WO2023074411A1 - 感光性着色樹脂組成物、カラーフィルタ、及び表示装置 - Google Patents

感光性着色樹脂組成物、カラーフィルタ、及び表示装置 Download PDF

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WO2023074411A1
WO2023074411A1 PCT/JP2022/038394 JP2022038394W WO2023074411A1 WO 2023074411 A1 WO2023074411 A1 WO 2023074411A1 JP 2022038394 W JP2022038394 W JP 2022038394W WO 2023074411 A1 WO2023074411 A1 WO 2023074411A1
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Prior art keywords
resin
group
mass
parts
resin composition
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English (en)
French (fr)
Japanese (ja)
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大貴 木本
智博 小滝
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DNP Fine Chemicals Co Ltd
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DNP Fine Chemicals Co Ltd
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Priority to JP2023556318A priority Critical patent/JPWO2023074411A1/ja
Priority to CN202280060169.9A priority patent/CN117940810A/zh
Publication of WO2023074411A1 publication Critical patent/WO2023074411A1/ja
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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
    • C08F290/08—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
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

Definitions

  • the present invention relates to a photosensitive colored resin composition, 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 an alkali-soluble 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 applied to a glass substrate, dried, 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 provides a colored resin composition that has a forward-tapered cross-sectional shape of the resulting pixel and has high solubility in a developer, which has been difficult to achieve in the past due to a trade-off relationship.
  • the object is to contain (A) a pigment, (B) a solvent, (C) a binder resin and (D) a polymerizable monomer, the (C) binder resin containing a specific unsaturated group-containing resin, and (D )
  • a colored resin composition is disclosed in which the polymerizable monomer comprises an acid group-containing monomer.
  • (C) As the specific unsaturated group-containing resin of the binder resin, a copolymer obtained by copolymerizing at least the following (C-1) and (C-3), (C-4) and (C-5) ) is disclosed.
  • Patent Document 2 discloses a coloring composition for a color filter that enables control of spectral characteristics and has less development residue and excellent color separation property.
  • a coloring composition for a color filter containing a polymerizable compound (C), a polymerization initiator (D), and a solvent (E), wherein the coloring agent (A) contains a quinacridone-based pigment, and a binder resin (B ) has an acid value of 70 to 200 mgKOH / g, and contains a photosensitive resin (B1) that is at least one selected from the following (B1-1), (B1-2), and (B1-3) ,
  • the polymerizable compound (C) contains a polymerizable compound (C1) having an acidic group, and a polyfunctional photocurable compound (C2) having an alkyleneoxy group having 2 or more carbon atoms, and a polyfunctional photocurable compound (
  • a coloring composition for color filters is disclosed in which C2) is a trimethylolpropane derivative.
  • Binder resin (B1-1) A copolymer obtained by copolymerizing the following (a-1) and (b-1) is reacted with (c-1) and then with (d).
  • JP 2017-122927 A Japanese Patent No. 6344462
  • the undercut length a is one end p in the width direction of the colored resin composition layer 3 ′ in the cross section of the colored resin composition layer 3 ′ after development,
  • the colored resin composition layer 3 ' is scooped out and there is no colored resin composition, and it is obtained as the distance between the part q farthest in the width direction from the one end p .
  • the line width of the light-shielding portion 2 is also narrowed.
  • the colored resin composition layer 3' is scooped out, resulting in a portion having no colored resin composition.
  • the colored resin composition layer 3' is scooped out to the colored layer forming region as shown in FIG.
  • the colored layer after post-baking is adjacent to the light shielding portion 2 as shown in FIG. A gap 5 is generated in the part. If voids 5 are formed, problems such as the color of the colored layer becoming pale, or an error in the inspection machine causing an impediment to production occur.
  • FIG. 6(A) the width of the light shielding portion 2 before the high definition was achieved was relatively wide. ' was generated, the colored resin composition layer 3' was not scooped out to the colored layer forming region.
  • FIG. 6B when the line width of the light shielding portion 2 is narrowed for higher definition, it is required to shorten the undercut length a.
  • the colored resin composition of Patent Document 1 and the colored composition for color filters of Patent Document 2 are each relatively good in suppressing development residue, but the undercut length after development is long, and the fine pattern is not formed. There was also a problem of chipping of the colored layer.
  • the present invention has been made in view of the above-mentioned circumstances, and a photosensitive coloring capable of forming a fine pattern colored layer with a short undercut length after development and suppressed chipping while suppressing the generation of development residues.
  • An object of the present invention is to provide a resin composition.
  • an object of this invention is to provide the color filter and display apparatus which were formed using the said photosensitive colored resin composition.
  • the photosensitive colored resin composition according to the present invention contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent
  • the alkali-soluble resin is characterized by containing at least one resin selected from the group consisting of the following (resin 1) and (resin 2).
  • (Resin 1) A polymer obtained by polymerizing at least the following (A1) is reacted with (C1), then (D1) is reacted, and then (E1) is reacted, or (E1) is reacted.
  • the color filter according to the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is a cured photosensitive colored resin composition according to the present invention. It is a thing.
  • the present invention also provides a display device having the color filter according to the present invention.
  • the present invention it is possible to provide a photosensitive colored resin composition capable of forming a fine patterned colored layer with a short undercut length after development and suppressed chipping while suppressing the generation of development residues. Moreover, according to this invention, the color filter and display apparatus which were formed using the said photosensitive colored resin composition can be provided.
  • FIG. 1 is a schematic cross-sectional view showing an example of the color filter of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing an example of the liquid crystal display device of the present invention.
  • FIG. 3 is a schematic cross-sectional view showing an example of the organic light-emitting display device of the present invention.
  • FIG. 4 is a schematic cross-sectional view for explaining the undercut length of the photosensitive colored resin layer after development.
  • FIG. 5 is a schematic cross-sectional view (A) showing the state of the photosensitive colored resin layer after development and a schematic cross-sectional view (B) showing the state of the colored layer after post-baking when the light-shielding portion having a narrow line width is provided. ).
  • FIG. 1 is a schematic cross-sectional view showing an example of the color filter of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing an example of the liquid crystal display device of the present invention.
  • FIG. 3 is a schematic cross-sectional
  • FIG. 6 is a schematic cross-sectional view (A) showing the state of the photosensitive colored resin layer after development when it has a light shielding part with a wide line width, and a photosensitive coloring after development when it has a light shielding part with a narrow line width. It is a schematic sectional drawing (B) which shows the state of a resin layer.
  • light includes electromagnetic waves with wavelengths in the visible and non-visible regions, and radiation
  • radiation includes, for example, microwaves and electron beams.
  • electromagnetic waves with a wavelength of 5 ⁇ m or less and electron beams.
  • (meth)acryloyl represents acryloyl and methacryloyl
  • (meth)acryl represents acrylic and methacrylic
  • (meth)acrylate represents acrylate and methacrylate.
  • the term "to" indicating a numerical range is used to include the numerical values before and after it as lower and upper limits.
  • the photosensitive colored resin composition of the present invention contains a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent,
  • the alkali-soluble resin contains at least one resin selected from the group consisting of (Resin 1) and (Resin 2) below.
  • (Resin 1) A polymer obtained by polymerizing at least the following (A1) is reacted with (C1), then (D1) is reacted, and then (E1) is reacted, or (E1) is reacted.
  • C1 unsaturated carboxylic acid and unsaturated
  • D1 carboxylic acid anhydrides
  • E1 polybasic acid anhydride
  • Resin 2 at least the following (A2 ) is reacted with (D2) and then (E2), or (E2) is reacted and then (D2) is reacted with the polymer obtained by polymerizing (A2 ): a monomer having a hydroxyl group and an ethylenically unsaturated bond (D2): a compound having a functional group capable of reacting with a hydroxyl group and an unsaturated bond (E2): a polybasic acid anhydride.
  • the photosensitive colored resin composition according to the present invention uses at least one resin selected from the group consisting of (resin 1) and (resin 2) as the alkali-soluble resin to suppress the generation of development residue.
  • resinsin 1 and (resin 2) as the alkali-soluble resin to suppress the generation of development residue.
  • the (resin 1) is obtained by reacting (C1) with a polymer obtained by polymerizing at least the (A1), then reacting (D1) and then reacting (E1), or (E1 ) is reacted and then (D1) is reacted, and since it is a resin obtained, in one structural unit, the unsaturated bond derived from (C1) and the unsaturated bond derived from (D1) are added to the side chain and, in another structural unit, the side chain has an unsaturated bond derived from (C1) and an acidic group distant from the main chain derived from (E1).
  • the above (resin 1) can have many unsaturated bonds in the side chain and has an acidic group distant from the main chain.
  • the (resin 2) is obtained by reacting (D2) with a polymer obtained by polymerizing at least the (A2) and then reacting (E2), or reacting (E2) and then Since it is a resin obtained by reacting (D2), one structural unit has an unsaturated bond derived from (D2) in the side chain, and another structural unit has the side chain ( E2) has an acidic group that is distant from the main chain.
  • the (resin 2) can have many unsaturated bonds in the side chain and has an acidic group distant from the main chain.
  • at least one resin selected from the group consisting of (Resin 1) and (Resin 2) can have a large number of unsaturated bonds in the side chain.
  • the photosensitive colored resin composition of the present invention can form a colored layer with a fine pattern in which chipping is suppressed while suppressing the generation of development residues.
  • the undercut length due to the improvement of the curability of the film, it is difficult for the undercut length to become long because it is difficult for gouging to occur during development. It is presumed that the undercut length after development is likely to be shortened because the tip portion of the shape is likely to be developed during development and the length of the undercut is less likely to be increased.
  • the photosensitive colored resin composition of the present invention improves the curability of the film, and thus the colored layer has excellent solvent resistance. Furthermore, the photosensitive colored resin composition of the present invention also has the effect that the line width shift amount is smaller than the design line width when forming a fine pattern. It is presumed that the photosensitive colored resin composition of the present invention has improved curability, and at the same time, the tapered tip that is slightly cured by the diffracted light of exposure is easily developed during development.
  • the photosensitive colored resin composition according to the present invention contains a colorant, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, as long as the effects of the present invention are not impaired. , and may further contain other components. Each component of the colored resin composition of the present invention will be described in detail below.
  • the coloring material is not particularly limited as long as it can develop a desired color when the colored layer of the color filter is formed, and various organic pigments, inorganic pigments, dispersible dyes, and dyes Salt-forming compounds and the like can be used alone or in combination of two or more.
  • organic pigments are preferably used because of their high color developability and high heat resistance. Examples of organic pigments include compounds classified as pigments in the Color Index (C.I.; published by The Society of Dyers and Colorists). .) numbered ones can be mentioned.
  • the inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, Prussian blue, oxide Chromium green, cobalt green, amber, titanium black, synthetic iron black, carbon black and the like can be mentioned.
  • a black pigment with high light-shielding properties is blended into the composition.
  • a black pigment with high light shielding properties for example, an inorganic pigment such as carbon black or triiron tetroxide, or an organic pigment such as cyanine black can be used.
  • the dispersible dyes include dyes that are made dispersible by adding various substituents to the dyes or by using them in combination with solvents having low solubility.
  • the salt-forming compound of the dye refers to a compound in which the dye forms a salt with a counterion. Examples thereof include a salt-forming compound of a basic dye and an acid, and a salt-forming compound of an acid dye and a base, which are soluble in solvents. It also includes a lake pigment obtained by insolubilizing the dye in a solvent using a known lake formation (chlorination) technique.
  • the dye can be appropriately selected from conventionally known dyes.
  • examples of such dyes include azo dyes, metal complex salt azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, and phthalocyanine dyes.
  • azo dyes metal complex salt azo dyes
  • anthraquinone dyes triphenylmethane dyes
  • xanthene dyes cyanine dyes
  • naphthoquinone dyes naphthoquinone dyes
  • quinoneimine dyes methine dyes
  • phthalocyanine dyes a guideline
  • the coloring material is at least one selected from the group consisting of diketopyrrolopyrrole pigments, quinophthalone pigments, copper phthalocyanine pigments, zinc phthalocyanine pigments, quinophthalone dyes, coumarin dyes, cyanine dyes, and salt-forming compounds of these dyes.
  • the coloring material preferably contains at least one selected from the group consisting of diketopyrrolopyrrole pigments, quinophthalone pigments, copper phthalocyanine pigments, zinc phthalocyanine pigments, and quinophthalone dyes.
  • diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, 255, 264, 272, 291, and diketopyrrolopyrrole pigments represented by the following general formula (i), among which C.I. I. Pigment Red 254, 272, 291, and at least one selected from diketopyrrolopyrrole pigments in which R p1 and R p2 in the following general formula (i) are each a 4-bromophenyl group are preferred.
  • R p1 and R p2 are each independently a 4-chlorophenyl group or a 4-bromophenyl group.
  • Examples of quinophthalone pigments include C.I. I. Pigment Yellow 138 and the like.
  • Examples of copper phthalocyanine pigments include C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, C.I. I. Pigment Green 7, 36 and the like, among which C.I. I. Pigment Blue 15:6 is preferred.
  • Examples of zinc phthalocyanine pigments include C.I. I. Pigment Green 58, 59 and the like.
  • Examples of quinophthalone dyes include C.I. I. Disperse Yellow 54, 64, 67, 134, 149, 160, C.I. I. Solvent Yellow 114, 157 and the like, among which C.I. I. Disperse Yellow 54 is preferred.
  • the average primary particle size of the 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 nm to 100 nm, more preferably in the range of 15 nm to 60 nm.
  • the display device equipped with the color filter produced using the photosensitive colored 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 colored resin composition varies depending on the type of colorant used, but is preferably in the range of 10 nm to 100 nm, and is in the range of 15 nm to 60 nm. is more preferred.
  • the average dispersed particle size of the colorant in the photosensitive colored resin composition is the dispersed particle size of the colorant particles dispersed in the dispersion medium containing at least a solvent, and is measured by a laser light scattering particle size distribution meter. It is a thing.
  • the solvent used in the photosensitive colored resin composition is diluted appropriately to a concentration that can be measured by a laser light scattering particle size distribution meter (for example, 1000 times), and measured at 23° C. by a dynamic light scattering method using a laser light scattering particle size distribution analyzer (for example, Nanotrack particle size distribution analyzer UPA-EX150 manufactured by Nikkiso Co., Ltd.).
  • the average distribution particle size here is the volume average particle size.
  • the coloring material used in the present invention can be produced by known methods such as recrystallization and solvent salt milling. Alternatively, a commercially available coloring material may be used after undergoing fine processing.
  • the content of the coloring material in the photosensitive colored resin composition according to the present invention is not particularly limited.
  • the total content of the coloring material from the viewpoint of dispersibility and dispersion stability, relative to the total solid content of the photosensitive colored resin composition, for example preferably 3% by mass to 65% by mass, more preferably 4% by mass to It is within the range of 60% by mass. If it is at least the above lower limit, the colored layer will have a sufficient color density when the photosensitive colored 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 15% by mass to 65% by mass, more preferably 15% by mass to 65% by mass, based on the total solid content of the photosensitive colored resin composition. It is in the range of 25% by mass to 60% by mass.
  • the solid content includes all substances other than the solvent described later, and liquid monomers and the like are also included.
  • the alkali-soluble resin used in the present invention has an acidic group, and can be appropriately selected and used from those that act as a binder resin and are soluble in an alkali developer used for pattern formation. can.
  • the alkali-soluble resin can be defined as having an acid value of 40 mgKOH/g or more.
  • the alkali-soluble resin used in the present invention contains at least one resin selected from the group consisting of (resin 1) and (resin 2) below.
  • (Resin 1) (Resin 1) is obtained by reacting (C1) with a polymer obtained by polymerizing at least the following (A1), then reacting (D1) and then reacting (E1), or (E1) is reacted, and then (D1) is reacted to obtain a resin. That is, the resin 1 is at least one resin selected from the group consisting of the following (resin 1-1) and (resin 1-2).
  • the following (Resin 1-1) and (Resin 1-2) may be either, but from the viewpoint of solubility in a solvent during production, the following (Resin 1-1) may be used.
  • (Resin 1-1) (C1) is reacted with a polymer obtained by polymerizing at least the following (A1), then (D1) is reacted, and then (E1) is reacted to obtain a resin (resin 1-2) Resin obtained by reacting (C1) with a polymer obtained by polymerizing at least the following (A1), then reacting (E1) and then reacting (D1)
  • (Resin 1) is obtained by reacting (C1) with a copolymer obtained by copolymerizing at least the following (A1) and (B1), then reacting (D1), and then reacting (E1). Alternatively, it may be a resin obtained by reacting (E1) and then reacting (D1).
  • E1 many Basic Acid Anhydride
  • a monomer having a cyclic ether skeleton having 2 to 4 carbon atoms and an ethylenically unsaturated bond is, for example, a monomer having an oxiranyl group and an ethylenically unsaturated bond (A1-1) , a monomer having an oxetanyl group and an ethylenically unsaturated bond (A1-2), a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (A1-3), and the like.
  • the monomer (A1-1) having an oxiranyl group and an ethylenically unsaturated bond includes a monomer having an epoxidized structure of a chain olefin and an ethylenically unsaturated bond, a structure obtained by epoxidizing a cycloalkene, monomers having an ethylenically unsaturated bond.
  • a monomer having an oxiranyl group and an ethylenically unsaturated bond a monomer having an oxiranyl group and a (meth)acryloyloxy group is preferred.
  • Examples of monomers having an epoxidized chain olefin structure and an ethylenically unsaturated bond include glycidyl (meth)acrylate, ⁇ -methylglycidyl (meth)acrylate, ⁇ -ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, ⁇ -methyl-o-vinylbenzyl glycidyl ether, ⁇ -methyl-m-vinylbenzyl glycidyl ether, ⁇ -methyl-p -vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(
  • the monomer having a structure obtained by epoxidizing a chain olefin and an ethylenically unsaturated bond may be a monomer having a glycidyl group and an ethylenically unsaturated bond.
  • Examples of monomers having an epoxidized cycloalkene structure and an ethylenically unsaturated bond include vinylcyclohexene monoxide and 1,2-epoxy-4-vinylcyclohexane (eg, Celoxide 2000; Daicel Chemical Industries, Ltd. ), 3,4-epoxycyclohexylmethyl acrylate (eg, Cychromer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (eg, Cychromer M100; manufactured by Daicel Chemical Industries, Ltd.) ), a compound represented by the following formula (a1-1-1), a compound represented by the formula (a1-1-2), and the like.
  • vinylcyclohexene monoxide and 1,2-epoxy-4-vinylcyclohexane eg, Celoxide 2000; Daicel Chemical Industries, Ltd.
  • 3,4-epoxycyclohexylmethyl acrylate eg,
  • R 1 and R 2 independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the alkyl group The contained hydrogen atoms may be substituted with hydroxy groups.
  • X 1 and X 2 each independently represent a single bond, *-R 3 -, *-R 3 -O-, *-R 3 -S-, *-R 3 -NH-.
  • R 3 represents an alkanediyl group having 1 to 6 carbon atoms. * represents a bond with O.
  • the alkyl group having 1 to 4 carbon atoms specifically includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n -butyl group, sec-butyl group, tert-butyl group and the like.
  • the alkyl group substituted with a hydroxy group includes a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, and a 1-hydroxypropyl group.
  • R 1 and R 2 are preferably hydrogen atom, methyl group, hydroxymethyl group, 1-hydroxyethyl group and 2-hydroxyethyl group, more preferably hydrogen atom and methyl group.
  • the alkanediyl group having 1 to 6 carbon atoms includes methylene group, ethylene group, propane-1,2-diyl group, propane-1, 3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group and the like.
  • X 1 and X 2 are preferably a single bond, a methylene group, an ethylene group, *—CH 2 —O— (* is O and ) group and *--CH 2 CH 2 --O-- group, more preferably a single bond and *--CH 2 CH 2 --O-- group.
  • the monomer (A1-2) having an oxetanyl group and an ethylenically unsaturated bond is preferably a monomer having an oxetanyl group and a (meth)acryloyloxy group.
  • Examples of the monomer (A1-2) having an oxetanyl group and an ethylenically unsaturated bond include 3-methyl-3-(meth)acryloyloxymethyloxetane, 3-ethyl-3-(meth)acryloyloxymethyloxetane , 3-methyl-3-(meth)acryloyloxyethyloxetane, 3-ethyl-3-(meth)acryloyloxyethyloxetane and the like.
  • the monomer (A1-3) having a tetrahydrofuryl group and an ethylenically unsaturated bond a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferable.
  • the monomer (A1-3) having a tetrahydrofuryl group and an ethylenically unsaturated bond include tetrahydrofurfuryl acrylate (eg, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate. etc.
  • (B1) a monomer having an unsaturated bond copolymerizable with (A1) and different from (A1)
  • (B1) is an optional component in the resin (1) and used when forming the copolymer , incorporated into the backbone.
  • Examples of (B1) include chain alkyl (meth)acrylate such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate and tert-butyl (meth)acrylate.
  • acrylates methoxypolyethylene glycol mono (meth) acrylate, alkoxypolyalkylene glycol mono (meth) acrylates such as methoxypolypropylene glycol mono (meth) acrylate; cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, di Cyclic alkyl (meth)acrylates such as cyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and isobornyl (meth)acrylate
  • Aryl (meth)acrylates or aralkyl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and dieth
  • Styrene ⁇ -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , isoprene, 2,3-dimethyl-1,3-butadiene, and the like.
  • (B1) can be used alone or in combination of two or more.
  • (meth)acrylates are preferred from the viewpoint of compatibility.
  • the content ratio of (B1) may be adjusted as appropriate, but from the viewpoint of curability, (B1) may be 0 parts by mass to 217 parts by mass with respect to 100 parts by mass of (A1), and 0 mass parts to 96 parts by mass, may be 0 to 50 parts by mass, and may be 0 to 11 parts by mass.
  • the total amount of structural units derived from (A1) may be 24 mol% to 100 mol%, or may be 42 mol% to 100 mol%, relative to all structural units constituting the main chain, It may be from 86 mol % to 100 mol %.
  • the total amount of structural units derived from (B1) may be 0 mol % to 76 mol %, or 0 mol % to 58 mol %, relative to all structural units constituting the main chain. Well, it can be from 0 mol % to 14 mol %.
  • the total sum of the structural units derived from (A1) and the sum of the structural units derived from (B1) used as needed is 100 mol% with respect to all structural units constituting the main chain. you can
  • (C1) at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (C1) includes, for example, acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m- Unsaturated monocarboxylic acids such as vinyl benzoic acid and p-vinyl benzoic acid; Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxy
  • (C1) is preferably a compound having an acryloyl group from the viewpoint of high reactivity and enhanced curability when a coating film is formed.
  • acrylic acid mono(2-acryloyloxyethyl) succinate, and the like are preferably used from the viewpoint of the reactivity of the unsaturated bond in the coating film.
  • the amount of (C1) introduced may be adjusted as appropriate, but from the viewpoint of curability, (C1) is 35 parts by mass to 152 parts by mass with respect to 100 parts by mass of (A1) in terms of charge. may be from 41 parts by mass to 152 parts by mass, and may be from 46 parts by mass to 152 parts by mass.
  • the amount of (C1) to be introduced may be adjusted as appropriate, but from the viewpoint of curability, the molar fraction with respect to the cyclic ether group having 2 to 4 carbon atoms of (A1) is 50% in terms of charge. It may be ⁇ 100% and may be between 70% and 100%.
  • the functional group capable of reacting with a hydroxyl group includes, for example, an isocyanate group, a carboxyl group, and a carboxylic acid chloride.
  • the functional group capable of reacting with a hydroxyl group is preferably an isocyanate group in terms of reactivity with the hydroxyl group.
  • the compound having a functional group capable of reacting with a hydroxyl group and an unsaturated bond is preferably a compound having a functional group capable of reacting with a hydroxyl group and a (meth)acryloyl group from the viewpoint of curability.
  • a compound having an acryloyl group is preferable from the viewpoint of high reactivity and enhanced curability when a coating film is formed.
  • one molecule may have two or more unsaturated bonds.
  • Examples of compounds having an isocyanate group and an unsaturated bond include 2-(meth)acryloyloxyethyl isocyanate and 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate.
  • Examples of compounds having a carboxyl group and an unsaturated bond include (meth)acrylic acid and mono(2-acryloyloxyethyl) succinate.
  • Examples of compounds having a carboxylic acid chloride and an unsaturated bond include (meth)acrylic acid chloride and the like.
  • a functional group capable of reacting with the hydroxyl group of (D1) reacts with the hydroxyl group generated when the carboxyl group or acid anhydride group of (C1) reacts with the polymerized cyclic ether of (A1), (D1) is introduced into the side chain. Therefore, a structural unit in which (D1) is introduced into the side chain can have both an unsaturated bond derived from (C1) and an unsaturated bond derived from (D1) in one structural unit.
  • the amount of (D1) introduced may be adjusted as appropriate, but from the viewpoint of curability, (D1) is 5 parts by mass to 215 parts by mass with respect to 100 parts by mass of (C1) in terms of charge.
  • the amount of (D1) to be introduced may be adjusted as appropriate, but from the viewpoint of curability, it may be 2% to 80%, and may be 30% to 70%, in terms of molar fraction with respect to the generated hydroxyl groups. you can
  • Polybasic acid anhydride represents an acid anhydride of an organic polybasic acid having a plurality of hydrogen atoms per molecule that can be ionized to form hydrogen ions.
  • Examples of (E1) include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride (1,4,5 ,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic anhydride); trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyl Polybasic acid anhydrides such as tetracarboxylic acid anhydrides are included.
  • the polybasic acid anhydride may be a polyvalent carboxylic acid anhydride.
  • tetrahydrophthalic anhydride or succinic anhydride is preferable from the viewpoint of the solubility of the polybasic acid anhydride in the solvent.
  • the acid anhydride group of (E1) reacts with the hydroxyl group generated when the carboxy group of (C1) reacts with the polymerized cyclic ether of (A1), whereby (E1) is introduced into the side chain. be done. Therefore, a structural unit in which (E1) is introduced into the side chain may have both an unsaturated bond derived from (C1) and a carboxy group distant from the main chain derived from (E1) in one structural unit. .
  • the amount of (E1) introduced may be adjusted as appropriate, but from the viewpoint of developability, (E1) is 18 parts by mass to 214 parts by mass with respect to 100 parts by mass of (C1) in terms of charge.
  • the amount of (E1) to be introduced may be adjusted as appropriate, but from the viewpoint of developability, it may be 20% to 98%, or 30% to 70%, in terms of the molar fraction of the generated hydroxyl groups. you can
  • (Resin 2) is obtained by reacting (D2) with a polymer obtained by polymerizing at least the following (A2) and then reacting (E2), or reacting (E2) and then (D2) It is a resin obtained by reacting That is, the resin 2 is at least one resin selected from the group consisting of the following (resin 2-1) and (resin 2-2). Either of the following (resin 2-1) and (resin 2-2) may be used, but from the viewpoint of solubility in a solvent during production, the following (resin 2-1) may be used.
  • (Resin 2) reacts a copolymer obtained by copolymerizing at least the following (A2) and (B2) with (D2) and then reacts (E2), or reacts (E2) It may be a resin obtained by reacting (D2) after allowing it to react.
  • B2 a monomer having an unsaturated bond copolymerizable with (A2) and different from (A2)
  • (D2) a hydroxyl group and Compound Having Reactive Functional Group and Unsaturated Bond
  • E2 Polybasic Acid Anhydride
  • A2 a monomer having a hydroxyl group and an ethylenically unsaturated bond
  • A2 includes, for example, hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4 -Hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, or hydroxyalkyl methacrylates such as cyclohexanedimethanol mono (meth)acrylate, which can be used alone or in combination of two or more may be used.
  • polyether mono(meth)acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide or the like to the above hydroxyalkyl (meth)acrylate, poly ⁇ -valerolactone, poly ⁇ Polyester mono(meth)acrylates, poly(alkyleneoxy)(meth)acrylates, and poly(alkyleneoxycarbonyl)(meth)acrylates added with -caprolactone and/or poly 12-hydroxystearic acid can also be used.
  • hydroxyalkyl (meth)acrylate from the viewpoint of controlling the unsaturated bond equivalent, among others, hydroxyalkyl (meth)acrylate, glycerol mono (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, poly (alkyleneoxy) (meth) acrylate, and poly(alkyleneoxycarbonyl) (meth)acrylates, more preferably hydroxyalkyl (meth)acrylates.
  • the hydroxyalkyl (meth)acrylate may have 2 to 6 or 2 to 4 alkyl carbon atoms.
  • (B2) a monomer having an unsaturated bond copolymerizable with (A2) and different from (A2). , incorporated into the backbone.
  • (B2) includes, for example, chain alkyl (meth)acrylates; alkoxypolyalkylene glycol mono(meth)acrylates; cyclic alkyl (meth)acrylates; aryl (meth)acrylates or aralkyl (meth)acrylates; Dicarboxylic acid diesters; Bicyclounsaturated compounds; Dicarbonylimide derivatives; Styrene, ⁇ -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride , vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,
  • (B2) can be used alone or in combination of two or more.
  • (meth)acrylates are preferred among them from the viewpoint of compatibility.
  • (B2) may be adjusted as appropriate, but from the viewpoint of curability, (B2) may be 0 parts by mass to 147 parts by mass with respect to 100 parts by mass of (A2), and 0 mass parts to 53 parts by mass, and may be 0 parts by mass to 25 parts by mass.
  • the total amount of structural units derived from (A2) may be 34 mol% to 100 mol%, or may be 59 mol% to 100 mol%, relative to all structural units constituting the main chain, It may be from 75 mol % to 100 mol %.
  • the total amount of structural units derived from (B2) may be 0 mol % to 66 mol %, or may be 0 mol % to 41 mol %, relative to all structural units constituting the main chain. , 0 mol % to 25 mol %.
  • the total sum of the structural units derived from (A2) and the sum of the structural units derived from (B2) used as necessary is 100 mol% with respect to all structural units constituting the main chain. you can
  • (D2) Compound Having a Functional Group Reactive with a Hydroxyl Group and an Unsaturated Bond
  • Examples of (D2) include the same compounds as those described for (D1) above.
  • (D2) is introduced into the side chain by reacting the polymerized hydroxyl group of (A2) with a functional group capable of reacting with the hydroxyl group of (D2).
  • a structural unit in which (D2) is introduced into the side chain has an unsaturated bond derived from (D2).
  • the amount of (D2) introduced may be adjusted as appropriate, but from the viewpoint of curability, (D2) is 41 parts by mass to 130 parts by mass with respect to 100 parts by mass of (A2) in terms of charge. may be from 78 parts by mass to 130 parts by mass.
  • the amount of (D2) introduced may be adjusted as appropriate, but from the viewpoint of curability, it may be 20% to 90% in terms of mole fraction with respect to the hydroxyl group of (A2), It may be from 30% to 70%.
  • Examples of (E2) include those similar to (E1).
  • (E2) is introduced into the side chain by reacting the polymerized hydroxyl group of (A2) with the acid anhydride group of (E2).
  • the structural unit in which (E2) is introduced into the side chain has a carboxy group distant from the main chain derived from (E2) generated by ring-opening of the polybasic acid anhydride.
  • the amount of (E2) introduced may be adjusted as appropriate, but from the viewpoint of developability, (E2) is 15 parts by mass to 76 parts by mass with respect to 100 parts by mass of (A2) in terms of charge. may be from 15 parts by mass to 41 parts by mass.
  • the amount of (E2) introduced may be adjusted as appropriate, but from the viewpoint of curability, it may be 10% to 80% in terms of mole fraction with respect to the hydroxyl group of (A2), It may be from 30% to 70%.
  • each of the above (resin 1) and (resin 2) preferably has an acid value of 50 mgKOH/g to 170 mgKOH/g.
  • the lower limit of the acid value of (Resin 1) and (Resin 2) is more preferably 60 mgKOH/g or more, still more preferably 70 mgKOH/g or more, still more preferably 90 mgKOH/g or more.
  • the upper limit of the acid value of (Resin 1) and (Resin 2) is more preferably 160 mgKOH/g or less, still more preferably 150 mgKOH/g or less.
  • the acid value represents the mass (mg) of potassium hydroxide required to neutralize the acidic component contained in 1 g of the solid content of the resin, and is measured by the method described in JIS K 0070: 1992. is the value to be
  • each of the (resin 1) and (resin 2) may have a hydroxyl value.
  • the hydroxyl values of (Resin 1) and (Resin 2) may be, for example, 120 mgKOH/g or less, 100 mgKOH/g or less, or 50 mgKOH/g or less from the viewpoint of curability.
  • the lower limit of the hydroxyl value may be 0 mgKOH/g.
  • the hydroxyl value represents the mass (mg) of potassium hydroxide equivalent to the hydroxyl group in 1 g of the solid content of the resin, and is a value measured by the method described in JIS K 0070:1992.
  • each of the (resin 1) and (resin 2) has an unsaturated bond equivalent of 200 g/mol to 450 g/mol.
  • the lower limit of the unsaturated bond equivalent weight of (Resin 1) and (Resin 2) is more preferably 210 g/mol or more, and may be 300 g/mol or more.
  • the upper limit of the unsaturated bond equivalent weight of (Resin 1) and (Resin 2) is more preferably 400 g/mol or less, still more preferably 350 g/mol or less.
  • the term "unsaturated bond equivalent” means the weight average molecular weight per mole of unsaturated bond in the above (resin 1) and (resin 2), and is represented by the following formula (1).
  • the unsaturated bond equivalent is, for example, in accordance with the iodine value test method described in JIS K 0070: 1992, the unsaturated It may be calculated by measuring the number of saturated bonds.
  • the preferred weight average molecular weight (Mw) of at least one resin selected from the group consisting of (Resin 1) and (Resin 2) is preferably in the range of 1,000 to 50,000, more preferably is between 3,000 and 20,000.
  • the weight average molecular weight can be determined by GPC measurement using polystyrene as a standard substance, and can be measured, for example, by Shodex GPC System-21H using THF as an eluent.
  • the alkali-soluble resin contains at least one resin selected from the group consisting of (Resin 1) and (Resin 2) as an essential component, and other alkali-soluble resins as long as the effects of the present invention are not impaired.
  • the content of at least one resin selected from the group consisting of (Resin 1) and (Resin 2) is preferably 70% by mass based on the total amount of the alkali-soluble resin. Above, more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, and may be 100% by mass.
  • alkali-soluble resins that may be further contained, conventionally known alkali-soluble resins can be appropriately selected and used. can be used.
  • Other preferred alkali-soluble resins in the present invention are resins having an acidic group, usually a carboxy group. Specifically, acrylic copolymers having a carboxy group, styrene-acrylic copolymers having a carboxy group, and the like. acrylic resins, epoxy (meth)acrylate resins having a carboxy group, etc., acrylic resins such as acrylic copolymers having a carboxy group and styrene-acrylic copolymers having a carboxy group are preferably used. be done.
  • acrylic copolymers having a carboxy group in the side chain and a photopolymerizable group such as an unsaturated bond in the side chain. This is because the film strength of the cured film formed by containing the photopolymerizable functional group is improved.
  • acrylic copolymers acrylic resins such as styrene-acrylic copolymers, and epoxy acrylate resins may be used in combination.
  • the alkali-soluble resins used in the photosensitive colored resin composition may be used singly or in combination of two or more.
  • the content of the alkali-soluble resin is not particularly limited, but is preferably 5% to 60% by mass, more preferably 10% to 40% by mass, based on the total solid content of the photosensitive colored resin composition. Within range. When the content of the alkali-soluble resin is at least the above lower limit, sufficient alkali developability is obtained, and when the content of the alkali-soluble resin is at most the above upper limit, film roughness and pattern chipping during development are prevented. can be suppressed.
  • the photopolymerizable compound used in the photosensitive colored resin composition of the present invention is not particularly limited as long as it can be polymerized by a photoinitiator, and usually a compound having two or more ethylenically unsaturated bonds.
  • Polyfunctional (meth)acrylates are preferably used, and particularly preferably have two or more acryloyl groups or methacryloyl groups. Such a polyfunctional (meth)acrylate may be appropriately selected from among conventionally known ones and used. Specific examples include those described in JP-A-2013-029832.
  • polyfunctional (meth)acrylates may be used alone, or two or more thereof may be used in combination.
  • polyfunctional (meth) acrylate is a compound having three (trifunctional) or more ethylenically unsaturated bonds Compounds containing 3 to 15 ethylenically unsaturated bonds are preferred, and compounds containing 3 to 6 ethylenically unsaturated bonds are more preferred.
  • the polymerizable compound is preferably a 3- to 15-functional (meth)acrylate compound, more preferably a 3- to 6-functional (meth)acrylate compound.
  • poly (meth) acrylates of trihydric or higher polyhydric alcohols and their dicarboxylic acid-modified products are preferable.
  • Methylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, succinic acid-modified pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta (Meth)acrylate, dipentaerythritol penta(meth)acrylate modified with succinic acid, dipentaerythritol hexa(meth)acrylate, and the like are preferred.
  • the photopolymerizable compound used in the photosensitive colored resin composition of the present invention may contain a photopolymerizable compound having an acidic group from the viewpoint of developability.
  • the acid group includes a carboxy group, a sulfo group, a phosphoric acid group and the like, and a carboxy group is preferred.
  • Commercially available photopolymerizable compounds having an acidic group include Aronix M-510, M-520 and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.).
  • the content of the photopolymerizable compound having an acidic group is, from the viewpoint of developability, the total amount of the photopolymerizable compound, 20 wt% or less. may be 10% by mass or less, may be 5% by mass or less, or may be 0% by mass from the viewpoint of the acid value of the alkali-soluble resin to be combined.
  • Photopolymerizable compound used in the photosensitive colored resin composition of the present invention is good in terms of curability adjustment, easy to form a fine pattern, easy to suppress chipping, photopolymerizable having a caprolactone structure It may contain a compound.
  • the photopolymerizable compound having a caprolactone structure may contain a ring-opened structure of ⁇ -caprolactone, and may contain a ring-opened structure of ⁇ -caprolactone as a repeating unit.
  • a photopolymerizable compound having a caprolactone structure can be obtained, for example, by esterifying an alcohol with (meth)acrylic acid and ⁇ -caprolactone. A compound obtained by esterifying caprolactone is preferably used.
  • a photopolymerizable compound having a caprolactone structure that is preferable from the viewpoint of curability includes a compound represented by the following general formula (1).
  • A is an n-valent alcohol residue, and each R i is independently a hydrogen atom, a group represented by the following general formula (2), or a group represented by the following general formula (3) and at least one of R i is a group represented by the following general formula (2).
  • n represents an integer of 2 or more.
  • R ii each independently represents a hydrogen atom or a methyl group
  • m represents the number of 1 or 2
  • * represents a bond.
  • the photopolymerizable compound having a caprolactone structure may have a hydroxyl value, and the hydroxyl value may be, for example, 300 mgKOH/g or less, or 260 mgKOH/g or less from the viewpoint of curability.
  • Polyhydric alcohols from which the n-valent alcohol residue A in the general formula (1) is derived include, for example, dipropylene glycol, glycerin, trimethylolethane, trimethylolpropane, triethylolpropane, 1,2,6-hexane triol, diglycerol, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, trimethylolmelamine and the like.
  • trihydric or higher alcohols are preferred.
  • the photopolymerizable compound having a caprolactone structure preferably has two or more caprolactone structures in one molecule, and the upper limit of the caprolactone structure may be the same as the valence of the polyhydric alcohol. Although n is not particularly limited, it may be 10 or less, or 8 or less.
  • a photopolymerizable compound having a caprolactone structure represented by the following general formula (1-1).
  • each R i is independently a group represented by the general formula (2) or a group represented by the general formula (3), and at least one R i is a group represented by the general formula (2).
  • j represents an integer of 1 to 3.
  • the photopolymerizable compound having a caprolactone structure may be used as the photopolymerizable compound having a caprolactone structure.
  • a commercial product it is marketed as KAYARAD DPCA series from Nippon Kayaku Co., Ltd., for example.
  • the content of the photopolymerizable compound having a caprolactone structure is, from the viewpoint of adjusting the curability, the total amount of the photopolymerizable compound, 0 mass % to 70% by mass, and may be 10% to 50% by mass.
  • the photopolymerizable compound used in the photosensitive colored resin composition of the present invention is good in terms of curability adjustment, easy to form a fine pattern, easy to suppress chipping, from the point of having an alkyleneoxy group It may contain a photopolymerizable compound.
  • the photopolymerizable compound having an alkyleneoxy group is preferably a photopolymerizable compound having an ethyleneoxy group and/or a propyleneoxy group, more preferably a photopolymerizable compound having an ethyleneoxy group, and has 4 to 20 ethyleneoxy groups.
  • 3- to 6-functional (meth)acrylate compounds having commercially available photopolymerizable compounds having an alkyleneoxy group include, for example, ethoxylated (4) pentaerythritol tetraacrylate (SR-494, manufactured by Sartomer), trimethylolpropane tripropoxy triacrylate (Nippon Kayaku Co., Ltd. manufactured by KAYARAD TPA-330), ethylene oxide 12 mol-modified dipentaerythritol hexaacrylate (trade name KAYARAD DPEA-12 manufactured by Nippon Kayaku Co., Ltd.), and New Frontier MF-001 manufactured by Daiichi Kogyo Seiyaku.
  • SR-494 pentaerythritol tetraacrylate
  • KAYARAD TPA-330 trimethylolpropane tripropoxy triacrylate
  • ethylene oxide 12 mol-modified dipentaerythritol hexaacrylate trade name KAYARAD DPEA-12 manufactured
  • the content of the photopolymerizable compound having an alkyleneoxy group is, from the viewpoint of adjusting the curability, the total amount of the photopolymerizable compound, 0 It may be from 5% by mass to 50% by mass, and may be from 5% by mass to 40% by mass.
  • the unsaturated bond equivalent is preferably 300 or less from the viewpoint of curability. , more preferably 250 or less, still more preferably 200 or less.
  • the unsaturated bond equivalent may be 97 or less from the viewpoint of curability.
  • the smaller unsaturated bond equivalent is preferable, but the lower limit may be about 50.
  • the unsaturated bond equivalent here refers to the weight average molecular weight per mole of unsaturated bond of the photopolymerizable compound, and is represented by the following formula (2).
  • the photopolymerizable compound used in the photosensitive colored resin composition of the present invention may contain a photopolymerizable compound having a molecular weight of 250 to 360 in order to easily shorten the undercut length.
  • the content of the photopolymerizable compound having a molecular weight of 250 to 360 may be 50% by mass or less, 5% by mass or more, or 10% by mass or more relative to the total amount of the photopolymerizable compound. .
  • the content of the photopolymerizable compound used in the photosensitive colored resin composition is not particularly limited, but relative to the total solid content of the photosensitive colored resin composition, for example preferably 5% by mass to 60% by mass, More preferably, it is within the range of 10% by mass to 40% by mass. If the content of the photopolymerizable compound is at least the above lower limit, photocuring will proceed sufficiently, and the exposed portion will be able to suppress elution during development. Adequate alkali developability.
  • the photoinitiator used in the photosensitive colored 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 photoinitiators.
  • Examples of the photoinitiator include polymerization initiators such as photopolymerization initiators, and specific examples thereof include those described in JP-A-2013-029832.
  • photoinitiators examples include aromatic ketones, benzoin ethers, halomethyloxadiazole compounds, ⁇ -aminoketones, biimidazoles, N,N-dimethylaminobenzophenone, halomethyl-S-triazine compounds, and thioxanthone. , oxime esters, and the like.
  • photoinitiator examples include photoinitiators described in International Publication No. 2018/062105, and other conventionally known photoinitiators can be appropriately selected and used.
  • the alkali-soluble resin since at least one resin selected from the group consisting of the above (resin 1) and (resin 2) is contained as the alkali-soluble resin, it is easy to form a narrow pattern line width, and thus sensitivity is improved. It is preferred to use high oxime ester photoinitiators.
  • Examples of the oxime ester photoinitiator used in the present invention include 1,2-octadione-1-[4-(phenylthio)phenyl]-,2-(o-benzoyloxime), ethanone, 1-[9- Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyloxime), JP 2000-80068, JP 2001-233842, JP 2010- 527339, JP-T-2010-527338, JP-A-2013-041153, WO-2015/152153, JP-A-2010-256891, etc. selected from among the oxime ester-based photoinitiators described as appropriate. can.
  • the oxime ester photoinitiator used in the present invention preferably contains at least one oxime ester compound represented by the following general formula (A) from the viewpoint of improving curability.
  • Z 1 , Z 3 , Z 4 and Z 5 are each independently a hydrogen atom, a straight or branched C 1-12 alkyl group, a C 3-20 represents a cycloalkyl group or a phenyl group, and the alkyl group, cycloalkyl group, and phenyl group are substituents selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and a phenyl group, respectively.
  • Z 2 represents an alkyl group having 1 to 20 carbon atoms substituted with a cycloalkyl group.
  • examples of linear or branched alkyl groups having 1 to 12 carbon atoms in Z 1 , Z 3 , Z 4 and Z 5 include methyl group, ethyl group and n-propyl group. , i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group , n-decyl group, n-undecyl group, n-dodecyl group and the like.
  • Examples of the cycloalkyl group having 3 to 20 carbon atoms in Z 1 , Z 3 , Z 4 and Z 5 include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and cyclooctadecyl. and the like.
  • the cycloalkyl group for Z 2 may be the same as the cycloalkyl group having 3 to 20 carbon atoms, and is preferably a cyclopentyl group or a cyclohexyl group.
  • alkyl group having 1 to 20 carbon atoms in Z 2 examples include, in addition to the linear or branched alkyl group having 1 to 12 carbon atoms, n-tetradecyl, n-hexadecyl, n-octadecyl groups, and the like. be done.
  • examples of the halogen atom which may be substituted on the alkyl group, cycloalkyl group and phenyl group include a fluorine atom, a chlorine atom and a bromine atom.
  • the alkoxy group having 1 to 6 carbon atoms which may be substituted by the alkyl group, cycloalkyl group and phenyl group includes, for example, a methoxy group and an ethoxy group. , n-propoxy group, i-propoxy group, n-butoxy group, t-butoxy group and the like.
  • Z 1 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group, more preferably a methyl group, an ethyl group, or a phenyl group, more preferably a methyl group, from the viewpoint of improving sensitivity. More preferred.
  • Z 3 , Z 4 and Z 5 are preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an i-propyl group from the viewpoint of brightness.
  • Z 2 is preferably an alkyl group having 1 to 14 carbon atoms substituted with a cycloalkyl group having 5 to 6 carbon atoms, and a cycloalkyl group having 5 to 6 carbon atoms.
  • An alkyl group having 1 to 10 carbon atoms substituted with a group is more preferred, a cyclohexylmethyl group or a cyclopentylmethyl group is even more preferred, and a cyclohexylmethyl group is particularly preferred.
  • the oxime ester compound represented by the general formula (A) is preferably an oxime ester compound represented by the following chemical formula (A-1) from the viewpoint of suppressing a decrease in luminance.
  • Commercially available products include TR-PBG-3057 (manufactured by Changzhou Yuan Electronics New Materials Co., Ltd.).
  • oxime ester compound represented by the general formula (A) for example, referring to JP-A-2012-526185, diphenyl sulfide or a derivative thereof is used, and depending on the material used, the solvent, reaction temperature, reaction time, It can be synthesized by appropriately selecting a purification method or the like. Moreover, you may obtain and use a commercial item suitably.
  • an ⁇ -aminoketone-based photoinitiator may be used in terms of curability adjustment.
  • the ⁇ -aminoketone-based photoinitiators it is preferable to contain a compound represented by the following general formula (B) from the viewpoint of suppressing sublimation and from the viewpoint of easily improving chipping resistance.
  • R a and R b are each independently an alkyl group having 2 to 8 carbon atoms.
  • R a and R b each independently represent an alkyl group having 2 or more and 8 or less carbon atoms.
  • the alkyl groups may be linear, branched, cyclic, or combinations thereof.
  • the alkyl group may be the same as the alkyl group of the general formula (A). Among them, a linear or branched alkyl group is preferable from the viewpoint of suppressing the generation of sublimate and precipitate during drying. Chain alkyl groups are more preferred.
  • the number of carbon atoms in the alkyl group is preferably 2 or more and 6 or less, more preferably 3 or more and 5 or less.
  • R a and R b in the general formula (B) may be the same or different, but when R a and R b are the same, synthesis is easy and productivity is improved. It is preferable from the point of being excellent.
  • Suitable specific examples of the compound represented by the general formula (B) include, but are not limited to, the following chemical formula (B-1).
  • the compound represented by the general formula (B) is, for example, Step 1, reacting fluorene with isobutyryl chlorochloride in the presence of aluminum trichloride to give 2-methyl-1-fluorenyl-2-chloro-1-propanone; 2-Methyl-1-fluorenyl-2-chloro-1-propanone obtained in step 1 above is epoxidized with sodium methoxide catalyzed by calcium oxide under a nitrogen atmosphere, and then further reacted with morpholine.
  • step 2 thereby obtaining 2-methyl-1-fluorenyl-2-morpholino-1-propanone;
  • 2-methyl-1-fluorenyl-2-morpholino-1-propanone obtained in step 2 with an alkyl chloride having 2 to 8 carbon atoms in the presence of tetrabutylammonium bromide (TBAB),
  • TBAB tetrabutylammonium bromide
  • a combination of the oxime ester photoinitiator and the compound represented by the general formula (B) from the viewpoint that the chipping resistance of the fine pattern tends to be improved.
  • the use of a combination of the oxime ester compound represented by the general formula (A) and the compound represented by the general formula (B) improves the adhesion of the fine pattern while maintaining the excellent formability of the fine pattern. is improved, the film tends to be tough, and chipping resistance and solvent resistance tend to be improved.
  • the total content of the photoinitiator used in the photosensitive colored resin composition of the present invention is not particularly limited as long as the effect of the present invention is not impaired, relative to the total solid content of the photosensitive colored resin composition, It is preferably in the range of 0.1% by mass to 12.0% by mass, more preferably in the range of 1.0% by mass to 8.0% by mass. When the content is at least the above lower limit, photocuring proceeds sufficiently to suppress the elution of the exposed portion during development. can be suppressed.
  • the total content of the oxime ester photoinitiator in the total amount of 100% by mass of the photoinitiator is 50 mass in terms of improving curability.
  • % or more may be 60 mass % or more, and the upper limit may be 100 mass %, but may be 90 mass % or less, and may be 80 mass % or less.
  • the total amount of the photoinitiator is 100% by mass, represented by the general formula (A)
  • the total content of one or more selected from the group consisting of compounds may be 10% by mass or more, 20% by mass or more, and 30% by mass or more. and the upper limit may be 70% by mass or less, 60% by mass or less, or 50% by mass or less.
  • the photoinitiator contains the compound represented by the general formula (B)
  • the total content of the compound represented by the general formula (B) in the total amount of 100% by mass of the photoinitiator is lacking.
  • the lower limit may be 10% by mass or more, 20% by mass or more, or 30% by mass or more
  • the upper limit may be 70% by mass or less, and 60% by mass or less. may be present, and may be 50% by mass or less.
  • solvent used in the present invention is not particularly limited as long as it does not react with each component in the photosensitive colored resin composition and is capable of dissolving or dispersing them.
  • a solvent can be used individually or in combination of 2 or more types.
  • Specific examples of solvents include alcohol solvents such as methyl alcohol, ethyl alcohol, N-propyl alcohol, i-propyl alcohol, methoxy alcohol and ethoxy alcohol; carbitol solvents such as methoxyethoxyethanol and ethoxyethoxyethanol; ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethyl lactate, methyl hydroxypropionate, ethyl hydroxypropionate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ester solvents such as
  • 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.
  • the content of the solvent is usually in the range of preferably 55% by mass to 95% by mass, more preferably 65% by mass to 88% by mass, based on the total amount of the photosensitive colored resin composition containing the solvent. When the content of the solvent is within the above range, excellent applicability can be obtained.
  • a dispersant in the photosensitive colored resin composition of the present invention, when the colorant is dispersed, a dispersant may be further included from the viewpoint of colorant dispersibility and colorant dispersion stability.
  • the dispersant can be appropriately selected and used from conventionally known dispersants.
  • the dispersing agent for example, a cationic, anionic, nonionic, amphoteric, silicone or fluorine surfactant can be used.
  • surfactants polymer dispersants are preferred because they can be uniformly and finely dispersed.
  • polymer dispersants include (meth)acrylate copolymer dispersants; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; amides obtained by reaction with free carboxyl group-containing polyesters and their bases); polyallylamine derivatives (polyallylamine and polyesters having free carboxyl groups, polyamides, or cocondensates of esters and amides (polyesteramides) (a reaction product obtained by reacting with one or more compounds selected from the compounds of ), and the like.
  • polymer dispersants include (meth)acrylate copolymer dispersants; polyurethanes; unsaturated polyamides; polysiloxanes; long-chain polyaminoamide phosphates; amides obtained by reaction with free carboxyl group-containing polyesters and their bases); polyallylamine derivatives (polyallylamine and polyesters having free carboxyl groups, polyamides, or cocondensates of esters and
  • a (meth)acrylate copolymer-based dispersant as the dispersant from the viewpoint of control of developability. Since the (meth)acrylate copolymer-based dispersant has good compatibility with the alkali-soluble resin and the photopolymerizable compound, it is presumed that generation of development residue is suppressed.
  • the (meth)acrylate copolymer-based dispersant refers to a dispersant that is a copolymer and contains at least a (meth)acrylate-derived structural unit.
  • the (meth)acrylate copolymer-based dispersant is preferably a copolymer containing a structural unit that functions as a coloring material adsorption site and a structural unit that functions as a solvent affinity site, and functions as a solvent affinity site. It is preferable that at least a (meth)acrylate-derived structural unit is included in the structural units to be used.
  • Structural units that function as colorant adsorption sites include structural units derived from monomers having ethylenically unsaturated bonds copolymerizable with structural units derived from (meth)acrylate (hereinafter referred to as ethylenically unsaturated monomers). can be done.
  • the coloring material adsorption site may be a structural unit derived from an ethylenically unsaturated monomer containing an acidic group, or a structural unit derived from an ethylenically unsaturated monomer containing a basic group.
  • a structural unit represented by the following general formula (I) is preferable from the viewpoint of excellent dispersibility.
  • R 71 is a hydrogen atom or a methyl group
  • a 1 is a divalent linking group
  • R 72 and R 73 are each independently a hydrogen atom, or a hydrocarbon which may contain a hetero atom. group, and R 72 and R 73 may combine with each other to form a ring structure.
  • a 1 is a divalent linking group.
  • the divalent linking group for example, a linear, branched or cyclic alkylene group, a linear, branched or cyclic alkylene group having a hydroxyl group, an arylene group, -CONH- group, -COO- group, -NHCOO- groups, ether groups (--O--groups), thioether groups (--S--groups), and combinations thereof.
  • the bonding direction of the divalent linking group is arbitrary.
  • a 1 in the general formula (I) is preferably a divalent linking group containing a -CONH- group or a -COO- group, and a -CONH- group or a -COO- group.
  • an alkylene group having 1 to 10 carbon atoms are more preferable.
  • Examples of the hydrocarbon group in the hydrocarbon group optionally containing a heteroatom for R 72 and R 73 include an alkyl group, an aralkyl group and an aryl group.
  • Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, isopropyl group, tert-butyl group, 2-ethylhexyl group, cyclopentyl group, cyclohexyl group and the like, and the number of carbon atoms in the alkyl group is 1. to 18 are preferable, and among them, a methyl group or an ethyl group is more preferable.
  • the aralkyl group includes, for example, a benzyl group, a phenethyl group, a naphthylmethyl group, a biphenylmethyl group and the like.
  • the number of carbon atoms in the aralkyl group is preferably 7-20, more preferably 7-14.
  • Aryl groups include phenyl, biphenyl, naphthyl, tolyl, and xylyl groups.
  • the number of carbon atoms in the aryl group is preferably 6-24, more preferably 6-12.
  • the number of carbon atoms of the substituent is not included in the preferable number of carbon atoms.
  • a hydrocarbon group containing a heteroatom has a structure in which a carbon atom in the hydrocarbon group is replaced with a heteroatom, or a structure in which a hydrogen atom in the hydrocarbon group is replaced by a substituent containing a heteroatom.
  • the heteroatom that the hydrocarbon group may contain include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom and the like.
  • hydrogen atoms in the hydrocarbon group may be substituted with halogen atoms such as fluorine, chlorine and bromine atoms.
  • R 72 and R 73 are bonded to each other to form a ring structure means that R 72 and R 73 form a ring structure via a nitrogen atom.
  • the ring structure formed by R72 and R73 may contain a heteroatom.
  • the ring structure is not particularly limited, examples thereof include pyrrolidine ring, piperidine ring, morpholine ring and the like.
  • R 72 and R 73 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, or R 72 and R 73 are bonded to form a pyrrolidine ring, piperidine It preferably forms a ring or a morpholine ring.
  • Examples of monomers that derive structural units represented by the general formula (I) include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, and the like.
  • Alkyl group-substituted amino group-containing (meth)acrylates, alkyl group-substituted amino group-containing (meth)acrylamides such as dimethylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, and the like can be mentioned.
  • dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dimethylaminopropyl (meth)acrylamide can be preferably used in terms of improving dispersibility and dispersion stability.
  • the structural unit represented by general 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 is selected from the group consisting of at least part of the nitrogen site of the structural unit represented by the general formula (I), an organic acid compound, and a halogenated hydrocarbon.
  • an organic acid compound such as phenylphosphonic acid or phenylphosphinic acid is preferable from the viewpoint of excellent dispersibility and dispersion stability of the coloring material.
  • an 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 copolymer having the structural unit represented by the general formula (I) has the structural unit represented by the general formula (I), and the graft polymer chain ( A graft copolymer having a meth)acrylate-derived structural unit, and a block having an A block containing a structural unit represented by the general formula (I) and a B block containing a (meth)acrylate-derived structural unit is more preferably at least one of copolymers.
  • a graft polymer chain having a structural unit derived from (meth)acrylate a conventionally known structure can be appropriately selected and used.
  • graft copolymer and the salt-type graft copolymer described in WO2021/006077 may be used.
  • block copolymer as the B block containing a structural unit derived from (meth)acrylate, a conventionally known structure can be appropriately selected and used.
  • block copolymers and salt-type block copolymers described in WO2016/104493 may be used.
  • the (meth)acrylate copolymer-based dispersant a commercially available product may be used, such as LP-N6919 (trade name), LP-N21116 (trade name) manufactured by Big Chemie Japan Co., Ltd., and the like.
  • the content of the dispersant is not particularly limited as long as it is selected so as to be excellent in the dispersibility and dispersion stability of the coloring material, but in the photosensitive colored resin composition
  • it is preferably in the range of 2% by mass to 30% by mass, more preferably 3% by mass to 25% by mass, based on the total solid content.
  • the dispersibility and dispersion stability of the coloring material are excellent, and the storage stability of the photosensitive colored resin composition is excellent.
  • developability will become favorable.
  • the content of the dispersant is, for example, preferably 2% by mass to 25% by mass, more preferably 2% by mass to 25% by mass, based on the total solid content of the photosensitive colored resin composition. It is in the range of 3% by mass to 20% by mass.
  • the photosensitive colored resin composition may contain various additives as necessary.
  • additives include antioxidants, polymerization terminators, chain transfer agents, leveling agents, plasticizers, surfactants, antifoaming agents, silane coupling agents, ultraviolet absorbers, adhesion promoters, and the like.
  • surfactants and plasticizers include those described in JP-A-2013-029832.
  • the photosensitive colored resin composition of the present invention further contains an antioxidant from the viewpoint of suppressing the amount of line width shift.
  • the photosensitive colored resin composition of the present invention by containing an antioxidant in combination with the specific photoinitiator, because it is possible to control excessive radical chain reaction without impairing the curability when forming a cured film When forming a fine line pattern, the linearity is further improved, and the ability to form a fine line pattern according to the design of the mask line width is improved.
  • the antioxidant used in the present invention is not particularly limited, and may be appropriately selected from those conventionally known.
  • antioxidants include hindered phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and hydrazine-based antioxidants. It is preferable to use a hindered phenol-based antioxidant from the viewpoint of improving the ability to form a fine line pattern as designed and from the viewpoint of heat resistance. It may be a latent antioxidant as described in WO2014/021023.
  • Hindered phenol antioxidants include, for example, pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (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, manufactured by Sumitomo Chemical) ), 6,6′-thiobis(2-tert-butyl-4-methylphenol) (trade name: Irganox 1081, manufactured by BASF), diethyl 3,5-
  • 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 0.1% by mass to 10.0% by mass, more preferably 0.5% by mass to 5.0% by mass, based on the total solid content of the photosensitive colored resin composition. %. If it is at least the above lower limit, the ability to form a fine line pattern as designed with a mask line width is improved, and the heat resistance is excellent. On the other hand, if it is below the above upper limit, the photosensitive colored resin composition of the present invention can be made into a highly sensitive photosensitive resin composition.
  • the method for producing a photosensitive colored resin composition of the present invention includes a coloring material, an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, a solvent, and optionally various additive components, which are mixed in a known manner. It can be prepared by mixing using means.
  • a method for preparing the resin composition for example, (1) first, 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, and optionally various additive components (3) adding an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and optionally various additive components to a solvent; (4) adding a coloring material, a dispersing agent, and an alkali-soluble resin to a solvent to prepare a coloring material dispersion;
  • the above methods (1) and (4) are preferable because they can effectively prevent the aggregation of the colorant and uniformly disperse the colorant.
  • 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 or more and 2.00 mm or less, more preferably 0.10 mm or more and 1.0 mm or less.
  • the color filter according to the present invention is a color filter comprising at least a substrate and a colored layer provided on the substrate, wherein at least one of the colored layers is the photosensitive colored resin composition according to the present invention. It is a hardened material.
  • FIG. 1 is a schematic cross-sectional view showing an example of the color filter of the present invention.
  • the color filter 10 of the present invention has a substrate 1, a light shielding portion 2 and a colored layer 3. As shown in FIG.
  • At least one of the colored layers used in the color filter of the present invention is a cured product of the photosensitive colored 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 a general arrangement such as a stripe type, mosaic type, triangle type, four-pixel arrangement type, or the like. Moreover, the width, area, etc. of the colored layer can be arbitrarily set.
  • the thickness of the colored layer can be appropriately controlled by adjusting the coating method, the solid content concentration and viscosity of the photosensitive colored resin composition, and is preferably in the range of 1 ⁇ m 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.
  • the wet coating film is dried by heating using a hot plate or an oven, and then exposed through a mask having a predetermined pattern to photopolymerize the alkali-soluble resin, the photopolymerizable compound, and the like. to form a cured coating film.
  • Light sources used for exposure include, for example, ultraviolet light from low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps, electron beams, and the like.
  • the amount of exposure is appropriately adjusted depending on the light source used, the thickness of the coating film, and the like.
  • heat treatment may be performed.
  • the heating conditions are appropriately selected according to the mixing ratio of each component in the photosensitive colored resin composition to be used, the thickness of the coating film, and the like.
  • a coating film is formed in a desired pattern by developing with a developer to dissolve and remove the unexposed portions.
  • a 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 is usually washed and the cured coating film of the photosensitive colored resin composition is dried to form a colored layer.
  • the heating conditions are not particularly limited and are appropriately selected according to the application of the coating film.
  • the colored layer may be a finely patterned colored layer with a line width of 40 ⁇ m or less, or may be a finely patterned colored layer with a line width of 20 ⁇ m or less.
  • the light-shielding portion in the color filter of the present invention is formed in a pattern on a substrate, which will be described later, and can be the same as those used as light-shielding portions in general color filters.
  • the pattern shape of the light shielding portion is not particularly limited, and examples thereof include a stripe shape and a matrix shape.
  • the light shielding portion may be a metal thin film of chromium or the like formed by a sputtering method, a vacuum deposition method, or the like.
  • the light-shielding portion may be a resin layer containing light-shielding particles such as carbon fine particles, metal oxides, inorganic pigments, or organic pigments in a resin binder.
  • a method of patterning by development using a photosensitive resist a method of patterning using an inkjet ink containing light-shielding particles, a method of thermally transferring a photosensitive resist, and the like can be used. be.
  • the film thickness of the light-shielding portion is set to about 0.2 ⁇ m to 0.4 ⁇ m in the case of a metal thin film, and is set to about 0.5 ⁇ m to 2 ⁇ m in the case of a black pigment dispersed or dissolved in a binder resin. be done.
  • substrate As the substrate, a transparent substrate, a silicon substrate, and a transparent substrate or a silicon substrate on which an aluminum, silver, silver/copper/palladium alloy thin film or the like is formed are used. Other color filter layers, resin layers, transistors such as TFTs, circuits, and the like may be formed on these substrates.
  • the 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. Although 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 includes, in addition to the above substrate, light shielding portion and colored layer, for example, an overcoat layer, a transparent electrode layer, an alignment film, alignment protrusions, columnar spacers, and the like. good too.
  • 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.
  • a liquid crystal display device includes the above-described color filter according to the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate. Such a liquid crystal display device of the present invention will be described with reference to the drawings.
  • FIG. 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention.
  • a liquid crystal display device 40 of the present invention includes a color filter 10, a counter substrate 20 having a TFT array substrate and the like, and a liquid crystal layer formed between the color filter 10 and the counter substrate 20. 30.
  • the liquid crystal display device of the present invention is not limited to the configuration shown in FIG. 2, and may have a known configuration as a liquid crystal display device generally using color filters.
  • 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 emitter 80 formed on another substrate onto the inorganic oxide film 60, and the like As for the transparent anode 71, the hole injection layer 72, the hole transport layer 73, the light emitting layer 74, the electron injection layer 75, the cathode 76, and other structures in the organic light emitter 80, 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.
  • Synthesis Example 4 Synthesis of Resin 1 (P1-4)
  • Synthesis Example 1 42.5 parts by mass of GMA (A1-1a) was changed to 40.7 parts by mass of GMA (A1-1a) and 4.5 parts by mass of benzyl methacrylate (BzMA) (B1-1), and C1 , D1, and E1 were changed as shown in Table 1, in the same manner as in Synthesis Example 1 to obtain a resin 1 (P1-4) solution.
  • Table 1 shows the weight average molecular weight, unsaturated bond equivalent, acid value, and hydroxyl value of Resin 1 (P1-4) obtained.
  • Synthesis Example 5 Synthesis of Resin 1 (P1-5)
  • Synthesis Example 1 42.5 parts by mass of GMA (A1-1a) was added to (3-ethyloxetan-3-yl)methyl methacrylate (trade name OXE-30, manufactured by Osaka Organic Chemical Industry Co., Ltd.) (A1-2a ) was changed to 49.1 parts by mass, and the amounts of C1, D1, and E1 were changed as shown in Table 1, in the same manner as in Synthesis Example 1 to obtain a resin 1 (P1-5) solution.
  • Table 1 shows the weight-average molecular weight, unsaturated bond equivalent, acid value, and hydroxyl value of Resin 1 (P1-5) obtained.
  • the reaction was continued while maintaining the temperature at 100°C, and the temperature of the reaction solution was raised to 130°C after 3 hours from the completion of dropping the main chain forming mixture.
  • the temperature of the reaction solution was raised to 130°C after 3 hours from the completion of dropping the main chain forming mixture.
  • it was cooled to 50° C. to complete the main chain formation reaction.
  • 0.051 parts by mass of p-methoxyphenol and 0.051 parts by mass of zirconium tetraacetylacetonate were added and dissolved, and then 37.0 parts by mass of 2-acryloyloxyethyl isocyanate (D2-1). and 34.9 parts by mass of diethylene glycol ethyl methyl ether were added, and the temperature was raised to 70°C.
  • Comparative Synthesis Example 1 Synthesis of Comparative Resin 1 (CP-1)
  • Comparative Resin 1 (CP-1) was synthesized in the same manner as in Synthesis Example 2 of JP-A-2017-122927. Specifically, 145 parts by mass of propylene glycol monomethyl ether acetate was stirred while substituting nitrogen, and the temperature was raised to 120°C.
  • the parts by mass in the table are the ratios so that the total of A1-1a, B1-2, B1-3, C1-1 and E1-2 is 100 parts by mass.
  • Table 4 shows the weight average molecular weight, unsaturated bond equivalent, acid value and hydroxyl value of Comparative Resin 1 (CP-1) obtained.
  • Comparative Resin 2 (CP-2) was synthesized in the same manner as Binder Resin Solution 1 of Japanese Patent No. 6344462. Specifically, 333 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, and the atmosphere in the flask was changed from air to nitrogen, and then heated to 100°C.
  • a comparative resin 2 (CP-2) solution rice field.
  • the parts by mass in the table are the ratios so that the total of A1-1a, B1-1, B1-3, C1-2 and E1-2 is 100 parts by mass.
  • Table 4 shows the weight average molecular weight, unsaturated bond equivalent, acid value and hydroxyl value of Comparative Resin 2 (CP-2) obtained.
  • reaction was continued while maintaining the temperature at 100°C, and the temperature of the reaction solution was raised to 130°C after 3 hours from the end of dropping the main chain forming mixture.
  • the temperature of the reaction solution was raised to 130°C after 3 hours from the end of dropping the main chain forming mixture.
  • it was cooled to 50° C. to complete the main chain formation reaction.
  • 0.088 parts by mass of p-methoxyphenol, 20.6 parts by mass of acrylic acid (AA) (C1-1), and 8.0 parts by mass of PGMEA were added, and the temperature was raised to 112°C.
  • 0.181 parts by mass of N,N-dimethylbenzylamine was added and addition reaction was carried out at 112° C. for 8 hours.
  • the temperature of the reaction solution is cooled to 50 ° C., 0.044 parts by mass of zirconium tetraacetylacetonate is added and dissolved, and then 2-acryloyloxyethyl isocyanate (trade name Karenz AOI, manufactured by Showa Denko Co., Ltd.) ( D1-1) 27.9 parts by mass and 8.0 parts by mass of PGMEA were added, and the temperature was raised to 70°C. The temperature was maintained at 70° C. and an addition reaction was carried out for 1 hour to obtain a comparative resin 6 (CP-6) solution.
  • Table 4 shows the weight average molecular weight, unsaturated bond equivalent, acid value and hydroxyl value of Comparative Resin 6 (CP-6) obtained.
  • the viscous liquid was extracted with dichloroethane, dried by adding 50 g of anhydrous MgSO4 , suction filtered, and the filtrate was rotary evaporated to remove the solvent to obtain an oily viscous material. Subsequently, the viscous substance was put into 150 ml of petroleum ether, stirred, precipitated, and subjected to suction filtration to obtain a white powdery solid. Then, it was dried at 60° C. for 5 hours to obtain Intermediate IA2 below.
  • Example 1 Production of photosensitive colored resin composition G1
  • 43.13 parts by mass of the colorant dispersion G-1 obtained in Production Example 1 3.70 parts by mass of Resin 1 (P1-1) obtained in Synthesis Example 1 as an alkali-soluble resin, and a photopolymerizable compound As M-403 (trade name Aronix M-403, manufactured by Toagosei Co., Ltd., unsaturated bond equivalent 98.8 to 99.6)
  • 5.02 parts by weight, obtained in Preparation Example 1 as a photoinitiator 0.55 parts by mass of compound IA, 0.30 parts by mass of a fluorosurfactant (trade name Megafac R-08MH, manufactured by DIC Corporation), and 47.57 parts by mass of PGMEA are added to prepare a photosensitive colored resin composition. I got the product G1.
  • Example 2 to 19 Production of photosensitive colored resin compositions G2 to G19
  • Resin 1 (P1-2) to Resin 1 (P1-13) and Resin 2 (P2) obtained in Synthesis Examples 2 to 19 were used instead of Resin 1 (P1-1) as the alkali-soluble resin.
  • -1) ⁇ resin 2 (P2-6) was used in the same manner as in Example 1 to obtain photosensitive colored resin compositions G2 ⁇ G19.
  • Example 20 Production of photosensitive colored resin composition G20
  • resin 1 (P1-1) instead of resin 1 (P1-1) as the alkali-soluble resin, resin 1 (P1-1) and resin 2 (P2-6) were used in parts by mass shown in Table 7. , in the same manner as in Example 1 to obtain a photosensitive colored resin composition G20.
  • Example 21 Production of photosensitive colored resin composition G21
  • resin 1 (P1-1) instead of resin 1 (P1-1) as an alkali-soluble resin, resin 1 (P1-1) and comparative resin (CP-5) were used in parts by mass shown in Table 7. , in the same manner as in Example 1 to obtain a photosensitive colored resin composition G21.
  • Example 22 Production of photosensitive colored resin composition G22
  • a photosensitive colored resin composition G22 was obtained.
  • Example 23 Production of photosensitive colored resin composition G23
  • a colored resin composition G23 was obtained.
  • Example 24 Production of photosensitive colored resin composition G24
  • a colored resin composition G24 was obtained.
  • Example 25 Production of photosensitive colored resin composition G25
  • the photopolymerizable compound M-403 (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.) and the photopolymerizable compound DPEA-12 (trade name KAYARAD DPEA-12, Photosensitization was performed in the same manner as in Example 1, except that the ethylene oxide-modified photopolymerizable compound, Nippon Kayaku Co., Ltd., unsaturated bond equivalent: 215.2) was used in the parts by mass shown in Table 7. A colored resin composition G25 was obtained.
  • Example 26 Production of photosensitive colored resin composition G26
  • Example 1 the same as in Example 1 except that the compound IA obtained in Preparation Example 1 and the compound IB obtained in Preparation Example 2 were used as photoinitiators in the parts by mass shown in Table 7. Then, a photosensitive colored resin composition G26 was obtained.
  • Example 27 Production of photosensitive colored resin composition G27
  • the antioxidant Irganox 1010 (trade name Irganox 1010, manufactured by BASF) was used as the antioxidant in the parts by weight shown in Table 7. product G27.
  • Example 28 Production of photosensitive colored resin composition G28
  • Example 20 the same as in Example 20 except that the compound IA obtained in Preparation Example 1 and the compound IB obtained in Preparation Example 2 were used as photoinitiators in the parts by mass shown in Table 7. Then, a photosensitive colored resin composition G28 was obtained.
  • Example 29 Production of photosensitive colored resin composition R1
  • a photosensitive colored resin composition R1 was obtained in the same manner as in Example 1, except that the colorant dispersion used in Example 1 was changed to the colorant dispersion R-1 obtained in Production Example 2. .
  • Example 30 Production of photosensitive colored resin composition B1
  • a photosensitive colored resin composition B1 was obtained in the same manner as in Example 1, except that the colorant dispersion used in Example 1 was changed to the colorant dispersion B-1 obtained in Production Example 3. .
  • Example 1 Production of photosensitive colored resin compositions CG1-CG2)
  • the comparative resin (CP-1) or comparative resin (CP-2) obtained in Comparative Synthesis Examples 1 and 2 was used instead of Resin 1 (P1-1) as the alkali-soluble resin, and ,
  • photopolymerizable compounds photopolymerizable compound M-403 (trade name Aronix M-403, manufactured by Toagosei Co., Ltd.) and photopolymerizable compound M-520 (trade name Aronix M-520, acidic group-containing light
  • Photosensitive colored resin compositions CG1 to CG2 were obtained in the same manner as in Example 1, except that the polymerizable compound, manufactured by Toagosei Co., Ltd., was used in the parts by mass shown in Table 8.
  • the glass substrate on which the colored layer was formed was subjected to shower development for 60 seconds using a 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer, and then washed with pure water for development treatment. Next, it was post-baked in a clean oven at 230° C. for 30 minutes to prepare a colored substrate on which an independent fine line pattern was formed.
  • the width of the fine line pattern of the formed colored layer was measured with an optical microscope at five points, and the amount of line width shift was evaluated from the difference between the average value of the line widths and the opening of the mask. (Evaluation criteria) 5: The line width shift amount was less than 1.5 ⁇ m. 4: The line width shift amount was 1.5 ⁇ m or more and less than 2.0 ⁇ m. 3: The line width shift amount was 2.0 ⁇ m or more and less than 2.5 ⁇ m. 2: The line width shift amount was 2.5 ⁇ m or more and less than 3.0 ⁇ m. 1: The line width shift amount was 3.0 ⁇ m or more.
  • the photosensitive colored resin compositions obtained in Examples and Comparative Examples are each coated on a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") to a thickness of 2.0 ⁇ m after post-baking using a spin coater. After coating with a film thickness that forms a colored layer, the colored layer was formed on the glass substrate by drying at 80° C. for 3 minutes using a hot plate. This colored layer was irradiated with ultraviolet rays of 40 mJ/cm 2 through a photomask having an opening of 90 ⁇ m using an ultra-high pressure mercury lamp.
  • the glass substrate on which the colored layer was formed was subjected to shower development for 60 seconds using a 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer, and then washed with pure water for development treatment.
  • An independent fine line pattern was formed on a glass substrate, and the number of pixel defects in the pattern on the 10 cm ⁇ 10 cm glass was counted. (Evaluation criteria) 5: Less than 5 pixel defects were confirmed. 4: 5 or more and less than 15 pixel defects were confirmed. 3: 15 or more and less than 30 pixel defects were confirmed. 2: 30 or more and less than 50 pixel defects were confirmed. 1: 50 or more pixel defects were confirmed.
  • the photosensitive colored resin compositions obtained in Examples and Comparative Examples are each coated on a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") to a thickness of 2.0 ⁇ m after post-baking using a spin coater. After coating with a film thickness that forms a colored layer, the colored layer was formed on the glass substrate by drying at 80° C. for 3 minutes using a hot plate. This colored layer was irradiated with ultraviolet rays of 60 mJ/cm 2 through a photomask having an opening of 90 ⁇ m using an ultra-high pressure mercury lamp.
  • the glass substrate on which the colored layer was formed was subjected to shower development for 60 seconds using a 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer to form an independent fine line pattern.
  • a cross section of the formed pattern was observed with a scanning electron microscope (SEM: Hitachi High-Technologies Corporation, SU-1510, magnification 10000) to measure the undercut length.
  • SEM Hitachi High-Technologies Corporation, SU-1510, magnification 10000
  • the undercut length was less than 2.0 ⁇ m. 4: The undercut length was 2.0 ⁇ m or more and less than 3.0 ⁇ m. 3: The undercut length was 3.0 ⁇ m or more and less than 5.0 ⁇ m. 2: The undercut length was 5.0 ⁇ m or more and less than 7.0 ⁇ m. 1: The undercut length was 7.0 ⁇ m or more.
  • the photosensitive colored resin compositions obtained in Examples and Comparative Examples are each coated on a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") to a thickness of 2.0 ⁇ m after post-baking using a spin coater. and then dried at 100° C. for 3 minutes using a hot plate to form a colored layer on the glass substrate. After that, the glass substrate on which the colored layer was formed was subjected to shower development for 60 seconds using a 0.05% by mass potassium hydroxide aqueous solution as an alkaline developer, and then washed with pure water for development treatment.
  • the photosensitive colored resin compositions obtained in Examples and Comparative Examples are each coated on a glass substrate (manufactured by NH Techno Glass Co., Ltd., "NA35") to a thickness of 2.0 ⁇ m after post-baking using a spin coater. After coating with a film thickness that forms a colored layer, the colored layer was formed on the glass substrate by drying at 80° C. for 3 minutes using a hot plate. This colored layer was irradiated with ultraviolet rays of 60 mJ/cm 2 using an ultra-high pressure mercury lamp. Next, the colored substrate was post-baked in a clean oven at 230° C. for 30 minutes to prepare a colored substrate.
  • the prepared colored substrate was immersed in N-methylpyrrolidone (NMP) at 60° C. for 5 minutes, and the color change ⁇ Eab) before and after immersion was evaluated.
  • NMP N-methylpyrrolidone
  • the photosensitive colored resin compositions of Comparative Examples 1 to 6 using conventional alkali-soluble resins can achieve both suppression of development residue generation, shortening of the undercut length after development, and suppression of chipping. revealed that it was not possible.
  • all of the photosensitive colored resin compositions of Examples 1 to 30 have a short undercut length after development, while suppressing the generation of development residues, forming a fine pattern colored layer in which chipping is suppressed. revealed to be possible.
  • the photosensitive colored resin compositions of Examples 1 to 30 when an alkali-soluble resin having a small unsaturated bond equivalent and a large number of unsaturated bonds is used, the undercut length after development is shortened and chipping occurs.

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013254127A (ja) * 2012-06-08 2013-12-19 Toyo Ink Sc Holdings Co Ltd カラーフィルタ用着色組成物、およびカラーフィルタ
JP2018131588A (ja) * 2017-02-17 2018-08-23 大阪有機化学工業株式会社 フォトスペーサー用樹脂、フォトスペーサー用樹脂組成物、フォトスペーサー及びカラーフィルタ
JP2019078878A (ja) * 2017-10-24 2019-05-23 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組成物、及びカラーフィルタ

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013254127A (ja) * 2012-06-08 2013-12-19 Toyo Ink Sc Holdings Co Ltd カラーフィルタ用着色組成物、およびカラーフィルタ
JP2018131588A (ja) * 2017-02-17 2018-08-23 大阪有機化学工業株式会社 フォトスペーサー用樹脂、フォトスペーサー用樹脂組成物、フォトスペーサー及びカラーフィルタ
JP2019078878A (ja) * 2017-10-24 2019-05-23 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組成物、及びカラーフィルタ

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