WO2023054597A1 - 感光性樹脂組成物、硬化物、隔壁、有機電界発光素子、及び画像表示装置 - Google Patents

感光性樹脂組成物、硬化物、隔壁、有機電界発光素子、及び画像表示装置 Download PDF

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WO2023054597A1
WO2023054597A1 PCT/JP2022/036476 JP2022036476W WO2023054597A1 WO 2023054597 A1 WO2023054597 A1 WO 2023054597A1 JP 2022036476 W JP2022036476 W JP 2022036476W WO 2023054597 A1 WO2023054597 A1 WO 2023054597A1
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monomer
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English (en)
French (fr)
Japanese (ja)
Inventor
恵理子 利光
明日香 木村
嘉秀 佐藤
久稔 倉
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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Priority to KR1020247005934A priority Critical patent/KR20240063867A/ko
Priority to CN202280065688.4A priority patent/CN118020026A/zh
Priority to JP2023551856A priority patent/JPWO2023054597A1/ja
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional [2D] radiating surfaces
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional [2D] radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional [2D] radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00

Definitions

  • the present invention relates to a photosensitive resin composition, a cured product obtained by curing the photosensitive resin composition, a partition made of the cured product, an organic electroluminescence element provided with the partition, and an image display device including the organic electroluminescence element.
  • an organic electroluminescence element included in an organic electric field display or the like is manufactured by forming partitions (banks) on a substrate and then laminating various functional layers in the region surrounded by the partitions. .
  • partitions banks
  • various functional layers in the region surrounded by the partitions.
  • a method for easily forming such partition walls a method of forming them by photolithography using a photosensitive resin composition is known.
  • an ink containing the materials constituting the functional layers is prepared, and then the prepared ink is injected into the region surrounded by the partition walls.
  • IJ inkjet
  • the partition wall should be made ink-repellent (liquid repellency) may be required.
  • the region surrounded by the partition wall (hereinafter also referred to as the opening) is used to prevent white spots in the organic light-emitting element and to laminate a flat organic light-emitting layer.
  • the ink must have a property of being easily wetted and spread.
  • Patent Document 1 poly (perfluoroalkylene ether chain) and a fluorine-containing curable resin having the ability to initiate photopolymerization, which are effective in antifouling properties, are used as UV curable hard coating materials for protective film coating materials. and compositions are described.
  • Patent Document 2 describes that by using a photosensitive composition containing an acrylic resin having a polycyclic saturated hydrocarbon skeleton and an ethylenic double bond, good ink repellency is obtained even after UV cleaning treatment. .
  • an object of the present invention is to provide a photosensitive resin composition, particularly a photosensitive resin composition for forming partition walls, which has sufficient liquid repellency and is compatible with inkjet coating properties.
  • the present invention also provides a cured product obtained by curing a photosensitive resin composition, a partition made of the cured product, an organic electroluminescence element provided with the partition, and an image display device including the organic electroluminescence element.
  • the gist of the present invention is as follows.
  • a photosensitive resin composition containing (A) a copolymer, (B) an alkali-soluble resin and (C) a photopolymerizable compound, A photosensitive resin composition in which the copolymer (A) contains the following monomer (a1), the following monomer (a2) and the following monomer (a3) as constituent monomers.
  • Monomer (a1) A monomer having an active group that generates a radical upon irradiation with an active energy ray.
  • Monomer (a2) a monomer having a fluorine atom.
  • Monomer (a3) a monomer having a cyclic ether group with 2 to 4 carbon atoms.
  • X is a hydrogen atom, a fluorine atom or a trifluoromethyl group
  • R f is a fluoroalkyl group having 1 or more and 20 or less carbon atoms, which may have an etheric oxygen atom, or a fluorine atom.
  • the active group in the monomer (a1) is one selected from the group consisting of a benzophenone group, an alkylphenone group, an ⁇ -hydroxyketone group, an ⁇ -aminoketone group, an ⁇ -diketone group and an ⁇ -diketone dialkyl ketal group.
  • the photosensitive resin composition according to any one of [1] to [3] above.
  • FIG. 1 is a schematic diagram showing evaluation criteria for inkjet applicability.
  • FIG. 2 is a schematic cross-sectional view of an example of a color filter provided with partition walls of the present invention.
  • (meth)acryl means “acryl and/or methacryl”.
  • total solid content means all components other than the solvent in the photosensitive resin composition, and even if the components other than the solvent are liquid at room temperature, the component is not included in the solvent and the total Included in solids.
  • a numerical range represented by “to” means a range including the numerical values before and after "to” as lower and upper limits.
  • a and/or B means one or both of A and B, specifically A, B, or A and B.
  • (co)polymer means including both a single polymer (homopolymer) and a copolymer (copolymer), and "polybasic acid (anhydride)” , means “polybasic acid and/or polybasic acid anhydride”.
  • the weight average molecular weight means the weight average molecular weight (Mw) in terms of polystyrene by GPC (gel permeation chromatography).
  • the acid value represents an acid value in terms of effective solid content and is calculated by neutralization titration.
  • a partition wall material means a bank material, a wall material, and a wall material, and similarly, a partition wall means a bank, a wall, and a wall.
  • a light-emitting portion means a portion that emits light when electrical energy is applied.
  • the photosensitive resin composition of the present invention contains (A) a copolymer, (B) an alkali-soluble resin, and (C) a photopolymerizable compound, and (A) a copolymer contains a specific monomer (a1), a specific monomer (a2) and a specific monomer (a3), which will be described later, as constituent monomers.
  • the photosensitive resin composition of the present invention may further contain other components as necessary, such as (D) a photopolymerization initiator, (E) a colorant, and (F) a chain transfer agent. good too.
  • the partition wall is, for example, for partitioning the functional layer (organic layer, light-emitting portion) in the active drive type organic electroluminescence device. It is used to form pixels including functional layers and partition walls by ejecting and drying ink, which is a material for forming.
  • the photosensitive resin composition of the present invention contains (A) a copolymer, (B) an alkali-soluble resin and (C) a photopolymerizable compound.
  • the (A) copolymer comprises monomer (a1), monomer (a2), and monomer (a3) as constituent monomers. contains That is, the (A) copolymer has, as its constituent units, units based on the monomer (a1), units based on the monomer (a2), and units based on the monomer (a3).
  • Monomer (a1) A monomer having an active group that generates a radical upon irradiation with an active energy ray.
  • Monomer (a2) a monomer having a fluorine atom.
  • Monomer (a3) a monomer having a cyclic ether group with 2 to 4 carbon atoms.
  • the copolymer is immobilized by the reaction of the cyclic ether group having 2 to 4 carbon atoms of the copolymer, and (A) the copolymer or its thermal decomposition product is Migration to the pixel portion can be suppressed.
  • ink is applied to a region surrounded by partition walls, such as a pixel portion, by using an inkjet method, it is possible to suppress the occurrence of color mixture between adjacent pixel portions and to achieve good inkjet coating properties of the pixel portion. can be considered to be compatible.
  • Monomer (a1) is a monomer having an active group that generates a radical upon irradiation with an active energy ray.
  • Examples of the monomer (a1) include compounds having an active group and a radically polymerizable group.
  • the active group of the monomer (a1) may have a structure capable of generating radicals upon exposure to active energy rays (a structure having photopolymerization initiation properties).
  • a structure having photopolymerization initiation properties various known structures can be employed, and examples thereof include a hydrogen abstraction type, an electron transfer type, and an intramolecular cleavage type.
  • active groups include benzophenone group, alkylphenone group, benzoin group, benzoin ether group, ⁇ -hydroxyketone group (eg, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2- a group obtained by removing one hydrogen atom from the "hydroxyl group in 2-hydroxyethoxy" of methyl-1-propanone), ⁇ -aminoketone group, ⁇ -diketone group, ⁇ -diketonedialkylacetal group, ⁇ -diketonedialkylketal group, Examples include anthraquinone group, thioxanthone group, ketocoumarin group, alkylphenylglyoxalate group, phosphine oxide group, and oxime ester group.
  • ⁇ -hydroxyketone group eg, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2- a group obtained by removing one hydrogen atom from the "hydroxyl group in 2-hydroxyethoxy" of methyl-1-propan
  • a benzophenone group, an alkylphenone group, an ⁇ -hydroxyketone group, an ⁇ -aminoketone group, an ⁇ -diketone group, and an ⁇ -diketone dialkyl ketal group are preferred in terms of their high radical generation efficiency, and a benzophenone group and an alkylphenone group.
  • an ⁇ -hydroxyketone group is more preferred, and an ⁇ -hydroxyketone group is particularly preferred.
  • the radically polymerizable group of the monomer (a1) includes a functional group containing a radically polymerizable unsaturated bond (carbon-carbon double bond, etc.), and specific examples thereof include a (meth)acryloyl group and a vinyl group. .
  • a (meth)acrylic acid ester having an active group is preferable from the viewpoint of easiness in synthesizing the (A) copolymer and easiness in adjusting the introduction amount of the active group.
  • Examples of the monomer (a1) include 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate, 4-methacryloyloxybenzophenone, 4-[(4-methacrylamido)thiophenyl] Benzophenone, 1-[(2-acryloyloxy)ethoxycarbonyl]thioxanthone, 1-[4-(2-acryloyloxyethylthio)phenyl]-2-methyl-2-morpholinopropan-1-one.
  • 2-[4-(2-hydroxy-2-methyl-1-oxopropyl)phenoxy]ethyl methacrylate is more preferable from the viewpoint of liquid repellency and inkjet applicability.
  • These monomers having active groups may be used alone or in combination of two or more.
  • Monomer (a2) is a monomer having a fluorine atom.
  • the monomer (a2) include compounds having a fluorine atom and a radically polymerizable group.
  • the radically polymerizable group is the same as described above.
  • the unit based on the monomer (a2) imparts at least one of water repellency and oil repellency to the cured product and contributes to the liquid repellency of the cured product. Further, if the copolymer (A) has this unit, the copolymer (A) is likely to segregate on the surface side of the coating film when the coating film of the photosensitive resin composition is formed.
  • the concentration of units based on the monomer (a2) on the surface side of the coating film increases, and liquid repellency can be efficiently imparted to the surface of the cured product.
  • the segregation of the (A) copolymer on the surface side of the coating film increases the concentration of the active groups on the surface side of the coating film, and when irradiated with an active energy ray, the activity of the (A) copolymer Radicals are generated from the group, and the polymerization reaction proceeds with the photopolymerizable compound (C) starting from the generated radicals, so the copolymer (A) is likely to be fixed near the surface of the coating film.
  • the liquid repellency of the upper surface of the partition wall can be maintained even after the step of developing the coating film after exposure. It is considered possible to suppress the occurrence of color mixture between adjacent pixel portions when ink is applied.
  • the degree of cure of the coating film depends on the amount of radically polymerizable groups and the amount of active groups in the photosensitive resin composition, that is, the amount of (A) the copolymer and (D) the photopolymerization initiator and the amount of exposure during plate making. etc. can be adjusted.
  • the monomer (a2) is preferably a monomer having a fluoroalkyl group, more preferably a monomer having a fluoroalkyl group and a radically polymerizable group.
  • the fluoroalkyl group in the monomer (a2) preferably has a structure represented by the following general formula (1).
  • -CFXR f Formula (1) (In formula (1), X is a hydrogen atom, a fluorine atom or a trifluoromethyl group, and R f is a fluoroalkyl group having 1 or more and 20 or less carbon atoms, which may have an etheric oxygen atom, or a fluorine atom.)
  • the number of carbon atoms in R f in formula (1) is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, particularly preferably 5 or more, and preferably 20 or less, more preferably is 10 or less, more preferably 6 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 20 are preferred, 2 to 20 are more preferred, 3 to 10 are even more preferred, and 5 to 6 are particularly preferred.
  • By making it more than a lower limit there exists a tendency for liquid repellency to express.
  • the amount is not more than the upper limit, the compatibility with other components constituting the photosensitive resin composition tends to be improved.
  • a (meth)acrylic acid ester having a fluoroalkyl group is preferable as the compound having a fluoroalkyl group and a radically polymerizable group.
  • a (meth)acrylic acid ester having a fluoroalkyl group is more preferably a (meth)acrylic acid ester having a perfluoroalkyl group.
  • (Meth)acrylic acid esters containing a fluoroalkyl group include, for example, 2,2,2-trifluoroethyl acrylate (Viscoat 3F manufactured by Osaka Organic Chemical Industry Co., Ltd.), 2,2,3,3-tetrafluoropropyl Acrylate (Viscoat 4F manufactured by Osaka Organic Chemical Industry Co., Ltd.), 2,2,3,3-tetrafluoropropyl methacrylate (DK-4F manufactured by Daikin Industries, Ltd.
  • Viscoat 8FM manufactured by the company 1H,1H,2H,2H-tridecafluorooctyl acrylate (Viscoat 13F manufactured by Osaka Organic Chemical Industry Co., Ltd., CHEMINOX FAAC-6 manufactured by Unimatec Co., Ltd.), 1H,1H,2H,2H-nonafluoro Hexyl acrylate (CHEMINOX FAAC-4 manufactured by Unimatec Co., Ltd.), 1H,1H,2H,2H-nonafluorohexyl methacrylate (CHEMINOX FAMAC-4 manufactured by Unimatec Co., Ltd.), 1H,1H,2H,2H-tridecafluorooctyl methacrylate (CHEMINOX FAMAC-6 manufactured by Unimatec Co., Ltd.).
  • the monomer (a2) may be a compound having a fluoroalkylene group and a radically polymerizable group, and although the fluoroalkylene group is not particularly limited, it preferably has a perfluoroalkylene ether chain. Specific examples include -CF 2 -O-, -(CF 2 ) 2 -O-, -(CF 2 ) 3 -O-, -CF 2 -C(CF 3 )O-, -C(CF 3 ) -CF 2 -O- and divalent groups having these repeating units are included. Examples of compounds having a fluoroalkylene group and a radically polymerizable group include the following monomers.
  • PFPE represents a perfluoroalkylene ether chain.
  • monomers having a fluoroalkyl group are preferred, monomers having a perfluoroalkyl group are more preferred, and methacrylic acid 3,3,4,4,5,5,6 ,6,7,7,8,8,8-tridecafluorooctyl groups are more preferred.
  • fluorine atom-containing monomers may be used alone or in combination of two or more.
  • Monomer (a3) is a monomer having a cyclic ether group having 2 to 4 carbon atoms.
  • Cyclic ether groups include, for example, an epoxy group, an oxetanyl group, or a tetrahydrofuryl group.
  • Examples of the monomer (a3) include compounds having a cyclic ether group having 2 to 4 carbon atoms and a radically polymerizable group.
  • An epoxy group is preferable as the cyclic ether group having 2 to 4 carbon atoms.
  • the radically polymerizable group is the same as described above.
  • Monomers having an epoxy group include, for example, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 6,7-epoxy heptyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, glycidyl vinyl ether, 1,2-epoxy-4-vinylcyclohexane, 2-vinylbenzyl glycidyl ether, 3-vinylbenzyl glycidyl ether, 4-vinylbenzyl glycidyl ether, ⁇ -methyl-2-vinylbenzyl glycidyl ether, ⁇ -methyl-3-vinylbenzyl glycidyl ether, ⁇ -methyl-4-vinyl
  • Examples of monomers having an oxetanyl group include 3-methyl-3-(meth)acryloyloxymethyloxetane, 3-ethyl-3-(meth)acryloyloxymethyloxetane, 3-methyl-3-(meth)acryloyloxyethyl oxetane, 3-ethyl-3-(meth)acryloyloxyethyl oxetane.
  • Examples of monomers having a tetrahydrofuryl group include tetrahydrofurfuryl (meth)acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, and (meth)acrylic acid tetrahydrofuran-3-yl ester.
  • glycidyl (meth)acrylate is preferable as the monomer (a3) from the viewpoint of ease of synthesis of (A) copolymer and ease of adjustment of the introduction amount of cyclic ether groups.
  • These monomers having a cyclic ether group may be used alone or in combination of two or more.
  • the (A) copolymer has, as a constituent monomer, a monomer (a4) having a hydroxyl group. (hereinafter also referred to as monomer (a4)) may be further contained.
  • Examples of the monomer (a4) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl ( meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, 2 - hydroxyalkyl (meth)acrylates such as hydroxy-3-phenoxypropyl (meth)acrylate, glycerol (meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate; ethyl- ⁇ -(hydroxymethyl)acrylate, p-hydroxy Phenylethyl (meth)acrylate is mentioned. These may be used alone or in combination of two or more.
  • the copolymer may further contain, as a constituent monomer, a monomer (a5) having a hydrogen-donating functional group (hereinafter also referred to as monomer (a5)).
  • a monomer (a5) having a hydrogen-donating functional group
  • the monomer (a1) has a hydrogen abstraction type active group, it preferably contains units based on the monomer (a5).
  • the copolymer has a unit based on the monomer (a5), it is possible to suppress the inhibition of polymerization by oxygen from the coating film surface of the photosensitive resin composition, and the coating film is effectively cured. It tends to be possible to make it easy to develop liquid repellency.
  • hydrogen-donating functional groups examples include alkylamino groups, mercapto groups, amide groups, and alkyl ether groups.
  • a mercapto group, an alkylamino group, and an amide group are preferable from the viewpoint that the curing reaction can proceed particularly efficiently and the reactivity with oxygen radicals is high.
  • Examples of the monomer (a5) include compounds having a hydrogen-donating functional group and a radically polymerizable group.
  • (Meth)acrylic acid esters and (meth)acrylamides having a hydrogen-donating functional group are preferred.
  • Examples of the monomer (a5) include N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-vinylcaprolactam, N-vinylpyrrolidone, N-isopropyl(meth)acrylamide, N,N -dimethylaminoethyl (meth)acrylate, 2-[(butylamino)carbonyl]oxy]ethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylamide, N,N-diethylaminopropyl (meth)acrylamide, N , N-diethylaminoethyl (meth)acrylate, N,N-dimethylamino
  • N,N-dimethylacrylamide, N,N-dimethylaminoethyl (meth)acrylate, and N,N-diethylaminoethyl (meth)acrylate are preferable from the viewpoint of excellent curing acceleration effect when used in combination with an active group.
  • N,N-diethylaminoethyl (meth)acrylate is more preferable from the standpoint that polymerization inhibition by oxygen can be suppressed, curing can be effectively performed, and liquid repellency can be easily developed.
  • These compounds may be used alone or in combination of two or more.
  • the copolymer has a monomer (a6) having an alkyl group having 4 or more carbon atoms (hereinafter, monomer (Also referred to as (a6).) may further contain one or more units based on.
  • the alkyl group having 4 or more carbon atoms in the monomer (a6) may be linear, branched or cyclic. Cyclic alkyl groups may be monocyclic or polycyclic. From the viewpoint of more effectively segregating the (A) copolymer on the surface of the coating film, the alkyl group is preferably linear. The number of carbon atoms in the alkyl group having 4 or more carbon atoms is preferably 4 to 30, more preferably 6 to 20, and still more preferably 12, from the viewpoint of more effectively segregating the (A) copolymer on the surface of the coating film. ⁇ 18.
  • Examples of the monomer (a6) include compounds having an alkyl group having 4 or more carbon atoms and a radically polymerizable group, and ease of synthesis of the compound and ease of adjustment of the introduction amount of the alkyl group having 4 or more carbon atoms. from the viewpoint of (meth)acrylic acid alkyl ester having an alkyl group having 4 or more carbon atoms is preferable.
  • Examples of the monomer (a6) include butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, ) acrylate, decyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, myristyl (meth)acrylate, cetyl (meth)acrylate , stearyl (meth)acrylate, isostearyl (meth)acrylate, tridecyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tricyclode
  • (meth)acrylic acid alkyl esters having a linear alkyl group having 4 or more carbon atoms are preferred.
  • the (meth)acrylic acid alkyl ester having a straight-chain alkyl group having 4 or more carbon atoms those in which the number of carbon atoms in the alkyl group is within the preferred range described above are preferable.
  • Ethylhexyl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, and stearyl (meth)acrylate are more preferred, and stearyl (meth)acrylate is particularly preferred.
  • These (meth)acrylic acid esters may be used alone or in combination of two or more.
  • the categories of monomers (a1) to (a6) are described. As long as the monomer has an active group that generates a radical upon irradiation with an active energy ray, the monomer (a1) can be used even if it has a fluorine atom or a functional group that is characteristic of the other monomers (a2) to (a6). I reckon. A monomer having a fluorine atom is regarded as the monomer (a2) even if it has a functional group that is characteristic of the other monomers (a3) to (a6). A monomer having a cyclic ether group with 2 to 4 carbon atoms is regarded as the monomer (a3) even if it has a functional group characteristic of the other monomers (a4) to (a6).
  • a monomer having a hydroxyl group is regarded as the monomer (a4) even if it has a functional group that is characteristic of the other monomers (a5) to (a6). As long as the monomer has a hydrogen-donating functional group, it is regarded as the monomer (a5) even if it has an alkyl group with 4 or more carbon atoms, which is characteristic of the monomer (a6).
  • the copolymer may further have units based on monomers other than those described above, if necessary.
  • Other monomers include, for example, a compound having a radically polymerizable group and not having an active group, a cyclic ether group having 2 to 4 carbon atoms, an alkyl group having 4 or more carbon atoms, a fluorine atom and a hydrogen-donating functional group. is mentioned.
  • Other monomers include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, citraconic acid, and salts thereof; methyl (meth) acrylate, ethyl (meth) acrylate.
  • (meth)acrylates such as propyl (meth)acrylate; nitrogen-containing monomers such as (meth)acrylonitrile; styrene compounds such as styrene, ⁇ -methylstyrene, divinylbenzene, and vinyltoluene; vinyls such as vinyl propionate and vinyl acetate esters; phosphorus-containing vinyl-based monomers; vinyl halides such as vinyl chloride and pyridene chloride; and conjugated dienes such as butadiene.
  • nitrogen-containing monomers such as (meth)acrylonitrile
  • styrene compounds such as styrene, ⁇ -methylstyrene, divinylbenzene, and vinyltoluene
  • vinyls such as vinyl propionate and vinyl acetate esters
  • phosphorus-containing vinyl-based monomers vinyl halides such as vinyl chloride and pyridene chloride
  • conjugated dienes such as butadiene.
  • the active group may be present at the end of the main chain of (A) the copolymer, or may be present in units based on the monomers constituting the (A) copolymer.
  • the copolymer preferably has a plurality of active groups in its molecule. This tends to increase the concentration of active groups in the vicinity of the coating film surface.
  • the content of active groups per gram of the copolymer is preferably 0.1 mmol/g or more, more preferably 0.5 mmol/g or more, still more preferably 0.8 mmol/g or more, and also preferably is 2.5 mmol/g or less, more preferably 2.0 mmol/g or less. The above upper and lower limits can be combined arbitrarily.
  • the content of active groups is at least the lower limit of the above range, curability tends to be more excellent and high liquid repellency can be exhibited. Moreover, it exists in the tendency for the storage stability of a photosensitive resin composition to be more excellent as it is below an upper limit.
  • the ratio of units based on the monomer (a1) to the total mass (100% by mass) of all units constituting the (A) copolymer is preferably is 1% by mass or more, more preferably 10% by mass or more, more preferably 20% by mass or more, particularly preferably 30% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, and more preferably is 70% by mass or less, particularly preferably 60% by mass or less.
  • the above upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 90% by mass, more preferably 10 to 80% by mass, still more preferably 20 to 70% by mass, and particularly preferably 30 to 60% by mass.
  • the ratio of units based on the monomer (a1) is at least the lower limit of the above range, the curability tends to be more excellent and high liquid repellency can be exhibited. When it is at most the upper limit, the image stability of the photosensitive resin composition tends to be more excellent.
  • the ratio of units based on the monomer (a2) to the total mass (100% by mass) of all units constituting the copolymer is preferably 5% by mass or more, more preferably 15% by mass or more, and still more preferably It is 25% by mass or more, more preferably 35% by mass or more, particularly preferably 40% by mass or more, and even more preferably 45% by mass or more. Also, it is preferably 70% by mass or less, more preferably 65% by mass or less, still more preferably 60% by mass or less, even more preferably 55% by mass or less, and particularly preferably 50% by mass or less.
  • the above upper and lower limits can be combined arbitrarily.
  • preferably 5 to 70% by mass preferably 15 to 70% by mass, still more preferably 25 to 65% by mass, even more preferably 35 to 60% by mass, particularly preferably 40 to 55% by mass, particularly preferably is 45 to 50% by mass.
  • the proportion of units based on the monomer (a2) is at least the lower limit of the above range, the liquid repellency tends to be more effectively enhanced.
  • the ink-jet applicability tends to be excellent.
  • the ratio of units based on the monomer (a3) to the total mass (100 mass) of all units constituting the (A) copolymer is preferably It is 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more. Also, it is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 20% by mass or less.
  • the above upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 50% by mass, more preferably 1 to 40% by mass, even more preferably 2 to 30% by mass, and particularly preferably 3 to 20% by mass. If the ratio of the units based on the monomer (a3) is within the above range, the liquid repellency tends to be exhibited more effectively.
  • the ratio of units based on the monomer (a4) to the total mass (100% by mass) of all units constituting the (A) copolymer is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 8% by mass or more, and is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass. Below, it is 50 mass % or less especially preferably.
  • the above upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 80% by mass, more preferably 1 to 70% by mass, still more preferably 5 to 60% by mass, and particularly preferably 8 to 50% by mass. If the ratio of the units based on the monomer (a4) is within the above range, the liquid repellency tends to be exhibited more effectively.
  • the ratio of units based on the monomer (a5) to the total mass (100% by mass) of all units constituting the (A) copolymer is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably 5% by mass or more, and is preferably 60% by mass or less, more preferably 30% by mass or less, and still more preferably 10% by mass. It is below.
  • the above upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 60% by mass, more preferably 1 to 30% by mass, still more preferably 3 to 30% by mass, and particularly preferably 1 to 10% by mass. If the ratio of the units based on the monomer (a5) is within the above range, there is a tendency that the liquid repellency can be exhibited more effectively.
  • the ratio of units based on the monomer (a6) to the total mass (100% by mass) of all units constituting the (A) copolymer is preferably 1% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more, and is preferably 60% by mass or less, more preferably 30% by mass or less, and still more preferably 10% by mass. It is below.
  • the above upper and lower limits can be combined arbitrarily. For example, it is preferably 1 to 60% by mass, more preferably 1 to 30% by mass, still more preferably 1 to 10% by mass. If the ratio of the units based on the monomer (a6) is within the above range, there is a tendency that the liquid repellency can be exhibited more effectively.
  • the copolymer contains monomers other than the monomers (a1) to (a6) as constituent monomers
  • the total mass (100% by mass) of all units constituting the copolymer other The proportion of monomer units is preferably 1% by mass or more, more preferably 5% by mass or more, and is preferably 40% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 40% by mass is preferable, 1 to 20% by mass is more preferable, and 5 to 10% by mass is even more preferable.
  • the fluorine atom content in the copolymer is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and even more preferably 20% by mass or more; Particularly preferably, it is 24% by mass or more. Also, it is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, and even more preferably 30% by mass or less.
  • the above upper and lower limits can be combined arbitrarily. For example, it is preferably 5 to 60% by mass, more preferably 10 to 60% by mass, still more preferably 15 to 50% by mass, still more preferably 20 to 40% by mass, and particularly preferably 24 to 30% by mass.
  • the weight average molecular weight (Mw) of the copolymer is preferably 10,000 or more, more preferably 30,000 or more, still more preferably 50,000 or more, still more preferably 70,000 or more, and particularly preferably 80,000 or more. . Also, it is preferably 500,000 or less, more preferably 300,000 or less, even more preferably 200,000 or less, and even more preferably 150,000 or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 10,000 to 500,000, more preferably 30,000 to 500,000, still more preferably 50,000 to 300,000, even more preferably 70,000 to 200,000, and particularly preferably 80,000 to 150,000.
  • Mw of the copolymer is a value converted to standard polystyrene measured by gel permeation chromatography (GPC). Detailed measurement conditions are as described in the examples below.
  • a copolymer is obtained by polymerizing a monomer component containing necessary monomers.
  • a monomer component containing necessary monomers.
  • the monomer component may further contain any one or more of monomer (a4), monomer (a5), monomer (a6) and other monomers, if necessary.
  • (A) Polymerization of the copolymer is typically carried out in the presence of a polymerization initiator. If necessary, a chain transfer agent may be used in combination during the polymerization.
  • a polymerization initiator e.g., ethylene glycol dimethacrylate (PET), ethylene glycol dimethacrylate (PET), ethylene glycol dimethacrylate (PET), ethylene glycol dimethacrylate (PE), ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, poly(ethylene glycol) terpolymerization, graft copolymer, graft copolymer, graft copolymer, graft copolymer, graft copolymer, graft copolymer, graft copolymer, graft copolymer, graft copolymer, graft copolymer, graft copolymer, graft copolymer, graft copolymer, graft
  • the content of the copolymer (A) in the photosensitive resin composition of the present invention is not particularly limited, the total solid content (100% by mass) of the photosensitive resin composition is preferably 0.01% by mass or more, More preferably 0.05% by mass or more, still more preferably 0.07% by mass or more, still more preferably 0.1% by mass or more, and preferably 50% by mass or less, more preferably 30% by mass or less, More preferably 20% by mass or less, still more preferably 10% by mass or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 0.01 to 30% by mass is preferable, 0.05 to 20% by mass is more preferable, 0.07 to 10% by mass is even more preferable, and 0.1 to 5% by mass is particularly preferable.
  • the ink repellency tends to be improved by making it equal to or higher than the lower limit. Compatibility with other components tends to be improved by adjusting the content to the above upper limit or less.
  • the photosensitive resin composition of the present invention contains (B) an alkali-soluble resin.
  • the alkali-soluble resin is not particularly limited as long as it is a resin that can be developed with an alkali developer.
  • the (B) alkali-soluble resin is a component different from the (A) copolymer, and when the alkali-soluble resin corresponding to the (A) copolymer is present, the (A) copolymer can be deal.
  • Alkali-soluble resins include various resins containing carboxy groups and/or hydroxyl groups. Among them, a resin having a carboxyl group is preferable from the viewpoint of obtaining partition walls with an appropriate taper angle and suppressing residue after development.
  • the (B) alkali-soluble resin is an alkali-soluble resin (b) having an ethylenic double bond (hereinafter sometimes abbreviated as "alkali-soluble resin (b)"). is preferably included.
  • alkali-soluble resin (b) having an ethylenic double bond
  • the curability is increased, and ink repellency of the partition walls obtained by suppressing outflow of the copolymer (A) and/or the liquid repellent agent during development. tend to be more sexual.
  • epoxy (meth)acrylate resin (b1) and acrylic copolymer resin (b2) are preferred from the viewpoint of developing solubility.
  • Epoxy (meth)acrylate resin (b1) is more preferable from the viewpoint of outgas reduction.
  • the epoxy (meth)acrylate resin (b1) is described in detail below.
  • Epoxy (meth)acrylate resin (b1) is a resin obtained by adding an acid or ester compound having an ethylenically unsaturated bond (ethylenic double bond) to an epoxy resin, and further adding a polybasic acid or its anhydride.
  • an ethylenically unsaturated bond is added to the epoxy resin via an ester bond (-COO-) by ring-opening addition of a carboxyl group of an acid having an ethylenically unsaturated bond to the epoxy group of the epoxy resin.
  • one carboxyl group of the polybasic acid anhydride is added to the hydroxyl group generated at that time.
  • the epoxy (meth)acrylate resin (b1) also includes a resin obtained by reacting the carboxy group of the resin obtained by the above reaction with a compound having a reactive functional group.
  • the epoxy (meth)acrylate resin has substantially no epoxy group due to its chemical structure, and is not limited to "(meth)acrylate", but an epoxy compound (epoxy resin) is a raw material. and "(meth)acrylate” is a typical example, so it is named in this way according to common practice.
  • the epoxy (meth)acrylate resin (b1) those having an aromatic ring in the main chain can be more preferably used from the viewpoint of improving the shape of the lower part of the partition wall and improving the development adhesion.
  • epoxy resin includes raw material compounds before forming a resin by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins and used.
  • the epoxy resin a compound obtained by reacting a phenolic compound and epihalohydrin can be used.
  • the phenolic compound is preferably a compound having a divalent or more divalent phenolic hydroxyl group, and may be a monomer or a polymer.
  • bisphenol A type epoxy resin bisphenol novolak epoxy resin, cresol novolak epoxy resin, epoxidized polymer of phenol and dicyclopentadiene, 9,9-bis(4'-hydroxyphenyl) Epoxidized fluorene is preferred, and bisphenol A type epoxy resin is more preferred.
  • Acids having an ethylenically unsaturated bond include, for example, (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, pentaerythritol tri(meth)acrylate succinic anhydride adduct, pentaerythritol tri(meth) Acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta(meth)acrylate succinic anhydride adduct, dipentaerythritol penta(meth)acrylate phthalic anhydride adduct, dipentaerythritol penta(meth)acrylate tetrahydrophthalic anhydride adduct , reaction products of (meth)acrylic acid and ⁇ -caprolactone.
  • (meth)acrylic acid is preferable from the viewpoint of sensitivity.
  • polybasic acids examples include succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4 - ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid , benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, and their anhydrides.
  • succinic anhydride succinic anhydride
  • maleic anhydride succinic anhydride
  • itaconic anhydride succinic anhydride is more preferred, from the viewpoint of reducing residues in pixel areas after development.
  • polyhydric alcohol tends to increase the molecular weight of the epoxy (meth)acrylate resin (b1), introduce branches into the molecule, and balance the molecular weight and viscosity. In addition, the rate of introduction of acid groups into the molecule can be increased, and there is a tendency to easily balance sensitivity, adhesion, and the like.
  • polyhydric alcohols include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. These may be used individually by 1 type, and may use 2 or more types together.
  • the acid value of the epoxy (meth)acrylate resin (b1) is not particularly limited, but is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, still more preferably 40 mgKOH/g or more, and even more preferably 60 mgKOH/g or more. Also, it is preferably 200 mgKOH/g or less, more preferably 180 mgKOH/g or less, still more preferably 150 mgKOH/g or less, even more preferably 120 mgKOH/g or less, and particularly preferably 100 mgKOH/g or less.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 10 to 200 mgKOH / g, more preferably 10 to 180 mgKOH / g, more preferably 20 to 150 mgKOH / g, even more preferably 40 to 120 mgKOH / g, 60-100 mg KOH/g is particularly preferred.
  • the amount is equal to or higher than the above lower limit, there is a tendency for the amount of residue after development to be reduced.
  • the content is equal to or less than the above upper limit, the film tends to be less likely to be dissolved by alkali during development, and the film strength tends to be improved.
  • the weight average molecular weight (Mw) of the epoxy (meth)acrylate resin (b1) is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, still more preferably 3000 or more, still more preferably 4000 or more, and even more preferably 5000. More preferably, it is 6,000 or more, most preferably 7,000 or more, preferably 30,000 or less, more preferably 20,000 or less, still more preferably 15,000 or less, and particularly preferably 10,000 or less.
  • the upper limit and lower limit can be arbitrarily combined, preferably 1000 to 30000, more preferably 2000 to 30000, still more preferably 3000 to 20000, even more preferably 4000 to 20000, even more preferably 5000 to 15000, particularly preferably 6000 to 15000 is particularly preferred, and 7,000 to 10,000 is most preferred.
  • the content is at least the above lower limit, the film becomes less likely to be dissolved by alkali during development, and the film strength tends to improve. Further, when the concentration is set to the above upper limit or less, there is a tendency that the residue after development is reduced.
  • the epoxy (meth)acrylate resin (b1) can be synthesized by a conventionally known method. Specifically, the epoxy resin is dissolved in an organic solvent, and in the presence of a catalyst and a thermal polymerization inhibitor, the acid or ester compound having the ethylenically unsaturated bond is added for addition reaction, and further polybasic acid or its A method of continuing the reaction by adding anhydride can be used.
  • organic solvents include methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate.
  • catalysts include tertiary amines such as triethylamine, benzyldimethylamine and tribenzylamine; ammonium salts; phosphorus compounds such as triphenylphosphine; stibines such as triphenylstibine;
  • Thermal polymerization inhibitors include, for example, hydroquinone, hydroquinone monomethyl ether, and methylhydroquinone. These may be used individually by 1 type, and may use 2 or more types together.
  • the acid or ester compound having an ethylenically unsaturated bond is preferably 0.7 to 1.3 chemical equivalents, more preferably 0.9 to 1.1 chemical equivalents, relative to 1 chemical equivalent of the epoxy group of the epoxy resin. can be used.
  • the temperature during the addition reaction is preferably 60 to 150°C, more preferably 80 to 120°C.
  • the amount of polybasic acid (anhydride) is preferably 0.1 to 1.2 chemical equivalents, more preferably 0.2 to 1.1 chemical equivalents, relative to 1 chemical equivalent of hydroxyl groups generated in the addition reaction. can be used.
  • the epoxy (meth)acrylate resin (b1) is an epoxy (meth)acrylate resin (b1-1 ) (hereinafter sometimes referred to as “epoxy (meth)acrylate resin (b1-1)”), epoxy (meth)acrylate resin (b1-2) containing a partial structure represented by the following general formula (ii) (hereinafter sometimes referred to as “epoxy (meth)acrylate resin (b1-2)”), and an epoxy (meth)acrylate resin (b1-3) containing a partial structure represented by the following general formula (iii) (hereinafter sometimes referred to as “epoxy (meth)acrylate resin (b1-3)”).
  • the epoxy (meth)acrylate resin (b1) is an epoxy (meth)acrylate resin containing a partial structure represented by the following general formula (i) from the viewpoint of reducing outgassing and improving the shape of the lower part of the partition wall. It preferably contains (b1-1), and more preferably an epoxy (meth)acrylate resin (b1-1) containing a partial structure represented by the following general formula (i).
  • a partial structure represented by the following general formula (i) is presumed to be that it has a rigid main skeleton, so that it is difficult to be decomposed by heat, and penetration of the developing solution into the exposed portion during development is reduced.
  • R a represents a hydrogen atom or a methyl group
  • R b represents a divalent hydrocarbon group which may have a substituent.
  • the benzene ring in formula (i) may be further substituted with any substituent. * represents a bond.
  • R b represents a divalent hydrocarbon group which may have a substituent.
  • the divalent hydrocarbon group includes a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked. mentioned.
  • the divalent aliphatic group includes linear, branched and cyclic ones. Among these, linear ones are preferable from the viewpoint of developing solubility, while cyclic ones are preferable from the viewpoint of reducing permeation of the developer into the exposed area.
  • the number of carbon atoms is preferably 1 or more, more preferably 3 or more, still more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less.
  • the above upper limit and lower limit can be combined arbitrarily. When the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • divalent linear aliphatic groups examples include methylene group, ethylene group, n-propylene group, n-butylene group, n-hexylene group and n-heptylene group. Among these, a methylene group is preferable from the viewpoint of residue reduction.
  • the divalent branched aliphatic group includes, for example, the aforementioned divalent straight-chain aliphatic group, and side chains of methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl. structures having a group, a sec-butyl group, and a tert-butyl group.
  • the number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, it is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less.
  • the above upper limit and lower limit can be combined arbitrarily. When the content is equal to or higher than the lower limit, there is a tendency that the residual film rate is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • the divalent cyclic aliphatic group includes, for example, a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a dicyclopentane ring, a norbornane ring, an isobornane ring, and an adamantane ring in which two hydrogen atoms are removed. groups.
  • a group obtained by removing two hydrogen atoms from an adamantane ring is preferable from the viewpoint of development adhesion.
  • divalent aliphatic group may have include, for example, alkoxy groups having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; Unsubstituted is preferred from the viewpoint of ease of synthesis.
  • Divalent aromatic ring groups include divalent aromatic hydrocarbon ring groups and divalent aromatic heterocyclic groups.
  • the number of carbon atoms is preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less.
  • the above upper limit and lower limit can be combined arbitrarily. When the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring.
  • the divalent aromatic hydrocarbon ring group includes, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.
  • the aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a monocyclic ring or a condensed ring.
  • divalent aromatic heterocyclic groups include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, and indole ring having two free valences.
  • substituents that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group, and a glycidyl ether group. Among these, unsubstituted is preferred from the viewpoint of curability.
  • one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic ring groups is linked to one or more.
  • the number of divalent aliphatic groups is not particularly limited, it is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
  • the above upper limit and lower limit can be combined arbitrarily. When the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • the number of divalent aromatic ring groups is not particularly limited, it is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
  • the above upper limit and lower limit can be combined arbitrarily. When the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • Examples of groups in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups represented by the following formulas (iA) to (iF). be done.
  • a group represented by the following formula (iA) is preferable from the viewpoint of rigidity of the skeleton and hydrophobicity of the membrane. * in the chemical formula represents a bond.
  • the benzene ring in formula (i) may be further substituted with optional substituents.
  • substituents on the benzene ring in formula (i) include hydroxyl group, methyl group, methoxy group, ethyl group, ethoxy group, propyl group and propoxy group.
  • the number of substituents is also not particularly limited, and may be one or two or more as long as it is chemically allowed. From the viewpoint of curability, non-substitution is preferred.
  • the partial structure represented by the formula (i) is preferably a partial structure represented by the following formula (i-1) from the viewpoint of development solubility.
  • R a and R b have the same definitions as in formula (i) above.
  • R 1 represents an optionally substituted divalent hydrocarbon group having 1 to 4 carbon atoms. * represents a bond.
  • the benzene ring in formula (i-1) may be further substituted with any substituent.
  • R 1 represents an optionally substituted divalent hydrocarbon group having 1 to 4 carbon atoms.
  • Divalent hydrocarbon groups include an alkylene group and an alkenylene group.
  • the alkylene group may be linear or branched, but is preferably linear from the viewpoint of development solubility.
  • the number of carbon atoms is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and preferably 4 or less, more preferably 3 or less.
  • the above upper limit and lower limit can be combined arbitrarily, and for example, 1 to 4 are preferred, 1 to 3 are more preferred, and 2 to 3 are even more preferred.
  • alkylene group examples include a methylene group, an ethylene group, a propylene group, and a butylene group. From the viewpoint of reducing outgassing, a methylene group and an ethylene group are preferred, and an ethylene group is more preferred.
  • the alkenylene group may be linear or branched, but is preferably linear from the viewpoint of development solubility.
  • the number of carbon atoms is not particularly limited, it is preferably 2 or more, preferably 4 or less, and more preferably 3 or less. For example, 2 to 4 are preferable, and 2 to 3 are more preferable.
  • the content is equal to or higher than the above lower limit, there is a tendency for the residual film rate to increase. In addition, there is a tendency that the amount of outgassing is reduced by making it equal to or less than the above upper limit.
  • alkenylene group examples include an ethenylene group, a propenylene group, and a butylenylene group, with the ethenylene group being preferred from the viewpoint of outgassing.
  • the substituent that the divalent hydrocarbon group having 1 to 4 carbon atoms may have is not particularly limited, and examples thereof include a halogen atom, an alkoxy group, a benzoyl group, and a hydroxyl group, from the viewpoint of ease of synthesis. is preferably unsubstituted.
  • R 1 is preferably a divalent alkylene group having 1 to 4 carbon atoms, more preferably a methylene group or an ethylene group, and even more preferably an ethylene group.
  • the partial structure represented by the formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin (b1-1) may be one type or two or more types.
  • the number of partial structures represented by the formula (i) contained in one molecule of the epoxy (meth)acrylate resin (b1-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and 3 or more. is more preferred, 10 or less is preferred, and 8 or less is even more preferred.
  • the above upper limit and lower limit can be arbitrarily combined, and for example, 1 to 10 are preferred, 2 to 10 are more preferred, and 3 to 8 are even more preferred.
  • the number of partial structures represented by the formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin (b1-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, 3 or more is more preferable, 10 or less is preferable, and 8 or less is more preferable.
  • the above upper limit and lower limit can be arbitrarily combined, and for example, 1 to 10 are preferred, 2 to 10 are more preferred, and 3 to 8 are even more preferred.
  • the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • epoxy (meth)acrylate resin (b1-1) Specific examples of the epoxy (meth)acrylate resin (b1-1) are given below.
  • the epoxy (meth)acrylate resin (b1) is an epoxy (meth)acrylate resin (b1-2) containing a partial structure represented by the following formula (ii) from the viewpoint of development adhesion. is preferred.
  • each R c independently represents a hydrogen atom or a methyl group.
  • R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. * represents a bond.
  • R d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
  • the cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.
  • the number of rings possessed by the aliphatic ring group is not particularly limited, it is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and still more preferably 3 or less.
  • the above upper limit and lower limit can be combined arbitrarily. When the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • the number of carbon atoms in the aliphatic ring group is preferably 4 or more, more preferably 6 or more, still more preferably 8 or more, preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less.
  • the above upper limit and lower limit can be arbitrarily combined, and for example, 4 to 40 are preferred, 4 to 30 are more preferred, 6 to 20 are even more preferred, and 8 to 15 are particularly preferred.
  • the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved.
  • the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring and adamantane ring.
  • an adamantane ring is preferable from the viewpoint of development adhesion.
  • the number of rings possessed by the aromatic ring group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, preferably 10 or less, more preferably 5 or less, and further preferably 4 or less. .
  • the above upper limit and lower limit can be combined arbitrarily. Residue tends to be reduced by making it equal to or higher than the lower limit. In addition, when the content is equal to or less than the above upper limit, there is a tendency that development adhesion is improved.
  • Aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups.
  • the number of carbon atoms in the aromatic ring group is preferably 4 or more, more preferably 6 or more, still more preferably 8 or more, still more preferably 10 or more, particularly preferably 12 or more, preferably 40 or less, and more preferably 30 or less. , is more preferably 20 or less, and particularly preferably 15 or less.
  • the above upper limit and lower limit can be arbitrarily combined, and for example, 4 to 40 are preferred, 6 to 40 are more preferred, 8 to 30 are more preferred, 10 to 20 are even more preferred, and 12 to 15 are particularly preferred. Residue tends to be reduced by making it equal to or higher than the lower limit. In addition, when the content is equal to or less than the above upper limit, there is a tendency that development adhesion is improved.
  • the aromatic ring in the aromatic ring group includes, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring.
  • a fluorene ring is preferable from the viewpoint of patterning properties.
  • the divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, and examples thereof include a divalent aliphatic group, a divalent aromatic ring group, one or more Examples thereof include groups in which a valent aliphatic group and one or more divalent aromatic ring groups are linked.
  • the divalent aliphatic group includes linear, branched and cyclic aliphatic groups. Among these, straight-chain aliphatic groups are preferable from the viewpoint of development solubility, while cyclic aliphatic groups are preferable from the viewpoint of reducing permeation of the developer into the exposed area.
  • the number of carbon atoms is preferably 1 or more, more preferably 3 or more, still more preferably 6 or more, and preferably 25 or less, more preferably 20 or less, and still more preferably 15 or less.
  • the above upper limit and lower limit can be arbitrarily combined, and for example, 1 to 25 are preferred, 3 to 20 are more preferred, and 6 to 15 are even more preferred.
  • the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • divalent linear aliphatic groups examples include methylene group, ethylene group, n-propylene group, n-butylene group, n-hexylene group and n-heptylene group. Among these, a methylene group is preferable from the viewpoint of residue.
  • the divalent branched aliphatic group includes, for example, the aforementioned divalent straight-chain aliphatic group, and side chains of methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl. structures having a group, a sec-butyl group, and a tert-butyl group.
  • the number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, it is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and still more preferably 3 or less.
  • the above upper limit and lower limit can be combined arbitrarily. When the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • divalent cyclic aliphatic groups include groups obtained by removing two hydrogen atoms from a cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, and adamantane ring.
  • a group obtained by removing two hydrogen atoms from an adamantane ring is preferable from the viewpoint of development adhesion.
  • divalent aliphatic group may have include, for example, alkoxy groups having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; Unsubstituted is preferred from the viewpoint of ease of synthesis.
  • Divalent aromatic ring groups include divalent aromatic hydrocarbon ring groups and divalent aromatic heterocyclic groups.
  • the number of carbon atoms is preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less.
  • the above upper limit and lower limit can be arbitrarily combined, and for example, 4 to 30 are preferred, 5 to 20 are more preferred, and 6 to 15 are even more preferred.
  • the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring.
  • the divalent aromatic hydrocarbon ring group includes, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.
  • the aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a monocyclic ring or a condensed ring.
  • divalent aromatic heterocyclic groups include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, and indole ring having two free valences.
  • substituents that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Among these, unsubstituted is preferred from the viewpoint of curability.
  • one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic ring groups is linked to one or more.
  • the number of divalent aliphatic groups is not particularly limited, it is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
  • the above upper limit and lower limit can be combined arbitrarily. When the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • the number of divalent aromatic ring groups is not particularly limited, it is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
  • the above upper limit and lower limit can be combined arbitrarily. When the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • Examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups represented by the above formulas (iA) to (iF). be done. Among these, the group represented by the above formula (iC) is preferable from the viewpoint of reducing residues.
  • the bonding mode of the cyclic hydrocarbon group, which is a side chain, to these divalent hydrocarbon groups is not particularly limited. and a mode in which a cyclic hydrocarbon group, which is a side chain, is formed by including one of the carbon atoms of the aliphatic group.
  • the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-1) from the viewpoint of development adhesion.
  • R c has the same meaning as in formula (ii) above.
  • R ⁇ represents a monovalent cyclic hydrocarbon group which may have a substituent.
  • n is an integer of 1 or more.
  • the benzene ring in formula (ii-1) may be further substituted with any substituent. * represents a bond.
  • R ⁇ represents a monovalent cyclic hydrocarbon group which may have a substituent.
  • the cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.
  • the number of rings possessed by the aliphatic ring group is not particularly limited, it is preferably 1 or more, more preferably 2 or more, and preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less.
  • the above upper limit and lower limit can be combined arbitrarily. For example, 1 to 6 are preferred, 1 to 4 are more preferred, and 2 to 3 are even more preferred.
  • the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • the number of carbon atoms in the aliphatic ring group is preferably 4 or more, more preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly 15 or less. preferable.
  • the above upper limit and lower limit can be arbitrarily combined, and for example, 4 to 40 are preferred, 4 to 30 are more preferred, 6 to 20 are even more preferred, and 8 to 15 are particularly preferred.
  • the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • Examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring and adamantane ring.
  • an adamantane ring is preferable from the viewpoint of development adhesion.
  • the number of rings possessed by the aromatic ring group is not particularly limited, it is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and preferably 10 or less, more preferably 5 or less.
  • the above upper limit and lower limit can be combined arbitrarily. When the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • Aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups.
  • the number of carbon atoms in the aromatic ring group is preferably 4 or more, more preferably 5 or more, still more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less.
  • the above upper limit and lower limit can be arbitrarily combined, and for example, 4 to 30 are preferred, 5 to 20 are more preferred, and 6 to 15 are even more preferred.
  • the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • aromatic ring in the aromatic ring group examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, and fluorene ring.
  • a fluorene ring is preferable from the viewpoint of development adhesion.
  • Substituents that the cyclic hydrocarbon group may have include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, amyl group, Alkyl groups having 1 to 5 carbon atoms such as isoamyl groups; alkoxy groups having 1 to 5 carbon atoms such as methoxy groups and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; , is preferably unsubstituted.
  • n represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less. For example, 1 to 3 are preferred, and 1 to 2 are more preferred.
  • R ⁇ is preferably a monovalent aliphatic cyclic group, more preferably an adamantyl group, from the viewpoint of strong film hardening degree and electrical properties.
  • the benzene ring in formula (ii-1) may be further substituted with any substituent.
  • substituents include, for example, hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, and propoxy groups.
  • the number of substituents is also not particularly limited, and may be one or two or more. From the viewpoint of curability, non-substitution is preferred.
  • the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-2) from the viewpoint of development adhesion.
  • R c has the same definition as in formula (ii) above.
  • R ⁇ represents a divalent cyclic hydrocarbon group which may have a substituent.
  • the benzene ring in formula (ii-2) may be further substituted with any substituent.
  • * represents a bond.
  • R ⁇ represents a divalent cyclic hydrocarbon group which may have a substituent.
  • the cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.
  • the number of rings possessed by the aliphatic ring group is not particularly limited, it is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less.
  • the above upper limit and lower limit can be combined arbitrarily. When the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • the number of carbon atoms in the aliphatic ring group is preferably 4 or more, more preferably 6 or more, still more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and still more preferably 30 or less.
  • the above upper limit and lower limit can be combined arbitrarily.
  • the aliphatic ring in the aliphatic ring group includes cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring and adamantane ring.
  • an adamantane ring is preferable from the viewpoint of development adhesion.
  • the number of rings possessed by the aromatic ring group is not particularly limited, it is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and preferably 10 or less, and preferably 5 or less.
  • the above upper limit and lower limit can be combined arbitrarily. When the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • Aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups.
  • the number of carbon atoms in the aromatic ring group is preferably 4 or more, more preferably 6 or more, more preferably 8 or more, particularly preferably 10 or more, preferably 40 or less, more preferably 30 or less, and further preferably 20 or less. It is preferred, and 15 or less is particularly preferred.
  • the above upper limit and lower limit can be combined arbitrarily. When the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • aromatic ring in the aromatic ring group examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, and fluorene ring.
  • a fluorene ring is preferable from the viewpoint of development adhesion.
  • Substituents that the cyclic hydrocarbon group may have include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, amyl group, Alkyl groups having 1 to 5 carbon atoms such as isoamyl groups; alkoxy groups having 1 to 5 carbon atoms such as methoxy groups and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; Among these, non-substituted groups are preferred from the viewpoint of ease of synthesis.
  • R ⁇ is preferably a divalent aliphatic cyclic group, more preferably a divalent adamantane cyclic group.
  • R ⁇ is preferably a divalent aromatic ring group, more preferably a divalent fluorene ring group.
  • the benzene ring in formula (ii-2) may be further substituted with any substituent.
  • substituents on the benzene ring in formula (ii-2) include hydroxyl group, methyl group, methoxy group, ethyl group, ethoxy group, propyl group and propoxy group.
  • the number of substituents is also not particularly limited, and may be one or two or more. From the viewpoint of curability, non-substitution is preferred.
  • the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-3).
  • R c and R d have the same definitions as in formula (ii) above.
  • R 1 has the same definition as in formula (i-1) above. * represents a bond.
  • the partial structure represented by the formula (ii-3) contained in one molecule of the epoxy (meth)acrylate resin (b1-2) may be one type or two or more types.
  • the number of partial structures represented by the formula (ii) contained in one molecule of the epoxy (meth)acrylate resin (b1-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and 20 or less is preferred, 15 or less is more preferred, and 10 or less is even more preferred.
  • the above upper limit and lower limit can be combined arbitrarily. When the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • the epoxy (meth)acrylate resin (b1) is an epoxy (meth)acrylate resin (b1-3) containing a partial structure represented by the following general formula (iii) from the viewpoint of easily reducing outgassing. is preferably
  • R e represents a hydrogen atom or a methyl group
  • ⁇ is a single bond, —CO—, an optionally substituted alkylene group, or an optionally substituted divalent represents a cyclic hydrocarbon group.
  • the benzene ring in formula (iii) may be further substituted with any substituent. * represents a bond.
  • ⁇ represents a single bond, —CO—, an optionally substituted alkylene group, or an optionally substituted divalent cyclic hydrocarbon group.
  • the alkylene group may be linear or branched, but is preferably linear from the viewpoint of development solubility, and preferably branched from the viewpoint of development adhesion.
  • the number of carbon atoms is not particularly limited, it is preferably 1 or more, more preferably 2 or more, and preferably 6 or less, and more preferably 4 or less.
  • the above upper limit and lower limit can be arbitrarily combined, and for example, 1 to 6 are preferable, and 2 to 4 are more preferable.
  • the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved.
  • alkylene group examples include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and a heptylene group. is preferred, and a dimethylmethylene group (2,2-propylene group) is more preferred.
  • substituents that the alkylene group may have include alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; From the viewpoint of compatibility with developing solubility, non-substitution is preferred.
  • the divalent cyclic hydrocarbon group includes a divalent aliphatic ring group or a divalent aromatic ring group.
  • the number of rings possessed by the aliphatic ring group is not particularly limited, it is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less.
  • the above upper limit and lower limit can be combined arbitrarily. When the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • the number of carbon atoms in the aliphatic ring group is preferably 4 or more, more preferably 6 or more, still more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and still more preferably 30 or less.
  • the above upper limit and lower limit can be combined arbitrarily.
  • the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring and adamantane ring.
  • an adamantane ring is preferable from the viewpoint of development adhesion.
  • the number of rings possessed by the aromatic ring group is not particularly limited, it is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and preferably 10 or less, more preferably 5 or less.
  • the above upper limit and lower limit can be combined arbitrarily. When the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • Aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups.
  • the number of carbon atoms in the aromatic ring group is preferably 4 or more, more preferably 6 or more, more preferably 8 or more, particularly preferably 10 or more, preferably 40 or less, more preferably 30 or less, and further preferably 20 or less, 15 or less is particularly preferred.
  • the above upper limit and lower limit can be combined arbitrarily. When the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, and fluorene ring. Among these, a fluorene ring is preferable from the viewpoint of development adhesion.
  • Substituents that the cyclic hydrocarbon group may have include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, amyl group, Alkyl groups having 1 to 5 carbon atoms such as isoamyl groups; alkoxy groups having 1 to 5 carbon atoms such as methoxy groups and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; , is preferably unsubstituted.
  • ⁇ is preferably an optionally substituted alkylene group, more preferably dimethylmethylene.
  • the benzene ring in formula (iii) may be further substituted with any substituent.
  • substituents on the benzene ring in formula (iii) include hydroxyl group, methyl group, methoxy group, ethyl group, ethoxy group, propyl group and propoxy group.
  • the number of substituents is also not particularly limited, and may be one or two or more. From the viewpoint of curability, non-substitution is preferred.
  • the partial structure represented by the formula (iii) is preferably a partial structure represented by the following formula (iii-1) from the viewpoint of development solubility.
  • R e and ⁇ have the same definitions as in formula (iii) above.
  • R 1 has the same definition as in formula (i-1) above. * represents a bond.
  • the benzene ring in formula (iii-1) may be further substituted with any substituent.
  • the number of partial structures represented by the formula (iii) contained in one molecule of the epoxy (meth)acrylate resin (b1-3) is not particularly limited, but is preferably 1 or more, more preferably 5 or more, and 10 or more. is more preferred, 18 or less is preferred, and 15 or less is even more preferred.
  • the above upper limit and lower limit can be arbitrarily combined, and for example, 1 to 18 are preferred, 5 to 18 are more preferred, and 10 to 15 are even more preferred.
  • the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • the number of partial structures represented by the formula (iii-1) contained in one molecule of the epoxy (meth)acrylate resin (b1-3) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, 5 or more is more preferable, 18 or less is preferable, and 15 or less is more preferable.
  • the above upper limit and lower limit can be combined arbitrarily, and for example, 1 to 18 are preferred, 3 to 18 are more preferred, and 5 to 15 are even more preferred.
  • the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • epoxy (meth)acrylate resin (b1-3) Specific examples of the epoxy (meth)acrylate resin (b1-3) are given below.
  • the acrylic copolymer resin (b2) preferably has an ethylenic double bond in its side chain.
  • an acrylic copolymer resin (b2-1) containing a partial structure represented by the following general formula (I) is preferable from the viewpoint of developing solubility and liquid repellency.
  • R A and R B each independently represent a hydrogen atom or a methyl group. * represents a bond.
  • the partial structure represented by formula (I) is preferably a partial structure represented by general formula (I-1) below.
  • R A and R B have the same definitions as in formula (I) above.
  • R 1 has the same definition as in formula (i-1) above.
  • the partial structure represented by formula (I) is preferably a partial structure represented by formula (I-2) below.
  • R A and R B have the same definitions as in formula (I) above.
  • the acrylic copolymer resin (b2-1) contains the partial structure represented by the general formula (I)
  • the content of is not particularly limited, it is preferably 5 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, even more preferably 50 mol% or more, particularly preferably 70 mol% or more, and 80 99 mol% or less is preferable, 97 mol% or less is more preferable, and 95 mol% or less is even more preferable.
  • the upper and lower limits can be combined arbitrarily, for example, preferably 5 to 99 mol%, more preferably 20 to 99 mol%, further preferably 30 to 97 mol%, even more preferably 50 to 97 mol%, Particularly preferred is 70-95 mol %, most preferred is 80-95 mol %. Residue tends to be reduced by making it equal to or higher than the lower limit. In addition, when the content is equal to or less than the above upper limit, there is a tendency that development adhesion is improved.
  • the acrylic copolymer resin (b2-1) contains a partial structure represented by the general formula (I-1), the partial structure represented by the general formula (I-1) contained in the acrylic copolymer resin (b2-1)
  • the content of the partial structure is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, still more preferably 8 mol% or more, even more preferably 10 mol% or more, and 99 mol%
  • the following is preferable, 60 mol% or less is more preferable, 40 mol% or less is still more preferable, 30 mol% or less is even more preferable, and 20 mol% or less is particularly preferable.
  • the upper and lower limits can be combined arbitrarily, for example, 1 to 99 mol% is preferable, 1 to 60 mol% is more preferable, 5 to 40 mol% is more preferable, 8 to 30 mol% is even more preferable, 10 to 20 mol % is particularly preferred.
  • the content is equal to or higher than the lower limit, the sensitivity tends to be high and the residue tends to be reduced.
  • the content is equal to or less than the above upper limit, there is a tendency that development adhesion is improved.
  • the acrylic copolymer resin (b2-1) contains a partial structure represented by the general formula (I-2), the partial structure represented by the general formula (I-2) contained in the acrylic copolymer resin (b2-1)
  • the content of the partial structure is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, even more preferably 40 mol% or more, and 50 mol% or more. It is particularly preferably 70 mol% or more, most preferably 99 mol% or less, more preferably 95 mol% or less, even more preferably 90 mol% or less, and particularly preferably 85 mol% or less.
  • the upper and lower limits can be combined arbitrarily, for example, preferably 10 to 99 mol%, more preferably 20 to 99 mol%, further preferably 30 to 95 mol%, even more preferably 40 to 95 mol%, Particularly preferred is 50-90 mol %, most preferred is 70-85 mol %.
  • Sensitivity tends to be increased by making it equal to or higher than the lower limit. Moreover, there exists a tendency for developability to improve by making it below the said upper limit.
  • the acrylic copolymer resin (b2-1) contains a partial structure represented by the general formula (I)
  • the other partial structure that may be contained is not particularly limited, but from the viewpoint of development adhesion, for example, It preferably contains a partial structure represented by the following general formula (I').
  • RD represents a hydrogen atom or a methyl group
  • RE represents an optionally substituted alkyl group, an optionally substituted aryl group (aromatic ring group ), or an optionally substituted alkenyl group.
  • R E is an optionally substituted alkyl group, an optionally substituted aryl group (aromatic ring group), or an optionally substituted represents a good alkenyl group.
  • alkyl group for R E include linear, branched and cyclic alkyl groups.
  • the number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, even more preferably 14 or less, and 12 or less. is particularly preferred.
  • the above upper limit and lower limit can be combined arbitrarily. When the content is at least the above lower limit, the film strength tends to increase and the development adhesion tends to improve. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • alkyl groups examples include methyl, ethyl, cyclohexyl, dicyclopentanyl, and dodecanyl groups. Among these, from the viewpoint of film strength, a dicyclopentanyl group and a dodecanyl group are preferred, and a dicyclopentanyl group is more preferred.
  • Substituents that the alkyl group may have include, for example, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group and carboxy group. , an acryloyl group, and a methacryloyl group, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
  • the aryl group (aromatic ring group) in R E includes a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group.
  • the number of carbon atoms is preferably 6 or more, preferably 24 or less, more preferably 22 or less, still more preferably 20 or less, and particularly preferably 18 or less.
  • 6 to 24 are preferred
  • 6 to 22 are more preferred
  • 6 to 20 are even more preferred
  • 6 to 18 are particularly preferred.
  • the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring.
  • Examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.
  • the aromatic heterocyclic group in the aromatic heterocyclic group may be monocyclic or condensed ring, and examples thereof include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring , benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquino
  • a benzene ring group and a naphthalene ring group are preferred, and a benzene ring group is more preferred.
  • Substituents that the aryl group may have include, for example, methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligo
  • An ethylene glycol group, a phenyl group, and a carboxy group can be mentioned, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
  • Alkenyl groups for R E include linear, branched and cyclic alkenyl groups.
  • the number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, still more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less.
  • 2 to 22 are preferred, 2 to 20 are more preferred, 2 to 18 are even more preferred, 2 to 16 are even more preferred, and 2 to 14 are particularly preferred.
  • the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • alkenyl groups include ethenyl, propenyl, butenyl, and cyclohexenyl groups. Among these, from the viewpoint of curability, an ethenyl group and a propenyl group are preferable, and an ethenyl group is more preferable.
  • Substituents that the alkenyl group may have include, for example, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxy group. , and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
  • R E is preferably an alkyl group or an alkenyl group, more preferably an alkyl group, and even more preferably a dicyclopentanyl group, from the viewpoint of developability.
  • the structure contained in the acrylic copolymer resin (b2-1) is represented by the general formula (I′)
  • the content of the partial structure is not particularly limited, but is preferably 0.5 mol% or more, more preferably 1 mol% or more, still more preferably 1.5 mol% or more, particularly preferably 2 mol% or more, and 90 mol. % or less, more preferably 70 mol % or less, even more preferably 50 mol % or less, even more preferably 30 mol % or less, and particularly preferably 10 mol % or less.
  • the above upper limit and lower limit can be combined arbitrarily, for example, 0.5 to 90 mol% is preferable, 0.5 to 70 mol% is more preferable, 1 to 50% mol is more preferable, 1.5 to 30 mol % is even more preferred, and 2 to 10 mol % is particularly preferred.
  • 0.5 to 90 mol% is preferable
  • 0.5 to 70 mol% is more preferable
  • 1 to 50% mol is more preferable
  • 1.5 to 30 mol % is even more preferred
  • 2 to 10 mol % is particularly preferred.
  • the acrylic copolymer resin (b2-1) contains a partial structure represented by the general formula (I)
  • the partial structure represented by the following general formula (I'') is used from the viewpoint of heat resistance and film strength. It is preferable to further include.
  • R represents a hydrogen atom or a methyl group
  • R represents an optionally substituted alkyl group, an optionally substituted alkenyl group, a hydroxyl group, represents a carboxy group, a halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkylsulfide group which may have a substituent
  • t represents an integer of 0 to 5;
  • R G is an optionally substituted alkyl group, an optionally substituted alkenyl group, a hydroxyl group, a carboxy group, a halogen atom, or a substituted group. represents an optionally substituted alkoxy group, a thiol group, or an optionally substituted alkylsulfide group.
  • Alkyl groups for R G include linear, branched and cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, even more preferably 14 or less, and 12 or less. is particularly preferred.
  • the above upper limit and lower limit can be combined arbitrarily.
  • the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved.
  • a tendency for a residue to reduce by making it below the said upper limit.
  • alkyl groups include methyl, ethyl, cyclohexyl, dicyclopentanyl, and dodecanyl groups.
  • a dicyclopentanyl group and a dodecanyl group are preferable, and a dicyclopentanyl group is more preferable, from the viewpoint of development adhesion.
  • Substituents that the alkyl group may have include, for example, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group and carboxy group.
  • an acryloyl group, and a methacryloyl group and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
  • Alkenyl groups for R G include linear, branched and cyclic alkenyl groups.
  • the number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, still more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less.
  • 2 to 22 are preferred, 2 to 20 are more preferred, 2 to 18 are even more preferred, 2 to 16 are even more preferred, and 2 to 14 are particularly preferred.
  • the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • alkenyl groups include ethenyl, propenyl, butenyl, and cyclohexenyl groups. Among these, from the viewpoint of curability, an ethenyl group and a propenyl group are preferable, and an ethenyl group is more preferable.
  • Substituents that the alkenyl group may have include, for example, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxy group. , and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.
  • the halogen atom in RG includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom is preferable from the viewpoint of ink repellency.
  • the alkoxy group for R G includes linear, branched or cyclic alkoxy groups.
  • the number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less.
  • 1 to 20 are preferred
  • 1 to 18 are more preferred
  • 1 to 16 are even more preferred
  • 1 to 14 are even more preferred
  • 1 to 12 are particularly preferred.
  • Substituents that the alkoxy group may have include, for example, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxy group.
  • an acryloyl group, and a methacryloyl group and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
  • the alkylsulfide group for R G includes linear, branched or cyclic alkylsulfide groups.
  • the number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, and even more preferably 14 or less. , 12 or less.
  • 1 to 20 are preferred, 1 to 18 are more preferred, 1 to 16 are even more preferred, 1 to 14 are even more preferred, and 1 to 12 are particularly preferred.
  • the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • the alkylsulfide group includes, for example, a methylsulfide group, an ethylsulfide group, a propylsulfide group, and a butylsulfide group.
  • a methylsulfide group and an ethylsulfide group are preferable from the viewpoint of developability.
  • substituents that the alkyl group in the alkylsulfide group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl group, carboxyl group, acryloyl group, and methacryloyl group, and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferred.
  • RG is preferably a hydroxy group or a carboxy group, more preferably a carboxy group, from the viewpoint of developability.
  • t represents an integer of 0-5. From the viewpoint of developability, 0 to 2 are preferred, 0 to 1 are more preferred, and 0 is even more preferred.
  • the acrylic copolymer resin (b2-1) contains a partial structure represented by the general formula (I'')
  • the content of the partial structure is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, further preferably 3 mol% or more, particularly preferably 4 mol% or more, and 90 mol% or less. is preferably 70 mol % or less, more preferably 50 mol % or less, even more preferably 30 mol % or less, particularly preferably 20 mol % or less, most preferably 10 mol % or less.
  • the upper limit and the lower limit can be arbitrarily combined, for example, preferably 1 to 90 mol%, more preferably 1 to 70 mol%, further preferably 2 to 50 mol%, even more preferably 2 to 30 mol%, 3 to 20 mol % is particularly preferred, and 4 to 10 mol % is most preferred.
  • the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • the acrylic copolymer resin (b2-1) contains a partial structure represented by the general formula (I), it further contains a partial structure represented by the following general formula (I''') from the viewpoint of developability. is preferred.
  • R H represents a hydrogen atom or a methyl group.
  • the acrylic copolymer resin (b2-1) contains a partial structure represented by the general formula (I'''), the general formula (I''') contained in the acrylic copolymer resin (b2-1)
  • the content of the partial structure represented by is not particularly limited, it is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 30 mol% or more, and preferably 90 mol% or less, and 80 mol%.
  • the following is more preferable, 70 mol% or less is more preferable, and 50 mol% or less is particularly preferable.
  • the above upper limit and lower limit can be combined arbitrarily. Residue tends to be reduced by making it equal to or higher than the lower limit. In addition, when the content is equal to or less than the above upper limit, there is a tendency that development adhesion is improved.
  • the acid value of the acrylic copolymer resin (b2) is not particularly limited, but is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, still more preferably 20 mgKOH/g or more, even more preferably 25 mgKOH/g or more, and It is preferably 100 mgKOH/g or less, more preferably 80 mgKOH/g or less, still more preferably 60 mgKOH/g or less, and even more preferably 40 mgKOH/g or less.
  • the above upper limit and lower limit can be arbitrarily combined, for example, 5 to 100 mgKOH/g is preferable, 10 to 80 mgKOH/g is more preferable, 20 to 60 mgKOH/g is more preferable, and 25 to 40 mgKOH/g is even more preferable. Residue tends to be reduced by making it equal to or higher than the lower limit. In addition, when the content is equal to or less than the above upper limit, there is a tendency that development adhesion is improved.
  • the weight average molecular weight (Mw) of the acrylic copolymer resin (b2) is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, still more preferably 3000 or more, even more preferably 4000 or more, and particularly preferably 5000 or more. Also, it is preferably 30,000 or less, more preferably 20,000 or less, even more preferably 15,000 or less, and even more preferably 10,000 or less. Especially preferably, it is 8000 or less.
  • the above upper limit and lower limit can be arbitrarily combined, for example, 1000 to 30000 is preferable, 2000 to 20000 is more preferable, 3000 to 15000 is more preferable, 4000 to 10000 is even more preferable, and 5000 to 8000 is particularly preferable. When the content is equal to or higher than the above lower limit, there is a tendency that development adhesion is improved. Moreover, there exists a tendency for a residue to reduce by making it below the said upper limit.
  • the (B) alkali-soluble resin may contain either one of the epoxy (meth)acrylate resin (b1) and the acrylic copolymer resin (b2) alone, or both of them. Furthermore, the alkali-soluble resin (B) may contain an alkali-soluble resin other than the alkali-soluble resin (b). Examples thereof include resins described in International Publication No. 2016/194619 and International Publication No. 2017/154439.
  • the content of (B) the alkali-soluble resin in the photosensitive resin composition of the present invention is preferably 5% by mass or more, more preferably 10% by mass, based on the total solid content (100% by mass) of the photosensitive resin composition. More preferably 20% by mass or more, still more preferably 30% by mass or more, particularly preferably 40% by mass or more, more preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass It is below.
  • the above upper limit and lower limit can be arbitrarily combined, for example, 5 to 90% by mass is preferable, 10 to 90% by mass is more preferable, 20 to 80% by mass is more preferable, and 30 to 70% by mass is even more preferable.
  • Developability tends to be improved by setting the content to be at least the above lower limit. Moreover, there exists a tendency which tends to secure high liquid repellency by making it below the said upper limit.
  • the content of the epoxy (meth)acrylate resin (b1) is not particularly limited. (100% by mass), preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, even more preferably 20% by mass or more, particularly preferably 25% by mass or more, and also preferably is 90% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, and particularly preferably 50% by mass or less.
  • the upper limit and the lower limit can be arbitrarily combined, for example, 5 to 90% by mass is preferable, 10 to 90% by mass is more preferable, 10 to 70% by mass is more preferable, 15 to 60% by mass is even more preferable, 20 to 50% by weight is particularly preferred.
  • the content is equal to or higher than the above lower limit, the developability tends to be improved, and the shape of the lower portion of the partition wall tends to be improved. Further, when the content is equal to or less than the above upper limit, there is a tendency that the liquid repellency is improved.
  • the content of the acrylic copolymer resin (b2) is not particularly limited, but the total solid content of the photosensitive resin composition (100 mass %), preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, even more preferably 30% by mass or more, particularly preferably 40% by mass or more, and preferably 90% by mass. % by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.
  • the above upper limit and lower limit can be arbitrarily combined, for example, 5 to 90% by mass is preferable, 10 to 90% by mass is more preferable, 20 to 80% by mass is more preferable, and 30 to 70% by mass is even more preferable.
  • the content is at least the lower limit, the developability tends to be improved and the liquid repellency tends to be improved.
  • the shape of the lower part of the partition wall tends to be improved by making it equal to or less than the above upper limit.
  • the content of the epoxy (meth)acrylate resin (b1) relative to the (B) alkali-soluble resin (100% by mass) is not particularly limited, 10% by mass or more is preferable, 20% by mass or more is more preferable, 30% by mass or more is still more preferable, and 35% by mass or more is even more preferable. Also, it is preferably 90% by mass or less, more preferably 70% by mass or less, and even more preferably 50% by mass or less.
  • the upper limit and the lower limit can be arbitrarily combined, for example, 10 to 90% by mass is preferable, 20 to 90% by mass is more preferable, 20 to 70% by mass is more preferable, 20 to 50% by mass is even more preferable, 30 to 50% by weight is particularly preferred.
  • 10 to 90% by mass is preferable
  • 20 to 90% by mass is more preferable
  • 20 to 70% by mass is more preferable
  • 20 to 50% by mass is even more preferable
  • 30 to 50% by weight is particularly preferred.
  • the content of the acrylic copolymer resin (b2) with respect to the (B) alkali-soluble resin (100% by mass) is not particularly limited, but is 20% by mass or more. is preferred, 40% by mass or more is more preferred, 50% by mass or more is even more preferred, and 60% by mass or more is even more preferred. Moreover, it is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.
  • the upper limit and the lower limit can be arbitrarily combined, for example, 20 to 90% by mass is preferable, 40 to 90% by mass is more preferable, 40 to 80% by mass is more preferable, 50 to 80% by mass is even more preferable, 50 to 70% by weight is particularly preferred.
  • 20 to 90% by mass is preferable
  • 40 to 90% by mass is more preferable
  • 40 to 80% by mass is more preferable
  • 50 to 80% by mass is even more preferable
  • 50 to 70% by weight is particularly preferred.
  • the total content of (B) the alkali-soluble resin and (C) the photopolymerizable compound in the total solid content (100% by mass) of the photosensitive resin composition is preferably 5% by mass or more, more preferably 10% by mass. % by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, particularly preferably 70% by mass or more, even more preferably 80% by mass or more, most preferably 90% by mass or more, Also, it is preferably 99% by mass or less, more preferably 97% by mass or less, and even more preferably 95% by mass or less.
  • the upper limit and lower limit can be combined arbitrarily, for example, 5 to 99% by mass is preferable, 10 to 99% by mass is more preferable, 30 to 99% by mass is more preferable, 50 to 97% by mass is even more preferable, 70 to 97% by weight is particularly preferred, 80 to 95% by weight is particularly preferred, and 90 to 95% by weight is most preferred.
  • Curability and liquid repellency tend to be improved by adjusting the content to be at least the above lower limit.
  • the amount of the coloring agent can be increased, thereby tending to improve the light-shielding property.
  • the mixing ratio of the (B) alkali-soluble resin to the (C) photopolymerizable compound in the photosensitive resin composition is preferably 50 parts by mass or more, and 60 parts by mass with respect to 100 parts by mass of the (C) photopolymerizable compound. 70 parts by mass or more is more preferred, 80 parts by mass or more is particularly preferred, 500 parts by mass or less is preferred, 400 parts by mass or less is more preferred, and 300 parts by mass or less is even more preferred. All upper and lower limits can be combined arbitrarily, and for example, 50 to 400 parts by mass is preferable, and 60 to 300 parts by mass is more preferable.
  • the tapered shape tends to be high when the thickness is equal to or higher than the lower limit. Further, when the content is set to the above upper limit or less, curability and liquid repellency tend to be improved.
  • (C) Photopolymerizable Compound The photosensitive resin composition of the present invention contains (C) a photopolymerizable compound. (C) It is considered that the inclusion of the photopolymerizable compound results in high sensitivity.
  • the photopolymerizable compound is a component different from the (A) copolymer, and when there is a photopolymerizable compound corresponding to (A) the copolymer, (A) the copolymer treated as a combination.
  • the (C) photopolymerizable compound used here means a compound having one or more ethylenically unsaturated bonds (ethylenic double bonds) in the molecule, but polymerizability, crosslinkability, and accompanying
  • a compound having two or more ethylenically unsaturated bonds in the molecule is preferable from the viewpoint of increasing the difference in developer solubility between the exposed area and the non-exposed area.
  • the unsaturated bond is more preferably derived from a (meth)acryloyloxy group, that is, a (meth)acrylate compound.
  • the photosensitive resin composition of the present invention it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated bonds in one molecule.
  • the number of ethylenically unsaturated groups possessed by the polyfunctional ethylenic monomer is not particularly limited, but is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and particularly preferably 5 or more. , and preferably 15 or less, more preferably 10 or less, still more preferably 8 or less, and particularly preferably 7 or less.
  • the above upper limit and lower limit can be combined arbitrarily. When the content is at least the above lower limit, the polymerizability tends to be improved and the sensitivity tends to be high.
  • the photopolymerizable compound includes, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; an aliphatic polyhydroxy compound, an aromatic polyhydroxy an ester obtained by an esterification reaction between a polyhydric hydroxy compound such as a compound and an unsaturated carboxylic acid or a polybasic carboxylic acid;
  • esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol ethane triacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate.
  • pentaerythritol tetraacrylate dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, and other aliphatic polyhydroxy compounds
  • esters itaconate esters in which itaconates are substituted for acrylates of these compounds
  • maleates in which maleates are substituted for acrylates in these compounds.
  • Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters and methacryl esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. acid esters.
  • the ester obtained by the esterification reaction of a polyhydric hydroxy compound such as an aliphatic polyhydroxy compound or an aromatic polyhydroxy compound with an unsaturated carboxylic acid or a polybasic carboxylic acid is not necessarily a single substance, but for example , acrylic acid, phthalic acid and ethylene glycol; acrylic acid, maleic acid and diethylene glycol; methacrylic acid, terephthalic acid and pentaerythritol; acrylic acid, adipic acid, butanediol and glycerol. things;
  • Examples of the (C) photopolymerizable compound used in the photosensitive resin composition of the present invention other than the above include, for example, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylic acid ester or a polyisocyanate compound and a polyol and a hydroxyl group-containing ( Urethane (meth)acrylates such as those obtained by reacting meth)acrylic acid esters; Epoxy acrylates such as addition reaction products of polyepoxy compounds and hydroxyl group-containing (meth)acrylic acid esters or (meth)acrylic acid acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate.
  • Urethane (meth)acrylates such as those obtained by reacting meth)acrylic acid esters
  • Epoxy acrylates such as addition reaction products of polyepoxy compounds and hydroxyl group-containing (meth)acrylic acid esters or (me
  • Urethane (meth)acrylates include, for example, DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U- 10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).
  • the molecular weight of the photopolymerizable compound (C) is not particularly limited, but is preferably 100 or more, more preferably 150 or more, and It is preferably 200 or more, more preferably 300 or more, particularly preferably 400 or more, most preferably 500 or more, and preferably 1000 or less, more preferably 700 or less.
  • the upper limit and the lower limit can be arbitrarily combined, for example, 100 to 1000 is preferable, 150 to 1000 is more preferable, 200 to 1000 is more preferable, 300 to 700 is even more preferable, 400 to 700 is particularly preferable, 500 ⁇ 700 is most preferred.
  • the number of carbon atoms in the photopolymerizable compound is not particularly limited, but from the viewpoint of sensitivity, ink repellency, and taper angle, it is preferably 7 or more, more preferably 10 or more, still more preferably 15 or more, and still more preferably 20. As mentioned above, it is particularly preferably 25 or more, preferably 50 or less, more preferably 40 or less, still more preferably 35 or less, and particularly preferably 30 or less. The above upper limit and lower limit can be combined arbitrarily.
  • esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids epoxy (meth)acrylates, and urethane (meth)acrylates are preferred.
  • the content of (C) the photopolymerizable compound in the photosensitive resin composition of the present invention is preferably 5% by mass or more, more preferably 10% by mass in the total solid content (100% by mass) of the photosensitive resin composition. More preferably 20% by mass or more, still more preferably 30% by mass or more, particularly preferably 40% by mass or more, more preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass Below, more preferably 55% by mass or less, particularly preferably 50% by mass or less.
  • the above upper limit and lower limit can be arbitrarily combined, for example, 5 to 80% by mass is preferable, 10 to 70% by mass is more preferable, 20 to 60% by mass is more preferable, and 30 to 55% by mass or more is even more preferable. , 40 to 50% by weight are particularly preferred.
  • the content is at least the above lower limit, there is a tendency for appropriate internal curability. Developability tends to be improved by adjusting the content to be equal to or less than the above upper limit.
  • the photosensitive resin composition of the present invention may further contain (D) a photopolymerization initiator in addition to (A) the copolymer.
  • the photopolymerization initiator is not particularly limited as long as it is a compound that polymerizes the (C) photopolymerizable compound by actinic rays, for example, polymerizes the ethylenically unsaturated bond of the (C) photopolymerizable compound.
  • a photopolymerization initiator commonly used in this field can be used as (D) the photopolymerization initiator.
  • photopolymerization initiators include metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197; JP-A-2000-56118. Hexaarylbiimidazole derivatives described in JP-A-10-39503; halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, and N-aryl- ⁇ such as N-phenylglycine described in JP-A-10-39503.
  • radical activators such as amino acids, N-aryl- ⁇ -amino acid salts, N-aryl- ⁇ -amino acid esters, ⁇ -aminoalkylphenone derivatives; Examples thereof include oxime ester compounds described in JP-A No. 2006-36750.
  • metallocene compounds include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis(2,3,4,5,6-pentafluorophenyl ), dicyclopentadienyl titanium bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyl titanium bis(2,4,6-trifluorophenyl), dicyclopentadienyl titanium di( 2,6-difluorophenyl), dicyclopentadienyl titanium di(2,4-difluorophenyl), di(methylcyclopentadienyl) titanium bis(2,3,4,5,6-pentafluorophenyl), Di(methylcyclopentadienyl) titanium bis(2,6-difluorophenyl), dicyclopentadienyl titanium [2,6-di-fluoro-3-(pyro-1-y
  • Biimidazole derivatives include, for example, 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole dimer, 2-(2′-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2′-methoxyphenyl)-4,5-diphenylimidazole dimer, (4′-methoxyphenyl )-4,5-diphenylimidazole dimer.
  • halomethylated oxadiazole derivatives examples include 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[ ⁇ -(2'- benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[ ⁇ -(2′-(6′′-benzofuryl)vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.
  • halomethyl-s-triazine derivatives examples include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis( trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl) -s-triazines.
  • Examples of ⁇ -aminoalkylphenone derivatives include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4 -morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one, 3,6-bis(2-methyl- 2-morpholinopropionyl)-9-octylcarbazole.
  • an oxime ester compound is particularly effective in terms of sensitivity and plate-making properties.
  • such oxime ester compounds with excellent sensitivity are useful.
  • the oxime ester compound has a high quantum yield of photoreaction and high activity of the generated radical, so that it has high sensitivity and is stable against thermal reaction, and a small amount of the photosensitive resin composition has high sensitivity. It is possible to obtain
  • oxime ester compounds include compounds represented by the following general formula (IV).
  • R 21a represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aromatic ring group.
  • R 21b represents any substituent containing an aromatic ring.
  • R 22a represents an optionally substituted alkanoyl group or an optionally substituted aroyl group.
  • n represents an integer of 0 or 1;
  • the number of carbon atoms in the alkyl group in R 21a is not particularly limited, it is preferably 1 or more, more preferably 2 or more, and preferably 20 or less, more preferably 20 or less, from the viewpoint of solubility in solvents, sensitivity, and inkjet applicability. It is 15 or less, more preferably 10 or less.
  • alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl and cyclohexylethyl groups.
  • alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, 4-(2-methoxy-1-methyl)ethoxy-2- Examples include a methylphenyl group and an N-acetyl-N-acetoxyamino group. From the viewpoint of ease of synthesis, the alkyl group is preferably unsubstituted.
  • the aromatic ring group for R 21a includes aromatic hydrocarbon ring groups and aromatic heterocyclic groups.
  • the number of carbon atoms in the aromatic ring group is not particularly limited, it is preferably 5 or more from the viewpoint of solubility in the photosensitive resin composition. From the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and even more preferably 12 or less. For example, 5-30 is preferred, 5-20 is more preferred, and 5-12 is even more preferred.
  • aromatic ring group examples include, for example, a phenyl group, a naphthyl group, a pyridyl group, and a furyl group.
  • substituent that the aromatic ring group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, and groups in which these substituents are linked. From the viewpoint of developability, an alkyl group, an alkoxy group, or a group in which these are linked is preferable, and a linked alkoxy group is more preferable.
  • R 21a is preferably an optionally substituted alkyl group.
  • R 21b is preferably an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, an optionally substituted diphenyl sulfide group, an optionally substituted fluorenyl group or an optionally substituted An indolyl group can be mentioned. Among these, an optionally substituted diphenyl sulfide group is preferred from the viewpoint of ink jet applicability.
  • the number of carbon atoms in the alkanoyl group in R 22a is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is preferably 2 or more, more preferably 20 or less, more preferably 15 or less, still more preferably 10 or less, and more preferably 10 or less. More preferably, it is 5 or less.
  • alkanoyl groups include acetyl, ethyloyl, propanoyl and butanoyl groups.
  • substituents that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, and an amide group. From the viewpoint of ease of synthesis, the alkanoyl group is preferably unsubstituted.
  • the number of carbon atoms in the aroyl group in R 22a is not particularly limited, it is preferably 7 or more, preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less from the viewpoint of solvent solubility and sensitivity.
  • Specific examples of the aroyl group include, for example, a benzoyl group and a naphthoyl group.
  • substituents that the aroyl group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, and an alkyl group. From the viewpoint of ease of synthesis, the aroyl group is preferably unsubstituted.
  • R 22a is preferably an optionally substituted alkanoyl group, more preferably an unsubstituted alkanoyl group, and even more preferably an acetyl group.
  • the photopolymerization initiator may be used singly or in combination of two or more.
  • the photopolymerization initiator (D) may optionally be blended with a sensitizing dye and a polymerization accelerator corresponding to the wavelength of the image exposure light source for the purpose of increasing sensitivity.
  • sensitizing dyes examples include the xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, JP-A-3-239703 and JP-A-5-289335. JP-A-3-239703, 3-ketocoumarin compounds described in JP-A-5-289335, and JP-A-6-19240.
  • amino group-containing sensitizing dyes are preferred, and compounds having an amino group and a phenyl group in the same molecule are more preferred.
  • 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 3,4-diamino Benzophenone compounds such as benzophenone; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2- (p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)-1,3,
  • polymerization accelerators examples include aromatic amines such as ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone, and 4-dimethylaminopropiophenone, and n-butylamine. , N-methyldiethanolamine, and 2-dimethylaminoethyl benzoate can be used.
  • the polymerization accelerator may be used alone or in combination of two or more.
  • the content of (D) the photopolymerization initiator is not particularly limited, but the total solid content of the photosensitive resin composition (100% by mass ), preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 1% by mass or more, even more preferably 2% by mass or more, particularly preferably 3% by mass or more, In addition, it is preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, even more preferably 10% by mass or less, particularly preferably 7% by mass or less, and most preferably 5% by mass or less. be.
  • the above upper and lower limits can be combined arbitrarily.
  • ink repellency tends to be improved by making it equal to or higher than the above lower limit. Residue tends to be reduced by adjusting the content to the above upper limit or less.
  • the mixing ratio of (D) the photopolymerization initiator to the (C) photopolymerizable compound in the photosensitive resin composition is C) with respect to 100 parts by mass of the photopolymerizable compound, preferably 1 part by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, and 20 parts by mass or more Particularly preferred is 200 parts by mass or less, more preferably 100 parts by mass or less, even more preferably 50 parts by mass or less, and particularly preferably 30 parts by mass or less.
  • the above upper and lower limits can be combined arbitrarily.
  • the ink repellency tends to be improved by making it equal to or higher than the lower limit.
  • a residue tends to be reduced by making it below the said upper limit.
  • the photosensitive resin composition of the present invention may contain (E) a colorant for the purpose of coloring the partition walls.
  • a coloring agent known coloring agents such as pigments and dyes can be used.
  • the type of (E) colorant used in the present invention is not particularly limited, and a pigment or a dye may be used. Among these, pigments are preferably used from the viewpoint of durability.
  • the pigment contained in the colorant may be of one type or two or more types. In particular, from the viewpoint of uniform light blocking in the visible region, two or more types are preferable.
  • the type of pigment that can be used as the colorant is not particularly limited, but examples thereof include organic pigments and inorganic pigments. Among these, it is preferable to use an organic pigment from the viewpoint of controlling the transmission wavelength of the photosensitive resin composition for efficient curing.
  • Organic pigments include organic coloring pigments and organic black pigments.
  • the organic coloring pigment means an organic pigment exhibiting a color other than black, and includes red pigment, orange pigment, blue pigment, purple pigment, green pigment, yellow pigment, and the like.
  • organic pigments it is preferable to use an organic coloring pigment from the viewpoint of ultraviolet absorption.
  • An organic coloring pigment may be used individually by 1 type, and may use 2 or more types together.
  • organic pigments are not particularly limited, but examples include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, and perylene-based pigments. Specific examples of pigments that can be used are shown below by pigment numbers. In the following, terms such as "C.I. Pigment Red 2" refer to the Color Index (C.I.).
  • C.I. I. Pigment Red 48 1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment Red 177, 209, 224, 254 may be mentioned.
  • C.I. I. Pigment Red 177, 254, and 272 are preferably used, and when the photosensitive resin composition is cured with ultraviolet rays, it is preferable to use a red pigment having a low ultraviolet absorption rate.
  • I. Pigment Red 254, 272 is more preferably used.
  • C.I. I. Pigment Orange 1 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 can be mentioned.
  • C.I. I. Pigment Orange 13, 43, 64, 72 is preferably used, and when the photosensitive resin composition is cured with ultraviolet rays, it is preferable to use an orange pigment having a low ultraviolet absorption rate.
  • C. I. More preferably, Pigment Orange 64, 72 is used.
  • C.I. I. Pigment Blue 1 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 can be mentioned.
  • C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 60 more preferably C.I. I. Pigment Blue 15:6 may be mentioned.
  • C.I. I. Pigment Blue 15:6, 16, 60 is preferably used, and when the photosensitive resin composition is cured with ultraviolet rays, it is preferable to use a blue pigment having a low ultraviolet absorption rate.
  • C. I. Pigment Blue 60 is more preferably used.
  • C.I. I. Pigment Violet 1 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 can be mentioned.
  • C.I. I. Pigment Violet 19, 23, more preferably C.I. I. Pigment Violet 23 may be mentioned.
  • C.I. I. Pigment Violet 23 and 29 are preferably used, and when the photosensitive resin composition is cured with ultraviolet rays, it is preferable to use a purple pigment having a low ultraviolet absorption rate.
  • I. Pigment Violet 29 is more preferably used.
  • organic coloring pigments examples include green pigments and yellow pigments.
  • green pigment C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 can be mentioned.
  • C.I. I. Pigment Green 7, 36 can be mentioned.
  • yellow pigment C.I. I.
  • C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, 180 can be mentioned.
  • At least one pigment selected from the group consisting of red pigments, orange pigments, blue pigments, and violet pigments from the viewpoint of light shielding properties and ink repellency.
  • Red pigment C.I. I. Pigment Red 177, 254, 272
  • Orange pigment C.I. I. Pigment Orange 43, 64, 72
  • Blue pigment C.I. I. pigment blue 15:6,60 Purple pigment: C.I. I. Pigment Violet 23, 29
  • organic black pigments include aniline black, perylene black, and organic black pigments represented by the following general formula (2). Among these, organic black pigments represented by the following general formula (2) are more preferable from the viewpoint of light shielding properties and dispersibility.
  • Inorganic pigments can also be used.
  • inorganic black pigments include carbon black, acetylene black, lamp black, bone black, graphite, iron black, cyanine black and titanium black.
  • carbon black can be preferably used from the viewpoint of light shielding properties and dispersibility.
  • white pigments include titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, and aluminum silicate. is mentioned. Among these, titanium oxide is preferable from the viewpoint of scattering properties.
  • a known dispersant or dispersing aid may be used in combination so that the pigment can stably exist in the photosensitive resin composition without aggregating.
  • the content of the (E) coloring agent is the total solid content of the photosensitive resin composition (100 % by mass), preferably 60% by mass or less, more preferably 40% by mass or less.
  • the lower limit is not particularly limited, it is preferably 0.01% by mass or more.
  • 0.01 to 60% by mass is preferable, and 0.01 to 40% by mass is more preferable.
  • the photosensitive resin composition contains (E) a coloring agent, the curability of the partition walls is lowered, the liquid repellency of the partition walls is lowered, and outgassing tends to occur easily.
  • the content of the (E) colorant in the photosensitive resin composition is low, for example, it is preferably 20% by mass or less, more preferably 10% by mass or less, relative to the total solid content of the photosensitive resin composition. .
  • 0.01 to 20% by mass is preferable, and 0.01 to 10% by mass is more preferable.
  • the photosensitive resin composition of the present invention may contain (F) a chain transfer agent.
  • a chain transfer agent By including (F) a chain transfer agent, radical deactivation due to oxygen inhibition or the like in the vicinity of the surface can be improved, surface curability can be improved, and the taper angle tends to increase.
  • by increasing the surface curability it is possible to suppress the outflow of (A) the copolymer and/or the liquid repellent agent, and (A) the copolymer and/or the liquid repellent agent can be easily fixed near the surface of the partition wall and the contact angle is high.
  • chain transfer agent (F) examples include mercapto group-containing compounds and carbon tetrachloride, and mercapto group-containing compounds are more preferable because they tend to have a high chain transfer effect.
  • a mercapto group-containing compound has a small SH bond energy, so bond cleavage is likely to occur, and chain transfer reaction is likely to occur, so there is a tendency that surface curability can be enhanced.
  • aromatic ring-containing mercapto group-containing compounds and aliphatic mercapto group-containing compounds are preferable from the viewpoint of taper angle and surface curability.
  • aliphatic mercapto group-containing compounds include butanediol bis(3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol bis(3-mercaptopropionate), and ethylene glycol bisthioglycolate.
  • trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tristhioglycolate, trishydroxyethyl tristhiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercapto propionate), butanediol bis(3-mercaptobutyrate), ethylene glycol bis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), Pentaerythritol tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione mentioned.
  • trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyric rate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2 ,4,6(1H,3H,5H)-trione is preferred, and pentaerythritol tetrakis(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptobutyrate) are more preferred.
  • 2-mercaptobenzothiazole 2-mercaptobenzimidazole
  • 2-mercaptobenzoxazole 2-mercaptobenzoxazole
  • 2-mercaptobenzothiazole 2-mercaptobenzimidazole
  • 2-mercaptobenzoxazole 2-mercaptobenzoxazole
  • 2-mercaptobenzothiazole 2-mercaptobenzimidazole
  • 2-mercaptobenzothiazole and 2-mercaptobenzimidazole may be used in combination.
  • pentaerythritol tetrakis(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptobutyrate) are preferred from the viewpoint of surface curability.
  • the content is not particularly limited, but the total solid content (100% by mass) of the photosensitive resin composition is preferably 0.01 % by mass or more, more preferably 0.025% by mass or more, still more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, particularly preferably 1% by mass or more, and preferably 5% by mass or more. % by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.
  • the upper and lower limits can be combined arbitrarily, for example, preferably 0.01 to 5% by mass, more preferably 0.025 to 5% by mass, further preferably 0.05 to 4% by mass, 0.1 to 4% by mass is even more preferred, and 1 to 3% by mass is particularly preferred.
  • the content is at least the lower limit, the surface curability tends to increase, and the liquid repellency tends to increase. Moreover, there exists a tendency which becomes easy to form a desired pattern by making it below the said upper limit.
  • the content thereof is 100 parts by mass of the mercapto group-containing compound having an aromatic ring.
  • the aliphatic mercapto group-containing compound is preferably 10 parts by mass or more, more preferably 50 parts by mass or more, still more preferably 80 parts by mass or more, and preferably 400 parts by mass or less, more preferably 300 parts by mass. It is 150 parts by mass or less, preferably 200 parts by mass or less, and more preferably 150 parts by mass or less.
  • the above upper limit and lower limit can be combined arbitrarily.
  • 10 to 400 parts by mass is preferable, 10 to 300 parts by mass is more preferable, 50 to 200 parts by mass is more preferable, and 80 to 150 parts by mass is particularly preferable.
  • the ink repellency tends to be enhanced by making it equal to or higher than the lower limit.
  • the sensitivity tends to be increased by making it equal to or less than the above upper limit.
  • the photosensitive resin composition of the present invention contains (F) a chain transfer agent and (D) a photopolymerization initiator
  • (F) the chain transfer agent is added to the (D) photopolymerization initiator in the photosensitive resin composition.
  • the ratio is preferably 1 part by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, particularly preferably 20 parts by mass or more, relative to 100 parts by mass of the photopolymerization initiator (D).
  • the upper and lower limits can be combined arbitrarily, for example, preferably 10 to 500 parts by mass, more preferably 10 to 400 parts by mass, more preferably 20 to 300 parts by mass, and even more preferably 20 to 200 parts by mass, 20 to 150 parts by weight is particularly preferred.
  • the content is at least the lower limit, the surface curability tends to increase, and the liquid repellency tends to increase. Moreover, there exists a tendency which becomes easy to form a desired pattern by making it below the said upper limit.
  • the photosensitive resin composition of the present invention may further contain (G) a liquid repellent agent in addition to (A) the copolymer.
  • a liquid repellent agent a fluorine atom-containing resin having a cross-linking group is preferable. Including a fluorine atom-containing resin having a cross-linking group makes it possible to impart ink repellency to the surface of the obtained partition wall, and thus it is thought that the obtained partition wall can prevent color mixture for each pixel.
  • the cross-linking group examples include an epoxy group and an ethylenically unsaturated group, and an ethylenically unsaturated group is preferable from the viewpoint of suppressing the outflow of the liquid repellent agent to the developer.
  • a liquid-repellent agent having a cross-linking group By using a liquid-repellent agent having a cross-linking group, the cross-linking reaction on the surface of the formed coating film can be accelerated when the coating film is exposed to light, and the liquid-repellent agent is less likely to flow out during the development process. can exhibit high ink repellency.
  • the (G) liquid-repellent agent which is a fluorine atom-containing resin, tends to be oriented on the surface of the partition walls and work to prevent ink bleeding and color mixing. More specifically, groups containing fluorine atoms tend to repel ink and prevent ink bleeding and color mixing due to ink crossing the partition walls and entering adjacent regions.
  • the fluorine atom-containing resin having a cross-linking group preferably has either one or both of a perfluoroalkyl group and a perfluoroalkylene ether chain. Having one or both of a perfluoroalkyl group and a perfluoroalkylene ether chain makes it easier for the fluorine atom-containing resin to be oriented on the surface of the partition wall, exhibits higher ink repellency, and prevents ink bleeding and color mixing. It tends to prevent more.
  • perfluoroalkyl groups include perfluorobutyl, perfluorohexyl, and perfluorooctyl groups.
  • perfluoroalkylene ether chains include -CF 2 -O-, -(CF 2 ) 2 -O-, -(CF 2 ) 3 -O-, -CF 2 -C(CF 3 )O-, - Examples thereof include C(CF 3 )--CF 2 --O-- and divalent groups having repeating units thereof.
  • fluorine atom-containing resin having a cross-linking group examples include, for example, an acrylic copolymer resin having an epoxy group and a perfluoroalkyl group, an acrylic copolymer resin having an epoxy group and a perfluoroalkylene ether chain, and an ethylenically unsaturated group.
  • an acrylic copolymer resin having a perfluoroalkyl group an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkylene ether chain, an epoxy group and an epoxy (meth) acrylate resin having a perfluoroalkyl group, an epoxy group and a per Epoxy (meth)acrylate resin having fluoroalkylene ether chain, Epoxy (meth)acrylate resin having ethylenically unsaturated group and perfluoroalkyl group, Epoxy (meth)acrylate having ethylenically unsaturated group and perfluoroalkylene ether chain resin.
  • acrylic copolymer resins having an ethylenically unsaturated group and a perfluoroalkyl group and acrylic copolymer resins having an ethylenically unsaturated group and a perfluoroalkylene ether chain are preferable from the viewpoint of ink repellency.
  • Acrylic copolymer resins having unsaturated groups and perfluoroalkylene ether chains are more preferred.
  • fluorine atom-containing resins having these crosslinking groups include DIC's "Megafac (registered trademark, hereinafter the same.) F116", “Megafac F120", “Megafac F142D”, and “Megafac F144D”.
  • “Megaface RS-72-K”, “Megaface RS-78” and “Megaface RS-90” are preferably used as acrylic copolymer resins having an ethylenically unsaturated group and a perfluoroalkylene group. can be used.
  • the content of fluorine atoms in the fluorine atom-containing resin having a cross-linking group is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more in the fluorine atom-containing resin (100% by mass) having a cross-linking group. % by mass or more is more preferable, and 25% by mass or more is even more preferable. Moreover, 50 mass % or less is preferable and 35 mass % or less is more preferable. The above upper and lower limits can be combined arbitrarily. For example, 5 to 50% by mass is preferable, 10 to 50% by mass is more preferable, 20 to 35% by mass is even more preferable, and 25 to 35% by mass is particularly preferable. When the content is equal to or greater than the lower limit value, there is a tendency that outflow to the pixel portion can be suppressed. When the content is equal to or less than the above upper limit, there is a tendency to exhibit a high contact angle.
  • the molecular weight of the fluorine atom-containing resin having a cross-linking group is not particularly limited, and it may be a low-molecular-weight compound or a high-molecular-weight compound.
  • a high-molecular-weight material is preferable because it suppresses fluidity due to post-baking and suppresses outflow from the partition wall.
  • the number average molecular weight of the fluorine atom-containing resin having a cross-linking group is preferably 100 or more, more preferably 500 or more, and preferably 100000 or less, and 10000 or less. more preferred.
  • the above upper and lower limits can be combined arbitrarily. For example, 100 to 100,000 is preferable, and 500 to 10,000 is more preferable.
  • the content of (G) liquid repellent agent in the photosensitive resin composition of the present invention is not particularly limited, but the total solid of the photosensitive resin composition content (100% by mass) is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, and preferably 5% by mass or less, more preferably is 3% by mass or less, more preferably 2% by mass or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 0.01 to 5% by mass is preferable, 0.1 to 3% by mass is more preferable, and 0.5 to 2% by mass is even more preferable.
  • the ink repellency tends to be improved by making it equal to or higher than the lower limit.
  • the thickness is equal to or less than the above upper limit, there is a tendency that a uniform coating film can be easily obtained when the ink is applied to the pixel portion after the formation of the partition walls.
  • the photosensitive resin composition of the present invention contains a fluorine atom-containing resin having a cross-linking group in addition to the copolymer (A), the fluorine atom-containing resin having a cross-linking group in the photosensitive resin composition of the present invention
  • the content is not particularly limited, the total solid content (100% by mass) of the photosensitive resin composition is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and still more preferably 0.5% by mass. % or more, preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less.
  • the above upper and lower limits can be combined arbitrarily.
  • the ink repellency tends to be improved by making it equal to or higher than the lower limit.
  • the thickness is equal to or less than the above upper limit, there is a tendency that a uniform coating film can be easily obtained when the ink is applied to the pixel portion after the formation of the partition walls.
  • Coatability improver, development improver The photosensitive resin composition of the present invention may contain a coatability improver and a development improver in order to improve the coatability and development solubility.
  • Known surfactants for example, can be used as coatability improvers or development improvers.
  • the surfactant can be used for the purpose of improving the coatability of the photosensitive resin composition as a coating liquid and the developability of the coating film. Among them, fluorine-based surfactants and silicone-based surfactants are preferred.
  • silicone-based surfactants are preferable, polyether-modified silicone-based Surfactants are more preferred.
  • a compound having a fluoroalkyl or fluoroalkylene group on at least one of the terminal, main chain and side chain is suitable as the fluorosurfactant.
  • 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether
  • 1,1,2,2-tetrafluorooctylhexyl ether 1,1,2,2-tetrafluoropropyl
  • 1,1,2,2-tetrafluorooctylhexyl ether 1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol di(1,1,2,2,3,3-hexafluoropentyl) ether
  • octapropylene glycol di(1,1,2,2- tetrafluorobutyl) ether 1,1,2,2,3,3-hexafluoropentyl) ether
  • sodium perfluorododecylsulfonate 1,1,2,2,8,8,
  • silicone surfactants examples include “DC3PA”, “SH7PA”, “DC11PA”, “SH21PA”, “SH28PA”, “SH29PA”, “8032Additive” and “SH8400” manufactured by Dow Corning Toray Co., Ltd. "BYK (registered trademark, the same shall apply hereinafter) 323" and “BYK330” manufactured by K.K.
  • the surfactant may contain other surfactants other than fluorine-based surfactants and silicone-based surfactants, and other surfactants include, for example, nonionic, anionic, cationic, and amphoteric surfactants. Surfactants are included.
  • Nonionic surfactants include, for example, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, glycerin Fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythrityl fatty acid esters, polyoxyethylene pentaerythritic fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbit fatty acid esters, polyoxyethylene sorbitol fatty acid esters.
  • examples of these commercially available products include polyoxyethylene-based surfactants such as "Emulgen (registered trademark; hereinafter the same.) 104P" and "Emulgen A60" manufactured by Kao Corporation.
  • anionic surfactants include alkylsulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, polyoxyethylene alkylethersulfonates, alkylsulfates, alkylsulfates, higher alcohol sulfates, Fatty alcohol sulfates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, special polymer Surfactants are included.
  • a special polymeric surfactant is preferable, and a special polycarboxylic acid type polymeric surfactant is more preferable.
  • anionic surfactants include, for alkyl sulfates, "Emal (registered trademark) 10" manufactured by Kao Corporation, and for alkylnaphthalene sulfonates, “Perex (registered trademark) NB-L” manufactured by Kao Corporation.
  • Kao Corporation "Homogenol (registered trademark, hereinafter the same.) L-18", “Homogenol L-100” and the like can be mentioned.
  • Cationic surfactants include, for example, quaternary ammonium salts, imidazoline derivatives, and alkylamine salts.
  • Amphoteric surfactants include, for example, betaine-type compounds, imidazolium salts, imidazolines, and amino acids. Among these, quaternary ammonium salts are preferred, and stearyltrimethylammonium salts are more preferred.
  • Examples of cationic surfactants or amphoteric surfactants include alkylamine salts such as "Acetamine (registered trademark) 24" manufactured by Kao Corporation, and quaternary ammonium salts such as "Cortamine (registered trademark, hereinafter the same) 24P” and “Cortamine 86W”.
  • One type of surfactant may be used alone, or two or more types may be used in combination. Examples thereof include a combination of silicone surfactant/fluorosurfactant, a combination of silicone surfactant/special polymer surfactant, and a combination of fluorine surfactant/special polymer surfactant. . Among them, a combination of silicone surfactant/fluorosurfactant is preferable.
  • silicone-based surfactant / fluorine-based surfactant for example, BYK-Chemie's "BYK-300” or “BYK-330” / Neos's "DFX-18" combination, BYK-Chemie's "BYK- 300” or “BYK-330” / AGC Seimi Chemical Co., Ltd. “S-393” combination, BYK Chemie Co., Ltd. “BYK-300” or “BYK-330” / DIC Co., Ltd. “F-554” or “F-559 "Combination of "KP340" manufactured by Shin-Etsu Silicone Co., Ltd.
  • the photosensitive resin composition of the present invention contains a coatability improver or a development improver, the content of the coatability improver or development improver is determined from the viewpoint of sensitivity by adjusting the total solid content of the photosensitive resin composition (100 %), preferably 20% by mass or less, more preferably 10% by mass or less.
  • the photosensitive resin composition of the present invention may contain an ultraviolet absorber.
  • the ultraviolet absorber is added for the purpose of controlling the photocuring distribution by absorbing a specific wavelength of the light source used for exposure by the ultraviolet absorber.
  • an ultraviolet absorber By including an ultraviolet absorber, there is a tendency to obtain effects such as improving the taper angle shape after development and reducing residues remaining in non-exposed areas after development.
  • the ultraviolet absorber for example, a compound having an absorption maximum between 250 nm and 400 nm can be used from the viewpoint of inhibiting light absorption by the photopolymerization initiator.
  • ultraviolet absorbers examples include benzotriazole compounds, triazine compounds, benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and its derivatives, dinaphthalene compounds, phenanthroline compounds, and dyes. These ultraviolet absorbers may be used alone or in combination of two or more.
  • benzotriazole compounds include 2-(5methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, octyl-3[3-tert -butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro -2H-benzotriazol-2-yl)phenyl]propionate mixture, 2-[2-hydroxy-3,5-bis( ⁇ , ⁇ -dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t Butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'- t-o
  • benzotriazole compounds include, for example, Sumisorb (registered trademark, hereinafter the same) 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350 (manufactured by Sumitomo Chemical Co., Ltd.), JF77, JF78, JF79, JF80, JF83 (manufactured by Johoku Chemical Industry Co., Ltd.), TINUVIN (registered trademark, hereinafter the same) PS, TINUVIN99-2, TINUVIN109, TINUVIN384-2, TINUVIN326, TINUVIN900, TINUVIN928, TINUVIN1130 (manufactured by BASF), EVERSORB70, EVERSORB71, EVERSORB72, EVER , EVERSORB74, EVERSORB75, EVERSORB76, EVERSORB234, EVERSORB77, EVERSORB78, EVERSORB80, EVERSORB81 (manufactured
  • triazine compounds examples include 2-[4,6-di(2,4-xylyl)-1,3,5-triazin-2-yl]-5-octyloxyphenol, 2-[4,6- Bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, 2-(2,4-dihydroxyphenyl) -4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)glycidate reaction product, 2,4-bis[2-hydroxy-4-butoxyphenyl ]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine.
  • hydroxyphenyltriazine compounds are preferred from the viewpoint of taper angle and exposure sensitivity.
  • Commercially available triazine compounds include, for example, TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477, and TINUVIN479 (manufactured by BASF).
  • UV absorbers include, for example, Sumisorb 130 (manufactured by Sumitomo Chemical Co., Ltd.), EVERSORB10, EVERSORB11, EVERSORB12 (manufactured by Taiwan Eikoh Chemical Co., Ltd.), Tomisorb 800 (manufactured by API Corporation), SEESORB100, SEESORB101, SEESORB101S, SEESORB102.
  • the content of the ultraviolet absorber in the photosensitive resin composition is preferably 0 in the total solid content (100% by mass) of the photosensitive resin composition. 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, particularly preferably 1% by mass or more, and also preferably is 15% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less.
  • the upper and lower limits can be combined arbitrarily, for example, preferably 0.01 to 15% by mass, more preferably 0.05 to 15% by mass, further preferably 0.1 to 10% by mass, 0.5 to 5% by mass is even more preferred, and 1 to 3% by mass is particularly preferred.
  • the taper angle tends to increase when the lower limit value or more is used.
  • the sensitivity becomes high by making it equal to or less than the above upper limit.
  • the blending ratio of the UV absorber to the (D) photopolymerization initiator is: (D) 100 mass of the photopolymerization initiator parts, preferably 1 part by mass or more, more preferably 10 parts by mass or more, still more preferably 30 parts by mass or more, even more preferably 50 parts by mass or more, particularly preferably 80 parts by mass or more, and also preferably is 500 parts by mass or less, more preferably 300 parts by mass or less, still more preferably 200 parts by mass or less, and particularly preferably 150 parts by mass or less.
  • the above upper limit and lower limit can be combined arbitrarily.
  • 10 to 500 parts by mass is preferable, 30 to 300 parts by mass is more preferable, 50 to 200 parts by mass is more preferable, and 80 to 150 parts by mass is particularly preferable.
  • the taper angle tends to increase when the lower limit value or more is used.
  • the photosensitive resin composition of the present invention may contain a polymerization inhibitor. It is thought that the taper angle of the obtained partition wall can be increased because the radical polymerization is inhibited by containing the polymerization inhibitor.
  • Polymerization inhibitors include, for example, hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT). Among these, methylhydroquinone and methoxyphenol are preferred, and methylhydroquinone is more preferred, from the viewpoint of the ability to inhibit polymerization.
  • the polymerization inhibitor may be used singly or in combination of two or more.
  • the resin may contain a polymerization inhibitor, which may be used as the polymerization inhibitor contained in the photosensitive resin composition of the present invention, In addition to the polymerization inhibitor contained in the resin, the same or different polymerization inhibitor may be added during production of the photosensitive resin composition.
  • the content of the polymerization inhibitor in the photosensitive resin composition is preferably 0 in the total solid content (100% by mass) of the photosensitive resin composition. 0.0005% by mass or more, more preferably 0.001% by mass or more, still more preferably 0.01% by mass or more, preferably 0.3% by mass or less, more preferably 0.2% by mass or less, and further Preferably, it is 0.1% by mass or less.
  • the upper and lower limits can be combined arbitrarily, for example, 0.0005 to 0.3% by mass is preferable, 0.001 to 0.2% by mass is more preferable, and 0.01 to 0.1% by mass is further preferable.
  • the taper angle tends to be increased by making it equal to or higher than the lower limit. In addition, there is a tendency that high sensitivity can be maintained by making it equal to or less than the above upper limit.
  • the photosensitive resin composition of the invention may contain a silane coupling agent in order to improve adhesion to the substrate.
  • a silane coupling agent for example, epoxy-based, methacrylic-based, amino-based, and imidazole-based silane coupling agents can be used. From the viewpoint of improving adhesion, epoxy-based and imidazole-based silane coupling agents are particularly preferred.
  • the content of the silane coupling agent is preferably in the total solid content (100% by mass) of the photosensitive resin composition from the viewpoint of adhesion. is 20% by mass or less, more preferably 15% by mass or less.
  • the photosensitive resin composition of the present invention may contain a phosphoric acid-based adhesion improver in order to improve adhesion to a substrate.
  • a phosphoric acid-based adhesion improver in order to improve adhesion to a substrate.
  • (Meth)acryloyloxy group-containing phosphates are preferable as the phosphoric acid-based adhesion improver, and among them, those represented by the following general formulas (Va), (Vb), and (Vc) are preferable.
  • R 8 represents a hydrogen atom or a methyl group
  • r and r' are integers of 1 to 10
  • s is 1, 2 or 3.
  • the content is not particularly limited, but 0.1% by mass in the total solid content (100% by mass) of the photosensitive resin composition 0.2% by mass or more is more preferable, 0.3% by mass or more is even more preferable, 5% by mass or less is preferable, 3% by mass or less is more preferable, and 1% by mass or less is even more preferable.
  • the above upper limit and lower limit can be combined arbitrarily. For example, 0.1 to 5% by mass is preferable, 0.2 to 3% by mass is more preferable, and 0.3 to 1% by mass is even more preferable.
  • Adhesion to the substrate tends to be improved by making it equal to or higher than the lower limit. Moreover, there is a tendency that the surface curability is improved by setting the content to the above upper limit or less.
  • the photosensitive resin composition of the present invention usually contains a solvent, and each component described above is dissolved or dispersed in the solvent before use.
  • the solvent is not particularly limited, and examples thereof include the organic solvents described below.
  • Ethylene glycol monomethyl ether ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, 3-methoxy-1-butanol, tri Glycol monoalkyl ethers such as ethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether
  • solvents corresponding to the above include, for example, Mineral Spirit, Valsol #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No. 1 and no. 2.
  • Solvesso #150 Shell TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names).
  • the solvent can dissolve or disperse each component in the photosensitive resin composition, and is selected according to the method of using the photosensitive resin composition of the present invention.
  • the boiling point at 1013.25 hPa) is preferably 60 to 280°C, more preferably 70 to 260°C.
  • propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate and 3-methoxy-1-butyl acetate are preferred.
  • a solvent may be used individually by 1 type, and may use 2 or more types together.
  • the total solid content of the solvent in the photosensitive resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 18% by mass or more, and preferably 90% by mass or less, more preferably It is preferably used in an amount of 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 30% by mass or less.
  • the above upper limit and lower limit can be arbitrarily combined, and for example, 10 to 90% by mass is preferable, 10 to 50% by mass is more preferable, 15 to 40% by mass is more preferable, and 18 to 30% by mass is particularly preferable.
  • the content is at least the above lower limit, there is a tendency that a coating film can be obtained even with a high film thickness.
  • appropriate coating uniformity can be obtained by setting the content to be equal to or less than the above upper limit.
  • the photosensitive resin composition of the present invention is prepared by mixing the above components with a stirrer. In addition, you may filter using a membrane filter, for example so that the prepared photosensitive resin composition may be uniform.
  • the photosensitive resin composition of the present invention can be suitably used for forming partition walls, particularly partition walls for partitioning the organic layers (light-emitting portions) of organic electroluminescence elements.
  • the partition wall of the present invention comprises a cured product obtained by curing the photosensitive resin composition of the present invention or a cured product obtained by curing the photosensitive resin composition of the present invention.
  • a method for forming partition walls using the photosensitive resin composition of the present invention is not particularly limited, and conventionally known methods can be employed.
  • a method for forming the partition walls includes, for example, a coating step of applying a photosensitive resin composition onto a substrate to form a photosensitive resin composition layer, and an exposure step of exposing the photosensitive resin composition layer. is mentioned.
  • a specific example of a method for forming such partition walls is a photolithographic method.
  • a photosensitive resin composition is applied to the entire area of the substrate where the partition walls are to be formed to form a photosensitive resin composition layer. After the formed photosensitive resin composition layer is exposed according to a predetermined partition pattern, the exposed photosensitive resin composition layer is developed to form partitions on the substrate.
  • the substrate used for forming the partition is not particularly limited, and is appropriately selected according to the type of the organic electroluminescence device manufactured using the substrate on which the partition is formed.
  • Suitable substrate materials include glass and various resin materials.
  • Specific examples of the resin material include polyester such as polyethylene terephthalate; polyolefin such as polyethylene and polypropylene; polycarbonate; poly(meth)methacrylic resin; polysulfone; and polyimide.
  • polyester such as polyethylene terephthalate
  • polyolefin such as polyethylene and polypropylene
  • polycarbonate poly(meth)methacrylic resin
  • polysulfone polysulfone
  • polyimide polyimide
  • glass and polyimide are preferable because of their excellent heat resistance.
  • a transparent electrode layer such as ITO or ZnO may be provided in advance on the surface of the substrate on which the barrier ribs are formed, depending on the type of organic electroluminescence element to be manufactured.
  • a contact transfer type coating device such as a roll coater, reverse coater, bar coater, etc., or a spinner (rotating The photosensitive resin composition is applied using a non-contact coating apparatus such as a coating apparatus) or a curtain flow coater, and if necessary, the solvent is removed by drying to form a photosensitive resin composition layer.
  • the coating amount varies depending on the application, but in the case of partition walls, for example, the dry film thickness is preferably 0.5 ⁇ m to 30 ⁇ m, more preferably 1 ⁇ m to 15 ⁇ m, and still more preferably 1 ⁇ m to 5 ⁇ m. It is important that the dry film thickness or the finally formed barrier rib height is uniform over the entire substrate. If the variation is small, it is possible to suppress mura defects that occur in the display device.
  • Drying after supplying the photosensitive resin composition onto the substrate is preferably by a drying method using a hot plate, IR oven, or convection oven.
  • a reduced pressure drying method in which drying is performed in a reduced pressure chamber without raising the temperature, may be combined.
  • the drying conditions can be appropriately selected according to the type of solvent component and the performance of the dryer used.
  • the drying time is preferably selected in the range of 15 seconds to 5 minutes at a temperature of 40° C. to 130° C., more preferably 50° C. to 110° C., depending on the type of solvent component, the performance of the dryer used, etc. is selected in the range of 30 seconds to 3 minutes at a temperature of
  • a negative mask is used to irradiate the photosensitive resin composition with active energy rays such as ultraviolet light and excimer laser light, and the photosensitive resin composition layer is partially exposed according to the partition wall pattern.
  • active energy rays such as ultraviolet light and excimer laser light
  • a light source that emits ultraviolet rays such as a high-pressure mercury lamp, an extra-high pressure mercury lamp, a xenon lamp, or a carbon arc lamp, can be used.
  • the amount of exposure varies depending on the composition of the photosensitive resin composition, it is preferably about 10 to 400 mJ/cm 2 , for example.
  • a partition pattern is formed by developing the exposed photosensitive resin composition layer according to the partition pattern with a developer.
  • the development method is not particularly limited, and an immersion method, a spray method, or the like can be used.
  • Specific examples of the developer include organic ones such as dimethylbenzylamine, monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts. mentioned.
  • an antifoaming agent or a surfactant can be added to the developer.
  • the barrier ribs are obtained by subjecting the developed barrier rib pattern to post-baking (thermosetting treatment) and heat curing.
  • Post-baking is preferably performed at 100 to 250° C. for 15 to 60 minutes.
  • a cleaning treatment may be performed for the purpose of cleaning the unexposed areas after the formation of the barrier ribs.
  • the cleaning method is not particularly limited, and includes plasma irradiation, excimer light irradiation, and UV irradiation.
  • excimer light irradiation or UV irradiation active oxygen can decompose and remove organic matter adhering to the pixel portion due to the light irradiation.
  • the organic electroluminescent device of the present invention includes the partition of the present invention.
  • Various organic electroluminescence devices are manufactured using the substrate provided with the barrier rib pattern manufactured by the method described above.
  • the method for forming the organic electroluminescence device is not particularly limited, but preferably, after forming the partition pattern on the substrate by the above method, ink is injected into the region surrounded by the partition on the substrate to form pixels and the like.
  • An organic electroluminescence device is manufactured by forming an organic layer. Types of organic electroluminescence devices include bottom emission type and top emission type.
  • partition walls are formed on a glass substrate laminated with transparent electrodes, and a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode layer are laminated in an opening surrounded by the partition walls.
  • barrier ribs are formed on a glass substrate laminated with metal electrode layers, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are stacked in an opening surrounded by the barrier ribs. be done.
  • the ink for forming the organic layer is repelled by the bottom of the partition, so the area surrounded by the partition may not be sufficiently covered with the ink for forming the organic layer.
  • the inside of the region surrounded by the partition can be sufficiently covered with the ink for forming the organic layer.
  • Organic solvent Water, an organic solvent, and a mixed solvent thereof can be used as the solvent used when forming the ink for forming the organic layer.
  • the organic solvent is not particularly limited as long as it can be removed from the film formed after injecting the ink.
  • organic solvents include toluene, xylene, anisole, mesitylene, tetralin, cyclohexylbenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropyl alcohol, ethyl acetate, butyl acetate, and 3-phenoxytoluene.
  • surfactants, antioxidants, viscosity modifiers, ultraviolet absorbers, and the like can be added to the ink.
  • an inkjet method is preferable because a small amount of ink can be easily injected into a predetermined location.
  • the ink used for forming the organic layer is appropriately selected according to the type of organic electroluminescence element to be manufactured.
  • the viscosity of the ink is not particularly limited as long as the ink can be discharged well from the inkjet head, but is preferably 4 to 20 mPa ⁇ s, more preferably 5 to 10 mPa ⁇ s.
  • the viscosity of the ink can be adjusted by adjusting the solid content in the ink, changing the solvent, adding a viscosity modifier, and the like.
  • examples of the light-emitting layer include organic electroluminescent layers as described in Japanese Patent Application Laid-Open No. 2009-146691 and Japanese Patent No. 5734681. Quantum dots as described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may also be used.
  • Color filter containing luminescent nanocrystalline particles is not particularly limited as long as it comprises the partition walls of the present invention, and pixels are formed in regions partitioned by the partition walls. formed ones.
  • FIG. 2 is a schematic cross-sectional view of an example of a color filter having partition walls of the present invention.
  • the color filter 100 includes a substrate 10 , partition walls 20 provided on the substrate, red pixels 30 , green pixels 40 and blue pixels 50 .
  • the red pixels 30, the green pixels 40, and the blue pixels 50 are arranged in a grid so as to repeat in this order.
  • a partition wall 20 is provided between these adjacent pixels. In other words, these adjacent pixels are partitioned by the partition walls 20 .
  • Red pixels 30 contain red-emitting nanocrystalline particles 12 and green pixels 40 contain green-emitting nanocrystalline particles 11 .
  • the blue pixels 50 are pixels that transmit blue light from the light source.
  • nanocrystalline particles are nano-sized crystals that absorb excitation light and emit fluorescence or phosphorescence, and have, for example, a maximum particle size of 100 nm or less as measured by a transmission electron microscope or scanning electron microscope. It is crystalline.
  • Luminescent nanocrystalline particles can emit light (fluorescence or phosphorescence) of a wavelength different from the absorbed wavelength by absorbing light of a predetermined wavelength.
  • red-emitting nanocrystalline particles 12 emit light (red light) having an emission peak wavelength in the range of 605 to 665 nm
  • the green-emitting nanocrystalline particles 11 emit light (green light) having an emission peak wavelength in the range of 500 to 560 nm. ).
  • the wavelength (emission color) of the light emitted by the luminescent nanocrystalline particles depends on the size (e.g., particle diameter) of the luminescent nanocrystalline particles. It also depends on the energy gap of the crystal grains. Therefore, the emission color can be selected by changing the constituent material and size of the luminescent nanocrystalline particles used.
  • Luminescent nanocrystalline particles include quantum dots and the like.
  • a method for producing a color filter containing luminescent nanocrystalline particles is not particularly limited, but a substrate having barrier ribs composed of the cured product of the present invention is prepared, and luminescent nanocrystalline particles are contained in regions partitioned by the barrier ribs.
  • a method of forming a layer is included.
  • the method for forming a layer containing luminescent nanocrystalline particles is not particularly limited. It can be manufactured by a method of curing an object.
  • the image display device of the present invention includes the partition wall of the present invention.
  • Examples of the image display device of the present invention include an image display device including the organic electroluminescent device of the present invention.
  • the image display device of the present invention is formed by the method described in "Organic EL Display” (Ohmsha, August 20, 2004, Shizuo Tokito, Chihaya Adachi, Hideyuki Murata). can do.
  • an image may be displayed by combining an organic electroluminescent element that emits white light and a color filter, or an image may be displayed by combining organic electroluminescent elements emitting different colors such as RGB.
  • the image display device of the present invention includes, for example, an image display device provided with a color filter containing the luminescent nanocrystalline particles of the present invention.
  • Examples of types of image display devices include liquid crystal display devices and image display devices including organic electroluminescent elements.
  • a liquid crystal display device includes a light source having a blue LED and a liquid crystal layer having an electrode for controlling the blue light emitted from the light source for each pixel portion.
  • an image display device including an organic electroluminescence element includes an organic electroluminescence element that emits blue light and is arranged at a position corresponding to each pixel portion of the color filter. Specifically, the method described in Japanese Patent Application Laid-Open No. 2019-87746 can be mentioned.
  • the photosensitive resin composition of the present invention will be described with reference to specific examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
  • the constituent components of the photosensitive resin compositions used in the following examples and comparative examples are as follows.
  • a copolymer resin containing dicyclopentanyl methacrylate/styrene/glycidyl methacrylate (molar ratio: 0.30/0.10/0.60) as constituent monomers is added with acrylic acid in an equivalent amount to the glycidyl methacrylate. and an alkali-soluble acrylic copolymer resin obtained by adding 0.39 mol of tetrahydrophthalic anhydride to 1 mol of the above copolymer resin.
  • the polystyrene equivalent weight average molecular weight (Mw) measured by GPC was 9000, the acid value was 80 mgKOH/g, and the double bond equivalent was 470 g/mol.
  • a copolymer resin containing dicyclopentanyl methacrylate/styrene/glycidyl methacrylate (molar ratio: 0.02/0.05/0.93) as constituent monomers is subjected to an addition reaction of an equivalent amount of acrylic acid and the glycidyl methacrylate, and An alkali-soluble acrylic copolymer resin to which 0.10 mol of tetrahydrophthalic anhydride is added per 1 mol of the above copolymer resin.
  • the polystyrene equivalent weight average molecular weight (Mw) measured by GPC was 7700, the acid value was 28.5 mgKOH/g, and the double bond equivalent was 260 g/mol.
  • DPHA Dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.
  • TMP-A Trimethylolpropane triacrylate manufactured by Kyoei Co., Ltd.
  • ⁇ Copolymer-1 to 7> (1) weight average molecular weight (Mw) The weight average molecular weight of the copolymer was measured by GPC under the following conditions.
  • the mixed solution of parts by mass was added dropwise over 4 hours. After completion of dropping, 0.18 parts by mass of AMBN was added three times every 30 minutes, and after 30 minutes, the internal temperature was raised to 110° C. and held for 1.5 hours. Thereafter, the reaction solution was cooled to 40° C., and 45.27 parts by mass of PGMEA was added to obtain a PGMEA solution of Copolymer-1 before purification.
  • the solid content (non-volatile content) of the PGMEA solution of Copolymer-1 before purification was 30% by mass.
  • the precipitate of copolymer-1 was collected using filter paper, dried under reduced pressure at 40 ° C. for 6 hours, and then prepared with PGMEA to a solid content (non-volatile content) of 15% by mass, and a weight average molecular weight of 102,600 after purification.
  • a PGMEA solution of copolymer-1 was obtained.
  • the content of active groups per 1 g of Copolymer-1 was 1.28 (mmol/g).
  • Pigment Dispersion-1 A pigment, a dispersant, an alkali-soluble resin, and a solvent were mixed so as to have the mass ratio shown in Table 2. This solution was dispersed for 3 hours at a temperature range of 25 to 45° C. using a paint shaker. Zirconia beads with a diameter of 0.5 mm were used as beads, and 2.5 times the mass of the dispersion liquid was added. After completion of dispersion, the beads and the dispersion liquid were separated by a filter to prepare a pigment dispersion liquid-1.
  • Examples 1 to 7 and Comparative Examples 1 to 2 Each component other than Pigment Dispersion-1 was mixed at the mixing ratio shown in Table 3, and after stirring and fully dissolving, Pigment Dispersion-1 was added and mixed, followed by washing with an ultrasonic cleaner for 10 minutes.
  • a photosensitive resin composition was prepared by stirring. Using each of the obtained photosensitive resin compositions, evaluation was performed by the method described later.
  • the blending ratios of the pigment dispersion liquid, the alkali-soluble resin, and the copolymer in Table 3 are solid content conversion values.
  • the photosensitive resin composition was applied onto a glass substrate so as to have a thickness of 10 ⁇ m after post-baking.
  • This coated substrate was dried in vacuum for 1 minute, and further dried by heating on a hot plate at 100° C. for 120 seconds.
  • the entire surface of the resulting coating film was exposed to light with an exposure amount of 80 mJ/cm 2 using a mirror projection type exposure machine (MPA-600FA, manufactured by Canon Inc.). At this time, the light intensity at a wavelength of 365 nm was 500 mW/cm 2 .
  • this substrate is spray-developed at 24° C.
  • the photosensitive resin composition was applied onto a glass substrate so as to have a thickness of 10 ⁇ m after post-baking.
  • This coated substrate was dried in vacuum for 1 minute, and further dried by heating on a hot plate at 100° C. for 120 seconds.
  • the obtained coated film substrate was exposed with an exposure amount of 80 mJ/cm 2 using a photomask with an MPA exposure machine.
  • the light intensity at a wavelength of 365 nm was 500 mW/cm 2 .
  • the photomask used was a photomask having openings of 15 ⁇ m width arranged in a grid pattern at intervals of 100 ⁇ m in length and 200 ⁇ m in width.
  • the substrate was developed under the same conditions as those used for manufacturing the substrate for contact angle measurement, and post-baked in an oven at 230° C. for 30 minutes to manufacture an IJ substrate having an IJ partition pattern.
  • a 10 pL compatible nozzle cartridge filled with YED216D (1,6-hexanediol diglycidyl ether) manufactured by Mitsubishi Chemical Corporation was installed in an inkjet device DMP-2831 manufactured by Fujifilm Corporation, and the pixel portion of the above IJ substrate was mounted.
  • One droplet (corresponding to 10 pL) was ejected into (an opening portion surrounded by partition walls on all sides).
  • the IJ coating property was evaluated according to the following evaluation criteria based on the size of the ejected liquid droplets that were wetted and spread.
  • FIG. 1 shows that the IJ coatability is excellent in order from the left. It is not widespread, and there is a problem in practical use.
  • the (A) copolymer has an active group that generates radicals upon irradiation with an active energy ray. I know it will be. This is probably because the (A) copolymer generates radicals during exposure and contributes to the radical polymerization of the photosensitive resin composition, so that the (A) copolymer is fixed in the bank and hardly exudes during development. When the (A) copolymer is not fixed and oozes out, the (A) copolymer contaminates the inside of the pixel and deteriorates the wetting and spreading of the IJ ink.

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PCT/JP2022/036476 2021-10-01 2022-09-29 感光性樹脂組成物、硬化物、隔壁、有機電界発光素子、及び画像表示装置 Ceased WO2023054597A1 (ja)

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CN202280065688.4A CN118020026A (zh) 2021-10-01 2022-09-29 感光性树脂组合物、固化物、分隔壁、有机电致发光元件、以及图像显示装置
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JP2011099974A (ja) * 2009-11-05 2011-05-19 Fujifilm Corp 着色感光性組成物、カラーフィルタ、及び液晶表示装置
JP2012093395A (ja) * 2010-10-22 2012-05-17 Fujifilm Corp 光重合性組成物、カラーフィルタ、その製造方法、低屈折反率硬化膜、及び、固体撮像素子
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JP7234946B2 (ja) 2018-01-26 2023-03-08 三菱ケミカル株式会社 感光性樹脂組成物、隔壁、有機電界発光素子、画像表示装置及び照明

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JP2011099974A (ja) * 2009-11-05 2011-05-19 Fujifilm Corp 着色感光性組成物、カラーフィルタ、及び液晶表示装置
JP2012093395A (ja) * 2010-10-22 2012-05-17 Fujifilm Corp 光重合性組成物、カラーフィルタ、その製造方法、低屈折反率硬化膜、及び、固体撮像素子
JP2017207532A (ja) * 2016-05-16 2017-11-24 東洋合成工業株式会社 レジスト組成物及びそれを用いたデバイスの製造方法

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