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WO2025225376A1 - Composition photodurcissable, procédé de production de pixels, film, filtre optique, élément d'imagerie à semi-conducteurs, dispositif d'affichage d'image et initiateur de photopolymérisation - Google Patents

Composition photodurcissable, procédé de production de pixels, film, filtre optique, élément d'imagerie à semi-conducteurs, dispositif d'affichage d'image et initiateur de photopolymérisation

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Publication number
WO2025225376A1
WO2025225376A1 PCT/JP2025/014108 JP2025014108W WO2025225376A1 WO 2025225376 A1 WO2025225376 A1 WO 2025225376A1 JP 2025014108 W JP2025014108 W JP 2025014108W WO 2025225376 A1 WO2025225376 A1 WO 2025225376A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
formula
alkyl group
photocurable composition
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/014108
Other languages
English (en)
Japanese (ja)
Inventor
雅臣 牧野
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fujifilm Corp
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Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Publication of WO2025225376A1 publication Critical patent/WO2025225376A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
    • C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
    • C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/46—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms
    • C07C323/47—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms to oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C07D209/12—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029

Definitions

  • the present invention relates to a photocurable composition containing a photopolymerization initiator and a polymerizable compound.
  • the present invention also relates to a pixel manufacturing method, a film, an optical filter, a solid-state imaging device, and an image display device using the photocurable composition.
  • the present invention also relates to a photopolymerization initiator.
  • Photocurable compositions containing a photopolymerization initiator and a polymerizable compound can be polymerized and cured by exposure to light, and are therefore used in optical filters, photocurable inks, photosensitive printing plates, various photoresists, and more.
  • Patent Document 1 discloses that pixels are formed by forming a pattern using a photolithography method using a photopolymerization initiator containing an oxime compound and a photosensitive coloring composition containing a polymerizable compound.
  • lowering the exposure illuminance can improve the contrast between exposed and unexposed areas, but lowering the exposure illuminance also tends to reduce sensitivity and result in insufficient curing of the film in the exposed areas.
  • an object of the present invention is to provide a photocurable composition that has little exposure illuminance dependency and is capable of forming pixels with excellent sensitivity and adhesion even when exposed to low illuminance.
  • Another object of the present invention is to provide a pixel manufacturing method, a film, an optical filter, a solid-state imaging device, an image display device, and a photopolymerization initiator.
  • the present invention provides the following:
  • a photocurable composition containing a photopolymerization initiator and a polymerizable compound is a photocurable composition containing a compound represented by formula (1-A) or formula (1-B);
  • X 1a represents a group represented by formula (X1-1):
  • Y 1a represents an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, or NR y1 R y2 —,
  • R y1 represents an alkyl group, an aryl group, or a heteroaryl group,
  • R y2 represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and
  • R y1 and R y2 may be bonded to each other via a single bond or a linking group to form a ring;
  • Ar 1a represents an aromatic hydrocarbon group or an aromatic heterocyclic group;
  • R 1a represents an aromatic hydrocarbon group
  • X11 and X12 each independently represent an aromatic hydrocarbon group
  • L 11 and L 12 each independently represent a single bond, —O—, —S—, —NR L1 —, —CR L2 R L3 —, or —CO—
  • R L1 to R L3 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group
  • L 11 and L 12 are not simultaneously single bonds
  • L13 represents a single bond or —CO—
  • X 13 represents a single bond or a group having a pyrrole ring or an indole ring, and when X 13 is a single bond, L 13 is a single bond
  • a represents 0 or 1, and when a is 0, L 11 is absent;
  • L 13 and X 13 are single bonds, X 11 and X 12 are benzene ring groups, and L 12 is -NR L1 -, a is 0, or a is 1 and L 11 is -O-
  • L Z1 represents a single bond or an alkylene group
  • L Z2 to L Z4 each independently represent —CR LZ1 R LZ2 —, —O—, —S— or —NR LZ3 —
  • R LZ1 to R LZ3 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group
  • R Z1 and R Z2 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group
  • R Z1 and R Z2 may be bonded to each other via a single bond or a linking group to form a ring
  • at least two of L Z2 to L Z4 are -CR LZ1 R LZ2 -.
  • L Z11 represents a single bond or an alkylene group having 1 to 3 carbon atoms; R Z11 to R Z14 each independently represent a hydrogen atom or an alkyl group; L Z11 may be bonded to R Z11 or R Z12 to form a ring; L Z12 represents —(CR LZ11 R LZ12 ) p —, R LZ11 and R LZ12 each independently represent a hydrogen atom or an alkyl group, and p represents an integer of 1 to 5.
  • ⁇ 5> The photocurable composition according to any one of ⁇ 1> to ⁇ 4>, further comprising a colorant.
  • ⁇ 7> The photocurable composition according to ⁇ 6>, wherein the resin includes a resin having a crosslinkable group.
  • the resin includes a graft resin.
  • the resin includes at least one selected from a (meth)acrylic resin, a polyester resin, a polyurethane resin, a polyamide resin, a polyimide resin, a polyamic acid resin, and a polybenzoxazole resin.
  • ⁇ 11> The photocurable composition according to any one of ⁇ 1> to ⁇ 10>, further comprising a chain transfer agent.
  • ⁇ 12> A step of forming a composition layer on a support using the photocurable composition according to any one of ⁇ 1> to ⁇ 11>; a step of patternwise exposing the composition layer to light having a wavelength of 150 to 400 nm; and developing and removing the unexposed portion of the composition layer.
  • ⁇ 13> A film obtained by curing the photocurable composition according to any one of ⁇ 1> to ⁇ 11>.
  • ⁇ 14> A solid-state imaging device comprising the film according to ⁇ 13>.
  • ⁇ 15> An image display device comprising the film according to ⁇ 13>.
  • X 1a represents a group represented by formula (X1-1):
  • Y 1a represents an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, or NR y1 R y2 —,
  • R y1 represents an alkyl group, an aryl group, or a heteroaryl group,
  • R y2 represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and
  • R y1 and R y2 may be bonded to each other via a single bond or a linking group to form a ring;
  • Ar 1a represents an aromatic hydrocarbon group or an aromatic heterocyclic group;
  • R 1a represents an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryl
  • X11 and X12 each independently represent an aromatic hydrocarbon group
  • L 11 and L 12 each independently represent a single bond, —O—, —S—, —NR L1 —, —CR L2 R L3 —, or —CO—
  • R L1 to R L3 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group
  • L 11 and L 12 are not simultaneously single bonds
  • L13 represents a single bond or —CO—
  • X 13 represents a single bond or a group having a pyrrole ring or an indole ring, and when X 13 is a single bond, L 13 is a single bond
  • a represents 0 or 1, and when a is 0, L 11 is absent;
  • L 13 and X 13 are single bonds, X 11 and X 12 are benzene ring groups, and L 12 is -NR L1 -, a is 0, or a is 1 and L 11 is -O-
  • the present invention can provide a photocurable composition that has little exposure illuminance dependency and can form pixels with excellent sensitivity and adhesion even when exposed to low illuminance.
  • the present invention can also provide a pixel manufacturing method, a film, an optical filter, a solid-state imaging device, an image display device, and a photopolymerization initiator.
  • the word "to” is used to mean that the numerical values before and after it are included as the lower limit and upper limit.
  • groups (atomic groups) when a notation does not specify whether the group is substituted or unsubstituted, it encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups).
  • alkyl group encompasses not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups).
  • exposure includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams.
  • Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, electron beams, and other actinic rays or radiation.
  • (meth)acrylate refers to either or both of acrylate and methacrylate
  • (meth)acrylic refers to either or both of acrylic and methacrylic
  • (meth)acryloyl refers to either or both of acryloyl and methacryloyl.
  • Me represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • the weight average molecular weight and number average molecular weight are values measured by GPC (gel permeation chromatography) in terms of polystyrene.
  • the total solid content refers to the total mass of all components of the composition excluding the solvent.
  • a pigment means a coloring material that is difficult to dissolve in a solvent.
  • the term "process” includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended effect of the process is achieved.
  • the photocurable composition of the present invention comprises A photocurable composition containing a photopolymerization initiator and a polymerizable compound,
  • the photopolymerization initiator is characterized by containing a compound represented by formula (1-A) or formula (1-B).
  • the photocurable composition of the present invention has little dependence on exposure illuminance, and even when exposed to low illuminance, it can form pixels with excellent sensitivity and adhesion.
  • the reason for this effect is presumed to be as follows.
  • the photopolymerization initiator contained in the photocurable composition of the present invention contains a compound represented by formula (1-A ) or formula (1-B). These compounds have a structure in which an acyloyloxy structure ("Y 1a -COO-" in formula (1-A) and "Y 1b -COO-" in formula (1-B)) is bonded to an aromatic hydrocarbon group or an aromatic heterocyclic group (Ar 1a in formula (1-A) and Ar 1b in formula (1-B)).
  • X 1a in formula (1-A) and X 1b in formula (1-B) are each a group represented by formula (X1-1), and it is presumed that the aromatic hydroxy group generated by the photo-Fries transition increases the transition dipole moment and results in a high absorption transition. Therefore, it is presumed that the light absorption of the photopolymerization initiator can be further increased in the exposed area, and that radicals can be efficiently generated even when exposed to low illuminance.
  • the photocurable composition of the present invention has little exposure illuminance dependency, and can form pixels with excellent sensitivity and adhesion even when exposed to low illuminance.
  • the photocurable composition has excellent developability and can further suppress the generation of development residues.
  • the generation of development residues can be further suppressed, and even when an alkaline developer with a low alkaline concentration is used, the generation of development residues can be suppressed. Therefore, even when the alkaline concentration of the alkaline developer varies, the generation of development residues can be suppressed.
  • the aromatic hydroxy group is generated in the exposed area of the compound by the photo-Friess transition. It is presumed that the aromatic hydroxy group generated by the photo-Friess transition improves the solubility of the decomposition products of the photopolymerization initiator in the alkaline developer, thereby achieving this effect.
  • the photocurable composition of the present invention preferably further contains a colorant.
  • Photocurable compositions containing a colorant are preferably used as photocurable compositions for optical filters.
  • optical filters include color filters, infrared transmission filters, and infrared cut filters, with color filters being preferred.
  • color filter is a filter having colored pixels that transmit light of a specific wavelength.
  • colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.
  • the colored pixels of a color filter can be formed using a photocurable composition containing a chromatic colorant.
  • the infrared cut filter's maximum absorption wavelength is preferably in the wavelength range of 700 to 1800 nm, more preferably in the wavelength range of 700 to 1300 nm, and even more preferably in the wavelength range of 700 to 1000 nm.
  • the transmittance of the infrared cut filter over the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.
  • the transmittance at at least one point in the wavelength range of 700 to 1800 nm is preferably 20% or less.
  • the ratio of the absorbance Amax at the infrared cut filter's maximum absorption wavelength to the absorbance A550 at a wavelength of 550 nm is preferably 20 to 500, more preferably 50 to 500, even more preferably 70 to 450, and particularly preferably 100 to 400.
  • the infrared cut filter can be formed using a photocurable composition containing an infrared-absorbing colorant.
  • the infrared transmission filter is a filter that transmits at least a portion of infrared light.
  • the infrared transmission filter is preferably a filter that blocks at least a portion of visible light and transmits at least a portion of infrared light.
  • Preferred examples of the infrared transmission filter include filters that satisfy the spectral characteristics of a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1100 to 1300 nm.
  • the infrared transmission filter is preferably a filter that satisfies any of the following spectral characteristics (1) to (5).
  • the photocurable composition of the present invention can also be used as a light-shielding film, etc.
  • the solids concentration of the photocurable composition of the present invention is preferably 5 to 30% by mass.
  • the lower limit is preferably 7.5% by mass or more, and more preferably 10% by mass or more.
  • the upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.
  • the photocurable composition of the present invention exhibits high sensitivity when exposed to light with a wavelength of 150 to 400 nm. Therefore, the photocurable composition of the present invention is preferably used as a curable composition for exposure to light with a wavelength of 150 to 400 nm.
  • Examples of light with a wavelength of 150 to 400 nm include i-line (wavelength 365 nm), KrF line (wavelength 248 nm), and ArF line (wavelength 193 nm), with i-line (wavelength 365 nm) or KrF line (wavelength 248 nm) being preferred.
  • the light with a wavelength of 150 to 400 nm is preferably excimer laser light with a wavelength of 150 to 400 nm.
  • the photocurable composition of the present invention contains a photopolymerization initiator, which is preferably a photoradical polymerization initiator.
  • the photopolymerization initiator used contains a compound represented by formula (1-A) or formula (1-B).
  • the compound represented by formula (1-A) and the compound represented by formula (1-B) are collectively referred to as specific compounds.
  • X 1a represents a group represented by formula (X1-1): Y 1a represents an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, or NR y1 R y2 —, R y1 represents an alkyl group, an aryl group, or a heteroaryl group, R y2 represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and R y1 and R y2 may be bonded to each other via a single bond or a linking group to form a ring; Ar 1a represents an aromatic hydrocarbon group or an aromatic heterocyclic group; R 1a represents an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, or a heteroaryloxy group; R2a represents an alkyl group, an aryl group, or a heteroaryl
  • X 1a and X 1b - X 1a in formula (1-A) and X 1b in formula (1-B) represent a group represented by formula (X1-1).
  • * represents a bond.
  • X11 and X12 each independently represent an aromatic hydrocarbon group;
  • L 11 and L 12 each independently represent a single bond, —O—, —S—, —NR L1 —, —CR L2 R L3 —, or —CO—;
  • R L1 to R L3 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group;
  • L 11 and L 12 are not simultaneously single bonds;
  • L13 represents a single bond or —CO—;
  • X 13 represents a single bond or a group having a pyrrole ring or an indole ring, and when X 13 is a single bond, L 13 is a single bond;
  • a represents 0 or 1, and when a is 0, L 11
  • X 11 and X 12 each independently represent an aromatic hydrocarbon group.
  • the number of carbon atoms in the aromatic hydrocarbon group represented by X11 and X12 is preferably 6 to 20, and more preferably 6 to 18.
  • the aromatic hydrocarbon group may be a single ring or a condensed ring. Specific examples of the aromatic hydrocarbon group include a benzene ring group, a naphthalene ring group, and an anthracene ring group, and a benzene ring group or a naphthalene ring group is preferred.
  • the aromatic hydrocarbon group represented by X11 and X12 may have a substituent.
  • substituents include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, and a heteroaryloxy group. Details of these groups include those described in the section on Y1a below.
  • L 11 and L 12 each independently represent a single bond, -O-, -S-, -NR L1 -, -CR L2 R L3 -, or -CO-, and R L1 to R L3 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. Details of these groups represented by R L1 to R L3 include those described in the section on Y 1a below.
  • L 11 and L 12 are preferably each independently a single bond, —O—, —S— or —CR L2 R L3 —.
  • a 0 or 1
  • L11 does not exist. That is, when a in formula (X1-1) is 0, the group represented by formula (X1-1) is a group represented by formula (X1-1a), and when a in formula (X1-1) is 1, the group represented by formula (X1-1) is a group represented by formula (X1-1b).
  • L 12 is preferably a single bond, —O—, —S— or —CR L2 R L3 —, and more preferably —O— or —S—.
  • L 11 is preferably a single bond
  • L 12 is preferably —O—, —S— or —CR L2 R L3 —.
  • Preferred combinations of L 11 and L 12 include the following embodiments. An embodiment in which L 11 is a single bond and L 12 is —O—. An embodiment in which L 11 is a single bond and L 12 is —S—. An embodiment in which L 11 is a single bond and L 12 is —CR L2 R L3 — (particularly preferably, R L2 and R L3 are each independently an alkyl group having 1 to 8 carbon atoms).
  • L 13 represents a single bond or —CO—, and preferably —CO—.
  • L 13 is also a single bond.
  • X13 in formula (X1-1) represents a single bond or a group having a pyrrole ring or an indole ring, preferably a group having a pyrrole ring or an indole ring, and more preferably a group having an indole ring.
  • groups having a pyrrole ring include groups represented by formula (X3-1).
  • groups having an indole ring include groups represented by formula (X3-2).
  • * and the wavy line each represent a bond, and * represents a bond to L13 in formula (X1-1), R and R each independently represent a substituent.
  • L and L each independently represent a single bond or a linking group; x represents an integer of 0 to 3; y represents an integer of 0 to 5;
  • Examples of the substituent represented by R X31 in formula (X3-1) and R X32 in formula (X3-2) include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, a heteroaryloxy group, a heteroarylthio group, an amino group, an acyl group, a cyano group, a nitro group, a hydroxy group, a thiol group, a carboxy group, and a halogen atom, and an alkyl group is preferable.
  • the aromatic hydrocarbon group may have a substituent.
  • substituents include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, and a heteroaryloxy group. Details of these groups include those described in the section on Y 1a below.
  • R a1 to R a32 and R b1 to R b32 each independently represent a substituent;
  • R ar1 to R ar25 each independently represent a hydrogen atom, an alkyl group, or an aryl group;
  • k1 to k32 each independently represent an integer of 0 to 3, n1 to n32 each independently represent an integer of 0 to 3;
  • L13 represents a single bond or —CO—;
  • X 13 represents a single bond or a group having a pyrrole ring or an indole ring, and when X 13 is a single bond, L 13 is a single bond;
  • L 13 is —CO—
  • X 13 is a group having a pyrrole ring or an indole ring.
  • L 13 and X 13 are as described above.
  • substituents represented by R a1 to R a32 and R b1 to R b32 include alkyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, and heteroaryloxy groups. Details of these groups include those described in the section on Y 1a below.
  • Y 1a represents an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, or NR y1 R y2 —, where R y1 represents an alkyl group, an aryl group, or a heteroaryl group, R y2 represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and R y1 and R y2 may be bonded to each other via a single bond or a linking group to form a ring.
  • the number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 5.
  • the alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear.
  • the alkyl group represented by R 1a and R 1b is particularly preferably a methyl group.
  • the number of carbon atoms in the alkoxy group is preferably 1 to 15, and more preferably 1 to 10.
  • the alkoxy group is preferably linear or branched, and more preferably linear.
  • the aryl group and aryloxy group preferably have 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, even more preferably 6 to 10 carbon atoms, and particularly preferably 6 or 7 carbon atoms.
  • the number of carbon atoms constituting the ring of the heteroaryl group and heteroaryloxy group is preferably 1 to 15, and more preferably 1 to 10.
  • Types of heteroatoms constituting the ring of the heteroaryl group and heteroaryloxy group include a nitrogen atom, an oxygen atom, and a sulfur atom.
  • the number of heteroatoms constituting the ring of the heteroaryl group and heteroaryloxy group is preferably 1 to 3, and more preferably 1 or 2.
  • the heteroaryl group and heteroaryloxy group may be a monocyclic ring or a fused ring.
  • R y1 and R y2 may be bonded via a single bond or a linking group to form a ring.
  • Examples of the linking group when forming the ring include -O-, -S-, -NR L101 -, and -CR L102 R L103 -.
  • R L101 to R L103 each independently represent a hydrogen atom, an alkyl group, or an aryl group, preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.
  • the alkyl group represented by R L101 to R L103 preferably has 1 to 15 carbon atoms, more preferably 1 to 10.
  • the alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, more preferably linear.
  • the aryl group represented by R L101 to R L103 preferably has 6 to 20 carbon atoms, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6 or 7.
  • Y 1a in formula (1-A) is preferably an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, more preferably an alkyl group, an aryl group, or an alkoxy group, still more preferably an alkyl group or an alkoxy group, and particularly preferably an alkyl group.
  • Y 1b - Y 1b in formula (1-B) represents a t-valent linking group.
  • the t-valent linking group represented by Y 1b include a hydrocarbon group, a heterocyclic group, a group in which two or more hydrocarbon groups are linked via a single bond or a linking group, a group in which two or more heterocycles are linked via a single bond or a linking group, and a group in which a hydrocarbon group and a heterocyclic group are linked via a single bond or a linking group, and a hydrocarbon group or a group in which two or more hydrocarbon groups are linked via a single bond or a linking group is preferred.
  • the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
  • the aliphatic hydrocarbon group may be cyclic or acyclic.
  • the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group.
  • the hydrocarbon group may have a substituent or may not have a substituent.
  • the cyclic aliphatic hydrocarbon group and the aromatic hydrocarbon group may be a monocyclic ring or a fused ring.
  • the heterocyclic group may be a single ring or a condensed ring.
  • the heterocyclic group is preferably a 5-membered or 6-membered ring.
  • the heterocyclic group may be an aromatic heterocyclic group.
  • heteroatoms constituting the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom.
  • linking groups that link the above hydrocarbon groups together, the heterocyclic groups together, or the hydrocarbon group and the heterocyclic group include -CH2- , -O-, -CO-, -COO-, -OCO-, -S-, -SO-, -SO2- , -NRx- , and groups combining two or more of these.
  • Rx represents a hydrogen atom, an alkyl group, or an aryl group, and is preferably a hydrogen atom.
  • Ar 1a in formula (1-A) and Ar 1b in formula (1-B) each independently represent an aromatic hydrocarbon group or an aromatic heterocyclic group.
  • the number of carbon atoms in the aromatic hydrocarbon group represented by Ar 1a and Ar 1b is preferably 6 to 20, more preferably 10 to 18.
  • the aromatic hydrocarbon group may be a monocyclic ring, but is preferably a fused ring.
  • Specific examples of the aromatic hydrocarbon group represented by Ar 1a and Ar 1b include: Examples include a benzene ring group, a naphthalene ring group, an anthracene ring group, a phenanthrene ring group, a benzophenanthrene ring group, and a pyrene ring group.
  • a benzene ring group, a naphthalene ring group, or an anthracene ring group is preferred, and a naphthalene ring group or an anthracene ring group is more preferred.
  • the number of carbon atoms constituting the ring of the aromatic heterocyclic group represented by Ar 1a and Ar 1b is preferably 1 to 15, and more preferably 1 to 10.
  • Examples of heteroatoms constituting the ring of the aromatic heterocyclic group include nitrogen atoms, oxygen atoms, and sulfur atoms.
  • the number of heteroatoms constituting the ring of the aromatic heterocyclic group is preferably 1 to 3, and more preferably 1 or 2.
  • the aromatic heterocyclic group may be a monocyclic ring or a fused ring.
  • aromatic heterocyclic group examples include a furan ring group, a thiophene ring group, a benzofuran ring group, a benzothiophene ring group, a pyrrole ring group, an indole ring group, a pyridine ring group, a quinoxaline ring group, an imidazole ring group, and a benzimidazole ring group, and a benzofuran ring group is preferred.
  • the above aromatic hydrocarbon groups and aromatic heterocyclic groups may have a substituent.
  • substituents include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylthio group, and an arylthio group, with an alkyl group, an alkoxy group, or an alkylthio group being preferred.
  • R 1a and R 1b each independently represent an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, or a heteroaryloxy group, preferably an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, and more preferably an alkyl group.
  • the number of carbon atoms in the alkyl group represented by R 1a and R 1b is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 5.
  • the alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear.
  • the alkyl group represented by R 1a and R 1b is particularly preferably a methyl group.
  • the number of carbon atoms in the alkoxy group represented by R 1a and R 1b is preferably 1 to 15, and more preferably 1 to 10.
  • the alkoxy group is preferably linear or branched, and more preferably linear.
  • the aryl group and aryloxy group represented by R 1a and R 1b preferably have 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, still more preferably 6 to 10 carbon atoms, and particularly preferably 6 or 7 carbon atoms.
  • the number of carbon atoms constituting the ring of the heteroaryl group and heteroaryloxy group represented by R 1a and R 1b is preferably 1 to 15, and more preferably 1 to 10.
  • Types of heteroatoms constituting the ring of the heteroaryl group and heteroaryloxy group include a nitrogen atom, an oxygen atom, and a sulfur atom.
  • the number of heteroatoms constituting the ring of the heteroaryl group and heteroaryloxy group is preferably 1 to 3, and more preferably 1 or 2.
  • the heteroaryl group and heteroaryloxy group may be a monocyclic ring or a fused ring.
  • R 2a and R 2b each independently represent an alkyl group, an aryl group, or a heteroaryl group, preferably an alkyl group or an aryl group, and more preferably an alkyl group.
  • R 2a and R 2b are preferably an unsubstituted linear alkyl group, an alkyl group having a branched structure, an alkyl group having a cyclic structure, or an alkyl group having at least one substituent selected from the following Group A, more preferably an alkyl group having a branched structure or an alkyl group having a cyclic structure, and even more preferably an alkyl group having a cyclic structure.
  • the alkyl group having a cyclic structure is preferably an alkyl group having a cyclic alkyl group as a substituent, more preferably an alkyl group having a 3- to 7-membered cyclic alkyl group as a substituent, even more preferably an alkyl group having a 5- to 7-membered cyclic alkyl group as a substituent, particularly preferably an alkyl group having a 5- or 6-membered cyclic alkyl group as a substituent, and most preferably an alkyl group having a 6-membered cyclic alkyl group as a substituent.
  • the position of the branched structure is preferably the ⁇ -position of the oxime group, and it is more preferable that one hydrogen atom ( ⁇ -hydrogen) be present at the ⁇ -position.
  • R2a and R2b are also preferably alkyl groups having a group having a heteroatom as a substituent.
  • the group having a heteroatom is preferably a group having an oxygen atom, a sulfur atom, or a nitrogen atom.
  • Each of the R a's is preferably an alkyl group, an aryl group or a heteroaryl group, more preferably an alkyl group, and particularly preferably a cyclic alkyl group.
  • Each R b is preferably a hydrogen atom or an alkyl group, more preferably an alkyl group.
  • the above Rc is preferably an alkyl group or an aryl group, and is preferably an alkyl group.
  • Each Rd is preferably an alkylene group, more preferably an ethylene group or a propylene group.
  • R a to R c may be bonded via a single bond or a linking group to form a ring.
  • the linking group when forming the ring include -O-, -S-, -NR L101 -, and -CR L102 R L103 -.
  • R L101 to R L103 each independently represent a hydrogen atom, an alkyl group, or an aryl group, and are preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
  • the alkyl group represented by R L101 to R L103 preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms.
  • the alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear.
  • the aryl group represented by R L101 to R L103 preferably has 6 to 20 carbon atoms, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6 or 7.
  • R 2a and R 2b are alkyl groups having at least one substituent selected from Group A
  • the substituent from Group A on the alkyl group is preferably an alkenyl group, an azaacyloyl group, or -SR a .
  • R a in -SR a is preferably an aryl group.
  • R 2a and R 2b each independently represent a group represented by formula (Z-1).
  • * represents a bond.
  • L Z1 represents a single bond or an alkylene group
  • L Z2 to L Z4 each independently represent —CR LZ1 R LZ2 —, —O—, —S— or —NR LZ3 —
  • R LZ1 to R LZ3 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group
  • R Z1 and R Z2 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group
  • R Z1 and R Z2 may be bonded to each other via a single bond or a linking group to form a ring;
  • at least two of L Z2 to L Z4 are -CR LZ1 R LZ2 -.
  • the alkylene group represented by L Z1 in formula (Z-1) preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, even more preferably 1 to 3 carbon atoms, still more preferably 1 or 2 carbon atoms, and particularly preferably 1 carbon atom.
  • L Z1 is preferably a single bond or a methylene group, more preferably a single bond.
  • L Z2 to L Z4 each independently represent —CR L1 R L2 —, —O—, —S— or —NR L3 —
  • R L1 to R L3 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group.
  • the number of carbon atoms in the alkyl group represented by R L1 to R L3 is preferably 1 to 15, and more preferably 1 to 10.
  • the alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear.
  • the aryl group represented by R L1 to R L3 preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, still more preferably 6 to 10 carbon atoms, and particularly preferably 6 or 7 carbon atoms.
  • the number of carbon atoms constituting the ring of the heteroaryl group represented by R L1 to R L3 is preferably 1 to 15, and more preferably 1 to 10.
  • Types of heteroatoms constituting the ring of the heteroaryl group include a nitrogen atom, an oxygen atom, and a sulfur atom.
  • the number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3, and more preferably 1 or 2.
  • the heteroaryl group may be a monocyclic ring or a fused ring.
  • R L1 to R L3 are each preferably independently a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
  • L Z2 to L Z4 are —CR L1 R L2 —.
  • a preferred embodiment is one in which L Z2 is —CR L1 R L2 —.
  • R L1 and R L2 in —CR L1 R L2 — represented by L Z2 are preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
  • Another preferred embodiment is one in which L Z3 and L Z4 are each independently -CR L1 R L2 -.
  • R L1 and R L2 in -CR L1 R L2 - represented by L Z3 and L Z4 are preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.
  • L Z2 to L Z4 in formula (Z-1) are each independently —CR L1 R L2 —.
  • L Z1 is a single bond or a methylene group and L Z2 is —CR L1 R L2 —, and it is more preferable that L Z1 is a single bond and L Z2 is —CR L1 R L2 —.
  • R 1 Z1 and R 2 Z2 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.
  • the number of carbon atoms in the alkyl group represented by R Z1 and R Z2 is preferably 1 to 15, and more preferably 1 to 10.
  • the alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear.
  • the aryl group represented by R 1 Z1 and R 1 Z2 preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, still more preferably 6 to 10 carbon atoms, and particularly preferably 6 or 7 carbon atoms.
  • the number of carbon atoms constituting the ring of the heteroaryl group represented by R Z1 and R Z2 is preferably 1 to 15, and more preferably 1 to 10.
  • Types of heteroatoms constituting the ring of the heteroaryl group include a nitrogen atom, an oxygen atom, and a sulfur atom.
  • the number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3, and more preferably 1 or 2.
  • the heteroaryl group may be a monocyclic ring or a fused ring. It is preferred that R 1 Z1 and R 1 Z2 each independently represent a hydrogen atom or an alkyl group.
  • R Z1 and R Z2 in formula (Z-1) may be bonded via a single bond or a linking group to form a ring.
  • the linking group when forming the ring include -O-, -S-, -NR L101 -, and -CR L102 R L103 -.
  • R L101 to R L103 each independently represent a hydrogen atom, an alkyl group, or an aryl group, and are preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
  • the alkyl group represented by R L101 to R L103 preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms.
  • the alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear.
  • the aryl group represented by R L101 to R L103 preferably has 6 to 20 carbon atoms, more preferably 6 to 12, even more preferably 6 to 10, and particularly preferably 6 or 7.
  • the ring formed is preferably a 3- to 8-membered ring, more preferably a 4- to 7-membered ring, and even more preferably a 5- or 6-membered ring.
  • the ring formed is preferably a non-aromatic ring, more preferably an aliphatic hydrocarbon ring.
  • the ring formed is particularly preferably a 5- or 6-membered aliphatic hydrocarbon ring.
  • a preferred embodiment of the group represented by formula (Z-1) is L Z1 is a single bond or a methylene group; L Z2 to L Z4 are each independently —CR L1 R L2 —, and R L1 and R L2 are each independently a hydrogen atom or an alkyl group; An embodiment in which R 1 Z1 and R 2 Z2 are each independently a hydrogen atom or an alkyl group is given. In this embodiment, R L1 , R L2 , R Z1 and R Z2 are each preferably a hydrogen atom.
  • L Z1 is a single bond or a methylene group
  • L Z2 to L Z4 are each independently —CR L1 R L2 —
  • R L1 and R L2 are each independently a hydrogen atom or an alkyl group
  • R L1 and R L2 are each preferably a hydrogen atom.
  • the ring formed by bonding R and R is preferably an aliphatic hydrocarbon ring, more preferably a 3- to 8-membered aliphatic hydrocarbon ring, even more preferably a 4- to 7-membered aliphatic hydrocarbon ring, and particularly preferably a 5- or 6-membered aliphatic hydrocarbon ring.
  • R 2a and R 2b each independently represent a group represented by formula (Z-2).
  • * represents a bond.
  • L Z11 represents a single bond or an alkylene group having 1 to 3 carbon atoms;
  • R Z11 to R Z14 each independently represent a hydrogen atom or an alkyl group;
  • L Z11 may be bonded to R Z11 or R Z12 to form a ring;
  • L Z12 represents —(CR LZ11 R LZ12 ) p —, R LZ11 and R LZ12 each independently represent a hydrogen atom or an alkyl group, and p represents an integer of 1 to 5.
  • L Z11 is preferably an alkylene group having 1 to 3 carbon atoms.
  • the number of carbon atoms in the alkyl groups represented by R Z11 to R Z14 , R LZ11 and R LZ12 is preferably 1 to 15, and more preferably 1 to 10.
  • the alkyl group may be linear, branched or cyclic, but is preferably linear or branched, and more preferably linear.
  • R Z11 to R Z14 , R LZ11 and R LZ12 are preferably hydrogen atoms.
  • p represents an integer from 1 to 5, preferably 3 or 4, and more preferably 3.
  • na and nb- na in formula (1-A) and nb in formula (1-B) each independently represent 0 or 1, and are preferably 1.
  • -About ma and mb- ma in formula (1-A) and mb in formula (1-B) each independently represent 0 or 1, and are preferably 1.
  • s represents an integer of 1 to 3, preferably 1 or 2, and more preferably 1.
  • t represents an integer of 2 to 4, and is preferably 2 or 3, more preferably 2, because this allows for further suppression of development residues.
  • the specific compound is preferably a compound represented by formula (1-A) because it can reduce the exposure illuminance dependency.
  • the molecular weight of the specific compound is preferably 200 to 2000.
  • the upper limit is preferably 1500 or less, and more preferably 1000 or less.
  • the lower limit is preferably 300 or more, and more preferably 400 or more.
  • the molar absorption coefficient of the specific compound at a wavelength of 248 nm is preferably 5,000 L mol cm or more, more preferably 10,000 L mol cm or more , even more preferably 20,000 L mol cm or more , and particularly preferably 30,000 L mol cm or more .
  • the molar absorption coefficient at a wavelength of 248 nm is preferably 200,000 L mol cm or less .
  • the molar absorption coefficient of the specific compound at a wavelength of 365 nm is preferably 500 L mol cm or more , more preferably 1000 L mol cm or more , even more preferably 2000 L mol cm or more , and particularly preferably 3000 L mol cm or more .
  • the specific compound preferably has a long wavelength absorption end (the longest wavelength at which the molar absorption coefficient is less than 100 L mol cm ) of 450 nm or less, more preferably 400 nm or less, and even more preferably 380 nm or less. Having the long wavelength absorption end in the above range prevents yellow light fogging and provides excellent light stability during synthesis. Furthermore, since the specific compound does not exhibit a yellow color, good color reproducibility is achieved when applied to optical filters such as color filters.
  • the molar absorption coefficient of a specific compound is measured by the following method. Accurately weigh out 12.5 mg of a specific compound and place it in a 100 mL volumetric flask. Add acetonitrile to this and dissolve completely. Take 2 mL of this solution with a volumetric pipette and make up to 25 mL in a volumetric flask. This is the measurement sample. Add the measurement sample to a 1 cm square 5 mL quartz glass cell, measure the absorbance in air, and calculate the molar extinction coefficient. Examples of measurement devices include an ultraviolet-visible-near-infrared spectrophotometer (UH4150, manufactured by Hitachi High-Tech Corporation).
  • the specific compound may be the E geometric isomer, the Z geometric isomer, or a mixture of the E and Z geometric isomers.
  • the maximum absorption wavelength of the specific compound preferably exists in the wavelength range of 230 to 380 nm.
  • the number of maximum absorption wavelengths may be one or two or more. If there are two or more maximum absorption wavelengths, the maximum absorption wavelengths are preferably at least 20 nm apart, and more preferably at least 50 nm apart.
  • the melting point of the specific compound is preferably 50 to 150°C, more preferably 60 to 130°C, and even more preferably 70 to 120°C.
  • the 50% cumulative value of the specific compound as measured by dynamic light scattering is preferably 0.001 to 1000 ⁇ m, more preferably 0.01 to 100 ⁇ m, and even more preferably 0.1 to 10 ⁇ m, from the standpoint of ease of handling and solubility in solvents.
  • the specific compound can be synthesized by the following methods (1) to (3).
  • They can be synthesized by subjecting an acid chloride or acid anhydride having an acyloyloxy group to a Friedel-Crafts reaction in the presence of a Lewis acid ( AlCl3 , SnCl4 , BCl3 , AlBr3 , FeCl3 , GaCl3 , SbCl5 , InCl3 , SnBr4 , AsCl5 , ZnCl2 , CdCl2 , HgCl2, etc.), followed by conversion to an oxime or ketoxime.
  • the conversion to an oxime or ketoxime can be carried out by a conventional method.
  • a methoxy-containing acid chloride or acid anhydride is subjected to a Friedel-Crafts reaction in the presence of a Lewis acid, followed by demethylation with BBr3 to synthesize an OH-free form.
  • the resulting OH-free form can then be acylated in the presence of a base.
  • Acylation can be carried out after oxime or ketoxime formation, or simultaneously with the oxime esterification step.
  • An acid chloride or acid anhydride having a tertiary alkoxy group (such as a tert-butoxy group) is subjected to a Friedel-Crafts reaction in the presence of a Lewis acid, followed by dealkylation with a Br ⁇ nsted acid (preferably with a pKa of ⁇ 0; for example, methanesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid, sulfuric acid, etc.) to synthesize an OH-free form.
  • the resulting OH-free form can be acylated in the presence of a base.
  • Acylation may be carried out after oxime formation or ketoxime formation, or may be carried out simultaneously in the oxime esterification stage.
  • the photocurable composition of the present invention may contain a precursor oxime body and a ketone body prior to oximation. If these are contained, the content of each of the oxime body and ketone body is preferably 0.001 to 10% by mass, more preferably 0.001 to 8% by mass, and even more preferably 0.001 to 5% by mass of the specific compound.
  • Specific examples of specific compounds include compounds A-1 to A-339 shown below.
  • Me represents a methyl group
  • Et represents an ethyl group
  • iPr represents an isopropyl group
  • tBu represents a tert-butyl group
  • MOM represents a methoxymethyl group
  • Ph represents a phenyl group
  • Fr represents a furanyl group
  • OMe represents a methoxy group
  • OPh represents a phenoxy group
  • NHHex represents an N-hexyl group
  • NHPh represents an N-phenyl group.
  • the photocurable composition of the present invention may use only one of the specific compounds described above, or two or more of them in combination. Using two or more of them in combination has the effect of achieving a better balance between resolution and sensitivity, whether the exposure light source is KrF line or i-line.
  • the impurities that may be contained in the specific compound will be described below.
  • the content of water contained in the specific compound is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, further preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less, relative to 100 parts by mass of the specific compound.
  • the lower limit can be 0 parts by mass, 0.0001 parts by mass, 0.001 parts by mass, or 0.01 parts by mass.
  • the content of the organic solvent contained in the specific compound is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, further preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less, relative to 100 parts by mass of the specific compound.
  • the lower limit can be 0 parts by mass, 0.0001 parts by mass, 0.001 parts by mass, or 0.01 parts by mass.
  • the content of the organic acid and organic acid anhydride contained in the specific compound is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less, relative to 100 parts by mass of the specific compound.
  • the lower limit can be 0 parts by mass, 0.0001 parts by mass, 0.001 parts by mass, or 0.01 parts by mass.
  • organic acids include formic acid, acetic acid, propionic acid, pivalic acid, succinic acid, phthalic acid, and benzoic acid.
  • organic acid anhydrides include anhydrides of these.
  • the content of the organic base contained in the specific compound is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less, relative to 100 parts by mass of the specific compound.
  • the lower limit can be 0 parts by mass, 0.0001 parts by mass, 0.001 parts by mass, or 0.01 parts by mass.
  • organic bases include triethylamine, dimethylamine, diethylamine, pyridine, piperidine, pyrrolidine, morpholine, and amines used in producing the specific compound.
  • the content of halogen contained in the specific compound is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 1 part by mass or less, relative to 100 parts by mass of the specific compound.
  • the lower limit can be 0 parts by mass, 0.0001 parts by mass, 0.001 parts by mass, or 0.01 parts by mass.
  • Halogen includes Cl, Br, F, I, etc., and may be an organic compound having these halogen atoms.Also, ions of these halogens may be used.
  • the content of the residual metal contained in the specific compound is preferably 0.1 parts by mass or less, more preferably 0.01 parts by mass or less, and even more preferably 0.001 parts by mass or less, per 100 parts by mass of the specific compound.
  • the type of residual metal is not particularly limited, but examples include Li, Na, Mg, Al, K, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb, Ti, V, As, Ag, Sn, Ba, W, Au, and Zr.
  • the photocurable composition of the present invention may further contain a photopolymerization initiator other than the specific compound described above (hereinafter also referred to as other photopolymerization initiator).
  • a photopolymerization initiator other than the specific compound described above hereinafter also referred to as other photopolymerization initiator.
  • the content of the other photopolymerization initiator is preferably 1 to 1,000 parts by mass per 100 parts by mass of the specific compound.
  • the upper limit is preferably 500 parts by mass or less, more preferably 200 parts by mass or less.
  • the lower limit is preferably 10 parts by mass or more, more preferably 50 parts by mass or more.
  • photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, etc.
  • halogenated hydrocarbon derivatives e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.
  • acylphosphine compounds e.g., acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, etc.
  • the other photopolymerization initiator is preferably a trihalomethyltriazine compound, a benzyl dimethyl ketal compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a hexaarylbiimidazole compound, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound, or a 3-aryl-substituted coumarin compound; more preferably an oxime compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, or an acylphosphine compound; even more preferably an ⁇ -aminoketone compound or an oxime compound; and particularly preferably an oxime compound
  • photopolymerization initiators include the compounds described in paragraphs 0065 to 0111 of JP 2014-130173 A, the compounds described in Japanese Patent No. 6301489 A, and the compounds described in MATERIAL STAGE pp. 37-60, vol. 19, No.
  • photopolymerization initiators that can be suitably used include SPI-02, SPI-03, SPI-05, SPI-06, and SPI-07 (all manufactured by SAMYANG Co., Ltd.), Nikkacure series YJ-04(T), IW-15, TG-05, TG-10, and TKG-01 (all manufactured by Nippon Chemical Industry Co., Ltd.), SpeedCure PDO (all manufactured by ARKEMA Co., Ltd.), HTPI-429 (all manufactured by Heraeus Co., Ltd.), Omnirad 1312, and Omnirad 1316 (all manufactured by IGM Resins B.V.), etc.
  • hexaarylbiimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole.
  • ⁇ -hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins B.V.), and Irgacure 184, Irgacure 1173, Irgacure 2959, and Irgacure 127 (all manufactured by BASF).
  • Commercially available ⁇ -aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins B.V.), and Irgacure 907, Irgacure 369, Irgacure 369E, and Irgacure 379EG (all manufactured by BASF).
  • acylphosphine compounds include Omnirad 819 and Omnirad TPO (all manufactured by IGM Resins B.V.), and Irgacure 819 and Irgacure TPO (all manufactured by BASF).
  • Examples of oxime compounds include the compounds described in paragraph 0142 of WO 2022/085485, the compounds described in Japanese Patent No. 5430746, the compounds described in Japanese Patent No. 5647738, the compounds represented by general formula (1) and the compounds described in paragraphs 0022 to 0024 of JP 2021-173858 A, the compounds represented by general formula (1) and the compounds described in paragraphs 0117 to 0120 of JP 2021-170089 A, and the like.
  • oxime compound examples include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime), and the like.
  • Irgacure OXE01 Irgacure OXE02, Irgacure OXE03, Irgacure OXE04, and Irgacure OXE05 (all manufactured by BASF), TR-PBG-301, TR-PBG-304, TR-PBG-305, TR-PBG-309, TR-PBG-3054, TR-PBG-3057, TR-PBG-314, TR-PBG-327, and TR-PBG-309.
  • oxime compound examples include R-PBG-345, TR-PBG-346, TR-PBG-358, TR-PBG-365, TR-PBG-380, TR-PBG-610, TR-NPI-807, TR-PBG-A, and TR-PBG-B (all manufactured by TRONLY), ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, photopolymerization initiator 2 described in JP-A 2012-014052), and Esacure 563 (manufactured by IGM).
  • ADEKA Arcles NCI-730, NCI-831, NCI-831E, and NCI-930 all manufactured by ADEKA Corporation).
  • photopolymerization initiators that can be used include oxime compounds having a fluorene ring, oxime compounds having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring, oxime compounds having a fluorine atom, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, oxime compounds in which a substituent having a hydroxy group is bonded to a carbazole skeleton, and compounds described in paragraphs 0143 to 0149 of WO 2022/085485.
  • Another photopolymerization initiator that can be used is a compound represented by formula (OX-1).
  • X 1a represents a divalent linking group containing at least one ring selected from the group consisting of an aromatic ring and a heterocyclic ring;
  • R 1a represents a hydrogen atom or an acyl group;
  • R2a represents an alkyl group or an aryl group;
  • R 3a and R 4a each independently represent a hydrogen atom or an alkyl group;
  • Alk 1 and Alk 2 each independently represent an alkyl group;
  • R 3a and R 4a may be bonded to form a ring;
  • Alk 1 and Alk 2 may be linked to form a ring;
  • n represents 0 or 1.
  • Examples of the divalent linking group represented by X 1a in formula (OX-1) include a divalent aromatic ring group, a divalent heterocyclic group, a divalent group in which two or more aromatic ring groups are bonded via a single bond or a linking group, a divalent group in which two or more heterocyclic groups are bonded via a single bond or a linking group, and a divalent group in which an aromatic ring group and a heterocyclic group are bonded via a single bond or a linking group.
  • Examples of the linking group that bonds the above-mentioned aromatic ring groups, heterocyclic groups, or aromatic ring groups and heterocyclic groups include -CH 2 -, -O-, -CO-, -S-, -NR x -, and groups formed by combining these.
  • R x represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.
  • X 1a in formula (OX-1) is preferably a group represented by any one of formulas (X-1) to (X-13), more preferably a group represented by formula (X-1), formula (X-2), formula (X-4), formula (X-6) or formula (X-8), and even more preferably a group represented by formula (X-2) or formula (X-6).
  • R X1 to R X9 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group, and * represents a bond.
  • the number of carbon atoms in the alkyl group represented by R X1 to R X9 is preferably 1 to 15, and more preferably 1 to 10.
  • the alkyl group may be linear, branched, or cyclic.
  • the alkyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, and a heteroaryl group.
  • the number of carbon atoms in the alkenyl group represented by R X1 to R X9 is preferably 2 to 15, and more preferably 2 to 10.
  • the alkenyl group may be linear, branched, or cyclic.
  • the alkenyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, and a heteroaryl group.
  • the number of carbon atoms in the aryl group represented by R X1 to R X9 is preferably 6 to 20, more preferably 6 to 12, still more preferably 6 to 10, and particularly preferably 6.
  • the aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and a heteroaryl group.
  • the heteroaryl group represented by R X1 to R X9 is preferably a 5- or 6-membered ring.
  • the heteroatoms contained in the heteroaryl group are preferably oxygen, nitrogen, or sulfur atoms.
  • the number of heteroatoms contained in the heteroaryl group is preferably 1 to 3.
  • the heteroaryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and an aryl group.
  • R 1a represents a hydrogen atom or an acyl group, and is preferably an acyl group.
  • the alkyl group represented by R 2a is preferably an unsubstituted linear or branched alkyl group, and more preferably an unsubstituted linear alkyl group.
  • the number of carbon atoms in the aryl group represented by R 2a is preferably 6 to 20, more preferably 6 to 12, still more preferably 6 to 10, and particularly preferably 6.
  • the aryl group may have a substituent, but is preferably an unsubstituted aryl group.
  • R 3a and R 4a each independently represent a hydrogen atom or an alkyl group, and preferably a hydrogen atom.
  • the number of carbon atoms in the alkyl group represented by R 3a and R 4a is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3.
  • the alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear.
  • the alkyl group may have a substituent, but is preferably an unsubstituted alkyl group.
  • R3a and R4a may be bonded to form a ring.
  • the formed ring is preferably a 5- or 6-membered ring, and more preferably a 5- or 6-membered aliphatic hydrocarbon ring.
  • the ring formed is preferably a 5- or 6-membered ring, more preferably a 5- or 6-membered aliphatic hydrocarbon ring, and more preferably a cyclopentane ring or a cyclohexane ring.
  • Examples of the substituent represented by R 1b and R 2b include an alkyl group and an aryl group, and an alkyl group is preferable.
  • the alkyl group preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms.
  • the alkyl group may be linear, branched, or cyclic.
  • the alkyl group may have a substituent.
  • Examples of the substituent include a halogen atom, an aryl group, an alkenyl group, an alkynyl group, and a heteroaryl group.
  • the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, even more preferably 6 to 10 carbon atoms, and particularly preferably 6 carbon atoms.
  • the aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and a heteroaryl group.
  • Ar 1b represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent, and Ar 1b is preferably an aryl group which may have a substituent.
  • the number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 12, still more preferably 6 to 10, and particularly preferably 6.
  • the substituent include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylthio group, an arylthio group, a nitro group, and an acyl group, and an acyl group is preferred.
  • Another photopolymerization initiator that can be used is a compound represented by formula (OX-3).
  • Ar 1c represents a (k+m+1)-valent aromatic ring group or a (k+m+1)-valent heterocyclic group
  • Ar 2c represents a (k+2)-valent aromatic ring group or a (k+2)-valent heterocyclic group
  • R 1c to R 3c each independently represent a substituent
  • L 1c represents a single bond or CR 11c R 12c
  • R 11c and R 12c each independently represent a hydrogen atom, an alkyl group, or an aryl group
  • X 1c represents —CH 2 —, —N—, —O— or —S—
  • k represents 0 or 1
  • m represents an integer of 0 to 4
  • n represents 0 or 1.
  • Examples of the substituent represented by R 1c and R 2c include an alkyl group and an aryl group, and an alkyl group is preferred.
  • the alkyl group preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms.
  • the alkyl group may be linear, branched, or cyclic.
  • the alkyl group may have a substituent.
  • Examples of the substituent include a halogen atom, an aryl group, an alkenyl group, an alkynyl group, and a heteroaryl group.
  • the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, even more preferably 6 to 10 carbon atoms, and particularly preferably 6 carbon atoms.
  • the aryl group may have a substituent.
  • substituents include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and a heteroaryl group.
  • R 2c is preferably an alkyl group having a branched or cyclic structure.
  • Examples of the substituent represented by R 3c include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group and an acyl group, with an acyl group being preferred.
  • L 1c represents a single bond or CR 11c R 12c
  • R 11c and R 12c each independently represent a hydrogen atom, an alkyl group, or an aryl group.
  • the alkyl group and aryl group in R 11c and R 12c have the same meanings as the alkyl group and aryl group in R 1c and R 2c .
  • L 1c is preferably a single bond.
  • X 1c represents —CH 2 —, —N—, —O— or —S—, and is preferably —O— or —S—.
  • Ar 1c represents a (k+m+1)-valent aromatic ring group or a (k+m+1)-valent heterocyclic group, and is preferably a (k+m+1)-valent aromatic ring group.
  • the aromatic ring group is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group.
  • Ar2c represents a (k+2)-valent aromatic ring group or a (k+2)-valent heterocyclic group, and is preferably a (k+2)-valent aromatic ring group.
  • the aromatic ring group is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group.
  • k represents 0 or 1, and is preferably 0.
  • m represents an integer of 0 to 4, preferably 0 or 1, and more preferably 1.
  • n represents 0 or 1, and is preferably 0.
  • oxime compounds include the compounds shown below.
  • bifunctional, trifunctional or higher functional photopolymerization initiators may also be used.
  • Specific examples of bifunctional, trifunctional or higher functional photopolymerization initiators include the compounds described in paragraph 0148 of WO 2022/065215.
  • the content of the photopolymerization initiator in the total solids content of the photocurable composition is preferably 1 to 20% by mass.
  • the lower limit is preferably 1.5% by mass or more, and more preferably 2% by mass or more.
  • the upper limit is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 8% by mass or less.
  • only one type of photopolymerization initiator may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof be within the above range.
  • the content of the specific compound in the photopolymerization initiator is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.
  • the content of the specific compound in the total solids of the photocurable composition is preferably 0.1 to 50% by mass.
  • the lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more.
  • the upper limit is preferably 45% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.
  • only one type of specific compound may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof be within the above range.
  • the photocurable composition of the present invention contains a polymerizable compound.
  • the polymerizable compound include a compound having an ethylenically unsaturated bond-containing group.
  • examples of the ethylenically unsaturated bond-containing group include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group.
  • the polymerizable compound used in the present invention is preferably a radically polymerizable compound.
  • the polymerizable compound may be in any chemical form, such as a monomer, prepolymer, or oligomer, but a monomer is preferred.
  • the molecular weight of the polymerizable compound is preferably 100 to 3,000.
  • the upper limit is more preferably 2,000 or less, and even more preferably 1,500 or less.
  • the lower limit is more preferably 150 or more, and even more preferably 250 or more.
  • the polymerizable compound is preferably a compound containing two or more ethylenically unsaturated bond-containing groups, more preferably a compound containing 2 to 15 ethylenically unsaturated bond-containing groups, and even more preferably a compound containing 2 to 6 ethylenically unsaturated bond-containing groups. Furthermore, the polymerizable compound is preferably a difunctional to 15functional (meth)acrylate compound, and more preferably a difunctional to hexafunctional (meth)acrylate compound. Specific examples of polymerizable compounds include the compounds described in paragraphs 0075 to 0083 of WO 2022/065215 and the compounds described in Taiwan Patent Application Publication No. 201832008.
  • Preferred polymerizable compounds include dipentaerythritol tri(meth)acrylate (commercially available product: KAYARAD D-330, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available product: KAYARAD D-320, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available product: KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available products: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., and NK Ester A-DPH-12E, manufactured by Shin-Nakamura Chemical Co., Ltd.), and compounds in which the (meth)acryloyl group is bonded via an ethylene glycol and/or propylene glycol residue (e.g.,
  • polymerizable compounds examples include diglycerin EO (ethylene oxide) modified (meth)acrylate (commercially available product: M-460, manufactured by Toagosei Co., Ltd.), pentaerythritol tetraacrylate (NK Ester A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (KAYARAD HDDA, manufactured by Nippon Kayaku Co., Ltd.), and RP-104.
  • diglycerin EO ethylene oxide modified (meth)acrylate
  • M-460 manufactured by Toagosei Co., Ltd.
  • pentaerythritol tetraacrylate NK Ester A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.
  • 1,6-hexanediol diacrylate KAYARAD HDDA, manufactured by Nippon Kayaku Co., Ltd.
  • a polymerizable compound having an ethylene oxide repeating chain can also be used. According to this embodiment, the effects of the present invention are more pronounced.
  • Examples of the polymerizable compound having an ethylene oxide repeating chain include a compound represented by formula (EO-1).
  • R E1 in formula (EO-1) represents a hydrogen atom or a methyl group.
  • L E1 represents an m-valent linking group.
  • Examples of the m-valent linking group represented by L E1 include a hydrocarbon group, a heterocyclic group, —O—, —S—, —NR A1 —, —CO—, —COO—, —OCO—, —SO 2 —, and groups combining two or more of these groups.
  • R A1 represents a hydrogen atom, an alkyl group, or an aryl group, and is preferably a hydrogen atom.
  • the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
  • the aliphatic hydrocarbon group may be cyclic or acyclic.
  • the acyclic aliphatic hydrocarbon group may be a linear aliphatic hydrocarbon group or a branched aliphatic hydrocarbon group.
  • the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group.
  • the hydrocarbon group may or may not have a substituent.
  • the cyclic aliphatic hydrocarbon group and the aromatic hydrocarbon group may be a monocyclic ring or a fused ring.
  • the heterocyclic group may be a single ring or a condensed ring.
  • the heterocyclic group is preferably a 5-membered or 6-membered ring.
  • the heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group.
  • examples of heteroatoms constituting the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom.
  • n represents an integer from 1 to 20
  • m represents an integer from 2 to 10.
  • n is preferably an integer from 1 to 15, and more preferably an integer from 1 to 10.
  • m is preferably an integer from 2 to 8, and more preferably an integer from 2 to 6.
  • a polymerizable compound having a fluorene skeleton can also be used.
  • the polymerizable compound having a fluorene skeleton is preferably a bifunctional polymerizable compound.
  • Commercially available polymerizable compounds having a fluorene skeleton include OGSOL EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., (meth)acrylate monomers having a fluorene skeleton).
  • a compound having an amino group and an ethylenically unsaturated bond-containing group (hereinafter also referred to as an amine monomer) can also be used.
  • the amine monomer is preferably a compound containing 1 to 10 ethylenically unsaturated bond-containing groups, more preferably a compound containing 2 to 10 groups, and even more preferably a compound containing 3 to 10 groups.
  • the pKaH of the amine monomer is preferably 5.5 or higher, more preferably 6.5 or higher, and even more preferably 7.5 or higher, because this effectively suppresses oxygen inhibition by the amine and further increases the sensitivity of the photosensitive composition.
  • pKaH is a value representing the pKa of the conjugate acid of the base.
  • the pKaH value of the amine monomer is calculated in accordance with the method described in A Web Server for Small Molecule pKa Prediction Using a Graph-Convolutional Neural Network, J. Chem. Inf. Model. 2021, 61, 7, 3159-3165.
  • the upper limit is preferably 10 mmol/g or less, and more preferably 9 mmol/g or less.
  • the lower limit is preferably 1 mmol/g or more, and more preferably 2 mmol/g or more.
  • the ethylenically unsaturated bond-containing group value of the amine monomer is a numerical value representing the molar amount of ethylenically unsaturated bond-containing groups per gram of solids in the amine monomer.
  • the amine value of the amine monomer is preferably 1 to 150 mgKOH/g.
  • the lower limit of the amine value is preferably 2.5 mgKOH/g or more, and more preferably 5 mgKOH/g or more.
  • the upper limit of the amine value is preferably 125 mgKOH/g or less, and more preferably 100 mgKOH/g or less.
  • the hydroxyl value of the amine monomer is preferably 75 mgKOH/g or less, more preferably 50 mgKOH/g or less, and even more preferably 30 mgKOH/g or less.
  • the molecular weight of the amine monomer is preferably 100 to 5,000, and more preferably 200 to 3,000.
  • amine monomers include Ebecryl 80, Ebecryl 81, Ebecryl 83, and Ebecryl 7100 manufactured by Daicel Allnex Corporation, Aronix MT-3041 and 3042 manufactured by Toagosei Co., Ltd., Light Ester DE and Light Ester DM manufactured by Kyoeisha Chemical Co., Ltd., and CN383, CN371 NS, CN386, CN549 NS, CN550, CN551 NS, and CN9906NS manufactured by Arkema.
  • the content of the polymerizable compound in the total solid content of the photocurable composition is preferably 1 to 30% by mass.
  • the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.
  • the lower limit is preferably 3% by mass or more, and more preferably 5% by mass or more.
  • the photocurable composition of the present invention may contain only one polymerizable compound or may contain two or more polymerizable compounds. When two or more polymerizable compounds are contained, the total amount thereof is preferably within the above range.
  • the photocurable composition of the present invention preferably contains a resin.
  • the resin is blended, for example, to disperse pigments or the like in the photocurable composition or as a binder.
  • Resins used primarily to disperse pigments or the like in the photocurable composition are also called dispersants.
  • these uses of resins are merely examples, and resins can also be used for purposes other than these uses.
  • the weight average molecular weight (Mw) of the resin is preferably 3,000 to 2,000,000.
  • the upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less.
  • the lower limit is preferably 4,000 or more, and more preferably 5,000 or more.
  • resins examples include (meth)acrylic resins, epoxy resins, (meth)acrylamide resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyurethane resins, polyamide resins, polyimide resins, polyamic acid resins, polybenzoxazole resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, and siloxane resins.
  • At least one resin selected from (meth)acrylic resins, polyester resins, polyurethane resins, polyamide resins, polyimide resins, polyamic acid resins, and polybenzoxazole resins is preferred.
  • Polyimide resins and polyamic acid resins are obtained by polycondensation of aromatic or aliphatic acid dianhydrides with aromatic or aliphatic diamines.
  • Polyimide resins and polyamic acid resins may contain crosslinkable groups. Examples of crosslinkable groups include ethylenically unsaturated bond-containing groups and cyclic ether groups.
  • Examples of ethylenically unsaturated bond-containing groups include vinyl groups, (meth)allyl groups, (meth)acryloyl groups, and styrene groups.
  • Examples of cyclic ether groups include epoxy groups and oxetanyl groups.
  • polyimide resins and polyamic acid resins include resins in which crosslinkable groups have been introduced into polyimides or polyamic acids having carboxylic acids, as described in JP 2023-166413 A; polyimide resins or polyamic acid resins, as described in WO 2022/019253; block resins having poly(meth)acrylic, polyether, or polyester structures or combinations thereof at both ends of polyimide resins or polyamic acid resins, as described in WO 2022/019254; and resins having both a polyester moiety with a graft polymer portion and a polyamic acid moiety, as described in WO 2022/019255.
  • Resins include those described in paragraphs 0091 to 0099 of WO 2022/065215, blocked polyisocyanate resins described in JP 2016-222891 A, resins described in JP 2020-122052 A, resins described in JP 2020-111656 A, resins described in JP 2020-139021 A, resins containing a structural unit having a ring structure in the main chain and a structural unit having a biphenyl group in the side chain described in JP 2017-138503 A, resins described in paragraphs 0199 to 0233 of JP 2020-186373 A, alkali-soluble resins described in JP 2020-186325 A, and Korean Patent Publication No.
  • a resin having an acid group examples include a carboxy group, a phosphate group, a sulfo group, and a phenolic hydroxy group.
  • the acid value of the resin having acid groups is preferably 30 to 500 mgKOH/g.
  • the lower limit is preferably 40 mgKOH/g or more, and more preferably 50 mgKOH/g or more.
  • the upper limit is preferably 400 mgKOH/g or less, more preferably 300 mgKOH/g or less, and even more preferably 200 mgKOH/g or less.
  • the weight average molecular weight (Mw) of the resin having acid groups is preferably 5,000 to 100,000, and more preferably 5,000 to 50,000.
  • the number average molecular weight (Mn) of the resin having acid groups is preferably 1,000 to 20,000.
  • the resin having an acid group preferably contains repeating units having an acid group on the side chain, and more preferably contains 5 to 70 mol% of repeating units having an acid group on the side chain out of all repeating units of the resin.
  • the upper limit of the content of repeating units having an acid group on the side chain is preferably 50 mol% or less, more preferably 30 mol% or less.
  • the lower limit of the content of repeating units having an acid group on the side chain is preferably 10 mol% or more, more preferably 20 mol% or more.
  • resins having acid groups please refer to paragraphs [0558] to [0571] of JP 2012-208494 A (corresponding paragraphs [0685] to [0700] of U.S. Patent Application Publication No. 2012/0235099) and paragraphs [0076] to [0099] of JP 2012-198408 A, the contents of which are incorporated herein by reference.
  • Commercially available resins having acid groups can also be used.
  • There are no particular restrictions on the method for introducing acid groups into the resin but examples include the method described in Japanese Patent No. 6,349,629 A.
  • Another method for introducing acid groups into the resin involves reacting an acid anhydride with the hydroxyl group generated by the ring-opening reaction of an epoxy group.
  • the photocurable composition of the present invention also preferably contains a resin having a basic group.
  • the resin having a basic group is preferably a resin containing a repeating unit having a basic group in the side chain, more preferably a copolymer having a repeating unit having a basic group in the side chain and a repeating unit not having a basic group, and even more preferably a block copolymer having a repeating unit having a basic group in the side chain and a repeating unit not having a basic group.
  • the resin having a basic group can also be used as a dispersant.
  • the amine value of the resin having a basic group is preferably 5 to 300 mgKOH/g.
  • the lower limit is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more.
  • the upper limit is preferably 200 mgKOH/g or less, more preferably 100 mgKOH/g or less.
  • resins with basic groups include DISPERBYK-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, and BYK-LPN6919 (all manufactured by BYK-Chemie), Solsperse 11200, 13240, 13650, 13940, and 24 000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 38500, 39000, 53095, 56000, 7100 (all manufactured by Lubrizol Japan), Efka PX 4300, 4330, 4046, 4060, 4080 (all manufactured by BASF), and the like.
  • the resin having a basic group may be the block copolymer (B) described in paragraphs [0063] to [0112] of JP 2014-219665 A, the block copolymer A1 described in paragraphs [0046] to [0076] of JP 2018-156021 A, or the vinyl resin having a basic group described in paragraphs [0150] to [0153] of JP 2019-184763 A, the contents of which are incorporated herein by reference.
  • the photocurable composition of the present invention contains both a resin having an acid group and a resin having a basic group.
  • This embodiment further improves the storage stability of the photocurable composition.
  • the content of the resin having a basic group is preferably 20 to 500 parts by mass, more preferably 30 to 300 parts by mass, and even more preferably 50 to 200 parts by mass per 100 parts by mass of the resin having an acid group.
  • a resin having an aromatic carboxy group may be contained in the main chain of the repeating unit or in the side chain of the repeating unit.
  • the aromatic carboxy group is preferably contained in the main chain of the repeating unit.
  • an aromatic carboxy group refers to a group having a structure in which one or more carboxy groups are bonded to an aromatic ring.
  • the number of carboxy groups bonded to the aromatic ring is preferably 1 to 4, and more preferably 1 to 2.
  • resins having an aromatic carboxy group include the resins described in paragraphs 0082 to 0107 of WO 2021/166858.
  • crosslinkable groups include ethylenically unsaturated bond-containing groups and cyclic ether groups.
  • ethylenically unsaturated bond-containing groups include vinyl groups, (meth)allyl groups, (meth)acryloyl groups, and styrene groups.
  • cyclic ether groups include epoxy groups and oxetanyl groups.
  • the resin preferably contains a graft resin.
  • graft resins include resins having repeating units with graft chains.
  • a graft chain refers to a polymer chain that branches off from the main chain of the repeating unit.
  • the graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2,000 atoms excluding hydrogen atoms, and even more preferably 60 to 500 atoms excluding hydrogen atoms.
  • the graft chain preferably contains repeating units of at least one structure selected from the group consisting of polyester structure, polyether structure, poly(meth)acrylic structure, polystyrene structure, polyurethane structure, polyurea structure, and polyamide structure; more preferably contains repeating units of at least one structure selected from the group consisting of polyester structure, polyether structure, poly(meth)acrylic structure, and polystyrene structure; even more preferably contains repeating units of at least one structure selected from the group consisting of polyester structure, polyether structure, and poly(meth)acrylic structure; still more preferably contains repeating units of a polyester structure or polyether structure; and particularly preferably contains repeating units of a polyester structure.
  • repeating units of polyester structures include repeating units of structures represented by the following formula (G-1), formula (G-4), or formula (G-5).
  • Examples of repeating units of polyether structures include repeating units of structures represented by the following formula (G-2).
  • Examples of repeating units of poly(meth)acrylic structures include repeating units of structures represented by the following formula (G-3).
  • Examples of repeating units of polystyrene structures include repeating units of structures represented by the following formula (G-6).
  • R G1 and R G2 each independently represent an alkylene group.
  • the number of carbon atoms in the alkylene group represented by R G1 is preferably 1 to 20, more preferably 2 to 16, and even more preferably 2 to 12.
  • the alkylene group is preferably linear or branched, and more preferably linear.
  • the number of carbon atoms in the alkylene group represented by R G2 is preferably 1 to 10, more preferably 1 to 5, even more preferably 2 to 5, and still more preferably 2 or 3.
  • the alkylene group is preferably linear or branched, and more preferably linear.
  • R G3 represents a hydrogen atom or a methyl group
  • Q G1 represents —O— or —NH—
  • L G1 represents a single bond or a divalent linking group
  • R G4 represents a hydrogen atom or a substituent.
  • Examples of the divalent linking group represented by L G1 include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms), an oxyalkylenecarbonyl group (preferably an oxyalkylenecarbonyl group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, -OCO-, -S-, and groups formed by combining two or more of these.
  • an alkylene group preferably an alkylene group having 1 to 12 carbon atoms
  • an alkyleneoxy group preferably an alkyleneoxy group having 1 to 12 carbon atoms
  • an oxyalkylenecarbonyl group preferably an oxyalkylenecarbonyl group having 1 to 12 carbon atoms
  • an arylene group preferably an
  • Examples of the substituent represented by R G4 include a hydroxy group, a carboxy group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthioether group, an arylthioether group, and a heterocyclic thioether group.
  • R G5 represents a hydrogen atom or a methyl group
  • R G6 represents an aryl group.
  • the number of carbon atoms in the aryl group represented by R G6 is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12.
  • the aryl group represented by R G6 may have a substituent. Examples of the substituent include a hydroxy group, a carboxy group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthioether group, an arylthioether group, and a heterocyclic thioether group.
  • the terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent.
  • substituent include a hydroxy group, a carboxy group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthioether group, an arylthioether group, and a heterocyclic thioether group.
  • groups that have a steric repulsion effect are preferred, and alkyl or alkoxy groups having 5 to 24 carbon atoms are preferred.
  • the alkyl and alkoxy groups may be linear, branched, or cyclic, with linear or branched groups being preferred.
  • the graft chain preferably has a structure represented by the following formula (G-1a), (G-2a), (G-3a), (G-4a), (G-5a) or (G-6a), and more preferably has a structure represented by formula (G-1a), (G-4a) or (G-5a).
  • R G1 and R G2 each represent an alkylene group
  • R G3 represents a hydrogen atom or a methyl group
  • Q G1 represents -O- or -NH-
  • L G1 represents a single bond or a divalent linking group
  • R G4 represents a hydrogen atom or a substituent
  • R G5 represents a hydrogen atom or a methyl group
  • R G6 represents an aryl group
  • W 100 represents a hydrogen atom or a substituent
  • n1 to n6 each independently represent an integer of 2 or more.
  • R G1 to R G6 , Q G1 , and L G1 have the same meanings and preferred ranges as R G1 to R G6 , Q G1 , and L G1 described in formulas (G-1) to (G-6).
  • W 100 is preferably a substituent.
  • the substituent include a hydroxy group, a carboxy group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthioether group, an arylthioether group, and a heterocyclic thioether group.
  • a group having a steric repulsion effect is preferred, and an alkyl group or an alkoxy group having 5 to 24 carbon atoms is preferred.
  • the alkyl group and the alkoxy group may be linear, branched, or cyclic, and linear or branched groups are preferred.
  • n1 to n6 are each preferably an integer from 2 to 100, more preferably an integer from 2 to 80, and even more preferably an integer from 8 to 60.
  • the R G1 in each repeating unit may be the same or different.
  • the arrangement of the repeating units is not particularly limited and may be random, alternating, or block. The same applies to formulas (G-2a) to (G-6a).
  • the graft chain has a structure represented by formula (G-1a), formula (G-4a), or formula (G-5a) and includes two or more different R G1 repeating units.
  • repeating unit having a graft chain examples include a repeating unit represented by formula (b1-2).
  • a b12 represents a trivalent linking group
  • L b12 represents a single bond or a divalent linking group
  • Y b12 represents a graft chain.
  • Examples of the trivalent linking group represented by A b12 include a poly(meth)acrylic linking group, a polyalkyleneimine linking group, a polyester linking group, a polyurethane linking group, a polyurea linking group, a polyamide linking group, a polyether linking group, and a polystyrene linking group.
  • a poly(meth)acrylic linking group or a polyalkyleneimine linking group is preferred, and a poly(meth)acrylic linking group is more preferred.
  • Examples of the divalent linking group represented by L b12 include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, -OCO-, -S-, and groups formed by combining two or more of these groups.
  • Examples of the graft chain represented by Y b12 include the graft chains described above.
  • the weight-average molecular weight of the repeating unit having a graft chain is preferably 1,000 or more, more preferably 1,000 to 10,000, and even more preferably 1,000 to 7,500.
  • the weight-average molecular weight of a repeating unit having a graft chain is a value calculated from the weight-average molecular weight of the raw material monomer used to polymerize the repeating unit.
  • a repeating unit having a graft chain can be formed by polymerizing a macromonomer.
  • a macromonomer refers to a polymeric compound in which a polymerizable group has been introduced at the polymer terminal.
  • the weight-average molecular weight of the macromonomer corresponds to the repeating unit having a graft chain.
  • the content of repeating units having graft chains is preferably 1 to 60 mol% of the total repeating units of the graft resin.
  • the upper limit is preferably 50 mol% or less, and more preferably 40 mol% or less.
  • the lower limit is preferably 2 mol% or more, and more preferably 5 mol% or more.
  • the graft resin further contains a repeating unit having a crosslinkable group.
  • crosslinkable groups include ethylenically unsaturated bond-containing groups and cyclic ether groups.
  • ethylenically unsaturated bond-containing groups include vinyl groups, (meth)allyl groups, (meth)acryloyl groups, and styrene groups.
  • cyclic ether groups include epoxy groups and oxetanyl groups.
  • the content of repeating units having crosslinkable groups is preferably 1 mol% or more, and more preferably 1 to 80 mol%, of all repeating units in the graft resin.
  • the upper limit is preferably 70 mol% or less, and more preferably 60 mol% or less.
  • the lower limit is preferably 2 mol% or more, and more preferably 5 mol% or more.
  • the graft resin further contains a repeating unit having an acid group.
  • the acid group include a carboxy group, a sulfo group, and a phosphate group.
  • the content of repeating units having an acid group is preferably 1 to 80 mol%, more preferably 5 to 80 mol%, and even more preferably 10 to 80 mol%, of all repeating units in the graft resin.
  • a resin containing a repeating unit represented by formula (Ac-2) can also be used.
  • Ar 10 represents a group containing an aromatic carboxy group
  • L 11 represents —COO— or —CONH—
  • L 12 represents a trivalent linking group
  • P 10 represents a polymer chain.
  • Examples of the group containing an aromatic carboxy group represented by Ar 10 in formula (Ac-2) include a structure derived from an aromatic tricarboxylic acid anhydride, a structure derived from an aromatic tetracarboxylic acid anhydride, etc.
  • Examples of the aromatic tricarboxylic acid anhydride and aromatic tetracarboxylic acid anhydride include compounds having the following structure:
  • Q 1 represents a single bond, —O—, —CO—, —COOCH 2 CH 2 OCO—, —SO 2 —, —C(CF 3 ) 2 —, a group represented by the following formula (Q-1) or a group represented by the following formula (Q-2).
  • the group containing an aromatic carboxy group represented by Ar 10 may have a crosslinkable group.
  • Specific examples of the group containing an aromatic carboxy group represented by Ar 10 include a group represented by formula (Ar-11), a group represented by formula (Ar-12), and a group represented by formula (Ar-13).
  • n1 represents an integer of 1 to 4, preferably 1 or 2, and more preferably 2.
  • n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 2.
  • n3 and n4 each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 1 or 2, and even more preferably 1. However, at least one of n3 and n4 is an integer of 1 or greater.
  • Q 1 represents a single bond, —O—, —CO—, —COOCH 2 CH 2 OCO—, —SO 2 —, —C(CF 3 ) 2 —, a group represented by formula (Q-1) above or a group represented by formula (Q-2) above.
  • *1 represents the bonding position with L10 .
  • L 11 in formula (Ac-2) represents —COO— or —CONH—, and is preferably —COO—.
  • Examples of the trivalent linking group represented by L 12 in formula (Ac-2) include hydrocarbon groups, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and groups combining two or more of these.
  • Examples of the hydrocarbon group include aliphatic hydrocarbon groups and aromatic hydrocarbon groups.
  • the aliphatic hydrocarbon group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 1 to 15.
  • the aliphatic hydrocarbon group may be linear, branched, or cyclic.
  • the aromatic hydrocarbon group preferably has 6 to 30 carbon atoms, more preferably 6 to 20, and even more preferably 6 to 10.
  • the hydrocarbon group may have a substituent. Examples of the substituent include a hydroxy group.
  • the trivalent linking group represented by L 12 is preferably a group represented by formula (L12-1), and more preferably a group represented by formula (L12-2).
  • L 12b represents a trivalent linking group
  • X 1 represents S
  • *1 represents the bonding position to L 11 in formula (Ac-2)
  • *2 represents the bonding position to P 10 in formula (Ac-2).
  • Examples of the trivalent linking group represented by L 12b include hydrocarbon groups and groups in which a hydrocarbon group is combined with at least one selected from -O-, -CO-, -COO-, -OCO-, -NH-, and -S-, and the like.
  • a hydrocarbon group or a group in which a hydrocarbon group is combined with -O- is preferred.
  • L 12c represents a trivalent linking group
  • X 1 represents S
  • *1 represents the bonding position to L 11 in formula (Ac-2)
  • *2 represents the bonding position to P 10 in formula (Ac-2).
  • Examples of the trivalent linking group represented by L 12c include hydrocarbon groups and groups in which a hydrocarbon group is combined with at least one selected from -O-, -CO-, -COO-, -OCO-, -NH-, and -S-, and a hydrocarbon group is preferred.
  • the polymer chain represented by P10 in formula (Ac-2) includes a polymer chain containing a repeating unit of at least one structure selected from the group consisting of a polyester structure, a polyether structure, a poly(meth)acrylic structure, a polystyrene structure, a polyurethane structure, a polyurea structure, and a polyamide structure.
  • Examples of the repeating unit of the polyester structure include a repeating unit of the structure represented by formula (G-1), formula (G-4), or formula (G-5) above.
  • Examples of the repeating unit of the polyether structure include a repeating unit of the structure represented by formula (G-2) above.
  • Examples of the repeating unit of the poly(meth)acrylic structure include a repeating unit of the structure represented by formula (G-3) above.
  • Examples of the repeating unit of the polystyrene structure include a repeating unit of the structure represented by formula (G-6) above.
  • the polymer chain represented by P10 may contain a repeating unit having a crosslinkable group.
  • the proportion of the repeating units having a crosslinkable group in all repeating units constituting P10 is preferably 1 mol% or more, more preferably 1 to 80 mol%.
  • the upper limit is preferably 70 mol% or less, more preferably 60 mol% or less.
  • the lower limit is preferably 2 mol% or more, more preferably 5 mol% or more.
  • the polymer chain represented by P10 may contain a repeating unit containing an acid group.
  • the acid group include a carboxy group, a phosphate group, a sulfo group, and a phenolic hydroxy group.
  • the proportion of the repeating unit having an acid group in all repeating units constituting P10 is preferably 1 to 80 mol%, more preferably 5 to 80 mol%, and even more preferably 10 to 80 mol%.
  • the weight average molecular weight of the polymer chain represented by P10 is preferably 500 to 20,000.
  • the lower limit is preferably 1,000 or more.
  • the upper limit is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.
  • X represents a 4+m-valent organic group
  • Y represents a 2+n-valent organic group
  • R and R each independently represent a group containing a polymerizable group
  • n represents an integer of 0 to 6
  • m represents an integer of 0 to 6
  • n+m is an integer of 1 or more
  • X represents a 4+m-valent organic group
  • Y represents a 2 +n-valent organic group
  • a and A each independently represent a monovalent organic group
  • R and R each independently represent a group containing a polymerizable group
  • n represents an integer of 0 to 6
  • m represents an integer of 0 to 6
  • n+m is an integer of 1 or more, provided that when at least one of A and A has a polymerizable group, n+m may be 0.
  • -X B1 - X B1 in formula (B-1) and formula (B-2) is preferably a structure derived from an acid anhydride monomer, but is not limited thereto.
  • the acid anhydride monomer is not particularly limited as long as it has two cyclic acid anhydride groups in one molecule. It may be an aromatic acid anhydride, an aliphatic acid anhydride, or a mixture thereof.
  • X B1 is preferably a group having an alicyclic hydrocarbon.
  • XB1 those represented by the following formulae (Xp-1) to (Xp-23) are preferably used.
  • *1 represents the bonding site to the carbonyl group represented by *1 in the following formula (BX-1) or formula (BX-2), respectively
  • *2 represents the bonding site to the carbonyl group represented by *2 in the following formula (BX-1) or formula (BX-2).
  • the following formulae (BX-1) and (BX-2) are obtained by adding the symbols *1 and *2 to formula (B-1) and formula (B-2), respectively.
  • R1 and R2 each independently represent a hydrogen atom or a substituent;
  • R1 and R2 may bond to form a ring structure, which may be an aromatic ring, or
  • R1 and R2 may combine to form a benzene ring.
  • Ls When multiple Ls are present in one molecule, they may be the same or different.
  • R3 , R4 , R5 , and R6 each independently represent a hydrogen atom, an alkyl group, or an aryl group ; adjacent R3 to R6 may be linked via a divalent organic group to form a ring.
  • R7 and R8 each represent an alkyl group, an aryl group, a fluoroalkyl group, a fluoroaryl group, an alkoxy group, an aryloxy group, a hydroxyl group, a carboxyl group, or a halogen atom.
  • n1 and n2 each independently represent an integer of 0 to 4. When geometrical isomers exist, the distinction between cis/trans and endo/exo is not particularly limited.
  • X 1 to X 4 represent a single bond or a divalent linking group, and are preferably a single bond, -C(Rx) 2 - (Rx represents a hydrogen atom or a substituent.
  • Rx When Rx is a substituent, they may be linked to each other to form a ring), -O-, -S( ⁇ O) 2 -, -C( ⁇ O), -S-, -NR N -, an alkylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, an arylene group, a heteroarylene group, -C( ⁇ O)O-, -C( ⁇ O)NH-, or a combination thereof, and more preferably a single bond or -C(Rx) 2 -.
  • Rx represents a substituent
  • specific examples thereof include an alkyl group, an alkyl group optionally substituted with a fluorine atom, and a fluorenyl group.
  • R 1 N represents a hydrogen atom or an organic group, preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or an alkyl group.
  • linking groups X 1 to X 4 are divalent linking groups represented by the following formula (X1-1) in terms of exhibiting excellent mechanical strength.
  • n and m each independently represent 0 or 1.
  • T1 and T2 each independently represent a single bond, -O-, -S-, or -NR-, where R represents a hydrogen atom, an alkyl group, or an aryl group.
  • P1 , P2 , and P3 each independently represent an aromatic group having 6 to 12 carbon atoms, a heterocyclic group having 5 to 12 carbon atoms, an aliphatic group having 1 to 12 carbon atoms, or an alicyclic group having 4 to 12 carbon atoms.
  • Each of the groups P1 , P2, and P3 may further have a substituent.
  • substituents examples include an alkyl group, a fluoroalkyl group, an aryl group, an alkoxy group, an aryloxy group, a hydroxyl group, a carboxyl group, and a halogen atom.
  • substitution position of these groups is not particularly limited.
  • R each independently represents a hydrogen atom, an alkyl group, a fluoroalkyl group, or an aryl group, and Rs may be bonded to each other to form a ring.
  • p and q each independently represent 0 or 1;
  • aromatic carboxylic dianhydrides such as pyromellitic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 4-chloroformylphthalic anhydride, trimellitic anhydride, tetrachlorophthalic anhydride, phthalic anhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-oxydiphthalic anhydride, 4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 4,4'-biphthalic anhydride, tetrabromophthalic anhydride, 3,4'-oxydiphthalic anhydride, 4-(1
  • aliphatic acid dianhydrides include bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, ethylenediaminetetraacetic acid dianhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic acid dianhydride, meso-butane-1,2,3,4-tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 4-(2,5-dioxotetrahydrofuran-3 Suitable examples of compounds that can be used include 1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, octahydrobiphenylene-4a,8b:4b,8a
  • -Y B1 - Y B1 in formula (B-1) and formula (B-2) is preferably a structure derived from a diamine monomer, but is not limited thereto.
  • the diamine monomer is not particularly limited as long as it has two primary amino groups in one molecule. It may be an aromatic diamine, an aliphatic diamine, or a mixture thereof.
  • Y B1 preferably has a structure of the following formulae (Yp-1) to (Yp-16), where * indicates the bonding site to the nitrogen atom.
  • R 10 to R 15 each independently represent an alkyl group, an aryl group, a fluoroalkyl group, a fluoroaryl group, an alkoxy group, an aryloxy group, a hydroxyl group, a carboxyl group, or a halogen atom.
  • R 16 and R 17 each independently represent a hydrogen atom, an alkyl group, or an aryl group.
  • a to f each independently represent an integer of 0 to 3.
  • n represents an integer of 1 to 12.
  • the substitution positions of R 10 to R 15 are not particularly specified.
  • Y 1 or Y 2 represents a single bond or a divalent linking group, and is preferably a single bond, -C(Rx) 2 - (Rx represents a hydrogen atom or a substituent.
  • Rx When Rx is a substituent, they may be linked to each other to form a ring), -O-, -S( ⁇ O) 2 -, -C( ⁇ O), -S-, -NR N -, an alkylene group, a cycloalkylene group, an alkenylene group, an alkynylene group, an arylene group, a heteroarylene group, -C( ⁇ O)O-, -C( ⁇ O)NH-, or a combination thereof, and more preferably a single bond or -C(Rx) 2 -.
  • Rx represents a substituent
  • specific examples thereof include an alkyl group, an alkyl group optionally substituted with a fluorine atom, and a fluorenyl group.
  • R 1 N represents a hydrogen atom or an organic group, preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom or an alkyl group.
  • the linking group Y1 or Y2 is more preferably a divalent linking group represented by the following formula (Y1-1) in terms of exhibiting excellent mechanical strength.
  • aromatic diamines such as 4,4'-diaminodiphenyl sulfone, 1,5-naphthalenediamine, 4,4'-diaminostilbene-2,2'-disulfonic acid, m-xylylenediamine, p-xylylenediamine, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 4,4'-methylenebis(2,6-diethylaniline), 1,3-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-methylenebis(2-chloroaniline), 1,4-bis[2-(4-aminophenyl)-2-propyl]benzene, 4,4'-diamino-2,2'-biphenyldisulfonic acid, 1,4-phenylenediamine, o-
  • aromatic diamines such as 4,4'-diamin
  • Suitable aliphatic diamines include, for example, bicyclo[2.2.1]heptane dimethanamine (mixture of isomers), 4,4'-methylenebis(cyclohexylamine) (mixture of isomers), 4,4'-methylenebis(2-methylcyclohexylamine) (mixture of isomers), isophoronediamine (mixture of cis- and trans-), 1,3-bis(aminomethyl)cyclohexane (mixture of cis- and trans-), 1,4-bis(aminomethyl)cyclohexane (mixture of cis- and trans-), 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-cyclohexanediamine (mixture of cis- and trans-), and 1,4-cyclohexanediamine (mixture of cis- and trans-).
  • R B1 and R B2 each independently represent a group containing a polymerizable group, and the polymerizable group is preferably a radically polymerizable group.
  • the polymerizable group include an ethylenically unsaturated bond-containing group, an epoxy group, an oxetanyl group, and a benzoxazolyl group, with an ethylenically unsaturated bond-containing group being preferred.
  • Examples of the ethylenically unsaturated bond-containing group include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a group having a norbornene skeleton.
  • a (meth)acryloyl group, a vinylphenyl group, or a maleimide group is preferred, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferred.
  • a vinylphenyl group or a maleimide group is preferred.
  • the (meth)acryloyl group preferably constitutes a (meth)acryloyloxy group or a (meth)acrylamide group, and from the viewpoint of reactivity, a (meth)acryloyloxy group is more preferred.
  • Lx 1 represents a single bond, —O—, —NR 1 —, —C( ⁇ O)O—, —OC( ⁇ O)—, —OC( ⁇ O)O—, —C( ⁇ O)NR 2 —, —NR 2 C( ⁇ O)—, —NR 2 C( ⁇ O)O—, —OC( ⁇ O)NR 2 —, —NR 2 C ( ⁇ O)NR 3 —, —NR 3 C( ⁇ O)NR 2 —, —CH 2 CH(OH)—CH 2 —, or —CH 2 CH(OR 4 )—CH 2 —;
  • Lb represents a hydrocarbon group having 1 to 12 carbon atoms and having a valence of r4+1, or a group represented by any one of formulas (Lb-1) to (Lb-3) or a combination thereof;
  • A represents an epoxy group, an oxetanyl group, or an ethylenically unsaturated bond-containing group;
  • r1 represents 0 or 1;
  • r2 represents 0 or 1;
  • r3 represents an integer of 0 to 5;
  • r4 represents an integer of 1 to 10; * indicates the bonding site to X B1 (when R B2 ) or Y B1 (when R B1 ) in formula (B-1) or formula (B-2).
  • Ra 1 and Ra 2 each independently represent a hydrogen atom, an alkyl group, or an aryl group; * indicates the binding site with Lx1 ; The wavy lines represent the binding sites to Lb or A.
  • Lc1 represents an alkylene group having 2 to 12 carbon atoms, an arylene group having 6 to 18 carbon atoms, or a combination thereof, and x, y, and z each independently represent an integer from 1 to 30.
  • L X1 is —C( ⁇ O)O—
  • the carbon atom is the bonding site to X B1 or Y B2 in formula (B-1) or formula (B-2)
  • the oxygen atom is the bonding site to La, Lb or A.
  • Lx 1 is preferably —O—, —C( ⁇ O)O—, —NR 2 C( ⁇ O)O—, —OC( ⁇ O)NR 2 —, —CH 2 CH(OH)—CH 2 —, or —CH 2 CH(OR 4 )—CH 2 —, and more preferably —O— or —C( ⁇ O)O—.
  • R 1 is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom.
  • R2 is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom.
  • R3 is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom.
  • R4 is preferably an alkyl group or an aryl group, more preferably an alkyl group.
  • La represents a group represented by formula (La-1)
  • Ra 1 and Ra 2 each independently represent preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and still more preferably a methyl group.
  • Another preferred embodiment is one in which one of Ra 1 and Ra 2 is a hydrogen atom and the other is an alkyl group having 1 to 10 carbon atoms (preferably a methyl group).
  • r1 is 1 or 0, and preferably 0.
  • Lx 2 is preferably —O—, —C( ⁇ O)O—, —NR 2 C( ⁇ O)O—, —OC( ⁇ O)NR 2 —, —CH 2 CH(OH)—CH 2 —, or —CH 2 CH(OR 4 )—CH 2 —, and more preferably —O—.
  • r2 is 1 or 0, and when Lb is any one of formulas (Lb-1) to (Lb-3) or a combination thereof, it is preferably 1.
  • Lb when Lb is an r4+1-valent hydrocarbon group having 1 to 12 carbon atoms, Lb is preferably an r4+1-valent saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms, and more preferably an r4+1-valent saturated aliphatic hydrocarbon group having 2 to 6 carbon atoms.
  • the hydrogen atoms in the hydrocarbon group or saturated aliphatic hydrocarbon group in Lb may be substituted with known substituents.
  • Lb is preferably a group represented by formula (Lb-1) to formula (Lb-3), or a bond thereof, and is also preferably a group represented by formula (Lb-1), formula (Lb-2), or a bond thereof.
  • Lc1 is preferably an alkylene group having 2 to 8 carbon atoms, an arylene group having 6 to 10 carbon atoms, or a combination thereof, and more preferably an alkylene group having 2 to 8 carbon atoms.
  • x, y, and z each independently represent an integer of 1 to 30, preferably an integer of 1 to 20, and more preferably an integer of 1 to 10.
  • r3 represents an integer of 0 to 5, preferably an integer of 0 to 3, and more preferably 0, 1 or 2.
  • An embodiment in which r3 is 1 to 5 and Lb includes any one of formulas (Lb-1) to (Lb-3) is also one of the preferred embodiments.
  • the structures represented by formulas (Lb-1) to (Lb-3) are thought to be easily decomposed by heating. Therefore, for example, when heating (for example, heating at 180°C or higher) is performed during film formation, the structures represented by formulas (Lb-1) to (Lb-3) are decomposed, which presumably makes it easier for the resin to be oriented in the film and reduces the CTE (coefficient of thermal expansion).
  • A represents an epoxy group, an oxetanyl group, or an ethylenically unsaturated bond-containing group, and is preferably an ethylenically unsaturated bond-containing group.
  • the ethylenically unsaturated bond-containing group is preferably a (meth)acryloyl group, a vinylphenyl group, or a maleimide group, but may also be a known group having an ethylenically unsaturated bond, such as a vinyl group or an allyl group.
  • r4 is preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and even more preferably 1 or 2.
  • -A x1 ,A x2 - AX1 and AX2 in formula (B-2) are preferably an alkyl group, an aryl group, or a group represented by formula (AA-1) above, and more preferably a group represented by formula (AA-1) above.
  • m is preferably an integer of 0 to 2. An embodiment in which m is 0 is also one of the preferred embodiments.
  • n is preferably an integer of 0 to 2, and more preferably 1 or 2.
  • n+m is preferably an integer of 1 to 4, and more preferably 1 or 2.
  • m is preferably an integer of 0 to 2. An embodiment in which m is 0 is also one of the preferred embodiments.
  • n is preferably an integer of 0 to 2.
  • n+m is preferably an integer of 0 to 4, and more preferably 0, 1, or 2.
  • R B1 and R B2 in formula (B-1), and R B1 , R B2 , A x1 and A x2 in formula (B-2) are ethylenically unsaturated bond-containing groups.
  • one of n and m in formula (B-1) may be 0, and at least one of n and m in formula (B-2) may be 0.
  • the terminal structure of the specific resin is not limited unless otherwise specified.
  • the terminal structure of the specific resin may be a monovalent organic group, an acidic functional group such as carboxylic acid, phosphoric acid, or sulfonic acid, or a structure in which the acidic group is protected, a basic functional group such as an amino group, or a structure in which the basic group is protected, or a polymerizable group.
  • the terminal structure may be represented by formula (AA-1) described above, in which case the * in formula (AA-1) indicates the bonding site between the terminal polymerizable monomer residue of the specific resin and the carboxylic acid, amino group, acid anhydride, imide group, etc.
  • the total content of the partial structure represented by formula (B-1) or the partial structure represented by formula (B-2) relative to all repeating units of the specific resin is preferably 50 mol% or more, more preferably 70 mol% or more, even more preferably 80 mol% or more, and particularly preferably 90 mol% or more. There is no particular upper limit to the content, and it may be 100 mol%.
  • the photocurable composition of the present invention preferably contains a resin as a dispersant.
  • dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins).
  • an acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of basic groups.
  • an acidic dispersant (acidic resin) a resin in which the amount of acid groups is 70 mol% or more is preferred, when the total amount of acid groups and basic groups is taken as 100 mol%.
  • the acid groups possessed by the acidic dispersant (acidic resin) are preferably carboxy groups.
  • the acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mg KOH/g.
  • a basic dispersant refers to a resin in which the amount of basic groups is greater than the amount of acid groups.
  • a resin in which the amount of basic groups is greater than the amount of acid groups is preferred, when the total amount of acid groups and basic groups is taken as 100 mol%.
  • the basic groups possessed by the basic dispersant are preferably amino groups.
  • the resin used as a dispersant is preferably a graft resin.
  • the resin used as a dispersant is also preferably a resin having an aromatic carboxy group.
  • the resin used as the dispersant is preferably a polyimine-based dispersant containing a nitrogen atom in at least one of the main chain and side chain.
  • the polyimine-based dispersant is preferably a resin having a main chain with a partial structure containing a functional group with a pKa of 14 or less, a side chain with 40 to 10,000 atoms, and a basic nitrogen atom in at least one of the main chain and side chain.
  • the basic nitrogen atom there are no particular restrictions on the basic nitrogen atom, as long as it is a nitrogen atom that exhibits basicity.
  • polyimine-based dispersants please refer to the description in paragraphs 0102 to 0166 of JP 2012-255128 A, the contents of which are incorporated herein by reference.
  • the resin used as a dispersant is preferably one with a structure in which multiple polymer chains are bonded to a core.
  • resins include dendrimers (including star-shaped polymers).
  • dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP 2013-043962 A.
  • the resin used as a dispersant is a resin containing repeating units having an ethylenically unsaturated bond-containing group in the side chain.
  • the content of repeating units having an ethylenically unsaturated bond-containing group in the side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, and even more preferably 20 to 70 mol%, of all repeating units in the resin.
  • resins described in JP 2018-087939 A, block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent No. 6432077 A, polyethyleneimine having polyester side chains described in WO 2016/104803 A, block copolymers described in WO 2019/125940 A, block polymers having acrylamide structural units described in JP 2020-066687 A, block polymers having acrylamide structural units described in JP 2020-066688 A, dispersants described in WO 2016/104803 A, and the like can also be used.
  • Dispersants are also commercially available, and specific examples include the DISPERBYK series manufactured by BYK Chemie, the SOLSPERSE series manufactured by Lubrizol Japan, the Efka series manufactured by BASF, and the AJISPER series manufactured by Ajinomoto Fine-Techno Co., Ltd. Additionally, the products described in paragraph 0129 of JP 2012-137564 A and paragraph 0235 of JP 2017-194662 A can also be used as dispersants.
  • the resin content of the total solid content of the photocurable composition is preferably 1 to 99 mass%. Furthermore, the combined content of the polymerizable compound and resin of the total solid content of the photocurable composition is preferably 1 to 99 mass%.
  • the resin content of the total solids of the photocurable composition is preferably 1 to 50% by mass.
  • the upper limit is preferably 40% by mass or less, and more preferably 30% by mass or less.
  • the lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more.
  • the photocurable composition of the present invention may contain only one type of resin, or may contain two or more types. When two or more types of resins are contained, it is preferable that the total amount thereof be within the above range.
  • the photocurable composition of the present invention preferably contains a coloring material.
  • the coloring material include a white coloring material, a black coloring material, a chromatic coloring material, and an infrared-absorbing coloring material.
  • the white coloring material includes not only pure white coloring materials but also light gray coloring materials close to white (e.g., grayish white, light gray, etc.).
  • the colorant may be a pigment or a dye.
  • a combination of pigment and dye may also be used.
  • the pigment may be either an inorganic pigment or an organic pigment, but organic pigments are preferred from the standpoint of a wide range of color variations, ease of dispersion, safety, etc.
  • the colorant preferably contains a pigment.
  • the average primary particle diameter of the pigment is preferably 1 to 200 nm.
  • the lower limit is preferably 5 nm or more, more preferably 10 nm or more.
  • the upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less.
  • the primary particle diameter of the pigment can be determined from a photograph obtained by observing the primary particles of the pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is determined, and the corresponding circle-equivalent diameter is calculated as the primary particle diameter of the pigment.
  • the crystallite size of the pigment determined from the half-width of a peak derived from any crystal plane in an X-ray diffraction spectrum when CuK ⁇ radiation is used as an X-ray source, is preferably 0.1 to 100 nm, more preferably 0.5 to 50 nm, even more preferably 1 to 30 nm, and particularly preferably 5 to 25 nm.
  • the specific surface area of the pigment is preferably 1 to 300 m 2 /g.
  • the lower limit is preferably 10 m 2 /g or more, and more preferably 30 m 2 /g or more.
  • the upper limit is preferably 250 m 2 /g or less, and more preferably 200 m 2 /g or less.
  • the specific surface area value can be measured in accordance with DIN 66131: determination of the specific surface area of solids by gas adsorption, in accordance with the BET (Brunauer, Emmett and Teller) method.
  • chromatic colorants include colorants having a maximum absorption wavelength in the wavelength range of 400 to 700 nm, such as green colorants, red colorants, yellow colorants, purple colorants, blue colorants, and orange colorants.
  • red colorants examples include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, azomethine compounds, xanthene compounds, quinacridone compounds, perylene compounds, and thioindigo compounds, with diketopyrrolopyrrole compounds, anthraquinone compounds, and azo compounds being preferred, and diketopyrrolopyrrole compounds being more preferred.
  • the red colorant is preferably a pigment (red pigment), and diketopyrrolopyrrole pigments are more preferred.
  • red colorants include C.I. (Color Index) Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149,
  • red pigments include 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 269, 270, 272, 279, 291, 294, 295, 296, and 297. Additionally, the compound described
  • C.I. Pigment Red 122, 177, 224, 254, 255, 264, 269, 272, and 291 are preferred, C.I. Pigment Red 254, 264, and 272 are more preferred, and C.I. Pigment Red 254 and 264 are even more preferred.
  • Green colorants include phthalocyanine compounds and squarylium compounds, with phthalocyanine compounds being preferred. Furthermore, the green colorant is preferably a pigment (green pigment), with phthalocyanine pigment being more preferred.
  • green colorants include green pigments such as C.I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66. Furthermore, halogenated zinc phthalocyanine pigments containing an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms per molecule can also be used as green colorants. Specific examples include the compounds described in WO 2015/118720. Other examples of green colorants that can be used include the compounds described in paragraph 0029 of WO 2022/085485, the aluminum phthalocyanine compounds described in JP 2020-070426 A, and the diarylmethane compounds described in JP 2020-504758 A.
  • Preferred green colorants are C.I. Pigment Green 7, 36, 58, 62, and 63.
  • Orange colorants include diketopyrrolopyrrole compounds and azo compounds.
  • the orange colorant is preferably a pigment (orange pigment).
  • Specific examples of orange colorants include orange pigments such as C.I. Pigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, and 73.
  • Yellow colorants include azo compounds, azomethine compounds, isoindoline compounds, pteridine compounds, quinophthalone compounds, and perylene compounds.
  • the yellow colorant is preferably a pigment (yellow pigment). Specific examples of yellow colorants include C.I.
  • an azobarbituric acid nickel complex having the following structure can also be used.
  • Yellow colorants that can be used include the compounds described in paragraphs 0031 to 0033 of WO 2022/085485, the methine dyes described in JP 2019-073695 A, and the methine dyes described in JP 2019-073696 A.
  • Purple colorants include oxazine compounds, quinacridone compounds, perylene compounds, and indigo compounds, with oxazine compounds being preferred.
  • the purple colorant is preferably a pigment (purple pigment).
  • Specific examples of purple colorants include purple pigments such as C.I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.
  • blue colorants examples include phthalocyanine compounds and squarylium compounds, with phthalocyanine compounds being preferred.
  • the blue colorant is preferably a pigment (blue pigment).
  • Specific examples of blue colorants include blue pigments such as C.I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87, and 88.
  • Aluminum phthalocyanine compounds containing phosphorus atoms can also be used as blue colorants. Specific examples include the compounds described in paragraphs 0022 to 0030 of JP-A No. 2012-247591 and paragraph 0047 of JP-A No. 2011-157478.
  • Dyes can also be used as chromatic colorants. There are no particular restrictions on the dyes, and known dyes can be used. Examples include pyrazole azo dyes, anilino azo dyes, triarylmethane dyes, anthraquinone dyes, anthrapyridone dyes, benzylidene dyes, oxonol dyes, pyrazolotriazole azo dyes, pyridone azo dyes, cyanine dyes, phenothiazine dyes, pyrrolopyrazole azomethine dyes, xanthene dyes, phthalocyanine dyes, benzopyran dyes, indigo dyes, and pyrromethene dyes.
  • known dyes can be used. Examples include pyrazole azo dyes, anilino azo dyes, triarylmethane dyes, anthraquinone dyes, anthrapyridone dyes, benzylidene dye
  • Dye polymers can also be used as chromatic colorants.
  • the dye polymer is preferably a dye dissolved in a solvent before use.
  • the dye polymer may also form particles. When the dye polymer is particulate, it is typically used in a dispersed state in a solvent.
  • Particulate dye polymers can be obtained, for example, by emulsion polymerization; examples of the compounds and manufacturing methods described in JP-A-2015-214682 include the compounds and manufacturing methods described in JP-A-2015-214682.
  • the dye polymer has two or more dye structures in one molecule, preferably three or more dye structures. The upper limit is not particularly limited, but can be 100 or less.
  • the multiple dye structures in one molecule may be the same or different dye structures.
  • the weight-average molecular weight (Mw) of the dye polymer is preferably 2,000 to 50,000.
  • the lower limit is more preferably 3,000 or more, and even more preferably 6,000 or more.
  • the upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less.
  • Dye multimers may also use compounds described in JP 2011-213925 A, JP 2013-041097 A, JP 2015-028144 A, JP 2015-030742 A, WO 2016/031442, etc.
  • 10-2020-0069062 halogenated zinc phthalocyanine pigments described in Japanese Patent No. 6809649, isoindoline compounds described in JP 2020-180176, phenothiazine compounds described in JP 2021-187913, halogenated zinc phthalocyanines described in WO 2022/004261, halogenated zinc phthalocyanines described in WO 2021/250883, and compounds represented by formula 1 described in Korean Patent Publication No. 10-2020-0030759.
  • the chromatic colorant may be a rotaxane.
  • the dye skeleton may be used in the cyclic structure of the rotaxane, in the rod-shaped structure, or in both structures.
  • Two or more chromatic colorants may be used in combination.
  • the combination of two or more chromatic colorants may form a black color. Examples of such combinations include the following embodiments (1) to (7).
  • the photocurable composition of the present invention can be preferably used as a photocurable composition for forming an infrared transmission filter.
  • An embodiment containing a red color material, a blue color material, a yellow color material, and a purple color material (3) An embodiment containing a red color material, a blue color material, a yellow color material, and a purple color material. (4) An embodiment containing a red color material, a blue color material, a yellow color material, a purple color material, and a green color material. (5) An embodiment containing a red color material, a blue color material, a yellow color material, and a green color material. (6) An embodiment containing a red color material, a blue color material, and a green color material. (7) An embodiment containing a yellow coloring material and a purple coloring material.
  • white coloring material examples include inorganic pigments such as titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, and zinc sulfide.
  • the white coloring material can be the white pigments described in paragraphs 0040 to 0043 of WO 2022/085485.
  • the black coloring material is not particularly limited, and known materials can be used.
  • the black coloring material may be an inorganic black coloring material or an organic black coloring material.
  • the black coloring material is preferably a pigment.
  • the black coloring material means a coloring material that exhibits absorption over the entire wavelength range of 400 to 700 nm.
  • Inorganic black colorants include carbon black, titanium black, graphite, etc., with carbon black and titanium black being preferred, and titanium black being more preferred. Titanium black is black particles containing titanium atoms, and low-order titanium oxide or titanium oxynitride is preferred. The titanium black described in paragraph 0044 of WO 2022/085485 can be used. Zirconium nitride powder described in JP 2023-048173 A can also be used as an inorganic black colorant.
  • organic black colorants examples include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds and perylene compounds being preferred.
  • the compounds described in paragraph 0166 of WO 2022/065215 can be used as organic black colorants.
  • perylene black such as Lumogen Black FK4280
  • perylene black described in paragraphs 0016 to 0020 of JP 2017-226821 A
  • black azo pigments described in JP 2022-121935 A may also be used as organic black colorants.
  • the infrared absorbing colorant is preferably a compound having a maximum absorption wavelength longer than 700 nm.
  • the infrared absorbing colorant is preferably a compound having a maximum absorption wavelength in the wavelength range of more than 700 nm to 1800 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of more than 700 nm to 1400 nm, even more preferably a compound having a maximum absorption wavelength in the wavelength range of more than 700 nm to 1200 nm, and particularly preferably a compound having a maximum absorption wavelength in the wavelength range of more than 700 nm to 1000 nm.
  • the ratio A1 / A2 of the absorbance A1 at a wavelength of 500 nm of the infrared absorbing colorant to the absorbance A2 at the maximum absorption wavelength is preferably 0.08 or less, more preferably 0.04 or less.
  • the infrared absorbing colorant is preferably a pigment, more preferably an organic pigment.
  • Infrared-absorbing colorants include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterrylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, pyrromethene compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, dithiolene metal complexes, metal oxides, and metal borides. Specific examples of these include the compounds described in paragraph 0114 of WO 2022/065215.
  • examples of infrared absorbing colorants include the compounds described in paragraph 0121 of WO 2022/065215, squarylium compounds described in JP 2020-075959 A, copper complexes described in Korean Patent Publication No. 10-2019-0135217, croconic acid compounds described in JP 2021-195515 A, infrared absorbing dyes described in JP 2022-022070 A, and the compounds described in WO 2019/021767.
  • the content of the colorant in the total solid content of the photocurable composition is preferably 30 to 80% by mass.
  • the upper limit is preferably 70% by mass or less, and more preferably 65% by mass or less.
  • the lower limit is preferably 35% by mass or more, and more preferably 40% by mass or more.
  • the pigment content of the total solids content of the photocurable composition is preferably 20 to 80% by mass.
  • the upper limit is preferably 75% by mass or less, more preferably 65% by mass or less, and even more preferably 63% by mass or less.
  • the lower limit is preferably 25% by mass or more, more preferably 30% by mass or more, and even more preferably 35% by mass or more.
  • the pigment content in the colorant is preferably 20 to 100% by mass, more preferably 50 to 100% by mass, and even more preferably 70 to 100% by mass.
  • the photocurable composition of the present invention preferably contains a chain transfer agent.
  • the chain transfer agent include a thiol compound, a thiocarbonylthio compound, and an aromatic ⁇ -methylalkenyl dimer, and a thiol compound is preferred.
  • the chain transfer agent include the compounds described in paragraphs 0093 to 0113 of WO 2019/188652.
  • the thiol compound used as a chain transfer agent is a compound having one or more thiol groups, preferably a compound having two or more thiol groups.
  • the upper limit of the number of thiol groups contained in the thiol compound is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. It is particularly preferable that the thiol compound be a compound having two thiol groups.
  • the thiol compound is preferably a compound represented by the following formula (SH-1): L S1 - (SH) n ...Formula (SH-1) (In the formula, SH represents a thiol group, L1 represents an n-valent group, and n represents an integer of 1 or more.)
  • Examples of the n-valent group represented by L S1 in formula (SH-1) include a hydrocarbon group, a heterocyclic group, —O—, —S—, —NR S1 —, —CO—, —COO—, —OCO—, —SO 2 —, or a group consisting of a combination thereof.
  • R S1 represents a hydrogen atom, an alkyl group, or an aryl group, and is preferably a hydrogen atom.
  • the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
  • the aliphatic hydrocarbon group may be cyclic or acyclic.
  • the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group.
  • the hydrocarbon group may have a substituent or may not have a substituent.
  • the cyclic aliphatic hydrocarbon group and the aromatic hydrocarbon group may be a monocyclic ring or a fused ring.
  • the heterocyclic group may be a monocyclic ring or a fused ring.
  • the heterocyclic group is preferably a 5- or 6-membered ring.
  • the heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. Examples of heteroatoms constituting the heterocyclic group include nitrogen atoms, oxygen atoms, and sulfur atoms.
  • the number of carbon atoms constituting L1 is preferably 3 to 100, and more preferably 6 to 50.
  • n represents an integer of 1 or greater.
  • the upper limit of n is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less.
  • the lower limit of n is preferably 2 or greater.
  • thiol compounds include the compounds described in the Examples below and the compounds described in paragraphs 0100 to 0103 of WO 2019/188652.
  • Commercially available thiol compounds include PEMP (manufactured by SC Organic Chemical Co., Ltd.), Suncera M (manufactured by Sanshin Chemical Industry Co., Ltd.), Karenz MTBD1, Karenz MTPE1, Karenz MTNR1, and Karenz MTTPMB (all manufactured by Resonac Corporation).
  • PEMP manufactured by SC Organic Chemical Co., Ltd.
  • Suncera M manufactured by Sanshin Chemical Industry Co., Ltd.
  • Karenz MTBD1, Karenz MTPE1, Karenz MTNR1, and Karenz MTTPMB all manufactured by Resonac Corporation.
  • the thiol compounds described in JP 2020-109068 A can also be used as chain transfer agents.
  • the molecular weight of the chain transfer agent is preferably 200 or more.
  • the upper limit is preferably 1000 or less, more preferably 800 or less, and even more preferably 600 or less, because this increases the SH valence per weight.
  • the content of the chain transfer agent in the total solids content of the photocurable composition is preferably 0.001 to 5% by mass.
  • the upper limit is preferably 3% by mass or less, and more preferably 1% by mass or less.
  • the lower limit is preferably 0.05% by mass or more, and more preferably 0.01% by mass or more. Only one type of chain transfer agent may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof be within the above range.
  • the curable compound of the present invention preferably contains an amine compound. According to this embodiment, the efficiency of generating radicals from the photopolymerization initiator during exposure can be further improved, and the polymerization reaction of the polymerizable compound can be further promoted.
  • the molecular weight of the amine compound is preferably 100 to 1,000.
  • the upper limit is preferably 800 or less, and more preferably 500 or less.
  • the lower limit is preferably 150 or more, and more preferably 200 or more.
  • the amine compound is preferably a compound having 1 to 8 amino groups per molecule, more preferably a compound having 1 to 4 amino groups, and even more preferably a compound having 1 to 2 amino groups.
  • the amine compound is preferably colorless, i.e., the molar absorption coefficient of the amine compound at a wavelength of 400 to 700 nm is preferably less than 200 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 , and more preferably less than 100 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 .
  • the amine compound may be a primary, secondary, or tertiary amine, but a tertiary amine is preferred.
  • the three groups connected to the nitrogen atom are preferably selected from a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group. Of these, a combination of an alkyl group and an aryl group is most preferred.
  • the amine compound preferably has a carboxyl group, sulfonic acid group, phosphate group, or hydroxyl group in order to enhance alkaline developability and reduce residues.
  • the amine compound is preferably a compound represented by formula (B-1).
  • R a and R b each independently represent a monovalent organic group having 1 to 10 carbon atoms which may contain a heteroatom;
  • R c represents a monovalent organic group which may contain a heteroatom;
  • m represents an integer of 0 to 5.
  • the organic groups represented by R a , R b , and R c include alkyl groups, aryl groups, and heteroaryl groups, and are preferably alkyl groups.
  • the alkyl groups, aryl groups, and heteroaryl groups may have a substituent. Examples of the substituent include a carboxy group, a sulfonic acid group, a phosphoric acid group, and a hydroxy group, and are preferably hydroxy groups.
  • m represents an integer of 0 to 5, preferably an integer of 0 to 3, more preferably 0 or 1, and even more preferably 0.
  • amine compounds include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and p-dimethylaminocinnamylidene.
  • Indanone p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-a
  • the aromatic hydrocarbons include cetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin,
  • the content of the amine compound is preferably 5 to 1,000 parts by mass per 100 parts by mass of the specific compound described above.
  • the upper limit is preferably 500 parts by mass or less, and more preferably 200 parts by mass or less.
  • the lower limit is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more. Only one type of amine compound may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof be within the above range.
  • the photocurable composition of the present invention may contain an acid anhydride. Even if the specific compound is hydrolyzed to a free OH form, the presence of the acid anhydride allows it to be restored to a photodecomposable oxime compound again. This makes it possible to suppress a decrease in sensitivity over time.
  • Acid anhydrides include carboxylic acid anhydrides and sulfonic acid anhydrides, with carboxylic acid anhydrides being preferred.
  • Specific examples of acid anhydrides include acetic anhydride, propionic anhydride, isobutyric anhydride, butyric anhydride, 2-methylbutyric anhydride, pivalic anhydride, isovaleric anhydride, valeric anhydride, 2-methylvaleric anhydride, 3-methylvaleric anhydride, 4-methylvaleric anhydride, hexanoic anhydride, 2-methylhexanoic anhydride, 3-methylhexanoic anhydride, 4-methylhexanoic anhydride, 5-methylhexanoic anhydride, heptanoic anhydride, 2-methylheptanoic anhydride, 3-methylheptanoic anhydride, 4-methylheptanoic anhydride, 5-methylhept ...
  • suitable anhydrides include aliphatic carboxylic acid anhydrides such as 6-methylheptanoic anhydride, 3-phenylpropionic anhydride, phenylacetic anhydride, methacrylic anhydride, acrylic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, and glutaric anhydride; aromatic carboxylic acid anhydrides such as benzoic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride; and sulfocarboxylic acid anhydrides such as 2-sulfobenzoic anhydride.
  • aliphatic carboxylic acid anhydrides such as 6-methylheptanoic anhydride, 3-phenylpropionic anhydride, phenylacetic anhydride, methacrylic an
  • the content of the acid anhydride is preferably 1 to 200 parts by mass per 100 parts by mass of the specific compound described above.
  • the upper limit is preferably 100 parts by mass or less, and more preferably 50 parts by mass or less.
  • the lower limit is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more. Only one type of acid anhydride may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof be within the above range.
  • the photocurable composition of the present invention may contain a pigment derivative.
  • the pigment derivative is used, for example, as a dispersing aid.
  • a dispersing aid is a material that enhances the dispersibility of a coloring material such as a pigment in the photocurable composition.
  • Pigment derivatives include compounds having at least one structure selected from the group consisting of a dye structure and a triazine structure, and an acid group or a basic group.
  • the dye structures include quinoline dye structures, benzimidazolone dye structures, benzisoindole dye structures, benzothiazole dye structures, iminium dye structures, squarylium dye structures, croconium dye structures, oxonol dye structures, pyrrolopyrrole dye structures, diketopyrrolopyrrole dye structures, azo dye structures, azomethine dye structures, phthalocyanine dye structures, naphthalocyanine dye structures, anthraquinone dye structures, quinacridone dye structures, dioxazine dye structures, perinone dye structures, perylene dye structures, thiazineindigo dye structures, thioindigo dye structures, isoindoline dye structures, isoindolinone dye structures, quinophthalone dye structures, dithiol dye structures, triarylmethane dye structures, and pyrromethene dye structures.
  • Examples of acid groups contained in the pigment derivative include a carboxy group, a sulfo group, a phosphate group, a boronic acid group, an imidic acid group, and salts thereof.
  • Examples of atoms or atomic groups constituting the salts include alkali metal ions (Li + , Na + , K +, etc.), alkaline earth metal ions (Ca2 + , Mg2 +, etc.), ammonium ions, imidazolium ions, pyridinium ions, and phosphonium ions.
  • the imidic acid group is preferably a group represented by -SO 2 NHSO 2 R X1 , -CONHSO 2 R X2 , -CONHCOR X3 or -SO 2 NHCOR X4, more preferably a group represented by -SO 2 NHSO 2 R X1 , -CONHSO 2 R X2 or -SO 2 NHCOR X4 , and even more preferably -SO 2 NHSO 2 R X1 or -CONHSO 2 R X2 .
  • R X1 to R X4 each independently represent an alkyl group or an aryl group.
  • the alkyl group and aryl group represented by R X1 to R X4 may have a substituent.
  • the substituent is preferably a halogen atom, more preferably a fluorine atom.
  • R X1 to R X4 each independently represent an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom, more preferably an alkyl group containing a fluorine atom.
  • the number of carbon atoms in the alkyl group containing a fluorine atom is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.
  • the number of carbon atoms in the aryl group containing a fluorine atom is preferably 6 to 20, more preferably 6 to 12, and still more preferably 6.
  • Basic groups possessed by pigment derivatives include amino groups, pyridinyl groups and their salts, salts of ammonium groups, and phthalimidomethyl groups.
  • Atoms or atomic groups that constitute the salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.
  • Examples of the amino group include a group represented by —NR x11 R x12 and a cyclic amino group.
  • R x11 and R x12 each independently represent a hydrogen atom, an alkyl group, or an aryl group, and are preferably alkyl groups. That is, the amino group is preferably a dialkylamino group.
  • the number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.
  • the alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear.
  • the alkyl group may have a substituent.
  • the number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12.
  • the aryl group may have a substituent.
  • cyclic amino groups include pyrrolidine groups, piperidine groups, piperazine groups, and morpholine groups. These groups may further have a substituent.
  • the pigment derivative may be a pigment derivative with excellent visible transparency (hereinafter also referred to as a transparent pigment derivative).
  • the maximum molar absorption coefficient ( ⁇ max) of the transparent pigment derivative in the wavelength region of 400 to 700 nm is preferably 3000 L mol cm ⁇ 1 or less, more preferably 1000 L mol cm ⁇ 1 or less , and even more preferably 100 L mol cm ⁇ 1 or less.
  • the lower limit of ⁇ max is, for example , 1 L mol cm ⁇ 1 or more , and may be 10 L mol cm ⁇ 1 or more .
  • pigment derivatives include the compounds described in the examples below, the compounds described in paragraph 0124 of WO 2022/085485, the benzimidazolone compounds or salts thereof described in JP 2018-168244 A, the compounds having an isoindoline skeleton described in general formula (1) of Japanese Patent No. 6996282, the compounds described in JP 2019-172968 A, and the compounds described in the specification of Chinese Patent Application Publication No. 115124889.
  • the content of the pigment derivative is preferably 1 to 30 parts by mass, and more preferably 3 to 20 parts by mass, per 100 parts by mass of the pigment. Furthermore, the total content of the pigment derivative and colorant is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more, of the total solids content of the photocurable composition.
  • the upper limit is preferably 80% by mass or less, and more preferably 70% by mass or less. Only one type of pigment derivative may be used, or two or more types may be used in combination.
  • the photocurable composition of the present invention may also contain a polyalkyleneimine.
  • the polyalkyleneimine is used, for example, as a dispersing aid for pigments.
  • a dispersing aid is a material for improving the dispersibility of coloring materials such as pigments in a photocurable composition.
  • the polyalkyleneimine is a polymer obtained by ring-opening polymerization of an alkyleneimine.
  • the polyalkyleneimine is preferably a polymer having a branched structure containing a primary amino group, a secondary amino group, and a tertiary amino group.
  • the alkyleneimine preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, even more preferably 2 or 3 carbon atoms, and particularly preferably 2 carbon atoms.
  • the molecular weight of the polyalkyleneimine is preferably 200 or more, more preferably 250 or more.
  • the upper limit is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, and particularly preferably 2,000 or less.
  • the molecular weight value of the polyalkyleneimine if the molecular weight can be calculated from the structural formula, the molecular weight of the polyalkyleneimine is the value calculated from the structural formula. On the other hand, if the molecular weight of the specific amine compound cannot be calculated from the structural formula or if calculation is difficult, the number average molecular weight value measured by the boiling point elevation method is used.
  • the number average molecular weight value measured by the viscosity method is used. Furthermore, if it is not possible or difficult to measure by the viscosity method, the number average molecular weight value measured in terms of polystyrene using GPC (gel permeation chromatography) is used.
  • the amine value of the polyalkyleneimine is preferably 5 mmol/g or more, more preferably 10 mmol/g or more, and even more preferably 15 mmol/g or more.
  • alkyleneimines include ethyleneimine, propyleneimine, 1,2-butyleneimine, and 2,3-butyleneimine. Ethyleneimine or propyleneimine is preferred, and ethyleneimine is more preferred.
  • the polyalkyleneimine is particularly preferably polyethyleneimine.
  • the polyethyleneimine preferably contains primary amino groups in an amount of 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, based on the total of primary amino groups, secondary amino groups, and tertiary amino groups.
  • Commercially available polyethyleneimines include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000 (all manufactured by Nippon Shokubai Co., Ltd.).
  • the content of polyalkyleneimine in the total solids content of the photocurable composition is preferably 0.1 to 5% by mass.
  • the lower limit is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more.
  • the upper limit is preferably 4.5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.
  • the content of polyalkyleneimine is preferably 0.5 to 20 parts by mass per 100 parts by mass of pigment.
  • the lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more.
  • the upper limit is preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less. Only one type of polyalkyleneimine may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.
  • the photocurable composition of the present invention preferably contains a solvent.
  • the solvent include organic solvents.
  • the type of solvent is not particularly limited as long as it satisfies the solubility of each component and the coatability of the composition.
  • organic solvents include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents. For details of these, please refer to paragraph [0223] of WO 2015/166779, the contents of which are incorporated herein by reference.
  • ester-based solvents substituted with a cyclic alkyl group and ketone-based solvents substituted with a cyclic alkyl group can also be preferably used.
  • organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol a
  • ethylene glycol monomethyl ether acetate examples include 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, gamma butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane-1,3-diyl diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol (also known as diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, and isopropyl alcohol.
  • diacetone alcohol also known as diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone
  • 2-methoxypropyl acetate 2-methoxy-1-propanol
  • the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as organic solvents for environmental reasons (for example, the amount may be 50 ppm by mass (parts per million) or less, 10 ppm by mass or less, or 1 ppm by mass or less, relative to the total amount of organic solvents).
  • aromatic hydrocarbons benzene, toluene, xylene, ethylbenzene, etc.
  • the amount may be 50 ppm by mass (parts per million) or less, 10 ppm by mass or less, or 1 ppm by mass or less, relative to the total amount of organic solvents).
  • the organic solvent it is preferable for the organic solvent to have a low metal content.
  • the metal content of the organic solvent is preferably 10 parts per billion (ppb) by mass or less. If necessary, organic solvents with metal contents at the ppt (parts per trillion) by mass level may be used. Such organic solvents are provided, for example, by Toyo Gosei Co., Ltd. (The Chemical Daily, November 13, 2015).
  • Methods for removing impurities such as metals from organic solvents include, for example, distillation (molecular distillation, thin-film distillation, etc.) and filtration using a filter.
  • the pore size of the filter used for filtration is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
  • the filter material is preferably polytetrafluoroethylene, polyethylene, or nylon.
  • the organic solvent may contain isomers (compounds with the same number of atoms but different structures). Furthermore, the organic solvent may contain only one type of isomer, or multiple types.
  • the peroxide content in the organic solvent is 0.8 mmol/L or less, and it is even more preferable that it contains substantially no peroxide.
  • the solvent content in the photocurable composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 30 to 90% by mass.
  • the photocurable composition of the present invention is substantially free of environmentally restricted substances.
  • substantially free of environmentally restricted substances means that the content of environmentally restricted substances in the photocurable composition is 50 ppm by mass or less, preferably 30 ppm by mass or less, more preferably 10 ppm by mass or less, and particularly preferably 1 ppm by mass or less.
  • environmentally restricted substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene.
  • distillation methods can be used at any stage, including the stage of the raw materials, the stage of the product obtained by reacting the raw materials (e.g., a resin solution or a polyfunctional monomer solution after polymerization), or the stage of the photocurable composition prepared by mixing these compounds.
  • the photocurable composition of the present invention may contain a compound having a cyclic ether group.
  • the cyclic ether group include an epoxy group and an oxetanyl group.
  • the epoxy group may be an alicyclic epoxy group.
  • the alicyclic epoxy group refers to a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are condensed.
  • the compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter also referred to as an epoxy compound).
  • Examples of epoxy compounds include compounds having one or more epoxy groups per molecule, and compounds having two or more epoxy groups are preferred.
  • the epoxy compound is preferably a compound having 1 to 100 epoxy groups per molecule.
  • the upper limit of the number of epoxy groups contained in the epoxy compound can be, for example, 10 or less, or 5 or less.
  • the lower limit of the number of epoxy groups contained in the epoxy compound is preferably 2 or more.
  • Examples of compounds having a cyclic ether group that can be used include the compounds described in paragraphs 0034 to 0036 of JP 2013-011869 A, paragraphs 0147 to 0156 of JP 2014-043556 A, paragraphs 0085 to 0092 of JP 2014-089408 A, the compounds described in JP 2017-179172 A, the xanthene-type epoxy resins described in JP 2021-195421 A, and the xanthene-type epoxy resins described in JP 2021-195422 A.
  • the compound having a cyclic ether group may be a low molecular weight compound (e.g., a molecular weight of less than 2000, or even less than 1000) or a high molecular weight compound (macromolecule) (e.g., a molecular weight of 1000 or more, or in the case of a polymer, a weight average molecular weight of 1000 or more).
  • the weight average molecular weight of the compound having a cyclic ether group is preferably 200 to 100,000, and more preferably 500 to 50,000.
  • the upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.
  • EHPE3150 manufactured by Daicel Corporation
  • EPICLON N-695 manufactured by DIC Corporation
  • Marproof G-0150M G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, and G-01758 (all manufactured by NOF Corporation, epoxy group-containing polymers).
  • the content of the compound having a cyclic ether group in the total solid content of the photocurable composition is preferably 0.1 to 20% by mass.
  • the lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more.
  • the upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less. Only one type of compound having a cyclic ether group may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof be within the above range.
  • the photocurable composition of the present invention may contain an ultraviolet absorber.
  • ultraviolet absorbers include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, triazine compounds, and dibenzoyl compounds. Specific examples of such compounds include the compounds described in paragraph 0179 of International Publication No. 2022/085485, the reactive triazine ultraviolet absorbers described in JP-A-2021-178918, the ultraviolet absorbers described in JP-A-2022-007884, the compounds described in Korean Patent Publication No.
  • the content of the ultraviolet absorber in the total solids content of the photocurable composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass.
  • the ultraviolet absorber may be used alone or in combination of two or more kinds. When two or more kinds are used, the total amount thereof is preferably in the above range.
  • the photocurable composition of the present invention may contain a polymerization inhibitor.
  • polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), and N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.). Of these, p-methoxyphenol is preferred.
  • the content of the polymerization inhibitor in the total solids content of the photocurable composition is preferably 0.0001 to 5 mass%.
  • One type of polymerization inhibitor may be used alone, or two or more types may be used. When two or more types are used, the total amount preferably falls within the above range.
  • the photocurable composition of the present invention may contain a silane coupling agent.
  • the silane coupling agent include silane compounds having a hydrolyzable group, and preferably silane compounds having both a hydrolyzable group and another functional group.
  • the hydrolyzable group refers to a substituent directly bonded to a silicon atom that can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction.
  • the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group, with an alkoxy group being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group.
  • Examples of functional groups other than the hydrolyzable group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, a thiol group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group, an isocyanate group, and a phenyl group, with an amino group, a (meth)acryloyl group, and an epoxy group being preferred.
  • Specific examples of the silane coupling agent include the compound described in paragraph 0177 of WO 2022/085485 and the compound described in JP 2019-183020 A.
  • the content of the silane coupling agent in the total solid content of the photocurable composition is preferably 0.1 to 15% by mass.
  • the upper limit is preferably 10% by mass or less, more preferably 5% by mass or less.
  • the lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. Only one type of silane coupling agent may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount be in the above range.
  • the photocurable composition of the present invention may contain a surfactant.
  • a surfactant various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
  • the surfactant is preferably a silicone-based surfactant or a fluorine-based surfactant, and more preferably a silicone-based surfactant.
  • nonionic surfactants include the compounds described in paragraph 0174 of WO 2022/085485.
  • Silicone surfactants include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, and SF 8419.
  • OIL all manufactured by Dow Toray Industries, Inc.
  • TSF-4300, TSF-4445, TSF-4460, TSF-4452 all manufactured by Momentive Performance Materials
  • KP-341, KF-6000, KF-6001, KF-6002, KF-6003 all manufactured by Shin-Etsu Chemical Co., Ltd.
  • BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 all manufactured by BYK-Chemie.
  • compounds having the following structure can also be used as the silicone surfactant.
  • the surfactant content of the total solids content of the photocurable composition is preferably 0.001% to 5.0% by mass, and more preferably 0.005 to 3.0% by mass. Only one type of surfactant may be used, or two or more types may be used. If two or more types are used, it is preferable that the total amount be within the above range.
  • the photocurable composition of the present invention may contain an antioxidant.
  • antioxidants include phenolic antioxidants, amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.
  • phenolic antioxidants include hindered phenol compounds.
  • the phenolic antioxidant is preferably a compound having a substituent at the position adjacent to the phenolic hydroxy group (ortho position).
  • the substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms.
  • the antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule.
  • phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, ethyl bis(2,4-di-tert-butyl-6-methylphenyl)phosphite, and tris(2,4-di-tert-butylphenyl)phosphite.
  • antioxidants include, for example, ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-60G, ADK STAB AO-80, ADK STAB AO-330 (manufactured by ADEKA Corporation), and JP-650 (manufactured by Johoku Chemical Industry Co., Ltd.).
  • Antioxidants include the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, the compounds described in WO 2017/006600, the compounds described in WO 2017/164024, and the compounds described in Korean Patent Publication No. 10-2019-0059371.
  • the content of the antioxidant in the total solid content of the photocurable composition is preferably 0.01 to 20 mass %, more preferably 0.3 to 15 mass %. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.
  • the photocurable composition of the present invention may contain, as needed, a thermal polymerization initiator, a thermal base generator, a photobase generator, an aluminum adhesion aid, a migration inhibitor, a light absorber, an organic titanium compound, a rust inhibitor, a sensitizer, a plasticizer, and other auxiliaries (e.g., conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling promoters, fragrances, surface tension modifiers, chain transfer agents, etc.).
  • auxiliaries e.g., conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling promoters, fragrances, surface tension modifiers, chain transfer agents, etc.
  • the photocurable composition of the present invention may contain a metal oxide to adjust the refractive index of the resulting film.
  • metal oxides include TiO 2 , ZrO 2 , Al 2 O 3 , and SiO 2 .
  • the primary particle size of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, and even more preferably 5 to 50 nm.
  • the metal oxide may have a core-shell structure. In this case, the core may be hollow.
  • the photocurable composition of the present invention may contain a light resistance improver.
  • light resistance improvers include the compounds described in paragraph 0183 of WO 2022/085485.
  • the photocurable composition of the present invention is substantially free of terephthalic acid esters.
  • substantially free means that the content of terephthalic acid esters in the total amount of the photocurable composition is 1,000 ppb by mass or less, more preferably 100 ppb by mass or less, and particularly preferably zero.
  • the photocurable composition of the present invention have a melamine content of 10,000 ppm by mass or less.
  • the photocurable composition of the present invention preferably has a free metal content of 100 ppm or less, more preferably 50 ppm or less. Furthermore, the free halogen content is preferably 100 ppm or less, more preferably 50 ppm or less.
  • Methods for reducing free metals and halogens in the photocurable composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification with ion-exchange resins.
  • perfluoroalkylsulfonic acids and their salts may be restricted.
  • the content of the above-mentioned compounds in the photocurable composition of the present invention is reduced, the content of perfluoroalkylsulfonic acids (particularly perfluoroalkylsulfonic acids having a perfluoroalkyl group with 6 to 8 carbon atoms) and their salts, and perfluoroalkylcarboxylic acids (particularly perfluoroalkylcarboxylic acids having a perfluoroalkyl group with 6 to 8 carbon atoms) and their salts is preferably in the range of 0.01 ppb to 1000 ppb, more preferably in the range of 0.05 ppb to 500 ppb, and even more preferably in the range of 0.1 ppb to 300 ppb, relative to the total solids content of the photocurable composition.
  • the photocurable composition of the present invention may be substantially free of perfluoroalkylsulfonic acids and their salts, and perfluoroalkylcarboxylic acids and their salts.
  • a photocurable composition that is substantially free of perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts may be selected.
  • compounds that can replace restricted compounds include compounds that are exempt from restrictions due to the difference in the number of carbon atoms in the perfluoroalkyl group.
  • the photocurable composition of the present invention may contain perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acid and its salts, within the maximum allowable range.
  • the water content of the photocurable composition of the present invention is typically 3% by mass or less, preferably 0.01 to 1.5% by mass, and more preferably 0.1 to 1.0% by mass.
  • the water content can be measured by the Karl Fischer method.
  • the photocurable composition of the present invention can be used by adjusting its viscosity to adjust the film surface condition (flatness, etc.) and film thickness.
  • the viscosity value can be selected as needed, but is preferably 0.3 mPa ⁇ s to 50 mPa ⁇ s at 25°C, and more preferably 0.5 mPa ⁇ s to 20 mPa ⁇ s. Viscosity can be measured, for example, using a cone-plate type viscometer with the temperature adjusted to 25°C.
  • the container for storing the photocurable composition is not particularly limited, and any known container can be used. Also, the container described in paragraph 0187 of WO 2022/085485 can be used as the container.
  • the photocurable composition of the present invention can be prepared by mixing the above-mentioned components.
  • all components may be simultaneously dissolved and/or dispersed in a solvent to prepare the photocurable composition, or, if necessary, each component may be prepared as two or more appropriate solutions or dispersions, which are mixed at the time of use (application) to prepare the photocurable composition.
  • a process for dispersing the pigment When preparing a photocurable composition, it is preferable to include a process for dispersing the pigment.
  • mechanical forces used to disperse the pigment include compression, squeezing, impact, shear, and cavitation.
  • Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high-speed impellers, sand grinders, flow jet mixers, high-pressure wet atomization, and ultrasonic dispersion.
  • grinding the pigment in a sand mill (bead mill) it is preferable to use small-diameter beads, increase the bead packing rate, and perform the process under conditions that increase grinding efficiency.
  • the process and disperser for dispersing pigments can be suitably used, as described in "Dispersion Technology Encyclopedia,” published by Joho Kiko Co., Ltd., July 15, 2005, or "Dispersion Technology and Industrial Applications Focused on Suspension (Solid/Liquid Dispersion System) - Comprehensive Data Collection,” published by the Management Development Center Publishing Department, October 10, 1978, as well as the process and disperser described in paragraph 0022 of JP 2015-157893 A.
  • the process for dispersing pigments can be performed by a salt milling process to refine the particles.
  • the materials, equipment, and processing conditions used in the salt milling process can be found in, for example, JP 2015-194521 A and JP 2012-046629 A.
  • materials for beads used for dispersion include zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, and glass.
  • the beads can also be made of inorganic compounds with a Mohs hardness of 2 or higher.
  • the photocurable composition may contain 1 to 10,000 ppm of these beads.
  • the photocurable composition When preparing the photocurable composition, it is preferable to filter the photocurable composition for purposes such as removing foreign matter and reducing defects.
  • filters and filtration methods used for filtration include those described in paragraphs 0196 to 0199 of WO 2022/085485.
  • the film of the present invention is obtained from the photocurable composition of the present invention described above.
  • the film of the present invention can be used in optical filters such as color filters, infrared transmission filters, and infrared cut filters.
  • the film thickness of the film of the present invention can be adjusted appropriately depending on the purpose.
  • the film thickness is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less.
  • the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, and even more preferably 0.3 ⁇ m or more.
  • the film of the present invention When the film of the present invention is used as a color filter, it is preferable that the film of the present invention has a green, red, blue, cyan, magenta, or yellow hue. Furthermore, the film of the present invention can be preferably used as the colored pixels of a color filter. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.
  • the method for manufacturing pixels includes the steps of forming a composition layer on a support using the photocurable composition of the present invention, exposing the composition layer to light in a pattern, and developing and removing the unexposed areas of the composition layer. If necessary, a step of drying the composition layer (pre-baking step) and a step of heat-treating the developed pattern (pixels) (post-baking step) may also be provided.
  • the photocurable composition of the present invention is used to form a composition layer on a support.
  • the support is not particularly limited and can be selected appropriately depending on the application. Examples include glass substrates and silicon substrates, with a silicon substrate being preferred.
  • the silicon substrate may also be formed with a charge-coupled device (CCD), a complementary metal-oxide semiconductor (CMOS), a transparent conductive film, or the like.
  • CCD charge-coupled device
  • CMOS complementary metal-oxide semiconductor
  • a black matrix is sometimes formed on the silicon substrate to isolate each pixel.
  • the silicon substrate may also be provided with a base layer to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the substrate surface.
  • the surface contact angle of the base layer is preferably 20 to 70° when measured with diiodomethane, and 30 to 80° when measured with water.
  • the photocurable composition can be applied using known methods. Examples include drop casting, slit coating, spraying, roll coating, spin coating, casting, slit-and-spin, pre-wetting (e.g., the method described in JP 2009-145395 A), various printing methods such as inkjet (e.g., on-demand, piezo, and thermal), nozzle jet printing, and other ejection-based printing, flexographic printing, screen printing, gravure printing, reverse offset printing, and metal mask printing, transfer methods using molds, and nanoimprinting.
  • inkjet e.g., on-demand, piezo, and thermal
  • nozzle jet printing ejection-based printing
  • flexographic printing screen printing
  • gravure printing reverse offset printing
  • metal mask printing transfer methods using molds, and nanoimprinting.
  • the composition layer formed on the support may be dried (prebaked). Prebaking is not necessary when producing a film using a low-temperature process. If prebaking is performed, the prebaking temperature is preferably 150°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower. The lower limit can be, for example, 50°C or higher, or 80°C or higher.
  • the prebaking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and even more preferably 80 to 220 seconds. Prebaking can be performed using a hot plate, oven, etc.
  • the composition layer is exposed to light in a pattern (exposure process).
  • the composition layer can be exposed to light in a pattern by using a stepper exposure machine or scanner exposure machine through a mask with a predetermined mask pattern. This allows the exposed portions to harden.
  • Light that can be used for exposure includes g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), KrF-line (wavelength 248 nm), and ArF-line (wavelength 193 nm).
  • the light used for exposure preferably has a wavelength of 150 to 400 nm, and is preferably excimer laser light with a wavelength of 150 to 400 nm. Long-wavelength light sources of 400 nm or more can also be used for exposure.
  • the composition layer In the exposure step, it is preferable to irradiate the composition layer with light having a wavelength of 150 to 400 nm (preferably excimer laser light having a wavelength of 150 to 400 nm) to expose it in a pattern.
  • light having a wavelength of 150 to 400 nm preferably excimer laser light having a wavelength of 150 to 400 nm
  • Pulse exposure is an exposure method in which light is applied and paused repeatedly in short cycles (for example, milliseconds or less).
  • the irradiation dose is preferably, for example, 0.03 to 2.5 J/ cm2 , and more preferably 0.05 to 1.0 J/ cm2 .
  • the oxygen concentration during exposure can be selected appropriately.
  • exposure can be performed, for example, in a low-oxygen atmosphere with an oxygen concentration of 19 vol% or less (e.g., 15 vol%, 5 vol%, or substantially oxygen-free), or in a high-oxygen atmosphere with an oxygen concentration of more than 21 vol% (e.g., 22 vol%, 30 vol%, or 50 vol%).
  • the exposure illuminance can also be set appropriately. For example, it is preferably 100 to 100,000 W/ m2 , and more preferably 500 to 50,000 W/ m2 . Generally, it is 10,000 to 50,000 W/ m2 , but may be 1,000 W/m2 or less to enhance optical contrast. In the present invention, the exposure time can be shortened even at such low illuminance, thereby improving yield.
  • the unexposed portions of the composition layer are developed and removed to form a pattern (pixels).
  • the unexposed portions of the composition layer can be developed and removed using a developer. This causes the unexposed portions of the composition layer in the exposure step to dissolve into the developer, leaving only the photocured portions.
  • the temperature of the developer is preferably, for example, 20 to 30°C.
  • the development time is preferably 20 to 180 seconds. Furthermore, to improve residue removal, the process of shaking off the developer every 60 seconds and then supplying fresh developer may be repeated several times.
  • the developer may be an organic solvent or an alkaline developer, with alkaline developers being preferred.
  • the developer and post-development washing (rinsing) method described in paragraph 0214 of WO 2022/085485 can be used.
  • Additional exposure or post-baking is a post-development curing treatment to ensure complete curing.
  • the heating temperature for post-baking is preferably 100 to 300°C, and more preferably 200 to 270°C.
  • Post-baking can be performed continuously or batchwise using a heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater to heat the developed film to the above conditions.
  • a heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater to heat the developed film to the above conditions.
  • the light used for exposure has a wavelength of 400 nm or less.
  • the additional exposure may also be performed using the method described in Korean Patent Publication No. 10-2017-0122130.
  • the optical filter of the present invention includes the above-described film of the present invention.
  • Types of optical filters include color filters, infrared cut filters, and infrared transmission filters, and color filters are preferred.
  • the color filter preferably has the film of the present invention as its pixel, and more preferably has the film of the present invention as its color pixel.
  • the optical filter may have a protective layer provided on the surface of the film of the present invention.
  • a protective layer By providing a protective layer, various functions can be imparted, such as oxygen blocking, low reflectivity, hydrophilicity/hydrophobicity, and blocking of light of specific wavelengths (ultraviolet rays, infrared rays, etc.).
  • the thickness of the protective layer is preferably 0.01 to 10 ⁇ m, more preferably 0.1 to 5 ⁇ m.
  • Methods for forming the protective layer include a method of applying a resin composition for forming the protective layer, a chemical vapor deposition method, and a method of attaching a molded resin with an adhesive.
  • components constituting the protective layer include (meth)acrylic resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, polyol resins, polyvinylidene chloride resins, melamine resins, urethane resins, aramid resins, polyamide resins, alkyd resins, epoxy resins, modified silicone resins, fluororesins, polyacrylonitrile resins, cellulose resins, Si, C, W, Al 2 O 3 , Mo, SiO 2 , and Si 2 N 4 , and the protective layer may contain two or more of these components.
  • the protective layer in the case of a protective layer intended to block oxygen, the protective layer preferably contains a polyol resin, SiO 2 , and Si 2 N 4.
  • the protective layer in the case of a protective layer intended to reduce reflection, the protective layer preferably contains a (meth)acrylic resin and a fluororesin.
  • a protective layer by applying a resin composition When forming a protective layer by applying a resin composition, known methods such as spin coating, casting, screen printing, and inkjet printing can be used to apply the resin composition. Known organic solvents (e.g., propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.) can be used as the organic solvent contained in the resin composition.
  • known chemical vapor deposition methods thermal chemical vapor deposition, plasma chemical vapor deposition, photochemical vapor deposition
  • the chemical vapor deposition method can be used as the chemical vapor deposition method.
  • the protective layer may contain additives such as organic or inorganic fine particles, absorbers of specific wavelengths of light (e.g., ultraviolet light, infrared light, etc.), refractive index adjusters, antioxidants, adhesives, surfactants, etc., as needed.
  • organic and inorganic fine particles include polymeric fine particles (e.g., silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride, magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate, etc.
  • Known absorbers of specific wavelengths of light can be used.
  • the content of these additives can be adjusted as appropriate, but is preferably 0.1 to 70% by weight, and more preferably 1 to 60% by weight, of the total weight of the protective layer.
  • the protective layer may be one described in paragraphs 0073 to 0092 of JP 2017-151176 A.
  • the optical filter may have a structure in which each pixel is embedded in a space partitioned by partitions, for example in a grid pattern.
  • the solid-state imaging device of the present invention has the above-described film of the present invention.
  • the configuration of the solid-state imaging device is not particularly limited as long as it has the film of the present invention and functions as a solid-state imaging device, but examples thereof include the following configurations.
  • the device has a substrate on which multiple photodiodes constituting the light receiving area of a solid-state imaging device (such as a CCD (charge-coupled device) image sensor or a CMOS (complementary metal-oxide semiconductor) image sensor) and transfer electrodes made of polysilicon or the like; a light-shielding film on the photodiodes and transfer electrodes with only the light-receiving portions of the photodiodes open; a device protective film made of silicon nitride or the like formed on the light-shielding film to cover the entire light-shielding film and the light-receiving portions of the photodiodes; and a color filter on the device protective film.
  • a solid-state imaging device such as a CCD (charge-coupled device) image sensor or a CMOS (complementary metal-oxide semiconductor) image sensor
  • transfer electrodes made of polysilicon or the like
  • a light-shielding film on the photodiodes and
  • the device protective film may have a light-focusing means (e.g., a microlens, etc.; the same applies below) on the device protective film below the color filter (closer to the substrate), or a light-focusing means on the color filter.
  • the color filter may also have a structure in which each colored pixel is embedded in a space partitioned by partitions, for example, in a grid pattern. In this case, it is preferable that the partitions have a lower refractive index than each colored pixel. Examples of imaging devices having such a structure include those described in JP 2012-227478 A, JP 2014-179577 A, and WO 2018/043654 A.
  • an ultraviolet absorbing layer may be provided within the structure of the solid-state imaging element to improve light resistance.
  • Imaging devices equipped with the solid-state imaging element of the present invention can be used in digital cameras, electronic devices with imaging functions (such as mobile phones), as well as in-vehicle cameras and surveillance cameras.
  • the image display device of the present invention has the above-described film of the present invention.
  • image display devices include liquid crystal display devices and organic electroluminescence display devices. Definitions of image display devices and details of each image display device are described, for example, in “Electronic Display Devices” (written by Akio Sasaki, published by Kogyo Chosakai Co., Ltd. in 1990) and “Display Devices” (written by Nobuaki Ibuki, published by Sangyo Tosho Co., Ltd. in 1989).
  • Liquid crystal display devices are described, for example, in “Next Generation Liquid Crystal Display Technology” (edited by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994). There are no particular limitations on the liquid crystal display device to which the present invention can be applied, and the present invention can be applied to various types of liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology.”
  • the photopolymerization initiator of the present invention includes a compound represented by the above formula (1-A) or formula (1-B).
  • Synthesis Example 8 Synthesis of Compound A-245 18.4 g of diphenyl sulfide was added to a three-neck flask and dissolved in 100 mL of chlorobenzene. After cooling to 5°C, 14.3 g of aluminum chloride was added, followed by the dropwise addition of 21.5 g of 4-(t-butoxy)benzoic acid chloride over 10 minutes. The reaction solution was heated to 25°C and stirred for an additional 2 hours. Next, the reaction solution was cooled again to 5°C, and 17.1 g of aluminum chloride was added, followed by the dropwise addition of 16.5 g of 3-cyclopentylpropanoyl chloride over 10 minutes. The reaction solution was heated to 25°C and stirred for an additional 2 hours. The resulting reaction solution was added to 100 mL of ice water and extracted with 200 mL of ethyl acetate. The organic layer was concentrated to obtain 35.0 g of intermediate (A-245a).
  • intermediate (A-245a) 35.0 g was dissolved in 100 mL of toluene, 30 mL of trifluoromethanemethanesulfonic acid was added, and the mixture was heated and stirred at 60°C for 5 hours to deprotect the tert-butyl group. The resulting reaction solution was washed with ethyl acetate and water, and the organic layer was concentrated, and then methanol was added to precipitate crystals, yielding 27.5 g of intermediate (A-245b).
  • intermediate (A-245b) 21.5 g was placed in a three-neck flask and dissolved in 100 mL of pyridine. 15.0 g of hydroxylamine hydrochloride was added to this, and the mixture was stirred at 25°C for 10 hours. The resulting reaction solution was added to 200 mL of isopropyl alcohol and 200 mL of 1 M aqueous hydrochloric acid solution, and the resulting solid was collected by filtration. This crude product was recrystallized from acetonitrile to obtain 20.5 g of intermediate (A-245c).
  • Pigment Red 264 (red pigment) PR272 C.I. Pigment Red 272 (red pigment)
  • PR291 C.I. Pigment Red 291 (red pigment)
  • PO71 C.I. Pigment Orange 71 (orange pigment)
  • PB15:6 C.I. Pigment Blue 15:6 (blue pigment)
  • PV23 C.I.
  • Pigment Violet 23 (purple pigment)
  • P-1 Compound having the following structure (pyrrolopyrrole compound, infrared absorbing pigment)
  • P-2 Compound having the following structure (squarylium compound, infrared absorbing pigment)
  • P-3 Titanium black (TiOxNy) (black pigment, manufactured by Mitsubishi Materials Corporation)
  • P-4 Titanium oxide (white pigment, TTO-51(C), manufactured by Ishihara Sangyo Kaisha, Ltd.)
  • P-5 Compound having the following structure (magenta dye)
  • (resin) C2-1 Resin having the following structure (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units.
  • C2-2 Resin having the following structure (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units.
  • C2-3 Resin having the following structure (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units.
  • Photocurable compositions were produced by mixing the types of materials shown in the table below with 0.2 parts by mass of KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a surfactant, 0.2 parts by mass of Adekastab AO-80 (manufactured by ADEKA Corporation) as an antioxidant, and 0.01 parts by mass of p-methoxyphenol as a polymerization inhibitor.
  • KF-6001 manufactured by Shin-Etsu Chemical Co., Ltd.
  • Adekastab AO-80 manufactured by ADEKA Corporation
  • p-methoxyphenol p-methoxyphenol
  • Dispersions R1 to R12, G1 to G12, B1 to B7, IR1 to IR7, Bk1 to Bk4, and Wh1 the above-mentioned dispersions R1 to R12, G1 to G12, B1 to B7, IR1 to IR7, Bk1 to Bk4, and Wh1
  • (resin) B-1 Resin having the following structure (the numbers attached to the main chain are molar ratios; weight average molecular weight: 11,000; acid value: 69 mg KOH/g)
  • B-2 Resin having the following structure (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units.
  • B-3 Resin having the following structure (the numbers attached to the main chain are molar ratios; weight average molecular weight: 12,000; acid value: 80 mg KOH/g)
  • B-4 Resin having the following structure (the number attached to the main chain is the molar ratio; weight-average molecular weight: 26,000, polyamic acid resin)
  • B-5 Resin having the following structure (the number attached to the main chain is the molar ratio; weight average molecular weight 25,000, polyimide resin)
  • B-6 Resin having the following structure (the numerical values attached to the main chain are molar ratios; weight average molecular weight 27,500, acid value 2 mg KOH/g, amine value 1 mg KOH/g, imidization rate 10%)
  • B-7 Resin having the following structure (the numerical values attached to the main chain are molar ratios; weight average molecular weight 24,500, acid value 4 mg KOH/g, amine value 2 mg KOH/g, imidization rate 92%)
  • M-1 A mixture of compounds having the following structure (a mixture of the compound on the left (a hexafunctional (meth)acrylate compound) and the compound on the right (a pentafunctional (meth)acrylate compound) in a molar ratio of 7:3)
  • M-2 Compound of the following structure
  • M-3 Compound having the following structure
  • M-4 Compound having the following structure
  • M-5 Compound having the following structure
  • M-6 CN9906NS (manufactured by Arkema, an aliphatic polyfunctional urethane acrylate having a tertiary amine structure (compound described in JP 2024-119784 A)
  • A-1 to A-339 Compounds A-1 to A-339 shown as specific examples of the specific compounds described above cA-1 and cA-2: Compounds having the following structures (comparative compounds) a-1 to a-14: Compounds having the following structures (other photopolymerization initiators) a-15: A mixture of 14 equal parts of TR-PBG-301, TR-PBG-304, TR-PBG-305, TR-PBG-309, TR-PBG-3054, TR-PBG-3057, TR-PBG-314, TR-PBG-327, TR-PBG-345, TR-PBG-346, TR-PBG-358, TR-PBG-365, TR-PBG-380, and TR-PBG-610 (all manufactured by TRONLY) (another photopolymerization initiator) a-16: A mixture of equal amounts of three types of NCI-730, NCI-831E, and NCI-930 (all manufactured by ADEKA Corporation) (another photopoly
  • T-1 to T-8 Compounds having the following structure.
  • T-9 A mixture of equal amounts of a thermal polymerization initiator (Perbutyl C (peroxide) (manufactured by NOF Corporation)), a thermal base generator (U-CAT SA102 (carboxylic acid salt of DBU) (manufactured by San-Apro Co., Ltd.)), a rust inhibitor (benzotriazole), a light absorber (ADK STAB AO-80 (manufactured by ADEKA Corporation)), and a polymerization inhibitor (di-t-butylhydroxytoluene (BHT)).
  • a thermal polymerization initiator Perbutyl C (peroxide) (manufactured by NOF Corporation)
  • U-CAT SA102 carboxylic acid salt of DBU) (manufactured by San-Apro Co., Ltd.)
  • a rust inhibitor benzotriazole
  • ADK STAB AO-80 manufactured by ADEKA Corporation
  • An underlayer-forming composition (CT-4000L, manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied to an 8-inch (20.32 cm) silicon wafer using a spin coater so that the thickness after post-baking would be 0.1 ⁇ m, and the wafer was heated at 220° C. for 300 seconds using a hot plate to form an underlayer, thereby obtaining a silicon wafer with an underlayer.
  • Each of the photocurable compositions obtained above was applied by spin coating onto the underlayer of a silicon wafer with an underlayer so that the film thickness after application would be 0.6 ⁇ m, and then heated using a hot plate at 110° C. for 2 minutes to form a composition layer.
  • the obtained composition layer was exposed to light (i-line) having a wavelength of 365 nm through a mask having a 0.45 ⁇ m square pattern using an i-line stepper exposure machine under exposure conditions of an illuminance of 20,000 W/m 2 and an exposure dose of 20 to 300 mJ/cm 2 (exposure condition 1), or an illuminance of 2,000 W/cm 2 and an exposure dose of 20 to 300 mJ/cm 2 (exposure condition 2).
  • the exposed composition layer was subjected to shower development at 23°C for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) as a developer.
  • TMAH tetramethylammonium hydroxide
  • Ea/Eb The ratio (Ea/Eb) of the exposure dose Ea required for the pattern line width to reach 0.5 ⁇ m when exposed under exposure condition 1 to the exposure dose Eb required for the pattern line width to reach 0.5 ⁇ m when exposed under exposure condition 2 was calculated, and the exposure illuminance dependency was evaluated according to the following criteria: The closer the value of Ea/Eb is to 1, the smaller the exposure illuminance dependency of the exposure dose is.
  • Each photocurable composition obtained above was spin-coated onto the underlayer of the underlayer-equipped silicon wafer so that the film thickness after coating was 0.6 ⁇ m, and then heated at 110° C. for 2 minutes using a hot plate to form a composition layer.
  • the resulting composition layer was exposed to light (i-line) with a wavelength of 365 nm through a mask having a 0.45 ⁇ m square pattern using an i-line stepper exposure machine at an illuminance of 20,000 W/m 2 and the above-mentioned exposure amount Ea.
  • the exposed composition layer was shower-developed for 60 seconds at 23° C.
  • TMAH tetramethylammonium hydroxide
  • TMAH tetramethylammonium hydroxide
  • Za/Zb The ratio (Za/Zb) of the residue area ratio Za when formed using developer 1 to the residue area ratio Zb when formed using developer 2 was calculated, and the developability was evaluated according to the following criteria. The closer Za/Zb is to 1, the smaller the developer concentration dependency and the more excellent the developability.
  • D: Za/Zb is 0.70 or more and less than 0.80, or 1.20 or more and less than 1.30.
  • Za/Zb is less than 0.70, or 1.30 or more.
  • Each photocurable composition obtained above was applied by spin coating onto the underlayer of the underlayer-equipped silicon wafer so that the film thickness after application was 0.6 ⁇ m, and then heated at 110°C for 2 minutes using a hot plate to form a composition layer.
  • the resulting composition layer was exposed to light (i-line) with a wavelength of 365 nm through a mask having a 0.45 ⁇ m square pattern using an i-line stepper exposure machine, with the illuminance being 2000 W/ m2 and the exposure dose varying within the range of 20 to 300 mJ/ cm2 .
  • the exposed composition layer was then shower-developed for 60 seconds at 23°C using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) as the developer.
  • TMAH tetramethylammonium hydroxide
  • Water droplets adhering to the pattern surface were then removed with air, and the pattern was allowed to dry naturally to form a pattern (pixels).
  • the silicon wafer with the formed pixels was observed at 20,000x magnification using a scanning electron microscope (S-4800H, manufactured by Hitachi High-Tech Corporation). In the observed pixel, the exposure dose Ea required for the pattern line width to reach 0.5 ⁇ m was calculated.
  • Ea is less than 100 mJ/cm 2
  • Ea is 100 mJ/cm 2 or more and less than 200 mJ/cm 2
  • C Ea is 200 mJ/cm 2 or more and less than 500 mJ/cm 2
  • D Ea is 500 mJ/cm 2 or more and less than 1000 mJ/cm 2
  • Ea is 1000 mJ/cm 2 or more

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Abstract

L'invention concerne une composition photodurcissable qui contient un initiateur de photopolymérisation et un composé polymérisable, l'initiateur de photopolymérisation comprenant un composé représenté par la formule (1-A) ou la formule (1-B). L'invention concerne également un procédé de production de pixels, un film, un filtre optique, un élément d'imagerie à semi-conducteurs et un dispositif d'affichage d'image utilisant ladite composition photodurcissable. L'invention concerne en outre un initiateur de photopolymérisation comprenant ledit composé.
PCT/JP2025/014108 2024-04-23 2025-04-09 Composition photodurcissable, procédé de production de pixels, film, filtre optique, élément d'imagerie à semi-conducteurs, dispositif d'affichage d'image et initiateur de photopolymérisation Pending WO2025225376A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2024069947 2024-04-23
JP2024-069947 2024-04-23

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WO2025225376A1 true WO2025225376A1 (fr) 2025-10-30

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PCT/JP2025/014108 Pending WO2025225376A1 (fr) 2024-04-23 2025-04-09 Composition photodurcissable, procédé de production de pixels, film, filtre optique, élément d'imagerie à semi-conducteurs, dispositif d'affichage d'image et initiateur de photopolymérisation

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WO (1) WO2025225376A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011525480A (ja) * 2008-06-06 2011-09-22 ビーエーエスエフ ソシエタス・ヨーロピア オキシムエステル光開始剤
JP2023517304A (ja) * 2020-03-04 2023-04-25 ベーアーエスエフ・エスエー オキシムエステル光開始剤
JP7442004B1 (ja) * 2023-03-01 2024-03-01 ａｒｔｉｅｎｃｅ株式会社 感光性組成物、それを用いた膜、光学フィルタ、固体撮像素子、画像表示装置、及び赤外線センサ

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011525480A (ja) * 2008-06-06 2011-09-22 ビーエーエスエフ ソシエタス・ヨーロピア オキシムエステル光開始剤
JP2023517304A (ja) * 2020-03-04 2023-04-25 ベーアーエスエフ・エスエー オキシムエステル光開始剤
JP7442004B1 (ja) * 2023-03-01 2024-03-01 ａｒｔｉｅｎｃｅ株式会社 感光性組成物、それを用いた膜、光学フィルタ、固体撮像素子、画像表示装置、及び赤外線センサ

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