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WO2022270349A1 - Composition de résine rouge photosensible, produit durci, filtre coloré et dispositif d'affichage - Google Patents

Composition de résine rouge photosensible, produit durci, filtre coloré et dispositif d'affichage Download PDF

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Publication number
WO2022270349A1
WO2022270349A1 PCT/JP2022/023753 JP2022023753W WO2022270349A1 WO 2022270349 A1 WO2022270349 A1 WO 2022270349A1 JP 2022023753 W JP2022023753 W JP 2022023753W WO 2022270349 A1 WO2022270349 A1 WO 2022270349A1
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Prior art keywords
group
mass
general formula
resin composition
carbon atoms
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English (en)
Japanese (ja)
Inventor
隆史 小梶
裕史 大島
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DNP Fine Chemicals Co Ltd
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DNP Fine Chemicals Co Ltd
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Priority to CN202280041762.9A priority Critical patent/CN117460974A/zh
Priority to JP2023530334A priority patent/JPWO2022270349A1/ja
Publication of WO2022270349A1 publication Critical patent/WO2022270349A1/fr
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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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • 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
    • G03F7/004—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

Definitions

  • the present invention relates to a photosensitive red resin composition, a cured product, a color filter, and a display device.
  • an organic light emitting element emitting white light or an inorganic light emitting element emitting white light may be used.
  • An organic light-emitting display device uses a color filter for color adjustment.
  • the color filter is generally formed on a substrate, a colored layer formed on the substrate and composed of colored patterns of the three primary colors of red, green, and blue, and formed on the substrate so as to partition each colored pattern. and a light shielding part.
  • a method for forming a colored layer in a color filter for example, a colored resin composition obtained by adding a binder resin, a photopolymerizable compound and a photoinitiator to a coloring material dispersion liquid in which a coloring material is dispersed using a dispersing agent or the like is prepared. After being coated on a glass substrate and dried, it is exposed using a photomask and developed to form a colored pattern, which is fixed by heating to form a colored layer. These steps are repeated for each color to form a color filter.
  • Patent Document 1 discloses a coloring agent (A), a resin (B), a photopolymerizable monomer (C), and an acylphosphine oxide-based A photopolymerization initiator (D) containing an organic compound or an oxime ester-based organic compound, and at least one UV absorber selected from the group consisting of benzotriazole-based organic compounds, triazine-based organic compounds, and benzophenone-based organic compounds ( E), and the resin (B) comprises the following (b1), (b2) and (b3): (b1); a compound having an alicyclic skeleton and an ethylenically unsaturated bond in one molecule (b2); a compound having an epoxy group and an ethylenically unsaturated bond in one molecule (b3); A compound having an ethylenically unsaturated bond other than (a2) is copolymerized to obtain a copolymer
  • a photosensitive coloring composition which is characterized by In Patent Document 1, a photosensitive coloring composition having high resolution that can correspond to high image quality and low power consumption, in particular, high resolution even in a thick film such as the COA method, and adhesion that does not cause pattern peeling The object is to obtain an excellent photosensitive coloring composition.
  • Patent Document 2 discloses a colorant (A), a resin (B), a photopolymerizable monomer (C), a photopolymerization initiator (D), a benzotriazole-based monomer and other monomers.
  • a coloring composition for a color filter characterized by comprising an ultraviolet absorber (E) obtained by polymerizing raw material monomers containing a monomer component, wherein a benzotriazole-based monomer is included in the raw material monomers. 10.0% by mass to 90.0% by mass of the body, and the ultraviolet absorber (E) is contained in the solid content of the entire color filter coloring composition in an amount of 0.5 to 6.0% by mass.
  • Coloring compositions for filters are disclosed.
  • Patent Document 2 aims at providing a coloring composition for color filters which is excellent in light resistance even when a finely divided pigment or dye is used as a coloring agent.
  • the red colored layer tends to have a reverse tapered cross-sectional shape compared to the green colored layer and the blue colored layer.
  • the cross-sectional shape of the colored layer pattern becomes an inversely tapered shape, various problems arise, such as that the transparent electrode such as ITO formed on the colored layer pattern is easily disconnected, and the solvent resistance of the colored layer is lowered.
  • the colored layer of the photosensitive colored resin composition cures the photocurable component by irradiating light (usually ultraviolet rays with a peak wavelength of 365 nm), but since it is difficult for light to reach near the substrate interface in the colored layer, compared to the surface of the colored layer Hardening becomes weak in the vicinity of the substrate interface. Therefore, the colored layer after development basically has an inversely tapered cross-sectional shape in which the width becomes narrower near the substrate interface. However, during post-baking after development, the green colored layer and the blue colored layer tend to undergo thermal flow in the insufficiently hardened portion near the substrate interface, so that the reverse tapered shape is eliminated.
  • the red colored layer has a higher transmittance at a wavelength of 365 nm used during light irradiation than the green colored layer and the blue colored layer. Curing proceeds more easily in the vicinity of the substrate interface than in the green colored layer and the blue colored layer. Therefore, in the red colored layer, heat flow is less likely to occur in the vicinity of the substrate interface during post-baking after development, and the reverse tapered shape is likely to be maintained.
  • the concentration of coloring materials in the colored layer of the color filter is higher than before, so the components required for photopolymerization are relatively reduced, and patterning is becoming more difficult, resulting in the generation of development residues. In addition, adhesion to the substrate is also a problem.
  • the present invention has been made in view of the above circumstances, and can form a red colored layer having a cross-sectional shape with a taper angle of less than 60 degrees and excellent adhesion to a substrate while suppressing the generation of development residues.
  • An object of the present invention is to provide a photosensitive red resin composition.
  • Another object of the present invention is to provide a color filter and a display device formed using the photosensitive red resin composition.
  • the photosensitive red resin composition according to the present invention contains a coloring material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a solvent
  • the coloring material is made of a pigment containing at least a red pigment
  • the dispersant contains at least one of a block copolymer and a graft copolymer
  • the UV absorber has a transmittance of 35% or less at a wavelength of 365 nm in a 0.002% by mass propylene glycol monomethyl ether acetate solution.
  • the color filter according to the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a cured photosensitive red resin composition according to the present invention. It is a thing.
  • a display device has the color filter according to the present invention.
  • a photosensitive red resin composition capable of forming a red colored layer having a cross-sectional shape with a taper angle of less than 60 degrees and excellent adhesion to a substrate while suppressing the generation of development residues. be able to.
  • the color filter and display apparatus which were formed using the said photosensitive red resin composition can be provided.
  • FIG. 1 is a schematic diagram showing an example of the color filter of the present invention.
  • FIG. 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention.
  • FIG. 3 is a schematic diagram showing an example of the organic light-emitting display device of the present invention.
  • FIG. 4 is a schematic diagram for explaining the taper angle ( ⁇ 1) of the cross-sectional shape of the colored layer of the fine line pattern.
  • light includes electromagnetic waves with wavelengths in the visible and non-visible regions, and radiation
  • radiation includes, for example, microwaves and electron beams. Specifically, it refers to electromagnetic waves with a wavelength of 5 ⁇ m or less and electron beams.
  • (meth)acryloyl represents acryloyl and methacryloyl
  • (meth)acryl represents acrylic and methacrylic
  • (meth)acrylate represents acrylate and methacrylate.
  • the term "to" indicating a numerical range is used to include the numerical values before and after it as lower and upper limits.
  • the photosensitive red resin composition according to the present invention contains a colorant, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a solvent,
  • the coloring material is made of a pigment containing at least a red pigment
  • the dispersant contains at least one of a block copolymer and a graft copolymer
  • the UV absorber has a transmittance of 35% or less at a wavelength of 365 nm in a 0.002% by mass propylene glycol monomethyl ether acetate solution.
  • the photosensitive red resin composition according to the present invention contains a colorant, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a solvent, and the colorant is made of a pigment containing at least a red pigment, and the ultraviolet absorber has a transmittance at a wavelength of 365 nm of 35% or less in a 0.002% by mass propylene glycol monomethyl ether acetate solution.
  • a red colored layer having a cross-sectional shape with a taper angle of less than 60 degrees and excellent adhesion to a substrate can be formed.
  • the red colored layer has a higher transmittance at a wavelength of 365 nm used during light irradiation than the green colored layer and the blue colored layer, so the same amount of light as the green colored layer and the blue colored layer
  • curing progresses more easily in the vicinity of the substrate interface than in the green colored layer or the blue colored layer, and during post-baking after development, heat flow is less likely to occur in the vicinity of the substrate interface, resulting in a reverse tapered shape. It was easy to maintain.
  • a UV absorber having a transmittance of 0.002% by mass at a wavelength of 365 nm in a propylene glycol monomethyl ether acetate solution of 35% or less was selected and combined.
  • the transmittance at a wavelength of 365 nm is effectively reduced, and curing near the substrate interface is suppressed like the green colored layer and the blue colored layer, and during post-baking after development, the same as the green colored layer and the blue colored layer.
  • heat flow is likely to occur in the vicinity of the base material interface, and a red colored layer having a cross-sectional shape with a taper angle of less than 60 degrees can be formed.
  • the red colored layer having a cross-sectional shape with a taper angle of less than 60 degrees has the advantage of improving the adhesion to the substrate compared to the colored layer having a cross-sectional shape with a taper angle of more than 60 degrees.
  • the red colored layer having a cross-sectional shape with a taper angle of less than 60 degrees can prevent disconnection when forming an electrode by coating, and can prevent unnecessary gaps from being formed between the base material and the colored layer. There is an advantage that it is possible to prevent air bubbles from being generated in the liquid crystal.
  • a dispersant having many pigment-adsorbing groups per molecule efficiently adsorbs to a pigment, It is possible to prevent the pigment alone from remaining on the substrate and becoming a development residue.
  • an ultraviolet absorber having a transmittance at a wavelength of 365 nm of 0.002% by mass in a propylene glycol monomethyl ether acetate solution of 35% or less is selected to form a block copolymer and a graft copolymer.
  • the synergistic effect improves the effect of suppressing the generation of development residues.
  • the coloring material is made of a pigment containing at least a red pigment
  • the red colored layer which is a cured product of the photosensitive red resin composition according to the present invention, has a chromaticity due to steps during production such as ultraviolet irradiation and post-baking. Change is suppressed.
  • the photosensitive red resin composition according to the present invention contains at least a coloring material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a solvent. , may further contain other components within a range that does not impair the effects of the present invention.
  • a coloring material e.g., a coloring material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a solvent.
  • the ultraviolet absorber in the present invention refers to a compound that has a maximum absorption wavelength of 400 nm or less and does not absorb visible light with a wavelength exceeding 420 nm.
  • the ultraviolet absorber used in the present invention may be a compound that does not absorb visible light with a wavelength exceeding 400 nm.
  • an ultraviolet absorbent having a transmittance of 35% or less in a 0.002% by mass propylene glycol monomethyl ether acetate solution at a wavelength of 365 nm is selected and used.
  • an ultraviolet absorber with a small transmittance at a wavelength of 365 nm in combination with a red colorant it is possible to ensure thermal fluidity near the substrate interface of the red colored layer during post-baking after development as described above.
  • a red colored layer having a cross-sectional shape with a taper angle of less than 60 degrees can be formed.
  • the transmittance of the UV absorber at a wavelength of 365 nm was determined by preparing a 0.002% by mass propylene glycol monomethyl ether acetate solution of the UV absorber, and measuring the transmittance of the 0.002% by mass propylene glycol monomethyl ether acetate solution by measuring the transmittance of the UV absorber at a wavelength of 365 nm. It can be measured using an external spectrophotometer (eg, JASCO Corporation V-770).
  • the ultraviolet absorber used in the present invention has a transmittance at a wavelength of 365 nm in a 0.002% by mass propylene glycol monomethyl ether acetate solution, more preferably 32% or less, may be 25% or less, or 20% or less. may be
  • the structure of the ultraviolet absorber used in the present invention is not particularly limited as long as the transmittance at a wavelength of 365 nm is 35% or less in a 0.002% by mass propylene glycol monomethyl ether acetate solution.
  • ultraviolet absorbers include benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, benzoic acid-based ultraviolet absorbers, anthranilic acid-based ultraviolet absorbers, and salicylic acid-based ultraviolet absorbers.
  • Absorbents, cinnamic acid-based UV absorbers, and the like can be mentioned.
  • the transmittance at a wavelength of 365 nm satisfies 35% or less in a 0.002 mass% propylene glycol monomethyl ether acetate solution
  • X 1 , X 2 and X 3 are each independently a hydrogen atom, a hydroxyl group, —OR a , or an optionally substituted hydrocarbon having 1 to 15 carbon atoms
  • R a represents an optionally substituted hydrocarbon group having 1 to 15 carbon atoms
  • at least one of X 1 , X 2 and X 3 is a hydroxyl group, —OR a , or an optionally substituted hydrocarbon group having 1 to 15 carbon atoms
  • X 4 represents a hydrogen atom or a halogen atom.
  • the hydrocarbon group having 1 to 15 carbon atoms in X 1 , X 2 and X 3 and R a is a linear or branched aliphatic hydrocarbon group, an aromatic hydrocarbon group groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, dodecyl group, phenyl group, naphthyl group and biphenyl group.
  • the hydrocarbon group may have 1 to 12 carbon atoms, or 1 to 8 carbon atoms.
  • the hydrocarbon group may be an aliphatic hydrocarbon group, may be a linear or branched alkyl group, a methyl group, a t-butyl group, a t-pentyl group, an n-octyl group, a t-octyl group. (1,1,3,3-tetramethylbutyl group), 2-ethylhexyl group.
  • substituents include halogen atoms, hydroxyl groups, cyano groups, or groups containing carbonyl groups, ester groups, ether groups, amide groups, imide groups, etc., and acyl groups, acyloxy groups, alkoxy groups, aryloxy groups, glycidyl groups, and the like.
  • the substituent of the aromatic hydrocarbon group may be an alkyl group.
  • hydrocarbon groups having substituents include -C 2 H 3 (OH)-CH 2 -O-C 8 H 17 , -C 2 H 3 (OH)-CH 2 -O-C 12 H 25 , —CH(CH 3 )—CO 2 —C 8 H 17 , methacryloyloxyethyl, etc., and also 4-methylphenyl, 3-chlorophenyl, 4-benzyloxyphenyl, 4-cyanophenyl, 4-phenoxyphenyl , 4-glycidyloxyphenyl, 4-isocyanuratephenyl, and the like.
  • the —C 8 H 17 , —C 12 H 25 , etc. may each be linear or branched.
  • the halogen atom includes a chlorine atom, a fluorine atom, a bromine atom, and the like.
  • X 1 , X 2 and X 3 , and R a having 1 to 15 carbon atoms which may have a substituent group
  • the hydrocarbon group may be an unsubstituted hydrocarbon group having 1 to 15 carbon atoms, an unsubstituted aliphatic hydrocarbon group, an unsubstituted linear or It may be a branched alkyl group.
  • X 2 is a hydrogen atom
  • X 1 and X 3 are each independently a hydrogen atom or have 1 carbon atom without a substituent.
  • 1 to 15 aliphatic hydrocarbon groups at least one of X 1 and X 3 is an unsubstituted aliphatic hydrocarbon group having 1 to 15 carbon atoms
  • X 4 is a hydrogen atom or chlorine Atoms are preferred.
  • the unsubstituted aliphatic hydrocarbon group having 1 to 15 carbon atoms of X 1 and X 3 may be an aliphatic hydrocarbon group having 1 to 12 carbon atoms and has 1 carbon atom. ⁇ 8 aliphatic hydrocarbon groups.
  • the transmittance at a wavelength of 365 nm satisfies 35% or less in a 0.002% by mass propylene glycol monomethyl ether acetate solution, and a triazine-based ultraviolet absorber having the following general formula (B) At least one UV absorber selected from the group consisting of
  • Y 1 , Y 2 , Y 3 , Y 4 , Y 5 and Y 6 each independently may have a hydrogen atom, a hydroxyl group, —OR b , or a substituent represents a hydrocarbon group having 1 to 15 carbon atoms
  • R b represents a hydrocarbon group having 1 to 15 carbon atoms which may have a substituent
  • Y 1 , Y 2 , Y 3 , Y 4 At least one of Y 5 and Y 6 represents a hydroxyl group, —OR b , or a hydrocarbon group having 1 to 15 carbon atoms which may have a substituent.
  • the optionally substituted hydrocarbon group having 1 to 15 carbon atoms in Y 1 , Y 2 , Y 3 , Y 4 , Y 5 and Y 6 and R b is the above X 1 , X 2 , X 3 , and R a may be the same as the hydrocarbon group having 1 to 15 carbon atoms which may have a substituent.
  • At least one of Y 2 , Y 4 and Y 6 may be a hydroxyl group and may be a hydroxyphenyltriazine-based UV absorber.
  • Y 1 , Y 2 , Y 3 , Y 4 , Y 5 and Y 6 are each independently a hydroxyl group, —OR b , or an unsubstituted aliphatic hydrocarbon group having 1 to 15 carbon atoms, R b being an optionally substituted aliphatic hydrocarbon group having 1 to 15 carbon atoms, Y 2 , At least one of Y 4 and Y 6 is preferably a hydroxyl group, and each of Y 1 , Y 2 , Y 3 , Y 4 , Y 5 and Y 6 is independently a hydroxyl group or -OR b .
  • R b is an aliphatic hydrocarbon group having 1 to 15 carbon atoms which may have an ester group, and at least one of Y 2 , Y 4 and Y 6 is more preferably a hydroxyl group.
  • Y 1 and Y 2 are each independently hydroxyl groups or —OR b
  • Y 4 and Y 6 are hydroxyl groups
  • Y 3 and Y 5 is —OR b and R b is an aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have an ester group such as —CH(CH 3 )—CO 2 —C 8 H 17 It's okay.
  • the benzophenone-based ultraviolet absorber includes a hydroxybenzophenone-based ultraviolet absorber, which has a transmittance of 35% or less in a 0.002% by mass propylene glycol monomethyl ether acetate solution at a wavelength of 365 nm, and has the following general formula ( At least one ultraviolet absorber selected from the group consisting of hydroxybenzophenone-based ultraviolet absorbers represented by C) can be mentioned.
  • Z 1 represents a hydroxyl group, —OR c , or an optionally substituted hydrocarbon group having 1 to 15 carbon atoms
  • Z 2 represents a hydrogen atom, a hydroxyl group, —OR c or an optionally substituted hydrocarbon group having 1 to 15 carbon atoms
  • Z 3 represents a hydrogen atom or a hydroxyl group
  • R c optionally has a substituent represents a hydrocarbon group having 1 to 15 carbon atoms.
  • the optionally substituted hydrocarbon group having 1 to 15 carbon atoms in Z 1 and Z 2 and R c is the above X 1 , X 2 and X 3 , and the hydrocarbon group having 1 to 15 carbon atoms which may have a substituent for R a .
  • Z 1 is a hydroxyl group, —OR c , or an aliphatic hydrocarbon having 1 to 8 carbon atoms having no substituents.
  • Z 2 is a hydrogen atom, a hydroxyl group, —OR c , or an unsubstituted aliphatic hydrocarbon group having 1 to 8 carbon atoms
  • Z 3 is a hydrogen atom or a hydroxyl group
  • R c is preferably an unsubstituted aliphatic hydrocarbon group having 1 to 8 carbon atoms
  • Z 1 is a hydroxyl group, —OR c , or an unsubstituted aliphatic group having 1 to 4 carbon atoms
  • it is a hydrocarbon group
  • Z 2 and Z 3 are a hydrogen atom or a hydroxyl group
  • R c is an unsubstituted aliphatic hydrocarbon group having 1 to 4 carbon atoms.
  • the weight average molecular weight of the ultraviolet absorber used in the present invention is usually 80 or more, preferably 150 or more, more preferably 300 or more, and usually 2000 or less, preferably 1500 or less, and more preferably 1500 or less, from the viewpoint of efficiently absorbing ultraviolet rays. is 900 or less.
  • the polymer of the ultraviolet absorber has a low ultraviolet absorbing ability, a non-polymeric compound having no repeating unit is preferable.
  • two or more ultraviolet absorbers may be mixed and used in the present invention as long as the transmittance at a wavelength of 365 nm is 35% or less in a 0.002% by mass propylene glycol monomethyl ether acetate solution. That is, the ultraviolet absorber used in the present invention alone has a transmittance of 0.002% by mass at a wavelength of 365 nm exceeding 35% in a propylene glycol monomethyl ether acetate solution. If the transmittance at a wavelength of 365 nm is 35% or less in a 0.002% by mass propylene glycol monomethyl ether acetate solution, an ultraviolet absorber of a mixture thereof can be used.
  • UV absorbers used in the present invention include 2-phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl), 5-chloro-2 -[3-(tert-butyl)-2-hydroxy-5-methylphenyl]-2H-benzotriazole, 2,2'-dihydroxy-4-methoxybenzophenone, and the like, but are not limited to these.
  • Commercially available UV absorbers used in the present invention include, but are not limited to, Tinuvin329, Tinuvin326, Tinuvin477, TinuvinPS (manufactured by BASF), KEMIISORB111, and KEMISORB73 (Kemipro Kasei). is not.
  • the content of the ultraviolet absorber while forming a cross-sectional shape with a taper angle of less than 60 degrees, is easy to suppress development residue, from the point that it is difficult to cause pixel chipping, the total solid content of the photosensitive red resin composition
  • it may generally be in the range of 0.1% by mass to 10.0% by mass, preferably in the range of 0.1% by mass to 7.0% by mass, more preferably 0.1% by mass % to 5.0 mass %, more preferably 0.1 mass % to 4.0 mass %.
  • the solid content is everything other than the solvent, and liquid photopolymerizable compounds and the like are also included.
  • the ratio of the total mass of the ultraviolet absorber to the total mass of the photoinitiator and the ultraviolet absorber is preferably in the range of 5% by mass to 70% by mass, more preferably 10% by mass to 50% by mass. Within range.
  • the content ratio of the ultraviolet absorber is within the above range, it is easy to form a cross-sectional shape with a taper angle of less than 60 degrees, it is easy to suppress development residues, and it is difficult to cause pixel chipping.
  • the coloring material is composed of a pigment containing at least a red pigment. That is, the pigment is 100% by mass with respect to the total amount of the coloring material. Since the coloring material is composed of a pigment containing at least a red pigment, it is possible to form a red colored layer in which chromaticity change due to manufacturing processes such as ultraviolet irradiation and post-baking is suppressed.
  • the term "pigment” as used herein means a solvent-insoluble dye compound.
  • the amount dissolved in 100 g of propylene glycol monomethyl ether acetate at 25° C. the amount dissolved in 100 g of water at 25° C.
  • Organic pigments are both preferably 0.1 g or less, and 0.1 g or less. It is more preferably 05 g or less, and even more preferably 0.01 g or less.
  • Organic pigments are preferably used because of their high color developability and high heat resistance. Examples of organic pigments include compounds classified as pigments in the Color Index (C.I.; published by The Society of Dyers and Colorists). .) numbered ones can be mentioned.
  • red pigment for example, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57: 1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243
  • R 61 and R 62 are each independently a 4-chlorophenyl group or a 4-bromophenyl group.
  • the red pigment from the viewpoint of expanding the color gamut, it is preferable to use a diketopyrrolopyrrole pigment, and the diketopyrrolopyrrole content in the total amount of the coloring material is preferably 30% by mass or more, preferably 40% by mass or more. Containing is more preferable.
  • diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, 255, 264, 272, 291, and diketopyrrolopyrrole pigments represented by the above general formula (i), among which C.I. I. Pigment Red 254, 272, 291, and at least one selected from diketopyrrolopyrrole pigments in which R 61 and R 62 in the general formula (i) are each a 4-bromophenyl group are preferred.
  • the red pigment is preferably at least one selected from Pigment Red 254, Pigment Red 177, and Pigment Red 291 from the viewpoint of improving brightness.
  • pigments may be used as the coloring material from the viewpoints of color adjustment, brightness improvement, and re-solubility improvement.
  • yellow pigments for example, yellow pigments, orange pigments and the like are preferably used.
  • yellow pigments include C.I. I.
  • the total content of other pigments other than the red pigment may be 0% by mass, may be 1% by mass or more, and may be 10% by mass with respect to the total amount of the colorant. On the other hand, it is usually 50% by mass or less, preferably 30% by mass or less.
  • the average primary particle diameter of the coloring material used in the present invention is not particularly limited as long as the coloring layer of the color filter can develop a desired color, and varies depending on the type of coloring material used. is preferably in the range of 10 to 100 nm, more preferably 15 to 60 nm. Since the average primary particle size of the colorant is within the above range, the display device equipped with the color filter produced using the photosensitive red resin composition according to the present invention has high contrast and high quality. be able to.
  • the average dispersed particle size of the colorant in the photosensitive red resin composition varies depending on the type of colorant used, but is preferably in the range of 10 to 100 nm, more preferably in the range of 15 to 60 nm. is more preferred.
  • the average dispersed particle size of the colorant in the photosensitive red resin composition is the dispersed particle size of the colorant particles dispersed in the dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. It is a thing.
  • the photosensitive red resin composition is diluted with a solvent used in the photosensitive red resin composition to a concentration that can be measured with a laser light scattering particle size distribution meter (for example, 1000 times), and measured at 23° C. by a dynamic light scattering method using a laser light scattering particle size distribution analyzer (eg, Nanotrack particle size distribution analyzer UPA-EX150 manufactured by Nikkiso Co., Ltd.).
  • the average distribution particle size here is the volume average particle size.
  • the coloring material used in the present invention can be produced by known methods such as recrystallization and solvent salt milling. Alternatively, a commercially available coloring material may be used after undergoing fine processing.
  • the content of the coloring material in the photosensitive red resin composition according to the present invention is not particularly limited.
  • the content of the coloring material is usually in the range of 3% to 65% by mass, preferably 4% to 60% by mass, based on the total solid content of the photosensitive red resin composition, from the viewpoint of dispersibility and dispersion stability. % by mass, more preferably 15% to 60% by mass. If it is at least the above lower limit, the colored layer will have a sufficient color density when the photosensitive red resin composition is applied to a predetermined film thickness (usually 1.0 ⁇ m to 5.0 ⁇ m). Moreover, if it is below the said upper limit, while being excellent in storage stability, the coloring layer which has sufficient hardness and adhesiveness with a board
  • the total content of the colorant is preferably 20% by mass to 65% by mass, more preferably 20% by mass to 65% by mass, based on the total solid content of the photosensitive red resin composition. It is within the range of 30% by mass to 60% by mass.
  • the colorant is dispersed in a solvent with a dispersant.
  • the dispersant used in the present invention contains at least one of a block copolymer and a graft copolymer from the viewpoint of being able to suitably disperse the colorant and suppress development residue.
  • At least one of the block copolymer and the graft copolymer contains a tertiary amine because it can disperse the coloring material appropriately, has good dispersion stability, and can easily suppress development residue. It is preferably at least one of a block copolymer containing a repeating unit and a graft copolymer containing a repeating unit having a tertiary amine.
  • a repeating unit having a tertiary amine is a site having affinity with the coloring material.
  • a block copolymer containing a repeating unit having a tertiary amine, and a graft copolymer containing a repeating unit having a tertiary amine are usually block copolymers containing a repeating unit that serves as a site having affinity with a solvent. Or it may be a graft copolymer.
  • the repeating unit having a tertiary amine may have a tertiary amine, and the tertiary amine may be contained in the side chain of the copolymer or may constitute the main chain. .
  • the site having affinity with the coloring material is preferably a repeating unit having a tertiary amine in the side chain, and the main chain skeleton is difficult to thermally decompose and has high heat resistance. ) is more preferred.
  • R 41 is a hydrogen atom or a methyl group
  • a 1 is a divalent linking group
  • R 42 and R 43 are each independently a hydrogen atom, or a hydrocarbon optionally containing a hetero atom. group, and R 42 and R 43 may combine with each other to form a ring structure.
  • a 1 is a divalent linking group.
  • the divalent linking group for example, a linear, branched or cyclic alkylene group, a linear, branched or cyclic alkylene group having a hydroxyl group, an arylene group, -CONH- group, -COO- group, -NHCOO- groups, ether groups (--O--groups), thioether groups (--S--groups), and combinations thereof.
  • the bonding direction of the divalent linking group is arbitrary.
  • a 1 in the general formula (I) is preferably a divalent linking group containing a -CONH- group or a -COO- group, and a -CONH- group or a -COO- group.
  • an alkylene group having 1 to 10 carbon atoms are more preferable.
  • Examples of the hydrocarbon group in the hydrocarbon group optionally containing a heteroatom for R 42 and R 43 include an alkyl group, an aralkyl group and an aryl group.
  • Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2-ethylhexyl group, cyclopentyl group, cyclohexyl group and the like, and the number of carbon atoms in the alkyl group is 1 to 18 are preferable, and among them, a methyl group or an ethyl group is more preferable.
  • the aralkyl group includes, for example, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like.
  • the number of carbon atoms in the aralkyl group is preferably 7-20, more preferably 7-14.
  • Aryl groups include phenyl, biphenyl, naphthyl, tolyl, and xylyl groups.
  • the number of carbon atoms in the aryl group is preferably 6-24, more preferably 6-12.
  • the preferable number of carbon atoms does not include the number of carbon atoms of the substituent.
  • a hydrocarbon group containing a heteroatom has a structure in which a carbon atom in the hydrocarbon group is replaced with a heteroatom, or a structure in which a hydrogen atom in the hydrocarbon group is replaced by a substituent containing a heteroatom.
  • the heteroatom that the hydrocarbon group may contain include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom and the like.
  • hydrogen atoms in the hydrocarbon group may be substituted with halogen atoms such as fluorine, chlorine and bromine atoms.
  • R 42 and R 43 are bonded to each other to form a ring structure means that R 42 and R 43 form a ring structure via a nitrogen atom.
  • the ring structure formed by R42 and R43 may contain a heteroatom.
  • the ring structure is not particularly limited, examples thereof include pyrrolidine ring, piperidine ring, morpholine ring and the like.
  • R 42 and R 43 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, or R 42 and R 43 are bonded to form a pyrrolidine ring, It preferably forms a piperidine ring or a morpholine ring.
  • Examples of monomers that derive structural units represented by the general formula (I) include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, and the like.
  • Alkyl group-substituted amino group-containing (meth)acrylates, alkyl group-substituted amino group-containing (meth)acrylamides such as dimethylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, and the like can be mentioned.
  • dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylaminopropyl (meth)acrylamide can be preferably used in terms of improving dispersibility and dispersion stability.
  • the structural unit represented by formula (I) may consist of one type, or may contain two or more types of structural units.
  • the structural unit that functions as the coloring material adsorption site includes at least a part of the nitrogen site of the structural unit represented by the general formula (I) and an organic At least one selected from the group consisting of acid compounds and halogenated hydrocarbons preferably forms a salt (hereinafter, such a copolymer may be referred to as a salt-type copolymer).
  • a salt-type copolymer As the organic acid compound, among others, a compound represented by the following general formula (1) and a compound represented by the following general formula (3) are preferable. ) are preferred. That is, at least one compound selected from the group consisting of the organic acid compound and the halogenated hydrocarbon is preferably one or more compounds selected from the group consisting of the following general formulas (1) to (3). can.
  • R a is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group which may have a substituent or a benzyl group, or -O- Represents R e
  • R e is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group which may have a substituent or a benzyl group, or a C 1 to 4 represents a (meth)acryloyl group via an alkylene group.
  • R b , R b′ , and R b′′ each independently represent a hydrogen atom, an acidic group or an ester group thereof, or a substituent.
  • a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms a vinyl group which may have a substituent, a phenyl group which may have a substituent or a benzyl group, or -O- R f represents an optionally substituted linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group optionally having a substituent, a substituted may be a phenyl group or a benzyl group, or a (meth)acryloyl group via an alkylene group having 1 to 4 carbon atoms, and X represents a chlorine atom, a bromine atom, or an iodine atom.
  • R c and R d are each independently a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl group or a benzyl group, Alternatively, —O—R e , where R e is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl group or a benzyl group, or a carbon number represents a (meth)acryloyl group via 1 to 4 alkylene groups, provided that at least one of R c and R d contains a carbon atom.
  • each code of the general formulas (1) to (3) may be the same as described in WO2016/104493.
  • the organic acid compound is an acidic organic phosphorus compound such as phenylphosphonic acid or phenylphosphinic acid from the viewpoint of excellent dispersibility and dispersion stability of the coloring material.
  • Specific examples of the organic acid compound used in such a dispersant include, for example, organic acid compounds described in JP-A-2012-236882 and the like as suitable ones.
  • the halogenated hydrocarbon is preferably at least one selected from allyl halides such as allyl bromide and benzyl chloride, and aralkyl halides, from the viewpoint of excellent dispersibility and dispersion stability of the coloring material.
  • the content of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons forms a salt with the terminal nitrogen moiety of the structural unit represented by general formula (I). Therefore, the total of at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons is 0 for the terminal nitrogen portion of the structural unit represented by general formula (I) It is preferably 0.01 mol or more, more preferably 0.05 mol or more, still more preferably 0.1 mol or more, and particularly preferably 0.2 mol or more. When it is at least the above lower limit, the effect of improving the dispersibility of the coloring material by salt formation is likely to be obtained.
  • At least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons may be used singly or in combination of two or more. When two or more are combined, the total content is preferably within the above range.
  • the salt-type copolymer As a method for preparing the salt-type copolymer, at least one selected from the group consisting of the organic acid compound and the halogenated hydrocarbon is added to the solvent in which the copolymer before salt formation is dissolved or dispersed, and the mixture is stirred. and a method of heating if necessary.
  • the terminal nitrogen portion of the structural unit represented by the general formula (I) of the copolymer and at least one selected from the group consisting of the organic acid compound and the halogenated hydrocarbon form a salt. and the ratio thereof can be confirmed by a known technique such as NMR.
  • the copolymer having a structural unit represented by the general formula (I) is a graft copolymer having a structural unit represented by the general formula (I), and It is more preferably at least one block copolymer having an A block and a B block containing the structural unit represented by the general formula (I).
  • the graft copolymer and the block copolymer will be described in order.
  • a graft copolymer having a structural unit represented by the general formula (I) As a graft copolymer having a structural unit represented by the general formula (I), a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the following general formula (II) a copolymer, and at least one selected from the group consisting of at least a portion of the nitrogen moieties possessed by the structural unit represented by the general formula (I) of the graft copolymer, an organic acid compound, and a halogenated hydrocarbon; and at least one salt-type graft copolymer in which a salt is formed.
  • R 41′ is a hydrogen atom or a methyl group
  • a 2 is a direct bond or a divalent linking group
  • Polymer represents a polymer chain
  • the constituent units of the polymer chain include (meth)acrylate (Contains structural units derived from
  • A2 is a direct bond or a divalent linking group.
  • the divalent linking group for A2 is not particularly limited as long as it can link the carbon atom derived from the ethylenically unsaturated bond and the polymer chain.
  • Examples of the divalent linking group for A 2 include those similar to the divalent linking group for A 1 .
  • a 2 in general formula (II) is preferably a divalent linking group containing a -CONH- group or a -COO- group, and a -CONH- group or a -COO- group. , and an alkylene group having 1 to 10 carbon atoms.
  • Polymer represents a polymer chain, and structural units of the polymer chain include structural units derived from (meth)acrylate.
  • the graft copolymer has a structural unit represented by the general formula (II) having a specific polymer chain, so that the solvent affinity is improved, and the dispersibility and dispersion stability of the coloring material are improved. and the compatibility with the photoinitiator, which will be described later, is also improved.
  • Examples of structural units of the polymer chain include structural units represented by the following general formula (IV).
  • R 44′′ is a hydrogen atom or a methyl group
  • a 4 is a divalent linking group
  • R 50 is a hydrogen atom or a hydrocarbon group which may contain a hetero atom.
  • Examples of the divalent linking group for A 4 include those similar to the divalent linking group for A 1 .
  • a structural unit derived from (meth)acrylate a structural unit represented by general formula (IV), in which A 4 in general formula (IV) is a divalent linking group containing a —COO— group, is , at least included.
  • a 4 in general formula (IV) may contain a divalent linking group containing a -CONH- group.
  • hydrocarbon groups in the hydrocarbon group optionally containing a heteroatom in R 50 include alkyl groups, alkenyl groups, aryl groups, and combinations thereof such as aralkyl groups and alkyl-substituted aryl groups.
  • the hydrocarbon group in the hydrocarbon group optionally containing a heteroatom for R 50 includes, for example, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an aryl group, an aralkyl group, and an alkyl-substituted Combinations of these, such as aryl groups, are included.
  • the alkyl group having 1 to 18 carbon atoms may be linear, branched, or cyclic, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, n- nonyl group, n-lauryl group, n-stearyl group, cyclopentyl group, cyclohexyl group, bornyl group, isobornyl group, dicyclopentanyl group, adamantyl group, lower alkyl group-substituted adamantyl group and the like.
  • the number of carbon atoms in the alkyl group is preferably 1-12, more preferably 1-6.
  • the alkenyl group having 2 to 18 carbon atoms may be linear, branched or cyclic. Examples of such alkenyl groups include vinyl groups, allyl groups, and propenyl groups. Although the position of the double bond of the alkenyl group is not limited, it is preferable that the alkenyl group has a double bond at the terminal from the viewpoint of the reactivity of the resulting polymer.
  • the alkenyl group preferably has 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms.
  • Aryl groups include phenyl, biphenyl, naphthyl, tolyl, and xylyl groups. The number of carbon atoms in the aryl group is preferably 6-24, more preferably 6-12.
  • the aralkyl group includes a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like, and may further have a substituent.
  • the number of carbon atoms in the aralkyl group is preferably 7-20, more preferably 7-14.
  • a linear or branched alkyl group having 1 to 30 carbon atoms may be bonded as a substituent to the aromatic ring such as the aryl group or the aralkyl group.
  • hydrocarbon group for R 50 from the viewpoint of dispersion stability, among them, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 12 carbon atoms which may be substituted with an alkyl group, and an alkyl group.
  • aralkyl groups having 7 to 14 carbon atoms, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n It is preferably one or more selected from the group consisting of -nonyl group, n-lauryl group, n-stearyl group, phenyl group optionally substituted with alkyl group, and benzyl group.
  • heteroatom examples include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom and the like.
  • the hydrocarbon group which may contain a heteroatom includes, for example, -CO-, -COO-, -OCO-, -O-, -S-, -CO-S-, - S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O- , —O—NH— and other connecting groups.
  • the hydrocarbon group may have a substituent as long as it does not interfere with the dispersion performance of the graft copolymer. Nitro group, cyano group, epoxy group, isocyanate group, thiol group and the like.
  • the hydrocarbon group optionally containing a heteroatom for R 50 may have a structure in which a polymerizable group such as an alkenyl group is added to the end of the hydrocarbon group via a linking group containing a heteroatom.
  • Examples of monomers that induce structural units represented by general formula (IV) include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) Acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate , dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, (meth) acrylic acid, 2-methacryloyloxyethyl succinate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- Hydroxybut
  • the R 50 it is preferable to use one having excellent solubility in the organic solvent described later, and it may be appropriately selected according to the organic solvent used in the colorant dispersion.
  • the organic solvent is an ether-alcohol acetate-based, ether-based, ester-based, or alcohol-based organic solvent generally used as an organic solvent for a colorant dispersion
  • a structural unit represented by the following general formula (III) and a structural unit represented by the following general formula (III') are added to the structural unit of the polymer chain in the structural unit represented by the general formula (II).
  • the inclusion of at least one structural unit selected from the group consisting of the structural units is the suppression of development residue, the shortening of the development time of the photosensitive resin composition, and the cured product of the photosensitive red resin composition It is preferable from the point that the solvent resistance of is further improved.
  • the structural unit represented by the following general formula (III) and the structural unit represented by the following general formula (III') are structural units included in the structural unit represented by the general formula (IV).
  • R 44 is a hydrogen atom or a methyl group
  • a 3 is a divalent linking group
  • R 45 is an ethylene group or a propylene group
  • R 46 is a hydrogen atom or a hydrocarbon group
  • m represents a number of 3 or more and 80 or less.
  • R 44′ is a hydrogen atom or a methyl group
  • a 3′ is a divalent linking group
  • R 47 is an alkylene group having 1 to 10 carbon atoms
  • R 48 has 3 to 7 carbon atoms.
  • the alkylene group of R 49 is a hydrogen atom or a hydrocarbon group
  • n represents a number of 1 or more and 40 or less.
  • Examples of the divalent linking group for A 3 include those similar to the divalent linking group for A 1 . Among them, from the viewpoint of solubility in organic solvents used for color filters, A 3 in general formula (III) is preferably a divalent linking group containing a -CONH- or -COO- group. , -CONH- group or -COO- group is more preferred, and -COO- group is even more preferred.
  • m represents the number of repeating units of an ethylene oxide chain or a propylene oxide chain, and represents a number of 3 or more. is more preferable.
  • the upper limit of m is 80 or less, but preferably 50 or less from the viewpoint of solubility in organic solvents used for color filters.
  • the hydrocarbon group for R 46 may be the same as the hydrocarbon group for R 50 .
  • an alkyl group having 1 to 18 carbon atoms an aryl group having 6 to 12 carbon atoms which may be substituted with an alkyl group
  • the alkyl group is preferably one or more selected from the group consisting of optionally substituted aralkyl groups having 7 to 14 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl. It is preferably one or more selected from the group consisting of groups, n-nonyl groups, n-lauryl groups, n-stearyl groups, phenyl groups optionally substituted with alkyl groups, and benzyl groups.
  • examples of the divalent linking group for A3 ' include the same divalent linking groups as the divalent linking groups for A1.
  • a 3' in general formula (III') is a divalent linking group containing a -CONH- or -COO- group. is preferred, a -CONH- group or a -COO- group is more preferred, and a -COO- group is even more preferred.
  • R 47 is an alkylene group having 1 to 10 carbon atoms, and an alkylene group having 2 to 8 carbon atoms is preferable from the viewpoint of solvent resolubility.
  • R 48 is an alkylene group having 3 to 7 carbon atoms. Among them, an alkylene group having 3 to 5 carbon atoms, and more preferably an alkylene group having 5 carbon atoms are preferable from the standpoint of substrate adhesion.
  • R 49 is a hydrogen atom or a hydrocarbon group, and the hydrocarbon group for R 49 may be the same as the hydrocarbon group for R 46 above.
  • n in the general formula (III′) represents the number of repeating units of the ester chain, and represents a number of 1 or more. There is preferably one, and more preferably 3 or more. On the other hand, the upper limit of n is 40 or less, but preferably 20 or less in terms of solubility in organic solvents used for color filters.
  • At least one structural unit selected from the group consisting of structural units represented by the general formula (III) and structural units represented by the following general formula (III') may be Although it is good, 2 or more types may be mixed.
  • the structural unit represented by the general formula (III) is included in the polymer chain, the effect of the solvent affinity portion due to the oxygen atom becomes more pronounced, suppressing development residue and developing the photosensitive resin composition. It is preferable from the viewpoint of shortening the time and improving the solvent resistance.
  • the general formula (I) is preferably 1% by mass or more, It is more preferably 2% by mass or more, and even more preferably 4% by mass or more.
  • the total proportion of at least one structural unit selected from the group consisting of structural units represented by the general formula (III) and structural units represented by the general formula (III') is the point of solvent re-solubility Therefore, it is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less when the total constituent units of the polymer chain are 100% by mass.
  • the structural unit represented by the general formula (IV) including the structural unit represented by the general formula (III) and the structural unit represented by the general formula (III') is one It may be used alone or in combination of two or more.
  • the total proportion of the structural units represented by the general formula (IV) is 70% by mass or more when the total structural units of the polymer chain are 100% by mass. It is preferably 90% by mass or more, more preferably 90% by mass or more.
  • the total proportion of the structural units represented by the general formula (IV) is 100 of the total structural units of the polymer chain. When expressed as % by mass, it may be 100% by mass.
  • the structural unit of the polymer chain in the structural unit represented by the general formula (II) of the graft copolymer includes the structural unit represented by the general formula (III) and the structural unit represented by the general formula (III').
  • Other structural units may be included in addition to the structural units represented by the general formula (IV) including the structural units represented by the formula (IV).
  • Examples of other structural units include structural units derived from monomers having unsaturated bonds copolymerizable with the monomers from which the structural units represented by general formula (IV) are derived.
  • monomers from which other structural units are derived include styrene, styrenes such as ⁇ -methylstyrene, vinyl ethers such as phenyl vinyl ether, and the like.
  • the total proportion of other structural units is 100% of the total structural units of the polymer chain, from the viewpoint of the effect of the present invention.
  • % by mass it is preferably 30% by mass or less, more preferably 10% by mass or less.
  • the weight average molecular weight Mw of the polymer chain in the polymer is preferably 2000 or more, more preferably 3000 or more, and even more preferably 4000 or more, from the viewpoint of the dispersibility and dispersion stability of the colorant. , 15000 or less, and even more preferably 12000 or less. Within the above range, a sufficient steric repulsion effect as a dispersant can be maintained, and the specific surface area of the solvent affinity part of the dispersant increases, allowing the solvent to penetrate the coating film and reach the coloring material.
  • the polymer chain in Polymer preferably has a solubility of 20 (g/100 g solvent) or more at 23° C. in the organic solvent used in combination.
  • the solubility of the polymer chain can be determined based on the solubility of the raw material into which the polymer chain is introduced when preparing the graft copolymer. For example, when a polymerizable oligomer (macromonomer) containing a group having an ethylenically unsaturated bond at the polymer chain and its terminal is used to introduce a polymer chain into the graft copolymer, the polymerizable oligomer has the above solubility. I wish I had it.
  • ethylenically unsaturated bond-containing monomer ethylenically unsaturated bond-containing monomer, hereinafter simply referred to as an ethylenically unsaturated monomer
  • the polymer chain containing the reactive group should have the aforementioned solubility.
  • the structural unit represented by the general formula (I) is preferably contained in a proportion of 3 to 60% by mass, more preferably 6 to 45% by mass, and 9 to 30% by mass. % is more preferred. If the structural unit represented by the general formula (I) in the graft copolymer is within the above range, the ratio of the affinity portion with the coloring material in the graft copolymer will be appropriate, and the solubility in the organic solvent will be good. Since the deterioration of the properties can be suppressed, the adsorptivity to the coloring material is improved, and excellent dispersibility and dispersion stability can be obtained.
  • the structural unit represented by the general formula (II) is preferably contained at a rate of 40 to 97% by mass, more preferably 55 to 94% by mass, and 70 to 70% by mass. 91% by mass is more preferred. If the structural unit represented by the general formula (II) in the graft copolymer is within the above range, the ratio of the solvent-affinity portion in the graft copolymer will be appropriate, resulting in sufficient stericity as a dispersant.
  • the repulsion effect can be maintained, and by increasing the specific surface area of the solvent affinity part of the dispersant, it is possible to suppress the penetration of the solvent into the coating film and the arrival of the coloring material, and the polyethylene oxide chain or polypropylene oxide When a chain is included, the interaction with oxygen atoms becomes remarkable, shortening the development time, improving the solvent resistance, and further improving the effect of suppressing the occurrence of water stains and the occurrence of development residues. can be done.
  • the graft copolymer used in the present invention other than the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II), within a range that does not impair the effects of the present invention
  • it may have other structural units.
  • an ethylenically unsaturated monomer that can be copolymerized with the ethylenically unsaturated monomer or the like that induces the structural unit represented by the general formula (I) is appropriately selected and copolymerized. Building blocks can be introduced.
  • Other structural units copolymerized with the structural units represented by the general formula (I) include, for example, structural units represented by the general formula (IV).
  • the content ratio of the structural units is, at the time of production, the structural unit represented by the general formula (I), the structural unit represented by the general formula (II), and the structural unit represented by the general formula (II) when synthesizing the graft copolymer. It is calculated from the charged amount of the monomer that induces the structural unit represented by the general formula (IV).
  • the weight average molecular weight Mw of the graft copolymer is preferably 4000 or more, more preferably 6000 or more, and even more preferably 8000 or more, from the viewpoint of dispersibility and dispersion stability. . On the other hand, it is preferably 50,000 or less, more preferably 30,000 or less, from the viewpoint of solvent resolubility.
  • the mass average molecular weight Mw in the present invention is a value measured by GPC (gel permeation chromatography).
  • the measurement was carried out using Tosoh's HLC-8120GPC, the elution solvent was N-methylpyrrolidone to which 0.01 mol/liter of lithium bromide was added, and the polystyrene standards for the calibration curve were Mw 377400, 210500, 96000, 50400, 20650, 10850, 5460, 2930, 1300, 580 (Easi PS-2 series manufactured by Polymer Laboratories) and Mw 1090000 (manufactured by Tosoh), and the measurement column was TSK-GEL ALPHA-M ⁇ 2 (manufactured by Tosoh). is.
  • graft copolymer (Method for producing graft copolymer)
  • a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II) is produced. It is not particularly limited as long as it can be done.
  • a graft copolymer having a structural unit represented by the general formula (I) and a structural unit represented by the general formula (II) for example, a monomer represented by the following general formula (Ia) and a polymerizable oligomer (macromonomer) comprising a group having an ethylenically unsaturated bond at the end of the polymer chain as a copolymerization component, and copolymerizing to produce a graft copolymer.
  • a monomer represented by the following general formula (Ia) and a polymerizable oligomer (macromonomer) comprising a group having an ethylenically unsaturated bond at the end of the polymer chain as a copolymerization component and copolymerizing to produce a graft copolymer.
  • other monomers may also be used, and the graft copolymer can be produced using known polymerization means.
  • the monomer represented by the general formula (Ia) and other ethylenically unsaturated monomers to form a copolymer using a polymer chain containing a reactive group capable of reacting with a reactive group contained in the copolymer, the polymer chain may be introduced.
  • a functional group that reacts with the substituent is added.
  • a polymer chain may be introduced by reacting with a polymer chain contained therein.
  • a copolymer having a glycidyl group in the side chain is reacted with a polymer chain having a terminal carboxyl group, or a copolymer having an isocyanate group in the side chain is reacted with a polymer chain having a hydroxyl group at the terminal.
  • additives commonly used in polymerization such as polymerization initiators, dispersion stabilizers, and chain transfer agents, may be used.
  • each block in the block copolymer is not particularly limited, and examples thereof include AB block copolymers, ABA block copolymers, and BAB block copolymers. Among them, an AB block copolymer or an ABA block copolymer is preferable because of its excellent dispersibility.
  • the A block is a block that functions as a coloring material adsorption site and contains at least the structural unit represented by the general formula (I). At least part of the nitrogen sites of the structural units represented by the general formula (I) of the block copolymer and at least one selected from the group consisting of organic acid compounds and halogenated hydrocarbons form a salt. It may be a salt-type block copolymer.
  • the A block may have a structural unit other than the structural unit represented by general formula (I) within the scope of achieving the object of the present invention, and the structural unit represented by general formula (I) and Any structural unit that can be copolymerized can be contained. Specific examples thereof include structural units represented by the general formula (IV).
  • the content ratio of the structural unit represented by general formula (I) in the A block in the block copolymer before salt formation is 50 to 100% by mass with respect to the total mass of all structural units in the A block. is preferred, 80 to 100% by mass is more preferred, and 100% by mass is most preferred. This is because the higher the ratio of the structural unit represented by the general formula (I), the better the adsorptive power to the coloring material, and the better the dispersibility and dispersion stability of the block copolymer.
  • the content ratio of the structural unit is calculated from the charged mass when synthesizing the A block having the structural unit represented by the general formula (I).
  • the content ratio of the structural unit represented by the general formula (I) is the total structural units of the block copolymer from the viewpoint of good dispersibility and dispersion stability. It is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, based on the total mass of. The content ratio of each structural unit in the block copolymer is calculated from the charged mass when synthesizing the block copolymer before salt formation.
  • the structural unit represented by the general formula (I) only needs to have an affinity with the colorant, and may consist of one type or may contain two or more types of structural units. good.
  • the B block is a block that functions as a solvent affinity site.
  • the B block is appropriately selected according to the solvent so as to have solvent affinity, from among monomers having an unsaturated bond that can be copolymerized with the monomer that derives the structural unit represented by general formula (I). It is preferably used As a guideline, it is preferable to introduce the B block so that the solubility of the copolymer at 23° C. in the solvent used in combination is 20 (g/100 g solvent) or more.
  • the structural unit constituting the B block part may consist of one type, or may contain two or more types of structural units. Examples of structural units contained in the B block include structural units represented by the general formula (IV).
  • the structural unit represented by the general formula (IV) at least one selected from the group consisting of the structural unit represented by the general formula (III) and the structural unit represented by the general formula (III') It is preferable from the viewpoint of suppressing development residue, shortening the development time of the photosensitive resin composition, and further improving the solvent resistance of the cured product of the photosensitive red resin composition.
  • the unit number m of the structural unit represented by the general formula (I) and the unit number n of other structural units constituting the solvent-affinity block portion is preferably in the range of 0.01 or more and 1 or less, and is preferably in the range of 0.05 or more and 0.7 or less from the viewpoint of dispersibility and dispersion stability of the coloring material. more preferred.
  • a block copolymer containing an A block containing a structural unit represented by the general formula (I) and a B block containing a structural unit derived from a carboxy group-containing monomer a polymer, and at least one selected from the group consisting of at least part of the nitrogen sites possessed by the structural units represented by the general formula (I) of the block copolymer, an organic acid compound, and a halogenated hydrocarbon contains at least one salt-type block copolymer forming a salt, the block copolymer and at least one of the salt-type block copolymers have an acid value of 1 to 18 mgKOH/g, and a glass transition temperature of It may be 30°C or higher. In this case, it is preferable from the viewpoint of suppressing the generation of development residues.
  • the B block in this case may be similar to the B block of WO2016/104493.
  • the mass average molecular weight Mw of the block copolymer is not particularly limited, but is preferably 1000 or more and 20000 or less, and 2000 or more and 15000 or less, from the viewpoint of improving the colorant dispersibility and dispersion stability. is more preferably 3000 or more and 12000 or less.
  • the weight average molecular weight (Mw) can be measured in the same manner as described above.
  • the content ratio of the structural unit represented by the general formula (IV) is, from the viewpoint of improving the dispersibility of the coloring material, relative to the total mass of all structural units of the block copolymer. It is preferably 40 to 95% by mass, more preferably 50 to 90% by mass. In addition, the content ratio of the structural unit is calculated from the charged mass when synthesizing the block copolymer before salt formation.
  • the copolymer containing the structural unit represented by the general formula (I) has an amine value of 40 mgKOH/g or more and 120 mgKOH/g or less. It is preferable from the viewpoint of improving brightness and contrast. When the amine value is within the above range, the viscosity stability over time and heat resistance are excellent, and alkali developability and solvent re-solubility are also excellent.
  • the amine value of the copolymer containing the structural unit represented by the general formula (I) is preferably 80 mgKOH/g or more, more preferably 90 mgKOH/g or more. preferable.
  • the amine value of the copolymer containing the structural unit represented by the general formula (I) is preferably 110 mgKOH/g or less, more preferably 105 mgKOH/g or less. more preferred.
  • the amine value refers to the number of mg of potassium hydroxide equivalent to perchloric acid required to neutralize the amine component contained in 1 g of the sample, and can be measured by the method defined in JIS-K7237. When measured by this method, even if the amino group forms a salt with the organic acid compound in the dispersant, the organic acid compound is usually dissociated. Amine value can be measured.
  • the content ratio (mol%) of each structural unit in the copolymer in the dispersant can be obtained from the amount of raw materials charged at the time of production, and can be measured using an analyzer such as NMR. Also, the structure of the dispersant can be measured using NMR, various mass spectrometry, and the like. In addition, if necessary, the dispersant is decomposed by thermal decomposition or the like, and the obtained decomposition product is subjected to high performance liquid chromatography, gas chromatograph mass spectrometer, NMR, elemental analysis, XPS / ESCA, TOF-SIMS, etc. can ask.
  • the content of the dispersant may be appropriately selected according to the type of coloring material used, the solid content concentration in the photosensitive red resin composition described later, and the like.
  • the content of the dispersant is preferably in the range of 1% by mass to 40% by mass, more preferably in the range of 2% by mass to 30% by mass, based on the total solid content of the photosensitive red resin composition. be.
  • it is at least the above lower limit the dispersibility and dispersion stability of the coloring material are excellent, and the storage stability of the photosensitive red resin composition is excellent. Moreover, if it is below the said upper limit, developability will become favorable.
  • the content of the dispersant is preferably 2% by mass to 45% by mass, more preferably 3% by mass, based on the total solid content of the photosensitive red resin composition. It is in the range of mass % to 40 mass %.
  • the alkali-soluble resin in the present invention has an acidic group, and can be appropriately selected and used from those that act as a binder resin and are soluble in an alkali developer used for pattern formation.
  • the alkali-soluble resin can be defined as having an acid value of 40 mgKOH/g or more.
  • a preferable alkali-soluble resin in the present invention is a resin having an acidic group, usually a carboxy group. resins, epoxy (meth)acrylate resins having a carboxyl group, and the like. Among these, particularly preferred are those having a carboxy group in the side chain and a photopolymerizable functional group such as an ethylenically unsaturated group in the side chain.
  • acrylic copolymers acrylic resins such as styrene-acrylic copolymers, and epoxy acrylate resins may be used in combination.
  • Acrylic resins such as acrylic copolymers having a structural unit having a carboxy group and styrene-acrylic copolymers having a carboxy group are, for example, a carboxy group-containing ethylenically unsaturated monomer and, if necessary, a copolymer. It is a (co)polymer obtained by (co)polymerizing other polymerizable monomers by a known method.
  • Carboxy group-containing ethylenically unsaturated monomers include, for example, (meth)acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer.
  • the alkali-soluble resin preferably further has a hydrocarbon ring from the viewpoint of excellent adhesion of the colored layer.
  • the present inventors have found that the presence of a hydrocarbon ring, which is a bulky group, in the alkali-soluble resin suppresses the solvent resistance of the resulting colored layer, particularly swelling of the colored layer. Although the action is not clear, the presence of bulky hydrocarbon rings in the colored layer suppresses the movement of molecules in the colored layer, which increases the strength of the coating film and suppresses swelling due to solvents.
  • hydrocarbon rings include cyclic aliphatic hydrocarbon rings which may have substituents, aromatic rings which may have substituents, and combinations thereof, and hydrocarbon rings may have a substituent such as a carbonyl group, a carboxy group, an oxycarbonyl group or an amide group.
  • hydrocarbon rings may have a substituent such as a carbonyl group, a carboxy group, an oxycarbonyl group or an amide group.
  • hydrocarbon rings include aliphatic hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornane, tricyclo[5.2.1.0(2,6)]decane (dicyclopentane), and adamantane.
  • Aromatic rings such as benzene, naphthalene, anthracene, phenanthrene, and fluorene; chain polycyclic rings such as biphenyl, terphenyl, diphenylmethane, triphenylmethane, and stilbene; cardo structures represented by the following chemical formula (ii); be done.
  • the alkali-soluble resin preferably has a maleimide structure represented by the following general formula (iii).
  • RM is an optionally substituted hydrocarbon ring.
  • the alkali-soluble resin has a maleimide structure represented by the above general formula (iii), it has a nitrogen atom in the hydrocarbon ring, so that it has very good compatibility with the dispersant of the present invention and an effect of suppressing development residue. improves.
  • Specific examples of the optionally substituted hydrocarbon ring in R 1 M of the general formula (iii) are the same as the specific examples of the hydrocarbon ring described above.
  • the heat resistance and adhesiveness of the colored layer are improved, and the brightness of the obtained colored layer is also preferably improved.
  • the curability of the colored layer is improved, and the solvent resistance (NMP swelling suppression) is improved, which is particularly preferable.
  • the alkali-soluble resin used in the present invention apart from the structural unit having a carboxy group, using an acrylic copolymer having a structural unit having the above hydrocarbon ring makes it easy to adjust the amount of each structural unit, and the above It is preferable from the viewpoint that the amount of structural units having a hydrocarbon ring can be increased to easily improve the functions of the structural units.
  • the acrylic copolymer having a structural unit having a carboxy group and the above hydrocarbon ring is prepared by using an ethylenically unsaturated monomer having a hydrocarbon ring as the above-mentioned "other copolymerizable monomer". be able to.
  • Examples of ethylenically unsaturated monomers having a hydrocarbon ring include cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, phenoxy Ethyl (meth) acrylate, styrene, etc., and from the point that the cross-sectional shape of the colored layer after development is maintained even in heat treatment, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (Meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate and styrene are preferred.
  • the alkali-soluble resin used in the present invention also preferably has an ethylenically unsaturated bond in its side chain.
  • the alkali-soluble resin and the dispersant of the present invention described above can form a crosslinked bond in the step of curing the resin composition during the production of a color filter, and
  • the alkali-soluble resins can form cross-links, or the alkali-soluble resins and the photopolymerizable compound can form cross-links.
  • an alkali-soluble resin having an ethylenically unsaturated bond in the side chain is used in combination with the dispersant of the present invention, the film strength of the cured film is further improved by a synergistic effect, so that the brightness of the colored layer and the ITO film are improved. Furthermore, the resistance to development is improved, and the heat shrinkage of the cured film is suppressed, resulting in excellent adhesion to the substrate.
  • a method for introducing an ethylenically unsaturated bond into an alkali-soluble resin may be appropriately selected from conventionally known methods.
  • a method in which a compound having both an epoxy group and an ethylenically unsaturated bond in the molecule, such as glycidyl (meth)acrylate, is added to the carboxyl group of the alkali-soluble resin to introduce an ethylenically unsaturated bond into the side chain is added to the carboxyl group of the alkali-soluble resin to introduce an ethylenically unsaturated bond into the side chain.
  • a structural unit having a hydroxyl group is introduced into a copolymer, a compound having an isocyanate group and an ethylenically unsaturated bond is added to the molecule, and an ethylenically unsaturated bond is introduced into the side chain.
  • the alkali-soluble resin used in the present invention may further contain other structural units such as a structural unit having an ester group such as methyl (meth)acrylate and ethyl (meth)acrylate.
  • a structural unit having an ester group functions not only as a component that suppresses the alkali solubility of the photosensitive colored resin composition, but also as a component that improves the solubility in a solvent and the solvent re-solubility.
  • the alkali-soluble resin used in the present invention should contain an alkali-soluble resin having a glass transition temperature (Tg) of 60° C. or less, since it is easy to form a red colored layer having a cross-sectional shape with a taper angle of less than 60 degrees. is preferable, and it is preferable to contain an alkali-soluble resin having a glass transition temperature (Tg) of 30° C. or less.
  • the alkali-soluble resin having a glass transition temperature (Tg) of 60° C. or lower may have a glass transition temperature (Tg) of 0° C. or higher from the viewpoint of improving the development adhesion.
  • the alkali-soluble resin used in the present invention preferably contains 30% by mass or more, preferably 35% by mass or more, of an alkali-soluble resin having a glass transition temperature (Tg) of 60° C. or less with respect to the total amount of the alkali-soluble resin. is more preferable, more preferably 40% by mass or more, and may be 100% by mass.
  • Tg glass transition temperature
  • the glass transition temperature (Tg) of the alkali-soluble resin is measured using differential scanning calorimetry (DSC) (for example, EXSTAR DSC 7020 manufactured by SII Nanotechnology) according to the method described in JIS K7121. be able to.
  • DSC differential scanning calorimetry
  • the peak area that is, the peak with the largest area of the portion protruding from the baseline of the obtained chart is taken as the representative value of the glass transition temperature.
  • the glass transition temperature (Tg) of the copolymer can be calculated by the following formula and used as a guideline.
  • Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer.
  • Tgi homopolymer glass transition temperature value of each monomer, the value in Polymer Handbook (3rd Edition) (J. Brandrup, EHImmergut (Wiley-Interscience, 1989)) can be adopted.
  • the glass transition temperature value (Tgi) of the homopolymer is derived from a monomer of 0°C or less, even if it contains —O— bonds. It preferably contains a structural unit containing a good hydrocarbon group in its side chain, and preferably contains 15% by mass or more of all structural units. Further, the glass transition temperature value (Tgi) of the monomer having a glass transition temperature value (Tgi) of 0° C. or less in the homopolymer is not particularly limited, but from the viewpoint of ensuring durability, it is ⁇ 100. °C or higher, and more preferably -60°C or higher.
  • monomers having a glass transition temperature value (Tgi) of 60° C. or less in a homopolymer include n-butyl methacrylate (Tgi: 20° C.), isobutyl methacrylate (Tgi: 48° C.), 2- Ethylhexyl methacrylate (Tgi: -10°C), 2-ethoxyethyl methacrylate (Tgi: -16°C), isodecyl methacrylate (Tgi: -41°C), methoxypolyethylene glycol #400 methacrylate (Tgi: -69°C), etc. be done.
  • the alkali-soluble resin used in the present invention is an acrylic resin such as an acrylic copolymer and a styrene-acrylic copolymer having a structural unit having a carboxyl group and a structural unit having a hydrocarbon ring.
  • Acrylic resins such as acrylic copolymers and styrene-acrylic copolymers preferably having a structural unit having a carboxy group, a structural unit having a hydrocarbon ring, and a structural unit having an ethylenically unsaturated bond. It is more preferable to have
  • the alkali-soluble resin can be made into an alkali-soluble resin with desired performance by appropriately adjusting the charging amount of each structural unit.
  • the amount of the carboxyl group-containing ethylenically unsaturated monomer to be charged is preferably 5% by mass or more, more preferably 10% by mass or more, based on the total amount of the monomers in order to obtain a good pattern.
  • the amount of the carboxyl group-containing ethylenically unsaturated monomer charged is preferably 50% by mass or less, and 40% by mass or less with respect to the total amount of the monomer.
  • the coating film obtained has sufficient solubility in an alkaline developer, and the proportion of the carboxy group containing ethylenically unsaturated monomer is at the above upper limit. If it is below, the formed pattern tends not to come off from the substrate and the film roughening on the pattern surface tends not to occur during development with an alkaline developer.
  • acrylic resins such as acrylic copolymers and styrene-acrylic copolymers having structural units having ethylenically unsaturated bonds, which are more preferably used as alkali-soluble resins, epoxy groups and ethylenically unsaturated
  • the compound having a bond is preferably 10% by mass to 95% by mass, more preferably 15% by mass to 90% by mass, based on the charged amount of the carboxy group-containing ethylenically unsaturated monomer.
  • a preferred weight average molecular weight (Mw) of the carboxy group-containing copolymer is in the range of 1,000 to 50,000, more preferably 3,000 to 20,000. If it is less than 1,000, the binder function after curing may be significantly deteriorated, and if it exceeds 50,000, pattern formation may become difficult during development with an alkaline developer.
  • the weight average molecular weight (Mw) of the carboxy group-containing copolymer can be measured by Shodex GPC System-21H using polystyrene as a standard substance and THF as an eluent.
  • the epoxy (meth)acrylate resin having a carboxy group is not particularly limited, but an epoxy (meth)acrylate obtained by reacting a reaction product of an epoxy compound and an unsaturated group-containing monocarboxylic acid with an acid anhydride.
  • Acrylate compounds are suitable. Epoxy compounds, unsaturated group-containing monocarboxylic acids, and acid anhydrides can be appropriately selected from known ones and used. Epoxy (meth)acrylate resins having a carboxy group may be used alone or in combination of two or more.
  • an alkali-soluble resin having an acid value of 50 mgKOH/g or more.
  • the alkali-soluble resin preferably has an acid value of 60 mgKOH/g or more and 300 mgKOH/g or less from the viewpoint of developability (solubility) in an alkaline aqueous solution used as a developer and adhesion to a substrate. It is preferably 70 mgKOH/g or more and 200 mgKOH/g or less.
  • the acid value of the alkali-soluble resin can be measured according to JIS K 0070:1992.
  • the ethylenically unsaturated bond equivalent when the side chain of the alkali-soluble resin has an ethylenically unsaturated group improves the film strength of the cured film, improves the development resistance, and provides the effect of excellent adhesion to the substrate. From the point of view, it is preferably in the range of 100 to 2000, more preferably in the range of 140 to 1500. If the ethylenically unsaturated bond equivalent is 2000 or less, the development resistance and adhesion are excellent. Also, if it is 100 or more, the ratio of other structural units such as structural units having a carboxy group and structural units having a hydrocarbon ring can be relatively increased, so that excellent developability and heat resistance can be obtained.
  • the ethylenically unsaturated bond equivalent is the weight average molecular weight per mole of the ethylenically unsaturated bond in the alkali-soluble resin, and is represented by the following formula (1).
  • Ethylenically unsaturated bond equivalent (g / mol) W (g) / M (mol) (In formula (1), W represents the mass (g) of the alkali-soluble resin, and M represents the number of moles (mol) of ethylenically unsaturated bonds contained in the alkali-soluble resin W (g).)
  • the ethylenically unsaturated bond equivalent is obtained, for example, by measuring the number of ethylenically unsaturated bonds contained per 1 g of the alkali-soluble resin in accordance with the iodine value test method described in JIS K 0070: 1992. can be calculated.
  • the alkali-soluble resin used in the photosensitive red resin composition may be used alone or in combination of two or more, and the content is not particularly limited, but the photosensitive red resin
  • the alkali-soluble resin is preferably in the range of 5% to 60% by mass, more preferably in the range of 10% to 40% by mass, based on the total solid content of the composition.
  • the content of the alkali-soluble resin is at least the above lower limit, sufficient alkali developability is obtained, and when the content of the alkali-soluble resin is at most the above upper limit, film roughness and pattern chipping during development are prevented. can be suppressed.
  • the photopolymerizable compound used in the photosensitive red resin composition is not particularly limited as long as it can be polymerized by the photoinitiator, and usually a compound having two or more ethylenically unsaturated bonds is suitable.
  • Polyfunctional (meth)acrylates having two or more acryloyl groups or methacryloyl groups are particularly preferred.
  • As such a polyfunctional (meth)acrylate it may be appropriately selected and used from conventionally known ones. Specific examples include those described in JP-A-2013-029832.
  • polyfunctional (meth)acrylates may be used singly or in combination of two or more. Further, when excellent photocurability (high sensitivity) is required for the photosensitive red resin composition of the present invention, the polyfunctional (meth)acrylate has three polymerizable ethylenically unsaturated bonds (three Functionality) or more is preferable, and poly(meth)acrylates of trihydric or higher polyhydric alcohols and their dicarboxylic acid-modified products are preferable.
  • trimethylolpropane tri(meth)acrylate penta Erythritol tri(meth)acrylate, succinic acid-modified pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol penta (Meth)acrylate modified with succinic acid, dipentaerythritol hexa(meth)acrylate and the like are preferred.
  • the content of the photopolymerizable compound used in the photosensitive red resin composition is not particularly limited, but is preferably in the range of 5% by mass to 60% by mass with respect to the total solid content of the photosensitive red resin composition. , more preferably in the range of 10% by mass to 40% by mass.
  • the content of the photopolymerizable compound is at least the above lower limit, photocuring sufficiently proceeds, the exposed portion can be suppressed from elution during development, the line width shift is suppressed, the solvent resistance is improved, and
  • the content of the photopolymerizable compound is equal to or less than the above upper limit, the alkali developability is sufficient.
  • the photoinitiator in the photosensitive red resin composition of the present invention is not particularly limited, and can be used alone or in combination of two or more of conventionally known various initiators.
  • photoinitiators include aromatic ketones, benzoin ethers, halomethyloxadiazole compounds, ⁇ -aminoketones, biimidazoles, N,N-dimethylaminobenzophenone, halomethyl-S-triazine compounds, and thioxanthone. , oxime esters, and the like.
  • a photoinitiator having an oxime ester skeleton hereinafter referred to as a photoinitiator (hereinafter referred to as It is preferable to use an oxime ester photoinitiator).
  • oxime ester photoinitiators examples include 1,2-octadione-1-[4-(phenylthio)phenyl]-,2-(o-benzoyloxime), ethanone, 1-[9-ethyl-6-( 2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyloxime), JP 2000-80068, JP 2001-233842, JP 2010-527339, JP It can be appropriately selected from among the oxime ester photoinitiators described in Table 2010-527338, JP-A-2013-041153, and the like.
  • the oxime ester photoinitiator preferably has a carbazole skeleton, a diphenyl sulfide skeleton or a fluorene skeleton from the viewpoint of improving sensitivity. It is also preferable from the viewpoint of improving the thermal stability and sensitivity of the oxime ester compound because of the internal electron transfer characteristics.
  • oxime ester photoinitiators having a carbazole skeleton examples include ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime ) (eg, Irgacure OXE02, manufactured by BASF), methanone, [8-[[(acetyloxy)imino][2-(2,2,3,3-tetrafluoropropoxy)phenyl]methyl]-11-(2 -ethylhexyl)-11H-benzo[a]carbazol-5-yl]-, (2,4,6-trimethylphenyl) (eg, Irgacure OXE-03, manufactured by BASF), ethanone, 1-[9-ethyl-6 -(1,3-dioxolane, 4-(2-methoxyphenoxy)-9H-carbazol-3-yl]-, 1-(o-acetylox
  • the oxime ester photoinitiator having a carbazole skeleton it may be used alone or in combination of two or more.
  • 9H-carbazol-3-yl]-,1-(o-acetyloxime) for example, TR-PBG-304, manufactured by Changzhou Tenryu Electric New Materials Co., Ltd.
  • ethanone 1-[9-ethyl-6-( 2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (eg, Irgacure OXE02, manufactured by BASF), and methanone, (9-ethyl-6-nitro-9H- carbazol-3-yl)[4-(2-methoxy-1-methylethoxy-2-methylphenyl]-, o-acetyloxime, among others, 1-propanone ,3-cyclopentyl-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl
  • Examples of the oxime ester photoinitiator having a diphenyl sulfide skeleton include an oxime ester compound represented by the following chemical formula (iv), 1,2-octadione, 1-[4-(phenylthio)phenyl]-, 2-( o-benzoyloxime] (e.g., Irgacure OXE01, manufactured by BASF), 1,2-propanedione, 3-cyclopentyl-1-[4-(phenylthio)phenyl]-,2-(o-benzoyloxime] (e.g., TR-PBG-305, manufactured by Changzhou Power Electronics New Materials Co., Ltd.), 1,2-propanedione, 3-cyclopentyl-1-[4-[(2-hydroxyethoxy)phenylthio]phenyl]-,2-(o-acetyl oxime], 1-pentanone, 1-[4-[4-(2-benzofuranylcarbonyl)phen
  • an oxime ester compound represented by the general formula (1) described in WO 2018/062105 (the following general formula (v)).
  • the oxime ester compound represented by the following general formula (v) may be the same as the oxime ester compound represented by general formula (1) described in WO 2018/062105.
  • R a and R b are each independently a hydrogen atom or an alkyl group, and R c is a thioether bond (-S-), an ether bond (-O-) and a carbonyl bond (- CO—) is a hydrocarbon group optionally containing at least one divalent linking group selected from Z is a hydrogen atom or —(C ⁇ O)R d , where R d is an oxygen atom and a hydrocarbon group optionally containing at least one selected from a sulfur atom, or a heterocyclic group containing no nitrogen atom and containing at least one selected from an oxygen atom and a sulfur atom, and Re is a hydrocarbon group having 1 to 10 carbon atoms.
  • a compound represented by the following chemical formula (v-1) is more preferable.
  • Commercially available products include, for example, TR-PBG-365 (manufactured by Changzhou Tenryu Electric New Materials Co., Ltd.).
  • the total content of the photoinitiator used in the photosensitive red resin composition of the present invention is not particularly limited as long as the effects of the present invention are not impaired, but with respect to the total solid content of the photosensitive red resin composition, It is preferably within the range of 0.1% by mass to 12.0% by mass, more preferably within the range of 1.0% by mass to 8.0% by mass.
  • photocuring proceeds sufficiently to suppress the elution of the exposed portion during development, resulting in good solvent resistance. A decrease in luminance due to yellowing of the layer and deterioration of developability can be suppressed.
  • the content ratio of the photopolymerizable compound and the photoinitiator used in the photosensitive red resin composition is such that the line width shift is suppressed, the solvent resistance is improved, and the development residue is suppressed.
  • the total content of the photoinitiator is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, preferably 40 parts by mass with respect to 100 parts by mass of the photopolymerizable compound. It is not more than 30 parts by mass, more preferably not more than 30 parts by mass.
  • the ratio of the total mass of the photoinitiator to the total mass of the photoinitiator and the ultraviolet absorber is preferably in the range of 30% to 95% by mass, more preferably 50% to 90% by mass. It is within the range of % by mass.
  • photocuring proceeds sufficiently to suppress the elution of the exposed portion during development, while when it is at most the above upper limit, a cross-sectional shape with a taper angle of less than 60 degrees is formed. It's easy to do.
  • the solvent used in the present invention is not particularly limited as long as it does not react with each component in the photosensitive red resin composition and is capable of dissolving or dispersing them.
  • a solvent can be used individually or in combination of 2 or more types.
  • Specific examples of solvents include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, i-propyl alcohol, methoxy alcohol and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ester solvents such
  • glycol ether acetate-based solvents examples include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl carbitol acetate (BCA), 3-methoxy-3-methyl-1-butyl acetate, ethyl ethoxypropionate, ethyl lactate, and one or more selected from the group consisting of 3-methoxybutyl acetate, from the viewpoint of solubility of other components and applicability.
  • BCA butyl carbitol acetate
  • 3-methoxy-3-methyl-1-butyl acetate ethyl ethoxypropionate
  • ethyl lactate examples include one or more selected from the group consisting of 3-methoxybutyl acetate, from the viewpoint of solubility of other components and applicability.
  • the content of the solvent may be appropriately set within a range in which the colored layer can be formed with high accuracy. It may generally be in the range of 55% by mass to 95% by mass, preferably in the range of 65% by mass to 88% by mass, based on the total amount of the photosensitive red resin composition containing the solvent. When the content of the solvent is within the above range, excellent applicability can be obtained.
  • the photosensitive red resin composition of the present invention may optionally contain various additives.
  • additives include antioxidants, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, antifoaming agents, silane coupling agents, ultraviolet absorbers, adhesion promoters, and the like.
  • specific examples of surfactants and plasticizers include those described in JP-A-2013-029832.
  • the photosensitive red resin composition of the present invention further contains an antioxidant from the viewpoint of suppressing the generation of development residues.
  • the photosensitive red resin composition of the present invention contains an antioxidant in combination with a photoinitiator, an alkali-soluble resin, and a photopolymerizable compound, so that during drying during the formation of a coating film of the photosensitive red resin composition, , the photoinitiator, the alkali-soluble resin, and the photopolymerizable compound can be prevented from thermally reacting and deteriorating the developability, so that residues are less likely to occur during development.
  • the heat resistance can be improved, and the decrease in luminance after exposure and post-baking can be suppressed, so that the luminance can be improved.
  • the antioxidant used in the present invention is not particularly limited, and may be appropriately selected from those conventionally known.
  • Specific examples of antioxidants include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hydrazine-based antioxidants, and the like. It is preferable to use a hindered phenol-based antioxidant from the viewpoint of improving the ability to form a fine line pattern according to the design of the line width and from the viewpoint of heat resistance. It may also be a latent antioxidant as described in WO 2014/021023.
  • Hindered phenol-based antioxidants include, for example, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: trade name: IRGANOX1010, manufactured by BASF), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (trade name: Irganox 3114, manufactured by BASF), 2,4,6-tris(4-hydroxy-3 ,5-di-tert-butylbenzyl)mesitylene (trade name: Irganox 1330, manufactured by BASF), 2,2′-methylenebis(6-tert-butyl-4-methylphenol) (trade name: Sumilizer MDP-S, Sumitomo Chemical), 6,6′-thiobis(2-tert-butyl-4-methylphenol) (trade name: Irganox 1081, manufactured by BASF), 3,5-di-
  • pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX1010, manufactured by BASF) is preferable from the viewpoint of heat resistance and light resistance. .
  • the content of the antioxidant is preferably in the range of 0.1% by mass to 10.0% by mass, more preferably 0.5% by mass to the total solid content of the photosensitive red resin composition. It is within the range of 5.0% by mass. If it is at least the above lower limit, it is excellent in that the suppression of generation of development residue is improved and heat resistance is improved. On the other hand, if it is the above upper limit or less, the colored resin composition of the present invention can be made into a highly sensitive photosensitive resin composition.
  • the content of the antioxidant is preferably 2 parts by mass to 100 parts by mass, more preferably 5 parts by mass to 80 parts by mass, with respect to 100 parts by mass of the total amount of the photoinitiator. Within the above range, the effect of the above combination is excellent.
  • silane coupling agents examples include KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-903, KBE-903, KBM573, KBM-403, KBE-402, KBE-403 , KBM-303, KBM-802, KBM-803, KBE-9007, X-12-967C (manufactured by Shin-Etsu Silicone Co., Ltd.) and the like.
  • KBM-502, KBM-503, KBE-502, KBE-503 and KBM-5103 having a methacrylic group or an acrylic group are preferable from the viewpoint of adhesion to SiN substrates.
  • the content of the silane coupling agent is preferably in the range of 0.05% by mass to 10.0% by mass, more preferably 0.1% by mass, relative to the total solid content of the photosensitive red resin composition. % to 5.0% by mass. If it is more than the said lower limit and below the said upper limit, it is excellent in board
  • the method for producing a photosensitive red resin composition of the present invention comprises a coloring material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, the specific ultraviolet absorber, a solvent, and a desired It is preferable from the viewpoint of improving the contrast that it is a method that contains various additive components used by and the coloring material can be uniformly dispersed in the solvent by the dispersant. By mixing using a known mixing means, can be prepared.
  • a coloring material and a dispersant are added to a solvent to prepare a coloring material dispersion, and an alkali-soluble resin and a light are added to the dispersion.
  • a method of mixing a polymerizable compound, a photoinitiator, the specific ultraviolet absorber, and various additive components optionally used (2) a colorant, a dispersant, an alkali-soluble resin, and A method of simultaneously adding and mixing a photopolymerizable compound, a photoinitiator, the specific ultraviolet absorber, and various additive components that are optionally used; (3) dispersing agent and alkali-soluble resin in solvent; , a method of adding a photopolymerizable compound, a photoinitiator, the specific ultraviolet absorber, and various additive components that are optionally used, mixing, and then adding and dispersing a coloring material; (4) in a solvent A coloring material, a dispersant, and an alkali-soluble resin are added
  • the above methods (1) and (4) are preferable because they can effectively prevent the aggregation of the colorant and uniformly disperse the colorant.
  • the method for preparing the colorant dispersion can be appropriately selected from conventionally known dispersion methods. For example, (1) a dispersant is mixed with a solvent in advance and stirred to prepare a dispersant solution, and then an organic acid compound is mixed as necessary to form a salt between the amino group of the dispersant and the organic acid compound.
  • a method of mixing this with a coloring material and, if necessary, other components and dispersing using a known stirrer or disperser (2) mixing and stirring a dispersant in a solvent to prepare a dispersant solution; , a coloring material and, if necessary, an organic acid compound, and if necessary, other components are mixed and dispersed using a known stirrer or disperser; (3) a dispersant is mixed with a solvent and stirred; , Prepare a dispersant solution, then mix the coloring material and other components as necessary, make a dispersion using a known stirrer or disperser, and then add an organic acid compound as necessary. methods and the like.
  • dispersing machines for dispersing include roll mills such as two-roll and three-roll roll mills, ball mills such as ball mills and vibrating ball mills, bead mills such as paint conditioners, continuous disk-type bead mills, and continuous annular-type bead mills.
  • the diameter of the beads used is preferably 0.03 mm to 2.00 mm, more preferably 0.10 mm to 1.0 mm.
  • the photosensitive red resin composition according to the present invention has a cross-sectional shape with a taper angle of less than 60 degrees while suppressing the generation of development residues, and can form a red colored layer with excellent substrate adhesion. , can be suitably used for color filter applications.
  • the color filter according to the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is the photosensitive red resin composition according to the present invention. It is a hardened material.
  • FIG. 1 is a schematic cross-sectional view showing an example of the color filter of the present invention.
  • the color filter 10 of the present invention has a substrate 1, a light shielding portion 2 and a colored layer 3. As shown in FIG.
  • At least one of the colored layers used in the color filter of the present invention is a colored layer that is a cured product of the photosensitive red resin composition of the present invention.
  • the colored layer is usually formed in the opening of the light shielding part on the substrate, which will be described later, and is usually composed of colored patterns of three or more colors.
  • the arrangement of the colored layers is not particularly limited, and may be, for example, a general arrangement such as a stripe type, a mosaic type, a triangle type, or a 4-pixel arrangement type.
  • the width, area, etc. of the colored layer can be arbitrarily set.
  • the thickness of the colored layer can be appropriately controlled by adjusting the coating method, solid content concentration and viscosity of the photosensitive red resin composition, and is preferably in the range of 1 to 5 ⁇ m.
  • the colored layer can be formed, for example, by the following method.
  • a coating method such as a spray coating method, a dip coating method, a bar coating method, a roll coating method, a spin coating method, or a die coating method.
  • the spin coating method and the die coating method can be preferably used.
  • After drying the wet coating film using a hot plate or an oven it is exposed to light through a mask of a predetermined pattern, and the alkali-soluble resin and the polyfunctional monomer are photopolymerized and cured. It is used as a coating film.
  • Light sources used for exposure include, for example, ultraviolet light from low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, and electron beams.
  • the amount of exposure is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
  • heat treatment may be performed.
  • the heating conditions are appropriately selected depending on the mixing ratio of each component in the photosensitive red resin composition to be used, the thickness of the coating film, and the like.
  • a coating film is formed in a desired pattern by developing with a developer to dissolve and remove the unexposed portions.
  • a developer a solution obtained by dissolving an alkali in water or a water-soluble solvent is usually used. An appropriate amount of a surfactant or the like may be added to this alkaline solution.
  • a general method can be adopted as the developing method.
  • the developer After development processing, the developer is usually washed and the cured coating film of the photosensitive red resin composition is dried to form a colored layer.
  • the heating conditions are not particularly limited and are appropriately selected according to the application of the coating film.
  • the light-shielding portion in the color filter of the present invention is formed in a pattern on a substrate to be described later, and can be the same as those used as light-shielding portions in general color filters.
  • the pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape, a matrix shape, and the like.
  • the light shielding portion may be a metal thin film of chromium or the like formed by a sputtering method, a vacuum deposition method, or the like.
  • the light-shielding portion may be a resin layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, or organic pigments in a resin binder.
  • a method of patterning by development using a photosensitive resist a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring a photosensitive resist, and the like can be used. be.
  • the film thickness of the light-shielding portion is set to about 0.2 to 0.4 ⁇ m in the case of a metal thin film, and is set to about 0.5 to 2 ⁇ m in the case of a black pigment dispersed or dissolved in a binder resin. be done.
  • a transparent substrate, a silicon substrate, and a transparent substrate or a silicon substrate on which an aluminum, silver, silver/copper/palladium alloy thin film or the like is formed are used.
  • Other color filter layers, resin layers, transistors such as TFTs, circuits, and the like may be formed on these substrates.
  • the transparent substrate in the color filter of the present invention is not particularly limited as long as it is transparent to visible light, and transparent substrates used in general color filters can be used. Specifically, transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible materials such as transparent resin films, optical resin plates, and flexible glass. material.
  • the thickness of the transparent substrate is not particularly limited, a thickness of about 100 ⁇ m to 1 mm, for example, can be used depending on the application of the color filter of the present invention.
  • the color filter of the present invention may be formed with, for example, an overcoat layer, a transparent electrode layer, an alignment film, columnar spacers, etc., in addition to the above substrate, light shielding portion and colored layer.
  • Display Device A display device according to the present invention includes the color filter according to the present invention.
  • the configuration of the display device is not particularly limited, and can be appropriately selected from conventionally known display devices, such as liquid crystal display devices and organic light-emitting display devices.
  • FIG. 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention.
  • a liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer formed between the color filter 10 and the counter substrate 20.
  • the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, and may have a known configuration as a liquid crystal display device generally using color filters.
  • the driving method of the liquid crystal display device of the present invention is not particularly limited, and a driving method generally used for liquid crystal display devices can be adopted. Examples of such driving methods include the TN method, IPS method, OCB method, and MVA method. Any of these methods can be suitably used in the present invention. Also, the counter substrate can be appropriately selected and used according to the driving method of the liquid crystal display device of the present invention. Further, as the liquid crystal forming the liquid crystal layer, various liquid crystals having different dielectric anisotropy and mixtures thereof can be used according to the driving method of the liquid crystal display device of the present invention.
  • a method for forming the liquid crystal layer a method generally used as a method for manufacturing a liquid crystal cell can be used, and examples thereof include a vacuum injection method and a liquid crystal dropping method. After the liquid crystal layer is formed by the above method, the liquid crystal cell is gradually cooled to room temperature, thereby aligning the enclosed liquid crystal.
  • FIG. 3 is a schematic diagram showing an example of the organic light-emitting display device of the present invention.
  • the organic light-emitting display device 100 of the present invention has a color filter 10 and an organic light-emitting body 80.
  • An organic protective layer 50 and an inorganic oxide film 60 may be provided between the color filter 10 and the organic light emitter 80 .
  • a transparent anode 71, a hole injection layer 72, a hole transport layer 73, a light emitting layer 74, an electron injection layer 75, and a cathode 76 are sequentially formed on the upper surface of the color filter.
  • method, and a method of bonding the organic light-emitting body 80 formed on another substrate onto the inorganic oxide film 60, and the like are known structures can be appropriately used.
  • the organic light-emitting display device 100 manufactured in this way can be applied to, for example, a passive drive type organic EL display and an active drive type organic EL display.
  • the organic light-emitting display device of the present invention is not limited to the configuration shown in FIG. 3, and may have a known configuration as an organic light-emitting display device generally using color filters.
  • the mass average molecular weight (Mw) of the copolymer before salt formation was determined as a standard polystyrene equivalent value by GPC (gel permeation chromatography) according to the measurement method described in the specification of the present invention.
  • the transmittance of the ultraviolet absorber at a wavelength of 365 nm was obtained by preparing a 0.002% by mass propylene glycol monomethyl ether acetate solution of each ultraviolet absorber, and measuring the transmittance of the 0.002% by mass propylene glycol monomethyl ether acetate solution by measuring the transmittance of the 0.002% by mass propylene glycol monomethyl ether acetate solution. It was measured using an infrared spectrophotometer (JASCO Corporation V-770). Table 1 shows the measurement results of the transmittance of the ultraviolet absorbent at a wavelength of 365 nm.
  • UV absorber 2 Tinuvin 326
  • BASF UV absorber 3 Tinuvin 477
  • BASF UV absorber 4 KEMISORB111
  • Chemipro Kasei comparative UV absorber C1 Tinuvin 400
  • BASF comparative UV absorber C2 Tinuvin 900
  • BASF comparative UV Absorbent C3 Tinuvin384-2, manufactured by BASF Comparative UV absorber C4: Kemisorb12, manufactured by Chemipro Kasei Comparative UV absorber C5: Tinuvin479, manufactured by BASF
  • Preparation Example 1 Preparation of alkali-soluble resin A
  • a polymerization tank was charged with 300 parts by mass of PGMEA, heated to 100° C. under a nitrogen atmosphere, and then 55.6 parts by mass of benzyl methacrylate (BzMA), 2.4 parts by mass of MMA, methoxypolyethylene glycol-methacrylate (manufactured by NOF 66 parts by mass of PME-1000), 56 parts by mass of methacrylic acid (MAA), 6 parts by mass of Perbutyl O (manufactured by NOF), and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) continuously over 1.5 hours. Dripped.
  • BzMA benzyl methacrylate
  • MMA methoxypolyethylene glycol-methacrylate
  • MAA methoxypolyethylene glycol-methacrylate
  • MAA methoxypolyethylene glycol-methacrylate
  • MAA methoxypolyethylene glyco
  • An addition reaction was carried out to obtain an alkali-soluble resin A solution (weight average molecular weight (Mw) of 8500, acid value of 75 mgKOH/g, Tg of 25°C, solid content of 40% by mass).
  • the weight average molecular weight was measured with a Shodex GPC System-21H using polystyrene as a standard and THF as an eluent.
  • the acid value was measured according to JIS K 0070.
  • the glass transition temperature (Tg) was measured using differential scanning calorimetry (EXSTAR DSC 7020, manufactured by SII Nano Technology Co., Ltd.) according to the method described in JIS K7121.
  • MMA methyl methacrylate
  • MMA methoxypolyethylene glycol-methacrylate
  • DMMA dimethylaminoethyl methacrylate
  • PGMEA propylene glycol monomethyl ether acetate
  • HLC-8220 manufactured by Tosoh Corporation equipped with an RI detector was used, the developing solvent was THF, the molecular weight standard polymer was standard polystyrene, and GPC was measured to obtain the molecular weight distribution and the mass average molecular weight. Moreover, the amine value was 67 mgKOH/g.
  • AIBN '-azobisisobutyronitrile
  • Example 1 Production of photosensitive red resin composition R-1)
  • Preparation of Colorant Dispersion R (1) In a 225 mL mayonnaise bottle, 64.3 parts by mass of PGMEA, 13.5 parts by mass of the alkali-soluble resin A solution of Preparation Example 1 (solid content: 40% by mass), Synthesis Example 1 10.1 parts by mass of a PGMEA solution (solid content 40% by mass) of the block copolymer (dispersant A) and 0.17 parts by mass of phenylphosphonic acid as a salt-forming agent a of the dispersant were added and stirred. there, C. I.
  • Example 2 Production of photosensitive red resin composition R-2)
  • Example 1 As shown in Table 2, the type of dispersant was changed from dispersant A to the graft copolymer (dispersant B) of Synthesis Example 2 to prepare a colorant dispersion.
  • a photosensitive red resin composition R-2 was obtained in the same manner as the red resin composition R-1.
  • Examples 3 to 5 Production of photosensitive red resin compositions R-3 to R-5)
  • photosensitive red resin compositions R-3 to R-5 were prepared in the same manner as the photosensitive red resin composition R-1, except that the type of ultraviolet absorber was changed as shown in Table 2. got
  • Example 6 to 8 Production of photosensitive red resin compositions R-6 to R-8
  • photosensitive red resin compositions R-6 to R-8 were obtained in the same manner as the photosensitive red resin composition R-1, except that the type of pigment was changed as shown in Table 2. rice field.
  • Example 8 instead of using 12 parts by mass of PR291, 10.2 parts by mass of PR291 and C.I. I. Pigment Yellow 150 (PY150) was used in an amount of 1.8 parts by mass.
  • Example 9 Production of photosensitive red resin composition R-9
  • a photosensitive red resin composition R-9 was obtained in the same manner as the photosensitive red resin composition R-1 except that the antioxidant was not added as shown in Table 2 in Example 1.
  • Example 10 to 12 Production of photosensitive red resin compositions R-10 to R-12
  • salt-forming agent a of the dispersant as shown in Table 2
  • salt-forming agent b benzyl chloride
  • salt-forming agent c benzyl bromide
  • Example 13 Production of photosensitive red resin composition R-13
  • the amount of the ultraviolet absorber was increased three times as shown in Table 2 (30 parts by weight per 100 parts by weight of the total solid content excluding the pigment component), except for the photosensitive red resin composition
  • a photosensitive red resin composition R-13 was obtained in the same manner as in product R-1.
  • Comparative Examples 1 and 2 Production of photosensitive red resin compositions CR-1 and CR-2)
  • Example 1 or Example 8 as shown in Table 2, the photosensitive red resin compositions of Comparative Examples 1 and 2 were prepared in the same manner as in Example 1 or Example 8, except that no ultraviolet absorber was used. Products CR-1 and CR-2 were manufactured.
  • Photosensitive red resin compositions CR-3 to CR-8 were prepared in the same manner as in Example 1, except that the types of ultraviolet absorbers in Example 1 were changed as shown in Table 2. -7 was produced.
  • a photosensitive red resin composition CR-8 of Comparative Example 8 was produced in the same manner as in Comparative Example 3, except that the type and amount of the ultraviolet absorbent in Comparative Example 3 were changed as shown in Table 2. .
  • Example 9 Production of photosensitive red resin composition CR-9)
  • the type of dispersant was changed from dispersant A to dispersant C (Solsperse 20000, manufactured by Lubrizol) to prepare a colorant dispersion.
  • a photosensitive red resin composition CR-9 was obtained in the same manner as the resin composition R-1.
  • the photosensitive red resin composition obtained in each example and each comparative example was coated on a glass substrate (manufactured by NH Techno Glass, "NA35") using a spin coater to form a cured coating film having a thickness of 3.0 ⁇ m. After the coating was applied so as to have a uniform thickness, it was dried at 80° C. for 3 minutes using a hot plate to form a coating film on the substrate. This coating film is exposed to ultraviolet rays of 50 mJ/cm 2 using an ultra-high pressure mercury lamp through a photomask (chromium mask) having a pattern with an opening size of 2 ⁇ m to 100 ⁇ m for forming independent thin lines, thereby exposing the glass. A post-exposure coating was formed on each substrate.
  • a photomask chromium mask
  • ⁇ Cross-sectional shape evaluation of fine line pattern colored layer The cross-sectional shape in the thickness direction of the resulting colored layer in the form of an independent thin line pattern was observed with a scanning electron microscope (manufactured by Shimadzu Corporation, super scan model 220, magnification of 10,000 times), and the cross-sectional shape of the colored layer was determined according to the following evaluation criteria.
  • the taper angle ( ⁇ 1) (see FIG. 4) was evaluated.
  • ⁇ Adhesion evaluation> The colored layer thus obtained was observed with an optical microscope to confirm the line width of the thinnest pattern as to how many ⁇ m of pattern the mask opening remained.
  • D The line width of the thinnest pattern is 26 ⁇ m or more If the evaluation result is B, the substrate adhesion is good. If the evaluation result is A, the adhesion to the substrate is excellent.
  • Examples 1 to 13 which are photosensitive red resin compositions according to the present invention, a coloring material, a dispersant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, an ultraviolet absorber, and a solvent , and the coloring material is made of a pigment containing at least a red pigment, and the ultraviolet absorber has a transmittance at a wavelength of 365 nm of 35% or less in a 0.002% by mass propylene glycol monomethyl ether acetate solution. It was shown that a red colored layer having a cross-sectional shape with a taper angle of less than 60 degrees and excellent adhesion to a substrate can be formed while suppressing the generation of residues.
  • the photosensitive red resin compositions of Comparative Examples 1 and 2 which differ from Examples 1 and 8 only in that they do not contain an ultraviolet absorber, have a taper angle ( ⁇ 1) exceeding 90 degrees in the cross-sectional shape. As a result, it was not possible to form a red colored layer with an excellent cross-sectional shape. Moreover, the photosensitive red resin compositions of Comparative Examples 1 and 2 were inferior to those of Examples 1 and 8 in terms of development residue.
  • the taper angle ( ⁇ 1) exceeded 90 degrees, and a red colored layer with an excellent cross-sectional shape could not be formed.
  • the photosensitive red resin composition of Comparative Example 8 which used a lot of ultraviolet absorbers having a transmittance of 0.002% by mass at a wavelength of 365 nm exceeding 35% in a propylene glycol monomethyl ether acetate solution, had a tapered cross-sectional shape.
  • the angle ([theta]1) exceeded 90 degrees, and a red colored layer with an excellent cross-sectional shape could not be formed, and the adhesion to the substrate was also poor.
  • the photosensitive red resin composition of Comparative Example 9 in which a dispersant different from at least one of the block copolymer and the graft copolymer was used as the dispersant, had poor development residue and poor dispersibility. was

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Abstract

L'invention concerne une composition de résine rouge photosensible qui contient un colorant, un dispersant, une résine soluble dans les alcalis, un composé photopolymérisable, un photo-initiateur, un absorbant d'ultraviolets et un solvant : le colorant étant composé de pigments qui comprennent au moins un pigment rouge ; le dispersant contenant au moins l'un d'un copolymère séquencé et d'un copolymère greffé ; et une solution d'acétate d'éther monométhylique de propylène glycol de 0,002 % en masse de l'absorbant d'ultraviolets ayant une transmittance à la longueur d'onde de 365 nm de 35 % ou moins.
PCT/JP2022/023753 2021-06-25 2022-06-14 Composition de résine rouge photosensible, produit durci, filtre coloré et dispositif d'affichage Ceased WO2022270349A1 (fr)

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JP2010224308A (ja) * 2009-03-24 2010-10-07 Fujifilm Corp カラーフィルタ及びその製造方法
WO2018124087A1 (fr) * 2016-12-28 2018-07-05 株式会社Ｄｎｐファインケミカル Liquide de dispersion de colorant pour filtres colorés, composition de résine colorante pour filtres colorés, filtre coloré et dispositif d'affichage
WO2019065185A1 (fr) * 2017-09-28 2019-04-04 株式会社Ｄｎｐファインケミカル Composition de résine colorante, produit durci, filtre couleur et dispositif d'affichage
JP2019128540A (ja) * 2018-01-26 2019-08-01 東洋インキＳｃホールディングス株式会社 カラーフィルタ用感光性着色組成物及びカラーフィルタ
JP2020177038A (ja) * 2019-04-15 2020-10-29 東洋インキＳｃホールディングス株式会社 カラーフィルタ用着色組成物、フィルタセグメント、およびカラーフィルタ
WO2021039409A1 (fr) * 2019-08-27 2021-03-04 富士フイルム株式会社 Composition durcissable, produit durci, filtre coloré, élément d'imagerie à semi-conducteurs et dispositif d'affichage d'image

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010224308A (ja) * 2009-03-24 2010-10-07 Fujifilm Corp カラーフィルタ及びその製造方法
WO2018124087A1 (fr) * 2016-12-28 2018-07-05 株式会社Ｄｎｐファインケミカル Liquide de dispersion de colorant pour filtres colorés, composition de résine colorante pour filtres colorés, filtre coloré et dispositif d'affichage
WO2019065185A1 (fr) * 2017-09-28 2019-04-04 株式会社Ｄｎｐファインケミカル Composition de résine colorante, produit durci, filtre couleur et dispositif d'affichage
JP2019128540A (ja) * 2018-01-26 2019-08-01 東洋インキＳｃホールディングス株式会社 カラーフィルタ用感光性着色組成物及びカラーフィルタ
JP2020177038A (ja) * 2019-04-15 2020-10-29 東洋インキＳｃホールディングス株式会社 カラーフィルタ用着色組成物、フィルタセグメント、およびカラーフィルタ
WO2021039409A1 (fr) * 2019-08-27 2021-03-04 富士フイルム株式会社 Composition durcissable, produit durci, filtre coloré, élément d'imagerie à semi-conducteurs et dispositif d'affichage d'image

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