WO2024043108A1 - Composition photodurcissable, procédé de production de film durci, film, élément d'imagerie à semi-conducteurs, dispositif d'affichage d'image et initiateur de polymérisation radicalaire - Google Patents

Composition photodurcissable, procédé de production de film durci, film, élément d'imagerie à semi-conducteurs, dispositif d'affichage d'image et initiateur de polymérisation radicalaire Download PDF

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WO2024043108A1
WO2024043108A1 PCT/JP2023/029178 JP2023029178W WO2024043108A1 WO 2024043108 A1 WO2024043108 A1 WO 2024043108A1 JP 2023029178 W JP2023029178 W JP 2023029178W WO 2024043108 A1 WO2024043108 A1 WO 2024043108A1
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group
photocurable composition
formula
resin
mass
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PCT/JP2023/029178
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Japanese (ja)
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雅臣 牧野
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富士フイルム株式会社
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    • 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
    • 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
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
    • C07D311/82—Xanthenes
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
    • C09B47/10—Obtaining compounds having halogen atoms directly bound to the phthalocyanine skeleton
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B47/00—Porphines; Azaporphines
    • C09B47/04—Phthalocyanines abbreviation: Pc
    • C09B47/30—Metal-free phthalocyanines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B55/00—Azomethine dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/04—Isoindoline dyes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures

Definitions

  • the present disclosure relates to a photocurable composition, a method for producing a cured film, a film, a solid-state imaging device, an image display device, and a radical polymerization initiator.
  • Optical filters such as color filters are manufactured using a photocurable composition containing a colorant, a photopolymerization initiator, and a polymerizable compound.
  • a photocurable composition containing a colorant, a photopolymerization initiator, and a polymerizable compound.
  • conventional photopolymerization initiators the photopolymerization initiators described in Japanese translations of PCT publication No. 2012-519191 or PCT publication No. 2016-531926 are known.
  • Japanese Patent Publication No. 2012-519191 describes a carbazole oxime ester photoinitiator.
  • 2016-531926 describes an oxime ester photoinitiator having an indole ring or the like.
  • a problem to be solved by the embodiments of the present disclosure is to provide a highly sensitive photocurable composition. Moreover, the problem to be solved by other embodiments of the present disclosure is to provide a method for producing a cured film, a film, a solid-state image sensor, or an image display device using the photocurable composition. Furthermore, a problem to be solved by other embodiments of the present disclosure is to provide a novel radical polymerization initiator.
  • Means for solving the above problems include the following aspects. ⁇ 1> A photocurable composition containing a colorant, a radical polymerization initiator represented by formula (1), and a radically polymerizable compound.
  • Ar 1 represents a (k+m+1)-valent aromatic group or a (k+m+1)-valent heteroaromatic group
  • Ar 2 represents a (k+2)-valent aromatic group or a (k+2)-valent heteroaromatic group.
  • R 1 represents an alkyl group, aryl group, heteroaryl group, alkoxy group, aryloxy group, or heteroaryloxy group
  • L represents a single bond or CR 11 R 12
  • R 11 and R 12 each independently represents a hydrogen atom, an alkyl group, or an aryl group
  • k represents 0 or 1
  • R 6 each independently represents a halogen atom or a monovalent organic group
  • Ar 1 may form a ring structure
  • Y 1 represents a group represented by the following formula (2)
  • m represents an integer of 0 to 4
  • n represents 0 or 1.
  • R 2 represents an alkyl group, provided that when L 2 is CHR, R 2 may be a hydrogen atom, R 3 represents a hydrogen atom or an alkyl group, and R 4 is an alkyl group.
  • L 1 and L 2 each independently represent CHR, O, S or NR
  • R each independently represents a hydrogen atom or an alkyl group, and among R 2 , R 3 , R 4 and R Two or more of these may be linked to each other to form a ring structure
  • Z represents a single bond or an alkylene group having 1 to 6 carbon atoms
  • * represents a linking portion with an oxime group.
  • L 3 and L 4 each independently represent CHR, O, S, or NR, at least one of L 3 and L 4 is CHR, and R represents a hydrogen atom or an alkyl group.
  • R5 each independently represents a hydrogen atom or an alkyl group, p represents an integer of 1 to 6, and * represents a linkage with an oxime group.
  • Ar 3 represents an aryl group or a heteroaryl group
  • * represents a linkage with Ar 1 .
  • Ar 3 represents an aryl group or a heteroaryl group
  • R 7 represents an alkyl group or an aryl group
  • L represents a single bond or CR 11 R 12
  • R 11 and R 12 each independently , represents a hydrogen atom, an alkyl group, or an aryl group
  • Z represents an alkylene group having 1 to 3 carbon atoms
  • k represents 0 or 1
  • n represents 0 or 1
  • p represents an integer of 1 to 6.
  • ⁇ 5> The photocurable composition according to any one of ⁇ 1> to ⁇ 4>, wherein the content of the colorant is 60% by mass or more based on the total solid content of the composition.
  • ⁇ 6> The photocurable composition according to any one of ⁇ 1> to ⁇ 5>, further comprising a resin.
  • the resin is a graft polymer having a graft chain, and the graft chain includes at least one selected from the group consisting of a polyether chain, a polyester chain, and a polyacrylic chain, and
  • the photocurable composition according to ⁇ 6> comprising a resin having a weight average molecular weight of 1,000 or more.
  • ⁇ 8> The photocurable composition according to ⁇ 6>, wherein the resin includes a resin having a (meth)acryloyl group, an epoxy group, or an oxetanyl group.
  • the resin includes a resin having a (meth)acryloyl group, an epoxy group, or an oxetanyl group.
  • ⁇ 9> The photocurable composition according to any one of ⁇ 1> to ⁇ 8>, further comprising a pigment derivative.
  • ⁇ 10> The photocurable composition according to any one of ⁇ 1> to ⁇ 9>, further comprising a chain transfer agent.
  • ⁇ 11> The photocurable composition according to any one of ⁇ 1> to ⁇ 10>, further comprising a sensitizer.
  • ⁇ 12> The photocurable composition according to any one of ⁇ 1> to ⁇ 11>, which is used for excimer laser exposure with a wavelength of 150 nm to 300 nm.
  • a method for producing a cured film comprising a step of irradiating the photocurable composition according to any one of ⁇ 1> to ⁇ 12> with excimer laser light having a wavelength of 150 nm to 300 nm.
  • ⁇ 14> A film that is a cured product of the photocurable composition according to any one of ⁇ 1> to ⁇ 12>.
  • ⁇ 15> A solid-state imaging device comprising the film according to ⁇ 14>.
  • An image display device including the film according to ⁇ 14>.
  • Ar 1 represents a (k+m+1)-valent aromatic group or a (k+m+1)-valent heteroaromatic group
  • Ar 2 represents a (k+2)-valent aromatic group or a (k+2)-valent heteroaromatic group.
  • R 1 represents an alkyl group, aryl group, heteroaryl group, alkoxy group, aryloxy group, or heteroaryloxy group
  • L represents a single bond or CR 11 R 12
  • R 11 and R 12 each independently represents a hydrogen atom, an alkyl group, or an aryl group
  • k represents 0 or 1
  • R 6 each independently represents a halogen atom or a monovalent organic group, and one or more R 6 is Ar 1 may form a ring structure
  • Y 1 represents a group represented by the following formula (2-1)
  • m represents an integer of 0 to 4
  • n represents 0 or 1.
  • R 3 represents a hydrogen atom or an alkyl group
  • L 1 and L 2 each independently represent CHR, O, S, or NR
  • L A is an alkylene group having 1 to 6 carbon atoms.
  • R each independently represents a hydrogen atom or an alkyl group
  • Z represents a single bond or an alkylene group having 1 to 6 carbon atoms
  • * represents a linkage with an oxime group.
  • a highly sensitive photocurable composition is provided. Further, according to other embodiments of the present disclosure, there are provided a method for producing a cured film, a film, a solid-state imaging device, or an image display device using the photocurable composition. Furthermore, according to other embodiments of the present disclosure, a novel radical polymerization initiator is provided.
  • alkyl group includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • exposure includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.
  • the light used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet (EUV) light, X-rays, and electron beams.
  • (meth)acrylate represents acrylate and/or methacrylate
  • (meth)acrylic represents both acrylic and/or methacrylic
  • (meth)acrylate represents acrylic and/or methacrylate.
  • "Acryloyl” refers to either or both of acryloyl and methacryloyl.
  • Me in the structural formula 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 polystyrene equivalent values measured by GPC (gel permeation chromatography).
  • the total solid content refers to the total mass of all components of the composition excluding the solvent.
  • pigment means a colorant that is difficult to dissolve in a solvent.
  • the term "process" is used not only to refer to an independent process, but also to include a process in which the intended effect of the process is achieved even if the process cannot be clearly distinguished from other processes. .
  • oxime compounds in which E-form and Z-form stereoisomers exist may be either E-form or Z-form unless otherwise specified. The present disclosure will be described in detail below.
  • the photocurable composition according to the present disclosure includes a colorant, a radical polymerization initiator represented by formula (1), and a radically polymerizable compound.
  • Ar 1 represents a (k+m+1)-valent aromatic group or a (k+m+1)-valent heteroaromatic group
  • Ar 2 represents a (k+2)-valent aromatic group or a (k+2)-valent heteroaromatic group.
  • R 1 represents an alkyl group, aryl group, heteroaryl group, alkoxy group, aryloxy group, or heteroaryloxy group
  • L represents a single bond or CR 11 R 12
  • R 11 and R 12 each independently represents a hydrogen atom, an alkyl group, or an aryl group
  • k represents 0 or 1
  • R 6 each independently represents a halogen atom or a monovalent organic group
  • Ar 1 may form a ring structure
  • Y 1 represents a group represented by the following formula (2)
  • m represents an integer of 0 to 4
  • n represents 0 or 1.
  • R 2 represents an alkyl group, provided that when L 2 is CHR, R 2 may be a hydrogen atom, R 3 represents a hydrogen atom or an alkyl group, and R 4 is an alkyl group.
  • L 1 and L 2 each independently represent CHR, O, S or NR
  • R each independently represents a hydrogen atom or an alkyl group, and among R 2 , R 3 , R 4 and R Two or more of these may be linked to each other to form a ring structure
  • Z represents a single bond or an alkylene group having 1 to 6 carbon atoms
  • * represents a linking portion with an oxime group.
  • the photocurable composition according to the present disclosure can be suitably used as a photocurable composition for exposure to light with a wavelength of 150 nm to 300 nm, and as a photocurable composition for exposure to excimer laser light with a wavelength of 150 nm to 300 nm. It can be used particularly preferably.
  • the radical polymerization initiator represented by the above formula (1) has a structure in which two aromatic rings are connected by an ether bond, so that the light absorption peak becomes sharper and the absorption efficiency is improved.
  • having the group represented by the above formula (2) promotes the generation of radicals from the oxime ester structure, resulting in a highly sensitive photocurable composition. .
  • the photocurable composition according to the present disclosure is preferably used as a photocurable composition for optical filters.
  • the optical filter include color filters and infrared transmission filters, and color filters are preferred. That is, the photocurable composition according to the present disclosure is preferably used as a photocurable composition for color filters. More specifically, it can be preferably used as a photocurable composition for forming pixels of color filters. Types of pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, yellow pixels, and the like.
  • the infrared transmission filter has a maximum transmittance of 20% or less, preferably 15% or less, more preferably 10% or less in the wavelength range of 400 nm to 640 nm, and has a maximum transmittance in the wavelength range of 1,100 nm to 1,300 nm.
  • Preferred examples include filters that satisfy spectral characteristics in which the minimum value of the ratio is 70% or more, preferably 75% or more, and more preferably 80% or more.
  • the infrared transmission filter is preferably a filter that satisfies any of the following spectral characteristics (1) to (5).
  • the maximum value of transmittance in the wavelength range of 400 nm to 640 nm is 20% or less, preferably 15% or less, more preferably 10% or less, and the minimum value of transmittance in the wavelength range of 800 nm to 1,500 nm. is 70% or more, preferably 75% or more, more preferably 80% or more.
  • the maximum value of transmittance in the wavelength range of 400 nm to 750 nm is 20% or less, preferably 15% or less, more preferably 10% or less, and the minimum value of transmittance in the wavelength range of 900 nm to 1,500 nm. is 70% or more, preferably 75% or more, more preferably 80% or more.
  • the maximum value of transmittance in the wavelength range of 400 nm to 830 nm is 20% or less, preferably 15% or less, more preferably 10% or less, and the transmittance in the wavelength range of 1,000 nm to 1,500 nm is A filter whose minimum value is 70% or more, preferably 75% or more, more preferably 80% or more.
  • the maximum value of transmittance in the wavelength range of 400 nm to 950 nm is 20% or less, preferably 15% or less, more preferably 10% or less, and the transmittance in the wavelength range of 1,100 nm to 1,500 nm is A filter whose minimum value is 70% or more, preferably 75% or more, more preferably 80% or more.
  • the maximum value of transmittance in the wavelength range of 400 nm to 1,050 nm is 20% or less, preferably 15% or less, more preferably 10% or less, and the transmittance in the wavelength range of 1,200 nm to 1,500 nm.
  • the photocurable composition according to the present disclosure is preferably used for solid-state imaging devices. More specifically, it is preferably used as a photocurable composition for optical filters used in solid-state imaging devices, and more preferably used as a photocurable composition for color filters used in solid-state imaging devices.
  • the solid content concentration of the photocurable composition according to the present disclosure is preferably 5% by mass to 40% by mass.
  • the lower limit is more preferably 7.5% by mass or more, and even more preferably 10% by mass or more.
  • the upper limit is more preferably 35% by mass or less, and even more preferably 30% by mass or less.
  • the photocurable composition according to the present disclosure includes a radical polymerization initiator represented by the above formula (1).
  • the radical polymerization initiator represented by the above formula (1) is preferably a radical photopolymerization initiator, more preferably a radical photopolymerization initiator that generates radicals by light with a wavelength of 150 nm to 300 nm.
  • the exposure wavelength at which the radical polymerization initiator represented by the above formula (1) generates radicals is preferably 150 nm to 460 nm, more preferably 150 nm to 420 nm, even more preferably 150 nm to 380 nm, and particularly preferably 150 nm to 300 nm.
  • Ar 1 in formula (1) is preferably a (k+m+1)-valent aromatic group from the viewpoint of sensitivity, adhesion, and undercut suppression, and has (k+m+1) hydrogen atoms from benzene which may be substituted. It is more preferable to be a group from which an atom is removed, or a group from which (k+m+1) hydrogen atoms are removed from naphthalene which may be substituted, and a group from which (k+m+1) hydrogen atoms are removed from benzene which may be substituted.
  • Ar 2 in formula (1) is preferably a (k+2)-valent aromatic group from the viewpoint of sensitivity, adhesion, and undercut suppression, and has (k+2) hydrogen atoms from the optionally substituted benzene. It is more preferable to be a group from which an atom is removed, or a group from which (k+2) hydrogen atoms are removed from naphthalene which may be substituted, and a group from which (k+2) hydrogen atoms are removed from benzene which may be substituted.
  • Ar 1 and Ar 2 in formula (1) are preferably line symmetrical with respect to the oxygen atoms bonded to Ar 1 and Ar 2 from the viewpoint of sensitivity, adhesion, and undercut suppression. .
  • the aromatic group and heteroaromatic group represented by Ar 1 and Ar 2 in formula (1) may further have a substituent.
  • the substituent is not particularly limited, and substituents having 0 to 100 carbon atoms are preferably mentioned, and substituents having 0 to 50 carbon atoms are more preferably mentioned.
  • substituents include halogen atoms, hydroxy groups, amino groups, alkyl groups, cycloalkyl groups, alkenyl groups, heterocyclic groups, aryl groups, heteroaryl groups, acyl groups, nitro groups, cyano groups, sulfo groups, Examples include an alkylaminocarbonyl group, an alkoxycarbonyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, a morpholino group, an alkoxyalkyl group, a carboxy group, and a carboxy-substituted alkyl group.
  • these substituents may further have a substituent, or the substituents may be bonded to each other to form a ring structure.
  • substituent for the aromatic group and heteroaromatic group in Ar 1 and Ar 2 in formula (1) a halogen atom is preferable, and a bromine atom is more preferable.
  • R 11 and R 12 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 10 carbon atoms, from the viewpoint of sensitivity, adhesion, and undercut suppression. It is preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, even more preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 2 to 4 carbon atoms. Particularly preferred. Further, the alkyl group and aryl group in R 11 and R 12 may have a substituent. Examples of the substituent include those mentioned above. Among these, as the substituent, an alkoxy group is preferably mentioned.
  • L in formula (1) is preferably a single bond from the viewpoints of sensitivity, adhesion, and undercut suppression. It is preferable that k in formula (1) is 1 from the viewpoints of sensitivity, adhesion, and undercut suppression.
  • X is at least one group selected from the group consisting of X-3, X-8, X-11 and X-12, and X-3 is more preferable. .
  • R 6 in formula (1) is preferably a group having at least a halogen atom, a nitro group, a cyano group, an aromatic ring, or a heteroaromatic ring, from the viewpoint of sensitivity, adhesion, and undercut suppression, and It is more preferably an atom, an aromatic acyl group, or a heteroaromatic acyl group, even more preferably a bromine atom or an aromatic acyl group, and particularly preferably an aromatic acyl group.
  • the aromatic ring, heteroaromatic ring, aromatic acyl group, heteroaromatic acyl group, etc. in R 6 may have a substituent. Examples of the substituent include those mentioned above.
  • the substituent is preferably a halogen atom, a nitro group, a cyano group, an alkoxy group, an alkylthio group, a trifluoromethyl group, a dimethylamino group, or a morpholino group, and more preferably a bromine atom.
  • m in formula (1) is preferably 1 or 2, and more preferably 1, from the viewpoints of sensitivity, adhesion, and undercut suppression.
  • R 6 in formula (1) is preferably a halogen atom, a nitro group, a cyano group, or a group represented by the following formula (4), and is preferably a bromine atom or a group represented by the following formula (4). It is more preferable that it is a group represented by the following formula (4), and even more preferable that it is a group represented by the following formula (4).
  • Ar 3 represents an aryl group or a heteroaryl group
  • * represents a linkage with Ar 1 .
  • Ar 3 in formula (4) is preferably an aryl group that may have a substituent, and is an aryl group having 6 to 14 carbon atoms that may have a substituent. More preferably, it is an aryl group having 6 to 10 carbon atoms which may have a substituent, and particularly preferably a naphthyl group which may have a substituent.
  • the aryl group for Ar 3 include a phenyl group, a naphthyl group, an anthracenyl group, and the like.
  • Examples of the heteroaryl group for Ar 3 include a furanyl group, a thienyl group, a pyrrole group, and the like.
  • the aryl group or heteroaryl group in Ar 3 may have a substituent.
  • substituents include those mentioned above.
  • the substituent is preferably a halogen atom, a nitro group, a cyano group, an alkoxy group, an alkylthio group, a trifluoromethyl group, a dimethylamino group, or a morpholino group, and more preferably a bromine atom.
  • R 6 in formula (1) Preferred specific examples of R 6 in formula (1) are shown below. Note that * represents the bonding position with Ar 1 . Preferred specific examples of R 6 include a halogen atom, a nitro group, and a cyano group.
  • R 6 is selected from the group consisting of bromine atom, R6-1, R6-12, R6-13, R6-14, R6-15, R6-16, R6-19 and R6-20.
  • R 1 in formula (1) is preferably an alkyl group, an aryl group, an alkoxy group, or an aryloxy group, more preferably an alkyl group or an aryl group, and preferably an alkyl group. More preferably, it is an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group.
  • the alkyl group, aryl group, alkoxy group, aryloxy group, etc. in R 1 may have a substituent. Examples of the substituent include those mentioned above.
  • Y 1 in formula (1) is a group represented by formula (2) below.
  • R 2 represents an alkyl group, provided that when L 2 is CHR, R 2 may be a hydrogen atom, R 3 represents a hydrogen atom or an alkyl group, and R 4 is an alkyl group.
  • L 1 and L 2 each independently represent CHR, O, S or NR
  • R each independently represents a hydrogen atom or an alkyl group, and among R 2 , R 3 , R 4 and R Two or more of these may be linked to each other to form a ring structure
  • Z represents a single bond or an alkylene group having 1 to 6 carbon atoms
  • * represents a linking portion with an oxime group.
  • R 2 in formula (2) is preferably an alkyl group.
  • R 3 in formula (2) is preferably a hydrogen atom.
  • R 4 in formula (2) is preferably an alkyl group.
  • R 2 and R 4 are preferably bonded to each other to form a ring structure, and R 2 and R 4 are bonded to each other to form an aliphatic structure. It is more preferable that the group hydrocarbon ring structure is formed.
  • L 1 in formula (2) is preferably O, S, or NR, and more preferably O or NR.
  • L 2 in formula (2) is preferably CHR.
  • R in the above NR is preferably an alkyl group, more preferably a methyl group or a cycloalkyl group, and particularly preferably a methyl group, a cyclopentyl group, or a cyclohexyl group.
  • R in the above CHR is preferably a hydrogen atom.
  • Z in formula (2) is preferably a single bond or an alkylene group having 1 to 4 carbon atoms, more preferably a single bond, a methylene group or an ethylene group, and is a single bond. is particularly preferred.
  • Y 1 in formula (1) is more preferably a group represented by the following formula (2-1) from the viewpoint of sensitivity.
  • R 3 represents a hydrogen atom or an alkyl group
  • L 1 and L 2 each independently represent CHR, O, S, or NR
  • L A is an alkylene group having 1 to 6 carbon atoms.
  • R each independently represents a hydrogen atom or an alkyl group
  • Z represents a single bond or an alkylene group having 1 to 6 carbon atoms
  • * represents a linkage with an oxime group.
  • R 3 , L 1 , L 2 , R and Z in formula (2-1) are the same as the preferred embodiments of R 3 , L 1 , L 2 , R and Z in formula (2), respectively.
  • L A in formula (2-1) is preferably an alkylene group having 3 or 4 carbon atoms, and more preferably a 1,3-propylene group.
  • Y 1 in formula (1) is more preferably a group represented by formula (3) below.
  • L 3 and L 4 each independently represent CHR, O, S, or NR, at least one of L 3 and L 4 is CHR, and R represents a hydrogen atom or an alkyl group.
  • R 5 each independently represents a hydrogen atom or an alkyl group, p represents an integer of 1 to 6, and * represents a linkage with an oxime group.
  • L 3 in formula (3) is preferably O, S, or NR.
  • L 4 in formula (3) is preferably CHR.
  • a preferred embodiment of R in formula (3) is the same as a preferred embodiment of R in formula (2).
  • R 5 in formula (3) is preferably a hydrogen atom.
  • p in formula (3) is preferably an integer of 3 to 5, more preferably 3 or 4, and particularly preferably 3.
  • Each group such as the alkyl group, aryl group, alkylene group, and alkyl group in the alkoxy group in R 1 to R 5 , R, L A and Z may further have a substituent.
  • the substituent the substituents mentioned above for Ar 1 are preferably mentioned.
  • n in formula (1) is preferably 0.
  • the radical polymerization initiator represented by the above formula (1) is preferably a compound represented by the following formula (5) from the viewpoints of sensitivity, adhesion, and undercut suppression properties.
  • Ar 3 represents an aryl group or a heteroaryl group
  • R 7 represents an alkyl group or an aryl group
  • L represents a single bond or CR 11 R 12
  • R 11 and R 12 each independently , represents a hydrogen atom, an alkyl group, or an aryl group
  • Z represents an alkylene group having 1 to 3 carbon atoms
  • k represents 0 or 1
  • n represents 0 or 1
  • p represents an integer of 1 to 6.
  • R 7 in formula (5) is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group.
  • the alkyl group or aryl group in R 7 may have a substituent. Examples of the substituent include those mentioned above.
  • the radical polymerization initiator represented by the above formula (1) may have absorption at a wavelength of 193 nm which is an ArF absorption region, a wavelength of 248 nm which is a KrF absorption region, or a wavelength of 365 nm which is an i-line absorption region.
  • the gram extinction coefficient of the radical polymerization initiator represented by the above formula (1) at either wavelength 248 nm or 365 nm is preferably 1,000 L ⁇ g ⁇ 1 ⁇ cm ⁇ 1 or more, It is more preferably 10,000 L ⁇ g ⁇ 1 ⁇ cm ⁇ 1 or more, and even more preferably 20,000 L ⁇ g ⁇ 1 ⁇ cm ⁇ 1 or more.
  • the gram extinction coefficient of the radical polymerization initiator represented by formula (1) is measured by the following method. 12.5 mg of the polymerization initiator was accurately weighed and poured into a 100 mL volumetric flask. Add acetonitrile to this and dissolve completely. Take out 2 mL of this polymerization initiator solution with a whole pipette and make up the volume in a 25 mL volumetric flask. This is taken as the measurement sample. A sample is added to a 1 cm square 5 mL quartz glass cell, the absorbance is measured under air, and the gram extinction coefficient is calculated. The measuring instrument used is (ultraviolet-visible-near-infrared spectrophotometer UH4150 (manufactured by Hitachi High-Tech Science Co., Ltd.)).
  • the molecular weight of the radical polymerization initiator represented by the above formula (1) is preferably 150 or more, more preferably 200 or more, and particularly preferably 250 or more. Further, the upper limit is preferably less than 1,000, more preferably less than 900, and even more preferably less than 800.
  • radical polymerization initiator represented by the above formula (1) examples include preferably A-1 to A-190, but it goes without saying that the radical polymerization initiator is not limited thereto.
  • X represents X which is a structure containing Ar 1 , Ar 2 , oxygen atom, L and k described above, and R6-1 to R6-28, X-1 to X-14 and Y-1 to Y- 25 are the same groups as R6-1 to R6-28, X-1 to X-14, and Y-1 to Y-25, respectively.
  • tBu represents a t-butyl group
  • Ph represents a phenyl group.
  • the photocurable composition according to the present disclosure may contain only one kind of radical polymerization initiator represented by the above formula (1), or may contain two or more kinds. When two or more types are used, the total amount thereof is preferably within the following range. From the viewpoint of sensitivity and coating film uniformity, the content of the radical polymerization initiator represented by the above formula (1) is 0.01% by mass to 30% by mass based on the total solid content of the photocurable composition. %, more preferably 0.05% to 25% by weight, even more preferably 0.1% to 20% by weight, particularly preferably 1% to 15% by weight.
  • the radical polymerization initiator represented by the above formula (1) preferably does not have absorption at a wavelength of 450 nm or more, more preferably does not have absorption at a wavelength of 420 nm or more, and absorbs at a wavelength range longer than 400 nm. It is particularly preferable not to have.
  • "having no absorption” means that the gram extinction coefficient at the wavelength is 100 L ⁇ g ⁇ 1 ⁇ cm ⁇ 1 or less.
  • the radical polymerization initiator represented by the above formula (1) is preferably white to light yellow in color. The above colors are preferable because they have little influence on the spectrum of the color filter.
  • the method for producing the radical polymerization initiator represented by the above formula (1) is not particularly limited, and may be produced by a known method or with reference to a known method. Further, as a method for producing the radical polymerization initiator represented by the above formula (1), for example, a method similar to the method described in Japanese Patent Publication No. 2016-531926 can be used. By using an ether-linked aromatic compound in place of carbazole or diphenyl sulfide in the method described in the above publication, it can be synthesized by a similar synthesis method.
  • the photocurable composition according to the present disclosure may contain a radical polymerization initiator other than the radical polymerization initiator represented by the above formula (1).
  • Other radical polymerization initiators include oxime compounds, ⁇ -aminoacetophenone compounds, ⁇ -hydroxyketone compounds, acylphosphine compounds, and the like. Among these, oxime compounds are preferred.
  • oxime compounds examples include the compound described in paragraph 0142 of International Publication No. 2022/085485, the polymer described in JP-A-2020-172619, and the compound represented by formula 1 described in International Publication No. 2020/152120. , oxime ester compounds described in International Publication No. 2021/023144, and the like.
  • compounds described in paragraph 0142 of International Publication No. 2022/085485 can be used.
  • TR-PBG-327 manufactured by Tronly
  • the oxime compound it is also preferable to use a compound without coloring property or a compound with high transparency and resistance to discoloration.
  • oxime compounds include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4,600,600.
  • the following compounds can be particularly preferably exemplified.
  • the mass ratio of the radical polymerization initiator represented by the above formula (1) and other radical polymerization initiators is not particularly limited, but from the viewpoint of sensitivity, the radical polymerization initiator represented by the above formula (1)
  • the content of the polymerization initiator is preferably 10% by mass or more, more preferably 50% by mass or more, even more preferably 80% by mass or more, and 90% by mass or more, based on the total mass of the polymerization initiator. It is particularly preferable that the amount is at least % by mass.
  • the photocurable composition according to the present disclosure includes a colorant.
  • the coloring agent include chromatic coloring agents and black coloring agents.
  • the chromatic colorant include colorants having a maximum absorption wavelength in the wavelength range of 400 nm to 700 nm. Examples include green coloring agent, red coloring agent, yellow coloring agent, purple coloring agent, blue coloring agent, orange coloring agent, and the like.
  • the coloring agent may be a pigment or a dye.
  • the coloring agents include diketopyrrolopyrrole pigments, quinacridone pigments, anthraquinone pigments, perylene pigments, phthalocyanine pigments, isoindoline pigments, quinophthalone pigments, azo pigments, azomethine pigments, and , dioxazine pigments, and at least one pigment selected from the group consisting of diketopyrrolopyrrole pigments, phthalocyanine pigments, and isoindoline pigments. More preferred. Additionally, black pigments can be used. As the black pigment, a pigment containing carbon black, a titanium atom, or a zirconium atom can be used.
  • the average primary particle diameter of the pigment is preferably 1 nm to 200 nm.
  • the lower limit is more preferably 5 nm or more, and even more preferably 10 nm or more.
  • the upper limit is more preferably 180 nm or less, even more preferably 150 nm or less, and particularly preferably 100 nm or less.
  • the primary particle diameter of a pigment can be calculated
  • the average primary particle diameter in this specification is the arithmetic mean value of the primary particle diameters of 400 pigment primary particles.
  • the primary particles of pigment refer to independent particles without agglomeration.
  • the crystallite size determined from the half-width of the peak derived from any crystal plane in the X-ray diffraction spectrum when the CuK ⁇ ray of the pigment is used as the X-ray source is preferably 0.1 nm to 100 nm, and preferably 0.1 nm to 100 nm.
  • the thickness is more preferably 5 nm to 50 nm, even more preferably 1 nm to 30 nm, and particularly preferably 5 nm to 25 nm.
  • the green coloring agent examples include phthalocyanine compounds and squarylium compounds, with phthalocyanine compounds being preferred.
  • the green coloring agent is a pigment.
  • Specific examples of green colorants include C.I. I. Examples include green pigments such as Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66.
  • compounds described in paragraphs 0143 to 0149 of International Publication No. 2022/085485, aluminum phthalocyanine compounds described in JP2020-070426A, diarylmethane described in Japanese Patent Publication No. 2020-504758, Compounds etc. can also be used.
  • the green colorant is C. I. Pigment Green 7, 36, 58, 59, 62, 63 are preferred; I. Pigment Green 7, 36, 58, and 59 are more preferred.
  • red colorants examples include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, azomethine compounds, xanthene compounds, quinacridone compounds, perylene compounds, thioindigo compounds, etc. It is preferably a compound, and more preferably a diketopyrrolopyrrole compound. Moreover, it is preferable that the red colorant is a pigment. Specific examples of red colorants include C.I. I.
  • the compound described in paragraph 0034 of International Publication No. 2022/085485 can also be used as a red colorant.
  • the red colorant Lumogen F Orange 240 (manufactured by BASF, red pigment, perylene pigment) can also be used.
  • the red colorant is C. I. Pigment Red 122, 177, 179, 254, 255, 264, 269, 272, 291 are preferred; I. Pigment Red 254, 264, and 272 are more preferred.
  • yellow coloring agent examples include azo compounds, azomethine compounds, isoindoline compounds, pteridine compounds, quinophthalone compounds, and perylene compounds.
  • the yellow colorant is preferably a pigment, more preferably an azo pigment, an azomethine pigment, an isoindoline pigment, a pteridine pigment, a quinophthalone pigment, or a perylene pigment, and even more preferably an azo pigment or an azomethine pigment.
  • Specific examples of yellow colorants include C.I. I.
  • a nickel azobarbiturate complex having the following structure can also be used as a yellow colorant.
  • the yellow colorant is C. I. Pigment Yellow 117, 129, 138, 139, 150, and 185 are preferred.
  • 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, 73, etc. orange pigments.
  • C. I. Examples include purple pigments such as Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.
  • C.I. 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, 88 etc. It will be done.
  • an aluminum phthalocyanine compound having a phosphorus atom can also be used as a blue colorant. Specific examples include compounds described in paragraph numbers 0022 to 0030 of JP-A No. 2012-247591 and paragraph number 0047 of JP-A No. 2011-157478.
  • Dyes can also be used as chromatic colorants. There are no particular restrictions on the dye, and known dyes can be used. For example, pyrazole azo series, anilinoazo series, triarylmethane series, anthraquinone series, anthrapyridone series, benzylidene series, oxonol series, pyrazolotriazole azo series, pyridone azo series, cyanine series, phenothiazine series, pyrrolopyrazole azomethine series, xanthene series, Examples include phthalocyanine-based, benzopyran-based, indigo-based, and pyrromethene-based dyes.
  • Pigment multimers can also be used as chromatic colorants.
  • the dye multimer is preferably a dye that is dissolved in an organic solvent. Further, the dye multimer may form particles. When the dye multimer is in the form of particles, it is usually used in a state of being dispersed in a solvent.
  • the dye multimer in a particle state can be obtained, for example, by emulsion polymerization, and specific examples include the compound and manufacturing method described in JP-A No. 2015-214682.
  • As the dye multimer a compound described in paragraph 0048 of International Publication No. 2022/085485 can also be used.
  • Chromatic colorants include diarylmethane compounds described in Japanese Patent Publication No. 2020-504758, triarylmethane dye polymers described in Korean Patent Publication No. 10-2020-0028160, and triarylmethane dye polymers described in Japanese Patent Application Publication No. 2020-117638.
  • a compound represented by formula 1 a compound represented by formula 1 described in Korean Publication Patent No. 10-2020-0069730, a compound represented by formula 1 described in Korean Publication Patent No.
  • 10-2020-0069070 Compound, compound represented by formula 1 described in Korean Publication Patent No. 10-2020-0069067, compound represented by formula 1 described in Korean Publication Patent No. 10-2020-0069062, patent No. 6809649
  • Isoindoline compounds aluminum phthalocyanine compounds described in International Publication No. 2022/024926, compounds described in JP2022-045895, and compounds described in International Publication No. 2022/050051 can be used.
  • the chromatic colorant may be a rotaxane, and the dye skeleton may be used in the cyclic structure of the rotaxane, the rod-like structure, or both structures.
  • Two or more chromatic colorants may be used in combination. Moreover, when using a combination of two or more types of chromatic colorants, black may be formed by a combination of two or more types of chromatic colorants.
  • the black colorant is not particularly limited, and known ones can be used.
  • examples of the inorganic black colorant include carbon black, titanium black, zirconium oxynitride, graphite, etc. Carbon black, titanium black, or zirconium oxynitride are preferred, and titanium black or zirconium oxynitride is more preferred. Titanium black is black particles containing titanium atoms, and lower titanium oxide and titanium oxynitride are preferable. As the titanium black, titanium black described in paragraph 0044 of International Publication No. 2022/085485 can be used.
  • organic black colorant examples include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds and perylene compounds being preferred.
  • organic black pigment a compound described in paragraph 0166 of International Publication No. 2022/065215 can be used.
  • perylene black Liogen Black FK4280, etc.
  • Paliogen Black S0084 described in paragraphs 0016 to 0020 of JP 2017-226821A may be used.
  • the photocurable composition according to the present disclosure may contain only one type of colorant, or may contain two or more types of colorants. When two or more types are used, the total amount thereof is preferably within the following range.
  • the content of the colorant is preferably 10% by mass to 75% by mass based on the total solid content of the photocurable composition, from the viewpoint of further exerting the effects of the present disclosure.
  • the upper limit is more preferably 70% by mass or less, and even more preferably 65% by mass or less.
  • the lower limit is more preferably 20% by mass or more, even more preferably 30% by mass or more, and particularly preferably 60% by mass or more.
  • the photocurable composition according to the present disclosure includes a radically polymerizable compound.
  • the radically polymerizable compound include compounds having an ethylenically unsaturated group.
  • resin-type radically polymerizable compounds include resins containing repeating units having radically polymerizable groups.
  • the weight average molecular weight (Mw) of the resin type polymerizable compound is preferably 2,000 to 2,000,000.
  • the upper limit of the weight average molecular weight is more preferably 1,000,000 or less, and even more preferably 500,000 or less.
  • the lower limit of the weight average molecular weight is more preferably 3,000 or more, and even more preferably 5,000 or more.
  • the molecular weight of the monomer-type radically polymerizable compound (polymerizable monomer) is preferably less than 2,000, more preferably 1,500 or less.
  • the lower limit of the molecular weight of the polymerizable monomer is preferably 100 or more, more preferably 200 or more.
  • the compound having an ethylenically unsaturated group as a polymerizable monomer is preferably a 3- to 15-functional (meth)acrylate compound, more preferably a 3- to 6-functional (meth)acrylate compound.
  • Specific examples include the compound described in paragraph 0128 of International Publication No. 2022/085485 and the compound described in JP 2017-194662, the contents of which are incorporated herein.
  • the compound having an ethylenically unsaturated group may be a compound having an acid group such as a carboxy group, a sulfo group, a phosphoric acid group, a compound having a caprolactone structure, a compound having an alkyleneoxy group, or a compound having a fluorene skeleton. It may also be a compound.
  • Examples of compounds having an ethylenically unsaturated group include UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), Light Acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.) It is also preferable to use products such as those manufactured by Co., Ltd.
  • the content of the radically polymerizable compound is preferably 0.1% by mass to 50% by mass based on the total solid content of the photocurable composition.
  • the lower limit is more preferably 0.5% by mass or more, and even more preferably 1% by mass or more.
  • the upper limit is more preferably 45% by mass or less, and even more preferably 40% by mass or less.
  • only one type of radically polymerizable compound may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount falls within the above range.
  • the photocurable composition according to the present disclosure further contains a resin.
  • a resin can be used as the radically polymerizable compound. It is preferable to use a radically polymerizable compound that contains at least a resin.
  • the resin is blended, for example, for dispersing pigments and the like in a photocurable composition or for use as a binder.
  • a resin used mainly for dispersing pigments and the like in a photocurable composition is also referred to as a dispersant.
  • this use of the resin is just an example, and the resin can also be used for purposes other than this use.
  • the resin having a radically polymerizable group also corresponds to a radically polymerizable compound.
  • the photocurable composition according to the present disclosure further contains a resin other than the radically polymerizable compound.
  • the weight average molecular weight of the resin is preferably 3,000 to 2,000,000.
  • the upper limit is preferably 1,000,000 or less, more preferably 500,000 or less.
  • the lower limit is preferably 4000 or more, more preferably 5000 or more.
  • resins include (meth)acrylic resin, epoxy resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, Examples include polyamide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, vinyl acetate resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyurethane resin, and polyurea resin. One type of these resins may be used alone, or two or more types may be used in combination.
  • norbornene resin is preferable from the viewpoint of improving heat resistance.
  • Commercially available norbornene resins include, for example, the ARTON series manufactured by JSR Corporation (eg, ARTON F4520).
  • the resin the resin described in paragraphs 0091 to 0099 of International Publication No. 2022/065215, the block polyisocyanate resin described in JP 2016-222891, and the resin described in JP 2020-122052, Resin, resin described in JP 2020-111656, resin described in JP 2020-139021, structural unit having a ring structure in the main chain and side chain described in JP 2017-138503 It is also possible to use a resin containing a structural unit having a biphenyl group.
  • a resin having a fluorene skeleton can also be preferably used.
  • the description in US Patent Application Publication No. 2017/0102610 can be referred to, the contents of which are incorporated herein.
  • examples of the resin include resins described in paragraphs 0199 to 0233 of JP2020-186373A, alkali-soluble resins described in JP2020-186325A, and Korean Patent Publication No. 10-2020-0078339.
  • a copolymer containing an epoxy group and an acid group described in International Publication No. 2022/030445 can also be used.
  • a resin having acid groups examples include a carboxy group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group. The number of these acid groups may be one, or two or more.
  • a resin having an acid group can be used, for example, as an alkali-soluble resin.
  • the acid value of the resin having acid groups is preferably 30 to 500 mgKOH/g.
  • the lower limit is preferably 50 mgKOH/g or more, more preferably 70 mgKOH/g or more.
  • the upper limit is preferably 400 mgKOH/g or less, more preferably 200 mgKOH/g or less, even more preferably 150 mgKOH/g or less, and most preferably 120 mgKOH/g or less.
  • the resin it is also preferable to use a resin having a polymerizable group.
  • the polymerizable group include an ethylenically unsaturated group and a cyclic ether group.
  • the resin has at least one type of repeating unit (hereinafter also referred to as repeating unit Ep) selected from a repeating unit represented by formula (Ep-1) and a repeating unit represented by formula (Ep-2).
  • a resin hereinafter also referred to as resin Ep
  • the resin Ep may contain only one of the repeating units represented by the formula (Ep-1) and the repeating unit represented by the formula (Ep-2), -1) and a repeating unit represented by formula (Ep-2).
  • the ratio of the repeating unit represented by formula (Ep-1) to the repeating unit represented by formula (Ep-2) is the molar ratio, which is the same as that represented by formula (Ep-1).
  • repeating unit: repeating unit represented by formula (Ep-2) preferably 5:95 to 95:5, more preferably 10:90 to 90:10, 20:80 to 80 :20 is more preferable.
  • L 1 represents a single bond or a divalent linking group
  • R 1 represents a hydrogen atom or a substituent.
  • substituent represented by R 1 include an alkyl group and an aryl group, and an alkyl group is preferable.
  • the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and still more preferably 1 to 3 carbon atoms.
  • R 1 is preferably a hydrogen atom or a methyl group.
  • the divalent linking group represented by L 1 includes 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-, Examples thereof include -SO 2 -, -CO-, -O-, -COO-, -OCO-, -S-, and groups formed by combining two or more of these.
  • the alkylene group may be linear, branched, or cyclic, and preferably linear or branched. Further, the alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxy group and an alkoxy group.
  • the content of the repeating unit Ep in the resin Ep is preferably 1 mol% to 100 mol% of all repeating units in the resin Ep.
  • the upper limit is more preferably 90 mol% or less, and even more preferably 80 mol% or less.
  • the lower limit is more preferably 2 mol% or more, and even more preferably 3 mol% or more.
  • the resin Ep may have other repeating units in addition to the above repeating unit Ep.
  • Examples of other repeating units include repeating units having an acid group and repeating units having an ethylenically unsaturated group.
  • Examples of the acid group include a phenolic hydroxy group, a carboxy group, a sulfo group, and a phosphoric acid group, with a phenolic hydroxy group or a carboxy group being preferred, and a carboxy group being more preferred.
  • ethylenically unsaturated groups include vinyl groups, styrene groups, (meth)allyl groups, (meth)acryloyl groups, and the like.
  • the content of the repeating unit having an acid group in the resin Ep is preferably 5 mol% to 85 mol% of the total repeating units of the resin Ep.
  • the upper limit is more preferably 60 mol% or less, and even more preferably 40 mol% or less.
  • the lower limit is more preferably 8 mol% or more, and even more preferably 10 mol% or more.
  • the content of the repeating unit having an ethylenically unsaturated group in the resin Ep is 1 mol% to 65 mol% of the total repeating units of the resin Ep. It is preferable.
  • the upper limit is more preferably 45 mol% or less, and even more preferably 30 mol% or less.
  • the lower limit is more preferably 2 mol% or more, and even more preferably 3 mol% or more.
  • the resin Ep further includes a repeating unit having an aromatic hydrocarbon ring.
  • the aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring, and preferably a benzene ring.
  • the aromatic hydrocarbon ring may have a substituent. Examples of the substituent include an alkyl group.
  • the content of the repeating unit having an aromatic hydrocarbon ring is 1 mol% of the total repeating units of the resin having a cyclic ether group. It is preferably 65 mol%.
  • the upper limit is more preferably 45 mol% or less, and even more preferably 30 mol% or less.
  • the lower limit is more preferably 2 mol% or more, and even more preferably 3 mol% or more.
  • the repeating unit having an aromatic hydrocarbon ring include repeating units derived from monofunctional polymerizable compounds having an aromatic hydrocarbon ring such as vinyltoluene and benzyl (meth)acrylate.
  • the resin it is also preferable to use a resin having an aromatic carboxy group (hereinafter also referred to as resin Ac).
  • the aromatic carboxy group may be included in the main chain of the repeating unit, or may be included 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, more preferably 1 to 2.
  • the resin Ac is preferably a resin containing at least one type of repeating unit selected from the repeating unit represented by formula (Ac-1) and the repeating unit represented by formula (Ac-2).
  • Ar 1 represents a group containing an aromatic carboxy group
  • L 1 represents -COO- or CONH-
  • L 2 represents a divalent linking group
  • 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. represents.
  • Examples of the group containing an aromatic carboxy group represented by Ar 1 in formula (Ac-1) include a structure derived from an aromatic tricarboxylic acid anhydride, a structure derived from an aromatic tetracarboxylic acid anhydride, and the like.
  • Examples of the aromatic tricarboxylic anhydride and aromatic tetracarboxylic anhydride include compounds having the following structures.
  • Q 1 is a single bond, -O-, -CO-, -COOCH 2 CH 2 OCO-, -SO 2 -, -C(CF 3 ) 2 -, represented by the following formula (Q-1). or a group represented by the following formula (Q-2).
  • the aromatic carboxy group-containing group represented by Ar 1 may have a polymerizable group.
  • the polymerizable group is preferably an ethylenically unsaturated group or a cyclic ether group, more preferably an ethylenically unsaturated group.
  • Specific examples of the group containing an aromatic carboxy group represented by Ar 1 include a group represented by formula (Ar-11), a group represented by formula (Ar-12), and a group represented by formula (Ar-13). Examples include groups such as
  • 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 preferably 1. More preferred. However, at least one of n3 and n4 is an integer of 1 or more.
  • Q 1 is a single bond, -O-, -CO-, -COOCH 2 CH 2 OCO-, -SO 2 -, -C(CF 3 ) 2 -, the above formula (Q- Represents a group represented by 1) or a group represented by the above formula (Q-2).
  • *1 represents the bonding position with L 1 .
  • L 1 represents -COO- or CONH-, preferably -COO-.
  • the divalent linking group represented by L 2 in formula (Ac-1) includes an alkylene group, an arylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and these. Examples include groups combining two or more of the following.
  • the alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 15 carbon atoms.
  • the alkylene group may be linear, branched, or cyclic.
  • the number of carbon atoms in the arylene group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 10.
  • the alkylene group and arylene group may have a substituent.
  • the divalent linking group represented by L 2 is preferably a group represented by -L 2a -O-.
  • L 2a is an alkylene group; an arylene group; a group combining an alkylene group and an arylene group; at least one selected from an alkylene group and an arylene group, and -O-, -CO-, -COO-, -OCO-, Examples include a group combining at least one selected from -NH- and S-, and an alkylene group is preferred.
  • the alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 15 carbon atoms.
  • the alkylene group may be linear, branched, or cyclic.
  • the alkylene group and arylene group may have a substituent. Examples of the substituent include a hydroxy group.
  • the aromatic carboxy group-containing group represented by Ar 10 in formula (Ac-2) has the same meaning as Ar 1 in formula (Ac-1), and its preferred embodiments are also the same.
  • L 11 represents -COO- or CONH-, preferably -COO-.
  • the trivalent linking group represented by L 12 includes a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and these two groups. Examples include groups that combine more than one species.
  • the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 30, 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 carbon atoms, and still more preferably 6 to 10 carbon atoms.
  • 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 with L 11 of formula (Ac-2)
  • *2 represents the bonding position of formula (Ac-2). It represents the bonding position of Ac-2) with P10 .
  • the trivalent linking group represented by L 12b is a hydrocarbon group; a hydrocarbon group, and at least one kind selected from -O-, -CO-, -COO-, -OCO-, -NH-, and -S-.
  • a hydrocarbon group or a group consisting of a hydrocarbon group and -O- is preferable.
  • L 12c represents a trivalent linking group
  • X 1 represents S
  • *1 represents the bonding position with L 11 of formula (Ac-2)
  • *2 represents formula ( It represents the bonding position of Ac-2) with P10 .
  • the trivalent linking group represented by L 12c is a hydrocarbon group; a hydrocarbon group, and at least one kind selected from -O-, -CO-, -COO-, -OCO-, -NH-, and -S-.
  • a hydrocarbon group is preferable.
  • P 10 represents a polymer chain.
  • the polymer chain represented by P 10 preferably has at least one type of repeating unit selected from poly(meth)acrylic repeating units, polyether repeating units, polyester repeating units, and polyol repeating units.
  • the weight average molecular weight of the polymer chain P 10 is preferably 500 to 20,000.
  • the lower limit is more preferably 1,000 or more.
  • the upper limit is more preferably 10,000 or less, and 5,000 The following is more preferable, and 3,000 or less is particularly preferable. If the weight average molecular weight of P 10 is within the above range, the pigment will have good dispersibility in the composition.
  • the resin having an aromatic carboxy group is a resin having a repeating unit represented by formula (Ac-2), this resin is preferably used as a dispersant.
  • the polymer chain represented by P 10 may contain a polymerizable group.
  • examples of the polymerizable group include ethylenically unsaturated groups.
  • the photocurable composition according to the present disclosure preferably contains a resin as a dispersant.
  • the dispersant include acidic dispersants (acidic resins) and basic dispersants (basic resins).
  • the acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of basic groups.
  • the acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol % or more when the total amount of acid groups and basic groups is 100 mol %.
  • the acid group that the acidic dispersant (acidic resin) has is preferably a carboxy group.
  • the acid value of the acidic dispersant (acidic resin) is preferably 10 mgKOH/g to 105 mgKOH/g.
  • the basic dispersant (basic resin) refers to a resin in which the amount of basic groups is greater than the amount of acid groups.
  • the basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of acid groups and basic groups is 100 mol%.
  • the basic group that the basic dispersant has is preferably an amino group.
  • the resin used as a dispersant is a graft polymer.
  • the graft polymer the descriptions in paragraphs 0025 to 0094 of JP-A No. 2012-255128 can be referred to, the contents of which are incorporated herein.
  • the resin is a graft polymer having a graft chain, and the graft chain includes at least one selected from the group consisting of a polyether chain, a polyester chain, and a polyacrylic chain.
  • the weight average molecular weight of the graft chain is preferably 1,000 or more.
  • the resin used as a dispersant is a polyimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain.
  • the polyimine dispersant has a main chain having a partial structure having a functional group with a pKa of 14 or less, a side chain having 40 to 10,000 atoms, and a basic nitrogen atom in at least one of the main chain and the side chain.
  • the resin has The basic nitrogen atom is not particularly limited as long as it exhibits basicity.
  • the description in paragraphs 0102 to 0166 of JP-A-2012-255128 can be referred to, and the contents thereof are incorporated herein.
  • the resin used as the dispersant has a structure in which a plurality of polymer chains are bonded to the core portion.
  • resins include dendrimers (including star-shaped polymers).
  • specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraph numbers 0196 to 0209 of JP-A No. 2013-043962.
  • the resin used as a dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated group in its side chain.
  • the content of repeating units having ethylenically unsaturated groups in their side chains is preferably 10 mol% or more, more preferably 10 mol% to 80 mol%, and 20 mol% of all repeating units in the resin. More preferably, it is 70 mol%.
  • the resin having an oxetane group for example, resins described in International Publication No. 2021/182268 or International Publication No. 2021/187257 can be used.
  • the resin used as the dispersant is preferably a resin containing an oxetane group in its side chain, and more preferably a resin containing a repeating unit having an oxetane group in its side chain.
  • the resin containing an oxetane group in its side chain is preferably a graft polymer.
  • Preferred examples of the resin containing an oxetane group in its side chain include those described in Examples below.
  • the content of repeating units having an oxetane group in the side chain in the resin is preferably 10 mol% or more, more preferably 10 mol% to 80 mol%, and 20 mol% of all repeating units in the resin. % to 70 mol % is more preferable.
  • resins described in JP 2018-087939, block copolymers (EB-1) to (EB-9) described in paragraph numbers 0219 to 0221 of Patent No. 6432077, Polyethyleneimine having a polyester side chain as described in International Publication No. 2016/104803, block copolymer as described in International Publication No. 2019/125940, block polymer having an acrylamide structural unit as described in JP-A No. 2020-066687 , a block polymer having an acrylamide structural unit described in JP-A-2020-066688, a dispersant described in International Publication No. 2016/104803, etc. can also be used.
  • a polyamic acid type dispersion resin or a polyimide type dispersion resin can also be used.
  • dispersants described in International Publication No. 2022/019253, International Publication No. 2022/019254, and International Publication No. 2022/019255 can also be used.
  • Dispersants are also available as commercial products, and specific examples include the Disperbyk series manufactured by Byk Chemie (for example, Disperbyk-111, 161, 2001, etc.), Solsperse manufactured by Nippon Lubrizol Co., Ltd. series (for example, Solsperse 20000, 76500, etc.), Ajisperse series manufactured by Ajinomoto Fine Techno, Inc., and the like. Further, the product described in paragraph number 0129 of JP 2012-137564A and the product described in paragraph 0235 of JP 2017-194662A can also be used as a dispersant.
  • the content of the resin is preferably 1% by mass to 70% by mass based on the total solid content of the photocurable composition. .
  • the lower limit is more preferably 2% by mass or more, even more preferably 3% by mass or more, and particularly preferably 5% by mass or more.
  • the upper limit is more preferably 65% by mass or less, and even more preferably 60% by mass or less.
  • the content of the resin having acid groups is preferably 1% by mass to 70% by mass based on the total solid content of the photocurable composition.
  • the lower limit is more preferably 2% by mass or more, even more preferably 3% by mass or more, and particularly preferably 5% by mass or more.
  • the upper limit is more preferably 65% by mass or less, and even more preferably 60% by mass or less.
  • the content of the alkali-soluble resin is preferably 1% by mass to 70% by mass based on the total solid content of the photocurable composition.
  • the lower limit is more preferably 2% by mass or more, even more preferably 3% by mass or more, and particularly preferably 5% by mass or more.
  • the upper limit is more preferably 65% by mass or less, and even more preferably 60% by mass or less.
  • the photocurable composition according to the present disclosure contains a resin as a dispersant
  • the content of the resin as a dispersant is 0.1% by mass to 30% by mass based on the total solid content of the photocurable composition. % is preferred.
  • the upper limit is more preferably 25% by mass or less, and even more preferably 20% by mass or less.
  • the lower limit is more preferably 0.5% by mass or more, and even more preferably 1% by mass or more.
  • the content of the resin as a dispersant is preferably 1 part by mass to 100 parts by mass with respect to 100 parts by mass of the colorant.
  • the upper limit is more preferably 80 parts by mass or less, even more preferably 70 parts by mass or less, and particularly preferably 60 parts by mass or less.
  • the lower limit is more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, and particularly preferably 20 parts by mass or more.
  • the photocurable composition according to the present disclosure may contain only one type of resin, or may contain two or more types of resin. When two or more types of resin are included, the total amount thereof is preferably within the above range.
  • the photocurable composition according to the present disclosure preferably contains a solvent.
  • the solvent include organic solvents.
  • the type of solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the composition.
  • the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.
  • paragraph number 0223 of International Publication No. 2015/166779 can be referred to, the contents of which are incorporated herein.
  • Ester solvents substituted with a cyclic alkyl group and ketone 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 acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N
  • aromatic hydrocarbons benzene, toluene, xylene, ethylbenzene, etc.
  • organic solvents for environmental reasons (for example, 50 mass ppm (parts) based on the total amount of organic solvents). per million), 10 mass ppm or less, and 1 mass ppm or less).
  • an organic solvent with a low metal content it is preferable to use an organic solvent with a low metal content. It is preferable that the metal content of the organic solvent is, for example, 10 mass ppb (parts per billion) or less. If necessary, an organic solvent at a mass ppt (parts per trillion) level may be used, and such an organic solvent is provided by Toyo Gosei Co., Ltd. (Kagaku Kogyo Nippo, November 13, 2015). .
  • Examples of methods for removing impurities such as metals from organic solvents include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
  • the filter pore diameter 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 material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon.
  • the organic solvent may contain isomers (compounds with the same number of atoms but different structures). Moreover, only one type of isomer may be included, or multiple types may be included.
  • the content of peroxide in the organic solvent is 0.8 mmol/L or less, and it is more preferable that the organic solvent contains substantially no peroxide.
  • the content of the solvent in the photocurable composition is preferably 10% to 95% by mass, more preferably 20% to 90% by mass, and 30% to 90% by mass. is even more preferable.
  • the photocurable composition according to the present disclosure preferably does not substantially contain environmentally regulated substances from the viewpoint of environmental regulations.
  • "not substantially containing environmentally controlled substances” means that the content of environmentally controlled substances in the photocurable composition is 50 mass ppm or less, and is 30 mass ppm or less. is preferable, more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less.
  • environmentally controlled substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene.
  • REACH Registration Evaluation Authorization and Restriction of CHemicals
  • PRTR Policy Release and It is registered as an environmentally regulated substance under the Transfer Register Act
  • VOC Volatile Organic Compounds
  • VOC Volatile Organic Compounds
  • the method is strictly regulated.
  • These compounds may be used as a solvent when producing each component used in the photocurable composition, and may be mixed into the photocurable composition as a residual solvent. From the viewpoint of human safety and environmental considerations, it is preferable to reduce the amount of these substances as much as possible.
  • methods for reducing environmentally controlled substances include a method of heating or reducing pressure in the system to raise the temperature above the boiling point of the environmentally controlled substance to distill off the environmentally controlled substances from the system.
  • distillation methods can be used at the stage of raw materials, at the stage of products obtained by reacting raw materials (for example, resin solution or polyfunctional monomer solution after polymerization), or at the stage of photocurable compositions prepared by mixing these compounds. This can be done at any stage, such as at any stage.
  • the photocurable composition according to the present disclosure further contains a pigment derivative.
  • Pigment derivatives are used, for example, as dispersion aids.
  • examples of pigment derivatives include compounds having a structure in which an acid group or a basic group is bonded to a pigment skeleton.
  • the pigment skeletons constituting the pigment derivatives include quinoline pigment skeleton, benzimidazolone pigment skeleton, benzisoindole pigment skeleton, benzothiazole pigment skeleton, iminium pigment skeleton, squarylium pigment skeleton, croconium pigment skeleton, oxonol pigment skeleton, and pyrrolopyrrole pigment.
  • diketopyrrolopyrrole dye skeleton azo dye skeleton, azomethine dye skeleton, phthalocyanine dye skeleton, naphthalocyanine dye skeleton, anthraquinone dye skeleton, quinacridone dye skeleton, dioxazine dye skeleton, perinone dye skeleton, perylene dye skeleton, thioindigo dye skeleton
  • Examples include isoindoline dye skeleton, isoindolinone dye skeleton, quinophthalone dye skeleton, iminium dye skeleton, dithiol dye skeleton, triarylmethane dye skeleton, and pyrromethene dye skeleton.
  • Examples of the acid group include a carboxyl group, a sulfo group, a phosphoric acid group, a boronic acid group, a carboxylic acid amide group, a sulfonic acid amide group, an imide acid group, and salts thereof.
  • Atoms or atomic groups constituting the salt include alkali metal ions (Li + , Na + , K + , etc.), alkaline earth metal ions (Ca 2+ , Mg 2+ , etc.), ammonium ions, imidazolium ions, pyridinium ions, Examples include phosphonium ions.
  • As the carboxylic acid amide group a group represented by -NHCOR X1 is preferable.
  • sulfonic acid amide group a group represented by -NHSO 2 R X2 is preferable.
  • the imide acid group is preferably a group represented by -SO 2 NHSO 2 R X3 , -CONHSO 2 R X4 , -CONHCOR X5 or SO 2 NHCOR X6 , and -SO 2 NHSO 2 R X3 is more preferred.
  • R X1 to R X6 each independently represent an alkyl group or an aryl group.
  • the alkyl group and aryl group represented by R X1 to R X6 may have a substituent.
  • the substituent is preferably a halogen atom, more preferably a fluorine atom.
  • Examples of the basic group include an amino group, a pyridinyl group and its salts, an ammonium group salt, and a phthalimidomethyl group.
  • Examples of atoms or atomic groups constituting the salt include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.
  • a pigment derivative having excellent visible transparency (hereinafter also referred to as a transparent pigment derivative) can also be used.
  • the maximum value ( ⁇ max) of the molar extinction coefficient in the wavelength range of 400 nm to 700 nm of the transparent pigment derivative is preferably 3,000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less, and 1,000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ It is more preferably 1 or less, and even more preferably 100 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less.
  • the lower limit of ⁇ max is, for example, 1 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or more, and may be 10 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or more.
  • pigment derivatives include the compound described in paragraph 0124 of International Publication No. 2022/085485, the benzimidazolone compound or salt thereof described in JP-A-2018-168244, and the general formula of Patent No. 6996282.
  • examples include compounds having an isoindoline skeleton as described in (1).
  • the content of the pigment derivative is preferably 1 part by mass to 30 parts by mass, more preferably 3 parts by mass to 20 parts by mass, per 100 parts by mass of the colorant. Further, the total content of the pigment derivative and the colorant is preferably 35% by mass or more, more preferably 40% by mass or more, and 45% by mass or more based on the total solid content of the photocurable composition. It is more preferable, and 50% by mass or more is particularly preferable.
  • the upper limit is preferably 70% by mass or less, more preferably 65% 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 according to the present disclosure preferably further contains a chain transfer agent from the viewpoint of adhesion.
  • chain transfer agents include thiol compounds, thiocarbonylthio compounds, aromatic ⁇ -methylalkenyl dimers, etc. Thiol compounds are used because the line width of the pattern can be easily adjusted even when incorporated in small amounts. is preferred. Further, the chain transfer agent is preferably a compound with little coloring.
  • the thiol compound 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 20 or less, more preferably 15 or less, even more preferably 10 or less, particularly preferably 8 or less, and most preferably 6 or less.
  • the lower limit of the number of thiol groups contained in the thiol compound is preferably 3 or more. From the viewpoint of adhesion, the thiol compound is particularly preferably a compound having four thiol groups.
  • the thiol compound is a compound derived from a polyfunctional alcohol.
  • the thiol compound is preferably a compound represented by the following formula (SH-1).
  • L 1 - (SH) n formula (SH-1) In the formula, SH represents a thiol group, L 1 represents an n-valent group, and n represents an integer of 1 or more.
  • the n-valent group represented by L 1 includes a hydrocarbon group, a heterocyclic group, -O-, -S-, -NR-, -CO-, -COO-, -OCO- , -SO 2 - or a combination thereof.
  • R represents a hydrogen atom, an alkyl group or an aryl group, and preferably a hydrogen atom.
  • the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Further, the aliphatic hydrocarbon group may be cyclic or acyclic. Further, 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 not. Further, the cyclic aliphatic hydrocarbon group and the aromatic hydrocarbon group may be monocyclic or fused rings.
  • the heterocyclic group may be a single ring or a condensed ring. The heterocyclic group is preferably a 5-membered ring or a 6-membered ring.
  • the heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. Further, examples of the heteroatom constituting the heterocyclic group include a nitrogen atom, an oxygen atom, a sulfur atom, and the like.
  • the number of carbon atoms constituting L 1 is preferably 3 to 100, more preferably 6 to 50.
  • n represents an integer of 1 or more.
  • the upper limit of n is preferably 20 or less, more preferably 15 or less, even more preferably 10 or less, particularly preferably 8 or less, and most preferably 6 or less.
  • the lower limit of n is preferably 2 or more, more preferably 3 or more. It is particularly preferred that n is 4.
  • thiol compounds include compounds with the following structure.
  • commercially available thiol compounds include PEMP (manufactured by SC Organic Chemical Co., Ltd., thiol compound), Suncella M (manufactured by Sanshin Kagaku Kogyo Co., Ltd., thiol compound), Karenz MT BD1 (manufactured by Showa Denko K.K., and thiol compounds).
  • dithioester compounds compounds represented by the following formula (SC-2)
  • trithiocarbonate compounds compounds represented by the following formula (SC-3)
  • dithiocarbamate compounds compounds represented by the following formula (SC-3)
  • dithiocarbamate compounds compounds represented by the following formula (SC-3)
  • Examples include compounds represented by the following formula (SC-4)), xanthate compounds (compounds represented by the following formula (SC-5)), and the like.
  • Z 1 to Z 11 each independently represent a substituent.
  • one or more of the hydrogen atoms bonded to a carbon atom may be substituted with a cyano group, a carboxy group, or the like.
  • the number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 15, even more preferably 1 to 8.
  • the alkyl group may be linear, branched, or cyclic, and preferably linear or branched.
  • 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 heteroaryl group is preferably a monocyclic heteroaryl group or a fused ring heteroaryl group having 2 to 8 fused rings, and more preferably a monocyclic heteroaryl group or a fused ring heteroaryl group having 2 to 4 fused rings. preferable.
  • the number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3.
  • the heteroatom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
  • the heteroaryl group preferably has a 5-membered ring or a 6-membered ring.
  • the number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, even more preferably 3 to 12.
  • bis(thiocarbonyl) disulfide compounds include tetraethylthiuram disulfide, tetramethylthiuram disulfide, bis(n-octylmercapto-thiocarbonyl) disulfide, bis(n-dodecylmercapto-thiocarbonyl) disulfide, and bis(benzylmercapto).
  • dithioester compounds include 2-phenyl-2-propylbenzothioate, 4-cyano-4-(phenylthiocarbonylthio)pentanoic acid, 2-cyano-2-propylbenzodithioate, and the like.
  • trithiocarbonate compounds include S-(2-cyano-2-propyl)-S-dodecyl trithiocarbonate, 4-cyano-4-[(dodecylsulfanyl-thiocarbonyl)sulfanyl]pentanoic acid, cyano Examples include methyldodecyltrithiocarbonate, 2-(dodecylthiocarbonothiolthio)-2-methylpropionic acid, and the like.
  • dithiocarbamate compounds include cyanomethylmethyl(phenyl)carbamodithioate, cyanomethyldiphenylcarbamodithioate, and the like.
  • xanthate compounds include xanthate esters and the like.
  • ⁇ -methylalkenyl dimer examples include 2,4-diphenyl-4-methyl-1-pentene.
  • trithiocarbonate compounds such as those used as RAFT agents in RAFT (Reversible Addition-Fragmentation Chain Transfer) polymerization, which is a type of living polymerization, can also be preferably used.
  • the molecular weight of the chain transfer agent is preferably 200 or more for reasons such as being able to suppress equipment contamination due to sublimation.
  • the upper limit is preferably 1,000 or less, more preferably 800 or less, and even more preferably 600 or less, since the SH valence per unit mass can be increased.
  • the content of the chain transfer agent is preferably 0.01% by mass to 10% by mass, and 0.01% by mass to 5% by mass, based on the total solid content of the photocurable composition. More preferably, it is 0.05% by mass to 1% by mass. Only one type of chain transfer agent may be used, or two or more types may be used in combination.
  • the photocurable composition according to the present disclosure further includes a sensitizer.
  • a sensitizer By including a sensitizer, exposure sensitivity not only to i-line (wavelength 365 nm) but also to KrF excimer laser (wavelength 248 nm) can be improved. Further, as the sensitizer, from the viewpoint of sensitivity, a sensitizer having absorption at a wavelength of 365 nm is preferably mentioned.
  • aromatic compounds such as benzophenone and derivatives thereof, thioxanthone and derivatives thereof, anthraquinone and derivatives thereof, coumarin and phenothiazine and derivatives thereof, as well as 3-(aroylmethylene)thiazoline, rhodanine, Examples include camphorquinone.
  • eosin, rhodamine, erythrosin, xanthene, thioxanthene, acridine for example, 9-phenylacridine, 1,7-bis(9-acridinyl)heptane, 1,5-bis(9-acridinyl) Pentane, cyanine dyes, and merocyanine dyes are also preferably mentioned.
  • sensitizers include the following. 1. Thioxanthone Thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-dodecylthioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 1-methoxycarbonylthioxanthone, 2- Ethoxycarbonylthioxanthone, 3-(2-methoxyethoxycarbonyl)thioxanthone, 4-butoxycarbonylthioxanthone, 3-butoxycarbonyl-7-methylthioxanthone, 1-cyano-3-chlorothioxanthone, 1-ethoxycarbonyl-3-chlorothioxanthone, 1-Ethoxycarbonyl-3-ethoxythioxanthone, 1-ethoxycarbonyl-3-aminothioxanthone, 1-
  • Benzophenones Benzophenone, 4-phenylbenzophenone, 4-methoxybenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-dimethylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(methylethylamino)benzophenone, 4,4'-bis(p-isopropylphenoxy)benzophenone, 4-methylbenzophenone, 2,4,6-trimethyl Benzophenone, 4-(4-methylthiophenyl)benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, methyl-2-benzoylbenzoate, 4-(2-hydroxyethylthio)benzophenone, 4-(4-tolylthio)benzophenone , 1-[4-(4-benzoyl-pheny
  • Rhodanines 4-dimethylaminobenzalrhodanine, 4-diethylaminobenzalrhodanine, 3-ethyl-5-(3-octyl-2-benzothiazolinylidene)rhodanine, disclosed in JP-A-8-305019 A rhodanine derivative represented by formula [1], [2], or [7];
  • the sensitizer is at least one compound selected from the group consisting of benzophenone and derivatives thereof, thioxanthone and derivatives thereof, anthraquinone and derivatives thereof, and coumarin and derivatives thereof. It is preferable.
  • amine compounds such as triethanolamine, N-methyldiethanolamine, ethyl-p-dimethylaminobenzoate, 2-(dimethylamino)ethylbenzoate, 2-ethylhexyl It is possible to add -p-dimethylaminobenzoate, octyl-pN,N-dimethylaminobenzoate, N-(2-hydroxyethyl)-N-methyl-p-toluidine or Michler's ketone.
  • the action of amine compounds can be enhanced by the addition of aromatic ketone compounds of the benzophenone type.
  • amine compounds that can be used as oxygen scavengers include substituted N,N-dialkylanilines as described in EP-A-339,841.
  • Other accelerators, co-initiators and autooxidizing agents include thiol compounds, thioether compounds, disulfide compounds, phosphonium salt compounds, phosphine oxide compounds or phosphine compounds, such as those described in EP-A-438-123 GB 2180358 and JP-A-6-68309.
  • the content of the sensitizer in the total solid content of the photocurable composition is preferably 0.01% by mass to 20% by mass, more preferably 0.05% by mass to 10% by mass, More preferably, it is 0.1% by mass to 5% by mass.
  • the photocurable composition according to the present disclosure may contain only one type of sensitizer, or may contain two or more types of sensitizer. When two or more types of sensitizers are included, the total amount thereof is preferably within the above range.
  • the photocurable composition according to the present disclosure can also contain polyalkyleneimine.
  • Polyalkyleneimines are used, for example, as dispersion aids for pigments.
  • a dispersion aid is a material for improving the dispersibility of pigments in a photocurable composition.
  • Polyalkyleneimine is a polymer obtained by ring-opening polymerization of alkyleneimine, and is a polymer having at least a secondary amino group.
  • the polyalkyleneimine may contain a primary amino group or a tertiary amino group in addition to the secondary amino group.
  • the polyalkyleneimine is preferably a polymer having a branched structure containing a primary amino group, a secondary amino group, and a tertiary amino group, respectively.
  • the alkylene imine 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 polyalkylene imine 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 of the polyalkylene imine if the molecular weight can be calculated from the structural formula, the molecular weight of the polyalkylene imine is the value calculated from the structural formula.
  • the molecular weight of the polyalkyleneimine cannot be calculated from the structural formula or is difficult to calculate, the value of the number average molecular weight measured by the boiling point elevation method is used.
  • the value of the number average molecular weight measured by the viscosity method is used. If the viscosity method cannot be used or it is difficult to measure, the number average molecular weight in terms of polystyrene measured by 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.
  • alkyleneimine examples include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, etc. Ethyleneimine or propyleneimine is preferable, and ethyleneimine is more preferable. preferable. It is particularly preferred that the polyalkyleneimine is polyethyleneimine. Further, the polyethyleneimine preferably contains 10 mol% or more, more preferably 20 mol% or more of primary amino groups based on the total of primary amino groups, secondary amino groups, and tertiary amino groups. , more preferably 30 mol% or more.
  • Commercial products of polyethyleneimine 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 solid content of the photocurable composition is preferably 0.1% by mass to 5% by mass.
  • the lower limit is more preferably 0.2% by mass or more, even more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more.
  • the upper limit is more preferably 4.5% by mass or less, even more preferably 4% by mass or less, and particularly preferably 3% by mass or less.
  • the content of polyalkyleneimine is preferably 0.5 parts by weight to 20 parts by weight based on 100 parts by weight of the pigment.
  • the lower limit is more preferably 0.6 parts by mass or more, even more preferably 1 part by mass or more, and particularly preferably 2 parts by mass or more.
  • the upper limit is more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less. Only one type of polyalkylene imine may be used, or two or more types may be used. When two or more types are used, the total amount thereof is preferably within the above range.
  • the photocurable composition according to the present disclosure can contain a curing accelerator.
  • the curing accelerator include thiol compounds, methylol compounds, amine compounds, phosphonium salt compounds, amidine salt compounds, amide compounds, base generators, isocyanate compounds, alkoxysilane compounds, onium salt compounds, and the like.
  • a specific example of the curing accelerator a compound described in paragraph 0164 of International Publication No. 2022/085485 can also be used.
  • the content of the curing accelerator in the total solid content of the photocurable composition is preferably 0.3% by mass to 8.9% by mass, and preferably 0.8% by mass to 6.4% by mass. More preferred.
  • the photocurable composition according to the present disclosure can contain an infrared absorber.
  • the wavelength of light transmitted through the film obtained by containing an infrared absorber in the photocurable composition can be increased. It can be shifted to the longer wavelength side.
  • the infrared absorber is preferably a compound having a maximum absorption wavelength on the longer wavelength side than the wavelength of 700 nm.
  • the infrared absorber is preferably a compound having a maximum absorption wavelength in a range of more than 700 nm and less than 1800 nm.
  • the ratio A 1 /A 2 between the absorbance A 1 at a wavelength of 500 nm and the absorbance A 2 at the maximum absorption wavelength of the infrared absorbent is preferably 0.08 or less, more preferably 0.04 or less. .
  • Infrared absorbers include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, pyrromethene compounds, and azomethine. compounds, anthraquinone compounds, dibenzofuranone compounds, dithiolene metal complexes, metal oxides, metal borides, and the like.
  • the compounds described in paragraphs 0114 to 0121 of WO 2022/065215, the compounds described in paragraphs 0144 to 0146 of WO 2021/049441, and the compounds described in JP 2021-195515 Croconic acid compounds, near-infrared absorbing dyes described in JP2022-022070A, croconium compounds described in International Publication No. 2019/021767, and the like can also be used.
  • the content of the infrared absorber in the total solid content of the photocurable composition is preferably 1% by mass to 40% by mass.
  • the lower limit is more preferably 2% by mass or more, even more preferably 5% by mass or more, and particularly preferably 10% by mass or more.
  • the upper limit is more preferably 30% by mass or less, and even more preferably 25% by mass or less.
  • the photocurable composition according to the present disclosure may contain only one type of infrared absorber, or may contain two or more types of infrared absorbers. When two or more types of infrared absorbers are included, the total amount thereof is preferably within the above range.
  • the photocurable composition according to the present disclosure can contain an ultraviolet absorber.
  • the ultraviolet absorber include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, and triazine compounds.
  • a compound described in paragraph 0179 of International Publication No. 2022/085485 can also be used.
  • the ultraviolet absorber the reactive triazine ultraviolet absorber described in JP-A No. 2021-178918 and the ultraviolet absorber described in JP-A No. 2022-007884 can be used.
  • the content of the ultraviolet absorber in the total solid content of the photocurable composition is preferably 0.01% by mass to 10% by mass, more preferably 0.01% by mass to 5% by mass. Only one type of ultraviolet absorber may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount falls within the above range.
  • the photocurable composition according to the present disclosure can 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), Examples include 2,2'-methylenebis(4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.). Among them, p-methoxyphenol is preferred.
  • the content of the polymerization inhibitor in the total solid content of the photocurable composition is preferably 0.0001% by mass to 5% by mass.
  • the number of polymerization inhibitors may be one, or two or more. In the case of two or more types, it is preferable that their total amount falls within the above range.
  • the photocurable composition according to the present disclosure can contain a silane coupling agent.
  • the silane coupling agent refers to a silane compound having a hydrolyzable group and other functional groups.
  • the term "hydrolyzable group" refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond through at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkoxy group is preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group.
  • Examples of functional groups other than hydrolyzable groups include vinyl groups, (meth)allyl groups, (meth)acryloyl groups, mercapto groups, epoxy groups, oxetanyl groups, amino groups, ureido groups, sulfide groups, and isocyanate groups. , phenyl group, etc., and amino group, (meth)acryloyl group and epoxy group are preferable.
  • the silane coupling agent a compound described in paragraph 0177 of International Publication No. 2022/085485 can also be used.
  • the content of the silane coupling agent in the total solid content of the photocurable composition is preferably 0.01% by mass to 15.0% by mass, and 0.05% by mass to 10.0% by mass. It is more preferable. Only one type of silane coupling agent may be used, or two or more types may be used. In the case of two or more types, it is preferable that their total amount falls within the above range.
  • the photocurable composition according to the present disclosure can contain a surfactant.
  • a surfactant various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used.
  • the surfactant is preferably a silicone surfactant or a fluorine surfactant.
  • the fluorine content in the fluorine-based surfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass.
  • a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid saving, and also has good solubility in a photocurable composition.
  • fluorine-based surfactant compounds described in paragraphs 0167 to 0173 of International Publication No. 2022/085485, fluorine-containing copolymers described in JP-A No. 2022-000494, etc. can also be used.
  • nonionic surfactant compounds described in paragraph 0174 of International Publication No. 2022/085485 can also be used.
  • silicone surfactants examples include DOWSIL (registered trademark: hereinafter the same) SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (all of which are manufactured by Dow Toray Industries, Inc.).
  • TSF -4300, TSF-4445, TSF-4460, TSF-4452 manufactured by Momentive Performance Materials
  • KP-341, KF-6000, KF-6001, KF-6002, KF-6003 manufactured by Shin-Etsu
  • BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 manufactured by BYK-CHEMY Co., Ltd.
  • the content of the surfactant in the total solid content of the photocurable composition is preferably 0.001% by mass to 5.0% by mass, and preferably 0.005% by mass to 3.0% by mass. is more preferable.
  • the number of surfactants may be one, or two or more. In the case of two or more types, it is preferable that their total amount falls within the above range.
  • the photocurable composition according to the present disclosure can contain an antioxidant.
  • antioxidants include phenol compounds, phosphite compounds, thioether compounds, and the like.
  • the phenol compound any phenol compound known as a phenolic antioxidant can be used.
  • Preferred phenol compounds include hindered phenol compounds.
  • a compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred.
  • the above-mentioned substituents are preferably substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms.
  • the antioxidant a compound having a phenol group and a phosphorous acid ester group in the same molecule is also preferable.
  • phosphorus-based antioxidants can also be suitably used.
  • a phosphorus antioxidant tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepine-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, ethylbis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like.
  • antioxidants include, for example, Adekastab (registered trademark) AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, and Adekastab AO. -60G, ADEKA STAB AO-80, ADEKA STAB AO-330 (manufactured by ADEKA Co., Ltd.).
  • antioxidants include compounds described in paragraph numbers 0023 to 0048 of Patent No. 6268967, compounds described in International Publication No. 2017/006600, compounds described in International Publication No. 2017/164024, Compounds described in Korean Patent Publication No. 10-2019-0059371 can also be used.
  • the content of the antioxidant in the total solid content of the photocurable composition is preferably 0.01% by mass to 20% by mass, more preferably 0.3% by mass to 15% by 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 their total amount falls within the above range.
  • the photocurable composition according to the present disclosure may contain a sensitizer, a curing accelerator, a filler, a thermosetting accelerator, a plasticizer, and other auxiliary agents (for example, conductive particles, antifoaming agents, (flame retardant, leveling agent, peel accelerator, fragrance, surface tension adjuster, etc.) may also be included.
  • auxiliary agents for example, conductive particles, antifoaming agents, (flame retardant, leveling agent, peel accelerator, fragrance, surface tension adjuster, etc.
  • properties such as film physical properties can be adjusted.
  • These components include the compound described in paragraph 0182 of International Publication No. 2022/085485, the xanthene-type epoxy resin described in JP-A No. 2021-195421, the xanthene-type epoxy resin described in JP-A No. 2021-195422, etc. You can also use
  • the photocurable composition according to the present disclosure may contain a metal oxide in order 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 diameter of the metal oxide is preferably 1 nm to 100 nm, more preferably 3 nm to 70 nm, even more preferably 5 nm to 50 nm.
  • the metal oxide may have a core-shell structure. Further, in this case, the core portion may be hollow.
  • the photocurable composition according to the present disclosure may contain a light resistance improver.
  • a light resistance improver a compound described in paragraph 0183 of International Publication No. 2022/085485 can also be used.
  • the photocurable composition according to the present disclosure does not substantially contain terephthalic acid ester.
  • substantially not containing means that the content of terephthalic acid ester is 1000 mass ppb or less in the total amount of the photocurable composition, and more preferably 100 mass ppb or less. Preferably, zero is particularly preferred.
  • perfluoroalkyl sulfonic acids and their salts may be regulated.
  • perfluoroalkylsulfonic acid particularly perfluoroalkylsulfonic acid whose perfluoroalkyl group has 6 to 8 carbon atoms
  • the content of perfluoroalkylcarboxylic acid is 0.0% relative to the total solid content of the photocurable composition.
  • the photocurable composition according to the present disclosure may be substantially free of perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt.
  • a compound that can be substituted for perfluoroalkylsulfonic acid and its salt and a compound that can be substituted for perfluoroalkylcarboxylic acid and its salt, perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid
  • Compounds that can be substituted for regulated compounds include, for example, compounds that are excluded from regulated targets due to differences in the number of carbon atoms in perfluoroalkyl groups.
  • the photocurable composition according to the present disclosure may include perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt within the maximum allowable range.
  • the water content of the photocurable composition according to the present disclosure is preferably 3% by mass or less, more preferably 0.01% by mass to 1.5% by mass, and 0.1% by mass to 1.0% by mass. It is more preferable that it is in the range of .
  • the water content can be measured by the Karl Fischer method.
  • the photocurable composition according to the present disclosure can be used by adjusting the viscosity for the purpose of adjusting the film surface condition (flatness, etc.), adjusting the film thickness, and the like.
  • the value of viscosity can be appropriately selected as required, but for example, at 25° C., 0.3 mPa ⁇ s to 50 mPa ⁇ s is preferable, and 0.5 mPa ⁇ s to 20 mPa ⁇ s is more preferable.
  • the viscosity can be measured using, for example, a cone plate type viscometer with the temperature adjusted to 25°C.
  • the amount of chloride ions in the photocurable composition is preferably 10,000 ppm or less from the viewpoint of environmental friendliness, suppression of foreign matter generation, suppression of equipment contamination, etc. More preferably, it is 1000 ppm or less.
  • it is necessary to use raw materials with a low chloride ion content, and to remove chloride ions using water washing, ion exchange resin, filter filtration, etc. can be mentioned.
  • Known methods can be used to measure chloride ions, such as ion chromatography and combustion ion chromatography.
  • the container for storing the photocurable composition is not particularly limited, and any known container can be used. Moreover, the container described in paragraph 0187 of International Publication No. 2022/085485 can also be used as the storage container.
  • the photocurable composition according to the present disclosure can be prepared by mixing the aforementioned components.
  • the photocurable composition may be prepared by dissolving and/or dispersing all components in a solvent at the same time, or, if necessary, each component may be suitably mixed in two or more solutions.
  • a photocurable composition may be prepared by preparing a dispersion and mixing these at the time of use (at the time of application).
  • a process of dispersing the pigment when preparing the photocurable composition.
  • mechanical forces used for dispersing pigments include compression, squeezing, impact, shearing, cavitation, and the like.
  • 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, ultrasonic dispersion, and the like.
  • pulverizing pigments in a sand mill (bead mill) it is preferable to use small-diameter beads, increase the filling rate of beads, etc.
  • the process and dispersion machine for dispersing pigments are described in ⁇ Complete Works of Dispersion Technology, Published by Information Technology Co., Ltd., July 15, 2005'' and ⁇ Dispersion technology centered on suspension (solid/liquid dispersion system) and industrial
  • the process and dispersion machine described in Paragraph No. 0022 of JP2015-157893A, ⁇ Practical Application Comprehensive Data Collection, Published by Management Development Center Publishing Department, October 10, 1978'' can be suitably used.
  • the particles may be made finer in a salt milling step.
  • the beads used for dispersion can be zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, glass, or combinations thereof. Further, an inorganic compound having a Mohs hardness of 2 or more can be used.
  • the composition may contain 1 to 10,000 ppm of the beads.
  • the photocurable composition In preparing the photocurable composition, it is preferable to filter the photocurable composition with a filter for the purpose of removing foreign substances and reducing defects.
  • a filter for the purpose of removing foreign substances and reducing defects.
  • the filters and filtration methods described in paragraphs 0196 to 0199 of International Publication No. 2022/085485 can also be used.
  • the cured product according to the present disclosure is a cured product of the photocurable composition according to the present disclosure.
  • the film according to the present disclosure is a film obtained from the photocurable composition according to the present disclosure, and is preferably a cured product (cured film) of the photocurable composition according to the present disclosure.
  • the film according to the present disclosure can be used for optical filters such as color filters and infrared transmission filters.
  • the film according to the present disclosure can be preferably used as a colored pixel of a color filter. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, yellow pixels, etc., preferably green pixels and blue pixels, and more preferably green pixels.
  • the thickness of the film according to the present disclosure can be adjusted as appropriate depending on the purpose.
  • the thickness of the film according to the present disclosure is preferably 0.1 ⁇ m to 20 ⁇ m.
  • the upper limit of the thickness of the film according to the present disclosure is more preferably 10 ⁇ m or less, even more preferably 5 ⁇ m or less, particularly preferably 3 ⁇ m or less, and most preferably 1.5 ⁇ m or less.
  • the lower limit of the film thickness is more preferably 0.2 ⁇ m or more, and even more preferably 0.3 ⁇ m or more.
  • the method for producing a cured product according to the present disclosure and the method for producing a film according to the present disclosure are not particularly limited, but include a step of irradiating the photocurable composition according to the present disclosure with light having a wavelength of 150 nm to 300 nm. It is preferable. Examples of light with a wavelength of 150 nm to 300 nm include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm). Further, the light having a wavelength of 150 nm to 300 nm is preferably an excimer laser. Although the shape of the obtained cured product is not particularly limited, it is preferably film-like. That is, the method for producing the cured product is preferably a method for producing a cured film.
  • the film according to the present disclosure can be manufactured through a step of applying the photocurable composition according to the present disclosure to a support.
  • the film manufacturing method preferably further includes a step of forming a pattern (pixel). Examples of methods for forming patterns (pixels) include photolithography and dry etching, with photolithography being preferred.
  • Pattern formation by the photolithography method includes a step of forming a photocurable composition layer on a support using the photocurable composition according to the present disclosure, and a step of exposing the photocurable composition layer to light in a pattern. It is preferable to include a step of developing and removing an unexposed portion of the photocurable composition layer to form a pattern (pixel). If necessary, a step of baking the photocurable composition layer (pre-bake step) and a step of baking the developed pattern (pixel) (post-bake step) may be provided.
  • a photocurable composition layer is formed on a support using the photocurable composition according to the present disclosure.
  • the support is not particularly limited and can be appropriately selected depending on the application.
  • a glass substrate, a silicon substrate, etc. may be mentioned, and a silicon substrate is preferable.
  • a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, etc. may be formed on the silicon substrate.
  • CMOS complementary metal oxide semiconductor
  • a black matrix that isolates each pixel may be formed on the silicon substrate.
  • the silicon substrate may be provided with a base layer for improving adhesion with the upper layer, preventing substance diffusion, or flattening the substrate surface.
  • the base layer may be formed using a composition obtained by removing the colorant from the photocurable composition described herein, or a composition containing the resin, polymerizable compound, surfactant, etc. described herein. It's okay.
  • the surface contact angle of the underlayer is preferably 20° to 70° when measured with diiodomethane. Further, it is preferable that the angle is 30° to 80° when measured with water.
  • a known method can be used.
  • the method described in paragraph 0207 of International Publication No. 2022/085485 can also be used.
  • the photocurable composition layer formed on the support may be dried (prebaked). If the film is manufactured by a low-temperature process, prebaking may not be 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 pre-bake time is preferably 10 seconds to 300 seconds, more preferably 40 seconds to 250 seconds, even more preferably 80 seconds to 220 seconds. Prebaking can be performed on a hot plate, oven, or the like.
  • the photocurable composition layer is exposed in a pattern (exposure step).
  • the photocurable composition layer can be exposed in a pattern by exposing it to light through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. This allows the exposed portion to be cured.
  • Radiation (light) that can be used during exposure includes g-line, i-line, etc. Furthermore, light with a wavelength of 300 nm or less (preferably light with a wavelength of 150 nm to 300 nm) can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm), ArF rays (wavelength 193 nm), and KrF rays (wavelength 248 nm). Furthermore, a long-wave light source of 300 nm or more can also be used.
  • pulse exposure is an exposure method in which exposure is performed by repeating light irradiation and pauses in short cycles (for example, on the millisecond level or less).
  • the irradiation amount is, for example, preferably 0.03 J/cm 2 to 2.5 J/cm 2 , more preferably 0.05 J/cm 2 to 1.0 J/cm 2 .
  • the oxygen concentration at the time of exposure can be appropriately selected, and in addition to being carried out in the atmosphere, for example, in a low oxygen atmosphere with an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially
  • the exposure may be performed in an oxygen-free atmosphere (without oxygen), or in a high oxygen atmosphere with an oxygen concentration exceeding 21 volume % (for example, 22 volume %, 30 volume %, or 50 volume %).
  • the exposure illuminance can be set appropriately, and is usually selected from the range of 1000W/m 2 to 100000W/m 2 (for example, 5000W/m 2 , 15000W/m 2 , or 35000W/m 2 ). I can do it.
  • the oxygen concentration and the exposure illuminance may be appropriately combined.
  • the illumination intensity may be 10,000 W/m 2 at an oxygen concentration of 10% by volume, or 20,000 W/m 2 at an oxygen concentration of 35% by volume.
  • the unexposed areas of the photocurable composition layer are developed and removed to form a pattern (pixel).
  • the unexposed areas of the photocurable composition layer can be removed by development using a developer.
  • the unexposed portions of the photocurable composition layer in the exposure step are eluted into the developer, leaving only the photocured portions.
  • the temperature of the developer is preferably 20°C to 30°C, for example.
  • the development time is preferably 20 seconds to 180 seconds. Furthermore, in order to improve the ability to remove residues, the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.
  • Examples of the developer include organic solvents, alkaline developers, and alkaline developers are preferably used.
  • the developer and development method described in paragraph 0214 of International Publication No. 2022/085485 can also be used.
  • Additional exposure processing and post-bake are post-development curing processing to complete curing.
  • the heating temperature in post-baking is, for example, preferably 100°C to 240°C, more preferably 200°C to 240°C.
  • Post-baking can be carried out in a continuous or batch manner using a heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater to maintain the developed film under the above conditions.
  • the light used for exposure is preferably light with a wavelength of 400 nm or less. Further, the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.
  • optical element An optical element according to the present disclosure includes a film according to the present disclosure.
  • optical elements include optical filters, lenses, prisms, reflective mirrors, and diffraction gratings. Among them, optical filters are preferred. Types of optical filters include color filters and infrared transmission filters, and color filters are preferred.
  • the color filter has a film according to the present disclosure as its colored pixels.
  • the film thickness of the film according to the present disclosure can be adjusted as appropriate 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 width of the pixels included in the optical filter is preferably 0.4 ⁇ m to 10.0 ⁇ m.
  • the lower limit is more preferably 0.4 ⁇ m or more, even more preferably 0.5 ⁇ m or more, and particularly preferably 0.6 ⁇ m or more.
  • the upper limit is more preferably 5.0 ⁇ m or less, even more preferably 2.0 ⁇ m or less, particularly preferably 1.0 ⁇ m or less, and most preferably 0.8 ⁇ m or less.
  • the Young's modulus of the pixel is preferably 0.5 GPa to 20 GPa, more preferably 2.5 GPa to 15 GPa.
  • each pixel included in the optical filter has high flatness.
  • the surface roughness Ra of the pixel is preferably 100 nm or less, more preferably 40 nm or less, and even more preferably 15 nm or less. Although the lower limit is not specified, it is preferably 0.1 nm or more, for example.
  • the surface roughness of a pixel can be measured using, for example, an AFM (atomic force microscope) Dimension 3100 manufactured by Veeco. Further, the contact angle of water on the pixel can be set to a suitable value, but is typically in the range of 50° to 110°.
  • the contact angle can be measured using, for example, a contact angle meter CV-DT-A type (manufactured by Kyowa Interface Science Co., Ltd.). Further, it is preferable that the volume resistance value of the pixel is high. Specifically, the volume resistance value of the pixel is preferably 10 9 ⁇ cm or more, more preferably 10 11 ⁇ cm or more. Although the upper limit of the volume resistance value of the pixel is not specified, it is preferably 10 14 ⁇ cm or less, for example.
  • the volume resistance value of a pixel can be measured using an ultra-high resistance meter 5410 (manufactured by Advantest).
  • a protective layer may be provided on the surface of the film according to the present disclosure.
  • various functions such as oxygen blocking, low reflection, hydrophilic and hydrophobic properties, and shielding of light of a specific wavelength (ultraviolet rays, near infrared rays, etc.) can be imparted.
  • the thickness of the protective layer is preferably 0.01 ⁇ m to 10 ⁇ m, more preferably 0.1 ⁇ m to 5 ⁇ m.
  • Examples of the method for forming the protective layer include a method of applying a composition for forming the protective layer, a chemical vapor deposition method, and a method of pasting a molded resin with an adhesive.
  • Components constituting the protective layer include (meth)acrylic resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide.
  • Resin polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, urethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluorine Examples include resin, polycarbonate resin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al 2 O 3 , Mo, SiO 2 , Si 2 N 4 and the like, and two or more of these components may be contained.
  • the protective layer preferably contains a polyol resin, SiO 2 and Si 2 N 4 .
  • the protective layer preferably contains a (meth)acrylic resin and a fluororesin.
  • the protective layer may contain organic particles, inorganic particles, absorbers for light of specific wavelengths (e.g., ultraviolet rays, near-infrared rays, etc.), refractive index adjusters, antioxidants, adhesives, surfactants, etc., as necessary. It may also contain an agent.
  • organic particles and inorganic particles include polymer particles (e.g., silicone resin particles, polystyrene particles, melamine resin particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, acid
  • examples include particles of titanium nitride, magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate, and the like.
  • the absorber for light of a specific wavelength a known absorber can be used.
  • the content of these additives can be adjusted as appropriate, but is preferably 0.1% by mass to 70% by mass, more preferably 1% by mass to 60% by mass, based on the total mass of the protective layer.
  • the protective layer the protective layers described in paragraph numbers 0073 to 0092 of JP-A No. 2017-151176 can also be used.
  • the optical filter may have a structure in which each pixel is embedded in a space partitioned, for example, in a grid pattern by partition walls.
  • An image sensor according to the present disclosure includes a film according to the present disclosure.
  • the image sensor include a solid-state image sensor, an X-ray image sensor, an organic thin film image sensor, and the like.
  • the image sensor according to the present disclosure can be suitably used for a solid-state image sensor.
  • a solid-state imaging device according to the present disclosure includes a film according to the present disclosure.
  • the configuration of the solid-state image sensor is not particularly limited as long as it functions as a solid-state image sensor, but examples include the following configurations.
  • a solid-state image sensor CCD (charge-coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.
  • a transfer electrode made of polysilicon or the like.
  • a device protective film made of silicon nitride or the like is formed on the light shielding film so as to cover the entire surface of the light shielding film and the light receiving part of the photodiode. It has a configuration in which a color filter is provided on the device protective film.
  • the color filter may have a structure in which each colored pixel is embedded in a space partitioned, for example, in a lattice shape by partition walls.
  • the partition wall preferably has a lower refractive index than each colored pixel. Examples of imaging devices having such a structure include devices described in Japanese Patent Application Publication No. 2012-227478, Japanese Patent Application Publication No. 2014-179577, and International Publication No.
  • an ultraviolet absorbing layer may be provided within the structure of the solid-state image sensor to improve light resistance.
  • An imaging device including a solid-state imaging device according to the present disclosure can be used not only for a digital camera, an electronic device having an imaging function (such as a mobile phone), but also for an in-vehicle camera, a surveillance camera, and the like.
  • An image display device includes a film according to the present disclosure.
  • Examples of the image display device include a liquid crystal display device and an organic electroluminescence display device.
  • Examples of image display devices and details of each image display device see, for example, “Electronic Display Devices (written by Akio Sasaki, published by Kogyo Chosenkai Co., Ltd., 1990)” and “Display Devices (written by Junaki Ibuki, published by Sangyo Tosho. Co., Ltd., published in 1989).
  • liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosenkai Co., Ltd., 1994)".
  • Next Generation Liquid Crystal Display Technology edited by Tatsuo Uchida, published by Kogyo Chosenkai Co., Ltd., 1994.
  • the present disclosure can be applied to various types of liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology.”
  • the radical polymerization initiator according to the present disclosure is represented by the following formula (1).
  • the radical polymerization initiator according to the present disclosure is preferably a radical photopolymerization initiator, and more preferably a radical photopolymerization initiator that generates radicals with light having a wavelength of 150 nm to 300 nm.
  • Ar 1 represents a (k+m+1)-valent aromatic group or a (k+m+1)-valent heteroaromatic group
  • Ar 2 represents a (k+2)-valent aromatic group or a (k+2)-valent heteroaromatic group.
  • R 1 represents an alkyl group, aryl group, heteroaryl group, alkoxy group, aryloxy group, or heteroaryloxy group
  • L represents a single bond or CR 11 R 12
  • R 11 and R 12 each independently represents a hydrogen atom, an alkyl group, or an aryl group
  • k represents 0 or 1
  • R 6 each independently represents a halogen atom or a monovalent organic group
  • Ar 1 may form a ring structure
  • Y 1 represents a group represented by the following formula (2)
  • m represents an integer of 0 to 4
  • n represents 0 or 1.
  • R 2 represents an alkyl group, provided that when L 2 is CHR, R 2 may be a hydrogen atom, R 3 represents a hydrogen atom or an alkyl group, and R 4 is an alkyl group.
  • L 1 and L 2 each independently represent CHR, O, S or NR
  • R each independently represents a hydrogen atom or an alkyl group, and among R 2 , R 3 , R 4 and R Two or more of these may be linked to each other to form a ring structure
  • Z represents a single bond or an alkylene group having 1 to 6 carbon atoms
  • * represents a linking portion with an oxime group.
  • a preferred embodiment of the radical polymerization initiator represented by formula (1) in the radical polymerization initiator according to the present disclosure is the same as a preferred embodiment of the radical polymerization initiator represented by formula (1) described above in the photocurable composition. The same is true.
  • the group represented by the above formula (2) is preferably a group represented by the following formula (2-1).
  • R 3 represents a hydrogen atom or an alkyl group
  • L 1 and L 2 each independently represent CHR, O, S, or NR
  • L A is an alkylene group having 1 to 6 carbon atoms.
  • R each independently represents a hydrogen atom or an alkyl group
  • Z represents a single bond or an alkylene group having 1 to 6 carbon atoms
  • * represents a linkage with an oxime group.
  • Preferred embodiments of the group represented by formula (2-1) in the radical polymerization initiator according to the present disclosure are the same as the preferred embodiments of the group represented by formula (2-1) described above in the photocurable composition. be.
  • radical polymerization initiators A-1 to A-190 used in the examples are the same as the radical polymerization initiators A-1 to A-190 described above as specific examples of the radical polymerization initiator represented by formula (1). Each is the same compound.
  • Radical polymerization initiator A-3 was obtained in the same manner as in the synthesis of radical polymerization initiator A-1, except that diphenyl ether was changed to dibenzofuran.
  • Radical polymerization initiator A-10 was obtained in the same manner as in the synthesis of radical polymerization initiator A-1, except that diphenyl ether was changed to 9,9-dimethylxanthene.
  • Radical polymerization initiator A-25 was obtained in the same manner as in the synthesis of radical polymerization initiator A-1, except that diphenyl ether was changed to dibenzofuran and o-toluoyl chloride was changed to o-bromobenzoyl chloride.
  • Radical polymerization initiator A-1 was synthesized using the same method except that diphenyl ether was changed to 4,6-dibromodibenzofuran and o-toluoyl chloride was changed to 2,6-dibromobenzoyl chloride. -88 was obtained.
  • Pigment Green 58 [zinc phthalocyanine complex, green pigment (G pigment)] PY129:C.
  • Pigment Yellow 129 Azomethine copper complex, yellow pigment (Y pigment)] PY139:C.
  • Pigment Yellow 139 [isoindoline compound, yellow pigment (Y pigment)] PY185:C.
  • Pigment Yellow 185 [isoindoline compound, yellow pigment (Y pigment)] PY215:C.
  • Pigment Yellow 215 [Pritedin compound, yellow pigment (Y pigment)] PB16:C.
  • Pigment Blue 16 [metal-free phthalocyanine compound, blue pigment (B pigment)] PB15:6:C.
  • Pigment Blue 15:6 [Copper phthalocyanine complex, blue pigment (B pigment)]
  • IR dye Compound with the following structure (near infrared absorbing pigment (colorant, also absorbs in the visible light region), in the following structural formula, Me represents a methyl group and Ph represents a phenyl group)
  • TiBk Titanium black [black pigment (Bk pigment)]
  • Zr oxynitride Zirconium oxynitride [black pigment (Bk pigment)]
  • P-1 30% by mass propylene glycol monomethyl ether acrylate (PGMEA) solution of a resin having the following structure.
  • the numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units.
  • Mw 20,000.
  • P-2 30% by mass PGMEA solution of resin with the following structure.
  • the numerical value appended to the main chain is the molar ratio
  • the numerical value appended to the side chain is the number of repeating units.
  • P-3 30% by mass PGMEA solution of resin with the following structure.
  • the numerical value appended to the main chain is the molar ratio
  • the numerical value appended to the side chain is the number of repeating units. Mw: 21,000.
  • P-4 30% by mass PGMEA solution of resin with the following structure.
  • the number appended to the side chain is the number of repeating units.
  • Mw 9,000.
  • P-5 30% by mass PGMEA solution of resin with the following structure.
  • the number appended to the side chain is the number of repeating units.
  • Mw 10,000.
  • a polymerization initiator a chain transfer agent listed in Tables 7 to 11 below, a sensitizer listed in Tables 7 to 11 below, a solvent listed in Tables 7 to 11 below, and an epoxy compound (EHPE- 3150, manufactured by Daicel Corporation), 1 part by mass of an ultraviolet absorber (TINUVIN326, manufactured by BASF), 1 part by mass of surfactant 1 shown below, and a polymerization inhibitor (p-methoxy 0.1 part by mass of phenol) to prepare photocurable compositions of each example and comparative example.
  • EHPE- 3150 manufactured by Daicel Corporation
  • an ultraviolet absorber TINUVIN326, manufactured by BASF
  • surfactant 1 shown below
  • a polymerization inhibitor p-methoxy 0.1 part by mass of phenol
  • Surfactant 1 1% by mass PGMEA solution of KF-6001 (polydimethylsiloxane modified with carbinol at both ends, manufactured by Shin-Etsu Chemical Co., Ltd.).
  • Ba-2 Resin with the following structure (the numerical value appended to the main chain is the molar ratio. Weight average molecular weight 15,000)
  • D-1 KAYARAD DPHA (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.)
  • D-2 NK ester A-DPH-12E (ethylene oxide (EO) modified hexafunctional acrylate compound, manufactured by Shin Nakamura Chemical Co., Ltd.)
  • D-3 NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • D-4 Aronix M-510 (3-4 functional acrylate compound, manufactured by Toagosei Co., Ltd.)
  • D-5 Light acrylate DCP-A (bifunctional alicyclic acrylate compound, manufactured by Kyoeisha Chemical Co., Ltd.)
  • a-5 Api-307, manufactured by YOUWEI, aminoacetophenone polymerization initiator a-6: Compound with the following structure
  • CA-1 The following compound
  • CA-2 The following compound
  • ⁇ Chain transfer agent> F-1: Karenz MT PE1, manufactured by Showa Denko K.K., tetrafunctional thiol compound
  • F-2 Karenz MT BD1, manufactured by Showa Denko K.K., difunctional thiol compound
  • G-1 2-isopropylthioxanthone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
  • G-2 4,4'-bis(diethylamino)benzophenone (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
  • G-3 7-diethylamino-4-methylcoumarin (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • G-4 6-chloro-2-methylthiochroman-4-one (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • 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. Thereafter, rinsing was performed using a spin shower using pure water to form pixels. The obtained pixels were observed at a magnification of 20,000 times using a scanning electron microscope (S-4800H, manufactured by Hitachi High-Tech Corporation). Based on the observed images, adhesion and residue were evaluated according to the following criteria.
  • TMAH tetramethylammonium hydroxide
  • the exposure amount required for the pattern line width to reach 0.7 ⁇ m was calculated, and the exposure sensitivity was evaluated based on the following criteria.
  • D The exposure amount is more than 150 mJ/cm 2 and less than 200 mJ/cm 2 .
  • Adhesion evaluation Among the areas of the obtained pixels exposed at an exposure dose of 100 mJ/cm 2 , 1,071 x 1,071 areas were observed with an optical microscope, and the number of peeled pixels was counted. Adhesion was determined based on the number of peeled pixels based on the following criteria. A: The number of peeled pixels is 10 or less. B: The number of peeled pixels is more than 10 and less than 20. C: The number of peeled pixels is more than 20 and less than 50. D: The number of peeled pixels is more than 50 and less than 200. E: The number of peeled pixels exceeds 200.
  • Pattern cross-sectional shape 1 was evaluated based on the following criteria. Note that the inclination of the cross section of the pattern is the inclination in the thickness direction of the pattern on the silicon wafer at the portion where the pattern is formed. Specifically, the angle between the surface of the silicon wafer and the side of the pattern in the thickness direction was measured.
  • the area of the pattern increases from the silicon wafer side to the surface side of the pattern, that is, the bottom of the pattern has an edge, which is not desirable.
  • -Evaluation criteria A: The angle is more than 80 degrees and less than 90 degrees. B: The angle is more than 90 degrees and less than 100 degrees. C: The angle is more than 100 degrees and less than 110 degrees. D: The angle is more than 110 degrees and less than 150 degrees. E: The angle exceeds 150 degrees.
  • the photocurable compositions of Examples had better sensitivity than the photocurable compositions of Comparative Examples. Furthermore, as shown in Tables 12 to 14 above, the photocurable compositions of Examples are also excellent in adhesion, undercut suppression, and coating film uniformity.
  • Example 301 Fabrication of solid-state image sensor
  • the photocurable composition of Example 1 was applied onto a silicon wafer by spin coating so that the film thickness after film formation was 0.4 ⁇ m. Then, using a hot plate, it was heated at 100° C. for 2 minutes. Next, using an i-line stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.), exposure was performed at 1,000 mJ/cm 2 through a mask with a 1.0 ⁇ m square dot pattern. Next, paddle development was performed at 23° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH).
  • TMAH tetramethylammonium hydroxide

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Abstract

L'invention concerne une composition photodurcissable contenant un agent colorant, un initiateur de polymérisation radicalaire représenté par la formule (1) et un composé polymérisable par voie radicalaire ; un procédé de production d'un film durci à l'aide de la composition photodurcissable ; un film ; un élément d'imagerie à semi-conducteurs ou un dispositif d'affichage d'image ; ou un nouvel initiateur de polymérisation radicalaire. Dans la formule (1) : Ar1 représente un groupe aromatique de valence (k+m+1) ou un groupe hétéroaromatique de valence (k+m+1) ; Ar2 représente un groupe aromatique de valence (k+2) ou un groupe hétéroaromatique de valence (k+2) ; les R6s représentent indépendamment un atome d'halogène ou un groupe organique monovalent ; L représente une liaison simple ou CR11R12 ; R11 et R12 représentent indépendamment un atome d'hydrogène, un groupe alkyle ou un groupe aryle ; et Y1 représente un groupe représenté par la formule (2).
PCT/JP2023/029178 2022-08-25 2023-08-09 Composition photodurcissable, procédé de production de film durci, film, élément d'imagerie à semi-conducteurs, dispositif d'affichage d'image et initiateur de polymérisation radicalaire WO2024043108A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014084412A (ja) * 2012-10-24 2014-05-12 Fujifilm Corp 着色組成物、カラーフィルタ及びその製造方法、画像表示装置、固体撮像素子、並びに、新規化合物
JP2016531926A (ja) * 2013-09-10 2016-10-13 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ オキシムエステル光開始剤
JP2017508738A (ja) * 2014-03-18 2017-03-30 常州強力電子新材料股▲ふん▼有限公司Ｃａｈｎｇｚｈｏｕ Ｔｒｏｎｌｙ Ｎｅｗ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ Ｃｏ．，Ｌｔｄ． ニトロ基含有ビスオキシムエステル系光重合開始剤及びその合成製造方法と応用
JP2017512886A (ja) * 2014-03-18 2017-05-25 常州強力先端電子材料有限公司Ｃａｈｎｇｚｈｏｕ Ｔｒｏｎｌｙ Ａｄｖａｎｃｅｄ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ Ｃｏ．，Ｌｔｄ． ビスオキシムエステル系光重合開始剤及びその製造方法と応用
JP2017523465A (ja) * 2014-07-15 2017-08-17 常州強力電子新材料股▲ふん▼有限公司Ｃａｈｎｇｚｈｏｕ Ｔｒｏｎｌｙ Ｎｅｗ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ Ｃｏ．，Ｌｔｄ． オキシムエステル類光開始剤含有感光性組成物及びその使用
JP2018141849A (ja) * 2017-02-27 2018-09-13 三菱ケミカル株式会社 画像表示装置用着色硬化膜、画像表示装置用感光性着色組成物及び画像表示装置

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014084412A (ja) * 2012-10-24 2014-05-12 Fujifilm Corp 着色組成物、カラーフィルタ及びその製造方法、画像表示装置、固体撮像素子、並びに、新規化合物
JP2016531926A (ja) * 2013-09-10 2016-10-13 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ オキシムエステル光開始剤
JP2017508738A (ja) * 2014-03-18 2017-03-30 常州強力電子新材料股▲ふん▼有限公司Ｃａｈｎｇｚｈｏｕ Ｔｒｏｎｌｙ Ｎｅｗ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ Ｃｏ．，Ｌｔｄ． ニトロ基含有ビスオキシムエステル系光重合開始剤及びその合成製造方法と応用
JP2017512886A (ja) * 2014-03-18 2017-05-25 常州強力先端電子材料有限公司Ｃａｈｎｇｚｈｏｕ Ｔｒｏｎｌｙ Ａｄｖａｎｃｅｄ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ Ｃｏ．，Ｌｔｄ． ビスオキシムエステル系光重合開始剤及びその製造方法と応用
JP2017523465A (ja) * 2014-07-15 2017-08-17 常州強力電子新材料股▲ふん▼有限公司Ｃａｈｎｇｚｈｏｕ Ｔｒｏｎｌｙ Ｎｅｗ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ Ｃｏ．，Ｌｔｄ． オキシムエステル類光開始剤含有感光性組成物及びその使用
JP2018141849A (ja) * 2017-02-27 2018-09-13 三菱ケミカル株式会社 画像表示装置用着色硬化膜、画像表示装置用感光性着色組成物及び画像表示装置

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