 5 or more, more preferably 10 or more, preferably 2000 or less, more preferably 1500 or less, still more preferably 1000 or less, even more preferably 500 or less, particularly preferably is 300 or less.
  • the above upper and lower limits can be combined arbitrarily.
  • it is preferably 5-2000, more preferably 5-1500, still more preferably 5-1000, even more preferably 10-500, and particularly preferably 10-300.
  • the ink repellency tends to be enhanced by making it equal to or higher than the lower limit.
  • the content is equal to or less than the above upper limit, there is a tendency that the uniformity of the coating film becomes high.
  • liquid repellent agents having a cross-linking group and a siloxane chain examples include compounds commercially available under the trade names of "BYK-UV3500 series” manufactured by BYK Chemie and "8SS” series manufactured by Taisei Fine Chemicals. .
  • compounds containing both fluorine and siloxane examples include those commercially available under the trade names of "8FS” series manufactured by Taisei Fine Chemicals Co., Ltd. and "KP series” manufactured by Shin-Etsu Chemical Co., Ltd.
  • the molecular weight of compound (e1) is not particularly limited, and it may be a low molecular weight compound or a high molecular weight compound. High-molecular-weight materials are preferable because they can suppress exudation during development and fluidity due to post-baking, and can suppress outflow from partition walls.
  • the number average molecular weight of the compound (e1) is preferably 100 or more, more preferably 500 or more, preferably 150000 or less, more preferably 140000 or less, and further preferably 130000 or less.
  • 120,000 or less is particularly preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 100 to 150,000 is preferred, 100 to 140,000 is more preferred, 500 to 130,000 is even more preferred, and 500 to 120,000 is particularly preferred.
  • the content of (e) liquid repellent agent in the colored photosensitive resin composition of the present invention is not particularly limited.
  • the total solid content of the colored photosensitive resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and preferably 5% by mass. % or less, more preferably 3 mass % or less, and still more preferably 2 mass % or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 0.01 to 5% by mass is preferable, 0.05 to 3% by mass is more preferable, and 0.1 to 2% by mass is even more preferable.
  • the ink repellency tends to be improved by making it equal to or higher than the lower limit. When the thickness is equal to or less than the above upper limit, there is a tendency that a uniform coating film can be easily obtained when the ink is applied to the pixel portion after the formation of the partition walls.
  • the content of compound (e1) in the colored photosensitive resin composition of the present invention is not particularly limited.
  • the total solid content of the colored photosensitive resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and preferably 5% by mass. Below, more preferably 3% by mass or less, still more preferably 2% by mass or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 0.01 to 5% by mass is preferable, 0.05 to 3% by mass is more preferable, and 0.1 to 2% by mass is even more preferable.
  • the ink repellency tends to be improved by making it equal to or higher than the lower limit. When the thickness is equal to or less than the above upper limit, there is a tendency that a uniform coating film can be easily obtained when the ink is applied to the pixel portion after the formation of the partition walls.
  • the content of the liquid-repellent agent having a cross-linking group and a fluorine atom in the colored photosensitive resin composition of the present invention is not particularly limited.
  • the total solid content of the colored photosensitive resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and preferably 5% by mass. Below, more preferably 3% by mass or less, still more preferably 2% by mass or less. The above upper and lower limits can be combined arbitrarily.
  • the ink repellency tends to be improved by making it equal to or higher than the lower limit.
  • the thickness is equal to or less than the above upper limit, there is a tendency that a uniform coating film can be easily obtained when the ink is applied to the pixel portion after the formation of the partition walls.
  • the content of the liquid repellent agent having a cross-linking group and a siloxane chain in the colored photosensitive resin composition of the present invention is not particularly limited.
  • the total solid content of the colored photosensitive resin composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.5% by mass or more, and preferably 5% by mass. Below, more preferably 3% by mass or less, still more preferably 2% by mass or less. The above upper and lower limits can be combined arbitrarily.
  • the ink repellency tends to be improved by making it equal to or higher than the lower limit.
  • the thickness is equal to or less than the above upper limit, there is a tendency that a uniform coating film can be easily obtained when the ink is applied to the pixel portion after the formation of the partition walls.
  • a surfactant may be used together with (e) the liquid repellent.
  • Surfactants for example, can be used for the purpose of improving the applicability as a coating liquid of the colored photosensitive resin composition and the developability of the coating film, and does not have a silicone-based surfactant or a cross-linking group. Fluorinated surfactants are preferred.
  • silicone-based surfactant is preferable, polyether-modified silicone system surfactants are more preferred.
  • fluoroalkyl or fluoroalkylene group on at least one of the terminal, main chain and side chain are suitable as the fluorosurfactant that does not have a cross-linking group.
  • fluorine-based surfactants having no cross-linking group include "BM-1000" and "BM-1100” manufactured by BM Chemie, "Megaface F142D” and “Megaface F172” manufactured by DIC, "Megafac F173", “Megafac F183", “Megafac F470", “Megafac F475", “Megafac F554", “Megafac F559", 3M Japan “FC430”, Neos "DFX-” 18” can be mentioned.
  • silicone-based surfactants examples include “DC3PA”, “SH7PA”, “DC11PA”, “SH21PA”, “SH28PA”, “SH29PA”, “8032Additive”, and “SH8400” manufactured by Dow Corning Toray Co., Ltd. , “BYK (registered trademark, hereinafter the same) 323" and “BYK330” manufactured by BYK-Chemie.
  • Surfactants other than fluorine-based surfactants and silicone-based surfactants may be included, and surfactants other than fluorine-based surfactants and silicone-based surfactants include nonionic and anionic surfactants. , cationic and amphoteric surfactants.
  • Nonionic surfactants include, for example, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, glycerin Fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythrityl fatty acid esters, polyoxyethylene pentaerythritic fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbit fatty acid esters, polyoxyethylene sorbitol fatty acid esters.
  • Examples of commercially available nonionic surfactants include polyoxyethylene-based surfactants such as "Emulgen (registered trademark, hereinafter the same.) 104P" and "Emulgen A60" manufactured by Kao Corporation.
  • anionic surfactants include alkylsulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, polyoxyethylene alkylethersulfonates, alkylsulfates, alkylsulfates, higher alcohol sulfates, Fatty alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, special polymer Surfactants are included.
  • a special polymeric surfactant is preferable, and a special polycarboxylic acid type polymeric surfactant is more preferable.
  • Commercially available anionic surfactants include, for example, “Emal (registered trademark, hereinafter the same.) 10" manufactured by Kao Corporation for alkyl sulfate ester salts, and "Perex (registered trademark) manufactured by Kao Corporation” for alkylnaphthalene sulfonates.
  • Registered trademark NB-L and special polymeric surfactants include, for example, “Homogenol (registered trademark, hereinafter the same) L-18” and “Homogenol L-100” manufactured by Kao Corporation.
  • Cationic surfactants include, for example, quaternary ammonium salts, imidazoline derivatives, and alkylamine salts.
  • amphoteric surfactants include betaine-type compounds, imidazolium salts, imidazolines, and amino acids. Quaternary ammonium salts are preferred, and stearyltrimethylammonium salts are more preferred.
  • commercially available cationic surfactants include alkylamine salts such as "Acetamine (registered trademark) 24" manufactured by Kao Corporation, and quaternary ammonium salts such as "Cortamine (registered trademark)” manufactured by Kao Corporation. The same.) 24P” and “Cortamine 86W”.
  • Surfactants may be used singly or in combination of two or more.
  • a combination of a silicone-based surfactant and a fluorine-based surfactant a combination of a silicone-based surfactant and a special polymer surfactant, and a combination of a fluorine-based surfactant and a special polymer-based surfactant.
  • a combination of a silicone surfactant and a fluorosurfactant is preferred.
  • a silicone-based surfactant and a fluorine-based surfactant for example, "DFX-18” manufactured by Neos, "BYK-300” or “BYK-330” manufactured by BYK-Chemie and "S-” manufactured by AGC Seimi Chemical Co., Ltd. 393”; Combination of Shin-Etsu Silicone Co., Ltd. “KP340” and DIC “F-554” or “F-559”; Toray Dow Corning Co., Ltd. “SH7PA” and Daikin Co., Ltd. “DS-401” Combination with: A combination of "L-77” manufactured by NUC and "FC4430" manufactured by 3M Japan.
  • the colored photosensitive resin composition of the present invention may contain a dispersant.
  • the dispersant (a) finely disperses the colorant and stabilizes the dispersed state.
  • a polymer dispersant having a functional group is preferable, and further, from the viewpoint of dispersion stability, a carboxy group; a phosphoric acid group; a sulfonic acid group; or a base thereof; Polymeric dispersants having functional groups such as amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine are preferred.
  • Polymer dispersants include, for example, urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants composed of amino group-containing monomers and macromonomers, and polyoxyethylene alkyl ether dispersants. Dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants can be mentioned.
  • polymer dispersants examples include trade names such as EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by BYK-Chemie), Disparon (registered trademark, manufactured by Kusumoto Kasei), SOLSPERSE (registered trademark). (trademark, manufactured by Lubrizol Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and Ajisper (registered trademark, manufactured by Ajinomoto Co., Inc.). Polymer dispersants may be used alone or in combination of two or more.
  • the weight average molecular weight (Mw) of the polymeric dispersant is preferably 700 or more, more preferably 1000 or more, and preferably 100,000 or less, more preferably 50,000 or less.
  • the above upper and lower limits can be combined arbitrarily.
  • the weight average molecular weight (Mw) of the polymeric dispersant is preferably 700-100,000, more preferably 1,000-50,000.
  • the dispersant preferably contains a polymer dispersant having an acidic or basic functional group.
  • a polymer dispersant having a basic functional group and either one or both of a polyester bond and a polyether bond is preferred.
  • an unsaturated group-containing monomer having a functional group (the functional group here is the functional group described above as the functional group contained in the polymer dispersant), It is preferable to use random copolymers, graft copolymers and block copolymers with unsaturated group-containing monomers having no functional groups. These copolymers can be produced by known methods.
  • unsaturated group-containing monomers having functional groups examples include (meth) acrylic acid, 2-(meth) acryloyloxyethyl succinic acid, 2-(meth) acryloyloxyethyl phthalate, 2-(meth) ) Acryloyloxyethylhexahydrophthalic acid, unsaturated monomers having a carboxyl group such as acrylic acid dimer, tertiary amino such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate and quaternary products thereof groups, unsaturated monomers with a quaternary ammonium base.
  • the unsaturated group-containing monomer having a functional group may be used alone or in combination of two or more.
  • unsaturated group-containing monomers having no functional group examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, cyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxymethyl (meth)acrylate, 2-ethylhexyl ( meth)acrylate, isobornyl (meth)acrylate, tricyclodecane (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N-vinylpyrrolidone, styrene and its derivatives, ⁇ -methylstyrene, N-cycl
  • the acrylic polymer dispersant is particularly preferably an AB or BAB block copolymer consisting of an A block having a functional group and a B block having no functional group.
  • the block may contain a partial structure derived from the unsaturated group-containing monomer that does not contain the functional group. may be contained in the A block in any form of random copolymerization or block copolymerization.
  • the content of the partial structure containing no functional group in the A block is preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less.
  • the B block consists of a partial structure derived from an unsaturated group-containing monomer that does not contain the above functional group, but one B block contains partial structures derived from two or more monomers. These may be contained in the B block in any form of random copolymerization or block copolymerization.
  • the AB or BAB block copolymer is prepared, for example, by the following living polymerization method.
  • the living polymerization method includes an anion living polymerization method, a cationic living polymerization method, and a radical living polymerization method.
  • the acrylic polymer dispersant that can be used in the present invention may be an AB block copolymer or a BAB block copolymer, and the A block constituting the copolymer
  • the /B block ratio is preferably 1/99 to 80/20 (mass ratio), and more preferably 5/95 to 60/40 (mass ratio).
  • the amount of the quaternary ammonium base in 1 g of the AB block copolymer or BAB block copolymer that can be used in the present invention is preferably 0.1 to 10 mmol. By setting the amount within the above range, there is a tendency that good dispersibility can be ensured.
  • the amine value is preferably 1 to 100 mgKOH/g, and from the viewpoint of dispersibility, preferably 10 mgKOH/g or more, more preferably. is 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, preferably 90 mgKOH/g or less, more preferably 80 mgKOH/g or less, still more preferably 75 mgKOH/g or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 100 mgKOH/g is preferred, 10 to 90 mgKOH/g is more preferred, 30 to 80 mgKOH/g is even more preferred, and 50 to 75 mgKOH/g is particularly preferred.
  • the amine value of a dispersant such as a block copolymer is expressed by the mass of KOH equivalent to the amount of base per 1 g of solid content excluding the solvent in the dispersant sample, and is measured by the following method.
  • Amine value [mgKOH / g] (561 ⁇ V) / (W ⁇ S) [W: dispersant sample weighed amount [g], V: titration amount at the end point of titration [mL], S: dispersant It represents the solid content concentration [mass %] of the sample. ]
  • the acid value of the block copolymer is preferably as low as possible, preferably 10 mgKOH/g or less, although it depends on the presence and type of acidic groups that are the source of the acid value.
  • the weight average molecular weight (Mw) of the block copolymer is preferably in the range of 1,000 to 100,000. Within the above range, there is a tendency to ensure good dispersibility.
  • the amine value is preferably 1 to 100 mgKOH/g, and from the viewpoint of dispersibility, preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, and still more preferably 50 mgKOH. /g or more, preferably 90 mgKOH/g or less, more preferably 80 mgKOH/g or less, still more preferably 75 mgKOH/g or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 100 mgKOH/g is preferred, 10 to 90 mgKOH/g is more preferred, 30 to 80 mgKOH/g is even more preferred, and 50 to 75 mgKOH/g is particularly preferred.
  • the acid value is preferably as low as possible, preferably 10 mgKOH/g or less, depending on the presence or absence and type of the acidic group.
  • the weight average molecular weight (Mw) of the polymer dispersant is preferably in the range of 1000-100000. Within the above range, there is a tendency to ensure good dispersibility.
  • the colored photosensitive resin composition of the present invention contains (f) a dispersant
  • its content is not particularly limited. It is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, preferably 8% by mass or less, and more preferably 5% by mass or less, relative to the total solid content of the colored photosensitive resin composition. 3% by mass or less is more preferable, and 2% by mass or less is particularly preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 0.1 to 8% by mass is preferable, 0.1 to 5% by mass is more preferable, 0.5 to 3% by mass is even more preferable, and 0.5 to 2% by mass is particularly preferable.
  • the content is equal to or higher than the lower limit, there is a tendency to suppress the generation of residue due to aggregates.
  • the amount is equal to or less than the above upper limit, ink repellency and developability tend to be improved.
  • the content of the dispersant is preferably 1 part by mass or more, more preferably 2 parts by mass or more, still more preferably 3 parts by mass or more, and 25 parts by mass or less with respect to 100 parts by mass of the (a) colorant. is preferred, 20 parts by mass or less is more preferred, 15 parts by mass or less is even more preferred, and 12 parts by mass or less is particularly preferred.
  • the above upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 25 parts by mass, more preferably 3 to 20 parts by mass, even more preferably 5 to 15 parts by mass, and particularly preferably 5 to 12 parts by mass.
  • the content is equal to or higher than the lower limit, there is a tendency to suppress the generation of residue due to aggregates.
  • the amount is equal to or less than the above upper limit, ink repellency and developability tend to be improved.
  • the content of the dispersing agent is preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, and 25 parts by mass with respect to 100 parts by mass of the (a1) titanium oxide particles.
  • the following is preferable, 20 parts by mass or less is more preferable, 15 parts by mass or less is even more preferable, and 12 parts by mass or less is particularly preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 25 parts by mass, more preferably 3 to 20 parts by mass, even more preferably 5 to 15 parts by mass, and particularly preferably 5 to 12 parts by mass.
  • the content is equal to or higher than the lower limit, there is a tendency to suppress the generation of residue due to aggregates.
  • the amount is equal to or less than the above upper limit, ink repellency and developability tend to be improved.
  • the colored photosensitive resin composition of the present invention may contain an ultraviolet absorber.
  • the UV absorber is added for the purpose of controlling the photocuring distribution by allowing the UV absorber to absorb a specific wavelength of the light source used for exposure.
  • the photosensitive resin composition of the present invention may contain a polymerization inhibitor. Since the inclusion of a polymerization inhibitor inhibits radical polymerization, there is a tendency that the taper angle of the obtained partition walls can be increased.
  • a polymerization inhibitor may be used individually by 1 type, and may use 2 or more types together.
  • the produced alkali-soluble resin may contain a polymerization inhibitor.
  • the polymerization inhibitor may be used as it is contained in the alkali-soluble resin, or in addition to the polymerization inhibitor contained in the resin, the same or a different polymerization inhibitor may be added during the production of the colored photosensitive resin composition. Further may be added.
  • the content is not particularly limited.
  • the total solid content of the colored photosensitive resin composition is preferably 0.0005% by mass or more, more preferably 0.001% by mass or more, still more preferably 0.01% by mass or more, and preferably 0 0.1% by mass or less, more preferably 0.08% by mass or less, and even more preferably 0.05% by mass or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 0.0005 to 0.1% by mass is preferable, 0.001 to 0.08% by mass is more preferable, and 0.01 to 0.05% by mass is even more preferable.
  • the taper angle tends to be increased by making it equal to or greater than the lower limit.
  • the ink repellency tends to be enhanced by making it equal to or less than the above upper limit.
  • Thermal polymerization initiator The colored photosensitive resin composition of the invention may contain a thermal polymerization initiator. Inclusion of a thermal polymerization initiator tends to increase the degree of cross-linking of the film.
  • Thermal polymerization initiators include, for example, azo compounds, organic peroxides, and hydrogen peroxide. The thermal polymerization initiator may be used singly or in combination of two or more.
  • the total content of the thermal polymerization initiator is It is preferable that the content ratio of the polymerization initiator is the same, and the ratio of the photopolymerization initiator and the thermal polymerization initiator used together is, from the viewpoint of ink repellency, relative to 100 parts by mass of the photopolymerization initiator. It is preferable to use 5 to 300 parts by mass of the thermal polymerization initiator.
  • the colored photosensitive resin composition of the present invention may contain an amino compound. Amino compounds accelerate thermosetting.
  • the content of the amino compound is preferably 40% by mass or less, more preferably 30% by mass, based on the total solid content of the colored photosensitive resin composition. % by mass or less, preferably 0.5% by mass or more, more preferably 1% by mass or more.
  • the above upper and lower limits can be combined arbitrarily. For example, 0.5 to 40% by mass is preferable, and 1 to 30% by mass is more preferable.
  • the content is equal to or less than the above upper limit, there is a tendency that the storage stability can be maintained. There is a tendency that sufficient thermosetting property can be ensured by setting the content to be at least the above lower limit.
  • amino compounds include amino compounds having a methylol group as a functional group and at least two alkoxymethyl groups obtained by subjecting the methylol group to condensation-denaturation with an alcohol having 1 to 8 carbon atoms.
  • melamine resin obtained by polycondensation of melamine and formaldehyde
  • benzoguanamine resin obtained by polycondensation of benzoguanamine and formaldehyde
  • glycoluril resin obtained by polycondensation of glycoluril and formaldehyde
  • Polycondensed urea resins resins obtained by co-polycondensing two or more of melamine, benzoguanamine, glycoluril, or urea with formaldehyde
  • modified resins obtained by modifying the methylol groups of the above resins by alcohol condensation. These may be used individually by 1 type, and may use 2 or more types together.
  • the colored photosensitive resin composition of the present invention may contain a silane coupling agent.
  • a silane coupling agent improves adhesion to the substrate.
  • silane coupling agent for example, epoxy-based, methacrylic-based, amino-based, and imidazole-based silane coupling agents can be used. From the viewpoint of improving adhesion, epoxy-based and imidazole-based silane coupling agents are particularly preferable. .
  • the content thereof is preferably 20% by mass or less based on the total solid content of the colored photosensitive resin composition from the viewpoint of adhesion. , more preferably 15% by mass or less.
  • the colored photosensitive resin composition of the present invention may contain an inorganic filler.
  • Inorganic fillers are blended for the purpose of improving the strength of the cured product and (b) improving the verticality and taper angle of the coating film by moderate interaction with the alkali-soluble resin (formation of the matrix structure). be done.
  • inorganic fillers examples include talc, silica, and those surface-treated with various silane coupling agents.
  • the average particle size of the inorganic filler is preferably 0.005-2 ⁇ m, more preferably 0.01-1 ⁇ m.
  • the average particle size is a value measured with a laser diffraction scattering particle size distribution measuring device such as manufactured by Beckman Coulter.
  • silica sol and modified silica sol are particularly preferable because they tend to be excellent in the effect of improving the taper angle as well as the dispersion stability.
  • the content thereof is preferably 5% by mass or more based on the total solid content of the colored photosensitive resin composition from the viewpoint of ink repellency. , more preferably 10% by mass or more, preferably 80% by mass or less, and more preferably 70% by mass or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 5 to 80% by mass is preferable, and 10 to 70% by mass is more preferable.
  • Adhesion Improver The colored photosensitive resin composition of the present invention may contain an adhesion improver.
  • the adhesion improver imparts adhesion to the substrate.
  • adhesion improvers examples include phosphoric acid-based ethylenic monomers.
  • phosphoric acid-based ethylenic monomer (meth)acryloyloxy group-containing phosphates are preferable, and those represented by the following general formulas (g1), (g2) and (g3) are preferable.
  • R 51 represents a hydrogen atom or a methyl group
  • l and l' are integers of 1-10
  • m is 1, 2 or 3.
  • the phosphoric acid-based ethylenic monomers may be used singly or in combination of two or more.
  • the content is 0.02 mass with respect to the total solid content of the colored photosensitive resin composition. % or more is preferable, 0.05% by mass or more is more preferable, 0.1% by mass or more is more preferable, 0.2% by mass or more is particularly preferable, and 4% by mass or less is preferable, and 3% by mass or less is more preferable. It is preferably 2% by mass or less, more preferably 1% by mass or less. The above upper and lower limits can be combined arbitrarily.
  • 0.02 to 4% by mass is preferable, 0.05 to 3% by mass is more preferable, 0.1 to 2% by mass is even more preferable, and 0.2 to 1% by mass is particularly preferable.
  • the effect of improving the adhesion to the substrate becomes sufficient.
  • the above upper limit there is a tendency to easily suppress deterioration of adhesion to the substrate.
  • the colored photosensitive resin composition of the present invention may contain a solvent.
  • each component contained in the colored photosensitive resin composition can be used in a state of being dissolved or dispersed in the solvent.
  • Ethylene glycol monomethyl ether ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, 3-methoxy-1-butanol, triethylene glycol monomethyl ether, Glycol monoalkyl ethers such as triethylene glycol monoethyl ether, tripropylene glycol methyl ether; Glycol dialkyl ethers such as ethylene glycol monoethyl ether, tripropylene glycol methyl
  • solvents include, for example, Mineral Spirit, Valsol #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No. 1 and no. 2, Solvesso #150, Shell TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names).
  • the solvent can dissolve or disperse each component contained in the colored photosensitive resin composition, and is selected according to the method of using the colored photosensitive resin composition of the present invention.
  • the boiling point of the solvent under atmospheric pressure is preferably 60 to 280°C, more preferably 70 to 260°C.
  • propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, and 3-methoxy-1-butyl acetate are preferred.
  • a solvent may be used individually by 1 type, and may use 2 or more types together.
  • the content of the solvent in the total solid content in the colored photosensitive resin composition solution is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and particularly preferably 25% by mass or more.
  • it is preferably used in an amount of 90% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, and particularly preferably 35% by mass or less.
  • the above upper and lower limits can be combined arbitrarily.
  • it is preferably used in an amount of 10 to 90% by mass, more preferably 15 to 50% by mass, still more preferably 20 to 40% by mass, and particularly preferably 25 to 35% by mass.
  • the colored photosensitive resin composition of the present invention is prepared by mixing each component contained in the colored photosensitive resin composition with a stirrer.
  • the colorant contains a solvent-insoluble component such as a pigment
  • it is preferably dispersed in advance using a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, or the like. Since the (a) colorant is finely divided by the dispersion treatment, the application properties of the colored photosensitive resin composition are improved.
  • a pigment dispersion containing at least (a) a colorant, a solvent, and (f) a dispersant. It is preferable to carry out dispersion treatment in a system in which (a) a coloring agent, a solvent, and (f) a dispersant are used in combination, or optionally a part or all of an alkali-soluble resin (b) is used in combination (hereinafter referred to as , the mixture subjected to dispersion treatment and the composition obtained by dispersion treatment may be referred to as "pigment dispersion").
  • a polymer dispersant as (f) the dispersant, since the obtained pigment dispersion and the colored photosensitive resin composition are excellent in dispersion stability, and increase in viscosity over time is suppressed.
  • the (a) colorant, organic solvent, and (f) dispersant that can be used in the pigment dispersion those described as those that can be used in the colored photosensitive resin composition can be preferably employed.
  • the content ratio of each colorant in (a) the colorant in the pigment dispersion the content ratio described as the content ratio in the colored photosensitive resin composition can be preferably employed.
  • the temperature is preferably from 0°C to 100°C, more preferably from room temperature to 80°C.
  • the appropriate dispersion time varies depending on the composition of the liquid, the size of the dispersion treatment apparatus, etc., and is therefore adjusted as appropriate.
  • the index of dispersion is to control the gloss of the ink so that the 20 degree specular gloss (JIS Z8741) of the colored photosensitive resin composition is in the range of 50-300.
  • the dispersed particle size of the pigment dispersed in the pigment dispersion liquid is preferably 0.03 to 0.3 ⁇ m, and is measured by a dynamic light scattering method or the like.
  • the pigment dispersion obtained by the dispersion treatment and other components contained in the colored photosensitive resin composition are mixed to form a uniform solution or dispersion.
  • fine dust since fine dust may be mixed in the liquid, it is desirable to filter the obtained colored photosensitive resin composition with a filter or the like.
  • the cured product of the present invention can be obtained by curing the colored photosensitive resin composition of the present invention.
  • the colored photosensitive resin composition of the present invention can be used to form partitions, for example, partitions for partitioning the organic layers of an organic electroluminescent device, and pixel portions in color filters containing luminescent nanoparticles. It can be suitably used for forming partitions for partitioning.
  • the partition wall of the present invention is composed of the cured product of the present invention.
  • the method for forming partition walls using the colored photosensitive resin composition of the present invention is not particularly limited, and conventionally known methods can be employed.
  • a method for forming the partition walls includes, for example, a coating step of applying a colored photosensitive resin composition onto a substrate to form a colored photosensitive resin composition layer, and an exposure step of exposing the colored photosensitive resin composition layer. , and the like.
  • Specific examples of the method for forming such partition walls include an inkjet method and a photolithography method.
  • a colored photosensitive resin composition whose viscosity has been adjusted by dilution with a solvent or the like is used as ink, and ink droplets are ejected onto a substrate along a predetermined pattern of partition walls by an inkjet method to obtain a colored photosensitive resin.
  • the composition is applied onto a substrate to form a pattern of uncured barrier ribs.
  • the pattern of uncured barrier ribs is then exposed to form cured barrier ribs on the substrate.
  • the exposure of the uncured barrier rib pattern is performed in the same manner as the exposure step in the photolithography method described later, except that no mask is used.
  • a colored photosensitive resin composition is applied to the entire area of the substrate where the partition walls are to be formed to form a colored photosensitive resin composition layer. After the formed colored photosensitive resin composition layer is exposed according to a predetermined pattern of barrier ribs, the exposed colored photosensitive resin composition layer is developed to form barrier ribs on the substrate.
  • a contact transfer coating device such as a roll coater, a reverse coater, a bar coater, or a spinner (rotating Coating device)
  • a curtain flow coater or other non-contact coating device is used to apply the colored photosensitive resin composition, and if necessary, the solvent is removed by drying to form a colored photosensitive resin composition layer.
  • a negative mask is used to irradiate the colored photosensitive resin composition with active energy rays such as ultraviolet rays and excimer laser light, and the colored photosensitive resin composition layer is formed according to the bank pattern.
  • active energy rays such as ultraviolet rays and excimer laser light
  • the colored photosensitive resin composition layer is formed according to the bank pattern.
  • Partial exposure a light source that emits ultraviolet rays, such as a high-pressure mercury lamp, an extra-high pressure mercury lamp, a xenon lamp, or a carbon arc lamp, can be used.
  • the amount of exposure varies depending on the composition of the colored photosensitive resin composition, it is preferably about 10 to 400 mJ/cm 2 , for example.
  • the partition walls are formed by developing the exposed colored photosensitive resin composition layer according to the pattern of the partition walls with a developer.
  • the development method is not particularly limited, and an immersion method, a spray method, or the like can be used.
  • Specific examples of the developer include organic ones such as dimethylbenzylamine, monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts. mentioned.
  • an antifoaming agent or a surfactant can be added to the developer.
  • the barrier ribs after development are post-baked and cured by heating.
  • Post-baking is preferably carried out at 80 to 250° C. for 15 to 180 minutes.
  • the partition of the present invention can be formed by the method described above.
  • (a1) a colored photosensitive resin composition containing titanium oxide particles and another coloring agent is prepared, and partition walls are first prepared from the colored photosensitive resin composition containing another coloring agent.
  • (a1) a colored photosensitive resin composition containing titanium oxide particles may be used to cover the outside of the partition walls.
  • the substrate used for forming the partition is not particularly limited, and is appropriately selected according to the type of organic electroluminescence device manufactured using the substrate on which the partition is formed.
  • Suitable substrate materials include glass and various resin materials.
  • Specific examples of the resin material include polyester such as polyethylene terephthalate; polyolefin such as polyethylene and polypropylene; polycarbonate; poly(meth)methacrylic resin; polysulfone; and polyimide.
  • polyester such as polyethylene terephthalate
  • polyolefin such as polyethylene and polypropylene
  • polycarbonate poly(meth)methacrylic resin
  • polysulfone polysulfone
  • polyimide polyimide
  • a transparent electrode layer such as ITO or ZnO may be provided in advance on the surface of the substrate on which the barrier ribs are formed, or a gas barrier layer such as SiNx or SiOx may be provided.
  • a layer, an adhesion improving layer, a color filter, a planarization lower layer, etc. may be provided.
  • the thickness of the partition wall of the present invention is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, still more preferably 5 ⁇ m or more, particularly preferably 10 ⁇ m or more, more preferably 1 mm or less, more preferably 100 ⁇ m or less, and still more preferably. is 50 ⁇ m or less, more preferably 30 ⁇ m or less, particularly preferably 20 ⁇ m or less.
  • the above upper and lower limits can be combined arbitrarily. For example, it is preferably 0.1 ⁇ m to 1 mm, more preferably 1 to 100 ⁇ m, even more preferably 5 to 50 ⁇ m, particularly preferably 10 to 30 ⁇ m.
  • the film thickness of the partition wall is measured by a level difference/surface roughness/fine shape measuring device, a scanning white light interference microscope, an ellipsometer, a reflection spectroscopic film thickness meter, and an electron microscope.
  • the color filter containing the quantum dot nanoparticles of the present invention is not particularly limited as long as it comprises the partition walls of the present invention.
  • a layer containing quantum dot nanoparticles is formed as a pixel in the region.
  • a method for forming a layer containing quantum dot nanoparticles is not particularly limited.
  • a quantum dot nanoparticle-containing composition containing quantum dot nanoparticles is selectively attached to a region partitioned by partition walls by an inkjet method, and the quantum dot nanoparticle-containing composition is cured by irradiation or heating with an active energy ray. can be manufactured.
  • the composition containing quantum dot nanoparticles is not particularly limited as long as it contains quantum dot nanoparticles, and may or may not contain a solvent.
  • the boiling point of the solvent is preferably 180° C. or higher from the viewpoint of the continuous ejection stability of the inkjet ink.
  • the boiling point of the solvent is 300 ° C. or less. is preferred.
  • the content is not particularly limited.
  • 0.001% by mass or more in the quantum dot nanoparticle composition more preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 1% by mass or more, 10% by mass or more More preferably, 20% by mass or more is even more preferable, and 30% by mass or more is particularly preferable.
  • it is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.
  • the above upper and lower limits can be combined arbitrarily.
  • 0.001 to 90% by mass is preferable, 0.01 to 90% by mass is more preferable, 0.1 to 90% by mass is more preferable, 1 to 80% by mass is even more preferable, and 10 to 80% by mass is More preferably, 20 to 70% by mass is even more preferable, and 30 to 70% by mass is particularly preferable.
  • the content is at least the above lower limit, the viscosity of the composition tends to be reduced, and suitability for known coating methods, particularly ink ejection, tends to be facilitated.
  • the thickness of the film after discharging and removing the solvent becomes thicker, and the film containing more quantum dot nanoparticles can be formed. There is a tendency to be able to obtain a large pixel portion.
  • the quantum dot nanoparticle-containing composition it is possible to disperse the quantum dot nanoparticles without a solvent by using a (meth)acrylate compound that functions as a dispersion medium. In this case, there is an advantage that the step of removing the solvent by drying is not required when forming the pixel portion.
  • the viscosity at 40° C. is not particularly limited. It is preferably 2 mPa ⁇ s or more, more preferably 5 mPa ⁇ s or more, still more preferably 7 mPa ⁇ s or more, and preferably 20 mPa ⁇ s or less, more preferably 15 mPa ⁇ s or less, and even more preferably 12 mPa ⁇ s or less.
  • the above upper and lower limits can be combined arbitrarily. For example, it is preferably from 2 to 20 mPa ⁇ s, more preferably from 5 to 15 mPa ⁇ s, even more preferably from 7 to 12 mPa ⁇ s.
  • the viscosity of the quantum dot nanoparticle-containing composition is measured with an E-type viscometer.
  • the viscosity at 23 ° C. of the quantum dot nanoparticle-containing composition when used in the present invention is not particularly limited. preferably 10 mPa ⁇ s or more, more preferably 15 mPa ⁇ s or more, preferably 40 mPa ⁇ s or less, more preferably 35 mPa ⁇ s or less, further preferably 30 mPa ⁇ s or less, and particularly preferably 25 mPa ⁇ s or less. .
  • the above upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 40 mPa ⁇ s, more preferably 5 to 35 mPa ⁇ s, still more preferably 10 to 30 mPa ⁇ s, and particularly preferably 15 to 25 mPa ⁇ s.
  • the surface tension of the quantum dot nanoparticle-containing composition when used in the present invention is not particularly limited, but it is preferably suitable for a known coating method, particularly a surface tension suitable for an inkjet method, specifically, 20 to 40 mN/m is preferred, and 25-35 mN/m is more preferred.
  • flight deflection means that when the quantum dot nanoparticle-containing composition is ejected from the ink ejection hole, the landing position of the quantum dot nanoparticle-containing composition deviates from the target position by 30 ⁇ m or more.
  • a composition in which light scattering particles such as titanium oxide are dispersed without containing quantum dot nanoparticles is used as an ink to be ejected into a section corresponding to a blue pixel. may be used.
  • FIG. 1 is a schematic cross-sectional view of an example of a color filter having partition walls of the present invention.
  • the color filter 100 includes a substrate 10 , partition walls 20 provided on the substrate, red pixels 30 , green pixels 40 and blue pixels 50 .
  • the red pixels 30, the green pixels 40, and the blue pixels 50 are arranged in a grid so as to repeat in this order.
  • a partition wall 20 is provided between these adjacent pixels. In other words, these adjacent pixels are partitioned by the partition walls 20 .
  • Red pixels 30 contain red quantum dot nanoparticles 2
  • green pixels 40 contain green quantum dot nanoparticles 1.
  • the blue pixels 50 are pixels that transmit blue light from the light source.
  • nanoparticles are nano-sized crystals that absorb excitation light and emit fluorescence or phosphorescence.
  • crystals having a maximum particle size of 100 nm or less as measured by a transmission electron microscope or scanning electron microscope is the body.
  • Quantum dot nanoparticles can emit light (fluorescence or phosphorescence) of a wavelength different from the absorbed wavelength by absorbing light of a predetermined wavelength. It emits light (red light) with an emission peak wavelength in the range of 665 nm, and the green quantum dot nanoparticles 1 emit light (green light) with an emission peak wavelength in the range of 500 to 560 nm.
  • the wavelength (emission color) of the light emitted by the quantum dot nanoparticles depends on the size (for example, particle diameter) of the quantum dot nanoparticles, but the energy gap of the quantum dot nanoparticles also depends on Therefore, the emission color can be selected by changing the constituent material and size of the quantum dot nanoparticles to be used.
  • the image display device of the present invention includes the partition wall of the present invention.
  • the image display device of the present invention includes, for example, an image display device including quantum dot nanoparticles in light emitting elements. There are no particular restrictions on the type and structure of the image display device as long as it contains quantum dot nanoparticles. and a type that uses quantum dot nanoparticles as color filters.
  • the type of the image display device may be a liquid crystal display device or an image display including an organic electroluminescence device. device and the like.
  • a liquid crystal display device includes a light source having a blue LED and a liquid crystal layer having an electrode for controlling the blue light emitted from the light source for each pixel portion.
  • An example of an image display device including organic electroluminescence elements is one in which blue-emitting organic electroluminescence elements are arranged at positions corresponding to respective pixel portions of a color filter. Specifically, the method described in Japanese Patent Application Laid-Open No. 2019-87746 can be mentioned.
  • the luminescent nanoparticles used in the image display device of the present invention include LED nanocolumns.
  • the colored photosensitive resin composition of the present invention will be described below with specific examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
  • PMEA propylene glycol monomethyl ether acetate
  • Dicyclopentanyl methacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) / styrene / glycidyl methacrylate (molar ratio: 0.3 / 0.1 / 0.6) is a copolymer resin composed of monomers, and acrylic acid is glycidyl methacrylate. and 0.39 mol of tetrahydrophthalic anhydride per 1 mol of the above copolymer resin.
  • the polystyrene equivalent weight average molecular weight (Mw) measured by GPC was 9000, and the solid content acid value was 80 mgKOH/g. It corresponds to the acrylic copolymer resin (b11) having an ethylenically unsaturated group in the side chain. Double bond equivalent weight 470 g/mol.
  • ⁇ Alkali-soluble resin-3> Copolymer resin of methacrylic acid and methyl methacrylate. (molar ratio 82:12, Mw 11400, acid number 97 mg KOH/g, no double bonds).
  • DPHA Dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.
  • Titanium oxide PT501R manufactured by Ishihara Sangyo Co., Ltd. average particle size of primary particles 0.18 ⁇ m
  • basic polymer acrylic dispersant (dispersant-1) basic polymer acrylic dispersant (dispersant-1), and solvent are mixed so that the mass ratio shown in Table 1 is achieved. did.
  • This mixture was subjected to dispersion treatment for 6 hours at a temperature of 25 to 45° C. using a paint shaker.
  • As the beads 0.3 mm ⁇ zirconia beads were used, and 2.5 times the mass of the mixed solution was added. After the dispersion was completed, the beads and the dispersion were separated by a filter to prepare a titanium oxide dispersion-1.
  • the blending ratio of the dispersant in Table 2 is a solid content conversion value
  • the blending ratio of the solvent includes the amount of the solvent derived from the dispersant.
  • Examples 1 to 4 and Comparative Examples 1 to 6 Using the titanium oxide dispersion-1 prepared above, each component was added so that the ratio of the solid content of each component in the total solid content of the colored photosensitive resin composition was the mixing ratio shown in Table 3, and the total solvent was added. Solvent-1 was added so that the ratio of solvent-2 in the mixture was 20% by mass and the content ratio of the total solid content was 31% by mass, followed by stirring, dissolving, and dispersing Examples 1 to 4 and Comparative Examples. 1-6 colored photosensitive resin compositions were prepared. Using the obtained colored photosensitive resin composition, performance evaluation was performed by the method described later. The mixing ratios of the titanium oxide dispersion, the alkali-soluble resin, and the liquid repellent in Table 3 are solid content conversion values.
  • the colored photosensitive resin composition obtained in Examples or Comparative Examples was applied onto a glass substrate using a spinner so as to have a thickness of 10.0 ⁇ m after heat curing. After that, it was vacuum-dried for 1 minute and further dried by heating on a hot plate at 100° C. for 2 minutes to obtain a coated film substrate.
  • the resulting coated film substrate was exposed to light of 100 mJ/cm 2 at a wavelength of 365 nm and an intensity of 500 mW/cm 2 using an exposure apparatus MPA-600FA (manufactured by Canon) through a photomask.
  • line-shaped openings opening width of 5 ⁇ m to 20 ⁇ m in increments of 1 ⁇ m, and up to 50 ⁇ m in increments of 5 ⁇ m, each having a length of 300 ⁇ m and three openings arranged at intervals of 100 ⁇ m) and openings of 1 cm square.
  • a mask with Next these were mixed at 24° C. with a spray pressure of 0.05 MPa using an aqueous solution in which 0.03% by mass of KOH and 0.05% by mass of Emulgen A-60 (surfactant manufactured by Kao Corporation) were dissolved as a developer. It was developed by spraying for 60 seconds, and then washed with pure water for 10 seconds at a spray pressure of 0.5 MPa.
  • This substrate was cured by heating in an oven at 120° C. for 30 minutes to obtain a substrate for evaluation.
  • the coated film substrate was exposed, it was prepared in the same manner as the evaluation substrate except that the entire surface was exposed without using a photomask.
  • Example 1 and Comparative Examples 3 and 4 From the results of Example 1 and Comparative Examples 3 and 4, it can be seen that if the content of titanium oxide particles is too high, it becomes difficult to adhere 10 ⁇ m lines. In the case of Comparative Example 3, the adhesion started from the 50 ⁇ m line, and in the case of Comparative Example 4, the adhesion was insufficient even at the 50 ⁇ m line.
  • Each pattern has a tapered shape as shown in FIG. 3, which indicates that the light required for patterning did not reach the substrate surface.
  • Comparative Example 6 the contact angle was small and sufficient ink repellency was not exhibited. Also, the 10 ⁇ m line (line) caused film reduction after development, and the target film thickness could not be obtained. From the comparison between Example 1 and Comparative Example 6, it can be said that the double bond equivalent of the alkali-soluble resin is 1000 g/mol or less, and the ink repellency is also improved.

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Abstract

The present invention provides a colored photosensitive resin composition capable of forming a partition wall having excellent patterning properties. This colored photosensitive resin composition is characterized by containing (a) a coloring agent, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) a photopolymerizable compound, and (e) a liquid repellent. The colored photosensitive resin composition is also characterized in that: the content ratio of the (a) coloring agent is 20% by mass or less with respect to the total solid content of the colored photosensitive resin composition; the (a) coloring agent contains (a1) titanium oxide particles; the (b) alkali-soluble resin has a double bond equivalent of 1000 g/mol or less; the (c) photopolymerization initiator contains an oxime ester-based photopolymerization initiator (c1) having a maximum absorption wavelength (λmax) between 300 nm and 350 nm wavelengths; and the (e) liquid repellent contains a compound (e1) that has a crosslinking group and has a fluorine atom and/or a siloxane chain.

Description

着色感光性樹脂組成物、硬化物、隔壁、カラーフィルタ及び画像表示装置Colored photosensitive resin composition, cured product, partition wall, color filter, and image display device
　本発明は、着色感光性樹脂組成物、硬化物、隔壁、カラーフィルタ及び画像表示装置に関する。
　本願は、２０２１年３月３１日に日本に出願された特願２０２１－０６１０５５号及び２０２１年５月２８日に日本に出願された特願２０２１－０９０３２３号に基づき優先権を主張し、その内容をここに援用する。 TECHNICAL FIELD The present invention relates to a colored photosensitive resin composition, a cured product, partition walls, a color filter and an image display device.
This application claims priority based on Japanese Patent Application No. 2021-061055 filed in Japan on March 31, 2021 and Japanese Patent Application No. 2021-090323 filed in Japan on May 28, 2021, and the content thereof is incorporated herein.
　近年、ディスプレイの低消費電力化や広色域化のため、量子ドット等の発光性ナノ粒子を用いた画素やカラーフィルタの形成が検討されている。画素やカラーフィルタの製造方法には、フォトリソグラフィー法とインクジェット法があり、後者の方がインク材料のロスを低減できることが知られている（例えば、特許文献１参照）。
　インクジェット法により発光性ナノ粒子を含む画素やカラーフィルタを製造する場合、予め作製した隔壁に囲まれた領域（画素部）に発光性ナノ粒子を含むインクを吐出して画素を形成する。
　有機電界ディスプレイなどに用いられる有機電界発光素子は、基板上に隔壁（バンク）を形成し、隔壁に囲まれた領域内に、種々の機能層を積層して製造されている。隔壁内に機能層を積層する方法には、インクジェット法が知られている。
　発光性ナノ粒子を含むカラーフィルタ用の隔壁も、有機電界発光素子用の隔壁も、インクジェットによりインクを吐出する際に、隣接する画素部間におけるインク同士の混合等を防ぐ必要があり、高い撥インク性が求められる。
　撥インク性を有する隔壁をフォトリソグラフィー法により形成する材料として、特許文献２には特定のアルカリ可溶性樹脂を２種類併用することで、撥インク性が高く、直線性が良好な着色感光性樹脂組成物が得られることが記載されている。
　特許文献３には光学センサ用の白色膜として酸化チタン粒子等をフッ素やシロキサンを含有する樹脂と共に用いて経時時の色ムラを回避する方法が記載されている。
　特許文献４には、ホワイト顔料を含有する量子ドット用の撥液性隔壁を用いた表示装置について記載されている。 In recent years, in order to reduce the power consumption and widen the color gamut of displays, the formation of pixels and color filters using luminescent nanoparticles such as quantum dots has been studied. Methods for manufacturing pixels and color filters include a photolithography method and an inkjet method, and the latter method is known to reduce the loss of ink materials (see, for example, Patent Document 1).
When pixels or color filters containing luminescent nanoparticles are manufactured by an ink jet method, pixels are formed by ejecting ink containing luminescent nanoparticles into regions (pixel portions) surrounded by prefabricated partition walls.
BACKGROUND ART Organic electroluminescence elements used in organic electric field displays and the like are manufactured by forming partitions (banks) on a substrate and laminating various functional layers in regions surrounded by the partitions. An inkjet method is known as a method for laminating a functional layer in the partition walls.
The barrier ribs for color filters containing luminescent nanoparticles and the barrier ribs for organic electroluminescent elements must prevent mixing of ink between adjacent pixel portions when ink is ejected by inkjet. Inkability is required.
As a material for forming ink-repellent partition walls by photolithography, Patent Document 2 discloses a colored photosensitive resin composition having high ink repellency and good linearity by using two types of specific alkali-soluble resins together. It is stated that a product is obtained.
Patent Document 3 describes a method for avoiding color unevenness over time by using titanium oxide particles or the like as a white film for an optical sensor together with a resin containing fluorine or siloxane.
Patent Document 4 describes a display device using liquid-repellent partition walls for quantum dots containing a white pigment.
日本国特開２０１９－０８６７４５号公報Japanese Patent Application Laid-Open No. 2019-086745 国際公開第２０１９／１４６６８５号WO2019/146685 日本国特許６６８８８７５号公報Japanese Patent No. 6688875 韓国公開１０－２０１９―００９４７９７号公報Korean publication 10-2019-0094797
　特許文献３に記載の組成物は、金属酸化物粒子の含有率が高いため、パターンが形成しにくいという問題があった。
　特許文献４に記載の量子ドット用の撥液性隔壁は、具体的な組成の内容が記載されておらず、隔壁のパターンが形成出来るのか否か不明である。 The composition described in Patent Document 3 has a problem that it is difficult to form a pattern because the content of metal oxide particles is high.
The liquid-repellent barrier ribs for quantum dots described in Patent Document 4 do not describe a specific content of the composition, and it is unclear whether or not a barrier rib pattern can be formed.
　本発明は、パターニング性に優れた隔壁を形成可能な着色感光性樹脂組成物を提供することを目的とする。
　本発明の別の態様は、前記着色感光性樹脂組成物を硬化させた硬化物、該硬化物から構成される隔壁、該隔壁を備えるカラーフィルタ及び画像表示装置を提供することを目的とする。 An object of the present invention is to provide a colored photosensitive resin composition capable of forming partition walls with excellent patterning properties.
Another aspect of the present invention aims to provide a cured product obtained by curing the colored photosensitive resin composition, partition walls composed of the cured product, a color filter and an image display device comprising the partition walls.
　本発明者らが鋭意検討した結果、特定の金属酸化物粒子を含有する着色感光性樹脂組成物において、特定の吸収波長を有するオキシムエステル系光重合開始剤を用いることで上記課題を解決出来ることを見出し、本発明を完成するに至った。
　即ち本発明の要旨は以下の通りである。 As a result of intensive studies by the present inventors, it was found that the above problems can be solved by using an oxime ester photopolymerization initiator having a specific absorption wavelength in a colored photosensitive resin composition containing specific metal oxide particles. and completed the present invention.
That is, the gist of the present invention is as follows.
［１］（ａ）着色剤、（ｂ）アルカリ可溶性樹脂、（ｃ）光重合開始剤、（ｄ）光重合性化合物及び（ｅ）撥液剤を含有する着色感光性樹脂組成物であって、
　前記（ａ）着色剤の含有割合が着色感光性樹脂組成物の全固形分量に対して２０質量％以下であり、
　前記（ａ）着色剤が、（ａ１）酸化チタン粒子を含有し、
　前記（ｂ）アルカリ可溶性樹脂の二重結合当量が１０００ｇ／ｍｏｌ以下であり、
　前記（ｃ）光重合開始剤が、波長３００～３５０ｎｍに極大吸収波長（λmax）を有するオキシムエステル系光重合開始剤（ｃ１）を含有し、
　前記（ｅ）撥液剤が、架橋基を有し、且つフッ素原子及び／又はシロキサン鎖を有する化合物（ｅ１）を含有することを特徴とする着色感光性樹脂組成物。
［２］前記（ｃ）光重合開始剤が、０．０１質量％のプロピレングリコールモノメチルエーテルアセテート溶液での波長３６０～４００ｎｍにおける最大吸光度が２以下である［１］の着色感光性樹脂組成物。
［３］前記（ａ）着色剤中の前記（ａ１）酸化チタン粒子の含有割合が５０質量％以上である［１］又は［２］の着色感光性樹脂組成物。
［４］前記（ａ１）酸化チタン粒子の一次粒子の平均粒子径が１００ｎｍ以上である［１］～［３］のいずれかの着色感光性樹脂組成物。
［５］前記化合物（ｅ１）が、架橋基及びフッ素原子を有し、且つ化合物（ｅ１）中のフッ素原子の含有割合が１５質量％以上である、［１］～［４］のいずれかの着色感光性樹脂組成物。
［６］前記（ｂ）アルカリ可溶性樹脂の二重結合当量が４００ｇ／ｍｏｌより大きい、［１］～［５］のいずれかの着色感光性樹脂組成物。
［７］溶剤を含有する［１］～［６］のいずれかの着色感光性樹脂組成物。
［８］隔壁形成用である［１］～［７］のいずれかの着色感光性樹脂組成物。
［９］［１］～［８］のいずれかの着色感光性樹脂組成物を硬化させた硬化物。
［１０］［９］の硬化物から構成される隔壁。
［１１］［１０］の隔壁を備える、量子ドットナノ粒子を含むカラーフィルタ。
［１２］［１０］の隔壁を備える画像表示装置。 [1] A colored photosensitive resin composition containing (a) a coloring agent, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) a photopolymerizable compound and (e) a liquid repellent agent,
The content of the (a) colorant is 20% by mass or less with respect to the total solid content of the colored photosensitive resin composition,
The (a) colorant contains (a1) titanium oxide particles,
The double bond equivalent of the (b) alkali-soluble resin is 1000 g/mol or less,
The (c) photopolymerization initiator contains an oxime ester photopolymerization initiator (c1) having a maximum absorption wavelength (λmax) at a wavelength of 300 to 350 nm,
The colored photosensitive resin composition, wherein the (e) liquid-repellent agent contains a compound (e1) having a cross-linking group and having a fluorine atom and/or a siloxane chain.
[2] The colored photosensitive resin composition of [1], wherein the photopolymerization initiator (c) has a maximum absorbance of 2 or less at a wavelength of 360 to 400 nm in a 0.01 mass% propylene glycol monomethyl ether acetate solution.
[3] The colored photosensitive resin composition of [1] or [2], wherein the content of the (a1) titanium oxide particles in the (a) colorant is 50% by mass or more.
[4] The colored photosensitive resin composition according to any one of [1] to [3], wherein the (a1) titanium oxide particles have an average primary particle size of 100 nm or more.
[5] Any one of [1] to [4], wherein the compound (e1) has a cross-linking group and a fluorine atom, and the fluorine atom content in the compound (e1) is 15% by mass or more. A colored photosensitive resin composition.
[6] The colored photosensitive resin composition of any one of [1] to [5], wherein the alkali-soluble resin (b) has a double bond equivalent of greater than 400 g/mol.
[7] The colored photosensitive resin composition of any one of [1] to [6] containing a solvent.
[8] The colored photosensitive resin composition according to any one of [1] to [7] for forming partition walls.
[9] A cured product obtained by curing the colored photosensitive resin composition of any one of [1] to [8].
[10] Partition walls composed of the cured product of [9].
[11] A color filter containing quantum dot nanoparticles, which has the barrier ribs of [10].
[12] An image display device comprising the partition of [10].
　本発明によれば、パターニング性に優れた隔壁を形成可能な着色感光性樹脂組成物を提供できる。 According to the present invention, it is possible to provide a colored photosensitive resin composition capable of forming partition walls with excellent patterning properties.
図１は、本発明の隔壁を備える、カラーフィルタの一例の模式断面図である。FIG. 1 is a schematic cross-sectional view of an example of a color filter having partition walls of the present invention. 図２は、本発明の隔壁の模式断面図である。FIG. 2 is a schematic cross-sectional view of the partition wall of the present invention. 図３は、比較例３及び４で形成した隔壁の模式断面図である。3 is a schematic cross-sectional view of partition walls formed in Comparative Examples 3 and 4. FIG. 図４は、反射率測定用基板の波長２５０～８００ｎｍにおける全反射率の測定結果である。FIG. 4 shows measurement results of the total reflectance of the substrate for reflectance measurement at a wavelength of 250 to 800 nm.
　以下、本発明を詳細に説明する。なお、以下の記載は本発明の実施形態の一例であり、本発明はその要旨を超えない限り、これらに特定されない。
　本発明において、「（メタ）アクリル」とは、「アクリル及びメタクリルのいずれか一方又は両方」を意味する。
　本発明において、「全固形分量」とは、着色感光性樹脂組成物における溶剤以外の全成分量を意味する。溶剤以外の成分が常温で液体であっても、その成分は溶剤には含めず、全固形分量に含める。
　本発明において「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
　本発明において、「（共）重合体」とは、単一重合体（ホモポリマー）と共重合体（コポリマー）の双方を含むことを意味し、「（酸）無水物」、「（無水）…酸」とは、酸とその無水物の双方を含むことを意味する。
　本発明において、「パー又はポリフルオロ」とは「パーフルオロ及びポリフルオロのいずれか一方又は両方」を意味する。
　本発明において、隔壁材とはバンク材、壁材、ウォール材をさし、同様に、隔壁とはバンク、壁、ウォールをさす。
　本発明において、重量平均分子量とは、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）によるポリスチレン換算の重量平均分子量（Ｍｗ）を意味する。
　本発明において、酸価とは、特に断りのない限り有効固形分換算の酸価を意味し、中和滴定により算出される。 The present invention will be described in detail below. It should be noted that the following description is an example of the embodiment of the present invention, and the present invention is not specified as long as it does not exceed the gist thereof.
In the present invention, "(meth)acryl" means "one or both of acryl and methacryl".
In the present invention, "total solid content" means the amount of all components other than the solvent in the colored photosensitive resin composition. Even if a component other than the solvent is liquid at room temperature, that component is not included in the solvent but is included in the total solid content.
In the present invention, a numerical range represented by "-" means a range including the numerical values described before and after "-" as lower and upper limits.
In the present invention, "(co)polymer" means including both a single polymer (homopolymer) and a copolymer (copolymer), and includes "(acid) anhydride", "(anhydrous) ... "Acid" is meant to include both acids and their anhydrides.
In the present invention, "perfluoro or polyfluoro" means "one or both of perfluoro and polyfluoro."
In the present invention, a partition wall material means a bank material, a wall material, and a wall material, and similarly, a partition wall means a bank, a wall, and a wall.
In the present invention, the weight average molecular weight means the weight average molecular weight (Mw) in terms of polystyrene by GPC (gel permeation chromatography).
In the present invention, the acid value means an acid value in terms of effective solid content, unless otherwise specified, and is calculated by neutralization titration.
　本発明において隔壁とは、例えば、発光性ナノ粒子として量子ドットナノ粒子を含むカラーフィルタや発光素子等の機能層を区画するためのものとして使用することができ、区画された領域（画素領域）に機能層を構成するための材料であるインクを吐出、必要に応じて乾燥や硬化することで、機能層及び隔壁を含む画素等を形成させていくために使用することができる。 In the present invention, the partition wall can be used, for example, for partitioning a functional layer such as a color filter or a light emitting element containing quantum dot nanoparticles as luminescent nanoparticles, and the partitioned region (pixel region) By ejecting ink, which is a material for forming the functional layer, and drying or curing as necessary, it can be used to form pixels and the like including the functional layer and partition walls.
［１］着色感光性樹脂組成物
　本発明の着色感光性樹脂組成物は、（ａ）着色剤、（ｂ）アルカリ可溶性樹脂、（ｃ）光重合開始剤、（ｄ）光重合性化合物及び（ｅ）撥液剤を必須成分として含有し、さらに必要に応じてその他の成分を含んでいてもよく、例えば、（ｆ）分散剤を含んでいてもよい。 [1] Colored photosensitive resin composition The colored photosensitive resin composition of the present invention includes (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) a photopolymerizable compound and ( e) contains a liquid-repellent agent as an essential component, and if necessary, may contain other components, for example, (f) a dispersant.
［１－１］着色感光性樹脂組成物の成分および組成
　本発明の着色感光性樹脂組成物を構成する成分およびその組成について順に説明する。 [1-1] Components and Composition of Colored Photosensitive Resin Composition Components constituting the colored photosensitive resin composition of the present invention and their compositions will be described in order.
［１－１－１］（ａ）着色剤
　本発明の着色感光性樹脂組成物は、（ａ）着色剤を含有し、（ａ）着色剤は（ａ１）酸化チタン粒子を含有する。（ａ）着色剤が（ａ１）酸化チタン粒子を含有することで、着色感光性樹脂組成物から形成される隔壁の反射率を高め、画像表示装置の輝度を向上できる傾向がある。 [1-1-1] (a) Colorant The colored photosensitive resin composition of the present invention contains (a) a colorant, and (a) the colorant contains (a1) titanium oxide particles. When the (a) colorant contains (a1) titanium oxide particles, the reflectance of the barrier ribs formed from the colored photosensitive resin composition tends to be increased, and the brightness of the image display device can be improved.
　酸化チタン粒子の結晶系は、例えば、アナターゼ型、ルチル型があり、特に限定されない。安定性の観点から触媒活性の低いルチル型が好ましい。 The crystal system of titanium oxide particles includes, for example, anatase type and rutile type, and is not particularly limited. From the viewpoint of stability, the rutile type with low catalytic activity is preferred.
　（ａ）着色剤は、（ａ１）酸化チタン粒子以外に、他の金属酸化物粒子を含有してもよい。
　他の金属酸化物粒子としては、例えば、酸化ジルコニウム、酸化ハフニウム、酸化アルミニウム、酸化鉄、酸化銅、酸化亜鉛、酸化イットリウム、酸化ニオブ、酸化モリブデン、酸化インジウム、酸化スズ、酸化タンタル、酸化タングステン、酸化鉛、酸化ビスマス、酸化セリウム、酸化アンチモン、酸化ゲルマニウム、チタン酸バリウムの粒子が挙げられ、特に酸化ジルコニウム、酸化ハフニウムが好ましい。２種以上の金属元素から構成される複合酸化物粒子も使用することができる。 (a) Colorant may contain other metal oxide particles in addition to (a1) titanium oxide particles.
Other metal oxide particles include, for example, zirconium oxide, hafnium oxide, aluminum oxide, iron oxide, copper oxide, zinc oxide, yttrium oxide, niobium oxide, molybdenum oxide, indium oxide, tin oxide, tantalum oxide, tungsten oxide, Examples include particles of lead oxide, bismuth oxide, cerium oxide, antimony oxide, germanium oxide and barium titanate, and zirconium oxide and hafnium oxide are particularly preferred. Composite oxide particles composed of two or more metal elements can also be used.
　（ａ１）酸化チタン粒子の一次粒子の平均粒子径は、特に限定されない。５００ｎｍ以下が好ましく、４００ｎｍ以下がより好ましく、３００ｎｍ以下がさらに好ましく、２５０ｎｍ以下が特に好ましい。また、１０ｎｍ以上が好ましく、５０ｎｍ以上がより好ましく、１００ｎｍ以上がさらに好ましく、１５０ｎｍ以上が特に好ましい。一次粒子の平均粒子径が前記上限値以下であると、分散液が安定し易い傾向がある。前記下限値以上であれば、効率的に散乱出来また遮光性も良好となる傾向がある。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１０～５００ｎｍが好ましく、５０～４００ｎｍがより好ましく、１００～３００ｎｍがさらに好ましく、１５０～２５０ｎｍが特に好ましい。 The average particle size of the primary particles of the (a1) titanium oxide particles is not particularly limited. It is preferably 500 nm or less, more preferably 400 nm or less, still more preferably 300 nm or less, and particularly preferably 250 nm or less. Moreover, it is preferably 10 nm or more, more preferably 50 nm or more, still more preferably 100 nm or more, and particularly preferably 150 nm or more. When the average particle size of the primary particles is equal to or less than the upper limit, the dispersion tends to be stable. If it is at least the above lower limit, there is a tendency that efficient scattering can be achieved and the light shielding property will be good.
The above upper and lower limits can be combined arbitrarily. For example, 10 to 500 nm is preferred, 50 to 400 nm is more preferred, 100 to 300 nm is even more preferred, and 150 to 250 nm is particularly preferred.
　（ａ１）酸化チタン粒子の一次粒子の平均粒子径は、透過型電子顕微鏡（ＴＥＭ）、又は走査型電子顕微鏡（ＳＥＭ）を使用して、その電子顕微鏡写真から一次粒子の大きさを直接計測する方法で測定する。具体的には、個々の粒子の一次粒子径を、円相当径として算出する。測定は、１００～５００ｎｍ四方の範囲をイメージングし、範囲内にある全粒子に対して実施する。何度か異なる範囲をイメージングし、合計２００～１０００個の一次粒子の粒子径を測定し、その数平均をとることで、平均粒子径を求める。一次粒子径の測定は、例えば、酸化チタン粒子の分散液、着色感光性樹脂組成物の硬化膜に対しても実施することができる。測定サンプルを作製する際は、サンプル中に（ａ１）酸化チタン粒子が均一に存在するようにしなければならない。分散液の場合は、分散直後の分散液を用いて、溶剤を揮発させてから測定を実施する。また、硬化膜の場合は、粒子が均一に分散された着色感光性樹脂組成物を用いて硬化膜を作製し、膜の厚さ方向に切断し、その断面を観察することで測定を実施する。 (a1) The average particle size of the primary particles of the titanium oxide particles is obtained by directly measuring the size of the primary particles from the electron micrograph using a transmission electron microscope (TEM) or a scanning electron microscope (SEM). method. Specifically, the primary particle diameter of each particle is calculated as the equivalent circle diameter. Measurements are performed on all particles within the imaging area of 100-500 nm square. Imaging different areas several times, measuring the particle size of a total of 200 to 1000 primary particles, and taking the number average, the average particle size is obtained. The measurement of the primary particle size can also be carried out on, for example, a dispersion of titanium oxide particles and a cured film of a colored photosensitive resin composition. When preparing a measurement sample, the (a1) titanium oxide particles must be uniformly present in the sample. In the case of a dispersion liquid, the dispersion liquid immediately after dispersion is used, and the measurement is performed after the solvent is volatilized. In the case of a cured film, a cured film is prepared using a colored photosensitive resin composition in which particles are uniformly dispersed, cut in the thickness direction of the film, and the cross section is observed to carry out the measurement. .
　（ａ１）酸化チタン粒子の分散粒子の平均粒子径は特に限定されないが、好ましくは５０ｎｍ以上、より好ましくは１００ｎｍ以上、さらに好ましくは１２０ｎｍ以上、特に好ましくは１４０ｎｍ以上である。また、好ましくは４００ｎｍ以下、より好ましくは３５０ｎｍ以下、さらに好ましくは３００ｎｍ以下、特に好ましくは２５０ｎｍ以下である。分散粒子の平均粒子径が前記上限値以下であると、分散が保たれ易い傾向がある。また、前記下限値以上であれば、隔壁の機能としての光散乱性や遮光性が良好となる傾向がある。
　上記の上限及び下限は任意に組み合わせることができる。例えば、５０～４００ｎｍが好ましく、１００～３５０ｎｍがより好ましく、１２０～３００ｎｍがさらに好ましく、１４０～２５０ｎｍが特に好ましい。
　分散粒子の平均粒子径は、動的光散乱法やレーザー回折法、さらには分散液の塗膜を作り乾燥した上で、ＳＥＭで粒径を計測する方法を使用して測定できる。 The average particle size of dispersed titanium oxide particles (a1) is not particularly limited, but is preferably 50 nm or more, more preferably 100 nm or more, still more preferably 120 nm or more, and particularly preferably 140 nm or more. Also, it is preferably 400 nm or less, more preferably 350 nm or less, even more preferably 300 nm or less, and particularly preferably 250 nm or less. When the average particle size of the dispersed particles is equal to or less than the above upper limit, there is a tendency that the dispersion is likely to be maintained. Further, when the content is at least the above lower limit, there is a tendency that the light scattering property and the light shielding property as a function of the partition wall become good.
The above upper and lower limits can be combined arbitrarily. For example, 50 to 400 nm is preferred, 100 to 350 nm is more preferred, 120 to 300 nm is even more preferred, and 140 to 250 nm is particularly preferred.
The average particle size of the dispersed particles can be measured using a dynamic light scattering method, a laser diffraction method, or a method of forming a coating film of the dispersion, drying it, and measuring the particle size with an SEM.
　（ａ１）酸化チタン粒子の形状は特に限定されないが、例えば、球状、中空状、多孔質状、棒状、板状、繊維状、又は不定形状であり、好ましくは球状である。中空状は粒子径が大きくても沈みにくいというメリットがあり、例えば、粒子径が２００ｎｍより大きい場合に有効である。 (a1) The shape of the titanium oxide particles is not particularly limited, but may be, for example, spherical, hollow, porous, rod-like, plate-like, fibrous, or irregular, preferably spherical. The hollow shape has the advantage that it does not easily sink even if the particle size is large, and is effective when the particle size is larger than 200 nm, for example.
　（ａ）着色剤は、（ａ１）酸化チタン粒子及び他の金属酸化物粒子以外の着色剤（以下、「その他の着色剤」とも称する場合がある。）を含有してもよい。
　（ａ１）酸化チタン粒子とその他の着色剤を併用することで、光散乱性と遮光性を両立できる傾向にある。
　その種類は特に限定されず、顔料を用いてもよいし、染料を用いてもよい。これらの中でも、耐久性の観点から、顔料を用いることが好ましい。 (a) The coloring agent may contain coloring agents other than (a1) titanium oxide particles and other metal oxide particles (hereinafter sometimes referred to as “other coloring agents”).
(a1) The combined use of titanium oxide particles and other colorants tends to achieve both light-scattering properties and light-shielding properties.
The type is not particularly limited, and pigments or dyes may be used. Among these, pigments are preferably used from the viewpoint of durability.
　その他の着色剤に含まれる顔料は、１種でも２種以上でもよい。
　その他の着色剤として用いることができる顔料の種類は特に限定されないが、例えば、有機顔料や無機顔料が挙げられる。これらの中でも、着色感光性樹脂組成物の透過波長をコントロールして効率的に硬化させるとの観点からは、有機顔料を用いることが好ましい。
　有機顔料としては、有機着色顔料や有機黒色顔料が挙げられる。ここで、有機着色顔料とは、黒色以外の色を呈する有機顔料のことを意味し、例えば、赤色顔料、橙色顔料、青色顔料、紫色顔料、緑色顔料、黄色顔料が挙げられる。 One or two or more pigments may be contained in the other colorant.
The types of pigments that can be used as other colorants are not particularly limited, and examples thereof include organic pigments and inorganic pigments. Among these, it is preferable to use an organic pigment from the viewpoint of controlling the transmission wavelength of the colored photosensitive resin composition for efficient curing.
Organic pigments include organic coloring pigments and organic black pigments. Here, the organic coloring pigment means an organic pigment exhibiting a color other than black, and examples thereof include red pigment, orange pigment, blue pigment, purple pigment, green pigment, and yellow pigment.
　有機顔料の中でも、紫外線吸収性の観点から有機着色顔料を用いることが好ましく、遮光性、絶縁性の観点から有機黒色顔料を用いることが好ましい。
　有機着色顔料は、１種を単独で用いてもよく、２種以上を併用してもよい。特に、遮光性の用途に用いる場合には、色の異なる有機着色顔料を組み合わせて用いることがより好ましく、黒に近い色を呈する有機着色顔料の組み合わせを用いることがさらに好ましい。 Among organic pigments, it is preferable to use an organic coloring pigment from the viewpoint of ultraviolet absorption, and it is preferable to use an organic black pigment from the viewpoint of light shielding properties and insulating properties.
An organic coloring pigment may be used individually by 1 type, and may use 2 or more types together. In particular, when it is used for light-shielding applications, it is more preferable to use a combination of organic coloring pigments having different colors, and it is even more preferable to use a combination of organic coloring pigments exhibiting a color close to black.
　これらの有機顔料の化学構造は特に限定されないが、例えば、アゾ系、フタロシアニン系、キナクリドン系、ベンズイミダゾロン系、イソインドリノン系、ジオキサジン系、インダンスレン系、ペリレン系が挙げられる。以下、使用できる顔料の具体例をピグメントナンバーで示す。以下に挙げる「Ｃ．Ｉ．ピグメントレッド２」等の用語は、カラーインデックス（Ｃ．Ｉ．）を意味する。 The chemical structures of these organic pigments are not particularly limited, but examples include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, and perylene-based pigments. Specific examples of pigments that can be used are shown below by pigment numbers. In the following, terms such as "C.I. Pigment Red 2" refer to the Color Index (C.I.).
　赤色顔料としては、Ｃ．Ｉ．ピグメントレッド１、２、３、４、５、６、７、８、９、１２、１４、１５、１６、１７、２１、２２、２３、３１、３２、３７、３８、４１、４７、４８、４８：１、４８：２、４８：３、４８：４、４９、４９：１、４９：２、５０：１、５２：１、５２：２、５３、５３：１、５３：２、５３：３、５７、５７：１、５７：２、５８：４、６０、６３、６３：１、６３：２、６４、６４：１、６８、６９、８１、８１：１、８１：２、８１：３、８１：４、８３、８８、９０：１、１０１、１０１：１、１０４、１０８、１０８：１、１０９、１１２、１１３、１１４、１２２、１２３、１４４、１４６、１４７、１４９、１５１、１６６、１６８、１６９、１７０、１７２、１７３、１７４、１７５、１７６、１７７、１７８、１７９、１８１、１８４、１８５、１８７、１８８、１９０、１９３、１９４、２００、２０２、２０６、２０７、２０８、２０９、２１０、２１４、２１６、２２０、２２１、２２４、２３０、２３１、２３２、２３３、２３５、２３６、２３７、２３８、２３９、２４２、２４３、２４５、２４７、２４９、２５０、２５１、２５３、２５４、２５５、２５６、２５７、２５８、２５９、２６０、２６２、２６３、２６４、２６５、２６６、２６７、２６８、２６９、２７０、２７１、２７２、２７３、２７４、２７５、２７６を挙げることができる。
　遮光性、分散性の観点から好ましくはＣ．Ｉ．ピグメントレッド４８：１、１２２、１４９、１６８、１７７、１７９、１９４、２０２、２０６、２０７、２０９、２２４、２４２、２５４、さらに好ましくはＣ．Ｉ．ピグメントレッド１７７、２０９、２２４、２５４を挙げることができる。
　分散性や遮光性の点で、Ｃ．Ｉ．ピグメントレッド１７７、２５４、２７２が好ましく、着色感光性樹脂組成物を紫外線で硬化させる場合には、赤色顔料としては紫外線吸収率の低いものが好ましく、係る観点からはＣ．Ｉ．ピグメントレッド２５４、２７２がより好ましい。 As a red pigment, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276.
C.I. I. Pigment Red 48: 1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment Red 177, 209, 224, 254 may be mentioned.
C.I. I. Pigment Red 177, 254, and 272 are preferable, and when the colored photosensitive resin composition is cured with ultraviolet rays, red pigments having a low ultraviolet absorption rate are preferable. I. Pigment Red 254, 272 are more preferred.
　橙色（オレンジ）顔料としては、Ｃ．Ｉ．ピグメントオレンジ１、２、５、１３、１６、１７、１９、２０、２１、２２、２３、２４、３４、３６、３８、３９、４３、４６、４８、４９、６１、６２、６４、６５、６７、６８、６９、７０、７１、７２、７３、７４、７５、７７、７８、７９を挙げることができる。
　分散性や遮光性の観点から、Ｃ．Ｉ．ピグメントオレンジ１３、４３、６４、７２が好ましく、着色感光性樹脂組成物を紫外線で硬化させる場合には、オレンジ顔料としては紫外線吸収率の低いものが好ましく、係る観点からはＣ．Ｉ．ピグメントオレンジ６４、７２がより好ましい。 As an orange pigment, C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 can be mentioned.
From the viewpoint of dispersibility and light-shielding properties, C.I. I. Pigment Orange 13, 43, 64, and 72 are preferable, and when the colored photosensitive resin composition is cured with ultraviolet rays, the orange pigment having a low ultraviolet absorption rate is preferable. I. Pigment Orange 64, 72 are more preferred.
　青色顔料としては、Ｃ．Ｉ．ピグメントブルー１、１：２、９、１４、１５、１５：１、１５：２、１５：３、１５：４、１５：６、１６、１７、１９、２５、２７、２８、２９、３３、３５、３６、５６、５６：１、６０、６１、６１：１、６２、６３、６６、６７、６８、７１、７２、７３、７４、７５、７６、７８、７９を挙げることができる。
　遮光性の観点から、好ましくはＣ．Ｉ．ピグメントブルー１５、１５：１、１５：２、１５：３、１５：４、１５：６、６０、さらに好ましくはＣ．Ｉ．ピグメントブルー１５：６を挙げることができる。
　分散性や遮光性の点で、Ｃ．Ｉ．ピグメントブルー１５：６、１６、６０が好ましく、着色感光性樹脂組成物を紫外線で硬化させる場合には、青色顔料としては紫外線吸収率の低いものが好ましく、かかる観点からはＣ．Ｉ．ピグメントブルー６０がより好ましい。 As a blue pigment, C.I. I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 can be mentioned.
From the viewpoint of light-shielding properties, C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 60, more preferably C.I. I. Pigment Blue 15:6 may be mentioned.
C.I. I. Pigment Blue 15:6, 16, 60 is preferable, and when the colored photosensitive resin composition is cured with ultraviolet rays, a blue pigment having a low ultraviolet absorption rate is preferable. I. Pigment Blue 60 is more preferred.
　紫色顔料としては、Ｃ．Ｉ．ピグメントバイオレット１、１：１、２、２：２、３、３：１、３：３、５、５：１、１４、１５、１６、１９、２３、２５、２７、２９、３１、３２、３７、３９、４２、４４、４７、４９、５０を挙げることができる。
　遮光性の観点から、好ましくはＣ．Ｉ．ピグメントバイオレット１９、２３、さらに好ましくはＣ．Ｉ．ピグメントバイオレット２３を挙げることができる。
　分散性や遮光性の点で、Ｃ．Ｉ．ピグメントバイオレット２３、２９を用いることが好ましく、着色感光性樹脂組成物を紫外線で硬化させる場合には、紫色顔料としては紫外線吸収率の低いものが好ましく、係る観点からはＣ．Ｉ．ピグメントバイオレット２９がより好ましい。 As a purple pigment, C.I. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 can be mentioned.
From the viewpoint of light-shielding properties, C.I. I. Pigment Violet 19, 23, more preferably C.I. I. Pigment Violet 23 may be mentioned.
C.I. I. Pigment Violet 23, 29 is preferably used, and when the colored photosensitive resin composition is cured with ultraviolet rays, the purple pigment preferably has a low ultraviolet absorption rate. I. Pigment Violet 29 is more preferred.
　緑色顔料としては、Ｃ．Ｉ．ピグメントグリーン１、２、４、７、８、１０、１３、１４、１５、１７、１８、１９、２６、３６、４５、４８、５０、５１、５４、５５を挙げることができる。
　好ましくはＣ．Ｉ．ピグメントグリーン７、３６を挙げることができる。 As a green pigment, C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 can be mentioned.
Preferably C.I. I. Pigment Green 7, 36 can be mentioned.
　黄色顔料としては、Ｃ．Ｉ．ピグメントイエロー１、１：１、２、３、４、５、６、９、１０、１２、１３、１４、１６、１７、２４、３１、３２、３４、３５、３５：１、３６、３６：１、３７、３７：１、４０、４１、４２、４３、４８、５３、５５、６１、６２、６２：１、６３、６５、７３、７４、７５、８１、８３、８７、９３、９４、９５、９７、１００、１０１、１０４、１０５、１０８、１０９、１１０、１１１、１１６、１１７、１１９、１２０、１２６、１２７、１２７：１、１２８、１２９、１３３、１３４、１３６、１３８、１３９、１４２、１４７、１４８、１５０、１５１、１５３、１５４、１５５、１５７、１５８、１５９、１６０、１６１、１６２、１６３、１６４、１６５、１６６、１６７、１６８、１６９、１７０、１７２、１７３、１７４、１７５、１７６、１８０、１８１、１８２、１８３、１８４、１８５、１８８、１８９、１９０、１９１、１９１：１、１９２、１９３、１９４、１９５、１９６、１９７、１９８、１９９、２００、２０２、２０３、２０４、２０５、２０６、２０７、２０８を挙げることができる。
　好ましくはＣ．Ｉ．ピグメントイエロー８３、１１７、１２９、１３８、１３９、１５０、１５４、１５５、１８０、１８５、さらに好ましくはＣ．Ｉ．ピグメントイエロー８３、１３８、１３９、１５０、１８０を挙げることができる。 As a yellow pigment, C.I. I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95,97,100,101,104,105,108,109,110,111,116,117,119,120,126,127,127:1,128,129,133,134,136,138,139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208 can be mentioned.
Preferably C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, 180 can be mentioned.
　遮光性や、撥インク性の観点から、赤色顔料、橙色顔料、青色顔料及び紫色顔料からなる群から選ばれる少なくとも１種を用いることが好ましい。 From the viewpoint of light shielding properties and ink repellency, it is preferable to use at least one pigment selected from the group consisting of red pigments, orange pigments, blue pigments and violet pigments.
　遮光性や、撥インク性の観点からは、以下の顔料のうち少なくとも１種以上を含有することが好ましい。
　赤色顔料：Ｃ．Ｉ．ピグメントレッド１７７、２５４、２７２
　橙色顔料：Ｃ．Ｉ．ピグメントオレンジ４３、６４、７２
　青色顔料：Ｃ．Ｉ．ピグメントブルー１５：６、６０
　紫色顔料：Ｃ．Ｉ．ピグメントバイオレット２３、２９ From the viewpoint of light shielding properties and ink repellency, it is preferable to contain at least one of the following pigments.
Red pigment: C.I. I. Pigment Red 177, 254, 272
Orange pigment: C.I. I. Pigment Orange 43, 64, 72
Blue pigment: C.I. I. pigment blue 15:6,60
Purple pigment: C.I. I. Pigment Violet 23, 29
　ある態様として、有機着色顔料を２種以上併用する場合、有機着色顔料の組み合わせについては特に限定されないが、遮光性の観点から、その他の着色剤として、赤色顔料及び橙色顔料からなる群から選ばれる少なくとも１種と、青色顔料及び紫色顔料からなる群から選ばれる少なくとも１種とを含有することが好ましい。
　色の組み合わせについては特に限定されない。遮光性の観点からは、例えば、赤色顔料と青色顔料の組み合わせ、青色顔料と橙色顔料の組み合わせ、青色顔料と橙色顔料と紫色顔料の組み合わせが挙げられる。
　遮光性としては、例えば、緑の量子ドットナノ粒子の発光が隣の赤い量子ドットナノ粒子を発光させるのを防ぐためには紫色顔料の吸収波長が好ましいと言うように、何を遮光したいかによって適宜好ましい吸収波長の顔料を選定できる。 In one aspect, when two or more organic coloring pigments are used in combination, the combination of the organic coloring pigments is not particularly limited, but from the viewpoint of light-shielding properties, the other coloring agent is selected from the group consisting of red pigments and orange pigments. It is preferable to contain at least one kind and at least one kind selected from the group consisting of blue pigments and violet pigments.
The combination of colors is not particularly limited. From the viewpoint of light-shielding properties, for example, a combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment, and a combination of a blue pigment, an orange pigment and a violet pigment can be mentioned.
As for the light-shielding property, for example, the absorption wavelength of the purple pigment is preferable in order to prevent the emission of the green quantum dot nanoparticles from causing the adjacent red quantum dot nanoparticles to emit light. A wavelength pigment can be selected.
　有機黒色顔料としては、例えば、ペリレンブラック、アニリンブラック、ファーストブラックＨＢ、ラクタム系化合物を挙げることができる。
　製版性の観点からは、ラクタム系化合物が好ましく、下記一般式（Ａ）で表される化合物（以下、「化合物（Ａ）」ともいう。）、化合物（Ａ）の幾何異性体、化合物（Ａ）の塩、及び化合物（Ａ）の幾何異性体の塩からなる群から選ばれる少なくとも１種を含む有機黒色顔料（以下、「一般式（Ａ）で表される有機黒色顔料」と称する場合がある。）を用いることがより好ましい。 Examples of organic black pigments include perylene black, aniline black, fast black HB, and lactam compounds.
From the viewpoint of plate-making properties, lactam compounds are preferred, and compounds represented by the following general formula (A) (hereinafter also referred to as "compound (A)"), geometric isomers of compound (A), compound (A ) and at least one selected from the group consisting of salts of geometric isomers of compound (A) (hereinafter sometimes referred to as “organic black pigment represented by formula (A)”) There is.) is more preferably used.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　このような有機黒色顔料の具体例としては、商品名で、Ｉｒｇａｐｈｏｒ（登録商標）　Ｂｌａｃｋ　Ｓ　０１００　ＣＦ（ＢＡＳＦ社製）が挙げられる。
　この有機黒色顔料は、好ましくは後述される分散剤、溶剤、方法によって分散して使用される。分散の際に化合物（Ａ）のスルホン酸誘導体が存在すると、分散性や保存性が向上する場合があるため、有機黒色顔料がこれらのスルホン酸誘導体を含むことが好ましい。 A specific example of such an organic black pigment is Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF).
This organic black pigment is preferably used by dispersing it with a dispersant, solvent, and method, which will be described later. If a sulfonic acid derivative of compound (A) is present during dispersion, the dispersibility and storage stability may be improved, so the organic black pigment preferably contains these sulfonic acid derivatives.
　無機顔料としては、例えば、カーボンブラック、アセチレンブラック、ランプブラック、ボーンブラック、黒鉛、鉄黒、チタンブラック等の無機黒色顔料を挙げることができる。 Examples of inorganic pigments include inorganic black pigments such as carbon black, acetylene black, lamp black, bone black, graphite, iron black, and titanium black.
　本発明の着色感光性樹脂組成物は、（ａ）着色剤の含有割合が、着色感光性樹脂組成物の全固形分量に対して２０質量％以下である。１５質量％以下が好ましく、１３質量％以下がより好ましく、１２質量％以下がさらに好ましく、１０質量％以下が特に好ましい。また、１質量％以上が好ましく、３質量％以上がより好ましく、４質量％以上がさらに好ましく、５質量％以上が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、３～２０質量％が好ましく、４～２０質量％がより好ましく、５～１５質量％がさらに好ましく、５～１３質量％がよりさらに好ましく、５～１２質量％がことさらに好ましく、５～１０質量％が特に好ましい。前記下限値以上とすることで遮光性を確保出来る傾向がある。前記上限値以下とすることで分散安定性とパターニング性を確保し易い傾向がある。 In the colored photosensitive resin composition of the present invention, the content of (a) the colorant is 20% by mass or less with respect to the total solid content of the colored photosensitive resin composition. 15% by mass or less is preferable, 13% by mass or less is more preferable, 12% by mass or less is even more preferable, and 10% by mass or less is particularly preferable. Moreover, it is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 4% by mass or more, and particularly preferably 5% by mass or more.
The above upper and lower limits can be combined arbitrarily. For example, 3 to 20% by mass is preferable, 4 to 20% by mass is more preferable, 5 to 15% by mass is more preferable, 5 to 13% by mass is even more preferable, 5 to 12% by mass is particularly preferable, and 5 to 10% by weight is particularly preferred. By making it equal to or higher than the above lower limit, there is a tendency that the light-shielding property can be ensured. By making it equal to or less than the above upper limit, there is a tendency to easily ensure dispersion stability and patterning properties.
　本発明の着色感光性樹脂組成物は、（ａ１）酸化チタン粒子の含有割合が、着色感光性樹脂組成物の全固形分量に対して２０質量％以下である。１５質量％以下が好ましく、１３質量％以下がより好ましく、１２質量％以下がさらに好ましく、１０質量％以下が特に好ましい。また、１質量％以上が好ましく、３質量％以上がより好ましく、４質量％以上がさらに好ましく、５質量％以上が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、３～２０質量％が好ましく、４～２０質量％がより好ましく、５～１５質量％がさらに好ましく、５～１３質量％がよりさらに好ましく、５～１２質量％がことさら好ましく、５～１０質量％が特に好ましい。前記下限値以上とすることで遮光性と光散乱性を確保できる傾向がある。前記上限値以下とすることで分散が安定し易い傾向がある。 In the colored photosensitive resin composition of the present invention, the content of (a1) titanium oxide particles is 20% by mass or less with respect to the total solid content of the colored photosensitive resin composition. 15% by mass or less is preferable, 13% by mass or less is more preferable, 12% by mass or less is even more preferable, and 10% by mass or less is particularly preferable. Moreover, it is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 4% by mass or more, and particularly preferably 5% by mass or more.
The above upper and lower limits can be combined arbitrarily. For example, 3 to 20% by mass is preferable, 4 to 20% by mass is more preferable, 5 to 15% by mass is more preferable, 5 to 13% by mass is even more preferable, 5 to 12% by mass is particularly preferable, and 5 to 10% by mass is more preferable. % by weight is particularly preferred. By making it equal to or higher than the above lower limit, there is a tendency that the light shielding property and the light scattering property can be secured. When the content is equal to or less than the above upper limit, there is a tendency that the dispersion tends to be stabilized.
　（ａ）着色剤中の（ａ１）酸化チタン粒子の含有割合は、好ましくは５０質量％以上であり、６０質量％以上がより好ましく、７０質量％以上がさらに好ましく、８０質量％以上が特に好ましく、また、１００質量％以下である。
　上記の上限及び下限は任意に組み合わせることができる。例えば、５０～１００質量％が好ましく、６０～１００質量％がより好ましく、７０～１００質量％がさらに好ましく、８０～１００質量％が特に好ましい。前記下限値以上とすることで光散乱性を確保し易い傾向がある。 The content of (a1) titanium oxide particles in (a) the colorant is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and particularly preferably 80% by mass or more. , and 100% by mass or less.
The above upper and lower limits can be combined arbitrarily. For example, 50 to 100% by mass is preferable, 60 to 100% by mass is more preferable, 70 to 100% by mass is even more preferable, and 80 to 100% by mass is particularly preferable. By making it more than the said lower limit, there exists a tendency which is easy to ensure light-scattering property.
［１－１－２］（ｂ）アルカリ可溶性樹脂
　本発明の着色感光性樹脂組成物は、（ｂ）アルカリ可溶性樹脂を含有する。本発明において、（ｂ）アルカリ可溶性樹脂としてはアルカリ現像液で現像可能なものであれば特に限定されない。
　（ｂ）アルカリ可溶性樹脂としては、カルボキシ基又は水酸基を有する各種樹脂が挙げられ、現像性に優れるとの観点からはカルボキシ基を有するものが好ましい。
　撥インク性を向上する観点からは、エチレン性不飽和基を有するアルカリ可溶性樹脂が好ましい。 [1-1-2] (b) Alkali-Soluble Resin The colored photosensitive resin composition of the present invention contains (b) an alkali-soluble resin. In the present invention, (b) the alkali-soluble resin is not particularly limited as long as it can be developed with an alkali developer.
(b) Alkali-soluble resins include various resins having a carboxy group or a hydroxyl group, and those having a carboxy group are preferable from the viewpoint of excellent developability.
From the viewpoint of improving ink repellency, an alkali-soluble resin having an ethylenically unsaturated group is preferable.
　本発明の着色感光性樹脂組成物の（ｂ）アルカリ可溶性樹脂は、撥インク性の観点から、側鎖にエチレン性不飽和基を有するアクリル共重合樹脂（ｂ１１）（以下、「アクリル共重合樹脂（ｂ１１）」と略記する場合がある。）を含むことが好ましい。パターンの直線性の観点からは、エポキシ（メタ）アクリレート樹脂（ｂ１２）を含むことが好ましい。 The (b) alkali-soluble resin of the colored photosensitive resin composition of the present invention is, from the viewpoint of ink repellency, an acrylic copolymer resin (b11) having an ethylenically unsaturated group in a side chain (hereinafter referred to as "acrylic copolymer resin (b11)" may be abbreviated.) is preferably included. From the viewpoint of the linearity of the pattern, it is preferable that the epoxy (meth)acrylate resin (b12) is included.
　撥インク性と直線性の両立の観点からは、（ｂ）アルカリ可溶性樹脂として、アクリル共重合樹脂（ｂ１１）と、エポキシ（メタ）アクリレート樹脂（ｂ１２）の両者を含むことが好ましい。 From the viewpoint of achieving both ink repellency and linearity, it is preferable that the (b) alkali-soluble resin includes both an acrylic copolymer resin (b11) and an epoxy (meth)acrylate resin (b12).
［アクリル共重合樹脂（ｂ１１）］
　アクリル共重合樹脂（ｂ１１）は、側鎖にエチレン性不飽和基を有する。エチレン性不飽和基を有するものとすることで、露光による光硬化が起こってより強固な膜となり、現像時にも撥液剤が流出しにくくなり、撥インク性が発現しやすくなると考えられる。 [Acrylic copolymer resin (b11)]
The acrylic copolymer resin (b11) has ethylenically unsaturated groups in side chains. By having an ethylenically unsaturated group, it is believed that photocuring by exposure occurs to form a stronger film, the liquid repellent agent is less likely to flow out during development, and ink repellency is likely to be exhibited.
（一般式（Ｉ）で表される部分構造）
　アクリル共重合樹脂（ｂ１１）が有する、エチレン性不飽和基を有する側鎖を含む部分構造は特に限定されない。膜の柔軟性に伴うラジカルの発散しやすさの観点から、例えば、下記一般式（Ｉ）で表される部分構造を有することが好ましい。 (Partial structure represented by general formula (I))
The partial structure containing a side chain having an ethylenically unsaturated group, which the acrylic copolymer resin (b11) has, is not particularly limited. From the viewpoint of easiness of radical divergence associated with flexibility of the film, it is preferable to have, for example, a partial structure represented by the following general formula (I).
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　式（Ｉ）中、Ｒ1及びＲ2は各々独立に、水素原子又はメチル基を表す。＊は結合手を表す。 In formula (I), R 1 and R 2 each independently represent a hydrogen atom or a methyl group. * represents a bond.
　式（Ｉ）で表される部分構造の中でも、感度やアルカリ現像性の観点から、下記一般式（Ｉ’）で表される部分構造が好ましい。 Among the partial structures represented by formula (I), partial structures represented by the following general formula (I') are preferable from the viewpoint of sensitivity and alkali developability.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　式（Ｉ’）中、Ｒ1及びＲ2は各々独立に、水素原子又はメチル基を表す。ＲXは水素原子又は多塩基酸残基を表す。 In formula (I'), R 1 and R 2 each independently represent a hydrogen atom or a methyl group. R X represents a hydrogen atom or a polybasic acid residue.
　多塩基酸残基とは、多塩基酸又はその無水物からＯＨ基を１つ除した１価の基を意味する。多塩基酸としては、例えば、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ベンゾフェノンテトラカルボン酸、メチルヘキサヒドロフタル酸、エンドメチレンテトラヒドロフタル酸、クロレンド酸、メチルテトラヒドロフタル酸、ビフェニルテトラカルボン酸から選ばれた１種又は２種以上が挙げられる。
　パターニング特性の観点から、好ましくは、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ビフェニルテトラカルボン酸であり、より好ましくは、テトラヒドロフタル酸、ビフェニルテトラカルボン酸である。 A polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Examples of polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylene. One or more selected from tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid can be used.
From the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and tetrahydrophthalic acid is more preferred. phthalic acid and biphenyltetracarboxylic acid.
　アクリル共重合樹脂（ｂ１１）が式（Ｉ）で表される部分構造を含む場合、その含有割合は特に限定されない。アクリル共重合樹脂（ｂ１１）の構成単位の総モル数に対して１０モル％以上が好ましく、２０モル％以上がより好ましく、３０モル％以上がさらに好ましく、４０モル％以上がよりさらに好ましく、５０モル％以上が特に好ましく、また、９９モル％以下が好ましく、９５モル％以下がより好ましく、９０モル％以下がさらに好ましく、８０モル％以下がよりさらに好ましく、７０モル％以下が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１０～９９モル％、好ましくは２０～９５モル％、より好ましくは３０～９０モル％、さらに好ましくは４０～８０モル％、よりさらに好ましくは５０～７０モル％である。前記下限値以上とすることで撥インク性が向上する傾向がある。前記上限値以下とすることで線幅の細い高精細な隔壁を形成できる傾向がある。 When the acrylic copolymer resin (b11) contains the partial structure represented by formula (I), the content is not particularly limited. It is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, still more preferably 40 mol% or more, and 50 99 mol% or less is particularly preferable, 95 mol% or less is more preferable, 90 mol% or less is even more preferable, 80 mol% or less is even more preferable, and 70 mol% or less is particularly preferable.
The above upper and lower limits can be combined arbitrarily. For example, it is 10 to 99 mol%, preferably 20 to 95 mol%, more preferably 30 to 90 mol%, even more preferably 40 to 80 mol%, still more preferably 50 to 70 mol%. The ink repellency tends to be improved by making it equal to or higher than the lower limit. When the content is equal to or less than the above upper limit, there is a tendency that high-definition partition walls with a narrow line width can be formed.
　アクリル共重合樹脂（ｂ１１）が式（Ｉ’）で表される部分構造を含む場合、その含有割合は特に限定されない。アクリル共重合樹脂（ｂ１１）の構成単位の総モル数に対して１０モル％以上が好ましく、２０モル％以上がより好ましく、３０モル％以上がさらに好ましく、４０モル％以上がよりさらに好ましく、５０モル％以上が特に好ましく、また、９９モル％以下が好ましく、９５モル％以下がより好ましく、９０モル％以下がさらに好ましく、８０モル％以下がよりさらに好ましく、７０モル％以下が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１０～９９モル％、好ましくは２０～９５モル％、より好ましくは３０～９０モル％、さらに好ましくは４０～８０モル％、よりさらに好ましくは５０～７０モル％である。前記下限値以上とすることで撥インク性が向上する傾向がある。前記上限値以下とすることで線幅の細い高精細な隔壁を形成できる傾向がある。 When the acrylic copolymer resin (b11) contains the partial structure represented by formula (I'), the content is not particularly limited. It is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, still more preferably 40 mol% or more, and 50 99 mol% or less is particularly preferable, 95 mol% or less is more preferable, 90 mol% or less is even more preferable, 80 mol% or less is even more preferable, and 70 mol% or less is particularly preferable.
The above upper and lower limits can be combined arbitrarily. For example, it is 10 to 99 mol%, preferably 20 to 95 mol%, more preferably 30 to 90 mol%, even more preferably 40 to 80 mol%, still more preferably 50 to 70 mol%. The ink repellency tends to be improved by making it equal to or higher than the lower limit. When the content is equal to or less than the above upper limit, there is a tendency that high-definition partition walls with a narrow line width can be formed.
（一般式（ＩＩ）で表される部分構造）
　アクリル共重合樹脂（ｂ１１）が式（Ｉ）で表される部分構造を含む場合、他に含まれる部分構造は特に限定されない。現像密着性の観点から、下記一般式（ＩＩ）で表される部分構造をさらに有してもよい。 (Partial structure represented by general formula (II))
When the acrylic copolymer resin (b11) contains the partial structure represented by formula (I), the other partial structure contained is not particularly limited. From the viewpoint of development adhesion, it may further have a partial structure represented by the following general formula (II).
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　式（ＩＩ）中、Ｒ3は水素原子又はメチル基を表し、Ｒ4は置換基を有していてもよいアルキル基、置換基を有していてもよい芳香族環基、又は置換基を有していてもよいアルケニル基を表す。 In formula (II), R3 represents a hydrogen atom or a methyl group, R4 represents an optionally substituted alkyl group, an optionally substituted aromatic ring group, or a substituent. represents an alkenyl group which may be present.
（Ｒ4）
　式（ＩＩ）において、Ｒ4は置換基を有していてもよいアルキル基、置換基を有していてもよい芳香族環基、又は置換基を有していてもよいアルケニル基を表す。
　Ｒ4におけるアルキル基としては直鎖状、分岐鎖状又は環状のアルキル基が挙げられる。その炭素数は、１以上が好ましく、３以上がより好ましく、５以上がさらに好ましく、８以上が特に好ましく、また、２０以下が好ましく、１８以下がより好ましく、１６以下がさらに好ましく、１４以下がよりさらに好ましく、１２以下が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～２０が好ましく、１～１８がより好ましく、３～１６がさらに好ましく、５～１４がよりさらに好ましく、８～１２が特に好ましい。前記下限値以上とすることで膜強度が高くなり、現像密着性が向上する傾向がある。前記上限値以下とすることで残渣が低減する傾向がある。 ( R4 )
In formula (II), R 4 represents an optionally substituted alkyl group, an optionally substituted aromatic ring group, or an optionally substituted alkenyl group.
Alkyl groups for R 4 include linear, branched and cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, more preferably 5 or more, particularly preferably 8 or more, and preferably 20 or less, more preferably 18 or less, further preferably 16 or less, and 14 or less. Even more preferably, 12 or less is particularly preferable.
The above upper and lower limits can be combined arbitrarily. For example, 1 to 20 are preferred, 1 to 18 are more preferred, 3 to 16 are even more preferred, 5 to 14 are even more preferred, and 8 to 12 are particularly preferred. When the content is at least the above lower limit, the film strength tends to increase and the development adhesion tends to improve. A residue tends to be reduced by making it below the said upper limit.
　アルキル基としては、例えば、メチル基、エチル基、シクロヘキシル基、ジシクロペンタニル基、ドデカニル基が挙げられる。現像性の観点から、ジシクロペンタニル基又はドデカニル基が好ましく、ジシクロペンタニル基がより好ましい。
　アルキル基が有していてもよい置換基としては、例えば、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシ基、アクリロイル基、メタクリロイル基が挙げられ、現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Examples of alkyl groups include methyl, ethyl, cyclohexyl, dicyclopentanyl, and dodecanyl groups. From the viewpoint of developability, a dicyclopentanyl group or a dodecanyl group is preferable, and a dicyclopentanyl group is more preferable.
Substituents that the alkyl group may have include, for example, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group and carboxy group. , an acryloyl group, and a methacryloyl group, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
　Ｒ4における芳香族環基としては、１価の芳香族炭化水素環基及び１価の芳香族複素環基が挙げられる。その炭素数は６以上が好ましく、また、２４以下が好ましく、２２以下がより好ましく、２０以下がさらに好ましく、１８以下が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、６～２４、好ましくは６～２２、より好ましくは６～２０、さらに好ましくは６～１８である。前記下限値以上とすることで現像密着性が向上する傾向がある。前記上限値以下とすることで残渣が低減する傾向がある。 The aromatic ring group for R 4 includes monovalent aromatic hydrocarbon ring groups and monovalent aromatic heterocyclic groups. The number of carbon atoms is preferably 6 or more, preferably 24 or less, more preferably 22 or less, still more preferably 20 or less, and particularly preferably 18 or less.
The above upper and lower limits can be combined arbitrarily. For example, 6-24, preferably 6-22, more preferably 6-20, and even more preferably 6-18. When the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. A residue tends to be reduced by making it below the said upper limit.
　芳香族炭化水素環基における芳香族炭化水素環としては、単環であっても縮合環であってもよく、例えば、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環が挙げられる。 The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.
　芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよく、例えば、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ベンゾイミダゾール環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環が挙げられる。
　Ｒ4における芳香族環基としては、現像性の観点から、ベンゼン環、ナフタレン環が好ましく、ベンゼン環がより好ましい。 The aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring, such as furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring and imidazole ring. , oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring.
From the viewpoint of developability, the aromatic ring group for R 4 is preferably a benzene ring or a naphthalene ring, more preferably a benzene ring.
　芳香族環基が有していてもよい置換基としては、例えば、メチル基、エチル基、プロピル基、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシ基が挙げられ、現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Substituents which the aromatic ring group may have include, for example, methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group and epoxy group. , an oligoethylene glycol group, a phenyl group, and a carboxy group, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
　Ｒ4におけるアルケニル基としては、直鎖状、分岐鎖状又は環状のアルケニル基が挙げられる。その炭素数は、２以上であり、また、２２以下が好ましく、２０以下より好ましく、１８以下さらに好ましく、１６以下よりさらに好ましく、１４以下特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、２～２２、好ましくは２～２０、より好ましくは２～１８、さらに好ましくは２～１６、よりさらに好ましくは２～１４である。前記下限値以上とすることで現像密着性が向上する傾向がある。前記上限値以下とすることで残渣が低減する傾向がある。 Alkenyl groups for R 4 include linear, branched and cyclic alkenyl groups. The number of carbon atoms is 2 or more, preferably 22 or less, more preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less.
The above upper and lower limits can be combined arbitrarily. For example, 2-22, preferably 2-20, more preferably 2-18, even more preferably 2-16, even more preferably 2-14. When the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. A residue tends to be reduced by making it below the said upper limit.
　アルケニル基が有していてもよい置換基としては、例えば、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシ基が挙げられ、現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Substituents that the alkenyl group may have include, for example, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxy group. , and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
　Ｒ4としては、現像性と膜強度の観点から、アルキル基又はアルケニル基が好ましく、アルキル基がより好ましい。 R 4 is preferably an alkyl group or an alkenyl group, more preferably an alkyl group, from the viewpoint of developability and film strength.
　アクリル共重合樹脂（ｂ１１）式（ＩＩ）で表される部分構造を含む場合、その含有割合は特に限定されないが、アクリル共重合樹脂（ｂ１１）の構成単位の総モル数に対して１モル％以上が好ましく、２モル％以上がより好ましく、５モル％以上がさらに好ましく、１０モル％以上が特に好ましく、２０モル％以上がことさら好ましく、また、７０モル％以下が好ましく、６０モル％以下がより好ましく、５０モル％以下がさらに好ましく、４０モル％以下が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～７０モル％、好ましくは２～７０モル％、より好ましくは５～６０モル％、さらに好ましくは１０～５０モル％、特に好ましくは２０～４０モル％である。前記下限値以上とすることで密着性が向上する傾向がある。前記上限値以下とすることで残渣が低減する傾向がある。 When the acrylic copolymer resin (b11) contains a partial structure represented by formula (II), the content ratio is not particularly limited, but 1 mol% with respect to the total number of moles of the structural units of the acrylic copolymer resin (b11). 2 mol% or more is more preferable, 5 mol% or more is more preferable, 10 mol% or more is particularly preferable, 20 mol% or more is particularly preferable, and 70 mol% or less is preferable, and 60 mol% or less is preferable. More preferably, 50 mol % or less is even more preferable, and 40 mol % or less is particularly preferable.
The above upper and lower limits can be combined arbitrarily. For example, 1 to 70 mol%, preferably 2 to 70 mol%, more preferably 5 to 60 mol%, still more preferably 10 to 50 mol%, particularly preferably 20 to 40 mol%. Adhesion tends to be improved by making it more than the said lower limit. A residue tends to be reduced by making it below the said upper limit.
（一般式（ＩＩＩ）で表される部分構造）
　アクリル共重合樹脂（ｂ１１）が式（Ｉ）で表される部分構造を含む場合、他に含まれる部分構造として、耐熱性、膜強度の観点から下記一般式（ＩＩＩ）で表される部分構造をさらに有してもよい。 (Partial structure represented by general formula (III))
When the acrylic copolymer resin (b11) contains a partial structure represented by formula (I), another partial structure to be included is a partial structure represented by the following general formula (III) from the viewpoint of heat resistance and film strength. may further have
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　式（ＩＩＩ）中、Ｒ5は水素原子又はメチル基を表し、Ｒ6は置換基を有していてもよいアルキル基、置換基を有していてもよいアルケニル基、置換基を有していてもよいアルキニル基、ヒドロキシ基、カルボキシ基、ハロゲン原子、置換基を有していてもよいアルコキシ基、チオール基、又は置換基を有していてもよいアルキルスルフィド基を表す。ｔは０～５の整数を表す。 In formula (III), R 5 represents a hydrogen atom or a methyl group, R 6 represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted represents an optionally substituted alkynyl group, a hydroxy group, a carboxy group, a halogen atom, an optionally substituted alkoxy group, a thiol group, or an optionally substituted alkylsulfide group. t represents an integer of 0 to 5;
（Ｒ6）
　式（ＩＩＩ）においてＲ6は置換基を有していてもよいアルキル基、置換基を有していてもよいアルケニル基、置換基を有していてもよいアルキニル基、ヒドロキシ基、カルボキシ基、ハロゲン原子、置換基を有していてもよいアルコキシ基、チオール基、又は置換基を有していてもよいアルキルスルフィド基を表す。 ( R6 )
In formula (III), R 6 is an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a hydroxy group, a carboxy group, represents a halogen atom, an optionally substituted alkoxy group, a thiol group, or an optionally substituted alkylsulfide group.
　Ｒ6におけるアルキル基としては、直鎖状、分岐鎖状又は環状のアルキル基が挙げられる。その炭素数は、１以上が好ましく、３以上がより好ましく、５以上がさらに好ましく、また、２０以下が好ましく、１８以下がより好ましく、１６以下がさらに好ましく、１４以下がよりさらに好ましく、１２以下が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～２０、好ましくは１～１８、より好ましくは３～１６、さらに好ましくは５～１４である。前記下限値以上とすることで現像密着性が向上する傾向がある。前記上限値以下とすることで残渣が低減する傾向がある。 Alkyl groups for R 6 include linear, branched and cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, even more preferably 14 or less, and 12 or less. is particularly preferred.
The above upper and lower limits can be combined arbitrarily. For example, 1 to 20, preferably 1 to 18, more preferably 3 to 16, even more preferably 5 to 14. When the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. A residue tends to be reduced by making it below the said upper limit.
　アルキル基としては、例えば、メチル基、エチル基、シクロヘキシル基、ジシクロペンタニル基、ドデカニル基が挙げられる。現像性と膜強度の観点から、ジシクロペンタニル基、ドデカニル基が好ましく、ジシクロペンタニル基がより好ましい。 Examples of alkyl groups include methyl, ethyl, cyclohexyl, dicyclopentanyl, and dodecanyl groups. From the viewpoint of developability and film strength, a dicyclopentanyl group and a dodecanyl group are preferred, and a dicyclopentanyl group is more preferred.
　アルキル基が有していてもよい置換基としては、例えば、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシ基、アクリロイル基、メタクリロイル基が挙げられ、現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Substituents that the alkyl group may have include, for example, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group and carboxy group. , an acryloyl group, and a methacryloyl group, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
　Ｒ6におけるアルケニル基としては、直鎖状、分岐鎖状又は環状のアルケニル基が挙げられる。その炭素数は、２以上であり、また、２２以下が好ましく、２０以下がより好ましく、１８以下がさらに好ましく、１６以下がよりさらに好ましく、１４以下が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、２～２２、好ましくは２～２０、より好ましくは２～１８、さらに好ましくは２～１６、よりさらに好ましくは２～１４である。前記下限値以上とすることで現像密着性が向上する傾向がある。前記上限値以下とすることで残渣が低減する傾向がある。 Alkenyl groups for R 6 include linear, branched and cyclic alkenyl groups. The number of carbon atoms is 2 or more, preferably 22 or less, more preferably 20 or less, still more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less.
The above upper and lower limits can be combined arbitrarily. For example, 2-22, preferably 2-20, more preferably 2-18, even more preferably 2-16, even more preferably 2-14. When the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. A residue tends to be reduced by making it below the said upper limit.
　アルケニル基が有していてもよい置換基としては、例えば、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシ基が挙げられ、現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Substituents that the alkenyl group may have include, for example, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxy group. , and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
　Ｒ6におけるアルキニル基としては、直鎖状、分岐鎖状又は環状のアルキニル基が挙げられる。その炭素数は、２以上であり、また、２２以下が好ましく、２０以下がより好ましく、１８以下がさらに好ましく、１６以下がよりさらに好ましく、１４以下が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、２～２２、好ましくは２～２０、より好ましくは２～１８、さらに好ましくは２～１６、よりさらに好ましくは２～１４である。前記下限値以上とすることで現像密着性が向上する傾向がある。前記上限値以下とすることで残渣が低減する傾向がある。 Alkynyl groups for R 6 include linear, branched and cyclic alkynyl groups. The number of carbon atoms is 2 or more, preferably 22 or less, more preferably 20 or less, still more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less.
The above upper and lower limits can be combined arbitrarily. For example, 2-22, preferably 2-20, more preferably 2-18, even more preferably 2-16, even more preferably 2-14. When the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. A residue tends to be reduced by making it below the said upper limit.
　アルキニル基が有していてもよい置換基としては、例えば、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシ基が挙げられ、現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Substituents that the alkynyl group may have include, for example, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group and carboxy group. , and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
　Ｒ6におけるハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられ、撥インク性の観点からはフッ素原子が好ましい。 The halogen atom for R 6 includes, for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferred from the viewpoint of ink repellency.
　Ｒ6におけるアルコキシ基としては、直鎖状、分岐鎖状又は環状のアルコキシ基が挙げられる。その炭素数は、１以上であり、また、２０以下が好ましく、１８以下がより好ましく、１６以下がさらに好ましく、１４以下がよりさらに好ましく、１２以下が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～２０、好ましくは１～１８、より好ましくは１～１６、さらに好ましくは１～１４、よりさらに好ましくは１～１２である。前記下限値以上とすることで現像密着性が向上する傾向がある。前記上限値以下とすることで残渣が低減する傾向がある。 Alkoxy groups for R 6 include linear, branched and cyclic alkoxy groups. The number of carbon atoms is 1 or more, preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less.
The above upper and lower limits can be combined arbitrarily. For example, 1-20, preferably 1-18, more preferably 1-16, even more preferably 1-14, even more preferably 1-12. When the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. A residue tends to be reduced by making it below the said upper limit.
　アルコキシ基が有していてもよい置換基としては、例えば、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシ基、アクリロイル基、メタクリロイル基が挙げられ、現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Substituents that the alkoxy group may have include, for example, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxy group. , an acryloyl group, and a methacryloyl group, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
　Ｒ6におけるアルキルスルフィド基としては、直鎖状、分岐鎖状又は環状のアルキルスルフィド基が挙げられる。その炭素数は、１以上が好ましく、また、２０以下が好ましく、１８以下がより好ましく、１６以下がさらに好ましく、１４以下がよりさらに好ましく、１２以下が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～２０、好ましくは１～１８、より好ましくは１～１６、さらに好ましくは１～１４、よりさらに好ましくは１～１２である。前記下限値以上とすることで現像密着性が向上する傾向がある。前記上限値以下とすることで残渣が低減する傾向がある。 The alkylsulfide group for R 6 includes linear, branched and cyclic alkylsulfide groups. The number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less.
The above upper and lower limits can be combined arbitrarily. For example, 1-20, preferably 1-18, more preferably 1-16, even more preferably 1-14, even more preferably 1-12. When the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. A residue tends to be reduced by making it below the said upper limit.
　アルキルスルフィド基におけるアルキル基が有していてもよい置換基としては、例えば、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシ基、アクリロイル基、メタクリロイル基が挙げられ、現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Examples of substituents that the alkyl group in the alkylsulfide group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl group, carboxyl group, acryloyl group, and methacryloyl group, and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferred.
　Ｒ6としては、現像性の観点から、ヒドロキシ基、カルボキシ基が好ましく、カルボキシ基がより好ましい。 R 6 is preferably a hydroxy group or a carboxy group, more preferably a carboxy group, from the viewpoint of developability.
　式（ＩＩＩ）においてｔは０～５の整数を表し、製造容易性の観点からはｔが０であることが好ましい。 In formula (III), t represents an integer of 0 to 5, and t is preferably 0 from the viewpoint of ease of production.
　アクリル共重合樹脂（ｂ１１）が式（ＩＩＩ）で表される部分構造を含む場合、その含有割合は特に限定されない。アクリル共重合樹脂（ｂ１１）の構成単位の総モル数に対して０．５モル％以上が好ましく、１モル％以上がより好ましく、２モル％以上がさらに好ましく、４モル％以上が特に好ましい。また、５０モル％以下が好ましく、３０モル％以下がより好ましく、２０モル％以下がさらに好ましく、１０モル％以下がよりさらに好ましく、６モル％以下が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、０．５～５０モル％、好ましくは１～３０モル％、より好ましくは１～２０モル％、さらに好ましくは２～１０モル％、よりさらに好ましくは４～６モル％である。前記下限値以上とすることで膜の均一性が向上する傾向がある。前記上限値以下とすることで残渣が低減する傾向がある。 When the acrylic copolymer resin (b11) contains the partial structure represented by formula (III), the content is not particularly limited. It is preferably 0.5 mol % or more, more preferably 1 mol % or more, still more preferably 2 mol % or more, and particularly preferably 4 mol % or more, relative to the total number of moles of the structural units of the acrylic copolymer resin (b11). Also, it is preferably 50 mol % or less, more preferably 30 mol % or less, even more preferably 20 mol % or less, even more preferably 10 mol % or less, and particularly preferably 6 mol % or less.
The above upper and lower limits can be combined arbitrarily. For example, it is 0.5 to 50 mol %, preferably 1 to 30 mol %, more preferably 1 to 20 mol %, even more preferably 2 to 10 mol %, still more preferably 4 to 6 mol %. When the content is equal to or higher than the lower limit, there is a tendency that the uniformity of the film is improved. A residue tends to be reduced by making it below the said upper limit.
（一般式（ＩＶ）で表される部分構造）
　アクリル共重合樹脂（ｂ１１）が式（Ｉ）で表される部分構造を有する場合、他に含まれる部分構造として、現像性の観点から下記一般式（ＩＶ）で表される部分構造をさらに有してもよい。 (Partial structure represented by general formula (IV))
When the acrylic copolymer resin (b11) has a partial structure represented by the formula (I), it further has a partial structure represented by the following general formula (IV) from the viewpoint of developability as another included partial structure. You may
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　上記式（ＩＶ）中、Ｒ7は水素原子又はメチル基を表す。 In formula (IV) above, R7 represents a hydrogen atom or a methyl group.
　アクリル共重合樹脂（ｂ１１）が式（ＩＶ）で表される部分構造を含む場合、その含有割合は特に限定されない。アクリル共重合樹脂（ｂ１１）の構成単位の総モル数に対して５モル％以上が好ましく、１０モル％以上がより好ましく、２０モル％以上がさらに好ましく、また、８０モル％以下が好ましく、７０モル％以下がより好ましく、６０モル％以下がさらに好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、５～８０モル％、好ましくは１０～７０モル％、より好ましくは２０～６０モル％である。前記下限値以上とすることで残渣が低減する傾向がある。前記上限値以下とすることで撥インク性が向上する傾向がある。 When the acrylic copolymer resin (b11) contains the partial structure represented by formula (IV), the content is not particularly limited. It is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, and preferably 80 mol% or less, based on the total number of moles of the structural units of the acrylic copolymer resin (b11). mol % or less is more preferable, and 60 mol % or less is even more preferable.
The above upper and lower limits can be combined arbitrarily. For example, 5 to 80 mol %, preferably 10 to 70 mol %, more preferably 20 to 60 mol %. Residue tends to be reduced by making it equal to or higher than the lower limit. The ink repellency tends to be improved by making it equal to or less than the above upper limit.
　アクリル共重合樹脂（ｂ１１）の酸価は特に限定されない。１０ｍｇＫＯＨ／ｇ以上が好ましく、２０ｍｇＫＯＨ／ｇ以上がより好ましく、３０ｍｇＫＯＨ／ｇ以上がさらに好ましく、５０ｍｇＫＯＨ／ｇ以上がよりさらに好ましく、６０ｍｇＫＯＨ／ｇ以上が特に好ましく、また、１５０ｍｇＫＯＨ／ｇ以下が好ましく、１４０ｍｇＫＯＨ／ｇ以下がより好ましく、１３０ｍｇＫＯＨ／ｇ以下がさらに好ましく、１２０ｍｇＫＯＨ／ｇ以下がよりさらに好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１０～１５０ｍｇＫＯＨ／ｇ、好ましくは２０～１４０ｍｇＫＯＨ／ｇ、より好ましくは３０～１３０ｍｇＫＯＨ／ｇ、さらに好ましくは５０～１２０ｍｇＫＯＨ／ｇ、よりさらに好ましくは６０～１２０ｍｇＫＯＨ／ｇである。前記下限値以上とすることで現像性が向上する傾向がある。前記上限値以下とすることで現像密着性が向上する傾向がある。 The acid value of the acrylic copolymer resin (b11) is not particularly limited. Preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, still more preferably 30 mgKOH/g or more, even more preferably 50 mgKOH/g or more, particularly preferably 60 mgKOH/g or more, and preferably 150 mgKOH/g or less, 140 mgKOH /g or less, more preferably 130 mgKOH/g or less, and even more preferably 120 mgKOH/g or less.
The above upper and lower limits can be combined arbitrarily. For example, 10 to 150 mgKOH/g, preferably 20 to 140 mgKOH/g, more preferably 30 to 130 mgKOH/g, still more preferably 50 to 120 mgKOH/g, even more preferably 60 to 120 mgKOH/g. Developability tends to be improved by setting the content to be at least the above lower limit. When the amount is set to the above upper limit or less, there is a tendency that development adhesion is improved.
　アクリル共重合樹脂（ｂ１１）の重量平均分子量（Ｍｗ）は特に限定されない。１０００以上が好ましく、２０００以上がより好ましく、４０００以上がさらに好ましく、６０００以上がよりさらに好ましく、７０００以上がことさらに好ましく、８０００以上が特に好ましく、また、３００００以下が好ましく、２００００以下がより好ましく、１５０００以下がさらに好ましく、１００００以下が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１０００～３００００が好ましく、２０００～２００００がより好ましく、４０００～２００００がさらに好ましく、６０００～１５０００がよりさらに好ましく、７０００～１５０００がことさらに好ましく、８０００～１００００が特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。前記上限値以下とすることで残渣が低減する傾向がある。 The weight average molecular weight (Mw) of the acrylic copolymer resin (b11) is not particularly limited. 1000 or more is preferable, 2000 or more is more preferable, 4000 or more is more preferable, 6000 or more is even more preferable, 7000 or more is particularly preferable, 8000 or more is particularly preferable, 30000 or less is preferable, and 20000 or less is more preferable, 15,000 or less is more preferable, and 10,000 or less is particularly preferable.
The above upper and lower limits can be combined arbitrarily. For example, 1,000 to 30,000 is preferred, 2,000 to 20,000 is more preferred, 4,000 to 20,000 is even more preferred, 6,000 to 15,000 is even more preferred, 7,000 to 15,000 is even more preferred, and 8,000 to 10,000 is particularly preferred. When the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. A residue tends to be reduced by making it below the said upper limit.
　（ｂ）アルカリ可溶性樹脂がアクリル共重合樹脂（ｂ１１）を含む場合、アルカリ可溶性樹脂に含まれるアクリル共重合樹脂（ｂ１１）の含有割合は特に限定されない。（ｂ）アルカリ可溶性樹脂の全質量に対して１０質量％以上が好ましく、３０質量％以上がより好ましく、４０質量％以上がさらに好ましく、５０質量％以上がよりさらに好ましく、５５質量％以上が特に好ましく、また、９０質量％以下が好ましく、８０質量％以下がより好ましく、７０質量％以下がさらに好ましく、６５質量％以下が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１０～９０質量％、好ましくは３０～８０質量％、より好ましくは４０～８０質量％、さらに好ましくは５０～７０質量％、よりさらに好ましくは５５～６５質量％である。前記下限値以上とすることで撥インク性が向上する傾向がある。前記上限値以下とすることで線幅の細い高精細な隔壁を形成できる傾向がある。 (b) When the alkali-soluble resin contains the acrylic copolymer resin (b11), the content of the acrylic copolymer resin (b11) contained in the alkali-soluble resin is not particularly limited. (b) is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, even more preferably 50% by mass or more, and particularly 55% by mass or more, relative to the total mass of the alkali-soluble resin 90% by mass or less is preferable, 80% by mass or less is more preferable, 70% by mass or less is even more preferable, and 65% by mass or less is particularly preferable.
The above upper and lower limits can be combined arbitrarily. For example, it is 10 to 90% by mass, preferably 30 to 80% by mass, more preferably 40 to 80% by mass, even more preferably 50 to 70% by mass, still more preferably 55 to 65% by mass. The ink repellency tends to be improved by making it equal to or higher than the lower limit. When the content is equal to or less than the above upper limit, there is a tendency that high-definition partition walls with a narrow line width can be formed.
　（ｂ）アルカリ可溶性樹脂がアクリル共重合樹脂（ｂ１１）とエポキシ（メタ）アクリレート樹脂（ｂ１２）の両方を含む場合、アクリル共重合樹脂（ｂ１１）の含有割合は、アクリル共重合樹脂（ｂ１１）とエポキシ（メタ）アクリレート樹脂（ｂ１２）との含有割合の合計に対して、１０質量％以上が好ましく、３０質量％以上がより好ましく、４０質量％以上がさらに好ましく、５０質量％以上がよりさらに好ましく、５５質量％以上が特に好ましく、また９０質量％以下が好ましく、８０質量％以下がより好ましく、７０質量％以下がさらに好ましく、６５質量％以下が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１０～９０質量％、好ましくは３０～８０質量％、より好ましくは４０～８０質量％、さらに好ましくは５０～７０質量％、よりさらに好ましくは５５～６５質量％以上である。前記下限値以上とすることで撥インク性が向上する傾向がある。前記上限値以下とすることで隔壁断面の垂直性が向上する傾向がある。 (b) When the alkali-soluble resin contains both the acrylic copolymer resin (b11) and the epoxy (meth)acrylate resin (b12), the content of the acrylic copolymer resin (b11) is It is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and even more preferably 50% by mass or more, relative to the total content of the epoxy (meth)acrylate resin (b12). , 55% by mass or more is particularly preferable, 90% by mass or less is preferable, 80% by mass or less is more preferable, 70% by mass or less is even more preferable, and 65% by mass or less is particularly preferable.
The above upper and lower limits can be combined arbitrarily. For example, it is 10 to 90% by mass, preferably 30 to 80% by mass, more preferably 40 to 80% by mass, even more preferably 50 to 70% by mass, still more preferably 55 to 65% by mass or more. The ink repellency tends to be improved by making it equal to or higher than the lower limit. By making it equal to or less than the above upper limit, there is a tendency that the verticality of the cross section of the partition wall is improved.
　アクリル共重合樹脂（ｂ１１）の具体例としては、例えば、日本国特開平８－２９７３６６号公報や日本国特開２００１－８９５３３号公報に記載の樹脂が挙げられる。 Specific examples of the acrylic copolymer resin (b11) include resins described in Japanese Patent Application Laid-Open Nos. 8-297366 and 2001-89533.
［エポキシ（メタ）アクリレート樹脂（ｂ１２）］
　エポキシ（メタ）アクリレート樹脂（ｂ１２）は、エポキシ樹脂にエチレン性不飽和モノカルボン酸又はエステル化合物を付加し、任意でイソシアネート基含有化合物を反応させた後、さらに多塩基酸又はその無水物を反応させた樹脂である。例えば、エポキシ樹脂のエポキシ基に、不飽和モノカルボン酸のカルボキシ基が開環付加されることにより、エポキシ化合物にエステル結合（－ＣＯＯ－）を介してエチレン性不飽和結合が付加されると共に、その際生じた水酸基に、多塩基酸無水物の一方のカルボキシ基が付加された樹脂が挙げられる。また、多塩基酸無水物を付加するときに、多価アルコールを同時に添加して付加された樹脂も挙げられる。 [Epoxy (meth)acrylate resin (b12)]
Epoxy (meth)acrylate resin (b12) is obtained by adding an ethylenically unsaturated monocarboxylic acid or an ester compound to an epoxy resin, optionally reacting with an isocyanate group-containing compound, and then further reacting with a polybasic acid or its anhydride. It is a resin that has been For example, ring-opening addition of a carboxyl group of an unsaturated monocarboxylic acid to an epoxy group of an epoxy resin results in addition of an ethylenically unsaturated bond to the epoxy compound via an ester bond (-COO-), Resins in which one carboxyl group of the polybasic acid anhydride is added to the hydroxyl group generated at that time are exemplified. Moreover, the resin added by adding a polyhydric alcohol simultaneously when adding a polybasic acid anhydride is also mentioned.
　また、上記反応で得られた樹脂のカルボキシ基に、さらに反応し得る官能基を有する化合物を反応させて得られる樹脂も、上記エポキシ（メタ）アクリレート樹脂（ｂ１２）に含まれる。
　エポキシ（メタ）アクリレート樹脂は化学構造上、実質的にエポキシ基を有さず、かつ「（メタ）アクリレート」に限定されるものではないが、エポキシ化合物（エポキシ樹脂）が原料であり、かつ、「（メタ）アクリレート」が代表例であるので慣用に従いこのように命名されている。（ｂ１２）エポキシ（メタ）アクリレート樹脂としては、パターンの直線性の観点から、主鎖に芳香族環を有するものをより好適に用いることができる。 The resin obtained by reacting the carboxy group of the resin obtained by the above reaction with a compound having a reactive functional group is also included in the epoxy (meth)acrylate resin (b12).
Epoxy (meth)acrylate resin has substantially no epoxy group in terms of chemical structure, and is not limited to "(meth)acrylate", but epoxy compound (epoxy resin) is a raw material, and Since "(meth)acrylate" is a representative example, the name is used in this way according to common practice. As the (b12) epoxy (meth)acrylate resin, those having an aromatic ring in the main chain can be more preferably used from the viewpoint of pattern linearity.
　ここで、エポキシ樹脂とは、熱硬化により樹脂を形成する以前の原料化合物をも含めて言うこととし、そのエポキシ樹脂としては、公知のエポキシ樹脂の中から適宜選択して用いることができる。また、エポキシ樹脂は、フェノール性化合物とエピハロヒドリンとを反応させて得られる化合物を用いることができる。フェノール性化合物としては、２価もしくは２価以上のフェノール性水酸基を有する化合物が好ましく、単量体でも重合体でもよい。
　具体的には、例えば、ビスフェノールＡエポキシ樹脂、ビスフェノールＦエポキシ樹脂、ビスフェノールＳエポキシ樹脂、フェノールノボラックエポキシ樹脂、クレゾールノボラックエポキシ樹脂、ビフェニルノボラックエポキシ樹脂、トリスフェノールエポキシ樹脂、フェノールとジシクロペンタジエンとの重合エポキシ樹脂、ジハイドロオキシルフルオレン型エポキシ樹脂、ジハイドロオキシルアルキレンオキシルフルオレン型エポキシ樹脂、９，９－ビス（４’－ヒドロキシフェニル）フルオレンのジグリシジルエーテル化物、１，１－ビス（４’－ヒドロキシフェニル）アダマンタンのジグリシジルエーテル化物、が挙げられ、主鎖に芳香族環を有するものを好適に用いることができる。 Here, the epoxy resin includes a raw material compound before forming a resin by thermosetting, and the epoxy resin can be appropriately selected and used from known epoxy resins. As the epoxy resin, a compound obtained by reacting a phenolic compound and epihalohydrin can be used. The phenolic compound is preferably a compound having a divalent or more divalent phenolic hydroxyl group, and may be a monomer or a polymer.
Specifically, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolac epoxy resin, trisphenol epoxy resin, polymerization of phenol and dicyclopentadiene. Epoxy resin, dihydroxylfluorene-type epoxy resin, dihydroxylalkyleneoxylfluorene-type epoxy resin, 9,9-bis(4′-hydroxyphenyl)diglycidyl ether of fluorene, 1,1-bis(4′-hydroxy phenyl)adamantane, and those having an aromatic ring in the main chain can be preferably used.
　高い硬化膜強度の観点から、ビスフェノールＡエポキシ樹脂、フェノールノボラックエポキシ樹脂、クレゾールノボラックエポキシ樹脂、フェノールとジシクロペンタジエンとの重合エポキシ樹脂、９，９－ビス（４’－ヒドロキシフェニル）フルオレンのジグリシジルエーテル化物、が好ましく、ビスフェノールＡエポキシ樹脂が特に好ましい。
　エポキシ樹脂としては、例えば、ビスフェノールＡ型エポキシ樹脂（例えば、三菱ケミカル社製の「ｊＥＲ（登録商標、以下同じ。）８２８」、「ｊＥＲ１００１」、「ｊＥＲ１００２」、「ｊＥＲ１００４」、日本化薬社製の「ＮＥＲ－１３０２」（エポキシ当量３２３，軟化点７６℃）等）、ビスフェノールＦ型樹脂（例えば、三菱ケミカル社製の「ｊＥＲ８０７」、「ｊＥＲ４００４Ｐ」、「ｊＥＲ４００５Ｐ」、「ｊＥＲ４００７Ｐ」、日本化薬社製の「ＮＥＲ－７４０６」（エポキシ当量３５０，軟化点６６℃）等）、ビスフェノールＳ型エポキシ樹脂、ビフェニルグリシジルエーテル（例えば、三菱ケミカル社製の「ｊＥＲＹＸ－４０００」）、フェノールノボラック型エポキシ樹脂（例えば、日本化薬社製の「ＥＰＰＮ（登録商標、以下同じ。）－２０１」、三菱ケミカル社製の「ｊＥＲ１５２」、「ｊＥＲ１５４」、ダウケミカル社製の「ＤＥＮ－４３８」）、（ｏ，ｍ，ｐ－）クレゾールノボラック型エポキシ樹脂（例えば、日本化薬社製の「ＥＯＣＮ（登録商標、以下同じ。）－１０２Ｓ」、「ＥＯＣＮ－１０２０」、「ＥＯＣＮ－１０４Ｓ」）、トリグリシジルイソシアヌレート（例えば、日産化学社製の「ＴＥＰＩＣ（登録商標）」）、トリスフェノールメタン型エポキシ樹脂（例えば、日本化薬社製の「ＥＰＰＮ－５０１」、「ＥＰＰＮ－５０２」、「ＥＰＰＮ－５０３」）、脂環式エポキシ樹脂（ダイセル社製の「セロキサイド（登録商標、以下同じ。）２０２１Ｐ」、「セロキサイドＥＨＰＥ」）、ジシクロペンタジエンとフェノールの反応によるフェノール樹脂をグリシジル化したエポキシ樹脂（例えば、ＤＩＣ社製の「ＥＸＡ－７２００」、日本化薬社製の「ＮＣ－７３００」）、下記一般式（ｉ－１１）～（ｉ－１４）で表されるエポキシ樹脂を好適に用いることができる。具体的には、例えば、下記一般式（ｉ－１１）で表されるエポキシ樹脂として日本化薬社製の「ＸＤ－１０００」、下記一般式（ｉ－１２）で表されるエポキシ樹脂として日本化薬社製の「ＮＣ－３０００」、下記一般式（ｉ－１４）で表されるエポキシ樹脂として新日鉄住金化学社製の「ＥＳＦ－３００」が挙げられる。 From the viewpoint of high cured film strength, bisphenol A epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, polymerized epoxy resin of phenol and dicyclopentadiene, and diglycidyl of 9,9-bis(4′-hydroxyphenyl)fluorene. Etherates are preferred, and bisphenol A epoxy resins are particularly preferred.
Examples of epoxy resins include bisphenol A type epoxy resins (e.g., "jER (registered trademark, hereinafter the same) 828", "jER1001", "jER1002", "jER1004" manufactured by Mitsubishi Chemical Corporation, manufactured by Nippon Kayaku Co., Ltd.). "NER-1302" (epoxy equivalent 323, softening point 76 ° C.), etc.), bisphenol F type resin (for example, Mitsubishi Chemical "jER807", "jER4004P", "jER4005P", "jER4007P", Nippon Kayaku "NER-7406" (epoxy equivalent 350, softening point 66 ° C.), etc. manufactured by Mitsubishi Chemical Corporation), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example, "jERYX-4000" manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (For example, "EPPN (registered trademark, hereinafter the same) -201" manufactured by Nippon Kayaku, "jER152" and "jER154" manufactured by Mitsubishi Chemical, "DEN-438" manufactured by Dow Chemical), (o , m, p-) cresol novolac-type epoxy resin (for example, Nippon Kayaku Co., Ltd. “EOCN (registered trademark, hereinafter the same)-102S”, “EOCN-1020”, “EOCN-104S”), triglycidyl isocyanate Nurate (e.g., "TEPIC (registered trademark)" manufactured by Nissan Chemical Industries, Ltd.), trisphenolmethane type epoxy resin (e.g., "EPPN-501", "EPPN-502", "EPPN-503" manufactured by Nippon Kayaku Co., Ltd.) ), alicyclic epoxy resins (“Celoxide (registered trademark) 2021P” and “Celoxide EHPE” manufactured by Daicel Corporation), epoxy resins obtained by glycidylating phenol resins by reaction of dicyclopentadiene and phenol (for example, "EXA-7200" manufactured by DIC Corporation, "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), epoxy resins represented by the following general formulas (i-11) to (i-14) can be suitably used. . Specifically, for example, as an epoxy resin represented by the following general formula (i-11), "XD-1000" manufactured by Nippon Kayaku Co., Ltd., and as an epoxy resin represented by the following general formula (i-12), Japan "NC-3000" manufactured by Kayaku Co., Ltd., and "ESF-300" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. as an epoxy resin represented by the following general formula (i-14).
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　式（ｉ－１１）において、ｎは平均値であり、０～１０の数を表す。Ｒ111は各々独立に水素原子、ハロゲン原子、炭素数１～８のアルキル基、炭素数３～１０のシクロアルキル基、フェニル基、ナフチル基、又はビフェニル基を表す。なお、１分子中に存在する複数のＲ111は、それぞれ同じであっても異なっていてもよい。 In formula (i-11), n is an average value and represents a number from 0 to 10. Each R 111 independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. Plural R 111 in one molecule may be the same or different.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　式（ｉ－１２）において、ｎは平均値であり、０～１０の数を表す。Ｒ121は各々独立に水素原子、ハロゲン原子、炭素数１～８のアルキル基、炭素数３～１０のシクロアルキル基、フェニル基、ナフチル基、又はビフェニル基を表す。なお、１分子中に存在する複数のＲ121は、それぞれ同じであっても異なっていてもよい。 In formula (i-12), n is an average value and represents a number from 0 to 10. Each R 121 independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. Plural R 121 in one molecule may be the same or different.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　式（ｉ－１３）において、Ｘは下記一般式（ｉ－１３－１）又は（ｉ－１３－２）で表される連結基を表す。但し、分子構造中に１つ以上のアダマンタン構造を含む。ｃは２又は３を表す。 In formula (i-13), X represents a linking group represented by general formula (i-13-1) or (i-13-2) below. However, it contains one or more adamantane structures in its molecular structure. c represents 2 or 3;
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　式（ｉ－１３－１）及び（ｉ－１３－２）において、Ｒ131～Ｒ134及びＲ135～Ｒ137は、各々独立に、置換基を有していてもよいアダマンチル基、水素原子、置換基を有していてもよい炭素数１～１２のアルキル基、又は置換基を有していてもよいフェニル基を表す。＊は結合手を表す。 In formulas (i-13-1) and (i-13-2), R 131 to R 134 and R 135 to R 137 each independently represent an optionally substituted adamantyl group, a hydrogen atom, It represents an optionally substituted alkyl group having 1 to 12 carbon atoms, or an optionally substituted phenyl group. * represents a bond.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　式（ｉ－１４）において、ｐ及びｑは各々独立に０～４の整数を表し、Ｒ141及びＲ142は各々独立に炭素数１～４のアルキル基又はハロゲン原子を表す。Ｒ143及びＲ144は各々独立に炭素数１～４のアルキレン基を表す。ｘ及びｙは各々独立に０以上の整数を表す。 In formula (i-14), p and q each independently represent an integer of 0 to 4, and R 141 and R 142 each independently represent an alkyl group having 1 to 4 carbon atoms or a halogen atom. R 143 and R 144 each independently represent an alkylene group having 1 to 4 carbon atoms. x and y each independently represent an integer of 0 or more.
　一般式（ｉ－１１）～（ｉ－１４）のいずれかで表されるエポキシ樹脂を用いることが好ましい。 It is preferable to use an epoxy resin represented by any one of general formulas (i-11) to (i-14).
　エチレン性不飽和モノカルボン酸としては、例えば、（メタ）アクリル酸、クロトン酸、マレイン酸、フマル酸、イタコン酸、シトラコン酸等、及び、ペンタエリスリトールトリ（メタ）アクリレート無水コハク酸付加物、ペンタエリスリトールトリ（メタ）アクリレートテトラヒドロ無水フタル酸付加物、ジペンタエリスリトールペンタ（メタ）アクリレート無水コハク酸付加物、ジペンタエリスリトールペンタ（メタ）アクリレート無水フタル酸付加物、ジペンタエリスリトールペンタ（メタ）アクリレートテトラヒドロ無水フタル酸付加物、（メタ）アクリル酸とε－カプロラクトンとの反応生成物が挙げられる。感度の観点から、（メタ）アクリル酸が好ましい。 Examples of ethylenically unsaturated monocarboxylic acids include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, pentaerythritol tri(meth)acrylate succinic anhydride adduct, penta Erythritol tri(meth)acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta(meth)acrylate succinic anhydride adduct, dipentaerythritol penta(meth)acrylate phthalic anhydride adduct, dipentaerythritol penta(meth)acrylate tetrahydro Examples include phthalic anhydride adducts and reaction products of (meth)acrylic acid and ε-caprolactone. From the viewpoint of sensitivity, (meth)acrylic acid is preferred.
　多塩基酸（無水物）としては、例えば、コハク酸、マレイン酸、イタコン酸、フタル酸、テトラヒドロフタル酸、３－メチルテトラヒドロフタル酸、４－メチルテトラヒドロフタル酸、３－エチルテトラヒドロフタル酸、４－エチルテトラヒドロフタル酸、ヘキサヒドロフタル酸、３－メチルヘキサヒドロフタル酸、４－メチルヘキサヒドロフタル酸、３－エチルヘキサヒドロフタル酸、４－エチルヘキサヒドロフタル酸、トリメリット酸、ピロメリット酸、ベンゾフェノンテトラカルボン酸、ビフェニルテトラカルボン酸、及びそれらの無水物が挙げられる。アウトガスの観点から、コハク酸無水物、マレイン酸無水物、テトラヒドロフタル酸無水物、ヘキサヒドロフタル酸無水物が好ましく、コハク酸無水物、テトラヒドロフタル酸無水物がより好ましい。 Examples of polybasic acids (anhydrides) include succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4 - ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid , benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, and their anhydrides. From the viewpoint of outgassing, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are preferable, and succinic anhydride and tetrahydrophthalic anhydride are more preferable.
　多価アルコールを用いることで、エポキシ（メタ）アクリレート樹脂（ｂ１２）の分子量を増大させ、分子中に分岐を導入することができ、分子量と粘度のバランスをとることができる傾向がある。また、分子中への酸基の導入率を増やすことができ、感度や密着性等のバランスがとれやすい傾向がある。
　多価アルコールとしては、例えばトリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリメチロールエタン、１，２，３－プロパントリオールの中から選ばれる１種又は２種以上の多価アルコールであることが好ましい。 The use of a polyhydric alcohol tends to increase the molecular weight of the epoxy (meth)acrylate resin (b12), introduce branches into the molecule, and balance the molecular weight and viscosity. In addition, the rate of introduction of acid groups into the molecule can be increased, and there is a tendency to easily balance sensitivity, adhesion, and the like.
The polyhydric alcohol is, for example, one or more polyhydric alcohols selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. Preferably.
　エポキシ（メタ）アクリレート樹脂としては、前述の樹脂以外に、韓国公開特許第１０－２０１３－００２２９５５号公報に記載の樹脂が挙げられる。 Examples of epoxy (meth)acrylate resins include resins described in Korean Patent Publication No. 10-2013-0022955 in addition to the resins described above.
　エポキシ（メタ）アクリレート樹脂（ｂ１２）の酸価は特に限定されない。１０ｍｇＫＯＨ／ｇ以上が好ましく、３０ｍｇＫＯＨ／ｇ以上がより好ましく、５０ｍｇＫＯＨ／ｇ以上がさらに好ましく、７０ｍｇＫＯＨ／ｇ以上がよりさらに好ましく、８０ｍｇＫＯＨ／ｇ以上が特に好ましく、また、２００ｍｇＫＯＨ／ｇ以下が好ましく、１８０ｍｇＫＯＨ／ｇ以下がより好ましく、１５０ｍｇＫＯＨ／ｇ以下がさらに好ましく、１２０ｍｇＫＯＨ／ｇ以下がよりさらに好ましく、１１０ｍｇＫＯＨ／ｇ以下が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１０～２００ｍｇＫＯＨ／ｇが好ましく、３０～１８０ｍｇＫＯＨ／ｇがより好ましく、５０～１５０ｍｇＫＯＨ／ｇがさらに好ましく、７０～１２０ｍｇＫＯＨ／ｇがよりさらに好ましく、８０～１１０ｍｇＫＯＨ／ｇが特に好ましい。前記下限値以上とすることで現像性が向上する傾向がある。前記上限値以下とすることで膜強度が向上する傾向がある。 The acid value of the epoxy (meth)acrylate resin (b12) is not particularly limited. 10 mgKOH/g or more is preferable, 30 mgKOH/g or more is more preferable, 50 mgKOH/g or more is still more preferable, 70 mgKOH/g or more is even more preferable, 80 mgKOH/g or more is particularly preferable, and 200 mgKOH/g or less is preferable, and 180 mgKOH/g is preferable. /g or less, more preferably 150 mgKOH/g or less, even more preferably 120 mgKOH/g or less, and particularly preferably 110 mgKOH/g or less.
The above upper and lower limits can be combined arbitrarily. For example, 10 to 200 mgKOH/g is preferred, 30 to 180 mgKOH/g is more preferred, 50 to 150 mgKOH/g is even more preferred, 70 to 120 mgKOH/g is even more preferred, and 80 to 110 mgKOH/g is particularly preferred. Developability tends to be improved by setting the content to be at least the above lower limit. When the content is equal to or less than the above upper limit, there is a tendency that the film strength is improved.
　エポキシ（メタ）アクリレート樹脂（ｂ１２）の重量平均分子量（Ｍｗ）は特に限定されない。１０００以上が好ましく、２０００以上がより好ましく、３０００以上がさらに好ましく、４０００以上がことさらに好ましく、５０００以上が特に好ましく、また、３００００以下が好ましく、２００００以下がより好ましく、１５０００以下がさらに好ましく、１００００以下がことさらに好ましく、８０００以下が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１０００～３００００が好ましく、２０００～２００００がより好ましく、３０００～１５０００がさらに好ましく、４０００～１００００がことさらに好ましく、５０００～８０００が特に好ましい。前記下限値以上とすることで膜強度が向上する傾向がある。前記上限値以下とすることで残渣が低減する傾向がある。 The weight average molecular weight (Mw) of the epoxy (meth)acrylate resin (b12) is not particularly limited. 1000 or more is preferable, 2000 or more is more preferable, 3000 or more is more preferable, 4000 or more is particularly preferable, 5000 or more is particularly preferable, 30000 or less is preferable, 20000 or less is more preferable, 15000 or less is more preferable, 10000 The following is particularly preferable, and 8000 or less is particularly preferable.
The above upper and lower limits can be combined arbitrarily. For example, 1,000 to 30,000 is preferred, 2,000 to 20,000 is more preferred, 3,000 to 15,000 is even more preferred, 4,000 to 10,000 is particularly preferred, and 5,000 to 8,000 is particularly preferred. When the content is equal to or higher than the lower limit, there is a tendency that the film strength is improved. A residue tends to be reduced by making it below the said upper limit.
　（ｂ）アルカリ可溶性樹脂がエポキシ（メタ）アクリレート樹脂（ｂ１２）を含む場合、その含有割合は特に限定されない。（ｂ）アルカリ可溶性樹脂の全質量に対して１０質量％以上が好ましく、２０質量％以上がより好ましく、３０質量％以上がさらに好ましく、３５質量％以上がよりさらに好ましく、４０質量％以上が特に好ましく、５０質量％以上が最も好ましく、また、９０質量％以下が好ましく、７０質量％以下がより好ましく、６０質量％以下がさらに好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１０～９０質量％、好ましくは２０～９０質量％、より好ましくは３０～７０質量％、さらに好ましくは３５～７０質量％、よりさらに好ましくは４０～６０質量％、特に好ましくは５０～６０質量％である。前記下限値以上とすることで直線性が向上する傾向がある。前記上限値以下とすることで線幅の細い高精細な隔壁を形成できる傾向がある。 (b) When the alkali-soluble resin contains the epoxy (meth)acrylate resin (b12), the content is not particularly limited. (b) is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, even more preferably 35% by mass or more, and particularly 40% by mass or more, relative to the total mass of the alkali-soluble resin 50% by mass or more is most preferable, 90% by mass or less is preferable, 70% by mass or less is more preferable, and 60% by mass or less is even more preferable.
The above upper and lower limits can be combined arbitrarily. For example, 10 to 90% by mass, preferably 20 to 90% by mass, more preferably 30 to 70% by mass, still more preferably 35 to 70% by mass, even more preferably 40 to 60% by mass, particularly preferably 50 to 60% by mass. % by mass. The linearity tends to be improved by making it equal to or higher than the lower limit. When the content is equal to or less than the above upper limit, there is a tendency that high-definition partition walls with a narrow line width can be formed.
　エポキシ（メタ）アクリレート樹脂（ｂ１２）は、従来公知の方法により合成することができる。具体的には、前記エポキシ樹脂を有機溶剤に溶解させ、触媒と熱重合禁止剤の共存下、前記エチレン性不飽和結合を有する酸又はエステル化合物を加えて付加反応させ、さらに多塩基酸又はその無水物を加えて反応を続ける方法を用いることができる。例えば日本国特許第３９３８３７５号公報、日本国特許第５１６９４２２号公報に記載されている方法が挙げられる。 The epoxy (meth)acrylate resin (b12) can be synthesized by a conventionally known method. Specifically, the epoxy resin is dissolved in an organic solvent, and in the presence of a catalyst and a thermal polymerization inhibitor, the acid or ester compound having the ethylenically unsaturated bond is added for addition reaction, and further polybasic acid or its A method of continuing the reaction by adding anhydride can be used. For example, the methods described in Japanese Patent No. 3938375 and Japanese Patent No. 5169422 can be mentioned.
　反応に用いる有機溶剤としては、例えば、メチルエチルケトン、シクロヘキサノン、ジエチレングリコールエ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アセテートなどの有機溶剤の１種または２種以上が挙げられる。
　触媒としては、例えば、トリエチルアミン、ベンジルジメチルアミン、トリベンジルアミン等の第３級アミン類、テトラメチルアンモニウムクロライド、メチルトリエチルアンモニウムクロライド、テトラエチルアンモニウムクロライド、テトラブチルアンモニウムクロライド、トリメチルベンジルアンモニウムクロライドなどの第４級アンモニウム塩類、トリフェニルホスフィンなどの燐化合物、トリフェニルスチビンなどのスチビン類などの１種または２種以上が挙げられる。
　熱重合禁止剤としては、例えば、ハイドロキノン、ハイドロキノンモノメチルエーテル、メチルハイドロキノンなどの１種または２種以上が挙げられる。 Examples of the organic solvent used for the reaction include one or more organic solvents such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate.
Examples of catalysts include tertiary amines such as triethylamine, benzyldimethylamine and tribenzylamine; One or more of ammonium salts, phosphorus compounds such as triphenylphosphine, stibines such as triphenylstibine, and the like can be used.
Examples of thermal polymerization inhibitors include one or more of hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, and the like.
　エチレン性不飽和結合を有する酸又はエステル化合物の使用量は、エポキシ樹脂のエポキシ基の１化学当量に対して０．７～１．３化学当量が好ましく、０．９～１．１化学当量がより好ましい。
　付加反応時の温度としては、６０～１５０℃が好ましく、８０～１２０℃がより好ましい。
　多塩基酸（無水物）の使用量は、付加反応で生じた水酸基の１化学当量に対して、０．１～１．２化学当量が好ましく、０．２～１．１化学当量がより好ましい。 The amount of the acid or ester compound having an ethylenically unsaturated bond is preferably 0.7 to 1.3 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents, per one chemical equivalent of the epoxy group of the epoxy resin. more preferred.
The temperature during the addition reaction is preferably 60 to 150°C, more preferably 80 to 120°C.
The amount of polybasic acid (anhydride) to be used is preferably 0.1 to 1.2 chemical equivalents, more preferably 0.2 to 1.1 chemical equivalents, with respect to 1 chemical equivalent of hydroxyl groups generated in the addition reaction. .
　エポキシ（メタ）アクリレート樹脂（ｂ１２）の中でも、膜強度や直線性の観点から、下記一般式（ｉ）で表される部分構造を有するエポキシ（メタ）アクリレート樹脂及び下記一般式（ｉｉ）で表される部分構造を有するエポキシ（メタ）アクリレート樹脂からなる群から選ばれる少なくとも１種を含むことが好ましい。 Among the epoxy (meth)acrylate resins (b12), from the viewpoint of film strength and linearity, epoxy (meth)acrylate resins having a partial structure represented by the following general formula (i) and epoxy (meth)acrylate resins represented by the following general formula (ii) It is preferable that at least one selected from the group consisting of epoxy (meth)acrylate resins having a partial structure is included.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　式（ｉ）中、Ｒaは水素原子又はメチル基を表し、Ｒbは置換基を有していてもよい２価の炭化水素基を表す。式（ｉ）中のベンゼン環は、さらに任意の置換基により置換されていてもよい。＊は結合手を表す。 In formula (i), R a represents a hydrogen atom or a methyl group, and R b represents a divalent hydrocarbon group which may have a substituent. The benzene ring in formula (i) may be further substituted with any substituent. * represents a bond.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　式（ｉｉ）中、Ｒcは各々独立に、水素原子又はメチル基を表す。Ｒdは、環状炭化水素基を側鎖として有する２価の炭化水素基を表す。＊は結合手を表す。 In formula (ii), each R c independently represents a hydrogen atom or a methyl group. R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. * represents a bond.
　式（ｉ）で表される部分構造を有するエポキシ（メタ）アクリレート樹脂（以下、「エポキシ（メタ）アクリレート樹脂（ｂ１２－１）」と称する場合がある。）について詳述する。 The epoxy (meth)acrylate resin having a partial structure represented by formula (i) (hereinafter sometimes referred to as "epoxy (meth)acrylate resin (b12-1)") will be described in detail.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　式（ｉ）中、Ｒaは水素原子又はメチル基を表し、Ｒbは置換基を有していてもよい２価の炭化水素基を表す。式（ｉ）中のベンゼン環は、さらに任意の置換基により置換されていてもよい。＊は結合手を表す。 In formula (i), R a represents a hydrogen atom or a methyl group, and R b represents a divalent hydrocarbon group which may have a substituent. The benzene ring in formula (i) may be further substituted with any substituent. * represents a bond.
（Ｒb）
　式（ｉ）において、Ｒbは置換基を有していてもよい２価の炭化水素基を表す。
　２価の炭化水素基としては、２価の脂肪族基、２価の芳香族環基、１以上の２価の脂肪族基と１以上の２価の芳香族環基とを連結した基が挙げられる。 (R b )
In formula (i), R b represents a divalent hydrocarbon group which may have a substituent.
The divalent hydrocarbon group includes a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked. mentioned.
　２価の脂肪族基は、直鎖状、分岐鎖状、環状の脂肪族基が挙げられる。現像溶解性の観点からは直鎖状の脂肪族基が好ましい。露光部への現像液の浸透低減の観点からは環状の脂肪族基が好ましい。２価の脂肪族基の炭素数は１以上が好ましく、３以上がより好ましく、６以上がさらに好ましく、また、２０以下が好ましく、１５以下がより好ましく、１０以下がさらに好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～２０が好ましく、３～１５がより好ましく、６～１０がさらに好ましい。前記下限値以上とすることで膜強度が向上する傾向がある。前記上限値以下とすることで撥インク性が向上する傾向がある。 The divalent aliphatic group includes linear, branched and cyclic aliphatic groups. A linear aliphatic group is preferred from the viewpoint of development solubility. A cyclic aliphatic group is preferred from the viewpoint of reducing permeation of the developer into the exposed area. The number of carbon atoms in the divalent aliphatic group is preferably 1 or more, more preferably 3 or more, still more preferably 6 or more, and is preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less.
The above upper and lower limits can be combined arbitrarily. For example, 1 to 20 are preferred, 3 to 15 are more preferred, and 6 to 10 are even more preferred. When the content is equal to or higher than the lower limit, there is a tendency that the film strength is improved. The ink repellency tends to be improved by making it equal to or less than the above upper limit.
　２価の直鎖状脂肪族基としては、例えば、メチレン基、エチレン基、ｎ－プロピレン基、ｎ－ブチレン基、ｎ－ヘキシレン基、ｎ－ヘプチレン基が挙げられる。撥インク性や製造コストの観点から、メチレン基が好ましい。
　２価の分岐鎖状脂肪族基としては、２価の直鎖状脂肪族基に、側鎖として、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基を有する構造が挙げられる。
　２価の環状の脂肪族基が有する環の数は特に限定されない。１以上が好ましく、２以上がより好ましく、また、１０以下が好ましく、５以下がより好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～１０が好ましく、２～５がより好ましい。前記下限値以上とすることで膜強度が向上する傾向がある。前記上限値以下とすることで現像性が向上する傾向がある。
　２価の環状の脂肪族基としては、例えば、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、シクロドデカン環等の環から水素原子を２つ除した基が挙げられる。膜強度と現像性の観点から、アダマンタン環から水素原子を２つ除した基が好ましい。 Examples of divalent linear aliphatic groups include methylene group, ethylene group, n-propylene group, n-butylene group, n-hexylene group and n-heptylene group. A methylene group is preferable from the viewpoint of ink repellency and manufacturing cost.
The divalent branched aliphatic group includes a divalent linear aliphatic group, and side chains such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group. , a sec-butyl group, and a structure having a tert-butyl group.
The number of rings that the divalent cyclic aliphatic group has is not particularly limited. 1 or more is preferable, 2 or more is more preferable, 10 or less is preferable, and 5 or less is more preferable.
The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 are preferred, and 2 to 5 are more preferred. When the content is equal to or higher than the lower limit, there is a tendency that the film strength is improved. The developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
As the divalent cyclic aliphatic group, for example, two hydrogen atoms are removed from a ring such as cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, and cyclododecane ring. groups. From the viewpoint of film strength and developability, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable.
　２価の脂肪族基が有していてもよい置換基としては、例えば、メトキシ基、エトキシ基等の炭素数１～５のアルコキシ基；水酸基；ニトロ基；シアノ基；カルボキシ基が挙げられる。合成容易性の観点から、無置換であることが好ましい。 Examples of substituents that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.
　２価の芳香族環基としては、２価の芳香族炭化水素環基及び２価の芳香族複素環基が挙げられる。その炭素数は４以上が好ましく、５以上がより好ましく、６以上がさらに好ましく、また、２０以下が好ましく、１５以下がより好ましく、１０以下がさらに好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、４～２０が好ましく、５～１５がより好ましく、６～１０がさらに好ましい。前記下限値以上とすることで膜強度が向上する傾向がある。前記上限値以下とすることで現像性が向上する傾向がある。 The divalent aromatic ring group includes a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The number of carbon atoms is preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less.
The above upper and lower limits can be combined arbitrarily. For example, 4 to 20 are preferred, 5 to 15 are more preferred, and 6 to 10 are even more preferred. When the content is equal to or higher than the lower limit, there is a tendency that the film strength is improved. The developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
　２価の芳香族炭化水素環基における芳香族炭化水素環としては、単環であっても縮合環であってもよい。２価の芳香族炭化水素環基としては、例えば、２個の遊離原子価を有する、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環が挙げられる。 The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. The divalent aromatic hydrocarbon ring group includes, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.
　芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよい。２価の芳香族複素環基としては、例えば、２個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環が挙げられる。
　２価の芳香族環基としては、製造コストの観点から、２個の遊離原子価を有するベンゼン環、ナフタレン環が好ましく、２個の遊離原子価を有するベンゼン環がより好ましい。 The aromatic heterocyclic ring in the aromatic heterocyclic group may be monocyclic or condensed. Examples of divalent aromatic heterocyclic groups include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, and indole ring having two free valences. ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring and azulene ring.
From the viewpoint of production cost, the divalent aromatic ring group is preferably a benzene ring or naphthalene ring having two free valences, more preferably a benzene ring having two free valences.
　２価の芳香族環基が有していてもよい置換基としては、例えば、ヒドロキシ基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基が挙げられる。硬化性の観点から、無置換が好ましい。 Examples of substituents that the divalent aromatic ring group may have include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. From the viewpoint of curability, non-substitution is preferred.
　１以上の２価の脂肪族基と１以上の２価の芳香族環基とを連結した基としては、前述の２価の脂肪族基を１以上と、前述の２価の芳香族環基を１以上とを連結した基が挙げられる。
　２価の脂肪族基の数は特に限定されないが、１以上が好ましく、２以上がより好ましく、また、１０以下が好ましく、５以下がより好ましく、３以下がさらに好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～１０が好ましく、１～５がより好ましく、２～３がさらに好ましい。前記下限値以上とすることで現像性が向上する傾向がある。前記上限値以下とすることで膜強度が向上する傾向がある。
　２価の芳香族環基の数は特に限定されないが、１以上が好ましく、２以上がより好ましく、また、１０以下が好ましく、５以下がより好ましく、３以下がさらに好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～１０が好ましく、１～５がより好ましく、２～３がさらに好ましい。前記下限値以上とすることで膜強度が向上する傾向がある。前記上限値以下とすることで現像性が向上する傾向がある。 As a group connecting one or more divalent aliphatic groups and one or more divalent aromatic ring groups, one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic ring groups is linked to one or more.
Although the number of divalent aliphatic groups is not particularly limited, it is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 are preferred, 1 to 5 are more preferred, and 2 to 3 are even more preferred. Developability tends to be improved by setting the content to be at least the above lower limit. When the content is equal to or less than the above upper limit, there is a tendency that the film strength is improved.
Although the number of divalent aromatic ring groups is not particularly limited, it is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 are preferred, 1 to 5 are more preferred, and 2 to 3 are even more preferred. When the content is equal to or higher than the lower limit, there is a tendency that the film strength is improved. The developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
　１以上の２価の脂肪族基と１以上の２価の芳香族環基とを連結した基としては、例えば、下記式（ｉ－Ａ）～（ｉ－Ｆ）で表される基が挙げられる。骨格の剛直性と膜の疎水化の観点から、下記式（ｉ－Ａ）で表される基が好ましい。 Examples of groups in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups represented by the following formulas (iA) to (iF). be done. A group represented by the following formula (iA) is preferable from the viewpoint of rigidity of the skeleton and hydrophobicity of the membrane.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　式（ｉ）中のベンゼン環に許容される置換基としては、例えば、ヒドロキシ基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基が挙げられる。置換基の数も特に限定されず、１つでもよいし、２つ以上でもよい。硬化性の観点から、無置換であることが好ましい。 Examples of acceptable substituents for the benzene ring in formula (i) include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is also not particularly limited, and may be one or two or more. From the viewpoint of curability, it is preferably unsubstituted.
　式（ｉ）で表される部分構造は、現像溶解性の観点から、下記式（ｉ－１）で表される部分構造であることが好ましい。 The partial structure represented by formula (i) is preferably a partial structure represented by formula (i-1) below from the viewpoint of development solubility.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　式（ｉ－１）中、Ｒa及びＲbは、式（ｉ）と同義である。ＲYは水素原子又は多塩基酸残基を表す。＊は結合手を表す。式（ｉ－１）中のベンゼン環は、さらに任意の置換基により置換されていてもよい。 In formula (i-1), R a and R b have the same definitions as in formula (i). RY represents a hydrogen atom or a polybasic acid residue. * represents a bond. The benzene ring in formula (i-1) may be further substituted with any substituent.
　多塩基酸残基とは、多塩基酸又はその無水物からＯＨ基を１つ除した１価の基を意味する。多塩基酸としては、例えば、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ベンゾフェノンテトラカルボン酸、メチルヘキサヒドロフタル酸、エンドメチレンテトラヒドロフタル酸、クロレンド酸、メチルテトラヒドロフタル酸、ビフェニルテトラカルボン酸から選ばれた１種又は２種以上が挙げられる。
　パターニング特性の観点から、好ましくは、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ビフェニルテトラカルボン酸であり、より好ましくは、テトラヒドロフタル酸、ビフェニルテトラカルボン酸である。 A polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Examples of polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylene. One or more selected from tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid can be mentioned.
From the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and tetrahydrophthalic acid is more preferred. phthalic acid and biphenyltetracarboxylic acid.
　エポキシ（メタ）アクリレート樹脂（ｂ１２－１）１分子中に含まれる、前記式（ｉ－１）で表される繰り返し単位構造は、１種でも２種以上でもよい。 The repeating unit structure represented by the formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin (b12-1) may be one or two or more.
　エポキシ（メタ）アクリレート樹脂（ｂ１２－１）１分子中に含まれる、式（ｉ）で表される部分構造の数は特に限定されない。１以上が好ましく、２以上がより好ましく、３以上がさらに好ましく、また、１０以下が好ましく、８以下がさらに好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～１０が好ましく、２～１０がより好ましく、３～８がさらに好ましい。前記下限値以上とすることで現像性が向上する傾向がある。前記上限値以下とすることで膜強度が向上する傾向がある。 The number of partial structures represented by formula (i) contained in one molecule of the epoxy (meth)acrylate resin (b12-1) is not particularly limited. 1 or more is preferable, 2 or more is more preferable, 3 or more is more preferable, 10 or less is preferable, and 8 or less is more preferable.
The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 are preferred, 2 to 10 are more preferred, and 3 to 8 are even more preferred. Developability tends to be improved by setting the content to be at least the above lower limit. When the content is equal to or less than the above upper limit, there is a tendency that the film strength is improved.
　エポキシ（メタ）アクリレート樹脂（ｂ１２－１）１分子中に含まれる、式（ｉ－１）で表される部分構造の数は特に限定されないが、１以上が好ましく、２以上がより好ましく、３以上がさらに好ましく、また、１０以下が好ましく、８以下がさらに好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～１０が好ましく、２～１０がより好ましく、３～８がさらに好ましい。前記下限値以上とすることで現像性が向上する傾向がある。前記上限値以下とすることで膜強度が向上する傾向がある。 The number of partial structures represented by formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin (b12-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and 3. Above is more preferable, 10 or less is preferable, and 8 or less is more preferable.
The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 are preferred, 2 to 10 are more preferred, and 3 to 8 are even more preferred. Developability tends to be improved by setting the content to be at least the above lower limit. When the content is equal to or less than the above upper limit, there is a tendency that the film strength is improved.
　以下にエポキシ（メタ）アクリレート樹脂（ｂ１２－１）の具体例を挙げる。 Specific examples of the epoxy (meth)acrylate resin (b12-1) are given below.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　式（ｉｉ）で表される部分構造を有するエポキシ（メタ）アクリレート樹脂（以下、「エポキシ（メタ）アクリレート樹脂（ｂ１２－２）」と称する場合がある。）について詳述する。 The epoxy (meth)acrylate resin having the partial structure represented by formula (ii) (hereinafter sometimes referred to as "epoxy (meth)acrylate resin (b12-2)") will be described in detail.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　式（ｉｉ）中、Ｒcは各々独立に、水素原子又はメチル基を表す。Ｒdは、環状炭化水素基を側鎖として有する２価の炭化水素基を表す。＊は結合手を表す。 In formula (ii), each R c independently represents a hydrogen atom or a methyl group. R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. * represents a bond.
（Ｒd）
　式（ｉｉ）において、Ｒdは、環状炭化水素基を側鎖として有する２価の炭化水素基を表す。
　環状炭化水素基としては、脂肪族環基又は芳香族環基が挙げられる。 ( Rd )
In formula (ii), R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
The cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.
　脂肪族環基が有する環の数は特に限定されない。１以上が好ましく、２以上が好ましく、また、１０以下が好ましく、５以下がより好ましく、３以下がさらに好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～１０が好ましく、１～５がより好ましく、２～３がさらに好ましい。前記下限値以上とすることで膜強度が向上する傾向がある。前記上限値以下とすることで現像性が向上する傾向がある。
　脂肪族環基の炭素数は４以上が好ましく、６以上がより好ましく、８以上がさらに好ましく、また、４０以下が好ましく、３０以下がより好ましく、２０以下がさらに好ましく、１５以下が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、４～４０が好ましく、４～３０がより好ましく、６～２０がさらに好ましく、８～１５が特に好ましい。前記下限値以上とすることで膜強度が向上する傾向がある。前記上限値以下とすることで現像性が向上する傾向がある。 The number of rings that the aliphatic ring group has is not particularly limited. 1 or more is preferable, 2 or more are preferable, 10 or less are preferable, 5 or less are more preferable, and 3 or less are more preferable.
The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 are preferred, 1 to 5 are more preferred, and 2 to 3 are even more preferred. When the content is equal to or higher than the lower limit, there is a tendency that the film strength is improved. The developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
The number of carbon atoms in the aliphatic ring group is preferably 4 or more, more preferably 6 or more, still more preferably 8 or more, preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less.
The above upper and lower limits can be combined arbitrarily. For example, 4 to 40 are preferred, 4 to 30 are more preferred, 6 to 20 are even more preferred, and 8 to 15 are particularly preferred. When the content is equal to or higher than the lower limit, there is a tendency that the film strength is improved. The developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
　脂肪族環基における脂肪族環としては、例えば、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、シクロドデカン環が挙げられる。膜強度と現像性の観点から、アダマンタン環が好ましい。 Examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, and cyclododecane ring. An adamantane ring is preferred from the viewpoint of film strength and developability.
　芳香族環基が有する環の数は特に限定されない。１以上が好ましく、２以上がより好ましく、３以上がさらに好ましく、また、１０以下が好ましく、５以下がより好ましく、４以下がさらに好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～１０が好ましく、２～５がより好ましく、３～４がさら好ましい。前記下限値以上とすることで膜強度が向上する傾向がある。前記上限値以下とすることで現像性が向上する傾向がある。 The number of rings that the aromatic ring group has is not particularly limited. It is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, preferably 10 or less, more preferably 5 or less, and even more preferably 4 or less.
The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 are preferred, 2 to 5 are more preferred, and 3 to 4 are even more preferred. When the content is equal to or higher than the lower limit, there is a tendency that the film strength is improved. The developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
　芳香族環基としては、芳香族炭化水素環基、芳香族複素環基が挙げられる。芳香族環基の炭素数は４以上が好ましく、６以上よりが好ましく、８以上がさらに好ましく、１０以上がよりさらに好ましく、１２以上が特に好ましく、また、４０以下が好ましく、３０以下がより好ましく、２０以下がさらに好ましく、１５以下が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、４～４０が好ましく、６～４０がより好ましく、８～３０がさらに好ましく、１０～２０がよりさらに好ましく、１２～１５が特に好ましい。前記下限値以上とすることで膜強度が向上する傾向がある。前記上限値以下とすることで現像性が向上する傾向がある。 Aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic ring group is preferably 4 or more, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, particularly preferably 12 or more, preferably 40 or less, and more preferably 30 or less. , is more preferably 20 or less, and particularly preferably 15 or less.
The above upper and lower limits can be combined arbitrarily. For example, 4 to 40 are preferred, 6 to 40 are more preferred, 8 to 30 are even more preferred, 10 to 20 are even more preferred, and 12 to 15 are particularly preferred. When the content is equal to or higher than the lower limit, there is a tendency that the film strength is improved. The developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
　芳香族環基における芳香族環としては、例えば、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環が挙げられる。パターニング特性の観点から、フルオレン環が好ましい。 The aromatic ring in the aromatic ring group includes, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring. A fluorene ring is preferred from the viewpoint of patterning properties.
　環状炭化水素基を側鎖として有する２価の炭化水素基における、２価の炭化水素基は特に限定されない。例えば、２価の脂肪族基、２価の芳香族環基、１以上の２価の脂肪族基と１以上の２価の芳香族環基とを連結した基が挙げられる。 The divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited. Examples thereof include divalent aliphatic groups, divalent aromatic ring groups, and groups in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked.
　２価の脂肪族基は、直鎖状、分岐鎖状、環状の脂肪族基が挙げられる。現像性の向上の観点からは直鎖状の脂肪族基が好ましく、膜強度の観点からは環状の脂肪族基が好ましい。２価の脂肪族基の炭素数は１以上が好ましく、３以上がより好ましく、６以上がさらに好ましく、また、２５以下が好ましく、２０以下がより好ましく、１５以下がさらに好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～２５が好ましく、３～２０がより好ましく、６～１５がさらに好ましい。前記下限値以上とすることで膜強度が向上する傾向がある。前記上限値以下とすることで現像性が向上する傾向がある。 The divalent aliphatic group includes linear, branched and cyclic aliphatic groups. A linear aliphatic group is preferred from the viewpoint of improving developability, and a cyclic aliphatic group is preferred from the viewpoint of film strength. The number of carbon atoms in the divalent aliphatic group is preferably 1 or more, more preferably 3 or more, still more preferably 6 or more, and is preferably 25 or less, more preferably 20 or less, and still more preferably 15 or less.
The above upper and lower limits can be combined arbitrarily. For example, 1 to 25 are preferred, 3 to 20 are more preferred, and 6 to 15 are even more preferred. When the content is equal to or higher than the lower limit, there is a tendency that the film strength is improved. The developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
　２価の直鎖状脂肪族基としては、例えば、メチレン基、エチレン基、ｎ－プロピレン基、ｎ－ブチレン基、ｎ－ヘキシレン基、ｎ－ヘプチレン基が挙げられる。撥インク性の観点から、メチレン基が好ましい。
　２価の分岐鎖状脂肪族基としては、前述の２価の直鎖状脂肪族基に、側鎖として例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基を有する構造が挙げられる。 Examples of divalent linear aliphatic groups include methylene group, ethylene group, n-propylene group, n-butylene group, n-hexylene group and n-heptylene group. A methylene group is preferable from the viewpoint of ink repellency.
The divalent branched aliphatic group includes the divalent linear aliphatic group described above, and side chains such as methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl. structures having a group, a sec-butyl group, and a tert-butyl group.
　２価の環状の脂肪族基が有する環の数は特に限定されない。１以上が好ましく、２以上がより好ましく、また、１０以下が好ましく、５以下がより好ましく、３以下がさらに好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～１０が好ましく、１～５がより好ましく、２～３がさらに好ましい。前記下限値以上とすることで膜強度が向上する傾向がある。前記上限値以下とすることで現像性が向上する傾向がある。 The number of rings that the divalent cyclic aliphatic group has is not particularly limited. 1 or more is preferable, 2 or more is more preferable, 10 or less is preferable, 5 or less is more preferable, and 3 or less is more preferable.
The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 are preferred, 1 to 5 are more preferred, and 2 to 3 are even more preferred. When the content is equal to or higher than the lower limit, there is a tendency that the film strength is improved. The developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
　２価の環状の脂肪族基としては、例えば、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、シクロドデカン環の環から水素原子を２つ除した基が挙げられる。膜強度の観点から、アダマンタン環から水素原子を２つ除した基が好ましい。 The divalent cyclic aliphatic group includes, for example, a group obtained by removing two hydrogen atoms from a cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, or cyclododecane ring. is mentioned. From the viewpoint of film strength, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable.
　２価の脂肪族基が有していてもよい置換基としては、例えば、メトキシ基、エトキシ基等の炭素数１～５のアルコキシ基；水酸基；ニトロ基；シアノ基；カルボキシ基が挙げられる。合成容易性の観点から、無置換であることが好ましい。 Examples of substituents that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.
　２価の芳香族環基としては、２価の芳香族炭化水素環基及び２価の芳香族複素環基が挙げられる。２価の芳香族環基の炭素数は４以上が好ましく、５以上がより好ましく、６以上がさらに好ましく、また、３０以下が好ましく、２０以下がより好ましく、１５以下がさらに好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、４～３０が好ましく、５～２０がより好ましく、６～１５がさらに好ましい。前記下限値以上とすることで膜強度が向上する傾向がある。前記上限値以下とすることで現像性が向上する傾向がある。 The divalent aromatic ring group includes a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The number of carbon atoms in the divalent aromatic ring group is preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less.
The above upper and lower limits can be combined arbitrarily. For example, 4 to 30 are preferred, 5 to 20 are more preferred, and 6 to 15 are even more preferred. When the content is equal to or higher than the lower limit, there is a tendency that the film strength is improved. The developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
　２価の芳香族炭化水素環基における芳香族炭化水素環としては、単環であっても縮合環であってもよい。２価の芳香族炭化水素環基としては、例えば、２個の遊離原子価を有する、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環が挙げられる。 The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. The divalent aromatic hydrocarbon ring group includes, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.
　また、２価の芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよい。２価の芳香族複素環基としては、例えば、２個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環が挙げられる。
　２価の芳香族環基としては、製造コストの観点から、２個の遊離原子価を有するベンゼン環、ナフタレン環が好ましく、２個の遊離原子価を有するベンゼン環がより好ましい。 In addition, the aromatic heterocycle in the divalent aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of divalent aromatic heterocyclic groups include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, and indole ring having two free valences. ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring and azulene ring.
From the viewpoint of production cost, the divalent aromatic ring group is preferably a benzene ring or naphthalene ring having two free valences, more preferably a benzene ring having two free valences.
　２価の芳香族環基が有していてもよい置換基としては、例えば、ヒドロキシ基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基が挙げられる。硬化性の観点から、無置換が好ましい。 Examples of substituents that the divalent aromatic ring group may have include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. From the viewpoint of curability, non-substitution is preferred.
　１以上の２価の脂肪族基と１以上の２価の芳香族環基とを連結した基としては、前述の２価の脂肪族基を１以上と、前述の２価の芳香族環基を１以上とを連結した基が挙げられる。
　２価の脂肪族基の数は特に限定されない。１以上が好ましく、２以上がより好ましく、また、１０以下が好ましく、５以下がより好ましく、３以下がさらに好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～１０が好ましく、１～５がより好ましく、２～３がさらに好ましい。前記下限値以上とすることで現像性が向上する傾向がある。前記上限値以下とすることで膜強度が向上する傾向がある。
　２価の芳香族環基の数は特に限定されない。１以上が好ましく、２以上がより好ましく、また、１０以下が好ましく、５以下がより好ましく、３以下がさらに好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～１０が好ましく、１～５がより好ましく、２～３がさらに好ましい。前記下限値以上とすることで膜強度が向上する傾向がある。前記上限値以下とすることで現像性が向上する傾向がある。 As a group connecting one or more divalent aliphatic groups and one or more divalent aromatic ring groups, one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic ring groups is linked to one or more.
The number of divalent aliphatic groups is not particularly limited. 1 or more is preferable, 2 or more is more preferable, 10 or less is preferable, 5 or less is more preferable, and 3 or less is more preferable.
The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 are preferred, 1 to 5 are more preferred, and 2 to 3 are even more preferred. Developability tends to be improved by setting the content to be at least the above lower limit. When the content is equal to or less than the above upper limit, there is a tendency that the film strength is improved.
The number of divalent aromatic ring groups is not particularly limited. 1 or more is preferable, 2 or more is more preferable, 10 or less is preferable, 5 or less is more preferable, and 3 or less is more preferable.
The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 are preferred, 1 to 5 are more preferred, and 2 to 3 are even more preferred. When the content is equal to or higher than the lower limit, there is a tendency that the film strength is improved. The developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
　１以上の２価の脂肪族基と１以上の２価の芳香族環基とを連結した基としては、例えば、前述した式（ｉ－Ａ）～（ｉ－Ｆ）で表される基が挙げられる。膜強度と撥インク性の両立の観点から、式（ｉ－Ｃ）で表される基が好ましい。 Examples of groups in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups represented by formulas (iA) to (iF) described above. mentioned. From the viewpoint of achieving both film strength and ink repellency, the group represented by formula (iC) is preferred.
　これらの２価の炭化水素基に対して、側鎖である環状炭化水素基の結合態様は特に限定されない。例えば、脂肪族基や芳香族環基の水素原子１つを側鎖である環状炭化水素基で置換した態様や、脂肪族基の炭素原子の１つを含めて側鎖である環状炭化水素基を構成した態様が挙げられる。 The bonding mode of the side chain cyclic hydrocarbon group is not particularly limited to these divalent hydrocarbon groups. For example, an aspect in which one hydrogen atom of an aliphatic group or an aromatic ring group is substituted with a cyclic hydrocarbon group that is a side chain, or a cyclic hydrocarbon group that is a side chain including one of the carbon atoms of the aliphatic group The aspect which constituted is mentioned.
　式（ｉｉ）で表される部分構造は、撥インク性の観点から、下記一般式（ｉｉ－１）で表される部分構造であることが好ましい。 From the viewpoint of ink repellency, the partial structure represented by formula (ii) is preferably a partial structure represented by general formula (ii-1) below.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
　式（ｉｉ－１）中、Ｒcは式（ｉｉ）と同義である。Ｒαは、置換基を有していてもよい１価の環状炭化水素基を表す。ｎは１以上の整数である。＊は結合手を表す。式（ｉｉ－１）中のベンゼン環は、さらに任意の置換基により置換されていてもよい。 In formula (ii-1), R c has the same meaning as in formula (ii). R α represents a monovalent cyclic hydrocarbon group which may have a substituent. n is an integer of 1 or more. * represents a bond. The benzene ring in formula (ii-1) may be further substituted with any substituent.
（Ｒα）
　式（ｉｉ－１）において、Ｒαは、置換基を有していてもよい１価の環状炭化水素基を表す。
　環状炭化水素基としては、脂肪族環基又は芳香族環基が挙げられる。 (R α )
In formula (ii-1), R α represents a monovalent cyclic hydrocarbon group which may have a substituent.
The cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.
　脂肪族環基が有する環の数は特に限定されない。１以上が好ましく、２以上がより好ましく、また、６以下が好ましく、４以下がより好ましく、３以下がさらに好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～６が好ましく、１～４がより好ましく、２～３がさらに好ましい。前記下限値以上とすることで膜強度が向上する傾向がある。前記上限値以下とすることで現像性が向上する傾向がある。
　脂肪族環基の炭素数は４以上が好ましく、６以上がより好ましく、８以上がさらに好ましく、また、４０以下が好ましく、３０以下がより好ましく、２０以下がさらに好ましく、１５以下が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、４～４０が好ましく、４～３０がより好ましく、６～２０がさらに好ましく、８～１５が特に好ましい。前記下限値以上とすることで膜強度が向上する傾向がある。前記上限値以下とすることで現像性が向上する傾向がある。 The number of rings that the aliphatic ring group has is not particularly limited. 1 or more is preferable, 2 or more is more preferable, 6 or less is preferable, 4 or less is more preferable, and 3 or less is more preferable.
The above upper and lower limits can be combined arbitrarily. For example, 1 to 6 are preferred, 1 to 4 are more preferred, and 2 to 3 are even more preferred. When the content is equal to or higher than the lower limit, there is a tendency that the film strength is improved. The developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
The number of carbon atoms in the aliphatic ring group is preferably 4 or more, more preferably 6 or more, still more preferably 8 or more, preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less.
The above upper and lower limits can be combined arbitrarily. For example, 4 to 40 are preferred, 4 to 30 are more preferred, 6 to 20 are even more preferred, and 8 to 15 are particularly preferred. When the content is equal to or higher than the lower limit, there is a tendency that the film strength is improved. The developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
　脂肪族環基における脂肪族環としては、例えば、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、シクロドデカン環が挙げられる。膜強度と現像性の両立の観点から、アダマンタン環が好ましい。 Examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, and cyclododecane ring. An adamantane ring is preferable from the viewpoint of compatibility between film strength and developability.
　芳香族環基が有する環の数は特に限定されない１以上が好ましく、２以上がより好ましく、３以上がさらに好ましく、また、１０以下が好ましく、５以下がより好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～１０が好ましく、２～１０がより好ましく、３～５がさらに好ましい。前記下限値以上とすることで膜強度が向上する傾向がある。前記上限値以下とすることで現像性が向上する傾向がある。
　芳香族環基としては、芳香族炭化水素環基、芳香族複素環基が挙げられる。また、芳香族環基の炭素数は４以上が好ましく、５以上がより好ましく、６以上がさらに好ましく、また、３０以下が好ましく、２０以下がより好ましく、１５以下がさらに好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、４～３０が好ましく、５～２０がより好ましく、６～１５がさらに好ましい。前記下限値以上とすることで膜強度が向上する傾向がある。前記上限値以下とすることで現像性が向上する傾向がある。 The number of rings possessed by the aromatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and preferably 10 or less, more preferably 5 or less.
The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 are preferred, 2 to 10 are more preferred, and 3 to 5 are even more preferred. When the content is equal to or higher than the lower limit, there is a tendency that the film strength is improved. The developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
Aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic ring group is preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less.
The above upper and lower limits can be combined arbitrarily. For example, 4 to 30 are preferred, 5 to 20 are more preferred, and 6 to 15 are even more preferred. When the content is equal to or higher than the lower limit, there is a tendency that the film strength is improved. The developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
　芳香族環基における芳香族環としては、例えば、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、フルオレン環が挙げられる。膜強度と現像性の両立の観点から、フルオレン環が好ましい。 Examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, and fluorene ring. A fluorene ring is preferable from the viewpoint of achieving both film strength and developability.
　環状炭化水素基が有していてもよい置換基としては、例えば、ヒドロキシ基、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、アミル基、イソアミル基等の炭素数１～５のアルキル基；メトキシ基、エトキシ基等の炭素数１～５のアルコキシ基；ニトロ基；シアノ基；カルボキシ基が挙げられる。合成の容易性の観点から、無置換が好ましい。 Substituents that the cyclic hydrocarbon group may have include, for example, hydroxy group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, Alkyl groups having 1 to 5 carbon atoms such as amyl group and isoamyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; nitro group; cyano group; and carboxy group. Unsubstituted is preferred from the viewpoint of ease of synthesis.
　ｎは１以上の整数を表し、２以上が好ましく、また、３以下が好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～３が好ましく、２～３がより好ましい。前記下限値以上とすることで現像性が向上する傾向がある。前記上限値以下とすることで膜強度が向上する傾向がある。 n represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less.
The above upper and lower limits can be combined arbitrarily. For example, 1 to 3 are preferred, and 2 to 3 are more preferred. Developability tends to be improved by setting the content to be at least the above lower limit. When the content is equal to or less than the above upper limit, there is a tendency that the film strength is improved.
　膜強度と現像性の両立の観点から、Ｒαが１価の脂肪族環基であることが好ましく、アダマンチル基であることがより好ましい。 From the viewpoint of achieving both film strength and developability, R α is preferably a monovalent aliphatic cyclic group, more preferably an adamantyl group.
　式（ｉｉ－１）中のベンゼン環に許容される置換基としては、例えば、ヒドロキシ基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基が挙げられる。置換基の数も特に限定されず、１つでもよいし、２つ以上でもよい。硬化性の観点から、無置換であることが好ましい。 Examples of acceptable substituents on the benzene ring in formula (ii-1) include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is also not particularly limited, and may be one or two or more. From the viewpoint of curability, it is preferably unsubstituted.
　以下に式（ｉｉ－１）で表される部分構造の具体例を挙げる。 Specific examples of the partial structure represented by formula (ii-1) are given below.
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
　式（ｉｉ）で表される部分構造は、現像密着性の観点から、下記一般式（ｉｉ－２）で表される部分構造であることが好ましい。 The partial structure represented by formula (ii) is preferably a partial structure represented by the following general formula (ii-2) from the viewpoint of development adhesion.
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
　式（ｉｉ－２）中、Ｒcは前記式（ｉｉ）と同義である。Ｒβは、置換基を有していてもよい２価の環状炭化水素基を表す。＊は結合手を表す。式（ｉｉ－２）中のベンゼン環は、さらに任意の置換基により置換されていてもよい。 In formula (ii-2), R c has the same definition as in formula (ii) above. R β represents a divalent cyclic hydrocarbon group which may have a substituent. * represents a bond. The benzene ring in formula (ii-2) may be further substituted with any substituent.
（Ｒβ）
　式（ｉｉ－２）において、Ｒβは、置換基を有していてもよい２価の環状炭化水素基を表す。
　環状炭化水素基としては、脂肪族環基又は芳香族環基が挙げられる。 ( Rβ )
In formula (ii-2), R β represents an optionally substituted divalent cyclic hydrocarbon group.
The cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.
　脂肪族環基が有する環の数は特に限定されない。１以上が好ましく、２以上がより好ましく、また、１０以下が好ましく、５以下がより好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～１０が好ましく、２～５がより好ましい。前記下限値以上とすることで膜強度が向上する傾向がある。前記上限値以下とすることで現像性が向上する傾向がある。
　脂肪族環基の炭素数は４以上が好ましく、６以上がより好ましく、８以上がさらに好ましく、また、４０以下が好ましく、３５以下がより好ましく、３０以下がさらに好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、４～４０が好ましく、６～３５がより好ましく、８～３０がさらに好ましい。前記下限値以上とすることで膜強度が向上する傾向がある。前記上限値以下とすることで現像性が向上する傾向がある。
　脂肪族環基における脂肪族環としては、例えば、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環、シクロドデカン環が挙げられる。膜強度と現像性の両立の観点から、アダマンタン環が好ましい。 The number of rings that the aliphatic ring group has is not particularly limited. 1 or more is preferable, 2 or more is more preferable, 10 or less is preferable, and 5 or less is more preferable.
The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 are preferred, and 2 to 5 are more preferred. When the content is equal to or higher than the lower limit, there is a tendency that the film strength is improved. The developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
The number of carbon atoms in the aliphatic ring group is preferably 4 or more, more preferably 6 or more, still more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and still more preferably 30 or less.
The above upper and lower limits can be combined arbitrarily. For example, 4 to 40 are preferred, 6 to 35 are more preferred, and 8 to 30 are even more preferred. When the content is equal to or higher than the lower limit, there is a tendency that the film strength is improved. The developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
Examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring and cyclododecane ring. An adamantane ring is preferable from the viewpoint of compatibility between film strength and developability.
　芳香族環基が有する環の数は特に限定されない。１以上が好ましく、２以上がより好ましく、３以上がさらに好ましく、また、１０以下が好ましく、５以下がより好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～１０が好ましく、２～１０がより好ましく、３～５がさらに好ましい。前記下限値以上とすることで膜強度が向上する傾向がある。前記上限値以下とすることで現像性が向上する傾向がある。
　芳香族環基としては、芳香族炭化水素環基、芳香族複素環基が挙げられる。芳香族環基の炭素数は４以上が好ましく、６以上がより好ましく、８以上がさらに好ましく、１０以上が特に好ましく、また、４０以下が好ましく、３０以下がより好ましく、２０以下がさらに好ましく、１５以下が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、４～４０が好ましく、６～３０がより好ましく、８～２０がさらに好ましく、１０～１５が特に好ましい。前記下限値以上とすることで膜強度が向上する傾向がある。前記上限値以下とすることで現像性が向上する傾向がある。 The number of rings that the aromatic ring group has is not particularly limited. It is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, preferably 10 or less, and more preferably 5 or less.
The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 are preferred, 2 to 10 are more preferred, and 3 to 5 are even more preferred. When the content is equal to or higher than the lower limit, there is a tendency that the film strength is improved. The developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
Aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic ring group is preferably 4 or more, more preferably 6 or more, more preferably 8 or more, particularly preferably 10 or more, preferably 40 or less, more preferably 30 or less, and further preferably 20 or less, 15 or less is particularly preferred.
The above upper and lower limits can be combined arbitrarily. For example, 4 to 40 are preferred, 6 to 30 are more preferred, 8 to 20 are even more preferred, and 10 to 15 are particularly preferred. When the content is equal to or higher than the lower limit, there is a tendency that the film strength is improved. The developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
　芳香族環基における芳香族環としては、例えば、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、フルオレン環が挙げられる。膜強度と現像性の観点から、フルオレン環が好ましい。 Examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, and fluorene ring. A fluorene ring is preferred from the viewpoint of film strength and developability.
　環状炭化水素基が有していてもよい置換基としては、例えば、ヒドロキシ基、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、アミル基、イソアミル基等の炭素数１～５のアルキル基；メトキシ基、エトキシ基等の炭素数１～５のアルコキシ基；ニトロ基；シアノ基；カルボキシ基が挙げられる。合成の簡易性の観点から、無置換が好ましい。 Substituents that the cyclic hydrocarbon group may have include, for example, hydroxy group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, Alkyl groups having 1 to 5 carbon atoms such as amyl group and isoamyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; nitro group; cyano group; and carboxy group. Unsubstituted is preferred from the viewpoint of ease of synthesis.
　膜強度と現像性の両立の観点から、Ｒβが２価の脂肪族環基であることが好ましく、２価のアダマンタン環基であることがより好ましい。
　膜強度と現像性の両立の観点から、Ｒβが２価の芳香族環基であることが好ましく、２価のフルオレン環基であることがより好ましい。 From the viewpoint of achieving both film strength and developability, R β is preferably a divalent aliphatic cyclic group, more preferably a divalent adamantane cyclic group.
From the viewpoint of achieving both film strength and developability, R β is preferably a divalent aromatic ring group, more preferably a divalent fluorene ring group.
　式（ｉｉ－２）中のベンゼン環に許容される置換基としては、例えば、ヒドロキシ基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基が挙げられる。置換基の数も特に限定されず、１つでもよいし、２つ以上でもよい。硬化性の観点から、無置換であることが好ましい。 Examples of acceptable substituents for the benzene ring in formula (ii-2) include hydroxy, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy groups. The number of substituents is also not particularly limited, and may be one or two or more. From the viewpoint of curability, it is preferably unsubstituted.
　以下に式（ｉｉ－２）で表される部分構造の具体例を挙げる。 Specific examples of the partial structure represented by formula (ii-2) are given below.
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
　式（ｉｉ）で表される部分構造は、現像性の観点から、下記一般式（ｉｉ－３）で表される部分構造であることが好ましい。 From the viewpoint of developability, the partial structure represented by formula (ii) is preferably a partial structure represented by general formula (ii-3) below.
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
　式（ｉｉ－３）中、Ｒc及びＲdは式（ｉｉ）と同義である。ＲZは水素原子又は多塩基酸残基を表す。 In formula (ii-3), R c and R d have the same definitions as in formula (ii). R Z represents a hydrogen atom or a polybasic acid residue.
　多塩基酸残基とは、多塩基酸又はその無水物からＯＨ基を１つ除した１価の基を意味する。多塩基酸としては、例えば、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ベンゾフェノンテトラカルボン酸、メチルヘキサヒドロフタル酸、エンドメチレンテトラヒドロフタル酸、クロレンド酸、メチルテトラヒドロフタル酸、ビフェニルテトラカルボン酸から選ばれた１種又は２種以上が挙げられる。
　パターニング特性の観点から、好ましくは、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸、ビフェニルテトラカルボン酸であり、より好ましくは、テトラヒドロフタル酸、ビフェニルテトラカルボン酸である。 A polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Examples of polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylene. One or more selected from tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid can be mentioned.
From the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and tetrahydrophthalic acid is more preferred. phthalic acid and biphenyltetracarboxylic acid.
　エポキシ（メタ）アクリレート樹脂（ｂ１２－２）１分子中に含まれる、式（ｉｉ－３）で表される部分構造は、１種でも２種以上でもよい。 The partial structure represented by the formula (ii-3) contained in one molecule of the epoxy (meth)acrylate resin (b12-2) may be one type or two or more types.
　エポキシ（メタ）アクリレート樹脂（ｂ１２－２）１分子中に含まれる、式（ｉｉ）で表される部分構造の数は特に限定されない。１以上が好ましく、３以上がより好ましく、また、２０以下が好ましく、１５以下がより好ましく、１０以下がさらに好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～２０が好ましく、１～１５がより好ましく、３～１０がさらに好ましい。前記下限値以上とすることで撥インク性が向上する傾向がある。前記上限値以下とすることで現像性が向上する傾向がある。 The number of partial structures represented by formula (ii) contained in one molecule of the epoxy (meth)acrylate resin (b12-2) is not particularly limited. 1 or more is preferable, 3 or more is more preferable, 20 or less is preferable, 15 or less is more preferable, and 10 or less is more preferable.
The above upper and lower limits can be combined arbitrarily. For example, 1 to 20 are preferred, 1 to 15 are more preferred, and 3 to 10 are even more preferred. The ink repellency tends to be improved by making it equal to or higher than the lower limit. The developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
　エポキシ（メタ）アクリレート樹脂（ｂ１２－２）１分子中に含まれる、式（ｉｉ－１）で表される部分構造の数は特に限定されない。１以上が好ましく、３以上がより好ましく、また、２０以下が好ましく、１５以下がより好ましく、１０以下がさらに好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～２０が好ましく、１～１５がより好ましく、３～１０がさらに好ましい。前記下限値以上とすることで撥インク性が向上する傾向がある。前記上限値以下とすることで現像性が向上する傾向がある。 The number of partial structures represented by formula (ii-1) contained in one molecule of the epoxy (meth)acrylate resin (b12-2) is not particularly limited. 1 or more is preferable, 3 or more is more preferable, 20 or less is preferable, 15 or less is more preferable, and 10 or less is more preferable.
The above upper and lower limits can be combined arbitrarily. For example, 1 to 20 are preferred, 1 to 15 are more preferred, and 3 to 10 are even more preferred. The ink repellency tends to be improved by making it equal to or higher than the lower limit. The developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
　エポキシ（メタ）アクリレート樹脂（ｂ１２－２）１分子中に含まれる、式（ｉｉ－２）で表される部分構造の数は特に限定されない。１以上が好ましく、３以上がより好ましく、また、２０以下が好ましく、１５以下がより好ましく、１０以下がさらに好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～２０が好ましく、１～１５がより好ましく、３～１０がさらに好ましい。前記下限値以上とすることで撥インク性が向上する傾向がある。前記上限値以下とすることで現像性が向上する傾向がある。 The number of partial structures represented by formula (ii-2) contained in one molecule of the epoxy (meth)acrylate resin (b12-2) is not particularly limited. 1 or more is preferable, 3 or more is more preferable, 20 or less is preferable, 15 or less is more preferable, and 10 or less is more preferable.
The above upper and lower limits can be combined arbitrarily. For example, 1 to 20 are preferred, 1 to 15 are more preferred, and 3 to 10 are even more preferred. The ink repellency tends to be improved by making it equal to or higher than the lower limit. The developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
　エポキシ（メタ）アクリレート樹脂（ｂ１２－２）１分子中に含まれる、式（ｉｉ－３）で表される部分構造の数は特に限定されない。１以上が好ましく、３以上がより好ましく、また、２０以下が好ましく、１５以下がより好ましく、１０以下がさらに好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～２０が好ましく、１～１５がより好ましく、３～１０がさらに好ましい。前記下限値以上とすることで撥インク性が向上する傾向がある。前記上限値以下とすることで現像性が向上する傾向がある。 The number of partial structures represented by formula (ii-3) contained in one molecule of the epoxy (meth)acrylate resin (b12-2) is not particularly limited. 1 or more is preferable, 3 or more is more preferable, 20 or less is preferable, 15 or less is more preferable, and 10 or less is more preferable.
The above upper and lower limits can be combined arbitrarily. For example, 1 to 20 are preferred, 1 to 15 are more preferred, and 3 to 10 are even more preferred. The ink repellency tends to be improved by making it equal to or higher than the lower limit. The developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
　以上のとおり、本発明における（ｂ）アルカリ可溶性樹脂は、アクリル共重合樹脂（ｂ１１）や、エポキシ（メタ）アクリレート樹脂（ｂ１２）以外のアルカリ可溶性樹脂を含んでいてもよい。 As described above, the (b) alkali-soluble resin in the present invention may contain an alkali-soluble resin other than the acrylic copolymer resin (b11) and the epoxy (meth)acrylate resin (b12).
　（ｂ）アルカリ可溶性樹脂の酸価は特に限定されない。１０ｍｇＫＯＨ／ｇ以上が好ましく、２０ｍｇＫＯＨ／ｇ以上がより好ましく、２５ｍｇＫＯＨ／ｇ以上がさらに好ましく、また、２００ｍｇＫＯＨ／ｇ以下が好ましく、１５０ｍｇＫＯＨ／ｇ以下がより好ましく、１００ｍｇＫＯＨ／ｇ以下がさらに好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１５～１５０ｍｇＫＯＨ／ｇが好ましく、２０～１２０ｍｇＫＯＨ／ｇがより好ましく、２５～１００ｍｇＫＯＨ／ｇがさらに好ましい。前記下限値以上とすることで現像性が向上する傾向がある。前記上限値以下とすることで現像密着性が向上する傾向がある。（ｂ）アルカリ可溶性樹脂が２種以上の混合物の場合、酸価は、その含有割合に応じた加重平均値を意味する。 (b) The acid value of the alkali-soluble resin is not particularly limited. 10 mgKOH/g or more is preferable, 20 mgKOH/g or more is more preferable, 25 mgKOH/g or more is still more preferable, 200 mgKOH/g or less is preferable, 150 mgKOH/g or less is more preferable, and 100 mgKOH/g or less is more preferable.
The above upper and lower limits can be combined arbitrarily. For example, 15 to 150 mgKOH/g is preferred, 20 to 120 mgKOH/g is more preferred, and 25 to 100 mgKOH/g is even more preferred. Developability tends to be improved by setting the content to be at least the above lower limit. When the amount is set to the above upper limit or less, there is a tendency that development adhesion is improved. (b) When the alkali-soluble resin is a mixture of two or more kinds, the acid value means a weighted average value according to the content ratio.
　（ｂ）アルカリ可溶性樹脂の二重結合当量は、１０００ｇ／ｍｏｌ以下であり、８００ｇ／ｍｏｌ以下が好ましく、７００／ｍｏｌ以下がより好ましく、６００ｇ／ｍｏｌ以下が特に好ましい。また、３００ｇ／ｍｏｌ以上が好ましく、３９０ｇ／ｍｏｌより大きいことがより好ましく、４００ｇ／ｍｏｌより大きいことがさらに好ましく、４５０ｇ／ｍｏｌ以上が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、３００～１０００ｇ／ｍｏｌが好ましく、３９０ｇ／ｍｏｌより大きく１０００ｇ／ｍｏｌ以下であることがより好ましく、４００ｇ／ｍｏｌより大きく１０００ｇ／ｍｏｌ以下であることがさらに好ましく、４５０～８００ｇ／ｍｏｌが特に好ましい。前記下限値以上とすることで現像性が向上する傾向がある。前記上限値以下とすることで撥インク性が向上する傾向がある。
　（ｂ）アルカリ可溶性樹脂が２種以上の混合物の場合、（ｂ）アルカリ可溶性樹脂の二重結合当量は、（ｂ）アルカリ可溶性樹脂全体の重量平均分子量を（ｂ）アルカリ可溶性樹脂全体のエチレン性不飽和二重結合の平均数で除した値で算出できる。もしくは、各々の二重結合当量の調和平均値で算出できる。 (b) The double bond equivalent of the alkali-soluble resin is 1000 g/mol or less, preferably 800 g/mol or less, more preferably 700 g/mol or less, and particularly preferably 600 g/mol or less. Also, it is preferably 300 g/mol or more, more preferably greater than 390 g/mol, even more preferably greater than 400 g/mol, and particularly preferably 450 g/mol or more.
The above upper and lower limits can be combined arbitrarily. For example, it is preferably from 300 to 1000 g/mol, more preferably from 390 g/mol to 1000 g/mol, even more preferably from 400 g/mol to 1000 g/mol, and particularly preferably from 450 to 800 g/mol. . Developability tends to be improved by setting the content to be at least the above lower limit. The ink repellency tends to be improved by making it equal to or less than the above upper limit.
(b) When the alkali-soluble resin is a mixture of two or more kinds, the double bond equivalent of the (b) alkali-soluble resin is the weight average molecular weight of the whole alkali-soluble resin (b) the ethylenicity of the whole alkali-soluble resin It can be calculated by dividing by the average number of unsaturated double bonds. Alternatively, it can be calculated from the harmonic average value of each double bond equivalent.
　本発明の着色感光性樹脂組成物における（ｂ）アルカリ可溶性樹脂の含有割合は特に限定されない。着色感光性樹脂組成物の全固形分量に対して、５質量％以上が好ましく、１０質量％以上がより好ましく、２０質量％以上がさらに好ましく、３０質量％以上がよりさらに好ましく、４０質量％以上がことさらに好ましく、５０質量％以上がよりことさらに好ましく、６０質量％以上が特に好ましく、また、９０質量％以下が好ましく、８０質量％以下がより好ましく、７０質量％以下がさらに好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、５～９０質量％、好ましくは１０～９０質量％、より好ましくは２０～９０質量％、さらに好ましくは３０～８０質量％、よりさらに好ましくは４０～８０質量％、特に好ましくは５０～７０質量％、最も好ましくは６０～７０質量％である。前記下限値以上とすることで残渣が低減する傾向がある。前記上限値以下とすることで撥インク性が向上する傾向がある。 The content of (b) the alkali-soluble resin in the colored photosensitive resin composition of the present invention is not particularly limited. The total solid content of the colored photosensitive resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, even more preferably 30% by mass or more, and 40% by mass or more. 50% by mass or more is even more preferable, 60% by mass or more is particularly preferable, 90% by mass or less is preferable, 80% by mass or less is more preferable, and 70% by mass or less is even more preferable.
The above upper and lower limits can be combined arbitrarily. For example, 5 to 90% by mass, preferably 10 to 90% by mass, more preferably 20 to 90% by mass, still more preferably 30 to 80% by mass, even more preferably 40 to 80% by mass, particularly preferably 50 to 70% by mass. % by weight, most preferably 60-70% by weight. Residue tends to be reduced by making it equal to or higher than the lower limit. The ink repellency tends to be improved by making it equal to or less than the above upper limit.
　着色感光性樹脂組成物の全固形分量に対する、（ｄ）光重合性化合物の含有割合及び（ｂ）アルカリ可溶性樹脂の含有割合の総和は、特に限定されない。１０質量％以上が好ましく、３０質量％以上がより好ましく、６０質量％以上がさらに好ましく、８０質量％以上が特に好ましく、また、９５質量％以下が好ましく、９２質量％以下がより好ましく、９０質量％以下がさらに好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１０～９５質量％が好ましく、３０～９５質量％がより好ましく、６０～９２質量％がさらに好ましく、８０～９０質量％が特に好ましい。前記下限値以上とすることで隔壁の基材への密着性が向上する傾向がある。前記上限値以下とすることで遮光性や撥インク性が向上する傾向がある。 The total content of (d) the photopolymerizable compound and (b) the alkali-soluble resin relative to the total solid content of the colored photosensitive resin composition is not particularly limited. 10% by mass or more is preferable, 30% by mass or more is more preferable, 60% by mass or more is more preferable, 80% by mass or more is particularly preferable, and 95% by mass or less is preferable, and 92% by mass or less is more preferable, and 90% by mass. % or less is more preferable.
The above upper and lower limits can be combined arbitrarily. For example, 10 to 95% by mass is preferable, 30 to 95% by mass is more preferable, 60 to 92% by mass is even more preferable, and 80 to 90% by mass is particularly preferable. When the content is equal to or higher than the above lower limit, there is a tendency that the adhesion of the partition wall to the base material is improved. When the content is equal to or less than the above upper limit, there is a tendency that the light shielding property and the ink repellency are improved.
［１－１－３］（ｃ）光重合開始剤
　本発明の着色感光性樹脂組成物は（ｃ）光重合開始剤を含有し、（ｃ）光重合開始剤は、波長３００～３５０ｎｍに極大吸収波長（λmax）を有するオキシムエステル系光重合開始剤（ｃ１）（以下、「オキシムエステル系光重合開始剤（ｃ１）」と略記する場合がある。）を含有する。 [1-1-3] (c) Photopolymerization initiator The colored photosensitive resin composition of the present invention contains (c) a photopolymerization initiator, and (c) the photopolymerization initiator has a maximum wavelength of 300 to 350 nm. It contains an oxime ester photopolymerization initiator (c1) having an absorption wavelength (λmax) (hereinafter sometimes abbreviated as “oxime ester photopolymerization initiator (c1)”).
　酸化チタン粒子を含有する着色感光性樹脂組成物の現像工程においては、酸化チタン粒子によって露光の光が散乱され、この散乱光が着色感光性樹脂組成物の硬化物のパターニング形状や線幅に影響を及ぼす傾向がある。
　本発明の着色感光性樹脂組成物は、波長３００～３５０ｎｍに極大吸収波長（λmax）を有するオキシムエステル系光重合開始剤（ｃ１）を含有することで、酸化チタン粒子による散乱光の影響を受けずに十分な硬化性を確保できるため、好ましいパターニング形状と線幅及び密着性の両立が可能となる。 In the process of developing a colored photosensitive resin composition containing titanium oxide particles, exposure light is scattered by the titanium oxide particles, and this scattered light affects the patterning shape and line width of the cured product of the colored photosensitive resin composition. tend to affect
The colored photosensitive resin composition of the present invention contains an oxime ester photopolymerization initiator (c1) having a maximum absorption wavelength (λmax) at a wavelength of 300 to 350 nm, so that it is affected by scattered light due to titanium oxide particles. Since sufficient curability can be ensured without the need for curing, it is possible to achieve a favorable patterning shape, line width, and adhesion at the same time.
［１－１－３－１］オキシムエステル系光重合開始剤（ｃ１）
　オキシムエステル系光重合開始剤（ｃ１）は波長３００～３５０ｎｍに極大吸収波長（λmax）を有する。
　オキシムエステル系光重合開始剤（ｃ１）の極大吸収波長は、３００ｎｍ以上であり、３１０ｎｍ以上が好ましく、３２０ｎｍ以上がより好ましい。また、３５０ｎｍ以下であり、３４５ｎｍ以下が好ましく、３４０ｎｍ以下がより好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、３１０～３４５ｎｍが好ましく、３２０～３４０ｎｍがより好ましい。前記下限値以上とすることで密着性が十分確保できる傾向がある。前記上限値以下とすることで裾引きの小さな形状が確保出来る傾向がある。 [1-1-3-1] Oxime ester photopolymerization initiator (c1)
The oxime ester photopolymerization initiator (c1) has a maximum absorption wavelength (λmax) at a wavelength of 300-350 nm.
The maximum absorption wavelength of the oxime ester photopolymerization initiator (c1) is 300 nm or longer, preferably 310 nm or longer, and more preferably 320 nm or longer. Moreover, it is 350 nm or less, preferably 345 nm or less, and more preferably 340 nm or less.
The above upper and lower limits can be combined arbitrarily. For example, 310-345 nm is preferable, and 320-340 nm is more preferable. By making it more than the said lower limit, there exists a tendency which can ensure adhesiveness enough. When the thickness is equal to or less than the above upper limit, there is a tendency that a shape with less skirting can be secured.
　オキシムエステル系光重合開始剤（ｃ１）の極大吸収波長の測定は、例えば、以下の方法で測定できる。まずオキシムエステル系光重合開始剤（ｃ１）の０．０１質量％のプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）溶液を作成し、１ｃｍ角の石英セルに入れ、分光光度計で波長２５０～４００ｎｍの光を照射して１ｎｍおきに測定して得ることができる。分光光度計としては、例えばＵＶ－３０００シリーズ、ＵＶ－３０００シリーズ（島津製作所社製）、Ｖ－７００シリーズ（日本分光社製）が挙げられるが、これに限定されるものではない。 The maximum absorption wavelength of the oxime ester photopolymerization initiator (c1) can be measured, for example, by the following method. First, a 0.01% by mass propylene glycol monomethyl ether acetate (PGMEA) solution of the oxime ester photopolymerization initiator (c1) was prepared, placed in a 1 cm square quartz cell, and irradiated with light having a wavelength of 250 to 400 nm with a spectrophotometer. It can be obtained by irradiating and measuring every 1 nm. Examples of spectrophotometers include UV-3000 series, UV-3000 series (manufactured by Shimadzu Corporation), and V-700 series (manufactured by JASCO Corporation), but are not limited to these.
　また、オキシムエステル系光重合開始剤（ｃ１）は、０．０１質量％のプロピレングリコールモノメチルエーテルアセテート溶液での３６０～４００ｎｍにおける最大吸光度が２以下であることが好ましく、１．５以下が特に好ましい。前記上限値以下にすることで裾引きの小さな形状が確保出来る傾向がある。 Further, the oxime ester photopolymerization initiator (c1) preferably has a maximum absorbance of 2 or less, particularly preferably 1.5 or less, at 360 to 400 nm in a 0.01% by mass propylene glycol monomethyl ether acetate solution. . By making the thickness equal to or less than the above upper limit, there is a tendency that a shape with a small skirting can be secured.
　オキシムエステル系光重合開始剤（ｃ１）は波長３００～３５０ｎｍに極大吸収波長（λmax）を有すれば、特に限定されないが、例えば、カルバゾール骨格、ジフェニルスルフィド骨格、チオキサントン骨格、フルオレン骨格を有する化合物が挙げられる。密着性の点でカルバゾール骨格を有する化合物が好ましい。極大吸収波長（λmax）を適切な波長にコントロールし易い点でジフェニルスルフィド骨格を有する化合物が好ましい。 The oxime ester photopolymerization initiator (c1) is not particularly limited as long as it has a maximum absorption wavelength (λmax) at a wavelength of 300 to 350 nm. mentioned. A compound having a carbazole skeleton is preferable in terms of adhesion. A compound having a diphenyl sulfide skeleton is preferred because the maximum absorption wavelength (λmax) can be easily controlled to an appropriate wavelength.
　オキシムエステル系光重合開始剤（ｃ１）の化学構造は特に限定されないが、下記一般式（ｃ１－１）、又は下記一般式（ｃ１－２）で表される化学構造を有する化合物であることが好ましい。 Although the chemical structure of the oxime ester-based photopolymerization initiator (c1) is not particularly limited, it may be a compound having a chemical structure represented by the following general formula (c1-1) or the following general formula (c1-2). preferable.
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
　式（ｃ１－１）中、Ｒ３は置換基を有していてもよいアルキル基、又は置換基を有していてもよい芳香族環基を表す。
　Ｒ４は置換基を有していてもよいアルキル基、又は置換基を有していてもよい芳香族環基を表す。
　Ｒ５は任意の１価の置換基を表す。
　ｑは０～３の整数を表す。
　Ｒ６は水素原子、置換基を有していてもよいアルキル基、又は置換基を有していてもよい芳香族環基を表す。 In formula (c1-1), R 3 represents an optionally substituted alkyl group or an optionally substituted aromatic ring group.
R 4 represents an optionally substituted alkyl group or an optionally substituted aromatic ring group.
R5 represents any monovalent substituent.
q represents an integer of 0 to 3;
R6 represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aromatic ring group.
　式（ｃ１－１）中のＲ３において、置換基を有していてもよいアルキル基としては、例えば、炭素数１～６のアルキル基、炭素数４～２０のシクロアルキル基が挙げられる。 Examples of optionally substituted alkyl groups for R 3 in formula (c1-1) include alkyl groups having 1 to 6 carbon atoms and cycloalkyl groups having 4 to 20 carbon atoms.
　式（ｃ１－１）中のＲ３において、置換基を有していてもよい芳香族環基としては、例えば、フェニル基、ナフチル基が挙げられる。 Examples of the optionally substituted aromatic ring group for R 3 in formula (c1-1) include a phenyl group and a naphthyl group.
　Ｒ３としては、撥液性の観点から、炭素数１～６のアルキル基が好ましく、メチル基がより好ましい。 From the viewpoint of liquid repellency, R 3 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group.
　式（ｃ１－１）中のＲ４において、置換基を有していてもよいアルキル基としては、例えば、炭素数２～１２のアルキル基、炭素数１～２０のヘテロアリールアルキル基、炭素数３～２５のアルケニル基、炭素数３～８のシクロアルケニル基、炭素数３～２０のアルコキシカルボニルアルキル基、炭素数８～２０のフェノキシカルボニルアルキル基、炭素数３～２０のヘテロアリ－ルオキシカルボニルアルキル基、炭素数３～２０のシクロアルキルアルキル基が挙げられる。 In R 4 in formula (c1-1), the optionally substituted alkyl group includes, for example, an alkyl group having 2 to 12 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 20 carbon atoms. alkenyl groups of 3 to 25 carbon atoms, cycloalkenyl groups of 3 to 8 carbon atoms, alkoxycarbonylalkyl groups of 3 to 20 carbon atoms, phenoxycarbonylalkyl groups of 8 to 20 carbon atoms, heteroaryloxycarbonyl groups of 3 to 20 carbon atoms Examples include alkyl groups and cycloalkylalkyl groups having 3 to 20 carbon atoms.
　式（ｃ１－１）中のＲ４において、置換基を有していてもよい芳香族環基としては、フェニル基、ナフチル基が挙げられる。 In R 4 in formula (c1-1), the aromatic ring group optionally having a substituent includes a phenyl group and a naphthyl group.
　Ｒ４はカルバゾール環と共に環を形成してもよく、その連結基は、例えば、それぞれ置換基を有していてもよい炭素数１～１０のアルキレン基、ポリエチレン基（－（ＣＨ＝ＣＨ）r－）、ポリエチニレン基（－（Ｃ≡Ｃ）r－）あるいはこれらを組み合わせてなる基が挙げられる。ｒは０～３の整数である。 R 4 may form a ring together with the carbazole ring, and the linking group is, for example, an alkylene group having 1 to 10 carbon atoms each optionally having a substituent, a polyethylene group (-(CH=CH) r -), a polyethylene group (-(C≡C) r -), or a group consisting of a combination thereof. r is an integer from 0 to 3;
　Ｒ４としては、パターニング性の観点から、メチル基、エチル基、プロピル基などの無置換の直鎖アルキル基、シクロアルキルアルキル基、又はＮ－アセチル－Ｎ－アセトキシアミノ基で置換されたプロピル基が好ましく、Ｎ－アセチル－Ｎ－アセトキシアミノ基で置換されたプロピル基がより好ましい。 From the viewpoint of patterning properties, R 4 is an unsubstituted linear alkyl group such as a methyl group, an ethyl group, a propyl group, a cycloalkylalkyl group, or a propyl group substituted with an N-acetyl-N-acetoxyamino group. is preferred, and a propyl group substituted with an N-acetyl-N-acetoxyamino group is more preferred.
　Ｒ５における１価の置換基としては、例えば、メチル基、エチル基等の炭素数１～１０のアルキル基；メトキシ基、エトキシ基などの炭素数１～１０のアルコキシ基；Ｆ、Ｃｌ、Ｂｒ、Ｉなどのハロゲン原子；炭素数１～１０のアシル基；炭素数１～１０のアルキルエステル基；炭素数１～１０のアルコキシカルボニル基；炭素数１～１０のハロゲン化アルキル基；炭素数４～１０の芳香族環基；アミノ基；炭素数１～１０のアミノアルキル基；水酸基；ＣＮ基；置換基を有していてもよいベンゾイル基；置換基を有していてもよいナフトイル基；置換基を有していてもよいテノイル基が挙げられる。撥液性の観点から、無置換のベンゾイル基、無置換のナフトイル基が好ましく、無置換のナフトイル基がより好ましい。 Examples of monovalent substituents for R 5 include alkyl groups having 1 to 10 carbon atoms such as methyl group and ethyl group; alkoxy groups having 1 to 10 carbon atoms such as methoxy group and ethoxy group; F, Cl and Br. , I and other halogen atoms; acyl groups having 1 to 10 carbon atoms; alkyl ester groups having 1 to 10 carbon atoms; alkoxycarbonyl groups having 1 to 10 carbon atoms; halogenated alkyl groups having 1 to 10 carbon atoms; ~10 aromatic ring group; amino group; aminoalkyl group having 1 to 10 carbon atoms; hydroxyl group; CN group; optionally substituted benzoyl group; optionally substituted naphthoyl group; A thenoyl group which may have a substituent is exemplified. From the viewpoint of liquid repellency, an unsubstituted benzoyl group and an unsubstituted naphthoyl group are preferable, and an unsubstituted naphthoyl group is more preferable.
　Ｒ６における置換基を有していてもよいアルキル基としては、炭素数２～１２のアルキル基、炭素数１～２０のヘテロアリールアルキル基、炭素数３～２５のアルケニル基、炭素数３～８のシクロアルケニル基、炭素数３～２０のアルコキシカルボニルアルキル基、炭素数８～２０のフェノキシカルボニルアルキル基、炭素数３～２０のヘテロアリ－ルオキシカルボニルアルキル基、炭素数３～２０のシクロアルキルアルキル基が挙げられる。
　Ｒ６における置換基を有していてもよい芳香族環基としては、フェニル基、ナフチル基が挙げられる。
　Ｒ６としては、無置換のメチル基、エチル基が好ましい。 The optionally substituted alkyl group for R 6 includes an alkyl group having 2 to 12 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, an alkenyl group having 3 to 25 carbon atoms, and an alkenyl group having 3 to 25 carbon atoms. 8 cycloalkenyl group, alkoxycarbonylalkyl group having 3 to 20 carbon atoms, phenoxycarbonylalkyl group having 8 to 20 carbon atoms, heteroaryloxycarbonylalkyl group having 3 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms An alkyl group is mentioned.
A phenyl group and a naphthyl group are mentioned as an aromatic ring group which may have a substituent in R6 .
R6 is preferably an unsubstituted methyl group or ethyl group.
　式（ｃ１－１）中、ｑは０～３の整数を表す。ラジカル生成効率の観点から、ｑは０又は１であることが好ましく、１であることがより好ましい。 In formula (c1-1), q represents an integer of 0-3. From the viewpoint of radical generation efficiency, q is preferably 0 or 1, more preferably 1.
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
　式（ｃ１－２）中、Ｒ13Aは、置換基を有していてもよいアルキル基、又は置換基を有していてもよい芳香族環基を表す。
　Ｒ14Aは、アルキル基、又は芳香族環基を表す。
　Ｒ15Aは、１価の置換基を表す。
　ｎは０又は１を表す。
　ｈは０～２の整数を表す。 In formula (c1-2), R 13A represents an optionally substituted alkyl group or an optionally substituted aromatic ring group.
R 14A represents an alkyl group or an aromatic ring group.
R 15A represents a monovalent substituent.
n represents 0 or 1;
h represents an integer of 0 to 2;
（Ｒ13A）
　式（ｃ１－２）中のＲ13Aにおけるアルキル基は、直鎖状でも、分岐鎖状でも、環状でも、それらが結合したものであってもよい。アルキル基の炭素数は特に限定されない。１以上が好ましく、２以上がより好ましく、４以上がさらに好ましく、また、２０以下が好ましく、１０以下がより好ましく、８以下がさらに好ましく、７以下がよりさらに好ましく、４以下が特に好ましい。前記上限値以下とすることで溶剤への溶解性が良好となる傾向がある。
　上記の上限及び下限は任意に組み合わせることができる。例えば、アルキル基の炭素数は１～２０が好ましく、１～１０がより好ましく、１～８がさらに好ましく、１～７がよりさらに好ましく、１～４が特に好ましい。 ( R13A )
The alkyl group for R 13A in formula (c1-2) may be linear, branched, cyclic, or a combination thereof. The number of carbon atoms in the alkyl group is not particularly limited. It is preferably 1 or more, more preferably 2 or more, still more preferably 4 or more, preferably 20 or less, more preferably 10 or less, even more preferably 8 or less, even more preferably 7 or less, and particularly preferably 4 or less. The solubility in a solvent tends to be improved by adjusting the content to the above upper limit or less.
The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkyl group is preferably 1-20, more preferably 1-10, still more preferably 1-8, even more preferably 1-7, and particularly preferably 1-4.
　アルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、イソペンチル基、ヘキシル基、シクロペンチル基、シクロヘキシル基、シクロペンチルメチル基、シクロペンチルエチル基、シクロヘキシルメチル基、シクロヘキシルエチル基が挙げられ、現像性の観点から、メチル基、ヘキシル基、イソペンチル基、へキシル基、シクロペンチルメチル基、シクロヘキシルメチル基が好ましく、ヘキシル基、シクロペンチルメチル基がより好ましい。 Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, isopentyl, hexyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, and cyclohexylethyl groups. From the viewpoint of developability, preferred are a methyl group, a hexyl group, an isopentyl group, a hexyl group, a cyclopentylmethyl group and a cyclohexylmethyl group, and more preferred are a hexyl group and a cyclopentylmethyl group.
　アルキル基が有していてもよい置換基としては、例えば、芳香族環基、水酸基、カルボキシ基、アルコキシカルボニル基が挙げられる。現像性の観点からは、メチル基が好ましい。溶解性の観点からは、アルコキシカルボニル基が好ましい。合成容易性の観点からは、無置換であることが好ましい。 Examples of substituents that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, and an alkoxycarbonyl group. A methyl group is preferred from the standpoint of developability. From the viewpoint of solubility, an alkoxycarbonyl group is preferred. From the viewpoint of ease of synthesis, it is preferably unsubstituted.
　式（ｃ１－２）中のＲ13Aにおける芳香族環基としては、芳香族炭化水素環基及び芳香族複素環基が挙げられる。芳香族環基の炭素数は特に限定されないが、４以上が好ましく、５以上がより好ましく、また、３０以下が好ましく、２０以下がより好ましく、１２以下がさらに好ましい。前記下限値以上とすることで溶剤への溶解性が良好となる傾向がある。前記上限値以下とすることで現像性が良好となる傾向がある。
　上記の上限及び下限は任意に組み合わせることができる。例えば、芳香族環基の炭素数は４～３０が好ましく、４～２０がより好ましく、４～１２がさらに好ましく、５～１２が特に好ましい。 The aromatic ring group for R 13A in formula (c1-2) includes an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 4 or more, more preferably 5 or more, preferably 30 or less, more preferably 20 or less, and still more preferably 12 or less. When the content is at least the above lower limit, there is a tendency that the solubility in a solvent becomes good. Developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
The above upper and lower limits can be combined arbitrarily. For example, the aromatic ring group preferably has 4 to 30 carbon atoms, more preferably 4 to 20 carbon atoms, still more preferably 4 to 12 carbon atoms, and particularly preferably 5 to 12 carbon atoms.
　芳香族環基としては、例えば、フェニル基、ナフチル基、ピリジル基、フリル基が挙げられ、これらの中でも現像性の観点から、フェニル基、ナフチル基が好ましく、フェニル基がより好ましい。 Examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, and a furyl group. Among these, from the viewpoint of developability, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.
　芳香族環基が有していてもよい置換基としては、例えば、水酸基、アルキル基が挙げられ、現像性の観点からアルキル基が好ましい。
　パターニング性の観点から、Ｒ13Aが、置換基を有していてもよいアルキル基であることが好ましく、メチル基、ヘキシル基、メトキシカルボニルエチル基がより好ましく、メトキシカルボニル基がさらに好ましい。 Examples of the substituent that the aromatic ring group may have include a hydroxyl group and an alkyl group, and an alkyl group is preferable from the viewpoint of developability.
From the viewpoint of patterning properties, R 13A is preferably an optionally substituted alkyl group, more preferably a methyl group, a hexyl group or a methoxycarbonylethyl group, and even more preferably a methoxycarbonyl group.
（Ｒ14A）
　式（ｃ１－２）中のＲ14Aにおけるアルキル基は、直鎖状でも、分岐鎖状でも、環状でも、それらが結合したものであってもよい。アルキル基の炭素数は特に限定されない。１以上が好ましく、また、５以下が好ましく、３以下がより好ましい。前記上限値以下とすることで感度が良好となる傾向がある。
　上記の上限及び下限は任意に組み合わせることができる。例えば、アルキル基の炭素数は１～５が好ましく、１～３がより好ましい。 ( R14A )
The alkyl group for R 14A in formula (c1-2) may be linear, branched, cyclic, or a combination thereof. The number of carbon atoms in the alkyl group is not particularly limited. 1 or more is preferable, 5 or less is preferable, and 3 or less is more preferable. The sensitivity tends to be good when the content is equal to or less than the above upper limit.
The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkyl group is preferably 1-5, more preferably 1-3.
　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、ペンチル基が挙げられ、これらの中でも感度の観点から、メチル基が好ましい。 Examples of the alkyl group include methyl group, ethyl group, propyl group, and pentyl group, and among these, the methyl group is preferable from the viewpoint of sensitivity.
　式（ｃ１－２）中のＲ14Aにおける芳香族環基としては、芳香族炭化水素環基及び芳香族複素環基が挙げられる。芳香族環基の炭素数は特に限定されない。４以上が好ましく、５以上がより好ましく、また、３０以下が好ましく、２０以下がより好ましく、１２以下がさらに好ましい。前記下限値以上とすることで溶剤への溶解性が良好となる傾向がある。前記上限値以下とすることで感度が良好となる傾向がある。
　上記の上限及び下限は任意に組み合わせることができる。例えば、芳香族環基の炭素数は４～３０が好ましく、４～２０がより好ましく、４～１２がさらに好ましく、５～１２が特に好ましい。 The aromatic ring group for R 14A in formula (c1-2) includes an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is not particularly limited. 4 or more is preferable, 5 or more is more preferable, 30 or less is preferable, 20 or less is more preferable, and 12 or less is more preferable. When the content is at least the above lower limit, there is a tendency that the solubility in a solvent becomes good. The sensitivity tends to be good when the content is equal to or less than the above upper limit.
The above upper and lower limits can be combined arbitrarily. For example, the aromatic ring group preferably has 4 to 30 carbon atoms, more preferably 4 to 20 carbon atoms, still more preferably 4 to 12 carbon atoms, and particularly preferably 5 to 12 carbon atoms.
　芳香族環基としては、例えば、フェニル基、ナフチル基、ピリジル基、フリル基が挙げられる。パターニング性の観点から、フェニル基、ナフチル基が好ましく、フェニル基がより好ましい。 Examples of aromatic ring groups include phenyl groups, naphthyl groups, pyridyl groups, and furyl groups. From the viewpoint of patterning properties, a phenyl group and a naphthyl group are preferred, and a phenyl group is more preferred.
　式（ｃ１－２）中のＲ14Aとしてはパターニング性の観点からは、芳香族環基が好ましく、フェニル基、ナフチル基がより好ましく、フェニル基がさらに好ましい。撥液性の観点からは、メチル基が好ましい。 From the viewpoint of patterning properties, R 14A in formula (c1-2) is preferably an aromatic ring group, more preferably a phenyl group or a naphthyl group, and still more preferably a phenyl group. From the viewpoint of liquid repellency, a methyl group is preferred.
（Ｒ15A）
　式（ｃ１－２）中のＲ15Aにおける１価の置換基は特に限定されない。現像性の観点から、Ｒ16A－Ｏ－、Ｒ16A－（Ｃ＝Ｏ）－が好ましい。 ( R15A )
The monovalent substituent for R 15A in formula (c1-2) is not particularly limited. From the viewpoint of developability, R 16A -O- and R 16A -(C=O)- are preferred.
　Ｒ16Aとしては、置換基を有してもよいアルキル基、置換基を有してもよい芳香族環基が挙げられる。
　Ｒ16Aにおけるアルキル基は、直鎖状でも、分岐鎖状でも、環状でも、それらが結合したものであってもよい。アルキル基の炭素数は特に限定されない。１以上が好ましく、２以上がより好ましく、３以上がさらに好ましく、また、８以下が好ましく、５以下がより好ましい。前記下限値以上とすることで現像性が良好となる傾向があり、また、前記上限値以下とすることでパターニング性が良好となる傾向がある。
　上記の上限及び下限は任意に組み合わせることができる。例えば、アルキル基の炭素数は１～８が好ましく、２～５がより好ましい。 R 16A includes an optionally substituted alkyl group and an optionally substituted aromatic ring group.
The alkyl group for R 16A may be linear, branched, cyclic, or a combination thereof. The number of carbon atoms in the alkyl group is not particularly limited. 1 or more is preferable, 2 or more is more preferable, 3 or more is still more preferable, 8 or less is preferable, and 5 or less is more preferable. The lower limit value or more tends to improve the developability, and the upper limit value or less tends to improve the patterning property.
The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkyl group is preferably 1-8, more preferably 2-5.
　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、ペンチル基が挙げられる。溶解性の観点から、メチル基、エチル基が好ましく、エチル基がより好ましい。
　アルキル基が有していてもよい置換基としては、例えば、水酸基、カルボキシ基が挙げられ、現像性の観点から水酸基が好ましい。 Examples of alkyl groups include methyl, ethyl, propyl, and pentyl groups. From the viewpoint of solubility, a methyl group and an ethyl group are preferred, and an ethyl group is more preferred.
Examples of the substituent that the alkyl group may have include a hydroxyl group and a carboxy group, and a hydroxyl group is preferable from the viewpoint of developability.
　Ｒ16Aにおける芳香族環基としては、芳香族炭化水素環基及び芳香族複素環基が挙げられる。芳香族環基の炭素数は特に限定されない。４以上が好ましく、５以上がより好ましく、また、３０以下が好ましく、２０以下がより好ましく、１２以下がさらに好ましい。前記下限値以上とすることで現像性が良好となる傾向がある。前記上限値以下とすることでパターニング性が良好となる傾向がある。
　上記の上限及び下限は任意に組み合わせることができる。例えば、芳香族環基の炭素数は４～３０が好ましく、４～２０がより好ましく、４～１２がさらに好ましく、５～１２が特に好ましい。 The aromatic ring group for R 16A includes aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic ring group is not particularly limited. 4 or more is preferable, 5 or more is more preferable, 30 or less is preferable, 20 or less is more preferable, and 12 or less is more preferable. The developability tends to be improved by making it equal to or higher than the above lower limit. The patterning property tends to be good by making it equal to or less than the above upper limit.
The above upper and lower limits can be combined arbitrarily. For example, the aromatic ring group preferably has 4 to 30 carbon atoms, more preferably 4 to 20 carbon atoms, still more preferably 4 to 12 carbon atoms, and particularly preferably 5 to 12 carbon atoms.
　芳香族環基としては、例えば、フェニル基、ナフチル基、チエニル基、フリル基、ベンゾチエニル基、ベンゾフリル基が挙げられる。パターニング性の観点から、ベンゾチエニル基、ベンゾフリル基が好ましく、ベンゾフリル基がより好ましい。
　芳香族環基が有していてもよい置換基としては、例えば、アルキル基、水酸基、カルボキシ基が挙げられ、合成性の観点から無置換が好ましい。 Examples of aromatic ring groups include phenyl, naphthyl, thienyl, furyl, benzothienyl, and benzofuryl groups. From the viewpoint of patterning properties, a benzothienyl group and a benzofuryl group are preferable, and a benzofuryl group is more preferable.
Examples of the substituent that the aromatic ring group may have include an alkyl group, a hydroxyl group, and a carboxy group, and unsubstituted is preferred from the viewpoint of synthesis.
　式（ｃ１－２）中のＲ15Aにおける１価の置換基としては、パターニング性の観点から、Ｒ16Aが水酸基置換のエチル基であるＲ16A－Ｏ－、Ｒ16Aがベンゾフリル基であるＲ16A－（Ｃ＝Ｏ）－が好ましく、Ｒ16Aが水酸基置換のエチル基であるＲ16A－Ｏ－がより好ましい。 The monovalent substituents for R 15A in formula (c1-2) include, from the viewpoint of patterning properties, R 16A —O— in which R 16A is a hydroxyl-substituted ethyl group, and R 16A in which R 16A is a benzofuryl group. -(C=O)- is preferred, and R 16A -O- in which R 16A is a hydroxyl-substituted ethyl group is more preferred.
（ｎ）
　式（ｃ１－２）において、パターニング性の観点からはｎが１であることが好ましく、感度の観点からはｎが０であることが好ましい。 (n)
In formula (c1-2), n is preferably 1 from the viewpoint of patterning properties, and preferably 0 from the viewpoint of sensitivity.
（ｈ）
　式（ｃ１－２）において、パターニング性の観点からはｈが０又は１であることが好ましく、０であることがより好ましい。
　ｈが１以上の整数の場合、Ｒ15Aの置換位置は特に限定されないが、合成上の観点からｏ位又はｐ位が好ましく、ｐ位がより好ましい。 (h)
In formula (c1-2), h is preferably 0 or 1, more preferably 0, from the viewpoint of patterning properties.
When h is an integer of 1 or more, the substitution position of R 15A is not particularly limited, but from the viewpoint of synthesis, the o-position or p-position is preferable, and the p-position is more preferable.
　オキシムエステル系光重合開始剤（ｃ１）としては、以下の化合物が挙げられる。 Examples of the oxime ester-based photopolymerization initiator (c1) include the following compounds.
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
　パターニング性の観点から、式（Ｃ１－２－２１）、（Ｃ１－１－１２）で表される化学構造の化合物が好ましい。一方で撥液性の観点から、前記式（Ｃ１－２－２３）、（Ｃ１－２－２５）で表される化学構造の化合物が好ましい。 From the viewpoint of patterning properties, compounds having chemical structures represented by formulas (C1-2-21) and (C1-1-12) are preferred. On the other hand, from the viewpoint of liquid repellency, compounds having chemical structures represented by the above formulas (C1-2-23) and (C1-2-25) are preferred.
　オキシムエステル系光重合開始剤（ｃ１）は、１種類を単独で用いても、２種類以上を組み合わせて使用してもよい。 The oxime ester photopolymerization initiator (c1) may be used alone or in combination of two or more.
　本発明の着色感光性樹脂組成物における（ｃ）光重合開始剤は、必要に応じて、オキシムエステル系光重合開始剤（ｃ１）以外の光重合開始剤（以下、「その他の光重合開始剤」と称する場合がある。）を含有してもよい。その他の光重合開始剤は、オキシムエステル系化合物であってもよいし、オキシムエステル系化合物以外のものであってもよい。 The (c) photopolymerization initiator in the colored photosensitive resin composition of the present invention is optionally a photopolymerization initiator other than the oxime ester photopolymerization initiator (c1) (hereinafter referred to as “other photopolymerization initiators ) may be included. Other photopolymerization initiators may be oxime ester compounds, or may be compounds other than oxime ester compounds.
　その他の光重合開始剤としては、この分野で通常用いられているものを使用することができる。例えば、日本国特開昭５９－１５２３９６号公報、日本国特開昭６１－１５１１９７号公報に記載のチタノセン化合物を含むメタロセン化合物；日本国特開２０００－５６１１８号公報に記載のヘキサアリールビイミダゾール誘導体類；日本国特開平１０－３９５０３号公報記載のハロメチル化オキサジアゾール誘導体類、ハロメチル－ｓ－トリアジン誘導体類、Ｎ－フェニルグリシン等のＮ－アリール－α－アミノ酸類、Ｎ－アリール－α－アミノ酸塩類、Ｎ－アリール－α－アミノ酸エステル類等のラジカル活性剤、α－アミノアルキルフェノン誘導体類が挙げられる。 As other photopolymerization initiators, those commonly used in this field can be used. For example, metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197; hexaarylbiimidazole derivatives described in JP-A-2000-56118 halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α- Examples include radical activators such as amino acid salts, N-aryl-α-amino acid esters, and α-aminoalkylphenone derivatives.
　具体的には、メタロセン化合物としては、例えば、ジシクロペンタジエニルチタニウムジクロリド、ジシクロペンタジエニルチタニウムビスフェニル、ジシクロペンタジエニルチタニウムビス（２，３，４，５，６－ペンタフルオロフェニル）、ジシクロペンタジエニルチタニウムビス（２，３，５，６－テトラフルオロフェニル）、ジシクロペンタジエニルチタニウムビス（２，４，６－トリフルオロフェニル）、ジシクロペンタジエニルチタニウムジ（２，６－ジフルオロフェニル）、ジシクロペンタジエニルチタニウムジ（２，４－ジフルオロフェニル）、ジ（メチルシクロペンタジエニル）チタニウムビス（２，３，４，５，６－ペンタフルオロフェニル）、ジ（メチルシクロペンタジエニル）チタニウムビス（２，６－ジフルオロフェニル）、ジシクロペンタジエニルチタニウム〔２，６－ジ－フルオロ－３－（ピロール－１－イル）－フェニル〕が挙げられる。 Specifically, the metallocene compounds include, for example, dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis(2,3,4,5,6-pentafluorophenyl ), dicyclopentadienyl titanium bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyl titanium bis(2,4,6-trifluorophenyl), dicyclopentadienyl titanium di( 2,6-difluorophenyl), dicyclopentadienyl titanium di(2,4-difluorophenyl), di(methylcyclopentadienyl) titanium bis(2,3,4,5,6-pentafluorophenyl), Di(methylcyclopentadienyl) titanium bis(2,6-difluorophenyl), dicyclopentadienyl titanium [2,6-di-fluoro-3-(pyrrol-1-yl)-phenyl].
　ビイミダゾール誘導体類としては、例えば、２－（２’－クロロフェニル）－４，５－ジフェニルイミダゾール２量体、２－（２’－クロロフェニル）－４，５－ビス（３’－メトキシフェニル）イミダゾール２量体、２－（２’－フルオロフェニル）－４，５－ジフェニルイミダゾール２量体、２－（２’－メトキシフェニル）－４，５－ジフェニルイミダゾール２量体、（４’－メトキシフェニル）－４，５－ジフェニルイミダゾール２量体が挙げられる。 Biimidazole derivatives include, for example, 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole dimer, 2-(2′-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2′-methoxyphenyl)-4,5-diphenylimidazole dimer, (4′-methoxyphenyl )-4,5-diphenylimidazole dimer.
　ハロメチル化オキサジアゾール誘導体類としては、例えば、２－トリクロロメチル－５－（２’－ベンゾフリル）－１，３，４－オキサジアゾール、２－トリクロロメチル－５－〔β－（２’－ベンゾフリル）ビニル〕－１，３，４－オキサジアゾール、２－トリクロロメチル－５－〔β－（２’－（６’’－ベンゾフリル）ビニル）〕－１，３，４－オキサジアゾール、２－トリクロロメチル－５－フリル－１，３，４－オキサジアゾールが挙げられる。 Examples of halomethylated oxadiazole derivatives include 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'- benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2′-(6″-benzofuryl)vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.
　ハロメチル－ｓ－トリアジン誘導体類としては、例えば、２－（４－メトキシフェニル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－メトキシナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－エトキシナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－エトキシカルボニルナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジンが挙げられる。 Examples of halomethyl-s-triazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis( trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl) -s-triazines.
　α－アミノアルキルフェノン誘導体類としては、例えば、２－メチル－１〔４－（メチルチオ）フェニル〕－２－モルフォリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）ブタン－１－オン、４－ジメチルアミノエチルベンゾエ－ト、４－ジメチルアミノイソアミルベンゾエ－ト、４－ジエチルアミノアセトフェノン、４－ジメチルアミノプロピオフェノン、２－エチルヘキシル－１，４－ジメチルアミノベンゾエート、２，５－ビス（４－ジエチルアミノベンザル）シクロヘキサノン、７－ジエチルアミノ－３－（４－ジエチルアミノベンゾイル）クマリン、４－（ジエチルアミノ）カルコンが挙げられる。 Examples of α-aminoalkylphenone derivatives include 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Morpholinophenyl)butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4 -dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, 4-(diethylamino)chalcone.
　また、その他の光重合開始剤として、オキシムエステル系光重合開始剤（ｃ１）以外のオキシムエステル系光重合開始剤を用いてもよい。
　その他の光重合開始剤は、１種類を単独で用いても、２種類以上を組み合わせて使用してもよい。 As another photopolymerization initiator, an oxime ester photopolymerization initiator other than the oxime ester photopolymerization initiator (c1) may be used.
Another photoinitiator may be used individually by 1 type, or may be used in combination of 2 or more types.
　（ｃ）光重合開始剤には、必要に応じて、感度を高める目的で、画像露光光源の波長に応じた増感色素、重合促進剤を配合させることができる。増感色素としては、例えば、日本国特開平４－２２１９５８号公報、日本国特開平４－２１９７５６号公報に記載のキサンテン色素、日本国特開平３－２３９７０３号公報、日本国特開平５－２８９３３５号公報に記載の複素環を有するクマリン色素、日本国特開平３－２３９７０３号公報、日本国特開平５－２８９３３５号公報に記載の３－ケトクマリン化合物、日本国特開平６－１９２４０号公報に記載のピロメテン色素、日本国特開昭４７－２５２８号公報、日本国特開昭５４－１５５２９２号公報、日本国特公昭４５－３７３７７号公報、日本国特開昭４８－８４１８３号公報、日本国特開昭５２－１１２６８１号公報、日本国特開昭５８－１５５０３号公報、日本国特開昭６０－８８００５号公報、日本国特開昭５９－５６４０３号公報、日本国特開平２－６９号公報、日本国特開昭５７－１６８０８８号公報、日本国特開平５－１０７７６１号公報、日本国特開平５－２１０２４０号公報、日本国特開平４－２８８８１８号公報に記載のジアルキルアミノベンゼン骨格を有する色素を挙げることができる。 (c) The photopolymerization initiator can be blended with a sensitizing dye and a polymerization accelerator according to the wavelength of the image exposure light source, if necessary, for the purpose of increasing sensitivity. Examples of sensitizing dyes include the xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, JP-A-3-239703 and JP-A-5-289335. JP-A-3-239703, 3-ketocoumarin compounds described in JP-A-5-289335, and JP-A-6-19240. pyrromethene dye, JP-A-47-2528, JP-A-54-155292, JP-B-45-37377, JP-A-48-84183, JP-A-48-84183, JP-A-54-155292 JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-69 , JP-A-57-168088, JP-A-5-107761, JP-A-5-210240, JP-A-4-288818 having a dialkylaminobenzene skeleton described in Pigments may be mentioned.
　増感色素としては、アミノ基含有増感色素が好ましく、アミノ基及びフェニル基を同一分子内に有する化合物がより好ましい。例えば、４，４’－ジメチルアミノベンゾフェノン、４，４’－ジエチルアミノベンゾフェノン、２－アミノベンゾフェノン、４－アミノベンゾフェノン、４，４’－ジアミノベンゾフェノン、３，３’－ジアミノベンゾフェノン、３，４－ジアミノベンゾフェノン等のベンゾフェノン系化合物；２－（ｐ－ジメチルアミノフェニル）ベンゾオキサゾール、２－（ｐ－ジエチルアミノフェニル）ベンゾオキサゾール、２－（ｐ－ジメチルアミノフェニル）ベンゾ［４，５］ベンゾオキサゾール、２－（ｐ－ジメチルアミノフェニル）ベンゾ［６，７］ベンゾオキサゾール、２，５－ビス（ｐ－ジエチルアミノフェニル）－１，３，４－オキサゾール、２－（ｐ－ジメチルアミノフェニル）ベンゾチアゾール、２－（ｐ－ジエチルアミノフェニル）ベンゾチアゾール、２－（ｐ－ジメチルアミノフェニル）ベンズイミダゾール、２－（ｐ－ジエチルアミノフェニル）ベンズイミダゾール、２，５－ビス（ｐ－ジエチルアミノフェニル）－１，３，４－チアジアゾール、（ｐ－ジメチルアミノフェニル）ピリジン、（ｐ－ジエチルアミノフェニル）ピリジン、（ｐ－ジメチルアミノフェニル）キノリン、（ｐ－ジエチルアミノフェニル）キノリン、（ｐ－ジメチルアミノフェニル）ピリミジン、（ｐ－ジエチルアミノフェニル）ピリミジン等のｐ－ジアルキルアミノフェニル基含有化合物がさらに好ましい。これらの中でも、４，４’－ジアルキルアミノベンゾフェノンが特に好ましい。
　増感色素は、１種を単独で用いてもよく、２種以上を併用してもよい。 As the sensitizing dye, an amino group-containing sensitizing dye is preferable, and a compound having an amino group and a phenyl group in the same molecule is more preferable. For example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 3,4-diamino Benzophenone compounds such as benzophenone; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2- (p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-oxazole, 2-(p-dimethylaminophenyl)benzothiazole, 2- (p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)-1,3,4- Thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, (p-diethylaminophenyl) ) p-dialkylaminophenyl group-containing compounds such as pyrimidine are more preferred. Among these, 4,4'-dialkylaminobenzophenone is particularly preferred.
The sensitizing dyes may be used singly or in combination of two or more.
　重合促進剤としては、例えば、４－ジメチルアミノ安息香酸エチル、４－ジメチルアミノ安息香酸２－エチルへキシル、４－ジメチルアミノアセトフェノン、４－ジメチルアミノプロピオフェノン等の芳香族アミン、ｎ－ブチルアミン、Ｎ－メチルジエタノールアミン、安息香酸２－ジメチルアミノエチル等の脂肪族アミンを用いることができる。
　重合促進剤は、１種を単独で用いても、２種以上を併用してもよい。 Examples of polymerization accelerators include aromatic amines such as ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone, and 4-dimethylaminopropiophenone, and n-butylamine. , N-methyldiethanolamine, and 2-dimethylaminoethyl benzoate can be used.
The polymerization accelerator may be used alone or in combination of two or more.
　本発明の着色感光性樹脂組成物における（ｃ）光重合開始剤の含有割合は特に限定されない。着色感光性樹脂組成物の全固形分量に対して、好ましくは０．０１質量％以上、より好ましくは０．１質量％以上、さらに好ましくは１質量％以上、よりさらに好ましくは１．５質量％以上、特に好ましくは２質量％以上であり、また、好ましくは２５質量％以下、より好ましくは２０質量％以下、さらに好ましくは１５質量％以下、よりさらに好ましくは１０質量％以下、特に好ましくは８質量％以下、最も好ましくは６質量％以下である。
　上記の上限及び下限は任意に組み合わせることができる。例えば、０．０１～２５質量％が好ましく、０．０１～２０質量％がより好ましく、０．１～１５質量％がさらに好ましく、１～１０質量％がよりさらに好ましく、１．５～７質量％がことさら好ましく、２～６質量％が特に好ましい。前記下限値以上とすることで撥インク性が向上する傾向がある。前記上限値以下とすることで残渣が低減する傾向がある。 The content of (c) the photopolymerization initiator in the colored photosensitive resin composition of the present invention is not particularly limited. Preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 1% by mass or more, and even more preferably 1.5% by mass, relative to the total solid content of the colored photosensitive resin composition Above, particularly preferably 2% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, even more preferably 10% by mass or less, particularly preferably 8 % by mass or less, most preferably 6% by mass or less.
The above upper and lower limits can be combined arbitrarily. For example, 0.01 to 25% by mass is preferable, 0.01 to 20% by mass is more preferable, 0.1 to 15% by mass is more preferable, 1 to 10% by mass is even more preferable, 1.5 to 7% by mass % is particularly preferred, and 2 to 6 mass % is particularly preferred. The ink repellency tends to be improved by making it equal to or higher than the lower limit. A residue tends to be reduced by making it below the said upper limit.
　本発明の着色感光性樹脂組成物における、オキシムエステル系光重合開始剤（ｃ１）の含有割合は特に限定されない。着色感光性樹脂組成物の全固形分量に対して、好ましくは０．０１質量％以上、より好ましくは０．１質量％以上、さらに好ましくは１質量％以上、よりさらに好ましくは１．５質量％以上、特に好ましくは２質量％以上であり、また、好ましくは２５質量％以下、より好ましくは２０質量％以下、さらに好ましくは１５質量％以下、よりさらに好ましくは１０質量％以下、特に好ましくは８質量％以下、最も好ましくは６質量％以下である。
　上記の上限及び下限は任意に組み合わせることができる。例えば、０．０１～２５質量％が好ましく、０．０１～２０質量％がより好ましく、０．１～１５質量％がさらに好ましく、１～１０質量％がよりさらに好ましく、１．５～７質量％がことさら好ましく、２～６質量％が特に好ましい。前記下限値以上とすることで撥インク性が向上する傾向がある。前記上限値以下とすることで残渣が低減する傾向がある。 The content of the oxime ester photopolymerization initiator (c1) in the colored photosensitive resin composition of the present invention is not particularly limited. Preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 1% by mass or more, and even more preferably 1.5% by mass, relative to the total solid content of the colored photosensitive resin composition Above, particularly preferably 2% by mass or more, preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, even more preferably 10% by mass or less, particularly preferably 8 % by mass or less, most preferably 6% by mass or less.
The above upper and lower limits can be combined arbitrarily. For example, 0.01 to 25% by mass is preferable, 0.01 to 20% by mass is more preferable, 0.1 to 15% by mass is more preferable, 1 to 10% by mass is even more preferable, 1.5 to 7% by mass % is particularly preferred, and 2 to 6 mass % is particularly preferred. The ink repellency tends to be improved by making it equal to or higher than the lower limit. A residue tends to be reduced by making it below the said upper limit.
　本発明の着色感光性樹脂組成物における、（ｃ）光重合開始剤中におけるオキシムエステル系光重合開始剤（ｃ１）の含有割合は特に限定されない。（ｃ）光重合開始剤の全質量に対して、３０質量％以上が好ましく、５０質量％以上がより好ましく、７０質量％以上がさらに好ましく、９０質量％以上が特に好ましい。また１００質量％以下が好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、３０～１００質量％が好ましく、５０～１００質量％がより好ましく、７０～１００質量％がさらに好ましく、９０～１００質量％が特に好ましい。前記下限値以上とすることで、十分な撥インク性が生じる傾向がある。前記上限値以下とすることでパターニング性が良好となる傾向がある。 The content of the oxime ester photopolymerization initiator (c1) in the photopolymerization initiator (c) in the colored photosensitive resin composition of the present invention is not particularly limited. (c) is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass or more, and particularly preferably 90% by mass or more, relative to the total mass of the photopolymerization initiator. Moreover, 100 mass % or less is preferable.
The above upper and lower limits can be combined arbitrarily. For example, 30 to 100% by mass is preferable, 50 to 100% by mass is more preferable, 70 to 100% by mass is even more preferable, and 90 to 100% by mass is particularly preferable. By making it more than the said lower limit, there exists a tendency for sufficient ink repellency to arise. The patterning property tends to be good by making it equal to or less than the above upper limit.
　着色感光性樹脂組成物中の（ｄ）光重合性化合物に対する（ｃ）光重合開始剤の配合比としては、（ｄ）光重合性化合物１００質量部に対して、１質量部以上が好ましく、５質量部以上がより好ましく、１０質量部以上がさらに好ましく、１５質量部以上がよりさらに好ましく、２０質量部以上が特に好ましく、また、２００質量部以下が好ましく、１００質量部以下がより好ましく、５０質量部以下がさらに好ましく、３０質量部以下が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～２００質量部が好ましく、５～２００質量部がより好ましく、１０～１００質量部がさらに好ましく、１５～５０質量部がよりさらに好ましく、２０～３０質量部が特に好ましい。前記下限値以上とすることで撥インク性が向上する傾向がある。前記上限値以下とすることで残渣が低減する傾向がある。 The mixing ratio of (c) photopolymerization initiator to (d) photopolymerizable compound in the colored photosensitive resin composition is preferably 1 part by weight or more with respect to 100 parts by weight of (d) photopolymerizable compound, More preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, preferably 200 parts by mass or less, more preferably 100 parts by mass or less, 50 parts by mass or less is more preferable, and 30 parts by mass or less is particularly preferable.
The above upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 200 parts by mass, more preferably 5 to 200 parts by mass, even more preferably 10 to 100 parts by mass, even more preferably 15 to 50 parts by mass, and particularly preferably 20 to 30 parts by mass. The ink repellency tends to be improved by making it equal to or higher than the lower limit. A residue tends to be reduced by making it below the said upper limit.
　着色感光性樹脂組成物中の（ｄ）光重合性化合物に対する、オキシムエステル光重合開始剤（ｃ１）の配合比としては、（ｄ）光重合性化合物１００質量部に対して、１質量部以上が好ましく、５質量部以上がより好ましく、１０質量部以上がさらに好ましく、１５質量部以上がよりさらに好ましく、２０質量部以上が特に好ましく、また、２００質量部以下が好ましく、１００質量部以下がより好ましく、５０質量部以下がさらに好ましく、３０質量部以下が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～２００質量部が好ましく、５～２００質量部がより好ましく、１０～１００質量部がさらに好ましく、１５～５０質量部がよりさらに好ましく、２０～３０質量部が特に好ましい。前記下限値以上とすることで撥インク性が向上する傾向がある。前記上限値以下とすることで残渣が低減する傾向がある。 The mixing ratio of the oxime ester photopolymerization initiator (c1) to the (d) photopolymerizable compound in the colored photosensitive resin composition is 1 part by mass or more with respect to 100 parts by mass of the (d) photopolymerizable compound. is preferable, 5 parts by mass or more is more preferable, 10 parts by mass or more is more preferable, 15 parts by mass or more is even more preferable, 20 parts by mass or more is particularly preferable, and 200 parts by mass or less is preferable, and 100 parts by mass or less is It is more preferably 50 parts by mass or less, and particularly preferably 30 parts by mass or less.
The above upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 200 parts by mass, more preferably 5 to 200 parts by mass, even more preferably 10 to 100 parts by mass, even more preferably 15 to 50 parts by mass, and particularly preferably 20 to 30 parts by mass. The ink repellency tends to be improved by making it equal to or higher than the lower limit. A residue tends to be reduced by making it below the said upper limit.
　（ｃ）光重合開始剤と併用して、連鎖移動剤を用いてもよい。連鎖移動剤としては、例えば、メルカプト基含有化合物、四塩化炭素が挙げられる。連鎖移動効果が高い傾向があることからメルカプト基含有化合物を用いることがより好ましい。Ｓ－Ｈ結合エネルギーが小さいことによって結合開裂が起こりやすく、水素引きぬき反応や連鎖移動反応を起こしやすいためであると考えられる。連鎖移動剤の使用は、感度向上や表面硬化性に有効であるため撥液性の発現にも有利である。 (c) A chain transfer agent may be used in combination with the photopolymerization initiator. Examples of chain transfer agents include mercapto group-containing compounds and carbon tetrachloride. It is more preferable to use a mercapto group-containing compound because it tends to have a high chain transfer effect. This is probably because bond cleavage is likely to occur due to the small SH bond energy, and hydrogen abstraction reaction and chain transfer reaction are likely to occur. The use of a chain transfer agent is effective in improving sensitivity and surface curability, and is therefore advantageous in developing liquid repellency.
　メルカプト基含有化合物としては、分子内にメルカプト基を複数有していてもよく、例えば、２－メルカプトベンゾチアゾール、２－メルカプトベンゾイミダゾール、２－メルカプトベンゾオキサゾール、３－メルカプト－１，２，４－トリアゾール、２－メルカプト－４（３Ｈ）－キナゾリン、β－メルカプトナフタレン、１，４－ジメチルメルカプトベンゼン等の芳香族環を有するメルカプト基含有化合物；
へキサンジチオール、デカンジチオール、ブタンジオールビス（３－メルカプトプロピオネート）、ブタンジオールビスチオグリコレート、エチレングリコールビス（３－メルカプトプロピオネート）、エチレングリコールビスチオグリコレート、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）、トリメチロールプロパントリスチオグリコレート、トリスヒドロキシエチルトリスチオプロピオネート、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、ペンタエリスリトールトリス（３－メルカプトプロピオネート）、ブタンジオールビス（３－メルカプトブチレート）、エチレングリコールビス（３－メルカプトブチレート）、トリメチロールプロパントリス（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－メルカプトブチレート）、ペンタエリスリトールトリス（３－メルカプトブチレート）、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）－トリオン等の脂肪族系のメルカプト基含有化合物が挙げられる。 The mercapto group-containing compound may have a plurality of mercapto groups in the molecule. - Mercapto group-containing compounds having an aromatic ring such as triazole, 2-mercapto-4(3H)-quinazoline, β-mercaptonaphthalene, 1,4-dimethylmercaptobenzene;
Hexanedithiol, decanedithiol, butanediol bis(3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol bis(3-mercaptopropionate), ethylene glycol bisthioglycolate, trimethylolpropane tris ( 3-mercaptopropionate), trimethylolpropane tristhioglycolate, trishydroxyethyl tristhiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), butane Diol bis(3-mercaptobutyrate), ethylene glycol bis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3- mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and other aliphatic mercapto group-containing compounds.
　芳香族環を有するメルカプト基含有化合物の中では２－メルカプトベンゾチアゾール、２－メルカプトベンゾイミダゾールが好ましく、脂肪族系のメルカプト基含有化合物の中では、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－メルカプトプロピオネート）、ペンタエリスリトールトリス（３－メルカプトプロピオネート）、トリメチロールプロパントリス（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－メルカプトブチレート）、ペンタエリスリトールトリス（３－メルカプトブチレート）、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）－トリオンが好ましい。 Among mercapto group-containing compounds having an aromatic ring, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred, and among aliphatic mercapto group-containing compounds, trimethylolpropane tris (3-mercaptopropionate) , pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol Tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione are preferred.
　感度の面からは、脂肪族系のメルカプト基含有化合物が好ましく、具体的には、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－メルカプトプロピオネート）、ペンタエリスリトールトリス（３－メルカプトプロピオネート）、トリメチロールプロパントリス（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－メルカプトブチレート）、ペンタエリスリトールトリス（３－メルカプトブチレート）、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）－トリオンが好ましく、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）、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）がより好ましい。
　連鎖移動剤は１種を単独で用いてもよく、２種以上を併用してもよい。 From the viewpoint of sensitivity, aliphatic mercapto group-containing compounds are preferred, and specifically, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris. (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5-tris (3-Mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione is preferred, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis ( 3-mercaptobutyrate) is more preferred.
A chain transfer agent may be used individually by 1 type, and may use 2 or more types together.
　テーパ角を高める観点から、２－メルカプトベンゾチアゾール、２－メルカプトベンゾイミダゾール、及び２－メルカプトベンゾオキサゾールよりなる群から選択された１又は２以上と、光重合開始剤とを組み合わせて、光重合開始剤系として使用することが好適である。例えば、２－メルカプトベンゾチアゾールを用いてもよく、２－メルカプトベンゾイミダゾールを用いてもよく、２－メルカプトベンゾチアゾールと２－メルカプトベンゾイミダゾールとを併用してもよい。
　感度の観点からは、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）、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）よりなる群から選択された１又は２以上を用いることが好ましい。さらに、感度の観点から、２－メルカプトベンゾチアゾール、２－メルカプトベンゾイミダゾール、及び２－メルカプトベンゾオキサゾールよりなる群から選択された１又は２以上と、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）、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）よりなる群から選択された１又は２以上と、光重合開始剤とを組み合わせて用いることが好ましい。 From the viewpoint of increasing the taper angle, one or more selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoxazole is combined with a photopolymerization initiator to initiate photopolymerization. It is suitable for use as a drug system. For example, 2-mercaptobenzothiazole may be used, 2-mercaptobenzimidazole may be used, and 2-mercaptobenzothiazole and 2-mercaptobenzimidazole may be used in combination.
From the viewpoint of sensitivity, it is preferable to use one or more selected from the group consisting of pentaerythritol tetrakis(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptobutyrate). Furthermore, from the viewpoint of sensitivity, one or more selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoxazole, and pentaerythritol tetrakis (3-mercaptopropionate), It is preferable to use one or more selected from the group consisting of pentaerythritol tetrakis(3-mercaptobutyrate) in combination with a photopolymerization initiator.
　本発明の着色感光性樹脂組成物が連鎖移動剤を含む場合、連鎖移動剤の含有割合は特に限定されないが、着色感光性樹脂組成物の全固形分量に対して、好ましくは０．０１質量％以上、より好ましくは０．１質量％以上、さらに好ましくは０．５質量％以上、よりさらに好ましくは０．８質量％以上であり、また、好ましくは５質量％以下、より好ましくは４質量％以下、さらに好ましくは３質量％以下、よりさらに好ましくは２質量％以下である。
　上記の上限及び下限は任意に組み合わせることができる。例えば、０．０１～５質量％が好ましく、０．１～４質量％がより好ましく、０．５～３質量％がさらに好ましく、０．８～２質量％が特に好ましい。前記下限値以上とすることで撥インク性が向上する傾向がある。前記上限値以下とすることで線幅の細い高精細な隔壁を形成できる傾向がある。 When the colored photosensitive resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is not particularly limited, but is preferably 0.01% by mass based on the total solid content of the colored photosensitive resin composition. Above, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, still more preferably 0.8% by mass or more, and preferably 5% by mass or less, more preferably 4% by mass Below, more preferably 3 mass % or less, still more preferably 2 mass % or less.
The above upper and lower limits can be combined arbitrarily. For example, 0.01 to 5% by mass is preferable, 0.1 to 4% by mass is more preferable, 0.5 to 3% by mass is even more preferable, and 0.8 to 2% by mass is particularly preferable. The ink repellency tends to be improved by making it equal to or higher than the lower limit. When the content is equal to or less than the above upper limit, there is a tendency that high-definition partition walls with a narrow line width can be formed.
　本発明の着色感光性樹脂組成物が連鎖移動剤を含む場合、（ｃ）光重合開始剤に対する連鎖移動剤の含有割合としては、（ｃ）光重合開始剤１００質量部に対して、５質量部以上が好ましく、１０質量部以上がより好ましく、１５質量部以上がさらに好ましく、２０質量部以上が特に好ましく、また、５００質量部以下が好ましく、３００質量部以下がより好ましく、１００質量部以下がさらに好ましく、５０質量部以下が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、５～５００質量部が好ましく、１０～３００質量部がより好ましく、１５～１００質量部がさらに好ましく、２０～５０質量部が特に好ましい。前記下限値以上とすることで撥インク性が向上する傾向がある。前記上限値以下とすることで線幅の細い高精細な隔壁を形成できる傾向がある。 When the colored photosensitive resin composition of the present invention contains a chain transfer agent, the content ratio of the chain transfer agent to the (c) photopolymerization initiator is 5 parts by weight with respect to 100 parts by weight of the (c) photopolymerization initiator. parts by mass or more, more preferably 10 parts by mass or more, more preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, and preferably 500 parts by mass or less, more preferably 300 parts by mass or less, and 100 parts by mass or less. is more preferable, and 50 parts by mass or less is particularly preferable.
The above upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 500 parts by mass, more preferably 10 to 300 parts by mass, even more preferably 15 to 100 parts by mass, and particularly preferably 20 to 50 parts by mass. The ink repellency tends to be improved by making it equal to or higher than the lower limit. When the content is equal to or less than the above upper limit, there is a tendency that high-definition partition walls with a narrow line width can be formed.
［１－１－４］（ｄ）光重合性化合物
　本発明の着色感光性樹脂組成物は、（ｄ）光重合性化合物を含有する。（ｄ）光重合性化合物を含むことで、塗膜の硬化性が上がり、また撥インク性が向上すると考えられる。
　（ｄ）光重合性化合物としては、エチレン性不飽和結合を分子内に１個以上有する化合物（以下、エチレン性不飽和化合物とも称する場合がある。）が挙げられる。重合性、架橋性、およびそれに伴う露光部と非露光部の現像液溶解性の差異を拡大できる等の点から、エチレン性不飽和結合を分子内に２個以上有する化合物であることが好ましく、また、その不飽和結合は（メタ）アクリロイルオキシ基に由来するもの、つまり、（メタ）アクリレート化合物であることがさらに好ましい。 [1-1-4] (d) Photopolymerizable compound The colored photosensitive resin composition of the present invention contains (d) a photopolymerizable compound. (d) It is believed that the inclusion of the photopolymerizable compound increases the curability of the coating film and improves the ink repellency.
(d) Photopolymerizable compounds include compounds having one or more ethylenically unsaturated bonds in the molecule (hereinafter also referred to as ethylenically unsaturated compounds). A compound having two or more ethylenically unsaturated bonds in the molecule is preferable from the viewpoint of being able to expand the difference in developer solubility between the exposed area and the non-exposed area due to polymerizability, crosslinkability, and the like. Further, the unsaturated bond is more preferably derived from a (meth)acryloyloxy group, that is, a (meth)acrylate compound.
　本発明においては、特に、１分子中にエチレン性不飽和結合を２個以上有する多官能エチレン性単量体を使用することが望ましい。多官能エチレン性単量体が有するエチレン性不飽和基の数は特に限定されないが、好ましくは２個以上、より好ましくは３個以上、さらに好ましくは５個以上であり、また、好ましくは１５個以下、より好ましくは１０個以下、さらに好ましくは８個以下、特に好ましくは７個以下である。
　上記の上限及び下限は任意に組み合わせることができる。例えば、２～１５個が好ましく、２～１０個がより好ましく、３～８個がさらに好ましく、５～７個が特に好ましい。前記下限値以上とすることで重合性が向上して撥インク性が高くなる傾向がある。前記上限値以下とすることで現像性がより良好となる傾向がある。
　エチレン性不飽和化合物としては、例えば、脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル；芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル；脂肪族ポリヒドロキシ化合物、芳香族ポリヒドロキシ化合物等の多価ヒドロキシ化合物と、不飽和カルボン酸及び多塩基性カルボン酸とのエステル化反応により得られるエステルが挙げられる。 In the present invention, it is particularly desirable to use polyfunctional ethylenic monomers having two or more ethylenically unsaturated bonds in one molecule. The number of ethylenically unsaturated groups possessed by the polyfunctional ethylenic monomer is not particularly limited, but is preferably 2 or more, more preferably 3 or more, still more preferably 5 or more, and preferably 15. Below, more preferably 10 or less, still more preferably 8 or less, particularly preferably 7 or less.
The above upper and lower limits can be combined arbitrarily. For example, 2 to 15 are preferred, 2 to 10 are more preferred, 3 to 8 are even more preferred, and 5 to 7 are particularly preferred. When the content is at least the above lower limit, there is a tendency that the polymerizability is improved and the ink repellency is increased. The developability tends to be better when the amount is set to the above upper limit or less.
Ethylenically unsaturated compounds include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds, etc. and esters obtained by an esterification reaction of polyhydric hydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids.
　脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルとしては、例えば、エチレングリコールジアクリレート、トリエチレングリコールジアクリレート、トリメチロールプロパントリアクリレート、トリメチロールエタントリアクリレート、ペンタエリスリトールジアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールテトラアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート、グリセロールアクリレート等の脂肪族ポリヒドロキシ化合物のアクリル酸エステル、これらの例示化合物のアクリレートをメタクリレートに代えたメタクリル酸エステル、これらの例示化合物のアクリレートをイタコネートに代えたイタコン酸エステル、これらの例示化合物のアクリレートをクロトネートに代えたクロトン酸エステルもしくはこれらの例示化合物のアクリレートをマレエートに代えたマレイン酸エステルが挙げられる。 Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol ethane triacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate. , pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, acrylic acid esters of aliphatic polyhydroxy compounds such as glycerol acrylate, methacrylics obtained by replacing the acrylates of these exemplary compounds with methacrylates acid esters, itaconate esters obtained by replacing the acrylates of these exemplary compounds with itaconates, crotonate esters obtained by replacing the acrylates of these exemplary compounds with crotonates, and maleate esters obtained by replacing the acrylates of these exemplary compounds with maleates. .
　芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルとしては、例えば、ハイドロキノンジアクリレート、ハイドロキノンジメタクリレート、レゾルシンジアクリレート、レゾルシンジメタクリレート、ピロガロールトリアクリレート等の芳香族ポリヒドロキシ化合物のアクリル酸エステル及びメタクリル酸エステルが挙げられる。
　脂肪族ポリヒドロキシ化合物、芳香族ポリヒドロキシ化合物等の多価ヒドロキシ化合物と、不飽和カルボン酸及び多塩基性カルボン酸とのエステル化反応により得られるエステルとしては必ずしも単一物ではないが、代表的な具体例を挙げれば、例えば、アクリル酸、フタル酸、及びエチレングリコールの縮合物、アクリル酸、マレイン酸、及びジエチレングリコールの縮合物、メタクリル酸、テレフタル酸及びペンタエリスリトールの縮合物、アクリル酸、アジピン酸、ブタンジオール及びグリセリンの縮合物が挙げられる。 Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters and methacryl esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. acid esters.
Esters obtained by the esterification reaction of polyhydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids are not necessarily single substances, but are representative. Specific examples include condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, and adipine. Condensates of acids, butanediol and glycerin may be mentioned.
　その他、本発明に用いられる多官能エチレン性単量体としては、例えば、ポリイソシアネート化合物と水酸基含有（メタ）アクリル酸エステル又はポリイソシアネート化合物とポリオール及び水酸基含有（メタ）アクリル酸エステルを反応させて得られるようなウレタン（メタ）アクリレート類；多価エポキシ化合物とヒドロキシ（メタ）アクリレート又は（メタ）アクリル酸との付加反応物のようなエポキシアクリレート類；エチレンビスアクリルアミド等のアクリルアミド類；フタル酸ジアリル等のアリルエステル類；ジビニルフタレート等のビニル基含有化合物が挙げられる。 In addition, as the polyfunctional ethylenic monomer used in the present invention, for example, a polyisocyanate compound and a hydroxyl group-containing (meth)acrylic acid ester or a polyisocyanate compound, a polyol and a hydroxyl group-containing (meth)acrylic acid ester are reacted. Urethane (meth)acrylates such as those obtained; epoxy acrylates such as addition reaction products of polyepoxy compounds and hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylenebisacrylamide; diallyl phthalate and vinyl group-containing compounds such as divinyl phthalate.
　ウレタン（メタ）アクリレート類としては、例えば、ＤＰＨＡ－４０Ｈ、ＵＸ－５０００、ＵＸ－５００２Ｄ－Ｐ２０、ＵＸ－５００３Ｄ、ＵＸ－５００５（日本化薬社製）、Ｕ－２ＰＰＡ、Ｕ－６ＬＰＡ、Ｕ－１０ＰＡ、Ｕ－３３Ｈ、ＵＡ－５３Ｈ、ＵＡ－３２Ｐ、ＵＡ－１１００Ｈ（新中村化学工業社製）、ＵＡ－３０６Ｈ、ＵＡ－５１０Ｈ、ＵＦ－８００１Ｇ（協栄社化学社製）、ＵＶ－１７００Ｂ、ＵＶ－７６００Ｂ、ＵＶ－７６０５Ｂ、ＵＶ－７６３０Ｂ、ＵＶ７６４０Ｂ（三菱ケミカル社製）が挙げられる。 Urethane (meth)acrylates include, for example, DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U- 10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B, Examples include UV-7600B, UV-7605B, UV-7630B, and UV7640B (manufactured by Mitsubishi Chemical Corporation).
　隔壁の基板に対する密着性と撥インク性の観点から（ｄ）光重合性化合物としては、脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル又はウレタン（メタ）アクリレート類が好ましく、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、２，２，２－トリス（メタ）アクリロイロキシメチルエチルフタル酸、ペンタエリスリトールテトラ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレートの二塩基酸無水物付加物、ペンタエリスリトールトリ（メタ）アクリレートの二塩基酸無水物付加物がより好ましい。
　（ｄ）光重合性化合物は１種を単独で用いてもよく、２種以上を併用してもよい。 From the viewpoint of the adhesion of the partition wall to the substrate and the ink repellency, (d) the photopolymerizable compound is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid or a urethane (meth)acrylate, and dipentaerythritol hexa (Meth)acrylates, dipentaerythritol penta(meth)acrylate, 2,2,2-tris(meth)acryloyloxymethylethyl phthalate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipenta A dibasic acid anhydride adduct of erythritol penta(meth)acrylate and a dibasic acid anhydride adduct of pentaerythritol tri(meth)acrylate are more preferred.
(d) Photopolymerizable compounds may be used singly or in combination of two or more.
　本発明において、（ｄ）光重合性化合物の分子量は特に限定されない。撥インク性、線幅の細い高精細な隔壁を形成する観点から、好ましくは１００以上、より好ましくは１５０以上、さらに好ましくは２００以上、よりさらに好ましくは３００以上、特に好ましくは４００以上、最も好ましくは５００以上であり、また、好ましくは１０００以下、より好ましくは７００以下である。
　上記の上限及び下限は任意に区合わせることができる。例えば、１００～１０００が好ましく、１５０～１０００がより好ましく、２００～１０００がさらに好ましく、３００～７００がよりさらに好ましく、４００～７００がことさらに好ましく、５００～７００が特に好ましい。 In the present invention, the molecular weight of (d) the photopolymerizable compound is not particularly limited. From the viewpoint of ink repellency and the formation of high-definition partition walls with a narrow line width, the is 500 or more, preferably 1000 or less, more preferably 700 or less.
The above upper and lower limits can be arbitrarily crossed. For example, 100 to 1000 is preferred, 150 to 1000 is more preferred, 200 to 1000 is even more preferred, 300 to 700 is even more preferred, 400 to 700 is even more preferred, and 500 to 700 is particularly preferred.
　（ｄ）光重合性化合物の炭素数は特に限定されない。撥インク性、残渣抑制の観点から、好ましくは７以上、より好ましくは１０以上、さらに好ましくは１５以上、よりさらに好ましくは２０以上、特に好ましくは２５以上であり、好ましくは５０以下、より好ましくは４０以下、さらに好ましくは３５以下、特に好ましくは３０以下である。
　上記の上限及び下限は任意に区合わせることができる。例えば、７～５０が好ましく、１０～５０がより好ましく、１５～４０がさらに好ましく、２０～３５がよりさらに好ましく、２５～３０が特に好ましい。 (d) The number of carbon atoms in the photopolymerizable compound is not particularly limited. From the viewpoint of ink repellency and residue suppression, it is preferably 7 or more, more preferably 10 or more, still more preferably 15 or more, even more preferably 20 or more, particularly preferably 25 or more, and preferably 50 or less, more preferably It is 40 or less, more preferably 35 or less, and particularly preferably 30 or less.
The above upper and lower limits can be arbitrarily crossed. For example, 7 to 50 are preferred, 10 to 50 are more preferred, 15 to 40 are even more preferred, 20 to 35 are even more preferred, and 25 to 30 are particularly preferred.
　（ｄ）光重合性化合物としては、撥インク性、線幅の細い高精細な隔壁を形成する観点から、エステル（メタ）アクリレート類、エポキシ（メタ）アクリレート類、およびウレタン（メタ）アクリレート類が好ましく、ペンタエリスリトールテトラ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレートジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート等３官能以上のエステル（メタ）アクリレート類、２，２，２－トリス（メタ）アクリロイロキシメチルエチルフタル酸、ジペンタエリスリトールペンタ（メタ）アクリレートの二塩基酸無水物付加物等の３官能以上のエステル（メタ）アクリレート類への酸無水物の付加物が、撥インク性、線幅の細い高精細な隔壁を形成する面でさらに好ましい。 (d) Photopolymerizable compounds include ester (meth)acrylates, epoxy (meth)acrylates, and urethane (meth)acrylates from the viewpoint of ink repellency and formation of high-definition partition walls with a narrow line width. Preferably, trifunctional or higher ester (meth)acrylates such as pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and dipentaerythritol penta(meth)acrylate, 2,2, 2-tris(meth)acryloyloxymethylethyl phthalic acid, acid anhydride adducts to tri- or higher functional ester (meth)acrylates such as dibasic acid anhydride adducts of dipentaerythritol penta(meth)acrylate is more preferable in terms of ink repellency and formation of fine partition walls with a narrow line width.
　本発明の着色感光性樹脂組成物中の（ｄ）光重合性化合物の含有割合は、特に限定されない。着色感光性樹脂組成物の全固形分量に対して、好ましくは１質量％以上、より好ましくは５質量％以上、さらに好ましくは１０質量％以上、よりさらに好ましくは１５質量％以上、特に好ましくは２０質量％以上であり、また、好ましくは８０質量％以下、より好ましくは６０質量％以下、さらに好ましくは５０質量％以下、よりさらに好ましくは４５質量％以下である。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～８０質量％が好ましく、５～８０質量％がより好ましく、１０～６０質量％がさらに好ましく、１５～４０質量％がよりさらに好ましく、２０～４５質量％が特に好ましい。前記下限値以上とすることで撥インク性が向上する傾向がある。前記上限値以下とすることで線幅の細い高精細な隔壁を形成できる傾向がある。 The content of (d) the photopolymerizable compound in the colored photosensitive resin composition of the present invention is not particularly limited. With respect to the total solid content of the colored photosensitive resin composition, preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, even more preferably 15% by mass or more, particularly preferably 20% by mass or more % by mass or more, preferably 80% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, and even more preferably 45% by mass or less.
The above upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 80% by mass, more preferably 5 to 80% by mass, even more preferably 10 to 60% by mass, even more preferably 15 to 40% by mass, and particularly preferably 20 to 45% by mass. The ink repellency tends to be improved by making it equal to or higher than the lower limit. When the content is equal to or less than the above upper limit, there is a tendency that high-definition partition walls with a narrow line width can be formed.
　（ｂ）アルカリ可溶性樹脂１００質量部に対する（ｄ）光重合性化合物の含有割合は特に限定されない。好ましくは５質量部以上、より好ましくは１０質量部以上、さらに好ましくは１５質量部以上、よりさらに好ましくは２０質量部以上、ことさらに好ましくは２５質量部以上、よりことさらに好ましくは３０質量部以上、最も好ましくは４０質量部以上であり、また、好ましくは１５０質量部以下、より好ましくは１００質量部以下、さらに好ましくは９０質量部以下、よりさらに好ましくは８０質量部以下、特に好ましくは７０質量部以下である。
　上記の上限及び下限は任意に組み合わせることができる。例えば、５～１５０質量部が好ましく、１０～１５０質量部がより好ましく、１５～１００質量部がさらに好ましく、２０～９０質量部がよりさらに好ましく、２５～８０質量部がことさら好ましく、３０～７５質量部が特に好ましく、４０～７０質量部が最も好ましい。前記下限値以上とすることで撥インク性が向上する傾向がある。前記上限値以下とすることで線幅の細い高精細な隔壁を形成できる傾向がある。 The content of (d) the photopolymerizable compound relative to 100 parts by mass of the alkali-soluble resin (b) is not particularly limited. Preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, still more preferably 20 parts by mass or more, even more preferably 25 parts by mass or more, even more preferably 30 parts by mass or more , Most preferably 40 parts by mass or more, preferably 150 parts by mass or less, more preferably 100 parts by mass or less, still more preferably 90 parts by mass or less, even more preferably 80 parts by mass or less, particularly preferably 70 parts by mass It is below the department.
The above upper and lower limits can be combined arbitrarily. For example, 5 to 150 parts by mass is preferable, 10 to 150 parts by mass is more preferable, 15 to 100 parts by mass is more preferable, 20 to 90 parts by mass is even more preferable, 25 to 80 parts by mass is particularly preferable, and 30 to 75 parts by mass is more preferable. Parts by weight are particularly preferred, with 40 to 70 parts by weight being most preferred. The ink repellency tends to be improved by making it equal to or higher than the lower limit. When the content is equal to or less than the above upper limit, there is a tendency that high-definition partition walls with a narrow line width can be formed.
［１－１－５］（ｅ）撥液剤
　本発明の着色感光性樹脂組成物は（ｅ）撥液剤を含有し、（ｅ）撥液剤は、架橋基を有し、且つフッ素原子及び／又はシロキサン鎖を有する化合物（ｅ１）を含有する。（ｅ）撥液剤を含有することによって、得られる隔壁の表面に撥インク性を付与できることから、得られる隔壁を画素ごとの混色を防ぐものとすることができる。 [1-1-5] (e) liquid repellent agent The colored photosensitive resin composition of the present invention contains (e) a liquid repellent agent, and (e) the liquid repellent agent has a cross-linking group and a fluorine atom and/or It contains a compound (e1) having a siloxane chain. (e) By containing a liquid-repellent agent, ink repellency can be imparted to the surface of the obtained partition wall, so that the obtained partition wall can prevent color mixture for each pixel.
　＜化合物（ｅ１）＞
　化合物（ｅ１）は架橋基、並びにフッ素原子及び／又はシロキサン鎖を有する。
　化合物（ｅ１）の架橋基としては、例えば、エポキシ基、エチレン性不飽和基、活性エネルギー線の照射によりラジカルを発生する活性基が挙げられ、撥液剤の現像液への流出抑制の観点から、エチレン性不飽和基が好ましい。
　架橋基を有する撥液剤を用いると、撥液剤自体が架橋反応に関わることで撥液剤が現像処理で流出しにくくなり、その結果、得られる隔壁が高い撥インク性を示すものと考えられる。 <Compound (e1)>
Compound (e1) has a cross-linking group, a fluorine atom and/or a siloxane chain.
Examples of the cross-linking group of the compound (e1) include an epoxy group, an ethylenically unsaturated group, and an active group that generates a radical upon irradiation with an active energy ray. Ethylenically unsaturated groups are preferred.
It is believed that when a liquid repellent agent having a cross-linking group is used, the liquid repellent agent itself participates in the cross-linking reaction, making it difficult for the liquid repellent agent to flow out during development, and as a result, the partition walls obtained exhibit high ink repellency.
　化合物（ｅ１）がフッ素原子及び／又はシロキサン鎖を有することで、撥液剤が隔壁の表面に配向して、インキのにじみや混色を防止する働きをする傾向がある。さらに詳しくは、フッ素原子を有する基及び／又はシロキサン鎖が、インキをはじき、インキが隔壁を越えて隣接する領域に進入することによるインキのにじみや混色を防ぐ働きをする傾向がある。 When the compound (e1) has a fluorine atom and/or a siloxane chain, the liquid repellent agent tends to be oriented on the surface of the partition wall and work to prevent ink bleeding and color mixing. More specifically, the fluorine atom-containing groups and/or siloxane chains tend to repel ink and prevent ink bleeding and color mixing due to ink crossing the partition into adjacent areas.
　化合物（ｅ１）としては、一分子中に架橋基、フッ素原子及びシロキサン鎖を有する撥液剤、架橋基とフッ素原子を有する撥液剤、架橋基とシロキサン鎖を有する撥液剤を１種単独で使用してもよく、２種以上を併用してもよい。 As the compound (e1), a liquid repellent agent having a cross-linking group, a fluorine atom and a siloxane chain in one molecule, a liquid repellent agent having a cross-linking group and a fluorine atom, and a liquid repellent agent having a cross-linking group and a siloxane chain are used singly. may be used, or two or more may be used in combination.
　化合物（ｅ１）がフッ素原子を有する場合、化合物（ｅ１）は、フルオロアルキル基、フルオロアルキレン基、フルオロアルキレンエーテル鎖及びフルオロ芳香族基からなる群のうち少なくとも１つを有することが好ましい。パーフルオロアルキル基、パーフルオロアルキレン基、パーフルオロアルキレンエーテル鎖、パーフルオロ芳香族基を有することが撥液性の点でより好ましい。フルオロアルキル基、フルオロアルキレン基、フルオロアルキレンエーテル鎖及びフルオロ芳香族基からなる群のうち少なくとも１つを有することで、化合物（ｅ１）がさらに隔壁の表面に配向しやすくなり、より高い撥インク性を示し、インキのにじみや混色をさらに防ぐ傾向がある。 When compound (e1) has a fluorine atom, compound (e1) preferably has at least one of the group consisting of a fluoroalkyl group, a fluoroalkylene group, a fluoroalkylene ether chain and a fluoroaromatic group. Having a perfluoroalkyl group, a perfluoroalkylene group, a perfluoroalkylene ether chain, or a perfluoroaromatic group is more preferable from the viewpoint of liquid repellency. Having at least one selected from the group consisting of a fluoroalkyl group, a fluoroalkylene group, a fluoroalkylene ether chain, and a fluoroaromatic group makes it easier for the compound (e1) to be oriented on the partition wall surface, resulting in higher ink repellency. and tend to further prevent ink bleeding and color mixing.
　以下にフルオロアルキル基、フルオロアルキレン基、フルオロアルキレンエーテル鎖及びフルオロ芳香族基の具体例を示すが、「フルオロ」と記載する場合、水素原子が全てフッ素原子に置換されている「パーフルオロ」、及び一部の水素原子が残っている「ポリフルオロ」の両方を含む。
　フルオロアルキル基としては、例えば、フルオロメチル基、フルオロエチル基、フルオロプロピル基、フルオロブチル基、フルオロヘキシル基が挙げられる。
　フルオロアルキレン鎖としては、例えば、フルオロメチレン鎖、フルオロエチレン鎖、フルオロプロピレン鎖、フルオロブチレン基、フルオロヘキシレン鎖が挙げられる。
　フルオロアルキレンエーテル鎖としては、例えば、－ＣＦ2－Ｏ－、－（ＣＦ2）2－Ｏ－、－（ＣＦ2）3－Ｏ－、－ＣＦ2－Ｃ（ＣＦ3）Ｏ－、－Ｃ（ＣＦ3）－ＣＦ2－Ｏ－及びこれらの繰り返し単位をもつ２価の基が挙げられる他、上記フルオロアルキレンエーテル鎖のフッ素原子の一部が水素原子であるものが挙げられる。
　フルオロ芳香族基としては、例えば、フルオロフェニル基、フルオロナフチル基、フルオロアントラシル基が挙げられる。 Specific examples of fluoroalkyl groups, fluoroalkylene groups, fluoroalkylene ether chains and fluoroaromatic groups are shown below. and "polyfluoro" with some hydrogen atoms remaining.
Examples of fluoroalkyl groups include fluoromethyl, fluoroethyl, fluoropropyl, fluorobutyl, and fluorohexyl groups.
Fluoroalkylene chains include, for example, fluoromethylene chains, fluoroethylene chains, fluoropropylene chains, fluorobutylene groups, and fluorohexylene chains.
Examples of fluoroalkylene ether chains include -CF 2 -O-, -(CF 2 ) 2 -O-, -(CF 2 ) 3 -O-, -CF 2 -C(CF 3 )O-, -C Examples thereof include (CF 3 )--CF 2 --O-- and divalent groups having repeating units thereof, and those in which a portion of the fluorine atoms in the above fluoroalkylene ether chain are hydrogen atoms.
Fluoroaromatic groups include, for example, fluorophenyl groups, fluoronaphthyl groups, and fluoroanthracyl groups.
　架橋基及びフッ素原子を有する撥液剤としては、例えば、エポキシ基及びフルオロアルキル基を有するアクリル共重合樹脂、エポキシ基及びフルオロアルキレンエーテル鎖を有するアクリル共重合樹脂、エチレン性不飽和基及びフルオロアルキル基を有するアクリル共重合樹脂、エチレン性不飽和基及びフルオロアルキレンエーテル鎖を有するアクリル共重合樹脂、エポキシ基及びフルオロアルキル基を有するエポキシ（メタ）アクリレート樹脂、エポキシ基及びフルオロアルキレンエーテル鎖を有するエポキシ（メタ）アクリレート樹脂、エチレン性不飽和基及びフルオロアルキル基を有するエポキシ（メタ）アクリレート樹脂、エチレン性不飽和基及びフルオロアルキレンエーテル鎖を有するエポキシ（メタ）アクリレート樹脂が挙げられる。撥インク性の観点から、エチレン性不飽和基及びフルオロアルキル基を有するアクリル共重合樹脂、エチレン性不飽和基及びフルオロアルキレンエーテル鎖を有するアクリル共重合樹脂が好ましく、エチレン性不飽和基及びフルオロアルキレンエーテル鎖を有するアクリル共重合樹脂がさらに好ましい。 Liquid repellent agents having a cross-linking group and a fluorine atom include, for example, an acrylic copolymer resin having an epoxy group and a fluoroalkyl group, an acrylic copolymer resin having an epoxy group and a fluoroalkylene ether chain, an ethylenically unsaturated group and a fluoroalkyl group. , an acrylic copolymer resin having an ethylenically unsaturated group and a fluoroalkylene ether chain, an epoxy (meth)acrylate resin having an epoxy group and a fluoroalkyl group, an epoxy having an epoxy group and a fluoroalkylene ether chain ( Examples include meth)acrylate resins, epoxy (meth)acrylate resins having an ethylenically unsaturated group and a fluoroalkyl group, and epoxy (meth)acrylate resins having an ethylenically unsaturated group and a fluoroalkylene ether chain. From the viewpoint of ink repellency, an acrylic copolymer resin having an ethylenically unsaturated group and a fluoroalkyl group, an acrylic copolymer resin having an ethylenically unsaturated group and a fluoroalkylene ether chain are preferable, and an ethylenically unsaturated group and a fluoroalkylene ether chain are preferable. An acrylic copolymer resin having an ether chain is more preferred.
　架橋基及びフッ素原子を有する撥液剤の市販品としては、例えば、ＤＩＣ社製「メガファック（登録商標、以下同じ。）Ｆ１１６」、「メガファックＦ１２０」、「メガファックＦ１４２Ｄ」、「メガファックＦ１４４Ｄ」、「メガファックＦ１５０」、「メガファックＦ１６０」、「メガファックＦ１７１」、「メガファックＦ１７２」、「メガファックＦ１７３」、「メガファックＦ１７７」、「メガファックＦ１７８Ａ」、「メガファックＦ１７８Ｋ」、「メガファックＦ１７９」、「メガファックＦ１８３」、「メガファックＦ１８４」、「メガファックＦ１９１」、「メガファックＦ８１２」、「メガファックＦ８１５」、「メガファックＦ８２４」、「メガファックＦ８３３」、「メガファックＲＳ１０１」、「メガファックＲＳ１０２」「メガファックＲＳ１０５」、「メガファックＲＳ２０１」、「メガファックＲＳ２０２」、「メガファックＲＳ３０１」、「メガファックＲＳ３０３」「メガファックＲＳ３０４」、「メガファックＲＳ４０１」、「メガファックＲＳ４０２」、「メガファックＲＳ５０１」、「メガファックＲＳ５０２」、「メガファックＲＳ－７２－Ｋ」、「メガファックＲＳ－７８」、「メガファックＲＳ－９０」、「ＤＥＦＥＮＳＡ（登録商標、以下同じ。）　ＭＣＦ３００」、「ＤＥＦＥＮＳＡ　ＭＣＦ３１０」、「ＤＥＦＥＮＳＡ　ＭＣＦ３１２」、「ＤＥＦＥＮＳＡ　ＭＣＦ３２３」、スリーエムジャパン社製「フロラードＦＣ４３０」、「フロラードＦＣ４３１」、「ＦＣ－４４３０」、「ＦＣ４４３２」、ＡＧＣ社製「アサヒガード（登録商標。）ＡＧ７１０」、「サーフロン（登録商標、以下同じ。）Ｓ－３８２」、「サーフロンＳＣ－１０１」、「サーフロンＳＣ－１０２」、「サーフロンＳＣ－１０３」、「サーフロンＳＣ－１０４」、「サーフロンＳＣ－１０５」、「サーフロンＳＣ－１０６」の商品名で市販されている含フッ素有機化合物を使用することができる。
　エチレン性不飽和基及びフルオロアルキレンエーテル鎖を有するアクリル共重合樹脂として、「メガファックＲＳ－７２－Ｋ」、「メガファックＲＳ－７８」、「メガファックＲＳ－９０」を好適に使用することができる。 Commercially available liquid repellent agents having a cross-linking group and a fluorine atom include, for example, DIC's "Megafac (registered trademark, hereinafter the same.) F116", "Megafac F120", "Megafac F142D", and "Megafac F144D". ”, “Megafuck F150”, “Megafuck F160”, “Megafuck F171”, “Megafuck F172”, “Megafuck F173”, “Megafuck F177”, “Megafuck F178A”, “Megafuck F178K”, "Megafuck F179", "Megafuck F183", "Megafuck F184", "Megafuck F191", "Megafuck F812", "Megafuck F815", "Megafuck F824", "Megafuck F833", "Megafuck F833" ``Fuck RS101'', ``Megafuck RS102'', ``Megafuck RS105'', ``Megafuck RS201'', ``Megafuck RS202'', ``Megafuck RS301'', ``Megafuck RS303'', ``Megafuck RS304'', ``Megafuck RS401'', "Megafuck RS402", "Megafuck RS501", "Megafuck RS502", "Megafuck RS-72-K", "Megafuck RS-78", "Megafuck RS-90", "DEFENSA (registered trademark, The same applies hereinafter.) MCF300", "DEFENSA MCF310", "DEFENSA MCF312", "DEFENSA MCF323", 3M Japan's "Florado FC430", "Florado FC431", "FC-4430", "FC4432", AGC's " Asahi Guard (registered trademark) AG710", "Surflon (registered trademark, hereinafter the same) S-382", "Surfron SC-101", "Surfron SC-102", "Surfron SC-103", "Surfron SC- 104”, “Surflon SC-105”, and “Surflon SC-106”.
"Megaface RS-72-K", "Megaface RS-78" and "Megaface RS-90" can be preferably used as acrylic copolymer resins having an ethylenically unsaturated group and a fluoroalkylene ether chain. can.
　化合物（ｅ１）がフッ素原子を有する場合、化合物（ｅ１）中のフッ素原子含有割合は特に制限されない。化合物（ｅ１）の全質量に対して５質量％以上が好ましく、１０質量％以上がより好ましく、１５質量％以上がさらに好ましく、２０質量％以上がよりさらに好ましい。また、５０質量％以下が好ましく、３５質量％以下がより好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、５～５０質量％が好ましく、１０～５０質量％がより好ましく、１５～３５質量％がさらに好ましく、２０～３５質量％が特に好ましい。前記下限値以上とすることで高い接触角を示す傾向がある。前記上限値以下とすることで画素部への流出を抑制できる傾向がある。 When compound (e1) has a fluorine atom, the fluorine atom content in compound (e1) is not particularly limited. It is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and even more preferably 20% by mass or more, relative to the total mass of compound (e1). Moreover, 50 mass % or less is preferable and 35 mass % or less is more preferable.
The above upper and lower limits can be combined arbitrarily. For example, 5 to 50% by mass is preferable, 10 to 50% by mass is more preferable, 15 to 35% by mass is even more preferable, and 20 to 35% by mass is particularly preferable. By making it more than the said lower limit, there exists a tendency which shows a high contact angle. When the content is equal to or less than the upper limit value, there is a tendency that the outflow to the pixel portion can be suppressed.
　化合物（ｅ１）の有するシロキサン鎖は、具体的には下記構造式（Ｅ）で表されるポリシロキサンが好ましい。
　Ｒ１Ｒ２Ｒ３Ｓｉ－Ｏ－（ＳｉＲ４Ｒ５－Ｏ）ｎ―ＳｉＲ６Ｒ７Ｒ８　（Ｅ）
　ここでＲ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６、Ｒ７、Ｒ８はそれぞれ独立して１価の有機基または水素原子を示す。
　１価の有機基として好ましくは、炭素数１～１０の炭化水素基であり、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基などのアルキル基；ビニル基、アリル基、ブテニル基、ペンテニル基、ヘキセニル基などのアルケニル基；フェニル基、トリル基、キシリル基などのアリール基；ベンジル基、フェネチル基などのアラルキル基；クロロメチル基、３－クロロプロピル基、３，３，３－トリフルオロプロピル基、ノナフルオロブチルエチル基などの置換アルキル基が挙げられ、これらの有機基はエステル結合を有していてもよい。
　ｎは０以上の整数であり、好ましくは５以上、より好ましくは１０以上であり、また、好ましくは２０００以下、より好ましくは１５００以下、さらに好ましくは１０００以下、よりさらに好ましくは５００以下、特に好ましくは３００以下である。
　上記の上限及び下限は任意に組み合わせることができる。例えば、好ましくは５～２０００、より好ましくは５～１５００、さらに好ましくは５～１０００、よりさらに好ましくは１０～５００、特に好ましくは１０～３００である。前記下限値以上とすることで撥インク性が高くなる傾向がある。前記上限値以下とすることで塗膜の均一性が高くなる傾向がある。 Specifically, the siloxane chain possessed by the compound (e1) is preferably polysiloxane represented by the following structural formula (E).
R 1 R 2 R 3 Si—O—(SiR 4 R 5 —O)n—SiR 6 R 7 R 8 (E)
Here, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 each independently represent a monovalent organic group or a hydrogen atom.
The monovalent organic group is preferably a hydrocarbon group having 1 to 10 carbon atoms, such as an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group; a vinyl group. , allyl group, butenyl group, pentenyl group, alkenyl group such as hexenyl group; aryl group such as phenyl group, tolyl group, xylyl group; benzyl group, aralkyl group such as phenethyl group; Examples thereof include substituted alkyl groups such as 3,3,3-trifluoropropyl group and nonafluorobutylethyl group, and these organic groups may have an ester bond.
n is an integer of 0 or more, preferably 5 or more, more preferably 10 or more, preferably 2000 or less, more preferably 1500 or less, still more preferably 1000 or less, even more preferably 500 or less, particularly preferably is 300 or less.
The above upper and lower limits can be combined arbitrarily. For example, it is preferably 5-2000, more preferably 5-1500, still more preferably 5-1000, even more preferably 10-500, and particularly preferably 10-300. The ink repellency tends to be enhanced by making it equal to or higher than the lower limit. When the content is equal to or less than the above upper limit, there is a tendency that the uniformity of the coating film becomes high.
　架橋基及びシロキサン鎖を有する撥液剤の市販品としては、例えば、ビックケミー社製「ＢＹＫ－ＵＶ３５００シリーズ」、大成ファインケミカル社製「８ＳＳ」シリーズの商品名で市販されている化合物を使用することができる。
　フッ素とシロキサンを両方含有するものとしては大成ファインケミカル社製「８ＦＳ」シリーズ、信越化学工業社製「ＫＰシリーズ」の商品名で市販されている化合物が挙げられる。 Examples of commercially available liquid repellent agents having a cross-linking group and a siloxane chain include compounds commercially available under the trade names of "BYK-UV3500 series" manufactured by BYK Chemie and "8SS" series manufactured by Taisei Fine Chemicals. .
Examples of compounds containing both fluorine and siloxane include those commercially available under the trade names of "8FS" series manufactured by Taisei Fine Chemicals Co., Ltd. and "KP series" manufactured by Shin-Etsu Chemical Co., Ltd.
　化合物（ｅ１）の分子量は特に制限されず、低分子量の化合物でも、高分子量体であってもよい。現像時の染み出しやポストベークによる流動性が抑えられ、隔壁からの流出を抑えることができるため、高分子量体が好ましい。化合物（ｅ１）が高分子量体である場合、化合物（ｅ１）の数平均分子量は、１００以上が好ましく、５００以上がより好ましく、また、１５００００以下が好ましく、１４００００以下がより好ましく、１３００００以下がさらに好ましく、１２００００以下が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１００～１５００００が好ましく、１００～１４００００がより好ましく、５００～１３００００がさらに好ましく、５００～１２００００が特に好ましい。 The molecular weight of compound (e1) is not particularly limited, and it may be a low molecular weight compound or a high molecular weight compound. High-molecular-weight materials are preferable because they can suppress exudation during development and fluidity due to post-baking, and can suppress outflow from partition walls. When the compound (e1) is a high molecular weight compound, the number average molecular weight of the compound (e1) is preferably 100 or more, more preferably 500 or more, preferably 150000 or less, more preferably 140000 or less, and further preferably 130000 or less. Preferably, 120,000 or less is particularly preferable.
The above upper and lower limits can be combined arbitrarily. For example, 100 to 150,000 is preferred, 100 to 140,000 is more preferred, 500 to 130,000 is even more preferred, and 500 to 120,000 is particularly preferred.
　本発明の着色感光性樹脂組成物における（ｅ）撥液剤の含有割合は特に限定されない。着色感光性樹脂組成物の全固形分量中に、好ましくは０．０１質量％以上、より好ましくは０．０５質量％以上、さらに好ましくは０．１質量％以上であり、また、好ましくは５質量％以下、より好ましくは３質量％以下、さらに好ましくは２質量％以下である。
　上記の上限及び下限は任意に組み合わせることができる。例えば、０．０１～５質量％が好ましく、０．０５～３質量％がより好ましく、０．１～２質量％がさらに好ましい。前記下限値以上とすることで撥インク性が向上する傾向がある。前記上限値以下とすることで隔壁形成後にインクを画素部に塗布する時に均一な塗膜が得られやすくなる傾向がある。 The content of (e) liquid repellent agent in the colored photosensitive resin composition of the present invention is not particularly limited. The total solid content of the colored photosensitive resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and preferably 5% by mass. % or less, more preferably 3 mass % or less, and still more preferably 2 mass % or less.
The above upper and lower limits can be combined arbitrarily. For example, 0.01 to 5% by mass is preferable, 0.05 to 3% by mass is more preferable, and 0.1 to 2% by mass is even more preferable. The ink repellency tends to be improved by making it equal to or higher than the lower limit. When the thickness is equal to or less than the above upper limit, there is a tendency that a uniform coating film can be easily obtained when the ink is applied to the pixel portion after the formation of the partition walls.
　本発明の着色感光性樹脂組成物における化合物（ｅ１）の含有割合は特に限定されない。着色感光性樹脂組成物の全固形分量中に好ましくは０．０１質量％以上、より好ましくは０．０５質量％以上、さらに好ましくは０．１質量％以上であり、また、好ましくは５質量％以下、より好ましくは３質量％以下、さらに好ましくは２質量％以下である。
　上記の上限及び下限は任意に組み合わせることができる。例えば、０．０１～５質量％が好ましく、０．０５～３質量％がより好ましく、０．１～２質量％がさらに好ましい。前記下限値以上とすることで撥インク性が向上する傾向がある。前記上限値以下とすることで隔壁形成後にインクを画素部に塗布する時に均一な塗膜が得られやすくなる傾向がある。 The content of compound (e1) in the colored photosensitive resin composition of the present invention is not particularly limited. The total solid content of the colored photosensitive resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and preferably 5% by mass. Below, more preferably 3% by mass or less, still more preferably 2% by mass or less.
The above upper and lower limits can be combined arbitrarily. For example, 0.01 to 5% by mass is preferable, 0.05 to 3% by mass is more preferable, and 0.1 to 2% by mass is even more preferable. The ink repellency tends to be improved by making it equal to or higher than the lower limit. When the thickness is equal to or less than the above upper limit, there is a tendency that a uniform coating film can be easily obtained when the ink is applied to the pixel portion after the formation of the partition walls.
　化合物（ｅ１）として、架橋基及びフッ素原子を有する撥液剤を含有する場合、本発明の着色感光性樹脂組成物における架橋基及びフッ素原子を有する撥液剤の含有割合は特に限定されない。着色感光性樹脂組成物の全固形分量中に好ましくは０．０１質量％以上、より好ましくは０．０５質量％以上、さらに好ましくは０．１質量％以上であり、また、好ましくは５質量％以下、より好ましくは３質量％以下、さらに好ましくは２質量％以下である。
　上記の上限及び下限は任意に組み合わせることができる。例えば、０．０１～５質量％が好ましく、０．０５～３質量％がより好ましく、０．１～２質量％がさらに好ましい。前記下限値以上とすることで撥インク性が向上する傾向がある。前記上限値以下とすることで隔壁形成後にインクを画素部に塗布する時に均一な塗膜が得られやすくなる傾向がある。 When the compound (e1) contains a liquid-repellent agent having a cross-linking group and a fluorine atom, the content of the liquid-repellent agent having a cross-linking group and a fluorine atom in the colored photosensitive resin composition of the present invention is not particularly limited. The total solid content of the colored photosensitive resin composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and preferably 5% by mass. Below, more preferably 3% by mass or less, still more preferably 2% by mass or less.
The above upper and lower limits can be combined arbitrarily. For example, 0.01 to 5% by mass is preferable, 0.05 to 3% by mass is more preferable, and 0.1 to 2% by mass is even more preferable. The ink repellency tends to be improved by making it equal to or higher than the lower limit. When the thickness is equal to or less than the above upper limit, there is a tendency that a uniform coating film can be easily obtained when the ink is applied to the pixel portion after the formation of the partition walls.
　化合物（ｅ１）として、架橋基及びシロキサン鎖を有する撥液剤を含有する場合、本発明の着色感光性樹脂組成物における架橋基及びシロキサン鎖を有する撥液剤の含有割合は特に限定されない。着色感光性樹脂組成物の全固形分量中に好ましくは０．１質量％以上、より好ましくは０．２質量％以上、さらに好ましくは０．５質量％以上であり、また、好ましくは５質量％以下、より好ましくは３質量％以下、さらに好ましくは２質量％以下である。
　上記の上限及び下限は任意に組み合わせることができる。例えば、０．１～５質量％が好ましく、０．２～３質量％がより好ましく、０．５～２質量％がさらに好ましい。前記下限値以上とすることで撥インク性が向上する傾向がある。前記上限値以下とすることで隔壁形成後にインクを画素部に塗布する時に均一な塗膜が得られやすくなる傾向がある。 When a liquid repellent agent having a cross-linking group and a siloxane chain is contained as the compound (e1), the content of the liquid repellent agent having a cross-linking group and a siloxane chain in the colored photosensitive resin composition of the present invention is not particularly limited. The total solid content of the colored photosensitive resin composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.5% by mass or more, and preferably 5% by mass. Below, more preferably 3% by mass or less, still more preferably 2% by mass or less.
The above upper and lower limits can be combined arbitrarily. For example, 0.1 to 5% by mass is preferable, 0.2 to 3% by mass is more preferable, and 0.5 to 2% by mass is even more preferable. The ink repellency tends to be improved by making it equal to or higher than the lower limit. When the thickness is equal to or less than the above upper limit, there is a tendency that a uniform coating film can be easily obtained when the ink is applied to the pixel portion after the formation of the partition walls.
　本発明の着色感光性樹脂組成物においては、（ｅ）撥液剤と共に界面活性剤を用いてもよい。界面活性剤は、例えば、着色感光性樹脂組成物の塗布液としての塗布性、および塗布膜の現像性の向上を目的として用いることができ、シリコーン系の界面活性剤や架橋基を有さないフッ素系の界面活性剤が好ましい。
　特に、現像の際、未露光部から着色感光性樹脂組成物の残渣を除去する作用があり、また、濡れ性を発現する機能を有することから、シリコーン系界面活性剤が好ましく、ポリエーテル変性シリコーン系界面活性剤がさらに好ましい。 In the colored photosensitive resin composition of the present invention, a surfactant may be used together with (e) the liquid repellent. Surfactants, for example, can be used for the purpose of improving the applicability as a coating liquid of the colored photosensitive resin composition and the developability of the coating film, and does not have a silicone-based surfactant or a cross-linking group. Fluorinated surfactants are preferred.
In particular, during development, there is an action to remove the residue of the colored photosensitive resin composition from the unexposed area, also, since it has a function to express the wettability, silicone-based surfactant is preferable, polyether-modified silicone system surfactants are more preferred.
　架橋基を有さないフッ素系界面活性剤としては、末端、主鎖及び側鎖の少なくとも何れかの部位にフルオロアルキル又はフルオロアルキレン基を有する化合物が好適である。
　架橋基を有さないフッ素系界面活性剤の市販品としては、例えば、ＢＭ　Ｃｈｅｍｉｅ社製「ＢＭ－１０００」、「ＢＭ－１１００」、ＤＩＣ社製「メガファックＦ１４２Ｄ」、「メガファックＦ１７２」、「メガファックＦ１７３」、「メガファックＦ１８３」、「メガファックＦ４７０」、「メガファックＦ４７５」、「メガファックＦ５５４」、「メガファックＦ５５９」、スリーエムジャパン社製「ＦＣ４３０」、ネオス社製「ＤＦＸ－１８」を挙げることができる。 Compounds having a fluoroalkyl or fluoroalkylene group on at least one of the terminal, main chain and side chain are suitable as the fluorosurfactant that does not have a cross-linking group.
Examples of commercially available fluorine-based surfactants having no cross-linking group include "BM-1000" and "BM-1100" manufactured by BM Chemie, "Megaface F142D" and "Megaface F172" manufactured by DIC, "Megafac F173", "Megafac F183", "Megafac F470", "Megafac F475", "Megafac F554", "Megafac F559", 3M Japan "FC430", Neos "DFX-" 18” can be mentioned.
　シリコーン系界面活性剤の市販品としては、例えば、東レ・ダウコーニング社製「ＤＣ３ＰＡ」、「ＳＨ７ＰＡ」、「ＤＣ１１ＰＡ」、「ＳＨ２１ＰＡ」、「ＳＨ２８ＰＡ」、「ＳＨ２９ＰＡ」、「８０３２Ａｄｄｉｔｉｖｅ」、「ＳＨ８４００」、ビックケミー社製「ＢＹＫ（登録商標、以下同じ。）３２３」、「ＢＹＫ３３０」を挙げることができる。 Examples of commercially available silicone-based surfactants include "DC3PA", "SH7PA", "DC11PA", "SH21PA", "SH28PA", "SH29PA", "8032Additive", and "SH8400" manufactured by Dow Corning Toray Co., Ltd. , "BYK (registered trademark, hereinafter the same) 323" and "BYK330" manufactured by BYK-Chemie.
　界面活性剤として、フッ素系界面活性剤及びシリコーン系界面活性剤以外のものを含んでいてもよく、フッ素系界面活性剤及びシリコーン系界面活性剤以外の界面活性剤としては、ノニオン性、アニオン性、カチオン性、両性界面活性剤が挙げられる。 Surfactants other than fluorine-based surfactants and silicone-based surfactants may be included, and surfactants other than fluorine-based surfactants and silicone-based surfactants include nonionic and anionic surfactants. , cationic and amphoteric surfactants.
　ノニオン性界面活性剤としては、例えば、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンポリオキシプロピレンアルキルエーテル類、ポリオキシエチレンアルキルフェニルエーテル類、ポリオキシエチレンアルキルエステル類、ポリオキシエチレン脂肪酸エステル類、グリセリン脂肪酸エステル類、ポリオキシエチレングリセリン脂肪酸エステル類、ペンタエリスリット脂肪酸エステル類、ポリオキシエチレンペンタエリスリット脂肪酸エステル類、ソルビタン脂肪酸エステル類、ポリオキシエチレンソルビタン脂肪酸エステル類、ソルビット脂肪酸エステル類、ポリオキシエチレンソルビット脂肪酸エステル類が挙げられる。
　ノニオン性界面活性剤の市販品としては、例えば、花王社製の「エマルゲン（登録商標、以下同じ。）１０４Ｐ」、「エマルゲンＡ６０」等のポリオキシエチレン系界面活性剤が挙げられる。 Nonionic surfactants include, for example, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, glycerin Fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythrityl fatty acid esters, polyoxyethylene pentaerythritic fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbit fatty acid esters, polyoxyethylene sorbitol fatty acid esters.
Examples of commercially available nonionic surfactants include polyoxyethylene-based surfactants such as "Emulgen (registered trademark, hereinafter the same.) 104P" and "Emulgen A60" manufactured by Kao Corporation.
　アニオン性界面活性剤としては、例えば、アルキルスルホン酸塩類、アルキルベンゼンスルホン酸塩類、アルキルナフタレンスルホン酸塩類、ポリオキシエチレンアルキルエーテルスルホン酸塩類、アルキル硫酸塩類、アルキル硫酸エステル塩類、高級アルコール硫酸エステル塩類、脂肪族アルコール硫酸エステル塩類、ポリオキシエチレンアルキルエーテル硫酸塩類、ポリオキシエチレンアルキルフェニルエーテル硫酸塩類、アルキル燐酸エステル塩類、ポリオキシエチレンアルキルエーテル燐酸塩類、ポリオキシエチレンアルキルフェニルエーテル燐酸塩類、特殊高分子系界面活性剤が挙げられる。中でも、特殊高分子系界面活性剤が好ましく、特殊ポリカルボン酸型高分子系界面活性剤がさらに好ましい。
　アニオン性界面活性剤の市販品としては、アルキル硫酸エステル塩類では、例えば、花王社製「エマール（登録商標、以下同じ。）１０」、アルキルナフタレンスルホン酸塩類では、例えば、花王社製「ペレックス（登録商標。）ＮＢ－Ｌ」、特殊高分子系界面活性剤では、例えば、花王社製「ホモゲノール（登録商標、以下同じ。）Ｌ－１８」、「ホモゲノールＬ－１００」が挙げられる。 Examples of anionic surfactants include alkylsulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, polyoxyethylene alkylethersulfonates, alkylsulfates, alkylsulfates, higher alcohol sulfates, Fatty alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, special polymer Surfactants are included. Among them, a special polymeric surfactant is preferable, and a special polycarboxylic acid type polymeric surfactant is more preferable.
Commercially available anionic surfactants include, for example, "Emal (registered trademark, hereinafter the same.) 10" manufactured by Kao Corporation for alkyl sulfate ester salts, and "Perex (registered trademark) manufactured by Kao Corporation" for alkylnaphthalene sulfonates. Registered trademark NB-L”, and special polymeric surfactants include, for example, “Homogenol (registered trademark, hereinafter the same) L-18” and “Homogenol L-100” manufactured by Kao Corporation.
　カチオン性界面活性剤としては、例えば、第４級アンモニウム塩類、イミダゾリン誘導体類、アルキルアミン塩類が挙げられる。また、両性界面活性剤としては、例えば、ベタイン型化合物類、イミダゾリウム塩類、イミダゾリン類、アミノ酸類が挙げられる。第４級アンモニウム塩類が好ましく、ステアリルトリメチルアンモニウム塩類がさらに好ましい。
　カチオン性界面活性剤の市販品としては、アルキルアミン塩類では、例えば、花王社製「アセタミン（登録商標。）２４」、第４級アンモニウム塩類では、例えば、花王社製「コータミン（登録商標、以下同じ。）２４Ｐ」、「コータミン８６Ｗ」が挙げられる。 Cationic surfactants include, for example, quaternary ammonium salts, imidazoline derivatives, and alkylamine salts. Examples of amphoteric surfactants include betaine-type compounds, imidazolium salts, imidazolines, and amino acids. Quaternary ammonium salts are preferred, and stearyltrimethylammonium salts are more preferred.
Examples of commercially available cationic surfactants include alkylamine salts such as "Acetamine (registered trademark) 24" manufactured by Kao Corporation, and quaternary ammonium salts such as "Cortamine (registered trademark)" manufactured by Kao Corporation. The same.) 24P” and “Cortamine 86W”.
　界面活性剤は１種単独で用いてもよく、２種類以上を組み合わせて使用してもよい。例えば、シリコーン系界面活性剤とフッ素系界面活性剤との組み合わせ、シリコーン系界面活性剤と特殊高分子系界面活性剤との組み合わせ、フッ素系界面活性剤と特殊高分子系界面活性剤との組み合わせが挙げられる。シリコーン系界面活性剤とフッ素系界面活性剤との組み合わせが好ましい。
　シリコーン系界面活性剤とフッ素系界面活性剤との組み合わせでは、例えば、ネオス社製「ＤＦＸ－１８」、ビックケミー社製「ＢＹＫ－３００」または「ＢＹＫ－３３０」とＡＧＣセイミケミカル社製「Ｓ－３９３」との組み合わせ；信越シリコーン社製「ＫＰ３４０」とＤＩＣ社製「Ｆ－５５４」または「Ｆ－５５９」との組み合わせ；東レ・ダウコーニング社製「ＳＨ７ＰＡ」とダイキン社製「ＤＳ－４０１」との組み合わせ；ＮＵＣ社製「Ｌ－７７」とスリーエムジャパン社製「ＦＣ４４３０」との組み合わせが挙げられる。 Surfactants may be used singly or in combination of two or more. For example, a combination of a silicone-based surfactant and a fluorine-based surfactant, a combination of a silicone-based surfactant and a special polymer surfactant, and a combination of a fluorine-based surfactant and a special polymer-based surfactant. is mentioned. A combination of a silicone surfactant and a fluorosurfactant is preferred.
In the combination of a silicone-based surfactant and a fluorine-based surfactant, for example, "DFX-18" manufactured by Neos, "BYK-300" or "BYK-330" manufactured by BYK-Chemie and "S-" manufactured by AGC Seimi Chemical Co., Ltd. 393”; Combination of Shin-Etsu Silicone Co., Ltd. “KP340” and DIC “F-554” or “F-559”; Toray Dow Corning Co., Ltd. “SH7PA” and Daikin Co., Ltd. “DS-401” Combination with: A combination of "L-77" manufactured by NUC and "FC4430" manufactured by 3M Japan.
［１－１－６］（ｆ）分散剤
　本発明の着色感光性樹脂組成物は、分散剤を含有してもよい。分散剤は、（ａ）着色剤を微細に分散させ、かつその分散状態を安定化させる。
　（ｆ）分散剤としては、官能基を有する高分子分散剤が好ましく、さらに、分散安定性の面からカルボキシ基；リン酸基；スルホン酸基；又はこれらの塩基；一級、二級又は三級アミノ基；四級アンモニウム塩基；ピリジン、ピリミジン、ピラジン等の含窒素ヘテロ環由来の基、等の官能基を有する高分子分散剤が好ましい。顔料を分散する際に少量の分散剤で分散することができるとの観点から、一級、二級又は三級アミノ基；四級アンモニウム塩基；ピリジン、ピリミジン、ピラジン等の含窒素ヘテロ環由来の基、等の塩基性官能基を有する高分子分散剤がより好ましい。 [1-1-6] (f) Dispersant The colored photosensitive resin composition of the present invention may contain a dispersant. The dispersant (a) finely disperses the colorant and stabilizes the dispersed state.
(f) As the dispersant, a polymer dispersant having a functional group is preferable, and further, from the viewpoint of dispersion stability, a carboxy group; a phosphoric acid group; a sulfonic acid group; or a base thereof; Polymeric dispersants having functional groups such as amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine are preferred. Primary, secondary or tertiary amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine, from the viewpoint of dispersing pigments with a small amount of dispersant Polymeric dispersants having basic functional groups such as .
　高分子分散剤としては、例えば、ウレタン系分散剤、アクリル系分散剤、ポリエチレンイミン系分散剤、ポリアリルアミン系分散剤、アミノ基を持つモノマーとマクロモノマーからなる分散剤、ポリオキシエチレンアルキルエーテル系分散剤、ポリオキシエチレンジエステル系分散剤、ポリエーテルリン酸系分散剤、ポリエステルリン酸系分散剤、ソルビタン脂肪族エステル系分散剤、脂肪族変性ポリエステル系分散剤を挙げることができる。 Polymer dispersants include, for example, urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants composed of amino group-containing monomers and macromonomers, and polyoxyethylene alkyl ether dispersants. Dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants can be mentioned.
　高分子分散剤としては、例えば、商品名で、ＥＦＫＡ（登録商標。ＢＡＳＦ社製。）、ＤＩＳＰＥＲＢＹＫ（登録商標。ビックケミー社製。）、ディスパロン（登録商標。楠本化成社製。）、ＳＯＬＳＰＥＲＳＥ（登録商標。ルーブリゾール社製。）、ＫＰ（信越化学工業社製）、ポリフロー（共栄社化学社製）、アジスパー（登録商標。味の素社製。）を挙げることができる。
　高分子分散剤は、１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of polymer dispersants include trade names such as EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by BYK-Chemie), Disparon (registered trademark, manufactured by Kusumoto Kasei), SOLSPERSE (registered trademark). (trademark, manufactured by Lubrizol Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and Ajisper (registered trademark, manufactured by Ajinomoto Co., Inc.).
Polymer dispersants may be used alone or in combination of two or more.
　高分子分散剤の重量平均分子量（Ｍｗ）は好ましくは７００以上、より好ましくは１０００以上であり、また好ましくは１０００００以下、より好ましくは５００００以下である。
　上記の上限及び下限は任意に組み合わせることができる。例えば、高分子分散剤の重量平均分子量（Ｍｗ）は７００～１０００００が好ましく、１０００～５００００がより好ましい。 The weight average molecular weight (Mw) of the polymeric dispersant is preferably 700 or more, more preferably 1000 or more, and preferably 100,000 or less, more preferably 50,000 or less.
The above upper and lower limits can be combined arbitrarily. For example, the weight average molecular weight (Mw) of the polymeric dispersant is preferably 700-100,000, more preferably 1,000-50,000.
　酸化チタン粒子の分散性の観点から、（ｆ）分散剤は酸性や塩基性の官能基を有する高分子分散剤を含むことが好ましい。
　分散性、保存性の面から、塩基性官能基を有し、ポリエステル結合及びポリエーテル結合のいずれか一方又は両方を有する高分子分散剤が好ましい。 From the viewpoint of dispersibility of titanium oxide particles, (f) the dispersant preferably contains a polymer dispersant having an acidic or basic functional group.
From the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and either one or both of a polyester bond and a polyether bond is preferred.
　アクリル系高分子分散剤としては、官能基（ここでいう官能基とは、高分子分散剤に含有される官能基として前述した官能基である。）を有する不飽和基含有単量体と、官能基を有さない不飽和基含有単量体とのランダム共重合体、グラフト共重合体、ブロック共重合体を使用することが好ましい。これらの共重合体は公知の方法で製造することができる。 As the acrylic polymer dispersant, an unsaturated group-containing monomer having a functional group (the functional group here is the functional group described above as the functional group contained in the polymer dispersant), It is preferable to use random copolymers, graft copolymers and block copolymers with unsaturated group-containing monomers having no functional groups. These copolymers can be produced by known methods.
　官能基を有する不飽和基含有単量体としては、例えば、（メタ）アクリル酸、２－（メタ）アクリロイロキシエチルコハク酸、２－（メタ）アクリロイロキシエチルフタル酸、２－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、アクリル酸ダイマー等のカルボキシ基を有する不飽和単量体、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート及びこれらの４級化物等の３級アミノ基、４級アンモニウム塩基を有する不飽和単量体が挙げられる。
　官能基を有する不飽和基含有単量体は１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of unsaturated group-containing monomers having functional groups include (meth) acrylic acid, 2-(meth) acryloyloxyethyl succinic acid, 2-(meth) acryloyloxyethyl phthalate, 2-(meth) ) Acryloyloxyethylhexahydrophthalic acid, unsaturated monomers having a carboxyl group such as acrylic acid dimer, tertiary amino such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate and quaternary products thereof groups, unsaturated monomers with a quaternary ammonium base.
The unsaturated group-containing monomer having a functional group may be used alone or in combination of two or more.
　官能基を有さない不飽和基含有単量体としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシメチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、トリシクロデカン（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、Ｎ－ビニルピロリドン、スチレン及びその誘導体、α－メチルスチレン、Ｎ－シクロヘキシルマレイミド、Ｎ－フェニルマレイミド、Ｎ－ベンジルマレイミド等のＮ－置換マレイミド、アクリロニトリル、酢酸ビニル及びポリメチル（メタ）アクリレートマクロモノマー、ポリスチレンマクロモノマー、ポリ２－ヒドロキシエチル（メタ）アクリレートマクロモノマー、ポリエチレングリコールマクロモノマー、ポリプロピレングリコールマクロモノマー、ポリカプロラクトンマクロモノマー等のマクロモノマーが挙げられる。
　官能基を有さない不飽和基含有単量体は１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of unsaturated group-containing monomers having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, cyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxymethyl (meth)acrylate, 2-ethylhexyl ( meth)acrylate, isobornyl (meth)acrylate, tricyclodecane (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N-vinylpyrrolidone, styrene and its derivatives, α-methylstyrene, N-cyclohexylmaleimide, N-phenylmaleimide , N-substituted maleimides such as N-benzylmaleimide, acrylonitrile, vinyl acetate and polymethyl (meth)acrylate macromonomers, polystyrene macromonomers, poly 2-hydroxyethyl (meth)acrylate macromonomers, polyethylene glycol macromonomers, polypropylene glycol macromonomers , and polycaprolactone macromonomers.
The unsaturated group-containing monomers having no functional group may be used singly or in combination of two or more.
　アクリル系高分子分散剤は、特に好ましくは、官能基を有するＡブロックと官能基を有さないＢブロックからなるＡ－Ｂ又はＢ－Ａ－Ｂブロック共重合体であるが、この場合、Ａブロック中には上記官能基を含む不飽和基含有単量体由来の部分構造の他に、上記官能基を含まない不飽和基含有単量体由来の部分構造が含まれていてもよく、これらがＡブロック中においてランダム共重合又はブロック共重合のいずれの態様で含有されていてもよい。
　官能基を含まない部分構造の、Ａブロック中の含有量は、好ましくは８０質量％以下であり、より好ましくは５０質量％以下、さらに好ましくは３０質量％以下である。 The acrylic polymer dispersant is particularly preferably an AB or BAB block copolymer consisting of an A block having a functional group and a B block having no functional group. In addition to the partial structure derived from the unsaturated group-containing monomer containing the functional group, the block may contain a partial structure derived from the unsaturated group-containing monomer that does not contain the functional group. may be contained in the A block in any form of random copolymerization or block copolymerization.
The content of the partial structure containing no functional group in the A block is preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less.
　Ｂブロックは、上記官能基を含まない不飽和基含有単量体由来の部分構造からなるものであるが、１つのＢブロック中に２種以上の単量体由来の部分構造が含有されていてもよく、これらは、Ｂブロック中においてランダム共重合又はブロック共重合のいずれの態様で含有されていてもよい。
　Ａ－Ｂ又はＢ－Ａ－Ｂブロック共重合体は、例えば、以下に示すリビング重合法にて調製される。
　リビング重合法には、アニオンリビング重合法、カチオンリビング重合法、ラジカルリビング重合法がある。 The B block consists of a partial structure derived from an unsaturated group-containing monomer that does not contain the above functional group, but one B block contains partial structures derived from two or more monomers. These may be contained in the B block in any form of random copolymerization or block copolymerization.
The AB or BAB block copolymer is prepared, for example, by the following living polymerization method.
The living polymerization method includes an anion living polymerization method, a cationic living polymerization method, and a radical living polymerization method.
　このアクリル系高分子分散剤を合成するに際しては、例えば、日本国特開平９－６２００２号公報、Ｐ．Ｌｕｔｚ，　Ｐ．Ｍａｓｓｏｎ　ｅｔ　ａｌ，　Ｐｏｌｙｍ．　Ｂｕｌｌ．　１２，　７９　（１９８４），　Ｂ．Ｃ．Ａｎｄｅｒｓｏｎ，　Ｇ．Ｄ．Ａｎｄｒｅｗｓ　ｅｔ　ａｌ，　Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ，　１４，　１６０１（１９８１），　Ｋ．Ｈａｔａｄａ，　Ｋ．Ｕｔｅ，ｅｔ　ａｌ，　Ｐｏｌｙｍ．　Ｊ．　１７，　９７７（１９８５），　１８，　１０３７（１９８６），　右手浩一、畑田耕一、高分子加工、３６，　３６６（１９８７），東村敏延、沢本光男、高分子論文集、４６，　１８９（１９８９），　Ｍ．Ｋｕｒｏｋｉ，　Ｔ．Ａｉｄａ，　Ｊ．　Ａｍ．　Ｃｈｅｍ．　Ｓｉｃ，　１０９，　４７３７（１９８７）、相田卓三、井上祥平、有機合成化学、４３，　３００（１９８５），　Ｄ．Ｙ．Ｓｏｇｏｈ，　Ｗ．Ｒ．Ｈｅｒｔｌｅｒ　ｅｔ　ａｌ，　Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ，　２０，　１４７３（１９８７）に記載の公知の方法を採用することができる。 In synthesizing this acrylic polymer dispersant, for example, Japanese Patent Laid-Open No. 9-62002, P.S. Lutz, P. Masson et al, Polym.　Bull. 12, 79 (1984), B. C. Anderson, G. D. Andrews et al, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym.　J. 17, 977 (1985), 18, 1037 (1986), Kouichi Ugi, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Kobunshi Ronbun, 46, 189 (1989), M. Kuroki, T. Aida, J.　Am.　Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D. Y. Sogoh, W. R. A known method described in Hertler et al, Macromolecules, 20, 1473 (1987) can be employed.
　本発明で用いることができるアクリル系高分子分散剤はＡ－Ｂブロック共重合体であっても、Ｂ－Ａ－Ｂブロック共重合体であってもよく、その共重合体を構成するＡブロック／Ｂブロック比は１／９９～８０／２０（質量比）が好ましく、特に５／９５～６０／４０（質量比）がより好ましい。前記範囲内にすることで分散性と保存安定性のバランスの確保ができる傾向がある。
　本発明で用いることができるＡ－Ｂブロック共重合体、Ｂ－Ａ－Ｂブロック共重合体１ｇ中の４級アンモニウム塩基の量は、０．１～１０ｍｍｏｌであることが好ましい。前記範囲内にすることで良好な分散性を確保できる傾向がある。 The acrylic polymer dispersant that can be used in the present invention may be an AB block copolymer or a BAB block copolymer, and the A block constituting the copolymer The /B block ratio is preferably 1/99 to 80/20 (mass ratio), and more preferably 5/95 to 60/40 (mass ratio). By setting the amount within the above range, there is a tendency that a balance between dispersibility and storage stability can be ensured.
The amount of the quaternary ammonium base in 1 g of the AB block copolymer or BAB block copolymer that can be used in the present invention is preferably 0.1 to 10 mmol. By setting the amount within the above range, there is a tendency that good dispersibility can be ensured.
　このようなブロック共重合体中に、製造過程で生じたアミノ基が含有される場合、そのアミン価は１～１００ｍｇＫＯＨ／ｇが好ましく、分散性の観点から、好ましくは１０ｍｇＫＯＨ／ｇ以上、より好ましくは３０ｍｇＫＯＨ／ｇ以上、さらに好ましくは５０ｍｇＫＯＨ／ｇ以上、また、好ましくは９０ｍｇＫＯＨ／ｇ以下、より好ましくは８０ｍｇＫＯＨ／ｇ以下、さらに好ましくは７５ｍｇＫＯＨ／ｇ以下である。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～１００ｍｇＫＯＨ／ｇが好ましく、１０～９０ｍｇＫＯＨ／ｇがより好ましく、３０～８０ｍｇＫＯＨ／ｇがさらに好ましく、５０～７５ｍｇＫＯＨ／ｇが特に好ましい。
　ブロック共重合体等の分散剤のアミン価は、分散剤試料中の溶剤を除いた固形分１ｇあたりの塩基量と当量のＫＯＨの質量で表し、次の方法により測定する。 When such a block copolymer contains an amino group generated in the production process, the amine value is preferably 1 to 100 mgKOH/g, and from the viewpoint of dispersibility, preferably 10 mgKOH/g or more, more preferably. is 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, preferably 90 mgKOH/g or less, more preferably 80 mgKOH/g or less, still more preferably 75 mgKOH/g or less.
The above upper and lower limits can be combined arbitrarily. For example, 1 to 100 mgKOH/g is preferred, 10 to 90 mgKOH/g is more preferred, 30 to 80 mgKOH/g is even more preferred, and 50 to 75 mgKOH/g is particularly preferred.
The amine value of a dispersant such as a block copolymer is expressed by the mass of KOH equivalent to the amount of base per 1 g of solid content excluding the solvent in the dispersant sample, and is measured by the following method.
　１００ｍＬのビーカーに分散剤試料の０．５～１．５ｇを精秤し、５０ｍＬの酢酸で溶解する。ｐＨ電極を備えた自動滴定装置を使って、この溶液を０．１ｍｏｌ／ＬのＨＣｌＯ4酢酸溶液にて中和滴定する。滴定ｐＨ曲線の変曲点を滴定終点とし次式によりアミン価を求める。 Accurately weigh 0.5 to 1.5 g of a dispersant sample in a 100 mL beaker and dissolve it in 50 mL of acetic acid. Using an automatic titrator equipped with a pH electrode, this solution is neutralized and titrated with a 0.1 mol/L HClO 4 acetic acid solution. The inflection point of the titration pH curve is defined as the end point of the titration, and the amine value is obtained by the following formula.
　アミン価［ｍｇＫＯＨ／ｇ］＝（５６１×Ｖ）／（Ｗ×Ｓ）〔但し、Ｗ：分散剤試料秤取量［ｇ］、Ｖ：滴定終点での滴定量［ｍＬ］、Ｓ：分散剤試料の固形分濃度［質量％］を表す。〕 Amine value [mgKOH / g] = (561 × V) / (W × S) [W: dispersant sample weighed amount [g], V: titration amount at the end point of titration [mL], S: dispersant It represents the solid content concentration [mass %] of the sample. ]
　ブロック共重合体の酸価は、その酸価の元となる酸性基の有無及び種類にもよるが、低い方が好ましく、好ましくは１０ｍｇＫＯＨ／ｇ以下である。
　ブロック共重合体の重量平均分子量（Ｍｗ）は、１０００～１０００００の範囲が好ましい。前記範囲内とすることで良好な分散性を確保できる傾向がある。 The acid value of the block copolymer is preferably as low as possible, preferably 10 mgKOH/g or less, although it depends on the presence and type of acidic groups that are the source of the acid value.
The weight average molecular weight (Mw) of the block copolymer is preferably in the range of 1,000 to 100,000. Within the above range, there is a tendency to ensure good dispersibility.
　高分子分散剤にアミノ基が含有される場合、そのアミン価は１～１００ｍｇＫＯＨ／ｇが好ましく、分散性の観点から、好ましくは１０ｍｇＫＯＨ／ｇ以上、より好ましくは３０ｍｇＫＯＨ／ｇ以上、さらに好ましくは５０ｍｇＫＯＨ／ｇ以上、また、好ましくは９０ｍｇＫＯＨ／ｇ以下、より好ましくは８０ｍｇＫＯＨ／ｇ以下、さらに好ましくは７５ｍｇＫＯＨ／ｇ以下である。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～１００ｍｇＫＯＨ／ｇが好ましく、１０～９０ｍｇＫＯＨ／ｇがより好ましく、３０～８０ｍｇＫＯＨ／ｇがさらに好ましく、５０～７５ｍｇＫＯＨ／ｇが特に好ましい。 When the polymer dispersant contains an amino group, the amine value is preferably 1 to 100 mgKOH/g, and from the viewpoint of dispersibility, preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, and still more preferably 50 mgKOH. /g or more, preferably 90 mgKOH/g or less, more preferably 80 mgKOH/g or less, still more preferably 75 mgKOH/g or less.
The above upper and lower limits can be combined arbitrarily. For example, 1 to 100 mgKOH/g is preferred, 10 to 90 mgKOH/g is more preferred, 30 to 80 mgKOH/g is even more preferred, and 50 to 75 mgKOH/g is particularly preferred.
　高分子分散剤に酸性基が含有される場合は、酸性基の有無及び種類にもよるが、その酸価は低い方が好ましく、好ましくは１０ｍｇＫＯＨ／ｇ以下である。 When the polymeric dispersant contains an acidic group, the acid value is preferably as low as possible, preferably 10 mgKOH/g or less, depending on the presence or absence and type of the acidic group.
　高分子分散剤の重量平均分子量（Ｍｗ）は、１０００～１０００００の範囲が好ましい。前記範囲内とすることで良好な分散性を確保できる傾向がある。 The weight average molecular weight (Mw) of the polymer dispersant is preferably in the range of 1000-100000. Within the above range, there is a tendency to ensure good dispersibility.
　本発明の着色感光性樹脂組成物が（ｆ）分散剤を含有する場合、その含有割合は特に限定されない。着色感光性樹脂組成物の全固形分量に対して、０．１質量％以上が好ましく、０．５質量％以上がより好ましく、また、８質量％以下が好ましく、５質量％以下がより好ましく、３質量％以下がさらに好ましく、２質量％以下が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、０．１～８質量％が好ましく、０．１～５質量％がより好ましく、０．５～３質量％がさらに好ましく、０．５～２質量％が特に好ましい。前記下限値以上とすることで凝集物による残渣発生を抑制できる傾向がある。前記上限値以下とすることで撥インク性や現像性が向上する傾向がある。 When the colored photosensitive resin composition of the present invention contains (f) a dispersant, its content is not particularly limited. It is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, preferably 8% by mass or less, and more preferably 5% by mass or less, relative to the total solid content of the colored photosensitive resin composition. 3% by mass or less is more preferable, and 2% by mass or less is particularly preferable.
The above upper and lower limits can be combined arbitrarily. For example, 0.1 to 8% by mass is preferable, 0.1 to 5% by mass is more preferable, 0.5 to 3% by mass is even more preferable, and 0.5 to 2% by mass is particularly preferable. When the content is equal to or higher than the lower limit, there is a tendency to suppress the generation of residue due to aggregates. When the amount is equal to or less than the above upper limit, ink repellency and developability tend to be improved.
　（ｆ）分散剤の含有割合は、（ａ）着色剤１００質量部に対し、１質量部以上が好ましく、２質量部以上がより好ましく、３質量部以上がさらに好ましく、また、２５質量部以下が好ましく、２０質量部以下がより好ましく、１５質量部以下がさらに好ましく、１２質量部以下が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～２５質量部が好ましく、３～２０質量部がより好ましく、５～１５質量部がさらに好ましく、５～１２質量部が特に好ましい。前記下限値以上とすることで凝集物による残渣発生を抑制できる傾向がある。前記上限値以下とすることで撥インク性や現像性が向上する傾向がある。 (f) The content of the dispersant is preferably 1 part by mass or more, more preferably 2 parts by mass or more, still more preferably 3 parts by mass or more, and 25 parts by mass or less with respect to 100 parts by mass of the (a) colorant. is preferred, 20 parts by mass or less is more preferred, 15 parts by mass or less is even more preferred, and 12 parts by mass or less is particularly preferred.
The above upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 25 parts by mass, more preferably 3 to 20 parts by mass, even more preferably 5 to 15 parts by mass, and particularly preferably 5 to 12 parts by mass. When the content is equal to or higher than the lower limit, there is a tendency to suppress the generation of residue due to aggregates. When the amount is equal to or less than the above upper limit, ink repellency and developability tend to be improved.
　（ｆ）分散剤の含有割合は、（ａ１）酸化チタン粒子１００質量部に対し、１質量部以上が好ましく、３質量部以上がより好ましく、５質量部以上がさらに好ましく、また、２５質量部以下が好ましく、２０質量部以下がより好ましく、１５質量部以下がさらに好ましく、１２質量部以下が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～２５質量部が好ましく、３～２０質量部がより好ましく、５～１５質量部がさらに好ましく、５～１２質量部が特に好ましい。前記下限値以上とすることで凝集物による残渣発生を抑制できる傾向がある。前記上限値以下とすることで撥インク性や現像性が向上する傾向がある。 (f) The content of the dispersing agent is preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, and 25 parts by mass with respect to 100 parts by mass of the (a1) titanium oxide particles. The following is preferable, 20 parts by mass or less is more preferable, 15 parts by mass or less is even more preferable, and 12 parts by mass or less is particularly preferable.
The above upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 25 parts by mass, more preferably 3 to 20 parts by mass, even more preferably 5 to 15 parts by mass, and particularly preferably 5 to 12 parts by mass. When the content is equal to or higher than the lower limit, there is a tendency to suppress the generation of residue due to aggregates. When the amount is equal to or less than the above upper limit, ink repellency and developability tend to be improved.
［１－１－７］紫外線吸収剤
　本発明の着色感光性樹脂組成物は、紫外線吸収剤を含有してもよい。紫外線吸収剤は、露光に用いられる光源の特定の波長を紫外線吸収剤によって吸収させることにより、光硬化分布を制御する目的で添加される。 [1-1-7] Ultraviolet Absorber The colored photosensitive resin composition of the present invention may contain an ultraviolet absorber. The UV absorber is added for the purpose of controlling the photocuring distribution by allowing the UV absorber to absorb a specific wavelength of the light source used for exposure.
［１－１－８］重合禁止剤
　本発明の感光性樹脂組成物は、重合禁止剤を含有してもよい。重合禁止剤を含有することでラジカル重合を阻害することから、得られる隔壁のテーパ角を大きくすることができる傾向がある。 [1-1-8] Polymerization Inhibitor The photosensitive resin composition of the present invention may contain a polymerization inhibitor. Since the inclusion of a polymerization inhibitor inhibits radical polymerization, there is a tendency that the taper angle of the obtained partition walls can be increased.
　重合禁止剤は、１種を単独で用いてもよく、２種以上を併用してもよい。
　（ｂ）アルカリ可溶性樹脂の製造方法によっては製造されたアルカリ可溶性樹脂に重合禁止剤が含まれることがある。その場合、アルカリ可溶性樹脂に重合禁止剤が含まれたまま用いてもよいし、樹脂中に含まれる重合禁止剤の他に、それと同一、又は異なる重合禁止剤を着色感光性樹脂組成物製造時にさらに添加してもよい。 A polymerization inhibitor may be used individually by 1 type, and may use 2 or more types together.
(b) Depending on the production method of the alkali-soluble resin, the produced alkali-soluble resin may contain a polymerization inhibitor. In that case, the polymerization inhibitor may be used as it is contained in the alkali-soluble resin, or in addition to the polymerization inhibitor contained in the resin, the same or a different polymerization inhibitor may be added during the production of the colored photosensitive resin composition. Further may be added.
　着色感光性樹脂組成物が重合禁止剤を含有する場合、その含有割合は特に限定されない。着色感光性樹脂組成物の全固形分量に対して、好ましくは０．０００５質量％以上、より好ましくは０．００１質量％以上、さらに好ましくは０．０１質量％以上であり、また、好ましくは０．１質量％以下、より好ましくは０．０８質量％以下、さらに好ましくは０．０５質量％以下である。
　上記の上限及び下限は任意に組み合わせることができる。例えば、０．０００５～０．１質量％が好ましく、０．００１～０．０８質量がより好ましく、０．０１～０．０５質量がさらに好ましい。前記下限値以上とすることでテーパ角を高くすることができる傾向がある。前記上限値以下とすることで撥インク性が高くなる傾向がある。 When the colored photosensitive resin composition contains a polymerization inhibitor, the content is not particularly limited. The total solid content of the colored photosensitive resin composition is preferably 0.0005% by mass or more, more preferably 0.001% by mass or more, still more preferably 0.01% by mass or more, and preferably 0 0.1% by mass or less, more preferably 0.08% by mass or less, and even more preferably 0.05% by mass or less.
The above upper and lower limits can be combined arbitrarily. For example, 0.0005 to 0.1% by mass is preferable, 0.001 to 0.08% by mass is more preferable, and 0.01 to 0.05% by mass is even more preferable. The taper angle tends to be increased by making it equal to or greater than the lower limit. The ink repellency tends to be enhanced by making it equal to or less than the above upper limit.
［１－１－９］熱重合開始剤
　本発明の着色感光性樹脂組成物は、熱重合開始剤を含有してもよい。熱重合開始剤を含有することで、膜の架橋度を高くできる傾向がある。
　熱重合開始剤としては、例えば、アゾ系化合物、有機過酸化物、過酸化水素が挙げられる。
　熱重合開始剤は１種を単独で用いてもよく、２種以上を併用してもよい。 [1-1-9] Thermal polymerization initiator The colored photosensitive resin composition of the invention may contain a thermal polymerization initiator. Inclusion of a thermal polymerization initiator tends to increase the degree of cross-linking of the film.
Thermal polymerization initiators include, for example, azo compounds, organic peroxides, and hydrogen peroxide.
The thermal polymerization initiator may be used singly or in combination of two or more.
　光重合開始剤に撥インク性の向上や膜の架橋密度の増大を期待して熱重合開始剤を併用する場合、熱重合開始剤の含有割合の合計が、着色感光性樹脂組成物中の光重合開始剤の含有割合となるようにすることが好ましく、また、光重合開始剤と熱重合開始剤との併用割合としては、撥インク性の観点から、光重合開始剤１００質量部に対して熱重合開始剤を５～３００質量部とすることが好ましい。 When a thermal polymerization initiator is used in combination with the expectation of improving the ink repellency of the photopolymerization initiator and increasing the crosslink density of the film, the total content of the thermal polymerization initiator is It is preferable that the content ratio of the polymerization initiator is the same, and the ratio of the photopolymerization initiator and the thermal polymerization initiator used together is, from the viewpoint of ink repellency, relative to 100 parts by mass of the photopolymerization initiator. It is preferable to use 5 to 300 parts by mass of the thermal polymerization initiator.
［１－１－１０］アミノ化合物
　本発明の着色感光性樹脂組成物は、アミノ化合物を含んでもよい。アミノ化合物は熱硬化を促進する。 [1-1-10] Amino Compound The colored photosensitive resin composition of the present invention may contain an amino compound. Amino compounds accelerate thermosetting.
　本発明の着色感光性樹脂組成物にアミノ化合物が含まれる場合、アミノ化合物の含有割合としては、着色感光性樹脂組成物の全固形分量に対して、好ましくは４０質量％以下、より好ましくは３０質量％以下であり、また、好ましくは０．５質量％以上、より好ましくは１質量％以上である。
　上記の上限及び下限は任意に組み合わせることができる。例えば、０．５～４０質量％が好ましく、１～３０質量％がより好ましい。前記上限値以下とすることで保存安定性を維持できる傾向がある。前記下限値以上とすることで十分な熱硬化性を確保できる傾向がある。 When the colored photosensitive resin composition of the present invention contains an amino compound, the content of the amino compound is preferably 40% by mass or less, more preferably 30% by mass, based on the total solid content of the colored photosensitive resin composition. % by mass or less, preferably 0.5% by mass or more, more preferably 1% by mass or more.
The above upper and lower limits can be combined arbitrarily. For example, 0.5 to 40% by mass is preferable, and 1 to 30% by mass is more preferable. When the content is equal to or less than the above upper limit, there is a tendency that the storage stability can be maintained. There is a tendency that sufficient thermosetting property can be ensured by setting the content to be at least the above lower limit.
　アミノ化合物としては、例えば、官能基としてメチロール基、それを炭素数１～８のアルコール縮合変性したアルコキシメチル基を少なくとも２個有するアミノ化合物が挙げられる。
　具体的には、例えば、メラミンとホルムアルデヒドとを重縮合させたメラミン樹脂；ベンゾグアナミンとホルムアルデヒドとを重縮合させたベンゾグアナミン樹脂；グリコールウリルとホルムアルデヒドとを重縮合させたグリコールウリル樹脂；尿素とホルムアルデヒドとを重縮合させた尿素樹脂；メラミン、ベンゾグアナミン、グリコールウリル、または尿素等の２種以上とホルムアルデヒドとを共重縮合させた樹脂；上述の樹脂のメチロール基をアルコール縮合変性した変性樹脂が挙げられる。
　これらは１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of amino compounds include amino compounds having a methylol group as a functional group and at least two alkoxymethyl groups obtained by subjecting the methylol group to condensation-denaturation with an alcohol having 1 to 8 carbon atoms.
Specifically, for example, melamine resin obtained by polycondensation of melamine and formaldehyde; benzoguanamine resin obtained by polycondensation of benzoguanamine and formaldehyde; glycoluril resin obtained by polycondensation of glycoluril and formaldehyde; Polycondensed urea resins; resins obtained by co-polycondensing two or more of melamine, benzoguanamine, glycoluril, or urea with formaldehyde; and modified resins obtained by modifying the methylol groups of the above resins by alcohol condensation.
These may be used individually by 1 type, and may use 2 or more types together.
［１－１－１１］シランカップリング剤
　本発明の着色感光性樹脂組成物は、シランカップリング剤を含んでもよい。シランカップリング剤は、基板との密着性を改善する。 [1-1-11] Silane Coupling Agent The colored photosensitive resin composition of the present invention may contain a silane coupling agent. A silane coupling agent improves adhesion to the substrate.
　シランカップリング剤としては、例えば、エポキシ系、メタクリル系、アミノ系、イミダゾール系のシランカップリング剤が使用できるが、密着性向上の観点から、特にエポキシ系、イミダゾール系のシランカップリング剤が好ましい。
　本発明の着色感光性樹脂組成物がシランカップリング剤を含有する場合、その含有量は、密着性の観点から、着色感光性樹脂組成物の全固形分量に対して、好ましくは２０質量％以下、より好ましくは１５質量％以下である。 As the silane coupling agent, for example, epoxy-based, methacrylic-based, amino-based, and imidazole-based silane coupling agents can be used. From the viewpoint of improving adhesion, epoxy-based and imidazole-based silane coupling agents are particularly preferable. .
When the colored photosensitive resin composition of the present invention contains a silane coupling agent, the content thereof is preferably 20% by mass or less based on the total solid content of the colored photosensitive resin composition from the viewpoint of adhesion. , more preferably 15% by mass or less.
［１－１－１２］無機充填剤
　本発明の着色感光性樹脂組成物は、無機充填剤を含んでもよい。無機充填材は、硬化物としての強度の向上と共に、（ｂ）アルカリ可溶性樹脂との適度な相互作用（マトリックス構造の形成）による塗布膜の優れた垂直性とテーパ角の向上等を目的として配合される。 [1-1-12] Inorganic filler The colored photosensitive resin composition of the present invention may contain an inorganic filler. Inorganic fillers are blended for the purpose of improving the strength of the cured product and (b) improving the verticality and taper angle of the coating film by moderate interaction with the alkali-soluble resin (formation of the matrix structure). be done.
　無機充填剤としては、例えば、タルク、シリカ、或いは、これらを各種シランカップリング剤により表面処理したものが挙げられる。 Examples of inorganic fillers include talc, silica, and those surface-treated with various silane coupling agents.
　無機充填剤の平均粒子径としては、好ましくは０．００５～２μｍ、より好ましくは０．０１～１μｍである。
　平均粒子径は、ベックマン・コールター社製等のレーザー回折散乱粒度分布測定装置にて測定した値である。
　無機充填剤のうち、特に、シリカゾルおよびシリカゾル変性物は、分散安定性と共にテーパ角の向上効果に優れる傾向があるため、好ましい。 The average particle size of the inorganic filler is preferably 0.005-2 μm, more preferably 0.01-1 μm.
The average particle size is a value measured with a laser diffraction scattering particle size distribution measuring device such as manufactured by Beckman Coulter.
Among inorganic fillers, silica sol and modified silica sol are particularly preferable because they tend to be excellent in the effect of improving the taper angle as well as the dispersion stability.
　本発明の着色感光性樹脂組成物が無機充填剤を含む場合、その含有量としては、撥インク性の観点から、着色感光性樹脂組成物の全固形分量に対して、好ましくは５質量％以上、より好ましくは１０質量％以上であり、好ましくは８０質量％以下、より好ましくは７０質量％以下である。
　上記の上限及び下限は任意に組み合わせることができる。例えば、５～８０質量％が好ましく、１０～７０質量％がより好ましい。 When the colored photosensitive resin composition of the present invention contains an inorganic filler, the content thereof is preferably 5% by mass or more based on the total solid content of the colored photosensitive resin composition from the viewpoint of ink repellency. , more preferably 10% by mass or more, preferably 80% by mass or less, and more preferably 70% by mass or less.
The above upper and lower limits can be combined arbitrarily. For example, 5 to 80% by mass is preferable, and 10 to 70% by mass is more preferable.
［１－１－１３］密着性向上剤
　本発明の着色感光性樹脂組成物は、密着性向上剤を含んでもよい。密着性向上剤は、基板との密着性を付与する。 [1-1-13] Adhesion Improver The colored photosensitive resin composition of the present invention may contain an adhesion improver. The adhesion improver imparts adhesion to the substrate.
　密着性向上剤としては、例えば、リン酸系のエチレン性単量体が挙げられる。
　リン酸系のエチレン性単量体としては、（メタ）アクリロイルオキシ基含有ホスフェート類が好ましく、下記一般式（ｇ１）、（ｇ２）、（ｇ３）で表されるものが好ましい。 Examples of adhesion improvers include phosphoric acid-based ethylenic monomers.
As the phosphoric acid-based ethylenic monomer, (meth)acryloyloxy group-containing phosphates are preferable, and those represented by the following general formulas (g1), (g2) and (g3) are preferable.
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
　式（ｇ１）、（ｇ２）、（ｇ３）において、Ｒ51は水素原子又はメチル基を示し、ｌ及びｌ’は１～１０の整数、ｍは１、２又は３である。 In formulas (g1), (g2) and (g3), R 51 represents a hydrogen atom or a methyl group, l and l' are integers of 1-10, and m is 1, 2 or 3.
　リン酸系エチレン性単量体は、１種類を単独で用いてもよく、２種以上を併用してもよい。 The phosphoric acid-based ethylenic monomers may be used singly or in combination of two or more.
　本発明の着色感光性樹脂組成物が密着性向上剤としてリン酸系エチレン性単量体を含む場合、その含有割合は、着色感光性樹脂組成物の全固形分量に対して、０．０２質量％以上が好ましく、０．０５質量％以上がより好ましく、０．１質量％以上がさらに好ましく、０．２質量％以上が特に好ましく、また、４質量％以下が好ましく、３質量％以下がより好ましく、２質量％以下がさらに好ましく、１質量％以下が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、０．０２～４質量％が好ましく、０．０５～３質量％がより好ましく、０．１～２質量％がさらに好ましく、０．２～１質量％が特に好ましい。前記下限値以上とすることで基板との密着性の改善効果が十分となる傾向がある。上記上限値以下とすることで基板との密着性の悪化を抑制しやすい傾向がある。 When the colored photosensitive resin composition of the present invention contains a phosphoric acid-based ethylenic monomer as an adhesion improver, the content is 0.02 mass with respect to the total solid content of the colored photosensitive resin composition. % or more is preferable, 0.05% by mass or more is more preferable, 0.1% by mass or more is more preferable, 0.2% by mass or more is particularly preferable, and 4% by mass or less is preferable, and 3% by mass or less is more preferable. It is preferably 2% by mass or less, more preferably 1% by mass or less.
The above upper and lower limits can be combined arbitrarily. For example, 0.02 to 4% by mass is preferable, 0.05 to 3% by mass is more preferable, 0.1 to 2% by mass is even more preferable, and 0.2 to 1% by mass is particularly preferable. By making it equal to or higher than the lower limit, there is a tendency that the effect of improving the adhesion to the substrate becomes sufficient. By making it equal to or less than the above upper limit, there is a tendency to easily suppress deterioration of adhesion to the substrate.
［１－１－１４］溶剤
　本発明の着色感光性樹脂組成物は、溶剤を含有してもよい。着色感光性樹脂組成物が溶剤を含有する場合、着色感光性樹脂組成物に含有される各成分を溶剤に溶解または分散させた状態で使用できる。 [1-1-14] Solvent The colored photosensitive resin composition of the present invention may contain a solvent. When the colored photosensitive resin composition contains a solvent, each component contained in the colored photosensitive resin composition can be used in a state of being dissolved or dispersed in the solvent.
　溶剤としては、特に制限されない。例えば、以下に記載する有機溶剤が挙げられる。
　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モノプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノ－ｎ－ブチルエーテル、プロピレングリコール－ｔ－ブチルエーテル、ジエチレングリコールモノメチルエーテル、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モノ－ｎ－ブチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、３－メチル－３－メトキシブタノール、３－メトキシ－１－ブタノール、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリプロピレングリコールメチルエーテルのようなグリコールモノアルキルエーテル類；
エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールエチルメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジプロピルエーテル、ジエチレングリコールジブチルエーテル、ジプロピレングリコールジメチルエーテルのようなグリコールジアルキルエーテル類；
エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノ－ｎ－ブ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アセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート、３－メトキシ－１－ブチルアセテート、メトキシペンチルアセテート、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノ－ｎ－ブチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、トリエチレングリコールモノメチルエーテルアセテート、トリエチレングリコールモノエチルエーテルアセテート、３－メチル－３－メトキシブチルアセテートのようなグリコールアルキルエーテルアセテート類；
エチレングリコールジアセテート、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、１，４－ブタンジオールジアセテート、１，６－ヘキサノールジアセテート等のグリコールジアセテート類；
シクロヘキサノールアセテート等のアルキルアセテート類；
アミルエーテル、ジエチルエーテル、ジプロピルエーテル、ジイソプロピルエーテル、ジブチルエーテル、ジアミルエーテル、エチルイソブチルエーテル、ジヘキシルエーテルのようなエーテル類；
アセトン、メチルエチルケトン、メチルイソプロピルケトン、メチルアミルケトン、メチルイソアミルケトン、ジイソプロピルケトン、ジイソブチルケトン、メチルイソブチルケトン、シクロヘキサノン、エチルアミルケトン、メチルブチルケトン、メチルヘキシルケトン、メチルノニルケトン、メトキシメチルペンタノンのようなケトン類；
メタノール、エタノール、プロパノール、ブタノール、ヘキサノール、シクロヘキサノール、エチレングリコール、プロピレングリコール、ブタンジオール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、メトキシメチルペンタノール、グリセリン、ベンジルアルコールのような１価又は多価アルコール類；
ｎ－ペンタン、ｎ－オクタン、ジイソブチレン、ｎ－ヘキサン、ヘキセン、イソプレン、ジペンテン、ドデカンのような脂肪族炭化水素類；
シクロヘキサン、メチルシクロヘキサン、メチルシクロヘキセン、ビシクロヘキシルのような脂環式炭化水素類；
ベンゼン、トルエン、キシレン、クメンのような芳香族炭化水素類；
アミルホルメート、エチルホルメート、酢酸エチル、酢酸プロピル、酢酸ブチル、酢酸アミル、メチルイソブチレート、エチルプロピオネート、プロピルプロピオネート、酪酸ブチル、酪酸イソブチル、イソ酪酸メチル、エチルカプリレート、安息香酸エチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－メトキシプロピオン酸プロピル、３－メトキシプロピオン酸ブチル、γ－ブチロラクトンのような鎖状又は環状エステル類；
３－メトキシプロピオン酸、３－エトキシプロピオン酸のようなアルコキシカルボン酸類；
ブチルクロライド、アミルクロライドのようなハロゲン化炭化水素類；
メトキシメチルペンタノンのようなエーテルケトン類；
アセトニトリル、ベンゾニトリルのようなニトリル類；
テトラヒドロフラン、ジメチルテトラヒドロフラン、ジメトキシテトラヒドロフランのようなテトラヒドロフラン類。 There are no particular restrictions on the solvent. Examples include the organic solvents described below.
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, 3-methoxy-1-butanol, triethylene glycol monomethyl ether, Glycol monoalkyl ethers such as triethylene glycol monoethyl ether, tripropylene glycol methyl ether;
Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;
ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, 3- Methoxy-1-butyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether glycol alkyl ether acetates such as acetate, 3-methyl-3-methoxybutyl acetate;
Glycol diacetates such as ethylene glycol diacetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, 1,6-hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;
Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl amyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methylhexyl ketone, methyl nonyl ketone, methoxymethyl pentanone ketones;
Monohydric or polyhydric alcohols such as methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol kind;
Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
amyl formate, ethyl formate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, methyl isobutyrate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, benzoin ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone linear or cyclic esters;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride, amyl chloride;
ether ketones such as methoxymethylpentanone;
Nitriles such as acetonitrile, benzonitrile;
Tetrahydrofurans such as tetrahydrofuran, dimethyltetrahydrofuran and dimethoxytetrahydrofuran.
　市販の溶剤としては、例えば、ミネラルスピリット、バルソル＃２、アプコ＃１８ソルベント、アプコシンナー、ソーカルソルベントＮｏ．１およびＮｏ．２、ソルベッソ＃１５０、シェルＴＳ２８　ソルベント、カルビトール、エチルカルビトール、ブチルカルビトール、メチルセロソルブ、エチルセロソルブ、エチルセロソルブアセテート、メチルセロソルブアセテート、ジグライム（いずれも商品名）が挙げられる。 Commercially available solvents include, for example, Mineral Spirit, Valsol #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No. 1 and no. 2, Solvesso #150, Shell TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names).
　溶剤は、着色感光性樹脂組成物に含有される各成分を溶解または分散させることができ、本発明の着色感光性樹脂組成物の使用方法に応じて選択される。塗布性の観点から、溶媒の大気圧下における沸点は、６０～２８０℃が好ましく、７０～２６０℃がより好ましい。中でも、プロピレングリコールモノメチルエーテル、３－メトキシ－１－ブタノール、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－１－ブチルアセテートが好ましい。 The solvent can dissolve or disperse each component contained in the colored photosensitive resin composition, and is selected according to the method of using the colored photosensitive resin composition of the present invention. From the viewpoint of coating properties, the boiling point of the solvent under atmospheric pressure is preferably 60 to 280°C, more preferably 70 to 260°C. Among them, propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, and 3-methoxy-1-butyl acetate are preferred.
　溶剤は１種を単独で用いてもよく、２種以上を併用してもよい。
　溶剤は、着色感光性樹脂組成物溶液中の全固形量の含有割合が、好ましくは１０質量％以上、より好ましくは１５質量％以上、さらに好ましくは２０質量％以上、特に好ましくは２５質量％以上、また、好ましくは９０質量％以下、より好ましくは５０質量％以下、さらに好ましくは４０質量％以下、特に好ましくは３５質量％以下となるように使用されることが好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、好ましくは１０～９０質量％、より好ましくは１５～５０質量％、さらに好ましくは２０～４０質量％、特に好ましくは２５～３５質量％となるように使用されることが好ましい。前記下限値以上とすることで塗布ムラの発生を抑制できる傾向がある。前記上限値以下とすることで異物、ハジキ等の発生を抑制できる傾向がある。 A solvent may be used individually by 1 type, and may use 2 or more types together.
The content of the solvent in the total solid content in the colored photosensitive resin composition solution is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and particularly preferably 25% by mass or more. Also, it is preferably used in an amount of 90% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, and particularly preferably 35% by mass or less.
The above upper and lower limits can be combined arbitrarily. For example, it is preferably used in an amount of 10 to 90% by mass, more preferably 15 to 50% by mass, still more preferably 20 to 40% by mass, and particularly preferably 25 to 35% by mass. By making it equal to or higher than the lower limit, there is a tendency that the occurrence of coating unevenness can be suppressed. When the content is equal to or less than the above upper limit, there is a tendency to suppress the occurrence of foreign matter, repelling, and the like.
［１－２］着色感光性樹脂組成物の調製方法
　本発明の着色感光性樹脂組成物は、着色感光性樹脂組成物に含有される各成分を撹拌機で混合することにより調製される。
　例えば、（ａ）着色剤として顔料等の溶剤不溶成分を含む場合には、予めペイントコンディショナー、サンドグラインダー、ボールミル、ロールミル、ストーンミル、ジェットミル、ホモジナイザー等を用いて分散処理することが好ましい。分散処理により（ａ）着色剤が微粒子化されるため、着色感光性樹脂組成物の塗布特性が向上する。 [1-2] Method for Preparing Colored Photosensitive Resin Composition The colored photosensitive resin composition of the present invention is prepared by mixing each component contained in the colored photosensitive resin composition with a stirrer.
For example, when (a) the colorant contains a solvent-insoluble component such as a pigment, it is preferably dispersed in advance using a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, or the like. Since the (a) colorant is finely divided by the dispersion treatment, the application properties of the colored photosensitive resin composition are improved.
　着色感光性樹脂組成物を製造する工程において、（ａ）着色剤、溶剤、及び（ｆ）分散剤を少なくとも含有する顔料分散液を製造することが好ましい。（ａ）着色剤、溶剤、及び（ｆ）分散剤を併用した系や、それらに任意で（ｂ）アルカリ可溶性樹脂の一部又は全部を併用した系にて分散処理を行うことが好ましい（以下、分散処理に供する混合物、及び分散処理にて得られた組成物を「顔料分散液」と称することがある。）。特に（ｆ）分散剤として高分子分散剤を用いると、得られた顔料分散液及び着色感光性樹脂組成物の分散安定性に優れ、経時の増粘が抑制されるため好ましい。
　顔料分散液に用いることができる（ａ）着色剤、有機溶剤、及び（ｆ）分散剤としては、それぞれ着色感光性樹脂組成物に用いることができるものとして記載したものを好ましく採用することができる。顔料分散液における（ａ）着色剤の各着色剤の含有割合としても、着色感光性樹脂組成物における含有割合として記載したものを好ましく採用することができる。 In the step of producing the colored photosensitive resin composition, it is preferable to produce a pigment dispersion containing at least (a) a colorant, a solvent, and (f) a dispersant. It is preferable to carry out dispersion treatment in a system in which (a) a coloring agent, a solvent, and (f) a dispersant are used in combination, or optionally a part or all of an alkali-soluble resin (b) is used in combination (hereinafter referred to as , the mixture subjected to dispersion treatment and the composition obtained by dispersion treatment may be referred to as "pigment dispersion"). In particular, it is preferable to use a polymer dispersant as (f) the dispersant, since the obtained pigment dispersion and the colored photosensitive resin composition are excellent in dispersion stability, and increase in viscosity over time is suppressed.
As the (a) colorant, organic solvent, and (f) dispersant that can be used in the pigment dispersion, those described as those that can be used in the colored photosensitive resin composition can be preferably employed. . As the content ratio of each colorant in (a) the colorant in the pigment dispersion, the content ratio described as the content ratio in the colored photosensitive resin composition can be preferably employed.
　サンドグラインダーで（ａ）着色剤を分散させる場合には、０．１～８ｍｍ程度の粒子径のガラスビーズ又はジルコニアビーズが好ましく用いられる。分散処理条件は、温度は０℃から１００℃が好ましく、室温から８０℃がより好ましい。分散時間は液の組成及び分散処理装置のサイズ等により適正時間が異なるため適宜調節する。着色感光性樹脂組成物の２０度鏡面光沢度（ＪＩＳ　Ｚ８７４１）が５０～３００の範囲となるように、インキの光沢を制御することが分散の目安である。 When dispersing (a) the colorant with a sand grinder, glass beads or zirconia beads with a particle size of about 0.1 to 8 mm are preferably used. Regarding the dispersion treatment conditions, the temperature is preferably from 0°C to 100°C, more preferably from room temperature to 80°C. The appropriate dispersion time varies depending on the composition of the liquid, the size of the dispersion treatment apparatus, etc., and is therefore adjusted as appropriate. The index of dispersion is to control the gloss of the ink so that the 20 degree specular gloss (JIS Z8741) of the colored photosensitive resin composition is in the range of 50-300.
　顔料分散液中に分散した顔料の分散粒径は０．０３～０．３μｍが好ましく、動的光散乱法等により測定される。
　次に、分散処理により得られた顔料分散液と、着色感光性樹脂組成物中に含まれる他の成分を混合し、均一な溶液又は分散液とする。着色感光性樹脂組成物の製造工程においては、微細なゴミが液中に混じることがあるため、得られた着色感光性樹脂組成物はフィルター等により濾過処理することが望ましい。 The dispersed particle size of the pigment dispersed in the pigment dispersion liquid is preferably 0.03 to 0.3 μm, and is measured by a dynamic light scattering method or the like.
Next, the pigment dispersion obtained by the dispersion treatment and other components contained in the colored photosensitive resin composition are mixed to form a uniform solution or dispersion. In the manufacturing process of the colored photosensitive resin composition, since fine dust may be mixed in the liquid, it is desirable to filter the obtained colored photosensitive resin composition with a filter or the like.
［２］隔壁及びその形成方法
　本発明の着色感光性樹脂組成物を硬化させることで、本発明の硬化物を得ることができる。本発明の着色感光性樹脂組成物は隔壁を形成するために用いることができ、例えば、有機電界発光素子の有機層を区画するための隔壁や、発光性ナノ粒子を含むカラーフィルタにおける画素部を区画するための隔壁を形成するために好適に用いることができる。本発明の隔壁は、本発明の硬化物から構成される。
　本発明の着色感光性樹脂組成物を用いて隔壁を形成する方法は特に限定されず、従来公知の方法を採用することができる。隔壁の形成方法としては、例えば、着色感光性樹脂組成物を、基板上に塗布し、着色感光性樹脂組成物層を形成する塗布工程と、着色感光性樹脂組成物層を露光する露光工程と、を含む方法が挙げられる。このような隔壁の形成方法の具体例としては、インクジェット法とフォトリソグラフィー法とが挙げられる。 [2] Partition walls and method for forming the same The cured product of the present invention can be obtained by curing the colored photosensitive resin composition of the present invention. The colored photosensitive resin composition of the present invention can be used to form partitions, for example, partitions for partitioning the organic layers of an organic electroluminescent device, and pixel portions in color filters containing luminescent nanoparticles. It can be suitably used for forming partitions for partitioning. The partition wall of the present invention is composed of the cured product of the present invention.
The method for forming partition walls using the colored photosensitive resin composition of the present invention is not particularly limited, and conventionally known methods can be employed. A method for forming the partition walls includes, for example, a coating step of applying a colored photosensitive resin composition onto a substrate to form a colored photosensitive resin composition layer, and an exposure step of exposing the colored photosensitive resin composition layer. , and the like. Specific examples of the method for forming such partition walls include an inkjet method and a photolithography method.
　インクジェット法では、溶剤による希釈等により粘度調整された着色感光性樹脂組成物をインクとして用い、所定の隔壁のパターンに沿ってインクジェット法によりインク液滴を基板上に吐出することで着色感光性樹脂組成物を基板上に塗布して未硬化の隔壁のパターンを形成する。そして、未硬化の隔壁のパターンを露光して、基板上に硬化した隔壁を形成する。未硬化の隔壁のパターンの露光は、マスクを用いないことの他は、後述するフォトリソグラフィー法における露光工程と同様に行われる。 In the inkjet method, a colored photosensitive resin composition whose viscosity has been adjusted by dilution with a solvent or the like is used as ink, and ink droplets are ejected onto a substrate along a predetermined pattern of partition walls by an inkjet method to obtain a colored photosensitive resin. The composition is applied onto a substrate to form a pattern of uncured barrier ribs. The pattern of uncured barrier ribs is then exposed to form cured barrier ribs on the substrate. The exposure of the uncured barrier rib pattern is performed in the same manner as the exposure step in the photolithography method described later, except that no mask is used.
　フォトリソグラフィー法では、着色感光性樹脂組成物を、基板の隔壁が形成される領域全面に塗布して着色感光性樹脂組成物層を形成する。形成された着色感光性樹脂組成物層を、所定の隔壁のパターンに応じて露光した後、露光された着色感光性樹脂組成物層を現像して、基板上に隔壁が形成される。 In the photolithography method, a colored photosensitive resin composition is applied to the entire area of the substrate where the partition walls are to be formed to form a colored photosensitive resin composition layer. After the formed colored photosensitive resin composition layer is exposed according to a predetermined pattern of barrier ribs, the exposed colored photosensitive resin composition layer is developed to form barrier ribs on the substrate.
　フォトリソグラフィー法における、着色感光性樹脂組成物を基板上に塗布する塗布工程では、隔壁が形成されるべき基板上に、ロールコーター、リバースコーター、バーコーター等の接触転写型塗布装置やスピンナー（回転式塗布装置）、カーテンフローコーター等の非接触型塗布装置を用いて着色感光性樹脂組成物を塗布し、必要に応じて、乾燥により溶媒を除去して、着色感光性樹脂組成物層を形成する。 In the coating step of applying a colored photosensitive resin composition onto a substrate in the photolithography method, a contact transfer coating device such as a roll coater, a reverse coater, a bar coater, or a spinner (rotating Coating device), a curtain flow coater or other non-contact coating device is used to apply the colored photosensitive resin composition, and if necessary, the solvent is removed by drying to form a colored photosensitive resin composition layer. do.
　次いで、露光工程では、ネガ型のマスクを利用して、着色感光性樹脂組成物に紫外線、エキシマレーザー光等の活性エネルギー線を照射し、着色感光性樹脂組成物層をバンクのパターンに応じて部分的に露光する。露光には、高圧水銀灯、超高圧水銀灯、キセノンランプ、カーボンアーク灯等の紫外線を発する光源を用いることができる。露光量は着色感光性樹脂組成物の組成によっても異なるが、例えば１０～４００ｍＪ／ｃｍ2程度が好ましい。 Next, in the exposure step, a negative mask is used to irradiate the colored photosensitive resin composition with active energy rays such as ultraviolet rays and excimer laser light, and the colored photosensitive resin composition layer is formed according to the bank pattern. Partial exposure. For exposure, a light source that emits ultraviolet rays, such as a high-pressure mercury lamp, an extra-high pressure mercury lamp, a xenon lamp, or a carbon arc lamp, can be used. Although the amount of exposure varies depending on the composition of the colored photosensitive resin composition, it is preferably about 10 to 400 mJ/cm 2 , for example.
　次いで、現像工程では、隔壁のパターンに応じて露光された着色感光性樹脂組成物層を現像液で現像することにより隔壁を形成する。現像方法は特に限定されず、浸漬法、スプレー法等を用いることができる。現像液の具体例としては、ジメチルベンジルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等の有機系のものや、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、アンモニア、４級アンモニウム塩等の水溶液が挙げられる。又、現像液には、消泡剤や界面活性剤を添加することもできる。 Next, in the developing step, the partition walls are formed by developing the exposed colored photosensitive resin composition layer according to the pattern of the partition walls with a developer. The development method is not particularly limited, and an immersion method, a spray method, or the like can be used. Specific examples of the developer include organic ones such as dimethylbenzylamine, monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts. mentioned. Moreover, an antifoaming agent or a surfactant can be added to the developer.
　その後、現像後の隔壁にポストベークを施して加熱硬化する。ポストベークは、８０～２５０℃で１５～１８０分間が好ましい。 After that, the barrier ribs after development are post-baked and cured by heating. Post-baking is preferably carried out at 80 to 250° C. for 15 to 180 minutes.
　本発明の隔壁は上述した方法で形成することができる。また、例えば、（ａ１）酸化チタン粒子、その他の着色剤を含有する着色感光性樹脂組成物を各々作成し、先ず、その他の着色剤を含有する着色感光性樹脂組成物で隔壁を作成した後、その上から（ａ１）酸化チタン粒子を含有する着色感光性樹脂組成物を用いて前記隔壁の外側を覆うことで形成することもできる。 The partition of the present invention can be formed by the method described above. Alternatively, for example, (a1) a colored photosensitive resin composition containing titanium oxide particles and another coloring agent is prepared, and partition walls are first prepared from the colored photosensitive resin composition containing another coloring agent. , and (a1) a colored photosensitive resin composition containing titanium oxide particles may be used to cover the outside of the partition walls.
　隔壁の形成に用いる基板は特に限定されず、隔壁が形成された基板を用いて製造される有機電界発光素子の種類に合わせて適宜選択される。好適な基板の材料としては、ガラスや、各種の樹脂材料が挙げられる。樹脂材料の具体例としては、例えば、ポリエチレンテレフタレート等のポリエステル；ポリエチレン、及びポリプロピレン等のポリオレフィン；ポリカーボネート；ポリ（メタ）メタアクリル樹脂；ポリスルホン；ポリイミドが挙げられる。これらの基板の材料の中では、耐熱性に優れることからガラス、及びポリイミドが好ましい。また、製造される有機電界発光素子の種類に応じて、隔壁が形成される基板の表面には、予めＩＴＯやＺｎＯ等の透明電極層を設けておいてもよいし、ＳｉＮｘやＳｉＯｘなどのガスバリヤ層や密着改善層、カラーフィルタや平坦下層などが設けられていても良い。 The substrate used for forming the partition is not particularly limited, and is appropriately selected according to the type of organic electroluminescence device manufactured using the substrate on which the partition is formed. Suitable substrate materials include glass and various resin materials. Specific examples of the resin material include polyester such as polyethylene terephthalate; polyolefin such as polyethylene and polypropylene; polycarbonate; poly(meth)methacrylic resin; polysulfone; and polyimide. Among these substrate materials, glass and polyimide are preferable because of their excellent heat resistance. Depending on the type of organic electroluminescence element to be manufactured, a transparent electrode layer such as ITO or ZnO may be provided in advance on the surface of the substrate on which the barrier ribs are formed, or a gas barrier layer such as SiNx or SiOx may be provided. A layer, an adhesion improving layer, a color filter, a planarization lower layer, etc. may be provided.
　本発明の隔壁の膜厚は好ましくは０．１μｍ以上であり、より好ましくは１μｍ以上、さらに好ましくは５μｍ以上、特に好ましくは１０μｍ以上、また、好ましくは１ｍｍ以下、より好ましくは１００μｍ以下、さらに好ましくは５０μｍ以下、よりさらに好ましくは３０μｍ以下、特に好ましくは２０μｍ以下である。
　上記の上限及び下限は任意に組み合わせることができる。例えば、好ましくは０．１μｍ～１ｍｍ、より好ましくは１～１００μｍ、さらに好ましくは５～５０μｍ、特に好ましくは１０～３０μｍである。前記下限値以上とすることで遮光性が向上する傾向がある。また、前記上限値以下とすることで密着性が向上する傾向がある。
　隔壁の膜厚は段差・表面粗さ・微細形状測定装置、走査型白色干渉顕微鏡、エリプソメーター、反射分光膜厚計、電子顕微鏡で測定される。 The thickness of the partition wall of the present invention is preferably 0.1 μm or more, more preferably 1 μm or more, still more preferably 5 μm or more, particularly preferably 10 μm or more, more preferably 1 mm or less, more preferably 100 μm or less, and still more preferably. is 50 μm or less, more preferably 30 μm or less, particularly preferably 20 μm or less.
The above upper and lower limits can be combined arbitrarily. For example, it is preferably 0.1 μm to 1 mm, more preferably 1 to 100 μm, even more preferably 5 to 50 μm, particularly preferably 10 to 30 μm. When the amount is equal to or higher than the lower limit, there is a tendency that the light shielding property is improved. Moreover, there exists a tendency for adhesiveness to improve by making it below the said upper limit.
The film thickness of the partition wall is measured by a level difference/surface roughness/fine shape measuring device, a scanning white light interference microscope, an ellipsometer, a reflection spectroscopic film thickness meter, and an electron microscope.
［３］量子ドットナノ粒子を含むカラーフィルタ
　本発明の量子ドットナノ粒子を含むカラーフィルタは、本発明の隔壁を備えていれば特に限定されず、例えば、本発明の硬化物から構成される隔壁で区画された領域に、量子ドットナノ粒子を含む層を画素として形成したものが挙げられる。
　量子ドットナノ粒子を含む層を形成する方法は特に限定されない。例えば、量子ドットナノ粒子を含む量子ドットナノ粒子含有組成物をインクジェット方式により、隔壁で区画された領域に選択的に付着させ、活性エネルギー線の照射又は加熱により量子ドットナノ粒子含有組成物を硬化させる方法により製造することができる。 [3] Color Filter Containing Quantum Dot Nanoparticles The color filter containing the quantum dot nanoparticles of the present invention is not particularly limited as long as it comprises the partition walls of the present invention. For example, a layer containing quantum dot nanoparticles is formed as a pixel in the region.
A method for forming a layer containing quantum dot nanoparticles is not particularly limited. For example, a quantum dot nanoparticle-containing composition containing quantum dot nanoparticles is selectively attached to a region partitioned by partition walls by an inkjet method, and the quantum dot nanoparticle-containing composition is cured by irradiation or heating with an active energy ray. can be manufactured.
　量子ドットナノ粒子含有組成物としては、量子ドットナノ粒子を含有していれば特に限定されず溶剤を含有していてもしていなくてもよい。溶剤を含む場合の溶剤の沸点は、インクジェット方式用インクの連続吐出安定性の観点から、１８０℃以上であることが好ましい。画素部の形成時には、量子ドットナノ粒子含有組成物の硬化前に量子ドットナノ粒子含有組成物から溶剤を除去する必要があるため、溶剤を除去しやすい観点から、溶剤の沸点は３００℃以下であることが好ましい。 The composition containing quantum dot nanoparticles is not particularly limited as long as it contains quantum dot nanoparticles, and may or may not contain a solvent. When a solvent is included, the boiling point of the solvent is preferably 180° C. or higher from the viewpoint of the continuous ejection stability of the inkjet ink. When forming the pixel portion, it is necessary to remove the solvent from the quantum dot nanoparticle-containing composition before curing the quantum dot nanoparticle-containing composition, so from the viewpoint of easy removal of the solvent, the boiling point of the solvent is 300 ° C. or less. is preferred.
　量子ドットナノ粒子含有組成物が溶剤を含む場合、その含有割合は特に限定されない。量子ドットナノ粒子組成物中に０．００１質量％以上が好ましく、０．０１質量％以上がより好ましく、０．１質量％以上がさらに好ましく、１質量％以上がよりさらに好ましく、１０質量％以上がことさらに好ましく、２０質量％以上がよりことさらに好ましく、３０質量％以上が特に好ましい。また、９０質量％以下が好ましく、８０質量％以下がより好ましく、７０質量％以下がさらに好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、０．００１～９０質量％が好ましく、０．０１～９０質量％がより好ましく、０．１～９０質量％がさらに好ましく、１～８０質量％がよりさらに好ましく、１０～８０質量％がことさらに好ましく、２０～７０質量％がよりことさらに好ましく、３０～７０質量％が特に好ましい。前記下限値以上とすることで、組成物の粘度を低減し、公知の塗布方法への適性、特にインクジェットの吐出が容易になる傾向がある。前記上限値以下とすることで、公知の塗布方法への適性、特に吐出した後、溶剤を除去後の膜の厚みが厚くなり、より多くの量子ドットナノ粒子を含む膜が形成できることで発光強度の大きい画素部を得ることができる傾向がある。 When the quantum dot nanoparticle-containing composition contains a solvent, the content is not particularly limited. Preferably 0.001% by mass or more in the quantum dot nanoparticle composition, more preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 1% by mass or more, 10% by mass or more More preferably, 20% by mass or more is even more preferable, and 30% by mass or more is particularly preferable. Moreover, it is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.
The above upper and lower limits can be combined arbitrarily. For example, 0.001 to 90% by mass is preferable, 0.01 to 90% by mass is more preferable, 0.1 to 90% by mass is more preferable, 1 to 80% by mass is even more preferable, and 10 to 80% by mass is More preferably, 20 to 70% by mass is even more preferable, and 30 to 70% by mass is particularly preferable. When the content is at least the above lower limit, the viscosity of the composition tends to be reduced, and suitability for known coating methods, particularly ink ejection, tends to be facilitated. By setting it to the above upper limit or less, the thickness of the film after discharging and removing the solvent becomes thicker, and the film containing more quantum dot nanoparticles can be formed. There is a tendency to be able to obtain a large pixel portion.
　量子ドットナノ粒子含有組成物では、分散媒として機能する（メタ）アクリレート化合物を用いることで、無溶剤で量子ドットナノ粒子を分散させることも可能である。この場合、画素部を形成する際に溶剤を乾燥により除去する工程が不要となる利点を有する。 In the quantum dot nanoparticle-containing composition, it is possible to disperse the quantum dot nanoparticles without a solvent by using a (meth)acrylate compound that functions as a dispersion medium. In this case, there is an advantage that the step of removing the solvent by drying is not required when forming the pixel portion.
　量子ドットナノ粒子含有組成物を本発明で用いるインクジェット用インクとする場合の４０℃における粘度は特に限定されないが、例えば、公知の塗布方法への適性、特にインクジェット印刷時の吐出安定性の観点から、２ｍＰａ・ｓ以上が好ましく、５ｍＰａ・ｓ以上がより好ましく、７ｍＰａ・ｓ以上がさらに好ましく、また、２０ｍＰａ・ｓ以下が好ましく、１５ｍＰａ・ｓ以下がより好ましく、１２ｍＰａ・ｓ以下がさらに好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、２～２０ｍＰａ・ｓが好ましく、５～１５ｍＰａ・ｓがより好ましく、７～１２ｍＰａ・ｓがさらに好ましい。
　量子ドットナノ粒子含有組成物の粘度は、Ｅ型粘度計によって測定される。 When the quantum dot nanoparticle-containing composition is used as an inkjet ink for use in the present invention, the viscosity at 40° C. is not particularly limited. It is preferably 2 mPa·s or more, more preferably 5 mPa·s or more, still more preferably 7 mPa·s or more, and preferably 20 mPa·s or less, more preferably 15 mPa·s or less, and even more preferably 12 mPa·s or less.
The above upper and lower limits can be combined arbitrarily. For example, it is preferably from 2 to 20 mPa·s, more preferably from 5 to 15 mPa·s, even more preferably from 7 to 12 mPa·s.
The viscosity of the quantum dot nanoparticle-containing composition is measured with an E-type viscometer.
　本発明に用いる場合の量子ドットナノ粒子含有組成物の２３℃における粘度は特に限定されないが、例えば、公知の塗布方法への適性、特にインクジェット印刷時の吐出安定性の観点から、５ｍＰａ・ｓ以上が好ましく、１０ｍＰａ・ｓ以上がより好ましく、１５ｍＰａ・ｓ以上がさらに好ましく、また、４０ｍＰａ・ｓ以下が好ましく、３５ｍＰａ・ｓ以下がより好ましく、３０ｍＰａ・ｓ以下がさらに好ましく、２５ｍＰａ・ｓ以下が特に好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、５～４０ｍＰａ・ｓが好ましく、５～３５ｍＰａ・ｓがより好ましく、１０～３０ｍＰａ・ｓがさらに好ましく、１５～２５ｍＰａ・ｓが特に好ましい。 The viscosity at 23 ° C. of the quantum dot nanoparticle-containing composition when used in the present invention is not particularly limited. preferably 10 mPa·s or more, more preferably 15 mPa·s or more, preferably 40 mPa·s or less, more preferably 35 mPa·s or less, further preferably 30 mPa·s or less, and particularly preferably 25 mPa·s or less. .
The above upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 40 mPa·s, more preferably 5 to 35 mPa·s, still more preferably 10 to 30 mPa·s, and particularly preferably 15 to 25 mPa·s.
　本発明で用いる場合の量子ドットナノ粒子含有組成物の表面張力は特に限定されないが、公知の塗布方法への適性、特にインクジェット方式に適した表面張力であることが好ましく、具体的には、２０～４０ｍＮ／ｍが好ましく、２５～３５ｍＮ／ｍがより好ましい。表面張力を前記範囲内とすることで飛行曲がりの発生を抑制することができる。なお、飛行曲がりとは、量子ドットナノ粒子含有組成物をインク吐出孔から吐出させたとき、量子ドットナノ粒子含有組成物の着弾位置が目標位置に対して３０μｍ以上のずれを生じることをいう。 The surface tension of the quantum dot nanoparticle-containing composition when used in the present invention is not particularly limited, but it is preferably suitable for a known coating method, particularly a surface tension suitable for an inkjet method, specifically, 20 to 40 mN/m is preferred, and 25-35 mN/m is more preferred. By setting the surface tension within the above range, the occurrence of flight deflection can be suppressed. The term "flight deflection" means that when the quantum dot nanoparticle-containing composition is ejected from the ink ejection hole, the landing position of the quantum dot nanoparticle-containing composition deviates from the target position by 30 μm or more.
　本発明の隔壁で量子ドットナノ粒子を含むカラーフィルタを形成させる場合は量子ドットナノ粒子を含まずに酸化チタン等の光散乱性粒子を分散させた組成物を青色ピクセルに該当する区画に吐出するインクとして用いてもよい。 In the case of forming a color filter containing quantum dot nanoparticles with the partition walls of the present invention, a composition in which light scattering particles such as titanium oxide are dispersed without containing quantum dot nanoparticles is used as an ink to be ejected into a section corresponding to a blue pixel. may be used.
　図１は、本発明の隔壁を備えるカラーフィルタの一例の模式断面図である。図１に示すように、カラーフィルタ１００は、基板１０と、基板上に設けられた隔壁２０、赤色画素３０、緑色画素４０、及び青色画素５０を備えている。赤色画素３０、緑色画素４０、及び青色画素５０は、この順に繰り返すように格子状に配列されている。隔壁２０は、これらの隣り合う画素の間に設けられている。言い換えれば、これらの隣り合う画素同士は、隔壁２０によって区画されている。 FIG. 1 is a schematic cross-sectional view of an example of a color filter having partition walls of the present invention. As shown in FIG. 1 , the color filter 100 includes a substrate 10 , partition walls 20 provided on the substrate, red pixels 30 , green pixels 40 and blue pixels 50 . The red pixels 30, the green pixels 40, and the blue pixels 50 are arranged in a grid so as to repeat in this order. A partition wall 20 is provided between these adjacent pixels. In other words, these adjacent pixels are partitioned by the partition walls 20 .
　赤色画素３０には赤色量子ドットナノ粒子２が含まれ、そして緑色画素４０には緑色量子ドットナノ粒子１が含まれる。青色画素５０は、光源からの青色光を透過する画素である。 Red pixels 30 contain red quantum dot nanoparticles 2, and green pixels 40 contain green quantum dot nanoparticles 1. The blue pixels 50 are pixels that transmit blue light from the light source.
　これらのナノ粒子は、励起光を吸収して蛍光又は燐光を発光するナノサイズの結晶体であり、例えば、透過型電子顕微鏡又は走査型電子顕微鏡によって測定される最大粒子径が１００ｎｍ以下である結晶体である。 These nanoparticles are nano-sized crystals that absorb excitation light and emit fluorescence or phosphorescence. For example, crystals having a maximum particle size of 100 nm or less as measured by a transmission electron microscope or scanning electron microscope is the body.
　量子ドットナノ粒子は、所定の波長の光を吸収することにより、吸収した波長とは異なる波長の光（蛍光又は燐光）を発することができるものであり、例えば、赤色量子ドットナノ粒子２は、６０５～６６５ｎｍの範囲に発光ピーク波長を有する光（赤色光）を発するものであり、緑色量子ドットナノ粒子１は、５００～５６０ｎｍの範囲に発光ピーク波長を有する光（緑色光）を発するものである。 Quantum dot nanoparticles can emit light (fluorescence or phosphorescence) of a wavelength different from the absorbed wavelength by absorbing light of a predetermined wavelength. It emits light (red light) with an emission peak wavelength in the range of 665 nm, and the green quantum dot nanoparticles 1 emit light (green light) with an emission peak wavelength in the range of 500 to 560 nm.
　量子ドットナノ粒子が発する光の波長（発光色）は、井戸型ポテンシャルモデルのシュレディンガー波動方程式の解によれば、量子ドットナノ粒子のサイズ（例えば粒子径）に依存するが、量子ドットナノ粒子が有するエネルギーギャップにも依存する。そのため、使用する量子ドットナノ粒子の構成材料及びサイズを変更することにより、発光色を選択することができる。 According to the solution of the Schrödinger wave equation of the well-type potential model, the wavelength (emission color) of the light emitted by the quantum dot nanoparticles depends on the size (for example, particle diameter) of the quantum dot nanoparticles, but the energy gap of the quantum dot nanoparticles also depends on Therefore, the emission color can be selected by changing the constituent material and size of the quantum dot nanoparticles to be used.
［４］画像表示装置
　本発明の画像表示装置は、本発明の隔壁を備える。
　本発明の画像表示装置として、例えば、量子ドットナノ粒子を発光素子に含む画像表示装置が挙げられる。量子ドットナノ粒子を含むものであれば画像表示装置の型式や構造については特に制限は無く、例えば、バックライト無しで量子ドットナノ粒子含有画素が自己発光するタイプのものや、ＯＬＥＤやＬＥＤ等のバックライトを用いて量子ドットナノ粒子をカラーフィルタをとして用いるタイプのものが挙げられる。 [4] Image display device The image display device of the present invention includes the partition wall of the present invention.
The image display device of the present invention includes, for example, an image display device including quantum dot nanoparticles in light emitting elements. There are no particular restrictions on the type and structure of the image display device as long as it contains quantum dot nanoparticles. and a type that uses quantum dot nanoparticles as color filters.
　本発明の画像表示装置として、例えば、本発明に係る量子ドットナノ粒子を含むカラーフィルタを備える画像表示装置の場合、画像表示装置の種類としては、液晶表示装置や、有機電界発光素子を含む画像表示装置などが挙げられる。液晶表示装置の場合、青色ＬＥＤを備えた光源と、光源から発せられた青色光を画素部ごとに制御する電極を備えた液晶層を含むものが挙げられる。
　有機電界発光素子を含む画像表示装置では、カラーフィルタの各画素部に対応する位置に青色発光の有機電界発光素子を配置したものが挙げられる。具体的には、日本国特開２０１９－８７７４６号公報に記載の方式が挙げられる。 As the image display device of the present invention, for example, in the case of an image display device equipped with a color filter containing the quantum dot nanoparticles according to the present invention, the type of the image display device may be a liquid crystal display device or an image display including an organic electroluminescence device. device and the like. A liquid crystal display device includes a light source having a blue LED and a liquid crystal layer having an electrode for controlling the blue light emitted from the light source for each pixel portion.
An example of an image display device including organic electroluminescence elements is one in which blue-emitting organic electroluminescence elements are arranged at positions corresponding to respective pixel portions of a color filter. Specifically, the method described in Japanese Patent Application Laid-Open No. 2019-87746 can be mentioned.
　その他、本発明の画像表示装置に用いる発光性ナノ粒子としてはＬＥＤのナノカラムなども挙げられる。 In addition, the luminescent nanoparticles used in the image display device of the present invention include LED nanocolumns.
　以下、本発明の着色感光性樹脂組成物について、具体的な実施例を挙げて説明するが、本発明はその要旨を越えない限り、以下の実施例に限定されるものではない。 The colored photosensitive resin composition of the present invention will be described below with specific examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
＜光重合開始剤－１＞
　以下の化学構造を有する化合物を用いた。 <Photoinitiator-1>
A compound having the following chemical structure was used.
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
＜光重合開始剤－２＞
　以下の化学構造を有する化合物を用いた。 <Photoinitiator-2>
A compound having the following chemical structure was used.
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000043
＜光重合開始剤－３＞
　以下の化学構造を有する化合物を用いた。 <Photoinitiator-3>
A compound having the following chemical structure was used.
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
＜光重合開始剤－４＞
　以下の化学構造を有する化合物を用いた。 <Photoinitiator-4>
A compound having the following chemical structure was used.
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
＜光重合開始剤－５＞
　以下の化学構造を有する化合物を用いた。 <Photoinitiator-5>
A compound having the following chemical structure was used.
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
＜光重合開始剤－６＞
　以下の化学構造を有する化合物を用いた。 <Photoinitiator-6>
A compound having the following chemical structure was used.
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
　光重合開始剤－１～６について、０．０１質量％のプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）溶液を作成し、１ｃｍ角の石英セルに入れ、分光光度計ＵＶ－３１００（島津製作所社製）で波長２５０～４００ｎｍの光を照射して１ｎｍおきに吸光度を測定し、最も長波長で吸収が極大となる波長及びその最大吸光度、並びに波長３６０～４００ｎｍにおける最大吸光度とその波長を下記表１に記載した。 A 0.01% by mass propylene glycol monomethyl ether acetate (PGMEA) solution was prepared for photopolymerization initiators-1 to 6, placed in a 1 cm square quartz cell, and measured with a spectrophotometer UV-3100 (manufactured by Shimadzu Corporation). Irradiate light with a wavelength of 250 to 400 nm and measure the absorbance at intervals of 1 nm. did.
Figure JPOXMLDOC01-appb-T000048
Figure JPOXMLDOC01-appb-T000048
＜アルカリ可溶性樹脂－１＞
　ジシクロペンタニルメタクリレート（日立化成社製ＦＡ－５１３Ｍ）／スチレン／グリシジルメタクリレート（モル比：０．３／０．１／０．６）を構成モノマーとする共重合樹脂に、アクリル酸をグリシジルメタクリレートに対して等量付加反応させ、さらに無水テトラヒドロフタル酸を上記の共重合樹脂１モルに対して０．３９モルになるように付加反応させた、アルカリ可溶性のアクリル共重合樹脂。ＧＰＣで測定したポリスチレン換算の重量平均分子量（Ｍｗ）は９０００、固形分酸価は８０ｍｇＫＯＨ／ｇ。側鎖にエチレン性不飽和基を有するアクリル共重合樹脂（ｂ１１）に該当する。二重結合当量４７０ｇ／ｍｏｌ。 <Alkali-soluble resin-1>
Dicyclopentanyl methacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) / styrene / glycidyl methacrylate (molar ratio: 0.3 / 0.1 / 0.6) is a copolymer resin composed of monomers, and acrylic acid is glycidyl methacrylate. and 0.39 mol of tetrahydrophthalic anhydride per 1 mol of the above copolymer resin. The polystyrene equivalent weight average molecular weight (Mw) measured by GPC was 9000, and the solid content acid value was 80 mgKOH/g. It corresponds to the acrylic copolymer resin (b11) having an ethylenically unsaturated group in the side chain. Double bond equivalent weight 470 g/mol.
＜アルカリ可溶性樹脂－２＞
　日本化薬社製「ＺＣＲ－１５６９Ｈ」（Ｍｗ３９００、酸価９８ｍｇＫＯＨ／ｇ、二重結合当量５００ｇ／ｍｏｌ）。 <Alkali-soluble resin-2>
"ZCR-1569H" manufactured by Nippon Kayaku Co., Ltd. (Mw 3900, acid value 98 mgKOH/g, double bond equivalent 500 g/mol).
＜アルカリ可溶性樹脂－３＞
　メタクリル酸とメタクリル酸メチルの共重合樹脂。（モル比８２：１２、Ｍｗ１１４００、酸価９７ｍｇＫＯＨ／ｇ、二重結合なし）。 <Alkali-soluble resin-3>
Copolymer resin of methacrylic acid and methyl methacrylate. (molar ratio 82:12, Mw 11400, acid number 97 mg KOH/g, no double bonds).
＜光重合性化合物－１＞
　ＤＰＨＡ：日本化薬社製　ジペンタエリスリトールヘキサアクリレート <Photopolymerizable compound-1>
DPHA: Dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.
＜撥液剤－１＞
　ＤＩＣ社製　メガファック　ＲＳ－９０（フッ素系、エチレン性二重結合を有する）　固形分濃度１０％の１，３－ビス（トリフルオロメチル）ベンゼンとメチルエチルケトンの溶液の状態で用いた。 <Liquid repellent agent -1>
Megafac RS-90 manufactured by DIC Corporation (fluorinated, having an ethylenic double bond) Used in the form of a solution of 1,3-bis(trifluoromethyl)benzene and methyl ethyl ketone having a solid concentration of 10%.
＜添加剤－１＞
　昭和電工社製　カレンズＭＴ　ＰＥ１（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）） <Additive-1>
Showa Denko Karenz MT PE1 (pentaerythritol tetrakis (3-mercaptobutyrate))
＜添加剤－２＞
　日本化薬社製、ＫＡＹＡＭＥＲ　ＰＭ－２１（メタクリロイル基含有ホスフェート） <Additive-2>
Nippon Kayaku Co., Ltd., KAYAMER PM-21 (methacryloyl group-containing phosphate)
＜溶剤－１＞
　ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート <Solvent-1>
PGMEA: propylene glycol monomethyl ether acetate
＜溶剤－２＞
　ＰＧＭＥ：プロピレングリコールモノメチルエーテル <Solvent-2>
PGME: propylene glycol monomethyl ether
＜酸化チタン分散液－１の調製＞
　石原産業社製の酸化チタン　ＰＴ５０１Ｒ（一次粒子の平均粒子径０．１８μｍ）、塩基性高分子アクリル分散剤（分散剤－１）、及び溶剤を、表１に記載の質量比となるように混合した。この混合液をペイントシェーカーにより２５～４５℃の範囲で６時間分散処理を行った。ビーズとしては、０．３ｍｍφのジルコニアビーズを用い、混合液の２．５倍の質量を加えた。分散終了後、フィルターによりビーズと分散液を分離して、酸化チタン分散液－１を調製した。
　なお、表２中の分散剤の配合割合は固形分換算値であり、溶剤の配合割合には分散剤由来の溶剤の量も含まれる。 <Preparation of Titanium Oxide Dispersion-1>
Titanium oxide PT501R manufactured by Ishihara Sangyo Co., Ltd. (average particle size of primary particles 0.18 μm), basic polymer acrylic dispersant (dispersant-1), and solvent are mixed so that the mass ratio shown in Table 1 is achieved. did. This mixture was subjected to dispersion treatment for 6 hours at a temperature of 25 to 45° C. using a paint shaker. As the beads, 0.3 mmφ zirconia beads were used, and 2.5 times the mass of the mixed solution was added. After the dispersion was completed, the beads and the dispersion were separated by a filter to prepare a titanium oxide dispersion-1.
The blending ratio of the dispersant in Table 2 is a solid content conversion value, and the blending ratio of the solvent includes the amount of the solvent derived from the dispersant.
Figure JPOXMLDOC01-appb-T000049
Figure JPOXMLDOC01-appb-T000049
［実施例１～４、及び比較例１～６］
　上記調製した酸化チタン分散液－１を用いて、着色感光性樹脂組成物の全固形分量中の各成分の固形分の比率が表３の配合割合となるように各成分を加え、さらに全溶剤中における溶剤－２の割合が２０質量％、かつ全固形分量の含有割合が３１質量％となるように、溶剤－１を加え、攪拌、溶解、分散させて、実施例１～４及び比較例１～６の着色感光性樹脂組成物を調製した。得られた着色感光性樹脂組成物を用いて、後述する方法で性能評価を行った。
　なお、表３中の酸化チタン分散液、アルカリ可溶性樹脂、撥液剤の配合割合は固形分換算値である。 [Examples 1 to 4 and Comparative Examples 1 to 6]
Using the titanium oxide dispersion-1 prepared above, each component was added so that the ratio of the solid content of each component in the total solid content of the colored photosensitive resin composition was the mixing ratio shown in Table 3, and the total solvent was added. Solvent-1 was added so that the ratio of solvent-2 in the mixture was 20% by mass and the content ratio of the total solid content was 31% by mass, followed by stirring, dissolving, and dispersing Examples 1 to 4 and Comparative Examples. 1-6 colored photosensitive resin compositions were prepared. Using the obtained colored photosensitive resin composition, performance evaluation was performed by the method described later.
The mixing ratios of the titanium oxide dispersion, the alkali-soluble resin, and the liquid repellent in Table 3 are solid content conversion values.
Figure JPOXMLDOC01-appb-T000050
Figure JPOXMLDOC01-appb-T000050
　以下に性能評価の方法を説明する。 The performance evaluation method is explained below.
＜評価用基板作成＞
　ガラス基板上にスピナーを用いて、加熱硬化後に１０．０μｍの厚みになるように、実施例又は比較例で得られた着色感光性樹脂組成物を塗布した。その後、１分間真空乾燥し、さらに１００℃で、２分間ホットプレート上で加熱乾燥して塗膜基板を得た。得られた塗膜基板に対して、フォトマスクを介して露光装置　ＭＰＡ－６００ＦＡ（Ｃａｎｏｎ社製）を用いて３６５ｎｍの波長で５００ｍＷ／ｃｍ２の強度にて１００ｍＪ／ｃｍ２の露光をした。フォトマスクとしては、ライン状の開口部（開口幅５μｍから１μｍ刻みで２０μｍまでと、５μｍ刻みで５０μｍまでをそれぞれ長さ３００μｍで、３本ずつ１００μｍ間隔で並べたもの）と１ｃｍ四方の開口部を有するマスクを使用した。次にこれらを０．０３質量％のＫＯＨ及び０．０５質量％のエマルゲンＡ－６０（花王社製界面活性剤）を溶解した水溶液を現像液として用いて２４℃で０．０５ＭＰａのスプレー圧で６０秒間スプレー現像し、その後０．５ＭＰａのスプレー圧で１０秒間純水にて洗浄した。この基板を１２０℃のオーブンで３０分間加熱硬化させ評価用基板を得た。 <Evaluation board creation>
The colored photosensitive resin composition obtained in Examples or Comparative Examples was applied onto a glass substrate using a spinner so as to have a thickness of 10.0 μm after heat curing. After that, it was vacuum-dried for 1 minute and further dried by heating on a hot plate at 100° C. for 2 minutes to obtain a coated film substrate. The resulting coated film substrate was exposed to light of 100 mJ/cm 2 at a wavelength of 365 nm and an intensity of 500 mW/cm 2 using an exposure apparatus MPA-600FA (manufactured by Canon) through a photomask. As a photomask, line-shaped openings (opening width of 5 μm to 20 μm in increments of 1 μm, and up to 50 μm in increments of 5 μm, each having a length of 300 μm and three openings arranged at intervals of 100 μm) and openings of 1 cm square. A mask with Next, these were mixed at 24° C. with a spray pressure of 0.05 MPa using an aqueous solution in which 0.03% by mass of KOH and 0.05% by mass of Emulgen A-60 (surfactant manufactured by Kao Corporation) were dissolved as a developer. It was developed by spraying for 60 seconds, and then washed with pure water for 10 seconds at a spray pressure of 0.5 MPa. This substrate was cured by heating in an oven at 120° C. for 30 minutes to obtain a substrate for evaluation.
＜反射率測定用基板の作成＞
　塗膜基板を露光する際、フォトマスクを用いずに全面露光する以外は全て上記評価用基板と同様に作成した。 <Preparation of substrate for reflectance measurement>
When the coated film substrate was exposed, it was prepared in the same manner as the evaluation substrate except that the entire surface was exposed without using a photomask.
＜ＰＧＭＥＡ接触角の測定＞
　協和界面科学社製Ｄｒｏｐ　Ｍａｓｔｅｒ　５００接触角測定装置を用いて、２３℃、湿度５０％の条件下でＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート）０．７μＬを前記評価用基板の１ｃｍ四方のベタ部に滴下した１秒後の接触角を測定し、結果を表３に示した。接触角が大きい方ほど撥インク性が高いことを表す。 <Measurement of PGMEA contact angle>
Using a Drop Master 500 contact angle measurement device manufactured by Kyowa Interface Science Co., Ltd., 0.7 μL of PGMEA (propylene glycol monomethyl ether acetate) was dropped onto a 1 cm square solid portion of the evaluation substrate under conditions of 23° C. and 50% humidity. The contact angle was measured after 1 second, and the results are shown in Table 3. A larger contact angle indicates higher ink repellency.
＜１０μｍラインの線幅の測定＞
　前記評価用基板のマスク開口１０μｍに該当するラインパターンの断面を走査電子顕微鏡で観察し、図２に示すようにラインパターン１０１の断面で最も太い部分を測長幅１０３とし、線幅を測定した。結果を表３に示す。線幅はマスク開口寸法と差が小さいことが好ましい。 <Measurement of line width of 10 μm line>
The section of the line pattern corresponding to the mask opening of 10 μm of the evaluation substrate was observed with a scanning electron microscope, and as shown in FIG. . Table 3 shows the results. It is preferable that the line width has a small difference from the mask aperture size.
＜反射率の測定＞
　分光光度計（ＨＩＴＡＣＨＩ製　Ｕ４１００）に積分球測定用の冶具を設置した。測定基板として前記反射率測定用基板を用い、酸化アルミニウム白板を基準板として、波長２５０～８００ｎｍにおける全反射率を測定した。結果を図４に表す。 <Measurement of reflectance>
A jig for integrating sphere measurement was installed in a spectrophotometer (U4100 manufactured by HITACHI). Total reflectance was measured at a wavelength of 250 to 800 nm using the above reflectance measurement substrate as a measurement substrate and an aluminum oxide white plate as a reference plate. The results are presented in FIG.
　図４より酸化チタン粒子含有膜の反射率は３５０ｎｍより長波長になると急激に上がることが分かる。 From FIG. 4, it can be seen that the reflectance of the titanium oxide particle-containing film sharply increases at wavelengths longer than 350 nm.
　表３より、実施例１～４と比べて比較例１、２の線幅値が非常に大きいことが分かる。これは比較例１、２に使用している光重合開始剤のλmaxが実施例１～４の開始剤より長波長で酸化チタン粒子の反射が増えてくる波長３５０ｎｍを超えているためと考えられる。露光の光が酸化チタン粒子で散乱され周囲に大きく広がるため、マスクの開口領域よりも広い部分の光重合開始剤が光の照射を受けるためであると考えられる。 From Table 3, it can be seen that the line width values of Comparative Examples 1 and 2 are much larger than those of Examples 1-4. This is probably because the λmax of the photopolymerization initiators used in Comparative Examples 1 and 2 exceeds the wavelength of 350 nm at which the reflection of the titanium oxide particles increases at a longer wavelength than the initiators of Examples 1 to 4. . This is probably because the exposure light is scattered by the titanium oxide particles and widely spreads around, so that the photopolymerization initiator in a portion wider than the opening region of the mask is irradiated with the light.
　実施例１と比較例３、４の結果から酸化チタン粒子の含有量が多すぎると１０μｍの線（ライン）が密着し難くなることが分かる。比較例３の場合５０μｍのラインから密着しており、比較例４の場合は５０μｍのラインでも密着は不十分であった。それぞれのパターンの形状は図３の様な下細りの形状であり基板面までパターニングに必要な光が到達しなかったことが伺える。 From the results of Example 1 and Comparative Examples 3 and 4, it can be seen that if the content of titanium oxide particles is too high, it becomes difficult to adhere 10 μm lines. In the case of Comparative Example 3, the adhesion started from the 50 μm line, and in the case of Comparative Example 4, the adhesion was insufficient even at the 50 μm line. Each pattern has a tapered shape as shown in FIG. 3, which indicates that the light required for patterning did not reach the substrate surface.
　比較例１と５の比較から比較例５の１０μｍのラインの線幅値は比較例１と同様に大きいにも関わらず十分な撥インク性が発現出来ていないことが分かる。このことから比較例１は光重合開始剤－５の感度が高すぎて線幅値が大きくなっているわけではなく、酸化チタン粒子による光散乱の影響を受けているために線幅値が大きくなっているということが言える。 From the comparison of Comparative Examples 1 and 5, it can be seen that although the line width value of the 10 μm line in Comparative Example 5 is as large as in Comparative Example 1, sufficient ink repellency cannot be expressed. Therefore, in Comparative Example 1, the sensitivity of the photopolymerization initiator-5 is not too high and the line width value is large, but the line width value is large because it is affected by light scattering by the titanium oxide particles. It can be said that it is.
　比較例６では、接触角が小さく、十分な撥インク性が発現しなかった。また１０μｍの線（ライン）は、現像後に膜減りが生じ、目的の膜厚が得られなかった。実施例１と比較例６の比較から、アルカリ可溶性樹脂の二重結合当量が１０００ｇ／ｍｏｌ以下であることで、撥インク性も良好となる、と言える。 In Comparative Example 6, the contact angle was small and sufficient ink repellency was not exhibited. Also, the 10 μm line (line) caused film reduction after development, and the target film thickness could not be obtained. From the comparison between Example 1 and Comparative Example 6, it can be said that the double bond equivalent of the alkali-soluble resin is 1000 g/mol or less, and the ink repellency is also improved.
１　緑色量子ドットナノ粒子
２　赤色量子ドットナノ粒子
１０　基板
２０　隔壁
３０　赤色画素
４０　緑色画素
５０　青色画素
１００　カラーフィルタ
１０１　ラインパターン
１０２　支持体
１０３　測長幅 1 green quantum dot nanoparticles 2 red quantum dot nanoparticles 10 substrate 20 partition wall 30 red pixel 40 green pixel 50 blue pixel 100 color filter 101 line pattern 102 support 103 length measurement width

Claims (12)

  1. 　（ａ）着色剤、（ｂ）アルカリ可溶性樹脂、（ｃ）光重合開始剤、（ｄ）光重合性化合物及び（ｅ）撥液剤を含有する着色感光性樹脂組成物であって、
    　前記（ａ）着色剤の含有割合が着色感光性樹脂組成物の全固形分量に対して２０質量％以下であり、
    　前記（ａ）着色剤が、（ａ１）酸化チタン粒子を含有し、
    　前記（ｂ）アルカリ可溶性樹脂の二重結合当量が１０００ｇ／ｍｏｌ以下であり、
    　前記（ｃ）光重合開始剤が、波長３００～３５０ｎｍに極大吸収波長（λmax）を有するオキシムエステル系光重合開始剤（ｃ１）を含有し、
    　前記（ｅ）撥液剤が、架橋基を有し、且つフッ素原子及び／又はシロキサン鎖を有する化合物（ｅ１）を含有することを特徴とする着色感光性樹脂組成物。     A colored photosensitive resin composition containing (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) a photopolymerizable compound and (e) a liquid-repellent agent,
    The content of the (a) colorant is 20% by mass or less with respect to the total solid content of the colored photosensitive resin composition,
    The (a) colorant contains (a1) titanium oxide particles,
    The double bond equivalent of the (b) alkali-soluble resin is 1000 g/mol or less,
    The (c) photopolymerization initiator contains an oxime ester photopolymerization initiator (c1) having a maximum absorption wavelength (λmax) at a wavelength of 300 to 350 nm,
    The colored photosensitive resin composition, wherein the (e) liquid-repellent agent contains a compound (e1) having a cross-linking group and having a fluorine atom and/or a siloxane chain.
  2. 　前記（ｃ）光重合開始剤が、０．０１質量％のプロピレングリコールモノメチルエーテルアセテート溶液での波長３６０～４００ｎｍにおける最大吸光度が２以下である請求項１に記載の着色感光性樹脂組成物。 The colored photosensitive resin composition according to claim 1, wherein the (c) photopolymerization initiator has a maximum absorbance of 2 or less at a wavelength of 360 to 400 nm in a 0.01% by mass propylene glycol monomethyl ether acetate solution.
  3. 　前記（ａ）着色剤中の前記（ａ１）酸化チタン粒子の含有割合が５０質量％以上である請求項１又は２に記載の着色感光性樹脂組成物。 The colored photosensitive resin composition according to claim 1 or 2, wherein the content of the (a1) titanium oxide particles in the (a) colorant is 50% by mass or more.
  4. 　前記（ａ１）酸化チタン粒子の一次粒子の平均粒子径が１００ｎｍ以上である請求項１～３のいずれか１項に記載の着色感光性樹脂組成物。 The colored photosensitive resin composition according to any one of claims 1 to 3, wherein the (a1) titanium oxide particles have an average primary particle size of 100 nm or more.
  5. 　前記化合物（ｅ１）が、架橋基及びフッ素原子を有し、且つ化合物（ｅ１）中のフッ素原子の含有割合が１５質量％以上である、請求項１～４のいずれか１項に記載の着色感光性樹脂組成物。 The coloring according to any one of claims 1 to 4, wherein the compound (e1) has a cross-linking group and a fluorine atom, and the content of fluorine atoms in the compound (e1) is 15% by mass or more. A photosensitive resin composition.
  6. 　前記（ｂ）アルカリ可溶性樹脂の二重結合当量が４００ｇ／ｍｏｌより大きい、請求項１～５のいずれか１項に記載の着色感光性樹脂組成物。 The colored photosensitive resin composition according to any one of claims 1 to 5, wherein the alkali-soluble resin (b) has a double bond equivalent of more than 400 g/mol.
  7. 　溶剤を含有する請求項１～６のいずれか１項に記載の着色感光性樹脂組成物。 The colored photosensitive resin composition according to any one of claims 1 to 6, which contains a solvent.
  8. 　隔壁形成用である請求項１～７のいずれか１項に記載の着色感光性樹脂組成物。 The colored photosensitive resin composition according to any one of claims 1 to 7, which is used for forming partition walls.
  9. 　請求項１～８のいずれか１項に記載の着色感光性樹脂組成物を硬化させた硬化物。 A cured product obtained by curing the colored photosensitive resin composition according to any one of claims 1 to 8.
  10. 　請求項９に記載の硬化物から構成される隔壁。 A partition made of the cured product according to claim 9.
  11. 　請求項１０に記載の隔壁を備える、量子ドットナノ粒子を含むカラーフィルタ。 A color filter comprising quantum dot nanoparticles, comprising the partition according to claim 10.
  12. 　請求項１０に記載の隔壁を備える画像表示装置。 An image display device comprising the partition according to claim 10.
PCT/JP2022/014893 2021-03-31 2022-03-28 Colored photosensitve resin composition, cured product, partition wall, color filter, and image display device WO2022210497A1 (en)

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