Photocurable composition, method for producing pixel, film, optical filter, solid-state image sensor, image display device, and photopolymerization initiator

Abstract

To provide a photocurable composition, a method for producing a pixel, a film, an optical filter, a solid-state image sensor, an image display device, and a photopolymerization initiator, capable of forming a film excellent in sensitivity and adhesion.SOLUTION: A photocurable composition comprises a photopolymerization initiator and a polymerizable compound, the photopolymerization initiator including a compound represented by formula (1); and a film, an optical filter, a solid-state image sensor, and an image display device using the photocurable composition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photocurable composition containing a photopolymerization initiator and a polymerizable compound. The present invention also relates to a pixel manufacturing method, a film, an optical filter, a solid-state imaging device, and an image display device using the photocurable composition. The present invention also relates to a photopolymerization initiator. [Background technology]

[0002] Photocurable compositions containing a photopolymerization initiator and a polymerizable compound can be polymerized and cured by irradiation with light, and are therefore used in optical filters, photocurable inks, photosensitive printing plates, various photoresists, and the like.

[0003] Patent Document 1 discloses that pixels of a color filter or the like are formed by forming a pattern by a photolithography method using a photopolymerization initiator containing a specific oxime ester compound and a photocurable composition containing a polymerizable compound. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Korean Patent Publication No. 10-2018-0077354 Summary of the Invention [Problem to be solved by the invention]

[0005] Photocurable compositions containing a photopolymerization initiator and a polymerizable compound are required to have further improvements in sensitivity to exposure light and adhesion of the resulting film to a support.

[0006] Furthermore, the inventors' investigations have revealed that there is room for further improvement in these properties of the photocurable composition disclosed in Patent Document 1.

[0007] Therefore, an object of the present invention is to provide a photocurable composition capable of forming a film having excellent sensitivity and adhesion. Another object of the present invention is to provide a method for producing a pixel, a film, an optical filter, a solid-state imaging device, an image display device, and a photopolymerization initiator. [Means for solving the problem]

[0008] The present inventors have found through their investigations that the above object can be achieved by using a photocurable composition as described below, and have thus completed the present invention.

[0009] <1> A photocurable composition containing a photopolymerization initiator and a polymerizable compound, The photopolymerization initiator is a photocurable composition containing a compound represented by formula (1); [ka] In formula (1), R 1 represents a hydrogen atom or a monovalent organic group, X 1 ~X 6 are each independently a group represented by formula (R-1), a group represented by formula (R-2), CR x1 or a nitrogen atom, R x1 represents a hydrogen atom or a substituent, X 1 ~X 6 At least one of the atoms is a nitrogen atom, and X 1 ~X 6 at least one of which is a group represented by formula (R-1) or a group represented by formula (R-2); However, X 1 , X 3 , X 5 and X 6 are each independently CR x1 So, X 2 is a nitrogen atom, X 4 is a group represented by formula (R-2); [ka] In the formula, the wavy line represents a bond. R 101 and R 102 each independently represents a monovalent organic group. <2> X in the above formula (1) 1 or X 2 is a group represented by the above formula (R-2), <1> The photocurable composition according to claim 1. <3> Further, the colorant may be <1> or <2> The photocurable composition according to claim 1. <4> Further, the resin may include a resin having a graft chain. <1> ~ <3> 1. The photocurable composition according to claim 1 . <5> <1> ~ <4> forming a composition layer on a support using the photocurable composition according to any one of the above items; a step of patternwise exposing the composition layer to light with a wavelength of 150 to 300 nm; and developing and removing the unexposed portion of the composition layer. <6> <1> ~ <4> 1. A film obtained by curing the photocurable composition according to any one of the above items. <7> <6> An optical filter comprising the film according to claim 1. <8> <6> A solid-state imaging device comprising the film according to claim 1. <9> <6> An image display device comprising the film according to claim 1. <10> a photopolymerization initiator containing a compound represented by formula (1); [ka] In formula (1), R 1 represents a hydrogen atom or a monovalent organic group, X 1 ~X 6 are each independently a group represented by formula (R-1), a group represented by formula (R-2), CR x1 or a nitrogen atom, R x1 represents a hydrogen atom or a substituent, X 1 ~X 6 At least one of the atoms is a nitrogen atom, and X 1 ~X 6at least one of which is a group represented by formula (R-1) or a group represented by formula (R-2); However, X 1 , X 3 , X 5 and X 6 are each independently CR x1 So, X 2 is a nitrogen atom, X 4 is a group represented by formula (R-2); [ka] In the formula, the wavy line represents a bond. R 101 and R 102 each independently represents a monovalent organic group. [Effects of the Invention]

[0010] According to the present invention, a photocurable composition capable of forming a film having excellent sensitivity and adhesion can be provided. The present invention also provides a pixel manufacturing method, a film, an optical filter, a solid-state imaging device, an image display device, and a photopolymerization initiator. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below. In this specification, the symbol "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit. In the description of groups (atomic groups) in this specification, when a notation does not specify whether they are substituted or unsubstituted, it encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, the term "alkyl group" encompasses not only alkyl groups without a substituent (unsubstituted alkyl groups) but also alkyl groups with a substituent (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, electron beams, and other actinic rays or radiation. In this specification, "(meth)acrylate" refers to either or both of acrylate and methacrylate, "(meth)acrylic" refers to either or both of acrylic and methacrylic, and "(meth)acryloyl" refers to either or both of acryloyl and methacryloyl. In this specification, Me in the structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the weight average molecular weight and number average molecular weight are values ​​measured by GPC (gel permeation chromatography) in terms of polystyrene. In this specification, the total solid content refers to the total mass of all components of the composition excluding the solvent. In this specification, a pigment means a coloring material that is difficult to dissolve in a solvent. In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended effect of the process is achieved.

[0012] <Photocurable composition> The photocurable composition of the present invention is a photocurable composition containing a photopolymerization initiator and a polymerizable compound, The photopolymerization initiator is characterized by containing a compound represented by formula (1).

[0013] The photocurable composition of the present invention has excellent sensitivity and can form a film with excellent adhesion. It is presumed that the compound represented by formula (1) has the above structure, and therefore easily interacts with other materials in the photocurable composition and remains stable in the photocurable composition. It is therefore presumed that the compound represented by formula (1) is less likely to decompose in the photocurable composition. For these reasons, it is presumed that the photocurable composition of the present invention has excellent sensitivity. Furthermore, because the photocurable composition of the present invention has excellent sensitivity, sufficient polymerization reaction can be promoted even at the bottom of the film (support side) upon exposure. It is therefore presumed that the photocurable composition of the present invention can form a film with excellent adhesion to the support.

[0014] The photocurable composition of the present invention preferably further contains a colorant. The photocurable composition containing a colorant is preferably used as a photocurable composition for an optical filter. Examples of the optical filter include a color filter, an infrared transmission filter, and an infrared cut filter, and a color filter is preferred.

[0015] The color filter may have colored pixels that transmit light of a specific wavelength. Examples of the colored pixels include red, green, blue, magenta, cyan, and yellow pixels. The colored pixels of the color filter may be formed using a photocurable composition containing a chromatic colorant.

[0016] The infrared cut filter preferably has a maximum absorption wavelength in the wavelength range of 700 to 1800 nm, more preferably in the wavelength range of 700 to 1300 nm, and even more preferably in the wavelength range of 700 to 1000 nm. The transmittance of the infrared cut filter over the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. The transmittance at at least one point in the wavelength range of 700 to 1800 nm is preferably 20% or less. The ratio of the absorbance Amax at the infrared cut filter's maximum absorption wavelength to the absorbance A550 at a wavelength of 550 nm (absorbance Amax / absorbance A550) is preferably 20 to 500, more preferably 50 to 500, even more preferably 70 to 450, and particularly preferably 100 to 400. The infrared cut filter can be formed using a photocurable composition containing an infrared-absorbing colorant.

[0017] The infrared transmission filter is a filter that transmits at least a portion of infrared light. The infrared transmission filter is preferably a filter that blocks at least a portion of visible light and transmits at least a portion of infrared light. Preferred examples of the infrared transmission filter include filters that satisfy the spectral characteristics of a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1100 to 1300 nm. The infrared transmission filter is preferably a filter that satisfies any one of the following spectral characteristics (1) to (5). (1): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 800 to 1500 nm. (2): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 750 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 900 to 1500 nm. (3): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 830 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1000 to 1500 nm. (4): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 950 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1100 to 1500 nm. (5): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 1050 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1200 to 1500 nm.

[0018] The photocurable composition of the present invention can also be used as a light-shielding film.

[0019] The solids concentration of the photocurable composition of the present invention is preferably 5 to 30% by mass. The lower limit is preferably 7.5% by mass or more, more preferably 10% by mass or more. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

[0020] The photocurable composition of the present invention exhibits high sensitivity when exposed to light having a wavelength of 150 to 300 nm. Therefore, the photocurable composition of the present invention is preferably used as a photocurable composition for exposure to light having a wavelength of 150 to 300 nm. Examples of light having a wavelength of 150 to 300 nm include KrF radiation (wavelength 248 nm) and ArF radiation (wavelength 193 nm), with KrF radiation (wavelength 248 nm) being preferred. The light having a wavelength of 150 to 300 nm is preferably excimer laser light having a wavelength of 150 to 300 nm.

[0021] Each component used in the photocurable composition of the present invention will now be described.

[0022] <<Photopolymerization initiator>> The photocurable composition of the present invention contains a photopolymerization initiator, which is preferably a photoradical polymerization initiator.

[0023] (Specific compound) In the photocurable composition of the present invention, the photopolymerization initiator used contains a compound represented by formula (1). Hereinafter, the compound represented by formula (1) may also be referred to as a specific compound. [ka]

[0024] -R 1 About- R in Equation (1) 1 represents a hydrogen atom or a monovalent organic group, preferably a monovalent organic group. Examples of the monovalent organic group include an alkyl group, an aryl group, a heteroaryl group, and an acyl group, preferably an aryl group or a heteroaryl group, and more preferably an aryl group.

[0025] The number of carbon atoms in the alkyl group is preferably 1 to 15, and more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear.

[0026] The aryl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 14 carbon atoms.

[0027] The number of carbon atoms constituting the ring of the heteroaryl group is preferably 1 to 15, more preferably 1 to 10. Types of heteroatoms constituting the ring of the heteroaryl group include nitrogen atoms, oxygen atoms, and sulfur atoms. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3, more preferably 1 or 2. The heteroaryl group may be a monocyclic ring or a condensed ring.

[0028] The acyl group may be -COR 201 It is preferable that the group is a group represented by the following formula:

[0029] The alkyl group, aryl group, and heteroaryl group may have a substituent. The substituent may be an alkyl group, an aryl group, a heteroaryl group, -OR 201 , -SR 201 , -COR 201 , -SO2R 201 , -NR 202 R 203 , -CONR 202 R 203 , -NR 204 COR 205 , -OCOR 201 , -COOR 201 , -SCOR 201 , -OCSR 201 , -COSR 201 , -CSOR 201 , a cyano group, a nitro group, a hydroxy group, a thiol group, a carboxy group, and a halogen atom; 201 or -SO2R 201 Preferably, -COR 201 It is more preferable that R 201 ~R 205 each independently represents a monovalent organic group.

[0030] R 201 ~R 205Examples of the monovalent organic group represented by include an alkyl group, an aromatic ring group, and a heterocyclic group, and an aromatic ring group or a heterocyclic group is preferred. R 201 ~R 205 The number of carbon atoms in the alkyl group represented by is preferably 1 to 15, and more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic. R 201 ~R 205 The number of carbon atoms in the aromatic ring group represented by is preferably 6 to 20, more preferably 6 to 12, still more preferably 6 to 10, and particularly preferably 6. The aromatic ring group may be a monocyclic ring or a condensed ring. R 201 ~R 205 The heterocyclic group represented by is preferably a 5-membered or 6-membered ring. The heteroatom contained in the heterocyclic group is preferably an oxygen atom, a nitrogen atom, or a sulfur atom. The number of heteroatoms contained in the heterocyclic group is preferably 1 to 3. The heterocyclic group may be a monocyclic ring or a condensed ring.

[0031] The aromatic ring group and the heterocyclic group may be a monocyclic aromatic ring group or heterocyclic group, or may be an aromatic ring group or heterocyclic group having two or more fused rings. Among these, an aromatic ring group or heterocyclic group having two or more fused rings is preferred, and an aromatic ring group or heterocyclic group having three or more fused rings is more preferred. Examples of aromatic ring groups or heterocyclic groups having two or more fused rings include a naphthalene ring group, a benzofuran ring group, a benzothiophene ring group, a naphthyl ring group, and a quinolyl ring group. These groups may have the aforementioned substituents. Examples of aromatic ring groups or heterocyclic groups having three or more fused rings include the following:

[0032] [ka] [ka] [ka]

[0033] In the above formula, * represents a bond. R a1 ~R a32 each independently represents a substituent, R ar1 ~R ar25 each independently represents a hydrogen atom, an alkyl group, or an aryl group, k1 to k32 each independently represent an integer of 0 to 4. R a1 ~R a32 The substituent represented by R 201 ~R 205 Examples of the substituents that can be possessed by the alkyl group, aromatic ring group and heterocyclic group represented by the formula (I) include the substituents explained above.

[0034] Above R 201 ~R 205 The alkyl group, aromatic ring group and heterocyclic group represented by may have a substituent. The substituent may be an alkyl group, an aryl group, a heteroaryl group, -OR 301 , -SR 301 , -COR 301 , -SO2R 301 , -NR 302 R 303 , -CONR 302 R 303 , -NR 304 COR 305 , -OCOR 301 , -COOR 301 , -SCOR 301 , -OCSR 301 , -COSR 301 , -CSOR 301 , a cyano group, a nitro group, a hydroxy group, a thiol group, a carboxy group, and a halogen atom; 301 , -SR 301 , -COR 301 , -SO2R 301 , -NR 302 R 303 or a nitro group, 301 or -SO2R 301 More preferably, -COR301 It is more preferable that R 301 ~R 305 R each independently represents a monovalent organic group. 301 ~R 305 Examples of the monovalent organic group represented by R include an alkyl group, an aromatic ring group, and a heterocyclic group. 301 ~R 305 The alkyl group, aromatic ring group and heterocyclic group represented by R 201 ~R 205 Specific examples of the monovalent organic group represented by the formula (I) include the alkyl group, aromatic ring group, and heterocyclic group shown above.

[0035] R in Equation (1) 1 is preferably an aryl group having a substituent or a heteroaryl group having a substituent, and more preferably an aryl group having a substituent. The substituent possessed by the aryl group or heteroaryl group is -COR 201 or -SO2R 201 Preferably, -COR 201 It is more preferable that R 201 is preferably an aromatic ring group which may have a substituent or a heterocyclic group which may have a substituent.

[0036] R in Equation (1) 1 is preferably a group represented by formula (Az-1). [ka] In formula (Az-1), * represents a bond. Rz 1 represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -ORz 101 , -SRz 101 , -CORz 101 , -SO2Rz 101 , -NRz 102 Rz 103 , -CONRz 102 Rz 103 , -NRz 104 CORz 105 , -OCORz 101 , -COORz101 , -SCORz 101 , -OCSRz 101 , -COSRz 101 , -CSORz 101 , a cyano group, a nitro group, a hydroxy group, a thiol group, a carboxy group, or a halogen atom; Rz 101 ~Rz 105 each independently represents a monovalent organic group, Rz 2 represents an alkyl group, an aryl group, or a halogen atom; p represents an integer of 0 to 4; Rz 1 and Rz 2 may be bonded via a single bond or a divalent linking group to form a ring, If p is 2 or more, multiple Rz 2 may be the same or different, and multiple Rz 2 Two of these may be bonded via a single bond or a divalent linking group to form a ring.

[0037] Rz in formula (Az-1) 1 is a hydrogen atom, -CORz 101 or -SO2Rz 101 Preferably, -CORz 101 or -SO2Rz 101 More preferably, -CORz 101 It is more preferable that:

[0038] Rz 101 ~Rz 105 Examples of the monovalent organic group represented by Rz include an alkyl group, an aromatic ring group, and a heterocyclic group, and an aromatic ring group or a heterocyclic group is preferred. 101 ~Rz 105 The alkyl group, aromatic ring group and heterocyclic group represented by R 201 ~R 205 Specific examples of the monovalent organic group represented by include the alkyl groups, aromatic ring groups, and heterocyclic groups shown above, and the preferred ranges are also the same.

[0039] In formula (Az-1), p represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

[0040] Rz 1 and Rz 2 may be linked via a single bond or a divalent linking group to form a ring. If p is 2 or more, multiple Rz 2 may be the same or different, and multiple Rz 2 Two of these may be bonded via a single bond or a divalent linking group to form a ring. The divalent linking group includes —O—, —S—, and —NR L1 -, -CR L2 R L3 -, -CR L4 =CR L5 -CR L6 =CR L7 -R L1 ~R L7 R each independently represents a hydrogen atom, an alkyl group, or an aryl group, and is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom. L1 ~R L7 The number of carbon atoms in the alkyl group represented by R is preferably 1 to 15, and more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. L1 ~R L7 The number of carbon atoms in the aryl group represented by is preferably 6 to 20, more preferably 6 to 12, still more preferably 6 to 10, and particularly preferably 6 or 7. The ring formed is preferably a 3- to 7-membered ring, more preferably a 5- or 7-membered ring, and even more preferably a 5- or 6-membered ring. The ring formed may be either an aromatic ring or a non-aromatic ring.

[0041] -X 1 ~X 6 About- X in equation (1) 1 ~X 6are each independently a group represented by formula (R-1), a group represented by formula (R-2), CR x1 or a nitrogen atom, R x1 represents a hydrogen atom or a substituent, X 1 ~X 6 At least one of the atoms is a nitrogen atom, and X 1 ~X 6 at least one of which is a group represented by formula (R-1) or a group represented by formula (R-2); However, X 1 , X 3 , X 5 and X 6 are each independently CR x1 So, X 2 is a nitrogen atom, X 4 is a group represented by formula (R-2).

[0042] CR x1 R in x1 The substituent represented by is an alkyl group, an aryl group, a heteroaryl group, -OR x101 , -SR x101 , -COR x101 , -SO2R x101 , -NR x102 R x103 , -CONR x102 R x103 , -NR x104 COR x105 , -OCOR x101 , -COOR x101 , -SCOR x101 , -OCSR x101 , -COSR x101 , -CSOR x101 , cyano groups, nitro groups, hydroxy groups, thiol groups, carboxy groups and halogen atoms. R x1 is preferably a hydrogen atom. R x101 ~R x105 R each independently represents a monovalent organic group. x101 ~R x105Examples of the monovalent organic group represented by R include an alkyl group, an aromatic ring group, and a heterocyclic group, and an aromatic ring group or a heterocyclic group is preferred. x101 ~R x105 The alkyl group, aromatic ring group and heterocyclic group represented by R 201 ~R 205 Specific examples of the monovalent organic group represented by include the alkyl groups, aromatic ring groups, and heterocyclic groups shown above, and the preferred ranges are also the same.

[0043] CR x1 R in x1 is preferably a hydrogen atom.

[0044] In formula (1), X 1 ~X 6 At least one of the X is a nitrogen atom, 1 ~X 6 Preferably, one or two of X are nitrogen atoms, and more preferably, one of X is nitrogen atom. 1 or X 3 is preferably a nitrogen atom, and X 1 It is particularly preferred that is a nitrogen atom.

[0045] In formula (1), X 1 ~X 6 It is preferable that any one of X is a group represented by formula (R-1) or a group represented by formula (R-2), and it is more preferable that it is a group represented by formula (R-2). 1 or X 2 is preferably a group represented by formula (R-1) or a group represented by formula (R-2), and more preferably a group represented by formula (R-2). In particular, X is preferably a group represented by formula (R-1) or a group represented by formula (R-2), because it can form a film with excellent adhesion even when the photocurable composition is used after long-term storage. 2 is preferably a group represented by formula (R-1) or a group represented by formula (R-2), and more preferably a group represented by formula (R-2).

[0046] [ka] In the formula, the wavy line represents a bond. R 101 and R 102 each independently represents a monovalent organic group.

[0047] R in formula (R-1) and formula (R-2) 101 Examples of the monovalent organic group represented by include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, and a heteroaryloxy group, and an alkyl group or an aryl group is preferred, and an alkyl group is more preferred. The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have a substituent, but is preferably an unsubstituted alkyl group. The alkyl group is preferably an unsubstituted linear or branched alkyl group, and more preferably an unsubstituted linear alkyl group. The number of carbon atoms in the alkoxy group is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3. The alkoxy group is preferably linear or branched, more preferably linear. The alkoxy group may have a substituent, but is preferably unsubstituted. The number of carbon atoms in the aryl group and aryloxy group is preferably 6 to 20, more preferably 6 to 12, still more preferably 6 to 10, and particularly preferably 6. The aryl group and aryloxy group may have a substituent, but are preferably unsubstituted. The heteroaryl group and heteroaryloxy group preferably have 1 to 15 carbon atoms constituting the ring, more preferably 1 to 10. Examples of heteroatoms constituting the ring of the heteroaryl group and heteroaryloxy group include a nitrogen atom, an oxygen atom, and a sulfur atom. The number of heteroatoms constituting the ring of the heteroaryl group and heteroaryloxy group is preferably 1 to 3, more preferably 1 to 2. The heteroaryl group and heteroaryloxy group may be a monocyclic ring or a condensed ring. The heteroaryl group and heteroaryloxy group may have a substituent.

[0048] R in formula (R-1) and formula (R-2) 102 Examples of the monovalent organic group represented by include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, a heteroaryloxy group, a heteroarylthio group, an amino group, a hydroxy group, a thiol group, and a carboxy group, and an alkyl group is preferred. The alkyl group is preferably an unsubstituted linear alkyl group, an alkyl group having a branched structure, an alkyl group having a cyclic structure, or an alkyl group having at least one substituent selected from the following Group A, more preferably an alkyl group having a branched structure or an alkyl group having a cyclic structure, and even more preferably an alkyl group having a cyclic structure. The alkyl group having a cyclic structure is preferably an alkyl group having a cyclic alkyl group as a substituent, more preferably an alkyl group having a 3- to 7-membered cyclic alkyl group as a substituent, even more preferably an alkyl group having a 5- to 7-membered cyclic alkyl group as a substituent, and particularly preferably an alkyl group having a 5- or 6-membered cyclic alkyl group as a substituent.

[0049] (Group A) Cyano group, alkenyl group, alkynyl group, -N(R a )2, -SR a , -COOH, -OR a , -O-COR c , -O-CO-OR c, -CONR a R b , -NR a -CO-R b , -O-CO-NR a R b , -NR a -CO-OR b , -NR a -CO-NR a R b , -SO-R c , -SO2-R c , -O-SO2-R c , -SO2-NR a R b , -NR a -SO2-R a , -CO-NR a -COR b , -CO-NR a -SO2-R b , -SO2-NR a -CO-R b , -SO2-NR a -SO2-R c , -Si(R a ) L (OR b ) K , heterocyclic groups, and -O(R d O) J -R a where R a and R b each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group; R c each independently represents an alkyl group, an aryl group, or a heteroaryl group; R d each independently represents an alkylene group, an arylene group, or a group combining two or more thereof; L and K each independently represent an integer of 0 to 3, satisfying L+K=3; and J represents an integer of 1 to 100.

[0050] Above R a are each independently preferably an alkyl group, an aryl group, or a heteroaryl group, more preferably an alkyl group, and particularly preferably a cyclic alkyl group. Above R bare each independently preferably a hydrogen atom or an alkyl group, more preferably an alkyl group. Above R c is preferably an alkyl group or an aryl group, and is preferably an alkyl group. Above R d are each independently preferably an alkylene group, more preferably an ethylene group or a propylene group.

[0051] Above R a ~R c Two or more of these may be bonded via a single bond or a divalent linking group to form a ring. Examples of the divalent linking group include -O-, -S-, and -NR L1 -, -CR L2 R L3 -R L1 ~R L3 R each independently represents a hydrogen atom, an alkyl group, or an aryl group, and is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom. L1 ~R L3 The number of carbon atoms in the alkyl group represented by R is preferably 1 to 15, and more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. L1 ~R L3 The aryl group represented by the formula (I) preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, further preferably 6 to 10 carbon atoms, and particularly preferably 6 or 7 carbon atoms.

[0052] In formula (1), X 1 ~X 6 As a preferred embodiment of X 1 is a nitrogen atom, and X 2 is a group represented by formula (R-2), and X 3 ~X 6 are each independently CR x1 An example of such an embodiment is: X 1 ~X 6 In another preferred embodiment, X 3 is a nitrogen atom, and X4 is a group represented by formula (R-2), and X 1 , X 2 , X 5 , X 6 are each independently CR x1 An example of such an embodiment is:

[0053] The molecular weight of the specific compound is preferably 200 to 2000. The upper limit is preferably 1000 or less, more preferably 900 or less. The lower limit is preferably 300 or more, more preferably 400 or more.

[0054] From the viewpoint of sensitivity, the molar absorption coefficient of a specific compound at a wavelength of 248 nm is 5000 L mol -1 ·cm -1 More than 10,000 L·mol is preferable. -1 ·cm -1 More than 20,000 L·mol is preferable. -1 ·cm -1 More preferably, 30,000 L·mol -1 ·cm -1 The upper limit of the molar absorption coefficient at a wavelength of 248 nm is not particularly limited, but is preferably 200,000 L mol -1 ·cm -1 It is preferable that: From the viewpoint of sensitivity, the molar extinction coefficient of a specific compound at a wavelength of 365 nm is 500 L mol -1 ·cm -1 More than 1000 L·mol is preferable. -1 ·cm -1 More than 2000 L·mol is preferable. -1 ·cm -1 More preferably, 3000 L·mol -1 ·cm -1 The upper limit of the molar absorption coefficient at a wavelength of 365 nm is not particularly limited, but is preferably 200,000 L mol -1 ·cm -1 It is preferable that: A specific compound is absorbed at the long-wave end (molar extinction coefficient 100 L mol -1 ·cm-1 The longest wavelength (below which the absorption peak is longer than the longest wavelength) is preferably 450 nm or shorter, more preferably 400 nm or shorter, and even more preferably 380 nm or shorter. When the long wavelength end of absorption is in the above-mentioned range, yellow light fogging is prevented and the light stability during synthesis is excellent. Furthermore, when the specific compound is applied to an optical filter such as a color filter, the color reproducibility is good because the specific compound does not exhibit a yellow color.

[0055] The molar absorption coefficient of a specific compound is measured by the following method. Accurately weigh out 12.5 mg of a specific compound and place it in a 100 mL volumetric flask. Add acetonitrile to this and dissolve it completely. Take 2 mL of this solution with a volumetric pipette and make up to 25 mL in a volumetric flask. This is the measurement sample. Add the measurement sample to a 1 cm square 5 mL quartz glass cell, measure the absorbance in air, and calculate the molar extinction coefficient. Examples of measurement equipment include an ultraviolet-visible-near-infrared spectrophotometer (UH4150, manufactured by Hitachi High-Tech Corporation).

[0056] When a specific compound has E and Z geometric isomers, the specific compound may be the E geometric isomer, the Z geometric isomer, or a mixture of the E and Z geometric isomers.

[0057] The method for producing the specific compound is not particularly limited, and the specific compound can be produced by referring to a known method. For example, the specific compound can be produced by a general method for synthesizing oxime esters or ketoxime esters. Specific production methods that can be referred to include JP-A-2012-519191, which uses hydroxylamine hydrochloride, and JP-A-2012-526185, which uses isoamyl nitrite.

[0058] When a compound having multiple carbonyl groups in one molecule is used as an intermediate, the carbonyl group to be oximed does not have to be only one. For example, a dioxime in which two carbonyl groups are oximed or a trioxime in which three carbonyl groups are oximed may be present. These dioximes and trioximes are converted into dioxime esters and trioxime esters through an esterification step. When these are present, the total amount of dioxime esters and trioxime esters is preferably 0.001 to 10% by mass, more preferably 0.001 to 8% by mass, and even more preferably 0.001 to 5% by mass of the specific compound.

[0059] The photocurable composition of the present invention may contain an oxime precursor and a ketone precursor before oximation. When these are contained, the content of each of the oxime precursor and the ketone precursor is preferably 0.001 to 10 mass%, more preferably 0.001 to 8 mass%, and even more preferably 0.001 to 5 mass%, of the mass of the specific compound.

[0060] Specific examples of the specific compound include compounds A-1 to A-70 shown below.

[0061] [ka] [Table 1] [Table 2]

[0062] R in the above table 1 , X 1 ~X 6 , R 101 , R 102 The structures described in abbreviations in the column are as follows. Note that the wavy lines and * in the structural formulas shown below represent bonds. [ka] [ka] [ka] [ka] [ka]

[0063] The photocurable composition of the present invention may use only one of the specific compounds described above, or two or more of them in combination.

[0064] The impurities that may be contained in the specific compound will be described below. The content of water contained in the specific compound is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, further preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less, relative to 100 parts by mass of the specific compound. The lower limit can be 0 parts by mass, 0.0001 parts by mass, 0.001 parts by mass, or 0.01 parts by mass. The content of the organic solvent contained in the specific compound is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, further preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less, relative to 100 parts by mass of the specific compound. The lower limit can be 0 parts by mass, 0.0001 parts by mass, 0.001 parts by mass, or 0.01 parts by mass. The content of organic acid and organic acid anhydride contained in the specific compound is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less, per 100 parts by mass of the specific compound. The lower limit can be 0 parts by mass, 0.0001 parts by mass, 0.001 parts by mass, or 0.01 parts by mass. Examples of organic acids include formic acid, acetic acid, propionic acid, pivalic acid, succinic acid, phthalic acid, and benzoic acid. Examples of organic acid anhydrides include anhydrides of these acids. The content of the organic base contained in the specific compound is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less, relative to 100 parts by mass of the specific compound. The lower limit can be 0 parts by mass, 0.0001 parts by mass, 0.001 parts by mass, or 0.01 parts by mass. Examples of organic bases include triethylamine, dimethylamine, diethylamine, pyridine, piperidine, pyrrolidine, morpholine, and amines used in producing the specific compound. The content of halogen contained in the specific compound is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 1 part by mass or less, per 100 parts by mass of the specific compound. The lower limit can be 0 parts by mass, 0.0001 parts by mass, 0.001 parts by mass, or 0.01 parts by mass. Examples of halogen include Cl, Br, F, and I, and may be organic compounds containing these halogen atoms. Ions of these halogens may also be used. The content of residual metals contained in the specific compound is preferably 0.1 parts by mass or less, more preferably 0.01 parts by mass or less, and even more preferably 0.001 parts by mass or less, per 100 parts by mass of the specific compound. It is even more preferable that the content be less than 0.0001 parts by mass, and particularly preferably be below the detection limit. The type of residual metal is not particularly limited, but examples include Li, Na, Mg, Al, K, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb, Ti, V, As, Ag, Sn, Ba, W, Au, and Zr.

[0065] (Other photoinitiators) The photocurable composition of the present invention may further contain a photopolymerization initiator other than the specific compound described above (hereinafter also referred to as other photopolymerization initiator). When the specific compound described above is used in combination with the other photopolymerization initiator, the content of the other photopolymerization initiator is preferably 1 to 1,000 parts by mass per 100 parts by mass of the specific compound. The upper limit is preferably 500 parts by mass or less, more preferably 200 parts by mass or less. The lower limit is preferably 10 parts by mass or more, more preferably 50 parts by mass or more.

[0066] Examples of other photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, etc. The other photopolymerization initiators are preferably trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, hexaarylbiimidazole compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds, or 3-aryl-substituted coumarin compounds, more preferably oxime compounds, α-hydroxyketone compounds, α-aminoketone compounds, or acylphosphine compounds, even more preferably α-aminoketone compounds or oxime compounds, and particularly preferably oxime compounds.

[0067] Other photopolymerization initiators include compounds described in paragraphs 0065 to 0111 of JP 2014-130173 A, compounds described in Japanese Patent No. 6301489 A, peroxide-based photopolymerization initiators described in MATERIAL STAGE pp. 37 to 60, vol. 19, No. 3, 2019, photopolymerization initiators described in WO 2018 / 221177 A, photopolymerization initiators described in WO 2018 / 110179 A, ​​photopolymerization initiators described in JP 2019-043864 A, photopolymerization initiators described in JP 2019-044030 A, peroxide-based initiators described in JP 2019-167313 A, and aminoacetophenones having an oxazolidine group described in JP 2020-055992 A system initiator, oxime-based photopolymerization initiator described in JP 2013-190459 A, polymer described in JP 2020-172619 A, compound represented by formula 1 described in WO 2020 / 152120 A, compound described in JP 2021-181406 A, photopolymerization initiator described in JP 2022-013379 A, ​​compound represented by formula (1) described in JP 2022-015747 A, fluorine-containing fluorene oxime ester-based photoinitiator described in JP 2021-507058 A, Chinese Patent Initiators described in Patent Publication No. 110764367, initiators described in JP-A-2022-518535, initiators described in WO 2021 / 175855, compounds described in Taiwan Patent Publication No. 202200534, compounds described in JP-A-2022-078550, compounds described in Korean Patent Publication No. 10-2017-0087330, compounds described in WO 2022 / 075452, oxime ester compounds described in Chinese Patent Publication No. 110066225, Compounds described in Japanese Patent Publication No. 10-2022-0076157, compounds having a triarylamine or N-arylcarbazole skeleton described in paragraphs 0042 to 0062 of WO 2019 / 013112, oxime ester-based photopolymerization initiators described in Japanese Patent Publication No. 7219378, photopolymerization initiators described in Korean Patent Publication No. 10-2021-0146174, photopolymerization initiators described in WO 2019 / 013112, photopolymerization initiators described in JP 2023-033731 A,Examples of initiators include those described in JP-T-2022-515524 and JP-T-2023-517304. Examples of initiators include those described in Chinese Patent Application Publication No. 114149517, aminoketone compounds described in Chinese Patent Application Publication No. 115925596, compounds described in Japanese Patent Application Publication No. 2023-159489, compounds described in Japanese Patent Application Publication No. 2023-159487, compounds described in Taiwan Patent Application Publication No. 202336003, and compounds described in Chinese Patent Application Publication No. 113527138.

[0068] Specific examples of the hexaarylbiimidazole compound include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole.

[0069] Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins BV), Irgacure 184, Irgacure 1173, Irgacure 2959, Irgacure 127 (manufactured by BASF), etc. Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins BV), Irgacure 907, Irgacure 369, Irgacure 369E, Irgacure 379EG (manufactured by BASF), etc. Commercially available acylphosphine compounds include Omnirad 819 and Omnirad TPO (both manufactured by IGM Resins BV), Irgacure 819 and Irgacure TPO (both manufactured by BASF).

[0070] Examples of oxime compounds include the compounds described in paragraph 0142 of International Publication No. 2022 / 085485, the compounds described in Japanese Patent No. 5430746, the compounds described in Japanese Patent No. 5647738, the compounds represented by general formula (1) and the compounds described in paragraphs 0022 to 0024 of Japanese Patent Publication No. 2021-173858, the compounds represented by general formula (1) and the compounds described in paragraphs 0117 to 0120 of Japanese Patent Publication No. 2021-170089, and the like. Specific examples of oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime), etc. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04, Irgacure Examples of suitable oxime compounds include OXE05 (manufactured by BASF), TR-PBG-301, TR-PBG-304, TR-PBG-305, TR-PBG-309, TR-PBG-3054, TR-PBG-3057, TR-PBG-314, TR-PBG-327, TR-PBG-345, TR-PBG-346, TR-PBG-358, TR-PBG-365, TR-PBG-380, TR-PBG-610, TR-PBG-A, and TR-PBG-B (manufactured by TRONLY), and ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation; photopolymerization initiator 2 described in JP 2012-014052 A). It is also preferable to use, as the oxime compound, a compound that is not colorable or a compound that is highly transparent and does not easily discolor. Commercially available products include ADEKA Arcles NCI-730, NCI-831, NCI-831E, and NCI-930 (all manufactured by ADEKA Corporation).

[0071] Other photopolymerization initiators that can be used include oxime compounds having a fluorene ring, oxime compounds having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring, oxime compounds having a fluorine atom, oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, oxime compounds in which a substituent having a hydroxy group is bonded to a carbazole skeleton, and the compounds described in paragraphs 0143 to 0149 of WO 2022 / 085485.

[0072] As another photopolymerization initiator, a compound represented by formula (OX-1) can also be used.

[0073] [ka] In formula (OX-1), X 1a represents a divalent linking group containing at least one ring selected from the group consisting of an aromatic ring and a heterocyclic ring, R 1a represents a hydrogen atom or an acyl group, R 2a represents an alkyl group or an aryl group, R 3a and R 4a each independently represents a hydrogen atom or an alkyl group, Alk 1 and Alk 2 each independently represents an alkyl group, R 3a and R 4a may be bonded to form a ring, Alk 1 and Alk 2 may be bonded to form a ring, n represents 0 or 1.

[0074] X in formula (OX-1) 1aExamples of the divalent linking group represented by include a divalent aromatic ring group, a divalent heterocyclic group, a divalent group in which two or more aromatic rings are bonded together via a single bond or a linking group, a divalent group in which two or more heterocyclic rings are bonded together via a single bond or a linking group, and a divalent group in which an aromatic ring and a heterocyclic ring are bonded together via a single bond or a linking group. Examples of the linking group that bonds the above-mentioned aromatic rings together, heterocyclic groups together, or aromatic rings and heterocyclic rings include -CH2-, -O-, -CO-, -S-, -NR x - and combinations thereof. x represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.

[0075] X in formula (OX-1) 1a is preferably a group represented by any one of formulas (X-1) to (X-13), more preferably a group represented by formula (X-1), formula (X-2), formula (X-4), formula (X-6) or formula (X-8), and further preferably a group represented by formula (X-2) or formula (X-6). [ka]

[0076] R in the formula X1 ~R X9 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group, and * represents a bond.

[0077] R X1 ~R X9 The number of carbon atoms in the alkyl group represented by is preferably 1 to 15, and more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic. The alkyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, and a heteroaryl group.

[0078] R X1 ~R X9The number of carbon atoms in the alkenyl group represented by is preferably 2 to 15, and more preferably 2 to 10. The alkenyl group may be linear, branched, or cyclic. The alkenyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, and a heteroaryl group.

[0079] R X1 ~R X9 The number of carbon atoms in the alkynyl group represented by is preferably 2 to 15, and more preferably 2 to 10. The alkynyl group may be linear, branched, or cyclic. The alkynyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, and a heteroaryl group.

[0080] R X1 ~R X9 The number of carbon atoms in the aryl group represented by is preferably 6 to 20, more preferably 6 to 12, still more preferably 6 to 10, and particularly preferably 6. The aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and a heteroaryl group.

[0081] R X1 ~R X9 The heteroaryl group represented by is preferably a 5-membered or 6-membered ring. The heteroatoms contained in the heteroaryl group are preferably oxygen, nitrogen, or sulfur atoms. The number of heteroatoms contained in the heteroaryl group is preferably 1 to 3. The heteroaryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and an aryl group.

[0082] R in formula (OX-1) 1a represents a hydrogen atom or an acyl group, and is preferably an acyl group.

[0083] R in formula (OX-1) 2a represents an alkyl group or an aryl group, and is preferably an alkyl group because the reactivity of the generated radical is high. R 2aThe number of carbon atoms in the alkyl group represented by R is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have a substituent, but is preferably an unsubstituted alkyl group. R 2a The alkyl group represented by is preferably an unsubstituted linear or branched alkyl group, and more preferably an unsubstituted linear alkyl group. R 2a The number of carbon atoms in the aryl group represented by is preferably 6 to 20, more preferably 6 to 12, still more preferably 6 to 10, and particularly preferably 6. The aryl group may have a substituent, but is preferably an unsubstituted aryl group.

[0084] R in formula (OX-1) 3a and R 4a each independently represents a hydrogen atom or an alkyl group, and is preferably a hydrogen atom. R 3a and R 4a The number of carbon atoms in the alkyl group represented by is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have a substituent, but is preferably an unsubstituted alkyl group. R 3a and R 4a may be bonded to form a ring. The ring formed is preferably a 5- or 6-membered ring, and more preferably a 5- or 6-membered aliphatic hydrocarbon ring.

[0085] Alk of formula (OX-1) 1 and Alk 2each independently represents an alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have a substituent, but is preferably an unsubstituted alkyl group. Alk 1 and Alk 2 may be bonded to form a ring, and preferably form a ring. The ring formed is preferably a 5- or 6-membered ring, more preferably a 5- or 6-membered aliphatic hydrocarbon ring, and more preferably a cyclopentane ring or a cyclohexane ring.

[0086] In formula (OX-1), n ​​represents 0 or 1, and is preferably 0.

[0087] Specific examples of the compound represented by formula (OX-1) include the compounds described in paragraphs 0092 to 0096 of JP-A No. 2012-113104 and the compound described in paragraph 0041 of JP-A No. 2012-189997.

[0088] As another photopolymerization initiator, a compound represented by formula (OX-2) can also be used.

[0089] [ka]

[0090] In formula (OX-2), R 1b and R 2b each independently represents a substituent, R 3b ~R 7b each independently represents a hydrogen atom or a substituent, and Ar 1b represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent; and n represents 0 or 1.

[0091] R 1b and R 2b Examples of the substituent represented by include an alkyl group and an aryl group, and an alkyl group is preferred. The alkyl group preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms. The alkyl group may be linear, branched, or cyclic. The alkyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, an alkenyl group, an alkynyl group, and a heteroaryl group. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12, still more preferably 6 to 10, and particularly preferably 6. The aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and a heteroaryl group.

[0092] R 3b ~R 7b Examples of the substituent represented by include a halogen atom, an alkyl group, and an aryl group. Examples of the alkyl group and aryl group include those described above. R 3b ~R 7b is preferably a hydrogen atom.

[0093] Ar 1b represents an optionally substituted aryl group or an optionally substituted heteroaryl group, Ar 1b is preferably an aryl group which may have a substituent. The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 12, still more preferably 6 to 10, and particularly preferably 6. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylthio group, an arylthio group, a nitro group, and an acyl group, and an acyl group is preferred.

[0094] As another photopolymerization initiator, a compound represented by formula (OX-3) can also be used.

[0095] [ka]

[0096] In formula (OX-3), Ar 1c represents a (k+m+1)-valent aromatic ring group or a (k+m+1)-valent heterocyclic group, Ar 2c represents a (k+2)-valent aromatic ring group or a (k+2)-valent heterocyclic group, R 1c ~R 3c each independently represents a substituent, L 1c is a single bond or CR 11c R 12c represents R 11c and R 12c each independently represents a hydrogen atom, an alkyl group, or an aryl group; X 1c represents -CH2-, -N-, -O- or -S-; k represents 0 or 1; m represents an integer of 0 to 4; and n represents 0 or 1.

[0097] R 1c and R 2c Examples of the substituent represented by include an alkyl group and an aryl group, and an alkyl group is preferred. The alkyl group preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms. The alkyl group may be linear, branched, or cyclic. The alkyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, an alkenyl group, an alkynyl group, and a heteroaryl group. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12, still more preferably 6 to 10, and particularly preferably 6. The aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and a heteroaryl group. R 2c is preferably an alkyl group having a branched or cyclic structure.

[0098] R 3cExamples of the substituent represented by include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group and an acyl group, and an acyl group is preferred.

[0099] L 1c is a single bond or CR 11c R 12c represents R 11c and R 12c R each independently represents a hydrogen atom, an alkyl group, or an aryl group. 11c and R 12c The alkyl and aryl groups in R 1c and R 2c When k is 1, L 1c is preferably a single bond.

[0100] X 1c represents -CH2-, -N-, -O- or -S-, and is preferably -O- or -S-.

[0101] Ar 1c represents a (k+m+1)-valent aromatic ring group or a (k+m+1)-valent heterocyclic group, and is preferably a (k+m+1)-valent aromatic ring group. The aromatic ring group is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group.

[0102] Ar 2c represents a (k+2)-valent aromatic ring group or a (k+2)-valent heterocyclic group, and is preferably a (k+2)-valent aromatic ring group. The aromatic ring group is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group.

[0103] k represents 0 or 1, and is preferably 0. m represents an integer of 0 to 4, preferably 0 or 1, and more preferably 1. n represents 0 or 1, and is preferably 0.

[0104] Specific examples of the oxime compound include the compounds shown below.

[0105] [ka]

[0106] [ka]

[0107] [ka]

[0108] [ka]

[0109] [ka]

[0110] As other photopolymerization initiators, bifunctional or trifunctional or higher functional photopolymerization initiators may be used. Specific examples of bifunctional or trifunctional or higher functional photopolymerization initiators include the compounds described in paragraph 0148 of WO 2022 / 065215.

[0111] The content of the photopolymerization initiator in the total solid content of the photocurable composition is preferably 1 to 20% by mass. The lower limit is preferably 1.5% by mass or more, and more preferably 2% by mass or more. The upper limit is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 8% by mass or less. In the photocurable composition of the present invention, only one type of photopolymerization initiator 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.

[0112] The content of the specific compound in the photopolymerization initiator is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.

[0113] The content of the specific compound in the total solid content of the photocurable composition is preferably 0.1 to 50% by mass. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 45% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. In the photocurable composition of the present invention, only one type of specific compound may be used, or two or more types may be used. When two or more types are used, the total amount thereof preferably falls within the above range.

[0114] <<Polymerizable compounds>> The photocurable composition of the present invention contains a polymerizable compound. Examples of the polymerizable compound include a compound having an ethylenically unsaturated bond-containing group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group. The polymerizable compound is preferably a radically polymerizable compound.

[0115] The polymerizable compound is preferably a monomer. The molecular weight of the polymerizable compound is preferably 100 to 2500. The upper limit is preferably 2000 or less, more preferably 1500 or less. The lower limit is preferably 150 or more, more preferably 250 or more.

[0116] The polymerizable compound is preferably a compound containing two or more ethylenically unsaturated bond-containing groups, more preferably a compound containing 2 to 15 ethylenically unsaturated bond-containing groups, and even more preferably a compound containing 2 to 6 ethylenically unsaturated bond-containing groups. The polymerizable compound is preferably a difunctional to 15-functional (meth)acrylate compound, and more preferably a difunctional to hexafunctional (meth)acrylate compound. Specific examples of the polymerizable compound include the compounds described in paragraphs 0075 to 0083 of WO 2022 / 065215 and the compounds described in Taiwan Patent Application Publication No. 201832008.

[0117] Preferred polymerizable compounds include dipentaerythritol tri(meth)acrylate (commercially available product: KAYARAD D-330, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available product: KAYARAD D-320, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available product: KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available products: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., and NK Ester A-DPH-12E, manufactured by Shin-Nakamura Chemical Co., Ltd.), and compounds in which the (meth)acryloyl groups are bonded via ethylene glycol and / or propylene glycol residues (e.g., SR454 and SR499, commercially available from Sartomer).Examples of polymerizable compounds include diglycerin EO (ethylene oxide)-modified (meth)acrylate (commercially available product: M-460, manufactured by Toagosei Co., Ltd.), pentaerythritol tetraacrylate (NK Ester A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (KAYARAD HDDA, manufactured by Nippon Kayaku Co., Ltd.), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix TO-2349 (manufactured by Toagosei Co., Ltd.), NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical 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.), and 8UH-1 006, 8UH-1012 (all manufactured by Taisei Fine Chemical Co., Ltd.), Light Acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), Aronix MT-3041, 3042 (manufactured by Toagosei Co., Ltd., polymerizable compounds containing amines), Aronix M-510, 520 (manufactured by Toagosei Co., Ltd., polymerizable compounds with acidic groups), Etercure 6361-100 (Eternal Materials, a polymerizable compound having a hyperbranched structure), EBECRYL80 (a tetrafunctional monomer containing an amine, manufactured by Daicel-Olknes Co., Ltd.), EBECRYL7100 (a bifunctional monomer containing an amine, manufactured by Daicel-Olknes Co., Ltd.), CN371NS (a bifunctional monomer containing an amine, manufactured by Arkema), HOA-MPL (2-acryloyloxyethyl-phthalic acid: manufactured by Kyoeisha Chemical Co., Ltd.), HOA-MPE (2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid: manufactured by Kyoeisha Chemical Co., Ltd.), polymerizable compounds having a dendrimer structure or hyperbranched structure described in JP 2023-043479 A, ​​polymerizable compounds described in JP 2023-529984 A, and polymerizable compounds described in WO 2023 / 190562 can also be used.

[0118] The polymerizable compound may also be a polymerizable compound having an ethylene oxide repeating chain. According to this embodiment, the effects of the present invention are more pronounced. Examples of the polymerizable compound having an ethylene oxide repeating chain include a compound represented by formula (EO-1). [ka]

[0119] R in formula (EO-1) E1 represents a hydrogen atom or a methyl group.

[0120] L in formula (EO-1) E1 represents a linking group having a valence of m. E1 The m-valent linking group represented by is a hydrocarbon group, a heterocyclic group, -O-, -S-, -NR A1 -, -CO-, -COO-, -OCO-, -SO2- and groups formed by combining two or more of these groups. A1 represents a hydrogen atom, an alkyl group, or an aryl group, with a hydrogen atom being preferred. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be cyclic or acyclic. The acyclic aliphatic hydrocarbon group may be a straight-chain aliphatic hydrocarbon group or a branched aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The hydrocarbon group may have a substituent or may not have a substituent. The cyclic aliphatic hydrocarbon group and the aromatic hydrocarbon group may be a monocyclic ring or a fused ring. The heterocyclic group may be a monocyclic ring or a fused ring. The heterocyclic group is preferably a 5- or 6-membered ring. The heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. Examples of heteroatoms constituting the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom.

[0121] In formula (EO-1), n ​​represents an integer of 1 to 20, and m represents an integer of 2 to 10. n is preferably an integer of 1 to 15, and more preferably an integer of 1 to 10. m is preferably an integer of 2 to 8, and more preferably an integer of 2 to 6.

[0122] As the polymerizable compound, a polymerizable compound having a fluorene skeleton can also be used. The polymerizable compound having a fluorene skeleton is preferably a bifunctional polymerizable compound. Examples of commercially available polymerizable compounds having a fluorene skeleton include OGSOL EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., (meth)acrylate monomers having a fluorene skeleton).

[0123] The content of the polymerizable compound in the total solid content of the photocurable composition is preferably 1 to 30% by mass. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less. The lower limit is preferably 3% by mass or more, and more preferably 5% by mass or more. The photocurable composition of the present invention may contain only one polymerizable compound or may contain two or more polymerizable compounds. When two or more polymerizable compounds are contained, the total amount thereof is preferably within the above range.

[0124] <<Solvent>> The photocurable composition of the present invention preferably contains a solvent. Examples of the solvent include organic solvents. The type of solvent is not particularly limited as long as it satisfies the solubility of each component and the coatability of the composition. Examples of organic solvents include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents. For details of these, please refer to paragraph 0223 of WO 2015 / 166779, the contents of which are incorporated herein by reference. Furthermore, ester-based solvents substituted with a cyclic alkyl group and ketone-based solvents substituted with a cyclic alkyl group can also be preferably used. Specific examples of 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 ... Examples of suitable methyl alcohols include ethylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, gamma butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane-1,3-diyl diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol (also known as diacetone alcohol or 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, and isopropyl alcohol.However, it may be better to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as organic solvents for environmental reasons (for example, the amount can be reduced to 50 ppm by mass (parts per million) or less, 10 ppm by mass or less, or 1 ppm by mass or less, relative to the total amount of organic solvents).

[0125] The metal content of the organic solvent is preferably low. For example, the metal content of the organic solvent is preferably 10 mass ppb (parts per billion) or less. If necessary, organic solvents with metal contents at the mass ppt (parts per trillion) level may be used, and such organic solvents are provided, for example, by Toyo Gosei Co., Ltd. (The Chemical Daily, November 13, 2015).

[0126] Methods for removing impurities such as metals from organic solvents include, for example, distillation (molecular distillation, thin-film distillation, etc.) and filtration using a filter. The pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon.

[0127] The organic solvent may contain isomers (compounds with the same number of atoms but different structures), and may contain only one type of isomer or multiple types of isomers.

[0128] The organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.

[0129] The content of the solvent in the photocurable composition is preferably from 10 to 95% by mass, more preferably from 20 to 90% by mass, and even more preferably from 30 to 90% by mass.

[0130] From the viewpoint of environmental regulations, the photocurable composition of the present invention preferably contains substantially no environmentally restricted substances. In the present invention, "substantially no environmentally restricted substances" means that the content of environmentally restricted substances in the photocurable composition is 50 ppm by mass or less, preferably 30 ppm by mass or less, more preferably 10 ppm by mass or less, and particularly preferably 1 ppm by mass or less. Examples of environmentally restricted substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These substances are registered as environmentally restricted substances under the REACH (Registration Evaluation Authorization and Restriction of Chemicals) regulations, the PRTR (Pollutant Release and Transfer Register) Act, and the VOC (Volatile Organic Compounds) regulations, and their usage amounts and handling methods are strictly regulated. These compounds may be used as solvents when producing components used in the photocurable composition and may be mixed into the photocurable composition as residual solvents. From the viewpoints of human safety and environmental considerations, it is preferable to reduce the content of these substances as much as possible. Methods for reducing environmentally regulated substances include heating or reducing the pressure in the system to a temperature above the boiling point of the environmentally regulated substance, thereby distilling off the environmentally regulated substance from the system. When distilling off a small amount of an environmentally regulated substance, it is also useful to perform azeotropy with a solvent having a boiling point similar to that of the solvent in question in order to increase efficiency. Furthermore, when a radically polymerizable compound is contained, a polymerization inhibitor or the like may be added before distillation under reduced pressure to prevent intermolecular crosslinking due to the progression of a radical polymerization reaction during distillation under reduced pressure. These distillation methods can be used at any stage, such as the stage of the raw materials, the stage of the product obtained by reacting the raw materials (e.g., a resin solution or a polyfunctional monomer solution after polymerization), or the stage of a photocurable composition prepared by mixing these compounds.

[0131] <<Resin>> The photocurable composition of the present invention preferably contains a resin. The resin is blended, for example, to disperse pigments or the like in the photocurable composition or as a binder. Resins used primarily to disperse pigments or the like in the photocurable composition are also called dispersants. However, these uses of resins are merely examples, and resins can also be used for purposes other than these uses.

[0132] The weight average molecular weight (Mw) of the resin is preferably 3,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 4,000 or more, more preferably 5,000 or more.

[0133] Examples of the resin include (meth)acrylic resin, epoxy resin, (meth)acrylamide 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, and siloxane resin. Further, examples of the resin include the resins described in paragraphs 0091 to 0099 of WO 2022 / 065215, the blocked polyisocyanate resins described in JP 2016-222891 A, the resins described in JP 2020-122052 A, the resins described in JP 2020-111656 A, the resins described in JP 2020-139021 A, the resins described in JP 2017-138503 A containing a structural unit having a ring structure in the main chain and a structural unit having a biphenyl group in the side chain, the resins described in paragraphs 0199 to 0233 of JP 2020-186373 A, the alkali-soluble resins described in JP 2020-186325 A, and the resins described in Korean Patent Publication No. Resins represented by formula 1 described in WO 2020-0078339, copolymers containing epoxy groups and acid groups described in WO 2022 / 030445, resins described in JP 2018-135514 A, copolymers described in JP 2020-041046 A, resins described in JP 2023-033156 A, resins described in JP 2023-030386 A, resins described in JP 2023-027753 A, resins described in JP 2020-139021 A, resins described in JP 2023-074038 A, resins described in JP 2023-079666 A, and cardo resins described in Chinese Patent Application Publication No. 115947929 can also be used.

[0134] The resin to be used is preferably a resin having an acid group, such as a carboxy group, a phosphate group, a sulfo group, or a phenolic hydroxy group.

[0135] The acid value of the resin having acid groups is preferably 30 to 500 mgKOH / g. The lower limit is preferably 40 mgKOH / g or more, more preferably 50 mgKOH / g or more. The upper limit is preferably 400 mgKOH / g or less, more preferably 300 mgKOH / g or less, and even more preferably 200 mgKOH / g or less. The weight average molecular weight (Mw) of the resin having acid groups is preferably 5,000 to 100,000, more preferably 5,000 to 50,000. The number average molecular weight (Mn) of the resin having acid groups is preferably 1,000 to 20,000.

[0136] The resin having an acid group preferably contains a repeating unit having an acid group on a side chain, and more preferably contains 5 to 70 mol% of repeating units having an acid group on a side chain based on all repeating units of the resin. The upper limit of the content of repeating units having an acid group on a side chain is preferably 50 mol% or less, more preferably 30 mol% or less. The lower limit of the content of repeating units having an acid group on a side chain is preferably 10 mol% or more, more preferably 20 mol% or more.

[0137] For resins having acid groups, please refer to paragraphs

[0558] to

[0571] of JP 2012-208494 A (corresponding to paragraphs

[0685] to

[0700] of U.S. Patent Application Publication No. 2012 / 0235099 A) and paragraphs

[0076] to

[0099] of JP 2012-198408 A, the contents of which are incorporated herein by reference. Commercially available resins having acid groups can also be used. There are no particular limitations on the method for introducing acid groups into the resin, and examples include the method described in Japanese Patent No. 6,349,629 A. Another method for introducing acid groups into the resin includes reacting an acid anhydride with a hydroxy group generated by a ring-opening reaction of an epoxy group to introduce the acid group.

[0138] The photocurable composition of the present invention also preferably contains a resin having a basic group. The resin having a basic group is preferably a resin containing a repeating unit having a basic group in a side chain, more preferably a copolymer having a repeating unit having a basic group in a side chain and a repeating unit not having a basic group, and even more preferably a block copolymer having a repeating unit having a basic group in a side chain and a repeating unit not having a basic group. The resin having a basic group can also be used as a dispersant. The amine value of the resin having a basic group is preferably 5 to 300 mgKOH / g. The lower limit is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more. The upper limit is preferably 200 mgKOH / g or less, more preferably 100 mgKOH / g or less.

[0139] Commercially available resins having basic groups include DISPERBYK-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, and BYK-LPN6919 (all manufactured by BYK-Chemie), and Solsperse 112. 00, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 38500, 39000, 53095, 56000, 7100 (all manufactured by Lubrizol Japan), Efka PX 4300, 4330, 4046, 4060, 4080 (all manufactured by BASF), and the like. In addition, the resin having a basic group may be the block copolymer (B) described in paragraphs 0063 to 0112 of JP 2014-219665 A, the block copolymer A1 described in paragraphs 0046 to 0076 of JP 2018-156021 A, or the vinyl resin having a basic group described in paragraphs 0150 to 0153 of JP 2019-184763 A, the contents of which are incorporated herein by reference.

[0140] The photocurable composition of the present invention preferably contains both a resin having an acid group and a resin having a basic group. This embodiment can further improve the storage stability of the photocurable composition. When a resin having an acid group and a resin having a basic group are used in combination, the content of the resin having a basic group is preferably 20 to 500 parts by mass, more preferably 30 to 300 parts by mass, and even more preferably 50 to 200 parts by mass per 100 parts by mass of the resin having an acid group.

[0141] It is also preferable to use a resin having an aromatic carboxy group as the resin. In a resin having an aromatic carboxy group, the aromatic carboxy group may be contained in the main chain of a repeating unit or may be contained in a side chain of the repeating unit. It is preferable that the aromatic carboxy group is contained in the main chain of a repeating unit. In this specification, an aromatic carboxy group refers to a group having a structure in which one or more carboxy groups are bonded to an aromatic ring. In the aromatic carboxy group, the number of carboxy groups bonded to the aromatic ring is preferably 1 to 4, and more preferably 1 to 2. Examples of resins having an aromatic carboxy group include the resins described in paragraphs 0082 to 0107 of WO 2021 / 166858.

[0142] It is also preferable to use a resin having a crosslinkable group as the resin. Examples of the crosslinkable group include an ethylenically unsaturated bond-containing group and a cyclic ether group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group. When a resin having a crosslinkable group is used, the content of the resin having the crosslinkable group in the resin contained in the photocurable composition is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more.

[0143] It is also preferable to use a resin having a graft chain (hereinafter also referred to as a graft resin) as the resin. In this specification, the graft chain means a polymer chain that branches off from the main chain of a repeating unit. The graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2,000 atoms excluding hydrogen atoms, and even more preferably 60 to 500 atoms excluding hydrogen atoms.

[0144] The graft chain preferably contains repeating units of at least one structure selected from a polyether structure, a polyester structure, a poly(meth)acrylic structure, a polystyrene structure, a polyurethane structure, a polyurea structure, and a polyamide structure, more preferably contains repeating units of at least one structure selected from a polyether structure, a polyester structure, a poly(meth)acrylic structure, and a polystyrene structure, further preferably contains repeating units of a polyether structure or a polyester structure, and particularly preferably contains repeating units of a polyester structure.

[0145] Examples of repeating units of polyester structures include repeating units of structures represented by formula (G-1), formula (G-4), or formula (G-5). Examples of repeating units of polyether structures include repeating units of structures represented by formula (G-2). Examples of repeating units of poly(meth)acrylic structures include repeating units of structures represented by formula (G-3). Examples of repeating units of polystyrene structures include repeating units of structures represented by formula (G-6). [ka]

[0146] In the above formula, R G1 and R G2 R each independently represents an alkylene group. G1 and R G2The alkylene group represented by is not particularly limited, but is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably a linear or branched alkylene group having 2 to 16 carbon atoms, and even more preferably a linear or branched alkylene group having 3 to 12 carbon atoms.

[0147] In the above formula, R G3 represents a hydrogen atom or a methyl group, and Q G1 represents -O- or -NH-, and L G1 represents a single bond or a divalent linking group, and R G4 represents a hydrogen atom or a substituent. L G1 Examples of the divalent linking group represented by the formula (I) include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms), an oxyalkylenecarbonyl group (preferably an oxyalkylenecarbonyl group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, and groups formed by combining two or more of these. R G4 Examples of the substituent represented by include a hydroxy group, a carboxy group, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, an ethylenically unsaturated bond-containing group, an epoxy group, an oxetanyl group, and a blocked isocyanate group.

[0148] R G5 represents a hydrogen atom or a methyl group, and R G6 represents an aryl group. G6 The number of carbon atoms in the aryl group represented by R is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12. G6The aryl group represented by may have a substituent, such as a hydroxy group, a carboxy group, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, or a crosslinkable group.

[0149] The terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. Examples of the substituent include a group represented by formula (W-1). -L w1 -R w1 ···(W-1) In the formula, L w1 represents a single bond or a divalent linking group, R w1 represents an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, or a heteroarylthioether group.

[0150] L w1 Examples of the divalent linking group represented by the formula (I) include an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -CONR L1 -, -S-, and groups combining two or more of these groups. L1 represents a hydrogen atom, an alkyl group, or an aryl group.

[0151] R w1 is preferably an alkyl group or an alkoxy group.

[0152] The graft chain preferably has a structure represented by the following formula (G-1a), (G-2a), (G-3a), (G-4a), (G-5a) or (G-6a), and more preferably has a structure represented by formula (G-1a), (G-4a) or (G-5a). [ka]

[0153] In the above formula, R G1 and R G2 each represents an alkylene group, and R G3 represents a hydrogen atom or a methyl group, and Q G1 represents -O- or -NH-, and L G1 represents a single bond or a divalent linking group, and R G4 represents a hydrogen atom or a substituent, and R G5 represents a hydrogen atom or a methyl group, and R G6 represents an aryl group, W 100 represents a hydrogen atom or a substituent, and n1 to n6 each independently represent an integer of 2 or more. G1 ~R G6 , Q G1 , L G1 Regarding R explained in formulas (G-1) to (G-6), G1 ~R G6 , Q G1 , L G1 The same applies to the preferred range.

[0154] In formulas (G-1a) to (G-6a), W 100 is preferably a substituent. Examples of the substituent include the group represented by the above formula (W-1).

[0155] In the formulae (G-1a) to (G-6a), n1 to n6 are each preferably an integer of 2 to 100, more preferably an integer of 2 to 80, and even more preferably an integer of 8 to 60.

[0156] In formula (G-1a), when n1 is 2 or more, R in each repeating unit G1 R may be the same or different. G1In the case where the repeating unit has two or more different repeating units, the arrangement of the repeating units is not particularly limited and may be random, alternating, or block. The same applies to formulas (G-2a) to (G-6a). The graft chain has a structure represented by formula (G-1a), formula (G-4a), or formula (G-5a), and R G1 It is also preferable that the repeating unit has a structure containing two or more different repeating units.

[0157] The graft resin is preferably a resin having a repeating unit having a graft chain. Examples of the repeating unit having a graft chain include a repeating unit represented by formula (e3). [ka]

[0158] In the formula, A e30 represents a trivalent linking group, L e30 represents a single bond or a divalent linking group, W e30 represents a graft chain.

[0159] A e30 Examples of the trivalent linking group represented by include a poly(meth)acrylic linking group, a polyalkyleneimine linking group, a polyester linking group, a polyurethane linking group, a polyurea linking group, a polyamide linking group, a polyether linking group, and a polystyrene linking group. A poly(meth)acrylic linking group or a polyalkyleneimine linking group is preferred, and a poly(meth)acrylic linking group is more preferred.

[0160] L e30 Examples of the divalent linking group represented by the formula (I) include an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -CONR x3 -, -S-, and groups combining two or more of these groups. x3represents a hydrogen atom, an alkyl group, or an aryl group. The alkylene group and arylene group may have a substituent.

[0161] W e30 Examples of the graft chain represented by include the graft chains described above.

[0162] The content of repeating units having graft chains in all repeating units of the graft resin is preferably 1 mol% or more, more preferably 2 mol% or more, and even more preferably 3 mol% or more, and the upper limit can be 90 mol% or less, 80 mol% or less, or 70 mol% or less.

[0163] The graft resin preferably has a crosslinkable group. By using a graft resin having a crosslinkable group, the moisture resistance of the resulting film can be improved. The graft resin having a crosslinkable group may be a resin having a repeating unit having a crosslinkable group and a repeating unit having a graft chain, or may be a resin having a graft chain containing a crosslinkable group. Examples of the crosslinkable group include those mentioned above.

[0164] The graft resin may further have a repeating unit having an acid group, such as a carboxy group, a sulfo group, or a phosphate group, with a carboxy group being preferred.

[0165] The content of repeating units having an acid group in all repeating units of the graft resin is preferably 1 mol% or more, more preferably 2 mol% or more, and even more preferably 3 mol% or more, and the upper limit can be set to 90 mol% or less, 80 mol% or less, or 70 mol% or less.

[0166] The weight average molecular weight of the graft resin is preferably 5000 to 100000. The upper limit is preferably 80000 or less, more preferably 60000 or less. The lower limit is preferably 6000 or more, more preferably 8000 or more. The acid value of the graft resin is preferably 5 to 250 mgKOH / g, more preferably 10 to 200 mgKOH / g, and even more preferably 20 to 180 mgKOH / g, because this allows further suppression of residue generation.

[0167] The photocurable composition of the present invention preferably contains a resin as a dispersant. Examples of dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, the term "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 the acid groups and the basic groups is taken as 100 mol %. The acid groups possessed by the acidic dispersant (acidic resin) are preferably carboxy groups. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH / g. Furthermore, the term "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 is greater than 50 mol % when the total amount of the acid groups and the basic groups is taken as 100 mol %. The basic groups possessed by the basic dispersant are preferably amino groups.

[0168] The resin used as the dispersant is preferably a graft resin, such as those mentioned above.

[0169] The resin used as the dispersant is preferably a resin having an aromatic carboxy group, such as those mentioned above.

[0170] The resin used as the dispersant is preferably a polyimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain. The polyimine-based dispersant is preferably a resin having a main chain with a partial structure having a functional group with a pKa of 14 or less and a side chain having 40 to 10,000 atoms, and having a basic nitrogen atom in at least one of the main chain and the side chain. There are no particular restrictions on the basic nitrogen atom, as long as it is a nitrogen atom that exhibits basicity. For details about polyimine-based dispersants, please refer to the description in paragraphs 0102 to 0166 of JP 2012-255128 A, the contents of which are incorporated herein by reference.

[0171] The resin used as a dispersant is preferably a resin having a structure in which multiple polymer chains are bonded to a core portion. Examples of such resins include dendrimers (including star-shaped polymers). Specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP 2013-043962 A.

[0172] The resin used as a dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated bond-containing group in a side chain. The content of the repeating unit having an ethylenically unsaturated bond-containing group in a side chain is preferably 10 mol % or more, more preferably 10 to 80 mol %, and even more preferably 20 to 70 mol %, of all repeating units of the resin.

[0173] As the dispersant, the resin described in JP 2018-087939 A, the block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent No. 6432077 A, polyethyleneimine having a polyester side chain described in WO 2016 / 104803 A, block copolymers described in WO 2019 / 125940 A, block polymers having an acrylamide structural unit described in JP 2020-066687 A, block polymers having an acrylamide structural unit described in JP 2020-066688 A, dispersants described in WO 2016 / 104803 A, and the like can also be used.

[0174] Dispersants are also available as commercially available products, and specific examples thereof include the DISPERBYK series manufactured by BYKChemie, the SOLSPERSE series manufactured by Lubrizol Japan, the Efka series manufactured by BASF, and the AJISPER series manufactured by Ajinomoto Fine-Techno Co., Ltd. In addition, the products described in paragraph 0129 of JP 2012-137564 A and the products described in paragraph 0235 of JP 2017-194662 A can also be used as dispersants.

[0175] The content of the resin in the total solid content of the photocurable composition is preferably 1 to 60% by mass. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and particularly preferably 20% by mass or more. The upper limit is preferably 50% by mass or less, more preferably 40% by mass or less. The content of the resin having an acid group in the total solid content of the photocurable composition is preferably 1 to 60% by mass. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and particularly preferably 20% by mass or more. The upper limit is preferably 50% by mass or less, more preferably 40% by mass or less. The content of the graft resin in the total solid content of the photocurable composition is preferably 0.1 to 50% by mass. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less. The photocurable composition of the present invention may contain only one type of resin or two or more types of resins. When two or more types of resins are contained, the total amount thereof is preferably within the above range.

[0176] <<Colorants>> The photocurable composition of the present invention preferably contains a coloring material. Examples of the coloring material include a white coloring material, a black coloring material, a chromatic coloring material, and an infrared-absorbing coloring material. In the present invention, the white coloring material includes not only pure white coloring materials but also light gray coloring materials close to white (e.g., grayish white, light gray, etc.).

[0177] The coloring material may be a pigment or a dye. A pigment and a dye may be used in combination. The pigment may be either an inorganic pigment or an organic pigment, but is preferably an organic pigment from the viewpoints of a wide range of color variations, ease of dispersion, safety, etc. The coloring material preferably contains a pigment.

[0178] The average primary particle diameter of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less. In this specification, the primary particle diameter of the pigment can be determined from a photograph obtained by observing the primary particles of the pigment with a transmission electron microscope. Specifically, the projected area of ​​the primary particles of the pigment is determined, and the corresponding circle-equivalent diameter is calculated as the primary particle diameter of the pigment.

[0179] The crystallite size of the pigment, determined from the half-width of a peak derived from any crystal plane in an X-ray diffraction spectrum obtained using CuKα radiation as an X-ray source, is preferably 0.1 to 100 nm, more preferably 0.5 to 50 nm, even more preferably 1 to 30 nm, and particularly preferably 5 to 25 nm.

[0180] The specific surface area of ​​pigments is 1 to 300 m 2 / g. The lower limit is 10m 2 / g or more is preferable, and 30m 2 / g or more is more preferable. The upper limit is 250m 2 / g or less, and 2 / g or less. The specific surface area value can be determined according to the BET (Brunauer, Emmett and Teller) method in accordance with DIN 66131: Determination of the specific surface area of ​​solids by gas adsorption.

[0181] (Chromatic color materials) Examples of chromatic colorants include colorants having a maximum absorption wavelength in the wavelength range of 400 to 700 nm, such as green colorants, red colorants, yellow colorants, purple colorants, blue colorants, and orange colorants.

[0182] Examples of red colorants include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, azomethine compounds, xanthene compounds, quinacridone compounds, perylene compounds, and thioindigo compounds, and are preferably diketopyrrolopyrrole compounds, anthraquinone compounds, and azo compounds, and more preferably diketopyrrolopyrrole compounds.Furthermore, the red colorant is preferably a pigment (red pigment), and more preferably a diketopyrrolopyrrole pigment.

[0183] Specific examples of red colorants include CI (Color Index) Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, Examples of red pigments include 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 269, 270, 272, 279, 291, 294, 295, 296, and 297. In addition, as a red colorant, the compound described in paragraph 0034 of WO 2022 / 085485 and the brominated diketopyrrolopyrrole compound described in JP 2020-085947 A can also be used.

[0184] As the red colorant, CI Pigment Red 122, 177, 224, 254, 255, 264, 269, 272, and 291 are preferred, CI Pigment Red 254, 264, and 272 are more preferred, and CI Pigment Red 254 and 264 are even more preferred.

[0185] Examples of green coloring materials include phthalocyanine compounds and squarylium compounds, and the phthalocyanine compounds are preferred. The green coloring material is preferably a pigment (green pigment), and more preferably a phthalocyanine pigment.

[0186] Specific examples of green colorants include green pigments such as CI Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66. Furthermore, halogenated zinc phthalocyanine pigments having an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms per molecule can also be used as green colorants. Specific examples include compounds described in International Publication No. 2015 / 118720. Furthermore, compounds described in paragraph 0029 of International Publication No. 2022 / 085485, aluminum phthalocyanine compounds described in JP-A-2020-070426, and diarylmethane compounds described in JP-A-2020-504758 can also be used as green colorants.

[0187] As the green colorant, CI Pigment Green 7, 36, 58, 62, and 63 are preferred.

[0188] Examples of orange colorants include diketopyrrolopyrrole compounds and azo compounds. The orange colorant is preferably a pigment (orange pigment). Specific examples of orange colorants include CI Pigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, and 73.

[0189] Examples of the yellow colorant include an azo compound, an azomethine compound, an isoindoline compound, a pteridine compound, a quinophthalone compound, and a perylene compound. The yellow colorant is preferably a pigment (yellow pigment). Specific examples of yellow colorants include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, and 120. , 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, 215, 228, 231, 232, 233, 234, 235, 236 and the like.

[0190] As the yellow coloring material, an azobarbituric acid nickel complex having the following structure can also be used. [ka]

[0191] As the yellow colorant, the compounds described in paragraphs 0031 to 0033 of WO 2022 / 085485, the methine dyes described in JP 2019-073695 A, and the methine dyes described in JP 2019-073696 A can be used.

[0192] Examples of purple colorants include oxazine compounds, quinacridone compounds, perylene compounds, and indigo compounds, with oxazine compounds being preferred. The purple colorant is preferably a pigment (purple pigment). Specific examples of purple colorants include CI Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.

[0193] Examples of blue colorants include phthalocyanine compounds and squarylium compounds, with phthalocyanine compounds being preferred. The blue colorant is preferably a pigment (blue pigment). Specific examples of blue colorants include CI Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87, and 88. Aluminum phthalocyanine compounds having phosphorus atoms can also be used as blue colorants. Specific examples include the compounds described in paragraphs 0022 to 0030 of JP-A No. 2012-247591 and paragraph 0047 of JP-A No. 2011-157478.

[0194] Dyes can also be used as chromatic colorants. There are no particular limitations on the dyes, and known dyes can be used. Examples include pyrazole azo dyes, anilino azo dyes, triarylmethane dyes, anthraquinone dyes, anthrapyridone dyes, benzylidene dyes, oxonol dyes, pyrazolotriazole azo dyes, pyridone azo dyes, cyanine dyes, phenothiazine dyes, pyrrolopyrazole azomethine dyes, xanthene dyes, phthalocyanine dyes, benzopyran dyes, indigo dyes, and pyrromethene dyes.

[0195] A dye multimer can also be used as a chromatic colorant. The dye multimer is preferably a dye dissolved in a solvent before use. The dye multimer may also form particles. When the dye multimer is in the form of particles, it is usually used in a state dispersed in a solvent. A particulate dye multimer can be obtained, for example, by emulsion polymerization, and specific examples of the compounds and production methods described in JP-A No. 2015-214682 include the compounds and production methods described in JP-A No. 2015-214682. The dye multimer has two or more dye structures in one molecule, preferably three or more dye structures. The upper limit is not particularly limited, but can be 100 or less. The multiple dye structures in one molecule may be the same dye structure or different dye structures. The weight-average molecular weight (Mw) of the dye multimer is preferably 2,000 to 50,000. The lower limit is more preferably 3,000 or more, and even more preferably 6,000 or more. The upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less. As the dye multimer, compounds described in JP-A Nos. 2011-213925, 2013-041097, 2015-028144, 2015-030742, WO 2016 / 031442, etc. can also be used.

[0196] Examples of chromatic colorants include triarylmethane dye polymers described in Korean Patent Publication No. 10-2020-0028160, xanthene compounds described in Japanese Patent Application Laid-Open No. 2020-117638, phthalocyanine compounds described in International Publication No. 2020 / 174991, isoindoline compounds or salts thereof described in Japanese Patent Application Laid-Open No. 2020-160279, compounds represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069442, compounds represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069730, and compounds represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069070. Compounds represented by the formula (I) described in Korean Patent Publication No. 10-2020-0069067, compounds represented by the formula (I) described in Korean Patent Publication No. 10-2020-0069062, halogenated zinc phthalocyanine pigments described in Japanese Patent No. 6809649, isoindoline compounds described in Japanese Patent Publication No. 2020-180176, phenothiazine compounds described in Japanese Patent Publication No. 2021-187913, halogenated zinc phthalocyanines described in International Publication No. 2022 / 004261, and halogenated zinc phthalocyanines described in International Publication No. 2021 / 250883 can be used. The chromatic colorant may be a rotaxane, and the dye skeleton may be used in the cyclic structure of the rotaxane, in the rod-shaped structure, or in both structures. As chromatic colorants, quinophthalone compounds represented by formula 1 in Korean Patent Publication No. 10-2020-0030759, polymer dyes described in Korean Patent Publication No. 10-2020-0061793, chromatic colorants described in JP 2022-029701 A, isoindoline compounds described in WO 2022 / 014635, aluminum phthalocyanine compounds described in WO 2022 / 024926, and JP 2022-045 895, compounds described in WO 2022 / 050051, compounds described in JP 2020-090676 A, compounds described in JP 2020-055956 A, compounds described in JP 2021-031681 A, compounds described in JP 2022-056354 A, compounds described in U.S. Patent Application Publication No. 2021 / 0355327, compounds described in WO 2022 / 065357,Compounds described in JP 2020-045436 A, compounds described in Korean Patent Publication No. 10-2021-0146726 A, compounds described in JP 2018-178039 A, compounds described in Chinese Patent Publication No. 113881244 A, compounds described in Chinese Patent Publication No. 113881245 A, compounds described in Chinese Patent Publication No. 113881246 A, compounds described in JP 2022-104822 A, compounds described in JP 2022-096701 A, compounds described in JP 2020-023652 A, green pigments described in JP 2022-143135 A, compounds described in JP 2022-140287 A, compounds described in WO 2022 / 136308 A, perylene compounds described in Chinese Patent Application Publication No. 113061349 A, cyan pigments described in Korean Patent Publication No. 10-2017-0018993 A, isoindoline compounds described in JP 2020-180176 A, compounds described in JP 2023-013209 A, compounds described in JP 2023-013166 A, Xanthene compounds described in JP-A-2023 / 286526, compounds described in JP-A-2021-155746, compounds described in JP-A-2021-155747, compounds described in JP-A-2021-155748, compounds described in JP-A-2021-155749, compounds described in WO 2018 / 051876, compounds described in JP-A-2020-083981, compounds described in JP-A-2023-056463, compounds described in JP-T-2023-515473, dioxane compounds described in JP-T-2022-549530, Pigment preparations described in JP 2022-061494 A, diketopyrrolopyrrole pigments described in JP 2023-057917 A, diketopyrrolopyrrole compounds described in JP 2023-061273 A, phthalocyanines described in JP-T-2023-519314 A, quinophthalones described in JP 2023-080419 A, phthalocyanine compounds described in JP 2023-103177 A, isoindoline compounds described in JP 2020-026521 A, squarylium compounds described in Korean Patent Publication No. 10-2023-0043000,Squarylium compounds described in Korean Patent Publication No. 10-2023-0050069, diketopyrrolopyrrole compounds described in JP 2023-127878, triarylmethane compounds described in JP 2023-150459, triarylmethane compounds described in JP 2023-149735, core-shell dyes described in JP 2023-123349, xanthene compounds described in JP-T-2023-543717, compounds described in Chinese Patent Publication No. 116102441, compounds described in JP 2023-150459, compounds described in JP 2023-167345, compounds described in Korean Patent Publication No. 10-2023-0061078, etc. can also be used.

[0197] Two or more chromatic colorants may be used in combination. When two or more chromatic colorants are used in combination, the combination of two or more chromatic colorants may form a black color. Examples of such combinations include the following embodiments (1) to (7). When the photocurable composition contains two or more chromatic colorants and exhibits black color through the combination of two or more chromatic colorants, the photocurable composition of the present invention can be preferably used as a photocurable composition for forming an infrared transmission filter. (1) An embodiment containing a red coloring material and a blue coloring material. (2) An embodiment containing a red coloring material, a blue coloring material, and a yellow coloring material. (3) An embodiment containing a red coloring material, a blue coloring material, a yellow coloring material, and a purple coloring material. (4) An embodiment containing a red color material, a blue color material, a yellow color material, a purple color material, and a green color material. (5) An embodiment containing a red coloring material, a blue coloring material, a yellow coloring material, and a green coloring material. (6) An embodiment containing a red coloring material, a blue coloring material, and a green coloring material. (7) An embodiment containing a yellow coloring material and a purple coloring material.

[0198] (white color material) Examples of white coloring materials include inorganic pigments such as titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, and zinc sulfide. The white coloring material can be the white pigments described in paragraphs 0040 to 0043 of WO 2022 / 085485.

[0199] (black color material) The black coloring material is not particularly limited, and known materials can be used. The black coloring material may be an inorganic black coloring material or an organic black coloring material. The black coloring material is preferably a pigment. In this specification, the black coloring material means a coloring material that exhibits absorption over the entire wavelength range of 400 to 700 nm.

[0200] Examples of inorganic black colorants include carbon black, titanium black, graphite, etc., with carbon black and titanium black being preferred, and titanium black being more preferred. Titanium black is a black particle containing titanium atoms, and low-order titanium oxide or titanium oxynitride is preferred. Titanium black can be the titanium black described in paragraph 0044 of International Publication No. 2022 / 085485. Zirconium nitride powder described in JP-A-2023-048173 can also be used as the inorganic black colorant.

[0201] Examples of organic black colorants include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds and perylene compounds being preferred. The organic black colorant may be a compound described in paragraph 0166 of International Publication No. 2022 / 065215. Furthermore, perylene black (such as Lumogen Black FK4280) described in paragraphs 0016 to 0020 of Japanese Patent Application Laid-Open No. 2017-226821, or a black azo pigment described in Japanese Patent Application Laid-Open No. 2022-121935 may also be used.

[0202] The black coloring material may be any of those described in pages 294 to 307 of the Journal of the Color Materials Association, Vol. 96, No. 9, 2023.

[0203] (Infrared absorbing colorant) The infrared absorbing colorant is preferably a compound having a maximum absorption wavelength longer than 700 nm. The infrared absorbing colorant is preferably a compound having a maximum absorption wavelength in the wavelength range of more than 700 nm to 1800 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of more than 700 nm to 1400 nm, even more preferably a compound having a maximum absorption wavelength in the wavelength range of more than 700 nm to 1200 nm, and particularly preferably a compound having a maximum absorption wavelength in the wavelength range of more than 700 nm to 1000 nm. In addition, the absorbance A of the infrared absorbing colorant at a wavelength of 500 nm is 1 and absorbance A at the maximum absorption wavelength 2 Ratio A 1 / A 2 is preferably 0.08 or less, more preferably 0.04 or less. The infrared absorbing colorant is preferably a pigment, more preferably an organic pigment.

[0204] Examples of infrared absorbing colorants include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterrylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, pyrromethene compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, dithiolene metal complexes, metal oxides, metal borides, etc. Specific examples of these include the compounds described in paragraph 0114 of WO 2022 / 065215.Examples of infrared absorbing colorants include the compounds described in paragraph 0121 of WO 2022 / 065215, squarylium compounds described in JP 2020-075959 A, copper complexes described in Korean Patent Publication No. 10-2019-0135217, croconic acid compounds described in JP 2021-195515 A, infrared absorbing dyes described in JP 2022-022070 A, croconium compounds described in WO 2019 / 021767, compounds described in JP 2019-127549 A, compounds described in WO 2022 / 059619, and compounds described in JP Compounds described in JP-A-2022-151682, squarylium compounds described in JP-A-2022-188858, compounds described in JP-A-2022-184710, compounds described in JP-A-2022-189736, squarylium compounds described in JP-A-2023-004570, squarylium compounds described in WO 2019 / 230660, squarylium compounds described in WO 2020 / compounds described in JP-A-2023-068643, diiminium compounds described in JP-A-2023-052770, squarylium compounds described in JP-A-2023-052770, phthalocyanine compounds described in Korean Patent Publication No. 10-2022-0163680, indigo monoboron complexes described in JP-A-2023-073064, phthalocyanine compounds described in JP-A-2023-066025, It is also possible to use the following compounds: phthalocyanine compounds described in JP 2020-041127 A; indigo compounds described in JP 2023-073064 A; indigo compounds described in Korean Patent Publication No. 10-2023-0016355 A; squarylium compounds described in WO 2019 / 230570 A; and diiminium compounds described in JP 2023-095824 A.

[0205] The content of the colorant in the total solid content of the photocurable composition is preferably 30 to 80% by mass, with the upper limit being preferably 70% by mass or less, and more preferably 65% ​​by mass or less, and the lower limit being preferably 35% by mass or more, and more preferably 40% by mass or more.

[0206] The content of the pigment in the total solid content of the photocurable composition is preferably 20 to 80% by mass. The upper limit is preferably 75% by mass or less, more preferably 65% ​​by mass or less, and even more preferably 63% by mass or less. The lower limit is preferably 25% by mass or more, more preferably 30% by mass or more, and even more preferably 35% by mass or more.

[0207] The content of the pigment in the coloring material is preferably 20 to 100% by mass, more preferably 50 to 100% by mass, and even more preferably 70 to 100% by mass.

[0208] <<Chain transfer agent>> The photocurable composition of the present invention preferably contains a chain transfer agent. According to this embodiment, the sensitivity can be further increased when exposed to light having a wavelength of 150 to 300 nm, such as KrF radiation. Examples of the chain transfer agent include thiol compounds, thiocarbonylthio compounds, and aromatic α-methylalkenyl dimers, and a thiol compound is preferred. Examples of the chain transfer agent include the compounds described in paragraphs 0093 to 0113 of WO 2019 / 188652.

[0209] The thiol compound used as a chain transfer agent is a compound having one or more thiol groups, preferably a compound having two or more thiol groups. The upper limit of the number of thiol groups contained in the thiol compound is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. The thiol compound is particularly preferably a compound having two thiol groups.

[0210] The thiol compound is preferably a compound represented by the following formula (SH-1). L S1 -(SH) n ...Formula (SH-1) (wherein SH represents a thiol group, L 1 represents an n-valent group, where n is an integer of 1 or more.

[0211] L in formula (SH-1) S1 The n-valent group represented by is a hydrocarbon group, a heterocyclic group, -O-, -S-, -NR S1 -, -CO-, -COO-, -OCO-, -SO2- or a group consisting of a combination thereof. S1 represents a hydrogen atom, an alkyl group, or an aryl group, with a hydrogen atom being preferred. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be cyclic or acyclic. The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The hydrocarbon group may have a substituent or may not have a substituent. The cyclic aliphatic hydrocarbon group and the aromatic hydrocarbon group may be a monocyclic or condensed ring. The heterocyclic group may be a monocyclic or condensed ring. The heterocyclic group is preferably a 5- or 6-membered ring. The heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. Examples of heteroatoms constituting the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom. L 1 The number of carbon atoms constituting the group is preferably 3 to 100, and more preferably 6 to 50.

[0212] In formula (SH-1), n ​​represents an integer of 1 or more. The upper limit of n is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. The lower limit of n is preferably 2 or more.

[0213] Specific examples of thiol compounds include the compounds described in paragraphs 0100 to 0103 of WO 2019 / 188652. Commercially available thiol compounds include PEMP (manufactured by SC Organic Chemical Co., Ltd.), Suncera M (manufactured by Sanshin Chemical Industry Co., Ltd.), Karenz MTBD1, Karenz MTPE1, Karenz MTNR1, and Karenz MTTPMB (all manufactured by Resonac Corporation). The thiol compounds described in JP 2020-109068 A can also be used as chain transfer agents.

[0214] The molecular weight of the chain transfer agent is preferably at least 200. The upper limit is preferably at most 1000, more preferably at most 800, and even more preferably at most 600, because this allows the SH valence per weight to be increased.

[0215] The content of the chain transfer agent in the total solid content of the photocurable composition is preferably 0.001 to 5% by mass. The upper limit is preferably 3% by mass or less, more preferably 1% by mass or less. The lower limit is preferably 0.05% by mass or more, more preferably 0.01% by mass or more. Only one type of chain transfer agent may be used, or two or more types may be used. When two or more types are used, the total amount thereof preferably falls within the above range.

[0216] <<Amine compounds>> The curable compound of the present invention preferably contains an amine compound. According to this embodiment, the efficiency of generating radicals from the photopolymerization initiator during exposure can be further improved, and the polymerization reaction of the polymerizable compound can be further promoted.

[0217] The molecular weight of the amine compound is preferably 100 to 1000. The upper limit is preferably 800 or less, more preferably 500 or less. The lower limit is preferably 150 or more, more preferably 200 or more.

[0218] The amine compound is preferably a compound having 1 to 8 amino groups in one molecule, more preferably a compound having 1 to 4 amino groups, and even more preferably a compound having 1 to 2 amino groups.

[0219] The amine compound is preferably colorless. That is, the molar absorption coefficient of the amine compound at wavelengths of 400 to 700 nm is 200 L mol -1 ·cm -1 Preferably less than 100 L mol -1 ·cm -1 It is more preferable that it is less than 10 ...

[0220] The amine compound may be a primary to tertiary amine, but is preferably a tertiary amine.

[0221] In the amine compound, the three groups connected to the nitrogen atom are preferably selected from a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group, and among these, a combination of an alkyl group and an aryl group is most preferred.

[0222] The amine compound preferably has any one of a carboxy group, a sulfonic acid group, a phosphoric acid group, and a hydroxy group, for the purpose of improving alkaline developability and reducing residues.

[0223] The amine compound is preferably a compound represented by formula (B-1). [ka] In formula (B-1), R a and R b each independently represents a monovalent organic group having 1 to 10 carbon atoms which may contain a heteroatom; R c represents a monovalent organic group which may contain a heteroatom, and m represents an integer of 0 to 5.

[0224] R a , R b and R c The organic group represented by the formula (I) includes an alkyl group, an aryl group, and a heteroaryl group, and is preferably an alkyl group. The alkyl group, the aryl group, and the heteroaryl group may have a substituent. Examples of the substituent include a carboxy group, a sulfonic acid group, a phosphoric acid group, and a hydroxy group, and is preferably a hydroxy group. m represents an integer of 0 to 5, preferably an integer of 0 to 3, more preferably 0 or 1, and even more preferably 0.

[0225] Specific examples of the amine compound include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, and p-dimethylaminocinnamylidene. Danone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-a Examples of the methylaminobenzoic acid include cetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, and 2-(p-dimethylaminobenzoyl)styrene. These may be used alone or in combination of, for example, 2 to 5 types.

[0226] The content of the amine compound is preferably 5 to 1000 parts by mass relative to 100 parts by mass of the specific compound. The upper limit is preferably 500 parts by mass or less, more preferably 200 parts by mass or less. The lower limit is preferably 10 parts by mass or more, more preferably 20 parts by mass or more. Only one type of amine compound may be used, or two or more types may be used. When two or more types are used, the total amount thereof preferably falls within the above range.

[0227] <<Acid anhydride>> The photocurable composition of the present invention may contain an acid anhydride. Even if a specific compound is hydrolyzed to a free OH form, the presence of the acid anhydride allows it to be restored to a photodecomposable oxime compound again. This makes it possible to suppress a decrease in sensitivity over time.

[0228] Examples of the acid anhydride include carboxylic acid anhydrides and sulfonic acid anhydrides, and carboxylic acid anhydrides are preferred.Specific examples of the acid anhydride include acetic anhydride, propionic acid anhydride, isobutyric acid anhydride, butyric acid anhydride, 2-methylbutyric acid anhydride, pivalic acid anhydride, isovaleric acid anhydride, valeric acid anhydride, 2-methylvaleric acid anhydride, 3-methylvaleric acid anhydride, 4-methylvaleric acid anhydride, hexanoic acid anhydride, 2-methylhexanoic acid anhydride, 3-methylhexanoic acid anhydride, 4-methylhexanoic acid anhydride, 5-methylhexanoic acid anhydride, heptanoic acid anhydride, 2-methylheptanoic acid anhydride, 3-methylheptanoic acid anhydride, 4-methylheptanoic acid anhydride, 5-methylheptanoic acid anhydride, Aliphatic carboxylic acid anhydrides such as 6-methylheptanoic anhydride, 3-phenylpropionic anhydride, phenylacetic anhydride, methacrylic anhydride, acrylic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride, and glutaric anhydride; aromatic carboxylic acid anhydrides such as benzoic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride; and sulfocarboxylic acid anhydrides such as 2-sulfobenzoic anhydride.

[0229] The content of the acid anhydride is preferably 1 to 200 parts by mass relative to 100 parts by mass of the specific compound. The upper limit is preferably 100 parts by mass or less, more preferably 50 parts by mass or less. The lower limit is preferably 5 parts by mass or more, more preferably 10 parts by mass or more. Only one type of acid anhydride may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.

[0230] <<Pigment derivatives>> The photocurable composition of the present invention may contain a pigment derivative. The pigment derivative is used, for example, as a dispersing aid. A dispersing aid is a material that enhances the dispersibility of a coloring material such as a pigment in the photocurable composition.

[0231] Examples of the pigment derivative include compounds having at least one structure selected from the group consisting of a dye structure and a triazine structure, and an acid group or a basic group.

[0232] Examples of the dye structure include a quinoline dye structure, a benzimidazolone dye structure, a benzisoindole dye structure, a benzothiazole dye structure, an iminium dye structure, a squarylium dye structure, a croconium dye structure, an oxonol dye structure, a pyrrolopyrrole dye structure, a diketopyrrolopyrrole dye structure, an azo dye structure, an azomethine dye structure, a phthalocyanine dye structure, a naphthalocyanine dye structure, an anthraquinone dye structure, a quinacridone dye structure, a dioxazine dye structure, a perinone dye structure, a perylene dye structure, a thiazineindigo dye structure, a thioindigo dye structure, an isoindoline dye structure, an isoindolinone dye structure, a quinophthalone dye structure, a dithiol dye structure, a triarylmethane dye structure, and a pyrromethene dye structure.

[0233] Examples of the acid group possessed by the pigment derivative include a carboxy group, a sulfo group, a phosphate group, a boronic acid group, an imidic acid group, and salts thereof. Examples of the atom or atomic group constituting the salt include an alkali metal ion (Li + , Na + , K.+ etc.), alkaline earth metal ions (Ca 2+ , Mg 2+ Examples of the imide acid group include -SO2NHSO2R X1 , -CONHSO2R X2 , -CONHCOR X3 or -SO2NHCOR X4 A group represented by the formula: -SO2NHSO2R is preferred. X1 , -CONHSO2R X2 , or -SO2NHCOR X4 A group represented by the formula: -SO2NHSO2R is more preferred. X1 or -CONHSO2R X2 is more preferred. X1 ~R X4 R each independently represents an alkyl group or an aryl group. X1 ~R X4 The alkyl group and aryl group represented by R may have a substituent. The substituent is preferably a halogen atom, more preferably a fluorine atom. X1 ~R X4 are each independently preferably an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom, and more preferably an alkyl group containing a fluorine atom. The number of carbon atoms in the alkyl group containing a fluorine atom is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. The number of carbon atoms in the aryl group containing a fluorine atom is preferably 6 to 20, more preferably 6 to 12, and even more preferably 6.

[0234] Examples of basic groups possessed by the pigment derivative include amino groups, pyridinyl groups and their salts, ammonium salts, and phthalimidomethyl groups. Examples of atoms or atomic groups that constitute the salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.

[0235] The amino group is -NR x11 R x12and a cyclic amino group.

[0236] -NR x11 R x12 In the group represented by x11 and R x12 are each independently a hydrogen atom, an alkyl group, or an aryl group, and are preferably an alkyl group. That is, the amino group is preferably a dialkylamino group. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have a substituent. An example of the substituent is the substituent T. The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20, and even more preferably 6 to 12. The aryl group may have a substituent. An example of the substituent is the substituent T.

[0237] Examples of the cyclic amino group include a pyrrolidine group, a piperidine group, a piperazine group, a morpholine group, etc. These groups may further have a substituent.

[0238] Pigment derivatives with excellent visible transparency (hereinafter referred to as transparent pigment derivatives) can also be used. The maximum molar absorption coefficient (εmax) of transparent pigment derivatives in the wavelength range of 400 to 700 nm is 3000 L·mol -1 ·cm -1 It is preferable that the concentration is less than 1000 L·mol -1 ·cm -1 It is more preferable that it is less than 100 L·mol -1 ·cm -1 The lower limit of εmax is, for example, 1 L mol -1 ·cm -1 is greater than or equal to 10 L mol -1 ·cm -1 More than that is fine.

[0239] Specific examples of pigment derivatives include the compounds described in paragraph 0124 of WO 2022 / 085485, the benzimidazolone compounds or salts thereof described in JP 2018-168244 A, the compounds having an isoindoline skeleton described in general formula (1) of Japanese Patent No. 6996282 A, the compounds described in JP 2019-172968 A, and the compounds described in Chinese Patent Application Publication No. 115124889 A.

[0240] The content of the pigment derivative is preferably 1 to 30 parts by mass, and more preferably 3 to 20 parts by mass, relative to 100 parts by mass of the pigment. The total content of the pigment derivative and colorant is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more, based on the total solid content of the photocurable composition. The upper limit is preferably 80% by mass or less, and more preferably 70% by mass or less. Only one type of pigment derivative may be used, or two or more types may be used in combination.

[0241] <<Polyalkyleneimine>> The photocurable composition of the present invention may also contain a polyalkyleneimine. The polyalkyleneimine is used, for example, as a dispersing aid for pigments. A dispersing aid is a material for improving the dispersibility of coloring materials such as pigments in a photocurable composition. The polyalkyleneimine is a polymer obtained by ring-opening polymerization of an alkyleneimine. The polyalkyleneimine is preferably a polymer having a branched structure containing a primary amino group, a secondary amino group, and a tertiary amino group. The alkyleneimine preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, even more preferably 2 or 3 carbon atoms, and particularly preferably 2 carbon atoms.

[0242] The molecular weight of the polyalkyleneimine is preferably 200 or more, more preferably 250 or more. The upper limit is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, and particularly preferably 2,000 or less. Regarding the molecular weight value of the polyalkyleneimine, if the molecular weight can be calculated from the structural formula, the molecular weight of the polyalkyleneimine is the value calculated from the structural formula. On the other hand, if the molecular weight of the specific amine compound cannot be calculated from the structural formula or calculation is difficult, the number average molecular weight value measured by boiling point elevation method is used. If the number average molecular weight cannot be measured by boiling point elevation method or measurement is difficult, the number average molecular weight value measured by viscosity method is used. If the number average molecular weight cannot be measured by viscosity method or measurement by viscosity method is difficult, the number average molecular weight value measured in terms of polystyrene by GPC (gel permeation chromatography) method is used.

[0243] 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.

[0244] Specific examples of alkyleneimines include ethyleneimine, propyleneimine, 1,2-butyleneimine, and 2,3-butyleneimine, with ethyleneimine or propyleneimine being preferred, and ethyleneimine being more preferred. The polyalkyleneimine is particularly preferably polyethyleneimine. Furthermore, the polyethyleneimine preferably contains primary amino groups in an amount of 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, based on the total of primary amino groups, secondary amino groups, and tertiary amino groups. Commercially available polyethyleneimines include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000 (all manufactured by Nippon Shokubai Co., Ltd.).

[0245] The content of the polyalkyleneimine in the total solid content of the photocurable composition is preferably 0.1 to 5% by mass. The lower limit is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is preferably 4.5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less. The content of the polyalkyleneimine is preferably 0.5 to 20 parts by mass per 100 parts by mass of the pigment. The lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more. The upper limit is preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less. Only one type of polyalkyleneimine may be used, or two or more types may be used. When two or more types are used, the total amount thereof is preferably within the above range.

[0246] <<Compounds with cyclic ether groups>> The photocurable composition of the present invention may contain a compound having a cyclic ether group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group. The epoxy group may be an alicyclic epoxy group. The alicyclic epoxy group refers to a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are condensed. The compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter also referred to as an epoxy compound). Examples of epoxy compounds include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups are preferred. The epoxy compound is preferably a compound having 1 to 100 epoxy groups in one molecule. The upper limit of the number of epoxy groups contained in the epoxy compound can be, for example, 10 or less, or 5 or less. The lower limit of the number of epoxy groups contained in the epoxy compound is preferably 2 or more.

[0247] Examples of compounds having a cyclic ether group include the compounds described in paragraphs 0034 to 0036 of JP 2013-011869 A, paragraphs 0147 to 0156 of JP 2014-043556 A, and paragraphs 0085 to 0092 of JP 2014-089408 A, the compounds described in JP 2017-179172 A, the xanthene-type epoxy resins described in JP 2021-195421 A, and the xanthene-type epoxy resins described in JP 2021-195422 A can be used.

[0248] The compound having a cyclic ether group may be a low molecular weight compound (for example, a molecular weight of less than 2000, or even less than 1000) or a high molecular weight compound (macromolecule) (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more). The weight average molecular weight of the compound having a cyclic ether group is preferably 200 to 100,000, and more preferably 500 to 50,000. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.

[0249] Commercially available compounds having a cyclic ether group include, for example, EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, and G-01758 (all manufactured by NOF Corporation, epoxy group-containing polymers).

[0250] The content of the compound having a cyclic ether group in the total solid content of the photocurable composition is preferably 0.1 to 20% by mass. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less. Only one type of compound having a cyclic ether group may be used, or two or more types may be used. When two or more types are used, the total amount thereof preferably falls within the above range.

[0251] <<Ultraviolet absorber>> The photocurable composition of the present invention may contain an ultraviolet absorber. Examples of ultraviolet absorbers include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, triazine compounds, and dibenzoyl compounds. Specific examples of such compounds include the compound described in paragraph 0179 of International Publication No. 2022 / 085485, the reactive triazine ultraviolet absorber described in Japanese Patent Application Laid-Open No. 2021-178918, the ultraviolet absorber described in Japanese Patent Application Laid-Open No. 2022-007884, the compound described in Korean Patent Publication No. 10-2022-0014454, and the compound described in Japanese Patent Application Laid-Open No. 2023-013321. The content of the ultraviolet absorber in the total solid content of the photocurable composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. The ultraviolet absorbent may be used alone or in combination of two or more kinds. When two or more kinds are used, the total amount thereof is preferably in the above range.

[0252] <<Polymerization inhibitor>> The photocurable composition of the present invention may contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), and N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.). Among these, p-methoxyphenol is preferred. The content of the polymerization inhibitor in the total solid content of the photocurable composition is preferably 0.0001 to 5 mass%. One type of polymerization inhibitor may be used alone, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.

[0253] <<Silane coupling agent>> The photocurable composition of the present invention may contain a silane coupling agent. Examples of the silane coupling agent include silane compounds having a hydrolyzable group, preferably a silane compound having both a hydrolyzable group and another functional group. The hydrolyzable group refers to a substituent directly bonded to a silicon atom that can form a siloxane bond through at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group, with an alkoxy group being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of functional groups other than the hydrolyzable group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, a thiol group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group, an isocyanate group, and a phenyl group, with an amino group, a (meth)acryloyl group, and an epoxy group being preferred. Specific examples of the silane coupling agent include the compound described in paragraph 0177 of WO 2022 / 085485 and the compound described in JP 2019-183020 A. The content of the silane coupling agent in the total solid content of the photocurable composition is preferably 0.1 to 15% by mass. The upper limit is preferably 10% by mass or less, and more preferably 5% by mass or less. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. Only one type of silane coupling agent may be used, or two or more types may be used. When two or more types are used, the total amount preferably falls within the above range.

[0254] <<Surfactants>> The photocurable composition of the present invention may contain a surfactant. Various surfactants can be used as the surfactant, such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, or a silicone-based surfactant. The surfactant is preferably a silicone-based surfactant or a fluorine-based surfactant, and more preferably a silicone-based surfactant. For details of the surfactant, see paragraphs 0238 to 0245 of WO 2015 / 166779, the contents of which are incorporated herein by reference.

[0255] As the fluorine-based surfactant, the compounds described in paragraphs 0167 to 0173 of WO 2022 / 085485 can be used.

[0256] Examples of nonionic surfactants include the compounds described in paragraph 0174 of WO 2022 / 085485.

[0257] Examples of silicone surfactants include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, and SF 8419 OIL (manufactured by Dow-Toray Industries, Inc.), TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (manufactured by Momentive Performance Materials, Inc.), KP-341, KF-6000, KF-6001, KF-6002, and KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd.), and BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, and BYK-UV3510 (manufactured by BYK-Chemie). Compounds having the following structure can also be used as silicone surfactants. [ka]

[0258] The content of the surfactant in the total solid content of the photocurable composition is preferably 0.001 to 5.0% by mass, more preferably 0.005 to 3.0% by mass. The surfactant may be one type or two or more types. When two or more types are used, the total amount preferably falls within the above range.

[0259] <<Antioxidants>> The photocurable composition of the present invention may contain an antioxidant. Examples of antioxidants include phenolic antioxidants, amine antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Examples of phenolic antioxidants include hindered phenol compounds. The phenolic antioxidant is preferably a compound having a substituent at the position adjacent to the phenolic hydroxy group (ortho position). The substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms. The antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, ethyl bis(2,4-di-tert-butyl-6-methylphenyl)phosphite, and tris(2,4-di-tert-butylphenyl)phosphite. Commercially available antioxidants include, for example, ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-60G, ADK STAB AO-80, and ADK STAB AO-330 (all manufactured by ADEKA Corporation), and JP-650 (manufactured by Johoku Chemical Industry Co., Ltd.). Antioxidants that can be used include compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, compounds described in International Publication No. WO 2017 / 006600, compounds described in International Publication No. WO 2017 / 164024, and compounds described in Korean Patent Publication No. 10-2019-0059371. The content of the antioxidant in the total solid content of the photocurable composition is preferably 0.01 to 20 mass %, more preferably 0.3 to 15 mass %. Only one antioxidant may be used, or two or more antioxidants may be used. When two or more antioxidants are used, the total amount thereof is preferably within the above range.

[0260] <<Other ingredients>> The photocurable composition of the present invention may contain, as needed, sensitizers, plasticizers, and other auxiliaries (for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling promoters, fragrances, surface tension modifiers, chain transfer agents, etc.). By appropriately incorporating these components, properties such as film physical properties can be adjusted. As these components, the compounds described in paragraph 0182 of WO 2022 / 085485 can be used.

[0261] The photocurable composition of the present invention may contain a metal oxide to adjust the refractive index of the resulting film. Examples of metal oxides include TiO2, ZrO2, Al2O3, and SiO2. The primary particle size of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, and even more preferably 5 to 50 nm. The metal oxide may have a core-shell structure. In this case, the core may be hollow.

[0262] The photocurable composition of the present invention may contain a light resistance improver. Examples of the light resistance improver include the compounds described in paragraph 0183 of WO 2022 / 085485.

[0263] It is also preferred that the photocurable composition of the present invention is substantially free of terephthalic acid esters. Here, "substantially free" means that the content of terephthalic acid esters in the total amount of the photocurable composition is 1000 ppb by mass or less, more preferably 100 ppb by mass or less, and particularly preferably zero.

[0264] In view of environmental regulations, the photocurable composition of the present invention preferably has a melamine content of 10,000 ppm by mass or less.

[0265] The photocurable composition of the present invention preferably has a free metal content of 100 ppm or less, more preferably 50 ppm or less. The free halogen content is preferably 100 ppm or less, more preferably 50 ppm or less. Methods for reducing the free metals and halogens in the photocurable composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification with ion-exchange resins.

[0266] From the viewpoint of environmental regulations, the use of perfluoroalkyl sulfonic acids and their salts, and perfluoroalkyl carboxylic acids and their salts may be restricted. When the content of the above-mentioned compounds in the photocurable composition of the present invention is reduced, the content of perfluoroalkyl sulfonic acids (particularly perfluoroalkyl sulfonic acids having a perfluoroalkyl group with 6 to 8 carbon atoms) and their salts, and perfluoroalkyl carboxylic acids (particularly perfluoroalkyl carboxylic acids having a perfluoroalkyl group with 6 to 8 carbon atoms) and their salts is preferably in the range of 0.01 ppb to 1000 ppb, more preferably in the range of 0.05 ppb to 500 ppb, and even more preferably in the range of 0.1 ppb to 300 ppb, based on the total solids content of the photocurable composition. The photocurable composition of the present invention may be substantially free of perfluoroalkyl sulfonic acids and their salts, and perfluoroalkyl carboxylic acids and their salts. For example, by using a compound that can replace perfluoroalkyl sulfonic acid and its salt, and a compound that can replace perfluoroalkyl carboxylic acid and its salt, a photocurable composition that is substantially free of perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt may be selected. Examples of compounds that can replace restricted compounds include compounds that are exempt from restrictions due to differences in the number of carbon atoms in the perfluoroalkyl group. However, the above does not preclude the use of perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt. The photocurable composition of the present invention may contain perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt, within the maximum allowable range.

[0267] The water content of the photocurable composition of the present invention is usually 3% by mass or less, preferably 0.01 to 1.5% by mass, and more preferably 0.1 to 1.0% by mass. The water content can be measured by the Karl Fischer method.

[0268] The photocurable composition of the present invention can be used by adjusting its viscosity for the purposes of adjusting the film surface state (flatness, etc.), film thickness, etc. The viscosity value can be selected appropriately as needed, but is preferably 0.3 mPa·s to 50 mPa·s, and more preferably 0.5 mPa·s to 20 mPa·s at 25°C. The viscosity can be measured, for example, using a cone-plate type viscometer at a temperature adjusted to 25°C.

[0269] <<Containment Container>> The container for storing the photocurable composition is not particularly limited, and a known container can be used. In addition, the container described in paragraph 0187 of WO 2022 / 085485 can be used as the container.

[0270] <Method for preparing photocurable composition> The photocurable composition of the present invention can be prepared by mixing the above-mentioned components. When preparing the photocurable composition, all components may be simultaneously dissolved and / or dispersed in a solvent to prepare the photocurable composition, or, if necessary, each component may be prepared as two or more appropriate solutions or dispersions, which are mixed at the time of use (application) to prepare the photocurable composition.

[0271] The preparation of the photocurable composition preferably includes a process for dispersing the pigment. In the process for dispersing the pigment, mechanical forces used to disperse the pigment include compression, squeezing, impact, shear, and cavitation. Specific examples of these processes include a bead mill, a sand mill, a roll mill, a ball mill, a paint shaker, a microfluidizer, a high-speed impeller, a sand grinder, a flow jet mixer, high-pressure wet atomization, and ultrasonic dispersion. Furthermore, when grinding the pigment in a sand mill (bead mill), it is preferable to use small-diameter beads, increase the bead packing ratio, or otherwise increase the grinding efficiency under such conditions. Furthermore, it is preferable to remove coarse particles after the grinding process by filtration, centrifugation, or the like. In addition, the process and disperser for dispersing pigments can be suitably used, as described in "Dispersion Technology Encyclopedia," published by Joho Kiko Co., Ltd., July 15, 2005, or "Dispersion Technology and Industrial Applications Focused on Suspension (Solid / Liquid Dispersion Systems) - Comprehensive Data Collection," published by the Management Development Center Publishing Department, October 10, 1978, and in paragraph 0022 of JP 2015-157893 A. The process for dispersing pigments can also include a salt milling step to refine the particles. For details on the materials, equipment, and processing conditions used in the salt milling step, see, for example, JP 2015-194521 A and JP 2012-046629 A. Examples of materials for beads used in dispersion include zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, and glass. The beads may also be made of an inorganic compound having a Mohs hardness of at least 2. The photocurable composition may contain 1 to 10,000 ppm of the above beads.

[0272] When preparing the photocurable composition, it is preferable to filter the photocurable composition with a filter for the purpose of removing foreign matter, reducing defects, etc. Examples of the types of filters and filtration methods used for filtration include the filters and filtration methods described in paragraphs 0196 to 0199 of WO 2022 / 085485.

[0273] <Membrane> The film of the present invention is obtained by curing the above-described photocurable composition of the present invention. The film of the present invention can be used in optical filters such as color filters, infrared transmission filters, and infrared cut filters.

[0274] The thickness of the film of the present invention can be adjusted appropriately depending on the purpose. For example, the thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

[0275] When the film of the present invention is used as a color filter, the film of the present invention preferably has a green, red, blue, cyan, magenta, or yellow hue. The film of the present invention can also be preferably used as a color pixel of a color filter. Examples of the color pixel include a red pixel, a green pixel, a blue pixel, a magenta pixel, a cyan pixel, and a yellow pixel.

[0276] <Pixel manufacturing method> A method for manufacturing pixels using the photocurable composition of the present invention will be described. The method for manufacturing pixels includes the steps of forming a composition layer on a support using the photocurable composition of the present invention, exposing the composition layer to light in a pattern, and developing and removing the unexposed areas of the composition layer. If necessary, a step of drying the composition layer (pre-baking step) and a step of heat-treating the developed pattern (pixels) (post-baking step) may also be provided.

[0277] In the step of forming a composition layer, a composition layer is formed on a support using the photocurable composition of the present invention. The support is not particularly limited and can be appropriately selected depending on the application. Examples include a glass substrate and a silicon substrate, with a silicon substrate being preferred. The silicon substrate may also be formed with a charge-coupled device (CCD), a complementary metal-oxide semiconductor (CMOS), a transparent conductive film, or the like. A black matrix is ​​sometimes formed on the silicon substrate to isolate each pixel. The silicon substrate may also be provided with an underlayer to improve adhesion with an upper layer, prevent diffusion of substances, or flatten the substrate surface. The surface contact angle of the underlayer is preferably 20 to 70° when measured with diiodomethane. It is also preferably 30 to 80° when measured with water.

[0278] Known methods can be used as the coating method for the photocurable composition. For example, a dropping method (drop casting); a slit coating method; a spray method; a roll coating method; a spin coating method; a casting coating method; a slit and spin method; a pre-wet method (for example, a method described in JP-A-2009-145395); various printing methods such as inkjet (for example, on-demand method, piezo method, thermal method), ejection printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing; a transfer method using a mold or the like; a nanoimprint method, etc. can also be used. In addition, the coating method described in paragraph 0207 of WO 2022 / 085485 can also be used.

[0279] The composition layer formed on the support may be dried (prebaked). When a film is produced by a low-temperature process, prebaking may not be performed. When prebaking is performed, the prebaking temperature is preferably 150°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower. The lower limit can be, for example, 50°C or higher, or can also be 80°C or higher. The prebaking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and even more preferably 80 to 220 seconds. Prebaking can be performed using a hot plate, an oven, or the like.

[0280] Next, the composition layer is exposed to light in a pattern (exposure step). For example, the composition layer can be exposed to light in a pattern by using a stepper exposure machine, a scanner exposure machine, or the like, through a mask having a predetermined mask pattern. This allows the exposed portions to be cured.

[0281] Examples of radiation (light) that can be used for exposure include g-rays and i-rays. Light with a wavelength of 150 to 300 nm can also be used. Examples of light with a wavelength of 150 to 300 nm include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm), with KrF rays (wavelength 248 nm) being preferred. Light with a wavelength of 150 to 300 nm is preferably excimer laser light with a wavelength of 150 to 300 nm. A long-wavelength light source of 300 nm or more can also be used for exposure.

[0282] In the exposure step, the composition layer is preferably exposed in a pattern by irradiating it with light having a wavelength of 150 to 300 nm (preferably excimer laser light having a wavelength of 150 to 300 nm).

[0283] The exposure may be performed by continuous irradiation with light or by pulsed irradiation (pulse exposure), which is an exposure method in which light is applied and paused repeatedly in short cycles (for example, on the order of milliseconds or less).

[0284] The irradiation amount (exposure amount) is, for example, 0.03 to 2.5 J / cm 2 is preferable, and 0.05 to 1.0 J / cm 2 The oxygen concentration during exposure can be appropriately selected. In addition to being performed in the atmosphere, exposure may be performed in a low-oxygen atmosphere with an oxygen concentration of 19% by volume or less (e.g., 15% by volume, 5% by volume, or substantially oxygen-free), or in a high-oxygen atmosphere with an oxygen concentration of more than 21% by volume (e.g., 22% by volume, 30% by volume, or 50% by volume). The exposure illuminance can be appropriately set, and is usually 1000 W / m 2~100,000W / m 2 (e.g., 5000W / m 2 , 15000W / m 2 , or 35,000 W / m 2 The oxygen concentration and exposure illuminance may be appropriately combined. For example, an oxygen concentration of 10% by volume and an illuminance of 10,000 W / m 2 , oxygen concentration 35% by volume, illuminance 20000W / m 2 etc.

[0285] Next, the unexposed portions of the composition layer are developed and removed to form a pattern (pixels). The unexposed portions of the composition layer can be developed and removed using a developer. As a result, the unexposed portions of the composition layer in the exposure step are dissolved into the developer, leaving only the photocured portions. The temperature of the developer is preferably, for example, 20 to 30°C. The development time is preferably 20 to 180 seconds. In addition, to improve residue removal, the process of shaking off the developer every 60 seconds and then supplying fresh developer may be repeated several times.

[0286] Examples of the developer include organic solvents and alkaline developers, and alkaline developers are preferably used. Regarding the developer and the washing (rinsing) method after development, the developer and washing method described in paragraph 0214 of WO 2022 / 085485 can be used.

[0287] After development and drying, it is preferable to perform additional exposure treatment or heating treatment (post-baking). The additional exposure treatment or post-baking is a post-development curing treatment to ensure complete curing. The heating temperature in post-baking is, for example, preferably 100 to 300°C, more preferably 200 to 270°C. Post-baking can be performed continuously or batchwise using a heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater to heat the developed film to the above conditions. When additional exposure treatment is performed, it is preferable that the light used for exposure has a wavelength of 400 nm or less. The additional exposure treatment may also be performed by the method described in Korean Patent Publication No. 10-2017-0122130.

[0288] <Optical filters> The optical filter of the present invention includes the above-described film of the present invention. Types of optical filters include color filters, infrared cut filters, and infrared transmission filters, and color filters are preferred. The color filter preferably has the film of the present invention as its pixel, and more preferably has the film of the present invention as its color pixel.

[0289] The optical filter may have a protective layer provided on the surface of the film of the present invention. By providing a protective layer, various functions can be imparted, such as oxygen blocking, low reflectivity, hydrophilicity / hydrophobicity, and blocking of light of specific wavelengths (ultraviolet rays, infrared rays, etc.). The thickness of the protective layer is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm. Methods for forming the protective layer include a method of applying a resin composition for forming the protective layer, a chemical vapor deposition method, and a method of attaching a molded resin with an adhesive. Components constituting the protective layer include (meth)acrylic resins, enethiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, polyol resins, polyvinylidene chloride resins, melamine resins, urethane resins, aramid resins, polyamide resins, alkyd resins, epoxy resins, modified silicone resins, fluororesins, polyacrylonitrile resins, cellulose resins, Si, C, W, Al2O3, Mo, SiO2, and Si2N4, and the like, and the protective layer may contain two or more of these components. For example, in the case of a protective layer intended to block oxygen, the protective layer preferably contains a polyol resin, SiO2, and Si2N4. Furthermore, in the case of a protective layer intended to reduce reflectivity, the protective layer preferably contains a (meth)acrylic resin and a fluororesin.

[0290] When forming a protective layer by applying a resin composition, known methods such as spin coating, casting, screen printing, and inkjet printing can be used as the method for applying the resin composition. Known organic solvents (e.g., propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.) can be used as the organic solvent contained in the resin composition. When forming the protective layer by chemical vapor deposition, known chemical vapor deposition methods (thermal chemical vapor deposition, plasma chemical vapor deposition, photochemical vapor deposition) can be used as the chemical vapor deposition method.

[0291] The protective layer may contain additives such as organic or inorganic fine particles, absorbers of light of specific wavelengths (e.g., ultraviolet light, infrared light, etc.), refractive index adjusters, antioxidants, adhesives, and surfactants, as needed. Examples of organic or inorganic fine particles include polymeric fine particles (e.g., silicone resin fine particles, polystyrene fine particles, and melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride, magnesium fluoride, hollow silica, silica, calcium carbonate, and barium sulfate. Known absorbers of specific wavelengths can be used. The content of these additives can be adjusted as needed, but is preferably 0.1 to 70% by mass, and more preferably 1 to 60% by mass, of the total mass of the protective layer.

[0292] As the protective layer, the protective layers described in paragraphs 0073 to 0092 of JP-A No. 2017-151176 can also be used.

[0293] The optical filter may have a structure in which each pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern.

[0294] <Solid-state imaging element> The solid-state imaging device of the present invention has the above-described film of the present invention. The configuration of the solid-state imaging device is not particularly limited as long as it has the film of the present invention and functions as a solid-state imaging device, but examples thereof include the following configurations.

[0295] The substrate includes a plurality of photodiodes constituting the light receiving area of ​​a solid-state imaging device (such as a CCD (charge-coupled device) image sensor or a CMOS (complementary metal-oxide semiconductor) image sensor) and transfer electrodes made of polysilicon or the like. A light-shielding film is formed on the photodiodes and transfer electrodes, with only the light-receiving portions of the photodiodes exposed. A device protection film made of silicon nitride or the like is formed on the light-shielding film so as to cover the entire light-shielding film and the light-receiving portions of the photodiodes. A color filter is also provided on the device protection film. Furthermore, the device protection film may include a light-collecting means (e.g., a microlens, etc.; the same applies hereinafter) below the color filter (closer to the substrate), or on the color filter. The color filter may have a structure in which each color pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern. In this case, the partition walls preferably have a lower refractive index than the color pixels. Examples of imaging devices having such a structure include those described in JP 2012-227478 A, JP 2014-179577 A, and WO 2018 / 043654 A. Furthermore, as shown in JP 2019-211559 A, an ultraviolet absorbing layer may be provided within the structure of the solid-state imaging element to improve light resistance. An imaging device including the solid-state imaging element of the present invention can be used in digital cameras, electronic devices with imaging functions (such as mobile phones), as well as in-vehicle cameras and surveillance cameras.

[0296] <Image display device> The image display device of the present invention has the above-described film of the present invention. Examples of image display devices include liquid crystal display devices and organic electroluminescence display devices. Definitions of image display devices and details of each image display device are described, for example, in "Electronic Display Devices" (written by Akio Sasaki, published by Kogyo Chosakai Co., Ltd. in 1990) and "Display Devices" (written by Nobuaki Ibuki, published by Sangyo Tosho Co., Ltd. in 1989). Liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology" (edited by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994). There are no particular limitations on the liquid crystal display device to which the present invention can be applied, and the present invention can be applied to various types of liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology."

[0297] <Photopolymerization initiator> The photopolymerization initiator of the present invention contains the compound represented by the above formula (1). [Example]

[0298] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, treatment details, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In the structural formulas shown below, Me is a methyl group, and Ph is a phenyl group.

[0299] <Synthesis example> (Synthesis Example 1) Synthesis of Compound A-1 A three-neck flask was charged with 20.0 g of benzothiophene and 100 mL of chlorobenzene and cooled to 0°C. To this was added 21.8 g of aluminum chloride and 31.3 g of 2-chloro-4-methylpyrimidine-5-carbonyl chloride (CAS Registry Number: 188781-13-7). The reaction mixture was stirred at room temperature (25°C, hereinafter the same) for 4 hours, added to 100 mL of 3 M hydrochloric acid cooled to 0°C, and extracted with 300 mL of ethyl acetate. The resulting organic layer was washed with water, saturated aqueous sodium bicarbonate, and saturated brine. This organic layer was dried over anhydrous sodium sulfate, and the solvent was then distilled off. The resulting solid was stirred in 200 mL of methanol for 3 hours, then filtered and washed with methanol to obtain 35.8 g of Intermediate A-1a. [ka]

[0300] A three-neck flask was charged with 20.0 g of indazole and 150 mL of chlorobenzene and cooled to 0°C under a nitrogen atmosphere. To this was added 48.5 g of tin tetrachloride and 21.0 g of pentanoyl chloride, followed by dropwise addition. The reaction mixture was stirred at room temperature for 4 hours, then added to 250 mL of 3 M hydrochloric acid cooled to 0°C and extracted with 500 mL of ethyl acetate. The resulting organic layer was washed with water, saturated aqueous sodium bicarbonate, and saturated brine. The organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and the mixture was purified by silica gel chromatography to yield 14.2 g of Intermediate A-1b. [ka]

[0301] 5.00 g of Intermediate A-1a and 3.85 g of Intermediate A-1b were placed in a three-neck flask and dissolved in 25 mL of 1,3-dimethyl-2-imidazolidinone. 4.79 g of potassium carbonate was added and the mixture was heated and stirred at 180°C for 12 hours, after which the reaction mixture was cooled to room temperature. 100 mL of water was added to the resulting reaction mixture, which was then extracted with 200 mL of ethyl acetate. The resulting organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate, and the solvent was then distilled off. The resulting concentrate was purified by silica gel chromatography to obtain 2.98 g of Intermediate A-1c. [ka]

[0302] 2.00 g of intermediate A-1c was added to a three-neck flask and dissolved in 10 mL of pyridine. 1.22 g of hydroxylamine hydrochloride was added to this mixture and heated and stirred at 50°C for 3 hours. The resulting mixture was cooled to room temperature, and 50 mL of ethyl acetate was added. The resulting organic layer was washed with 1 M hydrochloric acid, saturated aqueous sodium bicarbonate, and saturated brine. This organic layer was dried over anhydrous sodium sulfate, and the solvent was then evaporated. The resulting concentrate was dissolved in 10 mL of tetrahydrofuran and cooled to 0°C in a three-neck flask under a nitrogen atmosphere. 1.0 g of triethylamine was added to this reaction solution, and 0.6 g of acetyl chloride was added dropwise. This reaction solution was stirred at room temperature for 2 hours, and then 50 mL of ethyl acetate was added to the reaction mixture. The resulting organic layer was washed with water, dried over sodium sulfate, and the solvent was evaporated. The resulting solid was reslurried and purified in 6 mL of methanol and then filtered, yielding 0.95 g of compound A-1. The (M+H)(posi) value in the mass spectrum of the obtained compound A-1 was 512. [ka]

[0303] <Production of dispersion liquid> The mixture of the raw materials listed in the table below was mixed and dispersed for 3 hours using a bead mill (zirconia beads 0.1 mm in diameter). Then, a pressure of 2000 kg / cm was applied using a high-pressure disperser NANO-3000-10 equipped with a pressure reducing mechanism (manufactured by Nippon BEE Co., Ltd.). 2 The dispersion treatment was carried out under the conditions of a flow rate of 500 g / min. This dispersion treatment was repeated 10 times to obtain a dispersion liquid. The numerical value of parts by mass of the dispersant is the numerical value converted to solid content.

[0304] [Table 3] [Table 4]

[0305] (colorant) PR264: CI Pigment Red 264 (diketopyrrolopyrrole compound, red pigment) PR254: CI Pigment Red 254 (diketopyrrolopyrrole compound, red pigment) PR291: CI Pigment Red 291 (brominated diketopyrrolopyrrole compound, red pigment) PO71: CI Pigment Orange 71 (diketopyrrolopyrrole compound, orange pigment) PG36: CI Pigment Green 36 (copper phthalocyanine complex, green pigment) PG58: CI Pigment Green 58 (zinc phthalocyanine complex, green pigment) PY129: CI Pigment Yellow 129 (azomethine copper complex, yellow pigment) PY139: CI Pigment Yellow 139 (isoindoline compound, yellow pigment) PY185: CI Pigment Yellow 185 (isoindoline compound, yellow pigment) PY215: CI Pigment Yellow 215 (Puritidine compound, yellow pigment) PB16: CI Pigment Blue 16 (metal-free phthalocyanine compound, blue pigment) PB15:6: CI Pigment Blue 15:6 (copper phthalocyanine complex, blue pigment) IR-1: Compound with the following structure (pyrrolopyrrole compound, infrared absorbing pigment) [ka] TiBk: Titanium black (TiOxNy, black pigment, manufactured by Mitsubishi Materials Corporation) ZrON: Zirconium oxynitride (black pigment)

[0306] (pigment derivatives) Syn-1 to Syn-4: Compounds with the following structures [ka]

[0307] (dispersant) P-1: Resin with the following structure (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units. Weight average molecular weight: 20,000) [ka] P-2: Resin with the following structure (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units. Weight average molecular weight: 28,000) [ka] P-3: Resin with the following structure (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units. Weight average molecular weight: 21,000) [ka] P-4: Resin with the following structure (the number attached to the side chain is the number of repeating units. Weight average molecular weight: 9000) [ka] P-5: Resin with the following structure (the number attached to the side chain is the number of repeating units. Weight average molecular weight: 10,000) [ka]

[0308] (solvent) S-1: Propylene glycol monomethyl ether acetate (PGMEA) S-2: Propylene glycol monomethyl ether (PGME) S-3: Cyclohexanone

[0309] <Production of Photocurable Composition> The following components shown in the table below were mixed in the parts by mass shown in the table below, and then 1 part by mass of 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 0.1 parts by mass of a polymerization inhibitor (p-methoxyphenol) were added and mixed to produce photocurable compositions for each of the examples and comparative examples.

[0310] Surfactant 1: 1 mass % PGMEA solution of KF-6001 (a polydimethylsiloxane modified at both ends with carbinol, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0311] [Table 5] [Table 6] [Table 7] [Table 8] [Table 9]

[0312] Details of the materials indicated by the abbreviations in the table above are as follows:

[0313] (Dispersion) Dispersions R1 to R7, G1 to G5, B1 to B5, I1 to I3, Bk1 to Bk5, TBk1 to TBk5: the above-mentioned dispersions R1 to R7, G1 to G5, B1 to B5, I1 to I3, Bk1 to Bk5, TBk1 to TBk5

[0314] (resin) Ba-1: Resin with the following structure (the numbers attached to the main chain are molar ratios. Acid value: 32 mg KOH / g, weight average molecular weight: 11,000) [ka] Ba-2: Resin with the following structure (the number attached to the main chain is the molar ratio. Weight average molecular weight: 15,000) [ka] Ba-3: Resin with the following structure (the numbers attached to the main chain are molar ratios. The total value of x, y, and z is 50. Weight average molecular weight: 15,000) [ka]

[0315] (polymerizable compound) D-1: KAYARAD DPHA (a 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 (tri- to tetra-functional acrylate compound, manufactured by Toagosei Co., Ltd.) D-5: Light Acrylate DCP-A (bifunctional alicyclic acrylate compound, manufactured by Kyoeisha Chemical Co., Ltd.)

[0316] (Photopolymerization initiator) A-1 to A-70: Compounds A-1 to A-70 shown as specific examples of the specific compounds described above a-1, a-2, a-4: Compounds with the following structures [ka] I-1: Compound having the following structure (comparison compound) [ka]

[0317] (solvent) S-1: Propylene glycol monomethyl ether acetate (PGMEA) S-2: Propylene glycol monomethyl ether (PGME) S-3: Cyclohexanone

[0318] <Sensitivity evaluation> Each photocurable composition immediately after production was applied by spin coating onto an 8-inch (203.2 mm) silicon wafer with an undercoat layer so that the film thickness after application was 0.4 μm, and then heated at 100°C for 2 minutes using a hot plate to form a composition layer. Next, the resulting composition layer was irradiated with light (KrF rays) with a wavelength of 248 nm through a mask having a 0.7 μm square pattern using a KrF scanner exposure machine at an illuminance of 50,000 W / m 2 , exposure amount 30mJ / cm 2 ~200mJ / cm 2 The composition layer was then exposed to light at 23°C for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) as the developer. The exposed composition layer was then subjected to shower development at 23°C for 60 seconds. The layer was then rinsed with pure water by spin shower and heated at 230°C for 2 minutes to form pixels. The exposure dose required for the pixel line width to reach 1.0 μm was calculated, and the sensitivity was evaluated according to the following criteria. -Sensitivity evaluation criteria- A: Exposure dose is 100 mJ / cm 2 is B: Exposure dose 100 mJ / cm 2 exceeding 200mJ / cm 2 is C: Exposure dose 200 mJ / cm2 exceed

[0319] <Evaluation of Adhesion> The photocurable composition immediately after production or the photocurable composition stored at 50°C for 3 months was used, and the exposure dose was 100 mJ / cm 2 Pixels were formed in the same manner as in the sensitivity evaluation, except that the setting was 0.05. The obtained pixels were observed at a magnification of 20,000 times using a scanning electron microscope (S-4800H, manufactured by Hitachi High-Technologies Corporation). The number of peeled pixels was counted out of the total number of pixels (1071 × 1071) formed in a partial region of the observed image. Based on the number of peeled pixels, adhesion was evaluated according to the following criteria. The column "Adhesion 1" in the table below shows the evaluation results of adhesion when a photocurable composition immediately after production was used, and the column "Adhesion 2" shows the evaluation results of adhesion when a photocurable composition after 3 months of storage at 50°C was used. A: The number of peeled pixels is 100 or less B: The number of peeled pixels is more than 100 and less than 200 C: More than 200 peeled pixels

[0320] [Table 10] [Table 11] [Table 12] [Table 13]

[0321] As shown in the above table, in the examples, a film having excellent sensitivity and adhesiveness could be formed.

[0322] In each evaluation, the same effect was obtained even when the exposure light source was changed to i-line (wavelength 365 nm).

Claims

1. A photocurable composition containing a photopolymerization initiator and a polymerizable compound, The photopolymerization initiator is a photocurable composition containing a compound represented by formula (1); 【Chemical 1】 In formula (1), R １ represents a hydrogen atom or a monovalent organic group, X １ ~X ６ are each independently a group represented by formula (R-1), a group represented by formula (R-2), CR ｘ１ or a nitrogen atom, R ｘ１ represents a hydrogen atom or a substituent, X １ ~X ６ At least one of X is a nitrogen atom, and １ ~X ６ at least one of which is a group represented by formula (R-1) or a group represented by formula (R-2); However, X １ , X ３ , X ５ and X ６ Each is independently CR ｘ１ So, X ２ is a nitrogen atom, X ４ is a group represented by formula (R-2); 【Chemistry 2】 In the formula, the wavy line represents a bond. R １０１ and R １０２ each independently represents a monovalent organic group.

2. X in the formula (1) １ or X ２ is a group represented by formula (R-2).

3. The photocurable composition according to claim 1 or 2, further comprising a colorant.

4. The photocurable composition according to claim 1 or 2, further comprising a resin having a graft chain.

5. forming a composition layer on a support using the photocurable composition according to claim 1 or 2; a step of patternwise exposing the composition layer to light having a wavelength of 150 to 300 nm; and developing and removing the unexposed portion of the composition layer.

6. A film obtained by curing the photocurable composition according to claim 1 or 2.

7. An optical filter comprising the film of claim 6.

8. A solid-state imaging device comprising the film according to claim 6.

9. An image display device comprising the film according to claim 6.

10. a photopolymerization initiator containing a compound represented by formula (1); 【Chemistry 3】 In formula (1), R １ represents a hydrogen atom or a monovalent organic group, X １ ~X ６ are each independently a group represented by formula (R-1), a group represented by formula (R-2), CR ｘ１ or a nitrogen atom, R ｘ１ represents a hydrogen atom or a substituent, X １ ~X ６ At least one of X is a nitrogen atom, and １ ~X ６ at least one of which is a group represented by formula (R-1) or a group represented by formula (R-2); However, X １ , X ３ , X ５ and X ６ Each is independently CR ｘ１ So, X ２ is a nitrogen atom, X ４ is a group represented by formula (R-2); 【Chemistry 4】 In the formula, the wavy line represents a bond. R １０１ and R １０２ each independently represents a monovalent organic group.

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