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WO2023249070A1 - Composition de résine photosensible, produit durci et son procédé de formation, paroi de séparation et appareil d'affichage d'image - Google Patents

Composition de résine photosensible, produit durci et son procédé de formation, paroi de séparation et appareil d'affichage d'image Download PDF

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Publication number
WO2023249070A1
WO2023249070A1 PCT/JP2023/023061 JP2023023061W WO2023249070A1 WO 2023249070 A1 WO2023249070 A1 WO 2023249070A1 JP 2023023061 W JP2023023061 W JP 2023023061W WO 2023249070 A1 WO2023249070 A1 WO 2023249070A1
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Prior art keywords
group
ethylenically unsaturated
resin composition
photosensitive resin
formula
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PCT/JP2023/023061
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English (en)
Japanese (ja)
Inventor
紫陽 平岡
昌聡 池田
和裕 中谷
知子 砂留
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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Priority to KR1020247041501A priority Critical patent/KR20250025624A/ko
Priority to JP2024529063A priority patent/JPWO2023249070A1/ja
Priority to CN202380048098.5A priority patent/CN119404143A/zh
Publication of WO2023249070A1 publication Critical patent/WO2023249070A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • 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
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00

Definitions

  • the present invention relates to a photosensitive resin composition.
  • the present invention also relates to a cured product obtained by curing the photosensitive resin composition, a method for forming the same, a partition wall formed from the cured product, and an image display device equipped with the partition wall.
  • Image display devices that include organic electroluminescent elements (also referred to as organic electroluminescence, organic EL) have excellent visibility and responsiveness such as contrast and viewing angle, and are designed to reduce power consumption, be thinner and lighter, and display the display itself. Because it can be made flexible, it is attracting attention as a next-generation flat panel display (FPD).
  • organic electroluminescent elements also referred to as organic electroluminescence, organic EL
  • FPD next-generation flat panel display
  • An organic electroluminescent device has a structure in which a light emitting layer or an organic layer including various functional layers is sandwiched between a pair of electrodes, at least one of which is translucent.
  • An image display device displays an image by driving a panel in which an organic electroluminescent element is arranged for each pixel.
  • an organic electroluminescent device has been manufactured by forming barrier ribs (banks) on a substrate and then stacking a light emitting layer or various functional layers within a region surrounded by the barrier ribs.
  • Patent Document 1 describes a photosensitive colored resin composition that combines a specific organic pigment, a specific dispersant, and a specific resin.
  • a photosensitive colored resin composition is applied onto a substrate, and then dried under reduced pressure in a vacuum drying device, then heated and dried on a hot plate, and then subjected to image exposure and development. , hardening (curing) by high temperature treatment.
  • curing may be performed in an inert atmosphere such as nitrogen.
  • the present inventor investigated and found that the photosensitive colored resin composition described in Patent Document 1 is not inhibited by oxygen in curing in a nitrogen atmosphere, so it hardens quickly before heat flow occurs, and as a result, the partition wall A problem has been discovered in which the side surfaces of the partition wall become nearly perpendicular to the substrate surface, that is, the taper angle of the side surface of the partition wall becomes large. When the taper angle of the side surface of the partition wall becomes large, when various functional layers are laminated, each layer becomes discontinuous, which causes display defects.
  • the present inventors have discovered that the above-mentioned problems can be solved by a photosensitive resin composition containing an alkali-soluble resin and a specific ethylenically unsaturated compound in a predetermined ratio, and have arrived at the present invention. That is, the gist of the present invention is as follows.
  • a photosensitive resin composition containing (a) an alkali-soluble resin, (b) a photopolymerization initiator, and (c) an ethylenically unsaturated compound,
  • the mass ratio of the (a) alkali-soluble resin and the (c) ethylenically unsaturated compound ((a) alkali-soluble resin/(c) ethylenically unsaturated compound) is 5 or more
  • a photosensitive resin composition characterized in that the ethylenically unsaturated compound (c) contains an ethylenically unsaturated compound (c1) having an alkylene oxide group and having three or more ethylenically unsaturated groups. .
  • a photosensitive resin composition containing (a) an alkali-soluble resin, (b) a photopolymerization initiator, and (c) an ethylenically unsaturated compound,
  • the above (a) alkali is a weighted average value of the numerical value obtained by dividing the content (mass) of the above (a) alkali-soluble resin and the above (c) ethylenically unsaturated compound by the number of moles of each ethylenically unsaturated bond.
  • the total double bond equivalent of the soluble resin and (c) ethylenically unsaturated compound is 270 g/mol or more,
  • a photosensitive resin composition characterized in that the ethylenically unsaturated compound (c) contains an ethylenically unsaturated compound (c1) having an alkylene oxide group and having three or more ethylenically unsaturated groups. .
  • the mass ratio of the (a) alkali-soluble resin and the (c) ethylenically unsaturated compound ((a) alkali-soluble resin/(c) ethylenically unsaturated compound) is 8 or more, [5] The photosensitive resin composition described in .
  • the ethylenically unsaturated compound (c1) contains a compound (c1-1) represented by the following general formula (c1-1-1), according to any one of [1] to [9].
  • Photosensitive resin composition contains a compound (c1-1) represented by the following general formula (c1-1-1), according to any one of [1] to [9].
  • (X in formula (c1-1-1) is represented by the following general formula (c1-1-2). X may be different or the same.
  • Y is a methyl group or the following general formula (c1-1-2). (Represented by formula (c1-1-4).)
  • R 1 in formula (c1-1-2) represents an alkylene group having 2 to 4 carbon atoms.
  • a represents an integer of 1 to 9.
  • R2 is represented by the following general formula (c1-1-3). * represents a bond.
  • R 3 in formula (c1-1-3) represents a hydrogen atom or a methyl group. * represents a bond.
  • Y in the formula (c1-1-1) is represented by the formula (c1-1-4), and m in the formula (c1-1-4) is 1, [10] Or the photosensitive resin composition according to [11].
  • the benzene ring in formula (a1-0) may be further substituted with any substituent.
  • Q represents O, S, CO, or a direct bond. * represents a bond.
  • R 9 each independently represents a hydrogen atom or a methyl group.
  • Q represents O, S, CO, or indicates a direct bond.
  • n represents an integer from 0 to 4.
  • Plural Q's may be different or the same. * represents a bond.
  • the organic black pigment is at least one selected from the group consisting of a compound represented by the following general formula (d1), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound.
  • the photosensitive resin composition according to [17] which contains seeds.
  • R 11 and R 16 each independently represent a hydrogen atom, CH 3 , CF 3 , a fluorine atom, or a chlorine atom.
  • At least one combination selected from the group consisting of R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 17 and R 18 , R 18 and R 19 , and R 19 and R 20 is or may be bonded to each other via an oxygen atom, a sulfur atom, an NH or NR 21 bridge.
  • R 21 and R 22 each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or a cycloalkenyl group having 3 to 12 carbon atoms; Represents 2 to 12 alkynyl groups.
  • a method for forming a cured product comprising using a photosensitive resin composition containing (c1') and performing at least the following steps (1) to (4).
  • Step (3) A step of developing the coating film exposed in step (2).
  • step (4) is a step of baking the coating film developed in the step (3) in an inert atmosphere or under vacuum.
  • the mass ratio of the (a) alkali-soluble resin and the (c) ethylenically unsaturated compound in the photosensitive resin composition ((a) alkali-soluble resin/(c) ethylenically unsaturated compound) is 5 or more, the method for forming a cured product according to any one of [22] to [24].
  • the present invention provides a photosensitive resin composition capable of forming a cured product with an excellent tapered shape even when cured under an inert atmosphere, a cured product, a partition wall formed from the same, and an image display device equipped with such a partition wall. can do.
  • FIG. 1 is a schematic cross-sectional view of a partition wall showing a gently tapered shape.
  • (meth)acrylic means “one or both of acrylic and methacrylic.” The same applies to “(meth)acrylate” and “(meth)acryloyl.”
  • Total solid content means all components other than the solvent in the photosensitive resin composition. Even if components other than the solvent are liquid at room temperature, they are not included in the solvent but included in the total solid content.
  • the numerical range expressed using "-” means a range that includes the numerical values written before and after "-" as lower and upper limits.
  • a partition wall material refers to a bank material, a wall material, and a wall material
  • a partition wall refers to a bank, a wall, and a wall.
  • a partition wall is used to partition a functional layer (organic layer) in an active drive type organic electroluminescent device, and the material forming the functional layer is deposited or inkjet in the partitioned area (pixel area). It is used to form pixels and the like made up of functional layers and partition walls by coating and drying using a method such as a coating method.
  • the weight average molecular weight refers to the weight average molecular weight (Mw) in terms of polystyrene measured by GPC (gel permeation chromatography).
  • the "amine value” refers to the amine value in terms of effective solid content, unless otherwise specified, and is a value expressed by the mass of KOH equivalent to the amount of base per 1 g of solid content of the dispersant. . The method for measuring the amine value will be described later.
  • “Acid value” refers to the acid value in terms of effective solid content, unless otherwise specified, and is calculated by neutralization titration.
  • Photosensitive resin composition contains (a) an alkali-soluble resin, (b) a photopolymerization initiator, and (c) an ethylenically unsaturated compound as essential components. Depending on the conditions, further (d) colorants, dispersants, pigment derivatives, surfactants, liquid repellents, ultraviolet absorbers, polymerization inhibitors, thermal polymerization initiators, amino compounds, silane coupling agents, inorganic fillers, adhesion It contains an improver and other ingredients, and each ingredient is usually used in a state dissolved or dispersed in a solvent.
  • the photosensitive resin composition of the present invention contains (a) an alkali-soluble resin.
  • an alkali-soluble resin By containing an alkali-soluble resin, it becomes developable with an alkaline developer, and patterns such as partition walls can be created.
  • the alkali-soluble resin (a) in the photosensitive resin composition of the present invention can contain an alkali-soluble resin (a1) having a cardo skeleton. By containing the alkali-soluble resin (a1), the taper angle tends to become smaller.
  • alkali-soluble resin (a1) is not particularly limited as long as it contains a cardo skeleton, but from the viewpoint of the taper angle, it preferably has a partial structure represented by the following general formula (a1-0).
  • the benzene ring in formula (a1-0) may be further substituted with any substituent.
  • Q represents O, S, CO, or a direct bond. * represents a bond.
  • the partial structure represented by the above formula (a1-0) contained in the alkali-soluble resin (a1) may be one type or two or more types.
  • Q is preferably a direct bond from the viewpoint of the taper angle.
  • the benzene ring in formula (a1-0) may be unsubstituted or further substituted with any substituent.
  • the optional substituent include a methyl group and a methoxy group. From the viewpoint of ease of synthesis, non-substitution is preferred.
  • the partial structure represented by the formula (a1-0) has a partial structure represented by the following general formula (a1-1).
  • R 9 each independently represents a hydrogen atom or a methyl group.
  • Q represents O, S, CO, or indicates a direct bond.
  • n represents an integer from 0 to 4.
  • Plural Q's may be different or the same. * represents a bond.
  • R 9 is a hydrogen atom.
  • Q is preferably a direct bond from the viewpoint of the taper angle.
  • the benzene ring in formula (a1-1) may be unsubstituted or further substituted with any substituent.
  • substituents include a methyl group and a methoxy group. From the viewpoint of ease of synthesis, non-substitution is preferred.
  • the partial structure represented by the formula (a1-1) is preferably a partial structure represented by the following formula (a1-2).
  • R 9 , Q, and n have the same meanings as in formula (a1-1).
  • R X1 , R X2 and R X3 each independently represent a hydrogen atom or a polybasic acid residue. * represents a bond.
  • the polybasic acid residue means a monovalent or divalent group obtained by removing one or two OH groups from a polybasic acid.
  • the polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endo.
  • examples include methylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
  • maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and more preferred are Tetrahydrophthalic acid and biphenyltetracarboxylic acid are preferred, and tetrahydrophthalic acid is more preferred.
  • the acid value of the alkali-soluble resin (a1) is not particularly limited, but is preferably at least 20 mgKOH/g, more preferably at least 40 mgKOH/g, even more preferably at least 60 mgKOH/g, even more preferably at least 80 mgKOH/g, and even more preferably at least 100 mgKOH/g.
  • the above is particularly preferable. Further, it is preferably 150 mgKOH/g or less, more preferably 140 mgKOH/g or less, even more preferably 130 mgKOH/g or less, and even more preferably 120 mgKOH/g or less.
  • Developability tends to improve by setting the acid value of the alkali-soluble resin (a1) to the lower limit value or more. By setting the acid value of the alkali-soluble resin (a1) to be less than or equal to the upper limit value, resolution tends to improve.
  • the weight average molecular weight (Mw) of the alkali-soluble resin (a1) is not particularly limited, but is usually 1000 or more, preferably 2000 or more, more preferably 3000 or more, still more preferably 4000 or more, particularly preferably 4500 or more. Further, it is usually 20,000 or less, preferably 15,000 or less, more preferably 10,000 or less, even more preferably 8,000 or less, particularly preferably 6,000 or less.
  • Mw of the alkali-soluble resin (a1) By setting the Mw of the alkali-soluble resin (a1) to the above lower limit value or more, the development adhesion tends to improve.
  • the Mw of the alkali-soluble resin (a1) By setting the Mw of the alkali-soluble resin (a1) to be below the above-mentioned upper limit, developability tends to be improved.
  • the content ratio of the alkali-soluble resin (a1) to the total amount of the alkali-soluble resin is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 40% by mass or more, and particularly preferably 60% by mass or more. .
  • the taper angle is a tendency for the taper angle to be improved by making the content ratio of the alkali-soluble resin (a1) equal to or higher than the lower limit value.
  • the alkali-soluble resin (a) in the photosensitive resin composition of the present invention is an alkali-soluble resin other than the alkali-soluble resin (a1), that is, an alkali-soluble resin that does not have a cardo skeleton (hereinafter referred to as "other alkali-soluble resin"). ) may also be included.
  • the other alkali-soluble resins contained in the alkali-soluble resin may be one type or two or more types.
  • the other alkali-soluble resins preferably include an alkali-soluble resin (a2) having a partial structure represented by the following general formula (a2-1).
  • R 10 in formula (a2-1) represents a hydrogen atom or a methyl group. * represents a bond.
  • R 10 is preferably a methyl group from the viewpoint of reducing residue.
  • the partial structure represented by the above formula (a2-1) contained in the alkali-soluble resin (a2) may be one type or two or more types.
  • the partial structure represented by the formula (a2-1) is preferably a partial structure represented by the following formula (a2-2).
  • R 10 in formula (a2-2) has the same meaning as in formula (a2-1). * represents a bond.
  • R Y represents a hydrogen atom or a polybasic acid residue.
  • the polybasic acid residue has the same meaning as in formula (a1-2) above.
  • the polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endo.
  • examples include methylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
  • maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and more preferred are Tetrahydrophthalic acid and biphenyltetracarboxylic acid are preferred, and tetrahydrophthalic acid is more preferred.
  • the acid value of the alkali-soluble resin (a2) is not particularly limited, but is preferably at least 20 mgKOH/g, more preferably at least 40 mgKOH/g, even more preferably at least 60 mgKOH/g, even more preferably at least 80 mgKOH/g, and even more preferably at least 90 mgKOH/g.
  • the above is particularly preferable. Further, it is preferably 150 mgKOH/g or less, more preferably 140 mgKOH/g or less, even more preferably 130 mgKOH/g or less, and even more preferably 120 mgKOH/g or less.
  • Developability tends to improve by setting the acid value of the alkali-soluble resin (a2) to the above lower limit or more. When the acid value of the alkali-soluble resin (a2) is below the upper limit, resolution tends to improve.
  • the weight average molecular weight (Mw) of the alkali-soluble resin (a2) is not particularly limited, but is usually 1000 or more, preferably 1500 or more, more preferably 2000 or more, still more preferably 2500 or more, particularly preferably 3000 or more. be. Further, it is usually 20,000 or less, preferably 15,000 or less, more preferably 10,000 or less, still more preferably 6,000 or less, particularly preferably 4,000 or less.
  • Mw of the alkali-soluble resin (a2) is not particularly limited, but is usually 1000 or more, preferably 1500 or more, more preferably 2000 or more, still more preferably 2500 or more, particularly preferably 3000 or more. be. Further, it is usually 20,000 or less, preferably 15,000 or less, more preferably 10,000 or less, still more preferably 6,000 or less, particularly preferably 4,000 or less.
  • the content ratio of the alkali-soluble resin (a2) to the total amount of the alkali-soluble resin is preferably 1% by mass or more, more preferably 5% by mass or more, particularly preferably 10% by mass or more, and 90% by mass or less. It is preferably 70% by mass or less, more preferably 50% by mass or less, particularly preferably 30% by mass or less.
  • alkali-soluble resins include acrylic copolymer resin (A11) having an ethylenically unsaturated group in the side chain (hereinafter sometimes abbreviated as "acrylic copolymer resin (A11)"). You can stay there. Moreover, epoxy (meth)acrylate resin (A12) may be included.
  • the acrylic copolymer resin (A11) will be described in detail below.
  • the acrylic copolymer resin (A11) may have an ethylenically unsaturated group in the side chain.
  • the partial structure of the acrylic copolymer resin (A11) containing a side chain having an ethylenically unsaturated group is not particularly limited, but from the viewpoint of ease of radical dispersion due to the flexibility of the membrane, for example, the following general formula It is preferable to have a partial structure represented by (I).
  • R 111 and R 112 each independently represent a hydrogen atom or a methyl group. * represents a bond.
  • the partial structure represented by the above formula (I) contained in the acrylic copolymer resin (A11) may be one type or two or more types.
  • the partial structure represented by the following general formula (I') is preferable from the viewpoint of sensitivity and alkali developability.
  • R 111 and R 112 each independently represent a hydrogen atom or a methyl group.
  • R x represents a hydrogen atom or a polybasic acid residue. * represents a bond.
  • R x represents a hydrogen atom or a polybasic acid residue.
  • the polybasic acid residue means a monovalent or divalent group obtained by removing one or two OH groups from a polybasic acid.
  • the polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endo.
  • Examples include methylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
  • maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and more preferred are These are tetrahydrophthalic acid and succinic acid.
  • the content ratio is not particularly limited, but for example, the content ratio is based on the total number of moles of the constituent units of the acrylic copolymer resin (A11). It is 10 mol% or more and 90 mol% or less.
  • the content ratio is not particularly limited, but for example, based on the total number of moles of the constituent units of the acrylic copolymer resin (A11). It is 10 mol% or more and 80 mol% or less.
  • R 113 represents a hydrogen atom or a methyl group.
  • R 114 represents an alkyl group that may have a substituent, an aromatic ring group that may have a substituent, or a substituted Represents an alkenyl group that may have a group. * represents a bond.
  • the partial structure represented by the above formula (II) contained in the acrylic copolymer resin (A11) may be one type or two or more types.
  • R 114 represents an alkyl group that may have a substituent, an aromatic ring group that may have a substituent, or an alkenyl group that may have a substituent.
  • alkyl group for R 114 include linear, branched, or cyclic alkyl groups. The number of carbon atoms is, for example, 1 or more and 20 or less.
  • alkyl group for R 114 include, for example, a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, and a dodecanyl group.
  • substituents that the alkyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxy group. group, acryloyl group, and methacryloyl group.
  • Examples of the aromatic ring group for R 114 include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group.
  • the number of carbon atoms is, for example, 6 or more and 24 or less.
  • the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, such as a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, and a pyrene ring.
  • ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring may be a single ring or a condensed ring, such as a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, and a pyrene ring.
  • the aromatic heterocycle in the aromatic heterocyclic group may be a single ring or a condensed ring, such as a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, and an imidazole ring.
  • oxadiazole ring indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, Examples include benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring. .
  • substituents that the aromatic ring group may have include methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, and epoxy group. group, oligoethylene glycol group, phenyl group, and carboxy group.
  • alkenyl group for R 114 examples include linear, branched or cyclic alkenyl groups.
  • the number of carbon atoms is, for example, 2 or more and 22 or less.
  • alkenyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxy group. Examples include groups.
  • R 114 represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent.
  • the content ratio is not particularly limited, but for example, based on the total number of moles of the constituent units of the acrylic copolymer resin (A11), It is 1 mol% or more and 70 mol% or less.
  • R 115 represents a hydrogen atom or a methyl group.
  • R 116 represents an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an alkenyl group that may have a substituent.
  • t represents an optionally substituted alkynyl group, hydroxy group, carboxy group, halogen atom, optionally substituted alkoxy group, thiol group, or optionally substituted alkyl sulfide group. Represents an integer from 0 to 5. When t is 2 or more, multiple R 116 may be different or the same. * represents a bond.
  • the partial structure represented by the above formula (III) contained in the acrylic copolymer resin (A11) may be one type or two or more types.
  • R 116 is an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, a hydroxy group, or a carboxy group. , represents a halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkyl sulfide group which may have a substituent.
  • alkyl group for R 116 examples include linear, branched or cyclic alkyl groups.
  • the number of carbon atoms is, for example, 1 or more and 20 or less.
  • alkyl group for R 116 include, for example, a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, and a dodecanyl group.
  • substituents that the alkyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxy group. group, acryloyl group, methacryloyl group, etc.
  • Examples of the alkenyl group for R 116 include linear, branched or cyclic alkenyl groups. The number of carbon atoms is, for example, 2 or more and 22 or less.
  • Examples of substituents that the alkenyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxy group. Examples include groups.
  • alkynyl group for R 116 examples include linear, branched or cyclic alkynyl groups.
  • the number of carbon atoms is, for example, 2 or more and 20 or less.
  • alkynyl group may have examples include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxy group. Examples include groups.
  • halogen atom for R 116 examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • alkoxy group for R 116 examples include linear, branched or cyclic alkoxy groups.
  • the number of carbon atoms is, for example, 1 or more and 20 or less.
  • alkoxy group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxy group. group, acryloyl group, and methacryloyl group.
  • alkyl sulfide group for R 116 examples include linear, branched or cyclic alkyl sulfide groups.
  • the number of carbon atoms is, for example, 1 or more and 20 or less.
  • substituents that the alkyl group in the alkyl sulfide group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, Examples include phenyl group, carboxy group, acryloyl group, and methacryloyl group.
  • R116 is an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, a hydroxy group, a carboxy group, a halogen atom, a substituent represents an alkoxy group that may have a substituent, a thiol group, or an alkyl sulfide group that may have a substituent.
  • t represents an integer of 0 to 5.
  • the content ratio is not particularly limited, but for example, based on the total number of moles of the constituent units of the acrylic copolymer resin (A11) , 0.5 mol% or more and 50 mol% or less.
  • R 117 represents a hydrogen atom or a methyl group. * represents a bond.
  • the partial structure represented by the above formula (IV) contained in the acrylic copolymer resin (A11) may be one type or two or more types.
  • the content ratio is not particularly limited, but for example, based on the total number of moles of the constituent units of the acrylic copolymer resin (A11), It is 5 mol% or more and 80 mol% or less.
  • the acid value of the acrylic copolymer resin (A11) is not particularly limited, but is, for example, 30 mgKOH/g or more and 150 mgKOH/g or less.
  • the weight average molecular weight (Mw) of the acrylic copolymer resin (A11) is not particularly limited, but is, for example, 1000 or more and 30000 or less.
  • the content ratio of the acrylic copolymer resin (A11) to the total amount of the alkali-soluble resin is not particularly limited, but is, for example, 3% by mass or more and 70% by mass or less.
  • acrylic copolymer resin (A11) examples include, for example, the resins described in Japanese Unexamined Patent Publication No. 8-297366 and Japanese Unexamined Patent Publication No. 2001-89533.
  • Epoxy (meth)acrylate resin (A12) is produced by adding an ethylenically unsaturated monocarboxylic acid and/or its ester compound to an epoxy resin, optionally reacting with an isocyanate group-containing compound, and then adding a polybasic acid and/or This is a resin made by reacting the anhydride.
  • epoxy (meth)acrylate resins having an aromatic ring in the main chain can be preferably used.
  • an ethylenically unsaturated bond is added to the epoxy compound via an ester bond (-COO-), and examples include those in which one carboxy group of a polybasic acid anhydride is added to the hydroxyl group generated at that time. Further, when adding a polybasic acid and/or its anhydride, a polyhydric alcohol may also be added at the same time.
  • epoxy (meth)acrylate resin (A12) is a resin obtained by reacting a compound having a functional group that can further react with the carboxy group of the resin obtained in the above reaction.
  • epoxy (meth)acrylate resin has virtually no epoxy groups due to its chemical structure, and is not limited to "(meth)acrylate", but it is made from an epoxy compound (epoxy resin) as a raw material.
  • epoxy compound (epoxy resin) is a typical example, it is named this way according to common usage.
  • the epoxy resin includes the raw material compound before forming the resin by thermosetting.
  • the epoxy resin can be appropriately selected from known epoxy resins.
  • a compound obtained by reacting a phenolic compound and epihalohydrin can be used as the epoxy resin.
  • the phenolic compound is preferably a compound having a divalent or more than divalent phenolic hydroxyl group, and may be a monomer or a polymer.
  • raw material epoxy resins include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolac epoxy resin, trisphenol epoxy resin, and dihydrooxyl fluorene type.
  • examples include epoxy resins, dihydroxylalkyleneoxylfluorene type epoxy resins, diglycidyl etherified products of 1,1-bis(4'-hydroxyphenyl)adamantane, and those having an aromatic ring in the main chain are preferably used. Can be used.
  • bisphenol A epoxy resin bisphenol A epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, etc. are preferable.
  • epoxy resin examples include bisphenol A epoxy resins (for example, "jER (registered trademark, hereinafter the same applies)” manufactured by Mitsubishi Chemical Corporation, “jER1001", “jER1002”, “jER1004", manufactured by Nippon Kayaku Co., Ltd.).
  • R 121 is each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or represents a cycloalkyl group, phenyl group, naphthyl group, or biphenyl group. Multiple R 121s present in one molecule may be the same or different.
  • Z represents a linking group represented by the following general formula (i-13-1) or (i-13-2). However, if there is one or more adamantane structure in the molecular structure, (c represents 2 or 3.)
  • R 131 to R 134 and R 135 to R 137 each independently represent an adamantyl group that may have a substituent, a hydrogen atom, , represents an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent. * represents a bond.
  • ethylenically unsaturated monocarboxylic acids include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, pentaerythritol tri(meth)acrylate succinic anhydride adduct, and pentaerythritol tri(meth)acrylate succinic anhydride adduct.
  • Examples include phthalic anhydride adducts and reaction products of (meth)acrylic acid and ⁇ -caprolactone. Among these, (meth)acrylic acid is preferred from the viewpoint of sensitivity.
  • polybasic acids and/or anhydrides thereof include succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, and 3-ethyltetrahydrophthalic acid.
  • 4-ethyltetrahydrophthalic acid hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyro Mellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, and anhydrides thereof.
  • succinic anhydride succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are preferred, and succinic anhydride and tetrahydrophthalic anhydride are more preferred.
  • polyhydric alcohol As a raw material for epoxy (meth)acrylate resin (A12), it is possible to increase the molecular weight of epoxy (meth)acrylate resin (A12) and introduce branches into the molecule, which improves the molecular weight and viscosity. They tend to be able to balance things out. Furthermore, the rate of introduction of acid groups into the molecule can be increased, and sensitivity, adhesion, etc. tend to be more balanced.
  • the polyhydric alcohol include one or more polyhydric alcohols selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. is preferred.
  • epoxy (meth)acrylate resin (A12) for example, those described in Korean Patent Publication No. 10-2013-0022955 can be mentioned.
  • the acid value of the epoxy (meth)acrylate resin (A12) is not particularly limited, but is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, even more preferably 30 mgKOH/g or more, even more preferably 40 mgKOH/g or more, It is particularly preferably at least 50 mgKOH/g, preferably at most 200 mgKOH/g, more preferably at most 180 mgKOH/g, even more preferably at most 150 mgKOH/g, even more preferably at most 120 mgKOH/g, and particularly preferably at most 110 mgKOH/g.
  • Developability tends to improve by setting the acid value of the epoxy (meth)acrylate resin (A12) to the lower limit value or more.
  • the film strength tends to improve.
  • the acid value of the epoxy (meth)acrylate resin (A12) is preferably 10 to 200 mgKOH/g, more preferably 20 to 180 mgKOH/g, even more preferably 30 to 150 mgKOH/g, even more preferably 40 to 120 mgKOH/g. , 50 to 110 mgKOH/g is particularly preferred.
  • the weight average molecular weight (Mw) of the epoxy (meth)acrylate resin (A12) is not particularly limited, but is usually 1000 or more, preferably 2000 or more, more preferably 3000 or more, even more preferably 3500 or more, and usually 30000 or less. , preferably 15,000 or less, more preferably 10,000 or less, further preferably 8,000 or less, particularly preferably 6,000 or less.
  • the weight average molecular weight (Mw) of the epoxy (meth)acrylate resin (A12) is preferably 1,000 to 30,000, more preferably 2,000 to 15,000, even more preferably 3,000 to 10,000, even more preferably 3,500 to 8,000, and even more preferably 3,500 to 6,000. is particularly preferred.
  • the content ratio of the epoxy (meth)acrylate resin (A12) to the total amount of (a) alkali-soluble resin is not particularly limited, but for example, 50% by mass % or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more. There is a tendency for the residue to be reduced by making this content ratio equal to or higher than the lower limit value.
  • the epoxy (meth)acrylate resin (A12) can be synthesized by a conventionally known method. Specifically, the epoxy resin is dissolved in an organic solvent, the ethylenically unsaturated bond-containing acid and/or its ester compound is added thereto in the coexistence of a catalyst and a thermal polymerization inhibitor, and the polybasic acid is added to the epoxy resin. A method of continuing the reaction by adding an acid and/or its anhydride can be used. For example, methods described in Japanese Patent No. 3938375 and Japanese Patent No. 5169422 can be used.
  • examples of the organic solvent used in the reaction include one or more organic solvents such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate.
  • examples of the above-mentioned catalysts include tertiary amines such as triethylamine, benzyldimethylamine, and tribenzylamine; Examples include one or more of quaternary amminium salts, phosphorus compounds such as triphenylphosphine, and stibines such as triphenylstibine.
  • examples of the thermal polymerization inhibitor include one or more of hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, and the like.
  • the amount of ethylenically unsaturated monocarboxylic acid and/or its ester compound to be used is usually 0.7 to 1.3 chemical equivalents, preferably 0.9 to 1.3 chemical equivalents per chemical equivalent of the epoxy group of the epoxy resin.
  • the amount can be set to 1 chemical equivalent.
  • the amount of polybasic acid and/or its anhydride to be used is usually 0.1 to 1.2 chemical equivalents, preferably 0.2 to 1.1 chemical equivalents, per 1 chemical equivalent of the hydroxyl group produced in the addition reaction.
  • the amount can be set to a chemical equivalent.
  • the temperature during the addition reaction can be generally 60 to 150°C, preferably 80 to 120°C.
  • epoxy (meth)acrylate resins (A12) from the viewpoint of film strength and linearity, the following general formula (i), the following general formula (ii-1), the following general formula (ii-2), the following general formula ( Among the partial structures represented by iii), epoxy (meth)acrylate resins having at least one kind are preferred.
  • R a represents a hydrogen atom or a methyl group.
  • R b is a linear or branched divalent aliphatic group that may have a substituent, or a divalent aliphatic group that may have a substituent.
  • the formula (i ) The benzene ring in ) may be further substituted with any substituent. * represents a bond.
  • R c each independently represents a hydrogen atom or a methyl group.
  • R ⁇ represents a monovalent cyclic hydrocarbon group which may have a substituent.
  • q is 1 (The benzene ring in formula (ii-1) may be further substituted with any substituent.)
  • R c each independently represents a hydrogen atom or a methyl group.
  • R ⁇ represents a divalent cyclic hydrocarbon group which may have a substituent.
  • Formula (ii The benzene ring in -2) may be further substituted with any substituent.)
  • R e represents a hydrogen atom or a methyl group.
  • ⁇ is a single bond, -CO-, an alkylene group that may have a substituent, or 2 that may have a substituent
  • the benzene ring in formula (iii) may be further substituted with any substituent. * represents a bond.
  • epoxy (meth)acrylate resin (hereinafter sometimes referred to as "epoxy (meth)acrylate resin (A12-1)") having a partial structure represented by the following general formula (i) will be described in detail.
  • R a represents a hydrogen atom or a methyl group.
  • R b is a linear or branched divalent aliphatic group that may have a substituent, or a divalent aliphatic group that may have a substituent.
  • the formula (i ) The benzene ring in ) may be further substituted with any substituent. * represents a bond.
  • the partial structure represented by the above formula (i) contained in the epoxy (meth)acrylate resin (A12-1) may be one type or two or more types.
  • R b is a linear or branched divalent aliphatic group that may have a substituent, a divalent aromatic ring group that may have a substituent, or Represents a group in which one or more divalent aliphatic groups that may have a substituent and one or more divalent aromatic ring groups are connected.
  • the divalent aliphatic group examples include linear and branched aliphatic groups.
  • the number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
  • the film strength tends to improve.
  • the divalent aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • divalent linear aliphatic groups include, for example, methylene group, ethylene group, n-propylene group, n-butylene group, n-hexylene group, and n-heptylene group.
  • methylene groups are preferred from the viewpoint of resolution and manufacturing cost.
  • divalent branched aliphatic group examples include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group as a side chain to the above-mentioned divalent linear aliphatic group.
  • examples include structures having a group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
  • Examples of the substituent that the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group.
  • an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group.
  • unsubstituted compounds are preferred from the viewpoint of ease of synthesis.
  • Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
  • the number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
  • the divalent aromatic ring group preferably has 4 to 20 carbon atoms, more preferably 5 to 15 carbon atoms, and even more preferably 6 to 10 carbon atoms.
  • the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a fused ring.
  • Examples of the divalent aromatic hydrocarbon ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, Examples include triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.
  • the aromatic heterocycle in the aromatic heterocyclic group may be a single ring or a fused 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, each having two free valences.
  • benzimidazole ring examples include pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring.
  • benzene rings and naphthalene rings having two free valences are preferred, and benzene rings having two free valences are more preferred.
  • Examples of the substituents that the divalent aromatic ring group may have include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Among these, from the viewpoint of curability, non-substitution is preferred.
  • the group linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups includes one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic ring group.
  • Examples include groups linked to one or more of the following.
  • the number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. By setting the number of divalent aliphatic groups to the above lower limit or more, developability tends to improve. When the number of divalent aliphatic groups is below the upper limit, the film strength tends to be improved.
  • the number of divalent aliphatic groups is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3.
  • the number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less.
  • the film strength tends to improve.
  • the number of divalent aromatic ring groups is below the above upper limit, developability tends to improve.
  • the number of divalent aromatic ring groups is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3.
  • groups connecting one or more divalent aliphatic groups and one or more divalent aromatic ring groups include, for example, those represented by the following formulas (i-A) to (i-F). Examples include groups. Among these, a group represented by the following formula (i-A) is preferred from the viewpoint of skeletal rigidity and membrane hydrophobization. In the following, * represents a bond.
  • the benzene ring in formula (i) may be further substituted with any substituent.
  • substituents include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
  • the number of substituents is not particularly limited either, and may be one or two or more. Among these, unsubstituted compounds are preferred from the viewpoint of curability.
  • the partial structure represented by the formula (i) is preferably a partial structure represented by the following formula (i-1).
  • R a and R b have the same meanings as in formula (i) above.
  • R y represents a hydrogen atom or a polybasic acid residue. * represents a bond.
  • Formula ( The benzene ring in i-1) may be further substituted with any substituent.)
  • R y represents a hydrogen atom or a polybasic acid residue.
  • the polybasic acid residue means a monovalent or divalent group obtained by removing one or two OH groups from a polybasic acid.
  • the polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endo Examples include methylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
  • maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and more preferred are Tetrahydrophthalic acid and biphenyltetracarboxylic acid.
  • the partial structure represented by the above formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin (A12-1) may be one type or two or more types.
  • the number of partial structures represented by the formula (i) contained in one molecule of epoxy (meth)acrylate resin (A12-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and 3 or more. is more preferable, 10 or less is preferable, and 8 or less is even more preferable.
  • the number of partial structures By setting the number of partial structures to the above lower limit or more, developability tends to improve.
  • the number of partial structures below the above-mentioned upper limit the film strength tends to be improved.
  • the number of partial structures represented by the formula (i) contained in one molecule of epoxy (meth)acrylate resin (A12-1) is preferably 1 to 10, more preferably 2 to 8, and 3 to 8. is even more preferable.
  • the number of partial structures represented by the formula (i-1) contained in one molecule of epoxy (meth)acrylate resin (A12-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, It is more preferably 3 or more, more preferably 10 or less, and even more preferably 8 or less.
  • the number of partial structures By setting the number of partial structures to the above lower limit or more, developability tends to improve.
  • the number of partial structures below the above-mentioned upper limit the film strength tends to be improved.
  • the number of partial structures represented by the formula (i-1) contained in one molecule of epoxy (meth)acrylate resin (A12-1) is preferably 1 to 10, more preferably 2 to 8, and 3 -8 is more preferred.
  • epoxy (meth)acrylate resin (A12-1) Specific examples of the epoxy (meth)acrylate resin (A12-1) are listed below.
  • epoxy (meth)acrylate resin having a partial structure represented by the following general formula (ii-1) and the epoxy (meth)acrylate resin having a partial structure represented by the general formula (ii-2) will be described in detail. do. (Hereinafter, both may be collectively referred to as “epoxy (meth)acrylate resin (A12-2).")
  • R c represents a hydrogen atom or a methyl group.
  • R ⁇ represents a monovalent cyclic hydrocarbon group that may have a substituent.
  • q is an integer of 1 or more (The benzene ring in formula (ii-1) may be further substituted with any substituent.)
  • R ⁇ represents a monovalent cyclic hydrocarbon group which may have a substituent.
  • Examples of the monovalent cyclic hydrocarbon group in R ⁇ include an aliphatic ring group and an aromatic ring group.
  • the number of rings an aliphatic cyclic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, and more preferably 3 or less.
  • the film strength tends to be improved.
  • Developability tends to improve by controlling the number of rings in the aliphatic cyclic group to be equal to or less than the above upper limit.
  • the number of rings an aliphatic cyclic group has is preferably 1 to 6, more preferably 1 to 4, even more preferably 1 to 3, and particularly preferably 2 to 3.
  • the number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and especially 15 or less. preferable.
  • the number of carbon atoms is equal to or greater than the lower limit, the film strength tends to improve.
  • the number of carbon atoms is below the upper limit, developability tends to improve.
  • the aliphatic cyclic group preferably has 4 to 40 carbon atoms, more preferably 4 to 30 carbon atoms, even more preferably 6 to 20 carbon atoms, and particularly preferably 8 to 15 carbon atoms.
  • aliphatic ring in the aliphatic ring group include, for example, a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring.
  • adamantane rings are preferred from the viewpoint of achieving both film strength and developability.
  • the number of rings that the aromatic ring group has is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less.
  • the film strength tends to be improved.
  • Developability tends to improve by controlling the number of rings in the aromatic ring group to be equal to or less than the above upper limit.
  • the number of rings in the aromatic ring group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 5.
  • the aromatic ring group examples include aromatic hydrocarbon ring groups and aromatic heterocyclic groups.
  • the number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less.
  • the aromatic ring group preferably has 4 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, and even more preferably 6 to 15 carbon atoms.
  • aromatic ring in the aromatic ring group examples include, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring.
  • fluorene rings are preferred from the viewpoint of achieving both film strength and developability.
  • substituents that the cyclic hydrocarbon group R ⁇ may have include hydroxy group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert- Examples include alkyl groups having 1 to 5 carbon atoms such as butyl group, amyl group and isoamyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; nitro group; cyano group; and carboxy group. Among these, unsubstituted compounds are preferred from the viewpoint of ease of synthesis.
  • R ⁇ is preferably a monovalent aliphatic cyclic group, and more preferably an adamantyl group.
  • q represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less.
  • q is preferably an integer of 1 or more and 3 or less, more preferably an integer of 2 or more and 3 or less.
  • the benzene ring in formula (ii-1) may be further substituted with any substituent.
  • substituents include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
  • the number of substituents is not particularly limited either, and may be one or two or more. Among these, unsubstituted compounds are preferred from the viewpoint of curability.
  • R c represents a hydrogen atom or a methyl group.
  • R ⁇ represents a divalent cyclic hydrocarbon group which may have a substituent.
  • the benzene ring may be further substituted with any substituent.
  • R ⁇ represents a divalent cyclic hydrocarbon group which may have a substituent.
  • examples of the divalent cyclic hydrocarbon group for R ⁇ include a divalent aliphatic cyclic group and a divalent aromatic cyclic group.
  • the number of rings that the divalent aliphatic cyclic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less.
  • the film strength tends to be improved.
  • Developability tends to improve by controlling the number of rings in the divalent aliphatic group to be equal to or less than the above upper limit.
  • the number of rings that the divalent aliphatic cyclic group has is preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 5.
  • the carbon number of the divalent aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less.
  • the number of carbon atoms is equal to or greater than the lower limit, the film strength tends to improve.
  • the number of carbon atoms is below the upper limit, developability tends to improve.
  • the divalent aliphatic cyclic group preferably has 4 to 40 carbon atoms, more preferably 6 to 35 carbon atoms, and still more preferably 8 to 30 carbon atoms.
  • aliphatic ring in the divalent aliphatic ring include, for example, a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring.
  • adamantane rings are preferred from the viewpoint of achieving both film strength and developability.
  • the number of rings that the divalent aromatic ring group has is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less.
  • the film strength tends to be improved.
  • the number of rings included in the divalent aromatic ring group is equal to or greater than the lower limit, the film strength tends to be improved.
  • the number of rings that the divalent aromatic ring group has is preferably 1 to 10, more preferably 1 to 5, even more preferably 2 to 5, and particularly preferably 3 to 5.
  • divalent aromatic ring group examples include aromatic hydrocarbon ring groups and aromatic heterocyclic groups.
  • the carbon number of the divalent aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, even more preferably 10 or more, and preferably 40 or less, more preferably 30 or less, and 20 or less. More preferably, 15 or less is particularly preferable.
  • the divalent aromatic ring group preferably has 4 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, even more preferably 8 to 20 carbon atoms, and particularly preferably 10 to 15 carbon atoms.
  • aromatic ring in the divalent aromatic ring group examples include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring.
  • a benzene ring is preferred from the viewpoint of film strength and developability.
  • substituents that the divalent cyclic hydrocarbon group may have include a hydroxy group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group. , an alkyl group having 1 to 5 carbon atoms such as an amyl group and an isoamyl group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a nitro group; a cyano group; and a carboxy group.
  • unsubstituted is preferred from the viewpoint of ease of synthesis.
  • R ⁇ is preferably a divalent aliphatic cyclic group, and more preferably a divalent adamantane cyclic group.
  • the benzene ring in formula (ii-2) may be further substituted with any substituent.
  • substituents include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
  • the number of substituents is not particularly limited either, and may be one or two or more. Among these, unsubstituted compounds are preferred from the viewpoint of curability.
  • the partial structure represented by the formula (ii-1) is preferably a partial structure represented by the following formula (ii-3).
  • R c , R ⁇ , and q have the same meanings as in formula (ii-1) above.
  • R z1 and R z2 each independently represent a hydrogen atom or a polybasic acid residue. represent.
  • the partial structure represented by the formula (ii-2) is preferably a partial structure represented by the following formula (ii-4).
  • R c and R ⁇ have the same meanings as in formula (ii-2).
  • R v1 and R v2 each independently represent a hydrogen atom or a polybasic acid residue.
  • the polybasic acid residue means a monovalent or divalent group obtained by removing one or two OH groups from a polybasic acid.
  • the polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endo.
  • examples include methylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
  • maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and more preferred are Tetrahydrophthalic acid and biphenyltetracarboxylic acid.
  • the partial structure represented by may be one type or two or more types.
  • the number of partial structures represented by the formula (ii-1) contained in one molecule of epoxy (meth)acrylate resin (A12-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, Further, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. Resolution tends to improve by setting the number of partial structures represented by the formula (ii-1) to be equal to or greater than the lower limit. By setting the number of partial structures represented by the formula (ii-1) below the upper limit, developability tends to improve.
  • the number of partial structures represented by the formula (ii-1) contained in one molecule of epoxy (meth)acrylate resin (A12-2) is preferably 1 to 20, more preferably 1 to 15, and 3 -10 is more preferred.
  • the number of partial structures represented by the formula (ii-2) contained in one molecule of epoxy (meth)acrylate resin (A12-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, Further, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. Resolution tends to improve by setting the number of partial structures represented by the formula (ii-2) to be equal to or greater than the lower limit. By setting the number of partial structures represented by the formula (ii-2) below the upper limit, developability tends to improve.
  • the number of partial structures represented by the formula (ii-2) contained in one molecule of epoxy (meth)acrylate resin (A12-2) is preferably 1 to 20, more preferably 1 to 15, and 3 -10 is more preferred.
  • the number of partial structures represented by the formula (ii-3) contained in one molecule of epoxy (meth)acrylate resin (A12-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, Further, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. Resolution tends to improve by setting the number of partial structures represented by the formula (ii-3) to be equal to or greater than the lower limit. By setting the number of partial structures represented by formula (ii-3) below the upper limit, developability tends to improve.
  • the number of partial structures represented by the formula (ii-3) contained in one molecule of epoxy (meth)acrylate resin (A12-2) is preferably 1 to 20, more preferably 1 to 15, and 3 -10 is more preferred.
  • the number of partial structures represented by the formula (ii-4) contained in one molecule of epoxy (meth)acrylate resin (A12-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, Further, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
  • resolution tends to improve by setting the number of partial structures represented by formula (ii-4) above the lower limit value or more.
  • developability tends to be improved by setting the number of partial structures represented by the formula (ii-4) below the upper limit value.
  • the number of partial structures represented by the formula (ii-4) contained in one molecule of epoxy (meth)acrylate resin (A12-2) is preferably 1 to 20, more preferably 1 to 15, and 3 -10 is more preferred.
  • epoxy (meth)acrylate resin (hereinafter sometimes referred to as "epoxy (meth)acrylate resin (A12-3)) having a partial structure represented by the following general formula (iii) will be described in detail. .
  • R e represents a hydrogen atom or a methyl group.
  • ⁇ is a single bond, -CO-, an alkylene group that may have a substituent, or 2 that may have a substituent
  • the benzene ring in formula (iii) may be further substituted with any substituent. * represents a bond.
  • the partial structure represented by the above formula (iii) contained in the epoxy (meth)acrylate resin (A12-3) may be one type or two or more types.
  • ⁇ represents a single bond, -CO-, an alkylene group which may have a substituent, or a divalent cyclic hydrocarbon group which may have a substituent.
  • the alkylene group in ⁇ may be a straight chain or a branched chain, but from the viewpoint of development solubility it is preferably a straight chain, and from the viewpoint of development adhesion it is preferably a branched chain.
  • the number of carbon atoms in the alkylene group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less. When the number of carbon atoms is equal to or greater than the lower limit, the film strength tends to improve. When the number of carbon atoms is below the upper limit, developability tends to improve.
  • the alkylene group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 2 to 4 carbon atoms.
  • alkylene group examples include, for example, methylene group, ethylene group, propylene group, butylene group, hexylene group, and heptylene group, and from the viewpoint of achieving both film strength and developability, ethylene group and propylene group are preferable. , a propylene group is more preferred.
  • Examples of the substituent that the alkylene group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group.
  • an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxy group.
  • unsubstituted compounds are preferred from the viewpoint of ease of synthesis.
  • Examples of the divalent cyclic hydrocarbon group for ⁇ include a divalent aliphatic cyclic group and a divalent aromatic cyclic group.
  • the number of rings that the divalent aliphatic cyclic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less.
  • the film strength tends to be improved.
  • Developability tends to improve by controlling the number of rings in the divalent aliphatic group to be equal to or less than the above upper limit.
  • the number of rings that the divalent aliphatic cyclic group has is preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 5.
  • the carbon number of the divalent aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less.
  • the number of carbon atoms is equal to or greater than the lower limit, the film strength tends to improve.
  • the number of carbon atoms is below the upper limit, developability tends to improve.
  • the divalent aliphatic cyclic group preferably has 4 to 40 carbon atoms, more preferably 6 to 35 carbon atoms, and still more preferably 8 to 30 carbon atoms.
  • aliphatic ring in the divalent aliphatic ring include, for example, a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring.
  • adamantane rings are preferred from the viewpoint of achieving both film strength and developability.
  • the number of rings that the divalent aromatic ring group has is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less.
  • the film strength tends to be improved.
  • the number of rings included in the divalent aromatic ring group is equal to or greater than the lower limit, the film strength tends to be improved.
  • the number of rings that the divalent aromatic ring group has is preferably 1 to 10, more preferably 1 to 5, even more preferably 2 to 5, and particularly preferably 3 to 5.
  • the divalent aromatic ring group examples include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
  • the carbon number of the divalent aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, even more preferably 10 or more, and preferably 40 or less, more preferably 30 or less, and 20 or less. More preferably, 15 or less is particularly preferable.
  • the divalent aromatic ring group preferably has 4 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, even more preferably 8 to 20 carbon atoms, and particularly preferably 10 to 15 carbon atoms.
  • aromatic ring in the divalent aromatic ring group examples include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring.
  • a benzene ring is preferred from the viewpoint of achieving both film strength and developability.
  • substituents that the divalent cyclic hydrocarbon group may have include hydroxy group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert- Examples include alkyl groups having 1 to 5 carbon atoms such as butyl group, amyl group and isoamyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; and carboxy group. Among these, unsubstituted is preferred from the viewpoint of ease of synthesis.
  • ⁇ is preferably an alkylene group that may have a substituent, and more preferably a dimethylmethylene group.
  • the benzene ring in formula (iii) may be further substituted with any substituent.
  • substituents include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
  • the number of substituents is not particularly limited either, and may be one or two or more. Among these, unsubstituted compounds are preferred from the viewpoint of curability.
  • the partial structure represented by the formula (iii) is preferably a partial structure represented by the following formula (iii-1).
  • R e and ⁇ have the same meanings as in formula (iii) above.
  • R W represents a hydrogen atom or a polybasic acid residue. * represents a bond.
  • Formula (iii- The benzene ring in 1) may be further substituted with any substituent.)
  • the polybasic acid residue means a monovalent or divalent group obtained by removing one or two OH groups from a polybasic acid.
  • the polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endo.
  • examples include methylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
  • maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and more preferred are Tetrahydrophthalic acid and biphenyltetracarboxylic acid.
  • the number of partial structures represented by the formula (iii) contained in one molecule of epoxy (meth)acrylate resin (A12-3) is not particularly limited, but is preferably 1 or more, more preferably 5 or more, and 10 or more. is more preferable, 18 or less is preferable, and 15 or less is even more preferable.
  • the number of partial structures represented by the formula (iii) is equal to or greater than the lower limit, resolution tends to improve.
  • the number of partial structures represented by the formula (iii) contained in one molecule of epoxy (meth)acrylate resin (A12-3) is preferably 1 to 18, more preferably 5 to 15, and 10 to 15. is even more preferable.
  • the number of partial structures represented by the formula (iii-1) contained in one molecule of the epoxy (meth)acrylate resin (A12-3) is not particularly limited, but is preferably 1 or more, and more preferably 3 or more. It is preferably 5 or more, more preferably 18 or less, and even more preferably 15 or less. Resolution tends to improve by setting the number of partial structures represented by the formula (iii-1) to be equal to or greater than the lower limit. By setting the number of partial structures represented by the formula (iii-1) below the upper limit, developability tends to improve.
  • the number of partial structures represented by the formula (iii-1) contained in one molecule of epoxy (meth)acrylate resin (A12-3) is preferably 1 to 18, more preferably 3 to 15, and 5 -15 is more preferred.
  • epoxy (meth)acrylate resin (A12-3) Specific examples of the epoxy (meth)acrylate resin (A12-3) are listed below.
  • the content ratio of acrylic copolymer resin (A11) and acrylic copolymer resin (A11) is The total content with the epoxy (meth)acrylate resin (A12) is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, particularly preferably 40% by mass or more, and The content is preferably 90% by mass or less, more preferably 75% by mass or less, even more preferably 60% by mass or less, and particularly preferably 50% by mass or less. There is a tendency for the residue to be reduced by making this content ratio equal to or higher than the lower limit value.
  • Adhesion tends to improve by making this content ratio below the above-mentioned upper limit.
  • the alkali-soluble resin contains both acrylic copolymer resin (A11) and epoxy (meth)acrylate resin (A12), for example, acrylic copolymer resin (A11) and epoxy (meth)acrylate resin (A12)
  • the alkali-soluble resin (a) in the present invention may contain other alkali-soluble resins in addition to the acrylic copolymer resin (A11) and the epoxy (meth)acrylate resin (A12).
  • the content of the alkali-soluble resin (a) in the photosensitive resin composition of the present invention is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, based on the total solid content of the photosensitive resin composition. , more preferably 20% by mass or more, still more preferably 30% by mass or more, even more preferably 40% by mass or more, particularly preferably 50% by mass or more, and usually 90% by mass or less, preferably 80% by mass or less, and more. Preferably it is 70% by mass or less.
  • this content ratio is equal to or higher than the lower limit value, resolution tends to be improved. There is a tendency for surface hardness to improve by making this content ratio below the above-mentioned upper limit.
  • the content ratio of the alkali-soluble resin (a) to the total solid content of the photosensitive resin composition is preferably 5 to 90% by mass, more preferably 10 to 90% by mass, even more preferably 20 to 80% by mass, and even more preferably 30 to 90% by mass. Even more preferably 80% by weight, particularly preferably 40 to 70% by weight, particularly preferably 50 to 70% by weight.
  • the sum total of the content ratio of (c) ethylenically unsaturated compound and the content ratio of (a) alkali-soluble resin, which will be described later, with respect to the total solid content of the photosensitive resin composition is not particularly limited, but is preferably 10% by mass or more, and 30% by mass or more. More preferably at least 50% by mass, even more preferably at least 60% by mass, and preferably at most 90% by mass, more preferably at most 85% by mass, even more preferably at most 80% by mass, and even more preferably at most 75% by mass. % or less is more preferable. Adhesion tends to improve by making this content ratio equal to or higher than the lower limit value.
  • the total content of (c) ethylenically unsaturated compound and (a) alkali-soluble resin relative to the total solid content of the photosensitive resin composition is preferably 10 to 90% by mass, and 30 to 80% by mass. It is more preferably 50 to 80% by mass, even more preferably 60 to 75% by mass.
  • the photosensitive resin composition of the present invention contains (b) a photopolymerization initiator.
  • the photopolymerization initiator is a component that has the function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating polymerization-active radicals. If necessary, in addition to the photopolymerization initiator (b), additives such as a polymerization accelerator (chain transfer agent) and a sensitizing dye may be added.
  • photopolymerization initiator (b) a photopolymerization initiator commonly used in this field can be used.
  • photopolymerization initiators include, for example, metallocene compounds containing titanocene compounds described in Japanese Patent Application Laid-open Nos. 59-152396 and 61-151197; Japanese Patent Applications 2000-56118; N-aryl- ⁇ -amino acids such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, and N-phenylglycine described in Japanese Patent Publication No.
  • N-aryl- ⁇ -amino acid salts N-aryl- ⁇ -amino acid esters, etc., radical activators, ⁇ -aminoalkylphenone derivatives;
  • Examples include oxime ester compounds described in publications and the like.
  • 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), Examples include di(methylcyclopentadienyl) titanium bis(2,6-difluorophenyl) and dicyclopentadienyl titanium [2,6-di-fluoro-3-
  • hexaarylbiimidazole derivatives examples include 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'-methoxy phenyl)-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)- methyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)- Examples include s-triazine.
  • ⁇ -aminoalkylphenone derivatives examples include 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morphol) Linophenyl)-butanone-1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one is mentioned.
  • oxime ester compounds are particularly effective in terms of sensitivity and plate-making properties.
  • an alkali-soluble resin containing a phenolic hydroxyl group there is a disadvantage in terms of sensitivity, so oxime ester compounds with excellent sensitivity are particularly useful.
  • Oxime ester compounds have a high photoreaction quantum yield and a high activity of the generated radicals, so they have high sensitivity and are stable against thermal reactions, making it possible to create highly sensitive photosensitive resin compositions in small amounts. It is possible to obtain.
  • oxime ester compounds examples include compounds represented by the following general formula (b1).
  • R 21a represents a hydrogen atom, an alkyl group that may have a substituent, or an aromatic ring group that may have a substituent.
  • R 21b represents an arbitrary substituent containing an aromatic ring.
  • R 22a represents an alkanoyl group which may have a substituent or an aroyl group which may have a substituent.
  • nx represents an integer of 0 or 1.
  • R 21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
  • the number of carbon atoms in the alkyl group in R 21a is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less. It is.
  • Specific examples of the alkyl group include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, and a cyclohexylethyl group.
  • substituents that the alkyl group may have include aromatic ring groups, hydroxyl groups, carboxy groups, halogen atoms, amino groups, amide groups, 4-(2-methoxy-1-methyl)ethoxy-2 -methylphenyl group and N-acetyl-N-acetoxyamino group, and from the viewpoint of sensitivity, N-acetyl-N-acetoxyamino group is preferable.
  • Examples of the aromatic ring group for R 21a include aromatic hydrocarbon ring groups and aromatic heterocyclic groups.
  • the number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the photosensitive resin composition. Further, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and even more preferably 12 or less.
  • aromatic ring group examples include, for example, phenyl group, naphthyl group, pyridyl group, and furyl group. Among these, from the viewpoint of developability, phenyl group and naphthyl group are preferable, and phenyl group is more preferable.
  • substituents 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 a group in which these substituents are linked. From the viewpoint of developability, an alkyl group, an alkoxy group, or a group formed by connecting these groups is preferable, and a connected alkoxy group is more preferable.
  • R 21b represents an arbitrary substituent containing an aromatic ring.
  • R 21b is preferably an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, an optionally substituted fluorenyl group, an optionally substituted diphenyl sulfide group, or an optionally substituted diphenyl sulfide group.
  • a good example is the indolyl group.
  • an optionally substituted carbazolyl group is preferred from the viewpoint of sensitivity.
  • R 22a represents an alkanoyl group which may have a substituent or an aroyl group which may have a substituent.
  • the number of carbon atoms in the alkanoyl group in R 22a is not particularly limited, but is preferably 2 or more from the viewpoint of solubility in a solvent and sensitivity. Further, it is preferably 20 or less, more preferably 15 or less, even more preferably 10 or less, even more preferably 5 or less.
  • Specific examples of the alkanoyl group include, for example, an acetyl group, an ethyl group, a propanoyl group, and a butanoyl group.
  • alkanoyl group may have include aromatic ring groups, hydroxyl groups, carboxy groups, halogen atoms, amino groups, and amide groups.From the viewpoint of ease of synthesis, unsubstituted It is preferable that there be.
  • the number of carbon atoms in the aroyl group in R 22a is not particularly limited, but is preferably 7 or more from the viewpoint of solubility in solvents and sensitivity. Further, it is preferably 20 or less, preferably 15 or less, and more preferably 10 or less. Specific examples of the aroyl group include benzoyl group and naphthoyl group. Examples of the substituent 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, and from the viewpoint of ease of synthesis, it should be unsubstituted. is preferred.
  • R 22a is preferably an alkanoyl group that may have a substituent, more preferably an unsubstituted alkanoyl group, and even more preferably an acetyl group.
  • Examples of the oxime ester compound represented by the formula (b1) include Japanese Patent No. 4454067, International Publication No. 2002/100903, International Publication No. 2012/45736, International Publication No. 2015/36910, International Publication No. Publication No. 2006/18973, International Publication No. 2008/78678, Japanese Patent No. 4818458, International Publication No. 2005/80338, International Publication No. 2008/75564, International Publication No. 2009/131189, International Publication No. 2010 Photopolymerization initiators described in International Publication No./133077, International Publication No. 2010/102502, and International Publication No. 2012/68879 can be used.
  • the photopolymerization initiator may be used alone or in combination of two or more types.
  • the photopolymerization initiator may contain a sensitizing dye and a polymerization accelerator depending on the wavelength of the image exposure light source, if necessary, for the purpose of increasing the sensitivity.
  • the sensitizing dye include xanthene dyes described in Japanese Patent Application Laid-Open No. 4-221958 and Japanese Patent Application Publication No. 4-219756, Japanese Patent Application Publication No. 3-239703, and Japanese Patent Application Publication No. 5-289335.
  • sensitizing dyes preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule.
  • Particularly preferred sensitizing dyes include, for example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3' - Benzophenone compounds such as diaminobenzophenone and 3,4-diaminobenzophenone; 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-diethy
  • polymerization accelerator examples include aromatic amines such as ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone, and 4-dimethylaminopropiophenone; n-butylamine; , N-methyldiethanolamine, and 2-dimethylaminoethyl benzoate.
  • aromatic amines such as ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone, and 4-dimethylaminopropiophenone
  • n-butylamine , N-methyldiethanolamine, and 2-dimethylaminoethyl benzoate.
  • One type of polymerization accelerator may be used alone, or two or more types may be used in combination.
  • a chain transfer agent may also be used in combination with the photopolymerization initiator (b).
  • the chain transfer agent include mercapto group-containing compounds and carbon tetrachloride, and it is more preferable to use a mercapto group-containing compound because it tends to have a high chain transfer effect. This is thought to be because bond cleavage is likely to occur due to the small S--H bond energy, and hydrogen abstraction reactions and chain transfer reactions are likely to occur, which is effective for improving sensitivity and surface hardening.
  • Examples of mercapto group-containing compounds include 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4(3H)-quinazoline, ⁇ - Mercapto group-containing compounds with aromatic rings such as mercaptonaphthalene and 1,4-dimethylmercaptobenzene; hexanedithiol, decanedithiol, butanediol bis(3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol Bis(3-mercaptopropionate), ethylene glycol bisthioglycolate, trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tristhioglycolate, trishydroxyethyltristhiopropionate, pentaerythritol tetrakis (3-mercapto
  • 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred among mercapto group-containing compounds having an aromatic ring, and trimethylolpropane tris (3-mercaptopropane tris) is preferred among aliphatic mercapto group-containing compounds.
  • Various types of these can be used singly or in combination of two or more types.
  • 2-mercaptobenzothiazole 2-mercaptobenzimidazole
  • 2-mercaptobenzoxazole 2-mercaptobenzoxazole
  • 2-mercaptobenzothiazole 2-mercaptobenzoimidazole
  • 2-mercaptobenzothiazole and 2-mercaptobenzimidazole may be used in combination.
  • the photopolymerization initiator (b) it is preferable to use it in combination with biimidazole derivatives.
  • pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate).
  • one or more selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoxazole, and pentaerythritol tetrakis (3-mercaptopropionate) It is preferable to use one or more selected from the group consisting of pentaerythritol tetrakis (3-mercaptobutyrate) in combination with (b) a photopolymerization initiator.
  • the content ratio of the photopolymerization initiator (b) in the photosensitive resin composition of the present invention is not particularly limited, but is usually 0.01% by mass or more, preferably 0.01% by mass or more, based on the total solid content of the photosensitive resin composition. 1% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, particularly preferably 3% by mass or more, and usually 25% by mass or less, preferably 20% by mass or less, more preferably 15% by mass.
  • the content is more preferably 10% by mass or less, even more preferably 7% by mass or less, particularly preferably 5% by mass or less.
  • the blending ratio of (b) photopolymerization initiator to (c) ethylenically unsaturated compound described below in the photosensitive resin composition is 5 parts by mass per 100 parts by mass of (c) ethylenically unsaturated compound. parts by weight or more, more preferably 10 parts by weight or more, further preferably 20 parts by weight or more, even more preferably 25 parts by weight or more, particularly preferably 30 parts by weight or more, and preferably 200 parts by weight or less, 100 parts by weight. The following is more preferred, further preferably 50 parts by mass or less, particularly preferably 40 parts by mass or less.
  • the photosensitive resin composition of the present invention contains (c) an ethylenically unsaturated compound. (c) It is thought that the inclusion of an ethylenically unsaturated compound increases the curability of the coating film and improves its adhesion.
  • the ethylenically unsaturated compound (c) in the photosensitive resin composition of the present invention includes an ethylenically unsaturated compound (c1') containing an alkylene oxide group, and in particular, an ethylenically unsaturated compound containing an alkylene oxide group and an ethylenically unsaturated compound (c1'). It is preferably an ethylenically unsaturated compound (c1) having three or more groups, and more preferably an ethylenically unsaturated compound having an alkylene oxide group in its side chain.
  • Ethylenically unsaturated compound means a compound having one or more ethylenically unsaturated bonds in its molecule, but it has polymerizability, crosslinkability, and associated solubility of exposed and non-exposed areas in developer solution.
  • the compound has two or more ethylenically unsaturated bonds in the molecule, and the unsaturated bonds are derived from (meth)acryloyloxy groups, that is, ( More preferably, it is a meth)acrylate compound.
  • the ethylenically unsaturated compound (c1) has three or more alkylene oxide-modified ethylenically unsaturated groups.
  • the ethylenically unsaturated compound (c) it is particularly desirable to use a polyfunctional ethylenically monomer having two or more ethylenically unsaturated bonds in one molecule.
  • the number of ethylenically unsaturated groups that the polyfunctional ethylenic monomer has is not particularly limited, but is preferably 2 or more, more preferably 3 or more, and preferably 15 or less, more preferably 10.
  • the number is more preferably 8 or less, particularly preferably 6 or less.
  • the number of ethylenically unsaturated groups is less than or equal to the above upper limit, developability tends to be better.
  • the number of ethylenically unsaturated groups that the polyfunctional ethylenic monomer has is preferably 2 to 15, more preferably 2 to 10, even more preferably 2 to 8, even more preferably 3 to 8. , 3 to 6 are particularly preferred.
  • ethylenically unsaturated compound (c1) in the ethylenically unsaturated compound (c1') include, for example, an ester of an aliphatic polyhydroxy compound containing an alkylene oxide group in the side chain and an unsaturated carboxylic acid. Can be mentioned.
  • alkylene oxide group examples include polyethylene glycol and polypropylene glycol having any repeating unit.
  • Examples of the aliphatic polyhydroxy compound include ethylene glycol, triethylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, dipentaerythritol, glycerol, and the like.
  • Examples of the unsaturated carboxylic acid include acrylic acid and methacrylic acid.
  • the ethylenically unsaturated compound (c1) preferably contains an ethylenically unsaturated compound (c1-1) represented by the following general formula (c1-1-1).
  • (X in formula (c1-1-1) is represented by the following general formula (c1-1-2). X may be different or the same.
  • Y is a methyl group or the following general formula (c1-1-2). (Represented by formula (c1-1-4).)
  • R 1 in formula (c1-1-2) represents an alkylene group having 2 to 4 carbon atoms.
  • a represents an integer of 1 to 9.
  • R2 is represented by the following general formula (c1-1-3). * represents a bond.
  • R 3 in formula (c1-1-3) represents a hydrogen atom or a methyl group. * represents a bond.
  • Y in the above general formula (c1-1-1) is preferably represented by the above general formula (c1-1-4), and in the above general formula (c1-1-4), It is preferable that m is 1. Furthermore, from the viewpoint of ease of synthesis, it is preferable that X be the same.
  • the alkylene group having 2 to 4 carbon atoms in R 1 in formula (c1-1-2) may be linear, branched, cyclic, or a combination thereof.
  • a linear alkylene group is preferred from the viewpoint of solvent solubility and solvent resistance.
  • the number of carbon atoms in the alkylene group is not particularly limited as long as it is 2 to 4, but 2 to 3 is preferable, and 2 is more preferable. When the carbon number is within the above range, coating film sensitivity and solvent resistance tend to improve.
  • Examples of the alkylene group for R 1 include ethylene group, n-propylene group, n-butylene group, and isopropylene group. From the viewpoint of dissolution rate, n-propylene group and ethylene group are preferred, and ethylene group is more preferred.
  • a in the general formula (c1-1-2) is preferably an integer of 2 to 9, more preferably an integer of 2 to 4.
  • the ethylenically unsaturated compound (c) in the photosensitive resin composition of the present invention has an alkylene oxide group, and in addition to the ethylenically unsaturated compound (c1) having three or more ethylenically unsaturated groups, Other ethylenically unsaturated compounds may be included.
  • ethylenically unsaturated compounds used here mean compounds having one or more ethylenically unsaturated bonds in the molecule, but they have polymerizability, crosslinking properties, and associated development of exposed and non-exposed areas. From the viewpoint of expanding the difference in liquid solubility, it is preferable that the compound has two or more ethylenically unsaturated bonds in the molecule, and the unsaturated bond is derived from a (meth)acryloyloxy group. In other words, it is more preferably a (meth)acrylate compound.
  • the other ethylenically unsaturated compound it is particularly desirable to use a polyfunctional ethylenically monomer having two or more ethylenically unsaturated bonds in one molecule.
  • the number of ethylenically unsaturated groups that the polyfunctional ethylenic monomer has is not particularly limited, but is preferably 2 or more, more preferably 3 or more, and preferably 15 or less, more preferably 10. The number is more preferably 8 or less, particularly preferably 6 or less.
  • the number of ethylenically unsaturated groups is less than or equal to the above upper limit, developability tends to be better.
  • the number of ethylenically unsaturated groups that the polyfunctional ethylenic monomer has is preferably 2 to 15, more preferably 2 to 10, even more preferably 2 to 8, even more preferably 3 to 8. , 3 to 6 are particularly preferred.
  • esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatic Examples include esters obtained by an esterification reaction between a polyhydric hydroxy compound such as a group polyhydroxy compound, and an unsaturated carboxylic acid and a polybasic carboxylic acid.
  • ester of the aliphatic polyhydroxy compound and unsaturated carboxylic acid examples include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate.
  • Acrylic acid esters of aliphatic polyhydroxy compounds such as acrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, and methacrylates in which the acrylate of these exemplified compounds is replaced with methacrylate.
  • Acid esters may also be mentioned, such as itaconate esters in place of itaconate, crotonate esters in place of crotonate or maleate esters in place of maleate.
  • esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic esters and methacrylates of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.
  • esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic esters and methacrylates of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.
  • acid esters include acid esters.
  • Esters obtained by the esterification reaction of polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids are not necessarily single products, but are typical examples. Specific examples include, for example, condensates of acrylic acid, phthalic acid, and ethylene glycol; condensates of acrylic acid, maleic acid, and diethylene glycol; condensates of methacrylic acid, terephthalic acid, and pentaerythritol; acrylic acid, adipic acid. , a condensate of butanediol and glycerin;
  • examples of other polyfunctional ethylenic monomers used in the present invention include, for example, a polyisocyanate compound and a hydroxyl group-containing (meth)acrylic ester, or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth)acrylic ester.
  • Urethane (meth)acrylates such as those obtained by reacting; Epoxy acrylates such as addition reaction products of polyvalent epoxy compounds and hydroxy (meth)acrylate or (meth)acrylic acid; Acrylamides such as ethylene bisacrylamide ; Allyl esters such as diallyl phthalate; Vinyl group-containing compounds such as divinyl phthalate.
  • urethane (meth)acrylates examples include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U- 10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B, Examples include UV-7600B, UV-7605B, UV-7630B, and UV7640B (manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd.).
  • esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids or urethane (meth)acrylates as other ethylenically unsaturated compounds from the viewpoint of resolution, and trimethylolpropanetri Acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, 2,2,2-tris(meth)acryloyloxymethylethylphthalate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri( It is more preferable to use meth)acrylate, a dibasic acid anhydride adduct of dipentaerythritol penta(meth)acrylate, and a dibasic acid anhydride adduct of pentaerythritol tri(meth)acrylate. These may be used alone or in combination of two or more.
  • the molecular weight of the ethylenically unsaturated compound (c) is not particularly limited, but from the viewpoint of resolution, it is preferably 100 or more, more preferably 300 or more, particularly preferably 400 or more, and preferably 2000 or more. It is more preferably 1500 or less.
  • the molecular weight of the ethylenically unsaturated compound (c) is preferably 100 to 2,000, more preferably 300 to 2,000, particularly preferably 400 to 1,500.
  • the number of carbon atoms in the ethylenically unsaturated compound is not particularly limited, but from the viewpoint of resolution, it is preferably 7 or more, more preferably 10 or more, even more preferably 15 or more, preferably 50 or less, and more preferably 40 Below, it is more preferably 30 or less, particularly preferably 20 or less.
  • the number of carbon atoms in the ethylenically unsaturated compound (c) is preferably 7 to 50, more preferably 10 to 40, even more preferably 15 to 30, even more preferably 15 to 20.
  • the content of the ethylenically unsaturated compound (c) in the photosensitive resin composition of the present invention is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more based on the total solid content of the photosensitive resin composition.
  • the content is at least 20% by mass, preferably at most 20% by mass, and more preferably at most 10% by mass.
  • this content ratio is equal to or higher than the lower limit value, the dissolution rate tends to be improved.
  • the taper angle tends to be good.
  • the content of the ethylenically unsaturated compound (c) based on the total solid content of the photosensitive resin composition is preferably 1 to 20% by mass, more preferably 5 to 10% by mass.
  • the content ratio of the ethylenically unsaturated compound (c1) in the ethylenically unsaturated compound (c) is not particularly limited, but is preferably 30% by mass based on the total solid content of the ethylenically unsaturated compound (c). % or more, more preferably 50% by mass or more, still more preferably 80% by mass or more, particularly preferably 100% by mass. By setting this content to the lower limit value or more, the dissolution rate tends to become faster.
  • the mass ratio of the (a) alkali-soluble resin and the (c) ethylenically unsaturated compound in the photosensitive resin composition is 5 or more, preferably 6 or more, more preferably 8 or more. This mass ratio is preferably 15 or less, more preferably 12 or less.
  • the dissolution rate tends to be faster by keeping the amount of the above-mentioned upper limit below.
  • the mass ratio to the compound ((a) alkali-soluble resin/(c) ethylenic saturated compound) is preferably 5 to 15, more preferably 6 to 12, and even more preferably 8 to 12. .
  • the content (mass) of the alkali-soluble resin (a) and the ethylenically unsaturated compound (c) in the photosensitive resin composition is determined by the mole of each ethylenically unsaturated bond.
  • the total double bond equivalent of the (a) alkali-soluble resin and (c) ethylenically unsaturated compound, which is a weighted average value of the numerical values divided by the number, is 350 g/mol or more, preferably 380 g/mol or more, and more. Preferably it is 410 g/mol or more.
  • this total double bond equivalent is 600 g/mol or less, preferably 550 g/mol or less, more preferably 500 g/mol or less. If this total double bond equivalent is equal to or greater than the above lower limit, the taper angle tends to become low. If this total double bond equivalent is below the above upper limit, there is a tendency that the solubility of the resist can be ensured while obtaining a sufficient crosslinking density.
  • the total double bond equivalent is preferably 350 to 600 g/mol, more preferably 380 to 550 g/mol, even more preferably 410 to 500 g/mol.
  • the photosensitive resin composition of the present invention preferably satisfies both the above-mentioned (a) alkali-soluble resin/(c) ethylenically unsaturated compound amount ratio and total double bond equivalent.
  • the photosensitive resin composition of the present invention may contain (d) a colorant.
  • a coloring agent By containing a coloring agent, it is possible to obtain an appropriate light absorption property, particularly when used for forming a light blocking member such as a colored partition wall, an appropriate light blocking property.
  • the content ratio of the colorant is not particularly limited, but from the viewpoint of light-shielding properties, it is preferably 5% by mass or more, more preferably 10% by mass or more, 15% by mass or more based on the total solid content of the photosensitive resin composition. Particularly preferably % by mass or more.
  • the content is preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less.
  • the colorant (d) used in the present invention is not particularly limited, but preferably contains an organic pigment from the viewpoint of dielectric constant and resolution.
  • organic pigment is not particularly limited, but from the viewpoint of light-shielding properties, organic black pigments and organic colored pigments are preferred, and black pigments are more preferred.
  • the organic colored pigment means an organic pigment exhibiting a color other than black, and includes, for example, a red pigment, an orange pigment, a blue pigment, a violet pigment, a green pigment, and a yellow pigment.
  • One type of organic coloring pigment may be used alone, or two or more types may be used in combination.
  • organic pigments are not particularly limited, but examples thereof include azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. Specific examples of pigments that can be used are shown below using pigment numbers. Terms such as "C.I. Pigment Red 2" listed below mean color index (C.I.).
  • red pigments examples include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200
  • C. I. It is preferable to use Pigment Red 177, 254, and 272.
  • a red pigment with low ultraviolet absorbance When curing the photosensitive resin composition with ultraviolet rays, it is preferable to use a red pigment with low ultraviolet absorbance, and from this point of view, C.I. I. It is more preferable to use Pigment Red 254 and 272.
  • orange pigments examples include 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.
  • C. I. It is preferable to use Pigment Orange 13, 43, 64, and 72.
  • an orange pigment with a low ultraviolet absorbance and from this point of view, C.I. I. It is more preferable to use pigment orange 64 and 72, and C.I. I. It is more preferable to use Pigment Orange 64.
  • blue pigments examples include 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.
  • 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. Pigment Blue 15:6, 16, 60 is preferably used.
  • When curing the photosensitive resin composition with ultraviolet rays it is preferable to use a blue pigment with low ultraviolet absorbance, and from this point of view, C.I. I. It is more preferable to use Pigment Blue 60.
  • Examples of the purple pigment include 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, and 50.
  • C.I. I. Pigment Violet 19 23, more preferably C.I. I. Pigment Violet 23 may be mentioned.
  • C. I. It is preferable to use Pigment Violet 23, 29.
  • organic coloring pigments that can be used in addition to red pigments, orange pigments, blue pigments, and purple pigments include green pigments and yellow pigments.
  • green pigments examples include 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. Among these, C. I. Pigment Green 7 and 36 can be mentioned.
  • yellow pigments examples include C.I. I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184
  • red pigment C. I. Pigment Red 177, 254, 272
  • Orange pigment C. I. Pigment orange 43, 64, 72
  • Blue pigment C. I. Pigment Blue 15:6,60 Purple pigment: C. I. pigment violet 23, 29
  • Organic black pigments are not particularly limited, but from the viewpoint of light-shielding properties, compounds represented by the following general formula (d1) (hereinafter also referred to as “compound (d1)”), geometric isomers of compound (d1), etc.
  • An organic black pigment (hereinafter referred to as “an organic black pigment represented by the general formula (d1)") containing at least one selected from the group consisting of: ) is preferable.
  • R 11 and R 16 each independently represent a hydrogen atom, CH 3 , CF 3 , a fluorine atom, or a chlorine atom.
  • At least one combination selected from the group consisting of R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 17 and R 18 , R 18 and R 19 , and R 19 and R 20 is or may be bonded to each other via an oxygen atom, a sulfur atom, an NH or NR 21 bridge.
  • R 21 and R 22 each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or a cycloalkenyl group having 3 to 12 carbon atoms; Represents 2 to 12 alkynyl groups.
  • compound (d1) When compound (d1) is anionic, its charge can be transferred to any known suitable cation, such as a metal, organic, inorganic or metal-organic cation, in particular an alkali metal, alkaline earth metal, transition metal, primary ammonium , secondary ammonium, tertiary ammonium such as trialkylammonium, quaternary ammonium such as tetraalkylammonium, or a salt compensated with an organometallic complex. Moreover, when the geometric isomer of compound (d1) is anionic, a similar salt is preferable.
  • a metal, organic, inorganic or metal-organic cation in particular an alkali metal, alkaline earth metal, transition metal, primary ammonium , secondary ammonium, tertiary ammonium such as trialkylammonium, quaternary ammonium such as tetraalkylammonium, or a salt compensated with an organometallic complex.
  • R 12 , R 14 , R 15 , R 17 , R 19 and R 20 are each independently preferably a hydrogen atom, a fluorine atom or a chlorine atom, more preferably a hydrogen atom.
  • R 13 and R 18 each independently preferably represent a hydrogen atom, NO 2 , OCH 3 , OC 2 H 5 , bromine atom, chlorine atom, CH 3 , C 2 H 5 , N(CH 3 ) 2 , N(CH 3 ) ( C2H5 ), N( C2H5 ) 2 , SO3H or SO3- , more preferably a hydrogen atom or SO3H , particularly preferably a hydrogen atom .
  • R 11 and R 16 are each independently preferably a hydrogen atom, CH 3 or CF 3 , more preferably a hydrogen atom.
  • at least one combination selected from the group consisting of R 11 and R 16 , R 12 and R 17 , R 13 and R 18 , R 14 and R 19 , and R 15 and R 20 is the same, and more preferably R 11 is the same as R 16 , R 12 is the same as R 17 , R 13 is the same as R 18 , R 14 is the same as R 19 , and R 15 is the same as R 20 . be.
  • Examples of the alkyl group having 1 to 12 carbon atoms in R 21 and R 22 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, 2 -Methylbutyl group, n-pentyl group, 2-pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, n-heptyl group, n-octyl group, 1,1,3,3- These are tetramethylbutyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, and dodecyl group.
  • the cycloalkyl group having 3 to 12 carbon atoms for R 21 and R 22 is, for example, a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a trimethylcyclohexyl group, a tuzyl group, a norbornyl group. , bornyl group, norcalyl group, calyl group, menthyl group, norpinyl group, pinyl group, adamantan-1-yl group, and adamantan-2-yl group.
  • the alkenyl group having 2 to 12 carbon atoms in R 21 and R 22 is, for example, a vinyl group, an allyl group, a 2-propen-2-yl group, a 2-buten-1-yl group, a 3-buten-1-yl group. , 1,3-butadien-2-yl group, 2-penten-1-yl group, 3-penten-2-yl group, 2-methyl-1-buten-3-yl group, 2-methyl-3-butene -2-yl group, 3-methyl-2-buten-1-yl group, 1,4-pentadien-3-yl group, hexenyl group, octenyl group, nonenyl group, decenyl group, and dodecenyl group.
  • the cycloalkenyl group having 3 to 12 carbon atoms in R 21 and R 22 is, for example, a 2-cyclobuten-1-yl group, a 2-cyclopenten-1-yl group, a 2-cyclohexen-1-yl group, a 3-cyclohexen- 1-yl group, 2,4-cyclohexadien-1-yl group, 1-p-menthen-8-yl group, 4(10)-thujen-10-yl group, 2-norbornen-1-yl group, 2 , 5-norbornadien-1-yl group, 7,7-dimethyl-2,4-norcaladien-3-yl group, and camphenyl group.
  • the alkynyl group having 2 to 12 carbon atoms in R 21 and R 22 is, for example, 1-propyn-3-yl group, 1-butyn-4-yl group, 1-pentyn-5-yl group, 2-methyl-3 -butyn-2-yl group, 1,4-pentadiyn-3-yl group, 1,3-pentadiyn-5-yl group, 1-hexyn-6-yl group, cis-3-methyl-2-penten-4 -yn-1-yl group, trans-3-methyl-2-penten-4-yn-1-yl group, 1,3-hexadiyn-5-yl group, 1-octyn-8-yl group, 1-nonine -9-yl group, 1-decyn-10-yl group, and 1-dodecyn-12-yl group.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the organic black pigment represented by formula (d1) is preferably a compound represented by the following structural formula (2) (hereinafter also referred to as "compound (2)”), and a geometric isomer of compound (2).
  • organic black pigment of compound (2) is the trade name Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF).
  • the organic black pigment is preferably used after being dispersed using the dispersant, solvent, and method described below. Furthermore, the presence of the sulfonic acid derivative of compound (d1), especially the sulfonic acid derivative of compound (2), during dispersion may improve dispersibility and storage stability. It is preferable to include.
  • organic black pigments other than compound (d1) examples include aniline black and perylene black.
  • inorganic pigments may be contained in addition to these organic pigments.
  • the inorganic pigment it is preferable to contain an inorganic black pigment from the viewpoint of light-shielding properties.
  • 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 image characteristics.
  • examples of carbon black include the following carbon blacks.
  • Carbon black coated with resin may be used.
  • Use of resin-coated carbon black has the effect of improving adhesion to glass substrates and volume resistivity.
  • the resin-coated carbon black for example, carbon black described in Japanese Patent Application Laid-Open No. 09-71733 can be suitably used.
  • Resin-coated carbon black is preferably used in terms of volume resistivity and dielectric constant.
  • the total content of Na and Ca be 100 ppm or less in the carbon black to be subjected to the resin coating treatment.
  • Carbon black usually contains Na, Ca, K, Mg, Al, Fe, etc. mixed in from raw material oil, combustion oil (or gas), reaction stop water, granulation water, and reactor materials during manufacturing. Contains ash with a composition of Among these, Na and Ca are generally contained in amounts of several hundred ppm or more each, but by reducing their content, it is possible to suppress penetration into transparent electrodes (ITO) and other electrodes, and to This tends to prevent short circuits.
  • ITO transparent electrodes
  • a method for reducing the content of ash containing Na and Ca is to carefully select materials with as low a content as possible as raw material oil, fuel oil (or gas), and reaction termination water when producing carbon black. This can be achieved by minimizing the amount of alkaline substances added to adjust the structure.
  • Another method includes a method in which carbon black produced from a furnace is washed with water, hydrochloric acid, etc. to dissolve and remove Na and Ca.
  • the resin-coated carbon black is preferably a so-called acidic carbon black having a pH of 6 or less. Since the dispersion diameter (agglomerate diameter) in water becomes small, it is possible to coat even minute units, which is preferable. Furthermore, it is preferable that the average particle diameter is 40 nm or less and the dibutyl phthalate (DBP) absorption amount is 140 mL/100 g or less. By setting it within the above range, a coating film with good light-shielding properties tends to be obtained.
  • DBP dibutyl phthalate
  • the average particle diameter refers to the number average particle diameter, and particle image analysis involves taking several fields of view of photographs taken at tens of thousands of magnifications using an electron microscope, and measuring approximately 2000 to 3000 particles in these photographs using an image processing device. means the equivalent circle diameter determined by
  • Method 3 Mix and stir the resin solution and suspension prepared in the same manner as above to granulate the carbon black and resin, and then separate and heat the resulting granules to remove the remaining solvent and water. ..
  • a carboxylic acid such as maleic acid or fumaric acid is dissolved in the above-mentioned solvent, carbon black is added, mixed and dried, the solvent is removed to obtain carboxylic acid-impregnated carbon black, and a resin is added to this.
  • Method of dry blending 4 A suspension is prepared by stirring the reactive group-containing monomer component constituting the resin to be coated with water at high speed, and after polymerization, the reactive group-containing resin is obtained from the polymer suspension by cooling.
  • the type of resin to be coated is not particularly limited, but synthetic resins are common, and resins that have a benzene ring in their structure have a stronger action as an amphoteric surfactant. Preferred from the viewpoint of dispersibility and dispersion stability.
  • Specific synthetic resins include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyptal resin, epoxy resin, and alkylbenzene resin, as well as polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, and modified polyphenylene.
  • Thermoplastic resins such as oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyamino bismaleimide, polyethersulfopolyphenylenesulfone, polyarylate, and polyetheretherketone can be used.
  • the amount of coating resin is preferably 1 to 30% by mass based on the total amount of carbon black and resin. There is a tendency that sufficient coating can be achieved by setting the amount of coating resin to the above lower limit or more. By controlling the amount of coating resin to be less than or equal to the above upper limit, there is a tendency that adhesion between resins can be prevented and dispersibility can be improved.
  • the carbon black coated with a resin in this manner can be used as a coloring agent for colored partition walls according to a conventional method.
  • a colored partition wall with a high light shielding rate and a low surface reflectance tends to be formed at low cost. It is also assumed that by coating the carbon black surface with a resin, there is a function to confine ash containing Na and Ca into the carbon black.
  • the average primary particle diameter of the pigment is usually 0.2 ⁇ m or less, preferably 0.1 ⁇ m or less, and more preferably 0.05 ⁇ m or less.
  • the average primary particle diameter of the pigment is measured by using a transmission electron microscope (TEM) or a scanning electron microscope (SEM), and directly measuring the size of the primary particles from an electron micrograph.
  • TEM transmission electron microscope
  • SEM scanning electron microscope
  • dyes in addition to the above-mentioned organic coloring pigments and black pigments, dyes may be used.
  • dyes that can be used as colorants include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
  • azo dyes examples include C.I. I. Acid Yellow 11, C. I. Acid Orange 7, C. I. Acid Red 37, C. I. Acid Red 180, C. I. Acid Blue 29, C. I. Direct Red 28, C. I. Direct Red 83, C. I. Direct Yellow 12, C. I. Direct Orange 26, C. I. Direct Green 28, C. I. Direct Green 59, C. I. Reactive Yellow 2, C. I. Reactive Red 17, C. I. Reactive Red 120, C. I. Reactive Black 5, C. I. Disperse Orange 5, C. I. Dispersed Red 58, C. I. Disperse Blue 165, C. I. Basic Blue 41, C. I. Basic Red 18, C. I. Mordant Red 7, C. I. Mordant Yellow 5, C. I. Mordant Black 7 is mentioned.
  • anthraquinone dyes examples include C.I. I. Bat Blue 4, C. I. Acid Blue 40, C. I. Acid Green 25, C. I. Reactive Blue 19, C. I. Reactive Blue 49, C. I. Dispersed Red 60, C. I. Disperse Blue 56, C. I. An example is Disperse Blue 60.
  • phthalocyanine dyes examples include C.I. I. Bat Blue 5 is an example.
  • quinoneimine dyes include C.I. I. Basic Blue 3, C. I. Basic Blue 9 is an example.
  • quinoline dyes examples include C.I. I. Solvent Yellow 33, C. I. Acid Yellow 3, C. I. Disperse Yellow 64 is mentioned.
  • nitro dyes examples include C.I. I. Acid Yellow 1, C. I. Acid Orange 3, C. I. An example is Disperse Yellow 42.
  • the photosensitive resin composition of the present invention preferably contains a dispersant in order to finely disperse the colorant (d) and stabilize the dispersion state.
  • a polymer dispersant having a functional group is preferable, and from the viewpoint of dispersion stability, a carboxy group; a phosphoric acid group; a sulfonic acid group; or a base thereof; a primary, secondary or tertiary Polymer dispersants having functional groups such as amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine are preferred.
  • polymeric dispersants having basic functional groups such as primary, secondary or tertiary amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine disperse pigments. It is particularly preferred from the viewpoint that it can be dispersed with a small amount of dispersant.
  • polymeric dispersants include urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants made of monomers and macromonomers having amino groups, and polyoxyethylene alkyl ether dispersants.
  • examples include polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.
  • dispersants include, for example, the trade names EFKA (registered trademark, manufactured by BASF Corporation), DISPERBYK (registered trademark, manufactured by BYK Chemie Corporation), and DISPARBYK (registered trademark, manufactured by Kusumoto Kasei Co., Ltd.). , SOLSPERSE (registered trademark, manufactured by Lubrizol Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and Ajisper (registered trademark, manufactured by Ajinomoto Co., Ltd.). These polymer dispersants may be used alone or in combination of two or more.
  • the weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1,000 or more, and usually 100,000 or less, preferably 50,000 or less.
  • the weight average molecular weight (Mw) of the polymer dispersant is preferably 700 to 100,000, more preferably 1,000 to 50,000.
  • the dispersant preferably contains one or both of a urethane polymer dispersant having a functional group and an acrylic polymer dispersant, and an acrylic polymer dispersant. It is particularly preferable to include. Further, from the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and either or both of a polyester bond and a polyether bond is preferable.
  • Urethane-based and acrylic-based polymer dispersants include, for example, DISPERBYK-160 to 167, 182 series (all urethane-based), DISPERBYK-2000, 2001, BYK-LPN21116 (all acrylic-based), etc. (all of the above are manufactured by BYK Chemie) ).
  • a preferable chemical structure as a urethane-based polymer dispersant, for example, a polyisocyanate compound, a compound with a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule, and a compound having the same molecule
  • examples include dispersion resins having a weight average molecular weight of 1,000 to 200,000, which are obtained by reacting active hydrogen with a compound having a tertiary amino group. By treating these with a quaternizing agent such as benzyl chloride, all or part of the tertiary amino groups can be converted into quaternary ammonium bases.
  • polyisocyanate compounds examples include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolydine diisocyanate.
  • Aromatic diisocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate; isophorone diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), ⁇ , ⁇ '-diisocyanate, alicyclic diisocyanates such as dimethylcyclohexane; aliphatic diisocyanates having an aromatic ring such as xylylene diisocyanate, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylxylylene diisocyanate; lysine ester triisocyanate, 1, 6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate,
  • the polyisocyanate compound is treated with a suitable trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylic acid salts, etc. to form a portion of the isocyanate group.
  • a suitable trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylic acid salts, etc.
  • Compounds having a number average molecular weight of 300 to 10,000 and having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, etc., and compounds in which one terminal hydroxyl group of these compounds has 1 to 1 carbon atoms. Examples include those alkoxylated with 25 alkyl groups and mixtures of two or more of these.
  • polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these.
  • polyether diols include those obtained by copolymerizing alkylene oxides alone or by copolymerizing them, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and the like. Examples include mixtures of two or more of these.
  • Polyether ester diols include those obtained by reacting ether group-containing diols or mixtures with other glycols with dicarboxylic acids or their anhydrides, or by reacting polyester glycols with alkylene oxides, such as poly(polyester diols). Oxytetramethylene) adipate and the like.
  • the most preferred polyether glycols are polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or compounds in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.
  • Polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides, and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol).
  • the most preferred polyester glycol is polycaprolactone glycol or polycaprolactone using an alcohol having 1 to 25 carbon atoms as an initiator.
  • polycarbonate glycol examples include poly(1,6-hexylene) carbonate and poly(3-methyl-1,5-pentylene) carbonate.
  • polyolefin glycol examples include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. These may be used alone or in combination of two or more.
  • the number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, more preferably 1,000 to 4,000.
  • Active hydrogen that is, a hydrogen atom directly bonded to an oxygen atom, nitrogen atom, or sulfur atom
  • the tertiary amino group is not particularly limited, but includes, for example, an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically an imidazole ring or a triazole ring.
  • Examples of such compounds having active hydrogen and a tertiary amino group in the same molecule include N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, N, N-dipropyl-1,3-propanediamine, N,N-dibutyl-1,3-propanediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dipropylethylenediamine, N,N- Dibutylethylenediamine, N,N-dimethyl-1,4-butanediamine, N,N-diethyl-1,4-butanediamine, N,N-dipropyl-1,4-butanediamine, N,N-dibutyl-1, Examples include 4-butanediamine.
  • examples of the nitrogen-containing heterocycle include a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, an indazole ring, a benzimidazole ring, and a benzo ring.
  • 5-membered nitrogen-containing hetero rings such as triazole ring, benzoxazole ring, benzothiazole ring, and benzothiadiazole ring; 6-membered nitrogen-containing hetero rings such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring, etc. Examples include rings. Among these nitrogen-containing heterocycles, an imidazole ring or a triazole ring is preferred.
  • these compounds having an imidazole ring and an amino group include 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole, and 1-(2-aminoethyl)imidazole.
  • specific examples of compounds having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5-(2-amino-5-chlorophenyl)-3-phenyl-1H-1 , 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 , 4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole, and the like.
  • N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 1-(3-aminopropyl)imidazole, and 3-amino-1,2,4-triazole preferable. These may be used alone or in combination of two or more.
  • the preferred blending ratio of raw materials when producing a urethane polymer dispersant is 10 to 100 parts by mass of a compound having a number average molecular weight of 300 to 10,000 and having one or two hydroxyl groups in the same molecule to 100 parts by mass of the polyisocyanate compound. 200 parts by mass, preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and 0.2 to 25 parts by mass, preferably 0.3 to 25 parts by mass of a compound having active hydrogen and a tertiary amino group in the same molecule. It is 24 parts by mass.
  • the urethane polymer dispersant is produced according to a known method for producing polyurethane resins.
  • Solvents used during production usually include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone; esters such as ethyl acetate, butyl acetate, and cellosolve acetate; benzene, toluene, and xylene.
  • hydrocarbons such as hexane; some alcohols such as diacetone alcohol, isopropanol, sec-butanol, tertiary-butanol; chlorides such as methylene chloride and chloroform; ethers such as tetrahydrofuran and diethyl ether; dimethylformamide, N - Aprotic polar solvents such as methylpyrrolidone and dimethyl sulfoxide; etc. are used. These may be used alone or in combination of two or more.
  • a urethanization reaction catalyst is usually used.
  • this catalyst include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and stannath octoate; iron-based catalysts such as iron acetylacetonate and ferric chloride; grade amine type; etc. These may be used alone or in combination of two or more.
  • the amount of the compound having active hydrogen and a tertiary amino group introduced in the same molecule is preferably controlled within the range of 1 to 100 mgKOH/g, more preferably 5 to 95 mgKOH/g based on the amine value after reaction. .
  • the amine value is a value obtained by neutralizing and titrating a basic amino group with an acid and expressed in mg of KOH in correspondence with the acid value.
  • the weight average molecular weight (Mw) of the urethane polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 3,000 to 50,000.
  • Mw weight average molecular weight
  • the weight average molecular weight (Mw) of the urethane polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 3,000 to 50,000.
  • the acrylic polymer dispersant includes an unsaturated group-containing monomer having a functional group (the functional group referred to herein is the functional group described above as a functional group contained in the polymer dispersant); It is preferable to use a random copolymer, a graft copolymer, or a block copolymer with an unsaturated group-containing monomer having no functional group. These copolymers can be produced by known methods.
  • Examples of the unsaturated group-containing monomer having a functional group include (meth)acrylic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethyl phthalic acid, and 2-(meth)acryloyloxyethyl succinic acid.
  • Unsaturated monomers having a carboxy group such as acryloyloxyethyl hexahydrophthalic acid and acrylic acid dimer, tertiary amino acids such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and quaternized products thereof group, an unsaturated monomer having a quaternary ammonium base.
  • tertiary amino acids such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and quaternized products thereof group
  • an unsaturated monomer having a quaternary ammonium base may be used alone or in combination of two or more.
  • unsaturated group-containing monomers that do not have functional groups include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, Isobutyl (meth)acrylate, t-butyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, cyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxymethyl (meth)acrylate, 2-ethylhexyl ( meth)acrylate, isobornyl(meth)acrylate, tricyclodecane(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, N-vinylpyrrolidone, styrene and its derivatives, ⁇ -methylstyrene, N-cyclohe
  • the acrylic polymer dispersant is particularly preferably an AB or BAB block copolymer consisting of an A block having a functional group and a B block not having a functional group.
  • the A block in addition to the partial structure derived from the unsaturated group-containing monomer containing the above-mentioned functional group, the A block contains a partial structure derived from the unsaturated group-containing monomer that does not contain the above-mentioned functional group. These may be contained in the A block in either random copolymerization or block copolymerization.
  • the content of the partial structure not containing a functional group in the A block is usually 80% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less.
  • the B block consists of a partial structure derived from an unsaturated group-containing monomer that does not contain the above functional group, but one B block contains partial structures derived from two or more types of monomers. These may be contained in the B block in either random copolymerization or block copolymerization.
  • the AB or BAB block copolymer is prepared, for example, by the living polymerization method shown below.
  • Living polymerization methods include anionic living polymerization methods, cationic living polymerization methods, and radical living polymerization methods.
  • the acrylic polymer dispersant that can be used in the present invention may be an AB block copolymer or a BAB block copolymer.
  • the A block/B block ratio constituting the copolymer is preferably 1/99 to 80/20, particularly 5/95 to 60/40 (mass ratio). By keeping it within this range, it tends to be possible to ensure a balance between dispersibility and storage stability.
  • the amount of quaternary ammonium base in 1 g of the AB block copolymer or BAB block copolymer that can be used in the present invention is usually preferably 0.1 to 10 mmol, and within this range. There is a tendency that good dispersibility can be ensured by doing so.
  • Such a block copolymer may normally contain amino groups generated during the manufacturing process, but the amine value is about 1 to 100 mgKOH/g, and from the viewpoint of dispersibility, preferably It is 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, even more preferably 50 mgKOH/g or more, and preferably 90 mgKOH/g or less, more preferably 80 mgKOH/g or less, and still more preferably 75 mgKOH/g or less.
  • the amine value of the block copolymer is preferably 10 to 90 mgKOH/g, more preferably 30 to 80 mgKOH/g, even more preferably 50 to 75 mgKOH/g.
  • the amine value of the acrylic polymer dispersant such as these block copolymers is expressed as the amount of base per 1 g of solid content excluding the solvent in the dispersant sample, and the mass of KOH equivalent to the amount of base per gram of solid content excluding the solvent. Measured by Accurately weigh 0.5 to 1.5 g of the dispersant sample into a 100 mL beaker and dissolve it in 50 mL of acetic acid. This solution is neutralized and titrated with a 0.1 mol/L HClO 4 acetic acid solution using an automatic titrator equipped with a pH electrode.
  • the inflection point of the titration pH curve is taken as the titration end point, and the amine value is determined by the following formula.
  • Amine value [mgKOH/g] (561 ⁇ V)/(W ⁇ S) [However, W: weighed amount of dispersant sample [g], V: titration amount at titration end point [mL], S: solid content concentration of dispersant sample [mass %]. ]
  • the acid value of the acrylic polymer dispersant depends on the presence or absence and type of acidic groups that form the source of the acid value, but generally lower is preferable, and is usually 10 mgKOH/g or less, and its weight average molecular weight (Mw) is preferably in the range of 1,000 to 100,000. By keeping it within the above range, there is a tendency that good dispersibility can be ensured.
  • the acrylic polymer dispersant has a quaternary ammonium base as a functional group
  • its specific structure is not particularly limited, but from the viewpoint of dispersibility, repeating units (hereinafter referred to as , sometimes referred to as a "repeat unit (e1)").
  • R 31 to R 33 are each independently a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent-bearing aryl group) represents an aralkyl group which may be atomized. Two or more of R 31 to R 33 may be bonded to each other to form a cyclic structure.
  • R 34 is a hydrogen atom or a methyl group.
  • X 31 is a divalent aralkyl group. It is a linking group.
  • E - is a counter anion.
  • the number of carbon atoms in the alkyl group which may have a substituent in R 31 to R 33 of the above formula (e1) is not particularly limited, but it is preferably 1 or more and 10 or less, and 6 It is more preferable that it is below.
  • the number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6.
  • the alkyl group may be linear or branched. Further, the alkyl group may include a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
  • alkyl groups include, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl; among these, methyl, ethyl, propyl, A butyl group, a pentyl group, and a hexyl group are preferable, and a methyl group, an ethyl group, a propyl group, and a butyl group are more preferable.
  • the number of carbon atoms in the aryl group which may have a substituent in R 31 to R 33 of the above formula (e1) is not particularly limited, but is usually 6 or more, and preferably 16 or less, and 12 It is more preferable that it is below.
  • the number of carbon atoms in the aryl group is preferably 6 to 16, more preferably 6 to 12.
  • Specific examples of the aryl group include phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, diethylphenyl group, naphthyl group, and anthracenyl group.
  • phenyl group, methylphenyl group, ethylphenyl group A dimethylphenyl group, a diethylphenyl group are preferable, and a phenyl group, a methylphenyl group, and an ethylphenyl group are more preferable.
  • the number of carbon atoms in the optionally substituted aralkyl group in R 31 to R 33 of the above formula (e1) is not particularly limited, but is usually 7 or more, and preferably 16 or less, and 12 It is more preferable that it is below.
  • the number of carbon atoms in the aralkyl group is preferably 7 to 16, more preferably 7 to 12.
  • Specific examples of aralkyl groups include phenylmethyl group (benzyl group), phenylethyl group (phenethyl group), phenylpropyl group, phenylbutyl group, and phenylisopropyl group.
  • phenylmethyl group, phenyl Ethyl group, phenylpropyl group, and phenylbutyl group are preferable, and phenylmethyl group and phenylethyl group are more preferable.
  • R 31 to R 33 are each independently an alkyl group or an aralkyl group, and R 31 and R 33 are each independently a methyl group or an ethyl group, and , R 32 is more preferably a phenylmethyl group or a phenylethyl group, and it is even more preferable that R 31 and R 33 are a methyl group, and R 32 is a phenylmethyl group.
  • repeating unit (e2) a repeating unit represented by the following formula (e2) (hereinafter sometimes referred to as “repeat unit (e2)”) ) is preferable.
  • R 35 and R 36 are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent) R 35 and R 36 may be bonded to each other to form a cyclic structure.
  • R 37 is a hydrogen atom or a methyl group.
  • X 32 is a divalent linking group.
  • alkyl group which may have a substituent in R 35 and R 36 of the above formula (e2) those exemplified as R 31 to R 33 of the above formula (e1) can be preferably employed.
  • aryl group which may have a substituent in R 35 and R 36 of the above formula (e2) those exemplified as R 31 to R 33 of the above formula (e1) can be preferably employed.
  • aralkyl group which may have a substituent in R 35 and R 36 of the above formula (e2) those exemplified as R 31 to R 33 of the above formula (e1) can be preferably employed.
  • R 35 and R 36 are each independently an alkyl group which may have a substituent, and more preferably a methyl group or an ethyl group.
  • Examples of substituents that the alkyl group, aralkyl group, or aryl group in R 31 to R 33 of the above formula (e1) and R 35 and R 36 of the above formula (e2) may have include a halogen atom, an alkoxy group, benzoyl group, and hydroxyl group.
  • the divalent linking groups X 31 and X 32 include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CONH-R 43 - group, -COO-R 44 - group [wherein R 43 and R 44 are a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms]. , preferably -COO-R 44 - group.
  • examples of the counter anion E - include Cl - , Br - , I - , ClO 4 - , BF 4 - , CH 3 COO - and PF 6 - .
  • the content ratio of the repeating unit represented by the formula (e1) in the acrylic polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, the content ratio of the repeating unit represented by the formula (e1) in the total repeating units of the polymer dispersant is It is preferably 60 mol% or less, more preferably 50 mol% or less, and even more preferably is 40 mol% or less, particularly preferably 35 mol% or less, preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, and especially Preferably it is 30 mol% or more.
  • the content ratio of the repeating unit represented by the formula (e1) is 5 relative to the sum of the content ratio of the repeating unit represented by the formula (e1) and the repeating unit represented by the formula (e2). It is preferably 60 to 60 mol%, more preferably 10 to 50 mol%, even more preferably 20 to 40 mol%, and particularly preferably 30 to 35 mol%.
  • the content of the repeating unit represented by the formula (e1) in all repeating units of the acrylic polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 1 mol % or more, and 5 mol % or more, more preferably 10 mol% or more, further preferably 50 mol% or less, more preferably 30 mol% or less, and 20 mol% or less. is more preferable, and particularly preferably 15 mol% or less.
  • the content of the repeating unit represented by the formula (e1) in the total repeating units of the acrylic polymer dispersant is preferably 1 to 50 mol%, more preferably 5 to 30 mol%, and 10 to 20 mol%. % is more preferable, and 10 to 15 mol% is particularly preferable.
  • the content ratio of the repeating unit represented by the formula (e2) to all repeating units of the acrylic polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 5 mol% or more, and 10 mol % or more, more preferably 15 mol% or more, particularly preferably 20 mol% or more, and preferably 60 mol% or less, and 40 mol% or less. is more preferable, more preferably 30 mol% or less, and particularly preferably 25 mol% or less.
  • the content of the repeating unit represented by the formula (e2) in the total repeating units of the acrylic polymer dispersant is preferably 5 to 60 mol%, more preferably 10 to 40 mol%, and 15 to 30 mol%. % is more preferable, and 20 to 25 mol% is particularly preferable.
  • acrylic polymer dispersants contain repeating units represented by the following formula (e3) (hereinafter referred to as “repeating units (e3)”). ) is preferable.
  • R 40 is an ethylene group or a propylene group.
  • R 41 is an alkyl group that may have a substituent.
  • R 42 is a hydrogen atom or a methyl group.
  • k is 1 It is an integer between ⁇ 20.
  • the number of carbon atoms in the optionally substituted alkyl group in R 41 of the above formula (e3) is not particularly limited, but is 1 or more, preferably 2 or more, and 10 or less. It is preferably 6 or less, and more preferably 6 or less.
  • the number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 2 to 6.
  • the alkyl group may be linear or branched. Further, the alkyl group may include a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
  • alkyl groups include, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl; among these, methyl, ethyl, propyl, A butyl group, a pentyl group, and a hexyl group are preferable, and a methyl group, an ethyl group, a propyl group, and a butyl group are more preferable.
  • k in the above formula (e3) is 1 or more, preferably 2 or more, and preferably 10 or less, from the viewpoint of compatibility and dispersibility with binder components such as solvents, and is preferably 10 or less, and 5 or less. It is more preferable that For example, k is preferably 1 to 10, more preferably 2 to 5.
  • the content of the repeating unit represented by the formula (e3) in all repeating units of the acrylic polymer dispersant is not particularly limited, but is preferably 1 mol% or more, and preferably 2 mol% or more. It is more preferably 4 mol% or more, further preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less. When this content ratio is within the above range, it tends to be possible to achieve both compatibility with binder components such as solvents and dispersion stability.
  • the content of the repeating unit represented by the formula (e3) in all repeating units of the acrylic polymer dispersant is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and 4 to 10 mol%. % is more preferred.
  • the acrylic polymer dispersant is a repeating unit represented by the following formula (e4) (hereinafter referred to as a repeating unit (e4 )”) is preferable.
  • R 38 is an alkyl group that may have a substituent, an aryl group that may have a substituent, or an aralkyl group that may have a substituent.
  • R39 is a hydrogen atom or a methyl group.
  • the number of carbon atoms in the optionally substituted alkyl group in R 38 of the above formula (e4) is not particularly limited, but is 1 or more, preferably 2 or more, and preferably 4 or more. More preferably, it is 10 or less, and more preferably 8 or less.
  • the number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 2 to 8, even more preferably 4 to 8.
  • the alkyl group may be linear or branched. Further, the alkyl group may include a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
  • alkyl groups include, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl; among these, methyl, ethyl, propyl, A butyl group, a pentyl group, and a hexyl group are preferable, and a methyl group, an ethyl group, a propyl group, and a butyl group are more preferable.
  • the number of carbon atoms in the optionally substituted aryl group in R 38 of the above formula (e4) is not particularly limited, but is usually 6 or more, preferably 16 or less, and 12 or less. More preferably, it is 8 or less.
  • the aryl group preferably has 6 to 16 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 8 to 12 carbon atoms.
  • Specific examples of the aryl group include phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, diethylphenyl group, naphthyl group, and anthracenyl group.
  • phenyl group, methylphenyl group, ethylphenyl group A dimethylphenyl group, a diethylphenyl group are preferable, and a phenyl group, a methylphenyl group, and an ethylphenyl group are more preferable.
  • the number of carbon atoms in the optionally substituted aralkyl group in R 38 of the above formula (e4) is not particularly limited, but is usually 7 or more, preferably 16 or less, and 12 or less. More preferably, it is 10 or less.
  • the number of carbon atoms in the aralkyl group is preferably 7 to 16, more preferably 7 to 12, even more preferably 7 to 10.
  • Specific examples of aralkyl groups include phenylmethyl group (benzyl group), phenylethyl group (phenethyl group), phenylpropyl group, phenylbutyl group, and phenylisopropyl group.
  • phenylmethyl group, phenyl Ethyl group, phenylpropyl group, and phenylbutyl group are preferable, and phenylmethyl group and phenylethyl group are more preferable.
  • R 38 is preferably an alkyl group or an aralkyl group, and more preferably a methyl group, an ethyl group, or a phenylmethyl group.
  • Examples of the substituent that the alkyl group in R 38 may have include a halogen atom and an alkoxy group. Furthermore, examples of substituents that the aryl group and aralkyl group may have include an alkyl group, a halogen atom, and an alkoxy group.
  • the content of the repeating unit represented by the formula (e4) in all repeating units of the acrylic polymer dispersant is preferably 30 mol% or more, and 40 mol% or more.
  • the content is more preferably 50 mol% or more, further preferably 80 mol% or less, and more preferably 70 mol% or less.
  • the content of the repeating unit represented by formula (e4) in all repeating units of the polymer dispersant is preferably 30 to 80 mol%, more preferably 40 to 70 mol%, and 50 to 70 mol%. More preferred.
  • the acrylic polymer dispersant may have repeating units other than repeating units (e1), repeating units (e2), repeating units (e3), and repeating units (e4).
  • repeating units include, for example, styrene monomers such as styrene and ⁇ -methylstyrene; (meth)acrylate monomers such as (meth)acrylic acid chloride; (meth)acrylamide; Examples include repeating units derived from monomers such as (meth)acrylamide monomers such as N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; and N-methacryloylmorpholine.
  • the acrylic polymer dispersant has an A block having a repeating unit (e1) and a repeating unit (e2), and a repeating unit (e1) and a repeating unit (e2).
  • a block copolymer having a B block is preferable.
  • the block copolymer is preferably an AB block copolymer or a BAB block copolymer.
  • the B block has a repeating unit (e3), and more preferably a repeating unit (e4).
  • the repeating unit (e1) and the repeating unit (e2) may be contained in either random copolymerization or block copolymerization.
  • two or more types of repeating units (e1) and repeating units (e2) may be contained in one A block, and in that case, each repeating unit can be randomly copolymerized, It may be contained in any form of block copolymerization.
  • repeating units other than the repeating unit (e1) and the repeating unit (e2) may be contained in the A block, and examples of such repeating units include the above-mentioned (meth)acrylic acid ester unit. Examples include repeating units derived from polymers.
  • the content of repeating units other than the repeating unit (e1) and repeating unit (e2) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%; Most preferably, it is not contained in the block.
  • Repeating units other than repeating units (e3) and (e4) may be contained in the B block, and examples of such repeating units include styrene monomers such as styrene and ⁇ -methylstyrene. ; (meth)acrylate monomers such as (meth)acrylic acid chloride; (meth)acrylamide monomers such as (meth)acrylamide and N-methylol acrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, croton Acid glycidyl ether; repeating units derived from monomers such as N-methacryloylmorpholine can be mentioned.
  • the content of repeating units other than the repeating unit (e3) and repeating unit (e4) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%; Most preferably, it is not contained in the block.
  • the photosensitive resin composition of the present invention contains a dispersant
  • its content is not particularly limited, but it is preferably 1% by mass or more, and 2% by mass or more based on the total solid content of the photosensitive resin composition. More preferably, 4% by mass or more is particularly preferred. Further, it is preferably 12% by mass or less, more preferably 10% by mass or less, and particularly preferably 9% by mass or less.
  • the content ratio of the dispersant to the total solid content of the photosensitive resin composition is preferably 1 to 12% by mass, more preferably 2 to 10% by mass, and 4 to 10% by mass. Particularly preferred is 9% by weight.
  • the photosensitive resin composition of the present invention may contain a pigment derivative as a dispersion aid in order to improve dispersibility and storage stability.
  • pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, and diketopyrrolopyrrole. and dioxazine derivatives, among which phthalocyanine derivatives and quinophthalone derivatives are preferred.
  • substituents on pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxy groups, amide groups, etc. directly on the pigment skeleton, or alkyl groups, aryl groups, etc. Examples include those bonded via a group, a heterocyclic group, etc., and preferably a sulfonic acid group. Moreover, a plurality of these substituents may be substituted on one pigment skeleton.
  • pigment derivatives include sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, sulfonic acid derivatives of diketopyrrolopyrrole, and sulfonic acid derivatives of dioxazine. It will be done. These may be used alone or in combination of two or more.
  • the photosensitive resin composition of the present invention may contain a surfactant to improve coating properties.
  • surfactant various surfactants can be used, such as anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. Among them, it is preferable to use nonionic surfactants because they are less likely to adversely affect various properties, and among them, fluorine-based and silicone-based surfactants are effective in terms of coating properties.
  • fluorosurfactants examples include "BM-1000” and “BM-1100” manufactured by BM Chemie, "Megafac F-142D", “Megafac F-172” and “Mega ⁇ Fuck F-173'', ⁇ Mega Fuck F-183'', ⁇ Mega Fuck F-470'', ⁇ Mega Fuck F-475'', ⁇ Mega Fuck F-478'', ⁇ Mega Fuck F-554'', ⁇ Mega Fuck F -559'', ⁇ FC430'' manufactured by 3M Japan, and ⁇ DFX-18'' manufactured by Neos.
  • silicone surfactants examples include “DC3PA”, “SH7PA”, “DC11PA”, “SH21PA”, “SH28PA”, “SH29PA”, “8032Additive”, “SH8400” manufactured by Dow Corning Toray Industries, Inc., and BIC Chemie Co., Ltd.
  • Commercially available products include “BYK300”, “BYK323”, “BYK325", and “BYK330” manufactured by Shin-Etsu Silicone Co., Ltd., and “KP340” manufactured by Shin-Etsu Silicone Co., Ltd.
  • the surfactant may include things other than fluorine surfactants and silicone surfactants, and examples of other surfactants include nonionic surfactants, anionic surfactants, and cationic surfactants. Examples include surfactants and amphoteric surfactants.
  • One type of surfactant may be used alone, or two or more types may be used in combination in any combination and ratio. Among these, a combination of silicone surfactant/fluorosurfactant is preferred.
  • This silicone surfactant/fluorosurfactant combination includes, for example, BYK-300 or BYK-330 manufactured by BYK Chemie/F-475, F-478, and F-554 manufactured by DIC. ” or “F-559”.
  • the content ratio of the surfactant in the photosensitive resin composition of the present invention is usually 0.0% relative to the total solid content of the photosensitive resin composition. 01% by mass or more, preferably 0.03% by mass or more, more preferably 0.05% by mass or more, and usually 2% by mass or less, preferably 1.5% by mass or less, more preferably 1% by mass or less.
  • this content ratio is equal to or higher than the lower limit value, coating properties tend to improve.
  • this content ratio is below the above-mentioned upper limit, there is a tendency for residue to be easily generated.
  • the photosensitive resin composition of the present invention may contain a liquid repellent.
  • a liquid repellent it is preferable to contain a liquid repellent. By containing a liquid repellent, it can impart liquid repellency to the surface of the partition wall, so that the obtained partition wall can prevent color mixing in each pixel of the organic layer.
  • liquid repellent examples include silicone-containing compounds and fluorine-based compounds, and preferably a liquid repellent having a crosslinking group (hereinafter sometimes referred to as a "crosslinking group-containing liquid repellent").
  • crosslinking group-containing liquid repellent examples include an epoxy group or an ethylenically unsaturated group, and from the viewpoint of suppressing the outflow of the liquid-repellent component of the developer, the ethylenically unsaturated group is preferable.
  • the fluorine-based compound When a fluorine-based compound is used as a liquid repellent, the fluorine-based compound tends to be oriented on the surface of the partition wall and work to prevent ink bleeding and color mixing. More specifically, the group having a fluorine atom tends to repel ink and prevent ink from bleeding or color mixing due to ink overflowing beyond the partition wall into an adjacent region.
  • crosslinking group-containing liquid repellents particularly fluorine-based compounds containing ethylenically unsaturated groups
  • fluorine-based compounds containing ethylenically unsaturated groups include perfluoroalkyl sulfonic acids, perfluoroalkyl carboxylic acids, perfluoroalkyl alkylene oxide adducts, and perfluoroalkyl trialkylammonium.
  • an oligomer containing a perfluoroalkyl group and a hydrophilic group an oligomer containing a perfluoroalkyl group and a lipophilic group, an oligomer containing a perfluoroalkyl group, a hydrophilic group and a lipophilic group, a urethane containing a perfluoroalkyl group and a hydrophilic group
  • fluorine-containing organic compounds such as perfluoroalkyl esters and perfluoroalkyl phosphates.
  • fluorine-containing compounds include, for example, "DEFENSAMCF-300”, “DEFENSAMCF-310”, “DEFENSAMCF-312”, “DEFENSAMCF-323”, “Megafac RS-72-K” manufactured by DIC; 3M Japan “Florado FC-431”, “Florado FC-4430”, “Florado FC-4432", Asahi Glass Co., Ltd.
  • the content of fluorine atoms in the liquid repellent is not particularly limited, but the content of fluorine atoms is preferably 1% by mass or more, more preferably 5% by mass or more, and The content is preferably 50% by mass or less, more preferably 25% by mass or less.
  • this content ratio is equal to or higher than the lower limit value, a high contact angle tends to be exhibited. By setting this content ratio below the upper limit value, there is a tendency that outflow to the pixel portion can be suppressed.
  • the molecular weight of the liquid repellent is not particularly limited.
  • the content ratio of the liquid repellent in the photosensitive resin composition of the present invention is, for example, 0.01 with respect to the total solid content of the photosensitive resin composition. It is not less than 1% by mass and not more than 1% by mass. When this content ratio is equal to or higher than the lower limit value, high liquid repellency tends to be exhibited. By setting this content ratio to be below the upper limit value, there is a tendency that the outflow of the liquid repellent agent to the pixel portion can be suppressed.
  • 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 causing the ultraviolet absorber to absorb a specific wavelength of the light source used for exposure.
  • an ultraviolet absorber By adding an ultraviolet absorber, effects such as improving the perpendicularity of the side surfaces of the partition walls after development and eliminating residues remaining in unexposed areas after development can be obtained.
  • the ultraviolet absorber from the viewpoint of suppressing inhibition of light absorption of the photopolymerization initiator (b), for example, a compound having an absorption maximum between wavelengths of 250 nm and 400 nm can be used.
  • the ultraviolet absorber preferably contains one or both of a benzotriazole compound and a triazine compound.
  • a benzotriazole compound and a triazine compound By containing one or both of a benzotriazole compound and a triazine compound, (b) the light absorption rate of the photopolymerization initiator decreases, and the photocurability decreases, thereby reducing the melt flow during baking of the film. It is thought that the effect of decreasing the taper angle is obtained.
  • benzotriazole compounds include 2-(5methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 3-[3-tert- Octyl butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate, 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl) -yl)-4-hydroxyphenyl]ethylhexyl propionate, 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-t
  • 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 Kagaku Kogyo Co., Ltd.); TINUVIN (registered trademark, the same applies hereinafter) PS, TINUVIN99-2, TINUVIN109, TINUVIN384-2, TINUVIN 326, TINUVIN900, TINUVIN928, TINUVIN1130 (manufactured by BASF); EVERSORB70, EVERSORB71, EVERSORB72, EVERSORB73, EVERSORB74, EVERSORB75, EVERSORB76, EVERSORB234, EVERSORB77, EVERSORB78, EVERSORB80, EVERSORB
  • 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 glycidyl ether 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 perpendicularity of the side surfaces of partition walls and resolution.
  • examples of commercially available triazine compounds include TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477, and TINUVIN479 (manufactured by BASF).
  • ultraviolet absorbers examples include benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and its derivatives, dinaphthalene compounds, phenanthroline compounds, and dyes.
  • 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, SEESORB10 2, SEESORB103 , SEESORB105, SEESORB106, SEESORB107, SEESORB151 (manufactured by Cipro Kasei Co., Ltd.); benzoate compounds such as Sumisorb 400 (manufactured by Sumitomo Chemical Co., Ltd.), phenyl salicylate; 2-ethylhexyl cinnamate, paramethoxy 2-ethylhexyl cinnamate, methoxy Kay Cinnamic acid derivatives such as isopropyl cinnamate and isoamyl methoxyc
  • cinnamic acid derivatives and naphthalene derivatives it is preferable to use cinnamic acid derivatives.
  • These light absorbers can be used alone or in combination of two or more.
  • benzotriazole compounds either or both of benzotriazole compounds and hydroxyphenyltriazine compounds are preferred, and benzotriazole compounds are particularly preferred.
  • one type of compound may be used alone, or two or more types of compounds may be used in combination.
  • the photosensitive resin composition of the present invention contains an ultraviolet absorber
  • its content is not particularly limited, but is, for example, 0.01 to 15% by mass based on the total solid content of the photosensitive resin composition. .
  • the blending ratio to the photopolymerization initiator is (b) the blending amount of the ultraviolet absorber to 100 parts by mass of the photopolymerization initiator. , usually 1 part by mass or more, preferably 10 parts by mass or more, 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, usually 500 parts by mass or less, preferably 300 parts by mass. parts, more preferably 200 parts by mass or less, still more preferably 100 parts by mass or less.
  • this blending ratio to the lower limit value or more, resolution tends to be improved.
  • Adhesion tends to be enhanced by setting this blending ratio to be less than or equal to the above-mentioned upper limit.
  • the amount of the ultraviolet absorber to be blended is preferably 1 to 500 parts by weight, and preferably 10 to 300 parts by weight, relative to 100 parts by weight of the photopolymerization initiator (b). parts, more preferably 30 to 200 parts by weight, even more preferably 50 to 100 parts by weight, and particularly preferably 80 to 100 parts by weight.
  • the photosensitive resin composition of the present invention preferably contains a polymerization inhibitor. Since the inclusion of a polymerization inhibitor inhibits radical polymerization, it tends to be possible to adjust the tapered shape of the resulting partition walls.
  • polymerization inhibitor examples include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT).
  • hydroquinone and methoxyphenol are preferred, and methylhydroquinone is more preferred.
  • a polymerization inhibitor when producing an alkali-soluble resin, may be included in the resin, and it may be used as is, or in addition to the polymerization inhibitor contained in the resin, the same, Alternatively, a different polymerization inhibitor may be added during production of the photosensitive resin composition.
  • the photosensitive resin composition of the present invention contains a polymerization inhibitor
  • its content is not particularly limited, but is usually 0.0005% by mass or more, preferably 0.0005% by mass or more, based on the total solid content of the photosensitive resin composition.
  • the content is .001% by mass or more, more preferably 0.01% by mass or more, and usually 0.1% by mass or less, preferably 0.08% by mass or less, more preferably 0.05% by mass or less.
  • resolution to improve by making this content ratio equal to or higher than the lower limit value.
  • curability to improve by making this content ratio below the above-mentioned upper limit.
  • the content ratio of the polymerization inhibitor to the total solid content of the photosensitive resin composition is preferably 0.0005 to 0.1% by mass, and 0.001 to 0. 0.08% by mass is more preferred, and 0.01 to 0.05% by mass is even more preferred.
  • thermal polymerization initiator Furthermore, the photosensitive resin composition of the present invention may contain a thermal polymerization initiator. Containing a thermal polymerization initiator tends to increase the degree of crosslinking of the coating film. Specific examples of such thermal polymerization initiators include azo compounds, organic peroxides, and hydrogen peroxide. These may be used alone or in combination of two or more.
  • the total content of these initiators will increase the photopolymerization initiation rate in the photosensitive resin composition. It is preferable to adjust the content ratio of the agent.
  • the thermal polymerization initiator is used in an amount of 5 to 300 parts by mass per 100 parts by mass of the photopolymerization initiator. .
  • the photosensitive resin composition of the present invention may contain an amino compound to promote thermosetting.
  • amino compound examples include amino compounds having a methylol group as a functional group and at least two alkoxymethyl groups obtained by condensing and modifying the same with an alcohol having 1 to 8 carbon atoms.
  • melamine resin obtained by polycondensing melamine and formaldehyde
  • benzoguanamine resin obtained by polycondensing benzoguanamine and formaldehyde
  • glycoluril resin obtained by polycondensing glycoluril and formaldehyde
  • Examples include polycondensed urea resins; resins in which formaldehyde is copolycondensed with two or more of melamine, benzoguanamine, glycoluril, or urea; and modified resins in which the methylol groups of the above resins are modified by alcohol condensation.
  • melamine resins and modified resins thereof are preferred, modified resins in which the modification ratio of methylol groups is 70% or more are more preferred, and modified resins in which the modification ratio of methylol groups is 80% or more are particularly preferred.
  • melamine resins and modified resins thereof include “Cymel” (registered trademark, hereinafter the same) 300, 301, 303, 350, 736, 738, 370, 771 manufactured by Cytec Corporation, 325, 327, 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, "Nicalac” (registered trademark, same hereinafter) manufactured by Sanwa Chemical Co., Ltd. MW -390, MW-100LM, MX-750LM, MW-30M, MX-45, and MX-302.
  • Examples of the benzoguanamine resin and its modified resin include Cymel 1123, 1125, and 1128 manufactured by Cytec.
  • Examples of the glycoluril resin and its modified resin include Cymel 1170, 1171, 1174, and 1172 manufactured by Cytec Corporation, and Nikalac MX-270 manufactured by Sanwa Chemical Company.
  • examples of the above-mentioned urea resin and its modified resin include "UFR" (registered trademark) 65, 300 manufactured by Cytec Co., Ltd. and "Nikalac” MX-290 manufactured by Sanwa Chemical Company.
  • the content of the amino compound is usually 40% by mass or less, preferably 30% by mass or less, based on the total solid content of the photosensitive resin composition. be. Further, it is usually 0.5% by mass or more, preferably 1% by mass or more. There is a tendency that storage stability can be maintained by keeping this content ratio below the above upper limit. There is a tendency that sufficient thermosetting property can be ensured by setting this content ratio to the lower limit value or more.
  • the content of the photosensitive resin composition relative to the total solid content is preferably 0.5 to 40% by mass, more preferably 1 to 30% by mass.
  • Silane coupling agent It is also preferable to add a silane coupling agent to the photosensitive resin composition of the present invention in order to improve the adhesion with the substrate.
  • a silane coupling agent can be used, such as epoxy, methacrylic, amino, and imidazole, but epoxy and imidazole silane coupling agents are particularly preferred from the viewpoint of improving adhesion.
  • the photosensitive resin composition of the present invention contains a silane coupling agent, the content thereof is, for example, 0.1% by mass to 0.1% by mass based on the total solid content of the photosensitive resin composition from the viewpoint of adhesion. 1% by mass is preferred.
  • Inorganic filler The photosensitive resin composition of the present invention further improves the strength of the cured product and improves the strength of the coating film through appropriate interaction with the alkali-soluble resin (formation of a matrix structure).
  • An inorganic filler may be contained for the purpose of improving verticality and taper angle. Examples of such inorganic fillers include talc, silica, alumina, barium sulfate, magnesium oxide, titanium oxide, and those surface-treated with various silane coupling agents.
  • the average particle diameter of these inorganic fillers is usually 0.005 to 2 ⁇ m, preferably 0.01 to 1 ⁇ m.
  • the average particle diameter referred to in this embodiment is a value measured using a laser diffraction scattering particle size distribution measuring device manufactured by Beckman Coulter.
  • silica sol and silica sol modified products tend to have excellent dispersion stability and taper angle improvement effects, and are therefore preferably blended.
  • the photosensitive resin composition of the present invention contains these inorganic fillers, the content thereof is, for example, 5% by mass or more, based on the total solid content of the photosensitive resin composition, from the viewpoint of resolution. It is 80% by mass or less.
  • the photosensitive resin composition of the present invention may contain a phosphoric acid-based ethylenic monomer for the purpose of imparting adhesion to the substrate.
  • a phosphoric acid-based ethylenic monomer for the purpose of imparting adhesion to the substrate.
  • (meth)acryloyloxy group-containing phosphates are preferred, and those represented by the following general formulas (g1), (g2), and (g3) are preferred.
  • R 51 represents a hydrogen atom or a methyl group.
  • e and e' are each independently an integer of 1 to 10.
  • f is 1, 2, or 3; be.
  • These phosphoric acid-based ethylenic monomers may be used alone or in combination of two or more.
  • the photosensitive resin composition of the present invention contains these phosphoric acid-based ethylenic monomers, the content thereof is, for example, 0.02 to 4% by mass based on the total solid content of the photosensitive resin composition. be.
  • the photosensitive resin composition of the present invention usually contains a solvent, and the above-mentioned components are used in a state dissolved or dispersed in the solvent.
  • the solvent is not particularly limited, but includes, for example, the organic solvents described below.
  • Ethylene glycol monomethyl ether ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, 3-methoxy-1-butanol, triethylene glycol monomethyl ether, Glycol monoalkyl ethers such as triethylene glycol monoethyl ether and tripropylene glycol methyl ether; Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether,
  • solvents applicable to the above include, for example, Mineral Spirit, Valsol #2, Apco #18 Solvent, Apco Thinner, So Cal Solvent No. 1 and no. 2.
  • the above-mentioned solvent is capable of dissolving or dispersing each component in the photosensitive resin composition, and is selected depending on the method of using the photosensitive resin composition of the present invention. It is preferable to select one having a boiling point in the range of 60 to 280°C under atmospheric pressure. More preferably, it has a boiling point of 70°C or higher and 260°C or lower, such as propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, and 3-methoxy-1-butyl acetate.
  • solvents can be used alone or in a mixture of two or more.
  • the total solid content of the photosensitive resin composition is usually 1% by mass or more, preferably 5% by mass or more, more preferably 7% by mass or more, still more preferably 10% by mass or more, and usually 90% by mass. % or less, preferably 50% by mass or less, more preferably 45% by mass or less, still more preferably 40% by mass or less.
  • the solvent is such that the total solid content of the photosensitive resin composition is preferably 1 to 90% by mass, more preferably 5 to 50% by mass, even more preferably 7 to 45% by mass, particularly preferably 10 to 40% by mass. It is preferable to use it so that it becomes mass %.
  • the photosensitive resin composition of the present invention is prepared by mixing the above-mentioned components using a stirrer.
  • a dispersion treatment in advance using a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, etc. Since the colorant (d) is made into fine particles by the dispersion treatment, the coating properties of the photosensitive resin composition are improved.
  • Dispersion treatment is usually preferably carried out in a system that uses (d) a colorant, a solvent, and a dispersant in addition to a dispersion aid and (a) part or all of an alkali-soluble resin (hereinafter referred to as dispersion treatment).
  • dispersion treatment The mixture subjected to the treatment and the composition obtained by the treatment are sometimes referred to as "ink” or “pigment dispersion”).
  • a polymer dispersant as the dispersant because it suppresses thickening of the obtained ink and photosensitive resin composition over time (excellent dispersion stability).
  • a pigment dispersion containing at least (d) a colorant, a solvent, and a dispersant As described above, in the process of producing a photosensitive resin composition, it is preferable to produce a pigment dispersion containing at least (d) a colorant, a solvent, and a dispersant.
  • a colorant, solvent, and dispersant (d) that can be used in the pigment dispersion those described as those that can be used in the photosensitive resin composition can be preferably used.
  • the content ratio of each colorant in the colorant (d) in the pigment dispersion the content ratios described as the content ratios in the photosensitive resin composition can be preferably adopted.
  • the temperature is usually from 0°C to 100°C, preferably from room temperature to 80°C.
  • the appropriate dispersion time varies depending on the composition of the liquid, the size of the dispersion processing apparatus, etc., and is therefore adjusted as appropriate.
  • a guideline for dispersion is to control the gloss of the ink so that the 20 degree specular gloss (JIS Z8741) of the photosensitive resin composition is in the range of 50 to 300.
  • the dispersed particle size of the pigment dispersed in the ink is usually 0.03 to 0.3 ⁇ m, and is measured by a dynamic light scattering method or the like.
  • Dispersed particle size measurement by dynamic light scattering (DLS) is performed using sufficiently diluted ink (usually diluted to a pigment concentration of about 0.005 to 0.2% by mass. If there is a specific concentration, follow that concentration.) and measure at 25°C.
  • the obtained ink and other components contained in the photosensitive resin composition other than those mentioned above are mixed to form a uniform solution.
  • fine dust may be mixed into the liquid, so it is desirable to filter the obtained photosensitive resin composition using a filter or the like.
  • the cured product of the present invention can be obtained by curing the photosensitive resin composition of the present invention.
  • a cured product can be formed by Step (1): A step of forming a coating film of the photosensitive resin composition on a substrate.
  • the photosensitive resin composition of the present invention can be used to form partition walls, and particularly can be suitably used to form partition walls for partitioning organic layers of an organic electroluminescent device. That is, the cured product of the present invention forms partition walls, and the photosensitive resin composition of the invention itself becomes a partition material.
  • the method of forming partition walls using the photosensitive resin composition described above is not particularly limited, and conventionally known methods can be employed.
  • the method for forming the partition wall includes, for example, a coating step (step (1)) of applying a photosensitive resin composition onto a substrate to form a photosensitive resin composition layer, and exposing the photosensitive resin composition layer to light. Examples include a method including an exposure step (step (2)). Specific examples of methods for forming such banks include an inkjet method and a photolithography method.
  • a photosensitive resin composition whose viscosity has been adjusted by dilution with a solvent is used as an ink, and ink droplets are ejected onto a substrate along a predetermined pattern of partition walls. is applied onto a substrate to form an uncured barrier rib pattern. Then, the uncured barrier rib pattern is exposed to light to form cured barrier ribs on the substrate.
  • the uncured barrier rib pattern is exposed in the same manner as the exposure step in the photolithography method described later, except that a mask is not used.
  • 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 to light according to a predetermined partition pattern, the exposed photosensitive resin composition layer is developed to form partition walls on the substrate.
  • a contact transfer type coating device such as a roll coater, reverse coater, or bar coater or a spinner (rotary type) is used to coat the substrate on which partition walls are to be formed.
  • the photosensitive resin composition is applied using a non-contact type coating device such as a coating device) or a curtain flow coater, and if necessary, the solvent is removed by drying to form a photosensitive resin composition layer.
  • the photosensitive resin composition is irradiated with active energy rays such as ultraviolet rays and excimer laser light using a negative mask to partially expose the photosensitive resin composition layer according to the bank pattern. exposed to light.
  • active energy rays such as ultraviolet rays and excimer laser light using a negative mask
  • a light source that emits ultraviolet rays such as a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, or a carbon arc lamp, can be used.
  • the exposure amount varies depending on the composition of the photosensitive resin composition, it is preferably about 10 to 400 mJ/cm 2 , for example.
  • the exposed photosensitive resin composition layer according to the pattern of the partition walls is developed with a developer to form partition walls.
  • the developing method is not particularly limited, and a dipping method, a spray method, etc. can be used.
  • Specific examples of developing solutions 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. Can be mentioned.
  • an antifoaming agent and a surfactant can also be added to the developer.
  • Post-baking is preferably performed at 150-250°C for 15-60 minutes. Post-baking is normally performed in air, but if there are electrodes formed on the substrate or layers other than barrier ribs, post-baking may be performed in a non-containing environment such as a nitrogen atmosphere in order to reduce oxidation damage to these at high temperatures. It is preferable to perform post-baking under an active atmosphere or under vacuum.
  • the substrate used for forming the barrier ribs is not particularly limited, and is appropriately selected, for example, depending on the type of organic electroluminescent device to be manufactured using the substrate on which the barrier ribs are formed.
  • Suitable materials for the substrate include glass and various resin materials.
  • Specific examples of the resin material include polyesters such as polyethylene terephthalate; polyolefins such as polyethylene and polypropylene; polycarbonate; poly(meth)methacrylic resin; polysulfone; and polyimide.
  • glass and polyimide are preferred because they have excellent heat resistance.
  • a transparent electrode layer of ITO, ZnO, or the like may be provided in advance on the surface of the substrate on which the partition wall is formed.
  • the thickness of the partition wall of the present invention is usually 0.1 ⁇ m or more, preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, even more preferably 1.5 ⁇ m or more, usually 10 ⁇ m or less, preferably 8 ⁇ m or less, and more preferably 4 ⁇ m.
  • the thickness is more preferably 3 ⁇ m or less, particularly preferably 2 ⁇ m or less.
  • the image display device of the present invention includes the partition wall of the present invention.
  • the image display device is not particularly limited as long as it is a device that displays images or videos, and includes liquid crystal display devices, organic EL display devices, and the like.
  • the image display device of the present invention can be formed by the method described in "Organic EL Display” (Ohmsha, published August 20, 2004, written by Shizushi Tokito, Chihaya Adachi, and 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 that emit light of different colors, such as RGB.
  • alkali-soluble resin-I having an acid value of 100 mg KOH/g and a weight average molecular weight of 3,500.
  • Alkali-soluble resin-I does not correspond to a resin having a cardo skeleton.
  • alkali-soluble resin-II having an acid value of 110 mgKOH/g and a polystyrene-equivalent weight average molecular weight (Mw) of 5,200 measured by GPC.
  • Alkali-soluble resin-II has a cardo skeleton and a partial structure represented by the above formula (a1-0).
  • thermometer a stirrer
  • the mixture was placed in a flask equipped with a condenser and reacted at 90° C. with stirring until the acid value became 5 mgKOH/g or less.
  • the reaction required 12 hours to obtain an epoxy acrylate solution.
  • 25 parts by mass of the above epoxy acrylate solution, 0.74 parts by mass of trimethylolpropane (TMP), 3.95 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), and 2.7 parts by mass of tetrahydrophthalic anhydride (THPA). was placed in a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was slowly raised to 105°C while stirring to cause a reaction.
  • photopolymerization initiator-I The structure of photopolymerization initiator-I is as follows.
  • ⁇ Dispersant-I> An acrylic AB block copolymer consisting of an A block that has a quaternary ammonium base and a tertiary amino group in its side chain, and a B block that does not have a quaternary ammonium base and a tertiary amino group.
  • the A block of dispersant-I contains repeating units of the following formulas (1a) and (2a), and the B block contains repeating units of the following formula (3a). .
  • the content ratios of repeating units of the following formulas (1a), (2a), and (3a) in the total repeating units of dispersant-I are 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively. be.
  • Alkali-soluble resin-I Resin described in Synthesis Example 1
  • Alkali-soluble resin-II Resin described in Synthesis Example 2
  • Alkali-soluble resin-III Resin described in Synthesis Example 3
  • DPEA-12 "KAYARAD DPEA-12” (polyfunctional acrylate) manufactured by Nippon Kayaku Co., Ltd. It corresponds to ethylenically unsaturated compound (c1).
  • ATM-4E "NK Ester ATM-4E” (polyfunctional acrylate) manufactured by Shin-Nakamura Chemical Industry Co., Ltd. It corresponds to ethylenically unsaturated compound (c1).
  • A-9550 "A-9550” (polyfunctional acrylate) manufactured by Shin-Nakamura Chemical Industry Co., Ltd. It does not fall under ethylenically unsaturated compound (c1).
  • DPHA-40H "KAYARAD DPHA-40H” manufactured by Nippon Kayaku Co., Ltd. (polyfunctional acrylate). It does not fall under ethylenically unsaturated compound (c1).
  • TMP-A "Light Acrylate TMP-A” (multifunctional acrylate) manufactured by Kyoeisha Chemical Co., Ltd. It does not fall under ethylenically unsaturated compound (c1).
  • Photopolymerization initiator-I Photopolymerization initiator described in Synthesis Example 4
  • Photopolymerization initiator-II Oxime ester compound having the following chemical structure
  • BYK-330 “BYK-330” manufactured by BYK Chemie (silicone surfactant)
  • the proportions in the mixed liquid are: 100 parts by mass of organic black pigment, 24.1 parts by mass of dispersant-I, 50 parts by mass of alkali-soluble resin-I, 557 parts by mass of PGMEA, and 139 parts by mass of MB.
  • a mixed solution was obtained. Note that the blending ratio of the solvent also includes the amount of the dispersant and the solvent derived from the alkali-soluble resin.
  • This mixed solution was subjected to a dispersion treatment using a paint shaker at a temperature of 25 to 45° C. for 3 hours. Zirconia beads with a diameter of 0.5 mm were used as beads, and 2.5 times the mass of the dispersion was added. After the dispersion was completed, the beads and the dispersion liquid were separated using a filter to prepare a pigment dispersion liquid 1.
  • a photosensitive resin composition was heated and cured to a thickness of 1 nm. It was coated with a spin coater to a thickness of .5 ⁇ m, dried under reduced pressure for 1 minute, and then dried on a hot plate at 100° C. for 120 seconds.
  • the obtained coating film was exposed to ultraviolet light with an intensity of 500 mW/cm 2 at 365 nm using a mask having grid-like openings so that the exposure amount was 100 mJ/cm 2 . .
  • shower development was performed at 24° C. with a water pressure of 0.05 MPa using a developer consisting of a 2.38% by mass TMAH (tetramethylammonium hydroxide) aqueous solution, and then the development was stopped with pure water and washed with water spray. Washed with. At this time, the time during which the coating film in the unexposed area was dissolved and removed was defined as the dissolution time, and the shower development time was set to be twice the dissolution time.
  • TMAH tetramethylammonium hydroxide
  • the dissolution time during development is shown in Tables 1A and 1B.
  • the substrate was cured by heating at 230° C. for 30 minutes in a vacuum-depressurized oven to form lattice-shaped partition walls, thereby obtaining a substrate for taper angle evaluation.
  • the reason why the taper angle becomes vertical when firing under an inert atmosphere such as a nitrogen atmosphere or under vacuum will be discussed as follows. Normally, after firing starts, the initiator becomes active and reacts with unsaturated bonds to progress crosslinking, but when firing in an oxygen-containing atmosphere such as the air, components that simultaneously inhibit the action of radicals such as oxygen Since a large amount of is present, the reaction progresses while competing with the melt flow of the resin due to heat.
  • alkali-soluble resin/ethylenic unsaturated compound refers to the mass ratio of (a) alkali-soluble resin and (c) ethylenically unsaturated compound in the photosensitive resin composition ((a) alkali-soluble resin/ethylenic unsaturated compound). soluble resin/(c) ethylenically unsaturated compound).
  • Double bond equivalent is the weighted average value of the content (mass) of (a) alkali-soluble resin and (c) ethylenically unsaturated compound divided by the number of moles of each ethylenically unsaturated bond, That is, it is the total double bond equivalent of (a) the alkali-soluble resin and (c) the ethylenically unsaturated compound.
  • the oxygen atom contained in the alkylene oxide group forms a hydrogen bond with the hydroxy group or carboxy group of the alkali-soluble resin (a), so that the ethylenically unsaturated compound (c1) and the alkali-soluble resin (a) form a complex. It is considered that even if the content of (c) ethylenically unsaturated compound is small, it has the effect of shortening the dissolution time.
  • Partition wall 2 ITO film 3: Glass substrate T: Tangent line of hypotenuse in contact with boundary surface S H: Height of partition wall S: Interface between partition wall and ITO film

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Abstract

Cette composition de résine photosensible contient (a) une résine soluble dans les alcalis, (b) un photoinitiateur, et (c) un composé éthyléniquement insaturé, et est caractérisée en ce que le rapport en masse ((a) résine soluble dans les alcalis/(c) composé éthyléniquement insaturé) de la (a) résine soluble dans les alcalis et du (c) composé éthyléniquement insaturé est d'au moins 5, et le (c) composé éthyléniquement insaturé contient un composé éthyléniquement insaturé (c1) ayant un groupe oxyde d'alkylène et trois groupes éthyléniquement insaturés ou plus.
PCT/JP2023/023061 2022-06-22 2023-06-22 Composition de résine photosensible, produit durci et son procédé de formation, paroi de séparation et appareil d'affichage d'image Ceased WO2023249070A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013033207A (ja) * 2011-06-29 2013-02-14 Toyo Ink Sc Holdings Co Ltd 感光性樹脂組成物とその硬化物、及び感光性樹脂の製造方法
JP2014002285A (ja) * 2012-06-19 2014-01-09 Hitachi Chemical Co Ltd 隔壁形成材料、これを用いた感光性エレメント、隔壁の形成方法及び画像表示装置の製造方法
WO2020017576A1 (fr) * 2018-07-20 2020-01-23 三菱ケミカル株式会社 Composition de résine colorée photosensible, produit durci, dispositif d'affichage d'image et éclairage
JP2020515898A (ja) * 2017-03-31 2020-05-28 東友ファインケム株式会社Ｄｏｎｇｗｏｏ Ｆｉｎｅ−Ｃｈｅｍ Ｃｏ．， Ｌｔｄ． 青色感光性樹脂組成物、これを用いて製造されたカラーフィルタおよび画像表示装置

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CN109952535A (zh) 2016-12-02 2019-06-28 三菱化学株式会社 着色感光性树脂组合物、颜料分散液、间隔壁、有机场致发光元件、图像显示装置及照明

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013033207A (ja) * 2011-06-29 2013-02-14 Toyo Ink Sc Holdings Co Ltd 感光性樹脂組成物とその硬化物、及び感光性樹脂の製造方法
JP2014002285A (ja) * 2012-06-19 2014-01-09 Hitachi Chemical Co Ltd 隔壁形成材料、これを用いた感光性エレメント、隔壁の形成方法及び画像表示装置の製造方法
JP2020515898A (ja) * 2017-03-31 2020-05-28 東友ファインケム株式会社Ｄｏｎｇｗｏｏ Ｆｉｎｅ−Ｃｈｅｍ Ｃｏ．， Ｌｔｄ． 青色感光性樹脂組成物、これを用いて製造されたカラーフィルタおよび画像表示装置
WO2020017576A1 (fr) * 2018-07-20 2020-01-23 三菱ケミカル株式会社 Composition de résine colorée photosensible, produit durci, dispositif d'affichage d'image et éclairage

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